Tributylstannane → 4-Methoxy-6-methoxycarbonyl-10-phenylmethyl-6,7,8,9-tetrahydropyrido[1,2-a]indole

HRID 51466ノート

反応式

HRID 51466 の反応式
C([SnH](CCCC)CCCC)CCC.N(C(C)(C)C#N)=NC(C)(C)C#N.[CH3:26][O:27][C:28]1[CH:29]=[CH:30][CH:31]=[C:32]2[C:36]=1[N:35]1[CH:37]([C:41]([O:43][CH3:44])=[O:42])[CH2:38][CH2:39][CH2:40][CH:34]1[CH:33]2[CH2:45][C:46]1[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=1.C1(CC2C3C(=C(OC)C=CC=3)N(C(CCC)C(OC)=O)C=2)C=CC=CC=1>C1(C)C=CC=CC=1.O1CCOCC1>[CH3:26][O:27][C:28]1[CH:29]=[CH:30][CH:31]=[C:32]2[C:36]=1[N:35]1[CH:37]([C:41]([O:43][CH3:44])=[O:42])[CH2:38][CH2:39][CH2:40][C:34]1=[C:33]2[CH2:45][C:46]1[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=1

参加物

7

反応物 4

HCID 5948TributylstannaneHCID 6547AzobisisobutyronitrileHCID 22740584Methyl 2-[3-phenylmethyl-7-methoxyindol-1-yl]pentanoateHCID 22741322HCID 22741322、化合物

生成物 1

HCID 99029604-Methoxy-6-methoxycarbonyl-10-phenylmethyl-6,7,8,9-tetrahydropyrido[1,2-a]indole

試薬・触媒・溶媒 2

HCID 1140Toluene溶媒HCID 312751,4-Dioxane溶媒

実験手順

A solution of 1.8 gm (4.7 mmol) of the product from Part B and 4 mL (15 mmol) of tri-n-butyltin hydride in 50 mL of toluene was heated to reflux and treated dropwise with a solution of 85 mg (0.5 mmol) of 2,2′-azobis(2-methylpropionitrile). The solution was refluxed 1 hour after the addition, cooled, evaporated in vacuo, taken up in ethyl acetate, shaken with aqueous potassium floride, and filtered. The organic phase was washed with saturated sodium chloride, dried over sodium sulfate, and evaporated in vacuo to give a mixture of 4-methoxy-6-methoxycarbonyl-10-phenylmethyl-6,7,8,9,9a,10-hexahydropyrido[1,2-a]indole and methyl 2-[3-phenylmethyl-7-methoxyindol-1-yl]pentanoate which was dissolved in 25 mL of dioxane and stirred with 450 mg (2 mmol) of dichlorodicyanoquinone for 30 minutes. The solution was evaporated in vacuo, taken up in dichloromethane, filtered through florisil, and evaporated in vacuo. The residue was chromatographed on silica gel eluting with a gradient hexane/10-20% ethyl ether to give the title compound, 75 mg, 5%, as an amorphous solid. 1H NMR (CDCl3) δ: 1.70 (m, 1H), 1.85 (m, 1H), 2.20 (m, 1H), 2.35 (m, 1H), 2.70 (m, 1H), 3.00 (m, 1H), 3.70 (s, 3H), 3.80 (s, 3H), 4.00 (q, 2H), 5.65 (m, 1H), 6.50 (d, 1H), 6.90 (t, 1H), 7.00 (d, 1H), 7.10 (m, 1H), 7.20 (m, 4H).

後処理

  1. temperatureto reflux
  2. temperatureThe solution was refluxed 1 hour
  3. additionafter the addition
  4. temperaturecooled
  5. customevaporated in vacuo
  6. filtrationfiltered
  7. washThe organic phase was washed with saturated sodium chloride
  8. dry with materialdried over sodium sulfate
  9. customevaporated in vacuo
  10. customto give
  11. customThe solution was evaporated in vacuo
  12. filtrationfiltered through florisil
  13. customevaporated in vacuo
  14. customThe residue was chromatographed on silica gel eluting with a gradient hexane/10-20% ethyl ether

出典と根拠

ORDレコード
ord-aa7c1e4bdda34ee4962c52ad3b7a4ec1
出典データセット
uspto-grants-2004_03
特許番号
US06713645B1

反応ノート

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