Solid state selective synthesis of diaryl carbazone

Article abstract of DOI:10.1081/SCC-100103253

The selective synthesis of diaryl carbazone using K₃Fe(CN)₆ as oxidant under alkaline condition in solid state is reported for the first time. Eight diaryl carbazone have been synthesized in excellent yields, and this method only needs cheap reagents, and simple procedure under mild condition.

Full text of DOI:10.1081/SCC-100103253

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SOLID STATE SELECTIVE
SYNTHESIS OF DIARYL
CARBAZONE
Jun-Ping Xiao a , Yu-Lu Wang b & Qing-Xiang Zhou a
a Department of Chemistry , Henan Normal
University , Xinxiang, Henan, 453002, P. R. China
b Department of Chemistry , Henan Normal
University , Xinxiang, Henan, 453002, P. R. China
Published online: 16 Aug 2006.
To cite this article: Jun-Ping Xiao , Yu-Lu Wang & Qing-Xiang Zhou (2001) SOLID
STATE SELECTIVE SYNTHESIS OF DIARYL CARBAZONE, Synthetic Communications:
An International Journal for Rapid Communication of Synthetic Organic Chemistry,
31:5, 661-665, DOI: 10.1081/SCC-100103253
To link to this article: http://dx.doi.org/10.1081/SCC-100103253
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SYNTHETIC COMMUNICATIONS, 31(5), 661–665 (2001)
SOLID STATE SELECTIVE SYNTHESIS OF
DIARYL CARBAZONE
Jun-Ping Xiao, Yu-Lu Wang,* and Qing-Xiang Zhou
Department of Chemistry, Henan Normal University,
Xinxiang, 453002, Henan, P.R.China
ABSTRACT
The selective synthesis of diaryl carbazone using
K3Fe(CN)6 as oxidant under alkaline condition in solid
state is reported for the first time.Eight diaryl carbazone
have been synthesized in excellent yields, and this method
only needs cheap reagents, and simple procedure under mild
condition.
Solid state organic reactions have caused great interest in recent years,
having many advantages such as high efficiency and selectivity,1 easy
separation and purification, mild reaction condition,2 and environmental
acceptability, etc.3,4 This method has been widely used in a variety of
organic syntheses, but its application in synthesis of diaryl carbazone
under alkaline condition in solid state has not been reported before.
Diaryl carbazone is an important organic analytical reagent normally
synthesized by the oxidation of aryl substituted carbazide, and KClO3/
5
H2SO4/FeSO4 or FeCl3/H2SO4 have been used as oxidant.
In the previous work, our laboratory has used 2,4,6-t-(t-C4H9)3
C6H2OH/K3Fe(CN)6/KOH phase transfer system as oxidant system,
diaryl carbodiazone was the only product although the amount
* Corresponding author.
661
Copyright & 2001 by Marcel Dekker, Inc.
www.dekker.com

662
XIAO, WANG, AND ZHOU
of K3Fe(CN)6 was controlled (Scheme 1).FeCl has also been used as
3
oxidant under acid condition in solid state, if the amount of oxidant
was controlled, diaryl carbazone and diaryl carbodiazone were prepared
respectively.In this paper, We used K Fe(CN)6/KOH oxidation system to
3
synthesize diaryl carbazone from aryl substituted carbazide in solid state for
the first time (Scheme 2), at room temperature diaryl carbazone is the only
product even the excess oxidant is used, furthermore this method only
requires simple instrument, short reaction time and easy work-up
procedure.Eight diaryl carbazone compounds have been synthesized in
excellent yields.
Scheme 1.
Scheme 2.
EXPERIMENTAL
Melting points were determined on kofler micro melting point
apparatus without correction.Elemental analyses were performed on a
Perkin-Elmer 240C analytical instrument.Infrared spectra were recorded
1
on a SP3-300 spectra photometer using KBr pellets. HNMR spectra were
measured in CDCl3 using TMS as internal standard with a JEOL-Fx-90Q
NMR spectrometer.

DIARYL CARBAZONE
General Procedure of the Preparation of Diaryl Carbazone
663
A mixture of 0.01 mol of 1 and 0.041 mol of K3Fe(CN)6 and
0.3–0.4 mmol of KOH was ground in an agate mortar. After 20–30 minutes,
The color of the mixture turned orange yellow, orange or dark green.Then
20 ml of water was added, then yellow, orange and orange red and dark
green products were precipitated.The product was isolated by filtration, and
washed with water four times.The products were recrystallized from a
mixture of ethanol and water, and dried under vacuum.Structures of
1
these products were characterized by elemental analysis, IR and HNMR
spectroscopy.
Diphenyl Carbazone 2a
Orange needle; yield 89%; m.p. 154–155ꢀC; IR(KBr)ꢀ: 3448, 3306,
3035, 1710, 1665, 1604, 1527, 1485 cmÀ1
;
1HNMR(CDCl3) ꢁ: 7.91ꢁ8.11
(d,2H, NHNH), 7.13ꢁ7.58(m, 10H, 2C6H5).Anal.Calcd.for C 13H12N4O:
C, 64.99, H, 5.03; N, 22.98. Found: C, 64.72; H, 4.98; N, 23.02.
Di(2-Methylphenyl) Carbazone 2b
Yellow needle; yield 87%; m.p. 126–127ꢀC; IR(KBr)ꢀ: 3430, 3340,
3050, 2920, 2855, 1677, 1605, 1547, 1487 cmÀ1
;
1HNMR(CDCl3) ꢁ:
7.66ꢁ7.97(d, 2H, NHNH), 6.97ꢁ7.34(m, 8H, 2C6H4), 2.73(s, 3H, CH3);
2.31(s, 3H, CH3).Anal.Calcd.for C 15H16N4O: C, 67.14; H, 5.96; N,
20.88. Found: C, 66.94; H, 5.73; N, 20.54.
Di(3-Methylphenyl) Carbazone 2c
Brown Yellow leaflet; yield 84%; m.p. 167–168ꢀC; IR(KBr)ꢀ: 3380,
1
3330, 3040, 2920, 1645, 1610, 1585, 1465, 1410 cmÀ1; HNMR(CDCl3) ꢁ:
7.20ꢁ7.62(d, 2H, NHNH), 6.72ꢁ7.15(m, 8H, 2C6H4), 2.50(s, 3H, CH3);
2.32(s, 3H, CH3).Anal.Calcd.for C
20.88. Found: C, 66.75; H, 5.42; N, 20.51.
15H16N4O: C, 67.14; H, 5.96; N,
Di(4-Methylphenyl) Carbazone 2d
Orange red leaflet; yield 81%; m.p. 132–133ꢀC; IR(KBr)ꢀ: 3390, 3280,
3045, 2920, 2870, 1712, 1650, 1600, 1515, 1465 cmÀ1 1HNMR(CDCl3)
;

664
XIAO, WANG, AND ZHOU
ꢁ: 7.25ꢁ7.70(d, 2H, NHNH), 6.60ꢁ7.12(m, 8H, 2C6H4), 2.45 (s, 3H, CH3);
2.25 (s, 3H, CH3).Anal.Calcd.for C 15H16N4O: C, 67.14; H, 5.96; N, 20.88.
Found: C, 66.93; H, 5.68; N, 20.18.
Di(2,3-Methylphenyl) Carbazone 2e
Orange leaflet; yield 86%; m.p. 116–117ꢀC; IR(KBr)ꢀ: 3410, 3320,
1
3035, 2916, 2860, 1690, 1590, 1490, 1475, 1455 cmÀ1; HNMR(CDCl3) ꢁ:
7.37ꢁ7.85(d, 2H, NHNH), 6.64ꢁ7.20(m, 6H, 2C6H3), 2.13(s, 6H, 2CH3);
2.41(s, 6H, 2CH3).Anal.Calcd.for C 17H20N4O: C, 68.90; H, 6.80; N, 18.90.
Found: C, 68.53; H, 6.62; N, 18.51.
Di(2,6-Methylphenyl) Carbazone 2f
Yellow leaflet; yield 90%; m.p. 193–194ꢀC; IR(KBr)ꢀ: 3480, 3320,
1
3040, 2910, 2875, 1690, 1605, 1575, 1480, 1410 cmÀ1; HNMR(CDCl3) ꢁ:
7.25ꢁ7.83(d, 2H, NHNH), 6.50ꢁ7.25(m, 6H, 2C6H3), 2.15(s, 6H, 2CH3);
2.37(s, 6H, 2CH3).Anal.Calcd.for C 17H20N4O: C, 68.90; H, 6.80; N, 18.90.
Found: C, 68.22; H, 6.56; N, 18.40.
Di(4-Ethyloxyphenyl) Carbazone 2g
Orange leaflet; yield 89%; m.p. 159–161ꢀC; IR(KBr)ꢀ: 3390, 3205,
1
3027, 2970, 1705, 1675, 1601, 1573, 1503, 1465 cmÀ1; HNMR(CDCl3) ꢁ:
7.89ꢁ8.10(d, 2H, NHNH), 6.94ꢁ7.26(m, 8H, 2C6H4), 3.94ꢁ4.25(q, 4H,
2CH2); 1.37ꢁ1.65(t, 6H, 2CH3).Anal.Calcd.for C 17H20N4O3: C, 62.18;
H, 6.14; N, 17.06. Found: C, 61.78; H, 6.13; N, 16.97.
Di(4-Nitrophenyl) Carbazone 2h
Brown leaflet; yield 70%; m.p. 240–242ꢀC; IR(KBr)ꢀ: 3450, 3335,
3060, 2915, 2850, 1655, 1630, 1585, 1519, 1490 cmÀ1 1HNMR(CDCl3)
;
ꢁ: 8.12ꢁ9.15(d, 2H, NHNH), 6.60ꢁ7.45(m, 8H, 2C6H4), Anal.Calcd.
for C13H10N6O5: C, 47.28; H, 3.05; N, 25.45. Found: C, 46.91; H, 3.42;
N, 24.89.
REFERENCES
1. Desiraju, G.R. (Ed.). ‘‘Organic Solid State Chemistry’’, Elsevier Science
Publishers: Amsterdam, 1987, p.179.

DIARYL CARBAZONE
665
2. Rasmussen, M.O.; Axelsson, O.; Tanner, D. Synth Commun. 1997,
27, 4027.
3.Wang, L-M. .
Hua Xue Tong Bao 1992, 6, 14.
4. Li, X.-L.; Wang, Y.-M.; Meng, J.-B.; Du, C.-P. Youji Huaxue 1998,
18, 20.
5. Wang, Y.-L.; Shi, L.; Jia, X.-S.; etc. Synth. Commun. 1999, 29, 53–56.