Triphenylphosphine → (R)-6-Bromo-11-[3,5-dibromo-4-(1-bromomethyl-2-phenyl-ethoxy)-phenyl]-benzo[b]naphtho[2,3-d]thiophene

HRID 1873201Notes

Reaction equation

HRID 1873201 reaction equation
CCOC(/N=N/C(OCC)=O)=O.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Br-:32].[Li+].[Br:34][C:35]1[C:47]2[S:46][C:45]3[CH:48]=[CH:49][CH:50]=[CH:51][C:44]=3[C:43]=2[C:42]([C:52]2[CH:57]=[C:56]([Br:58])[C:55]([O:59][C@@H:60]([CH2:68]O)[CH2:61][C:62]3[CH:67]=[CH:66][CH:65]=[CH:64][CH:63]=3)=[C:54]([Br:70])[CH:53]=2)=[C:41]2[C:36]=1[CH:37]=[CH:38][CH:39]=[CH:40]2>C1COCC1>[Br:34][C:35]1[C:47]2[S:46][C:45]3[CH:48]=[CH:49][CH:50]=[CH:51][C:44]=3[C:43]=2[C:42]([C:52]2[CH:53]=[C:54]([Br:70])[C:55]([O:59][C@@H:60]([CH2:68][Br:32])[CH2:61][C:62]3[CH:63]=[CH:64][CH:65]=[CH:66][CH:67]=3)=[C:56]([Br:58])[CH:57]=2)=[C:41]2[C:36]=1[CH:37]=[CH:38][CH:39]=[CH:40]2

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 82050Lithium BromideHCID 5462977Diethyl azodicarboxylateHCID 53810433(R)-6-Bromo-11-[3,5-dibromo-4-(1-hydroxymethyl-2-phenyl-ethoxy)-phenyl]-benzo[b]naphtho[2,3-d]thiophene

Product 1

HCID 53895472(R)-6-Bromo-11-[3,5-dibromo-4-(1-bromomethyl-2-phenyl-ethoxy)-phenyl]-benzo[b]naphtho[2,3-d]thiopheneYield 73%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

Diethylazodicarboxylate (0.151 mL, 0.96 mmol) was added dropwise to a 0° C., stirred solution of triphenylphosphine (0.257 g, 0.98 mmol) in THF (6 mL) under a dry nitrogen atmosphere. After 20 min., lithium bromide was added to a nearly colorless reation mixture, followed by adding a solution of (R)-6-bromo-1 1-[3,5-dibromo-4-(1-hydroxymethyl-2-phenyl-ethoxy)-phenyl]-benzo[b]naphtho[2,3-d]thiophene (0.273 g, 0.392 mmol) in THF (3 mL). After 1 h, the solution was allowed to warm to ambient temperature. After 2 h, the reaction mixture was quenched with water (0.2 mL) and further diluted with ethyl ether (50 mL). Silica gel (8 mL) was added. Solvent was removed and the silica adsorbate was flash chromatographed (eluent 98:2 petroleum ether:ethyl acetate) to provide the title compound as a white solid (0.23 g, 73%): mp >90° C. (dec.): MS (EI): [M+], 4 bromine isotope pattern, 756, 758, 760, 762, 764; Anal. Calc. for C28H17Br3N203S.0.25 hexane: C, 49.97, H, 2.97, N, 0.00. Found: C, 49.97, H, 2.83, N, 0.02.

Workup

  1. waitAfter 1 h
  2. waitAfter 2 h
  3. customthe reaction mixture was quenched with water (0.2 mL)
  4. additionfurther diluted with ethyl ether (50 mL)
  5. additionSilica gel (8 mL) was added
  6. customSolvent was removed
  7. customchromatographed (eluent 98:2 petroleum ether:ethyl acetate)

Sources & evidence

ORD record
ord-2f26905b81ae4259bcceb9df97c8c2bf
Source dataset
uspto-grants-2000_08
Patent number
US06110962

Reaction notes

Loading…