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 653338Notes

Reaction equation

HRID 653338 reaction equation
[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]

Participants

6

Reactant 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

Product 1

HCID 867416452-(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-glucopyranosideYield 52.9%

Reagents, catalysts & solvents 2

HCID 887MethanolSolvent2×HCID 8028TetrahydrofuranSolvent

Procedure

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.

Workup

  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

Sources & evidence

ORD record
ord-dce3570b5005459bb4eaef0ed9b98d4b
Source dataset
uspto-grants-1987_06
Patent number
US04675392

Reaction notes

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