This article was downloaded by: [b-on: Biblioteca do conhecimento online UL] On: 07 May 2014, At: 02:29 Publisher: Taylor & Francis Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK Phosphorus, Sulfur, and Silicon and the Related Elements Publication details, including instructions for authors and subscription information: http://www.tandfonline.com/loi/gpss20 One-Pot Synthesis and Fungicidal Activity of Pyrimidinylidenamido- and Thiazolinylidenamidomonothiophosphoric Esters Neelima Gupta a , Vijaya Kabra a , Varsha Saxena a , Sama Jain a & Kalpana Bhatnager b a University of Rajasthan , Jaipur, India b A.R.S. , Jaipur, India Published online: 27 Oct 2010. To cite this article: Neelima Gupta , Vijaya Kabra , Varsha Saxena , Sama Jain & Kalpana Bhatnager (2003) One-Pot Synthesis and Fungicidal Activity of Pyrimidinylidenamido- and Thiazolinylidenamidomonothiophosphoric Esters, Phosphorus, Sulfur, and Silicon and the Related Elements, 178:4, 851-861, DOI: 10.1080/10426500307803 To link to this article: http://dx.doi.org/10.1080/10426500307803 PLEASE SCROLL DOWN FOR ARTICLE Taylor & Francis makes every effort to ensure the accuracy of all the information (the “Content”) contained in the publications on our platform. However, Taylor & Francis, our agents, and our licensors make no representations or warranties whatsoever as to the accuracy, completeness, or suitability for any purpose of the Content. Any opinions and views expressed in this publication are the opinions and views of the authors, and are not the views of or endorsed by Taylor & Francis. The accuracy of the Content should not be relied upon and should be independently verified with primary sources of information. Taylor and Francis shall not be liable for any losses, actions, claims, proceedings, demands, costs, expenses, damages, and other liabilities whatsoever or howsoever caused arising directly or indirectly in connection with, in relation to or arising out of the use of the Content. This article may be used for research, teaching, and private study purposes. Any substantial or systematic reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in any form to anyone is expressly forbidden. Terms & Conditions of access and use can be found at http:// www.tandfonline.com/page/terms-and-conditions
Transcript
This article was downloaded by: [b-on: Biblioteca do conhecimento online UL]On: 07 May 2014, At: 02:29Publisher: Taylor & FrancisInforma Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House,37-41 Mortimer Street, London W1T 3JH, UK
Phosphorus, Sulfur, and Silicon and the RelatedElementsPublication details, including instructions for authors and subscription information:http://www.tandfonline.com/loi/gpss20
One-Pot Synthesis and FungicidalActivity of Pyrimidinylidenamido- andThiazolinylidenamidomonothiophosphoric EstersNeelima Gupta a , Vijaya Kabra a , Varsha Saxena a , Sama Jain a & Kalpana Bhatnager ba University of Rajasthan , Jaipur, Indiab A.R.S. , Jaipur, IndiaPublished online: 27 Oct 2010.
To cite this article: Neelima Gupta , Vijaya Kabra , Varsha Saxena , Sama Jain & Kalpana Bhatnager (2003) One-Pot Synthesisand Fungicidal Activity of Pyrimidinylidenamido- and Thiazolinylidenamidomonothiophosphoric Esters, Phosphorus, Sulfur, andSilicon and the Related Elements, 178:4, 851-861, DOI: 10.1080/10426500307803
To link to this article: http://dx.doi.org/10.1080/10426500307803
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the information (the “Content”) containedin the publications on our platform. However, Taylor & Francis, our agents, and our licensors make norepresentations or warranties whatsoever as to the accuracy, completeness, or suitability for any purpose of theContent. Any opinions and views expressed in this publication are the opinions and views of the authors, andare not the views of or endorsed by Taylor & Francis. The accuracy of the Content should not be relied upon andshould be independently verified with primary sources of information. Taylor and Francis shall not be liable forany losses, actions, claims, proceedings, demands, costs, expenses, damages, and other liabilities whatsoeveror howsoever caused arising directly or indirectly in connection with, in relation to or arising out of the use ofthe Content.
This article may be used for research, teaching, and private study purposes. Any substantial or systematicreproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in anyform to anyone is expressly forbidden. Terms & Conditions of access and use can be found at http://www.tandfonline.com/page/terms-and-conditions
ONE-POT SYNTHESIS AND FUNGICIDAL ACTIVITYOF PYRIMIDINYLIDENAMIDO- AND
THIAZOLINYLIDENAMIDOMONOTHIOPHOSPHORICESTERS
Neelima Gupta,a Vijaya Kabra,a Varsha Saxena,a Sama Jain,aand Kalpana Bhatnagerb
University of Rajasthan, Jaipur, Indiaa andA.R.S., Jaipur, Indiab
(Received August 12, 2002; accepted September 29, 2002)
A novel one-pot synthesis of four new classes of amidothiophosphoricesters and trisamidothiophosphoric esters is developed. (1-Alkyl-2-pyrimidinylidenamido)bis(diethylamido)thiophosphates, (1-alkyl-2-pyrimidinylidenamido)bis (O-2/4-methylphenyl)thiophosphates,(3-alkyl-2-thiazolinylidenamido)bis (diethylamido)thiophosphateand (3-alkyl-2-thiazolinylidenamido)bis(O-2/4-methylphenyl)thio-phosphates are obtained from the nucleophilic substitution andoxidation of N-alkyl-2-cycloiminylidenaminodichlorophosphines gen-erated in situ from the reaction of the corresponding N-alkyl-2-amino-cycloiminium halide with phosphorus trichloride and triethylamine.The synthesized thiophosphoric esters have been investigated forfungicidal properties.
Functionalized halophosphines have been used widely as precursorsfor the synthesis of a variety of organophosphorus compounds hav-ing phosphorus in different oxidation states;1,2 including phosphoricesters, thiophosphoric esters, and amidophosphoric esters; a numberof representatives of which are known for their insecticidal and fungici-dal properties.3–6 Synthesis of amidophosphoric, amidothiophosphoric,
We acknowledge CSIR, New Delhi for financial support and ARS, Jaipur for providingfacilities for determination of fungicidal activity. Thanks also are due to RSIC, Lucknowfor providing C, H, N analysis data and NMR spectra.
Address correspondence to Vijaya Kabra, University of Rajasthan, Department ofChemistry, Jaipur 302 004, India. E-mail: [email protected]
851
Dow
nloa
ded
by [
b-on
: Bib
liote
ca d
o co
nhec
imen
to o
nlin
e U
L]
at 0
2:29
07
May
201
4
March 20, 2003 15:32 GPSS TJ683-14
852 N. Gupta et al.
and trisamidophosphoric ester derivatives has been reported fromthe reaction of 2-aminopyridine with dimethylphosphoric chloride, di-ethylthiophosphoric chloride, and bis(phenylamido)phosphoric chlo-ride respectively.7 Alternatively, trisamidophosphoric esters have beenprepared from the reaction of amidophosphoric dichloride withamines8,9 or oxidation of tris-amidophosphorus.8 Dehydrosulfurationof (OR)2P(S)NHCSNHPh yielded (OR)2P(S)N:C:NPh; the latter onfurther reaction with 2-bromoethylamine hydrobromide gave imida-zolidinylidenamidothiophosphoric esters.10 Alkylidenamido-bis(amido)phosphoric esters have been obtained from the reaction ofbis(dimethylamino)chlorophosphine with ketoximes11 or the substi-tution of chlorines from alkylidenamidophosphoric dichloride withamines.12,13
Recently, a novel class of halophosphines, namely N-alkyl-2-cycloiminylidenaminodichlorophosphines has been reported as anintermediate during the synthesis of anellated diazaphospholes.14–16
In view of the electrophilic as well as nucleophilic nature of thephosphorus of the halophosphine moiety,17 the chlorine atoms of theseaminodichlorophosphines may undergo substitution accompanied bythe oxidation of phosphorus18 to form a novel class of alkylidenamidoth-iophosphates incorporating a variety of nitrogen heterocycles. A novelone-pot synthesis of four new classes of amidothiophosphoric estersand trisamidothiophosphoric esters namely, (1-alkyl-2-pyrimidinyl-idenamido)bis(diethylamido)thiophosphates, (1-alkyl-2-pyrimidinyli-denamido)bis(O-2/4-methylphenyl)thiophosphates, (3-alkyl-2-thiazoli-nylidenamido)bis(diethylamido)thiophosphate, and (3-alkyl-2-thiazol-inylidenamido)bis(O-2/4-methylphenyl)thiophosphates from N-alkyl-2-cycloiminylidenaminodichlorophosphines generated in situ fromthe reaction of corresponding N-cycloiminium salt with phosphorustrichloride is reported here. Fungicidal properties of these thiophos-phates have been investigated against Fusarium oxysporium andAlternaria cymopsidies.
RESULTS AND DISCUSSION
(1-Alkyl-2-pyrimidinylidenamino)dichlorophosphine 2a–c is generatedin situ (δ 31P∼ 191) from the reaction of 1-alkyl-2-aminopyrimidiniumhalide 1a–c with phosphorus trichloride (1 equivalent) and triethy-lamine (2 equivalents) in methylene chloride at 0–5◦C. Further ad-dition of a four-fold amount of diethylamine and equimolar amountof sulfur results in the formation of (1-alkyl-2-pyrimidinylidenamido)bis(diethylamido)thiophosphates 3a–c (Scheme 1).
Dow
nloa
ded
by [
b-on
: Bib
liote
ca d
o co
nhec
imen
to o
nlin
e U
L]
at 0
2:29
07
May
201
4
March 20, 2003 15:32 GPSS TJ683-14
Synthesis and Fungicidal Activity of Amidothiophosphoric 853
SCHEME 1
Analogously, from the reaction of 2-amino-3-methylthiazoliniumiodide 5a with phosphorus trichloride (1 equivalent) and tri-ethylamine (2 equivalent) followed by reaction with diethylamine(4 equivalents) and simultaneous oxidation with sulfur (3-methyl-2-thiazolinylidenamido)bis(diethylamido)thiophosphate 7a is obtained(Scheme 2).
SCHEME 2
The reaction of 1a or 1b with o-cresol (2 equivalents) and 1a or5c with p-cresol (2 equivalents) and triethylamine (2 equivalents)
Dow
nloa
ded
by [
b-on
: Bib
liote
ca d
o co
nhec
imen
to o
nlin
e U
L]
at 0
2:29
07
May
201
4
March 20, 2003 15:32 GPSS TJ683-14
TA
BL
EI
Ph
ysic
alan
dS
pect
ralD
ata
ofC
ompo
un
ds1,
3,4,
5,7,
8
m.p
.Y
ield
Mol
.for
m.
31P
-NM
RC
pd.
(◦C
)(%
)(m
ol.w
t.)
(CD
Cl 3
)1H
-NM
Rδ
ppm
(JH
z)
1a15
8–15
985
C11
H12
N3B
r—
5.61
(s,2
H,N
CH
2);
6.73
(t,1
H,3
JH
H=
8.5
Hz,
5-H
);7.
22(b
rs,
5H,C
6H
5);
(266
.1)
8.58
(d,2
H,3
JH
H=
8.5
Hz,
4-H
,6-H
);8.
88(b
rs,
2H,N
H2)
1b17
8–18
078
C12
H14
N3C
l—
2.29
(s,3
H,
p-C
H3);
5.67
(s,2
H,N
CH
2);
6.82
(dd,
1H,3
JH
H=
8.5,
5.7
Hz,
5-H
);(2
35.7
)7.
06(d
,2H
,3J
HH=
7.1
Hz,
m-H
);7.
31(d
,2H
,3J
HH=
7.1
Hz,
o-H
);8.
37(d
d,1H
,3J
HH=
8.5,
4J
HH=
2.8
Hz,
4-H
);8.
58(d
d,1H
,3J
HH=
5.7,
4J
HH=
2.8
Hz,
6-H
);9.
36(b
rs,
2H,N
H2)
1c23
3–23
587
C5H
8N
3I
—3.
56(s
,3H
,NC
H3);
6.73
(t,
1H,3
JH
H=
7.1
Hz,
5-H
);8.
43(
d,2H
,3J
HH=
7.1,
(237
.0)
4-H
,6-H
);8.
74(b
rs,
2H,N
H2)
3a12
3–12
455
C19
H30
N5S
P66
.40.
99(t
,12H
,3J
HH=
7.1
Hz,
NC
H2C
H3);
3.03
(dq,
8H,3
JH
H=
7.1,
3J
PH=
19.8
Hz,
(391
.5)
NC
H2C
H3);
4.96
(s,2
H,N
CH
2C
6H
5);
6.04
(dd,
1H,3
JH
H=
7.1,
4.5
Hz,
5-H
);7.
01(b
rs,
5H,C
6H
5);
7.30
(d,1
H,3
JH
H=
7.1
Hz,
4-H
);8.
30(d
,1H
,3J
HH=
4.5
Hz,
6-H
)3b
122–
123
46C
20H
32N
5S
P66
.20.
99(t
,12H
,3J
HH=
7.1
Hz,
NC
H2C
H3);
2.25
(s,3
H,
p-C
H3);
3.04
(dq,
8H,3
JP
H=
17.3
,(4
05.5
)3J
HH=
7.1
Hz,
NC
H2C
H3);
5.03
(s,2
H,N
CH
2);
6.10
(dd
,1H
,3J
HH=
7.1,
5.7
Hz,
5-H
);7.
11(
s,4H
,C6H
4);
7.28
(d,1
H,3
JH
H=
7.1
Hz,
4-H
);8.
34(u
nre
solv
edd,
1H,6
-H)
3c12
4–12
550
C13
H16
N5S
P65
.01.
0(t
,12H
,3J
HH=
7.1
Hz,
NC
H2C
H3);
3.06
(dq,
8H,3
JH
H=
5.7,
3J
PH=
19.8
Hz,
(305
.3)
NC
H2C
H3);
3.40
(s,3
H,N
CH
3);
6.12
(dd,
1H,3
JH
H=
5.7,
3J
HH=
4.5
Hz,
5-H
),7.
51(d
,1H
,3J
HH=
5.7
Hz,
4-H
);8.
39(d
,1H
,3J
HH=
4.5
Hz,
6-H
)4a
99–1
0045
C25
H24
N3O
2S
P58
.52.
30(s
,6H
,o-C
H3);
4.99
(s,2
H,N
CH
2);
6.38
(dd,
1H,3
JH
H=
6.6,
4.2
Hz,
5-H
);6.
98(4
61.5
)(d
,2H
,3J
HH=
7.3
Hz,
3′-H
ofO
C6H
4);
7.04
(dd,
2H,3
JH
H=
7.6,
6.8
Hz,
5′-H
ofO
C6H
4);
7.09
(t,2
H,3
JH
H=
6.5
Hz,
4′-H
ofO
C6H
4);
7.12
(d,2
H,3
JH
H=
6.8
Hz,
6′-H
ofO
C6H
4);
7.29
(un
reso
lved
,2H
,m-H
ofC
6H
5);
7.33
(dd,
1H,3
JH
H=
5.6,
4J
HH=
2.9
Hz,
p-H
ofC
6H
5);
7.42
(d,2
H,3
JH
H=
8.1
Hz,
o-H
ofC
6H
5);
7.68
(dd,
1H,3
JH
H=
6.6,
4J
HH=
2.7
Hz,
4-H
);8.
54(d
d,1H
,3J
HH=
4.8,
4J
HH=
2.9
Hz,
6-H
)4b
105–
107
44C
26H
26N
3O
2S
P58
.82.
34(s
,9H
,o-C
H3
&p-
CH
3);
4.97
(s,2
H,N
CH
2);
6.42
(un
reso
lved
,1H
,5-H
);(4
75.5
)6.
89–7
.27
(m,1
2H,C
6H
4);
7.42
(d,1
H,3
JH
H=
5.7
Hz,
4-H
);8.
56(u
nre
solv
ed,1
H,6
-H)
4c89
–90
40C
25H
24N
3O
2S
P58
.72.
25(s
,6H
,p-
CH
3);
5.10
(s,2
H,N
CH
2);
6.43
(dd,
1H,3
JH
H=
7.1,
5.7
Hz,
5-H
);(4
61.5
)6.
91–7
.47
(m,1
3H,O
C6H
4,C
6H
5);
7.59
(d,1
H,3
JH
H=
7.1
Hz,
4-H
);7.
69(d
,1H
,3J
HH=
5.7
Hz,
6-H
)
854
Dow
nloa
ded
by [
b-on
: Bib
liote
ca d
o co
nhec
imen
to o
nlin
e U
L]
at 0
2:29
07
May
201
4
March 20, 2003 15:32 GPSS TJ683-14
4d—
—C
19H
20N
3O
2S
P58
.62.
37(s
,6H
,o-C
H3);
3.49
(s,3
H,N
CH
3);
6.41
(un
reso
lved
,1H
,5-H
);(3
85.4
)7.
01–7
.54
(un
reso
lved
m,8
H,O
C6H
4);
7.81
(d,1
H,3
JH
H=
6.7
Hz,
4-H
);8.
62(d
,1H
,3J
HH=
6.9
Hz,
6-H
)4d′
——
C12
H13
N3O
SP
Cl
61.4
2.42
(s,3
H,o
-CH
3);
3.56
(s,3
H,N
CH
3);
6.79
(un
reso
lved
,1H
,5-H
);7.
01–7
.54
(313
.7)
(m,4
H,O
C6H
4);
7.84
(d,1
H,3
JH
H=
6.8
Hz,
4-H
);8.
74(d
,1H
,3J
HH=
7.1
Hz,
6-H
)5a
155–
156
96C
4H
9N
2S
I—
2.80
(s,3
H,N
CH
3);
3.59
(t,2
H,3
JH
H=
7.1
Hz,
5-H
);4.
18(t
,2H
,3J
HH=
7.1
Hz,
4-H
);(2
44.1
)9.
90(s
,2H
,NH
2)
5b10
7–10
883
C10
H13
N2S
Br
—3.
13(t
,2H
,3J
HH=
8.0
Hz,
5-H
);3.
90(t
,2H
,3J
HH=
8.0
Hz,
4-H
);(2
73.2
)4.
91(s
,2H
,NC
H2);
7.21
(br
s,5H
,C6H
5);
10.1
1(b
rs,
2H,N
H2)
5c22
0–22
289
C11
H15
N2S
Br
—1.
85(s
,3H
,p-
CH
3);
2.80
(t,2
H,3
JH
H=
7.5
Hz,
5-H
);3.
23(t
,2H
,3J
HH=
7.5
Hz,
4-H
);(2
87.2
)4.
12(s
,2H
,NC
H2);
7.46
(br
s,4H
,o-H
&m
-H);
10.0
6(s
,2H
,NH
2)
7a49
–50
56C
12H
27N
4S
2P
66.8
1.05
(t,1
2H,3
JH
H=
7.1
Hz,
NC
H2C
H3);
2.93
(t,2
H,3
JH
H=
7.1
Hz,
5-H
);2.
97(s
,3H
,(3
22.5
)N
CH
3);
3.20
(q,8
H,3
JH
H=
7.1
Hz,
NC
H2C
H3);
3.58
(t,2
H,3
JH
H=
7.1
Hz,
4-H
)8a
95–9
740
C25
H27
N2O
2S
2P
60.6
2.29
(s,6
H,O
C6H
4C
H3);
2.32
(s,3
H,N
CH
2C
6H
4C
H3);
3.12
(t,2
H,3
JH
H=
7.6
Hz,
5-H
);(4
54.6
)3.
49(t
,2H
,3J
HH=
7.6
Hz,
4-H
);4.
52(s
,2H
,NC
H2);
6.95
(d,2
H,3
JH
H=
7.3
Hz,
o-H
ofN
CH
2C
6H
4);
6.98
(d,2
H,3
JH
H=
7.3
Hz,
m-H
ofN
CH
2C
6H
4);
7.07
(dd,
4H,3
JH
H=
8.3,
4J
PH=
3.4
Hz,
o-H
ofO
C6H
4);
7.15
(dd,
4H,3
JH
H=
8.3,
4J
PH=
1.5
Hz,
m-H
ofO
C6H
4)
8b—
—C
18H
21N
2O
2S
2P
61.3
2.26
(s,6
H,
p-C
H3);
2.99
(s,3
H,N
CH
3);
3.23
(un
reso
lved
trip
let,
2H,5
-H),
(392
.5)
3.65
(un
reso
lved
trip
let,
2H,4
-H),
7.08
–7.1
4(m
,8H
,C6H
4)
8b′
——
C11
H14
N2O
S2P
Cl
64.8
2.33
(s,3
H,
p-C
H3),
3.05
(s,3
H,N
CH
3);
3.32
(t,2
H,3
JH
H=
8.0
Hz,
5-H
);(3
20.8
)3.
74(t
,2H
,3J
HH=
8.0
Hz,
4-H
);7.
15(d
,2H
,3J
HH=
8.3
Hz,
m-H
);7.
22(d
d,2H
,3J
HH=
8.28
Hz,
4J
PH=
1.9
Hz,
o-H
)8c
——
C18
H21
N2O
2S
2P
60.2
2.32
(s,6
H,o
-CH
3);
2.93
(s,3
H,N
CH
3);
3.21
(t,2
H,3
JH
H=
7.6
Hz,
5-H
);(3
92.5
)3.
63(t
,2H
,3J
HH=
7.6
Hz,
4-H
);7.
09–7
.47
(m,8
H,C
6H
4)
8c′
——
C11
H14
N2O
S2P
Cl
63.7
2.36
(s,3
H,o
-CH
3);
3.00
(s,3
H,N
CH
3);
3.31
(t,2
H,3
JH
H=
7.6
Hz,
5-H
);(3
20.8
)3.
72(t
,2H
,3J
HH=
7.6
Hz,
4-H
);7.
09–7
.47
(m,4
H,C
6H
4)
8d—
—C
24H
25N
2O
2S
2P
2.24
(s,6
H,o
-CH
3);
3.11
(t,2
H,3
JH
H=
7.7
Hz,
5-H
);3.
21(t
,2H
,3J
HH=
7.7,
4-H
);(4
68.6
)4.
49(s
,2H
,NC
H2);
7.02
–7.3
7(m
,13H
,C6H
5,O
C6H
4)
8d′
——
C17
H18
N2O
S2P
Cl
61.2
2.29
(s,3
H,o
-CH
3);
3.44
(t,2
H,3
JH
H=
7.6
Hz,
5-H
);3.
57(t
,2H
,3J
HH=
7.6
Hz,
4-H
);(3
96.9
)4.
54(s
,2H
,NC
H2);
7.02
–7.3
7(m
,9H
,C6H
5,O
C6H
4)
a1H
-NM
Rof
1an
d5
inC
DC
l 3+
DM
SO
-d6
and
3,4,
7an
d8
inC
DC
l 3.
855
Dow
nloa
ded
by [
b-on
: Bib
liote
ca d
o co
nhec
imen
to o
nlin
e U
L]
at 0
2:29
07
May
201
4
March 20, 2003 15:32 GPSS TJ683-14
856 N. Gupta et al.
in place of diethylamine under similar conditions affords (1-benzyl-2-pyrimidinylidenamido)bis(O-2-methylphenyl) thiophosphate 4a,{1-(4-methylbenzyl)-2-pyrimidinylidenamido}bis(O-2-methylphenyl)thiophosphate 4b, (1-benzyl-2-pyrimidinylidenamido)bis(O-4-methyl-phenyl) thiophosphate 4c, and {3-(4-methylbenzyl)-2-thiazolinylidena-mido}bis(O-4-methylphenyl)thiophosphate 8a respectively (Schemes 1and 2).
The products thus obtained are stable cream to yellow crystallinesolids characterized by elemental analysis and NMR spectroscopy(Table I). The 31P NMR signal of 3 and 5 appears at δ∼ 66, which is inthe range of trisamidothiophosphates.19 The 31P NMR signals of 4a–cand 8a in the range δ 58–61 is again characteristic for tetracoordinatedpentavalent phosphorus compounds.19,20 However, the reaction of 2cgenerated from 1c with o-cresol and sulfur is not complete and a mono-substituted product 4d′ also is obtained in addition to 4d, as revealedby the appearance of two signals at δ 61.5 and 58.6 in the 31P NMR spec-trum of the isolated product. In 1H NMR spectrum a singlet at δ 2.37is assigned to the six protons of the two methyl groups of cresol corre-sponding to 4d and the singlet at δ 2.42 to three protons of one 2-methylsubstituent of 4d′. Similarly, the products isolated from the reactions of6a with p-cresol and 6a,b with o-cresol also are found to be mixtures ofmono-(8b′–d′) and disubstituted (8b–d) compounds (Scheme 2), separa-tion of which could not be accomplished by recrystallization. In the caseof the 4-methyl substituent, disubstituted product (8b) is obtained inlarger amount (85%); while in the case of the 2-methyl substituent, themajor component (71–63%) of the product mixture is monosubstituted(8c′ and 8d′), indicating that the steric crowding plays an importantrole on the completion of reaction.
FUNGICIDAL PROPERTIES
The products 3, 4, 7, and 8 have been screened for fungicidal propertiesagainst two fungi, namely Fusarium oxysporium and Alternaria cy-mopsidies at two concentrations of 100 and 500 ppm, and the results interms of the radial growth and statistical analysis are given in Table II.All the compounds tested for both test fungi have been found to showsignificant fungicidal properties in terms of the reduced radial growthwth reference to the control average growths of 84–85% at two con-centrations of 5% and 1%. More significant results have been obtainedat 5% concentration. Among the trisamodothiophosphate derivatives,those (3a,b) with bulkier benzyl or p-methylbenzyl substituent at en-docyclic nitrogen show stronger fungitoxic activity against both fungi.
Dow
nloa
ded
by [
b-on
: Bib
liote
ca d
o co
nhec
imen
to o
nlin
e U
L]
at 0
2:29
07
May
201
4
March 20, 2003 15:32 GPSS TJ683-14
Synthesis and Fungicidal Activity of Amidothiophosphoric 857
TABLE II Fungicidal Activity of the Compounds 3, 4, 7, 8
However, in the case of amidothiophosphates 4 and 8, the fungitoxic ac-tivity is more significant against Fusarium oxysporum than Alternariacymopsidies.
EXPERIMENTAL
All reactions were carried out under nitrogen atmosphere using Schlenktechniques. Solvents were distilled and dried using standard proce-dures and commercial reagents were freshly distilled under nitrogenatmosphere before use. Melting points were determined by capillarymethod and are uncorrected. NMR data were recorded on FT NMR spec-trometer Jeol FX-90Q at 89.5 MHz (1H NMR) and 36.23 MHz (31P NMR)or Bruker WM-400 at 399.65 MHz (1H NMR), 161.7 MHz (31P NMR) orBruker DRX-300 at 300.13 MHz (1H NMR) and 121.5 MHz (31P NMR)with reference to TMS (internal) or 85% H3PO4 (external). Elementalanalyses were carried out on Heraeus Carlo Erba 1108 analyzer.
N-Alkyl-2-aminopyrimidinium Halides (1a–c) and N-Alkyl-2-amino/thiazolinium Halides 5a–c. General Procedure
To a solution of 2-aminopyrimidine (2.853 g, 30 mmol) or 2-amino-thiazoline (3.064 g, 30 mmol) in tetrahydrofuran (60 mL) was added
Dow
nloa
ded
by [
b-on
: Bib
liote
ca d
o co
nhec
imen
to o
nlin
e U
L]
at 0
2:29
07
May
201
4
March 20, 2003 15:32 GPSS TJ683-14
858 N. Gupta et al.
an equimolar amount of benzyl bromide (3.6 mL), p-methylbenzylchloride (4.0 mL)/p-methylbenzyl bromide (5.552 g) or methyl io-dide (1.9 mL) and the resulting mixture was stirred at room tem-perature for 5–10 days. White or cream colored solid thus separatedwas filtered, washed with diethyl ether, and used without furtherpurification.
(1-Alkyl-2-pyrimidinylidenamido)bis(diethylamido)-thiophosphate (3a–c). General Procedure
To a suspension of 1-alkyl-2-aminopyrimidinium bromide (10 mmol) inmethylene chloride (30 mL) was added phosphorus trichloride (1.0 mL,10 mmol) at 0–5◦C. A solution of triethylamine (2.8 mL, 20 mmol) inmethylene chloride (10 mL) was added dropwise with stirring. The re-action mixture was brought to room temperature and the stirring wascontinued for 4–5 h. To this was added sulfur powder (320 mg, 10 mmol)followed by dropwise addition of a solution of diethylamine (4.2 mL,40 mmol) in methylene chloride (10 mL) while maintaining the tem-perature at 0–5◦C and the resulting mixture was stirred overnightat room temperature. Solvent was removed under reduced pressureand the residue extracted with diethyl ether (3 × 50 mL). On leavingthe combined and concentrated extract in refrigerator, 3a–c separatedas creamish white solid, which was filtered washed with hexane anddried.
3a Yield 55%; %Calc C 58.28 H 7.22 N 17.88%Found 58.08 7.18 17.95
3b Yield 46%; %Calc C 59.18 H 7.89 N 17.26%Found 59.03 7.92 17.45
3c Yield 50%; %Calc C 49.49 H 8.30 N 22.20%Found 49.37 8.33 22.17
(1-Alkyl-2-pyrimidinylidenamido)bis(O-2/4-methylphenyl)thiophosphates (4a–d). General Procedure
Phosphorus trichloride (1.8 mL, 20 mmol) was added to a well-stirredsuspension of 1-alkyl-2-aminopyrimidinium halide (20 mmol) in methy-lene chloride (50 mL) at 0–5◦C. A solution of triethylamine (5.6 mL,40 mmol) in methylene chloride (10 mL) was added dropwise slowlywith constant stirring. The reaction mixture was brought to roomtemperature and the stirring was continued for 5 h. To this wasadded sulfur powder (640 mg, 20 mmol) and triethylamine (5.6 mL,
Dow
nloa
ded
by [
b-on
: Bib
liote
ca d
o co
nhec
imen
to o
nlin
e U
L]
at 0
2:29
07
May
201
4
March 20, 2003 15:32 GPSS TJ683-14
Synthesis and Fungicidal Activity of Amidothiophosphoric 859
40 mmol) followed by dropwise addition of a solution of o- or p-cresol(4.2 mL, 40 mmol) in methylene chloride (10 mL) over 15–20 minwhile maintaining the temperature at 0–5◦C. The resulting reactionmixture stirred overnight at room temperature. Solvent was removedunder reduced pressure and the residue extracted with diethyl ether(2 × 50 mL). On leaving the combined and concentrated extract inrefrigerator, 4a–c deposited as light yellow crystalline solid, whichwas filtered washed with hexane and dried. However, the productobtained from the reaction of 1c with o-cresol was found to be amixture of (1-methyl-2-pyrimidinylidenamido)bis(O-2-methylphenyl)-thiophosphate (4d, 25%) and (1-methyl-2-pyrimidinylidenamido)-(O-2-methylphenyl)thiophosphoric chloride (4d′, 75%).
4a Yield 45%; %Calc C 65.06 H 5.24 N 9.10%Found 65.27 5.21 9.06
4b Yield 44%; %Calc C 65.66 H 5.51 N 8.83%Found 65.79 5.47 8.77
4c Yield 40%; %Calc C 65.06 H 5.24 N 9.10%Found 65.19 5.28 9.17
To a suspension of 2-amino-3-methylthiazolinium iodide (3.904 g,16 mmol) in methylene chloride (30 mL) was added phosphorus trichlo-ride (1.4 mL, 16 mmol) at 0–5◦C. A solution of triethylamine (4.4 mL,32 mmol) in methylene chloride (10 mL) was added dropwise with stir-ring. The reaction mixture was brought to room temperature and thestirring was continued for 4 h. To this was added sulfur powder (512 mg,16 mmol) followed by dropwise addition of a solution of diethylamine(6.6 mL, 64 mmol) in methylene chloride (10 mL) while maintaining thetemperature at 0–5◦C and the resulting mixture was stirred overnightat room temperature. Solvent was removed under reduced pressureand the residue extracted with diethyl ether (3 × 50 mL). On leavingthe combined and concentrated extract in refrigerator, 7a separatedas creamish white solid, which was filtered washed with hexane anddried.
7a Yield 56%; %Calc C 44.69 H 8.37 N 17.36%Found 44.75 8.28 17.11
Dow
nloa
ded
by [
b-on
: Bib
liote
ca d
o co
nhec
imen
to o
nlin
e U
L]
at 0
2:29
07
May
201
4
March 20, 2003 15:32 GPSS TJ683-14
860 N. Gupta et al.
(3-Alkyl-2-thiazolinylidenamido)bis(O-2/4-methylphenyl)thiophosphate (8a–d) and(3-Alkyl-2-thiazolinylidenamido)(O-2/4-methylphenyl)-thiophosphoric Chloride (8b’–d’). General Procedure
Phosphorus trichloride (0.9 mL, 10 mmol) was added to a well-stirredsuspension of 3-alkyl-2-aminothiazolinium halide (10 mmol) in methy-lene chloride (40 mL) at 0–5◦C. A solution of triethylamine (2.8 mL,20 mmol) in methylene chloride (10 mL) was added dropwise with con-stant stirring. The reaction mixture was brought to room temperatureand the stirring was continued for 6 h. To this was added sulfur pow-der (320 mg, 10 mmol) and triethylamine (2.8 mL, 20 mmol) followedby dropwise addition of a solution of o- or p-cresol (2.1 mL, 20 mmol)in methylene chloride (10 mL) over 15–20 min while maintaining thetemperature again at 0–5◦C. The resulting reaction mixture was stirredovernight at room temperature. Solvent was removed under reducedpressure and the residue extracted with diethyl ether (2 × 50 mL). Onleaving the combined and concentrated extract in refrigerator, white topale crystalline solid deposited, which was filtered washed with hexaneand dried. Except 8a, the product was found to be a mixture of 8 and 8′.
8a Yield 40%; %Calc C 62.21 H 5.60 N 5.80%Found 62.34 5.54 5.71
Fungicidal Activity
A standard method to evaluate the fungitoxic properties of the com-pounds was adopted here. Using the poison food technique, the twopathogens, Fusarium oxysporium and Alternaria cymopsidies, were iso-lated from the Cumin (Cuminum cyminum) and cluster bean (Cymopsistetragonal) crops, respectively on 2% sterile potato-dextrose agar (PDA)medium. Test compounds were added to this in two concentrations (100ppm and 500 ppm). This poisoned medium was poured into petriplates(90 mm diameter) and was inoculated by inoculum disk of 3 mm diam-eter cut from the margin of a 6-day old culture of the test pathogen andincubated at 26◦C. Each experiment was replicated three times and asuitable control without the test compound was also maintained. Theradial growth of the mycelium was measured in mm after 6 days.
REFERENCES
[1] M. Regitz, Ed., Houben Weyl-Methoden der Organischen Chemie (Thieme Stuttgart,New York, 1982), Vol. E1 and E2.
Dow
nloa
ded
by [
b-on
: Bib
liote
ca d
o co
nhec
imen
to o
nlin
e U
L]
at 0
2:29
07
May
201
4
March 20, 2003 15:32 GPSS TJ683-14
Synthesis and Fungicidal Activity of Amidothiophosphoric 861
[2] M. Regitz and O. J. Scherer, Eds., Multiple Bonds and Low Coordination inPhosphorus Chemistry (Thieme Stuttgart, 1990).
[3] M. I. Kabachnik, E. I. Golubeva, D. M. Paikin, M. P. Shabanova, N. M. Gamper, andL. F. Efimova, Zh. Obshch. Khim., 29, 1671 (1959).
[4] M. I. Kabachnik, N. N. Godovikov, D. M. Paikin, M. P. Shabanova, and N. M. Gamper,Zh. Obshch. Khim., 29, 2182 (1959).
[5] Y. L. Nene and P. N. Thapliyal, Fungicides in Plant Disease Control (Oxford, IBH,New Delhi, 1979).
[6] G. S. Gruzdyev, V. A. Zinchenko, V. A. Kalinin, and R. I. Slovtsov, The ChemicalProtection of Plants, edited by G. S. Gruzdyev (MIR, Moscow, 1983).
[7] B. A. Arbuzov, V. M. Zoroatrova, and M. P. Osipova, Izv. Akad. Nauk SSSR, Otdel.Khim. Nauk., 2163 (1961).
[8] A. P. Marchenko, A. M. Pinchuk, and N. G. Fashchenko, Zh. Obshch. Khim., 43,1900 (1973).
[9] H. Dorn, H. Graubaum, V. Zeigan, and R. Radeglia, Z. Chem., 15, 485 (1975).[10] R. M. Kamalov, N. A. Khailova, and M. A. Pudovik, Zh. Obshch. Khim., 64, 1994
(1994).[11] C. Brown, R. F. Hudson, A. Maron, and K. A. F. Racord, J. Chem. Soc., Chem. Comm.,
663 (1976).[12] Z. M. Ivanova, N. I. Gusar, and Y. G. Gololobov, Zh. Obshch. Khim., 44, 538
(1974).[13] G. I. Derkach and N. I. Liptuga, Zh. Obshch. Khim., 38, 1779 (1968).[14] R. K. Bansal, D. C. Sharma, and R. Mahnot, Tetrahedron Lett., 32, 6433
(1991).[15] R. K. Bansal, V. Kabra, R. Munjal, and N. Gupta, Indian J. Chem., 33B, 992
(1994).[16] K. Karaghiosoff, R. K. Bansal, and N. Gupta, Z. Naturforsch., 47B, 373 (1992).[17] A. Scmidtpeter and W. Zeiß, Chem. Ber., 104, 1199 (1971).[18] R. K. Bansal, V. Kabra, R. Munjal, and N. Gupta, Phosphorus, Sulfur, and Silicon,
97, 141 (1994).[19] R. S. Edmundson, Handbook of Phosphorus-31 Nuclear Magnetic Resonance data,
edited by J. C. Tebby (CRC Press, 1991), p. 231, Boca Raton, FL.[20] J. C. Tebby, Phosphorus-31 NMR Spectroscopy in Stereochemical Analysis, Methods
in Stereochemical Analysis, edited by J. G. Verkade and L. D. Quinn (VCH, 1987).
