DE2151716A1 - Process for the preparation of amino alcohol esters - Google Patents

Description

PATENT LAWYERS DR. INQ. OTTO STÜRNER. DR. FRIEDRIOH E. MAYER

f ~ Dr. Irtfl.O. Störn »r-Dr. F. M "y" f7öa Pforzheim, Juliu "-N" * h "r-Str.1S ~ |

763 Pforzheim

Jullua-Naeher-Str.

October 16, 1971

Unttr Zelohen

2153-Kr.

Your Z "loh" n

Patent application

Applicant: JOUVEINAL S.A., 19, Rue de la Gare, CAOHAN ,. YaI de Marne, France

Name: Process for the production of amino alcohol esters

The invention relates to an improved process for the specific production of amino alcohol esters, for which the applicant has already completed the process in their French patent no. 1.344.4-55 of 17. October 1962.

In particular, the invention relates to a process for transesterification between an ester of an aliphatic Low molecular weight alcohol and a hollow molecular weight amino alcohol.

The transesterification immediately gives a pure reaction product without the need for further purification, which entails considerable losses.

209849 / 1U8

ORIGINAL INSPECTED

The methods of the present invention allow for Production of amino alcohols of the type:

where R ₁ denotes hydrogen or a lower alkyl radical and where η can be either equal to O or equal to 1, 2 or 3
Rg denotes a lower alkyl radical.

According to the invention, amino alcohol esters are produced according to the following formula

^c \

wherein Y is a halogen or hydroxyl radical, a nitro or aminodiolate or an alkyl or alkyloxy radical, a is either 0 or 1, 2, 3, X is oxygen or nitrogen

ρ can either be equal to O or equal to 1,2,3 and R ₁ , Rp, η have the same meaning as above,

by using amino alcohols of type II by means of acid esters of the formula
<* X ^m (CMo) p WUUK \ // ο

where R is an alcohol radical of low molecular weight and Y, a, X, p have the same meaning as above,

esterified.

209849/1148

It can be seen that this transesterification-based process is immediately a reaction product shows that no more loss-producing cleaning is required.

The esters obtained can be used to facilitate their use be converted into salts in a known manner.

It can be seen that such a reaction cannot be carried out under arbitrary conditions can if you want to achieve industrially interesting results

So one must have certain 'proportions in the reaction participants, Observe reaction temperature ranges and reaction times and environments.

Another object of the invention is to provide the optimal process conditions for achieving perfect results. ~

In the course of its investigations, the applicant has established a number of parameters to be observed, which are essentially compiled in the following table: ^J

Mole Mole Mole Reaction solvent ₊ Ester Amino alcohol Alcoholate Benzene toluene xylene N / A ^ü i5 1 0.075 1 1 0.075 1 1 0.020 1 »5 1 0.075 l »5 1 0.075 1 »5 1 0.075 1 0.075 2 1 0.075 2 1 0.100 +

2 09849/1148

(Continuation of the table)

reaction time Gross mole Ester (Type III) 3 hours. 0.2 . 3 hours. 0.5 4 hours 0.3 0.5 hours 0.4- 1 H. 0.6 2 hours. 0.7. 2 hours. 0.6 2 hours. 0.7 4 hours 0.45

What is the molar ratio between the ester used Type 1 and the amino alcohol used. of type II, so these can fluctuate between 0.5 and 2 »However, the most favorable ratio is around 1.5 ·

In order to achieve the specific effect of the reaction, which is one of the objectives of the invention, the temperature of the reaction medium must be kept in a range between 70 and 145 ⁰ O. According to a preferred embodiment of the invention, the temperature is between 100 and HO ⁰ O.

. Depending on these temperatures, the reaction time * must be between 30 minutes and 4 hours, but advantageously between 1 and 2 hours.

The reaction medium, which is of paramount importance, consists of non-polar solvents such as benzene, toluene and xylene. Two of these solvents can be mixed in different proportions in order to obtain a binary reaction medium, or they can also be used together in a mixture of three in different proportions _e

To don JSrbra; * and dio npozifincho effect of the reaction ?, \ I vorbosnorn, int; <lLo Vorwondunp; olnon Umontorungn-Katfilyaators wünachonuwort. The Rüaktionamiliou Metallalkoholate, Iniibonondoro

209849/1148 BAD ORfGlNAU

Sodium methylate or ethylate in proportions between Add 0.02 to 0.1 mole per mole of type II amino alcohol, as can be seen from the table above is.

Failure to observe these parameters and their so determined Limits leads to the formation of secondary substances that contaminate the product produced and thus make costly and laborious cleaning necessary.

In particular, reaction times of more than 4 hours result to the occurrence of side reactions, which in turn lead to the formation of secondary substances.

The implementation of the inventive method in Within the limits defined above, however, allows the ^ production of immediately pure amino alcohol esters Type III with excellent yield at the same time.

A few examples for carrying out the process according to the invention are given below, but these examples in no way represent a restriction of the scope of the invention. _: .

Example I - trimethoxy -3,4-, 5 phenybenzoate - 2 - dimethylamine - 2n - butyl.

A solution of 19.5 kg phenyl -2 dimethylamine - 2n butanol and 34 kg of methyl ester of 3,4,5 benzoic acid dissolved in 400 l of toluene is brought to reflux. After dehydration, the solution is cooled to 80 °. 5 kg of sodium methylate are added, the reaction medium is gradually heated to about 110 ° and this temperature is maintained Upright for 2 hours. After the solution has cooled to about 25 °, 25 liters of concentrated hydrochloric acid are added. The aqueous acidic fraction is washed out with tuluene. It is made alkaline this aqueous phase with soda and extracted with methylene chloride. The organic phase is up washed out to neutrality, then dried and

2 0 9 8 A 9/1 U 8

steams. Of? Evaporation residue is at 70 ° in ethanol crystallized. . '"

Weight: 22 kg product, final temperature: 78-80 °,

Example 2 - trimethoxymaleate - 5,4,5 phenyl benzoate 2 - dimethylamine - 2n - butyl »

87.4 kg of trimethoxy - 3,4,5 phenyl benzoate - are heated. 2 dimethylamine - 2n - butyl and 28.8 kg? Maleic acid in 350 l of water until it is homogenized. The solution is filtered and then left to rest. G. IO5-106 ^0: After crystallization 160 kg product is obtained · final temperature

Example 5 - Chlorohydrate of phenyl-p-chlorophenoxyacetate-2-dimethylamine-2η -butyl.

19 »5 kg phenyl - 2 dimethylamine - 2 η - butanol and 32.5 kg of ethyl p-chlorophenoxyacetate, dissolved in 400 1 Toluene - are dehydrated by partial distillation of the solvent.

The solution is ^{cooled to 80 0} g. Awake addition of 5 kg of sodium methylate. the .ßeaktionsmilieu _{i is} heated progressively to 110 ° and held at this temperature for 2 hours.

After cooling, the medium is extracted with a hydrochloric acid solution. The aqueous-acidic fraction is in Washed out toluene, then alkalized with sodium hydroxide solution

The emulsion is extracted using methyl chloride, then washed out to neutrality and dried.

The evaporation ■ of the organic phase leads to an oily phase Cane residue that hardens after cooling. .

Weight: 29 kg.

209 849/11 k 8

The product is dissolved in 200 liters of di-isopropyl ether When gaseous hydrochloric acid is bubbled out, the crude chlorohydrate of the product is centrifuged out.

The product is purified by recrystallization from ethyl acetate

Weight: 22 kg. Final temperature: 101-103 ⁰ Co

209849/114

Claims (13)

EXPECTATIONS 1.) "Process for the preparation of amino alcohol esters of Formula. · - ° - ° - ^c * & Ü ^p <ζ ^> ^{N (CH} 3> 2 (Ι ») R-. Denotes hydrogen or a lower alkyl radical and η can be either zero or 1, 2 or 3, Rp denotes a lower alkyl radical, T a halogen radical, hydroxyl radical, a nitro or amino derivative, ' is an alkyl radical or an alkyloxy radical and a is either 0 or 1 ,. Can be 2 or 3, X oxygen or nitrogen, ρ is either zero or 1, 2 or 3, characterized in that there is between an ester of an aliphatic alcohol of low molecular weight the formula • α Y, X, a, p have the same meaning as given above and R is a low molecular weight alcohol residue, and an amino alcohol of higher molecular weight of the formula carries out a transesterification. _ '^ x tr-u \ R ₂ ^N i ^CH 3 '2 2e) Method according to claim 1, characterized in that that the molar ratios between the ester and the amino alcohol are between 0.5 and 2. 3.) Process according to claims 1 and 2, characterized in that the temperature of the reaction medium is between 70 and 14-5 ⁰ G. 2098A9 / 1U8 4.) The method according to claim 3 »characterized in that that the reaction time is between 30 minutes and four Hours lies. 5 «) method nach.den claims 1 hmä 4, characterized in that one consisting of a metal alcoholate Accelerator is used. ■ 6.) Method according to claim 5 »characterized in that that the accelerator used is sodium methylate. 7.) The method according to claim 5 »characterized in that that sodium ethylate is used as an accelerator. 8.) Process according to Claims 7 to 8, characterized in that that the addition ratio for the accelerator is between 0.02 and 0.1 moles per mole of amino alcohol lies. 9 ··) Method according to claim 1, characterized in that that toluene is used as the reaction solvent. 10.) Method according to AnsPmch 1, dadiirch, characterized that xylene is used as the reaction solvent o 11.) The method according to claim 1, characterized in that al3 reaction solvent benzene is used. 12.) The method according to claim 1, characterized in that, as Re aktichnslösemittel a binary β mixture from the following ingredients is used: benzene, 'foluene, xylene. 13.) The method according to claim 1, characterized in that the solvent is a three-component mixture Benzene, tuluene and xylene is used o 209 8 49/1 U 8 _{0RielNAL 1NSPE} CTED