DE1593212B2 - Process for the preparation of maleamic acid derivatives - Google Patents
Process for the preparation of maleamic acid derivativesInfo
- Publication number
- DE1593212B2 DE1593212B2 DE1966O0011436 DEO0011436A DE1593212B2 DE 1593212 B2 DE1593212 B2 DE 1593212B2 DE 1966O0011436 DE1966O0011436 DE 1966O0011436 DE O0011436 A DEO0011436 A DE O0011436A DE 1593212 B2 DE1593212 B2 DE 1593212B2
- 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.)
- Granted
Links
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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyrrole Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
H2N- (CH2)n - NH 2 N- (CH 2 ) n -N
worin n, 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 50° C verwendet wird.in which n, R 1 and R 2 have the abovementioned meanings, in the presence of a solvent which is characterized in that ethyl acetate or tert-butyl alcohol at temperatures up to and including 50 ° C. is used as the solvent.
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 50° C, vorzugsweise unter 30° C, 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 using ethyl acetate or tert-butyl alcohol as a solvent after the reaction has ended, the maleamic acid derivatives precipitate in crystallized form. The implementation at temperatures up to and including 50 ° C, preferably below 30 ° C carried out. The total concentration the reactant is advantageously 30 to 40 percent by weight. When applying of tert-butyl alcohol as a solvent is advantageously a reaction temperature of 50 ° C 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.
CH-COOH R2 CH-CONH- (CH 2 ), -N
CH-COOH R 2
mittelSolution
middle
peraturTem
temperature
konzen
tration der
Realctions-
teilnehmer
in g/100 gtotal
concentrate
tration of
Realctions-
Attendees
in g / 100 g
in Milliäqu
berechnetAminst
in milliequ
calculated
ivalenten/g
gefundennitrogen
equivalents / g
found
in Milliäqu
berechnetacid
in milliequ
calculated
ivalenten/g
gefunden“Eh
equivalents / g
found
acetatethyl
acetate
5°CO to
5 ° C
Butyl
alkoholtert.-
Butyl
alcohol
Butyl
alkoholtert.-
Butyl
alcohol
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.
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 Maleinsäureanhydrids 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.
Beispiel 2To 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. The temperature is kept between 0 and 5 ° C. during the addition of the maleic anhydride. 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.
Example 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 - Dimet^ylaminopropyl - 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-dimethylaminopropyl maleamic acid formed precipitates out. 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)
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 true DE1593212B2 (en) | 1975-01-16 |
DE1593212C3 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)
Country | Link |
---|---|
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)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3948909A (en) * | 1974-06-26 | 1976-04-06 | Toa Nenryo Kogyo Kabushiki Kaisha | Ashless detergent dispersant for hydrocarbon oils |
US4216238A (en) | 1979-02-13 | 1980-08-05 | Stauffer Chemical Company | Dialkyl amino ethyl amides, their salts and their use as anti-ripening agents |
-
0
- NL NL127233D patent/NL127233C/xx active
-
1965
- 1965-06-15 FR FR20933A patent/FR1459800A/en not_active Expired
-
1966
- 1966-01-18 CH CH64466A patent/CH448125A/en unknown
- 1966-01-19 NL NL6600691A patent/NL6600691A/xx unknown
- 1966-01-19 BE BE675312D patent/BE675312A/xx unknown
- 1966-02-04 AT AT102766A patent/AT258263B/en active
- 1966-02-10 DE DE1966O0011436 patent/DE1593212C3/en not_active Expired
- 1966-05-10 GB GB2073166A patent/GB1134344A/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
CH448125A (en) | 1967-12-15 |
AT258263B (en) | 1967-11-10 |
NL127233C (en) | |
NL6600691A (en) | 1966-12-16 |
BE675312A (en) | 1966-07-19 |
DE1593212A1 (en) | 1970-07-16 |
DE1593212C3 (en) | 1975-08-28 |
FR1459800A (en) | 1966-06-17 |
GB1134344A (en) | 1968-11-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CH642352A5 (en) | MALEINIMIDE AND SUCCINIMIDE DERIVATIVES, METHOD FOR PRODUCING THE SAME AND HERBICIDES CONTAINING THESE DERIVATIVES. | |
DE1593212C3 (en) | Process for the preparation of maleamic acid derivatives | |
DE2535930A1 (en) | ABIETAMIDE DERIVATIVES AND METHOD FOR THEIR PRODUCTION | |
DE1212984B (en) | Process for the production of basic substituted coumarones | |
DE2246111C3 (en) | Process for the preparation of naphthalimide-43-dicarboxylic acids | |
DE1918253A1 (en) | 3-hydroxyisoxazoles (soil fungicides) prodn | |
DE1009623B (en) | Process for the preparation of ª ‡ -oxy-1,2,5,6-tetrahydrobenzylphosphinous acid or its alkali metal salts | |
DE1912941B2 (en) | 1 -PhenyM-amino-e-methoxypridazinium salts | |
DE2521347B2 (en) | Hydroxyl-substituted 2-chloro-a - (tert-butylaminomethyl-benzyl alcohols, manufacturing processes and pharmaceuticals | |
DE2612615C2 (en) | Process for the preparation of optically active α-phenylglycine and intermediates therefor | |
DE2512702C2 (en) | Substituted 1-amino-3-phenyl-indoles, their salts and process for their preparation | |
DE3135728C2 (en) | Process for the preparation of apovincamic acid esters | |
DE2705601C3 (en) | containing medicinal products | |
DE850297C (en) | Process for the preparation of amidine salts | |
DE1670143C3 (en) | ||
DE3490340T1 (en) | Herbicidal crotonic acid derivatives, their preparation and compositions containing them | |
DE935667C (en) | Process for the preparation of phenanthridinium salts | |
DE2239400A1 (en) | NEW TRIAZOLINIUM COMPOUNDS, THE PROCESS FOR THEIR PRODUCTION AND THEIR CONTAINING MEANS TO INHIBIT PLANT GROWTH | |
DE415318C (en) | Process for the preparation of 4-arylamino-1-arylimino-2-naphthoquinones | |
DE883897C (en) | Process for the preparation of 17- (ª ‡) -oxy-20-ketopregnanes | |
DE2747121A1 (en) | 6- (M-AMINOPHENYL-2,3,5,6-TETRAHYDROIMIDAZO SQUARE CLAMP ON 2.1-B SQUARE CLAMP FOR THIAZOLE DERIVATIVES, PROCESS FOR THEIR PRODUCTION AND THEIR USE | |
CH527144A (en) | Aqueous formaldehyde solns stabilised with | |
DE1418527C (en) | Process for the preparation of amino acid derivatives. Note 9 Nippon Shinyaku Co., Ltd., Kyoto (Japan) | |
AT284850B (en) | Process for the preparation of new N- (cycloalkyloxy-alkyl) piperazine derivatives, their salts and quaternary derivatives | |
DE1071336B (en) | Process for the production of nitrogen-containing synthetic resins |
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 |