Triphenylphosphine → (13E)-(6RS,9alpha,11alpha,15S)-6,9-epithio-11,15-bis(tetrahydropyran-2-yloxy)prost-13-enoic acid 1,3-bisstearoyloxy-2-propyl ester

HRID 1164162

Reaktionsgleichung

Reaktionsgleichung von HRID 1164162
[S:1]1[C@H:12]2[CH2:13][C@@H:14]([O:31][CH:32]3[CH2:37][CH2:36][CH2:35][CH2:34][O:33]3)[C@H:15](/[CH:16]=[CH:17]/[C@@H:18]([O:24][CH:25]3[CH2:30][CH2:29][CH2:28][CH2:27][O:26]3)[CH2:19][CH2:20][CH2:21][CH2:22][CH3:23])[C@H:11]2[CH2:10][CH:2]1[CH2:3][CH2:4][CH2:5][CH2:6][C:7]([OH:9])=[O:8].S1[C@H]2C[C@@H](O)[C@H](/C=C/[C@@H](O)CCCCC)[C@H]2CC1CCCCC(O)=O.[C:63]([O:82][CH2:83][CH:84](O)[CH2:85][O:86][C:87](=[O:105])[CH2:88][CH2:89][CH2:90][CH2:91][CH2:92][CH2:93][CH2:94][CH2:95][CH2:96][CH2:97][CH2:98][CH2:99][CH2:100][CH2:101][CH2:102][CH2:103][CH3:104])(=[O:81])[CH2:64][CH2:65][CH2:66][CH2:67][CH2:68][CH2:69][CH2:70][CH2:71][CH2:72][CH2:73][CH2:74][CH2:75][CH2:76][CH2:77][CH2:78][CH2:79][CH3:80].N1C=CC=CC=1SSC1C=CC=CN=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>O.C1(C)C(C)=CC=CC=1>[C:63]([O:82][CH2:83][CH:84]([O:8][C:7](=[O:9])[CH2:6][CH2:5][CH2:4][CH2:3][CH:2]1[S:1][C@H:12]2[CH2:13][C@@H:14]([O:31][CH:32]3[CH2:37][CH2:36][CH2:35][CH2:34][O:33]3)[C@H:15](/[CH:16]=[CH:17]/[C@@H:18]([O:24][CH:25]3[CH2:30][CH2:29][CH2:28][CH2:27][O:26]3)[CH2:19][CH2:20][CH2:21][CH2:22][CH3:23])[C@H:11]2[CH2:10]1)[CH2:85][O:86][C:87](=[O:105])[CH2:88][CH2:89][CH2:90][CH2:91][CH2:92][CH2:93][CH2:94][CH2:95][CH2:96][CH2:97][CH2:98][CH2:99][CH2:100][CH2:101][CH2:102][CH2:103][CH3:104])(=[O:81])[CH2:64][CH2:65][CH2:66][CH2:67][CH2:68][CH2:69][CH2:70][CH2:71][CH2:72][CH2:73][CH2:74][CH2:75][CH2:76][CH2:77][CH2:78][CH2:79][CH3:80]

Komponenten

8

Edukt 5

HCID 11776TriphenylphosphineHCID 650932,2'-Dipyridyl disulfideHCID 101269Glyceryl 1,3-distearateHCID 86738733(13E)-(6RS,9alpha,11alpha,15S)-6,9-epithio-11,15-dihydroxyprost-13-enoic acidHCID 86738740(13E)-(6RS,9alpha,11alpha,15S)-6,9-epithio-11,15-bis(tetrahydropyran-2-yloxy)prost-13-enoic acid

Produkt 1

HCID 86738739(13E)-(6RS,9alpha,11alpha,15S)-6,9-epithio-11,15-bis(tetrahydropyran-2-yloxy)prost-13-enoic acid 1,3-bisstearoyloxy-2-propyl esterAusbeute 19,7 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 962WaterLösungsmittelHCID 7237O-XyleneLösungsmittel

Versuchsvorschrift

Under an atmosphere of nitrogen, a mixture of 122 mg of (13E)-(6RS,9α,11α,15S)-6,9-epithio-11,15-bis(tetrahydropyran-2-yloxy)prost-13-enoic acid [prepared from (13E)-(6RS,9α,11α,15S)-6,9-epithio-11,15-dihydroxyprost-13-enoic acid (prepared as described in Example 2) by the tetrahydropyran-2-ylation procedure described in Reference Example 1], 143 mg of 1,3-bisstearoyloxy-2-propanol, prepared as described above, 75 mg of dipyridyl disulphide, 90 mg of triphenylphosphine and 3 ml of xylene was stirred at room temperature for 2 hours, then at 40° C. for 2 hours, and at 80° C. overnight. The reaction mixture was poured into water, extracted with ethyl acetate, the extract was washed with water, and a threaded aqueous solution of sodium chloride, dried over magnesium sulphate and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel using a mixture of cyclohexane and ethyl acetate (8:1) as eluent to give 51 mg of (13E)-(6RS,9α,11α,15S)-6,9-epithio-11,15-bis(tetrahydropyran-2-yloxy)prost-13-enoic acid 1,3-bisstearoyloxy-2-propyl ester having the following physical characteristic:

Aufarbeitung

  1. customprepared
  2. waitat 40° C. for 2 hours
  3. customat 80° C.
  4. customovernight
  5. extractionextracted with ethyl acetate
  6. washthe extract was washed with water
  7. dry with materiala threaded aqueous solution of sodium chloride, dried over magnesium sulphate
  8. concentrationconcentrated under reduced pressure
  9. customThe residue was purified by column chromatography on silica gel using
  10. additiona mixture of cyclohexane and ethyl acetate (8:1) as eluent

Quellen und Nachweise

ORD-Eintrag
ord-7e087dd5a6804b28ac2bbbddfdf33957
Quelldatensatz
uspto-grants-1983_01
Patentnummer
US04367237

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