Sodium borohydride → 4-(2-Hydroxy-2-phenylethylthiomethyl)pyridine

HRID 1389796Notes

Reaction equation

HRID 1389796 reaction equation
[N:1]1[CH:6]=[CH:5][C:4]([CH2:7][S:8][CH2:9][C:10]([C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)=[O:11])=[CH:3][CH:2]=1.[BH4-].[Na+]>C(O)(C)C>[OH:11][CH:10]([C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)[CH2:9][S:8][CH2:7][C:4]1[CH:3]=[CH:2][N:1]=[CH:6][CH:5]=1

Participants

4

Reactant 2

HCID 4311764Sodium borohydrideHCID 13490316Alpha-(4-Picolylthio)acetophenone

Product 1

HCID 202712964-(2-Hydroxy-2-phenylethylthiomethyl)pyridineYield 71%

Reagents, catalysts & solvents 1

HCID 3776IsopropanolSolvent

Procedure

Under a nitrogen atmosphere, alpha-(4-picolylthio)acetophenone (852 mg., 3.5 mmoles) was dissolved in 8.75 ml. of isopropyl alcohol. Sodium borohydride (54 mg., 1.4 mmoles, 1.6 equiv.) was added. After stirring for 0.5 hour at room temperature, the reaction mixture was refluxed for 1 hour. The reaction mixture was cooled somewhat and then evaporated to an oil. With stirring, hydrochloric acid (4 N, 10 ml.) was added slowly to the oil, so as to control heating and foaming. Once addition was complete and there was no evidence of gas evolution, the acid solution was made strongly basic with 20% sodium hydroxide. The oil which precipiated was extracted into chloroform. The chloroform was back-washed with dilute sodium hydroxide, dried over anhydrous sodium sulfate and concentrated to an oil (0.87 g.) which crystallized to a waxy solid on standing. The solid was triturated with ether and filtered to yield crude product (0.61 g.). Recrystallization from ethyl acetate gave purified 4-(2-hydroxy-2-phenylethylthiomethyl)pyridine [0.42 g.; m.p. 116.5°- 119° C. (incomplete); ir (KBr): 3.17, 5.1-5.8, 6.22, 6.88, 9.49, 12.25, 13.88 and 14.25μ; mass spectra: m/e calcd.: 245, found: 245; pnmr/CDCl3 /TMS/δ: 8.73-8.37 (m, 2H), 7.57-7.10 (m, 7H), 4.75 (t, 1H), 3.63 (s, 2H), 3.10 (s, 1H, exchanges with D2O) and 2.72 (d, 2H)].

Workup

  1. temperaturethe reaction mixture was refluxed for 1 hour
  2. temperatureThe reaction mixture was cooled somewhat
  3. customevaporated to an oil
  4. stirringWith stirring
  5. additionhydrochloric acid (4 N, 10 ml.) was added slowly to the oil
  6. temperatureso as to control heating
  7. additionOnce addition
  8. extractionThe oil which precipiated was extracted into chloroform
  9. washThe chloroform was back-washed with dilute sodium hydroxide
  10. dry with materialdried over anhydrous sodium sulfate
  11. concentrationconcentrated to an oil (0.87 g.) which
  12. customcrystallized to a waxy solid
  13. customThe solid was triturated with ether
  14. filtrationfiltered

Sources & evidence

ORD record
ord-4f2c7f80789f400f9f6100dcbbdf6ea7
Source dataset
uspto-grants-1981_01
Patent number
US04246263

Reaction notes

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