Reaction of dibromoalkanes with silyl phosphites. Synthesis and properties of mono-and diphosphonoalkanes

Article abstract of DOI:10.1134/S1070363206050094

Reactions of dibromoethane and dibromopropane with silyl phosphites are studied. Mono-and diphosphonoalkanes of various structures were prepared, and their chemical properties were studied. Pleiades Publishing, Inc., 2006.

Full text of DOI:10.1134/S1070363206050094

ISSN 1070-3632, Russian Journal of General Chemistry, 2006, Vol. 76, No. 5, pp. 714 719.
Pleiades Publishing, Inc., 2006.
Original Russian Text M.A. Pudovik, S.A. Terent’eva, L.K. Kibardina, A.N. Pudovik, 2006, published in Zhurnal Obshchei Khimii, 2006, Vol. 76, No. 5,
pp. 750 756.
Reaction of Dibromoalkanes with Silyl Phosphites.
Synthesis and Properties of Mono- and Diphosphonoalkanes
M. A. Pudovik, S. A. Terent’eva, L. K. Kibardina, and A. N. Pudovik
Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center,
Russian Academy of Sciences, ul. Arbuzova 8, Kazan, Tatarstan, 420088 Russia
Received October 30, 2005
Abstract Reactions of dibromoethane and dibromopropane with silyl phosphites are studied. Mono- and
diphosphonoalkanes of various structures were prepared, and their chemical properties were studied.
DOI: 10.1134/S1070363206050094
Over the past years we have developed procedures
for synthesis of chloro(bromo)methyl(thio)phos-
phonylated(phosphinytaled) ureas, thioureas, uretha-
nes, and thiourethanes by the addition of amines, al-
cohols, and thiols to corresponding halomethyl iso-
silyl) phosphite (II) occur under heating to form silyl
phosphonates IIIa, IIIb. The latter were chlorinated
with PCl5 to obtain bromoalkylphosphonic dichlorides
IVa, IVb that are basic starting materials for synthesis
of linear and cyclic compounds with a P C bond.
(thio)cyanatophosphonates(phosphinates).
In
the
Br(CH2)nBr + (Me3SiO)3P
presence of bases, the products undergo intramole-
cular transformations to form cyclic compounds of
various compositions and structures [1 4]. To find out
if this approach is feasible for preparing larger cycles,
specifically sixmembered, we set ourselves the task to
introduce to the phosphorus atom a 2-haloalkyl group
instead of halomethyl. According to published data,
haloalkylphosphonic acid esters are most commonly
synthesized by reactions of dihaloalkanes with trialkyl
phosphites [5 12]. At present much interest is at-
tached to silyl esters of P(III) acids. On the one hand,
this interest is associated with the fact that silyl phos-
phites(phosphonites) can be easily and effectively
prepared by silylation of available P(III) acids with
compounds (including those produced industrially)
with a Si N bond (hexamethyldisilazane, heptame-
Ia, Ib
II
O
O
Br(CH2)nPCl2,
IVa, IVb
PCl5
Br(CH2)nP(OSiMe3)2
IIIa, IIIb
n = 2 (Ia, IIIa, IVa), 3 (Ib, IIIb, IVb).
(Bromoethyl)phosphonic dichloride IVa was also
prepared in comparable yield by the reaction of di-
bromoethane with diethyl trimethylsilyl phosphite.
As follows from the 31P spectrum, the latter reaction
involves intermediate formation of phosphonates V
25.09, 14.35 ppm) in roughly equal
amounts. Treatment of the reaction mixture with PCl5,
and VI (
P
thyldisilazane,
trimethylsilyldiethylamine,
etc.)
too, gave phosphonic dichloride IVa.
[13 17]. On the other hand, silyl esters of P(III) acids
are highly reactive toward various electrophilic agents
and have found wide application in organic synthesis
[18, 19]. In particular, reactions of dihaloalkanes with
silyl phenylphosphonites were used as the basis for
the procedures for synthesis of vinylphosphoryl
derivatives [17] and phosphorus-containing amino-
carboxylic acids [20]. With this in mind, we made an
attempt to develop synthetic procedures for - and
-bromoalkylphosphonates and diphosphonoalkanes,
relying on reactions of dibromoalkanes with silyl
phosphites.
O
Ia + (EtO)2POSiMe3
Br(CH2)2POSiMe3
OEt
V
O
PCl5
+ Br(CH2)2P(OEt)2
VI
IVa.
The (bromoalkyl)phosphonic dichlorides react with
alcohols to give, depending on the reactant molar
ration, partial or full alkoxylation products VIIa VIIc,
VIII.
The reactions of equimolar amounts of dibromo-
ethane Ia or dibromopropane Ib with tris(trimethyl-
714

REACTION OF DIBROMOALKANES WITH SILYL PHOSPHITES
715
O
VIIa, VIIc + MeC(O)N(SiMe3)2
IX
ROH
Br(CH2)nPCl
O
OR
VIIa VIIc
O
Br(CH2)nPOSiMe3,
IVa, IVb
Me3SiCl, MeCN
OEt
2EtOH
Xa, Xb
Br(CH2)nP(OEt)2
VIII
X, n = 2, R = Et (a); n = 3, R = Et (b).
VII, n = 2, R = Et (a), Ph (b); n = 3, R = Et (c).
thiocyanate gave phosphonoisothiocyanatidate XI.
However, we failed to add diethyl- or dimethylamine
by the isothiocyanato group to prepare phosphorylated
thiourea XII. It was found that the major process in
these conditions was dehydrobromination yielding an
unstable vinylphosphonoisothiocyanatidate XIV (that
probably undergoes fast isomerization), as evidenced
by the isolation of dialkylamine hydrobromides.
The example of phosphonochloridates VIIa, VIIc
was used to show that our previous procedure involv-
ing bis(trimethylsilyl)acetamide [21] allows introduc-
tion of a siloxy group to phosphorus to obtained
mixed bromoalkylphosphonates Xa, Xb.
The reaction of compound VIIa with potassium
O
O
S
B
S
,
EtOP
Br(CH2)2PNHCNR2
OEt
B HBr
N
C
O
NR2
XIII
R2NH
KSCN
VIIa
Br(CH2)2PNCS
XII
OEt
O
XI
[CH2=CHPNCS]n + R2NH HBr,
OEt
XIV
R = Me, Et.
To suppress dehydrohalogenation, we decided to
obtain an analog of compound XI, phosphonoisothio-
cyanatidate XIX in which the halogen and phosphorus
atoms are intervened by an ethylene bridge. Taking
account of the data in [22], we reacted PCl3 with
propene oxide to obtain tris(2-chloropropyl) phosphite
(XV) that isomerized into bis(2-chloropropyl) (2-chlo-
ropropyl)phosphonate (XVI) under prolonged heating.
Treatment of the latter with PCl5 gave the base reac-
tion product, viz. (2-chloropropyl)phosphonic dichlo-
ride (XVII).
Cl
Cl
Cl
O
PCl3 + 3Me CH CH2
O
P(OCH2CHMe)3
MeCHCH2P(OCH2CHMe)2
XV
XVI
Cl
Cl
O
Cl
O
O
PCl5
KSCN
KCl
PhOH
MeCHCH2PCl2
MeCHCH2P Cl
MeCHCH2PNCS.
HCl
OPh
OPh
XIX
XVII
XVIII
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716
PUDOVIK et al.
The reaction of equimolar amounts of phosphonic
XVIII and XIX, that have two chiral centers, are mix-
tures of two diastereomers in nearly 1:1 ratios. Com-
pound XIX was found to decompose on vacuum dis-
tillation, and, therefore, it was further used without
isolation.
dichloride XVII and phenol afforded phosphonochlo-
ridate XVIII whose prolonged heating with potassium
thiocyanate yielded phosphonoisothiocyanatidate XIX.
According to the 31P NMR spectrum, compounds
Cl
O
S
N
P
NMe2
C
S
O
Me3NH
IX + Me2NH
MeCHCH2PNHCNMe2
OPh
Me2NH HCl
PhO
Me
XXI
XX
Excess dimethylamine was bubbled through a
benzene solution of phosphonoisothiocyanatidate XIX.
The crystals that formed were a mixture of cycle XXI
and dimethylamine hydrochloride. The cyclization
probably involves intermediate formation of phos-
phorylated thiourea XX that fast cyclizes into final
compound XXI. Since the reaction was performed in
the presence of excess dimethylamine, we consider
the most probable the following cyclization pathway:
First a complex between base (dimethylamine) and
thiourea is formed, which is accompanied by weaken-
ing of the N H bond and, probably, ion pair formation.
The subsequent nucleophilic attack of the thiourea
sulfur atom on the -carbon atom of the chloropropyl
group is accompanied by chlorine expulsion from the
latter and ring formation. Triple crystallization of the
precipitate from benzene provided individual phos-
elemental analysis. The mass spectrum of phospha-
cyclane XXI contains a molecular ion peak at m/z 284.
According to X-ray diffraction data, the molecular
conformation of XXI is half-chair: The four-atomic
fragment S1C2N3P4 is planar [within 0.02(1) ], and
C5 and C6 deviate from this plane by 0.440(7) and
0.380(6) , respectively, i.e. locate on different sides
of this fragment. The chiral atoms P4 and C6 have an
R configuration. Note that compound XXI crystallizes
in a P21 space group, the molecule is chiral, and we
could establish its absolute configuration in crystal. In
whole crystals of compound XXI are a conglomerate,
i.e. crystallization is accompanied by spontaneous
enantiomeric resolution. Thus, by cyclizing a thiourea
containing a 2-chloropropylphosphinoyl we could
5
prepare a substituted 5,6-dihydro-1,3,4 -thiazaphos-
phinine, the first representative of P,N,S-containing
unsaturated six-membered heterocycles of this type.
pohacyclane XXI as a single diastereomer (
P
1
15.74 ppm). In the H NMR spectrum of compound
XXI, the methyl group at carbon appears as a doublet
The reaction of dibromoethane with a double molar
excess of silyl phosphite II resulted in isolation of
diphosphonate XXII whose treatment with PCl5 gave
compound XXIII.
3
4
of doublets ( 1.36 ppm, JHH 6.8, JHP 2.7 Hz). The
composition and structure of compound XXI were
also proved by its electron impact mass spectrum and
O
O
O
O
PCl5
Ia + II
(Me3SiO)2P(CH2)2P(OSiMe3)2
Cl2P(CH2)2PCl2
2Me3SiBr
XXII
XXIII
O
O
PhOP(CH2)2POPh
Cl
Cl
XXIV
2PhOH, 2Et3N
O
O
(PhO)2P(CH2)2P(OPh)2
XXV
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REACTION OF DIBROMOALKANES WITH SILYL PHOSPHITES
717
It should be noted that we failed to effect partial
phenoxylation of bisphosphonate XXIII with phenol
in the presence of base (reagent ratio 1:2:2) to pre-
pare dichloride XXIV. The major reaction product
was tetraphenyl diphosphonate XXV. A mixed di-
phosphonate in which each phosphorus atom is bound
with an ethoxy group and a chlorine atom (compound
XXVII), was prepared by the action of PCl5 on di-
phosphonate XXVI [23]. The reaction of diphos-
phonate XXVII with a double molar excess of me-
thylamine, performed with the aim to prepare new
P,N-containing heterocycles, failed to provide target
azadiphospholanes XXVIII. According to the 31P
NMR spectrum, a complex mixture of products
formed in this case. Mixed diphosphonate XXIX was
obtained by the reaction of compound XXVII with
excess methylamine.
NMR spectrum, P, ppm: 11.58. Found, %: P 8.42; Si
15.76. C9H24BrO3PSi2. Calculated, %: P 8.93; Si
16.13.
(2-Bromoethyl)phosphonic dichloride (IVa).
a. Phosphorus pentachloride, 42.0 g, was added in
portions to a mixture of 33.3 g of phosphonate IIIb
and 0.3 g of Cu2Cl2, heated to 100 C. Vacuum frac-
tionation gave 12.8 g (57%) of compound IVa, bp
68 C (0.06 mm Hg). 31P NMR spectrum, P, ppm:
44.21 [5].
b. A mixture of 21.0 g of diethyl trimethylsilyl
phosphite and 75.2 g of dibromoethane was heated
for 1 h at 150 C. Volatile compounds were removed,
the residue was treated with 41.6 g of PCl5, and the
mixture was allowed to stand for 2 h. Fractionation in
a vacuum gave 12.2 g (54%) of compound IVa, bp
68 70 C (0.06 mm Hg). 31P NMR spectrum, P, ppm:
44.21.
EXPERIEMNTAL
(3-Bromopropyl)phosphonic dichloride (IVb).
Phosphorus pentachloride, 22.5 g, was added in por-
tions with heating to 18 g of phosphonate IIIb. After
5 h, chlorotrimethylsilane and PCl5 were removed by
distillation, and the residue was fractionated in a
vacuum to obtain 10.5 g (87%) of compound IVb, bp
The IR spectrum was measured on a UR-20 in-
1
strument in the range 400 3600 cm in mineral oil.
1
The H NMR spectra were measured on a Bruker
WM-250 spectrometer (250.132 MHz), internal refe-
rence TMS. The 31P NMR spectra were obtained on
a Bruker MSL-400 Fourier spectrometer (100.62 MHz).
86 C (0.1 mm Hg). 31P NMR spectrum, P, ppm:
48.76. Found P, %: 12.71. C3H6BrCl2OP. Calculated
P, %: 12.92.
The electron impact mass spectra were obtained on
a Finnigan-MAT TRACE-MS instrument at 70 eV,
ion source temperature 200 C. Direct sample admis-
sion into the ion source was applied. The inlet probe
ampule was heated from 35 to 150 C at steps of
Ethyl (2-bromoethyl)phosphonochloridate
(VIIa). A solution of 0.92 g of ethanol in 10 ml of
chloroform was added to 4.5 g of dichloride IVa in
15 ml of chloroform. The reaction mixture was al-
lowed to stand for 12 h and then fractionated to obtain
1.8 g (38%) of compound VIIa, bp 75 C (0.1 mm
Hg). 31P NMR spectrum, P, ppm: 36.34. Found, %:
Br 34.44; Cl 15.31; P 12.48. C3H6BrCl2OP. Calcu-
lated, %: Br 33.97; Cl 15.07; P 13.16.
1
35 deg min . The mass spectra were treated using the
XCALIBUR program. The X-ray diffraction analysis
of compound XXI was performed on an Enraf Nonius
CAD-4 diffractometer at 20 C ( MoK radiation,
/2 scanning, 2qmax < 27.8 ).
Phosphite XV and phosphonate XVI were prepared
by known procedures [22, 24].
Phenyl (2-bromoethyl)phosphonochloridate
(VIIb). A mixture of 4.5 g of dichloride IVa and
1.9 g of phenol was heated for 15 h at 160 C and then
fractionated to obtain 2.2 g (40%) of compound VIIb,
Bis(trimethylsilyl) (2-bromoethyl)phosphonate
(IIIa). A mixture of 45 g of silyl phosphite II and
61 g of dibromoethane was heated for 2 h at 160 C
and then fractionated in a vacuum to obtain 42 g
(37%) of compound IIIa, bp 78 79 C (0.08 mm Hg),
n2D0 1.4437. 31P NMR spectrum, P, ppm: 7.28. Found,
%: P 9.39; Si 16.96. C8H22BrO3PSi2. Calculated,
%: P 9.30; Si 16.81.
bp 132 135 C (0.1 mm Hg). 31P NMR spectrum,
,
P
ppm: 33.54. Found Cl, %: 12.08. C8H9BrClO2P.
Calculated Cl, %: 12.58.
Ethyl (3-bromopropyl)phosphonochloridate
(VIIc). A solution of 1.5 g of ethanol and 3.03 g of
triethylamine in 10 ml of diethyl ether was added to a
solution of 7.2 g of dichloride IVb in 30 ml of diethyl
ether at 30 C. After 20 h triethylamine hydrochloride
was separated, the solvent was removed, and the
residue was fractionated in a vacuum to obtain 2.4 g
(32%) of compound VIIc, bp 104 C (0.08 mm Hg),
Bis(trimethylsilyl) 3-(bromopropyl)phospho-
nate (IIIb). A mixture of 15.0 g silyl phosphite II and
40 g of dibromopropane was heated for 2 h at 160 C,
bromotrimethylsilane and excess dibromopropane
were removed by distillation. The residue was frac-
tionated in a vacuum to obtain 9.5 g (55%) of com-
pound IIIb, bp 115 C (0.1 mm Hg), n2D0 1.4508. 31P
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 5 2006

718
PUDOVIK et al.
n2D0 1.4872. 31P NMR spectrum, P, ppm: 42.22.
Found P, %: 12.80. C5H11BrClO2P. Calculated P,
%: 12.42.
(66%) of diethylamine hydrobromide, mp 218 220 C
[25]. Found, %: Br 51.88; N 8.81. C4H12BrN. Cal-
culated, %: Br 51.95; N 9.09. 31P NMR spectrum,
ppm: 18.33, 26.29.
,
P
Diethyl (3-bromopropyl)phosphonate (VIII).
Phosphonic dichloride IVb, 3.6 g, was added to a
mixture of 1.4 g of ethanol and 3.0 g of triethylamine
in 30 ml of ether. After 2 h triethylamine hydrochlo-
ride was separated, the solvent was removed, and the
residue was fractionated in a vacuum to obtain 1.7 g
(44%) of phosphonate VIII, bp 87 C (0.06 mm Hg),
n2D0 1.4632. 31P NMR spectrum, P, ppm: 30.22.
Found, %: Br 31.36; P 12.24. C7H16BrO3P. Calcu-
lated, %: Br 30.80; P 11.97.
(2-Chloropropyl)phosphonic dichloride (XVII).
Phosphorus pentachloride, 49.5 g, was added with
stirring to 37 g of compound XVI heated to 140 C, in
the presence of a catalytic amount (0.3 g) of CuCl.
The reaction mixture was heated for 3 h at 140 C,
volatile compounds were removed, and the residue
was fractionated in a vacuum to obtain 10 g (43%) of
compound XVII, bp 70 74 C (0.06 mm Hg). 31P
NMR spectrum, P, ppm: 44.22. Found, %: Cl 54.12;
P 15.54. C3H6Cl3OP. Calculated, %: Cl 54.47;
P 15.86.
Ethyl trimethylsilyl (2-bromoethyl)phospho-
nate (Xa). Silylamide IX, 6.0 g, was slowly added to
7.0 g of chloride VIIa heated to 100 C. The mixture
was allowed to stand for 20 h at 20 C and fractionated
in a vacuum to obtain 4.2 g (49.4 %) of compound
Xa, bp 85 C (0.1 mm Hg), n2D0 1.4413. 31P NMR
spectrum, P, ppm: 17.26. Found, %: P 10.89; Si 9.63.
C7H18BrO3PSi. Calculated, %: P 10.72; Si 9.68.
Phenyl (2-chloropropyl)phosphonochloridate
(XVIII). A mixture of 7.7 g of dichloride XVII and
3.7 g of phenol was heated for 18 h at 160 C. Frac-
tionation gave 4 g (40%) of compound XVIII, bp
105 110 C (0.06 mm Hg). 31P NMR spectrum,
,
P
ppm: 32.07, 33.08. Found, %: Cl 28.04; P 12.90.
C9H11Cl2O2P. Calculated, %: Cl 28.06; P 12.25.
Ethyl trimethylsilyl (3-bromopropyl)phos-
phonate (Xb). A solution of 5 g of chloride VIIc and
4.0 g of silylamide IX in 30 ml of diethyl ether was
allowed to stand for 48 h at 20 C and then frac-
tionated in a vacuum to obtain 3.4 g (56%) of com-
pound Xb, bp 92 C (0.06 mm Hg). 31P NMR spec-
trum, P, ppm: 21.13. Found P, %: 8.87. C8H20BrO3
PSi. Calculated P, %: 9.12.
2-(Dimethylamino)-6-methyl-4-oxo-4-phenoxy-
5
5,6-dihydro-1,3,4 -thiazaphosphinine (XXI).
A
mixture of chloride XVIII and 0.77 g of potassium
thiocyanate in 5 ml of anhydrous acetonitrile was
heated for 10 h at 80 C. Potassium chloride, 0.58 g
(100%), was separated from the solution of compound
XIX ( 8.03, 9.86 ppm) that formed, acetonitrile was
removePd, the residue was dissolved in 5 ml of an-
hydrous benzene, and excess dimethylamine was
passed through the solution. After 24 h compound
XXI was filtered off, thrice recrystallized from
benzene, and dried in a vacuum. Yield 1.2 g (53%),
Ethyl (2-bromoethyl)phosphonoisothiocyana-
tidate (XI). A mixture of 5.6 g of chloride VIIa and
2.3 g of potassium thiocyanate was allowed to stand
for 24 h at 20 C. Potassium chloride was filtered off,
the solvent was removed, and the residue was frac-
tionated in a vacuum to obtain 1.3 g (21%) of com-
pound XI, bp 119 121 C (0.1 mm Hg). 31P NMR
spectrum, P, ppm: 12.82. Found, %: Br 31.36; P
11.77. C5H9BrNO2PS. Calculated, %: Br 31.00; P
12.01.
1
mp 200 202 C. IR spectrum (KBr), , cm : 1580
(C=N), 1250 (P=O). 1H NMR spectrum (CDCl3
3
C6D64), , ppm (J, Hz): 1.36 d.d (3H, CH3C, JHCCH
6.8, JHCCP 2.7), 1.71 m and 2.28 m (2H, HA, HB,
CH2), 3.07 br.s (3H, CH3N), 3.60 m (1H, CHS), 7.0
7.3 m (5H, C6H5). 31P NMR spectrum (DMSO-d6),
,
P
Reaction of isothiocyanate XI with dialkyl-
amines. a. Excess dimethylamine was passed through
a benzene solution of 2.58 g of phosphonoisothio-
cyanatidate XI, and the reaction mixture was allowed
to stand for 24 h at 20 C. Dimethylamine hydro-
bromide, 0.89 g (71%), was separated [25], mp 140
142 C. Found, %: C 19.89; H 7.12; Br 63.68; N
11.84. C2H8BrN. Calculated, %: C 19.04; H 6.34; Br
ppm: 15.03. Found, %: C 51.15; H 6.00; N 10.13;
P 10.86; S 10.86. C12H17N2O2PS. Calculated, %: C
50.70; H 5.98; N 9.85; P 10.91; S 11.26.
Ethylenebis(trimethylsilyl phosphonate) (XXII).
A mixture of 9.4 g of dibromoethane and 29.8 g of
silyl phosphite II was heated for 2 h at 160 C, volatile
products were removed, and the residue was frac-
tionated in a vacuum to obtain 12.5 g (52%) of com-
pound XXII, bp 147 151 C (0.08 mm Hg), solidifies
at room temperature. 31P NMR spectrum, P, ppm:
11.55. Found, %: P 12.73; Si 23.08. C14H40O6P2Si4.
Calculated, %: P 12.97; Si 23.43.
63.49; N 11.11. The 31P NMR spectrum of the residue
showed two signals at
18.89 and 29.69 ppm.
P
b. The reaction of 2.58 g of phosphonoisothio-
cyanatidate XI and 0.73 g of diethylamine gave 1.02 g
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 5 2006

REACTION OF DIBROMOALKANES WITH SILYL PHOSPHITES
719
Ethylenebis(phosphonic dichloride) (XXIII).
Phosphorus pentachloride, 20.9 g, was added in
portions to 12 g of diphosphonate XXII at 120 C.
Volatile compounds (chlorotrimethylsilane, PCl3)
were removed, and the residue was washed with ether
to obtain 6.1 g (91%) of compound XXIII, mp 110 C
[26].
6. Ford-Moore, A.H. and Williams, J.H., J. Chem. Soc.,
1947, p. 1465.
7. Schroeder, J.P., Few, L.B., and Peters, V.M., J. Org.
Chem., 1970, vol. 35, no. 9, p. 3181.
8. Gololobov, Yu.G., Voitekunas, Yu.B., Petrovskii, P.V.,
and Polyakova, A.M., Izv. Akad. Nauk SSSR, Ser.
Khim., 1983, no. 9, p. 2170.
Ethylenebis(phenyl phosphonate) (XXV).
A
9. Horner, L. and Lindel, H., Phosphorus, Sulfur Relat.
Elem., 1984, vol. 20, no. 2, p. 161.
solution of 5.28 g of diphosphonate XXIII, 3.76 g of
phenol, and 4.0 g of triethylamine in 80 ml of me-
thylene chloride was refluxed for 1 h. Triethylamine
hydrochloride was separated, the solvent was removed,
and the residue was dried in a vacuum to obtain 3.9 g
(79%) of compound XXV, mp 152 156 C. 31P NMR
spectrum, P, ppm: 21.89. Found P, %: 12.41.
C26H24O6P2. Calculated P, %: 12.55 [27].
10. Hewitt, D.J. and Teese, M.W., Aust. J. Chem., 1984,
vol. 37, no. 1, p. 205.
11. Afaque, S., Ansari, M., Ahmad, F., and Siddiqui, M.,
Indian J. Chem., Sect. B, 1989, vol. 28, no. 4, p. 308.
12. Montoneri, E. and Ricca, G., Phosphorus, Sulfur Relat.
Elem., 1991, vol. 55, nos. 1 4, p. 111.
13. Abel, E.W. and Illingworth, S.M., Organomet. Chem.
Rev. A, 1970, no. 5, p. 143.
Ethylenebis(ethyl N-methylphosphonamidate)
(XXIX). Excess methylamine was passed through a
solution of 5.6 g of chloride XXVII in 30 ml of
methylene chloride. After 4 h methylamine hydro-
chloride was separated, and the solvent was removed
to obtain 4.3 g (79%) of compound XXIX, mp 118
121 C. 31P NMR spectrum, P, ppm: 35.58. Found,
%: N 10.28; P 22.73. C8H16N2O4P2. Calculated, %: N
10.29; P 22.79.
14. Chernyshev, E.A., Bugerenko, E.F., Akat’eva, A.S.,
and Naumov, A.D., Zh. Obshch. Khim., 1975, vol. 45,
no. 1, p. 242.
15. Pudovik, M.A., Medvedeva, M.D., and Pudovik, A.N.,
Zh. Obshch. Khim., 1975, vol. 45, no. 3, p. 700.
16. Lebedev, E.P., Pudovik, A.N., Tsyganov, B.N., Naz-
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ACKNOWLEDGMENTS
The work was financially supported by the Russian
Foundation for Basic Research (project no. 03-03-
33064).
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