Benzaldehyde → HCID 178477573、化合物

HRID 853125ノート

反応式

HRID 853125 の反応式
[NH2:1][CH:2]1[CH2:7][CH2:6][CH:5]([C:8]([OH:17])([C:13]([F:16])([F:15])[F:14])[C:9]([F:12])([F:11])[F:10])[CH2:4][CH2:3]1.CCN(CC)CC.[CH:25](=O)[C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1.C1CCN2C(=NCCC2)CC1.[Si:44](Cl)([CH2:49][CH3:50])([CH2:47][CH3:48])[CH2:45][CH3:46].[NH4+].[Cl-].[BH4-].[Na+]>C(O)C.CN(C=O)C.CCOCC>[CH2:25]([NH:1][C@H:2]1[CH2:3][CH2:4][C@@H:5]([C:8]([O:17][Si:44]([CH2:49][CH3:50])([CH2:47][CH3:48])[CH2:45][CH3:46])([C:13]([F:14])([F:15])[F:16])[C:9]([F:11])([F:12])[F:10])[CH2:6][CH2:7]1)[C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1.[CH2:25]([NH:1][C@H:2]1[CH2:3][CH2:4][C@H:5]([C:8]([O:17][Si:44]([CH2:49][CH3:50])([CH2:47][CH3:48])[CH2:45][CH3:46])([C:13]([F:14])([F:15])[F:16])[C:9]([F:11])([F:12])[F:10])[CH2:6][CH2:7]1)[C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1

参加物

12

反応物 7

HCID 240BenzaldehydeHCID 8471TriethylamineHCID 13819ChlorotriethylsilaneHCID 25517Ammonium ChlorideHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 4311764Sodium borohydrideHCID 86605616HCID 86605616、化合物

生成物 2

HCID 178477572HCID 178477572、化合物収率 14%HCID 178477573HCID 178477573、化合物収率 20%

試薬・触媒・溶媒 3

HCID 702Ethanol溶媒HCID 3283Diethyl Ether溶媒HCID 6228Dimethylformamide溶媒

実験手順

A solution of 17 g (78.23 mmol) of the acetate salt of 2-(4-amino-cyclohexyl)-1,1,1,3,3,3-hexafluoro-propan-2-ol (example 2.1) in 250 mL of ethanol was treated with 27.2 mL (196 mmol) of NEt3 and 8.75 mL (86.1 mmol) of benzaldehyde. The mixture was stirred overnight at RT and the solvents evaporated i.v. The brown oil obtained was dissolved in 120 mL of DMF and treated with 8.76 mL (58.7 mmol) of DBU and then dropwise with 9.85 mL (58.7 mmol) of TESCl. The mixture was stirred for 4 hrs at RT and distributed between a saturated aqueous solution of NH4Cl and Et2O. The crude material obtained after drying of the combined organic phases over Na2SO4 and evaporation of the solvent was dissolved in 250 mL of ethanol and treated portionwise with 2.2 g (58.7 mmol) of NaBH4 and stirred for 2 hrs at RT. Evaporation of the solvent, distribution between Et2O and an aqueous solution of NaOH, drying of the combined organic phases over Na2SO4 and chromatography on silica gel with heptane/EtOAc (gradient from 6:1 to 2:1) yielded 3.3 g (14%) of cis benzyl-[4-(2,2,2-trifluoro-1-triethylsilanyloxy-1-trifluoromethyl-ethyl)-cyclohexyl]-amine and 4.7 g (20%) trans benzyl-[4-(2,2,2-trifluoro-1-triethylsilanyloxy-1-trifluoromethyl-ethyl)-cyclohexyl]-amine as a yellow oil, MS: 470 (M+H)+.

後処理

  1. customthe solvents evaporated i.v
  2. customThe brown oil obtained
  3. stirringThe mixture was stirred for 4 hrs at RT
  4. customThe crude material obtained
  5. dry with materialafter drying of the combined organic phases over Na2SO4 and evaporation of the solvent
  6. dissolutionwas dissolved in 250 mL of ethanol
  7. stirringstirred for 2 hrs at RT
  8. customEvaporation of the solvent, distribution between Et2O
  9. dry with materialan aqueous solution of NaOH, drying of the combined organic phases over Na2SO4 and chromatography on silica gel with heptane/EtOAc (gradient from 6:1 to 2:1)

出典と根拠

ORDレコード
ord-47020953a69a4f0f9e1f02403498ad36
出典データセット
uspto-grants-2007_08
特許番号
US07253282B2

反応ノート

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