Dimethylformamide → HCID 131733230, compound

HRID 508708Notes

Reaction equation

HRID 508708 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([N:8]2[C:14]3[CH:15]=[CH:16][C:17](B4[O:23][C:22](C)(C)[C:21](C)(C)[O:20]4)=[CH:18][C:13]=3[CH2:12][N:11]([CH3:28])[CH2:10][CH2:9]2)=[CH:4][CH:3]=1.[CH3:29][S:30]([C:33]1[CH:38]=[CH:37][C:36](Br)=[CH:35][CH:34]=1)(=[O:32])=[O:31].[C:40](=[O:43])([O-:42])[O-].[Cs+].[Cs+].CN([CH:49]=[O:50])C>O.C1C=CC([PH+]([C]2[CH][CH][CH][CH]2)C2C=CC=CC=2)=CC=1.C1C=CC([PH+]([C]2[CH][CH][CH][CH]2)C2C=CC=CC=2)=CC=1.C(Cl)Cl.Cl[Pd]Cl.[Fe]>[C:40]([C@@H:21]([C@H:22]([C:49]([OH:50])=[O:31])[OH:23])[OH:20])([OH:42])=[O:43].[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([N:8]2[C:14]3[CH:15]=[CH:16][C:17]([C:36]4[CH:37]=[CH:38][C:33]([S:30]([CH3:29])(=[O:32])=[O:31])=[CH:34][CH:35]=4)=[CH:18][C:13]=3[CH2:12][N:11]([CH3:28])[CH2:10][CH2:9]2)=[CH:4][CH:3]=1

Participants

7

Reactant 4

HCID 6228DimethylformamideHCID 10796Cesium carbonateHCID 770141-Bromo-4-(methylsulphonyl)benzeneHCID 68555637HCID 68555637, compound

Product 1

HCID 131733230HCID 131733230, compoundYield 11%

Reagents, catalysts & solvents 2

HCID 53485975CID 53485975CatalystHCID 962WaterSolvent

Procedure

Following a procedure similar to the one in Example 36, 1-(4-chlorophenyl)-4-methyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,3,4,5-tetrahydro-1H-benzo[e][1,4]diazepine (100 mg, 0.251 mmol), 4-(methanesulfonyl)bromobenzene (76 mg, 0.301 mmol), cesium carbonate (245 mg, 0.752 mmol) and dichloro[1,1′-bis(diphenylphosphino)ferrocene]palladium(II) dichloromethane adduct (20 mg, 0.0251 mmol) in DMF (2.0 mL) and water (0.5 mL) gave the desired product (11.2 mg, 11%) as a colorless oil. To a solution of the benzodiazepine (11.2 mg, 0.026 mmol) in methanol (1 mL) and water (3 mL) was added L-tartaric acid (4.1 mg, 0.026 mmol) and the resultant solution was lyophilized overnight to give 1-(4-chlorophenyl)-4-methyl-7-(4-(methylsulfonyl)phenyl)-2,3,4,5-tetrahydro-1H-benzo[e][1,4]diazepine, L-tartrate salt (15.0 mg, 98%, AUC HPLC>99%) as a yellow solid: 1H NMR (CD3OD, 500 MHz) δ 8.04 (d, J=8.3 Hz, 2H), 7.92 (d, J=8.4 Hz, 2H), 7.88 (s, 1H), 7.76 (d, J=8.3 Hz, 1H), 7.28 (d, J=8.3 Hz, 1H), 7.22 (d, J=9.0 Hz, 2H), 6.89 (d, J=8.9 Hz, 2H), 4.43 (s, 1H), 4.21 (s, 2H), 3.96 (bs, 2H), 3.44 (bs, 2H), 3.17 (s, 3H), 2.84 (s, 3H); ESI MS m/z 427 [M+H]+.

Sources & evidence

ORD record
ord-6566ad245bb54287a2e14d6ae89c7df3
Source dataset
uspto-grants-2015_08
Patent number
US09096546B2

Reaction notes

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