p-Toluenesulfonic acid → HCID 86750150, compound

HRID 233379

Reaction equation

HRID 233379 reaction equation
[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

Participants

6

Reactant 3

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

Product 1

HCID 86750150HCID 86750150, compoundYield 96.6%

Reagents, catalysts & solvents 2

HCID 241BenzeneSolventHCID 21875354TriethylorthoaceateSolvent

Procedure

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)-.

Workup

  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

Sources & evidence

ORD record
ord-00491fa86f9d4e2f925b372ccd963a83
Source dataset
uspto-grants-1997_01
Patent number
US05591835

Linked notes

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