Reaction of arenediazonium tetrafluroborates with N,N-methylenediacryalmide in the presence of thiocyanate anions

Article abstract of DOI:10.1023/A:1026317221544

The reactions of arenediazonium tetrafluoroborates with N,N-methylenediacrylamide in H₂O-DMF (1:3) and H₂O-DMSO (1:4) in the presence of thiocyanate anions involve thiocyanatoarylation by one or two multiple bonds to give [(3-aryl-2-

Full text of DOI:10.1023/A:1026317221544

Russian Journal of General Chemistry, Vol. 73, No. 6, 2003, pp. 957 960. Translated from Zhurnal Obshchei Khimii, Vol. 73, No. 6, 2003,
pp. 1011 1014.
Original Russian Text Copyright
2003 by Grishchuk, Baranovskii, Gorbovoi, Ganushchak.
Reaction of Arenediazonium Tetrafluroborates
with N,N-Methylenediacryalmide in the Presence
of Thiocyanate Anions
B. D. Grishchuk, V. S. Baranovskii, P. M. Gorbovoi, and N. I. Ganushchak
Gnatyuk Ternopol State Pedagogical University, Ternopol, Ukraine
Received May 21, 2001
Abstract The reactions of arenediazonium tetrafluoroborates with N,N-methylenediacrylamide in H2O
DMF (1 : 3) and H2O DMSO (1 : 4) in the presence of thiocyanate anions involve thiocyanatoarylation by one
or two multiple bonds to give [(3-aryl-2-thiocyanatopropionylamino)methyl]-2-acryalmides and N,N-me-
thylenebis(2-thiocyanato-3-arylpropionamides).
At present we have studied thiocyanatoarylation of
various monounsaturated compounds like CHR1=
CR2R3 and effects of various factors on this reaction
revealing unknown regularities of reaction of aromatic
diazonium salts with unsaturated compounds contain-
ing two isolated multiple bonds, we brought into thio-
[1, 2]. In [3], we have found that arenediazonium tetra- cyanatoarylation N,N-methylenediacrylamide.
fluoroborates react with acrylamide in the presence of
alkali metal or ammonium thiocyanates with elimina-
tion of diazo nitrogen and formation of -thiocyanato-
-arylpropionamides which may present interest as
antimicrobials. The reactions occur in aqueous acetone
(1:2) and only in the presence of a catalyst, copper or
iron salt.
It was found that arenediazonium tetrafluoroborates
react with N,N-methylenediacrylamide in the pre-
sence of thiocyanate ions. The reaction involves
evolution of diazo nitrogen and addition of the aryl
and thiocyanato groups by the site of cleavage of one
ortwo multiple bonds: [(3-aryl-2-thiocyanatopropionyl-
amino)methyl]-2-acrylamides I VII or N,N-methylene-
bis(2-thiocyanato-3-arylpropionamides) VIII XIV.
Proceeding with the studies in [2] and aiming at
N2BF4
+ H2C
O
O
+ MSCN
C
CH2
NH
CH2
CH
C
CH
O
NH
CH
NH
O
R
(1)
(2)
C
C
CH2
CH2
CH2
CH
NH
SCN
O
I VII
R
O
CH2
C
C
CH2
CH2
+ MBF4 + N2
NH
CH
SCN
CH
SCN
NH
R
VIII XIV
R
R = H (I, VIII), 2-CH3 (II, IX), 3-CH3 (III, X), 4-CH3 (IV, XI), 4-CH3O (V, XII), 4-NO2 (VI, XIII), 2,5-Cl2 (VII, XIV);
M = Na, K, NH4.
The reaction occurs in aqueous dimethylformamide
(1:3) or aqueous dimethyl sulfoxide (1:4) in the
presence of thiocyanate anions and catalytic amounts
of copper(II) tetrafluoroborate at 10 15 C. At the
arenediazonium
salt:N,N-methylenediacrylamide:
thiocyanate:copper(II) tetrafluoroborate ratio of
1.1:1:1.1:0.1, monoadducts I VII are formed, and
at double the quantities of diazonim salt, thiocyanate,
1070-3632/03/7306-0957$25.00 2003 MAIK Nauka/Interperiodica

958
GRISHCHUK et al.
Table 1. Yields, constants and elemental analyses of [(3-aryl-2-thiocyanatopropionylamino)methyl]-2-acrylamides I VII
and N,N-methylenebis(2-thiocyanato-3-arylpropionamides) VIII XIV
Found, %
Calculated, %
Comp.
no.
Yield, %
mp, Ca
Formula
N
S
N
S
I
II
91
82
55
85
85
63
90
86
74
42
79
74
46
81
218
191
194
199
188
164
186
205
184
188
193
176
160
179
14.29
13.77
13.84
13.65
13.02
16.67
11.58
13.09
12.14
12.21
12.11
11.41
16.19
9.77
10.99
10.41
10.48
10.34
9.89
C14H15N3O2S
C15H17N3O2S
C15H17N3O2S
C15H17N3O2S
C15H17N3O3S
C14H14N4O4S
C14H13Cl2N3O2S
C21H20N4O2S2
C23H24N4O2S2
C23H24N4O2S2
C23H24N4O2S2
C23H24N4O4S2
C21H18N6O6S2
C21H16Cl4N4O2S2
14.52
13.85
13.85
13.85
13.16
16.76
11.73
13.20
12.38
12.38
12.38
11.56
16.33
9.96
11.08
10.57
10.57
10.57
10.04
9.59
III
IV
V
VI
VII
VIII
IX
X
XI
XII
XII
XIV
9.62
8.85
8.95
15.00
14.10
14.12
13.99
13.01
12.27
11.24
15.10
14.17
14.17
14.17
13.23
12.46
11.40
a
From ethanol.
and catalyst, bisadducts VIII XIV.
JBX 7.2, and JAB 14 Hz). The respective coupling
constants for monoadducts are 7.2, 7.8, and 14.4 Hz.
In addition, the spectra of monoadducts I VII show
signals of the methylene [doublets of doublets at
5.65 5.60 (cis-H) and 6.15 6.10 ppm (trans-H),
coupling constants 10 and 17 Hz, respectively] and
methine protons (multiplet at 6.22 6.17 ppm) of the
terminal vinyl groups.
Bisadducts VIII XIV were also obtained by thio-
cyanatoarylation of monoadducts I VII.
Cu(BF4)2
(3)
VIII XIV.
I VII + ArN2BF4 + MSCN
N2, MBF4
Bisadducts VIII XIV obtained by schemes (2)
and (3) have the same physicochemical constants.
EXPERIMENTAL
The obtained experimental evidence gives us
grounds to state that the thiocyanatoarylation of N,N-
methylenebisacrylamide occurs stepwise: first by one
multiple bond and then by the second, which is
consistent with the earlier proposed mechanism of
anionarylation [4].
The IR spectra of compounds I XIV were recorded
in mineral oil on a Specord M-80 instrument. The H
NMR spectra were measured in DMSO-d6 on a Varian
VXR-300 instrument (300 MHz), external reference
HMDS. The purity of the synthesized compounds was
established by TLC on Silufol UV-254 plates (eluent
ethanol acetone, 4:1).
1
1
The yields, constants, elemental analyses, and H
NMR and IR spectra of monoadducts I VII and bis-
adducts VIII XIV are given in Tables 1 and 2.
[(3-Phenyl-2-thiocyanatopropionylamino)me-
thyl]-2-acrylamide (I). Benzenediazonium tetrafluoro-
borate, 5.5 g, was added for 30 min to 4.0 g of N,N-
methylenediacrylamide, 0.9 g of copper(II) tetra-
fluoroborate hexahydrate, and 2.2 g of ammonium
thiocyanate in 150 ml of H2O DMF (1:3). Nitrogen
evolution was observed at 10 15 C for 45 min. When
nitrogen no longer evolved, 150 ml of water was
added to the reaction mixture, and the precipitate that
formed was filtered off, dried, and twice recrystallized
from ethanol to obtain 6.8 g (91%) of compound I.
The structures of adducts I XIV are confirmed by
1
their H NMR and IR spectra. The IR spectra of these
compounds contain absorption bands of the carbonyl,
thiocyanato, and amido groups at 1720 1728, 2152
1
2160, and 3412 3420 cm .
1
The H NMR spectra of compounds I XIV contain
multiplets of aromatic protons at 7.7 6.8 ppm. The
CH2 Ar methylene protons and the asymmetric
CH CSN protons form an ABX system and appear as
two doublets of doublets and a triplet at 3.40 3.30,
3.05 3.27, and 4.23 4.32 ppm, respectively (JAX 6.6,
Compounds II VII were prepared in a similar way.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 6 2003

REACTION OF ARENEDIAZONIUM TETRAFLUROBORATES
959
Table 2. IR and 1H NMR spectra of [(3-aryl-2-thiocyanatopropionylamino)methyl]-2-acrylamides I VII and N,N-me-
thylenebis(2-thiocyanato-3-arylpropionamides) VIII XIV
IR spectrum,
1
Comp.
no.
, cm
1H NMR spectrum, , ppm
SCN
2152
C=O
I
1720 9.05 8.89 m (2H, 2NH); 7.53 7.36 m (5H, Ph); 6.20 m (1H, CH=); 6.13 d.d (JHH 17 Hz)
(H-trans, CH2=); 5.64 d.d (JHH 10 Hz) (H-cis, CH2=); 4.48 t (2H, N CH2 N); 4.31 t (JAB
14.4 Hz) (1H, CH); 3.38 d.d (JAX 7.8 Hz), 3.25 d.d (JBX 7.2 Hz) (2H, CH2Ph)
II
2152
2156
2156
2156
1720 8.99 8.81 m (2H, 2NH); 7.22-7.01 m (4H, C6H4); 6.22 m (1H, CH=); 6.15 d.d (JHH 17 Hz)
(H-trans, CH2=); 5.65 d.d (JHH 10 Hz) (H-cis, CH2=); 4.45 t (2H, N CH2 N); 4.29 t
(JAB 14.4 Hz) (1H, CH); 3.39 d.d (JAX 7.8 Hz), 3.26 d.d (JBX 7.2 Hz) (2H, CH2C6H4); 2.24 s
(3H, CH3C6H4)
III
IV
V
1720 8.99 8.84 m (2H, 2NH); 7.14 6.91 m (4H, C6H4); 6.19 m (1H, CH=); 6.15 d.d (JHH 17 Hz)
(H-trans, CH2=); 5.63 d.d (JHH 10 Hz) (H-cis, CH2=); 4.44 t [2H, N CH2 N); 4.29 t
(JAB 14.4 Hz) (1H, CH); 3.38 d.d (JAX 7.8 Hz), 3.26 d.d (JBX 7.2 Hz) (2H, CH2C6H4); 2.28 s
(3H, CH3C6H4)
1720 9.04 8.82 m (2H, 2NH); 7.17 7.00 m (4H, C6H4); 6.21 m (1H, CH=); 6.15 d.d (JHH 17 Hz)
(H-trans, CH2=); 5.65 d.d (JHH 10 Hz) (H-cis, CH2=); 4.44 t (2H, N CH2 N); 4.27 t
(JAB 14.4 Hz) (1H, CH); 3.40 d.d (JAX 7.8 Hz), 3.27 d.d (JBX 7.2 Hz) (2H, CH2C6H4); 2.28 s
(3H, CH3C6H4)
1724 9.08 8.91 m (2H, 2NH); 7.04 6.88 m (4H, C6H4); 6.20 m (1H, CH=); 6.12 d.d (JHH 17 Hz)
(H-trans, CH2=); 5.63 d.d (JHH 10 Hz) (H-cis, CH2=); 4.44 t (2H, N CH2 N); 4.27 t
(JAB 14.4 Hz) (1H, CH); 3.71 s (3H, CH3OC6H4); 3.36 d.d (JAX 7.8 Hz), 3.25 d.d (JBX 7.2 Hz)
(2H, CH2C6H4)
VI
2152
2152
1724 9.07 8.91 m (2H, 2NH); 7.66 7.41 m (4H, C6H4); 6.17 m (1H, CH=); 6.10 d.d (JHH 17 Hz)
(H-trans, CH2=); 5.60 d.d (JHH 10 Hz) (H-cis, CH2=); 4.45 t (2H, N CH2 N); 4.29 t
(JAB 14.4 Hz) (1H, CH); 3.40 d.d (JAX 7.8 Hz), 3.27 d.d (JBX 7.2 Hz) (2H, CH2C6H4)
VII
1720 8.98 8.84 m (2H, 2NH); 7.64 7.52 m (5H, C6H3); 6.22 m (1H, CH=); 6.14 d.d (JHH 17 Hz)
(H-trans, CH2=); 5.62 d.d (JHH 10 Hz) (H-cis, CH2=); 4.46 t (2H, N CH2 N); 4.32 t
(JAB 14.4 Hz) (1H, CH); 3.38 d.d (JAX 7.8 Hz), 3.25 d.d (JBX 7.2 Hz) (2H, CH2C6H3)
VIII
IX
2156
2160
1724 9.06 br.s (2H, 2NH); 7.35 7.24 m (10H, 2Ph); 4.43 t (2H, N CH2 N); 4.23 t (JAB 14 Hz)
(2H, 2CH); 3.30 d.d (JAX 7.2 Hz), 3.05 d.d (JBX 6.6 Hz) (4H, 2CH2Ph)
1724 9.02 br.s (2H, 2NH); 7.15 7.04 m (8H, 2C6H4); 4.45 t (2H, N CH2 N); 4.21 t (JAB 14 Hz)
(2H, 2CH); 3.32 d.d (JAX 7.2 Hz), 3.03 d.d (JBX 6.6 Hz) (4H, 2CH2C6H4); 2.24 s [6H,
2(CH3C6H4)]
X
2160
2160
2168
1728 9.08 br.s (2H, 2NH); 7.11 6.97 m (8H, 2C6H4); 4.44 t (2H, N CH2 N); 4.22 t (JAB 14 Hz)
(2H, 2CH); 3.30 d.d (JAX 7.2 Hz), 3.04 d.d (JBX 6.6 Hz) (4H, 2CH2C6H4); 2.27 s [6H,
2(CH3C6H4)]
XI
XII
1724 9.02 br.s (2H, 2NH); 7.14 7.07 m (8H, 2C6H4); 4.44 t (2H, N CH2 N); 4.23 t (JAB 14 Hz)
(2H, 2CH); 3.31 d.d (JAX 7.2 Hz), 3.06 d.d (JBX 6.6 Hz) (4H, 2CH2C6H4); 2.28 s [6H,
2(CH3C6H4)]
1724 9.02 br.s (2H, 2NH); 7.09 6.85 m (8H, 2C6H4); 4.44 t (2H, N CH2 N); 4.22 t (JAB 14 Hz)
(2H, 2CH); 3.72 s [6H, 2(CH3OC6H4)]; 3.34 d.d (JAX 7.2 Hz), 3.06 d.d (JBX 6.6 Hz) (4H,
2CH2C6H4)
XIII
XIV
2152
2160
1720 9.08 br.s (2H, 2NH); 7.42 7.18 m (8H, 2C6H4); 4.41 t (2H, N CH2 N); 4.23 t (JAB 14 Hz)
(2H, 2CH); 3.35 d.d (JAX 7.2 Hz), 3.09 d.d (JBX 6.6 Hz) (4H, 2CH2C6H4)
1724 9.04 br.s (2H, 2NH); 7.45 7.29 m (6H, 2C6H3); 4.43 t (2H, N CH2 N); 4.23 t (JAB 14 Hz)
(2H, 2CH); 3.31 d.d (JAX 7.2 Hz), 3.05 d.d (JBX 6.6 Hz) (4H, 2CH2C6H3)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 6 2003

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GRISHCHUK et al.
N,N-Methylenebis(3-phenyl-2-thiocyanatopro-
for 45 min. The precipitate was treated as described in
procedure a to obtain 1.9 g (80%) of compound VIII.
pionamide) (VIII). a. Benzenediazonium tetrafluro-
borate, 8.1 g, was added for 45 min to 3.1 g of N,N-
methylenediacrylamide, 1.4 g of copper(II) tetra-
fluoroborate hexahydrate, and 3.2 g of potassium
thiocyanate in 150 ml of H2O DMF (1:3). Nitrogen
evolution was observed at 10 15 C for 1 h. When
nitrogen no longer evolved, 200 ml of water was
added to the reaction mixture, and the precipitate that
formed was filtered off, dried, and crystallized from
ethanol to obtain 7.3 g (86%) of compound VIII.
REFERENCES
1. Grishchuk, B.D., Gorbovoi, P.M., Ganushchak, N.I.,
and Dombrovskii, A.V., Usp. Khim., 1994, vol. 63,
no. 3, p. 269.
2. Grishchuk, B.D. and Gorbovii, P.M., Abstracts of
Papers, XVIII Ukrains’ka konferentsiya z organichnoi
khimii (XVIII Ukrainian Conf. on Organic Chemistry),
Dnepropetrovsk, 1998, p. 22.
3. Grishchuk, B.D., Gorbovoi, P.M., Kudrik, E.Ya., and
Ganushchak, N.I., Zh. Org. Khim., 1991, vol. 61, no. 10,
p. 2335.
b. Benzenediazonium tetrafluoroborate, 0.72 g,
was added for 20 min to 1.0 g of [(3-phenyl-2-thio-
cyanatopropionylamino)methyl]-2-acrylamide, 0.12 g
of copper(II) tetrafluoroborate hexahydrate, and 0.37 g
of potassium thiocyanate in 100 ml of H2O DMF
(1:3). Nitrogen evolution was observed at 15 20 C
4. Grishchuk, B.D., Gorbovoi, P.M., Kudrik, E.Ya., and
Ganushchak, N.I., Zh. Org. Khim., 1991, vol. 61, no. 11,
p. 2583.
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