Formaldehyde → 9-(3,4-Dichloro-phenyl)-3-methyl-3-aza-spiro[5.5]undec-8-ene

HRID 419281노트

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HRID 419281 반응식
[Cl:1][C:2]1[CH:3]=[C:4]([C:9]2[CH2:19][CH2:18][C:12]3([CH2:17][CH2:16][NH:15][CH2:14][CH2:13]3)[CH2:11][CH:10]=2)[CH:5]=[CH:6][C:7]=1[Cl:8].C=O.[C:22](O[BH-](OC(=O)C)OC(=O)C)(=[O:24])C.[Na+].ClCCl.CO>ClC(Cl)C.CO>[OH-:24].[NH4+:15].[Cl:1][C:2]1[CH:3]=[C:4]([C:9]2[CH2:19][CH2:18][C:12]3([CH2:13][CH2:14][N:15]([CH3:22])[CH2:16][CH2:17]3)[CH2:11][CH:10]=2)[CH:5]=[CH:6][C:7]=1[Cl:8]

참가 물질

8

반응물 4

HCID 712FormaldehydeHCID 5049666Sodium triacetoxyborohydrideHCID 160063269-(3,4-Dichlorophenyl)-3-azaspiro[5.5]undec-8-eneHCID 21226129Dichloromethane methanol

생성물 2

HCID 14923Ammonium Hydroxide수율 1%HCID 160064359-(3,4-Dichloro-phenyl)-3-methyl-3-aza-spiro[5.5]undec-8-ene수율 105.1%

시약·촉매·용매 2

HCID 887Methanol용매HCID 63651,1-Dichloroethane용매

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온도
0 °C

실험 절차

To an ice cooled solution of 9-(3,4-dichloro-phenyl)-3-aza-spiro[5.5]undec-8-ene (410 mg, 1.38 mmol) in dichloroethane (12 mL) and methanol (4 mL), formaldehyde (37% in water, 157 μL, 2.08 mmol) was added and stirred for 1 h at 0° C. Sodium triacetoxy-borohydride (585 mg, 2.76 mmol) was added and the mixture stirred at room temperature over night. The reaction was quenched with aqueous sodium hydrogen-carbonate and evaporated. The remaining aqueous phase was extracted four times with dichloromethane and the combined organic phase was dried (sodium sulfate), filtered and evaporated to give 320 mg of crude material. Flash chromatography (dichloromethane/methanol 9:1 with 1% ammonium hydroxide) gave 225 mg (52%) of 9-(3,4-dichloro-phenyl)-3-methyl-3-aza-spiro[5.5]undec-8-ene as an yellow oil.

후처리

  1. stirringthe mixture stirred at room temperature over night
  2. customThe reaction was quenched with aqueous sodium hydrogen-carbonate
  3. customevaporated
  4. extractionThe remaining aqueous phase was extracted four times with dichloromethane
  5. dry with materialthe combined organic phase was dried (sodium sulfate)
  6. filtrationfiltered
  7. customevaporated
  8. customto give 320 mg of crude material

출처 및 근거

ORD 기록
ord-1f3b281e26c54128b69c48a8d55c379b
출처 데이터셋
uspto-grants-2012_01
특허 번호
US08093388B2

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