WO2004069780A1 - Process for production of adipic acids having side chains - Google Patents

Abstract

A process for the production of adipic acids having side chains as represented by the general formula (II): (wherein R1, R2, R3, R4, R5 and R6 are each independently hydrogen or alkyl, with the proviso that at least one of R1, R2, R3, R4, R5 and R6 is alkyl), characterized by comprising the step of subjecting a compound represented by the general formula (I): (wherein R1, R2, R3, R4, R5 and R6 are each as defined above; R7 is formyl or hydroxymethyl; and the symbol ===== represents a single bond or a double bond) to reaction in the presence of an alkali metal hydroxide or an alkaline earth metal hydroxide.

Description

 Specification

 Method for producing branched adipic acid

Technical field

 The present invention relates to a method for producing a branched adipic acid which is useful for applications such as a polyamide modifier, a polyester modifier, a cosmetic base, and a raw material of polyester or polyamide.

Background art

 Conventionally, the following methods (1) and (2) have been known as methods for producing branched adipic acid.

(1) The method for producing 2,5-getyl adipic acid is as follows: 1,3-butadiene and sodium metal are reacted in dimethyl ether at -70 ° C, and magnesium bromide; There is known a method for producing the desired 2,5-getyl adipic acid by reacting (see US Pat. No. 3,375,272).

 (2) As a method for producing 2,5-dimethylazivic acid, a peroxide such as ditert-butylperoxide is used as a catalyst, and propionic acid and acetylene are reacted at 120 ° C in n-nonane. A method for producing the desired 2,5-dimethyladipic acid is known (see US Pat. No. 3,549,977).

 However, in the case of the method for producing ①2,5-getyl adipic acid, sodium metal is used, and this compound has properties such as spontaneous combustion and explosion upon reaction with water. There are safety issues.

 (2) In the case of the method for producing 2,5-dimethylazivic acid, it has a very wide explosion limit due to mixing with air or oxygen and a peroxidic sulphate which has the property of exploding by heating, impact, etc. There are safety issues due to the use of acetylene.

 As described above, these two methods are not practically satisfactory as industrial manufacturing methods.

Disclosure of the invention

 An object of the present invention is to provide an industrially suitable method for producing a branched adipic acid.

 The present invention provides the following (1) to (3).

(1) General formula (I)

(Wherein, RR ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different and represent a hydrogen atom or alkyl, R ⁷ represents formyl or hydroxymethyl, and is a single bond or a double bond. Represents a heavy bond, provided that at least one of II ¹ , R ² , R ³ , R ⁴ ; R ⁵ and R ⁶ is alkyl) A general formula (II) characterized by including a step of reacting in the presence of a hydroxide of an alkaline earth metal.

R ¹ R ² R ⁴ R ⁶

 HOOC— C—— C C C— COOH

HR ³ R ⁵ H (Π)

(Wherein, RR ² , R ³ , R ⁴ , ⁵ and R ⁶ are each as defined above).

(2) The method for producing a branched adipic acid according to the above (1), wherein R ¹ and R ⁶ are alkyl and R ² , R ³ , R ⁴ and R ⁵ are hydrogen atoms.

 (3) The method for producing branched adipic acid according to the above (1) or (2), wherein the hydroxide of alkali metal or alkaline earth metal is sodium hydroxide or lithium hydroxide. Hereinafter, the compound represented by the general formula (I) may be referred to as a compound (I), and the branched adipic acid represented by the general formula (II) may be referred to as a compound (II).

 In the definition of each group in the general formula, examples of the alkyl include linear or branched alkyl having 1 to 1 ° carbon atoms, and specific examples thereof include methyl, ethyl, propyl, isopropyl, and butyl. And isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl and the like, and among them, methyl or ethyl is preferable.

Compound (I), which is a raw material of the production method of the present invention, can be obtained by cyclizing an acrolein derivative by a known method (US Pat. Accordingly, the obtained dihydropyran derivative is converted to hydrogen It can be obtained by reduction.

 Examples of hydroxides of alkaline metal or alkaline earth metals include hydroxide hydroxide, sodium hydroxide, magnesium hydroxide, calcium hydroxide, and the like. These may be used alone or in combination of two or more.

 The amount of hydroxide of alkali metal or earth metal used is preferably 1.5 mol or more, more preferably 1.5 to 5.5 mol, per 1 mol of compound (I). It is preferably 0 mol, and more preferably 1.8 to 3.0 mol. '' In the production method of the present invention, the reaction temperature is preferably from 200 to 320 ° C, more preferably from 200 to 250 ° C, and further preferably from 220 to 250 ° C. More preferably, the temperature is 250 ° C.

 The reaction is carried out at normal pressure or under pressure, preferably at most 2.0 MPa, more preferably at most 1.0 MPa.

 The reaction time is not particularly limited, but is preferably 5 hours or more, and more preferably 5 to 20 hours.

 In the reaction, a reaction solvent may be used, and the reaction solvent is not particularly limited as long as it does not affect the reaction. Examples of the reaction solvent include ether solvents such as dibenzyl ether, hydrocarbon solvents such as liquid paraffin, and the like, and these may be used as a mixture. The amount of the reaction solvent is not particularly limited, but is preferably 50 to 200% by weight, more preferably 70 to 150% by weight, based on the compound (I). '

 Further, for the purpose of shortening the reaction time and improving the yield, the reaction may be performed by adding a metal oxide such as zinc oxide or copper oxide as a catalyst. The amount of the catalyst to be used is preferably 0.1 to 5% by weight based on the compound (I). '

 After the reaction, the compound (II) can be obtained in the form of a salt of an alkali metal or an alkaline earth metal. The compound (II) can be obtained by adding an aqueous solution of sulfuric acid, hydrochloric acid or the like thereto.

 The obtained compound (II) may be subjected to a purification operation such as extraction, crystallization, or distillation from the reaction solution or the like in order to improve the purity.

The production method of the present invention is an industrially suitable production method that is simple, inexpensive, and excellent in safety. Compound (II) is useful for applications such as polyamide modifiers, polyester modifiers, cosmetic bases, and raw materials for polyesters or polyamides.

BEST MODE FOR CARRYING OUT THE INVENTION

Example 1: Synthesis of 2,5-getyl adipic acid

 2,5-Jetyl-1,3,4-dihydro-1H-pyran-1-2-methanol

.170.0 g (1.0 mol), sodium hydroxide (manufactured by Kanto Chemical Co., Ltd.) 170.0 g (2.4 mol 1) and liquid paraffin 60 S (manufactured by Chuo Kasei Co., Ltd.) 200 g It was charged into a 1 L nickel autoclave equipped with a pressure control valve and an electric furnace capable of controlling the temperature, and heated and stirred at 1.0 MPa or less. The generated hydrogen gas was measured overnight, and the reaction was carried out at 220 to 230 ° C. for 10 hours while checking the progress of the reaction. After the reaction, the reaction solution containing 2,5-getyl sodium adipic acid salt was cooled to 100 ° C or less, dissolved in 400 g of distilled water, and further precipitated by adding dropwise 420 g of 30% sulfuric acid. , 5-Jetyl adipine yeast was collected by filtration. The obtained crude 2,5-diethyladipate was dissolved in 300 ml of methyl isobutyl ketone, washed with water, and concentrated under reduced pressure at 60 ° C to obtain 183 g of a residue containing 2,5-diethyladipate. Obtained. The residue was crystallized from n-hexane to obtain 170 g (yield: 85%) of white crystals of 2,5-getyladipic acid. The physical property values of the obtained 2,5-getyladipic acid are shown below.

_{^ -NM (400MHz, CDC 1 3} , TMS) δ (iii): 0. 90 (t, 6H), 1. 48- 1. 63 (m, 8H), 2. 23 - 2, 25 (m, 2 ^{H) 13 C - NMR (100MHz} , CDC 1 3, TMS) δ (m): 1 1. 92, 25. 81, 30. 38, 47. 55, 177. 23

GC-MS (CI): (Analysis after derivation to dimethyl ester)

Retention time 8.50 minutes (m / z): 230 (M + 1)

Retention time 8.60 minutes (m / z): 230 (M + 1)

GC-MS analysis conditions and dimethyl ester preparation method

Column: Capillary column CP-Wax 58 (FFAP) CB (GL Science) (25mx0.2m)

Column temperature: After holding at 100 ° C for 1 minute, raise the temperature to 270 ° C at 8 ° C / min.

Injection temperature: 270 ° C Detector temperature: 280 ° C

 After dissolving the sample in a benzene / methanol (3/7 volume / volume) solution, add trimethylsilyldiazomethane (10% n-hexane, solution) and stir at room temperature for 30 minutes to remove the dimethyl ester solution. Prepared.

Example 2: Synthesis of 2,5-getyladipate

 The starting materials were 2,5-diethyltetrahydropyran-1-methanol 172.0 g (1. Omo 1), potassium hydroxide (manufactured by Kanto Chemical Co., Ltd.) 99.0 g (3.0 mo 1) and liquid paraffin 60 The same operation as in Example '1 was carried out except that S (manufactured by Chuo Kasei Co., Ltd.) was changed to 200 g, to give 158 g (yield 79%) of white crystals of 2,5-getyladipic acid. '' Example 3: Synthesis of 2,5-diethyladipate

 The raw materials were 2,5-tetraethyl-1,4-dihydro-2H-pyran-1-2-carboaldehyde '168.0 g (1.0 Omo 1), hydroxide hydroxide (Kanto Chemical Co., Ltd.) 99.0 g ( 3. Omo 1) and liquid paraffin 60 S (manufactured by Chuo Kasei Co., Ltd.) were changed to 200 g, and the same operation as in Example 1 was carried out to obtain 131 g of 2,5-getylazivic acid as white crystals (yield 65 %).

Reference Example 1: Synthesis of 2,5-diethyl-3,4-dihydro-2H-pyran-1-2-carbaldehyde

 To an autoclave having an internal volume of 10 Oml and containing a stirring chip was added 50 g of 2-ethyl acetate (Aldrich, purity: 85%), and the mixture was reacted at 150 to 160 ° C for 8 hours. Then, the reaction mixture was subjected to distillation under reduced pressure to obtain 36.8 g of 2,5-getyl-1,3,4-dihydro-2H-pyran-1-carbaldehyde as a fraction at 82 to 84 ° C./50 Pa. (Yield 87%).

Reference Example 2:. 2 ₃ 5 Jechirute synthesis tiger tetrahydropyran one 2- methanol

In a photoclave containing a stirring chip and having an internal volume of 10 Oml, 2,5-dimethyl-1,3,4-dihydro-12H-pyran-12-carbaldehyde 10. Og and sponge nickel catalyst (Nikki Chemical Co., Ltd. —113) 0.3 g was added, and the mixture was reacted at a hydrogen pressure of 2.0 MPa and a temperature of 150 ° C for 6 hours. After the completion of the reaction, the sponge nickel catalyst was filtered off from the reaction solution, and the obtained filtrate was subjected to silica gel column chromatography [solvent: n-hexane / ethyl acetate (volume ratio)] to give a solution. twenty five- 9.8 g of getyltetrahydropyran-12-methanol was obtained (98% yield) .o Reference Example 3: Synthesis of 2,5-diethyl-1,3,4-dihydro-12H-pyran-12-methanol

 In a 100 ml autoclave containing a stirring chip, 2,5-diethyl-1,3,4-dihydro-1 2 H-pyran-1-carbaldehyde 10.0 § "ぉ 11-〇-based catalyst (118 0.52 g, manufactured by 1 311 octane ", and reacted at a hydrogen pressure of 2.0 MPa and a temperature of 130 ° C. for 5 hours. After completion of the reaction, the Cu—Cr system catalyst was separated from the reaction solution by filtration, and the obtained filtrate was subjected to silica gel column chromatography [solvent: n-hexane / ethyl acetate = 9Z1 (volume ratio)]. 9.6 g of 2,5-diethyl-1,3,4-dihydro-1H-pyran-12-methanol was obtained (yield 95%).

Industrial applicability

 According to the present invention, there is provided an industrially suitable method for producing a branched adipic acid which is useful for applications such as a polyamide modifier, a polyester modifier, a cosmetic base, a polyester or a polyamide raw material, and the like.

Claims

The scope of the claims  1. General formula (I)

(Wherein, RR \ RR ⁴ , R ⁵ and R ⁶ are the same or different and represent a hydrogen atom or alkyl, R ⁷ represents formyl or hydroxymethyl, and represents a single bond or a double bond Provided that at least one of II ¹ , R ² , R ³ ,. R ⁴ , R ^5, and R ⁶ is alkyl) is converted to an alkali metal or alkaline earth metal water. General formula (II), characterized by comprising a step of reacting in the presence of an oxide. R ¹ R ² R ⁴ R ⁶  HOOC— C— C— -C—— C— COOH HR ³ R ⁵ H (Π) (Wherein, RRR ³ , RR ⁵ and R ⁶ have the same meanings as described above, respectively). 2. The method for producing branched adipic acid according to claim 1, wherein R ¹ and R ⁶ are alkyl, and R ² , R ³ , and R ⁴ and R ⁵ are hydrogen atoms.  3. The method for producing branched adipic acid according to claim 1, wherein the hydroxide of the alkaline metal or the alkaline earth metal is sodium hydroxide or the hydroxide of the alkaline metal. '