Reaction of organosilicon amines with dicarboxylic anhydrides

Article abstract of DOI:10.1023/B:RUGC.0000007614.35160.41

Organosilicon amines react with cyclic dicarboxylic anhydrides to form previously unknown amido acids, which are converted into ammonium salts by the reaction with an equimolar amount of the amine. The structures of the compounds were studied by NMR spectroscopy.

Full text of DOI:10.1023/B:RUGC.0000007614.35160.41

Russian Journal of General Chemistry, Vol. 73, No. 7, 2003, pp. 1072 1076. Translated from Zhurnal Obshchei Khimii, Vol. 73, No. 7, 2003,
pp. 1134 1138.
Original Russian Text Copyright
2003 by Kovyazin, Nikitin, Kopylov, Sokol’skaya.
Reaction of Organosilicon Amines with Dicarboxylic Anhydrides
V. A. Kovyazin, A. V. Nikitin, V. M. Kopylov, and I. B. Sokol’skaya
State Research Institute of Chemistry and Technology of Organometallic Compounds,
Federal State Unitary Enterprise, Moscow, Russia
Received July 19, 2001
Abstract Organosilicon amines react with cyclic dicarboxylic anhydrides to form previously unknown
amido acids, which are converted into ammonium salts by the reaction with an equimolar amount of the amine.
The structures of the compounds were studied by NMR spectroscopy.
Carbofunctional organosilicon compounds are of
interest as intermediates in synthesis. In particular,
reactions of organosilicon amines allow preparation of
a wide range of compounds from commercially avail-
able chemicals, e.g., of carbamates [1], thiocarba-
mates [2], sulfones, sulfoxides [3], etc. Addition of
one or two glycidyl methacrylate molecules to 3-ami-
nopropyltriethoxysilane gave silicon-containing amino
acrylates [4, 5]. Opening of the epoxy ring is accom-
panied by isomerization and formation of amido alco-
hols [6]:
nopropyltriethoxysilane I with maleic anhydride was
performed in the bulk, with gradual addition of maleic
anhydride to the amine and with cooling.
O
O
(EtO)3Si(CH2)3NH2 +
I
O
(EtO)3SiCH2CH2CH2NHCOCH=CHCOOH.
II
1
Comparison of the H NMR spectra of amino sil-
CH3
ane I and compound II suggests that the latter exists in
the form of the ammonium salt (EtO)3SiCH2CH2CH2
N+H2COCH=CHCOO . In the spectrum of I, the NH2
protons give a narrow singlet at 1.17 ppm. In the
1H NMR spectrum of II (Fig. 1), two protons at the
nitrogen atom also give a singlet, but this signal is
considerably broadened and shifted downfield (
(EtO)3Si(CH2)3NH2 + CH2 CHCH2OOCC=CH2
O
CH3
(EtO)3Si(CH2)3NHCH2CHCH2OOCC=CH2
OH
CH3
O
C C=CH2
(EtO)3Si(CH2)3N
CH2CHCH2OH
OH
Products of reactions of amino alkoxysilanes with
dicarboxylic anhydrides are mentioned in patents
[7 11]. The reactions performed with amino silanes
containing various numbers of nitrogen atoms at vari-
ous anhydride : amine ratios could be the routes to
compounds differing in the structure and functionality.
However, published structural data for these products
are lacking.
In this work we studied the reactions of carbo-
functional amino alkoxysilanes with cyclic dicarbox-
ylic anhydrides and the structures and conditions of
formation of the resulting products.
8.5
7.5 6.5 4.5 3.5 2.5
1.5
0.5
, ppm
All the reactions of amino alkoxysilanes with cy-
clic anhydrides are exothermic. The reaction of 3-ami-
1
Fig. 1. H NMR spectrum of II.
1070-3632/03/7307-1072$25.00 2003 MAIK Nauka/Interperiodica

REACTION OF ORGANOSILICON AMINES WITH DICARBOXYLIC ANHYDRIDES
Table 1. 1H NMR spectra of amino silane I, diamine, and compounds II XIII ( , ppm)
Comp.
1073
SiCH2
CH2
CH2N
CH3
CH2O NH2
+NH2 NHCO COOH
CH=CH
CH3O
no.
I
II
III
IV
0.56
0.66
0.62
0.53
1.48
1.73
2.61
3.38
1.16
1.21
1.18
1.18
3.76
3.81
3.79
3.76
1.17
8.11
7.61
6.28, 6.43
5.83, 6.14
5.48 5.79
1.74, 1.61 3.22, 2.83
9.50
6.30
1.56
1.80, 1.60
1.70
3.11
methylcyclo-
hexenylidene
5.53 5.90
methylcyclo-
hexenylidene
8.04, 7.77,
7.67, 7.39
phenylene
V
0.64
0.61
2.85
1.25
1.15
1.20
3.80
3.64
3.74
5.40
9.30
VI
3.31, 2.90
3.29, 2.69
VII
Diamine
VIII
0.45,
0.68
0.58
1.66
1.52
1.82
6.65
8.48
7.46, 7.61
phenylene
2.53, 2.58,
2.71
3.01, 3.18,
3.63
1.17
3.49
3.55
0.69
6.05, 6.16
IX
X
0.58
0.62
1.74
1.53
2.95, 3.22
2.63, 2.90,
3.80
8.89 5.99, 6.33
7.70, 7.82
3.48
3.50
7.35
phenylene
XI
0.67
0.59
1.85
1.50
3.00, 3.35,
4.05
2.5 3.0
10.00
7.27 7.88
phenylene
5.51 5.79
3.40
3.53
XII
methylcyclo-
hexenylidene
5.43 5.78
XIII
0.70
1.75
2.0 3.4
9.22
3.54
methylcyclo-
hexenylidene
8.11 ppm). At the same time, protonation of the nitro-
gen atom strongly affects the position of the signals
of the propylene group, especially of the CH2N pro-
tons: their signal is shifted downfield by 0.77 ppm as
compared to I. The signals of the two CH2 groups
more remote from the nitrogen atom are also shifted
downfield but to a lesser extent (Table 1).
The signals of the methylene groups of the propylene
bridges are located at a sufficient distance from each
other and can be identified as follows: a, f, 0.62; b,
1.61; e, 1.74; c, 2.83; and d, 3.22. As judged from the
integral intensity, the broadened signal at 7.61 ppm
+
is due to the NH+ protons of the NH3 group, and the
singlet at
9.50 ppm, to the NHCO proton.
The ammonium form of II can react with amino
silane I, which is a stronger base than the amido group
in II. The reaction of II with I in an equimolar ratio
gives product III.
A similar reaction was performed with 3-methyl-
1,2,3,6-tetrahydrophthalic anhydride:
O
II + (EtO)3SiCH2CH2CH2NH2
O
(EtO)3Si(CH2)3NH2 +
a
(EtO)3SiCH2CHb 2CcH2NHCOCH=CHCOO
O
CH3
O
d
e
f
N+H3CH2CH2CH2Si(OEt)3.
III
(EtO)3Si(CH2)3NHC
COOH
CH3
1
Using the H NMR data for I and II, we assigned
the signals in the H NMR spectrum of III (Fig. 2).
1
IV
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 7 2003

1074
KOVYAZIN et al.
VI + (EtO)3SiCH2CH2CH2NH2
O
COO N+H3(CH2)3Si(OEt)3
(EtO)3Si(CH2)3NHC
VII
that compound VI exists in two forms, acid and salt
VIa, apparently occuring in an equilibrium:
O
(EtO)3Si(CH2)3N+H2C
VI
COO
VIa
In VIa, the CH2N group should give a triplet;
therefore, from the ratio of the integral intensities of
the two CH2N signals, we can determine the ratio
VI : VIa = 1.2 : 1.
Compounds VII and III appreciably differ in the
positions of signals of the propylene group: whereas
the CH2Si groups in III give one signal ( 0.60 ppm),
in VII they give two multiplets ( 0.45 and 0.68 ppm).
The middle CH2 groups in VII give two partially
overlapping multiplets, in contrast to III where they
are separated by 0.35 ppm. The CH2N groups, as in
III, give a triplet ( 2.69 ppm) and a multiplet (
3.29 ppm).
9.5
7.5
6.5 5.5 3.5
2.5
1.5
0.5
, ppm
1
Fig. 2. H NMR spectrum of III.
The reaction of IV with one more molecule of I
yields neutral compound V.
IV + (EtO)3SiCH2CH2CH2NH2
An attempt to perform the reaction of 3-(2-amino-
ethyl)aminopropyltrimethoxysilane (diamine) with
maleic anhydride in the bulk failed, because the heat
evolution was so strong that cause tarring. To provide
milder reaction conditions, the reactions of the di-
amine with dicarboxylic anhydrides were performed
in ethyl acetate. The spectral characteristics of the
products are listed in Table 1. The spectral data and
the titration results show that the reactions of equi-
molar amounts of the diamine and anhydride yield
neutral products, and at the ratio diamine : anhy-
dride = 1 : 2 dicarboxylic acids are formed:
O
COO N+H3(CH2)3Si(OEt)3
(EtO)3Si(CH2)3NHC
CH3
V
Similar results were obtained in the reaction of I
with phthalic anhydride.
1
The H NMR spectrum of VI contains two singlets
of CH2N protons: a triplet at 2.90 ppm and a multiplet
at 3.31 ppm; the CH2 group in the middle of the prop-
ylene chain gives a multiplet at 1.66 1.75 ppm. The
fact that the CH2N group gives two signals suggests
C=O
(MeO)3Si(CH2)3NH(CH2)2NH2 + R
O
C=O
(MeO)3Si(CH2)3N+H2(CH2)2NHC(O)RCOO
O
VIII, X, XII
O
(EtO)3Si(CH2)3NH2 +
(EtO)3Si(CH2)3NHC
C=O
O
C=O
VIII, X, XII + R
O
O
(MeO)3Si(CH2)3N(CH2)2NHC(O)RCOOH
COOH
C(O)RCOOH
IX, XI, XIII
VI
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 7 2003

REACTION OF ORGANOSILICON AMINES WITH DICARBOXYLIC ANHYDRIDES
1075
Table 2. Yields, refractive indices, and elemental analyses of II XIII
Found, %
Calculated, %
Comp.
no.
Yield, %
n2D0
Formula
C
H
N
Si
C
H
N
Si
II
99
99
98
99
99
98
97
96
97
97
97
96
48.45
49.01
56.02
52.98
55.42
52.97
45.23
45.77
51.45
55.42
52.65
56.13
7.53
8.78
8.40
9.13
7.43
8.39
7.36
6.14
7.23
5.61
8.13
7.41
4.41
5.05
3.55
4.60
3.55
4.58
8.66
6.55
7.45
5.31
7.11
4.98
8.98
10.46
7.32
9.25
7.48
9.35
8.89
6.87
7.78
5.68
7.33
5.23
C13H25NO6Si
C22H48N2O9Si2
C18H33NO6Si
C27H56N2O9Si2
C17H27NO6Si
C26H50N2O9Si2
C12H24N2O6Si
C16H26N2O9Si
C16H26N2O6Si
C24H30N2O9Si
C17H32N2O6Si
C26H42N2O9Si
48.90
48.89
55.81
53.29
55.28
52.88
45.00
45.93
51.89
55.60
52.58
56.31
7.84
8.89
8.53
9.21
7.31
8.47
7.50
6.22
7.03
5.79
8.25
7.58
4.39
5.19
3.61
4.61
3.79
4.75
8.75
6.70
7.56
5.41
7.22
5.05
8.78
10.37
7.24
9.21
7.59
9.49
8.75
6.70
7.56
5.41
7.22
5.05
III
IV
V
VI
VII
VIII
IX
X
1.4587
1.4740
1.4645
1.4950
1.4740
XI
XII
XIII
1
Compounds IX, XI, and XIII can be converted
into the neutral form by the reaction with one diamine
molecule or with two molecules of I.
Compounds II XIII were identified by H NMR
spectroscopy; these substances are soluble in water
and polar organic solvents.
(MeO)3Si(CH2)3N(CH2)2NHC(O)RCOO
C(O)RCOO N+H3(CH2)2N+H2(CH2)3Si(OMe)3
IX, XI, XIII + (MeO)3Si(CH2)3NH(CH2)2NH2
The high solubility in water and alcohols makes
these compounds fairly promising for the use as dress-
ing agents for treatment of mineral fillers. However,
in industrial use of dressing agents, it is desirable to
use as solvents lower alcohols, in particular, ethanol.
In this connection, we performed the reactions of I
and the diamine with maleic anhydride in absolute
ethanol. The reaction of I with maleic anhydride in
ethanol (molar ratio amine : maleic anhydride 2 : 1,
50% solution) gave a neutral reaction product. Hence,
under these conditions maleic anhydride has no time
to react with ethanol. Otherwise unchanged amino sil-
ane I would remain in the reaction mixture, imparting
to it an alkaline reaction. A similar result was ob-
tained in the reaction of the diamine with maleic
anhydride in ethanol at the equimolar ratio of the
diamine and maleic anhydride.
determined by titration with 0.1 N NaOH (phenol-
phthalein indicator).
(E)-Butenedioic acid 3-(triethoxysilyl)propyl-
amide II. Maleic anhydride (98 g) was added with
stirring and cooling to 221 g of amino silane I; the
reaction temperature was maintained within the range
50 60 C. After adding the whole amount of the anhy-
dride, the mixture was cooled to room temperature;
318 g of II was obtained as an amorphous solid, mp
38 C.
3-(Triethoxysilyl)propylammonium (E)-3-{N-[3-
(triethoxysilyl)propyl]carbamoyl}propenoate III
was prepared by the reaction of 221 g of I with 49 g
of maleic anhydride with stirring and cooling. The
reaction temperature was maintained within the range
50 60 C. After adding the whole amount of the anhy-
dride, the mixture was cooled to room temperature,
and 268 g of III was obtained as a viscous liquid.
EXPERIMENTAL
1
The H NMR spectra were recorded on a Bruker
Compounds IV VII were prepared similarly.
AM-360 spectrometer (360 MHz) in CDCl3.
(E)-3-{N-[3-(Triethoxysilyl)propylammonio-
ethyl]carbamoyl}propenoate VIII was prepared
The acid numbers of the synthesized products were
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 7 2003

1076
KOVYAZIN et al.
from 222 g of the diamine and 98 g of maleic an-
hydride in 320 g of ethyl acetate with stirring and
cooling. The reaction temperature was maintained
within the range 50 60 C. After adding the whole
amount of the anhydride, the mixture was cooled to
room temperature, and the solvent was distilled off at
reduced pressure. Compound VIII (312 g) was ob-
tained as an amorphous solid; mp 56 58 C.
4. Kopylov, V.M., Prikhod’ko, P.L., Kireev, V.V.,
Rudman, E.V., Korshunov, M.A., Mikhlin, V.S., and
Kovyazin, V.A., USSR Inventor’s Certificate 1122662,
1984, Byll. Izobret., 1984, no. 41.
5. Kovyazin, V.A., Kopylov, V.M., Shkol’nik, M.I., Saf-
rygina, I.A., Demina, N.M., and Ezhova, V.A., RF
Patent 2084456, 1994, Byull. Izobret., 1997, no. 20.
6. Rudman, E.V. and Kovyazin, V.A., Abstracts of
Papers, Vsesoyuznaya konferentsiya po proizvodstvu
kremniiorganicheskikh produktov i primeneniyu ikh
dlya povysheniya dolgovechnosti i kachestva materia-
lov i izdelii otraslei narodnogo khozyaistva (All-
Union Conf. on Production of Organosilicon Com-
pounds and Their Use for Extending the Service Life
and Improving the Quality of Materials and Articles
in the National Economy), Moscow, 1988, p. 68.
Compounds IX XIII were prepared similarly. The
refractive indices of III VII and analytical data for
II XIII are listed in Table 2.
ACKNOWLEDGMENTS
The study was financially supported by ISTC
(grant 1891).
7. CSSR Inventor’s Certificate 221786, 1985, Ref. Zh.
Khim., 1986, 4N77P.
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