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Metal derivatives of amidoximes V. Dialkyl- or diphenyl-silyl derivatives of amidoximes
327
Journal
of Organometallic
0 Elsevier Sequoia
METAL
Chemishy.
S.A., Lauaanne
DERIVATIVES
V. DLALKYL-
A.B. GOEL
Chemishy
85 (1975)
327-333
- Printed in The Netherlands
OF AMIDOXIMES
OR DI?HENYLSlLYL
DERIVATIVES
OF AMiDO?UMES
and V.D. GUF’TA
Department.
(Received September
Ralasthan
University,
Jaipur 302004
(India)
3rd, 1974)
Summary New monomeric dialkyl- or diphenyl-silyibisamidoximes and dialkyl(ethosy)silylamidoximes have been characterised. Their infrared spectra have been interpreted and diamagnetic susceptibility of some of them has been determined.
Introduction Apart from analytical applications, metal compleses of amidoximes [l] have received very little attention. Studies on metal derivatives of amidoximes, R’(H,N)C=N-OH, have been initiated by us recently [ 2-51, and in continuation of our Li~estigations on organosilicon derivatives, we report here the synthesis and properties of some new dialkyl- or diphenyl-silylbisamidoximes and dialkyl(ethoxy)silyiamidosimes.
Results and discussion Dial!@- or diphenyl-diethoxysilanes were refluxed with the amidoximes in l/2 molar ratio in benzene, in the presence of a small amount of sodium. The progress of the reaction was checked by estimating the liberated ethanol. I
R,Si(OEt),
a, b, c, d,
+ 2 R’C(NH,)=NOH
-9
R.$i[ON=C(R’)NH,], (1)
R = Me, R’ R = Me, R’ R = Me, R’ R = Me, R’
= Me Et = Pr = Ph =
e, R = Ph, R’ = Et f, R = Ph, R’ = Pr g, R=Ph,R’=Ph
+ 2 EtOH
328
Attempted preparation of mono-derivatives by carrying out the reactions in equimolar proportions invariably resulted in bis-products (I). These results are consistent with earlier findings [5,6] that, in contrast, the dialkyldichlorosilanes reacted readily with amidosimes in equimolar ratio in the presence of triethylamine
resulting in the formation of cyclic derivatives, RISi
/ON\CR.
\ N’ [4]. However, the mono-products (II) could be obtained by treating dialkyl(ethoxy)chlorosilanes, R2Si(OEt)CI, with amidosimes in the presence of triethylamine: &Si(OEt)Cl
+ R’C(NH?)=NOH
+ Et-,N%
R,Si(OEt)ON=C(R’)NH,
(11) a, b, c, d,
R R R R
= = = =
Me, Me, Me, Me,
R’ R’ R’ R’
= = = =
Me Et Pr Ph
+ Et3N - HCI
e, R = Et, R’ = Et f, R = Et, R’ = Pr
All mono- (II) and bis- (I) derivatives are monomeric (Tables 1 and 2).
in refluxing benzene
Infrared spectra The v(OH) observed at 3570-3650 cm-’ in the parent amidoximes
[ 71 disappear in compounds I and II and two strong bands in the regions 3455-3475 cm-’ and 3320-3360 cm-’ due to ZJ(NH,) and its deformation at 1575 c 5 cm-’ are present, suggesting that the products are O-substituted. An intense band in the region 1640-1652 cm-’ can be assigned to v(C=N) of the osime moiety. In clialkylsilyl products, the vibrations of the & group on silicon show characteristic bands [8, 91, at ca. 805 and 840-850 cm-’ due to v,(Si-C) and methyl rocking along with the 6,(Me) at ca. 1255 cm-’ and 6,(Et) at ca. 1238 cm-‘. Absorption bands at 1070-1110 cm-’ with two or three split band groups characteristic of cg,(Si-O-C), (S+O-N) and v(C-0) frequencies have been observed in both mono- (II) and his- (I) products. A medium to strong band at 935 5 12 cm-’ is due to z~(N-0) and at 720-735 cm-’ is assigned to vJSi-0). The positions of v(Si--C), ~(Si-0) in comparison to dialkyldiethorysilane [ 10, 111, and v(NH~) with respect to parent amidoxime [ 21 are almost unchanged, indicating the absence of any intramolecular coordination (Si-N) [ 121. PMR spectra The PMR spectra of Ilb gave two multiplets due to methylene protons of ethosy and ethyl groups each of which splits into two sets of quartets at T 6.14, 6.20 and 7 7.79, 7.84 respectively, suggesting the presence of some isomeric forms. Methyl protons could be distinguished at r 8.82 (ethory) and 8.97 (ethyl). The presence of isomers is also indicated by three closely spaced signals (r 9.80, 9.91 and 9.97) due to Me,Si protons. Methylene (two multiplets), methyl and Me,Si protons are observed in the ratio l/1/3/3. The most likely
Ib
Et 1.92 Pr 1.77 Ph 2.33
M0
Ill
36
38
If
PK
Ph 1.27
37
Ie
EL 0.96
Ph 1.27
38
Id
0.74
40
IC
Ph 1.46 Ph 0.99
1.63 Me 1.2Q Me 1.27
42
In
Me 2.06
Me 2.07 39
fh)
Reoctlon tlnlc
R’(HlN)C=N-OH R’
Product
Crystd. from hot benzene Cryetd. from hot benzene
Crystd. from hot bcnzcnc
7910.1
6810.1
12810.1
B.P. (DC/mm)
Ilqutd
0.40
(0.44)
(94)
0.46 (0.49) 0.30 (0.33)
0.06 (1.00) 0.76 (0.00) 0.76 (0.79)
1.22 (1.28)
Elhnnol In nzeotrope (B)
6.12 (6.20)
(7.30)
7.81 (7.88) 7.24
12.04 (12.09) 10.68 (10.78) 6.46 (8.66)
13.72 (13.76)
SI (sb)
Analysis found (c&d.)
Whlw solld
(88)
(98) Whlta eolld
Vkous
(92)
(80) Whtto solid
(84) Colourlens Ilquld
(8b) Colourlebs liquid
White crystn. solid
Nnturc and yield (‘F)
AND ANALYSES OF DIMETHYL- AND DIPHENYL~SILYLBISAMIDOXIMES
R@(OEL)Z R
Reoctnnte (g)
PREPARATION
TABLE 1
12.30 (12.36)
lB.60 (16.71) 14.60 (14.67)
24.06 (24.12) 21.60 (21.61) 17.01 (17.00)
29.20 (29.38)
N (%I
460 (462.6)
387 (366.6) 389 (384.6)
248 (232.3) 276 (260.4) 327 (328.6)
264 (204.3)
Mol. wt. found (cnlcd.)
1.4630
1.4495
I, JS D
R’(H2N)C=N-OH R’
hlo
0.60 El 0.74 Pr 0.87
Ph
1.17 EI 0.68 PI 0.60
Ma
1.13 Me 1.17 Mtl 1.18
Me
1.10 Et 1.10 Et 1.08 0.00
0.72
0.00
0.87
0.80
0.84
EcjN
a AU the products nre colourlesa Ilqulde wewcd
R
R~WOEtlCI
Rcnatants (8)
Reuctlon
30 min
30 min
26 mln
26 mln
30 mln
lh
LlrnC
nt room tompernture.
III
Ik
Hd
IIC
IIb
Iln
Product
PREPARATION AND ANALYSES OI: DIALKYL(ETHOXY)SlLYLAMIDOXlhlES~
TABLE 2
7410.7
7311.0
6710.2
8710.1
8610.1
14010.2
-
B.P, (“C/mm)
86
66
78
86
88
80
Yluld 04
15.80 (lG.92) 14.66 (14.76) 13.04 (13.7G) 11.70 (11.70) 12.77 (12.86) 12.01 112.08)
SI
16.81 (lB.UD) 14.70 (14.72) 13.71 (13.72) 11.72 (11.76) 12.78 (12.82) 12.02 (12.06)
N
160 (176.3) 107 (100.3) 211 (204.3) 233 (238.4) 237 (218A) 230 (232.6)
(enled. )
hnnlyslo found kulcd.)(%) hlol. wt. found
1.4515
1.4616
-
1.4466
1.4466
1.4470
ng
0
w w
331 TABLE
3
DIAMAGNETIC SlJSCEPTlBILITY DlhlETHYL(ETAOXY)SILYLAMlDOXlhlE~ Compound
(R’)
DATA
FOR
DIMETHYLSiLYLBISAMIDOXlMES
xhl observed
% Difference between observed calculated XM
ib (Et) Ic (R)
124.4 146.9 169.4
-4.8 -4.4 -3.7
Ila (Me) .lrn (Et) Ilc (PI)
113.4 124.5 135.8
-3.6 -3.5 -3.2
La (Me)
a lo+
AND
and
C.&s. umts.
isomers are syn and anti forzns for which evidence has been gathered in the PMR data of trimethylsilylamidoxime
Diamagnetic
[ 21.
suscep tibrlity
A wave-mechanical
method using the concept of bond susceptibiliky has been used [ 13,141. The esperimentally determined values and the percentage difference between observed and calculated diamagnetic susceptibilities of the compounds have been summarised in Table 3.
The values reported (Table 3) have been treated graphically for each individual series by plotting molar susceptibility against the length of the alkyl chains in the homologous compounds. Both plots were linear and the information obtained from them for each series is given in Table 4. xsi have been calculated using the standard x values of different groups [14-161. The lower values of Gi (17.90 and 17.85) for both series (Table 4) in comparison with h for the S-C system (reported to be 21.00 for tetra-compounds [ 17 1) are explainable by “back-bonding” to the silicon atom from the oxygen lone-pair. These observations are consistent with the data of Abel et al. [171. TABLE VALUES CENTRAL Senes
4 OF THE METAL
DIAhlAGNETIC ATOM IN THE Gradient plot
of
SUSCEPTIBILITIES SERIES STUDIED
OF THE
METHYLENE
XCH?
.%&I
11.25 11.20
100.4 101.7
GROUPS
intercept
AND
THE
Xsi
Xp%q againsr n 1 I1
11.25 11.20
17.90 17.86
332
Experimental Experimental details and analytical methods are as described in an earlier report [ 51. Freshly distilled dimethyldiethoxysilane (113.8”) and diphenyldiethoxysilane (151-153”/6.0 mm) were used. Dimethyl(ethoxy)chlorosihme (95-96’) and diethyl(ethoxy)chIorosilane (146-147”) were prepared [ 181 and distilled before use. Amidoximes were synthesized by the standard methods 11,191. Infrared spectra were recorded on neat samples or on nujol mulls, using KBr optics (Perkin-Elmer 337) in the range 4000400 cm-‘. Molecular weights were determined in refluxing benzene in a semi-micro (Gallenkamp) ebulliometer. Refractive indices were determined with an Abbe retiactometer. The PMR spectrum was run on a Varian A-60 in CCI, using TMS as internal standard. All diamagnetic susceptibility measurements have been carried out at room temperature (26”) by the Gouy method. Benzene was used as a reference liquid having specific susceptibility -0.702 X 10m6c.g.s. units. The accuracy of the determination of the Gouy force was of the order of f. 0.05 mg. Reaction between dimethylor diphenyl-diethoxysilane and amidoxime (molar ratio l/2) Dimethyl- or diphenyl-diethorysilane and the appropriate amidoxime were added to anhydrous benzene (ca. 50 ml). A small piece of metallic sodium was added and the reaction mixture was retlured and the ethanol Liberated was fractionated azeotropically with benzene for ca. 30-40 h. Solvent was removed under reduced pressure and the residue was distilled in vacua or crystallized to give the product. The details are given in Table 1. Reactions of dialkylchloroethoxysilanes with amidoximes in the presence of triethylamrne (molar ratio l/l/l) To the amidoxime in benzene (ca. 40 ml), triethylamine and dialkylchloroethoxysikme were added. The mivture was stirred at room temperature for ca. l/2 h and filtered. The solvent was removed and the residue on distillation in vacua gave the product. Results are collected in Table 2. Acknowledgements Thanks are due to Prof. R-C. Mehrotra and Prof. K.C. Joshi for providing the laboratory facilities. One of us (A.B.G.) is grateful to the C.S.I.R., New Delhi for the award of a Junior Research Fellowship. References 1 F. Elog and R. Leaaers. Chem. Rev.. 62 (1962) 155. Gupta. J. Organomehl. Chem.. 72 (1974) 3 A.B. Gael and V.D. Gupta. J. OrganometaL Chem.. 77 (1974) 4 A-B. Gael and V.D. Gupta. Aust. J. Chem.. (1974) in p5 kB. Gael d V.D. Gupta Indirs J. Cbem.. (1974) in press_ 6 E. -II. Acts Chem. Scan&. 8 (1954) 898. 7 L. Brandt. Meded. Vlaam. Chem. Vu.. 29 (1967) 57.
2 -4-R Goel and V.D.
171. 183.
333 8 E.W.
Abel
9
Coltbup.
10 11 12 13
14 15 16 17 18 19
N.B.
and R.P. Bush. J. Organometal. L-H.
Daly
and
SE.
Wiberley.
C&m..
3 (1965)
Introduction
245. to Infrared
and Raman
Spectroscopy.
Press. London. 1964. R. Forneris and E. Funk 2. Electmcbem.. 62 (1958) 1130. T. Tanaka, Bull. Chem. Sot. Jap.. 33 (1960) 446. R.C. hlehrotra and P. Baja~. J. Organomet-al. Cbem.. 24 (1970) 611. J. Baudet. J. Cbim. Phys.. 58 (1961) 228. A. Pacault. J. Hoarau and A. Mar&and. Advances III Chemical f%yslcs. hterscmm. New York, 1961. p. 171. YaG. Dorfman. Duunagnetisn and Cheoucal bond. EJsewer. New York. 1965. P. 24. W.R. rsPguq G.I.W. Lleweiyn and G. Scott. Tranr Faraday Sot.. 55 (1959) 887. E.W. Abel. R.P. Bush. C.R. Jenkinsand T. Zobel. Trans. Faraday Sot.. 60 (1964) 1214. L.W. Breed. J.W. Hageer~y Jr. and F. Biuoccbi. J. 0%. Chcm.. 25 (1960) 1633. J. Banaos. R. hlarhrs-Noel and F. Maths, C.R. Acad. Sci Paris. 245 (1957) 419.
Acad
,dC
Journal
of Organometallic
0 Elsevier Sequoia
METAL
Chemishy.
S.A., Lauaanne
DERIVATIVES
V. DLALKYL-
A.B. GOEL
Chemishy
85 (1975)
327-333
- Printed in The Netherlands
OF AMIDOXIMES
OR DI?HENYLSlLYL
DERIVATIVES
OF AMiDO?UMES
and V.D. GUF’TA
Department.
(Received September
Ralasthan
University,
Jaipur 302004
(India)
3rd, 1974)
Summary New monomeric dialkyl- or diphenyl-silyibisamidoximes and dialkyl(ethosy)silylamidoximes have been characterised. Their infrared spectra have been interpreted and diamagnetic susceptibility of some of them has been determined.
Introduction Apart from analytical applications, metal compleses of amidoximes [l] have received very little attention. Studies on metal derivatives of amidoximes, R’(H,N)C=N-OH, have been initiated by us recently [ 2-51, and in continuation of our Li~estigations on organosilicon derivatives, we report here the synthesis and properties of some new dialkyl- or diphenyl-silylbisamidoximes and dialkyl(ethoxy)silyiamidosimes.
Results and discussion Dial!@- or diphenyl-diethoxysilanes were refluxed with the amidoximes in l/2 molar ratio in benzene, in the presence of a small amount of sodium. The progress of the reaction was checked by estimating the liberated ethanol. I
R,Si(OEt),
a, b, c, d,
+ 2 R’C(NH,)=NOH
-9
R.$i[ON=C(R’)NH,], (1)
R = Me, R’ R = Me, R’ R = Me, R’ R = Me, R’
= Me Et = Pr = Ph =
e, R = Ph, R’ = Et f, R = Ph, R’ = Pr g, R=Ph,R’=Ph
+ 2 EtOH
328
Attempted preparation of mono-derivatives by carrying out the reactions in equimolar proportions invariably resulted in bis-products (I). These results are consistent with earlier findings [5,6] that, in contrast, the dialkyldichlorosilanes reacted readily with amidosimes in equimolar ratio in the presence of triethylamine
resulting in the formation of cyclic derivatives, RISi
/ON\CR.
\ N’ [4]. However, the mono-products (II) could be obtained by treating dialkyl(ethoxy)chlorosilanes, R2Si(OEt)CI, with amidosimes in the presence of triethylamine: &Si(OEt)Cl
+ R’C(NH?)=NOH
+ Et-,N%
R,Si(OEt)ON=C(R’)NH,
(11) a, b, c, d,
R R R R
= = = =
Me, Me, Me, Me,
R’ R’ R’ R’
= = = =
Me Et Pr Ph
+ Et3N - HCI
e, R = Et, R’ = Et f, R = Et, R’ = Pr
All mono- (II) and bis- (I) derivatives are monomeric (Tables 1 and 2).
in refluxing benzene
Infrared spectra The v(OH) observed at 3570-3650 cm-’ in the parent amidoximes
[ 71 disappear in compounds I and II and two strong bands in the regions 3455-3475 cm-’ and 3320-3360 cm-’ due to ZJ(NH,) and its deformation at 1575 c 5 cm-’ are present, suggesting that the products are O-substituted. An intense band in the region 1640-1652 cm-’ can be assigned to v(C=N) of the osime moiety. In clialkylsilyl products, the vibrations of the & group on silicon show characteristic bands [8, 91, at ca. 805 and 840-850 cm-’ due to v,(Si-C) and methyl rocking along with the 6,(Me) at ca. 1255 cm-’ and 6,(Et) at ca. 1238 cm-‘. Absorption bands at 1070-1110 cm-’ with two or three split band groups characteristic of cg,(Si-O-C), (S+O-N) and v(C-0) frequencies have been observed in both mono- (II) and his- (I) products. A medium to strong band at 935 5 12 cm-’ is due to z~(N-0) and at 720-735 cm-’ is assigned to vJSi-0). The positions of v(Si--C), ~(Si-0) in comparison to dialkyldiethorysilane [ 10, 111, and v(NH~) with respect to parent amidoxime [ 21 are almost unchanged, indicating the absence of any intramolecular coordination (Si-N) [ 121. PMR spectra The PMR spectra of Ilb gave two multiplets due to methylene protons of ethosy and ethyl groups each of which splits into two sets of quartets at T 6.14, 6.20 and 7 7.79, 7.84 respectively, suggesting the presence of some isomeric forms. Methyl protons could be distinguished at r 8.82 (ethory) and 8.97 (ethyl). The presence of isomers is also indicated by three closely spaced signals (r 9.80, 9.91 and 9.97) due to Me,Si protons. Methylene (two multiplets), methyl and Me,Si protons are observed in the ratio l/1/3/3. The most likely
Ib
Et 1.92 Pr 1.77 Ph 2.33
M0
Ill
36
38
If
PK
Ph 1.27
37
Ie
EL 0.96
Ph 1.27
38
Id
0.74
40
IC
Ph 1.46 Ph 0.99
1.63 Me 1.2Q Me 1.27
42
In
Me 2.06
Me 2.07 39
fh)
Reoctlon tlnlc
R’(HlN)C=N-OH R’
Product
Crystd. from hot benzene Cryetd. from hot benzene
Crystd. from hot bcnzcnc
7910.1
6810.1
12810.1
B.P. (DC/mm)
Ilqutd
0.40
(0.44)
(94)
0.46 (0.49) 0.30 (0.33)
0.06 (1.00) 0.76 (0.00) 0.76 (0.79)
1.22 (1.28)
Elhnnol In nzeotrope (B)
6.12 (6.20)
(7.30)
7.81 (7.88) 7.24
12.04 (12.09) 10.68 (10.78) 6.46 (8.66)
13.72 (13.76)
SI (sb)
Analysis found (c&d.)
Whlw solld
(88)
(98) Whlta eolld
Vkous
(92)
(80) Whtto solid
(84) Colourlens Ilquld
(8b) Colourlebs liquid
White crystn. solid
Nnturc and yield (‘F)
AND ANALYSES OF DIMETHYL- AND DIPHENYL~SILYLBISAMIDOXIMES
R@(OEL)Z R
Reoctnnte (g)
PREPARATION
TABLE 1
12.30 (12.36)
lB.60 (16.71) 14.60 (14.67)
24.06 (24.12) 21.60 (21.61) 17.01 (17.00)
29.20 (29.38)
N (%I
460 (462.6)
387 (366.6) 389 (384.6)
248 (232.3) 276 (260.4) 327 (328.6)
264 (204.3)
Mol. wt. found (cnlcd.)
1.4630
1.4495
I, JS D
R’(H2N)C=N-OH R’
hlo
0.60 El 0.74 Pr 0.87
Ph
1.17 EI 0.68 PI 0.60
Ma
1.13 Me 1.17 Mtl 1.18
Me
1.10 Et 1.10 Et 1.08 0.00
0.72
0.00
0.87
0.80
0.84
EcjN
a AU the products nre colourlesa Ilqulde wewcd
R
R~WOEtlCI
Rcnatants (8)
Reuctlon
30 min
30 min
26 mln
26 mln
30 mln
lh
LlrnC
nt room tompernture.
III
Ik
Hd
IIC
IIb
Iln
Product
PREPARATION AND ANALYSES OI: DIALKYL(ETHOXY)SlLYLAMIDOXlhlES~
TABLE 2
7410.7
7311.0
6710.2
8710.1
8610.1
14010.2
-
B.P, (“C/mm)
86
66
78
86
88
80
Yluld 04
15.80 (lG.92) 14.66 (14.76) 13.04 (13.7G) 11.70 (11.70) 12.77 (12.86) 12.01 112.08)
SI
16.81 (lB.UD) 14.70 (14.72) 13.71 (13.72) 11.72 (11.76) 12.78 (12.82) 12.02 (12.06)
N
160 (176.3) 107 (100.3) 211 (204.3) 233 (238.4) 237 (218A) 230 (232.6)
(enled. )
hnnlyslo found kulcd.)(%) hlol. wt. found
1.4515
1.4616
-
1.4466
1.4466
1.4470
ng
0
w w
331 TABLE
3
DIAMAGNETIC SlJSCEPTlBILITY DlhlETHYL(ETAOXY)SILYLAMlDOXlhlE~ Compound
(R’)
DATA
FOR
DIMETHYLSiLYLBISAMIDOXlMES
xhl observed
% Difference between observed calculated XM
ib (Et) Ic (R)
124.4 146.9 169.4
-4.8 -4.4 -3.7
Ila (Me) .lrn (Et) Ilc (PI)
113.4 124.5 135.8
-3.6 -3.5 -3.2
La (Me)
a lo+
AND
and
C.&s. umts.
isomers are syn and anti forzns for which evidence has been gathered in the PMR data of trimethylsilylamidoxime
Diamagnetic
[ 21.
suscep tibrlity
A wave-mechanical
method using the concept of bond susceptibiliky has been used [ 13,141. The esperimentally determined values and the percentage difference between observed and calculated diamagnetic susceptibilities of the compounds have been summarised in Table 3.
The values reported (Table 3) have been treated graphically for each individual series by plotting molar susceptibility against the length of the alkyl chains in the homologous compounds. Both plots were linear and the information obtained from them for each series is given in Table 4. xsi have been calculated using the standard x values of different groups [14-161. The lower values of Gi (17.90 and 17.85) for both series (Table 4) in comparison with h for the S-C system (reported to be 21.00 for tetra-compounds [ 17 1) are explainable by “back-bonding” to the silicon atom from the oxygen lone-pair. These observations are consistent with the data of Abel et al. [171. TABLE VALUES CENTRAL Senes
4 OF THE METAL
DIAhlAGNETIC ATOM IN THE Gradient plot
of
SUSCEPTIBILITIES SERIES STUDIED
OF THE
METHYLENE
XCH?
.%&I
11.25 11.20
100.4 101.7
GROUPS
intercept
AND
THE
Xsi
Xp%q againsr n 1 I1
11.25 11.20
17.90 17.86
332
Experimental Experimental details and analytical methods are as described in an earlier report [ 51. Freshly distilled dimethyldiethoxysilane (113.8”) and diphenyldiethoxysilane (151-153”/6.0 mm) were used. Dimethyl(ethoxy)chlorosihme (95-96’) and diethyl(ethoxy)chIorosilane (146-147”) were prepared [ 181 and distilled before use. Amidoximes were synthesized by the standard methods 11,191. Infrared spectra were recorded on neat samples or on nujol mulls, using KBr optics (Perkin-Elmer 337) in the range 4000400 cm-‘. Molecular weights were determined in refluxing benzene in a semi-micro (Gallenkamp) ebulliometer. Refractive indices were determined with an Abbe retiactometer. The PMR spectrum was run on a Varian A-60 in CCI, using TMS as internal standard. All diamagnetic susceptibility measurements have been carried out at room temperature (26”) by the Gouy method. Benzene was used as a reference liquid having specific susceptibility -0.702 X 10m6c.g.s. units. The accuracy of the determination of the Gouy force was of the order of f. 0.05 mg. Reaction between dimethylor diphenyl-diethoxysilane and amidoxime (molar ratio l/2) Dimethyl- or diphenyl-diethorysilane and the appropriate amidoxime were added to anhydrous benzene (ca. 50 ml). A small piece of metallic sodium was added and the reaction mixture was retlured and the ethanol Liberated was fractionated azeotropically with benzene for ca. 30-40 h. Solvent was removed under reduced pressure and the residue was distilled in vacua or crystallized to give the product. The details are given in Table 1. Reactions of dialkylchloroethoxysilanes with amidoximes in the presence of triethylamrne (molar ratio l/l/l) To the amidoxime in benzene (ca. 40 ml), triethylamine and dialkylchloroethoxysikme were added. The mivture was stirred at room temperature for ca. l/2 h and filtered. The solvent was removed and the residue on distillation in vacua gave the product. Results are collected in Table 2. Acknowledgements Thanks are due to Prof. R-C. Mehrotra and Prof. K.C. Joshi for providing the laboratory facilities. One of us (A.B.G.) is grateful to the C.S.I.R., New Delhi for the award of a Junior Research Fellowship. References 1 F. Elog and R. Leaaers. Chem. Rev.. 62 (1962) 155. Gupta. J. Organomehl. Chem.. 72 (1974) 3 A.B. Gael and V.D. Gupta. J. OrganometaL Chem.. 77 (1974) 4 A-B. Gael and V.D. Gupta. Aust. J. Chem.. (1974) in p5 kB. Gael d V.D. Gupta Indirs J. Cbem.. (1974) in press_ 6 E. -II. Acts Chem. Scan&. 8 (1954) 898. 7 L. Brandt. Meded. Vlaam. Chem. Vu.. 29 (1967) 57.
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