Interaction of polyfluoroaromatic imidoyl chloride derivatives with compounds containing nitrogen-carbon multiple bonds in the presence of AlCl3

Article abstract of DOI:10.1016/S0022-1139(99)00257-2

Interactions of polyfluoroaromatic imidoyl chloride derivatives with compounds containing nitrogen-carbon multiple bond in the presence of AlCl₃ proceed as a cycloaddition type process and lead to five- or six-membered N-containing ring systems

Full text of DOI:10.1016/S0022-1139(99)00257-2

Journal of Fluorine Chemistry 103 (2000) 63±73
Interaction of poly¯uoroaromatic imidoyl chloride derivatives
with compounds containing nitrogen±carbon multiple
bonds in the presence of AlCl3
T.D. Petrova*, V.E. Platonov, I.V. Kolesnikova, T.V. Ribalova,
I.Yu. Bagryanskaya, Yu.V. Gatilov
N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Division of Russian Academy of Science,
9 Lavrentiev ave., Novosibirsk 630090, Russia
Received 16 July 1999; accepted 5 October 1999
Abstract
Interactions of poly¯uoroaromatic imidoyl chloride derivatives with compounds containing nitrogen±carbon multiple bond in the
presence of AlCl3 proceed as a cycloaddition type process and lead to ®ve- or six-membered N-containing ring systems. N-(p-R±
tetra¯uorophenyl)carbonimidoyl dichlorides (R ˆ F, CH3) react with N-penta¯uorophenyltrichloroacetimidoyl chloride and AlCl3 to give
in good yields 1-(p-R±tetra¯uorophenyl)-3-penta¯uorophenyl-4,4,5,5-tetrachloro-2-imidazolidones. N-Penta¯uorophenyltrichloroacetimi-
doyl chloride ``dimerizes'' by heating with AlCl3 to 1,3-bis(penta¯uorophenyl)-4,5-dichloro-2-imidazolone. This compound was also
obtained from 1,3-bis(penta¯uorophenyl)-4,4,5,5-tetrachloro-2-imidazolidone under the action of AlCl3. Heating of 1,3-bis(penta¯uor-
ophenyl)-4,4,5,5-tetrachloro-2-imidazolidone with AlCl3 in toluene leads to 1,3-bis(penta¯uorophenyl)-4,5-dichloro-2-imidazolone and its
5-tolyl derivatives as a result of a reaction with toluene. Interaction of N-penta¯uorophenylcarbonimidoyl dichloride with benzonitrile and
AlCl3 leads to 1-penta¯uorophenyl-4,6-diphenyl-1,3,5-triazine-2-one along with N-penta¯uorophenyl-N0-benzoylurea and an N-penta¯uoro-
phenylurea complex with benzamide. # 2000 Elsevier Science S.A. All rights reserved.
Keywords: Poly¯uoroaromatic imidoyl chloride derivatives; 2-Imidazolidones; 2-Imidazolones; 1-Penta¯uorophenyl-4,6-diphenyl-1,3,5-triazine-2-one;
AlCl3
1. Introduction
electrophilic reagents towards electron-donating substrates,
for example, aromatic amines [5] or benzene and alkylben-
zenes [6]. This work describes the ability of such electro-
philic reagents to undergo cycloaddition reactions with
compounds containing a nitrogen±carbon multiple bond
(preliminary communication [7]).
It is known that aromatic imidoyl chlorides react with
Lewis acids to give nitrilium salts which can further interact
with starting imidoyl chloride to give heterocyclic deriva-
tives [1]. The transformation of per¯uoroazapropene to the
cyclic trimer Ð 1,3,5-tris(tri¯uoromethyl)hexa¯uorohexa-
hydrotriazine [2] or 3,5-bis(tri¯uoromethyl)-4,4-di¯uoro-
hexahydrotriazine-4,6-dione [3] under the action of SbF5
has been shown. Nitrilium salts forming from N-arylimidoyl
chloride derivatives by AlCl3 react with aliphatic or aro-
matic nitriles to give new nitrilium salts which transform to
quinazoline derivatives if at least one ortho-position in the
N-aromatic ring of the starting imidoyl chloride derivative is
unoccupied [4].
2. Results and discussion
N-Penta¯uorophenylcarbonimidoyl dichloride 1 did not
change during heating with 1±3 mol of AlCl3 at 1108C. At
the same time N-penta¯uorophenyltrichloroacetimidoyl
chloride 2 under similar conditions turns into 1,3-bis(penta-
¯uorophenyl)-4,5-dichloro-2-imidazolone 3 (Scheme 1).
Imidazolone 3 is probably formed as a result of a cyclic
``dimerization'' of 2 with subsequent hydrolysis of the
product formed. This assumption is in agreement with the
ability of 2 to undergo cycloaddition type reactions with
imidoyl chlorides 1 and 4 in the presence of AlCl3. Thus, the
We have previously shown that poly¯uoroarylimidoyl
chlorides in the presence of AlCl3 can act as ef®cient
* Corresponding author. Fax: ‡7-383-234-4752.
E-mail address: petrova@nioch.nsc.ru (T.D. Petrova).
0022-1139/00/$ ± see front matter # 2000 Elsevier Science S.A. All rights reserved.
PII: S 0 0 2 2 - 1 1 3 9 ( 9 9 ) 0 0 2 5 7 - 2

64
T.D. Petrova et al. / Journal of Fluorine Chemistry 103 (2000) 63±73
Scheme 1.
reaction of 2 with 1 in the presence of AlCl3 at 1108C
(7 h) gave 1,3-bis(penta¯uorophenyl)-4,4,5,5-tetrachloro-
2-imidazolidone 5 (ꢀ90% yield). Compound 2 reacts
with N-(4-methyl-2,3,5,6-tetra¯uorophenyl)carbonimidoyl
dichloride 4 under similar conditions to give 1-penta¯uoro-
phenyl-3-(40-methyl-20,30,50,60-tetra¯uorophenyl)-4,4,5,5-
tetrachloro-2-imidazolidone 6 (ꢀ60% yield). Formation of
5 from 1 and 2 is observed at 608C to give 15±20% of 5
(GLC data). At a higher temperature (808C), the yield of 5
may run to 90%. At the same time the imidoyl chloride 2
changes to a small extent at 808C in the presence of AlCl3. A
reaction mixture containing only ꢀ4% of 3 (GLC) was
formed. The transformation of 2 under the action of AlCl3
took place at a higher temperature (1108C).
It should be noted that the reaction of 2 with compounds 1
or 4 and AlCl3 leads mainly to the corresponding imida-
zolidones 5 and 6, but not the derivatives of imidazolone.
The reaction mixture after interaction of the compounds 2
and 1 contained no or ꢀ2% of imidazolone 3. Compound 5
was partially transformed into imidazolone 3 when pure 5
was heated with AlCl3 at 1108C. The reaction did not take
place without AlCl3. The attempt to increase the conversion
of 5 into 3 by use of toluene as a solvent and potential
chlorine acceptor led to the mixture of compound 3 and the
products of interaction with toluene in the ratio ꢀ1:1 (19F
NMR and GC±MS). These products 7 have the structure of
5-tolyl derivatives of 1,3-bis(penta¯uorophenyl)-4-chloro-
2-imidazolone with different positions of CH3-groups in the
aromatic ring. By GC±MS-analysis three isomers were
monitored (38, 6 and 1%). The p-CH3 isomer probably
predominates. These isomers have identical 19F NMR spec-
tra. The reaction in toluene did not take place in the absence
of AlCl3. One of the possible schemes for the transformation
is presented in Scheme 2.
According to this scheme a cationic intermediate having
in the limit the structure of a nitrilium ion of type 8 is formed
at the ®rst stage of the reaction. The formation of such a type
of a cationic intermediate from the compound 1 and AlCl3
was previously proposed by us and supported by reactions
with aromatic amines or benzene and alkylbenzenes [5,6].
This intermediate interacts with a molecule of 2 to give
cyclic intermediate cation 9 stabilized by resonance parti-
cipation of the nitrogen lone pairs. Intermediate 9 reacts
with water to give compounds 5 and 6. Intermediate 10 with
X ˆ CCl3 with AlCl3 could be transformed into a cationic
intermediate 11. In this intermediate spatial nonvalent ``1,3-
interaction'' of the bulky CCl3-group and a chlorine atom of
the CCl2-group may be hypothesized which should favor the
rupture (for example, the heterolysis) of the C±Cl bond and
the formation of the fragment with a double bond. Futher
reactions with AlCl3 and water could result in compound 3.
Reactions of compounds 1 or 4 with 2 proceed more
readily than ``dimerization'' of 2 (lower temperature of the
reactions and the higher yields of the end products). This
could be explained by the ease of the formation of cationic
intermediate 8 when X ˆ Cl owing to increased stability of
the former in comparison with X ˆ CCl3 as well as greater
stability of 9 when X ˆ Cl in comparison with X ˆ CCl3.

T.D. Petrova et al. / Journal of Fluorine Chemistry 103 (2000) 63±73
65
Scheme 2.
There is also the possibility of the formation of allylic type
‡
AlCl3 to give imidazolone 3 and N,N0-bis(penta¯uorophe-
nyl)trichloroacetamidine 12 (Scheme 1). The structure of
compound 12 is supported by analytical and spectral data.
The stability of this compound towards the action of a base
on heating agrees with this structure.
It is reasonable to suppose the formation of cationic
intermediates 11 in Scheme 2 taking into account data
obtained in experiments with compound 5 and AlCl3 in
toluene. These can be explained by the proposal (Scheme 3)
that imidazolone 5 reacts with AlCl3 to give cationic inter-
cationic intermediates ‰C6F5N ˆ CCl CCl2 Á AlCl4 Š from
compound 2 and AlCl3. The interaction of such an inter-
mediate with 2 should also result in compound 3 but this
possibility is less probable from the literature and our data
about the reactivity of a trichloroacetimidoyl chloride
group. According to Ref. [8], only the chlorine atom and
C=N bond participate in a reaction, for example, with
nucleophiles, CCl3-group remains unchanged. According
to our data, compound 2 reacts with penta¯uoroaniline and
Scheme 3.

66
T.D. Petrova et al. / Journal of Fluorine Chemistry 103 (2000) 63±73
Fig. 1. X-ray crystal structure of 1-pentafluorophenyl-3-(40-methyl-20,30,50,60-tetrafluorophenyl)-4.4.5,5-tetrachloro-2-imidazolidone 6.
mediate 5a, similarly 11 is transformed to 3 in the absence
of toluene and to 5-tolyl derivatives 7 in the presence of
toluene. Eclipsed interaction of the tolyl-group and chlorine
atom should favor the rupture of the C±Cl bond and the
formation of a double bond.
The structures of compounds 3, 5, 7 and 12 were estab-
lished on the basis of their analytical and spectroscopic
data and by comparison with analogues. The structure of
compound 6 was determined by X-ray structural analysis
(Fig. 1).
hydrolyzed to ureas 14 and 15. The compounds 15 and
16 formed gave a complex 17.
The structure of 13 was determined by X-ray structural
analysis (Fig. 2).
The structure of 17 is based on X-ray structural analysis
data (Fig. 3) and spectroscopic characteristics.
The 19F NMR data for 17 are very similar to those for
compound 15 obtained by us in the reaction of penta¯uor-
oaniline with NaOCN (cf. [9]). 1-Penta¯uorophenyl biuret
18 was also isolated from the reaction mixture along with
15. Its 19F NMR spectra is similar to that of compound 14.
This, together with PMR, IR and MS data con®rms the
structure of 14.
The results obtained by us in the study of interaction of
carbonimidoyl dichloride 1 with nitriles are shown in
Scheme 4.
Compound 1 did not react with acetonitrile on boiling in
the presence of AlCl3. The 1:1 reaction of 1 and AlCl3 in
benzonitrile at 1508C gave 1-penta¯uorophenyl-4,6-diphe-
nyl-1,3,5-triazine-2-one 13 although unreacted starting
material 1 remained in the mixture (ratio of 1 and 13
was ꢀ3:1 according to 19F NMR data). A temperature rise
to 1758C, increased the amount of AlCl3 and further heating
favored the formation of 13 although unreacted starting
compound 1 also remained in the mixture. The reaction is
complicated due to the formation of N-penta¯uorophenyl-
N0-benzoylurea 14 and of N-penta¯uorophenylurea
15 which was isolated as a complex with benzamide 16.
Amide 16 could result from a side reaction. The suggested
reaction Scheme 5 can explain the formation of observed
products.
3. Experimental
19F and 1H spectra were recorded on a Bruker WP-200SY
instrument, internal standards were hexa¯uorobenzene
(‡162.9 ppm from CCl3F) and hexamethyldisiloxane
(0.04 ppm). IR spectra were measured on a Specord M-
80 instrument for a 5% CCl4 solution. GLC analyses were
carried out on an LHM-7a instrument with a thermal con-
ductivity detector and a linear temperature program of
108C min, using internal normalization (180±2708C, a
4000 Â 4 mm2 column packed with methylsilicon E-30,
¯uorosilicon QF-1/Chromosorb W, silicon SKTFT-50 and
SKTFV-803/Celite, 5:100 and 15:100 with He carrier at
60 ml min 1). Column chromatography was carried out on
silica gel 140±315 mesh. GC±MS analyses of the reaction
mixtures were performed with a Hewlett-Packard apparatus
5890 (70 eV) using a 30 m capillary column coated with
It can be supposed that a cationic intermediate formed
from compound 1 and AlCl3 reacts with benzonitrile to give
a new intermediate. This reacting with another molecule of
benzonitrile could be transformed to heterocycle 13 or
Scheme 4.

T.D. Petrova et al. / Journal of Fluorine Chemistry 103 (2000) 63±73
67
Scheme 5.
HP5 oil. Molecular weights and molecular formulae were
determined mass spectrometrically on a Finnigan-MAT-
8200 instrument. The nominal energy of the ionizing elec-
trons was 70 eV. The starting compounds 1 and 2 were
obtained by described procedures [10,11].
with ether. The ether layer was washed with water, dried
over CaCl2, the solvent distilled off and the residue (0.15 g)
was analyzed by 19F NMR spectroscopy and GLC. The
residue contained only starting compound 1.
3.2. 1,3-Bis(pentafluorophenyl)-4,5-dichloro-2-
imidazolone 3
3.1. Heating of compound 1 with AlCl3
1. To 0.09 g of AlCl3 was added 0.3 g of compound 2,
0.5 ml of hexafluorobenzene and the mixture was
vigorously stirred for 7 h at 1108C. The treatment of
A mixture of carbonimidoyl dichloride 1 (0.26 g) and
AlCl3 (0.4 g) was vigorously stirred for 7 h at 1108C. After
cooling the mixture was poured into water and extracted
Fig. 2. X-ray crystal structure of 1-pentafluorophenyl-4,6-diphenyl-1,3,5-triazine-2-one 13.

68
T.D. Petrova et al. / Journal of Fluorine Chemistry 103 (2000) 63±73
unidentified unfluorinated compound (66%) (GC±MS
and 19F NMR data). The eluents were hexane and
CCl4.
1,3-Bis(pentafluorophenyl)-4-chloro-5-tolyl-2-imida-
zolones 7. 19F NMR (CCl4): d ˆ 18.48 (4Fo), 11.49 (Fp),
11.03 (Fp), 1.34 (4Fm). Anal. Calc. for C22H7ClF10N2O:
M, 540.00871. Found: M, 540.00745.
3.3. 1,3-Bis(pentafluorophenyl)-4,4,5,5-tetrachloro-2-
imidazolidone 5
1. A mixture of trichloroacetimidoyl chloride 2 (0.35 g),
carbonimidoyl dichloride 1 (0.26 g), AlCl3 (0.4 g) and
hexafluorobenzene (0.5 ml) was stirred vigorously for
7 h at 1108C. After reaction, the mixture was poured
into water and extracted with ether. The ether layer was
washed with water, dried over CaCl2, the solvent
distilled off and solid residue (0.59 g) was sublimed at
105±1108C/7 mm Hg to afford 0.48 g of compound 5,
m.p. 114±1158C. 19F NMR (CHCl3): d ˆ 24.17 (4Fo),
14.42 (2Fp), 2.22 (4Fm). Anal. Calc. for C15Cl4F10N2O:
C, 32.37; Cl, 25.54; F, 34.17; N, 5.04%; M, 553.86050.
Found: C, 32.56; Cl, 25.16; F, 33.73; N, 4.99%; M,
553.86108.
2. Analogously, the reaction of trichloroacetimidoyl chlor-
ide 2 (0.35 g) with 1 (0.26 g) and AlCl3 (0.4 g) in
hexafluorobenzene (0.5 ml) at 808C (10 h) afforded a
residue containing compounds 1 and 5 in the ratio 2:19
(19F NMR). The reaction of trichloroacetimidoyl
chloride 2 (0.7 g) with 1 (0.52 g) and AlCl3 (0.8 g) in
hexafluorobenzene (1.5 ml) at 808C (10 h) afforded
1.1 g of 5 which was purified by sublimation at 105±
1108C/7 mm Hg.
3. Analogously, the reaction of trichloroacetimidoyl chlor-
ide 2 (0.35 g), carbonimidoyl dichloride 1 (0.26 g) and
AlCl3 (0.4 g) in chloroform (2 ml) at 608C (10 h)
afforded a residue containing compounds 1, 2 and 5 in
the ratio 1:1:0.5 (19F NMR).
Fig. 3. X-ray crystal structure of complex 17.
the reaction mixture was similar to that described above.
The residue (0.28 g) was washed with a small amount of
petroleum ether (70±1008C), sublimed at 908C/5 mm
Hg and then recrystallized from hexane to give 0.08 g of
compound 3. m.p. 95.5±978C. 19F NMR (ether):
d ˆ 19.43 (4Fo), 12.62 (2Fp), 1.76 (4Fm). IR:
n ˆ 1005vs, 1140m, 1300m, 1530vs, 1765vs, 1800w.
Anal. Calc. for C15Cl2F10N2O: C, 37.11; Cl, 14.64; F,
39.18; N, 5.77%; M, 483.9228. Found: C, 37.68; Cl,
14.93; F, 38.68; N, 5.53%; M, 483.9278.
The reaction mixture obtained after stirring 0.3 g of
compound 2, 0.22 g of AlCl3 and 5 ml of hexafluor-
obenzene at 808C for 7 h contained starting compound 2
and 4% of compound 3 by GLC data.
3.4. 1-Pentafluorophenyl-3-(40-methyl-20,30,50,60-
tetrafluorophenyl)-4,4,5,5,-tetrachloro-2-
imidazolidone 6
2. A mixture of compound 5 (0.05 g) and AlCl3 (0.04 g)
was heated in a sealed glass ampoule for 7 h at 1108C.
After reaction, the mixture was poured into water, the
precipitate was filtered off, washed with water, and air-
dried to give 0.04 g of the mixture of starting compound
5 and imidazolone 3 in a ratio 4:1 (19F NMR and GLC
data).
3. A mixture of compound 5 (0.2 g) and AlCl3 (0.14 g) in
2 ml of anhydrous toluene was stirred for 7 h at 1108C.
Subsequent treatment was similar to that described in
step 1. The residue contained imidazolone 3 and tolyl
derivatives 7. This residue was subjected to column
chromatography on silica gel into 0.06 g of compound 3
and 0.21 g of the mixture of 3 (19%) and 7 (15%) and
A mixture of trichloroacetimidoyl chloride 2 (0.35 g),
carbonimidoyl dichloride 4 (0.26 g) and AlCl3 (0.4 g) in
hexa¯uorobenzene (1.5 ml) was stirred vigorously for 9 h at
808C. Treatment of reaction mixture was similar to that
described above. A solid residue was recrystallized from
hexane, 0.32 g of imidazolidone 6 was obtained which was
further puri®ed by sublimation at 1408C/12 mm Hg. m.p.
146.5±1488C. 1H NMR (CDCl3): d ˆ 2.41 (CH3). 19F NMR
(CDCl3): d ˆ 24.29 (2Fo), 14.09 (Fp), 2.03 (2Fm), 21.19
(2F), 20.45 (2F). IR (CHCl3): n ˆ 1000vs, 1140s, 1160s,
1300vs, 1360m, 1520vs, 1785vs. Anal. Calc. for
C16H3Cl4F9N2O: C, 34.78; H, 0.54; Cl, 25.72; F, 30.98;

T.D. Petrova et al. / Journal of Fluorine Chemistry 103 (2000) 63±73
69
N, 5.07%; M, 549.8856. Found: C, 34.98; H, 0.57; Cl, 26.02;
F, 31.46; N, 5.26%; M, 549.8822.
3.6. Heating of 12 with a base
To a vigorously stirred suspension of freshly prepared
anhydrous K2CO3 (0.04 g) in anhydrous benzene (3 ml) was
added amidine 12 (0.15 g) and this mixture was re¯uxed for
11 h. The precipitate was ®ltered off and solvent was
distilled off from the ®ltrate. The residue contained only
starting amidine 12 (19F NMR data).
3.5. Bis(pentafluorophenyl)trichloroacetamidine 12
To a suspension of trichloroacetimidoyl chloride 2 (1.5 g)
and AlCl3 (0.66 g) was added penta¯uoroaniline (0.3 g).
The mixture was stirred vigorously for 7 h at 1108C. Sub-
sequent work-up was similar to that described above. A
residue (1.5 g) contained starting material 2, imidazolone 3
and amidine 12 in the ratio 1:3.25:2.75 (19F NMR). This
residue was subjected to column chromatography on silica
gel into 1.4 g of the mixture of compound 3 and 12 (eluent
hexane/benzene (20:1 by vol.)). Then this procedure was
repeated to yield compound 3 (0.24 g) and amidine 12
(0.66 g) along with a mixture of compounds 3 and 12
(0.18 g) (eluent hexane/benzene (1:1 by vol.)). Amidine
12 was puri®ed by recrystallization from hexane, m.p. 76±
788C. 19F NMR (CCl4): d ˆ 17.7 (2F), 13.3 (2F), 8.2 (F), 0.5
(2F), 0.2 (F), 1.6 (2F). IR: n ˆ 1005vs, 1050s, 1530vs,
3.7. Interaction of carbonimidoyldichloride 1 with
benzonitrile in the presence of AlCl3
A mixture of compound 1 (0.26 g) and AlCl3 in benzo-
nitrile (1.5 ml) was stirred vigorously at the temperature
indicated in Table 1. After reaction, the mixture was poured
into cold water and extracted with ether. The ether layer was
dried over CaCl2, the ether distilled off and the residue
analyzed by 19F NMR spectroscopy, GLC and GC±MS. The
results are shown in Table 1. The solid precipitate ®ltered off
and analyzed. In experiment 1 (see Table 1), solid com-
pound 13 was obtained when benzonitrile was removed
under vacuum from residue and puri®ed by recrystallization
from acetone. A mixture of compounds 14 and 17 was
treated with the solution of 25% aq. NH3. The insoluble
precipitate of 14 was ®ltered off, washed with water and
recrystallized from acetone and ethanol. After evaporation
‡
1700s, 3400m, 3430m. MS (m/z, formula): 492 (M , 3Cl),
473 (M±F), 457 (M±Cl), 375 (M±CCl3), 310 (M±NHC6F5).
Anal. Calc. for C14HCl3F10N2: C, 34.04; H, 0.20; Cl, 21.58;
F, 38.50; N, 5.67%; M, 491.9045. Found: C, 33.99; H, 0; Cl,
21.64; F, 38.60; N, 5.36%; M, 491.9057.
Table 1
Interaction of compound 1 with benzonitrile in the presence of AlCl3
Experiment
AlCl3, g (mmol)
Reaction temperature, 8C (time, h)
Reaction products
Compound
Ratio by 19F NMR (g)
Residue after reaction
Precipitate
1
2
0.14 (1)
0.14 (1)
150 (7.5)
1
3
1 (0.06)
13
1
150 (19.5)
6
13
14
15
1
3.8
1
1
1.7 (0.06)
1
3
4
5
6
7
0.27 (2)
0.4 (3)
150 (6.5)
150 (15)
175 (6)
9.6
3.6
1
13
14
15
1
1
4.5 (0.02)
1.4
6.5a
13
2
13
14
15
1
1
1.7 (0.06)
2
1
0.14 (1)
0.14 (1)
0.27 (2)
3.5
7.5
2
13
14
15
1
1
1
2a
1 (0.09)
175 (9.5)
175 (7)
13
14
15
1
7
2
2
5 (0.15)
4
1
1
13
14
15
12.5
9
1
2.5 (0.06)
1.25
4
aRatio of the products in filtrate.

70
T.D. Petrova et al. / Journal of Fluorine Chemistry 103 (2000) 63±73
Table 2
Atomic coordinates (Â104) and equivalent isotropic displacement
of aq. NH3 the residue of 17 was recrystallized (petroleum
ether (70±1008C) and acetone (1:1 by vol.)).
parameters (A2 Â 103) for compound 6
1-Penta¯uorophenyl-4,6-diphenyl-1,3,5-triazine-2-one 13.
m.p. 227±2318C (in sealed capillary). 1H NMR (d-acetone):
d ˆ 7.49±7.75 (2C6H5). 19F NMR (d-acetone): d ˆ 20.22
(2Fo), 11.99 (Fp), 1.73 (2Fm). IR (KBr): n ˆ 990vs, 1360vs,
1436m, 1480m, 1525vs, 1590m, 1710vs, 3050w. Anal. Calc.
for C21H10F5N3O: M, 415.07439. Found: M, 415.07458.
N-Penta¯uorophenyl-N0-benzoylurea 14. m.p. 189±
Atom
x/a
y/b
z/c
U(eq)a
O(1)
6289(2)
6345(2)
6054(3)
5413(2)
5233(3)
5995(3)
7060(3)
7211(3)
7903(3)
8472(3)
8307(3)
7621(3)
9222(4)
4904(3)
4608(3)
4112(3)
3895(3)
4186(4)
4690(4)
6687(2)
8029(2)
8836(2)
7504(2)
4820(2)
3848(2)
3402(2)
3986(3)
4987(3)
4716(1)
4749(1)
6007(1)
6373(1)
422(2)
13136(5)
10200(6)
11808(7)
11597(6)
9828(7)
8987(7)
10034(7)
9227(8)
9080(9)
9647(8)
10431(8)
10642(8)
9397(15)
12924(7)
13562(8)
14813(9)
15487(9)
14900(9)
13642(8)
8666(5)
8278(5)
11049(6)
11486(5)
12966(5)
15442(6)
16715(5)
15583(6)
13107(5)
9193(2)
9290(2)
6908(2)
8931(2)
8234(5)
5323(6)
6899(7)
6700(6)
4920(8)
4148(8)
5098(7)
4275(8)
4078(8)
4663(8)
5517(9)
5720(8)
4405(14)
8014(7)
8660(8)
9909(8)
10515(8)
9920(8)
8684(8)
8086(5)
10518(5)
11732(5)
10539(6)
8173(5)
6576(5)
6178(6)
3249(5)
3663(5)
4176(2)
4401(2)
812(2)
50(1)
34(1)
37(1)
35(1)
38(1)
39(1)
36(1)
44(1)
50(2)
48(2)
50(2)
44(1)
69(2)
35(1)
43(1)
54(2)
65(2)
67(2)
54(2)
62(1)
72(1)
76(1)
66(1)
63(1)
88(1)
103(2)
118(2)
87(1)
52(1)
57(1)
59(1)
63(1)
54(1)
44(1)
39(1)
42(1)
48(2)
47(2)
40(1)
45(1)
50(2)
46(2)
49(2)
44(1)
65(2)
40(1)
42(1)
49(2)
50(2)
49(2)
44(1)
62(1)
72(1)
77(1)
78(1)
59(1)
65(1)
72(1)
71(1)
62(1)
62(1)
63(1)
N(1)
C(2)
913(2)
955(2)
N(3)
1192(2)
1212(2)
1219(2)
775(2)
C(4)
C(5)
C(10)
C(20)
C(30)
C(40)
1
1948C. H NMR (acetone): d ˆ 10.48 (NH), 10.44 (NH),
8.10 (2HAr), 7.74±7.54 m (3HAr) 19F NMR (acetone):
d ˆ 17.83 (2Fo), 4.70 (Fp), 1.15 (2Fm). IR (KBr): n ˆ
1025s, 1270vs, 1325m, 1450±1475vs, 1525vs, 1670s, 1700±
1715vs, 3175m, 3250m. Anal. Calc. for C14H7F5N2O2: M,
330.04276. Found: M, 330.04175.
318(2)
185(2)
481(2)
C(50)
935(2)
C(600)
1076(2)
328(4)
C(700)
Complex 17 of N-penta¯uorophenylurea 15 and benza-
mide 16. m.p. 127±1308C. 19F NMR (acetone): d ˆ 16.40
(2Fo), 2.10 (Fp), 1.95 (2Fm).
C(100)
C(200)
C(3 )
C(400)
C(500)
C(600)
F(200)
1180(2)
724(2)
716(3)
1171(3)
1630(3)
1634(2)
2(1)
3.8. N-Pentafluorophenylurea 15 and N-
pentafluorophenylbiuret 18
F(30)
266(1)
F(500)
1251(2)
1509(1)
278(1)
A solution of 0.33 g NaNCO in 3 ml water was added to a
solution of 0.91 g penta¯uoroaniline in 3 ml of acetic acid
and stirred for 2 h at 50±608C, then cooled to room tem-
perature. The reaction mixture contained (19F NMR)
unreacted penta¯uoroaniline together with 15 and 18 and
an unidenti®ed product having a C6F5-group (ratio was
9.8:1.9:2.6:1). A precipitate (0.08 g) from the reaction
mixture was ®ltered off, washed with water and a small
amount of hexane to give compound 18 (m.p. 194±1968C)
after recrystallization from aq. ethanol. 1H NMR (acetone):
d ˆ 9.86 (NH), 8.86 (NH), 6.54 (NH2). 19F NMR (acetone):
d ˆ 17.28 (2Fo), 4.05 (Fp), 1.35 (2Fm). IR (KBr): n ˆ
1000±1010s, 1240m, 1250m, 1325m, 1460m, 1500±1525vs,
1610s, 1700vs, 1705s, 3000m, 3200s, 3480vs. Anal. Calc.
for C8H4F5N3O2: M, 269.02236. Found: M, 269. 02292. The
®ltrate was diluted with water and the precipitate formed
(0.12 g) was ®ltered off, washed with water and recrystal-
lized from aq. ethanol. It contained 15 and 18 and the above
unidenti®ed product (19F NMR (acetone): d ˆ 17.59 (2Fo),
4.62 (Fp), 1.14 (2Fm)) in the ratio 2.5:1.4:1 (19F NMR).
N-Penta¯uorophenylurea 15. 19F NMR (acetone): d ˆ
16.40 (2Fo), 2.56 (Fp), 1.72 (2Fm). Anal. Calc. for
C7H3F5N2O: M, 226.01655. Found:M, 226.01753.
F(600)
F(200)
F(300)
269(2)
F(4 )
1159(2)
2066(2)
2080(1)
652(1)
F(500)
F(600)
Cl(1)
Cl(2)
1747(1)
979(1)
Cl(3)
Cl(4)
1858(1)
1269(2)
1398(2)
1453(2)
1773(2)
1832(2)
1771(2)
1116(2)
646(2)
O(1A)
N(1A)
C(2A)
N(3A)
C(4A)
C(5A)
C(10A)
C(20A)
C(30A)
C(40A)
C(50A)
C(600A)
C(700A)
C(100A)
C(200A)
C(3 A)
C(400A)
C(500A)
C(600A)
F(200A)
F(300A)
F(400A)
F(500A)
F(600A)
F(60A)
F(50A)
F(30A)
F(20A)
Cl(1A)
Cl(2A)
321(2)
628(3)
1239(2)
1395(3)
632(3)
334(3)
348(3)
961(3)
355(2)
1601(3)
1586(3)
971(3)
512(2)
972(2)
1273(2)
194(4)
2282(5)
1751(3)
2111(3)
2615(3)
2778(3)
2421(3)
1920(3)
1952(2)
2954(2)
3281(2)
2580(2)
1558(2)
983(2)
1841(2)
1427(2)
1507(2)
1984(2)
2394(2)
2319(2)
953(1)
3.9. X-ray structural analysis of compounds 6, 13 and
complex 17
1105(1)
2058(2)
2863(1)
2722(1)
1716(1)
1145(1)
101(1)
Molecular structures of compounds 6, 13 and 17 are
illustrated in Figs. 1±3. X-ray data were measured on a
Syntex P21 diffractometer with graphite monochromated Cu
Ka radiation using y/2y scans with 2y < 1308 for 6 and
2y < 1408 for 13 and 17. Numerical corrections for absorp-
tion were applied. The structures were solved using direct
methods (SHELXS-86) [12] and re®ned in the anisotropic±
2185(2)
944(2)
255(2)
469(1)
1923(1)
1849(1)
1324(1)
2412(1)

T.D. Petrova et al. / Journal of Fluorine Chemistry 103 (2000) 63±73
71
Table 2 (Continued )
Table 4
Atomic coordinates (Â104) and equivalent isotropic displacement
U(eq)a
parameters (A2 Â 103) for compound 13
Atom
x/a
y/b
z/c
Atom
x/a
y/b
z/c
U(eq)a
Cl(3A)
Cl(4A)
596(1)
200(1)
2016(2)
4286(2)
1568(1)
2364(1)
61(1)
66(1)
N(1)
C(2)
278(6)
6067(5)
7237(7)
7002(6)
5763(7)
4642(5)
4832(6)
6194(6)
5381(7)
5434(9)
6293(9)
7155(8)
7067(6)
5444(8)
6326(8)
6011(10)
4880(10)
3990(10)
4291(8)
3682(6)
2357(6)
1259(8)
1472(8)
2809(8)
3919(7)
4545(5)
4636(6)
6326(6)
8019(5)
7891(4)
8317(4)
5223(2)
4860(2)
4349(2)
4203(2)
4543(2)
5037(2)
5756(2)
5937(3)
6449(3)
6817(3)
6634(2)
6116(2)
3640(2)
3251(2)
2725(3)
2572(3)
2946(3)
3478(2)
5422(2)
5340(3)
5683(3)
6107(3)
6189(3)
5842(2)
5594(2)
6623(2)
7320(2)
6976(2)
5961(2)
5036(2)
50(1)
55(2)
55(1)
53(1)
53(1)
47(1)
51(1)
63(2)
79(2)
80(2)
66(2)
52(1)
60(2)
68(2)
86(2)
98(3)
96(3)
76(2)
47(1)
64(2)
76(2)
78(2)
78(2)
61(2)
89(1)
124(2)
115(2)
97(2)
71(1)
67(1)
aU(eq) is defined as one-third of the trace of the orthogonalized Uij
tensor.
12(8)
N(3)
C(4)
376(6)
978(8)
N(5)
C(6)
1354(6)
1043(7)
289(7)
isotropic approximation using SHELXL-93 [13] program
package. The positions of hydrogen atoms were located
from different Fourier synthesis 6, 17 or given geometrically
13.
C(7)
C(8)
1681(8)
2169(10)
1333(11)
3(9)
C(9)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
C(20)
C(21)
C(22)
C(23)
C(24)
F(1)
Compound 6 (Fig. 1) is monoclinic, space group P21/c,
Ê
a ˆ 18.894(6), b ˆ 7.834(2), c ˆ 26.070(9) A, b ˆ
484(8)
Ê 3
93.01(3)8 V ˆ 5853(2) A , C16H3Cl4F9N2O, M ˆ 552.00,
1239(8)
528(9)
Z ˆ 8, Dc ˆ 1.903 g cm 3, m ˆ 6.546 mm 1, F(0 0 0) ˆ
2160, crystal size 0.10 Â 0.17 Â 0.90 mm3, 6340 indepen-
dent re¯ections (transmission 0.20±0.64), wR2 ˆ 0.1480,
S ˆ 0.983 for all re¯ections (R ˆ 0.0596 for 3547 F >
4s) (see Tables 2 and 3).
767(11)
1730(13)
2432(13)
2212(10)
1472(7)
783(9)
Compound 13 (Fig. 2) is orthorhombic, space group
Ê
1145(10)
2215(11)
2956(10)
2594(9)
2516(6)
3501(7)
1802(8)
793(7)
P212121, a ˆ 7.766(3), b ˆ 9.349(3), c ˆ 25.180(10) A,
Ê 3
V ˆ 1828(1) A , C21H10F5N3O, M ˆ 415.32, Z ˆ 4,
3
1
Dc ˆ 1.509 g cm
,
m ˆ 1.139 mm
,
F(0 0 0) ˆ 840,
crystal size 0.04 Â 0.70 Â 0.85 mm3, 1767 independent
re¯ections (transmission 0.56±0.96), wR2 ˆ 0.1930, S ˆ
1.016, for all re¯ections (R ˆ 0.0619 for 1180 F > 4s).
Delocalized p-system of s-triazine is broken in compound
13 (Fig. 2) and a new one is formed on atoms N(1), C(2),
N(3), C(4), C(13), C(14), C(15), C(16), C(17), C(18). This
conclusion was drawn on the basis of bond lengths. Bonds
F(2)
F(3)
F(4)
F(5)
1825(5)
703(6)
O(1)
aU(eq) is defined as one-third of the trace of the orthogonalized Uij
tensor.
Ê
N(1)±C(2) (1.441(8) A) and C(4)±N(5) (1.384(7) A) are
Ê
Table 3
Ê
Bond lengths (A) and selected torsional angles (8) for compound 6
O(1)±C(2)
1.198(6)
1.381(7)
1.422(6)
1.425(7)
1.398(7)
1.414(6)
1.428(7)
1.583(7)
1.759(5)
1.785(5)
1.745(6)
1.780(5)
13.2(6)
O(1A)±C(2A)
1.206(6)
1.369(7)
1.417(6)
1.441(7)
1.398(6)
1.417(7)
1.432(7)
1.564(8)
1.746(6)
1.798(6)
1.752(6)
1.790(6)
13.3(6)
N(1)±C(2)
N(1)±C(10)
N(1)±C(5)
N(1A)±C(2A)
N(1A)±C(10)
N(1A)±C(5A)
C(2)±N(3)
N(3)±C(100)
C(2A)±N(3A)
N(3A)±C(100A)
N(3)±C(4)
C(4)±C(5)
N(3A)±C(4A)
C(4A)±C(5A)
C(4)±Cl(2)
C(4A)±Cl(2A)
C(4)±Cl(1)
C(4A)±Cl(1A)
C(5)±Cl(3)
C(5)±Cl(4)
C(5A)±Cl(3A)
C(5A)±Cl(4A)
C(5)±N(1)±C(2)±N(3)
C(10)±N(1)±C(2)±N(3)
C(60)±C(10)±N(1)±C(5)
N(1)±C(2)±N(3)±C(4)
O(1)±C(2)±N(3)±C(4)
C(2)±N(3)±C(4)±C(5)
N(3)±C(4)±C(5)±N(1)
C(4)±C(5)±N(1)±C(2)
C(100)±N(3)±C(2)±N(1)
C(600)±C(100)±N(3)±C(2)
C(5A)±N(1A)±C(2A)±N(3A)
C(10A)±N(1A)±C(2A)±N(3A)
C(60A)±C(10A)±N(1A)±C(5A)
N(1A)±C(2A)±N(3A)±C(4A)
O(1A)±C(2A)±N(3A)±C(4A)
C(2A)±N(3A)±C(4A)±C(5A)
N(3A)±C(4A)±C(5A)±N(1A)
C(4A)±C(5A)±N(1A)±C(2A)
C(100A)±N(3A)±C(2A)±N(1A)
C(600A)±C(100A)±N(3A)±C(2A)
168.3(6)
88.4(6)
176.5(6)
92.7(6)
11.0(6)
12.0(7)
168.0(6)
27.4(5)
32.5(5)
168.3(7)
29.5(6)
34.6(5)
28.7(5)
30.1(6)
164.8(6)
119.8(6)
168.8(6)
120.6(6)

72
T.D. Petrova et al. / Journal of Fluorine Chemistry 103 (2000) 63±73
Table 6
Atomic coordinates (Â104) and equivalent isotropic displacement
markedly lengthened by comparison with analogues
Ê
1.412(4) and 1.351(4) A in 4,6-dimethoxy-3-methyl-1,3,5-
Ê
triazine-2(3H)-one [14] and 1.382(4) and 1.353(4) A in 4,6-
dimethoxy-1,3,5-triazine-2(1H)-one [15]. Bond C(5)=N(6)
Ê
(1.279(6) A) is the same as the literature double bond CAr±
Ê
C=N±C# 1.279(8) A [16] (see Tables 4 and 5).
parameters (A2 Â 103) for molecular complex 17
Atom
x/a
2566(3)
y/b
z/c
U(eq)a
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
C(10)
C(11)
C(12)
C(13)
C(14)
N(1)
N(2)
N(3)
O(1)
O(2)
F(1)
2353(2)
2360(3)
2912(3)
3521(3)
3525(3)
2906(3)
2998(3)
1951(2)
2556(3)
2745(4)
2351(4)
1752(4)
1539(3)
1750(3)
1790(2)
2319(3)
2685(3)
4560(2)
755(2)
2850(1)
1956(1)
1354(1)
1630(1)
2511(1)
3104(1)
4135(1)
2516(1)
2509(2)
1717(2)
938(2)
43(1)
49(1)
55(1)
52(1)
48(1)
44(1)
42(1)
46(1)
58(1)
78(1)
89(1)
81(1)
60(1)
53(1)
48(1)
55(1)
72(1)
55(1)
80(1)
71(1)
83(1)
76(1)
67(1)
60(1)
3177(3)
1884(3)
Molecular complex 17 (Fig. 3) is triclinic, space group
Ê
77(3)
739(3)
559(3)
P1, a ˆ 6.837(1), b ˆ 7.120(1), c ˆ 15.283(2) A, a ˆ
Ê 3
91.09(1), b ˆ 96.16(1), g ˆ 97.79(1)8, V ˆ 732.4(2) A ,
3
C14H10F5N3O2, M ˆ 347.25, Z ˆ 2, Dc ˆ 1.575 g cm
,
4167(2)
10581(3)
12603(3)
13814(4)
13036(5)
11055(5)
9825(4)
9160(3)
3897(2)
5540(3)
9714(3)
3161(2)
7547(2)
5101(2)
2531(2)
1345(2)
2649(2)
152(2)
m ˆ 1.333 mm 1, F(0 0 0) ˆ 352, crystal size 0.08 Â
0.35 Â 0.8 mm3, 2717 independent re¯ections (transmis-
sion 0.49±0.90), wR2 ˆ 0.1132, S ˆ 1.048 for all re¯ections
(R ˆ 0.0394 for 2064 F > 4s) (see Tables 6 and 7).
The molecular complex is formed by hydrogen bonds
943(2)
1723(2)
3335(1)
3462(1)
4651(1)
4033(1)
4271(1)
3359(1)
1669(1)
494(1)
Ê
N(1)±HÁ Á ÁO(2) (N±H 0.85(2), OÁ Á ÁH 2.06(2) A, N±HÁ Á ÁO
157(2)8) and N(2)±H(2A)Á Á ÁO(2) (N±H 0.82(2), OÁ Á ÁH
Ê
2.28(2) A, N±HÁ Á ÁO 147(2)8).
Atomic coordinates, bond lengths and angles have
been deposited at the Cambridge Crystallographic Data
Center.
1805(2)
2888(2)
4107(2)
4131(2)
2826(2)
F(2)
F(3)
F(4)
1051(1)
2787(1)
3954(1)
Table 5
F(5)
Ê
Bond lengths (A) and selected torsional angles (8) for compound 13
aU(eq) is defined as one-third of the trace of the orthogonalized Uij
tensor.
N(1)±C(6)
1.380(7)
1.418(7)
1.441(8)
1.226(7)
1.342(7)
1.301(8)
1.384(7)
1.463(8)
1.279(6)
1.485(8)
1.360(8)
1.398(8)
1.333(7)
1.345(9)
1.348(9)
1.386(11)
1.320(7)
1.392(10)
1.332(7)
1.357(8)
1.353(7)
1.378(10)
1.395(9)
1.369(9)
1.352(11)
1.370(11)
1.380(9)
1.365(8)
1.388(8)
1.369(9)
1.369(10)
1.391(10)
1.386(9)
71.7(2)
N(1)±C(7)
N(1)±C(2)
C(2)±O(1)
C(2)±N(3)
N(3)±C(4)
C(4)±N(5)
C(4)±C(13)
N(5)±C(6)
Table 7
Ê
Bond lengths (A) and selected torsional angles (8) for molecular complex
17
C(6)±C(19)
C(7)±C(12)
C(7)±C(8)
C(1)±C(2)
C(1)±C(6)
C(1)±N(1)
C(2)±F(1)
1.386(3)
1.386(2)
1.400(2)
1.344(2)
1.370(3)
1.340(2)
1.370(3)
1.339(2)
1.373(3)
1.339(2)
1.373(3)
1.343(2)
1.228(2)
1.337(2)
1.371(2)
1.388(3)
1.390(3)
1.492(3)
1.386(3)
1.373(4)
1.362(4)
1.377(4)
1.224(2)
1.331(3)
59.9(7)
C(8)±F(1)
C(8)±C(9)
C(9)±F(2)
C(9)±C(10)
C(10)±F(3)
C(2)±C(3)
C(3)±F(2)
C(10)±C(11)
C(11)±F(4)
C(3)±C(4)
C(4)±F(3)
C(11)±C(12)
C(12)±F(5)
C(4)±C(5)
C(5)±F(4)
C(13)±C(18)
C(13)±C(14)
C(14)±C(15)
C(15)±C(16)
C(16)±C(17)
C(17)±C(18)
C(19)±C(20)
C(19)±C(24)
C(20)±C(21)
C(21)±C(22)
C(22)±C(23)
C(23)±C(24)
C(2)±N(1)±C(7)±C(8)
N(1)±C(6)±C(19)±C(24)
N(3)±C(4)±C(13)±C(14)
C(5)±C(6)
C(6)±F(5)
C(7)±O(1)
C(7)±N(2)
C(7)±N(1)
C(8)±C(13)
C(8)±C(9)
C(8)±C(14)
C(9)±C(10)
C(10)±C(11)
C(11)±C(12)
C(12)±C(13)
C(14)±O(2)
C(14)±N(3)
C(6)±C(1)±N(1)±C(7)
60.1(2)
13.2(3)

T.D. Petrova et al. / Journal of Fluorine Chemistry 103 (2000) 63±73
73
[8] Yu.I. Matveyev, V.I. Gorbatenko, L.I. Samarai, Tetrahedron 47
(1991) 1563.
References
[9] L.J. Belf, British patent 923 365 [Chem. Abstr. 59 (1963) P
9886f].
[1] J.C. Jochims, R. Abu-El-Halawa, L. Zsolnai, G. Huttner, Chem. Ber.
117 (1984) 1167.
[10] T.I. Savchenko, I.V. Kolesnikova, T.D. Petrova, V.E. Platonov, J.
Fluorine Chem. 22 (1983) 439.
[2] L. Knunyants, A.F. Gontar, Soviet Scientific Rev. Section B 5 (1984)
219.
[11] T.D. Petrova, T.I. Savchenko, V.E. Platonov, G.G. Yakobson,
Izv. Sib. Otd. Akad. Nauk SSSR, Ser. Khim. Nauk 5 (1981) 109.
[12] G.M. Sheldrick, Acta Crystallogr. A46 (1990) 467.
[13] G.M. Sheldrick, Acta Crystallogr. A49 (Suppl.) (1993) C53.
[14] E. Handelsman-Benory, M. Botoshansky, M. Kaftory, Acta Crystal-
logr. C51(11) (1995) 2421.
[3] H. BuÈrger, R. KoÈplin, G. Pawelke, C. KruÈger, J. Fluorine Chem. 22
(1983) 175.
[4] H. Meerwein, P. Laasch, R. Mersch, J. Nentwig, Chem. Ber. 89
(1956) 224.
[5] T.D. Petrova, V.E. Platonov, Zh. Org. Khim. 33 (1997) 745.
[6] T.D. Petrova, I.V. Kolesnikova, V.I. Mamatyuk, V.P. Vetchinov, V.E.
Platonov, I.Yu. Bagryanskaya, Yu.V. Gatilov, Russ. Chem. Bull., Ser.
Khim. 42 (1993) 1540.
[15] M.L. Glowka, V. Bertolasi, Acta Crystallogr. C43(1) (1987) 149.
[16] F.A. Allen, O. Kennard, D.G. Watson, L. Brammer, A.G. Orpen, R.
Taylor, J. Chem. Soc., Perkin Trans. II (1987) 1.
[7] I.V. Kolesnikova, T.D. Petrova, V.E. Platonov, E.G. Ron'zhina, J.
Fluorine Chem. 45 (1989) 74.