1,1-Dimethylhydrazine → N-[(E)-[(E)-3-(4-bromo-2-prop-2-ynoxyphenyl)prop-2-enylidene]amino]-N-methylmethanamine

HRID 2369481Notes

Reaction equation

HRID 2369481 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5](/[CH:8]=[CH:9]/[CH:10]=O)=[C:4]([O:12][CH2:13][C:14]#[CH:15])[CH:3]=1.[O-]S([O-])(=O)=O.[Mg+2].[CH3:22][N:23]([CH3:25])[NH2:24]>ClCCl>[Br:1][C:2]1[CH:7]=[CH:6][C:5](/[CH:8]=[CH:9]/[CH:10]=[N:24]/[N:23]([CH3:25])[CH3:22])=[C:4]([O:12][CH2:13][C:14]#[CH:15])[CH:3]=1

Participants

5

Reactant 3

HCID 59761,1-DimethylhydrazineHCID 24083Sulfuric acid magnesium salt (1:1)HCID 866958863-(4-Bromo-2-prop-2-ynyloxy-phenyl)-propenal

Product 1

HCID 89791447N-[(E)-[(E)-3-(4-bromo-2-prop-2-ynoxyphenyl)prop-2-enylidene]amino]-N-methylmethanamineYield 90%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A solution of (E)-3-(4-bromo-2-(prop-2-ynyloxy)phenyl)acrylaldehyde (2.85 g, 10.8 mmol) in dichloromethane (200 mL) containing anhydrous MgSO4 (16 g) was cooled in an ice bath with stirring. To the ice-cold solution was added 1,1-dimethylhydrazine (2.45 mL, 32.4 mmol) dropwise and the reaction mixture was allowed to warm up to ambient temperature and was stirred for 18 h. The volatiles were concentrated under reduced pressure and the residue was coevaporated sequentially with dichloromethane (50 mL), dichloroethane (50 mL) and heptane (50 mL). (E)-2-((E)-3-(4-bromo-2-(prop-2-ynyloxy)phenyl)allylidene)-1,1-dimethylhydrazine (2.7 g, 8.79 mmol, 90% yield, 90% purity) was obtained as a yellow powder. 1H NMR (500 MHz, CDCl3) δ 7.39 (d, J=7.9 Hz, 1H), 7.20-7.10 (m, 3H), 7.00-6.86 (m, 2H), 4.75 (d, J=2.3 Hz, 2H), 2.95 (s, 6H), 2.58 (t, J=2.3 Hz, 1H); LCMS (Method B) (ESI) m/e 307.0, 309.0 Br pattern [(M+H)+, calcd for C14H15BrN2O 307.0].

Workup

  1. temperaturewas cooled in an ice bath
  2. stirringwas stirred for 18 h
  3. concentrationThe volatiles were concentrated under reduced pressure

Sources & evidence

ORD record
ord-7869d09514fd4a4186a0c6e318d64e43
Source dataset
uspto-grants-2014_04
Patent number
US08703953B2

Reaction notes

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