Hydrochloric Acid → HCID 137329064, compound

HRID 2395159Notes

Reaction equation

HRID 2395159 reaction equation
C([Li])(C)(C)C.[C:6]([SiH2:10][O:11][C:12]([CH3:29])([CH3:28])[C:13]1[C:26]2[S:25][C:24]3[C:19](=[CH:20][CH:21]=[CH:22][CH:23]=3)[N:18]([CH3:27])[C:17]=2[CH:16]=[CH:15][CH:14]=1)([CH3:9])([CH3:8])[CH3:7].CN(C)CCN(C)C.[CH:38](N1CCCCC1)=[O:39].Cl>C(OCC)C>[C:6]([SiH2:10][O:11][C:12]([CH3:29])([CH3:28])[C:13]1[CH:14]=[CH:15][CH:16]=[C:17]2[C:26]=1[S:25][C:24]1[C:23]([CH2:38][OH:39])=[CH:22][CH:21]=[CH:20][C:19]=1[N:18]2[CH3:27])([CH3:9])([CH3:8])[CH3:7]

Participants

7

Reactant 5

HCID 313Hydrochloric AcidHCID 8037N,N,N',N'-TetramethylethylenediamineHCID 174291-PiperidinecarboxaldehydeHCID 131720851HCID 131720851, compoundHCID 178418306HCID 178418306, compound

Product 1

HCID 137329064HCID 137329064, compoundYield 30.1%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Procedure

36.4 ml of tert-butyllithium solution (1.4M in pentane) were slowly added dropwise under argon at -78° to a solution of 14.0 g (39.2 mmol) of 4-(tert-butyl-dimethyl-silanyloxymethyl)-10-methyl-phenothiazine and 6.39 ml of N,N,N',N'-tetramethylethylenediamine in 120 ml of diethyl ether. The reaction mixture was stirred at -78° for 30 minutes, brought slowly to room temperature, stirred for 3 hours, thereupon treated with 5.66 ml (51.0 mmol) of N-formylpiperidine, stirred at 0° for 40 minutes and then poured into 50 g of ice, 50 ml of 0.1N aqueous hydrochloric acid solution and 250 ml of diethyl ether. The aqueous phase was extracted several times with diethyl ether. The combined organic phases were dried over magnesium sulphate and concentrated. The crude 6-(tert-butyl-dimethyl-silanyloxymethyl)-10-methyl-phenothiazine-4-carbaldehyde (about 14 g) remaining as the residue was dried in a high vacuum, dissolved in 120 ml of tetrahydrofuran and treated at 0° with 50 ml of lithium borohydride solution (1N in tetrahydrofuran). The reaction mixture was stirred at room temperature for 1 hour and then poured into 100 ml of 0.1N aqueous hydrochloric acid solution, 100 g of ice and 150 ml of diethyl ether. The aqueous phase was extracted with diethyl ether and the combined organic fractions were dried over magnesium sulphate and concentrated. The residue was chromatographed on 1.3 kg of silica gel with ethyl acetate/hexane (1:4), whereupon, after drying in a high vacuum, 4.57 g (30.0%) of [6-(tert-butyl-dimethyl-silanyloxymethyl)-10-methyl-phenothiazin-4-yl]-methanol were obtained as a colourless oil. MS: 387 (M+ ; 100), 238(91), 224(24), 75(97).

Workup

  1. custombrought slowly to room temperature
  2. stirringstirred for 3 hours
  3. stirringstirred at 0° for 40 minutes
  4. extractionThe aqueous phase was extracted several times with diethyl ether
  5. dry with materialThe combined organic phases were dried over magnesium sulphate
  6. concentrationconcentrated
  7. customwas dried in a high vacuum
  8. dissolutiondissolved in 120 ml of tetrahydrofuran
  9. additiontreated at 0° with 50 ml of lithium borohydride solution (1N in tetrahydrofuran)
  10. stirringThe reaction mixture was stirred at room temperature for 1 hour
  11. additionpoured into 100 ml of 0.1N aqueous hydrochloric acid solution, 100 g of ice and 150 ml of diethyl ether
  12. extractionThe aqueous phase was extracted with diethyl ether
  13. dry with materialthe combined organic fractions were dried over magnesium sulphate
  14. concentrationconcentrated
  15. customThe residue was chromatographed on 1.3 kg of silica gel with ethyl acetate/hexane (1:4), whereupon
  16. customafter drying in a high vacuum

Sources & evidence

ORD record
ord-36e41a43f45a4fe093533341bb7043d9
Source dataset
uspto-grants-1998_09
Patent number
US05811548

Reaction notes

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