- Email: [email protected]
Synthesis of trichlorophosphazo-trifluoromethane and - pentafluoroethane
85
JoumaZofFluorine Chemistry, 19 (1981/82) 85-88 0 Elsevier Sequoia S.A., Lawanne - Printed in the Netherlands Received: April 6, 1981
Synthesis
of
trichlorophosphazo-trifluoromethane
and
-pentafluoroethane
WALTER LEIDINGER
Department
and WOLFGANG
of Inorganic
D-6900 Heidelberg,
SUNDERMEYER+
Chemistry,
Im Neuenheimer
University
of Heidelberg,
Feld 27o,(Federal
Republic
of Germany)
SUMMARY The trichlorophosphazo could be obtained dichloroamines
INTRODUCTION
and phosphorous
the smallest
to nitrogen,
compounds
have been studied
perfluorinated
monomer in the
have not yet been prepared.
may have been the difficulty
easily
for preparing
polarities
relative
trichlorophosphazo
[1,2], CF3-NH2
to use the dichloroamines
to react the dichloroamines
CF3-NPC13
reason for this
lose HF to give the corresponding
It seemed reasonable of the different
compounds,
the free amines, which
As is known from the literature
as CF3-CF2-NH2
for a long time.
d-position
A probable
in obtaining
are the usual starting materials
chloride
and C2F5-N=PC13 perfluoroalkyl
trichloride.
(2) = with fluorine
(1) and C2F5-NPC13
compounds.
CF3-N=PC13
the corresponding
AND RESULTS
Trichlorophosphazo However,
compounds
by reacting
of N-Cl and P-Cl bonds with phosphorous
as well
nitriles.
instead.
Because
[31, we decided
pentachloride
when
should be eliminated. cf<#
&-1, c1 RF-CF2-N
? +
' Cl RF = F, CF3 +Autkor
to
wkm
correspomkme
Lpc4cc) 3
---+RF-CF2-N=PC13
Cl' I, 2 = = should be addressed.
+ Cl2
86 It has been reported ween FC(O)NC12 during
[3] that no reaction was observed
and chlorinating
our experiments
we observed
and PC15, which was catalysed were poor. The main
reaction
to form the azocompound, Accordingly, amine to interact PC18 we obtained fluoroethane
agents
a side reaction
by W-light.
between
The yields
was the reduction
CFS-N=N-CFS
bet-
(PC13, PC15, A12C16);
however,
CFS-NC12
obtained
of the dichloroamine
[41.
it was thought
convenient
with a reagent
susceptible
to allow the dichloroto oxidation.
the trichlorophosphazo-trifluoromethane
Thus using
and -penta-
in high yields.
RF-CF2-NC12
+
B
2 PC18
RF-CF2-N=PClS
RF = F, CF8
Both compounds They hydrolyse
PC15
I, 2 = =
are colourless
very rapidly
1 and ? were confirmed
+
liquids under normal conditions.
and decompose
by IR, I'F-NMR,
above
31P-NMR
105'C. Structures and mass spectro-
metry.
EXPERIMENTAL
The IR-spectra
were recorded
on a Perkin-Elmer
the lg F-NMR on a JEOL C 60 HL; the 31P-NMR spectrometer
and the mass spectra
The dichloroamines sulfurdifluorides extremely
RF-CF2-NSF2
RF- CF2-NSC12, distillation.
distillation.
with Cl-F in CF3C1.
to separate
the crude dichloroamines
PC15 at -4O'C and afterwards were obtained
by the reaction
from commercial
of the imido-
They must be
of SF4 (from their preparation)
which was difficult Therefore
on a BRUKER HFX-90
on a VARIAN MAT CH7.
were obtained
pure, since traces
457 spctrometer;
with mercury. sources
gave
by 'trap to trap' were shaken with
Other starting
and purified
materials
by drying
or
a7 General
procedure:
0.05 mol dichloroamine 0.1 mol phosphorous
was condensed
trichloride.
slowly from -196'C to -1OO’C and stirred l/2 h until a precipitate filtering
in the absence
ice. The crude product The pure compounds 0.2 cm column
was formed. of air while
(filtrate)
were obtained
amounted
the filtrate
to a yield
after separation
The 31P-NMR
constant
shows a quartet
+ 7.3 ppm (H3P04 external J(P-CF3)=
at this temperature
cooling
of & shows a doublet
with a coupling
for
at t41.8
by
with dry
of about 75 %.
by GLC on a 400 x P-AW 80-100 mesh.
ppm (CFC13 external
of J(F-P) = 33.8 cps.
at t4.4 ppm; t5.3 ppm; t6.3 ppm and
standard)
with a coupling
32.9 cps. The IR-spectrum
1490 m, 1415 vs, 1330 m, 1195 vs,
was warmed
The solid was separated
packed with 30% FS 1265 on chromosorb
The "F-NMR standard)
in a glass bulb containing
The reaction mixture
constant
shows absorptions
1145 vs,
of
at (cm-I):
820 m, 650 m, 600 s and
580 S. The mass spectrum
(70eV; m/e; % rel.int.):
219 (M') 43.8;
200 (K-F) 100; 184 (M-Cl) 28.8; 114 (CF3NP) 10.6; 101 (PC12) 15.4; 95 (CF2NP) 18.3; 85 (PFCl) 8.7; 69 (CF3) 11.5.
It shows metastable
peaks at: m/e 42, 92.5 and 105.5 for the transitions: 155 -
m/e 114 --+ 69;
120 and 184 -+ 139. The lg F-NMR of E shows two doublets,
pond to an a:b = 2:3 ratio;da
= t78.6
d, = t86.6
constant
ppm with a coupling
(CFC13 external curious C2F5NX
standard).
fact has already
No CF3-CF2
the coupling
consisting constant
the basic triplet
corres-
= 33.3
of J(CF3-P)
= 5 cps.
coupling
been described
(X = SF2, SC12, SO) compounds
plex triplet,
their intensities
ppm; J(CF2-P)
was observed;
in the literature
151. The 31P-NMR
of three quartets
cps and
this
for
shows a com-
at to.6 ppm,tl.5 ppm and t2.4 ppm;
for them is 5 cps. The coupling
ist 34.1 cps. The IR-spectrum
constant
for
shows absorptions
at (cm-'): 1475 m, 1450 s, 1420 m, 1335 VS, 1235 vs, 1145 m, 1110 m, 1050 m, 705 w, 630 sh, 600 S. The mass spectrum
(70eV; m/e; % rel.int.):
(M-cl) 13.5; 200 (M-CF3)
100; 184 (CF3NPC12)
101 (PC12) 8.5;85(PFCl)l2.8; peaks at: m/e 55.8, 92.5, m/e 130 +
85, 200 -
250 (M-F)' 4.9; 234
36.8; 130 (CF2NPC1)
69 (CF3) 12.8. It shows metastable
120, 145 and 160 for the transitions:
136, 200 -
155, 234 -
184 and 250 -
200.
7.1;
88
We thank the Fonds der Chemischen tion and the Deutsche in this work.
Forschungsgemeinschaft
W. Leidinger
the Alcoa
for financial
has a DAAD scholarship.
Dr. R. Geist for the GLC-MS-coupling G. Schilling
Industrie,
measurements
Foundasupport
- We also thank as well as Dr.
for the "P-NMR-spectra.
REFERENCES
1
G. Kldter,
W. Lutz, K. Seppelt
and W. Sundermeyer,
Chem. -89 (1977) 754; Angew.Chem.Int.Ed.Engl., 2
R.C. Kumar,
J.M. Shreeve,
3
R.A. De Marco,
4
J.8. Hynes, B.C. Bishop and L.A. Bigelow,
J.M.
J.Am.Chem.Soc.,
Shreeve,
J. Fluorine
Angew.
-16 (1977) 707.
-102 (1980) 4958. Chem., 1 (1971/72)
269 - 276.
417. 5
M. Lustig,
Inorg. Chem. 2 (1966) 1317.
Inorg. Chem. fi (1967)
JoumaZofFluorine Chemistry, 19 (1981/82) 85-88 0 Elsevier Sequoia S.A., Lawanne - Printed in the Netherlands Received: April 6, 1981
Synthesis
of
trichlorophosphazo-trifluoromethane
and
-pentafluoroethane
WALTER LEIDINGER
Department
and WOLFGANG
of Inorganic
D-6900 Heidelberg,
SUNDERMEYER+
Chemistry,
Im Neuenheimer
University
of Heidelberg,
Feld 27o,(Federal
Republic
of Germany)
SUMMARY The trichlorophosphazo could be obtained dichloroamines
INTRODUCTION
and phosphorous
the smallest
to nitrogen,
compounds
have been studied
perfluorinated
monomer in the
have not yet been prepared.
may have been the difficulty
easily
for preparing
polarities
relative
trichlorophosphazo
[1,2], CF3-NH2
to use the dichloroamines
to react the dichloroamines
CF3-NPC13
reason for this
lose HF to give the corresponding
It seemed reasonable of the different
compounds,
the free amines, which
As is known from the literature
as CF3-CF2-NH2
for a long time.
d-position
A probable
in obtaining
are the usual starting materials
chloride
and C2F5-N=PC13 perfluoroalkyl
trichloride.
(2) = with fluorine
(1) and C2F5-NPC13
compounds.
CF3-N=PC13
the corresponding
AND RESULTS
Trichlorophosphazo However,
compounds
by reacting
of N-Cl and P-Cl bonds with phosphorous
as well
nitriles.
instead.
Because
[31, we decided
pentachloride
when
should be eliminated. cf<#
&-1, c1 RF-CF2-N
? +
' Cl RF = F, CF3 +Autkor
to
wkm
correspomkme
Lpc4cc) 3
---+RF-CF2-N=PC13
Cl' I, 2 = = should be addressed.
+ Cl2
86 It has been reported ween FC(O)NC12 during
[3] that no reaction was observed
and chlorinating
our experiments
we observed
and PC15, which was catalysed were poor. The main
reaction
to form the azocompound, Accordingly, amine to interact PC18 we obtained fluoroethane
agents
a side reaction
by W-light.
between
The yields
was the reduction
CFS-N=N-CFS
bet-
(PC13, PC15, A12C16);
however,
CFS-NC12
obtained
of the dichloroamine
[41.
it was thought
convenient
with a reagent
susceptible
to allow the dichloroto oxidation.
the trichlorophosphazo-trifluoromethane
Thus using
and -penta-
in high yields.
RF-CF2-NC12
+
B
2 PC18
RF-CF2-N=PClS
RF = F, CF8
Both compounds They hydrolyse
PC15
I, 2 = =
are colourless
very rapidly
1 and ? were confirmed
+
liquids under normal conditions.
and decompose
by IR, I'F-NMR,
above
31P-NMR
105'C. Structures and mass spectro-
metry.
EXPERIMENTAL
The IR-spectra
were recorded
on a Perkin-Elmer
the lg F-NMR on a JEOL C 60 HL; the 31P-NMR spectrometer
and the mass spectra
The dichloroamines sulfurdifluorides extremely
RF-CF2-NSF2
RF- CF2-NSC12, distillation.
distillation.
with Cl-F in CF3C1.
to separate
the crude dichloroamines
PC15 at -4O'C and afterwards were obtained
by the reaction
from commercial
of the imido-
They must be
of SF4 (from their preparation)
which was difficult Therefore
on a BRUKER HFX-90
on a VARIAN MAT CH7.
were obtained
pure, since traces
457 spctrometer;
with mercury. sources
gave
by 'trap to trap' were shaken with
Other starting
and purified
materials
by drying
or
a7 General
procedure:
0.05 mol dichloroamine 0.1 mol phosphorous
was condensed
trichloride.
slowly from -196'C to -1OO’C and stirred l/2 h until a precipitate filtering
in the absence
ice. The crude product The pure compounds 0.2 cm column
was formed. of air while
(filtrate)
were obtained
amounted
the filtrate
to a yield
after separation
The 31P-NMR
constant
shows a quartet
+ 7.3 ppm (H3P04 external J(P-CF3)=
at this temperature
cooling
of & shows a doublet
with a coupling
for
at t41.8
by
with dry
of about 75 %.
by GLC on a 400 x P-AW 80-100 mesh.
ppm (CFC13 external
of J(F-P) = 33.8 cps.
at t4.4 ppm; t5.3 ppm; t6.3 ppm and
standard)
with a coupling
32.9 cps. The IR-spectrum
1490 m, 1415 vs, 1330 m, 1195 vs,
was warmed
The solid was separated
packed with 30% FS 1265 on chromosorb
The "F-NMR standard)
in a glass bulb containing
The reaction mixture
constant
shows absorptions
1145 vs,
of
at (cm-I):
820 m, 650 m, 600 s and
580 S. The mass spectrum
(70eV; m/e; % rel.int.):
219 (M') 43.8;
200 (K-F) 100; 184 (M-Cl) 28.8; 114 (CF3NP) 10.6; 101 (PC12) 15.4; 95 (CF2NP) 18.3; 85 (PFCl) 8.7; 69 (CF3) 11.5.
It shows metastable
peaks at: m/e 42, 92.5 and 105.5 for the transitions: 155 -
m/e 114 --+ 69;
120 and 184 -+ 139. The lg F-NMR of E shows two doublets,
pond to an a:b = 2:3 ratio;da
= t78.6
d, = t86.6
constant
ppm with a coupling
(CFC13 external curious C2F5NX
standard).
fact has already
No CF3-CF2
the coupling
consisting constant
the basic triplet
corres-
= 33.3
of J(CF3-P)
= 5 cps.
coupling
been described
(X = SF2, SC12, SO) compounds
plex triplet,
their intensities
ppm; J(CF2-P)
was observed;
in the literature
151. The 31P-NMR
of three quartets
cps and
this
for
shows a com-
at to.6 ppm,tl.5 ppm and t2.4 ppm;
for them is 5 cps. The coupling
ist 34.1 cps. The IR-spectrum
constant
for
shows absorptions
at (cm-'): 1475 m, 1450 s, 1420 m, 1335 VS, 1235 vs, 1145 m, 1110 m, 1050 m, 705 w, 630 sh, 600 S. The mass spectrum
(70eV; m/e; % rel.int.):
(M-cl) 13.5; 200 (M-CF3)
100; 184 (CF3NPC12)
101 (PC12) 8.5;85(PFCl)l2.8; peaks at: m/e 55.8, 92.5, m/e 130 +
85, 200 -
250 (M-F)' 4.9; 234
36.8; 130 (CF2NPC1)
69 (CF3) 12.8. It shows metastable
120, 145 and 160 for the transitions:
136, 200 -
155, 234 -
184 and 250 -
200.
7.1;
88
We thank the Fonds der Chemischen tion and the Deutsche in this work.
Forschungsgemeinschaft
W. Leidinger
the Alcoa
for financial
has a DAAD scholarship.
Dr. R. Geist for the GLC-MS-coupling G. Schilling
Industrie,
measurements
Foundasupport
- We also thank as well as Dr.
for the "P-NMR-spectra.
REFERENCES
1
G. Kldter,
W. Lutz, K. Seppelt
and W. Sundermeyer,
Chem. -89 (1977) 754; Angew.Chem.Int.Ed.Engl., 2
R.C. Kumar,
J.M. Shreeve,
3
R.A. De Marco,
4
J.8. Hynes, B.C. Bishop and L.A. Bigelow,
J.M.
J.Am.Chem.Soc.,
Shreeve,
J. Fluorine
Angew.
-16 (1977) 707.
-102 (1980) 4958. Chem., 1 (1971/72)
269 - 276.
417. 5
M. Lustig,
Inorg. Chem. 2 (1966) 1317.
Inorg. Chem. fi (1967)