1,1-Dimethyl-1-(trialkoxysilylmethyl)hydrazinium and 1,1-dimethyl-1-(silatranylmethyl)hydrazinium Halides

Article abstract of DOI:10.1007/s11176-005-0335-6

Formerly unknown 1,1-dimethyl-1-(trialkoxysilylmethyl)- and 1,1-dimethyl-1-(silatranylmethyl)hydrazinium halides were prepared by reaction of 1,1-dimethylhydrazine with (halomethyl)trialkoxysilanes XCH ₂Si(OR)₃ (X = Cl, I; R=Me, Et) and 1-(halomethyl)silatranes XCH₂Si(OCH₂CH₂) ₃N (X = Cl, Br). 1,1-Dimethyl-1-(silatranylmethyl)hydrazinium chloride and iodide were also obtained by transetherification of corresponding 1,1-dimethyl-1-(trimethoxysilylmethyl)hydrazinium halides with tris(2-hydroxyethyl)amine.

Full text of DOI:10.1007/s11176-005-0335-6

Russian Journal of General Chemistry, Vol. 75, No. 6, 2005, pp. 862 866. Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 6, 2005,
pp. 915 919.
Original Russian Text Copyright
2005 by Sorokin, Voronkov.
1
,1-Dimethyl-1-(trialkoxysilylmethyl)hydrazinium
and 1,1-Dimethyl-1-(silatranylmethyl)hydrazinium Halides
M. S. Sorokin and M. G. Voronkov
Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, Irkutsk, Russia
Received February 6, 2004
Abstract Formerly unknown 1,1-dimethyl-1-(trialkoxysilylmethyl)- and 1,1-dimethyl-1-(silatranylmethyl)-
hydrazinium halides were prepared by reaction of 1,1-dimethylhydrazine with (halomethyl)trialkoxysilanes
XCH Si(OR) (X = Cl, I; R=Me, Et) and 1-(halomethyl)silatranes XCH Si(OCH CH ) N (X = Cl, Br).
2
3
2
2
2 3
1
,1-Dimethyl-1-(silatranylmethyl)hydrazinium chloride and iodide were also obtained by transetherification of
corresponding 1,1-dimethyl-1-(trimethoxysilylmethyl)hydrazinium halides with tris(2-hydroxyethyl)amine.
We recently prepared organosilicon compounds
simultaneously containing a five-coordinate silicon
and an onium nonmetal atoms (nitrogen, phosphorus,
sulfur, silicon, and tellurium) intervened by a me-
thylene bridge. They all had the general formula
alkoxysilanes II and IV, the reactions are complete
within 8 h, and the yields of the iodides come close
to quantitative. The reactions of dimethylhydrazine
with the less active (chloromethyl)trialkoxysilanes I
and III are complete within 14 h. The yields of chlo-
rides V and VII reach 85%.
+
+
+
N(CH CH O) SiCH Y I , where
Y
=
N Me ,
2
2
3
2
3
+
+
+
+
N HEt , N H C H , N= C H , N C H , etc [1]; P Ph
2
2
6
5
5
5
9
7
3
+
+
+
+
+
[
(
2]; S Me , S MeEt, S MePh, S Me(CH Ph), S Me
CH Ph), S Me(CH COOH), S Me(CH CH OH),
S Me[CH Si(OCH CH ) N],
CH ) N] , etc.[3]; Se Me , Se MeEt, Se MePh [4];
(RO) SiCH X + Me NNH
2
2
3
2
2
2
+
+
I IV
2
2
2
2
+
+
+
S [CH Si(OCH
(RO) SiCH Me NNH X ,
(1)
2
2
2 3
2
2
3
2
2
2
+
+
+
V VIII
2
3
2
2
+
+
Te Me , Te Vin [5]. Along with these compounds,
2
2
R = Me, X = Cl (I, V), I (II, VI); R = Et, X = Cl (III, VII),
I (IV, VIII).
we also prepared their analogs containing a four-co-
ordinate silicon and an onium nitrogen, sulfur, or s
+
elenium atom of the general formula R SiCH Y I
3
2
+
+
The reaction of dimethylhydrazine with (chloro-
methyl)trimethoxysilane (I) under the conditions of
the synthesis of (1,1-dimethylhydrazinomethyl)di-
methylmethoxysilane Me NNHCH SiMe (OMe) from
where R = Me, Y = N Me [6, 7], R = MeO, Y =
S MeEt; R = EtO, Y = S MeEt; R = EtO, Y =
S Me [3], R = EtO, Y = Se Me [8]. The crystal and
3
+
+
+
+
2
2
2
2
2
molecular structure of trimethyl(silatranylmethyl)-
ammonium [9], triphenyl(silatranylmethyl)phospho-
nium [2], dimethyl(silatranylmethyl)sulfonium [10],
and trimethyl(trimethylsilylmethyl)ammonium iodides
dimethylhydrazine and (chloromethyl)methoxydime-
thylsilane [11] leads to 1,1-dimethyl-1-(trimethoxy-
silylmethyl)hydrazinium chloride (V) in 45% yield.
Along with this product, other products were formed,
among which (1,1-dimethylhydrazinomethyl)trime-
thoxysilane Me NNHCH Si(OMe) was identified by
[7] was established by means of X-ray diffraction.
Developing this aspect of our research, we have
studied reactions of 1,1-dimethylhydrazine with (halo-
2
2
2
+
GC MS (M 194), but its fraction was no more
methyl)trialkoxysilanes XCH Si(OR) I IV in the
than 10%.
2
3
absence of solvent and in hexane, as well as reactions
of 1,1-dimethylhydrazine with 1-(halomethyl)sila-
tranes XCH Si(OCH CH ) N IX, X in methanol,
acetonitrile, and DMF. It was found that anhydrous
dimethylhydrazine reacts with (halomethyl)trialkoxy-
silanes I IV in the absence of solvent already at room
temperature. Independent of the reagent molar ratio
1
,1-Dimethyl-1-(trialkoxysilylmethyl)hydrazinium
halides V VIII are easily cleaved with lower alcohols
methanol, ethanol) by the Si C bond to form cor-
2
2
2 3
(
responding 1,1,1-trimethylhydrazinium halides IX and
X and tetraalkoxysilane.
+
V VIII + ROH
(RO) Si + Me NNH X , (2)
4
3
2
(
1:1 or 1:2), the major reaction product is 1,1-di-
methyl-1-(trialkoxysilylmethyl)hydrazinium halide
V VIII [Scheme (1)]. In the case of (iodomethyl)tri-
IX, X
X = Cl (IX), I (X).
1
070-3632/05/7506-0862 2005 Pleiades Publishing, Inc.

1,1-DIMETHYL-1-(TRIALKOXYSILYLMETHYL)HYDRAZINIUM
863
Similar Si C bond cleavage we observed in the
reaction of lower alcohols with methylorganyl(trial-
koxysilylmethyl)sulfonium iodides [3].
zinium halides V VIII, are readily soluble in lower
alcohols but without Si C bond cleavage.
The structure of compounds V VIII, XIII, and
1
13
29
Unlike (halomethyl)trialkoxysilanes I IV, 1-(chlo-
romethyl)silatrane (XI) and 1-(iodomethyl)silatrane
XIV is confirmed by their H, C, and Si NMR
1
(see table) and IR spectra. In the H NMR spectra of
(
XII) in the absence of solvent fail to react even with
1,1-dimethyl-1-(trialkoxysilylmethyl)hydrazinium
boiling dimethylhydrazine. At the same time, boiling
of 1-(iodomethyl)silatrane with dimethylhydrazine in
methanol or acetonitrile for 6 h leads to 1,1-dimethyl-
halides V VIII, the proton signal of the CH Si bound
2
with the onium nitrogen atom is near 3.60 ppm. The
1
signal of the same protons in the H NMR spectra of
1
-(silatranylmethyl)hydrazinium iodide (XIV) though
silatranyl derivatives XIII and XIV is shifted upfield
in moderate yield (about 30%). However, the yield
of iodide XIV upon heating of a mixture of 1-(iodo-
methyl)silatrane (XII) with dimethylhydrazine in
DMF at 100 110 C for 2 h reaches 82%. The reaction
of 1-(chloromethyl)silatrane ((26)XI) with dimethyl-
hydrazine under analogous conditions for 6 h leads to
( 2.80 ppm). The Me N proton signals of halides V
2
VIII and XIII, XIV are observed near 3.70 and
3.50 ppm, respectively. The proton signals of the
Si(OMe) and Si(OEt) bands in compounds V VIII
2
3
and endocyclic OCH groups of the silatrane skeleton
2
in compounds XIII, XIV appear at almost the same
values as the respective signals of starting (halome-
thyl)trimethoxysilanes I and II, (halomethyl)triethoxy-
silanes III and V, 1-(halomethyl)silatranes XI and XII,
respectively (see table). The chemical shifts ( 3.0
1
,1-dimethyl-1-(silatranylmethyl)hydrazinium
chlo-
ride (XIII) in ca. 70% yield.
N(CH CH O) SiCH X + Me NNH
2
2
2
3
2
2
XI, XII
3.1 ppm) of signals of the endocyclic NCH group of
2
+
N(CH CH O) SiCH Me NNH X ,
(3)
the silatrane skeleton in compounds XIII and XIV
provides evidence for their hydrazinium structure with
the positive charge on the nitrogen atom of the
2
2
3
2
2
2
XIII, XIV
X = Cl (XI, XIII), I (XII, XIV).
+
H NN Me CH fragment. The same chemical shifts
2
2
2
of endocyclic NCH proton signals are observed in
the H NMR spectra of dialkyl(silatranylmethyl)-
ammonium [1, 12], -sulfonium [3, 13, 14], -seleno-
2
1
,1-Dimethyl-1-(silatranylmethyl)hydrazinium
1
halides XIII and XIV were also prepared by trans-
etherification of 1,1-dimethyl-1-(trimethoxysilylme-
thyl)hydrazinium halides (V and VII) with tris(2-
hydroxyethyl)amine.
nium [4], and -telluronium iodides [5]. The chemical
13
shifts of the Me N carbon signals in the C NMR
2
spectra of these compounds vary only slightly and lie
in the range 58 60 ppm. At the same time, the CH Si
carbon signals of compounds V VIII, XIII, and XIV
N(CH CH OH) + V, VII
XIII, XIV + 3ROH. (4)
2
2
2
3
In chloroform, the reactions proceed almost im-
mediately in the absence of any catalyst. The yields
are appreciably downfield from those of the CH N
group in starting (halomethyl)trialkoxysilanes I IV
2
of
1,1-dimethyl-1-(silatranylmethyl)hydrazinium
and 1-(halomethyl)silatranes XI and XII. The
in-
C
3
halides XIII and XIV are 75 and 85%, respectively.
The by-product of these reactions is 1,1,1-trimethyl-
hydrazinium halide XI or XII formed by Si C bond
cleavage in starting 1,1-dimethyl-1-(trimethoxysilyl-
methyl)hydrazinium halides V and VII by the evolv-
ing methanol.
crease with increasing bulk of substituent R on the
silicon atom and is equal to 51 ppm for V, 58 ppm
for VII, VIII, and 64 ppm for XIII, XIV. The
chemical shifts in the 29Si NMR spectra of halides
V VIII, XIII, and XIV are determined by the cha-
racter of substitution (R ) and the coordination
3
number of silicon, equaling 58 ppm for V and VI,
1
,1-Dimethyl-1-(trialkoxysilylmethyl)hydrazinium
6
2 ppm for VII and VII, and 85 ppm for XIII and
halides V VIII and 1,1-dimethyl-1(silatranylmethyl)-
hydrazinium halides XIII and XIV are colorless fine
crystals. Compounds V VIII are readily soluble in
chloroform, acetonitrile, and DMF and insoluble in
ether and alkanes (pentane, hexane). Compared to tri-
alkoxysilyl derivatives V VIII, 1,1-dimethyl-1-(sila-
tranylmethyl)hydrazinium halides XIII and XIV have
considerably higher melting points and are worse
soluble in chloroform. At the same time, 1,1-dime-
thyl-1-(silatranylmethyl)hydrazinium halides XIII and
XIV, like 1,1-dimethyl-1-(trialkoxysilylmethyl)hydra-
XIV, respectively.
The IR spectra of 1,1-dimethyl-1-(trialkoxysilylme-
thyl)hydrazinium halides V VIII and 1,1-dimethyl-1-
(silatranylmethyl)hydrazinium halides XIII and XIV
contain bands of stretching and deformation vibrations
1
of the NH group ( 3200, 3100, and 1600 cm ,
2
respectively) and a set of characteristic Si O C
stretching vibration bands. The absence of the broad
+
strong band of stretching vibrations of the N H group
2
at 2700 cm 1 and bands of stretching vibrations of
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 6 2005

864
SOROKIN, VORONKOV
1H, 13C, and 29Si NMR chemical shifts of (halomethyl)trialkoxysilanes I IV, 1-(halomethyl)silatranes XI and XII, 1,1-
dimethyl-1-trialkoxysilylmethyl)hydrazinium halides V VIII, and 1,1-dimethyl-1-(silatranylmethyl)hydrazinium halides
XIII and XIV in CDCl3
,
ppm
SiR3
C, ppm
Comp.
no.
Si, ppm
Me N+ CH Si
NH2 Me N
+
CH Si
SiR3
2
2
2
2
I
II
III
2.81 s 3.62 s (9H, 3MeO)
1.95 s 3.62 s (9H, 3MeO)
2.79 s 1.24 t (9H, 3Me),
22.6
26.0
23.7
51.0 (MeO)
51.5 (MeO)
18.1 (CH3 in Et), 59.2
54.9
53.4
58.2
3
.90 q (6H, 3CH O)
(CH O)
2
2
IV
1.87 s 1.20 t (9H, 3Me),
25.8
18.1 (CH3 in Et), 59.1
56.7
3
.84 q (6H, 3CH O)
(CH O)
2
2
V
VI
3.67 s 3.58 s 3.70 s (9H, 3MeO)
3.69 s 3.52 s 3.70 s (9H, 3MeO)
6.8 s
6.4 s
7.2 s
57.7
57.8
58.5
51.7
51.7
57.8
59.6 (MeO)
59.8 (MeO)
18.0 (CH3 in Et), 59.7
58.7
58.9
62.3
VII 3.70 s 3.57 s 1.29 t (9H, 3Me),
.94 q (6H, 3CH O)
3
(CH O)
2
2
VIII 3.69 s 3.58 s 1.25 t (9H, 3MeCH2),
.92 q (6H, 3CH O)
6.4 s
59.5
58.5
31.1
12.8
64.0
64.7
18.0 (CH3 in Et), 59.7
62.7
77.2a
77.0a
84.8
85.0
3
(CH O)
2
2
XI
2.63 s 2.89 t (6H, 3NCH2),
.84 t (6H, 3CH O)
51.2 (NCH ), 57.42
2
3
(CH O)
2
2
XII
1.88
2.87 t (6H, NCH2),
.82 t (6H, 3CH O)
51.3 (NCH ), 57.5 (CH O)
2
2
3
2
XIII 3.48 s 2.82 s 3.00 t (6H, 3CH N),
6.5 s
6.2 s
59.8
60.7
50.8 (NCH ), 57.1 (CH O)
2 2
2
3
.85 t (6H, 3CH O)
2
XIV 3.50 s 2.82 s 3.04 t (6H, NCH2),
.88 t (6H, CH O)
51.1 (NCH ), 57.4 (CH O)
2 2
3
2
a
The
values for compounds XI and XII were taken from [12].
Si
the methyl substituents on nitrogen (2700 2850 cm 1)
show that the positive charge is localized on this
nitrogen atom [16] and thus provide evidence for the
presence in 1,1-dimethyl-1-(trialkoxysilylmethyl)-
ydrazinium halides V VIII and 1,1-dimethyl-1-(sila-
tranylmethyl)hydrazinium halides XIII and XIV
1,1-Dimethyl-1-(trimethoxysilylmethyl)hydrazi-
nium chloride (V). A mixture of 1.7 g of (chloro-
methyl)trimethoxysilane and 1.2 g of 1,1-dimethyl-
hydrazine was kept in a sealed ampule for 14 h until
a syrup-like material formed and then placed in a
refrigerator. When the syrup crystallized, the ampule
was unsealed, and volatile admixtures were removed
in a vacuum (1 2 mm Hg). The solid residue was
loosened up, washed with anhydrous ether (3 5 ml),
filtered off, and dried in a vacuum to obtain 2.1 g
(91%) of compound V as a colorless finely crystalline
+
of a nMe N NH fragment.
2
2
EXPERIMENTAL
The H, 13C, and 29Si NMR spectra were registered
on a Bruker DPX-400 spectrometer at 400.13, 100.61,
and 79.49 MHz, respectively, for 10-15% solutions in
CDCl (I IV, VII) and CD OD (V VIII). The IR
1
1
powder, mp 92 94 C. IR spectrum (KBr), cm : 780,
845, 1080, 1180 [ , (SiOC)], 1630 [ (NH )], 3090,
2
3190 [ (NH )]. Found, %: C 31.02; H 8.17; Cl 15.12;
3
3
2
spectra were obtained on Specord 75IR spectrophoto-
meter for KBr pellets. Technical grade 1,1-dimethyl-
hydrazine was kept for 48 h over potassium hydroxide
and twice distilled over metallic sodium. The solvents
were purified and dried according to conventional
procedures [17].
N 11.76; Si 11.88. C H ClN O Si. Calculated, %: C
31.23; H 8.30; Cl 15.36; N 12.14; Si 12.17.
6
19
2
3
1,1-Dimethyl-1-(trimethoxysilylmethyl)hydrazi-
nium iodide (VI). A mixture of 2.5 g of (iodome-
thyl)trimethoxysilane and 2.0 g of 1,1-dimethylhyd-
razine was placed in a sealed glass ampule and kept
The starting (iodomethyltrimethoxy)-, (iodomethyl)- at room temperature until crystals formed ( 8 h). The
triethohysilane, and 1-(iodomethyl)silatrane were
prepared as described in [18].
ampule was unsealed, and volatile admixtures were
removed in a vacuum ((1 2 mm Hg). The crystalline
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 6 2005

1,1-DIMETHYL-1-(TRIALKOXYSILYLMETHYL)HYDRAZINIUM
865
product was loosened up, washed with anhydrous
ether (3 5 ml), filtered off, and dried in a vacuum to
obtain 4.32 g (96%) of iodide VII as a colorless finely
crystalline powder, mp 74 76 C. IR spectrum (KBr),
DMF. The resulting mixture was heated to 90 100 C
and stirred until 1-(chloromethyl)silatrane dissolved
completely. The solution was cooled to 60 C, and
4.5 g of 1,1-dimethylhydrazine was added to it drop-
wise over the course of 20 min. The mixture was then
stirred for 4 h with gradual heating to 80 90 C and
then cooled 50 C. The flaky precipitate of polymeric
admixtures was filtered off. The filtrate was eva-
porated by half in a vacuum (1 2 mm Hg), and the
residue was kept for 12 h in a refrigerator (ca. 10 C).
Crystals formed and were filtered off, washed with
several portions of anhydrous ether, and dried in a
vacuum to obtain 5.5 g of chloride XIII. The mother
liquor was evapotared in a vacuum to obtain an ad-
ditional 1.2 g of compound XIII. Total yield of
product VII 6.7 g (79%), mp 184 187 C (decomp.).
1
cm : 785, 815, 840, 1050, 1070, 1185 [ , (SiOC)],
1
615 [ (NH )], 3100, 3200 [ (NH )]. Found, %:
2 2
C 22.08; H 6.06; I 38.78; N 8.46; Si 8.52. C H
6
19
IN O Si. Calculated, %: C 22.37; H 5.94; I 39.38;
2
3
N 8.69; Si 8.72.
1
,1-Dimethyl-1-(triethoxysilylmethyl)hydra-
zinium chloride (VII) was prepared in a similar way
from 2.1 g of (chloromethyl)triethoxysilane and 1.2 g
of 1,1-dimethylhydrazine. Yield 2.5 g (93%), color-
less finely crystalline powder, mp 77 78 C. IR spec-
1
trum (KBr), cm : 780, 790, 815, 1060, 1155 [ ,
(
SiOC)], 1620 [ (NH )], 3090, 3200 [ (NH )].
1
2
2
IR spectrum (KBr), cm : 865, 890, 915, 1065, 1150
Found, %: C 39.37; H 9.07; Cl 12.38; N 10.12; Si
.89. C H ClN O Si. Calculated, %: C 39.62; H 9.24;
[
, (Si O C)], 1620 [ (NH )], 3090, 3200 [ (NH )].
2 2
9
9
25
2
3
Found, %: C 38.29; H 7.86; Cl 12.31; N 14.56; Si
.78. C H ClN O Si. Calculated, %: C 38.17; H
Cl 12.99; N 10.26; Si 10.29.
9
1
0
22
3
3
1
,1-Dimethyl-1-(triethoxysilylmethyl)hydra-
8.18; Cl 12.52; N 14.84; Si 10.27.
zinium iodide (VIII) was prepared in a similar way
from 1.5 g of (iodomethyl)triethoxysilane and 0.6 g of
b. [by scheme (4)]. To a stirred solution of 2.3 g of
,1-dimethyl-1-(trimethoxysilylmethyl)hydrazinium
1
1
9
1
[
,1-dimethylhydrazine. Yield 1.9 g (94%), mp 92
4 C. IR spectrum (KBr), cm : 780, 790, 815, 1065,
1
chloride V in 5 ml of chloroform, a solution of 1.5 g
of tris(2-hydroxyethyl)amine in 3 ml of chloroform
was added dropwise with stirring. After heat release
was no longer observed (40 C, 2 min), the solution
was cooled to 20 C, and the precipitate of 1,1,1-tri-
methylhydrazinium chloride was filtered off to give a
chloroform solution of chloride XIII. The chloroform
was distilled off, and the solid residue was crystallized
from 2-propanol to obtain 2.1 g (74.6%) of compound
XIII, mp 194 195 C (decomp.). IR spectrum (KBr),
155 [ , ( Si-O-C)], 1610 [ (NH )], 3110, 3210 cm
2
[NH )]. Found, %: C 29.23; H 6.68; I 34.26; N 7.28;
2
Si 7.39. C H IN O Si. Calculated, %: 29.67; H 6.92;
9
25
2
3
I 34.8; N 7.69; Si 7.71.
Reaction of 1,1-dimethyl-1-(trimethoxysilyl-
methyl)hydrazinium chloride (V) with methanol.
Chloride I, 1 g, was dissolved in 3 ml of anhydrous
methanol. The reaction mixture was kept for 1 h and
then evaporated in a vacuum (1.5 mm Hg). The solid
residue was crystallized from 2-propanol to obtain
1
cm : 865, 890, 915, 1065, 1150 [ , (Si O C)],
1
3
620 [ (NH )], 3090, 3200 [ (NH )]. Found, %: C
2 2
8.29; H 7.86; Cl 12.31; N 14.56; Si 9.78. C H
10 22
0
.35 g (73%) of chloride V, mp 250 252 C (decomp.)
1
ClN O Si. Calculated, %: C 38.17; H 8.18; Cl 12.52;
{
published data [19]: 255 C (decomp.)}. H NMR
spectrum (CD OD), , ppm: 3.40 s (9H, 3Me).
3
3
1
3
N 14.84; Si 10.27.
C
3
NMR spectrum:
58.9 ppm. Distillation of the
C
1,1-Dimethyl-1-(silatranylmethyl)hydrazinium
iodide (XIV). a [by scheme (3)]. 1-(Iodomethyl)sila-
trane, 8.0 g, was treated with 50 ml of anhydrous
DMF. The mixture was stirred with heating until
condensate from the vacuum trap gave 0.4 g of tetra-
methoxysilane, bp 119 120 C {published data [20]:
bp 121 C}.
1-(iodomethyl)silatrane dissolved completely. The
Treatment of the solution of 1.5 g of 1,1-dimethyl-
solution was cooled to 60 C, and 4.0 g of 1,1-di-
methylhydrazine was added to it dropwise over the
course of 30 min. The reaction mixture was stirred
for extra 4 h with gradual heating to 80 100 C and
then cooled to 20 25 C and evaporated by half in a
vacuum (1 2 mm Hg). The residue was kept for 12 h
in a refrigerator at ca. 10 C. Crystals formed and
were filtered off, washed with several portions of an-
hydrous ether, and dried in a vacuum to give 4 g of
iodide XIV. Evaporation of the mother liquor in a
vacuum gave an additional 4 g of compound XIV.
1
-(trimethoxysilylmethyl)hydrazinium iodide (VII) in
methanol according to the same procedure gave 0.75 g
80%) of 1,1,1-trimethoxysilylmethylhydrazinium
iodide (VI), mp 25 C {published data [21]: mp 229
(
1
2
30 C}. H NMR spectrum (CD OD), , ppm: 3.38 s
3
(9H, 3Me). In addition, 0.5 g of tetramethoxysilane
was isolated.
1
,1-Dimethyl-1-(silatranylmethyl)hydrazinium
chloride (XIII). a [by scheme (3)]. 1-(Chloromethyl)-
silatrane, 6.7 g, was treated with 40 ml of anhydrous
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 6 2005

866
SOROKIN, VORONKOV
Total yield of product XIV 8 g (84%), mp 184 186 C
decomp.). Found, %: C 28.38; H 5.47; I 32.19; N
1.21; Si 6.95. C H IN O Si. Calculated, %: C 29.00;
Obshch. Khim., 1982, vol. 52, no. 9, p. 2055.
(
1
7
. Gurkova, S.N., Gusev, A.I., Abrosimova, A.T., Alek-
seev, N.V., and Voronkov, M.G., Dokl. Akad. Nauk
SSSR, 1981, vol. 260, no. 5, p. 1115.
9
22
3
3
H 5.89; I 33.49; N 11.69; Si 7.46.
b [by scheme (4)]. To a stirred solution of 3 g of
8. Sorokin, M.S. and Voronkov, M.G., Zh. Obshch.
Khim., 2001, vol. 71, no. 12. p. 1988.
1
,1-dimethyl-1-(triethoxysilylmethyl)hydrazinium
iodide (VIII) in 5 ml of chloroform, a solution of
.2 g of tris(2-hydroxyethyl)amine in 3 ml of chloro-
9. Demidov, M.P., Shklover, V.E., Lukina, Yu.L.,
D’yakov, V.M., Struchkov, Yu.T., and Voronkov M.G.,
Zh. Strukt. Khim., 1985, vol. 26, no. 4, p. 103.
1
form was added dropwise. After heat release was no
longer observed (35 C, 2 min), the reaction mixture
was cooled to 20 C, and the precipitate of 1,1,1-tri-
methylhydrazinium chloride was removed from the
chloroform solution of iodide XIV. The chloroform
was distilled off, and the solid residue was crystallized
from 2-propanol to obtain 2.3 g (76%) of compound
XIV, mp 175 177 C (decomp.).
1
1
1
0. Shklover, V.E., Struchkov, Yu.T., Sorokin, M.S.,
and Voronkov, M.G., Dokl. Akad. Nauk SSSR, 1984,
vol. 274, no. 3, p. 612.
1. Kirilin, A.D., Dokuchaev, A.A., Sokova, N.B., and
Chernyshov, E.A., Izv. Akad. Nauk SSSR, Ser. Khim.,
1
999, no. 1, p. 169.
2. Pestunovich, V.A., Tandura, S.N., Voronkov, M.G.,
Engel’gardt, G., Lipmaa, E., Pekh, T., Sidorkin, V.F.,
Zelchyan, G.I., and Baryshok, V.P., Dokl. Akad. Nauk
SSSR, 1978, vol. 240, no. 4, p. 914.
ACKNOWLEDGMENTS
The authors express their gratitude to A.I. Albanov
1
13
29
13. Pestunovich, V.A., Popelis, Yu.Yu., Lukevits, E.Ya.,
and Voronkov, M.G., Izv. Akad. Nauk Latv. SSR, Ser.
Khim., 1973, p. 365.
for recording the H, C, and Si NMR spectra and
to N.N. Chipanina for the aid in assignment of the IR
spectra.
1
4. Tandura, S.N., Pestunovich, V.A., Zelchyan, G.I.,
Baryshok, V.P., Lukina, Yu.A., Sorokin, M.S., and
Voronkov, M.G., Izv. Akad. Nauk SSSR, Ser. Khim.,
The work was financially supported by the Grant
Council of the President of the Russian Federation
grant no. NSh-1129-2003.3).
(
1
981, no. 2, p. 295.
1
1
5. Voronkov, M.G., Tandura, S.N., Sorokin, M.S.,
Shterenberg, B.Z., and Pestunovich, V.A., Izv. Akad.
Nauk SSSR, Ser. Khim., 1979, no. 2, p. 464.
REFERENCES
1
2
. Voronkov, M.G., Lukina, Yu.A., D’yakov, V.M.,
Frolov, Yu.L., and Tandura S.N., Zh. Obshch. Khim.,
982, vol. 52, no. 2, p. 349.
. Demidov, M.P., Shklover, V.E., Lukina, Yu.L., D’ya-
kov, V.M., Struchkov, Yu.T., and Voronkov, M.G.,
Zh. Strukt. Khim., 1991, vol. 32, no. 1, p. 177.
. Sorokin, M.S. and Voronkov, M.G., Zh. Obshch.
Khim., 1979, vol. 49, no. 12, p. 2671.
6. Nakanishi, K., Infrared Absorption Spectroscopy.
Practical, San Francisco: Holden-Day, 1962.
1
17. Gordon, A.J. and Ford, R.A., The Chemist’s Compa-
nion, New York: Wiley, 1972.
18. Sorokin, M.S., Lopyrev, V.A., Chipanina, N.N.,
Sherstyannikova, L.V., and Voronkov, M.G., Zh.
Obshch. Khim., 2004, vol. 74, no. 4, p. 603.
3
4
5
6
. Voronkov, M.G. and Sorokin, M.S., Zh. Obshch.
Khim., 1986, vol. 56, no. 8, p. 1818.
19. Klages, K. and Wolf, H., Chem. Ber., 1959, vol. 92,
no. 8, p. 1842.
. Voronkov, M.G. and Sorokin, M.S., Zh. Obshch.
Khim., 1989, vol. 59, no. 3, p. 590.
20. Forbes, G.S. and Anderson, N.N., J. Am. Chem. Soc.,
1944, vol. 66, p. 1703.
. Voronkov, M.G., Kirpichenko, S.V., Abrosimo-
21. Wawzonek, S. and Kellen, J., J. Org. Chem., 1973,
va, A.T., Albanov, A.I., and Lavrent’ev, V.I., Zh.
vol. 38, no. 11, p. 2058.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 6 2005