Benzene → HCID 131714688, compound

HRID 1981656Notes

Reaction equation

HRID 1981656 reaction equation
[CH3:1][CH:2]([NH:6][CH2:7][C@H:8]1[O:22][C@H:12]([O:13]CCC2C=CC=CC=2)[C@@H:11]([OH:23])[C@H:10]([OH:24])[C@@H:9]1[OH:25])[CH2:3][O:4][CH3:5].O1CCO[CH2:28][CH2:27]1.[CH:32]1[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1.[Cl:38][CH2:39][CH2:40][N:41]([N:54]=[O:55])[C:42](=O)[O:43]C1C=CC([N+]([O-])=O)=CC=1.C[OH:57]>CC(C)=O.C(OC(C)C)(C)C>[CH3:1][CH:2]([N:6]([CH:7]([OH:57])[C@H:8]1[O:22][C@:12]([CH2:27][CH2:28][C:32]2[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=2)([OH:13])[C@@H:11]([OH:23])[C@H:10]([OH:24])[C@@H:9]1[OH:25])[C:42](=[O:43])[N:41]([CH2:40][CH2:39][Cl:38])[N:54]=[O:55])[CH2:3][O:4][CH3:5]

Participants

8

Reactant 5

HCID 241BenzeneHCID 887MethanolHCID 312751,4-DioxaneHCID 415054-Nitrophenyl (2-chloroethyl)nitrosocarbamateHCID 53813387HCID 53813387, compound

Product 1

HCID 131714688HCID 131714688, compoundYield 65.8%

Reagents, catalysts & solvents 2

HCID 180AcetoneSolventHCID 7914Diisopropyl EtherSolvent

Procedure

A solution of β-phenylethyl 6-(1-methyl-2-methoxyethylamino)-6-deoxy-α-D-altropyranoside (6.65 g, 18.7 mmol) in a mixture of methanol (30 ml), dioxane (20 ml), and benzene (10 ml) was dropped into a solution of p-nitrophenyl N-(2-chloroethyl)-N-nitrosocarbamate (5.64 g, 20.6 mmol) in a mixture of acetone (50 ml) and isopropyl ether (20 ml) with well stirring at 0° to 5° C. spending 5 minutes, and reaction was continued for further 2 hours at the same temperature. After confirmation by TLC that the reaction was finished, the reaction mixture was vacuum-concentrated at 25° C. and fractionated by column chromatography (packing: Kiesel gel 60; eluent: chloroform→chloroform/methanol 39:1) to separate the objective product of α-form. The objective fractionated solution was vacuum-concentrated at 25° C. and crystallized from methanol and water, giving 6.03 g of 3-(1-methyl-2-methoxyethyl)-3-(β-phenylethyl α-D-altropyranose-6-yl)-1-(2-chloroethyl)-1 -nitrosourea; yield 65.8%, m.p. 55°-57° C., [α]D20 +17.8° (C 1.0, methanol).

Workup

  1. customreaction
  2. waitwas continued for further 2 hours at the same temperature
  3. concentrationthe reaction mixture was vacuum-concentrated at 25° C. and fractionated by column chromatography (packing: Kiesel gel 60; eluent: chloroform→chloroform/methanol 39:1)
  4. customto separate the objective product of α-form
  5. concentrationThe objective fractionated solution was vacuum-concentrated at 25° C.
  6. customcrystallized from methanol and water

Sources & evidence

ORD record
ord-a3396b5dfc4145b9aea97690321c3262
Source dataset
uspto-grants-1986_06
Patent number
US04593090

Reaction notes

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