Hexane → (2E,4E,6E)-Ethyl 7-(3-propoxy-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalen-2-yl)-6-fluoro-3-methylnona-2,4,6-trienoate

HRID 1744915ノート

反応式

HRID 1744915 の反応式
C([Li])CCC.CCCCCC.C(OP([CH2:20][C:21]([CH3:28])=[CH:22][C:23]([O:25][CH2:26][CH3:27])=[O:24])(OCC)=O)C.[CH2:29]([O:32][C:33]1[C:34](/[C:47](/[CH2:52][CH3:53])=[C:48](/[F:51])\[CH:49]=O)=[CH:35][C:36]2[C:37]([CH3:46])([CH3:45])[CH2:38][CH2:39][C:40]([CH3:44])([CH3:43])[C:41]=2[CH:42]=1)[CH2:30][CH3:31]>C1COCC1.CN1CCCN(C)C1=O>[CH2:29]([O:32][C:33]1[C:34](/[C:47](/[CH2:52][CH3:53])=[C:48](/[F:51])\[CH:49]=[CH:20]\[C:21](\[CH3:28])=[CH:22]\[C:23]([O:25][CH2:26][CH3:27])=[O:24])=[CH:35][C:36]2[C:37]([CH3:46])([CH3:45])[CH2:38][CH2:39][C:40]([CH3:44])([CH3:43])[C:41]=2[CH:42]=1)[CH2:30][CH3:31]

参加物

7

反応物 4

HCID 8058HexaneHCID 2773818Ethyl 4-(diethoxyphosphoryl)-3-methylcrotonateHCID 22226104(E)-3-(3-Propoxy-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalen-2-yl)-2-fluoropent-2-enal2 回HCID 178418339Butyllithium

生成物 1

HCID 22226101(2E,4E,6E)-Ethyl 7-(3-propoxy-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalen-2-yl)-6-fluoro-3-methylnona-2,4,6-trienoate

試薬・触媒・溶媒 2

HCID 8028Tetrahydrofuran溶媒2 回HCID 816462(1H)-Pyrimidinone, tetrahydro-1,3-dimethyl-溶媒

反応条件

温度
0 °C

実験手順

A solution of n-butyl lithium and hexane (6.75 mL, 1.6 M, 10.8 mmol) was added over 20 minutes down the side of the flask into a stirring solution of ethyl 4-(diethoxyphosphoryl)-3-methylbut-2-enoate (2.86 g, 10.8 mmol) and THF (40 mL) and 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone (0.70 mL) at −78° C. After 30 min, the solution was treated with a solution of (E)-3-(3-propoxy-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalen-2-yl)-2-fluoropent-2-enal (Intermediate 9, 1.80 g, 5.42 mmol) in THF (10 mL). The solution was stirred for 2 h at 0° C. and then cooled again to −78° C. The reaction was quenched at −78° C. by adding saturated aqueous ammonium chloride. The solution was warmed to room temperature, and the products were extracted three times with ether. The combined organic layers were washed with water, brine and dried over magnesium sulfate. The solvent was removed in vacuo to give the title compound after purification by silica gel chromatography using a 94:6 mixture of hexane:ethyl acetate.

後処理

  1. temperaturecooled again to −78° C
  2. customThe reaction was quenched at −78° C.
  3. additionby adding saturated aqueous ammonium chloride
  4. temperatureThe solution was warmed to room temperature
  5. extractionthe products were extracted three times with ether
  6. washThe combined organic layers were washed with water, brine
  7. dry with materialdried over magnesium sulfate
  8. customThe solvent was removed in vacuo

出典と根拠

ORDレコード
ord-3f4fca079bdd40f6b901d45f50a56a68
出典データセット
uspto-grants-2006_03
特許番号
US07019034B2

反応ノート

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