Bicyclic amino derivatives and PGD2, antagonist containing them

Abstract

A compound of the formula (I): wherein: for example, a compound below: wherein:R1 is CH3, H or Na; and X1—X2—X3 is: or its salt or a hydrate thereof is useful as PGD2 antagonist and can be used as a drug for treating diseases in which mast cell dysfunction is involved, for example, systemic mastocytosis and disorder of systemic mast cell activation, and also tracheal contraction, asthma, allergic rhinitis, allergic conjunctivitis, urticaria, injury due to ischemic reperfusion, and as an anti-inflammatory agent. It is particularly useful in the treatment of nasal occlusion.

Description

FIELD OF THE INVENTION

The present invention relates to bicyclic amino derivatives and prostaglandin D 2 (hereinafter, referred to as PGD 2 ) antagonist containing them.

BACKGROUND OF THE INVENTION

Some of bicyclic amino derivatives of the present invention have known to be useful as thromboxane A 2 (TXA 2 ) antagonists (Japanese Patent Publication (KOKOKU) No. 79060/1993). However, the Japanese Patent Publication (KOKOKU) No. 79060/1993 only describes that the compounds are useful as TXA 2 antagonist, and does not suggest the usefulness thereof as PGD 2 antagonist as disclosed by the present invention.

Namely, the TXA 2 is known to have activities such as action against platelet agglutination, thrombogenesis, etc. The TXA 2 antagonist has therefore been considered to be useful as anti-thrombotic agent, and also in the treatment of myocardial infarction or asthma by antagonizing against TXA 2 .

On the other hand, the PGD 2 antagonist of the present invention is useful in the improvement of conditions due to excessive production of PGD 2 . Specifically, it is useful as a drug for treating diseases in which mast cell dysfunction is involved, for example, systemic mastocytosis and disorder of systemic mast cell activation, and also tracheal contraction, asthma, allergic rhinitis, allergic conjunctivitis, urticaria, injury due to ischemic reperfusion, and inflammation.

As is apparent from the above, the TXA 2 antagonist and the PGD 2 antagonist are completely different from each other in terms of the active site, mechanism of action, and application, and have quite different characteristics. Accordingly, it has never been expected that any compound could possess these activities simultaneously.

PGD 2 is produced through PGG 2 and PGH 2 from arachidonic acid by the action of cyclooxygenase activated by immunological or unimmunological stimulation and is the major prostanoid that is produced and released from mast cells. PGD 2 has various potent physiological and pathological activities. For example, PGD 2 can cause strong tracheal contraction, which leads to bronchial asthma, and, in a systemic allergic state, it can dilate the peripheral vessels, which leads to an anaphylactic shock. Especially, much attention has been paid on the idea that PGD 2 is one of the causal substances responsible to the onset of nasal occlusion in the allergic rhinitis. Therefore, it has been proposed to develop an inhibitor against the biosynthesis of PGD 2 or an antagonist of PGD 2 receptor as a drug for the reduction of nasal occlusion. However, the inhibitor of PGD 2 biosynthesis possibly affects greatly the synthesis of prostaglandins in other organisms, and therefore, it is desirable to develop an antagonist (blocker) specific to PGD 2 receptor.

DISCLOSURE OF THE INVENTION

The present inventors have studied intensively to develop PGD 2 receptor antagonists (blockers) specific to PGD 2 receptor, and found that compounds of the formula (I) below or its salt possess a potent activity as PGD 2 receptor antagonist, and are chemically and biochemically stable.

Accordingly, the present invention provides a PGD 2 antagonist which comprises a compound of the general formula (I) below or its salt or a hydrate thereof as an active ingredient:

wherein:

A is alkylene which optionally is intervened by hetero atom or phenylene, contains oxo group, and/or has an unsaturated bond;

B is hydrogen, alkyl, aralkyl or acyl;

R is COOR 1 , CH 2 OR 2 or CON(R 3 )R 4 ;

R 1 is hydrogen or alkyl;

R 2 is hydrogen or alkyl;

R 3 and R 4 each are independently hydrogen, alkyl, hydroxy or alkylsulfonyl;

X 1 is a single bond, phenylene, naphtylene, thiophenediyl, indolediyl, or oxazolediyl;

X 2 is a single bond, —N═N—, —N═CH—, —CH═N—, —CH═N—N—, —CH═N—O—, —C═NNHCSNH—, —C═NNHCONH—, —CH═CH—, —CH(OH)—, —C(Cl)═C(Cl)—, —(CH 2 )n-, ethynylene, —N(R 5 )—, —N(R 51 )CO—, —N(R 52 )SO 2 —, —N(R 53 )CON(R 54 )—, —CON(R 55 )— —SO 2 N(R 56 )—, —O—, —S—, —SO—, —SO 2 —, —CO—, oxadiazolediyl, thiadiazolediyl or tetrazolediyl;

X 3 is alkyl, alkenyl, alkynyl, aryl, aralkyl, heterocyclic group, cycloalkyl, cycloalkenyl, thiazolinylidenemethyl, thiazolidinylidenemethyl, —CH═NR 6 or —N═C(R 7 )R 3 ;

R 5 , R 51 , R 52 , R 53 , R 54 , R 55 and R 56 each are hydrogen or alkyl;

R 6 is hydrogen, alkyl, hydroxy, alkoxy, carbamoyloxy, thiocarbamoyloxy, ureido or thioureido;

R 7 and R 8 each are independently alkyl, alkoxy or aryl;

n is 1 or 2;

Z is —SO 2 — or —CO—; and

m is 0 or 1;

wherein a cyclic substituent may has one to three substituents selected from the group consisting of nitro, alkoxy, sulfamoyl, substituted- or unsubstituted-amino, acyl, acyloxy, hydroxy, halogen, alkyl, alkynyl, carboxy, alkoxycarbonyl, aralkoxycarbonyl, aryloxycarbonyl, mesyloxy, cyano, alkenyloxy, hydroxyalkyl, trifluoromethyl, alkylthio, —N═PPh 3 , oxo, thioxo, hydroxyimino, alkoxyimino, phenyl and alkylenedioxy.

THE BEST EMBODIMENT FOR PRACTICING THE INVENTION

Specific examples of compounds usable as a PGD 2 antagonist above include a compound of the formula (I) wherein:

is

m is 0; and when Z is SO 2 , both X 1 and X 2 are a single bond; X 3 is alkyl, phenyl, naphthyl, stylyl, quinolyl or thienyl; and a cyclic substituent among these substituents optionally has one to three substituents selected from a group consisting of nitro, alkoxy, substituted- or unsubstituted-amino, halogen, alkyl and hydroxyalkyl, or its salt or hydrate thereof.

Similarly, specific examples include a compound of the formula (I) wherein:

when m is 1, both X 1 and X 2 are a single bond; and X 3 is phenyl optionally substituted with halogen, or its salt or hydrate thereof.

Similarly, specific examples include a compound of the formula (I) wherein:

when m is 1, X 1 is phenyl, X 2 is —CH 2 — or —N═N— and X 3 is phenyl, or its salt or hydrate thereof.

Similarly, examples of compounds of the formula (I) include those of the formula (Ia):

wherein A, B, R, X 1 , X 2 and X 3 are as defined above, or its salt or hydrate thereof, provided that those wherein (1) X 1 and X 2 are a single bond, and X 3 is substituted- or unsubstituted-phenyl, or naphthyl; and (2) A is 5-heptenylene, R is COOR 1 (R 1 is hydrogen or methyl), X 1 is 1,4-phenylene, X 2 is a single bond, and X 3 is phenyl are excluded.

Similarly, examples of compounds of the formula (I) include those of the formula (Ib):

wherein:

A, B, R, X 1 , X 2 and X 3 are as defined above, or its salt or hydrate thereof, provided that those wherein X 1 and X 2 are a single bond, and X 3 is phenyl, and wherein X 1 is a single bond, X 2 is —O—, and X 3 is benzyl are excluded.

More specifically, examples of compounds of the formula (I) include those of the formula (Ia) wherein X 1 and X 2 are a single bond, X 3 is isoxazolyl, thiadiazolyl, isothiazolyl, morpholyl, indolyl, benzofuryl, dibenzofuryl, dibenzodioxinyl, benzothienyl, dibenzothienyl, carbazolyl, xanthenyl, phenanthridinyl, dibenzoxepinyl, dibenzothiepinyl, cinnolyl, chromenyl, benzimidazolyl or dihydrobenzothiepinyl, or its salt or hydrate thereof.

Similarly, examples of compounds of the formula (I) include those of the formula (Ia) wherein X 1 is a single bond, X 2 is phenylene, X 3 is alkenyl, alkynyl, —CH═NR 6 or —N═C(R 7 )R 8 , or its salt or hydrate thereof.

Similarly, examples of compounds of the formula (I) include those of the formula (Ia) wherein R is COOR 1 , X 1 is phenylene or thiophenediyl, X 2 is a single bond, —N═N—, —CH═CH—, —CONH—, —NHCO— or ethynylene and X 3 is phenyl, thiazolinylidenemethyl, thiazolidinylidenemethyl or thienyl, or its salt or hydrate thereof.

More specifically, examples of the compound (I) of the present invention include those of the formula (Ib) wherein:

is

or its salt orhydrate thereof. Examples of more preferred compounds include those of the formula (Ib) wherein R is COOR 1 (R 1 is as defined above) or its salt or hydrate thereof.

Similarly, examples of compound (I) include those of the formula (Ib) wherein X 1 is phenylene or thiophenediyl, X 2 is a single bond, —N═N—, —CH═CH—, ethynylene, —O—, —S—, —CO—, —CON(R 55 )— (R 55 is as defined above), —N(R 51 )CO— (R 51 is as defined above) and X 3 is phenyl, or its salt or hydrate thereof.

More specifically, examples of compound (I) include those of the formula (Ib) wherein:

or its salt or hydrate thereof. Examples of more preferred embodiment include those wherein B is hydrogen, both X 1 and X 2 are a single bond, X 3 is thienyl, thiazolyl, thiadiazolyl, isothiazolyl, pyrrolyl, pyridyl, benzofuryl, benzimidazolyl, benzothienyl, dibenzofuryl, dibenzothienyl, quinolyl or indolyl or its salt or hydrate thereof. Similarly, examples include those wherein X 1 is phenylene, thiophenediyl, indolediyl or oxazolediyl, X 2 is a single bond, —N═N—, —CH═CH—, ethynylene, —S— or —O—, and X 3 is aryl or heterocyclic group, or its salt or hydrate thereof.

The compounds of the general formula (Ia) and (Ib) are novel compounds synthesized by the present inventors.

The terms used throughout the present specification are as defined below.

The term “alkyleneu” means C 1 -C 9 straight or branched chain alkylene, for example, methylene, methylmethylene, dimethylmethylene, methylethylmethylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethyene, nonamethylene, or the like. The alkylene above can be intervened by a hetero atom(s) (oxygen, sulfur, nitrogen atom, or the like) or phenylene (e.g., 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, or the like), contain an oxo group, and/or have one or more double- or triple-bonds at any positions on the chain. Examples include —(CH 2 ) 2 —O—CH 2 —, —(CH 2 ) 2 —O—(CH 2 ) 2 —, —(CH 2 ) 2 —O—(CH 2 ) 3 —, —(CH 2 ) 2 —O—(CH 2 ) 4 —, —(CH 2 ) 2 —O—(CH 2 ) 5 —, —(CH 2 ) 2 —O—(CH 2 ) 6 —, —(CH 2 ) 2 —S—(CH 2 ) 2 —, —(CH 2 ) 3 —S—(CH 2 ) 2 —, —CH 2 —S—CH 2 —, —CH 2 —S—(CH 2 ) 4 —, —CH 2 —N(CH 3 )—CH 2 —, —CH 2 —NH—(CH 2 ) 2 —, —(CH 2 ) 2 —N(CH 2 CH 3 )—(CH 2 ) 3 —, —(CH 2 ) 2 -1,4-phenylene-CH 2 —, —(CH 2 ) 2 —O-1,3-phenylene-CH 2 —, —(CH 2 ) 2 —O-1,2-phenylene-CH 2 —, —(CH 2 ) 2 —O-1,4-phenylene-CH 2 —, —CH═CH—S—CH 2 -1,4-phenylene-CH 2 —, —CH═CH—S-1,3-phenylene-(CH 2 ) 2 —, 2-oxopropylene, 3-oxbpentylene, 5-oxohexylene, vinylene, 1-propenylene, 2-propenylene, 1-butenylene, 2-butenylene, 3-butenylene, 1,2-butadienylene, 1,3-butadienylene, 1-pentenylene, 2-pentenylene, 3-pentenylene, 4-pentenylene, 1,2-pentadienylene, 1,3-pentadienylene, 1,4-pentadienylene, 2,3-pentadienylene, 2,4-pentadienylene, 1-hexyenylene, 2-hexenylene, 3-hexenylene, 4-hexenylene, 5-hexenylene, 1,2-hexadienylene, 1,3-hexadienylene 1,4-hexadienylene, 1,5-hexadienylene, 2,3-hexadienylene, 2,4-hexadienylene 2,5-hexadienylene, 3,4-hexadienylene, 3,5-hexadienylene, 4,5-hexadienylen, 1,1-dimethyl-4-hexenylen, 1-heptenylene, 2-heptenylene, 3-heptenylene, 4-heptenylene, 5-heptenylene, 2,2-dimethyl-5-heptenylene, 6-heptenylene, 1,2-heptadienylene, 1,3-heptadienylene, 1,4-heptadienylene, 1,5-heptadienylene, 1,6-heptadienylene, 2,3-heptadienylene, 2,4-heptadienylene, 2,5-heptadienylene, 2,6-heptadienylene, 3,4-heptadienylene, 3,5-heptadienylene, 3,6-heptadienylene, 4,5-heptadienylene, 4,6-heptadienylene or 5,6-heptadienylene, 1-propynylene, 3-butynylene, 2-pentynylene, 5-hexynylene, 6-heptynylene, —(CH 2 )—CH═CH—O—(CH 2 ) 2 —, —CH 2 —S—(CH 2 ) 3 —, —CH 2 -cis-CH═CH-1,2-phenylene-CH 2 —, —CH═CH-1,4-phenylene-(CH 2 ) 2 —, -4-oxo-4,5-hexenylene-, and the like.

The term “alkyl” means C 1 -C 20 straight or branched chain alkyl, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, i-pentyl, neopentyl, t-pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, and the like.

The term “aryl” means C 6 -C 14 monocyclic or condensed ring, for example, phenyl, naphthyl (e.g., 1-naphthyl, 2-naphtyl), anthryl (e.g., 1-anthryl, 2-anthryl, 9-anthryl), phenanthryl (e.g., 2-phenanthryl, 3-phenanthryl, 9-phenanthryl), fluorenyl (e.g., 2-fluorenyl), and the like. Phenyl is especially preferred.

The term “aralkyl” means a group formed by substituting an alkyl as defined above with an aryl above at any substitutable positions on the alkyl. Examples include benzyl, phenethyl, phenylpropyl (e.g., 3-phenylpropyl), naphtylmethyl (e.g., α-naphtylmethyl), anthrylmethyl (e.g., 9-anthrylmethy), phenanthrylmethyl (e.g., 3-phenanthrylmethyl), and the like.

The term “acyl” means C 1 -C 9 acyl derived from aliphatic carboxylic acid, for example, formyl, acetyl, propionyl, butyryl, valeryl, and the like.

The term “alkylsulfonyl” means a group formed by substituting a sulfonyl with an alkyl above, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, and the like.

The term “alkenyl” is C 2 -C 20 straight or branched chain alkenyl, which corresponds to an alkyl above containing one or more double bonds. Examples include vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1,2-butadienyl, 1-pentenyl, 1,2-pentadienyl, 2-hexyenyl, 1,2-hexadienyl, 3-heptenyl, 1,5-heptadienyl, and the like.

The term “alkynyl” is C 2 -C 20 straight or branched chain, alkynyl, which corresponds to an alkyl above containing one or more triple bonds. Examples include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, and the like.

The term “heterocyclic group” means 5-7 membered cyclic group containing one or more hetero atoms selected independently from the group consisting of oxygen, sulfur and/or nitrogen atom on the ring, and is optionally condensed with a carbon ring or other heterocyclic group at any substitutable positions. Examples include pyrrolyl (e.g., 1-pyrrolyl, 3-pyrrolyl), indolyl (e.g., 2-indolyl, 3-indolyl, 6-indolyl), carbazolyl (e.g., 2-carbazolyl, 3-carbazolyl), imidazolyl (e.g., 1-imidazolyl, 4-imidazolyl), pyrazolyl (e.g., 1-pyrazolyl, 3-pyrazolyl), benzimidazolyl (e.g., 2-benzimidazolyl, 5-benzimidazolyl), indazolyl (e.g., 3-indazolyl), indolizinyl (e.g., 6-indolyzinyl), pyridyl (e.g., 2-pyridyl, 3-pyridyl, 4-pyridyl), quinolyl (e.g., 8-quinolyl), isoquinolyl (e.g., 3-isoquinolyl), acridyl (e.g., 1-acridyl), phenanthrydinyl (e.g., 2-phenanthrydinyl, 3-phenanthrydinyl), pyridazinyl (e.g., 3-pydidazinyl), pyrimidinyl (e.g., 4-pyrimidinyl), pyrazinyl (e.g., 2-pyrazinyl), cinnolinyl (e.g., 3-cinnolinyl), phthaladinyl(e.g., 5-phthaladinyl), quinazolinyl (e.g., 2-quinazolinyl), isoxazolyl (e.g., 3-isoxazolyl, 4-isoxazolyl), benzisoxazolyl (e.g., 1,2-benzisoxazol-4-yl, 2,1-benzisoxazol-3-yl), oxazolyl (e.g., 2-oxazolyl, 4-oxazolyl, 5-oxazolyl), benzoxazolyl (e.g., 2-benzoxazolyl), benzoxadiazolyl (e.g., 4-benzoxadiazolyl), isothiazolyl (e.g., 3-isothiazolyl, 4-isothiazolyl) benzisothiazolyl (e.g., 1,2-benzisothiazol-3-yl, 2,1-benzisothizol-5-yl), thiazolyl (e.g., 2-thiazolyl), benzothiazolyl (e.g., 2-benzothiazolyl), thiadiazolyl (e.g., 1,2,3-thiadiazol-4-yl), oxadiazolyl (e.g., 1,3,4-oxadiazol-2-yl), dihydroxadiazolyl (e.g., 4,5-dihydro-1,2,4-oxadiazol-3-yl), furyl (e.g., 2-furyl, 3-furyl), benzofuryl (e.g., 3-benzofuryl), isobenzofuryl (e.g., 1-isobenzofuryl), thienyl (e.g., 2-thienyl, 3-thienyl), benzothienyl (1-benzothiophen-2-yl, 2-benzothiophen-1-yl), tetrazolyl (e.g., 5-tetrazolyl), benzodioxolyl (e.g., 1,3-benzodioxol-5-yl), dibenzofuryl (e.g., 2-dibenzofuryl, 3-dibenzofuryl), dibenzoxepinyl (e.g., dibenz[b,f]oxepin-2-yl), dihydrodibenzoxepinyl (e.g., dihydrodibenz[b,f]oxepin-2-yl, chromenyl (e.g., 2H-chromen-3-yl, 4H-chromen-2-yl), dibenzothiepinyl (e.g., dibenzo[b,f]thiepin-3-yl, dihydrodibenzo[b,f]thiepin-3-yl), morpholinyl (e.g., 1,4-morpholin-4-yl), phenothiadinyl (2-phenothiadinyl), cyclopentathienyl (e.g., cyclopenta[b]thiophen-3-yl), cyclohexathienyl (e.g., cyclohexa[b]thiophen-3-yl), and the like.

The term “cycloalkyl” means C 3 -C 8 cyclic alkyl, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.

The term “cycloalkenyl” means C 3 -C 8 cyclic alkenyl, for example, cyclopropenyl (e.g., 1-cyclopropenyl), cyclobutenyl (e.g., 2-cyclobuten-1-yl), cyclopentenyl (1-cyclopenten-1-yl), cyclohexenyl (1-cyclohexen-1-yl), and the like.

The term “cycloalkyl” means C 1 -C 6 alkoxy, for example, methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, and the like.

Examples of the substituted amino in the definition of “substituted- or un-substituted-amino” include mono- or di-substituted amino such as methylamino, ethylamino, dimethylamino, cyclohexylamino, phenylamino, diphenylamino, or cyclic amino such as piperidino, piperadino or morpholino.

The term “acyloxy” means an acyloxy derived from the “acyl” above, for example, acetyloxy, propionyloxy, butyryloxy, valeryloxy, and the like.

The term “halogen” means fluorine, chlorine, bromine and iodine.

The term “alkoxycarbonyl” means an alkoxycarbonyl group derived from the “alkoxy” above, for example, methoxycarbonyl, ethoxycarbonyl, phenyloxycarbonyl, and the like.

The term “aralkyloxycarbonyl” means an aralkyloxycarbonyl group derived from the “aralkyl” above, for example, benzyloxycarbonyl, phenethyloxycarbonyl, and the like.

The term “aryloxycarbonyl” means an aryloxycarbonyl group derived from the “aryl” above, for example, phenyloxycarbonyl, naphtyloxycarbonyl, and the like.

The term “alkenyloxy” means an alkenyloxy group derived from the “alkenyl” above, for example, vinyloxy, 1-propenyloxy, 2-butenyloxy, and the like.

The term “hydroxyalkyl” means a hydroxyalkyl group derived from the “alkyl” above, for example, hydroxymethyl, hydroxyethyl, hydroxypropyl, and the like.

The term “alkylthio” means an alkylthio group derived from the “alkyl” above, for example, methylthio, ethylthio, propylthio, and the like. The term “alkylenedioxy” means C 1 -C 3 alkylenedioxy, for example, methylenedioxy, ethylenedioxy, propylenedioxy, and the like.

In the case of “phenylene, “naphtylene”, “thiophenediyl”, “indolediyl”, “oxazolediyl”, “oxadiazolediyl” and tetrazolediyl”, the said group can bind to the neighboring groups at any two substitutable sites.

In the definitions above, when a substituent(s) is cyclic, it may be substituted by one to three substituents selected from nitro, alkoxy, sulfamoyl, substituted- or un-substituted-amino, acyl, acyloxy, hydroxy, halogen, alkyl, alkynyl, carboxy, alkoxycarbonyl, aralkoxycarbonyl, aryloxycarbonyl, mesyloxy, cyano, alkenyloxy, hydroxyalkyl, trifluoromethyl, alkylthio, —N═PPh 3 , oxo, thioxo, hydroxyimino, alkoxyimino, phenyl and alkylenedioxy. The substituent(s) may bind to any substitutable positions on the ring.

Examples of salts of the compound (I) include those formed with an alkali metal (e.g., lithium, sodium or potassium), an alkali earth metal (e.g., calcium), an organic base (e.g., tromethamine, trimethylamine, triethylamine, 2-aminobutane, t-butylamine, diisopropylethylamine, n-butylmethylamine, cyclohexylamine, dicyclohexylamine, N-isopropylcyclohexylamine, furfurylamine, benzylamine, methylbenzylamine, dibenzylamine, N,N-dimethylbenzylamine, 2-chlorobenzylamine, 4-methoxybenzylamine, 1-naphthylenemethylamine, diphenylbenzylamine, triphenylamine, 1-naphthylamine, 1-aminoanthoracene, 2-aminoanthoracene, dehydroabiethylamine, N-methylmorpholine or pyridine), an amino acid (e.g., lysine, or arginine), and the like.

The term “hydrate” means a hydrate of the compound of the formula (I) or its salt. Examples include mono- and dihydrates.

The present compounds are shown by the formula (I) and are inclusive of the form of any types of stereoisomers (e.g., diastereomer, epimer, enantiomer) and racemic compounds.

Among the compounds of the general formula (I), those wherein m=1, especially, those shown in Tables 3b and 3c below are known compounds described in Japanese Patent Publication (KOKAI) No. 180862/1990.

Among the compounds of the general formula (I), those wherein m=0, [i.e., those shown by the general formula (I′)], can be prepared by reacting an amino compound of the general formula (II) with a reactive derivative of sulfonic acid or carboxylic acid corresponding to the partial structure: Z—X 1 —X 2 —X 3 as shown below.

Wherein A, B, R, X 1 , X 2 , X 3 , Y and Z are as defined above.

A sulfonic acid corresponding to the partial structure: Z—X 1 —X 2 —X 3 is a compound of the general formula X 3 —X 2 —X 1 —SO 2 OH and a carboxylic acid corresponding to the said partial structure is a compound of the general formula X 3 —X 2 —X 1 —COOH. Reactive derivative of these sulfonic or carboxylic acids means a corresponding halide (e.g., chloride, bromide, iodide), acid anhydride (e.g., mixed acid anhydride with formic acid or acetic acid), active ester (e.g., succinimide ester), and examples thereof generally include acylating agents used for the acylation of amino group. The carboxylic acid X 3 —X 2 —X 1 —COOH can be used in the reaction as it is without converting into a reactive derivative, in the presence of a condensing agent (e.g., dicyclohexylcarbodiimide (DCC), 1-ethyl-3-(3-dimetylaminopropyl)carbodiimide, N,N′-carbonyldiimidazole) which are used in the condensing reaction between amine and carboxylic acid.

The reaction can be conducted under the conditions generally used for the. acylation of amino group. For example, in the case of condensation using an acid halide, the reaction is carried out using a solvent such as an ether solvent (e.g., diethylether, tetrahydrofuran, dioxane), benzene solvent (e.g., benzene, toluene, xylene), halogenated hydrocarbon solvent (e.g., dichloromethane, dichloroethane, chloroform), ethyl acetate, dimethylformamide, dimethyl sulfoxide, acetonitrile, or the like, if necessary, in the presence of a base (e.g., organic base such as triethylamine, pyridine, N,N-dimethylaminopyridine, N-methylmorpholine; inorganic base such as sodium hydroxide, potassium hydroxide, potassium carbonate, or the like) under cooling, at room temperature or under heating, preferably at temperature ranging from −20° C. to a temperature under cooling, or from room temperature to a refluxing temperature of the reaction system, for several min to several hr, preferably for 0.5 hr to 24 hr, more preferably, for 1 hr to 12 hr.

The reaction conditions for the reaction between other reactive derivative or a free acid and an amine (II) can be determined in a conventional manner depending on the characteristics of the respective reactive derivative or free acid.

The reaction product can be purified by conventional purification methods, for example, the extraction with a solvent, chromatography, recrystallization, or the like.

Specific examples of the compound (II) as a starting material for the present method are as follows. Examples of 3-amino[2.2.1]bicyclic compound include 7-(3-aminobicyclo[2.2.1]hept-2-yl)-5-heptenoic acid, 7-(3-aminobicyclo[2.2.1]hept-2-yl)-2,2-dimethyl-5-heptenoic acid, 7-(N-metnyl-3-aminobicyclo[2.2.1]hept-2-yl)-5-heptenoic acid, 6-(3-aminobicyclo[2.2.1]hept-2-yl)-5-hexenoic acid. Specific examples of 2-amino-6,6-dimethyl[3.1.1]bicyclic compound include 7-(2-amino-6,6-dimethylbicyclo[3.1.1]hept-3-yl)-5-heptenoic acid. In these starting compounds, the heptenoic acid chain may be saturated to form heptanoic acid chain, intervened by a hetero atom(s) or a hetero group(s) such as —O—, —S—, —NH—, or a phenylene(s), or substituted with an oxo group. Examples of such compounds include 7-(3-aminobicyclo[2.2.1]hept-2-yl)heptanoic acid, 4-[2-(2-aminobicyclo[3.1.1]hept-3-yl)ethoxyphenylacetic acid, 7-(3-aminobicyclo[2.2.1]hept-2-yl)-6-oxo-heptanoic acid. These starting compounds are either described in the Japanese Patent Publication (KOKOKU) No. 79060/1993 or 23170/1991, or can be prepared according to the method described therein.

Sulfonic acid X 3 —X 2 —X 1 —SO 2 OH and carboxylic acid X 3 —X 2 —X 1 —COOH corresponding to the partial structure Z—X 1 —X 2 —X 3 mean a sulfonic acid or carboxylic acid having substituents corresponding to the Xs above. That is, examples include alkane-sulfonic acid or -carboxylic acid, alkene-sulfonic acid or -carboxylic acid, alkyne-sulfonic acid or -carboxylic acid, cycloalkane-sulfonic acid or -carboxylic acid, cycloalkene-sulfonic acid or -carboxylic acid, aryl-sulfonic acid or -carboxylic acid, aralkyloxy-sulfonic acid or -carboxylic acid, heterocyclic-substituted-sulfonic acid or -carboxylic acid, heteroarylalkyl-sulfonic acid or -carboxylic acid, and substituted-amino-sulfonic acid or -carboxylic acid. Each of sulfonic and carboxylic acids may have a substituent(s) above. These sulfonic acids and carboxylic acids are commercially available or can be easily synthesized from a known compound(s) in accordance with a known method. Upon reaction, the sulfonic or carboxylic acid can be converted into the corresponding reactive derivative above, if necessary. For example, when an acid halide is needed, the compound is reacted with thionyl, halide (e.g., thionyl chloride), phosphorous halide (e.g., phosphorous trichloride, phosphorous pentachloride) or oxalyl halide (e.g., oxalyl chloride) in accordance with a known method such as those described in a literature (e.g., Shin-Jikken-Kagaku-Koza, vol. 14, pp. 1787 (1978); Synthesis, 852-854 (1986); Shin-Jikken-Kagaku-Koza, vol. 22, pp. 115 (1992)). The other reactive derivatives can also be prepared in accordance with a known method.

Among the objective compounds (I), those wherein the side chain A contains an unsaturated bond, especially, a double bond, can also be prepared by reacting an aldehyde derivative of the general formula (III) below with an ylide compound corresponding to the rest part of the side chain A—R under the conditions for the Wittig reaction:

wherein A, B, R, X 1 , X 2 , X 3 , Y and Z are as defined above.

The starting compound (III) can be prepared in accordance with a method described in, for example, Japanese Patent Publication (KOKAI) No. 256650/1990. Further, an ylide compound corresponding to the rest part of the side chain A—R can be synthesized by reacting triphenylphosphine with a corresponding halogenated alkanoic acid, or an ester derivative, ether derivative or amide derivative thereof in the presence of a base according to a known method.

Among the objective compounds (I), those wherein R is COOH can be converted into a corresponding ester derivative, alcohol fare derivative, ether derivative, amide derivative, if desired. For example, ester derivatives can be prepared by esterifying a carboxylic acid in a conventional manner. An ester derivative, when reduced, gives an alcohol derivative, and amidated, gives an amide derivative. An ether derivative can be obtained by O-alkylating an alcohol derivative.

The compound (I) of the present invention shows antagonistic effect against PGD 2 in vitro through the binding to PGD 2 receptor, and is useful as a drug for treating diseases in which mast cell dysfunction due to excessive production of PGD 2 is involved. For example, the compound (I) is useful as a drug for treating diseases, such as systemic mastocytosis and disorder of systemic mast cell activation, and also tracheal contraction, asthma, allergic rhinitis, allergic conjunctivitis, urticaria, injury due to ischemic reperfusion, and inflammation. The compound (I) shows preventive effect on nasal occlusion in vivo, and therefore is especially useful as a drug for treating them.

When using a compound (I) of the present invention in treatment, it can be formulated into ordinary formulations for oral and parenteral administration. A pharmaceutical composition containing a compound (I) of the present invention can be in the form for oral and parenteral administration. Specifically, it can be formulated into formulations for oral administration such as tablets, capsules, granules, powders, syrup, and the like; those for parenteral administration such as injectable solution or suspension for intravenous, intramuscular or subcutaneous injection, inhalant, eye drops, nasal drops, suppositories, or percutaneous formulations such as ointment.

In preparing the formulations, carriers, excipients, solvents, and bases known to one ordinary skilled in the art may be used. In case of tablets, they are prepared by compressing or fomulating an active ingredient together with auxiliary components. Examples of usable auxiliary components include pharmaceutically acceptable excipients such as binders (e.g. cornstarch), fillers (e.g., lactose, microcrystalline cellulose), disintegrants (e.g., starch sodium glycolate) or lubricants (e.g., magnesium stearate). Tablets may be coated appropriately. In the case of liquid formulations such as syrups, solutions, or suspensions, they may contain suspending agents (e.g., methyl cellulose), emulsifiers (e.g., lecithin), preservatives, and the like. In the case of injectable formulations, it may be in the form of solution or suspension, or oily or aqueous emulsion, which may contain suspension-stabilizing agent or dispensing agent, and the like. In the case of an inhalant, it is formulated into a liquid formulation applicable to an inhaler. In the case of eye drops, it is formulated into a solution or a suspension. Especially, in the case of nasal drug for treating nasal occlusion, it can be used as a solution or suspension prepared by a conventional formulating method, or as a powder formulated using a powdering agent (e.g., hydroxypropyl cellulose, carbopole), which are administered into the nasal cavity. Alternatively, it can be used as an aerosol after filling into a special container together with a solvent of lowboiling point.

Although an appropriate dosage of the compound (I) varies depending on the administration route, age, body weight, sex, or conditions of the patient, and the kind of drug(s) used together, if any, and should be determined by the physician in the end, in the case of oral administration, the daily dosage can generally be between about 0.01-100 mg, preferably about 0.01-10 mg, more preferably about 0.1-10 mg, per kg body weight. In the case of parenteral administration, the daily dosage can generally be between about 0.001-100 mg, preferably about 0.001-1 mg, more preferably about 0.01-1 mg, per kg body weight. The daily dosage can be administered in 1-4 divisions.

The following Examples are provided to further illustrate the present invention and are not to be construed as limiting the scope thereof.

EXAMPLE 1

Methyl (Z)-7-[(1S,2R,3R,4R)-3-aminobicyclo[2.2.1]hept-2-yl]-5-heptenoate (II-1) (251 mg, 1.00 mmol) was dissolved inmethylene chloride (8 ml) and triethylamine (0.238 ml, 2.00 mmol) was added thereto under a nitrogen atmosphere. To the mixture was added 2-chlorosulfonyldibenzofuran (350 mg, 1.31 mmol) under ice-cooling, and the mixture was stirred for 30 min and allowed to warm up to room temperature. The reaction mixture was purified by column chromatography on silica gel (n-hexane/ethyl acetate (1:4)) and recrystallized from n-hexane (10 ml) to yield methyl (Z)-7-[(1S,2R,3R,4R)-3-(2-dibezofuryl)sulfonylaminobicyclo[2.2.1]hept-2-yl]-5-heptenoate (1a-1) (342 mg, 0.710 mmol). Yield 71 %, mp 115-116° C.

Elemental analysis (C 27 H 31 NO 5 S) Calcd. (%): C, 67.34; H, 6.49; N, 2.91; S, 6.66 Found (%): C, 67.16; H, 6.47 ; N, 2.99; S, 6.66

IR (CHCl 3 ): 3382,3024,2952,2874,1726,1583,1465,1442,1319,1245,1154,1121,1104,1071,1019,890,840,817/cm.

1 H NMR(CDCl 3 ) δ: 0.94-1.92(14H,m),2.15-2.24(3H,m),2.99-3.07(1H,m), 3.66(3H,s),4.98(1H,d,J=6.6 Hz),5.10-5.22(2H,m),7.39-7.46(1H,m),7.51-7.70(3H,m),7.87-8.13(2H,m),8.53(1H,d,J=2.1 Hz)

[α] D =−0.6° (CHCl 3 ,c=1.01%,23° C.).

([α] 365 =+37.0° (CHCl 3 ,c=1.01%,23° C.).

Methyl (Z)-7-[(1S,2R,3R,4R)-3-(2-dibezofuryl)sulfonylaminobicyclo[2.2.1]hept-2-yl]-5-heptenoate (1a-1) (234 mg, 0.50 mmol) was dissolved in methanol (6 ml)/tetrahydrofuran (4 ml). To the solution was added 1 N potassium hydroxide (1.50 ml, 1.50 mmol)under ice-cooling. After the reaction mixture was warmed up to room temperature, it was allowed to react for 16 hr and concentrated to remove the solvent. To the residue were added ethyl acetate (50 ml) and water (10 ml), and then 1 N HCl (2.00 ml, 2.00 mmol), and the organic layer was separated. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate and concentrated. The residue was purified by column chromatography on silica gel (n-hexane/ethyl acetate (1:1) containing 0.2 % acetic acid) to yield (Z)-7-[(1S,2R,3R,4R)-3-(2-dibezofuryl)sulfonylaminobicyclo[2.2.1]hept-2-yl]-5-heptenoic acid (1a-2) (203 mg, 0.434 mmol). Yield 87 %, oil.

IR (CHCl 3 ): 3266, 3026, 2952, 2874, 1708, 1465, 1443, 1423, 1319, 1267, 1245, 1153, 1121, 1104, 1072, 906/cm.

1 H NMR(CDCl 3 ) δ: 0.93-1.94(14H,m),2.12-2.19(1H,m), 2.26(2H,t, J=7.2 Hz), 3.00-3.08(1H,m),5.12-5.25(2H,m), 5.26(1H,d,J=6.6 Hz), 7.38-7.45(1H,m),7.51-7.70(3H,m),7.87-8.13(2H,m), 8.54(1H,d, J=2.1 Hz).

[α] D =+6.8° (CHCl 3 ,c=1.08 %, 23° C.).

(Z)-7-[(1S,2R,3R,4R)-3-(2-Dibezofuryl)sulfonylamino-bicyclo[2.2.1]hept-2-yl]-5-heptenoic acid (1a-2) (453 mg, 0.97 mmol) was dissolved in methanol (5 ml). After addition of 1 N sodium methoxide/methanol (1.034 N, 0.937 ml, 0.97 mmol), the mixture was allowed to warm up to room temperature and to react for 1 hr. The solvent was removed by distillation to yield the sodium salt (1a-3) (457 mg, 0.933 mmol). Yield 96 %. Amorphous powder.

Elemental analysis (C 26 H 28 NO 5 SNa 0.6H 2 O) Calcd.(%): C,62.41;H,5.88;N,2.80;S,6.41;Na,4.59 Found (%): C,62.45;H,5.92;N,2.99;S,6.49;Na,4.46

IR (KBr): 434, 3280, 3074, 3007, 2952, 2873, 1566, 1467, 1444, 1417, 1344, 1315, 1270, 1248, 1200, 1189, 1154, 1124, 1107, 1075, 1058, 895, 842, 818/cm.

1 H NMR(CD 3 OD) δ: 1.02-2.05(16H, m), 2.16-2.23(1H, m), 2.94-3.00(1H, m), 4.98-5.05(2H, m), 7.41-7.48(1H, m), 7.53-7.62(1H, m), 7.66(1H, d, J=8.4 Hz), 7.77(1H, d, J=8.4 Hz), 8.57(1H, d, J=2.1 Hz).

[α] D =−15.2° (CH 3 OH, c=1.07%, 22° C.).

EXAMPLE 2

Methyl (Z)-7-[(1S,2R,3R,4R)-3-aminobicyclo[2.2.1]hept-2-yl]-5-heptenoate trifrluroroacetate (II-2) (232 mg, 0.636 mmol), which was prepared by the method described in Reference Example 4 of the Japanese Patent Publication (KOKOKU) No.79060/1993, was dissolved in methylenechloride (5ml). To the solution were added triethylamine (0.279 ml, 2.00 mmol) and 4-biphenylcarbonyl chloride under ice-cooling and stirred for 7 hr at the same temperature. The reaction mixture was purified by column chromatography on silica gel (ethyl acetate/n-hexane (1:4)) to yield methyl (Z)-7-[(1S,2R,3R,4R)-3-(4-biphenyl)carbonylaminobicyclo[ 2.2.1]hept-2-yl]-5-heptenoate (1k-11) (221 mg, 0.512 mmol). The compound (1k-11) (190 mg, 0.440 mmol) was dissolved in methanol (6 ml). To the solution was added 1 N KOH (1.10 ml, 1.10 mmol) under ice-cooling and stirred for 15 hr at room temperature. The reaction mixture was concentrated in vacuo. The residue, after the addition of water (20 ml) and 1 N HCl (2 ml), was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate and concentrated. The residue was purified by column chromatography on silica gel (ethyl acetate/hexane (1:1) containing 0.3% acetic acid) to yield (Z)-7-[(1S,2R,3R,4R)-3-(4-biphenyl)carbonylaminobicyclo[2.2.1]hept-2-yl]-5-heptenoic acid (1k-12) (172 mg, 0.412 mmol). Yield 94%.

The following compounds can also be prepared in the following manner.

EXAMPLE 3

To a suspension of 4-carboxybutyltriphenylphosphonium bromide (14.8 g, 33.3 mmol) and tetrahydrofuran (80 ml) was added potassium t-butyrate (7.55 g, 67.3 mmol) at room temperature under a nitrogen atmosphere. After stirring for 1 hr at room temperature, the mixture was cooled to −20° C. and a solution of N-[ (1S,2S,3S,4R)-3-formylmethylbicyclo[2.2.1]hept-2-yl]benzenesulfonamide (III-1) (Japanese Patent Publication (KOKAI) No. 256650/1990, Reference Example 2) (3.25 g, 11.1 mmol) in tetrahydrofuran (20 ml) was added slowly. After stirring for about 1 hr at −20° C., the ice bath was removed and the mixture was further stirred for 1 hr. To the reaction solution was added 2 N HCl and the mixture was extracted with ethyl acetate, washed with water and brine, and concentrated. After the addition of toluene and 1 N sodium hydroxide to the resultant crude product, aqueous layer was separated. The organic layer was washed with water again and the washing was combined with the previously obtained aqueous layer. After the addition of 2 N HCl, the aqueous solution was extracted with ethyl acetate. The extract was washed with water and brine, dried over sodium sulfate, and concentrated. The residue was purified by column chromatography on silica gel to obtain calcium (Z)-7-[(1R,2S,3S,4S)-3-phenylsulfonylaminobicyclo[2.2.1]hept-2-yl]-5-heptenoate (1d-1) (3.29 g, yield 79%, mp 62° C.).

Elemental analysis (C 20 H 27 NO 4 S) Calcd.(%): C, 63.63; H, 7.21; N, 3.71; S, 8.49 Found (%): C, 63.56; H, 7.21; N, 3.83; S, 8.43

[α] D =+5.3±0.5° (CHCl 3 , c=1.003%, 22° C.)

[α] D =+27.1 ±0.70 (MeOH, c=1.015% 24° C.)

IR(Nujol) 3282, 3260, 3300, 2400, 1708, 1268, 1248, 1202, 1162, 1153, 1095, 1076/cm.

1 H NMR δ0.88-2.10(m,14H), 2.14(br S, 1H), 2.34(t, J=7.2 Hz, 2H), 2.95-3.07(m, 1H), 5.13-5.35(m, 3H), 7.45-7.64(m, 3H), 7.85-7.94(m, 2H), 9.52(brS, 1H).

Compounds prepared in accordance with a method described in Examples above are shown in Tables below.

TABLE 1a
No.	R 1	X 1 —X 2 —X 3
1a-1 1a-2 1a-3	CH 3 H Na
1a-4 1a-5	CH 3 H
1a-6 1a-7	CH 3 H
1a-8 1a-9	CH 3 H
1a-10 1a-11	CH 3 H
1a-12 1a-13	CH 3 H
1a-14 1a-15	CH 3 H
1a-16 1a-17	CH 3 H
1a-18 1a-19	CH 3 H
1a-20 1a-21	CH 3 H
1a-22	H
1a-23	H
1a-24 1a-25 1a-26	CH 3 H Na
1a-27 1a-28 1a-29	CH 3 H Na
1a-30 1a-31	CH 3 H
1a-32 1a-33	CH 3 H
1a-34	CH 3
1a-35 1a-36	CH 3 H
1a-37 1a-38	CH 3 H
1a-39 1a-40	CH 3 H
1a-41	H
1a-42 1a-43	CH 3 H
1a-44 1a-45	CH 3 H
1a-46 1a-47 1a-48	CH 3 H Na
1a-49 1a-50	CH 3 H
1a-51 1a-52	CH 3 H
1a-53 1a-54	CH 3 H
1a-55 1a-56	CH 3 H
1a-57 1a-58	CH 3 H
1a-59 1a-60	CH 3 H
1a-61 1a-62	CH 3 H
1a-63 1a-64	CH 3 H
1a-65 1a-66	CH 3 H
1a-67 1a-68	CH 3 H
1a-69 1a-70	CH 3 H
1a-71 1a-72	CH 3 H
1a-73 1a-74	CH 3 H
1a-75 1a-76	CH 3 H
1a-77 1a-78	CH 3 H
1a-79	H
1a-80 1a-81	CH 3 H
1a-82 1a-83	CH 3 H
1a-84	H
1a-85	H
1a-86	H
1a-87	H
1a-88 1a-89	CH 3 H
1a-90 1a-91	CH 3 H
1a-92 1a-93	CH 3 H
1a-94	H
1a-95	H
1a-96	H
1a-97	H
1a-98 1a-99	H Na
1a-100 1a-101	CH 3 H
1a-102	CH 3
1a-103 1a-104	CH 3 H
1a-105 1a-106	CH 3 H
1a-107 1a-108	CH 3 H
1a-109 1a-110	CH 3 H
1a-111 1a-112	CH 3 H
1a-113 1a-114	CH 3 H
1a-115 1a-116 1a-117 1a-118	CH 3 H Na i-Pr
1a-119 1a-120 1a-121	CH 3 Na H
1a-122 1a-123	CH 3 H
1a-124	CH 3
1a-125 1a-126	CH 3 H
1a-127 1a-128	CH 3 H
1a-129	CH 3
1a-130 1a-131	CH 3 H
1a-132 1a-133	CH 3 H
1a-134	H
1a-135 1a-136	CH 3 H
1a-137 1a-138	CH 3 H
1a-139 1a-140	CH 3 H
1a-141 1a-142	CH 3 H
1a-143	H
1a-144	H
1a-145	H
1a-146	H
1a-147	H
1a-148	H
1a-149	H
1a-150	H
1a-151	H
1a-152	H
1a-153	H
1a-154	H
1a-155	H
1a-156	H
1a-157	H
1a-158	H
1a-159	H
1a-160	H
1a-161	H
1a-162	H
1a-163	H
1a-164	H
1a-165	H
1a-166	H
1a-167	H
1a-168	H
1a-169	H
1a-170	H
1a-171 1a-172	CH 3 H
1a-173	H
1a-174	H
1a-175 1a-176	CH 3 H
1a-177 1a-178	CH 3 H
1a-179 1a-180	CH 3 H
1a-181	H
1a-182 1a-183	CH 3 H
1a-184	H
1a-185	H
1a-186 1a-187	CH 3 H
1a-188 1a-189	CH 3 H
1a-190 1a-191	CH 3 H
1a-192 1a-193	CH 3 H
No.	X 1 —X 2 —X 3
1a-194
1a-195
1a-196
1a-197
1a-198
1a-199
1a-200
1a-201
1a-202
1a-203
1a-204
1a-205
1a-206
1a-207
1a-208
1a-209
1a-210
1a-211
1a-212
1a-213
1a-214
1a-215
1a-216
1a-217
1a-218
1a-219
1a-220
1a-221
1a-222
1a-223
1a-224
1a-225
1a-226
1a-227
1a-228
1a-229
1a-230
1a-231
1a-232
1a-233
1a-234
1a-235
1a-236
1a-237
1a-238
1a-239
1a-240
1a-241
1a-242
1a-243
1a-244
1a-245
1a-246
1a-247
1a-248
1a-249
1a-250
1a-251
1a-252
1a-253
1a-254
1a-255
1a-256
1a-257
1a-258
1a-259
1a-260
1a-261
1a-262
1a-263
1a-264
1a-265
1a-266
1a-267
1a-268
1a-269
1a-270
1a-271
1a-272
1a-273
1a-274
1a-275
1a-276
1a-277
1a-278
1a-279
1a-280
1a-281
1a-282
1a-283
1a-284
1a-285
1a-286
1a-287
1a-288
1a-289
1a-290
1a-291
1a-292
1a-293
1a-294
1a-295
1a-296
1a-297
1a-298
1a-299
1a-300
1a-301
1a-302
1a-303
1a-304
1a-305

TABLE 1b
No.	R 1	X 1 —X 2 —X 3
1b-1	CH 3
1b-2	CH 3
1b-3	H
1b-4	H
1b-5	H
1b-6	H
1b-7	H
1b-8	H
1b-9	H
1b-10	H
1b-11	H
1b-12	H
1b-13	H
1b-14	H
1b-15	H

TABLE 1c
No.	R 1	X 1 —X 2 —X 3
1c-1	CH 3
1c-2	CH 3
1c-3	K
1c-4	H
1c-5	H
1c-6	H
1c-7	H
1c-8	H
1c-9	H
1c-10	H
1c-11	H
1c-12	H

TABLE 1d
No.	R 3	R 4	X 1 —X 2 —X 3
1d-1	H	SO 2 CH 3
1d-2 1d-3 1d-4	H H H	H OH SO 2 CH 3
1d-5	H	SO 2 CH 3
1d-6	H	SO 2 CH 3
1d-7	H	SO 2 CH 3
1d-8	H	SO 2 CH 3
1d-9	H	SO 2 CH 3
1d-10	H	SO 2 CH 3
1d-11	H	SO 2 CH 3
1d-12	H	SO 2 CH 3
1d-13	H	SO 2 CH 3
1d-14	H	SO 2 CH 3
1d-15	H	SO 2 CH 3

TABLE 1e
No.	R 1	X 1 —X 2 —X 3
1e-1	H
1e-2	H
1e-3	H
1e-4	H
1e-5	H
1e-6	H
1e-7	H
1e-8	H
1e-9	H
1e-10	H

TABLE 1f
No.	R 2	X 1 —X 2 —X 3
1f-1	H
1f-2	H
1f-3	H
1f-4	H
1f-5	H
1f-6	H
1f-7	H
1f-8	H
1f-9	H
1f-10	H

TABLE 1g
No.	R 1	X 1 —X 2 —X 3
1g-1	H
1g-2	H
1g-3	H
1g-4	H
1g-5	H
1g-6	H
1g-7	H
1g-8	H
1g-9	H
1g-10	H
1g-11	H

TABLE 1h
No.	R 1	X 1 —X 2 —X 3
1h-1	H
1h-2	H
1h-3	H
1h-4	H
1h-5	H
1h-6	H
1h-7	H
1h-8	H
1h-9	H
1h-10	H

TABLE 1i
No.	R 2	X 1 —X 2 —X 3
1i-1	H
1i-2	H
1i-3	H
1i-4	H
1i-5	H
1i-6	H
1i-7	H
1i-8	H
1i-9	H
1i-10	H
1i-11	H
1i-12	H

TABLE 1j
No.	R 1	X 1 —X 2 —X 3
1j-1 1j-2 1j-3	CH 3 H Na
1j-4 1j-5	H CH 3
1j-6 1j-7	CH 3 H
1j-8	CH 3
1j-9 1j-10	CH 3 H
1j-11 1j-12	CH 3 H
1j-13 1j-14	CH 3 H
1j-15 1j-16	CH 3 H
1j-17	H
1j-18 1j-19	CH 3 H
1j-20 1j-21	CH 3 H
1j-22	H
1j-23 1j-24	CH 3 H
1j-25 1j-26	CH 3 H
1j-27	H
1j-28 1j-29	CH 3 H
1j-30	H
1j-31	H
1j-32	H
1j-33	H
1j-34	H
1j-35	H
1j-36	H
1j-37	H
1j-38	H

TABLE 1k
No.	R 1	X 1 —X 2 —X 3
1k-1	H
1k-2 1k-3	CH 3 H
1k-4	H
1k-5	H
1k-6	H
1k-7	H
1k-8	H
1k-9	H
1k-10	H
1k-11	CH 3
1k-12	H
1k-13	H
1k-14	H
1k-15	H
1k-16	H
1k-17	H
1k-18	H
1k-19	H
1k-20	H

TABLE 1m
No.	R 1	X 1 —X 2 —X 3
1m-1 1m-2	CH 3 H
1m-3 1m-4	CH 3 H
1m-5 1m-6	CH 3 H
1m-7 1m-8	CH 3 H
1m-9 1m-10	CH 3 H
1m-11 1m-12	CH 3 H
1m-13 1m-14	CH 3 H
1m-15 1m-16	CH 3 H
1m-17 1m-18	CH 3 H
1m-19 1m-20	CH 3 H
1m-21	H
1m-22	H
1m-23 1m-24	CH 3 H
1m-25 1m-26	CH 3 H
1m-27 1m-28	CH 3 H
1m-29 1m-30	CH 3 H
1m-31	H
1m-32	H
1m-33	H
1m-34	H
1m-35	H
1m-36	H
1m-37	H
1m-38	H
1m-39	H
1m-40	H

TABLE 2a
No.	R 1	X 1 —X 2 —X 3
2a-1 2a-2	CH 3 H
2a-3 2a-4 2a-5	CH 3 H Na
2a-6 2a-7	CH 3 H
2a-8 2a-9	CH 3 H
2a-10 2a-11	CH 3 H
2a-12 2a-13	CH 3 H
2a-14 2a-15	CH 3 H
2a-16 2a-17	CH 3 H
2a-18 2a-19	CH 3 H
2a-20 2a-21 2a-22	CH 3 H Na
2a-23 2a-24	CH 3 H
2a-25 2a-26	CH 3 H
2a-27 2a-28	CH 3 H
2a-29 2a-30	CH 3 H
2a-31	CH 3
2a-32 2a-33	CH 3 H
2a-34 2a-35	CH 3 H
2a-36 2a-37	CH 3 H
2a-38 2a-39	CH 3 H
2a-40 2a-41	CH 3 H
2a-42 2a-43	CH 3 H
2a-44 2a-45	CH 3 H
2a-46 2a-47	CH 3 H
2a-48 2a-49	CH 3 H
2a-50 2a-51	CH 3 H
2a-52 2a-53	CH 3 H
2a-54 2a-55	CH 3 H
2a-56 2a-57	CH 3 H
2a-58 2a-59	CH 3 H
2a-60 2a-61	CH 3 H
2a-62 2a-63	CH 3 H
2a-64 2a-65	CH 3 H
2a-66 2a-67	CH 3 H
2a-68 2a-69	CH 3 H
2a-70 2a-71	CH 3 H
2a-72 2a-73	CH 3 H
2a-74 2a-75	CH 3 H
2a-76 2a-77	CH 3 H
2a-78 2a-79	CH 3 H
2a-80 2a-81	CH 3 H
2a-82 2a-83	CH 3 H
2a-84 2a-85	CH 3 H
2a-86 2a-87	CH 3 H
2a-88 2a-89	CH 3 H
2a-90 2a-91	CH 3 H
2a-92 2a-93	CH 3 H
2a-94 2a-95 2a-96 2a-97	CH 3 H Na Ca ½
2a-98 2a-99	CH 3 H
2a-100 2a-101	CH 3 H
2a-102 2a-103	CH 3 H
2a-104 2a-105	CH 3 H
2a-106 2a-107	CH 3 H
2a-108 2a-109 2a-110	CH 3 H Na
2a-111 2a-112	CH 3 H
2a-113 2a-114	CH 3 H
2a-115 2a-116	CH 3 H
2a-117 2a-118	CH 3 H
2a-119	H
2a-120	H
2a-121	H
2a-122	H
2a-123	H
2a-124	H
2a-125	H
2a-126	H
2a-127	H
2a-128	H
2a-129	H
2a-130	H
2a-131	H
2a-132	H
2a-133	H
2a-134	H
2a-135	H
2a-136	H
2a-137	H
2a-138	H
2a-139	H
2a-140	H
2a-141	H
2a-142	H
2a-143	H
2a-144	H
2a-145	H
2a-146	H
2a-147	H
2a-148	H
2a-149	H
2a-150	H
2a-151	H
2a-152	H
2a-153	H
2a-154	H
2a-155	H
2a-156	H
2a-157	H
2a-158	H
2a-159	H
2a-160	H
2a-161	H
2a-162	H
2a-163	H
2a-164	H
2a-165	H
2a-166	H
2a-167	H
2a-168	H
2a-169	H
2a-170	H
2a-171	H
2a-172	H
2a-173	H
2a-174	H
2a-175	H
2a-176	H
2a-177	H
2a-178	H
2a-179	H
2a-180	H
2a-181	H
2a-182	H
2a-183	H
2a-184	H
2a-185	H
2a-186	H
2a-187	H
2a-188	H
2a-189	H
2a-190	H
2a-191	H
2a-192	H
2a-193	H
2a-194	H
2a-195	H
2a-196	H
2a-197	H
2a-198	H
2a-199	H
2a-200	H
2a-201	H
2a-202	H
2a-203	H
No.	X 1 —X 2 —X 3
2a-204
2a-205
2a-206
2a-207
2a-208
2a-209
2a-210
2a-211
2a-212
2a-213
2a-214
2a-215
2a-216
2a-217
2a-218
2a-219
2a-220
2a-221
2a-222
2a-223
2a-224
2a-225
2a-226
2a-227
2a-228
2a-229
2a-230
2a-231
2a-232
2a-233
2a-234
2a-235
2a-236
2a-237
2a-238
2a-239
2a-240
2a-241
2a-242
2a-243
2a-244
2a-245
2a-246
2a-247
2a-248
2a-249
2a-250
2a-251
2a-252
2a-253
2a-254
2a-255
2a-256
2a-257
2a-258
2a-259
2a-260
2a-261
2a-262
2a-263
2a-264
2a-265
2a-266
2a-267
2a-268
2a-269
2a-270
2a-271
2a-272
2a-273
2a-274
2a-275
2a-276
2a-277
2a-278
2a-279
2a-280
2a-281
2a-282
2a-283
2a-284
2a-285
2a-286
2a-287
2a-288
2a-289
2a-290
2a-291
2a-292
2a-293
2a-294
2a-295
2a-296
2a-297
2a-298
2a-299
2a-300
2a-301
2a-302
2a-303
2a-304
2a-305
2a-306
2a-307
2a-308
2a-309
2a-310
2a-311
2a-312
2a-313
2a-314
2a-315

TABLE 2b
No.	R 1	X 1 —X 2 —X 3
2b-1	H
2b-2	H

TABLE 2b
No.	R 1	X 1 —X 2 —X 3
2b-1	H
2b-2	H

TABLE 2b
No.	R 1	X 1 —X 2 —X 3
2b-1	H
2b-2	H

TABLE 2e
No.	R 1	X 1 —X 2 —X 3
2e-1	H
2e-2	H
2e-3	H

TABLE 2e
No.	R 1	X 1 —X 2 —X 3
2e-1	H
2e-2	H
2e-3	H

TABLE 2e
No.	R 1	X 1 —X 2 —X 3
2e-1	H
2e-2	H
2e-3	H

TABLE 2h
No. X                                                                        1                                                                    —X                                                                        2                                                                    —X                                                                        3
2h-1
2h-2
2h-3
2h-4
2h-5
2h-6

TABLE 2h
No. X                                                                        1                                                                    —X                                                                        2                                                                    —X                                                                        3
2h-1
2h-2
2h-3
2h-4
2h-5
2h-6

TABLE 2j
No. X                                                                        1                                                                    —X                                                                        2                                                                    —X                                                                        3
2j-1
2j-2
2j-3
2j-4
2j-5
2j-6

TABLE 2j
No. X                                                                        1                                                                    —X                                                                        2                                                                    —X                                                                        3
2j-1
2j-2
2j-3
2j-4
2j-5
2j-6

TABLE 3a
No.	R 1	X 1 —X 2 —X 3
3a-1  3a-2	CH 3 H
3a-3  3a-4  3a-5  3a-6  3a-7	CH 3 H H 3 N + C(CH 2 OH) 3 Na ½Ca
3a-8	H
3a-9	H
3a-10 3a-11	CH 3 H
3a-12 3a-13	CH 3 H
3a-14	CH 3
3a-15 3a-16	CH 3 H
3a-17 3a-18	CH 3 H
3a-19 3a-20	CH 3 H
3a-21 3a-22	CH 3 H
3a-23 3a-24	CH 3 H
3a-25	H	—(CH 2 ) 3 CH 3
3a-26	CH 3	—(CH 2 ) 7 CH 3
3a-27	H
3a-28	CH 3
3a-29	H
3a-30	CH 3
3a-31 3a-32 3a-33	CH 3 H Na
3a-34 3a-35	H Na

TABLE 3b
No.	R 1	X 1 —X 2 —X 3
3b-1 3b-2	CH 3 H
3b-3	H
3b-4	H

TABLE 3b
No.	R 1	X 1 —X 2 —X 3
3b-1 3b-2	CH 3 H
3b-3	H
3b-4	H

TABLE 3d
No.	R 1	X 1 —X 2 —X 3
3d-1  3d-2	½Ca Na
3d-3	Na
3d-4	Na
3d-5  3d-6	CH 3 H
3d-7  3d-8  3d-9	CH 3 H Na
3d-10 3d-11 3d-12 3d-13	CH 3 H Na ½Ca
3d-14 3d-15	H Na
3d-16	H
3d-17	H
3d-18	H	—(CH 2 ) 3 CH 3
3d-19	CH 3	—NHCH 3
3d-20	H
3d-21 3d-22	CH 3 H
3d-23	H
3d-24	H
3d-25 3d-26	H Na		racemic compound
3d-27 3d-28	H Na		racemic compound
3d-29 3d-30	H Na		racemic compound

TABLE 3e
No.	R 1	X 1 —X 2 —X 3
3e-1	½Ca

Physicochemical properties of compounds above are shown below. The compound number below corresponds to that described in Tables above.

No.1a-4

[α] D =−11.5° (CHCl 3 ,c=1.01,23.50° C.).

No.1a-5

[α] D =−10.00 (CHCl 3 ,c=1.01,25° C.).

No.1a-6

CDCl 3 300 MHz 0.93-1.96(14H,m),2.20-2.26(3H,m),3.03(1H,m),3.67(3H,s),4.99(1H,d,J=6.6H z),5.10-5.24(2H,m),7.37-7.51(3H,m),7.54-7.64(3H,m),7.76-7.88(2H,m), 8.11(1H,m).

IR (CHCl 3 ):3384,3278,3026,2952,2874,1727,1436,1411,1324,1155,1097/cm.

[α] D =−9.0° (CHCl 3 ,c=1.04,22.0° C.).

No.1a-7

CDCl 3 300 MHz 0.93-2.00(14H,m),2.18(1H,m),2.28(2H,t,J=7.2 Hz),3.04(1H,m),5.15-5.25(2H,m), 5.28(1H,d,J=6.9 Hz),7.36-7.50(3H,m),7.54-7.63(3H,m),7.76-7.89(2H,m), 8.12(1H,m).

IR(CHCl 3 ):3268,3028,2952,2872,1708,1452,1410,1324,1155,1097/cm.

[α] D =−9.1° (CHCl 3 ,c=1.01,24.0° C.).

No.1a-8

CDCl 3 300 MHz 0.94-1.99(14H,m),2.21-2.29(3H,m),3.05(1H,m),3.67(3H,s),4.92(1H,d,J=6.3 Hz), 5.14-5.30(2H,m),7.70-7.78(6H,m),7.96-8.01(2H,m).

IR(CHCl 3 ):3376,3272,3018,2946,2868,1727,1616,1435,1388,1324,1162,1130,1069/cm.

[α] D =+1.6° (CHCl 3 ,c=1.01,24.0° C.). mp.117-119° C.

No.1a-9

CDCl 1 300 MHz 0.95-2.08(14H,m),2.19(1H,m), 2.32(2H,t,J=7.2 Hz),3.06(1H,m),5.20-5.30(2H,m),5.34(1H,d,J=6.6 Hz),7.69-7.78(6H,m),7.96-8.03(2H,m).

IR(CHCl 3 ):3260,3020,2950,2868,1708,1389,1324,1162,1130,1069/cm.

[α] D =+13.30° (CHCl 3 ,c=1.05,24.0° C.).

mp.118-120° C.

No.1a-10

CDCl 3 300 MHz 0.96-1.98(14H,m),2.15-2.32(3H,m),3.04(1H,m),3.66(3H,s),5.12-5.26(5H,m), 7.67-7.78(4H,m),7.93-8.07(4H,m).

IR(CHCl 3 ):3276,3018,2946,2868,1726,1595,1435,1341,1162,1095/cm.

[α] D =−1.5.° (CHCl 3 ,c=1.01,25.0° C.).

mp.133-139° C.

No.1a-11

CD 3 OD 300 MHz 1.05-1.98(14H,m),2.13-2.22(3H,m),2.97(1H,m),5.09-5.22(2H,m),7.85-7.92(4H,m),7.95-8.05(4H,m).

IR(KBr):3385,3261,3069,3003,2954,2872,1708,1596,1428,1413,1378,1343,1326,1236,1186,1160,1096/cm.

mp.144-146° C.

No.1a-12

CDCl 3 300 MHz 0.96-1.96(14H,m),2.22-2.27(3H,m),3.03(1H,m),3.66(3H,s),3.87(3H,s),4.86(1H,d,J=6.9 Hz),5.18-5.24(2H,m),6.99-7.02(2H,m),7.55-7.66(2H,m),7.66-7.69(2H,m),7.89-7.92(2H,m).

IR(CHCl 3 ):3374,3270,3016,2948,2870,1726,1608,1518,1487,1458,1437,1248,1157,1037.

[α] D =+4.2° (CHCl 3 ,c=1.01,24° C.).

mp.85-87° C.

No.1a-13

CDCl 3 300 MHz 0.97-1.99(14H,m),2.18(1H,m),2.30(2H,t,J=7.2 Hz),3.04(1H,m),3.86(3H,s),5.18(1H,d,J=5.7 Hz),5.23-5.26(2H,m),6.99-7.02(2H,m),7.55-7.58(2H,m),7.68(2H,m),7.89-7.92(2H,m).

IR(CHCl 3 ):3380,3260,3020,2948,2868,1708,1608,1519,1487,1458,1306,1293,1248,1156/cm.

[α] D =+18.3° (CHCl 3 ,c=1.00,25.5° C.).

No.1a-14

CDCl 3 300 MHz 0.98-2.00(14H,m),2.20(1H,m),2.25(2H,t,J=7.2Hz),3.02(1H,m),3.67(3H,s),4.85(1H,d,J=6.3Hz),5.19-5.25(2H,m),7.13(1H,dd,J4.8,3.6 Hz),7.39(1H,d,J=4.8 Hz),7.40(1H,d,J=3.6 Hz),7.71-7.74(2H,m),7.86-7.89(2H,m).

IR(CHCl 3 ):3374,3270,3018,2946,2868,1727,1593,1434,1322/cm.

[α] D =+5.6° (CHCl 3 ,c=1.01,24° C.).

mp.69-71° C.

No.1a-15

CDCl 3 300 MHz 0.95-2.00(14H,m),2.17(1H,m),2.32(2H,t,J=7.2Hz),3.03(1H,m),5.20(1H,d,J=6.9 Hz),5.24-5.28(2H,m),7.13(1H,dd,J=4.8,3.3 Hz),7.38(1H,d,J=4.8 Hz),7.43(1H,d,J=3.3 Hz),7.73(2H,d,J=8.4 Hz),7.87(2H,d,J=8.4 Hz).

IR(CHCl 3 ):3260,3022,2948,2868,1709,1593,1404,1321,1154/cm.

[α] D =+20.8° (CHCl 3 ,c=1.07,23° C.).

mp.71-73° C.

No.1a-16

CDCl 3 300 MHz 0.98-2.00(14H,m),2.27(2H,t,J=7.5 Hz),2.28(1H,m),3.13(1H,m),3.66(3H,s) 4.90(1H,d,J=6.9Hz),5.25-5.29(2H,m),7.40-7.65(6H,m),7.76(1H,d,J=8.4Hz),7.90-8.02(4H,m).

IR(CHCl 3 ):3376,3276,3018,2946,2868,1726,1593,1435,1394,1322,1159/cm.

[α] D =+7.0° (CHCl 3 ,c=1.07,24° C.).

No.1a-17

CDCl 3 300 MHz 1.02-2.07(14H,m),2.25(1H,m),2.34(2H,t,J=6.6 Hz),3.14(1H,m),5.28-5.33(3H,m),7.39-7.57(4H,m),7.62-7.65(2H,m),7.76(1H,d,J=8.1 Hz),7.89-8.02(4H,m).

IR(CHCl 3 ):3260,2948,2868,1709,1593,1394,1324,1157/cm.

[α] D =+20.2° (CHCl 3 ,c=1.02,24° C.).

No.1a-18

CDCl 3 300 MHz 1.05-1.97(14H,m),2.25(2H,t,J=7.2 Hz),2.33(1H,m),3.12(1H,m),3.67(3H,s), 4.90(1H,d,J=6.6Hz),5.24-5.29(2H,m),7.24(1H,d,J=3.9Hz),7.39-7.45(1H,m),7.56(1H,d,J=3.9 Hz),7.59-7.62(2H,m).

IR(CHCl 3 ):3372,3272,3018,2946,2868,1727,1433,1331,1152/cm.

[α] D =−5.7° (CHCl 3 ,c=1.01,23° C.).

No.1a-19

CDCl 3 300 MHz 1.05-2.05(14H,m),2.28-2.33(3H,m),3.13(1H,m),5.18(1H,d,J=6.3 Hz),5.27-5.31(2H,m),7.24(1H,d,J=4.2 Hz),7.39-7.42(3H,m),7.56(1H,d,J=4.2 Hz),7.58-7.62(2H,m).

IR(CHCl 3 ):3372,3254,3018,2948,2868,1707,1431,1328,1151/cm.

No.1a-20

CDCl 3 300 MHz 1.05-2.00(14H,m),2.26(2H,t,J=7.5 Hz),2.33(1H,m),3.11(1H,m),3.68(3H,s) 4.92(1H,d,J=6.0 Hz),5.27(2H,m),7.05(1H,m),7.10(1H,d,J=3.6 Hz),7.25(1H,m), 7.32(1H,m),7.49(1H,d,J=3.6 Hz).

IR(CHCl 3 ):3372,3272,3018,2946,2686,1727,1438,1417,1333,1151/cm.

[α] D =−9.2° (CHCl 3 ,c=1.01,25° C.).

No.1a-21

CDCl 3 300 MHz 1.02-2.01(14H,m),2.28-2.34(3H,m),3.13(1H,m),5.12(1H,d,J=6.9 Hz),5.28-5.32(2H,m),7.06 (1H,m),7.10(1H,d,J=3.9 Hz),7.25(1H,m),7.32(1H,m),7.50(1H,d,J=3.9 Hz).

IR(CHCl 3 ):3350,3250,2948,1709,1440,1420,1330,1151.

[α] D =+2.5° (CHCl 3 ,c=1.00,25° C.).

No.1a-22

CDCl 3 300 MHz 0.96-2.05(14H,m),2.25(1H,m),2.35(2H,t,J=7.0 Hz),3.11(1H,m),5.20 -5.34m),(2H,m), 5.41(1H,d,J=6.6 Hz),7.31-7.49(5H,m),7.62(1H,d,J=7.8 Hz),8.1(1H,d,J=1.8 and 7.8 Hz),8.35(1H,d,J=1.8 Hz).

IR(CHCl 3 ):3384,3271,3025,2958,1708,1608,1559,1537,1357,1168/cm.

[α] D =+18.3° (CHCl 3 ,c=0.31,22° C.).

No.1a-23

CDCl 3 300 MHz 0.97-2.07(14H,m),2.24(1H,m),2.35(2H,t,J=6.9 Hz),3.09(1H,m),1H,m), 3.86(3H,s),5.24-5.35(2H,m),5.44(1H,d,J=6.3 Hz),6.97-7.00(2H,m),7.26-7.28(2H,m),7.59(1H,d,J=8.1 Hz),8.06(1H,d.d,J=2.1and8.1 Hz),8.29(1H,d,J=2.1 Hz).

IR(CHCl 3 ):3384,3270,2959,1709,1609,1535,1519,1357,1302,1255,1226,1169/cm.

[α] D =+17.0° (CHCl 3 ,c=1.00,21° C.).

No.1a-24

CDCl 3 300 MHz 0.95-2.00(14H,m),2.20-2.25(1H,m),2.26(2H,t,J=7.2 Hz),3.0-3.0(1H,m), 3.66(3H,s),4.92(1H,d,J=6.6 Hz),5.16-5.31(2H,m),7.52-7.60(3H,m),7.94-8.06(6H,m).

IR(CHCl 3 ):3376,3020,2946,2868,1726,1436,1366,1298,1164,1090,890/cm.

[α] D =+11.2±0.5° (CHCl 3 ,c=1.04,23.5° C.)

mp.101-103° C.

No.1a-25

CDCl 3 300 MHz 0.95-2.08(14H,m),2.15-2.22(1H,m),2.33(2H,t,J=6.9 Hz),3.02-3.10(1H,m), 5.21-5.31(2H,m),5.34(1H,d,J=6.3 Hz),7.51-7.59(3H,m),7.92-8.07(6H,m).

IR(CHCl 3 ):3258,3022,2948,2868,1707,1399,1328,1298,1163,1089,1051,892/cm.

[α] D =+29.8±0.7° (CHCl 3 ,c=1.05,25° C.)

mp.158-160° C.

No.1a-26

Anal. Calcd for C 32 H 30 N 3 O 4 SNa 0.8H 2 O: C,60.29;H,6.15;N,8.11;S,6.19;Na, 4.44; Found: C,60.15;H,6.19;N,8.15;S,6.03;Na,4.98.

[α] D =−16.60° (CHCl 3 ,c=1.04,25.0° C.).

No.1a-27

CDCl 3 300 MHz 0.92-1.98(14H,m),2.20(1H,m),2.26(2H,t,J=7.5 Hz),3.03(1H,m),3.12(6H,s),3.66(3H,s),4.87(1H,d,J=6.6 Hz),5.16-5.32(2H,m),6.73-6.80(2H,m),7.88-8.00(6H,m).

IR(CHCl 3 ):3376,3020,2946,1726,1601,1518,1442,1419,1362,1312,1163,1133,1088/cm.

[α] D =+55.3° (CHCl 3 ,c=0.53,24.0° C.).

mp.158-168° C.

No.1a-28

CDCl 3 +C 3 O 300 MHz 0.99-2.14(14H,m),2.21 (1H,m),2.31 (2H,t,J=7.2 Hz),2.94(1H,m), 3.12(6H,s),5.22-5.38(2H,m),6.73-6.81(2H,m),7.87-8.00(6H,m).

IR(KBr):3434,3309,2946,1708,1604,1520,1442,1416,1366,1312,1252,1164,1155,1134,1091/cm.

[α] D =not measurable (colored, insufficient energy)

mp.193-196° C.

No.1a-29

CD 3 OD 300 MHz 1.02-1.96(14H,m),2.10(2H,t,J=7.8 Hz),2.16(1H,m),2.98(1H,m),3.11(6H,s) 5.07-5.27(2H,m),6.80-6.87(2H,m),7.84-8.00(6H,m).

IR(KBr):3433,3087,3004,2949,2871,1604,1565,1520,1444,1420,1364,1312,1253,11638,1136,1090/cm.

[α] D =not measurable

No.1a-30

CDCl 3 300 MHz 0.95-1.99(14H,m),2.22(1H,m),2.26(2H,t,J=7.2 Hz),2.35(3H,s),3.06(1H,m) 3.6(3H,s),4.95(1H,d,J=6.9 Hz),5.15-5.30(2H,m),7.26-7.32(2H,m),7.97-8.06(6H,m).

IR(CHCl 3 ):3374,2996,2946,2868,1763,1728,1591,1495,1435,1368,1299,1228,1192,1163,1139/cm.

[α] D =+12.9° (CHCl 3 ,c=1.04,26.0° C.).

No.1a-31

CDCl 3 300 MHz 0.93-2.01(14H,m),2.19(1H,m),2.31 (2H,t,J=7.2 Hz),2.35(3H,s),3.06(1H,m), 5.17-5.32(2H,m),7.25 -7.32(2H,m), 7.96-8.07(6H,m).

IR(CHCl 3 ):3267,3028,2952,2874,1759,1708,1592,1495,1368,1328,1299,1163,1138,1088,1050,1008/cm.

[α] D =+21.7° (CHCl 3 ,c=0.51,22° C.).

No.1a-32

CDCl 3 300 MHz 0.93-1.99(14H,m),2.21(1H,m),2.27(2H,t,J=7.2 Hz),3.05(1H,m),3.67(3H,s),4.92(1H,d,J=6.6 Hz),5.15-5.30(2H,m),6.72(1H,s),6.96-7.00(2H,m),7.86-8.04(6H,m).

IR(CHCl 3 ):3374,3276,3018,2946,2686,1725,1605,1589,1502,1433,1396,1330,1271,1164,1135,1089 /cm. [α] D =+18.60° (CHCl 3 ,c=1.00,26.0° C.).

No.1a-33

CDCl 3 +CD 3 OD 300 MHz 0.98-2.08(14H,m),2.20(1H,m),2.28(2H,t,J=7.2 Hz),2.98(1H,m),5.18-5.32(2H,m),6.92-6.99(2H,m),7.85-8.02(6H,m).

IR(KBr):3385,3248,2948,2876,1717,1601,1505,1430,1399,1296,1280,1219,1165,1136,1092/cm.

[α] D =−16.0° (CH 3 OH,c=1.08,26.0° C.).

mp.208-210° C.

No.1a-34

mp.82-83° C. [α] D +1.8° (CHCl 3 ,c=1.07,23.5° C.).

No.1a-35

mp.80-82° C. [α] D =−1.8° (CHCl 3 ,c=1.07,22.0° C).

No.1a-36

TLC Rf=(ethyl acetate/n-hexane=1:1(0.3% acetic acid))

No.1a-37

CDCl 3 300 MHz 0.92-1.96(14H,m),2.21(1H,m),2.27(2H,t,J=7.4 Hz),3.01(1H,m),3.66(3H,s),4.71(1H,d,J=6.6 Hz),5.14-5.29(2H,m),7.12(1H,d,J=16.2Hz),7.24(1H,d,J=16.2 Hz), 728-7.42(3H,m),7.52-7.56(2H,m),7.62(2H,d,J=8.7 Hz),7.85(2H,d,J=8.7 Hz).

IR(CHCl 3 ):3384,3283,3023,2954,2876,1730,1595,1494,1317,1163,1147/cm.

[α] D =+10.5° (CHCl 3 ,c=1.01,24° C.).

mp 116-117 ° C.

No.1a-38

CDCl 3 300 MHz 0.92-1.99(14H,m),2.17(1H,m),2.32(2H,t,J=7.2 Hz),3.02(1H,m),5.23-5.29(3H,m),7.11(1H,d,J=16.2 Hz),7.23(1H,d,J=16.2 Hz),7.28-7.41(3H,m),7.52-7.55(2H,m),7.61(2H,d,J=8.7 Hz),7.86(2H,d,J=8.7 Hz).

IR(CHCl 3 ):3515,3384,3270,3022,3015,2957,2876,2669,1708,1595,1496,1320,1157/cm.

[α] D =+27.1° (CHCl 3 ,c=1.02,24° C.).

No.1a-39

CDCl 3 300 MHz 0.92-1.99(14H,m),2.15(1H,m),2.28(2H,t,J=7.4 Hz),3.01(1H,m),3.68(3H,s)4.96(1H,d,J=6.6 Hz),5.16-5.32(2H,m),6.60(1H,d,J12.0 Hz),6.74(1H,d,J=12.0 Hz), 7.16-7.23 (5H,m), 7.35(2H,d,J8.4 Hz).

IR(CHCl 3 ):3384,3283,3023,3015,2954,2876,1730,1595,1493,1324,1163,1147/cm.

[α] D =+13.7° (CHCl 3 ,c=1.00,24° C.).

No.1a-40

CDCl 3 300 MHz 0.90-2.16(14H,m),2.12(1H,m),2.34(2H,t,J=7.2 Hz),3.02(1H,m),5.16(1H,d,J=6.9 Hz),5.23-5.34(2H,m),6.60(1H,d,J=12.3 Hz),6.74(1H,d,J=12.3 Hz),7.14-7.24(5H,m),7.35(2H,d,J=8.1 Hz),7.72(2H,d,J=8.1 Hz).

IR(CHCl 3 ):3515,3384,3269,3025,3021,3014,2957,2876,2668,1709,1595,1322,1162,1147/cm.

[α] D =+26.4° (CHCl 3 ,c=1.00,24° C.).

No.1a-41

CDCl 3 300 MHz 0.98-1.99(14H,m),2.17(1H,m),2.32(2H,t,J=7.2 Hz),3.00(1H,m),3.84(3H,s), 5.20-5.26(3H,m),6.90-6.95(2H,m),6.98(1H,d,J=16.2 Hz),7.17(1H,d,J=16.2 Hz),7.46-7.49(2H,m),7.58(2H,d,J=8.4 Hz),7.83(2H,d,J=8.4 Hz).

IR(CHCl 3 ):3258,3018,3002,2950,1709,1590,1509,1457,1404,1302,1250,1153/cm.

[α] D =+30.20° (CHCl 3 ,c=1.00,23° C.).

mp.99-100° C.

No.1a-42

CDCl 3 300 MHz 1.01-1.99(14H,m),2.28(2H,t,J=7.2 Hz),2.30(1H,m),3.10(1H,m),3.66(3H,s), 5.07(1H,br),5.25-5.30(2H,m),6.98-7.04(2H,m),7.16(1H,d,J=16.2 Hz),7.28-7.37(3H,m),7.47-7.50(3H,m).

IR(CHCl 3 ):3372,3276,3020,2946,2870,1727,1491,1433,1331,1152/cm.

[α] D =−11.5° (CHCl 3 ;c=1.07,21.5° C.).

No.1a-43

CDCl 3 300 MHz 0.98-2.00(14H,m),2.11-2.36(3H,m),3.12(1H,m),5.10(1H,d,J=6.6 Hz),5.29-5.32(2H,m),6.99-7.04(2H,m),7.23(1H,d,J=21.6 Hz),7.32-7.49(6H,m).

IR(CHCl 3 ):3380,3248,3020,2948,2868,1709,1491,1430,1329,1151/cm.

[α] D =+3.4° (CHCl 3 ,c=1.03,25° C.).

No.1a-44

CDCl 3 300 MHz 1.00-2.00(14H,m),2.13(1H,m),2.29(2H,t,J=7.4 Hz),2.90-3.13(5H,m),3.68(3H,s),4.74(1H,d,J=6.6 Hz),5.15-5.30(2H,m),7.18-7.29(7H,m),7.76(2H,d,J=8.1 Hz)

IR(CHCl 3 ):3384,3282,3063,3028,3023,3016,2953,2876,1730,1599,1496,1319,1157/cm.

[α] D =+2.3° (CHCl 3 ,c=1.00,25° C.).

mp.85.0-86.0° C.

No.1a-45

CDCl 3 300 MHz 0.90-2.05(14H,m),2.09(1H,m),2.35(2H,t,J=6.9 Hz),2.90-3.13(5H,m),5.18(1H,d,J=6.6 Hz),5.24-5.34(2H,m),7.10-7.27(7H,m),7.76(2H,d,J=8.4 Hz).

IR(CHCl 3 ):3510,3384,3270,3087,3063,3026,3018,3014,2955,2876,2670,1708,1599,1496,1318,1157/cm.

[α] D =+8.5° (CHCl 3 ,c=1.01,25° C.).

No.1a-46

[α] D =+6.80° (CHCl 3 ,c=1.05,25° C.). mp.99-100° C.

No.1a-47

CDCl 3 300 MHz 0.97-2.01(14H,m),2.14(1H,m),2.36(2H,t,J=7.2 Hz),3.02(1H,m),5.23(1H,d,J=5.4 Hz),5.26-5.30(2H,m),7.37-7.39(3H,m), 7.54-7.58(2H,m),7.63-7.66(2H,m), 7.85-7.88(2H,m).

IR(CHCl 3 ):3375,3260,3022,2948,2212,1707,1596,1497,1396,1322,1160/cm.

[α] D =+25.0° (CHCl 3 ,c=1.02,24° C.). mp.117-118° C.

No.1a-48

CD 3 OD 300 MHz 1.05-1.93(14H,m),2.10-2.15(3H,m),2.96(1H,m),5.08-5.28(2H,m),7.38-7.40(3H,m),7.554-7.56(2H,m),7.69(1H,d,J=8.4 Hz),7.87(1H,d,J=8.4 Hz).

No.1a-49

CDCl 3 300 MHz 0.96-1.97(14H,m),2.24(1H,m),2.31(2H,t,J=6.9Hz),3.05(1H,m),3.69(3H,s),5.15(1H,d,J=6.6 Hz),5.25-5.27(2H,m),7.40-7.43(3H,m),7.61-7.64(2H,m),7.85(1H,d,J=8.1 Hz), 8.07(1H,dd,J=8.1,1.8 Hz),8.58(1H,d,J=1.8 Hz).

IR(CHCl 3 ):3374,3020,2948,2870,2212,1726,1606,1530,1493,1437,1345,1167/cm.

[α] D =+2.4° (CHCl 3 ,c=1.03,25° C.). mp.77-79° C.

No.1a-50

CDCl 3 300 MHz 1.00-2.02(14H,m),2.20(1H,m),2.34(2H,t,J=6.6 Hz),3.08(1H,m),5.26-5.29(2H,m),5.41 (1H,d,J=6.9Hz),7.40-7.43(3H,m),7.61-7.64(2H,m),7.84(1H,d,J=8.1 Hz),8.07(1H,dd,J=8.4,1.8 Hz),8.57(1H,dd,J=1.8 Hz).

IR(CHCl 3 ):3380,3254,2952,2880,2212,1707,1606,1531,1493,1409,1344,1166.

[α] D =+23.4° (CHCl 3 ,c=1.00,25° C.).

No.1a-51

CDCl 3 300 MHz 0.95-1.98(14H,m),2.23(1H,m),2.30(2H,t,J=7.2 Hz),3.00(1H,m),3.66(3H,s),4.56(2H,br),4.70(1H,d,J=6.9 Hz),5.20-5.29(2H,m),7.15(1H,dd,J=7.8,1.8 Hz), 7.23(1H,d,J=1.8 Hz),7.36-7.39(3H,m),7.46(1H,d,J=7.8 Hz), 7.53-7.56(2H,m).

IR(CHCl 3 ):3494,3386,3028,2952,2874,1725,1611,1559,1497,1422,1317,1162/cm.

No.1a-52

CDCl 3 300 MHz 0.96-2.04(16H,m),2.20(1H,m),2.36(2H,t,J=6.9 Hz),2.99(1H,m),5.17(1H,d,J=6.3 Hz),5.28-5.31(2H,m),7.18(1H,dd,J=9.6,1.8 Hz),7.25(1H,m),7.36-7.39(3H,m), 7.46(1H,d,J=7.8 Hz),7.52-7.56(2H,m).

IR(CHCl 3 ):3482,3378,3260,3022,2948,2868,1708,1612,1495,1422,1317/cm.

[α] D =+15.0° (CHCl 3 ,c=1.00,24° C.).

No.1a-53

CDCl 3 300 MHz 1.01-2.05(15H,m),2.31(2H,t,J=7.2 Hz),3.10(1H,m),3.67(3H,s),5.02(1H,br),5.26-5.33(2H,m),7.18(1H,d,J=4.2 Hz),7.36-7.39(3H,m),7.48(1H,d,J=4.2 Hz),7.51-7.55(2H,m).

IR(CHCl 3 ):3372,3270,3018,3004,2946,2868,2202,1726,1486,1433,1336,1154/cm.

[α] D =+0.60° (CHCl 3 ,c=1.11,25° C.), [α] 436 +17.8° (CHCl 3 ,c=1.11,25° C.).

No.1a-54

CDCl 3 300 MHz 0.99-2.11(14H,m),2.27(1H,m),2.37(2H,t,J=7.5 Hz),3.13(1H,m),5.16(1H,d,J=6.6 Hz),5.31-5.35(2H,m),7.18(1H,d,J=3.6 Hz),7.37-7.39(3H,m),7.50(1H,d,J=3.6 Hz),7.52-7.55(2H,m).

IR(CHCl 3 ):3484,3370,3246,2948,2868,2202,1708,1486,1429,1335,1153/cm.

[α] D =+17.8° (CHCl 3 ,c=1.00,24° C.). mp.95-96° C.

No.1a-55

CDCl 3 300 MHz 0.95-1.92(14H,m),2.15(1H,m),2.24(2H,t,J=7.5 Hz),3.00(1H,m),3.66(3H,s)5.10-5.30(3H,m),7.40-7.60(7H,m),7.70(1H,d,J=7.8 Hz),8.08(1H,d,J=8.1 Hz).

IR(CHCl 3 ):3356,3020,2948,2868,2210,1727,1490,1458,1437,1341,1165/cm.

[α] D =−58.4° (CHCl 3 ,c=1.00,260° C.). mp.84-85° C.

No.1a-56

CDCl 3 300 MHz 0.95-1.95(14H,m),2.10(1H,m),2.27(2H,t,J=6.9 Hz),3.00(1H,m),5.17-5.21(2H,m),5.38(1H,d,J=6.9 Hz),7.39-7.60(7H,m),7.70(1H,dd,J=7.8,1.5 Hz),8.07(1H,J=6.6,1.5 Hz).

IR(CHCl 3 ):3364,3026,2952,2874,2212,1707,1597,1491,1458,1411,1341,1164/cm.

[α] D =−43.10° (CHCl 3 ,c=1.00,25° C.).

No.1a-57

CDCl 3 300 MHz 0.99-1.97(14H,m),2.23-2.30(3H,m),3.01(1H,m),3.67(3H,s),5.17-5.26(3H,m),7.36-7.38(3H,m), 7.50-7.56(3H,m), 7.60(1H,m), 7.83(1H,m),8.05(1H,m).

IR(CHCl 3 ):3376,3020,2946,2870,1727,1598,1491,1437,1412,1330,1245,1163/cm.

[α] D =−12.7° (CHC 3 ,c=1.00,240° C.).

No.1a-58

CDCl 3 300 MHz 0.97-1.98(14H,m),2.20(1H,m),2.33(2H,t,J=6.9Hz),3.02(1H,m),5.19-5.28(3H,m),7.36-7.38(3H,m),7.47-7.55(3H,m),7.69(1H,m),7.83(1H,m),8.04(1H,m).

IR(CHCl 3 ):3376,3260,3022,3002,2948,2868,2220,1708,1598,1490,1455,1412,1327,1162/cm.

[α] D =−8.6° (CHCl 3 ,c=1.01,24° C.).

No.1a-59

CDCl 3 300 MHz 0.95-1.99(14H,m),2.20(1H,m),2.28(2H,t,J=7.8 Hz),2.53(1H,s),2.96(1H,m),3.69( 3 H,s),4.99(1H,d,J=6.6 Hz),5.18-5.20(2H,m),7.53(2H,d,J=8.4 Hz),7.82),2H,d,J=8.4 Hz).

IR(CHCl 3 ):3583,3376,3002,2936,2852,1725,1591,1490,1437,1393,1325,1160/cm.

[α] D =−8.8° (CHCl 3 ,c=1.00,24° C.).

No.1a-60

CDCl 3 300 MHz 0.96-2.05(24H,m),2.22(1H,m),2.33(2H,m),2.88(1H,m),5.22-5.26(5.30(1H,d,J=5.7 Hz),7.50(2H,d,J=8.7 Hz),7.80(2H,d,J=8.7 Hz).

IR(CHCl 3 ):3376,3260,3022,2936,2852,1710,1592,1491,1452,1395,1325,1159/cm.

[α] D =−8.9° (CHCl 3 ,c=1.06,24° C.),

mp.88-91° C.

No.1a-61

CDCl 3 300 MHz 0.95-2.24(23H,m),2.29(2H,m),2.99(1H,m),3.69(3H,s),4.76(1H,d,J=6.3 Hz),5.21-5.24(2H,m),6.28(1H,m),7.50-7.53(2H,m),7.77-7.80(2H,m).

IR(CHCl 3 ):3374,3270,3018,2942,2868,2196,1726,1589,1490,1435,1324,1158/cm.

[α] D =+7.7° (CHCl 3 ,c=1.02,24° C.), mp.93-95° C.

No.1a-62

CDCl 3 300 MHz 0.96-2.45(23H,m),2.36(2H,d,J=6.9Hz),2.99(1H,m),5.24(1H,d,J=6.3Hz),5.24-5.32(2H,m),6.28(1H,m),7.50-7.53(2H,m),7.78-7.81(2H,m).

IR(CHCl 3 ):3468,3374,3260,3020,2942,2868,2196,1598,1490,1455,1398,1322,1157/cm.

[α] D =+19.4° (CHCl 3 ,c=1.03,24° C.).

No.1a-63

CDCl 3 300 MHz 0.93-1.95(25H,m),2.16(1H,m),2.29(2H,t,J=7.2 Hz),2.43(2H,t,J=6.9 Hz),2.94(1H,m),3.69(3H,s),4.95(1H,d,J=6.9 Hz),5.21-5.24(2H,m),7.49(2H,d,J=8.7 Hz),7.79(2H,J=8.7 Hz).

IR(CHCl 3 ):3376,3018,2946,2866,2222,1727,1592,1456,1435,1325,1158/cm.

[α] D =+3.7° (CHCl 3 ,c=1.00,25° C.).

No.1a-64

CDCl 3 300 MHz 0.93-1.97(26H,m),2.35(2H,t,J=7.2 Hz),2.43(2H,t,J=7.2 Hz),3.00(1H,m),5.08(1H,d,J=6.6 Hz),5.26-5.27(2H,m),7.49(2H,d,J=8.7 Hz),7.78(2H,d,J=8.7 Hz).

IR(CHCl 3 ):3260,3020,2948,2864,2222,1708,1592,1489,1456,1397,1324,1156/cm.

[α] D =+14.4° (CHCl 3 ,c=1.00,25° C.) mp.70-71° C.

No.1a-65

CDCl 3 300 MHz 0.95-1.98(14H,m),2.18(1H,m),2.30(2H,t,J=7.2 Hz),3.00(1H,m),3.67(3H,s)4.3(1H,d,J=6.9 Hz),5.22-5.26(2H,m),5.54(1H,br),6.82-6.85(2H,m),7.42-7.45(2H,m),7.59-7.62(2H,m),7.82-7.85(2H,m).

IR(CHCl 3 ):3576,3374,3018,2946,2868,2208,1725,1607,1587,1514,1435,1325,1270,1162,1133/cm.

[α] D =+9.1° (CHCl 3 ,c=1.03,24° C.), mp.111-112° C.

No.1a-66

CDCl 3 300 MHz 0.97-2.03(14H,m),2.15(1H,m),2.35(2H,t,J=7.5 Hz),3.00(1H,m),5.17(1H,d,J=6.6 Hz),5.26-5.30(2H,m),6.82-6.85(2H,m),7.42-7.45(2H,m),7.59-7.62(2H,m),7.82-7.85(2H,m).

IR(CHCl 3 ):3260,2948,2870,2208,1709,1607,1587,1514,1396,1325,1270,1162,1133/cm.

[α] D =−21.0° (CHCl 3 ,c=1.00,23° C.), mp.161-162° C.

No.1a-67

CDCl 3 300 MHz 0.95-1.98(14H,m),2.20(1H,m),2.29(2H,t,J=7.2 Hz),3.01(1H,m),3.67(3H,s),4.82(1H,d,J=6.6 Hz),5.19-5.27(2H,m),7.05-7.10(2H,m),7.51-7.56(2H,m),7.61-7.64(2H,m),7.84-7.87(2H,m).

IR(CHCl 3 ):3374,3280,3020,2946,2868,2214,1727,1589,1509,1435,1327,1233,1161,1134/cm.

[α] D =+6.7° (CHCl 3 ,c=1.01,240° C.), mp.84-85° C.

No.1a-68

CDCl 3 300 MHz 0.96-2.01(14H,m),2.15(1H,m),2.34(2H,t,J=6.9 Hz),3.02(1H,m),5.23-5.27(3Hm),7.04-7.10(2H,m),7.51-7.56(2H,m),7.61-7.64(2H,m),7.85-7.88(2H,m).

IR(CHCl 3 ):3374,3258,3020,2948,2868,2214,1708,1589,1509,1455,1398,1322,1156/cm.

[α] D =+22.6° (CHCl 3 ,c=1.02,24° C.), mp.135-136° C.

No.1a-69

CDCl 3 300 MHz 0.95-1.98(14H,m),2.19(1H,m),2.29(2H,t,J=7.2 Hz),2.39(3H,s),3.01(1H,m),3.69(3H,s),4.80(1H,d,J=6.6 Hz),5.20-5.29(2H,m),7.18(2H,d,J=8.1 Hz),7.44(2H,d,J=8.1 Hz),7.62(2H,d,J=8.4 Hz),7.84(2H,d,J=8.4 Hz).

IR(CHCl 3 ):3374,3022,2946,2868,2210,1727,1589,1511,1436,1323,1161,1133/cm.

[α] D =+9.2° (CHCl 3 ,c=1.02,24° C.).

mp.116-118° C.

No.1a-70

CDCl 3 300 MHz 1.15-2.00(14H,m),2.13(1H,m),2.33-2.38(5H,m),3.04(1H,m),5.14(1H,d,J=6.6 Hz),5.25-5.30(2H,m),7.17(2H,d,J=7.8 Hz),7.44(2H,d,J=7.8 Hz),7.62(2H,d,J=8.4 Hz),7.85(2H,d,J=8.4 Hz).

IR(CHCl 3 ):3380,3260,3020,2948,2868,2210,1708,1590,1511,1396,1324,1160,1133/cm.

[α] D =+24.6(CHCl 3 ,c=1.00,24° C.).

No.1a-71

CDCl 3 300 MHz 0.95-1.96(14H,m),2.19(1H,m),2.29(2H,t,J=7.2 Hz),3.00(1H,m),3.20(1H,s),3.65(3H,s),4.81(1H,d,J=6.6 Hz),5.20-5.27(2H,m),7.46-7.54(4H,m),7.62-7.65(2H,m),7.85-7.88(2H,m).

IR(CHCl 3 ):3374,3290,3018,3002,2946,2868,2212,2110,1726,1591,1507,1435,1401,1324,1161/cm.

[α] D =+9.6° (CHCl 3 ,c=1.01,24° C.), mp.136-138° C.,

No.1a-72

CDCl 3 300 MHz 0.96-2.01(14H,m),2.14(1H,m),2.35(2H,t,J=7.2 Hz),3.05(1H,m),3.20(1H,s),5.16(1H,d,J=7.2 Hz),5.26-5.29(2H,m),7.45-7.53(4H,m),7.63(2H,d,J=8.4 Hz),7.87(2H,d,J=8.4 Hz).

IR(CHCl 3 ):3462,3374,3290,3024,2948,2868,2212,2110,1708,1591,1508,1455,1401,1321,1274,1160,1132/cm.

[α] D =+24.3° (CHCl 3 ,c=1.03,24° C.), mp.96-99° C.

No.1a-73

CDCl 3 300 MHz 0.95-1.98(14H,m),2. 19(1H,m),2.27-2.32(5H,m),3.01 (1H,m),3.67(3H,s),4.80H,d,J=6.6 Hz),5.20-5.27(2H,m),7.12(2H,m),7.56(2H,m),7.63(2H,m),7.84(2H,m.)

IR(CHCl 3 ):3374,3276,3018,2946,2868,2214,1762,1730,1589,1506,1435,1368,1161/cm.

[α] D =+7.8(CHCl 3 ,c=1.02,24° C.), mp.102-104° C.

No.1a-74

CDCl 3 300 MHz 0.95-2.05(14H,m),2.15(1H,m),2.32-2.37(5H,m),3.02(1H,m), 5.14(1H,d,J=6.6 Hz),5.26-5.30(2H,m),7.10-7.13(2H,m),7.54-7.57(2H,m),7.62-7.64(2H,m),7.87(2H,m).

IR(CHCl 3 ):3482,3250,3022,2946,2868,2214,1716,1709,1589,1507,1454,1396,I 1368,1322,1195,1161/cm.

[α] D =+15.0° (CHCl 3 ,c=1.00,24° C.), mp.129-131° C.

No.1a-75

CDCl 3 300 MHz 0.95-1.99(14H,m),2.20(1H,m),2.30(2H,t,J=7.2 Hz),3.02(1H,m),3.67(3.94(3H,s),4.79(1H,d,J=6.6 Hz),5.19-5.29(2H,m),7.60-7.63(2H,m),7.65-7.67(2H,m),7.86-7.89(2H,m),8.04-8.06(2H,m).

IR(CHCl 3 ):3378,3018,2946,2880,1720,1604,1435,1307,1276,1161,1106/cm.

[α] D =+7.3° (CHCl 3 ,c=1.01,25° C.), mp.132-133° C.

No.1a-76

CDCl 3 +CD 3 OD 300 MHz 1.04-2.05(14H,m),2.19(1H,m),2.32(2H,t,J=6.9 Hz),2.93(1H,m),5.27-5.31(2H,m), 7.60-7.63(2H,m), 7.65-7.68(2H,m), 7.86-7.89(2H,m),8.05-8.07(2H,m).

IR(CHCl 3 ):3402,3299,2955,2876,2665,2549,1455,1422,1313,1281,1164/cm.

[α] D =−21.1° (CH 3 OH,c=1.03,23° C.), mp.227-229(dec.)

No.1a-77

CDCl 3 300 MHz 0.96-1.99(14H,m),2.20(1H,m),2.30(2H,t,J=7.2Hz),3.02(1H,m),3.68(3H,s),4.88(1H,d,J=6.3 Hz),5.19-5.29(2H,m),7.67-7.72(4H,m),7.89-7.91(2H,m),8.24-8.27(2H,m).

IR(CHCl 3 ):3376,3276,3020,2946,2870,2214,1726,1594,1519,1455,1435,1389,1344,1161/cm.

[α] D =+7.7(CHCl 3 ,c=1.02), mp.87-89° C.

No.1a-78

CDCl 3 300 MHz 0.98-2.00(14H,m),2.18(1H,m),2.34(2H,t,J=7.2 Hz),3.02(1H,m),5.24-5.28(2H,m),5.32(1H,d,J=5.7 Hz),7.67-7.72(4H,m),7.89-7.92(2H,m),8.23-8.26(2H,m).

IR(CHCl 3 ):3374,3260,2948,2214,1708,1595,1344,1160/cm.

[α] D =+23.3° (CHCl 3 ,c=1.00), mp.102-103° C.

No.1a-79

CDCl 3 300 MHz 0.93-2.02(14H,m),2.13(1H,m),2.36(2H,t,J=7.1 Hz),3.05(1H,m),3.84(3H,s)5.18(1H,br),5.27-5.31(2H,m),6.88-6.91(2H,m),7.48-7.50(2H,m),7.60-7.63(2H,m),7.83-7.85(2H,m).

IR(CHCl 3 ):3380,3252,3020,2950,2868,2208,1708,1589,1511,1457,1396,1321,1286,1160/cm.

[α] D =+26.7° (CHCl 3 ,c=1.00). mp.75-77° C.

No.1a-80

CDCl 3 300 MHz 0.96-1.99(14H,m),2.21(1H,m),2.30(2H,t,J=7.8 Hz),3.02(1H,m),3.68(3H,s),4.80(1H,d,J=6.6 Hz),5.19-5.28(2H,m),7.51-7.77(5H,m),7.87-7.90(2H,m),8.13(1H,m).

IR(CHCl 3 ):3374,3270,3018,2946,2868,2216,1726,1607,1567,1527,1495,1456,1436,1344,1296,1161/cm.

[α] D =+7.4° (CHCl 3 ,c=1.00,22° C.), mp.68-70° C.

No.1a-81

CDCl 3 300 MHz 0.97-2.01(14H,m),2.16(1H,m),2.34(2H,t,J=7.2 Hz),3.01(1H,m),5.22-5.28(3H,m),7.51(1H,m),7.65(1H,m),7.70-7.76(3H,m), 7.88-7.91(2H,m),8.12(1H,dd,J=6.9 Hz,1.5 Hz).

IR(CHCl 3 ):3480,3382,3262,3026,2952,2872,2218,1708,1607,1567,1526,1396,1343,1225,1160/cm.

[α] D =+22.0° (CHCl 3 ,c=1.00), mp.92-94° C.

No.1a-82

CDCl 3 300 MHz 0.95-1.98(14H,m),2.20(1H,m),2.29(2H,t,J=7.2Hz),3.01(1H,m),3.67(3H,s),4.30(2H,br),4.79(1H,d,J=6.9 Hz),5.20-5.29(2H,m),6.71-6.76(2H,m),7.18(1H,m),7.37(1H,dd,J=7.8,1.2 Hz),7.61-7.65(2H,m),7.83-7.87(2H,m).

IR(CHCl 3 ):3376,3020,2946,2868,2202,1725,1613,1589,1484,1454,1315,1253,1161/cm.

[α] D =+8.9° (CHCl 3 ,c=1.00,22° C.). mp.68-70° C.

No.1a-83

CDCl 3 300 MHz 0.97-1.99(14H,m),2.17(1H,m),2.33(2H,t,J=6.9 Hz),2.99(1H,m),5.20-5.28(2H,m),5.37(1H,d,J=6.9 Hz),6.45(2H,br),6.71-6.76(2H,m),7.19(1H,dd,J=7.8,6.6 Hz),7.37(1H,m),7.62(2H,d,J=8.4 Hz),7.85(2H,d,J=8.4 Hz).

IR(CHCl 3 ):3478,3378,3260,3022,2950,2868,2204,1708,1613,1589,1484,1454,1396,1316,1160/cm.

[α] D =+17.1° (CHCl 3 ,c=1.01).

No.1a-84

CDCl 3 300 MHz 1.00-2.08(14H,m),2.21(1H,m),2.37(2H,t,J=6.9Hz),3.06(1H,m),3.86(3H,s),5.29-5.33(2H,m),5.45(1H,d,J=6.6 Hz),6.91-6.94(2H,m),7.56-7.59(2H,m),7.81(1H,d.t,J=8.1 Hz),8.04(1H,d.d,J=8.1&1.8 Hz),8.57(1H,d,J=2.1 Hz).

IR(CHCl 3 ):3492,3254,3028,2954,2202,1708,1597,1512,1344,1291,1250/cm.

[α] D =+27.4° (CHCl 3 ,c=0.53,23° C.).

No.1a-85

CDCl 3 300 MHz 0.96-2.05(14H,m),2.20(1H,m),2.35(2H,t,J=6.9Hz),2.99(1H,m),3.84(3H,B),5.22-5.31(3H,m),6.89(2H,d,J=8.7 Hz),7.19(1H,brs),7.29(1H,brs),7.45-7.50(3H,m).

IR(CHCl 3 ):3478,3378,3020,2950,2868,2202,1708,1606,1511,1421,1311,1287,1248,1155/cm.

[α] D =+17.1° (CHCl 3 ,c=1.00,23° C.).

No.1a-86

CDCl 3 300 MHz 1.03-2.05(14H,m),2.21(1H,m),2.37(2H,t,J=6.9 Hz),3.04(1H,m),5.29-5.33(2H,m),5.57(1H,d,J=6.3 Hz),6.84-6.87(2H,m),7.50-7.53(2H,m),7.79(1H,d,J=8.1 Hz),8.03(1H,d,d,J=1.5 and 8.1 Hz),8.57(1H,d,J=1.5 Hz).

IR(CHCl 3 ):3250,3024,2950,2868,2200,1707,1515,1344,1271,1166,1143/cm.

[α] D =+21.2° (CHCl 3 ,c=0.26,22° C.).

No.1a-87

CD 3 OD 300 MHz 1.04-2.00(14H,m),2.18(1H,m),2.26(2H,t,J=5.4 Hz),2.93(1H,m),5.19-5.24(2H,m),6.77-6.80(2H,m),7.05(1H,d.d,J=2.1 and 8.1 Hz),7.22(1H,d,J=2.1 Hz),7.38-7.42(3H,m).

IR(CHCl 3 ):3377,2952,2873,2204,1705,1607,1515,1425,1312,1267,1222,1153/cm.

[α] D =−15.6° (CH 3 OH,c=1.02,22° C.).

No.1a-88

CDCl 3 300 MHz 0.90-1.96(14H,m),2.22-2.31(3H,m),2.95(1H,m),3.65(3H,s),4.87(1H,d,J=6.6Hz),5.13-5.28(2H,m),7.46-7.62(3H,m),7.82-7.89(4H,m),7.90-7.96(2H,m), 8.42(1H,brs).

IR(CHCl 3 ):3376,3016,2946,2868,1720,1677,1592,1514,1498,1429,1376,1314,1241,1156,1094/cm.

[α] D =−10.7° (CHCl 3 ,c=1.04,22.0° C.) mp. 134-136° C.

No.1a-89

CDCl 3 +CD 3 OD 300 MHz 0.96-2.08(14H,m),2.23(1H,m),2.28(2H,t,J=7.2 Hz),2.89(1H,m),5.20-5.32(2H,m),7.46-7.62(3H,m),7.82-7.97(6H,m).

IR(KBr):3272,3007,2952,2874,1708,1660,1592,1527,1498,1433,1400,1317,1260,1152,1094/cm.

[α] D =−24.4° (CH 3 OH,c=1.02,25.0° C.).

No.1a-90

CDCl 3 300 MHz 0.89-1.96(14H,m),2.23-2.33(3H,m),2.92(1H,m),3.67(3H,s),4.85(1H,d,J=6.3 Hz),5.10-5.25(2H,m),7.81-7.90(4H,m),8.10-8.18(2H,m),8.31-8.40(2H,m),8.77(1H,s).

IR(CHCl 3 ):3372,3018,2946,2868,1718,1685,1592,1527,1436,1397,1346,1318,1256,1154,1099/cm.

[α] D =−16.1° (CHCl 3 ,c=1.00,23.0° C.).

No.1a-91

CDCl 3 +CD 3 OD 300 MHz 0.94-2.02(14H,m),2.18-2.36(3H,m),2.87(1H,m),5.15-5.30(2H,m),7.82-7.92(4H,m),8.09-8.16(2H,m),8.30-8.37(2H,m).

IR(KBr):3284,3112,3006,2952,2874,1707,1593,1528,1498,1399,1348,1320,1259,1153,1093/cm.

[α] D =−26.3° (CH 3 OH,c=1.01,22° C.).

No.1a-92

CDCl 3 300 MHz 0.93-1.95(14H,m),2.22-2.31(3H,m),2.98(1H,m),3.68(3H,s),5.07(1H,d,J=6.9 Hz),5.10-5.24(2H,m),7.18(1H,m),7.35-7.43(2H,m),7.70(2H,d,J=7.8 Hz),7.88-8.05(4H,m),8.50(1H,brs).

IR(CHCl 3 ):3382,3008,2952,1720,1675,1599,1525,1499,1438,1321,1253,1161,1087/cm.

[α] D =−16.6° (CHCl 3 ,c=1.03,24.0° C.) mp.100-101° C.

No.1a-93

CDCl 3 +CD 3 OD 300 MHz 0.96-2.00(14H,m),2.18-2.35(3H,m),2.90(1H,m),5.15-5.30(2H,m),7.18(1H,m),7.33-7.42(2H,m),7.65-7.74(2H,m),7.90-8.08(4H,m).

IR(KBr):3347,3194,3011,2955,2875,1706,1650,1602,1544,1499,1443,1325,1265,1165,1091/cm.

[α] D =−19.4° (CH 3 OH,c=1.00,24.0° C.) mp.158-159° C.

No.1a-94

CD 3 OD 300 MHz 1.05-2.00(14H,m),2.14(1H,m),2.23(2H,t,J=7.2 Hz),2.98(1H,m),3.80(3H,s)5.13-5.27(2H,m),6.88-6.98(2H,m),7.54-7.64(2H,m),7.94-8.12(4H,m).

IR(KBr):3370,3006,2953,1708,1649,1604,1541,1512,1460,1441,1414,1328,1302,1248,1162,1107,1090,1032/cm.

[α] D =−19.1° (CH 3 OH,c=1.01,24° C.).

No.1a-95

CD 3 OD 300 MHz 104-2.02(14H,m),2.14(1H,m),2.23(2H,t,J=7.2 Hz),2.93-3.02(7H,m),5.13-5.27(2H,m),6.82-6.92(2H,m),7.51-7.59(2H,m),7.95-8.02(2H,m),8.04-8.11(2H,m).

IR(KBr):3370,3006,2953,1708,1649,1604,1541,1511,1460,1441,1414,1328,1302,1248,1162,1107,1090,1032/cm.

[α] D =−17.6° (CH 3 OH,c=1.01,24° C.).

No.1a-96

CD 3 OD 300 MHz 1.05-2.02(14H,m),2.14(1H,m),2.23(2H,t,J=7.2 Hz),2.98(1H,m),5.13-5.27(2H,m),6.75-6.84(2H,m),7.43-7.52(2H,m),7.94-8.12(4H,m).

IR(KBr):3339,3197,2953,2875,1707,1644,1606,1541,1514,1446,1325,1293,1259,1240,1225,1161,1091/cm.

[α] D =−18.7° (CH 3 OH,c=1.00,24° C.). mp.193-196° C.

No.1a-97

d 6 -DMSO 300 MHz 1.05-2.08(15H,m),2.15(2H,t,J=7.5 Hz),2.89(1H,m),5.18-5.28(2H,m),6.78-7.12(3H,m),7.73(1H,d.d,J=1.4 and 7.8 Hz),7.91-7.95(3H,m),8.14(2H,d,J=8.4 Hz),9.71(1H,s).

IR(KBr):3407,3191,2953,1711,1646,1614,1603,1537,1457,1326,1162,1151/cm.

[α] D =−20.7° (CH 3 OH,c=1.01,21° C.).

No.1a-98

CDCl 3 300 MHz

0.93-2.00(14H,m),2.21(1H,m),2.31(2H,t,J=7.2Hz),2.93(1H,m),3.84(3H,s),3.85(6H,s),5.15-5.30(2H,m),5.45(1H,d,J=6.3 Hz),7.04(2H,s),7.78-7.86(2H,m), 7.90-7.98(2H,m),8.58(1H,s).

IR(CHCl 3 ):3264,3008,2954,2874,1707,1670,1607,1537,1506,1451,1421,1308,1158,1129,1088/cm.

[α] D =−7.2° (CHCl 3 ,c=1.01,23.5° C.). mp.147-149° C.

No.1a-99

CD 3 OD 300 MHz 1.04-1.98(14H,m),2.21(1H,m),2.10(2H,t,J=7.2 Hz),2.95(1H,m),3.76(3H,s),3.86(6H,s),5.07-5.24(2H,m),7.19(2H,s),7.99(2H,d,J=8.7 Hz),8.13(1H,d,J=8.7 Hz).

IR(KBr):3354,3002,2950,2874,1656,1607,1570,1508,1452,1413,1314,1233,1185,1157,1127,1092/cm.

[α] D =−20.3° (CH 3 OH,c=1.00,23.5° C.).

No.1a-100

CDCl 3 300 MHz 1.14-1.97(14H,m),2.19(1H,m),2.28(2H,t,J=7.4 Hz),3.04(1H,m),3.69(3H,s),5.03(1H,d,J=6.9 Hz),5.15-5.29(2H,m),7.65(2H,d,J=8.4 Hz),7.87(1H,s),7.98(2H,d,J=8.4 Hz).

IR(CHCl 3 ):3386,3271,3025,3015,2955,2877,1755,1712,1608,1331,1162/cm.

[α] D =−29.4° (CH 3 OH,c=1.01,25° C.).

No.1a-101

d 6 -DMSO 1.00-2.20(17H,m),2.84(1H,m),5.00-5.20(2H,m),7.78(2H,d,J=8.2 Hz),7.84(1H,s),7.89-7.95(3H,m).

IR(KBr):3269,3065,3008,2952,2874,2763,1746,1707,1607,1322,1157/cm.

[α] D =−26.2° (CH 3 OH,c=1.01,25° C.).

No.1a-102

CD 3 OD 1.00-2.25(17H,m),2.92(1H,s),3.64(3H,s),5.07-5.21(2H,m), 7.53(1H,s),7.77(2H,d,J=8.6 Hz),7.90(2H,d,J=8.6).

IR(KBr):3430,3277,3006,2952,2873,1720,1687,1620,1571,1438,1312,1156/cm.

[α] D =−27.3° (CH 3 OH,c=0.51,26° C.), mp 230-232° C.

No.1a-103

CDCl 3 300 MHz 0.94-1.96(14H,m),2.19(1H,m),2.28(2H,t,J=7.2 Hz),3.04(1H,m),3.69(3H,s),5.11(1H,d,J=6.6Hz),5.15-5.28(2H,m),7.60(2H,d,J=8.4 Hz),7.67(1H,s),7.98(2H,d,J=8.4 Hz).

IR(CHCl 3 ):3381,3021,2955,2876,1735,1605,1437,1411,1325,1231,1177/cm.

[α] D =+8.6° (CHCl 3 ,c=1.00,23° C.).

No.1a-104

CDCl 3 300 MHz 0.94-1.96(14H,m),2.21(1H,m),2.31(2H,t,J=6.8 Hz),2.99(1H,m),5.18-5.28(2H,m),5.45(1H,d,J=6.6 Hz),7.61(2H,d,J=8.7 Hz),7.67(1H,s),7.99(2H,d,J=8.7 Hz).

IR(CHCl 3 ):3382,3222,3028,3019,2957,2876,1736,1709,1604,1412,1322,1301,1286,1179,1162/cm.

[α] D =+10.4° (CHCl 3 ,c=1.00,23° C.).

No.1a-105

CDCl 3 300 MHz 0.92-1.98(14H,m),2.17(1H,m),2.26(2H.d,J=7.5 Hz),3.01(1H,m),3.69(3H,s),4.01(3H,s),4.84(1H,d,J=6.3 Hz),5.14-5.30(2H,m),7.71(2H,d,J=8.7 Hz),7.87(2H,d),J=8.7 Hz),8.09(1H,s).

IR(CHCl 3 ):3385,3284,3025,3015,2954,2877,2821,1730,1598,1459,1438,1403,1341,1160,1052/cm.

[α] D =+3.6° (CHCl 3 ,c=1.00,26° C.).

No.1a-106

CDCl 3 300 MHz 0.92-2.08(14H,m),2.14(1H,m),2.34(2H,d,J=7.2 Hz),3.02(1H,m),4.01(3H,s),5.19(1H,d,J=6.9 Hz),5.23-5.32(2H,m),7.71(2H,d,J=8.4 Hz),7.88(2H,d,J=8.4 Hz),8.09(1H,s).

IR(CHCl 3 ):3510,3384,3268,3028,3021,3014,2957,2877,2821,2667,2821,2666,1707,1598,1459,1404,1341,1324,1160,1052/cm.

[α] D =+11.8° (CHCl 3 ,c=1.01,25° C.). mp 95-96° C.

No.1a-107

CDCl 3 300 MHz 0.92-1.97(14H,m), 1.34(3H,t,J=7.2 Hz),2.18(1H,m),2.28(2H,d,J=7.4 Hz),3.01(1H,m),3.68(3H,s),4.26(2H,q,J=7.2 Hz),4.86(1H,d,J=6.6 Hz),5.15-5.29(2H,m),7.71(2H,d,J=8.7 Hz),7.87(2H,d,J=8.7 Hz),8.09(1H,s).

IR(CHCl 3 ):3385,3282,3025,3026,3015,2954,2877,1729,1599,1480,1458,1438,1403,1338,1161/cm.

[α] D =+4.4° (CHCl 3 ,c=1.00,25° C.).

No.1a-108

CDCl 3 300 MHz 0.90-2.04(14H,m),1.34(3H,t,J=7.2 Hz),2.14(1H,m),2.34(2H,d,J=7.1 Hz),3.01(1H,m),4.27(2H,q,J=7.2 Hz),5.20(1H,d,J=6.6 Hz),5.21-5.35(2H,m),7.71(2H,d,J=8.4 Hz),7.88(2H,d,J=8.4 Hz),8.10(1H,s).

IR(CHCl 3 ):3514,3384,3270,3025,3015,3015,2957,2877,1708,1599,1458,1403,1324,1324,1160,1050/cm.

[α] D =+12.7° (CHCl 3 ,c=1.00,25° C.).

No.1a-109

[α] D =+8.5° (CHCl 3 ,c=1.00,25° C.). mp119.0-111.0° C.

No.1a-110

CDCl 3 :CD 3 OD(95:5) 0.92-2.06(14H,m),2.20(1H,m),2.30(2H,d,J=7.2 Hz),2.99(1H,m),5.22-5.33(2H,m),7.54-7.66(3H,m),8.07(2H,d,J=9.0 Hz),8.12-8.20(2H,m),8.29(2H,d,J=9.0 Hz).

IR(Nujol):3270,2956,2924,2854,1716,1548,1485,1319,1167/cm.

[α] D =+17.0° (CHCl 3 ,c=1.00,25° C.). mp.166.5-168° C.

No.1a-111

[α] D =+2.6° (CHCl 3 ,c=1.00,24° C.). mp.120.0-121.0° C.

No.1a-112

CDCl 3 300 MHz 0.96-2.04(14H,m),2.19(1H,m),2.33(2H,d,J=7.1 Hz),3.07(1H,m),5.28-5.31(2H,m),5.33(1H,d,J=6.6 Hz),7.54-7.63(3H,m),8.05(2H,d,J=8.4 Hz),8.18-8.23(2H,m),8.41(2H,d,J=8.4 Hz).

IR(CHCl 3 ):3384,3269,3025,3015,2957,2877,1708,1598,1496,1457,1417,1326,1164/cm.

[α] D =+12.2° (CHCl 3 ,c=1.00,24° C.). mp.163-164° C.

No.1a-113

[α] D =+22.1° (CHCl 3 ,c=1.05,25° C.). mp.90-92° C.

No.1a-114

[α] D =+2.2° (CHCl 3 ,c=1.02;25° C.).

No.1a-115

CDCl 3 300 MHz 0.90-1.98(14H,m),2.15-2.22(1H,m),2.27(2H,t,J=7.2 Hz),2.95-3.04(1H,m), 3.68(3H,s),4.04(2H,s),4.85(1H,d,J=6.6 Hz),5.10-5.27(2H,m),7.12-7.34(7H,m), 7.76-7.82(2H,m).

IR(CHCl 3 ):3384,3026,2952,1727,1595,1493,1436,1318,1155,1091,890/cm.

[α] D =0°

[α] 436 =+4.9±0.4° (CHC 3 ,c=1.05,23° C.)

No.1a-116

CDCl 3 300 MHz 0.90-2.10(14H,m),2.10-2.18(1H,m),2.32(2H,t,J=7.2 Hz),2.96-3.04(1H,m),4.04(2H,s),5.14(1H,d,J=6.6 Hz),5.16-5.28(2H,m),7.12-7.34(7H,m),7.76-7.82(2H,m).

IR(CHCl 3 ):3260,3020,2950,1709,1407,1318,1154,1091,892/cm.

[α] D =+9.1±0.5° (CHCl 3 ,c=1.04,23° C.)

No.1a-117

CD 3 OD 300 MHz 0.96-2.18(17H,m),2.89-2.92(1H,m),4.05(2H,s),4.95-5.22(2H,m),7.15-7.42(7H,m),7.75-7.81 (2H,m).

IR(KBr):3429,3279,2951,2872,1563,1494,1453,1408,1313,1155,1093,1057/cm.

[α] D =−16.3±0.5° (CH 3 OH,c=1.06,25° C.)

No.1a-118

CDCl 3 300 MHz 0.98-1.70(15H,m), 1.80-2.00(5H,m),2.20-2.40(3H,m),2.98(1H,m),4.06(2H,s),4.72(1H,d,J=6.3 Hz),5.00-5.23(3H,m), 7.16(2H,d,J=8.4 Hz),7.26-7.33(5H,m),7.79(2H,d,J=8.1 Hz).

IR(CHCl 3 ):3376,3020,2948,2868,1716,1596,1492,1453,1407,1318,1155,1105/cm.

[α] D =+2.4° (CHCl 3 ,c=1.08,24° C.).

No.1a-119

CDCl 3 300 MHz 0.90-2.02(14H,m),2.20(1H,m),2.29(2H,t,J=7.2 Hz),3.00(1H,m),3.68(3H,s),4.86(1H,d,J=6.9 Hz),5.13-5.34(2H,m),7.00-7.09(4H,m),7.22(1H,m),7.37-7.45(2H,m),7.79-7.86(2H,m).

IR(CHCl 3 ):3376,3018,2946,2868,1727,1582,1486,1321,1243,1151,1093/cm.

[α] D =+4.5° (CHCl 3 ,c=1.05,23.5° C.).

No.1a-120

CD 3 OD 300 MHz 1.00-2.00(14H,m),2.13(2H,t,J=7.5 Hz),2.16(1H,m),2.91(1H,m),5.05-5.33(2H,m),7.04-7.11(4H,m),7.18-7.25(1H,m),7.38-7.48(2H,m),7.80-7.87(2H,m).

IR(KBr):3430,3278,3006,2952,2873,1583,1487,1410,1322,1298,1245,1152,1095/cm.

[α] D =−8.8° (CH 3 OH,c=1.05,25.0° C.).

No.1a-121

CDCl 3 300 MHz 0.90-2.10(14H,m),2.15(1H,m),2.35(2H,t,J=7.2 Hz),3.01(1H,m),5.20(1H,d,J=6.9 Hz),5.22-5.35(2H,m),7.00-7.09(4H,m),7.18-7.25(1H,m),7.37-7.45(2H,m),7.79-7.86(2H,m).

IR(CHCl 3 ):3260,3020,2948,2868,1708,1582,1486,1409,1321,1296,1243,1151,1093/cm.

[α] D =+13.1° (CHCl 33 ,c=1.04,24.0° C.).

No.1a-122

CDCl 3 300 MHz 0.90-2.00(14H,m),2.23(1H,m),2.28(2H,t,J=7.5 Hz),2.96(1H,m),3.67(3H,s),4.69(1H,d,J=6.6 Hz),5.15-5.32(2H,m),6.22(1H,s),6.98-7.40(5H,m),7.30-7.38(2H,m),7.68-7.74(2H,m).

IR(CHCl 3 ):3416,3370,3018,2946,2868,1725,1587,1508,1437,1400,1320,1149,1094/cm.

[α] D =+6.2° (CHCl 3 ,c=1.04,25.0° C.).

No.1a-123

CDCl 3 300 MHz 0.90-2.04(14H,m),2.18(1H,m),2.33(2H,t,J=7.2 Hz),2.96(1H,m),5.04-5.35(3H,m),6.98-7.12(3H,m),7.12-7.20(2H,m),7.28-7.38(2H,m),7.66-7.74(2H,m).

IR(CHCl 3 ):3424,3270,3028,2952,2872,1708,1587,1508,1445,1399,1320,1148,1092/cm.

[α] D =+20.9° (CHCl 3 ,c=1.06,23.0° C.).

No.1a-124

CDCl 3 300 MHz 0.90-2.00(14H,m),2.18(1H,m),2.28(2H,t,J=7.2 Hz),3.00(1H,m),3.14(3H,s)3.68(3H,s),4.56(2H,s),4.84(1H,d,J=6.3 Hz),5.10-5.29(2H,m),7.16-7.26(4H,m),7.26-7.34(2H,m),7.78-7.84(2H,m).

IR(CHCl 3 ):3384,3028,2952,2874,1727,1598,1501,1435,1410,1370,1329,1172,1148,1091/cm.

[α] D =+2.7° (CHCl 3 ,c=1.09,23.0° C.).

No.1a-125

CDCG 3 300 MHz 0.90-2.00(14H,m),2.18(1H,m),2.28(2H,t,J=7.2 Hz),2.29(3H,s),3.00(1H,m),3.68(3H,s),4.04(2H,s),4.80(1H,d,J=6.6 Hz),5.11-5.29(2H,m),6.99-7.06(2H,m),7.12-7.19(2H,m),7.31(2H,d,J=8.1 Hz),7.79(2H,d,J=8.1 Hz).

IR(CHCl 3 ):3382,3280,3024,2950,2874,1730,1596,1504,1435,1407,1367,1318,1196,1155,1091/cm.

[α] D =+2.9° (CHCl 3 ,c=1.06,23.0° C.).

No.1a-126

CDCl 3 300 MHz 0.90-2.02(14H,m),2.14(1H,m),2.29(3H,s),2.32(2H,t,J=7.2 Hz),3.01(1H,m),4.03(2H,s),5.10(1H,d,J=6.6 Hz),5.15-5.30(2H,m),6.98-7.06(2H,m),7.11-7.18(2H,m),7.30(2H,d,J=8.1 Hz),7.79(2H,d,J=8.1 Hz).

IR(CHCl 3 ):3374,3260,3020,2948,2868,1749,1708,1596,1504,1407,1369,1317,1195,1155,1091/cm.

[α] D =+10.0° (CHCl 3 ,c=1.09,23.0° C.).

No.1a-127

CDCl 3 300 MHz 0.87-1.95(14H,m),2.18-2.32(3H,m),2.95(1H,m),3.69(3H,s),3.96(2H,s),4.79(1H,d, J=6.6 Hz),4.97-5.17(2H,m),5.54(1H,s),6.75-6.82(2H,m),6.97-7.05(2H,m),7.25-7.33 (2H,m),7.75-7.81 (2H,m).

IR(CHCl 3 ):3382,3026,2950,2874,1722,1595,1511,1436,1407,1317,1257,1154,1090/cm.

[α] D =−2.1° (CHCl 3 ,c=1.00,21.5° C.).

No.1a-128

CDCl 3 300 MHz 0.85-2.02(14H,m),2.18(1H,m),2.31(2H,t,J=7.2 Hz),2.96(1H,m),3.95(2H,s),5.05-5.27(3H,m),6.73-6.82(2H,m),6.96-7.04(2H,m),7.25-7.32(2H,m),7.74-7.81(2H,m).

IR(CHCl 3 ):3262,3020,2948,2868,1708,1596,1511,1407,1315,1242,1154,1091/cm.

[α] D =+4.8° (CHCl 3 ,c=1.04,22° C.).

No.1a-129

CDCl 3 300 MHz 0.89-1.98(14H,m),2.18(1H,m),2.27(2H,t,J=7.2 Hz),2.99(1H,m),3.68(3H,s),3.79(3H,s),3.98(2H,s),4.81(1H,d,J=6.6 Hz),5.10-5.27(2H,m),6.81-6.87(2H,m),7.03-7.10(2H,m),7.25-7.32(2H,m),7.75-7.82(2H,m).

IR(CHCl 3 ):3382,3276,3006,2950,2874,1726,1609,1509,1457,1436,1407,1315,1244,1154,1091,1033/cm.

[α] D =+19.3° (CHCl 3 ,c=1.05,23° C.).

No.1a-130

CDCl 3 300 MHz 0.90-2.00(14H,m),2.20(1H,m),2.30(2H,t,J=7.2 Hz),2.98(1H,m),3.69(3H,s),4.81(1H,d,J=6.6 Hz),5.12-5.32(2H,m),5.46(1H,brs),6.84-7.01(6H,m),7.76-7.83(2H,m).

IR(CHCl 3 ):3380,3284,3024,2952,2874,1724,1588,1504,1488,1436,1321,1296,1149,1091/cm.

[α] D =+28.9° (CHCl 3 ,c=1.01,23° C.).

No.1a-131

CDCl 3 300 MHz 0.92-2.10(14H,m),2.18(1H,m),2.34(2H,t,J=6.9 Hz),2.96(1H,m),5.18-5.35(3H,m),6.84-7.01(6H,m),7.75-7.83(2H,m).

IR(CHCl 3 ):3270,3028,2952,2874,1708,1589,1505,1489,1456,1322,1297,1238,1148,1091/cm.

[α] D =+7.7° (CHCl 3 ,c=1.09,24° C.).

No.1a-132

CDCl 3 300 MHz 0.91-2.02(14H,m),2.19(1H,m),2.29(2H,t,J=7.2 Hz),2.99(1H,m),3.68(3H,s),3.83(3H,s),4.82(1H,d,J=6.6 Hz),5.14-5.33(2H,m),6.90-7.04(6H,m),7.76-7.83(2H,m).

IR(CHCl 3 ):3384,3006,2952,2874,1727,1589,1502,1488,1459,1488,1321,1295,1231,1150,1092,1033/cm.

[α] D =+3.1° (CHCl 3 ,c=1.01,23° C.).

No.1a-133

TLC Rf=0.21 (ethyl acetate/n-hexane=1:1 (0.3% acetic acid))

No.1a-134

CDCl 3 300 MHz 0.97-2.10(14H,m),2.20(1H,m),2.36(2H,t,J=6.9 Hz),3.04(1H,m),5.22-5.33(2H,m),5.41(1H,d,J=6.6 Hz),7.02(1H,d,J=9.0 Hz),7.09-7.13(2H,m),7.26-7.32(1H,m),743-7.49(2H,m),7.93(1H,d.d,J=2.4 and 9.0 Hz),8.46(1H,d,J=2.4 Hz).

IR(CHCl 3 ):3384,3270,3020,2958,1709,1610,1587,1537,1479,1352,1271,1252,1167/cm.

[α] D =+20.9° (CHCl 3 ,c=0.51,22° C.).

No.1a-135

CDCl 3 300 MHz 0.96-2.02(14H,m),2.21(1H,m),2.29(2H,t,J=7.2 Hz),3.07(1H,m),3.68(3H,s),5.04(1H,d,J=6.9 Hz),5.16-5.33(2H,m),7.48-7.55(2H,m),7.64 (1H,m),7.76-7.82(2H,m),7.88-7.94(2H,m),7.98-8.04(2H,m).

IR(CHCl 3 ):3384,3282,3026,2952,2874,1727,1663,1596,1446,1396,1316,1274,1163,1090/cm

[α] D =+3.1° (CHCl 3 ,c=1.03,22.0° C.).

No.1a-136

CDCl 3 300 MHz 0.95-2.05(14H,m),2.19(1H,m),2.34(2H,t,J=7.2 Hz),3.08(1H,m),5.10-5.40(2H,m),5.35(1H,d,J=6.8 Hz),7.45-7.58(2H,m),7.64(1H,m),7.74-7.84(2H,m),7.84-7.95(2H,m),7.95-8.06(2H,m).

IR(CHCl 3 ):3260,3018,2950,2870,1708,1662,1595,1446,1395,1316,1274,1162,1090/cm.

[α] D =+12.9° (CHCl 3 ,c=1.05,21.5° C.).

No.1a-137

CDCl 3 300 MHz 0.97-2.04(14H,m),2.27(1H,m),2.31(2H,t,J=7.2 Hz),3.07(1H,m),3.70(3H,s),5.15-5.30(3H,m),7.48-7.68(5H,m),7.96-8.02(2H,m).

IR(CHCl 3 ):3382,3030,2952,2878,1725,1446,1329,1154,1098/cm.

[α] D =−12.1° (CHCl 13 ,c=1.03,22.0° C.).

No.1a-138

CDCl 3 300 MHz 0.95-2.04(14H,m),2.25(1H,m),2.35(2H,t,J=7.2 Hz),3.08(1H,m),5.15-5.34(2H,m),5.41(1H,d,J=6.6 Hz),7.48-7.68(5H,m),7.98-8.03(2H,m).

IR(CHCl 3 ):3370,3242,3022,2950,2870,1707,1445,1408,1329,1154,1099/cm.

[α] D =−0.6° (CHCl 3 ,c=1.06,21.5° C.) [α] 365 +30.7° (CHCl 3 ,c=1.06,21.5° C.).

No.1a-139

CDCl 3 300 MHz 0.92-2.19(14H,m),2.27-2.34(3H,m),3.26(1H,m),3.65(3H,s),4.28(2H,s),4.37(1H,d,J=7.4 Hz),5.34-5.50(2H,m),7.37-7.62(9H,m).

IR(CHCl 3 ):3389,3294,3028,3015,2954,2877,1730,1600,1488,1325,1151,1129/cm.

[α] D =−24.8° (CHCl 3 ,c=1.01,24° C.).

No.1a-140

CDCl 3 300 MHz 0.92-2.22(15H,m),2.34(2H,t,J=7.1 Hz),3.24(1H,m),4.29(2H,s),4.81(1H,d,J=7.4 Hz),5.32-5.52(2H,m),7.36-7.62(9H,m).

IR(CHCl 3 ):3510,3388,3251,3031,3015,2956,2877,2668,1708,1601,1488,1318,1151,1129/cm.

[α] D =−24.6° (CHCl 3 ,c=1.02,25° C.).

No.1a-141

CDCl 3 300 MHz 0.92-2.19(15H,m),2.32(2H,t,J=7.2 Hz),3.26(1H,m),3.65(3H,s),4.31(2H,s),4.48(1H,d,J=7.4 Hz),5.33-5.49(2H,m),7.42-7.80(8H,m).

IR(CHCl 3 ):3388,3285,3018,2955,2877,2225,1730,1597,1479,1320,1152,1129/cm.

[α] D=− 20.1° (CHCl 3 ,c=0.96,25° C.).

No.1a-142

CDCl 3 300 MHz 0.92-2.22(15H,m),2.35(2H,t,J=6.8 Hz),3.25(1H,m),4.32(2H,s),4.86(1H,d,J=7.4 Hz),5.33-5.53(2H,m),7.43-7.80(8H,m).

IR(CHCl 3 ):3512,3388,3258,3031,3023,3014,2956,2877,2225,1708,1597,1479,1319,1151,1128/cm.

[α] D =−19.3° (CHCl 3 ,c=1.09,23° C.).

No.1a-143

CDCl 3 300 MHz 1.00-1.93(14H,m),2.17(1H,m),2.27(2H,t,J=7.2 Hz),3.07(1H,m),5.17-5.22(2H,m),5.36(1H,d,J=6.9 Hz),7.77(1H,d,J=9.0 Hz),8.11-8.17(2H,m),8.36(1H,d.d,J=2.1 and 9.0 Hz),8.5 1(1H,d,J=1.8 Hz),8.65(1H,d,J=2.1 Hz).

IR(CHCl 3 ):3382,3266,3026,2954,2874,1708,1632,1585,1528,1458,1419,1345,1153/cm.

[α] D =+7.6° (CHCl 3 ,c=1.04,22° C.).

No.1a-144

CDCl 3 300 MHz 0.95-1.90(14H,m),2.17(1H,m),2.25(2H,t,J=7.5 Hz),3.02(1H,m),5.09(1H,d,J=6.6 Hz),5.15-5.21(2H,m),6.72(1H,d,J=8.4 Hz),6.85(1H,s),7.54(1H,d,J=8.4 Hz),7.72(1H,d,J=9.0 Hz),7.83(1H,d.d,J=1.8 and 9.0 Hz),8.32(1H,d,J=1.8 Hz).

IR(CHCl 3 ):3380,3260,3022,2948,2868,2352,1709,1636,1460,1425,1313,1291,1265,1148,1130/cm.

[α] D =+12.9° (CHCl 3 ,c=1.02,22.5° C.).

No.1a-145

CDCl 13 300 MHz 0.97-1.90(14H,m),2.15(1H,m),2.27(2H,t,J=6.9 Hz),3.02(1H,m),3.08(6H,s),5.12(1H,d,J=6.3 Hz),5.19-5.25(2H,m),6.78-6.84(2H,m),7.53(1H,d,J=8.7 Hz),7.76-7.83(2H,m),8.30(1H,d,J=1.8 Hz).

IR(CHCl 3 ):3272,3030,2950,2874,1708,1635,1601,1511,1457,1425,1357,1328,1151,1124/cm.

[α] D =+6.3° (CHCl 3 ,c=1.04,23° C.).

No.1a-146

CDCl 3 300 MHz 0.95-2.00(14H,m),2.16(1H,m),2.29(2H,t,J=7.2 Hz),3.05(1H,m),4.10(3H,s),5.13-5.28(2H,m),5.38(1H,d,J=6.9 Hz),7.67-7.74(2H,m),8.08(1H,d.d,J=1.8 and 9.0 Hz),8.11 (1H,s),8.61 (1H,d,J=1.8 Hz).

IR(CHCl 3 ):3260,3020,2948,2868,1708,1639,1606,1528,1470,1455,1424,1349,1311,1238,1174,1149,1120,1079,1060,1022/cm.

[α] D =+7.8° (CHCl 3 ,c=1.00,23° C.).

No.1a-147

CDCl 3 300 MHz 0.92-1.92(14H,m),2.25(2H,t,J=7.2 Hz),3.01(1H,m),3.97(3H,s),5.10-5.27(5H,m),6.92(1H,s),7.29(1H,s),7.52(1H,d,J=8.7Hz),7.82(1H,d.d,J=2.1 and 8.7 Hz),8.33(1H,d,J=2.1 Hz).

IR(CHCl 3 ):3380,3264,3002,2950,2868,1708,1634,1476,1452,1426,1317,1264,1218,1169,1147,1115,1068,1031/cm.

[α] D =+5.6° (CHCl 3 ,c=1.02,23° C.).

No.1a-148

CDCl 3 300 MHz 0.90-1.98(14H,m),2.15(1H,m),2.28(2H,t,J=6.9 Hz),2.91(6Hs),3.03(1H,m),4.01(3H,s),5.15-5.26(3H,m),7.18(1H,s),7.38(1H,s),7.59(1H,d,J=8.7 Hz),7.87(1H,d.d,J=2.1 and 8.7 Hz),8.40(1H,d,J=2.1 Hz).

IR(CHCl 3 ):3384,3266,2956,1709,1632,1602,1495,1473,1458,1430,1317,1231,1148,1121/cm.

[α] D =+11.2° (CHCl 3 ,c=1.01,23° C.).

No.1a-149

CDCl 3 300 MHz 0.99-1.90(14H,m),2.17(1H,m),2.28(2H,t,J=7.2 Hz),3.00(1H,m),5.13-5.19(2H,m),5.43(1H,d,J=6.0 Hz),7.02(1H,d.d,J=2.4 and 9.0 Hz),7.38-7.41(2H,m),7.58(1H,d,J=8.7 Hz),7.96(1H,d.d,J=1.8 and 8.7 Hz),8.45(1H,d,J=1.8 Hz).

IR(CHCl 3 ):3270,3020,2948,2868,1709,1601,1478,1448,1419,1315,1147,1120/cm.

[α] D =−11.4° (CHCl 3 ,c=1.01,23° C.).

No.1a-150

CDCl 3 300 MHz 0.97-1.88(14H,m),2.12-2.31(3H m),2.38(3H,s),3.01(1H,m),5.14-5.19(2H,m),5.36(1H,d,J=6.6 Hz),7.24(1H,d.d,J=2.4 and 9.0 Hz),7.59(1H,d,J=6.3 Hz),7.66(1H,d,J=8.7 Hz),7.72(1H,d,J=2.4 Hz),8.01(1H,d.d,J=1.8 and 8.7 Hz),8.49(1H,d,J=1.8 Hz).

IR(CHCl 3 ):3470,3374,3260,3018,2950,2868,1709,1474,1444,1412,1370,1319,1266,1162,1145,1118/cm.

[α] D =+4.90° (CHCl 3 ,c=1.00,24° C.).

No.1a-151

CDCl 3 300 MHz 0.97-1.89(14H,m),2.17(1H,m),2.25(2H,t,J=7.2 Hz),3.03(1H,m),3.92(3H,s),5.15-5.20(2H,m),5.32(1H,d,J=6.6 Hz),7.11(1H,d.d,J=2.4 and 9.3 Hz),7.45(1H,d,J=2.4 Hz),7.50(1H,d,J=9.3 Hz),7.62(1H,d,J=8.7H),7.97(1H,d.d,J=2.1 and 8.7 Hz ), 8.50(1H,d,J=2.1 Hz).

IR(CHCl 3 ):3260,3018,2948,1708,1483,1454,1432,1314,1287,1268,1188,1169,1147/cm.

[α] D =+4.9° (CHCl 3 ,c=1.01,23.5° C.).

No.1a-152

CDCl 3 300 MHz 0.98-2.04(14H,m),2.15(1H,m),2.30(2H t,J=6.6 Hz),3.04(1H,m),5.17-5.29(3H,m),7.41(1H,d.d,J=1.5 and 8.1 Hz),7.64-7.68(2H,m),7.92(1H,d,J=8.4 Hz),8.00(1H,d.d,J=1.8 and 8.4 Hz),8.49(1H,d,J=1.8 Hz).

IR(CHCl 3 ):3266,3028,2952,2872,1707,1629,1591,1456,1416,1318,1275,1150/cm.

[α] D =+3.2° (CHCl 3 c=1.04,23° C.).

No.1a-153

CDCl 3 300 MHz 0.97-1.88(14H,m),2.16(1H,m),2.26(2H,t,J=7.2 Hz),3.03(1H,m),4.64-4.65(2H,m),5.16-5.50(5H,m),6.13(1H,m),7.14(1H,d.d,J=2.7 and 9.0 Hz),7.46-7.52(2H,m),7.63(1H,d,J=8.7 Hz),7.97(1H,d.d,J=1.8 and 8.7 Hz),8.49(1H,d,J=1.8 Hz).

IR(CHCl 3 ):3374,3260,3020,2948,2868,1708,1599,1478,1446,1414,1314,1284,1268,1184,1148,1120/cm.

[α] D =+5.3° (CHCl 3 ,c=1.00,23° C.).

No.1a-154

CDCl 3 300 MHz 0.99-2.00(15H,m),2.26(2H,t,J=7.2 Hz),3.03(1H,m),4.07(3H,s),5.23-5.27(2H,m),5.36(1H,d,J=7.2 Hz),7.20(1H,s),7.36-7.48(2H,m),7.55-7.58(1H,m),7.91-7.93(1H,m),8.52(1H,s).

IR(CHCl 3 ):3362,3257,3020,2948,2868,1708,1637,1602,1579,1488,1457,1437,1413,1345,1318,1301,1276,1182,1104/cm.

[α] D =+19.4° (CHCl 3 ,c=1.01,25° C.).

mp.88-90° C.

No.1a-155

CDCl 3 300 MHz 0.92-2.02(14H,m),2.15(1H,m),2.31(2H,t,J=7.2 Hz),3.01(1H,m),4.10(2H,s),5.10(1H,d,J=6.6 Hz),5.18-5.35(2H,m),7.04-7.26(5H,m),7.67-7.76(2H,m).

IR(CHCl 3 ):3266,3028,2952,2952,2872,1708,1599,1574,1478,1457,1418,1301,1258,1147,1124,1101,1080/cm.

[α] 365 +33.4° (CHCl 3 ,c=1.00,23° C.).

No.1a-156

CDCl 3 300 MHz 0.91-2.21(15H,m),2.33(2H,t,J=6.9 Hz),3.01(1H,m),5.11(1H,d,J=6.6 Hz),5.27-5.35(2H,m),6.85-6.96(5H,m),7.35(1H,d,J=2.1 Hz),7.42(1H,d.d,J=2.1 and 8.7Hz).

IR(CHCl 3 ):3384,3263,2957,1708,1587,1489,1462,1416,1290,1222,1151,1123/cm.

[α] D =+6.4° (CHCl 3 ,c=1.00,23° C.).

No.1a-157

CDCl 3 300 MHz 0.97-1.91(14H,m),2.18(1H,m),2.26(2H,t,J=6.9 Hz),3.04(1H,m),5.18-5.26(3H,m),7.52-7.56(2H,m),7.88-8.00(3H,m),8.25(1H,m),8.69(1H,m).

IR(CHCl 3 ):3382,3268,2952,2874,1707,1457,1425,1409,1318,1152/cm.

[α] D =+4.4° (CHCl 3 ,c=1.02,22° C.).

No.1a-158

CDCl 3 300 MHz 1.02-1.97(14H,m),2.20(1H,m),2.29(2H,t,J=7.2 Hz),3.06(1H,m),5.19-5.24(2H,m),5.58(1H,d,J=6.6 Hz),7.62(1H,m),7.72(1H,m), 7.86-7.91(2H,m),7.96(1H,d,J=7.8 Hz),8.04(1H,d.d,J=1.5 and 8.1 Hz),8.34(1H,d,J=1.2 Hz).

IR(CHCl 3 ):3490,3260,3020,2950,2870,1707,1456,1399,1312,1165/cm.

[α] D =−8.3° (CHCl 3 ,c=1.00,23° C.).

No.1a-159

CDCl 3 300 MHz 0.92-1.88(14H,m),2.13(1H,m),2.24(2H,m),3.02(1H,m),3.90(3H,s),5.12-5.26(3H,m),7.29-7.58(4H,m),7.97(1H,d.d,J=1.8 and 7.5 Hz),8.13(1H,d,J=7.5 Hz),8.64(1H,d,J=1.8 Hz).

IR(CHCl 3 ):3382,3266,3018,2956,1708,1629,1594,1476,1467,1325,1245,1227,1158,1146/cm.

[α] D =+14.6° (CHCl 3 c=1.00,22° C.).

No.1a-160

CDCl 3 300 MHz 0.93-1.88(14H,m),2.18-2.24(3H,m),3.00(1H,m),5.08-5.21(3H,m),7.28-7.33(1H,m),7.47-7.51(3H,m),7.90(1H,d.d,J=1.5 and 7.8 Hz),8.10(1H,d,J=7.8 Hz),8.63-8.64(2H,m).

IR(CHCl 3 ):3465,3380,3275,3020,2957,2876,1708,1627,1604,1495,1473,1457,1328,1240,1222,1156,1149/cm.

[α] D =+8.2° (CHCl 3 ,c=1.01,22° C.).

No.1a-161

CDCl 3 300 MHz 0.98-1.88(14H,m),2.17(1H,m),2.24(2H,t,J=7.2 Hz),3.05(1H,m),5.16-5.20(2H,m),5.35(1H,d,J=6.6 Hz),7.40(1H,m),7.55(1H,m),7.63(1H,d,J=8.1 Hz),7.89(1H,d.d,J=1.5 and 8.1 Hz),8.01(1H,m),8.06(1H,d,J=8.1 Hz),8.12(1H,d,J=1.5 Hz).

IR(CHCl 3 ):3478,3266,3028,2952,2874,1708,1454,1417,1323,1196,1148/cm.

[α] D =+21.9° (CHCl 3 ,c=1.01,23° C.).

No.1a-162.

CDCl 3 300 MHz 0.96-1.98(14H,m),2.02(1H,m),2.25(2H,t,J=7.2 Hz),3.05(1H,m),4.10(3H,s),5.14-5.25(2H,m),5.41(1H,d,J=7.2 Hz),7.35-7.42(1H,m),7.51-7.64(3H,m),7.94-8.00(1H,m),8.16(1H,s).

IR(CHCl 3 ):3368,3274,3028,2952,2874,1708,1633,1583,1465,1452,1438,1413,1315,1151,1103,1053,1024/cm.

[α] D =+15.1° (CHCl 3 ,c=1.01,23° C.). mp.108-110° C.

No.1a-163

d 6 -DMSO 300 MHz 0.97-1.84(14H,m), 1.92(1H,m),2.04(2H,t,J=7.5 Hz),2.90(1H,m),5.08-5.23(2H,m),7.32(1H,s), 7.38-7.61(2H,m),7.62(1H,s),7.68-7.71(1H,m),7.92(1H,s),8.14-8.17(1H,m),10.7(1H,s),11.9(1H,s).

IR(KBr):3350,3295,2952,2874,1707,1636,1601,1466,1431,1389,1315,174,1146,1106/cm.

[α] D =−25.3° (CH 3 OH,c=1.01,25° C.). mp.159-162° C.

No.1a-164

CDCl 3 300 MHz 0.98-1.96(17H,m),2.05(1H,m),2.25(2H,t,J=7.2 Hz),3.07(1H,m),4.32(2H,q,J=7.2 Hz),5.19-5.23(2H,m),5.31(1H,d,J=7.8 Hz),7.38(1H,m),7.41-7.62(3H,m),7.95(1H,m),8.15(1H,s).

IR(CHCl 3 ):3360,3018,2946,2870,1709,1633,1457,1445,1425,1394,1314,1176,1152,1105/cm.

[α] D =+12.7° (CHCl 3 ,c=1.02,25° C.). mp.108-109° C.

No.1a-165

CDCl 3 300 MHz 0.95-1.98(15H,m),2.26(2H,t,J=7.5 Hz),3.04(1H,m),4.15(3H,s),5.20-5.26(2H,m),5.34(1H,d,J=6.9 Hz),7.41-7.47(1H,m), 7.65-7.68(2H,m),7.89-7.92(1H,m),8.32(1H,s).

IR(CHCl 3 ):3366,3087,3022,2957,1708,1632,1538,1463,1408,1364,1346,1308,1227,1212,1205,1167/cm.

[α] D =+19.6° (CHCl 3 ,c=1.01,25° C.).

No.1a-166

CDCl 3 300 MHz 0.97-2.02(15H,m),2.27(2H,t,J=6.9 Hz),3.07(1H,m),4.14(3H,s),5.21-5.27(2H,m),5.47(1H,d,J=6.9 Hz),7.64(1H,s),7.72(1H,d.d,J=0.6 and 9.0 Hz),8.25(1H,s),8.47(1H,d.d,J=2.4 and 9.0 Hz),8.94(1H,d.d,J=0.6 and 2.4 Hz).

IR(CHCl 3 ):3373,2957,1708,1639,1587,1528,1467,1428,1415,1345,1221,1184,1155/cm.

[α] D =+14.4° (CHCl 3 ,c=0.50,25° C.)

No.1a-167

CDCl 3 300 MHz 0.92-2.00(14H,m),2.15(1H,m),2.27(2H,t,J=7.2 Hz),3.04(1H,m),3.97(2H,S),5.15-5.30(3H,m),7.35-7.47(2H,m),7.55-7.63(1H,m),7.80-7.96(3H,m),8.05(1H,d,J=0.3 Hz).

IR(CHCl 3 ):3260,3020,2948,2868,1707,1451,1413,1319,1172,1144,1101,1071/cm.

[α] D =+18.2° (CHCl 3 ,c=1.04,22° C.).

No.1a-168

CDCl 3 300 MHz 0.90-1.88(14H,m),2.16(1H,m),2.25(2H,t,J=6.9 Hz),3.00(1H,m),5.00-5.19(2H,m),5.35(1H,d,J=6.6 Hz),7.25-7.30(1H,m),7.48-7.50(2H,m),7.73(1H,d.d,J=1.5 and 8.1 Hz),8.08-8.14(3H,m),8.93(1H,s).

IR(CHCl 3 ):3466,3380,3276,3016,2957,1708,1630,1495,1458,1324,1241,1150/cm.

[α] D =+18.0° (CHCl 3 ,c=1.00,22° C.).

No.1a-169

CDCl 3 300 MHz 0.87-1.86(14H,m),2.15(1H,m),2.25(2H,t,J=6.9 Hz),2.98(1H,m),3.89(3H,s),5.00-5.22(2H,m),5.27(1H,d,J=6.9 Hz),6.88(1H,d.d,J=2.1 and 8.4 Hz),6.94(1H,d,J=2.1 Hz),7.69(1H,d.d,J=1.5 and 7.8 Hz),7.9-8.01(3H,m),8.83(1H,s).

IR(CHCl 3 ):3465,3378,3276,3022,2957,1708,1630,1609,1569,1459,1433,1314,1281,1229,1151/cm.

[α] D =+19.3° (CHCl 3 ,c=1.01,21° C.).

No.1a-170

CDCl 3 300 MHz 0.88-2.25(17H,m),3.04(1H,M),3.84(3H,s),3.95(3H,s),5.06-5.26(3H,m),6.87-6.93(2H,m),7.69(1H,d.d,J=1.6 and 8.2 Hz),7.93-9.05(3H,m).

IR(CHCl 3 ):3026,2957,1708,1630,1601,1460,1331,1243,1224,1152/cm.

[α] D =+17.2° (CHCl 3 ,c=1.00,22° C.).

No.1a-171

CDCl 3 300 MHz 0.95-2.00(14H,m),2.16-2.32(3H,m),2.66(3H,s),3.14(1H,m),3.68(3H,s),5.09(1H,d,J=6.8 Hz),5.10-5.28(2H,m),7.45(1H,d.d.,J=1.8 & 8.6 Hz),7.75-7.84(2H,m).

IR(CHCl 3 ):3374,3018,2946,2868,1725,1585,1513,1436,1340,1278,1153,1112/cm.

[α] D =−14.7° (CHCl 3 ,c=1.07,25.0° C.).

No.1a-172

CDCl 3 300 MHz 0.97-2.02 (14H,m),2.23(1H,m),2.28(2H,t,J=7.2 Hz),2.66(3H, s),3.14(1H, m),5.12-5.22(2H,m),5.41(1H,d,J=7.2 Hz),7.45(1H,d.d.,J=2.1 & 8.7 Hz),7.76(1H,d,J=8.7 Hz),7.78(1H,d,J=2.1 Hz).

IR(CHCl 3 ):3372,3250,3022,2950,2868,1707,1514,1419,1336,1279,1154,1112/cm.

[α] D =−4.1° (CHCl 3 ,c=1.08,26.0° C.) m.p.141-143° C.

No.1a-173

CDCl 3 300 MHz 1.15-2.42(17H,m),2.91(1H,m),5.15(1H,d,J=4.2 Hz),5.25-5.40(2H,m),7.85(1H,t,J=7.2 Hz),8.00(1H,t,J=8.1 Hz),8.15-8.20(2H,m),8.67(1H,d,J=8.1 Hz),8.73(1H,d,J=8.1 Hz),8.83(1H,s),9.43(1H,s).

IR(KBr):3422,3269,3046,2952,2871,1711,1617,1447,1333,1243,1161,1146/cm.

[α] D =−41.0° (CH 3 OH,c=1.01,23° C.).

No.1a-174

CDCl 3 +d 6 -DMSO 300 MHz 1.00-1.92(14H,m),2.20(2H,t,J=6.6 Hz),2.35(1H,m),2.92(1H,m),5.05-5.22(2H,m),6.63(1H,d,J=5.4 Hz),7.77-7.92(3H,m),8.31(1H,d.d,J=1.8 and 8.7 Hz),8.59(1H,d,J=8.7 Hz),8.73(1H,d,J=8.7 Hz),9.01(1H,s),9.55(1H,d,J=1.8 Hz).

IR(KBr):3433,322,2952,2871,1696,1578,1423,1335,1308,1219,1185,1106/cm.

[α] D =−19.3° (DMSO,c=0.50,23° C.).

No.1a-175

CDCl 3 300 MHz 0.96-1.87(14H,m),2.20-2.25(3H,m),2.95(1H,m),3.66(3H, s),4.74(1H,d,J=6.6 Hz),5.10-5.12(2H,m),6.88(1H,d,J=1.2 Hz),7.37-7.50(3H,m),7.56(1H,dd,J=8.7,1.5 Hz),7.68-7.77(3H,m),8.06(1H,s),9.44(1H,dd,J=1.2 Hz).

IR(CHCl 3 ):3462,3374,3026,3006,2952,2872,1724,1610,1580,1484,1452,1358,1309,1147.

[α] D =−16.4° (CHCl 3 ,c=1.05,26° C.). mp.130-132° C.

No.1a-176

CDCl 3 +CD 3 OD 300 MHz 1.00-2.02(14H,m),2.22(1H,m),2.29(2H,t,J=6.9 Hz),2.88(1H,m),5.16-5.26(2H,m),6.87(1H,s),7.28-7.67(4H,m),7.69(1H,d,J=8.4 Hz),7.75-7.78(2H,m),7.99(1H,s).

IR(KBr):3254,2944,1704,1484,1453,1358,1305,1147.

[α] D =+13.0° (CH 3 OH,c=1.02,24° C.), mp.160-161° C.

No.1a-177

CDCl 3 300 MHz 0.96-1.88(14H,m),1.88-2.26(3H,m),2.94(1H,m),3.67(3H,s),3.87(3H,s),4.67(1H,brs),5.08-5.14(2H,m),6.77(1H,d,J=1.5 Hz),6.99-7.02(2H,m), 7.53-7.57(1H,m),7.65-7.70(3H,m),8.00(1H,s),9.27(1H,brs).

IR(CHCl 3 ):3426,3376,3006,2952,1724,1610,1495,1438,1357,1308,1282,1249,1177,1147/cm.

[α] D =+18.1° (CHCl 3 ,c=1.02,22° C.).

No.1a-178

CDCl 3 +CD 3 OD 300 MHz 0.96-1.91(14H,m),2.19(1H,m),2.27(2H,t,J=6.0 Hz),2.85(1H,m),3.87(3H,s),5.16-5.23(2H,m),6.99-7.02(2H,m),7.41(1H,m),7.64-7.73(3H,m),7.92(1H,m).

IR(CHCl 3 ):3366,3261,3004,2954,2873,1705,1611,1496,1458,1438,1304,1286,1253,1180,1149,1128/cm.

[α] D =+14.6° (CHCl 3 ,c=1.02,22° C.).

No.1a-179

CDCl 3 +CD 3 OD 300 MHz 0.96-1.87(1-4H,m),2.15-2.23(3H,m),2.93(1H,m),3.85(3H,s),5.10-5.16(2H,m),6.90-6.93( 2 H,m),7.50(1H,m),7.60-7.65(3H,m),7.91(1H,d,J=0.9 Hz).

IR(CHCl 3 ):3369,3270,2950,2873,1719,1612,1498,1456,1440,1359,1306,1269,1219,1146,1127/cm.

[α] D =+18.1° (CH 3 OH,c=1.00,22° C.).

No.1a-180

CDCl 3 +CD 3 OD 300 MHz 1.03-1.86(14H,m),2.08-2.17(3H,m),2.91(1H,m),5.06-5.10(2H,m),6.76(1H,m),6.86-6.90(2H,m),7.48(1H,m),7.61-7.69(3H,m),7.89(1H,m).

IR(CHCl 3 ):3360,3259,2954,2873,1706,1612,1497,1457,1360,1306,1272,1230,1176,1148,1126/cm.

[α] D =+20.3° (CH 3 OH,c=1.00,22° C.).

No.1a-181

CDCl 3 300 MHz 0.97-1.96(14H,m),2.15(1H,m),2.29(2H,t,J=6.9 Hz),3.05(1H,m),3.81(3H,s),5.08(1H,d,J=6.9 Hz),5.23-5.25(2H,m),6.62(1H,s),7.47-7.54(5H,m),7.59(1H,m),7.70(1H,m),7.97(1H,m).

IR(CHCl 3 ):3380,3260,3020,2946,2868,1708,1466,1388,1328,1149/cm.

[α] D =+32.9° (CHCl 3 ,c=1.07,22° C.).

No.1a-182

CDCl 3 300 MHz 0.94-1.90(14H,m),2.25(2H,t,J=7.5 Hz),2.30(1H,m),2.98(1H,m),3.70(3H,s),4.83(1H,d,J=6.6 Hz),5.13-5.16(2H,m),6.95(1H,d,J=1.5 Hz),7.11-7.23(2H,m),7.43(1H,d,J=8.1 Hz),7.65(1H,d,J=8.1 Hz),7.79-7.93(4H,m),9.08(1H,br).

IR(CHCl 3 ):3458,3372,3020,3002,2946,2868,1719,1598,1452,1422,1321,1300,1157/cm.

[α] D =−6.6° (CHCl 3 ,c=1.00), mp150-151° C.

No.1a-183

CDCl 3 300 MHz 0.95-1.94(14H,m),2.26(1H,m),2.28(2H,t,J=7.5 Hz),3.00(1H,m),5.16-5.19(2H,m),5.32(1H,d,J=7.2 Hz),6.93(1H,d,J=1.2 Hz),7.13(1H,m),7.22(1H,dd,J=7.8,6.6 Hz),7.42(1H,d,J=7.8 Hz),7.63(1H,d,J=7.8 Hz),7.76(2H,d,J=8.4 Hz),7.90(2H,d,J=8.4 Hz),8.95(1H,br).

IR(CHCl 3 ):3458,3374,3260,3020,3002,2948,2868,1708,1598,1452,1422,1301,1156/cm.

[α] D =+17.9° (CHCl 3 ,c=1.01,22° C.).

No.1a-184

CDCl 3 200 MHz 0.92-2.00(14H,m),2.20(1H,m),2.34(2H,t,J=6.8 Hz),3.05(1H,m),5,20-5.36(3H,m),7.39-7.44(2H,m),7.61-7.66(1H,m),7.80-7.84(1H,m),8.05(2H,d,J=8.6 Hz),8.40(2H,d,J=8.6 Hz).

IR(CHCl 3 ):3384,3271,3019,2958,1709,1615,1599,1551,1453,1405,1344,1326, 1243,1163/cm.

[α] D =+18.5° (CHCl 3 ,C=1.00,21° C.).

No.1a-185

CDCl 3 300 MHz 0.89-2.20(15H,m),2.26(2H,d.t,J=2.1 and 7.2 Hz),2.99(1H,m),5.08(1H,d,J=6.3 Hz),5.09-5.24(2H,M),6.90(1H,d,J=1,2 Hz),7.32-7.48(4H,m),7.64-7.72(3H,m),8.20(1H,d,J=1.2 Hz),9.00(1H,s).

IR(CHCl 3 ):3464,3375,3022,2956,1707,1605,1490,1449,1356,1322,1219, 1147,1131/cm.

[α] D =+21.6° (CHCl 3 ,C=1.01,23° C.).

No.1a-186

CDCl 3 :300 MHz 1.36-2.24(14H,m),2.31(2H,t,J=7.4 Hz),2.49(1H,brs),3.37(1H,m),3.67(3H,s),5.38-5.50(2H,m),7.40-7.68(9H,m).

IR(CHCl 3 ):3375,1727,1602,1435,1362,1221,1207,1168,1045/cm.

No.1a-187

CDCl 3 :300 MHz 1.10-2.25(14H,m),2.36(2H,t,J=7.2 Hz),2.47(1H,m),3.37(1H,m),5.35-5.54(2H,m),5.62(1H,d,J=7.2 Hz),7.39-7.70(9H,m).

IR(CHCl 3 ):3674,3496,3376,3234,3012,2952,2880,2650,1725(sh),1709,1602,1485, 1420,1360,1167/cm.

[α] D =+32° (CHCl 3 ,c=1.69).

No.1a-188

CDCl 3 200 MHz 0.86-1.92(14H,m),2.22(3H,m),2.36(3H,s),2.95(1H,m),3.67(3H,s),3.93(3H,s),4.81(1H,d,J=6.2 Hz),5.04-5.20(2H,m),7.02-7.05(2H,m),7.31(1H,d,J=8.6 Hz), 7.39(1H,d,J=7.8 Hz),7.79-7.89(3H,m).

IR(CHCl 3 ):3385,3286,3029,3019,3015,2954,2877,1718,1617,1598,1567,1507,1311,1269,1153/cm.

[a] D =−29.4° (CHCl 3 ,c=1.01,25° C.).

No.1a-189

[α] D =−7.7° (CHCl 3 ,c=1.00,24° C.).

No.1a-190

[α] D =−17.3° (CHCl 3 ,c=1.00,24° C.).

No.1a-191

CDCl 3 300 MHz 0.95-2.20(14H,m),2.30(1H,m),2.36(2H,d,J=6.9 Hz),3.21(1H,m),4.25(2H,s),5.07(1H,d,J=7.8 Hz),5.35-5.48(2H,m),7.25(1H,dd,J=1.8 and 8.1 Hz),7.32-7.35(2H,m),7.59(1H,d,J=8.1 Hz),7.94(1H,s),8.14(1H,d,J=2.7 Hz),8.23(1H,d.d,J=2.7 and 8.7 Hz).

IR(CHCl 3 ):3386,3026,3015,2957,2877,2633,1702,1617,1573,1530,1348,1123/cm.

[α] D =−6.1° (CHCl 3 s,c=1.01,25° C.).

No.1a-192

CDCl 3 300 MHz 0.92-2.20(14H,m),2.13(3H,m),3.23(1H,m),3.64(3H,s),3.94(3H,s),4.22(2H,s),4.36(1H,d,J=7.8 Hz),5.37-5.42(2H,m), 7.16-7.42(6H,m),7.53(1H,d,J=8.4 Hz),7.94(1H,s).

IR(CHCl 3 ):3389,3022,3013,2953,2877,1716,1616,1560,1485,1340,1326,1124/cm.

[α] D =−15.2° (CHCl 3 ,c=1.01,25° C.).

No.1a-193

CDCl 3 300 MHz 0.92-2.20(14H,m),2.25(1H,m),2.35(2H,t,J=7.2 Hz),3.17(1H,m),4.22(2H,s),4.91(1H,d, J=7.5 Hz), 5.37-5.42(2H, m),7.13-7.43(6H,m), 7.60(1H,d,J=8.1 Hz),8.05(1H,s).

IR(CHCl 3 ):3511,3387,3029,3020,3011,2957,2877,2651,1698,1614,1560,1505,1320,1280,1252,1126/cm.

[α] D =−0.9° (CHCl 3 ,c=1.00,25° C.).

No.1b-1

CDCl 3 300 MHz 0.98-1.56(15H,m),1.85-1.90(5H,m),2.23(1H,m),3.05(1H,m),3.66(3H,s),4.77(1H,d,J=6.0 Hz),5.08-5.28(2H,m),7.46(3H,m),7.38-7.54(2H,d,J=7.5 Hz),7.72(2H,d,J,8.4 Hz),7.93(2H,d,J=8.4 Hz).

IR(CHCl 3 ):3384,3028,2952,2876,1719,1595,1391,1322,1155/cm.

[α] 436 +4.0˜+6.0(CHCl 3 ,c=1.00,23° C.).

mp.96-98° C.

No.1b-2

CDCl 3 300 MHz 0.98-1.52(15H,m),1.85-1.90(5H,m),2.17(1H,m),3.00(1H,m),3.67(3H,s),4.05(2H,s),4.83(1H,d,J=6.0 Hz),5.05-5.23(2H,m),7.14(2H,d,J=7.2 Hz),7.17-7.32(5H,m),7.78(2H,d,J=8.4 Hz).

IR(CHCl 3 ):3384,3026,2952,2874,1719,1595,1453,1407,1320,1180/cm.

[α] D =+2.5° (CHCl 3 ,c=1.02,24° C.).

No.1b-3

CDCl 3 300 MHz 0.96-2.65(20H,m),2.07(1H,m),3.07(1H,m),4.04(2H,s),5.21-5.35(2H,m),5.55(1H,d,J=6.9 Hz),7.14(2H,d,J=6.6 Hz),7.20-7.32(5H,m),7.78(2H,d,J=8.1H).

IR(CHCl 3 ):3250,3022,2950,1699,1596,1495,1453,1405,1318,1153/cm.

[α] D =+17.1° (CHCl 3 ,c=1.01,25° C.).

mp.129-131° C.

No.1b-4

CDCl 13 200 MHz 0.90-2.10(15H,m),1.19(3H,s),1.20(3H,s),3.11(1H,m),5.24-5.32(2H,m)5.70 1H,d,J=6.6 Hz),7.38-7.68(4H,m),7.96-8.04(2H,m),8.53(1H,d,J=1.4 Hz).

IR(CHCl 3 ):3384,3246,2958,1701,1632,1595,1468,1445,1322,1216,1202,1190,1155,1122/cm.

[α] D =+10.8(CHCl 3 ,c=0.51,23° C.).

No.1b-5 1.02-2.10(15H,m),1.16(6H,s),3.02(1H,m),4.09(3H,s),5.23-5.28(2H,m),5.76(1H,d,J=7.2 Hz),7.36-7.63(4H,m),7.97(1H,d,J=7.8 Hz),8.16(1H,s).

IR(CHCl 3 ):3369,2959,1702,1635,1585,1468,1454,1441,1415,1318,1222,1189,1170,1154/cm.

[α] D =+9.9° (CHCl 3 ,c=1.00,23° C.).

No.1c-1

CDCl 3 300 MHz 1.10-2.02(14H,m),2.27(2H,t,J=7.5 Hz),2.50(1H,m),2.89(3H,s),3.31(1H,m),3.64(3H,s),5.16-5.30(2H,m),7.34-7.42(3H,m),7.50-7.59(2H,m),7.62-7.68(2H,m), 7.76-7.82(2H,m).

IR(CHCl 3 ):3020,2946,2868,2212,1727,1596,1495,1437,1339,1156,1135,1084/cm.

[α] D =−16.1° (CHCl 3 ,c=1.05,25.° C.).

m.p.100-102

No.1c-2

CDCl 3 300 MHz 1.10-2.05(14H,m),2.23(2H,t,J=7.5 Hz),2.53(1H,m),2.91(3H,s),3.35(1H,m),3.64(3H,s),5.02-5.30(2H,m),7.50-7.60(3H,m),7.90-8.08(6H,m).

IR(CHCl 3 ):3016,2946,2868,1728,1437,1398,1340,1160,1086/cm.

[α] D =−32.5° (CHCl 3 ,c=1.00,25.° C.).

No.1c-3

CD 3 300 MHz 1.15-2.05(14H,m),2.13(2H,t,J=7.2 Hz),2.47(1H,m),2.91(3H,s),3.27(1H,m),4.9-5.30(2H,m),7.37-7.44(3H,m),7.53-7.61(2H,m),7.71-7.77(2H,m),7.81-7.87(2H,m).

IR(KBr):3412,2999,2951,2871,2217,1560,1399,1243,1159,1137,1103,1084.

[α] D =−8.6° (CH 3 OH,c=1.03,23° C.).

No.1d-1

CDCl 3 300 MHz 1.00-2.16(15H,m),2.36(2H,t,J=7.2 Hz),3.17(1H,m),3.33(3H,s),5.23-5.43(3H,m),7.51-7.59(3H,m),7.91-8.10(6H,m),9.02(1H,brs).

IR(CHCl 3 ):3382,3268,3028,2954,2874,1715,1442,1400,1337,1162,1120,10891/cm.

[α] D =+40.0(CHCl 3 ,c=0.53,22° C.).

No.1d-2

CDCl 3 300 MHz 1.03-2.30(17H,m),3.03(1H,m),4.03(2H,s),5.26(2H,m),5.84(1H,br),5.25-5.29(1H,d,J=6.6 Hz),6.03(1H,br),7.14(2H,d,J=8.1 Hz),7.26-7.3(5H,m),7.80(2H,d, 8.1 Hz).

IR(CHCl 3 ):3376,3002,2946,1669,1595,1492,1454,1406,1318,1154/cm.

[α] D =+4.3° (CHCl 3 ,c=1.00,23° C.).

No.1d-3

CDCl 3 300 MHz 0.96-2.17(17H,m),2.33(2H,t,J=6.9 Hz),3.01(1H,m),4.04(2H,s),5.10(1H,d,J=6.6 Hz),5.21-5.26(2H,m),7.14(2H,d,J=8.7 Hz),7.16-7.32(5H,m),7.78(2d,h,J=8.4 Hz).

IR(CHCl 3 ):3260,3020,2946,1711,1596,1492,1457,1407,1318,1 154 /cm.

[α] D =+9.3° (CHCl 3 ,c=1.09,25° C.).

No.1d-4

CDCl 3 300 MHz 0.95-2.14(15H,m),2.34(2H,t,J=7.2 Hz),3.09(1H,m),3.30(3H,s),4.04(2H,s) (1H,d,J=7.2 Hz),5.22-5.39(2H,m),7.10-7.35(7H,m),7.81(2H,d,J=8.1 Hz),9.10(1H,brs). H,brs).

IR(CHCl 3 ):3382,3260,3028,2952,2874,2670,1713,1595,1492,1450,1405,1338,1160,1120,1092/cm.

[α] D =+22.2° (CHCl 3 ,c=1.07,22° C.).

No.1d-5

CDCl 3 300 MHz 1.00-2.10(14H,m),2.30-2.39(3H,m),3.15(1H,m),3.35(3H,s),5.18-5.40(3H,m),7.41(1H,d.t.,J=0.9and 7.8 Hz),7.50-7.69(3H,m),7.88-8.15(2H,m),8.60(1H,d,J=1.5 Hz),9.06(1H,s).

IR(CHCl 3 ):3382,3268,3028,2954,2874,1714,1442,1402,1338,1188,1155,1121,1072/cm.

[α] D =+15.3° (CHCl 3 s,c=1.00,22° C.).

No.1e-1

CDCl 3 300 MHz 1.19-2.45(19H,m),2.58(1H,m),5.63(1H,d,J=3.0 Hz),7.42-7.65(4H,m),7.94-8.03 (2H,m),8.49-8.50(1H,m).

IR(CHCl 3 ):3293,3024,1710,1595,1584,1467,1445,1410,1324,1222,1213,1206,1190,1160/cm.

[α] D =−41.1° (CHCl 3 ,c=1.01,23° C.).

No.1e-2

CDCl 3 300 MHz 1.10-2.25(19H,m),2.94(1H,m),4.12(3H,s),5.53(1H,d,J=7.2 Hz),7.39(1H,m), 7.50-7.62(3H,m),7.96(1H,d,J=7.5 Hz),8.13(1H,s).

IR(CHCl 3 ):3367,3025,29 55,1711,1634,1600,1584,1468,1454,1440,1415,1342,1317,1222,1189,1157/cm.

[α] D =+1.2° (CHCl 3 ,c=1.00,25° C.).

No.1f-1

CDCl 3 300 MHz 1.08-2.47(19H,m),2.56(1H,m),3.52(2H,t,J=6.6 Hz),5.59(1H,d,J=2.4 Hz),7.40-7.66(4H,m),7.95-8.04(2H,m),8.50(1H,d,J=1.8 Hz).

IR(CHCl 3 ):3624,3383,3295,2950,2877,1705,1595,1584,1468,1445,1405,1347,1337,1324,1224,1190,11601/cm.

[α] D =−54.1° (CHCl 3 ,c=1.01,23° C.).

No.1f-2

CDCl 3 300 MHz 1.08-2.24(19H,m),2.94(1H,m),3.53(2H,t,J=6.3 Hz),4.13(3H,s),5.47(1H,d,J=6.6 Hz),7.36-7.63(4H,m),7.96(1H,d,J=6.3 Hz),8.14(1H,s).

IR(CHCl 3 ):3625,3368,3025,3013,2949,2877,1710,1634,1600,1584,1468,1454,1440,1415,1342,1317,1232,1220,1189,1157/cm.

[α] D =−5.6° (CHCl 3 ,c=1.00,25° c.).

No.1g-1

CDCl 3 200 MHz 1.17-2.34(15H,m), 3.22(1H,m),5.10-5.16(2H,m), 5.45(1H,d,J=7.0 Hz), 7.35-7.66(4H,m),7.95-8.01(2H,m),8.51(1H,d,J=2.0 Hz).

IR(CHCl 3 ):3383,3275,2959,1707,1595,1584,1468,1445,1425,1319,1269,1248,1190,1149,1123/cm.

[α] D =+64.3° (CHCl 3 ,c=1.01,23° C.).

No.1g-2

CDCl 3 300 MHz 1.10-2.15(13H,m),2.36(2H,t,J=7.2 Hz),3.21(1H,m),4.09(3H,s),5.10-5.22(2H,m),5.43(1H,d,J=7.8 Hz),7.36-7.62(4H,m),7.96(1H,d,J=7.8 Hz),8.12(1H,s).

IR(CHCl 3 ):3366,2959,1708,1635,1600,1585,1467,1454,1440,1415,1345,1318,1233,1189,1152/cm.

[α] D =+103.1° (CHCl 3 ,c=1.01,23° C.).

No.1h-1

CDCl 3 300 MHz 0.90-1.60(17H,m),1.83(1H,m),2.11(1H,m),2.22(2H,t,J=7.2 Hz),3.07(1H,m) 5.11(1H,d,J=7.2 Hz),7.38-7.47(1H,m),7.50-7.60(1H,m),7.60-7.72(2H,m),7.88-8.12(2H,m),8.54(1H,d,J=0.9 Hz).

IR(CHCl 3 ):3382,3274,2926,1707,1464,1442,1318,1266,1188,1153,1121,1105,1071,1019/cm.

[α] D =−2.8° (CHCl 3 ,c=1.01,23° C.).

No.1i-1

[α] 365 +50.09° (CHCl 3 ,c=1.01,24° C.).

No.1i-2

CDCl 3 300 MHz 0.98-1.70(11H,m),1.80-2.00(5H,m),2.19(1H,m),3.03(1H,m),3.64(2H,t,J=6.6 Hz), 4.05(2H,s),4.69(1H,d,J=6.6 Hz),5.15(1H,m),5.25(1H,m),7.16.(2H,d,J=7.2 Hz), 7.27-7.32(5H,m),7.77(2H,d,J=8.4 Hz).

IR(CHCl 3 ):3376,3004,2946,2316,1596,1492,1453,1407,1318,1154/cm.

[α] D =+3.5° (CHCl 3 ,c=1.00,22° C.).

mp.80.5-82.0° C.

No.1j-1

[α] 436 =−7.5±0.5° (CHCl 3 ,c=1.05,22° C.).

No.1j-2

[α] D =−9.7±0.5° (CHCl 3 ,c=1.06,22° C.).

No.1j-3

[α] D =+15.0±0.5° (CH 3 OH,c=1.06,24.5° C.).

mp.101-108° C.

No.1j-4

[α] D =−28.0±0.6° (CHCl 3 ,c=1.06,24° C.).

mp.159-161° C.

1j-5

[α] D =−12.5±0.5° (CHCl 3 ,c=1.04,23° C.).

mp.99-101° C.

No.1j-6

CDCl 3 300 MHz 0.90-2.03(14H,m),2.20(1H,m),2.30(2H,t,J=7.3 Hz),3.00(1H,m)3.68(3H,s),4.76 (1H,d,J=6.8 Hz),5.13-5.35(2H,m),7.01-7.08(4H,m),7.19-7.26(1H,m),7.37-7.46 (2H,m),7.80-7.84(2H,m).

IR(CHCl 3 ):3382,3280,3080,3016,2952,2900,1727,1582,1486,1432,1322,1150/cm.

[α] D =−31.0° (CHCl 3 ,c=1.05,26° C.).

No.1j-7

CDCl 3 300 MHz 0.91-2.09(14H,m),2.15(1H,m),2.35(2H,t,J=7.5 Hz),3.01(1H,m),5.17(1H,d,J=6.8 Hz),5.21-5.34(2H,m),7.01-7.08(4H,m),7.15-7.27(1H,m),7.37-7.43(2H,m),7.80-7.85(2H,m).

IR(CHCl 3 ):3474,3386,3270,3024,2958,2900,2675,1711,1584,1488,1420,1323,1298,1150/cm.

[α] D =−13.4° (CHCl 3 ,c=1.01,26° C.).

No.1j-8

CDCl 3 300 MHz 0.95-2.14(13H,m),2.30(2H,t,J=7.5 Hz),2.36(1H,m),2.84(1H,m),2.91(1J=4.8 ),3.66(3H,s),5.33-5.52(2H,m),6.82-6.87(1H,m),6.93-7.00(2H,m),7.09-715(4H,m),7.28-7.36(2H,m),7.54-7.59(1H,m).

IR(CHCl 3 ):3350,3010,2950,2880,1728,1603,1582,1489 1461,1438,1360,1160/cm.

[α] D =+75.1° (CHCl 3 ,c=1.13,26° C.).

No.1j-9

CDCl 3 300 MHz 0.95-2.03(14H,m),2.20(1H,m),2.29(2H,t,J=7.5 Hz),3.06(1H,m),3.68(3H,s),4.98(1H,d,J=7.4 Hz),5.14-5.34(2H,m),7.46-7.54(2H,m),7.60-7.68(1H,m), 7.75-7.80(2H,m),7.88-7.92(2H,m),7.99-8.03(2H,m).

IR(CHCl 3 ):3384,3280,3020,2960,2888,1727,1662,1600,1316,1273,1163/cm.

[α] D =−41.0° (CHCl 3 ,c=1.17,26° C.).

No.1j-10

CDCl 3 +CD 3 OD 300 MHz 0.94-2.08(14H,m),2.21(1H,m),2.34(2H,t,J=6.2 Hz),3.04(1H,m),5.21-5.35(2H,m),5.40(1H,m),7.49-7.58(2H,m),7.64-7.68(1H,m),7.79-8.06(6H,m).

IR(CHCl 3 ):3475,3370,3250,3018,2956,2976,2650,1709,1662,1595,1445,1420,1395,1317,1274,1163/cm.

[α] D =−17.1° (CHCl 3 ,c=1.13,25° C.).

No.1j-11

CDCl 3 300 MHz 1.06-1.98(14H,m),2.24-2.29(3H,m),3.13(1H,m),3.66(3H,s),5.10-5.24(2H,m),5.40(1H,d,J=6.3 Hz),7.39-7.49(3H,m),7.59-7.64(3H,m),7.80-7.83(2H,m),8.08-8.11(1H,m).

IR(CHCl 3 ):3302,3012,2948,2905,1727,1661,1593,1435,1332,1312,1287,1271,1165/cm.

[α] D =+15.6° (CHCl 3 ,c=1.03,26° C.).

No.1j-12

CDCl 3 300 MHz 1.08-1.98(14H,m),2.23(1H,m),2.33(2H,t,J=7.5 Hz),3.16(1H,m),5.18-5.26(2H,m),5.39-5.45(1H,m),7.39-7.49(3H),7.60-7.49(3H,m),7.60-7.83(2H,m),8.09-8.12(1H,m).

IR(CHCl 3 ):3325,3022,2956,2872,2680,1708,1662,1603,1598,1425,1340,1316,1288,1271,1165/cm.

[α] D =+9.7° (CHCl 3 ,c=0.52,25° C.).

No.1j-13

CDCl 3 300 MHz 0.95-2.00(14H,m),2.20(1H,m),2.27(2H,t,J=6.3 Hz),3.03(1H,m),3.67(3H,s),4.99(1H,d,J6.6 Hz),5.12-5.31(2H,m),7.47-7.55(2H,m),7.60-7.69(2H,m), 7.76-7.781(2H,m),7.96-8.05(1H,m),8.08-8.14(1H,m),8.27-8.28(1H,m).

IR(CHCl 3 ):3674,3538,3376,3276,3012,2948,2860,1726,1662,1595,1440,1335,1317,1297,1274,1166,1150/cm.

[α] D =+10.2° (CHCl 3 ,c=1.00,25° C.).

No.1j-14

CDCl 3 300 MHz 0.93-2.08(14H,m),2.21(1H,m),2.32(2H,t,J=6.3 Hz),3.00(1H,m),5.20-5.36(2H,m), 5.38(1H,d,J=6.2 Hz),7.50-7.55(2H,m),7.63-7.71(2H,m),7.77-7.81(2H,m),7.99-8.04(1H,m),8.10-8.18(1H,m),8.32-8.36(1H,m).

IR(CHCl 3 ):3674,3480,3374,3258,3012,2950,2875,2650,1709,1662,1598,1418,1335,1317,1274,1143/cm.

[α] D =+61.0° (CHCl 3 ,c=1.19,25° C.).

No.1j-15

CDCl 3 300 MHz 0.90-2.00(14H,m),2.19(1H,m),2.30(2H,t,J=7.3 Hz),3.01(1H,m),3.67(3H,s), 4.82(1H,d,J=6.6 Hz),5.14-5.34(2H,m),7.36-7.39(3H,m),7.53-7.57(2H,m),7.62-7.66(2H,m),7.83-7.88(2H,m).

IR(CHCl 3 ):3376,3276,3010,2948,2868,2212,1727,1597,1500,1437,1325,11611 /cm.

[α] D =−7.2° (CHCl 3 ,c=1.00,26° C.).

No.1j-16

CDCl 3 300 MHz 0.93-2.03(14H,m),2.15(1H,m),2.36(2H,t,J=7.5 Hz),3.05(1H,m),5.20-5.40(3H,m),7.36-7.39(3H,m),7.55-7.66(4H,m),7.84-7.88(2H,m).

IR(CHCl 3 ):3470,3376,3260,3012,2950,2868,2675,2212,1708,1596,1503,1416,1396,1322,1160.

[α] D =−22.4° (CHCl 3 ,c=1.00,26° C.).

No.1j-17

CDCl 3 300 MHz 1.00-1.60(9H,m),1.79-1.89(5H,m),2.17(1H,brs),2.23(2H,t,J=7.2 Hz),3.03(1H,m), 5.10-5.23(2H,m),5.49(1H,d,J=6.6 Hz),7.40(1H,t,J=7.4 Hz),7.53(1H,t,J=7.2 Hz), 7.60-7.68(2H,m),7.98-8.03(2H,m),8.55(1H,d,J=1.5 Hz).

IR(CHCl 3 ):3516,3384,3270,2666,1708,1632,1595,1584,1467,1445,1425,1374,1345,1321,1269,1248,1218/cm.

[α] D =−7.8° (CHCl 3 ,c=1.01,22° C.).

No.1j-18

CDCl 3 300 MHz 0.90-2.03(14H,m),2.19(1H,m),2.30(2H,t,J=7.5 Hz),3.00(1H,m),3.67(3H,s), 4.80(1H,d,J=6.4 Hz),5.14-5.35(2H,m),6.99-7.04(2H,m),7.16-7.22(2H,m),7.34-7.49(4H,m),7.57-7.61(1H,m).

IR(CHCl 3 ):3376,3276,3012,2948,2875,1727,1583,1488,1471,1432,1330,1311,1150/cm.

[α] D =+54.0° (CHCl 3 ,c=0.99,25° C.).

No.1j-19

CDCl 3 300 MHz 0.91-2.09(14H,m),2.15(1H,m),2.34(2H,t,J=7.5 Hz),3.01(1H,m),5.16(1H,d,J=6.6 Hz),5.24-5.40(2H,m),7.01-7.08(2H,m),7.15-7.25(2H,m),7.35-7.53(4H,m),7.59-7.65(1H,m).

IR(CHCl 3 ):3470,3376,3260,3012,2950,2875,2640,1708,1583,1488,1471,1430,1335,1305,1149/cm.

[α] D =−21.0° (CHCl 3 ,c=1.30,25° C.).

No.1j-20

CDCl 3 300 MHz 1.17(1H,m),1.26-1.34(2H,m),1.54-2.24(11H,m),2.31(2H,t,J=7.4 Hz),2.48(1H,brs),3.37(1H,m),3.67(3H,s),5.35-5.50(2H,m),7.39-7.68(9H,m).

IR(CHCl 3 ):3377,1727,1601,1435,1362,11681/cm.

No.1j-21

CDCl 3 300 MHz 1,10-2.25(14H,m),2.36(2H,t,J=7.2 Hz),2.47(1H,m),2.89(1H,m),5.35-5.53(2H,m),5.63(1H,d,J=7.2 Hz),7.40-7.71(9H,m).

IR(CHCl 3 ):3674,3496,3374,3234,3010,2952,2870,2640,1730,1710,1605,1485,1425,1360,11671/cm.

[α] D =−43.0° (CHCl 3 ,c=1.01,25° C.).

No.1j-22

CDCl 3 300 MHz 0,98-1.95(14H,m),2.25-2,31(3H,m),2.95(1H,m),5.19-5.30(2H,m),5.33(1H,d,J=3.9 Hz),6.58(1H,d,J=7.5 Hz),6.80(1H,t,J=7.5 Hz),6.99-7.05(1H,m),7.44-7.53(6H,m),7.60-7.73(9H,m),7.94-7.73(3H,m),8.23-9.26(2H,m),10.66(1H,s).

IR(CHCl 3 ):3475,3372,3260,3008,2952,2868,2722,1725,1710,1663,1590,1571,1525,1448,1437,1345,1314,1161,1112/cm.

[α] D =+12.9° (CHCl 3 ,c=0.12,23° C.).

No.1j-23

CDCl 3 300 MHz 0.94˜1.94(14H,m),2.23-2.30(3H,m),2.98(1H,m),3.68(3H,9),5.09(1H,d,J=6.2 Hz),5.15-5.28(2H,m),7.14-7.22(1H,m),7.34-7.42(2H,m),7.68-7.73(2H,m),7.89-8.03(4H,m),8.51(1H,s).

IR(CHCl 3 ):3372,3275,1724,1673,1599,1438,1320,1161/cm.

[α] D =+17.0° (CHCl 33 ,c=1.38,25° C.).

No.1j-24

CDCl 3 C 3 O 300 MHz 0.96-2.05(14H,m),2,25-2.34(3H,m),2.92(1H,m),5.16-5.34(2H,m),7.14-7.22(1H,m),7.29-7.42(2H,m),7.70(2H,d,J=7.6 Hz),7.92-8.05(4H,m).

IR(CHCl 3 ):3616,3426,3375,3010,2950,2828,2645,1708,1672,1599,1439,1323,1161/cm.

[α] D =+21.0° (CH 3 OH,c=1.00,22° C.).

No.1j-25

CDCl 3 300 MHz 1.03(1H,m),1.18-2.01(13H,m),2.20(1H,brs),2.27(2H,t,J=7.4 Hz),3.08(1H,m),3.66(3H,s),5.11(1H,d,J=6.6 Hz),5.14-5.34(2H,m),7.54-7.62(3H,m),8.04-8.32(6H,m).

IR(CHCl 3 ):3384,3278,1726,1605,1484,1448,1331,1161/cm.

No.1j-26

CDCl 3 +CD 3 OD 300 MHz 1,03-2.10(14H,m),2.22(1H,m),2.31(2H,t,J=7.5 Hz),2.98(1H,m),5.23-5.38(2H,m),7.55-7.66(3H,m),8.05-8.08(2H,m),8.14-8.18(2H,m),8.28-8.31(2H,m).

IR(Nujol):3260,2720,2660,1711,1545,1460,1317,1163/cm.

[α] D =+15.8° (CH 3 OH,c=1.01,22° C.).

No.1j-27

[α] D =+16.7° (CHCl 3 ,c=1.00,23° C.).

No.1j-28

CDCl 3 300 MHz 1.01(1H,m),1.14-1.29(2H,m),1.46-2.19(11H,m),2.33(2H,t,J=7.2 Hz),2.41(1H,brs),3.18-3.21(5H,m),3.68(3H,s),3.73-3.76(4H,m),4.37(1H,d,J=7.2 Hz),5.35-5.45(2H,m).

IR(CHCl 3 ):3392,1727,1435,1335,1148/cm.

[α] D =+10.7° (CHCl 3 ,c=1.39,26° C.).

No.1j-29

CDCl 3 300 MHz 1.00(1H,m),1.20-1.29(2H,m),1,48-2.25(12H,m),2.37(2H,t,J=7.2 Hz),3.17-3.22(5H,m),3.74-3.79(4H,m),4.79(1H,d,J=7.8 Hz),5.34-5.54(2H,m).

IR(CHCl 3 ):3470,3390,3270,2675,1709,1455,1420,1315,1147/cm.

[α] D =+16.8° (CHCl 3 ,c=1.42,26° C.).

No.1k-1

[α] D =−25.4° (CHCl 3 ,c=1.08,23° C.).

No.1k-2

CDCl 3 200 MHz 1.07-2.28(14H,m),2.32(2H,t,J=7.4Hz),2.63(1H,m),3.63(3H,s),3.93(1H,m),5.30-5.52(2H,m),6.35(1H,d,J=7.0 Hz);7.48-7.60(3H,m),7.88-8.02(6H,m).

IR(CHCl 3 ):3438,3002,2946,2868,1727,1652,1514,1485,1363,1310,1245,1154/cm.

[α] D =−80.4° (CHCl 3 ,c=1.01,24.0° C.).

No.1k-3

CDCl 3 200 MHz 1.10-2.26(14H,m),2.37(2H,t,J=7.2 Hz),2.60(1H,m),3.93(1H,m),5.30-5.50(2H,m),6.33(1H,d,J=7.5 Hz),7.48-7.5 8(3H,m),7.88-7.99(6H,m).

IR(CHCl 3 ):3446,3004,2952,2874,1709,1652,1515,1485,1305,1153 /cm.

[α] D =−96.4° (CHCl 3 ,c=1.05,23.0° C.).

No.1k-4

CDCl 3 300 MHz 1.05-2.17(14H,m),2.38(2H,t,J=7.2 Hz),2.52(1H,m),3.81(1H,m),5.33-5.50(2H,m),6.08(1H,d,J=7.6 Hz),7.39-7.53(3H,m),7.57-7.62(6H,m).

IR(CHCl 3 ):3420,3250,3008,2948,2870,2660,2208,1735,1705,1640,1500/cm.

[α] D =−21.9±0.6° (CHCl 3 ,c=1.02,22° C.).

No.1k-5

CDCl 3 300 MHz 1.05-2.14(14H,m),2.38(2H,t,J=7.2 Hz),2.51(1H,m),3.81(1H,m),5.34-6.46(2H,m),6.07(1H,d,J=7.6 Hz),7.33-7.5 6(5H,m).

IR(CHCl 3 ):3422,3250,3010,2950,2876,2664,2558,2210,1735,1705,1645,1502,1441,1410,1307,1276/cm.

[α] D =−63.6±1.9° (CHCl 3 ,c=0.56,22° C.).

No.1k-6

CDCl 3 300 MHz 1.04-2.24(14H,m),2.36(2H,t,J=7.5 Hz),2.58(1H,m),3.88(1H,m),5.30-5.43(2H,m),6.21(1H,d,J=7.2 Hz),7.41-7.49(3H,m),7.73-7.77(2H,m).

IR(CHCl 3 ):3447,3011,2955,1708,1653,1603,1578,1515,1486,1457,1312,1211,1164/cm.

[α] D =−60.3° (CHCl 3 ,c=1.00,23° C.).

No.1k-7

CDCl 3 300 MHz 1.04-2.22(14H,m),2.36(2H,t,J=7.2 Hz),2.57(1H,m),3.87(1H,m),5.30-5.44(2H,m),6.17(1H,d,J=8.7 Hz),6.99-7.40(7H,m),7.73(2H,d,J=7.5 Hz).

IR(CHCl 3 ):3449,3013,2955,1739,1708,1651,1609,1588,1522,1487,1243,1227,1169/cm.

[α] D =−60.2° (CHCl 3 ,c=0.92,23° C.).

No.1k-8

CDCl 3 300 MHz 1.04-2.25(14H,m),2.34(2H,t,J=7.5 Hz),2.56(1H,m),3.87(1H,m),5.30-5.44(2H,m),6.19(1H,d,J=7.5 Hz),6.83-6.94(6H,m),7.69(2H,d,J=8.7 Hz).

IR(CHCl 3 ):3599,3455,3012,2955,1711,1644,1604,1577,1524,1507,1492,1290,1236,1197,1170/cm.

[α] D =−47.7° (CHCl 3 ,c=1.01,22° C.).

No.1k-9

CDCl 3 300 MHz 1.04-2.20(14H,m),2.31(3H,s),2.36(2H,t,J=7.2 Hz),2.56(1H,m),3.86(1H,m),5.30-5.43(2H,m),6.16(1H,d,J=7.2 Hz),7.00-7.11(6H,m),7.74(2H,d,J=8.7 Hz).

IR(CHCl 3 ):3450,3010,2955,1750,1709,1651,1609,1596,1523,1489,1370,1247,1227,1183/cm.

[α] D =−54.7° (CHCl 3 ,c=1.01,22° C.).

No.1k-10

CDCl 3 300 MHz 1.04-2.22(14H,m),2.35(2H,t,J=7.2Hz),2.56(1H,m),3.82(3H,s),3.86(1H,m),5.30-5.43(2H,m),6.17(1H,d,J=6.9 Hz),6.89-7.01(6H,m),7.70(2H,d,J=8.7 Hz).

IR(CHCl 3 ):3023,2955,1742,1708,1649,1613,1602,1577,1522,1507,1490,1227,1210,1170/cm.

[α] D =−58.1° (CHCl 3 ,c=1.01,22° C.).

No.1m-1

CDCl 3 300 MHz 1.06-2.25(14H,m),2.32(2H,t,J=7.4 Hz),2.61(1H,m),3.63(3H,s),3.91(1H,m),5.33-5.47(2H,m),6.24(1H,d,J=6.9 Hz),7.35-7.38(3H,m),7.53-7.60(4H,m),7.75-7.78(2H,m).

IR(CHCl 3 ):3438,3008,2946,2875,2212,1732,1650,1605,1519,1496/cm.

[α] D =+76° (CHCl 3 ,c=1.39,24° C.)

No.1m-2

CDCl 3 300 MHz 1.05-2.20(14H,m),2.36(2H,t,J=6.2 Hz),2.59(1H,m),3.89(1H,m),5.29-5.48(2H,m),6.26(1H,d,J=7.0 Hz),7.26-7.38(3H,m),7.52-7.60(4H,m),7.73-7.77(2H,m).

IR(CHCl 3 ):3444,3012,2952,2874,2664,2214,1718,1708,1649,1605,1520,1498/cm.

[α] D =+81.4° (CHCl 3 ,c=1.01,23° C.)

No.1m-3

CDCl 3 300 MHz 1.06-2.23(14H,m),2.32(2H,t,J=7.0 Hz),2.62(1H,m),3.63(3H,s),3.93(1H,m),5.30-5.50(2H,m),6.28(1H,d,J=7.0 Hz),7.38-7.51(3H,m),7.58-7.67(4H,m),7.83-7.88(2H,m).

IR(CHCl 3 ):3438,3008,2948,2875,1783,1727,1650,1608,1580,1523,1501,1482/cm.

[α] D =+59° (CHCl 3 ,c=1.49,25° C.)

No.1m-4

CDCl 3 300 MHz 1.08-2.25(14H,m),2.36(2H,t,J=7.4 Hz),2.59(1H,m),3.91(1H,m),5.28-5.48(3H,m),6.29(1H,d,J=7.4 Hz),7.38-7.50(3H,m),7.61-7.67(4H,m),7.81-7.86(2H,m).

IR(CHCl 3 ):3436,3010,2948,2868,1727,1715,1649,1615,1524,1502,1482,1372/cm. [α] D =+72° (CHCl 3 ,c=0.98,25° C.)

No.1m-5

CDCl 3 300 MHz 1.09-2.20(14H,m),2.32(2H,t,J=7.2 Hz),2.63(1H,m),3.63(3H,s),3.92(1H,m),5.31-5.51(2H,m),6.35(1H,d,J=7.0 Hz),7.51-7.60(3H,m),7.92-7.97(6H,m).

IR(CHCl 3 ):3436,3008,2946,2875,1727,1652,1608,1515,1484/cm.

[α] D =+82° (CHCl 3 ,c=0.99,25° C.)

No.1m-6

CDCl 3 300 MHz 1.09-2.23(14H,m),2.37(2H,t,J=7.2 Hz),2.60(1H,m),3.92(1H,m),5.30-5.49(2H,m),6.32(1H,d,J=7.4 Hz),7.51-7.55(3H,m),7.85-7.98(6H,m).

IR(CHCl 3 ):3436,3010,2950,2875,2670,1727,1715,1650,1605,1515,1484/cm.

[α] D =+84° (CHCl 3 ,c=1.54,25° C.)

No.1m-7

CDCl 3 300 MHz 1.03-2.18(14H,m),2.32(2H,t,J=7.4 Hz),2.59(1H,m),3.64(3H,s), 3.89(1H,m),5.29-5.49(2H,m),6.16(1H,d,J=7.8 Hz),6.98-7.06(4H,m),7.14-7.20(1H,m),7.34-741(2H,m),7.73-7.78(2H,m).

IR(CHCl 3 ):3438,3008,2946,2868,1727,1648,1610,1586,1519,1485/cm.

[α] D =+54° (CHCl 3 ,c=1.29,25° C.).

No.1m-8

CDCl 3 300 MHz 1.06-2.21(14H,m),2.36(2H,t,J=7.5 Hz),2.58(1H,m),3.88(1H,m),5.31-5.46(2H,m),6.17(1H,d,J=6.9 Hz),6.99-7.05(4H,m),7.15-7.21(1H,m),7.36-7.41(2H,m),7.72-7.75(2H,m).

IR(CHCl 3 ):3436,3010,2948,2868,2675,1730,1709,1647,1608,1586,1520,1485/cm.

[α] D =+56° (CHCl 3 ,c=0.97,25° C.)

No.1m-9

CDCl 3 300 MHz 1.05-2.18(14H,m),2.29-2.34(5H,m),2.59(1H,m),3.64(3H,s),3.89(1H,m),5.32-5.46(2H,m),6.16(1H,d,J=7.5 Hz),7.00-7.11(6H,m),7.74-7.77(2H,m).

IR(CHCl 3 ):3440,3010,2946,2868,1729,1649,1595,1519,1488/cm.

[α] D =+47° (CHCl 3 ,c=0.82,25° C.).

No.1m-10

CDCl 3 300 MHz 1.04-2.20(14H,m),2.31-2.39(5H,m),2.57(1H,m),3.87(1H,m),5.28-5.47(2H,m), 6.17(1H,d,J=7.0 Hz),6.99-7.12(6H,m),7.72-7.76(2H,m).

IR(CHCl 3 ):3674,3572,3438,3010,2948,2868,2626,1748,1710,1648,1615,1595,1520,1489/cm.

[α] D =+51° (CHCl 3 ,c=0.91,25° C.)

No.1m-11

CDCl 3 300 MHz 1.04-2.16(14H,m),2.31(2H,t,J=7.2 Hz),2.59(1H,m),3.63(3H, s),3.89(1H,m),5.29-5.49(2H,m),6.24(1H,d,J=7.4 Hz),6.54(1H,s),6.83-6.93(6H,m),7.69-7.73(2H,m).

IR(CHCl 3 ):3674,3588,3438,3296,3010,2946,2868,1725,1646,1603,1520,1504,1489/cm.

[α] D =+51° (CHCl 3 ,c=0.91,25° C.)

No.1m-12

CDCl 3 300 MHz 1.04-2.21(14H,m),2.33(2H,t,J=8.0 Hz),2.56(1H,m),3.87(1H,m),5.28-5.48(2H,m),6.23(1H,d,J=8.0 Hz),6.75(1H,m),6.87-6.94(6H,m),7.66-7.71(2H,m),9.63(1H,brs).

IR(CHCl 3 ):3674,3582,3436,3275,3010,2950,2868,2675,1727,1710(sh),1643,1603,1522,1504,1490/cm.

[α] D =+30° (CHCl 3 ,c=0.97,25° C.)

No.1m-13

CDCl 3 300 MHz 1.01-2.18(14H,m),2.31(2H,t,J=7.4 Hz),2.58(1H,m),3.63(3H,s),3.82(3H,s),3.89(1H,m),5.29-5.48(2H,m),6.14(1H,d,J=7.0 Hz),6.88-7.02(6H,m),7.70-7.74(2H,m).

IR(CHCl 3 ):3442,3402,3004,2946,2868,1727,1648,1600,1518,1499/cm.

[α] D =+42(CHCl 3 ,c=1.8.2,26° C.)

No.1m-14

CDCl 3 300 MHz 1.05-2.21(14H,m),2.35(2H,t,J=7.2 Hz),2.55(1H,m),3.82(3H,s),3.88(1H,m)5.27-5.46(2H,m),6.16(1H,d,J=7.2 Hz),6.88-7.02(6H,m),7.68-7.73(2H,m).

IR(CHCl 3 ):3438,3012,2948,2870,2650,1730(sh),1709,1647,1615(sh),1601,1519,1492/cm.

[α] D =+64° (CHCl 3 ,c=0.70,25° C.)

No.1m-15

CDCl 3 300 MHz 1.05-2.20(14H,m),2.29-2.36(5H,m),2.62(1H,m),3.63(3H,s),3.92(1H,m),5.30-5.50(2H,m),6.25(1H,d,J=7.2 Hz),7.16-7.21(2H,m),7.59-7.64(4H,m),7.83-7.87(2H,m).

IR(CHCl 3 ):3446,3010,2946,2868,1745,1728,1650,1615,1525,1507,1486/cm.

[α] D =+65.0° (CHCl 3 ,c=1.02,23° C.)

No.1m-16

CDCl 3 300 MHz 1.08-2.21(14H,m),2.34-2.40(5H,m),2.59(1H,m),3.90(1H,m),5.29-5.48(2H,m), 6.29(1H,d,J=7.0 Hz),7.18(2H,d,J=8.6 Hz),7.58-7.64(4H,m),7.83(2H,d,J=8.2 Hz).

IR(CHCl 3 ):3438,3012,2948,2870,2622,1749,1710,1649,1610,1526,1508,1487/cm.

[α] D =+66° (CHCl 3 ,c=1.21,24° C.)

No.1m-17

CDCl 3 300 MHz 1.06-2.19(14H,m),2.32(2H,t,J=7.2 Hz),2.62(1H,m),3.63(3H,s),3.93(1H,m),5.30-5.50(2H,m),6.32(1H,d,J=7.6 Hz),6.41(1H,s),6.94(2H,d J=9.0 Hz),7.47(2H,d,J=9.0 Hz),7.58(2H,d,J=8.6 Hz),7.81(2H,d,J=8.6 Hz).

IR(CHCl 3 ):3580,3434,3284,3010,2946,2868,1726,1646,1606,1528,1490/cm. [α] D =+62.4° (CHCl 3 ,c=1.01,23° C.)

No.1m-18

CDCl 3 +CD 3 OD 300 MHz 1.11-2.18(14H,m),2.32(2H,t,J=7.4 Hz),2.59(1H,m),3.88(1H,m),5.30-5.49(2H,m),6.55(1H,d,J=7.0 Hz),6.92(2H,d,J=8.6 Hz),7.47(2H,d,J=8.6 Hz),7.59(2H,d,J=8.6 Hz),7.79(2H,d,J=8.2 Hz).

IR(Nujol):3398,3175,2725,1696,1635,1601,1531,1510/cm.

[α] D =+99.5° (CH 3 OH,c=1.011,25° C.)

No.1m-19

CDCl 3 300 MHz 1.05-2.20(14H,m),2.32(2H,t,J=7.4 Hz),2.61(1H,m),3.63(3H,s),3.86(3H,s),3.94(1H,m),5.30-5.50(2H,m),6.24(1H,d,J=7.0 Hz),6.99(2H,d,J=8.6 Hz),7.53-7.63(4H,m),7.82(2H,d,J=8.6 Hz).

IR(CHCl 3 ):3440,3006,2946,2875,1726,1649,1606,1527,1510,1489/cm.

[α] D =+68° (CHCl 3 ,c=0.88,26° C.)

No.1m-20

CDCl 3 300 MHz 1.09-2.20(14H,m),2.35(2H,t,J=7.3 Hz),2.58(1H,m),3.85(3H,s),3.89(1H,m),5.28-5.48(2H,m),6.35(1H,d,J=7.2 Hz),6.98(2H,d,J=8.8 Hz),7.51-7.61(4H,m),7.81(2H,d,J=8.4 Hz),8.34(1H,brs).

IR(CHCl 3 ):3446,3012,2952,2881,2640,1730,1707,1647,1606,1527,1510,1489/cm.

[α] D =+83(CHCl 3 ,c=1.00,25° C.).

No.1m-21

CDCl 3 300 MHz 1.05-2.14(14H,m),2.37(2H,t,J=7.2 Hz),2.51(1H,m),3.81(1H,m),5.34-5.46(2H,m),6.11(1H,d,J=7.5 Hz),7.33-7.48(3H,m),7.53-7.55(2H,m).

IR(CHCl 3 ):3420,3250,3008,2948,2870,2660,2210,1735,1705,1645,1503,1441,1409/cm.

[α] D =+59.2±1.0° (CHCl 3 ,c=1.023,22° C.).

No.1m-22

CDCl 3 300 MHz 1.05-2.17(14H,m),2.37(2H,t,J=7.2 Hz),2.52(1H,m),3.82(1H,m),5.32-5.47(2H,m),6.20(1H,d,J=7.6 Hz),7.38-7.53(3H,m),7.58-7.61(6H,m),9.11(1H,brs).

IR(CHCl 3 ):3420,3250,3010,2984,2870,2675,2208,1730,1705,1640,1500,1406/cm.

[α] D =+57.4° (CHCl 3 ,c=1.83,23° C.).

No.1m-23

CDCl 3 300 MHz 1.05-2.18(14H,m),2.31(2H,t,J=7.5 Hz),2.60(1H,m),3.63(3H,s),3.90(1H,m),5.32-5.47(2H,m),6.22(1H,d,J=6.9 Hz),7.40-7.49(3H,m),7.76-7.79(2H,m).

IR(CHCl 3 ):3438,3008,2946,2868,1727,1651,1603,1585,1512,1484/cm.

[α] D =+52° (CHCl 3 ,c=1.49,25° C.).

No.1m-24

CDCl 3 300 MHz 1.05-2.21(14H,m),2.36(2H,t,J=7.2 Hz),2.57(1H,m),3.89(1H,m),5.28-5.47(2H,m),6.22(1H,d,J=7.0 Hz),7.39-7.55(3H,m),7.73-7.79(2H,m).

IR(CHCl 3 ):3676,3572,3436,3010,2948,2875,1730,1709,1650,1600,1580,1514,1484/cm.

[α] D =+57° (CHCl 3 ,c=0.97,26° C.).

No.1m-25

CDCl 3 300 MHz 1.04-2.18(14H,m),2.28-2.35(5H,m),2.59(1H,m),3.62(3H,s),3.88(1H,m),5.29-5.49(2H,m),6.20(1H,d,J=7.2 Hz),7.15(2H,d,J=9.0 Hz), 7.80(2H,d,J=8.8 Hz).

IR(CHCl 3 ):3436,3010,2946,2868,1752,1727,1653,1602,1519,1491/cm.

[α] D =+53° (CHCl 3 ,c=1.63,25° C.).

No.1m-26

CDCl 3 300 MHz 1.05-2.19(14H,m),2.32-2.38(5H,m),2.56(1H,m),3.88(1H,m),5.29-5.47(2H,m),6.25(1H,d,J=7.4 Hz),7.15(2H,d,J=9.0 Hz),7.78(2H,d,J=8.6 Hz).

IR(CHCl 3 ):3434,3016,3006,2948,2880,2622,1752,1730,1710,1651,1605,1520,1492/cm.

[α] D =+58° (CHCl 3 ,c=3.68,24° C.)

No.1m-27

CDCl 3 300 MHz 1.05-2.16(14H,m),2.30(2H,t,J=7.6 Hz),2.57(1H,m),3.62(3H,s),3.87(1H,m),5.27-5.47(2H,m),6.32(1H,d,J=7.4 Hz),6.85(2H,d,J=8.6 Hz),7.62(2H,d,J=8.35(1H,s).

IR(CHCl 3 ):3580,3450,3216,3010,2946,2868,1726,1640,1608,1584,1528,1496/cm.

[fa] D =+56.2° (CHCl 3 ,c=0.713,23° C.)

No.1m-28

CDCl 3 200 MHz 1.10-2.25(14H,m),2.32(2H,t,J=7.2 Hz),2.55(1H,brs),3.82-3.93(1H,m),5.27-5.47(2H,m),6.25(1H,d,J=7.4 Hz),6.86(2H,d,J=8.6 Hz),7.62(2H,d,J=8.6 Hz).

IR(CHCl 3 ):3438,3242,2675,1730,1708,1639,1607,1585/cm.

No.1m-29

CDCl 3 300 MHz 1.05-2.18(14H,m),2.31(2H,t,J=7.4 Hz),2.58(1H,m),3.64(3H,s),3.85(3H,s),3.89(1H,m),5.29-5.48(2H,m),6.14(1H,d,J=6.6 Hz),6.92(2H,d,J=9.0 Hz),7.74(2H,d,J=9.0 Hz).

IR(CHCl 3 ):3445,3008,2946,2868,1727,1646,1606,1578,1523,1493/cm.

[α] D =+53° (CHCl 3 ,c=2.03,24° C.)

No.1m-30

CDCl 3 300 MHz 1.04-2.21(14H,m),2.36(2H,t,J=7.3 Hz),2.56(1H,m),3.85(3H,s),3.88(1H,m),5.27-5.46(2H,m),6.15(1H,d,J=7.2 Hz),6.92(2H,d,J=8.6 Hz),7.73(2H,d,J=8.6 Hz)

IR(CHCl 3 ):3440,3010,2950,2870,2645,1727,1710,1646,1606,1575,1524,1494/cm.

[α] D =+62° (CHCl 3 ,c=1.10,24° C.).

No.1m-31

CDCl 3 +CD 3 OD 300 MHz 1.16-2.20(14H,m),2.31(2H,t,J=7.2 Hz),2.59(1H,m),3.85(1H,m),5.31-5.51(2H,m),7.13-7.21(1H,m),7.31-7.42(2H,m),7.68-7.93(6H,m).

IR(Nujol):3344,3175,2715,2675,1699,1631,1566/cm.

[α] D =+67° (CH 3 OH,c=1.01,24° C.).

No.1m-32

CDCl 3 200 MHz 1.09-2.23(14H,m),2.33(2H,t,J=7.1 Hz),2.57(1H,brs),3.40-3.93(9H,m),4.41(1H,brs),5.29-5.48(2H,m),6.44(1H,d,J=7.4 Hz),7.43(2H,d,J=8.2 Hz),7.80(2H,d,J=7.8 Hz).

IR(CHCl 3 ):3434,3354,1726,1720,1660,1626/cm.

No.1m-33

CDCl 3 200 MHz 1.14-2.25(14H,m),2.37(2H,t,J=7.3 Hz),2.64(1H,brs),3.93-4.01(1H,m),5.30-5.51(2H,m),6.47(1H,d,J=7.4 Hz),7.63-7.74(2H,m),7.79(2H,s),7.89-7.93(1H,m),8.00(1H,dd,J=2.3,1.0 Hz),8.30(1H,d,J=10 Hz),8.65-8.73(2H,m).

IR(CHCl 3 ):3450,2675,1728,1707,1649,1528,1509/cm.

[α] D =+82.8±1.2° (CHCl 3 ,c=1.01,23° C.).

No.2a-1

[α] D =+69.0° (MeOH,c=1.01,25° C.)

No.2a-2

CDCl 3 300 MHz 0.99(1H,d,J=10.2 Hz),1.15 and 1.24(each 3H,each s),1.50-2.50(14H,m),4.30(1H,m),5.35-5.52(2H,m),6.32(1H,d,J=8.7 Hz),7.36-7.49(3H,m),7.58-7.62(2H,m),7.66 and 7.80(each 2H,each d,J=8.7 Hz).

IR(CHCl 3 ):3116,3014,2925,2870,2663,1708,1651,1610,1524,1504,1484,1472/cm.

[α] D =+64.1° (MeOH,c=1.02,25° C.).

No.2a-3

[α] D =+76.6° (MeOH,c=1.18,26° C.).

No.2a-4

CDCl 3 300 MHz 0.99(1H,d,J=10.2 Hz),1.15 and 1.25(each 3H,each s),1.64-2.51(14H,m),4.31(1H,m),5.36-5.53(2H,m),6.33(1H,d,J=8.4z),7.50-7.56(3H,m),7.85-7.98(6H,m).

IR(CHCl 3 ):3515,3452,3014,2925,2870,1740,1708,1654,1517,1486,1470/cm.

[α] D =+79.5° (MeOH,c=1.18, 22° C.).

No.2a-5

CD 3 OD 300 MHz 0.98(1H,d,J=9.9 Hz),1.18 and 1.25(each 3H,each s),1.56-1.71(3H,m),1.98-2.40(11H,m),4.17(1H,m),5.41-5.52(2H,m),7.52-7.61(3H,m),7.91-8.01(6H,m).

IR(KBr):3416,3063,2983,2921,2869,1704,1643,1566,1518,1488,1408/cm.

[α] D =+62.0° (MeOH,c=1.00, 25° C.).

No.2a-6

[α] D =+64.1° (MeOH,c=1.01,25° C.).

No.2a-7

[α] D =+65.3° (MeOH,c=0.99,25° C.).

No.2a-8

[α] D =+74.0° (MeOH,c=1.01,25° C.).

No.2a-9

[α] D =+71.0° (MeOH,c=1.10,25° C.).

No.2a-10

[α] D =+74.7° (MeOH,c=1.00,25° C.).

No.2a-11

[α] D =+72.1° (MeOH,c=1.00,25° C.).

No.2a-12

[α] D =+53.1° (CHCl 3 ,c=1.01,26° C.).

m.p.155.0-156.0° C.

No.2a-13

CDCl 3 300 MHz 0.98(1H,d,J=10.2 Hz),1.18 and 1.25(each 3H,each s), 1.63-2.40(14H,m),4.30(1H,m),5.46-5.58(2H,m),6.44(1H,d,J=8.4 Hz),7.49 and 7.77(each 2H,each d,J=8.7 Hz),7.54(1H,s).

IR(CHCl 3 ):3689,3378,3028,3014,2924,1713,1652,1602,1522,1496/cm.

[α] D =+78.3° (MeOH,c=0.84,25° C.).

m.p.205.0-206.0° C.

No.2a-14

[α] D =+72.5° (MeOH,c=1.07,26° C.).

No.2a-15

CDCl 3 300 MHz 0.99(1H,d,J=9.9 Hz),1.14 and 1.24(each 3H,each s),1.55-2.44(14H,m),4.27(1H,m),5.30-5.50(2H,m),6.29(1H,d,J=9.0 Hz),7.11 and 7.20(each 1H,each d,J=16.2 Hz),7.29-7.55(5H,m),7.57 and 7.72(each 2H,each d,J=8.7 Hz).

IR(CHCl 3 ):8453,3083,3022,3013,2925,2870,1708,1650,1607,1560,1522,1496/cm.

[α] D =+72.3° (MeOH,c=1.00,27° C.).

m.p.115.0-117.0° C.

No.2a-16

CDCl 3 300 MHz 0.92(1H,d,J=10.2 Hz),1.11 and 1.23(each 3H,each s),1.50-2.48(14H,m),3.62(3H,s),4.29(1H,m),5.30-5.50(2H,m),6.20(1H,d,J=8.7 Hz),6.59 and 6.68 each 1H,each,d,J=12.3 Hz),7.23(5H,s),7.29 and 7.59(each 2H,each d,J=8.1 Hz).

IR(CHCl 3 ):3453,3024,3016,2924,2870,1730,1651,1607,1520,1495/cm.

[] D =+56.8° (MeOH,c=1.04,24° C.).

No.2a-17

CDCl 3 300 MHz

0.97(1H,d,J=10.2 Hz),1.11 and 1.23(each 3H,each s),1.50-2.38(14H,m),4.26(1H,m),5.30-5.50(2H,m),6.23(1H,d,J=8.4 Hz),6.59 and 6.70(each 1H,each d,J=12.3 Hz),7.23(5H,s),7.30 and 7.57(each 2H,each d,J=8.7 Hz).

IR(CHCl 3 ):3452,3081,3019,3014,2925,2870,2665,1708,1650,1607,1521,1495/cm.

[(1] D =+61.6° (MeOH,c=1.00,27° C.).

No.2a-18

CDCl 3 300 MHz

0.97(1H,d,J=10.2 Hz),1,11 and 1.23(each 3H,each,s),1.50-2.50(14H,m),3.61(3H,s),4.31(1H,m),5.35-5.51(2H,m),6.33(1H,d,J=8.4 Hz),7.48-7.64(4H,m)7.79-7.83(2H,m),7.91(1H,dt,J=1.5 and 7.8 Hz),8.01(1H,dt,J=1.5 and 7.8 Hz),8.13(1H,t,J=1.5 Hz).

IR(CHCl 3 ):3450,3026,3013,2925,2870,1730,1659,1600,1510/cm.

[] D =+56.0° (MeOH,c=1.01,25° C.).

No.2a-19

CDCl 3 300 MHz 0.95(1H,d,J=9.9 Hz),1.14 and 1.21(each 3H,each s),1.53-2.60(14H,m),4.25(1H,m),5.35-5.64(2H,m),7.21(1H,d,J=7.8 Hz),7.49-7.68(4H,m),7.76-7.84(3H,m),8.25(1H,m),8.43(1H,m).

IR(CHCl 3 ):3382,3196,3025,3015,2925,2870,1725,1652,1599,1577,1521/cm.

[α] D =+55.9° (MeOH,c=1.00,25° C.).

No.2a−20

CDCl 3 300 MHz 0.98(1H,d,J=10.2 Hz),1.13 and 1.24(each 3H,each s),1.50-2.50(14H,m),3.62(3H,s),4.31(1H,m),5.35-5.51(2H,m),6.24(1H,d,J=8.4 Hz),7.40-7.52(3H,m),7.71-7.76(2H,m).

IR(CHCl 3 ):3453,3025,3013,2925,2870,1730,1753,1579,1514,1486/cm.

[α] D =+61.2° (MeOH,c=1.04,25° C.).

No.2a-21

CDCl 3 300 MHz (0.98(1H,d,J=10.2 Hz),1.13 and 1.23(each 3H,each s),1.52-2.50(14H,m),4.28(1H,m),5.34-5.51(2H,m),6.27(1H,d,J=8.7 Hz),7.41-7.53(3H,m),7.71-7.74(2H,m).

IR(CHCl 3 ):3452,3063,3027,3014,2925,2871,1708,1652,1578,1515,1486/cm.

[α] D =+62.0° (MeOH,c=1.01,27° C.).

No.2a-22

d 6 -DMSO 300 MHz 0.86(1H,d,J=9.9 Hz),1.10 and 1.16(each 3H,each s),1.42-1.52(3H,m),1.85-2.46(11H,m),3.98(1H,m),5.32-5.43(2H,m),7.41(3H,m),7.88(2H,d,J=6.6 Hz),8.19(1H,d,J=6.6 Hz).

IR(KBr):3367,3060,2984,2922,2868,1634,1563,1529,1487/cm.

[α] D =+47.7° (MeOH,c=1.00,25° C.).

No.2a-23

[α] D =+62.7° (MeOH,c=1.01,27° C.).

No.2a-24

CDCl 3 300 MHz 0.99(1H,d,J=10.2 Hz),1.14 and 1.25(each 3H,each s),1.52-2.50(14H,m),4.31(1H,m),5.36-5.52(2H,m),6.34(1H,d,J=8.4 Hz),7.47-7.52(2H,m),7.59-7.64(1H,m),7.78-7.83(6H,m).

IR(CHCl 3 ):3449,3027,3013,2925,2869,1708,1656,1599,1518,1493/cm.

[α] D =+63.1° (MeOH,c=1.00,25° C.).

No.2a-25

[α] D =+35.1° (MeOH,c=1.00,25° C.).

No.2a-26

[α] D =+35.5° (MeOH,c=1.02,25° C.).

No.2a-27

CDCl 3 300 MHz 0.97(1H,d,J=10.2 Hz),1.12 and 1.23(each 3H,each s),1.52-2.50(14H,m),3.63(3H,s),4.29(1H,m),5.36-5.51(2H,m),6.18(1H,d,J=8.4 Hz),7.01 and 7.71 (each 2H,each d,J=8.7 Hz,),6.98-7.05(2H,m),7.16(1H,t,J=7.5 Hz),7.34-7.41(2H,m).

IR(CHCl 3 ):3455,3024,3016,2924,2870,1730,1651,1588,1520,1487/cm.

[α] D =+56.4° (MeOH,c=1.01,25° C.).

No.2a-28

CDCl 3 300 MHz 0.98(1H,d,J=10.2 Hz),1.12 and 1.23(each 3H,each s),1.52-2.50(14H,m),4.26(1H,m),5.34-5.51(2H,m),6.20(1H,d,J=9.0 Hz),7.01 and 7.70(each 2H,each d,J=9.0 Hz,),6.98-7.15(2H,m),7.17(1H,t,J=7.5 Hz),7.34-7.40(2H,m).

IR(CHCl 3 ):3454,3031,3018,2925,2870,1708,1650,1588,1523,1487/cm.

[α] D =+56.2° (MeOH,c=1.00,25° C.).

No.2a-29

[α] D =+53.0° (MeOH,c=1.03,25° C.).

No.2a-30

CDCl 3 300 MHz 0.97(1H,d,J=10.2 Hz),1.10 and 1.23(each 3H,each s),1.52-2.50(14H,m),4.25(1H,m),5.30-5.50(2H,m),6.23(1H,d,J=8.7 Hz),6.36(1H,s),7.26-7.39(10H,m),7.60 and 7.68(each 2H,each d,J=8.4 Hz,).

IR(CHCl 3 ):3451,3088,3064,3029,3014,2925,2869,1707,1652,1522,1495/cm.

[α] D =+54.2° (MeOH,c=1.00,25° C.).

No.2a-31

CDCl 3 300 MHz 0.98(1H,d,J=10.2 Hz),1.14 and 1.24(each 3H,each s),1.50-2.50(14H,m),3.63(3H,s),4.31(1H,m),5.30-5.50(2H,m),6.26(1H,d,J=8.4 Hz),6.90(1H,t,J=7.4 Hz), 7.13(1H,d,J=8.7 Hz),7.29(2H,t,J=8.0 Hz),7.67-7.75(5H,m),7.82(1H,s).

IR(Nujol):3380,3244,1723,1638,1601,1578,1535,1495/cm.

[α] D =+73.6° (MeOH,c=0.50,26° C.).

m.p.133.0-134.° C.

No.2a-32

[α] D =+56.1° (MeOH,c=1.02,26° C.).

No.2a-33

CDCl 3 300 MHz 0.95(1H,d,J=10.2 Hz),1.10 and 1.21 (each,3H,each s),1.50-2.50(14H,m),4.25(1H,m),5.13(2H,s),5.30-5.70(3H,m),6.41(1H,d,J=8.2 Hz),6.89(1H,s),7.09(1H,s),7.17 and 7.72(each 2H,each d,J=8.2 Hz),7.62(1H,s).

IR(CHCl 3 ):3450,3125,3031,3013,2925,2870,2467,1917,1708,1654,1615,1575,1523,1497/cm.

[α] D =+55.2° (MeOH,c=1.01,26° C.).

No.2a-34

[α] D =+72.9° (MeOH,c=1.03,25° C.).

No.2a-35

CDCl 3 300 MHz 0.98(1H,d,J=10.2 Hz),1.13 and 1.24(each 3H,each s),1.52-2.48(14H,m),4.28(1H,m),5.35-5.51(2H,m),6.28(1H,d,J=8.7 Hz),7.34-7.37(3H,m),7.52-7.55(2H,m),7.58 and 7.71(each 2H,each d,J=8.7 Hz).

IR(CHCl 3 ):3515,3452,3030,3012,2925,2870,1739,1708,1652,1607,1655,1521,1497/cm.

[α] D =+74.3° (MeOH,c=1.01,25° C.).

No.2a-36

[α] D =+23.4° (MeOH,c=1.07,25° C.).

No.2a-37

CDCl 3 300 MHz 0.83(1H,d,J=10.5 Hz),0.95 and 1.18(each 3H,each s),1.44-2.46(14H,m),3.92(1H,m),5.34-5.52(3H,m),7.26-7.54(9H,m),7.62(1H,s).

IR(CHCl 3 ):3432,3310,3189,3023,3014,2924,2870,1704,1610,1594,1523,1487/cm.

[α] D =+25.3° (MeOH,c=1.00,26° C.).

No.2a-38

[α] D =+70.9° (MeOH,c=1.02,25° C.).

No.2a-39

[α] D =+70.6° (MeOH,c=1.01,25° C.).

No.2a-40

[α] D =+74.7° (MeOH,c=1.00,25° C.).

No.2a-41

[α] D =+72.1° (MeOH,c=1.01,24° C.).

No.2a-42

[α] D =+69.2° (MeOH,c=1.00,25° C.).

No.2a-43

[α] D =+70.8° (MeOH,c=1.00,25° C.).

No.2a-44

[α] D =+60.4° (MeOH,c=1.00,26° C.).

No.2a-45

CDCl 3 300 MHz 0.97(1H,d,J=9.9 Hz),1.13 and 1.23(each 3H,each s),1.55-2.52(14H,m),4.29(1H,m),5.34-5.54(2H,m),6.33(1H,d,J=9.0 Hz),7.10(1H,t,J=7.4 Hz),7.34(2H,t,J=7.4 Hz),7.52(2H,m),7.68 and 7.75(each 2H,each d,J=8.4 Hz),7.80(1H,s),8.10(1H,s),10.09(1H,s).

IR(CHCl 3 ):3393,3195,3093,3033,3013,2925,2870,1698,1656,1598,1537,1498/cm.

[α] D =+59.4° (MeOH,c=1.01,24° C.).

No.2a-46

[α] D =+63.5° (MeOH,c=1.00,25° C.).

No.2a-47

CDCl 3 300 MHz 0.97(1H,d,J=9.9 Hz),1.12 and 1.23(each 3H,each s),1.54-2.48(14H,m),4.29(1H,m),5.35-5.52(2H,m),6.32(1H,d,J=8.7 Hz),7.26(1H,m),7.41(2H,t,J=7.8 Hz),7.64(2H,d,J=7.5 Hz),7.73 and 7.77(each 2H,each d,J=8.4 Hz),7.95(1H,s),9.20(1H,s),10.38(1H,s).

IR(CHCl 3 ):3450,3339,3003,2992,2925,2870,1706,1653,1596,1523,1495/cm.

[α] D =+63.3° (MeOH,c=1.00,25° C.).

No.2a-48

[α] D =+63.8° (MeOH,c=1.00,24° C.).

No.2a-49

CDCl 3 300 MHz 1.00(1H,d,J=10.5 Hz),1.17 and 1.26(each 3H,each s),1.55-2.52(14H,m),4.34(1H,m),5.36-5.54(2H,m),6.35(1H,d,J=9.0 Hz),7.50-7.62(3H,m),7.90 and 8.33(each 2H,each d,J=8.4 Hz),8.21(2H,m).

IR(CHCl 3 ):3451,3029,3022,3016,2925,2870,1708,1655,1542,1508,1498,1471,1459/cm.

[α] D =+63.5° (MeOH,c=1.02,25° C.).

m.p.135.0-137.° C.

No.2a-50

[α] D =+68.9° (MeOH,c=1.01,24° C.).

No.0.2a-51

d 6 -DMSO 300 MHz 0.87(1H,d,J=9.9 Hz),1.10 and 1.17(each 3H,each s),1.40-1.60(3H,m),1.90-2.40(11H,m),3.98(1H,m),5.35-5.46(2H,m),7.64(1H,s),7.65 and 7.91(each 2H, each d,J=8.7 Hz),8.06(1H,d,J=6.0 Hz),9.32(1H,brs).

IR(KBr):3385,2962,1734,1707,1632,1529,1498/cm.

[α] D =+68.4° (MeOH,c=1.01,24° C.).

No.2a-52

[α] D =+76.2° (MeOH,c=1.01,24° C.).

No.2a-53

[α] D =+73.9° (MeOH,c=1.02,24° C.).

No.2a-54

[α] D =+68.1° (MeOH,c=1.00,24° C.).

No.2a-55

[α] D =+67.8° (MeOH,c=1.00,24° C.).

No.2a-56

[α] D =+65.4° (MeOH,c=1.03,25° C.).

No.2a-57

[α] D =+63.4° (MeOH,c=1.01,24° C.).

No.2a-58

[α] D =+66.6° (MeOH,c=1.01,24° C.).

No.2a-59

[α] D =+65.5° (MeOH,c=1.00,24° C.).

No.2a-60

[α] D =+60.9° (MeOH,c=1.02,25° C.).

No.2a-61

CDCl 3 300 MHz 0.97(1H,d,J=10.0 Hz),1.10 and 1.22(each 3H,each s),1.50-2.50(14H,m),4.26(1H,m),5.30-5.54(2H,m),6.28(1H,d,J=8.6 Hz),6.60 and 6.82(each 1H,each d,J=12.4 Hz,),7.12(2H,d,J=6.0 Hz),7.25 and 7.62(each 2H,each d,J=8.6 Hz), 8.47(2H,d,J=6.0 Hz).

IR(CHCl 3 ):3452,3027,3019,3013,2925,2870,2480,1708,1651,1606,1520,1494/cm.

[α] D =+61.6° (MeOH,c=1.01,25° C.).

No.2a-62

[α] D =+72.0° (MeOH,c=0.93,25° C.).

No.2a-63

CDCl 3 300 MHz 0.99(1H,d,J=10.2 Hz),1.14 and 1.24(each 3H,each s),1.50-2.50(14H,m),4.29(1H,m),5.36-5.55(2H,m),6.35(1H,d,J=9.1 Hz),7.04 and 7.27(each 1H,each d,J=16.5 Hz),7.37(2H,d,J=6.6 Hz),7.56 and 7.76(each 2H,each d,J=8.4 Hz), 8.57(2H,d,J=6.6 Hz).

IR(CHCl 3 ):3452,3024,3018,3014,2925,2870,2470,1933,1708,1652,1605,1521,1496/cm.

[α] D =+69.2° (MeOH,c=1.01,25° C.).

No.2a-64

[α] D =+56.9° (MeOH,c=1.24,25° C.).

No.2a-65

CDCl 3 300 MHz 0.98(1H,d,J=10.5 Hz),1.12 and 1.23(each 3H,each s),1.54-2.46(14H,m),4.27(1H,m),5.23(2H,s),5.34-5.52(2H,m),6.26(1H,d,J=8.4 Hz),7.32-7.45(5H,m),7.64 and 7.71(each 2H,each d,J=8.4 Hz),8.15(1H,s).

IR(CHCl 3 ):3452,3088,3065,3032,3013,2925,2870,1708,1653,1611,1559,1522,1496/cm.

[α] D =+61.0° (MeOH,c=0.91,25° C.).

No.2a-66

[α] D =+76.0° (MeOH,c=1.01,25° C.).

No.2a-67

CDCl 3 300 MHz 0.98(1H,d,J=10.4 Hz),1.14 and 1.24(each 3H,each s),1.54-2.46(14H,m),4.28(1H,m),5.32-5.53(2H,m),6.27(1H,d,J=8.6 Hz),6,92-7.31(each 1H,each d,J=16.4 Hz),7.02(1H,dd,J=5.8 and 3.6 Hz),7.12(1H,d,J=3.6 Hz),7.24(1H,d,J=5.8 Hz),7.51 and 7.70(each 2H,each d,J=8.4 Hz).

IR(CHCl 3 ):3453,3029,3013,2925,2870,1739,1650,1604,1524,1515,1494/ cm.

[α] D =+76.2° (MeOH,c=1.00,24° C.).

m.p.104.0-106.0° C.

No.2a-68

[α] D =+57.7° (MeOH,c=1.01,25° C.).

No.2a-69

CDCl 3 300 MHz 0.99(1H,d,J=10.2 Hz),1.14 and 1.24(each 3H,each s), 1.54-2.48(14H,m), 4.28(1H,m),5.34-5.53(2H,m),6.29(1H,d,J=9.0 Hz),6,54-6.74(each 1H,each d,J=12.0 Hz),7.02(1H,dd,J=4.8 and 3.3 Hz),6.97(1H,dd,J=3.3 and 1.2 Hz),7.13(1 H,dd,J=4.8 and 1.2 Hz),7.44 and 7.70(each 2H,each d,J=8.7 Hz).

IR(CHCl 3 ):3453,3025,3010,2925,2870,1708,1650,1607,1559,1523,1493/ cm.

[α] D =+58.4° (MeOH,c=1.00,25° C.).

No.2a-70

[α] D =+48.6° (MeOH,c=1.00,25° C.).

No.2a-71

CDCl 3 300 MHz 0.98(1H,d,J=10.2 Hz),1.12 and 1.23(each 3H,each s),1.52-2.46(14H,m),2.31(3H,s),4.26(1H,m),5.33-5.52(2H,m),6.20(1H,d,J=9.3 Hz),7.02-7.11 (6H,m)7.70(2H,d,J=9.0 Hz).

IR(CHCl 3 ):3460,3031,3022,3011,2925,2870,1750,1708,1650,1608,1597,1523,1490/ cm.

[α] D =+48.9° (MeOH,c=1.01,25° C.).

No.2a-72

[α] D =+51.2° (MeOH,c=1.02,25° C.).

No.2a-73

CDCl 3 300 MHz 0.97(1H,d,J=9.9 Hz),1.11 and 1.23(each 3H,each s),1.54-2.48(14H,m),4.27(1H,m),5.32-5.52(2H,m),6.24(1H,d,J=9.0 Hz),6.83-6.94(6H,m),7.65(2H,d,J=9.0 Hz).

IR(CHCl 3 ):3598,3451,3199,3033,3012,2925,2870,1708,1642,1604,1524,1507,1491/ cm.

[α] D =+52.2° (MeOH,c=1.01,25° C.).

No.2a-74

[α] D =+51.5° (MeOH,c=0.92,25° C.).

No.2a-75

CDCl 3 300 MHz 0.97(1H,d,J=10.2 Hz),1.11 and 1.23(each 3H,each s),1.55-2.46(14H,m),3.82(3H,s),4.25(1H,m),5.32-5.52(2H,m),6.19(1H,d,J=8.7 Hz),6.89-7.01(6H,m),7.65-7.68(2H,m).

IR(CHCl 3 ):3450,3025,3008,2925,2870,2837,1741,1649,1612,1521,15605,1490/ cm.

[α] D =+51.1° (MeOH,c=1.00,25° C.).

No.2a-76

[α] D =+60.4° (MeOH,c=0.98,25° C.).

No.2a-77

CDCl 3 300 MHz 0.99(1H,d,J=10.5 Hz),1.15 and 1.24(each 3H,each s),1.54-2.48(14H,m),2.34(3H,s),4.29(1H,m),5.32-5.54(2H,m),6.32(1H,d,J=8.4 Hz),7.19 and 7.60 (each 2H,each d,J=8.4 Hz),7.63 and 7.79(each 2H,each d,J=8.4 Hz).

IR(CHCl 3 ):3452,3027,3012,2925,2870,1751,1709,1651,1611,1560,1527,1509,1489/ cm.

[α] D =+61.2° (MeOH,c=1.00,25° C.).

No.2a-78

[α] D =+67.4° (MeOH,c=1.01,25° C.).

No.2a-79

CDCl 3 300 MHz 0.99(1H,d,J=10.2 Hz),1.15 and 1.24(each 3H,each s),1.54-2.54(14H,m),4.31(1H,m),5.32-5.54(2H,m),6.36(1H,d,J=8.2 Hz),6.93 and 7.48(each 2H,each d,J=8.6 Hz),7.59 and 7.75(each 2H,each d,J=8.4 Hz).

IR(CHCl 3 ):3593,3448,3192,3030,3010,2925,2870,1708,1644,1608,1591,1559,1530,1516,1491/ cm.

[α] D =+65.8° (MeOH,c=1.01,25° C.).

No.2a-80

[α] D =+66.9° (MeOH,c=1.01,25° C.).

No.2a-81

CDCl 3 300 MHz 0.99(1H,d,J=10.5 Hz),1.15 and 1.24(each 3H,each s),1.54-2.48(14H,m),3.86(3H,s),4.29(1H,m),5.34-5.52(2H,m),6.20(1H,d,J=8.7 Hz),6.99 and 7.55 (each 2H,each d,J=9.0 Hz),7.61 and 7.77(each 2H,each d,J=8.7 Hz).

IR(CHCl 3 ):3450,3009,2925,2870,2838,1740,1708,1650,1608,1557,1528,1512,1491/ cm.

[α] D =+66.2° (MeOH,c=1.01,25° C.).

No.2a-82

[α] D =+57.7° (MeOH,c=1.02,24° C.).

No.2a-83

CDCl 3 300 MHz 0.97(1H,d,J=10.2 Hz),1.12 and 1.23(each 3H,each s),1.54-2.48(14H,m),2.33(3H,8),4.26(1H,m),5.32-5.52(2H,m),6.25(1H,d,J=8.7 Hz),7.16 and 7.75 (each 2H,each d,J=8.7 Hz).

IR(CHCl 3 ):3452,3030,3022,3012,2925,2870,1754,1709,1654,1604,1585,1522,1493/ cm.

[α] D =+57.4° (MeOH,c=1.01,24° C.).

No.2a-84

[α] D =+57.8° (MeOH,c=1.01,24° C.).

No.2a-85

CDCl 3 300 MHz 0.95(1H,d,J=10.2 Hz),1.12 and 1.22(each 3H,each s),1.54-2.48(14H,m),4.25(1H,m),5.32-5.52(2H,m),6.28(1H,d,J=8.7 Hz),6.87 and 7.57(each 2H,each d,J=9.0 Hz).

IR(CHCl 3 ):3590,3450,3166,3019,3012,2925,2871,1708,1637,1608,1583,1531,1498/ cm.

[α] D =+56.0° (MeOH,c=1.01,24° C.).

No.2a-86

[α] D =+59.3° (MeOH,c=1.01,22° C.).

No.2a-87

CDCl 3 300 MHz 0.98(1H,d,J=10.0 Hz),1.13 and 1.23(each 3H,each s),1.54-2.48(14H,m),3.85(3H,s),4.25(1H,m),5.32-5.53(2H,m),6.19(1H,d,J=8.8 Hz),6.93 and 7.69 (each 2H,each d,J=9.0 Hz).

IR(CHCl 3 ):3450,3030,3017,3012,2925,2870,2840,1740,1708,1647,1606,1575, 1525,1496/ cm.

[α] D =+58.2° (MeOH,c=0.99,22° C.).

No.2a-88

[α] D =+50.9° (MeOH,c=1.02,25° C.).

No.2a-89

CDCl 3 300 MHz 0.99(1H,d,J=10.2 Hz),1.18 and 1.26(each 3H,each s), 1.56-2.48 (14H,m),4.29(1H,m),5.36-5.54(2H,m),7.03(1H,d,J=8.7 Hz),7.21(1H,s),7.43(2H,m),7.74(1H,ddd,J=1.8,6.9 and 8.7 Hz),8.22(1H,dd,J=1.8 and 8.1 Hz).

IR(CHCl 3 ):3443,3087,3023,3014,2925,2870,1708,1685,1658,1630,1517,1466/ cm.

[α] D =+57.1° (MeOH,c=1.01,22° C.).

m.p.117.0-118.0° C.

No.2a-90

[α] D =+54.1° (MeOH,c=1.01,22° C.).

No.2a-91

CDCl 3 300 MHz 0.97(1H,d,J=10.2 Hz),1.13 and 1.23(each 3H,each s),1.52-2.46(14H,m),4.24(1H,m),5.34-5.52(2H,m),6.49-6.53(2H,m),7.11(1H,dd,J=0.9 and 3.6 Hz),7.44(1H,dd,J=0.9 and 1.8 Hz).

IR(CHCl 3 ):3437,3033,3022,3014,2925,2870,1739,1708,1655,1595,1520,1472/ cm.

[α] D =+55.0° (MeOH,c=1.00,22° C.).

No.2a-92

[α] D =+50.3° (MeOH,c=1.00,22° C.).

No.2a-93

CDCl 3 300 MHz 0.95(1H,d,J=10.5 Hz),1.12 and 1.23(each 3H,each s),1.52-2.46(14H,m),4.25(1H,m),5.34-5.52(2H,m),6.12(1H,d,J=8.7 Hz),7.07(1H,dd,J=3.9 and 5.1 Hz), 7.45-7.48(2H,m).

IR(CHCl 3 ):3450,3023,3011,2925,2870,1739,1708,1645,1531,1501,1471/ cm.

[α] D =+49.1° (MeOH,c=1.02,24° C.).

No.2a-94

[α] D =+51.5° (MeOH,c=1.00,24° C.).

No.2a-95

CDCl 3 300 MHz 0.96(1H,d,J=10.5 Hz),1.11 and 1.23(each 3H,each s),1.52-2.46(14H,m),4.25(1H,m),5.34-5.56(2H,m),6.14(1H,d,J=8.7 Hz),7.34(2H,d,J=2.0 Hz),7.85(1H,t, J=2.0 Hz).

IR(CHCl 3 ):3452,3114,3030,3013 2925,2870,1708,1649,1535,1498,1471/cm.

[α] D =+55.5° (MeOH,c=1.00,25° C.).

m.p.87.0-88.0° C.

No.2a-96

CD 3 OD 300 MHz 0.94(1H,d,J=10.2 Hz),1.13 and 1.22(each 3H,each s),1.50-1.76(3H,m),1.94-2.39(11H,m),4.11(1H,m),5.39-5.49(2H,m),7.43-7.51(2H,m),8.05(1H,m).

IR(KBr):3369,3084,2985,2921,2868,1630,1566,1538,1503/ cm.

[α] D =+38.8° (MeOH,c=1.01,22° C.).

No.2a-97

CD 3 OD 300 MHz 0.93(1H,d,J=9.9 Hz),1.13 and 1.22(each 3H,each s),1.48-1.58(3H,m),1.96-2.36(11H,m),4.10(1H,m),5.35-5.50(2H,m),7.42-7.51(2H,m),8.06(1H,m).

IR(KBr):3447,3087,2987,2922,2868,1629,1545,1501/ cm.

[α] D =+52.9° (MeOH,c=1.01,24° C.).

No.2a-98

[α] D =+53.2° (MeOH,c=1.02,23° C.).

No.2a-99

CDCl 3 300 MHz 0.97(1H,d,J=10.2 Hz),1.12 and 1.22(each 3H,each s),1.26-2.45(24H,m),4.25(2H,m),5.34-5.62(2H,m),6.18(1H,d,J=8.7 Hz),6.91 and 7.66(each 2H,each d,J=9.0 Hz).

IR(CHCl 3 ):3455,3029,3019,2939,2862,1738,1709,1645,1605,1523,1494/ cm.

[α] D =+51.4° (MeOH,c=1.00,23° C.).

No.2a-100

[α] D =+49.3° (MeOH,c=1.00,24° C.).

No.2a-101

[α] D =+51.3° (MeOH,c=1.00,24° C.).

No.2a-102

[α] D =+48.8° (MeOH,c=1.01,23° C.).

No.2a-103

CDCl 3 300 MHz 0.94(1H,d,J=10.2 Hz),1.12 and 1.22(each 3H,each s),1.52-2.46(14H,m),2.48(3H,d,J=0.3 Hz),4.20(1H,m),5.32-5.54(2H,m),6.46(1H,brs),7.12(1H,d,J=9.0 Hz).

IR(CHCl 3 ):3416,3144,3029,3011,2926,2871,1708,1671,1598,1538,14564/ cm

[α] D =+49.6° (MeOH,c=1.01,23° C.).

No.2a-104

[α] D =+77.0° (MeOH,c=1.02,23° C.).

No.2a-105

CDCl 3 300 MHz 93(1H,d,J=9.9 Hz),1.09 and 1.21(each 3H,each s),1.51-2.44(14H,m),3.90(6H,s),4.20(1H,m),5.38-5.50(2H,m),5.87(1H,d,J=9.0 Hz),6.25 and 7.54 (each 1H,each d,J=15.6 Hz),6.84(1H,d,J=8.1 Hz),7.03(1H,d,J=1.8 Hz),7.09(1H,dd,J=1.8 and 8.1 Hz).

IR(CHCl 3 ):3439,3028,3012,2937,2871,2841,1739,1708,1661,1620,1600,1513/ cm.

[α] D =+77.3° (MeOH,c=1.01,23° C.).

No.2a-106

[α] D =+67.0° (MeOH,c=1.00,25° C.).

No.2a-107

[α] D =+66.6° (MeOH,c=1.01,24° C.).

m.p.168.0-170.0° C.

No.2a-108

[α] D =+61.8° (MeOH,c=1.00,22° C.).

No.2a-109

CDCl 3 300 MHz 0.96(1H,d,J=10.2 Hz),1.10 and 1.22(each 3H,each s),1.51-2.45(14H,m),4.25(1H,m),5.33-6.49(2H,m),6.21(1H,d,J=8.7 Hz),7.25 and 7.60(each 2H,each d,J=8.7 Hz),7.33-7.41(5H,s).

IR(CHCl 3 ):3453,3062,3028,3014,2925,2870,1739,1708,1651,1594,1557,1515,1481/ cm.

[α] D =+61.0° (MeOH,c=1.01,22° C.).

No.2a-110

CD 3 OD 300 MHz 0.94(1H,d,J=9.9 Hz),1.13 and 1.22(each 3H,each s),1.54-2.37(14H,m),4.12(1H,m),5.38-5.49(2H,m),7.25 and 7.68(each 2H,each d,J=8.7 Hz),7.41(5H,s).

IR(KBr):3435,3058,2986,2920,2866,1635,1595,1562,1521,1482,1439,1411/ cm.

[α] D =+47.3° (MeOH,c=1.01,23° C.).

No.2a-111

[α] D =+65.6° (MeOH,c=1.01,24° C.).

No.2a-112

CDCl 3 300 MHz 0.97(1H,d,J=10.2 Hz),1.12 and 1.23(each 3H,each s),1.51-2.46(14H,m),4.27(1H,m),5.35-5.50(2H,m),6.22(1H,d,J=8.4 Hz),7.40 and 7.66(each 2H,each d,J=9.0 Hz).

IR(CHCl 3 ):3439,3028,3012,2937,2871,2841,1739,1708,1661,1620,1600,1513/ cm.

[α] D =+65.6° (MeOH,c=1.01,22° C.).

No.2a-113

[α] D =+59.6° (MeOH,c=1.00,24° C.).

No.2a-114

CDCl 3 300 MHz 0.98(1H,d,J=10.2 Hz),1.12 and 1.24(each 3H,each s),1.52-2.46(14H,m),4.29(1H,m),5.35-5.51(2H,m),6.28(1H,d,J=8.4 Hz),7.70 and 7.83(each 2H,each d,J=8.4 Hz).

IR(CHCl 3 ):3439,3028,3012,2937,2871,2841,1739,1708,1661,1620,1600,1513/cm.

[α] D =+60.6° (MeOH,c=1.01,22° C.).

No.2a-115

[α] D =+59.7° (MeOH,c=0.99,24° C.).

No.2a-116

CDCl 3 300 MHz 0.97(1H,d,J=10.2 Hz),1.12 and 1.23(each 3H,each s),1.52-2.46(14H,m),2.39(3H,s),4.27(1H,m),5.33-5.51(2H,m),6.24(1H,d,J=9.0 Hz),7.23 and 7.62(each 2H,each d,J=8.4 Hz).

IR(CHCl 3 ):3439,3028,3012,2937,2871,2841,1739,1708,1661,1620,1600,1513/ cm.

[α] D =+59.7° (MeOH,c=0.99,24° C.).

No.2a-117

[α] D =+56.7° (MeOH,c=1.00,23° C.).

No.2a-118

CDCl 3 300 MHz 0.96(1H,d,J=10.2 Hz),1.11 and 1.23(each 3H,each s),1.53-2.44(14H,m),4.23(1H,m),5.34-5.51(2H,m),6.02(2H,s),6.13(1H,d,J=8.7 Hz),6.83(1H,dd,J=1.2 and 7.8 Hz),7.22-7.25(2H,m).

IR(CHCl 3 ):3453,3031,3020,3012,2924,2870,1740,1708,1650,1619,1605,1519,1504,1480/ cm.

[α] D =+57.2° (MeOH,c=1.02,23° C.).

No.2a-119

CDCl 3 300 MHz 0.96(1H,d,J=10.5 Hz),1.07 and 1.23(each 3H,each s),1.51-2.44(14H,m),2.32(3H,s),4.26(1H,m),5.37-5.52(2H,m),6.40(1H,d,J=9.0 Hz),7.09(1H,m),7.30(1H,m),7.46(1H,m),7.66(1H,m).

IR(CHCl 3 ):3443,3028,3012,2925,2870,1766,1747,1709,1657,1607,1516,1479/ cm.

[α] D =+53.2° (MeOH,c=0.99,21° C.).

No.2a-120

CDCl 3 300 MHz 0.98(1H,d,J=10.2 Hz),1.14 and 1.24(each 3H,each s),1.53-2.44(14H,m),4.30(1H,m),5.35-5.52(2H,m),6.42(1H,d,J=8.7 Hz),6.85(1H,m),6.99(1H,dd,J=1.2 and 8.4 Hz),7.27(1H,m),7.39(1H,m).

IR(CHCl 3 ):3463,3033,3021,3014,2992,2924,28,1708,1643,1597,1523,1488/cm.

[α] D =+46.3° (MeOH,c=1.01,21° C.).

No.2a-121

CDCl 3 300 MHz 0.98(1H,d,J=10.2 Hz),1.14 and 1.23(each 3H,each s),1.47-2.47(14H,m),3.95(3H,s),4.31(1H,m),5.32-5.50(2H,m),6.98(1H,dd,J=0.9 and 8.4 Hz),7.09(1H, ddd,J=0.9,7.7 and 8.4 Hz),7.45(1H,m),8.19(1H,dd,J=2.1 and 8.1 Hz),8.32(1H,d,J=9.0 Hz).

IR(CHCl 3 ):3400,3078,3028,3020,3007,2924,2870,2842,1736,1708,1640,1600,1536,1483,1470/ cm.

[α] D =+38.1° (MeOH,c=1.02,23° C.).

No.2a-122

[α] D =+42.3° (MeOH,c=0.99,23° C.).

No.2a-123

[α] D =+38.7° (MeOH,c=1.00,21° C.).

No.2a-124

[α] D =+45.0° (MeOH,c=1.01,21° C.).

m.p. 119.0-120.0° C.

No.2a-125

[α] D =+49.8° (MeOH,c=1.01,22° C.).

No.2a-126

CDCl 3 300 MHz 0.97(1H,d,J=10.2 Hz),1.11 and 1.23(each 3H,each s),1.52-2.47(14H,m),4.26(1H,m),5.34-5.50(2H,m),6.22(1H,d,J=8.7 Hz),7.55-7.61(4H,m).

IR(CHCl 1 ):3400,3078,3028,3020,3007,2924,2870,2842,1736,1708,1640,1600,1536,1483,1470/ cm.

[α] D =+63.0° (MeOH,c=1.01,23° C.).

No.2a-127

CDCl 3 300 MHz 0.91(1H,d,J10.2 Hz),1.10 and 1.20(each 3H,each s),1.50-2.42(14H,m),4.23(1H,m),5.31-5.51(2H,m),6.45(1H,d,J=8.4 Hz),7.01(1H,t,J=7.4 Hz),7.22-7.27(2H,m),7.33-7.40(4H,m),7.53(2H,d,J=9.0 Hz),8.30 and 8.48(each 1H,each s)

IR(CHCl 3 ):3452,3028,3022,3015,2925,2870,1708,1654,1590,1514,1478/ cm.

[α] D =+59.5° (MeOH,c=1.01,23° C.).

No.2a-128

d 6 -DMSO 300 MHz 0.84(1H,d,J=9.9 Hz),1.06 and 1.19(each 3H,each s),1.37-2.37(14H,m),3.79(1H,m),5.35-5.51(2H,m),6.08(1H,d,J=8.7 Hz),6.85-6.90(1H,m),7.18-7.23(2H,m),7.35-7.38(2H,m),8.42(1H,s),12.00(1H,s).

IR(Nujol):3395,3345,2925,2866,2623,2506,1697,1658,1638,1597,1557/ cm.

[α] D =+26.0° (MeOH,c=1.01,23° C.).

m.p.164.0-166.0° C.

No.2a-129

CDCl 3 300 MHz 1.01(1H,d,J=10.0 Hz),1.17 and 1.25(each 3H,each s),1.54-2.52(14H,m),4.34(1H,m),5.36-5.57(2H,m),6.42(1H,d,J=8.6 Hz),7.51-7.60(2H,m),7.77(1H,dd,J=1.8 and 8.6 Hz),7.85-7.96(3H,m),8.24(1H,brs).

IR(CHCl 3 ):3451,3060,3028,3010,2925,2870,1708,1652,1629,1600,1517,1502/cm.

[α] D =+68.6° (MeOH,c=1.00,22° C.).

No.2a-130

CDCl 3 300 MHz 1.02(1H,d,J=10.2 Hz),1.04 and 1.26(each 3H,each s),1.54-2.52(14H,m),4.41(1H,m),5.41-6.68(2H,m),6.14(1H,d,J=9.0 Hz),7.43-7.59(4H,m),7.85-7.92(2H, m),8.27(1H,dd,J=1.8 and 7.2 Hz).

IR(CHCl 3 ):3436,3032,3010,2924,2870,2664,1708,1652,1512,1498/ cm.

[α] D =+93.9° (MeOH,c=1.00,22° C.)

m.p.94.0-96.0° C.

No.2a-131

[α] D =+50.2° (MeOH,c=0.95,21° C.).

No.2a-132

[α] D =+10.9° (MeOH,c=0.92,21° C.).

No.2a-133

[α] D =+60.4° (MeOH,c=1.00,21° C.).

No.2a-134

[α] D =+38.5° (MeOH,c=1.01,23° C.).

No.2a-135

[α] D =+52.5° (MeOH,c=1.01,23° C.).

m.p.180.0-182.0° C.

No.2a-136

[α] D =+35.3° (MeOH,c=1.02,23° C.).

m.p.79.0-80.0° C.

No.2a-137

CDCl 3 300 MHz 0.97(1H,d,J=10.2 Hz),1.11 and 1.22(each 3H,each s),1.43(3H,t,J=6.9 Hz),1.52-2.44(14H,m),4.03(2H,q,J=6.9 Hz),4.26(1H,m),5.33-5.50(2H,m),6.19(1H,d, J=8.7 Hz),6.88-7.00(6H,m),7.65-7.68(2H,m).

IR(CHCl 3 ):3455,3031,3024,3014,2988,2925,2870,1741,1708,1649,1602,1521,1504,1490/ cm.

[α] D =+52.0° (MeOH,c=1.01,23° C.).

No.2a-138

CDCl 3 300 MHz 0.97(1H,d,J=10.2 Hz),1.11 and 1.22(each 3H,each s),1.35(6H,d,J=6.0 Hz),1.53-2.46(14H,m),4.25(1H,m),4.51(1H,m),5.33-5.50(2H,m),6.12(1H,d,J=9.0 Hz),6.87-6.99(6H,m),7.65-7.68(2H,m).

IR(CHCl 3 ):3454,3031,3014,2980,2925,2870,1741,1708,1649,1602,1522,1490/ cm.

[α] D =+50.0° (MeOH,c=1.05,22° C.).

No.2a-139

CDCl 3 300 MHz 1.00(1H,d,J=10.2 Hz),1.16 and 1.24(each 3H,each s),1.59-2.52(14H,m),4.31(1H,m),5.40-5.53(2H,m),6.36(1H,d,J=8.7 Hz),6.70(1H,d,J=1.5 Hz),7.12(1H, m),7.30(1H,m),7.47(1H,dd,J=0.6 and 8.1 Hz),7.61(1H,d,J=8.4 Hz).

IR(CHCl 3 ):3449,3243,3029,3022,3013,2925,2871,1707,1631,1542,1505/ cm.

[α] D =+63.4° (MeOH,c=1.00,23° C.).

m.p.178.0-179.0° C.

No.2a-140

CDCl 3 300 MHz 0.97(1H,d,J=10.2 Hz),1.18 and 1.23(each 3H,each s),1.57-2.50(14H,m),4.35(1H,m),5.32-5.55(2H,m),6.42(1H,d,J=8.7 Hz),6.70(1H,d,J=1.5 Hz),7.21-7.24(2H m),7.46(1H,m),7.76(1H,m),7.86(1H,d,J=3.0 Hz),10.20(1H,s).

IR(CHCl 3 ):3466,3010,2924,1739,1604,1546,1504/ cm.

[α] D =+39.4° (MeOH,c=1.01,22° C.).

m.p.167.0-168.0° C.

No.2a-141

CDCl 3 300 MHz 0.99(1H,d,J=10.2 Hz),1.14 and 1.24(each 3H,each s), 1.55-2.44(14H,m),3.84(3H,s),4.27(1H,m),5.34-5.52(2H,m),6.28(1H,d,J=9.0 Hz),6.91 and 7.47 (each 2H,each d,J=9.0 Hz),6.98 and 7.14(each 1H,each d,J=16.5 Hz),7.54 and 7.70(each 2H,each d,J=8.7 Hz).

IR(CHCl 3 ):3453,3025,3015,2925,2870,2839,1740,1708,1649,1602,1510,1493, 1470/ cm.

[α] D =+73.4° (MeOH,c=1.02,22° C.).

m.p.155.0-157.0° C.

No.2a-142

CDCl 3 300 MHz 0.97(1H,d,J=10.2 Hz),1.11. and 1.23(each 3H,each s),1.52-2.45(14H,m),3.79(3H,s),4.27(1H,m),5.34-5.50(2H,m),6.24(1H,d,J=9.0 Hz),6.49 and 6.62 (each 1H each d,J=12.3 Hz),6.77 and 7.16(each 2H,each d,J=8.7 Hz),7.32 and 7.59(each 2H,each d,J=8.1 Hz).

IR(CHCl 3 ):3453,3025,3014,2925,2870,2839,1739,1708,1649,1606,1510, 1494/ cm.

[α] D =+60.7° (MeOH,c=0.99,22° C.).

No.2a-143

[α] D =+57.3° (MeOH,c=1.01,23° C.).

No.2a-144

[α] D =+12.2° (MeOH,c=1.00,23° C.).

m.p.114.0-116.0° C.

No.2a-145

CDCl 3 300 MHz 0.95(1H,d,J=10.2 Hz),1.10 and 1.21(each 3H,each s),1.52-2.44(14H,m),4.25(1H,m),5.33-5.49(2H,m),6.37(1H,d,J=8.7 Hz),7.45-7.47(3H,m),7.62-7.66(2H, m),7.69 and 7.80(each 2H,each d,J=7.5 Hz,).

IR(CHCl 3 ):3449,3058,3027,3012,2925,2870,1708,1655,1513,1481,1043/ cm.

[α] D =+61.0° (MeOH,c=1.01,23° C.).

No.2a-146

CDCl 3 300 MHz 0.95(1H,d,J=10.5 Hz),1.09 and 1.21(each 3H,each s),1.50-2.41(14H,m),4.25(1H,m),5.33-5.49(2H,m),6.33(1H,d,J=8.4 Hz),7.49-7.61(3H,m),7.91-7.92(2H, m),7.82 and 7.97(each 2H,each d,J=8.7 Hz).

IR(CHCl 3 ):3447,3029,3023,3015,2925,2870,1708,1660,1514,1484,1321,1161/ cm.

[α] D =+62.0° (MeOH,c=1.00,22° C.).

No.2a-147

CDCl 3 300 MHz 0.97(1H,d,J=10.2 Hz),1.12 and 1.23(each 3H,each s),1.52-2.46(14H,m),2.51(3H,s),4.26(1H,m),5.34-5.51(2H,m),6.23(1H,d,J=8.4 Hz), 7.26 and 7.64 (each 2H,each d,J=8.4 Hz).

IR(CHCl 3 ):3453,3027,3015,2925,2870,2665, 1708, 1648, 1596,1516,1484/ cm.

[α] D =+67.7° (MeOH,c=0.82,22° C.).

No.2a-148

[α] D =+72.5° (MeOH,c=1.01,25° C.).

No.2a-149

[α] D =+67.8° (MeOH,c=0.98,25° C.).

No.2a-150

CDCl 3 300 MHz 0.94(1H,d,J=10.2 Hz), 1.10 and 1.23(each 3H,each s), 1.52-2.50(14H,m),4.22(1H,m),5.36-5.55(2H,m),6.48(1H,d,J=8.4 Hz),8.35(1H,s),8.90(1H,s).

IR(CHCl 3 ):3443,3374,3091,3024,3012,2925,2871,1709,1652,1525,1494/ cm.

[α] D =+58.1° (MeOH,c=1.01,23° C.).

m.p.120.0-122.0° C.

No.2a-151

[α] D =+40.6° (MeOH,c=1.01,23° C.).

No.2a-152

CDCl 3 300 MHz 0.96(1H,d,J=10.5 Hz),1.10 and 1.24(each 3H,each s),1.50-2.50(14H,m),2.71(3H,s),4.26(1H,m),5.37-5.5 1(2H,m),6.02(1H,d,J=9.0 Hz),8.73(1H,s).

IR(CHCl 3 ):3463,3435,3087,3025,3014,2925,2870,1708,1649,1523,1503/ cm.

[α] D =+54.1° (MeOH,c=1.02,22° C.).

No.2a-153

CDCl 3 300 MHz 0.95(1H,d,J=9.9 Hz),1.11 and 1.23(each 3H,each s),1.50-2.50(14H,m),2.50(3H,s),4.26(1H,m),5.36-5.51(2H,m),6.01(1H,d,J=8.4 Hz),6.88(1H,d,J=5.1 Hz), 7.26(1H,d,J=5.1 Hz).

IR(CHCl 3 ):3469,3431,3025,3013,2925,2871,2664,1708,1639,1544,1505/ cm.

[α] D =+35.8° (MeOH,c=1.03,22° C.).

No.2a-154

CDCl 3 300 MHz 0.95(1H,d,J=9.9 Hz),1.10 and 1.22(each 3H,each s),1.52-2.46(14H,m),2.51(3H,d,J=1.2 Hz),4.26(1H,m),5.34-5.50(2H,m),6.00(1H,d,J=8.4 Hz),6.73(1H,dd, J=5.1 and 3.6 Hz),7.29(1H,d,J=3.6 Hz).

IR(CHCl 3 ):3450,3431,3026,3011,2925,2869,1739,1708,1639,1547,1508/ cm.

[α] D =+50.5° (MeOH,c=1.01,22° C.).

No.2a-155

CDCl 3 300 MHz 0.99(1H,d,J=10.2 Hz),1.19 and 1.25(each 3H,each s),1.53-2.48(14H,m),4.31(1H,m),5.36-5.51(2H,m),6.79(1H,d,J=9.3 Hz),7.29(1H,m),7.41(1H,m),7.48(1H,s),7.51(1H,m),7.66(1H,d,J=8.1 Hz).

IR(CHCl 3 ):3436,3029,3024,3015,2925,2871,2670,1708,1659,1598,1510/ cm.

[α] D =+69.1° (MeOH,c=1.01,22° C.).

No.2a-156

CDCl 3 :CD 3 O D =10:1 300 MHz 0.99(1H,d,J=9.9 Hz),1.11 and 1.21(each 3H,each s),1.56-2.58(14H,m),4.22(1H,m),5.35-5.59(2H,m),6.83(1H,d,J=8.4 Hz),7.48(1H,d,J=8.4 Hz),7.61(1H,dd J=1.5 and 8.4 Hz),8.09(1H,d,J=1.5 Hz),8.12(1H,s).

IR(KBr):3422,3115,2985,2922,2869,2609,1708,1636,1578,1529,1470/ cm.

[α] D =+62.8° (MeOH,c=1.01,22° C.).

No.2a-157

[α] D =+40.0° (MeOH,c=0.95,22° C.).

No.2a-158

CDCl 3 300 MHz 1.00(1H,d,J=10.5 Hz),1.17 and 1.24(each 3H,each s),1.54-2.50(14H,m),4.34(1H,m),5.36-5.52(2H,m),7.80(1H,d,J=9.0 Hz),9.30(1H,s).

IR(CHCl 3 ):3410,3122,3030,3012,2925,2871,2668,1709,1667,1538,1466/ cm.

[α] D =+44.9° (MeOH,c=0.99,22° C.).

No.2a-159

CDCl 3 300 MHz 0.97(1H,d,J=10.2 Hz),1.13 and 1.22(each 3H,each s),1.55-2.43(14H,m),3.03(6H,s),4.23(1H,m),5.32-5.51(2H,m),6.16(1H,d,J=8.7 Hz),6.87 and 7.63 (each 2H,each d,J=8.7 Hz).

IR(CHCl 3 ):3457,3028,3006,2924,2870,2654,1739,1709,1637,1608,1608,1534, 1501/ cm.

[α] D =+64.8° (MeOH,c=1.01,22° C.).

No.2a-160

d 6 -DMSO 300 MHz 0.83(1H,d,J=9.9 Hz),1.02 and 1.19(each 3H,each s),1.38-1.61(3H,m),1.90-2.32(11H,m),3.90(1H,m),5.41-5.44(2H,m),7.32(1H,dd,J=0.9 and 7.2 Hz),7.45-7.60(2H,m),7.77(1H,dd,J=0.9 and 7.8 Hz),8.03(1H,d,J=6.9 Hz),12.40(1H,s).

IR(Nujol):3315,2924,2856,2656,2535,1737,1703,1637,1598,1581,1541/ cm. [α] D =+78.5° (MeOH,c=1.01,24° C.).

m.p.161.0-162.0° C.

No.2a-161

[α] D =+65.3° (MeOH,c=1.00,22° C.).

No.2a-162

CDCl 3 300 MHz 0.99(1H,d,J=10.2 Hz),1.13 and 1.25(each 3H,each s), 1.53-2.45(14H,m),4.30(1H,m),5.36-5.51(2H,m),6.32(1H,d,J=8.4 Hz),7.88 and 8.28(each 2H,each d,J=9.0 Hz).

IR(CHCl 3 ):3448,3029,3016,2925,2870,1708,1664,1602,1527,1484,1347/ cm.

[α] D =+72.7° (MeOH,c=1.02,22° C.).

No.2a-163

CDCl 3 300 MHz 0.96(1H,d,J=10.2 Hz),1.11 and 1.23(each 3H,each s),1.55-2.51(14H,m),4.26(1H,m),5.36-5.57(2H,m),6.68(1H,d,J=7.8 Hz),7.41(1H,dd,J=4.8 and 8.1 Hz), 8.20(1H,d,J=8.1 Hz),8.66(1H,d,J=4.8 Hz),9.00(1H,s).

IR(CHCl 3 ):3448,3026,3013,2925,2870,2534,1709,1658,1590,1515,1471/ cm.

[α] D =+71.3° (MeOH,c=1.01,22° C.).

No.2a-164

[α] D =+40.8° (MeOH,c=0.98,22° C.).

No.2a-165

CDCl 3 300 MHz 0.96(1H,d,J=10.5 Hz),1.11 and 1.24(each 3H,each s),1.55-2.52(14H,m),4.24(1H,m),5.37-5.57(2H,m),6.63(1H,d,J=7.8 Hz),7.59 and 8.63(each 2H each d,J=6.0 Hz).

IR(CHCl 3 ):3447,3346,3028,3016,2925,2870,2538,1941,1708,1662,1556,1516/ cm.

[α] D =+75.4° (MeOH,c=1.01,22° C.).

No.2a-166

CDCl 3 300 MHz 0.97(1H,d,J=10.2 Hz),1.11 and 1.22(each 3H,each s),1.51-2.44(14H,m),2.95(6H,s),4.25(1H,m),5.33-5.50(2H,m),6.19(1H,d,J=8.7 Hz),6.77 and 6.97 (each 2H,each d,J=8.4 Hz),6.94 and 7.65(each 2H,each d,J=9.0 Hz).

IR(CHCl 3 ):3463,3024,3016,2924,2871,2806,1739,1708,1647,1612,1604,1515,1490/ cm.

[α] D =+53.1° (MeOH,c=1.02,23° C.).

m.p.104.0-105.5° C.

No.2a-167

CDCl 3 300 MHz 1.01(1H,d,J=9.9 Hz),1.19 and 1.26(each 3H,each s),1.56-2.53(14H,m),4.37(1H,m),5.35-5.55(2H,m),6.47(1H,d,J=8.4 Hz),7.61-7.71(2H,m),7.79(2H,s),7.89-7.97(2H,m),8.27(1H,d,J=2.1 Hz),8.66-8.73(2H,m).

IR(CHCl 3 ):3450,3024,3014,2925,2870,2667,1707,1650,1531,1509/ cm.

[α] D =+70.5° (MeOH,c=1.00,22° C.).

No.2a-168

CDCl 3 300 MHz 1.02(1H,d,J=10.2 Hz),1.20 and 1.26(each 3H,each s),1.56-2.50(14H,m),4.38(1H,m),5.36-5.56(2H,m),6.51(1H,d,J=8.4 Hz),7.61-7.93(7H,m),8.74(1H,d,J=8.4 Hz),9.15(1H,s).

IR(CHCl 3 ):3517,3451,3060,3028,3011,2925,2870,2664,1709,1651,1519,1498/ cm.

[α] D =+54.4° (MeOH,c=1.00,23° C.).

No.2a-169

CDCl 3 300 MHz 0.96(1H,d,J=10.5 Hz),1.09 and 1.21(each 3H,each s),1.50-2.44(14H,m),3.85(3H,s),4.24(1H,m),5.32-5.48(2H,m),6.19(1H,d,J=8.4 Hz),6.94 and 7.45 (each 2H,each d,J=9.0 Hz),7.11 and 7.45(each 2H,each d,J=8.7 Hz).

IR(CHCl 3 ):3516,3453,3029,3009,2925,2870,2840,2665,1708,1650,1593,1515,1493,1482/ cm.

[α] D =+57.8° (MeOH,c=1.00,23° C.).

No.2a-170

CDCl 3 300 MHz 0.98(1H,d,J=10.2 Hz),1.15 and 1.24(each 3H,each s),1.52-2.50(14H,m),4.28(1H,m),5.33-5.54(2H,m),6.25(1H,d,J=8.2 Hz),7.38-7.44(2H,m),7.74(1H,s),7.81-7.86(2H,m).

IR(CHCl 3 ):3517,3448,3427,3024,3013,2925,2870,2669,1708,1650,1562,1535,1500/ cm.

[α] D =+61.6° (MeOH,c=1.00,23° C.).

No.2a-171

CDCl 3 300 MHz 0.96(1H,d,J=10.2 Hz,1.11 and 1.22(each 3H,each s),1.52-2.42(14H,m),2.48 (3H,s),4.21(1H,m),5.31-5.52(2H,m),6.06(1H,d,J=8.2 Hz),6.97 and 7.59 (each 1H,each d,J=1.2 Hz).

IR(CHCl 3 ):3452,3113,3028,3007,2925,2870,2669,1708,1645,1554,1509/ cm.

[α] D =+52.4° (MeOH,c=1.00,23° C.).

No.2a-172

CDCl 3 300 MHz 0.96(1H,d,J=10.2 Hz),1.09 and 1.28(each 3H,each s),1.50-2.40(14H,m),2.69(3H,s),4.24(1H,m),5.35-5.51(2H,m),5.96(1H,d,J=8.7 Hz),7.03 and 7.07 (each 1H,each d,J=5.4 Hz).

IR(CHCl 3 ):3451,3031,3013,2925,2870,2666,1708,1647,1542,1497/ cm.

[α] D =+51.2° (MeOH,c=1.00,23° C.).

No.2a-173

CDCl 3 300 MHz 0.95(1H,d,J=10.2 Hz),1.10 and 1.23(each 3H,each s),1.50-2.45(14H,m),4.22(1H,m),5.35-5.49(2H,m),6.05(1H,d,J=8.4 Hz),7.26 and 7.75(each 1H,each d,J=1.5 Hz).

IR(CHCl 3 ): 3451,3011,3029,3011,2925,2870,1708,1652,1538,1500/ cm.

[α] D =+50.6° (MeOH,c=1.01,23° C.).

No.2a-174

CDCl 3 300 MHz 0.96(1H,d,J=10.2 Hz),1.13 and 1.23(each 3H,each s),1.52-2.50(14H,m),4.29(1H,m),5.35-5.51(2H,m),7.02(1H,d,J=8.4 Hz),7.32 and 8.16(each 1H,each d,J=3.9 Hz).

IR(CHCl 3 ):3417,3115,3023,3014,2925,2870,1708,1645,1530/ cm.

[α] D =+48.8° (MeOH,c=1.02,23° C.).

No.2a-175

CDCl 3 300 MHz 0.97(1H,d,J=10.2 Hz),1.14 and 1.23(each 3H,each s),1.50-2.52(14H,m),2.52(3H,s),4.29(1H,m),5.34-5.51(2H,m),7.78(1H,d,J=9.0 Hz),7.24 and 7.52 (each 1H,each d,J=5.4 Hz).

IR(CHCl 3 ):3329,3093,3023,3015,2924,2871,1708,1640,1526/ cm.

[α] D =+45.0° (MeOH,c=1.01,23° C.).

No.2a-176

CDCl 3 300 MHz 0.95(1H,d,J=10.5 Hz),1.09 and 1.23(each 3H,each s),1.52-2.46(14H,m),2.40(3H,d,J=0.9 Hz),4.24(1H,m),5.35-5.51(2H,m),6.05(1H,d,J=8.7 Hz),6.95(1H, m),7.57(1H,d,J=3.3 Hz).

IR(CHCl 3 ):3517,3444,3103,3024,3013,2926,2870,1739,1708,1649,1636,1507/ cm.

[α] D =+54.8° (MeOH,c=1.01,23° C.).

m.p.97.0-99.0° C.

No.2a-177

CDCl 3 300 MHz 0.97(1H,d,J=10.2 Hz);1.11 and 1.23(each 3H,each s),1.52-2.45(14H,m),3.93(3H,s),4.27(1H,m),5.34-5.50(2H,m),6,35(1H,d,J=3.3 Hz), 7.80(1H,d,J=8.7 Hz),8.10(1H,d,J=3.3 Hz).

IR(CHCl 3 ):3395,3121,3031,3019,3012,2925,2871,1739,1709,1640,1557,1533/ cm.

[α] D =+22.8° (MeOH,c=1.01,23° C.).

m.p.109.0-112.0° C.

No.2a-178

CDCl 3 300 MHz 0.96(1H,d,J=10.5 Hz),1.10 and 1.23(each 3H,each s),1.51-2.45(14H,m),4.24(1H,m),5.35-5.50(2H,m),6.09(1H,d,J=8.4 Hz),7.17-7.31(6H,m),7.95(1H,d,J=1.5 Hz).

IR(CHCl 3 ):3510,3451,3062,3031,3022,3011,2925,2870,2662,1708,1651,1582,1535,1497,1477/ cm.

[α] D =+47.9° (MeOH,c=1.01,25° C.).

No.2a-179

CDCl 3 300 MHz 0.96(1H,d,J=10.2 Hz),1.14 and 1.24(each 3H,each s),1.52-2.48(14H,m),4.30(1H,m),5.36-5.52(2H,m),6.73(1H,d,J=9.0 Hz),6.26 and 7.37(each 1H,each d,J=6.0 Hz).

IR(CHCl 3 ):3509,3429,3115,3094,3025,3014,2925,2871,2666,1708,1649,1529,1510/ cm.

[α] D =+51.0° (MeOH,c=1.02,25° C.).

No.2a-180

CDCl 3 300 MHz 0.95(1H,d,J=10.2 Hz),1.14 and 1.24(each 3H,each s),1.52-2.46(14H,m),3.89(3H,s),4.21(1H,m),5.35-5.50(2H,m),6.05(1H,d,J=8.4 Hz),6.46 and 7.04 (each 1H,each d,J=1.8 Hz).

IR(CHCl 3 ):3516,3450,3114,3031,3010,2925,2871,1708,1648,1546,1511,1477/ cm.

[α] D =+49.1° (MeOH,c=1.01,25° C.).

No.2a-181

CDCl 3 300 MHz 0.97(1H,d,J=10.2 Hz),1.14 and 1.23(each 3H,each s),1.52-2.48(14H,m),2.42(3H,s),4.31(1H,m),5.34-5.52(2H,m),8.07(1H,d,J=9.3 Hz),7.27 and 8.17 (each 1H,each d,J=3.3 Hz).

IR(CHCl 3 ):3510,3301,3112,3023,3007,2924,2871,2663,1708,1636,1534/ cm.

[α] D =+41.0° (MeOH,c=0.96,25° C.).

No.2a-182

CDCl 3 300 MHz 0.96(1H,d,J=10.2 Hz),1.11 and 1.23(each 3H,each s),1.53-2.46(14H,m),2.51(3H,s), 4.21 (1H,m),5.35-5.51(2H,m),6.05(1H,d,J= 8.1Hz), 7.26 and 7.78 (each 1H,each d,J=1.8 Hz).

IR(CHCl 3 ):3509,3450,3109,3024,3012,2925,2870,2666,1708,1650,153 ,498,1471/ cm.

[α] D =+52.9° (MeOH,c=0.95,25° C.).

No.2a-183

CDCl 3 300 MHz 0.96(1H,d,J=10.5 Hz),1.12 and 1.22(each 3H,each s),1.52-2.46(14H,m),4.25(1H,m),5.33-5.51(2H,m),6.17(1H,d,J=8.7 Hz),7.01-7.05(3H,m),7.14 and 7.62(each 2H,each d,J=8.7 Hz),7.27-7.34(2H,m).

IR(CHCl 3 ):3428,3026,3015,2925,2870,2666,1739,1708,1643,1613,1594,1526,1499/ cm.

[α] D =+64.8° (MeOH,c=1.02,23° C.).

No.2a-184

CDCl 3 300 MHz 1.01(1H,d,J=10.2 Hz),1.18 and 1.26(each 3H,each s),1.55-2.50(14H,m),4.35(1H,m),5.35-5.55(2H,m),6.42(1H,d,J=8.7 Hz),7.46-7.52(2H,m).7.73(1H,dd,J=1.8 and 8.4 Hz),7.83-7.89(2H,m),8.21(1H,m),8.59(1H,d,J=1.5 Hz).

IR(CHCl 3 ):3451,3031,3014,2925,2870,2660,1739,1708,1650,1604,1513,1463/ cm.

[α] D =+58.3° (MeOH,c=1.00,23° C.).

No.2a.185

CDCl 3 300 MHz 1.00(1H,d,J=10.2 Hz),1.18 and 1.25(each 3H,each s),1.55-2.50(14H,m),4.34(1H,m),5.35-5.54(2H,m),6.36(1H,d,J=8.7 Hz),7.37(1H,t,J=7.4 Hz),7.50(1H,m),7.57-7.59(2H,m),7.79(1H,dd,J=1.8 and 8.1 Hz),7.99(1H,d,J=7.8 Hz),8.39(1H,d,J=1.8 Hz).

IR(CHCl 3 ):3451,3030,3020,2870,2665,1708,1652,1632,1603,1586,1514,1469,1448/ cm.

[α] D =+59.4° (MeOH,c=1.01,24° C.).

No.2a-186

CDCl 3 300 MHz 1.00(1H,d,J=10.5 Hz),1.17 and 1.25(each 3H,each s),1.54-2.50(14H,m),4.33(1H,m),5.36-5.54(2H,m),6.37(1H,d,J=8.7 Hz),7.37(1H,t,J=7.4 Hz),7.51(1H,t, J=7.8 Hz),7.56(1H,m),7.70(1H,dd,J=1.2 and 8.4 Hz),7.97(3H,m).

IR(CHCl 3 ):3451,3030,3014,2924,2870,2671,1739,1708,1652,1577,1517,1488,1471/ cm.

[α] D =+72.2° (MeOH,c=1.00,24° C.).

No.2a-187

CDCl 3 300 MHz 1.00(1H,d,J=9.8 Hz),1.18 and 1.25(each 3H,each s),1.54-2.53(14H,m),4.07(3H,s),4.37(1H,m),5.30-5.54(2H,m),7.34(1H,m),7.47(1H,s),7.47-7.60(2H,m),7.93(1H,d,J=7.8 Hz),8.43(1H,s),8.49(1H,d,J=9.0 Hz).

IR(CHCl 3 ):3397,3074,3027,3020,3009,2924,1738,1708,1647,1633,1534,1465, 1453/cm.

[α] D =+43.7° (MeOH,c=1.01,25° C.).

No.2a-188

CDCl 3 300 MHz 0.97(1H,d,J=10.2 Hz),1.11 and 1.23(each 3H,each s),1.53-2.50(14H,m),4.23(1H,m),5.37-5.50(2H,m),6.10(1H,d,J=9.0 Hz),6.20(1H,m),6.51(1H,m),6.971H,m),10.81(1H,brs).

IR(CHCl 3 ):3450,3236,3112,3029,3015,2925,2871,2645,1701,1616,1558,15161cm.

[α] D =+50.6° (MeOH,c=1.01,24° C.).

No.2a-189

CDCl 3 300 MHz 0.94(1H,d,J=9.9 Hz),1.11 and 1.23(each 3H,each s),1.50-2.46(14H,m),3.93(3H,s),4.18(1H,m),5.35-5.52(2H,m),6.03(1H,d,J=9.3 Hz),6.09(1H,m),6.48(1H, m),6.73(1H,m).

IR(CHCl 3 ):3452,3102,3028,3007,2925,2871,2666,1739,1708,1650,1536,1499,1471/cm.

[α] D =+49.8° (MeOH,c=1.01,23° C.).

m.p.101.5-103.5° C.

No.2a-190

CDCl 3 300 MHz 0.94(1H,d,J=10.2 Hz),1.11 and 1.21(each 3H,each s),1.54-2.47(14H,m),4.23(1H,m),5.33-5.52(2H,m),6.06(1H,d,J=9.0 Hz),6.34(1H,m),6.75(1H,m),6.36(1H,m),9.71(1H,brs).

IR(CHCl 3 ):3470,3215,3030,3020,3010,2925,2871,2664,1709,1613,1564,1510/cm.

[α] D =+43.3° (MeOH,c=1.01,24° C.).

No.2a-191

CDCl 3 300 MHz 0.96(1H,d,J=10.2 Hz),1.11 and 1.22(each 3H,each s),1.55-2.44(14H,m),3.66(3H,s),4.20(1H,m),5.35-5.51(2H,m),5.93(1H,d,J=8.4 Hz),6.27(1H,dd,J=1.8 and 2.7 Hz),6.56(1H,t,J=2.7 Hz),7.19(1H,t,J=1.8 Hz).

IR(CHCl 3 ):3452,3031,3018,3006,2925,2871,2662,1736,1710,1634,1609,1556,1498/cm.

[α] D =+43.1° (MeOH,c=1.01,23° C.).

No.2a-192

CDCl 3 300 MHz 0.96(1H,d,J=10.5 Hz),1.11 and 1.21(each 3H,each s),1.43(3H,t,J=7.5 Hz),1.54-2.44(14H,m),3.93(2H,q,J=7.5 Hz),4.21(1H,m),5.33-5.51(2H,m),5.94(1H,d, J=8.4 Hz),6.27(1H,dd,J=1.8 and 2.7 Hz),6.62(1H,t,J=2.7 Hz),7.26(1H,t,J=1.8 Hz).

IR(CHCl 3 ):3630,3452,3032,3018,3006,2925,2871,2661,1735,1710,1633,1610,1555,1497/cm.

[α] D =+40.1° (MeOH,c=1.00,23° C.).

No.2a-193

CDCl 3 300 MHz 0.95(1H,d,J=10.2 Hz),1.10 and 1.22(each 3H,each s),1.53-2.49(14H,m),2.58(3H,s), 4.21 (1H,m),5.35-5.54(2H,m),6.15(1H,d,J=8.1 Hz),6.52(1H,dd,J=1.8 and 3.6 Hz),7.29(1H,t,J=3.6 Hz),7.94(1H,t,J=1.8 Hz).

IR(CHCl 3 ):3516,3450,3410,3152,3027,3015,2925,2871,2670,1732,1648,1574,1509/cm.

[α] D =+45.0° (MeOH,c=1.01,25° C.).

No.2a-194

CDCl 3 300 MHz 0.99(1H,d,J=10.2 Hz),1.11 and 1.24(each 3H,each s),1.52-2.53(14H,m),4.34(1H,m),5.33-5.57(2H,m),6.21(1H,d,J=8.6 Hz),7.35-7.50(2H,m),7.83(1H,s),7.86(1H,m), .8.31 (1H,m).

IR(CHCl 3 ):3443,3067,3013,2925,2870,2665,1708,1651,1515,1493/cm.

[α] D =+55.7° (MeOH,c=1.01,238° C.).

No.2a-195

CDCl 3 300 MHz 1.01(1H,d,J=10.0 Hz),1.06 and 1.26(each 3H,each s),1.50-2.64(14H,m),2.68(3H,s),4.40(1H,m),5.36-5.61(2H,m),6.02(1H,d,J=9.4 Hz),7.30-7.42(2H,m),7.73-7.86(2H,m).

IR(CHCl 3 ):3510,3434,3062,3029,3014,2924,2871,2669,1708,1650,1563,1539,1500/cm.

[α] D =+72.4° (MeOH,c=1.00,23° C.).

m.p.111.0-112.0° C.

No.2a-196

CDCl 3 300 MHz 0.42 and 1.04(each 3H,each s),0.80(1H,d,J=10.0 Hz),1.11-2.48(14H,m),2.24(3H,s),4.02(1H,m);5.23-5.44(2H,m),5.53(1H,d,J=8.8 Hz), 7.27-7.31(2H,m)7.42-7.48(3H,m),7.93(1H,s).

IR(CHCl 3 ):3419,3114,3025,3006,2924,2871,2662,1737,1709,1636,1540,1519/cm.

[α] D =+43.7° (MeOH,c=1.01,23° C.).

No.2a-197

CDCl 3 300 MHz 0.95(1H,d,J=10.0 Hz),1.09 and 1.23(each 3H,each s),1.54-2.46(18H,m),2.77(4H,brs),4.21(1H,m),5.32-5.54(2H,m),6.02(1H,d,J=8.6 Hz),7.43(1H,s).

IR(CHCl 3 ):3445,3101,3024,3014,2928,2865,2661, 1 739,1708 1646,1550,1507/cm.

[α] D =+51.9° (MeOH,c=1.01,23° C.).

No.2a-198

CDCl 3 300 MHz 0.96(1H,d,J=10.2 Hz),1.11 and 1.22(each 3H,each s),1.50-2.44(14H,m),4.24(1H,m),4.42(2H,s),5.35-5.49(2H,m),6.25(1H,d,J=8.1 Hz),7.33(1H,m),7.43(1H,dd,J=1.5and 7.5 Hz),7.49(1H,d,J=8.1 Hz),7.60-7.63(1H,m),7.68(1H,dd,J=1.8 and 7.8 Hz),8.02(1H,d,J=1.8 Hz),8.19(1H,dd,J=1.5 and 8.1 Hz).

IR(CHCl 3 ):3448,3030,3012,2925,2870,1739,1708,1671,1588,1559,1514,1472/cm.

[α] D =+56.9° (MeOH,c=1.01,24° C.).

No.2a-199

CDCl 3 300 MHz 0.96(1H,d,J=10.2 Hz),1.11 and 1.22(each 3H,each s),1.51-2.46(14H,m),3.40(1H,m),3.76(1H,m),4.24(1H,m),5.33-5.51(3H,m),6.25(1H,m),7.16(1H,m),7.24-7.33(2H,m),7.46(1H,d,J=7.5 Hz),7.52-7.60(2H,m),7.85(1H,dd,J=1.8 and 4.5 Hz).

IR(CHCl 3 ):3583,3447,3062,3028,3013,2924,2871,2663,1708,1651,1600,1557,1514,1471/cm.

[α] D =+54.8° (MeOH,c=1.00,23° C.).

No.2a−200

CDCl 3 300 MHz 0.96(1H,d,J=10.2 Hz),1.12 and 1.23(each 3H,each s),1.51-2.46(14H,m),4.25(1H,m),5.34-5.51(2H,m),6.25(1H,d,J=8.4 Hz),7.02 and 7.10(each,1H,each d,J=12.3 Hz),7.23-7.33(4H,m),7.50(1H,m),7.64(1H,dd,J=1.8 and 7.8 Hz),7.82(1H,d,J=1.8 Hz).

IR(CHCl

1453):3450,3060,3025,3014,2925,2871,2662,1708,1653,1596,1542,1513,1473/cm.

[α] D =+62.5° (MeOH,c=1.00,24° C.).

No.2a−201

CDCl 3 300 MHz 0.95(1H,d,J=9.9 Hz),1.15 and 1.22(each 3H,each s),1.55-2.60(14H,m),4.26(1H,m),5.35-5.63(2H,m),7.14(1H,d,J=9.9 Hz),7.34 and 7.40(each,1H,each d, J=12.9 Hz),7.62-7.73(4H,m),8.25-8.30(2H,m),8.72(1H,d,J=1.5 Hz).

IR(CHCl 3 ):3443,3389,3297,3061,3030,3016,2925,2870,1726,1708 1652,1603,1521,1483,1472,1309/cm.

[α] D =+61.1° (MeOH,c=1.01,23° C.).

No.2a−202

CDCl 3 300 MHz 0.96(1H,d,J=10.2 Hz),1.09 and 1.22(each 3H,each s, 1.52-2.43(14H,m),2.63(3H,s),4.25(1H,m),5.33-5.49(2H,m),6.19(1H,d,J=8.4 Hz),7.10 and 7.58 (each,2H,each d,J=9.0 Hz),7.21(1H,m),7.30-7.32(2H,m),7.46(1H,d,J=7.5 Hz)

IR(CHCl 3 ):3511,3453,3062,3032,3014,2925 2870,1739,1708,1650,1595,1556,1516,1482,1471/cm.

[α] D =+60.2° (MeOH,c=1.01,25° C.).

No.2a−203

CDCl 3 300 MHz 0.96(1H,d,J=10.5 Hz),1.09 and 1.23(each 3H,each s),1.52-2.43(14H,m),4.23(1H,m),5.35-5.51(2H,m),5.93(1H,d,J=8.7 Hz),6.56(1H,dd,J=0.9 and 1.8 Hz), 7.43(1H,t,J=1.8 Hz),7.92(1H,dd,J=0.9 and 1.8 Hz).

IR(CHCl 3 ):3517,3450,3134,3031,3008,2925,2870,2667,1708,1656,1588,1570,1514/cm.

[α] D =+46.7° (MeOH,c=0.92,25° C.).

No.2b-1

[α] D =+25.6° (MeOH,c=1.01,23° C.).

No.2b-2

[α] D =+38.9° (MeOH,c=1.01,24° C.).

No.2c-1

[α] D =+60.5° (MeOH,c=1.01,22° C.).

No.2c-2

[α] D =+55.8° (MeOH,c=0.92,22° C.).

No.2c-3

[α] D =+54.7° (MeOH,c=1.01,22° C.).

No.2d-1

[α] D =−6.2° (MeOH,c=1.00,21° C.).

No.2d-2

[α] D =+15.8° (MeOH,c=0.34,22° C.).

No.2d-3

[α] D =+31.6° (MeOH,c=1.01,22° C.).

No.2e-1

[α] D =−9.4° (MeOH,c=1.00,22° C.).

No.2e-2

[α] D =−1.8° (MeOH,c=1.02,23° C.).

No.2e-3

[α] D =−6.7° (MeOH,c=1.01,23° C.).

No.2f-1

[α] D =+6.8° (MeOH,c=1.01,23° C.).

No.2f-2

[α] D =−2.6° (MeOH,c=1.00,22° C.).

No.2f-3

[α] D =−3.6° (MeOH,c=1.01,22° C.).

No.2g-1

[α] D =+54.6° (MeOH,c=1.01,24° C.).

No.3a-2

CDCl 3 300 MHz 0.98-2.15(14H,m),2.31(2H,t,J=7.2 Hz),2.35-2.40(1H,m),3.10-3.20(1H,m), 5.00(1H,d,J=6.9 Hz),5.30-5.48(2H,m),6.75(1H,d,J=10.2H,z),7.38-7.52(6H,m).

IR(CDCl 3 ):3266,3028,2954,2874,1709,1620,1448,1412,1318,1141,970,892/cm.

[α] D =+20.3±0.6° (CHCl 3 ,c=1.05,24° C.).

No.3a-3

CDCl 3 300 MHz 0.95-2.00(14H,m),2.20-2.29(3H,m),3.00-3.08(1H,m),3.66(3H,s),5.00(1H,d, J=6.6 Hz),5.13-5.29(2H,m),7.38-7.52(8H,m),7.59-7.65(2H,m),7.69-7.75(2H,m),7.92-7.98(2H,m).

IR(CHCl 3 ):3376,3018,2946,2868,1727,1594,1436,1395,1322,1157,1095,890/cm.

[α] D =+2.3±0.4° (CHCl 3 ,c=1.03,22° C.).

mp.65-66.5° C.

No.3a-4

CDCl 3 300 MHz 0.93-2.05(14H,m),2.15-2.22(1H,m),2.31(2H,t,J=7.2 Hz),3.01-3.10(1H,m), 5.18-5.31(3H,m),7.38-7.52(3H,m),7.58-7.66(2H,m),7.69-7.76(2H,m),7.92-7.98(2H,m)

IR(CHCl 3 ):3374,3260,3020,2948,2868,1708,1594,1479,1396,1319,1156,1095,211052,891/cm.

[α] D =+13.1±0.5° (CHCl 3 ,c=1.16,24° C.).

No.3a-6

CD 3 OD 300 MHz 1.04-1.95(14H,m),2.07(2H,t,J=7.8 Hz),2.14-2.22(1H,m),2.94-3.00(1H,m 5.04-5.25(2H,m),7.36-7.52(3H,m),7.66-7.71(2H,m),7.78-7.85(2H,m),7.91-7.97(2H,m).

IR(KBr):3421,3278,2951,2872,1562,1481,1409,1317,1156,1097,1057,895/cm

[α] D =−15.3±0.5° (CHCl 3 ,c=1.06,23° C.).

mp.105-112° C.

No.3a-11

CDCl 3 300 MHz 0.90-2.04(14H,m),2.08-2.19(1H,m),2.35(2H,t,J=7.2 Hz),2.95-3.04(1H,m), 5.17-5.32(3H,m),7.56-7.63(2H,m),7.83-7.95(2H,m).

IR(CHCl 3 ):3260,3020,2948,2868,1707,1569,1456,1383,1325,1268,1160,1088,1053,1006,892/cm.

[α] D =+8.3±0.5 °(CHCl 3 ,c=1.00,22° C.).

No.3a-16

CDCl 3 300 MHz 0.80-1.90(14H,m),1.98-2.04(1H,m),2.27(2H,t,J=7.2 Hz),2.88(6H,s),2.90-2.98(1H,m),4.88-5.00(2H,m),5.13(1H,d,J=7.2 Hz),7.18(1H,d,J=7.5 Hz),7.48-7.60(2H,m),8.25-8.33(2H,m),8.53(1H,d,J=8.7 Hz).

IR(CHCl 3 ):3272,3020,2946,2866,2782,1708,1573,1455,1407,1311,1229,1160,1142,1070,942,891/cm.

[α] D =−19.7±0.6° (CHCl 3 ,c=1.08,23.5° C.).

No.3a-31

CDCl 3 300 MHz 0.80-1.85(14H,m),2.02-2.08(1H,m),2.20(2H,t,J=7.2 Hz),2.85-2.95(1H,m), 3.68(3H,s),4.80-4.92(2H,m),4.96(1H,d,J=6.9 Hz),7.50-7.70(3H,m),7.92-7.98(1H,m),8.07(1H,d,J=8.4 Hz),8.29(1H,dd,J=1.5&c=7.5 Hz),8.65(1H,d,J=8.7 Hz).

IR(CHCl 3 ):3374,3016,2946,2868,1727,1506,1435,1318,1160,1133,1105,1051,984,890/cm.

[α] D =−39.3±0.8° (CHCl 3 ,c=1.07,22° C.).

No.3a-32

CDCl 3 300 MHz 0.80-1.90(14H,m), 1.95-2.05(1H,m),2.27(2H,t,J=7.2 Hz),2.90-2.96(1H,m), 4.85-5.00(2H,m),5.23(1H,d,J=6.6 Hz),7.50-7.72(3H,m),7.95(1H,d,J=8.1 Hz), 8.07(1H,d,J=8.4 Hz),8.29(1H,dd,J=1.2&7.5 Hz),8.66(1H,d,J=9.0 Hz).

IR(CHCl 3 ):3270,3020,2948,2868,1708,1455,1412,1317,1159,1132,1104,1079,1051,983,891/cm.

[α] D =−29.2±0.6° (CHCl 3 ,c=1.08,22° C.).

No.3a-33

CD 3 OD 300 MHz 0.94-1.84(14H,m),1.96-2.08(3H,m),2.77-2.84(1H,m),4.67-4.84(2H,m),7.55-7.75(3H,m),8.02(1H,d,J=7.8 Hz),8.12-8.26(2H,m),8.74(1H,d,J=8.7 Hz).

IR(KBr):3432,3298,2951,2872,1564,1412,1315,1159,1134,1107,1082,1058,986/cm.

[α] D =−79.9±1.2° (CH 3 OH,c=1.00,23° C.).

No.3a-34

CDCl 3 300 MHz 0.97-1.91(14H,m),2.13-2.20(1H,m),2.42(2H,t,J=7.2 Hz),3.00-3.07(1H,m), 5.06-5.24(2H,m),5.33(1H,d,J=6.9 Hz),7.57-7.68(2H,m), 7.82-8.00(4H,m), 8.45(1H,d,J=1.2 Hz)

IR(CHCl 3 ):3260,3020,2948,1708,1408,1319,1154,1129,1073,953,893/cm.

[α] D =+20.7±0.6 °(CHCl 3 ,c=1.07,22° C.).

No.3a-35

CD 3 OD 300 MHz 1.03-2.20(m,17H),2.97(m,1H),5.02(m,2H),7.64(m,2H),8.00(m,4H),8.43 (S,1H).

IR(KBr):3360,3285,1562,1407,1316,1153,1130,1075/cm.

[α] D ≈0

[α] 365 =+20.9±0.6° (CH 3 OH,c=1.04,23° C.).

No.3d-1

CDCl 3 300 MHz 0.93-2.55(m,17H),3.02(m,1H),5.24(m,2H),6.48(m, 1H),7.35-7.60(m,3H),7.85-8.00(m,2H)

IR(Nujol): 3275,1548,1160,1094,758,719,689,591,557/cm.

[α] D =+19.0±0.6° (CH 3 OH,c=1.010,26.5° C.).

Elemental analysis (C 20 H 26 NO 4 S 1/2Ca 1.0 H 2 O) Calcd.: C, 57.94; H, 6.82; N, 3.38; ° Ca, 4.83; H 2 0, 4.35 Found: C, 57.80; H. 6.68; N, 3.68; ° Ca, 5.06; H20, 4.50

No.3d-6

[α] D =−2.7±0.6° (CHCl 3 ,c=1.00,24° C.).

No.3d-7

[α] D =−3.2±0.4° (CHCl 3 :c=1.03,22° C.).

mp.65-67° C.

No.3d-8

[α] D =−14.5±0.5° (CHCl 3 ,c=1.07,24° C.).

No.3d-9

[α] D =+12.2±0.5° (CH 3 OH,c=1.00,23° C.).

mp.119-125° C.

No.3d-10

[α] D =+39.7±0.8° (CHCl 3 ,c=1.07,22° C.).

No.3d-11

[α] D =+29.2±0.7° (CHCl 3 ,c=1.06,22° C.).

No.3d-12

[α] D =+76.4±1.1° (CH 3 OH,c=1.03,24° C.).

No.3d-14

[α] D =−20.6±0.6° (CHCl 3 ,c=1.07,22° C.).

No.3d-15

[α] 365 =−28.0±0.7° (CH 3 OH,c=1.03,24.5° C.).

No.3d-16

[α] D =−8.7±0.5° (CHCl 3 ,c=1.06,22° C.).

No.3d-17

CDCl 3 300 MHz 080-2.15(m,24H),2.32(t,J=7 Hz,2H),2.68(t,J=7 Hz,2H),3.02(m, 1H),2.15 (m,24H),2.32(t,J=7 Hz,2H),2.68(t,J=7 Hz,2H),3.02(m, 1H),5.22(m,2H),5.38(d,J=7 Hz, 1H),7.30(A2B2q-Apart,J=8 Hz,2H), 7.81 (A2B2qBpart,J=8 Hz,2H), 9.86 (brs,1H).

[α] D ≈0

[α] 365 =<9.7±0.5° (CHCl 3 ,c=1.03,22° C.).

No.3 d-24

[α] D =+19.2±0.6° (CHCl 3 ,c=1.05,23° C.).

No.3d-26

CD 3 OD 300 MHz 0.90-2.20(20H,m),2.88(1H,m),3.07(2H,q,J=7.0 Hz),5.00-5.40(2H,m),7.20-7.60(4H,m),7.95(1H,m).

IR(KBr):3415,3254,1698,1564,1314,1154/cm.

No.3 d-28

CD 3 OD 300 MHz 0.90-2.20(20H,m),2.73(2H,q,J=7.0 Hz),2.93(1H,m),5.00-5.30(2H,m),7.40-7.50(2H,m),7.60-7.77(2H,m).

IR(KBr):3435,3280,1562,1323,1304,1151/cm.

No.3d-30

Elemental analysis (C 20 H 25 BrNO 4 SNa) Calcd.: C, 50.21; H, 5.27; Brl, 6.70; N, 2.93; S, 6.70; Na, 4.81Found: C, 50.22; H, 5.40; Brl, 5.57; N, 2.88; S, 6.41; Na, 5.10

IR(KBr):3425,3280,3085,1697,1570,1410,1321,1165,1155/cm.

No.3e-1

CD3OD 300 MHz 0.71(1H,d,J=10.2 Hz),1.04(3H,s), 1.12(3H,s), 1.35-2.28(14H,m), 2.42(3H,s),3.17-3.25(1H,m),5.18-5.39(2H,m),7.37(2H,d,J=8.4 Hz),7.75(2H,d,J=8.4 Hz).

IR(CHCl 3 ):3400,3289,2986,2924,2870, 1559,1424,1322,1305,1160,1095,1075, 1030/cm.

[α] D =+25.9±0.7° (CH 3 OH,c=1.00,23° C.).

Compounds prepared in Examples above were tested for the in vivo and in vitro activity according to the method shown in Experimental examples below.

Experiment 1

Binding to PGD 2 Receptor

Material and Method

(1) Preparation of Human Platelet Membrane Fraction

Blood sample was obtained using a plastic syringe containing 3.8% sodium citrate from a venous of healthy volunteers (adult male and female), put into a plastic test tube and mixed gently by inversion. The sample was then centrifuged at 1800 rpm, 10 min at room temperature, and supernatant containing PRP (platelet rich plasma) was collected. The PRP was re-centrifuged at 2300 rpm, 22 min at room temperature to obtain platelets. The platelets were homogenized using a homogenizer (Ultra-Turrax) followed by centrifugation 3 times at 20,000 rpm, 10 min at 4° C. to obtain platelet membrane fraction. After protein determination, the membrane fraction was adjusted to 2 mg/ml and preserved in a refrigerator at −8° C. until use.

(2) Binding to PGD 2 Receptor

To a binding-reaction solution (50 mM Tris/HCl, pH 7.4, 5 mM MgCl 2 ) (0.2 ml) were added human platelet membrane fraction (0.1 mg) and 5 nM [3H]PGD 2 (115 Ci/mmol), and reacted at 4° C. for 90 min. After the reaction completed, the reaction mixture was filtered through the glass fiber filter paper, washed several times with cooled saline, and measured radioactivity retained on the filter paper. The specific binding was calculated by subtracting the non-specific binding (the binding in the presence of 10 μM PGD 2 ) from the total binding. The binding-inhibitory activity of each compound was expressed as concentration required for 50% inhibition (IC 50 ), which was determined by depicting a substitution curve by plotting the binding ratio (%) in the presence of each compound, where the binding ratio in the absence of a test compound is 100%. The results are shown in Table below.

Compound Activity
number   (μM)
3a-4     0.6
1a-115   8.6
1a-28    0.045
1a-47    0.0086
1a-100   0.56
1a-176   0.047
1a-2     0.13
2a-4     0.54
2a-17    0.12
2a-21    5.2
2a-28    0.046
2a-95    1.6
2a-109   0.003
1a-162   0.027

Experiment 2

Evaluation of Antagonistic Activity Against PGD 2 Receptor Using Human Platelet

Peripheral blood was obtained from a healthy volunteer using a syringe in which {fraction (1/9)} volume of citric acid/dextrose solution has been previously added. The syringe was subjected to centrifugation at 180 g for 10 min to obtain the supernatant (PRP: platelet rich plasma). The resultant RRP was washed 3 times with a washing buffer and the number of platelet was counted with a micro cell counter. A suspension adjusted to contain platelet at a final concentration of 5×10 8 /ml was warmed at 37° C., and then subjected to the pre-treatment with 3-isobutyl-1-methylxanthine (0.5 mM) for 5 min. To the suspension was added a test compound diluted at various concentration. Ten-minute later, the reaction was induced by the addition of 0.1-2.0 μM PGD 2 and, 15-minute later, stopped by the addition of HCl. The platelet was destroyed with an ultrasonic homogenizer. After centrifugation, the cAMP in the supernatant was determined by radioassay. PGD 2 receptor antagonism of a drug was evaluated as follows. The inhibition rate regarding cAMP increased by the addition of PGD 2 was determined at individual concentration, and then the concentration of the drug required for 50% inhibition (IC 50 ) was calculated. The results are shown in Table below.

         Inhibition of Increase of
Compound Human Platelet cAMP
number   (IC                                                                        50                                                                    ) (μM)
3a-16    0.37
1a-12    12.11
1a-28    0.30
1a-47    2.09
2a-2     0.77
2a-4     0.94
2a-35    1.52
2a-75    0.71

Experiment 3

Experiment Using Nasal Occlusion Model

The method used for measuring the nasal cavity resistance and evaluating the anti-nasal occlusion using a guinea pig are described below.

A 1% ovalbumin (OVA) solution was treated with ultrasonic nebulizer to obtain an aerosol. Hartley male guinea pig was sensitized by inhaling twice the aerosol for 10 min at one-week interval. Seven-day after the sensitization, the guinea pig was exposed to an antigen to initiate the reaction. Then the trachea was incised under the anesthesia with pentobarbital (30 mg/kg, i.p.) and cannulas were inserted into the trachea at the pulmonary and nasal cavity sides. The canal inserted at the pulmonary side was connected with an artificial respirator that provides 4 ml air 60 times/min. After arresting the spontaneous respiration of a guinea pig with Garamin (2 mg/kg, i.v.), air was supplied to the snout side with an artificial respirator at the frequency of 70 times/min, and the flow rate of 4 ml air/time, and the atmospheric pressure required for the aeration was measured by the use of a transducer fitted at the branch. The measurement was used as a parameter of the nasal cavity resistance. The exposure of an antigen was carried out by generating aerosol of 3% OVA solution for 3 min between the respirator and nasal cavity cannula. The test drug was injected intravenously 10 min before the antigen exposure. The nasal resistance between 0 to 30 min was measured continuously and the effect was expressed as inhibition rate to that obtained for vehicle using the AUC for 30 min (on the vertical axis, nasal cavity resistance (cm H 2 O), and on the horizontal axis, time (0-30 min)) as an indication. The result is shown below.

	Compound	Inhibition Rate (%)
	number	1 mg/kg (i.v.)	Remarks
	1a-28	44
	1a-98	69
	1a-100	50
	1a-115	66
	1a-116	48
	1a-120	58	3 mg/kg (i.v.)
	1a-2	82
	1a-162	80
	1a-176	60
	1a-267	62
	2a-4	60
	2a-21	52
	2a-28	54
	2a-95	77
	2a-96	77	10 mg/kg (p.o.)
	2a-109	73
	2a-110	66	10 mg/kg (p.o.)
	22a-194	79

Formulation 1

Preparation of Tablets

Tablets each containing 40 mg of active ingredient were prepared in a conventional manner. The ingredients for 40 mg tablet are as follows:

Calcium (+)-(z)-7-[(1R,2S,3S,4S)- 40.0 mg
3-benzenesulfonamidobicyclo[2.2.1]hept-
2-yl-]-5-heptenoate dihydrate
Hydroxypropyl cellulose          3.6 mg
Magnesium stearate               0.4 mg
Cornstarch                       18.0 mg
Lactose                          58.0 mg
Total                            120.0 mg

Formulation 2

Preparation of Granules

Ingredients:

Calcium (+)-(z)-7-[(1R,2S,3S,4S)- 100.0 mg
3-benzenesulfonamidobicyclo[2.2.1]hept-
2-yl-]-5-heptenoate dihydrate
Hydroxypropyl cellulose          30.0 mg
Carmellose Calcium               30.0 mg
Talc                             10.0 mg
Poloxamer 188                    20.0 mg
Crystalline cellulose            70.0 mg
Cornstarch                       300.0 mg
Lactose                          440.0 mg
Total                            1000.0 mg

Claims

1. A compound of the formula (Ib): wherein A is alkylene which optionally is intercalated by a hetero atom or phenylene, contains an oxo group, and/or has an unsaturated bond; B is hydrogen, alkyl, aralkyl or acyl; R is COOR1, CH2OR2 or CON(R3)R4; R1 is hydrogen or alkyl; R2 is hydrogen or alkyl; R3 and R4 each are independently hydrogen, alkyl, hydroxy or alkylsulfonyl X1 is a single bond, phenylene, naphthylene, thiophenediyl, indolediyl, or oxazolediyl; X2 is a single bond, —N═N—, —N═CH—, —CH═N—, —CH═N—N—, —CH═N—O—, —C═NNHCSNH—, —C═NNHCONH—, —CH═CH—, —CH(OH)—, —C(Cl)═C(Cl)—, —(CH2)n—, ethynylene, —N(R5)—, —N(R51)CO—, —N(R52)SO2—, —N(R53)CON(R54)—, —CON (R55)——SO2N(R56)—, —O—, —S—, —SO—, —SO2—, —CO—, oxadiazolediyl, thiadiazolediyl or tetrazolediyl; X3 is alkyl, alkenyl, alkynyl, aryl, aralkyl, heterocyclic group, cycloalkyl, cycloalkenyl, thiazolinylidenemethyl, thiazolidinylidenemethyl, —CH═NR6 or —N═C(R7)R8, R5, R51, R52, R53, R54, R55 and R56 each are hydrogen or alkyl; R6 is hydrogen, alkyl, hydroxy, alkyoxy, carbamoyloxy, thiocarbamoyloxy, ureido or thioureido; R7 and R8 each are independently alkyl, alkoxy or aryl; and n is 1 or 2; wherein a cyclic substituent may have one to three substituents selected from the group consisting of nitro, alkoxy, sulfamoyl, substituted- or unsubstituted-amino, acyl, acyloxy, hydroxy, halogen, alkyl, alkynyl, carboxy, alkoxycarbonyl, aralkoxycarbonyl, aryloxycarbonyl, mesyloxy, cyano, alkenyloxy, hydroxyalkyl, trifluoromethyl, alkylthio, —N═PPh3, oxo, thioxo, hydroxyimino, alkoxyimino, phenyl and alkylenedioxy, or its salt or hydrate thereof, provided that those wherein X, and X2 are a single bond, and X3 is unsubstituted phenyl, and wherein X1 is a single bond, X2 is —O—, and X3 is benzyl or tert-butyl are excluded.

2. The compound of claim 1, its salt or hydrate thereof, wherein:

3. The compound of claim 2, its salt or hydrate thereof, wherein R is COOR1.

4. The compound of claim 2, its salt or hydrate thereof, wherein X1 is phenylene or thiophenediyl, X2 is a single bond, —N═N—, —CH═CH—, ethynylene, —O—, —S—, —CO—, —CON(R55)—, —N(R51)CO— and X3 is phenyl or thienyl.

5. The compound of claim 1, its salt or hydrate thereof, wherein:

6. The compound of claim 5, its salt or hydrate thereof, wherein B is hydrogen, both X1 and X2 are a single bond, X3 is thienyl, thiazolyl, thiadiazolyl, isothiazolyl, pyrrolyl, pyridyl, benzofuryl, benzimidazolyl, benzothienyl, dibenzofuryl, dibenzothienyl, quinolyl or indolyl.

7. The compound of claim 5, its salt or hydrate thereof, wherein X1 is phenylene, thiophenediyl, indolediyl or oxazolediyl, X2 is a single bond, —N═N—, —CH═CH—, ethynylene, —S—or —O—, and X3 is aryl or a heterocyclic group.

8. A composition comprising a compound according to claim 1 and a pharmaceutically acceptable carrier thereof.

9. A method for treating a PGD2-mediated disease comprising administering to a subject in need thereof, a PGD2 antagonist according to claim 1.

10. A compound A method according to claim 9 wherein said PGD2-mediated disease is selected from the group consisting of systemic mastocytosis, disorder of systemic mast cell activation, tracheal contraction, asthma, allergic rhinitis, allergic conjunctivitis, urticaria, injury due to ischemic reperfusion and inflammation.

11. A method according to claim 18 wherein said PGD2-mediated disease is nasal occlusion.

12. The compound of claim 1, its salt or hydrate thereof, wherein: A is alkylene which optionally contains oxo group and/or has an unsaturated bond; B is hydrogen, R is COOH or CH2OH; X1 is a single bond; X2 is a single bond; X3 is substituted- or unsubstituted-benzothienyl.