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

HRID 1660977

반응식

HRID 1660977 반응식
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]

참가 물질

10

반응물 4

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

생성물 1

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

시약·촉매·용매 5

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)촉매HCID 498840Bis(benzonitrile)palladium chloride촉매2회HCID 962Water용매HCID 8857Ethyl Acetate용매HCID 312751,4-Dioxane용매

실험 절차

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).

후처리

  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)

출처 및 근거

ORD 기록
ord-48463f684ac441b68d3df8c38e2b99c5
출처 데이터셋
uspto-grants-2011_10
특허 번호
US08030311B2

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