Sodium Carbonate → 5-(2,8-Difluoro-10,11-dihydro-dibenzo[a,d]cyclohepten-5-ylidenemethyl)-1,3-dihydro-benzoimidazol-2-one

HRID 2218745Notes

Reaction equation

HRID 2218745 reaction equation
CC1(C)C(C)(C)OB([C:9]2[CH:18]=[CH:17][C:12]3[NH:13][C:14](=[O:16])[NH:15][C:11]=3[CH:10]=2)O1.BrC1C=CC2NC(=O)NC=2C=1.[N+](C1C=C(C=CC=1)C=C1OC2C=CC=CC=2CC2C=CC=CC1=2)([O-])=O.Br[CH:57]=[C:58]1[C:64]2[CH:65]=[CH:66][C:67]([F:69])=[CH:68][C:63]=2[CH2:62][CH2:61][C:60]2[CH:70]=[C:71]([F:74])[CH:72]=[CH:73][C:59]1=2.C([O-])([O-])=O.[Na+].[Na+]>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.O1CCOCC1>[F:69][C:67]1[CH:66]=[CH:65][C:64]2[C:58](=[CH:57][C:9]3[CH:18]=[CH:17][C:12]4[NH:13][C:14](=[O:16])[NH:15][C:11]=4[CH:10]=3)[C:59]3[CH:73]=[CH:72][C:71]([F:74])=[CH:70][C:60]=3[CH2:61][CH2:62][C:63]=2[CH:68]=1

Participants

8

Reactant 5

HCID 10340Sodium CarbonateHCID 122280605-Bromo-1,3-dihydro-2H-benzimidazol-2-oneHCID 438110655-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-benzo[d]imidazol-2(3H)-oneHCID 688911995-bromomethylene-2,8-difluoro-10,11-dihydro-5H-dibenzo[a,d]cyclohepteneHCID 866039843-Nitro-benzylidene-6,11-dihydro-dibenzo[b,e]oxepine

Product 1

HCID 99075895-(2,8-Difluoro-10,11-dihydro-dibenzo[a,d]cyclohepten-5-ylidenemethyl)-1,3-dihydro-benzoimidazol-2-oneYield 44.5%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 312751,4-DioxaneSolvent

Procedure

Following procedures essentially as described in Example 219, mix 5-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-1,3-dihydro-benzoimidazol-2-one (535 mg, 2.06 mmol) (prepared from 5-bromo-1,3-dihydro-benzoimidazol-2-one (Preparation 27) according to the procedure reported by M Murata, T Takashi, S Watanabe and Y Yusuru, J. Org. Chem.; 65 (1) 164-168 (2000)), 5-bromomethylene-2,8-difluoro-10,11-dihydro-5H-dibenzo[a,d]cycloheptene (550 mg, 1.71 mmol), 2N Na2CO3 (2 mL), dioxane (14 mL) and (Ph3P)4Pd (200 mg, 0.17 mmol). Purify the crude product by column chromatography using dichloromethane/ethyl acetate to give 285 mg white solid, mp 257° C. HPLC (ISO80-10M) t=2.62 (97%), MS (ES) 373 (M−1). H NMR 10.55 (s, 1H), 10.45 (s, 1H), 7.48 (dd, 1H, J=8.4, 6.2 Hz), 7.21 (dd, 1H, J=9.7, 2.2 Hz), 7.01 (td, 1H, J=12.2, 4.2 Hz), 6.94 (dd, 1H, J10.1, 2.2 Hz), 6.90 (d, 2H, J=6.2 Hz), 6.85 (dd, 1H, J=8.6, 2.4 Hz), 6.78 (s, 1H), 6.72 (d, 1H, J=8.4 Hz), 6.67 (d, 1H, J=7.9 Hz), 6.51 (s, 1H), 3.30 (s, 2H), 2.89 (s, 2H), 6.90 (d, 1H, J=6.2 Hz).

Workup

  1. customPurify the crude product by column chromatography

Sources & evidence

ORD record
ord-d7dfaa4842b841189a74a9ad249583ec
Source dataset
uspto-grants-2008_08
Patent number
US07411072B2

Reaction notes

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