86796-01-2Relevant academic research and scientific papers
Chemistry of 2,4-Diaminothiopyranylium Iodides Syntheses of α,β,γ,δ-Unsaturated Thiocarboxamides
Schweiger, Klaus
, p. 317 - 332 (2007/10/02)
Aminolyses of 4-dialkylamino- and 4-alkylamino-2-methylthiothiopyranyliden iodids 2 resp. under various reaction conditions leads to assymmetrically or symmetrically substituted 2,4-bisamino- or 2,4-bisdialkylamino- and 2-alkylamino-4-dialkylamino- or 2-dialkylamino-4-alkylamino- or 2-amino-4-dialkylaminodihydrothiopyranylium iodides 3, 4, 5, 6 resp.On treatment with alkali 4-alkylamino- and 4-dialkylamino-2-alkylaminothiopyranylium iodides 3, 4 are hydrolysed to the 2-alkylimino-2H-thiopyranes 7. 4-Alkylamino-2-dialkylaminothiopyranylium iodides 5 react with alkali to give three products: the two stereoisomeres 2-dialkylamino-4-alkylimino-4H-thiopyranes 9 A,B and the N,N-substituted α,β,γ,δ-unsaturated thiocarboxamide 10.The hydrolysis of 2,4-bisdialkylaminothiopyranylium iodide 6a leads to the 2-dialkylamino-4H-thiopyran-4-one 11a, the 4-dialkylamino-2H-thiopyrane-2-one 12 and the N,N-substituted unsaturated thiocarboxamide 10d. α,β,γ,δ-unsaturated thiocarboxamides 10 a-c are formed by the reaction of 2-amino-4-dialkylaminothiopyranylium iodides 3 a-c with diluted alkali.By heating with acids 10 a-c are cyclisized to the 2-aminothiopyranylium derivates 3. - Keywords: Alkylaminothiopyranylium iodides; 2-Alkylimino-2H-thiopyranes; 4-Alkylimino-4H-thiopyranes; 2,4-Diaminothiopyranylium iodides; Thiocarboxamides, α,β,γ,δ-unsaturated
Syntheses of 1-Substituted 4-Amino-2(1H)-pyridinethione by Dimroth-Reaction of 2,4-Diaminothiopyranylium Halogenides
Schweiger, Klaus
, p. 581 - 592 (2007/10/02)
4-Amino-2-alkylimino-2H-thiopyranes (5) and 4-amino-2-alkylaminothiopyranylium halogenides (4) resp. on heating in refluxing D M F A are rearranged in the presence of Na-ethylate to 1-alkyl-4-aminodihydro-2(1H)-pyridinethiones (2).Also 2-methylthiothiopyranylidenammonium iodides (6) and 2-methylthio-4H-thiopyrane-4-one (7) can be transformed into 1-substituted 2(1H)-pyridinethiones (2) by heating in prim. amines.On treatment with alkali, 4-dimethylaminothiopyranylium iodide (4a) is transformed into its base 5a and hydrolyzed to 8. 5a and 8 are rearranged to the pyridinethiones 2a and the tautomers 9 A, B.The structure of the rearranged pyridinethiones 2 was proved by the 1-phenylderivate 2a.Thus 4-methyl-3-penten-2-on reacts with phenylthiourea via the phenylimino-1,3-thiazine (14) to give 3-phenyl-2(1H)pyridinethione (15). 15 is transformed by the methylpyrimidine-pyridine-rearrangement to the 1-phenylpyridinethione 2a.The mechanism of the Dimroth-reaction of 2-alkylimino-2H-thiopyranes (5) and the stereochemistry of the 1-benzyl-6-phenyl-2(1H)-pyridinethiones 2 are discussed. - Keywords: Conformational analysis of benzyl phenyl 2(1H) pyridinethiones; Dimroth-reaction; Keto-enol-tautomerism of 1-substituted 4-hydroxy-2(1H)-pyridinethiones; 2-Methylthiothiopyranylidenammonium iodides and 2-methylthio-4H-thiopyrane-4-one, reaction with primary amines
