Reaction of Anhydrides of Mono-, Di-, and Tetracarboxylic Acids with Hexamethyldisilazane: A New Method for Synthesis of N-Trimethylsilylamides and -Imides

Full text of DOI:10.1023/A:1022976622134

Doklady Chemistry, Vol. 389, Nos. 1–3, 2003, pp. 51–53. Translated from Doklady Akademii Nauk, Vol. 389, No. 1, 2003, pp. 55–57.
Original Russian Text Copyright © 2003 by Basenko, Voronkov.
CHEMISTRY
Reaction of Anhydrides of Mono-, Di-, and Tetracarboxylic
Acids with Hexamethyldisilazane: A New Method for Synthesis
of N-Trimethylsilylamides and -Imides
S. V. Basenko and Academician M. G. Voronkov
Received October 24, 2002
Previously, we found that the reaction of hexame-
thyldisilazane (HMDS) with carboxylic acids [1] or
their ammonium salts [2] resulted in the corresponding
trimethylacyloxysilanes.
Continuing this research, we showed that the reac-
tion of anhydrides of monocarboxylic acids with
HMDS resulted in the formation of their N-trimethyl-
silylamides and trimethylacyloxysilanes:
O
Q =
,
,
C
O
The yields of cyclic N-trimethylsilylimides are 50–
9%. All these compounds are yellowish crystalline
substances, which are readily soluble in common
organic solvents.
9
(
RCO) O + Me SiNHSiMe
2 3 3
(1)
RCONHSiMe + RCOOSiMe .
3
3
The yields of the products of reaction (1) are close
to quantitative. In contrast to this, the reaction of
HMDS with dicarboxylic acid anhydrides gives cyclic
N-trimethylsilylimides:
The cyclic anhydrides of 1,2-alkanedicarboxylic acids,
as well as phthalic anhydride derivatives with electroneg-
ative substituents (Cl, NO ), react with HMDS to produce
2
acyclic 1-(trimethylsiloxycarbonyl)-2-(trimethylsilylami-
nocarbonyl) derivatives rather than cyclic imides:
O
C
O
C
Y[
O] + (Me Si) NH
3 2
C
O
Y[
O] + (Me Si) NH
3 2
C
O
(2)
(
4)
O
C
C
O
Y[
NSiMe ] + Me SiOH,
3
3
Me SiOCOYCONHSiMe ,
3 3
Cl
Cl
Y = cis-CH=CH, cis-ClC=CCl, and 1,2-C H .
6
4
Y = –CHCH –,
, and
2
Tetracarboxylic acid anhydrides react analogously:
O N
2
Cl
O
C
C
O
O
C
C
O
Cl
In the above reactions, 1,1,3,3-tetramethyldisila-
zane can be used along with HMDS. Thus, for example,
the former reacts with phthalic anhydride according to
the scheme
O
Q
O + 2(Me Si) NH
3 2
(3)
O
C
O
O
C
C
O
C
C
O
O + (Me HSi) NH
Me SiN
Q
NSiMe + 2Me SiOH,
2
2
3
3
3
C
O
O
(5)
C
NHSiMe H + Me HSiOH.
2
2
Favorskii Institute of Organic Chemistry, Siberian Division,
Russian Academy of Sciences, ul. Favorskogo 1,
Irkutsk, 664033 Russia
C
O
0
012-5008/03/0001-0051$25.00 © 2003 åÄIä “Nauka /Interperiodica”

5
2
BASENKO, VORONKOV
Table 1. Physicochemical constants and elemental analysis data for N-trimethylsilylimides of di- and tetracarboxylic acids
Found, wt %
Calculated, wt %
Compound
Yield, %
Tm, °C
Empirical formula
C H NO Si
C
H
C
H
I. C H (CO) NSiMe
42
87
–
–
50.01
35.07
60.32
6.72
4.10
6.03
49.67
35.31
60.24
6.55
3.81
5.98
2
2
2
3
7
11
2
II. C Cl (CO) NSiMe
C H NO Cl Si
7 9 2 2
2
2
2
3
9
9
66–67
C H NO Si
11 14 2
*
III. C H (CO) NSiMe
3
6
5
2
*
*
IV. O[C H (CO) NSiMe ]
6
3
2
3 2
98
97
126–128
120–122
58.84
–
5.18
–
C H N O Si
58.40
–
5.30
–
2
2
24
2
5
2
*
**
V. CO[C H (CO) NSiMe ]
6
3
2
3 2
–
–
1
*
Bp 120(1)°C. IR (ν, cm ): 1700 (C=O); 1295 (C–N); 1070 (Si–N).
–
1
*
* IR (ν, cm ): 1700, 1710 (C=O); 1300 (C–N); 1070 (Si–N).
–1
+
+
*
** IR (ν, cm ): 1680, 1720 (C=O); 1070 (Si–N). MS, m/z (intensities, % of maximum): 464(1) M ; 449(57) (M–Me); 376(27) (M–NHSiMe ) ;
3
+
+
3
48(19) (M–CO–NHSiMe ) ; 73(100) (SiMe ).
3
3
Table 2. Physicochemical constants and elemental analysis data for O,N-bis(trimethylsilyl) derivatives of monoamides of
dicarboxylic acids Me SiOC(O)YC(O)NHSiMe
3
3
Found, wt %
Calculated, wt %
Com-
pound
Yield,
%
Empirical
formula
Y
Tb, °C
C
H
N
Si
C
H
N
Si
*
VI
CH CH
96
90
110 (1) 45.90 8.63 5.68 21.42 C H NO Si
2
54.197 8.81 5.36 21.40
47.45 6.21 7.90 15.80
2
2
10 23
3
VII C H (NO )**
63 (mp) 47.02 6.27 7.40 15.80 C H N O Si
14 22 2 5 2
6
3
2
*
**
VIII C Cl
96
147–9 (1)
–
–
–
–
–
–
–
–
–
6
4
2
0
20
–1
*
d4 1.0036; nD 1.4525. IR (ν, cm ): 3418 (N–H); 2955 (CH ); 1716( C(O)–O); 1682 (C(O)–N); 1450, 1370 (CH ); 1250, 850, 755
3 3
(
Si–CH ); 1055 (Si–O).
3
1
–1
*
* H NMR (δ, ppm): 0.27 (Me SiO); 0.48 (Me SiNH); 7.58 (C H NO ); IR (ν, cm ): 3420 (N–H); 2960 (CH ); 1728 (C(O)–C);
1
3
3
6
3
2
3
718 (C(O)–N); 1600 (C H ); 1450, 1345 (CH ); 1245, 840, 755 (Si–CH ); 1055 (Si–O).
6 3 3 3
1
+
+
*
** H NMR (δ, ppm): 0.22 (Me SiO); 0.28 (Me SiNH). MS, m/z (intensities, % of maximum): 445(3) M ; 430(20) (M–Me) ; 357(19)
3
3
+
2
+
(
M–NHSiMe ) ; 146(100) Me SiNHSiMe .
3 3
The primary act in the reaction of HMDS with car- cyclization, with elimination of trimethylsilanol:
boxylic acid anhydrides is the cleavage of one anhy-
dride C–O bond. In the case of acyclic anhydrides,
this reaction is the final one, which is shown in
Eq. (1). For cyclic anhydrides of di- and tetracarbox-
ylic acids (for example, phthalic), this stage is
described by the scheme
O
COSiMe3
CNHSiMe3
O
O
C
O
C
O
(
7)
COSiMe3
NHSiMe H + Me SiOH.
2
3
O + (Me Si) NH
3
2
C
O
C
O
CNHSiMe3
O
(6)
The yields of the obtained N-trimethylsilylamides
The intermediate 1-(trimethylsiloxycarbonyl)-2-(tri- and -imides, their physical constants, and analytical
methylsilylaminocarbonyl)benzene undergoes further data are summarized in Tables 1 and 2, respectively.
DOKLADY CHEMISTRY Vol. 389 Nos. 1–3 2003

REACTION OF ANHYDRIDES OF MONO-, DI-, AND TETRACARBOXYLIC ACIDS
53
1
Their structures were confirmed by H NMR and IR were isolated by distillation, and the solid ones, by
recrystallization.
spectroscopy (the parameters are shown in the same
tables) and by mass spectrometry.
REFERENCES
The anhydrides and HMDS were taken in a 1 : 1 or
: 2 molar ratio. The reactions were carried out at
30–140°ë. The mixtures were stirred for 2–3 h (in
the case of the solid aromatic anhydrides, until they
completely dissolved). The liquid reaction products
1
2
. Basenko, S.V., Bormashev, P.A., Mirskov, R.G., and
1
1
Voronkov, M.G., Dokl. Akad. Nauk, 1993, vol. 331,
no. 2, pp. 177–178.
. Voronkov, M.G. and Yarosh, O.G., Zh. Obshch. Khim.,
1972, vol. 42, no. 10, pp. 2030–2032.
DOKLADY CHEMISTRY Vol. 389 Nos. 1–3 2003