Shin-etsu Chemical Co., Ltd.

Miyoshi Yamashita

Takeshi Kinsho

Yuki Miyake

Takehiko Fukumoto

Naoki Ishibashi

Yusuke Nagae

Akihiro Baba

Shinnosuke Wakamori

Takeru Watanabe

Tomohiro Watanabe

Tatsuya Hojo

Fumiaki Mochizuki

Erina Ohno

The present invention relates to a process for preparing a (2-cyclopentenyl)acetate ester compound of general formula (2) as described herein, the process comprising: subjecting a haloacetaldehyde alkyl 2-cyclopentenyl acetal compound of general formula (1) as described herein to a dehydrohalogenation reaction in the presence of a base, followed by a rearrangement reaction to form the (2-cyclopentenyl)acetate ester compound of general formula (2). The present invention also relates to a process for preparing a (2-cyclopentenyl)acetic acid compound of general formula (3) as described herein, the process comprising hydrolyzing the (2-cyclopentenyl)acetate ester compound of general formula (2) to form the (2-cyclopentenyl)acetic acid compound of general formula (3). The present invention also relates to a haloacetaldehyde alkyl 2-cyclopentenyl acetal compound of general formula (1) as described herein.

Haloacetaldehyde alkyl 2-cyclopentenyl acetal compound and a process for preparing the same, a process for preparing a (2-cyclopentenyl)acetate ester compound therefrom, and a process for preparing a (2-cyclopentenyl)acetic acid compound therefrom

The present invention relates to a process for preparing a (1S,2R)-(2-hydroxy-3,5,5-trimethyl-3-cyclopentenyl)methyl carboxylate compound of the following general formula (S,R)-(2), wherein Rrepresents a monovalent hydrocarbon group having 1 to 6 carbon atoms, and a bold wedged bond represents the absolute configuration, and a (1R,2S)-(2-acetoxy-3,5,5-trimethyl-3-cyclopentenyl)methyl carboxylate compound of the following general formula (R,S)-(3), wherein Ris as defined above, a hashed wedged bond represents the absolute configuration, and Ac represents an acetyl group, the process comprising: subjecting a (1RS,2SR)-(2-hydroxy-3,5,5-trimethyl-3-cyclopentenyl)methyl carboxylate compound of the following general formula (RS,SR)-(2), wherein Ris as defined above, and a hashed unwedged bond represents a relative configuration, to a kinetic resolution reaction with a lipase in the presence of vinyl acetate to obtain the (1S,2R)-(2-hydroxy-3,5,5-trimethyl-3-cyclopentenyl)methyl carboxylate compound ((S,R)-(2)) and the (1R,2S)-(2-acetoxy-3,5,5-trimethyl-3-cyclopentenyl)methyl carboxylate compound ((R,S)-(3)).

Kinetic resolution reaction of a (1RS,2SR)-(2-hydroxy-3,5,5-trimethyl-3-cyclopentenyl)methyl carboxylate compound, a process for preparing optically active trans-&#x3b1;-necrodyl isobutyrate, and a process for preparing optically active &#x3b3;-necrodyl isobutyrate

The present invention provides a process for preparing a (1,2-dimethyl-3-methylenecyclopentyl)acetate compound of the following general formula (3), wherein R represents a linear or branched alkyl group having 1 to 4 carbon atoms, the process comprising subjecting a haloacetaldehyde alkyl 2,3-dimethyl-2-cyclopentenyl acetal compound of the following general formula (1), wherein R is as defined above, and Y represents a halogen atom, to a dehydrohalogenation reaction in the presence of a base, followed by a rearrangement reaction to obtain a (1,2-dimethyl-2-cyclopentenyl)acetate compound of the following general formula (2), wherein R is as defined above, and subjecting the (1,2-dimethyl-2-cyclopentenyl)acetate compound (2) to an epoxidation reaction, followed by an isomerization reaction and then a methylenation reaction to obtain the (1,2-dimethyl-3-methylenecyclopentyl)acetate compound of the following general formula (3). The present invention also provides a process for preparing (1,2-dimethyl-3-methylenecyclopentyl)acetaldehyde of the following formula (4), the process comprising the aforesaid process for preparing the (1,2-dimethyl-3-methylenecyclopentyl)acetate compound (3), and converting an alkoxycarbonylmethyl group (i.e., &#x2014;CHC(&#x2550;O)OR) of the (1,2-dimethyl-3-methylenecyclopentyl)acetate compound (3) to a formylmethyl group (i.e., &#x2014;CHCHO) to obtain (1,2-dimethyl-3-methylenecyclopentyl)acetaldehyde (4).

Processes for preparing a (1,2-dimethyl-3-methylenecyclopentyl)acetate compound and (1,2-dimethyl-3-methylenecyclopentyl)acetaldehyde

The present invention provides a process for preparing a compound of the following general formula (2): wherein Rrepresents a monovalent hydrocarbon group having 1 to 10 carbon atoms, and Rrepresents a hydrogen atom or a methyl group, the process comprising: subjecting a compound of the following general formula (1): wherein Rand Rrepresent, independently of each other, a monovalent hydrocarbon group having 1 to 10 carbon atoms, Rrepresents a hydrogen atom or a methyl group, and the wavy bond represents an E-configuration, a Z-configuration, or a mixture thereof, to a Dieckmann condensation in the presence of base to form the compound (2). 

Processes for preparing 5,5-dimethyl-2-oxo-3-cyclopentene-1-carboxylate compounds and 3,5,5-trimethyl-2-oxo-3-cyclopentene-1-carboxylate compounds from 3,3-dimethyl-1-butene-1,4-dicarboxylate compounds and 1,3,3-trimethyl-1-butene-1,4-dicarboxylate compounds, and 1,3,3-trimethyl-1-butene-1,4-dicarboxylate compounds

The present invention provide for preparing a formylalkenyl alkoxymethyl ether compound of the following general formula (2): RCHOCHO(CH)CH&#x2550;CHCHO (2), wherein Rrepresents a hydrogen atom, an n-alkyl group having 1 to 9 carbon atoms, or a phenyl group; and 'a' represents an integer of 1 to 10, the process comprising: hydrolyzing a dialkoxyalkenyl alkoxymethyl ether compound of the following general formula (1): RCHOCHO(CH)CH&#x2550;CHCH(OR)(OR) (1), wherein Rand Rrepresent, independently of each other, a monovalent hydrocarbon group having 1 to 15 carbon atoms, or Rand Rmay form together a divalent hydrocarbon group, R-R, having 2 to 10 carbon atoms; and Rand 'a' are as defined above, in the presence of an acid while removing an alcohol compound thus generated to form the formylalkenyl alkoxymethyl ether compound (2).

Process for preparing a formylalkenyl alkoxymethyl ether compound and processes for preparing conjugated diene compounds from the same

The present invention provides a process for preparing an alkoxymethyl alkynyl ether compound having a terminal triple bond of the following formula (4): H&#x2014;C&#x2261;C(CH)OCHOCHR (4), wherein R represents a hydrogen atom, an n-alkyl group having 1 to 9 carbon atoms, or a phenyl group, and 'a' represents an integer of 1 to 10, the method comprising subjecting an alkynol compound having a terminal triple bond of the following formula (1): H&#x2014;C&#x2261;C(CH)OH (1), wherein 'a' is as defined above, to an alkoxymethylation with a halomethyl alkyl ether compound of the following formula (3): RCHOCHX (3), wherein X represents a halogen atom, and R is as defined above, in the presence of a dialkylaniline compound of the following formula (2): [CH(CH)][CH(CH)]NCH(2), wherein b and c represent, independently of each other, an integer of 0 to 9, to form the alkoxymethyl alkynyl ether compound (4) having a terminal triple bond.

Process for preparing an alkoxymethyl alkynyl ether compound having a terminal triple bond

The present invention provides a process for preparing 2-isopropenyl-5-methyl-4-hexenoic acid of the following formula (4), comprising steps of: subjecting a Grignard reagent of the following general formula (1), wherein Rrepresents a linear, branched, or aromatic monovalent hydrocarbon group having 1 to 8 carbon atoms, and X represents a chlorine atom, a bromine atom, or an iodine atom, and 1,1,1,3,3,3-hexamethyldisilazane to a deprotonation reaction to form a 1,1,1,3,3,3-hexamethyldisilazane derivative; and subjecting 2-methyl-3-buten-2-yl 3-methyl-2-butenoate of the following formula (3) to a rearrangement reaction in the presence of the 1,1,1,3,3,3-hexamethyldisilazane derivative to form 2-isopropenyl-5-methyl-4-hexenoic acid (4). 

Processes for preparing 2-isopropenyl-5-methyl-4-hexenoic acid, 2-isopropenyl-5-methyl-4-hexen-1-ol, and a carboxylate ester thereof

Provided are methods including a method for industrially producing (2S,12Z)-2-acetoxy-12-heptadecene, which is, for example, a sex pheromone of pistachio twig borer. The methods can include a production method comprising a step of reacting racemic (2RS,12Z)-2-hydroxy-12-heptadecene with vinyl benzoate in the presence of a lipase to obtain a mixture of optically active (2R,12Z)-2-benzoyloxy-12-heptadecene of Formula (R,Z-2) and optically active (2S,12Z)-2-hydroxy-12-heptadecene of Formula (S,Z-1), a step of heating the mixture to distill out the optically active (2S,12Z)-2-hydroxy-12-heptadecene (S,Z-1), and a step of acetylating the optically active (2S,12Z)-2-hydroxy-12-heptadecene (S,Z-1) to obtain optically active (2S,12Z)-2-acetoxy-12-heptadecene of Formula (S,Z-3). 

Method for producing (Z)-2-benzoyloxy-12-heptadecene and (2S,12Z)-2-hydroxy-12-heptadecene and method for producing (2S,12Z)-2-acetoxy-12-heptadecene

The object of the present invention is to provide an industrial and economical process for preparing (E2)-cis-6,7-epoxy-2-nonenal of the following formula (3):  The present invention provides a process for preparing (E2)-cis-6,7-epoxy-2-nonenal (3), comprising at least steps of: to form (E2,Z6)-2,6-nonadienal of the following formula (2); and 

Process for preparing (E2)-cis-6,7-epoxy-2-nonenal

The object of the present invention is to provide an industrial and economical process for preparing (E2,Z6)-2,6-nonadienal of the following formula (4):  The present invention provides a process for preparing (E2,Z6)-2,6-nonadienal (4), comprising at least steps of: to oxidation with a sulfoxide compound of the following formula (2):CH(R)S&#x2550;O&#x2003;&#x2003;(2)

Process for preparing (E2,Z6)-2,6-nonadienal

Provided are a sustained release pheromone preparation capable of maintaining a high amount of pheromone release throughout a control period of vine mealybug (VMB) having lavandulyl senecioate (LVSN) as a pheromone substance; and a control method with the preparation. More specifically, provided are a sustained release pheromone preparation comprising a first pheromone substance, and a first container having the first pheromone substance sealed therein and comprising a first polymer membrane made of an ethylene vinyl acetate copolymer containing vinyl acetate units of from 0.5 to 10% by weight, wherein the first pheromone substance is lavandulyl senecioate, which is a pheromone substance of vine mealybug, and the lavandulyl senecioate can be released into the air through the first polymer membrane for 150 days or more; and others.

Sustained release pheromone preparation of vine mealybug and control method using the preparation

Provided are industrial and economical methods for producing 2,6-dimethyl-1,5-heptadien-3-yl acetate (3), which is, for example, a sex pheromone component of Comstock mealybug, and 2,6-dimethyl-1,5-heptadien-3-ol (2), which is an intermediate of the acetate (3). More specifically, provided are a method for producing 2,6-dimethyl-1,5-heptadien-3-ol comprising a step of subjecting 2-methyl-3-buten-2-yl 2-methyl-2-propenyl ether (1) to a rearrangement reaction in the presence of a base to obtain 2,6-dimethyl-1,5-heptadien-3-ol (2), and a method for producing 2,6-dimethyl-1,5-heptadien-3-yl acetate comprising a step of acetylating the produced 2,6-dimethyl-1,5-heptadien-3-ol (2) to obtain 2,6-dimethyl-1,5-heptadien-3-yl acetate (3). 

Methods for producing 2,6-dimethyl-1,5-heptadien-3-ol and 2,6-dimethyl-1,5-heptadien-3-yl acetate

A method for the preparation of a sex pheromone of Obscure Mealy bug (OMB), (&#xb1;)(2,3,4,4-tetramethycyclopentyl) methyl acetate includes a step of subjecting alpha-halotetramethylcyclohexanone to a Favorskii rearrangement to obtain a 2,3,4,4-tetramethylcyclopentane compound (2), a step of subjecting the compound (2) to reduction to obtain (2,3,4,4-tetramethylcyclopentyl)methanol compound (3) and a step of subjection the compound (3) to acylation to obtain a (2,3,4,4-tetramethylcyclopentyl)methyl carboxylate compound (4).

Alpha-halotetramethycyclohexanone, a method for the preparation thereof, and a method for the preparation of a (2,3,4,4-tetramethylcyclopentyl)methy carboxylate compound

Provided are a method for efficiently producing an asymmetric conjugated diyne from an inexpensive and safe alternative compound to hydroxylamine hydrochloride and a method for producing a Z,Z-conjugated diene compound from the asymmetric conjugated diyne compound thus obtained. More specifically, provided is a method for producing an asymmetric conjugated diyne compound comprising a step of subjecting a terminal alkyne compound (1): HC&#x2261;C&#x2014;Z&#x2014;Yto a coupling reaction with an alkynyl halide (2): Y&#x2014;Z&#x2014;C&#x2261;C&#x2014;X by using sodium borohydride in water and an organic solvent in the presence of a copper catalyst and a base to obtain the asymmetric conjugated diyne compound (3): Y&#x2014;Z&#x2014;C&#x2261;C&#x2014;C&#x2261;C&#x2014;Z&#x2014;Y. In addition, provided is a method for producing a Z,Z-conjugated diene compound by reducing the resulting asymmetric conjugated diyne compound, or the like.

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Joetsu, Japan

Miyoshi Yamashita