Dimethyl Sulfoxide → HCID 67782100, compound

HRID 1463185Notes

Reaction equation

HRID 1463185 reaction equation
Br.[Br-].[N:3]1([CH2:8][CH2:9][CH2:10][P+](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[CH2:7][CH2:6][CH2:5][CH2:4]1.C([Li])CCC.[Br:35][C:36]1[CH:52]=[CH:51][C:39]2[O:40][CH2:41][C:42]3[CH:49]=[CH:48][C:47]([Br:50])=[CH:46][C:43]=3[C:44](=O)[C:38]=2[CH:37]=1.CS(C)=O>CCCCCC.O1CCCC1>[Br:35][C:36]1[CH:52]=[CH:51][C:39]2[O:40][CH2:41][C:42]3[CH:49]=[CH:48][C:47]([Br:50])=[CH:46][C:43]=3/[C:44](=[CH:10]/[CH2:9][CH2:8][N:3]3[CH2:4][CH2:5][CH2:6][CH2:7]3)/[C:38]=2[CH:37]=1

Participants

7

Reactant 4

HCID 679Dimethyl SulfoxideHCID 20085912HCID 20085912, compoundHCID 20085916HCID 20085916, compoundHCID 178418339Butyllithium

Product 1

HCID 67782100HCID 67782100, compound

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Procedure

Anhydrous 3-(N-pyrrolidinyl)propyltriphenylphosphonium bromide hydrobromide (47 g, 0.08 mole), 0.20 mole of n-butyl lithium in hexane (1.6 M), and 2,9-dibromo-6,11-dihydrodibenz[b,e]oxepin-11-one (25 g, 0.07 mole) in one liter of dry tetrahydrofuran by the procedure of Example 1, Step a. The crude product was chromatographed on a silica gel column (Waters Associates - Prep 500) with ethyl acetate/methanol (95:5) to give the product as 98% pure Z-isomer (0.30 g), mp 102°-103° C. pmr (DMSO-d6) δ: 7.31-7.54 (m, 5H, aromatic H), 6.79 (d, J=7.8 Hz, H4 of 98% Z), 6.67 (d, J=7.8 Hz, H of 2% E), 6.11 (t, CH= of 2% E), 5.78 (t, CH= of 98% Z), 2.34-2.56 (m, 8H, CH2 and 3NHCH2), 1.63 (m, 4H, 2CH2). And it gave another batch of the product as 90% pure E-isomer (0.18 g), mp 115°-116° C., pmr (DMSO) δ: 7.71-7.68 (m, 5H, aromatic H), 6.80 (d, J=7.8 Hz, H4 of 10% Z), 6.70 (d, J=7.8 Hz, H4 of 90% E), 6.10 (t, CH= of 90% E), 5.81 (t, CH= of 10% Z), 2.26-2.40 (m, 8H, CH2 and 3NCH2), 1.60 (m, 4H, 2CH2).

Workup

  1. customThe crude product was chromatographed on a silica gel column (Waters Associates - Prep 500) with ethyl acetate/methanol (95:5)
  2. customto give the product as 98% pure Z-isomer (0.30 g), mp 102°-103° C. pmr (DMSO-d6) δ

Sources & evidence

ORD record
ord-49718430a44b4d2581ac82c7e2bd4a5c
Source dataset
uspto-grants-1994_04
Patent number
US05300282

Reaction notes

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