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Патент USA US3079441

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United Etates Pater
Patented Feb. 26, 1953
lows: Ten grams of bis(triiluoromethyl)phosphinous
amide, (CF3)2PNH2, was transferred in an air-free system
3 079 431
svmrmsrs or retires-hare srsmnarmrono
to a three-neck ?ask ?tted with stirrer, Dewar condenser
and inlet for gas. About 50 ml. of CHCl3 was then in
troduced as a solvent and the ?ask cooled at —30° C.
with a Dry-Ice/ acetone bath. The stoichiometric amount
of chlorine was introduced through the gas inlet keeping
Giorgio Tesi and Catherine M. Douglas, Riverside, Calif”
asslgnors to the United States of America as represented
by the Secretary of the Navy
No Brawing. Fiied July 6, 1961, Ser. No. 122,365)
3 Claims. (Cl. 2643-551)
(Granted under Title 35, US. Code (1952), see. 26-5)
the solution in the ?ask under vigorous stirring. A
smooth reaction took place and the whole amount of C12
The invention herein described may be manufactured 10 was used. After the addition was completed, the mixture
and used by or for the Government of the United States
was slowly treated with two equivalents of the tertiary
of America for governmental purposes without the pay
amine, trimethylamine. A White precipitate was im
ment of any royalties thereon or therefor.
mediately formed. The mixture was then allowed to
The present invention relates to the preparation of
warm up to room temperature. The volatile materials
polymeric materials and more particularly to the polymer 15 were then removed under reduced pressure and the white
ic materials having a backbone of alternated atoms of
solid material left was thoroughly extracted with CHCls
phosphorus in the pentavalent state and nitrogen, and
in a Soxhlet extractor to remove the trirnethylamine hy
having per?uoroalkyl groups as substitutes on the phos
drochloride present. The white powder left Was dried
under vacuum. A high yield (about 60%) of a com
Materials producw by the synthesis of the present in
pound corresponding to the composition [(CF3)2PN]n
vention possess remarkable resistance toward oxidation
and thermal decomposition, and have uses in any system
where these properties are desired.
was thus obtained. Other compounds having the same
elemental composition but different structure and char
acteristics have been isolated from this reaction and are
A compound, polymeric bis(per?uoromethyl)phos
phinic nitride, has been obtained through decomposition
described and claimed in copending application Serial No.
25 122,353, ?led July 6, 1961, for Trimeric and Tetrarneric
Bis (Tri?uoromethyl ) Phosphinic Nitrides.
Another example of synthesis performed through the
of the corresponding azide, (CF3)2PN3, as described in
copending patent application Serial No. 97,700, ?led
March 22, 1961, for Bisper?uoromethylphosphinic Ni
tride. However, due to the exposive character of the
procedure of the present invention is the preparation of
trimeric ‘bis(hepta?uoropropyl) phosphinic nitride,
intermediate azide in the previous method, due care must 30
be taken in preparing the compound by that process. The
which was obtained in a 70% yield employing the same
synthesis of the present invention overcomes the disad
procedure as previously described herein, starting from
vantage of the previous method, and di?erent and new
bis(hepta?uoropropyl) phosphinous amide, (C3F7)2PNH2.
compounds are obtainable thereby.
This compound is described and claimed in another co
It is an object of the invention to provide a new and
improved synthesis for the preparation of compounds
having the molecular structure (RF)2PN where R=any
per?uoroalkyl groups.
It is another object of the invention to provide a com
pletely safe technique for synthesizing polymeric bis(per
?uoromethyDphosphinic nitride.
pending application, Serial No. 122,354, ?led July 6, 1961,
for Trimeric Bis (hepta?uoropropyl)Phosphinic Nitride.
The whole operation of the present synthesis is greatly
more convenient and practical than the technique of the
decomposition of the azide, vand provides entirely safe
reactions and yields of high pure grade compound.
Obviously many modi?cations and variations of the
It is still another object of the invention to provide a
present invention are possible in the light of the above
synthesis for the preparation of polymeric materials hav
teachings. It is therefore to be understood that Within the
ing a backbone of alternated atoms of phosphorus in the
scope of the appended claims the invention may be prac
pentavalent state and nitrogen, and having per?uoroalkyl
ticed otherwise than as speci?cally described.
groups as substitutes on the phosphorus.
What is claimed is:
It is a further object of the invention to provide the
1. A method for the synthesis of bis(tri?uoromethyl
synthesis of polymeric bis(per?uoroalkyl)phosphinic ni
and hepta?uoropropyl)phosphinic nitrides which com
trides, wherein the yield is quantitative and the compound
prises reacting a chloroform solution of bis(per?uo-ro
high in purity.
Other objects and many of the attendant advantages of
this invention will become readily appreciated as the same
alkyl)phosphinous amide of the formula (RF)2PNH2,
where RF is from the group consisting of tri?uoromethyl
and hepta?uoropropyl, with chlorine at a temperature of
becomes better understood by reference to the following
—30° C. in an inert atmosphere and subsequent dehydro
detailed description:
h-alogenation of the reaction mixture with trimethylamine.
In the synthesis of the present invention, chlorination
2. A method for the synthesis of bis(tri?uoromethyl)
of bis(per?uoroalkyl)phosphinous amides, (RF)2PNH2,
phosphinic nitride which comprises reacting a chloroform
leads to the formation of bis(per?uoroalkyl) dischloro
solution of bis(tri?uoromethyl)phosphinous with chlorine
phosphinic amides, (RF)2P(Cl2)NI-I2, which in turn can
in an inert atmosphere ‘at a temperature of ——30° C. and
be dehydrohalogenated by use of a tertiary amine, such as
the subsequent dehydrohalogenation of the reaction mix
trimethylamine, thus forming bis (per?uoroalkylphosphin~
ic nitrides, as shown by the following reactions:
ture with a trimethylamine.
3. A method for the synthesis of bis(hepta?uoropro
pyl)phosphinic nitride comprising reacting a chloroform
solution of bis(hepta?uoropropyl)phosphinous amide
chlorine in an inert atmosphere at a temperature of
where RF=per?uoroalkyl groups, and NR3 may be tri 65 with
C. and the subsequent dehydrohalogenation of the
reaction mixture with trimethylamine.
This technique is completely safe, the yield is quantita
tive and the resulting compound can be obtained in high
purity by solvent extraction of the tertiary amine hydro
chloride from the mixture.
References Cited in the ?le of this patent
Audrieth et a1. Chemical Reviews, volume 32, pages
This can be accomplished 70 125-130 (1940).
Harris: J. Chem. Soc. (London), pages 512-519
very easily because of the insolubility of the polymer.
An example of the foregoing synthesis is given as fol
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