Phenyl isocyanate → HCID 86761309, compound

HRID 547838Notes

Reaction equation

HRID 547838 reaction equation
Cl.[NH2:2][CH2:3][CH2:4][O:5][CH2:6][C:7]1[CH:20]=[CH:19][C:10]([C:11]([C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)=[O:12])=[CH:9][CH:8]=1.C(N(CC)CC)C.[C:28]1([N:34]=[C:35]=[O:36])[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1>C(Cl)Cl>[C:11]([C:10]1[CH:19]=[CH:20][C:7]([CH2:6][O:5][CH2:4][CH2:3][NH:2][C:35]([NH:34][C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)=[O:36])=[CH:8][CH:9]=1)(=[O:12])[C:13]1[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=1

Participants

5

Reactant 3

HCID 7672Phenyl isocyanateHCID 8471TriethylamineHCID 86761310HCID 86761310, compound

Product 1

HCID 86761309HCID 86761309, compoundYield 67%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

To a stirred suspension of (X) (3.49 g, 12 mmol) in dry DCM (10 ml) was added dry triethylamine (10 ml). After 0.25 h. stirring a solution of phenyl isocyanate (2.14 g, 18 mmol) in dry DCM (10 ml) was added in one portion. The mixture was stirred for a further 16 h. then quenched with water (10 ml). The organic layer was collected and washed sequentially with water, 2M HCl, and water. The organic layer was dried over MgSO4 and purified by flash chromatography on silica gel eluting with 2:1 petrol 40/60:ethyl acetate (Rf=0.1) to yield (XI) (3.01 g, 67%) as a white solid; m.p. 129-132° C.; δH (DMSO-d, 200 MHz) 3.39 (q, 2H, J=5.1 Hz, NHCH2), 3.58 (t, 2H, J=5.0 Hz, OCH2CH2), 4.65 (s, 2H, OCH2Ar), 6.32 (t, 1H, J=5.2 Hz CH2NHC(O)NHAr), 6.90 (t, 1H, J=7.3 Hz, 4″-H), 7.24 (t, 2H, J=7.4 Hz, 3″-, 5″-H), 7.44 (d, 2H, J=7.6 Hz, 2″-, 6″-H), 7.56 (m, 4H, 3-, 5-, 3′-, 5′-H), 7.70 (m, 5H, 2-, 4-, 6-, 2″-, 6″-H) 8.63 (s, 1H, CH2NHC(O)NHAr) ppm; δC (DMSO-d, 400 MHz) 39.9 (CH2CH2NH), 70.4 (CH2CH2O), 72.1 (ArCH2O), 118.4 (2″-, 6″-C), 121.9 (4″-C), 128.1 (2-, 6-, 2′-, 6′-C), 129.4 (3″-, 5″-C), 130.4, 130.6 (3-, 5-, 3′-, 5′-C), 133.5 (4′-C), 136.9, 138.0 (1-, 1″-C), 141.3 (4-C), 144.4 (1″-C), 156.1 (N(H)C(O)NH), 196.3 (Ar2C(O)) ppm; max 3431 (N—Hstr), 1724 ((R(H)N)2C═Ostr), 1658 (Ar2C═Ostr) cm−1; m/z 375 [M+H]+ (5%), 397 [M+Na]+ (10%), 433 [M+MeCN+NH4]+ (100%); found 375.1703, C23H23N2O3 requires 375.1709.

Workup

  1. additionwas added in one portion
  2. customthen quenched with water (10 ml)
  3. customThe organic layer was collected
  4. washwashed sequentially with water, 2M HCl, and water
  5. dry with materialThe organic layer was dried over MgSO4
  6. custompurified by flash chromatography on silica gel eluting with 2:1 petrol 40/60

Sources & evidence

ORD record
ord-8dd750915e73449eb8105ac8bfb03aff
Source dataset
uspto-grants-2011_05
Patent number
US07939581B2

Reaction notes

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