Terpene analogues of dithiophospate pesticides

Article abstract of DOI:10.1080/10426507.2010.514310

New optically active O,O-diterpenyl dithiophosphoric and O-terpenyl aryldithiophosphonic acids were prepared when chiral terpenols such as (1R)-endo-(+)-fenchyl alcohol, (1S)-endo-(-)-borneol, (1R)-(-)-nopol, and (1R,2S,3S,5R)-(+)-isopinocampheol were inv

Full text of DOI:10.1080/10426507.2010.514310

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Phosphorus, Sulfur, and Silicon and the
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Terpene Analogues of Dithiophospate
Pesticides
Rafael A. Cherkasov a , Artem V. Sofronov a , Yevgeniy M. Martianov a
, Il’yas S. Nizamov a b & Dmitriy A. Terenzhev c
a Kazan State University , Kazan , Russia
b A. E. Arbuzov Institute of Organic and Physical Chemistry , Kazan ,
Russia
c Tatar State Humanitarian Pedagogical University , Kazan , Russia
Published online: 25 Apr 2011.
To cite this article: Rafael A. Cherkasov , Artem V. Sofronov , Yevgeniy M. Martianov , Il’yas S.
Nizamov & Dmitriy A. Terenzhev (2011) Terpene Analogues of Dithiophospate Pesticides, Phosphorus,
Sulfur, and Silicon and the Related Elements, 186:4, 1003-1004, DOI: 10.1080/10426507.2010.514310
To link to this article: http://dx.doi.org/10.1080/10426507.2010.514310
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Phosphorus, Sulfur, and Silicon, 186:1003–1004, 2011
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2010.514310
TERPENE ANALOGUES OF DITHIOPHOSPATE
PESTICIDES
Rafael A. Cherkasov,1 Artem V. Sofronov,1 Yevgeniy M.
Martianov,1 Il’yas S. Nizamov,1,2 and Dmitriy A. Terenzhev3
1Kazan State University, Kazan, Russia
2A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan, Russia
3Tatar State Humanitarian Pedagogical University, Kazan, Russia
Abstract New optically active O,O-diterpenyl dithiophosphoric and O-terpenyl aryldithio-
phosphonic acids were prepared when chiral terpenols such as (1R)-endo-(+)-fenchyl
alcohol, (1S)-endo-(−)-borneol, (1R)-(−)-nopol, and (1R,2S,3S,5R)-(+)-isopinocampheol
were involved in reactions with tetraphosphorus decasulfide and 2,4-diaryl 1,3,2,4-
dithiadiphosphetane-2,4-disulfides.
Keywords Chiral terpenols; 2,4-diaryl 1,3,2,4-dithiadiphosphetane-2,4-disulfides; dithiophos-
phonic acids; dithiophosphoric acids; optical activity; tetraphosphorus decasulfide
INTRODUCTION
Common methods of synthesizing dithiophosphate pesticides are usually based on
the reactions of the O,O-dialkyl dithiophosphoric acids or their salts with chloroanhydrides
of carboxylic acids, esters, and amides of α-chlorocarboxylic acids or diethyl maleate. This
approach allows traditional dithiophosphate pesticides bearing pharmacophoric functional-
ities in the S-organyl substituents to be obtained. In contrast to this, we have developed a new
approach for synthesizing terpene analogues of dithiophospate pesticides with additional
pharmacophoric functionalities in O-organyl group.
RESULTS AND DISCUSSION
The interest in O-terpenyl derivatives of tetracoordinated phosphorus thioacids is
due to their potential metabolic regulation activity. We have used a series of chiral ter-
penols such as (1R)-endo-(+)-fenchyl alcohol, (1S)-endo-(−)-borneol, (1R)-(−)-nopol,
and (1R,2S,3S,5R)-(+)-isopinocampheol. Optically active O,O-diterpenyl dithiophospho-
ric acids were prepared when (1S)-endo-(−)-borneol and (1R)-endo-(+)-fenchyl alcohol
were involved in reactions with tetraphosphorus decasulfide at 50◦C for 1 h in the benzene
suspension. These acids were transformed into the corresponding ammonium salts. The
Received 9 July 2010; accepted 30 July 2010.
Address correspondence to Rafael A. Cherkasov, Kazan State University, Kremlyovskays, 18, Kazan 420008,
Russia. E-mail: rafael.cherkasov@ksu.ru
1003

1004
R. A. CHERKASOV ET AL.
reactions of these salts with benzoyl chloride, methyl chloroacetate, or epichlorohydrin at
20◦C for 1 h result in novel S-organyl O,O-diterpenyl dithiophosphates [Eq. (1)].
S
P
S
P
O
P4S10
–H2S
NH3
OH
O
O
O
_
HS
(1)
S NH4
ClCH2COOMe
S
Cl-C(O)Ph
–NH4Cl
–NH4Cl
O
S
O
O
P
O
P
S-CH2COOMe
S-C(O)Ph
Thiophosphorylation of (1R)-endo-(+)-fenchyl alcohol, (1S)-endo-(−)-borneol,
and (1R,2S,3S,5R)-(+)-isopinocampheol by 2,4-diaryl 1,3,2,4-dithiadiphosphetane-
2,4-disulfides at 50◦C for 1 h in the benzene suspension yields new O-terpenyl
aryldithiophosphonic acids. Similarly, the corresponding ammonium salts were obtained
from these O-terpenyl aryldithiophosphonic acids. These salts were transformed into the
pesticide analogues containing the dithiophosphonic units by the reactions with benzoyl
chloride, methyl chloroacetate, or epichlorohydrin at 20◦C for 1 h [Eq. (2)].
S
NH3
S
P
S
S
OH
P
OH
HO
P
S
OH
O
SH
(2)
OH
S
S
ClCH2COOMe
–NH4Cl
OH
P
P
OH
O
O
_
S NH4
OH
S-CH2COOMe
OH
–NH4Cl
Cl-CH2
O
S
P
OH
O
S-CH2
OH
O
The S-organyl O,O-diterpenyl dithiophosphates and O-terpenyl aryldithiophospho-
nates that were prepared possess antimicrobial activity.