Sodium Nitrite → HCID 131714703, compound

HRID 1981665Notes

Reaction equation

HRID 1981665 reaction equation
[N:1]([O-:3])=O.[Na+].[OH:5][CH:6]([CH3:31])[CH2:7][N:8]([CH:15]([OH:30])[C@H:16]1[O:22][C:20]([CH2:23][CH:24]([CH3:26])[CH3:25])([OH:21])[C@H:19]([OH:27])[C@@H:18]([OH:28])[C@@H:17]1[OH:29])[C:9](=[O:14])[NH:10][CH2:11][CH2:12][Cl:13]>C(O)C.C(O)(=O)C>[OH:5][CH:6]([CH3:31])[CH2:7][N:8]([CH:15]([OH:30])[C@H:16]1[O:22][C@:20]([CH2:23][CH:24]([CH3:25])[CH3:26])([OH:21])[C@H:19]([OH:27])[C@@H:18]([OH:28])[C@@H:17]1[OH:29])[C:9](=[O:14])[N:10]([CH2:11][CH2:12][Cl:13])[N:1]=[O:3]

Participants

5

Reactant 2

HCID 23668193Sodium NitriteHCID 131714704HCID 131714704, compound

Product 1

HCID 131714703HCID 131714703, compoundYield 28.5%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 702EthanolSolvent

Procedure

Sodium nitrite (2 g) was added to a solution of the above fractionated α,β-mixed form of 3-(2-hydroxy-n-propyl)-3-(isobutyl D-glucopyranose-6-yl)-1-(2-chloroethyl)urea (4.48 g, 11.7 mmol) in a mixture of ethanol (60 ml) and 80% aqueous acetic acid (30 ml) with well stirring at 0° to 5° C. spending 30 minutes. This reaction mixture was allowed to stand in a refrigerator at 0° to 5° C. for 18 hours to complete reaction, which was confirmed by TLC. An ion exchange resin (H+ form, registered trade mark: Amberlite IR-120) (20 ml) was added to the reaction mixture and the mixture was stirred at 0° to 5° C. for 1 hour. The ion exchange resin was filtered off, and the filtrate was vacuum-concentrated at 25° C. and fractionated by column chromatography (packing: Kiesel gel 60; eluent: chloroform/ethanol 9:1) to separate the α- and β-forms. Each fractionated solution was vacuum-concentrated at 25° C. and crystallized from ether and petroleum ether. Thus, there were obtained 1.43 g of 3-(2-hydroxy-n-propyl)-3-(isobutyl α-D-glucopyranose-6-yl)-1-(2-chloroethyl)-1-nitrosourea; yield 28.5%, m.p. 62°-64° C., [α]D20 +66.9° (C 1.0, methanol); and 1.14 g of 3-(2-hydroxy-n-propyl)-3-(isobutyl β-D-glucopyranose-6-yl)-1-(2-chloroethyl)-1-nitrosourea; yield 22.7%, m.p. 80°-82° C., [α]D20 -12.5° (C 1.0, methanol).

Workup

  1. customto stand in a refrigerator at 0° to 5° C. for 18 hours to complete reaction, which
  2. additionAn ion exchange resin (H+ form, registered trade mark: Amberlite IR-120) (20 ml) was added to the reaction mixture
  3. stirringthe mixture was stirred at 0° to 5° C. for 1 hour
  4. filtrationThe ion exchange resin was filtered off
  5. concentrationthe filtrate was vacuum-concentrated at 25° C. and fractionated by column chromatography (packing: Kiesel gel 60; eluent: chloroform/ethanol 9:1)
  6. customto separate the α- and β-forms
  7. concentrationEach fractionated solution was vacuum-concentrated at 25° C.
  8. customcrystallized from ether and petroleum ether

Sources & evidence

ORD record
ord-533f4ca1937848898aff43baaf2631ae
Source dataset
uspto-grants-1986_06
Patent number
US04593090

Reaction notes

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