2-Bromophenol → HCID 9930388, compound

HRID 992677Notes

Reaction equation

HRID 992677 reaction equation
C(Cl)(=O)C(Cl)=O.[I:7][C:8]1[CH:9]=[C:10]([C:13]([OH:15])=[O:14])[NH:11][CH:12]=1.[Br:16][C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][C:18]=1O.C(N(CC)CC)C>C(Cl)Cl.CN(C1C=CN=CC=1)C>[I:7][C:8]1[CH:9]=[C:10]([C:13]([O:15][C:18]2[CH:19]=[CH:20][CH:21]=[CH:22][C:17]=2[Br:16])=[O:14])[NH:11][CH:12]=1

Participants

7

Reactant 4

HCID 72442-BromophenolHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 110318974-iodo-1H-pyrrole-2-carboxylic Acid

Product 1

HCID 9930388HCID 9930388, compoundYield 92%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
18 °C

Procedure

Oxalyl chloride (203 mL, 2.32 mmol) was added to a magnetically stirred suspension of 4-iodopyrrole-2-carboxylic acid (8) (500 mg, 2.11 mmol) in dry CH2Cl2 (15.0 ml) containing dmf (1 drop). After stirring the resulting solution at 18° C. for 2 h it was added to a magnetically stirred solution of o-bromophenol (363 mg, 2.11 mmol), triethylamine (660 ml, 4.73 mmol) and 4-(N,N-dimethylamino)pyridine (dmap, several crystals) in CH2Cl2 (10 ml). After 1 h the reaction mixture was concentrated onto silica gel (5 g) and the residue subjected to flash chromatography (silica gel, 3:1 hexane/ether elution). Concentration of the appropriate fractions (Rf 0.2) then gave the title compound (761 mg, 92%) as a white crystalline solid, m.p. 126-127° C. (Found: C, 33.9; H, 1.7; Br, 20.4; I, 32.4; N, 4.0. C11H7BrINO2 requires C, 33.7; H, 1.8; Br, 20.4; I, 32.4; N, 3.6%). nmax (KBr) 3383, 2969, 1709, 1580, 1541, 1472, 1444, 1377, 1312, 1218, 1169, 1133, 1043 cm−1. 1H n.m.r. d 9.57, broad s, 1H; 7.65, dd, J 8.1 and 1.5 Hz, 1H; 7.37, td, J 8.1 and 1.5 Hz, 1H; 7.27, m, 2H; 7.18, td, J 8.1 and 1.5 Hz, 1H; 7.08, m, 1H. 13C n.m.r. d 158.0 (C), 148.3 (C), 134.0 (CH), 129.8 (CH), 129.1 (CH), 128.1 (CH), 124.4 (CH), 124.3 (CH), 123.6 (C), 116.9 (C), 62.9 (C). Mass spectrum m/z 393 (24%) 391 (22) (M+.); 220 (100) [(M−C6H4BrO)+.].

Workup

  1. additioncontaining dmf (1 drop)
  2. concentrationAfter 1 h the reaction mixture was concentrated onto silica gel (5 g)
  3. washthe residue subjected to flash chromatography (silica gel, 3:1 hexane/ether elution)

Sources & evidence

ORD record
ord-d504f5762570414d9d0f5299f7d2d74d
Source dataset
uspto-grants-2002_10
Patent number
US06469171B1

Reaction notes

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