DE975633C - Process for the preparation of acylaminocarboxylic acid esters - Google Patents

Process for the preparation of acylaminocarboxylic acid esters

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Publication number
DE975633C
DE975633C DEF13369A DEF0013369A DE975633C DE 975633 C DE975633 C DE 975633C DE F13369 A DEF13369 A DE F13369A DE F0013369 A DEF0013369 A DE F0013369A DE 975633 C DE975633 C DE 975633C
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Prior art keywords
acid esters
organic
preparation
textbook
edition
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DEF13369A
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German (de)
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Konrad Dr Nagel
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Bayer AG
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Bayer AG
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Priority to DEF13369A priority Critical patent/DE975633C/en
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00Carboxylic acid amides
    • C07C233/01Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/45Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

AUSGEGEBENAM 15. MÄRZ 1962ISSUED MARCH 15, 1962

F 13369 IVb/'12 qF 13369 IVb / '12 q

Es ist bekannt, Acylaminocarbonsäureester durch Einwirkung von Carbonsäurehalogeniden auf Aminocarbonsäureester in Gegenwart von säurebindenden Mitteln herzustellen. Die dazu benötigten Aminocarbonsäureester können durch Einwirkung von Alkoholen auf Salze, z. B. Hydrochloride, von Aminocarbonsäuren und nachträgliches Infreiheitsetzen der Aminogruppe erhalten werden. Handelt es sich hierbei um Aminocarbonsäuren mit mehr als 2 Kohlenstoffatomen zwischen der Amino- und der Carboxylgruppe, so sind die Ausbeuten an Estern gering, da diese freien Ester verhältnismäßig unbeständig sind und sehr leicht, schon beim Stehen bei gewöhnlicher Temperatur, unter Abspaltung des Alkohols und Bildung monomerer oder polymerer Lactame reagieren.It is known to use acylaminocarboxylic acid esters Effect of carboxylic acid halides on aminocarboxylic acid esters in the presence of acid-binding agents To produce means. The aminocarboxylic acid esters required for this can by action from alcohols to salts, e.g. B. Hydrochloride, of aminocarboxylic acids and subsequent Liberation of the amino group can be obtained. If these are aminocarboxylic acids with more than 2 carbon atoms between the amino and carboxyl groups, they are Yields of esters are low, since these free esters are relatively unstable and very easy to even when standing at ordinary temperature, with elimination of alcohol and formation of monomers or polymeric lactams react.

Es wurde nun gefunden, daß man Acylaminocarbonsäureester in bemerkenswert guter Ausbeute dadurch erhalten kann, daß man N-acylierte Lactame mit Alkoholen in Gegenwart von Vereste- ao rungskatalysatoren, vorzugsweise bei höheren Temperaturen, umsetzt.It has now been found that acylaminocarboxylic acid esters can be obtained in a remarkably good yield can be obtained by N-acylated lactams with alcohols in the presence of Vereste- ao approximately catalysts, preferably at higher temperatures, implemented.

Obwohl bekannt ist, daß die Alkoholyse von Lactamen, ζ. B. Caprolactam, zu den entsprechenden Aminocarbonsäureestern, z. B. zu den ε-Aminocapronsäureestern, führt, ist das Ergebnis des erfindungsgemäßen Verfahrens dennoch überraschend, da bei der Einwirkung des Alkohols auf N-acylierte Lactame zwei am gleichen Stickstoffatom gebundene Carbonylgruppen miteinander konkurrieren, so daß nicht vorauszusehen war, ob N-acylierte Carbonsäureester oder Carbonsäureester und Aminocarbonsäureester bzw. Lactame gebildet würden.Although it is known that the alcoholysis of lactams, ζ. B. caprolactam, to the corresponding Aminocarboxylic acid esters, e.g. B. to the ε-aminocaproic acid esters, leads, the result of the process according to the invention is nevertheless surprising, since the action of the alcohol on N-acylated Lactams with two carbonyl groups attached to the same nitrogen atom compete with each other, so that it could not be foreseen whether N-acylated carboxylic acid esters or carboxylic acid esters and Aminocarboxylic acid esters or lactams would be formed.

Unter den als Ausgangsstoffe für das Verfahren geeigneten N-acylierten Lactamen seien z. B. ge-Among the N-acylated lactams suitable as starting materials for the process are, for. B. ge

209 535/4209 535/4

nannt: N-Acetylbutyrolactam, N-Benzoylcaprolactatn, N -Terephthalsäuremonomethylestercaprolactam, Ν,Ν'-Adipinyl-bis-butyrolactam, N, N'-Adipinyl - bis - valerolactam, N, N'- Adipinyl - bis caprolactam und Ν,Ν'-Terephthalyl-bis-caprolactam. named: N-Acetylbutyrolactam, N-Benzoylcaprolactatn, N-Terephthalic acid monomethyl ester caprolactam, Ν, Ν'-adipinyl-bis-butyrolactam, N, N'-adipinyl - bis - valerolactam, N, N'-adipinyl - bis caprolactam and Ν, Ν'-terephthalyl-bis-caprolactam.

Für die Alkoholyse solcher N-Acyllactame können z.B. verwendet werden: Methanol, Äthanol, Propanol, Isopropanol, Butanol, Isobutanol undFor the alcoholysis of such N-acyllactams, for example, the following can be used: methanol, ethanol, Propanol, isopropanol, butanol, isobutanol and

ίο Glykol.ίο glycol.

Als Veresterungskatalysatoren eignen sich für das vorliegende Verfahren z. B. Chlorwasserstoff, Schwefelsäure, Kaliumsulfat, Phosphorsäure und Essigsäure.As esterification catalysts are suitable for the present process, for. B. hydrogen chloride, Sulfuric acid, potassium sulfate, phosphoric acid and acetic acid.

Bei Normaltemperatur verläuft die Umsetzung sehr langsam. Es ist daher vorteilhaft, erhöhte Temperaturen, z. B. zwischen etwa 40 und ioo° C und insbesondere zwischen etwa 50 und 700 C, anzuwenden.The reaction takes place very slowly at normal temperature. It is therefore advantageous to use elevated temperatures, e.g. B. between about 40 and 100 ° C and in particular between about 50 and 70 0 C, apply.

ao Die N-acylierten Aminocarbonsäureester sind wertvolle Zwischenprodukte z. B. zur Herstellung von Polykondensationsprodukten. Außerdem können sie als Weichmacher für Kunststoffe, z. B. für Celluloseacetat und Polyvinylchlorid, verwendet werden.ao The N-acylated aminocarboxylic acid esters are valuable intermediates z. B. for the production of polycondensation products. Also can use them as plasticizers for plastics, e.g. B. for cellulose acetate and polyvinyl chloride used will.

Beispielexample

90 Gewichtsteile Ν,Ν'-Terephthalyl-bis-caprolactam (Fp. 1980 C) werden mit 600 Volumteilen Methanol unter Zusatz von 5 Gewichtsteilen konzentrierter Schwefelsäure 20 Minuten unter Rückfluß bis zur vollständigen Lösung erhitzt.90 parts by weight Ν, Ν'-terephthalyl bis-caprolactam (mp. 198 0 C) are mixed with 600 parts by volume of methanol with the addition of 5 parts by weight of concentrated sulfuric acid for 20 minutes under reflux until complete solution heated.

Zur Beiseitigung von ungelösten Verunreinigungen wird die Lösung heiß filtriert. Nach dem Abkühlen kristallisieren 90 Gewichtsteile Terephthalyl-bis -aminocapronsäuredimethylester (Fp. i6o° C) aus. Durch Einengen und Neutralisieren der Mutterlauge können weitere Mengen des Esters gewonnen werden. Bereits durch einmaliges Umkristallisieren aus Methanol oder Glykoläthyläther erhält man den Ester rein (Fp. 1650 C).The solution is filtered hot to remove undissolved impurities. After cooling, 90 parts by weight of dimethyl terephthalyl bisaminocaproate (melting point 160 ° C.) crystallize out. Further quantities of the ester can be obtained by concentrating and neutralizing the mother liquor. Already by a single recrystallization from methanol or Glykoläthyläther yields the pure ester (mp. 165 0 C).

Claims (1)

PATENTANSPKUCH:PATENT APPLICATION: Verfahren zur Herstellung von Acylaminocarbonsäureestern, dadurch gekennzeichnet, daß man N-acylierte Lactame mit Alkoholen in Gegenwart von Veresterungskatalysatoren, vorzugsweise bei höheren Temperaturen, umsetzt.Process for the preparation of acylaminocarboxylic acid esters, characterized in that one N-acylated lactams with alcohols in the presence of esterification catalysts, preferably at higher temperatures. In Betracht gezogene Druckschriften:Considered publications: USA.-Patentschriften Nr. 2277152, 2303177; britische Patentschrift Nr. 693 645;U.S. Patent Nos. 2277152, 2303177; British Patent No. 693,645; französische Patentschrift Nr. 889 683;French Patent No. 889,683; Organic Syntheses, 17, S. 7/8, (1937);Organic Syntheses, 17, pp. 7/8, (1937); Gattermann, Praxis des organischen Chemikers, 1947, S. 78/79;Gattermann, Praxis des Organic Chemist, 1947, pp. 78/79; deutsche Patentanmeldung D 4332 IVb/12q;German patent application D 4332 IVb / 12q; Hollemann—Richter, Lehrbuch der organischen Chemie, 23. Auflage (1942), S. 282;Hollemann-Richter, textbook of organic Chemie, 23rd Edition (1942), p. 282; Helvetica chimica acta, Band XII (1929) S. 361;Helvetica chimica acta, Volume XII (1929) p. 361; K a r r e r, Lehrbuch der organischen Chemie, 9. Auflage (i943)> S. 280;K a r r e r, Textbook of Organic Chemistry, 9th edition (1943)> P. 280; Langenbeck, Lehrbuch der organischen Chemie, 7. Auflage (1948), S. 143;Langenbeck, Textbook of Organic Chemistry, 7th Edition (1948), p. 143; Helvetica chimica acta, 4 (1921), S. 477 bis 479.Helvetica chimica acta, 4 (1921), pp. 477 to 479. ©209 535/4 3.62© 209 535/4 3.62
DEF13369A 1953-12-02 1953-12-02 Process for the preparation of acylaminocarboxylic acid esters Expired DE975633C (en)

Priority Applications (1)

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DEF13369A DE975633C (en) 1953-12-02 1953-12-02 Process for the preparation of acylaminocarboxylic acid esters

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5717118A (en) * 1995-09-05 1998-02-10 Eastman Chemical Company Process for preparing amido-carboxylic acid esters having internal amide linkages

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2277152A (en) * 1938-12-08 1942-03-24 Du Pont Preparation of polyamides
US2303177A (en) * 1938-12-06 1942-11-24 Schlack Paul Polyvalent lactams
GB693645A (en) * 1950-07-28 1953-07-01 Wingfoot Corp Method of increasing the molecular weight of polyesters, polyesteramides or polyamides or polyamides

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2303177A (en) * 1938-12-06 1942-11-24 Schlack Paul Polyvalent lactams
US2277152A (en) * 1938-12-08 1942-03-24 Du Pont Preparation of polyamides
GB693645A (en) * 1950-07-28 1953-07-01 Wingfoot Corp Method of increasing the molecular weight of polyesters, polyesteramides or polyamides or polyamides

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5717118A (en) * 1995-09-05 1998-02-10 Eastman Chemical Company Process for preparing amido-carboxylic acid esters having internal amide linkages

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