Synthesis of stabilized diaminophosphonium diazaylides

Article abstract of DOI:10.1055/s-2001-9748

The first examples of metalated stabilized diaminophosphonium diazaylides 7 have been synthesized in good yields from acylazides by two different synthetic pathways involving either an original and direct Staudinger reaction with the sodium phosphide (diazaylides 7′) or a more classical Staudinger reaction with diphenylphosphine and a subsequent deprotonation (diazaylides 7″). Additionally, the related new diaminophosphonium monoazaylides 6 and diaminophosphonium salts 5 have also been synthesized.

Full text of DOI:10.1055/s-2001-9748

PAPER
69
Synthesis of Stabilized Diaminophosphonium Diazaylides
Henri-Jean Cristau,* Marc Taillefer,* Isabelle Jouanin
Laboratoire de Chimie Organique, ENSCM, UMR 5076 du CNRS, 8 rue de l’Ecole Normale, 34296 Montpellier Cedex 5, France
Fax +33(0)467144319; E-mail: cristau@cit.enscm.fr and taillefe@cit.enscm.fr
Received 11 May 2000
as well as those of the corresponding monoazaylides 6 and
diaminophosphonium salts 5.
Abstract: The first examples of metalated stabilized diaminophos-
phonium diazaylides 7 have been synthesized in good yields from
acylazides by two different synthetic pathways involving either an
original and direct Staudinger reaction with the sodium phosphide
(diazaylides 7’) or a more classical Staudinger reaction with diphe-
nylphosphine and a subsequent deprotonation (diazaylides 7"). Ad-
ditionally, the related new diaminophosphonium monoazaylides 6
and diaminophosphonium salts 5 have also been synthesized.
Key words: Staudinger reaction, diaminophosphonium diazaylide,
diaminophosphonium monoazaylide, diaminophosphonium salt
We have shown that phosphonium diylides 2, thanks to
their increased reactivity in comparison with the corre-
sponding monoylides 1, are excellent tools in organic syn-
thesis.1 In order to enlarge the application field of this
diylide family, we have also developed a method to syn-
thesize the related nitrogen compounds, the non-stabilized
and semi-stabilized diazaylides 3 and 4.2
Figure 2
In the first method (Scheme 1, path A), the new stabilized
sodium diaminodiphenylphosphonium diazaylides par-
ents 7’a, 7’b and 7’d are directly obtained by the reaction
of two equivalents of corresponding azide (EwN3), with
one equivalent of the in situ prepared sodium diphe-
nylphosphide Ph2Pna. The electron-withdrawing substi-
tuted azides EwN3 are obtained by the reaction of the
corresponding acyl chlorides with sodium azide,6 and
Ph2PNa is obtained by reaction of chlorodiphenylphos-
phine with sodium. Apart from the synthesis of new stabi-
lized diazaylides, the originality of this pathway lies in the
new variation of the Staudinger reaction5,7 involving here
for the first time, a phosphide as phosphorus center.
Figure 1
Another synthetic pathway leads to stabilized lithium di-
aminodiphenylphosphonium diazaylides 7"b-f by simple
deprotonation of the corresponding intermediates
monoylides 6 (Scheme 1, path B). A double Staudinger
reaction of two equivalents of the corresponding azides
EwN3, in acetone, with the diphenylphosphine Ph2PH, af-
fords the monoazaylides 6b-f. Then, by addition of one
equivalent of n-BuLi after exchange of the solvent, reac-
tion takes place under mild conditions, and gives good to
excellent yields in diazaylides 7". Besides, the corre-
sponding monoazaylides 6b-f are easily recovered pure
by simple filtration of the medium and recrystallization in
suitable solvents. It is noteworthy that these molecules are
interesting as precursors of diazaylides because they are
easy to handle (solid, stable at room temperature, not sen-
sitive to oxidation). Until now, only one single prepara-
tion of the monoazaylide 6b has been described, with
limited spectral characterization.8
Recently, we have found that these reagents, until now
mainly used in coordination chemistry,3 are also interest-
ing in organic synthesis. Indeed, they behave as equiva-
lents of the RNH- synthon, and thus permit the synthesis
of primary and secondary amines.2 The study of the dia-
zaylides also afforded a new method for the synthesis,
under mild conditions, of diphenyl-N-(substituted)keten-
imines, a family of very non-stable compounds.4 In spite
of many attempts, the method used to synthesize 3 and 42
has not allowed the preparation of the corresponding sta-
bilized diazaylides 7 (R = electronwith-drawing group),
which are also potentially interesting reagents of synthe-
sis. However, we have recently described in one case the
synthesis in an original way of the first example of such
stabilized diazaylide5 (7’a, Ew = CN), which is a precur-
sor of phosphorus guanidines, molecules of agrochemical
interest. We describe here the synthesis, by two different
ways, of a family of new stabilized diazaylides 7’ and 7",
Concerning the diazaylide 7’g, with the tosyl group, the
formation is probably quantitative in situ (Table 1: path
Synthesis 2001, No. 1, 69–74 ISSN 0039-7881 © Thieme Stuttgart · New York

70
H.-J. Cristau et al.
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1
due to the P=N bond. The H and 13C NMR data for all
compounds are given in Table 2.
The experiments were performed under dry N2 (except in the case
of 5b-f), using Schlenk techniques. Acyl chlorides, sodium azide,
chlorodiphenylphosphine and diphenylphosphine were purchased
from Aldrich. All solvents were dried and distilled according to the
usual procedures. The acyl azides were prepared according to the
procedure described in the literature starting from acyl chlorides
and sodium azide.6 Solutions of n-BuLi in hexane were purchased
from Aldrich and titrated according to the usual techniques.9 Mps
were determined using a Wild Leitz 350 apparatus and are uncor-
1
rected. H, 31P and 13C NMR were recorded on a Bruker AC-200
spectrometer (200.132 MHz, 81.0 MHz and 50.323 MHz, respec-
tively). IR spectra were obtained with a Perkin-Elmer 377. Mass
spectra were measured with a JEOL SX 102 using FAB techniques
with GT (glycerol/thioglycerol) matrix.
Diaminodiphenylphosphonium Chlorides 5b-f; Typical Proce-
dure
Into a three necked round-bottomed flask was placed the monoylide
6 (1.18 mmol) in THF (20 mL), and gaseous HCl was bubbled at
20 °C through the solution (15 min). After 3 h at this temperature,
the mixture was composed of a colorless solution and a white solid
corresponding to the diaminodiphenylphosphonium chloride 5,
which was recuperated after filtration (yield of the pure compounds:
100%, 1.18 mmol, Tables 1 and 2).
Scheme 1
Diaminodiphenylphosphonium Monoazaylides 6b-f and Cor-
responding Lithium Diaminophosphonium Diazaylides 7"b-f;
Typical Procedure
A), but we observed its decomposition during the purifi-
cation. Pathway B also failed, but a small amount of the
corresponding monoazaylide 6g could be obtained and
characterized, using a different approach involving the
double nucleophilic substitution of the phosphorane
Ph2PClBr2 by the corresponding tosylamide (Scheme 2).
The same problem of decomposition as for path A was en-
countered when we tried to isolate the diazaylide 7"g after
treatement of 6g with one equivalent of BuLi.
Into a three necked round-bottomed flask, the solution of acyl azide
(50 mmol) in anhyd acetone (50 mL) was introduced under N2.6 The
solution was cooled to -5 °C and diphenylphosphine (4.3 mL,
25 mmol) was added dropwise at this temperature. The colorless
solution turns yellow and N2 was evolved (measured by H2O dis-
placement). At the end of the addition, the solution was allowed to
warm up at r.t. and after 3 h at 20 °C, the color disappeared and a
white precipitate appeared.
6b-f
The white precipitate, corresponding to the monoylide 6, was col-
lected by filtration, and dried under vacuum (50 mm Hg) in pres-
ence P4O10. It was then recrystallized in acetone (yields of the pure
compounds after recrystallization: 70-90%, 17.5-22.5 mmol:
Tables 1 and 2).
7"b-f
The acetone was eliminated with a filtrating cannula and replaced
by THF (150 mL). After cooling (-50 °C), a solution n-BuLi in
hexane (1.52 M, 16.4 mL, 25 mmol) was added dropwise (10 min).
After 1 h at this temperature, the solution was allowed to warm up
at 20 °C and evaporated to dryness. The residue was recrystallized
in a suitable solvent, to give, after filtration, the corresponding diaz-
aylide 7" (yields of the pure compounds: 65-90%, 16.2-22.5
mmol, Tables 1 and 2).
Scheme2
The diaminophosphonium salts 5b-f were also prepared
by the direct and quantitative protonation with gaseous
hydrogen chloride of the corresponding beforehand iso-
lated monoazaylides 6b-f. These new phosphonium salts,
stable and easy to store, are also of interest as precursors
of the corresponding diazaylides 7".
Bis(p-tosylamino)diphenylphosphonium Monoazaylide (6g)
Ph2PClBr2
From a spectroscopic point of view, it can be pointed out
that the chemical shifts in 31P NMR decrease from the
more positive phosphorus (d Y 42 ppm for 5) to the lesser
To a cooled (5 °C) solution of Ph2PCl (4.5 mL, 25 mmol) in dry
CH2Cl2 (25 mL), was added under N2 a solution of Br2 (1.3 mL,
25 mmol) in dry CH2Cl2 (25 mL). After the addition, stirring was
one (dY 27 ppm for 6 and Y 7 ppm for 7). It is also noticed maintained for 1 h at 20 °C.
that the infrared data show higher nC=O absorbtions for the
phosphonium chloride 5 because there is no delocalisation
Monoazaylide 6g
To a cooled (0 °C) solution of NaH (2.89 g in oil, 65% titrated,
78 mmol) in dry THF (30 mL) was added dropwise under N2 a
Synthesis 2001, No. 1, 69–74 ISSN 0039-7881 © Thieme Stuttgart · New York

PAPER
Synthesis of Stabilized Diaminophosphonium Diazaylides
71
Table 1 Diaminodiphenylphosphonium Chlorides 5 and the Corresponding Monoazaylides 6 and Diazaylides 7’ and 7"a
Com-
pound
R
Yieldb
(%)
Mp (°C)
(Solvent)
IR (KBr), n (cm−1)
FAB-MS c 31P NMRd
(81 MHz)
EW = C(O)R
d (ppm)
5b
Ph
100
100
100
100
100
90
185-186
3420, 1670 (C=O), 1450, 1390 (P-N), 1340, 1320, 1250,
1110, 1060
425
453
485
493
525
425
453
485
493
525
42.2
41.9
41.7
42.5
42.4
27.5
27.2
26.9
27.7
27.8
15.8
19.2
7.4
(THF)
5c
p-MeC6H4
p-MeOC6H4
p-ClC6H4
naphtyl
Ph
152
(THF)
3425, 1660 (C=O), 1605, 1380 (P-N), 1260, 1185, 1120,
1070
5d
200
(THF)
3390, 1650 (C=O), 1600, 1570, 1425 (P-N), 1400, 1250,
1170
5e
180
(THF)
3420, 1660 (C=O), 1590, 1410 (P-N), 1390, 1310, 1260,
1090
5f
190
(THF)
3420, 1660 (C=O), 1620, 1440, 1410 (P-N), 1280, 1120
6b
169-171
(acetone)
3435, 1590 (C=O), 1540, 1450, 1440, 1350 (P=N), 1170,
1125, 1080, 1020
6c
p-MeC6H4
p-MeOC6H4
p-ClC6H4
naphtyl
tosylf
72
149
(acetone)
3420, 1670, 1605 (C=O), 1560, 1540, 1435, 1390 (P=N),
1115
6d
70
167-169
(acetone)
3435, 1670, 1600 (C=O), 1585, 1530, 1430, 1420, 1350
(P=N), 1240, 1180, 1150, 1030
6e
71
210
(acetone)
3500, 1700, 1615 (C=O), 1570, 1520, 1465, 1390 (P=N),
1210, 1150, 1140, 1120
6f
70
208-209
(acetone)
3410, 1660, 1580 (C=O), 1540, 1460, 1430, 1360 (P=N),
1335, 1230, 1120
6g
5
195-199
(EtOH)
3400, 2900, 2600, 1600, 1380, 1260, 1200, 1160, 1150, 1130, 525
1110, 1080
7’a
7"b
7’b
7"c
7"d
7’d
7"e
7"f
7’g
CNf,5
80
182
(CH3CN)
3070, 3060, 2190 (NCN), 2140 (NCN), 1630, 1440, 1300,
1280, 1130, 1115
265
431
447
459
491
507
499
531
-
Ph
90
(100)
145-150e
(THF)
3400, 3050, 2900, 1590 (C=O), 1530 (C=N), 1500, 1430,
1370-1350 (P=N), 1340, 1300, 1110
Ph
40
>280
(EtOH)
3420, 3120, 1590 (C=O), 1570, 1530 (C=N), 1470, 1440,
1350-1330 (P=N), 1300, 1110, 920
7.4
p-MeC6H4
p-MeOC6H4
p-MeOC6H4
p-ClC6H4
naphtyl
Tosylf
72
(100)
176-182e
(THF)
3400, 3120, 1600 (C=O), 1550 (C=N), 1430, 1370-1350
(P=N), 1180, 1020, 1000, 800
7.7
65
(90)
154-160e
(THF)
3400, 3100, 1600 (C=O), 1540 (C=N), 1420, 1360-1340
(P=N), 1320, 1110, 770
6.5
40
>280
(CH2Cl2)
3400, 3000, 1600 (C=O), 1590, 1530 (C=N), 1500, 1360-
1340 (P=N), 1310, 1170, 1110
7.1
65
(90)
130-135e
(THF)
3400, 2900, 1585 (C=O), 1550-1530 (C=N), 1380, 1350-
1330 (P=N), 1110, 1010, 760
8.2
65
(90)
120-130e
(THF)
3420, 3020, 1590, 1580 (C=O), 1530 (C=N), 1390, 1370-
1350 (P=N), 1330, 1120, 780
7.9
99
-
-
11.5
a Satisfactory elemental analyses were obtained for 5, 6, 7’ and 7".
b Pure isolated compound (except for 7’g: formation rate). For 7"b−f the yields in brackets are obtained by reaction of one equivalent of n-
BuLi with the corresponding beforehand isolated monoazaylides 6.
c 5: FAB+ MS (GT), [M-35Cl]+. 6, 7", 7’b and 7’d: FAB+ MS (GT), [M+H]+. 7’a: FAB− MS (GT), [M-Na]−.
d 5, 6 and 7"c (solvent: CDCl3). 7’b, 7"b (11.5 ppm in DMSOD), 7"d, 7’d, 7"e, 7"f and 7’g (solvent: THF). 7’a (solvent: DMSOD).
e Decomposition point.
f Ew = tosyl (6g and 7’g); Ew = CN (7’a).
Synthesis 2001, No. 1, 69–74 ISSN 0039-7881 © Thieme Stuttgart · New York

72
H.-J. Cristau et al.
PAPER
Table 2 Diaminodiphenylphosphonium Chlorides 5 and the Corresponding Monoazaylides 6 and Diazaylides 7’ and 7"
Com-
pound
1H NMR (200 MHz, DMSOD)
d (ppm), J (Hz)
13C NMR (50 MHz, DMSOD)
d (ppm), J (Hz) a
5b
5c
5d
7.50-7.76 (m, 12 H, m- and p-H), 8.16 (q,
4 H, 3JH,P = 15, 3JH,H = 8, o-H, C6H5), 8.40
(d, 4 H, 3JH,H = 7.8, o-H, C6H5), 12.65 (d,
2 H, 2JH,P = 7.5, NH)
119.70 (d, 1JC,P = 120.6, i-C, P-C6H5), 128.95 (m-C, C-C6H5), 129.32 (d, 3JC,P
=
15.3, m-C, P-C6H5), 129.3 (o-C, C-C6H5), 129.77 (d, 3JC,P = 7.1, i-C, C-C6H5),
133.63 (d, 2JC,P = 13.3, o-C, P-C6H5), 134.29 (p-C, C-C6H5), 135.11 (d, 4JC,P = 3.2,
p-C, P-C6H5), 169.90 (C=O)
2.36 (s, 6 H, Me), 7.26 (d, 4 H, 3JH,H = 7.4,
21.72 (Me), 119.30 (d, 1JC,P = 120.4, i-C, C6H5), 124.40 (m-C, C6H4), 127.2 (d, 3JC,P
m-H, C6H4), 7.50-7.82 (m, 6 H, m- and p-H, = 7.1, i-C, C6H4), 129.22 (d, 3JC,P = 15.3, m-C, C6H5), 130.38 (o-C, C6H4), 133.15
C6H5), 8.00-8.20 (m, 8 H, o-H), 12.51 (s,
2 H, NH)
(d, 2JC,P = 13.3, o-C, C6H5), 135.26 (d, 4JC,P = 3.0, p-C, C6H5), 137.71 (p-C, C6H4),
169.52 (C=O)
3.80 (s, 6 H, OMe), 6.94 (d, 4 H, 3JH,H = 8.9, 50.58 (OMe), 114.17 (m-C, C6H4), 119.0 (d, 1JC,P = 120.6, i-C, C6H5), 122.18 (d,
m-H, C6H4), 7.50-7.72 (m, 6 H, m- and p-H, 3JC,P = 7.1, i-C, C6H4), 129.11 (d, 3JC,P = 15.4, m-C, C6H5), 131.83 (o-C, C6H4),
C6H5), 8.11 (q, 4 H, 3JH,P = 14.9, 3JH,H = 7.1, 133.58 (d, 2JC,P = 13.3, o-C, C6H5), 134.89 (d, 4JC,P = 3.2, p-C, C6H5), 164.40 (p-C,
o-H, C6H5), 8.34 (d, 4 H, 3JH,H = 8.9, o-H,
C6H4), 12.33 (d, 2 H, 2JH,P = 7.7, NH)
C6H4), 169.15 (C=O)
5e
7.50 (d, 4 H, 3JH,H = 8.6, m-H, C6H4), 7.60- 119.30 (d, 1JC,P = 120.1, i-C, C6H5), 128.19 (d, 3JC,P = 7.7, i-C, C6H4), 129.31 (m-C,
7.80 (m, 6 H, m- and p-H, C6H5), 8.10 (q,
C6H4), 129.33 (d, 3JC,P = 15.4, m-C, C6H5), 130.98 (o-C, C6H4), 133.69 (d, 2JC,P
4 H, 3JH,P = 15, 3JH,H = 7.1, o-H, C6H5), 8.34 13.4, o-C, C6H5), 135.3 (d, 4JC,P = 3.1, p-C, C6H5), 141.03 (p-C, C6H4), 168.88
=
(d,
(C=O)
4 H, 3JH,H = 8.5, o-H, C6H4), 12.65 (d, 2 H,
2JH,P = 7.5, NH)
5f
7.50-7.70 (m, 10 H), 7.85-7.95 (m, 4 H),
120.20 (d, 1JC,P = 120.0, i-C, C6H5), 124.37, 126.83, 127.65, 128.73, 129.14,
8.10-8.26 (m, 8 H), 9.3 (s, 2 H, 1-H, naph), 129.44, 130.2, 132.07 (1-, 3-, 4-, 5-, 6-, 7- and 8-C of naph ; m-C, C6H5), 126.83 (2-
12.85 (d, 2 H, 2JH,P = 7.5, NH)
C, naph), 132.49, 135.99 (9- and 10-C, naph), 133.80 (d, 2JC,P = 13.3, o-C, C6H5),
135.11 (d, 4JC,P = 3.2, p-C, C6H5), 170.06 (C=O)
6b
6c
6d
7.43-7.70 (m, 12 H, m- and p-H), 8.00-
8.10 (m, 4 H, o-H), 8.16-8.20 (m, 4 H,
o-H), 11.65 (s, 1 H, NH)
127.59 (d, 1JC,P = 128.0, i-C, P-C6H5), 128.44 (m-C, C-C6H5), 128.95 (d, 3JC,P
=
14.1, m-C, P-C6H5), 129.21 (d, 4JC,P = 1.0, o-C, C-C6H5), 132.20 (p-C, C-C6H5),
133.10 (d, 2JC,P = 11.5, o-C, P-C6H5), 133.55 (d, 4JC,P = 3.0, p-C, P-C6H5), 135.58
(d, 3JC,P = 14.3, i-C, C-C6H5), 173.15 (C=O)
2.40 (s, 6 H, Me), 7.26 (d, 4 H, 3JH,H = 8,
21.63 (Me), 127.79 (d, 1JC,P = 127.3, i-C, C6H5), 128.0 (d, 3JC,P = 13.9, i-C, C6H4),
m-H, C6H4), 7.50-7.55 (m, 6 H, m- and p-H, 128.63 (d, 3JC,P = 14.4, m-C, C6H5), 128.95 (d, 4JC,P = 1.1, o-C, C6H4), 129.11 (m-C,
C6H5), 7.90-8.07 (m, 8 H, o-H), 11.55 (s,
1 H, NH)
C6H4), 132.72 (d, 2JC,P = 11.5, o-C, C6H5), 133.09 (d, 4JC,P = 3.0, p-C, C6H5), 142.79
(p-C, C6H4), 173.46 (C=O)
3.84 (s, 6 H, OMe), 6.94 (d, 4 H, 3JH,H = 8.8, 55.43 (OMe), 113.54 (m-C, C6H4), 128.48 (d, 3JC,P = 14.0, i-C, C6H4), 128.77 (d,
m-H, C6H4), 7.50-7.56 (m, 6 H, m- and p-H, 1JC,P = 128.2, i-C, C6H5), 129.38 (d, 3JC,P = 14.0, m-C, C6H5), 131.71 (o-C, C6H4),
C6H5), 8.00 (q, 4 H, 3JH,P = 14, 3JH,H = 7.9,
o-H, C6H5), 8.10 (d, 4 H, 3JH,H = 8.8, o-H,
C6H4), 11.30 (s, 1 H, NH)
133.51 (d, 2JC,P = 11.5, o-C, C6H5), 134.83 (d, 4JC,P = 3.0, p-C, C6H5), 164.10 (p-C,
C6H4), 172.32 (C=O)
6e
7.41 (d, 4 H, 3JH,H = 8.6, m-H, C6H4), 7.50- 127.21 (d, 1JC,P = 128.08, i-C, C6H5), 128.08 (d, 3JC,P = 14.1, i-C, C6H4), 128.62
7.64 (m, 6 H, m- and p-H, C6H5), 8.00 (q,
4 H, 3JH,P = 14, 3JH,H = 8, o-H, C6H5), 8.10
(d, 4 H, 3JH,H = 8.6, o-H, C6H4), 11.80 (s, 1
H, NH)
(m-C, C6H4), 128.72 (d, 3JC,P = 14.1, m-C, C6H5), 130.31 (d, 4JC,P = 1.2, o-C, C6H4),
132.66 (d, 2JC,P = 11.5, o-C, C6H5), 133.33 (d, 4JC,P = 3.0, p-C, C6H5), 138.62 (p-C,
C6H4), 171.71 (C=O)
6f
7.50-7.54 (m, 10 H), 7.88-8.30 (m, 12 H), 125.14, 126.53, 127.75, 127.91, 128.18, 129.51, 129.94 (1-, 3-, 4-, 5-, 6-, 7- and
8.81 (s, 2 H, 1-H, naph), 11.80 (s, 1 H, NH) 8-C of naph), 126.34 (2-C, naph), 132.73, 135.32 (9- and 10-C, naph), 128.74 (d,
3JC,P = 15.0, m-C, C6H5), 132.83 (d, 2JC,P = 11.5, o-C, C6H5), 133.23 (d, 4JC,P = 3.2,
p-C, C6H5), 172.90 (C=O)
6g
2.37 (s, 6 H, Me), 4.31 (br s, 1 H, NH), 7.00 26.19 (s, Me), 131.03 (s, m-C, tosyl), 133.30 (d, 3JC,P = 13.9, m-C, C6H5), 133.84
(d, 4 H, 3JH,H = 8.1, m-H, tosyl), 7.27-7.40 (d, 1JC,P = 130.0, i-C, C6H5), 134.83 (s, o-C, tosyl), 137.40 (d, 2JC,P = 11.3, o-C,
(m, 6 H, m- and p-H, C6H5), 7.55 (d, 4 H,
3JH,H = 7.1, m-H, tosyl), 7.70 (q, 4 H, 3JH,P
14.3, 3JH,H = 7.3, o-H, C6H5)
C6H5), 137.60 (s, p-C, C6H5), 146.38 (s, p-C, tosyl), 146.91 (d, , 3JC,P = 2.3, i-C, to-
=
syl).
7’a5
7.40 (m, 4 H, C6H5), 7.80 (m, 6 H, C6H5)
119.30 (s, NCN), 131.50 (d, 4JC,P = 2.3, p-C, C6H5), 128.40 (d, 3JC,P = 12.6, m-C,
C6H5), 131.0 (d, 2JC,P = 9.6, o-C, C6H5), 133.10 (d, 1JC,P = 129.3, i-C, C6H5)
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Synthesis of Stabilized Diaminophosphonium Diazaylides
73
Table 2 (continued)
Com-
pound
1H NMR (200 MHz, DMSOD)
d (ppm), J (Hz)
13C NMR (50 MHz, DMSOD)
d (ppm), J (Hz) a
7"b
7’b
7.38-7.45 (m, 12 H, m- and p-H, C6H5),
7.93-8.05 (m, 4 H, o-H, P-C6H5), 8.23-
8.28 (m, 4 H, o-H, C-C6H5)
127.35 (m-C, C-C6H5), 127.80 (d, 3JC,P = 11.7, m-C, P-C6H5), 128.92, 128.95,
129.81 (p-C and o-C, C-C6H5; p-C, P-C6H5), 131.38 (d, 2JC,P = 8.7, o-C, P-C6H5),
136.46 (d, 1JC,P = 123.0, i-C, P-C6H5), 140.27 (d, 3JC,P = 20.4, i-C, C-C6H5), 172.91
(d, 2JC,P = 7.9, C=O)
7.40-7.42 (m, 12 H, m- and p-H, C6H5),
7.98-8.05 (m, 4 H, o-H, P-C6H5), 8.23-
8.26 (m, 4 H, o-H, C-C6H5)
127.19 (m-C, C-C6H5), 127.60 (d, 3JC,P = 11.6, m-C, P-C6H5), 128.93 (d, 4JC,P = 1.5,
o-C, C-C6H5), 129.43, 129.48 (p-C, C6H5), 131.40 (d, 2JC,P = 8.7, o-C, P-C6H5),
137.0 (d, 1JC,P = 120.0, i-C, P-C6H5), 140.73 (d, 3JC,P = 20.8, i-C, C-C6H5), 172.43
(d, 2JC,P = 7.0, C=O)
7"c
7"d
7’d
2.37 (s, 6 H, Me), 7.08 (d, 4 H, 3JH,H = 7.85, 21.10 (Me), 127.69 (d, 3JC,P = 12.2, m-C, C6H5), 127.89 (m-C, C6H4), 129.28 (d,
m-H, C6H4), 7.27-7.30 (m, 6 H, m- and p-H, 4JC,P = 1.3, o-C, C6H4), 129.71 (p-C, C6H5), 131.33 (d, 2JC,P = 8.76, o-C, C6H5),
C6H5), 7.86-7.95 (m, 4 H, o-H, C6H5), 8.00 135.88 (d, 1JC,P = 128.3, i-C, C6H5), 136.96 (d, 3JC,P = 19.4, i-C, C6H4), 139.79
(d, 4 H, 3JH,H = 7.9, o-H, C6H4)
(p-C, C6H4), 173.94 (d, 2JC,P = 8.3, C=O)
3.81 (s, 6 H, OMe), 6.96 (d, 4 H, 3JH,H = 8.7, 55.07 (OMe), 112.51 (m-C, C6H4), 127.74 (d, 3JC,P = 11.9, m-C, C6H5), 130.72,
m-H, C6H4), 7.38-7.40 (m, 6 H, m- and p-H, 130.80 (p-C, C6H5 ; o-C, C6H4), 131.35 (d, 2JC,P = 8.6, o-C, C6H5), 132.74 (d, 3JC,P
C6H5), 7.85-8.01 (m, 4 H, o-H, C6H5), 8.19 = 20.6, i-C, C6H4), 136.74 (d, 1JC,P = 123.0, i-C, C6H5), 160.85 (p-C, C6H4), 172.72
(d, 4 H, 3JH,H = 8.7, o-H, C6H4)
(d, 2JC,P = 7.7, C=O)
3.80 (s, 6 H, OMe), 6.91 (d, 4 H, 3JH,H = 8.7, 55.03 (OMe), 112.28 (m-C, C6H4), 127.44 (d, 3JC,P = 11.4, m-C, C6H5), 129.26 (d,
m-H, C6H4), 7.34-7.38 (m, 6 H, m- and p-H, 4JCP = 1.8, p-C, C6H5), 130.47 (d, 4JCP = 1.6, o-C, C6H4), 131.50 (d, 2JC,P = 8.6, o-C,
C6H5), 7.91-8.00 (m, 4 H, o-H, C6H5), 8.12 C6H5), 133.56 (d, 3JC,P = 20.9, i-C, C6H4), 137.45 (d, 1JC,P = 119.2, i-C, C6H5),
(d, 4 H, 3JH,H = 8.7, o-H, C6H4)
160.43 (p-C, C6H4), 172.07 (d, 2JC,P = 7.3, C=O)
7"e
7"f
7.38-7.48 (m, 6 H, m- and p-H, C6H5), 7.46 127.31 (m-C, C6H4), 127.75 (d, 3JC,P = 11.7, m-C, C6H5), 129.75 (d, 4JCP = 1.6, p-C,
(d, 4 H, 3JH,H = 8.4, m-H, C6H4), 7.91-8.00 C6H5), 130.76 (d, 4JCP = 1.4, o-C, C6H4), 131.35 (d, 2JC,P = 8.7, o-C, C6H5), 134.62
(m, 4 H, o-H, C6H5), 8.22 (d, 4 H, 3JH,H
8.4, o-H, C6H4)
=
(p-C, C6H4), 136.15 (d, 1JC,P = 119.2, i-C, C6H5), 139.19 (d, 3JC,P = 20.9, i-C, C6H4),
171.6 (d, 2JC,P = 7.6, C=O)
7.44-7.55 (m, 10 H), 7.94-8.15 (m, 10 H), 125.8, 126.5, 126.6, 126.84, 127.44, 128.64, 128.8, 129.81 (1-, 3-, 4-, 5-, 6-, 7- and
8.44 (d, 2 H, 3JH,H = 8.5, 3-H, naph), 8.81 (s, 8-C of naph ; p-C, C6H5), 127.82 (d, 3JC,P = 11.57, m-C, C6H5), 131.55 (d, 2JC,P
2 H, 1-H, naph)
8.55, o-C, C6H5), 132.4, 133.92 (9- and 10-C, naph), 136.42 (d, 1JC,P = 121.8, i-C,
C6H5), 137.91 (d, 3JC,P = 20.3, 2-C, naph), 172.86 (d, 2JC,P = 7.9, C=O)
=
a Concerning the compounds 7"c−e and 7’d, the ipso position for C(O)Ar corresponds to the aromatic carbon linked to the C=O group.
Concerning 6g, the ipso position for the tosyl corresponds to the aromatic carbon linked to the sulphur atom.
solution of tosylamide (13.35 g, 78 mmol) in dry THF (120 mL).
After the addition, stirring was maintained 10 h at 20 °C. To this so-
lution was added under N2 the solution of Ph2PClBr2 dropwise at
0 °C over 30 min . After 3 days at 20 °C, a white fine powder was
eliminated by filtration. The solution was then evaporated to dry-
ness and EtOH (15 mL) was added. After cooling (-20 °C), the
monoylide 6g was obtained as a white solid and filtered (yield of the
pure compound after recrystallization in EtOH: 5%, 1.25 mmol,
Tables 1 and 2).
2). Compound 7’g was not stable enough to be isolated but it was
probably detected in situ by 31P NMR (Table 1) as the lone phospho-
rus product of the reaction.
Acknowledgement
The authors thank Alix Contreras for his contribution to this work
and the M.E.S.R and the CNRS for the financial support.
Sodium Diaminodiphenylphosphonium Diazaylides 7’b, 7’d,
7’g; Typical Procedure
References
(1) Cristau, H. J. Chem. Rev. 1994, 94, 1299.
Cristau, H. J.; Taillefer, M.; Urbani, J. P.; Fruchier, A.
Tetrahedron 1996, 52, 2005.
Into a three necked round-bottomed flask, chlorodiphenylphos-
phine Ph2PCl (1.8 mL, 10 mmol) in anhyd THF (60 mL) was intro-
duced under N2, and Na (0.46 g, 20 mmol) was then added at 25 °C.
The mixture turns first yellow and then orange after 18 h in reflux-
ing THF. After cooling to 20 °C and elimination of excess Na by fil-
tration, the solution was introduced under N2, dropwise, to a
solution of freshly prepared acyl azide (20 mmol) in anhyd acetone
(25 mL).6 N2 evolution can be measured by H2O displacement. Af-
ter 48 h at 20 °C, the yellow and turbid solution was filtrated. The
filtrate was evaporated to dryness to give a solid corresponding to
the crude diylide 7’. After recrystallization, 7’b (EtOH) and 7’d
(CH2Cl2) were both obtained in 40% yield (4 mmol) (Tables 1 and
Cristau, H. J.; Taillefer, M. Tetrahedron 1998, 54, 1507.
Taillefer, M.; Cristau, H. J. Tetrahedron Lett. 1998, 39, 7857.
(2) Cristau, H. J.; Garcia, C.; Kadoura, J.; Torreilles, E.
Phosphorus, Sulfur, Silicon 1990, 49/50, 151.
Cristau, H. J.; Garcia, C. Synthesis 1990, 315.
(3) Witt, M.; Roesky H. W. Chem. Rev. 1994, 94, 1163.
(4) Cristau, H. J.; Jouanin, I.; Taillefer, M. J. Organomet. Chem.
1999, 584, 68.
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H.-J. Cristau et al.
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(5) Taillefer, M.; Inguimbert, N.; Jäger L.; Merzweiler K.;
Cristau, H. J. Chem. Commun. 1999, 565.
Article Identifier:
1437-210X,E;2001,0,01,0069,0074,ftx,en;P03700SS.pdf
(6) Froyen, P. Phosphorus, Sulfur, Silicon 1993, 78, 161.
(7) Staudinger, H.; Meyer, J. Helv. Chim. Acta. 1919, 2, 635.
Gololobov,Y.; Kasukhin, L. F. Tetrahedron. 1992, 48, 1353.
(8) Derkach, G. I., Gubnitskaya, E. S. Zh. Obshch. Khim. 1964,
34, 604.
(9) Gilman, H.; Cartlege, F. K J. Organomet. Chem. 1964, 2, 447.
Synthesis 2001, No. 1, 69–74 ISSN 0039-7881 © Thieme Stuttgart · New York