Thiocyanatoarylation of diethylene glycol diacrylate

Article abstract of DOI:10.1023/A:1021677913217

The example of diethylene glycol diacrylate was used to demonstrate the possibility of thiocyanatoarylation both by one and by two multiple bonds of compounds with two isolated multiple bonds. The reactions of arenediazonium tetrafluoroborates with diethy

Full text of DOI:10.1023/A:1021677913217

Russian Journal of General Chemistry, Vol. 72, No. 9, 2002, pp. 1410 1413. Translated from Zhurnal Obshchei Khimii, Vol. 72, No. 9, 2002,
pp. 1497 1500.
Original Russian Text Copyright
2002 by Grishchuk, Baranovskii, Gorbovoi, Koval’skii, Ganushchak.
Thiocyanatoarylation of Diethylene Glycol Diacrylate
B. D. Grishchuk, V. S. Baranovskii, P. M. Gorbovoi,
Ya. P. Koval’skii, and N. I. Ganushchak
Gnatyuk Ternopol State Pedagogical University, Ternopol, Ukraine
Lvivs’ka Politekhnika National University, Lviv, Ukraine
Franko National University, Lviv, Ukraine
Received December 29, 2000
Abstract The example of diethylene glycol diacrylate was used to demonstrate the possibility of thio-
cyanatoarylation both by one and by two multiple bonds of compounds with two isolated multiple bonds. The
reactions of arenediazonium tetrafluoroborates with diethylene glycol diacrylate in aqueous acetone (1: 2) in
the presence of catalytic amounts of copper gave 1-acryloyloxy-2-[2-(2-thiocyanato-3-arylpropionyloxy)-
ethoxy]ethanes. The latter were reacted with arenediazonium tetrafluoroborates in aqueous acetone (1:3) to
obtain
1-[2-(2-thiocyanato-3-arylpropionyloxy)ethoxy]-2-(2-thiocyanato-3-arylpropionyloxy)ethanes
via
thiocyanatoarylation by two multiple bonds.
We earlier established that thiocyanatoarylation of
monounsaturated and diene compounds [1 4] can take
different ways depending on the type of the unsaturated
compound. Thus, arenediazonium tetrafluoroborates
react with acrylic and methacrylic acid esters in the
presence of potassium thiocyanate to give 1-thio-
cyanato-1-alkoxycarbonyl-2-arylethanes via loss of
diazo group nitrogen and addition of the aryl and
thiocyanato groups by the site of cleavage of the
multiple bond of the monounsaturated compound [5].
Independent of reactant ratio, the second allyl frag-
ment of diallyl ether takes no part in the reaction.
Preceeding with these studies, in the present work
we reacted diazonium salts with unsaturated com-
pounds containing two isolated multiple bonds, in the
presence of foreign nucleophiles. For the model un-
saturated compound we chose an ester, diethylene
glycol diacrylate, which has never been brought into
anionarylation reactions [3].
It was found that arenediazonium tetrafluoroborates
react with diethylene glycol diacrylate in aqueous
acetone (1:2) in the presence of alkali metal or
ammonium thiocyanates and catalytic amounts of
copper tetrafluroborate and at 5 0 C to give
1-acryloyloxy-2-[2-(2-thiocyanato-3-arylpropionyl-
oxy)ethoxy]ethanes I V via loss of diazo group
nitrogen and addition by one of the two multiple
bonds.
The thiocyanatoarylations with divinyl and iso-
prene involve 1,2 addition to form 2-isothiocyanato-
1-aryl-3-butenes have been reported [6]. Thus, for
mally, dienes behave in this reaction as unsaturated
compounds with two isolated multiple bonds.
As shown in [7], diazonium salts react with diallyl
ether in the presence of the thiocyanate nucleophile,
yielding 3-allyloxy-1-aryl-2-thiocyanatopropanes.
N2BF4
SCN
O
O
O
O
+ MBF4 + N2
O
+ MSCN
+
O
O
O
O
O
R
R
I V
R = H (I), o-CH3 (II), m-CH3 (III), p-CH3 (IV), p-CH3O (V); M = Na, K, NH4.
1070-3632/02/7209-1410$27.00 2002 MAIK Nauka/Interperiodica

THIOCYANATOARYLATION OF DIETHYLENE GLYCOL DIACRYLATE
1411
The yields of monoadducts I V are 35 59%. Ortho-,
meta-, or para-methyl substituents in the aromatic
ring decrease the yields of the target products by
10 25%. Therewith, the lowest yield is observed in
the reaction of diethylene glycol diacrylate with o-
toluenediazonium tetrafluoroborate.
It was found that the free multiple bond of mono-
adducts I and IV can be involved in thiocyanatoaryla-
tion via reaction with arenediazonium tetrafluoro-
borates in aqueous acetone (1:3).
The reaction occurs at 10 15 C in the presence
copper(II) tetrafluoroborate and 1.5-fold excesses of
diazonium salt and thiocyanate. Adducts VI VI were
obtained in 39 47% yields. They are white crystalline
substances melting at 69 80 C.
The optimal arenediazonium salt:ester:sodium
(potassium, ammonium) tihocyanate:copper tetra-
fluoroborate ratio was found to be 1.2:1:1.4:0.1. The
by-products are aryl isothiocyanates (9 15%) and aryl
thiocyanates (2 3%).
Compound VII was obtained from benenediazo-
nium tetrafluoroborate and monoadduct I, as well as
from p-toluenediazonium tetrafluoroborate and mono-
adduct IV. The two samples had identical physico-
chemical characteristics.
The reaction temperature is reduced to 25 to
20 C if alkali metal or ammonium thiocyanates are
introduced in the reaction medium last.
The same result was obtained if diazonium salt and
diethylene glycol diacrylate were first reacted at a 1:1
ratio and then, when nitrogen no longer evolved,
additional amounts of benzenediazonium tetrafluro-
borate, ammonium thiocyanate, and catalyst were
introduced in a ratio optimal counting upon the
second multiple bond.
IV + PhN2BF4 + KSCN
VII
I + p-CH3C6H4N2BF4 + KSCN
Heating of monoadducts I V adducts VI VIII in
alcohol produced both no isomerization of thio-
cyanates into isothocyanates and no heterocyclization.
1
The yields, constants, elemental analyses, and H
NMR and IR spectra of compounds I VIII are given
in Tables 1 and 2.
With doubled quantities of diazonium salt, catalyst,
and thiocyanate compared with optimal, the yields of
aryl isothiocyanates and thiocyanates are sharply
increased (58 65 and 8 10%, respectively).
The IR spectra of compounds I V, in agreement
with the proposed structures, contain carbonyl and
thiocyanate absorption bands at 1724 and 2156
Thus, using diethylene glycol diacylate as example,
we showed that a compound containing two isolated
multiple bonds undergoes anionarylation by only one
multiple bond under the given conditions. Apparently,
this anomalous behavior is explained by a much lower
solubility in aqueous acetone (1:2) of monoadducts
I V compared with the starting ester. For this reason,
the products leave the reaction medium, thereby
giving way to prevailing formation of Sandmeyer
adducts, aryl isothiocyanates and thiocyanates.
1
2160 cm , respectively. Moreover, in the spectra of
1
compounds I V, bands at 1636 1640 cm appeared
due to vinyl absorption. The narrow bands at 812 and
1
988 cm are assignable to out-of-plane CH vibrations
of the vinyl group.
1
The H NMR spectra of compounds I VIII show
aromatic proton signals at 7.39 7.08 ppm (multiplet).
The proton signals of the vinyl CH2 group of mono-
adducts I V appear as a doublet of doublets at 6.30
6.34 (cis-H) and 5.92 5.94 ppm (trans-H) with
coupling constants of 10 and 15 Hz, and the methine
proton signals of the vinyl group appear as a doublet
of doublets at 6.14 6.16 ppm and a coupling constant
of 10 Hz.
SCN
O
O
+ MSCN
O
N2BF4
O
O
+
R
R
SCN
1
In the H NMR spectra of compounds VI VIII,
SCN
the protons of the CH groups bound with the thio-
canato group (a triplet at 4.47 4.48 ppm) and protons
of the methylene groups (two doublets of doublets at
3.33 3.34 and 3.10 3.11 ppm) bound with the aro-
matic nuclei form an ABX system (JAX 8, JBX 7, and
JAB 14 Hz).
O
O
O
O
O
+ MBF4 + N2
R
R
VI VIII
EXPERIMENTAL
R = R = H (VI); R = R = p-CH3 (VII); R = H, R =
p-CH3 (VIII); M = Na, K, NH4.
The IR spectra of compounds I V were recorded
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 9 2002

1412
GRISHCHUK et al.
Table 1. Yields, constants, and elemental analyses of 1-acryloyloxy-2-[2-(2-thiocyanato-3-arylpropionyloxy)ethoxy]-
ethanes I V and 1-[2-(2-thiocyanato-3-arylpropionyloxy)ethoxy]-2-(2-thiocyanato-3-arylpropionyloxy)ethanes VI VIII
MRD
Found, %
Calculated, %
Comp. Yield,
n2D0
d240
Formula
no.
%
(mp, C)a
found calculated
N
S
N
S
I
II
59
35
42
47
44
47
39
45
1.5052
1.5136
1.5124
1.5128
1.4956
(80)
1.1580
1.1598
1.1608
1.1588
1.1513
89.53
94.28
94.01
94.23
96.21
89.85
94.50
94.50
94.50
96.28
3.87
3.61
3.58
3.76
3.72
5.59
5.51
5.40
9.06
8.70
8.63
8.67
8.21
13.10
12.71
12.42
C17H19NO5S
C18H21NO5S
C18H21NO5S
C18H21NO5S
C18H21NO6S
C24H24N2O5S2
C25H26N2O5S2
C26H28N2O5S2
4.01
3.85
3.85
3.85
3.69
5.78
5.62
5.46
9.18
8.82
8.82
8.82
8.45
13.23
12.86
12.51
III
IV
V
VI
VII
VIII
(69)
(74)
a
Recrystallized from ethanol.
Table 2. IR and 1H NMR spectra of 1-acryloyloxy-2-[2-(2-thiocyanato-3-arylpropionyloxy)ethoxy]ethanes I V and
1-[2-(2-thiocyanato-3-arylpropionyloxy)ethoxy]-2-(2-thiocyanato-3-arylpropionyloxy)ethanes VI VIII
1
IR spectrum, , cm
Comp.
no.
1H NMR spectrum, , ppm (J, Hz)
SCN CH=CH2 C=O
I
2156 1636
1724 7.30 7.20 m (5H, Ph), 6.30 d.d (cis-H, =CH2, JHH 10), 6.14 d.d (1H, =CH , JHH 10),
5.93 d.d (trans-H, =CH2, JHH 15), 4.50 4.44 m (1H, CH), 4.20 t (4H, 2OCH2), 3.48 d.d
(4H, CH2 O CH2, JHH 2), 3.33 d.d (JHH 7), 3.10 d.d (2H, CH2Ph, JHH 7)
1720 7.22 7.10 m (4H, C6H4), 6.32 d.d (cis-H, =CH2, JHH 10), 6.15 d.d (1H, =CH, JHH 10),
5.94 d.d (trans-H, =CH2, JHH 15), 4.51 4.45 m (1H, CH), 4.22 t (4H, 2OCH2), 3.46 d.d
(4H, CH2 O CH2, JHH 2), 3.32 d.d (JHH 7), 3.09 d.d (2H, CH2 C6H4, JHH 7), 2.25 s
(3H, o-CH3 C6H4)
II
2156 1640
III
IV
V
2160 1636
2156 1636
2156 1636
1724 7.34 7.16 m (4H, C6H4), 6.34 d.d (cis-H, =CH2, JHH 10), 6.15 d.d (1H, =CH, JHH 10),
5.94 d.d (trans-H, =CH2, JHH 15), 4.50 4.44 m (1H, CH), 4.24 t (4H, 2OCH2), 3.45 d.d
(4H, CH2 O CH2, JHH 2), 3.31 d.d (JHH 7), 3.10 d.d (2H, CH2 C6H4, JHH 7),
2.31 s (3H, m-CH3 C6H4)
1724 7.24 7.08 m (4H, C6H4), 6.32 d.d (cis-H, =CH2, JHH 10), 6.16 d.d (1H, =CH, JHH 10),
5.92 d.d (trans-H, =CH2, JHH 15), 4.50 4.44 m (1H, CH), 4.23 t (4H, 2OCH2), 3.46 d.d
(CH2 O CH2, JHH 2), 3.33 d.d (JHH 7), 3.12 d.d (2H, CH2 C6H4, JHH 7), 2.37 s (3H,
p-CH3 C6H4)
1724 7.24 7.14 m (4H, C6H4), 6.32 d.d (cis-H, =CH2, JHH 10), 6.16 d.d (1H, =CH, JHH 10),
5.91 d.d (trans-H, =CH2, JHH 15), 4.51 4.45 m (1H, CH), 4.22 t (4H, 2OCH2), 3.70 s
(3H, p-CH3O C6H4), 3.46 d.d (4H, CH2 O CH2, JHH 2), 3.33 d.d (JHH 7), 3.13 d.d
(2H, CH2 C6H4, JHH 7)
VI
2152
2152
1716 7.34 7.24 m (10H, 2Ph), 4.47 t (2H, 2CH, JAB 14), 4.22 t (4H, 2OCH2), 3.49 d.d (4H,
(CH2 O CH2), 3.34 d.d (JAX 8), 3.10 d.d (4H, 2CH2Ph, JBX 7)
1716 7.39 7.30 m (5H, Ph), 7.22 7.14 m (4H, C6H4), 4.52 t, 4.47 t (2H, 2CH), 4.22 t (4H,
2OCH2), 3.48 d.d (4H, CH2 O CH2), 3.39 3.27 m, 3.17 3.07 m (4H, CH2 C6H4, CH2Ph),
2.26 s (3H, p-CH3 C6H4)
VII
VIII 2156
1720 7.21 7.13 m (8H, 2C6H4), 4.48 t (1H, CH, JAB 14), 4.21 t (4H, 2OCH2), 3.48 d.d (4H,
CH2 O CH2), 3.33 d.d (JAX 8), 3.11 d.d (4H, 2CH2 C6H4, JBX 7), 2.27 s (6H,
2p-CH C6H4)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 9 2002

THIOCYANATOARYLATION OF DIETHYLENE GLYCOL DIACRYLATE
1413
in thin films and of compounds VI VIII, as suspen-
nitrogen no longer evolved. We obtained 8.3 g of com-
pound I, 20.5 g of phenyl isothiocyanate, and 3.3 g
of benzenethiocyanate.
sions in mineral oil, on a Specord M-80 instrument.
1
The H NMR spectra were obtained in DMSO on a
Varian Gemini instrument, working frequency
300 MHz, internal reference HMDS. The individuality
of the synthesized compounds was proved by TLC on
Silufol UV-254 plates (eluent hexane chloroform d
iethyl ether, 7:5:2). Chromatographic separation of
the reaction products was performed on a column of
Al2O3 [eluents hexane chloroform diethyl ether,
7:5:2 (compounds VI VIII), and hexane chloroform,
3:1].
1-[2-(2-Thiocyanato-3-phenylpropionyloxy)-
ethoxy]-2-(2-thiocyanato-3-phenylpropionyloxy)-
ethane (VI). Benzenediazonium tetrafluoroborate,
0.045 mol, was added over the course of 60 min to
0.03 mol of 1-acryloyloxy-2-[2-(2-thiocyanato-3-
phenylpropionyloxy)ethoxy]ethane, 0.003 mol of
copper(II) tetrafluoroborate, and 0.045 mol of potas-
sium thiocyanate in 150 ml of aqueous acetone (1:3).
Nitrogen vigorously evolved at 10 15 C for 60 min.
When the reaction had been complete, the mixture
1-Acryloyloxy-2-[2-(2-thiocyanato-3-phenylpro-
pionyloxy)ethoxy]ethane (I). Benzenediazonium tetra- was treated with 100 ml of diethyl ether, the extract
fluoroborate, 0.12 mol, was added over the course of was washed with water, dried with sodium sulfate,
60 75 min to 0.10 mol of diethylene glycol diacrylate, the ether was evaporated, and the residue was sub-
0.01 mol of copper(II) tetrafluoroborate, and 0.14 mol
of ammonium thiocyanate in 200 ml of aqueous
acetone (1:2). Nitrogen evolution was observed at
5 0 C for 2 h. When nitrogen evolution had ceased,
the reaction mixture was treated with 250 ml of di-
ethyl ether and the extract was washed with water and
dried with magnesium sulfate. The solvent was then
removed, and the residue was subjected to chromato-
graphy to obtain 20.7 g (59%) of compound I.
jected to column chromatography on Al2O3 (eluent
hexane chlorform, 3:1) to obtain 6.1 g (44%) of a
viscous oily substance that crystallized on standing.
Double recrystallization from ethanol gave 4.3 g of
compound VI.
Compounds VII and VIII were obtained in a
similar way.
REFERENCES
Compounds II V were obtained in a similar way.
1. Grishchuk, B.D., Gorbovoi, P.M., Ganushchak, N.I.,
and Dombrovskii, A.V., Usp. Khim., 1994, vol. 63,
no. 3, p. 269.
Reaction of diethylene glycol diacrylate with a
double excess of benzenediazonium tetrafluoro-
borate. a. Benzenediazonium tetrafluoroborate,
0.13 mol, was added over the course of 120 min to
0.05 mol of diethylene glycol diacrylate, 0.01 mol of
copper(II) tetrafluoroborate, and 0.14 mol of ammo-
nium thiocyanate in 200 ml of aqueous acetone (1:2).
Nitrogen evolution was observed at 5 0 C for 2.5 h.
The mixture was then treated with 250 ml of diethyl
ether, and the extract was washed with water and
dried with magnesium sulfate. The ether was removed,
and the residue was subjected to chromatography to
obtain 8.2 g of compound I, 10.8 g of phenyl isothio-
cyanate, and 1.4 g of phenyl thiocyanate.
2. Ganushchak, M. and Obushak, M., Pratsi Nauk. Tovar.
im. Shevchenka, 1997, vol. 1, p. 224.
3. Grishchuk, B.D. and Gorbovii, P.M., Naukovi Zapiski,
Ser. Khim., Ternopil. Peduniv., 1998, no. 2, issue 6,
p. 3.
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Papers, XVIII Ukrains’ka konferentsiya z organichnoi
khimii (XVIII Ukrainian Conf. on Organic Chemistry),
Dnipropetrovsk, 1998, p. 22.
5. Grishchuk, B.D., Gorbovoi, P.M., and Ganushchak, N.I.,
Zh. Obshch. Khim., 1989, vol. 59, no. 8, p. 1868.
b. By analogy with procedure a, when nitrogen
evolution had ceased, additional 0.01 mol of cop-
per(II) tetrafluoroborate and 0.14 mol of ammonium
thiocyanate were added and then, over the course of
2 h, 0.13 mol of benzenediazonium tetrafluoroborate.
The reaction mixture was kept for 3 h at 0 C until
6. Grishchuk, B.D., Gorbovoi, P.M., Vovk, M.V.,
Dyachuk, A.A., Martinyak, I.E., and Ganushchak, N.I.,
Ukr. Khim. Zh., 1991, vol. 57, no. 1, p. 89.
7. Gorbovoi, P.M., Zagrichuk, G.Ya., and Grishchuk, B.D.,
Zh. Obshch. Khim., 2000, vol. 70, no. 5, p. 809.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 9 2002