FR2458529A1 - PROCESS FOR THE PREPARATION OF 3,3-DIMETHYL-ALLYL ALCOHOL - Google Patents

Abstract

THE SUBJECT OF THE PRESENT INVENTION IS A PROCESS FOR THE PREPARATION OF 3,3-DIMETHYL-ALLYL ALCOHOL. IT IS CHARACTERIZED IN THAT 3,3-DIMETHYL-ALLYL HALOGENIDE, POSSIBLY DISSOLVED IN AN INERT SOLVENT NOT MISCIBLE TO WATER, IS CAUSED TO REACT WITH AN ALKALINE SALT OF CARBOXYL ACID IN AN AQUEOUS SOLUTION AND IN THE PRESENCE OF PHASE TRANSFER CATALYST, IN A CONDUCTIVE WAY TO A 3,3-DIMETHYL-ALLYL ESTER WHICH, POSSIBLY DISSOLVED IN AN INERT SOLVENT, NON-MISCIBLE TO WATER, IS THEN HYDRAULIZED BY TREATMENT USING AN AQUEOUS ALKALINE HYDROXIDE SOLUTION IN THE PRESENCE OF A PHASE TRANSFER CATALYST. IT RELATES TO THE PREPARATION OF THESE COMPOUNDS.

Description

PROCESS FOR THE PREPARATION OF 3,3-DIMETHYL-ALLYL ALCOHOL

  The subject of the present invention is a process for the preparation of 3,3-dimethylallyl alcohol (3-methyl-but-2-en-1-ol), and more particularly relates to a process for obtaining said alcohol, this process comprising converting the 3,3-dimethyl-allyl halide to a 3,3-dimethyl-allyl carboxylic ester, and then hydrolyzing said ester. These two reactions are performed by the so-called phase transfer method. A number of methods are known from the state of the art for

  synthetically produce 3,3-dimethylallyl alcohol.

  Some of these methods use organo-magnesium compounds (compounds

of Grignard).

  Among these reactions, mention may be made of that which occurs between 2,2-dimethylvinylmagnesium bromide and formaldehyde: ## STR1 ## )

H3C / H3C

H3C

  [H.Normant, "Proceedings Acad Science" (Paris), 240,314 (1955)] and the reaction

  between acetone and 2-bromoethyl acetate, in the presence of magnesium and mercuric chloride, followed by hydrolysis:

H3C

  mg 'HgCL2 C = O + Br-CH2-O-C-CH3 Mg HgCl2 H3C il H3C

- C = CH-CH 2 -O-C-CH 3 (II)

(I)

H3C

KOH, H20

(II) - - (I) (yield: 25%)

  [R.F. Miiller, F. F. North, "Day of Org Chem 16, 728 (1951) 1.

  The aforementioned methods have low industrial applications.

  In fact, it is necessary that they be implemented in an environment

  anhydrous and their yields are low.

  Synthetic methods are also known which involve the isomeric

  2-methyl-buten-4-ol: 1) H2. Pd / C CH 2 = C-CH 2 -CH 2 OH (yield: 70%) 1 CH 3 2) 125-130 ° C., 6 hours CH 3 [according to German Patent Application No. 1,901,709 (BASF)] Fe ( CO) 5

CH2 = C-CH2-CH20H O (I)

0 [sln150-200C, 50 atm.

CH3

  [according to French Patent No. 1,594,968 (BASF)].

  These methods, however, are carried out in the presence of

  flammable and explosive and, in the case where carbon monoxide is used,

even toxic gases.

  A synthetic method has also been described which comprises reducing the e, e-dimethyl-acrylic acid: H3C H3C \ LiALH4 C = CH-COOH LiA [H (I) / H3C

  ["Day of Chem Soc." (C) 811 (1971)].

  However, the dangers of using aluminum-lithium hydride

  acting as a reducing agent are well known.

  Direct hydrolysis of the 3,3-dimethyl-allyl halogen with bases in an aqueous medium does not lead to 3,3-dimethyl-allyl alcohol except in very small amounts, the main product obtained consisting of the isomerization product of 3-methyl-buten-3-ol (III):

H3C H3C OH

C = CH-CH2cL Na2CO3 / H2O C / (II) + (I)

H3C CH CH3

He CH2

[BeiLstein R. III 1 page 7951.

  The tertiary alcohol thus obtained (III) can be converted to 3,3-dimethylallyl alcohol by treatment with boric acid: (III) H3BO3 (I) (yield: 50%)

- 110 C

  [I.N. Nazarov, S.S. Yufit, "Zhur, Khim Obs." 29,783 (1959),

"Chemical Abstract" 54, 1280b].

3 2458529

  A reasonable process could therefore involve a series of passages

  borieux consisting of the hydrolysis of the halide, the isomerisation of

  compound (III) to the compound I) by boric acid (which would lead

  When the compound is enriched in the mixture, the yield of the

  50%), separation by fractional distillation of the compound (I)

  to compound (III) and recycling thereof.

  A method has also been described which includes the acetoxylation of the halo

  3,3-dimethyl-allyl creatine and the successive hydrolysis of the acetoxylated product obtained:

H3C

C = C-CH2Cl CH3COOK, CH3COOH

C: = CH-CH2C [

H3C HnC H3C CH3

/ C = CH-CH2-O-C-CH3 + \

H3C O CH O-C-CH3

#

CH2 0

(II) C (IV)

KOH / H20

(II) + (IV) (I) + (III)

  [I.N. Nazarov, I.N. Azerbayev, "Zhur, Khim Obs." 18, 407 (1968),

  "Chemical Abstract" 43, 114 g (1969)].

  This acetoxylation, however, is not free of isomerization reaction.

  tion. In fact, about 30% of the acetoxylated (IV) isomer is formed.

  When the mixture is then subjected to hydrolysis, this product is then an additional isomerization, so that the tertiary alcohol (III) forms the

main product of the reaction.

  Relatively recently, a method for the acetoxylation of 3,3-dimethyl-allyl chloride has been described, without the formation of undesired isomerization products: ## STR2 ## CH3COOK, DMF (or DMSO) = CH-CH2Cl. At H3CI 800C, 6 hours

H3C

(II) (yield: 88%)

  [Japanese Patent Application No. J 52 095606, Nippon Zeon K.K.].

  The above method, however, has the major disadvantage of requiring the use of aprotic polar solvents which are very expensive and whose

recovery is difficult.

  In addition, once the acetoxylated product (II) has been obtained, it is

  necessary to carry out the hydrolysis with the disadvantages indicated above.

  It has been found, and this forms the object of the present invention, that it is

  possible to implement a process for the synthesis of 3,3-dimethyl alcohol

  allylic in two stages or successive stages.

  In the first step, a 3,3-dimethyl-allyl halide, optionally

  dissolved in an organic solvent, is reacted with an alkaline salt of the carboxylic acid in aqueous solution, in the presence of a catalyst of

  phase transfer to yield the 3,3-dimethyl-allyl ester cor-

sponding.

  In the second step, the 3,3-dimethyl-allylic ester, optionally dissolved in an organic solvent, is hydrolysed by treatment using a

  aqueous solution of an alkaline hydroxide in the presence of a

live fertility.

  The process thus described can be presented schematically by the following reaction: H3C_

H3C \ CC X - R-COOM / H20

HC C / C2 Cat.

H3C

H3C \ MOH / H20

  C = CH-CH 2 -O-C-R Cat.I) wherein: X is Cl, Br; R is H, or a radical alkyl, benzyl or aryl; M is Na or K;

  Cat. is a phase transfer catalyst.

  The preparation method which is the subject of the present invention makes it possible

  to obtain 3,3-dimethylallyl alcohol in a high yield, without

  non-desired isomerization products. In this method, relatively inexpensive solvents and low hazard reagents are used, which makes it extremely easy to

implementation of this method.

  In more detail, the first step of the reaction is practically based on the use of a two-phase system, consisting of an aqueous phase and an organic phase, and this in the presence of a phase transfer catalyst. The organic phase is formed of 3,3-dimethyl-allyl halide, either as such or dissolved in an inert organic solvent immiscible with water,

  such as, for example, benzene, methylene chloride, petroleum ether.

  In general, it is preferable to operate in the absence of organic solvent for reasons of economy and ease. Excellent results have also been obtained when using technical halide, impure because of the presence of isoprene. The aqueous phase is formed mainly of an aqueous solution of an alkaline salt of a carboxylic acid such as, for example, propionate, phenyl acetate or sodium or potassium benzoate, or even more

  especially potassium or sodium acetate.

  The amount of alkali carboxylate used is generally of the order

  a molar ratio of between 1 and 2 with respect to the allyl halide.

  In order to minimize the volumes involved in this reaction, it is preferable to use a saturated aqueous solution, optionally

  presence of an undissolved alkaline carboxylate at room temperature.

  As a phase transfer catalyst, a salt can be employed

  phosphonium, a crown ether or, preferably, a quaternary ammonium salt

  ternary which, in general, is cheaper. It is also possible to use salts

  of ammonium based on a polymer support.

  As a quaternary ammonium salt, a halide may be used

  ammonium (chloride or bromide) such as, for example,

  methylbenzylammonium, tricaprylylmethylammonium chloride or bromide

tetrabutylammonium.

  The amount of quaternary ammonium salt used is between

  0.1 and 10% in molar proportions relative to the substrate.

  In order to have a better control of the initial isothermal activity of the reaction, it is preferable to operate in the presence of a quantity

  ammonium salt of the order of 0.5 to 1% in molar proportions.

  The reaction temperature is not critical and it is possible to

  easily at temperatures between 0 and 80 ° C although, in general, it is preferable to operate at a temperature between

ambient and 500C.

  The duration of the reaction depends on the nature of the reagents and the amount of

  catalyst temperature as well as the reaction temperature.

  In general, the reaction is complete in 1 to 3 hours.

  The first step of this process, according to a practical embodiment of the invention, is carried out as follows: In a reactor equipped with a stirrer and a thermometer, the pre-run quantity is introduced at room temperature. alkali metal carboxylate, a sufficient amount of water to dissolve most of the carboxylate

  alkali and the phase transfer catalyst.

  The reaction mixture is then stirred while the 3,3-dimethyl-allyl halide, which may be dissolved, is slowly added thereto.

  in an organic solvent. The temperature tends to rise spon-

  It is therefore necessary to maintain it at about 350 ° C using an external refrigeration bath made of cold water. When the mixture is complete and the exothermic reaction is stopped, the mixture

  can be heated for 1 to 2 hours at 50-60 ° C to complete the reaction.

  The organic phase is separated and treated according to laboratory methods.

  conventional techniques to allow the separation of the 3,3-dimethylallyl ester.

  To operate the next step, it is not necessary to purify the ester which

  can therefore be used as is.

  - Similarly, in the second stage of the process are present: * an organic phase, * an aqueous phase, and

  the phase transfer catalyst.

  The organic phase is formed of the 3,3-dimethyl-allyl ester, obtained for example according to the abovementioned method, optionally dissolved in an organic solvent which is immiscible with water, such as benzene, methylene chloride, ether;

of oil.

  The aqueous phase consists of an aqueous solution of an alkaline hydrocyanide;

(KOH, NaOH).

  The concentration of the aqueous alkali hydroxide solution is not critical, although it is preferable to employ solutions having concentrations of about 50 to 60%. In general, an excess of alkaline hydroxide compared to

the ester can be used.

  As a phase transfer catalyst, any of the catalysts

  mentioned above with regard to the first step, used in

  the same quantities, can be used.

  The reaction time depends on many factors such as: * the nature of the reagents, * the amount of catalyst, and

* the reaction temperature.

  In general, the reaction is completed in a period of between 1 and

3 hours.

7 22458529

  According to a practical mode of implementation of the invention, the second stage of the process is carried out as follows: In a reactor equipped with an agitator and a thermometer, it introduces

  the aqueous solution of alkaline hydroxide and the phase transfer catalyst.

  The mixture is then stirred vigorously while the 3,3-dimethyl-allyl ester, optionally dissolved in an organic solvent, is slowly added thereto. The initial exothermicity is controlled, so that the temperature is maintained at a value of about 350C, using an external bath of water

Cold.

  Then, the mixture is optionally heated for 1 to 2 hours at 50% C so that the reaction can be terminated. The organic phase is then separated

  and treated according to conventional laboratory techniques.

  The 3,3-dimethylallyl alcohol thus obtained can be purified by distillation.

  It is important to note that under the experimental conditions de-

  in the second stage, the direct hydrolysis of the 3,3-di-

  methyl-allyl does not occur (see Example 3).

  The process of the present invention therefore has many advantages, the main ones of which can be summarized as follows: the method described makes it possible to obtain 3,3-dimethylallyl alcohol in high yields; the product of the reaction is free of by-products due to isomerization reactions; the implementation of the process is particularly simple and does not require any sophisticated equipment such as, for example, high pressure reactors, etc .; no reagent, catalyst or solvent, dangerous handling or high price is necessary; the starting material, in both steps, is not necessarily of high purity, because it is possible to use 3,3-dimethyl-allyl halides having a technical quality, which can contain up to 20% of isoprenous, and

  therefore it is not necessary to purify the 3,3-dimethyl ester.

  allyl obtained in the first step.

  From all that has been said so far, it is obvious that the two steps of the method can be implemented independently of one another.

  In fact, the first step can be used also for the preparation

  3,3-dimethyl-allyl esters without the need for conversion of these

  to 3,3-dimethylallyl alcohol.

2458529

  In addition, the second step can be used separately for the hydrolysis of the 3,3-dimethyl-allyl ester of any origin, because it is not limited to the hydrolysis of the esters of 3, Prepared 3-dimethyl-allyl

  according to the method described in the first step.

  If one takes into account what is known phase-catalyzed reactions, it seems reasonable to provide that the method forming the subject of the present invention can be implemented also

  according to other methods which consist of purely technological alternatives

  such as, for example, polyphase systems generally including phase transfer techniques such as those given in Chapter I of the book "Phase transfer catalysis - Principles".

  and Techniques ", by C. M. Starks and C. Liotta - Academic Press, New York, 1978.

  3,3-dimethylallyl alcohol has many applications in

Organic chemistry.

  The most common use relates to the synthesis of natural organic substances

  (terpene derivatives), the production of flavoring substances and

to the production of pesticides.

  For example, 3,3-dimethylallyl alcohol is the starting material of

  the synthesis of pesticides belonging to the pyrethroid class.

  [K. Kondo, K. Matsui, A. Negishi, "Synthetic Pyrethroids", T. Elliot Publisher,

  ACS Symposium Series No. 42, pages 128-135].

  Other objects and advantages of the present invention will be apparent from

  reading of the following description and examples given for illustrative purposes

but not limiting.

EXAMPLE 1

  Preparation of 3,3-dimethyl-allyl acetate (II)

  In a glass flask, provided with an agitator and a thermometer, are introduced: 2 moles of potassium acetate, 0.01 mole of tetrabutylammonium chloride,

- 50 ml of water.

  The mixture is then kept under constant stirring at ambient temperature, and then 1 mol of 3,3-dimethyl-allyl bromide (technical grade, containing about 20% by weight of isoprene) is slowly mixed over 1 hour. The reaction mixture spontaneously increases its temperature during the addition, so it is necessary to maintain it at a temperature of

  the order of 35 C with an external bath of cold water.

  When the addition is complete, the reaction mixture is maintained under stirring.

at 600C for 2 hours.

  After cooling to room temperature, the reaction mixture is

  filtered to remove undissolved salts.

  The organic phase is then separated, washed with water until a neutral pH is obtained, and finally rendered anhydrous by the addition of sodium sulfate.

anhydrous sodium.

  There is thus obtained 1309 of a crude product which consists of 92% (determined by liquid gas chromatography) of 3,3-dimethyl-allyl acetate (yield: 93%) which can be purified by distillation (boiling point). of the order of

149 to 1510C).

  Infrared (IR) and nuclear magnetic resonance (NMR) spectra are in agreement with the predicted structure. Liquid gas chromatography (GLC)

  does not show any peak corresponding to the presence of isomeric products.

authorization.

EXAMPLE 2

  * Preparation of a cool 3,3-dimethyl-propytic (I).

  To a mixture consisting of: - 2 moles of potassium hydroxide at a concentration of 85%, - 0.01 mole of tetrabutylammonium bromide, ml of water, kept under constant stirring at room temperature, added slowly during 1 hour 130 g of the crude product obtained according to the method described in

  Exempt containing about 92% 3,3-dimethyl-allyl acetate.

  During the addition, the temperature tends to rise spontaneously and it is therefore necessary to control it with an external bath

of cold water.

  When the mixture is complete and the exothermic activity has disappeared,

  the reaction mixture is stirred for 2 hours at a temperature of 500C.

  The reaction mixture is then cooled to room temperature, filtered, the organic phase is separated and the mass is washed on the filter with water until a neutral pH is obtained, after which it is made anhydrous by addition

anhydrous sodium sulphate.

  The 3,3-dimethylallyl alcohol obtained is then purified by distillation

  (Boiling point of the order of 140 to 1420C).

  69 g of the pure product (I) are thus obtained, having a purity of 96% (determined by liquid gas chromatography). We do not see the presence

  no peak relative to the presence of isomerization products.

  Infrared (IR) and nuclear magnetic resonance (NMR) spectra are in agreement with the predicted structure. The total yield of the process is

  % relative to 3,3-dimethyl-allyl bromide.

EXAMPLE 3

  The purpose of this example is to show that under experimental conditions

  described in Example 2 no hydrolysis of 3,3-di-bromide occurs.

  methyl-allyl. 0.1 mole of 3,3-dimethyl-allyl bromide of technical grade is added. in 5 minutes to an 85% solution of potassium hydroxide (0.2 mole) in

  5 ml of water in the presence of 0.32 g of tetrabutyl ammonium bromide.

  It is found that no exothermic reaction occurs.

  The reaction mixture is then stirred for 1 hour.

  at room temperature. During this time period, we periodically withdraw

  samples that are examined by infrared spectroscopy.

  In 1 hour, no reaction was observed.

  The 3,3-dimethyl-allyl bromide is completely recovered.

  Of course, the present invention is not limited to the examples

  and modes of implementation mentioned above; it is likely to

  Many variants accessible to those skilled in the art, depending on the applications

  visages and without departing from the spirit of the invention.

Claims (18)

  1. Process for the preparation of 3,3-dimethylallyl alcohol from 3,3-dimethyl-allyl halide, characterized in that the halide of   3,3-dimethyl-allyl, optionally dissolved in an inert non-ionic solvent   target with water, is reacted with an alkali metal salt of carboxylic acid in an aqueous solution and in the presence of phase transfer catalyst, so as to lead to a 3,3-dimethyl-allyl ester which optionally dissolved in an inert solvent, immiscible with water, is then hydraulised   by treatment with an aqueous solution of alkaline hydroxide, in pre-   the presence of a phase transfer catalyst, according to the following reaction scheme: H3C R-COOM, H20 H3C X'C-CH / C = CH-CH2XCC -O-C-R Cat. i H3C Cat. H3C H3C / 0 H3C MOH, H20 = CH-CH20   Cat. H3C wherein: X is Cl or Br; R is H, or an alkyl, benzyl or aryl radical; M is Na or K; and   Cat. is a phase transfer catalyst.   2. A process according to claim 1, characterized in that the phase transfer catalyst used is a cyclic polyether (crown ether), a   phosphonium salt or, preferably, a quaternary ammonium salt, optionally   attached to a polymer support.   3. Process according to claim 1 or 2, characterized in that   In the case of phase transfer, a quaternary ammonium halide is used.   4. A process according to any one of claims 1 to 3, characterized   in that as a phase transfer catalyst, tetra-butylammonium bromide is used in amounts of 0.1 to 10% (relative to   molar) relative to the 3,3-dimethyl-allyl halide.   5. A process according to any one of claims 1 to 4, characterized   in that the 3,3-dimethyl-allyl halide is dissolved in an inert solvent which is immiscible with water, such as benzene, methylenether or ether of oil.   6. A process according to any one of claims 1 to 4, characterized   in that the 3,3-dimethyl-allyl halide is used as it is in the absence of organic solvents.   7. A process according to any one of claims 1 to 6, characterized   in that the alkaline salt of the carboxylic acid is used in molar ratio   between 1 and 2 relative to the 3,3-dimethyl-allyl halide.   8. Process according to any one of Claims 1 to 7, characterized   in that the alkaline salt of the carboxylic acid is sodium acetate or potassium acetate.   9. A process according to any one of claims 1 to 8, characterized   in that the aqueous solution of the alkaline salt of the carboxylic acid is a saturated solution, optionally in the presence of undissolved salts 10.Procédé according to any one of claims 1 to 9, characterized in that the reaction between the 3,3-dimethyl-allyl halide and the alkali metal salt of the carboxylic acid is carried out slowly, the halide dissolved in a water-immiscible organic solvent, optionally being slowly added to a concentrated solution of the alkaline salt, in the presence of a phase transfer catalyst, the aqueous solution being furthermore   kept vigorously stirred.   11. A process according to any one of claims 1 to 10, characterized   in that the reaction between the 3,3-dimethyl-allyl halide and the alkaline salt of the carboxylic acid is carried out at a temperature between   0 and 80% C and preferably between room temperature and 600C.   12. Process according to any one of Claims 1 to 4, characterized   in that the 3,3-dimethyl-allyl ester is reacted with the aqueous solution of the alkali metal hydroxide, dissolved in an inert organic solvent, immiscible with water, such as benzene methylene chloride or ether of oil.   13.- Method according to any one of claims 1 to 4, characterized   in that the 3,3-dimethyl-allyl ester is reacted with the solution   aqueous alkali hydroxide as such, in the absence of organic solvent.   14.- Method according to claim 1, 12 or 13, characterized in that   the 3,3-dimethyl-allyl ester is 3,3-dimethyl-allyl acetate.   15.- Method according to any one of claims 1 or 12 to 14,   characterized in that the alkaline hydroxide is NaOH or KOH.   16. A process according to any one of claims 1 or 12 to 15,   characterized in that the alkaline hydroxide is used in a molar ratio   between 1 and 2 relative to the 3,3-dimethyl-allyl ester.   17.- Method according to any one of claims 1 or 12 to 16,   characterized in that the reaction between the 3,3-dimethyl-allyl ester and the aqueous alkali hydroxide solution is carried out slowly, the ester being added as such or dissolved in a non-organic inert organic solvent. miscible with water, with the alkaline solution, in the presence of a phase transfer catalyst, the alkaline solution being maintained vigorously stirring.   18. Process according to any one of claims 1 or 12 to 17,   characterized in that the reaction between the 3,3-dimethyl-allyl ester and the alkaline solution is carried out at a temperature between 0 and 60 ° C,   and preferably between room temperature and 500C.