Modification of some mono- and bispiperidols exhibiting growth-regulating properties

Article abstract of DOI:10.1134/S107042720803035X

Procedures for esterification of biologically active mono-and bispiperidols by reactions with benzoyl and terephthaloyl chlorides were developed.

Full text of DOI:10.1134/S107042720803035X

ISSN 1070-4272, Russian Journal of Applied Chemistry, 2008, Vol. 81, No. 3, pp. 506 508. Pleiades Publishing, Ltd., 2008.
Original Russian Text B.A. Zhubanov, R.F. Mukhamedova, G.I. Boiko, T.P. Maimakov, N.P. Lyubchenko, K.B. Erzhanov, 2008, published in Zhurnal
Prikladnoi Khimii, 2008, Vol. 81, No. 3, pp. 521 523.
BRIEF
COMMUNICATIONS
Modification of Some Mono- and Bispiperidols
Exhibiting Growth-Regulating Properties
B. A. Zhubanov, R. F. Mukhamedova, G. I. Boiko, T. P. Maimakov,
N. P. Lyubchenko, and K. B. Erzhanov
Bekturov Institute of Chemical Sciences, Ministry of Education and Science of the Kazakhstan Republic,
Almaty, Kazakhstan
Satpaev Kazakh National University, Almaty, Kazakhstan
Unat Higher School, Almaty, Kazakhstan
Received October 11, 2007
Abstract Procedures for esterification of biologically active mono- and bispiperidols by reactions with
benzoyl and terephthaloyl chlorides were developed.
DOI: 10.1134/S107042720803035X
The development of highly effective chemical
agents increasing the output of agricultural production
is one of priority problems of chemical science and
industry. Regulators of plant growth and development
occupy an important place among such chemical
agents. Numerous low-molecular-weight compounds,
both natural (auxins, gibberellins, kinins, abscisic
acid) and synthetic, exerting growth-regulating, stimu-
lating, and herbicidal effect are known. At the same
time, active studies aimed to develop new plant
growth regulators and their derivatives are continued.
increase the productivity of crops (potatoes, sugar-
beet) by 20 30% on the average, and the saccharinity
of sugar-beet, by 1.5%. Polymeric plant growth regu-
lators increase the germination energy of seeds (lu-
cerne, goose-foot, licorice) by 12 18%, and the ger-
1
minating power, by 60 80% on the average.
Here we report on a new route to modified BASs.
As modification substrates we chose a series of mono-
and bispiperidols and their analogs: 1,2,5-trimethyl-4-
(butoxypropyn-1-yl)piperid-4-ol, di(1-hydroxycyclo-
hexyl)buta-1,3-diyne, and 1,4-bis(1,2,5-trimethyl-4-
hydroxypiperid-4-yl)buta-1,3-diyne. These agents in-
crease the productivity and improve the quality of
crops such as potatoes, sugar-beet, corn, etc.
Numerous studies showed that the performance of
biologically active substances (BASs) can be consid-
erably enhanced by their chemical modification, main-
ly with various polymers [1, 2].
For a long period we perform comprehensive stu-
dies dealing with immobilization of low-molecular-
weight BASs on a polymeric matrix with the aim to
enhance and prolong their action and to ensure con-
trolled release of the growth-regulating agent. We
developed and implemented polymer-analogous trans-
formations of copolymers of maleic anhydride with
derivatives of acetylenic nitrogen- and phosphorus-
containing carbo- and heterocyclic systems [3 7].
As a result, we obtained a new generation of polymer-
ic water-soluble agents controlling the growth and
development of plants and exhibiting durable action.
We developed new polymeric preparations surpassing
in the performance the known plant growth regulators.
The laboratory, field, and commercial trials show that
the polymeric preparations Zhiger, PAG, and PASA
EXPERIMENTAL
The starting compounds and solvents were purified
by standard procedures. The IR spectra were measured
on an IR-25 spectrophotometer (KBr pellets).
As the BASs under consideration contain hydroxy
groups, one of the ways of their modification is con-
densation with acid chlorides. In our study we used
benzoyl and terephthaloyl chlorides.
The products were identified by IR spectroscopy
and elemental analysis. The main characteristics of the
compounds are given in the table.
1
Data of the Gur’ev Agricultural Station, Kazakh Research
Institute of Feed Production and Pastures.
506

MODIFICATION OF SOME MONO- AND BISPIPERIDOLS
Characteristics of the esters synthesized
507
Found, %/Calculated, %
Com-
pound
Yield,
%
Structural formula
Tm, C
C
H
N/Cl
I
28
116 118
75.27
74.86
7.74
6.92
5.16
5.15
CO
O
O
C
CH
H3C
CH3
N
CH3
14
62
102 104
79.29
76.80
6.60
7.02
II
CO
C
C
C
C
O CO
III
97 99
60.30
61.10
7.03
6.94
4.69
3.99
CO
H3C
O
C
CH
CH3
HC
C
O
CO
CH3
H3C
N
N
CH3
CH3
30
18
73
110 114
123 125
132 134
68.81
66.97
6.06
5.62
3.13
2.84
IV
V
H
O
C
C
C
C
O
CO
CO
OH
n
_
n
=3 4
75.27
70.14
7.71
6.59
5.16
4.63
O
CO
CH3
CO
H3C
O
C
C
C
C
N
N
CH3 H3C
CH3
CH3
67.41
64.95
7.02
7.60
N
5.61
VI
H
CO
O
CO OH
O
C
C
C
C
H3C
CH3
5.61
CH3 H3C
HCl
N
N
.
.
Cl
7.12
HCl
CH3
CH3
n
_
8.08
n
3 4
=
First we prepared monoesters of the above-men-
tioned BASs with benzoyl chloride. Monoesters I, II,
and V (see table) were prepared at 60 C in a benzene
solution in excess benzoyl chloride in the presence of
triethylamine. The reaction progress was monitored
by thin-layer chromatography. The synthesis was per-
formed for 7 8 h. After removing benzene and excess
benzoyl chloride, an only product was obtained,
which crystallized on trituration in petroleum ether.
In the IR spectrum of the products, there is an absorp-
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508
ZHUBANOV et al.
1
tion band at about 1730 cm , corresponding to vibra-
tions of the ester group.
CONCLUSIONS
(1) New esters derived from benzoyl and tere-
phthaloyl chlorides and biologically active mono- and
bispiperidols and their analogs [1,2,5-trimethyl-4-
(butoxypropyn-1-yl)piperid-4-ol, di(1-hydroxycyclo-
hexyl)buta-1,3-diyne, and 1,4-bis(1,2,5-trimethyl-
4-hydroxypiperid-4-yl)buta-1,3-diyne] were prepared
and identified by IR spectroscopy and elemental
analysis.
Diester III (see table) derived from 1,2,5-trimethyl-
4-(3-butoxypropyn-1-yl)piperid-4-ol and terephthaloyl
chloride was synthesized by the procedure for prepar-
ing activated diesters at 60 C in dioxane in the pres-
ence of pyridine. The synthesis was performed for
10 h, after which the mixture was evaporated to dry-
ness, thoroughly washed with cold water, dried, and
recrystallized from ethanol petroleum ether. The
product was identified by elemental analysis and IR
spectroscopy.
(2) The synthesized mono-, di-, and oligoesters
taken in low concentrations exhibit a growth-stimulat-
ing effect.
Terephthalic acid esters of di(1-hydroxycyclohex-
yl)buta-1,3-diyne and 1,4-bis(1,2,5-trimethyl-4-hy-
droxypiperid-4-yl)buta-1,3-diyne (compounds IV and
V, see table) were prepared by reaction of these alco-
hols with terephthaloyl chloride in a three-necked
flask equipped with a bubbler, a stirrer, and an outlet
pipe equipped with a calcium chloride tube. The reac-
tion was performed in dichloroethane at 60 80 C in
the presence of triethylamine. The synthesis time was
12 h. After the reaction completion, the product was
precipitated with acetone, washed on the filter alter-
nately with methanol and cold distilled water, and
dried in a vacuum oven. The esters are readily soluble
in amide solvents.
REFERENCES
1. Shtil’man, M.I., Soros. Obraz. Zh., 1998, no. 10,
pp. 44 49.
2. Shtil’man, M.I., Polimery mediko-biologicheskogo na-
znacheniya (Polymers for Medicobiological Purposes),
Moscow: Akademkniga, 2006.
3. RF Patent 1/88/26.
4. Kazakh Patent 1762534.
5. Kazakh Patent 1239.
6. Boiko, G.I., Lyubchenko, N.P., Maimakov, T.P., et al.,
in Trudy IV Mezhdunarodnogo simpoziuma Fizika i
khimiya uglerodnykh materialov/nanoinzheneriya
(Proc. IV Int. Symp. Physics and Chemistry of Carbon
Materials/Nanoengineering ), Almaty, 2006, pp. 140
144.
7. Boiko, G.I., Mukhamedova, R.F., Lyubchenko, N.P.,
et al., Vestn. Kaz. Nats. Univ., Ser. Khim., 2007, no. 1
(45), pp. 207 211.
Tests performed with dicotyledonous cereals
showed that the mono-, di-, and oligoesters we pre-
pared, taken in low concentrations, exhibit a growth-
stimulating effect. At the same time, esters derived
from di(1-hydroxycyclohexyl)buta-1,3-diyne (see
table, products II and IV) exhibit a herbicidal effect.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 81 No. 3 2008