Ammonia → 2,2-difluoro-2-pyridin-2-yl-ethylamine benzenesulphonate, (1:1 salt)

HRID 45574

反応式

HRID 45574 の反応式
C[C:2]1[CH:7]=[CH:6][C:5]([S:8]([O:11][CH2:12][C:13]([F:21])([F:20])[C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][N:15]=2)(=[O:10])=[O:9])=[CH:4][CH:3]=1.[Na+].[I-].[NH3:24].C1(S(O)(=O)=O)C=CC=CC=1>C(OC(C)C)(=O)C.CS(C)=O>[C:5]1([S:8]([OH:11])(=[O:10])=[O:9])[CH:6]=[CH:7][CH:2]=[CH:3][CH:4]=1.[F:20][C:13]([F:21])([C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][N:15]=1)[CH2:12][NH2:24]

参加物

7

反応物 4

HCID 222Ammonia2 回HCID 5238Sodium IodideHCID 7371Benzenesulfonic AcidHCID 582496422,2-Difluoro-2-pyridin-2-ylethyl 4-methylbenzenesulfonate

生成物 1

HCID 783578632,2-difluoro-2-pyridin-2-yl-ethylamine benzenesulphonate, (1:1 salt)収率 49.5%

試薬・触媒・溶媒 2

HCID 679Dimethyl Sulfoxide溶媒HCID 7915Isopropyl Acetate溶媒

反応条件

温度
80 °C

実験手順

10 g of 2,2-Difluoro-2-pyridin-2-ylethyl 4-methylbenzenesulfonate (J) obtained in step 3, 5 g of NaI, 20 mL of DMSO and 90 mL of aqueous ammonia were taken in a 500 mL autoclave vessel. The reaction mixture was heated to 80° C. and a pressure of 15 to 17 kg of ammonia maintained for 30-40 hours. The volume of the reaction mass was reduced by vacuum distillation. The RM was washed with 60 mL of IPE. The pH of the RM was adjusted to 10-14 by adding a 50% NaOH solution and extracted three times with 60 mL of MDC. The combined MDC layers were washed with brine, dried over sodium sulphate and distilled under vacuum (crude weight=8 g). The crude mass obtained was dissolved with 10 mL of MDC, and to this 4.5 g benzene sulphonic acid (BSA) dissolved in 30 mL isopropyl acetate (IPAc) was added dropwise over a period of 30 minutes with stirring at RT. The RM was stirred for 30 minutes at RT. The solid obtained was filtered and washed with IPAc and dried under vacuum, resulting in 5 g of the titled compound (Yield=49.5%).

後処理

  1. distillationThe volume of the reaction mass was reduced by vacuum distillation
  2. washThe RM was washed with 60 mL of IPE
  3. additionby adding a 50% NaOH solution
  4. extractionextracted three times with 60 mL of MDC
  5. washThe combined MDC layers were washed with brine
  6. dry with materialdried over sodium sulphate
  7. distillationdistilled under vacuum (crude weight=8 g)
  8. customThe crude mass obtained
  9. dissolutionwas dissolved with 10 mL of MDC
  10. additionwas added dropwise over a period of 30 minutes
  11. stirringThe RM was stirred for 30 minutes at RT
  12. customThe solid obtained
  13. filtrationwas filtered
  14. washwashed with IPAc
  15. customdried under vacuum

出典と根拠

ORDレコード
ord-ac1aafe395f44b6fa336ed0ef1904144
出典データセット
uspto-grants-2013_09
特許番号
US08541580B2

関連ノート

読み込み中…