Synthese von 4,4‐disubstituierten 1,3‐Thiazol‐5(4<i>H</i>)‐thionen

Jenny, C.; Heimgartner, Heinz

doi:10.1002/hlca.19860690217

Cited by 50 publications

(17 citation statements)

References 44 publications

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“…In addition to 8a and 9a, 22 mg (7%) of 4,4-dimethyl-2-phenyl-1,3-thiazol-5(4H)-one (5a) were isolated (cf. [13]). Yellow oil.…”

Section: 2mentioning

confidence: 93%

Reaction of 1,3-Thiazole-5(4H)-thiones with 1,2-Epoxycycloalkanes: Formation of Spirocyclic 1,3-Oxathiolanes

Blagoev¹,

Linden²,

Heimgartner³

1999

HCA

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Treatment of solutions of 1,3‐thiazole‐5(4H)‐thiones 1 in CH2Cl2 at room temperature with BF3⋅Et2O and 1,2‐epoxycyclohexane (7‐oxabicyclo[4.1.0]heptane; 2a) or 1,2‐epoxycyclopentane (6‐oxabicyclo[3.1.0]hexane; 2b) yielded mixtures of diastereoisomeric spirocyclic 1,3‐oxathiolanes (3/4 and 8/9, respectively). In addition, the corresponding 1,3‐dithiolane 6 was formed as a minor product in the reaction of 4,4‐dimethyl‐2‐phenyl‐1,3‐thiazole‐5(4H)‐thione (1a) with 2a. The structures of the different types of products have been established by X‐ray crystal‐structure analysis. An ionic two‐step mechanism via nucleophilic ring‐opening of the complexed oxirane by the attack of the thiocarbonyl S‐atom is proposed. This proposal is supported by the formation of the propellane 10 with a Wagner‐Meerwein rearrangement as the key step.

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“…In addition to 8a and 9a, 22 mg (7%) of 4,4-dimethyl-2-phenyl-1,3-thiazol-5(4H)-one (5a) were isolated (cf. [13]). Yellow oil.…”

Section: 2mentioning

confidence: 93%

Reaction of 1,3-Thiazole-5(4H)-thiones with 1,2-Epoxycycloalkanes: Formation of Spirocyclic 1,3-Oxathiolanes

Blagoev¹,

Linden²,

Heimgartner³

1999

HCA

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“…We recognize that this mechanism is speculative but note that similar analogous sulfur products have been documented in the reaction of di-amides with Lawesson's reagent. [38][39][40] All new compounds 1 -8, 11 and 13 were fully characterized by multi-nuclear ( 1 H, 13 43 and in methyl dimethyldiselenocarbamate (δ Se = 602 ppm), 44 however, these values are drastically shifted to high-field, compared to that in the six-membered systems such as 1-thia-3,3,5,5-tetramethyl-4-cyclohexanselenone (δ Se = 2131 ppm) and selenofenchone (δ Se = 1613 ppm). 45 With respect to heterocycles 12 and 13, the 13 C chemical shifts for the C=O in 13 being at δ C = 198.4 ppm falls with the range of 160-220 ppm for carbonyl carbon atoms.…”

Section: Scheme 5 Selenation Of the Adducts 4 Into The Selenamide 11mentioning

confidence: 99%

Synthesis and Selenation of Tandem Multicomponent Condensation Adducts

Hua¹,

Du²,

Fuller³

et al. 2015

Synlett

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A number of four-component condensation adducts, which were readily obtained from one-pot reaction of aryl carboxylic acids, arylaldehydes, arylamines and chexylisocyanide, were treated with two equivalents of Woollins' reagent leading to the formation of a series of novel selenoamides with one or two C=Se groups, or heterocyclic compounds such as 1,3-selenazole and 1,3-selenazolidin-5-one. [15][16][17][18][19] to generate structural diversity and a high degree of complexity in a minimal number of reaction steps. To our knowledge, however, there is no protocol for the synthesis of chalcogenated amides in such condensation adducts so far. Thus, the development of an efficient approach for the synthesis of chalcoginated adducts remains a challenge.2,4-Bis(phenyl)-1,3-diselenadiphosphethane-2,4-diselenide [{PhP(Se)(µ-Se)} 2 ] (Woollins' reagent), a selenium counterpart of the well-known Lawesson's reagent, has been well documented as an efficient phosphorus-selenium building block or selenation reagent in organic synthetic chemistry in recent years. 20 The reaction of Woollins' reagent with a variety of organic substrates exhibits a diverse spectrum ranging from simple oxygen-selenium exchange to the formation of complex phosphorus-selenium small-and macro-heterocycles as well as the surprising phosphorus-selenium-free products. [21][22][23][24][25][26][27][28][29][30][31][32][33] In light of our continuing interest in the application of Woollins' reagent in organic synthesis, herein, we report the synthesis of a series of new adducts via tandem four-component condensation, and their corresponding selenation derivatives.It has been well known that a highly flexible multicomponent reaction between aldehydes, amines, carbonyl compounds, and isocyanides to form N-aryl amines. 34,35 While searching for new acidic substituents in the Ugi reaction, we thought that a suitable electron-withdrawing group on a carbonyl group could trigger both the imine activation and the irreversible rearrangement in the key step of the reaction.Indeed, we found that phenylglyoxylic acid reacting with an equivalent of cyclohexyl isocyanide, p-chloroaniline and substituted benzaldehydes such as 2,3-dimethoxybenzaldehyde or 3-methoxybenzaldehyde or 4-chlorobenzaldehyde is a very straightforward and efficient four-component reaction. This reaction proceeded smoothly at room temperature in methanol medium within 18 hours to provide the desired N-aryl amines 1 -3 in excellent yields (Scheme 1). 36Scheme 1 Formation of four-component condensation adducts 1 -3The high yield, simple reaction protocol, and originality of this tandem process prompted us to explore the reaction more widely with a variety of substrates. Phenylacetic acid and benzoic acid are proved to be good substrates for this process and reacted with various amines, isocyanides and arylaldehydes. The reaction of phenylacetic acid with one equivalent of cyclohexylisocyanide, 2,3-dimethoxybenzaldehyde and 4-bromoaniline gave rise to the expected adduct 4 in 99% yield under ...

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“…932w, 910w, 870m, 778m, 760w, 738w, 692w. 'H-NMR: 9,34 (br.s, NH); 3,50, 3,19 (2br.s,(CH,),N); 1,9-1,85 (s, 2 CH,). ',C-NMR: 164.5 (s, C(5)); 161,9 (q.,J(C,F) = 30,1, CF,C=O); 151,7 (s, C(2)); 140,7 (s, CH,=C);…”

Section: 5-(dimethylamino)-34-dihydro-4-methyl-2-oxo-4-(propen-2-ymentioning

confidence: 99%

“…(CH,),N); 35.8 ( 4 (CH,),CH); 239 (4. CH,-C(5)); 17, 4,15,O (2q,(CH,),CH). MS: 198 (27,M+,), 155 (loo), 99 (ll), 42 (15).…”

Section: Allgemeines S [26][27] Wenn Nicht Anders Vermerkt Ir-spementioning

confidence: 99%

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Dipolare (1:1)‐Addukte aus der Reaktion von 3‐Amino‐2H‐azirinen mit 1,3,4‐Oxadiazol‐ und 1,3,4‐Thiadiazol‐2(3H)‐onen

Ametamey

Vincent

Heimgartner

1990

Helvetica Chimica Acta

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Umsetzungen von 3-Amino-2H-azirinen rnit 5-(Trifluoromethyl)-l,3,4-oxa-diazol-2(3H)-on (2). -Die 3-Amino-2H-azirine lb-g wurden, in analoger Weise wie l a [ 1 11, in i-PrOH bei Raumtemperatur rnit 2 umgesetzt. Dabei reagierten lb, If und l g in guten Ausbeuten zu den dipolaren (1: 1)-Addukten 3b, 3f und 3g (Schema 3, Tab. 1), die jeweils durch Zugabe von Et,O direkt aus dem Reaktionsgemisch ausgefallt und anschliessend umkristallisiert wurden. Erwiihnenswert ist die Beobachtung, dass die Umsetzung mit dem N-Methyl-N-phenyl-Derivat l b deutlich langsamer verlief als die Schema 3 1 3 4 3, Stabile dipolare Addukte wurden schon friiher bei Umsetzungen von 3-Amino-2H-azirinen mit Isothiocyanaten [ 18][19] und mit CS, [20][21] isoliert. 3. Hydrolyse einiger (1:l)-Addukte. -Einen chemischen Beweis fur die Strukturen 3a und 6e lieferte die Hydrolyse rnit wasseriger 2~ HCl in MeOH (Schema 7). Im Falle von 3a wurde nach 2 h bei 55" in 53% Ausbeute das Hydantoin 7 erhalten. In analoger Weise lieferte 6e das Hydantoin 8 (58%), wobei in diesem Beispiel die Reaktion schon bei Raumtemperatur erfolgte. Schema 7 H H 3a 7

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Synthese von 4,4‐disubstituierten 1,3‐Thiazol‐5(4H)‐thionen

Cited by 50 publications

References 44 publications

Reaction of 1,3-Thiazole-5(4H)-thiones with 1,2-Epoxycycloalkanes: Formation of Spirocyclic 1,3-Oxathiolanes

Reaction of 1,3-Thiazole-5(4H)-thiones with 1,2-Epoxycycloalkanes: Formation of Spirocyclic 1,3-Oxathiolanes

Synthesis and Selenation of Tandem Multicomponent Condensation Adducts

Dipolare (1:1)‐Addukte aus der Reaktion von 3‐Amino‐2H‐azirinen mit 1,3,4‐Oxadiazol‐ und 1,3,4‐Thiadiazol‐2(3H)‐onen

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