Method for producing amides of alpha-aminoacids

专利摘要:
The invention relates to amides of amino acids (AMC), in particular compounds of the general formula I: RCH-ClUNH) -C (0) NHj, where R-H,, or phenyl are used in medicine, veterinary medicine, in the manufacture of food and perfumery products. Increasing the yield of | AMK and simplifying the process of catalytic hydrolysis of oi-amino acids or their hydrochloride. In an aqueous-alkaline solution is achieved using a different catalyst, an alkali-insoluble polymer resin of general formula II: PR ,, where P is the matrix of a polyacrylic resin of the structure ((-) -, having a network structure, RJ is the residue of an aliphatic ketoamine of formula III: NHX, where X is CH, IC (O) CH ,; ((O) CH
公开号:SU1316554A3
申请号:SU833534108
申请日:1983-01-11
公开日:1987-06-07
发明作者:Андре Огюст；Коммейрас Эме；Робер Тайлладес Жак；Брюжиду Жан；Золя Режин；Превьеро Альдо；Мион Луи；Жан РОБЕР；Паскаль Эмиль；Ласперас Моник；Руссе Ален
申请人:Сантр Насьональ Де Ля Решерш Сьянтифик (Фирма)；
IPC主号:

专利说明:

one . 1316554.2
The invention relates to a method. containing 1.4 g of immobilized keta for obtaining amides of α-amino acids, a co-tonic polymer (I) with 1.8 -1 СG, equatorial are intermediate products of these ketones of the ketone group per gram prosthesis of α-amino acids found islemer At the exit of the reactor, the utilization rate in medicine, veterinary medicine5 The transformation stump about α-aminomethylmer and in the production of food or perfume-captobutyramide is 95%. Surveying products. Ability of the reactor operating
The purpose of the invention is to simplify the process at room temperature, compose the process and increase the target yield of 0.5710 mol / min in terms of
duct. . 1l. reactor and 1 g of resin.
Example 1. A solution of O, 10 mol. Example 5. A solution. (0.05-n)
hydrochloride L-aminopropionitrile vchlorogiprata about-aminopropionitrile in
0.01 N HC1 is injected simultaneously; 0.01 N hydrochloric acid is injected
but with the same amount of 0.21 n guide — simultaneously with the same amount
sodium oxide in the upper part of the re-0.11 n sodium hydroxide. in the upper
A plate containing 1.4 g of immobilized part of a reactor containing 1.3 g of a ketone polymer (I) from 1.8 tons of polymer (III), immobilized with 10 equivalents of the ketone group of 2.0 to 10, equivalents of the ketone gram of the polymer. At the exit of the reactor groups per gram of polymer. Power
degree of conversion to ob-aminopropio-conversion to ob-aminopropionamide
namide is 95%. Manufacturer-outlet reactor is 85%. .
A reactor operating at a com — the capacity of a reactor operating at a temperature of 1.2 ppm at room temperature, is 10 mol / min in terms of 1 liter, 0.49–10 mol / min in terms of
actor and 1 g of resin. .in 1 liter of reactor and 1 g of resin.
Example 2. A solution of 0.1 mol. Example 6. A solution of hydrochloride — oC-aminopropionitrile vta oi, α-aminopropionitrile (0.10 mol) 0.01 N HC1 is injected simultaneously — 0.01 N HC1 is injected simultaneously with such the same amount of 0.21 n hydraulically with the same amount of 0.15 n sodium roxide in the upper part of sodium re-hydroxide in the upper part of the reactor, containing 1.5 g of immobilizator-actor, containing 1.3 g of ketone bath ketone ( II) spolymer (IV) immobilized from 1.2 to 10 equivalents of the ketone group 3.0-10 equivalents of the ketone group per gram of polymer . At the outlet of the reactor-to gram of polymer. At the outlet of the reactor, the degree of conversion to the α-aminopro 35, the degree of conversion to α-amino-pionamide is 90%. Production-propionamide is 99.1%. The capacity of the reactor, operating the capacity of the reactor, working with SO, is 0.55 10 mol / min at room temperature, it is in terms of 1 liter of the reactor and 1 het 1.53-10 mol / min in terms of resins. 1 liter of reactor and 1 g of resin.
Example 3. To 20 ml of 0.2 mol p-Example 7. A solution (0.10 mol) of a solution of about-aminonitrile add-. OR Idrata Fr. α-aminopropionitrile in 4 ml of 1N sodium hydroxide is injected simultaneously; 1 g of insoluble ketrn polymeric with an amount of 0.21 n. hydra (I) (1.8 mg / g) and stirred in sodium oxide in the upper part of the reaction for 1 h at room temperature - ° P containing 3.3 g of ketone pore. After neutralization of the hydrochloric acid of the immobilized (V) with 0.85 "lot and centrifugation of the heterogen-O equivalents of the ketone group in the mixture, analysis of the polymer floating on the top. At the outlet of the reactor nose b of the substance show that step-. The degree of conversion to ob-aminopropionamide is 35%. The production of the transformation of the α-aminopropionitrile of the reactor, operating at
la in ed -aminoamide is 91%.
tt / t, at room temperature, is
Example 4. A solution of 0.10 mol ". I i JH,
sb-aminomethyl mercapto-chlorohydrate mol / min in terms of 1 l of rebutironitrile in 0.01 N hydrochloric acid, ° P
those are injected simultaneously with that. Example 8. A suspension of 1.50 g
KIM same amount of 0.21 n giproksipaketonny polymer (IV) with 2,6-10 Eknati in the upper part of the reactor, co-i vials of ketone groups per gram
31
polymer in 15 ml of a 0.2 n solution of sodium hydroxide, 80 mg of α-aminopropionitrile hydrochloride are added. The mixture is stirred for 10 minutes. After neutralization with hydrochloric acid and centrifuging, NMR analysis of the substance floating on the surface shows that the conversion to ob-aminopropionamide is 97%.
Ex. 9. To the suspension 0.60 g (VI) with the content
ketogroups on
gram of polymer in 15 ml of 0.25 n sodium hydroxide solution added 0.16 g of α-aminopropionitrile hydrochloride. The mixture is stirred for 1 h at 20 ° C. After neutralizing the hydrochloric acid and centrifuging, the NMR analysis of the supernatant gives a degree of conversion to 98% alaninamide. .
Example 10. To a suspension of 1, 1 5 of a ketone polymer (VII) containing 5.0–10 equivalents of ketone groups per gram of polymer in 15 ml of 0.9 n sodium hydroxide solution and 10 n
ketone polymer 3,310 equivalents

Miak, 0.640 g of aminopropionitrile hydrochloride is added. The mixture is stirred for 2 hours at 10 ° C. After neutralizing hydrochloric acid and centrifuging, the NMR analysis of the supernatant gives a degree of conversion to alaninamide of 93%.
In these examples, used polymer resins (I-VII), having 2 types of matrices based on (-CH-CH-) p with
- (
the net structure formed by P - with the help of divinylbenzene, Pg - with the help of K, N-bis-acryloyl polymethylenediamine formula
CH2 CH-CO-N-lClA2VN-CO-CH CH
 -
AT
R
where X 1-6,, methyl, ethyl or radicals R together form an alkylene group () and, 50 where y 1-4.
The polymer resin (IV-V1I) catalysts mentioned in the examples have the following structure:
I-
55
Nf
11 -№1- {0
) - MN (Sh 2.1gS-1 (2) 0
111-1
IV- (K)
-f
V 11-1
@ - ЫНСН2С 7, 0
VI-MI (T)
@) (SNGSSN
-xs
about
Example 11.. Preparation of polyme -Oo
hlorangid
Ridny resin. A mixture of acrylic resin (10 g, 0.10 eq), crosslinked with 30% divinylbenzene, with thionyl chloride (20 ml, 0.27 mol) and anhydrous dimethylformamide (8 ml) in 100 ml of anhydrous chloroform was heated to 60 ° C for 6 h with stirring. The resin was filtered, washed chloro. form, then ether and dried under reduced pressure. The capacity of the acid chloride groups was 0.5 mEq / g.
The resulting acid chloride resin (3.0 g, 0.015 eq) is added to the solution of aza-8-diox-1,4-spiro (4-5) -decan (4.3 g, 0.030 mol) and triethyl-amine (1, 6 g, 0,016 mol) in 65 ml of dimethylformamide. The mixture is stirred for 7 hours at room temperature. After filtration, the resin is washed with distilled water, then suspended and stirred for 3 hours in a mixture of soda diluted with dimethylformamide. The resin is filtered, washed with distilled water and suspended in 4n. hydrochloric acid. Stir for 6 hours at room temperature. After filtration, the resin is washed successively with distilled water, ethanol and ether, and then dried under reduced pressure. The capacity for carbonyl groups is 2.5 mEq / g.
51316554
Example 12. Preparation of polymethyls according to
ra
@ - NH- {0
a solution of 4-aminocyclohexanol (3.0 g, 0.026 mol) and triethylamine (2.9 g of 0.029 mol) in 60 ml of dimethylformamide was added with the acid chloride resin (Example 11) with a capacity of 3.8 mg eq / g (4.0 g, 0.015 eq), the mixture is stirred for 7 hours at room temperature, then filtered. The resin is washed successively with DMF, distilled water, ethanol and ether. After drying under reduced pressure, 1.0 g of the resin thus obtained is oxidized as follows: this amount of resin is added to a solution of chromic anhydride (0.9 g, 9) in 40 ml of dimethylformamide containing a few drops of concentrated sulfuric acid. The mixture is stirred for 19 hours at room temperature, then filtered. The resin is washed successively with water, ethanol, a mixture of dilute soda and ethanol, then again with water. It is then acidified by washing with dilute hydrochloric acid, followed by washing with distilled water, ethanol and ether. After drying under reduced pressure, the capacity of the resin in carbonyl groups is 1.2 mEq / g.
Example 13. Obtaining polymer
-TSlH (CH2l2C-T O III
about
The acid chloride resin of Example 11 (3.0 g, 0.015 eq.) Is added to a solution of x-alanine (3.35 g, 0.06 mol) in 36 MP of a water-H-ethylmorphramine DMF mixture (1 / 3f1 / 341 / 3). After stirring for 17 hours at room temperature, filtration is carried out. The resin is washed successively with distilled water, dilute hydrochloric acid, water, ethanol and ether, and then dried under reduced pressure.
3.6 g of this resin are reacted with a solution of thionyl chloride (8 ml, 0.11 mol) and anhydrous dimethylformamide (3 ml) in 40 ml of anhydrous chloroform. The mixture is heated to 6 ° C for 6 hours with stirring. After filtration, the resin is washed by

hence chloroform, anhydrous ether, and then dried under reduced pressure. The total capacity for acid chloride groups was 5.5 megaeq / g.
This resin (3.2 g, 0.014 eq.) Is added to a solution of aza-8-dioxa-1,4-spiro (4-5) decane (4.5 g 0.032 mol) and triethylamine (1.8 g, 0.018 mol ) at
 70 ml of dimethylformamide. The mixture is stirred for 9 hours at room temperature, then filtered. The resin is washed with distilled water, suspended and stirred in
 -) for 3 h in a mixture of dilute sodium alkali with dimethylformamide.
Filtration is carried out; the resin is washed with distilled water and suspended in 4N. hydrochloric acid.
20 Stir for 6 hours at room temperature. After filtration, the resin is successively washed with distilled water, ethanol and ether, and then dried under reduced pressure. The capacity for carbonyl groups is 2.0 mEq / g. Example 14. Getting polyme25
thirty
ra
(Iv)
For 15 minutes, a stream of nitrogen is passed through a solution of N-acryloyl-aza-8-diox-1,4-spiro- (4-5) decane (Example 18 (5.46 g, 0.028 mol) and
N, N-methylenebisacrylamide (0.71 g, 0.0046 mol) in distilled water (18 ml). After adding a few milligrams of calcium persulfate and riboflavin, the solution is subjected to
10 minutes to the effect of radiation of a 500 watt lamp.
The polymer obtained is washed with water, ethanol, ether, and then dried under reduced pressure.
Then for 24 hours the suspension of the obtained polymer in 1N is stirred. hydrochloric acid. The polymer is separated by filtration, washed with water, ethanol, and ether, then dried under reduced pressure. The capacity of the polymer obtained in terms of carbonyl groups is 4 mEq / g. Example 15. Obtaining polyme
ra
(V)
; A) -lNSN2SSNz. )
to a solution of amino-1-propanol-2 (2.3 g, 0.30 mol) and triethylamine
(3.3 g, 0.030 mol) in 70 ml of dimethylormamide was added an acid chloride resin (limer 11) with a capacity of 3.8 mEq / g (5.0 g, 0.019 eq). The mixture is stirred for 7 hours at room temperature, then filtered. The resin is washed sequentially with distilled water, ethanol, and ether. After drying under reduced pressure, oxidation is carried out: 5.9 g of the alcohol resin thus obtained are added to a solution of chromic anhydride (10 g, 0.1 mol) in 120 ml of dimethylformamide containing a few drops of concentrated sulfuric acid. The mixture is stirred for 20 hours at room temperature, after which it is filtered. The resin is washed successively with water, ethanol, a mixture of diluted soda and ethanol, and distilled water. The resin is then acidified by washing with dilute hydrochloric acid, followed by washing with distilled water, ethanol, and ether. The resin, dried under reduced pressure, has a capacity in carbonyl groups of 0.85 mg-eq / g.
Example 16. Getting polypepa
)about
(Vi)
for 1 h, a stream of nitrogen is passed into a solution of N-acryloyl-1,4-dioxapiro (4,5) -8-decanamine (Example 19 (3.12 g, 0.015 mol) and N, N - bisacryloyl piperazine (0, 70 g, 0.0036 mol) in a mixture of 50/50 distilled water and methanol (15 mp). 50 μm N, H-tetramethylethylenediamine and 47.5 mg of ammonium persulfate dissolved in distilled water (1 ml) are added. The mixture is triturated in a mortar, washed several times with methanol and water, and the suspension of the copolymer in 1N salt is stirred for 45 hours at room temperature. Hydrochloric acid, replacing the acid solution with a new 2 times. Then the polymer is washed with water, drained and dried under reduced pressure in the presence of. The content of carbonyl groups in it is 4.3 mEq / g.
Example 17. Obtaining polymer
@ - yn№2ssss
about
(Vii)
five
0
five
0
five
0
five
0
five
for 45 minutes, a stream of nitrogen is passed into a solution of N-acryloyl-4,4-ethylenedioxy-n-pentylamine (as in Example 20 (4.38 g, 0.0022 mol) and N, N-bisacryloyl piperazine (0.466 g, 0 0024 mol) in distilled water (11 ml). Cooled to 0 ° C and 70 µl of NN-tetramethylethylenediamine (TEMED) and 70 mg of ammonium persulphate dissolved in distilled water (2.5 ml) are added. 17 hours at room temperature. The polymer obtained is triturated in a mortar and washed with water, then suspended in 1N hydrochloric acid, and the mixture is stirred for 48 hours at room temperature. filtered, pressed and dried under reduced pressure in the presence of .. The content of carbonyl groups in it is 5.3 mEq / g.
Example 18. N-Acryloyl-aza-8-diox-1,4-spiro- (4-5) -decan (for synthesis of polymer IV).
A solution of 28.6 g (0.20 mol) of aza-8-diox-1,4-spiro- (4-5) -decane in 100 ml of anhydrous ester is cooled-until, to which a solution of acryloyl chloride is added dropwise to it with stirring. - read (9.06 g, 0.10 mol) in 33 ml of anhydrous ether. Two hours after the start of the addition, the white precipitate was removed by filtration, the ether solution was evacuated. A crude product is obtained (yield 97%), which is then distilled. Bp IIO-IU C (0.06 mm), m.p. 43-44 ° C (pentane-ether). The yield of pure product is 85%.
Example 19. N-Acryloyl-1,4-diox-spiro- (4,5) -8-decanamine (for synthesizing polymer VI).
A solution of 1,4-dioxa-spipo (4,5) -8-decanamine (6.29 g, 0.040 mol) and triethylamine (4.05 g, 0.040 mol) in anhydrous ether (40 ml) is stirred and cooled to O C A solution of acryloyl chloride (3.67 g, 0.041 mol) in anhydrous ether (5 ml) is added. Stir under stirring for 30 minutes at 0-5 C, for 2 hours at room temperature.
The precipitate is filtered off, washed with anhydrous ether and then with a small amount of methanol. Uterine solutions are concentrated at poniken
Mr. pressure. Triethylamine hydrochloride precipitated is removed by filtration. The filtrate is treated with methanol again, concentrated and filtered. Repeat this operation for several times. remove maximum hydrochloride. and triethylamine. Then the filtrate is evaporated in a dry state and the residue is chromatographed on a silica column (eluent ether-methanol 95: 5). 6.11 tons of product are obtained (yield 80%) as a white solid, which crystallizes from a mixture of methanol and ether (colorless needles, tons, pieces 154.5 C).
Example 20. K-Acryloyl-4,4-ethylenedioxy-n-pentyl-amine (for polymer synthesis VII).
A solution of 4,4-ethylenedioxy-n-pentylamine (15.0 g, 0.103 mol) in an anhydrous ester (100 ml) is cooled to 0 ° C. A solution of acryloyl chloride (4.69 g, 0.052 mol) in 15 ml of anhydrous ether is added dropwise, maintaining the temperature. Then it is stirred at room temperature for 1.5 hours, after which the hydrochloride of the starting amine is filtered. The filtrate is concentrated and the residue is chromatographed on a silica column (eluent ether-methanol 1: 1). The pure product is obtained as a colorless oil (9.57 g, 93% yield).
The effectiveness of various polymer catalysts was compared by the example of hydrolysis of α-aminopropionitrile.
Comparative analysis of the effectiveness of various ketone polymers for the process carried out in a tubular reactor at 25 ° C, concentration of α-aminopropionitrile at the inlet of the O reactor, 05 MOL / L, and NaOH concentration of 0.02 mol / L (the reactor contains 1.3 g of catalyst and 4 , 5 ml of solution) are given in tab. one.
As follows from the data table. 1, cyclic ketone polymers (for example, IV) are more effective than aliphatic (V).
In tab. 2 shows the results on the effect of various parameters on the degree of conversion of oi-aminopropionitrile to ob-aminopropionamide in a tubular reactor in the presence of a polymer catalyst (I) (1.3 g of catalyst and 4.5 ml of solution). From these data it follows that the conversion increases with increasing temperature,
to
. 50
16554I o
the reaction, the concentration of Hcp ions and the number of carbonyl catalytic sites per unit mass of the polymer.
Preferably, the oi-aminonitrile solution comes in contact with the carbonyl polymer at a rate of 0.1-50 equivalents of carbonyl compounds per mole of the starting oL-aminonitrile.
The proposed method for producing amides of α-amino acids by hydrolyzing nitriles of α-amino acids in the presence of a carbonylated catalyst insoluble in the reaction medium instead of liquid catalysts (acetone) simplifies the process due to its continuity and the possibility of recycling the catalyst and its yield. quality by conducting the process in a heterogeneous phase.

权利要求:
Claims (2)
[1]
1. A method for producing α-amino acid amides of the general formula
RCH2, CHC01 H2 NH
where R-H, CH ,,, phenyl, by the catalytic hydrolysis of nitriles. about -amino acid formula
KSH2SNS NH
or nitrile chlorohydrates of α-amino acids 3 aqueous alkaline solution, characterized in that, in order to simplify the process and increase the yield of the target product, the process is carried out in the presence of a total form insoluble in alkaline polymer resin as a catalyst))
mules
- poly50 matrix
acrylic resin building () j
having a network structure, and R is the residue of the aliphatic ketoamine of the formula 55Xmultiple NHX, where X is - CKj, C (0) CH3, - (CHj), C (0) CH ,,
, - ((0)
or the heterocyclic ketoamine residue of the formula -.
П131655412
divinylbenzene or N, N -bis-acrylo ilpolymethylenediamine formula
CH2-CH-CO-1 ICH VN-CO-CHf CH-i,
[2]
2. Pop method, 1, distinguish-5R R
u and with the fact that they use poly where x 1-6, R-H, methyl, ethyl or
an acrylic resin, the matrix of which, when the radicals R together form an alkylene end, a net-like structure with the help of the group () y, where y 1-4,
 .g
Table 1
(V)
0.85
(Ii)
1.2
(I)
1.5
(Iii) 2
table 2

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同族专利:

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IE54389B1|1989-09-13|

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US3062883A|1960-07-13|1962-11-06|Allied Chem|Preparation of alkanoic acid amides through hydrolysis of alkyl cyanides|

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FR2405924B1|1977-10-12|1980-05-16|Anvar|FR2565225B1|1984-06-05|1986-10-17|Centre Nat Rech Scient|PROCESS FOR THE CONTINUOUS SYNTHESIS OF AN A-AMINO ACID BY CHEMICAL CATALYTIC HYDROLYSIS AND DEVICE FOR CARRYING OUT THE METHOD|

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JPS63179877A|1987-01-19|1988-07-23|Agency Of Ind Science & Technol|Novel vinyl compound|

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DE4235295A1|1992-10-20|1994-04-21|Degussa|Continuously feasible process for the preparation of methionine or methionine derivatives|

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FR2785609B1|1998-11-06|2000-12-15|Rhone Poulenc Nutrition Animal|PROCESS FOR THE PREPARATION OF METHIONINE|

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EP3632894A1|2018-10-01|2020-04-08|Evonik Operations GmbH|Production of methionine from methionine nitrile with low by-product content|

法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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FR8200600A|FR2519973B1|1982-01-15|1982-01-15|LV931336A| LV5460A3|1982-01-15|1993-12-15|The alpha-amino acid amide yield|