TREA

Herbicidal composition containing 2-benzyloxypyrimidine derivatives, processes for producing the derivatives and 2-benzyloxypyrimidine derivatives

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  • Patent Grant
  • 5599770
  • Patent Number
    5,599,770
  • Date Filed
    Wednesday, June 21, 1995
    29 years ago
  • Date Issued
    Tuesday, February 4, 1997
    27 years ago
Information
Abstract
A herbicidal composition comprising a herbicidally effective amount of a 2-benzyloxypyrimidine derivative represented by the formula (I): ##STR1## wherein R.sup.1 and R.sup.2 are each independently H, a halogen, hydroxyl, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.3 -C.sub.5 alkenyl, C.sub.3 -C.sub.5 alkynyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 haloalkoxy, C.sub.3 -C.sub.5 alkenyloxy, C.sub.3 -C.sub.5 alkynyloxy, C.sub.1 -C.sub.4 alkylthio, or phenyl;n is an integer of 0 to 5; andeach X which may be identical or different if n is greater than 1, is a halogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 alkylthio, C.sub.7 -C.sub.9 aralkyloxy, phenyl, hydroxymethyl, hydroxycarbonyl, C.sub.1 -C.sub.4 alkoxycarbonyl, or nitro, andan adjuvant.
Description

BACKGROUND OF THE INVENTION
The present invention relates to a herbicidal composition containing a 2-benzyloxypyrimidine derivative, processes for the production of the derivative as well as a novel 2-benzyloxypyrimidine derivative.
Among 2-benzyloxypyrimidine derivatives, three compounds, that is, 2-benzyloxypyrimidine, 2-benzyloxy-4-ethoxypyrimidine and 2-benzyloxy-4,6-dimethylpyrimidine are respectively described in the following documents: 2-benzyloxypyrimidine: J. Chem. Soc., 1965, 5542-5549; 2-benzyloxy-4-ethoxypyrimidine: J. Chem. Soc., Perkin Trans. 1, 1975, 1798-1802; and 2-benzyloxy-4,6-dimethylpyrimidine: J. Chem. Soc., 1959, 525-530.
However, there hasn't been any known document which describes herbicidal activity of 2-benzyloxypyrimidine derivatives including these three compounds.
The present inventors have found the 2-benzyloxypyrimidine derivatives having herbicidal activity and, after having studied herbicidal properties thereof and processes for the production thereof, have attained the present invention.
SUMMARY OF THE INVENTION
In a first aspect of the invention, it is provided a herbicidal composition comprising a herbicidally effective amount of a 2-benzyloxypyrimidine derivative represented by the formula (I): ##STR2## wherein R.sup.1 and R.sup.2 are each independently H, a halogen, hydroxyl, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.3 -C.sub.5 alkenyl, C.sub.3 -C.sub.5 alkynyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 haloalkoxy, C.sub.3 -C.sub.5 alkenyloxy, C.sub.3 -C.sub.5 alkynyloxy, C.sub.1 -C.sub.4 alkylthio, or phenyl;
n is an integer of 0 to 5; and
each X which may be identical or different if n is greater than 1, is a halogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 alkylthio, C.sub.7 -C.sub.9 aralkyloxy, phenyl, hydroxymethyl, hydroxycarbonyl, C.sub.1 -C.sub.4 alkoxycarbonyl, or nitro, and
an adjuvant.
In a second aspect of the invention, it is provided a process for producing a 2-benzyloxypyrimidine derivative of the formula (I): ##STR3## wherein R.sup.1, R.sup.2, X, and n are as defined above, comprising reacting a compound of the formula (II): ##STR4## wherein X and n are as defined above, with a compound of the formula (III): ##STR5## wherein R.sup.1 and R.sup.2 are as defined above; and
Z is a halogen, C.sub.1 -C.sub.4 alkylsulfonyl, C.sub.7 -C.sub.9 aralkylsulfonyl, or arylsulfonyl, in the presence of a basic compound,
with a proviso that the case in which 2-benzyloxy-4,6-dimethylpyrimidine is prepared by starting with 2-chloro-4,6-dimethylpyrimidine and benzyl alcohol is excluded.
In a third aspect of the invention, it is provided a process for producing a 2-benzyloxypyrimidine derivative of the formula (I-b): ##STR6## wherein R.sup.1 b is C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 haloalkoxy, C.sub.3 -C.sub.5 alkenyloxy, C.sub.1 -C.sub.4 alkylthio, or C.sub.3 -C.sub.5 alkynyloxy;
R.sup.2 is H, a halogen, hydroxyl, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.3 -C.sub.5 alkenyl, C.sub.3 -C.sub.5 alkynyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 haloalkoxy, C.sub.3 -C.sub.5 alkenyloxy, C.sub.3 -C.sub.5 alkynyloxy, C.sub.1 -C.sub.4 alkylthio, or phenyl;
n is an integer of 0 to 5, and
each X which may be identical or different if n is greater than 1, is a halogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 alkylthio, C.sub.7 -C.sub.9 aralkyloxy, phenyl, hydroxymethyl, hydroxycarbonyl, C.sub.1 -C.sub.4 alkoxycarbonyl, or nitro, comprising reacting a 2-benzyloxypyrimidine derivative of the formula (I-a): ##STR7## wherein R.sup.1 a is a halogen; and
R.sup.2, X, and n are as defined above, with an alcohol or alkanethiol to nucleophilically substitute for either one or both of halogens at the positions 4 and 6 on the pyrimidine ring of the 2-benzyloxypyrimidine derivative of the formula (I-a).
In a fourth aspect of the invention, it is provided a 2-benzyloxypyrimidine derivative represented by the formula (I): ##STR8## wherein R.sup.1 and R.sup.2 are each independently H, a halogen, hydroxyl, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.3 -C.sub.5 alkenyl, C.sub.3 -C.sub.5 alkynyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 haloalkoxy, C.sub.3 -C.sub.5 alkenyloxy, C.sub.3 -C.sub.5 alkynyloxy, C.sub.1 -C.sub.4 alkylthio or phenyl;
n is an integer of 0 to 5; and
each X which may be identical or different if n is greater than 1, is a halogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 alkylthio, C.sub.7 -C.sub.9 aralkyloxy, phenyl, hydroxymethyl, hydroxycarbonyl, C.sub.1 -C.sub.4 alkoxycarbonyl, or nitro,
with a proviso that 2-benzyloxypyrimidine, 2-benzyloxy-4-ethoxypyrimidine and 2-benzyloxy-4,6-dimethylpyrimidine are excluded.
DETAILED DESCRIPTION OF THE INVENTION
The terms "haloalkyl" and "haloalkoxy" used herein mean respectively alkyl and alkoxy in which at least one hydrogen is substituted with a halogen.
R.sup.1 and R.sup.2 each independently, preferably includes the following atoms and groups:
hydrogen;
a halogen such as chlorine and bromine;
hydroxyl;
C.sub.1 -C.sub.4 alkyl such as methyl (abbreviated as "Me" in the Table 1 (1/15 to 15/15), Table 3 and Table 4 given below. The following substituents are also shown therein by the abbreviations or rational formulae in parentheses), ethyl (Et), 1-methylethyl (i-Pr), propyl (Pr), and butyl;
C.sub.1 -C.sub.4 haloalkyl such as trifluoromethyl (CF.sub.3), fluoromethyl, difluoromethyl, and 2,2,2-trifluoroethyl;
C.sub.3 -C.sub.5 alkenyl such as allyl and crotyl;
C.sub.3 -C.sub.5 alkynyl such as 2-propynyl;
C.sub.1 -C.sub.4 alkoxy such as methoxy (OMe), ethoxy (OEt), (1-methylethyl)oxy (O-i-Pr), propoxy (OPr), (2-methylpropyl)oxy (O-i-Bu), (1-methylpropyl)oxy, and butoxy (OBu);
C.sub.1 -C.sub.4 haloalkoxy such as difluoromethoxy (OCHF.sub.2), 1,1,2,2-tetrafluoroethoxy, 2,2,2-trifluoroethoxy (OCH.sub.2 CF.sub.3), 2-fluoroethoxy, 2-bromo-1,1,2-trifluoroethoxy, 2,2,3,3,3-pentafluoropropoxy (OCH.sub.2 C.sub.2 F.sub.5), 1,1,2,3,3,3-hexafluoropropoxy, and 2-chloro-1,1,2-trifluoroethoxy;
C.sub.3 -C.sub.5 alkenyloxy such as allyloxy (OCH.sub.2 CH.dbd.CH.sub.2), (2-methyl-2-propenyl)oxy (OCH.sub.2 C(Me).dbd.CH.sub.2), crotyloxy (OCH.sub.2 CH.dbd.CHMe), (3-methyl-2-butenyl)oxy (OCH.sub.2 CH.dbd.C(Me).sub.2), and (3-methyl-3-butenyl)oxy (OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2);
C.sub.3 -C.sub.5 alkynyloxy such as (2-propynyl)oxy (OCH.sub.2 CCH);
C.sub.1 -C.sub.4 alkylthio such as methylthio (SMe), ethylthio (SEt), and propylthio (SPr); and
phenyl (Ph).
More preferably, R.sup.1 and R.sup.2 each independently represents methyl or methoxy, and at least one of R.sup.1 and R.sup.2 is methoxy.
X preferably includes the following atoms and groups:
a halogen such as fluorine, chlorine, bromine, and iodine;
C.sub.1 -C.sub.4 alkyl such as methyl (Me), ethyl (Et), 1-methylethyl (i-Pr), and butyl;
C.sub.1 -C.sub.4 haloalkyl such as trifluoromethyl (CF.sub.3), fluoromethyl, difluoromethyl, and 2,2,2-trifluoroethyl;
C.sub.1 -C.sub.4 alkoxy such as methoxy (OMe), ethoxy (OEt), (1-methylethyl)oxy, and (1-methylpropyl)oxy;
C.sub.1 -C.sub.4 alkylthio such as methylthio (SMe) and (1-methylethyl)thio;
C.sub.7 -C.sub.9 aralkyloxy such as benzyloxy (OBn), (1-phenylethyl)oxy, (1-phenylpropyl)oxy, and (3-phenylpropyl)oxy;
phenyl;
hydroxymethyl (CH.sub.2 OH);
hydroxycarbonyl (COOH);
C.sub.1 -C.sub.4 alkoxycarbonyl such as methoxycarbonyl (COOMe), ethoxycarbonyl (COOEt), (1-methylethyl)oxycarbonyl, propoxycarbonyl, and butoxycarbonyl; and
nitro (NO.sub.2).
More preferably, X is a halogen.
If n is greater than 1, each X may be identical or different.
Also preferably, n is an integer of 0 to 3, more preferably 0 to 2.
Z preferably includes the following atoms and groups:
a halogen such as chlorine and bromine;
C.sub.1 -C.sub.4 alkylsulfonyl such as methylsulfonyl and ethylsulfonyl;
C.sub.7 -C.sub.9 aralkylsulfonyl such as benzylsulfonyl; and arylsulfonyl (usually C.sub.6 -C.sub.8) such as phenylsulfonyl and p-tolylsulfonyl.
According to the present invention, solvents are generally used for the production of derivatives represented by the formula (I). Examples of the solvents which may be suitably used are set forth below and, when the preparing process of the present invention is carried out in a solvent, solvents below may be used alone or in combination of two or more:
water;
organic acids such as formic acid, acetic acid, and propionic acid;
aromatic hydrocarbons such as benzene, toluene, xylene, and methylnaphthalene;
aliphatic hydrocarbons such as petroleum ether, pentane, hexane, heptane, and methylcyclohexane;
halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, and chlorobenzene;
alcohols such as methanol, ethanol, i-propanol, and t-butanol;
amides such as dimethylformamide, dimethylacetamide, and N-methyl-2-pyrrolidinone;
ethers such as diethyl ether, dimethoxyethane, diisopropyl ether, tetrahydrofuran, diglyme, and dioxane;
ketones such as acetone and methyl ethyl ketone; and
others including carbon disulfide, acetonitrile, ethyl acetate, acetic anhydride, pyridine, dimethyl sulfoxide, hexamethylphosphoric amide, and the like.
When the combination of the solvents incapable of forming a homogeneous phase is used, the reaction may suitably be conducted in the presence of a phase transfer catalyst such as a conventional quaternary ammonium salt or crown ether.
Examples of the basic compounds which may be used in the process of the present invention are as follows:
alkaline metal carbonates such as sodium carbonate and potassium carbonate;
alkaline earth metal carbonates such as magnesium carbonate, calcium carbonate, and barium carbonate;
alkaline metal hydroxides such as sodium hydroxide and potassium hydroxide;
alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide;
alkaline earth metal oxides such as magnesium oxide and calcium oxide;
alkaline metals such as lithium, sodium, and potassium as well as alkaline earth metals such as magnesium;
alkaline metal alkoxides such as sodium methoxide, sodium ethoxide, and potassium t-butoxide;
alkaline metal hydrides such as sodium hydride and potassium hydride;
alkaline earth metal hydrides such as calcium hydride;
organic metal compounds such as methyl lithium, ethyl lithium, n-butyl lithium, and phenyl lithium;
organic Grignard reagents such as methylmagnesium iodide, ethylmagnesium bromide, and n-butylmagnesium bromide;
organic metal compounds of alkaline metals and organic copper compounds prepared from Grignard reagents and copper(I) salts;
alkaline metal amides such as lithium diisopropylamide;
ammonium hydroxides which may be unsubstituted or N-substituted with alkyl or aralkyl such as aqueous ammonia, benzyltrimethylammonium hydroxide, and tetramethylammonium hydroxide; and
organic amines such as methylamine, ethylamine, n-propylamine, benzylamine, ethanolamine, dimethylamine, benzylmethylamine, dibenzylamine, triethylamine, triethanolamine, and pyridine.
Also, an acid may be used in the present invention for, for example, post-treatment in the production, if necessary. Examples of the acid include inorganic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, perchloric acid, and sulfuric acid; organic acids such as formic acid, acetic acid, butyric acid, and p-toluenesulfonic acid; and Lewis acids such as boron trifluoride, aluminum chloride, and zinc chloride.
Examples of 2-benzyloxypyrimidine derivatives of the formula (I) are shown in Table 1 (1/15 to 15/15).
TABLE 1______________________________________(1/15)Xn and positionNo. 2 3 4 5 6 R.sup.1 R.sup.2______________________________________I-1 Cl H H H H H HI-2 H Cl H H H H HI-3 H H Cl H H H HI-4 Cl H H H H Me HI-5 H Cl H H H Me HI-6 H H Cl H H Me HI-7 H H H H H Me HI-8 Cl H H H H Me MeI-9 H Cl H H H Me MeI-10 F H H H H Me MeI-11 Br H H H H Me MeI-12 OMe H H H H Me MeI-13 H F H H H Me MeI-14 H Br H H H Me MeI-15 H OMe H H H Me MeI-16 H H Cl H H Me MeI-17 H H F H H Me MeI-18 H H Br H H Me MeI-19 H H OMe H H Me MeI-20 H H H H H Me MeI-21 F H F H H Me O-i-PrI-22 Et H H H H Me O-i-PrI-23 H F F H H Me O-i-PrI-24 H H H H H Me OCH.sub.2 CF.sub.3I-25 F F H H H OMe OMeI-26 Me Me OMe H H OMe OMeI-27 OMe OMe H H H OMe OMeI-28 Cl H Cl H H OMe OMeI-29 F H F H H OMe OMeI-30 Me H Me H H OMe OMeI-31 OMe Me OMe H H OMe OMeI-32 OMe H OMe H H OMe OMeI-33 Cl H H Cl H OMe OMeI-34 F H H F H OMe OMeI-35 Me H H Me H OMe OMeI-36 OMe H H OMe H OMe OMeI-37 Cl H H H Cl OMe OMeI-38 F H H H F OMe OMeI-39 OEt H H H H OMe OMeI-40 Cl H H H F OMe OMeI-41 CF.sub.3 H H H H OMe OMeI-42 OMe H H H H OMe OMeI-43 I H H H H OMe OMeI-44 H OMe OMe OMe H OMe OMeI-45 H Cl Cl H H OMe OMeI-46 H F F H H OMe OMeI-47 H Me Me H H OMe OMeI-48 H Cl H Cl H OMe OMeI-49 H F H F H OMe OMeI-50 H Me H Me H OMe OMeI-51 H OMe H OMe H OMe OMeI-52 H CF.sub.3 H CF.sub.3 H OMe OMeI-53 H CF.sub.3 H H H OMe OMeI-54 H OEt Me H H OMe OMeI-55 H OEt OMe H H OMe OMeI-56 H NO.sub.2 H H H OMe OMeI-57 H OBn H H H OMe OMeI-58 H OMe H H H OMe OMeI-59 H I H H H OMe OMeI-60 H H i-Pr H H OMe OMeI-61 H H CF.sub.3 H H OMe OMeI-62 H OMe OEt H H OMe OMeI-63 H H Ph H H OMe OMeI-64 OMe H Br H H OMe OMeI-65 H OMe OBn H H OMe OMeI-66 H H OBn H H OMe OMeI-67 H H SMe H H OMe OMeI-68 H H OMe H H OMe OMe______________________________________
TABLE 1______________________________________(2/15)Xn and positionNo. 2 3 4 5 6 R.sup.1 R.sup.2______________________________________I-69 F H F H H Br BrI-70 Cl H H H H Br BrI-71 F H H H H Br BrI-72 H F F H H Br BrI-73 H F H F H Br BrI-74 H Cl H H H Br BrI-75 H F H H H Br BrI-76 H H Cl H H Br BrI-77 H H CF.sub.3 H H Br BrI-78 H H F H H Br BrI-79 H H Me H H Br BrI-80 H H OMe H H Br BrI-81 H H H H H Br BrI-82 F F H H H Cl CF.sub.3I-83 F H F H H Cl CF.sub.3I-84 F H H F H Cl CF.sub.3I-85 F H H H F Cl CF.sub.3I-86 CF.sub.3 H H H H Cl CF.sub.3I-87 COOMe H H H H Cl CF.sub.3I-88 Cl H H H H Cl CF.sub.3I-89 F H H H H Cl CF.sub.3I-90 Br H H H H Cl CF.sub.3I-91 Me H H H H Cl CF.sub.3I-92 OMe H H H H Cl CF.sub.3I-93 I H H H H Cl CF.sub.3I-94 H F F H H Cl CF.sub.3I-95 H F H F H Cl CF.sub.3I-96 H CF.sub.3 H H H Cl CF.sub.3I-97 H Cl H H H Cl CF.sub.3I-98 H F H H H Cl CF.sub.3I-99 H Br H H H Cl CF.sub.3I-100 H Me H H H Cl CF.sub.3I-101 H OMe H H H Cl CF.sub.3I-102 H I H H H Cl CF.sub.3I-103 H H CF.sub.3 H H Cl CF.sub.3I-104 H H Cl H H Cl CF.sub.3I-105 H H F H H Cl CF.sub.3I-106 H H Br H H Cl CF.sub.3I-107 H H Me H H Cl CF.sub.3I-108 H H OMe H H Cl CF.sub.3I-109 H H I H H Cl CF.sub.3I-110 H H H H H Cl CF.sub.3I-111 F F H H H Cl ClI-112 Me Me OMe H H Cl ClI-113 OMe OMe H H H Cl ClI-114 Cl H Cl H H Cl ClI-115 F H F H H Cl ClI-116 Me H Me H H Cl ClI-117 OMe Me OMe H H Cl ClI-118 OMe H OMe H H Cl ClI-119 Cl H H Cl H Cl ClI-120 F H H F H Cl ClI-121 Me H H Me H Cl ClI-122 OMe H H OMe H Cl ClI-123 Cl H H H Cl Cl ClI-124 F H H H F Cl ClI-125 COOEt H H H H Cl ClI-126 CF.sub.3 H H H H Cl ClI-127 COOH H H H H Cl ClI-128 CH.sub.2 OH H H H H Cl ClI-129 COOMe H H H H Cl ClI-130 Et H H H H Cl ClI-131 OEt H H H H Cl ClI-132 Cl H H H F Cl ClI-133 Cl H H H H Cl ClI-134 F H H H H Cl ClI-135 Br H H H H Cl ClI-136 Me H H H H Cl ClI-137 OMe H H H H Cl ClI-138 I H H H H Cl ClI-139 H OMe OMe OMe H Cl ClI-140 H Cl Cl H H Cl ClI-141 H F F H H Cl ClI-142 H Me Me H H Cl ClI-143 H OMe H OMe H Cl ClI-144 H Cl H Cl H Cl ClI-145 H F H F H Cl ClI-146 H Me H Me H Cl ClI-147 H CF.sub.3 H CF.sub.3 H Cl ClI-148 H CF H H H Cl ClI-149 H OBn H H H Cl ClI-150 H OEt OMe H H Cl ClI-151 H Cl H H H Cl ClI-152 H NO.sub.2 H H H Cl ClI-153 H F H H H Cl ClI-154 H Br H H H Cl ClI-155 H Me H H H Cl ClI-156 H OMe H H H Cl ClI-157 H I H H H Cl ClI-158 H H i-Pr H H Cl ClI-159 H H CF.sub.3 H H Cl ClI-160 H OMe OBn H H Cl ClI-161 H H OBn H H Cl ClI-162 H H SMe H H Cl ClI-163 H H CO.sub.2 Me H H Cl ClI-164 H OMe OEt H H Cl ClI-165 H H Cl H H Cl ClI-166 H H Ph H H Cl ClI-167 H H F H H Cl ClI-168 OMe H Br H H Cl ClI-169 H H Br H H Cl ClI-170 H H Me H H Cl ClI-171 H H OMe H H Cl ClI-172 H H I H H Cl ClI-173 H H H H H Cl ClI-174 F F H H H Cl EtI-175 F H F H H Cl EtI-176 F H H F H Cl EtI-177 F H H H F Cl EtI-178 CF.sub.3 H H H H Cl EtI-179 COOMe H H H H Cl EtI-180 Cl H H H H Cl EtI-181 F H H H H Cl EtI-182 Br H H H H Cl EtI-183 Me H H H H Cl EtI-184 OMe H H H H Cl EtI-185 I H H H H Cl EtI-186 H F F H H Cl EtI-187 H F H F H Cl EtI-188 H CF.sub.3 H H H Cl EtI-189 H Cl H H H Cl EtI-190 H F H H H Cl EtI-191 H Br H H H Cl EtI-192 H Me H H H Cl EtI-193 H OMe H H H Cl EtI-194 H I H H H Cl EtI-195 H H CF.sub.3 H H Cl EtI-196 H H Cl H H Cl EtI-197 H H F H H Cl EtI-198 H H Br H H Cl EtI-199 H H Me H H Cl EtI-200 H H OMe H H Cl EtI-201 H H I H H Cl EtI-202 H H H H H Cl EtI-203 F F H H H Cl MeI-204 Cl H Cl H H Cl MeI-205 F H F H H Cl MeI-206 Me H Me H H Cl MeI-207 Cl H H Cl H Cl MeI-208 F H H F H Cl MeI-209 Me H H Me H Cl MeI-210 Cl H H H Cl Cl MeI-211 F H H H F Cl MeI-212 CF.sub.3 H H H H Cl MeI-213 COOMe H H H H Cl MeI-214 Cl H H H H Cl MeI-215 F H H H H Cl MeI-216 Br H H H H Cl MeI-217 Me H H H H Cl MeI-218 OMe H H H H Cl MeI-219 I H H H H Cl MeI-220 H Cl Cl H H Cl MeI-221 H F F H H Cl MeI-222 H Me Me H H Cl MeI-223 H Cl H Cl H Cl MeI-224 H F H F H Cl MeI-225 H Me H Me H Cl MeI-226 H CF.sub.3 H H H Cl MeI-227 H Cl H H H Cl MeI-228 H F H H H Cl MeI-229 H Br H H H Cl MeI-230 H Me H H H Cl MeI-231 H OMe H H H Cl MeI-232 H I H H H Cl MeI-233 H H CF.sub.3 H H Cl MeI-234 H H Cl H H Cl MeI-235 H H F H H Cl MeI-236 H H Br H H Cl MeI-237 H H Me H H Cl MeI-238 H H OMe H H Cl MeI-239 H H I H H Cl MeI-240 H H H H H Cl MeI-241 F F H H H Cl PhI-242 F H F H H Cl PhI-243 F H H F H Cl PhI-244 F H H H F Cl PhI-245 CF.sub.3 H H H H Cl PhI-246 COOMe H H H H Cl PhI-247 Cl H H H H Cl PhI-248 F H H H H Cl PhI-249 Br H H H H Cl PhI-250 Me H H H H Cl PhI-251 OMe H H H H Cl PhI-252 I H H H H Cl PhI-253 H F F H H Cl PhI-254 H F H F H Cl PhI-255 H CF.sub.3 H H H Cl PhI-256 H Cl H H H Cl PhI-257 H F H H H Cl PhI-258 H Br H H H Cl PhI-259 H Me H H H Cl PhI-260 H OMe H H H Cl PhI-261 H I H H H Cl PhI-262 H H CF.sub.3 H H Cl PhI-263 H H Cl H H Cl PhI-264 H H F H H Cl PhI-265 H H Br H H Cl PhI-266 H H Me H H Cl PhI-267 H H OMe H H Cl PhI-268 H H I H H Cl PhI-269 H H H H H Cl PhI-270 F F H H H Cl PrI-271 F H F H H Cl PrI-272 F H H F H Cl PrI-273 F H H H F Cl PrI-274 CF.sub.3 H H H H Cl PrI-275 COOMe H H H H Cl PrI-276 Cl H H H H Cl PrI-277 F H H H H Cl PrI-278 Br H H H H Cl PrI-279 Me H H H H Cl PrI-280 OMe H H H H Cl PrI-281 I H H H H Cl PrI-282 H F F H H Cl PrI-283 H F H F H Cl PrI-284 H CF.sub.3 H H H Cl PrI-285 H Cl H H H Cl PrI-286 H F H H H Cl PrI-287 H Br H H H Cl PrI-288 H Me H H H Cl PrI-289 H OMe H H H Cl PrI-290 H I H H H Cl PrI-291 H H CF.sub.3 H H Cl PrI-292 H H Cl H H Cl PrI-293 H H F H H Cl PrI-294 H H Br H H Cl PrI-295 H H Me H H Cl PrI-296 H H OMe H H Cl PrI-297 H H I H H Cl PrI-298 H H H H H Cl PrI-299 F F H H H Cl i-PrI-300 F H F H H Cl i-PrI-301 F H H F H Cl i-PrI-302 F H H H F Cl i-PrI-303 CF.sub.3 H H H H Cl i-PrI-304 H H H H H Cl i-PrI-305 Cl H H H H Cl i-PrI-306 F H H H H Cl i-PrI-307 Br H H H H Cl i-PrI-308 Me H H H H Cl i-PrI-309 OMe H H H H Cl i-PrI-310 I H H H H Cl i-PrI-311 H F F H H Cl i-PrI-312 H F H F H Cl i-PrI-313 H CF.sub.3 H H H Cl i-PrI-314 H Cl H H H Cl i-PrI-315 H F H H H Cl i-PrI-316 H Br H H H Cl i-PrI-317 H Me H H H Cl i-PrI-318 H OMe H H H Cl i-PrI-319 H I H H H Cl i-PrI-320 H H CF.sub.3 H H Cl i-PrI-321 H H Cl H H Cl i-PrI-322 H H F H H Cl i-PrI-323 H H Br H H Cl i-PrI-324 H H Me H H Cl i-PrI-325 H H OMe H H Cl i-PrI-326 H H I H H Cl i-PrI-327 H H H H H Cl i-Pr______________________________________
TABLE 1__________________________________________________________________________(3/15)No. X.sub.n R.sup.1 R.sup.1__________________________________________________________________________I-328 n = 0 for OCHF.sub.2 OCHF.sub.2I-329 Compound I-328 CF.sub.3 OCH.sub.2 C(Me).dbd.CH.sub.2I-330 through CF.sub.3 OCH.sub.2 CCHI-331 Compound I-437 CF.sub.3 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-332 CF.sub.3 OCH.sub.2 CH.dbd.C(Me).sub.2I-333 CF.sub.3 OCH.sub.2 CH.dbd.CH.sub.2I-334 CF.sub.3 OCH.sub.2 CH.dbd.CHMeI-335 Cl O-i-BuI-336 Cl OBuI-337 Cl OCH.sub.2 C(Me).dbd.CH.sub.2I-338 Cl OCH.sub.2 C.sub.2 F.sub.5I-339 Cl OCH.sub.2 CCHI-340 Cl OCH.sub.2 CF.sub.3I-341 Cl OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-342 Cl OCH.sub.2 CH.dbd.C(Me).sub.2I-343 Cl OCH.sub.2 CH.dbd.CH.sub.2I-344 Cl OCH.sub.2 CH.dbd.CHMeI-345 Cl OEtI-346 Cl OMeI-347 Cl OPrI-348 Et OCH.sub.2 C(Me).dbd.CH.sub.2I-349 Et OCH.sub.2 CCHI-350 Et OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-351 Et OCH.sub.2 CH.dbd.C(Me).sub.2I-352 Et OCH.sub.2 CH.dbd.CH.sub.2I-353 Et OCH.sub.2 CH.dbd.CHMeI-354 Me O-i-PrI-355 Me OCH.sub.2 C(Me).dbd.CH.sub.2I-356 Me OCH.sub.2 CCHI-357 Me OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-358 Me OCH.sub.2 CH.dbd.C(Me).sub.2I-359 Me OCH.sub.2 CH.dbd.CH.sub.2I-360 Me OCH.sub.2 CH.dbd.CHMeI-361 Me OEtI-362 Me OMeI-363 O-i-Bu O-i-BuI-364 OBu OBuI-365 OCH.sub.2 C(Me).dbd.CH.sub.2 OCH.sub.2 C(Me).dbd.CH.sub.2I-366 OCH.sub.2 CCH OCH.sub.2 CCHI-367 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-368 OCH.sub.2 CH.dbd.C(Me).sub.2 OCH.sub.2 CH.dbd.C(Me).sub.2I-369 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.dbd.CH.sub.2I-370 OCH.sub.2 CH.dbd.CHMe OCH.sub.2 CH.dbd.CHMeI-371 OEt OEtI-372 OMe OMeI-373 OPr OPrI-374 Pr OCH.sub.2 C(Me).dbd.CH.sub.2I-375 Pr OCH.sub.2 CCHI-376 Pr OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-377 Pr OCH.sub.2 CH.dbd.C(Me).sub.2I-378 Pr OCK21CN.dbd.CN2I-379 Pr OCH.sub.2 CH.dbd.CHMeI-380 i-Pr OCH.sub.2 C(Me).dbd.CH.sub.2I-381 i-Pr OCH.sub.2 CCHI-382 i-Pr OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-383 i-Pr OCH.sub.2 CH.dbd.C(Me).sub.2I-384 i-Pr OCH.sub.2 CH.dbd.CH.sub.2I-385 i-Pr OCH.sub.2 CH.dbd.CHMeI-386 O-i-Bu OCH.sub.2 C(Me).dbd.CH.sub.2I-387 O-i-Bu OCH.sub.2 CCHI-388 O-i-Bu OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-389 O-i-Bu OCH.sub.2 CH.dbd.C(Me).sub.2I-390 O-i-Bu OCH.sub.2 CH.dbd.CH.sub.2I-391 O-i-Bu OCH.sub.2 CH.dbd.CHMeI-392 OBu O-i-BuI-393 OBu OCH.sub.2 C(Me).dbd.CH.sub.2I-394 OBu OCH.sub.2 CCHI-395 OBu OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-396 OBu OCH.sub.2 CH.dbd.C(Me).sub.2I-397 OBu OCH.sub.2 CH.dbd.CH.sub.2I-398 OBu OCH.sub.2 CH.dbd.CHMeI-399 OCH.sub.2 CF.sub.3 OCH.sub.2 C(Me).dbd.CH.sub.2I-400 OCH.sub.2 CF.sub.3 OCH.sub.2 C.sub.2 F.sub.5I-401 OCH.sub.2 CF.sub.3 OCH.sub.2 CCHI-402 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-403 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.dbd.C(Me).sub.2I-404 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.dbd.CH.sub.2I-405 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.dbd.CHMeI-406 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 C(Me).dbd.CH.sub.2I-407 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CCHI-408 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-409 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.dbd.C(Me).sub.2I-410 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.dbd.CHMeI-411 OEt O-i-BuI-412 OEt OBuI-413 OEt OCH.sub.2 C(Me).dbd.CH.sub.2I-414 OEt OCH.sub.2 CCHI-415 OEt OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-416 OEt OCH.sub.2 CH.dbd.C(Me).sub.2I-417 OEt OCH.sub.2 CH.dbd.CH.sub.2I-418 OEt OCH.sub.2 CH.dbd.CHMeI-419 OEt OPrI-420 OMe O-i-BuI-421 OMe OBuI-422 OMe OCH.sub.2 C(Me).dbd.CH2-I-423 OMe OCH.sub.2 CCHI-424 OMe OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-425 OMe OCH.sub.2 CH.dbd.C(Me).sub.2I-426 OMe OCH.sub.2 CH.dbd.CH.sub.2I-427 OMe OCH.sub.2 CH.dbd.CHMeI-428 OMe OEtI-429 OMe OPrI-430 OPr O-i-BuI-431 OPr OBuI-432 OPr OCH.sub.2 C(Me).dbd.CH.sub.2I-433 OPr OCH.sub.2 CCHI-434 OPr OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-435 OPr OCH.sub.2 CH.dbd.C(Me).sub.2I-436 OPr OCH.sub.2 CH.dbd.CH.sub.2I-437 OPr OCH.sub.2 CH.dbd.CHMe I-2001 n = 0 for Me SMe I-2002 Compound I-2001 Me SEt I-2003 through Me SPr I-2004 Compound I-2015 OMe SMe I-2005 OMe SEt I-2006 OMe SPr I-2007 SMe SMe I-2008 SEt SEt I-2009 SPr SPr I-2010 OCH.sub.2 CH.dbd.CH.sub.2 SMe I-2011 OCH.sub.2 CH.dbd.CH.sub.2 SEt I-2012 OCH.sub.2 CH.dbd.CH.sub.2 SPr I-2013 Cl SMe I-2014 Cl SEt I-2015 Cl SPr__________________________________________________________________________
__________________________________________________________________________(4/15)No. X.sub.n R.sup.1 R.sup.1__________________________________________________________________________I-438 A chlorine atom OCHF.sub.2 OCHF.sub.2I-439 at 2-position CF.sub.3 OCH.sub.2 C(Me).dbd.CH.sub.2I-440 (2-Cl) for CF.sub.3 OCH.sub.2 CCHI-441 Compound I-438 CF.sub.3 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-442 through CF.sub.3 OCH.sub.2 CH.dbd.C(Me).sub.2I-443 Compound I-547 CF.sub.3 OCH.sub.2 CH.dbd.CH.sub.2I-444 CF.sub.3 OCH.sub.2 CH.dbd.CHMeI-445 Cl O-i-BuI-446 Cl OBuI-447 Cl OCH.sub.2 C(Me).dbd.CH.sub.2I-448 Cl OCH.sub.2 C.sub.2 F.sub.5I-449 Cl OCH.sub.2 CCHI-450 Cl OCH.sub.2 CF.sub.3I-451 Cl OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-452 Cl OCH.sub.2 CH.dbd.C(Me).sub.2I-453 Cl OCH.sub.2 CH.dbd.CH.sub.2I-454 Cl OCH.sub.2 CH.dbd.CHMeI-455 Cl OEtI-456 Cl OMeI-457 Cl OPrI-458 Et OCH.sub.2 C(Me).dbd.CH.sub.2I-459 Et OCH.sub.2 CCHI-460 Et OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-461 Et OCH.sub.2 CH.dbd.C(Me).sub.2I-462 Et OCH.sub.2 CH.dbd.CH.sub.2I-463 Et OCH.sub.2 CH.dbd.CHMeI-464 Me O-i-PrI-465 Me OCH.sub.2 C(Me).dbd.CH.sub.2I-466 Me OCH.sub.2 CCHI-467 Me OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-468 Me OCH.sub.2 CH.dbd.C(Me).sub.2I-469 Me OCH.sub.2 CH.dbd.CH.sub.2I-470 Me OCH.sub.2 CH.dbd.CHMeI-471 Me OEtI-472 Me OMeI-473 O-i-Bu O-i-BuI-474 OBu OBuI-475 OCH.sub.2 C(Me).dbd.CH.sub.2 OCH.sub.2 C(Me).dbd.CH.sub.2I-476 OCH.sub.2 CCH OCH.sub.2 CCHI-477 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-478 OCH.sub.2 CH.dbd.C(Me).sub.2 OCH.sub.2 CH.dbd.C(Me).sub.2I-479 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.dbd.CH.sub.2I-480 OCH.sub.2 CH.dbd.CHMe OCH.sub.2 CH.dbd.CHMeI-481 OEt OEtI-482 OMe OMeI-483 OPr OPrI-484 Pr OCH.sub.2 C(Me).dbd.CH.sub.2I-485 Pr OCH.sub.2 CCHI-486 Pr OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-487 Pr OCH.sub.2 CH.dbd.C(Me).sub.2I-488 Pr OCH.sub.2 CH.dbd.CH.sub.2I-489 Pr OCH.sub.2 CH.dbd.CHMeI-490 i-Pr OCH.sub.2 C(Me).dbd.CH.sub.2I-491 i-Pr OCH.sub.2 CCHI-492 i-Pr OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-493 i-Pr OCH.sub.2 CH.dbd.C(Me).sub.2I-494 i-Pr OCH.sub.2 CH.dbd.CH.sub.2I-495 i-Pr OCH.sub.2 CH.dbd.CHMeI-496 O-i-Bu OCH.sub.2 C(Me).dbd.CH.sub.2I-497 O-i-Bu OCH.sub.2 CCHI-498 O-i-Bu OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-499 O-i-Bu OCH.sub.2 CH.dbd.C(Me).sub.2I-500 O-i-Bu OCH.sub.2 CH.dbd.CH.sub.2I-501 O-i-Bu OCH.sub.2 CH.dbd.CHMeI-502 OBu O-i-BuI-503 OBu OCH.sub.2 C(Me).dbd.CH.sub.2I-504 OBu OCH.sub.2 CCHI-505 OBu OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-506 OBu OCH.sub.2 CH.dbd.C(Me).sub.2I-507 OBu OCH.sub.2 CH.dbd.CH.sub.2I-508 OBu OCH.sub.2 CH.dbd.CHMeI-509 OCH.sub.2 CF.sub.3 OCH.sub.2 C(Me).dbd.CH.sub.2I-510 OCH.sub.2 CF.sub.3 OCH.sub.2 C.sub.2 F.sub.5I-511 OCH.sub.2 CF.sub.3 OCH.sub.2 CCHI-512 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-513 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.dbd.C(Me).sub.2I-514 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.dbd.CH.sub.2I-515 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.dbd.CHMeI-516 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 C (Me) .dbd.CH.sub.2I-517 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CCHI-518 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-519 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.dbd.C(Me).sub.2I-520 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.dbd.CHMeI-521 OEt O-i-BuI-522 OEt OBuI-523 OEt OCH.sub.2 C(Me).dbd.CH.sub.2I-524 OEt OCH.sub.2 CCHI-525 OEt OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-526 OEt OCH.sub.2 CH.dbd.C(Me).sub.2I-527 OEt OCH.sub.2 CH.dbd.CH.sub.2I-528 OEt OCH.sub.2 CH.dbd.CHMeI-529 OEt OPrI-530 OMe O-i-BuI-531 OMe OBuI-532 OMe OCH.sub.2 C(Me).dbd.CH.sub.2I-533 OMe OCH.sub.2 CCHI-534 OMe OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-535 OMe OCH.sub.2 CH.dbd.C(Me).sub.2I-536 OMe OCH.sub.2 CH.dbd.CH.sub.2I-537 OMe OCH.sub.2 CH.dbd.CHMeI-538 OMe OEtI-539 OMe OPrI-540 OPr O-i-BuI-541 OPr OBuI-542 OPr OCH.sub.2 C(Me).dbd.CH.sub.2I-543 OPr OCH.sub.2 CCHI-544 OPr OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-545 OPr OCH.sub.2 CH.dbd.C(Me).sub.2I-546 OPr OCH.sub.2 CH.dbd.CH.sub.2I-547 OPr OCH.sub.2 CH.dbd.CHMe__________________________________________________________________________
TABLE 1__________________________________________________________________________(5/15)No. X.sub.n R.sup.1 R.sup.1__________________________________________________________________________I-548 A fluorine atom OCHF.sub.2 OCHF.sub.2I-549 at 2-position CF.sub.3 OCH.sub.2 C(Me).dbd.CH.sub.2I-550 (2-F) for CF.sub.3 OCH.sub.2 CCHI-551 Compound I-548 CF.sub.3 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-552 through CF.sub.3 OCH.sub.2 CH.dbd.C(Me).sub.2I-553 Compound I-657 CF.sub.3 OCH.sub.2 CH.dbd.CH.sub.2I-554 through CF.sub.3 OCH.sub.2 CH.dbd.CHMeI-555 Compound Cl O-i-BuI-556 I-657 Cl OBuI-557 Cl OCH.sub.2 C(Me).dbd.CH.sub.2I-558 Cl OCH.sub.2 C.sub.2 F.sub.5I-559 Cl OCH.sub.2 CCHI-560 Cl OCH.sub.2 CF.sub.3I-561 Cl OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-562 Cl OCH.sub.2 CH.dbd.C(Me).sub.2I-563 Cl OCH.sub.2 CH.dbd.CH.sub.2I-564 Cl OCH.sub.2 CH.dbd.CHMeI-565 Cl OEtI-566 Cl OMeI-567 Cl OPrI-568 Et OCH.sub.2 C(Me).dbd.CH.sub.2I-569 Et OCH.sub.2 CCHI-570 Et OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-571 Et OCH.sub.2 CH.dbd.C(Me).sub.2I-572 Et OCH.sub.2 CH.dbd.CH.sub.2I-573 Et OCH.sub.2 CH.dbd.CHMeI-574 Me O-i-PrI-575 Me OCH.sub.2 C(Me).dbd.CH.sub.2I-576 Me OCH.sub.2 CCHI-577 Me OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-578 Me OCH.sub.2 CH.dbd.C(Me).sub.2I-579 Me OCH.sub.2 CH.dbd.CH.sub.2I-580 Me OCH.sub.2 CH.dbd.CHMeI-581 Me OEtI-582 Me OMeI-583 O-i-Bu O-i-BuI-584 OBu OBuI-585 OCH.sub.2 C(Me).dbd.CH.sub.2 OCH.sub.2 C(Me).dbd.CH.sub.2I-586 OCH.sub.2 CCH OCH.sub.2 CCHI-587 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-588 OCH.sub.2 CH.dbd.C(Me).sub.2 OCH.sub.2 CH.dbd.C(Me).sub.2I-589 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.dbd.CH.sub.2I-590 OCH.sub.2 CH.dbd.CHMe OCH.sub.2 CH.dbd.CHMeI-591 OEt OEtI-592 OMe OMeI-593 OPr OPrI-594 Pr OCH.sub.2 C(Me).dbd.CH.sub.2I-595 Pr OCH.sub.2 CCHI-596 Pr OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-597 Pr OCH.sub.2 CH.dbd.C(Me).sub.2I-598 Pr OCH.sub.2 CH.dbd.CH.sub.2I-599 Pr OCH.sub.2 CH.dbd.CHMeI-600 i-Pr OCH.sub.2 C(Me).dbd.CH.sub.2I-601 i-Pr OCH.sub.2 CCHI-602 i-Pr OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-603 i-Pr OCH.sub.2 CH.dbd.C(Me).sub.2I-604 i-Pr OCH.sub.2 CH.dbd.CH.sub.2I-605 i-Pr OCH.sub.2 CH.dbd.CHMeI-606 O-i-Bu OCH.sub.2 C(Me).dbd.CH.sub.2I-607 O-i-Bu OCH.sub.2 CCHI-608 O-i-Bu OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-609 O-i-Bu OCH.sub.2 CH.dbd.C(Me).sub.2I-610 O-i-Bu OCH.sub.2 CH.dbd.CH.sub.2I-611 O-i-Bu OCH.sub.2 CH.dbd.CHMeI-612 OBu O-i-BuI-613 OBu OCH.sub.2 C(Me).dbd.CH.sub.2I-614 OBu OCH.sub.2 CCHI-615 OBu OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-616 OBu OCH.sub.2 CH.dbd.C(Me).sub.2I-617 OBu OCH.sub.2 CH.dbd.CH.sub.2I-618 OBu OCH.sub.2 CH.dbd.CHMeI-619 OCH.sub.2 CF.sub.3 OCH.sub.2 C(Me).dbd.CH.sub.2I-620 OCH.sub.2 CF.sub.3 OCH.sub.2 C.sub.2 F.sub.5I-621 OCH.sub.2 CF.sub.3 OCH.sub.2 CCHI-622 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-623 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.dbd.C(Me).sub.2I-624 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.dbd.CH.sub.2I-625 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.dbd.CHMeI-626 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 C(Me).dbd.CH.sub.2I-627 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CCHI-628 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-629 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.dbd.C(Me).sub.2I-630 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.dbd.CHMeI-631 OEt O-i-BuI-632 OEt OBuI-633 OEt OCH.sub.2 C(Me).dbd.CH.sub.2I-634 OEt OCH.sub.2 CCHI-635 OEt OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-636 OEt OCH.sub.2 CH.dbd.C(Me).sub.2I-637 OEt OCH.sub.2 CH.dbd.CH.sub.2I-638 OEt OCH.sub.2 CH.dbd.CHMeI-639 OEt OPrI-640 OMe O-i-BuI-641 OMe OBuI-642 OMe OCH.sub.2 C(Me).dbd.CH.sub.2I-643 OMe OCH.sub.2 CCEI-644 OMe OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-645 OMe OCH.sub.2 CH.dbd.C(Me).sub.2I-646 OMe OCH.sub.2 CH.dbd.CH.sub.2I-647 OMe OCH.sub.2 CH.dbd.CHMeI-648 OMe OEtI-649 OMe OPrI-650 OPr O-i-BuI-651 OPr OBuI-652 OPr OCH.sub.2 C(Me).dbd.CH.sub.2I-653 OPr OCH.sub.2 CCHI-654 OPr OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-655 OPr OCH.sub.2 CH.dbd.C(Me).sub.2I-656 OPr OCH.sub.2 CH.dbd.CH.sub.2I-657 OPr OCH.sub.2 CH.dbd.CHMe__________________________________________________________________________
TABLE 1__________________________________________________________________________(6/15)No. X.sub.n R.sup.1 R.sup.1__________________________________________________________________________I-658 A bromine atom OCHF.sub.2 OCHF.sub.2I-659 at 2-position CF.sub.3 OCH.sub.2 C(Me).dbd.CH.sub.2I-660 (2-Br) for CF.sub.3 OCH.sub.2 CCHI-661 Compound I-658 CF.sub.3 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-662 through CF.sub.3 OCH.sub.2 CH.dbd.C(Me).sub.2I-663 Compound I-767 CF.sub.3 OCH.sub.2 CH.dbd.CH.sub.2I-664 CF.sub.3 OCH.sub.2 CH.dbd.CHMeI-665 Cl O-i-BuI-666 Cl OBuI-667 Cl OCH.sub.2 C(Me).dbd.CH.sub.2I-668 Cl OCH.sub.2 C.sub.2 F.sub.5I-669 Cl OCH.sub.2 CCHI-670 Cl OCH.sub.2 CF.sub.3I-671 Cl OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-672 Cl OCH.sub.2 CH.dbd.C(Me).sub.2I-673 Cl OCH.sub.2 CH.dbd.CH.sub.2I-674 Cl OCH.sub.2 CH.dbd.CHMeI-675 Cl OEtI-676 Cl OMeI-677 Cl OPrI-678 Et OCH.sub.2 C (Me) .dbd.CH.sub.2I-679 Et OCH.sub.2 CCHI-680 Et OCH.sub.2 CH.sub.2 C(Me).dbd.CHiI-681 Et OCH.sub.2 CH.dbd.C(Me).sub.2I-682 Et OCH.sub.2 CH.dbd.CH.sub.2I-683 Et OCH.sub.2 CH.dbd.CHMeI-684 Me O-i-PrI-685 Me OCH.sub.2 C (Me) .dbd.CH.sub.2I-686 Me OCH.sub.2 CCHI-687 Me OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-688 Me OCH.sub.2 CH.dbd.C(Me).sub.2I-689 Me OCH.sub.2 CH.dbd.CH.sub.2I-690 Me OCH.sub.2 CH.dbd.CHMeI-691 Me OEtI-692 Me OMeI-693 O-i-Bu O-i-BuI-694 OBu OBuI-695 OCH.sub.2 C(Me).dbd.CH.sub.2 OCH.sub.2 C(Me).dbd.CH.sub.2I-696 OCH.sub.2 CCH OCH.sub.2 CCHI-697 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-698 OCH.sub.2 CH.dbd.C(Me).sub.2 OCH.sub.2 CH.dbd.C(Me).sub.2I-699 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.dbd.CH.sub.2I-700 OCH.sub.2 CH.dbd.CHMe OCH.sub.2 CH.dbd.CHMeI-701 OEt OEtI-702 OMe OMeI-703 OPr OPrI-704 Pr OCH.sub.2 C(Me).dbd.CH.sub.2I-705 Pr OCH.sub.2 CCHI-706 Pr OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-707 Pr OCH.sub.2 CH.dbd.C(Me).sub.2I-708 Pr OCH.sub.2 CH.dbd.CH.sub.2I-709 Pr OCH.sub.2 CH.dbd.CHMeI-710 i-Pr OCH.sub.2 C(Me).dbd.CH.sub.2I-711 i-Pr OCH.sub.2 CCHI-712 i-Pr OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-713 i-Pr OCH.sub.2 CH.dbd.C(Me).sub.2I-714 i-Pr OCH.sub.2 CH.dbd.CH.sub.2I-715 i-Pr OCH.sub.2 CH.dbd.CHMeI-716 O-i-Bu OCH.sub.2 C(Me).dbd.CH.sub.2I-717 O-i-Bu OCH.sub.2 CCHI-718 O-i-Bu OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-719 O-i-Bu OCH.sub.2 CH.dbd.C(Me).sub.2I-720 O-i-Bu OCH.sub.2 CH.dbd.CH.sub.2I-721 O-i-Bu OCH.sub.2 CH.dbd.CHMeI-722 OBu O-i-BuI-723 OBu OCH.sub.2 C(Me).dbd.CH.sub.2I-724 OBu OCH.sub.2 CCHI-725 OBu OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-726 OBu OCH.sub.2 CH.dbd.C(Me).sub.2I-727 OBu OCH.sub.2 CH.dbd.CH.sub.2I-728 OBu OCH.sub.2 CH.dbd.CHMeI-729 OCH.sub.2 CF.sub.3 OCH.sub.2 C(Me).dbd.CH.sub.2I-730 OCH.sub.2 CF.sub.3 OCH.sub.2 C.sub.2 F.sub.5I-731 OCH.sub.2 CF.sub.3 OCH.sub.2 CCHI-732 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-733 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.dbd.C(Me).sub.2I-734 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.dbd.CH.sub.2I-735 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.dbd.CHMeI-736 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 C(Me).dbd.CH.sub.2I-737 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CCHI-738 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-739 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.dbd.C(Me).sub.2I-740 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.dbd.CHMeI-741 OEt O-i-BuI-742 OEt OBuI-743 OEt OCH.sub.2 C(Me).dbd.CH.sub.2I-744 OEt OCH.sub.2 CCHI-745 OEt OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-746 OEt OCH.sub.2 CH.dbd.C(Me).sub.2I-747 OEt OCH.sub.2 CH.dbd.CH.sub.2I-748 OEt OCH.sub.2 CH.dbd.CHMeI-749 OEt OPrI-750 OMe O-i-BuI-751 OMe OBuI-752 OMe OCH.sub.2 C(Me).dbd.CH.sub.2I-753 OMe OCH.sub.2 CCHI-754 OMe OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-755 OMe OCH.sub.2 CH.dbd.C(Me).sub.2I-756 OMe OCH.sub.2 CH.dbd.CH.sub.2I-757 OMe OCH.sub.2 CH.dbd.CHMeI-758 OMe OEtI-759 OMe OPrI-760 OPr O-i-BuI-761 OPr OBuI-762 OPr OCH.sub.2 C(Me).dbd.CH.sub.2I-763 OPr OCH.sub.2 CCHI-764 OPr OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-765 OPr OCH.sub.2 CH.dbd.C(Me).sub.2I-766 OPr OCH.sub.2 CH.dbd.CH.sub.2I-767 OPr OCH.sub.2 CH.dbd.CHMe__________________________________________________________________________
__________________________________________________________________________(7/15)No. X.sub.n R.sup.1 R.sup.1__________________________________________________________________________I-768 A methyl group OCHF.sub.2 OCHF.sub.2I-769 at 2-position CF.sub.3 OCH.sub.2 C(Me).dbd.CH.sub.2I-770 (2-Me) for CF.sub.3 OCH.sub.2 CCHI-771 Compound I-768 CF.sub.3 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-772 through CF.sub.3 OCH.sub.2 CH.dbd.C(Me).sub.2I-773 Compound I-877 CF.sub.3 OCH.sub.2 CH.dbd.CH.sub.2I-774 CF.sub.3 OCH.sub.2 CH.dbd.CHMeI-775 Cl O-i-BuI-776 Cl OBuI-777 Cl OCH.sub.2 C(Me).dbd.CH.sub.2I-778 Cl OCH.sub.2 C.sub.2 F.sub.5I-779 Cl OCH.sub.2 CCHI-780 Cl OCH.sub.2 CF.sub.3I-781 Cl OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-782 Cl OCH.sub.2 CH.dbd.C(Me).sub.2I-783 Cl OCH.sub.2 CH.dbd.CH.sub.2I-784 Cl OCH.sub.2 CH.dbd.CHMeI-785 Cl OEtI-786 Cl OMeI-787 Cl OPrI-788 Et OCH.sub.2 C(Me).dbd.CH.sub.2I-789 Et OCH.sub.2 CCHI-790 Et OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-791 Et OCH.sub.2 CH.dbd.C(Me).sub.2I-792 Et OCH.sub.2 CH.dbd.CH.sub.2I-793 Et OCH.sub.2 CH.dbd.CHMeI-794 Me O-i-PrI-795 Me OCH.sub.2 C(Me).dbd.CH.sub.2I-796 Me OCH.sub.2 CCHI-797 Me OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-798 Me OCH.sub.2 CH.dbd.C(Me).sub.2I-799 Me OCH.sub.2 CH.dbd.CH.sub.2I-800 Me OCH.sub.2 CH.dbd.CHMeI-801 Me OEtI-802 Me OMeI-803 O-i-Bu O-i-BuI-804 OBu OBuI-805 OCH.sub.2 C(Me).dbd.CH.sub.2 OCH.sub.2 C(Me).dbd.CH.sub.2I-806 OCH.sub.2 CCH OCH.sub.2 CCHI-807 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-808 OCH.sub.2 CH.dbd.C(Me).sub.2 OCH.sub.2 CH.dbd.C(Me).sub.2I-809 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.dbd.CH.sub.2I-810 OCH.sub.2 CH.dbd.CHMe OCH.sub.2 CH.dbd.CHMeI-811 OEt OEtI-812 OMe OMeI-813 OPr OPrI-814 Pr OCH.sub.2 C(Me).dbd.CH.sub.2I-815 Pr OCH.sub.2 CCHI-816 Pr OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-817 Pr OCH.sub.2 CH.dbd.C(Me).sub.2I-818 Pr OCH.sub.2 CH.dbd.CH.sub.2I-819 Pr OCH.sub.2 CH.dbd.CHMeI-820 i-Pr OCH.sub.2 C(Me).dbd.CH.sub.2I-821 i-Pr OCH.sub.2 CCHI-822 i-Pr OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-823 i-Pr OCH.sub.2 CH.dbd.C(Me).sub.2I-824 i-Pr OCH.sub.2 CH.dbd.CH.sub.2I-825 i-Pr OCH.sub.2 CH.dbd.CHMeI-826 O-i-Bu OCH.sub.2 C(Me).dbd.CH.sub.2I-827 O-i-Bu OCH.sub.2 CCHI-828 O-i-Bu OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-829 O-i-Bu OCH.sub.2 CH.dbd.C(Me).sub.2I-830 O-i-Bu OCH.sub.2 CH.dbd.CH.sub.2I-831 O-i-Bu OCH.sub.2 CH.dbd.CHMeI-832 OBu O-i-BuI-833 OBu OCH.sub.2 C(Me).dbd.CH.sub.2I-834 OBu OCH.sub.2 CCHI-835 OBu OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-836 OBu OCH.sub.2 CH.dbd.C(Me).sub.2I-837 OBu OCH.sub.2 CH.dbd.CH.sub.2I-838 OBu OCH.sub.2 CH.dbd.CHMeI-839 OCH.sub.2 CF.sub.3 OCH.sub.2 C(Me).dbd.CH.sub.2I-840 OCH.sub.2 CF.sub.3 OCH.sub.2 C.sub.2 F.sub.5I-841 OCH.sub.2 CF.sub.3 OCH.sub.2 CCHI-842 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-843 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.dbd.C(Me).sub.2I-844 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.dbd.CH.sub.2I-845 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.dbd.CHMeI-846 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 C(Me).dbd.CH.sub.2I-847 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CCHI-848 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-849 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.dbd.C(Me).sub.2I-850 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.dbd.CHMeI-851 OEt O-i-BuI-852 OEt OBuI-853 OEt OCH.sub.2 C(Me).dbd.CH.sub.2I-854 OEt OCH.sub.2 CCHI-855 OEt OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-856 OEt OCH.sub.2 CH.dbd.C(Me).sub.2I-857 OEt OCH.sub.2 CH.dbd.CH.sub.2I-858 OEt OCH.sub.2 CH.dbd.CHMeI-859 OEt OPrI-860 OMe O-i-BuI-861 OMe OBuI-862 OMe OCH.sub.2 C(Me).dbd.CH.sub.2I-863 OMe OCH.sub.2 CCHI-864 OMe OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-865 OMe OCH.sub.2 CH.dbd.C(Me).sub.2I-866 OMe OCH.sub.2 CH.dbd.CH.sub.2I-867 OMe OCH.sub.2 CH.dbd.CHMeI-868 OMe OEtI-869 OMe OPrI-870 OPr O-i-BuI-871 OPr OBuI-872 OPr OCH.sub.2 C(Me).dbd.CH.sub.2I-873 OPr OCH.sub.2 CCHI-874 OPr OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-875 OPr OCH.sub.2 CH.dbd.C(Me).sub.2I-876 OPr OCH.sub.2 CH.dbd.CH.sub.2I-877 OPr OCH.sub.2 CH.dbd.CHMe__________________________________________________________________________
TABLE 1__________________________________________________________________________(8/15)No. X.sub.n R.sup.1 R.sup.2__________________________________________________________________________I-878 A chlorine atom OCHF.sub.2 OCHF.sub.2I-879 at 3-position CF.sub.3 OCH.sub.2 C(Me).dbd.CH.sub.2I-880 (3-Cl) for CF.sub.3 OCH.sub.2 CCHI-881 Compound I-878 CF.sub.3 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-882 through CF.sub.3 OCH.sub.2 CH.dbd.C(Me).sub.2I-883 Compound I-987 CF.sub.3 OCH.sub.2 CH.dbd.CH.sub.2I-884 CF.sub.3 OCH.sub.2 CH.dbd.CHMeI-885 Cl O-i-BuI-886 Cl OBuI-887 Cl OCH.sub.2 C(Me).dbd.CH.sub.2I-888 Cl OCH.sub.2 C.sub.2 F.sub.5I-889 Cl OCH.sub.2 CCHI-890 Cl OCH.sub.2 CF.sub.3I-891 Cl OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-892 Cl OCH.sub.2 CH.dbd.C(Me).sub.2I-893 Cl OCH.sub.2 CH.dbd.CH.sub.2I-894 Cl OCH.sub.2 CH.dbd.CHMeI-895 Cl OEtI-896 Cl OMeI-897 Cl OPrI-898 Et OCH.sub.2 C(Me).dbd.CH.sub.2I-899 Et OCH.sub.2 CCHI-900 Et OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-901 Et OCH.sub.2 CH.dbd.C(Me).sub.2I-902 Et OCH.sub.2 CH.dbd.CH.sub.2I-903 Et OCH.sub.2 CH.dbd.CHMeI-904 Me O-i-PrI-905 Me OCH.sub.2 C(Me).dbd.CH.sub.2I-906 Me OCH.sub.2 CCHI-907 Me OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-908 Me OCH.sub.2 CH.dbd.C(Me).sub.2I-909 Me OCH.sub.2 CH.dbd.CH.sub.2I-910 Me OCH.sub.2 CH.dbd.CHMeI-911 Me OEtI-912 Me OMeI-913 O-i-Bu O-i-BuI-914 OBu OBuI-915 OCH.sub.2 C(Me).dbd.CH.sub.2 OCH.sub.2 C(Me).dbd.CH.sub.2I-916 OCH.sub.2 CCH OCH.sub.2 CCHI-917 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-918 OCH.sub.2 CH.dbd.C(Me).sub.2 OCH.sub.2 CH.dbd.C(Me).sub.2I-919 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.dbd.CH.sub.2I-920 OCH.sub.2 CH.dbd.CHMe OCH.sub.2 CH.dbd.CHMeI-921 OEt OEtI-922 OMe OMeI-923 OPr OPrI-924 Pr OCH.sub.2 C(Me).dbd.CH.sub.2I-925 Pr OCH.sub.2 CCHI-926 Pr OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-927 Pr OCH.sub.2 CH.dbd.C(Me).sub.2I-928 Pr OCH.sub.2 CH.dbd.CH.sub.2I-929 Pr OCH.sub.2 CH.dbd.CHMeI-930 i-Pr OCH.sub.2 C(Me).dbd.CH.sub.2I-931 i-Pr OCH.sub.2 CCHI-932 i-Pr OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-933 i-Pr OCH.sub.2 CH.dbd.C(Me).sub.2I-934 i-Pr OCH.sub.2 CH.dbd.CH.sub.2I-935 i-Pr OCH.sub.2 CH.dbd.CHMeI-936 O-i-Bu OCH.sub.2 C(Me).dbd.CH.sub.2I-937 O-i-Bu OCH.sub.2 CCHI-938 O-i-Bu OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-939 O-i-Bu OCH.sub.2 CH.dbd.C(Me).sub.2I-940 O-i-Bu OCH.sub.2 CH.dbd.CH.sub.2I-941 O-i-Bu OCH.sub.2 CH.dbd.CHMeI-942 OBu O-i-BuI-943 OBu OCH.sub.2 C(Me).dbd.CH.sub.2I-944 OBu OCH.sub.2 CCHI-945 OBu OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-946 OBu OCH.sub.2 CH.dbd.C(Me).sub.2I-947 OBu OCH.sub.2 CH.dbd.CH.sub.2I-948 OBu OCH.sub.2 CH.dbd.CHMeI-949 OCH.sub.2 CF.sub.3 OCH.sub.2 C(Me).dbd.CH.sub.2I-950 OCH.sub.2 CF.sub.3 OCH.sub.2 C.sub.2 F.sub.5I-951 OCH.sub.2 CF.sub.3 OCH.sub.2 CCHI-952 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-953 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.dbd.C(Me).sub.2I-954 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.dbd.CH.sub.2I-955 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.dbd.CHMeI-956 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 C(Me).dbd.CH.sub.2I-957 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CCHI-958 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-959 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.dbd.C(Me).sub.2I-960 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.dbd.CHMeI-961 OEt O-i-BuI-962 OEt OBuI-963 OEt OCH.sub.2 C(Me).dbd.CH.sub.2I-964 OEt OCH.sub.2 CCHI-965 OEt OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-966 OEt OCH.sub.2 CH.dbd.C(Me).sub.2I-967 OEt OCH.sub.2 CH.dbd.CH.sub.2I-968 OEt OCH.sub.2 CH.dbd.CHMeI-969 OEt OPrI-970 OMe O-i-BuI-971 OMe OBuI-972 OMe OCH.sub.2 C(Me).dbd.CH.sub.2I-973 OMe OCH.sub.2 CCHI-974 OMe OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-975 OMe OCH.sub.2 CH.dbd.C(Me).sub.2I-976 OMe OCH.sub.2 CH.dbd.CH.sub.2I-977 OMe OCH.sub.2 CH.dbd.CHMeI-978 OMe OEtI-979 OMe OPrI-980 OPr O-i-BuI-981 OPr OBuI-982 OPr OCH.sub.2 C(Me).dbd.CH.sub.2I-983 OPr OCH.sub.2 CCHI-984 OPr OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-985 OPr OCH.sub.2 CH.dbd.C(Me).sub.2I-986 OPr OCH.sub.2 CH.dbd.CH.sub.2I-987 OPr OCH.sub.2 CH.dbd.CHMe__________________________________________________________________________
TABLE 1__________________________________________________________________________(9/15)No. X.sub.n R.sup.1 R.sup.2__________________________________________________________________________I-988 A fluorine atom OCHF.sub.2 OCHF.sub.2I-989 at 3-position CF.sub.3 OCH.sub.2 C(Me).dbd.CH.sub.2I-990 (3-F) for CF.sub.3 OCH.sub.2 CCHI-991 Compound I-988 CF.sub.3 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-992 through CF.sub.3 OCH.sub.2 CH.dbd.C(Me).sub.2I-993 Compound I-1097 CF.sub.3 OCH.sub.2 CH.dbd.CH.sub.2I-994 CF.sub.3 OCH.sub.2 CH.dbd.CHMeI-995 Cl O-i-BuI-996 Cl OBuI-997 Cl OCH.sub.2 C(Me).dbd.CH.sub.2I-998 Cl OCH.sub.2 C.sub.2 F.sub.5I-999 Cl OCH.sub.2 CCHI-1000 Cl OCH.sub.2 CF.sub.3I-1001 Cl OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1002 Cl OCH.sub.2 CH.dbd.C(Me).sub.2I-1003 Cl OCH.sub.2 CH.dbd.CH.sub.2I-1004 Cl OCH.sub.2 CH.dbd.CHMeI-1005 Cl OEtI-1006 Cl OMeI-1007 Cl OPrI-1008 Et OCH.sub.2 C(Me).dbd.CH.sub.2I-1009 Et OCH.sub.2 CCHI-1010 Et OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1011 Et OCH.sub.2 CH.dbd.C(Me)2I-1012 Et OCH.sub.2 CH.dbd.CH.sub.2I-1013 Et OCH.sub.2 CH.dbd.CHMeI-1014 Me O-i-PrI-1015 Me OCH.sub.2 C(Me).dbd.CH.sub.2I-1016 Me OCH.sub.2 CCHI-1017 Me OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1018 Me OCH.sub.2 CH.dbd.C(Me).sub.2I-1019 Me OCH.sub.2 CH.dbd.CH.sub.2I-1020 Me OCH.sub.2 CH.dbd.CHMeI-1021 Me OEtI-1022 Me OMeI-1023 O-i-Bu O-i-BuI-1024 OBu OBuI-1025 OCH.sub.2 C(Me).dbd.CH.sub.2 OCH.sub.2 C(Me).dbd.CH.sub.2I-1026 OCH.sub.2 CCH OCH.sub.2 CCHI-1027 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1028 OCH.sub.2 CH.dbd.C(Me).sub.2 OCH.sub.2 CH.dbd.C(Me).sub.2I-1029 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.dbd.CH.sub.2I-1030 OCH.sub.2 CH.dbd.CHMe OCH.sub.2 CH.dbd.CHMeI-1031 OEt OEtI-1032 OMe OMeI-1033 OPr OPrI-1034 Pr OCH.sub.2 C(Me).dbd.CH.sub.2I-1035 Pr OCH.sub.2 CCHI-1036 Pr OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1037 Pr OCH.sub.2 CH.dbd.C(Me).sub.2I-1038 Pr OCH.sub.2 CH.dbd.CH.sub.2I-1039 Pr OCH.sub.2 CH.dbd.CHMeI-1040 i-Pr OCH.sub.2 C(Me).dbd.CH.sub.2I-1041 i-Pr OCH.sub.2 CCHI-1042 i-Pr OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1043 i-Pr OCH.sub.2 CH.dbd.C(Me).sub.2I-1044 i-Pr OCH.sub.2 CH.dbd.CH.sub.2I-1045 i-Pr OCH.sub.2 CH.dbd.CHMeI-1046 O-i-Bu OCH.sub.2 C(Me).dbd.CH.sub.2I-1047 O-i-Bu OCH.sub.2 CCHI-1048 O-i-Bu OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1049 O-i-Bu OCH.sub.2 CH.dbd.C(Me).sub.2I-1050 O-i-Bu OCH.sub.2 CH.dbd.CH.sub.2I-1051 O-i-Bu OCH.sub.2 CH.dbd.CHMeI-1052 OBu O-i-BuI-1053 OBu OCH.sub.2 C(Me).dbd.CH.sub.2I-1054 OBu OCH.sub.2 CCHI-1055 OBu OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1056 OBu OCH.sub.2 CH.dbd.C(Me).sub.2I-1057 OBu OCH.sub.2 CH.dbd.CH.sub.2I-1058 OBu OCH.sub.2 CH.dbd.CHMeI-1059 OCH.sub.2 CF.sub.3 OCH.sub.2 C(Me).dbd.CH.sub.2I-1060 OCH.sub.2 CF.sub.3 OCH.sub.2 C.sub.2 F.sub.5I-1061 OCH.sub.2 CF.sub.3 OCH.sub.2 CCHI-1062 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1063 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.dbd.C(Me).sub.2I-1064 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.dbd.CH.sub.2I-1065 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.dbd.CHMeI-1066 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 C(Me).dbd.CH.sub.2I-1067 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CCHI-1068 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1069 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.dbd.C(Me).sub.2I-1070 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.dbd.CHMeI-1071 OEt O-i-BuI-1072 OEt OBuI-1073 OEt OCH.sub.2 C(Me).dbd.CH.sub.2I-1074 OEt OCH.sub.2 CCHI-1075 OEt OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1076 OEt OCH.sub.2 CH.dbd.C(Me).sub.2I-1077 OEt OCH.sub.2 CH.dbd.CH.sub.2I-1078 OEt OCH.sub.2 CH.dbd.CHMeI-1079 OEt OPrI-1080 OMe O-i-BuI-1081 OMe OBuI-1082 OMe OCH.sub.2 C(Me).dbd.CH.sub.2I-1083 OMe OCH.sub.2 CCHI-1084 OMe OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1085 OMe OCH.sub.2 CH.dbd.C(Me)2I-1086 OMe OCH.sub.2 CH.dbd.CH.sub.2I-1087 OMe OCH.sub.2 CH.dbd.CHMeI-1088 OMe OEtI-1089 OMe OPrI-1090 OPr O-i-BuI-1091 OPr OBuI-1092 OPr OCH.sub.2 C(Me).dbd.CH.sub.2I-1093 OPr OCH.sub.2 CCHI-1094 OPr OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1095 OPr OCH.sub.2 CH.dbd.C(Me).sub.2I-1096 OPr OCH.sub.2 CH.dbd.CH.sub.2I-1097 OPr OCH.sub.2 CH.dbd.CHMe__________________________________________________________________________
TABLE 1__________________________________________________________________________(10/15)No. X.sub.n R.sup.1 R.sup.2__________________________________________________________________________I-1098 A bromine atom OCHF.sub.2 OCHF.sub.2I-1099 at 3-position CF.sub.3 OCH.sub.2 C(Me).dbd.CH.sub.2I-1100 (3-Br) for CF.sub.3 OCH.sub.2 CCHI-1101 Compound I-1098 CF.sub.3 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1102 through CF.sub.3 OCH.sub.2 CH.dbd.C(Me).sub.2I-1103 Compound I-1207 CF.sub.3 OCH.sub.2 CH.dbd.CH.sub.2I-1104 CF.sub.3 OCH.sub.2 CH.dbd.CHMeI-1105 Cl O-i-BuI-1106 Cl OBuI-1107 Cl OCH.sub.2 C(Me).dbd.CH.sub.2I-1108 Cl OCH.sub.2 C.sub.2 F.sub.5I-1109 Cl OCH.sub.2 CCHI-1110 Cl OCH.sub.2 CF.sub.3I-1111 Cl OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1112 Cl OCH.sub.2 CH.dbd.C(Me).sub.2I-1113 Cl OCH.sub.2 CH.dbd.CH.sub.2I-1114 Cl OCH.sub.2 CH.dbd.CHMeI-1115 Cl OEtI-1116 Cl OMeI-1117 Cl OPrI-1118 Et OCH.sub.2 C(Me).dbd.CH.sub.2I-1119 Et OCH.sub.2 CCHI-1120 Et OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1121 Et OCH.sub.2 CH.dbd.C(Me).sub.2I-1122 Et OCH.sub.2 CH.dbd.CH.sub.2I-1123 Et OCH.sub.2 CH.dbd.CHMeI-1124 Me O-i-PrI-1125 Me OCH.sub.2 C(Me).dbd.CH.sub.2I-1126 Me OCH.sub.2 CCHI-1127 Me OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1128 Me OCH.sub.2 CH.dbd.C(Me).sub.2I-1129 Me OCH.sub.2 CH.dbd.CH.sub.2I-1130 Me OCH.sub.2 CH.dbd.CHMeI-1131 Me OEtI-1132 Me OMeI-1133 O-i-Bu O-i-BuI-1134 OBu OBuI-1135 OCH.sub.2 C(Me).dbd.CH.sub.2 OCH.sub.2 C(Me).dbd.CH.sub.2I-1136 OCH.sub.2 CCH OCH.sub.2 CCHI-1137 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1138 OCH.sub.2 CH.dbd.C(Me).sub.2 OCH.sub.2 CH.dbd.C(Me)2I-1139 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.dbd.CH.sub.2I-1140 OCH.sub.2 CH.dbd.CHMe OCH.sub.2 CH.dbd.CHMeI-1141 OEt OEtI-1142 OMe OMeI-1143 OPr OPrI-1144 Pr OCH.sub.2 C(Me).dbd.CH.sub.2I-1145 Pr OCH.sub.2 CCHI-1146 Pr OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1147 Pr OCH.sub.2 CH.dbd.C(Me).sub.2I-1148 Pr OCH.sub.2 CH.dbd.CH.sub.2I-1149 Pr OCH.sub.2 CH.dbd.CHMeI-1150 i-Pr OCH.sub.2 C(Me).dbd.CH.sub.2I-1151 i-Pr OCH.sub.2 CCHI-1152 i-Pr OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1153 i-Pr OCH.sub.2 CH.dbd.C(Me).sub.2I-1154 i-Pr OCH.sub.2 CH.dbd.CH.sub.2I-1155 i-Pr OCH.sub.2 CH.dbd.CHMeI-1156 O-i-Bu OCH.sub.2 C(Me).dbd.CH.sub.2I-1157 O-i-Bu OCH.sub.2 CCHI-1158 O-i-Bu OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1159 O-i-Bu OCH.sub.2 CH.dbd.C(Me).sub.2I-1160 O-i-Bu OCH.sub.2 CH.dbd.CH.sub.2I-1161 O-i-Bu OCH.sub.2 CH.dbd.CHMeI-1162 OBu O-i-BuI-1163 OBu OCH.sub.2 C(Me).dbd.CH.sub.2I-1164 OBu OCH.sub.2 CCHI-1165 OBu OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1166 OBu OCH.sub.2 CH.dbd.C(Me).sub.2I-1167 OBu OCH.sub.2 CH.dbd.CH.sub.2I-1168 OBu OCH.sub.2 CH.dbd.CHMeI-1169 OCH.sub.2 CF.sub.3 OCH.sub.2 C(Me).dbd.CH.sub.2I-1170 OCH.sub.2 CF.sub.3 OCH.sub.2 C.sub.2 F.sub.5I-1171 OCH.sub.2 CF.sub.3 OCH.sub.2 CCHI-1172 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1173 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.dbd.C(Me).sub.2I-1174 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.dbd.CH.sub.2I-1175 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.dbd.CHMeI-1176 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 C(Me).dbd.CH.sub.2I-1177 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CCHI-1178 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1179 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.dbd.C(Me).sub.2I-1180 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.dbd.CHMeI-1181 OEt O-i-BuI-1182 OEt OBuI-1183 OEt OCH.sub.2 C(Me).dbd.CH.sub.2I-1184 OEt OCH.sub.2 CCHI-1185 OEt OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1186 OEt OCH.sub.2 CH.dbd.C(Me).sub.2I-1187 OEt OCH.sub.2 CH.dbd.CH.sub.2I-1188 OEt OCH.sub.2 CH.dbd.CHMeI-1189 OEt OPrI-1190 OMe O-i-BuI-1191 OMe OBuI-1192 OMe OCH.sub.2 C(Me).dbd.CH.sub.2I-1193 OMe OCH.sub.2 CCHI-1194 OMe OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1195 OMe OCH.sub.2 CH.dbd.C(Me).sub.2I-1196 OMe OCH.sub.2 CH.dbd.CH.sub.2I-1197 OMe OCH.sub.2 CH.dbd.CHMeI-1198 OMe OEtI-1199 OMe OPrI-1200 OPr O-i-BuI-1201 OPr OBuI-1202 OPr OCH.sub.2 C(Me).dbd.CH.sub.2I-1203 OPr OCH.sub.2 CCHI-1204 OPr OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1205 OPr OCH.sub.2 CH.dbd.C(Me).sub.2I-1206 OPr OCH.sub.2 CH.dbd.CH.sub.2I-1207 OPr OCH.sub.2 CH.dbd.CHMe__________________________________________________________________________
TABLE 1__________________________________________________________________________(11/15)No. X.sub.n R.sup.1 R.sup.2__________________________________________________________________________I-1208 A methyl group OCHF.sub.2 OCHF.sub.2I-1209 at 3-position CF.sub.3 OCH.sub.2 C(Me).dbd.CH.sub.2I-1210 (2-Me) for CF.sub.3 OCH.sub.2 CCHI-1211 Compound I-1208 CF.sub.3 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1212 through CF.sub.3 OCH.sub.2 CH.dbd.C(Me).sub.2I-1213 Compound I-1317 CF.sub.3 OCH.sub.2 CH.dbd.CH.sub.2I-1214 CF.sub.3 OCH.sub.2 CH.dbd.CHMeI-1215 Cl O-i-BuI-1216 Cl OBuI-1217 Cl OCH.sub.2 C(Me).dbd.CH.sub.2I-1218 Cl OCH.sub.2 C.sub.2 F.sub.5I-1219 Cl OCH.sub.2 CCHI-1220 Cl OCH.sub.2 CF.sub.3I-1221 Cl OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1222 Cl OCH.sub.2 CH.dbd.C(Me).sub.2I-1223 Cl OCH.sub.2 CH.dbd.CH.sub.2I-1224 Cl OCH.sub.2 CH.dbd.CHMeI-1225 Cl OEtI-1226 Cl OMeI-1227 Cl OPrI-1228 Et OCH.sub.2 C(Me).dbd.CH.sub.2I-1229 Et OCH.sub.2 CCHI-1230 Et OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1231 Et OCH.sub.2 CH.dbd.C(Me).sub.2I-1232 Et OCH.sub.2 CH.dbd.CH.sub.2I-1233 Et OCH.sub.2 CH.dbd.CHMeI-1234 Me O-i-PrI-1235 Me OCH.sub.2 C(Me).dbd.CH.sub.2I-1236 Me OCH.sub.2 CCHI-1237 Me OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1238 Me OCH.sub.2 CH.dbd.C(Me).sub.2I-1239 Me OCH.sub.2 CH.dbd.CH.sub.2I-1240 Me OCH.sub.2 CH.dbd.CHMeI-1241 Me OEtI-1242 Me OMeI-1243 O-i-Bu O-i-BuI-1244 OBu OBuI-1245 OCH.sub.2 C(Me).dbd.CH.sub.2 OCH.sub.2 C(Me).dbd.CH.sub.2I-1246 OCH.sub.2 CCH OCH.sub.2 CCHI-1247 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1248 OCH.sub.2 CH.dbd.C(Me).sub.2 OCH.sub.2 CH.dbd.C(Me).sub.2I-1249 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.dbd.CH.sub.2I-1250 OCH.sub.2 CH.dbd.CHMe OCH.sub.2 CH.dbd.CHMeI-1251 OEt OEtI-1252 OMe OMeI-1253 OPr OPrI-1254 Pr OCH.sub.2 C(Me).dbd.CH.sub.2I-1255 Pr OCH.sub.2 CCHI-1256 Pr OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1257 Pr OCH.sub.2 CH.dbd.C(Me).sub.2I-1258 Pr OCH.sub.2 CH.dbd.CH.sub.2I-1259 Pr OCH.sub.2 CH.dbd.CHMeI-1260 i-Pr OCH.sub.2 C(Me).dbd.CH.sub.2I-1261 i-Pr OCH.sub.2 CCHI-1262 i-Pr OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1263 i-Pr OCH.sub.2 CH.dbd.C(Me).sub.2I-1264 i-Pr OCH.sub.2 CH.dbd.CH.sub.2I-1265 i-Pr OCH.sub.2 CH.dbd.CHMeI-1266 O-i-Bu OCH.sub.2 C(Me).dbd.CH.sub.2I-1267 O-i-Bu OCH.sub.2 CCHI-1268 O-i-Bu OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1269 O-i-Bu OCH.sub.2 CH.dbd.C(Me).sub.2I-1270 O-i-Bu OCH.sub.2 CH.dbd.CH.sub.2I-1271 O-i-Bu OCH.sub.2 CH.dbd.CHMeI-1272 OBu O-i-BuI-1273 OBu OCH.sub.2 C(Me).dbd.CH.sub.2I-1274 OBu OCH.sub.2 CCHI-1275 OBu OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1276 OBu OCH.sub.2 CH.dbd.C(Me).sub.2I-1277 OBu OCH.sub.2 CH.dbd.CH.sub.2I-1278 OBu OCH.sub.2 CH.dbd.CHMeI-1279 OCH.sub.2 CF.sub.3 OCH.sub.2 C(Me).dbd.CH.sub.2I-1280 OCH.sub.2 CF.sub.3 OCH.sub.2 C.sub.2 F.sub.5I-1281 OCH.sub.2 CF.sub.3 OCH.sub.2 CCHI-1282 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1283 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.dbd.C(Me)2I-1284 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.dbd.CH.sub.2I-1285 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.dbd.CHMeI-1286 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 C(Me).dbd.CH.sub.2I-1287 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CCHI-1288 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1289 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.dbd.C(Me).sub.2I-1290 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.dbd.CHMeI-1291 OEt O-i-BuI-1292 OEt OBuI-1293 OEt OCH.sub.2 C(Me).dbd.CH.sub.2I-1294 OEt OCH.sub.2 CCHI-1295 OEt OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1296 OEt OCH.sub.2 CH.dbd.C(Me).sub.2I-1297 OEt OCH.sub.2 CH.dbd.CH.sub.2I-1298 OEt OCH.sub.2 CH.dbd.CHMeI-1299 OEt OPrI-1300 OMe O-i-BuI-1301 OMe OBuI-1302 OMe OCH.sub.2 C(Me).dbd.CH.sub.2I-1303 OMe OCH.sub.2 CCHI-1304 OMe OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1305 OMe OCH.sub.2 CH.dbd.C(Me).sub.2I-1306 OMe OCH.sub.2 CH.dbd.CH.sub.2I-1307 OMe OCH.sub.2 CH.dbd.CHMeI-1308 OMe OEtI-1309 OMe OPrI-1310 OPr O-i-BuI-1311 OPr OBuI-1312 OPr OCH.sub.2 C(Me).dbd.CH.sub.2I-1313 OPr OCH.sub.2 CCHI-1314 OPr OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1315 OPr OCH.sub.2 CH.dbd.C(Me).sub.2I-1316 OPr OCH.sub.2 CH.dbd.CH.sub.2I-1317 OPr OCH.sub.2 CH.dbd.CHMe__________________________________________________________________________
TABLE 1__________________________________________________________________________(12/15)No. X.sub.n R.sup.1 R.sup.2__________________________________________________________________________I-1318 A chlorine atom OCHF.sub.2 OCHF.sub.2I-1319 at 4-position CF.sub.3 OCH.sub.2 C(Me).dbd.CH.sub.2I-1320 (4-Cl) for CF.sub.3 OCH.sub.2 CCHI-1321 Compound I-768 CF.sub.3 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1322 through CF.sub.3 OCH.sub.2 CH.dbd.C(Me)2I-1323 Compound I-877 CF.sub.3 OCH.sub.2 CH.dbd.CH.sub.2I-1324 CF.sub.3 OCH.sub.2 CH.dbd.CHMeI-1325 Cl O-i-BuI-1326 Cl OBuI-1327 Cl OCH.sub.2 C(Me).dbd.CH.sub.2I-1328 Cl OCH.sub.2 C.sub.2 F.sub.5I-1329 Cl OCH.sub.2 CCHI-1330 Cl OCH.sub.2 CF.sub.3I-1331 Cl OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1332 Cl OCH.sub.2 CH.dbd.C(Me).sub.2I-1333 Cl OCH.sub.2 CH.dbd.CH.sub.2I-1334 Cl OCH.sub.2 CH.dbd.CHMeI-1335 Cl OEtI-1336 Cl OMeI-1337 Cl OPrI-1338 Et OCH.sub.2 C(Me).dbd.CH.sub.2I-1339 Et OCH.sub.2 CCHI-1340 Et OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1341 Et OCH.sub.2 CH.dbd.C(Me).sub.2I-1342 Et OCH.sub.2 CH.dbd.CH.sub.2I-1343 Et OCH.sub.2 CH.dbd.CHMeI-1344 Me O-i-PrI-1345 Me OCH.sub.2 C(Me).dbd.CH.sub.2I-1346 Me OCH.sub.2 CCHI-1347 Me OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1348 Me OCH.sub.2 CH.dbd.C(Me).sub.2I-1349 Me OCH.sub.2 CH.dbd.CH.sub.2I-1350 Me OCH.sub.2 CH.dbd.CHMeI-1351 Me OEtI-1352 Me OMeI-1353 O-i-Bu O-i-BuI-1354 OBu OBuI-1355 OCH.sub.2 C(Me).dbd.CH.sub.2 OCH.sub.2 C(Me).dbd.CH.sub.2I-1356 OCH.sub.2 CCH OCH.sub.2 CCHI-1357 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1358 OCH.sub.2 CH.dbd.C(Me).sub.2 OCH.sub.2 CH.dbd.C(Me).sub.2I-1359 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.dbd.CH.sub.2I-1360 OCH.sub.2 CH.dbd.CHMe OCH.sub.2 CH.dbd.CHMeI-1361 OEt OEtI-1362 OMe OMeI-1363 OPr OPrI-1364 Pr OCH.sub.2 C(Me).dbd.CH.sub.2I-1365 Pr OCH.sub.2 CCHI-1366 Pr OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1367 Pr OCH.sub.2 CH.dbd.C(Me).sub.2I-1368 Pr OCH.sub.2 CH.dbd.CH.sub.2I-1369 Pr OCH.sub.2 CH.dbd.CHMeI-1370 i-Pr OCH.sub.2 C(Me).dbd.CH.sub.2I-1371 i-Pr OCH.sub.2 CCHI-1372 i-Pr OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1373 i-Pr OCH.sub.2 CH.dbd.C(Me).sub.2I-1374 i-Pr OCH.sub.2 CH.dbd.CH.sub.2I-1375 i-Pr OCH.sub.2 CH.dbd.CHMeI-1376 O-i-Bu OCH.sub.2 C(Me).dbd.CH.sub.2I-1377 O-i-Bu OCH.sub.2 CCHI-1378 O-i-Bu OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1379 O-i-Bu OCH.sub.2 CH.dbd.C(Me).sub.2I-1380 O-i-Bu OCH.sub.2 CH.dbd.CH.sub.2I-1381 O-i-Bu OCH.sub.2 CH.dbd.CHMeI-1382 OBu O-i-BuI-1383 OBu OCH.sub.2 C(Me).dbd.CH.sub.2I-1384 OBu OCH.sub.2 CCHI-1385 OBu OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1386 OBu OCH.sub.2 CH.dbd.C(Me).sub.2I-1387 OBu OCH.sub.2 CH.dbd.CH.sub.2I-1388 OBu OCH.sub.2 CH.dbd.CHMeI-1389 OCH.sub.2 CF.sub.3 OCH.sub.2 C(Me).dbd.CH.sub.2I-1390 OCH.sub.2 CF.sub.3 OCH.sub.2 C.sub.2 F.sub.5I-1391 OCH.sub.2 CF.sub.3 OCH.sub.2 CCHI-1392 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1393 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.dbd.C(Me).sub.2I-1394 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.dbd.CH.sub.2I-1395 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.dbd.CHMeI-1396 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 C(Me).dbd.CH.sub.2I-1397 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CCHI-1398 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.21-1399 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.dbd.C(Me).sub.2I-1400 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.dbd.CHMeI-1401 OEt O-i-BuI-1402 OEt OBuI-1403 OEt OCH.sub.2 C(Me).dbd.CH.sub.2I-1404 OEt OCH.sub.2 CCHI-1405 OEt OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1406 OEt OCH.sub.2 CH.dbd.C(Me).sub.2I-1407 OEt OCH.sub.2 CH.dbd.CH.sub.2I-1408 OEt OCH.sub.2 CH.dbd.CHMeI-1409 OEt OPrI-1410 OMe O-i-BuI-1411 OMe OBuI-1412 OMe OCH.sub.2 C(Me).dbd.CH.sub.2I-1413 OMe OCH.sub.2 CCHI-1414 OMe OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1415 OMe OCH.sub.2 CH.dbd.C(Me).sub.2I-1416 OMe OCH.sub.2 CH.dbd.CH.sub.2I-1417 OMe OCH.sub.2 CH.dbd.CHMeI-1418 OMe OEtI-1419 OMe OPrI-1420 OPr O-i-BuI-1421 OPr OBuI-1422 OPr OCH.sub.2 C(Me).dbd.CH.sub.2I-1423 OPr OCH.sub.2 CCHI-1424 OPr OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1425 OPr OCH.sub.2 CH.dbd.C(Me).sub.2I-1426 OPr OCH.sub.2 CH.dbd.CH.sub.2I-1427 OPr OCH.sub.2 CH.dbd.CHMeI-2021 A chlorine atom Me SMeI-2022 at 4-position Me SEtI-2023 (4-Cl) for Me SPrI-2024 Compound I-2021 OMe SMeI-2025 through OMe SEtI-2026 Compound I-2035 OMe SPrI-2027 SMe SMeI-2028 SEt SEtI-2029 SPr iSPrI-2030 OCH.sub.2 CH.dbd.CH.sub.2 SMeI-2031 OCH.sub.2 CH.dbd.CH.sub.2 SEtI-2032 OCH.sub.2 CH-CH.sub.2 SPrI-2033 Cl SMeI-2034 Cl SEtI-2035 Cl SPr__________________________________________________________________________
TABLE 1__________________________________________________________________________(13/15)No. X.sub.n R.sup.1 R.sup.2__________________________________________________________________________I-1428 A fluorine atom OCHF.sub.2 OCHF.sub.2I-1429 at 4-position CF.sub.3 OCH.sub.2 C(Me).dbd.CH.sub.2I-1430 (4-F) for CF.sub.3 OCH.sub.2 CCHI-1431 Compound I-1428 CF.sub.3 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1432 through CF.sub.3 OCH.sub.2 CH.dbd.C(Me).sub.2I-1433 Compound I-1537 CF.sub.3 OCH.sub.2 CH.dbd.CH.sub.2I-1434 CF.sub.3 OCH.sub.2 CH.dbd.CHMeI-1435 Cl O-i-BuI-1436 Cl OBuI-1437 Cl OCH.sub.2 C(Me).dbd.CH.sub.2I-1438 Cl OCH.sub.2 C.sub.2 F.sub.5I-1439 Cl OCH.sub.2 CCHI-1440 Cl OCH.sub.2 CF.sub.3I-1441 Cl OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1442 Cl OCH.sub.2 CH.dbd.C(Me).sub.2I-1443 Cl OCH.sub.2 CH.dbd.CH.sub.2I-1444 Cl OCH.sub.2 CH.dbd.CHMeI-1445 Cl OEtI-1446 Cl OMeI-1447 Cl OPrI-1448 Et OCH.sub.2 C(Me).dbd.CH.sub.2I-1449 Et OCH.sub.2 CCHI-1450 Et OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1451 Et OCH.sub.2 CH.dbd.C(Me).sub.2I-1452 Et OCH.sub.2 CH.dbd.CH.sub.2I-1453 Et OCH.sub.2 CH.dbd.CHMeI-1454 Me O-i-PrI-1455 Me OCH.sub.2 C(Me).dbd.CH.sub.2I-1456 Me OCH.sub.2 CCHI-1457 Me OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1458 Me OCH.sub.2 CH.dbd.C(Me).sub.2I-1459 Me OCH.sub.2 CH.dbd.CH.sub.2I-1460 Me OCH.sub.2 CH.dbd.CHMeI-1461 Me OEtI-1462 Me OMeI-1463 O-i-Bu O-i-BuI-1464 OBu OBuI-1465 OCH.sub.2 C(Me).dbd.CH.sub.2 OCH.sub.2 C(Me).dbd.CH.sub.2I-1466 OCH.sub.2 CCH OCH.sub.2 CCHI-1467 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1468 OCH.sub.2 CH.dbd.C(Me).sub.2 OCH.sub.2 CH.dbd.C(Me).sub.2I-1469 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.dbd.CH.sub.2I-1470 OCH.sub.2 CH.dbd.CHMe OCH.sub.2 CH.dbd.CHMeI-1471 OEt OEtI-1472 OMe OMeI-1473 OPr OPrI-1474 Pr OCH.sub.2 C(Me).dbd.CH.sub.2I-1475 Pr OCH.sub.2 CCHI-1476 Pr OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1477 Pr OCH.sub.2 CH.dbd.C(Me).sub.2I-1478 Pr OCH.sub.2 CH.dbd.CH.sub.2I-1479 Pr OCH.sub.2 CH.dbd.CHMeI-1480 i-Pr OCH.sub.2 C(Me).dbd.CH.sub.2I-1481 i-Pr OCH.sub.2 CCHI-1482 i-Pr OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1483 i-Pr OCH.sub.2 CH.dbd.C(Me).sub.2I-1484 i-Pr OCH.sub.2 CH.dbd.CH.sub.2I-1485 i-Pr OCH.sub.2 CH.dbd.CHMeI-1486 O-i-Bu OCH.sub.2 C(Me).dbd.CH.sub.2I-1487 O-i-Bu OCH.sub.2 CCHI-1488 O-i-Bu OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1489 O-i-Bu OCH.sub.2 CH.dbd.C(Me).sub.2I-1490 O-i-Bu OCH.sub.2 CH.dbd.CH.sub.2I-1491 O-i-Bu OCH.sub.2 CH.dbd.CHMeI-1492 OBu O-i-BuI-1493 OBu OCH.sub.2 C(Me).dbd.CH.sub.2I-1494 OBu OCH.sub.2 CCHI-1495 OBu OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1496 OBu OCH.sub.2 CH.dbd.C(Me).sub.2I-1497 OBu OCH.sub.2 CH.dbd.CH.sub.2I-1498 OBu OCH.sub.2 CH.dbd.CHMeI-1499 OCH.sub.2 CF.sub.3 OCH.sub.2 C(Me).dbd.CH.sub.2I-1500 OCH.sub.2 CF.sub.3 OCH.sub.2 C.sub.2 F.sub.5I-1501 OCH.sub.2 CF.sub.3 OCH.sub.2 CCHI-1502 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1503 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.dbd.C(Me).sub.2I-1504 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.dbd.CH.sub.2I-1505 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.dbd.CHMeI-1506 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 C(Me).dbd.CH.sub.2I-1507 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CCHI-1508 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1509 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.dbd.C(Me).sub.2I-1510 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.dbd.CHMeI-1511 OEt O-i-BuI-1512 OEt OBuI-1513 OEt OCH.sub.2 C(Me).dbd.CH.sub.2I-1514 OEt OCH.sub.2 CCHI-1515 OEt OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1516 OEt OCH.sub.2 CH.dbd.C(Me).sub.2I-1517 OEt OCH.sub.2 CH.dbd.CH.sub.2I-1518 OEt OCH.sub.2 CH.dbd.CHMeI-1519 OEt OPrI-1520 OMe O-i-BuI-1521 OMe OBuI-1522 OMe OCH.sub.2 C(Me).dbd.CH.sub.2I-1523 OMe OCH.sub.2 CCH1-1524 OMe OCH.sub.2 CH.sub.2 C(me).dbd.CH.sub.2I-1525 OMe OCH.sub.2 CH.dbd.C(Me).sub.2I-1526 OMe OCH.sub.2 CH.dbd.CH.sub.2I-1527 OMe OCH.sub.2 CH.dbd.CHMeI-1528 OMe OEtI-1529 OMe OPrI-1530 OPr O-i-BuI-1531 OPr OBuI-1532 OPr OCH.sub.2 C(Me).dbd.CH.sub.2I-1533 OPr OCH.sub.2 CCHI-1534 OPr OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1535 OPr OCH.sub.2 CH.dbd.C(Me).sub.2I-1536 OPr OCH.sub.2 CH.dbd.CH.sub.2I-1537 OPr OCH.sub.2 CH.dbd.CHMeI-2041 A fluorine atom Me SMeI-2042 at 4-position Me SEtI-2043 (4-F) for Me SPrI-2044 Compound I-2041 OMe SMeI-2045 through OMe SEtI-2046 Compound I-2055 OMe SPrI-2047 SMe SMeI-2048 SEt SEtI-2049 SPr SPrI-2050 OCH.sub.2 CH.dbd.CH.sub.2 SMeI-2051 OCH.sub.2 CH.dbd.CH.sub.2 SEtI-2052 OCH.sub.2 CH.dbd.CH.sub.2 SPrI-2053 Cl SMeI-2054 Cl SEtI-2055 Cl SPr__________________________________________________________________________
TABLE 1__________________________________________________________________________(14/15)No. X.sub.n R.sup.1 R.sup.2__________________________________________________________________________I-1538 A bromine atom OCHF2 OCHF.sub.2I-1539 at 4-position CF.sub.3 OCH.sub.2 C(Me).dbd.CH.sub.2I-1540 (4-Br) for CF.sub.3 OCH.sub.2 CCHI-1541 Compound I-1538 CF.sub.3 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1542 through CF.sub.3 OCH.sub.2 CH.dbd.C(Me).sub.2I-1543 Compound I-1647 CF.sub.3 OCH.sub.2 CH.dbd.CH.sub.2I-1544 CF.sub.3 OCH.sub.2 CH.dbd.CHMeI-1545 Cl O-i-BuI-1546 Cl OBuI-1547 Cl OCH.sub.2 C(Me).dbd.CH.sub.2I-1548 Cl OCH.sub.2 C.sub.2 F.sub.5I-1549 Cl OCH.sub.2 CCHI-1550 Cl OCH.sub.2 CF.sub.3I-1551 Cl OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1552 Cl OCH.sub.2 CH.dbd.C(Me).sub.2I-1553 Cl OCH.sub.2 CH.dbd.CH.sub.2I-1554 Cl OCH.sub.2 CH.dbd.CHMeI-1555 Cl OEtI-1556 Cl OMeI-1557 Cl OPrI-1558 Et OCH.sub.2 C(Me).dbd.CH.sub.2I-1559 Et OCH.sub.2 CCHI-1560 Et OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1561 Et OCH.sub.2 CH.dbd.C(Me).sub.2I-1562 Et OCH.sub.2 CH.dbd.CH.sub.2I-1563 Et OCH.sub.2 CH.dbd.CHMeI-1564 Me O-i-PrI-1565 Me OCH.sub.2 C(Me).dbd.CH.sub.2I-1566 Me OCH.sub.2 CCHI-1567 Me OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1568 Me OCH.sub.2 CH.dbd.C(Me).sub.2I-1569 Me OCH.sub.2 CH.dbd.CH.sub.2I-1570 Me OCH.sub.2 CH.dbd.CHMeI-1571 Me OEtI-1572 Me OMeI-1573 O-i-Bu O-i-Bu1-1574 OBu OBuI-1575 OCH.sub.2 C(Me).dbd.CH.sub.2 OCH.sub.2 C(Me).dbd.CH.sub.2I-1576 OCH.sub.2 CCH OCH.sub.2 CCHI-1577 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1578 OCH.sub.2 CH.dbd.C(Me).sub.2 OCH.sub.2 CH.dbd.C(Me).sub.2I-1579 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.dbd.CH.sub.2I-1580 OCH.sub.2 CH.dbd.CHMe OCH.sub.2 CH.dbd.CHMeI-1581 OEt OEtI-1582 OMe OMeI-1583 OPr OPrI-1584 Pr OCH.sub.2 C(Me).dbd.CH.sub.2I-1585 Pr OCH.sub.2 CCHI-1586 Pr OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1587 Pr OCH.sub.2 CH.dbd.C(Me).sub.2I-1588 Pr OCH.sub.2 CH.dbd.CH.sub.2I-1589 Pr OCH.sub.2 CH.dbd.CHMeI-1590 i-Pr OCH.sub.2 C(Me).dbd.CH.sub.2I-1591 i-Pr OCH.sub.2 CCHI-1592 i-Pr OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1593 i-Pr OCH.sub.2 CH.dbd.C(Me).sub.2I-1594 i-Pr OCH.sub.2 CH.dbd.CH.sub.2I-1595 i-Pr OCH.sub.2 CH.dbd.CHMeI-1596 O-i-Bu OCH.sub.2 C(Me).dbd.CH.sub.2I-1597 O-i-Bu OCH.sub.2 CCHI-1598 O-i-Bu OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1599 O-i-Bu OCH.sub.2 CH.dbd.C(Me).sub.2I-1600 O-i-Bu OCH.sub.2 CH.dbd.CH.sub.2I-1601 O-i-Bu OCH.sub.2 CH.dbd.CHMeI-1602 OBu O-i-BuI-1603 OBu OCH.sub.2 C(Me).dbd.CH.sub.2I-1604 OBu OCH.sub.2 CCHI-1605 OBu OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1606 OBu OCH.sub.2 CH.dbd.C(Me).sub.2I-1607 OBU OCH.sub.2 CH.dbd.CH.sub.2I-1608 OBu OCH.sub.2 CH.dbd.CHMeI-1609 OCH.sub.2 CF.sub.3 OCH.sub.2 C(Me).dbd.CH.sub.2I-1610 OCH.sub.2 CF.sub.3 OCH.sub.2 C.sub.2 F.sub.5I-1611 OCH.sub.2 CF.sub.3 OCH.sub.2 CCHI-1612 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1613 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.dbd.C(Me).sub.2I-1614 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.dbd.CH.sub.2I-1615 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.dbd.CHMeI-1616 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 C(Me).dbd.CH.sub.2I-1617 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CCHI-1618 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1619 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.dbd.C(Me).sub.2I-1620 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.dbd.CHMeI-1621 OEt O-i-BuI-1622 OEt OBuI-1623 OEt OCH.sub.2 C(Me).dbd.CH.sub.2I-1624 OEt OCH.sub.2 CCHI-1625 OEt OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1626 OEt OCH.sub.2 CH.dbd.C(Me).sub.2I-1627 OEt OCH.sub.2 CH.dbd.CH.sub.2I-1628 OEt OCH.sub.2 CH.dbd.CHMeI-1629 OEt OPrI-1630 OMe O-i-BuI-1631 OMe OBuI-1632 OMe OCH.sub.2 C(Me).dbd.CH.sub.2I-1633 OMe OCH.sub.2 CCHI-1634 OMe OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1635 OMe OCH.sub.2 CH.dbd.C(Me).sub.2I-1636 OMe OCH.sub.2 CH.dbd.CH.sub.2I-1637 OMe OCH.sub.2 CH.dbd.CHMeI-1638 OMe OEtI-1639 OMe OPrI-1640 OPr O-i-BuI-1641 OPr OBuI-1642 OPr OCH.sub.2 C(Me).dbd.CH.sub.2I-1643 OPr OCH.sub.2 CCHI-1644 OPr OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1645 OPr OCH.sub.2 CH.dbd.C(Me).sub.2I-1646 OPr OCH.sub.2 CH.dbd.CH.sub.2I-1647 OPr OCH.sub.2 CH.dbd.CHMe__________________________________________________________________________
TABLE 1__________________________________________________________________________(15/15)No. X.sub.n R.sup.1 R.sup.2__________________________________________________________________________I-1648 A methyl group OCHF.sub.2 OCHF.sub.2I-1649 at 4-position CF.sub.3 OCH.sub.2 C(Me).dbd.CH.sub.2I-1650 (4-Me) for CF.sub.3 OCH.sub.2 CCHI-1651 Compound I-1648 CF.sub.3 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1652 through CF.sub.3 OCH.sub.2 CH.dbd.C(Me).sub.2I-1653 Compound I-1757 CF.sub.3 OCH.sub.2 CH.dbd.CH.sub.2I-1654 CF.sub.3 OCH.sub.2 CH.dbd.CHMeI-1655 Cl O-i-BuI-1656 Cl OBuI-1657 Cl OCH.sub.2 C(Me).dbd.CH.sub.2I-1658 Cl OCH.sub.2 C.sub.2 F.sub.5I-1659 Cl OCH.sub.2 CCHI-1660 Cl OCH.sub.2 CF.sub.3I-1661 Cl OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1662 Cl OCH.sub.2 CH.dbd.C(Me).sub.2I-1663 Cl OCH.sub.2 CH.dbd.CH.sub.2I-1664 Cl OCH.sub.2 CH.dbd.CHMeI-1665 Cl OEtI-1666 Cl OMeI-1667 Cl OPrI-1668 Et OCH.sub.2 C(Me).dbd.CH.sub.2I-1669 Et OCH.sub.2 CCHI-1670 Et OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1671 Et OCH.sub.2 CH.dbd.C(Me).sub.2I-1672 Et OCH.sub.2 CH.dbd.CH.sub.2I-1673 Et OCH.sub.2 CH.dbd.CHMeI-1674 Me O-i-PrI-1675 Me OCH.sub.2 C(Me).dbd.CH.sub.2I-1676 Me HI-1677 Me OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1678 Me OCH.sub.2 CH.dbd.C(Me).sub.2I-1679 Me OCH.sub.2 CH.dbd.CH.sub.2I-1680 Me OCH.sub.2 CH.dbd.CHMeI-1681 Me OEtI-1682 Me OMeI-1683 O-i-Bu O-i-BuI-1684 OBu OBuI-1685 OCH.sub.2 C(Me).dbd.CH.sub.2 OCH.sub.2 C(Me).dbd.CH.sub.2I-1686 OCH.sub.2 CCH OCH.sub.2 CCHI-1687 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1688 OCH.sub.2 CH.dbd.C(Me).sub.2 OCH.sub.2 CH.dbd.C(Me).sub.2I-1689 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.dbd.CH.sub.2I-1690 OCH.sub.2 CH.dbd.CHMe OCH.sub.2 CH.dbd.CHMeI-1691 OEt OEtI-1692 OMe OMeI-1693 OPr OPrI-1694 Pr OCH.sub.2 C(Me).dbd.CH.sub.2I-1695 Pr OCH.sub.2 CCHI-1696 Pr OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1697 Pr OCH.sub.2 CH.dbd.C(Me).sub.2I-1698 Pr OCH.sub.2 CH.dbd.CH.sub.2I-1699 Pr OCH.sub.2 CH.dbd.CHMeI-1700 i-Pr OCH.sub.2 C(Me).dbd.CH.sub.2I-1701 i-Pr OCH.sub.2 CCHI-1702 i-Pr OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1703 i-Pr OCH.sub.2 CH.dbd.C(Me).sub.2I-1704 i-Pr OCH.sub.2 CH.dbd.CH.sub.2I-1705 i-Pr OCH.sub.2 CH.dbd.CHMeI-1706 O-i-Bu OCH.sub.2 C(Me).dbd.CH.sub.2I-1707 O-i-Bu OCH.sub.2 CCHI-1708 O-i-Bu OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1709 O-i-Bu OCH.sub.2 CH.dbd.C(Me).sub.2I-1710 O-i-Bu OCH.sub.2 CH.dbd.CH.sub.2I-1711 O-i-Bu OCH.sub.2 CH.dbd.CHMeI-1712 OBu O-i-BuI-1713 OBu OCH.sub.2 C(Me).dbd.CH.sub.2I-1714 OBu OCH.sub.2 CCHI-1715 OBu OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1716 OBu OCH.sub.2 CH.dbd.C(Me).sub.2I-1717 OBu OCH.sub.2 CH.dbd.CH.sub.2I-1718 OBu OCH.sub.2 CH.dbd.CHMeI-1719 OCH.sub.2 CF.sub.3 OCH.sub.2 C(Me).dbd.CH.sub.2I-1720 OCH.sub.2 CF.sub.3 OCH.sub.2 C.sub.2 F.sub.5I-1721 OCH.sub.2 CF.sub.3 OCH.sub.2 CCHI-1722 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1723 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.dbd.C(Me).sub.2I-1724 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.dbd.CH.sub.2I-1725 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.dbd.CHMeI-1726 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 C(Me).dbd.CH.sub.2I-1727 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CCHI-1728 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1729 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.dbd.C(Me).sub.2I-1730 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.dbd.CHMeI-1731 OEt O-i-BuI-1732 OEt OBuI-1733 OEt OCH.sub.2 C(Me).dbd.CH.sub.2I-1734 OEt OCH.sub.2 CCHI-1735 OEt OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1736 OEt OCH.sub.2 CH.dbd.C(Me).sub.2I-1737 OEt OCH.sub.2 CH.dbd.CH.sub.2I-1738 OEt OCH.sub.2 CH.dbd.CHMeI-1739 OEt OPrI-1740 OMe O-i-BuI-1741 OMe OBuI-1742 OMe OCH.sub.2 C(Me).dbd.CH.sub.2I-1743 OMe OCH.sub.2 CCHI-1744 OMe OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1745 OMe OCH.sub.2 CH.dbd.C(Me).sub.2I-1746 OMe OCH.sub.2 CH.dbd.CH.sub.21-1747 OMe OCH.sub.2 CH.dbd.CHMeI-1748 OMe OEtI-1749 OMe OPrI-1750 OPr O-i-BuI-1751 OPr OBuI-1752 OPr OCH.sub.2 C(Me).dbd.CH.sub.2I-1753 OPr OCH.sub.2 CCHI-1754 OPr OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2I-1755 OPr OCH.sub.2 CH.dbd.C(Me).sub.2I-1756 OPr OCH.sub.2 CH.dbd.CH.sub.2I-1757 OPr OCH.sub.2 CH.dbd.CHMeI-2061 A methyl group Me SMeI-2062 at 4-position Me SEtI-2063 (4-Me) for Me SPrI-2064 Compound I-2061 OMe SMeI-2065 through OMe SEtI-2066 Compound I-2075 OMe SPrI-2067 SMe SMeI-2068 SEt SEtI-2069 SPr SPrI-2070 OCH.sub.2 CH.dbd.CH.sub.2 SMeI-2071 OCH.sub.2 CH.dbd.CH.sub.2 SEtI-2072 OCH.sub.2 CH.dbd.CH.sub.2 SPrI-2073 Cl SMeI-2074 Cl SEtI-2075 Cl SPr__________________________________________________________________________
2-Benzyloxypyrimidine derivatives of the formula (I) shown in Table 1 (1/15 to 15/15) can be synthesized in accordance with the following scheme: ##STR9##
As shown in the above Reaction scheme I, the compound of the formula (I) may be produced by reacting the compound of the formula (II) with a substantially equal molar amount of the compound of the formula (III) in the presence of a basic compound, preferably in a solvent such as amides (e.g., dimethylformamide, dimethylacetamide, and N-methyl-2-pyrrolidinone), ethers (e.g., diethyl ether, dimethoxyethane, diisopropyl ether, tetrahydrofuran, diglyme, and dioxane), and aromatic hydrocarbons (e.g., benzene, toluene, xylene, and methylnaphthalene), preferably at a temperature in the range of -20.degree. C. to 150.degree. C. for a period of about 0.5 hour to one night (about 12 hours).
An iodide such as sodium iodide and potassium iodide or a crown ether such as 18-crown-6 and dibenzo-18-crown-6 may be added to the reaction as a reaction accelerator.
Examples of the compounds (II) which can be used for the production of the compounds (I) are shown in Table 2.
TABLE 2______________________________________No. Compound______________________________________II-1 2,3-DifluorobenzylalcoholII-2 2,3-Dimethyl-4-methoxybenzylalcoholII-3 2,3-DimethoxybenzylalcoholII-4 2,4-DichlorobenzylalcoholII-5 2,4-DifluorobenzylalcoholII-6 2,4-DimethylbenzylalcoholII-7 2,4-Dimethoxy-3-methylbenzylalcoholII-8 2,4-DimethoxybenzylalcoholII-9 2,5-DichlorobenzylalcoholII-10 2,5-DifluorobenzylalcoholII-11 2,5-DimethylbenzylalcoholII-12 2,5-DimethoxybenzylalcoholII-13 2,6-DichlorobenzylalcoholII-14 2,6-DifluorobenzylalcoholII-15 2-(Ethoxycarbonyl)benzylalcoholII-16 2-(Trifluoromethyl)benzylalcoholII-17 2-(Hydroxycarbonyl)benzylalcoholII-18 2-(Hydroxymethyl)benzylalcoholII-19 2-(Methoxycarbonyl)benzylalcoholII-20 2-EthylbenzylalcoholII-21 2-EthoxybenzylalcoholII-22 2-Chloro-6-fluorobenzylalcoholII-23 2-ChlorobenzylalcoholII-24 2-FluorobenzylalcoholII-25 2-BromobenzylalcoholII-26 2-MethylbenzylalcoholII-27 2-MethoxybenzylalcoholII-28 2-IodobenzylalcoholII-29 3,4,5-TrimethoxybenzylalcoholII-30 3,4-DichlorobenzylalcoholII-31 3,4-DifluorobenzylalcoholII-32 3,4-DimethylbenzylalcoholII-33 3,5-DichlorobenzylalcoholII-34 3,5-DifluorobenzylalcoholII-35 3,5-DimethylbenzylalcoholII-36 3,5-DimethoxybenzylalcoholII-37 3,5-Bis(triluoromethyl)benzylalcoholII-38 3-(Trifluoromethyl)benzylalcoholII-39 3-Ethoxy-4-methylbenzylalcoholII-40 3-Ethoxy-4-methoxybenzylalcoholII-41 3-ChlorobenzylalcoholII-42 3-NitrobenzylalcoholII-43 3-FluorobenzylalcoholII-44 3-BromobenzylalcoholII-45 3-BenzyloxybenzylalcoholII-46 3-MethylbenzylalcoholII-47 3-MethoxybenzylalcoholII-48 3-IodobenzylalcoholII-49 4-(1-Methylethyl)benzylalcoholII-50 4-(Trifluoromethyl)benzylalcoholII-51 4-(Methylthio)benzylalcoholII-52 4-(Methoxycarbonyl)benzylalcoholII-53 4-Ethoxy-3-methoxybenzylalcoholII-54 4-ChlorobenzylalcoholII-55 4-PhenylbenzylalcoholII-56 4-FluorobenzylalcoholII-57 4-Bromo-2-methoxybenzylalcoholII-58 4-BromobenzylalcoholII-59 4-Benzyloxy-3-methoxybenzylalcoholII-60 4-BenzyloxybenzylalcoholII-61 4-MethylbenzylalcoholII-62 4-MethoxybenzylalcoholII-63 4-IodobenzylalcoholII-64 Benzylalcohol______________________________________
The compounds of the formula (III) which may be used as starting materials in the Reaction scheme I can be either commercially available or easily synthesized.
As those in which Z represents a halogen among substituted pyrimidine derivatives of the formula (III) to be used as starting materials in the Reaction scheme I, commercially available reagents such as 2-chloropyrimidine, 2,4-dichloro-6-methylpyrimidine, and 2,4,6-trichloropyrimidine may be used. Alternatively, they may be synthesized by the process described in J. Chem. Soc. (C), 2031, (1966).
Among substituted pyrimidine derivatives of the formula (III), those of the formula (III-e) in which Z is linked to the pyrimidine ring through the sulfonyl thereof can be synthesized by oxidizing sulfur of 2-(alkylthio, aralkylthio, or arylthio)pyrimidine derivatives of the formula (IV-e), as shown in Reaction scheme II: ##STR10## wherein R.sup.1 and R.sup.2 each independently represents hydrogen, a halogen, hydroxyl, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C3-C.sub.5 alkenyl, C.sub.3 -C.sub.5 alkynyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 haloalkoxy, C.sub.3 -C.sub.5 alkenyloxy, C.sub.3 -C.sub.5 alkynyloxy, C.sub.1 -C.sub.4 alkylthio, or phenyl;
Z.sup.1 e represents C.sub.1 -C.sub.4 alkylthio, C.sub.7 -C.sub.9 aralkylthio, or arylthio (usually C.sub.6 -C.sub.8); and
Ze represents C.sub.1 -C.sub.4 alkylsulfonyl, C.sub.7 -C.sub.9 aralkylsulfonyl or arylsulfonyl (usually C.sub.6 -C.sub.8).
Ze preferably includes the following groups:
C.sub.1 -C.sub.4 alkylsulfonyl such as methylsulfonyl and ethylsulfonyl;
C.sub.7 -C.sub.9 aralkylsulfonyl such as benzylsulfonyl; and
arylsulfonyl (usually C.sub.6 -C.sub.8) such as phenylsulfonyl and p-tolylsulfonyl.
Z.sup.1 e preferably includes the following groups:
C.sub.1 -C.sub.4 alkylthio such as methylthio and ethylthio;
C.sub.7 -C.sub.9 aralkylthio such as benzylthio; and
arylthio (usually C.sub.6 -C.sub.8) such as phenylthio and p-tolylthio.
Examples of oxidants which may be used in the above oxidation reaction are peracids, sodium hypochloride, chlorine, potassium permanganate, and sodium tungstate.
Peracids are preferably selected from peracetic acid, perbenzoic acid, m-chloroperbenzoic acid, and perphthalic acid.
Peracetic acid may optionally be in situ produced in a reaction vessel by adding hydrogen peroxide to an acetic acid solution of the compound (IV-e).
Solvents which may be used in the oxidation reaction are halogenated alkyls (e.g., dichloromethane and chloroform), esters, aromatic hydrocarbons, lower fatty acids and water. Depending on the oxidants (e.g., chlorine), water should be used as solvent.
This oxidation reaction may be conducted at a temperature from under ice to the reflux point of the solvent (when a solvent is used).
Compounds (III-e) may be produced by oxidizing sulfur of commercially available reagents such as 4,6-dichloro-2-(methylthio)pyrimidine. They may also be produced by oxidizing sulfur contained in methylthio of 2-(methylthio)pyrimidine derivatives which can be prepared according to the process described in J. Chem. Soc., 1957, 1830 or in Grand Organic Chemistry, vol.17, p.94 (1959, published by Asakura Shoten).
Among substituted pyrimidine derivatives of the formula (III-e), examples of those in which Ze represents methylsulfonyl are shown in Table 3. These compounds may be used as starting materials for the production of the compounds (I) shown in Table 1 (1/15 to 15/15). In Table 3, R.sup.1 and R.sup.2 are identified by the same abbreviations as used in Table 1 (1/15 to 15/15).
TABLE 3______________________________________No. R.sup.1 R.sup.2______________________________________III-1 Me HIII-2 Me MeIII-3 Br BrIII-4 Cl CF.sub.3III-5 Cl ClIII-6 Cl EtIII-7 Cl MeIII-8 Cl PhIII-9 Cl PrIII-10 Cl i-PrIII-11 OCHF.sub.2 OCHF.sub.2III-12 CF.sub.3 OCH.sub.2 C(Me).dbd.CH.sub.2III-13 CF.sub.3 OCH.sub.2 CCHIII-14 CF.sub.3 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2III-15 CF.sub.3 OCH.sub.2 CH.dbd.C(Me).sub.2III-16 CF.sub.3 OCH.sub.2 CH.dbd.CH.sub.2III-17 CF.sub.3 OCH.sub.2 CH.dbd.CHMeIII-18 Cl O-i-BuIII-19 Cl OBuIII-20 Cl OCH.sub.2 C(Me).dbd.CH.sub.2III-21 Cl OCH.sub.2 C.sub.2 F.sub.5III-22 Cl OCH.sub.2 CCHIII-23 Cl OCH.sub.2 CF.sub.3III-24 Cl OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2III-25 Cl OCH.sub.2 CH.dbd.C(Me).sub.2III-26 Cl OCH.sub.2 CH.dbd.CH.sub.2III-27 Cl OCH.sub.2 CH.dbd.CHMeIII-28 Cl OEtIII-29 Cl OMeIII-30 Cl OPrIII-31 Et OCH.sub.2 C(Me).dbd.CH.sub.2III-32 Et OCH.sub.2 CCHIII-33 Et OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2III-34 Et OCH.sub.2 CH.dbd.C(Me).sub.2III-35 Et OCH.sub.2 CH.dbd.CH.sub.2III-36 Et OCH.sub.2 CH.dbd.CHMeIII-37 Me O-i-PrIII-38 Me OCH.sub.2 C(Me).dbd.CH.sub.2III-39 Me OCH.sub.2 CCHIII-40 Me OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2III-41 Me OCH.sub.2 CH.dbd.C(Me).sub.2III-42 Me OCH.sub.2 CH.dbd.CH.sub.2III-43 Me OCH.sub.2 CH.dbd.CHMeIII-44 Me OEtIII-45 Me OMeIII-46 O-i-Bu O-i-BuIII-47 OBu OBuIII-48 OCH.sub.2 C(Me).dbd.CH.sub.2 OCH.sub.2 C(Me).dbd.CH.sub.2III-49 OCH.sub.2 CCH OCH.sub.2 CCHIII-50 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2III-51 OCH.sub.2 CH.dbd.C(Me).sub.2 OCH.sub.2 CH.dbd.C(Me).sub.2III-52 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.dbd.CH.sub.2III-53 OCH.sub.2 CH.dbd.CHMe OCH.sub.2 CH.dbd.CHMeIII-54 OEt OEtIII-55 OMe OMeIII-56 OPr OPrIII-57 Pr OCH.sub.2 C(Me).dbd.CH.sub.2III-58 Pr OCH.sub.2 CCHIII-59 Pr OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2III-60 Pr OCH.sub.2 CH.dbd.C(Me).sub.2III-61 Pr OCH.sub.2 CH.dbd.CH.sub.2III-62 Pr OCH.sub.2 CH.dbd.CHMeIII-63 i-Pr OCH.sub.2 C(Me).dbd.CH.sub.2III-64 i-Pr OCH.sub.2 CCHIII-65 i-Pr OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2III-66 i-Pr OCH.sub.2 CH.dbd.C(Me).sub.2III-67 i-Pr OCH.sub.2 CH.dbd.CH.sub.2III-68 i-Pr OCH.sub.2 CH.dbd.CHMeIII-69 O-i-Bu OCH.sub.2 C(Me).dbd.CH.sub.2III-70 O-i-Bu OCH.sub.2 CCHIII-71 O-i-Bu C(Me).dbd.CH.sub.2III-72 O-i-Bu OCH.sub.2 CH.dbd.C(Me).sub.2III-73 O-i-Bu OCH.sub.2 CH.dbd.CH.sub.2III-74 O-i-Bu OCH.sub.2 CH.dbd.CHMeIII-75 OBu O-i-BuIII-76 OBu OCH.sub.2 C(Me).dbd.CH.sub.2III-77 OBu OCH.sub.2 CCHIII-78 OBu OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2III-79 OBu OCH.sub.2 CH.dbd.C(Me).sub.2III-80 OBu OCH.sub.2 CH.dbd.CH.sub.2III-81 OBu OCH.sub.2 CH.dbd.CHMeIII-82 OCH.sub.2 CF.sub.3 OCH.sub.2 C(Me).dbd.CH.sub.2III-83 OCH.sub.2 CF.sub.3 OCH.sub.2 C.sub.2 F.sub.5III-84 OCH.sub.2 CF.sub.3 OCH.sub.2 CCHIII-85 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2III-86 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.dbd.C(Me).sub.2III-87 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.dbd.CH.sub.2III-88 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.dbd.CHMeIII-89 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 C(Me).dbd.CH.sub.2III-90 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CCHIII-91 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2III-92 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.dbd.C(Me).sub.2III-93 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.dbd.CHMeIII-94 OEt O-i-BuIII-95 OEt OBuIII-96 OEt OCH.sub.2 C(Me).dbd.CH.sub.2III-97 OEt OCH.sub.2 CCHIII-98 OEt OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2III-99 OEt OCH.sub.2 CH.dbd.C(Me).sub.2III-100 OEt OCH.sub.2 CH.dbd.CH.sub.2III-101 OEt OCH.sub.2 CH.dbd.CHMeIII-102 OEt OPrIII-103 OMe O-i-BuIII-104 OMe OBuIII-105 OMe OCH.sub.2 C(Me).dbd.CH.sub.2III-106 OMe OCH.sub.2 CCHIII-107 OMe OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2III-108 OMe OCH.sub.2 CH.dbd.C(Me).sub.2III-109 OMe OCH.sub.2 CH.dbd.CH.sub.2III-110 OMe OCH.sub.2 CH.dbd.CHMeIII-111 OMe OEtIII-112 OMe OPrIII-113 OPr O-i-BuIII-114 OPr OBuIII-115 OPr OCH.sub.2 C(Me).dbd.CH.sub.2III-116 OPr OCH.sub.2 CCHIII-117 OPr OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2III-118 OPr OCH.sub.2 CH.dbd.C(Me).sub.2III-119 OPr OCH.sub.2 CH.dbd.CH.sub.2III-120 OPr OCH.sub.2 CH.dbd.CHMe______________________________________
Compounds of the formula (III) including Compounds III-1 to III-120 of Table 3 each may be produced as follows.
In chloroform, to each 1 mol of Compounds IV-1 to IV-120 of Table 4 below, about twice molar amount of m-chloroperbenzoic acid is added and then stirred for a period of from 1 hour to one night at room temperature. The reaction mixture is partitioned by using saturated aqueous sodium hydrogen carbonate. An organic phase is washed with saturated aqueous sodium chloride and then dried over anhydrous sodium sulfate. Thereafter, the solvent is distilled off to afford a crude product, which is then purified on column chromatography to obtain the compound of the formula (III) (Compounds III-1 to III-120).
Alternatively, Compound III-1 to III-120 may be produced through oxidation by adding hydrogen peroxide to an acetic acid solution of Compounds IV-1 to IV-120 while producing in situ peracetic acid in a reaction vessel. In this case, the reaction may be performed at a temperature in the range of from room temperature to 100.degree. C. for a period of from 2 hours to one night.
Other compounds of the formula (III) can be obtained in a similar manner.
Among the above 2-(alkylthio, aralkylthio, or arylthio)pyrimidine derivatives, 2-(alkylthio or aralkylthio)pyrimidine derivatives can be synthesized by using the following processes.
Process (a): A compound having a 1,3-dicarbonyl group is cyclo-condensed with S-alkyl(or aralkyl)isothiourea.
This process (a) is suitable for the synthesis of the compounds in which a hydroxyl group is bonded to the positions 4 and/or 6 of 2-(alkylthio or aralkylthio)pyrimidine derivatives.
Process (b): A compound having a 1,3-dicarbonyl group is cyclo-condensed with thiourea to afford a 2-mercaptopyrimidine derivative, which is then alkylated or aralkylated at the 2-mercapto group thereof.
This process (b) is suitable for the synthesis of the compounds in which substituents are bonded to the positions 4 and 6 of the pyrimidine ring by a carbon-carbon bond, the compounds in which a hydrogen atom is bonded to either one of the positions 4 and 6 of the pyrimidine ring and a substituent is bonded to the other position by a carbon-carbon bond as well as the compounds in which a hydrogen atom is bonded to each of the positions 4 and 6 of the pyrimidine ring.
Compounds in which a halogen atom is bonded to the positions 4 and/or 6 of the pyrimidine ring can be derived from the compounds obtained by the process (a) or (b) as follows:
Process (c1), process (c2): A hydroxyl group is converted to a halogen atom by using phosphorus oxychloride (identical with phosphoryl chloride), phosphorus pentachloride, phosphorus oxybromide (identical with phosphoryl bromide or phosphoryl tribromide).
For convenience of explanation, dihalogenation and monohalogenation are designated as (c1) and (c2), respectively.
Further, a chlorine atom at the position 4 or 6 may be converted to an iodine atom through nucleophilic displacement by using potassium iodide or concentrated aqueous hydroiodic acid. Compounds in which a halogen atom and a hydroxyl group is bonded thereto can be synthesized as follows:
Process (d): Either one of the halogen atoms at the positions 4 and 6 obtained by (c1) or (c2) is converted to a hydroxyl group.
Compounds in which a substituent is ether-linked to the position 4 and/or 6 of the pyrimidine ring can be synthesized as follows:
Process (e): An oxygen atom of the hydroxyl group at the position 4 or 6 of the pyrimidine ring of the compound which was obtained from (a) or (b) is etherified in the presence of a basic compound.
Process (f): A halogen atom at the position 4 or 6 of the pyrimidine ring of the compound which was obtained from (c1) or (c2) is etherified through nucleophilic displacement in the presence of a basic compound.
Among the compounds in which a substituent is ether-linked to each of the positions 4 and 6 of the pyrimidine ring, those in which the substituent of the position 4 is different from that of the position 6 can be synthesized as follows:
Process (g): A halogen atom at the position 4 (or the position 6) of the compound obtained by (c1) is etherified through nucleophilic displacement, and then, a halogen atom at the position 6 (or 4) is etherified through nucleophilic displacement.
Process (h): A hydroxyl group of the compound obtained by (d) is etherified, and then, a halogen atom at the position 4 (or 6) is etherified.
Compounds having both an ether-linked substituent and a halogen atom, besides the above described process (f), can be synthesized as follows:
Process (i): A halogen atom at the position 4 (or 6) of the compounds obtained by (c1) is converted to a hydroxyl group, which is then etherified.
Compounds having both an ether-linked substituent and a hydroxyl group can be synthesized as follows:
Process (j): An oxygen atom of the hydroxyl group at either position 4 or position 6 of the pyrimidine ring of the compounds obtained by the process (a) or (b) is etherified in the presence of a basic compound.
Process (k): A halogen atom at the position 4 (or 6) of the compounds obtained by the process (c1) is converted to a hydroxyl group, an oxygen atom of which is then etherified. Then, a halogen atom at the position 6 (or 4) is converted to a hydroxyl group.
Examples compounds (IV-e) usable as starting materials for the production of compounds shown in Table 3 are listed in Table 4.
R.sup.1 and R.sup.2 in Table 4 are represented in a similar manner as in Table 1 (1/15 to 15/15). In the column of "Z.sup.1 e", SMe represents methylthio.
In the column of "process" in Table 4, symbols a, b, c1, c2, e, f and g corresponds to the processes (a), (b), (c1), (c2), (e), (f) and (g) above, respectively.
TABLE 4__________________________________________________________________________No. R.sup.1 R.sup.2 Z.sup.1 e Process__________________________________________________________________________IV-1 Me H SMe bIV-2 Me Me SMe bIV-3 Br Br SMe c1IV-4 Cl CF.sub.3 SMe c2IV-5 Cl Cl SMe c1IV-6 Cl Et SMe c2IV-7 Cl Me SMe c2IV-8 Cl Ph SMe c2IV-9 Cl Pr SMe c2IV-10 Cl i-Pr SMe c2IV-11 OCHF.sub.2 OCHF.sub.2 SMe eIV-12 CF.sub.3 OCH.sub.2 C(Me).dbd.CH.sub.2 SMe fIV-13 CF.sub.3 OCH.sub.2 CCH SMe fIV-14 CF.sub.3 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2 SMe fIV-15 CF.sub.3 OCH.sub.2 CH.dbd.C(Me).sub.2 SMe fIV-16 CF.sub.3 OCH.sub.2 CH.dbd.CH.sub.2 SMe fIV-17 CF.sub.3 OCH.sub.2 CH.dbd.CHMe SMe fIV-18 Cl O-i-Bu SMe fIV-19 Cl OBu SMe fIV-20 Cl OCH.sub.2 C(Me).dbd.CH.sub.2 SMe fIV-21 Cl OCH.sub.2 C.sub.2 F.sub.5 SMe fIV-22 Cl OCH.sub.2 CCH SMe fIV-23 Cl OCH.sub.2 CF.sub.3 SMe fIV-24 Cl OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2 SMe fIV-25 Cl OCH.sub.2 CH.dbd.C(Me).sub.2 SMe fIV-26 Cl OCH.sub.2 CH.dbd.CH.sub.2 SMe fIV-27 Cl OCH.sub.2 CH.dbd.CHMe SMe fIV-28 Cl OEt SMe fIV-29 Cl OMe SMe fIV-30 Cl OPr SMe fIV-31 Et OCH.sub.2 C(Me).dbd.CH.sub.2 SMe fIV-32 Et OCH.sub.2 CCH SMe fIV-33 Et OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2 SMe fIV-34 Et OCH.sub.2 CH.dbd.C(Me).sub.2 SMe fIV-35 Et OCH.sub.2 CH.dbd.CH.sub.2 SMe fIV-36 Et OCH.sub.2 CH.dbd.CHMe SMe fIV-37 Me O-i-Pr SMe fIV-38 Me OCH.sub.2 C(Me).dbd.CH.sub.2 SMe fIV-39 Me OCH.sub.2 CCH SMe fIV-40 Me OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2 SMe fIV-41 Me OCH.sub.2 CH.dbd.C(Me).sub.2 SMe fIV-42 Me OCH.sub.2 CH.dbd.CH.sub.2 SMe fIV-43 Me OCH.sub.2 CH.dbd.CHMe SMe fIV-44 Me OEt SMe fIV-45 Me OMe SMe fIV-46 O-i-Bu O-i-Bu SMe fIV-47 OBu OBu SMe fIV-48 OCH.sub.2 C(Me).dbd.CH.sub.2 OCH.sub.2 C(Me).dbd.CH.sub.2 SMe fIV-49 OCH.sub.2 CCH OCH.sub.2 CCH SMe fIV-50 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2 SMe fIV-51 OCH.sub.2 CH.dbd.C(Me).sub.2 OCH.sub.2 CH.dbd.C(Me).sub.2 SMe fIV-52 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.dbd.CH.sub.2 SMe fIV-53 OCH.sub.2 CH.dbd.CHMe OCH.sub.2 CH.dbd.CHMe SMe fIV-54 OEt OEt SMe fIV-55 OMe OMe SMe fIV-56 OPr OPr SMe fIV-57 Pr OCH.sub.2 C(Me).dbd.CH.sub.2 SMe fIV-58 Pr OCH.sub.2 CCH SMe fIV-59 Pr OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2 SMe fIV-60 Pr OCH.sub.2 CH.dbd.C(Me).sub.2 SMe fIV-61 Pr OCH.sub.2 CH.dbd.CH.sub.2 SMe fIV-62 Pr OCH.sub.2 CH.dbd.CHMe SMe fIV-63 i-Pr OCH.sub.2 C(Me).dbd.CH.sub.2 SMe fIV-64 i-Pr OCH.sub.2 CCH SMe fIV-65 i-Pr OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2 SMe fIV-66 i-Pr OCH.sub.2 CH.dbd.C(Me).sub.2 SMe fIV-67 i-Pr OCH.sub.2 CH.dbd.CH.sub.2 SMe fIV-68 i-Pr OCH.sub.2 CH.dbd.CHMe SMe fIV-69 O-i-Bu OCH.sub.2 C(Me).dbd.CH.sub.2 SMe gIV-70 O-i-Bu OCH.sub.2 CCH SMe gIV-71 O-i-Bu OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2 SMe gIV-72 O-i-Bu OCH.sub.2 CH.dbd.C(Me).sub.2 SMe gIV-73 O-i-Bu OCH.sub.2 CH.dbd.CH.sub.2 SMe gIV-74 O-i-Bu OCH.sub.2 CH.dbd.CHMe SMe gIV-75 OBu O-i-Bu SMe gIV-76 OBu OCH.sub.2 C(Me).dbd.CH.sub.2 SMe gIV-77 OBu OCH.sub.2 CCH SMe gIV-78 OBu OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2 SMe gIV-79 OBu OCH.sub.2 CH.dbd.C(Me).sub.2 SMe gIV-80 OBu OCH.sub.2 CH.dbd.CH.sub.2 SMe gIV-81 OBu OCH.sub.2 CH.dbd.CHMe SMe gIV-82 OCH.sub.2 CF.sub.3 OCH.sub.2 C(Me).dbd.CH.sub.2 SMe gIV-83 OCH.sub.2 CF.sub.3 OCH.sub.2 C.sub.2 F.sub.5 SMe gIV-84 OCH.sub.2 CF.sub.3 OCH.sub.2 CCH SMe gIV-85 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2 SMe gIV-86 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.dbd.C(Me).sub.2 SMe gIV-87 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.dbd.CH.sub.2 SMe gIV-88 OCH.sub.2 CF.sub.3 OCH.sub.2 CH.dbd.CHMe SMe gIV-89 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 C(Me).dbd.CH.sub.2 SMe gIV-90 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CCH SMe gIV-91 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2 SMe gIV-92 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.dbd.C(Me).sub.2 SMe gIV-93 OCH.sub.2 CH.dbd.CH.sub.2 OCH.sub.2 CH.dbd.CHMe SMe gIV-94 OEt O-i-Bu SMe gIV-95 OEt OBu SMe gIV-96 OEt OCH.sub.2 C(Me).dbd.CH.sub.2 SMe gIV-97 OEt OCH.sub.2 CCH SMe gIV-98 OEt OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2 SMe gIV-99 OEt OCH.sub.2 CH.dbd.C(Me).sub.2 SMe gIV-100 OEt OCH.sub.2 CH.dbd.CH.sub.2 SMe gIV-101 OEt OCH.sub.2 CH.dbd.CHMe SMe gIV-102 OEt OPr SMe gIV-103 OMe O-i-Bu SMe gIV-104 OMe OBu SMe gIV-105 OMe OCH.sub.2 C(Me).dbd.CH.sub.2 SMe gIV-106 OMe OCH.sub.2 CCH SMe gIV-107 OMe OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2 SMe gIV-108 OMe OCH.sub.2 CH.dbd.C(Me).sub.2 SMe gIV-109 OMe OCH.sub.2 CH.dbd.CH.sub.2 SMe gIV-110 OMe OCH.sub.2 CH.dbd.CHMe SMe gIV-111 OMe OEt SMe gIV-112 OMe OPr SMe gIV-113 OPr O-i-Bu SMe gIV-114 OPr OBu SMe gIV-115 OPr OCH.sub.2 C(Me).dbd.CH.sub.2 SMe gIV-116 OPr OCH.sub.2 CCH SMe gIV-117 OPr OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2 SMe gIV-118 OPr OCH.sub.2 CH.dbd.C(Me).sub.2 SMe gIV-119 OPr OCH.sub.2 CH.dbd.CH.sub.2 SMe gIV-120 OPr OCH.sub.2 CH.dbd.CHMe SMe gIV-121 CF.sub.3 OH SMe aIV-122 Et OH SMe aIV-123 Me OH SMe aIV-124 OH OH SMe aIV-125 Ph OH SMe aIV-126 Pr OH SMe aIV-127 i-Pr OH SMe a__________________________________________________________________________
Compounds represented in Table 4 can be synthesized as follows:
Each of Compounds IV-121 to IV-127 can be synthesized by using the process (a) in a manner as described in either (1) or (2) below.
(1) 0.1 mol of methyl trifluoroacetoacetate or methyl acetoacetate, about 0.05 mol of methylisothiourea sulfate (2-methyl-2-thiopseudourea sulfate) (i.e., about 1 chemical equivalent of methylisothiourea) and 0.1 mol of sodium methoxide are reacted in 500 ml of methyl alcohol at a temperature of from room temperature to a reflux point for a period of from 4 hours to one night. Then, the reaction mixture is cooled with iced water and 0.1 mol of hydrochloric acid is added thereto. After insoluble matter is filtered off, the solvent is distilled off from the filtrate to afford a crude product, which is then recrystallized to obtain a purified product.
(2) 0.1 mol of ethyl trifluoroacetacetate, ethyl propionylacetate, ethyl acetoacetate, diethyl malonate, ethyl benzoylacetate, ethyl butyrylacetate, or ethyl isobutyrylacetate, about 0.05 mol of methylisothiourea sulfate (2-methyl-2-thiopseudourea sulfate) (i.e., about 1 chemical equivalent of methylisothiourea), and 0.1 mol of sodium ethoxide are reacted in 500 ml of ethyl alcohol at a temperature of from room temperature to a reflux point for a period of from 4 hours to one night. The reaction mixture is allowed to cool to room temperature, and then, while further cooling with iced water, 0.1 mol of hydrochloric acid is added thereto. After insoluble matter is filtered off, the solvent is distilled off from the filtrate to afford a crude product, which is then recrystallized to obtain a purified product.
Each of Compounds IV-1 and IV-2 can be synthesized by the process (b).
0.1 mol of acetylacetone or acetylacetaldehyde dimethylacetal is reacted with 0.1 mol of thiourea in 300 ml of ethyl alcohol containing 10 ml of 35% hydrochloric acid for 5 hours at room temperature. The reaction mixture is allowed to cool to room temperature, and then, while further water-cooling, sodium hydrogen carbonate is added thereto. After stirring for 2 hours, insoluble matter is filtered off. Additional sodium hydrogen carbonate is added to the filtrate, and then, while stirring at room temperature, 0.1 mol of dimethyl sulfate is added and the mixture is stirred for another 3 hours. The solvent is distilled off from the reaction mixture, and thereafter, the residue is redissolved in chloroform and washed with water. After dried over sodium sulfate, the solvent is distilled off to afford a crude product, which is then purified on column chromatography to obtain a purified product.
Each of Compounds IV-3 and IV-5 can be synthesized by the process (c1).
To 1 mol of 4,6-dihydroxy-2-methylthiopyrimidine (Compound IV-124), about 2 to 3 mol of phosphorus oxychloride (identical with phosphoryl chloride) or phosphorus oxybromide (identical with phosphoryl bromide) is added to react at a temperature of 70.degree. C. to 100.degree. C. for a period of about 0.5 hours to about 2 hours while stirring. The reaction mixture is post-treated by using ethyl acetate and water. Ethyl acetate layer is washed successively with aqueous sodium hydrogen carbonate and water, and then, dried over sodium sulfate. The solvent is distilled off to afford an end product, which may be purified on column chromatography as desired.
Each of Compounds IV-4 and IV-6 to IV-10 can be synthesized by the process (c2).
These compounds can be synthesized by using a similar reaction procedure for the synthesis of Compound IV-5, starting from each of Compounds IV-121 to IV-123 and Compounds IV-125 to IV-127 and phosphorus oxychloride employed at a molar ratio of about 1:1 to 1:2. The obtained product may be purified on column chromatography as desired.
Compound IV-11 can be synthesized by the process (e).
0.1 mol of Compound IV-124, 100 ml of dioxane, 20 ml of 40% aqueous sodium hydroxide, and 15 ml of water are stirred at a temperature of 60.degree. C. to 70.degree. C. 0.65 mol of chlorodifluoromethane and 80 ml of aqueous 40% sodium hydroxide are added thereto over a period of 4 hours. At 30 minutes after addition, 30% sulfuric acid is added to adjust pH to about 6. Precipitate is filtered off from the reaction mixture, an organic phase is separated from the filtrate, an aqueous phase is extracted with 75 ml of dioxane to separate another organic phase, which is combined with the previously obtained organic phase. To the combined organic phase, 20 ml of 40% aqueous sodium hydroxide is added, and then, 0.15 mol of chlorodifluoromethane is added thereto over a period of 1 hour at a temperature of 60.degree. C. to 70.degree. C. Precipitate is filtered off from the reaction mixture, an organic phase is separated from the filtrate and the obtained organic phase is washed with 20 ml of 50.degree. C. warm water. Dioxane is distilled off from the organic phase and the residue is distilled under reduced pressure to obtain a purified product.
Each of Compounds IV-12 to IV-17 can be synthesized by the process (f).
Substantially equal molar amounts of Compound IV-4 and sodium hydride are mixed with an excessive amount of 2-methyl-2-propen-1-ol (identical with methallyl alcohol), propargyl alcohol (identical with 2-propyn-1-ol), 3-methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol, allyl alcohol or crotyl alcohol serving also as solvent while removing heat as desired, and stirred for 1 hour at room temperature. The reaction mixture is post-treated by using ethyl acetate and saturated aqueous sodium hydrogen carbonate solution. Organic phase is washed with saturated aqueous sodium chloride and then dried over anhydrous sodium sulfate. Organic solvent is distilled off to obtain an end product, which can then be purified on column chromatography as desired.
Compounds IV-31 to IV-36 can be synthesized by a similar reaction procedure as above, starting from Compound IV-6 in place of Compound IV-4.
Compounds IV-57 to IV-62 can be synthesized by a similar reaction procedure as above, starting from Compound IV-9 in place of Compound IV-4.
Compounds IV-63 to IV-68 can be synthesized by a similar reaction procedure as above, starting from Compound IV-10 in place of Compound IV-4.
Each of Compounds IV-18 to IV-30 can be synthesized by the process (f).
In dimethylformamide or tetrahydrofuran, Compound IV-5 and any one of 2-methyl-1-propanol, butanol, 2-methyl-2-propen-1-ol (identical with methallyl alcohol), 2,2,3,3,3-pentafluoro-1-propanol, propargyl alcohol (identical with 2-propyn-1-ol), 3,3,3-trifuoroethanol, 3-methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol, allyl alcohol, crotyl alcohol, ethanol, methanol and propanol are mixed at a molar ratio of about 1:1 and stirred while cooling with iced water. About 1 to 1.1 molar equivalents of 60% sodium hydride is added thereto and the mixture is stirred for a period of from 3 hours to one night at room temperature. Then, the reaction mixture is post-treated by using ethyl acetate and iced water. An organic phase is washed with aqueous sodium chloride, dried over anhydrous sodium sulfate, and thereafter, organic solvent is distilled off to obtain an end product, which can then be purified on column chromatography as desired.
Each of Compounds IV-37 to IV-45 can be synthesized by the process (f).
Substantially equal molar amounts of the Compound IV-7 and sodium hydride are mixed with an excessive amount of 1-methylethylalcohol, 2-methyl-2-propen-1-ol (identical with methallyl alcohol), propargyl alcohol (identical with 2-propyn-1-ol), 3-methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol, allyl alcohol, crotyl alcohol, ethanol, or methanol serving also as solvent while removing heat as desired, and then stirred about 1 hour at room temperature. The reaction mixture is post-treated by using ethyl acetate and saturated aqueous sodium hydrogen carbonate. An organic phase is washed with saturated aqueous sodium chloride and then dried over anhydrous sodium sulfate. An organic solvent is distilled off to obtain an end product, which can then be purified on column chromatography as desired.
Each of Compounds IV-46 to IV-56 can be synthesized by the process (f).
50 ml of 2-methyl-1-propanol, butanol, 2-methyl-2-propen-1-ol (identical with methallyl alcohol), propargyl alcohol (identical with 2-propyn-1-ol), 3-methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol, allyl alcohol, crotyl alcohol, ethanol, methanol, or propanol is stirred while cooling with iced water. 0.2 mol of 60% sodium hydride is added thereto and the mixture is stirred for 1 hour. Then, 0.1 mol of Compound IV-5 is added thereto to react at a temperature of 35.degree. C. to 45.degree. C. for 4 hours. Alcohol is distilled off from the reaction mixture, then the residue is redissolved in ether, washed with water and dried over sodium sulfate. Ether is distilled off to afford a crude product, which can then be purified on column chromatography to obtain a purified product.
Each of Compounds IV-69 to IV-74 can be synthesized by the process (g).
0.1 mol of 2-methyl-2-propen-1-ol (identical with methallyl alcohol), propargyl alcohol (identical with 2-propyn-1-ol), 3-methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol, allyl alcohol or crotyl alcohol and 50 ml of dimethylacetamide are stirred while cooling with iced water. 0.1 mol of 60% sodium hydride is added thereto and stirred for 0.5 hour to prepare sodium alkoxide.
0.1 mol of Compound IV-18 and 50 ml of dimethylacetamide are stirred while cooling with iced water, then the previously prepared sodium alkoxide is added thereto over a period of 2 hours. After the addition and another 2 hours of stirring, dimethylacetamide is distilled off under reduced pressure from the reaction mixture. Thereafter, the residue is redissolved in ether, washed with water and dried over sodium sulfate. Ether is distilled off to afford a crude product, which can then be purified on column chromatography to obtain a purified product.
Each of Compounds IV-75 to IV-81 can be synthesized by the process (g).
0.1 mol of 2-methyl-1-propanol, 2-methyl-2-propen-1-ol (identical with methallyl alcohol), propargyl alcohol (identical with 2-propyn-1-ol), 3-methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol, allyl alcohol, or crotyl alcohol and 50 ml of dimethylacetamide are stirred while cooling with iced water. 0.1 mol of 60% sodium hydride is added thereto and the mixture is stirred for 0.5 hour to prepare sodium alkoxide.
0.1 mol of Compound IV-19 and 50 ml of dimethylacetamide are stirred while cooling with iced water, then the previously prepared sodium alkoxide is added thereto over a period of 2 hours. After the addition and another 2 hours of stirring, dimethylacetamide is distilled off under reduced pressure from the reaction mixture. Thereafter, the residue is redissolved in ether, washed with water and dried over sodium sulfate. Ether is distilled off to afford a crude product, which can then be purified on column chromatography to obtain a purified product.
Each of Compounds IV-82 to IV-88 can be synthesized by the process (g).
0.1 mol of 2-methyl-2-propen-1-ol (identical with methallyl alcohol), 2,2,3,3,3-pentafluoro-1-propanol, propargyl alcohol (identical with 2-propyn-1-ol), 3-methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol, allyl alcohol, or crotyl alcohol and 50 ml of dimethylacetamide are stirred while cooling with iced water. 0.1 mol of 60% sodium hydride is added thereto and the mixture is stirred for 0.5 hour to prepare sodium alkoxide.
0.1 mol of Compound IV-23 and 50 ml of dimethylacetamide are stirred while cooling with iced water, then the previously prepared sodium alkoxide is added thereto over a period of 2 hours. After the addition and another 2 hours of stirring, dimethylacetamide is distilled off under reduced pressure from the reaction mixture. Thereafter, the residue is redissolved in ether, washed with water and dried over sodium sulfate. Ether is distilled off to afford a crude product, which can then be purified on column chromatography to obtain a purified product.
Each of Compounds IV-89 to IV-93 can be synthesized by the process (g).
0.1 mol of 2-methyl-2-propen-1-ol (identical with methallyl alcohol), propargyl alcohol (identical with 2-propyn-1-ol), 3-methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol, or crotyl alcohol and 50 ml of dimethylacetamide are stirred while cooling with iced water. 0.1 mol of 60% sodium hydride is added thereto and the mixture is stirred for 0.5 hour to prepare sodium alkoxide.
0.1 mol of Compound IV-26 and 50 ml of dimethylacetamide are stirred while cooling with iced water, then the previously prepared sodium alkoxide is added thereto over a period of 2 hours. After the addition and another 2 hours of stirring, dimethylacetamide is distilled off under reduced pressure from the reaction mixture. Thereafter, the residue is redissolved in ether, washed with water and dried over sodium sulfate. Ether is distilled off to afford a crude product, which can then be purified on column chromatography to obtain a purified product.
Each of Compounds IV-94 to IV-102 can be synthesized by the process (g).
0.1 mol of 2-methyl-1-propanol, butanol, 2-methyl-2-propen-1-ol (identical with methallyl alcohol), propargyl alcohol (identical with 2-propyn-1-ol), 3-methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol, allyl alcohol, crotyl alcohol, or propanol and 50 ml of dimethylacetamide are stirred while cooling with iced water. 0.1 mol of 60% sodium hydride is added thereto and the mixture is stirred for 0.5 hour to prepare sodium alkoxide.
0.1 mol of Compound IV-28 and 50 ml of dimethylacetamide are stirred while cooling with iced water, then the previously prepared sodium alkoxide is added thereto over a period of 2 hours. After the addition and another 2 hours of stirring, dimethylacetamide is distilled off under reduced pressure from the reaction mixture. Thereafter, the residue is redissolved in ether, washed with water and dried over sodium sulfate. Ether is distilled off to afford a crude product, which can then be purified on column chromatography to obtain a purified product.
Each of Compounds IV-103 to IV-112 can be synthesized by the process (g).
0.1 mol of 2-methyl-1-propanol, butanol, 2-methyl-2-propen-1-ol (identical with methallyl alcohol), propargyl alcohol (identical with 2-propyn-1-ol), 3-methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol, allyl alcohol, crotyl alcohol, ethanol or propanol and 50 ml of dimethylacetamide are stirred while cooling with iced water. 0.1 mol of 60% sodium hydride is added thereto and the mixture is stirred for 0.5 hour to prepare sodium alkoxide.
0.1 mol of Compound IV-29 and 50 ml of dimethylacetamide are stirred while cooling with iced water, then the previously prepared sodium alkoxide is added thereto over a period of 2 hours. After the addition and another 2 hours of stirring, dimethylacetamide is distilled off under reduced pressure from the reaction mixture. Thereafter, the residue is redissolved in ether, washed with water and dried over sodium sulfate. Ether is distilled off to afford a crude product, which can then be purified on column chromatography to obtain a purified product.
Each of Compounds IV-113 to IV-120 can be synthesized by the process (g).
0.1 mol of 2-methyl-1-propanol, butanol, 2-methyl-2-propen-1-ol (identical with methallyl alcohol), propargyl alcohol (identical with 2-propyn-1-ol), 3-methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol, allyl alcohol, or crotyl alcohol and 50 ml of dimethylacetamide are stirred while cooling with iced water. 0.1 mol of 60% sodium hydride is added thereto and the mixture is stirred for 0.5 hour to prepare sodium alkoxide.
0.1 mol of Compound IV-30 and 50 ml of dimethylacetamide are stirred while cooling with iced water, then the previously prepared sodium alkoxide is added thereto over a period of 2 hours. After the addition and another 2 hours of stirring, dimethylacetamide is distilled off under reduced pressure from the reaction mixture. Thereafter, the residue is redissolved in ether, washed with water and dried over sodium sulfate. Ether is distilled off to afford a crude product, which can then be purified on column chromatography to obtain a purified product.
Other compounds of the formula (IV) can also be obtained in the same way.
Among 2-benzyloxypyrimidine derivatives of the above formula (I), 2-benzyloxypyrimidine derivatives of the formula (I-b) may be prepared by an process in accordance with Reaction scheme III, starting from 2-benzyloxypyrimidine derivatives of the formula (I-a), which are also included in the formula (I). ##STR11## wherein, R.sup.2, X, and n are as defined above; R.sup.1 a represents a halogen such as chlorine and bromine; and
R.sup.1 b represents:
C.sub.1 -C.sub.4 haloalkyl such as trifluoromethyl (CF.sub.3), fluoromethyl, difluoromethyl, and 2,2,2-trifluoroethyl;
C.sub.1 -C.sub.4 haloalkoxy such as difluoromethoxy (OCHF.sub.2), 1,1,2,2-tetrafluoroethoxy, 2,2,2-trifluoroethoxy (OCH.sub.2 CF.sub.3), 2-fluoroethoxy, difluoromethoxy, 2-bromo-1,1,2-trifluoroethoxy, 2,2,3,3,3-pentafluoropropoxy (OCH.sub.2 C.sub.2 F.sub.5), 1,1,2,3,3,3-hexafluoropropoxy, and 2-chloro-1,1,2-trifluoroethoxy;
C.sub.3 -C.sub.5 alkenyloxy such as allyloxy (OCH.sub.2 CH.dbd.CH.sub.2), (2-methyl-2-propenyl)oxy (OCH.sub.2 C(Me).dbd.CH.sub.2), crotyloxy (OCH.sub.2 CH=CHMe), (3-methyl-2-butenyl)oxy (OCH.sub.2 CH.dbd.C(Me).sub.2), and (3-methyl-3-butenyl)oxy (OCH.sub.2 CH.sub.2 C(Me).dbd.CH.sub.2);
C.sub.1 -C.sub.4 alkylthio such as methylthio (SMe), ethylthio (SEt), and propylthio (SPr); and
C.sub.3 -C.sub.5 alkynyloxy such as (2-propynyl)oxy (OCH.sub.2 CCH).
When compounds (I-b) are produced from compounds (I-a) in accordance with the above Reaction scheme III, the reaction conditions are usually as follows.
A compound (I-a) having a halogen atom at the position 4 or 6 is reacted with an alcohol which can induce the nucleophilic substitution of the above halogen atom with C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 haloalkoxy, C.sub.3 -C.sub.5 alkenyloxy, or C.sub.3 -C.sub.5 alkynyloxy, or an alkanethiol which can induce the nucleophilic substitution of the above halogen atom with C.sub.1 -C.sub.4 alkylthio, preferably in an amide such as dimethylformamide, dimethylaCetamide, and N-methyl-2-pyrrolidinone, or an ether such as diethyl ether, dimethoxyethane, diisopropyl ether, tetrahydrofuran, diglyme, and dioxane, in the presence of a basic compound, preferably at a temperature of -20.degree. C. to 150.degree. C. for from about 0.5 to several hours (about 3 hours) to obtain a compound (I-b).
When conducting the above reaction, iodides such as sodium iodide and potassium iodide or crown ethers such as 18-crown-6 and dibenzo-18-crown-6 may be added as a reaction accelerator.
Examples of the alcohols are 2-methyl-1-propanol, butanol, 2-methyl-2-propen-1-ol (identical with methallyl alcohol), 2,2,3,3,3-pentafluoro-1-propanol, propargyl alcohol (identical with 2-propyn-1-ol), 3,3,3-trifluoroethanol, 3-methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol, allyl alcohol, crotyl alcohol, ethanol, methanol, and propanol, etc.
Examples of the alkanethiols are methanethiol, ethanethiol, and propanethiol.
The method of application of 2-benzyloxypyrimidine derivatives of the formula (I) will now be described.
Although the derivatives of the formula (I) may be applied as it is, they are generally applied after formulated with adjuvants into various forms of compositions such as powders, wettable powders, granules, or emulsifiable concentrates.
The composition is usually formulated in such a way that it contains one or more of the derivatives of the formula (I) in an amount of 0.1 to 95% by weight, preferably 0.5 to 90% by weight, more preferably 2 to 70% by weight.
Among adjuvants including carriers, diluents, and surface active agents, suitable solid carriers include talc, kaolin, bentonite, diatomaceous earth, white carbon, clay, and the like. Suitable liquid diluents include water, xylene, toluene, chlorobenzene, cyclohexane, cyclohexanone, dimethylsulfoxide, dimethylformamide, alcohol, and the like.
Surface active agents may be properly selected depending upon their effects, and suitable emulsifying agents include polyoxyethylene alkyl aryl ether, polyoxyethylene solbitan monolaurate, and the like. Suitable dispersing agents include lignin sulfonate, dibutylnaphthalene sulfonate, and the like. Suitable wetting agents are alkyl sulfonates, alkylphenyl sulfonates and the like.
The above mentioned compositions include those which are to be applied as it is and those which are to be applied after diluted to a proper concentration by using a diluent such as water. When applied in diluted form, the concentration of the derivatives of the formula (I) are preferably 0.001 to 1.0% by weight. Application dose of the compounds of the present invention is usually 0.01 to 10 kg/ha, preferably 0.05 to 5 kg/ha.
The concentrations and application doses defined above are varied depending on dosage forms, time of application, way of application, application sites, plants to be treated and the like. Thus modifications thereof are possible without limited to the above defined range. Further, the derivatives of the formula (I) may be used in combination with other active ingredients such as fungicides, insecticides, acaricides, and herbicides.





EXAMPLES
2-Benzyloxypyrimidine derivatives of the present invention, production processes and use thereof will now be described in more detail by way of synthesis examples, formulation examples and test examples. "%" means percent by weight unless otherwise noted.
Synthesis Example 1
Synthesis of 4,6-dibromo-2-(phenylmethoxy)pyrimidine (Compound I-81)
4,6-dibromo-2-(methysulfonyl)pyrimidine (Compound III-3) (1.5 g, 0.00476 mol) was dissolved in toluene, and benzyl alcohol (Compound II-64) (0.515 g, 0.00476.times.1.0 mol) was added thereto. While cooling with ice, 60% sodium hydride (0.21 g, 0.00476.times.1.1 mol) was added while stirring. After stirred for 6 hours, the reaction solution was poured into water and extracted with toluene. The organic phase was washed with saturated aqueous sodium chloride, dried over anhydrous sodium sulfate and filtered, and thereafter, the solvent was distilled off. The residue was purified on silica gel column chromatography (Wakogel C300, 100 ml, ethyl acetate/hexane=20 ml/400 ml) to obtain the compound (I-81) as an oily product from the fraction of 100 ml to 120 ml.
Yield: 0.5 g.
Synthesis Example 2
Synthesis of 4,6-dichloro-2-(phenylmethoxy)pyrimidine (Compound I-173)
4, 6-Dichloro-2-(methysulfonyl)pyrimidine (Compound III-5) (21.3 g, 93.8 mmol) and benzyl alcohol (Compound II-64) (10.1 g, 93.8.times.1.0 mmol) were introduced into a 500 ml eggplant type flask, to which dimethylformamide (150 ml) was added to form a solution. While stirring in ice bath, 60% sodium hydride (3.94 g, 93.8.times.1.05 mmol) which had been washed with hexane was added. After bubbling was ceased, ice bath was removed and the reaction solution was stirred for 2 hours at room temperature. The reaction mixture was poured onto ice and the separated organic matter was extracted with ethyl acetate. The organic phase was washed successively with diluted hydrochloric acid and saturated aqueous sodium chloride, dried over anhydrous sodium sulfate, and thereafter, the solvent was distilled off. The residue was purified on silica gel column chromatography (Wakogel C300, ethyl acetate/hexane=1/50(v/v)) to obtain the compound (I-173) as an oily product.
Yield: 6.5 g (27%).
Synthesis Example 3
Synthesis of 4-chloro-6-methyl-2-(phenylmethoxy)pyrimidine (Compound I-240)
In tetrahydrofuran, benzyl alcohol (Compound II-64) (1.65 g, 0.010.times.1.5 mol) and sodium hydride (ca. 0.43 g, (60% in mineral oil), 0.010.times.1.05 mol) were mixed to form an alkoxide. 4-Chloro-6-methyl-2-(methylsulfonyl)pyrimidine (Compound III-7) (2.10 g, 0.010 mol) was added thereto and was allowed to react for 2 hours at room temperature. The reaction solution was partitioned between ethyl acetate and saturated aqueous sodium hydrogen carbonate, the organic phase was separated and washed with saturated aqueous sodium chloride, dried over anhydrous sodium sulfate and concentrated, and thereafter, purified on silica gel column to obtain the compound (I-240) as an oily product.
Yield: 1.31 g (56%).
.sup.1 H-NMR (60 MHz, CDCl.sub.3, .delta.): 2.37(3H,s), 5.33(2H,s), 6.73(1H,s), 7.1-7.6(5H,m).
Synthesis Example 4
Synthesis of 4-chloro-6-(3-methyl-2-butenyloxy)-2-(phenylmethoxy)pyrimidine (Compound I-342)
4-Chloro-6-(3-methyl-2-butenyloxy)-2-(methysulfonyl)pyrimidine (Compound III-25) (0.50 g, 1.8 mmol) and benzyl alcohol (Compound II-64) (0.195 g, 1.8.times.1.0 mmol) were introduced into a 50 ml eggplant type flask, to which dimethyl formamide (10 ml) was added to form a solution. While cooling with ice, 60% sodium hydride (79.5 mg, 1.8.times.1.1 mmol) which had been washed with hexane was added. After stirred for one night at room temperature, the reaction solution was poured into iced water and extracted with toluene (20 ml). The organic phase was washed with saturated aqueous sodium chloride, dried over anhydrous sodium sulfate, and thereafter, the solvent was distilled off to afford an oily product (0.6 g), which was then purified on silica gel column chromatography (Wakogel C300, 100 ml, hexane/ethyl acetate=300 ml/30 ml) to obtain the compound (I-342).
Yield: 0.3 g (54.7%).
Purity: 91.9% (Rt=10.7 min: ODSF.sub.411 A, acetonitrile/water=70/30 (v/v), 1 ml/min, 250 nm).
Synthesis Example 5
Synthesis of 6-chloro-2-phenylmethoxy-4-(2-propenyloxy)pyrimidine (compound I-343)
4,6-Dichloro-2-(phenylmethoxy)pyrimidine (Compound I-173) (1.5 g, 5.9 mmol) and allyl alcohol (0.342 g, 5.9.times.1.0 mmol) were introduced into a 50 ml eggplant type flask, to which dimethylformamide (20 ml) was added to form a solution. While cooling with ice, 60% sodium hydride (0.247 g, 5.9.times.1.05 mmol) which had been washed with hexane was added. After stirred for one night at room temperature, the reaction solution was poured into iced water and extracted with toluene (40 ml). The organic phase was washed with saturated aqueous sodium chloride, dried over anhydrous sodium sulfate, and thereafter, the solvent was distilled off to afford an oily product, which was then purified on silica gel column chromatography (Wakogel C300, 300 ml, hexane/ethyl acetate=25/1000(v/v)) to obtain the compound (I-343).
Yield: 0.7 g (42.9%).
Synthesis Example 6
Synthesis of 4-chloro-6-methoxy-2-(phenylmethoxy)pyrimidine (Compound I-346)
4-Chloro-6-methoxy-2-(methylsulfonyl)pyrimidine (Compound III-29) (0.80 g, 0. 0036 mol) and benzyl alcohol (Compound II-64) (0.39 g, 0.0036 mol) were dissolved in toluene (10 ml), and then 60% sodium hydride (0.16 g, 0.0036.times.1.1 mol) was added while cooling with ice. After stirred for one night at room temperature, the reaction solution was poured into water and extracted with ethyl acetate. The organic phase was washed with saturated aqueous sodium chloride, dried over anhydrous sodium sulfate and filtered, and thereafter, the solvent was distilled off to afford a crude product (0.92 g), which was then purified on silica gel column chromatography to obtain the compound (I-346) as an oily product.
Yield: 0.5 g.
Synthesis Example 7
Synthesis of 4-ethoxy-6-methyl-2-(phenylmethyl)pyrimidine (Compound I-361)
To benzyl alcohol (Compound II-64) (0.35 g, 0.0016.times.2.0 mol) in tetrahydrofuran, sodium hydride (0.085 g, (60% in mineral oil), 0.0016.times.1.3 mol) and 4-ethoxy-6-methyl-2-(methylsulfonyl)pyrimidine (Compound III-44) (0.35 g, 0.0016 mol) prepared as described in Reference synthesis example 1 below were successively added and the solution was allowed to react for about 1 hour at room temperature.
Then, the reaction solution was partitioned between ethyl acetate and saturated aqueous sodium hydrogen carbonate, organic phase was washed with saturated aqueous sodium chloride, and thereafter, dried over anhydrous sodium sulfate. The dried organic phase was concentrated with a rotary evaporator, then, in a tubular oven, unreacted starting materials were distilled off under reduced pressure with a vacuum pump, and thereafter, purified on silica gel column to obtain the compound (I-361).
Yield: 0.32 g (81%).
Synthesis Example 8
Synthesis of 4,6-dimethoxy-2-(phenylmethoxy)pyrimidine (Compound I-372)
Benzyl alcohol (Compound II-64) (0.434 g, 4.0 mmol) and 2-chloro-4,6-dimethoxypyrimidine were dissolved in dimethylformamide (10 ml) and cooled with ice. Sodium hydride (168 mg, 4.0.times.1.05 mmol) which had been washed with hexane (1 ml.times.2) was added thereto. After allowed to react for 2 hours, the reaction solution was poured onto ice and extracted with toluene. The organic phase was concentrated and thereafter purified on silica gel column chromatography (Wakogel C300, 100 ml, ethyl acetate/hexane=30 ml/300 ml) to obtain the compound (I-372).
Yield: 600 mg (61%).
Synthesis Example 9
Synthesis of 4,6-dimethylthio-2-(phenylmethoxy)pyrimidine (Compound I-2007)
To 15% aqueous sodium thiomethoxide (11 g, 0.0118.times.2.0 mol) dissolved in dimethylformaldehyde, 4,6-dichloro-2-(phenylmethoxy)pyrimidine (Compound I-173) (3 g, 0.0118.times.1.0 mol) was added and the solution was stirred for about 3 hours at room temperature.
The reaction solution was partitioned between ethyl acetate and saturated aqueous sodium hydrogen carbonate, then the organic phase was separated and washed with saturated aqueous sodium chloride, and thereafter, dried, concentrated and purified on silica gel column to obtain the compound (I-2007) as an oily product.
Yield: 3.2 g (98%).
Synthesis Example 10
Synthesis of 4-chloro-6-(ethylthio)-2-(phenylmethoxy)pyrimidine (Compound I-2014)
Ethanethiol (0.366 g, 0.0059.times.1.0 mol) was dissolved in tetrahydrofuran and sodium hydride (0.24 g, (ca. 60% in mineral oil), 0.0059.times.1.0 mol) was added thereto. The resulting solution was added dropwise to 4,6-dichloro-2-(phenylmethoxy)pyrimidine (Compound I-173) (1.5 g, 0.0059 mol) dissolved in tetrahydrofuran and then the solution was stirred for about 3 hours at room temperature.
In order to completely remove the unreacted starting materials (Compound I-173), 40% aqueous methylamine (0.23 g, 0.0059.times.0.5 mol) was added and stirred for about 1 hour at room temperature. The reaction solution was poured into water and extracted with ethyl acetate. The organic phase was separated and washed with saturated aqueous sodium chloride, and thereafter, dried, concentrated and purified on silica gel column to obtain the compound (I-2014).
Yield: 1.55 g (94%).
m.p. 55.degree. to 57.degree. C.
Reference Synthesis Example 1
Synthesis of 4,6-dibromo-2-(methylsulfonyl)pyrimidine (Compound III-3)
(1) Synthesis of an intermediate, 4,6-dibromo-2-(methylthio)pyrimidine (Compound IV-3)
Into a 300 ml eggplant type flask, 4,6-dihydroxy-2-(methylthio)pyrimidine (Compound IV-124) (12.5 g, 0.079 mol) and phosphoryl tribromide (49.8 g, 0.079.times.2.1 mol) were introduced, and the flask was immersed in 80.degree. C. oil bath and the solution was stirred for 30 minutes. The reaction mixture was cooled to room temperature, then ethyl acetate was added thereto and dissolved. The resulting solution was poured onto ice and an organic phase was separated. The separated organic phase was washed with saturated aqueous sodium chloride, dried over anhydrous sodium sulfate and filtered, and thereafter, the solvent was distilled off. The residue was purified on silica gel column chromatography (Wakogel C300, 300 ml, ethyl acetate/hexane=35 ml/700 ml) to obtain the compound (IV-3) as a white crystalline product from the fraction of 20 ml to 480 ml.
Yield: 14.6 g.
m.p. 90.degree. to 92.degree. C.
(2) Synthesis of Compound III-3 from the intermediate
Into a 100 ml eggplant type flask, the compound (IV-3) (5.7 g, 20.1 mmol) which was the intermediate obtained in the step (1) above was introduced and acetic acid (50 ml) was added and dissolved. 31% aqueous hydrogen peroxide (4.5 g, 20.1.times.2.1 mmol) was added thereto and allowed to react at 100.degree. C. for 3 hours.
Since HPLC monitoring showed the presence of 13.2% of unreacted starting materials (Rt=5.1 min, acetonitrile/water=70/30 (v/v), 1 ml/min, 250 nm), 31% aqueous hydrogen peroxide (1.0 g, 20.1.times.0.47 mmol) was further added thereto and allowed to react for 1 hour. After cooled to room temperature, the reaction solution was poured into iced water and extracted with toluene. After washed with saturated aqueous sodium chloride, the organic phase was dried over anhydrous sodium sulfate and the solvent was distilled off to obtain the compound (III-3) as a white crystalline product.
Yield: 4.5 g (72.5%).
Purity: 97.5% (Rt=2.3 min: ODS411A, acetonitrile/water=70/30(v/v), 1 ml/min, 250 nm).
m.p. 121.degree. to 124.degree. C.
Reference Synthesis Example 2
Synthesis of 4,6-dichloro-2-(methylsulfonyl)pyrimidine (Compound III-5)
(1) Synthesis of an intermediate, 4,6-dichloro-2-(methylthio)pyrimidine (Compound IV-5)
Into a 500 ml eggplant type flask, 4,6-dihydroxy-2-(methylthio)pyrimidine (Compound IV-124) (75.0 g, 474 mmol) and phosphorus oxychloride (250 g, 474.times.3.44 mmol) were introduced. After stirred for 2 hours at 100.degree. C., HPLC monitoring showed the presence of 96.8% of the end product (Rt=4.5 min, acetonitrile/water=70/30 (v/v), 1 ml/min, 250 nm). After allowed to cool to room temperature, the reaction solution was carefully poured into iced water, extracted with ethyl acetate (500 ml). The organic phase was washed successively with saturated aqueous sodium hydrogen carbonate and saturated aqueous sodium chloride, then dried over anhydrous sodium sulfate, and thereafter, the solvent was distilled off to obtain the compound (IV-5).
Yield: 92.3 g (99.8%).
Purity 96.8%. (Rt=4.5 min: ODS411A, acetonitrile/water=70/30 (v/v), 1 ml/min, 250 nm).
(2) Synthesis of Compound III-5 from the intermediate
Into a 500 ml eggplant type flask, the compound (IV-5) (25.0 g, 128 mmol) obtained in the above step (1) was introduced, and dissolved by the addition of acetic acid (100 ml). While stirring, 31% aqueous hydrogen peroxide (30.9 g, 128.times.2.2 mmol) was added thereto. After stirred for one night at room temperature, HPLC monitoring showed the presence of 75% of remaining unreacted starting material (Rt=4.6 min, acetonitrile/water=70/30 (v/v), 1 ml/min, 250 nm). Thus, the reaction solution was heated to 80.degree. C. and allowed to react for another 3 hours.
HPLC monitoring showed the presence of 95.1% of the end product (Rt=2.3 min). After cooled to room temperature, the reaction solution was poured into iced water and extracted with ethyl acetate (200 ml). After washed with saturated aqueous sodium chloride, the organic phase was dried over anhydrous sodium sulfate, and thereafter, the solvent was distilled off to obtain the compound (III-5) as a white crystalline product.
Yield: 22.4 g (77.0%).
Purity: 99.4% (Rt=2.3 min: ODS411A, acetonitrile/water=70/30(v/v), 1 ml/min, 250 nm).
m.p. 115.degree. to 121.degree. C.
Reference Synthesis Example 3
Synthesis of 4-chloro-6-methyl-2-(methylsulfonyl)pyrimidine (Compound III-7)
4-Chloro-6-methyl-2-(methylthio)pyrimidine (Compound IV-7) (2.0 g, 0.0114 mol) was dissolved in chloroform, m-chloroperbenzoic acid (5.64 g, (purity ca. 70%), 0.0114.times.2.0 mol) was added thereto and the solution was stirred for about 2 hours at room temperature. The reaction solution was partitioned between chloroform and saturated aqueous sodium hydrogen carbonate to separate an organic phase, which was then washed with saturated aqueous sodium chloride, dried over anhydrous sodium sulfate, concentrated, and thereafter, purified on silica gel column to obtain the compound (III-7).
Yield: 2.25 g (95%).
m.p. 67.degree. to 70.degree. C.
.sup.1 H-NMR (60 MHz, CDCl.sub.3, .delta.): 2.63(3H,s), 3.30(3H,s), 7.38 (1H,s).
Reference Synthesis Example 4
Synthesis of 4-chloro-6-methoxy-2-(methylsulfonyl)pyrimidine (Compound III-29)
(1) Synthesis of an intermediate, 4-chloro-6-methoxy-2-(methylthio)pyrimidine (Compound IV-29)
4,6-dichloro-2-(methylthio)pyrimidine (Compound IV-5) (19.5 g, 0.100 mol) was dissolved in tetrahydrofuran (200 ml) just after distilled, then methyl alcohol (3.2 g, 0.100.times.1.0 mol) was added thereto. While cooling with ice, 60% sodium hydride (4.4 g, 0.100.times.1.1 mol) was added thereto while stirring. After stirred for 3 hours, the reaction solution was poured into water and extracted with toluene. The organic phase was washed with saturated aqueous sodium chloride, dried over anhydrous sodium sulfate and filtered, and thereafter, the solvent was distilled off to obtain the compound (IV-29).
Yield: 19.0 g.
.sup.1 H-NMR (60 MHz, CDCl.sub.3, .delta.): 2.47(3H,s), 3.85(3H,s), 6.27 (1H,s)
(2) Synthesis of Compound III-29 from the intermediate
The compound (IV-29) (19.0 g, 0.100 mol) which was the intermediate obtained in the step (1) above, was dissolved in acetic acid (200 ml), then 31% aqueous hydrogen peroxide (25.2 g, 0.100.times.2.3 mol) was added, and the solution was heated to 100.degree. C. while stirring. After stirred for 2 hours, the reaction solution was poured into water and extracted with ethyl acetate. The organic phase was washed with saturated aqueous sodium chloride, dried over anhydrous sodium sulfate and filtered, and thereafter, the solvent was distilled off to obtain a crude product (20.0 g), which was then purified on silica gel column chromatography (Wakogel C300, 300 ml, ethyl acetate/hexane=400 ml/400 ml) to obtain the compound (III-29) as a white crystalline product from the fraction of 300 ml to 600 ml.
Yield: 11.5 g.
m.p. 68.degree. to 74.degree. C.
.sup.1 H-NMR (60 MHz, CDCl.sub.3, .delta.): 3.30(3H,s), 4.07(3H,s), 6.87 (1H,s).
Reference Synthesis Example 5
Synthesis of 4-chloro-6-(3-methyl-2-butenyloxy)-2-(methylsulfonyl)pyrimidine (Compound III-25)
(1) Synthesis of an intermediate, 4-chloro-6-(3-methyl-2-butenyloxy)-2-(methylthio)pyrimidine (Compound IV-25)
Into a 100 ml eggplant type flask, 4,6-dichloro-2-(methylthio)pyrimidine (Compound IV-5) (7.4 g, 37.9 mmol) and 3-methyl-2-buten-1-ol (3.27 g, 37.9.times.1.0 mmol) were introduced, then dimethyl formaldehyde (20 ml) was added thereto to form a solution. 60% sodium hydride (1.59 g, 7.9.times.1.05 mmol) which had been washed with hexane was added thereto while cooling with ice.
After stirred for one night at room temperature, the reaction solution was poured into iced water and extracted with toluene (50 ml). The organic phase was washed with saturated aqueous sodium chloride and dried over anhydrous sodium sulfate, and thereafter, the solvent was distilled off to obtain an oily product, which was then purified on silica gel column chromatography (Wakogel C300 , 300 ml, hexane=1000 ml) to obtain the compound (IV-25).
Yield: 7.3 g (78.5%).
Purity: 91.2%. (Rt=8.9 min: ODSF.sub.411 A, acetonitrile/water=70/30(v/v), 1 ml/min, 250 nm)
.sup.1 H-NMR (60 MHz, CDCl.sub.3, .delta.): 1.70(6H,s), 2.48(3H,s), 4.6-4.9(2H,m), 5.2-5.6(1H, m), 6.27(1H,s)
(2) Synthesis of Compound III-25 from the intermediate
Into a 100 ml eggplant type flask, the compound (IV-25) (2.45 g, 10.0 mmol) which was the intermediate obtained in the above step was introduced, then dichloromethane (40 ml) was added thereto to form a solution. While cooling with ice, m-chloroperbenzoic acid (3.45 g, 10.0.times.2.0 mmol) was added by small portions. 1 hour later from the end of addition, ice bath was removed, and the reaction solution was stirred one night at room temperature. Saturated aqueous sodium hydrogen carbonate was added to the reaction solution and shaken to separate an organic phase. The obtained organic phase was then washed with saturated aqueous sodium chloride and dried over anhydrous sodium sulfate, thereafter, the solvent was distilled off to obtain an oily product (2.5 g), which was purified on silica gel column chromatography (Wakogel C300, 300 ml, hexane/ethyl acetate=300 ml/150 ml) to obtain the compound (III-25) from the fraction of 300 ml to 380 ml.
Yield: 0.7 g (2.53%).
Oily product.
.sup.1 H-NMR (60 MHz, CDCl.sub.3, .delta.): 1.77(6H,s), 3.30(3H,s), 4.9-5.1(2H, d,7Hz), 5.3-5.6(1H,m), 6.90(1H,s)
Reference Synthesis Example 6
Synthesis of 4-ethoxy-6-methyl-2-methylsulfonylpyrimidine (Compound III-44)
(1) Synthesis of an intermediate, 4-ethoxy-6-methyl-2-(methylthio)pyrimidine (Compound IV-44)
To sodium hydride (2.75 g (60% in mineral oil), 0.046.times.1.5 mmol) dissolved in ethanol (20 ml), 4-chloro-6-methyl-2-methylmercaptopyrimidine (Compound IV-7) (8.0 g, 0.046 mmol) was added and the solution was stirred for about 1 hour at room temperature.
Then, the reaction solution was partitioned between ethyl acetate and saturated aqueous sodium hydrogen carbonate. The organic phase was washed with saturated aqueous sodium chloride and dried over anhydrous sodium sulfate. After dried, the residue was concentrated and purified on silica gel column to obtain the compound (IV-44).
Yield: 6.02 g (71%).
(2) Synthesis of Compound III-44 from the intermediate
The compound (IV-44) (5.82 g, 0.0316 mol) which was the intermediate obtained by the above step (1), was dissolved in chloroform, then m-chloroperbenzoic acid (15.6 g, 0.0316.times.2.0 mol) was added thereto and the solution was allowed to react for about 2 hours at room temperature. The reaction solution was partitioned between chloroform and saturated aqueous sodium hydrogen carbonate, organic layer was washed with saturated aqueous sodium chloride, and then dried over anhydrous sodium sulfate. After dried, the residue was concentrated and purified on silica gel column to obtain the compound (III-44).
Yield: 3.87 g (57%).
Physico-chemical properties of the compounds produced in the Synthesis examples 1 to 10 and those produced in accordance with the Synthesis examples 1 to 10 are shown in Table 5.
TABLE 5______________________________________ property or m.p.No. (.degree.C.) NMR (60 MHz, CDCl.sub.3, .delta.)______________________________________I-1 oily 5.44(2H, s), 6.83(1H, t, J=4.8Hz), 7.0-7.8(4H, m), 8.43(2H, d, J=4.8Hz)I-2 101-102 5.49(2H, s), 6.83(1H, t, J=4.8Hz), 7.0-7.6(4H, m), 8.42(2H, d, J=4.8Hz)I-3 65-67 5.36(2H, s), 6.87(1H, t, J=4.8Hz), 7.33(4H, s), 8.46(2H, d, J=4.8Hz)I-4 oily 2.44(3H, s), 5.50(2H, s), 6.76(1H, d, J=5.0Hz), 6.9-7.8(4H, m), 8.31(1H, d, J=5.0Hz)I-5 61-63 2.42(3H, s), 5.34(2H, s), 6.74(1H, d, J=5.0Hz), 7.0-7.6(4H, m), 8.28(1H, d, J=5.0Hz)I-6 54-57 2.41(3H, s), 5.35(2H, s), 6.74(1H, d, J=5.0Hz), 7.1-7.7(4H, m), 8.30(1H, d, J=5.0Hz)I-7 66-67 2.42(3H, s), 5.36(2H, s), 6.90(1H, d, J=5.0Hz), 7.0-7.7(5H, m), 8.25(1H, d, J=5.0Hz)I-8 48-53 2.33(6H, s), 5.43(2H, s), 6.58(1H, s), 7.0-7.7(4H, m)I-9 oily 2.36(6H, s), 5.30(2H, s), 6.59(1H, s), 7.1-7.8(4H, m)I-10 oily 2.34(6H, s), 5.41(2H, s), 6.56(1H, s), 6.6-7.7(4H, m)I-11 39-40 2.36(6H, s), 5.41(2H, s), 6.58(1H, s), 6.8-7.7(4H, m)I-12 50-54 2.34(6H, s), 3.76(3H, s), 5.37(2H, s), 6.55(1H, s), 6.6-7.6(4H, m)I-13 oily 2.34(6H, s), 5.34(2H, s), 6.56(1H, s), 6.6-7.5(4H, m)I-14 oily 2.35(6H, s), 5.30(2H, s), 6.58(1H, s), 7.1-7.8(4H, m)I-15 oily 2.36(6H, s), 3.73(3H, s), 5.32(2H, s), 6.57(1H, s), 6.5-7.4(4H, m)I-16 oily 2.33(6H, s), 5.30(2H, s), 6.57(1H, s), 7.1-7.5(4H, m)I-17 oily 2.36(6H, s), 5.30(2H, s), 6.59(1H, s), 6.7-7.7(4H, m)I-18 oily 2.34(6H, s), 5.27(2H, s), 6.56(1H, s), 7.0-7.6(4H, m)I-19 oily 2.38(6H, s), 3.42(3H, s), 5.24(2H, s), 6.55(1H, s), 6.80(2H, d, J=8.3Hz), 7.37(2H, d, J=8.3Hz)I-20 oily 2.33(6H, s), 5.16(2H, s), 6.47(1H, s), 7.1-7.7(5H, m)I-21 oily 1.26(6H, d, J=6.3Hz), 2.27(3H, s), 5.14(1H, sept., J=6.3Hz), 5.30(2H, s), 6.06(1H, s), 6.4-7.7(3H, m)I-22 oily 1.28(6H, d, J=6.3Hz), 1.33(3H, t, J=6.3Hz), 2.29(3H, s), 3.98(2H, q, J=6.3Hz), 5.28(1H, sept., J=6.3Hz), 5.39(2H, s), 6.05(1H, s), 6.6-7.6(4H, m)I-23 oily 1.30(6H, d, J=6.3Hz), 2.30(3H, s), 5.29(1H, sept., J=6.3Hz), 5.27(2H, s), 6.11(1H, s), 6.8-7.5(3H, m)I-24 oily 2.36(3H, s), 4.67(2H, q, J=8.3Hz), 5.35(2H,s), 6.29(1H, s), 7.1-7.7(5H, m)I-25 70-72 3.83(6H, s), 5.33(2H, bs), 5.63(1H, s), 6.9-7.3(3H, m)I-26 81-84 2.13(3H, s), 2.27(3H, s), 3.73(3H, s), 3.86(6H, s), 5.33(2H, bs), 5.67(1H, s), 6.60(1H, d, J=8Hz), 7.20(1H, d, J=8Hz)I-27 68-70 3.77(3H, s), 3.80(3H, s), 3.83(6H, s), 5.40(2H, s), 5.60(1H, s), 6.8-7.1(3H, m)I-28 125-127 3.83(6H, s), 5.40(2H, s), 5.65(1H, s), 7.1-7.5(3H, m)I-29 66-68 3.83(6H, s), 5.33(2H, s), 5.60(1H, s), 6.6-7.5(3H, m)I-30 88-90 2.30(3H, s), 2.33(3H, s), 3.83(6H, s), 5.30(2H, s), 5.63(1H, s), 6.8-7.4(4H, m)I-31 82-84 2.13(3H, s), 3.73(3H, s), 3.76(3H, s), 3.83(6H, s), 5.33(2H, s), 5.63(1H, s), 6.57(1H, d, J=8Hz), 7.23(1H, d, J=8Hz)I-32 86-88 3.73(6H, s), 3.83(6H, s), 5.30(2H, s), 5.60(1H, s), 6.3-6.5(2H, m), 7.27(1H, d, J=8Hz)I-33 74-76 3.83(6H, s), 5.43(2H, s), 5.67(1H, s), 7.1-7.6(3H, m)I-34 68-70 3.76(6H, s), 5.30(2H, bs), 5.57(1H, s), 6.7-7.3(3H, m)I-35 35-39 2.27(3H, s), 2.33(3H, s), 3.83(6H, s), 5.33(2H, s), 5.63(1H, s), 6.9-7.3(3H, m)I-36 82-84 3.67(3H, s), 3.70(3H, s), 3.83(6H, s), 5.37(2H, s), 5.63(1H, s), 6.7-7.5(3H, m)I-37 94-96 3.87(6H, s), 5.57(2H, s), 5.67(1H, s), 7.2-7.3(3H, m)I-38 88-90 3.83(6H, s), 5.40(2H, bs), 5.63(1H, s), 6.6-7.4(3H, m)I-39 38-40 1.33(3H, t, J=7Hz), 3.83(6H, s), 4.00(2H, q, J=7Hz), 5.40(2H, s), 5.63(1H, s), 6.7-7.5(4H, m)I-40 88-91 3.83(6H, s), 5.43(2H, d, J=2Hz), 5.63(1H, s), 6.7-7.3(3H, m)I-41 66-68 3.83(6H, s), 5.30(2H, s), 5.60(1H, s), 7.0-7.3(3H, m)I-42 oily 3.73(3H, s), 3.83(6H, s), 5.37(2H, s) 5.60(1H, s), 6.7-7.5(4H, m)I-43 81-83 3.83(6H, s), 5.33(2H, s), 5.63(1H, s) 6.7-7.9(4H, m)I-44 75-77 3.80(9H, s), 3.87(6H, s), 5.27(2H, s), 5.63(1H, s), 6.67(2H, s)I-45 93-95 3.83(6H, s), 5.27(2H, s), 5.63(1H, s), 7.1-7.6(3H, m)I-46 72-74 3.83(6H, s), 5.27(2H, s), 5.63(1H, s), 6.9-7.4(3H, m)I-47 37-39 2.20(6H, s), 3.83(6H, s), 5.27(2H, s), 5.60(1H, s), 7.0-7.2(3H, m)I-48 115-117 3.83(6H, s), 5.27(2H, s), 5.63(1H, s), 7.2-7.4(3H, m)I-49 94-95 3.83(6H, s), 5.30(2H, s), 5.67(1H, s), 6.5-7.1(3H, m)I-50 58-61 2.23(6H, s), 3.83(6H, s), 5.23(2H, s), 5.60(1H, s), 6.83(1H, bs), 7.00(2H, bs)I-51 60-62 3.70(6H, s), 3.83(6H, s), 5.27(2H, s), 5.63(1H, s), 6.30(1H, t, J=3Hz), 6.57(2H, d, J=3Hz)I-52 123-125 3.83(6H, s), 5.40(2H, s), 5.63(1H, s), 7.73(1H, bs), 7.83(2H, bs)I-53 80-82 3.83(6H, s), 5.37(2H, s), 5.63(1H, s), 7.3-7.7(4H, m)I-55 60-62 1.40(3H, t, J=7Hz), 3.77(3H, s), 3.83(6H, s), 4.03(2H, q, J=7Hz), 5.23(2H, s), 5.60(1H, s), 6.7-7.2(3H, m)I-56 144-146 3.87(6H, s), 5.43(2H, bs), 5.67(1H, s), 7.2-8.3(4H, m)I-57 oily 3.80(6H, s), 4.63(2H, s), 5.27(2H, s), 5.60(1H, s), 6.7-7.4(9H, m)I-58 oily 3.67(3H, s), 3.80(6H, s), 5.27(2H, s), 5.60(1H, s), 6.8-7.3(4H, m)I-59 oily 3.83(6H, s), 5.27(2H, s), 5.63(1H, s), 6.8-7.8(4H, m)I-60 oily 1.20(6H, d, J=7Hz), 2.87(1H, sept., J=7Hz), 3.83(6H, s), 5.30(2H, s), 5.60(1H, s), 7.0-7.3(4H, m)I-61 oily 3.83(6H, s), 5.37(2H, s), 5.63(1H, s), 7.50(4H, s)I-62 80-82 1.40(3H, t, J=7Hz), 3.80(3H, s), 3.87(6H, s), 4.00(2H, q, J=7Hz), 5.23(2H, s), 5.60(1H, s), 6.7-7.2(3H, m)I-63 79-81 3.83(6H, s) , 5.37(2H, s), 5.63(1H, s), 7.1-7.6(9H, m)I-64 126-128 3.73(3H, s), 3.83(6H, s), 5.30(2H, s), 5.63(1H, s), 6.67(1H, d, J=8Hz), 7.20(1H, d, J=3Hz), 7.43(1H, dd, J=8Hz, J=3Hz)I-65 95-98 3.77(3H, s), 3.83(6H, s), 5.03(2H, s), 5.23(2H, s), 5.60(1H, s), 6.7-7.4(8H, m)I-66 73-75 3.80(6H, s), 4.93(2H, s), 5.23(2H, s), 5.60(1H, s), 6.7-7.4(9H, m)I-67 oily 2.40(3H, s), 3.83(6H, s), 5.23(2H, s), 5.60(1H, s), 7.0-7.6(4H, m)I-68 oily 3.63(3H, s), 3.80(6H, s), 5.23(2H, s), 5.60(1H, s), 6.77(2H, d, J=8Hz), 7.30(2H, d, J=8Hz)I-81 oily 5.20(2H, s), 7.10(1H, s), 7.1-7.8(5H, m)I-173 oily 5.33(2H, s), 6.90(1H, s), 7.2-7.5(5H, m)I-240 oily 2.37(3H, s), 5.33(2H, s), 6.73(1H, s), 7.1-7.6(5H, m)I-342 oily 1.70(6H, s), 4.75(2H, d, 7Hz), 5.2-5.5(1H, m), 5.33(2H, s), 6.27(1H, s), 7.1-7.5(5H, m)I-343 oily 4.7-4.9(2H, m), 5.0-6.3(3H, m), 5.27(2H, s), 6.23(1H, s), 7.1-7.47(5H, m)I-346 oily 3.80(3H, s), 5.30(2H, s), 6.20(1H, s), 7.1-7.5(5H, m)I-354 oily 1.25(6H, d, J=6.3Hz), 2.29(3H, s), 5.24(1H, sept., J=6.3Hz), 5.30(2H, s), 6.56(1H, s), 7.1-7.6(5H, m)I-359 oily 2.31(3H, s), 4.5-4.9(2H, m), 4.9-5.6(2H, m), 5.32(2H, s), 5.6-6.2(1H, m), 6.15(1H, s), 6.9-7.6(5H, m)I-361 oily 1.30(3H, t, J=6.9Hz), 2.29(3H, s), 4.29(2H, q, J=6.9Hz), 5.31(2H, s), 6.09(1H, s), 7.1-7.7(5H, m)I-362 oily 2.30(3H, s), 3.85(3H, s), 5.33(2H, s), 6.12(1H, s), 7.1-7.6(5H, m)I-371 39-41 1.30(6H, t, J=6.9Hz), 4.26(4H, q, J=6.9Hz), 5.30(2H, s), 5.57(1H, s), 7.1-7.6(5H, m)I-372 64-66 3.80(6H, s), 5.30(2H, s), 5.60(1H, s), 7.1-7.5(5H, m)I-464 oily 1.24(6H, d, J=6.3Hz), 2.28(3H, s), 5.24(1H, sept., J=6.3Hz), 5.41(2H, s), 6.06(1H, s), 6.9-7.7(4H, m)I-471 oily 1.29(3H, t, J=6.9Hz), 2.31(3H, s), 4.30(2H, q, J=6.9Hz), 5.44(2H, s), 6.12(1H, s), 7.0-7.7(4H, m)I-472 oily 2.30(3H, s), 3.85(3H, s), 5.44(2H, s), 6.14(1H, s), 7.0-7.8(4H, m)I-482 80-82 3.83(6H, s), 5.47(2H, s), 5.63(1H, s), 7.1-7.6(4H, m)I-574 oily 1.25(6H, d, J=6.3Hz), 2.28(3H, s), 5.27(1H, sept., J=6.3Hz), 5.37(2H, s), 6.06(1H, s), 6.7-7.6(4H, m)I-581 oily 1.30(3H, t, J=6.9Hz), 2.30(3H, s), 4.32(2H, q, J=6.9Hz), 5.40(2H, s), 6.13(1H, s), 6.6-7.8(4H, m)I-582 48-49.5 2.30(3H, s), 3.86(3H, s), 5.43(2H, s), 6.14(1H, s), 6.7-7.7(4H, m)I-592 67-69 3.83(6H, s), 5.40(2H, s), 5.60(1H, s), 6.8-7.6(4H, m)I-692 oily 2.32(3H, s), 3.85(3H, s), 5.45(2H, s), 6.16(1H, s), 6.8.varies.7.8(4H, m)I-702 67-69 3.83(6H, s), 5.43(2H, s), 5.63(1H, s), 7.0-7.6(4H, m)I-812 68-70 2.37(3H, s), 3.83(6H, s), 5.33(2H, s), 5.63(1H, s), 7.1-7.5(4H, m)I-904 oily 1.26(6H, d, J=6.3Hz), 2.29(3H, s), 5.26(1H, sept., J=6.3Hz), 5.28(2H, s), 6.08(1H, s), 7.1-7.6(4H, m)I-911 oily 1.32(3H, t, J=6.3Hz), 2.32(3H, s), 4.28(2H, q, J=6.3Hz), 5.34(2H, s), 6.16(1H, s), 7.0-7.6(4H, m)I-912 oily 2.30(3H, s), 3.85(3H, s), 5.29(2H, s), 6.13(1H, s), 7.0-7.6(4H, m)I-922 78-80 3.83(6H, s), 5.27(2H, s), 5.63(1H, s), 7.1-7.5(4H, m)I-1014 oily 1.27(6H, d, J=6.3Hz), 2.29(3H, s), 5.25(1H, sept., J=6.3Hz), 5.29(2H, s), 6.07(1H, s), 6.6-7.4(4H, m)I-1021 oily 1.31(3H, t, J=6.9Hz), 2.31(3H, s), 4.30(2H, q, J=6.9Hz), 5.31(2H, s), 6.11(1H, s), 6.6-7.6(4H, m)I-1022 oily 2.30(3H, s), 3.84(3H, s), 5.32(2H, s), 6.14(1H, s), 6.6-7.5(4H, m)I-1032 35-37 3.83(6H, s), 5.30(2H, s), 5.63(1H, s), 6.8-7.3(4H, m)I-1132 oily 2.30(3H, s), 3.85(3H, s), 5.29(2H, s), 6.14(1H, s), 6.9-7.9(4H, m)I-1142 58-60 3.87(6H, s), 5.30(2H, s), 5.63(1H, s), 7.0-7.7(4H, m)I-1252 48-50 2.30(3H, s), 3.80(6H, s), 5.30(2H, s), 5.60(1H, s), 7.0-7.3(4H, m)I-1344 oily 1.26(6H, d, J=6.3Hz), 2.27(3H, s), 5.24(1H, sept., J=6.3Hz), 5.25(2H, s) 6.05(1H, s), 7.26(4H, s)I-1351 oily 1.31(3H, t, J=6.9Hz), 2.29(3H, s), 4.29(2H, q, J=6.9Hz), 5.27(2H, s), 6.11(1H, s), 7.28(4H, m)I-1352 oily 2.30(3H, s), 3.84(3H, s), 5.29(2H, s), 6.14(1H, s), 7.2-7.5(4H, m)I-1362 58-60 3.83(6H, s), 5.27(2H, s), 5.63(1H, s), 7.30(4H, s)I-1454 oily 1.27(6H, d, J=6.3Hz), 2.28(3H, s), 5.27(1H, sept., J=6.3Hz), 5.28(2H, s), 6.08(1H, s), 6.7-7.6(4H, m)I-1461 61-62 1.34(3H, t, J=6.9Hz), 2.32(3H, s), 4.32(2H, q, J=6.9Hz), 5.29(2H, s), 6.12(1H, s), 6.7-7.7(4H,m)I-1462 oily 2.30(3H, s), 3.85(3H, s), 5.29(2H, s), 6.14(1H, s), 6.7-7.7(4H, m)I-1472 oily 3.83(6H, s), 5.30(2H, s), 5.63(1H, s), 6.8-7.5(4H, m)I-1572 oily 2.28(3H, s), 3.83(3H, s), 5.27(2H, s), 6.13(1H, s), 7.1-7.6(4H, m)I-1582 oily 3.83(6H, s), 5.30(2H, s), 5.67(1H, s), 7.2-7.6(4H, m)I-1692 oily 2.27(3H, s), 3.80(6H, s), 5.27(2H, s), 5.60(1H, s), 7.03(2H, d, J=8Hz), 7.30(2H, d, J=8Hz)I-2007 oily 2.44(6H, s), 5.33(2H, s), 6.54(1H, s), 7.0-7.5(5H, m)I-2014 55-57 1.30(3H, t, J=6.9Hz), 3.08(2H, q, J=6.9Hz), 5.34(2H, s), 6.70(1H, s), 7.0-7.6(5H, m)______________________________________
Formulation examples and test examples will now be described. Kinds of carriers (diluents) and additives to be used, as well as mixing ratios thereof and active ingredient contents therein may be modified in a broad range.
In each of the formulation examples, the term "parts" denotes "parts by weight" unless otherwise noted.
______________________________________Formulation Example 1 (wettable powder)______________________________________Compound (I-372) 50 partsLignin sulfonate 5 partsAlkyl sulfonate 3 partsDiatomaceous earth 42 parts______________________________________
The above ingredients were mixed together and ground finely to form a wettable powder, which may be applied after diluted with water.
______________________________________Formulation Example 2 (emulsifiable concentrate)______________________________________Compound (I-912) 25 partsXylene 65 partsPolyoxyethylene alkyl aryl ether 10 parts______________________________________
The above ingredients were homogeneously mixed to form an emulsifiable concentrate, which may be applied after diluted with water.
______________________________________Formulation Example 3 (granule)______________________________________Compound (I-1362) 8 partsBentonite 40 partsClay 45 partsLignin sulfonate 7 parts______________________________________
The above ingredients were homogeneously mixed, blended with the addition of water and processed into granular form with an extrusion granulator to give granules.
Test Example 1 (Weed control test by foliage treatment)
Wettable powders were formulated as described in Formulation example 1 and diluted to a predetermined concentration. Each of the formulated test compound was applied at a rate of 500 g/10 a onto the foliage of each plant grown to the 1 to 2 leaf stage. The tested plants were pot-cultured redroot pigweed (Amaranthus retroflexus, AR), wild mustard (Sinapis arvensis, SA), sicklepod (Cassia obtusifolia, CO), black nightshade (Solanum nigrum, SN), velvetleaf (Abutilon theophrasti, AT), cleavers (Galium aparine, GA) and ivyleafspeedwell (Veronica hederaefolia, VH).
On the 14th day after the application, weed control effects were evaluated by the following criterion. Evaluation rating:
1: less than 30%
2: 30% to less than 70%
3: 70% or more
The results are shown in Table 6.
TABLE 6______________________________________Dosage Herbage speciesNo. g/10a AR SA CO SN AT GA VH______________________________________I-1 500 3 2 3 2 3 2 2I-3 500 3 2 3 2 2 3 3I-4 500 3 2 3 3 2 2 2I-5 500 2 2 2 2 2 2 3I-6 500 2 2 3 3 2 2 2I-7 500 3 2 2 2 2 2 2I-8 500 3 3 3 3 3 3 2I-9 500 3 3 3 3 2 3 2I-12 500 2 2 3 3 3 2 2I-15 500 2 2 3 3 3 2 2I-16 500 3 3 3 3 3 3 3I-20 500 3 3 3 3 2 3 2I-24 500 2 2 2 3 2 2 2I-25 500 2 2 3 3 2 2 2I-27 500 2 3 2 3 2 2 2I-29 500 3 3 3 3 3 3 3I-32 500 3 2 2 2 2 2 2I-34 500 2 2 2 3 2 2 2I-35 500 2 2 2 3 2 2 2I-36 500 3 2 2 2 3 2 2I-37 500 2 3 2 2 2 2 3I-38 500 2 3 2 3 2 2 2I-39 500 3 2 3 3 2 2 2I-41 500 3 3 2 2 2 2 2I-43 500 2 2 3 3 2 2 2I-44 500 3 3 2 2 2 2 2I-45 500 2 3 2 2 3 2 2I-46 500 3 3 3 3 3 3 3I-47 500 3 3 2 3 3 3 3I-49 500 3 3 3 3 2 2 2I-50 500 3 2 2 3 2 3 2I-51 500 2 3 2 2 2 2 2I-53 500 3 3 2 2 2 3 2I-57 500 3 3 3 3 3 3 3I-58 500 3 3 3 3 3 2 2I-59 500 3 2 3 3 3 3 2I-60 500 3 3 2 2 2 3 2I-61 500 3 3 3 3 2 2 2I-62 500 2 3 2 2 2 2 2I-66 500 2 3 2 2 2 2 2I-67 500 2 2 2 3 2 2 2I-68 500 3 3 3 3 2 3 2I-173 500 1 3 3 3 3 2 3I-342 500 1 3 3 3 2 2 3I-343 500 1 3 2 2 2 2 2I-359 500 3 3 3 3 3 3 3I-361 500 3 3 3 3 3 2 2I-362 500 2 3 3 3 3 2 3I-371 500 3 3 3 3 3 3 3I-372 500 3 2 3 3 3 3 3I-464 500 2 3 2 2 2 2 2I-471 500 3 3 3 3 2 2 2I-472 500 2 3 3 3 2 3 3I-482 500 3 3 3 3 2 2 2I-581 500 3 2 3 3 2 2 2I-582 500 2 2 3 2 2 3 2I-592 500 3 3 3 3 3 3 3I-692 500 2 2 3 3 3 2 3I-702 500 3 3 3 3 3 2 2I-812 500 2 3 3 3 2 3 2I-911 500 3 3 3 3 3 2 2I-912 500 2 3 3 3 3 3 3I-922 500 3 3 3 3 3 2 3I-1021 500 2 2 3 3 2 2 2I-1022 500 2 2 3 2 2 2 2I-1032 500 3 3 3 3 3 3 3I-1132 500 3 2 3 3 2 3 3I-1142 500 3 3 3 3 3 3 3I-1252 500 2 3 3 3 2 3 2I-1351 500 3 3 3 3 2 2 2I-1352 500 3 3 3 3 3 3 3I-1362 500 3 3 3 3 3 3 3I-1454 500 2 3 3 3 3 2 2I-1461 500 3 3 3 3 2 2 2I-1462 500 2 2 3 2 2 2 2I-1472 500 3 3 3 3 3 3 3I-1572 500 2 2 3 2 2 2 2I-1582 500 3 3 3 3 3 3 3I-1692 500 3 3 3 3 3 3 2______________________________________ AR: Amaranthus retroflexus SA: Sinapis arvensis CO: Cassia obtusifolia SN: Solanum nigrum AT: Abutilon theophrasti GA: Galium aparine VH: Veronica hederaefolia
Test Example 2 (Germination test)
In a 9 cm diameter Petri dish having the bottom covered with double sheets of filter paper, 6 ml of aqueous suspension of a test compound (containing 50 ppm of active ingredient) was poured and ten seeds of each weed were placed. The tested weeds were redroot pigweed (Amaranthus retroflexus, AR), black nightshade (Solanum nigrum, SN), wild chamomile (Matricaria chamomilla, MC), green foxtail (Setaria viridis, SV) and rice flatsedge (Cyperus iria, CI).
The seeds was allowed to germinate in a greenhouse at 28.degree. C., and on the 14th day after the sowing, the inhibition of germination and the retarding of growth were visually observed and evaluated by the following 3-grade criterion. Evaluation rating:
1: less than 30%
2: 30% to less than 70%
3: 70% or more
The results are shown in Table 7.
TABLE 7______________________________________Dosage Herbage speciesNo. ppm AR SN MC SV CI______________________________________I-3 50 3 2 2 2 2I-7 50 3 2 2 2 2I-8 50 3 2 2 2 2I-9 50 3 2 2 2 2I-16 50 3 2 2 2 2I-20 50 3 2 2 2 2I-24 50 3 1 1 3 3I-25 50 3 3 2 3 3I-29 50 3 2 2 3 3I-35 50 2 2 2 3 2I-36 50 3 2 2 2 2I-38 50 2 2 2 3 2I-41 50 3 2 2 3 2I-45 50 3 2 2 3 3I-46 50 3 3 3 3 3I-49 50 3 3 3 3 3I-53 50 3 2 2 3 2I-57 50 3 2 2 2 2I-58 50 3 2 2 3 3I-59 50 2 2 2 2 2I-61 50 3 2 2 2 2I-66 50 3 2 2 2 2I-68 50 3 2 2 3 3I-173 50 3 1 1 1 1I-343 50 3 1 1 3 3I-359 50 3 2 2 3 2I-361 50 3 3 3 3 3I-362 50 3 3 3 3 3I-371 50 3 1 1 3 3I-372 50 3 3 3 3 3I-471 50 3 2 2 2 3I-472 50 3 2 2 2 2I-482 50 3 2 2 3 3I-581 50 3 2 2 2 2I-592 50 3 2 3 3 3I-812 50 3 2 2 3 3I-912 50 3 2 2 3 3I-922 50 3 2 2 3 3I-1021 50 3 3 3 3 3I-1032 50 3 3 3 3 3I-1142 50 3 2 2 2 3I-1252 50 3 2 2 3 3I-1351 50 3 2 2 2 2I-1352 50 3 2 3 3 2I-1362 50 3 2 3 3 3I-1454 50 2 2 3 2 2I-1461 50 3 2 2 2 2I-1462 50 3 2 2 3 3I-1472 50 3 3 3 3 3I-1582 50 3 2 2 3 3I-1692 50 3 2 2 3 3______________________________________ AR: Amaranthus retroflexus SN: Solanum nigrum MC: Matricaria chamomilla SV: Setaria viridis CI: Cyperus iria
Claims
  • 1. A herbicidal composition comprising a herbicidally effective amount of a 2-benzyloxypyrimidine derivative represented by the formula (I): ##STR12## wherein R.sup.1 and R.sup.2 are each independently H, a halogen, hydroxyl, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.3 -C.sub.5 alkenyl, C.sub.3 -C.sub.5 alkynyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 haloalkoxy, C.sub.3 -C.sub.5 alkenyloxy, C.sub.3 -C.sub.5 alkynyloxy, C.sub.1 -C.sub.4 alkylthio, or phenyl;
  • n is an integer of 0 to 5; and
  • each X which may be identical or different if n is greater than 1, is a halogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 alkylthio, C.sub.7 -C.sub.9 aralkyloxy, phenyl, hydroxymethyl, hydroxycarbonyl, C.sub.1 -C.sub.4 alkoxycarbonyl, or nitro, and
  • an adjuvant.
  • 2. A herbicidal composition according to claim 1, wherein R.sup.1 and R.sup.2 are each independently methyl or methoxy, at least one of R.sup.1 and R.sup.2 is methoxy, n is 0 to 2, and X is a halogen.
  • 3. A 2-benzyloxypyrimidine derivative represented by the formula (I): ##STR13## wherein R.sup.1 and R.sup.2 are each independently H, a halogen, hydroxyl, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.3 -C.sub.5 alkenyl, C.sub.3 -C.sub.5 alkynyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 haloalkoxy, C.sub.3 -C.sub.5 alkenyloxy, C.sub.3 -C.sub.5 alkynyloxy, C.sub.1 -C.sub.4 alkylthio or phenyl;
  • n is an integer of 0 to 5; and
  • each X which may be identical or different if n is greater than 1, is a halogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 alkylthio, C.sub.7 -C.sub.9 aralkyloxy, phenyl, hydroxymethyl, hydroxycarbonyl, C.sub.1 -C.sub.4 alkoxycarbonyl, or nitro,
  • with a proviso that 2-benzyloxypyrimidine, 2-benzyloxy-4-ethoxypyrimidine and 2-benzyloxy-4,6-dimethylpyrimidine are excluded.
  • 4. A 2-benzyloxypyrimidine derivative according to claim 3, wherein R.sup.1 and R.sup.2 are each independently methyl or methoxy, at least one of R.sup.1 and R.sup.2 is methoxy, n is 0 to 2, and X is a halogen.
Priority Claims (1)
Number Date Country Kind
6-186707 Jul 1994 JPX
US Referenced Citations (4)
Number Name Date Kind
4941910 Muller et al. Jul 1990
5139563 Astles et al. Aug 1992
5238907 Kruger et al. Aug 1993
5401711 Sato et al. Mar 1995
Foreign Referenced Citations (4)
Number Date Country
0249708 Dec 1987 EPX
0398692 Nov 1990 EPX
2360581 Mar 1978 FRX
WO9219603 Nov 1992 WOX
Non-Patent Literature Citations (5)
Entry
Patent Abstracts of Japan, vol. 12, No. 22 (C-470) (2869) 22 Jan. 1988.
Chemical Abstracts, vol. 86, No. 5, 31 Jan. 1977, Abstract No. 25844s.
J. Chem. Soc., 1965, 5542-5551--Brown et al., "The Dimroth Rearrangement. Part IV".
J. Chem. Soc., 1975, 1798-1802--Kaspersen et al., "Unconventional Nucleotide Analogues. Part XIV".
J. Chem. Soc., 1959, 525-530--Hunt et al., "Pyrimidines. Part X".