2-Chloroethyl vinyl ether → 4-(Diphenylamino)benzaldehyde N-(Vinyloxyethyl)-N-Phenylhydrazone

HRID 1270030

Reaction equation

HRID 1270030 reaction equation
[C:1]1([NH:7][N:8]=[CH:9][C:10]2[CH:15]=[CH:14][C:13]([N:16]([C:23]3[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=3)[C:17]3[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=3)=[CH:12][CH:11]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[CH:29]([O:31][CH2:32][CH2:33]Cl)=[CH2:30].[OH-].[K+].C(=O)([O-])[O-].[K+].[K+]>C(C(C)=O)C>[CH:29]([O:31][CH2:32][CH2:33][N:7]([C:1]1[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1)[N:8]=[CH:9][C:10]1[CH:15]=[CH:14][C:13]([N:16]([C:23]2[CH:24]=[CH:25][CH:26]=[CH:27][CH:28]=2)[C:17]2[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=2)=[CH:12][CH:11]=1)=[CH2:30]

Participants

6

Reactant 4

HCID 80742-Chloroethyl vinyl etherHCID 11430Potassium CarbonateHCID 14797Potassium HydroxideHCID 41696414-(Diphenylamino) benzaldehyde phenylhydrazone

Product 1

HCID 693354534-(Diphenylamino)benzaldehyde N-(Vinyloxyethyl)-N-Phenylhydrazone

Reagents, catalysts & solvents 1

HCID 6569Methyl Ethyl KetoneSolvent

Procedure

A mixture of 4-(diphenylamino)benzaldehyde N-phenylhydrazone (10 g, 0.027 mol) and methyl ethyl ketone (50 ml) was added to 100 ml 3-neck round bottom flask equipped with a reflux condenser and a mechanical stirrer. The mixture was stirred at room temperature until all solid entered into solution. Then, 2-chloroethyl vinyl ether (5.5 ml, 0.054 mol, from Aldrich) was added to the mixture, followed by the addition of potassium hydroxide (3.02 g, 0.054 mol) and potassium carbonate (3.73 g, 0.027 mol) in two portions. The mixture was refluxed for 15 hours. The solvent was evaporated off and the crude product was purified by column chromatography using a mixture of hexane-acetone in a volume ratio of 7:1 as the eluant. Fractions containing the product were collected and the solvents were evaporated. The product was dried at 50° C. in a vacuum oven for 5 hours to yield 3.5 g (38%). The melting point was found to be 107–108° C. The 1H-NMR spectrum (100 MHz) of the product in CDCl3 was characterized by the following chemical shifts (δ, ppm): 3.52–4.47 (m, 6H, N—CH2—CH2—O, CH2═); 6.43 (q, 1H, O—CH═); 6.70–8.03 (m, 20H, Ar, CH═N). The IR spectrum of the product was characterized by the following absorption frequencies (KBr, cm−1): ν(C—H) 2983; 2926; 2878, ν(arene C—H) 3033, ν(C═C, in Ar) 1618; 1591; 1494, ν(C—N) 1315; 1276, γ(Ar) 751; 693. The mass spectrum of the product was characterized by the following mass peaks (m/z): 434.4 (100%, M+1), 148.2.

Workup

  1. additionwas added to 100 ml 3-neck round bottom flask
  2. customequipped with a reflux condenser and a mechanical stirrer
  3. temperatureThe mixture was refluxed for 15 hours
  4. customThe solvent was evaporated off
  5. customthe crude product was purified by column chromatography
  6. additiona mixture of hexane-acetone in a volume ratio of 7:1 as the eluant
  7. additionFractions containing the product
  8. customwere collected
  9. customthe solvents were evaporated
  10. customThe product was dried at 50° C. in a vacuum oven for 5 hours
  11. customto yield 3.5 g (38%)
  12. customto be 107–108° C
  13. customThe IR spectrum of the product was characterized by the following absorption frequencies (KBr, cm−1)

Sources & evidence

ORD record
ord-05352ce00e8440e3be457f3a89e12921
Source dataset
uspto-grants-2007_04
Patent number
US07202002B2

Linked notes

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