Reaction of dialkyl phosphites with N-2-methyl-2- chloropropylidenealkylamines

Full text of DOI:10.1134/S0012500810070025

ISSN 0012ꢀ5008, Doklady Chemistry, 2010, Vol. 433, Part 1, pp. 186–190. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © M.B. Gaziziov, R.A. Khairullin, A.A. Minnikhanova, A.I. Alekhina, A.A. Bashkirtsev, O.G. Sinyashin, 2010, published in Doklady Akademii Nauk, 2010,
Vol. 433, No. 3, pp. 352–356.
CHEMISTRY
Reaction of Dialkyl Phosphites
with Nꢀ2ꢀMethylꢀ2ꢀchloropropylidenealkylamines
M. B. Gaziziov, R. A. Khairullin, A. A. Minnikhanova, A. I. Alekhina,
A. A. Bashkirtsev, and Academician O. G. Sinyashin
Received February 16, 2010
DOI: 10.1134/S0012500810070025
Organophosphorus compounds (OPCs) containꢀ
The reaction of dialkyl phosphites
I with comꢀ
ing aminoalkylphosphoryl fragments are of large pracꢀ pounds II leads to the initial formation of addition
tical and theoretical interest. These compounds show products showing phosphorus resonance signals at
a wide spectrum of useful properties. The addition of
26–29 ppm. Addition product III with R2 =
tꢀBu and
R1 = Me is a crystalline solid and can be stored in the
dialkyl phosphites to imines is one of the main methꢀ
ods for the preparation of aminoalkylphosphonates.
pure state for a long time without change.
We have shown recently [1] that 2ꢀhaloꢀsubstituted
alkylpropylidenamines react with dialkyl phosphites
to form new types of OPCs, along with addition prodꢀ
ucts. It was found that the structure of final products is
dependent on the halogen nature.
When the reaction mixture was stored for 15–
20 days, the primary addition products undergo furꢀ
ther transformations and the structure of the reaction
products depends on the nature of the substituents at
P(IV) and N(III). Thus, the ease of the transformation
and the structure of the products are dependent on the
To reveal the effect of the nature of substituents at
P(IV) and N(III) on the structure of resulting products
and the synthesis of polyfunctional OPCs of new
types, we have studied the reactions of dimethyl,
nature of the substituents at N(III): if R2 =
iꢀPr and
Bz, further transformation of the addition product
proceeds much more readily as compared with the
compound with R2 =
t
ꢀBu. It is likely that cyclic interꢀ
mediate IV in the case of R2 =
ꢀBu is more difficult to
amiꢀnes (II) containing tertꢀbutyl, benzyl, and isoproꢀ form as compared with R2 =
Pr and Bz on account of
pyl substituents at the nitrogen atom. steric hindrances.
diethyl, diisopropyl, diꢀnꢀbutylꢀ, and diꢀ2ꢀchloroetꢀ
t
hyl phosphites ( ) with (2ꢀchloropropylidene)alkylꢀ
I
iꢀ
Cl
(R1O) P(O)H + Me CCH=NR2
Cl
(R1O) P(O)–CH–CMe →
2
2
2
2
I
II
III
NHR2
(R1O) P(O)–CH–CMe
(R1O) P(O)–CH–CMe
2
2
2
2
+
IV
: R1 = Me (a), Et (b),
II: R2 =
ꢀBu (a), Bz (b),
ꢀBu (a); R1 = Et, R2 = ꢀBu (b); R1 = ClCH2CH2, R2 =
NHR2
V
Cl NHR2
ꢀBu (d), ClCH2CH2 (e).
ꢀPr (c).
Cl
I
iꢀPr (c),
n
t
i
III: R1 = Me, R2 =
R1 =
t
t
t
ꢀBu (c); R1 = Me, R2 = Bz (d);
ꢀPr (h);
i
ꢀPr, R2 = Bz (e); R1 = ꢀBu, R2 = Bz (f); R1 = ClCH2CH2, R2 = Bz (g); R1 = ClCH2CH2, R2 =
i
n
a Kazan State Technological University, ul. Karla Marksa 68, Kazan, 420015 Tatarstan, Russia
b Arbuzov Institute of Organic and Physical Chemistry, ul. Akademika Arbuzova 8, Kazan,
420083 Tatarstan, Russia
186

REACTION OF DIALKYL PHOSPHITES
187
Cl
(R1O) P(O)CH–CMe + (R1O) P(O)CH–CMe →
2
2
2
2
+
V
IV
ClR2N–H
:NHR2
(R1O) P(O)CH–CMe + (R1O) P(O)CH–CMe
2
2
2
2
VI
Cl +NH2R2Cl
VII
NR2
VI: R1 =
i
ꢀPr, R2 = Bz (a); R1 =
n
ꢀBu, R2 = Bz (b); R1 = ClCH2CH2, R2 = Bz (c); R1 = ClCH2CH2, R2 =
ꢀBu (a); R1 = Me, R2 = Bz (b); R1 = ꢀPr, R2 = Bz (c); R1 =
R1 = ClCH2CH2, R2 = Bz (e); R1 = ClCH2CH2, R2 =
ꢀPr (f).
i
ꢀPr (d).
VII: R1 = Me, R2 =
t
i
n
ꢀBu, R2 = Bz (d);
i
The reaction of dialkyl phosphite
pounds II containing isopropyl and benzyl substituꢀ
ents leads to 2ꢀaminoalkylphosphonate hydrochloride
VI) and aziridinephosphonateꢀ2 (VII). The treatꢀ
ment of the reaction mixture with ether results in salt
VI as a crystalline product. Compound VII with a converts into betaine IX
I with comꢀ small admixture of addition product III was isolated
from the ethereal mother liquor.
The stability of salt VI depends on the nature of
substituents at P(IV): when R1 = ClCH2CH2 and R2 =
(
i
ꢀPr and t
ꢀBu, the salt is stable, while with R1 = Me, it
.
Cl
MeO Cl
+
CH–CMe2
H–NHR2Cl
Me–O–P–CH–CMe2
Cl–
(MeO)2–P
VI
NHR2
OH
+
O
Cl
O
O Cl
CH–CMe2
:NHR2
MeO–P
MeO–P–CH–CMe2
+
–MeCl
–O
O–H
VIII
IX: R2 =
NHR2
IX
t
ꢀBu (a); R2 = Bz (b).
The phosphoryl oxygen in compound VI deprotoꢀ
Reaction of Nꢀ(2ꢀmethylꢀ2ꢀchloropropylidene)ꢀ
nates the ammonium fragment to form quasiꢀphosꢀ tertꢀbutylamine (IIa) with dimethyl phosphite (Ia)
phonium center that undergoes dealkylation like the
second stage of the Arbuzov reaction. The amino
group in intermediate compound VIII deprotonates
the fragment of phosphonic acid monoester, which
A. Compound Ia (118 mmol) and amine IIa
(118 mmol) were mixed in a dry argon flow. The reacꢀ
tion mixture was slightly warmed up. The mixture was
allowed to stand at ambient temperature for 24 h. A
slight turbidity was observed when the reaction mixꢀ
ture was dissolved in ether, which was removed by filꢀ
tration. The precipitate was found to be the second
reaction product Va formed in considerable amounts
when the reaction mixture was allowed to stand for a
long time (see item B). The ether was removed from
leads to betaine compound IX
.
The structure of the compounds obtained was conꢀ
1
31
firmed by elemental analysis and H and P NMR
spectra.
the mother liquor to give 97.6 mmol (83%) of
dimethyl (1ꢀtertꢀbutylaminoꢀ2ꢀmethylꢀ2ꢀchloroproꢀ
pyl)phosphonate IIIa, mp 76 C.
1H NMR (CDCl3,
, ppm,
O,Oꢀ
EXPERIMENTAL
°
1H NMR spectra were recorded on a Tesla BSꢀ
567A spectrometer operating at 100 MHz. Proton
chemical shifts were referenced to TMS. P NMR
spectra were recorded on a CXPꢀ100 spectrometer
operating at 36.5 MHz; 85% H3PO4 was used as an
external reference.
δ
J, Hz): 1.29 (s, 9H,
CMe3), 1.83 and 1.90 (both s, 6H, CMe2), 1.82–1.87
(br s, 1H, NH), 3.37 (d, 1H, PCH, 2JРН = 20 Hz), 3.93
and 3.94 (both d, 6H, P(OMe)2, 3JРН = 11 Hz).
31
31Р NMR (CCl4,
, ppm): 29.3.
δ
DOKLADY CHEMISTRY Vol. 433
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2010

188
GAZIZIOV et al.
B. Compound Ia (40 mmol) and amine IIa
Reaction of Nꢀ(2ꢀmethylꢀ2ꢀchloropropylidene)benꢀ
(40 mmol) were mixed in a dry argon flow. The reacꢀ zylamine (IIb) with dimethyl phosphite (Ia)
tion mixture was slightly warmed up. The mixture was
kept for 30–35 days at ambient temperature. The reacꢀ
tion mixture was treated with ether, the precipitated
crystals were separated by filtration and dried in vacꢀ
A. Amine IIb (77 mmol) was added dropwise on
stirring to compound Ia (77 mmol) in a dry argon flow.
The temperature of the reaction mixture increased to
30
perature, and volatile products were removed in a high
vacuum to give 71.9 mmol (94%) of crude ꢀdimeꢀ
thyl (1ꢀbenzylaminoꢀ2ꢀmethylꢀ2ꢀchloropropyl)phosꢀ
phonate IIId
1H NMR (CDCl3,
°
C. The mixture was stirred for 24 h at ambient temꢀ
uum to give 16.8 mmol (45%) of
butylammonioꢀ2ꢀmethylꢀ1ꢀchloropropyl)phosphoꢀ
nate IX, mp 150–151 C.
O
ꢀmethyl (2ꢀtert
ꢀ
O,O
°
.
1H NMR (CDCl3,
, ppm,
δ
J
, Hz): 1.63 (s, 9H,
δ
, ppm, J, Hz): 1.69 and 1.70
4
CMe3), 1.71 s and 1.80 d (6H, CMe2, JРН = 0 and
2.3 Hz), 4.61 (d, 1H, PCH, 2JРН = 9 Hz), 3.93 (d, 3H,
(both s, 6H, CMe2), 1.85 (br s, 1H, NH), 2.29 and
3.74 (both d, 1H, PCH, 2JРН = 16.2 Hz), 3.73 and 3.78
3
POMe, JРН = 10 Hz), 9.6 and 10.9 (both br d, 2H,
3
(both d, 6H, 2MeO, JРН = 10.6 Hz), 4.00 and 3.85
N+H2).
(both d, 2H, CH2Ph, 2JHH = 12.6 Hz), 7.17–7.29 (m,
31Р NMR (CHCl3,
, ppm): 11.32.
δ
5H, Ph).
31Р NMR (CHCl3,
, ppm): 25.5.
δ
The residue after ether evaporation (10.2 mmol)
according to 1H and 31Р NMR spectra is a 2 : 1 mixture
B. Compound Ia (77 mmol) and amine IIb
(77 mmol) were mixed in a dry argon flow. The reacꢀ
tion mixture was slightly warmed up. The mixture was
kept for 30–35 days at ambient temperature. The reacꢀ
tion mixture was treated with ether five times during
this period. The resulting crystals each time were sepꢀ
arated by filtration and dried in vacuum. The ether was
removed from the mother liquor and the residue was
allowed to stand at ambient temperature until next
of addition product IIIa
28.8) and ꢀdimethyl (1ꢀtertꢀbutylaminoꢀ3,3ꢀdimꢀ
ethylaziridinꢀ2ꢀyl)phosphonate VIIa
31Р NMR
(CCl4, , ppm): 26.5).
(
31Р NMR (CCl4,
, ppm):
δ
O,O
(
δ
Synthesis of
O,Oꢀdiethyl (1ꢀtertꢀbutylaminoꢀ2ꢀ
methylꢀ2ꢀchloropropyl)phosphonate IIIb
Diethyl phosphite (Ib) (40 mmol) and
Nꢀ(2ꢀ
dilution with ether to give 38.2 mmol (63%) of
methyl (2ꢀbenzylammonioꢀ2ꢀmethylꢀ1ꢀchloroproꢀ
pyl)phosphonate IXb, mp 161–163 C.
1H NMR (CD3OD,
, ppm, , Hz): 1.65 and 1.67
(both s, 6H, CMe2), 3.74 (d, 3H, MeOP, JРН
Oꢀ
methylꢀ2ꢀchloropropylidene)ꢀtertꢀbutylamine (IIa
)
(40 mmol) were mixed in a dry argon flow. The temꢀ
perature of the reaction mixture increased to 31 C.
°
°
The mixture was allowed to stand at ambient temperꢀ
ature for 24 h. The reaction mixture was treated with
ether, and the resulting slight turbidity was removed by
filtration. The ether was removed from the mother
liquor in vacuum to give 65.8 mmol (81%) of comꢀ
pound IIIb, which was identified as a crude product on
account of its thermal lability.
δ
J
3
=
10.3 Hz), 4.22 (d, 1H, PCH, 2JРН = 10.6 Hz), 4.23 and
4.29 (both d, 2H, CH2Ph, 2JHH = 12.6 Hz), 7.44–7.56
(m, 5H, Ph), 9.5 (br s, 2H, N+H2).
31Р NMR (CH3OH,
, ppm): 13.6.
δ
1H NMR (CDCl3,
CMe3), 1.28 (t, 6H, РОСН2Ме
δ
, ppm,
J
, Hz): 1.08 (s, 9H,
For C12H19NClPO3 anal. calcd. (%): N, 4.60; Cl,
12.00; P, 10.10. Found (%): N, 5.00; Cl, 11.85; P,
10.45.
After removal of the ether from the mother liquor,
the residue (27.4 mmol) was found to be O,Oꢀdimethyl
,
3JНН = 7 Hz), 1.28–
1.44 (br s, 1H, NH), 1.60 and 1.64 (both s, 6H,
CMe2), 3.03 (d, 1H, PCH, 2JРН = 19 Hz), 4.05 (quin,
4H, POCH2, 3JНН
=
3JРН =7 Hz).
, ppm): 26.43.
O,Oꢀdiꢀ2ꢀchloroethyl (1ꢀtertꢀbutylꢀ
(1ꢀbenzylꢀ3,3ꢀdimethylaziridinꢀ2ꢀyl)phosphonate (VIIb
)
31Р NMR (CDCl3,
δ
of 90% purity.
31Р NMR (CH3OH,
(3%), 10.5 (7%).
δ
, ppm): 24.9 (90%), 18.3
Synthesis of
aminoꢀ2ꢀmethylꢀ2ꢀchloropropyl)phosphonate IIIc
1H NMR (CDCl3,
δ
, ppm, , Hz): 1.45 (d, 1H,
PCH, JРН = 18 Hz), 1.33 and 1.42 (d and s, respecꢀ
tively, 6H, CMe2, JРН = 2.5 and 0 Hz, respectively),
3.7 (d, 2H, CH2Ph, JРН = 3.2 Hz), 3.64 and
3.51 (both d, 6H, 2MeO, 3JРН = 10.7 Hz), 7.2–7.4 (m,
J
By a similar procedure, the reaction of 81 mmol of
3
diꢀ2ꢀchloroethyl phosphite (Ic) and 81 mmol of
4
N
ꢀ(2ꢀmethylꢀ2ꢀchloropropylidene)ꢀtertꢀbutylamine IIa
4
gave 67.9 mmol (84%) of crude compound IIIc
.
1H NMR (CDCl3,
δ
, ppm, , Hz): 1.03 (s, 9H,
J
5H, Ph).
CMe3), 1.54 and 1.64 (both s, 6H, CMe2), 1.58–1.62
(br s overlapped with the signals from CMe2, 1H,
NH), 3.1 (d, 1H, PCH, 2JРН = 18.5 Hz), 3.6 (m, 4H,
CH2Cl), 4.19 (m, 4H, CH2OP).
Reaction of Nꢀ(2ꢀmethylꢀ2ꢀchloropropylidene)benꢀ
zylamine (IIb) with diisopropyl phosphite (Ic)
Compound Ia (23 mmol) was mixed with amine
IIb (23 mmol) in a dry argon flow. The mixture was
kept for 60 days at ambient temperature. The reaction
31Р NMR (CHCl3,
, ppm): 27.1.
δ
DOKLADY CHEMISTRY Vol. 433
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REACTION OF DIALKYL PHOSPHITES
189
3JH4H6
3
1.31 (both d, 6H, CH33CH34 CH6OP, JH3H6
=
=
mixture was treated with ether four times during this
period to give 4.7 mmol (21%) of ꢀdiisopropyl (2ꢀ
benzylaminoꢀ2ꢀmethylꢀ1ꢀchloropropyl)phosphoꢀ
nate hydrochloride VIa, mp 145 C.
1H NMR (CDCl3,
, ppm,
O,O
6 Hz), 7.20–7.26 (m, 5H, Ph)].
°
Reaction of
Nꢀ(2ꢀmethylꢀ2ꢀchloropropylidene)ꢀ
benzylamine (IIb) with dibutyl phosphite (Id)
δ
J
, Hz): 1.36 and 1.38
3
By a similar procedure, the reaction of compound
Id (30.7 mmol) with amine IIb (30.7 mmol) afforded
7.6 mmol (27%) of
(both d, 6H, CH13CH32 СН5ОР, JH1H5
= =
3JH2H5
6.0 Hz), 1.38 and 1.43 (both d, 6H, CH33CH34 CH6OP,
O,Oꢀdibutyl (2ꢀbenzylaminoꢀ2ꢀ
methylꢀ1ꢀchloropropyl)phosphonate hydrochloride
VIc, mp 122 C.
1H NMR (CHCl3,
(both t, 6H, 2CH2 CH3
3JH3H6
=
3JH4H6 = 6.1 Hz), 1.6 and 1.82 (both s, 6H,
°
δ
, ppm,
,
J, Hz): 0.945 and 0.950
3JНН = 7.0 Hz), 1.69 (quin,
2
CMe2), 4.01 and 4.29 (both d, 2H, CH2, JНH
=
12.7 Hz), 4.83 (sextet, 1H, РО CH5CH31CH32
3JH1H5
РО CH6CH33CH43
,
3JPH5
=
4H, 2CH3CH2
,
3JНН = 7.0 Hz), 1.43 (m, 4H,
=
3JH2H5 = 6.0 Hz), 4.98 (sextet, 1H,
2ОCH2 CH2 ), 1.63 and 1.82 (both s, 6H, CMe2), 4.03
3JH4H6 = 6.0 Hz),
and the second doublet is overlapped with POCH2 sigꢀ
nals (2H, CH2Рh, 2JНH = 12.7 Hz), 4.19–4.35 (m, 4H,
2CH2OP), 5.25 (d, 1H, PCH, JРН = 10 Hz), 7.42–
,
3JPH6
=
3JH3H6
=
2
5.18 (d, 1H, PCH, JРН = 9.5 Hz), 8.84 and 12.04
2
N
+ H2).
(both br s, 2H,
31Р NMR (CHCl3,
N
+ H2).
7.58 (m, 5H, Ph), 11.9 and 8.9 (both br s, 2H,
31Р NMR (CHCl3,
, ppm): 17.91.
δ
, ppm): 16.29.
δ
For C17H30NCl2PO3 anal. calcd. (%): N, 3.50; Cl,
17.80; P, 7.80. Found (%): N, 3.65; Cl, 17.50; P, 7.45.
The residue (5.8 mmol) after the last removal of the
For C17H34 NCl2PO3 anal. calcd. (%): N, 3.30; Cl,
16.70; P, 7.30. Found (%): N, 3.65; Cl, 16.90; P, 7.40.
The residue (7.6 mmol) after removal of the ether
was shown by 31Р and 1H NMR to be a 3 : 1 mixture of
1
ether was established by 31Р and H NMR spectrosꢀ
copy to be a 3 : 1 mixture of addition product IIIe
NMR (CH3CH2OCH2CH3, , ppm): 21.9.
[
31Р
addition product IIIf
(1ꢀbenzylꢀ3,3ꢀdimethylaziridinꢀ2ꢀyl)phosphonate
VIId δP 22.5 ppm).
Reaction of
(δP 23.3 ppm) and O,Oꢀdibutyl
δ
1H NMR (CDCl3,
(both d, 6Н, CH13CH32 СН5ОР, JH1H5
δ
, ppm, J, Hz): 1.29 and 1.32
(
= =
3JH2H5
3
N
ꢀ(2ꢀmethylꢀ2ꢀchloropropylidene)benꢀ
zylamine (IIb) with diꢀ2ꢀchloroethyl phosphite (Ie)
6.3 Hz), 1.32 and 1.34 (both d, 6H, CH33CH34 CH6OP,
3JH3H6 3JH4H6 = 6.3 Hz), 1.75 and 1.71 (both s, 6H,
By a similar procedure, the reaction of compound
Ie (68.3 mmol) with amine IIb (68.3 mmol) gave
32.7 mmol (45%) of O,Oꢀdiꢀ2ꢀchloroethyl (2ꢀbenzyꢀ
=
CMe2), 2.1 (br s, 1H, NH), 2.93 (d, 1H, PCH, 2JРН
17.34 Hz), 4.10 and 4.89 (both d, 2H, CH2 Ph, 2JНH
=
=
laminoꢀ2ꢀmethylꢀ1ꢀchloropropyl)phosphonate
hydrochloride VIc, mp 152–153 C.
1H NMR (CDCl3,
, ppm, , Hz): 1.67 and 1.81
°
δ
J
12.3 Hz), 4.75 (hept, 1H, РО CH5CH31CH32
3JH1H5
РО CH6CH33CH43
7.28–7.38 (m, 5H, Ph)] and
,
3JPH5
=
(both s, 6H, CMe2), 3.76 (m, 4H, CH2OP), 4.50 and
4.59 (m, 4H, CH2Cl), 4.02 and 4.29 (both d, 2H,
=
3JH2H5 = 6.3 Hz), 4.78 (hept, 1H,
3JPH6 3JH3H6 3JH4H6 = 6.3 Hz),
ꢀdiisopropyl (1ꢀbenꢀ
2
2
CH2Ph, JНH = 12.3 Hz), 5.5 (d, 1H, PCH, JРН = 9
Hz), 7.28–7.57 (m, 5H, Ph), 8.5 and 12.1 (both br s,
,
=
=
2H,
31Р NMR (CDCl3,
N
+ H2).
O,O
zylꢀ3,3ꢀdimethylaziridinꢀ2ꢀyl)phosphonate VIIc
[
31Р
δ, ppm): 18.7.
NMR (CH3CH2OCH2CH3, , ppm): 22.3.
δ
For C15H24NCl4PO3 anal. calcd. (%): N, 3.00; Cl,
32.25; P, 6.70. Found (%): N, 3.25; Cl, 32.00; P, 7.05.
The residue (84.3 mmol, 21%) after removal of the
ether was established by 31Р and 1H NMR to be a 1 : 4
1H NMR (CDCl3,
, ppm, , Hz): 1.25 and 1.24 (d
δ
J
4
and s, respectively, 6H, CMe2, JРН = 3 and 0 Hz,
respectively), 1.44 (d, 1H, PCH, 2JРН = 17.3 Hz), 3.64
and 3.74 (both d, 2H, CH2 Ph, 2JНH = 14.2 Hz), 4.59
mixture of addition product IIIg
[
31Р NMR (CDCl3,
δ
, ppm): 24.5.
(hept, 1H, РО CH5CH31CH32
,
3JPH5
=
3JH1H5
=
3JH2H5
=
1H NMR (CDCl3,
(both s, 6H, CMe2), 3.08 (d, 1H, PCH, JРН
16.3 Hz), 7.10–7.26 (m, 5H, Ph)] and ꢀdiꢀ
δ
, ppm, J, Hz): 1.75 and 1.76
6.0 Hz), 4.61 (hept, 1H, РО CH6CH33CH34
,
3JPH6
=
2
=
O,O
3JH3H6
=
3JH4H6 = 6.0 Hz), 1.24 and 1.26 (both d, 6H,
2ꢀchloroethyl
(1ꢀbenzylꢀ3,3ꢀdimethylaziridinꢀ2ꢀ
yl)phosphonate (VIIe) [31Р NMR (CDCl3,
, ppm):
δ
3
CH31CH32 СН5ОР, JH1H5
=
3JH2H5 = 6.0 Hz), 1.29 and
25.6.
DOKLADY CHEMISTRY Vol. 433
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2010

190
GAZIZIOV et al.
1H NMR (CDCl3,
, ppm, J, Hz): 1.21 and 1.32
δ
For C11H24NCl4PO3 anal. calcd. (%): N, 3.82; Cl,
38.65; P, 8.44. Found (%): N, 3.62; Cl, 38.25; P, 8.58.
The residue (17.8 mmol) after removal of the ether
was established by 31Р and 1H NMR to be a 1 : 4 mixꢀ
2
(both s, 6H, CMe2), 1.47 (m, 1H, PCH, JРН
18.9 Hz), 3.44 and 3.67 (both d, 2H, СН2Ph, JHH
=
=
2
13.5 Hz), 7.16–7.24 (m, 5H, Ph)].
ture of addition product IIIh
ppm): 25.9. H NMR (CDCl3,
[
31Р NMR (CDCl3,
, ppm, , Hz): 1.75
and 1.76 (both s, 6H, CMe2), 3.08 (d, 1H, PCH,
2JРН = 16.3 Hz)] and
ꢀdiꢀ2ꢀchloroethyl (1ꢀisoproꢀ
pylꢀ3,3ꢀdimethylaziridinꢀ2ꢀyl)phosphonate VIIf).
δ
,
Reaction of
Nꢀ(2ꢀmethylꢀ2ꢀchloropropylidene)isoꢀ
1
δ
J
propylamine (IIc) with diꢀ2ꢀchloroethyl phosphite (Ie)
Compound Ie (97.3 mmol) was mixed with amine
IIc (97.3 mmol) in a dry argon flow. The reaction mixꢀ
ture was slightly warmed up. The mixture was kept for
three weeks at ambient temperature. The reaction
mixture was treated with ether five times during this
period and the precipitated reaction product was isoꢀ
lated by filtration each time to give 46.7 mmol (53%)
O,O
(
The mixture was identified in a crude state on account
of its thermal instability.
31Р NMR (CDCl3,
1H NMR (CDCl3,
δ
, ppm): 25.6.
, ppm, , Hz): 1.08 and 1.14
,
3JНН = 7.0 Hz), 1.38 (s, 6H,
δ
J
of
O
,
O
ꢀdiꢀ2ꢀchloroethyl
VId), mp 101 C.
1H NMR (CDCl3,
(2ꢀisopropylaminoꢀ2ꢀ
(both d, 6H, CН Me2
methylꢀ1ꢀchloropropyl)phosphonate hydrochloride
CMe2), 1.43 (d, 1H, PCH, 2JРН = 18 Hz), 2.3 (m, 1H,
CH Me2), 3.68 (m, 4H, CH2O), 4.35 (m, 4H,
(
°
δ
, ppm,
J, Hz): 1.88 (d, 6H,
3
CH2Cl).
C
Me2 ), 1.58 and 1.82 (both d, 6H, CH Me2, JHH
=
7.0 Hz), 2.3 (m, 1H, CНMe2), 3.9 (m, 4H, CH2OP),
2
4.7 (m, 4H, CH2Cl), 5.85 (d, 1H, PCH, JРН
=
REFERENCES
13 Hz), 8.3 and 11.2 (br d and br s, respectively, 2H,
1. Gazizov, M.B, Khairullin, R.A., Alekhina, A.I., Litviꢀ
nov, I.A., Krivolapov, D.B., Latypov, Sh.K., Balanꢀ
dina, A.A., Musin, R.Z., and Sinyashin, O.G., Menꢀ
deleev Commun., 2008, vol. 18, no. 5, pp. 262–264.
N
+ H2).
31Р NMR (CHCl3,
δ, ppm): 18.89.
DOKLADY CHEMISTRY Vol. 433
Part 1
2010