Reactions of N-(perfluorophenyl)carbonimidoyl dichloride with aromatic acids and their derivatives in the presence of AlCl3. Formation of 2-(perfluorophenyl)isoindoline-1,3-dione and its derivatives

Article abstract of DOI:10.1007/s11178-005-0147-5

Reactions of N-(perfluorophenyl)carbonimidoyl dichloride with benzoic acid, benzoyl chloride, ethyl benzoate, and also with phthalic acid, phthaloyl dichloride, and phthalic anhydride in the presence of AlCl₃ at 170°C afford2-(perfluorophenyl)isoindoline-1,3-dione. With benzoic acid and benzoyl chloride form also 2-(perfluorophenyl)-3-[(perfluorophenyl)imino] isoindolin-1-one. In reactions with compounds of the benzene series arise also derivatives of arylimidoyl chlorides and amide type compounds containing a CONHC₆F₅ moiety. 2005 Pleiades Publishing, Inc.

Full text of DOI:10.1007/s11178-005-0147-5

Russian Journal of Organic Chemistry, Vol. 41, No. 2, 2005, pp. 218-226. Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 2, 2005,
pp. 228-236.
Original Russian Text Copyright Ó 2005 by Petrova, Platonov.
Reactions of N-(Perfluorophenyl)carbonimidoyl Dichloride
with Aromatic Acids and Their Derivatives
in the Presence of AlCl3. Formation
of 2-(Perfluorophenyl)isoindoline-1,3-dione and its Derivatives
T.D. Petrova and V.E. Platonov
Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Division, Russian Academy of Sciences
Novosibirsk, 630090 Russia
e-mail: petrova@nioch.nsc.ru
Receved June 22, 2004
Abstract—Reactions of N-(perfluorophenyl)carbonimidoyl dichloride with benzoic acid, benzoyl chloride, ethyl
benzoate, and also with phthalic acid, phthaloyl dichloride, and phthalic anhydride in the presence of AlCl3 at
170°C afford 2-(perfluorophenyl)isoindoline-1,3-dione. With benzoic acid and benzoyl chloride form also
2-(perfluorophenyl)-3-[(perfluorophenyl)imino]isoindolin-1-one. In reactions with compounds of the benzene
series arise also derivatives of arylimidoyl chlorides and amide type compounds containing a CONHC6F5 moiety.
We formerly demonstrated that polyfluoroaromatic
compounds containing an imidoyl chloride moiety in the
presence ofAlCl3 acted as efficient electrophilic reagents
capable of reacting with various aromatic compounds.
Reactions with benzane and alkyl benzenes gave rise to
imidoyl chlorides and azomethines [1], and with
fluorinated benzenes depending on the number of fluorine
atoms in the benzene ring the process afforded imidoyl
chlorides, azomethines, or polyfluorinated derivatives of
1,2,3,4-tetrahydroquinazoline-2,4-dione [2]. The reaction
with aromatic amines occurred at the amino group
nitrogen affording the corresponding guanidines [3]. The
reaction at the multiple carbon–nitrogen bond in the
aromatic imidoyl chlorides or nitriles furnished 5- or 6-
membered heterocyclic derivatives [4].
of GC-MS analysis. According to these data the final
mixtures contained unreacted initial compound I, 2-
(perfluorophenyl)isoindoline-1,3-dione (IIIa), 2-(per-
fluorophenyl)-3-[(perfluorophenyl)imino]isoindolin-1-
one (IV), compounds of amide type with a moiety
CONHC6F5 V, imidoyl chloride derivatives
C6F5N=C6H4R VI, decafluorodiphenylurea (VII),
pentafluoroaniline (VIII), and unidentified compounds
present in small amounts (Scheme 1). In reaction with
ethyl benzoate (IIc) the reaction mixture obtained at
130°C contained also a considerable amount of compound
presumably having structure of ethyl(perfluorophenyl)-
carbamoyl chloride (IX). A specific feature of reaction
with ester IIc consisted in formation of isomeric ethyl
derivatives IIIb–IIId where the number of the ethyl
groups in the benzene ring grew with growing temperature
from one to three.
We report here on the study of reactions between N-
(perfluorophenyl)carbonimidoyl dichloride (I) and some
aromatic acids and their derivatives in the presence of
AlCl3.
The qualitative composition of the final reaction
mixtures obtained with compounds IIa–IIc was not
affected by increased reaction temperature and prolonged
heating, but the conversion of substrate I grew and the
relative quantity of the reaction products changed.
Therewith the amounts of cyclic compounds III and IV
and amides V increased.
The reactions of equimolar amounts of dichloride I
and benzoic acid (IIa) and also its derivatives, benzoyl
chloride (IIb) and ethyl benzoate (IIc), in the presence
of 2.5-molar amount ofAlCl3 at 130 and 170°C occurred
with a considerable tarring and resulted in complex
mixtures of products the majority of which were identified
with the use of 19F NMR and IR spectroscopy, and also
Heterocyclic compounds IIIa and IV are the main
products of the reaction between dichloride I and benzoyl
1070-4280/05/4102-0218Ó2005 Pleiades Publishing, Inc.

REACTIONS OF N-(PERFLUOROPHENYL)CARBONIMIDOYL DICHLORIDE
219
Scheme 1.
2
2
$O&O ꢀ'
&21+& )
& ) 1 &&O & + &25
,,D ,,F
1 & )
1 & )
1 & )
,
5
5 5
2
,,,D ,,,G
9D 9F
,9
& ) 1 &&O& + 5ꢀꢁꢀꢂ& ) 1+ꢃ &2ꢀꢁꢀ& ) 1+ ꢀꢁꢀ& ) 1ꢂ& + ꢃ&2&O
9,Dꢀꢁ9,E
9,,,
,;
9,,
II, R = OH (a), Cl (b), OEt (c); III, R1 = R2 = R3 = H (a); R1 = R2 = H, R3 = Et (b); R1 = H, R2 = R3 = Et (c); R1 = R2 = R3 = Et (d); V,
R = H (a), CONHC6F5 (b), COOH (c) ; VI, R = H (a), COCl (b).
Scheme 2.
2
+ 2
,,,D
,9
2
1 & )
&O
, RU 9,,,ꢁ $O&O
+
$O&O
,
1 & )
&O
&O
,ꢀꢀꢀ,,E
& + &2
;
+ 2
&O
$
& + &21+& )
9D
chloride IIb. With an enhanced molar amount of com-
pound I andAlCl3 [ratio equal to (I):(IIb):AlCl3 = 2:1:5]
at 170°C the relative formation of compound IV some-
what grew, but under these conditions the product IIIa
still prevailed in the reaction mixture that also contained
a large quantity of unreacted initial dichloride I.
benzoyl cation is intermediately formed and taking into
consideration the already mentioned [3, 4] capability of
imidoyl chloride moiety to react with electrophiles at the
nitrogen
Possible patterns of compounds IIIa and IV formation
in reaction of acyl chloride IIa involving an intermediate
A are presented in Scheme 2.
In contrast to the reaction with acyl chloride IIb
dichloride Iwith acid IIa in the presence of AlCl3 afforded
in the temperature range studied mainly amide derivatives
V as the main reaction mixture components. At 130°C
formed predominantly amide Va, and at 170°C alongside
this compound the reaction mixture contained diamides
Vb with prevailing content of one of the isomers. Initial
compound I is virtually lacking in the final mixtures, and
compounds IIIa, IV and VI–VIII are present as minor
components.
This scheme is corroborated by transformation into
reaction products IIIa and IV of independently syn-
thesized 3,3-dichloro-2-(perfluorophenyl)isoindolin-1-one
(X). The synthesis of substituted isoindolin-1-one X was
performed by heating cyclic compound IIIa with PCl5
(Scheme 3). This reaction provided also 1,1,3,3-tetra-
chloro-2-(perfluorophenyl)isoindoline (XI), and the ratio
X:XI depended on the amount of PCl5 used. Both
compounds are very prone to hydrolysis, especially the
tetrachloro derivative XI, and they are converted into
dione IIIa even during column chromatography on silica
gel, and therefore preparation of these compounds in a
pure state has been a difficult task. Compound X by
reaction with initial dichloride I or polyfluorinated aniline
VIII is converted into (imino)isoindolin-1-one IV, and
tetrachloroisoindoline XI is transformed into 1,3-bis-
[(perfluorophenyl)imino]-2-(pentafluorophenyl)isoindoline
(XII). The possibility of (imino)isoindolin-1-one IV
formation from isoindoline-1,3-dione IIIa was checked
The reaction of dichloride I with ester IIc alongside
compounds III and IX also gave rise to a large quantity
of amide derivatives V, but here at 130°C amide Va is
a minor component of the mixture, and in reaction at
170°C it was not detected even by GC-MS method.
Compound IV also was not identified in this reaction.
At the first glance the formation in reactions under
study of compounds IIIa and IV containing a phthalimide
fragment seems unexpected. However it can be
understood assuming that in the course of the reaction a
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 41 No. 2 2005

220PETROVA,
PLATONOV
Scheme 3.
&O
1 & )
1 & )
&O
$O&O
3&O
9,,,
,,,D
ꢀ
;
1 & )
&O
,ꢁRUꢁ9,,, $O&O
9,,, $O&O
&O
1 & )
;,
2
;,,
2
,9
1+& )
1+& )
&O
&O
9,,,
,,,D
Rꢂ9E
,9
2
2
;,,,
Scheme 4.
+ 2
$O&O
& + &&O2&&O
Rꢂ9E
9,E
9F
1& )
$O&O
,,E
& ) 1 &&O $O&O
$O&O
,
& + &&O 2&&O 1& )
%
$O&O
& + &&O $O&O
9,,,
& ) 1 & 2
1& )
& + &&O 2&
$O+&O
+ 2 9,,,
$O&O
9,,,
9D
,,E
9,D
9,,,
9D
9,,
+ 2
%
& ) 1 &&O& + &21+& )
9E
by a special experiment of heating the latter with penta-
fluoroaniline VIII in the presence of AlCl3, but the
conversion of compound IIIa into substance IV was
small, and besides a significant amount N,N'-bis-
(perfluorophenyl)phthalamide (o-Vb) was obtained.
Inasmuch as the latter compound was not detected in
notable quantities in the products of reaction between
dichloride I and acyl chloride IIb the contribution of
isoindoline-1,3-dionea IIIa conversion into (imino)-
isoindolin-1-one IV under the action of pentafluoroaniline
VIII in the presence ofAlCl3 was minimal. The structure
of phthalimide o-Vb was confirmed by an independent
synthesis from phthaloyl dichloride (XIII) by treating with
pentafluoroaniline VIII. The reaction occurred already
at room temperature and afforded a mixture of products
o-Vb and IIIa. On adding N,N-dimethylaniline as base
the only reaction product formed was dione IIIa. Probably
amide o-Vb transformed into dione IIIa. In any case in
the analysis of individual compound o-Vb by GC-MS
procedure only isoindoline-1,3-dione IIIa and penta-
fluoroaniline VIII were detected.
The presumable paths of amides V formation in reac-
tions of dichloride I with acyl chloride IIb are shown on
Schemes 2 and 4. The formation of imidoyl chloride
derivatives in this reaction may be due to participation of
a cationoid intermediate B of nitrilium type that reacts
with compound IIb along Scheme 4. We formerly already
pointed out the ability if of polyfluoroaromatic compounds
containing an imidoyl chloride moiety to act in the
presence of AlCl3 as active electrophiles of this type [1–
4]. The stage of imidoyl chloride VIa formation presented
on Scheme 4 involving the a,a-dichlorobenzyl cation is
analogous to the process we have suggested before for
the formation of this compound from benzotrichloride,
aniline VIII, and AlCl3 [5]. Scheme 4 provides also
an understanding of appearance in the system of penta-
fluoroaniline VIII and urea VII involving perfluorophenyl
isocyanate; however, these compounds may arise from
a side reaction: a hydrolysis of initial dichloride I effected
by traces of moisture that we have observed previously
[4].
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 41 No. 2 2005

REACTIONS OF N-(PERFLUOROPHENYL)CARBONIMIDOYL DICHLORIDE
221
The reaction products of processes involving acid IIa
and ester IIc apparently arise along pathways similar to
those shown on Schemes 2 and 4. Therewith in reaction
of acid IIa the intermediate formation of a benzoyl cation
requires water liberation that may facilitate the hydrolysis
of initial dichloride I and accumulation of aniline VIII in
the system. Its reaction with the benzoyl cation should
furnish amide Va. This reaction pattern probably accounts
for the larger amount of amide Va in reaction products of
acid IIa compared to those obtained from its chloride
IIb.
the amides to suffer transformations in the course of GC-
MS analysis complicated the individual identification of
these compounds when obtained in a mixture.
Imidoyl chlorides VI were identified in the reaction
mixtures without separation using the data of GC-MS
analysis and fluorine chemical shifts in the 19F NMR
spectra. The chemical shifts were close in values to those
for the previously described [10] imidoyl chloride derivative
VIa and other polyfluoroaromatic imidoyl chloride
derivatives [11].
The spectral characteristics of compound IX which
was detected but not isolated were similar to those of
the previously described N-methyl analog [10] and thus
they confirm the assumed structure.
Heterocyclic compounds IIIb–IIId with the ethyl
groups attached to the benzene ring form in reaction of
dichloride I and ester IIc in the presence of AlCl3
apparently from dione IIIa by Friedel–Crafts reaction.
The ethylation of initial dichloride I at the nitrogen atom
with subsequent hydrolysis may be responsible for
compound IX formation.
The formation of heterocyclic compounds in reaction
of dichloride I with compounds IIa–IIc promoted the
extension of the range of aromatic acids to be brought
into reaction with it in the presence of AlCl3. In this
connection it was interesting to study the behavior in this
reaction of aromatic dicarboxylic acids and their
derivatives since in this case it was expectable to obtain
tricyclic systems containing two phthalimide fragments.
Taking into account the experience obtained in this study
we investigated the reaction of dichloride I with phthalic
acid (XIV), phthaloyl dichloride (XIII), and phthalic
anhydride (XV). It proved however that in all cases
formed predominantly compound IIIa in a high yield. In
the reaction mixture obtained from phthaloyl dichloride
(XIII) among the reaction products was identified also
a small amount of cyclic dichloride X, and in the case of
acid XIV formed a little urea VII.
The structure of reaction products obtained from
dichloride I and acid IIa or its derivatives IIb, IIc was
derived mainly from their analysis and spectral
characteristics. Compound IIIa was synthesized earlier
by other methods [6, 7]. Its 19F NMR spectrum [7] was
identical to that registered by us. However the
characteristics given in [6] were unlike those obtained in
the present study. We reproduced the synthesis described
in [6] and obtained a sample of isoindoline-1,3-dione IIIa
completely identical to our product. ,
The structure of ethyl derivatives IIIb–IIId that were
not isolated in an individual state was assigned to them
based on the data of GC-MS analysis, the elemental
analyses and molecular weights deduced from the high
resolution mass spectra, and on the composition of
fragment ions in the mass spectra (formation of a fragment
ion [M – CH3]+ characteristic of compounds with an ethyl
group attached to a benzene ring), on the appearance of
ethyl group proton signals at ~1 and ~2.8 ppm in the 1H
NMR spectra, and close values of fluorine chemical shifts
in the 19F NMR spectra of these compounds and
substance IIIa.
The formation of compound IIIa in these reactions
can be understood by assuming (as in the case of benzoic
acid IIa and its derivatives IIb, IIc) that in the processes
take part cationoid intermediates of A or B type arising
from initial carbonyl compounds XIII–XV and dichloride
I under the action of AlCl3. One of the reaction routes
involving the ionization of a carbonyl compound is shown
on Scheme 5 by an example of phthaloyl dichloride (XIII).
In the scheme reaction of dichloride I is assumed to occur
with a cationoid intermediate of benzoyl type formed from
phthaloyl dichloride (XIII) which at high temperature and
in the presence ofAlCl3 can exist either in cyclic or open
form [12]. The resulting cationoid intermediate A', similar
to intermediate A, is involved into a sequence of
transformations leading finally to dione IIIa and CCl4.
The latter was detected in the reaction products by GLC
and GC-MS methods. Thus this scheme of compound
IIIa formation seems quite likely. No CCl4 was found in
Amide derivatives V were identified mainly using their
19F NMR spectra with characteristic position of signals
from ortho-fluorine in the region 17.5–18.5, from para-
fluorine in the region 4.2–4.9, and from meta-fluorine in
the region 0.4–1.2 ppm. The close values of the fluorine
chemical shifts in the amide derivatives of different
structure (cf., e.g., our data for amide Va, for o-isomer
o-Vb, and published data for o-isomer o-Vc [7] and m-
isomer m-Vb [8, 9]) and also the ability of some among
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 41 No. 2 2005

222
PETROVA, PLATONOV
Scheme 5.
2
2
2
2
&O
&O
$O&O
$O&O
$O&O
&O
,
;,,,
&&O
&O
1
1
2
&O
2
& )
$ꢁ
& )
2
2
$O&O
&&O
& )
,,,D
1
&&O
&&O
$O&O
ꢂ&&O ꢃ
1
2
2
& )
Scheme 6.
2
2
&O
2
1
& )
&O
& )
1
2
,
$O&O
&O
&O
&O
2
2
&O $O2
&O $O2
&O $O2
;9
2
2
2
2
& )
&O
1
2
%
1 & )
&O
2
2
& )
&O
2
1
2
1
,,,D
&O
& )
2
ꢀ&2&Oꢁ
2
2
the reaction products of acid XIV and anhydride XV,
therefore these compounds presumably are converted in
compound IIIa by another route. One possible pathway
for anhydride XV is presented in Scheme 6.
EXPERIMENTAL
19F and 1H NMR spectra were registered on a spectro-
meter Bruker WP-200SY (at 188.3 and 200 MHz
respectively) using as internal standards hexafluoro-
benzene (–162.9 ppm from CCl3F) and HMDS (0.04 ppm
from TMS). 13C NMR spectrum was measured on
a spectrometer Bruker AM-400 (100.6 MHz), internal
reference CDCl3 (76.9 ppm from TMS). IR spectra were
recorded on a spectrophotometer Specord M-80 from
samples pelletized with KBr.
For acid XIV similar schemes presumably exist
involving seven-membered cationoid intermediates. On
the other hand if the reaction with acid XIV would proceed
as with benzoic acid IIa and at least one carboxy group
of compound XIV would be converted into amide moiety
CONHC6F5 then an ortho-isomer o-Vc would arise that
is known [7] to undergo cyclization at heating into dione
IIIa.
Analysis of the reaction mixtures by GC-MS method
was carried out on a Hewlett-Packard G 1081A instrument
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 41 No. 2 2005

REACTIONS OF N-(PERFLUOROPHENYL)CARBONIMIDOYL DICHLORIDE
223
including a gas chromatograph HP 5890 (of II series)
coupled with a mass-selective detector HP 5971 (nominal
ionizing energy 70 eV); capillary column HP-5MS
(5% of diphenyl- and 95% of dimethylsilicone), 30 m ´
0.25 mm; carrier gas helium, flow rate 1 ml/min, vaporizer
temperature 280°C, ion source temperature 170°C, mass
range 30–650. Molecular weight and elemental composi-
tion were determined on a high resolution mass spectro-
meter Finnigan MAT-8200 (nominal ionizing energy
70 eV). Column chromatography was performed on silica
gel (140–315 mesh). The ratio of products in the reaction
mixtures was evaluated by 19F NMR spectroscopy.
b. The heating at 170°C was continued for 17 h; on
evaporating the solvent from the ether extract we obtained
0.3 g of solid residue containing compounds IIIa, IV–
VII in a ratio ~13:4:65:14:4. The residue was treated
with 10 ml of CCl4 to extract compounds IIIa, IV, and
VI, and the residue insoluble in CCl4 (0.19 g) was filtered
off; it contained a mixture of amides V and urea VII in
–1
a ratio ~ 94:6. IR spectrum of the residue, n, ñm : 994
(CF), 1524 (C6F5), 1651, 1676, 1699 (CO), 3071 (CH),
3261 (NH). Amides V, 19F NMR spectrum (acetone), d,
ppm: –1.1...–0.7 m (2Fm), 4.8–5.2 m (1Fï), 17.9–18.2 m
(2FO).
Initial dichloride I was prepared by procedure [10].
Compound XIII was obtained by method [12]. Freshly
sublimedAlCl3 was used in the reactions. Petroleum ether
of bp 70–100°C was used as one of the solvents.
Reactions with benzoylchloride (IIb). a. The
heating at 130°C was continued for 8 h; on evaporating
the solvent from the ether extract we obtained 0.32 g of
a mixture containing I, IIIa, IV–VIII in a ratio
~38 : 13 : 13 : 6 : 14 : 3 : 13. Amides V (2 compounds in
a ratio ~ 1:2.3), 19F NMR spectrum (ethyl ether), d,
ppm: –1.4 m (2Fm), 4.3 t (1Fï , J 21 Hz ), 4.9 t (1Fï,
J 21 Hz), 17.7 m (2FO). Imidoyl chlorides VI (2 compounds
in a ratio ~ 1:6), 19F NMR spectrum (ethyl ether), d,
ppm: –0.6...–0.3 m (2Fm), 1.6 t (1Fï, J 21 Hz), 2.4 t (1Fï,
J 21 Hz), 12.0–12.3 m (2FO).
Reaction of N-(perfluorophenyl)carbonimidoyl
dichloride (I) with benzoic acid (IIa) and its deriva-
tives. A mixture of 0.26 g (1 mmol) of dichloride I,
1 mmol of the acid or its derivative, and 0.34 g
(2.5 mmol) of AlCl3 was heated in a sealed glass ampule
at the appropriate bath temperature. On cooling the
obtained reaction mixture that had suffered tarring was
cautiously treated with cold water (30 ml), extracted with
ethyl ether (50 ml), the extract was washed with water
till neutral washings, and dried on CaCl2. The solvent
was partially removed on a rotary evaporator, and the
solution obtained was analyzed by 19F NMR spectroscopy
and GC-MS method. Then ethyl ether was completely
evaporated, the residue was washed with 3–5 ml of
petroleum ether to remove unreacted initial dichloride I,
imidoyl chloride derivatives VI, and pentafluoroaniline
VIII, the insoluble residue was filtered off and extracted
with 8–10 ml of CCl4. The insoluble part was again
separated; it contained mainly amide substances V and
urea VII. The solution in CCl4 was evaporated to dryness,
and from the residue compounds III and IV were separat-
ed by sublimation and by chromatography on a column
packed with silica gel.
b. The heating at 170°C was continued for 18 h; on
evaporating the solvent from the ether extract we obtained
0.32 g of a mixture containing I, IIIa, IV–VIII in a ratio
~ 19:24:9:24:3:7:14. From the solution in petroleum ether
we obtained 0.07 g of a mixture of compounds I, IIIa,
IV, V, and VIII in a ratio ~ 61 : 15 : 8 : 6 : 9. From solution
in CCl4 on evaporating the solvent we obtained 0.09 g of
solid residue that was sublimed at 170°C (5 mm Hg.).
The sublimed product combined from several runs
(0.16 g) was subjected to chromatography on a column
packed with silica gel, eluent CHCl3. We obtained 0.03 g
of compound IIIa, 0.05 g of compound IV, 0.02 g of a
mixture of cyclic products IIIa and IV (in a ratio 5:95),
and 0.02 g of a mixture of compounds IIIa and IV (in a
ratio 98:2). Compounds IIIa and IV were additionally
purified by sublimation at 170°C (5 mm Hg.) and
recrystallization from a mixture petroleum ether–CCl4,
10:1.
Reactions with acid (IIa). a. The heating at 130°C
was continued for 9 h; on evaporating the solvent from
the ether extract we obtained 0.3 g of solid residue
containing compounds I, IIIa, IV, Va, VI (in particular
VIa), VII, and VIII in a ratio ~24:1.5 : 1 : 53.5 : 6 : 10 : 4.
(Here and hereinafter to simplify the evaluation of the
products ratio we took into account for amides V only
one group CONHC6F5).
N-(Perfluorophenyl)benzamide (Va). 19F NMR
spectrum (ethyl ether), d, ppm: –1.2 m (2Fm), 4.2 t (1Fï ,
J 20 Hz), 17.8 m (2FO).
2-(Perfluorophenyl)isoindoline-1,3-dione (IIIa),
mp 169.5–171°C (in a sealed capillary) (publ.: mp 128–
–1
130°C [7]). IR spectrum (CCl4), n, cm : 1012 (CF),
1
1518 (C6F5 ), 1734, 1790 (CO), 3101 (CH). H NMR
spectrum, d, ppm, in CCl4: 7.81 m (2H), 7.96 m (2H); in
acetone-d6: 8.02 m (4H) (publ.: 7.50 m [6]). 19F, d, ppm,
in CCl4: 0.6 m (2Fm), 10.1 t (1Fï , J 22 Hz), 18.9 m (2FO);
in acetone-d6: 1.0, 10.8, 20.1 (publ.: 1.3, 7.9, 21.6 [6]); in
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 41 No. 2 2005

224
PETROVA, PLATONOV
DMSO-d6 1.3 m, 11.5 t (J 22 Hz), 19.5 m (publ.: 1.7,
11.9, 19.9 [7]). 13C NMR spectrum (CDCl3), d, ppm:
106.9 (C1', J 14.5 Hz), 124.3 (2C, C4,7), 131.5 (2C, C3a,7a),
134.9 (2C, C5,6), 137.9 (2C, C2',6', JCF 253 Hz), 141.9
(C4', JCF 258, J 13.8 Hz), 144.0 (2C, C3',5', JCF 256 Hz),
164.7 (2C, C1,3). Mass spectrum, m/z (Irel, %): 313 (100)
[M]+, 294 (3.38) [M –F]+, 269 (78.51) [M – CO2]+, 104
(47.53) [C6H4CO]+, 76 (78.01) [C6H4]+. Found, %:
C 53.43; H 0.89; F 30.23; N 4.30. [M]+ 313.01588.
C14H4F5NO2. Calculated, %: C 53.67; H 1.28; F 30.35;
N 4.47. M 313.01621.
b. The ether extract of the reaction mixture obtained
at 170°C (17 h) was filtered from black soot-like
precipitate (0.1 g), and on distilling off the ethyl ether we
obtained 0.18 g of residue containing compounds III, V,
VII, VIII in a ratio ~40 : 36 : 8 : 16. According to GC-
MS data the mixture of diones III contained mainly two
isomers IIIb and four isomers IIIc, and also trace
amounts of compounds IIIa and IIId. On evaporating
the solvent from the extract in petroleum ether we
obtained 0.02 g of a mixture of cyclic derivatives III and
aniline VIII in a ratio 67 : 33. 19F NMR spectrum of
diones III mixture (CCl4), d, ppm: 0.2–0.6 m (2Fm), 9.5–
9.9 m (1Fï), 18.9 m (2FO).
2-(Perfluorophenyl)-3-[(perfluorophenyl)imino]-
isoindolin-1-one (IV), mp 171–173°C (in a sealed
–1
Ethyl-2-(perfluorophenyl)isoindoline-1,3-diones
(IIIb). Found: [M]+ 341.04707. C16H8F5NO2. Calculated:
M 341.04751.
capillary). IR spectrum, n, cm : 990, 1090 (CF), 1517
1
(C6F5), 1686 (C=N), 1769 (CO), 2851, 2920 (CH). H
NMR spectrum (CCl4), d, ppm: 7.43 d (H4, J 7.7 Hz),
7.88 t (1H, J 7.7 Hz), 8.03 t (1H, J 7.7 Hz), 8.27 d (H7,
J 7.7 Hz). 19F NMR spectrum (CCl4), d, ppm: 0.0 m (2F,
F3,5), 0.6 m (2Fm), 1.1 t (1F4, J 21.5 Hz), 10.4 t (1Fï,
J 21.5 Hz), 10.7 m (2F, F2,6), 19.5 m (2FO). Mass spec-
trum, m/z (Irel, %): 478 (53.39) [M]+, 459 (100.00)
[M – F]+, 431 (2.81) [M – F–CO]+, 269 (14.96), 167
(3.67) [C6F5]+, 117 (5.00) [C5F3]+, 76 (40.76)
[C6H4]+. Found, %: C 49.68; H 1.14; F 39.92; N 5.75.
[M]+ 478.01645. C20H4F10N2O. Calculated, %: C 50.21;
H 0.83; F 39.75; N 5.86. M 478.01638.
Diethyl-2-(perfluorophenyl)isoindoline-1,3-
diones (IIIc). Found: [M]+ 369.07689. C18H12F5NO2.
Calculated: M 369.07881.
Triethyl-2-(perfluorophenyl)isoindoline-1,3-
dione (IIId). Found: [M]+ 397.11007. C20H16F5NO2.
Calculated: M 397.11011.
From the extract in CCl4 after removing the solvent
we obtained 0.05 g of a solid mixture of compounds IIIa–
IIId (mainly IIIb, IIIc), amides V, and aniline VIII in a
ratio ~61 : 23 : 16. The solid residue insoluble in petroleum
ether and CCl4 (0.07 g) was composed of a mixture of
amide derivatives V and urea VII in a ratio ~63 : 37.
The residue insoluble in petroleum ether and CCl4
(0.1 g) contained a mixture of amides V and urea VII in
a ratio 73 : 21. Among amide derivatives V by means of
GC-MS method only compound Va was identified.
19F NMR spectrum of a mixture of amide derivatives V
(ethyl ether), d, ppm: –0.8...–0.4 m (2Fm), 4.3–4.9 m
(main signal 4.3 t) (1Fï), 18.0 m (2FO).
–1
Compounds of amide type V, IR spectrum, n, cm : 993
(CF), 1524 (C6F5), 1651, 1675, 1700 (CO), 2887 (CH),
3296, 3439 (NH). 19F NMR spectrum (ethyl ether), d,
ppm: –1.7 ´ –1.1 m (2Fm), 4.2–4.3 m (1Fï), 17.8–18.2 m
(2FO).
c. A mixture of 0.52 g (2 mmol) of dichloride I, 0.14 g
(1 mmol) of acyl chloride IIa, and 0.68 g (5 mmol) of
AlCl3 was heated at 170°C for 21 h. After evaporating
ether we obtained 0.5 g of reaction mixture, containing
compounds I, IIIa–VIII in a ratio ~29 : 13 : 11 : 11 : 13 :
7:16.
Reaction of N-(perfluorophenyl)carbonimidoyl
dichloride (I) with phthalic acid (XIV), phthaloyl
dichloride (XIII), and phthalic anhydride (XV). A
mixture of 0.26 g (1 mmol) of dichloride I, 1 mmol of the
carbonyl compound, and 0.34 g (2.5 mmol) ofAlCl3 was
heated in a sealed glass ampule at 170°C for 10 h. The
cooled reaction mixture was cautiously treated with
20 ml of cold water and worked up along procedure a or b.
Reactions with ethyl benzoate (IIc). a. The heating
at 130°C was continued for 9 h; on evaporating the solvent
from the ether extract we obtained 0.34 g of reaction
mixture containing compounds I, III (mostly IIIb), V,
VIII, IX in a ratio ~ 35 : 7 : 24 : 6 : 28.
a. The separated precipitate was filtered off, washed
with water till neutral washings, and dried in air. We
obtained 0.3 g of reaction product containing over 90%
of dione IIIa that was purified by sublimation at 170°C
(5 mm Hg), yield of compound IIIa 0.24 g (78%), mp
170–171°C (in a sealed capillary).
Ethyl(perfluorophenyl)carbamoyl chloride (IX).
19F NMR spectrum (ethyl ether), d, ppm: 1.2 m (2Fm),
10.2 t (1Fï, J 20 Hz), 17.9 m (2FO) [methyl(perfluoro-
phenyl)carbamoyl chloride [10]: 1.6 m (2Fm), 10.3 t (1Fï),
17.4 m (2FO)].
b. The reaction mixture was extracted with ethyl ether,
the ether solution was washed with water till neutral
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REACTIONS OF N-(PERFLUOROPHENYL)CARBONIMIDOYL DICHLORIDE
225
washings, dried with CaCl2, and analyzed by 19F NMR
and GC-MS methods. On removing the solvent on a rotary
evaporator we obtained 0.3 g of residue that was purified
as in procedure a. In the case of phthaloyl dichloride
(XIII) the ether extract contained according to 19F NMR
data compounds IIIa and X in a ratio ~ 94:6. Data of
GC-MS analysis: ~70% of compound IIIa, ~19% of CCl4,
~3% of cyclic dichloride X. Content of CCl4 according
to GLC data (internal normalization procedure) was 17%.
The ether extract of the reaction mixture obtained from
acid XIV contained compounds IIIa and VII in a ratio
~ 91 : 9.
0.4 g (2 mmol) of phthaloyl dichloride (XIII), and the
solution was boiled for 6 h. Then the benzene was
removed on a rotary evaporator, the residue was ground
with 20 ml of 5% HCl, the precipitate was filtered off,
washed with water till pH ~7, and dried in air. We obtained
0.58 g (92%) of compound IIIa.
Reactions of 2-(perfluorophenyl)isoindoline-1,3-
dione (IIIa).
Reaction with N-(perfluorophenyl)carbonimidoyl
dichloride (I). From 0.11 g (0.4 mmol) of dichloride I,
0.13 g (0.4 mmol) of compound IIIa, and 0.13 g (1 mmol)
ofAlCl3 after heating at 170°C for10 h and workup along
procedure described above we obtained ether solution of
the reaction mixture containing initial dione IIIa and urea
VII in a ratio 78:32.
Reaction of phthaloyl dichloride (XIII) with
pentafluoroaniline VIII. a.Asolution of 0.4 g (2 mmol)
of phthaloyl dichloride (XIII) and 0.37 g (2 mmol) of
aniline VIII in 3 ml of anhydrous benzene was maintained
for 4 days at room temperature, the separated precipitate
was filtered off (0.37 g). The precipitate containing a
mixture of compounds IIIa, o-Vb, and VIII was
extracted with 4 ml of CCl4. Diamide o-Vb insoluble in
CCl4 (0.24 g, 48%) was filtered off and recrystallized
from aqueous acetone (1:1) and from a mixture CHCl3–
acetone, 3:1.
Reaction with pentafluoroaniline VIII. From
0.1 g (0.32 mmol) of compound IIIa, 0.06 g (0.32 mmol)
of aniline VIII, and 0.11 g (0.8 mmol) of AlCl3 after
heating at 170°C for18 h and workup along procedure
described above we obtained ether solution of the reaction
mixture containing compounds IIIa, IV, o-Vb, VIII in a
ratio ~25:18:1.4:0.9. After distilling off the solvent 0.15 g
of residue was isolated that was extracted in succession
with 2 ml of petroleum ether and 1.5 ml of CCl4. From
the petroleum ether extract after removing the solvent
we obtained 0.03 g of a mixture of compounds IIIa, IV,
VIII in a ratio 21 : 26 :53. From the solution in 1.5 ml
CCl4 after removing the solvent we obtained 0.05 g of
a mixture of cyclic compounds IIIa and IV in a ratio
61:39. The residue insoluble in petroleum ether and CCl4
(0.03 g) was diamide o-Vb.
N,N'-Bis(perfluorophenyl)phthalamide (o-Vb), mp
–1
209–212°C. IR spectrum, n, cm : 1005 (CF), 1503, 1525
(C6F5), 1670, 1686 (CO), 2977, 3075 (CH), 3291 (NH).
1H NMR spectrum (acetone-d6), d, ppm: 7.69 m (2Harom),
7.83 m (2Harom), 9.69 C (NH). 19F NMR spec-trum
(acetone-d6), d, ppm: –1.0 m (4Fm), 4.5 t (2Fï, J 21
Hz), 18.5 m (4FO). Found, %: C 48.85; H 1.23; F
37.70; N 5.77. C20H6F10N2O2. Calculated, %: C 48.38;
H 1.21; F 38.31; N 5.64.
Reaction with PCl5. a.Amixture of 0.1 g (0.33 mmol)
of dione IIIa and 0.21 g (1 mmol) of PCl5 was heated
for 10 h in a sealed glass ampule at the bath temperature
200°C. To a cooled reaction mixture was added 2 ml of
anhydrous CCl4 to obtain a solution containing compounds
IIIa, X, XI in a ratio 3 : 32 : 65. This extract was washed
with 5 ml of cold water, dried over CaCl2, the solvent
was removed to afford 0.09 g of a solid residue containing
a mixture of initial dione IIIa and reaction products X
and XI in a ratio 9 : 70 : 21.
From the benzene filtrate after distilling off benzene
we obtained 0.09 g of a mixture of compound IIIa and
amide o-Vb in a ratio 41 : 59.
b. To a solution of 0.37 g (2 mmol) of aniline VIII in
3 ml of anhydrous benzene was added 0.24 g (2 mmol)
of N,N-dimethylaniline, 0.4 g (2 mmol) of phthaloyl
dichloride (XIII), and the mixture was left standing at
room temperature for 24 h.Then the benzene was
evaporated without heating on a rotary evaporator, the
residue was ground with 20 ml of 5% HCl and extracted
with ethyl ether. The ether solution was washed with
water till neutral washings, dried over CaCl2, and the
solvent was distilled off. We obtained 0.4 g (63.5%) of
compound IIIa.
b. From 0.1 g (0.33 mmol) dione IIIa and 0.34 g
(1.6 mmol) of PCl5 by procedure a we obtained a solution
of the reaction mixture in CCl4 that on removing a solvent
gave 0.14 g of solid residue containing compounds X and
XI in a ratio 4:96.
3,3-Dichloro-2-(perfluorophenyl)isoindolin-1-
c. To a solution of 0.37 g (2 mmol) of aniline VIII in
2 ml of anhydrous benzene was added 0.24 g (2 mmol)
of N,N-dimethylaniline in 2 ml of anhydrous benzene,
1
one (X). H NMR spectrum (CCl4), d, ppm: 7.29 d (H4,
J 7 Hz), 7.65 t (H6, J 7 Hz), 7.80 t (H5, J 7 Hz), 7.87 d
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 41 No. 2 2005

226
PETROVA, PLATONOV
(H7, J 7 Hz). 19F NMR spectrum (CCl4), d, ppm: 1.0 m
(2Fm), 12.3 t (1Fï, J 21.5 Hz), 23.3 m (2FO). Mass
spectrum, m/z (Irel, %): 332 (100) [M – Cl]+, 313 (3.15)
[M – Cl–F]+, 304 (2.98) [M – Cl–CO]+, 269 (9.42) [M –
2Cl–CO]+, 167 (8.30) [C6F5]+, 148 (14.33) [C6F4]+, 117
(10.86) [C5F3]+, 76 (13.49) [C6H4]+. Found: [M]+
366.95906. C14H4Cl 2F5NO. Calculated: M 366.95900.
d. From 0.14 g (0.33 mmol) of tetrachloro deriva-
tive XI, 0.30 g (1.6 mmol) of aniline VIII, and 0.28 g
(2.1 mmol) of AlCl3 we obtained 0.28 g of black residue
that was extracted with 1.5 ml of petroleum ether, and
0.15 g (71.5%) of compound XII was filtered off and
purified by column chromatography on silica gel, eluent
CHCl3. We obtained 0.12 g of bis(imino)isoindoline
derivative XII, that was recrystallized from a mixture
petroleum ether–CCl4, 10 : 1.
1,1,3,3-Tetrachloro-2-(perfluorophenyl)iso-
1
indoline (XI). H NMR spectrum (CCl4), d, ppm:
7.65 m (2H, H5,6), 7.77 m (2H, H4,7). 19F NMR spectrum
(CCl4), d, ppm: 1.4 m (2Fm), 13.7 t.t (1Fï, J 22, J 5 Hz ),
29.7 m (2FO). Mass spectrum, m/z (Irel, %): 386 (46.33)
[M – Cl]+, 351 (53.38) [M – 2Cl]+, 316 (40.91) [M –
3Cl]+, 184 (14.56) [M – 2Cl–C6F5]+, 176 (15.96), 167
(15.07) [C6F5]+. Found: [M – Cl]+ 385.93294.
C14H4Cl3F5N. Calculated: [M – Cl] 385.93294.
1,3-Bis[(perfluorophenyl)imino]-2-(perfluoro-
phenyl)isoindoline (XII), mp 245.5–247°C (in a sealed
–1
capillary). IR spectrum, n, cm : 990 (CF), 1501, 1516
(C6F5), 1684 (C=N). 1H NMR spectrum (CCl4), d, ppm:
7.23 br.m (2Harom), 7.58 br.m (2Harom). 19F NMR
spectrum (CCl4), d, ppm: 0 m (4F, 2F3, 2F5), 0.5–1.0 m
(4F, 2Fm, 2F4), 10.7 t (1Fï , J 21.5 Hz ), 10.9 m (4F, 2F2,
2F6), 19.7 m (2FO). Mass spectrum, m/z (Irel, %): 643
(62.52) [M]+, 624 (100) [M – F]+, 476 (1.68) [M – C6F5]+,
438 (5.61), 321 (7.36), 295 (8.06), 167 (5.43) [C6F5]+,
117 (7.36) [C5 F3]+, 76 (10.08) [C6 H4]+. Found, %:
C 48.66; H 0.57; F 43.75; N 6.36. C26H4F15N3.Calculated,
%: C 48.52; H 0.62; F 44.32; N 6.53.
Reactions of cyclic chlorides X, XI. A mixture of
chloride, reagent, and AlCl3 was heated for 17 h in a
sealed glass ampule at the bath temperature 170°C, to a
cooled reaction mixture was added 10 ml of cold water,
it was extracted with 20 ml of diethyl ether, the ether
extract was dried with CaCl2, and the solvent was distilled
off on a rotary evaporator.
REFERENCES
a. From 0.06 g of a mixture of cyclic dichloro derivative
X and dione IIIa (89 : 11), 0.04 g (0.16 mmol) of carbon-
imidoyl dichloride I, and 0.05 g (0.4 mmol) of AlCl3 we
obtained 0.06 g of dark solid residue containing compounds
I, IIIa, IV, VII, VIII, X in a ratio ~26 : 38 : 10 : 18 : 3 : 5.
1. Petrova, T.D., Kolesnikova, I.V., Mamatyuk, V.I., Vetchin-
ov, V.P., Platonov, V.E., Bagryanskaya, I.Yu., and Gati-
lov, Yu.V., Izv. Akad. Nauk. Ser. Khim., 1993, p. 1605.
2. Petrova, T.D., Platonov, V.E., Pokrovskii, L.M., Rybalo-
va, T.V., and Gatilov, Yu.V., Coll. Czech. Commun., 2002,
vol. 67, p. 1449.
3. Petrova, T.D. and Platonov, V.E., Zh. Org. Khim., 1997,
vol. 33, p. 745.
4. Petrova, T.D., Platonov, V.E., Kolesnikova, I.V., Ribalo-
va, T.V., Bagryanskaya, I.Yu., and Gatilov,Yu.V., J. Fluorine
Chem., 2000, vol. 103, p. 63.
5. Petrova, T.D., Popova, I.S., Kolesnikova, I.V., and Plato-
nov, V.E., Izv. Akad. Nauk, Ser. Khim., 1994, p. 1089.
6. Shizheng, Zhu, Bin, Xu, and Jie, Zhang, J. Fluorine Chem.,
1995, vol. 74, p. 203.
7. Shinji,Ando and Tohru, Matsuura, Magn. Res. Chem., 1995,
vol. 33, p. 639.
8. Adams, H., Blanco, J.L.J., Chessari, G., Hunter, Ch.A.,
Low, C.M.R., Sanderson, J.M., and Vinter, J.G., Chemistry
Eur. J., 2001, vol. 7, p. 3494.
9. Adams, H., Hunter, Ch.A., Lawson, K.R., Perkins, J.,
Spey, Sh.E., Urch, Ch.J., and Sanderson, J.M., Chemistry
Eur. J., 2001, vol. 7, p. 4863.
b. From 0.09 g of a mixture of cyclic dichloro derivative
X and dione IIIa (96:4), 0.05 g (0.25 mmol) of aniline
VIII, and 0.08 g (0.62 mmol) of AlCl3 we obtained
0.09 g of dark residue containing compounds IIIa, IV,
VIII in a ratio 5:43:52. The residue was extracted with
1.5 ml of petroleum ether, and 0,04 g (36%) of compound
IV was filtered off and purified by sublimation at 170°C
(3 mm Hg) followed by recrystallization from petroleum
ether.
c. From 0.19 g of a mixture of cyclic di- and tetra-
chloro derivatives X and XI (63 : 37), 0.1 g (0.6 mmol)
of aniline VIII, and 0.24 g (1.8 mmol) of AlCl3 we
obtained 0.17 g of residue containing compounds IIIa,
IV, VIII in a ratio 13 : 42 : 45.Amixture of this composition
(0.26 g) was subjected to column chromatography on
silica gel, eluent CHCl3. We obtained 0.05 g of (imino)-
isoindolin-1-one (IV), 0.05 g of a mixture of isoindoline
derivatives IIIa and IV, 9:91, and 0.04 g of dione IIIa.
Compound IV was purified by recrystallization from
petroleum ether and by sublimation at 170°C (4 mm Hg).
10. Savchenko, T.I., Kolesnikova, I.V., Petrova, T.D., and
Platonov, V.E., J. Fluorine Chem., 1983, vol. 22, p. 439.
11. Kryuchkova, E.N., Kolesnikova, I.V., Drizhd, L.P., Savelo-
va, V.A., Petrova, T.D., and Platonov, V.E., Zh. Org.Khim.,
1988, vol. 24, p. 2042.
12. Sint. Org. Prep., 1949, vol. 2, p. 547.
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 41 No. 2 2005