The Preparation and Desulfurization of Some Unsymmetrically Substituted Thiiranes

Schuetz, Robert D.; Jacobs, Richard L.

doi:10.1021/jo01067a106

Cited by 58 publications

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“…Thiirane (IIa) was commercial product (Aldrich). Thiiranes IIb and IIc were synthesized according to the procedures described in [4] and [5], respectively.…”

Section: 3-dimethyl-67-dihydro[13]thiazolo[23-f]-purine-24(1h3mentioning

confidence: 99%

New synthesis of 6,7-dihydro[1,3]thiazolo[2,3-f]purine-2,4(1H,3H)-diones

Халиуллин

Клен

2009

Russ J Org Chem

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SHORT COMMUNICATIONSSeveral methods of synthesis of 6,7-dihydro[1,3]-thiazolo[2,3-f]purine-2,4(1H,3H)-diones have been reported, e.g., from 8-brom-7-(2-haloethyl)-3,7-dihydro-1H-purine-2,6-diones and sodium sulfide [1], by reaction of 8-halo-7-(thiiran-2-ylmethyl)-3,7-dihydro-1H-purin-2,6-diones with nucleophilic reagents [2], etc. We now propose a new one-step procedure for the preparation of 6,7-dihydro[1,3]thiazolo[2,3-f]purin-2,4(1H,3H)-dione derivatives via reaction of 8-halo-3,7-dihydro-1H-purine-2,6-diones with thiiranes. The reactions were carried out in DMF with 8-halo-3,7-dihydro-1H-purine-2,6-diones Ia-Ic as free bases (in the presence of a base) or potassium salts and an equimolar amount of thiirane IIa-IIc. 6,7-Dihydro[1,3]-thiazolo[2,3-f]purine-2,4(1H,3H)-diones IIIa-IIIc were thus obtained in 59-68% yield.The structure of compounds IIIa-IIIc was confirmed by elemental analyses and 1 H and 13 C NMR spectra. The properties of compound IIIa were consistent with published data [1]. Substituted thiiranes IIb and IIc gave rise to 7-substituted dihydrothiazolopurines IIIb and IIIc whose structure was additionally proved by independent synthesis of compound IIIb from 8-bromo-1,3-dimethyl-7-(thiiran-2-ylmethyl)-3,7-dihydro-1H-purine-2,6-dione and diethylamine [2]. Samples of IIIb prepared by the two methods showed no depression of the melting point on mixing, and their 1 H NMR spectra were fully identical. Our results indicated that opening of the thiirane ring follows the Krasuskii rule [3]. 1,3-Dimethyl-6,7-dihydro[1,3]thiazolo[2,3-f]-purine-2,4(1H,3H)-dione (IIIa).A solution of 2.59 g (10 mmol) of purine Ia, 0.56 g (10 mmol) of potassium hydroxide, and 0.60 g (10 mol) of thiirane IIa in 40 ml of DMF was heated for 3 h at 45-50°C. The mixture was cooled, and the precipitate was filtered off and washed with water. Yield 1.40 g (59%), mp 259-260°C (from i-BuOH) [1]. 1 H NMR spectrum, δ, ppm: 3.38 s (3H, 3-CH 3 ), 3.54 s (3H, 1-CH 3 ), 3.88-4.00 m (2H, SCH 2 ), 4.42-4.53 m (2H, NCH 2 ). Found, %: C 45.56; H 4.33; N 23.18. C 14 H 21 N 5 O 2 S. Calculated, %: C 45.37; H 4.23; N 23.51.7-(Diethylaminomethyl)-1,3-dimethyl-6,7-dihydro[1,3]thiazolo[2,3-f]purine-2,4(1H,3H)-dione (IIIb). A solution of 1.49 g (5 mmol) of purine Ib potassium salt and 0.73 g (5 mmol) of thiirane IIb in 30 ml of DMF was heated for 1 h under reflux. The mixture was cooled and diluted with water until a solid separated. The precipitate was filtered off and washed with water. Yield 1.10 g (68%), mp 177-178°C (from EtOH). 1 H NMR spectrum, δ, ppm: 0.99 t (6H, CH 2 CH 3 , 3 J = 7.1 Hz), 2.55 q (4H, NCH 2 CH 3 , 3 J = I, R = Me, Hlg = Br, X = H (a), K (b); R = H, Hlg = Cl, X = K (c); II, R′ = H (a), Et 2 NCH 2 (b), MeOCH 2 (c); III, R = Me, R′ = H (a), Et 2 NCH 2 (b); R = H, R′ = MeOCH 2 (c).

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“…Thiirane (IIa) was commercial product (Aldrich). Thiiranes IIb and IIc were synthesized according to the procedures described in [4] and [5], respectively.…”

Section: 3-dimethyl-67-dihydro[13]thiazolo[23-f]-purine-24(1h3mentioning

confidence: 99%

New synthesis of 6,7-dihydro[1,3]thiazolo[2,3-f]purine-2,4(1H,3H)-diones

Халиуллин

Клен

2009

Russ J Org Chem

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“…Thiirane (IIa) was commercial product (from Aldrich). Thiirane IIb was synthesized according to the procedure reported in [5], and thiirane IIc was prepared as described in [6].…”

Section: -Bromo-5-methoxymethyl-56-dihydrothiazolo-[32-b][124]trmentioning

confidence: 99%

New synthesis of 5,6-dihydrothiazolo[3,2-b][1,2,4]triazoles

Клен

Халиуллин

2009

Russ J Org Chem

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SHORT COMMUNICATIONS Fused 5,[1,2,4]triazole system may be constructed in several ways: (1) by reaction of 1,2,4-triazole-3(5)-thiols with 1,2-dibromoethane [1, 2], (2) by cyclization of 3-allylsulfanyl-1,2,4-triazoles by the action of iodine [3], and (3) by reaction of 3,5-dibromo-1-(thiiran-2-ylmethyl)-1,2,4-triazole with nucleophiles [4]. In the first two methods, isomeric 5,6-dihydrothiazolo[2,3-c][1,2,4]triazoles are formed as by-products [1][2][3].We now propose a new one-step procedure for the synthesis of 5,6-dihydrothiazolo[3,2-b][1,2,4]triazole derivatives by reaction of 3,5-dibromo-1,2,4-triazole with thiiranes. 5,6-Dihydrothiazolo[3,2-b][1,2,4]triazoles IIIa-IIIc were synthesized in 44-67% yield by heating triazole I with an equimolar amount of thiirane IIa-IIc in dimethylformamide in the presence of potassium hydroxide. The structure of compounds IIIa-IIIc was confirmed by elemental analysis and IR and 1 H and 13 C NMR spectroscopy. methods showed no depression of the melting point on mixing, and their IR spectra completely coincided. These data indicated that the thiirane ring is opened according to the Krasuskii rule [5]. 2-Bromo-5,6-dihydrothiazolo[3,2-b][1,2,4]triazole (IIIa).A solution of 2.26 g (10 mmol) of triazole I, 0.56 g (10 mmol) of KOH, and 0.60 g (10 mmol) of thiirane (IIa) in 20 ml of DMF was heated for 5 h at 45-50°C. The mixture was diluted with water to a ratio of 1 : 10 and extracted with ethyl acetate (2 × 50 ml), and the extract was evaporated. Yield 0.98 g (48%), mp 115-117°C (from i-PrOH). 2-Bromo-5-morpholinomethyl-5,6-dihydrothiazolo[3,2-b][1,2,4]triazole (IIIb).A solution of 1.59 g (7 mmol) of triazole I, 0.39 g (7 mmol) of KOH, and 1.10 g (7 mmol) of thiirane IIb in 15 ml of DMF was heated for 2 h under reflux. The mixture was cooled and diluted with water until a solid separated, and the precipitate was filtered off. Yield 1.43 g (67%), mp 163.5-165°C (from i-PrOH). IR spectrum, ν, cm -1 : . Found, %: C 35.34; H 4.35; N 18.24. C 9 H 13 BrN 4 OS. Calculated, %: C 35.42; H 4.29; N 18.36. 2-Bromo-5-methoxymethyl-5,6-dihydrothiazolo-[3,2-b][1,2,4]triazole (IIIc) was synthesized as described above for compound IIIb from 2.26 g (10 mmol) of triazole I and 1.04 g (10 mmol) of thiirane IIc in the presence of 0.56 g (10 mmol) of KOH. The mixture was diluted with water to a ratio of 1 : 10 and extracted with diethyl ether (3 × 40 ml), and the extract was evaporated. Yield 1.09 g (44%), mp 69-70°C

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“…Outros métodos utilizam reagentes que realizam derivatização in situ, como por exemplo, cloreto de trimetilsilila/iodeto de sódio 18 , trifenilfosfina/imidazol/iodo 19 e tribrometo de fósforo/ brometo cuproso/éter, seguida por reação com zinco em pó. 20 A desoxigenação indireta de dióis vicinais pode ser obtida através de uma conversão prévia em derivados de ésteres sulfonatos 22 , bisditiocarbonatos 23 , tiocarbonatos cíclicos [24][25][26][27] , oxiranos 28 , epissulfetos (tiiranos) [29][30][31][32][33][34] , ortoformiatos cíclicos 35 , fosfatos e fosforamidatos 36 e sulfatos [37][38][39][40][41] .…”

Section: Estratégias Para As Sínteses De 2'3'-desoxinucleosídeos E Aunclassified

Estratégias para a síntese de desoxinucluosídeos

Soares¹,

Souza²,

Ferreira³

2001

Quím. Nova

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Recebido em 18/2/00; aceito em 16/8/00 STRATEGIES FOR THE SYNTHESES OF DEOXINUCLEOSIDES. The number of agents available for the treatment of viral infections has increased dramatically during the past decade most of them belonging to the nucleoside class. The accomplishment of many syntheses for these nucleosides in recent years offers evidence that the field is very important for the organic synthesis. The discussion of several approaches for preparing deoxy and dehydronucleosides is reviewed in a simplified way.

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The Preparation and Desulfurization of Some Unsymmetrically Substituted Thiiranes

Cited by 58 publications

References 0 publications

New synthesis of 6,7-dihydro[1,3]thiazolo[2,3-f]purine-2,4(1H,3H)-diones

New synthesis of 6,7-dihydro[1,3]thiazolo[2,3-f]purine-2,4(1H,3H)-diones

New synthesis of 5,6-dihydrothiazolo[3,2-b][1,2,4]triazoles

Estratégias para a síntese de desoxinucluosídeos

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