Reactions of N,N′-dialkylcyclohexane-1,2-diimines with trivalent phosphorus acid chlorides

Article abstract of DOI:10.1023/A:1012325622135

N,N′-Dialkylcyclohexane-1,2-diimines react with trivalent phosphorus acid chlorides to give, depending on the structure of the organophosphorus reagent and reaction conditions, either 1,3,2-diazaphospholanes (three-coordinate phosphorus) containing the cy

Full text of DOI:10.1023/A:1012325622135

Russian Journal of General Chemistry, Vol. 71, No. 3, 2001, pp. 437 442. Translated from Zhurnal Obshchei Khimii, Vol. 71, No. 3, 2001,
pp. 473 478.
Original Russian Text Copyright
2001 by Lodochnikov, Gryaznova, Gryaznov, Musin, Kibardin.
Reactions of N,N -Dialkylcyclohexane-1,2-diimines
with Trivalent Phosphorus Acid Chlorides
V. G. Lodochnikov, T. V. Gryaznova, P. I. Gryaznov,
R. Z. Musin, and A. M. Kibardin
Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center,
Russian Academy of Sciences, Kazan, Tatarstan, Russia
Received December 28, 1999
Abstract N,N -Dialkylcyclohexane-1,2-diimines react with trivalent phosphorus acid chlorides to give,
depending on the structure of the organophosphorus reagent and reaction conditions, either 1,3,2-diazaphos-
pholanes (three-coordinate phosphorus) containing the cyclohexadiene fragment in positions 4 and 5, or 1,3,2-
diazaphospholines (four-coordinate phosphorus).
Previously we have demonstrated the feasibility of
preparing P,N-containing heterocycles by reactions of
acyclic -diimines with electrophilic phosphorus com-
pounds [1 4]. We suggested that the reaction of -di-
imines with trivalent phosphorus acid chlorides fol-
lows the pattern [1+4]-cycloaddition, with diimine as
the diene component. Therefore, it seemed interesting
to perform such reactions with -diimines having a
rigid s-cis arrangement of the C=N bonds. However,
the reactions of diimines containing endocyclic C=N
bonds (5,6-dihydropyrazines) with both three- and
four-coordinate phosphorus acid chlorides involved
only one of the two C=N bonds and yielded the cor-
responding N-phosphorylated tetrahydropyrazines [5].
Here we will not discuss in detail the tautomeric
transformations of cyclohexanediimines and the spec-
tral evidences of the presence of particular isomers; it
will be a subject of a separate paper. Here we report
on reactions of cyclohexanediimines I and II with
mono- and dichlorides of various trivalent phosphorus
acids.
We have shown previously that cyclic N,N -dibu-
tyl-2,3-butanediimine reacts with ethyl phosphorodi-
chloridite and diethyl phosphorochloridite exclusively
by the scheme of [1+4]-cycloaddition [1]. The reac-
tion occurs via intermediate formation of phosphor-
anes or phosphonium salts, which undergo dealkyla-
tion to give the final 1,3,2-diazaphospholines with the
four-coordinate phosphorus atom. The reaction path-
way and the structures of the final products are not
affected by the presence of an organic base.
Alternative objects with such a feature are N,N -di-
alkylcyclohexane-1,2-diimines with exocyclic location
of the C=N bonds. The cisoid arrangement of the
C=N bonds gives strong grounds to believe that this
compounds will actively participate in [1+4]-cycload-
dition reactions with trivalent phosphorus derivatives,
yielding new P,N-containing heterocycles.
Cyclohexanediimines I and II react with both ethyl
phosphorous dichloride and diethyl phosphorous
chloride under mild conditions. A specific feature of
such reactions is the fact that formation of one or
another product depends on the presence of a base.
Reaction of cyclohexanediimine II with ethyl phos-
phorous dichloride in the presence of triethylamine in
a 1 : 1 : 2 ratio yields a product whose 31P NMR spec-
N,N -Dialkylcyclohexane-1,2-diimines I and II
theoretically can exist as tautomers A C. According
1
to the H and 13C NMR and IR data, tautomer B pre-
vails, although the presence of minor amounts of tau-
tomers A and C cannot be ruled out.
trum contains a signal at
107 ppm, indicative of a
trivalent phosphorus atom. PThe spectra of the isolated
product allow its identification as 1,3-dibutyl-2-
ethoxy-5,6-dihydro-1,3,2-diazaphosphindane (III).
NR
NHR
NHR
NR
NR
NHR
NBu
A
B
C
2B
II + EtOPCl2
I, II
P OEt
2B HCl
NBu
III
R = Me (I), Bu (II).
1070-3632/01/7103-0437$25.00 2001 MAIK Nauka/Interperiodica

438
LODOCHNIKOV et al.
1
The H NMR spectrum of III contains two triplets
at 0.82 and 1.03 ppm due to methyl protons of the
butyl groups and ethoxy substituent at the phosphorus
atom. The , -methylene protons of the butyl group
give a multiplet at 1.25 1.65 ppm, and the methyl-
ene protons of the cyclohexyl substituent give a nar-
row multiplet centered at 2.24 ppm. The spectrum
also contains a doublet of triplets from -methylene
protons of the butyl groups and a doublet of quartets
from the methylene protons of the ethoxy group.
a doublet at 2.42 ppm (3JPH 8 Hz) from N-methyl
protons, and a broadened singlet at 4.38 ppm from
methine protons. The IR spectrum contains character-
istic absorption bands of the diene system of the cy-
clohexadiene substituent.
Cyclohexanediimines I and II react with phosphor-
ous monochlorides in the presence of a base at a
molar ratio of the reactants of 1 : 2 : 2. With diethyl
phosphorochloridite as the second reactant, we iso-
lated and characterized 2-ethoxy-1,3,2-diazaphospho-
lanes III and V and triethyl phosphite.
A broadened singlet at
methine protons of the cyclohexadiene ring. The IR
4.43 ppm belongs to the
spectrum of III contains the bands of the P O C
NR
1
2B
bonds (1030 cm ), C=C bonds of the cyclohexadiene
I, II + 2(EtO)2PCl
P OEt
1
2B HCl
ring (1615 s and 1670 w, cm ), and C H bonds at
NR
III, V
1
the sp2-hybridized carbon atom (3040 cm ).
The structure and composition of the resulting di-
azaphospholane III were confirmed by high-resolution
mass spectrometry. The spectrum contains a peak at
m/z 296 assignable to the molecular ion [M]+ of III.
The accurately measured weight of this ion, 296.2016,
is nicely consistent with the calculated weight of the
molecule C16H29N2OP, 296.2017. The main fragmen-
tation pathway of [M]+ involves the loss of olefin
molecules C2H4 and C4H8 and of radicals OC2H5,
C2H5, and C4H9 from substituents at N and P. Fur-
ther fragmentation involves the loss of the C4H8 or
C4H9 group from the other nitrogen atom. The se-
quence of losses can also be inverse. The base peak,
m/z 179, is due to the ion [C6H5N(C4H9)P]+ originat-
ing probably from cleavage of the C N and P N
bonds in the ion [M OC2H5]. For all the fragment
ions mentioned above, the experimental m/z values
agree with the values calculated from the elemental
composition. The fragmentation pattern under electron
impact is also consistent with the proposed structure.
+ (EtO)3P,
R = Bu (III), Me (V).
The reaction of II with ethyl diethylamidophos-
phorous chloride in the presence of a base occurs si-
milarly, yielding exclusively 2-ethoxydiazaphospho-
lane III and ethyl ethyl phosphorous tetraethyldiamide.
OEt
2B
II + ClP
III + (Et2N)2POEt.
2B HCl
NEt2
The above-described amidodiazaphospholane IV
was also prepared by reaction of diimine II with tetra-
methylphosphorodiamidous chloride in the presence
of triethylamine.
2B
II + 2(Me2N)2PCl
IV + (Me2N)3P.
2B HCl
The reaction occurs under mild conditions (ben-
zene, room temperature), as in the case of alkyl phos-
phorochloridites. It should be noted that the previ-
ously studied reactions of acyclic N,N -dibutyl-2,3-
butanediimine with phosphorodiamidous chlorides in
the presence of a base are complete in 30 days, or in
14 h under refluxing in benzene [6].
The reaction of cyclohexanediimine II with di-
methylamidophosphorous dichloride in the presence
of a base at the reactant ratio of 1 : 1 : 2 occurs si-
milarly. Its product, 1,3-dibutyl-2-dimethylamino-5,6-
dihydro-1,3,2-diazaphosphindane IV, was isolated and
characterized.
NBu
2-Aminophospholane IV readily takes up sulfur to
give 1,3-dibutyl-2-dimethylamino-5,6-dihydro-1,3,2-
diazaphosphindane 2-sulfide VI.
2B
II + Me2NPCl2
P NMe2
NBu
2B HCl
IV
NBu
S
The 31P NMR spectrum of IV consists of a single
IV + S
P
NBu
1
NMe2
signal at
107 ppm. The H and IR spectra confirm
P
1
VI
the structure of the product. The H NMR spectrum,
along with the signals from butyl protons, contains a
narrow multiplet centered at 2.29 ppm, belonging
to the methylene protons of the cyclohexadiene ring,
Our results suggest that reactions of cyclohexane-
diimines with trivalent phosphorus acid chlorides
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 3 2001

REACTIONS OF N,N -DIALKYLCYCLOHEXANE-1,2-DIIMINES
439
occur in steps. First, apparently, nucleophilic substitu-
tion at phosphorus yields monophosphorylation prod-
uct VII, enamino imine D occurring in equilibrium
with diamine E, which subsequently reacts with the
second molecule of phosphorous chloride to give
N,N -diphosphorylated cyclohexadienediamine VIII.
The latter undergoes cyclization to give the final prod-
ucts, 1,3,2-diazaphospholanes III and IV.
N(R)PR2
NR
NHR
ClR2, B
ClR2, B
B HCl
III, IV + PR3.
I, II
B HCl
N(R)PR2
N(R)PR2
N(R)PR2
D
E
VII
With phosphorous dichlorides, the cyclization can
occur in the stage of formation of monophosphoryl-
ated diamine VII of type D.
tra of the reaction products contain no bands charac-
teristic of the cyclohexadiene moiety but contain a
1
weak band at 1680 cm . The 1H NMR spectra
contain no signals assignable to the methine proton of
the cyclohexadiene moiety. Therefore, we suggested
that these reactions yielded 2-R-1,3-dibutyl-4,5,6,7-
tetrahydro-1,3,2-diazaphosphindane 2-oxides X and
XI, similar to the reactions of acyclic N,N -dibutyl-
butanediimine with phosphorus acid chlorides [1].
Since cyclohexanediimines I and II exist mainly in
the form of tautomer B, we suggested that they would
react with phosphorous triamides similarly to second-
ary amines [7]. We found, however, that diimine II
does not react with hexamethylphosphorous triamide
even on heating to 150 C in a sealed ampule.
NBu
O
OEt
R
We expected that the reactions of cyclohexanedi-
imines of phosphorus acid chlorides in the absence of
a base would yield diazaphospholines with four-coor-
dinate phosphorus, similar to reactions of acyclic
N,N -dibutyl-2,3-butanediimine with phosphorous
chlorides [1]. However, the 31P NMR spectrum of the
reaction mixture of cyclohexanediimine II with alkyl
dialkylamidophosphorous chloride contains a single
P
NBu
II + ClP
EtCl
R
X, XI
R = OEt (X), Cl (XI).
The poor yield of X and XI is probably due to the
fact that in the absence of organic base both [1+4]-
cycloaddition and nucleophilic substitution at phos-
phorus are possible. In the latter case the reaction
mixture will contain, along with trivalent phosphorus
compounds, also HCl and C2H5OH molecules, which
will induce cleavage of the endocyclic P N bond in
the forming diazaphospholanes [8]. Therefore, it is
feasible to isolate only diazaphospholines X and XI
with a four-coordinate phosphorus atom, since they
are more resistant to HCl and C2H5OH.
signal at
106.8 ppm. Based on the spectroscopic
P
data, physicochemical constants, and previous results,
we ascribed to the product the structure of III. Along
with diazaphospholane III, we isolated a crystalline
compound identified by analysis as diethylamine
hydrochloride. Apparently, similar to all the above-
described reaction systems, the reaction starts with the
nucleophilic attack of the diimine nitrogen atom at
the phosphorus atom of the amidophosphorous chlo-
ride, yielding the monophosphorylated enamino imine
or its tautomer IX occurring in the form of hydro-
chloride as the reaction mixture contains no organic
base. The subsequent elimination of diethylamine
hydrochloride and intramolecular cyclization ultimate-
ly yield 1,3,2-diazaphospholane III.
Cyclohexanediimine I reacts with ethyldichloro-
phosphine in the absence of triethylamine under mild
conditions exclusively by the [1+4]-cycloaddition
scheme to give phosphonium salt XII which was iso-
lated and characterized. Hydrolysis of salt XII yields
1,3-dimethyl-2-ethyl-4,5,6,7-tetrahydro-1,3,2-diaza-
phosphindane 2-oxide XIII identified by elemental
analysis and spectroscopy.
Reaction of cyclohexanediimine II with ethyl
phosphorous dichloride or diethyl phosphorous chlo-
ride in a 1 : 1 ratio in the absence of triethylamine, in
contrast to the process described above, yields the
four-coordinate phosphorus compounds. The IR spec-
Thus, reactions of cyclohexanediimines with tri-
valent phosphorus acid chlorides can yield two differ-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 3 2001

440
LODOCHNIKOV et al.
1,3-Dibutyl-2-ethoxy-5,6-dihydro-1,3,2-diaza-
Me
N
phosphindane III. a. A solution of 3.67 g of ethyl
phosphorous dichloride in 50 ml of benzene was added
dropwise with stirring to a solution of 5.55 g of di-
imine II and 5.05 g of triethylamine in 150 ml of
benzene, cooled to 10 C. The mixture was left over-
night, after which the precipitate of triethylamine
hydrochloride was filtered off; yield 6.3 g (92%).
The solvent was removed in vacuo, and the residue
was distilled; 3.71 g (50%) of diazaphospholane III
was obtained, bp 140 C (0.06 mm), d240 1.01336.
Cl
Cl
Et
+
I + EtPCl2
P
N
Me
XII
Me
N
O
H2O, 2B
2B HCl
P
n2D0 1.5158. 31P NMR spectrum:
107 ppm. Mass
P
Et
N
spectrum, m/z (Irel, %): 297 (9.3), 296 (37), M+
[C16H29N2OP]+, 296 (14) [M C2H4]+, 267 (29) [M
Me
XIII
C2H5]+, 251 (21) [M
OC2H5]+, 240 (13) [M
C4H8]+, 239 (36) [M C4H9] , 212 (14) [M C2H4
C2H8]+, 211 (21) [M C2H4 C7H9]+, 210 (3.8) [M
OC2H5 C4H9]+, 195 (1.5) [M OC2H5 C4H8]+,
194 (5.9) [M OC2H5 C4H9]+, 180 (15), 179 (100)
[C6H5N(C4H9)P]+, 156 (2.6) [M C2H4 (C4H8)2]+,
+
+
ent types of products depending on the presence of a
base (HCl acceptor) in the reaction mixture. In the
presence of a base, the reaction yields 1,3,2-diaza-
phospholanes containing a cyclohexadiene moiety,
and in the absence of a base, bicyclic 1,3,2-diaza-
phospholenes containing a four-coordinate phosphorus
atom are formed.
154 (7.5) [M
C2H4
(C4H9)2] , 153 (5.5) [M
C2H5 (C4H9)2]+, 139 (7.7) [M OC2H5 (C4H8)2]+,
138 (6.6) [M OC2H5 C4H8 C4H9]+, 137 (11)
[M
OC2H5
(C4H9)2]+.
EXPERIMENTAL
b. A solution of 7.82 g of diethyl phosphorous
The IR spectra were taken on a UR-20 spectro-
photometer in the 400 3600 cm range from thin
chloride in 25 ml of benzene was added dropwise with
stirring to a solution of 5.55 g of diimine II and 5.05 g
of triethylamine in 150 ml of benzene, cooled to 10
15 C. The mixture was left overnight, after which the
precipitate of triethylamine hydrochloride was filtered
off; yield 5.4 g (79%). The solvent was removed in
vacuo, and the residue was distilled. Triethyl phos-
phite and diazaphospholane III were isolated. Triethyl
phosphite: yield 2.01 g (48%), bp 42 43 C (10 mm),
1
films of substances on KBr and NaCl supports; the
1
wave numbers were determined to within 2 cm .
The NMR spectra of solutions and reaction mix-
tures were recorded on a Bruker WM-250 NMR
Fourier spectrometer (working frequency 101.3 MHz,
internal reference deuterium signal of deuterated
solvent, pulse length 7 s). The spectra of a number
of pure substances were measured on a KGU-4 cus-
tom-made NMR spectrometer (working frequency
10.2 MHz) with broad-band 31P {1H} decoupling
n2D0 1.4108. 31P NMR spectrum:
139 ppm.
Compound III: yield 3.1 g (42%), bpP 138 139 C
(0.06 mm Hg), n2D0 1.5157. IR spectrum, , cm :
1
1030 (POC), 1620 s, 1675 w (=C C=), 3040 (HC=).
1H NMR spectrum (C6D6), , ppm: 0.82 t (6H,
CH3CH2CH2CH2, 3JHH 6 Hz), 1.05 t (3H, CH3CH2O,
3JHH 7 Hz), 1.18 1.65 m (8H, CH3CH2CH2CH2),
2.22 m (4H, cyclo-CH2 CH2), 3.03 d.t (4H, CH3CH2
1
(external reference 85% H3PO4). The H NMR spectra
were measured on a Varian T-60 spectrometer (work-
ing frequency 60.0 MHz) in calibrated ampules; sam-
ples were prepared as 10 vol % solutions, with TMS
as internal reference.
3
3
CH2CH2, JHH 6.5, JPH 13 Hz), 3.17 d.q (2H,
3
3
The mass spectra were taken on an MKh-1310
spectrometer at the ionizing electron energy of 70 eV
and electron collector current of 30 A. The samples
were introduced with an SVP-5 direct inlet system at
the vaporizer temperature of 120 C. The accurate
weights were determined by off-line processing of the
mass spectra with an SM-4 computer using reference
peaks of perfluorokerosene. The m/z values were
CH3CH2O, JHH 7, JPH 14 Hz), 4.38 br.s (2H, CH).
31P NMR spectrum:
107 ppm. Found P, %: 10.13.
P
C16H29N2OP. Calculated P, %: 10.47.
c. A solution of 3.75 g of ethyl diethylamidophos-
phorous chloride in 20 ml of benzene was added drop-
wise with stirring to a solution of 2.27 g of diimine II
and 2.07 g of triethylamine in 100 ml of benzene,
cooled to 10 15 C. The precipitate of triethylamine
hydrochloride was filtered off; yield 2.7 g (96%).
The solvent was removed in vacuo, and the residue
was distilled. Ethyl tetraethylamidophosphite and
6
determined to within 5 10 amu.
All experiments were performed under argon with
absolute solvents and freshly distilled chemicals.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 3 2001

REACTIONS OF N,N -DIALKYLCYCLOHEXANE-1,2-DIIMINES
441
diasaphospholane III were isolated. Ethyl tetraethyl-
The mixture was left overnight, after which the pre-
cipitate of triethylamine hydrochloride was filtered
off; yield 1.31 g (95%). The solvent was removed in
vacuo, and the residue was distilled. Diazaphospho-
lane IV was obtained; yield 0.75 g (51%), bp 140
142 C (0.06 mm), d240 0.9969, nD20 1.5272. 31P
amidophosphite: yield 1.31 g (58%), bp 92 95 C
(10 mm). 31P NMR spectrum:
130 ppm.
P
Compound III: yield 1.85 g (61%), bp 138 140 C
(0.06 mm Hg), d240 1.0135, n2D0 1.5150. 31P NMR
spectrum:
107 ppm.
P
NMR spectrum:
107 ppm. Found P, %: 10.21.
C16H30N3P. CalculPated P, %: 10.51.
d. A solution of 2.05 g of ethyl diethylamidophos-
phorous chloride in 25 ml of benzene was added drop-
wise with stirring to a solution of 2.48 g of II in 50 ml
of benzene, cooled to 10 15 C. The mixture was left
for 12 h, after which the precipitate of diethylamine
hydrochloride was filtered off; yield 1 g (82%),
1,3-Dimethyl-2-ethoxy-5,6-dihydro-1,3,2-diaza-
phosphindane V. A solution of 7.03 g of diethyl
phosphorous chloride in 50 ml of diethyl ether was
added dropwise with stirring to a solution of 3.1 g of
diimine I and 4.54 g of triethylamine in 150 ml of
diethyl ether, cooled to 15 C. The mixture was left
for 12 h, after which the precipitate of triethylamine
hydrochloride was filtered off; yield 6.1 g (99%). The
solvent was removed in vacuo, and the residue was
distilled. Triethyl phosphite and diazaphospholine V
were obtained. Triethyl phosphite: yield 1.81 g (49%),
bp 40 41 C (10 mm), n2D0 1.4102. 31P NMR spec-
1
mp 230 C. H NMR spectrum, , ppm: 1.84 t (6H,
3
3
CH3CH2, JHH 7 Hz), 2.97 q (4H, CH3CH2, JHH
7 Hz), 7.95 br.s (2H, NH2+). The solvent was removed
in vacuo, and the residue was distilled. Diazaphospho-
lane III (1.52 g, 46%) was obtained; bp 136 138 C
(0.06 mm), n2D0 1.5154. IR spectrum, , cm :
1
1030 (POC), 1615 s, 1670 w (=C C=), 3040 (HC=).
1H NMR spectrum (C6D6), , ppm: 0.82 t (6H,
3
CH3CH2CH2CH2, JHH 6 Hz), 1.1 t (3H, CH3CH2O,
trum:
140 ppm. Compound V: yield 2.84 g (60%),
3JHH 7 Hz), 1.13 1.60 m (8H, CH3CH2CH2CH2),
2.27 m (4H, cyclo-CH2CH2), 3.07 d.t (4H, CH3CH2
bp 123P 124 C (0.08 mm), d420 1.0134, n2D0 1.4937.
1
IR spectrum, , cm : 1035 (POC), 1625 s, 1675 w
3
3
1
CH2CH2, JHH 6.5, JPH 13 Hz), 3.15 d.q (2H,
(=C C=), 3035 (HC=). H NMR spectrum (C6D6), ,
3
3
CH3CH2O, JHH 7, JPH 14 Hz), 4.33 br.s (2H, CH).
31P NMR spectrum:
106.8 ppm.
ppm: 1.15 t (3H, CH3CH2O, 3JHH 7 Hz), 2.27 m (4H,
3
cyclo-CH2CH2), 2.64 d (6H, NCH3, JPH 9 Hz),
P
3.95 m (2H, CH3CH2O), 4.35 br.s (2H, =CH2). 31P
1,3-Dibutyl-2-dimethylamino-5,6-dihydro-1,3,2-
diazaphosphindane IV. a. A solution of 6.96 g of
tetramethylamidophosphorous chloride in 50 ml of
benzene was added dropwise with stirring to a solu-
tion of 5 g of II and 4.55 g of triethylamine in 150 ml
of benzene, cooled to 10 C. The mixture was left
overnight, after which the precipitate of triethylamine
hydrochloride was filtered off; yield 5.7 g (92%). The
solvent was removed in vacuo, and the residue was
NMR spectrum:
C10H17N2OP. Calculated P, %: 14.62.
110 ppm. Found P, %: 14.88.
P
1,3-Dibutyl-2-dimethylamino-5,6-dihydro-1,3,2-
diazaphosphindane 2-sulfide VI. A 0.217-g portion
of sulfur was gradually added to a solution of 2 g of
diazaphospholane IV in 20 ml of benzene. The mix-
ture was left for 12 h, after which the solvent was
removed in vacuo. The residue was distilled, and
distilled. Phosphorous hexamethyltriamide and diaza- 1.73 g (78%) of VI was obtained, bp 196 198 C
phospholane
IV
were
obtained.
Phosphor-
(0.1 mm Hg), d240 1.05824, n2D0 1.54874. IR spectrum,
1
ous hexamethyltriamide: yield 2.71 g (74%), bp 47
48 C (10 mm Hg), n2D0 1.4657. 31P NMR spectrum:
120 ppm. Compound IV: yield 5.15 g (78%), bp 143P
144 C (0.08 mm), d240 0.9961, n2D0 1.5275. IR
, cm : 745 (P=S), 1595, 1670 (=C C=), 3050
1
(H C=). H NMR spectrum (C6D6), , ppm: 0.82 t
3
(6H, CH3CH2CH2CH2, JHH 6.5 Hz), 1.18 1.59 m
(8H, CH3CH2CH2CH2), 2.21 m (4H, cyclo-CH2);
1
3
spectrum, , cm : 1620 s, 1670 w (=C C=), 3035
2.35 d (6H, N CH3, JPH 8 Hz), 3.14 d.t (4H, CH3
1
3
3
(HC=). H NMR spectrum (C6D6), , ppm: 0.85 t
CH2CH2CH2, JHH 6, JPH 10 Hz), 4.35 br.s (4H,
(6H, CH3CH2CH2CH2, 3JHH 6 Hz), 1.65 1.17 m (8H,
CH3CH2CH2CH2), 2.29 m (4H, cyclo-CH2CH2),
2.37 d (6H, N CH3, 3JPH 7 Hz), 3.5 d.t (4H, CH3CH2
=CH). 31P NMR spectrum:
74 ppm. Found P, %:
9.14. C16H30N3PS. CalculatePd P, %: 9.48.
3
3
1,3-Dibutyl-2-ethoxy-4,5,6,7-tetrahydro-1,3,2-
diazaphosphindane 2-oxide X. A solution of 2.45 g
of diethyl phosphorous chloride in 50 ml of benzene
was added dropwise with stirring to a solution of
3.33 g of II in 100 ml of benzene, cooled to 10 C.
The mixture was left for 12 h, after which the solvent
was removed in vacuo, and the residue was distilled.
Diazaphospholine X was obtained; yield 2.01 g
CH2CH2, JHH 6, JPH 10 Hz), 4.38 br.s (2H, =CH).
31P NMR spectrum:
106 ppm. Found P, %: 10.29.
P
C16H30N3P. Calculated P, %: 10.51.
b. A solution of dimethylamidophosphorous dichlo-
ride in 50 ml of benzene was added dropwise with
stirring to a solution of 1.11 g of II and 1.01 g of
triethylamine in 50 ml of benzene, cooled to 5 10 C.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 3 2001

442
LODOCHNIKOV et al.
(43%), bp 150 151 C (0.06 mm), n2D0 1.4979. IR
overnight, after which the precipitate of triethylamine
hydrochloride (12.5 g, 99%) was filtered off. The
solvent was removed in vacuo, and the residue was
distilled. Diazaphospholine XIII was obtained; yield
7.5 g (76%), bp 133 C (0.05 mm Hg), n2D0 1.5300.
1
spectrum, , cm : 1040 (POC), 1230 (P=O), 1680
1
(C=C). H NMR spectrum (C6D6), , ppm: 0.77 t
3
(6H, CH3CH2CH2CH2, JHH 6 Hz), 1.01 t (3H,
3
CH3CH2O, JHH 7 Hz), 1.21 1.60 m (8H, CH3CH2
1
1
CH2CH2), 1.65 m (4H, cyclo-CH2CH2), 2.03 m (4H,
IR spectrum, , cm : 1240 (P=O), 1675 (C=C). H
NMR spectrum (CCl4), , ppm: 1.10 t (3H, CH3CH2),
1.61 m (4H, cyclo-CH2CH2), 1.90 m (2H, CH3CH2),
3
cyclo-CH2C=), 2.71 d.t (4H, CH3CH2CH2CH2, JHH
3
3
3
6, JPH 12 Hz), 2.93 d.q (2H, CH3CH2O, JHH 7, JPH
14 Hz). 31P NMR spectrum:
18.9 ppm. Found P,
2.33 m (4H, cyclo-CH2=C), 2.76 d (6H, NCH3, JPH
3
%: 9.42. C16H31N2O2P. CalcuPlated P, %: 9.87.
10 Hz). 31P NMR spectrum:
44 ppm. Found P, %:
P
14.32. C10H19N2OP. Calculated P, %: 14.49.
1,3-Dibutyl-2-chloro-4,5,6,7-tetrahydro-1,3,2-di-
azaphosphindane 2-oxide XI. A solution of 1.96 g
of ethyl phosphorous dichloride in 50 ml of benzene
was added dropwise with stirring to a solution of 3 g
of II in 100 ml of benzene, cooled to 10 C. The
mixture was left for 2 h, after which the solvent was
removed in vacuo, and the residue was distilled. Diaza-
phospholene XI was obtained; yield 1.96 g (48%), bp
REFERENCES
1. Kibardin, A.M., Gazizov, T.Kh., and Pudovik, A.N.,
Izv. Akad. Nauk SSSR, Ser. Khim., 1980, no. 6, p. 1452.
2. Kibardin, A.M., Mikhailov, Yu.B., Gryaznova, T.V.,
and Pudovik, A.N., Izv. Akad. Nauk SSSR, Ser. Khim.,
1986, no. 7, p. 1684.
155 158 C (0.06 mm), n2D0 1.5196. IR spectrum,
,
1
1
cm : 530 (P Cl), 1235 (P=O), 1680 (C=C). H NMR
3. Kibardin, A.M., Gryaznova, T.V., Enikeev, K.M., Mi-
khailov, Yu.B., and Pudovik, A.N., Izv. Akad. Nauk
SSSR, Ser. Khim., 1987, no. 7, p. 1684.
spectrum (C6D6), , ppm: 0.87 t (6H, CH3CH2CH2
3
CH2, JHH 7 Hz), 1.16 1.62 m (8H, CH3CH2CH2
CH2), 1.78 m (4H, cyclo-CH2CH2), 2.05 m (4H,
4. Kibardin, A.M. and Pudovik, A.N., Zh. Obshch. Khim.,
3
cyclo-CH2C=), 3.03 d.t (4H, CH3CH2CH2CH2, JHH
1993, vol. 63, no. 11, pp. 2430 2441.
3
7, JPH 7 Hz). 31P NMR spectrum: P 25 ppm. Found,
5. Lodochnikov, V.G., Gryaznova, T.V., Gryaznov, P.I.,
Musin, R.Z., and Kibardin, A.M., Zh. Obshch. Khim.,
1999, vol. 69, no. 12, pp. 1970 1974.
%: Cl 10.84; P 9.42. C14H26ClN2OP. Calculated, %:
Cl 11.66; P 10.18.
1,3-Dimethyl-2-ethyl-4,5,6,7-tetrahydro-1,3,2-di-
azaphosphindane 2-oxide XIII. A solution of 6.01 g
of ethyldichlorophosphine in 50 ml of diethyl ether
was added dropwise with stirring to a solution of
6.33 g of I in 150 ml of diethyl ether, cooled to
10 C. Salt XII precipitated; mp 53 C. 31P NMR
6. Kibardin, A.M., Litvinov, I.A., Naumov, V.A., Efre-
mov, Yu.Ya., Gryaznova, T.V., and Pudovik, A.N.,
Dokl. Akad. Nauk SSSR, 1987, vol. 297, no. 2,
pp. 376 379.
7. Burgada, R., Ann. Chim., 1963, vol. 8, nos. 5 6,
pp. 347 381.
spectrum (CHCl3):
75.4 ppm. After 1 h, we added
P
9.27 g of triethylamine and then, dropwise, 0.82 g of
water with cooling to 0 5 C. The mixture was left
8. Kibardin, A.M., Gryaznova, T.V., and Pudovik, A.N.,
Zh. Obshch. Khim., 1996, vol. 66, no. 3, pp. 376 382.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 3 2001