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Photolytic rearrangement of phosphorus azide : evidence for a transient metaphosphonimidate.
Tetrahedron Letter8 Vol. 21, pp 5015 - 5010 @Per-n Prese Ltd. 1980. Printed In Great Britain
0040-4059/80/1222-5015$02.00/O
PHOTOLYTIC REARRANGEMENT OF PHOSPHORUS AZIDE : EVIDENCE FOR A TRANSIENT METAPHOSPHONIMIDATE.
Guy BERTRAND *, Jean-Pierre MAJORAL -,
Antoine BACEIREDO *
* Laboratoire des Organom?Xalliques,ERA 829, Universite Paul Sabatier, 118 route de Narbonne, 31062 Toulouse Cedex France. x* Laboratoire des Heterocycles du Phosphore et de l'Azote, Universite Paul Sabatier 118 route de Narbonne, 31062 Toulouse Cedex France.
Photolysis of the oxide of diphenylphosphineazide gives rise to a transient metaphosphonimidate,a new tricoordinated pentavalent phosphorus compound. Evidence for this species was given by trapping reactions on a variety of substrates.
Although chemistry of unusually hybridized phosphorus compounds has been the subject of one of the most exciting areas in the last ten years, only few papers report investigations on tricoordinatedpentavalent phosphorus derivatives (l-8) (l-15). --
(N-R
RzN-P* N-R
S
//N-R
R-P& %NR
R2N-p\
CR2
(1)
(1) 0
R,N-Pfi +N-R
R-P<
S
S
(4)
R-p+’
R-P+ *0
%R2
0
Compounds (1) and (2) were found to be stable (Im5) but most of these phosphorus entities have a very short lifetime. They have been postulated as synthetic intermediates __ or caracterized by trappingwithdethylenic ketones (2) (13) methanol (1) (14-15) (3-5)
P2)
or amines (8) (16). Here we wish to report photolysis of the oxide of diphenylphosphineazide (2) which leads univoqually to the metaphosphonimidate(IO), a new tricoordinatedpentavalent phosphorus compound. Note that this type of rearrangement-migration - nitrogen loss-is the carbon series (17).
//O
g2p\
N3
hu -N2
5015
wellknown in
5016
Compound trapping
(2) was irradiated
overnight
agent or with an excess of alcohols, Thus photolysis
head to tail dimerization
of (2) without
at 2537 i, in benzene,
diols, amines,
trapping
in the absence
methyliodide,
epox$de
agent gave phosphodiazetidine
of the metaphosphonimidate
(10) in quantitative -
of
or diene.
(ll) (18) by
yield.
0
I
hv (9)
S31P = + 6 ppm
O,, /N\ //O
-$-+
0
,P\N/P,
(11)
0
m.p = 290 "C
-
0 When (z)was (18) were obtained
irradiated
in the presence
by addition
of ROH on the phosphorus 0
(9)
hv RIM
of alcohol
'
(methanol nitrogen
or ethanol)
double
631P = + 19 , 6 ppm
BP/NH0
(12)
g"OR
The cyclic derivative Howewer
(14) which -
(13) (lg) was obtained -
the use of ethylene
is slowly converted
of the reaction
glycol allowed
to dioxaphospholane
(14) to (15) is temperature -
-
OH
(l2)
bond of (l0)
m.p = 101 "C 105 "C
pinacol.
esters
when photolysis
us to caracterize
, R = CH3 , R = C2H5
was carried monoaddition
out with product
(l5) (20). Note that the rate enhancement
sensitive.
0
7H
&31P = t 28,7 ppm
ZP
0
I
(13) (9)
1
o>P<;OH
LL
0
OH
;>p
-0NH2
OH
(15)
(14) h31P = +19 , 8 ppm Two competitive diate
(10) with formation -
ding to compound
reactions
occured with aniline
of (16) (21) and aminolysls -
(17) (22). This second reaction -
hv (9)
: addition of amine on the interme-
0Lp/NHO 0'
'NH0 (16)
0NH2
-r
1
02P-NH0 II 0
631P = t 19 ppm m.p = 242-244
(17) -
631P = t 38,4 ppm
of the starting
is self catalysed
>
O-
"C
phosphorus
by the amine
azide (23).
,31P = t 8 ,5 ppm
lea-
5017
Phosphorus do phenyl
species
(10) reacts also with methyl
(methylphenyl)amino
hv (9)
phosphine
0 01 'P \N' 0 o//
s-
ICH3
iodide
leading to the oxide of io-
(18) -
‘CH
A31P = t 31 ppm = 11,9 Hz
JP-N-CH3
3
(18) -
In order to provide evidence the presence
of propylene
peak at 30,8 ppm which (20) (23) and another vg
for a ring insertion
71
oxide."' P n.m.r spectroscopy
can be attributed complex
reaction,
(2) was irradiated
showed two groups of signals
to 2-oxo-2-phenyl-1,3,2-oxazaphospholanes
signal at + 18,6 ppm which
is probably
in
: a wide (19) and -
due to acyclic
derivati,
(21) and (22) -
0\ /0 HPIN 3 0
B \/
t
0
HP\ O
Y
0
; (19) -
A
(20)
hu >
(9) &
0lp/NHO
0,p/NHO
t
Ofi 'OCH=CHMe
Ofi 'O-C=CH2
I
Me (11) It is interesting
(22)
to note that no trapping
reaction
occurs
in the presence
of
dimethylbutadiene (II) -
r (9) A --L
2t2
These preliminary this tricoordinated
in the tetracoordinated by low temperature stabilization
results
pentavalent
indicate
phosphorus
derivative.
31P n.m.r
2t4
or
that the phosphorus
derivative
Attemptsto
spectroscopy
of this type of compound
adducts
nitrogen
double bond of
(10) has a marked polar character
caracterize
this tricoordinated
have so far been unsuccessfull.
with bulky substituents
species( -10)
Efforts
are underway.
as
towards
5016
1 E. NIECKE, (1974).
W. FLICK, Angew.
Chem. 3,
128, (1974)
; Angew Chem. Int. Ed. Engl., g,
* O.J. SCHERER, N. KUHN, Chem. Ber. 107, 2123, 1974 ; O.J. SCHERER, Engl. 13, 811, (1974). 86, 899 (1974) ; Angew. Chem. 1nt.m. 3 L.N. MARKOVSKI,
V.O. ROMANENKO,
4 E. NIECKE and D.A. WILBREDT, 199 (1978).
A.V. RUBAN, Synthesis
Angew.
N. KUHN, Angew.
134,
Chem.,
811 (1979).
Chem. 90, 209 (1978)
; Angew. Chem. Int. Ed. Engl. 17,
5 E. NIECKE and D.A. WILBREDT Chem. Ber. 113, 1549 (1980) 6 S. TRIPPETT,
J. Chem. Sot. 4731 (1962).
7 B.K. ATHAWALE,
J.B. CHATTOPADHYAYA
a J. REBECK and F. GAVINA, ' E.W. CRUNDEN lo P.S. TAYLOR "
and A.V.R.
RAO Indian J. Chem. 2,
J. Amer. Chem. Sot., 97,
812 (1975).
1591 (1975).
and R.F. HUDSON J. Chem. Sot. 3591 (1962). and F.H. WESTHEIMER,
A.F. GERRARD
J. Amer. Chem. Sot. 87, 553, 1965.
and N.K. HAMER, J. Chem. Sot. B, 539, (1968)
; 369 (1969).
l2 D.F. HEATH, J. Chem. Sot. 3796 (1956). 13
See for ex M. REGITZ Angew. Chem., 8_7, 259, 1975 ; Angew. Chem. 1975 ; h. ECKES and M. REGITZ, Tetrahedron Letters, 447 (1975) Ann., 1766 (1977).
l4 M. J.P. HARGER, 15 16
J. WISEMAN
20
and F.H. WESTHEIMER,
edited by W. LWOWSKI,
la MICHAELIS, 19
23
and F.H. WESTHEIMER,
Interscience
Publishers
(1974). J. Amer. Chem. Sot. 2,
1970.
M. REVEL, M. BON and J. NAVECH, C.R. Acad. Sci., 274, C, 430 (1972). M. REVEL and J. NAVECH,
C.R. Acad. Sci., 275, C, 1451 (1972).
J.V. PUSTINGER
B.B. HUNT and B.C. SAUNDERS, M. REVEL, J.P. MAJORAL
and J. STROBEL,
and J. NAVECH,
J. DEVILLERS,
M. CORNUS, ibid. 2, 211 (1974).
3. DEVILLERS,
(Received
J. ROUSSEL,
in Franoe
3. Chem. Eng. Data 2, 167 (1964).
J. Chem. Sot., 2413 (1957).
R.A. BALDWIN and R.M. WASHBURN,
24
J. Amer. Chem. Sot., 9&, 4262,
Ann. 407, 290, 1915.
21 M.L. NIELSEN, 22
3. Chem. Sot. 2605, (1974).
see for ex : C.H. CLAPP, A. SATTERTHWAITE 6873 (1975).
17*Nitrene<
Int. Ed. Engl. 14, 222,
; M. HEYOT ana KREGITZ,
Colloque
Greco Phosphore,
J. Org. Chem. 30,
3. ROUSSEL
and J. NAVECH,
J. NAVECH and R. BURGADA,
29 September
1980)
?ennes, mai 1980.
3860, (1965). Org. Magn. Reson., 5, 205 (1974)
;
Org. Magn. Reson., 5, 511 (1973).
0040-4059/80/1222-5015$02.00/O
PHOTOLYTIC REARRANGEMENT OF PHOSPHORUS AZIDE : EVIDENCE FOR A TRANSIENT METAPHOSPHONIMIDATE.
Guy BERTRAND *, Jean-Pierre MAJORAL -,
Antoine BACEIREDO *
* Laboratoire des Organom?Xalliques,ERA 829, Universite Paul Sabatier, 118 route de Narbonne, 31062 Toulouse Cedex France. x* Laboratoire des Heterocycles du Phosphore et de l'Azote, Universite Paul Sabatier 118 route de Narbonne, 31062 Toulouse Cedex France.
Photolysis of the oxide of diphenylphosphineazide gives rise to a transient metaphosphonimidate,a new tricoordinated pentavalent phosphorus compound. Evidence for this species was given by trapping reactions on a variety of substrates.
Although chemistry of unusually hybridized phosphorus compounds has been the subject of one of the most exciting areas in the last ten years, only few papers report investigations on tricoordinatedpentavalent phosphorus derivatives (l-8) (l-15). --
(N-R
RzN-P* N-R
S
//N-R
R-P& %NR
R2N-p\
CR2
(1)
(1) 0
R,N-Pfi +N-R
R-P<
S
S
(4)
R-p+’
R-P+ *0
%R2
0
Compounds (1) and (2) were found to be stable (Im5) but most of these phosphorus entities have a very short lifetime. They have been postulated as synthetic intermediates __ or caracterized by trappingwithdethylenic ketones (2) (13) methanol (1) (14-15) (3-5)
P2)
or amines (8) (16). Here we wish to report photolysis of the oxide of diphenylphosphineazide (2) which leads univoqually to the metaphosphonimidate(IO), a new tricoordinatedpentavalent phosphorus compound. Note that this type of rearrangement-migration - nitrogen loss-is the carbon series (17).
//O
g2p\
N3
hu -N2
5015
wellknown in
5016
Compound trapping
(2) was irradiated
overnight
agent or with an excess of alcohols, Thus photolysis
head to tail dimerization
of (2) without
at 2537 i, in benzene,
diols, amines,
trapping
in the absence
methyliodide,
epox$de
agent gave phosphodiazetidine
of the metaphosphonimidate
(10) in quantitative -
of
or diene.
(ll) (18) by
yield.
0
I
hv (9)
S31P = + 6 ppm
O,, /N\ //O
-$-+
0
,P\N/P,
(11)
0
m.p = 290 "C
-
0 When (z)was (18) were obtained
irradiated
in the presence
by addition
of ROH on the phosphorus 0
(9)
hv RIM
of alcohol
'
(methanol nitrogen
or ethanol)
double
631P = + 19 , 6 ppm
BP/NH0
(12)
g"OR
The cyclic derivative Howewer
(14) which -
(13) (lg) was obtained -
the use of ethylene
is slowly converted
of the reaction
glycol allowed
to dioxaphospholane
(14) to (15) is temperature -
-
OH
(l2)
bond of (l0)
m.p = 101 "C 105 "C
pinacol.
esters
when photolysis
us to caracterize
, R = CH3 , R = C2H5
was carried monoaddition
out with product
(l5) (20). Note that the rate enhancement
sensitive.
0
7H
&31P = t 28,7 ppm
ZP
0
I
(13) (9)
1
o>P<;OH
LL
0
OH
;>p
-0NH2
OH
(15)
(14) h31P = +19 , 8 ppm Two competitive diate
(10) with formation -
ding to compound
reactions
occured with aniline
of (16) (21) and aminolysls -
(17) (22). This second reaction -
hv (9)
: addition of amine on the interme-
0Lp/NHO 0'
'NH0 (16)
0NH2
-r
1
02P-NH0 II 0
631P = t 19 ppm m.p = 242-244
(17) -
631P = t 38,4 ppm
of the starting
is self catalysed
>
O-
"C
phosphorus
by the amine
azide (23).
,31P = t 8 ,5 ppm
lea-
5017
Phosphorus do phenyl
species
(10) reacts also with methyl
(methylphenyl)amino
hv (9)
phosphine
0 01 'P \N' 0 o//
s-
ICH3
iodide
leading to the oxide of io-
(18) -
‘CH
A31P = t 31 ppm = 11,9 Hz
JP-N-CH3
3
(18) -
In order to provide evidence the presence
of propylene
peak at 30,8 ppm which (20) (23) and another vg
for a ring insertion
71
oxide."' P n.m.r spectroscopy
can be attributed complex
reaction,
(2) was irradiated
showed two groups of signals
to 2-oxo-2-phenyl-1,3,2-oxazaphospholanes
signal at + 18,6 ppm which
is probably
in
: a wide (19) and -
due to acyclic
derivati,
(21) and (22) -
0\ /0 HPIN 3 0
B \/
t
0
HP\ O
Y
0
; (19) -
A
(20)
hu >
(9) &
0lp/NHO
0,p/NHO
t
Ofi 'OCH=CHMe
Ofi 'O-C=CH2
I
Me (11) It is interesting
(22)
to note that no trapping
reaction
occurs
in the presence
of
dimethylbutadiene (II) -
r (9) A --L
2t2
These preliminary this tricoordinated
in the tetracoordinated by low temperature stabilization
results
pentavalent
indicate
phosphorus
derivative.
31P n.m.r
2t4
or
that the phosphorus
derivative
Attemptsto
spectroscopy
of this type of compound
adducts
nitrogen
double bond of
(10) has a marked polar character
caracterize
this tricoordinated
have so far been unsuccessfull.
with bulky substituents
species( -10)
Efforts
are underway.
as
towards
5016
1 E. NIECKE, (1974).
W. FLICK, Angew.
Chem. 3,
128, (1974)
; Angew Chem. Int. Ed. Engl., g,
* O.J. SCHERER, N. KUHN, Chem. Ber. 107, 2123, 1974 ; O.J. SCHERER, Engl. 13, 811, (1974). 86, 899 (1974) ; Angew. Chem. 1nt.m. 3 L.N. MARKOVSKI,
V.O. ROMANENKO,
4 E. NIECKE and D.A. WILBREDT, 199 (1978).
A.V. RUBAN, Synthesis
Angew.
N. KUHN, Angew.
134,
Chem.,
811 (1979).
Chem. 90, 209 (1978)
; Angew. Chem. Int. Ed. Engl. 17,
5 E. NIECKE and D.A. WILBREDT Chem. Ber. 113, 1549 (1980) 6 S. TRIPPETT,
J. Chem. Sot. 4731 (1962).
7 B.K. ATHAWALE,
J.B. CHATTOPADHYAYA
a J. REBECK and F. GAVINA, ' E.W. CRUNDEN lo P.S. TAYLOR "
and A.V.R.
RAO Indian J. Chem. 2,
J. Amer. Chem. Sot., 97,
812 (1975).
1591 (1975).
and R.F. HUDSON J. Chem. Sot. 3591 (1962). and F.H. WESTHEIMER,
A.F. GERRARD
J. Amer. Chem. Sot. 87, 553, 1965.
and N.K. HAMER, J. Chem. Sot. B, 539, (1968)
; 369 (1969).
l2 D.F. HEATH, J. Chem. Sot. 3796 (1956). 13
See for ex M. REGITZ Angew. Chem., 8_7, 259, 1975 ; Angew. Chem. 1975 ; h. ECKES and M. REGITZ, Tetrahedron Letters, 447 (1975) Ann., 1766 (1977).
l4 M. J.P. HARGER, 15 16
J. WISEMAN
20
and F.H. WESTHEIMER,
edited by W. LWOWSKI,
la MICHAELIS, 19
23
and F.H. WESTHEIMER,
Interscience
Publishers
(1974). J. Amer. Chem. Sot. 2,
1970.
M. REVEL, M. BON and J. NAVECH, C.R. Acad. Sci., 274, C, 430 (1972). M. REVEL and J. NAVECH,
C.R. Acad. Sci., 275, C, 1451 (1972).
J.V. PUSTINGER
B.B. HUNT and B.C. SAUNDERS, M. REVEL, J.P. MAJORAL
and J. STROBEL,
and J. NAVECH,
J. DEVILLERS,
M. CORNUS, ibid. 2, 211 (1974).
3. DEVILLERS,
(Received
J. ROUSSEL,
in Franoe
3. Chem. Eng. Data 2, 167 (1964).
J. Chem. Sot., 2413 (1957).
R.A. BALDWIN and R.M. WASHBURN,
24
J. Amer. Chem. Sot., 9&, 4262,
Ann. 407, 290, 1915.
21 M.L. NIELSEN, 22
3. Chem. Sot. 2605, (1974).
see for ex : C.H. CLAPP, A. SATTERTHWAITE 6873 (1975).
17*Nitrene<
Int. Ed. Engl. 14, 222,
; M. HEYOT ana KREGITZ,
Colloque
Greco Phosphore,
J. Org. Chem. 30,
3. ROUSSEL
and J. NAVECH,
J. NAVECH and R. BURGADA,
29 September
1980)
?ennes, mai 1980.
3860, (1965). Org. Magn. Reson., 5, 205 (1974)
;
Org. Magn. Reson., 5, 511 (1973).