DD158103A1 - PROCESS FOR THE PREPARATION OF 1 [PYRIDYL- (2) AND 1 [CHINOLYL (2)] - 1 ACYL-2-BITEUBSTITUTED ETHENEES - Google Patents
PROCESS FOR THE PREPARATION OF 1 [PYRIDYL- (2) AND 1 [CHINOLYL (2)] - 1 ACYL-2-BITEUBSTITUTED ETHENEES Download PDFInfo
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- DD158103A1 DD158103A1 DD22920981A DD22920981A DD158103A1 DD 158103 A1 DD158103 A1 DD 158103A1 DD 22920981 A DD22920981 A DD 22920981A DD 22920981 A DD22920981 A DD 22920981A DD 158103 A1 DD158103 A1 DD 158103A1
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- acyl
- pyridyl
- ethenes
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- Pyridine Compounds (AREA)
Abstract
Die Erfindung betrifft ein Verfahren zur Herstellung von 1-(Pyridyl-(2)- und 1-(Chinolyl-(2)-1-acyl-2-bissubstituiierten-ethenen durch Umsetzung von Acylpicolinen beziehungsweise Acylchinaldinen mit Phenylisothiocyanat in aprotischen dipolaren Loesungsmitteln und unter Verwendung von Natriumhydrid als Base. Das intermediaer gebildete Salz wird mit Alkylhalogeniden oder anderen halogenaktiven Verbindungen alkyliert. Es ist bekannt, dass Pyridin- und Chinolinderivate als biologisch aktive Substanzen verwendet werden.The invention relates to a process for preparing 1- (pyridyl- (2) - and 1- (quinolyl- (2) -1-acyl-2-bis-substituted-ethenes by reacting acylpicolines or acylchinaldines with phenylisothiocyanate in aprotic dipolar solvents and under Use of Sodium Hydride as Base The intermediately formed salt is alkylated with alkyl halides or other halogenated compounds It is known that pyridine and quinoline derivatives are used as biologically active substances.
Description
Tite1 der Erfindung . . · , Tite1 he d e rf in dung. , ·,
Verfahren zur Herstellung von 1- [Pyridyl-(2)] - und 1- [Chinolyl-(2)]-1-acyl-ethenenProcess for the preparation of 1- [pyridyl- (2)] - and 1- [quinolyl- (2)] - 1-acyl-ethenes
Anwendungsgebiet der ErfindungField of application of the invention
O " :—O " : -
Die Erfindung "betrifft ein Verfahren zur Herstellung von substituierten 1- [Pyridyl-(2)] - und 1-[Chinolyl-(2)]-1-The invention "relates to a process for the preparation of substituted 1- [pyridyl- (2)] - and 1- [quinolyl- (2)] - 1-
• Ί• Ί
acyl-ethenen der allgemeinen Formeln I.und II, in denen Racyl ethenes of the general formulas I. and II, in which R
2 3 eine Alkyl-, Aryl- oder Hetarylgruppe, R und r gleich oder verschieden sind und eine Alkylthio- oder eine Arylaminogruppe bedeuten.2 3 is an alkyl, aryl or hetaryl group, R and r are identical or different and denote an alkylthio or an arylamino group.
Es ist bekannt, daß Pyridin- und Chinolinderivate als biologisch aktive Substanzen verwendet werden.It is known that pyridine and quinoline derivatives are used as biologically active substances.
'Charakteristik der bekannten technischen Lösungen ' Characteristic of the known technical solutions
Derartige substituierte 1-[Pyridyl-(2)] - und 1-[Chinolyl-(2)]-1-acyl-ethene sind'bisher noch nicht beschrieben worden. Bekannt ist, daß unter basischen Bedingungen Additionen von methylenaktiven Verbindungen an Heterokumulenen ablaufen. Es war jedoch aufgrund der bisherigen Erkenntnis nicht zu er-> warten, daß derartige Additionen von Carbanionen der Acylpicoline bzw„ -chinaldine an Phenylisothiocyanate gelingen, da wegen der vorliegenden Tautomerieverhältnisse auch das Sauerstoff- bzw.' das Stickstoffatom als nucleophiles Zentrum fungieren kann.Such substituted 1- [pyridyl- (2)] - and 1- [quinolyl- (2)] - 1-acyl-ethenes have not been described before. It is known that under basic conditions, additions of methylene-active compounds to heterocumulenes take place. However, it was not to be expected on the basis of the previous finding that such additions of carbanions of the acylpicolines or "-quinaldines to phenyl isothiocyanates succeed, since, owing to the present tautomerization ratios, the oxygen and / or the nitrogen atom can act as a nucleophilic center.
' Ziel der Erfindung ' Object of the invention
Das Ziel der Erfindung ist die Herstellung dieser neuen Verbindungen. ·The aim of the invention is the preparation of these new compounds. ·
^P- ««··& ν* &· W «J* ^^ P- «« ·· & ν * & · W «J * ^
Der Erfindung liegt die Aufgabe zugrunde, nach einem einfachen Verfahren substituierte 1-[Pyridyl-(2)]- bzw, 1-[Chinolyl-(2)]-1-acyl-ethene herzustellen. Erfindungsgemäß v/erden substituierte .1— [Pyridyl-(2 )~] -1-acyl-ethene und 1-[Chinolyl-(2)] -1-acyl-ethene der allgemeinen Formel I bzw. II hergestellt durch Umsetzung von Acylpicolinen bzw. Acylchinaldinen der allgemeinen Formel III, in der R die gleiche Bedeutung wie in den Formeln I bzw, II hat, mit Phenylisothiocyanat in einem aprotisch dipolaren lösungsmittel, vorzugsweise Dimethylformamid, und Hatriumhydrid als Base bei O0C bis Raumtemperatur und nachfolgende Alkylierung mittels Alky!halogeniden oder <**- Halogencarbonylverbindungen.'The invention is based on the object by a simple process substituted 1- [pyridyl (2)] -, 1- [quinolyl (2)] - 1-acyl-ethene produce. Substituted .1- [pyridyl- (2 ) -] -1-acyl-ethenes and 1- [quinolyl- (2)] -1-acyl-ethenes of general formula I or II are prepared according to the invention by reacting acylpicolines or Acylchinaldinen of the general formula III, in which R has the same meaning as in the formulas I or, II, with phenyl isothiocyanate in an aprotic dipolar solvent, preferably dimethylformamide, and sodium hydride as base at 0 0 C to room temperature and subsequent alkylation by means of Alky ! halides or <** - halocarbonyl compounds.
Das erfindungsgemäße Verfahren zur Herstellung der erfindungsgemäßen Verbindungen wird durch die Gleichung 1 veranschaulicht.The process according to the invention for the preparation of the compounds according to the invention is illustrated by equation 1.
Als Alkyliarungsmittel eignen sich z. B. Methyliodid, Brom- und Chloressigsäurederivate, Phenacylbromide, Chloracetonitril sowie p-Uitrobenzylbromid.Suitable alkylating agents are, for. As methyl iodide, bromine and chloroacetic acid derivatives, phenacyl bromides, chloroacetonitrile and p-Uitrobenzylbromid.
.Die Acylpicoline und Acylchinaldine lassen sich durch Esterkondensation mit <X--Picolin bzw. Chinaldin nach bekannten Verfahren herstellen..The Acylpicoline and Acylchinaldine can be prepared by ester condensation with <X - picoline or quinaldine by known methods.
Nach dem erfindungsgemäßen Verfahren sind beispielsweise die Verbindungen der Tabelle 1 und 2 darstellbar.By the method according to the invention, for example, the compounds of Table 1 and 2 can be represented.
Bei_sp_iel_1__:Example 1__:
2-Anilino-i- [furoyl-(2)] -2-methylthio-i - [pyridyl-(2)]-ethen2-Anilino-i- [furoyl- (2)] -2-methylthio-i - [pyridyl (2)] - ethene
0,05 Mol Puroyl-2-picolin wird in 100 ml Dimethylformamid gelöst und unter Eiskühlung werden 0,05 Mol Natriumhydrid eingetragen . Man rührt eine Stunde bei Raumtemperatur und tropft dann bei 8-10 0C das Phenylisothiocyanat ( 0,05 Mol ) zu· Nach zweistündigem Rühren v/erden o,05 Mol Hethyliodid zugetropft. . 0.05 mol of puroyl-2-picoline is dissolved in 100 ml of dimethylformamide and under ice-cooling, 0.05 mol of sodium hydride are added. The mixture is stirred for one hour at room temperature and then added dropwise at 8-10 0 C, the phenylisothiocyanate (0.05 mol) · After two hours of stirring, v / o ground, 05 mol Hethyliodid added dropwise. ,
Nach 4 Stunden gießt man in Eis, saugt das Produkt ab und kristallisiert aus Ethanol um. Der Schmelzpunkt der Verbindung ist 129 - 130 °C und man erhält sie in 49 % iger Ausbeute. .After 4 hours, it is poured into ice, the product is filtered off with suction and recrystallized from ethanol. The melting point of the compound is 129-130 ° C and they are obtained in 49 % yield. ,
Be,is£iel_2__: .Be, iel_2__:.
2-Anilino-1-isobutyryl-2-(4-nitrobenzylthio)-1- [pyridyl (2)]-ethen2-Anilino-1-isobutyryl-2- (4-nitrobenzylthio) -1- [pyridyl (2)] - ethene
0,01 Mol Isobutyrylpicolin löst man in 80 ml Dirnethylformamid und versetzt unter Eiskühlung mit 0,01 Mol Natriumhydrid. Man tropft 0,01 Mol Phenylisothiocyanat hinzu und alkyliert mit p-Nitrobenzylbromid. Nach Gießen in Eis isoliert man in 53. % Ausbeute die Verbindung, die bei 131 - 132 0C schmilzt.0.01 mol of isobutyrylpicoline is dissolved in 80 ml of dimethylformamide and mixed with 0.01 mol of sodium hydride while cooling with ice. 0.01 mol of phenyl isothiocyanate is added dropwise and alkylated with p-nitrobenzyl bromide. After pouring in ice is isolated in 53% yield the compound at 131 - 132 0 C melts.
Be isp_i £l_3_:Be isp_i l_3_:
2-Anilino-i- [chinolyl-(2)]-2-ethoxycarbony!methylthio-1-isobutyryl-ethen2-Anilino-i- [quinolyl- (2)] - 2-ethoxycarbonylthio-1-isobutyryl-ethene
'0,05 Mol Isobutyrylchinaldin v/erden in 100 ml abs. DMP unter Eiskühl.ung portionsweise mit 0,05 Mol Natriumhydrid versetzt.0.05 mol of isobutyrylchinaldine in 100 ml of abs. DMP under ice cooling. Added portionwise with 0.05 mol of sodium hydride.
Phenylisothiocyanat und Bromessigsäureethylester werden zugetropft. Man hydrolisiert und isoliert die Verbindung mit einem Schmelzpunkt von 102 - 103 0C in 42 % Ausbeute.Phenylisothiocyanate and ethyl bromoacetate are added dropwise. It is hydrolyzed and the compound is isolated with a melting point of 102 - 103 0 C in 42 % yield.
Tabelle 1 :Table 1 :
SRSR
NH PhNH Ph
Schmp.(°C) Ausb.(%)M.p. (° C) yield (%)
Tabelle 2 :Table 2:
NH PhNH Ph
Schmp. ( C) Ausb.(%)M.p. (C) yield (%)
CH, CH-CH, CH-
C6H5 C 6 H 5
CH3 CH2CNCH 3 CH 2 CN
COoCoHr-COoCoHr-
c. c. J.c. c. J.
CH2CO2C2H5 CH 2 CO 2 C 2 H 5
143 -145143 -145
175 -178175-178
100 -103100-103
118 -119118-119
51 38 40 5851 38 40 58
ί, m ί, m
f/ %. si f / %. si
Allgemeine FormelnGeneral formulas
— C = C I C- C = C I C
Gleichung 1Equation 1
NaH/ DMF PhNCS NaH / DMF PhNCS
R2HaIR 2 shark
IlIl
S RS R
-C =C-C = C
NHPhNHPh
IIIIII
Claims (2)
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DD22920981A DD158103A1 (en) | 1981-04-14 | 1981-04-14 | PROCESS FOR THE PREPARATION OF 1 [PYRIDYL- (2) AND 1 [CHINOLYL (2)] - 1 ACYL-2-BITEUBSTITUTED ETHENEES |
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DD22920981A DD158103A1 (en) | 1981-04-14 | 1981-04-14 | PROCESS FOR THE PREPARATION OF 1 [PYRIDYL- (2) AND 1 [CHINOLYL (2)] - 1 ACYL-2-BITEUBSTITUTED ETHENEES |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN103601677A (en) * | 2013-11-19 | 2014-02-26 | 清华大学 | Preparation method of 2-alkylsulfenylquinoline derivative |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103601677A (en) * | 2013-11-19 | 2014-02-26 | 清华大学 | Preparation method of 2-alkylsulfenylquinoline derivative |
CN103601677B (en) * | 2013-11-19 | 2015-11-18 | 清华大学 | Prepare the method for 2-alkylthio quinoline |
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