Reaction of 3-(ethylamino)-2,2-dimethylpropanal with alkylene phosphites

Full text of DOI:10.1134/S1070363211070292

ISSN 1070-3632, Russian Journal of General Chemistry, 2011, Vol. 81, No. 7, pp. 1566–1567. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © M.B. Gazizov, R.A. Khairullin, A.I. Alekhina, A.A. Bashkirtsev, 2011, published in Zhurnal Obshchei Khimii, 2011, Vol. 81, No. 7,
pp. 1219–1220.
LETTERS
TO THE EDITOR
Reaction of 3-(Ethylamino)-2,2-dimethylpropanal
with Alkylene Phosphites
M. B. Gazizov, R. A. Khairullin, A. I. Alekhina, and A. A. Bashkirtsev
Kazan State Technological University, ul. K. Marksa 68, Kazan, Tatarstan, 420015 Russia
e-mail: mukattisg@mail.ru
Received February 28, 2011
DOI: 10.1134/S1070363211070292
It is known that dialkylphosphites react with 3-(mono-
alkylamino)-substituted aldehydes to form 3-(alkyl-
amino)-1-hydroxyphosphonates [1]. Alkylene phosphites
were not previously entered into this reaction.
absence of additional catalyst because the alkylamine
group of the starting aldehyde II played the role of a
basic catalyst. When adding dropwise the compound II
to alkylene phosphites I, the reaction mixture
temperature rose to 30–35ºC. The reaction mixture was
stirred at 25ºC for 24 h (till the disappearance of the
The aim of this work was to determine the structure
of products of the reaction of alkylene phosphite I with
3-(ethylamino)-2,2-dimethylpropanal II and their
subsequent acylation to obtain new polyfunctional
organophosphorus compounds.
1
signal of the aldehyde proton at δ 9 ppm in the H
NMR spectrum).
О,О-Alkylene-1,3-[1-hydroxy-3-(ethylamino)-2,2-
dimethylpropyl]phosphonates III are heat-sensitive, so
they are identified in the crude form after removal of
volatile substances in a high vacuum.
We first found that the reaction between com-
pounds I and II proceeds under mild conditions in the
O
O
O
O
O
P
+ EtNHCH2CMe2CHO
P
HC CMe2CH2NHEt
H
O
OH
III
R
R
I
II
III, R = H (а), Me (b).
The structure of compounds III, besides the 1H and
31P NMR spectral data, was confirmed by acylation with
benzoyl chloride. Compounds III have two reaction
centers capable of acylating: hydroxy and secondary
amine groups. Previously, we have found that acyclic
phosphorus analog IV of compound III is exclusively
acylated at the nitrogen to yield product V, in whose
spectrum the CH-proton resonates at δ 3.76 ppm [1].
AcCl, Et3N
–Et3N·HCl
(MeO)2P(O)CH(OH)CMe2CH2NHEt
(MeO)2P(O)CH(OH)CMe2CH2N(Ac)Et
IV
V
We found that the acylation occurred at the hydroxy
group at the ratio of amino phosphonate III and
benzoyl chloride 1:1.
the value of the proton chemical shift in the spectrum
of acetoxy derivatives: 5.21–5.40 ppm [2]. In addition,
in the H NMR spectrum of compound VI there is a
1
multiplet signal of NH-proton at δ 2.27 ppm. This
fundamental difference in the direction of acylation of
amino phosphonates with acyclic and cyclic phos-
1
The H NMR spectrum of compound VI contains
the methine proton signal at δ 5.92–5.94 ppm, close to
1566

REACTION OF 3-(ETHYLAMINO)-2,2-DIMETHYLPROPANAL
1567
O
P
O
O
O
O
CH(OH)CMe2CH2NHEt + PhC(O)Cl + Et3N
CH(OCOPh)CMe2CH2NHEt
P
−Et3N HCl
O
R1
R1
III
VI
VI, R = H (а), Me (b).
phorus moieties is probably due to the stronger
screening of hydroxy group with the O,O-dialkyl-
phosphoryl group rather than with O,O-alkylene phos-
phoryl group.
tained from 1.0 g (0.004 mol) of phosphonate IIIа in
50 ml of benzene, 0.56 g (0.004 mol) of benzoyl
chloride, and 0.4 g (0.004 mol) of triethylamine. Yield
1.44 g (58%), mp 144ºС (benzene). 1Н NMR spectrum
3
(CDCl3), δ, ppm: 0.94 t (3Н, JHH 7.0 Hz), 1.12 s and
Thus, we first studied the reaction of alkylene
phosphites I with 3-(ethylamino)-2,2-dimethylpropanal
II, which results in a previously unknown compounds
III. The reaction takes place under the mild conditions
without a catalyst, since the alkylamine group of the
starting aldehyde acts as the main catalyst. The reac-
tion products III are acylated with benzoyl chloride at
the hydroxy group.
1.27 s (6H, СМе2), 1.72 q and 2.44 q [2Н,
СН1Н2СН2ОР, 4J(PH1) 4.5, 4J(PH2) 2.2, 2J(H1H2) 14.2 Hz],
2.27 m (1Н, NН), 3.73 d and 4.15 q [2Н, CH1H2N,
3
4
4
3J(H1H2) 14.2, J(H2H) 15.1, J(PH2) 5.7, J(PH1)
0 Hz], 3.60 d.q and 3.15 d.q [2Н, NСН1Н2Me,
2J(H1H2) 14.5, 3J(H1H) = 3J(H2H) = 7 Hz], 4.29 m and
4.79 m (4Н, СН2ОР), 5.94 d and 5.92 d (1Н, РСН,
2JРH 28 Hz), 7.26–7.40 m (5Н, С6Н5). 31Р NMR
(CНCl3): δP 16.4 ppm. Found, %: N 4.14; Р 8.40.
С17Н30NО5Р. Calculated, %: N 3.89; Р 8.70.
О,О-Propylene-1,3-[1-hydroxy-3-(ethylamino)-2,2-
dimethylpropyl]phosphonate (IIIa). At room tem-
perature were mixed 2.69 g (0.022 mol) of propylene-
1,3-phosphorous acid Ia and 2.84 g (0.022 mol) of 3-
(ethylamino)-2,2-dimethylpropanal II. An increase in
the reaction mixture temperature to 35ºC was ob-
served. The mixture thickened immediately. After
removal of volatile substances the mixture was
distilled in a vacuum to yield the heat-sensitive product
О,О-Butylene-1,3-[1-(benzoyloxy)-2,2-dimethyl-
3-(ethylamino)propyl]phosphonate (VIb) was ob-
tained from 5.15 g (0.03 mol) of phosphonate IIIb in
100 ml of benzene, 4.22 g (0.003 mol) of benzoyl
chloride, and 3.03 g (0.003 mol) of triethylamine.
Yield 4.01 g (50%), mp 150ºС (benzene). 31Р NMR
spectrum (CНCl3): δP 19.97 ppm. Found, %: N 3.70; Р
8.48. С18Н32NО5Р. Calculated, %: N 3.79; Р 8.40.
1
IIIa. Yield 5.0 g (90%). Н NMR spectrum (CDCl3),
δ, ppm: 1.11 t (3Н, NCH2Me, 3JHH 7.0 Hz), 1.14 s (6H,
СМе2), 1.65–2.40 m (2Н, РОСН2СН2), 2.59 q and
1
The Н NMR spectra were registered on a Tesla
2
4
2.93 q [2Н, СН1Н2N, J(H1H2) 12.4, J(PH1) 4.0,
BS-567A spectrometer operating at 100 MHz, internal
reference TMS. The 31Р NMR spectra were recorded
on a RYa-2303 instrument (21 MHz) relative to 85%
Н3РО4.
4J(PH2) 3.0 Hz], 2.65 q (2Н, NCH2Me, JHH 7.0 Hz),
3
2
3.79 d (1Н, РСН, JРH 7.0 Hz), 4.15–4.88 m (4Н,
РОСН2), 5.12 br.s (2Н, NН, ОН). 31Р NMR spectrum
(CНCl3): δP 16.29 ppm. Found, %: N 5.50; Р 12.45;
С10Н24NО4Р. Calculated, %: N 5.58; Р 12.35.
This work was financially supported by the Federal
Target Program “Research and Scientific-Pedagogical
Personnel of Innovative Russia for 2009–2013” (contract
no. P-1108).
О,О-Butylene-1,3-[1-hydroxy-3-(ethylamino)-2,2-
dimethylpropyl]phosphonate (IIIb) was obtained
similarly from 8.16 g (0.06 mol) of compound II and
8.60 g (0.06 mol) of butylene-1,3-phosphorous acid Ib.
Yield of the crude product 16.2 g (97%). 31Р NMR
spectrum (CНCl3): δP 15.18 ppm. Found, %: N 5.25; Р
11.68. С11Н24NО4Р. Calculated, %: N 5.28; Р 11.70.
REFERENCES
1. Gazizov, M.B., Khairullin, R.A., Bagauva, L.R., and
Sinyashin, O.G., Zh. Obshch. Khim., 2006, vol. 76,
no. 5, p. 873.
2. Gazizov, M.B., Khairullin, R.A., Bagauva, L.R., Safi-
na, G.G., Karimova, R.F., and Sinyashin, O.G., Zh.
Obshch. Khim., 2004, vol. 74, no. 6, p. 1043.
О,О-Propylene-1,3-[1-(benzoyloxy)-2,2-dimethyl-
3-(ethylamino)propyl]phosphonate (VIа) was ob-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 7 2011