Pyrazole oxime derivatives and compositions

The present invention relates to a pyrazole oxime derivative, its production and an insecticidal and acaricidal composition containing it as an active ingredient for use in agriculture and horticulture, said pyrazole oxime derivative being represented by the general formula (I), ##STR2## wherein R.sup.1 represents C.sub.1 -C.sub.4 alkyl or phenyl; R.sup.2 represents hydrogen, C.sub.1 -C.sub.5 alkyl, C.sub.1 -C.sub.3 haloalkyl or phenyl; R.sup.3 represents hydrogen, C.sub.1 -C.sub.4 alkyl or phenyl; R.sup.4 represents hydrogen, C.sub.2 -C.sub.4 alkylcarbonyl, benzoyl, naphthyl or a substituent of the formula ##STR3## [in which X represents hydrogen; halogen; C.sub.1 -C.sub.12 alkyl; C.sub.1 -C.sub.6 alkyl substituted with halogen, cyano, hydroxy, C.sub.1 -C.sub.5 alkoxy or C.sub.2 -C.sub.6 alkoxycarbonyl; C.sub.3 -C.sub.8 cycloalkyl; cycloalkyl substituted with from one to three members selected from the group consisting of C.sub.1 -C.sub.4 alkyl, halogen and cyano; C.sub.2 -C.sub.4 alkenyl substituted with halogen, hydroxy, C.sub.2 -C.sub.4 alkoxycarbonyl or C.sub.2 -C.sub.6 alkylcarbonyl; phenyl; hydroxy; C.sub.1 -C.sub.6 alkoxy; C.sub.1 -C.sub.4 alkoxy substituted with halogen or C.sub.2 -C.sub.6 alkoxycarbonyl; phenoxy which may or may not be substituted with C.sub.1 -C.sub.3 haloalkyl; benzyloxy; C.sub.1 -C.sub.3 alkylenedioxy formed by two adjacent Xs; pyridyloxy which may or may not be substituted with halogen or C.sub.1 -C.sub.3 haloalkyl; a substituent of the formula, --S(O).sub.p R.sup.5 (in which R.sup.5 represents C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.5 haloalkyl or phenyl, and p represents an integer of 0, 1 or 2; cyano; formyl; nitro; a substituent of the formula --COOR.sup.6 {in which R.sup.6 represents hydrogen; alkali metal; C.sub.1 -C.sub.10 alkyl; C.sub.1 -C.sub.5 alkyl substituted with halogen, C.sub.1 -C.sub.4 alkoxy, phenoxy, C.sub.2 -C.sub.4 alkoxycarbonyl or phenoxyphenyl; C.sub.2 -C.sub.7 alkenyl; C.sub.3 -C.sub.7 alkynyl; C.sub.3 -C.sub.8 cycloalkyl; C.sub.3 -C.sub.8 cycloalkyl substituted with C.sub.1 -C.sub.3 alkyl; phenyl; or a substituent of the formula, ##STR4## (in which R.sup.7, R.sup.8 and R.sup.9, which may be the same or different, represent C.sub.1 -C.sub.4 alkyl or C.sub.3 -C.sub.8 cycloalkyl)}; C.sub.2 -C.sub.6 alkylcarbonyl; C.sub.2 -C.sub.6 alkylcarbonyl substituted with cyano or C.sub.2 -C.sub.6 alkylcarbonyl; benzoyl which may or may not be substituted with halogen or C.sub.1 -C.sub.6 alkyl; C.sub.2 -C.sub.6 alkylthiocarbonyl; C.sub.3 -C.sub.7 alkoxycarbonylcarbonyl; a substituent of the formula, ##STR5## (in which R.sup.10 and R.sup.11, which may be the same or different, represent hydrogen, C.sub.1 -C.sub.6 alkyl or phenyl); piperidinocarbonyl; morpholinocarbonyl which may or may not be substituted with one or two C.sub.1 -C.sub.4 alkyls; a substituent of the formula, ##STR6## (in which R.sup.12 represents hydrogen or C.sub.1 -C.sub.5 alkyl, and R.sup.13 represents formyl, C.sub.2 -C.sub.12 alkoxycarbonyl, or C.sub.2 -C.sub.5 alkoxycarbonyl substituted with halogen or C.sub.1 -C.sub.4 alkoxy); a substituent of the formula, ##STR7## (in which R.sup.14 represents hydrogen, C.sub.1 -C.sub.4 alkyl or C.sub.2 -C.sub.6 alkoxyalkyl); a substituent of the formula, ##STR8## (in which R.sup.15 and R.sup.16, which may be the same or different, represent C.sub.1 -C.sub.4 alkyl or, taken together, may form C.sub.1 -C.sub.4 alkylene, R.sup.17 represents C.sub.1 -C.sub.5 alkyl, cyano or C.sub.2 -C.sub.6 alkoxycarbonyl, and Z.sup.1 represents oxygen or sulfur); a substituent of the formula, ##STR9## (in which R.sup.18 represents hydrogen or C.sub.2 -C.sub.4 alkylcarbonyl, and R.sup.19 and R.sup.20, which may be the same or different, represent hydrogen or C.sub.1 -C.sub.6 alkyl); a substituent of the formula, ##STR10## (in which R.sup.21, R.sup.22 and R.sup.23, which may be the same or different, represent C.sub.1 -C.sub.4 alkyl); or a substituent of the formula, ##STR11## (in which R.sup.24, R.sup.25, and R.sup.26, which may be the same or different, represent C.sub.1 -C.sub.4 alkyl), and n represents an integer of from 1 to 5, and when n represents an integer of from 2 to 5, X may be the same or different]; Y represents hydrogen, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.4 haloalkyl, halogen, hydroxy, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 haloalkoxy, C.sub.1 -C.sub.3 alkylenedioxy, phenoxy which may or may not be substituted with trifluoromethyl, a substituent of the formula, --S(O).sub.q R.sup.27 (in which R.sup.27 represents C.sub.1 -C.sub.3 alkyl and q represents an integer of 0, 1 or 2), hydroxycarbonyl, C.sub.2 -C.sub.5 alkoxycarbonyl or a substituent of the formula ##STR12## (in which R.sup.28 and R.sup.29, which may be the same or different, represent hydrogen, C.sub.1 -C.sub.4 alkyl, or benzyl which may or may not be substituted with C.sub.2 -C.sub.6 alkoxycarbonyl); Z.sup.1 represents oxygen or sulfur; Z.sup.2 represents oxygen, sulfur or single bond; Q represents C.sub.1 -C.sub.8 alkylene, C.sub.1 -C.sub.8 alkylene substituted with halogen or phenyl, C.sub.3 -C.sub.12 alkenylene, C.sub.3 -C.sub.12 haloalkenylene or C.sub.3 -C.sub.6 alkylene; and m represents an integer of from 1 to 3, and when m represents an integer of 2 or 3, Y may be the same or different.
The terms "alkyl, alkylene, alkenylene and alkynylene" as used herein mean straight-chain or branched alkyl, alkylene, alkenylene and alkynylene groups, respectively. The term "halo" means halogen such as fluorine, bromine, chlorine, etc., and the term "haloalkyl" means an alkyl group substituted with one or more halogen atoms which may be the same or different.
The compounds represented by the foregoing general formula (I) are novel compounds not described in the literatrues. They have excellent insecticidal activity against insects belonging to Lepidoptera such as diamond-back moth, cabbage armyworm, tobacco cutworm, rice stem borer, etc., insects belonging to Hemiptera such as brown planthoper, green peach aphid, etc. and mites. In addition, they have ecellent fungicidal activity against diseases of vegetables, fruit trees, flowers and ornamental plants, etc., such a rice blast, powdery mildew, downy mildew, crown rust, leaf blight, sheath blight, purple stain, etc.
Of the compounds of the present invention, those which are particularly useful as an insecticide and acaricide will be shown below:
Tert-butyl 4-[(1,3-dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl]benzoate
Tert-butyl 4-[{5-(4-fluorophenoxy)-1,3-dimethylpyrazol-4-yl}-methyleneaminooxymethyl]benzoate
Tert-pentyl 4-[(1,3-dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl]benzoate
Cyclohexyl 4-[(1,3-dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl]benzoate
1-Methylcyclohexyl 4-[1,3-dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl]benzoate
2-Chloromethyl-2-propyl 4-[(1,3-dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl]benzoate
Tert-pentyl 4-[(1-methyl-5-phenoxy-3-trifluoromethylpyrazol-4-yl)methyleneaminooxymethyl]benzoate
1,3-Dimethyl-5-phenoxypyrazole-4-carbaldehyde oxime O-4-tert-butylbenzyl ether
1,3-Dimethyl-5-phenoxypyrazole-4-carbaldehyde oxime O-4-(1-cyanocyclopentyl)benzyl ether
1,3-Dimethyl-5-phenoxypyrazole-4-carbaldehyde oxime O-4-(2,2-dichloro-1-methylcyclopropyl)benzyl ether
1,3-Dimethyl-5-phenoxypyrazole-4-carbaldehyde oxime O-4-trimethylsilylbenzyl ether
1,3-Dimethyl-5-phenoxypyrazole-4-carbaldehyde oxime O-4-(1,1,2,2-tetrafluoroethoxy)benzyl ether
1,3-Dimethyl-5-phenoxypyrazole-4-carbaldehyde oxime O-4-tert-butoxybenzyl ether
1,3-Dimethyl-5-phenoxypyrazole-4-carbaldehyde oxime O-4-(heptafluoropropylthio)benzyl ether
1,3-Dimethyl-5-phenoxypyrazole-4-carbaldehyde oxime O-4-(heptafluoropropylsulfinyl)benzyl ether
1,3-Dimethyl-5-phenoxypyrazole-4-carbaldehyde oxime O-4-(1,1,2,2-tetrafluoroethylthio)benzyl ether
N,N-diisopropyl 4-[(1,3-dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl]benzamide
Tert-butyl 4-[(1,3-dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl]phenyl ketone
2-Isopropyl-2-[4-{(1,3-dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl}phenyl]-1,3-dioxolane
2-Isopropyl-2-[4-{(1,3-dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl}phenyl]-1,3-dithiolane
Tert-butyl N-4-[(1,3-dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl]phenyl-N-ethylcarbamate
1,3-Dimethyl-5-phenoxypyrazole-4-carbaldehyde oxime O-2-(4-tert-butylphenoxy)ethyl ether
Also, compounds particularly useful as a fungicide will be shown below:
Isopropyl 4-[(1,3-dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl]benzoate
Isopropyl 4-[{5-(4-fluorophenoxy)-1,3-dimethylpyrazol-4-yl}-methyleneaminooxymethyl]benzoate
1,3-Dimethyl-5-phenoxypyrazole-4-carbaldehyde oxime O-4-(methylthio)benzyl ether
1,3-Dimethyl-5-phenoxypyraxole-4-carbaldehyde oxime O-4-(difluoromethylsulfinyl)benzyl ether
N,N-dimethyl 4-[(1,3-dimethyl-5-phenoxyprazol-4-yl)methyleneaminooxymethyl]benzamide
Methyl N-4-[(1,3-dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl]phenyl-N-ethylcarbamate
5-Ethyl-3-[N'-4-{(1,3-dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl}phenyl]-2-oxazolidine
The compounds represented by the general formula (I) can be synthesized, for example, by methods A, B, C and D shown below in chemical formulae. ##STR13## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, Q, Y, Z.sup.1, Z.sup.2, m and n are as defined above, Hal represents a halogen atom and M.sup.1 represents a hydrogen atom or an alkali metal atom.
The pyrazole oxime derivatives represented by the general formula (I) ca be obtained by reacting a compound of the general formula (II) what a compound of the general formula (III) in an inert solvent in the presence or absence of a base.
Solvents which can be used in the present invention may be any of those not disturbing the reaction, and include for example alcohols (e.g. isopropanol, tert-butanol, diethylene glycol), ketones (e.g. acetone, methyl ethyl ketone, cyclohexanone), ethers (e.g. diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, monoglyme, diglyme) halogenated hydrocarbons (e.g. dichloroethane, chloroform, carbon tetrachloride, tetrachloroethane), aromatic hydrocarbons (e.g. benzene, chlorobenzene, nitrobenzene, toluene), nitriles (e.g. acetonitrile), dimethyl sulfoxide, dimethylformamide and water. These solvents can be used alone or in combination. When a two-phase reaction is carried out using the solvents in combination, phase transfer catalysts such as triethylbenzylammonium chloride, trioctylmethylammonium chloride, etc. may be used.
For the base, inorganic and organic bases can be used. The inorganic bases include for example alkali or alkaline earth metal carbonates such as sodium carbonate, potassium carbonate, calcium carbonate, sodium hydrogencarbonate, etc., alkali or alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide, etc., and alkali metal hydrides such as lithium hydride, sodium hydride, etc.
The organic bases include for example diethylamine, triethylamine, pyridine, 4-dimethylaminopyridine, etc.
As to the amount of the base used, it suffices to use an amount equimolar to the compound represented by the general formula (II), but amounts in excess thereof will do.
The compound of the general formula (II) used in the present invention can be produced, for example, by the method described below: ##STR14## wherein R.sup.1, R.sup.2, R.sup.3, Y, Z.sup.1, m, Hal and M.sup.1 are as defined above.
That is, the compound of the general formula (II) can be produced by reacting a compound of the general formula (IV) with a compound of the general formula (V) in a suitable solvent and subsequently reacting the resulting compound of the general formula (VI) with hydroxylamine.
Among the compounds represented by the general formula (III), especially when Q is methylene, Z.sup.2 is a single bond and R.sup.4 is substituted phenyl group, are also some novel compounds, but they can be produced in the same manner as in the case of the known compounds. ##STR15## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, Q, Y, Z.sup.1, Z.sup.2, m and n are as defined above.
The pyrazole oxime derivatives represented by the general formula (I) can be obtained by reacting a compound of the general formula (VI) with a compound of the general formula (VII) in an inert solvent.
For the solvent which can be used in this reaction, there are mentioned the solvents except ketones shown in Method A.
The compound represented by the general formula (VII) can be produced according to the well-known method, for example, described in Methoden der Organishen Chemie (Hougen Weyl) Band X/I Stickstoffverbindungen Teil I, P 1192. ##STR16## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, Q, Y, Z.sup.1, Z.sup.2, m and n are as defined above, and M.sup.2 represents a hydrogen atom or an alkali metal atom.
The pyrazole oxime derivatives represented by the general formula (I) can be obtained by reacting a compound of the general formula (VIII) with a compound of the general formula (IX) in an inert solvent in the presence or absence of a base.
For the solvent and base which can be used in this reaction, there are mentioned the solvents and bases shown in Method A. ##STR17## wherein R.sup.1, R.sup.2, R.sup.3, Q, Y, Z.sup.1, Z.sup.2 and m are as defined above; X.sup.1 represents hydrogen or C.sub.1 -C.sub.4 alkyl; and R represents a substituent of the formula, --OW {in which W represents alkali metal; C.sub.1 -C.sub.10 alkyl; alkyl substituted with halogen, C.sub.1 -C.sub.4 alkoxy, phenoxy, C.sub.2 -C.sub.4 alkoxycarbonyl or phenyl; C.sub.2 -C.sub.7 alkenyl; C.sub.3 -C.sub.8 cycloalkyl; C.sub.3 -C.sub.8 cycloalkyl substituted with C.sub.1 -C.sub.3 alkyl; phenyl; or a substituent of the formula, ##STR18## (in which R.sup.7, R.sup.8, R.sup.9, which may be the same or different, represent C.sub.1 -C.sub.4 alkyl or C.sub.3 -C.sub.8 cycloalkyl)}, a substituent of the formula, ##STR19## (in which R.sup.10 and R.sup.11, which may be the same or different, represent hydrogen, C.sub.1 -C.sub.6 alkyl or phenyl); piperidino; morpholino which may or may not be substituted with one or two C.sub.1 -C.sub.4 alkyls; or C.sub.2 -C.sub.6 alkylthio.
That is, the pyrazole oxime derivatives represented by the general formula (Ia) can be obtained by reacting a compound of the general formula (X) with a compound of the general formula (XI) in an inert solvent in the presence of a dehydrating agent. The compound (X) may be reacted with the compound (XI) after converting it to acid chloride.
Solvents which can be used in this reaction may be any of those not disturbing the reaction, and include for example ethers (e.g. diethyl ether, tetrahydrofuran, dioxane, diethylene glycol), halogenated hydrocarbons (e.g. dichloromethane, chloroform, carbon tetrachloride), dimethyl sulfoxide, dimethylformamide, etc. These solvents may be used alone or in combination.
In the methods A to D, the reaction temperature may properly be selected from a range of from room temperature to the boiling point of the solvent. The reaction time depends upon the reaction temperature and reaction scale, but it may properly be selected from a range of from 1 minute to 48 hours.
As to the molar ratio of the reagents in practicing the reaction of the present invention, they are used in equimolar amounts because this reaction is an equimolar reaction, but either one of them may be used in excess of the other.
After completion of the reaction, the desired compound can be separated by the usual methods, and if necessary, can be purified by recrystallization, column chromatography, etc.
The pyrazole oxime derivatives represented by the general formula (I) have two isomers, E-isomer and Z-isomer. In the scope of the present invention are also included the both isomers and their mixtures. ##STR20##
Representative examples of the pyrazole oxime derivatives represented by the general formula (I) will be shown in Table 1, but the derivatives are not limited to these examples.
TABLE 1(a) ##STR21## ##STR22## Physical property m.p. (.degree.C.) Compound No. R.sup.1 R.sup.2 R.sup.3 X.sub.n Y.sub.m Z.sup.1 or refractive index 1 CH.sub.3 CH.sub.3 H 2-COOCH.sub.3 H O n.sub.D.sup.20 1.5772 2 CH.sub.3 CH.sub.3 H 2-COOCH.sub.3 4-F O n.sub.D.sup.20 1.5656 3 CH.sub.3 CH.sub.3 H 2-COOCH.sub.3 4-Cl O n.sub.D.sup.20 1.5788 4 CH.sub.3 CH.sub.3 H 2-COOCH.sub.3 4-OCH.sub.3 O n.sub.D.sup.20 1.5654 5 CH.sub.3 CH.sub.3 H 2-COOC.sub.4 H.sub.9t H O n.sub.D.sup.20 1.5462 6 CH.sub.3 CH.sub.3 H 2-COOC.sub.4 H.sub.9t 4-F O n.sub.D.sup.20 1.5446 7 CH.sub.3 CH.sub.3 H 2-COOC.sub.4 H.sub.9t 4-OCH.sub.3 O n.sub.D.sup.20 1.5579 8 CH.sub.3 CH.sub.3 H 3-COOC.sub.4 H.sub.9t H O n.sub.D.sup.20 1.5548 9 CH.sub.3 CH.sub.3 H 3-COOC.sub.4 H.sub.9t 4-F O n.sub.D.sup.20 1.5457 10 CH.sub.3 CH.sub.3 H 3-COOC.sub.4 H.sub.9t 4-OCH.sub.3 O n.sub.D.sup.20 1.5560 11 CH.sub.3 CH.sub.3 H 3-COOC(CH.sub.3).sub.2 C.sub.2 H.sub.5 H O n.sub.D.sup.20 1.5429 12 CH.sub.3 CH.sub.3 H 3-COOC(CH.sub.3).sub.2 C.sub.2 H.sub.5 3-F O n.sub.D.sup.20 1.5501 13 CH.sub.3 CH.sub.3 H 3-COOC(CH.sub.3).sub.2 C.sub.2 H.sub.5 4-OCH.sub.3 O n.sub.D.sup.20 1.5555 14 CH.sub.3 CH.sub.3 H 4-COOH H O m.p. 183.3 15 CH.sub.3 CH.sub.3 H 4-COONa H O .sup. m.p. >300 16 CH.sub.3 CH.sub.3 H 4-COOCH.sub.3 H O n.sub.D.sup.20 1.5612 17 CH.sub.3 CH.sub.3 H 4-COOCH.sub.3 4-F O m.p. 66.0 18 CH.sub.3 CH.sub.3 H 4-COOCH.sub.3 4-Cl O n.sub.D.sup.20 1.5800 19 CH.sub.3 CH.sub.3 H 4-COOCH.sub.3 4-OCH.sub.3 O m.p. 55.7 20 CH.sub.3 CH.sub.3 H 4-COOC.sub.2 H.sub.5 H O n.sub.D.sup.20 1.5613 21 CH.sub.3 CH.sub.3 H 4-COOC.sub.2 H.sub.5 4-F O n.sub.D.sup.20 1.5561 22 CH.sub.3 CH.sub.3 H 4-COOC.sub.2 H.sub.5 4-Cl O n.sub.D.sup.20 1.5658 23 CH.sub.3 CH.sub.3 H 4-COOC.sub.2 H.sub.5 4-OCH.sub.3 O n.sub.D.sup.20 1.5664 24 CH.sub.3 CH.sub.3 H 4-COOC.sub.3 H.sub.7n H O n.sub.D.sup.20 1.5660 25 CH.sub.3 CH.sub.3 H 4-COOC.sub.3 H.sub.7n 4-F O n.sub.D.sup.20 1.5579 26 CH.sub.3 CH.sub.3 H 4-COOC.sub.3 H.sub.7n 4-OCH.sub.3 O n.sub.D.sup.20 1.5628 27 CH.sub.3 CH.sub.3 H 4-COOC.sub.3 H.sub.7i H O n.sub.D.sup.20 1.5321 28 CH.sub.3 CH.sub.3 H 4-COOC.sub.3 H.sub.7i 4-CH.sub.3 O n.sub.D.sup.20 1.5608 29 CH.sub.3 CH.sub.3 H 4-COOC.sub.3 H.sub.7i 3-C.sub.2 H.sub.5 O n.sub.D.sup.20 1.5512 30 CH.sub.3 CH.sub.3 H 4-COOC.sub.3 H.sub.7i 4-C.sub.2 H.sub.5 O n.sub.D.sup.20 1.5579 31 CH.sub.3 CH.sub.3 H 4-COOC.sub.3 H.sub.7i 4-C.sub.4 H.sub.9t O n.sub.D.sup.20 1.5471 32 CH.sub.3 CH.sub.3 H 4-COOC.sub.3 H.sub.7i 2-F O n.sub.D.sup.20 1.5523 33 CH.sub.3 CH.sub.3 H 4-COOC.sub.3 H.sub.7i 3-F O n.sub.D.sup.20 1.5531 34 CH.sub.3 CH.sub.3 H 4-COOC.sub.3 H.sub.7i 4-F O n.sub.D.sup.20 1.5541 35 CH.sub.3 CH.sub.3 H 4-COOC.sub.3 H.sub.7i 3-Cl O n.sub.D.sup.20 1.5610 36 CH.sub.3 CH.sub.3 H 4-COOC.sub.3 H.sub.7i 4-Cl O n.sub.D.sup.20 1.5608 37 CH.sub.3 CH.sub.3 H 4-COOC.sub.3 H.sub.7i 2,4-Cl.sub.2 O n.sub.D.sup.20 1.5640 38 CH.sub.3 CH.sub.3 H 4-COOC.sub.3 H.sub.7i 3,4-Cl.sub.2 O n.sub.D.sup.20 1.5648 39 CH.sub.3 CH.sub.3 H 4-COOC.sub.3 H.sub.7i 4-Br O n.sub.D.sup.20 1.5618 40 CH.sub.3 CH.sub.3 H 4-COOC.sub.3 H.sub.7i 2-OCH.sub.3 O n.sub.D.sup.20 1.5586 41 CH.sub.3 CH.sub.3 H 4-COOC.sub.3 H.sub.7i 3-OCH.sub.3 O n.sub.D.sup.20 1.5585 42 CH.sub.3 CH.sub.3 H 4-COOC.sub.3 H.sub.7i 4-OCH.sub.3 O n.sub.D.sup.20 1.5597 43 CH.sub.3 CH.sub.3 H 4-COOC.sub.3 H.sub.7i 3,5-(OCH.sub.3).sub.2 O n.sub.D.sup.20 1.5621 44 CH.sub.3 CH.sub.3 H 4-COOC.sub.3 H.sub.7i 4-OC.sub.2 H.sub.5 O n.sub.D.sup.20 1.5536 45 CH.sub.3 CH.sub.3 H 4-COOC.sub.3 H.sub.7i 4-SCH.sub.3 O n.sub.D.sup.20 1.5819 46 CH.sub.3 CH.sub.3 H 4-COOC.sub.3 H.sub.7i 4-S(O)CH.sub.3 O n.sub.D.sup.20 1.5729 47 CH.sub.3 CH.sub.3 H 4-COOC.sub.3 H.sub.7i 4-S(O).sub.2 CH.sub.3 O n.sub.D.sup.20 1.5633 48 CH.sub.3 CH.sub.3 H 4-COOC.sub.3 H.sub.7i 3,4(OCH.sub.2 O) O n.sub.D.sup.20 1.5593 49 CH.sub.3 CH.sub.3 H 4-COOC.sub.3 H.sub.7i 3-N(CH.sub.3).sub.2 O n.sub.D.sup.20 1.5649 50 CH.sub.3 CH.sub.3 H 4-COOC.sub.4 H.sub.9n H O n.sub.D.sup.20 1.5619 51 CH.sub.3 CH.sub.3 H 4-COOC.sub.4 H.sub.9n 4-F O n.sub.D.sup.20 1.5536 52 CH.sub.3 CH.sub.3 H 4-COOC.sub.4 H.sub.9n 4-Cl O n.sub.D.sup.20 1.5629 53 CH.sub.3 CH.sub.3 H 4-COOC.sub.4 H.sub.9n 4-OCH.sub.3 O n.sub.D.sup.20 1.5536 54 CH.sub.3 CH.sub.3 H 4-COOC.sub.4 H.sub.9s H O n.sub.D.sup.20 1.5602 55 CH.sub.3 CH.sub.3 H 4-COOC.sub.4 H.sub.9s 4-F O n.sub.D.sup.20 1.5541 56 CH.sub.3 CH.sub.3 H 4-COOC.sub.4 H.sub.9s 4-OCH.sub.3 O n.sub.D.sup.20 1.5594 57 CH.sub.3 CH.sub.3 H 4-COOC.sub.4 H.sub.9i H O n.sub.D.sup.20 1.5629 58 CH.sub.3 CH.sub.3 H 4-COOC.sub.4 H.sub.9i 4-F O n.sub.D.sup.20 1.5561 59 CH.sub.3 CH.sub.3 H 4-COOC.sub.4 H.sub.9i 4-OCH.sub.3 O n.sub.D.sup.20 1.5608 60 CH.sub.3 CH.sub.3 H 4-COOC.sub.4 H.sub.9t H O m.p. 101.7 61 CH.sub.3 CH.sub.3 H 4-COOC.sub.4 H.sub.9t 4-CH.sub.3 O m.p. 73.0 62 CH.sub.3 CH.sub.3 H 4-COOC.sub.4 H.sub.9t 3-C.sub.2 H.sub.5 O n.sub.D.sup.20 1.5542 63 CH.sub.3 CH.sub.3 H 4-COOC.sub.4 H.sub.9t 4-C.sub.2 H.sub.5 O n.sub.D.sup.20 1.5440 64 CH.sub.3 CH.sub.3 H 4-COOC.sub.4 H.sub.9t 4-C.sub.4 H.sub.9t O n.sub.D.sup.20 1.5423 65 CH.sub.3 CH.sub.3 H 4-COOC.sub.4 H.sub.9t 2-F O m.p. 92.1 66 CH.sub.3 CH.sub.3 H 4-COOC.sub.4 H.sub.9t 3-F O m.p. 73.9 67 CH.sub.3 CH.sub.3 H 4-COOC.sub.4 H.sub.9t 4-F O m.p. 86.8 68 CH.sub.3 CH.sub.3 H 4-COOC.sub.4 H.sub.9t 3-Cl O n.sub.D.sup.20 1.5632 69 CH.sub.3 CH.sub.3 H 4-COOC.sub.4 H.sub. t 9 4-Cl O Paste 70 CH.sub.3 CH.sub.3 H 4-COOC.sub.4 H.sub.9t 4-Br O n.sub.D.sup.20 1.5660 71 CH.sub.3 CH.sub.3 H 4-COOC.sub.4 H.sub.9t 3-CF.sub.3 O n.sub.D.sup.20 1.5150 72 CH.sub.3 CH.sub.3 H 4-COOC.sub.4 H.sub.9t 2-OCH.sub.3 O m.p. 72.3 73 CH.sub.3 CH.sub.3 H 4-COOC.sub.4 H.sub.9t 3-OCH.sub.3 O n.sub.D.sup.20 1.5663 74 CH.sub.3 CH.sub.3 H 4-COOC.sub.4 H.sub.9t 4-OCH.sub.3 O n.sub.D.sup.20 1.5566 75 CH.sub.3 CH.sub.3 H 4-COOC.sub.4 H.sub.9t 4-OH O m.p. 145.0 76 CH.sub.3 CH.sub.3 H 4-COOC.sub.4 H.sub.9t 4-OC.sub.2 H.sub.5 O n.sub.D.sup.20 1.5487 77 CH.sub.3 CH.sub.3 H 4-COOC.sub.4 H.sub.9t 4-SCH.sub.3 O n.sub.D.sup.20 1.5653 78 CH.sub.3 CH.sub.3 H 4-COOC.sub.4 H.sub.9t 4-S(O)CH.sub.3 O n.sub.D.sup.20 1.5620 79 CH.sub.3 CH.sub.3 H 4-COOC.sub.4 H.sub.9t 4-S(O).sub.2 CH.sub.3 O n.sub.D.sup.20 1.5521 80 CH.sub.3 CH.sub.3 H 4-COOC.sub.4 H.sub.9t 4-CO.sub.2 C.sub.3 H.sub.7n O n.sub.D.sup.20 1.5641 81 CH.sub.3 CH.sub.3 H 4-COOC.sub.4 H.sub.9t 3,4(OCH.sub.2 O) O n.sub.D.sup.20 1.5515 82 CH.sub.3 CH.sub.3 H 4-COOC.sub.4 H.sub.9t 3-N(CH.sub.3).sub.2 O n.sub.D.sup.20 1.5538 83 CH.sub.3 CH.sub.3 H 4-COOC.sub.4 H.sub.9t ##STR23## O n.sub.D.sup.20 1.5605 84 CH.sub.3 CH.sub.3 H 4-COOC.sub.4 H.sub.9t ##STR24## O n.sub.D.sup.20 1.5689 85 CH.sub.3 CH.sub.3 H 4-COOC(CH.sub.3).sub.2 C.sub.2 H.sub.5 H O n.sub.D.sup.20 1.5564 86 CH.sub.3 CH.sub.3 H 4-COOC(CH.sub.3).sub.2 C.sub.2 H.sub.5 3-F O n.sub.D.sup.20 1.5413 87 CH.sub.3 CH.sub.3 H 4-COOC(CH.sub.3).sub.2 C.sub.2 H.sub.5 4-F O n.sub.D.sup.20 1.5529 88 CH.sub.3 CH.sub. 3 H 4-COOC(CH.sub.2).sub.2 C.sub.2 H.sub.5 3-OCH.sub.3 O n.sub.D.sup.20 1.5530 89 CH.sub.3 CH.sub.3 H 4-COOC(CH.sub.3).sub.2 C.sub.2 H.sub.5 4-OCH.sub.3 O n.sub.D.sup.20 1.5592 90 CH.sub.3 CH.sub.3 H 4-COOCH(C.sub.2 H.sub.5).sub.2 H O n.sub.D.sup.20 1.5590 91 CH.sub.3 CH.sub.3 H 4-COOCH(C.sub.2 H.sub.5).sub.2 4-F O n.sub.D.sup.20 1.5502 92 CH.sub.3 CH.sub.3 H 4-COOCH(C.sub.2 H.sub.5).sub.2 4-OCH.sub.3 O n.sub.D.sup.20 1.5591 93 CH.sub.3 CH.sub.3 H 4-COOCH.sub.2 C.sub.4 H.sub.9t H O n.sub.D.sup.20 1.5538 94 CH.sub.3 CH.sub.3 H 4-COOCH.sub.2 C.sub.4 H.sub.9t 4-F O n.sub.D.sup.20 1.5470 95 CH.sub.3 CH.sub.3 H 4-COOCH.sub.2 C.sub.4 H.sub.9t 4-OCH.sub.3 O n.sub.D.sup.20 1.5509 96 CH.sub.3 CH.sub.3 H ##STR25## H O n.sub.D.sup.20 1.5653 97 CH.sub.3 CH.sub.3 H ##STR26## 4-F O n.sub.D.sup.20 1.5537 98 CH.sub.3 CH.sub.3 H ##STR27## 4-OCH.sub.3 O n.sub.D.sup.20 1.5695 99 CH.sub.3 CH.sub.3 H ##STR28## H O n.sub.D.sup.20 1.5604 100 CH.sub.3 CH.sub.3 H ##STR29## 4-F O n.sub.D.sup.20 1.5525 101 CH.sub.3 CH.sub.3 H ##STR30## 4-OCH.sub.3 O n.sub.D.sup.20 1.5599 102 CH.sub.3 CH.sub.3 H 4-COOC(CH.sub.3).sub.2 CHCH.sub.2 H O n.sub.D.sup.20 1.5611 103 CH.sub.3 CH.sub.3 H 4-COOC(CH.s ub.3).sub.2 CHCH.sub.2 4-F O n.sub.D.sup.20 1.5558 104 CH.sub.3 CH.sub.3 H 4-COOC(CH.sub.3).sub.2 CHCH.sub.2 4-OCH.sub.3 O n.sub.D.sup.20 1.5620 105 CH.sub.3 CH.sub.3 H 4-COOCH(C.sub.2 H.sub.5)CCH H O n.sub.D.sup.20 1.5633 106 CH.sub.3 CH.sub.3 H 4-COOC.sub.6 H.sub.13n H O n.sub.D.sup.20 1.5543 107 CH.sub.3 CH.sub.3 H 4-COOC.sub.6 H.sub.13n 4-F O n.sub.D.sup.20 1.5468 108 CH.sub.3 CH.sub.3 H 4-COOC.sub .6 H.sub.13n 4-OCH.sub.3 O n.sub.D.sup.20 1.5549 109 CH.sub.3 CH.sub.3 H 4-COOC(CH.sub.3).sub.2 C.sub.3 H.sub.7i H O n.sub.D.sup.20 1.5525 110 CH.sub.3 CH.sub.3 H 4-COOC(CH.sub.3).sub.2 C.sub.3 H.sub.7i 3-F O n.sub.D.sup.20 1.5465 111 CH.sub.3 CH.sub.3 H 4-COOC(CH.sub.3).sub.2 C.sub.3 H.sub.7i 4-F O n.sub.D.sup.20 1.5425 112 CH.sub.3 CH.sub.3 H 4-COOC(C.sub.2 H.sub.5).sub.2 CH.sub.3 H O n.sub.D.sup.20 1.5480 113 CH.sub.3 CH.sub.3 H 4-COOC(C.sub.2 H.sub.5).sub.2 CH.sub.3 4-F O n.sub.D.sup.20 1.5431 114 CH.sub.3 CH.sub.3 H 4-COOC(C.sub.2 H.sub.5).sub.2 CH.sub.3 4-OCH.sub.3 O n.sub.D.sup.20 1.5540 115 CH.sub.3 CH.sub.3 H 4-COOCH(CH.sub.3)C.sub.4 H.sub.9t H O n.sub.D.sup.20 1.5529 116 CH.sub.3 CH.sub.3 H 4-COOCH(CH.sub.3)C.sub.4 H.sub.9 t 4-F O n.sub.D.sup.20 1.5478 117 CH.sub.3 CH.sub.3 H 4-COOCH(CH.sub.3)C.sub.4 H.sub.9t 4-OCH.sub.3 O n.sub.D.sup.20 1.5509 118 CH.sub.3 CH.sub.3 H ##STR31## H O Paste 119 CH.sub.3 CH.sub.3 H ##STR32## 4-F O n.sub.D.sup.20 1.5863 120 CH.sub.3 CH.sub.3 H ##STR33## 4-Cl O n.sub.D.sup.20 1.5960 121 CH.sub.3 CH.sub.3 H ##STR34## 4-OCH.sub.3 O n.sub.D.sup.20 1.5976 122 CH.sub.3 CH.sub.3 H ##STR35## H O n.sub.D.sup.20 1.5621 123 CH.sub.3 CH.sub.3 H ##STR36## 4-F O n.sub.D.sup.20 1.5511 124 CH.sub.3 CH.sub.3 H ##STR37## 4-OCH.sub.3 O n.sub.D.sup.20 1.5541 125 CH.sub.3 CH.sub.3 H ##STR38## H O n.sub.D.sup.20 1.5584 126 CH.sub.3 CH.sub.3 H ##STR39## 4-F O n.sub.D.sup.20 1.5370 127 CH.sub.3 CH.sub.3 H ##STR40## 4-OCH.sub.3 O n.sub.D.sup.20 1.5492 128 CH.sub.3 CH.sub.3 H ##STR41## H O n.sub.D.sup.20 1.5552 129 CH.sub.3 CH.sub.3 H ##STR42## 4-OCH.sub.3 O n.sub.D.sup.20 1.5541 130 CH.sub.3 CH.sub.3 H 4-COOCH(C.sub.3 H.sub.7i).sub.2 H O n.sub.D.sup.20 1.5471 131 CH.sub.3 CH.sub.3 H 4-COOCH(C.sub.3 H.sub.7i).sub.2 4-F O n.sub.D.sup.20 1.5400 132 CH.sub.3 CH.sub.3 H 4-COOCH(C.sub.3 H.sub.7i).sub.2 4-OCH.sub.3 O n.sub.D.sup.20 1.5490 133 CH.sub.3 CH H 4-COOC(C.sub.2 H.sub.5).sub.3 H O n.sub.D.sup.20 1.5465 134 CH.sub.3 CH.sub.3 H 4-COOC(C.sub.2 H.sub.5).sub.3 4-F O n.sub.D.sup.20 1.5462 135 CH.sub.3 CH.sub.3 H 4-COOC(C.sub.2 H.sub.5).sub.3 4-OCH.sub.3 O n.sub.D.sup.20 1.5518 136 CH.sub.3 CH.sub.3 H ##STR43## H O n.sub.D.sup.20 1.5730 137 CH.sub.3 CH.sub.3 H ##STR44## H O n.sub.D.sup.20 1.5901 138 CH.sub.3 CH.sub.3 H ##STR45## H O n.sub.D.sup.20 1.5675 139 CH.sub.3 CH.sub.3 H 4-COOC.sub.2 H.sub.4 OCH.sub.3 H O n.sub.D.sup.20 1.5672 140 CH.sub.3 CH.sub.3 H 4-COOCH(CH.su b.3)CH.sub.2 OCH.sub.3 H O n.sub.D.sup.20 1.5563 141 CH.sub.3 CH.sub.3 H 4-COOC(CH.sub.3).sub.2 CO.sub.2 CH.sub.3 H O n.sub.D.sup.20 1.5583 142 CH.sub.3 CH.sub. 3 H ##STR46## 4-F O n.sub.D.sup.20 1.5655 143 CH.sub.3 CH.sub.3 H ##STR47## 4-Cl O n.sub.D.sup.20 1.5685 144 CH.sub.3 CH.sub.3 H ##STR48## 4-OCH.sub.3 O n.sub.D.sup.20 1.5764 145 CH.sub.3 CH.sub.3 H 4-COOC.sub.2 H.sub.4 OCH.sub.3 4-OCH.sub.3 O n.sub.D.sup.20 1.5695 146 CH.sub.3 CH.sub.3 H 4-COOCH.sub.2 CF.sub.3 H O n.sub.D.sup.20 1.5491 147 CH.sub.3 CH.sub.3 H 4-COOCH.sub.2 CF.sub.3 4-F O n.sub.D.sup.20 1.5409 148 CH.sub.3 CH.sub.3 H 4-COOCH.sub.2 CF.sub.3 4-Cl O n.sub.D.sup.20 1.5450 149 CH.sub.3 CH.sub.3 H 4-COOCH.sub.2 CF.sub.3 4-OCH.sub.3 O n.sub.D.sup.20 1.5459 150 CH.sub.3 CH.sub.3 H 4-COOCH(CF.sub.3).sub.2 H O n.sub.D.sup.20 1.5563 151 CH.sub.3 CH.sub.3 H 4-COOCH(CF.sub.3).sub.2 4-F O n.sub.D.sup.20 1.5632 152 CH.sub. 3 CH.sub.3 H 4-COOCH(CF.sub.3).sub.2 4-OCH.sub.3 O n.sub.D.sup.20 1.5664 153 CH.sub.3 CH.sub.3 H 4-COOCH(CH.sub.2 Cl).sub.2 H O n.sub.D.sup.20 1.5451 154 CH.sub.3 CH.sub.3 H 4-COOC(CH.sub.3).sub.2 CH.sub.2 Cl H O n.sub.D.sup.20 1.5662 155 CH.sub.3 CH.sub.3 H 4-COOC(CH.sub.3).sub.2 CH.sub.2 Cl 3-F O n.sub.D.sup.20 1.5520 156 CH.sub.3 CH.sub.3 H 4-COOC(CH.sub.3). sub.2 CH.sub.2 Cl 4-F O n.sub.D.sup.20 1.5598 157 CH.sub.3 CH.sub.3 H 4-COOC(CH.sub.3).sub.2 CH.sub.2 Cl 3-Cl O n.sub.D.sup.20 1.5651 158 CH.sub.3 CH.sub.3 H 4-COOC(CH.sub.3).sub.2 CH.sub.2 Cl 4-Cl O n.sub.D.sup.20 1.5639 159 CH.sub.3 CH.sub.3 H 4-COOC(CH.sub.3) .sub.2 CH.sub.2 Cl 3-OCH.sub.3 O n.sub.D.sup.20 1.5602 160 CH.sub.3 CH.sub.3 H 4-COOC(CH.sub.3).sub.2 CH.sub.2 Cl 4-OCH.sub.3 O n.sub.D.sup.20 1.5665 161 CH.sub.3 CH.sub.3 H ##STR49## H O n.sub.D.sup.20 1.5656 162 CH.sub. 3 CH.sub.3 H 4-COOSn(C.sub.4 H.sub.9n).sub.3 H O n.sub.D.sup.20 1.5600 163 CH.sub.3 CH.sub.3 H ##STR50## H O n.sub.D.sup.20 1.5603 164 CH.sub.3 CF.sub.3 H 4-COOC(CH.sub.3).sub.2 C.sub.2 H.sub.5 H O n.sub.D.sup.20 1.5260 165 CH.sub.3 CH.sub.3 CH.sub.3 4-COOH H O Paste 166 CH.sub.3 CH.sub.3 CH.sub.3 4-COOC.sub.4 H.sub.9t H O m.p. 94.4 167 CH.sub.3 CH.sub.3 C.sub.2 H.sub.5 4-COOC.sub.4 H.sub.9t H O n.sub.D.sup.20 1.5536 168 CH.sub.3 CH.sub.3 ##STR51## 4-COOC.sub.4 H.sub.9t H O n.sub.D.sup.20 1.5644 169 CH.sub.3 CH.sub.3 CH.sub.3 4-COOC(CH.sub.3).sub.2 C.sub.2 H.sub.5 H O m.p. 60.9 170 CH.sub.3 CH.sub.3 CH.sub.3 ##STR52## H O n.sub.D.sup.20 1.5570 171 CH.sub.3 CH.sub.3 CH.sub.3 4-COOC(CH.sub.3).sub.2 CH.sub.2 Cl H O n.sub.D.sup.20 1.5578 172 CH.sub.3 C.sub.3 H.sub.7i H 4-COOC.sub.3 H.sub.7i H O n.sub.D.sup.20 1.5491 173 CH.sub.3 H H 4-COOC.sub.4 H.sub.9t H O Paste 174 CH.sub.3 CH.sub.3 H 4-COOC.sub.3 H.sub.7i H S n.sub.D.sup.20 1.5821 175 CH.sub.3 CH.sub.3 H 4-COOC.sub.4 H.sub.9t H S m.p. 112.3 176 CH.sub.3 CH.sub.3 H 4-COOC.sub.4 H.sub.9t H S(O) n.sub.D.sup.20 1.5649 177 CH.sub.3 CH.sub.3 H 4-COOC.sub .4 H.sub.9t H S(O).sub.2 n.sub.D.sup.20 1.5689 178 CH.sub.3 CH.sub.3 H 4-COOC.sub.4 H.sub.9t, 5-CH.sub.3 H O Paste 179 CH.sub.3 CH.sub.3 H 4-COOC.sub.4 H.sub.9t, 3-CH.sub.3 H O Paste 180 CH.sub.3 CH.sub.3 H 4-COOC(CH.sub.3).sub.2 CH.sub.2 F H O Paste 181 CH.sub.3 CH.sub.3 H H H O n.sub.D.sup.20 1.5517 182 CH.sub.3 CH.sub.3 H H 2-CH.sub.3 O n.sub.D.su p.20 1.5800 183 CH.sub.3 CH.sub.3 H H 3-CH.sub.3 O n.sub.D.sup.20 1.5778 184 CH.sub.3 CH.sub.3 H H 2-Cl O n.sub.D.sup.20 1.5895 185 CH.sub.3 CH.sub.3 H H 3-Cl O n.sub.D.sup.20 1.5834 186 CH.sub.3 CH.sub.3 H H 4-Cl O n.sub.D.sup.20 1.5766 187 CH.sub.3 CH.sub.3 H H 2,4-Cl.sub.2 O n.sub.D.sup.20 1.5498 188 CH.sub.3 CH.sub.3 H H 4-OCH.sub.3 O n.sub.D.sup .20 1.5765 189 CH.sub.3 CH.sub.3 H H ##STR53## O n.sub.D.sup.20 1.5823 190 CH.sub.3 CH.sub.3 H 2-CH.sub.3 H O n.sub.D.sup.20 1.5773 191 CH.sub.3 CH.sub.3 H 3-CH.sub.3 H O n.sub.D.sup. 20 1.5749 192 CH.sub.3 CH.sub.3 H 4-CH.sub.3 H O n.sub.D.sup.20 1.5783 193 CH.sub.3 CH.sub.3 H 4-CF.sub.3 H O n.sub.D.sup.20 1.5468 194 CH.sub.3 CH.sub.3 H 4-CF.sub.3 4-F O n.sub.D.sup.20 1.5355 195 CH.sub.3 CH.sub.3 H 4-CF.sub.3 4-Cl O n.sub.D.sup.20 1.5539 196 CH.sub.3 CH.sub.3 H 4-C.sub.2 H.sub.5 H O n.sub.D.sup.20 1.5739 197 CH.sub.3 CH.sub.3 H 4-C.sub.3 H.sub.7i H O n.sub.D.sup.20 1.5594 198 CH.sub.3 CH.sub.3 H 4-C(CH.sub.3).sub.2 CN H O m.p. 77.4 199 CH.sub.3 CH.sub.3 H ##STR54## H O m.p. 109.1 200 CH.sub.3 CH.sub.3 H 4-C(CH.sub.3).sub.2 CN 4-F O m.p. 94.7 201 CH.sub.3 CH.sub.3 H 4-C.sub.4 H.sub.9n H O n.sub.D.sup.20 1.5567 202 CH.sub.3 CH.sub.3 H 4-C.sub.4 H.sub.9n 4-Cl O n.sub.D.sup.20 1.5665 203 CH.sub.3 CH.sub.3 H 4-C.sub.4 H.sub.9s H O n.sub.D.sup.20 1.5631 204 CH.sub.3 CH.sub.3 H 4-C.sub.4 H.sub.9i H O n.sub.D.sup.20 1.5628 205 CH.sub.3 CH.sub.3 H 4-C.sub.4 H.sub.9t H O n.sub.D.sup.20 1.5402 206 CH.sub.3 CH.sub.3 H 4-C.sub.4 H.sub.9t 3-CH.sub.3 O n.sub.D.sup.20 1.5605 207 CH.sub.3 CH.sub.3 H 4-C.sub.4 H.sub.9 t 4-CH.sub.3 O m.p. 112.4 208 CH.sub.3 CH.sub.3 H 4-C.sub.4 H.sub.9t 3-C.sub.2 H.sub.5 O n.sub.D.sup.20 1.5539 209 CH.sub.3 CH.sub.3 H 4-C.sub.4 H.sub.9t 4-C.sub.2 H.sub.5 O m.p. 79.0 210 CH.sub.3 CH.sub.3 H 4-C.sub.4 H.sub.9t 4-C.sub.4 H.sub.9t O n.sub.D.sup.20 1.5475 211 CH.sub.3 CH.sub.3 H 4-C.sub.4 H.sub.9t 2-F O m.p. 67.7 212 CH.sub.3 CH.sub.3 H 4-C.sub.4 H.sub.9t 3-F O m.p. 66.9 213 CH.sub.3 CH.sub.3 H 4-C.sub.4 H.sub.9t 4-F O n.sub.D.sup.20 1.5507 214 CH.sub.3 CH.sub.3 H 4-C.sub.4 H.sub.9t 2-Cl O n.sub.D.sup.20 1.5633 215 CH.sub.3 CH.sub.3 H 4-C.sub.4 H.sub.9t 3-Cl O n.sub.D.sup.20 1.5573 216 CH.sub.3 CH.sub.3 H 4-C.sub.4 H.sub.9t 4-Cl O n.sub.D.sup.20 1.5653 217 CH.sub.3 CH.sub.3 H 4-C.sub.4 H.sub.9t 4-Br O n.sub.D.sup.20 1.5636 218 CH.sub.3 CH.sub.3 H 4-C.sub.4 H.sub.9t 3-CF.sub. 3 O n.sub.D.sup.20 1.5352 219 CH.sub.3 CH.sub.3 H 4-C.sub.4 H.sub.9t 2-OCH.sub.3 O m.p. 76.3 220 CH.sub.3 CH.sub.3 H 4-C.sub.4 H.sub.9t 3-OCH.sub.3 O n.sub.D.sup.20 1.6590 221 CH.sub.3 CH.sub.3 H 4-C.sub.4 H.sub.9t 4-OCH.sub.3 O n.sub.D.sup.20 1.5584 222 CH.sub.3 CH.sub.3 H 4-C.sub.4 H.sub.9t 3,5-(OCH.sub.3).sub.2 O n.sub.D.sup.20 1.5535 223 CH.sub.3 CH.sub.3 H 4-C.sub.4 H.sub.9t 4-OC.sub.2 H.sub.5 O n.sub.D.sup.20 1.5555 224 CH.sub.3 CH.sub.3 H 4-C.sub.4 H.sub.9t 4-CO.sub.2 C.sub.3 H.sub.7n O n.sub.D.sup.20 1.5532 225 CH.sub.3 CH.sub.3 H 4-C.sub.4 H.sub.9t 3,4(OCH.sub.2 O) O m.p. 111.4 226 CH.sub.3 CH.sub.3 H 4-C.sub.4 H.sub.9t 3-N(CH.sub.3).sub.2 O n.sub.D.sup.20 1.5858 227 CH.sub.3 CH.sub.3 H 4-C.sub.4 H.sub.9t ##STR55## O n.sub. D.sup.20 1.5712 228 CH.sub.3 CH.sub.3 H 4-C.sub.5 H.sub.11n H O n.sub.D.sup.20 1.5546 229 CH.sub.3 CH.sub.3 H 4-CH(CH.sub.3)C.sub.3 H.sub.7n H O n.sub.D.sup.20 1.5640 230 CH.sub.3 CH.sub.3 H 4-CH(CH.sub.3) C.sub.3 H.sub.7n 4-F O n.sub.D.sup.20 1.5568 231 CH.sub.3 CH.sub.3 H 4-CH(CH.sub.3)C.sub.3 H.sub.7n 4-Cl O n.sub.D.sup.20 1.5650 232 CH.sub.3 CH.sub.3 H 4-C(CH.sub.3).sub.2 C.sub.2 H.sub.5 H O n.sub.D.sup.20 1.5633 233 CH.sub.3 CH.sub.3 H 4-C(CH.sub.3).sub.2 C.sub.2 H.sub.5 2-F O n.sub.D.sup.20 1.5440 234 CH.sub.3 CH.sub.3 H 4-C(CH.sub.3).sub.2 C.sub.2 H.sub.5 4-F O n.sub.D.sup.20 1.5539 235 CH.sub.3 CH.sub.3 H 4-C(CH.sub.3).sub.2 C.sub.2 H.sub.5 4-Cl O n.sub.D.sup.20 1.5678 236 CH.sub.3 CH.sub.3 H 4-C(CH.sub.3).sub.2 C.sub.2 H.sub.5 4-OCH.sub.3 O n.sub.D.sup.20 1.5584 237 CH.sub.3 CH.sub.3 H ##STR56## H O n.sub.D.sup.20 1.5612 238 CH.sub.3 CH.sub.3 H ##STR57## 3-OCH.sub.3 O n.sub.D.sup.20 1.5632 239 CH.sub.3 CH.sub.3 H 4-CH(OH)C.sub.4 H.sub.9t H O n.sub.D.sup.20 1.5500 240 CH.sub.3 CH.sub.3 H 4-CH(OH)C.sub.4 H.sub.9t 4-F O n.sub.D.sup.20 1.5445 241 CH.sub.3 CH.sub.3 H 4-CH(OH)C.s ub.4 H.sub.9t 4-Cl O n.sub.D.sup.20 1.5500 242 CH.sub.3 CH.sub.3 H 4-C.sub.6 H.sub.13n H O n.sub.D.sup.20 1.5545 243 CH.sub.3 CH.sub.3 H ##STR58## H O n.sub.D.sup.20 1.5635 244 CH.sub.3 CH.sub.3 H ##STR59## 2-F O n.sub.D.sup.20 1.5591 245 CH.sub.3 CH.sub.3 H ##STR60## 4-F O n.sub.D.sup.20 1.5577 246 CH.sub.3 CH.sub.3 H ##STR61## 4-Cl O n.sub.D.sup.20 1.5728 247 CH.sub.3 CH.sub.3 H ##STR62## 3,5-(OCH.sub.3).sub.2 O n.sub.D.sup.20 1.5590 248 CH.sub.3 CH.sub.3 H ##STR63## H O n.sub.D.sup.20 1.5656 249 CH.sub.3 CH.sub.3 H ##STR64## 4-OCH.sub.3 O n.sub.D.sup.20 1.5596 250 CH.sub.3 CH.sub.3 H 4-C.sub.7 H.sub.15n H O n.sub.D.sup.20 1.5480 251 CH.sub.3 CH.sub.3 H 4-C.sub.8 H.sub.17n H O n.sub.D.sup.20 1.5532 252 CH.sub.3 CH.sub.3 H ##STR65## H O m.p. 121.7 253 CH.sub.3 CH.sub.3 H 4-C(CH.sub.3).sub.2 OCH.sub.3 H O n.sub.D.sup.20 1.5645 254 CH.sub.3 CH.sub.3 H 4-C(CH.sub.3).sub.2 OCH.sub.3 4-F O n.sub.D.sup.20 1.5513 255 CH.sub.3 CH.sub.3 H 4-CHCHCOC.s ub.4 H.sub.9t H O n.sub.D.sup.20 1.5701 256 CH.sub.3 CH.sub.3 H 4-CHCHCH(OH)C .sub.4 H.sub.9t H O n.sub.D.sup.20 1.5580 257 CH.sub.3 CH.sub.3 H 4-CHCHCOC.sub.4 H.sub.9t 4-F O n.sub.D.sup.20 1.5526 258 CH.sub.3 CH.sub.3 H 4-CHCHCOC.sub.4 H.sub.9t 4-OCH.sub.3 O n.sub.D.sup.20 1.5576 259 CH.sub.3 CH.sub.3 H 4-CHCHCO.sub.2 C.sub.2 H.sub.5 H O n.sub.D.sup.20 1.5919 260 CH.sub.3 CH.sub.3 H 4-CHCHCO.sub.2 C.sub.2 H.sub.5 4-F O n.sub.D.sup.20 1.5821 261 CH.sub.3 CH.sub.3 H C 4-CHHCO.sub.2 C.sub.2 H.sub.5 4-OCH.sub.3 O n.sub.D.sup.20 1.5887 262 CH.sub.3 CH.sub.3 H 4-CHCBr.sub.2 H O m.p. 109.3 263 CH.sub.3 CH.sub.3 H 4-C(CH.sub.3).sub.2 CO.sub.2 C.sub.2 H.sub.5 H O n.sub.D.sup.20 1.5320 264 CH.sub.3 CH.sub.3 H 4-C(CH.sub.3).sub.2 CO.sub.2 C.sub.2 H.sub.5 4-F O n.sub.D.sup.20 1.5502 265 CH.sub.3 CH.sub.3 H 4-C(CH.sub.3).sub.2 CO.sub.2 C.sub.3 H.sub.7i H O n.sub.D.sup.20 1.5492 266 CH.sub.3 CH.sub.3 H ##STR66## H O n.sub.D.sup.20 1.5680 267 CH.sub.3 CH.sub.3 H ##STR67## 4-F O n.sub.D.sup.20 1.5654 268 CH.sub.3 CH.sub.3 H ##STR68## 4-Cl O n.sub.D.sup.20 1.5660 269 CH.sub.3 CH.sub.3 H ##STR69## 4-OCH.sub.3 O n.sub.D.sup.20 1.5653 270 CH.sub.3 CH.sub.3 H 2,4-(CH.sub.3).sub.2 4-F O n.sub.D.sup.20 1.5654 271 CH.sub.3 CH.sub.3 H 2,4-(CH.sub.3).sub.2 4-Cl O n.sub.D.sup.20 1.5672 272 CH.sub.3 CH.sub.3 H 3-OCH.sub.3, 4-C.sub.4 H.sub.9t H O n.sub.D.sup.20 1.5567 273 CH.sub.3 CH.sub.3 H 3-OCH.sub.3, 4-C.sub.4 H.sub.9t 4-Cl O n.sub.D.sup.20 1.5572 274 CH.sub.3 CH.sub.3 H 2,4,6-(CH.s ub.3).sub.3 H O m.p. 94.5 275 CH.sub.3 CH.sub.3 H 2,6-(CH.sub.3).sub.2, 4-C.sub.4 H.sub.9t H O m.p. 111.0 276 CH.sub.3 CH.sub.3 H 2,6-(CH.sub.3).sub.2, 4-C.sub.4 H.sub.9t 4-F O m.p. 97.9 277 CH.sub.3 CH.sub.3 H 2,6-(CH.sub.3).sub.2, 4-C.sub.4 H.sub.9t 4-Cl O Paste 278 CH.sub.3 CH.sub.3 H 2,6-(CH.sub.3).sub.2, 4-C.sub.4 H.sub.9t 4-OCH.sub.3 O n.sub.D.sup.20 1.5528 279 CH.sub.3 H H H 4-Cl O n.sub.D.sup.20 1.5933 280 CH.sub.3 H H 4-C.sub.4 H.sub.9t H O n.sub.D.sup.20 1.5689 281 CH.sub.3 CH.sub.3 CH.sub.3 4-C.sub.4 H.sub.9t H O n.sub.D.sup.20 1.5850 282 CH.sub.3 CH.sub.3 C.sub.2 H.sub.5 4-C.sub.4 H.sub.9t H O n.sub.D.sup.20 1.5536 283 CH.sub.3 CH.sub.3 CH.sub.3 ##STR70## H O n.sub.D.sup.20 1.5775 284 CH.sub.3 C.sub.2 H.sub.5 H 4-C.sub.4 H.sub.9t H O m.p. 99.2 285 CH.sub.3 C.sub.3 H.sub.7i H 4-C.sub.4 H.sub.9t H O m.p. 71.5 286 CH.sub.3 ##STR71## H H 4-Cl O n.sub.D.sup.20 1.5966 287 CH.sub.3 ##STR72## H ##STR73## 4-Cl O n.sub.D.sup.20 1.6000 288 C.sub.2 H.sub.5 CH.sub.3 H 4-C.sub.4 H.sub.9t H O n.sub.D.sup.20 1.5521 289 ##STR74## CH.sub.3 H 4-C.sub.4 H.sub.9t H O n.sub.D.sup.20 1.5905 290 CH.sub.3 CH.sub.3 H H 4-Cl S n.sub.D.sup.20 1.5562 291 CH.sub.3 CH.sub.3 H 4-C.sub.4 H.sub.9t H S n.sub.D.sup.20 1.5760 292 CH.sub.3 CH.sub.3 H 4-C(CH.sub.3)(CO.sub.2 C.sub.2 H.sub.5).sub.2 H O n.sub.D.sup.20 1.5515 293 CH.sub.3 CH.sub.3 H 4-C(CH.sub.3)(CO.sub.2 C.sub.2 H.sub.5).sub.2 4-F O n.sub.D.sup.20 1.5462 294 CH.sub.3 CH.sub.3 H 4-C(CH.sub.3)(CO.sub. 2 C.sub.2 H.sub.5).sub.2 4-Cl O n.sub.D.sup.20 1.5567 295 CH.sub.3 CH.sub.3 H 4-C(CH.sub.3)(CO.sub.2 C.sub.2 H.sub.5).sub.2 4-OCH.sub.3 O n.sub.D.sup.20 1.5553 296 CH.sub.3 CH.sub.3 H 4-C.sub.4 H.sub.9t 4-SCH.sub.3 O n.sub.D.sup.20 1.5853 297 CH.sub.3 CH.sub.3 H 4-C.sub.4 H.sub.9t 4-S(O)CH.sub.3 O n.sub.D.sup.20 1.5698 298 CH.sub.3 CH.sub.3 H 4-C.sub.4 H.sub.9t 4-S(O).sub.2 CH.sub.3 O m.p. 133.6 299 CH.sub.3 CH.sub.3 H 4-C(CH.sub.3).sub.2 CH.sub.2 F H O Paste 300 CH.sub.3 H H 4-Cl H O n.sub.D.sup.20 1.5586 301 CH.sub.3 H H 4-Cl 4-Cl O n.sub.D.sup.2 0 1.5859 302 CH.sub.3 H H 4-SCHF.sub.2 H O n.sub.D.sup.20 1.5558 303 CH.sub.3 H H 4-SCHF.sub.2 4-Cl O n.sub.D.sup.20 1.5896 304 CH.sub.3 H H 4-S(O)CHF.sub.2 H O n.sub.D.sup.20 1.5526 305 CH.sub.3 CH.sub.3 H 4-F H O n.sub.D.sup.20 1.5681 306 CH.sub.3 CH.sub.3 H 4-F 4-Cl O n.sub.D.sup.20 1.5724 307 CH.sub.3 CH.sub.3 H 2,3,4,5,6-F.sub.5 H O n.sub.D.sup.20 1.5886 308 CH.sub.3 CH.sub.3 H 2-Cl H O n.sub.D.sup.20 1.5868 309 CH.sub.3 CH.sub.3 H 2-Cl 4-Cl O n.sub.D.sup.20 1.5760 310 CH.sub.3 CH.sub.3 H 3-Cl H O n.sub.D.sup.20 1.5490 311 CH.sub.3 CH.sub.3 H 3-Cl 4-Cl O n.sub.D.sup.20 1.5820 312 CH.sub.3 CH.sub.3 H 4-Cl H O n.sub.D.sup .20 1.5750 313 CH.sub.3 CH.sub.3 H 4-Cl H S n.sub.D.sup.20 1.5563 314 CH.sub.3 CH.sub.3 H 4-Cl 2-Cl O n.sub.D.sup.20 1.5892 315 CH.sub.3 CH.sub.3 H 4-Cl 3-Cl O n.sub.D.sup.20 1.5905 316 CH.sub.3 CH.sub.3 H 4-Cl 4-Cl O n.sub.D.sup.20 1.5785 317 CH.sub.3 CH.sub.3 H 4-Cl 4-Cl S m.p. 96.7 318 CH.sub.3 CH.sub.3 H 4-Cl 4-Cl SO n.sub.D.sup.20 1.5569 319 CH.sub.3 CH.sub.3 H 4-Cl 4-Cl SO.sub.2 n.sub.D.sup.20 1.5642 320 CH.sub.3 CH.sub.3 H 4-Cl 2,4-Cl.sub.2 O m.p. 117.9 321 CH.sub.3 CH.sub.3 H 4-Cl 4-OCH.sub.3 O n.sub.D.sup. 20 1.5809 322 CH.sub.3 CH.sub.3 H 4-Cl ##STR75## O m.p. 97.8 323 CH.sub.3 CH.sub.3 H 2,4-Cl.sub.2 4-Cl O n.sub.D.sup.20 1.5811 324 CH.sub.3 CH.sub.3 H 3,4-Cl.sub.2 4-Cl O n.sub.D.sup.20 1.5958 325 CH.sub.3 CH.sub.3 H 2,5-Cl.sub.2 4-Cl O n.sub.D.sup.20 1.5826 326 CH.sub.3 CH.sub.3 H 3,5-Cl.sub.2 4-Cl O n.sub.D.sup.20 1.5778 327 CH.sub.3 CH.sub.3 H 2,6-Cl.sub.2 4-Cl O n.sub.D.sup.20 1.5825 328 CH.sub.3 CH.sub.3 H 4-Br H O n.sub.D.sup.20 1.5878 329 CH.sub.3 CH.sub.3 H 4-Br 4-Cl O n.sub.D.sup.20 1.5972 330 CH.sub.3 CH.sub.3 H 4-I 4-Cl O n.sub.D.sup.20 1.6131 331 CH.sub.3 CH.sub.3 H 4-CN H O n.sub.D.sup.20 1.5882 332 CH.sub.3 CH.sub.3 H 4-NO.sub.2 H O n.sub.D.sup.20 1.5942 333 CH.sub.3 CH.sub.3 H 4-Si(CH.sub.3).sub.3 H O m.p. 50.8 334 CH.sub.3 CH.sub.3 CH.sub.3 4-Si(CH.sub.3).sub.3 H O m.p. 61.2 335 CH.sub.3 CH.sub.3 H 4-OH H O .sup. m.p. >300 336 CH.sub.3 CH.sub.3 H 4-OCH.sub.3 H O n.sub.D.sup.20 1.5739 337 CH.sub.3 CH.sub.3 H 4-OCHF.sub.2 H O n.sub.D.sup.20 1.5422 338 CH.sub.3 CH.sub.3 H 4-OCHF.sub.2 H S n.sub.D.su p.20 1.5772 339 CH.sub.3 CH.sub.3 H 4-OCHF.sub.2 H SO n.sub.D.sup.20 1.5583 340 CH.sub.3 CH.sub.3 H 4-OCHF.sub.2 4-CH.sub.3 O n.sub.D.sup.20 1.5745 341 CH.sub.3 CH.sub.3 H 4-OCHF.sub.2 4-C.sub.4 H.sub.9t O n.sub.D.sup.20 1.5396 342 CH.sub.3 CH.sub.3 H 4-OCHF.sub.2 4-F O n.sub.D.sup.20 1.5455 343 CH.sub.3 CH.sub.3 H 4-OCHF.sub.2 3-Cl O n.sub.D.sup.20 1.5630 344 CH.sub.3 CH.sub.3 H 4-OCHF.sub.2 4-Cl O n.sub.D.sup.20 1.5584 345 CH.sub.3 CH.sub.3 H 4-OCHF.sub.2 3,4-Cl.sub.2 O n.sub.D.sup.20 1.5460 346 CH.sub.3 CH.sub.3 H 4-OCHF.sub.2 4-OCH.sub.3 O n.sub.D.sup.20 1.5462 347 CH.sub.3 CH.sub.3 H 4-OCF.sub.3 H O n.sub.D.s up.20 1.5386 348 CH.sub.3 CH.sub.3 H 4-OCF.sub.3 H S n.sub.D.sup.20 1.5510 349 CH.sub.3 CH.sub.3 H 4-OCF.sub.3 3-Cl O n.sub.D.sup.20 1.5399 350 CH.sub.3 CH.sub.3 H 4-OCF.sub.3 4-Cl O n.sub.D.sup.20 1.5244 351 CH.sub.3 CH.sub.3 H 4-OC.sub.2 H.sub.5 H O n.sub.D.sup.20 1.5736 352 CH.sub.3 CH.sub.3 H 4-OC.sub.2 H.sub.5 4-Cl O n.sub.D.sup.20 1.5744 353 CH.sub.3 CH.sub.3 H 4-OCF.sub.2 CHF.sub.2 H O n.sub.D.sup.20 1.5287 354 CH.sub.3 CH.sub.3 C.sub.2 H.sub.5 4-OCF.sub.2 CHF.sub.2 H O n.sub.D.sup.20 1.5252 355 CH.sub.3 CH.sub.3 H 4-OCF.sub.2 CHF.sub.2 2-F O n.sub.D.sup.20 1.5130 356 CH.sub.3 CH.sub.3 H 4-OCF.sub.2 CHF.sub.2 4-F O n.sub.D.sup.20 1.5242 357 CH.sub.3 CH.sub.3 H 4-OCF.sub.2 CHF.sub.2 4-Cl O m.p. 83.8 358 CH.sub.3 CH.sub.3 H 4-OCF.sub.2 CHF.sub.2 4-OCH.sub.3 O n.sub.D.sup.20 1.5300 359 CH.sub.3 CH.sub.3 H 4-OC.sub.3 H.sub.7i H O n.sub.D.sup.20 1.5686 360 CH.sub.3 CH.sub.3 H 4-OC.sub.3 H.sub.7i 4-F O n.sub.D.sup.20 1.5665 361 CH.sub.3 CH.sub.3 H 4-OC.sub.3 H.sub.7i 4-Cl O n.sub.D.sup.20 1.5689 362 CH.sub.3 CH.sub.3 H 4-OC.sub.3 H.sub.9i 4-OCH.sub.3 O n.sub.D.sup.20 1.5642 363 CH.sub.3 CH.sub.3 H 4-OC.sub.4 H.sub.9t H O n.sub.D.sup.20 1.5562 364 CH.sub.3 CH.sub.3 H 4-OC.sub.4 H.sub.9t 4-F O n.sub.D.sup.20 1.5682 365 CH.sub.3 CH.sub.3 H 4-OC.sub.4 H.sub.9t 4-Cl O m.p. 89.4 366 CH.sub.3 CH.sub.3 H 4-OC.sub.4 H.sub.9t 4-OCH.sub.3 O n.sub.D.sup.20 1.5663 367 CH.sub.3 CH.sub.3 H ##STR76## H O n.sub.D.sup.20 1.5896 368 CH.sub.3 CH.sub.3 H ##STR77## 2,4-Cl.sub.2 O n.sub.D.sup.20 1.5586 369 CH.sub.3 CH.sub.3 H ##STR78## H O n.sub.D.sup.20 1.5945 370 CH.sub. 3 CH.sub.3 H ##STR79## 4-F O n.sub.D.sup.20 1.5852 371 CH.sub.3 CH.sub.3 H ##STR80## 4-Cl O n.sub.D.sup.20 1.5921 372 CH.sub.3 CH.sub.3 H ##STR81## H O n.sub.D.sup.20 1.5640 373 CH.sub.3 CH.sub.3 H 3,4(OCH.sub.2 O) H O n.sub.D.sup.20 1.5850 374 CH.sub.3 CH.sub.3 H 3,4(OCH.sub.2 O) 4-F O n.sub.D.sup.20 1.5750 375 CH.sub.3 CH.sub.3 H 3,4(OCH.sub.2 O) 4-Cl O n.sub.D.sup.20 1.5867 376 CH.sub.3 CH.sub.3 H ##STR82## H O n.sub.D.sup.20 1.5505 377 CH.sub.3 CH.sub.3 H ##STR83## H O n.sub.D.sup.20 1.5447 378 CH.sub.3 CH.sub.3 H ##STR84## 4-F O n.sub. D.sup.20 1.5560 379 CH.sub.3 CH.sub.3 H ##STR85## 4-Cl O n.sub.D.sup.20 1.5600 380 CH.sub.3 CH.sub.3 H ##STR86## 4-OCH.sub.3 O n.sub.D.sup.20 1.5431 381 CH.sub.3 CH.sub.3 H ##STR87## 4-OCH.sub.3 O n.sub.D.sup.20 1.5480 382 CH.sub.3 CH.sub.3 H ##STR88## H O n.sub.D.sup.20 1.5408 383 CH.sub.3 CH.sub.3 H ##STR89## 4-F O n.sub.D.sup.20 1.5300 384 CH.sub.3 CH.sub.3 H ##STR90## 4-OCH.sub.3 O n.sub.D.sup.20 1.5380 385 CH.sub.3 CH.sub.3 H ##STR91## H O n.sub.D.sup.20 1.5448 386 CH.sub.3 CH.sub.3 H ##STR92## H O n.sub.D.sup.20 1.5553 387 CH.sub.3 CH.sub.3 H ##STR93## H O n.sub.D.sup.20 1.5522 388 CH.sub.3 CH.sub.3 H ##STR94## H O n.sub.D.sup.20 1.5565 389 CH.sub.3 CH.sub.3 H ##STR95## H O n.sub.D.sup.20 1.5423 390 CH.sub.3 CH.sub.3 H 4-SCH.sub.3 H O m.p. 81.8 391 CH.sub.3 CH.sub.3 H 4-SCH.sub.3 4-F O n.sub.D.sup.20 1.5930 392 CH.sub.3 CH.sub.3 H 4-SCH.sub.3 4-Cl O n.sub.D.sup.20 1.5955 393 CH.sub.3 CH.sub.3 H 4-SCH.sub.3 4-OCH.sub.3 O n.sub.D.sup.20 1.5995 394 CH.sub.3 CH.sub.3 H 4-SOCH.sub.3 H O n.sub.D.sup.20 1.5865 395 CH.sub.3 CH.sub.3 H 4-SOCH.sub.3 4-F O n.sub.D.sup.20 1.5700 396 CH.sub.3 CH.sub.3 H 4-SOCH.sub.3 4-Cl O n.sub.D.sup.20 1.5908 397 CH.sub.3 CH.sub.3 H 4-SOCH.sub.3 4-OCH.sub.3 O n.sub.D.sup.20 1.5864 398 CH.sub.3 CH.sub.3 H 4-SO.sub.2 CH.sub.3 H O n.sub.D.sup.20 1.5745 399 CH.sub.3 CH.sub.3 H 4-SO.sub.2 CH.sub.3 4-F O n.sub.D.sup.20 1.5658 400 CH.sub.3 CH.sub.3 H 4-SO.sub.2 CH.sub.3 4-Cl O n.sub.D.sup.20 1.5672 401 CH.sub.3 CH.sub.3 H 4-SO.sub.2 CH.sub.3 4-OCH.sub.3 O n.sub.D.sup.20 1.5866 402 CH.sub.3 CH.sub.3 H 4-SC.sub.2 H.sub.5 H O n.sub.D.sup.20 1.6026 403 CH.sub.3 CH.sub.3 H 4-SC.sub.2 H.sub.5 4-F O n.sub.D.sup.20 1.5940 404 CH.sub.3 CH.sub.3 H 4-SOC.sub.2 H.sub.5 H O n.sub.D.sup.20 1.5899 405 CH.sub.3 CH.sub.3 H 4-SOC.sub.2 H.sub.5 4-F O n.sub.D.sup.20 1.5740 406 CH.sub.3 CH.sub.3 H 4-SO.sub.2 C.sub.2 H.sub.5 H O m.p. 118.9 407 CH.sub.3 CH.sub.3 H 4-SO.sub.2 C.sub.2 H.sub.5 4-F O n.sub.D.sup.20 1.5891 408 CH.sub.3 CH.sub.3 H 2-SC.sub.3 H.sub.7i, 5-CH.sub.3 H O n.sub.D.sup.20 1.5830 409 CH.sub.3 CH.sub.3 H 4-SC.sub.3 H.sub.7i H O n.sub.D.sup.20 1.5902 410 CH.sub.3 CH.sub.3 H 2-SC.sub.3 H.sub.7i H O n.sub.D.sup.20 1.5872 411 CH.sub.3 CH.sub.3 H 4-SC.sub.3 H.sub.7i 4-F O n.sub.D.sup.20 1.5752 412 CH.sub.3 CH.sub.3 H 4-SC.sub.3 H.sub.7i 4-Cl O n.sub.D.sup.20 1.5928 413 CH.sub.3 CH.sub.3 H 4-SC.sub.3 H.sub.7i 4-OCH.sub.3 O n.sub.D.sup.20 1.5862 414 CH.sub.3 CH.sub.3 H 4-SOC.sub.3 H.sub.7i H O n.sub.D.sup.20 1.5802 415 CH.sub.3 CH.sub.3 H 4-SOC.sub.3 H.sub.7i 4-F O n.sub.D.sup.20 1.5669 416 CH.sub.3 CH.sub.3 H 4-SOC.sub.3 H.sub.7i 4-Cl O n.sub.D.sup.20 1.5810 417 CH.sub.3 CH.sub.3 H 4-SOC.sub.3 H.sub.7i 4-OCH.sub.3 O n.sub.D.sup.20 1.5748 418 CH.sub.3 CH.sub.3 H 4-SO.sub.2 C.sub.3 H.sub.7i H O n.sub.D.sup.20 1.5626 419 CH.sub.3 CH.sub.3 H 4-SO.sub.2 C.sub.3 H.sub.7i 4-F O n.sub.D.sup.20 1.5594 420 CH.sub.3 CH.sub.3 H 4-SO.sub.2 C.sub.3 H.sub.7i 4-OCH.sub.3 O n.sub.D.sup.20 1.5652 421 CH.sub.3 CH.sub.3 H 4-SC.sub.4 H.sub.9t H O n.sub.D.sup.20 1.5853 422 CH.sub.3 CH.sub.3 H 4-SCHF.sub.2 H O n.sub.D.sup.20 1.5733 423 CH.sub.3 CH.sub.3 H 4-SCHF.sub .2 H S n.sub.D.sup.20 1.6056 424 CH.sub.3 CH.sub.3 CH.sub.3 4-SCHF.sub.2 H O n.sub.D.sup.20 1.5482 425 C.sub.2 H.sub.5 CH.sub.3 H 4-SCHF.sub.2 H O n.sub.D.sup.20 1.5659 426 CH.sub.3 CH.sub.3 ##STR96## 4-SCHF.sub.2 H O n.sub.D.sup.20 1.5917 427 CH.sub.3 CH.sub.3 H 4-SCHF.sub.2 2-CH.sub.3 O n.sub.D.sup.20 1.5715 428 CH.sub.3 CH.sub.3 H 4-SCHF.sub.2 3-CH.sub.3 O n.sub.D.sup.20 1.5741 429 CH.sub.3 CH.sub.3 H 4-SCHF.sub.2 4-CH.sub.3 O n.sub.D.sup.20 1.5780 430 CH.sub.3 CH.sub.3 H 4-SCHF.sub.2 4-C.sub.4 H.sub.9t O n.sub.D.sup.20 1.5569 431 CH.sub.3 CH.sub.3 H 4-SCHF.sub.2 4-F O n.sub.D.sup.20 1.5679 432 CH.sub.3 CH.sub.3 H 4-SCHF.sub.2 2-Cl O n.sub.D.sup.20 1.5750 433 CH.sub.3 CH.sub.3 H 4-SCHF.sub.2 3-Cl O n.sub.D.sup.20 1.5721 434 CH.sub.3 CH.sub.3 H 4-SCHF.sub.2 4-Cl O n.sub.D.sup.20 1.5395 435 CH.sub.3 CH.sub.3 H 4-SCHF.sub.2 3,4-Cl.sub.2 O n.sub.D.sup.20 1.5852 436 CH.sub.3 CH.sub.3 H 4-SCHF.sub.2 4-Br O n.sub.D.sup.20 1.5855 437 CH.sub.3 CH.sub.3 H 4-SCHF.sub.2 4-OCH.sub.3 O n.sub.D.sup.20 1.5694 438 CH.sub.3 CH.sub.3 H 4-SOCHF.sub.2 H O n.sub.D.sup.20 1.5575 439 CH.sub.3 CH.sub.3 H 4-SOCHF.sub.2 4-F O Paste 440 CH.sub.3 CH.sub.3 H 4-SOCHF.sub. 2 4-Cl O n.sub.D.sup.20 1.5748 441 CH.sub.3 CH.sub.3 H 4-SOCHF.sub.2 4-Br O n.sub.D.sup.20 1.5768 442 CH.sub.3 CH.sub.3 H 4-SOCHF.sub.2 4-OCH.sub.3 O n.sub.D.sup.20 1.5704 443 CH.sub.3 CH.sub.3 H 4-SO.sub.2 CHF.sub.2 H O n.sub.D.sup.20 1.5765 444 CH.sub.3 CH.sub.3 H 4-SO.sub. 2 CHF.sub.2 4-F O n.sub.D.sup.20 1.5500 445 CH.sub.3 CH.sub.3 H 4-SO.sub.2 CHF.sub.2 4-Cl O n.sub.D.sup.20 1.5612 446 CH.sub.3 CH.sub.3 H 4-SO.sub.2 CHF.sub.2 4-Br O n.sub.D.sup.20 1.5643 447 CH.sub.3 CH.sub.3 H 4-SO.sub.2 CHF.sub.2 4-OCH.sub.3 O n.sub.D.sup.20 1.5597 448 CH.sub.3 CH.sub.3 H 4-SCF.sub.2 Br H O n.sub.D.sup.20 1.5801 449 CH.sub.3 CH.sub.3 H 4-SCF.sub.2 Br 4-F O m.p. 82.3 450 CH.sub.3 CH.sub.3 H 4-SCF.sub.2 CFCl.sub.2 H O n.sub.D.sup.20 1.5557 451 CH.sub.3 CH.sub.3 H 4-SCF.sub.2 CFCl.sub.2 4-F O n.sub.D.sup.20 1.5557 452 CH.sub.3 CH.sub.3 H 4-SCF.sub. 2 CFCl.sub.2 4-Cl O n.sub.D.sup.20 1.5676 453 CH.sub.3 CH.sub.3 H 4-SCF.sub.2 CFCl.sub.2 4-OCH.sub.3 O n.sub.D.sup.20 1.5640 454 CH.sub.3 CH.sub.3 H 4-SOCF.sub.2 CFCl.sub.2 H O n.sub.D.sup.20 1.5889 455 CH.sub.3 CH.sub.3 H 4-SO.sub.2 CF.sub.2 CFCl.sub.2 H O n.sub.D.sup.20 1.5958 456 CH.sub.3 CH.sub. 3 H 4-SCH.sub.2 CF.sub.3 H O n.sub.D.sup.20 1.5722 457 CH.sub.3 CH.sub.3 H 4-SCH.sub.2 CF.sub.3 4-F O n.sub.D.sup.20 1.5569 458 CH.sub.3 CH.sub.3 H 4-SCH.sub.2 CF.sub.3 4-Cl O n.sub.D.sup.20 1.5732 459 CH.sub.3 CH.sub.3 H 4-SCH.sub. 2 CF.sub.3 4-OCH.sub.3 O n.sub.D.sup.20 1.5568 460 CH.sub.3 CH.sub.3 H 4-SOCH.sub.2 CF.sub.3 4-F O n.sub.D.sup.20 1.5501 461 CH.sub.3 CH.sub.3 H 4-SOCH.sub.2 CF.sub.3 4-Cl O n.sub.D.sup.20 1.5620 462 CH.sub.3 CH.sub.3 H 4-SOCH.sub.2 CF.sub.3 4-OCH.sub.3 O n.sub.D.sup.20 1.5518 463 CH.sub.3 CH.sub.3 H 4-SO.sub.2 CH.sub.2 CF.sub.3 4-F O n.sub.D.sup.20 1.5449 464 CH.sub.3 CH.sub.3 H 4-SO.sub.2 CH.sub.2 CF.sub.3 4-Cl O n.sub.D.sup.20 1.5497 465 CH.sub.3 CH.sub.3 H 4-SCF.sub.2 CHF.sub.2 H O n.sub.D.sup.20 1.5527 466 CH.sub.3 CH.sub.3 CH.sub.3 4-SCF.sub.2 CHF.sub.2 H O n.sub.D.sup.20 1.5514 467 CH.sub.3 CH.sub.3 H 4-SCF.sub.2 CHF.sub. 2 2-F O n.sub.D.sup.20 1.5462 468 CH.sub.3 CH.sub.3 H 4-SCF.sub. 2 CHF.sub.2 3-F O n.sub.D.sup.20 1.5450 469 CH.sub.3 CH.sub.3 H 4-SCF.sub. 2 CHF.sub.2 4-F O n.sub.D.sup.20 1.5536 470 CH.sub.3 CH.sub.3 H 4-SCF.sub. 2 CHF.sub.2 2-Cl O n.sub.D.sup.20 1.5540 471 CH.sub.3 CH.sub.3 H 4-SCF.sub.2 CHF.sub.2 4-Cl O n.sub.D.sup.20 1.5636 472 CH.sub.3 CH.sub.3 H 4-SCF.sub.2 CHF.sub.2 2-OCH.sub.3 O n.sub.D.sup.20 1.5547 473 CH.sub.3 CH.sub.3 H 4-SCF.sub.2 CHF.sub.2 3-OCH.sub.3 O n.sub.D.sup.20 1.5541 474 CH.sub.3 CH.sub.3 H 4-SCF.sub.2 CHF.sub.2 4-OCH.sub.3 O n.sub.D.sup.20 1.5645 475 CH.sub.3 CH.sub.3 H 4-SCF.sub.2 CHF.sub.2 3,5-(OCH.sub.3).sub.2 O n.sub.D.sup.20 1.5477 476 CH.sub.3 CH.sub.3 H 4-SOCF.sub.2 CHF.sub.2 H O n.sub.D.sup.20 1.5865 477 CH.sub.3 CH.sub.3 H 4-SOCF.sub.2 CHF.sub.2 4-F O n.sub.D.sup.20 1.5684 478 CH.sub.3 CH.sub.3 H 4-SOCF.sub.2 CHF.sub.2 4-Cl O n.sub.D.sup.20 1.5498 479 CH.sub.3 CH.sub.3 H 4-SOCF.sub.2 CHF.sub.2 4-OCH.sub.3 O n.sub.D.sup.20 1.5786 480 CH.sub.3 CH.sub.3 H 4-SO.sub.2 CF.sub.2 CHF.sub.2 4-F O Paste 481 CH.sub.3 CH.sub.3 H 4-SO.sub.2 CF.sub.2 CHF.sub.2 H O Paste 482 CH.sub.3 CH.sub.3 H 4-SO.sub.2 CF.sub.2 CHF.sub.2 4-Cl O n.sub.D.sup.20 1.5420 483 CH.sub.3 CH.sub.3 H 4-SO.sub.2 CF.sub.2 CHF.sub.2 4-OCH.sub.3 O n.sub.D.sup.20 1.5890 484 CH.sub.3 CH.sub.3 H 4-SCF.sub.2 CF.sub.2 Br H O n.sub.D.sup.20 1.5632 485 CH.sub.3 CH.sub.3 H 4-SCF.sub.2 CF.sub.2 Br 4-F O n.sub.D.sup.20 1.5585 486 CH.sub.3 CH.sub.3 H 4-SCF.sub.2 CF.sub.2 Br 4-Cl O n.sub.D.sup.20 1.5655 487 CH.sub.3 CH.sub.3 H 4-SCF.sub.2 CF.sub.2 Br 4-OCH.sub.3 O n.sub.D.sup.20 1.5622 488 CH.sub.3 CH.sub.3 H 4-SOCF.sub.2 CF.sub.2 Br H O n.sub.D.sup.20 1.5680 489 CH.sub.3 CH.sub.3 H 4-SOCF.sub.2 CF.sub.2 Br 4-F O n.sub.D.sup.20 1.5503 490 CH.sub.3 CH.sub.3 H 4-SO.sub.2 CF.sub.2 CF.sub.2 Br 4-F O n.sub.D.sup.20 1.5686 491 CH.sub.3 CH.sub.3 H 4-SOCF.sub.2 CF.sub.2 Br 4-Cl O n.sub.D.sup.20 1.5611 492 CH.sub.3 CH.sub.3 H 4-SOCF.sub.2 CF.sub.2 Br 4-OCH.sub.3 O n.sub.D.sup.20 1.5588 493 CH.sub.3 CH.sub.3 H 4-SC.sub.3 F.sub.7 H O n.sub.D.sup.20 1.5250 494 CH.sub.3 CH.sub.3 CH.sub.3 4-SC.sub.3 F.sub.7 H O n.sub.D.sup.20 1.5217 495 CH.sub.3 CH.sub.3 H 4-SC.sub.3 F.sub.7 4-CH.sub.3 O n.sub.D.sup.20 1.5228 496 CH.sub.3 CH.sub.3 H 4-SC.sub.3 F.sub.7 3-F O n.sub.D.sup.20 1.5172 497 CH.sub.3 CH.sub.3 H 4-SC.sub.3 F.sub.7 4-F O n.sub.D.sup.20 1.5175 498 CH.sub.3 CH.sub.3 H 4-SC.sub.3 F.sub.7 3-Cl O n.sub.D.sup.20 1.5298 499 CH.sub.3 CH.sub.3 H 4-SC.sub.3 F.sub.7 4-Cl O Paste 500 CH.sub.3 CH.sub.3 H 4-SC.sub.3 F.sub.7 3-CF.sub.3 O n.sub.D.sup.20 1.5020 501 CH.sub.3 CH.sub.3 H 4-SC.sub.3 F.sub.7 3-OCH.sub.3 O n.sub.D.sup.20 1.5263 502 CH.sub.3 CH.sub.3 H 4-SC.sub.3 F.sub.7 4-OCH.sub.3 O n.sub.D.sup.20 1.5137 503 CH.sub.3 CH.sub.3 H 4-SOC.sub.3 F.sub.7 H O n.sub.D.sup.20 1.5289 504 CH.sub.3 CH.sub.3 H 4-SOC.sub.3 F.sub.7 4-F O Paste 505 CH.sub.3 CH.sub.3 H 4-SOC.sub.3 F.sub.7 4-F O Paste 506 CH.sub.3 CH.sub.3 H ##STR97## H O n.sub.D.sup.20 1.6134 507 CH.sub.3 CH.sub.3 H ##STR98## H O n.sub.D.sup.20 1.5980 508 CH.sub.3 CH.sub.3 H ##STR99## H O n.sub.D.sup.20 1.5940 509 CH.sub.3 CH.sub.3 H 4-Cl 4-Cl O n.sub.D.sup.20 1.6052 510 CH.sub.3 CH.sub.3 H 4-SOCHF.sub.2 4-Cl O n.sub.D.sup.20 1.5643 511 CH.sub.3 CH.sub.3 H 4-SCF.sub.3 H O n.sub.D.sup.20 1.5320 512 CH.sub.3 CH.sub.3 H 4-SOCF.sub.3 H O n.sub.D.sup.20 1.5324 513 CH.sub.3 CH.sub. 3 H 4-SO.sub. 2 CF.sub.3 H O n.sub.D.sup.20 1.5876 514 CH.sub.3 CH.sub.3 H 4-SC.sub.3 F.sub.7 4-OCHF.sub.2 O n.sub.D.sup.20 1.5235 515 CH.sub.3 CH.sub.3 H 4-SC.sub.3 F.sub.7 4-OCF.sub.3 O n.sub.D.sup.20 1.5201 516 CH.sub.3 CH.sub.3 H 4-COSC.sub.2 H.sub.5 H O n.sub.D.sup.20 1.5889 517 CH.sub.3 CH.sub.3 H 4-COSC.sub.3 H.sub.7i H O n.sub.D.sup.20 1.5812 518 CH.sub.3 CH.sub.3 H 4-COSC.sub.4 H.sub.9t H O n.sub.D.sup.20 1.5896 519 CH.sub.3 CH.sub.3 H 4-CONHCH.sub.3 H O Crystal 520 CH.sub.3 CH.sub.3 H 4-CONHCH.su b.3 4-F O n.sub.D.sup.20 1.5576 521 CH.sub.3 CH.sub.3 H 4-CONHC.sub.3 H.sub.7i H O m.p. 94.4 522 CH.sub.3 CH.sub.3 H 4-CONHC.sub.3 H.sub.7i 4-F O m.p. 136.4 523 CH.sub.3 CH.sub.3 H 4-CONHC.sub.4 H.sub.9t H O m.p. 106.7 524 CH.sub.3 CH.sub.3 H 4-CONHC.sub.4 H.sub.9t 4-F O n.sub.D.sup.20 1.5582 525 CH.sub.3 CH.sub.3 H 4-CONHC.sub .4 H.sub.9t 4-OCH.sub.3 O n.sub.D.sup.20 1.5662 526 CH.sub.3 CH.sub.3 H 4-CON(CH.sub.3).sub.2 H O n.sub.D.sup.20 1.5808 527 CH.sub.3 CH.sub.3 H 4-CON(C.sub.3 H.sub.7i).sub.2 H O n.sub.D.sup.20 1.5263 528 CH.sub.3 CH.sub.3 H 4-CON(C.sub.3 H.sub.7i).sub.2 4-F O n.sub.D.sup.20 1.5245 529 CH.sub.3 CH.sub.3 H 4-CON(C.sub.3 H.sub.7i).sub.2 4-Cl O n.sub.D.sup.20 1.5326 530 CH.sub.3 CH.sub.3 H 4-CON(C.sub.3 H.sub.7i).sub.2 4-OCH.sub.3 O n.sub.D.sup.20 1.5328 531 CH.sub.3 CH.sub.3 H ##STR100## H O n.sub.D.sup.20 1.5803 532 CH.sub.3 CH.sub.3 H ##STR101## H O n.sub.D.sup.20 1.5689 533 CH.sub.3 CH.sub.3 H ##STR102## 4-F O n.sub.D.sup.20 1.5755 534 CH.sub.3 CH.sub.3 H ##STR103## 4-Cl O n.sub.D.sup.20 1.5657 535 CH.sub.3 CH.sub.3 H ##STR104## 4-OCH.sub.3 O Paste 536 CH.sub.3 CH.sub.3 H ##STR105## H O n.sub.D.sup.20 1.5632 537 CH.sub.3 CH.sub.3 H ##STR106## 4-F O n.sub.D.sup.20 1.5600 538 CH.sub.3 CH.sub.3 H ##STR107## 4-OCH.sub.3 O n.sub.D.sup.20 1.5498 539 CH.sub.3 CH.sub.3 H ##STR108## H O n.sub.D.sup.20 1.5617 540 CH.sub.3 CH.sub.3 H ##STR109## 4-F O n 1.5643 541 CH.sub.3 CH.sub.3 H 4-COCH.sub.3 H O m.p. 88.0 542 CH.sub.3 CH.sub.3 H 4-COCOOC.sub.2 H.sub.5 H O n.sub.D.sup.20 1.5709 543 CH.sub.3 CH.sub.3 H 4-COCOOC.sub.3 H.sub.7i H O n.sub.D.sup.20 1.5756 544 CH.sub.3 CH.sub.3 H 4-COC.sub.2 H.sub.5 H O m.p. 59.0 545 CH.sub.3 CH.sub.3 H 4-COC.sub.2 H.sub.5 4-F O n.sub.D.sup.20 1.5664 546 CH.sub.3 CH.sub.3 H 4-COC.sub.3 H.sub.7i H O n.sub.D.sup.20 1.5705 547 CH.sub.3 CH.sub.3 H 4-COC.sub.4 H.sub.9t H O n.sub.D.sup.20 1.5853 548 CH.sub.3 CH.sub.3 H 4-COC.sub.4 H.sub.9t 4-F O n.sub.D.sup.20 1.5567 549 CH.sub.3 CH.sub.3 H 4-COC.sub.4 H.sub.9t 4-Cl O n.sub.D.sup.20 1.5896 550 CH.sub.3 CH.sub.3 H ##STR110## H O n.sub.D.sup.20 1.5865 551 CH.sub.3 CH.sub.3 H ##STR111## H O n.sub.D.sup.20 1.5630 552 CH.sub.3 CH.sub.3 H ##STR112## H O n.sub.D.sup.20 1.5941 553 CH.sub.3 CH.sub.3 H ##STR113## 4-Cl O n.sub.D.sup.20 1.5850 554 CH.sub.3 CH.sub.3 H ##STR114## H O n.sub.D.sup.20 1.5952 555 CH.sub.3 CH.sub.3 H ##STR115## 4-F O n.sub.D.sup.20 1.5935 556 CH.sub.3 CH.sub.3 H ##STR116## 4-Cl O n.sub.D.sup.20 1.5967 557 CH.sub.3 CH.sub.3 H ##STR117## 4-OCH.sub.3 O n.sub.D.sup.20 1.5937 558 CH.sub.3 CH.sub.3 H ##STR118## H O n.sub.D.sup.20 1.5764 559 CH.sub.3 CH.sub.3 H ##STR119## 4-F O n.sub.D.sup.20 1.5643 560 CH.sub.3 CH.sub.3 H ##STR120## 4-Cl O n.sub.D.sup.20 1.5830 561 CH.sub.3 CH.sub.3 H ##STR121## 4-OCH.sub.3 O n.sub.D.sup.20 1.5782 562 CH.sub.3 CH.sub.3 H ##STR122## H O n.sub.D.sup.20 1.5698 563 CH.sub.3 CH.sub.3 H ##STR123## 4-F O n.sub.D.sup.20 1.5555 564 CH.sub.3 CH.sub.3 H ##STR124## 4-Cl O n.sub.D.sup.20 1.5569 565 CH.sub.3 CH.sub.3 H ##STR125## H O n.sub.D.sup.20 1.5619 566 CH.sub.3 CH.sub.3 H ##STR126## 4-F O Paste 567 CH.sub.3 CH.sub.3 H ##STR127## 4-Cl O n.sub.D.sup.20 1.5689 568 CH.sub.3 CH.sub.3 H ##STR128## 4-OCH.sub.3 O n.sub.D.sup.20 1.5593 569 CH.sub.3 CH.sub.3 H ##STR129## H O n.sub.D.sup.20 1.5630 570 CH.sub.3 CH.sub.3 H ##STR130## 4-F O n.sub.D.sup.20 1.5472 571 CH.sub.3 CH.sub.3 H ##STR131## 4-OCH.sub.3 O n.sub.D.sup.20 1.5623 572 CH.sub.3 CH.sub.3 H ##STR132## H O n.sub.D.sup.20 1.5560 573 CH.sub.3 CH.sub.3 H ##STR133## H O n.sub.D.sup.20 1.5526 574 CH.sub.3 CH.sub.3 H ##STR134## 4-F O n.sub.D.sup.20 1.5656 575 CH.sub.3 CH.sub.3 H ##STR135## 4-OCH.sub.3 O n.sub.D.sup.20 1.5123 576 CH.sub.3 CH.sub.3 H ##STR136## H O n.sub.D.sup.20 1.6188 577 CH.sub.3 CH.sub.3 H ##STR137## H O n.sub.D.sup.20 1.6089 578 CH.sub.3 CH.sub.3 H ##STR138## 4-F O n.sub.D.sup.20 1.5978 579 CH.sub.3 CH.sub.3 H ##STR139## H O n.sub.D.sup.20 1.5831 580 CH.sub.3 CH.sub.3 H ##STR140## H O n.sub.D.sup.20 1.5952 581 CH.sub.3 CH.sub.3 H ##STR141## H O Paste 582 CH.sub.3 CH.sub.3 H ##STR142## H O n.sub.D.sup.20 1.5665 583 CH.sub.3 CH.sub.3 H ##STR143## H O n.sub.D.sup.20 1.5685 584 CH.sub.3 CH.sub.3 H ##STR144## H O n.sub.D.sup.20 1.5748 585 CH.sub.3 CH.sub.3 H ##STR145## H O n.sub.D.sup.20 1.5623 586 CH.sub.3 CH.sub.3 H ##STR146## H O n.sub.D.sup.20 1.5682 587 CH.sub.3 CH.sub.3 H ##STR147## H O n.sub.D.sup.20 1.5768 588 CH.sub.3 CH.sub.3 H ##STR148## H O n.sub.D.sup.20 1.5620 589 CH.sub.3 CH.sub.3 H ##STR149## H O m.p. 105.3 590 CH.sub.3 CH.sub.3 H ##STR150## H O n.sub.D.sup.20 1.5808 591 CH.sub.3 CH.sub.3 H ##STR151## H O n.sub.D.sup.20 1.5705 592 CH.sub.3 CH.sub.3 H ##STR152## 4-F O n.sub.D.sup.20 1.5621 593 CH.sub.3 CH.sub.3 H ##STR153## 4-OCH.sub.3 O n.sub.D.sup.20 1.5659 594 CH.sub.3 CH.sub.3 H ##STR154## H O m.p. 115.2 595 CH.sub.3 CH.sub.3 H ##STR155## 4-F O n.sub.D.sup.20 1.5645 596 CH.sub.3 CH.sub.3 H ##STR156## H O Paste 597 CH.sub.3 CH.sub.3 H ##STR157## 4-F O n.sub.D.sup.20 1.5561 598 CH.sub.3 CH.sub.3 H ##STR158## 4-OCH.sub.3 O n.sub.D.sup.20 1.5599 599 CH.sub.3 CH.sub.3 H ##STR159## H O n.sub.D.sup.20 1.5764 600 CH.sub.3 CH.sub.3 H ##STR160## 4-F O n.sub.D.sup.20 1.5685 601 CH.sub.3 CH.sub.3 H ##STR161## 4-OCH.sub.3 O n.sub.D.sup.20 1.5723 602 CH.sub.3 CH.sub.3 H ##STR162## H O Paste 603 CH.sub.3 CH.sub.3 H ##STR163## 4-F O Paste 604 CH.sub.3 CH.sub.3 H ##STR164## H O n.sub.D.sup.20 1.5683 605 CH.sub.3 CH.sub.3 H ##STR165## H O n.sub.D.sup.20 1.5662 606 CH.sub.3 CH.sub.3 H ##STR166## 4-F O n.sub.D.sup.20 1.5582 607 CH.sub.3 CH.sub.3 H ##STR167## 4-OCH.sub.3 O n.sub.D.sup.20 1.5625 608 CH.sub.3 CH.sub.3 H ##STR168## H O n.sub.D.sup.20 1.5564 609 CH.sub.3 CH.sub.3 H ##STR169## 4-F O n.sub.D.sup.20 1.5559 610 CH.sub.3 CH.sub.3 H ##STR170## 4-Cl O n.sub.D.sup.20 1.5595 611 CH.sub.3 CH.sub.3 H ##STR171## 4-OCH.sub.3 O n.sub.D.sup.20 1.5557 612 CH.sub.3 CH.sub.3 H ##STR172## H O n.sub.D.sup.20 1.5648 613 CH.sub.3 CH.sub.3 H ##STR173## 4-F O n.sub.D.sup.20 1.5529 614 CH.sub.3 CH.sub.3 H ##STR174## H O n.sub.D.sup.20 1.5582 615 CH.sub.3 CH.sub.3 H ##STR175## 4-F O n.sub.D.sup.20 1.5421 616 CH.sub.3 CH.sub.3 H ##STR176## 4-Cl O n.sub.D.sup.20 1.5573 617 CH.sub.3 CH.sub.3 H ##STR177## 4-OCH.sub.3 O n.sub.D.sup.20 1.5538 618 CH.sub.3 CH.sub.3 H ##STR178## 3,4(OCH.sub.2 O) O n.sub.D.sup.20 1.5621 619 CH.sub.3 CH.sub.3 H ##STR179## H O n.sub.D.sup.20 1.5638 620 CH.sub.3 CH.sub.3 H ##STR180## 4-F O Paste 621 CH.sub.3 CH.sub.3 H ##STR181## 4-OCH.sub.3 O n.sub.D.sup.20 1.5656 622 CH.sub.3 CH.sub.3 CH.sub.3 ##STR182## H O m.p. 83.4 623 CH.sub.3 CH.sub.3 H ##STR183## H O n.sub.D.sup.20 1.5706 624 CH.sub.3 CH.sub.3 H ##STR184## 4-F O Paste 625 CH.sub.3 CH.sub.3 H ##STR185## 4-OCH.sub.3 O n.sub.D.sup.20 1.5695 626 CH.sub.3 CH.sub.3 H ##STR186## H O n.sub.D.sup.20 1.5605 627 CH.sub.3 CH.sub.3 H ##STR187## 4-F O n.sub.D.sup.20 1.5532 628 CH.sub.3 CH.sub.3 H ##STR188## 4-OCH.sub.3 O n.sub.D.sup.20 1.5602 629 CH.sub.3 CH.sub.3 H ##STR189## H O n.sub.D.sup.20 1.5549 630 CH.sub.3 CH.sub.3 H ##STR190## 4-F O n.sub.D.sup.20 1.5448 631 CH.sub.3 CH.sub.3 H ##STR191## 4-OCH.sub.3 O n.sub.D.sup.20 1.5513 632 CH.sub.3 CH.sub.3 H ##STR192## H O n.sub.D.sup.20 1.5689 633 CH.sub.3 CH.sub.3 H ##STR193## 4-F O n.sub.D.sup.20 1.5701 634 CH.sub.3 CH.sub.3 H ##STR194## H O n.sub.D.sup.20 1.5481 635 CH.sub.3 CH.sub.3 H ##STR195## 4-F O n.sub.D.sup.20 1.5415 636 CH.sub.3 CH.sub.3 H ##STR196## H O m.p. 73.3 637 CH.sub.3 CH.sub.3 H ##STR197## 4-F O n.sub.D.sup.20 1.5685 638 CH.sub.3 CH.sub.3 H ##STR198## 4-OCH.sub.3 O n.sub.D.sup.20 1.5710 639 CH.sub.3 CH.sub.3 H ##STR199## H O n.sub.D.sup.20 1.5520 640 CH.sub.3 CH.sub.3 H ##STR200## 4-F O Paste 641 CH.sub.3 CH.sub.3 H ##STR201## 4-OCH.sub.3 O n.sub.D.sup.20 1.5610 642 CH.sub.3 CH.sub.3 H ##STR202## H O n.sub.D.sup.20 1.5516 643 CH.sub. 3 CH.sub.3 H ##STR203## 4-F O n.sub.D.sup.20 1.5489 644 CH.sub.3 CH.sub.3 H ##STR204## 4-OCH.sub.3 O n.sub.D.sup.20 1.5542 645 CH.sub.3 CH.sub.3 H ##STR205## H O n.sub.D.sup.20 1.5545 646 CH.sub.3 CH.sub.3 H ##STR206## 4-F O n.sub.D.sup.20 1.5448 647 CH.sub.3 CH.sub.3 H ##STR207## H O Paste 648 CH.sub.3 CH.sub.3 H ##STR208## H O m.p. 85.0 649 CH.sub.3 CH.sub.3 H ##STR209## 4-F O Paste 650 CH.sub.3 CH.sub.3 H ##STR210## 4-OCH.sub.3 O n.sub.D.sup.20 1.5861 651 CH.sub.3 CH.sub.3 H ##STR211## H O m.p. 115.1 652 CH.sub.3 CH.sub.3 H ##STR212## 4-F O n.sub.D.sup.20 1.5718 653 CH.sub.3 CH.sub.3 H ##STR213## H O n.sub.D.sup.20 1.5730 654 CH.sub.3 CH.sub.3 H ##STR214## 4-F O n.sub.D.sup.20 1.5551 655 CH.sub.3 CH.sub.3 H ##STR215## 4-OCH.sub.3 O n.sub.D.sup.20 1.5660 656 CH.sub.3 CH.sub.3 H ##STR216## H O n.sub.D.sup.20 1.5718 657 CH.sub.3 CH.sub.3 H ##STR217## 4-F O n.sub.D.sup.20 1.5601
TABLE I(b)__________________________________________________________________________ ##STR218##This formula corresponds to the general formula (I) wherein Z.sup.1 is anoxygen atom. Physical propertyCompound m.p. (.degree.C.) orNo. R.sup.1 R.sup.2 R.sup.3 Q Z.sup.2 R.sup.4 Y.sub.m refractive__________________________________________________________________________ index658 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR219## H n.sub.D.sup.20 1.5657659 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR220## H n.sub.D.sup.20 1.5760660 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR221## H n.sub.D.sup.20 1.5683661 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR222## H n.sub.D.sup.20 1.5704662 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR223## 4-F n.sub.D.sup.20 1.5524663 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR224## H m.p. 63.4664 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR225## H n.sub.D.sup.20 1.5592665 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR226## 4-Cl n.sub.D.sup.20 1.5641666 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR227## 3-Cl n.sub.D.sup.20 1.5669667 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR228## 4-OCH.sub.3 n.sub.D.sup.20 1.5606668 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR229## H n.sub.D.sup.20 1.5509669 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR230## 3-OCH.sub.3 n.sub.D.sup.20 1.5459670 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR231## 4OCH.sub.3 m.p. 59.6671 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR232## 3-CF.sub. n.sub.D.sup.20 1.5287672 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR233## H n.sub.D.sup.20 1.5612673 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR234## 4-Cl n.sub.D.sup.20 1.5741674 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR235## H n.sub.D.sup.20 1.5618675 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR236## H n.sub.D.sup.20 1.5657676 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR237## 4-Cl m.p. 100.2677 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR238## H n.sub.D.sup.20 1.5552678 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR239## 4-Cl n.sub.D.sup.20 1.5738679 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR240## 3-Cl n.sub.D.sup.20 1.5730680 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR241## 4-OCH.sub.3 n.sub.D.sup.20 1.5681681 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR242## H m.p. 51.2682 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR243## H n.sub.D.sup.20 1.5722683 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR244## H n.sub.D.sup.20 1.5936684 CH.sub. 3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR245## 4-Cl n.sub.D.sup.20 1.5936685 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR246## 4-Cl m.p. 101.5686 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR247## H m.p. 86.1687 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR248## H n.sub.D.sup.20 1.5833688 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR249## 4-F m.p. 87.7689 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR250## 4-OCH.sub.3 n.sub.D.sup.20 1.5777690 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR251## H m.p. 58.6691 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR252## H n.sub.D.sup.20 1.5769692 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR253## 4-Cl n.sub.D.sup.20 1.5583693 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR254## 4-Cl m.p. 90.3694 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR255## 4-F n.sub.D.sup.20 1.5565695 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR256## 4-OCH.sub.3 m.p. 81.5696 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR257## H n.sub.D.sup.20 1.5682697 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR258## 4-F m.p. 53.0698 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR259## 4-OCH.sub.3 m.p. 103.6699 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR260## H n.sub.D.sup.20 1.5800700 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR261## H n.sub.D.sup.20 1.5901701 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR262## H n.sub.D.sup.20 1.5835702 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR263## H n.sub.D.sup.20 1.5742703 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR264## H n.sub.D.sup.20 1.5851704 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR265## H m.p. 60.6705 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR266## H m.p. 60.5706 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR267## H n.sub.D.sup.20 1.5577707 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR268## H n.sub.D.sup.20 1.5579708 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR269## 4-Cl n.sub.D.sup.20 1.5581709 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR270## H n.sub.D.sup.20 1.5632710 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR271## H n.sub.D.sup.20 1.5577711 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR272## H n.sub.D.sup.20 1.5555712 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR273## H n.sub.D.sup.20 1.5490713 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR274## H n.sub.D.sup.20 1.5616714 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR275## 4-Cl m.p. 92.5715 CH.sub.3 CH.sub. 3 H CH.sub.2 CH.sub.2 O ##STR276## 3-Cl n.sub.D.sup.20 1.5701716 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR277## 4-OCH.sub.3 n.sub.D.sup.20 1.5598717 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR278## H n.sub.D.sup.20 1.5813718 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR279## H n.sub.D.sup.20 1.5813719 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR280## H n.sub.D.sup.20 1.5846720 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR281## H m.p. 80.3721 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR282## H n.sub.D.sup.20 1.5862722 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR283## H n.sub.D.sup.20 1.5816723 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR284## 4-Cl n.sub.D.sup.20 1.5756724 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR285## 4-OCH.sub.3 n.sub.D.sup.20 1.5798725 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR286## 4-F m.p. 72.2726 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR287## H m.p. 73.8727 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR288## 4-Cl n.sub.D.sup.20 1.5694728 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR289## 4-OCH.sub.3 n.sub.D.sup.20 1.5665729 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR290## 4-F n.sub.D.sup.20 1.5588730 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR291## H n.sub.D.sup.20 1.5677731 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR292## 4-Cl n.sub.D.sup.20 1.5650732 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR293## 4-F n.sub.D.sup.20 1.5552733 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR294## 4-OCH.sub.3 n.sub.D.sup.20 1.5657734 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR295## 4-OCH.sub.3 n.sub.D.sup.20 1.5682735 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR296## 4-F n.sub.D.sup.20 1.5612736 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR297## H n.sub.D.sup.20 1.5737737 CH.sub.3 C.sub.2 H.sub.5 H CH.sub.2 CH.sub.2 O ##STR298## H n.sub.D.sup.20 1.5626738 CH.sub.3 C.sub.3 H.sub.7i H CH.sub.2 CH.sub.2 O ##STR299## H n.sub.D.sup.20 1.5571739 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.2 O ##STR300## H n.sub.D.sup.20 1.5530740 CH.sub.3 CH.sub.3 H ##STR301## O ##STR302## H n.sub.D.sup.20 1.5530741 CH.sub.3 CH.sub.3 H ##STR303## O ##STR304## 4-F n.sub.D.sup.20 1.5484742 CH.sub.3 CH.sub.3 H ##STR305## O ##STR306## H n.sub.D.sup.20 1.5520743 CH.sub.3 CH.sub.3 H ##STR307## O ##STR308## H n.sub.D.sup.20 1.5405744 CH.sub.3 CH.sub.3 H ##STR309## O ##STR310## 4-F n.sub.D.sup.20 1.5368745 CH.sub.3 CH.sub.3 H ##STR311## O ##STR312## H n.sub.D.sup.20 1.5482746 CH.sub.3 CH.sub.3 H ##STR313## O ##STR314## H n.sub.D.sup.20 1.5693747 CH.sub.3 CH.sub.3 H ##STR315## O ##STR316## H n.sub.D.sup.20 1.5453748 CH.sub.3 CH.sub.3 H ##STR317## O ##STR318## 4-F n.sub.D.sup.20 1.5418749 CH.sub.3 CH.sub.3 H ##STR319## O ##STR320## 4-Cl n.sub.D.sup.20 1.5613750 CH.sub.3 CH.sub.3 H ##STR321## O ##STR322## 4-OCH.sub.3 n.sub.D.sup.20 1.5440751 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 S ##STR323## H n.sub.D.sup.20 1.5594752 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 S ##STR324## H n.sub.D.sup.20 1.5902753 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 S ##STR325## H n.sub.D.sup.20 1.5775754 Ch.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 S ##STR326## H m.p. 87.4755 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 S ##STR327## H m.p. 96.4756 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 CH.sub.2 O ##STR328## H n.sub.D.sup.20 1.5647757 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 CH.sub.2 O ##STR329## 4-F n.sub.D.sup.20 1.5593758 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR330## 4-Cl n.sub.D.sup.20 1.5766759 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 CH.sub.2 O ##STR331## 4-OCH.sub.3 n.sub.D.sup.20 1.5700760 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 CH.sub. 2 O ##STR332## H n.sub.D.sup.20 1.5520761 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR333## H n.sub.D.sup.20 1.5746762 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 CH.sub.2 O ##STR334## H n.sub.D.sup.20 1.5647763 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR335## 4-F n.sub.D.sup.20 1.5648764 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 CH.sub.2 O ##STR336## 4-OCH.sub.3 n.sub.D.sup.20 1.5748765 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 CH.sub.2 O ##STR337## H n.sub.D.sup.20 1.5689766 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 CH.sub.2 O ##STR338## H n.sub.D.sup.20 1.5670767 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 O ##STR339## 4-F n.sub.D.sup.20 1.5553768 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 O ##STR340## 4-Cl n.sub.D.sup.20 1.5678769 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 O ##STR341## 4-OCH.sub.3 n.sub.D.sup.20 1.5605770 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 O ##STR342## H n.sub.D.sup.20 1.5620771 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 O ##STR343## H n.sub.D.sup.20 1.5511772 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 CH.sub. 2 CH.sub.2 O ##STR344## H n.sub.D.sup.20 1.5672773 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 O ##STR345## H n.sub.D.sup.20 1.5653774 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 O ##STR346## H n.sub.D.sup.20 1.5638775 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 O ##STR347## H n.sub.D.sup.20 1.5763776 CH.sub.3 CH.sub.3 H CH.sub.2 CHCHCH.sub.2 O ##STR348## H n.sub.D.sup.20 1.5712777 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 O ##STR349## 4-OCH.sub.3 n.sub.D.sup.20 1.5635778 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 O ##STR350## H n.sub.D.sup.10 1.5511779 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 O ##STR351## H n.sub.D.sup.10 1.5671780 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 O ##STR352## H n.sub.D.sup.20 1.5583781 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.21ab,4 O ##STR353## H n.sub.D.sup.10 1.5478782 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 O ##STR354## H n.sub.D.sup.10 1.5631783 CH.sub. 3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR355## 4-Cl m.p. 110.1784 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR356## H m.p. 107.4785 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR357## H n.sub.D.sup.20 1.6107786 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O COCH.sub.3 H n.sub.D.sup.20 1.5411787 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O ##STR358## H n.sub.D.sup.20 1.5632788 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O C.sub.4 H.sub.9t H n.sub.D.sup.20 1.5273789 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 O C.sub.2 H.sub.5 H n.sub.D.sup.20 1.5407__________________________________________________________________________
TABLE I(c)__________________________________________________________________________ ##STR359## (I) Physical property m.p. (.degree.C.) orCompound No. R.sup.1 R.sup.2 R.sup.3 QZ.sup.2R.sup.4 Y.sub.m refractive__________________________________________________________________________ index790 CH.sub.3 CH.sub.3 H CH.sub.3 H m.p. 70.2791 CH.sub.3 CH.sub.3 H C.sub.2 H.sub.5 H n.sub.D.sup.20 1.5504792 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 Br H n.sub.D.sup.20 1.5721793 CH.sub.3 CH.sub.3 H C.sub.3 H.sub.7i H n.sub.D.sup.20 1.5432794 CH.sub.3 CH.sub.3 H CH.sub.2 CHCH.sub.2 H n.sub.D.sup.20 1.5560795 CH.sub.3 CH.sub.3 H CH.sub.2 CCH 4-Cl n.sub.D.sup.20 1.5670796 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 Br H n.sub.D.sup.20 1.5618797 CH.sub.3 CH.sub.3 H CH.sub.2 CHC(CH.sub.3).sub.2 H n.sub.D.sup.20 1.5494798 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 Hr n.sub.D.sup.20 1.5571799 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 Br H n.sub.D.sup.20 1.5522800 CH.sub.3 CH.sub.3 H ##STR360## H n.sub.D.sup.20 1.5267801 CH.sub.3 CH.sub.3 H ##STR361## 4-F n.sub.D.sup.20 1.5294802 CH.sub.3 CH.sub.3 H ##STR362## 4-Cl n.sub.D.sup.20 1.5290803 CH.sub.3 CH.sub.3 H ##STR363## H n.sub.D.sup.20 1.5408804 CH.sub.3 CH.sub.3 H CH.sub.2 CClCHCl H n.sub.D.sup.20 1.5578805 CH.sub.3 CH.sub.3 H ##STR364## 4-Cl n.sub.D.sup.20 1.5653806 CH.sub.3 CH.sub.3 H ##STR365## H n.sub.D.sup.20 1.5470807 CH.sub.3 CH.sub.3 H ##STR366## H n.sub.D.sup.20 1.5662808 CH.sub.3 CH.sub.3 H ##STR367## H n.sub.D.sup.20 1.5675809 CH.sub.3 CH.sub.3 H ##STR368## H m.p. 86.9810 CH.sub.3 CH.sub.3 H ##STR369## H n.sub.D.sup.20 1.5716811 CH.sub.3 CH.sub.3 H ##STR370## H n.sub.D.sup.20 1.5674812 CH.sub.3 CH.sub.3 H ##STR371## H n.sub.D.sup.20 1.5602813 CH.sub.3 CH.sub.3 H ##STR372## 4-F n.sub.D.sup.20 1.5524814 CH.sub.3 CH.sub.3 H ##STR373## 4-Cl n.sub.D.sup.20 1.5621815 CH.sub.3 CH.sub.3 H ##STR374## 4-OCH.sub.3 n.sub.D.sup.20 1.5588816 CH.sub.3 CH.sub. 3 H ##STR375## H n.sub.D.sup.20 1.5653817 CH.sub.3 CH.sub.3 H ##STR376## 4-F n.sub.D.sup.20 1.5547818 CH.sub.3 CH.sub.3 H ##STR377## 4-Cl n.sub.D.sup.20 1.5688819 CH.sub.3 CH.sub.3 H ##STR378## 4-OCH.sub.3 n.sub.D.sup.20 1.5643820 CH.sub.3 CH.sub.3 H ##STR379## H n.sub.D.sup.20 1.5755821 CH.sub.3 CH.sub.3 H ##STR380## H n.sub.D.sup.20 1.5747822 CH.sub.3 CH.sub.3 H ##STR381## H n.sub.D.sup.20 1.5654823 CH.sub.3 CH.sub.3 H ##STR382## H n.sub.D.sup.20 1.5757824 CH.sub.3 CH.sub.3 H ##STR383## 4-Cl n.sub.D.sup.20 1.5751825 CH.sub.3 CH.sub.3 H ##STR384## 4-OCH.sub.3 n.sub.D.sup.20 1.5733826 CH.sub.3 CH.sub.3 H ##STR385## H n.sub.D.sup.20 1.5543827 CH.sub.3 CH.sub.3 H ##STR386## 4-F n.sub.D.sup.20 1.5450828 CH.sub.3 CH.sub.3 H ##STR387## 4-Cl n.sub.D.sup.20 1.5578829 CH.sub.3 CH.sub.3 H ##STR388## 4-OCH.sub.3 n.sub.D.sup.20 1.5539830 CH.sub.3 CH.sub.3 H ##STR389## H n.sub.D.sup.20 1.5463831 CH.sub.3 CH.sub.3 H ##STR390## H n.sub.D.sup.20 1.5695832 CH.sub.3 CH.sub.3 H ##STR391## 4-F n.sub.D.sup.20 1.5332833 CH.sub.3 CH.sub.3 H ##STR392## 4-F n.sub.D.sup.20 1.5613834 CH.sub.3 CH.sub.3 H ##STR393## 4-Cl n.sub.D.sup.20 1.5760835 CH.sub.3 CH.sub.3 H ##STR394## 4-OCH.sub.3 n.sub.D.sup.20 1.5690836 CH.sub.3 CH.sub.3 H ##STR395## H n.sub.D.sup.20 1.5545837 CH.sub.3 CH.sub.3 H ##STR396## H n.sub.D.sup.20 1.5722838 CH.sub.3 CH.sub.3 H ##STR397## H n.sub.D.sup.20 1.5577839 CH.sub.3 CH.sub.3 H ##STR398## H n.sub.D.sup.20 1.5660840 CH.sub.3 CH.sub.3 H ##STR399## 4-F n.sub.D.sup.20 1.5576841 CH.sub.3 CH.sub.3 H ##STR400## 4-Cl n.sub.D.sup.20 1.5960842 CH.sub.3 CH.sub.3 H ##STR401## H n.sub.D.sup.20 1.5647843 CH.sub.3 CH.sub.3 H ##STR402## 4-Cl n.sub.D.sup.20 1.5829844 CH.sub.3 CH.sub.3 H ##STR403## 4-OCH.sub.3 n.sub.D.sup.20 1.5732845 CH.sub.3 CH.sub.3 H ##STR404## H n.sub.D.sup.20 1.5972846 CH.sub.3 ##STR405## H ##STR406## 4-Cl n.sub.D.sup.20 1.5980847 CH.sub.3 CH.sub.3 H ##STR407## H m.p. 119.9848 CH.sub.3 CH.sub.3 H ##STR408## H n.sub.D.sup.20 1.6045849 CH.sub.3 CH.sub.3 H ##STR409## 4-Cl n.sub.D.sup.20 1.5886850 CH.sub.3 CH.sub.3 H ##STR410## H Paste851 CH.sub.3 CH.sub.3 H ##STR411## 4-F n.sub.D.sup.20 1.5828852 CH.sub.3 CH.sub.3 H ##STR412## H Paste853 CH.sub.3 CH.sub.3 H ##STR413## 4-F Paste854 CH.sub.3 CH.sub.3 H ##STR414## 4-Cl Paste855 CH.sub.3 CH.sub.3 H ##STR415## 4-OCH.sub.3 n.sub.D.sup.20 1.5815856 CH.sub.3 CH.sub.3 ##STR416## CH.sub.3 H n.sub.D.sup.20 1.5822857 CH.sub.3 CH.sub.3 ##STR417## CH.sub.2 CHCH.sub.2 H n.sub.D.sup.20 1.5800__________________________________________________________________________ Note 1. .sup.1 HNMR value (CDCl.sub.3, TMS) of Compound No. 180: 1.62 (6H s), 2.33 (3H, s), 3.53 (3H, s), 4.83 (2H, d, J=48Hz), 4.95 (2H, s), 6.7-7.9 (9H, m), 7.75 (1H, s) Note 2. .sup.1 HNMR value (CDCl.sub.3, TMS) of compound No. 299: 1.37 (6H s), 2.34 (3H, s), 3.55 (3H, s), 4.53 (2H, d, J=47.5Hz), 4.95 (2H, s), 6.7-7.4 (9H, m), 7.76 (1H, s)

Production of the compounds of the present invention will be illustrated with reference to the following examples, but it is not limited to these examples.
EXAMPLE 1
Methyl 4-[(1,3-dimethyl-5-phenoxyprazol-4-yl)methyleneaminooxymethyl]benzoate (compound No. 16) ##STR418##
2.0 Grams (0.00865 mole) of 1,3-dimethyl-5-phenoxypyrazole-4-carbaldehyde oxime, 1.98 g (0.00865 mole) of methyl 4-bromomethylbenzoate and 1.19 g (0.009 mole) of potassium carbonate were added to 50 ml of acetone, and the resulting mixture was heated under reflux for 8 hours. After completion of the reaction, acetone was removed by evaporation under reduced pressure, after which water was added to the residue and extraction was carried out with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation to obtain an oily product. This oily product was column-chromatographed on silica gel to obtain 2.0 g of the desired product.
Yield 61%. n.sub.D.sup.20 1.5612.
EXAMPLE 2
Tert-butyl 4-[(1,3-dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl]benzoate (compound No. 60) ##STR419##
2.0 Grams (0.00855 mole) of 1,3-dimethyl-5-phenoxypyrazole-4-carbaldehyde oxime was dissolved in 20 ml of dimethyl sulfoxide, and after adding 0.65 g (0.0116 mole) of powdery potassium hydroxide, the resulting mixture was stirred at 30.degree. C. for 30 minutes. To this solution was added 2.32 g (0.00855 mole) of tert-butyl 4-bromomethylbenzoate, and reaction was carried out at from 50.degree. to 60.degree. C. for 1 hour. After completion of the reaction, water was added to the reaction solution which was then extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation to obtain crude crystals. The crystals were recrystallized from methanol to obtain 2.4 g of the desired compound.
Yield 67.0%. m.p. 101.7.degree. C.
EXAMPLE 3
Methyl 2-[{5-(4-chlorophenoxy)-1,3-dimethylpyrazol-4-yl}methyleneaminoxymethyl]benzoate (compound No. 3) ##STR420##
2.0 Grams (0.00755 mole) of 5-(4-chlorophenoxy)-1,3-dimethyl-pyrazole-4-carbaldehyde oxime was dissolved in 20 ml of dimethylformamide, and after adding 0.5 g (0.0125 mole) of powdery sodium hydroxide, the resulting mixture was thoroughly stirred. To this solution was added 1.73 g (0.00755 mole) of methyl 2-bromomethylbenzoate, and reaction was carried out at from 70.degree. to 80.degree. C. for 5 hours. After completion of the reaction, water was added to the reaction solution which was then extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation to obtain an oily product. This oily product was column-chromatographed on silica gel to obtain 2.0 g cf the desired compound.
Yield 64.0%. n.sub.D.sup.20 1.5788.
EXAMPLE 4
Isopropyl 4-[(1,3-dimethyl-5-phenylthiopyrazol-4-yl)methyleneaminooxymethyl]benzoate (compound No. 174) ##STR421##
3.0 Grams (0.0121 mole) of 1,3-dimethyl-5-phenylthiopyrazole-4-carbaldehyde oxime, 2.57 g (0.0121 mole) of isopropyl 4-chloromethylbenzoate and 2.8 g (0.026 mole) of sodium carbonate were added to 50 ml of methyl ethyl ketone, and the resulting mixture was heated under reflux for 5 hours. After completion of the reaction, methyl ethyl ketone was removed by evaporation under reduced pressure, after which water was added to the residue and extraction was carried out with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation to obtain an oily product. This oily product was column-chromatographed on silica gel to obtain 3.0 g of the desired compound.
Yield 59.0%. n.sub.D.sup.20 1.5821.
EXAMPLE 5
Tert-butyl 4-[1-(1,3-dimethyl-5-phenoxypyrazol-4-yl)-ethylideneaminooxymethyl]benzoate (compound No. 1669 ##STR422##
2.0 Grams (0.00816 mole) of methyl 1,3-dimethyl-5-phenoxy-pyraxol-4-yl ketone oxime, 2.2 g (0.00816 mole) of tert-butyl 4-bromomethylbenzoate and 4.0 g (0.028 mole) of potassium carbonate were added to 50 ml of acetonitrile, and the resulting mixture was heated under reflux for 5 hours. After completion of the reaction, acetonitrile was removed by evaporation under reduced pressure, after which water was added to the residue and extraction was carried out with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation to obtain crude crystals. The crystals were recrystallized from methanol to obtain 2.8 g of the desired compound.
Yield 79.0%. m.p. 94.4.degree. C.
EXAMPLE 6
Cyclohexyl 4-[{5-(4-fluorophenoxy)-1,3-dimethylpyrazol-4-yl}methyleneaminooxymethyl]benzoate (compound No. 119) ##STR423##
2.0 Grams (0.008 mole) of 5-(4-fluorophenoxy)-1,3-dimethylpyrazole-4-carbaldehyde oxime and 0.5 g (0.0125 mole) of powdery sodium hydroxide were added to 50 ml of dimethyl sulfoxide, and the resulting mixture was stirred for 30 minutes. To this solution was added 2.38 g (0.008 mole) of cyclohexyl 4-bromomethylbenzoate, and reaction was carried out at from 70.degree. to 80.degree. C. for 6 hours. After completion of the reaction, water was added to the reaction solution which was then extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation to obtain an oily product. This oily product was column-chromatographed on silica gel to obtain 3.0 g of the desired compound.
Yield 80.0%. n.sub.D.sup.20 1.5863.
EXAMPLE 7
Tert-butyl 4-[(1-methyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl]benzoate (compound No. 174) ##STR424##
1.0 Gram (0.0049 mole) of 1-methyl-5-phenoxypyrazole-4-carbaldehyde and 1.1 g (0.0049 mole) of tert-butyl 4-aminooxymethylbenzoate were added to 20 ml of ethanol, and the resulting mixture was heated under reflux to carry out reaction. After completion of the reaction, ethanol was removed by evaporation, after which water was added to the residue and extraction was carried out with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation to obtain an oily product. This oily product was column-chromatographed on silica gel to obtain 1.6 g of the desired compound.
Yield 80%. Form of product: paste.
NMR (CDCl.sub.3, TMS): .delta. (ppm) 1.56 (s, 9H), 3.60 (s, 3H), 4.96 (s, 2H), 6.60-7.40 (m, 7H), 7.63 (s, 1H), 7.66 (s, 1H), 7.75-8.00 (m, 2H).
EXAMPLE 8
2-phenoxyethyl 4-[{5-(4-fluorophenoxy)-1,3-dimethylpyrazol-4-yl}methyleneaminooxymethyl]benzoate (compound No. 142) ##STR425##
2.0 Grams (0.008 mole) of 5-(4-fluorophenoxy)-1,3-dimethylpyrazole-4-carbaldehyde oxime was dissolved in 20 ml of dimethyl sulfoxide, and after adding 0.65 g (0.0116 mole) of powdery potassium hydroxide, the resulting solution was stirred at 30.degree. C. for 30 minutes. To this solution was added 2.5 g (0.00865 mole) of 2-phenoxyethyl 4-chloromethylbenzoate, and reaction was carried out at from 50.degree. to 60.degree. C. for 1 hour. After completion of the reaction, water was added to the reaction solution which was then extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation to obtain an oily product. This oily product was column-chromatographed on silica gel to obtain 3.0 g of the desired compound.
Yield 75.0%. n.sub.D.sup.20 1.5655.
EXAMPLE 9
Phenyl 4-[(1,3-dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxy]benzoate (compound No. 161) ##STR426##
1.0 Gram (0.0027 mole) of 4-[(1,3-dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl]benzoic acid, 0.25 g (0.0027 mole) of phenol and 0.7 g (0.0027 mole) of triphenylphosphine were added to 50 ml of ether, and the resulting mixture was stirred. To this solution was added 0.47 g (0.0027 mole) of diethyl azodicarboxylate, and the resulting solution was heated under reflux for 3 hours. After completion of the reaction, the ether layer was filtered, and ether was removed by evaporation to obtain an oily product. This oily product was column-chromatographed on silica gel to obtain 0.9 g of the desired compound.
Yield 76.0%. n.sub.D.sup.20 1.5656.
EXAMPLE 10
4-[(1,3-Dimethyl-5-phenoxypyrazol-4-yl)-methyleneaminooxymethyl]benzoic acid (compound No. 14) ##STR427##
Three grams (0.0079 mole) of methyl 4-[(1,3-dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl]benzoate was dissolved in 20 ml of methanol and a solution of 0.24 g of lithium hydroxide in 5 ml of water was added. Reaction was then carried out at room temperature for 2 hours. After completion of the reaction, methanol was removed by evaporation, and after adding water, the solution was acidified with hydrochloric acid to precipitate crystals. The crystals were collected by filtration to obtain 2 g of the desired compound.
Yield 70%. m.p. 183.3.degree. C.
EXAMPLE 11
Sodium 4-[(1,3-dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl]benzoate (compound No. 15) ##STR428##
1.0 Gram (0.0027 mole) of 4-[(1,3-dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl]benzoic acid and 0.07 g (0.0028 mole) of sodium hydroxide were added to 10 ml of water, and the resulting mixture was stirred for 2 hours. After completion of the reaction, water was removed by evaporation under reduced pressure to obtain the desired compound in a quantitative yield.
m.p.>300.degree. C.
EXAMPLE 12
1,3-Dimethyl-5-phenoxypyrazole-4-carbaldehyde oxime O-benzyl ether (compound No. 181) ##STR429##
2.0 Grams (0.00866 mole) of 1,3-dimethyl-5-phenoxypyrazole-4-carbaldehyde oxime, 1.5 g (0.0087 mole) of benzyl bromide and 2.0 g (0.0145 mole) of potassium carbonate were dissolved in 50 ml of acetone, and the resulting solution was heated under reflux for 7 hours. After completion of the reaction, acetone was removed by evaporation under reduced pressure, after which water was added and extraction was carried out with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation to obtain an oily product. This oily product was column-chromatographed on silica gel to obtain 2.6 g of the desired compound.
Yield 93.0%. n.sub.D.sup.20 1.5517.
EXAMPLE 13
5-(4-Chlorophenoxy)-1,3-dimethylpyrazole-4-carbaldehyde oxime O-4-trifluoromethylbenzyl ether (compound No. 195) ##STR430##
2.0 Grams (0.0075 mole) of 5-(chlorophenoxy)-1,3-dimethylpyrazole-4-carbaldehyde oxime was dissolved in 40 ml of tetrahydrofuran, and after adding 0.19 g (0.0079 mole) of sodium hydride at room temperature, the resulting solution was stirred. Thereafter, 1.7 g (0.0071 mole) of 4-trifluoromethylbenzyl bromide was added, followed by heating under reflux for 3 hours. After completion of the reaction, 100 ml of water was added to the reaction solution which was then extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation to obtain an oily product. This oily product was column-chromatographed on silica gel to obtain 2.7 g of the desired compound.
Yield 85.0%. n.sub.D.sup.20 1.5539.
EXAMPLE 14
1,3-Dimethyl-5-phenoxypyrazole-4-carbaldehyde oxime 0-4-(1-cyanocyclopropyl)benzyl ether (compound No. 199) ##STR431##
2.0 Grams (0.0086 mole) of 1,3-dimethyl-5-phenoxypyrazole-4-carbaldehyde oxime was dissolved in 30 ml of dimethylformamide, and a solution of 0.5 g (0.0125 mole) of sodium hydroxide in 5 ml of water was added. After stirring was continued for 30 minutes, 2.0 g (0.0086 mole) of 1-(4-bromomethylphenyl)cyclopropane-1-carbonitrile was added to the solution, and reaction was carried out at from 60.degree. to 70.degree. C. for 3 hours. After completion of the reaction, 100 ml of water was added to the reaction solution which was then extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation to obtain an oily product. This oily product was column-chromatographed on silica gel to obtain 2.8 g of the desired compound.
Yield 84.0%. m.p. 109.1.degree. C.
EXAMPLE 15
1,3-Dimethyl-5-phenoxypyrazole-4-carbaldehyde oxime 4-tert-butylbenzyl ether (compound No. 205) ##STR432##
2.0 Grams (0.0086 mole) of 1,3-dimethyl-5-phenoxypyrazole-4-carbaldehyde oxime was dissolved in 20 ml of dimethyl sulfoxide, and after adding 1.0 g (0.0178 mole) of potassium hydroxide, the resulting solution was stirred at room temperature for 30 minutes. To this solution was added 1.5 g (0.0086 mole) of 4-tert-butylbenzyl chloride, and reaction was carried out at from 50.degree. to 60.degree. C. for 3 hours. After completion of the reaction, 100 ml of water was added to the reaction solution which was then extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation to obtain an oily product. This oily product was column-chromatographed on silica gel to obtain 2.4 g of the desired compound.
Yield 74.0%. n.sub.D.sup.20 1.5402.
EXAMPLE 16
5-(4-Chlorophenoxy)-1-methylpyrazole-4-carbaldehyde oxime O-benzyl ether (compound No. 279) ##STR433##
2.0 Grams (0.0092 mole) of 5-(4-chlorophenoxy)-1-methylpyrazole-4-carbaldehyde oxime, 1.5 g (0.0092 mole) of benzyl bromide and 2.0 g (0.0145 mole) of potassium carbonate were dissolved in 50 ml of acetonitrile, and the resulting solution was heated under reflux for 9 hours. After completion of the reaction, 100 ml of water was added to the reaction solution which was then extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation to obtain an oily product. This oily product was column-chromatographed on silica gel to obtain 2.2 g of the desired compound.
Yield 78.0%. n.sub.D.sup.20 1.5933.
EXAMPLE 17
1,3-Dimethyl-5-phenoxypyrazol-4-yl methyl ketone oxime O-4-cyclohexylbenzyl ether (compound No. 283) ##STR434##
2.0 Grams (0.0040 mole) of 1,3-dimethyl-5-phenoxypyrazol-4-yl methyl ketone oxime was dissolved in 30 ml of dioxane, and 0.1 g (0.0042 mole) of sodium borohydride was added to the solution with thorough stirring. After 30 minutes, 1.6 g (0.0038 mole) of 4-cyclohexylbenzyl bromide was added to the reaction solution which was then heated under reflux for 5 hours. After completion of the reaction, 100 ml of water was added to the reaction solution which was then extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation to obtain an oily product. This oily product was column-chromatographed on silica gel to obtain 1.2 g of the desired compound.
Yield 72.0%. n.sub.D.sup.20 1.5775
EXAMPLE 18
5-(4-Chlorophenylthio)-1,3-dimethylpyrazole-4-carbaldehyde oxime O-benzyl ether (compound No. 290) ##STR435##
2.0 Grams (0.0071 mole) of 5-(4-chlorophenylthio)-1,3-dimethylpyrazole-4-carbaldehyde oxime was dissolved in 20 ml of dimethyl sulfoxide, and to this solution was added a solution of 0.5 g (0.009 mole) of potassium hydroxide in 5 ml of water. After thorough stirring, 0.9 g (0.0071 mole) of benzyl choride was added, and reaction was carried out at from 60.degree. to 70.degree. C. for 2 hours. After completion of the reaction, 100 ml of water was added to the reaction solution which was then extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation to obtain an oily product. This oily product was column-chromatographed on silica gel to obtain 2.3 g of the desired compound.
Yield 87.0%. n.sub.D.sup.2 1.5562.
EXAMPLE 19
5-(4-Methoxyphenoxy)-1,3-dimethylpyrazole-4-carbaldehyde oxime O-4-(1-cyanocyclopentyl)benzyl ether (compound No. 238) ##STR436##
2.0 Grams (0.0081 mole) of 1,3-dimethyl-5-(4-methoxyphenoxy)pyrazole-4-carbaldehyde was dissolved in 50 ml of ethanol, and 1.7 g (0.0081 mole) of O-4-(1-cyanocyclopentyl)benzylhydroxylamine was added, after which reaction was carried out at from 50.degree. to 60.degree. C. for 3 hours. After completion of the reaction, ethanol was removed by evaporation under reduced pressure, after which water was added and extraction was carried out with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation to obtain an oily product. This oily product was column-chromatographed on silica gel to obtain 3.0 g of the desired compound.
Yield 83.0%. n.sub.D.sup.20 1.5632.
EXAMPLE 20
1,3-Dimethyl-5-phenoxypyrazole-4-carbaldehyde oxime O-4-(2,2-dibromovinyl)benzyl ether (compound No. 262) ##STR437##
2.0 Grams (0.0093 mole) of 1,3-dimethyl-5-phenoxypyrazole-4-carbaldehyde was dissolved in 50 ml of methanol, and 2.8 g (0.0091 mole) of O-4-(2,2-dibromovinyl)benzylhydroxylamine was added to the solution which was then heated under reflux for 3 hours. After completion of the reaction, methanol was removed by evaporation under reduced pressure, after which water was added and extraction was carried out with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation to obtain an oily product. This oily product was column-chromatpgraphed on silica gel to obtain 3.5 g of the desired compound.
Yield 76.0%. m.p. 109.3.degree. C.
EXAMPLE 21
1,3-dimethyl-5-phenoxypyrazole-4-carbaldehyde oxime O-4-fluorobenzyl ether (compound No. 305) ##STR438##
1.0 Gram (0.0043 mole) of 1,3-dimethyl-5-phenoxypyrazole-4-carbaldehyde oxime was dissolved in 20 ml of dimethyl sulfoxide, and after adding 0.3 g (0.0053 mole) of powdery potassium hydroxide, the resulting solution was stirred. To this reaction solution was added 0.81 g (0.0043 mole) of 4-fluorobenzyl bromide, and reaction was carried out at room temperature for 3 hours. After completion of the reaction, 200 ml of water was added to the reaction solution which was then extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation to obtain an oily product. This oily product was column-chromatographed on silica gel to obtain 1.3 g of the desired compound.
Yield 89%. n.sub.D.sup.20 1.5681.
EXAMPLE 22
5-(4-Chlorophenoxy)-1,3-dimethyopyrazole-4-carbaldehyde oxime O-2-chlorobenzyl ether (compound No. 309) ##STR439##
1.0 Gram (0.0038 mole) of 5-(4-chlorophenoxy)-1,3-dimethylpyrazole-4-carbaldehyde oxime, 0.78 g (0.0038 mole) of 2-chlorobenzyl bromide and 1.0g (0.0072 mole) of potassium carbonate were added to 20 ml of acetonitrile, and the resulting mixture was heated under reflux for 6 hours. After completion of the reaction, acetonitrile was removed by evaporation under reduced pressure, after which water was added and extraction was carried out with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation to obtain an oily product. This oily product was column-chromatographed on silica gel to obtain 1.2 g of the desired compound.
Yield 81%. n.sub.D.sup.20 1.5760.
EXAMPLE 23
5-(4-Chlorophenoxy)-1,3-dimethylpyrazole-4-carbaldehyde oxime O-4-(4-trifluoromethylphenoxy)benzyl ether (compound No. 322) ##STR440##
1.0 Gram (0.0038 mole) of 5-(4-chlorophenoxy)-1,3-dimethylpyrazole-4-carbaldehyde oxime, 1.1 g (0.0038 mole) of 4-(4-trifluoromethylphenoxy)benzyl chloride and 0.8 g (0.076 mole) of sodium carbonate were added to 40 ml of acetone, and the resulting mixture was heated under reflux for 8 hours. After completion of the reaction, acetone was removed by evaporation under reduced pressure, after which water was added and extraction was carried out with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation to obtain an oily product. This oily product was column-chromatographed on silica gel to obtain 1.4 g of the desired compound.
Yield 72%. m.p. 97.8.degree. C.
EXAMPLE 24
1,3-Dimethyl-5-phenoxypyrazol-4-yl methyl ketone oxime O-4-trimethylsilylbenzyl ether (compound No. 334) ##STR441##
1.0 Gram (0.0041 mole) of 1,3-dimethyl-5-phenoxypyrazol-4-yl methyl ketone oxime was dissolved in 20 ml of dimethyl sulfoxide, and after adding 0.3 g (0.0053 mole) of potassium hydroxide, the resulting solution was stirred. To this reaction solution was added 1.0 g (0.0041 mole) of 4-trimethylsilylbenzyl bromide, and reaction was carried out at room temperarture for 4 hours. After completion of the reaction, 200 ml of water was added to the reaction solution which was then extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation to obtain an oily product. This oily product was column-chromatographed on silica gel to obtain 1.5 g of the desired compound.
Yield 92%. m.p. 61.2.degree. C.
EXAMPLE 25
1,3-Dimethyl-5-phenoxypyrazol-4-yl ethyl ketone oxime O-4-(1,1,2,2-tetrafluoroethoxy)benzyl ether (compound No. 354) ##STR442##
1.0 Gram (0.0035 mole) of sodium salt of 1,3-dimethyl-5-phenoxypyrazol-4-yl ethyl ketone sodium and 1.0 g (0.0035 mole) of 4-(1,1,2,2-tetrafluoroethoxy)benzyl bromide were added to 50 ml of acetone, and the resulting mixture was heated for 5 hours to carry out reaction. After completion of the reaction, acetone was removed by evaporation under reduced presure, after which water was added and extraction was carried out with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation to obtain an oily product. This oily product was column-chromatographed on silica gel to obtain 1.3 g of the desired compound.
Yield 76%. n.sub.D.sup.20 1.5252.
EXAMPLE 26
5-(4-Methoxyphenoxy)-1,3-dimethylpyrazole-4-carbaldehyde oxime O-4-tert-butoxybenzyl ether (compound No. 366) ##STR443##
1.0 Gram (0.0038 mole) of 5-(4-methoxyphenoxy)-1,3-dimethyl-pyrazole-4-carbaldehyde oxime was dissolved in 30 ml of tetrahydrofuran, and 0.092 g of sodium hydride was added to synthesize the sodium salt of said oxime. To this solution was added 0.92 g (0.0038 mole) of 4-tert-butoxybenzyl bromide, and reaction was carried out at from 50.degree. to 60.degree. C. for 5 hours. After completion of the reaction, 200 ml of water was added to the reaction solution which was then extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation to obtain an oily product. THis oily product was column-chromatographed on silica gel to obtain 1.3 g of the desired compound.
Yield 80%. n.sub.D.sup.20 1.5653
EXAMPLE 27
5-(4-Fluorophenoxy)-1,3-dimethylpyrazole-4-carbaldehyde oxime O-3,4-methylenedioxybenzyl ether (compound No. 374) ##STR444##
1.0 Gram (0.0040 mole) of 5-(4-fluorophenoxy)-1,3-dimethylpyrazole-4-carbaldehyde oxime was dissolved in 20 ml of dimethylformamide, and after adding 0.2 g (0.005 mole) of sodium hydroxide, the resulting solution was stirred for 30 minutes. To this reaction solution was added 0.86 g (0.004 mole) of 3,4-methylenedioxybenzyl bromide, and reaction was carried out at from 40.degree. to 50.degree. C. for 3 hours. After completion of the reaction, 200 ml of water was added to the reaction solution which was then extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation to obtain an oily product. This oily product was column-chromatographed on silica gel to obtain 1.1 g of the desired compound.
Yield 72%. n.sub.D.sup.20 1.5750.
EXAMPLE 28
5-(4-(Methoxyphenoxy)-1,3-dimethylpyrazole-4-carbaldehyde oxime O-4-methylsulfonylbenzyl ether (compound No. 401) ##STR445##
1.0 Gram (0.0038 mole) of 5-(4-methoxyphenoxy)-1,3-dimethylpyrazole-B 4-carbaldehyde oxime and 0.79 g (0.0038 mole) of 4-methylsulfonylbenzyl chloride were dissolved in 30 ml of tetrahydrofuran. To this solution was added 0.6 g (0.0039 mole) of 1,8-diazabicyclo[5.4.0]-7-undecene, and reaction was carried out at from 40.degree. to 50.degree. C. for 5 hours. After completion of the reaction, 200 ml of water was added to the reaction solution which was then extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation to obtain an oily product. This oily product was column-chromatographed on silica gel to obtain 1.2 g of the desired compound.
Yield 74%. n.sub.D.sup.20 1.5866.
EXAMPLE 29
1,3-Dimethyl-5-phenoxypyrazol-4-yl phenyl ketone oxime O-4-difluoromethylthiobenzyl ether (compound No. 426) ##STR446##
1.0 Gram (0.0033 mole) of 1,3-dimethyl-5-phenoxypyrazol-4-yl phenyl ketone oxime, 0.82 g (0.0033 mole) of 4-difluoromethylthiobenzyl bromide and 1.0 g (0.0072 mole) of potassium carbonate were added to 50 ml of acetone, and the resulting mixture was heated for 6 hours to carry out reaction. After completion of the reaction, acetone was removed by evaporation under reduced pressure, after which water was added and extraction was carried out with ethyl acetate. The ethyl acetate was washed with water and dried, and ethyl acetate was removed by evaporation to obtain an oily product. This oily product was column-chromatographed on silica gel to obtain 1.4 g of the desired compound.
Yield 86%. n.sub.D.sup.20 1.5917.
EXAMPLE 30
5-(2-Fluorophenoxy)-1,3-dimethylpyrazole-4-carbaldehyde oxime O-4-(1,1,2,2-tetrafluoroethylthio)benzyl ether (compound No. 467) ##STR447##
1.1 Gram (0.0043 mole) of 5-(2-fluorophenoxy)-1,3-dimethylpyrazole-4-carbaldehyde was dissolved in 30 ml of ethanol, and 1,1g (0.0043 mole) of O-[4-(1,1,2,2-tetrafluoroethylthio)benzyl]hydroxylaine was added. Reaction was then carried out at from 50.degree. to 60.degree. C. for 2 hours. After completion of the reaction, ethanol was removed by evaporation under reduced pressure, after which water was added and extraction was carried out with chloroform. The chloroform extract was dried, chloroform was removed by evaporation to obtain an oily product. This oily product was column-chromatographed on silica gel to obtain 1.3 g of the desired compound.
Yield 64%. n.sub.D.sup.20 1.5462.
EXAMPLE 31
1,3-Dimethyl-5-phenoxypyrazol-4-yl methyl ketone oxime O-4-heptafluoropropylthiobenzyl ether (compound No. 494) ##STR448##
1.0 Gram (0.0043 mole) of 4-acetyl-1,3-dimethyl-5-phenoxypyrazole and 1.4 g (0.0043 mole) of O-(4-heptafluoropropylthiobenzyl)hydroxylamine were added to 30 ml of methanol, and the resulting mixture was heated for 5 hours to carry out reaction. After completion of the reaction, methanol was removed by evaporation under reduced pressure, after which water was added and extraction was carried out with chloroform. The chloroform extract was dried, and chloroform was removed by evaporation to obtain an oily product. This oily product was column-chromatographed on silica gel to 1.4 g of the desired compound.
Yield 60%. n.sub.D.sup.20 1.5217.
EXAMPLE 32
S-Ethyl 4-[(1,3-dimethyl-5-phenoxypyrazol-4-yl)methyleneaminoxymethyl]benzothioate (compound No. 516) ##STR449##
1.0 Gram (0.0043 mole) of 1,3-dimethyl-5-phenoxypyrazole-4-carbaldehyde oxime was dissolved in 20 ml of dimethyl sulfoxide, and after adding 0.3 g (0.0053 mole) of powdery potassium hydroxide, the resulting solution was stirred. To this solution was added 0.92 g (0.0043 mole) of S-ethyl 4-cloromethylbenzothiate, and reaction was carried out at room temperature for 3 hours. After completion of the reaction, 200 ml of water was added to the reaction solution which was then extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation to obtain an oily product. This oily product was column-chromatographed on silica gel to obtain 1.4 g of the desired compound.
Yield 80%. n.sub.D.sup.20 1.5889.
EXAMPLE 33
N-Tert-butyl 4-[{-(4-methoxyphenoxy)-1,3-dimethylpyrazol-4-yl}methyleneaminomethyl]benzamide (compound No. 525) ##STR450##
1.0 Gram (0.0038 mole) of 5-(4-methoxyphenoxy)-1,3-dimethylpyrazole-4-carbaldehyde oxime, 0.86 g (0.0038 mole) of N-tert-butyl-4-chloromethylbenzamide and 1.0 g (0.0072 mole) of potassium carbonate were added to 20 ml of acetonitrile, and the resulting mixture was heated under reflux for 6 hours. After completion of the reaction, acetonitrile was removed by evaporation under reduced pressure, after which water was added to the residue and extraction was carried out with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation to obtain an oily product. This oily product was column-chromatographed on silica gel to obtain 1.4 g of the desired compound.
Yield 82%. n.sub.D.sup.20 1.5662.
EXAMPLE 34
5-(4-Fluorophenoxy)-1,3-dimethyopyrazole-4-carbaldehyde oxime O-4-pivaloylbenzyl ether (compound No. 548) ##STR451##
1.0 Gram (0.0040 mole) of 5-(4-fluoropheoxy)-1,3-dimethylpyrazole-4-carbaldehyde oxime, 1.0 g (0.0039 mole) of tert-butyl 4-bromomethylphenyl ketone and 1.0 g (0.0094 mole) of sodium carbonate were added to 40 ml of acetone, and the resulting mixture was heated to carry out reaction. After completion of the reaction, acetone was removed by evaporation under reduced pressure, after which water was added to the residue and extraction was carried out with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation to obtain an oily product. This oily product was column-chromatographed on silica gel to obtain 1.5 g of the desired compound.
Yield 89%. n.sub.D.sup.20 1.5567.
EXAMPLE 35
2-Methyl-2-[4-{(1,3-dimethyl-5-phenoxypyrazol-4-yl)methyleneaminoxymethyl}phenyl]-1,3-dioxolane (compound No. 562) ##STR452##
1.0 Gram (0.0043 mole) of 1,3-dimethyl-5-phenoxypyrazole-4-carbaldehyde oxime was dissolved in 20 ml of dioxane, and 0.14 g (0.0058 mole) of sodium hydride was added. Thereafter, 1.1 g (0.0043 mole) of 2-(4-bromomethylphenyl)-2-methyl-1,3-dioxolane was added to this solution which was then heated under reflux for 3 hours. After completion of the reaction, the reaction solution was poured into 200 ml of cold water and extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation to obtain an oily product. This oily product was column-chromatographed on silica gel to obtain 1.3 g of the desired compound.
Yield 74%. n.sub.D.sup.20 1.5698.
EXAMPLE 36
2-[4-[{-(4-Fluorophenoxy)-1,3-dimethylpyrazol-4-yl}methyleneaminoxymethyl]phenyl]-2-methyl-1,3-dioxolane (compound No. 563) ##STR453##
1.1 Gram (0.0043 mole) of 5-(4-fluorophenoxy)-1,3-dimethylpyrazol-4-carbaldehyde and 0.9 g (0.0043 mole) of 2-[4-(aminooxymethyl)phenyl]-2-methyl-1,3-dioxolane were added to 20 ml of ethanol, and the resulting mixture was heated for 3 hours to carry out reaction. After completion of the reaction, ethanol was removed by evaporation under reduced pressure, after which water was added to the residue and extraction was carried out with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation to obtain an oily product. This oily product was column-chromatographed on silca gel to obtain 1.3 g of the desired compound.
Yield 72%. n.sub.D.sup.20 1.5555.
EXAMPLE 37
1,3-Dimethyl-5-phenoxypyrazole-4-carbaldehyde oxime O-4-(1-hydroxyethyl)benzyl ether (compound No. 584) ##STR454##
1.0 Gram (0.0028 mole) of 1,3-dimethyl-5-phenoxypyrazole-4-carbaldehyde oxime-0-4-acetylbenzyl ether, 1.0 g (0.0026 mole) of sodium borohydride and 1 g (0.025 mole) of sodium hydroxide were added to 100 ml of methanol, and the resulting mixture was heated under reflux for 3 hours. After completion of the reaction, methanol was removed by evaporation under reduced pressure, after which water added to the residue and extraction was carried out with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation to obtain an oily product. This oily product was column-chromatographed on silica gel to obtain 0.8 g of the desired compound.
Yield 78%. n.sub.D.sup.20 1.5748.
EXAMPLE 38
N-4-[(1,3-dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl]phenylfomamide (compound No. 589) ##STR455##
1.0 Gram (0.0043 mole) of 1,3-dimethyl-5-phenoxypyrazole-4-carbaldehyde oxime was dissolved in 20 ml of dimethyl sulfoxide, and after adding 0.3 g (0.0053 mole) of powdery potassium hydroxide, the resulting solution was stirred. To this reaction solution was added 0.92 g (0.0043 mole) of N-(4-bromomethyphenyl)formamide, and reaction was carried out at room temperature for 3 hours. After completion of the reaction, the reaction solution was poured into 200 ml of water and extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation to obtain an oily product. This oily product was column-chromatographed on silica gel to obtain 1.2 g of the desired compound.
Yield 76%. m.p. 105.3.degree. C.
EXAMPLE 39
Isopropyl N-4-[{5-(4-fluorophenoxy)-1,3-dimenthylpyrazol-4-yl}methyleneaminooxymethyl]phenylcarbamate (compound No. 595) ##STR456##
1.0 Gram (0.0040 mole) of 5-(4-fluorophenoxy)-1,3-dimethylpyrazole-4-carbaldehyde oxime, 1.1 g (0.0040 mole) of isopropyl N-4-bromomethylphenylcarbamate and 1.0 g (0.0072 mole) of potassium carbonate were added to 20 ml of acetonitrile, and the resulting mixture was heated under reflux for 6 hours. After completion of the reaction, acetonitrile was removed by evaporation under reduced pressure, after which water was added and extraction was carried out with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation to obtain an oily product. This oily product was column-chromatographed on silica gel to obtain 1.5 g of the desired compound.
Yield 85%. n.sub.D.sup.20 1.5645.
EXAMPLE 40
Isobutyl N-4 -[{5-(4-methoxyphenoxy)-1,3-dimethylpyrazol-4-yl}methyleneaminooxymethyl]phenylcarbamate (compound No. 617) ##STR457##
1.0 Gram (0.0038 mole) of 5-(4-methoxyphenoxy)-1,3-dimethylpyrazole-4-carbaldehyde oxime, 1.1 g (0.0038 mole) of isobutyl N-4-bromomethylphenyl-N-methylcarbamate and 1.0 g (0.0094 mole) of sodium carbonate were added to 40 ml of acetone, and the resulting mixture was heated to carry out reaction. After completion of the reaction, acetone was removed by evaporation under reduced pressure, after which water was added and extraction was carried out with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation to obtain an oily product. This oily product was column-chromatographed on silica gel to obtain 1.5 g of the described compound.
Yield 83%. n.sub.D.sup.20 1.5538.
EXAMPLE 41
N-4-[(1,3-dimethyl-5-phenoxypyrazol-4yl) methyleneaminooxymethyl]phenyl-N-isopropylformamide (compound No. 636) ##STR458##
1.0 Gram (0.0043 mole) of 1,3-dimethyl-5-phenoxypyrazole-4-carbaldehyde oxime was dissolved in 20 ml of dioxane, and 0.1 g (0.0043 mole) of sodium hydride was added to synthesize the sodium salt of said oxime. To this reaction solution was added 1.1 g (0.0043 mole) of N-4-bromomethylphenyl-N-isopropylformamide, and reaction was carried out at from 40.degree. to 50.degree. C. for 3 hours. After completion of the reaction, the reaction solution was poured into 200 ml of water and extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation to obtain an oily product. This oil product was column-chromatographed on silica gel to obtain 1.3 g of the desired compound.
Yield 75%. m.p. 73.3.degree. C.
EXAMPLE 42
N-4-[(1,3-dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl]phenyl-N-ethylpivalamide (compound No. 647) ##STR459##
1.0 Gram (0.0043 mole) of 1,3-dimethyl-5-phenoxypyrazole-4-carbaldehyde oxime, 1.3 g (0.0043 mole) of N-4-bromomethylphenyl-N-ethylpivalamide and 0.2 g (0.005 mole) of potassium hydroxide were dissolved in 30 ml of dimethyl sulfoxide, and reaction was carried out at from 40.degree. to 50.degree. C. for 6 hours. After completion of the reaction, the reaction solution was poured into 200 ml of water and extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation to obtain an oily product. This oily product was column-chromatographed on silica gel to obtain 1.5 g of the desired compound.
Yield 78%. Form of product: paste.
EXAMPLE 43
5-Ethyl-3-[N-4[{5-(4-fluorophenoxy)-1,3-dimethylpyrazol-4-yl}methyleneaminooxymethyl]-phenyl]-2-oxazolidone (compound No. 657) ##STR460##
1.0 Gram (0.0040 mole) of 5-(4-fluorophenoxy)-1,3-dimethylpyrazole-4-carbaldehyde oxime and 1.1 g (0.0040 mole) of 3-(4-bromomethylphenyl)-5-ethyl-2-oxazolidone were dissolved in 20 ml of dimethyl sulfoxide, and 0.3 g (0.0053 mole) of powdery potassium hydroxide was added. Reaction was then carried out at from 40.degree. to 50.degree. C. for 5 hours. After completion of the reaction, the reaction solution was poured into 200 ml of water and extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation to obtain an oily product. This oily product was column-chromatographed on silica gel to obtain 1.3 g of the desired compound.
Yield 72%. n.sub.D.sup.20 1.5601.
EXAMPLE 44
1,3-Dimethyl-5-phenozypyrazole-4-carbaldehyde oxime O-2-phenoxyethyl ether (compound No. 658) ##STR461##
1.0 Gram (0.0043 mole) of 1,3-dimethyl-5-phenoxypyrazole-4-carbaldehyde oxime was dissolved in 20 ml of dimethyl sulfoxide, and after adding 0.3 g (0.0053 mole) of powdery potassium hydroxide, the resulting solution was stirred. To this solution was added 0.86 g (0.0043 mole) of 2-bromoethoxybenzene, and reaction was carried out at room temperature for 3 hours. After completion of the reaction, water was added to the reaction solution which was then extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation to obtain an oily product. This oily product was column-chromatographed on silica gel to obtain 1.3 g of the desired compound.
Yield 86%. n.sub.D.sup.20 1.5657.
EXAMPLE 45
1,3-Dimethyl-5-(3-trifluoromethyphenoxy)pyrazole-4-carbaldehyde oxime O-2-(4-tert-butylphenoxy)ethyl ether (compound No. 671) ##STR462##
1.0 Gram (0.0030 mole) of 1,3-dimethyl-5-(3-trifluoromethylphenoxy)pyrazole-4-carbaldehyde oxime, 0.86 g (0.0034 mole) of p-(2-bromoethoxy)-tert-butylbenzene and 1.38 g of potassium carbonate were added to 50 ml of acetonitrile, and the resulting mixture was heated under reflux for 8 hours. After completion of the reaction, water was added to the reaction solution which was then extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation to obtain an oily product. This oily product was column-chromatographed on silica gel to obtain 1.4 g of the desired compound.
Yield 89%. n.sub.D.sup.20 1.5287.
EXAMPLE 46
Ethyl 4-[2-{(1,3-dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxy}ethoxy]benzoate (compound No. 706) ##STR463##
1.0 Gram (0.0043 mole) of 1,3-dimethyl-5-phenoxypyrazole-4-carbaldehyde oxume and 0.3 g (0.0075 mole) of powdery sodium hydroxyde were added to 30 ml of dimethylformamide, and the resulting mixture was stirred. To this solution was added 0.99 g (0.0043 mole) of ethyl p-(2-chloroethoxy)benzoate, and reaction was carried out at from 30.degree. to 40.degree. C. for 3 hours. After completion of the reaction, water was added to the reaction solution which was then extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation to obtain an oily product. This oily product was column-chromatographed on silica gel to obtain 1.3 g of the desired compound.
Yield 72%. n.sub.D.sup.20 1.5577.
EXAMPLE 47
5-(4-Chlorophenoxy)-1,3-dimethylpyrazole-4-carbaldehyde oxime O-2-(3,4-dichlorophenoxy)ethyl ether (compound No. 723) ##STR464##
1.0 Gram (0.0038 mole) of 5-(4-chlorophenoxy)-1,3-dimethylpyrazole-4-carbaldehyde oxime, 1.0 g (0.0038 mole) of 2-bromoethoxy-3,4-dichlorobenzene and 0.58 g (0.0038 mole) of 1,8-diazabicyclo[5.4.0]-7-undecene were dissolved in 50 ml of dioxane, and rection was carried out at from 60.degree. to 80.degree. C. for 5 hours with stirring. After completion of the reaction, water was added to the reaction solution which was then extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation to obtain an oily product. This oily product was column-chromatographed on silica gel to obtain 1.5 g of the desired compound.
Yield 87%. n.sub.D.sup.20 1.5756.
EXAMPLE 48
5-(4-Fluorophenoxy)-1,3-dimethylpyazole-4-carbaldehyde oxime O-2-phenoxypropyl ether (compound No. 741) ##STR465##
1.0 Gram (0.0037 mole) of sodium 5-(4-chlorophenoxy)-1,3-dimethylpyrazole-4-carbaldehyde oxime and 0.63 g (0.037 mole) of 2-chloro-1-methylethoxybenzene were added to 50 ml of tetrahydrofuran, and the resulting mixture was heated under reflux for 5 hours with stirring. After completion of the reaction, water was added to the reaction solution which was then extracted with ethyl acetate. The ethyl acetate was washed with water and dried, and ethyl acetate was removed by evaporation to obtain an oily product. This oily product was column-chromatographed on silica gel to obtain 1.3 g of the desired compound.
Yield 87%. n.sub.D.sup.20 1.5484.
EXAMPLE 49
1,3-Dimethyl-5-phenoxypyrazole-4-carbaldehyde oxime O-2-(4-tert-butylphenylthio)ethyl ether (compound No. 753) ##STR466##
1.0 Gram (0.0030 mole) of 1,3-dimethyl-5-phenoxypyrazole-4-carbaldehyde oxime O-2-bromoethyl ether, 0.5 g (0.0030 mole) of p-tert-butylbenzenethiol and 1.0 g (0.0072 mole) of potassium carbonate were added to 60 ml of acetonitrile, and the resulting mixture was heated under reflux for 5 hours. After completion of the reaction, water was added to the reaction solution which was then extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation to obtain an oily product. This oily product was column-chromatographed on silica gel to obtain 1.1 g of the desired compound.
Yield 87%. n.sub.D.sup.20 1.5775.
EXAMPLE 50
1,3-Dimethyl-5-phenoxypyrazole-4-carbaldehyde oxime O-3-(4-chlorophenoxy)propyl ether (compound No. 761) ##STR467##
1.0 Gram (0.0043 mole) of 1,3-dimethyl-5-phenoxypyrazole-4-carbaldehyde oxime and 0.3 g (0.0053 mole) of potassium hydroxide were added to 20 ml of dimethyl sulfoxide, and the resulting mixture was stirred for 1 hour. To this solution was added 1.07 g (0.0043 mole) of p-chloro-3-bromopropoxybenzene, and reaction was carried out at from 40.degree. to 50.degree. C. for 4 hours. After completion of the reaction, water was added to the reaction solution which was then extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation to obtain an oily product. This oily product was column-chromatographed on silica gel to obtain 1.3 g of the desired compound.
Yield 76%. n.sub.D.sup.20 1.5746.
EXAMPLE 51
1,3-Dimethyl-5-phenoxypyrazole-4-carbaldehyde oxime O-4-(4-chlorophenoxy)-2-butenyl ether (compound No. 776) ##STR468##
1.0 Gram (0.0031 mole) of 1,3-dimethyl-5-phenoxypyrazole-4-carbaldehyde oxime O-4-chloro-2-butenyl ether and 0.6 g (0.0036 mole) of the potassium salt of p-chlorophenol were added to 50 ml of tetrahydrofuran, and the resulting mixture was heated under reflux for 3 hours with stirring. After completion of the reaction, water was added to the reaction solution which was then extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation to obtain on oily product. This oily product was column-chromatographed on silica gel to obtain 1.2 g of the desired compound.
Yield 93%. n.sub.D.sup.20 1.5712.
EXAMPLE 52
1,3-Dimethyl-5-phenoxypyrazole-4-carbaldehyde oxime O-6-phenoxyphenyl ether (compound No. 780) ##STR469##
1.0 Gram (0.0043 mole) of 1,3-dimethyl-5-phenoxypyrazole-4-carbaldehyde oxime was dissolved in 10 ml of dimethyl sulfoxide, and after adding 0.11 g (0.0045 mole) of sodium hydride at room temperature, the resulting solution was stirred for 30 minutes. To this solution was added 1.1 g (0.0043 mole) of 6-bromohexyloxybenzene, and reaction was carried out at from 50.degree. to 60.degree. C. for 3 hours. After completion of the reaction, water was added to the reaction solution which was then extracted with acetate. The ethyl acetate was washed with water and dried, and ethyl acetate was removed by evaporation to obtain an oily product. This oily product was column-chromatographed on silica gel to obtain 1.4 g of the desired compound.
Yield 80%. n.sub.D.sup.20 1.5583.
EXAMPLE 53
2-[(1,3-Dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxy]ethyl benzoate (compound No. 787) ##STR470##
1.0 Gram (0.0043 mole) of 1,3-dimethyl-5-phenoxypyrazole-4-carbaldehyde oxime and 0.3 g (0.0054 mole) of powdery potassium hydroxide were added to 20 ml of dimethyl sulfoxide, and the resulting mixture was stirred for 30 minutes. To this solution was added 0.8 g (0.0043 mole) of 2-chloroethyl benzoate, and reaction was carried out at from 40.degree. to 50.degree. C. for 3 hours. After completion of the reaction, water was added to the reaction solution which was then extracted with ethyl acetate. The ethyl acetate was washed with water and dried, and ethyl acetate was removed by evaporation to obtain an oily product. This oily product was column-chromatographed on silica gel to obtain 1.3 g of the desired compound.
Yield 86%. n.sub.D.sup.20 1.5632.
EXAMPLE 54
1,3-Dimethyl-5-phenoxypyrazole-4-carbaldehyde oxime O-2-ethoxyethyl ether (compound No. 789) ##STR471##
1.0 Gram (0.0046 mole) of 1,3-dimethyl-5-phenoxypyrazole-4-carbaldehyde was dissolved in 40 ml of ethanol, and 0.48 g (0.0046 mole) of O-(2-ethoxyethyl)hydroxylamine was added with stirring. Reaction was then carried out at room temperature for 3 hours. After completion of the reaction, water was added to the reaction solution which was then extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation to obtain an oily product. This oily product was column-chromatographed on silica gel to obtain 1.2 g of the desired compound.
Yield 86%. n.sub.D.sup.20 1.5407.
EXAMPLE 55
1,3-Dimethyl-5-phenoxypyrazole-4-carbaldehyde oxime O-methyl ether (compound No. 790) ##STR472##
1.0 Gram (0.0043 mole) of 1,3-dimethyl-5-phenoxypyrazole-4-carbaldehyde oxime was dissolved in 20 ml of dimethyl sulfoxide, and after adding 0.3 g (0.0053 mole) of powdery potassium hydroxide, the resulting mixture was stirred. To this reaction was added 1.0 g (0.0063 mole) of methyl iodide, and reaction was carried out at room temperature for 3 hours. After completion of the reaction, the reaction solution was poured into 200 ml of water and extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation under reduced pressure to obtain an oily product. This oily product was column-chromatographed on silica gel to obtain 0.3 g of the desired compound.
Yield 76%. m.p. 70.2.degree. C.
EXAMPLE 56
5-(4-Chlorophenoxy)-1,3-dimethylpyrazole-4-carbaldehyde oxime O-2-propynyl ether (compound No. 795) ##STR473##
1.0 Gram (0.0033 mole) of 5-(4-chlorophenoxy)-1,3-dimethylpyrazole-4-carbaldehyde oxime, 0.5 g (0.0042 mole) of propargyl bromide and 1.0 g (0.0072 mole) of potassium carbonate were added to 50 ml of acetone, and the resulting mixture was heated under reflux. After completion of the reaction, the reaction solution was poured into 200 ml of water and extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation under reduced pressure to obtain an oily product. This oily product was column-chromatographed on silica gel to obtain 0.9 g of the desired compound.
Yield 87%. n.sub.D.sup.20 1.5670.
EXAMPLE 57
5-(4-Methoxyphenoxy)-1,3-dimethylpyrazole-4-carbaldehyde oxime O-2-(4-fluorophenyl)ethyl ether (compound No. 815) ##STR474##
1.0 Gram (0.0038 mole) of 5-(4-methoxyphenoxy)-1,3-dimethylpyrazole-4-carbaldehyde oxime was dissolved in 20 ml of dioxane, and after adding 0.1 g (0.0042 mole) of sodium hydride, the resulting mixture was stirred. To this reaction solution was added 0.78 g (0.0038 mole) of 2-(4-fluorophenyl)ethyl bromide, and reaction was carried out at from 40.degree. to 50.degree. C. for 3 hours. After completion of the reaction, the reaction solution was poured into 200 ml of water and extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation under reduced pressure to obtain an oily product. This oily product was column-chromatograhed on silica gel to obtain 1.2 g of the desired compound.
Yield 82%. n.sub.D.sup.20 1.5588.
EXAMPLE 58
5-(4-Chlorophenoxy)-1,3 -dimethylpyrazole-4-carbaldehyde oxime O-3-(4-chlorophenyl)propyl ether (compound No. 824) ##STR475##
1.0 Gram (0.004 mole) of 5-(4-chlorophenoxy)-1,3-dimethylpyrazole-4-carbaldehyde was dissolved in 30 ml of methanol, and 0.74 g (0.004 mole) of O-[3-(4-chlorophenyl)propyl]hydroxylamine was added at room temperature with stirring. Reaction was then carried out at from 40.degree. to 50.degree. C. for 2 hours. Methanol was then removed by evaporation under reduced pressure, after which water was added to the residue and extraction was carried out with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation under reduced pressure to obtain an oily product. This oily product was column-chromatographed on silica gel to obtain 1.1 g of the desired compound.
Yield 66%. n.sub.D.sup.20 1.5751.
EXAMPLE 59
5-(4-Chlorophenoxy)-1-methyl-3-phenylpyrazole-4-carbaldehyde oxime O-4-chlorocinnamyl ether (compound No. 846) ##STR476##
1.0 Gram (0.0030 mole) of 5-(4-chlorophenoxy)-1-methyl-3-phenylpyrazole-4-carbaldehyde oxime was reacted with 0.7 g (0.0030 mole) of p-chlorocinnamyl bromide and 0.2 g (0.005 mole) of sodium hydroxide at 30.degree. C. for 6 hours in 30 ml of dimethyl sulfoxide. After completion of the reaction, the reaction solution was poured into 200 ml of water and extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation under reduced pressure to obtain an oily product. This oily product was column-chromatographed on silica gel to obtain 1.1 g of the desired compound.
Yield 76%. n.sub.D.sup.20 1.5980.
EXAMPLE 60
1,3-Dimethyl-5-phenoxypyrazol-4-yl phenyl ketone oxime O-allyl ether (compound No. 857) ##STR477##
1.0 Gram (0.0033 mole) of 1,3-dimethyl-5-phenoxypyrazol-4-yl phenyl ketone oxime, 0.5 g (0.0041 mole) of allyl bromide and 1.0 g of potassium carbonate were added to 50 ml of acetone, and the resulting mixture was heated for 6 hours to carry out reaction. After compltion of the reaction, the reaction solution was poured into 200 ml of water and extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, and ethyl acetate was removed by evaporation under reduced pressure to obtain an oily product. This oily product was column-chromatographed on silica gel to obtain 0.9 g of the desired compound.
Yield 79%. n.sub.D.sup.20 1.5800.
Synthesis of Starting Materials
Synthetic Example 1 ##STR478##
13.2 Grams (0.006 mole) of tert-butyl 4-methylbenzoate, 0.3 g (0.0012 mole) of benzoyl peroxide and 6 g (0.006 mole) of sodium carbonate were suspended in 100 ml of carbon tetrachloride, and 9.6 g (0.06 mole) of bromine was added dropwise at 50.degree. C. over 30 minutes with stirring. After completion of the addition, reaction was continued for further 30 minutes. The reaction solution was then cooled and filtered to remove carbon tetrachloride-insoluble matters. Carbon tetrachloride was then removed by evaporation under reduced pressure to obtain 16.2 g of tert-butyl 4-bromomethylbenzoate as crystals.
Yield 90%. m.p. 53.4.degree. C.
Synthetic Example 2 ##STR479##
15.0 Grams (0.049 mole) of tert-butyl 4-bromomethylbenzoate, 8.2 g (0.05 mole) of N-hydroxyphthalimide and 3.0 (0.054 mole) of potassium hydroxide were added to 200 ml of dimethylformamide, and the resulting mixture was stirred at room temperature for 30 minutes and then an 50.degree. C. for 30 minutes. The reaction solution was cooled with ice water and filtered to obtain crystals. The crystals were dissolved in 50 ml of methylene chloride, and to this solution was slowly added dropwise 3 ml of isopropanol containing 0.5 g (0.05 mole) of hydrazine hydrate at room temperature. After completion of the addition, the reaction solution was heated under reflux for 2 hours. The reaction solution was cooled and filtered, and the filtrate was concentrated to obtain 11.0 g of tert-butyl 4-(aminoxymethyl)benzoate.
Yield 90%. n.sub.D.sup.15.6 1.5296.
Synthetic Example 3 ##STR480##
3.0 Grams (0.02 mole) of 1-p-tolylcyclopropane-1-carbonitrile and 0.1 g (0.0004 mole) of benzoyl peroxide were dissolved in 50 ml of carbon tetrachloride, and 3.2 g of bromine was added dropwise over 30 minutes under reflux. After completion of the addition, reaction was continued for further 30 minutes. After cooling the reaction solution, carbon tetrachloride was removed by evaporation to obtain 4.4 g of 1-(4-bromomethylphenyl)cyclopropane-1-carbonitrile.
Yield 90%. Form of product: paste.
NMR: .delta. (ppm) 1.15-1.40 (2H, m), 2.50-2.75 (2H, m), 4.45 (1H, s), 7.35 (4H, s).
Synthetic Example 4 ##STR481##
5.0 Grams (0.00216 mole) of 1,3-dimethyl-5-phenoxypyrazole-4-carbaldehyde oxime and 41.0 g (0.218 mole) of 1,2-dibromethane were dissolved in 100 ml of dimethyl sulfoxide, and after adding 14.4 g (0.219 mole) of 85% powdery potassium hydroxide with ice-cooling, the resulting solution was stirred for 30 minutes. After completion of the reaction, the reaction solution was poured into 300 ml of water, extracted with three 80-ml portions of ether and washed with 300 ml of water. The ether extract was dried over anydrous sodium sulfate, and ether was removed by evaporation. The residue was dry column-chromatographed on silica gel to obtain 5.2 g of 1,3-dimethyl-5-phenoxypyrazol-4-carbaldehyde oxime 0-2-bromoethyl ether.
Yield 71.2%. n.sub.D.sup.23.8 1.5721.
The present invention provides a technique for exterminating or controlling injurious insects and mites using the physiological activity of the compounds of the present invention. In one of the embodiments of the invention, the compounds are directly applied as such to the objects to be protected or to the pests to be controlled (undiluted spray). For instance, the compounds of the present invention in the form of a liquid of 95% or higher purity can be sprayed from aeroplanes to form a fog of extremely fine liquid particles.
The compounds of the present invention can also be used to treat ponds and pools in which the larvae of the insects or treat environmental water or irrigative water grown with hosts for the larvae to render the living environment or feet (hosts) toxic to the larvae.
As is customary in the art, however, in order to exterminate or control injurious insects and mites using the physiological activity of the compounds of the present invention, the compounds are applied in most cases in a form suitable for use, for example, as supported on or diluted with inert carriers and if necessary, mixed with auxiliary agents.
General suggestions regarding the formulation of insecticidal compositions with the compounds of the present invention will be described below.
The compounds of the present invention are mixed with a suitable proportion of suitable inert carriers together with auxiliary agents if necessary to allow the compounds to dissolve, disperse, suspend, mix, impregnate, adsorb or adhere, and thus they are formed into suitable preparations such as for example solutions, suspensions, emulsifiable concentrates, oil sprays, wettable powders, dusts, granules, tablets, pellets, pastes, aerosols, etc.
The inert carriers used in the formulation may be either solid or liquid. As examples of the solid carriers, there may be mentioned vegetable powders such as soybean flour, cereal flour, wood flour, bark flour, saw dust, powdered tobacco stalk, powdered walnut shell, bran, powdered cellulose, and extraction residues of vegetables; fibrous materials such as paper, corrugated paperboard, and waste cloth; synthetic polymers such as powdered synthetic resins; inorganic or mineral products such as clays (e.g. Kaolin, bentonite, and acid clay), talcs (e.g. talc and pyrophylite), siliceous substances [e.g. diatomaceous earth, silica sand, mica, and "white carbon" (highly dispersed synthetic silicon dioxide, also called finely divided hydrated silica or hydrated silicon dioxide, some commercial products containing calcium silicate as major constituent)], activated carbon, powdered sulfur, pumice, calcined diatomaceous earth, ground brick, fly ash, sand, calcium carbonate, and calcium phosphate; chemical fertilizers such as ammonium sulfate, ammonium nitrate, urea, and ammonium chloride; and farmyard manure. These materials are used alone or in combination. Materials usable as liquid carriers are selected from those which will dissolve the active ingredients and those which do not dissolve them, but can disperse them with the aid of adjuvants. For example, the following materials can be used alone or in combination: Water, alcohols (e.g. methanol, ethanol, isopropanol, butanol, ethylene glycol), ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone and cyclohexanone), ethers (e.g. ethyl ether, dioxane, cellosolves, dipropyl ether and tetrahydrofuran), aliphatic hydrocarbons (e.g. gasoline and mineral oils), aromatic hydrocarbons (e.g. benzene, toluene, xylene, solvent naphtha and alkylnapththalenes), halohydrocarbons (e.g. dichloroethane, chlorinated benzenes, chloroform and carbon tetrachloride), esters (e.g. ethyl acetate, dibutyl phthalate, diisopropyl phthalate and dioctyl phthalate), acid amides (e.g. dimethylformamide, diethylformamide and dimethylacetamide), nitriles (e.g. acetonitrile), and dimethyl sulfoxide.
Gaseous carriers include freons and other aerosol propellants which are a gas under normal conditions.
The adjuvants, which are mentioned below, are used according to individual purposes. In some cases, they are used in combination with one another. In some other cases, no adjuvant is used at all.
For the purpose of emulsification, dispersion, solubilization and/or wetting of the active ingredients, there are used surface active agents such as for example polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl ethers, polyoxyethylene higher fatty acid esters, polyoxyethylene resinates, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monooleate, alkylarylsulfonates, naphthalenesulfonic acid condensation products, ligninsulfonates and higher alcohol sulfate esters.
For the purpose of stabilizing the dispersion, tackification and/or agglomeration of the active ingredients, there may be used for example casein, gelatin, starch, alginic acid, methylcellulose, carboxymethylcellulose, gum arabic, polyvinyl alcohol, turpentine oil, rice bran oil, bentonite and ligninsulfonates.
For the purpose of improving the flow property of the solid compositions, it is recommendable to use waxes, stearates or alkyl phosphates.
As peptizers for dispersible compositions, it is also recommendable to use naphthalenesulfonic acid condensation products and polyphosphates.
It is also possible to add a defoamer such as for example a silicone oil.
The content of the active ingredient may be adjusted as occasion demands. For the preparation of powdered or granulated products, the content is usually from 0.5 to 20% by weight, and for the preparation of emulsifiable concentrates, suspension concentrates or wettable powders, it is preferably from 0.1 to 50% by weight.
For controlling various insects, mites and fungi, inhibiting their growth and protecting useful plants from damage caused by these insects, mites and fungi, the compositions of the present invention for use in agriculture and horticulture are applied in insecticidally, acaricidally or fungicidally effective amounts. In applying the present compositions, they are applied, as such or after properly diluted with or suspended in water or other suitable medium, to soil or the foliage of crops to be protected from the attack of insects, mites and fungi.
The amount of the active ingredient used depends upon various factors such as for example the purpose of application, growth state of crops, weather, environmental conditions, the form of the composition, the mode of application, the type of fields to be treated, and the like.
In applying the present fungicidal compositions alone, the dosage of the present active ingredient is preferably selected from a range of from 0.1 to 500 g per 10 ares.
Furthermore, the present compounds can be applied in the form of mixed formulations with other fungicides, insecticides, fertilizers and plant growth regulators, as far as such agents can be used in combination with the present compounds.
Examples of pesticides usable in admixture with the insecticide of the present invention will be shown below:
O,O-dimethyl O-(4-nitro-3-methylphenyl)thiophosphate (Phenitrothion)
O,O-dimethyl O-(3-methyl-4-methylthiophenyl)thiophosphate (Baycid)
O,O-dimethyl S-(carbethoxyphenylmethyl)dithiophosphate (Elsan)
O,O-diethyl O-(2-isopropyl-4-methylpyrimidyl-6)thiophosphate (Diazinon)
O,O-dimethyl 2,2,2-trichloro-1-hydroxyethylphosphate (Dipterex)
O-ethyl O-p-cyanophenyl phenylphosphonothioate (Surecide)
O-ethyl O-p-nitrophenyl phenylthiophosphonate (EPN)
O,O-dipropyl O-4-methylthiophenylphosphate (Propaphos)
O,O-dimethyl S-phthalimidomethyl dithiophosphate (Imidan)
O,O-dimethyl O-dichlorovinyl phosphate (DDVP)
O,O-dimethyl S-(N-methylcarbamoylmethyl)dithiophosphate (Dimethoate)
O,O-dimethyl S-(1,2-dicarbethoxyethyl)dithiophosphate (Malathon)
1-Naphthyl N-methylcarbamate (NAC)
m-Tolyl N-methylcarbamate (MTMC)
2-Isopropoxyphenyl N-methylcarbamate (PHC)
Ethyl N-(diethyl-dithiophosphorylacetyl)-N-methylcarbamate (Mecarbam)
3,4-Xylyl N-methylcarbamate (MPMC)
2-s-Butylphenyl N-methylcarbamate (BPMC)
2-Isopropylphenyl N-methylcarbamate (MIPC)
2-Chlorophenyl N-methylcarbamate (CPMC)
3,5-Xylyl N-methylcarbamate (XMC)
2-(1,3-Dioxolan-2-)phenyl N-methylcarbamate (Dioxacarb)
3-tert-Butylphenyl N-methylcarbamate (Terbam)
4-Diallylamino-3,5-dimethylphenyl N-methylcarbamate (APC)
S-methyl-N-(methylcarbamoyloxy) thioacetoimidate (Methomil)
N-(2-methyl-4-chlorophenyl)-N,N-dimethylformamidine hydrochloride (Chlorophenamidine)
1,3-Bis(carbamoylthio)-2-(N,N-dimethylamino)propane hydrochloride (Cartap)
Diisopropyl-1,3-dithiolan-2-ylidene malonate (Isoprothiolan)
N-[[(4-chlorophenyl)amino]carbonyl]-2,6-difluorobenzamide (Diflubenzuron)
O,O-Dimethyl-S-[2-(isopropylthio)ethyl]-phosphorodithioate (Isothioate)
O,O-Diethyl-S-[2-(ethylthio)ethyl]-phosphorodithioate (Disulfoton)
2,3-Dihydro-2,2-dimethylbenzofuran-7-yl methylcarbamate (Carbofuran)
O-Ethyl S,S-diphenyl phosphorodithioate (Edibenfos)
N-(trichloromethylthio)cyclohex-4-ene-1,2-dicarboxamide (Captan)
2,4,5,6-Tetrachloro-1,3-isophthalonitril (Chlorothalonil)
N-(1,1,2,2-tetrachloroethylthio)cyclohex-4-ene-1,2-dicarboxamide (Captafol)
Dimethyl 4,4-o-phenylene bis(3-thioallophanate) (Thiophanate methyl)
Methyl 3-(butylcarbamoyl)-3H-benzimidazol-2-ylcarbamate (Benomyl)
Zinc ethylenebis(dithiocarbamate)(polymeric) (Zineb)
Manganese ethylenebis(dithiocarbamate)(polymeric) (Maneb)
In order to demonstrate the effectiveness of the present compounds, some test examples and formulation examples will be shown below, but the present invention is not limited to these examples only.
TEST EXAMPLE 1
Fungicidal activity against the powdery mildow of barley (Erysiphe graminis f. sp. hordei)
Barley seedlings at 2-leaf stage were sprayed with test compound (200 ppm) one day after inoculation with conidia of Erysiphe graminis f. sp. hordei. The seedlings were kept in a constant-temperature room at 25.degree. C. for one week and the percentage of the infected area per leaf was examined. The fungicidal activity was judged based on the following criterion in comparison with the untreated plot.
The results are shown in Table 2.
TABLE 2______________________________________Com- Com- Com-pound Fungicidal pound Fungicidal pound FungicidalNo. activity No. activity No. activity______________________________________ 4 B 55 A 97 C 9 C 56 A 98 A 16 B 57 C 102 A 17 A 58 C 103 C 18 B 59 A 105 A 19 A 60 A 109 A 20 B 66 A 110 B 21 A 67 A 111 A 22 A 68 A 112 A 23 A 69 A 113 A 24 A 71 B 114 A 25 A 73 A 118 B 26 A 74 A 119 C 27 A 85 A 120 B 33 A 86 A 123 A 34 A 87 A 124 B 35 A 88 A 133 A 36 A 89 A 134 B 41 A 90 A 136 A 42 A 91 A 140 B 50 A 92 A 142 C 51 A 93 B 144 C 52 B 94 A 145 A 53 A 95 B 153 A 54 A 96 C 154 A155 A 212 A 249 C156 A 213 A 250 A157 A 216 A 251 B158 A 217 B 252 A159 A 219 C 253 A160 A 220 A 254 A161 B 221 A 255 A167 A 222 C 257 B181 C 228 B 258 B186 B 229 A 262 B188 A 230 A 263 A190 C 231 A 264 A193 A 232 A 265 A194 A 234 A 266 A195 A 235 A 267 A197 A 236 C 268 A198 A 237 A 269 B199 A 238 C 270 B200 A 239 A 281 B201 A 240 A 282 C202 A 241 A 283 A203 A 242 A 300 C204 B 243 A 302 B205 A 245 A 303 B206 C 246 B 304 B207 C 248 A 305 B306 A 351 A 391 A309 B 352 B 392 A311 C 353 A 393 A312 B 356 A 394 A315 A 357 A 395 A316 A 358 A 396 A321 A 363 A 397 A323 A 364 A 398 A324 C 365 A 399 A328 B 366 A 400 A329 A 369 A 401 A330 A 370 A 402 A331 A 371 C 403 A332 A 372 A 404 A333 A 373 C 405 A334 A 374 A 406 A336 B 375 A 407 A337 B 382 A 409 A340 A 383 A 421 A342 A 384 A 422 A343 A 385 A 424 A344 A 386 A 427 A346 A 387 A 428 A347 A 388 C 429 A349 B 389 A 431 A350 A 390 A 432 B433 A 470 B 496 A434 A 471 A 497 A435 B 472 A 498 A436 A 473 A 499 A437 A 474 A 501 A438 A 475 B 502 A439 A 476 A 503 A440 A 477 A 504 A441 A 478 B 505 A443 A 479 A 506 A444 A 480 A 507 A445 A 481 A 508 A446 A 482 A 518 C447 A 483 A 522 B448 A 484 A 523 B449 A 485 A 524 B450 A 486 A 527 A451 A 487 A 528 A452 A 488 B 529 B453 A 489 B 530 B454 A 490 B 532 A455 A 491 C 533 A465 A 492 B 534 C466 A 493 A 535 B468 A 494 A 536 A469 A 495 A 537 B538 A 574 B 612 A541 A 576 A 613 A545 A 578 B 614 A546 A 579 B 615 A547 A 580 B 616 A548 A 581 C 617 A549 B 584 B 618 A550 C 586 C 619 A551 C 587 B 620 A552 C 589 A 621 A553 A 591 B 622 A554 C 592 A 623 A555 C 593 A 624 A556 B 594 B 625 A557 A 595 C 626 A562 A 596 C 627 B563 A 597 C 628 B565 A 598 C 629 A566 A 601 C 630 A567 A 602 A 631 A568 A 603 A 636 A569 B 604 A 637 A570 A 608 A 638 A571 A 609 A 639 A572 B 610 A 640 A573 B 611 A 641 B642 C 677 A 727 A643 A 678 A 729 A644 B 680 A 730 B645 A 682 A 731 B646 A 683 A 732 A648 A 684 A 733 A649 A 691 B 737 A650 B 692 B 739 C652 C 693 A 740 A653 B 694 A 741 A654 B 695 A 746 B655 A 696 B 751 B656 B 697 B 753 B657 B 700 C 754 A658 A 701 A 755 A659 B 702 B 757 A660 A 707 B 758 A661 B 708 A 759 A662 B 713 A 763 B663 A 715 A 766 A667 C 716 B 767 A668 A 718 C 768 A670 A 719 A 769 A672 B 720 B 772 B675 B 724 A 773 A676 B 726 B 775 B783 B 823 A 841 B784 B 824 A 842 A795 A 825 A 843 A796 B 827 B 844 A803 A 828 C 848 A804 C 829 A 849 A805 C 831 C 850 A816 A 833 B 851 A817 A 834 A 852 B818 A 835 B 853 A819 A 836 A 854 C821 B 839 A 855 A822 B 840 B______________________________________ A: Control of disease 100-95% B: Control of disease 94-80% C: Control of disease 79-60% D: Control of disease 59-0%
TEST EXAMPLE 2
Fungicidal activity against the crown rust of oat (Puccinia coronata f.sp. avenae)
Oat seedling at 8-leaf stage were sprayed with test compound (200 ppm) one day after inoculation with uredospores of Puccinia coronata f.sp. avenae. The seedlings were kept in a constant-temperature room at 25.degree. C. for ten days and the percentage of the infected area per leaf was examined. The fungicidal activity was judged according to the same criterion as in Test example 1.
The results are shown in Table 3.
TABLE 3______________________________________Com- Com- Com-pound Fungicidal pound Fungicidal pound FungicidalNo. activity No. activity No. activity______________________________________ 14 B 60 A 111 A 18 C 66 A 112 A 19 C 67 A 113 A 21 C 68 A 114 A 22 B 69 A 133 A 23 B 71 A 134 A 24 B 73 A 135 B 25 B 74 A 136 A 27 A 85 A 138 A 33 A 86 A 139 A 34 A 87 A 140 A 35 A 88 B 142 A 36 A 89 A 143 A 41 A 90 A 144 A 42 A 91 A 145 A 50 A 92 C 153 A 51 A 93 B 154 A 52 A 94 B 155 A 53 A 95 A 156 A 54 A 96 A 157 A 55 A 97 C 158 A 56 A 98 A 159 B 57 A 105 A 160 B 58 A 109 A 161 A 59 A 110 A 186 A188 A 241 A 328 A193 A 242 B 329 A194 A 243 A 330 A195 A 245 A 331 A198 A 246 A 332 A199 A 248 C 333 A200 A 250 A 337 A201 B 251 A 340 B202 C 254 B 342 A203 A 257 A 343 A204 B 258 A 344 A205 B 263 A 345 B212 A 264 A 346 A213 C 265 A 347 A217 C 266 B 349 A220 B 267 B 350 A221 A 268 B 351 B228 B 283 B 353 A229 A 303 C 355 C230 A 305 B 356 A231 A 306 A 357 A234 A 309 C 358 A237 A 312 A 363 A238 B 315 A 364 A239 A 316 A 366 A240 A 323 B 369 A370 A 402 A 446 C371 A 403 A 447 A372 A 404 A 448 A373 A 405 A 449 A374 A 406 A 450 A375 A 407 A 451 A381 C 409 A 452 A382 A 421 A 453 A383 A 422 A 454 A384 A 427 C 455 A385 A 428 A 465 A386 A 429 A 468 A387 B 431 A 469 A388 C 433 A 470 A390 A 434 A 471 A391 A 435 B 472 A392 A 436 A 473 A393 A 437 A 474 A394 A 438 C 475 A395 A 439 A 476 B396 A 440 A 477 A397 A 441 A 478 A398 A 442 A 479 A399 A 443 B 480 A400 A 444 A 481 C401 A 445 B 482 A483 A 523 A 557 A484 A 524 A 558 C485 A 525 A 559 C486 A 527 C 560 B487 A 528 A 561 A488 A 529 A 562 B489 A 530 A 563 A490 A 531 A 565 A491 A 532 A 566 A492 A 533 A 567 A493 A 534 A 568 A494 A 535 A 569 A495 A 536 A 570 A496 A 537 A 571 A497 A 538 A 572 A498 A 544 B 573 C499 A 545 A 574 B500 C 546 A 576 A501 A 548 A 577 A502 A 550 C 578 A503 A 551 A 579 A504 A 552 C 580 A505 A 553 B 585 C506 A 554 A 586 A507 A 555 A 587 A508 A 556 A 589 A590 A 621 A 651 B591 A 622 A 652 A592 A 623 A 653 B593 A 624 A 654 A594 A 625 A 655 A595 A 626 A 656 A596 B 627 A 657 A599 B 628 A 658 A602 A 629 A 659 B603 A 630 A 660 A604 A 631 A 661 A606 C 636 A 662 A607 A 637 A 663 A608 A 638 A 667 C609 A 639 A 668 A610 A 640 A 669 B611 A 641 A 670 B612 A 642 A 672 B613 A 643 A 674 B614 A 644 A 675 A615 A 645 A 677 A616 A 646 A 678 A617 A 647 A 679 B618 A 648 A 680 A619 A 649 A 682 A620 A 650 A 683 A684 A 727 A 784 B685 A 729 A 794 C690 C 730 A 796 A691 C 731 A 804 A692 A 732 A 812 B693 A 733 A 813 A694 A 737 B 814 B695 A 746 B 815 B696 A 751 B 817 C697 A 755 A 821 A699 A 757 B 822 C701 A 758 A 823 A706 B 759 A 824 A709 A 763 A 825 A710 A 764 B 829 A711 A 766 A 830 C712 A 767 A 831 A713 B 768 A 832 C715 B 769 A 833 A717 C 770 B 834 A719 A 772 A 835 A720 C 773 A 838 A723 B 780 B 842 A724 A 781 C 843 A725 A 782 A 844 A726 A 783 B 848 A849 B 851 A 853 A850 A 852 B 854 A______________________________________
TEST EXAMPLE 3
Fungicidal activity against the downy mildew of cucumber (Pseudoperonospora cubensis)
Cucumber plants at 2-leaf stage were sprayed with test compound (200 ppm) one day before inoculation with zoospores of Psudopernospora cubensis. After the plants were kept in a humid room at 25.degree. C. one day and then in a greenhouse for six days, the degree of infection per leaf was examined and the fungicidal activity was judged according to the same criterion as in Test example 1.
The results are shown in Table 4.
TABLE 4______________________________________Compound FungicidalNo. activity______________________________________4 B9 A10 B12 C13 B16 C17 A18 C19 A20 B21 A22 A23 A24 A25 A26 A27 A33 A34 A36 A41 A42 A45 A47 C50 A51 B52 B53 C54 A55 A56 A57 A58 C59 C60 A65 C66 A67 A68 A69 B73 C74 A75 B77 B78 A79 C85 A86 B87 A88 C90 A91 A92 A93 A94 A95 A96 A97 A98 A99 A100 A101 A102 A103 B104 C105 B109 B110 A111 A112 B113 A114 A115 A116 A117 B118 B121 C122 A123 B130 A131 A133 C136 A137 B138 B139 A140 A141 C145 B147 A153 B154 A155 A156 A159 C160 B161 A162 A171 C173 A178 A179 A180 A181 C182 A183 B186 C188 A192 A193 A194 A195 B196 B197 A198 A199 A200 A201 B202 B203 A204 A205 A212 A213 A216 C220 B221 A228 B229 B230 B231 C232 B234 A237 A239 C240 A242 C243 A245 A246 B251 C252 B253 A254 A255 B256 B257 C258 C262 C263 C264 C265 A266 B267 C269 B270 C284 C288 C292 A293 B296 B297 A298 C299 A302 A303 C304 A305 B306 B312 B316 C321 A326 B328 B329 B330 B331 A332 A333 A336 A337 B342 A343 C344 B346 A350 B351 A352 B353 A354 C355 C356 A357 A358 A363 A364 A365 A366 A369 A370 A371 B372 A373 A374 A375 A376 B377 B378 C383 A385 A386 B387 B388 A389 B390 A391 A392 A393 A394 A395 A396 A397 A398 A399 A400 A401 A402 A403 A404 A405 A406 A407 A409 A420 B421 A424 A428 B429 A431 A432 B433 B434 B436 A437 A438 A439 A440 A441 A442 B444 A445 A446 B447 A448 B449 A450 A451 A452 A453 A454 A455 A465 A468 A469 A471 A473 C474 C476 B477 A478 A479 B480 A481 A482 A483 B484 A485 A486 A487 A488 A489 A490 A491 B492 C493 B496 A497 A498 C499 C502 C503 C504 A505 C506 A507 A508 A511 A512 A513 A514 A515 A516 B518 C523 A524 A525 A527 B528 A529 B531 C532 A533 A534 A535 A536 A537 A538 A541 B544 A546 A548 A551 A553 C554 C555 B556 C557 B562 A563 A565 A566 A567 B568 B569 A570 A572 A574 B576 A577 A578 C579 B584 B585 B586 A588 C589 A590 A591 A592 A593 A594 A595 A596 C597 C598 C599 B602 A603 A604 A605 A608 A609 A610 A611 A612 A613 A614 A615 A616 A617 A618 A619 A620 A621 A622 B623 A624 A625 A626 A627 A628 A629 A630 A631 C632 A633 A636 A637 A638 A639 A640 A641 A642 A643 C644 B645 A646 A647 A648 A649 A650 A651 A652 A653 A654 A655 A656 A657 A658 A659 A660 A661 A662 A663 A668 A669 A670 A673 B674 A675 A676 A677 A678 A680 A681 A682 A683 A684 A685 A686 A690 B691 A692 A693 A694 A695 A696 A697 A698 A699 C700 C701 A702 A705 A706 C709 A713 A714 B715 B716 B717 A719 B720 A725 B726 B727 B728 B729 A730 A731 B732 A733 A737 C739 B740 B741 A742 A746 A751 A752 A754 B755 A756 A757 A758 A759 A761 C763 C764 A765 B766 A767 A768 A769 A770 B772 A773 A774 A775 A776 A777 A780 A782 B783 A784 A787 B789 B804 A812 A813 A814 A815 C817 C820 C821 A822 A823 A824 A825 A826 B827 B828 B829 A831 A833 A834 A835 A836 A837 B838 C839 C840 C841 C842 A843 A844 A845 B848 A849 A850 A851 A852 A853 A854 A855 A______________________________________
TEST EXAMPLE 4
Insecticidal activity against the brown planthopper (Nilaparvata lugens)
Rice seedlings were dipped into the aqueous emulsion of the compound at 200 ppm for 30 seconds. After air-drying, the seedling were placed in a glass tube, and the 3rd instar nymphs were inoculated on the plants. On 8th day after treatment, the corrected mortality was caluculated and the insecticidal activity was judged based on the following criterion.
The results are shown in Table 5.
TABLE 5______________________________________ Compound Insecticidal No. activity______________________________________ 16 A 17 A 19 A 20 A 21 A 22 A 23 A 27 A 32 A 33 A 34 A 35 A 36 A 40 C 41 A 42 A 54 A 55 A 56 B 60 A 65 C 66 A 67 A 68 A 69 A 71 A 72 B 73 A 74 A 85 A 86 A 87 A 88 A 89 A 90 A 91 A 92 A 95 A 96 C 102 A 103 A 104 A 105 A 109 A 110 A 111 A 112 A 113 A 114 A 122 A 123 A 124 A 125 A 133 A 134 A 135 A 136 A 140 A 154 A 155 A 157 A 158 A 159 A 160 A 161 A 166 A 193 A 194 A 195 A 198 A 199 B 200 A 203 A 204 A 211 C 212 A 214 B 217 C 221 A 229 A 230 A 231 A 232 A 234 A 235 B 236 A 237 A 239 A 240 A 241 A 242 A 248 A 250 A 255 A 257 A 258 A 260 C 266 A 267 A 268 C 269 C 283 A 302 A 303 B 304 C 305 C 306 A 310 A 311 A 314 C 315 A 316 A 321 A 328 A 329 A 330 A 331 A 332 A 333 A 334 A 336 A 337 A 339 C 340 A 342 A 343 A 344 A 345 A 346 C 347 A 349 A 350 A 351 A 352 A 353 A 355 A 356 A 357 A 358 A 363 A 364 A 365 A 366 A 369 A 370 A 371 A 372 A 373 A 374 A 375 A 388 A 389 A 390 A 391 A 392 A 394 A 395 A 396 A 397 A 398 A 399 A 400 B 401 A 402 A 403 A 404 A 405 A 406 A 407 A 409 A 421 A 422 A 424 A 427 A 428 A 429 A 431 A 433 A 434 A 435 B 436 A 437 A 438 A 439 A 440 A 441 B 442 A 443 A 444 B 445 C 446 B 447 A 448 A 449 A 450 A 451 A 452 A 453 A 454 A 465 A 466 A 467 A 468 A 469 A 470 A 471 A 472 A 473 A 474 A 475 A 476 A 477 A 479 A 480 A 481 A 482 A 483 A 484 A 485 A 486 A 487 A 488 A 489 A 499 A 500 B 501 A 502 A 503 A 504 A 505 A 506 A 507 A 508 A 516 C 517 A 518 A 523 A 524 A 525 A 527 A 528 A 529 A 531 A 532 A 533 A 534 A 535 A 536 A 537 A 538 A 541 A 544 A 545 A 546 A 547 A 548 A 549 A 551 A 552 A 553 A 554 A 555 A 556 A 557 A 562 A 563 A 564 A 565 A 566 A 567 A 568 A 569 A 570 A 571 A 572 A 573 A 574 A 575 A 576 A 577 B 578 B 579 A 580 B 581 A 584 B 585 A 586 A 587 A 588 B 589 B 594 B 595 A 602 A 603 A 604 A 608 A 609 A 610 A 611 A 612 A 613 A 614 A 615 A 616 A 617 A 618 A 619 A 620 A 621 A 623 A 624 A 625 A 626 A 627 A 628 A 629 A 630 A 631 A 636 A 637 A 638 A 639 A 640 A 641 C 642 A 643 A 644 A 645 A 646 A 647 A 648 A 649 B 652 B 653 A 654 A 655 A 656 B 657 A 658 A 659 C 660 A 661 A 662 A 663 A 668 A 669 A 670 A 671 A 672 C 673 C 674 B 675 A 677 A 679 A 680 A 682 A 683 A 684 A 685 A 686 C 691 A 692 A 693 A 694 B 695 B 696 A 697 A 698 A 699 A 701 A 702 A 703 C 710 C 713 A 715 A 716 A 717 A 719 A 720 C 723 B 724 A 725 A 726 A 727 A 728 A 729 A 730 C 731 A 732 A 733 A 734 A 735 A 739 B 740 A 741 A 742 A 744 A 745 A 746 A 751 A 752 C 753 A 756 A 757 A 758 A 759 A 761 A 762 A 763 A 764 A 766 A 767 A 768 A 769 A 770 A 772 A 774 A 775 A 776 A 790 A 791 A 792 C 793 A 794 A 795 A 799 A 801 C 812 C 813 A 814 C 815 C 816 A 817 A 818 C 819 C 820 A 821 A 822 A 823 A 824 A 825 A 826 A 827 A 828 A 829 A 830 A 831 A 832 A 833 A 834 A 835 A 836 A 837 C 838 A 839 A 840 A 841 A 842 A 843 A 844 A 845 A 847 B 848 A 849 A 850 A 851 A 852 A 853 A 854 A 855 A______________________________________ A: Reviced Mortality 100-90% B: Reviced Mortality 89-80% C: Reviced Mortality 79-50%
TEST EXAMPLE 5
Insecticidal activity against the diamondback moth (Plutella xylostella)
Eggs laid on a leaf piece (6 cm.times.5 cm) of a chinese cabbage were dipped into the aqueous emulsion of the compound at 500 ppm for 30 seconds. After air-drying, the insects and the plant were placed in a petri dish. On 6th day after treatment, the corrected mortality was calculated and the insecticidal activity was judged according to the same criterion as in the test example 4.
The results are shown in Table 6.
TABLE 6______________________________________ Insecti- Insecti- Insecti-Compound cidal Compound cidal Compound cidalNo. activity No. activity No. activity______________________________________8 A 74 A 133 A18 C 85 A 136 B26 A 86 C 142 C27 C 87 A 154 A33 A 88 B 155 A34 A 89 A 156 A35 A 90 A 157 B36 B 91 A 158 A41 A 92 A 159 B42 A 94 A 160 A51 C 95 A 169 C52 A 97 C 192 A53 B 98 A 193 A54 B 102 A 195 A55 B 103 A 196 A56 A 104 A 197 B57 C 105 C 198 A59 A 109 A 199 A60 A 110 B 200 A66 A 111 B 201 A67 A 112 A 202 A68 A 113 A 203 A69 A 122 A 204 A72 A 123 A 205 B73 A 126 C 206 B207 A 251 C 328 A212 A 252 C 329 A213 A 253 A 330 A215 A 254 A 331 B216 A 255 B 333 A217 A 256 A 337 A220 B 257 A 340 A221 C 262 A 342 A228 A 263 A 343 A229 A 264 A 344 A230 A 265 C 345 B231 A 266 A 346 A232 B 267 A 347 A234 B 268 A 349 A235 A 269 C 350 A237 C 280 B 351 A239 B 281 A 352 A240 A 283 A 353 A241 A 284 A 355 A242 A 300 A 356 A243 A 302 C 357 A244 A 303 A 358 A245 A 312 A 365 A246 A 316 A 366 A248 B 321 A 369 A250 B 324 A 370 B371 B 407 A 449 A372 A 409 A 450 A373 A 420 A 451 A374 A 421 A 452 A375 A 424 B 453 A383 C 425 A 454 A384 B 427 A 455 A386 C 428 A 465 A388 A 429 A 466 A390 A 431 A 467 A391 A 432 B 468 A392 A 433 A 469 A393 A 434 A 470 A394 A 435 A 471 A395 A 436 A 472 A396 A 437 A 473 A397 A 438 A 474 A398 A 439 A 475 A399 A 440 A 476 A400 A 441 A 477 A401 A 442 A 478 A402 A 444 A 479 A403 A 445 A 480 A404 A 446 A 481 A405 A 447 A 482 A406 A 448 A 483 A484 A 524 B 564 A485 A 525 B 567 A486 A 527 A 568 A487 A 531 A 569 A489 A 532 A 570 A490 A 533 A 571 A491 A 534 A 572 A492 A 535 C 573 A493 A 536 A 576 A494 A 537 A 577 A495 A 538 C 578 A496 A 544 C 579 A497 A 545 A 580 B498 A 546 A 581 A499 A 547 A 585 C500 C 548 A 586 B501 A 549 A 587 C502 A 551 A 588 C503 A 552 C 589 B504 A 553 B 590 C505 A 554 B 592 B506 A 555 C 593 C507 A 556 C 599 C508 A 557 C 602 A517 C 562 A 603 A518 C 563 A 604 A606 C 636 A 676 A607 C 638 A 677 A608 A 639 C 678 A609 A 640 A 679 A610 A 641 A 680 A611 B 642 A 682 A612 A 643 A 683 A613 B 648 B 684 A614 B 649 A 685 A615 B 650 A 686 B616 A 651 C 687 C617 B 653 B 688 C618 A 657 A 691 C619 A 658 A 692 B620 A 659 B 693 A621 A 660 A 694 A622 A 661 A 695 A623 A 662 A 696 B624 A 663 A 698 C625 B 667 C 699 C626 A 668 A 701 A627 A 670 A 702 A628 A 671 C 703 C629 A 673 A 710 C630 A 674 A 713 A631 A 675 B 714 A715 A 760 B 818 A716 A 761 B 819 A717 A 762 A 821 A719 A 763 C 822 A720 A 764 A 823 A721 A 766 A 824 A723 A 767 A 825 A724 A 768 A 826 A725 A 769 A 827 A726 A 770 A 828 A727 A 772 A 829 A728 A 773 A 830 A729 A 774 A 831 A731 A 775 A 832 B732 A 776 C 833 A733 A 777 A 834 A734 A 780 C 835 A735 A 784 C 836 A737 B 786 C 837 A740 A 795 A 838 A741 A 799 C 839 A742 A 802 A 840 B746 A 805 C 841 A756 A 812 C 842 A757 A 815 C 843 A759 B 817 A 844 A845 A 850 A 853 A847 A 851 A 854 A848 B 852 A 855 A849 A______________________________________
TEST EXAMPLE 6
Insecticidal activity against the green peach aphid (Myzus percicae)
All stages of the aphids ware inoculated on a chinese cabbage. Insects and the plant were sprayed with the aqueous emulsion of the compound at 200 ppm. On 3rd day after treatment, the insecticidal activity was judged according to the same criterion as in the test example 4.
The results are shown in Table 7.
TABLE 7______________________________________ Insecti- Insecti- Insecti-Compound cidal Compound cidal Compound cidalNo. activity No. activity No. activity______________________________________9 B 54 A 99 A10 B 55 A 100 B12 C 56 A 101 A14 C 57 A 102 B16 C 58 A 103 A18 A 59 A 104 A19 A 60 A 105 C20 A 66 A 106 A21 A 67 A 107 C22 A 68 A 108 C23 A 69 A 109 A24 B 71 A 110 A26 A 72 B 111 A27 A 73 A 112 A33 A 74 A 113 A34 A 77 A 114 C35 B 85 A 115 A36 A 86 B 116 A41 C 87 A 117 A42 A 88 A 122 B45 A 89 A 123 C50 A 90 A 124 C51 A 91 A 130 A52 A 92 A 131 A53 A 95 A 132 A133 A 197 A 237 A134 A 198 A 238 B135 C 199 A 239 A136 A 200 A 240 A138 C 201 A 241 C139 B 202 A 243 A140 A 203 A 245 B141 A 204 A 246 A143 A 205 A 248 B145 A 207 C 249 B153 A 211 A 250 C154 B 212 A 251 A155 B 213 A 253 C156 B 215 A 254 A157 A 216 B 255 A158 B 217 C 257 C159 C 220 A 258 A160 A 221 A 262 C161 C 228 C 263 B163 A 229 A 264 A173 A 230 A 265 A180 A 231 A 266 B193 A 232 A 267 A194 A 234 A 268 A195 A 235 A 282 C196 A 236 A 296 A299 A 355 A 401 B302 B 356 A 402 B306 A 357 A 403 A311 C 358 A 404 A315 A 364 B 405 A316 B 365 A 406 C321 A 366 A 407 B328 A 370 B 409 A329 A 371 B 421 A330 A 372 C 422 A331 A 373 B 424 B332 B 374 B 427 A333 A 375 A 428 A334 B 388 B 429 A337 A 389 A 431 A340 A 390 A 432 A342 A 391 A 433 A343 A 392 A 434 A344 A 393 B 435 A345 A 394 A 436 A346 A 395 A 437 A347 A 396 A 438 A349 A 397 A 439 B350 A 398 B 440 A352 A 399 B 441 A353 A 400 A 442 A443 A 479 A 507 A444 A 480 A 508 A445 A 481 A 511 A446 A 482 A 512 A447 B 483 A 513 A448 A 484 A 514 A449 A 485 A 515 A450 A 486 A 517 C451 A 487 A 518 C452 A 488 A 527 A453 A 489 A 532 A454 A 490 A 533 A455 B 491 A 534 A465 B 492 A 537 A466 A 493 A 538 A467 A 495 A 541 B468 A 496 B 544 C469 B 497 A 545 A470 A 498 A 546 A471 B 499 A 547 A472 B 501 A 548 A473 A 502 A 549 A474 A 503 A 550 C476 A 504 A 551 C477 A 505 A 552 C478 B 506 A 553 A554 A 595 A 630 A555 B 602 A 631 A556 B 603 A 633 A557 C 604 B 634 B561 A 608 A 636 A562 A 609 A 637 A563 B 610 A 638 B564 A 611 C 639 C565 C 612 A 640 A566 A 613 A 642 B567 A 614 B 643 B568 A 615 B 644 C569 A 616 C 645 A570 A 617 A 646 A571 A 618 B 652 A572 B 619 A 654 B573 C 620 A 656 A574 A 621 B 657 A576 B 622 B 658 A577 A 623 C 660 A578 C 624 A 661 A580 C 625 A 662 B584 C 626 A 663 A585 A 627 A 664 C586 C 628 A 665 C588 C 629 A 667 B668 A 697 A 737 A669 A 698 C 741 C670 A 699 A 742 C671 A 701 A 743 C673 B 702 A 746 C674 A 703 C 751 C675 B 710 C 752 C676 B 713 A 757 B677 A 715 A 758 A678 A 716 A 759 A679 A 717 C 762 A680 A 719 A 763 C681 C 720 C 764 C682 A 723 B 766 A683 A 724 A 767 A684 B 725 A 768 A685 C 726 A 769 A686 A 727 A 770 A687 B 728 A 772 A689 B 729 A 774 A691 B 730 A 775 B692 A 731 A 776 B693 A 732 A 777 B694 A 733 A 779 A695 A 734 A 798 A696 A 735 A 799 A801 C 824 B 840 C804 C 825 B 841 A805 C 826 B 842 A812 A 827 A 843 A813 B 828 A 844 A814 B 829 A 848 C815 B 831 A 849 A816 C 832 A 850 B817 C 833 A 851 A818 C 834 A 852 A819 C 835 A 853 A821 A 836 A 854 A822 A 837 A 855 B823 A 839 A______________________________________
TEST EXAMPLE 7
Acaricidal acitivity against the citrus red mite (Panonychus citri)
Female adults were inoculated on a grapefruit leaf, and were sprayed with the aqueous emulsion of the compound at 200 ppm. On 10th day after treatment, the number of the progeny survived was counted and acaricidal activity was judged according to the same criterion as in the test example 4.
The results are shown in Table 8.
TABLE 8______________________________________Compound AcaricidalNo. activity______________________________________8 A9 A10 A11 A12 A13 B24 A25 B27 A32 A33 A34 A35 A41 A42 A50 A51 A53 C54 A55 A56 A57 A65 A68 A69 A71 A74 A86 A87 A88 A89 A90 A91 A92 A94 B95 A96 A97 A98 A102 A103 A105 A109 A112 A113 A114 A118 A119 B120 B121 A122 A124 A125 A126 A133 A134 A135 A136 A140 B147 B150 C152 A153 A154 A155 A156 A157 A158 A159 A160 A161 C164 A166 A167 B169 A170 A171 A193 A194 A195 B196 C197 A198 A199 A200 A201 A202 A206 A207 C211 A212 A214 A217 A218 A219 A220 A221 C227 A230 A232 A233 B235 A237 A238 A239 A240 A241 A242 A243 A245 A246 A248 A251 B252 A253 A254 A255 B256 A257 A258 A262 A263 A264 A265 A266 A267 A268 A269 A282 A283 A284 C300 C329 B330 B333 A334 A335 A337 A342 A343 A344 A347 A349 A350 A351 A353 A354 A355 A356 A357 A358 A363 A364 A365 A366 A367 A369 A370 A371 A373 A374 A375 B376 B377 B381 A385 A387 A388 A389 A390 A391 A392 A393 A394 A397 C399 A400 B401 A402 A403 A404 A406 B407 C408 C409 A410 C421 A422 A431 A432 A433 A434 B437 A439 C442 A443 A444 A447 A448 A449 A450 A451 A452 A453 A455 A465 A466 A467 C468 A469 A470 A471 A472 A473 A476 A477 A478 C479 A480 A481 A482 A483 A484 A485 A486 A487 A488 A489 A516 A517 A518 A523 A524 A525 A527 A529 A532 A533 A534 A535 B537 A538 A541 B543 C544 A545 A546 A547 B548 A549 A552 A553 A554 A555 A556 A557 A562 A563 A564 A565 A566 A567 A568 A569 A570 A571 A572 A573 B574 A575 A576 A577 A578 A579 B580 A584 A585 A586 A587 A588 A589 C592 C594 A595 A596 B597 A598 B599 B602 B603 C604 A605 B606 A607 A608 A609 A610 A611 A612 A613 A614 A615 A616 A617 A618 A619 B620 A621 A623 A624 A625 A626 A627 A628 A629 A630 A631 A636 A637 A638 A639 A640 A641 A642 A643 A644 B645 A646 A647 A648 A649 A650 B651 A652 A653 A654 B655 B656 B657 C658 A659 A660 A661 A662 A663 A664 A665 A666 A667 A668 A669 A670 A671 A672 A673 A674 A675 A677 A678 A680 A681 A682 A683 A684 A685 B686 B688 C690 A691 A692 A693 A694 A695 A696 A697 A698 A699 A700 A701 A702 C703 A705 A710 A711 C712 A713 A714 A715 A716 A717 A719 A720 A725 A726 A727 C728 A729 A730 A731 A732 A733 A734 A735 A737 A739 A740 A741 A742 A743 A744 A745 A746 A749 A750 C751 A754 A755 A756 A757 A758 B759 A760 A761 A763 B764 C766 A767 A768 A769 A772 B773 C774 A775 A777 A778 B795 A800 A801 B802 A812 A813 A815 A816 A817 A818 A819 A821 A822 A823 A824 B825 A826 A827 A828 A829 A830 A831 B832 B834 C835 A836 A839 B840 C842 A843 B845 A848 A850 A851 A852 A853 A854 B856 B857 B______________________________________
TEST EXAMPLE 8
Acaricidal activity against the twospotted spidermite (Tetranychus urticae)
All stages of the mites were inoculated on a soybean plant. The mites and the plant were sprayed with the aqueous emulsion of the compound at 200 ppm. On 8th day after treatment, the acaricidal activity was judged according to the same criterion as in the test example 4.
The results are shown in table 9.
TABLE 9______________________________________Compound AcaricidalNo. activity______________________________________8 A9 A10 A11 A12 A13 A17 C19 A20 A21 A22 A23 A24 A25 A32 A33 B34 A35 A36 A40 A41 A42 B50 A51 B52 A53 A54 A55 A56 A57 A58 A59 A60 A65 B66 A67 A68 A69 A71 A72 A73 A74 A85 A86 A87 A88 A89 A90 A91 A92 A93 A94 A95 A96 A97 A98 A102 A103 A104 A105 A109 A110 A111 A112 A113 A114 A118 A119 A120 A121 A122 A123 A124 A125 A126 A127 A133 A134 A135 A136 A138 A139 A140 A141 A142 C143 A144 C145 A146 A147 A149 C150 C151 C152 B153 A154 A155 A156 A157 A158 A159 A160 A161 C164 A166 A167 A169 A170 A171 A193 A194 A195 A197 B198 A199 A200 A201 A202 A203 A204 A205 A206 A207 A211 A212 A213 B214 A215 A217 A219 A220 A221 A228 A229 A230 A231 A232 B233 A234 A235 A236 A237 A238 A239 A240 A241 A242 A243 A244 A245 A246 A248 A249 A250 A251 A253 A254 A255 A256 A257 A258 A262 A263 A264 A265 A266 A267 A268 A269 A281 B282 A283 A302 B304 C328 C331 C332 C333 A334 A335 B337 C342 B343 C344 B350 C353 A354 A355 A356 A357 A358 B363 A364 A365 A366 A367 B369 A370 B371 A372 A373 A374 A375 A376 B377 C378 C379 C382 A383 A384 A385 B386 A387 A388 A389 A390 A391 A392 A393 A394 A395 A396 B397 B399 A400 A401 A402 A403 A404 A405 A406 A407 A409 A421 A422 A424 B427 B428 B431 B432 B433 C434 C436 A437 C438 A439 A440 B441 A443 A444 A445 A446 A447 C448 A449 A450 A451 A452 A453 A454 A455 A465 A466 A467 A468 A469 A470 A471 A472 A473 A474 A476 A477 A478 C479 A480 A481 A482 A483 A484 A485 A486 A487 A488 A489 A490 A491 A492 A493 A494 A495 A496 A497 A498 A499 A500 A501 A502 A503 A504 A505 A506 A507 A508 C516 C517 A518 A523 A524 A525 A527 A531 A532 A533 A534 A535 A536 A537 A538 A541 A544 A545 A546 A547 A548 A549 A550 B551 A552 A553 A554 A555 A556 A557 A558 A559 B561 A562 A563 A564 A565 B566 B567 A568 A569 A570 A571 A572 A573 A574 A575 B576 A577 A578 A579 A580 A584 A585 A587 A588 A594 A595 A596 C597 B599 B600 B602 A603 A604 A605 A606 A607 B608 A609 A610 A611 A612 A613 A614 A615 A616 A617 A618 A619 A620 A621 A623 A624 A625 A626 A627 A628 A629 A630 A631 A636 A637 A638 A639 A640 A642 A643 A644 C645 A646 A647 A648 A650 C652 A653 B654 A655 A656 A657 A658 A659 A660 A661 A662 A663 A664 A665 A666 A667 A668 A669 A670 A671 A672 A673 A674 A675 A677 A678 A680 A681 A682 A683 A684 A691 A692 A694 A695 C696 A697 A699 A701 A702 A703 A704 B705 A706 A709 A710 A712 A713 A714 B715 A716 A717 A718 C719 A720 A721 A723 A724 A725 A726 A727 A728 A729 A730 A731 A732 A733 A734 A735 B736 C737 A739 A740 A741 A742 A743 A745 B746 A751 A752 A753 A754 B756 B757 A758 A759 A760 A761 A762 B763 A764 B765 C766 A767 A768 A769 A770 A771 A772 A773 A774 A775 A776 A777 A778 A779 A780 A782 A785 B789 C791 C792 B799 B800 B801 B804 A811 C816 A817 A818 A819 A821 A822 A823 A824 A825 B826 A827 A828 A829 A830 A831 A832 A833 A834 A835 A836 A837 A838 B839 A840 A842 A843 A844 A845 C848 A850 A851 A852 A853 A854 A855 A______________________________________
Next, formulation examples will be shown. In the examples, all parts are by weight.
FORMULATION EXAMPLE 1
Wettable powder
______________________________________Compound No. 60 50 partsMixture of diatomaceous earth and clay 45 partsPolyoxyethylene nonylphenyl ether 5 parts______________________________________
The above materials were uniformly mixed and ground to obtain a wettable powder.
FORMULATION EXAMPLE 2
Emulsion
______________________________________Compound No. 154 20 partsTetrahydrofuran 20 partsXylene 45 partsMixture of polyoxyethylene nonylphenyl 15 partsether and a salt of alkylbenzenesulfonicacid______________________________________
The above materials were uniformly mixed and dissolved to obtain an emulsion.
FORMULATION EXAMPLE 3
Dust
______________________________________Compound No. 503 4 partsMixture of diatomaceous earth, clay and 95 partstalcCalcium stearate 1 part______________________________________
The above materials were univormly mixed and ground to obtain a dust.
FORMULATION EXAMPLE 4
Granule
______________________________________Compound No. 237 3 partsMixture of bentonite and clay 92 partsCalcium ligninsulfonate 5 parts______________________________________
The above materials were uniformly mixed and ground. The resulting ground mixture were thoroughly kneaded with a proper amount of water and pelletized to obtain granules.

Number	Date	Country
60-295759	Dec 1985	JPX
60-295760	Dec 1985	JPX
61-26582	Feb 1986	JPX
61-151187	Jun 1986	JPX
61-206442	Sep 1986	JPX
61-206993	Sep 1986	JPX

Pyrazole oxime derivatives and compositions

Information

Patent Number

Date Filed

Date Issued

Inventors

Original Assignees

Examiners

Agents

CPC

US Classifications

Field of Search

US

International Classifications

Abstract

Description

Claims

Priority Claims (6)

US Referenced Citations (1)