Diisopropylamine → (E,E)-5,9,13-Trimethyl-4,8,12-tetradecatrienoic acid, 1,1-dimethylethyl ester

HRID 727488

反応式

HRID 727488 の反応式
C(NC(C)C)(C)C.C([Li])CCC.[C:13]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])(=[O:15])[CH3:14].CN(C)P(N(C)C)(N(C)C)=O.[CH3:32]/[C:33](/[CH2:37][CH2:38]/[CH:39]=[C:40](\[CH3:47])/[CH2:41][CH2:42][CH:43]=[C:44]([CH3:46])[CH3:45])=[CH:34]\[CH2:35]Br>O1CCCC1>[CH3:32]/[C:33](/[CH2:37][CH2:38]/[CH:39]=[C:40](\[CH3:47])/[CH2:41][CH2:42][CH:43]=[C:44]([CH3:46])[CH3:45])=[CH:34]\[CH2:35][CH2:14][C:13]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15]

参加物

7

反応物 5

HCID 7912DiisopropylamineHCID 10908tert-Butyl acetateHCID 12679HexamethylphosphoramideHCID 5366048(2E,6E)-1-bromo-3,7,11-trimethyldodeca-2,6,10-trieneHCID 178418339Butyllithium

生成物 1

HCID 11782198(E,E)-5,9,13-Trimethyl-4,8,12-tetradecatrienoic acid, 1,1-dimethylethyl ester収率 65%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
0 °C

実験手順

To a solution of 9.60 mL (68.5 mmol, 1.5 eq.) of diisopropylamine in 100 mL of tetrahydrofuran (THF) at -78° C. under argon was added 28.2 mL (45.0 mmol, 1.0 eq.) of 1.6M n-butyllithium in hexanes over 20 minutes. After warming to 0° C. for 15 minutes, the solution was recooled to -78° C. and 6.05 mL (45 mmol, 1.0 eq.) of t-butyl acetate was added over 20 minutes. After an additional 15 minutes, 16.0 mL (92 mmol, 2.05 eq.) of hexamethylphosphoramide (HMPA) was added, followed by a solution of 12.53 g (45.0 mmol) of Part A(1) farnesyl bromide in 100 mL of THF over 20 minutes. The reaction was stirred at -78° C. for 2.5 hours, quenched with saturated NH4Cl and allowed to warm to room temperature. After diluting with 400 mL of ethyl acetate, the mixture was washed with four 100 mL portions of water, and 200 mL of brine, dried over MgSO4 and evaporated to provide 12.96 g of crude product as a yellow oil. Purification by flash chromatography on 1 kg of silica gel, eluted with 1:9 ethyl acetate:petroleum ether afforded 9.39 g (65%) of title compound as a pale yellow oil.

後処理

  1. customwas recooled to -78° C.
  2. customquenched with saturated NH4Cl
  3. temperatureto warm to room temperature
  4. additionAfter diluting with 400 mL of ethyl acetate
  5. washthe mixture was washed with four 100 mL portions of water, and 200 mL of brine
  6. dry with materialdried over MgSO4
  7. customevaporated
  8. customto provide 12.96 g of crude product as a yellow oil
  9. customPurification by flash chromatography on 1 kg of silica gel
  10. washeluted with 1:9 ethyl acetate

出典と根拠

ORDレコード
ord-ac7f7bb9ec234832a71f88de88c2f9cf
出典データセット
uspto-grants-1998_01
特許番号
US05712396

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