3,4-Dichloroaniline → HCID 14650028, compound

HRID 1722701Notes

Reaction equation

HRID 1722701 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([NH2:9])[CH:5]=[CH:6][C:7]=1[Cl:8].Br[CH2:11][C:12]#[CH:13].C(N(C(C)C)C(C)C)C.C(OCC)(=O)C>C1(C)C=CC=CC=1>[Cl:1][C:2]1[CH:3]=[C:4]([NH:9][CH2:13][C:12]#[CH:11])[CH:5]=[CH:6][C:7]=1[Cl:8]

Participants

6

Reactant 4

HCID 72573,4-DichloroanilineHCID 7842Propargyl bromideHCID 8857Ethyl AcetateHCID 81531Diisopropylethylamine

Product 1

HCID 14650028HCID 14650028, compound

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent2×

Procedure

A solution of 16.20 g (0.1 mol) of 3,4-dichlorobenzenamine, 16.36 g (0.11 mol) of an 80% solution of 3-bromo-1-propyne in toluene, and 17.4 ml (0.11 mol) of N-ethyl-N-(1-methylethyl)-2-propanamine in 350 ml of toluene is heated at 90° for six hours. Ethyl acetate is added to the reaction suspension, and the suspension is washed three times with water. The organic layer is separated, dried (magnesium sulfate), and concentrated to give 19.85 g of a dark brown liquid. This is applied to a column of 1 kg of flash silica gel packed in hexane/dichloromethane (5:1). Elution with the same solvent gives 1.48 g (11.3%) of 3,4-dichloro-N,N-di-2-propynylbenzenamine as a yellow oil which crystallizes on standing; mp 48°-50° C. Further elution gives 15.80 g (79%) of the desired product as a gold liquid. NMR (200 MHz, DMSO) δ=3.13 (t, J<3 Hz, 1, C≡CH), 3.92 (d, J<3 Hz, 2, CH2), 6.48 (br s, 1, NH, disappears on D2O addition), 6.64 (dd, J=8.9 Hz, 2.8 Hz, 1, 6H), 6.84 (d, J<3 Hz, 1, 2H), 7.32 (d, J=8.9 Hz, 1, 5H); MS (DEI): m/e=199 (M+); IR (LF): =3297, 1601, 1494 cm-1.

Workup

  1. washthe suspension is washed three times with water
  2. customThe organic layer is separated
  3. dry with materialdried (magnesium sulfate)
  4. concentrationconcentrated

Sources & evidence

ORD record
ord-1275f3d8d56f4fa1a852e7b9ad6e2518
Source dataset
uspto-grants-1989_08
Patent number
US04857530

Reaction notes

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