Reactions of β-imino-nitriles and -esters with carbon disulphide. A new synthesis and some reactions of 2-cyano-3-imino-dithiocarboxylic acids

Muraoka, Motomu; Yamamoto, Tatsuo; Yamaguchi, Sadaki; TONOSAKI, F.; Takeshima, Tatsuo; Fukada, Naoaki

doi:10.1039/p19770001273

Cited by 24 publications

(4 citation statements)

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“… Literature methods for the formation of carbamic carboxylic trithioanhydride rings: a) with CS 2 and phenylisothiocyanate;25,26 b) 4‐arylthiazolidene‐2,5‐dithiones27 and c) 1,3‐thiazine‐2,6‐dithiones;28 d) from diaminobenzene and CS 2 29…”

Section: Resultsmentioning

confidence: 99%

Contrasting Reactivity of CS₂ with Cyclic vs. Acyclic Amidines

et al. 2015

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The interaction between carbon dioxide (CO2) and amidines such as 1,8‐diazabicyclo[5.4.0]undecane (DBU) has been extensively studied, but the reaction of isovalent CS2 with such bases has been largely ignored, apart from a single crystallography report. Acyclic acetamidines are cleaved by CS2 at room temperature to give an isothiocyanate and a thioacetamide. Because the pathway to that cleavage involves a rotation that is difficult for cyclic amidines, the reaction of CS2 with cyclic amidines produces an entirely different product: a cyclic carbamic carboxylic trithioanhydride structure. The path to that product involves sp3 C‐H activation leading to the formation of a new C–C bond at a carbon α to the central carbon of the amidine group. Alkylation and ring‐opening of the cyclic carbamic carboxylic trithioanhydride has also been demonstrated under ambient conditions.

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Section: Resultsmentioning

confidence: 99%

Contrasting Reactivity of CS₂ with Cyclic vs. Acyclic Amidines

et al. 2015

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“…12, 2015 3-amino-2-cyanodithiocinnamic acid and its homologous dithioacids bearing an alkyl substituent on the aromatic ring. 3 Reactions of 3-amino-2,3-unsaturated alicyclic dithiocarboxylic acids, 3-amino-2-cyanodithiocrotonic and -2-cyanodithiocinnamic acids with carbonyl compounds, carbon disulfide, or phenyl isothiocyanate to give 1,3-thiazine-6-thiones 2,4,[5][6][7] or -2,6-dithiones 4,8,9 have been reported by Takeshima, Muraoka, and their co-workers. Unstable 2-thioxodithiocarboxylic acids generated during the procedure of reaction mixture were oxidized by air to give 1,2-dithiol-3-thiones.…”

Section: Introductionmentioning

confidence: 94%

“…9 Subsequently 1,2,4-trithiols were formed by the oxidation of stable 2-imino-1-dithiocarboxylic acids with I2. 2,3 The 1,3-dithietanes 2,3 were produced by the intramolecular elimination of H2S with DCC or upon heating to about 70 °С. The 1,3benzodithiols 2,3,6 were produced by the reaction of these dithiocarboxylic acids with picryl chloride.…”

Section: Introductionmentioning

confidence: 99%

Novel Synthesis of 1,2-Dihydro-4H-3,1-benzoxazine-4-thiones by the Reaction of Newsynthesized Methyl Dithioanthranilate Hydrobromide with Carbonyl Compounds and the Formation of Another New Class of 1,2-Dihydro-4H-3,1-benzothiazine-4-thiones from the Same Reactants in the Presence of Excess Sodium Hydrogensulfide

Yamamoto¹,

Muraoka²

2015

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Methyl dithioanthranilate hydrobromide (6) was synthesized by the deprotection of Z-protected methyl dithioanthranilate (5) which was obtained by treatment of Z-protected methylthioiminium iodide 4 with H2S. The 1,2-dihydro-4H-3,1-benzoxazine-4-thiones 10a-m were first synthesized by the reaction of methyl dithioanthranilate hydrobromide (6) with each aldehyde or ketone. Formaldehyde, in this reaction, gave N-(methylthio)methyl-4H-3,1benzoxazine-4-thione (11). Another new class of 1,2-dihydro-4H-3,1benzothiazine-4-thiones 12a-e were synthesized from the same reactants in the presence of two equivalents of sodium hydrogensulfide. Pyrazole derivatives 6 were also obtained when the iminodithiocarboxylic acids were treated with hydrazine. In addition to the above-mentioned reactions of the dithioacids to form various heterocyclic compounds, addition reactions of 2-aminocyclopent-1-ene-1-dithiocarboxylic acid to strongly electrophilic olefins to form stable dithioesters were also reported. 10 No further studies regarding the synthesis of heterocyclic compounds using 3-amino-2,3-unsaturated alicyclic dithiocarboxylic acids or 3-amino-2-cyanodithiocinnamic acids have thus been reported for over 36 years until we began to study the synthesis and reactions of methyl dithioanthranilate. Dithioanthranilic acid is considered to be a special case of 3-amino-2,3-unsaturated dithiocarboxylic acids, and is expected to give rise to some new types of heterocyclic compounds fused to benzene ring by allowing it to react with electrophilic reagents such as carbonyl compounds. Jourdan and co-workers 11 reported the formation of sodium dithioanthranilate by the reaction of 2-aminobenzotrifluoride with sodium sulfide in boiling dimethyl sulfoxide, but they isolated neither free dithioanthranilic acid nor any of its esters. The synthesis of the regioisomer of methyl dithioanthranilate, methyl 4-aminodithiobenzoate, which is utilized as a precursor compound for dyeing keratin fibers, was reported by Leon and co-worker. 12 Mckinnon and co-workers reported the synthesis of N-methyl derivative of methyl dithioanthranilate. 13 RESULTS AND DISCUSSION We are strongly interested in the physical and chemical properties and reactions of dithioanthranilic acid and its ester with electrophiles. These do not seem to be any way to introduce dithiocarboxyl group to the 2328

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“…Further, the authors tried to synthesize various new types of heterocyclic and fused heterocyclic compounds by the reactions of 1,3-thiazine-2,6-dithiones [7][8][9] with many types of nucleophiles and found to be obtained fruitful results. Thus, in the reaction with 1, -diaminoalkanes, the 1,3-thiazine-2,6-dithiones produced imidazo [ In contrast, the same 1,3-thiazine-2,6-dithiones yielded pyrimidobenzimidazole-4-thiones in the reaction with o-phenylenediamine.…”

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confidence: 99%