HCID 9939669, compound → HCID 9831055, compound

HRID 1954277Notes

Reaction equation

HRID 1954277 reaction equation
[Br:1][C:2]1[C:11]2[S:12][C:13]([CH3:16])=[C:14]([CH3:15])[C:10]=2[C:9]([C:17]2[CH:36]=[CH:35][C:20]([O:21][S:22]([C:25]3[S:29][CH:28]=[C:27]([C:30]([OH:32])=[O:31])[C:26]=3[O:33]C)(=[O:24])=[O:23])=[C:19]([CH:37]3[CH2:41][CH2:40][CH2:39][CH2:38]3)[CH:18]=2)=[C:8]2[C:3]=1[CH:4]=[CH:5][CH:6]=[CH:7]2.B(Br)(Br)Br.C(Cl)Cl.C(=O)=O.CC(C)=O>C(Cl)Cl>[Br:1][C:2]1[C:11]2[S:12][C:13]([CH3:16])=[C:14]([CH3:15])[C:10]=2[C:9]([C:17]2[CH:36]=[CH:35][C:20]([O:21][S:22]([C:25]3[S:29][CH:28]=[C:27]([C:30]([OH:32])=[O:31])[C:26]=3[OH:33])(=[O:24])=[O:23])=[C:19]([CH:37]3[CH2:41][CH2:40][CH2:39][CH2:38]3)[CH:18]=2)=[C:8]2[C:3]=1[CH:4]=[CH:5][CH:6]=[CH:7]2

Participants

5

Reactant 3

HCID 9939669HCID 9939669, compoundHCID 18522661Acetone cardiceHCID 22277759Boron tribromide dichloromethane

Product 1

HCID 9831055HCID 9831055, compoundYield 97.4%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

At -78° C., to a stirred suspension of 5-[4-(9-bromo-2,3-dimethyl-naphtho[2,3-b]thiophen-4-yl)-2-cyclopentyl-phenoxysulfonyl]-4-methoxy-thiophene-3-carboxylic acid (0.286 g, 0.426 mmol) in CH2Cl2 (2.86 mL) was added 1M BBr3 /CH2Cl2 (1.32 mL, 1.32 mmol). After the addition was complete the dry ice/acetone bath was replaced with an ice water bath and the reaction was stirred for 1 h. The reaction was quenched with crushed ice, diluted with H2O (40 mL) and extracted with EtOAc. The combined organic extracts were combined with product from an identical experiment and concentrated. Purification on 2% H3PO4 /MeOH treated Biotage KP-Sil, eluting with 35% EtOAc/hexane gave 0.273 g (95%) of the title compound as a pale yellow solid, mp >230° C.; 1H NMR (DMSO-d6) δ 1.31-1.40 (m, 2 H), 1.47 (s, 3 H), 1.50-1.67 (m, 5 H), 1.80-1.83 (m, 1 H), 2.42 (s, 3 H), 3.32 (quintet, 1 H), 7.22 (dd, 1 H), 7.31-7.37 (m, 3 H), 7.48 (t, 1 H), 7.64 (t, 1 H), 8.19 (d, 1 H), 8.64 (s, 1 H). IR (KBr) 3400, 2950, 1650, 1375 and 1150 cm-1. mass spectrum (-ACPI), n/z 665 (M-H). Anal. Calcd. for C30H25BrO6S3.0.5H2O: C, 54.05; H, 3.93 N, 0.00. Found: C, 54.09; H, 3.98 N, 0.05.

Workup

  1. additionAfter the addition
  2. customwas replaced with an ice water bath
  3. customThe reaction was quenched with crushed ice
  4. additiondiluted with H2O (40 mL)
  5. extractionextracted with EtOAc
  6. concentrationconcentrated
  7. customPurification on 2% H3PO4 /MeOH treated Biotage KP-Sil
  8. washeluting with 35% EtOAc/hexane

Sources & evidence

ORD record
ord-b1d5d939372a49c28c8675aae6dcd1af
Source dataset
uspto-grants-2000_09
Patent number
US06121271

Reaction notes

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