alpha-Bromo-o-chlorotoluene → 1-Benzyl-3-[4-(tert-butyl-dimethyl-silanyloxy)-3,5-dimethyl-phenyl]-3-hydroxy-1,3-dihydro-indol-2-one

HRID 1297775Notes

Reaction equation

HRID 1297775 reaction equation
[C:1]([Si:5]([CH3:27])([CH3:26])[O:6][C:7]1[C:12]([CH3:13])=[CH:11][C:10]([C:14]2([OH:24])[C:22]3[C:17](=[CH:18][CH:19]=[CH:20][CH:21]=3)[NH:16][C:15]2=[O:23])=[CH:9][C:8]=1[CH3:25])([CH3:4])([CH3:3])[CH3:2].C(N=P1(N(CC)CC)N(C)CCCN1C)(C)(C)C.Cl[C:47]1[CH:54]=[CH:53][CH:52]=[CH:51][C:48]=1[CH2:49]Br>C(#N)C.CN(C=O)C>[CH2:49]([N:16]1[C:17]2[C:22](=[CH:21][CH:20]=[CH:19][CH:18]=2)[C:14]([C:10]2[CH:9]=[C:8]([CH3:25])[C:7]([O:6][Si:5]([C:1]([CH3:2])([CH3:4])[CH3:3])([CH3:27])[CH3:26])=[C:12]([CH3:13])[CH:11]=2)([OH:24])[C:15]1=[O:23])[C:48]1[CH:51]=[CH:52][CH:53]=[CH:54][CH:47]=1

Participants

5

Reactant 3

HCID 11905alpha-Bromo-o-chlorotolueneHCID 35138512-((1,1-Dimethylethyl)imino)-N,N-diethylhexahydro-1,3-dimethyl-2lambda5-1,3,2-diazaphosphorin-2-amineHCID 589146893-[4-(tert-Butyl-dimethyl-silanyloxy)-3,5-dimethyl-phenyl]-3-hydroxy-1,3-dihydro-indol-2-one

Product 1

HCID 695228771-Benzyl-3-[4-(tert-butyl-dimethyl-silanyloxy)-3,5-dimethyl-phenyl]-3-hydroxy-1,3-dihydro-indol-2-oneYield 81.1%

Reagents, catalysts & solvents 1

HCID 21891449acetonitrile N,N-dimethylformamideSolvent

Procedure

Using a method similar to Preparation 17 with 3-[4-(tert-butyl-dimethyl-silanyloxy)-3,5-dimethyl-phenyl]-3-hydroxy-1,3-dihydro-indol-2-one (3.83 g, 10 mmol), 2-tert-butylimino-2-diethylamino-1,3-dimethyl-perhydro-1,3,2-diazaphosphorine (3.5 ml, 12 mmol) and 2-chlorobenzyl bromide (1.56 mL, 12 mmol) in acetonitrile/DMF (60 mL/20 mL) gives 5.9 g of a crude yellow gum. Purify by flash chromatography (CH2Cl2 to 10% EtOAc/CH2Cl2) gives 3.84 g (76%) of the title compound as a white solid. Mp 147.1° C. MS (ES): m/z=490 (M+1−H2O); 1H NMR(DMSO-d6): δ7.52 (dd, J=1.7, 1.4 Hz, J=7.7, 7.4 Hz, 1H), 7.37-7.14 (m, 5H), 7.05 (t, J=7.7 Hz, 1H), 6.93 (s, 2H), 6.86 (d, J=7.7 Hz, 1H), 6.73 (s, 1H), 4.96 (abq, 2H), 2.11 (s, 6H), 0.98 (s, 9H), 0.16 (s, 6H).

Workup

  1. customgives 5.9 g of a crude yellow gum
  2. customPurify by flash chromatography (CH2Cl2 to 10% EtOAc/CH2Cl2)

Sources & evidence

ORD record
ord-9fe58d07d22d44f4a0701d009cb424dc
Source dataset
uspto-grants-2007_07
Patent number
US07250442B2

Reaction notes

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