Acrylonitrile → HCID 22184038, compound

HRID 926917Notes

Reaction equation

HRID 926917 reaction equation
NCC[NH:4][C:5](=[O:14])[O:6]CC1C=CC=CC=1.C(#N)C=C.[C:19]([O:23][C:24](=[O:42])[N:25]([CH2:39][CH2:40][NH2:41])[CH2:26][CH2:27][NH:28][C:29]([O:31][CH2:32][C:33]1[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1)=[O:30])([CH3:22])([CH3:21])[CH3:20].CN1CCOCC1.ClC(O[C:54]1[CH:59]=[CH:58][C:57]([N+:60]([O-:62])=[O:61])=[CH:56][CH:55]=1)=O>C(Cl)Cl.O>[C:19]([O:23][C:24](=[O:42])[N:25]([CH2:39][CH2:40][NH2:41])[CH2:26][CH2:27][NH:28][C:29]([O:31][CH2:32][C:33]1[CH:34]=[CH:35][CH:36]=[CH:37][CH:38]=1)=[O:30])([CH3:20])([CH3:22])[CH3:21].[C:5](=[O:6])([O:14][C:56]1[CH:55]=[CH:54][CH:59]=[CH:58][C:57]=1[N+:60]([O-:62])=[O:61])[NH2:4]

Participants

9

Reactant 5

HCID 7855AcrylonitrileHCID 79724-MethylmorpholineHCID 821294-Nitrophenyl chloroformateHCID 2794257Benzyl N-(2-aminoethyl)carbamateHCID 58348984HCID 58348984, compound

Product 2

HCID 22184038HCID 22184038, compoundYield 74%HCID 58348984HCID 58348984, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

(2-Amino-ethyl)-(2-benzyloxycarbonylamino-ethyl)-carbamic acid tert-butyl ester was prepared from benzyl 2-aminoethylcarbamate using the same reaction sequence outlined by Andruszkiewicz et al in Synthetic Communications 2008, 38, p. 905-913 (reaction with acrylonitrile, followed by protection of the secondary amine with the BOC group, and conversion of the nitrile group to an amino group with one less methylene unit using the Hoffmann rearrangement). (2-Amino-ethyl)-(2-benzyloxycarbonylamino-ethyl)-carbamic acid tert-butyl ester (500 mg, 1.48 mmol) was taken up in 15 mL of CH2Cl2 along with 4-methylmorpholine (449 mg, 4.44 mmol) and cooled to 0° C. 4-Nitrophenyl chloroformate (328 mg, 1.63 mmol) was then added at 0° C. The resulting reaction mixture was warmed to room temperature and stirred for 16 h. It was then diluted with water. The organic layer was separated, dried (Na2SO4), and concentrated under reduced pressure. Purification by chromatography (95% CH2Cl2, 5% MeOH) afforded the intermediate nitrophenyl carbamate (480 mg; 74%).

Workup

  1. customThe resulting reaction mixture
  2. temperaturewas warmed to room temperature
  3. customThe organic layer was separated
  4. dry with materialdried (Na2SO4)
  5. concentrationconcentrated under reduced pressure
  6. customPurification by chromatography (95% CH2Cl2, 5% MeOH)

Sources & evidence

ORD record
ord-79f7ba1a66204dad81107d55c1394b06
Source dataset
uspto-grants-2016_03
Patent number
US09289503B2

Reaction notes

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