Mixed anionoarylation of tetramethylene and diethylene glycol diacrylates

Article abstract of DOI:10.1007/s11176-005-0281-3

The example of tetramethylene and diethylene glycol diacrylates was used to accomplish the first mixed anionoarylation. The reaction of diazonium salts with these unsaturated compounds gave chloroarylation adducts by one multiple bond: 1-acryloyloxy-4-(2-

Full text of DOI:10.1007/s11176-005-0281-3

Russian Journal of General Chemistry, Vol. 75, No. 4, 2005, pp. 613 616. Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 4, 2005,
pp. 650 653.
Original Russian Text Copyright
2005 by Grishchuk, Baranovskii, Gorbovoi.
Mixed Anionoarylation of Tetramethylene
and Diethylene Glycol Diacrylates
B. D. Grishchuk, V. S. Baranovskii, and P. M. Gorbovoi
Gnatyuk National Pedagogical University, Ternopol, Ukraine
Received October 15, 2003
Abstract The example of tetramethylene and diethylene glycol diacrylates was used to accomplish the
first mixed anionoarylation. The reaction of diazonium salts with these unsaturated compounds gave chloro-
arylation adducts by one multiple bond: 1-acryloyloxy-4-(2-chloro-3-arylpropyonyloxy)butanes and 1-acryl-
oyloxy-2-[2-(2-chloro-3-arylpropyonyloxy)ethoxy]ethanes. The latter were subjected to thiocyanatoarylation
to obtain diadducts: 1-(2-chloro-3-arylpropyonyloxy)-4-(2-thiocyanato-3-arylpropyonyloxy)butanes and
1
-(2-chloro-3-arylpropyonyloxy)-2-[2-(2-thiocyanato-3-arylpropyonyloxy)ethoxy]ethanes.
We previously showed [1 4] that under aniono-
arylation conditions tetramethylene and diethylene
glycol and N,N-methylenecarboxamide undergo thio-
cyanatoarylation first by one multiple bond and then
by the other to give mono- and diadducts. These data
lead us to expect that anionoarylation of monoadducts
in the presence of other anions would result in mixed
anionoarylation.
bond to form 1-acryloyloxy-4-(2-chloro-3-arylpro-
pyonyloxy)butanes I and II and 1-acryloyloxy-2-[2-
(2-chloro-3-arylpropyonyloxy)ethoxy]ethanes III and
IV. The reactions occur in aqueous acetone (1:2) at
10 15 C and produce much aryl chlorides, phenols,
and unidentified tarry products. The yields of the
monoadducts are 10 15%.
To improve the yields of the target products, we
performed direct chloroarylation of the starting un-
saturated compounds. In this case, the yields of the
chloroarylation monoadducts were 25 45%. It should
be noted that the copper-catalyzed chloroaryaltion of
glycol diacrylates, like thiocyanatoarylation, stops on
the stage of monoadduct I IV formation.
As model compounds we chose tetramethylene and
diethylene glycol diacrylates. It was found that the
reactions of these unsaturated compounds react with
arenediazonium tetrafluoroborates in the presence of
sodium chloride and catalytic amounts of copper(II)
chloride involves chloroarylation by one multiple
N BF
2
4
Cu(BF4)2
O
O
O
O
1
.
.
+ NaCl
+
+
O
O
X
X
N , NaBF4
2
X
O
O
O
O
O
O
R
R
N Cl
2
Cl
CuCl2
R
I IV
2
N2
X = (CH ) (I, II), (CH ) O(CH ) (III, IV); R = H (I, III), 4-CH (II, IV).
2
4
2 2
2 2
3
The reaction occurs in aqueous acetone (1:2) at
0 to 5 C in the presence of catalytic amounts of
salt and catalyst, no adducts by two multiple bonds
are formed.
1
copper(II) chloride. The optimal diazonium salt:un-
saturated compound:catalyst ratio is 1.6:1:0.12.
With double the optimal quantities of the diazonium
Compounds I IV are viscous orange liquids
tending to polymerize on storage. Their yields,
1
070-3632/05/7504-0613 2005 Pleiades Publishing, Inc.

614
GRISHCHUK et al.
Table 1. Yields, constants, and elemental analyses of 1-acryloyloxy-4-(2-chloro-3-arylpropyonyloxy)butanes I and II
and 1-acryloyloxy-2-[2-(2-chloro-3-arylpropyonyloxy)ethoxy]ethanes III and IV
MRD
Comp.
no.
Yield,
%
Found,
Cl, %
Calculated
Cl, %
2
0
20
n
d
Formula
D
4
found
calculated
I
II
III
IV
41
45
44
38
1.5153
1.5144
1.5085
1.5197
1.1623
1.1429
1.1815
1.1840
80.67
85.61
82.51
87.46
80.94
85.77
82.69
87.51
11.35
10.80
10.66
10.19
C H ClO
11.41
10.92
10.85
10.40
1
6
19
4
4
5
5
C H ClO
17 21
C H ClO
16 19
C H ClO
1
7 21
1
Table 2. IR and H NMR spectral data for 1-acryloyloxy-4-(2-chloro-3-arylpropyonyloxy)butanes I and II and 1-acryloyl-
oxy-2-[2-(2-chloro-3-arylpropyonyloxy)ethoxy]ethanes III and IV
IR spectrum,
1
Comp.
no.
, cm
1H NMR spectrum, , ppm (J, Hz)
CH=CH2
C=O
1716 7.34 7.26 m (5H, Ph), 6.33 d.d (cis-H, =CH , J 11), 6.16 d.d (1H, =CH, JHH 10), 5.93 d.d
I
1636
1636
1644
1640
HH
2
(
trans-H, =CH , J 14), 4.88 d.d (1H, CH, JHH 7), 4.12 t (4H, 2OCH ), 3.36 d.d (J 8),
2 HH 2 HH
3
.12 d.d (2H, CH Ph, J
8), 1.68 1.48 m (4H, CH CH )
HH 2 2
2
II
1724 7.26 7.06 m (4H, C6H4), 6.35 d.d (cis-H, =CH , J
11), 6.18 d.d (1H, =CH, JHH 10),
2
HH
5
.97 d.d (trans-H, =CH , J 14), 4.92 d.d (1H, CH, JHH 7), 4.10 t (4H, 2OCH ), 3.33 d.d
2 HH 2
(
JHH 8), 3.13 d.d (2H, CH C H , J 8), 2.31 s (3H, CH C H ), 1.69 1.46 m (4H, CH CH )
2 6 4 HH 3 6 4 2 2
III
IV
1720 7.30 7.20 m (5H, Ph), 6.30 d.d (cis-H, =CH , J 10), 6.14 d.d (1H, =CH, JHH 10), 5.93 d.d
2 HH
(
trans-H, =CH , J
15), 4.92 4.86 m (1H, CH), 4.20 t (4H, 2OCH ), 3.48 d.d (4H,
HH 2
2
CH OCH , J
2), 3.33 d.d (JHH 7), 3.10 d.d (2H, CH Ph, J
7)
2
2
HH
2
HH
1720 7.24 7.08 m (4H, C H ), 6.32 d.d (cis-H, =CH , J 10), 6.16 d.d (1H, =CH, JHH 10),
6
4
2
HH
5
.92 d.d (trans-H, CH2, JHH 15), 4.94 4.87 m (1H, CH), 4.23 t (4H, 2OCH ), 3.46 d.d (4H,
2
CH OCH , J 2), 3.33 d.d (JHH 7), 3.12 d.d (2H, CH C H , J 7), 2.31 s (3H, CH C H )
2
2
HH
2
6
4
HH
3 6 4
1
constants, elemental analyses, and H NMR and IR
spectra are given in Tables 1 and 2. The samples of
compounds I IV, synthesized by schemes 1 and 2,
are identical to each other.
Thus, the use as chloroarylating agents of arenedi-
azonium chlorides does not alter the regioselectivity
of the anionoarylation of glycol diacrylates, and the
reaction does not go further monoadduct formation.
The lower yields of arylalkyl chlorides compared with
those of monothiocyanatoarylation products [1] are
explained by a considerable difference in nucleo-
philicity between chloride and thiocyanate anions. In
this connection we considered it important to react the
monoadducts obtained with arenediazonium tetrafluo-
roborates in the presence of the thiocyanato group.
1
The structure of adducts I IV is proved by their H
and IR spectra. The IR spectra contain carbonyl ab-
sorption bands (1716 1724 cm ), as well as bands
due to stretching (1636 1644 cm ) and deformation
vibrations (808 812 and 980 984 cm ) of the multi-
ple bond of the free acrylic fragment. The H NMR
spectra contain aromatic proton signals at 7.34
1
1
1
1
7
.06 ppm (multiplet). The methylene proton signals
Monoadducts I IV react with arenediazonium tetra-
fluoroborates in the presence of potassium thiocyanate
to form diadducts: 1-(2-chloro-3-arylpropionyloxy)-
of the terminal vinyl group form a doublet of doublets
at 6.35 6.30 (cis-H) and 5.97 5.92 ppm (trans-H)
with coupling constants of 10 and 15 Hz, and the
methane protons of the same group appear as a
doublet of doublets at 6.18 6.14 ppm (coupling
constant 10 Hz). The asymmetrical proton of the CH
group attached to chlorine resonates at 4.94 4.86 ppm
4-(2-thiocyanato-3-arylpropionyloxy)butanes V and
VI and 1-(2-chloro-3-arylpropionyloxy)-2-[2-(2-thio-
cyanato-3-arylpropionyloxy)ethoxy]ethanes VII
and VIII.
(
multiplet).
The reaction was accomplished in aqueous acetone
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 4 2005

MIXED ANIONOARYLATION OF TETRAMETHYLENE
615
N BF
O
O
2
4
X
O
O
Cu(II)
N , KBF4
+
I IV + KSCN
Cl
SCN
2
R
R
R
V VIII
X = (CH ) (V, VI), (CH ) O(CH ) (VII, VIII); R = H (V, VII), 4-CH (VI, VIII).
2
4
2 2
2 2
3
(
1:3) at 10 15 C in the presence of a catalyst, cop-
triplets at 4.77 4.74 and 4.51 4.48 ppm, and the
per(II) tetrafluoroborate, with a 1,3-fold excess of the
arenediazonium salt and potassium thiocyanate. The
yields of diadducts V VIII were 26 38%. The mixed
chloro- and thiocyanatoarylation diadducts are white
crystalline substances melting at 86 99 C (from
methanol). The yields and constants of compounds
V VIII are listed in Tables 3 and 4.
protons of the CH groups attached to the aromatic
2
fragments, multiplets at 3.38 3.27 and 3.16 3.06 ppm
(Table 4).
Thus, the presence of two identical unsaturated re-
action centers in the molecules of glycole diacrylates
and their successive involvement into reaction allows
synthesis of polyfunctional arylalkyl derivatives not
only with different aromatic substituents, but also
The structure of diadducts V VIII is proved by
1
their H and IR spectra. The IR spectra contain absorp- with different anions.
tion bands of the thiocyanato group at 2152
2
1
1
156 cm . The H NMR spectra contain aromatic
EXPERIMENTAL
proton signals at 7.35 7.01 ppm (multiplet). The
asymmetric protons of the CH groups attached to the
chlorine atom and the thiocyanato group form two
The IR spectra were recorded on a Specord M-80
instrument for thin films (adducts I IV) or Nujol
Table 3. Yields, constants, and elemental analyses of 1-(2-chloro-3-arylpropionyloxy)- 4-(2-thiocyanato-3-arylpropionyl-
oxy)butanes V and VI and 1-(2-chloro-3- arylpropionyloxy)-2-[2-(2-thiocyanato-3-arylpropionyloxy)ethoxy]ethanes VII
and VIII
Found, %
N
Calculated, %
N
Comp. no. Yield, %
mp, Ca
Formula
Cl
S
Cl
S
V
VI
VII
VIII
38
30
39
26
99
88
93
86
7.71
7.39
7.51
7.13
3.00
2.91
2.95
2.82
7.05
6.59
6.82
6.50
C H ClNO S
7.95
7.48
7.67
7.24
3.14
2.95
3.03
2.86
7.19
6.76
6.94
6.54
2
3
24
4
C H ClNO S
25 28 4
C H ClNO S
23 24 5
C H ClNO S
2
5
28
5
a
Recrystallized from methanol.
Table 4. IR and 1H NMR spectra of diadducts V VIII
Comp. IR spectrum,
1H NMR spectrum, , ppm
1
no.
(SCN), cm
V
2156
7.35 7.22 m (10H, 2Ph), 4.74 t [1H, CH(Cl)], 4.50 t [1H, CH(SCN)], 4.12 t (4H, 2OCH2),
.36 3.29 m, 3.15 3.06 m (4H, 2CH Ph), 1.65 1.57 m (4H, CH CH )
3
2
2
2
VI
2156
7.14 7.02 m (8H, 2C H ), 4.77 t [1H, CH(Cl)], 4.49 t [1H, CH(SCN)], 4.10 t (4H, 2OCH ),
6
4
2
3
.35 3.27 m, 3.14 3.06 m (4H, 2CH C H ), 2.25 s (6H, 2CH C H ), 1.64 1.56 m (4H, CH CH )
2 6 4 3 6 4 2 2
VII
VIII
2152
7.33 7.18 m (10H, 2Ph), 4.75 t [1H, CH(Cl)], 4.51 t [1H, CH(SCN)], 4.24 t (4H, 2OCH2),
.52 d.d (4H, CH OCH ), 3.38 3.28 m, 3.16 3.08 m (4H, 2CH Ph)
3
2
2
2
2152
7.16 7.01 m (8H, 2C H ), 4.76 t [1H, CH(Cl)], 4.48 t [1H, CH(SCN)], 4.23 t (4H, 2OCH ),
6
4
2
3
.51 d.d (4H, CH OCH ), 3.38 3.29 m, 3.16 3.07 m (4H, 2CH C H ), 2.26 s (6H, 2CH C H )
2 2 2 6 4 3 6 4
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 4 2005

616
GRISHCHUK et al.
1
mulls (adducts V VII). The H NMR spectra were
butane (I), 0.003 mol if copper(II) tetrafluroborate
hexahydrate, and 0.045 mol of potassium thiocyanate
in 150 ml of aqueous acetone (1:3), 0.045 mol of
benzenediazonium tetrafluroborate was added over
the course of 1 h. Vigorous nitrogen evolution was
observed at 10 15 C for 1 h. When nitrogen no longer
evolved, the reaction mixture was treated with 100 ml
of diethyl ether, and the extract was washed with
water and dried with magnesium sulfate. The ether
was removed by distillation, and the residue was
subjected to column chromatography on Al O (eluent
obtained on a Varian VXR-300 instrument for
DMSO-d solutions (300 MHz), external reference
HMDS. The purity of the synthesized compounds was
established by TLC on Silufol UV-254 plates (eluent
hexane chloroform, 3:1).
6
1
-Acryloyloxy-4-(2-chloro-3-phenylpropionyl-
oxy)butane (I). a. To 0.05 mol of tetramethylene
glycol diacrylate, 0.075 mol of sodium chloride, and
.0076 mol of copper(II) tetrafluoroborate hexahyd-
rate in 250 ml of aqueous acetone (1:2), benzenedi-
azonium tetrafluoroborate, 0.075 mol, was added over
the course of 1.5 h. Nitrogen evolution was observed
at 10 15 C for 1.5 h. When nitrogen no longer
evolved, the reaction mixture was treated with 200 ml
of diethyl ether, and the extract was washed with
water and dried with calcium chloride. The ether was
removed by distillation, and the residue was subjected
to column chromatography on Al O (eluent hexane
0
2
3
hexane chloroform, 3:1). Yield 5.7 g (38%), viscous
oily substance crystallizing on standing. Recrystalliza-
tion from methanol gave 3.7 g of compound V, mp
9
9 C.
Compounds VI VIII were prepared in a similar
way.
ACKNOWLEDGMENTS
2
3
chloroform, 3:1). The fractions collected were
analyzed by IR spectroscopy and TLC. Yield 2.9 g
19%), oily orange substance.
The work was financially supported by the Mi-
nistry of Science and Education of Ukraine.
(
b. To 0.05 mol of tetramethylene glycol diacrylate
and 0.0061 mol of copper(II) chloride hexahydrate in
REFERENCES
2
0
00 ml of aqueous acetone (1:2), a solution of
.081 mol of benzenediazonium chloride was added
1
. Grishchuk, B.D., Baranovs’kii, V.S., Gorbovii, P.M.,
and Drozdova, E.L., Nauk. Zapiski Ternopil. Derzh.
Ped. Univ., Ser. Khim., 2001, no. 5, p. 3.
over the course of 1 h. Nitrogen evolution was ob-
served at 5 to 10 C for 2 h. When nitrogen no
longer evolved, the reaction mixture was treated with
2. Gorbovoi, P.M., Baranovskii, V.S., Koval’skii, Ya.P.,
and Grishchuk, B.D., Zh. Obshch. Khim., 2002, vol. 72,
no. 8, p. 1311.
1
50 ml of diethyl ether, and the extract was washed
with water and dried with calcium chloride. Com-
pound I was isolated like in procedure a. Yield 6.4 g
3
. Grishchuk, B.D., Baranovskii, V.S., Gorbovoi, P.M.,
Koval’skii, Ya.P., and Ganushchak, N.I., Zh. Obshch.
Khim., 2002, vol. 72, no. 9, p. 1497.
(
41%).
Compounds II IV were obtained in a similar way.
-(2-Chloro-3-phenylpropionyloxy)-4-(3-phenyl-
-thiocyanatopropionyloxy)butane (V). To 0.03 mol
1
4. Grishchuk, B.D., Baranovskii, V.S., Gorbovoi, P.M.,
and Ganushchak, N.I., Zh. Obshch. Khim., 2003,
vol. 73, no. 6, p. 1011.
2
of 1-acryloyloxy-4-(2-chloro-3-phenylpropionyloxy)-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 4 2005