DE1593212C3 - Process for the preparation of maleamic acid derivatives - Google Patents

Process for the preparation of maleamic acid derivatives

Info

Publication number
DE1593212C3
DE1593212C3 DE1966O0011436 DEO0011436A DE1593212C3 DE 1593212 C3 DE1593212 C3 DE 1593212C3 DE 1966O0011436 DE1966O0011436 DE 1966O0011436 DE O0011436 A DEO0011436 A DE O0011436A DE 1593212 C3 DE1593212 C3 DE 1593212C3
Authority
DE
Germany
Prior art keywords
acid derivatives
maleamic acid
preparation
formula
tert
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
DE1966O0011436
Other languages
German (de)
Other versions
DE1593212B2 (en
DE1593212A1 (en
Inventor
Gregoire Kalopissis
Andre Viout
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LOreal SA
Original Assignee
LOreal SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by LOreal SA filed Critical LOreal SA
Publication of DE1593212A1 publication Critical patent/DE1593212A1/en
Publication of DE1593212B2 publication Critical patent/DE1593212B2/en
Application granted granted Critical
Publication of DE1593212C3 publication Critical patent/DE1593212C3/en
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/12—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms
    • C07D295/125—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • C07D295/13—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Pyrrole Compounds (AREA)

Description

H2N-(CH2),,-NH 2 N- (CH 2 ) ,, - N

worin ;i, R1 und R2 die obengenannten Bedeutungen haben, in Gegenwart eines Lösungsmittels, das dadurch gekennzeichnet ist, daß als Lösungsmittel Äthylacetat oder tert.-Butylalkohol bei Temperaturen bis einschließlich 5O0C verwendet wird.wherein i, R 1 and R 2 have the abovementioned meanings, in the presence, of a solvent, which is characterized in that the solvent used is ethyl acetate or tert-butyl alcohol at temperatures up to and including 5O 0 C.

Die Herstellung derartiger Maleinamidsäurederivate ist aus der USA.-Patentschrift 2 821 521 bereits bekannt; bei der dort beschriebenen Kondensation werden jedoch als Lösungsmittel aromatische Kohlenwasserstoffe, wie Benzol, Toluol, Xylol usw., verwendet. Diese Lösungsmittel zeigen jedoch verschiedene Nachteile. So wird beispielsweise bei Anwendung von Ν,Ν-Diäthylaminopropylamin das entsprechende Maleinamidsäurederivat in Form einer gefärbten klebrigen Paste erhalten, die nur schwer kristallisiert. Die Reinigung der so erhaltenen Maleinamidsäurederivate ist daher sehr umständlich. Dieser Nachteil wirkt sich insbesondere dann sehr unangenehm aus, wenn die Maleinamidsäurederivate unmittelbar für die Synthese weiterer Produkte, wie z. B. von Asparaginderivaten, verwendet werden sollen.The preparation of such maleamic acid derivatives is already known from US Pat. No. 2,821,521 known; in the condensation described there, however, aromatic hydrocarbons are used as solvents, such as benzene, toluene, xylene, etc. are used. However, these solvents show different ones Disadvantage. For example, when Ν, Ν-diethylaminopropylamine is used, the corresponding Maleamic acid derivative obtained in the form of a colored sticky paste which crystallizes only with difficulty. The purification of the maleamic acid derivatives obtained in this way is therefore very laborious. This disadvantage has a particularly unpleasant effect when the maleamic acid derivatives directly for the synthesis of other products, such as. B. of asparagine derivatives are to be used.

Es wurde nun gefunden, daß bei Anwendung von Äthylacetat oder tert.-Butylalkohol als Lösungsmittel nach Beendigung der Reaktion die Maleinamidsäurederivate in kristallisierter Form ausfallen. Die Umsetzung bei Temperaturen bis einschließlich 500C, vorzugsweise unter 300C, durchgeführt. Die Gesamtkonzentration der Reaktionsteilnehmer beträgt vorteilhafterweise 30 bis 40 Gewichtsprozent. Bei Anwendung von tert.-Butylalkohol als Lösungsmittel wird vorteilhafterweise eine Reaktionstemperatur von 50° C eingehalten.It has now been found that when ethyl acetate or tert-butyl alcohol is used as the solvent, the maleamic acid derivatives precipitate in crystallized form after the reaction has ended. The reaction at temperatures up to and including 50 ° C., preferably below 30 ° C., is carried out. The total concentration of the reactants is advantageously 30 to 40 percent by weight. When using tert-butyl alcohol as solvent, a reaction temperature of 50 ° C. is advantageously maintained.

Wie aus der Tabelle hervorgeht, ist die Einhaltung der optimalen Reaktionsbedingungen bei Anwendung der genannten Lösungsmittel von der Art der Radikale R1 und R2 abhängig.As can be seen from the table, compliance with the optimal reaction conditions when using the solvents mentioned depends on the nature of the radicals R 1 and R 2.

TabelleTabel

CH- CONH — (CH2)- N
CH-COOH R2 CH-CONH - (CH 2 ) - N
CH-COOH R 2 Lösungs
mittelSolution
middle Tem
peraturTem
temperature Gesamt
konzen
tration der
Reaktions
teilnehmertotal
concentrate
tration of
Reaction
Attendees Ausbeuteyield Aminst
in MilliäquAminst
in milliequ ickstoff
ivalcntcn/gnitrogen
ivalcntcn / g Säure
in Milliäquacid
in milliequ gehalt
ivalcnten/gsalary
ivalcnten / g in g/100 gin g / 100 g berechnetcalculated gefundenfound berechnetcalculated gefundenfound R1 = R2 = C2H5, η = 3R 1 = R 2 = C 2 H 5 , η = 3 Äthyl
acetatethyl
acetate O bis
50CO to
5 0 C 38,8%38.8% 100%100% 4,384.38 4,394.39 4,384.38 4,414.41 tert.-
Butyl
alkoholtert.-
Butyl
alcohol 50° C50 ° C 33,4%33.4% 98%98% 5,005.00 4,874.87 5,005.00 5,135.13 R1 = R2 = C2H5, /! = 2 R 1 = R 2 = C 2 H 5 , /! = 2 tert.-
Butyl
alkoholtert.-
Butyl
alcohol 500C50 0 C 35%35% 89%89% 4,674.67 4,594.59 4,674.67 4.494.49

Nachstehend wird das erfindungsgemäße Verfahren an Hand weiterer Beispiele näher erläutert.The process according to the invention is explained in more detail below with the aid of further examples.

Beispiel 1example 1

Zu einer Lösung von 390 g (3 Mol) N,N-Diäthylaminopropylamin in 600 cm3 Äthylacetat wird unter Rühren und mit Hilfe eines Einfülltrichters 297 g Maleinsäureanhydrid, gelöst im 600 cm3 Äthylacetat, hinzugefügt. Während der Zugabe des Maleinsäureanhydride wird die Temperatur zwischen 0 und 5° C gehalten. Die Dauer dieses Vorganges beträgt 21I2 Stunden. Einige Minuten vor Beendigung des Eintragens beginnt die Ν,Ν-Diäthylaminopropylmaleinamidsäure auszufallen, die nach mehreren Stunden Stehen des Reaktionsgemisches bei Raumtemperatur durch Filtration abgetrennt wird. Nach dem Waschen mit Äthylacetat, Abtrennen und Trocknen wird ein weißes Pulver in 100%iger Ausbeute gewonnen.To a solution of 390 g (3 mol) of N, N-diethylaminopropylamine in 600 cm 3 of ethyl acetate, 297 g of maleic anhydride, dissolved in 600 cm 3 of ethyl acetate, are added with stirring and with the aid of a funnel. During the addition of the maleic anhydride, the temperature is kept between 0 and 5 ° C. The duration of this process is 2 1 I 2 hours. A few minutes before the end of the entry, the Ν, Ν-diethylaminopropylmaleamic acid begins to precipitate, which is separated off by filtration after the reaction mixture has stood for several hours at room temperature. After washing with ethyl acetate, separating and drying, a white powder is obtained in 100% yield.

Beispiel 2Example 2

204 g (2 Mol) Ν,Ν-Dimethylaminopropylamin werden in 800 g tert.-Butylalkohol gelöst und die Lösung auf 500C erwärmt. Sodann wird unter Rühren 198 g pulverisiertes Maleinsäureanhydrid im Laufe einer Stunde bei 500C eingetragen. Nach einigen Stunden Stehen des Reaktionsgemisches fällt die gebildete N,N - Dimetjiylaminopropyl - maleinamidsäure aus. Nach dem Abfiltrieren, Waschen mit Aceton und Trocknen wird ein weißes Pulver in einer Ausbeute von 98% erhalten (Fp. = 56 bis 59° C).204 g (2 mol) Ν, Ν-dimethylaminopropylamine are dissolved in 800 g tert-butyl alcohol and the solution at 50 0 C heated. 198 g of powdered maleic anhydride are then introduced at 50 ° C. over the course of one hour, with stirring. After the reaction mixture has stood for a few hours, the N, N-dimethylaminopropylmaleamic acid formed precipitates. After filtering off, washing with acetone and drying, a white powder is obtained in a yield of 98% (melting point = 56 to 59 ° C.).

Claims (1)

Patentanspruch:Claim: Verfahren zur Herstellung von Maleinamidsäurederivaten der FormelProcess for the preparation of maleamic acid derivatives the formula CH — CO — NH — (CH2),, — N CH-COOHCH - CO - NH - (CH 2 ) ,, - N CH-COOH R,R, worin R1 und R2 gleiche oder verschiedene Alkylreste mit bis zu 4 C-Atomen sind oder zusammengenommen auch den Morpholino- oder Piperidinorest bilden und η eine ganze Zahl von 2 bis 5 bedeutet, durch Kondensation von Maleinsäureanhydrid mit einem Alkylendiamin der Formelwhere R 1 and R 2 are identical or different alkyl radicals with up to 4 carbon atoms or, taken together, also form the morpholino or piperidino radical and η denotes an integer from 2 to 5, by condensation of maleic anhydride with an alkylenediamine of the formula H2N-(CH2),,-NH 2 N- (CH 2 ) ,, - N 2525th worin n, R1 und R2 die oben angegebene Bedeutung haben, in Gegenwart eines Lösungsmittels, dadurch gekennzeichnet, daß als Lösungsmittel Äthylacetat oder tert.-Butylalkohol unter Einhaltung von Temperaturen bis einschließlich 500C verwendet wird.wherein n, R 1 and R 2 have the abovementioned meaning, in the presence of a solvent, characterized in that the solvent used is ethyl acetate or tert-butyl alcohol in compliance with temperatures up to 50 0 C. 3535 Die Erfindung betrifft ein Verfahren zur Herstellung von Maleinamidsäurederivaten der FormelThe invention relates to a process for the preparation of maleamic acid derivatives of the formula R,R, 4040 CH — CO — NH — (CH2)„ — N CH-COOH R2 CH - CO - NH - (CH 2 ) "- N CH-COOH R 2 worin R1 und R2 gleiche oder verschiedene Alkylreste mit bis zu 4 C Atomen sind oder zusammen-wherein R 1 and R 2 are identical or different alkyl radicals with up to 4 C atoms or together 45 genommen auch den Morpholino- oder Piperidinorest bilden und η eine ganze Zahl von 2 bis 5 bedeutet, durch Kondensation von Maleinsäureanhydrid mit einem Alkylendiamin der Formel45 taken also form the morpholino or piperidino radical and η denotes an integer from 2 to 5, by condensation of maleic anhydride with an alkylenediamine of the formula
DE1966O0011436 1965-06-15 1966-02-10 Process for the preparation of maleamic acid derivatives Expired DE1593212C3 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR20933A FR1459800A (en) 1965-06-15 1965-06-15 New process for the preparation of maleamic acid derivatives

Publications (3)

Publication Number Publication Date
DE1593212A1 DE1593212A1 (en) 1970-07-16
DE1593212B2 DE1593212B2 (en) 1975-01-16
DE1593212C3 true DE1593212C3 (en) 1975-08-28

Family

ID=8582122

Family Applications (1)

Application Number Title Priority Date Filing Date
DE1966O0011436 Expired DE1593212C3 (en) 1965-06-15 1966-02-10 Process for the preparation of maleamic acid derivatives

Country Status (7)

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AT (1) AT258263B (en)
BE (1) BE675312A (en)
CH (1) CH448125A (en)
DE (1) DE1593212C3 (en)
FR (1) FR1459800A (en)
GB (1) GB1134344A (en)
NL (2) NL6600691A (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2431160C2 (en) * 1974-06-26 1986-04-30 Toa Nenryo Kogyo K.K., Tokio/Tokyo Process for making an ashless detergent dispersant composition and its use in hydrocarbon oil compositions
US4216238A (en) 1979-02-13 1980-08-05 Stauffer Chemical Company Dialkyl amino ethyl amides, their salts and their use as anti-ripening agents

Also Published As

Publication number Publication date
FR1459800A (en) 1966-06-17
GB1134344A (en) 1968-11-20
DE1593212B2 (en) 1975-01-16
NL6600691A (en) 1966-12-16
NL127233C (en)
DE1593212A1 (en) 1970-07-16
BE675312A (en) 1966-07-19
AT258263B (en) 1967-11-10
CH448125A (en) 1967-12-15

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Legal Events

Date Code Title Description
C3 Grant after two publication steps (3rd publication)
E77 Valid patent as to the heymanns-index 1977
8339 Ceased/non-payment of the annual fee