Triphenylphosphine → HCID 76138884, compound

HRID 1873188Notes

Reaction equation

HRID 1873188 reaction equation
CCOC(/N=N/C(OCC)=O)=O.[Br:13][C:14]1[CH:19]=[C:18]([C:20]2[C:29]3[C:30]4[CH:36]=[CH:35][CH:34]=[CH:33][C:31]=4[S:32][C:28]=3[C:27]([Br:37])=[C:26]3[C:21]=2[CH:22]=[CH:23][CH:24]=[CH:25]3)[CH:17]=[C:16]([Br:38])[C:15]=1[OH:39].[C:40]([O:49][CH3:50])(=[O:48])[C@H:41]([CH2:43][C:44]([O:46][CH3:47])=[O:45])O.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C1C=CC=CC=1.C(Cl)Cl>[CH3:47][O:46][C:44](=[O:45])[CH:43]([O:39][C:15]1[C:16]([Br:38])=[CH:17][C:18]([C:20]2[C:29]3[C:30]4[CH:36]=[CH:35][CH:34]=[CH:33][C:31]=4[S:32][C:28]=3[C:27]([Br:37])=[C:26]3[C:21]=2[CH:22]=[CH:23][CH:24]=[CH:25]3)=[CH:19][C:14]=1[Br:13])[CH2:41][C:40]([O:49][CH3:50])=[O:48]

Participants

7

Reactant 4

HCID 11776Triphenylphosphine2×HCID 5462977Diethyl azodicarboxylate2×HCID 10285815(S)-(-)-Dimethyl malate2×HCID 108406542,6-Dibromo-4-(6-bromo-benzo[b]naphtho[2,3-d]thiophen-11-yl)-phenol

Product 1

HCID 76138884HCID 76138884, compoundYield 51%

Reagents, catalysts & solvents 2

HCID 241BenzeneSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
79 °C

Procedure

Diethylazodicarboxylate (0.254 mL, 1.61 mmol) was added dropwise to a stirred, room temperature suspension of 2,6-dibromo-4-(6-bromo-benzo [b]naphtho[2,3-d]thiophen-11-yl)-phenol (0.600 g, 1.10 mmol), dimethyl (S)-(-)-malate (0.213 mL, 1.61 mmol) and triphenylphosphine (0.421 g, 1.61 mmol) in benzene (7.5 mL) under a dry nitrogen atmosphere. The solution was heated in an 79° C. oil bath for 23 h. Additional Dimethyl (S)-(-)-malate (0.043 mL, 0.321 mmol) and triphenylphosphine (0.084 g, 0.321 mmol) and diethylazodicarboxylate (0.050 mL, 0.321 mmol) were added and the reaction mixture was heated for an additional 10 hours. The reaction mixture was cooled to room temperature, diluted with methylene chloride combined with silica gel (20 mL) and concentrated. The silica adsorbate was flash chromatographed (92:8 petroleum ether:ethyl acetate) to provide the title compound as a white solid (0.389 g, 51%): mp 118-121° C.: NMR (CDCl3); δ8.36 (dd, J=8, 0.5 Hz, 1 H), 7.83 (dd, J=8, 0.5 Hz, 1 H), 7.68 (ddd, J=8, 7, 1 Hz, 1 H), 7.61 - 7.59 (m, 3 H), 7.55 -7.43 (m, 2 H), 7.26 - 7.21 (m, 1 H), 6.79 (d, J=8 Hz, 1 H), 5.46 (t, J=6 Hz, 1 H), 3.90 (s, 3 H), 3.77 (s, 3 H), 3.32 - 3.30 (m, 1 H); MS (EI): [M+], 3 bromine isotope pattern, 704 (5%), 706 (15%), 708 (15%), 710 (4%); Anal. Calc. for C28H19Br3O5S: C, 47.55, H, 2.71, N, 0.00. Found: C, 47.93, H, 2.65, N, 0.14.

Workup

  1. temperaturethe reaction mixture was heated for an additional 10 hours
  2. temperatureThe reaction mixture was cooled to room temperature
  3. concentrationconcentrated
  4. customchromatographed (92:8 petroleum ether:ethyl acetate)

Sources & evidence

ORD record
ord-b8c41e015de646a2b76ef5a778ece0ce
Source dataset
uspto-grants-2000_08
Patent number
US06110962

Reaction notes

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