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DD250318A1 - PROCESS FOR PREPARING NEW 3,6-DIHYDRO-2H-THIOPYRANE-2-CARBONATEAMIDE AMIDES - Google Patents

PROCESS FOR PREPARING NEW 3,6-DIHYDRO-2H-THIOPYRANE-2-CARBONATEAMIDE AMIDES Download PDF

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Publication number
DD250318A1
DD250318A1 DD28970586A DD28970586A DD250318A1 DD 250318 A1 DD250318 A1 DD 250318A1 DD 28970586 A DD28970586 A DD 28970586A DD 28970586 A DD28970586 A DD 28970586A DD 250318 A1 DD250318 A1 DD 250318A1
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DD
German Democratic Republic
Prior art keywords
dihydro
chem
formula
methylthio
amides
Prior art date
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DD28970586A
Other languages
German (de)
Inventor
Hans W Modrow
Wilfried Thiel
Ernst-Adolf Jauer
Roland Mayer
Original Assignee
Bitterfeld Chemie
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 Bitterfeld Chemie filed Critical Bitterfeld Chemie
Priority to DD28970586A priority Critical patent/DD250318A1/en
Publication of DD250318A1 publication Critical patent/DD250318A1/en

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Abstract

Die Erfindung betrifft ein Verfahren zur Herstellung von 3,6-Dihydro-2H-thiopyran-2-carbonsaeureamiden, die als Zwischenprodukte von Bedeutung sind. In einem einfachen Verfahren werden 1,1-Dithiooxalsaeureesteramide mit 2,3-Dimethylbutadien, gegebenenfalls in Anwesenheit eines Loesungsmittels zu 3,6-Dihydro-2H-thiopyran-2-carbonsaeureamiden der Formel II, in der XNH2, NHR, NR2 und RAlkyl, Aralkyl und Aryl bedeuten, cyclisiert. Formel IIThe invention relates to a process for the preparation of 3,6-dihydro-2H-thiopyran-2-carbonsaeureamiden, which are of importance as intermediates. In a simple process, 1,1-dithiooxalic acid ester amides with 2,3-dimethylbutadiene, optionally in the presence of a solvent, are converted to 3,6-dihydro-2H-thiopyran-2-carboxylic acid amides of the formula II in which XNH 2, NHR, NR 2 and R alkyl, Aralkyl and aryl, cyclized. Formula II

Description

in der X und R die oben genannte Bedeutung haben, umgesetzt werden. Als Lösungsmittel eignen sich infolge guter Löslichkeit der Verbindungen der Formel I besonders Dichlormethan und Trichlormethan. Die Umsetzung läuft bei Temperaturen von 0 bis 1000C mit quantitativer Ausbeute ab.in which X and R have the abovementioned meaning, be implemented. As solvents, owing to good solubility of the compounds of the formula I, dichloromethane and trichloromethane are particularly suitable. The reaction proceeds at temperatures from 0 to 100 0 C with quantitative yield.

Ausführungsbeispieleembodiments Beispiel 1example 1

4,5-Dimethyl-2-methylthio-3,6-dihydro-2H-thiopyran-2-carbonsäureamid4,5-dimethyl-2-methylthio-3,6-dihydro-2H-thiopyran-2-carboxamide

1,35g (0,01 Mol)1,1-Dithiooxalsäuremethylester-amidund 1,6,5 g (0,02 Mol) 2,3-Dimethylbutadien werden ca. 4 Stunden in 20 ml Dichlormethan bis zur Entfärbung erhitzt. Danach wird das Lösungsmittel im Vakuum entfernt. Das in quantitativer Ausbeute als Rohprodukt anfallende Thiopyran wird in wenig Ethanol oder Ligroin umkristallisiert. Man erhält 1,5g (69% derTheorie) weiße Nadeln, F. 95 bis 980C.1.35 g (0.01 mol) of 1,1-dithiooxalic acid methyl ester amide and 1.6.5 g (0.02 mol) of 2,3-dimethylbutadiene are heated for about 4 hours in 20 ml of dichloromethane until discolored. Thereafter, the solvent is removed in vacuo. The obtained in quantitative yield as a crude product thiopyran is recrystallized in a little ethanol or ligroin. This gives 1.5 g (69% derTheorie) of white needles, mp 95 to 98 0 C.

Beispiel 2 bis 9Example 2 to 9

Es wird analog Beispiel 1 verfahren. Die erhaltenen Verbindungen der Formel Il sind in der Tabelle aufgeführt.The procedure is analogous to Example 1. The resulting compounds of formula II are listed in the table.

Tabelle Weitere Verbindungen der Formel Il Beispiel R XTable Further compounds of the formula II Example R X

Schmp. in °C/Umkrist. in Ausb. in % d. Th.M.p. in ° C / Umkrist. in training in% d. Th.

Et CH2C6H5Et CH2C6H5

NH2 NH2 NH 2 NH 2

80-82/EtOH 117-118/EtOH80-82 / EtOH 117-118 / EtOH

71 8071 80

Meme

NH-< O NH- < O

139-140/Ligroin139-140 / ligroin

8282

Meme

Meme

Meme

Meme

Meme

NHNH

88-90/EtOH88-90 / EtOH

85-86/EtOH85-86 / EtOH

145-147/EtOH145-147 / EtOH

140-142/EtOH140-142 / EtOH

140-142/EtOH140-142 / EtOH

8585

7474

8080

6868

7676

Formelblatt 2940 WP C 0? D/289 705 4Formula sheet 2940 WP C 0? D / 289 705 4

3? ο r. m e 1 II3? ο r. m e 1 II

r'-Jr 'J

Claims (1)

Verfahren zur Herstellung neuer 3,6-Dihydro-2H-thiopyran-2-carbonsäureamide der FormelProcess for the preparation of novel 3,6-dihydro-2H-thiopyran-2-carboxamides of the formula Meme (ID,(ID, in der X= NH2, NHR, NR2 und R = Alkyl; Äralkyi,Aryl bedeuten, gekennzeichnet dadurch, daß 1,1-Dithiooxalsäureesteramide der Formelin which X = NH 2 , NHR, NR 2 and R = alkyl; Äralkyi, aryl, characterized in that 1,1-Dithiooxalsäureamide the formula (D(D RS ORS O in der R und X die oben genannte Bedeutung haben, mit 2,3-Dimethylbutadien, gegebenenfalls in Gegenwart eines Lösungsmittels, umgesetzt werden.in which R and X have the abovementioned meaning, be reacted with 2,3-dimethylbutadiene, if appropriate in the presence of a solvent. Hierzu 1 Seite FormelnFor this 1 page formulas Anwendungsgebiet der ErfindungField of application of the invention Die Erfindung betrifft ein Verfahren zur Herstellung neuer S^-Diriydro^H-thiopyran^-carbonsäureamide, die als Zwischenprodukte von Interesse sind.The invention relates to a process for the preparation of novel S ^ -Diriydro ^ H-thiopyran ^ -carboxamides, which are of interest as intermediates. Charakteristik der bekannten technischen LösungenCharacteristic of the known technical solutions 3,6-Dihydro-2H-thiopyrane sind durch Diels-Alder-Cycloadditionsreaktion von Thiocarbonylverbindungen mit Butadienderivaten darstellbar. Eine hohe Dienophilie zeigen aber nur acceptorsubstituierte Thiocarbonylsystenne. So konnten bislang nur2-Methylthio-2-cyano- (J. Chem. Soc. D'1971,1411; J. Chem. Soc. Perkin 11975,180), substituierte 2-Amino-2-cyano-(Tetrahedron Letters 1977, 2139; Chem. Ber. 112 [1979] 1867), 2-Methylthio-2-methylthio-thiocarbonyl-(Liebigs Ann. Chem. 1980,1482), 2-Methoxy-2-methoxythiocarbonyl- (Liebigs Ann. Chem. 1980,1665), a-Fluor^-trifluormethyl- und 2-Alkylthio-2-trifluormethyl-(J. Org. Chem. 30 [1965] 1390) sowie 2-Methylthio-2-alkoxycarbonyl- (J. Org. Chem. 1980,2601) -S^-dih thiopyraneausThionooxalsäurederivaten dargestellt werden.3,6-Dihydro-2H-thiopyrans can be prepared by Diels-Alder cycloaddition reaction of thiocarbonyl compounds with butadiene derivatives. However, high dienophilia only show acceptor-substituted thiocarbonylsystenee. So far, only 2-methylthio-2-cyano- (J. Chem. Soc. D'1971, 1411, J. Chem. Soc.Perkin 11975, 180), substituted 2-amino-2-cyano- (Tetrahedron Letters 1977, Chem. Ber. 112 [1979] 1867), 2-methylthio-2-methylthio-thiocarbonyl (Liebigs Ann. Chem. 1980, 1482), 2-methoxy-2-methoxythiocarbonyl (Liebigs Ann. Chem. 1665), α-fluoro-trifluoromethyl and 2-alkylthio-2-trifluoromethyl (J. Org. Chem. 30 [1965] 1390) and 2-methylthio-2-alkoxycarbonyl (J. Org. Chem. 2601) -Si-thiopyranes of thionooxalic acid derivatives. Ziel der ErfindungObject of the invention Ziel der Erfindung ist es, bisher unbekannte 3,6-Dihydro-2H-thiopyrancarbonsäureamide durch ein eifaches Verfahren herzustellen.The aim of the invention is to produce hitherto unknown 3,6-dihydro-2H-thiopyrancarboxamides by a simple method. Darlegung des Wesens der ErfindungExplanation of the essence of the invention Aufgabe der Erfindung ist es, S^-Dihydro^H-thiopyrancarbonsäureamide aus geeigneten Verfahren zu synthetisieren. Erfindungsgemäß wird die Aufgabe dadurch gelöst, daß die 1,1-Dithiooxalsäureester-amide der FormelThe object of the invention is to synthesize S ^ -Dihydro ^ H-thiopyrancarboxamides from suitable processes. According to the invention the object is achieved in that the 1,1-Dithiooxalsäureester-amides of the formula RS ORS O in der X= NH2, NHR, NR2 und R = Alkyl, Aralkyl und Aryl bedeuten, mit 2,3-Dimethylbutadien, gegebenenfalls unter Anwendung eines Lösungsmittels, zu S.e-Dihydro^H-thiopyran^-carbonsäureamiden der Formelin which X = NH 2 , NHR, NR 2 and R = alkyl, aralkyl and aryl, with 2,3-dimethylbutadiene, optionally with the use of a solvent, to give Se-dihydro-H-thiopyrancarboxylic acid amides of the formula
DD28970586A 1986-04-29 1986-04-29 PROCESS FOR PREPARING NEW 3,6-DIHYDRO-2H-THIOPYRANE-2-CARBONATEAMIDE AMIDES DD250318A1 (en)

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DD28970586A DD250318A1 (en) 1986-04-29 1986-04-29 PROCESS FOR PREPARING NEW 3,6-DIHYDRO-2H-THIOPYRANE-2-CARBONATEAMIDE AMIDES

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DD28970586A DD250318A1 (en) 1986-04-29 1986-04-29 PROCESS FOR PREPARING NEW 3,6-DIHYDRO-2H-THIOPYRANE-2-CARBONATEAMIDE AMIDES

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0326297A1 (en) * 1988-01-21 1989-08-02 May & Baker Limited Thioformamide derivatives

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0326297A1 (en) * 1988-01-21 1989-08-02 May & Baker Limited Thioformamide derivatives

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