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Mesoionic 2-Benzoyl-1-benzoylimino-4 5-dimethyl-1 2 3-triazole.

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111 F. Bentz and G.-E. Nischk, DAS 1235300 (1967), Farbenfabriken Bayer AG.
121 F. Bentz and G.-E. Nischk, DAS 1235302 (1967), Farbenfabriken Bayer AG.
131 Cf. P. A . Petjunin and V. P. Cernyek, 2. org. Chim. 1966,285.
[4] F. Bentz, R . Braden, and G.-E. Nischk, DAS 1293741 (1969),
Farbenfabriken Bayer AG.
m.p. 144 "C). A further 28 g can be recovered by concentration of the mother liquor, m.p. 142"C, total yield 91 %. If
recrystallized starting material is used, yields of more than
93 of the ether can be obtained.
Received: September 5, 1969
[Z 86 1El
German version: Angew. Chem. 82, 19 (1970)
Publication delayed at authors' request
[*I Dr. H. Witt, Prof. Dr. H. Holtschmidt, and Dr. E. Miiller
A New Synthesis of Substituted Diphenyl Ethers
By H . Witt, H . Holtschmidt, and E . Miiller[*]
Dedicaied to Professor K . Hansen on the occasion of his
60 th birthday
It has already been reported 111 that phenyl o-phenoxybenzoate can be prepared in high yields by heating a melt of
diphenyl carbonate in the presence of small amounts of
KzC03 a t 23&270 "C. We have now found that the diphenyl
ethers (2) can be prepared from 0- and/or p-substituted diphenyl carbonates ( I ) when subjected to similar reaction
conditions.
Wissenschaftliches Hauptlaboratorium
der Farbenfabriken Bayer A G
509 Leverkusen-Bayerwerk (Germany)
[l] P . W . Bachmann and B. W. Hammarin, US-Pat. 2319197
(May 18, 1943) General Chemical Co.; Chem. Abstr. 37, 62807
(1943); A . Davis and 1. H . Golden, J. chem. Soc. (London)
B 1968, 40.
121 H . Witt, H . Holtschmidt, and E . Miiller, DAS 1290148
(May 13, 1967), Farbenfabriken Bayer AG.
13) Cf. Th. K . Brotherton and J. W. Lynn, US-Pat. 3256220
(June 14,1966) Union Carbide Corp.; Chem. Abstr. 65,18498 G
(1966); J . M . A . Hoeflake, Recueil Trav. chim. Pays-Bas 36, 62
(1916); 40, 510, 513 (1921).
Mesoionic 2-Benzoyl-1-benzoylimino4,5-dimethyl-l,2,3-triazole
'R3
(1)
By S. Petersen and H . Heitzer [*I
Dedicated to Professor K, Hunsen on the occasion of his 60th
birthday
The oxidation product first prepared by H . v. Pechmann and
W. Bauer by reaction of 2,3-butanedione bis(benzoy1hydrazone) ( I ) [11with potassium hexacyanoferratefrrr) wasformulat(2).
ed [21 as 2,3-dibenzoyl-5,6-dimethyl-2,3-diliydrotetraazine
Catalyst
wt.- % calc.
w. r. t. ( I )
H
H
NO2
NO2
CI
H
H
H
H
H
1 K2CO3
0.5 KOCOCH,
NO2 1 KOCOCH,
NO2 1 KOCOCHi
c1 1 K2C03
H
1 KzCO,
H
1 K2CO3
H
1 K2C03
Temp.
f "C)
H3C
210-250
180-205
190-220
156-1 86
186-226
200-242
240-260
200-2 14
x
H3C ,N-NH-CO-C,H,
N-NH-CO-CBH,
H3C
17
> 90
41
89
31
65
66
22
[ a ] Not optimized.
A prerequisite for this reaction is that a t least one of the
groups R1-R" is a second order substituent; preparatively
useful yields, however, are obtainable only from symmetrically substituted, particularly p,p'-disubstituted, diphenyl
carbonates. Numerous other alkali metal compounds may
be used as catalysts (in amounts of 0.5-2 wt.-%) instead of
potassium carbonate.
The 1H-NMR spectra (in CDC13) of the oxidation product at
60 and 220 MHz 131 show that the compound does not have
a symmetrical structure. Two methyl-group signals appear in
the 60 MHz spectrum at 2.23 ppm and 2.36 ppm in addition
to a multiplet (signal width ca. 20 Hz) centered at 8.1 ppm
which is due to the protons of both aromatic rings that are
ortho to the carbonyl groups. i n the 220 MHz spectrum the
multiplet is resolved into two pseudo doublets at 8.116 ppm
and 8.236 ppm ( J = 7.8 to 8.0 Hz). The remaining six aromatic protons absorb between 7.4 and 7.8 ppm. On the basis
of these findings, therefore, we suggest that the oxidation
product has the structure of a mesoionic triazole (3),
4,4'-Dinitrodiphenyl ether (2), Rl=R2=N02, R3=R4=H [21
4,4'-Dinitrodiphenyl carbonate (1000 g) (crude phosgenation
product, m.p. 140 " C )[3J is melted (silicone oil bath) in a 2 1
three-necked flask fitted with stirrer, internal thermometer,
and a delivery tube connected via a bubble counter. Potassium acetate (5 g) is added slowly, with stirring, to the melt
'C,
a t a temperature of 150 'C. Decarboxylation (18@-205
bath temperature 190-215 "C) is complete after 4-5 hours.
The temperature of the mixture is then allowed to drop to
150 'C, and, after the apparatus has been fitted with a reflux
condenser, toluene (580 g) is added slowly. The solution is
filtered hot from insoluble residue (ca. 8 g). The filtrate is
then cooled and the 4,4'-dinitrodiphenyl ether which crystallizes out is recovered by filtration, washed with a little
methanol, and finally dried in a vacuum (yield 749 g (88 %),
Angew. Chem. internat. Edit. 1 Vol. 9 (1970)
1 No. I
(3), R = CO-C6H5
which is in agreement with the chemical properties of this
compound. The ready hydrolytic and thermal loss of a
benzoyl group is now understandable since the compound is
being considered as a n azolider41. As is already known, compound (3) affords l-(dibenzoylamin0)-4,5-dimethyl-1,2,3triazole ( 4 ) 151 when heated and l-benzoylamino-1,2,3-triazole ( 5 ) when treated with hydrochloric acid. Hydrolysis of
(3) with concentrated hydrochloric acid at higher temperatures leads to formation of the free 1-amino-4,s-dimethyl1,2,3-triazole ( 6 ) [21. We have obtained 4-chlorobenzoic anhydride as reaction product by recrystallizing compound ( 7 )
67
,R
from aqueous dimethylformamide. All these secondary reactions can now be adequately explained without recourse, as
previously, to complicated assumptions of rearrangement
and ring contraction.
Received: August 25, 1969
[Z 93 IEI
German version: Angew. Chem. 82, 81 (1970)
Publication delayed at authors’ request
[*I Prof. Dr. S. Petersen and Dr. H. Heitzer
Wissenschaftliches HauptIaboratorium und
Ingenieurabteilung Angewandte Physik,
Farbenfabriken Bayer AG
509 Leverkusen-Bayerwerk (Germany)
[ l ] H. v. Pechmann and W. Bauer, Chem. Ber. 33, 645 (1900);
42, 664 (1909).
[2] R. Srollk, J. prakt. Chem. 78,554 (1908); Chem. Ber. 59,1742
(1926).
[3I We thank Dr. 5. Wendisch for the recording of the 220 MHz
spectrum.
[4] H. A. Staab, Angew. Chem. 74, 407 (1962); Angew. Chem.
internat. Edit. I, 351 (1962).
151 See dissertations by K . Th. KeIler, 0. Wul’; and by E. Theobald, Heidelberg 1909-1912.
Table. Representative carboximide derivatives.
I:
:1
CI
H
H
H
H
H
CI
Br
~.~-(CH~)Z-C~H~-O
~-CHJ-C~H~-O
CsK5-0
CI3C-CH2-0
2,4-(CH3),-C6H3-0
Morpholino
(C2Hs)zN
(CHZ=CH-CH~)~N
Piperidino
C6Hs-CH2-N(CH3)
Morpholino
Morpholino
H
CH3
174- 176
152-154
148-150
138-139
197- 198
205-207
119-120
77-78
158- 159
112-114
249-250
287-288
(decomp.)
163- 165
122-124
81
-
35
46
78
53
76
80
65
62
49
25
-
stirring, the reaction mixture is cooled, mixed with about
50-80 ml alcohol, and the compound ( 4 a ) which separates
is recovered by filtration (48 g = 81 % yield).
Received: November 4, 1969
[Z 118 IEl
German version: Angew. Chem. 82, 81 (1970)
I*] Dr. E. Grigat
Direct Conversion of Cyclic Carboxylic Acid
Anhydrides into Carboximide Derivatives
By E. Grigat [*I
Dedicated t o Professor K . Hansen on the occasion of his 60th
birthday.
Although cyanates (2),X = OR, react with carbonyl halides
to give N-acyliminocarbonic halides [I], attempted reactions
with carboxylic anhydrides have so far been unsuccessful [*,31.
Cyclic anhydrides of aromatic and cycloaliphatic dicarboxylic acids ( I ) are exceptions. They react exothermally with
cyanates (2), X = OR, at 150 OC in the presence of catalytic
amounts of triethylamine to give N-acylated cyclic dicarboximides ( 4 ) , X = OR. Cyanamides react analogously, even
without addition of triethylamine, to give ( 4 ) , X = NR2 (see
Table). The reaction probably proceeds, like reaction of (2)
with acid halides, via a primary N-acylation of the CN group.
The non-isolable primary addition product (3) is stabilized
by intramolecular transacylation to (4).
The compounds ( 4 ) , X = OR, can be converted into compounds (4), X = NR2, by reaction with amines.
Wissenschaftliches Laboratorium der
Zwischenproduktenabteilung der Farbenfabriken Bayer AG
509 Leverkusen-Bayerwerk (Germany)
[l] E. Grigat, Angew. Chem. 81, 623 (1969); Angew. Chem.
internat. Edit. 8, 607 (1969).
[2] E. Crigat and R . Putter, Chem. Ber. 98, 1359 (1965).
[3] Reviews: E. Grigat and R . Putter, Angew. Chem. 79, 219
(1967); Angew. Chem. internat. Edit. 6, 206 (1967); D . Martin,
Z. Chem. 7, 123 (1967).
Separation of Nucleosides on Polymer Gels
Containing Thymine or Cytidine
By G . Greber and H . Schott [*I
By using Amberlite ion exchangers, which contained covalent
built-in nucleoside species, Tuppy and Kuchler[ll were able to
separate via the base-pairing reaction of Watson and Crick 121
the corresponding nucleoside from a n aqueous solution of
two nucleosides. These experiments were carried out with
extremely small amounts of substance (0.04 mg/0.04 ml).
In the meantime it has been established %41 that measurable
base pairing of nucleosides takes place only in chloroform or
N-(2,4-DimethyIphenoxycarbonyl)phthalimide( 4 a )
A mixture of phthalic anhydride (29.6 g, 0.20 mole) and 2,4dimethylphenyl cyanate (32.5 g, 0.22 mole) is heated and
stirred a t 180 “C. On adding a few drops of triethylamine the
temperature of the mixture rises to 230 ‘C. After 15 minutes’
68
Angew. Chem. internat. Edit. 1 Vol. 9 (1970)
1 No. I
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