Acetic Acid → 3-(Cyclopropylmethyl)-3-azaspiro[5,5]undecane

HRID 1042243

反応式

HRID 1042243 の反応式
[CH2:1]1[C:6]2([CH2:11][CH2:10][CH2:9][CH2:8][CH2:7]2)[CH2:5][CH2:4][NH:3][CH2:2]1.[CH:12]1([CH:15]=O)[CH2:14][CH2:13]1.[BH-](OC(C)=O)(OC(C)=O)OC(C)=O.[Na+].CC(O)=O>ClC(Cl)C>[CH:12]1([CH2:15][N:3]2[CH2:4][CH2:5][C:6]3([CH2:11][CH2:10][CH2:9][CH2:8][CH2:7]3)[CH2:1][CH2:2]2)[CH2:14][CH2:13]1

参加物

6

反応物 4

HCID 176Acetic AcidHCID 123114CyclopropanecarboxaldehydeHCID 4174123-Azaspiro(5.5)undecane hydrochlorideHCID 5049666Sodium triacetoxyborohydride

生成物 1

HCID 441853723-(Cyclopropylmethyl)-3-azaspiro[5,5]undecane収率 94%

試薬・触媒・溶媒 1

HCID 63651,1-Dichloroethane溶媒

実験手順

To a solution of 3-azaspiro[5,5]undecane (0.34 g, 2.2 mmol), cyclopropanecarbaldehyde (0.14 g, 2 mmol) and NaBH(OAc)3 (0.64 g, 3 mmol) in dichloroethane (10 mL) were added AcOH (0.12 mL, 2 mmol), the resulting suspension was stirred overnight, quenched with NaHCO3 and extracted with CH2Cl2 twice, the combined organic layer was washed with brine, and dried with MgSO4. The solution was filtered, concentrated in vacuo and purified by flash chromatography. The compound was converted to the hydrochloride by passing HCl gas into the ether solution of 3-(cyclopropylmethyl)-3-azoniaspiro[5,5]undecane at 0° C., followed by decanting the ether supernatant, the final white solid (0.39 g, 80% yield) was dried in vacuo. 1H NMR (360 MHz, CDCl3) δ 2.45 (t, J=5.66 Hz, 4H), 2.23 (d, J=6.51 Hz 2H), 1.49 (t, J=5.66 Hz, 4H), 1.48-1.40 (m, 6H), 1.38-1.30 (m, 4H), 0.92-0.82 (m, 1H), 0.52-0.47 (m, 2H), 0.11-0.17 (m, 2H); 13C NMR (90 MHz, CDCl3) δ 64.55, 49.67, 36.47, 35.46, 31.00, 27.12, 21.73, 8.74, 4.19; ESI-MS: Calculated for C14H25N (M+H)+ 208.4, Found: 208.4.

後処理

  1. customquenched with NaHCO3
  2. extractionextracted with CH2Cl2 twice
  3. washthe combined organic layer was washed with brine
  4. dry with materialdried with MgSO4
  5. filtrationThe solution was filtered
  6. concentrationconcentrated in vacuo
  7. custompurified by flash chromatography
  8. customat 0° C.
  9. customby decanting the ether supernatant

出典と根拠

ORDレコード
ord-e0f2b1f1d79144b2aea112e119feb9ce
出典データセット
uspto-grants-2013_10
特許番号
US08557836B2

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