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Hydrazine hydrate (1:1) → 2-(Octadecylthio)ethyl 2-acetamido-2-deoxy-3,6-di-O-acetyl-4-O-[2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-alpha-D-galactopyranosyl)-beta-D-galactopyranosyl]-beta-D-glucopyranoside

HRID 653338
ノート
印刷プレビュー

反応式

HRID 653338 の反応式
[C:1]([O:4][C@H:5]1[C@H:32]([O:33][C@@H:34]2[O:71][C@H:70]([CH2:72][O:73][C:74](=[O:76])[CH3:75])[C@H:45]([O:46][C@H:47]3[O:64][C@H:63]([CH2:65][O:66][C:67](=[O:69])[CH3:68])[C@H:58]([O:59][C:60](=[O:62])[CH3:61])[C@H:53]([O:54][C:55](=[O:57])[CH3:56])[C@H:48]3[O:49][C:50](=[O:52])[CH3:51])[C@H:40]([O:41][C:42](=[O:44])[CH3:43])[C@H:35]2[O:36][C:37](=[O:39])[CH3:38])[C@@H:31]([CH2:77][O:78][C:79](=[O:81])[CH3:80])[O:30][C@@H:7]([O:8][CH2:9][CH2:10][S:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH3:29])[C@@H:6]1[N:82]1C(=O)C2=CC=CC=[C:84]2[C:83]1=[O:92])(=[O:3])[CH3:2].C[O-].[Na+].O.NN>CO.O1CCCC1>[C:83]([NH:82][C@@H:6]1[C@@H:5]([O:4][C:1](=[O:3])[CH3:2])[C@H:32]([O:33][C@@H:34]2[O:71][C@H:70]([CH2:72][O:73][C:74](=[O:76])[CH3:75])[C@H:45]([O:46][C@H:47]3[O:64][C@H:63]([CH2:65][O:66][C:67](=[O:69])[CH3:68])[C@H:58]([O:59][C:60](=[O:62])[CH3:61])[C@H:53]([O:54][C:55](=[O:57])[CH3:56])[C@H:48]3[O:49][C:50](=[O:52])[CH3:51])[C@H:40]([O:41][C:42](=[O:44])[CH3:43])[C@H:35]2[O:36][C:37](=[O:39])[CH3:38])[C@@H:31]([CH2:77][O:78][C:79](=[O:81])[CH3:80])[O:30][C@H:7]1[O:8][CH2:9][CH2:10][S:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH3:29])(=[O:92])[CH3:84]
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 24654Hydrazine hydrate (1:1)HCID 10942334Sodium MethoxideHCID 186083192-(Octadecylthio)ethyl 3,6-di-O-acetyl-2-deoxy-2-phthalimido-4-O-[2,3,6-tri O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-alpha-D-galactopyranosyl)-beta-D-galactopyranosyl]-beta-D-glucopyranoside

生成物 1

HCID 86741645
2-(Octadecylthio)ethyl 2-acetamido-2-deoxy-3,6-di-O-acetyl-4-O-[2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-alpha-D-galactopyranosyl)-beta-D-galactopyranosyl]-beta-D-glucopyranoside
収率 52.9%

試薬・触媒・溶媒 2

HCID 887Methanol溶媒2 回HCID 8028Tetrahydrofuran溶媒

実験手順

Compound 80 (1.46 g, 1.1 mmol) was dissolved in a mixure of methanol (75 ml) and tetrahydrofuran (10 ml) by warming. The clear solution was rapidly cooled to ~40° C. and methanolic sodium methoxide (0.2 M, 5 ml) was added. The mixture was stirred at room temperature for 5 h, after which time the deacetylation was complete. (TLC; SiO2,chloroform:methanol:water 65:35:10, lower phase), neutralized by addition of acidic ion-exchange resin (Duolite C-26), filtered and evaporated. The residue was re-dissolved in refluxing methanol (50 ml) and hydrazine hydrate (0.5 g, 10 mmol) was added. The reflux was continued for 17.5 h, whereafter the solvent was evaporated. The residue was acetylated by stirring for 22 h at room temperature in a mixture of pyridine and acetic anhydride (1:1, 50 ml). After evaporation, the residue was subjected to chromatography (SiO2 -column, 5×18 cm, ethyl acetate: isooctane gradient: 2:1-4:1-ethyl acetate) which gave amorphous 83 (0.72 g, 52%) with [α]D21 +32° (c 1.1, chloroform). 1H-NMR (CDC13, Me4Si) δ 5.67 (d, 1H, J=9.5 Hz, NH), 5.58 (bd, 1H, J=3 Hz, H4"), 5.39 (dd, 1H, J=11 and 3 Hz, H3"), 5.23-5.01 (3H, H2', H2" and H3), 4.99 (d, 1H, J=3.5, H1"), 4.75 (dd, 1H, J=11 and 2.5 Hz, H3') 4.58-4.37 (5H, inter alia H1and H1'), 4.54 and 4.49 (2d, each 1H, J=8 Hz each, H1 and H1'), 4.23-3.90 (7H), 3.85-3.55 (4H), 2.69 (t, 2H, J=7 Hz, OCH2CH2S), 2.51 (t, 2H, J=7 Hz, SCH2), 2.13, 2.12, 2.11, 2.08 (4s, each 3H, MeCO), 2.075, 2.05 (2s, each 6H, MeCO), 1.99, 1.97 (2s, each 3H, MeCO), 1.66-1.20, 0.88 (t, 3H, J=6.5 Hz, CH3CH2). 13C-NMR (CDC13, Me4Si) δ 170.6 (2C), 170.4 (3C), 170.2, 170.1, 169.6, 169.0, 101.1, 101.0 (d, J each 160 Hz, C1 and C1'), 99.6 (d, J=172 Hz, C1"), 76.9, 75.9, 72.7, 72.6 (2C), 71.8, 69.1 (OCH2CH2), 68.9, 68.7, 67.8, 67.1, 67.0, 62.4 (CH2), 61.3 (CH2), 60.2 (CH2), 53.3 (C2), 32.5-28.8, 23.3 (CH3CONH), 22.7 (CH2), 20.9-20.5, 14.1.

後処理

  1. temperatureby warming
  2. temperatureThe clear solution was rapidly cooled to ~40° C.
  3. filtrationfiltered
  4. customevaporated
  5. dissolutionThe residue was re-dissolved
  6. additionwas added
  7. waitThe reflux was continued for 17.5 h, whereafter the solvent
  8. customwas evaporated
  9. stirringby stirring for 22 h at room temperature in a mixture of pyridine and acetic anhydride (1:1, 50 ml)
  10. customAfter evaporation

出典と根拠

ORDレコード
ord-dce3570b5005459bb4eaef0ed9b98d4b
出典データセット
uspto-grants-1987_06
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US04675392

反応ノート

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