Shin-etsu Chemical Co., Ltd.

Other

Akihiro Baba

Takeshi Kinsho

Yusuke Nagae

Naoki Ishibashi

Yuki Miyake

Tomohiro Watanabe

Miyoshi Yamashita

Tatsuya Hojo

Tatsuya Fujii

Yasuhiko Kutsuwada

Provided is a 3-acyloxymethyl-3-butenal acetal compound of General Formula (10): wherein Rand R, which may be the same or different, are each an alkyl group having 1 to 6 carbon atoms, or are bonded to each other to form a divalent alkylene group having 2 to 12 carbon atoms, and Xis an acyloxy group having 1 to 6 carbon atoms.

3-acyloxymethyl-3-butenal acetal compounds

A process for process for preparing 6-isopropenyl-3-methyl-9-decenyl acetate of the following formula (3), wherein Ac represents an acetyl group, the process comprising steps of: preparing a nucleophilic reagent, 5-isopropenyl-2-methyl-8-nonenyl compound, of the following general formula (1): wherein Mrepresents Li, MgZ, ZnZ, Cu, CuZ, or CuLiZ, wherein Zrepresents a halogen atom or a 5-isopropenyl-2-methyl-8-nonenyl group, from a 5-isopropenyl-2-methyl-8-nonenyl halide compound of the following general formula (4): wherein Xrepresents a halogen atom; subjecting the nucleophilic reagent (1), 5-isopropenyl-2-methyl-8-nonenyl compound, to an addition reaction with at least one electrophilic reagent selected from the group consisting of formaldehyde, paraformaldehyde, and 1,3,5-trioxane, followed by a hydrolysis reaction to form 6-isopropenyl-3-methyl-9-decenol of the following formula (2); and acetylating 6-isopropenyl-3-methyl-9-decenol (2) to form 6-isopropenyl-3-methyl-9-decenyl acetate (3).

Process for preparing 6-isopropenyl-3-methyl-9-decenyl acetate and intermediates thereof

A method for producing a 7-methyl-3-methylene-7-octenyl carboxylate compound (1), the method including the step of coupling a nucleophilic reagent of General Formula (8): wherein M is a cationic moiety, with an acetal compound of General Formula (9): wherein Rand R, which may be the same or different, are each an alkyl group having 1 to 6 carbon atoms, or are bonded to each other to form a divalent alkylene group having 2 to 12 carbon atoms, and X is a leaving group, to obtain the 7-methyl-3-methylene-7-octenal acetal compound.

Method for producing 7-methyl-3-methylene-7-octenal acetal compound

The present invention relates to a process for preparing a 3-isopropenyl-6-heptenal compound of the following formula (2): wherein Rrepresents a hydrogen atom or a methyl group, the process comprising: subjecting a 3-isopropenyl-6-heptenoate ester compound of the following formula (1): wherein Ris as defined above, and Rrepresents a monovalent hydrocarbon group having 1 to 10 carbon atoms, to a reduction reaction with a reducing agent to form the 3-isopropenyl-6-heptenal compound (2).

Processes for preparing a 3-isopropenyl-6-heptenal compound and a 6- isopropenyl-3-methyl-3,9-decadienyl carboxylate compound, and an intermediate therefor

The present invention provides a process for preparing 6-isopropenyl-3-methyl-9-decenyl acetate (5): wherein Ac represents an acetyl group, the process comprising steps of: subjecting a 2-methyl-2,6-heptadiene compound (1) having a leaving group X at position 1: wherein X represents an acyloxy group having 1 to 10 carbon atoms including the carbon atom of the carbonyl group, an alkanesulfonyloxy group having 1 to 10 carbon atoms, an arenesulfonyloxy group having 6 to 20 carbon atoms, or a halogen atom, to a nucleophilic substitution reaction with a 3-methylpentyl nucleophilic reagent (2) having a protected hydroxyl group at position 5: wherein M represents Li, MgZ, ZnZ, Cu, CuZ, or CuLiZ, wherein Zrepresents a halogen atom or a CHCHCH(CH)CHCHOR group, and R represents a protecting group for a hydroxyl group, to form a 6-isopropenyl-3-methyl-9-decene compound (3) having a protected hydroxyl group at position 1: wherein R is as defined above; subjecting the 6-isopropenyl-3-methyl-9-decene compound (3) having the protected hydroxyl group at position 1 to a deprotection reaction to form 6-isopropenyl-3-methyl-9-decenol (4); and acetylating 6-isopropenyl-3-methyl-9-decenol (4) to form 6-isopropenyl-3-methyl-9-decenyl acetate (5).

Process for preparing 6-isopropenyl-3-methyl-9-decenyl acetate, and intermediates therefor

A process for process for preparing 6-isopropenyl-3-methyl-9-decenyl acetate of the following formula (3), wherein Ac represents an acetyl group, the process comprising steps of: preparing a nucleophilic reagent, 5-isopropenyl-2-methyl-8-nonenyl compound, of the following general formula (1): wherein Mrepresents Li, MgZ, ZnZ, Cu, CuZ, or CuLiZ, wherein Zrepresents a halogen atom or a 5-isopropenyl-2-methyl-8-nonenyl group, from a 5-isopropenyl-2-methyl-8-nonenyl halide compound of the following general formula (4): wherein Xrepresents a halogen atom; subjecting the nucleophilic reagent (1), 5-isopropenyl-2-methyl-8-nonenyl compound, to an addition reaction with at least one electrophilic reagent selected from the group consisting of formaldehyde, paraformaldehyde, and 1,3,5-trioxane, followed by a hydrolysis reaction to form 6-isopropenyl-3-methyl-9-decenol of the following formula (2); and acetylating 6-isopropenyl-3-methyl-9-decenol (2) to form 6-isopropenyl-3-methyl-9-decenyl acetate (3). 

There are provided methods of efficiently producing compounds that are, for example, sex pheromones of San Jose Scale. For example, there is provided a method for producing a 7-methyl-3-methylene-7-octenyl carboxylate compound (4), the method including the steps of: hydrolyzing a 7-methyl-3-methylene-7-octenal acetal compound (1) to obtain 7-methyl-3-methylene-7-octenal (2); reducing the 7-methyl-3-methylene-7-octenal (2) to obtain 7-methyl-3-methylene-7-octenol (3); and esterifying the 7-methyl-3-methylene-7-octenol (3) to obtain a 7-methyl-3-methylene-7-octenyl carboxylate compound (4). 

7-methyl-3-methylene-7-octenal acetal compound and methods for producing aldehyde compound and ester compound using 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

Provided are a method for producing a terminal conjugated dienal compound without an oxidation reaction and a terminal hydroxyacetal compound useful as an intermediate in the method. More specifically, provided are a method for producing an (E)-dienal compound comprising the steps of: a metalation reaction of an alkynal acetal compound (1) to obtain an organic metal compound (2), an addition reaction of (2) to ethylene oxide to obtain a hydroxyalkynal acetal compound (3), a reduction reaction of (3) to obtain an (E)-hydroxyalkenal acetal compound (4), a functional group conversion reaction of (4) to obtain an (E)-alkenal acetal compound (5) having a leaving group X, an elimination reaction of (5) to obtain an (E)-dienal acetal compound (6), and a hydrolysis reaction of (6) to obtain the (E)-dienal compound (7); and others. 

Method of producing aliphatic aldehyde compound having terminal conjugated diene structure and intermediate therefor

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.

Method for producing asymmetric conjugated diyne compound and method for producing Z,Z-conjugated diene compound using the same

Provided is a process for producing 3,5-dimethyldodecanoic acid, which is an active ingredient of the pheromone of California prionus. More specifically provided is a method for producing 3,5-dimethyldodecanoic acid (5) comprising the steps of converting 2-methylnonyl halide (1) to a 2-methylnonyl metal reagent (2), and reacting the 2-methylnonyl metal reagent (2) with 2-ethylidene malonic acid ester (3) to form 2-(1,3-dimethyldecyl)malonic acid ester (4) as a result of 1,4-addition of the 2-methylnonyl metal reagent (2) to the 2-ethylidene malonic acid ester (3), as shown in the following scheme: 

Method for producing 3,5-dimethyldodecanoic acid

Provided is a process for producing 3,5-dimethyldodecanoic acid, which is an active ingredient of the pheromone of California, and 4-carboxy-3,5-dimethyl-3,5-dodecadienoic acid which is an intermediate useful for producing 3,5-dimethyldodecanoic acid. More specifically, provided is a method for producing 3,5-dimethyldodecanoic acid, comprising the steps of subjecting 3-methyl-2-pentene-1,5-diacid diester (1) and 2-nonanone (2) to a condensation reaction and subsequent hydrolysis into 4-carboxy-3,5-dimethyl-3,5-dodecadienoic acid (3); decarboxylating or decarboxylating and hydrolyzing the 4-carboxy-3,5-dimethyl-3,5-dodecadienoic acid (3) into 3,5-dimethyl-2,4-dodecadienoic acid (4); and hydrogenating the 3,5-dimethyl-2,4-dodecadienoic acid (4) into 3,5-dimethyldodecanoic acid (5), as shown in the following scheme: 

Method for producing 3,5-dimethyldodecanoic acid; and 4-carboxy-3,5-Dimethyl-3,5-dodecadienoic acid

Provided is a simple and efficient method for producing 2-isopropylidene-5-methyl-4-hexenyl butyrate. More specifically, provided is a method for producing 2-isopropylidene-5-methyl-4-hexenyl butyrate, the method including the steps of: isomerizing 2-isopropenyl-5-methyl-4-hexenoic acid ester (1) into 2-isopropylidene-5-methyl-4-hexenoic acid ester (2), reducing thus formed 2-isopropylidene-5-methyl-4-hexenoic acid ester (2) into 2-isopropylidene-5-methyl-4-hexenol (3), and butyrylating thus formed 2-isopropylidene-5-methyl-4-hexenol (3) into 2-isopropylidene-5-methyl-4-hexenyl butyrate (4), wherein R represents a Chydrocarbon group.

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Akihiro Baba