Phosphine, triphenyl-, hydrobromide → Zeinoxanthin

HRID 1981984

반응식

HRID 1981984 반응식
[Br-].C1([PH+](C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[CH3:21][C:22]1[CH2:27][CH2:26][CH2:25][C:24]([CH3:29])([CH3:28])[C:23]=1/[CH:30]=[CH:31]/[C:32](/[CH3:61])=[CH:33]/[CH:34]=[CH:35]/[C:36](/[CH3:60])=[CH:37]/[CH:38]=[CH:39]/[CH:40]=[C:41](/[CH:43]=[CH:44]/[CH:45]=[C:46](/[CH:48]=[CH:49]/[C:50]1[C:55]([CH3:57])([CH3:56])[CH2:54][C@H:53]([OH:58])[CH2:52][C:51]=1[CH3:59])\[CH3:47])\[CH3:42]>O1C(CC)C1.CC1C[C@@H](O)CC(C)(C)C=1/C=C/C(/C)=C/C=C/C(/C)=C/C=C/C=C(\C)/C=C/C=C(\C)/C=C/C1C(C)(C)C[C@H](O)CC=1C>[CH3:59][C:51]1[CH2:52][C@@H:53]([OH:58])[CH2:54][C:55]([CH3:56])([CH3:57])[C:50]=1/[CH:49]=[CH:48]/[C:46](/[CH3:47])=[CH:45]/[CH:44]=[CH:43]/[C:41](/[CH3:42])=[CH:40]/[CH:39]=[CH:38]/[CH:37]=[C:36](/[CH:35]=[CH:34]/[CH:33]=[C:32](/[CH:31]=[CH:30]/[C@@H:23]1[C:24]([CH3:29])([CH3:28])[CH2:25][CH2:26][CH:27]=[C:22]1[CH3:21])\[CH3:61])\[CH3:60]

참가 물질

5

반응물 2

HCID 517696Phosphine, triphenyl-, hydrobromideHCID 5281235Cryptoxanthin

생성물 1

HCID 5281234Zeinoxanthin

시약·촉매·용매 2

HCID 78341,2-Epoxybutane용매2회HCID 5280899Zeaxanthin용매

실험 절차

The ketone 1 prepared from isophorone is reacted with a Grignard reagent prepared from but-3-yn-2-ol to give the diol 2, from which the dihydroxyketone 3 is formed by eliminating the ethylenedioxy protective group. The dihydroxyketone 3 can be reduced with lithium aluminum hydride to the triol 4, which can be reacted with acetic anhydride in pyridine to give the acetate 5. Dehydration of 5 with phosphoryl chloride in pyridine gives the enyne diacetate 7, which can be reduced with lithium aluminum hydride to the enynediol 6 and, when the reaction is carried out under more stringent conditions, to 3-hydroxy-β-ionol. Selective oxidation of 8 with manganese dioxide gives 3-hydroxy-β-ionone 9. Reaction of the latter with vinyl magnesium bromide gives the vinyl alcohol 10, which, when treated with triphenylphosphonium bromide, forms the Wittig reagent 11. When the latter is heated with the dialdehyde 12 in 1,2-epoxybutane, zeaxanthin 14 is obtained in good yield. Condensation of the Wittig salt 11 with (C25 -)-β-apo-12'-carotenal 16 in 1,2-epoxybutane gives β-cryptoxanthin 18, or condensation of 11 with racemic (C25 -)-α-apo-12'-carotenal gives zeinoxanthin 17. Equation 1 below illustrates the synthetic route described:

후처리

  1. customis obtained in good yield
  2. customgives

출처 및 근거

ORD 기록
ord-fe45a8443881482fb3fe263a4bcee634
출처 데이터셋
uspto-grants-1986_06
특허 번호
US04594456

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