Acetone → 9-Ethyl-3-carbazolecarbaldehyde n-2,3-epoxypropyl-n-phenylhydrazone

HRID 1295541Notes

Reaction equation

HRID 1295541 reaction equation
[C:1]1([NH:7][N:8]=[CH:9][C:10]2[CH:11]=[CH:12][C:13]3[N:14]([CH2:23][CH3:24])[C:15]4[C:20]([C:21]=3[CH:22]=2)=[CH:19][CH:18]=[CH:17][CH:16]=4)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[OH-].[K+].C(=O)([O-])[O-].[K+].[K+].[CH3:33][C:34]([CH3:36])=[O:35]>C(C1OC1)Cl.CCOCC.CCCCCC>[O:35]1[CH2:36][CH:34]1[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:11]=[CH:12][C:13]2[N:14]([CH2:23][CH3:24])[C:15]3[C:20]([C:21]=2[CH:22]=1)=[CH:19][CH:18]=[CH:17][CH:16]=3

Participants

8

Reactant 4

HCID 180AcetoneHCID 11430Potassium CarbonateHCID 14797Potassium HydroxideHCID 688623579-Ethyl-3-carbazolecarbaldehyde phenylhydrazone

Product 1

HCID 731765569-Ethyl-3-carbazolecarbaldehyde n-2,3-epoxypropyl-n-phenylhydrazoneYield 81.2%

Reagents, catalysts & solvents 3

HCID 3283Diethyl EtherSolventHCID 7835EpichlorohydrinSolventHCID 8058HexaneSolvent

Procedure

A mixture of 9-ethyl-3-carbazolecarbaldehyde phenylhydrazone (3.1 g, 0.01 mol), 85% powdered potassium hydroxide (2.0 g, 0.03 mol) and anhydrous potassium carbonate (˜5 g) in 25 ml of epichlorohydrin was stirred vigorously at 55–60° C. for 1.5–2 h. The course of the reaction was monitored using thin layer chromatography on silica gel 60 F254 plates (commercially obtained from Merck) using a 1:4 volume per volume mixture of acetone and hexane as the eluant. After termination of the reaction, the mixture was cooled to room temperature, diluted with ether and washed with water until the wash water was neutral in pH. The organic layer was dried over anhydrous magnesium sulfate, treated with activated charcoal, and filtered. Ether was removed, and the residue was dissolved in the mixture of toluene and 2-propanol in 1:1 ratio by volume. The crystals formed upon standing were filtered off, and washed with 2-propanol to give 3.0 g (81.2%) of 9-ethyl-3-carbazolecarbaldehyde N-2,3-epoxypropyl-N-phenylhydrazone. The solid product had a melting point (m.p.) of 136–137° C. after being recrystallized from a mixture of toluene and 2-propanol in 1:1 ratio by volume. A 1H-NMR spectrum of 9-ethyl-3-carbazolecarbaldehyde N-2,3-epoxypropyl-N-phenylhydrazone was obtained in CDCl3 with a 250 MHz NMR. The peaks were found at (ppm) δ=8.35 (s, 1H, 4-HHt); δ=8.14 (d, J=7,8 Hz, 1H, 1-HHt); δ=7.93 (d, J=7,6 Hz, 1H, 2-HHt); δ=7.90 (s, 1H, CH═N); δ=7.54–7.20 (m, 8H, Ph, Ht); δ=6.96 (t, J=7.2 Hz, 1H, 4-HPh); δ=4.37 (m, 3H, CH2CH3, one of the NCH2 protons); δ=4.04 (dd, J1=4.3 Hz, J2=16.4 Hz, 1H, next of the NCH2 protons); δ=3.32 (m, 1H, CH); δ=2.88 (dd, 1H, part of the ABX system, cis-HA of CH2O, JAX=2.6 Hz, JAB=4.9 Hz); δ=2.69 (dd, 1H, part of the ABX system, trans-HB of CH2O, JBX=4.0 Hz); δ=1.44 (t, J=7.2 Hz, 3H, CH3). An elemental analysis found the following weight percents of the elements: C, 78.32; H, 6.41; N, 11.55. which compares with the following calculated elemental weight percent for a compound with the formula C24H23N3O: C, 78.02; H, 6.28; N, 11.37.

Workup

  1. customAfter termination of the reaction
  2. washwashed with water until the wash water
  3. dry with materialThe organic layer was dried over anhydrous magnesium sulfate
  4. additiontreated with activated charcoal
  5. filtrationfiltered
  6. customEther was removed
  7. dissolutionthe residue was dissolved in the mixture of toluene and 2-propanol in 1:1 ratio by volume
  8. customThe crystals formed
  9. filtrationupon standing were filtered off
  10. washwashed with 2-propanol

Sources & evidence

ORD record
ord-0681a17062ed42698bc3b61f08fd4ef3
Source dataset
uspto-grants-2007_07
Patent number
US07244541B2

Reaction notes

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