1,3,4-Thiadiazol-2-amine → N-(2,4-dimethoxybenzyl)-1,3,4-thiadiazol-2-amine

HRID 46318

반응식

HRID 46318 반응식
[CH3:1][O:2][C:3]1[CH:10]=[C:9]([O:11][CH3:12])[CH:8]=[CH:7][C:4]=1[CH:5]=O.[NH2:13][C:14]1[S:15][CH:16]=[N:17][N:18]=1.[BH4-].[Na+].C(=O)([O-])O.[Na+]>C1(C)C(C)=CC=CC=1.CC1CCCO1.O.CO>[CH3:1][O:2][C:3]1[CH:10]=[C:9]([O:11][CH3:12])[CH:8]=[CH:7][C:4]=1[CH2:5][NH:13][C:14]1[S:15][CH:16]=[N:17][N:18]=1

참가 물질

9

반응물 4

HCID 199091,3,4-Thiadiazol-2-amineHCID 691752,4-DimethoxybenzaldehydeHCID 516892Sodium BicarbonateHCID 4311764Sodium borohydride

생성물 1

HCID 58042278N-(2,4-dimethoxybenzyl)-1,3,4-thiadiazol-2-amine수율 73.5%

시약·촉매·용매 4

HCID 887Methanol용매HCID 962Water용매HCID 7237O-Xylene용매HCID 73012-Methyltetrahydrofuran용매

실험 절차

2,4-Dimethoxybenzaldehyde (771.37 g, 4.64 moles) was added to a suspension of 2-amino-1,3,4-thiadiazole (391.2 g, 3.87 moles) in xylene (5.87 L) and heated to reflux. Dean-Stark apparatus was used to remove the water and the reaction was stirred overnight. After cooling to room temperature, the reaction was further cooled to 5° C. and diluted with 2-methyltetrahydrofuran (2.93 L). Sodium tetrahydroborate (73.17 g, 1.93 moles) was added as a single portion. Methanol (782.8 mL) was then added slowly over 30 minutes, maintaining the temperature below 15° C. After a further 30 minutes water (1 L) was added followed by saturated aqueous sodium hydrogencarbonate solution (1 L) and the mixture stirred at room temperature overnight. The biphasic mixture was diluted with 2-methyltetrahydrofuran and heated to 43° C. to aid dissolution. The layers were separated and the organic layer washed with water (3 L) before concentrating in vacuo. The resulting solid was slurried in heptanes (2.5 L), homogenised, filtered, washed with tert-butylmethyl ether and dried to afford 715 g of the title compound.

후처리

  1. temperatureheated to reflux
  2. customto remove the water
  3. temperaturethe reaction was further cooled to 5° C.
  4. additiondiluted with 2-methyltetrahydrofuran (2.93 L)
  5. temperaturemaintaining the temperature below 15° C
  6. stirringthe mixture stirred at room temperature overnight
  7. temperatureheated to 43° C.
  8. dissolutiondissolution
  9. customThe layers were separated
  10. washthe organic layer washed with water (3 L)
  11. concentrationbefore concentrating in vacuo
  12. stirringhomogenised
  13. filtrationfiltered
  14. washwashed with tert-butylmethyl ether
  15. customdried

출처 및 근거

ORD 기록
ord-af710dbdaf82476fa13e16dd34a0e920
출처 데이터셋
uspto-grants-2013_09
특허 번호
US08541588B2

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