WO2001010843A1 - Derives de 4-(phenyl substitue)-5-halopyrimidine et herbicides contenant ces derives comme ingredients actifs - Google Patents

Derives de 4-(phenyl substitue)-5-halopyrimidine et herbicides contenant ces derives comme ingredients actifs Download PDF

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WO2001010843A1
WO2001010843A1 PCT/JP2000/005222 JP0005222W WO0110843A1 WO 2001010843 A1 WO2001010843 A1 WO 2001010843A1 JP 0005222 W JP0005222 W JP 0005222W WO 0110843 A1 WO0110843 A1 WO 0110843A1
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atom
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hydrogen atom
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Masashi Kishida
Fumihiko Ohno
Bunji Natsume
Shinji Kawaguchi
Noriko Katagiri
Osamu Ikeda
Hahime Motegi
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Mitsubishi Chemical Corporation
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/32—One oxygen, sulfur or nitrogen atom
    • C07D239/42—One 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • 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
    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
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    • C07D211/10—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with radicals containing only carbon and hydrogen atoms attached to ring carbon atoms
    • C07D211/16—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with radicals containing only carbon and hydrogen atoms attached to ring carbon atoms with acylated ring nitrogen atom
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    • C07D211/20—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms with hydrocarbon radicals, substituted by singly bound oxygen or sulphur atoms
    • C07D211/22—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms with hydrocarbon radicals, substituted by singly bound oxygen or sulphur atoms by oxygen atoms
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    • C07D211/18—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D211/30—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms with hydrocarbon radicals, substituted by doubly bound oxygen or sulfur atoms or by two oxygen or sulfur atoms singly bound to the same carbon atom
    • C07D211/32—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms with hydrocarbon radicals, substituted by doubly bound oxygen or sulfur atoms or by two oxygen or sulfur atoms singly bound to the same carbon atom by oxygen atoms
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    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members 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
    • C07D211/40—Oxygen atoms
    • C07D211/44—Oxygen atoms attached in position 4
    • C07D211/46—Oxygen atoms attached in position 4 having a hydrogen atom as the second substituent in position 4
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    • 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
    • C07D213/24—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 substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/36—Radicals substituted by singly-bound nitrogen atoms
    • C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
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    • 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
    • C07D213/72—Nitrogen atoms
    • C07D213/74—Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon radicals
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    • C07D217/06—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with only hydrogen atoms or radicals containing only carbon and hydrogen atoms, directly attached to carbon atoms of the nitrogen-containing ring; Alkylene-bis-isoquinolines with the ring nitrogen atom acylated by carboxylic or carbonic acids, or with sulfur or nitrogen analogues thereof, e.g. carbamates
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    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
    • C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
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    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
    • C07D317/50—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to atoms of the carbocyclic ring
    • C07D317/58—Radicals substituted by nitrogen atoms
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    • C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
    • C07D317/62—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring 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 atoms of the carbocyclic ring
    • C07D317/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
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    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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Definitions

  • the present invention relates to a novel 4-substituted phenyl-5-halopyrimidine derivative, a herbicide containing the same as an active ingredient, and an intermediate effective for producing the derivative.
  • Desirable herbicide conditions include having a high herbicidal effect at a low dose, having a broad herbicidal spectrum, having an appropriate residual effect, and having sufficient safety for crops, etc.
  • many of the existing herbicides do not fully satisfy these conditions.
  • various studies have been made to solve such problems relating to herbicides. For example, as a compound having a structure having a nitrogen-containing hetero ring and a substituted phenyl group, a tetrahydrophthalimid ring has been proposed.
  • Various studies have been made to use a compound having a structure in which a phenyl group is bonded to an N atom as an active ingredient of a herbicide.
  • An object of the present invention is to provide a novel compound having a high herbicidal activity, a broad herbicidal spectrum, and high safety for crops. Disclosure of the invention
  • the present inventors have conducted intensive studies on the synthesis of 4-substituted phenyl-5-halopyrimidine derivatives and their herbicidal activity in order to solve the above-mentioned problems of the herbicides. As a result, it was found that a phenyl group having a specific substituent was found.
  • 5-Halopyrimidine derivatives which are substituents at the 4-position of the pyrimidine ring, are particularly characterized by a substituent on the pyrimidine ring and a substituent on the phenyl group. It has been found that a 5-halopyrimidine derivative, which is a certain combination, has a high herbicidal effect and shows sufficient safety for some important crops, thereby completing the present invention.
  • the 4-substituted phenyl-5-halopyrimidine derivative according to the present invention is represented by the general formula (I).
  • j and k both indicate 0, or one of them is 0 and the other is 1. Among these, it is preferable that both j and k are 0.
  • Z is a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a chlorine atom or a bromine atom, and particularly preferably a chlorine atom.
  • R 1 and R 2 are each independently the following groups:
  • a 1 is an oxygen atom, a sulfur atom, a sulfinyl group, a sulfonyl group, or a group represented by 1 NR 4 —, and the above R 4 is a hydrogen atom; or a linear or branched alkyl group, It is an alkenyl group or an alkynyl group.
  • R 3 is a hydrogen atom; or a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group which may be optionally substituted (the above substituents include a halogen atom and an alkoxycarbonyl group. ). ).
  • alkyl group alkenyl group and alkynyl group in R 1 and R 2
  • lower groups having 8 or less carbon atoms are preferred, and those having 6 or less carbon atoms are particularly preferred.
  • R 1 is preferably 1) a halogen atom, 2) a linear or branched alkyl group, alkenyl group or alkynyl group which may be optionally substituted (as the substituent, a halogen atom and a hydroxyl group are preferred) . cited), or 3) - group (wherein represented by a i- R 3a, a 1 are as defined above, R 3a is (c port) alkyl group, an alkenyl or alkynyl group And more preferably a Ci—C 6 alkyl group, a C!
  • —C 6 haloalkyl group or a group represented by one A la —R 3b (where A la is an oxygen atom, A sulfur atom or —NH—, and R 3b is a C 6 alkyl group or a C i —C 6 haloalkyl group.) And particularly preferably, a C 3 alkyl group, a haloalkyl group, or an alkoxy group. And a group selected from a haloalkoxy group.
  • R 2 is preferably a hydrogen atom, an alkyl group, an alkoxy group or an alkylthio group, and more preferably a hydrogen atom, a Ci—C 6 alkyl group, a Ci—C 6 alkoxy group or a C—C 6 group. O, particularly preferably a hydrogen atom o
  • Ar is a group represented by the following general formula (Ar-1) or (Ar-2).
  • Y is a hydrogen atom or a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and is preferably a hydrogen atom, a fluorine atom, or It is a chlorine atom, more preferably a fluorine atom.
  • X is a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or a cyano group, preferably a fluorine atom, a chlorine atom or a bromine atom, and more preferably a chlorine atom.
  • R 5 is 1) a hydrogen atom; 2) a linear or branched alkyl group which may be optionally substituted (the above substituent includes a halogen atom, an acyloxy group and an alkoxy group. An alkylenedioxy group may be bonded to the same carbon of the group); 3) a nitro group, or 4) a compound represented by the following formulas (II) to (IV):
  • a 2 represents an oxygen atom, a sulfur atom, a sulfinyl group, a sulfonyl group, or a group represented by —NR 7 —
  • R 7 is 1) a hydrogen atom; 2) an optionally substituted straight-chain, branched or cyclic alkyl group, alkenyl group or alkynyl group (the above substituents include a halogen atom, an alkoxy group And phenyl groups). 3) acetyl, propionyl, butyryl, isoptyryl, valeryl, isovaleryl, 2-methylbutyryl, hexanoyl, 2,2-dimethylbutyryl, 2-ethylbutyryl, 2-methylvaleryl, 3-methylvaleryl An acyl group such as a 4-methylpareryl group;
  • alkoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, proviroxycarbonyl group, isopropyloxycarbonyl group, butoxycarbonyl group, pentyloxycarbonyl group;
  • R 6 is 1) a hydrogen atom; 2) a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group which may be optionally substituted (the above substituent is a nitrogen atom, a cyano group , An alkoxy group, an alkylthio group, an alkylsulfonyl group, an acyl group, a phenyl group and a 3- to 6-membered heterocyclic group.);
  • acyl group such as a 4-methylvaleryl group
  • R 8 and R 9 each independently represent a hydrogen atom; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Atoms; linear or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl; or acetyl, propionyl, It is an acyl group such as a butyryl group and an isoptyryl group.
  • W 1 is an oxygen atom, a sulfur atom, or a group represented by —NR 11 —
  • R 1 1 is hydrogen;.
  • R 1 Q is: 1) a hydrogen atom
  • An acyl group, an acyloxy group, a group represented by C ( 0) OR 12 (wherein, R 12 is a hydrogen atom, an alkyl group, an alkenyl group, or an alkynyl group, ), A phenyl group, and
  • T is an oxygen atom or a group represented by N—OR 6 (wherein R 6 has the same meaning as in the general formula (II)); R 15 is a hydrogen atom or a linear or branched alkyl group.
  • alkyl group alkenyl group, the alkynyl group, Ashiru group, Ashiruokishi group, an alkoxycarbonyl group, an alkoxy group, an alkyl Chiomoto, an alkylsulfonyl group, ⁇ Luque sulfonyl sulfonyl group, carbon Lower ones having a number of 8 or less are preferred, and those having 6 or less carbon atoms are particularly preferred.
  • R 5 is preferably 1) a hydrogen atom; 2) a linear or branched alkyl group which may be arbitrarily substituted (the above substituents include a halogen atom, an acyloxy group and an alkoxy group. An alkylenedioxy group may be bonded to the same carbon of the alkyl group.); 3) a nitro group, or 4) a group represented by the following formulas (II) 'to (IV)'.
  • ⁇ represents an oxygen atom, a sulfur atom, a sulfinyl group, or a group represented by —NR 7a — (wherein, R 7a represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl Group, an alkoxycarbonyl group, or an (c) alkylsulfonyl group.).
  • R 6a is 1) a hydrogen atom; 2) optionally substituted, linear, branched or branched Is a cyclic alkyl group, alkenyl group, or alkynyl group (the substituents include a halogen atom, a cyano group, and a phenyl group);
  • W la is an oxygen atom, a sulfur atom, or a group represented by —NR 1 la — (where R R la represents a hydrogen atom or an alkyl group).
  • R 1Qa is a hydrogen atom; a linear, branched or cyclic alkyl, alkenyl, or alkynyl group; or an alkyl group substituted with a phenyl group.
  • L has the same meaning as described in the general formula (III), and W 2 represents an oxygen atom, a sulfur atom, or a group represented by —NR 11 lb— (in the formula, ,: R 1 is a hydrogen atom, an alkyl group, or an alkoxy group.).
  • T 1 is an oxygen atom or a group represented by N—0R 6b (in the formula, R 6b is a hydrogen atom; a linear, branched or cyclic alkyl group, alkenyl group, or An alkynyl group; an alkoxycarbonylalkyl group, an alkenyloxycarbonylalkyl group or a carboxyalkyl group), and R 15 has the same meaning as that in the above formula (IV).
  • R 5 is particularly preferably a hydrogen atom or a group represented by the following general formulas (II) '' to (IV).
  • a 2b is an oxygen atom, a sulfur atom, or a group represented by —NR 7b — (where R 7b is a hydrogen atom, a C ⁇ —C 6 alkyl group Or 1 C 6 alkylsulfonyl group.), And particularly preferably an oxygen atom.
  • R 6b is, CI- (iii port) alkyl C 6, C 2 - (C port) alkenyl group C 6, C 2 - alkynyl group C 6, C 3 - cycloalkyl group C 6, C 2 — A C 6 alkyl group or a group represented by the general formula (V) ′.
  • W lb is an oxygen atom or a group represented by one NR 1 le — (wherein, R l lc is a hydrogen atom or a C i —C 4 alkyl group) R 8a is a hydrogen atom or a C i —C 4 alkyl group, R 9a is a hydrogen atom or a methyl group, R 10d is a Ci—C 6 alkyl group, C 2 — C 6 alkenyl group or C 3 —C 6 cycloalkyl group.)
  • W 2a is an oxygen atom, a sulfur atom, or a group represented by —NR l ld — (wherein, R 1 is a hydrogen atom, a C 1 -C 4 alkyl group, Or a C i -C 4 alkoxy group.).
  • R 1 Qc is a hydrogen atom, an alkyl group of Ci—Cs, C 2 Alkenyl group -c 6, c 2 - alkynyl group c 6, c 3 - a cycloalkyl group c 6,
  • R 1Qe is a hydrogen atom or a C 6 alkyl group.
  • R 13 and R 14 R 13 is preferably a hydrogen atom
  • R 14 is a hydrogen atom, a chlorine atom or a methyl group.
  • T 2 is a group represented by N—OR 6e (where R 6c is a C 6 alkyl group, C 2 —C 6 alkenyl group, C 2 — C 6 alkynyl group or C 3 -C 8 alkoxycarbonylalkyl group
  • R 6 is Ru synonymous der and R 6 in the general formula (II).
  • a hydrogen atom; or a chain, branched or cyclic alkyl group, alkenyl group or alkynyl group which may be optionally substituted, and particularly preferably a Ci—C 6 ) alkyl group, (iii port of C 2 -C 6) alkenyl group, C 2 - alkynyl group C 6, C 3 - cycloalkyl group C 6, or CH (with R 8a) C ( 0) oR 1Qc Wherein R 8a is a hydrogen atom or a C i -C 4 alkyl group, and R 10c is a C -C 6 alkyl group.
  • U is a group represented by an oxygen atom, a sulfur atom or —NH—, preferably an oxygen atom or a sulfur atom, and particularly preferably an oxygen atom.
  • n is 0 or 1, and preferably 1.
  • the 2,4-dihalophenylboric acid derivative represented by the following general formula (VI) is an important intermediate for synthesizing the compound (I) of the present invention, and is a novel compound.
  • X 1 is preferably a fluorine atom or a chlorine atom, and particularly preferably a chlorine atom.
  • Y 1 is preferably a fluorine atom or a chlorine atom, and particularly preferably a fluorine atom.
  • R 16 is a hydrogen atom; or a linear or branched alkyl group, or two R 16s taken together to form an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, or the like. May form an alkylene group.
  • a lower alkyl group having 6 or less carbon atoms is preferable, and an alkyl group having 4 or less carbon atoms is particularly preferable.
  • the alkylene group preferably has 2 to 8 carbon atoms, and particularly preferably has 2 to 6 carbon atoms.
  • R 16 is particularly preferably a hydrogen atom.
  • R 17 is a group excluding the hydrogen atom and the methoxy group from the groups exemplified as R 5 above, and is preferably an alkyl group, a haloalkyl group, a nitro group, a group represented by —A 2c —R 6c (Wherein, A 2e is an oxygen atom or a sulfur atom, and R 6e is substituted with a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group, haloalkyl group, or 1-2 phenyl groups.
  • R 6 is a group other than a methyl group.
  • a formyl group or a group represented by the following general formula (VI I)
  • R 18 and R 19 each independently represent an alkyl group, and R 18 and R 19 And may form a C 2 -C 8 alkylene group.).
  • the alkyl group, alkenyl group or alkynyl group is preferably a lower group having 8 or less carbon atoms, particularly preferably a group having 6 or less carbon atoms.
  • 3-dimethylbutyl group 3,3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1,1,2-trimethylpropyl group, 1-ethyl-1-methylpropyl group, 1-ethyl-2-methylpropyl group ;
  • Hydroxymethyl group 1-hydroxyxethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 1-hydroxybutyl group, 1-hydroxypentyl group, 1-hydroxyhexyl group;
  • Acetyloxymethyl group 1- (acetyloxy) ethyl group, 2- (acetyloxy) ethyl group, 1- (propionyloxy) ethyl group, 2- (propionyloxy) ethyl group, 2- (butyryloxy) ethyl group Group, 2- (isobutyryloxy) ethyl group, 2- (valeryloxy) ethyl group, 2- (isovaleryloxy) ethyl group, 2- (bivaloyloxy) ethyl group, 2- (acryloyloxy) ) Ethyl group, 2- (propioyloxy) ethyl group, 2- (methacryloyloxy) ethyl group, 2- (crotonyloxy) ethyl group, 3- (acetyloxy) propyl group, 41- (acetyloxy) group Butyl group, 5- (acetyloxy) pentyl group; methoxy
  • 2,2,2-Trifluoroethoxycarbonylmethyl group 1- (2,2,2-Trifluoroethoxycarbonyl) ethyl group, 1-Methyl-1- (2,2,2-Trifluoro Ethoxycarbonyl) ethyl group;
  • Propargyloxycarbonylmethyl group 1- (propargyloxycarbonyl) ethyl group, 1-methyl-1- (propargyloxycarbonyl) ethyl group; carboxymethyl group, 1-carboxyethyl group, 2-carboxyethyl group, 1-carboxypropyl group, 2-carboxypropyl group, 3-carboxypropyl group, 1-carboxy-1-methylethyl group;
  • Methoxymethyl group, ethoxymethyl group, propoxymethyl group isopropoxymethyl group, butoxymethyl group, 2-methoxyxyl group, 2-ethoxyxyl group, 2-propoxyethyl group, 2-isopropoxyethyl group, 2-butoxyethyl group , 3-methoxypropyl group, 4-methoxybutyl group, 5-methoxypentyl group; Dimethoxymethyl group, diethoxymethyl group, dipropoxymethyl group, diisopropoxymethyl group, dibutoxymethyl group, bis (pentyloxy) methyl group, bis
  • Ethylenedioxymethyl group trimethylenedioxymethyl group, tetramethylenedioxymethyl group, benzenemethylenedioxymethyl group, hexamethylenedioxymethyl group;
  • 2-oxopropyl group 1-methyl-2-oxopropyl group, 1-methyl-2-oxobutyl group, 1-ethyl-2-oxopropyl group, 1-propyl-2-oxopropyl group;
  • Benzyl group 1-phenylethyl group, 2-phenylethyl group, 1-phenylpropyl group, 3-phenylpropyl group, 1-methyl-1-phenylphenyl group, diphenylmethyl group;
  • 2-cycloprobenyl group 2-cyclobutenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 2-cyclohexenyl group, 3-cyclohexenyl group;
  • 2-chloroallyl group 2-bromoallyl group, 3- Chloroallyl group, 3-bromoaryl group, 2,3-dichloroallyl group, 3,3-dichloroallyl group, 2-chloro-2-butenyl group, 3-chloro-2-butenyl group;
  • Ethynyl 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3 _Pentynyl, 4-pentynyl, 1-methyl-3-butynyl, 1,1-dimethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4- Hexynyl group, 5-hexynyl group.
  • 3- to 6-membered heterocyclic group described in the above description of the substituent include, for example, those containing 13 oxygen atoms, sulfur atoms and / or nitrogen atoms shown below. Is mentioned.
  • substituents R 5, R 6, 13 ⁇ 4 7 and 1 1 (but if a groups including phenyl group or a 3-6 membered double ring group, the phenyl group and the heterocyclic group, a fluorine atom Halogen atoms such as, chlorine, bromine, and iodine; Ci—C 4 such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, and t-butyl; C i -C 4 haloalkyl group such as trifluoromethyl group; methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, t-butoxy ⁇ alkoxy group of CI- C 4 such groups; Asechiruokishi group, a propionyloxy Ruo alkoxy group, Puchiriruokishi group, I Sobuchiriruokishi group, Bruno Rerir
  • the compound of the present invention represented by the general formula (I) can be produced, for example, according to any of the following production methods.
  • Manufacturing method (1) R 2 N person Ar
  • J is a halogen atom such as a chlorine atom, a bromine atom, or an iodine atom; a lower alkylsulfonyl group such as a methylsulfonyloxy group.
  • a lower haloalkylsulfonyloxy group such as a trifluoromethylsulfonyloxy group; or an arylsulfonyloxy group such as a p-toluenesulfonyloxy group, wherein K is — B (OR 16 ) 2 (R 16 represents a hydrogen atom or an alkyl group.
  • R 16 may be taken together to form an alkylene group.
  • -Sn (R 20 ) 3 R 20 is an alkyl group Represents a group.
  • -M 1 M 1 represents a monovalent metal atom such as lithium and sodium
  • — M 2 — Q M 2 represents a divalent metal such as magnesium, zinc and copper
  • Q represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. Represents a halogen atom.
  • the process comprises the steps of: pyrimidines (VI II); substituted phenylboronic acids; substituted phenyltrialkyltins; substituted phenylmetal halides such as substituted phenyl Grignard reagents or substituted phenyl zinc halides.
  • the compound (I-A) of the present invention is produced by coupling the compound (IX) with the compound (IX).
  • the above reaction is carried out in the absence of a solvent or in a solvent inert to the reaction, usually at a temperature of from 120 to 200 ° C, preferably from 0 to 150 ° C.
  • the amount of the compound used in the reaction is usually 1.0 to 3.0 equivalents, preferably 1.0 to 1.5 equivalents of the compound (IX) to 1 equivalent of the compound (VIII).
  • the above reaction is preferably performed in a solvent.
  • Suitable solvents to be used include aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane; and aromatic hydrocarbons such as benzene, toluene, xylene and cumene.
  • Hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, etc .; getyl ether, diisopropyl ether, dibutyl ether, dimethoxetane, Ethers such as tetrahydrofuran and dioxane; esters such as ethyl acetate and butyl acetate; ketones such as acetone and methylethyl ketone; alcohols such as methanol, ethanol and propanol; nitriles such as acetonitrile; —Dimethylformamide, N-Methylpyro Water;, dimethyl sulfoxide, non pro ton polar solvents such as sulfolane ⁇ beauty mixed solvent of two or more thereof.
  • the amount of the solvent to be used is usually within 100 times, preferably 1 to 50 times, the
  • the above reaction is optionally used in combination with 1) a metal or metal complex catalyst, and 2) a base.
  • metal or metal complex catalyst examples include metals such as nickel, iron, ruthenium, cobalt, rhodium, iridium, palladium, and platinum; tetrakis (triphenylphosphine) palladium, tris (dibenzylideneaceton) dipalladium.
  • the amount of the metal or metal complex catalyst to be used is generally 0.01 to 1.0 equivalent, preferably 0.01 to 0.5 equivalent, per 1 equivalent of compound (V
  • Examples of the base include triethylamine, N, N-diisopropylethylamine, Biridine, bicholine, lutidine, collidine, N, N-Jetylaniline, 41- (dimethylamino) pyridine, 1,8-diazabicyclo [5.4.0] — 7-indene, 1,5-diazabicyclo [4. 3.
  • Nitrogen-containing organic bases such as octane; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; sodium carbonate, potassium carbonate, and carbonic acid Alkali metal or alkaline earth metal carbonates such as calcium; sodium bicarbonate, alkaline metal bicarbonates such as hydrogencarbonate lithium; sodium methoxide, sodium methoxide, potassium t-butoxide, etc. Metallic alcohols and the like.
  • the amount of the base to be used is generally up to 5 equivalents, preferably up to 2 equivalents, per 1 equivalent of compound (VIII).
  • phase transfer catalyst may be added to the reaction system.
  • the phase transfer catalyst used include quaternary ammonium salts such as tetrabutylammonium bromide, tetrabutylammonium chloride, and benzyltriethylammonium chloride.
  • the amount of the phase transfer catalyst to be used is generally within 2 equivalents, preferably within 1 equivalent, relative to 1 equivalent of the compound (VIII).
  • the compound (I-C) or (I-D) of the present invention is produced by halogenating the compound (I-B) of the present invention.
  • the inventive compound (IB) can be produced, for example, by the above-mentioned production method (1).
  • a halogenating agent is carried out without solvent or in a solvent inert to the reaction.
  • the temperature is usually in the range of 0 to 200 ° C., preferably 0 to 150 ° C.
  • the halogenating agent to be used include fluorine, chlorine, bromine, iodine, N-methyl succinimide, N-prosuccinimide, N-succinimide, sulfuryl chloride and the like.
  • the amount of the halogenating agent is 1.0 to 5.0, preferably 1.0 to 2.5 equivalents relative to 1 equivalent of the compound (IB).
  • Suitable solvents used include aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane; aromatic hydrocarbons such as benzene; dichloromethane; Halogenated hydrocarbons such as chloroform, carbon tetrachloride, 1,2-dichloroethane, cyclobenzene, dichlorobenzene, etc .; Jethyl ether, diisopropyl ether, dibutyl ether, dimethoxetane, tetrahydrofuran, dioxane Ethers; esters such as ethyl acetate and butyl acetate; water; and a mixed solvent of two or more of these.
  • the amount of the solvent used is usually within 100 times, preferably 1 to 50 times, the weight of the compound (IB).
  • a radical initiator may be used, if necessary.
  • the radical initiator to be used include dibenzoyl peroxide, azobisisobutyronitrile (AIBN), and the like.
  • AIBN azobisisobutyronitrile
  • the amount of the radical initiator to be used per one equivalent of the compound (IB) is used. Is from 0.005 to 0.2 equivalent, preferably from 0.001 to 0.1 equivalent.
  • the compound (I-E) of the present invention is produced by reacting the compound (I-C) of the present invention with a lower carboxylic acid or a lower carboxylic acid salt.
  • the inventive compound (I-C) can be produced, for example, by the above-mentioned production method (2).
  • the above reaction is carried out without solvent or in a solvent inert to the reaction, in the presence or absence of a base, usually at a temperature in the range of 0 to 200 ° C; preferably 0 to 150 ° C.
  • a base usually at a temperature in the range of 0 to 200 ° C; preferably 0 to 150 ° C.
  • the lower carboxylic acid or carboxylate include acetic acid, propionic acid, butyric acid, sodium salt and potassium salt thereof, and the amount of the compound (I-C) is 1 equivalent to 1 equivalent. 0 to 3.0 equivalents, preferably 1.0 to: L. 5 equivalents.
  • Examples of the base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal or alkaline earth metal carbonates such as sodium carbonate, potassium carbonate and calcium carbonate; sodium hydrogen carbonate, hydrogen carbonate and the like.
  • Metal hydrides such as sodium hydride and the like; and the amount of compound (I-C) is 1.0 to 3. It is 0 equivalent, preferably 1.0 to 1.5 equivalent. However, when a carboxylate is used, a base need not be used.
  • Suitable solvents to be used include aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane; and aromatic hydrocarbons such as benzene, toluene, xylene and cumene.
  • Hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, etc .; getyl ether, diisopropyl ether, dibutyl ether, dimethoxetane, Ethers such as tetrahydrofuran and dioxane; esters such as ethyl acetate and butyl acetate; ketones such as acetone and methylethyl ketone; nitriles such as acetonitrile; N, N-dimethylformamide, N-methylpyrrolidone; Non-dimethyl sulfoxide, sulfolane, pyridine, etc. Water, and a mixed solvent of two or more thereof. The amount of solvent used is usually within 100 times the weight of compound (I-C), Or 150 times,
  • the compound (IG) of the present invention is produced by nitrating the compound (IF) of the present invention.
  • the inventive compound (IF) can be produced by the above-mentioned production method (1).
  • the above reaction is carried out by reacting a ditoxin with a solvent at a temperature of usually ⁇ 20 to 150 ° C., preferably ⁇ 10 to 80 ° C. in a solvent or in a solvent inert to the reaction.
  • nitrifying agent examples include a mixture of nitric acid or nitrate (sodium nitrate, potassium nitrate, etc.) and sulfuric acid, nitric acid, acetyl nitrate, nitrodimethyltetrafluoroborate, nitronium trifluoromethane sulfonate. And those commonly used as nitro-lumping agents.
  • the amount of the nitrating agent to be used is generally 1.03.0 equivalents, preferably 1.02.0 equivalents, per 1 equivalent of compound (IF).
  • the above reaction is preferably carried out in a solvent.
  • suitable solvents to be used include sulfuric acid, acetic acid, acetic anhydride, halogenated hydrocarbons (dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloromethane). Nitroalkanes (nitromethane, etc.), and mixed solvents of two or more of these.
  • the amount of the solvent used is within 100 times, preferably 1 to 50 times the weight of the compound (IF).
  • R 22 represents an alkyl group substituted with an alkyl group, an alkenyl group, a haloalkyl group, an alkoxyalkyl group, a cycloalkyl group, or a phenyl group. Shown.
  • the compound of the present invention is converted into a substituted phenol (I-I) by cleaving the ether bond of the substituted phenyl ether (I-H).
  • the substituted phenyl ethers (IH) can be produced by the production method (1).
  • the above reaction is carried out in the absence of a solvent or in a solvent inert to the reaction, in the presence of an acidic reagent, at a temperature of usually ⁇ 200 ° C., preferably ⁇ 10 ° C. to 150 ° C.
  • the acidic reagent include brenstead acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, and trifluoroacetic acid; and Lewis acids such as aluminum trichloride, boron trichloride, and boron tribromide.
  • the amount of the acidic reagent used is usually 1 to 100 equivalents to 1 equivalent of the compound (I—H).
  • Suitable solvents to be used include aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane; and aromatic hydrocarbons such as benzene, toluene, xylene and cumene.
  • Hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, cyclobenzene, dichlorobenzene; alcohols such as methanol, ethanol and propanol; N, Non-protonic polar solvents such as N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, and sulfolane; water; and a mixed solvent of two or more thereof.
  • the amount of the solvent to be used is usually within 100 times, preferably 150 times, the weight of the compound (I-H). Manufacturing method (6)
  • the substituted anilines (I-J) are produced by reducing the nitro compound (I-G) in the compound of the present invention.
  • the inventive compound (IG) can be produced by the above-mentioned production method (1) or (4).
  • the above-mentioned reduction reaction is usually carried out at 20 to 200 ° in the absence of a solvent or in a solvent inert to the reaction in the presence of a metal or metal compound and an acidic reagent. , Preferably in a temperature range of 50 to 150 ° C.
  • Examples of the above-mentioned metal or metal compound include metals or metal compounds usually used for the reduction reaction of a nitro group, such as iron, zinc, tin, and tin (II) chloride.
  • the amount of the metal or metal compound to be used is usually 1 to 20 equivalents, preferably 2 to 10 equivalents, per 1 equivalent of compound (IG).
  • the acidic reagent examples include inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as acetic acid.
  • the amount of the acid reagent to be used is usually 0.01 to 20 equivalents per 1 equivalent of the compound (IG). The amount is preferably 0.01 to 10 equivalents.
  • Suitable solvents to be used include aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane; and aromatic hydrocarbons such as benzene, toluene, xylene and cumene.
  • Halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, etc .
  • Jethyl ether diisopropyl ether, dibutyl ether, dimethoxetane, tetrahi Ethers such as drofuran and dioxane
  • esters such as ethyl acetate and butyl acetate
  • ketones such as acetone and methyl ethyl ketone
  • alcohols such as methanol, ethanol and propanol
  • Nitriles such as cetonitrile
  • non-protonic polar solvents such as N, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide and sulfolane
  • organic acids such as acetic acid; water; and two or more of these A mixed solvent and the like can be mentioned.
  • the above reaction is carried out using sodium sulfide, sodium hydrosulfide, sodium dithionite, ammonium sulfide, a hydrogen / metal catalyst (palladium-carbon, platinum
  • a hydrogen / metal catalyst palladium-carbon, platinum
  • Other reduction methods, such as carbon, rhodium-alumina, platinum, Raney-nickel, etc., can be used.
  • This production method is by transposition of the substituted benzoic acids of the present invention compounds (iota-kappa) after induced to acid azides and Isoshiana one DOO acids, which is reacted with an alcohol (R 23 - ⁇ ) Is converted to substituted phenylcarbamic acid esters ( ⁇ -L).
  • the substituted benzoic acids ( ⁇ - ⁇ ) can be produced, for example, by the above-mentioned production method (1).
  • the reaction is in a solventless or in a solvent inert to the reaction, azide, a base, and alcohols - the presence of (R 23 OH), usually one 20 ⁇ 200 ° C, preferably 20 ⁇ 0.99 ° It is performed in the temperature range of C.
  • the azidating agent examples include diphenyl phosphorodiazide, trimethinoresilyl Azide, sodium azide and the like can be mentioned, and the amount of the compound to be used is generally 1.0 to 3.0 equivalents, preferably 1.0 to 1.5 equivalents, per 1 equivalent of compound (I—).
  • the amount of the compound to be used is generally 1.0 to: L00 equivalent, preferably 1.0 to 5.0 equivalent per 1 equivalent of compound (I-K).
  • Suitable solvents to be used include aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane; and aromatic hydrocarbons such as benzene, toluene, xylene and cumene.
  • Hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene; etc .; Jethyl ether, diisopropyl ether, dibutyl ether, dimethoxetane, Ethers such as tetrahydrofuran and dioxane; esters such as ethyl acetate and butyl acetate; ketones such as acetone and methylethyl ketone; alcohols such as methanol, ethanol and propanol; nitriles such as acetonitrile; N-dimethylformamide, N-methylbiamide
  • Non-protonic polar solvents such as don, dimethyl sulfoxide, sulfolane, etc .; water; and a mixed solvent of two or more thereof, and preferably alcohols which are reaction reagents.
  • the present production method is characterized in that the substituted phenylcarbamic acid esters (I-L) Is converted to substituted anilines (I-J).
  • the substituted phenyl carbamates (I-L) can be produced, for example, by the above-mentioned production method (7).
  • the above reaction is carried out in the presence of water, usually under acidic or alkaline conditions, usually at a temperature of from 20 to 200 ° C, preferably from 0 to 150 ° C.
  • examples of the acidic reagent used include hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, and the like.
  • the amount of the compound used is usually the compound (I-J). With respect to 1 equivalent, 1.0 to: L 00 equivalent, preferably 1.0 to 10.0 equivalent.
  • the base used may be an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide; an alkali metal hydroxide such as sodium carbonate, carbonated calcium carbonate, calcium carbonate or the like.
  • the amount of the compound used is usually 1 equivalent of the compound (I-J). It is 1.0 to 100 equivalents, preferably 1.0 to 10.0 equivalents.
  • Suitable solvents to be used include aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane; and aromatic hydrocarbons such as benzene, toluene, xylene and cumene.
  • Hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, cyclobenzene, dichlorobenzene, etc .; getyl ether, diisopropyl ether, dibutyl ether, dimethoxetane, tetrahydrofuran, Ethers such as dioxane; ketones such as acetone and methyl ethyl ketone; alcohols such as methanol, ethanol and propanol; N, N-dimethylformamide, N-methylvinylidone, dimethylsulfoxide, sulfolane
  • Non-protonic polar solvents such as acetic acid Organic acids; water; and mixed solvents of two or more thereof.
  • the amount of the solvent used is usually within 100 times, preferably 1 to 50 times the weight of the compound (I-J).
  • a sulfoxide (I-N) is produced by oxidizing a sulfide (IM) in the compound of the present invention.
  • the sulfides (I-M) can be produced, for example, by the production method (1).
  • the above reaction is usually carried out in the absence of a solvent or in a solvent inert to the reaction in the presence of an oxidizing agent, usually at a temperature of from 20 to 200 ° C (preferably from 0 to 150 ° C).
  • the oxidizing agent examples include hydrogen peroxide; organic peracids such as peracetic acid and metachloroperbenzoic acid; metaperiodates such as sodium metaperiodate; halogens such as chlorine and bromine; N-chlorosuccinic acid
  • the oxidizing agent usually used for the oxidation reaction of a sulfide group, such as a halide such as imide and N-bromosuccinic acid imide.
  • the amount of the oxidizing agent to be used is usually 1 to 3 equivalents, preferably: 1 !, equivalent to 1 equivalent of the compound (IM). ⁇ 2 equivalents.
  • Suitable solvents to be used include aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane; and aromatic hydrocarbons such as benzene, toluene, xylene and cumene.
  • Hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene; etc .; Jethyl ether, diisopropyl ether, dibutyl ether, dimethoxetane, tetrahydrofuran Esters such as ethyl acetate and butyl acetate; ketones such as acetone and methylethyl ketone; alcohols such as methanol, ethanol and propanol; nitriles such as acetonitrile; N, N— Dimethylformamide, N-methylpyro Non-protonic polar solvents such as lidone, dimethyl sulfoxide, and sulfolane; water; and a mixed solvent of two or more thereof.
  • the amount of the solvent used is usually within 100 times, preferably 1 to 50 times the weight of the compound (I-M). Manufacturing method
  • the sulfoxides (1-0) in the compound of the present invention are reacted with trifluoroacetic anhydride, and the product is hydrolyzed with a base to convert the substituted thiophenols (I-P). It is manufactured.
  • the sulfoxides (I-I) can be produced by the production method (9).
  • trifluoroacetic anhydride is reacted in a solvent-free or inert solvent in a temperature range of ⁇ 20 to 200 ° C., preferably 0 to 150 ° C., and then the product is treated with a base.
  • a solvent-free or inert solvent in a temperature range of ⁇ 20 to 200 ° C., preferably 0 to 150 ° C.
  • the amount of trifluoroacetic anhydride to be used is generally 1 to 50 equivalents, preferably 1 to 20 equivalents, per 1 equivalent of compound (1-0).
  • bases examples include triethylamine, N, N-diisoprovirethylamine, 1,8-diazabicyclo [5.4.0] —7-indene, 1,5-diazabicyclo [4.3.0] — Nitrogen-containing organic bases such as 5-nonene and 1,4-diazabicyclo [2.2.2] octane; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; sodium carbonate, potassium carbonate; Alkali metal or alkaline earth metal carbonates such as calcium carbonate; sodium bicarbonate, alkaline metal bicarbonates such as hydrogen bicarbonate, etc., and the amount used is usually the compound (1_0) Is 1 The amount is 1 to 200 equivalents, preferably 1 to 100 equivalents, relative to the equivalent.
  • Suitable solvents to be used include, in the first-stage reaction, aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane; benzene and toluene.
  • Aromatic hydrocarbons such as benzene, xylene, cumene; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, etc .; Jethyl ether, diisopro Ethers such as bil ether, dibutyl ether, dimethoxane, tetrahydrofuran, and dioxane; esters such as ethyl acetate and butyl acetate; ketones such as acetone and methyl ethyl ketone; nitriles such as acetonitrile; N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, sulfo Aprotic polar solvents such as lan; and mixed solvents of two or more of these.
  • halogenated hydrocarbons such as dichloromethane, chloroform, carbon
  • alcohols such as methanol, ethanol, and propanol; and water, etc. No.
  • the amount of the solvent used is usually within 100 times, preferably 1 to 50 times the weight of the compound (1-0).
  • This production method comprises the step of condensing a substituted phenol, a substituted thiophenol or a substituted aniline (I-Q) in a compound of the present invention with a halide or a sulfonate (X) to obtain the compound of the present invention (I — R).
  • the above substituted phenols, substituted thiophenols, and substituted anilines (I-Q) They can be produced by the above-mentioned production methods (5), (6), (8) and (10).
  • the condensation reaction is carried out in the absence of a solvent or in a solvent inert to the reaction in the presence of a base, usually at a temperature in the range of -20 to 200 ° C, preferably 0 to 150 ° C.
  • the amount of the compound to be used is 1 to 10 equivalents, preferably 1 to 2 equivalents of the compound (X) to 1 equivalent of the compound (I-Q).
  • Examples of the base include triethylamine, N, N-diisopropylethylamine, pyridine, bicholine, lutidine, collidine, N, N-getylaniline, 4- (dimethylamino) pyridine, 1,8-diazabicyclo [5.4] 0] — 7-Pendecene, 1,5-Diazabicyclo [4. 3.
  • Suitable solvents to be used include aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane; and aromatic hydrocarbons such as benzene, toluene, xylene and cumene.
  • Hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, etc .; Jethyl ether, diisopropyl ether, dibutyl ether, dimethoxetane, Ethers such as tetrahydrofuran and dioxane; esters such as ethyl acetate and butyl acetate; ketones such as acetone and methylethyl ketone; nitriles such as acetonitrile; N, N-dimethylformamide; Non-protons such as don, dimethyl sulfoxide and sulfolane A polar solvent; water; and a mixed solvent of two or more of these.
  • the amount of the solvent used is usually within 100 times, preferably 1 to 50 times the weight of the compound (I-Q). Manufacturing method (1 2)
  • R 24 represents an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an alkylcycloalkyl group, a (cyclo Alkyl) alkyl group, cycloalkenyl group, haloalkyl group, haloalkenyl group, halocycloalkyl group, cyanoalkyl group, alkoxyalkyl group, alkylthioalkyl group, alkylsulfonylalkyl group, alkyl group substituted with phenyl group, or 3- Represents an alkyl group substituted by a 6-membered heterocyclic group, and R 25 represents a lower alkyl group.
  • This production method is substituted Fuwenoru compounds of the present invention compounds (I one I) and alcohols - by dehydration condensation reaction between (R 24 OH) (XI) , to produce a substituted phenylalanine ethers (I- S) Things.
  • the substituted phenols (II) can be produced, for example, by the production method described above.
  • the above reaction is carried out without solvent or in a solvent inert to the reaction, in the presence of triphenylphosphine and dialkyl azodicarboxylate, usually at 120 to 200 ° C, preferably 0 to: L50 °. It is performed in the temperature range of C.
  • the amount of the compound to be used is 1 to 3 equivalents, preferably 1 to 1.5 equivalents of the compound (XI) to 1 equivalent of the compound (I-I).
  • the amount of triphenyl phosphine is usually compound (I- I) force 5 1, based on the equivalents, 1-3 equivalents, preferably 1 to 1.5 equivalents, the amount of Azojikarubon dialkyl typically compound (I-I) is 1 to 3 equivalents, preferably 1 to 0.5 equivalents, per 1 equivalent.
  • Suitable solvents used include aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane; benzene, Aromatic hydrocarbons such as toluene, xylene and cumene; Halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, cyclobenzene, dichlorobenzene, etc .; Jethyl ether, diisopro Ethers such as bil ether, dibutyl ether, dimethoxetane, tetrahydrofuran and dioxane; esters such as ethyl acetate and butyl acetate; ketones such as acetone and methyl ethyl ketone; nitriles such as acetonitrile; N, N— Non-protonic polar solvent
  • the esters (I-T) in the compound of the present invention are hydrolyzed to convert them into the carboxylic acids (I-U) in the compound of the present invention.
  • the invention compound (IT) can be produced, for example, by the above-mentioned production method (1).
  • the above reaction is carried out under the conditions generally carried out in the hydrolysis reaction of ordinary esters in the absence of a solvent or in a solvent inert to the reaction, usually in the range of —20 to 200 ° C., preferably 1 to 100 ° C. It is performed in the temperature range of C.
  • the amount of water used in the above hydrolysis is generally 1 to 100 equivalents, preferably 1 to 50 equivalents, per 1 equivalent of compound (IT).
  • examples of the acidic reagent used include hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, and the like.
  • T) is 1 to 100 equivalents to 1 equivalent.
  • the base used may be an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide; an alkali metal hydroxide such as sodium carbonate, carbonated calcium carbonate, calcium carbonate or the like.
  • Earth metal carbonates sodium hydrogen carbonate, hydrogen carbonate metal hydride and other metal hydrogen carbonates and the like.
  • the amount of the compound is usually 1 to 1 equivalent of the compound (I_T). 100 equivalents.
  • the above reaction is preferably carried out in a solvent.
  • Suitable solvents to be used include aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane; and aromatic hydrocarbons such as benzene, toluene, xylene and cumene.
  • Hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, etc .; getyl ether, diisopropyl ether, dibutyl ether, dimethoxetane, Ethers such as tetrahydrofuran and dioxane; ketones such as acetone and methyl ethyl ketone; alcohols such as methanol, ethanol and propanol; Non-protonic polar solvents such as water and sulfolane; water And a mixed solvent of two or more of these.
  • the amount of the solvent used is usually 100 times or less, preferably 1 to 50 times the weight of the compound (I-II). Manufacturing method (14)
  • This production method comprises preparing an ester, a thioester or an acid amide from the carboxylic acid (I-U) in the compound of the present invention and an alcohol, a thiol or an amine (XI I). (14-a) to (14-d) below.
  • the carboxylic acids (IU) can be produced, for example, by the above-mentioned production method (13).
  • Carboxylic acids (I-U) are converted to acid halides with a halogenating agent such as thionyl chloride, phosphorus trichloride, phosphorus pentachloride, phosphoryl chloride, phosgene, etc., usually in the presence of a base. It is converted to esters, thioesters, and acid amides (IV) by reacting with an alcohol, thiol, or amine (XI I).
  • a halogenating agent such as thionyl chloride, phosphorus trichloride, phosphorus pentachloride, phosphoryl chloride, phosgene, etc.
  • Carboxylic acids (I-U) are usually converted into mixed acid anhydrides with alkyl chloroformate, trifluoroacetic anhydride or the like in the presence of a base, which is usually converted to an alcohol, thiol, Alternatively, they are converted to esters, thioesters, or acid amides (IV) by reacting with amines (XI I).
  • the above-mentioned reactions (14_a) to (14-d) are usually performed in a solvent-free or inert solvent in a temperature range of -20 to 200 ° C, preferably -10 to 150 ° C.
  • the amount of the amine or the amine (XI I) is usually 1 to 20 equivalents, preferably 1 to 5 equivalents to 1 equivalent of the compound (IU).
  • the amount of the alcohol (XI I) used in the reaction (14-d) is usually 1 to 100 equivalents, preferably 1 to 20 equivalents, per 1 equivalent of the compound (IU).
  • suitable bases include triethylamine, N, N-diisoprovirethylamine, pyridine, picoline, lutidine, collidine, N, N-Jetylaniline, 4- (Dimethylamino) pyridine, 1,8-Diazabicyclo [5.4.0] —7-Pendecene, 1,5-Diazabicyclo [4.3.0] —5-Nonene, 1, 4- Nitrogen-containing organic bases such as diazabicyclo [2.2.2] octane; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metals such as sodium carbonate, potassium carbonate and calcium carbonate or alkaline earths Metal carbonates: alkali metal bicarbonates such as sodium bicarbonate and bicarbonate lime.
  • the amount of the base to be used is generally 1-3 equivalents, preferably 1-2 equivalents, per 1 equivalent of compound (IU).
  • the amount of the acid catalyst used in the reaction of (14-d) is 0.001 to 10 equivalents, preferably 0.01 to 2 equivalents, per 1 equivalent of the compound (IU).
  • Suitable solvents to be used include aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane; Aromatic hydrocarbons such as benzene, toluene, xylene, and cumene; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, and dichlorobenzene; getyl ether, diisopropyl ether And ethers such as dibutyl ether, dimethoxetane, tetrahydrofuran and dioxane; ketones such as acetone and methyl ethyl ketone; N, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide and sulfolane
  • Non-protonic polar solvent water; mixed solvent of two or more of these And the like.
  • a large excess of the alcohol (XI I) may be used as a solvent.
  • the amount of solvent used is usually Within 100 times, preferably 1 to 50 times, the weight of the product (I_U), production method (15)
  • the substituted aniline (I-J) in the compound of the present invention is diazotized, and then the unsaturated carboxylic acid derivative (XIV) is reacted with a metal halide to give the compound (I-W) of the present invention. It is manufactured.
  • the substituted anilines (IJ) can be produced, for example, by the above-mentioned production methods (1), (6) and (8).
  • the substituted aniline (I-J) is converted to an unsaturated carboxylic acid derivative (XIV), an alkyl nitrite (t-butyl nitrite, isoamyl nitrite, etc.) in a solvent or in a solvent inert to the reaction. ) And in the presence of a metal halide, usually at a temperature of from 120 to 200 ° C, preferably from 110 to 100 ° C.
  • the amount of compound used is usually the compound (I- J) force s 1 eq, compound (XIV) is 1-5 0 equivalents, preferably 2-20 equivalents, alkyl nitrite is 1 to 3 Equivalent, preferably 1-2 equivalent.
  • the above-mentioned metal halides are usually copper chloride (1), copper chloride (11), copper bromide (I), copper bromide (II), iodide Copper halides such as copper (I) and copper (II) iodide are used, and the amount of the compound is usually 1 to 3 equivalents, preferably 1 to 2 equivalents, per 1 equivalent of the compound (I-J). It is.
  • Suitable solvents used include aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane; benzene, Aromatic hydrocarbons such as toluene, xylene and cumene; Halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, cyclobenzene, dichlorobenzene, etc .; Jethyl ether, diisopro Ethers such as vir ether, dibutyl ether, dimethoxetane, tetrahydrofuran and dioxane; esters such as ethyl acetate and butyl acetate; ketones such as acetone and methyl ethyl ketone; alcohols such as methanol, ethanol and propanol; acetonitrile And non-pro
  • the compound (I-Y) of the present invention is produced by reacting the compound (I-X) of the present invention with an unsaturated carboxylic acid derivative (XIV).
  • the inventive compound (I-X) can be produced, for example, by the production methods (1) and (11).
  • the above reaction is usually carried out without solvent or in a solvent inert to the reaction.
  • the reaction is carried out at a temperature of 0 ° C, preferably 0 to 150 ° C.
  • the amount of the compound used in the reaction is usually 1 to 10 equivalents, preferably 1 to 3 equivalents of the compound (XIV) to 1 equivalent of the compound (IX).
  • the above reaction is optionally used in combination with 1) a metal or metal complex catalyst, and 2) a base.
  • metal or metal complex catalyst examples include metals such as nickel, iron, ruthenium, copper, rhodium, iridium, palladium, and platinum; tetrakis (triphenylphosphine) palladium, tris (dibenzylideneacetone) dipalladium , Dichlorobis (triphenylphosphine) palladium, dichloro [1,3-bis (diphenylphosphino) propane] nickel, dichloro [1,2-bis (diphenylphosphino) ethane] nickel, bis (acetylacetonato) ) Nickel, dichloro [1,1,1-bis (diphenylphosphino) phenecene] palladium or other such metals or their chlorides and triphenylphosphine, tri (o-tolyl) phosphine, 1 , 2-bis (diphenylphosphino) propane, 1, 1, 1 Bis (diphenylphosphino) metal complex
  • Examples of the base include triethylamine, N, N-diisopropylethylamine, pyridine, picoline, lutidine, collidine, N, N-getylaniline, 4- (dimethylamino) pyridine, 1,8-diazabicyclo [5.4.
  • phase transfer catalyst may be added to the reaction system.
  • phase transfer catalyst include quaternary ammonium salts such as tetrabutylammonium bromide, tetrabutylammonium chloride, and benzyltriethylammonium chloride.
  • the amount of compound (IX) is within 2 equivalents, preferably within 1 equivalent, relative to 1 equivalent.
  • Suitable solvents to be used include aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane; and aromatic hydrocarbons such as benzene, toluene, xylene and cumene.
  • Hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, etc .; getyl ether, diisopropyl ether, dibutyl ether, dimethoxetane, Ethers such as tetrahydrofuran and dioxane; esters such as ethyl acetate and butyl acetate; ketones such as acetone and methylethyl ketone; alcohols such as methanol, ethanol and propanol; nitriles such as acetonitrile; N, N— Dimethylformamide, N-methylbi mouth Water;, dimethyl sulfoxide, non pro ton polar solvents such as sulfolane ⁇ beauty mixed solvent of two or more thereof.
  • the amount of the solvent used is usually within 100 times, preferably 1 to 50 times, the weight of the solvent used.
  • the present production method comprises reducing the compound (I-Y) of the present invention to obtain the compound of the present invention.
  • (IZ) inventive compound
  • the inventive compound (I-Y) can be produced, for example, by the above-mentioned production methods (1) and (16).
  • This reduction reaction is carried out by hydrogenation in a solvent-free or inert solvent in the presence of a catalyst, usually at a temperature of 0 to 150 ° C, preferably 20 to 100 ° C. .
  • the catalyst examples include those used in ordinary hydrogenation reactions, such as metal catalysts such as palladium-carbon, platinum-carbon, rhodium-alumina, platinum, Raney nickel, and the like. It is 0.001 to 0.2 times the weight of (I-Y).
  • Suitable solvents to be used include aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane; and aromatic hydrocarbons such as benzene, toluene, xylene and cumene.
  • ethers such as Jethyl ether, diisopropyl ether, dibutyl ether, dimethoxane, tetrahydrofuran, dioxane
  • esters such as ethyl acetate and butyl acetate
  • ketones such as acetone and methyl ethyl ketone Alcohols such as methanol, ethanol and propanol
  • water and mixed solvents of two or more of these.
  • the amount of the solvent used is usually within 100 times, preferably 1 to 50 times the weight of the compound (I-Y). Manufacturing method (18)
  • Examples of the acidic reagent used include mineral acids such as sulfuric acid and hydrochloric acid and silver nitrate.
  • the amount of the reagent used is usually 1 equivalent of the compound (ID), and 2 to 2 in the case of a mineral acid.
  • the equivalent is 100 equivalents, preferably 10 to 100 equivalents, and in the case of silver nitrate, 1 to 10 equivalents, and preferably 1 to 3 equivalents.
  • the reaction is usually carried out in the absence of a solvent or in a solvent inert to the reaction in the presence of water and a base, usually at ⁇ 20 to 200 ° C., preferably at 0 to 15 Performed in a temperature range of 0 ° C.
  • Examples of the base to be used include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal or alkaline earth metal carbonates such as sodium carbonate, potassium carbonate and calcium carbonate; sodium hydrogen carbonate and carbonate Alkali metal bicarbonates such as hydrogen lime; Alkali metal salts of organic acids such as sodium formate, potassium formate, sodium acetate, potassium acetate, sodium oxalate and oxalate potassium; sodium methoxide, sodium Examples thereof include alkali metal alcoholates such as ethoxide, potassium t-butoxide, and the like. The amount of the alcohol is usually 1 to 5 equivalents, preferably 1 to 3 equivalents, per equivalent of (I-D). Is equivalent.
  • Suitable solvents to be used include aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane; and aromatic hydrocarbons such as benzene, toluene, xylene and cumene.
  • Hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, etc .; getyl ether, diisopropyl ether, dibutyl ether, dimethoxetane, Ethers such as tetrahydrofuran and dioxane; ketones such as acetone and methyl ethyl ketone; alcohols such as methanol, ethanol and propanol; N, N-dimethylformamide, N-methylbi Non-protonic polar solvents such as mouth ridone, dimethyl sulfoxide and sulfolane; water; and a mixed solvent of two or more of these.
  • the amount of the solvent used is usually within 100 times, preferably 1 to 50 times the weight of the compound (ID).
  • the keels (I-b) in the compound of the present invention are converted to the corresponding carbonyl compounds (I-a) by hydrolysis.
  • the invention compound (Ib) can be produced, for example, by the production method (1).
  • the above reaction is carried out in the absence of a solvent or in a solvent inert to the reaction, in the presence of an acidic reagent, usually at a temperature in the range of 0 to 200 ° (preferably 20 to 150 ° C.).
  • the acidic reagent examples include hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, brenstead acid such as trifluoroacetic acid, p-toluenesulfonic acid; or aluminum trichloride, boron tribromide, Examples thereof include Lewis acids such as boron chloride and the like, and the amount to be used is generally 0.05 to 10 equivalents, preferably 0.01 to 2 equivalents, per 1 equivalent of compound (I-b). .
  • Suitable solvents to be used include aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane; and aromatic hydrocarbons such as benzene, toluene, xylene and cumene. Hydrocarbons; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, etc .; getyl ether, diisopropyl ether, dibutyl ether, dimethoxetane, Tetrahydrofuran, dioxane, etc.
  • ketones such as acetone and methylethyl ketone
  • alcohols such as methanol, ethanol, and propanol
  • non-protonic properties such as N, N-dimethylformamide, N-methylvinylidone, dimethylsulfoxide, and sulfolane A polar solvent
  • water and a mixed solvent of two or more thereof.
  • the amount of the solvent used is usually within 100 times, preferably 1 to 50 times the weight of the compound (I-b).
  • the compound (I-Y) 'of the present invention is produced by reacting the compound (I-a) of the present invention with the corresponding phosphorane (XVI).
  • the compound (Ia) of the present invention can be produced, for example, by the above-mentioned production methods (1), (18) and (19).
  • the above reaction is carried out usually in a solvent-free or inert solvent in a temperature range of from 120 to 200 ° C, preferably from 0 to 150 ° C.
  • the amount of the compound used is usually 1 to 3 equivalents of the corresponding phosphorane (XVI), preferably 1 to 1.5 equivalents to 1 equivalent of the compound (I_a).
  • Suitable solvents to be used include aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane; and aromatic hydrocarbons such as benzene, toluene, xylene and cumene.
  • Hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, etc .; getyl ether, diisopropyl ether, dichlorobenzene Ethers such as butyl ether, dimethoxetane, tetrahydrofuran and dioxane; esters such as ethyl acetate and butyl acetate; ketones such as acetone and methyl ethyl ketone; alcohols such as methanol, ethanol and propanol; nitriles such as acetonitrile Aprotic polar solvents such as N, N-dimethylformamide, N-methylbipyridine, dimethylsulfoxide and sulfolane; water; and a mixed solvent of two or more of these.
  • the amount of the solvent used is usually within 100 times, preferably 1 to 50
  • the corresponding phosphorane or ylide may be prepared in the system using the corresponding phosphonium salt and a base in place of the phosphorane (XVI).
  • Corresponding phosphonate carbonions may be used as in reactions.
  • the present production method is based on the compound (I-a) of the present invention and a hydroxylamine (XV II ) Or a salt thereof to produce an oxime derivative (Ic).
  • the invention compound (I-a) can be produced, for example, according to the production methods (1), (18) and (19).
  • the above reaction is carried out usually in a solvent-free or inert solvent in a temperature range of 120 to 200 ° C, preferably 0 to 150 ° C.
  • the amount of the compound to be used is usually 1.0 to 3.0 equivalents, preferably 1.0 to 1.5 equivalents of the hydroxyamine (XVII) per 1 equivalent of the compound (Ia). is there.
  • the above reaction involves hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, trifluoroacetic acid, p -Brensted acid such as toluenesulfonic acid and pyridinum p-toluenesulfonic acid; or acid reagent such as aluminum trichloride, boron tribromide, Lewis acid such as boron trichloride, or triethylamine, N, N-diisopropyle Tyramine, pyridine, bicholine, lutidine, collidine, N, N-getylaniline, 4- (dimethylamino) pyridine, 1,8-diazabicyclo [5.4.0] —7-indene, 1,5-diazabicyclo [ 4.3.0] — 5-nonene, 1,4-diazabicyclo [2.2.2] octane and other nitrogen-containing organic bases; sodium hydroxide, potassium hydroxide and other alkali metal
  • the amount of the acidic reagent or base to be used is generally 1 to 20 equivalents, preferably 2 to 10 equivalents, per 1 equivalent of compound (Ia).
  • Suitable solvents to be used include aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane; and aromatic hydrocarbons such as benzene, toluene, xylene and cumene.
  • Hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, etc .; getyl ether, diisopropyl ether, dibutyl ether, dimethoxetane, Ethers such as tetrahydrofuran and dioxane; esters such as ethyl acetate and butyl acetate; alcohols such as methanol, ethanol and propanol; nitriles such as acetonitrile; N, N-dimethylformamide; Ridone, dimethyl sulfoxide, sulfolane, etc.
  • the amount of the solvent used is usually within 100 times, preferably 1 to 50 times the weight of the compound (I-a).
  • the compound (Ic) of the present invention is produced by condensing the compound (Id) of the present invention with a halide or a sulfonate (X).
  • the inventive compound (Id) can be produced, for example, by the production methods (1) and (21).
  • the above reaction is carried out without solvent or in a solvent inert to the reaction in the presence of a base, usually at a temperature in the range of ⁇ 20 to 200 ° C .; preferably 0 to 150 ° C.
  • the amount of the compound to be used is generally 1 to 10 equivalents, preferably 1 to 2 equivalents of the compound (X) relative to 1 equivalent of the compound (Id).
  • Examples of the base include triethylamine, N, N-diisoprovirethylamine, pyridine, bicholine, lutidine, collidine, N, N-getylaniline, 4- (dimethylamino) pyridine, 1,8-diazabicyclo [5.4] 0] — 7-Pendecene, 1,5-Diazabicyclo [4.3.0] — 5-Nonene, 1,4-Diazabicyclo [2.2.2]
  • Nitrogen-containing organic bases such as octane; sodium hydroxide Alkali metal hydroxides such as sodium hydroxide, potassium hydroxide; alkaline metal or alkaline earth metal carbonates such as sodium carbonate, potassium carbonate and calcium carbonate; alkaline metals such as sodium hydrogen carbonate and hydrogen carbonate Metal hydride; metal hydrides such as sodium hydride and the like;
  • the amount of the base to be used is generally 1-3 equivalents, preferably 1-2 equivalents, per 1 equivalent of compound (
  • Suitable solvents used include aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane; benzene, Aromatic hydrocarbons such as toluene, xylene and cumene; Halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, cyclobenzene, dichlorobenzene, etc .; Jethyl ether, diisopro Ethers such as virether, dibutylether, dimethoxetane, tetrahydrofuran, and dioxane; esters such as ethyl acetate and butyl acetate; ketones such as acetone and methylethylketone; nitriles such as acetonitrile; N, N-dimethylform Non-protonic polar
  • the compound of the present invention (Ie) is produced by reducing and simultaneously cyclizing a nitro compound (XVIII).
  • the above reduction reaction is usually carried out in the absence of a solvent or in a solvent inert to the reaction, in the presence of a metal or metal compound, and an acidic reagent, at a temperature of usually 20 to 200 ° (preferably 50 to 150 °). .
  • Examples of the above-mentioned metal or metal compound include metals or metal compounds usually used in the reduction reaction of a nitro group, such as iron, zinc, tin and tin (II) chloride.
  • the amount of the metal or metal compound to be used is generally 1 to 20 equivalents, preferably 2 to 10 equivalents, per 1 equivalent of compound (XVI II).
  • Examples of the acidic reagent include inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as acetic acid.
  • the amount of the acid reagent to be used is generally 0.01 to 20 equivalents to 1 equivalent of the compound (XVIII). And preferably 0.01 to 10 equivalents.
  • Suitable solvents to be used include aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane; and aromatic hydrocarbons such as benzene, toluene, xylene and cumene.
  • Hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, etc .; getyl ether, diisopropyl ether, dibutyl ether, dimethoxetane, Ethers such as tetrahydrofuran and dioxane; esters such as ethyl acetate and butyl acetate; ketones such as acetone and methylethyl ketone; alcohols such as methanol, ethanol and propanol; nitritols such as acetonitrile; , N-dimethylformamide, N-methylbi mouth Water; organic acids such as acetic acid;, dimethyl sulfoxide, non pro ton polar solvents such as sulfolane and solvent mixtures of two or more of these, and the like.
  • the amount used is usually within 100
  • the above reaction is carried out using sodium sulfide, sodium hydrosulfide, sodium nitrite, ammonium sulfide, a hydrogen / metal catalyst (palladium-carbon, platinum Other reduction methods can be used, such as carbon, rhodium-alumina, platinum, Raney nickel, etc.). Manufacturing method (2 4)
  • the compound (If) of the present invention is produced by condensing the compound (Ie) of the present invention with a halide or a sulfonate (X).
  • the inventive compound (Ie) can be produced, for example, by the above-mentioned production methods (1) and (23).
  • the condensation reaction is carried out in the absence of a solvent or in a solvent inert to the reaction, in the presence of a base, usually at a temperature in the range of 120 to 200 ° C, preferably 0 to 150 ° C.
  • the amount of the compound to be used is 1 to 10 equivalents, preferably 1 to 2 equivalents of the compound (X) to 1 equivalent of the compound (I-e).
  • Examples of the above bases include triethylamine, N, N-diisoprovirethylamine, pyridine, bicholine, lutidine, collidine, N, N-getylaniline, 4- (dimethylamino) pyridine, 1,8-diazabicyclo [5.4] 0] — 7-Pendecene, 1,5-Diazabicyclo [4.3.0] — 5-Nonene, 1,4-Diazabicyclo [2.2.2]
  • Nitrogen-containing organic bases such as octane; sodium hydroxide Alkali metal hydroxides such as potassium hydroxide and potassium hydroxide; Alkali metal or alkaline earth metal carbonates such as sodium carbonate, potassium carbonate and calcium carbonate; Alkali metals such as sodium hydrogen carbonate and potassium hydrogen carbonate Metal hydride; metal hydride such as sodium hydride;
  • the amount of the base to be used is generally 1-3 equivalents, preferably 1-2 equivalents, per 1 equivalent of compound (I
  • Suitable solvents to be used include aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane; and aromatic hydrocarbons such as benzene, toluene, xylene and cumene.
  • Hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, etc .; getyl ether, diisopropyl ether, dibutyl ether, dimethoxetane, tetrahi Ethers such as drofuran and dioxane; esters such as ethyl acetate and butyl acetate; ketones such as acetone and methylethyl ketone; nitriles such as acetonitrile; N, N-dimethylformamid And non-protonic polar solvents such as N-methylpyrrolidone, dimethylsulfoxide, and sulfolane; water; and a mixed solvent of two or more of these.
  • the amount of the solvent used is usually within 100 times, preferably 1 to 50 times the weight of the compound (I-e).
  • a 11 represents an oxygen atom, a sulfur atom or a —NR 4 — group of A 1 And R 4 have the same meanings as described above.
  • the compound (Ih) of the present invention is produced from the compound (Ig) of the present invention and an alcohol, thiol or amine (XIX).
  • the invention compound (Ig) can be produced, for example, by the above-mentioned production method (1).
  • the condensation reaction is carried out in the absence of a solvent or in a solvent inert to the reaction in the presence of a base, usually at a temperature in the range of -20 to 200 ° C, preferably 0 to 150 ° C.
  • the amount of the compound to be used is 1 to 20 equivalents, preferably 1 to 5 equivalents of the compound (XIX) per 1 equivalent of the compound (Ig).
  • Examples of the above base include triethylamine, N, N-diisoprovirethylamine, pyridine, picoline, lutidine, collidine, N, N-getylaniline, 4- (dimethylamino) pyridine, 1,8-diazabicyclo [5.4] 0] —7-Pendecene, 1,5-Diazabicyclo [4.3.0] — 5-Nonene, 1,4-Diazabicyclo [2.2.2] Octane and other nitrogen-containing organic bases; sodium hydroxide Alkali metal hydroxides, such as potassium hydroxide and potassium hydroxide; alkaline metal or alkaline earth metal carbonates such as sodium carbonate, potassium carbonate, calcium carbonate; sodium hydrogen carbonate, charcoal Metal hydrides such as hydrogen oxyhydrogen and the like; metal hydrides such as sodium hydrogen hydride and the like.
  • the amount of the base to be used is generally 1-3 equivalents, preferably 1-2 equivalents, per 1 equivalent of compound (Ig
  • Suitable solvents to be used include aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane; and aromatic hydrocarbons such as benzene, toluene, xylene and cumene.
  • Hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene; etc .; Jethyl ether, diisopropyl ether, dibutyl ether, dimethoxetane, Ethers such as tetrahydrofuran and dioxane; esters such as ethyl acetate and butyl acetate; ketones such as acetone and methylethyl ketone; nitriles such as acetonitrile; N, N-dimethylformamide; Non-protons such as don, dimethyl sulfoxide and sulfolane Polar solvent; water; and mixed solvents of two or more thereof.
  • the amount of the solvent used is usually within 100 times, preferably 1 to 50 times the weight of the compound (I-g). Manufacturing method (26)
  • R 1 ′ is an alkyl group, an alkenyl group, an alkynyl group, or a trialkylsilylethynyl group.
  • This production method comprises reacting a substituted phenylpyrimidine (I-g) with the corresponding R 1 — H (XX) or a metal salt thereof R 1 — K (XXI) to obtain the substituted phenyl pyrimidine (I-g).
  • R 1 — H (XX) or a metal salt thereof R 1 — K (XXI) to obtain the substituted phenyl pyrimidine (I-g).
  • R 1 — H (XX) or a metal salt thereof R 1 — K (XXI) to obtain the substituted phenyl pyrimidine (I-g).
  • — I) is manufactured.
  • substituted phenylpyrimidi The compounds (Ig) can be produced, for example, by the above-mentioned production method (1).
  • the above reaction is carried out in the absence of a solvent or in a solvent inert to the reaction, usually at a temperature of from 120 to 200 ° C, preferably from 0 to 150 ° C.
  • the amount of the compound used in the reaction is usually 1.0 to 3.0 equivalents, preferably 1.0 to 1.0 equivalent of the compound (XX) or (XXI) per 1 equivalent of the compound (I-g). 5 equivalents.
  • Examples of the base include triethylamine, N, N-diisopropylethylamine, pyridine, picoline, lutidine, collidine, N, N-getylaniline, 4- (dimethylamino) pyridine, 1,8-diazabicyclo [5.4.0] ] — 7-Pendecene, 1,5-Diazabicyclo [4. 3.
  • metal halide, metal or metal complex catalyst examples include copper iodide, copper chloride, or zinc chloride; nickel, iron, ruthenium, cobalt, rhodium, iridium, noradium, platinum, and other metals; tetrakis (triphenyl).
  • Rifenyl phosphine tri- (o-tolyl) phosphine, 1,2-bi (Diphenyl phosphine Ino) propane, 1, 1, One-bis (diphenyl phosphine b Roh)
  • Examples include metal complexes formed with ligands such as phenethylene, dibenzylideneacetone, and acetylacetone.
  • the amount of the metal halide, metal or metal complex catalyst used is usually 0.001 to 3.0 equivalents, preferably 0.05 to 3.0 equivalents: 1 equivalent of the compound (I-g). It is.
  • Suitable solvents to be used include aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane; and aromatic hydrocarbons such as benzene, toluene, xylene and cumene.
  • Hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, and dichlorobenzene; getyl ether, diisopropyl ether, dibutyl ether, dimethyl ether Ethers such as toxetane, tetrahydrofuran and dioxane; esters such as ethyl acetate and butyl acetate; ketones such as acetone and methylethyl ketone; alcohols such as methanol, ethanol and propanol; nitriles such as acetonitrile; N-dimethylformamide, N-methylbi mouth Water;, dimethyl sulfoxide, non pro ton polar solvents such as sulfolane ⁇ beauty mixed solvent of two or more thereof.
  • the amount of the solvent used is usually within 100 times, preferably 1 to 50 times the weight of the compound (Ig)
  • the present production method comprises the steps of removing a trialkylsilyl group of a substituted phenyltrialkylsilylethynylpyrimidine (Ij) to obtain a substituted phenyltrialkylsilyl ethynylpyrimidine. (I-k).
  • the substituted phenyltrialkylsilylethyl-2-virimidine (I-1j) can be produced, for example, by the above-mentioned production method (26).
  • the above reaction is carried out without solvent or in a solvent inert to the reaction, in the presence of a base, usually at a temperature in the range of -20 to 200 ° C, preferably 0 to 150 ° C.
  • the base examples include tetrabutylammonium fluoride (TBAF), triethylamine, pyridine, picoline, N, N-getylaniline, 4- (dimethylamino) pyridine, 1,8-diazabicyclo [5,4,0] — Nitrogen-containing organic bases such as 7-ndecene, 1,5-diazabicyclo [4,3,0] -5-nonene, 1,4-diazabicyclo [2,2,2] octane; sodium hydroxide, hydroxide hydroxide Alkali metal hydroxides such as sodium carbonate, potassium carbonate, calcium carbonate and the like; Alkali metal carbonates such as sodium carbonate, potassium carbonate and calcium carbonate; Alkali metal salts of organic acids such as sodium acetate and potassium acetate; Alkali metal hydrides such as sodium hydride; sodium fluoride, potassium fluoride, calcium fluoride The amount of the compound is usually 1.0 to 3.0 equivalents, preferably
  • Suitable solvents to be used include aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane; benzene, toluene, xylene, cumene and the like.
  • Aromatic hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, and dichlorobenzene; getyl ether, diisopropyl: ter, dibutyl ether, dimethyl Ethers such as toxetane, tetrahydrofuran and dioxane; esters such as ethyl acetate and butyl acetate; ketones such as acetone and methylethyl ketone; alcohols such as methanol, ethanol and propanol; nitriles such as acetonitrile; , ⁇ -dimethylformamide, ⁇ -methylpi Water; Li, dimethyl sulfoxide, non pro ton polar solvents such as sulfolane ⁇ beauty mixed solvent of two or more thereof.
  • the amount of solvent used is usually It is within 100 times, preferably 1 to 50 times the weight
  • R 29 represents a hydrogen atom or a lower alkyl group.
  • a substituted alkenyl pyrimidine (Im) is produced by reducing a substituted alkynyl pyrimidine (1-1) in the compound of the present invention.
  • the substituted alkynylpyrimidines (1-1) can be produced, for example, by the production methods (1) and (27).
  • This reduction reaction is carried out by hydrogenation in a solvent-free or inert solvent in the presence of a catalyst, usually at a temperature in the range of 0 to 150 ° C, preferably 20 to 100 ° C. .
  • the catalyst examples include those used in ordinary hydrogenation reactions, such as metal catalysts such as palladium-one-carbon, platinum-one-carbon, rhodium-alumina, platinum, Raney nickel, and the like. It is 0.001 to 0.2 times the weight of (I-1).
  • Suitable solvents to be used include aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane; and aromatic hydrocarbons such as benzene, toluene, xylene and cumene.
  • ethers such as Jethyl ether, diisopropyl ether, dibutyl ether, dimethoxane, tetrahydrofuran, and dioxane
  • esters such as ethyl acetate and butyl acetate
  • ketones such as acetone and methyl ethyl ketone Alcohols such as methanol, ethanol and propanol
  • water and mixed solvents of two or more of these.
  • the amount of the solvent is usually 1100 times, preferably 1 to 20 times the weight of (1-1). Manufacturing method (29)
  • R 3Q and R 31 each independently represent a hydrogen atom or a lower alkyl group.
  • the compound (1-0) of the present invention is produced by halogenating the substituted phenylpyrimidines (In) in the compound of the present invention.
  • the substituted phenylpyrimidine (In) can be produced, for example, by the above-mentioned production method (1).
  • the above reaction is carried out without solvent or in a solvent inert to the reaction, in the presence of a halogenating agent, usually at a temperature of 0 to 200 ° C, preferably 0 to 150 ° C.
  • a halogenating agent usually at a temperature of 0 to 200 ° C, preferably 0 to 150 ° C.
  • the halogenating agent include the same halogenating agents as exemplified in the production method (2).
  • the amount of the halogenating agent to be used is usually 1 equivalent of the compound (In) and 1 equivalent of the halogenating agent. 0 3.0 equivalents, preferably 1.0 1.5 equivalents.
  • the above reaction is preferably carried out in a solvent.
  • Suitable solvents to be used include those exemplified in the production method (2), and the amount used is usually 100 parts by weight of the compound (I-n). It is up to 150 times, preferably 150 times.
  • a radical initiator may be used as necessary.
  • the radical initiator used include dibenzoyl peroxide, azobisisobutyronitrile (AIBN), and the like.
  • the amount of the compound (I-n) used per equivalent of the radical initiator is used. Is 0.0005 0.2 equivalent, preferably 0.001 to 0.1 equivalent. Manufacturing method (30)
  • the compound (I-P) of the present invention is produced by reacting the compound (I-o) of the present invention with a lower carboxylate or a lower carboxylic acid.
  • the inventive compound (Io) can be produced, for example, according to the production methods (1) and (29).
  • the compound of the present invention (IP) is hydrolyzed.
  • the compound (Iq) of the present invention is produced.
  • the inventive compound (IP) can be produced, for example, by the aforementioned production methods (1) and (30).
  • the present production method is a method for preparing a hydroxyl group of the compound (I-q) of the present invention.
  • the compound (1-0) of the present invention is produced by halogenation.
  • the inventive compound (Iq) can be produced by the production methods (1) and (31).
  • the above reaction is carried out in the absence of a solvent or in a solvent inert to the reaction, in the presence or absence of a base, in the presence of a halogenating agent, usually —20 to 200 ° C., preferably 0 to 1 ° C. It is performed in a temperature range of 50 ° C.
  • halogenating agent examples include tetrabutylammonium fluoride (TB AF), sulfur tetrafluoride, getylamino sulfur trifluoride, morpholino sulfur trifluoride, thionyl chloride, phosphorus trichloride, phosphorus pentachloride, hydrochloric acid, Phosphorus oxychloride, hydrobromic acid, phosphorus tribromide, thionyl bromide, etc. are generally used in amounts of 1.0 to 3.0 equivalents per 1 equivalent of (I-q). Preferably it is 1.0 to 2.0 equivalents.
  • suitable bases to be used include triethylamine, N, N-diisopropylethylamine, pyridine, picolin, lutidine, collidine, N, N-getylaniline, 4- ( Dimethylamino) pyridin, 1,8-diazabicyclo [5.4.0] — 7-indene, 1,5-diazabicyclo [4.3.0] — 5-nonene, 1,4-diazabicyclo [2.2.2] ]
  • Nitrogen-containing organic bases such as octane; alkaline metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal or alkaline earth metal carbonates such as sodium carbonate, potassium carbonate and calcium carbonate; Examples thereof include alkali metal hydrogencarbonates such as sodium hydrogencarbonate and potassium hydrogencarbonate, and the amount of (I-q) used is usually 3 equivalents or less, preferably 2 equivalents or less per equivalent of (I-q).
  • the above reaction is preferably performed in a solvent.
  • suitable solvents to be used include aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane; and aromatic hydrocarbons such as benzene, toluene, xylene and cumene.
  • Hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, etc .; getyl ether, diisopropyl ether, dibutyl ether, dimethoxetane, tetrahydrofuran, Ethers such as dioxane; esters such as ethyl acetate and butyl acetate; ketones such as acetone and methylethyl ketone; nitriles such as acetonitrile; N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide; Non-proton properties such as sulfolane A polar solvent; water; and a mixed solvent of two or more thereof.
  • the amount of the solvent used is usually within 100 times, preferably 1 to 50 times the weight of the compound (Iq). Manufacturing method (33)
  • a sulfoxide (I_s) is produced by oxidizing a sulfide (I-r) in the compound of the present invention.
  • the sulfides (Ir) can be produced, for example, by the production methods (1) and (25) described above.
  • sulfones (It) are produced by oxidizing sulfoxides (Is) in the compound of the present invention.
  • the sulfoxides (Is) can be produced, for example, according to the production methods (1) and (33).
  • the above reaction can be carried out under the same conditions as in the sulfide oxidation reaction as described in Production method (9).
  • the present production method comprises oxidizing a pyrimidine nitrogen atom of the compound (Iu) of the present invention,
  • the present invention is to produce the compound (IV) of the present invention.
  • the invention compound (Iu) can be produced, for example, by the above-mentioned production method (1).
  • the above reaction is carried out in the absence of a solvent or in a solvent inert to the reaction in the presence of an oxidizing agent, usually at a temperature in the range of ⁇ 20 to 200 ° C., preferably 0 to 150 ° C.
  • the oxidizing agent examples include hydrogen peroxide; peracids such as peracetic acid and methyl chloroperbenzoic acid; methyl periodate such as sodium metaperiodate; halogens such as chlorine and bromine; Examples include halogen compounds such as —chlorosuccinic acid imide and N-bromosuccinic acid imide.
  • the amount of the oxidizing agent to be used is generally 1 to 30 equivalents, preferably 1 to 2 equivalents, per 1 equivalent of compound (I-u).
  • Suitable solvents to be used include aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane; and aromatic hydrocarbons such as benzene, toluene, xylene and cumene.
  • Hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, and dichlorobenzene; getyl ether, diisopropyl ether, dibutyl ether, dimethoxetane; Ethers such as tetrahydrofuran and dioxane; esters such as ethyl acetate and butyl acetate; ketones such as acetone and methylethyl ketone; alcohols such as methanol, ethanol and propanol; nitriles such as acetonitrile; N-dimethylformamide, N-methylbi mouth Water;, dimethyl sulfoxide, non pro ton polar solvents such as sulfolane ⁇ beauty mixed solvent of two or more thereof.
  • the amount of the solvent used is usually within 100 times, preferably 1 to 50 times, the weight of the compound (Iu)
  • the substituted phenylboric acids (compound (IX), wherein K is —B (OR 16 ) 2 ), which is an intermediate in the production method (1), may be produced, for example, according to any of the following production methods Can be. Manufacturing method (36) Mg
  • R 16 excludes a hydrogen atom.
  • R 32 represents a lower alkyl group.
  • a borate ester such as trimethyl borate is allowed to act on a substituted phenylglyaryl reagent (IX-A) or a substituted phenyllithium reagent (IX-B) prepared from a substituted halobenzene (XXI I).
  • XXI I substituted phenyl borate
  • VI I-B substituted phenyl borate
  • the above reaction is performed in the following three steps 1) to 3).
  • 1 to 10 equivalents, preferably 1 to 2 equivalents of metal magnesium or alkyllithium is added to 1 equivalent of compound (XXIII), usually at -50 to 200 ° C.
  • the substituted phenyl Grignard reagent (IX-A) or the substituted phenyl lithium reagent (IX-B) is prepared by operating in a temperature range of -20 to 80 ° C.
  • Solvents used in the above reactions 1) and 2) include aliphatic hydrocarbons such as hexane, heptane, octane, and cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, and cumene; Ethers such as getyl ether, diisopropyl ether, dibutyl ether, dimethoxetane, tetrahydrofuran, and dioxane; and a mixed solvent of two or more thereof.
  • the amount of the compound is usually the compound (XXI It is within 100 times, preferably 1 to 50 times the weight of I).
  • Examples of the solvent used in the above reaction 3) include, in addition to those described above, alcohols such as methanol and ethanol; water, and the like.
  • the amount of the solvent is usually 100 parts by weight of the compound (XXII I). It is within 1 times, preferably 1 to 50 times.
  • the compound (VII-D) of the present invention is produced by nitrating the compound (VII-C).
  • the compound (VIIC) of the present invention can be produced, for example, by the above-mentioned production method (36).
  • the above reaction is carried out usually in the absence of a solvent or in a solvent inert to the reaction.
  • the reaction is carried out at 0 ° C, preferably at a temperature in the range of -50 ° C to 0 ° C, by reacting the diluent.
  • the compound of the present invention (VIIF) is produced by oxidizing the compound of the present invention (VIII-II).
  • the compound (VII-II) of the present invention can be produced, for example, by the above-mentioned production method (36).
  • the above reaction is carried out usually in the absence of a solvent or in a solvent inert to the reaction.
  • the reaction is carried out by operating the oxidizing agent at a temperature of 0 ° C, preferably 0 to 150 ° C.
  • Examples of the oxidizing agent include those usually used for the oxidation reaction of an alkyl group such as sodium dichromate and potassium permanganate.
  • the amount of the oxidizing agent usually, the compound (VII-E) per 1 equivalent, It is 1 to 10 equivalents, preferably 1 to 3 equivalents.
  • the above reaction is preferably performed under basic or acidic conditions.
  • Examples of the base used include sodium hydroxide, potassium hydroxide and the like, and examples of the acidic reagent used include sulfuric acid and the like.
  • the above reaction is preferably carried out in a solvent such as water or acetic acid.
  • the amount of the reaction is usually within 100 times, preferably 1 to 50 times the weight of compound (VI I-E). Manufacturing method (39)
  • This production method produces an ester, a thioester, or an acid amide (VII-F ') from the carboxylic acid (VII-F) in the compound of the present invention and an alcohol, thiol, or amine (XII). Things.
  • the present production method comprises halogenating the compound (VII-H) of the present invention to obtain the compound of the present invention. (VII_I) or (VII-J).
  • the compound (VII-H) in the invention compound can be produced, for example, by the above-mentioned production method (36).
  • the present production method corresponds by hydrolyzing the compound (VII-J) of the present invention. It is converted into a carbonyl compound (VII-K).
  • the inventive compound (VII-J) can be produced, for example, by the above-mentioned production method (40).
  • the carbonyl compound (VII-K) in the compound of the present invention is converted to a compound (VII-L) by ketalization.
  • the compound (VI I-K) can be produced, for example, according to the production method (41).
  • the above reaction is carried out in the absence of a solvent or in a solvent inert to the reaction with the corresponding alcohol in the presence of an acidic reagent, usually at a temperature of 0 to 200 ° C, preferably 0 to 150 ° C. .
  • the alcohols include monohydric alcohols such as methanol, ethanol, propanol, and butanol, and dihydric alcohols such as ethylene glycol, 1,3-propanediol, and 1,4-butanediol.
  • the amount of the compound to be used is generally 1 to 30 equivalents, preferably 1 to 10 equivalents, per 1 equivalent of compound (VII-K).
  • the acidic reagent examples include hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, brenstead acid such as trifluoroacetic acid, p-toluenesulfonic acid; or aluminum trichloride, boron tribromide, A Lewis acid such as boron chloride and the like can be used.
  • the amount of the compound to be used is generally 0.005 to 10 equivalents, preferably 0.005 to 0.2 equivalent, per 1 equivalent of compound (VII-K). is there.
  • Suitable solvents to be used include aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane; and aromatic hydrocarbons such as benzene, toluene, xylene and cumene.
  • Hydrocarbons Chloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, benzene, dichlorobenzene Halogenated hydrocarbons such as ethylene; ethers such as getyl ether, diisopropyl ether, dibutyl ether, dimethoxetane, tetrahydrofuran, and dioxane; alcohols such as methanol, ethanol, and propanol; and a mixed solvent of two or more of these And the like.
  • the amount of the solvent to be used is usually within 100 times, preferably 1 to 50 times the amount of the compound (VII-K).
  • substituted phenyltrialkyltins (compound (IX) in which K is Sn (R 20 ) 3 ), which is an intermediate compound of production method (1), may be, for example, as described below.
  • a substituted phenyl Grignard reagent (IX-A) or a substituted phenyl lithium reagent (IX-B) was prepared from the substituted halobenzenes (XX II) in the same manner as described in the production method (36). After that, it can be produced by reacting trialkyltin chlorides.
  • (XVI II) which is a starting compound of the production method (23) is produced by reacting the compound (IG) with the compound (XXIII) in the presence of a base, for example, as described below. can do.
  • the compound of the present invention has isomers such as optical isomers, diastereomers, and isomers depending on the structure.
  • the present invention includes all of these. Each of these isomers can be obtained by isolation from a mixture or by selective production according to a known method.
  • each isomer may be used alone or as a mixture of isomers.
  • the drug substance When the compound of the present invention is used as a herbicide, the drug substance may be applied as it is, but it is usually used in the form of a wettable powder, a granule, an emulsion, a flowable and the like using an appropriate auxiliary agent. .
  • the content of the compound of the present invention in the preparation varies depending on the form of the preparation. In general, for example, 1 to 90% by weight for a wettable powder, 0.1 to 30% by weight for a granule, and 1 to 50% for an emulsion. 5% by weight is appropriate for flowables.
  • These preparations containing the compound of the present invention are applied as they are or diluted with water before application.
  • Auxiliaries used in the preparation of drug products include, for example, solid carriers such as kaolin, bentonite, talc, diatomaceous earth, white carbon, starch; water, alcohols (methanol, ethanol, propanol, butanol, Ethylene glycol, etc.), Ketones (acetone, methyl ethyl ketone, cyclohexanone, isophorone, etc.), Ethers (getyl ether, dioxane, cellosolves, etc.), Aliphatic hydrocarbons (kerosene, kerosene, etc.) ), Aromatic hydrocarbons (benzene, toluene, xylene, cumene, solvent naphtha, methylnaphthylene, etc.), halogenated hydrocarbons (dichloroethane, carbon tetrachloride, trichlorobenzene, etc.), acid amides (dimethylformamide) , Dimethyl
  • an adjuvant such as a spreading agent is added to the spray liquid to improve the adhesiveness and spreadability and enhance the herbicidal effect. Is also good.
  • auxiliary agents such as spreading agents used include surfactants (the above-mentioned nonionic surfactants, cationic surfactants, anionic surfactants, amphoteric surfactants), paraffin, and polyvinyl acetate. , Polyacrylates, ethylene glycol, polyethylene glycol, crop oils (mineral oils, animal and vegetable oils, etc.), liquid fertilizers and the like. These adjuvants may be used in combination of two or more if necessary.
  • auxiliary agents used such as spreading agents, varies depending on the type, but it is usually appropriate to add 0.01 to 5% by weight to the spray liquid. Depending on the type of adjuvant, it may be added in advance as a component in the drug product.
  • the application amount of the compound of the present invention varies depending on conditions such as the structure of the compound, the target weed, the treatment time, the treatment method, and the properties of the soil.
  • the amount of the active ingredient per hectare is usually 2 to 2000 g, and is preferably 2 to 2000 g. A range of 5 to 1000 grams is appropriate.
  • the weeds targeted by the compound of the present invention include, for example, Shiroza, Akaza, Inuyu-de, Haruyu-de, Inubu, Aobu, Hakobe, Hotokenoza, Ichibi, Ona Momi, Malva Asagao, Dwarf Asagao, Seiyokarashina , Broadleaf weeds such as jaemgra, sayeosumire, oroshigiku, kosendangusa, and narrow leaf weeds such as mehishiba, ohishiba, inubie and enocologusa.
  • broadleaf weeds such as Kikasigusa, Azena, Konagi, Abnome, Mizohakobe, Heramoda power, Omodaka, Patricia, etc.
  • narrow leaf weeds such as Yuinubie, Yumagayari, Hoyurui and Mizugayari are mentioned.
  • the compound of the present invention can be used for soil treatment, foliage treatment and flooding treatment in upland fields and paddy fields.
  • the above weeds can be controlled by any treatment method.
  • the compound of the present invention has little effect on cultivated crops such as corn, wheat, barley, rice, soybean and the like in both soil treatment and foliage treatment, and is a selective herbicide in cultivation of these crops. It can be used as
  • the herbicide containing the compound of the present invention as an active ingredient can be mixed and applied with other pesticides such as insecticides, fungicides, and plant growth regulators used in the same field, and fertilizers. In order to further stabilize the herbicidal effect, it can be mixed and applied with other herbicides.
  • the respective preparations may be mixed at the time of application, or may be applied as a preparation containing both in advance. Examples of the herbicides that can be suitably mixed and applied with the compound of the present invention include the following.
  • Triazine herbicides are Triazine herbicides:
  • Example 1 the present invention will be described more specifically with reference to examples of the present invention. However, the present invention is not limited to the following examples unless it exceeds the gist.
  • Example 1 the present invention is not limited to the following examples unless it exceeds the gist.
  • 4,5-Dichloro-6-ethylpyrimidine (0.40 g, 2.24 mmol), tetrakis (triphenylphosphine) palladium in a 4 mL solution of 4-chloro-3-isopropoxyphenylboric acid (0.48 g, 2.24 mmol) in toluene (0) (0.26 g, 0.22 mmol), ethanol (1 mL), sodium carbonate (0.24 g, 2.24 mmol) and water (2 mL) were added, and the mixture was heated to 105 ° C for 4.5 hours with stirring.
  • Carbonic acid rim (0.31 g) was added to a 5-mL solution of 5-ku-guchi- 4- (4-ku-guchi- 2-fluoro-5-hydroxy xyphenyl) -6-ethylpyrimidine (0.53 g, 1.85 mmol) in acetone. , 2.22 mmol) and methyl bromoacetate (0.34 g, 2.22 mmol), and the mixture was heated under reflux with stirring for 5 hours. After acetone was distilled off under reduced pressure, a saturated aqueous solution of ammonium chloride was added, and the mixture was extracted with ethyl acetate.
  • N, N-dimethylformamide of ethyl acrylate (1.00 g, 10.0 mmol), triethylamine (0.56 g, 5.5 mmol), triphenylphosphine (0.26 g, 1.0 mmol), and palladium acetate (0.11 g, 0.49 mmol)
  • 5-chloro-4- (4-chloro-2-fluoro-5-trifluoromethylsulfonyloxyphenyl) -6-ethylpyrimidine (2.10 g, 5.0 mmol). The mixture was stirred for 24 hours while heating at 120 ° C.
  • Ethyl triphenylphosphoranylidene acetate (1.20 g, 3.5 mmol) was added to dilute hydrochloric acid (concentrated hydrochloric acid 0.29 g, distilled water 17 mL), and the mixture was heated to 60 ° C.
  • a solution of Kulamin-T (0.94 g, 4.1 mmol) in water (7 mL) was slowly added thereto, and the mixture was further stirred at 60 ° C for 10 minutes.
  • Ethyl acetate was added thereto and cooled to room temperature. The organic layer was washed with water and then with saturated saline, dried over anhydrous sodium sulfate, and concentrated under reduced pressure.
  • Iron powder (l.OOg), acetic acid (0.5 mL) and water (2.0 mL) were charged into a 100 mL three-necked flask equipped with a mechanical stirrer, and the mixture was stirred at 60 ° C for 20 minutes while heating. Then, N-methylbilysine (10.0 mL) was added, and the temperature was raised to 80 ° C.
  • Ethyl 4- (5-chloro-6-ethylpyrimidine-4-yl) -5-fluoro-2--2-nitrophenoxacetate (1.00 g, 2.6 mmol) was slowly added thereto over 5 minutes. After completion, the mixture was stirred at 80 ° C for 3.5 hours.
  • aqueous sodium hydroxide solution prepared from 4.3 g of sodium hydroxide and 290 mL of water
  • aqueous sodium hydroxide solution was placed in a 1-L three-necked flask equipped with a mechanical stirrer and a thermometer, followed by 4-chloro-2-fluoro-5-methylphenylborane.
  • Acid (10.00 g, 0.053 mol) was added and the temperature was raised to 35 ° C.
  • an aqueous solution of potassium permanganate (18.50 g, 0.12 mol) (220 mL) was slowly added dropwise over 1.5 hours while maintaining the internal temperature at 35-40 ° C. After completion of the dropwise addition, the mixture was further stirred at 50 ° C for 3 hours.
  • Table 1-12 The compounds of the present invention obtained by any of the above Examples are exemplified in Table 1-12.
  • Table 13 shows their physical properties and NMR spectrum data. Further, a method for producing a starting compound other than the above-mentioned 5-substituted-2,4-dihaphenylphenylboric acid will be described as a reference example.
  • the analytical values of this compound were as follows.

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Abstract

L'invention concerne des 4-(phényl substitué)-5-halopyrimidines de formule générale (I) utilisées comme herbicides, ainsi que des composés de bore de formule générale (IV) utilisés comme intermédiaires pour la préparation des produits précités, formules dans lesquelles j et k sont tous deux 0 ou, en variante, l'un d'eux est égal à 0 et l'autre est égal à 1; Z, X1 et Y1 désignent chacun un halogéno; R1 et R2 désignent chacun un alkyle ou analogue; R16 désigne un alkyle ou analogue; et R17 désigne un substituant sur Ar.
PCT/JP2000/005222 1999-08-05 2000-08-03 Derives de 4-(phenyl substitue)-5-halopyrimidine et herbicides contenant ces derives comme ingredients actifs WO2001010843A1 (fr)

Priority Applications (1)

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AU64718/00A AU6471800A (en) 1999-08-05 2000-08-03 4-(substituted phenyl)-5-halopyrimidine derivatives and herbicides containing the same as the active ingredient

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JP22224899 1999-08-05
JP11/222248 1999-08-05

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001068613A1 (fr) * 2000-03-17 2001-09-20 Nissan Chemical Industries, Ltd. Dérivés pyrimidinone et herbicides
JP2003034682A (ja) * 2000-09-19 2003-02-07 Sumitomo Chem Co Ltd ピリミジン化合物及びその用途
KR101350071B1 (ko) * 2006-01-13 2014-01-14 다우 아그로사이언시즈 엘엘씨 6-(다-치환 아릴)-4-아미노피콜리네이트 및 그의제초제로서의 용도
WO2023169984A1 (fr) * 2022-03-11 2023-09-14 Syngenta Crop Protection Ag Composés herbicides
WO2023222589A1 (fr) * 2022-05-20 2023-11-23 Syngenta Crop Protection Ag Composés herbicides

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6422858A (en) * 1987-07-16 1989-01-25 Mitsui Toatsu Chemicals Fluorine-containing pyrimidine derivative and its preparation
WO1993015074A1 (fr) * 1992-01-29 1993-08-05 E.I. Du Pont De Nemours And Company Composes herbicides phenylheterocycliques substitues
GB2277928A (en) * 1993-05-12 1994-11-16 Merck Patent Gmbh Cyclohexyl- and cyclohexylethyl- fluorobiphenyls and liquid-crystalline compositions thereof
WO1998011070A1 (fr) * 1996-09-12 1998-03-19 Basf Aktiengesellschaft Procede pour la preparation de (2'-fluorophenyl)-3-halopyridines

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6422858A (en) * 1987-07-16 1989-01-25 Mitsui Toatsu Chemicals Fluorine-containing pyrimidine derivative and its preparation
WO1993015074A1 (fr) * 1992-01-29 1993-08-05 E.I. Du Pont De Nemours And Company Composes herbicides phenylheterocycliques substitues
GB2277928A (en) * 1993-05-12 1994-11-16 Merck Patent Gmbh Cyclohexyl- and cyclohexylethyl- fluorobiphenyls and liquid-crystalline compositions thereof
WO1998011070A1 (fr) * 1996-09-12 1998-03-19 Basf Aktiengesellschaft Procede pour la preparation de (2'-fluorophenyl)-3-halopyridines

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KONDO Y. ET AL.: "Studies on pyrimidin derivatives. XLI.", CHEMICAL AND PHARMACEUTICAL BULLETIN, vol. 37, no. 10, 1989, pages 2814 - 2816, XP002933782 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001068613A1 (fr) * 2000-03-17 2001-09-20 Nissan Chemical Industries, Ltd. Dérivés pyrimidinone et herbicides
JP2003034682A (ja) * 2000-09-19 2003-02-07 Sumitomo Chem Co Ltd ピリミジン化合物及びその用途
KR101350071B1 (ko) * 2006-01-13 2014-01-14 다우 아그로사이언시즈 엘엘씨 6-(다-치환 아릴)-4-아미노피콜리네이트 및 그의제초제로서의 용도
WO2023169984A1 (fr) * 2022-03-11 2023-09-14 Syngenta Crop Protection Ag Composés herbicides
WO2023222589A1 (fr) * 2022-05-20 2023-11-23 Syngenta Crop Protection Ag Composés herbicides

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