Water → [5-(4-Hydroxy-2,6,6-trimethyl-1-cyclohexen-1-yl)-3-methyl-2,4-pentadienyl]triphenylphosphonium chloride

HRID 463911

反応式

HRID 463911 の反応式
O.[Cl-:2].[OH:3][C@H:4]1[CH2:9][C:8]([CH3:11])([CH3:10])[C:7]([C:12]#[C:13]/[C:14](/[CH3:36])=[CH:15]/[CH2:16][P+:17]([C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=2)([C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)[C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)=[C:6]([CH3:37])[CH2:5]1.[H][H]>CO.OCCSCCSCCO>[Cl-:2].[OH:3][CH:4]1[CH2:9][C:8]([CH3:11])([CH3:10])[C:7]([CH:12]=[CH:13][C:14]([CH3:36])=[CH:15][CH2:16][P+:17]([C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=2)([C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[C:24]2[CH:25]=[CH:26][CH:27]=[CH:28][CH:29]=2)=[C:6]([CH3:37])[CH2:5]1

参加物

6

反応物 3

HCID 962WaterHCID 10896556Phosphonium, ((2E)-5-((4R)-4-hydroxy-2,6,6-trimethyl-1-cyclohexen-1-yl)-3-methyl-2-penten-4-ynyl)triphenyl-, chlorideHCID 178418361HCID 178418361、化合物2 回

生成物 1

HCID 73090609[5-(4-Hydroxy-2,6,6-trimethyl-1-cyclohexen-1-yl)-3-methyl-2,4-pentadienyl]triphenylphosphonium chloride収率 84.7%

試薬・触媒・溶媒 2

HCID 78904Dithiaoctanediol触媒HCID 887Methanol溶媒2 回

実験手順

A suspension of 46.6 g of water-moist Raney-nickel and 518 mg of 1,2-bis(2-hydroxyethylthio)ethane in 1 l of methanol was pre-hydrogenated at 30° C. under normal pressure in a sulphonation flask provided with a gasification stirrer. Subsequently, a solution of 320 g of (4R,2E)-[5-(4-hydroxy-2,6,6-trimethyl-1-cyclohexen-1-yl)-3-methyl-2-penten-4-ynyl]triphenylphosphonium chloride in 2.1 l of methanol was added thereto and the mixture was hydrogenated at 40° C. and 1.1 bar of hydrogen. 15.6 l of hydrogen were taken up within 5 hours. The catalyst was filtered off and the filtrate was concentrated to a weight of 575 g. The product was crystallized by slowly pouring in 9.6 l of ethyl acetate. The suspension was stirred at room temperature for 2 hours and filtered. The crystals were washed with a small amount of methanol/ethyl acetate and dried at 60° C./0.01 mbar, there being obtained 272.2 g (84.7%) of [5-(4-hydroxy-2,6,6-trimethyl-1-cyclohexen-1-yl)-3-methyl-2,4-pentadienyl]triphenylphosphonium chloride (containing 97% of the (4R,2E,4Z)-isomer and 2% of the (4R,2Z,4Z)-isomer in accordance with HPLC) of melting point 211°-212° C. and [α]D20 =-26.2° (c=1, chloroform).

後処理

  1. customwas pre-hydrogenated at 30° C. under normal pressure in a sulphonation flask
  2. customprovided with a gasification stirrer
  3. customwas hydrogenated at 40° C.
  4. filtrationThe catalyst was filtered off
  5. concentrationthe filtrate was concentrated to a weight of 575 g
  6. customThe product was crystallized
  7. additionby slowly pouring in 9.6 l of ethyl acetate
  8. filtrationfiltered
  9. washThe crystals were washed with a small amount of methanol/ethyl acetate
  10. customdried at 60° C./0.01 mbar, there

出典と根拠

ORDレコード
ord-0c47e3291b114f7dbdf6ed48fab6c4a3
出典データセット
uspto-grants-1985_10
特許番号
US04544770

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