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

HRID 2395176

Reaktionsgleichung

Reaktionsgleichung von HRID 2395176
[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]

Komponenten

8

Edukt 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

Produkt 1

HCID 137329065[6-(Tert.-butyl-dimethyl-silanyloxymethyl)-3,7-dimethoxy-10-methyl-phenothiazine4-yl]methanolAusbeute 67,6 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 8028TetrahydrofuranLösungsmittelHCID 21868444Ether tetrahydrofuranLösungsmittel

Versuchsvorschrift

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°.

Aufarbeitung

  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

Quellen und Nachweise

ORD-Eintrag
ord-61bd023a24a041baae1217958ce2ca3c
Quelldatensatz
uspto-grants-1998_09
Patentnummer
US05811548

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