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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
ノート
印刷プレビュー

反応式

HRID 233379 の反応式
[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
参加物実験手順後処理出典と根拠反応ノート

参加物

6

反応物 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

生成物 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
収率 96.6%

試薬・触媒・溶媒 2

HCID 241Benzene溶媒HCID 21875354Triethylorthoaceate溶媒

実験手順

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)-.

後処理

  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

出典と根拠

ORDレコード
ord-00491fa86f9d4e2f925b372ccd963a83
出典データセット
uspto-grants-1997_01
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US05591835

反応ノート

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