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p-Toluenesulfonic acid → Benzyl 2.6-di-O-benzoyl-4-O-(4-O-acetyl-2,6-di-O-benzoyl-beta-D-galactopyranosyl)-3-O-(2,3,4-tri-O-benzyl-alpha-L-fucopyranosyl)-beta-D-glucopyranoside

HRID 233379
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HRID 233379 반응식
[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
참가 물질실험 절차후처리출처 및 근거반응 노트

참가 물질

6

반응물 3

HCID 6101p-Toluenesulfonic acidHCID 8471TriethylamineHCID 22868658Benzyl 2,6-di-O-benzoyl-3-O-(2,3,4-tri-O-benzyl-alpha-L-fucopyranosyl)-4-O-(2,6-di-O-benzoyl-beta-D-galactopyranosyl)-beta-D-glucopyranoside

생성물 1

HCID 86750150Benzyl 2.6-di-O-benzoyl-4-O-(4-O-acetyl-2,6-di-O-benzoyl-beta-D-galactopyranosyl)-3-O-(2,3,4-tri-O-benzyl-alpha-L-fucopyranosyl)-beta-D-glucopyranoside
수율 96.6%

시약·촉매·용매 2

HCID 241Benzene용매HCID 21875354Triethylorthoaceate용매

실험 절차

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)-.

후처리

  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

출처 및 근거

ORD 기록
ord-00491fa86f9d4e2f925b372ccd963a83
출처 데이터셋
uspto-grants-1997_01
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US05591835

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