3,232,958
(e
rates Patent 0 1C6
Patented Feb. 1, 1966
1
2
3,232,958
METALLOID AZIDES AND PROCESS FOR
PREPARING THE SAME
Robert M. Washburn, Whittier, Cali?, assignor to Ameri
can Potash 8: Chemical Corporation, Los Angeles,
and the like;
Arylthio: C6H5S—-; o, In, and p-CH3--C6H4S—; and
Calif., acorporation of Delaware
No Drawing. Filed Nov. 3, 1961, Ser. No. 149,885
10 Claims. (Cl. 260-349)
the like.
'
I
V
The syn-thesis of the metalloid azides of this invention
The present invention relates to novel metalloid azides 10 can be carried out in a variety of solvents including, for
example, di-n-butyl ether, pyridine, triethylamine, toluene,
and to processes for preparing the same.
acetonitrile, and the like, and at reaction temperatures
Broadly, the metalloid azides of this invention may be
from about room temperature to about 150° C. for periods
of several hours to several days.
represented by the following formula:
15
wherein R is selected from the group consisting of aryl,
alkyl, halogen, alkoxy, aryloxy, amino, alkylthio, and aryl
Compound (a) above, is a metal halide in which the
metal is either silicon, germanium, or tin. Examples of
‘ silicon halides which are suitable for use in this invention
thio groups; M is a metal selected from the ‘group consist
include phenyltrichlorosilane, diphenyldibromosilane, tri
ing of silicon, germanium, and tin; and n is a Whole number
phenyl?uorosilane, phenyldimethylbromosilane, diphenyl
ethyl?uorosilane, tri-n~propylchlorosilane, phenylidiphen~
from 1 to 3.
20
These novel compounds can be prepared by reacting one
oxychlorosilane, diphenyldimethylaminochlorosilane, ‘tri
p-tolylchlorosilane, a-naphthylphenylmethylbromosilane,
di(o-chlorophenyl)phenylthiobromosilane, tri(m-phen
mole of
(a) a compound having the formula
25
oxyphenyl) chlorosilane, ‘and the like.
Examples of germanium halides which are suitable for
wherein R is selected from the group consisting of aryl,
use in this invention include phenyldimethylchloroger
alkyl, alkoxy, aryloxy, amino, alkylthio, and arylthio
mane, diphenyldichlorogermane, phenyltribromogermane,
groups; M is a metal selected from the group consist
tri~n-butylfluorogermane, di(p-tolyl)dibromogermane, a
ing of silicon, germanium, and tin; X is a halogen
naphthyltrichlorogermante,
atom; and n is a whole number from 1 to 3; with
phenyldiphenoxychloroger
30 mane, di(o-chlorophenyl)methylthiobromogermane, m
(b) from one to three moles of a compound having the
tolylmethyldimethylaminobromogermane, and the like.
formula
Examples of tin halides which may be used in this in
vention include triphenylchlorostanne, diphenyldibromo
stanne, trimethyl?uorost‘anne, m-tolyltrichlorostanne, tri
M’Na
wherein M’ is a metal selected from the group consist
ing of alkali metals and alkaline earth metals.
(o~chlorophenyl)?uorostanne,
di(a-naph.thyl)dibromo
starine, tris(dimethylamino)chlorostanne, phenyldiphenyl
In carrying out the novel reaction of the present inven- ’
thiochlorostanne, and the like.
tion, it has been found that for each one mole of compound
(a) there must be used from one to three moles of compound
(b). The reaction must be carried out under anhydrous
In order to illustrate this invention even more fully the
following speci?c examples are set forth.
Example I
conditions to prevent the hydrolysis of the starting metal
loid halides and the resulting metalloid azide products.
This can be achieved conveniently by carrying out the re
One mole of triphenylchlorosilane and one mole of so~
dium azide are re?uxed in pyridine for 24 hrs. to yield
action in an inert atmosphere or under vacuum.
triphenylazidosilane after removing the sodium chloride by
In the formulae above it is indicated that R is selected
?ltration and distilling the solvent.
from a number of listed chemical groups. Examples of 45
Example ll
slllitable radicals falling within these chemical groups in
c ude:
When two moles of lithium azide are reacted with one
mole of dimethyldichlorosilane in toluene at room tem
50 ‘perature for 3 days, a toluene solution of dimethyldiazido
silane is obtained.
'
Halogen: F, Cl, Br, I;
Example III
The interaction of phenyltrichlorogermane (one mole)
‘and potassium ‘azide (3 moles) in re?uxing acetonitrile for
55 24 hrs. yields phenyltriazid-ogermane.
Example I V
Triethylchlorostanne (1 mole) reacts in toluene with so
dium azide (1 mole) to yield triethylazidostanne.
60
Example V
The interaction of phenyldimethylbromosilane (one
mole) and sodium azide (one mole) in re?uxing pyridine
for 36 hrs. yields phenyldimethylaZidost-anne.
65
In addition to the ‘above described metalloid azides, a
class of di'function metalloid azides having the generalized
formula shown below also can be synthesized.
In the formula, R and M are as de?ned above, L is an
arylene or alkylene group, and n is a whole number of
from 1 to 3.
3,232,958
3
‘
,
-‘
'
I
.
Examples of suitable arylene and alkylene groupings
represented by L in the formula are 1,4-C6H4-——; 1,3
The mono and difunction metalloid azides illustrated in
C6H4—; 4,4’-C6H4—-O—C6H4—; 1,4-naphthy1ene; penta
Examples I-X have utility as insecticides, herbicides, fungi
cides, oil additives, blowing agents, and the like. They
rnethylene; and the like.
These difunctional metalloid azides can be prepared
are also useful as chemical intermediates for the synthesis
of metalloid phosphoranes, arsanes, and stibanes as de
by reacting one mole of (i) a difunctional metalloid halide,
having the generalized formula shown below,
scribed in copending application Serial No. 149,887, ?led
Nov. 3, 1961, now US. Patent 3,112,331, which is assigned
XnR3_nM—L—MR3_nXn
to the same assignee as the present invention.
where 'R, M, and L are as de?ned for the above difunctional
10
The azide compounds of this invention may be incorpo
metalloid azide, n is a whole number from 1 to 3, and X
rated into resin compositions where they function as blow
is halogen, with (ii), from 2 to 6 moles of a compound
ing agents during curing of the resins. The following ex
having the formula
ample illustrates this use.
M'N3
wherein M’ is ‘as de?ned above.
Examples of suitable difunctional metalloid halides are
Example XI
Twenty grams of an epoxy resin (having a melting point
of 8°—12° C., and epoxide equivalency of 190 to 210 and
a viscosity of Z-S to Z-6 on the Gardner-Holdt scale) are
20 admixed with about2.9 grams of tetraethylenepentamine as
a catalyst therefor. Thereafter, 0.4 gram of trimethyl—
phosphite and 0.4 gram of triphenylsilyl azide are added
to the mixture. The resultant mixture is heated to about
100° C. whereupon the phosphite and azide react to lib—
erate nitrogen which passes out of the mixture and foams
the resin. After about 10 minutes a ?rm, thermoset
foamed resin results having a density of about O.2—0.3
l,5-ClSi(C6H5) 2(CH2) 5Si (CGH5)2Cl
and the like.
The following examples illustrate the preparation of di
functional metalloid azides.
Example VI
A mixture of one mole of 1,4-Cl3Si—C6H4—SiCl3 and
v6 moles of lithium azide is re?uxed in pyridine for 36 hrs.
grams per cc.
While the present invention has been described with re
spect to what at present are preferred embodiments thereof
it will be understood, of course, that certain changes, sub
stitutions, modi?cations and the like may be made therein
After one week at room temperature, a mixture of two
without departing from the true scope of the invention as
‘moles of sodium azide and one mole of
de?ned in the appended claims.
35
1,3-BrGe (CH3 ) 2—C6H4—Ge (CH3 ) 2Br
What is claimed is:
‘to
1,4-(N3)3Si—C6H4-——Sl(N3)3'
Example VII
30
‘results in the formation of
. Triphenylazidosilane.
. Dimethyldiazidosilane.
. Phenyltriazidogermane.
1,3-N3Ge (CH3 ) 2—C6H4-—Ge (CH3 ) 2N3
Example VIII
40
When one mole of
4,4’-F2Sn(C6H5)——C6H4~o-C6H44n(Cal-I5)F2
. 1,3-bis(dimethylazidogermanyl)benzene.
. 4,4'-bis(phenyldiazidostannyl)diphenylether.
. 1,5-bis(diphenylazidosilyl)pentane.
and four moles of sodium azide are reacted in xylene sol
vent at 100° for 48 hrs.
. Triethylazidostanne.
. Phenyldimethylazidostanne.
. l,4-bis(triazidosilyl)benzene.
-
10. p,p'-bis(dimethylazidostannyl)-2,2-diphenylpro
4,4"(Na)2S1'1(c6H5)c6H4—0*C6H4_S11(CsH5) (N3 ) 2
pane.
is recovered.
References Cited by the Examiner
UNITED STATES PATENTS
Example 1X
The interaction of one mole of
2,712,026
3,030,388
3,047,589
1.5-C1Si (C6H5 ) 2(CH2 ) 5Si (C6H5 ) 2C1
and two moles of potassium ‘azide in the absence of a sol
vent at 100°' C. for 24 hrs. “yields
‘
1:5'N3Si(C6H5)2(CH2)5Si(C6H5)2N3
Example X
One mole of
ClSn (CH3 ) 2C6H.,—O(CH3 ) 2—C5H4Sn(CI-I3 ) 2C1
and two moles of lithium azide are re?uxed in pyridine
for 24 hrs. to yield
55
6/ 1955
4/1962
7/1962
Schrader __________ __ 260—349
Moore et al. ______ __ 260—~349
Scott ____________ .._ 260-—349
OTHER REFERENCES
Moeller, “Inorganic Chemistry,” pp. 661, 669, 670, 673
and 676 (Wiley) '(1952).
Rochow et al., J.A.C.S., Vol. 75, pp. 3099—3101 (1953).
WALTER A. MODANCE, Primary Examiner
IRVING MARCUS, Examiner.