Ammonia → (1SR,2RS)-2-(hydroxymethyl)-1-(3-nitrophenyl)cyclopropanecarboxamide

HRID 1422599Notes

Reaction equation

HRID 1422599 reaction equation
[N+:1]([C:4]1[CH:5]=[C:6]([C:10]23[CH2:15][CH:14]2[CH2:13][O:12][C:11]3=[O:16])[CH:7]=[CH:8][CH:9]=1)([O-:3])=[O:2].[NH3:17]>>[OH:12][CH2:13][CH:14]1[CH2:15][C:10]1([C:6]1[CH:7]=[CH:8][CH:9]=[C:4]([N+:1]([O-:3])=[O:2])[CH:5]=1)[C:11]([NH2:17])=[O:16]

Participants

3

Reactant 2

HCID 222AmmoniaHCID 71183845HCID 71183845, compound

Product 1

HCID 71184082(1SR,2RS)-2-(hydroxymethyl)-1-(3-nitrophenyl)cyclopropanecarboxamideYield 85.9%

Conditions

Temperature
60 °C

Procedure

A mixture of (1SR,5RS)-1-(3-nitrophenyl)-3-oxabicyclo[3.1.0]hexan-2-one (intermediate B5a) (11.47 g, 52.3 mmol, Eq: 1.00) in ammonia (7 M in MeOH) (140 ml, 980 mmol, Eq: 18.7) was stirred in 10 sealed tubes at 60° C. for 3.5 days, but still not complete (ca. 75% conversion). Evaporated all volatiles, coated on silica gel and the crude material was purified by flash chromatography (silica gel, 200 g, 70% to 100% EtOAc in heptane to EtOH/THF 3:1->2:1) to give recovered (1SR,5RS)-1-(3-nitrophenyl)-3-oxabicyclo[3.1.0]hexan-2-one (1.957 g, 16%, which was converted under the same conditions to product) and (1SR,2RS)-2-(hydroxymethyl)-1-(3-nitrophenyl)cyclopropanecarboxamide (10.61 g, 44.9 mmol, 85.8% yield) as a light brown solid. MS (ISN): m/z=235.1 [(M−H)−].

Workup

  1. customEvaporated all volatiles
  2. customthe crude material was purified by flash chromatography (silica gel, 200 g, 70% to 100% EtOAc in heptane to EtOH/THF 3:1->2:1)
  3. customto give
  4. customrecovered (1SR,5RS)-1-(3-nitrophenyl)-3-oxabicyclo[3.1.0]hexan-2-one (1.957 g, 16%, which

Sources & evidence

ORD record
ord-9813aaf9f8f04ec8adaa89dfd8f13a7e
Source dataset
uspto-grants-2015_01
Patent number
US08927535B2

Reaction notes

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