Pentafluorotellurium hypofluorite and pentafluorotellurium hypochlorite have been reacted with olefinic reactants to form fluorocarbon adducts containing the oxypentafluorotellurium group (TeF.sub.5 O--).

BACKGROUND OF THE INVENTION 
This invention relates to a method for synthesizing fluorocarbon fluids 
containing oxypentafluorotellurium (TeF.sub.5 O--) substituents. The 
TeF.sub.5 O-- group is inherently dense and when incorporated into 
fluorocarbon fluids it provides enhanced density to those materials. In 
addition, the ether-like oxygen link furnishes molecular flexibility, 
lessening of steric hindrances, and retention of fluid properties. 
These fluids find particular utility as agents for a wide variety of 
industrial applications requiring the utilization of highly dense fluids. 
They are especially useful as flotation agents for gyroscopes, compasses 
and other like instruments which must be dampened to minimize excessive 
vibration and oscillation problems. 
To the best of our knowledge, no previous examples have been reported in 
the literature incorporating the TeF.sub.5 O-- groups into fluorocarbons. 
Compounds containing the analogous sulfur substituent, SF.sub.5 OR.sub.f, 
are known, being mainly obtained by reactions of SF.sub.5 OCl and SF.sub.5 
OF with olefins. This work showed that the addition of SF.sub.5 OX to 
olefins proceeded according to the general equation: 
##STR1## 
For both of these hypohalites, good yields of the adducts are often 
obtained but the hypofluorite reactions are sometimes difficult to control 
and much lower yields are realized. This is not surprising in view of the 
fact that CF.sub.3 OF reacts explosively with some olefins and its 
addition to them is superseded by fluorination reactions. 
In the case of SeF.sub.5 OF reactions with olefins such as CF.sub.2 
.dbd.CF.sub.2, CF.sub.3 CF.dbd.CF.sub.2 and CH.sub.2 .dbd.CH.sub.2, no 
products containing the SeF.sub.5 O-- group were identified. With 
perfluorocyclopentene a good yield of the adduct, SeF.sub.5 OC.sub.5 
F.sub.9, was obtained. No examples of the addition of SeF.sub.5 OCl to 
olefin have been reported. 
Based on the observed trends in the reactivity of the Group VI 
hypofluorites with respect to olefins, one would expect that TeF.sub.5 OX, 
where X is F or Cl, should not undergo a facile addition reaction. 
Therefore, it was unexpected that the recently discovered TeF.sub.5 OF 
would react smoothly with olefins to provide TeF.sub.5 O-- substituted 
fluorocarbons in high yield by addition across the olefin double bond. 
Furthermore, it has been found that TeF.sub.5 OCl also adds to olefins. In 
this instance, the reaction is more difficult to control to achieve the 
desired addition, and yields of the adducts are lower. All of the 
TeF.sub.5 O-- substituted fluorocarbons are thermally stable fluids. Their 
either-like structure provides the desirable fluid properties exhibited by 
that class of compounds. In addition, they have enhanced density due to 
the presence of the TeF.sub.5 O-- group. 
SUMMARY OF THE INVENTION 
In accordance with this invention, a novel class of high density fluids 
based on TeF.sub.5 O-- substituted fluorocarbons and a process for their 
synthesis have been discovered. The synthesis utilizes 
oxypentafluorotellurium hypohalites as reactants to effect an addition 
reaction with aliphatic or alicyclic halogen substituted olefins to 
produce useful fluorocarbons substituted with the TeF.sub.5 O-- group. The 
synthesis involves condensing the oxypentafluorotellurium hypohalite and 
an olefin together at subambient temperature, and allowing the mixture to 
gradually warm to ambient temperature. After a day, or longer if desired, 
the products are separated by fractional condensation. The following 
general equation describes this addition reaction. 
##STR2## 
Yields of the adduct of this reaction are 60-86% in the case of the 
hypofluorite and 22-30% in the case of the hypochlorite. 
Accordingly, the primary object of the invention is to provide a method for 
synthesizing novel high density halogen substituted hydrocarbon fluids. 
Another object of this invention is to provide a method for synthesizing 
high density fluorocarbon fluids that utilizes pentafluorotellurium 
hypofluorite as a reactant. 
Still another object of this invention is to provide a method for 
synthesizing halogen substituted hydrocarbons containing 
oxypentafluorotellurium substituents. 
A further object of this invention is to provide a novel class of 
pentafluorotellurium oxide fluorocarbons. 
The above and still further objects and advantages of the present invention 
will become more readily apparent upon consideration of the following 
detailed description thereof. 
DESCRIPTION OF THE PREFERRED EMBODIMENT 
Pursuant to the above-defined objects, the present invention concerns 
itself with a novel method for synthesizing pentafluorotellurium oxide 
fluorocarbons and to the novel high density fluids prepared thereby. The 
invention is brought into effect by accomplishing an addition reaction at 
subambient temperatures between a pentafluorotellurium hypohalite, such as 
pentafluorotellurium hypofluorite or pentafluorotellurium hypochlorite, 
and an appropriate halogen substituted, aliphatic or alicyclic, 
hydrocarbon olefin. The resulting fluids are highly dense, thermally 
stable and contain oxypentafluorotellurium (TeF.sub.5 O--) as a 
substituent on the fluorocarbon chain. Such highly dense fluids are 
especially desired as flotation agents in improved gyroscopes. 
The reaction for synthesizing the novel fluorocarbon fluids of this 
invention is illustrated by the following equation. 
EQU TeF.sub.5 OX+olefin.fwdarw.TeF.sub.5 OR.sub.f (II) 
wherein X is F or Cl and R.sub.f is the radical --CF.sub.2 CF.sub.3 ; 
--CF.sub.2 CF.sub.2 Cl; --CFClCF.sub.3 ; --CF.sub.2 CF.sub.2 CF.sub.3 ; 
--CF(CF.sub.3).sub.2 ; --CF.sub.2 CFClCF.sub.3 ; or 
##STR3## 
This novel reaction represents a new route to the preparation of 
halocarbons containing TeF.sub.5 O-- substituents. The hypohalite reactant 
and the olefinic reactant are cocondensed at subambient temperatures and 
then allowed to gradually warm up to ambient temperature. The reaction 
mixture is then maintained at ambient temperature for at least a 24 hour 
period and then the resulting reaction products are separated by 
fractional condensation. 
The volatile materials used in the reaction scheme of this invention were 
manipulated in a stainless steel vacuum line equipped with Teflon FEP 
U-traps, 316 stainless steel bellows-seal valves, and a Heise Bourdon 
tube-type gauge. The synthetic reactions employed here were usually 
conducted in stainless steel cylinders. Infrared spectra were recorded on 
a Perkin Elmer Model 283 spectrophotometer using cells equipped with AgCl, 
AgBr, or CsI windows. The .sup.19 F NMR spectra were recorded at 84.6 MHz 
on a Varian Model EM 390 spectrometer with internal CFCl.sub.3 as a 
standard with a negative chemical shift being upfield from CFCl.sub.3. 
The TeF.sub.5 OF employed herein was prepared from Cs.sup.+ TeF.sub.5 
O.sup.- and FOSO.sub.2 F by reaction at -45.degree. C. as shown in Example 
1 which follows. The TeF.sub.5 OCl was prepared by reacting TeF.sub.5 OH 
and ClOSO.sub.2 F at temperatures below and up to ambient in accordance 
with the procedure described in J. Fluorine Chem. 1982, 21, 393. 
The reaction scheme for synthesizing the TeF.sub.5 OF reactant used in the 
method of this invention is further illustrated with greater specificity 
by Example I which follows.

EXAMPLE I 
A 30 ml stainless steel Hoke cylinder was loaded with CsTeF.sub.5 O (3.42 
mmol) in the glove box. After evacuation and cooling of the cylinder to 
-196.degree. C., FOSO.sub.2 F (2.79 mmol) was added from the vacuum line. 
The closed cylinder was slowly warmed to -78.degree. C. in a liquid 
nitrogen-CO.sub.2 slush bath and finally kept at -45.degree. C. for 9d. 
Upon recooling to -196.degree. C. about 4-5 cm.sup.3 noncondensable gas 
was observed to be present. This was pumped away and the condensable 
products were separated by fractional condensation in a series of U-traps 
cooled at -78.degree., -126.degree., and -196.degree. C. The -78.degree. 
C. fraction was TeF.sub.5 OH (0.19 mmol) while the -196.degree. C. 
fraction was TeF.sub.6 (0.49 mmol). 
A white solid was retained at -126.degree. C. which changed to a colorless 
glass and melted, over a range of a few degrees, near -80.degree. C. to a 
clear, colorless liquid. This material was identified as TeF.sub.5 OF 
(1.91 mmol, 68% yield) based on its vapor density molecular weight; found, 
256.2; calc., 257.6 g/mol. Further identification was based on its 
spectroscopic properties and on the preparation of derivatives. The 
observed weight loss of the solid (0.375 g) agreed well with that 
calculated (0.389 g) for the conversion of 2.79 mmol CsTeF.sub.5 O to 
CsSO.sub.3 F. Vapor pressure-temperature data of TeF.sub.5 OF were 
measured: T.degree.C., Pmm; -79.3, 16; -64.2, 45, -57.6, 63; -46.9, 108; 
-32.5, 210; -23.0,312. 
The TeF.sub.5 OF compound of Example 1 is colorless as a gas and liquid. 
Its vapor pressure-temperature relationship for the range -79.degree. to 
-23.degree. C. is given by the equation,. 
EQU log P.sub.mm =6.9022-1101.2/T.degree.K. 
The extrapolated boiling point is 0.6.degree. C. The derived heat or 
vaporization is .DELTA.H.sub.vap =5039 cal mol.sup.-1 and the Trouton 
constant is 19.4 indicating little or no association in the liquid phase. 
Vapor density measurements showed that in the gas phase the compound is 
also not associated. A sharp melting point for TeF.sub.5 OF was not 
observed because the samples showed a tendency to form a glass near 
-80.degree. C. The compound appears to be completely stable at ambient 
temperature and has been stored in stainless steel cylinders for more than 
four months without any sign of decomposition. Examples 2 to 7, which 
follow, disclose in detail the reaction scheme and the resulting high 
density fluids illustrated by equation (II) above. 
EXAMPLE 2 
A 10 ml cylinder was evacuated, cooled to -196.degree. C., and then 
successively TeF.sub.5 OF (1.42 mmol) and C.sub.2 F.sub.4 (2.30 mmol) were 
condensed into it. The closed cylinder was allowed to warm slowly in a 
dewar containing solid carbon dioxide cooled to -196.degree. C. After warm 
up, the reactor was kept at ambient temperature for a day. The products 
were separated by fractional condensation through a series of connected 
U-traps cooled to -112.degree. and -196.degree. C. The more volatile 
material collected at -196.degree. C. was mainly unreacted C.sub.2 F.sub.4 
together with TeF.sub.6. The latter is both a common contaminant of 
TeF.sub.5 OF and a degradation product thereof. Retained in the trap at 
-112.degree. was TeF.sub.5 OCF.sub.2 CF.sub.3 (0.85 mmol. 60% yield). This 
material was a clear, colorless liquid and had a vapor pressure of about 4 
mm of Hg at -78.degree. C. and had a measured vapor density of 355.2 g/mol 
(theory for TeF.sub.5 OC.sub.2 F.sub.5 is 357.6 g/mol). Storage at ambient 
temperature or heating for a day to 95.degree. C. in stainless steel 
vessels did not result in any detectable decomposition. 
Further identification was based on its spectroscopic properties. The 
.sup.19 F NMR spectrum was that expected for an AB.sub.4 spin system 
(TeF.sub.5 O-- possesses one apical and four equatorial fluorines) and an 
alkyl fluorocarbon. Observed NMR parameters were [ppm(multiplicity)] where 
b-broad, c-complex, d-doublet, t-triplet, qi-quintet, s-sextet, and 
m-multiplet. For F.sup.A TeF.sub.4.sup.B OCF.sub.2.sup.X CF.sub.3.sup.Y : 
A-49.7, B-40.0 (t of B.sub.4), X-80.2 (cm), Y-87.4(t); J.sub.AB =185, 
J.sub.BX =5.5, J.sub.XY 2.3 Hz. The measured area ratios for these four 
types of fluorine were in the anticipated ratio of 1:4:2:3. Infrared bands 
noted were cm.sup.-1 (intensity): 1247(vs), 1190(vs), 1110(vs), 745(vs), 
722(s), and 328(s). The position and intensity of the three bands at about 
745,722, and 325 cm.sup.-1 are very characteristic of stretching and 
bending vibrations of the TeF.sub.5 group. 
EXAMPLE 3 
A 10 ml cylinder was loaded as above with TeF.sub.5 OF(0.65 mmol) and 
perfluoropropene (0.81 mmol). After slowly warming from -196.degree. C. to 
ambient temperature the reactor was kept at ambient temperature for 2 
days. Fractional condensation through U-traps cooled at -78.degree., 
-95.degree., and -196.degree. C. was used to separate the products. The 
-95.degree. C. trap contained TeF.sub.5 OC.sub.3 F.sub.7 (0.51 mmol, 78% 
yield) which was a clear, colorless liquid and had a vapor density of 404 
g/mol (theory=407.6 g/mol). Storage at ambient temperature or heating for 
a day at 95.degree. C. in stainless steel vessels did not result in any 
detectable decomposition. 
Further identification was based on spectroscopic properties. The .sup.19 F 
NMR spectrum revealed that the product was a mixture of isomers as shown 
in the equation. 
EQU TeF.sub.5 OF+CF.sub.3 CF.dbd.CF.sub.2 .fwdarw.TeF.sub.5 OCF.sub.2 CF.sub.2 
CF.sub.3 +TeF.sub.5 OCF(CF.sub.3).sub.2 (III) 
These two isomers are the result of a non-regiospecific addition of 
TeF.sub.5 O-- and F-- to the olefin double bond. Based on the NMR 
spectrum, the ratio of the n-propyl to the iso-propyl derivative was 
70:30. Again the AB.sub.4 patterns, characteristic for the TeF.sub.5 O-- 
groups were observed. The NMR parameters were ppm(multiplicity) for 
F.sup.A TeF.sub.4.sup.B OCF.sub.2.sup.X CF.sub.2.sup.Y CF.sub.3.sup.Z : 
A-53.9, B-42.6 (t of B.sub.4), X-76.6(cm), Y-132.8(t,m), Z-84,6(t); 
J.sub.AB =180, J.sub.BX =5.4, J.sub.XY =0.9, J.sub.YZ =8.1 Hz. The correct 
data ratios for these assignments (1:4:2:2:3) was observed. For F.sup.A 
TeF.sub.4.sup.B OCF.sup.X (CF.sub.3).sub.2.sup.Y : A-53.4, 
B-41.8(bB.sub.4), X-132.7(bqi), Y-84.3(s); J.sub.AB =185, J.sub.BX =11, 
J.sub.XY =2.2, J.sub.BY =2.2 Hz and the measured area ratios were 
respectively 1:4:1:6 in agreement with those expected for this isomer. 
An infrared spectrum of the mixture showed bands at cm.sup.-1 (int.): 
1350(w), 1320(m), 1300(w), 1265(sh), 1245(vs), 1210(m), 1180(sh), 1170(s), 
1145(s), 1005(s), 754(s), 723(s), and 322(s). Bands typical of the 
TeF.sub.5 group are prominent and confirm its presence in this material. 
EXAMPLE 4 
As in the preceeding examples TeF.sub.5 OF(1.65 mmol) and 
perfluorocyclopentene (1.78 mmol) were reacted in a stainless steel 
cylinder. Fractional condensation resulted in retention of TeF.sub.5 
OC.sub.5 F.sub.9 (1.42 mmol, 86% yield) in a trap cooled at -78.degree. C. 
This material was a colorless liquid with a vapor pressure of about 24 mm 
Hg at 20.degree. C. and a vapor density of 467 g/mol (theory=469.6 g/mol). 
It exhibited the same good storability and thermal stability of the other 
TeF.sub.5 OR.sub.f examples. 
The .sup.19 F NMR for TeF.sub.5 OC.sub.5 F.sub.9 showed the typical 
AB.sub.4 pattern for the TeF.sub.5 group and a very complex multiplet, 
expected for a cyclic C.sub.5 compound; [ppm (multiplicity)] F.sup.A 
TeF.sub.4.sup.B OC.sub.5 F.sub.9.sup.X : A-50.7, B-40.0(m), X-131(m). The 
area ratio for the three types of fluorine were as expected (1:4:9). 
Infrared bands for TeF.sub.5 OC.sub.5 F.sub.9 were at cm.sup.-1 (int.); 
1320(s), 1280(m), 1224(vs), 1166(s), 988(vs), 744(vs), 711(s), and 319(s) 
and are in agreement with the above formulation. The synthesis of the 
product of this example is illustrated by the following equation: 
##STR4## 
EXAMPLE 5 
As in the preceeding examples, TeF.sub.5 OF(0.41 mmol) and 
chlorotrifluoroethylene (0.47 mmol) were reacted. On workup an adduct of 
the empirical formula TeF.sub.5 OC.sub.2 F.sub.4 Cl was retained in a trap 
cooled at -112.degree. C. (0.27 mmol). This adduct was stable and storable 
in the same way as the preceeding examples. 
The .sup.19 F NMR spectrum of this product revealed the presence of two 
isomers resulting from the non-regiospecific addition of TeF.sub.5 OF as 
shown in the following equation. 
##STR5## 
The ratio of I to II in the mixture was 40:60 indicating that steric 
factors were not governing the direction of the addition since the more 
hindered isomer was formed in a larger percentage. Measured NMR parameters 
were [ppm (multiplicity)] F.sup.A TeF.sub.4.sup.B OCF.sub.2.sup.X 
CF.sub.2.sup.Y Cl: A-49.5, B-40.2 (t of B.sub.4), X-78.0(qi,t), Y-73.1(t): 
J.sub.AB 179, J.sub.BX 5.3, J.sub.XY 1.45 Hz. The correct area ratios 
(1:4:2:2) for this assignment were observed. For F.sup.A TeF.sub.4.sup.B 
OCF.sup.X ClCF.sub.3.sup.Y : A-49.0, B-38.3(d of B.sub.4), X-69.5(qi,q), 
Y-85.8(d); J.sub.AB 180, J.sub.BX 6.6, J.sub.XY 1.7 Hz were measured with 
the correct area ratios of 1:4:1:3. 
From the known infrared spectrum of pure TeF.sub.5 OCF.sub.2 CF.sub.2 Cl 
prepared as in Example 5, the infrared spectrum of TeF.sub.5 OCFClCF.sub.3 
in the above isomer mixture was obtained by difference, cm.sup.-1 (int.): 
1320(s), 1245(vs), 1130(s), 1105(vs), 968(s), 743(s), 708(m), and 322(s). 
Again the last three bands are indicative of the presence of a TeF.sub.5 
group in the molecule. 
EXAMPLE 6 
A 30 ml cylinder was loaded at -196.degree. C. with TeF.sub.5 OCl (2.58 
mmol) and tetrafluoroethylene (3.07 mmol) and allowed to warm slowly to 
ambient temperature overnight. Pumping on the reactor at that time through 
traps cooled at -78.degree., -112.degree., and -196.degree. C. resulted in 
the isolation of TeF.sub.5 OCF.sub.2 CF.sub.2 Cl in the -112.degree. C. 
trap (0.78 mmol, 30% yield) with a measured vapor density of 372 g/mol 
(theory=374 g/mol). This clear, colorless liquid was stable and unchanged 
after heating for 16 hours at 95.degree. C. and was storable in stainless 
steel. 
The .sup.19 F NMR spectrum of the product showed it to be the expected 
adduct with the measured parameters being identical to those noted for 
this compound in its isomer mixture with TeF.sub.5 OCFClCF.sub.3 as 
described in Example 4. Infrared bands for the pure TeF.sub.5 OCF.sub.2 
CF.sub.2 Cl obtained by this reaction were at cm.sup.-1 (int.): 1310(w), 
1198(vs), 1182(vs), 1128(s), 981(s), 743(s), 724(s), and 324 (ms). The 
presence of the TeF.sub.5 group is apparent from the last three observed 
bands which are characteristic for that group. 
The main products from this reaction were CF.sub.3 CF.sub.2 Cl which was 
trapped at -196.degree. C. and a non-volatile, colorless oily liquid which 
remained in the reaction cylinder. This oily liquid was assumed to be 
(TeF.sub.4 O).sub.2. Both it and the CF.sub.3 CF.sub.2 Cl arose from the 
following reaction. 
EQU TeF.sub.5 OCl+CF.sub.2 =CF.sub.2 .fwdarw.CF.sub.3 CF.sub.2 Cl+(TeF.sub.4 
O).sub.2 +TeF.sub.5 OCF.sub.2 CF.sub.2 Cl (VI) 
Because of the great difference in volatility between these materials, the 
desired TeF.sub.5 OCF.sub.2 CF.sub.2 Cl adduct was easily separated out of 
the reaction mixture. 
EXAMPLE 7 
A sample of perfluoropropene (2.78 mmol) was cooled at -95.degree. C. in a 
Teflon FEP U-trap on the vacuum line. From a reservoir at ambient 
temperature, TeF.sub.5 OCl (2.59 mmol) was slowly bled into the trap 
containing the cold C.sub.3 F.sub.6. This addition was monitored by 
reading the pressure in the reservoir and in 2 hours the stated amount was 
added. The mixture was left at -78.degree. C. overnight and the products 
were separated by fractional condensation in U-traps cooled at 
-78.degree., -95.degree., and -196.degree. C. Collected at -95.degree. C. 
was TeF.sub.5 OCF.sub.2 CFClCF.sub.3 (0.57 mmol, 22% yield), a clear, 
colorless liquid with a vapor density of 426 g/mol (theory=424 g/mol). 
This compound was stable at 95.degree. C. and storable at ambient 
temperature for long periods as noted for the other TeF.sub.5 OR.sub.f 
materials. 
Further identification based on .sup.19 F NMR measurements confirmed the 
composition of this product. Observed parameters were [ppm (multiplicity)] 
F.sup.A TeF.sub.4.sup.B OCF.sub.2.sup.X CF.sup.Y ClCF.sub.3.sup.Z : 
A-49.7, B-39.9(t of B.sub.4), X-71.7(cm), Y-139.7(s), Z-79.2(t,d); 
J.sub.AB 185, J.sub.BX 5.4, J.sub.XY 6.7, J.sub.YZ 6.7, J.sub.XZ 9.5 Hz. 
Area ratios for the various fluorine resonances (1:4:2:1:3) agreed with 
assignments. Infrared bands for this compound were at cm.sup.-1 (int.): 
1297(ms), 1268(s), 1242(vs), 1177(s), 1136(ms), 987(s), 973(s), 744(s), 
721(s), and 325(s). These bands also indicate the assigned composition to 
be correct. It should be noted that only one addition isomer was found 
although a second isomer, ClCF.sub.2 CF(OTeF.sub.5)CF.sub.3, is 
theoretically also possible. 
The major products of this reaction were CF.sub.3 CFClCF.sub.3, TeF.sub.5 
OCF.sub.2 CFClCF.sub.3, and the oily, non-volatile liquid, (TeF.sub.4 
O).sub.2 as shown in the following reaction. 
EQU TeF.sub.5 OCl+CF.sub.3 CF=CF.sub.2 .fwdarw.CF.sub.3 CFClCF.sub.3 
+(TeF.sub.4 O).sub.2 +TeF.sub.5 OCF.sub.2 CFClCF.sub.3 (VII) 
These are readily separable from the desired TeF.sub.5 OCF.sub.2 
CFClCF.sub.3 adduct due to their great volatility differences. 
From a consideration of the above it can be seen that the present invention 
provides a novel class of high density fluids and a simple, direct, and 
effective route for their synthesis. 
While this invention has been described with reference to preferred 
embodiments thereof, it should be understood by those skilled in the art 
that various alterations and modifications that come within the purview of 
the appended claims are intended to be included herein.