Diisopropylamine → Dimethyl-[3-(4-nitro-2-trifluoromethyl-phenyl)-prop-2-ynyl]-amine

HRID 1660977

反応式

HRID 1660977 の反応式
P(C(C)(C)C)(C(C)(C)C)C(C)(C)C.[CH3:14][N:15]([CH3:19])[CH2:16][C:17]#[CH:18].N(C(C)C)C(C)C.[N+:27]([C:30]1[CH:31]=[CH:32][C:33](Br)=[C:34]([C:36]([F:39])([F:38])[F:37])[CH:35]=1)([O-:29])=[O:28]>O1CCOCC1.CCOC(C)=O.O.[Cu]I.C1C=CC(C#N)=CC=1.C1C=CC(C#N)=CC=1.Cl[Pd]Cl>[CH3:14][N:15]([CH3:19])[CH2:16][C:17]#[C:18][C:33]1[CH:32]=[CH:31][C:30]([N+:27]([O-:29])=[O:28])=[CH:35][C:34]=1[C:36]([F:37])([F:38])[F:39]

参加物

10

反応物 4

HCID 7912DiisopropylamineHCID 81643N,N-DimethylpropargylamineHCID 83681Tris(1,1-dimethylethyl)phosphineHCID 1361982-Bromo-5-nitrobenzotrifluoride

生成物 1

HCID 67021317Dimethyl-[3-(4-nitro-2-trifluoromethyl-phenyl)-prop-2-ynyl]-amine

試薬・触媒・溶媒 5

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 498840Bis(benzonitrile)palladium chloride触媒2 回HCID 962Water溶媒HCID 8857Ethyl Acetate溶媒HCID 312751,4-Dioxane溶媒

実験手順

t-Bu3P (0.25 M in dioxane, 8.9 mL, 2.2 mmol, 0.2 equiv), 3-dimethylamino-1-propyne (FLUKA) (1.65 mL, 15.6 mmol, 1.4 equiv), and i-Pr2NH (2.0 mL, 14.4 mmol, 1.3 equiv) are added sequentially to a mixture of 5-nitro-2-bromobenzotrifluoride (ALDRICH) (3 g, 11.1 mmol), CuI (0.148 g, 0.78 mmol, 0.07 equiv), and Pd(PhCN)2Cl2 (0.427 g, 1.1 mmol, 0.1 equiv) in dioxane (10 mL). The reaction mixture is stirred for 48 h at rt. Then, Pd(PhCN)2Cl2 (0.100 g) is added. After stirring for additional 24 h, the reaction mixture is diluted with EtOAc and H2O and filtered through a pad of Celite. The filtrate is extracted with EtOAc. The organic phase is washed with brine, dried (Na2SO4), filtered and concentrated. Purification of the crude material by silica gel column chromatography (CH2Cl2/NH3 (2 N in MeOH), 95:5) affords the title compound as a brown oil: ES-MS: 273.0 [M+H]+; single peak at tR=3.06 min (System 1); Rf=0.13 (CH2Cl2/NH3 (2 N in MeOH), 95:5).

後処理

  1. stirringAfter stirring for additional 24 h
  2. filtrationfiltered through a pad of Celite
  3. extractionThe filtrate is extracted with EtOAc
  4. washThe organic phase is washed with brine
  5. dry with materialdried (Na2SO4)
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customPurification of the crude material by silica gel column chromatography (CH2Cl2/NH3 (2 N in MeOH), 95:5)

出典と根拠

ORDレコード
ord-48463f684ac441b68d3df8c38e2b99c5
出典データセット
uspto-grants-2011_10
特許番号
US08030311B2

関連ノート

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