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Патент USA US3083244

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United States Patent 0
ICC
3,083,237
Patented Mar. 26, 1963
1
2
3,083,237
formula are those having the general formulae listed be
low:
CHEMICAL PROCESS
Robert Neville Haszeldine, “Windyridge,” Lyme Road,
Disley, England
No Drawing. Filed June 20, 1960, Ser. No. 37,099
Claims priority, application Great Britain Nov. 17, 1959
16 Claims. (Cl. 260-647)
5
where X represents ?uorine or chlorine.
n
F F
This invention is concerned with the preparation of
?uorinated nitroso compounds.
10
Fluorinated nitroso compounds are of importance in
that they may be polymerized with ?uorinated alkenes or
where X represents ?uorine or chlorine and R represents
dienes to give useful oils, greases, Waxes, or elastomers,
a
hydrocarbon group, which may contain innocuous sub
the latter being of particular interest in that they exhibit
stituents such as ?uorine and chlorine.
excellent solvent resistance and low temperature charac 15
teristics.
Hitherto the only practicable method available for the
preparation of ?uorinated nitroso compounds has in
volved the reaction of a ?uorine-containing organic iodide
where X represents ?uorine or chlorine and R’ represents
and nitric oxide under conditions favoring the formation
a hydrocarbon group containing substituents including at
of free radicals from the iodide. From a commercial
least two ?uorine atoms on the carbon atom a to that
point of view, however, this method suffers from the dis
shown in the formula, with the proviso that when X rep
advantage that the iodide starting materials require the
resents chlorine, R' is a per?uorocarbon group. R repre~
use of expensive chemicals for their preparation. This is
particularly the case where, as is usual, the iodide is pre 25 sents a hydrocarbon group which may contain innocuous
substituents such as ?uorine or chlorine.
pared by the reaction of elemental iodine and a silver salt
IV
R;
of a ?uorinated carboxylic acid, e.g.
R-i-i-Br
I
R'r-é-Br
It has now been discovered that ?uorinated nitroso com
pounds suitable for polymerizing with ?uoroalkenes and
30
‘I
where R‘, R’, and R’, represent per?uorocarbon groups.
?uorodienes to form useful copolymers can be prepared
by employing, for the reaction with nitric oxide, a ?uorine
containing organic bromide instead of the corresponding
where R3, represents a cyclic per?uorocarbon group, the
iodide. This new method is of advantage because the 35 bromine atom being attached to a cyclic carbon atom.
bromide starting materials are less expensive and more
Typically, the R groups in Formulae II and III repre
readily available than the corresponding iodides.
The bromides preferred for use in the present inven
tion are those in which the bromine is attached to a
sent (1) alkyl or alkenyl groups preferably containing not
more than 20 carbon atoms; (2) cycloalkyl (including
alkylcycloalkyl and cycloalkyl alkyl) groups preferably
?uorine-dominated nucleus. By this it is meant that there
containing not more than 20 carbon atoms and not more
is sufficient ?uorine on the carbon atom or atoms adjacent
than 6 cyclic carbon atoms; (3) aryl (including aralkyl
to the bromine to change the reactivity of the bromine
from that normally observed in alkyl bromides, speci?
cally by making it possible to produce free radicals by
and alkaryl) groups preferably containing not more than
20 carbon atoms and not more than 6 carbon atoms in the
aromatic ring or rings; and (4) any of the above listed
?ssion of the bromine carbon bond under conditions which 45 groups substituted by ?uorine and/or chlorine. The R‘
will not cause breakdown of other bonds in the molecule.
group in Formula III is typically an analogue of the
Thus, for example, in the case of saturated and ole?ni
hydrocarbon groups listed under (1), ( 2) and (3) above,
cally unsaturated bromides these conditions will normally
substituted wholly or in part by ?uorine as indicated in
be satis?ed when there are two ?uorine atoms attached to
the de?nition under Formula III. Similarly the groups
the carbon atom to which the bromine is attached; or one 50 R’, R’, and R’, in Formula IV, when separate groups,
?uorine atom and one group having at least two ?uorine
are typically the per?uoro analogues of the various groups
atoms on the carbon atom a: to carbon atom to which the
listed under (1), (2) and (3) above for the R groups of
bromine is attached. If no ?uorine is attached directly
Formulae II and III. R’, may be a per?uoro group of the
to the carbon atom to which the bromine is attached, there
type speci?ed in (2) or (3) above.
must be at least one per?uorocarbon group attached there 55
Of particular interest are per?uorocarbon bromides and
to.
poly?uoro-, poly?uorochloro- and per?uorochloro bro
In the case of aromatic compounds in which the bromine
mides of Formulae I to III which contain either at least
is bound to a carbon atom in the aromatic ring, adjacent
two ?uorine atoms on the carbon atom to which the bro
carbon atoms should be saturated with ?uorine.
mine is attached or contain at least one ?uorine atom on
Of course the bromide should be free from groups 60 the carbon atom to which the bromine is attached and at
more reactive towards homolytic ?ssion than the bromine
least two ?uorine atoms on at ieast one carbon atom a to
such as iodine, mercaptan and hydroxyl. The compound
the carbon atom to which the bromine is attached.
may, however, have two or more bromine atoms, provided
Typical individual bromides which may be employed
they are not both located on the same carbon atom.
to form nitroso compounds by reaction with nitric oxide
Bromides of particular suitability for use in the present 65 are the following: cFaBr, CF,ClBr, CFaCFaBr,
3,083,237
4
Example I
CFaBr (60 g.) and N0 (18 g.) (molar ratio of 1.0 to
1.5) were passed into a 20 litre ?ask. A pressure of 700
mm. was attained. The 20 litre ?ask carried a central
insert of silica into which ?tted a 500 watt u.v. lamp.
Mercury (100 ml.) was put in the ?ask which was rocked
gently during the reaction to facilitate reaction with the
liberated bromine.
After irradiation for 4 hours at room temperature, a
blue colour could be seen developing, and after 24 hours
It will be noted that all the bromides de?ned above con
tain ?uorine either on the carbon atom to which the
bromine is attached or closely adjacent thereto. In gen
eral, such bromides behave in a similar manner to the
simplest and most typical members of the class, viz, the
compounds tri?uoromethyl bromide and penta?uoroethyl
bromide. Yet the behaviour of tri?uoromethyl bromide
in reacting with nitric oxide is itself wholly unexpected
in view of the known marked chemical stability of the
bromide and, in particular, in view of the prior knowledge
that in numerous reactions in which its corresponding
iodide CF31 will participate, no reaction at all takes place
with the bromide. This is illustrated by the following
reactions involving CF31, none of which will proceed with
it was very marked. Air was then admitted to convert
the excess of NO to N02 which was removed by reaction
with the mercury. Distillation of the condensible prod
ucts gave unchanged CFaBr and CFQNO (20% yield;
40% based on CF3Br used) B.P. —86° C. and shown, by
infra-red spectroscopy, to be identical with a sample pre
pared by the older route involving the reaction of CF31 and
NO.
Additional experiments were carried out using differ
ent proportions and reaction times, the other conditions
being as set out above.
Mole ratio, CF; BI'INO
the bromide, CFaBr.
(1')
Reaction
time
(hrs)
u.v.
Yield of
C FaNO
based on
CIQBR
used,
percent
CF31 -|-- C2114 '————’ OFaCHzClIgI
(ii)
u.v.
(iii)
CFqI —|- Call: ——-—v CF3.CII:CHI
CF31 + KOII ——> CFgII + K01
(iv)
(a)
heat or u.v.
CFII-l- S
(iii)
The results are summarized in
the table below.
-—--——--> CFsSSCFa
u.v.
CF31 + hydrocarbon —-> CF31]:
or heat;
1:2_
1:1_
1:1.
0
11. 5
33
19
21
30
Example II
The procedure of Example I was repeated using 2.50
g. (CF3)2CFBr and 0.45 g. NO (molar ratio, bromidezNO
of 1.0115). The yield of (CF3)2CFNO was found to be
approximately 40%.
Example 111'
The abbreviation “u.v.” denotes ultra-violet radiation.
It will be evident from the above-listed reactions in 40
The procedure of Example I was repeated using 3.0 g.
which CFaBr will not participate, that the speci?c reac
of (CF3)3CBr and 0.61 g. NO (molar ratio, bromide:NO
tivity of this compound, and its related ?uorinated bro
of 1.0:2.0). The yield of (CF3)3C.NO was 35%.
mides, towards nitric oxide is very surprising.
Example IV
The reaction between the bromide and nitric oxide is
carried out under conditions conducive to the formation
of free radicals from the bromide. Preferred conditions
involve the use of ultraviolet light as an energization
agency, with or without heat. When ultraviolet light is
used, the reaction may be carried out at a temperature in
the range from 0° C. to 100° C., preferably 20—60‘‘ C.
Pressures may vary from 0.1 to 20 atmospheres with 0.5
to 5 atmospheres preferred. When it is feasible to use
heat alone as the energizing agency, temperatures of the
order of 100° C. and higher, up to say 300“ C., are indi
cated to carry out the reaction.
The procedure of Example I was repeated using
c F¢—C F Dr
F,- F;
and NO (molar ratio, bromidezNO of 1.0:3.0).
compound
The
C Fz-C F N 0
C F?- F,
was obtained.
Reaction times will normally be between about 0.5 and
Example V
about 200 hours.
The procedure of Example I was repeated using
The reaction is preferably carried out in the presence
CF'zClBr and NO (molar ratio, bromidezNO of 1.0:2.5).
of an acceptor for bromine and it is also preferable to
remove any N02 formed during the reaction. The reac 60 The compound CFgClNO was obtained.
tion is conveniently carried out in the presence of mer
cury as this serves to remove both bromine and any N02
formed during the course of the reaction.
When mercury is used, it will normally be in a molar
proportion of from say 1 to 40 times the proportion of
NO.
Other halogen acceptors which may be used include
aqueous potassium iodide, copper powder and iron
Example VI
The procedure of Example I was repeated using
CF3(CF2)6Br and NO (molar ratio, bromidezNO of
10:30). The compound CF3(CF2)5NO was obtained.
Example VII
The compound CFSNO produced as in Example I was
reacted with tetra?uoroetbylene for 48 hours at 0° C.
The molar ratio of nitric oxide and the bromide may 70 and 140 p.s.i.g. initial pressure. The product was an
vary widely. In general, however, nitric oxidezbrornide
oily 1:1 copolymer which was used successfully to lubri
molar ratios from 1:5 to 10:1 will be used, the preferred
cate a laboratory stirrer being used in the presence of a
range being 1.5:] to 3:1.
high concentration of chlorine; the outstanding chemical
resistance of the polymer enabled the apparatus to func
The method of the invention is illustrated by the fol
tion perfectly. The 1:1 copolymer has also been ob
lowing speci?c examples.
powder.
3,083,237
.5
tained as an elastomer which can be coated on to metal
to give a chemically resistant surface.
I claim:
1. A method for making organic ?uorine compounds
containing nitroso groups which comprises reacting a
?uorine-containing organic bromide in which the bromine
6
halogeno groups being free from iodine, and where, when
X is ?uorine, R’ is selected from the group consisting of
halogenoalkyl, halogenoalkenyl, halogenocycloalkyl and
halogenoaryl groups free from iodine, having not more
than about 20 carbon atoms, not more than 6 carbon
atoms in a ring, and in which the carbon atom nearest
the C1 carbon atom has at least two ?uorine atoms at
tached thereto and when X is chlorine, R’ is selected from
is attached to a ?uorine-dominated nucleus and which is
free from other reactive groups with nitric oxide.
the group consisting of pertluoroalkyl, per?uoroalkenyl,
2. The method claimed in claim 1 wherein the reaction
is carried out using ultra violet radiation as an initiator 10 per?uorocycloalkyl and per?uoroaryl groups having not
more than about 20 carbon atoms and not more than
at a temperature of between about 0 and about 100“ (3.,
about 6 carbon atoms in a ring, with nitric oxide.
and at a pressure of from about 0.1 to about 20 atmos
9. A method of making organic ?uorine compounds
pheres, absolute, the molar ratio of nitric oxide: bromide
containing nitroso groups which comprises reacting a
being between about 1:5 and about 10:1.
?uorine-containing organic bromide having the general
3. The method claimed in claim 1 wherein the reaction
formula
is carried out at temperatures between about 100° C. and
about 300° C. and at pressures between about 0.1 and
about 20 atmospheres, absolute, the molar ratio of nitric
oxide:bromide being between about 1:5 and about 10:].
4. The method claimed in claim 1 wherein the reaction
R’:
is carried out in the presence of a bromine acceptor.
where R‘, R’, and R3, are selected from the group con
5. The method claimed in claim 1 wherein the reaction
is carried out in the presence of mercury.
sisting of pertiuoroalkyl, per?uoroalkenyl, per?uorocyclo
6. A method for making organic ?uorine-containing
nitroso compounds which comprises reacting a compound
about 20 carbon atoms and not more than 6 carbon atoms
in a ring, with nitric oxide.
having the general formula
10. A method of making organic ?uorine-containing
nitroso compounds which comprises reacting a ?uorine
alkyl and per?uoroaryl groups having not more than
containing organic bromide having the general formula
where X is selected from the group consisting of ?uorine
and chlorine, with nitric oxide.
3O
7. A method for making organic ?uorine-containing
nitroso compounds which comprises reacting a compound
having the general formula
where R5’ is a cyclic pet-?uorocarbon group having not
more than about 20 carbon atoms and not more than 6
carbon atoms in a ring, the bromine atom being attached
to a cyclic carbon atom, with NO.
11. A method for making the compound CFSNO which
comprises reacting CF3Br with NO.
12. A method for making the compound (CFQZCFNO
which comprises reacting (CF8)2CFBr with NO.
where X is selected from the group consisting of ?uorine
13. The method for making the compound (CFQECNO
and chlorine, and R is selected from the group consisting
of alkyl and alkenyl groups having not more than about 40 which comprises reacting (CF3)3CBr with NO.
20 carbon atoms, halogenoalkyl and halogenoalkenyl
14. A method for making the compound
groups having not more than about 20 carbon atoms, and
CFr-CFNO
cycloalkyl, halogenocycloalkyl, aryl and halogenoaryl
groups having not more than about 20 carbon atoms, and
not more than 6 carbon atoms in a ring, said halogeno
groups being free from iodine, with nitric oxide.
8. A method of making ?uorine-containing organic
nitroso compounds which comprises reacting a ?uorine
containing organic bromide having the general formula
Fr- F5
which comprises reacting
CFr-CFBI‘
F2‘ F;
with NO.
15. A method for making the compound
CFzClNO
which comprises reacting CFgClBl' with NO.
where X is selected from the group consisting of ?uorine
and chlorine, where R is selected from the group consist
ing of alkyl and alkenyl groups having not more than
about 20 carbon atoms, halogenoalkyl and halogena
16. A method for making the compound
CFs(CFa)aNO
which comprises reacting CF3(CF,) ,Br with N0.
References Cited in the tile of this patent
alkenyl groups having not more than about 20 carbon
atoms, and cycloalkyl, halogenocycloalkyl, aryl and halo
FOREIGN PATENTS
genoaryl groups having not more than about 20 carbon
atoms and not more than 6 carbon atoms in a ring, said
770,619
Great Britain _________ -- Mar. 20, 1957
Notice of Adverse Decision in Interference
In ‘Interference No. 94,123 involving Patent No. 3,083,237, R. N.
Haszelchne, Chemical process, ?nal judgment adverse to the pabentee was ren
dered Oct. 7, 1964, as to claim 11.
[O?icz'al Gazette N o'vember Q4, 1964.]
3,083,237
.5
tained as an elastomer which can be coated on to metal
to give a chemically resistant surface.
I claim:
1. A method for making organic ?uorine compounds
containing nitroso groups which comprises reacting a
?uorine-containing organic bromide in which the bromine
6
halogeno groups being free from iodine, and where, when
X is ?uorine, R’ is selected from the group consisting of
halogenoalkyl, halogenoalkenyl, halogenocycloalkyl and
halogenoaryl groups free from iodine, having not more
than about 20 carbon atoms, not more than 6 carbon
atoms in a ring, and in which the carbon atom nearest
the C1 carbon atom has at least two ?uorine atoms at
tached thereto and when X is chlorine, R’ is selected from
is attached to a ?uorine-dominated nucleus and which is
free from other reactive groups with nitric oxide.
the group consisting of pertluoroalkyl, per?uoroalkenyl,
2. The method claimed in claim 1 wherein the reaction
is carried out using ultra violet radiation as an initiator 10 per?uorocycloalkyl and per?uoroaryl groups having not
more than about 20 carbon atoms and not more than
at a temperature of between about 0 and about 100“ (3.,
about 6 carbon atoms in a ring, with nitric oxide.
and at a pressure of from about 0.1 to about 20 atmos
9. A method of making organic ?uorine compounds
pheres, absolute, the molar ratio of nitric oxide: bromide
containing nitroso groups which comprises reacting a
being between about 1:5 and about 10:1.
?uorine-containing organic bromide having the general
3. The method claimed in claim 1 wherein the reaction
formula
is carried out at temperatures between about 100° C. and
about 300° C. and at pressures between about 0.1 and
about 20 atmospheres, absolute, the molar ratio of nitric
oxide:bromide being between about 1:5 and about 10:].
4. The method claimed in claim 1 wherein the reaction
R’:
is carried out in the presence of a bromine acceptor.
where R‘, R’, and R3, are selected from the group con
5. The method claimed in claim 1 wherein the reaction
is carried out in the presence of mercury.
sisting of pertiuoroalkyl, per?uoroalkenyl, per?uorocyclo
6. A method for making organic ?uorine-containing
nitroso compounds which comprises reacting a compound
about 20 carbon atoms and not more than 6 carbon atoms
in a ring, with nitric oxide.
having the general formula
10. A method of making organic ?uorine-containing
nitroso compounds which comprises reacting a ?uorine
alkyl and per?uoroaryl groups having not more than
containing organic bromide having the general formula
where X is selected from the group consisting of ?uorine
and chlorine, with nitric oxide.
3O
7. A method for making organic ?uorine-containing
nitroso compounds which comprises reacting a compound
having the general formula
where R5’ is a cyclic pet-?uorocarbon group having not
more than about 20 carbon atoms and not more than 6
carbon atoms in a ring, the bromine atom being attached
to a cyclic carbon atom, with NO.
11. A method for making the compound CFSNO which
comprises reacting CF3Br with NO.
12. A method for making the compound (CFQZCFNO
which comprises reacting (CF8)2CFBr with NO.
where X is selected from the group consisting of ?uorine
13. The method for making the compound (CFQECNO
and chlorine, and R is selected from the group consisting
of alkyl and alkenyl groups having not more than about 40 which comprises reacting (CF3)3CBr with NO.
20 carbon atoms, halogenoalkyl and halogenoalkenyl
14. A method for making the compound
groups having not more than about 20 carbon atoms, and
CFr-CFNO
cycloalkyl, halogenocycloalkyl, aryl and halogenoaryl
groups having not more than about 20 carbon atoms, and
not more than 6 carbon atoms in a ring, said halogeno
groups being free from iodine, with nitric oxide.
8. A method of making ?uorine-containing organic
nitroso compounds which comprises reacting a ?uorine
containing organic bromide having the general formula
Fr- F5
which comprises reacting
CFr-CFBI‘
F2‘ F;
with NO.
15. A method for making the compound
CFzClNO
which comprises reacting CFgClBl' with NO.
where X is selected from the group consisting of ?uorine
and chlorine, where R is selected from the group consist
ing of alkyl and alkenyl groups having not more than
about 20 carbon atoms, halogenoalkyl and halogena
16. A method for making the compound
CFs(CFa)aNO
which comprises reacting CF3(CF,) ,Br with N0.
References Cited in the tile of this patent
alkenyl groups having not more than about 20 carbon
atoms, and cycloalkyl, halogenocycloalkyl, aryl and halo
FOREIGN PATENTS
genoaryl groups having not more than about 20 carbon
atoms and not more than 6 carbon atoms in a ring, said
770,619
Great Britain _________ -- Mar. 20, 1957
Notice of Adverse Decision in Interference
In ‘Interference No. 94,123 involving Patent No. 3,083,237, R. N.
Haszelchne, Chemical process, ?nal judgment adverse to the pabentee was ren
dered Oct. 7, 1964, as to claim 11.
[O?icz'al Gazette N o'vember Q4, 1964.]
Disclaimer
3,083,237.—1~?0bert Neville Haszeldz'ne, Disle , England. CHEMICAL Pnoonss.
Patent dated Mar. 26, 1963. Disclaimer ?led Feb. 3, 1965, by the
inventor.
Hereb
patent.
y enters this disclaimer to claims 1, ‘2, 4, 6, 6, 7, 11, 15 and 16 of said
[O?’ioial Gazette March 9, 1965.]
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