DE1770041A1 - Process for the preparation of alpha-amino-maleimides - Google Patents
Process for the preparation of alpha-amino-maleimidesInfo
- Publication number
- DE1770041A1 DE1770041A1 DE19681770041 DE1770041A DE1770041A1 DE 1770041 A1 DE1770041 A1 DE 1770041A1 DE 19681770041 DE19681770041 DE 19681770041 DE 1770041 A DE1770041 A DE 1770041A DE 1770041 A1 DE1770041 A1 DE 1770041A1
- Authority
- DE
- Germany
- Prior art keywords
- parts
- amino
- hydroxy
- general formula
- maleimides
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims description 9
- TUZVMPXGFZSNBG-UHFFFAOYSA-N 3-aminopyrrole-2,5-dione Chemical class NC1=CC(=O)NC1=O TUZVMPXGFZSNBG-UHFFFAOYSA-N 0.000 title claims description 4
- 238000002360 preparation method Methods 0.000 title claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 13
- 239000007858 starting material Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 150000003951 lactams Chemical class 0.000 description 9
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- 229960000583 acetic acid Drugs 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000012362 glacial acetic acid Substances 0.000 description 5
- -1 heterocyclic radical Chemical class 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000002373 5 membered heterocyclic group Chemical group 0.000 description 2
- 125000004070 6 membered heterocyclic group Chemical group 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SOWPGKJPEXNMCS-OWOJBTEDSA-N (e)-2-bromobut-2-enedioic acid Chemical compound OC(=O)\C=C(\Br)C(O)=O SOWPGKJPEXNMCS-OWOJBTEDSA-N 0.000 description 1
- UBAHEZQPAINIOT-UHFFFAOYSA-N 1-benzyl-3-morpholin-4-ylpyrrole-2,5-dione Chemical compound N1(CCOCC1)C1=CC(=O)N(C1=O)CC1=CC=CC=C1 UBAHEZQPAINIOT-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- VMCICDADKZXNHW-UHFFFAOYSA-N 1h-triazin-2-amine Chemical compound NN1NC=CC=N1 VMCICDADKZXNHW-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- YHWMFDLNZGIJSD-UHFFFAOYSA-N 2h-1,4-oxazine Chemical compound C1OC=CN=C1 YHWMFDLNZGIJSD-UHFFFAOYSA-N 0.000 description 1
- VIUDTWATMPPKEL-UHFFFAOYSA-N 3-(trifluoromethyl)aniline Chemical compound NC1=CC=CC(C(F)(F)F)=C1 VIUDTWATMPPKEL-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- ROMURMXNNUEGCC-ZRDIBKRKSA-N diethyl (e)-2-anilinobut-2-enedioate Chemical class CCOC(=O)\C=C(C(=O)OCC)\NC1=CC=CC=C1 ROMURMXNNUEGCC-ZRDIBKRKSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- LJXQPZWIHJMPQQ-UHFFFAOYSA-N pyrimidin-2-amine Chemical compound NC1=NC=CC=N1 LJXQPZWIHJMPQQ-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- GLQWRXYOTXRDNH-UHFFFAOYSA-N thiophen-2-amine Chemical compound NC1=CC=CS1 GLQWRXYOTXRDNH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
- C07D207/444—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5
- C07D207/456—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to other ring carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyrrole Compounds (AREA)
Description
Verfahren zur Herstellung von &-Amino-maleinimiden Gegenstand dieser Erfindung ist ein Verfahren zur Herstellung von α-Amino-maleinimiden durch Umsetzung von α,ß-Dihalogen-γ-hydroxycrotonlactamen mit Ammoniak oder Aminen.Process for making & -amino-maleimide article This invention is a process for the preparation of α-amino-maleimides by reacting α, ß-dihalo-γ-hydroxycrotone lactams with ammonia or amines.
Es ist bekannt Monobrommaleinsäure mit Anilin zu Phenylamidomaleinsäureanil umzusetzen (Berichte der Deutschen Chemischen Gesellachaft, Band 19, Seite 1377 (1886)). Ebenfalls laasen sich substituierte Amino-maleinimide durch Umsetzung von Monohalogenmaleinimiden mit Aminen bzw. von Anilino-maleinsäure-diäthylestern mit Anilin herstellen (Journal of the American Chemical Society, Band 68, Seiten 514 - 517 (1946); Journal of the Chemical Society, Band 125, Seite 466 (1924)). Alle diese Verfahren liefern die gewünschten Endprodukte in unbefriedigender Ausbeute und Reinheit.It is known monobromomaleic acid with aniline to phenylamidomaleic anil implement (Reports of the German Chemical Society, Volume 19, Page 1377 (1886)). Substituted amino-maleimides can also be obtained by reacting Monohalogenmaleimides with amines or of anilino-maleic acid diethyl esters with Making aniline (Journal of the American Chemical Society, Volume 68, pages 514 - 517 (1946); Journal of the Chemical Society, vol. 125, p. 466 (1924)). All these processes give the desired end products in unsatisfactory yields and purity.
Es wurde nun gefunden, daß man A-Amino-maleinimide der allgemeinen Formel in der R1, R2 und R3 gleich oder verschieden sein können und Jeweils ein Wasserstoffatom, einen aliphatischen, cycloaliphtischen, araliphatischen, aromatischen oder heterocyclischen Rest bedeuten, darüber hinaus auch R2 und R3 zusammen mit dem benachbarten Stickstoffatom einen heterocyclischen Ring bilden können, vorteilhaft erhält, wenn man α,ß-Dihalogen-γ-hydroxy-crotonlactame der allgemeinen Formel in der R1 die vorgenannte Bedeutung hat und X flir ein Halogenatom steht, mit Ammoniak oder Aminen der allgemeinen Formel in der R2 und R3 die vorgenannte Bedeutung haben, bei einer Temperatur >50°C umsetzt.It has now been found that A-amino-maleimides of the general formula in which R1, R2 and R3 can be identical or different and each represent a hydrogen atom, an aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic radical, in addition also R2 and R3 can form a heterocyclic ring together with the adjacent nitrogen atom, is advantageously obtained, when using α, ß-dihalo-γ-hydroxy-crotonlactams of the general formula in which R1 has the aforementioned meaning and X stands for a halogen atom, with ammonia or amines of the general formula in which R2 and R3 have the aforementioned meaning, reacts at a temperature> 50 ° C.
Die Reaktion läßt aich für den Fall der Verwendung von ß-Dichlor-γ-hydroxy-N-cyclohexyl-crotonlactam und Pyrrolidin durch folgende Formeln wiedergeben: Das Verfahren nach der Erfindung liefert im Vergleich zu den bekannten Verfahren eine große Zahl von &-Amino-maleinsäureimiden in besserer Ausbeute und Reinheit. Es war im Hinblick auf den Stand der Technik Uberraschend, daß nach dem Verfahren in einer Stufe ein Halogenatom durch das Amin und das andere durch ein Wasserstoffatom unter gleichzeitiger Umwandlung des $-Hydroxycrotonlactams zum Maleinsäureimid substituiert werden.If ß-dichloro-γ-hydroxy-N-cyclohexyl-crotonlactam and pyrrolidine are used, the reaction can be represented by the following formulas: Compared to the known processes, the process according to the invention provides a large number of & -amino-maleic acid imides in better yield and purity. In view of the prior art, it was surprising that, according to the process, one halogen atom is substituted in one step by the amine and the other by a hydrogen atom with simultaneous conversion of the $ -hydroxycrotonlactam to the maleic acid imide.
Als Ausgangsstoffe verwendet man α,ß-Dihalogen-γ-hydroxy-crotonlactame der allgemeinen Formel II, die z. B. durch Umsestzung von Mucohalogensäurechlorid mit primären Aminen hergestellt werden können (siehe Patent . ... ... Patentanmeldung . .,. ..., O.Z.The starting materials used are α, ß-dihalo-γ-hydroxy-croton lactams of the general formula II, the z. B. by conversion of mucohalogen acid chloride can be prepared with primary amines (see patent. ... ... patent application . .,. ..., O.Z.
25 467). Bevorzugte Ausgangsstoffe II und dementsprechend bevorzugte Endstoffe I sind solche, in deren Formeln R1 ein Wasserstoffatom, einen Alkyl-, Cycloalkyl-, Aralkyl-, Arylrest mit jeweils bis zu 12 Kohlenstoffatomen oder einen 5- oder 6-gliedrigen heterocyclischen Ring, der 1 bis 3 Stickstoffatome, 1 Sauerstoff-oder ein Schwefelatom bzw. 2 bis 3 verschiedene oder teilweise verschiedene Heteroatome in einem Ring enthalten kann, bedeutet und die einzelnen Reste X gleich oder verschieden sein können und jeweils für ein Chlor- oder Bromatom stehen. In den bevorzugten Ausgangsatoffen kann R1 in seiner Bedeutung als heterocyclischer Ring auch durch Alkylgruppen mit bis zu 4 Eohlenstoffatomen mit dem Stickstoffatom verbunden sein und/oder am heterocyclischen Ring noch ein Benzolkern annelliert sein.25 467). Preferred starting materials II and accordingly preferred End products I are those in whose formulas R1 is a hydrogen atom, an alkyl, Cycloalkyl, aralkyl, aryl radicals each with up to 12 carbon atoms or one 5- or 6-membered heterocyclic ring containing 1 to 3 nitrogen atoms, 1 oxygen or a sulfur atom or 2 to 3 different or partially different heteroatoms may contain in a ring, and the individual radicals X are identical or different can be and each stand for a chlorine or bromine atom. In the preferred R1 in its meaning as a heterocyclic ring can also be used as starting materials Alkyl groups with up to 4 carbon atoms can be linked to the nitrogen atom and / or a benzene nucleus can also be fused to the heterocyclic ring.
Es können z. B. folgende Ausgangsstoffe II verwendet werden: α,ß-Dichlor-γ-hydroxy-crotonlactam, α,ß-Dichlor-γ-hydroxy-N-äthylcrotonlactam, i, ,ß-Dichlor-γ-hydroxy-N-(ß-indoyl)-äthyl-crotonlactam, , ß-Dichlor-γ-hydroxy-N-cyclohexyl-crotonlactam, (, ß-Dibrom-γ-hydroxy-N-(p-nitro)-phenyl-crotonlactam, α,ß-Dichlor-γ-hydroxy-N-(pyrimidyl-2 ) -crotonlactam, ot-Chlor-ß-bromhydroxy-N-benzyl-crotonlactam sowie analoge N-(furany1-2)-, N-(thiophenyl-2)-, N-(morpholinyl-2)-, N-(triazinyl-2)-crotonlactame.It can e.g. B. the following starting materials II are used: α, ß-dichloro-γ-hydroxy-crotonlactam, α, ß-dichloro-γ-hydroxy-N-äthylcrotonlactam, i,, ß-dichloro-γ-hydroxy-N- (ß-indoyl) -ethyl-crotonlactam, , ß-dichloro-γ-hydroxy-N-cyclohexyl-crotonlactam, (, ß-dibromo-γ-hydroxy-N- (p-nitro) -phenyl-crotonlactam, α, ß-dichloro-γ-hydroxy-N- (pyrimidyl-2) -crotone lactam, ot-chloro-ß-bromohydroxy-N-benzyl-crotone lactam as well as analogous N- (furany1-2) -, N- (thiophenyl-2) -, N- (morpholinyl-2) -, N- (triazinyl-2) -crotone lactams.
Bevorzugte Ausgangsstoffe der allgemeinen Formel III und dementsprechend bevorzugte Endstoffe I sind solche, in deren Formeln R2 und R3 untereinander und zu R1 gleich oder verschieden sein können und jeweils die für R1 genannten bevorzugten Bedeutungen haben, darüber hinaus können R2 und R3 auch zusammen mit dem benachbarten Stickstoffatom einen 5- oder 6-gliedrigen hetsrocyclischen Ring, der noch ein weiteres Stickstoff-, Sauerstoff-und/oder ein Schwefelatom enthalten kann, bilden. Die Ausgangsstoffe III können in stöchiometrischer Menge, bezogen auf Ausgangsstoff II, oder in vorzugsweise bis zu 20-fachem Uberßchuß umgesetzt werden. Es können z.B. Ammoniak und die folgenden primären oder sekundären Amine als Ausgangsstoffe II verwendet werden: Methylamin, Diäthyl-, Nethylbenzyl-, Cyclohexylamin, Anilin, m-Trifluormethylanilin, 2-Amino-pyrimidln, Pyrrolidin, Morpholin, 2-Amino-triazin, 2-Amino-tiophen, 1,4-Oxazin, Piperazin.Preferred starting materials of the general formula III and accordingly preferred end products I are those in their formulas R2 and R3 with one another and may be identical to or different from R1 and in each case those preferred for R1 Have meanings, in addition, R2 and R3 can also be used together with the neighboring Nitrogen atom a 5- or 6-membered heterocyclic ring, which is still another May contain nitrogen, oxygen and / or a sulfur atom. The starting materials III can be in a stoichiometric amount, based on starting material II, or preferably in up to 20-fold excess can be implemented. For example, ammonia and the following primary or secondary amines are used as starting materials II: methylamine, Diethylamine, Nethylbenzylamine, Cyclohexylamine, aniline, m-trifluoromethylaniline, 2-amino-pyrimidine, Pyrrolidine, morpholine, 2-amino-triazine, 2-amino-thiophene, 1,4-oxazine, piperazine.
Die Reaktion wird bei einer Temperatur >50°C, in der Regel bei einer Temperatur zwischen 50 und 1500C, vorzugsweise zwischen 110 und 140°C, drucklos oder unter Druck, kontinuierlich oder diskontinuierlich durchgeführt. Zweckmäßig setzt man bei der Umsetzung schwache organische Säuren mit einer Dissoziationskonstante zwischen 1#10-4 und 1#10-5 zu, z.B. Alkancarbonsäuren wie Essigsäure oder Propionsäure; Benzoesäure, Glutarsäure, Adipin-Säure. Es werden im allgemeinen Mengen von 10 bis 50, vorsugsweise von 30 bis 50 Mol Säure, bezogen auf 1 Mol Ausgangsstoff III, angewendet.The reaction takes place at a temperature> 50 ° C, usually at a temperature between 50 and 1500C, preferably between 110 and 140 ° C, without pressure or carried out under pressure, continuously or batchwise. Appropriate you put in the implementation weak organic acids with a Dissociation constant between 1 # 10-4 and 1 # 10-5, e.g. alkanecarboxylic acids such as Acetic acid or propionic acid; Benzoic acid, glutaric acid, adipic acid. It will in general amounts from 10 to 50, preferably from 30 to 50 mol of acid, based on applied to 1 mole of starting material III.
Die Reaktion kann wie folgt durchgeftihrt werden: Ein Gemisch von Ausgangsstoff II und III, gegebenenfalls zusammen mit der Säure, wird während 0, 5 bis 10 Stunden bei Reaktionstemperatur gehalten.The reaction can be carried out as follows: A mixture of Starting material II and III, optionally together with the acid, is during 0, Maintained at reaction temperature for 5 to 10 hours.
Dann wird das Gemisch gekühlt, gegebenenfalls eingeengt und dann in Wasser gegeben. Der gebildete Endstoff wird nun in üblicher Weise, z. B. durch Filtration oder Extraktion, aus dem Gemisch abgetrennt.The mixture is then cooled, concentrated if necessary and then in Given water. The end product formed is now in the usual way, for. B. by filtration or extraction, separated from the mixture.
Die nach dem Verfahren herstellbaren Verbindungen sind wertvolle Zwischenprodukte für die Herstellung von Pflanzenschutzmitteln und Insekticiden.The compounds which can be prepared by the process are valuable intermediates for the production of pesticides and insecticides.
Die in den Beispielen genannten Teile bedeuten Gewichtsteile.The parts mentioned in the examples are parts by weight.
Beispiel 1 500 Teile α,ß-Dichlor-γ-hydroxy-N-cyclohexyl-crotonlactam löst Mn in 6 000 Teilen Eisessig, ftigt 7 000 Teile Pyrrolidin zu und erhitzt dann 2 Stunden auf 120°C. Nach dem Abkühlen gießt man das Gemisch in Wasser und filtriert den abgeschiedenen Endstoff. Man erhält 450 Teile (entspricht 90 % der Theorie) N-Cyclohexyl -α-pyrrolidino-maleinimid vom Fp. 128°C (aus Äther). Example 1 500 parts of α, β-dichloro-γ-hydroxy-N-cyclohexyl-crotone lactam dissolves Mn in 6,000 parts of glacial acetic acid, adds 7,000 parts of pyrrolidine and then heats 2 hours at 120 ° C. After cooling, the mixture is poured into water and filtered the separated end product. 450 parts are obtained (corresponds to 90% of theory) N-cyclohexyl -α-pyrrolidino-maleimide with a melting point of 128 ° C (from Ether).
Analyse: C14H20N2O2 (248,3) berechnet: C 67,72 % H 8,12 % N 11,28 % gefunden: C 67,55 % H 8,49 % N 11,38 %.Analysis: C14H20N2O2 (248.3) Calculated: C 67.72% H 8.12% N 11.28 % Found: C 67.55% H 8.49% N 11.38%.
Beispiel 2 500 Teile α,ß-Dichlor-γ-hydroxy-N(ß-indolyl)-äthyl-crotonlactam werden 2 Stunden mit 7 000 Teilen Pyrrolidin und 6 000 Teilen Eisessig auf 1900C erhitzt. Nach Aufarbeitung analog Beispiel 1 erhält man 360 Teile (entspricht 72 % der Theorie) N-(ß-Indolyl)-äthyl-α-pyrrolidino-maleinimid vom Fp. 2120C (aus Methylenchlorid). Example 2 500 parts of α, ß-dichloro-γ-hydroxy-N (ß-indolyl) -ethyl-crotonlactam are 2 hours with 7,000 parts of pyrrolidine and 6,000 parts of glacial acetic acid at 1900C heated. After working up as in Example 1, 360 parts are obtained (corresponds to 72 % of theory) N- (ß-indolyl) -ethyl-α-pyrrolidino-maleimide of melting point 2120C (from methylene chloride).
Analyse: C18H19N3O2 (309,4) berechnet: C 69,87 % H 6,19 % N 13,58 % gefunden: C 69,65 % H 6,43 % N 13,73 %.Analysis: C18H19N3O2 (309.4) Calculated: C 69.87% H 6.19% N 13.58 % Found: C 69.65% H 6.43% N 13.73%.
Beispiel 3 500 Teile α,ß-Dichlor-γ-hydroxy-N-benzyl-crotonlactam werden 2 Stunden mit 7 000 Teilen Pyrrolidin und 6 000 Teilen Eisessig auf 1200C erhitzt. Nach Aufarbeitung analog Beispiel 1 erhält man 450 Teile (entspricht 90 % der Theorie) N-=Benzyl-α-pyrrolidino-maleinimid vom Fp. 107°C. Example 3 500 parts of α, β-dichloro-γ-hydroxy-N-benzyl-croton lactam are 2 hours with 7,000 parts of pyrrolidine and 6,000 parts of glacial acetic acid at 1200C heated. After working up as in Example 1, 450 parts are obtained (corresponds to 90 % of theory) N- = Benzyl-α-pyrrolidino-maleimide with a melting point of 107 ° C.
Analyse: C15H16O2N2 (256,6) berechnet: C 70,21 % H 6,29 % N 10,92 % gefunden: C 70,58 % H 6,32 % N 10,92 f.Analysis: C15H16O2N2 (256.6) Calculated: C 70.21% H 6.29% N 10.92 % Found: C 70.58% H 6.32% N 10.92 f.
Beispiel 4 500 Teile e α,ß-Dichlor-γ-hydroxy-N-benzyl-crotonlactam werden 2 Stunden mit 7 000 Teilen Moipholin und 6 000 Teilen Eisessig auf 1200C erhitzt. Nach Aufarbeitung analog Beispiel 1 erhält man 425 Teile (entspricht 85 % der Theorie) N-Benzyl-α-morpholinomaleinimid vom Fp. 134°C. Example 4 500 parts of α, β-dichloro-γ-hydroxy-N-benzyl-crotone lactam are 2 hours with 7,000 parts of Moipholin and 6,000 parts of glacial acetic acid at 1200C heated. After working up as in Example 1, 425 parts (corresponds to 85 % of theory) N-benzyl-α-morpholinomaleimide with a melting point of 134 ° C.
Analyse: C15H16O3N2 (272,6) berechnet: C 66,09 % H 5,92 % N 10,28 % gefunden: C 65,87 % H 5,91 % N 10,27 .Analysis: C15H16O3N2 (272.6) Calculated: C 66.09% H 5.92% N 10.28 % Found: C 65.87% H 5.91% N 10.27.
Beispiel 5 500 Teile α,ß-Dichlor-γ-hydroxy-N-benzyl-crotonlactam werden 2 Stunden mit 7 000 Teilen Diäthylamin und 6 000 Teilen Eisessig auf 1200C erhitzt. Nach Aufarbeitung analog Beispiel 1 erhält man 470 Teile (entspricht 94 % der Theorie) N-Äthyl-α-diäthylamino-maleinimid vom Fp. 948C. Example 5 500 parts of α, β-dichloro-γ-hydroxy-N-benzyl-crotone lactam are 2 hours with 7,000 parts of diethylamine and 6,000 parts of glacial acetic acid at 1200C heated. After working up as in Example 1, 470 parts are obtained (corresponds to 94 % of theory) N-ethyl-α-diethylamino-maleimide of melting point 948C.
Analyse: C15H18O2N2 (258,3) berechnet: C 69,75 ffi H 7,02 % N 10,85 % gefunden: a 69,70 % H 6,74 % N 10,93 %.Analysis: C15H18O2N2 (258.3) Calculated: C 69.75 ffi H 7.02% N 10.85 % found: a 69.70%, H 6.74%, N 10.93%.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19681770041 DE1770041A1 (en) | 1968-03-23 | 1968-03-23 | Process for the preparation of alpha-amino-maleimides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19681770041 DE1770041A1 (en) | 1968-03-23 | 1968-03-23 | Process for the preparation of alpha-amino-maleimides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1770041A1 true DE1770041A1 (en) | 1971-09-16 |
Family
ID=5700371
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19681770041 Pending DE1770041A1 (en) | 1968-03-23 | 1968-03-23 | Process for the preparation of alpha-amino-maleimides |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1770041A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007039749A3 (en) * | 2005-10-06 | 2008-05-08 | Univ Aston | Antibacterial pyrrols |
-
1968
- 1968-03-23 DE DE19681770041 patent/DE1770041A1/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007039749A3 (en) * | 2005-10-06 | 2008-05-08 | Univ Aston | Antibacterial pyrrols |
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