p-Toluenesulfonic acid → HCID 86750150, Verbindung

HRID 233379

Reaktionsgleichung

Reaktionsgleichung von HRID 233379
[C:1]([O:9][C@@H:10]1[C@@H:23]([O:24][C@@H:25]2[O:54][C@@H:53]([CH3:55])[C@@H:44]([O:45][CH2:46][C:47]3[CH:52]=[CH:51][CH:50]=[CH:49][CH:48]=3)[C@@H:35]([O:36][CH2:37][C:38]3[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=3)[C@@H:26]2[O:27][CH2:28][C:29]2[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=2)[C@H:22]([O:56][C@@H:57]2[O:73][C@H:72]([CH2:74][O:75][C:76](=[O:83])[C:77]3[CH:82]=[CH:81][CH:80]=[CH:79][CH:78]=3)[C@H:70]([OH:71])[C@H:68]([OH:69])[C@H:58]2[O:59][C:60](=[O:67])[C:61]2[CH:66]=[CH:65][CH:64]=[CH:63][CH:62]=2)[C@@H:21]([CH2:84][O:85][C:86](=[O:93])[C:87]2[CH:92]=[CH:91][CH:90]=[CH:89][CH:88]=2)[O:20][C@H:11]1[O:12][CH2:13][C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C1(C)C=CC(S(O)(=O)=[O:101])=CC=1.C(N([CH2:110][CH3:111])CC)C>C1C=CC=CC=1.C(C(CC)(CC)C([O-])([O-])[O-])C>[C:1]([O:9][C@@H:10]1[C@@H:23]([O:24][C@@H:25]2[O:54][C@@H:53]([CH3:55])[C@@H:44]([O:45][CH2:46][C:47]3[CH:52]=[CH:51][CH:50]=[CH:49][CH:48]=3)[C@@H:35]([O:36][CH2:37][C:38]3[CH:39]=[CH:40][CH:41]=[CH:42][CH:43]=3)[C@@H:26]2[O:27][CH2:28][C:29]2[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=2)[C@H:22]([O:56][C@@H:57]2[O:73][C@H:72]([CH2:74][O:75][C:76](=[O:83])[C:77]3[CH:78]=[CH:79][CH:80]=[CH:81][CH:82]=3)[C@H:70]([O:71][C:110](=[O:101])[CH3:111])[C@H:68]([OH:69])[C@H:58]2[O:59][C:60](=[O:67])[C:61]2[CH:62]=[CH:63][CH:64]=[CH:65][CH:66]=2)[C@@H:21]([CH2:84][O:85][C:86](=[O:93])[C:87]2[CH:88]=[CH:89][CH:90]=[CH:91][CH:92]=2)[O:20][C@H:11]1[O:12][CH2:13][C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)(=[O:8])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Komponenten

6

Edukt 3

HCID 6101p-Toluenesulfonic acidHCID 8471TriethylamineHCID 22868658HCID 22868658, Verbindung

Produkt 1

HCID 86750150HCID 86750150, VerbindungAusbeute 96,6 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 241BenzeneLösungsmittelHCID 21875354TriethylorthoaceateLösungsmittel

Versuchsvorschrift

Compound 10b (0.56 g) was dissolved in a mixture of benzene (30 mL) and triethylorthoacetate (30 mL), containing 4-toluenesulfonic acid (0.15 g), and the mixture stirred for 1 h at room temperature. The acid was neutralized with a little triethylamine, and the mixture evaporated to dryness. It was then taken in 80% aqueous acetic acid (50 mL) and stirred for 40 min at room temperature. T.l.c. (4:1 toluene-ethyl acetate) showed the presence of a major product,faster-migrating than diol 10b. The acetic acid was removed under diminished pressure, and several portion of toluene were added to, and evaporated from the residue to furnish 11b (0.56 g, 96.6%) as an amorphous solid, [α]D -14.3° (c,1.1, chloroform). 1H NMR (CDCl3): δ8.20-7.00 (m, 40 H, arom.), 5.51 (t, 1 H, J 8.0 Hz, H-2'), 5.38 (d, 1 H, J 3.8 Hz, H-1 fuc), 5.30 (d, 1 H, J 3.8 Hz, H-4'), 5.20 (dd, 1 H, J 8.1 and 10.0 Hz, H-2), 4.62 (d, 1 H, J 8.2 Hz, H-1), 4.44 (d, 1 H, J 7.9 Hz, H-1'), 1.82 (s, 3 H, CH3CO), and 1.34 (d, 3 H, J 6.4 Hz, H-6 fuc). 13C NMR (CDCl3): δ170.38 (CH3CO), 166.15, 165.72, 165.57, 164.56 (4×PhCO), 100.45, 99.23 (C-1, C-1'), 97.54 C-1 fuc), 79.48 (C-3), 77.57 (C-4), 74.08, 72.94, 72.70, 70.15 (4×PhCH2), 62.54, 60.78 (C-6, C-6'), 20.59 (CH3CO), and 16.88 (C-6 fuc); positive ion LSIMS: 1307.1 (M+H)+), 1200.8 (M-OBn)+, negative ion LSIMS: 1460.9 (M+mNBA)-, 1353.6 (M+NO2)-, 1306.8 (M-H)-.

Aufarbeitung

  1. customthe mixture evaporated to dryness
  2. stirringstirred for 40 min at room temperature
  3. customThe acetic acid was removed under diminished pressure, and several portion of toluene
  4. additionwere added to, and
  5. customevaporated from the residue

Quellen und Nachweise

ORD-Eintrag
ord-00491fa86f9d4e2f925b372ccd963a83
Quelldatensatz
uspto-grants-1997_01
Patentnummer
US05591835

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