a Farnesol → 1-Chloro-3,7,11-trimethyldodeca-2,6,10-triene

HRID 63807

反応式

HRID 63807 の反応式
P(Cl)(Cl)Cl.O[CH2:6][CH:7]=[C:8]([CH2:10][CH2:11][CH:12]=[C:13]([CH2:15][CH2:16][CH:17]=[C:18]([CH3:20])[CH3:19])[CH3:14])[CH3:9].P(Cl)(Cl)[Cl:22].CN(C=O)C.C([O-])(O)=O.[Na+]>O.CC(OC)(C)C.CN(C=O)C>[Cl:22][CH2:6][CH:7]=[C:8]([CH3:9])[CH2:10][CH2:11][CH:12]=[C:13]([CH3:14])[CH2:15][CH2:16][CH:17]=[C:18]([CH3:20])[CH3:19]

参加物

8

反応物 4

HCID 3327a Farnesol2 回HCID 24387Phosphorus trichlorideHCID 516892Sodium BicarbonateHCID 86609618PCl3 DMF

生成物 1

HCID 40734091-Chloro-3,7,11-trimethyldodeca-2,6,10-triene収率 92%

試薬・触媒・溶媒 3

HCID 962Water溶媒HCID 6228Dimethylformamide溶媒2 回HCID 15413tert-Butyl methyl ether溶媒

実験手順

A 3-N 100 mL flask was charged with PCl3 (2.8 mL, 31.6 mmol) and dry DMF (32 mL) then stirred at RT for 1 h. In a separate 50 mL flask, farnesol (Ex-1B-5) (10.0 g, 45.2 mmol) and DMF (10 mL) was charged. The PCl3/DMF solution was then transferred to the farnesol, solution and the resulting dark orange solution was stirred for 1 h. The reaction was quenched by addition of solid NaHCO3 (2.5 g, 63.2 mmol). The solvent was removed by high vacuum rotary evaporation to yield an oily orange residue. To the residue was added MTBE (40 mL) and water (40 mL). The aqueous phase was washed with MTBE (3×20 mL). The MTBE layers were combined, washed with brine (2×20 mL), dried over MgSO4, filtered and finally concentrated by rotary evaporation to yield 1-chloro-3,7,11-trimethyl-dodeca-2,6,10-triene (Ex-1B-6) as a yellow oil (9.89 g, 92%). 1H NMR (400 MHz, CDCl3) δ (ppm): 5.47 (broad-t, J=8.3 Hz, 1H), 5.15-5.07 (m, 2H), 4.12 (d, J=8.1 Hz, 2H), 2.18-1.95 (m, 8H), 1.75 (s, 3H), 1.70 (s, 3H), 1.62 (s, 6H).

後処理

  1. stirringthe resulting dark orange solution was stirred for 1 h
  2. customThe solvent was removed by high vacuum rotary evaporation
  3. customto yield an oily orange residue
  4. washThe aqueous phase was washed with MTBE (3×20 mL)
  5. washwashed with brine (2×20 mL)
  6. dry with materialdried over MgSO4
  7. filtrationfiltered
  8. concentrationfinally concentrated by rotary evaporation

出典と根拠

ORDレコード
ord-20f954d2daf74c78bbee280c80666baf
出典データセット
uspto-grants-2016_09
特許番号
US09447006B2

関連ノート

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