Synthesis of 1,3,5,2λ5-triazaphosphinines by intramolecular cyclisation of (N-cyanophosphorimidoyl)guanidines and diguanidinophosphonium chlorides

Article abstract of DOI:10.1002/ejoc.200400217

The sodium phosphonium diylide Na[Ph₂P(NCN)₂] (3) - the first example of a stabilised phosphonium diylide - was synthesised by treatment of sodium diphenylphosphide with 2 equiv. of cyanic azide. Compound 3 reacted with alkyl- and ar

Full text of DOI:10.1002/ejoc.200400217

FULL PAPER
Synthesis of 1,3,5,2λ5-Triazaphosphinines by Intramolecular Cyclisation of
(N-Cyanophosphorimidoyl)guanidines and Diguanidinophosphonium Chlorides
Nicolas Inguimbert,[a] Lothar Jäger,*[b] Marc Taillefer,*[a] Matthias Biedermann,[b] and
Henri-Jean Cristau[a]
Dedicated to Professor Reinhard Schmutzler on the occasion of his 70th birthday
Keywords: Azides / Guanidines / P heterocycles / Phosphorus ylides
The sodium phosphonium diylide Na[Ph2P(NCN)2] (3) − the
first example of a stabilised phosphonium diylide − was syn-
1,3,5,2λ5-triazaphosphinines 11. The fusion of compound 10
allowed the formation of the same 1,3,5,2λ5-triazaphosphin-
thesised by treatment of sodium diphenylphosphide with 2 ines 11, along with the formation of NH4Cl or [PhNH3]Cl. A
equiv. of cyanic azide. Compound 3 reacted with alkyl- and
arylammonium salts [RRЈNH2]Cl {R = PhCH2, tBu, Ph; RЈ =
H; RRЈ = −[(CH2)2O(CH2)2]−}. Depending on the molar ratios
(1:1 or 1:2), (N-cyano-P,P-diphenylphosphorimidoyl)guanid-
ines Ph2P(NCN)N=C(NH2)NRRЈ (8) or diguanidinodiphenyl-
crystal structure analysis of 4-amino-6-morpholino-2,2-di-
phenyl-1,3,5,2λ5-triazaphosphinine (11a) revealed an almost
planar six-membered ring for the 1,3,5,2λ5-triazaphosphin-
ine template.
phosphonium chlorides [Ph2P{N=C(NH2)NRRЈ}2]Cl (10) were (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
formed. When molten, compounds 8 yielded new cyclic
Germany, 2004)
Introduction
RSO2: 2c] species.[5,6] While the first compound of the non-
stabilised type, Li[tBu2P(NH)2], was first synthesised in
1969,[7] synthetic strategies for the preparation of stabilised
diazadiylides have appeared only recently.[5,6]
Phosphonium ylides and diylides represent a well-charac-
terised and growing group of compounds known as valu-
able and versatile reagents in organic synthesis.[1] Homolo-
gous nitrogen compounds Ϫ azaylides 1 and diazadiylides
2 Ϫ have also been described (Scheme 1).[2Ϫ4] Depending
on their substituents RЈ (Scheme 1), the diazadiylides can
variously be non-stabilised (RЈ ϭ H, alkyl: 2a), semi-stabil-
ised (RЈ ϭ aryl, vinyl: 2b) or stabilised [RЈ ϭ CN, RC(O),
Generally, non- and semi-stabilised diazadiylides can be
prepared by lithiation of diaminophosphonium salts[2,3,8]
However, this synthetic route failed for the preparation of
stabilised diazadiylides 2c. In the literature, series of cyan-
amidophosphates such as Na3[PSO3Ϫn(NCN)n] (n
ϭ
1Ϫ3), or the phosphinates and phosphonates analogues,
like Na[Ph2P(O)NCN] or Na2[PhP(O)(NCN)2], are
described;[9Ϫ11] therefore the synthesis of M[Ph2P(NCN)2]
(3) as the first stabilised diazadiylide appeared promising.
With regard to their potential applications, special diaza-
diylides usually serve as chelating ligands in coordination
chemistry,[12] while the first examples of their applications
as organic synthesis tools were described recently. They can
be used, for instance, as precursors of primary and second-
ary amines[3] and have also afforded a new approach
Scheme 1. Phosphonium aza- and diazadiylides
[a]
´
Ecole Nationale Superieure de Chimie, Laboratoire de Chimie
Organique UMR 5076,
towards ketenimines Ph2CϭCϭNR [R
ϭ alkyl, Ph,
8, rue de l’Ecole Normale, 34296 Montpellier cedex 05, France
Fax: (internat.) ϩ 33-4-67144319
C(O)Ph] under very mild conditions.[13] We now report the
synthesis of sodium phosphonium diylide 3 and its reactiv-
ity towards substituted amine hydrochlorides [RRЈNH2]Cl
E-mail: taillefe@cit.enscm.fr
[b]
Fachbereich Chemie, University of Halle-Wittenberg,
06099 Halle/Saale, Germany
{R
ϭ
PhCH2, tBu, Ph; RЈ
ϭ
H; RRЈ
ϭ
Fax: (internat.) ϩ 49-345-5527028
E-mail: l.jaeger@chemie.uni-halle.de
Ϫ[(CH2)2O(CH2)2]Ϫ} to afford novel (phosphorimidoyl)-
4870
© 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
DOI: 10.1002/ejoc.200400217
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Synthesis of 1,3,5,2λ5-Triazaphosphinines
FULL PAPER
guanidines, which, when molten, underwent intramolecular observed a shift of the νas(NCN) vibrations to lower wave
cyclisation to yield 1,3,5,2λ5-triazaphosphinines.
numbers in the IR spectra.
Results and Discussion
Reactivity of the Sodium Phosphonium Diylides
Synthesis of Sodium Phosphonium Diylides
We had previously reported that the sodium phosphin-
ates Na[Ph2P(Y)NCN] [Y ϭ O (4a), S (4b)] and triphenyl-
phosphoranylidenecyanamide (Ph3PNCN, 5) reacted with
alkylamine or arylamine hydrochlorides to give the corre-
sponding phosphoryl-, phosphorothioyl- or phosphoniogu-
anidines 6Ϫ7 (Scheme 3).[15,16] The conditions applied de-
pend on the acidity of the ammonium salts used, their reac-
tivities decreasing in the order [PhNH3]Cl (pKa ϭ 4.63),
morpholinium hydrochloride (morph·HCl) (pKa ϭ 8.21),
benzylammonium chloride (pKa ϭ 9.33) and [tBuNH3]Cl
(pKa ϭ 10.83). The aryl and morpholinium compounds 4
rearranged even in acetonitrile at reflux, but in the case of
the alkylammonium salts the rearrangement took place
only at temperatures higher than the melting point of 4.
The reactions between dibromodiphenylphosphonium
bromide and amines represent a facile, efficient and versa-
tile synthetic route to direct precursors of non- or semi-
stabilised diazaylides, developed in our group.[3] This reac-
tion did not proceed, however, in the presence of the less
nucleophilic amides RC(O)NH2 in place of substituted am-
ines. On the other hand, the oxidation of phosphorus(iii)
compounds with azides (Staudinger reaction[2]), such as cy-
anic azide, is a very clean method by which to introduce an
imide function.[10,14] Treatment of phosphanes or phos-
phites with N3CN, for instance, yields the corresponding
monoylides R3PNCN or (RO)3PNCN in high yields under
mild conditions.
A new variant of the Staudinger reaction in which so-
dium diphenylphosphide reacts with 2 equiv. of cyanic
azide[6] has proved suitable for the synthesis of
Na[Ph2P(NCN)2] (3), the first example of a stabilised diaza-
diylide. To the best of our knowledge this is the first ex-
ample of a Staudinger reaction involving a phosphide. Un-
der an inert gas, a solution of N3CN in acetonitrile was
added at Ϫ30 °C to NaPPh2 in absolute THF. The reaction
was monitored by collection of the liberated nitrogen. After
recrystallisation,
(Scheme 2).
3 could be isolated in 80% yield
Scheme 3. Synthesis and selected examples of phosphoryl-, phos-
phorothioyl- and phosphonioguanidines 6Ϫ7[15,16]
Scheme 2. Synthesis of sodium phosphonium diylide 3
Similar behaviour may be expected for 3, but the reaction
with primary or secondary ammonium salts may be carried
out either with only one or with both NCN groups, yielding
phosphorus-functionalised mono- or diguanidines. At first
we studied the behaviour of 3 in ethanol towards 1 equiv.
of an ammonium salt [RNH3]Cl (R ϭ Ph, PhCH2) and
morpholine hydrochloride, respectively (Scheme 4). In order
to favour the 1:1 reaction we used a 30% excess of 3 and
monitored the reaction by 31P NMR spectroscopy. Reaction
conditions (temperature, time) varied according to the pKa
values of the ammonium salts used. At 20 °C with aniline
hydrochloride the reaction was complete after 24 h, whereas
in the case of benzylamine hydrochloride the reaction was
achieved after 72 h of heating at 78 °C. The resulting guani-
dines 8 were isolated in yields ranging from 36 to 66%
after recrystallisation.
Compound 3 is a member of the homologous series
[Ph2PY2Ϫn(NCN)n]Ϫ (Y ϭ O, S; n ϭ 1, 2).[10] In the 13C
NMR spectra, the NCN carbon resonances shifted to lower
fields in the order 3, 4a, 4b, because of the ability of the
cyanamido group to accept a greater part of the ionic
charge than one chalcogen atom in mixed chalcogeno-cyan-
imino compounds (Table 1). For the same reason, we also
Table 1. Selected spectroscopic data of 3, 4a and 4b
δ(13C) [ppm] νas(NCN) [cmϪ1
]
Ref.
Na[Ph2P(NCN)2] (3)
Na[Ph2P(O)NCN] (4a) 121.7
Na[Ph2P(S)NCN] (4b) 130.5
119.3
2190 vs, 2140 vs
2190 vs
2145 vs
[9]
[9]
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N. Inguimbert, L. Jäger, M. Taillefer, M. Biedermann, H.-J. Cristau
FULL PAPER
Synthesis of 1,3,5,2λ5-Triazaphosphinines
Different routes to 1,3,5,2λ5-triazaphosphinines have
been described in the literature,[17Ϫ20] but no intramolecular
cyclisation had been reported until now. Most of these com-
pounds were isolated from reactions between phosphorus
halides PCl5ϪnPhn (n ϭ 0Ϫ2) and dicyanamide or amidines,
resulting in 1,3,5,2λ5-triazaphosphinines bearing halogen
substituents at the ring carbon and phosphorus atoms.
These halotriazaphosphinines react with various nucleo-
philes such as amines,[21,22] phenols,[23] alcohols[24] or sulf-
ides[25] and yield the corresponding substituted hetero-
cycles. It is worth noting that only a few 4,6-diamino-
1,3,5,2λ5-triazaphosphinines have so far been synthesised.
For Ph2P(Y)NϭC(NH2)NHPh (Y ϭ O, S) in the crystal-
line state, intramolecular hydrogen bonds of the NϪH···Y
type between the NH2 group and the chalcogen atom have
been observed, resulting in the formation of a almost planar
six-membered ring.[26] A comparable geometry was also to
be expected for the N-cyanophosphorimidoyl homologues
Ph2P(NCN)NϭC(NH2)NHR 8aϪ8c; thus, an intramolecu-
lar nucleophilic attack of the ϪNH2 nitrogen atom on the
carbon atom of the NCN group should be possible.
Scheme 4. Synthesis of (N-cyano-P,P-diphenylphosphorimidoyl)-
guanidines 8
Nevertheless, primary ammonium chlorides such as tert-
butylamine hydrochloride, being slightly less acidic than
benzylamine hydrochloride, showed different behaviour.
After combination of 3 and [tBuNH3]Cl, the only product
isolated was compound 9 {[tBuNH3][Ph2P(NCN)2]}, in a
yield of 71%. The ammonium salt 9 is stable in boiling etha-
nol, and formation of the corresponding guanidine 8d could
not be established even after a few days (Scheme 5).
According to the same procedure as used for the con-
version of alkylammonium cyanophosphorylazanide
[RNH3][Ph2P(O)NCN] into the corresponding (diphenyl-
phosphoryl)guanidines 6,[13] we heated the ammonium salt
9 (Scheme 5) up to 185 °C in the absence of solvent for
25 min, and a rearrangement to 1,3,5,2λ5-triazaphosphinine
11e occurred. After purification by column chromatogra-
phy, we isolated 11e in a yield of 44%. The guanidine 8d
could not be clearly detected in the crude product but it
can reasonably be postulated as an intermediate in the ring-
closure reaction (Scheme 5). In support of this hypothesis,
heating of the guanidines 8aϪ8c up to 185 °C resulted in
the formation of 1,3,5,2λ5-triazaphosphinines 11aϪ11c,
which could be isolated in good yields, varying from 75 to
90%, after purification by column chromatography
(Scheme 7).
Scheme 5. Synthesis of ammonium salt 9 and 1,3,5,2λ5-triazaphos-
phinine 11e
In the presence of a sixfold excess of the ammonium salts
[RNH3]Cl at either 20 °C (R ϭ Ph) or 78 °C (R ϭ PhCH2
or morpholine hydrochloride, Scheme 6), on the other
hand, addition reactions on both NCN groups took place,
and diguanidinodiphenylphosphonium chlorides 10aϪ10c
could be isolated after recrystallisation in yields between 42
and 55% (Scheme 6). The reaction course was studied by
31P NMR spectroscopy. At first the resonance signal of the
monoguanidine 8 was observed, disappearing again after
formation of 10. As already discussed above, [PhNH3]Cl
reacts more rapidly (20 h, 25 °C) than [PhCH2NH3]Cl (10
d, 78 °C) because of the different basic strengths of the
related amines.
Scheme 7. Synthesis of the 1,3,5,2λ5-triazaphosphinines 11aϪ11c
starting from 8aϪ8c
The behaviour of the diguanidinodiphenylphosphonium
chlorides 10a and 10c at 185 °C is depicted in Scheme 8.
According to a differential thermal analysis, compound 10c
decomposed at its melting point (218Ϫ223 °C) with a mass
loss of 15.8%, corresponding to the evolution of aniline hy-
Scheme 6. Synthesis of diguanidinodiphenylphosphonium chlo-
rides 10
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Synthesis of 1,3,5,2λ5-Triazaphosphinines
FULL PAPER
drochloride and ammonium chloride, and produced 11c
and 11d in yields of 50 and 20%. The formation of two
different heterocycles (11c, 11d) can be understood by the
fact that the liberation of both ammonium chloride and
aniline hydrochloride gave the intermediates 8c and 12c,
thus cyclising to afford both the non-symmetrical N-mono-
phenyl and the symmetrical N,NЈ-diphenyl derivatives.
Figure 1. Molecular structure of the 1,3,5,2λ5-triazaphosphinine
11a (H atoms are omitted for clarity)
˚
Table 2. Selected bond lengths [A] and angles [°] for compound 11a
P(1)ϪN(1)
P(1)ϪN(2)
P(1)ϪC(3)
P(1)ϪC(9)
N(1)ϪC(1)
N(2)ϪC(2)
N(3)ϪC(2)
N(3)ϪC(1)
1.607(2) N(4)ϪC(2)
1.610(2) N(5)ϪC(1)
1.797(2)
1.346(3)
1.329(3)
1.800(3)
1.343(3) N(4)ϪC(18a)
1.339(3) N(4)ϪC(15a)
1.338(3) N(4)ϪC(18b)
1.345(3) N(4)ϪC(15b)
1.480(4)
1.481(5)
1.475(5)
1.485(4)
N(1)ϪP(1)ϪN(2) 112.90(10) N(1)ϪC(1)ϪN(3)
N(1)ϪP(1)ϪC(3) 107.45(11) N(3)ϪC(2)ϪN(2)
N(2)ϪP(1)ϪC(3) 111.04(11) N(3)ϪC(2)ϪN(4)
N(2)ϪP(1)ϪC(9) 108.98(12) N(2)ϪC(2)ϪN(4)
N(1)ϪP(1)ϪC(9) 110.84(11) C(2)ϪN(4)ϪC(18a)
C(3)ϪP(1)ϪC(9) 105.38(11) C(2)ϪN(4)ϪC(15a)
128.3(2)
128.9(2)
115.1(2)
116.0(2)
121.3(3)
123.0(3)
C(1)ϪN(1)ϪP(1) 114.9(2)
C(2)ϪN(2)ϪP(1) 114.9(2)
C(2)ϪN(3)ϪC(1) 118.7(2)
N(5)ϪC(1)ϪN(1) 116.2(2)
N(5)ϪC(1)ϪN(3) 115.5(2)
C(18A)ϪN(4)ϪC(15a) 110.0(4)
C(2)ϪN(4)ϪC(18b)
C(2)ϪN(4)ϪC(15b)
123.4(3)
121.3(3)
C(18B)ϪN(4)ϪC(15b) 109.9(3)
Scheme 8. Synthesis of the 1,3,5,2λ5-triazaphosphinines 11aϪc
starting from diguanidinophosphonium chlorides 10aϪc and pos-
tulated intermediates
The phosphorus atom shown adopts a distorted tetra-
hedral geometry, with maximum and minimum angles
between
N(1)ϪP(1)ϪN(1)
[ϭ
112.90(10)°]
and
In the case of the morpholine-modified diguanidinodi-
phenylphosphonium chloride 10a, on the other hand, only
one outcome of the reaction is possible, because the forma-
tion of a carbodiimide corresponding with 12c is ruled out.
Therefore, exclusively one product (11a) can be expected
from this ring-closure reaction (Scheme 8).
C(3)ϪP(1)ϪC(9) [ϭ 105.38(11)°], respectively. The
P(1)ϪC(3) [ϭ 1.797(2) A] and P(1)ϪC(9) [ϭ 1.800(3) A]
˚
˚
bond lengths correspond with observed values for
P(4)ϪC(arom.).[34,35] The P(1)ϪN(1) [ϭ 1.607(2) A] and
˚
˚
P(1)ϪN(2) [ϭ 1.610(2) A] distances are somewhat longer
[34]
˚
than those expected for the PϭN bond type (ϭ 1.55 A),
but they are in good agreement with these distances meas-
ured in other triazaphosphinines such as 2,2-dichloro-4,6-
[26]
˚
bis(trifluoromethyl)- [1.616(2) A]
or 2,2-bis(diisopropyl-
Crystal and Molecular Structure of 11a
amino)-4,6-diphenyl-1,3,5,2λ5-triazaphosphinine [1.630(2)
[32]
˚
A].
The mean value for the endocyclic CϭN bond
˚
The molecular structure, the labelling scheme and selec- lengths was 1.341(3) A, which corresponded to those in py-
ted geometric parameters of 6-amino-4-morpholino-2,2-di- rimidines[32] and triazaphosphinines.[26Ϫ32] The P-heterocy-
phenyl-1,3,5,2λ5-triazaphosphinine (11a) are shown in Fig- cle is almost planar; the maximum deviations from the
ure 1 and Table 2; the crystallographic data and refinement mean plane (formed by the six ring atoms) amounting to
˚
˚
details are summarised in the Exp. Sect. Crystal structures 0.0829(5) A and Ϫ0.068(2) A for P(1) and N(1), respec-
of differently substituted 1,3,5,2λ5-triazaphosphinines have tively. Moreover, the exocyclic atoms N(4) and N(5) deviate
already been described in the literature.[27Ϫ33]
˚
only slightly from this plane [Ϫ0.094(2) and 0.003(3) A]
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N. Inguimbert, L. Jäger, M. Taillefer, M. Biedermann, H.-J. Cristau
FULL PAPER
2
4
˚
12.6 Hz, m-C), 131.0 (d, JP,C ϭ 9.6 Hz, o-C), 131.5 (d, JP,C
ϭ
and, at the same time, the C(1)ϪN(5) [ϭ 1.329(3) A] and
2.3 Hz, p-C), 133.1 (d, JP,C ϭ 129.3 Hz, ipso-C) ppm. FABϩ MS:
m/z (%) ϭ 289 (15). FABϪ MS: m/z (%) ϭ 265 (100). C14H10N4NaP
(288): calcd. C 58.37, H 3.50, N 19.45; found C 58.35, H 3.81,
N 19.13.
1
˚
˚
C(2)ϪN(4) [ϭ 1.346(3) A] bonds are shorter than expected:
2
3
[34]
C(sp )ϪN(sp ) ϭ 1.43 A. The ring atoms of the morph-
oline ring from C(15a/b) to C(18a/b) and O(1a/b) are dis-
ordered; both positions are split with occupation factors of
50%. Both rings have a chair conformation, which, how-
ever, are oppositely folded with dihedral angles
N(4)ϪC(15a/b)ϪC(16a/b)ϪO(1a/b) ϭ 60.2(7)°/Ϫ59.6(7)°.
Within the lattice the phosphinine molecules are held
General Procedure for the Synthesis of the (N-Cyano-P,P-diphenyl-
phosphorimidoyl)guanidines 8a؊c: A mixture of 3 (5 mmol) and the
corresponding amine hydrochloride (3.5 mmol) in dry ethanol
(20 mL) was placed in the reaction vessel. Reaction times and tem-
peratures depended on the amine hydrochloride (see below). The
reaction was monitored by 31P NMR spectroscopy. After com-
pletion of the reaction, the solvent was evaporated under vacuum,
and the oily residue was partitioned between water and chloroform.
The organic layer was separated and dried with Na2SO4. Filtration
and concentration, followed by recrystallisation of the crude prod-
uct in a minimal volume of acetonitrile, afforded the guanidines 8.
together
by
intermolecular
hydrogen
bonds
N(5)ϪH(1)···O(1a/b)Ј (1 Ϫ x, 0.5 ϩ y, 1.5 Ϫ z) with proton
donorϪacceptor distances N1···O(1a/b)Ј
ϭ
3.034(8)/
˚
2.908(9) A and angles N(5)ϪH(1)···O(1)Ј ϭ 166(2)/174(3)°.
Conclusion
NЈ-(N-Cyano-P,P-diphenylphosphorimidoyl)morpholine-4-carbox-
imidamide (8a): Reaction time: 6 h at 78 °C. Yield: 0.77 g,
2.2 mmol, 63%. White solid, m.p. 193Ϫ195 °C (acetonitrile). IR
(KBr): ν˜ ϭ 3420 (NH2), 3280 (NH2), 3180 (NH), 1635 (CϭN),
The sodium phosphonium diylide 3 is of special interest
as a precursor for new types of phosphorylated guanidines
8 and 10. This study complements the application of phos-
phorylated cyanamides as synthetic tools towards P-func-
tionalised guanidines.[15] Finally, the use of (N-cyanophos-
phorimidoyl)guanidines 8 and diguanidinophosphonium
chlorides 10 as a precursor for 1,3,5,2λ5-triazaphosphinines
11 represents an interesting alternative route to these heter-
ocycles. All these molecules, especially the 1,3,5,2λ5-triaza-
phosphinines 11, because they are 1,3,5-triazine analogues,
could find agricultural applications.[36]
2160 (CN) cmϪ1 31P NMR (CDCl3): δ ϭ 16.70 ppm. 1H NMR
.
(CDCl3): δ ϭ 3.61 (m, 4 H, CH2N), 3.68 (m, 4 H, CH2O), 6.5 (s,
2 H, NH2), 7.5 (m, 6 H, aromatic H), 7.8 (m, 4 H, aromatic H)
ppm. 13C NMR (CDCl3): δ ϭ 44.9 (CH2N), 66.3 (CH2O), 120.6
3
2
(CN), 128.7 (d, JP,C ϭ 13.2 Hz, m-C), 131.2 (d, JP,C ϭ 10.1 Hz,
1
4
o-C), 131.3 (d, JP,C ϭ 132.3 Hz, ipso-C), 132.0 (d, JP,C ϭ 2.5 Hz,
p-C), 157.2 (CϭN) ppm. FABϩ MS: m/z (%) ϭ 354 (100).
C18H20N5OP (353): calcd. C 61.18, H 5.70, N 19.81; found C 60.98,
H 5.75, N 19.72.
N-[Amino(benzylamino)methylene]-NЈ-cyano-P,P-dimethylphos-
phinimidic Amide (8b): Reaction time: 72 h at 78 °C. Yield: 0.46 g,
1.2 mmol, 36%. White solid, m.p. 155Ϫ156 °C (acetonitrile). IR
(KBr): ν˜ ϭ 3450 (NH2), 3305 (NH2), 3180 (NH), 2150 (CN), 1615
Experimental Section
(CϭN) cmϪ1 31P NMR (CDCl3): δ ϭ 17.2 ppm. 1H NMR
.
General Remarks: The starting materials were purchased from com-
mercial sources and were used without further purification, unless
mentioned otherwise. Acetonitrile was distilled from phosphorus
pentoxide, and tetrahydrofuran from sodium/benzophenone. Melt-
ing points are uncorrected. Fast atom bombardment (FAB) MS
was carried out with a JEOL JMS-DX 300 apparatus in a m-nitro-
benzyl alcohol matrix. 1H NMR spectra were recorded at
200 MHz. 13C NMR spectra were recorded at 50.3 MHz with use
of the JMOD pulse sequence. 31P NMR spectra were recorded at
80 MHz.
(CDCl3): δ ϭ 4.45 (d, J ϭ 5.6 Hz, 2 H, PhCH2), 6.05 (s, 2 H, NH2),
7.03 (br. s, 1 H, NH), 7.35 (m, 5 H, aromatic H), 7.4 (m, 6 H,
aromatic H), 7.8 (m, 4 H, aromatic H) ppm. 13C NMR (CDCl3):
δ ϭ 45.1 (PhCH2), 121.3 (CN), 127.0 (p-C), 127.2 (o-C), 128.4
3
(ipso-C), 128.5 (m-C), 128.5 (d, JP,C ϭ 13.2 Hz, m-C), 131.3 (d,
4
2JP,C ϭ 10.1 Hz, o-C), 131.8 (d, JP,C ϭ 2.8 Hz, p-C), 131.9 (d,
1JP,C ϭ 131.6 Hz, ipso-C), 158.7 (CϭN) ppm. FABϩ MS: m/z
(%) ϭ 374 (100). C21H20N5P (373): calcd. C 67.54, H 5.40, N 18.76;
found C 67.62, H 5.40, N 18.27.
N-[(Amino(anilino)methylene]-NЈ-cyano-P,P-dimethylphosphinimidic
Amide (8c): Reaction time: 24 h at 20 °C. Yield: 0.82 g, 2.31 mmol,
66%. White solid, m.p. 193Ϫ195 °C (acetonitrile). IR (KBr): ν˜ ϭ
Sodium Cyano (N-cyano-P,P-diphenylphosphorimidoyl)azanide (3):
A solution of cyanic azide (65 mmol) in dry acetonitrile (80 mL),
prepared by a known method,[14] was added at Ϫ30 °C to a stirred
solution of sodium diphenyl phosphide[37] (65 mmol) in THF
(80 mL) under nitrogen. After collection of about 90% of the
theoretical volume of N2 in a gas burette, the mixture was stirred
at 25 °C for 12 h to complete the reaction and to avoid residual
N3CN. Subsequently, the yellow solution was filtered through
Celite and the solvent was removed under reduced pressure. The
residual brown oil was taken up in 1,4-dioxane (30 mL). After
about 12 h at room temperature, the white solid obtained was fil-
tered off and dried under vacuum. It was analytically pure. Yield
14.99 g (52 mmol, 80%). White solid, m.p. 182Ϫ184 °C (dioxane).
3410 (NH2), 3300 (NH2), 3200 (NH), 2140 (CN), 1630 (CϭN)
1
cmϪ1
.
31P NMR (CDCl3): δ ϭ 16.8 ppm. H NMR (CDCl3): δ ϭ
6.5 (s, 2 H, NH2), 7.1 (t, J ϭ 7.2 Hz, 1 H, aromatic H), 7.4 (m, 2
H, aromatic H), 7.6 (m, 8 H, aromatic H), 7.7 (m, 4 H, aromatic
H), 9.3 (d, J ϭ 5.6 Hz, 1 H, NH) ppm. 13C NMR (CDCl3): δ ϭ
118.4 (CN), 121.3 (m-C), 123.7 (p-C), 128.7 (o-C), 128.8 (d, 2JP,C ϭ
7.5 Hz), 130.9 (d, 3JP,C ϭ 9.8 Hz), 131.8 (d, 1JP,C ϭ 129.8 Hz, ipso-
4
C), 132.0 (d, JP,C ϭ 2.6 Hz), 138.4 (ipso-C), 158.9 (CϭN) ppm.
FABϩ MS: m/z (%) ϭ 360 (100). C20H18N5P (359): calcd. C 66.84,
H 5.04, N 19.43; found C 66.42, H 5.44, N 18.22.
IR (KBr): ν˜ ϭ 2190, 2140 (NCN) cmϪ1
.
31P NMR ([D6]DMSO):
tert-Butylammonium Cyano(N-cyano-P,P-diphenylphosphorimidoyl)-
azanide (9): A mixture of 3 (10 mmol) and tert-butylammonium
3
δ ϭ 19.23 ppm. 15N NMR ([D6]DMSO): δ ϭ Ϫ219.27 (d, JN,P
ϭ
2.32 Hz, CN), Ϫ339.45 (d, JN,P ϭ 29.5 Hz, CN) ppm. 1H NMR chloride (10 mmol) in dry ethanol (50 mL) was stirred at 25 °C for
1
([D6]DMSO): δ ϭ 7.4 (m, 4 H, aromatic H), 7.8 (m, 6 H, aromatic 20 h. The sodium chloride was removed by filtration, and the fil-
H) ppm. 13C NMR ([D6]DMSO): δ ϭ 119.3 (CN), 128.4 (d, 3JP,C ϭ
4874
trate was concentrated under vacuum, leaving a viscous colourless
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Eur. J. Org. Chem. 2004, 4870Ϫ4876

Synthesis of 1,3,5,2λ5-Triazaphosphinines
FULL PAPER
oil, which crystallised from acetonitrile. Yield: 2.4 g, 7.1 mmol,
heated at 180 °C under reduced pressure under nitrogen for 25 min.
71%. White solid, m.p. 169Ϫ170 °C (acetonitrile). IR (KBr): ν˜ ϭ After cooling, the colourless glass was dissolved in chloroform (15
3400 (NH2), 2180 (CN), 2160 (CN) cmϪ1
.
31P NMR (CDCl3): δ ϭ
mL) and this solution was concentrated in vacuo. The products
1
21.9 ppm. H NMR (CDCl3): δ ϭ 1.2 [s, 9 H, (CH3)3C]), 7.4 (m, 6 were purified as follows: Procedure a gave a mixture of two
H, aromatic H), 7.8 (m, 4 H, aromatic H) ppm. C18H22N5P (339): 1,3,5,2λ5-triazaphosphinines, which were separated by chromatog-
calcd. C 63.70, H 6.53, N 20.64; found C 62.79, H 6.34. N 20.29.
raphy on neutral alumina (eluent: ethyl acetate/methanol, 96:4).
Procedure b gave the 4-alkylamino(arylamino)-6-amino-2,2-di-
phenyl-1,3,5,2λ5-triazaphosphinines, which were purified by recrys-
tallisation from the solvent given in parentheses.
General Procedure for the Synthesis of the Diguanidinodiphenylphos-
phonium Chlorides 10a؊c: A mixture of diylide 3 (2.5 mmol) and
the corresponding amine hydrochloride (15 mmol) was stirred in
dry ethanol (50 mL). Reaction times and temperatures depended
on the amine hydrochloride (see below). The reaction was moni-
tored by 31P NMR, and after full disappearance of the diylide 3,
the reaction was quenched by concentration under vacuum, the oily
residue then being taken up in H2O and CHCl3. The organic layer
was separated, washed with water and dried (Na2SO4). Filtration
and concentration, followed by recrystallisation of the crude prod-
uct in a minimal volume of ethyl acetate, afforded the guanidines
10aϪc.
6-(Morpholin-4-yl)-2,2-diphenyl-1,3,5,2λ5-triazaphosphinine-4-
amine (11a): Yield: 0.353 g, 1.0 mmol, 41% (Procedure a); 0.79 g,
2.25 mmol, 90% (procedure b). Colourless solid, m.p. 165Ϫ166 °C
(ethyl acetate). IR (KBr): ν˜ ϭ 3380 (NH2), 3295 (NH), 3185 (NH),
1
1630 (CϭN) cmϪ1
.
31P NMR (CDCl3): δ ϭ 33.06 ppm. H NMR
(CDCl3): δ ϭ 3.67 (m, 4 H, CH2N), 3.81 (m, 4 H, CH2O), 4.89 (d,
J ϭ 3.4 Hz, 2 H, NH2), 7.5 (m, 6 H, aromatic H), 7.7 (m, 4 H,
aromatic H) ppm. 13C NMR (CDCl3): δ ϭ 43.7 (d, 4JP,C ϭ 2.4 Hz,
3
CH2N), 66.9 (CH2O), 128.4 (d, JP,C ϭ 12.9 Hz, m-C), 130.8 (d,
4
2JP,C ϭ 10.0 Hz, o-C), 131.6 (d, JP,C ϭ 2.7 Hz, p-C), 134.0 (d,
Bis{[amino(morpholino-4-yl)methylene]amino}diphenylphosphonium
Chloride (10a): Reaction time 15 h at 78 °C. Yield: 0.54 g,
1.13 mmol, 45%. White solid, m.p. 199Ϫ201 °C (ethyl acetate). IR
(KBr): ν˜ ϭ 3490 (NH2), 3410 (NH2), 3370 (NH2), 3120 (NH), 1640
2
1JP,C ϭ 127.8 Hz, ipso-C), 164.8 (d, JP,C ϭ 2.5 Hz, CϭN), 167.1
(CNH2) ppm. FABϩ MS (NBA): m/z (%)
ϭ 354 (100).
C18H20N5OP (353): calcd. C 61.8, H 5.70, N 19.81; found C 61.05,
H 5.74, N 19.35.
(CϭN) cmϪ1 31P NMR (CDCl3): δ ϭ 9.31 ppm. 1H NMR
.
(CDCl3): δ ϭ 3.7 (m, 8, CH2N), 3.8 (m, 8 H, CH2O), 6.6 (s, 4 H,
NH2), 7.45 (m, 6 H, aromatic H), 7.7 (m, 4 H, aromatic H) ppm.
13C NMR (CDCl3): δ ϭ 43.5 (CH2N), 66.3 (CH2O), 128.9 (d,
X-ray Crystallographic Study of 6-(Morpholin-4-yl)-2,2-diphenyl-
1,3,5,2λ5-triazaphosphinine-4-amine (11a): Colourless, transparent
prisms were grown from ethyl acetate. The X-ray measurement was
performed with a STOE STADI4 diffractometer with use of graph-
2
3JP,C ϭ 12.9 Hz, m-C), 131.1 (d, JP,C ϭ 9.9 Hz, o-C), 131.3 (d,
1JP,C ϭ 132.0 Hz, ipso-C), 131.9 (d, 4JP,C ϭ 2.3 Hz, p-C), 157.2 (Cϭ
˚
ite-monochromatised Mo-Kα radiation (λ ϭ 0.71073 A) at room
N) ppm. FABϩ MS: m/z (%)
ϭ Ϫ
441 (100) [Mϩ ClϪ].
temperature. The structure was solved by direct methods
(SHELXS-86)[38] and refined with anisotropic displacement param-
eters for all non-H-atoms on F2 (SHELXL-93).[39] All H-atoms
were placed at their idealised positions; their parameters were re-
fined isotropically according to the riding model. For the plot of
the molecular structure the program DIAMOND[40] was used.
C18H22N5OP (Mr ϭ 353.36); crystal dimensions: 0.46 ϫ 0.36 ϫ
C22H30ClN6O2P (476.5): calcd. C 55.40, H 6.34, N 17.62; found C
54.98, H 6.37, N 17.35.
Bis{[amino(benzylamino)methylene]amino}diphenylphosphonium
Chloride (10b): Reaction time: 10 d at 78 °C. Yield: 0.55 g,
1.1 mmol, 42%. White solid, m.p. 194Ϫ195 °C (ethyl acetate). IR
(KBr): ν˜ ϭ 3475 (NH2), 3440 (NH2), 3260 (NH2), 3130 (NH), 1630
0.27 mm; monoclinic, P21/c; a ϭ 8.889(1), b ϭ 13.018(1), c ϭ
(CϭN) cmϪ1 31P NMR (CDCl3): δ ϭ 9.44 ppm. 1H NMR
.
3
˚
˚
16.925(2) A, β ϭ 104.03(1)°, Z ϭ 4, V ϭ 1900.1(3) A , ρcalcd.
ϭ
(CDCl3): δ ϭ 4.53 (d, J ϭ 5.81 Hz, 4 H, CH2Ph), 4.87 (s, 4 H,
NH2), 7.4 (m, 16 H, aromatic H), 8.3 (sl, 2 H, NH) ppm. 13C NMR
([D6]methanol): δ ϭ 46.2 (CH2), 128.2 (o-C), 128.3 (p-C), 129.7 (m-
1.235 g/cm3, T ϭ 293(2) K, F(000) ϭ 744; intensities measured:
6664 (2.00° Ͻ θ Ͻ 24.95°); independent reflections: 3332 (Rint
ϭ
0.0203); observed reflections: 2555 [I Ͼ 2σ(I)]; R1/wR2/S (observed
data): 0.436/0.1076/1.115; R1/wR2/S (all data): 0.0646/0.1268/1.111;
maximum residual electron density was between Ϫ0.280 and 0.200
3
2
C), 129.8 (d, JP,C ϭ 12.8 Hz, m-C), 132.6 (d, JP,C ϭ 10.1 Hz, o-
C), 132.8 (d, 1JP,C ϭ 131.9 Hz, ipso-C), 133.2 (d, 4JP,C ϭ 2.9 Hz, p-
C), 140.8 (ipso-C), 160.1 (CϭN) ppm. FABϩ MS: m/z (%) ϭ 481
(100) [Mϩ Ϫ ClϪ]. C28H30ClN6P (516.5): calcd. C 66.05, H 5.85,
N 16.26; found C 65.17, H 6.13, N 16.25.
e·AϪ3. CCDC-221378 contains the supplementary crystallographic
˚
data for this paper. These data can be obtained free of charge at
www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge
Bis{[amino(anilino)methylene]amino}diphenylphosphonium Chloride
(10c): Reaction time: 25 h at 20 °C. Yield: 0.67 g, 1.4 mmol, 55%.
White solid, m.p. 222Ϫ223 °C (ethyl acetate). IR (KBr): ν˜ ϭ 3445
CB2 1EZ, UK; Fax: (internat.)
deposit@ccdc.cam.ac.uk].
ϩ 44-1223/336-033; E-mail:
(NH2), 3395 (NH2), 3295 (NH2), 3180 (NH), 1625 (CϭN) cmϪ1
.
N-Benzyl-2,2-diphenyl-1,3,5,2λ5-triazaphosphinine-4,6-diamine
(11b): Yield: 0.72 g, 1.95 mmol, 78% (Procedure b). Colourless
solid, m.p. 178Ϫ179 °C (dichloromethane). IR (KBr): ν˜ ϭ 3480
(NH2), 3265 (NH), 3100 (NH),1625 (CϭN), 1570, 1330 (PϭN)
31P NMR (CDCl3): δ ϭ 10.1 ppm. H NMR (CDCl3): δ ϭ 6.2 (br.
s, 4 H, NH2), 7.1 (m, 2 H, aromatic H), 7.3 (m, 4 H, aromatic H),
7.4 (m, 6 H, aromatic H), 7.7 (m, 6 H, aromatic H), 9.8 (d, J ϭ
1.6 Hz, 2 H, NH) ppm. 13C NMR (CDCl3): δ ϭ 121.9 (m-C), 124.3
1
cmϪ1 31P NMR (CDCl3): δ ϭ 33.28 ppm. 1H NMR (CDCl3): δ ϭ
.
4.54 (s, 2 H, CH2Ph), 5.54 (br. s, 2 H, NH2), 6.28 (br. s, 1 H, NH),
7.25 (m, 5 H, aromatic H), 7.46 (m, 6 H, aromatic H), 7.62 (m, 4
3
(p-C), 128.7 (o-C), 129.1 (d, JP,C ϭ 13.2 Hz, m-C), 130.7 (d,
2
1JP,C ϭ 132.2 Hz, ipso-C), 131.4 (d, JP,C ϭ 10.4 Hz, o-C), 132.5
4
(d, JP,C ϭ 2.9 Hz, p-C), 138.1 (ipso-C), 156.8 (CϭN) ppm. FABϩ
4
H, aromatic H) ppm. 13C NMR (CDCl3): δ ϭ 44.3 (d, JP,C
ϭ
MS: m/z (%) ϭ 453 (100) [Mϩ Ϫ ClϪ]. C26H26ClN6P (488.5): calcd.
2.7 Hz, CH2Ph), 126.7 (p-C), 127.4 (o-C), 128.3 (d, 3JP,C ϭ 12.9 Hz,
C 63.86, H 5.36, N 17.19; found C 63.54, H 5.28, N 16.97.
m-C), 128.4 (m-C), 130.9 (d, 2JP,C ϭ 10.1 Hz, o-C), 131.6 (d, 4JP,C ϭ
General Procedure for the Synthesis of the 2,2-Diphenyl-1,3,5,2λ5-
triazaphosphinines 11: Diguanidinophosphonium chloride 10 (Pro-
cedure a), (N-cyanophosphorimidoyl)guanidine 8 (Procedure b), or
2.7 Hz, p-C), 133.7 (d, JP,C ϭ 127.8 Hz, ipso-C), 140.2 (ipso-C),
1
166.1 (CNH2), 166.8 (CϭN) ppm. FABϩ MS: m/z (%) ϭ 340 (100).
C21H20N5P (339): calcd. C 67.55, H 5.40, N 18.76; found C 67.57,
H 5.39, N 18.60.
tert-butylammonium phosphonium diylide (2.5 mmol)
9 were
Eur. J. Org. Chem. 2004, 4870Ϫ4876
www.eurjoc.org
© 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4875

N. Inguimbert, L. Jäger, M. Taillefer, M. Biedermann, H.-J. Cristau
FULL PAPER
[11]
N,2,2-Triphenyl-1,3,5,2λ5-triazaphosphinine-4,6-diamine (11c):
Yield: (0.45 g, 1.25 mmol) 50%. (Procedure a), (0.67 g, 1.87 mmol)
75% (procedure b). White solid, m.p. 128Ϫ129 °C (ethyl acetate).
IR (KBr): ν˜ ϭ 3460 (NH2), 3400 (NH), 3380 (NH), 1630 (CϭN).
H. Köhler, D. Glanz, Z. Anorg. Allg. Chem. 1987, 554,
123Ϫ131.
[12]
A. Steiner, S. Zacchini, P. Richards, Coord. Chem. Rev. 2002,
227, 193Ϫ216.
H-J. Cristau, I. Jouanin, M. Taillefer, J. Organomet. Chem.
[13]
31P NMR (CDCl3): δ ϭ 32.37 ppm. H NMR (CDCl3): δ ϭ 5.57
1
1999, 584, 68Ϫ72.
(d, J ϭ 4.2 Hz, 2 H, NH2), 6.95 (t, J ϭ 7.3 Hz, 1 H aromatic H),
7.23 (t, J ϭ 8.2 Hz, 2 H, aromatic H), 7.40 (m, 6 H, aromatic H),
7.62 (d, J ϭ 7.76 Hz, 2 H, aromatic H), 7.8 (m, 5 H, aromatic H
and NH) ppm. 13C NMR (CDCl3): 120.2 (o-C), 122.3 (p-C), 128.5
[14]
F. D. Marsh, M. E. Hermes, J. Am. Chem. Soc. 1964, 86,
4506Ϫ4507.
[15]
L. Jäger, N. Inguimbert, M. Taillefer, H-J. Cristau, Synth. Com-
mun. 1995, 25, 2857Ϫ2864.
N. Inguimbert, L. Jäger, M. Taillefer, H-J. Cristau, J. Or-
[16]
3
2
(d, JC,P ϭ 13.0 Hz, m-C), 128.6 (m-C), 130.9 (d, JC,P ϭ 10.3 Hz,
4
1
ganomet. Chem. 1997, 529, 257Ϫ265.
o-C), 131.9 (d, JC,P ϭ 2.7 Hz, p-C), 133.1 (d, JC,P ϭ 120.3 Hz,
ipso-C), 139.0 (ipso-C), 164.1 (CϪNH2), 166.9 (CϭN) ppm. FABϩ
MS: m/z ϭ 360 (100). C20H18N5P (359): calcd. C 66.84, H 5.05, N
19.49; found C 64.84, H 4.95, N 18.53.
[17]
A. Schmidpeter, J. Ebeling, Angew. Chem. 1967, 79, 534Ϫ535,
Angew. Chem. Int. Ed. Engl. 1967, 565.
[18]
M. Becke-Goering, D. Jung, Z. Anorg. Allg. Chem. 1970, 372,
233Ϫ247.
[19]
K. J. L. Paciorek, D. H. Harris, J. H. Nakahara, M. E. Smythe,
N,NЈ,2,2-Tetraphenyl-1,3,5,2λ5-triazaphosphinine-4,6-diamine (11d):
Yield: (0.44 g, 1 mmol) 20% (procedure a). Pale yellow solid, m.p.
R. H. Kratzer, J. Fluorine Chem. 1985, 29, 399Ϫ416.
G. Alcaraz, V. Piquet, A. Baceireido, F. Dahan, W. W. Scho-
[20]
201Ϫ202 °C (ethyl acetate). IR (KBr): ν˜ ϭ 3400 (NH), 1590 (Cϭ
eller, G. Bertrand, J. Am. Chem. Soc. 1996, 118, 1060Ϫ1065.
W. Pinkert, G. Schoening, O. Glemser, Z. Anorg. Allg. Chem.
N) cmϪ1
.
31P NMR (CDCl3): δ ϭ 31.97 ppm. H NMR (CDCl3):
1
[21]
δ ϭ 7.03 (t, J ϭ 7.3 Hz, 2 H, aromatic H), 7.28 (t, J ϭ 7.5 Hz, 4
H, aromatic H), 7.51 (m, 6 H, aromatic H), 7.62 (d, J ϭ 7.76 Hz,
1977, 436, 136Ϫ139.
P. P. Kornuta, N. V. Kolotilo, L. N. Markovskii, J. Gen. Chem.
[22]
USSR 1982, 52, 2418Ϫ2421.
4 H, aromatic H), 8.0 (m, 4 H, aromatic H), 8.1 (s, 2 H, NH) ppm.
[23]
3
13C NMR (CDCl3): 120.3 (p-C), 122.4 (m-C), 128.6 (d, JC,P
ϭ
V. P. Kukar, T. N. Kasheva, J. Gen. Chem. USSR 1976, 46,
2
239Ϫ244.
13.0 Hz, m-C), 128.7 (m-C), 131.0 (d, JC,P ϭ 10.2 Hz, o-C), 132.0
[24]
P. P. Kornuta, N. V. Kolotilo, L. N. Markovskii, J. Gen. Chem.
4
1
(d, JC,P ϭ 2.7 Hz, p-C), 133.4 (d, JC,P ϭ 128 Hz, ipso-C),
140.0 (ipso-C), 163.9 (CϭN) ppm. FABϩ MS: m/z ϭ 436 (100).
C22H26N5P (435): calcd. C 71.71, H 5.09, N 16.08; found C 71.14,
H 5.24, N 15.87.
USSR 1982, 52, 519Ϫ525.
[25]
M. Meyer, U. Klingebiel, Chem. Ber. 1988, 121, 1119Ϫ1122.
[26]
N. Inguimbert, M. Biedermann, H. Stoeckli-Evans, H. Har-
tung, A. Kolbe, M. Taillefer, L. Jäger, H. J. Cristau, J. Mol.
Struct. 2000, 519, 211Ϫ218.
I. E. Boldeskul, A. S. Tarasevich, A. E. Obodovskaya, Z. A.
Starikova, P. P. Kornuta, J. Gen. Chem. USSR (Engl. Transl.)
1990, 60, 1763Ϫ1767.
A. N. Chernega, I. E. Boldeskul, M. Yu. Antipin, Yu. T. J.
N-(tert-Butyl)-2,2-diphenyl-1,3,5,2λ5-triazaphosphinine-4,6-diamine
(11e): Yield: 0.37 g, 1.1 mmol, 44%. White solid, m.p. 197Ϫ198 °C
(methanol). IR (KBr): ν˜ ϭ 3390 (NH2), 3300 (NH), 3160 (NH),
[27]
1640Ϫ1620 (CϭN) cmϪ1 31P NMR (CDCl3): δ ϭ 31.7 ppm. 1H
.
[28]
NMR (CDCl3): δ ϭ 1.42 [s, 9 H, (CH3)3C], 4.9 (br. s, 3 H, NH2,
NH), 7.40 (m, 6 H, aromatic H), 7.7 (m, 4 H, aromatic H) ppm.
13C NMR (CDCl3): δ ϭ 29.5 [(CH3)3C], 50.6 [(CH3)3C], 128.4 (d,
Struchkov, Struct. Chem. (Engl. Transl.) 1990, 31, 363Ϫ365.
[29]
S. J. Chen, K. Brychcy, U. Behrens, W. D. Stohrer, R. Mews,
Z. Naturforsch., Teil B 1995, 50, 86Ϫ90.
A. N. Chernega, I. E. Boldeskul, M. Yu. Antipin, Yu. T.
Struchkov, P. P. Kornuta, M. V. Kolotilo, J. Gen. Chem. USSR
(Engl. Transl.) 1987, 57, 1772Ϫ1777.
F. Belaj, Z. Naturforsch., Teil B 1996, 51, 1428Ϫ1432.
N. D. Reddy, A. J. Elias, A. Vij, J. Chem. Soc., Dalton Trans.
[30]
2
3JC,P ϭ 12.9 Hz, m-C), 130.6 (d, JC,P ϭ 10.0 Hz, o-C), 131.6 (p-
1
C), 134 (d, JC,P ϭ 128.6 Hz, ipso-C), 165.1 (CNH2), 166.3 (CϭN)
ppm. FABϩ MS: m/z (%) ϭ 340 [Mϩ] (100). C18H22N5P (339):
[31]
calcd. C 63.70, H 6.53, N 20.63; found C 62.46, H 6.47, N 19.66.
[32]
1999, 1515Ϫ1518.
G. Alcaraz, A. Baceireido, M. Nieger, W. W. Schoeller, G. Ber-
[33]
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A. F. Barlow, in P. T. Haskel (Ed.), Pesticide Application Prin-
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H.-J. Cristau, C. Garcia, J. Kadoura, E. Toreilles, Phosphorus,
[36]
Sulfur Silicon Relat. Elem. 1990, 49/50, 151Ϫ154.
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H.-J. Cristau, M. Taillefer, I. Jouanin, Synthesis 2001, 1,
[37]
69Ϫ74.
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