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

HRID 419281ノート

反応式

HRID 419281 の反応式
[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]

参加物

8

反応物 4

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

生成物 2

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

試薬・触媒・溶媒 2

HCID 887Methanol溶媒HCID 63651,1-Dichloroethane溶媒

反応条件

温度
0 °C

実験手順

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.

後処理

  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

出典と根拠

ORDレコード
ord-1f3b281e26c54128b69c48a8d55c379b
出典データセット
uspto-grants-2012_01
特許番号
US08093388B2

反応ノート

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