Ammonia → 1,3,4-THIADIAZOLE, 2-METHYL-5-[(PHENYLMETHYL)THI

HRID 2413333ノート

反応式

HRID 2413333 の反応式
C[Si](C)(C)N[Si](C)(C)C.[SH:10][C:11]1[S:15][C:14]([CH3:16])=[N:13][N:12]=1.N.C[Si](C)(C)SC1SC(C)=NN=1.[CH2:29](Br)[C:30]1[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=1>S1(C2C(=CC=CC=2)C(=O)N1)(=O)=O.CN(C)P(=O)(N(C)C)N(C)C.C(#N)C>[CH2:29]([S:10][C:11]1[S:15][C:14]([CH3:16])=[N:13][N:12]=1)[C:30]1[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=1

参加物

9

反応物 5

HCID 222AmmoniaHCID 7498Benzyl BromideHCID 13838HexamethyldisilazaneHCID 127899522-Methyl-5-[(trimethylsilyl)sulfanyl]-1,3,4-thiadiazoleHCID 178434161HCID 178434161、化合物

生成物 1

HCID 51582181,3,4-THIADIAZOLE, 2-METHYL-5-[(PHENYLMETHYL)THI収率 96.4%

試薬・触媒・溶媒 3

HCID 5143Saccharin触媒HCID 6342Acetonitrile溶媒HCID 12679Hexamethylphosphoramide溶媒

実験手順

15 ml (72 mmoles) of hexamethyldisilazane were added to a refluxing mixture of 9.9 g (75 mmoles) of 5-mercapto-2-methyl-1,3,4-thiadiazole, 27 mg (0.15 mmole) of saccharin, 50 ml of acetonitrile and 20 ml of hexamethylphosphoric triamide and after refluxing for 4.5 hours, the calculated amount of ammonia had been evolved. Refluxing was continued for 30 minutes and the mixture containing 5-trimethylsilylthio-2-methyl-1,3,4-thiadiazole was cooled to room temperature and 9.9 ml (80 mmoles) of benzyl bromide were added thereto which raised the temperature to about 50° C. All starting material was consumed within 5 minutes. The acetonitrile was removed by evaporation and 100 ml of ethyl acetate were added to the residue. The solution was poured into 250 ml of water and the aqueous layer was extracted three times with 30 ml of ethyl acetate. The combined organic extracts were washed with a 10% sodium chloride solution, dried, filtered and evaporated to dryness. The solid residue was washed with hexane containing some diethyl ether to obtain 15.91 g (96.4% yield) of 5-benzylthio-2-methyl-1,3,4-thiadiazole melting at 60°-63° C. Crystallization from a mixture of ethyl acetate and petroleum ether (boiling range 40°-60° C.) provided 14.27 g of the pure substance melting at 62.5°-63.5° C.

後処理

  1. temperatureafter refluxing for 4.5 hours
  2. temperatureRefluxing
  3. temperaturewhich raised the temperature to about 50° C
  4. customwas consumed within 5 minutes
  5. customThe acetonitrile was removed by evaporation and 100 ml of ethyl acetate
  6. additionwere added to the residue
  7. additionThe solution was poured into 250 ml of water
  8. extractionthe aqueous layer was extracted three times with 30 ml of ethyl acetate
  9. washThe combined organic extracts were washed with a 10% sodium chloride solution
  10. customdried
  11. filtrationfiltered
  12. customevaporated to dryness
  13. washThe solid residue was washed with hexane containing some diethyl ether

出典と根拠

ORDレコード
ord-a0149f65eed74d57bb5b4c8585524d50
出典データセット
uspto-grants-1985_01
特許番号
US04496720

反応ノート

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