M-Cresol → 2-Hydroxy-4-methylbenzonitrile

HRID 8915

반응식

HRID 8915 반응식
B(Cl)(Cl)Cl.[CH:5]1[C:10]([OH:11])=[CH:9][CH:8]=[CH:7][C:6]=1[CH3:12].CS[C:15]#[N:16].[Al+3].[Cl-].[Cl-].[Cl-]>ClCCCl>[OH:11][C:10]1[CH:5]=[C:6]([CH3:12])[CH:7]=[CH:8][C:9]=1[C:15]#[N:16]

참가 물질

6

반응물 4

HCID 342M-CresolHCID 11168Methyl thiocyanateHCID 25135Boron TrichlorideHCID 6451240Aluminum(III) Chloride

생성물 1

HCID 143886562-Hydroxy-4-methylbenzonitrile수율 91.1%

시약·촉매·용매 1

HCID 111,2-Dichloroethane용매

반응 조건

온도
80 °C

실험 절차

2-Hydroxy-4-methylbenzonitrile was prepared following a modification of the procedure reported by Makoto Adachi and Tsutomu Sugasawa (Synthetic Communications 1990, 20, 71–84.). To a cold (0° C.) solution of BCl3 (1.0 M in heptane, 12.0 mL, 12.0 mmol) in 1,2-dichloroethane was added neat m-cresol (1.00 mL, 9.56 mmol) followed by CH3SCN (0.83 mL, 12.1 mmol) and AlCl3 (1.38 g, 10.4 mmol). The cooling bath was removed and the resultant mixture was heated to 80° C. for 3 hours then cooled to room temperature. The mixture was poured into 4 N NaOH (35 mL) and the mixture was heated at 80° C. for 45 minutes then cooled to room temperature. The phases were separated and the aqueous phase was extracted with CH2Cl2 (3×50 mL). The aqueous phase was acidified with 6 N HCl (30 mL) and extracted with diethyl ether (3×50 mL). The combined ether extracts were dried (MgSO4) and concentrated. Purification of the crude material by column chromatography on silica gel (20:1 CH2Cl2—EtOAc) provided 1.16 g (91%) of 2-Hydroxy-4-methylbenzonitrile as a white solid. 1H NMR (CDCl3) δ 2.36 (s, 3H), 6.20 (br s, 1H), 6.79–6.81 (m, 2H), 7.38 (d, 1H, J=9 Hz).

후처리

  1. custom2-Hydroxy-4-methylbenzonitrile was prepared
  2. customThe cooling bath was removed
  3. temperaturethen cooled to room temperature
  4. additionThe mixture was poured into 4 N NaOH (35 mL)
  5. temperaturethe mixture was heated at 80° C. for 45 minutes
  6. temperaturethen cooled to room temperature
  7. customThe phases were separated
  8. extractionthe aqueous phase was extracted with CH2Cl2 (3×50 mL)
  9. extractionextracted with diethyl ether (3×50 mL)
  10. dry with materialThe combined ether extracts were dried (MgSO4)
  11. concentrationconcentrated
  12. customPurification of the crude material by column chromatography on silica gel (20:1 CH2Cl2—EtOAc)

출처 및 근거

ORD 기록
ord-1460cafe3e734ae289235f35d72669f6
출처 데이터셋
uspto-grants-2006_08
특허 번호
US07091217B2

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