Reactions of bisdiazonium salts derived from monosubstituted m-phenylenediamines with amides and nitriles of unsaturated acids under anionarylation conditions

Article abstract of DOI:10.1134/S1070363215080058

Reactions of 5-carboxy and 4-methylphenylene-1,3-bisdiazonium tetrafluoroborates with amides and nitriles of acrylic and methacrylic acids in the presence of chloride, bromide, and thiocyanate anions proceed as anionarylation at one of the diazo groups and nucleophilic substitution at another one. With 4-methylphenylene- 1,3-bisdiazonium tetrafluoroborate as the arylating agent, the anionarylation and the Sandmeyer reaction occur involving para- and ortho-positioned diazo groups, respectively.

Full text of DOI:10.1134/S1070363215080058

ISSN 1070-3632, Russian Journal of General Chemistry, 2015, Vol. 85, No. 8, pp. 1821–1825. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © V.S. Baranovskii, V.N. Yatsyuk, A.N. Vasilenko, B.D. Grishchuk, 2015, published in Zhurnal Obshchei Khimii, 2015, Vol. 85, No. 8,
pp. 1262–1266.
Reactions of Bisdiazonium Salts Derived
from Monosubstituted m-Phenylenediamines with Amides
and Nitriles of Unsaturated Acids
under Anionarylation Conditions
V. S. Baranovskiia, V. N. Yatsyuka, A. N. Vasilenkob, and B. D. Grishchuka
a Hnatiuk Ternopil National Pedagogical University, ul. M. Kryvonosa 2, Ternopil, 46027 Ukraine
e-mail: baranovsky@tnpu.edu.ua
b Institute of Bioorganic Chemistry and Petrochemistry, National Academy of Sciences of Ukraine, Kiev, Ukraine
Received March 19, 2015
Abstract—Reactions of 5-carboxy and 4-methylphenylene-1,3-bisdiazonium tetrafluoroborates with amides
and nitriles of acrylic and methacrylic acids in the presence of chloride, bromide, and thiocyanate anions
proceed as anionarylation at one of the diazo groups and nucleophilic substitution at another one. With 4-methyl-
phenylene-1,3-bisdiazonium tetrafluoroborate as the arylating agent, the anionarylation and the Sandmeyer
reaction occur involving para- and ortho-positioned diazo groups, respectively.
Keywords: anionarylation, Sandmeyer reaction, phenylenebisdiazonium tetrafluoroborate, unsaturated acid
amide, unsaturated acid nitrile
DOI: 10.1134/S1070363215080058
It has been earlier shown that m-phenylenebis-
diazonium chlorides afford the products of chloro-
arylation of esters and nitriles of acrylic and metha-
crylic acids at a single diazo group under the
Meerwein reaction conditions, probably, due to elec-
tronic and steric effects [1]. Similar regioselectivity
has been observed in the case of thiocyanatoarylation
of acrylamide and methacrylamide with p- and m-
phenylenebisdiazonium tetrafluoroborates [2].
halogen or thiocyanate. Anionarylation of acrylamide
and methacrylamide with 4-methylphenylene-1,3-
bisdiazonium tetrafluoroborate yielded the correspond-
ing propionamides XI–XVI (Scheme 1).
The reactions occurred in a water–acetone (1 : 2.5)
medium at –25 to 10°C in the presence of copper(II)
tetrafluoroborate as a catalyst. The products yield was
of 33–71%; the reactions were accompanied by
nucleophilic substitution of the diazo group to give the
corresponding products in 10–30% yield with respect
to the diazonium salt.
In order to extend the knowledge on the anio-
narylation and broaden its synthetic applications, we
studied the reaction involving bisdiazonium salts
derived from monosubstituted m-phenylenediamines:
5-carboxyphenylene-1,3-bisdiazonium and 4-methyl-
phenylene-1,3-bisdiazonium tetrafluoroborates [3–5].
The attempts to perform anionarylation of acrylic
and methacrylic acids nitriles with 4-methylphenylene-
1,3-bisdiazonium tetrafluoroborate or thiocyanato-
arylation of the nitriles with 5-carboxyphenylene-1,3-
bisdiazonium tetrafluoroborate failed. The major
reaction products were 4-methyl-1,3-dichloro(bromo,
thiocyanato)benzene and 3,5-dithiocyanatobenzoic acid.
Probably, the presence of a strong nucleophile (thio-
cyanate anion) and/or an active arylating agent induced
the Sandmeyer reaction, normally occurring at higher
temperature than anionarylation.
We found that the interaction of 5-carboxy-
phenylene-1,3-bisdiazonium tetrafluoroborate with
amides and nitriles of acrylic and methacrylic acids in
the presence of chloride, bromide, or thiocyanate anion
afforded the corresponding substituted benzoic acids
I–X via anionarylation at one of the diazo groups and
simultaneous substitution of another diazo moiety with
1821

1822
BARANOVSKII et al.
Scheme 1.
COOH
COOH
N2BF4
R
MHlg
KSCN
+
_N2, _MBF4
_N2, _KBF4
X
Hlg
R
NCS
HOOC
N2BF4
R
X
Hlg
I_IV, VII_X
X
NCS
V, VI
CH3
CH3
CH3
N2BF4
Hlg
X
SCN
R
MHlg
KSCN
+
_N2, _KBF4
_N2, _KBF4
X
R
R
N2BF4
X
SCN
XV, XVI
Hlg
XI_XIV
X = C(O)NH2 (I–VI, IX–XVI), CN (VII–X); Hlg = Cl (I, II, VII, VIII, IX, XII), Br (III, IV, IX, X, XIII, XIV); R = H
(I, III, V, VII, IX, XI, XIII, XV), CH3 (II, IV, VI, VIII, X, XII, XIV, XVI); M = Na, K.
Scheme 2.
O
NCS
R
NCS
NH2
Hlg(SCN)
CH3
O
R
H3C
NH2
(SCN)Hlg
A
B
1
Yields and H NMR data of the obtained com-
group (compounds I–VI and XI–XVI) were observed
at 8.19–7.52 ppm. In the spectra of compounds I, III,
V, VI, IX, XI, XIII, and XV, the methine protons
resonated at 5.52–4.27 ppm. The broadened signals of
carboxyl group of compounds I–X were observed in
weaker field (about 13.4–13.2 ppm). The ratio of the
signals integral intensity indicated the presence of a
single propionylamide (nitrile) moiety in the structure
of compounds I–XVI, thus confirming that anionaryla-
tion involved only one of the diazo groups.
pounds I–XVI are collected in Table 1.
IR spectra of compounds I–VI and IX–XVI
contained the absorption bands of the carbonyl and
amide groups at 1660–1688 and 3382–3404 cm–1,
respectively. Absorption band of the nitrile group of
compounds VII–X was observed at 2232–2244 cm–1.
Spectra of thiocyanatoamides V, VI, XV, and XVI
additionally contained the absorption band of thio-
cyanate group at 2152–2164 cm–1.
Since anionarylation could involve the both ortho-
and para-positioned diazo groups, H NMR data did
not ambiguously reveal the structure of amides XI–
XVI: the possible structural isomers of XI–XVI were
expected to reveal similar spectral characteristics
(Scheme 2).
1H NMR spectra of compounds 1–XVI contained
the signals of the aromatic protons at 8.07–7.28 ppm.
In the cases of acrylic and methacrylic acids deri-
vatives, the signals of protons of methylene moieties
adjacent to the aromatic rings were observed as two
doublets of doublets (3.56–3.29 and 3.47–3.15 ppm)
and two doublets (3.55–3.41 and 3.49–3.13 ppm),
respectively. The signals of protons of the amide NH2
1
In order to elucidate the structure of thiocyanato-
amide XVI, we took advantage of 2D NMR spectral
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REACTIONS OF BISDIAZONIUM SALTS DERIVED
1823
Table 1. Yields, melting points, and NMR spectral data for compounds I–XVI
Comp.
no.
Yield, % mp, °Сa
δН, ppm (J, Hz)
I
40
45
58
51
63
71
33
38
50
53
36
40
44
53
59
65
165
139
174
162
197
191
121
148
149
155
116
134
129
144
169
164
13.27 br.s (1Н, HOOC), 7.72 s and 7.51 s (2Н, NH2); 7.83 s, 7.80 s and 7.62 s (3Н, С6Н3),
4.57 t [1Н, СН(Cl), J 12.4], 3.52 d.d and 3.33 d.d [2H, CH2С6Н3, J 13.7]
II
13.19 br.s (1Н, HOOC), 7.70 s and 7.52 s (2Н, NH2); 7.91 s, 7.89 s and 7.70 s (3H, C6H3),
3.55 d and 3.49 d [2H, CH2C6H3, J 14.1], 1.83 s (3H, CH3)
III
13.41 br.s (1H, HOOC), 7.66 c and 7.59 s (2H, NH2); 7.89 s, 7.82 s and 7.69 s (3H, C6H3),
4.49 t [1H, CH(Br), J 11.8], 3.46 d.d and 3.27 d.d [2H, CH2C6H3, J 13.9]
IV
13.34 br.s (1H, HOOC), 7.63 s and 7.55 s (2H, NH2); 7.93 s, 7.88 s and 7.73 s (3H, C6H3),
3.52 d and 3.45 d [2H, CH2C6H3, J 14.1], 1.76 s (3H, CH3)
V
13.45 br.s (1H, HOOC), 7.77 s and 7.52 s (2H, NH2); 8.04 s, 7.96 s and 7.80 s (3H, C6H3),
4.30 t [1H, CH(SCN), J 12.4], 3.42 d.d and 3.21 d.d [2H, CH2C6H3, J 13.7]
VI
13.27 br.s (1H, HOOC), 8.19 s and 8.00 s (2H, NH2); 8.07 s, 7.92 s and 7.70 s (3H, C6H3),
3.55 d and 3.23 d [2H, CH2C6H3, J 14.0], 1.87 s (3H, CH3)
VII
VIII
IX
13.30 br.s (1H, HOOC); 8.03 s, 7.99 s and 7.74 s (3H, C6H3), 5.52 t [1H, CH(Cl), J 11.8],
3.50 d.d and 3.41 d.d [2H, CH2C6H3, J 13.7]
13.18 br.s (1H, HOOC); 7.99 s, 7.96 s and 7.72 s (3H, C6H3), 3.60 d and 3.47 d [2H,
CH2C6H3, J 13.4]), 1.97 s (3H, CH3)
13.42 br.s (1H, HOOC); 7.98 s, 7.96 s and 7.87 s (3H, C6H3), 5.43 t [1H, CH(Br), J 12.2],
3.56 d.d and 3.47 d.d [2H, CH2C6H3, J 13.4]
X
13.38 br.s (1H, HOOC); 8.02 s, 7.99 s and 7.91 s (3H, C6H3), 3.53 d and 3.44 d [2H,
CH2C6H3, J 13.1], 1.82 s (3H, CH3)
XI
8.03 s and 7.80 s (2H, NH2); 7.45 s, 7.30 s and 7.22 s (3H, C6H3), 4.52 t [1H, CH(Cl),
J 11.6], 3.38 d.d and 3.25 d.d [2H, CH2C6H3, J 13.8], 2.42 s (3H, CH3C6H3)
XII
XIII
XIV
XV
XVI
8.06 s and 7.88 s (2H, NH2); 7.48 s, 7.34 s and 7.25 s (3H, C6H3), 3.41 d and 3.22 d [2H,
CH2C6H3, J 13.6], 2.44 s (3H, CH3C6H3), 1.80 s (3H, CH3)
8.10 s and 7.95 s (2H, NH2); 7.51 s, 7.40 s and 7.32 s (3H, C6H3), 4.46 t [1H, CH(Br),
J 12.0], 3.36 d.d and 3.19 d.d [2H, CH2C6H3, J 13.4], 2.41 s (3H, CH3C6H3)
8.14 s and 7.98 s (2H, NH2); 7.55 s, 7.44 s and 7.32 s (3H, C6H3), 3.42 d and 3.18 d [2H,
CH2C6H3, J 13.5], 2.40 s (3H, CH3C6H3), 1.84 s (3H, CH3)
8.17 s and 7.91 s (2H, NH2); 7.50 s, 7.36 s and 7.28 s (3H, C6H3), 4.27 t [1H, CH(SCN),
J 12.0], 3.29 d.d and 3.15 d.d [2H, CH2C6H3, J 13.4], 2.44 s (3H, CH3C6H3)
8.17 s and 7.94 s (2H, NH2); 7.53 s, 7.40 s and 7.29 s (3H, C6H3), 3.47 d and 3.13 d [2H,
CH2C6H3, J 13.4], 2.42 s (3H, CH3C6H3), 1.83 s (3H, CH3)
a The substances were recrystallized from methanol.
analysis (NOESY, COSY, HSQC, and HMBC); its
results are shown in the Figure and in Table 2.
methyl-3-thiocyanatophenyl)-2-methyl-2-thiocyanato-
propionamide. It should be noted that no correlations
between the signals at 113.92 and 111.34 ppm was
found in the HMBC spectrum, so assignment of those
signals was performed accounting to the general views
on the electron density distribution.
The cross-peaks in the NOESY spectrum of
compound XVI (3.13↔7.29, 3.13↔7.53, 3.47↔7.29,
3.47↔7.53, and 2.42↔7.40), as well as in the HMBC
spectrum (2.42↔123.75, 2.42↔131.71, 3.13↔132.30,
3.13↔133.67, 3.47↔132.30, and 3.47↔133.67) confirmed
that the questionable structure corresponded to 3-(4-
In summary, when using 4-methylphenylene-1,3-
bisdiazonium tetrafluoroborate as arylating reagent, the
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1824
BARANOVSKII et al.
Table 2. Cross-peaks (δ, ppm) in the COSY, NOESY, HSQC, and HMBC spectra of compound XVI
1H
COSY
–
NOESY
HSQC
26.98
HMBC
1.83
3.13, 3.47, 7.29, 7.53, 7.94, 8.17
43.02, 171.75
123.75, 138.75
2.42
3.13
3.47
7.29
7.40
7.53
7.94
8.17
7.40
7.40
19.95
43.02
43.02
132.30
131.71
133.67
–
3.47
1.83, 3.47, 7.29, 7.53
1.83, 3.13, 7.29, 7.53, 7.94, 8.17
1.83, 3.13, 3.47, 7.40, 7.53, 7.94, 8.17
2.42, 7.29
67.50, 171.75, 135.83, 132.30, 133.67
3.13
67.50, 171.75, 135.83, 132.30, 133.67
7.53, 7.40
133.67, 138.75
123.75, 135.83
138.75, 132.30
67.50
7.29, 2.42
7.29
–
1.83, 3.13, 3.47, 7.29, 7.94, 8.17
1.83, 3.47, 7.53, 7.29
1.83, 3.47, 7.53, 7.29
–
–
–
thiocyanatoarylation and the Sandmeyer reactions
occurred at the para- and ortho-positioned diazo groups,
respectively. Interaction of 5-carboxy- and 4-methyl-
phenylene-1,3-bisdiazonium tetrafluoroborates with
amides and nitriles of acrylic and methacrylic acids in
the presence of halide or thiocyanate anions yielded
monoanionarylated derivatives. Such chemoselectivity
was probably due to the high reactivity of the arylating
agents and the nucleophilic anions, in agreement with
the data presented in [1, 2].
d6 or CDCl3) were registered with a Varian Mercury
(400 MHz) and a Bruker Avance DRX-500 (500 MHz)
spectrometers relative to the internal TMS reference.
Purity of the products was confirmed by TLC
performed on Silufol UV-254 plates (eluents: benzene–
methanol, 4 : 1 or methanol–benzene–acetone, 1 : 3 : 1).
3-(3-Amino-2-chloro-3-oxopropyl)-5-chloroben-
zoic acid (I). 5-Carboxyphenylene-1,3-bisdiazonium
tetrafluoroborate (7.6 g, 0.022 mol) was added to a
mixture of 1.7 g (0.024 mol) of acrylamide, 0.8 g
(0.0023 mol) of copper(II) tetrafluorborate hexa-
hydrate, and 2.8 g (0.048 mol) of sodium chloride in
150 mL of a water–acetone (1 : 2.5) mixture over
30 min. After nitrogen evolution had ceased (60 min),
30 mL of water was added, and the mixture was
extracted with 50 mL of methylene chloride. The
organic layer was separated, washed with water, dried
over anhydrous calcium chloride, and evaporated. The
residue was incubated at –20°C till complete crys-
tallization and then recrystallized from methanol to
yield 2.3 g (40%) of compound I and 0.9 g (21%) of
3,5-dichlorobenzoic acid melting at 183°C (methanol)
(mp 181°C [7]).
EXPERIMENTAL
IR spectra (paraffin oil) were recorded using a
SPECORD M80 instrument. 1H NMR spectra (DMSO-
Amides II, XI, and XII and nitriles VII and VIII
were prepared similarly.
3-(3-Amino-2-bromo-3-oxopropyl)-5-bromobenzoic
acid (III). 5-Carboxyphenylene-1,3-bisdiazonium tetra-
fluoroborate (7.6 g, 0.022 mol) was added to a mixture
of 1.9 g (0.026 mol) of acrylamide, 0.9 g (0.0025 mol)
of copper(II) tetrafluorborate hexahydrate, and 6.3 g
(0.053 mol) of potassium bromide in 150 mL of a
Main correlations in the HMBC and NOESY spectra of
compound XVI.
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REACTIONS OF BISDIAZONIUM SALTS DERIVED
water–acetone (1 : 2.5) mixture over 60 min. After
REFERENCES
1825
nitrogen evolution had ceased (60 min), the reaction
mixture was treated as described above for compound
I. 4.4 g (58%) of compound 3 and 1.0 g (16%) of 3,5-
dibromobenzoic acid melting at 218°C (methanol) (mp
219–220°C [8]) were obtained.
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Amides IV, XIII, and XIV, and nitriles IX and X
were prepared similarly.
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3-(3-Amino-2-thiocyanato-3-oxopropyl)-5-thio-
cyanatobenzoic acid (V). 5-Carboxyphenylene-1,3-
bisdiazonium tetrafluoroborate (6.4 g, 0.018 mol) was
added to a mixture of 1.4 g (0.02 mol) of acrylamide,
0.7 g (0.002 mol) of copper(II) tetrafluorborate hexa-
hydrate, and 3.9 g (0.04 mol) of potassium thiocyanate
in 120 mL of a water–acetone (1 : 2.5) mixture over
60 min. After nitrogen evolution had ceased (60 min),
the reaction mixture was treated as described above for
compound I. 3.5 g (63%) of compound V and 0.8 g
(19%) of 3,5-dithiocyanatobenzoic acid melting at
202°C (methanol) were obtained.
8. Bogert, M.T. and Hand, W.F., J. Chem. Soc., 1903,
vol. 25, p. 942.
Amides VI, XV, and XVI were obtained similarly.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 8 2015