1-Piperidinecarboxaldehyde → [6-(Tert.-butyl-dimethyl-silanyloxymethyl)-3,7-dimethoxy-10-methyl-phenothiazine4-yl]methanol

HRID 2395176

反応式

HRID 2395176 の反応式
[C:1]([SiH2:5][O:6][C:7]([CH3:28])([CH3:27])[C:8]1[C:21]2[S:20][C:19]3[C:14](=[CH:15][CH:16]=[C:17]([O:22][CH3:23])[CH:18]=3)[N:13]([CH3:24])[C:12]=2[CH:11]=[CH:10][C:9]=1[O:25][CH3:26])([CH3:4])([CH3:3])[CH3:2].C([Li])CCC.[CH:34](N1CCCCC1)=[O:35].COC1C(C(C)(C)O[SiH2]C(C)(C)C)(C=O)C2SC3C(=CC=C(OC)C=3)N(C)C=2C=C1.[BH4-].[Li+]>C(OCC)C.O1CCCC1.O1CCCC1>[C:1]([SiH2:5][O:6][C:7]([CH3:28])([CH3:27])[C:8]1[C:9]([O:25][CH3:26])=[CH:10][CH:11]=[C:12]2[C:21]=1[S:20][C:19]1[C:18]([CH2:34][OH:35])=[C:17]([O:22][CH3:23])[CH:16]=[CH:15][C:14]=1[N:13]2[CH3:24])([CH3:4])([CH3:3])[CH3:2]

参加物

8

反応物 5

HCID 174291-PiperidinecarboxaldehydeHCID 4148881Lithium borohydrideHCID 131720844Tert-butyl-[2-(3,7-dimethoxy-10-methylphenothiazin-4-yl)propan-2-yloxy]silaneHCID 178418339ButyllithiumHCID 1784873354-(2-tert-butylsilyloxypropan-2-yl)-3,7-dimethoxy-10-methyl-3H-phenothiazine-4-carbaldehyde

生成物 1

HCID 137329065[6-(Tert.-butyl-dimethyl-silanyloxymethyl)-3,7-dimethoxy-10-methyl-phenothiazine4-yl]methanol収率 67.6%

試薬・触媒・溶媒 2

HCID 8028Tetrahydrofuran溶媒HCID 21868444Ether tetrahydrofuran溶媒

実験手順

A solution of 4.56 g (10.9 mmol) of 4-(tert.-butyl-dimethyl-silanyloxymethyl)-3,7-dimethoxy-10-methyl-phenothiazine in 50 ml of diethyl ether/tetrahydrofuran (4:1) was reacted with 7.5 ml of n-butyllithium solution (1.6M in hexane) and 1.89 g (16.84 mmol) of N-formylpiperidine analogously to that described in Example 4.1.1c. The resulting 3,7-dimethoxy-4-(tert.butyldimethyl-silanyloxymethyl)-10-methyl-phenothiazine-4-carbaldehyde was dissolved in 50 ml of tetrahydrofuran and reduced with 12.0 ml of lithium borohydride solution (1M in tetrahydrofuran) analogously to that described in Example 4.1.8.b. The reaction mixture was poured into ice/1M sodium dihydrogen phosphate solution, whereupon the mixture was extracted three times with ethyl acetate. The combined organic phases were washed with saturated sodium chloride solution, dried over magnesium sulphate and concentrated. The residue was chromatographed on silica gel with ethyl acetate/hexane (1:1), whereupon, after recrystallization from ethyl acetate/hexane and drying, 3.30 g (67.6%) of [6-(tert.-butyl-dimethyl-silanyloxymethyl)-3,7-dimethoxy-10-methyl-phenothiazine-4-yl]methanol were obtained as a white solid of m.p. 46°-47°.

後処理

  1. extractionwas extracted three times with ethyl acetate
  2. washThe combined organic phases were washed with saturated sodium chloride solution
  3. dry with materialdried over magnesium sulphate
  4. concentrationconcentrated
  5. customThe residue was chromatographed on silica gel with ethyl acetate/hexane (1:1), whereupon
  6. customafter recrystallization from ethyl acetate/hexane
  7. customdrying

出典と根拠

ORDレコード
ord-61bd023a24a041baae1217958ce2ca3c
出典データセット
uspto-grants-1998_09
特許番号
US05811548

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