Trityl chloride → (S)-Hexahydro-6-[(triphenylmethyl)amino]-2,2-dimethyl-2H-azepine-7-one

HRID 264985

反応式

HRID 264985 の反応式
O.NN.C1(=O)[N:8]([C@@H:9]2[C:15](=[O:16])[NH:14][C:13]([CH3:18])([CH3:17])[CH2:12][CH2:11][CH2:10]2)C(=O)C2=CC=CC=C12.C(N(CC)CC)C.[C:32]1([C:38]([C:46]2[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=2)([C:40]2[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=2)Cl)[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1>CO>[C:32]1([C:38]([NH:8][C@@H:9]2[C:15](=[O:16])[NH:14][C:13]([CH3:18])([CH3:17])[CH2:12][CH2:11][CH2:10]2)([C:46]2[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=2)[C:40]2[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=2)[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1

参加物

6

反応物 4

HCID 6456Trityl chloride2 回HCID 8471TriethylamineHCID 24654Hydrazine hydrate (1:1)HCID 10755636(S)-hexahydro-6-phthalimido-2,2-dimethyl-2H-azepine-7-one

生成物 1

HCID 10715893(S)-Hexahydro-6-[(triphenylmethyl)amino]-2,2-dimethyl-2H-azepine-7-one

試薬・触媒・溶媒 1

HCID 887Methanol溶媒

実験手順

Hydrazine monohydrate (4.59 ml., 94.6 mmol.) was added to a solution of (S)-hexahydro-6-phthalimido-2,2-dimethyl-2H-azepine-7-one [preparred as described in Example 66(e), 19.98 g., 68.76 mmol.] in methanol (250 ml.) at room temperature under argon. The resulting mixture was stirred for 72 hours then filtered to remove the white precipitate. The volatiles were evaporated and the residue was dissolved in methylene chloride (560 ml.) and filtered to remove additional precipitate. To this filtrate was added triethylamine (13.3 ml., 96.21 mmol.) followed by triphenylchloromethane (20.65 g., 74.07 mmol.) and the resulting mixture was stirred for 1.5 hours. Additional triphenylchloromethane (958 mg., 3.44 mmol.) was added and the solvent was removed. The residue was partitioned between ethyl acetate and water. The organic layer was washed with brine, dried, filtered and concentrated to give a pale yellow foam. Following a crystallization from ethyl acetate and hexanes, 7.47 g. of title product was obtained as off-white crystals. The mother liquor was concentrated and crystallized from ethyl acetate and pentane to give a second crop (8.02 g.) of title product. The mother liquor was concentrated and the residue was flash chromatographed (E Merck silica gel) eluting with 4.5:5.5 ethyl acetate/hexanes to give 6.0 g of title compound as a white foam. The combined yield of title product was 21.49 g.; m.p. 139°-140° C.; [α]D =+43.4° (c=0.37, methylene chloride). TLC (2:3 hexane:ethyl acetate) Rf =0.63.

後処理

  1. filtrationthen filtered
  2. customto remove the white precipitate
  3. customThe volatiles were evaporated
  4. dissolutionthe residue was dissolved in methylene chloride (560 ml.)
  5. filtrationfiltered
  6. customto remove additional precipitate
  7. stirringthe resulting mixture was stirred for 1.5 hours
  8. customthe solvent was removed
  9. customThe residue was partitioned between ethyl acetate and water
  10. washThe organic layer was washed with brine
  11. customdried
  12. filtrationfiltered
  13. concentrationconcentrated
  14. customto give a pale yellow foam
  15. customa crystallization from ethyl acetate and hexanes, 7.47 g

出典と根拠

ORDレコード
ord-57087d404193485ea2a01e6f561431c4
出典データセット
uspto-grants-1997_07
特許番号
US05646276

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