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Hydrochloric Acid → HCID 24769019、化合物

HRID 2422857
ノート
印刷プレビュー

反応式

HRID 2422857 の反応式
FC1C=CC(OC)=C(C2C=CC(C=NS(CC(C)C)=O)=CC=2)C=1.C([N+](CCCC)(CCCC)CCCC)CCC.FC([Si](C)(C)C)(F)F.FC(F)(F)C(NS(CC(C)C)=O)C1C=CC(C2C=C(F)C=CC=2OC)=CC=1.Cl.Cl.[F:78][C:79]([F:98])([F:97])[CH:80]([NH2:96])[C:81]1[CH:86]=[CH:85][C:84]([C:87]2[CH:92]=[C:91]([F:93])[CH:90]=[CH:89][C:88]=2[O:94][CH3:95])=[CH:83][CH:82]=1.[F:99][C:100]([F:113])([F:112])[O:101][C:102]1[CH:107]=[CH:106][CH:105]=[CH:104][C:103]=1[S:108](Cl)(=[O:110])=[O:109]>O1CCCC1.CO.CCOCC.N1C=CC=CC=1.ClCCl>[F:98][C:79]([F:78])([F:97])[CH:80]([NH:96][S:108]([C:103]1[CH:104]=[CH:105][CH:106]=[CH:107][C:102]=1[O:101][C:100]([F:99])([F:112])[F:113])(=[O:110])=[O:109])[C:81]1[CH:82]=[CH:83][C:84]([C:87]2[CH:92]=[C:91]([F:93])[CH:90]=[CH:89][C:88]=2[O:94][CH3:95])=[CH:85][CH:86]=1
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

13

反応物 7

HCID 313Hydrochloric Acid2 回HCID 16028TetrabutylammoniumHCID 552549(Trifluoromethyl)trimethylsilaneHCID 27772152-(Trifluoromethoxy)benzene-1-sulfonyl chlorideHCID 672450682,2,2-Trifluoro-1-(5'-fluoro-2'-methoxy-biphenyl-4-yl)-ethylamine hyrochlorideHCID 67245151HCID 67245151、化合物
HCID 67245222
HCID 67245222、化合物

生成物 1

HCID 24769019HCID 24769019、化合物

試薬・触媒・溶媒 5

HCID 887Methanol溶媒HCID 1049Pyridine溶媒HCID 3283Diethyl Ether溶媒HCID 6344Dichloromethane溶媒HCID 8028Tetrahydrofuran溶媒

反応条件

温度
-10 °C

実験手順

To a solution of 4-bromobenzaldehyde (3.06 g, 16.5 mmol) in toluene (60 ml) was added 5-fluoro-2-methoxyphenyl boronic acid (3.10 g, 18.2 mmol), 2M sodium carbonate solution (16.5 ml) and tetrakis(triphenylphosphine)palladium (0) (1 g, 0.86 mmol). The solution was refluxed for 48 h then cooled to ambient temperature, washed with water, brine and dried over anhydrous sodium sulfate. Evaporation of solvent gave a residue that was flash chromatographed over silica gel eluting with 1:1 ethyl acetate/heptane. Evaporation of solvent gave 5′-fluoro-2′-methoxy-biphenyl-4-carbaldehyde (2.63 g) as a crystalline solid. To a solution of 5′-fluoro-2′-methoxy-biphenyl-4-carbaldehyde (1.5 g, 6.9 mmol) in tetrahydrofuran (20 ml) was added titanium tetraisopropoxide (10 ml) and (±)-tert-butyl sulfinamine. The solution was stirred for 48 h then poured into brine and dichloromethane added with stirring. The organic layer was separated, dried over anhydrous magnesium sulfate and the solvent evaporated. Heptane was added to the oil which induced crystallisation and gave 2-methyl-propane sulfinic acid 5′-fluoro-2′-methoxy-biphenyl-4-ylmethylene amide (1.85 g) as a white solid. To a solution of 2-methyl-propane sulfinic acid 5′-fluoro-2′-methoxy-biphenyl-4-ylmethylene amide (1 g, 3 mmol) and tetrabutyl ammonium difluorotriphenylsilica gelte (1.8 g, 3.3 mmol) in tetrahydrofuran (50 ml) at −55° C. was added trifluoromethyltrimethylsilane with stirring. The reaction mixture was kept below −40° C. for 3 h then warmed to −10° C. for 1 h. The reaction mixture was cooled to −30° C. then quenched with saturated ammonium chloride solution and extracted with ethyl acetate. The organic phase was dried over anhydrous magnesium sulfate, evaporated to a low volume and heptane added. The crystalline 2-methyl-propane sulfinic acid [2,2,2-trifluoro-1-(5′-fluoro-2′-methoxy-biphenyl-4-yl)-ethyl]-amide (0.75 g) was collected by filtration. To a solution of 2-methyl-propane sulfinic acid [2,2,2-trifluoro-1-(5′-fluoro-2′-methoxy-biphenyl-4-yl)-ethyl]-amide (0.73 g, 1.8 mmol) in methanol (10 ml) at room temperature was added a 1M solution of Hydrogen chloride in ether with stirring. The reaction mixture was stirred for 2 h, then the solvent was evaporated and ether added. The crystalline 2,2,2-trifluoro-1-(5′-fluoro-2′-methoxy-biphenyl-4-yl)-ethylamine hydrochloride (0.38 g) was collected by filtration. To a solution of 2,2,2-trifluoro-1-(5′-fluoro-2′-methoxy-biphenyl-4-yl)-ethylamine hyrochloride (60 mg, 0.15 mmol) in pyridine (3 ml) was added 2-trifluoromethoxyphenyl sulfonyl chloride with stirring. The reaction was stirred for 3 days at 100° C. then cooled to room temperature and 5M Hydrogen chloride and dichloromethane added. The organic layer was separated and the solvent evaporated. The residue was flash chromatographed over silica gel eluting with 1:1 heptane/dichloromethane and the solvent evaporated to give the title compound (29 mg). 1H NMR (400 MHz, CDCl3): 7.58-7.41 (m, 4H), 7.27-7.11 (m, 3H), 7.04-6.90 (m, 3H), 5.51 (d, 1H), 5.00 (app quin, 1H), 3.78 (s, 3H) ppm; MS (ESI) m/z: 546 [M+Na]+.

後処理

  1. temperatureThe reaction mixture was cooled to −30° C.
  2. customthen quenched with saturated ammonium chloride solution
  3. extractionextracted with ethyl acetate
  4. dry with materialThe organic phase was dried over anhydrous magnesium sulfate
  5. customevaporated to a low volume and heptane
  6. additionadded
  7. filtrationThe crystalline 2-methyl-propane sulfinic acid [2,2,2-trifluoro-1-(5′-fluoro-2′-methoxy-biphenyl-4-yl)-ethyl]-amide (0.75 g) was collected by filtration
  8. stirringwith stirring
  9. stirringThe reaction mixture was stirred for 2 h
  10. customthe solvent was evaporated
  11. additionether added
  12. filtrationThe crystalline 2,2,2-trifluoro-1-(5′-fluoro-2′-methoxy-biphenyl-4-yl)-ethylamine hydrochloride (0.38 g) was collected by filtration
  13. stirringwith stirring
  14. stirringThe reaction was stirred for 3 days at 100° C.
  15. temperaturethen cooled to room temperature
  16. customThe organic layer was separated
  17. customthe solvent evaporated
  18. customchromatographed over silica gel eluting with 1:1 heptane/dichloromethane
  19. customthe solvent evaporated

出典と根拠

ORDレコード
ord-e73eed74752b49feb81f080e50c0c279
出典データセット
uspto-grants-2011_06
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US07960365B2

反応ノート

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