Potassium Carbonate → 2'-Hydroxymethyl-3-methylamino-4-nitro-biphenyl-2-carbonitrile

HRID 2246896ノート

反応式

HRID 2246896 の反応式
Cl[C:2]1[C:7]([C:8]#[N:9])=[C:6]([NH:10][CH3:11])[C:5]([N+:12]([O-:14])=[O:13])=[CH:4][CH:3]=1.[OH:15][CH2:16][C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][C:18]=1B(O)O.C(=O)([O-])[O-].[K+].[K+].C1(P(C2CCCCC2)C2C=CC=CC=2C2C=CC=CC=2N(C)C)CCCCC1>CC(N(C)C)=O.CCOC(C)=O.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[OH:15][CH2:16][C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][C:18]=1[C:2]1[C:7]([C:8]#[N:9])=[C:6]([NH:10][CH3:11])[C:5]([N+:12]([O-:14])=[O:13])=[CH:4][CH:3]=1

参加物

8

反応物 4

HCID 11430Potassium CarbonateHCID 27342172-(Dicyclohexylphosphino)-2'-(dimethylamino)biphenylHCID 43742622-(Hydroxymethyl)phenylboronic AcidHCID 112180896-Chloro-2-(methylamino)-3-nitrobenzonitrile

生成物 1

HCID 592186742'-Hydroxymethyl-3-methylamino-4-nitro-biphenyl-2-carbonitrile収率 82%

試薬・触媒・溶媒 3

HCID 9811564Bis(dibenzylideneacetone)palladium触媒HCID 8857Ethyl Acetate溶媒HCID 31374Dimethylacetamide溶媒

反応条件

温度
68 °C

実験手順

6-Chloro-2-methylamino-3-nitro-benzonitrile (500 mg, 2.4 mmol), 2-hydroxymethyl-phenylboronic acid (466 mg, 3.1 mmol), and potassium carbonate (1.30 g, 6.1 mmol) were combined in DMA (10 mL) in a flask purged with nitrogen. Tris(dibenzylideneacetone)dipalladium(0) (108 mg, 0.12 mmol) and 2-dicyclohexylphosphino-2′-(N,N-dimethyl-amino)biphenyl (93 mg, 0.24 mmol) were added, and the reaction stirred at 68° C. under nitrogen for 16 h. The solution was diluted with EtOAc (50 mL), and washed with 1N HCl and brine. Organics were dried (MgSO4) and concentrated in vacuo. Purification by silica gel chromatography (2:1:1 hexanes/CHCl3/EtOAc) gave 550 mg (82%) of the title compound as an orange solid. 1H NMR (400 MHz, CDCl3): δ 8.49 (br s, 1H), 8.35 (d, 1H, J=8.8 Hz), 7.59 (d, 1H, J=7.6 Hz), 7.46 (td, 1H, J=7.6, 1.2 Hz), 7.40 (td, 1H, J=7.6, 1.2 Hz), 7.20 (dd, 1H, J=7.6, 1.2 Hz), 6.60 (d, 1H, J=8.8 Hz), 4.52 (qAB, 2H, J=31.6, 12.8 Hz), 3.46 (s, 3H). MS (ES) [m+H] calc'd for C15H13N3O3, 284; found 284.

後処理

  1. custompurged with nitrogen
  2. washwashed with 1N HCl and brine
  3. dry with materialOrganics were dried (MgSO4)
  4. concentrationconcentrated in vacuo
  5. customPurification by silica gel chromatography (2:1:1 hexanes/CHCl3/EtOAc)

出典と根拠

ORDレコード
ord-5d7fcc08241f4d88bd462a222a786760
出典データセット
uspto-grants-2010_03
特許番号
US07687638B2

反応ノート

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