AU703619B2 - Benzylsulfide derivatives suitable for use as intermediates in the production of pesticides - Google Patents

Benzylsulfide derivatives suitable for use as intermediates in the production of pesticides Download PDF

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AU703619B2
AU703619B2 AU52800/98A AU5280098A AU703619B2 AU 703619 B2 AU703619 B2 AU 703619B2 AU 52800/98 A AU52800/98 A AU 52800/98A AU 5280098 A AU5280098 A AU 5280098A AU 703619 B2 AU703619 B2 AU 703619B2
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group
formula
halogen atom
atom
benzylsulfide
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AU52800/98A
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AU5280098A (en
Inventor
Mieko Kawashima
Yutaka Kurihara
Naoshi Masuyama
Tomonori Shimazu
Keiji Toriyabe
Hiroyuki Yano
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Ihara Chemical Industry Co Ltd
Kumiai Chemical Industry Co Ltd
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Ihara Chemical Industry Co Ltd
Kumiai Chemical Industry Co Ltd
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Priority claimed from AU53467/96A external-priority patent/AU685025B2/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/26—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C317/28—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to acyclic carbon atoms of the carbon skeleton
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/26—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds containing nitrogen-to-nitrogen bonds, e.g. azides, diazo-amino compounds, diazonium compounds, hydrazine derivatives
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    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/04—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing aldehyde or keto groups, or thio analogues thereof, directly attached to an aromatic ring system, e.g. acetophenone; Derivatives thereof, e.g. acetals
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    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen
    • A01N35/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen containing a carbon-to-nitrogen double bond
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    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • A01N37/28—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof containing the group; Thio analogues thereof
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    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • A01N41/04—Sulfonic acids; Derivatives thereof
    • A01N41/06—Sulfonic acid amides
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    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • A01N41/10—Sulfones; Sulfoxides
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
    • A—HUMAN NECESSITIES
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
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    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/34—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N51/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds having the sequences of atoms O—N—S, X—O—S, N—N—S, O—N—N or O-halogen, regardless of the number of bonds each atom has and with no atom of these sequences forming part of a heterocyclic ring
    • C—CHEMISTRY; METALLURGY
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/72—Hydrazones
    • C07C251/86—Hydrazones having doubly-bound carbon atoms of hydrazone groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C323/46—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having at least one of the nitrogen atoms, not being part of nitro or nitroso groups, further bound to other hetero atoms
    • C07C323/48—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having at least one of the nitrogen atoms, not being part of nitro or nitroso groups, further bound to other hetero atoms to nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/60—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton with the carbon atom of at least one of the carboxyl groups bound to nitrogen atoms
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Description

P:\OPER\RM\S3467-96. DIV 1911198 -la- The present application is a divisional application of Australian patent application No. 53467/96, filed 18 April 1996, the entire contents of which is incorporated herein by reference.
The present invention relates to novel benzylsulfide derivatives. The benzylsulfide derivatives are suitable for use as intermediates for the production of novel benzylsulfide pesticides.
Heretofore, it has been reported, for example, in U.S. Patent 3,732,307 and Japanese Unexamined Patent Publications No. 122261/1979 and No. 45452/1981 that S. benzohydrazonophenylsulfide derivatives are useful as insecticides. However benzylsulfide derivatives of the Spresent invention are unknown.
1 5 In recent years, some of conventional commercial insecticides have been restricted in their use in view of problems such as the residual effects, accumulation or environmental pollution, and some have become not so effective as the pests have acquired resistance during their use for a long period of time. Therefore, it has been desired to develop a new insecticide which is highly effective at a low dose and which is excellent in safety.
The present inventors have synthesized various benzylsulfide derivatives and have studied their physiological activities. As a result, it has been found that the pesticide compounds of the present invention exhibit P:\OPE\RMHS346796.DIV 19/1/98 -2outstanding pesticidal activities against various pests, particularly against agricultural and horticultural pests including lepidopteran injurious insects represented by diamond back (Plutella xylostella), Asiatic rice borer (Chio suppressalis) and beat armyworm (Spodoptera exiqua), hemipteran injurious insects represented by brown planthopper (Nilaparvata luqens), green rice leafhopper (Nephotetlix cincticeps) and cotton aphid (Aphis gossypii) and elytron injurious insects represented by adzuki bean weevil (Callosobrunchus chinensis). The present invention has been accomplished on the basis of this discovery.
That is, the present invention provides a benzylsulfide derivative of the formula (II): 15
R
B C-SOnR 1 13
R
R
wherein
R
1 is a C 1 -6 alkyl group, a C 1 _4 cyanoalkyl group, a C 1
L
4 hydroxyalkyl group, a C 3 6 cycloalkyl group, a C 1 6 haloalkyl group, a C 2 -4 alkenyl group, a C 2 4 alkynyl group, a phenyl group (which may be substituted by a halogen atom or a C 1 4 alkyl group), a cyano group, a benzyl group (which may be substituted by a halogen atom), a thiazolyl group, a C 1 4 alkylcarbamoyl group or P:\OPER\RMH\53467.96.DIV 191198 -3a group of the formula -N(R 5
)R
6 each of R 2 and R 3 which are independent of each other, is a hydrogen atom, a halogen atom, a cyano group, a C 1 4 alkyl group, a C1-3 haloalkyl group, a C_ 4 alkylthio group, a C,_ 4 alkylcarbonyl group, a carboxyl group, or a CI_ 4 alkoxycarbonyl group; or R 2 and R 3 may form a 3- to 6membered ring together with the carbon atom to which they are bonded; or R 1 and R 2 may form a 3- to 8-membered ring having one or more hetero atoms, together with the sulfur and carbon atoms to which they are respectively bonded;
R
4 is a hydrogen atom, a halogen atom, a C 1 4 alkyl group, a C 1 4 haloalkyl group, a C 1 4 alkoxy group or a C* 1
C
4 haloalkoxy group; each of R 5 and R 6 which are independent of each other, is a hydrogen atom, a C 1 -6 alkyl group or a C 1 4 haloalkyl group; or R 5 and R 6 may together form a group of the formula =CR 7
R
8 or R 5 and R 6 may form a 4- to 8-membered ring having one or more hetero atoms, together with the nitrogen atom to which they are bonded; R 7 is a hydrogen atom, a C 1 3 alkyl group or a C 1 3 alkylthio group; R 8 is a C 1 3 alkylthio group or a C01 3 alkylamino group;. or R 7 and R 8 may form a saturated or unsaturated 4- to 8-membered ring together with the carbon atom to which they are bonded; B is an aralkyl or arylcarbonyl group of the formula (Bl) or (B2): 9 R28R 9 m C- m C-
R
1 c-Q [Bl] CB2] P:\OPERXRMII'53467-96. DIV 2011/98 -4-
R
9 is a hydrogen atom, a halogen atom, a nitro group, a cyano group, a C 1 4 alkyl group, a C1- 4 haloalky. group, a
C,
1 4 alkoxy group, a CI..
4 haloalk-oxy group, a C 1 4 alkylthio group, a C 1 4 haloalkylthio group, a C 1 4 alkylsulfonyl group, a C 2 4 alkylsulfonylmethyl group, a C1- 4 haloalkylsulfonyloxy group, a phenyl group (which may be substituted by a halogen atom) or a phenoxy group (which- may be substitutedby a halogen atom); or two R9 may together form a 5- or 6-rnembered ring; RIO is a hydrogen atom or a C 1 4 alkyl group;
R
28 is a halogen atom or a hydroxyl group; each of Q 1 and Q 2 is a. nitrogen atom or a group of the formula
-CR
9 m is an integer from 1 to 3; and n is 0, 1 or 2.
The present invention also provides a benzylsulfide derivative of the formula MI or its salt; C SOn-R 1 R 4 R?1 .wherein
R
2 R 3 R 4 and n are as defined above; A is a hydrazinoaralkyl or hydrazonoaralkyl group of the formula (Al) or (A2); P:\OPER\RMH\53467-96.DIV 20/1/98 R11
R
12 R12 9 /N R13 13 9 N 9 NN R R Rm I Qh-Q 2 11 Q=Q 2
R
[Al] [A2] wherein R 9 Rio, m, Q 1 and Q 2 are as defined above; and each of R 1 1
R
1 2 and R 13 which are independent of one another, is a hydrogen atom, a cyano group, a
C
1 6 alkyl group, a C 1 4 haloalkyl group, a C2-10 alkoxyalkyl group, a C 3 8 alkoxyalkoxyalkyl group, a C2- 6 alkylthioalkyl group, a C 2 -6 alkenyl group, a C2- 4 alkynyl group, a C 4 cyanoalkyl group, a benzyl group (which may be substituted by a halogen atom, a C 4 1-4 haloalkyl group or a C 1 4 alkyl group), a group of the formula -COR 1 4 a group of the formula -CSR 1 4 a group of the formula -COOR 15 a group of the formula
-COSR
15 a group of the formula -CON(R 1 6
)R
7 a group of the formula
-CSN(R
1 6
)R
1 7 a group of the formula
-SN(R
1 8
)R
1 9 a group of the formula -SO2R20 or a group of the formula
-C(R
1
)=CHR
2 2 or R 1 2 and-R 1 3 may together form a group of the formula =CR 23
R
24 or R 12 and R 13 may form a 4- to 8membered ring having one or more hetero atoms, together with the nitrogen atom to which they are bonded;
R
14 is a hydrogen atom, a C1- 20 alkyl group, a C 1 _g haloalkyl group, a C 2 1 2 alkoxyalkyl group, a C2- 10 haloalkoxyalkyl group, a C 3 16 alkoxyalkoxyalkyl group, a C4- 22 alkoxyalkoxyalkoxyalkyl group, a C 2 -6 alkylthioalkyl P:\OPER\RMH\53467-%..DIV 20/1/98 -6group, a C 3 6 cycloalkyl group, a C 1 6 hydroxyalkyl group, a C 1 6 aminoalkyl group, a C_- 6 amidoalkyl group, a Ci_ 8 cyanoalkyl group, a C3- 12 alkoxycarbonylalkyl group, a
C
2 -6 alkenyl group, a C2- 4 alkynyl group, a phenyl group (which may be substituted by a halogen atom, a nitro group, a C 1 4 alkyl group, a C 1 4 haloalkyl group, a phenoxy group or a C 1 4 alkoxy group), a naphthyl group (which may be substituted by a halogen atom or a C_ 4 alkyl group) or a hetero aromatic ring group (which may be substituted by a halogen atom or a C 1 4 alkyl group);
R
1 5 is a C 1 2 0 alkyl group, a C2_ 8 haloalkyl group, a C2_ 12 alkoxyalkyl group, a C 2 6 alkenyl group, a C2- 4 alkynyl group, a benzyl group (which may be substituted by a halogen atom, a C 1 _4 alkoxy group or a C 1 4 alkyl group) S* 15 or a phenyl group (which may be substituted by a halogen atom); R 16 is a hydrogen atom or a C 1 4 alkyl group; R 1 7 is a hydrogen atom, a C 1 6 alkyl group or a phenyl group (which may be substituted by a halogen atom, a C1 haloalkoxy group or a C 1 4 alkyl group); each of R 18 and
R
19 which are independent of each other, is a C 1 4 alkyl group (which may be substituted by a C 1 4 alkoxycarbonyl group), or a C2_ 5 alkoxyalkyl group; or R 18 and R 19 may form a 5- or 6-membered ring together with the nitrogen atom to which they are bonded; R 2 0 is a C 1 -4 alkyl group, a C1- 4 haloalkyl group or a C 2 4 dialkylamino group; R 21 is a hydrogen atom or a C 1 _g alkyl group; R 22 is a C 2 -4 acyl group or a C 2 -6 alkoxycarbonyl group; each of R 23 and P:\OPER\RMH\53467-96. DIV 201198 -7-
R
24 which are independent of each other, is a hydrogen atom, a halogen atom, a C_g 6 alkyl group or a group of the formula -N(R 25
)R
26 each of R 25 and R 26 which are independent of each other, is a hydrogen atom, a C 1 4 alkyl group, a C 1 4 alkoxy group, a C2- 1 2 alkoxyalkyl group or a group of the formula -SO 2
R
2 7 or R 25 and R 2 6 may form a 5- or 6-membered ring together with the nitrogen atom to which they are bonded; R 27 is a C1 8 alkyl group or a phenyl group (which may be substituted by a halogen atom or a C 1 4 alkyl group).
The present invention further provides benzophenonehydrazone derivatives of the formula (III), processes for preparing benzylsulfide derivatives of formula and pesticides containing same as an active 1 5 ingredient, all of which are disclosed in the hereinbefore mentioned Australian patent application No. 53467/96.
In the present invention, the halogen atom represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
The alkyl group means a linear or branched C2 alkyl group such as a methyl group, an ethyl group, a npropyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, an isoamyl group, a neopentyl group, a nhexyl group, an isohexyl group, a 3,3-dimethylbutyl group, a n-heptyl group, a n-octyl group, a n-nonyl group or a n-decyl group.
P:\OPER\RMH\S346796. DIV 20/1/98 -8- The cycloalkyl group represents a,C3_ 6 cycloalkyl group such as a cyclopropyl group, a cyclopentyl group or a cyclohexyl group.
The alkenyl group represents a linear or branched C 1 6 alkenyl group such as an ethenyl group or a 2-propenyl group.
The haloalkyl group represents a linear or branched Ci_ 8 alkyl group which is substituted from 1 to halogen atoms which may be the same or different such as a chloromethyl group, a trifluoromethyl group or a tetrafluoroethyl group.
The cyanoalkyl group represents a linear or branched
C-_
8 alkyl group which is substituted by a cyano group.
The hydroxyalkyl group represents a linear or 1 branched C 1 8 alkyl group which is substituted by a hydroxyl group.
The alkoxy group represents an alkyl-O- group wherein the alkyl moiety is as defined above, and it may, for example, be a methoxy group or an ethoxy group.
The haloalkoxy group represents a haloalkyl-0- group wherein the haloalkyl moiety is as defined above, and it may, for example, be a trifluoromethoxy group or a 2chloroethoxy group.
The alkylthio group represents an alkyl-S- group wherein the alkyl moiety is as defined above, and it may, for example, be a methylthio group or an ethylthio group.
The haloalkylthio group represents a haloalkyl-S- P:\OPER\RMH\53467-96.DIV 20/1/98 -9group wherein the haloalkyl moiety is as defined above, and it may, for example, be a trifluoromethylthio group or a 2-chloroethylthio group.
The alkylsulfonyl group represents an alkyl-SOzgroup wherein the alkyl moiety is as defined above, and it may, for example, be a methylsulfonyl group or an ethylsulfonyl group.
The alkylsulfonylmethyl group represents an alkyl-
SO
2
CH
2 group wherein the alkyl moiety is'as defined above, and it may, for example, be a methylsulfonylmethyl group or an ethylsulfonylmethyl group.
The alkylene group means a linear C 1 8 alkylene group such as a methylene group, an ethylene group, a 'o trimethylene group or a tetramethylene group.
15 The alkoxyalkyl group represents an alkyl-O-alkylene group wherein the alkyl moiety and the alkylene moiety are as defined above, and it may, for example, be a e methoxymethyl group or an ethoxymethyl group.
The alkylthioalkyl group represents an alkyl-Salkylene group wherein the alkyl moiety and the alkylene moiety are as defined above, and it may, for example, be a methylthiomethyl group or an ethythiomethyl group.
The alkoxyalkoxyalkyl group represents an alkyl-Oalkylene-O-alkylene group wherein the alkyl moiety and each alkylene moiety are as defined above.
The alkoxyalkoxyalkoxyalkyl group represents an alkyl-O-alkylene-O-alkylene-O-alkylene group, wherein the P:\OPER\RMH\53467-96.DIV 20/1/99 alkyl and each alkylene group are as defined above.
The aminoalkyl group- represents a linear or branched
CI_
8 alkyl group which is substituted by an amino group, a monoalkylamino group or a dialkylamino group.
The amidealkyl group represents a linear or branched
C
1 8 alkyl group which is substituted by an acylamino group or an N-alkyl-N-acylamino group.
The alkynyl group represents a linear C 1 4 alkynyl group.
The hetero aromatic ring group represents a membered aromatic ring group containing from 1 to 4 nitrogen, oxygen or sulfur atoms or a fused ring thereof with a benzene ring, or a 6-membered aromatic ring group containing from 1 to 3 nitrogen atoms or a fused ring thereof with a benzene ring, and it may, for example, be a furyl group, a thienyl group, a pyrazolyl group, an imidazolyl group, a benzofuranyl group, a benzothiazolyl
S.*
group, a pyridyl group, a pyrimidinyl group, a pyridazinyl group, a triazinyl group, a quinolyl group or a quinoxalinyl group.
A preferred group of compounds of the above formula (II) may, for example, be a group of compounds wherein:
R
1 is a C 1 _4 alkyl group, a cyanomethyl group, a hydroxyethyl group, a cyclopentyl group, a C 1 3 haloalkyl group, a phenyl group (which may be substituted by a halogen atom), a cyano group, a C,_ 4 alkylcarbamoly group or a thiazolyl group; P:\OPER\RMH\53467-96.DIV 20/1/98 -11each of R 2 and R 3 which are independent of each other, is a hydrogen atom, a methyl group or a C,_ 2 alkoxycarbonyl group; or R 1 and R 2 may form a ring together with the sulfur and carbon atoms to which they are respectively bonded;
R
4 is a hydrogen atom or a fluorine atom; B is an aralkyl or arylcarbonyl group of the formula (Bl) or (B2);
R
9 is a halogen atom, a trifluoromethyl group, a methoxy group, a C 1 -2 fluoroalkoxy group or a phenoxy group (which may be substituted by a halogen atom);
R
10 is a hydrogen atom;
R
28 is a chlorine atom or a hydroxyl group; each of Q 1 and Q2 is a nitrogen atom or a group of 15 the formula -CR 9 m is an integer of 1 or 2; and n is 0 when R 1 is a cyano group or a C 1 4 alkylcarbamoyl group, or 0, 1 or 2 in other cases.
Now, typical specific examples of the compounds of the formula (II) of the present invention will be given in Tables 29 to 34. The compound numbers used in the tables will be referred to in the subsequent description.
It should be understood that among the compounds of the present invention, those which are capable of having tautonomers, have such corresponding tautonomers even if such tautonomers are not specifically mentioned.
12 Table 29
R
9 6 1 2 3 R- 3 2 R 4 6 Cm. 91 2 3 4 MP *)9 cm-Rm R R R R n ,;iracttI.: VI-1I 4-Cl CHU H H H 0 59- 6L VI- 2 4-Cl CHU 3 H H H 1 116-118 VI- 3 4-Cl CH 3 H H IH 12 164-166 VI- 4 4-Cl CA H H H 0 3-3 2 5 VI- 6 4-Cl C 2 HA H H H 2 117-118 VI- 7 4-Cl C 3 H 7 H H H 2 128-129 VI- 8 4-Cl C 3 H 7 1 H H H 2 '135-137 Yi- 9 4-Cl C 4
H
9 H H H 2 118-119 VI-10 4-Cl CH C1 H H H 2 148-150 2 YI-11 4-Cl C H Br H H H 2 105-107 *3 6 VI-12 4-Cl CF H H H 0 63- .3 :VI-13 4-Cl CF 3 H H H 1 114-115 3 VI-14 4-CL CF 3 F, H Y, 2 123-125 4-Cl CHF 2 H H H 0 34- VI-16 4-Cl CHF 2 H R H 2 154-157 VI-17 4-Cl C F 5 H H H 0 52- 53 VI-18 4-Cl C F H HH 2 94- 96 2 5 VI-19 4-Cl CH 2 CF 3 H H H 2 148-150 *VI-20 4-Cl CF 2 CHF 2 H H H 0 48- VI-21 4-Cl CF 2 CHF 2 H H H 2 68- *VI-22 4-Cl CF 2 CHFCF 3 H H H 0 Unmeasurable *VI-23 4-Cl CH 2 CN H H H 0 54- *VI-24 4-Cl CH 2 CN H H H 2 179-181 13 Table Comp. R9 No.
I
4-Cl VI-26 4-Cl VI-27 4-CF 3 VI-28 4-Cl VI-29 4-Cl YV1-30 4-F VI-31 4-F YI-32 4-F VY1-33 4-F VI-34 4-F 4-Cl 4-Cl VI3 4-C VI-38 4-Cl VI-3 4-I *I4 4*i :VI-41 4-C1l V.-4 4-C C *.VI-43 4-Cl C VI-44 4-Cl C 4 .VI-45 4-Cl C *VI-46 4-Cl CI 14 Table 31 9*
S.
S
S..
*5 S *5 5.5.
5* 5 55.*.
S
S
S. S S S
L
Comp. 9 No. R m
R
2 3 4 *p()e R R R n tff.cti..
Ine I.9 VI-51 H CH 3 CH 3 H H 0 143-145 VI-52 4-F CF H H H 2 84- 3 VI-53 4-F CH 2 C1 H H H 2 110-112 VI-54 4-F CHF 2 H H H 0 1.5572 4-F CHF 2 H H H 2 155-167 '/1-56 4-F CN H H IH 0 1 116-117 VI1-57 4-OCHF 2 CH 3 H H H 2 130-131 VI-58 4-OCHF 2
CF
3 H H H 2 95- 96 VI-59 4-OCH 2 CF 3 CH 3 H H H 2 110-112 4-OCH 2 CF 3
CF
3 H H H 2 105-107 VI-61 3. 4.5-F 3 CF 3 H H H 2 83- 84 VI-62 4-GCF 3 CF 3 H H RI 2 116-117 VI-63 3-F. 4-Cl CF 3 H H H 2 79- 81 VI-64 3-F. 4-Cl CN H H H 0 93- VI-65 3-F.4-CI C 2
R
5 H H H 0 1.6129 YI-66 3-F. 4-Cl CHF 2 H H H 0 1.5922 YI-67 3-F. 4-Cl CF 3 H H H 0 69- YI-68 4-Br CN H H H 0 145-148 YI1-69 4-Br CF 3 H H Hi1 0 74- VI1-70 4-Br CAF 2 H H H 0 63- 64 VI1-71 4-Br CHF 2 H H H 1 118-119 VI-72 4-Br CN CH 3 H H 0 53- 54 V/1-73 4-Br CF 3 CH 3 H H 0 39- '/1-74 3, 4-F 2 C 2 H 5 H H H 1 176-178 VI-75 4-0-C)-C1 CF 3 H H H 2 125-126 VI-76 4-OCH 3 Cli H H H 0 79- 81 '/I-77 4-OCH 3 CF 3 H H H 0 57- 59 15 Table 32 Table 33 R9 a a a a.
a.
a Oa* a a a a a. a a a. a.
a as..
a a. 56 0 2 3 42R 4 I R R 4' c 4L C-SOnR 1 Qh=Q2 6 5 A 3 2 9r 1- (C Comp. R m R R ^IR' Q 1 Q' n ro.Uctiv No. 1widex& vi 1-1 VI 1-2 VII 1-3 VI 1-4 V 11-5 VI11-6 VII-7 viI1-8 4-Cl 4-Cl 4-Cl 4-Cl 4-ClI 4-Cl 4-Cl 4-Cl CH 3 CF 3 CF 3
CN
CH 3 CF 3 162-164 97- 99 1. 5820 94- 96 155- 156 93- 94 153- 155 38- 39 I A. I. ii I 16 Table 34 Rr R 5 28 2 9 R R~ jC I I I
I
3 2 R46-5 R'SO 3 Coxnp. 9 R 1
R
2 3 4 28 p.C N. R m R R R n index VI[I-1 4-Cl C 2H 5 H H H OH 2 1. 5959 '/111-2 4-Cl CF 3 H H H OH 2 113-115 '/111-3 4-Cl CF 3 H H 9 OH 0 1.5601 VIIJ-4 4-Cl CHF' H H H OH 2 85- 87 '/111-5 4-C! C 2 H 5 H H H CI 2 1.6044 VIII-6 4-F CH 3 H H H OH 2 139-140 V/1II-7 4-F CF 3 H H H OH 2 99-100 a
S
a a a a a.
S S a. S P:\OPER\RMH\53467-96. DI V -22/1/98 17 Now, processes for producing the compounds of the present invention will be described.
The novel intermediates of the above formula
(II)
can be produced, for example in accordance with the following Processes, Process 12 R 9 0 RZ R 0 R 2 Q-q" -an6-X A"
SOR
[XXX)1
M
2 SCN (XXXI I [XXX I I R: R
R
2 *R 0 R 2 6SR 1 C SR R [XXXIII1) X IY In, the above formulas, RI is a C,- 6 alkyl group, a 50.5..C1- 4 cyanoalkyl group, a C 1 4 hydroxylalkyl group, a C 3 6 cycloalkyl group, a C 1 -6 haloalkyl group, a phenyl group (which may be substituted by a halogen. atom or a C 1 4 alkyl group), a benzyl group (which may be substituted by a halogen atom) or a thiazolyl group; 'X 4 is a halogen 18 atom, a Cl_ 4 alkylsulfonyloxy group or a benzenesulfonyloxy group (which may be substituted by a methyl group);
M
1 is an alkali metal;
M
2 is an alkali metal or an ammonium ion;
R
2
R
3
R
4 m, Q1 and Q2 are as defined above; and n is 1 or 2.
Namely, a benzyl sulfone derivative of the formula (XXXI) can be obtained by reacting 1 mol of a benzyl halide of the formula (XXX) with from 1.0 to 3.0 mols of an alkali metal salt of sulfinic acid of the formula (V9) in the presence of from 0 to 10 e of a solvent.
The solvent which can be used here, may, for example, be an ether, an aromatic hydrocarbon, an aprotic polar solvent, an alcohol, a halogenated hydrocarbon, an aliphatic hydrocarbon or. water, or a solvent mixture thereof. The reaction temperature is an optional temperature within a range of from 0OC to the reflux temperature in the reaction system, preferably from 10 to 100 0
C.
The salt of sulfinic acid to be used here, may be 20 available as a reagent or can be prepared by a conventional method a method disclosed in J. Chem.
Soc., vol. 636 (1945), or J. A. Chem. Soc., vol 96, No.
7, p. 2275 (1974)).
Further, under similar reaction conditions, a 25 compound of the formula (XXXII) can be obtained from a compound of the formula (XXX) and a thiocyanate of the formula 19 Furthermore, a sulfide of the formula (XXXIII) can be obtained by reacting 1 mol of the compound of the formula (XXX) with from 1.0 to 3.0 mols of a mercaptan of the formula (Vll) in the presence of from 0 to 5 e of a solvent in the presence of from 1.0 to 0.3 mol of a base.
The solvent and the base may, for example, be the same as used in Process 6. The reaction temperature is an optional temperature within a range of from -10 0 C to the reflux temperature in the reaction system, preferably from 0 to 100 0
C.
A compound of the formula (XXXIV) of'the present invention can be obtained by reacting 1 mol of the compound of the formula (XXXIII) thus obtained with from to 10.0 mols of an oxidizing agent in the presence of from 0 to 5 e of a solvent, if necessary in the presence of from 0.01 to 1.0 mol of a catalyst.
The oxidizing agent may, for example, be hydrogen peroxide, m-chloroperbenzoic acid, sodium periodate, OXONE (tradename for an agent containing potassium 20 hydrogen peroxosulfate, manufactured by E.I. DuPont), Nchlorosuccinimide, N-bromosuccinimide, tert-butyl hypochlorite or sodium hypochlorite.
The catalyst may, for example, be sodium tungstate.
The solvent which can be used here, may, for example, 25 be an ether, an aromatic hydrocarbon, an aprotic polar solvent, an alcohol, a halogenated hydrocarbon, an aliphatic hydrocarbon, as used in Process 1, acetic acid, 20 water or a ketone such as acetone, methyl ethyl ketone or cyclohexanone, or a solvent mixture thereof.
The reaction temperature is an optional temperature within a range of from -20 0 C to the reflux temperature in the reaction system, preferably from 10 to 100 0
C.
The benzyl halide of the formula (XXX) to be used as the starting material, is commonly known or can be prepared by a conventional method a method disclosed in Org. Synth., vol. 4, p. 921 (1963)) by halogenating the methyl group of the corresponding arylcarbonyltoluene with a halogenating agent (such as chlorine, bromine, N-chlorosuccinimide,
N-
bromosuccinimide, sulfuryl chloride or sulfuryl bromide).
The arylcarbonyltoluene can be obtained usually by reacting toluene with an aryl carboxylic acid halide in the presence of a Lewis acid such as aluminum chloride.
Process 13 a. a a a a S a.
R
9 0 R2
RIX
4 [V12 (Xc II
Q
X4 R4 kO 1 xxx V R1 OS02CF3
R
9 0 R2 k
R
4 R [XXX II!] *aa.
a a. a a xxxvI]
F
2 C=CFRf [xxxvii] PIq j, SCF 2 CHFRf
XXXR
4 I [XXXV1II] 21 In the above formulas,
R
I is a C 1 -6 alkyl group, a
C
3 -6 cycloalkyl group, a C 1 6 haloalkyl group, a C 1 4 cyanoalkyl group or a C 1 4 hydroxyalkyl group; Rf is a fluorine atom or a perfluoroalkyl group; X 4 is a halogen atom, a C 1 4 alkylsulfonyloxy group or a benzenesulfonyloxy group (which may be substituted by a methyl group);
R
2
R
3
R
4 m, Q 1 and Q 2 are as defined above; and n is 1 or 2.
The sulfide of the formula_(XXXIII) or (XXXVIII) can be obtained by reacting 1 mol of benzyl mercaptan of the formula (XXXV) with from 1.0 to 3.0 mols of an alkylating agent of the formula (V12) and a dibenzothiopheniumtrifluoromethane sulfonate of the formula (XXXVI), or a perfluoroalkene of the formula (XXXVII), in the presence of from 0 to 10 4 of a solvent, if necessary in the presence of from 1.0 to 3.0 mols of a base.
The base and the solvent which can be used here, may, for example, be the same as used in Process 6. The 20 reaction temperature is an optional temperature within a range of from 0OC to the reflux temperature in the reaction system, preferably from 10 to 150 0
C.
a By oxidizing the sulfide of the formula (XIII) or (XVIII) thus obtained by the same oxidizing method as 25 used in Process 12, it is possible to obtain the corresponding sulfoxide or sulfone derivative.
The benzyl mercaptan of the formula (XXXV) to be used 22 as the starting material, is already known or can be prepared in accordance with a conventional method a method disclosed in Org. Synth., vol. 3, p. 363 (1955)) or a similar method. Namely, it can be obtained by reacting a benzyl halide of the formula (XXX) as the starting material in Process 12, with sodium sulfide, or reacting it-in the presence of thiourea and a base, followed by hydrolysis.
Process 14 09 I R- RI 0 QQ CSOn l CJN CH-SO XXXIX]
[XL]
R3-X 4 R 0 2 1 5 SpnR1 n
CXLIJ]
In the above formulas,
R
1
R
4 R, m n, Q1 and Q 2 are as defined above; each of R 2 and R 3 is an alkyl group 20 or a haloalkyl group; and X 4 is a halogen atom, a C1- 4 alkylsulfonyloxy group or a benzene sulfonyloxy group (which may be substituted by a methyl group).
Namely, the compound of the formula (XL) or (XVI) can be prepared by reacting 1 mol of a compound of the 25 formula (XXXIX) with from 1.0 to 5.0 mols of an alkylating agent of the formula (V13) or (V14) in the presence of from 0 to 5 e of a solvent and from 1.0 to 23 mols of a base. When X 4 is present in a side chain of R 1
R
1 and R 2 will form a from 3- to 8-membered ring having one or more hetero atoms, together with the sulfur and carbon atoms to which they are respectively bonded.
The base and the solvent which can be used here, may, for example, be the same as used in Process 6. The reaction temperature is an optional temperature within a range of from 0°C to the reflux temperature in the reaction system, preferably from 10 to 150°C.
Process
R
9 0 Ri R 9 0 SCH2SC
R'
ql~q2 vlov X-- Q R4 1[XLI II R4 [XLI1] XLiy] *o In the above formulas, R 4
R
9 m, n, Q 1 and 02 are as defined above; and R 1 is an alkyl group or a haloalkyl group.
to *9 .o Namely, a compound of the formula (XLIV) can be 20 produced by reacting 1 mol of the compound of the formula (XLII) of the present invention with from 1.0 to 5.0 mols of a carbanion of the formula (XLIII) in the presence of from 0 to 10 e of a solvent. The method for generating the carbanion of the formula (XLIII), may, for example, 25 be 1) a method of contacting from 1.0 to 15.0 mols of a trihalomethane with from 1.0 to 15.0 mols of a base, if necessary in the presence of from 0.01 to 1.0 mol of a 24 phase transfer catalyst such as a tetraalkyl ammonium salt, a benzyltrialkylammonium salt, a tetraalkylphosphonium salt or a crown ether, 2) a method of contacting from 1.0 to 15.0 mols of a (trialkylsilyl)alkyl halide with from 1.0 to 15.0 mols of a fluoride such as potassium fluoride or tetrabutylammonium fluoride, or 3) a method of contacting from 1.0 to 5.0 mols of an alkyl halide or a haloalkyl halide with from 1.0 to 5.0 mols.of a metal such as lithium, sodium, copper or zinc, or with an organometallic compound such as lithium diisopropylamide, phenyl lithium or butyl lithium.
The solvent which can be used, may, for example, be an ether, an aromatic hydrocarbon, an aprotic polar solvent, an alcohol, an aliphatic hydrocarbon or water, or a solvent mixture thereof.
The reaction temperature is an optional temperature within a range of from -70oC to the reflux temperature in the reaction system, preferably from -50 to 50 0
C.
20 Process 16 0 *4 .o Q1q 2 C.J CHsR' 4 R CXLYIJ Q 1 Q2 C-9 -R 4
R
LXLV]
.:XLV]
XLVII]
25 In the above formula, R 2
R
3
R
4
R
9 m, n, Q 1 and Q 2 are as defined above; X 5 is a halogen atom, a cyano group or a group of the formula
SR
1 and R 1 is an alkyl group
MMMM
25 or a haloalkyl group.
Namely, a compound of the formula (XLVII) can be prepared by reacting 1 mol of a compound of the formula (XLV) of the present invention with from 1.0 to 5.0 mols of a compound of the formula (XLVI) in the presence of from 0 to 5 e of a solvent and from 1.0 to 5.0 mols of a base.
The base and the solvent which can be used here, may, for example, be the same as used in Process 6.
The reaction temperature is an optional temperature within a range of from -70°C to the reflux temperature in the reaction system, preferably from -50 to 50 0
C.
Process 17
R
9 0 9 15
C
2 0H R SSR 1 C C 2
S
R
R 4 UXLVI II [XLI X] In the above formulas, R 1
R
4
R
9 m, n, Q1 and Q 2 20 are as defined above.
Namely, a compound of the formula (XLIX) of the present invention can be obtained by reacting 1 mol of a benzyl alcohol of the formula (XLVIII) with from 1.0 to 3.0 mol of a dialkylaminochlorophosphine usually in the 25 presence of a solvent and a base, i.e. in the presence of from 0.1 to 5 e of a solvent and from 1.0 to 3.0 mols of a base, to obtain a phosphite, followed by reacting from 26 to 5.0 mols of a disulfide of the formula (V15) in the presence of from 0 to 5 e of a solvent.
The solvent which can be used here, may, for example, be an ether such as diethyl ether, tetrahydrofuran or dioxane, an aromatic hydrocarbon such as benzene, toluene, xylene or chlorobenzene, an aprotic polar solvent such as N,N-dimethylformamide,
N,N-
dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide or sulfolane,.a halogenated hydrocarbon such as methylene chloride or chloroform, a nitrile such as acetonitrile or propionitrile, an ester such as ethyl acetate or ethyl propionate, an aliphatic hydrocarbon such as pentane, hexane, cyclohexane or heptane, a pyridine such as pyridine or picoline, or a solvent mixture thereof.
.*99 The base may, for example, be an inorganic base e.g.
an alkali metal hydroxide such as sodium hydroxide Or potassium hydroxide, an alkaline earth metal hydroxide such as calcium hydroxide or magnesium hydroxide, an S9. 20 alkali metal carbonate such as sodium carbonate or potassium carbonate, or an alkali metal bicarbonate such as sodium hydrogen carbonate or potassium hydrogen carbonate, a metal hydride such as sodium hydride or potassium hydride, or an organic base such as 25 triethylamine, N,N-dimethylaniline, pyridine, 4-N,Ndimethylaminopyridine or 1,8-diazabicyclo(5.4.0]-7undecene.
27 The reaction temperature is an optional temperature within a range of from -40 0 c to the reflux temperature in the reaction system, preferably from -30 to 50 0
C.
The reaction time varies depending upon the particular compound, but can be set within a range of from 10 minutes to 20 hours.
Process 18 Reducing agent
R
9 0 R 2 or 9 OH R 2 0 ~ZR-
R'M
3
I
m\,zq 4 13 RiO 61
R
9 V/ C0RI in6]Q Q lk. R R
R
4
R
[LI]
In the above formulas,
R
1
R
2
R
3
R
4
R
9 RIO, Q1'
Q
2
M
3 m and n are as defined above.
Namely, a compound of the formula (LI) of the present invention can be obtained by reacting a compound of the formula of the present invention with from 1.0 to 50.0 mols of a reducing agent in the presence of from 0 o S to 5 -e of a solvent, if necessary, in the presence of from 0.01 to 1.0 mol of a catalyst, or by reacting it 20 with from 1.0 to 5.0 mols of an alkyl metal compound of the formula (V16).
The reducing agent may, for example, be molecular hydrogen, sodium borohydride, lithium aluminum hydride or aluminum hydride or diisobutylaluminum hydride.
25 The catalyst may, for example, be platinum, nickel, cobalt or palladium.
The solvent which can be used here, may, for example, 28 be an ether, an aromatic hydrocarbon, an aprotic polar solvent, an alcohol, an aliphatic hydrocarbon, acetic acid or water, or a solvent mixture thereof.
The reaction temperature is an optional temperature within a range of from -20°C to the reflux temperature in the reaction system, preferably from 10 to 100 0 c. The reaction time varies depending upon the particular compound, but can be set within a range of from minutes to 20 hours.
Process 19
R
9 O ff Halogenating
R
9
X
3
R
2
R
1 SOagent I i q1=0-2 I N -C-S-n (r-c-vcs nR
R
10 3 nQ2 .1 oO 3Q -2 f/ i" n
R
R R R 4 R 3 r, j- R 5'LI) .[LI
I]
15 In the above formulas,
R
1
R
2
R
3
R
4
R
9 RiO, QI, 2 m and n are as defined above; and X 3 is a chlorine atom or a bromine atom.
•A new compound of the formula (LII) of the present invention can be obtained by reacting 1 mol of a compound of the formula (LI) of the present invention with from 1.0 to 10.0 mols of a halogenating agent in the presence of from 0 to 5 e of a solvent.
The halogenating agent may, for example, be hydrogen chloride, hydrogen bromide, phosphorus trichloride, phosphorus tribromide, thionyl chloride, a mixture of triphenylphosphine/carbon tetrachloride or a mixture of a P:\OPER\RMH\53467-96.DIV 23/1/98 -29triphenylphosphine/bromine.
The solvent which can be used here, may, for example, be an ether such as diethyl ether, tetrahydrofuran or dioxane, an aromatic hydrocarbon such as benzene, toluene, xylene or chlorobenzene, a halogenated hydrocarbon such as methylene chloride or chloroform, a nitrile such as acetonitrile or propionitrile, an aliphatic hydrocarbon such as pentane, hexane, cyclohexane or heptane, or a solvent mixture thereof.
1 0 Further, the halogenating agent may serve as a solvent.
The reaction temperature is an optional temperature within a range of from 0°C to the reflux temperature in the reaction system, preferably from 10 to 180 0 C. The reaction time varies depending upon the particular 15 compound, but can be set within a rang of from 10 minutes to 20 hours.
Now, the present invention will be described in further detail with reference to the following Preparation Examples.
PREPARATION EXAMPLE 23 Preparation of 4-chloro-4'-methylsulfonylmethylbenzophenone (Compound No. VI-3) 4-bromomethyl-4'-chlorobenzophenone (3.1 g) and sodium methanesulfinate (1.5 g) were added to N,Ndinethylformamide (50 ml), and the mixture was stirred for 16 hours at room temperature. Water was added to the reaction mixture, and the mixture was extracted with P: \OPER\RMI\S346796. DIV 23/1/98 ethyl acetate. The ethyl acetate layer was washed with water and dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure. The residual solid was washed with n-hexane to obtain the desired product (2.8 g, melting point: 164 to 166 0 c, yield: 1H-NMR data (60MHz, CDC1 3 solvent, 8 value) 2.90 (3H, s) 4.47 (2H, s) 1. 0 7.37-7.83 (8H, m) PREPARATION EXAMPLE 24 Preparation of 4-chloro-4 '-ethylsulfonylmethylbenzophenone (Compound No. VI-6) Sodium sulfite (24.5 g) and sodium hydrogen carbonate 15 (33 g) were dissolved in water (200 ml). Ethane sulfonyl chloride (25 g) was dropwise added to this solution at a o: room temperature in 30 minutes, and the mixture was stirred for one hour. This reaction mixture was concentrated, and the residue was suspended in N,Ndimethylformamide (200 ml). Then, 4-bromomethyl-4'chlorobenzophenone (10.0 g) was added thereto, and the mixture was stirred for 16 hours at room temperature.
Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The ethyl acetate layer was washed with water and then dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure. The residual solid was washed with n- P:\OPER\RMH\53467-96, DIV 23/1/98 -31 hexane to obtain the desired product (7.5 g, melting point: 117 to 118oC, yield: 72%).
'H-NMR data (60MHz, CDC1 3 solvent, 6 value) 1.37 (3H, t) 2.93 (2H, q) 4.27 (2H, s) 7.20-7.83 (SH, m) PREPARATION EXAMPLE Preparation of 4-chloro-4 '-eth1 thiomethylbenzophenone 10 (Compound No. VI-4) 4-chloro-4'-mercaptomethylbenzophenone (16.0 g), ethyl bromide (7.4 g) and potassium hydroxide (4.3 g) were added to methanol (250 ml), and the mixture was stirred for 30 minutes under reflux. The reaction 15 mixture was cooled to room temperature and then concentrated. Water was added to the residue, and the mixture was extracted with ethyl acetate. The ethyl acetate layer was washed with water and then dried over anhydrous magnesium sulfate and concentrated. The residue was purified by silica gel column chromatography (n-hexane:ethyl acetate=10:1) to obtain the desired product 14.0 g, melting point: 33 to 34°C, yield; 79%).
1 H-NMR data (60MHz, CDCl 3 solvent, S value) 2.23 (3H, t) 2.45 (2H, s) 3.75 (2H, s) 7.10-7.90 (8H, m) P:\OPER\RMH\53467-96. DIV 23/1/98 -32- PREPARATION EXAMPLE 26 Preparation of 4-chloro-4' -difluoromethylthiomethy1benzophenone (Compound No. VI-iS) 4-chloro-4' -mercaptomethylbenzophenone (14.*7 g) and potassium hydroxide (15 was added to a solvent comprising dioxane (100 ml) and water (100 ml) Difluoromethyl chloride was blown into this solution at until the starting' material 4-chloro-41mercaptomethylbenzophenone disappeared. The reaction product was cooled to room temperature and then subjected to filtration. The organic layer as the filtrate was dried over anhydrous magnesium sulfate afid concentrated.
The residue was purified by silica gel column chromatography (n-hexane:ethyl acetate=5:l) to obtain the 15 desired product (6.4 g. melting point; 34 to 35*C, yield: 36%) 1 H-NMR data (60MHz, CDC1 3 solvent, 6 value) 4.03 (2H, s) 6.69 (11*9 t) 7.15-7.71 m) PREPARATION EXAMPLE 27 Preparation of 4-chloro-4 -difluoromethylsulfonylmethylbeflzophenone (Compound No. VI-16) 4-chloro-4 '-difluoromethylthiomethylbenzophenone 2 g) and m-chloroperbenzoic acid (5.3 g) were added to chloroform (150 ml). This suspension was stirred for 3 hours under reflux. The reaction mixture was P:\OPER\RMH\53467-96.DIV 23/1/98 -33concentrated, and water was added to the residue. The mixture was extracted with ethyl acetate. The ethyl acetate layer was washed with water and then dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure. The residual solid was washed with n-hexane to obtain the desired product (2.7 g, melting point: 154 to 157°C, yield: 78%).
1 H-NMR data (60MHz, CDCl 3 solvent, 6 value) 4.57 (2H, s) 6.41 (1H, t) 7.27-7.87 (8H, m) PREPARATION EXAMPLE 28 Preparation of 4-chloro-4'-trifluoromethylthiomethylbenzophenone (Compound No. VI-12) 15 4 -chloro- 4 '-mercaptomethylbenzophenone (4.5 g) was dissolved in tetrahydrofuran (150 ml). 60% sodium hydride (0.8 g) was added to this solution, and the mixture was stirred for 30 minutes at room temperature.
Then, S-(trifluoromethyl)dibenzothiopheniumtrifluoromethane sulfonate (6.4 g) was added thereto, and the mixture was further stirred for 30 minutes. The reaction mixture was concentrated, and water was added thereto. The mixture was extracted with ethyl acetate.
The ethyl acetate layer was washed with water and then dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (nhexane;ethyl acetate=4:l) to obtain the desired product P:\OPER\RMH\53467-96. DIV 23/1/98 34 g, melting point: 63 to 650C, yield: 'H-NMR data (60MHz, CDC1 3 solvent, a value) 4.14 (2B, s) 7.30-7.77 (811, m) PREPARATION EXAMPLE 29 Preparation of 4 -chloro-4'-(,l22tetrafluoroethv...
thiomethylbenzophenone (Comp~ound No. VI-201_ 4 -chloro-4'-mercaptomethylbenzophenone (5.0 g) and potassium tert-butoxide (0.9 g) were added to ethanol (150 ml). Perfluoroethylene (2.9 g) were blown thereinto at room temperature, and the mixture was then stirred for 16 hours. The reaction mixture was filtered and concentrated. The residue was purified by silica gel column chromatography (n-hexane;ethyl acetate=4:1) to 15 obtain the desired product 5.3g, melting point: 48 to 500C, yield: 77%).
1 H-NM.R data (6014Hz, CDC1 3 solvent, 8 value) 4.13 (2H1, s) .5.77 (111, tt) 7.23-7.73 (8H, m) PREPARATION EXAMPLE Preparation of 4-chloro-4 '-methylthiomethvlbenzophenone (Compound No. VI-l) 4 -bromomethyl-4'-chlorobenzophenone (3.1 g) and methylmercaptan-sodium aqueous solution (5.6 g) were added to methanol (150 ml), and the mixture was stirred for 30 minutes under reflux. The reaction mixture was concentrated and extracted with ethyl acetate. The ethyl P:\OPER\RMH\53467-96.DIV 23/1/98 acetate layer was washed with water and then dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure. The residual solid was washed with n-hexane to obtain the desired product (2.3 g, melting point: 59 to 61 0 C, yield: 83%).
IH-NMR data (60MHz, CDCi 3 solvent, 8 value)* 2.00 (3H, s) 3.70 (2H, s) 7.13-7.74 (8H, m) 10 PREPARATION EXAMPLE 31 Preparation of 4-chloro-4'- •t methylsulfinvlmethylbenzophenone (Compound No. VI-2) 4-chloro-4'-methylthiomethylbenzophenone (4.2 g) was added to methanol (150 ml). Sodium periodate (3.6 g) 15 dissolved in water (20 ml), was added to this solution, and the mixture was stirred for 16 hours at room temperature. The reaction mixture was concentrated, and water was added thereto. The mixture was extracted with ethyl acetate. The ethyl acetate layer was washed with water and then dried over anhydrous magnesium sulfate.
Ethyl acetate was distilled off under reduced pressure.
The residual solid was washed with n-hexane to obtain the desired product (4.1 g, melting point: 116 to 118 0
C,
yield: 93%).
IH-NMR data (60MHz, CDC1 3 solvent, 6 value) 2.50 (3H, s) 4.00 (2H, s) 7.30-7.80 (8H, m) P:\OPER\RMH\53467-96.DIV 23/1/98 -36- PREPARATION EXAMPLE 32 Preparation of 4-i3-bromopropyl)sulfonlmethyl-4'chlorobenzophenone (Compound No. VI-ll) 4-(3-bromopropyl)thiomethyl-4'-chlorobenzophenone (5.1 g) and a 31% hydrogen peroxide aqueous solution (6 g) was added to acetic acid (200 ml), and the mixture was stirred for one hour at 80 0 C and further for one hour under reflux. The reaction mixture was concentrated, and water was added thereto. The mixture was extracted with ethyl acetate. The ethyl acetate layer was washed with So.
an aqueous potassium carbonate solution and water and .i dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure. The residual solid was washed with n-hexane to obtain the desired product (5.0 g, melting pint: 105 to 1070C, yield: 91%).
H-NMR data (60MHz, CDC13 solvent, 6 value) 2.17-2.60 (2H, m) 3.00-3.17 (2H, m) 3.53 (2H, t) 4.33 (2H, s) 7.23-7.87 8H) PREPARATION EXAMPLE 33 Preparation of 4-chloro-4'-(l,l-dioxothiolan-2yl)benzophenone (Compound No. VI-36) 4-( 3 -bromopropyl)sulfonylmethyl-4 -chlorobenzophenone g) and 60% sodium hydride (0.3 g) were added to N,Ndimethylacetamide (70 ml), and the mixture was stirred for 16 hours at room temperature. Water was added to the P:\OPER\RMH\53467-96. DIV 23/1/98 -37reaction mixture, and the mixture was extracted with ethyl acetate. The ethyl acetate layer was washed with water and then dried over anhydrous magnesium sulfate.
Ethyl acetate was distilled off under reduced pressure.
The residue was purified by silica gel column chromatography (n-hexane:ethyl acetate=l:l) to obtain the desired product as a slightly yellow viscous substance g, yield: 1 H-NMR data (60MHz, CDC1 3 solvent, 8 value) 10 2.67-2.73 (4H, m) 2.87-3.33 (2H, m) 4.02-4.37 (1H, m) :7.23-7.97 (8H, m) PREPARATION EXAMPLE 34 15 Preparation of 4-chloro-4'-(2trifluoromethylsulfonylpropyl)benzophenone (Compound No.
VI-28) 4-chloro-4'-trifluoromethylsulfonylmethylbenzophenone (3.3 g) and 60% sodium hydride (0.8 g) were added to N,Ndimethylacetamide (150 ml), and the mixture was stirred for one hour at room temperature. Methyl iodide (0.8 g) was added to this solution, and the mixture was stirred for 16 hours at room temperature. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The ethyl acetate layer was washed with water and then dried over anhydrous magnesium sulfate.
Ethyl acetate was distilled off under reduced pressure.
The residue was purified- by silica gel column P:\OPER\RMH\53467-96. DIV 23/1/98 -38chromatography (n-hexane:ethyl acetate=4:l) to obtain the desired product (3.1 g, melting point 107 to 109 0
C,
yield: 86%).
IH-NMR data (60MHz, CDC1 3 solvent, 6 value) 2.00 (6H, s) 7.20-7.70 (8H1, m) PREPARATION EXAMPLE Preparation of 4-chloro-4 -thiocyanatomethvlbenzophenone (Compound No. 4-bromomethyl-4 -chlorobenzophenone (5.7 g) and sodium thiocyanate (5.5 g) were added to ethanol (50 ml), and the mixture was stirred for one hour at 600C. The reaction mixture was concentrated, and water was added to the residue. The mixture was extracted with ethyl acetate. The ethyl acetate layer was washed with water and then dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure. The residual solid was washed with a solvent mixture of n- ~hexane;ethyl acetate=l0:1 to obtain the desired product (2.2 g, melting point: 129 to 131 0 C, yieJld:42%).
1 H-NM4R data (60MHz, CDC1 3 solvent, 6 value) 4.18 (2H, s) 7.23-7.87 (8H1, PREPARATION EXAMPLE 36 Preparation of diethyl 4-chlorobenzoyl)phenJ. -2trifluoromethylthiomalonate (Compound No. VI-8O) sodium hydride g) was dispersed in P:\OPER\RMH\53467-96. DIV 23/1/98 -39tetrahydrofuran (150 and diethyl chlorobenzoyl)phenyl) malonate (4.4 g) was dropwise added thereto at 0 0 C with stirring. After generation of hydrogen ceased, trifluoromethylsulphenyl chloride was blown thereinto at OOC, and the mixture was then Stirred for one hour at room temperature. The reaction mixture was concentrated, and water was added to 'the residue.
The mixture was extracted with ethyl acetate. The ethyl acetate layer was washed with water and then dried over anhydrous magnesium sulfate. Ethyl acetate was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane~ethyl acetate=8;1) to obtain the desired product (4.7 g, n.D0.1.5362, yield:87%).
1 Hi-NMR data (60MHz, CDC1 3 solvent, 6 value) 1.3 (6H, t) .4.35 (4H, q) 7.4 (2H, d) 7.75 (2H, d) .20 7.8 (4H1, s) PREPARATION EXAMPLE 37 Preparation of 4-chloro-4'trichloromethlthiomethvlbenzophen2~on~uq!Cd.VT 81) Methylbenzophenone 4 -chloro-4'-thiocyanate (5.5 g) and triethylbenzylammonium chloride (0.5 g) were dispersed in chloroform (30 ml), and a 48% sodiuim P:\OPER\RMf\53467-96.DIV 23/1/98 hydroxide aqueous solution (4 ml) was added thereto at Then, the mixture was stirred for 3 hours.
Cool water was added thereto, and the mixture was subjected to liquid separation. The organic layer was washed with water and dried over anhydrous magnesium sulfate. Then, chloroform was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (n-hexane:ethyl acetate=9:l) to obtain the desired product (1.0 g, melting point: 103 to 10 105°C, yield: 13%).
1
I
1 -NMR data (60MHz, CDC1 3 solvent, 6 value) 4.45 (2H, s) 7.15-7.8 (8H, m) PREPARATION EXAMPLE 38 15 Preparation of 4-chloro-4'trifluoromethylsulfonvlmethylbenzhydrol (Compound Mo.
VIII-2) 4-chloro-4'-trifluoromethylsulfonylmethylbenzophenone (5.5 g) was dispersed in methanol (200 ml). Sodium borohydride was gradually added thereto at room temperature with stirring, and the mixture was further stirred overnight at room temperature. After completion of the reaction, methanol was distilled off under reduced pressure. The residue was extracted with ethyl acetate (250 ml). The extract was washed with water and dried over anhydrous magnesium sulfate. Then, ethyl acetate was distilled off under reduced pressure. The residue
F-
P:\OPER\RMH-\53467-96. DIV 23/1/98 41 was purified by silica gel column chromatography (nhexane:ethyl acetate=2:1) to obtain the desired product as a white powder (4.2 g, melting point: 113 to 115 0
C,
yield: 77%).
1 HE-NMR data (60MHz, CDC1 3 solvent, 8 value) 4.7 (2H, s) 5.77 (2H, s) 7.3 (4H1, s) 7.47 (4H1, s) PREPARATION EAPE39 Preparation of 4 -chloro-41-ethane *sulfonvlmethylbenzhydryl chloride (Compound No. S4-chloro-4 '-ethane sulfonylmethylbenzhydrol (6.0 g), thionyl chloride (5.4 toluene (200 ml) and a 15 catalytic amount of NfN-dimet hylforrnamide were mixed and gradually heated with stirring to a refluxing temperature. The mixture was stirred for 4 hours under reflux and then left to cool. Then, the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (nhexane:ethyl acetate=2:l) to obtain the desired product as a slight yellow viscous substance 4 .6g, nD 20 1.6044, yield: 1 'I-Nl4R data (60MHz, CDC1 3 solvent, 6 valule) 1.33 (3F, t) 2.88 (2H, q) 4.37 (2H, s) P:\OPER\RMH\53467-96. DIV 23/1/98 42 6.05 (ls) 7.27 (4H1, s) 7.35 (4H1, s) PREPARATION EXAMPLE Preparation of 6-chloro-3-pyridyl)(4trifluoromethylphenyl) ketone (Compound No. VII-3) (6-chloro-3-pyridyl) 4 -thicyanatemethylphenyl) ketone g) was dissolved in te'trahydrofuran (300 ml), and trifluoromethyltrimethyl silane (5.0 g) was added thereto at room temperature. Then, the mixture was cooled to Tetrabutylammonium fluoride (1.0 M tetrahydrofuran :::isolution, 23 g) was gradually dropwise added thereto :under cooling, and then, the mixture was stirred over night. Tetrahydrof ran was distilled off under reduced pressure, and the residue was extracted with ethyl acetate. The extract was washed with water and dried over anhydrous magnesium sulfate. Then, ethyl acetate was distilled of f under reduced pressure. The residue was purified by silica gel column chromatography (nhexarie:ethyl acetate=4:1) to obtain the desired product g, nD 0 1.5820, yield: 2H-NMR data (6014Hz, CDC1 3 solveot, c 5 value) 4.15 (29, s) 7.4 (3H1, dd) 7.72 (2H1, dd) 8.05 (211, dd) 8.67 (2H1, d) P: \OPER\RMH\53467-96. DIV 23/1/98 -43- The benzylsulfide derivatives of the formula
(II)
of the present invention are suitable for use as intermediates in the production of novel benzylsulfide derivatives of the formula Specific examples thereof, use of the benzylsulfide derivatives of the formula so produced as a pesticide, and pesticides containing same as the active ingredient are disclosed in the hereinbefore mentioned Australian Patent Application No. 53467/96.
.e oo P:\OPER\RMH\53467-96.DIV 23/1/98 -44- THE CLAIMS DEFINING THE INVENTION ARE AS FOLLOWS: 1. A benzylsulfide derivative of the formula
(II):
R
2 C
S
OnR I I
R
3 4 R wherein
R
1 is a C-6 alkyl group, a C 1 4 cyanoalkyl group, a C,_4 hydroxyalkyl group, a C 3 -6 cycloalkyl group, a C1- 6 1 0 haloalkyl group, a C2- 4 alkenyl group, a C 2 -4 alkynyl group, a phenyl group (which may be substituted by a halogen atom or a C 1 4 alkyl group), a cyano group, a benzyl group (which may be substituted by a halogen atom), a thiazolyl group, a C1-4 alkylcarbamoyl group or a group of the formula -N(R 5
)R
6 each of R 2 and R 3 which are independent of each other, is a hydrogen atom, a o* o halogen atom, a cyano group, a Cl_ alkyl group, a C 1 3 haloalkyl group, a C,_ 4 alkylthio group, a C 1 4 alkylcarbonyl group, a carboxyl group, or a C_ 4 alkoxycarbonyl group; or R 2 and R 3 may form a 3- to 6membered ring together with the carbon atom to which they are bonded; or R 1 and R 2 may form a 3- to 8-membered ring having one or more hetero atoms, together with the sulfur and carbon atoms to which they are respectively bonded;
R
4 is a hydrogen atom, a halogen atom, a C,_ 4 alkyl group, a C 1 4 haloalkyl group, a C 1 4 alkoxy group or a
C
1 4 haloalkoxy group; each of R 5 and R 6 which are

Claims (1)

  1. 4- to 8-membered ring together 9 10 with the carbon atom to which they are banded; B is an aralkyl or arylcarbonyl group of the formula (Bi) or (B2):R 2 9 9 IlQ Q 2 R 1 [B [i B23J R 9 is a hydrogen atom, a halogen atom, a nitro group, a **cyano group, a C,- 4 alkyl group, a C 1 4 haloalkyl group, a 0* alkoxy group, a C 4 haloalkoxy group, aC alkylthio group, a C 1 4 haloalkylthio group, a C 1 4 alkylsulfony. group, a C 2 4 alkylsulfonylmethyl group, a C 1 4 haloalkylsulfonyloxy group, a phenyl group (which may be substituted by a halogen atom) or a phenoxy group (which-may be substituted by a halogen atom); or two R 9 may together form a 5- or 6-inembered ring; R 1 0 is a hydrogen atom or a C 1 4 R 2 1 is a halogen atom or a hydroxyl group; each of Q 1 and Q 2 is a nitrogen atom or a P:\OPER\RMH\53467-96.DIV 13/1/99 -46- group of the formula -CR 9 m is an integer from 1 to 3; and n is 0, 1 or 2. 2. A benzylsulfide derivative of the formula (II) as defined in claim 1, when used as an intermediate in the preparation of a benzylsulfide derivative of the formula as hereinbefore defined. 3. Benzylsulfide derivatives of formula (II) substantially as hereinbefore described with reference to the Examples. DATED this 13th day of January, 1999 15 Kumiai Chemical Industry Co. Ltd and Ihara Chemical Industry Co. Ltd by DAVIES COLLISON CAVE Patent Attorneys for the Applicants oe *ee eee P:\OPER\RMI-1\5346796. DIV .23/1/98 ABSTRACT The present invention provides a benzylsulfide derivative of the formula (II): R 2 B C SOnR 3 R 4 R 10 wherein Ri is a C 1 6 alkyl group, a Cl, 6 haloalkyl group, a, C 2 -4 alkenyl group, a cyano group, etc., and each of R 2 and R 3 is a hydrogen atom, a halogen atom, a cyano group, a C.-4 alkyl group, a C 1 3 haloalkyl group, etc., R is a hydrogen atom, a halogen atom, a C 1 4 alkyl group, etc., B is an aralkyl group or arylcarbonyl group, and n is 0, 1 or 2; suitable for use as an intermediate for the production of novel benzylsulfide pesticides. o* ooi
AU52800/98A 1995-04-19 1998-01-29 Benzylsulfide derivatives suitable for use as intermediates in the production of pesticides Ceased AU703619B2 (en)

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JP7-117838 1995-04-19
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