6-Octenal, 3,7-dimethyl-, (3R)- → Citronellol

HRID 1392895

반응식

HRID 1392895 반응식
[H-].[H-].[H-].[H-].[Li+].[Al+3].[CH3:7][C:8](=[CH:10][CH2:11][CH2:12][C@H:13]([CH2:15][CH:16]=[O:17])[CH3:14])[CH3:9]>C1COCC1>[CH3:7][C:8](=[CH:10][CH2:11][CH2:12][CH:13]([CH2:15][CH2:16][OH:17])[CH3:14])[CH3:9]

참가 물질

4

반응물 2

HCID 754276-Octenal, 3,7-dimethyl-, (3R)-HCID 21226445Aluminium lithium hydride

생성물 1

HCID 8842Citronellol수율 114.6%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매

반응 조건

온도
0 °C

실험 절차

Powdered LiAlH4 (12.5 g, 329 mmol) was introduced into a 5 L round bottom flask along with 2 L of THF (dried over 3 Å molecular sieve). The slurry was stirred mechanically under N2 and the temperature was lowered to 0° C. (R)-citronellal (5, Takasago, Rockleigh, N.J.) (100 g, 648 mmol) was added neat over about 15 min and the residue was rinsed into the flask with an additional 500 mL of THF. Notwithstanding the fact that TLC indicated complete consumption of citronellal, the mixture was warmed to a gentle reflux and subsequently cooled to 0° C. The reaction was worked up by sequential dropwise addition of the following to the vigorously stirring mixture: 12.5 mL water, 12.5 mL 3 M NaOH, and a solution of 37.5 mL water in 37.5 mL THF. After filtration through celite and thorough washing of the solids with MTBE, the solvent was evaporated to yield 116 g of crude citronellol. This oil was distilled (bulb-to-bulb, 120-140° C., 0.8 mm Hg) to give 6 (93.4 g, 92%) as a clear oil, TLC Rf (10% MTBE/petroleum ether) =0.09. 1H NMR (CDCl3) (δ): 5.10 (m, 1H), 3.66 (m, 2H), 2.1-1.8 (m, 3H), 1.68 (s, 3H), 1.7-1.5 (m, 2H), 1.60 (s, 3H), 1.4-1.3 (m, 2H), 1.17 (m, 1H), 0.90 (d, J=6.66 Hz, 3H); 13C NMR (CDCl3) (δ): u: 131.2, 61.0, 39.8, 37.1, 25.4; d: 124.6, 29.1, 25.6, 19.4, 17.6; IR (cm−1): 3331 (b), 2927, 1454, 1377, 1058; MS (m/z, %): 55 (64), 69 (100), 82 (44), 95 (33), 109 (14), 123 (18), 138 (6), 156 (6); HRMS calcd for C10H20O: 156.1514. Found: 156.1514; [α]D17=+3.74 (c 1.02, EtOH).

후처리

  1. customwas lowered to 0° C.
  2. additionwas added neat over about 15 min
  3. washthe residue was rinsed into the flask with an additional 500 mL of THF
  4. customconsumption of citronellal
  5. temperaturethe mixture was warmed to
  6. temperaturea gentle reflux
  7. additionThe reaction was worked up by sequential dropwise addition of the following to the
  8. stirringvigorously stirring mixture
  9. filtrationAfter filtration through celite
  10. washthorough washing of the solids with MTBE
  11. customthe solvent was evaporated

출처 및 근거

ORD 기록
ord-804c686b3186439c96d0665994d47f1c
출처 데이터셋
uspto-grants-2008_03
특허 번호
US07345035B2

연결된 노트

불러오는 중…