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Патент USA US3080283

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d?hh?'i'g
United States Patent 6" ice
Patented Mar. 5, 19%3
2
3
Included within the above general formula is a pre
ferred group of ‘compounds which have the structure:
3,089,273
AMINOBUTYNYL PHO§PHATES
ROX
Joseph ‘W. Baker and John P. Chupp, Kirlrwood, and
Peter E. Newailis, Crestwood, Mm, assignors to Mon
santo Chemical Company, St. Louis, Man, a corpora
\ ||
PSCHzCEC CHzY
tion of Delaware
No Drawing. Filed Nov. 9, 1%59, Ser. No. 851,555
14 Claims. (Cl. 167-22)
where R, R’ and X have the same meaning as above,
and Y is selected from di-lower acyclic amino radicals
This invention relates to new organic phosphorus com 10 or morpholino. Such compounds display an optimum
degree of biocidal activity against a Wide variety of pests.
pounds and to insecticidal formulations comprising such
compounds. More particularly, the invention is con
cerned with those phosphorous compounds which are
derived from the interaction of an amine and a halo
genated butynyl salt of a phosphoric acid.
The new compounds of this invention may be readily
prepared by reacting a primary or secondary amine with
the reaction product of a dihalogenated butyne and a
The proportions of reactants
15 salt of a phosphoric acid.
will vary in accordance with the particular resultant prod
It is an object of this invention to provide new and
uct. The reaction of the amine, the ‘butyne and the acid
salt may also be carried out in situ.
The invention will be more fully understood by ref
insecticides. Still a further object is to provide new
and useful formulations comprising such insecticides. 20 erence to the following examples. These examples, how
ever, are given for the purpose of illustration only and
The compounds of the present invention are phosphorus
are not to be construed as limiting the scope of the present
derivatives of the general formula:
invention in any way.
useful compounds of phosphorus. It is a further object
of this invention to provide a new class of highly useful
ROX
EXAMPLE I
25
0,0-Diethyl S-(4-Diezhylamino)~2-Butynyl
Fhosphorothiolate
wherein R and R’ represent like or unlike lower alkyl
radicals or alkoxy substituted lower alkyl radicals, and
X and X’ are oxygen or sulfur.
As employed herein,
the term “lower” connotes radicalshaving from 1.to '
about 4 carbon atoms.
In the above formula, Y rep
021550
0
@3115
021150
CzH5
In a suitable reactor was placed 56.1 grams (0.3 mole)
resents heterocyclic amino radicals, quaternary ammoni 35 of ammonium 0,0-diethyl phosphorothioate dissolved
um salt radicals or an amino radical of the general struc
in 150 ml; of acetone at 50° C.
There was added 37.5
grams (0.3 mole) of 1,4-dichlorobutyne-2, and the mix
ture
'
ture was heated to re?ux for 3 hours.
Rn
45.2 grams (0.62
mole) of diethyl amine was then added, and this mix
ture was re?uxed for 4 hours. The reaction product
wherein R” and R’” are selected from hydrogen, acyclic
was ?ltered and Washed with fresh acetone. The ?ltrate
was then stripped of acetone, and the residue was diluted
with water. It was then extracted with chloroform,
radicals, alicyclic radicals or aryl radicals. As employed
washed with sodium carbonate solution, and ?nally
herein, the term “quaternary ammonium salt radical” 45 stripped to 130° C. at 4 mm. pressure. There was ob
connotes a quaternary ammonium salt which has an open
tained 37.0 grams (63% of theory) of 0,0-diethyl S-(4
valence on the nitrogen atom. The acyclic and alicyclic
diethylamino)-2-butynyl phosphorothiolate as a viscous
radicals contemplated by this invention are those con
amber liquid.
EXAMPLE II
taining up to about 8 carbon atoms.
Illustrative, but not limitative, of the heterocyclic amino 50
radicals represented by Y are azirino, aziridino, azetino,
azetidino, pyrrolyl, pyrro-linyl, pyrrolidinyl, pyrazolyl,
imidazolyl, triazolyl, pyridyl, piperidyl, morpholino,
0,0-Diethyl S- (4-Diallylamino ) -2-Butynyl
Phosphorothiolare
pyrazinyl, piperazino, azepidino, diazepino and the like.
Among the quaternary salt radicals represented by Y 55
021550 0
are those wherein the anion is chloride, bromide, iodide,
C2Ha0
?uoride, sulfate, phosphate, nitrate, citrate, oxalate,
tartrate or the like.
CH2CH=OH1
\ ll
rsoniozocum
CHsCH=CHz
A suitable reactor was charged with 25.7 grams (0.1
mole) of S-(4-chloro-2-butynyl) 0,0-diethyl phosphoro
Exemplary of the radicals represented by R" and R’”
are the alkyls such as methyl, ethyl, n-propyl, isopropyl, 60 thiolate and 21.4 grams (0.22 mole) of diallylarnine.
The mixture was re?uxed for 4 hours, and a precipitate
appeared. It was then cooled. The mixture was ?ltered,
and
the precipitate washed with acetone. The latter was
etc.; the alkenyls and alkynyls such as vinyl, allyl, n
stripped off, and the residue was extracted with chloro
butenyl-Z, diisobutenyl, pr-opynyl, 2-butynyl, 3-hexynyl,
etc.; other \acyclics such as methoxyethyl, ethoxyethyl, 2 65 form, washed with water, and stripped to a temperature
of 110° C. at 3 mm. pressure. A yield of 23.5 grams
chloroethyl, 2-chloroallyl, benzyl, cyanoethyl, cyanobutyl,
n-‘outyl, tertiary butyl, isoamyl, n-hexyl, Z-methyl-l
pentyl, n-heptyl, 3-ethyl-2-pentyl, n»octyl, 2-e-thylhexyl,
hydroxypropyl,
hydroxypentyl,
ethoxycarbonylethyl,
(75% of theory) of 0,0-diethyl S~(4-diallylamino)-2
butynyl phospho-rothiolate was obtained as an amber
rnethoxycarbonylpropyl, etc; alicyclics such as cyclo
propyl, cyclopentyl, cycloheptyl, etc.; and aryls such as 70 liquid. Analysis showed 9.5% phosphorus and 4.1% ni
trogen as compared to the calculated values of 9.8%
phenyl, naphthyl, xenyl, chlorophenyl, nitrophenyl,
phosphorus and 4.4% nitrogen.
methoxyphenyl, etc.
'5
$080,273
a
a)
4
A reactor was charged with 13.7 grams (0.05 mole) of
EXAMPLE III
S-(4-chloro-2-butynyl) 0,0-diethyl phosphorodithioate,
0,0-Diethyl S-(4-Dimethylamino)-2-Butynyl
Plwsphorothiolate
6.5 grams (0.05 mole) of N-ethylaniline, 5.1 grams (0.05
mole) of triethylamine and 200 ml. of benzene. The
mixture was stirred at re?ux for 6 hours. The reaction
product was ?ltered, and the ?ltrate was washed with
water and stripped to 120° C. at 2 mm. pressure. A yield
CH3
PSOHzCEGCHzN
C2H5O
CH:
In the procedure of Example II, 10 grams (0.22 mole)
of dimethylarnine was substituted for the diallylamine.
of 10.5 grams (59% of theory) of 0,0-diethyl S-(N-ethyl
The phosphorothiolate was dissolved in 100 ml. of acetone 10
and the gaseous amine was introduced. The yield was
amber liquid.
anilino)-2-butynyl phosphorodithioate was obtained as an
10.0 vvgrams (39.2% of theory) of 0,0-diethyl S-(4-di
0,0-Diethyl S-(4-N-Ethyl4znilino)-2-Butynyl
methy'lamino)-2~butynyl phosphorothiolate as an amber
liquid. As compared to calculated value of 11.7% ~phos-,
porous, it analyzed as 12.1% phosphorous.
EXAMPLE IV
Phosphorothiolate
15
0,0-Dyiethyl S-(4-Ethylamirz0)~2-Buty?yl
Phosphorothiolate
(377350 0
\illsoHgozcoHrN
C3H50/
EXAMPLE VIII
C2H5O
O
Psomozoomrt/
Q1350
w
CZHs
05H:
In the procedure of Example VII, 12.8 grams (0.05
CzHs
20
mole) of S-(4-chloro-2-butynyl) 0,0-diethyl phosphoro
thiolate was substituted for the dithioate, and only 100
ml. of benzene was employed. There was obtained 13.5
H
grams (80% of theory) of 0,0-diethyl S-(N-‘ethylanilinoy
A reactor was charged with 12.9 grams (0.05 mole) of:
Z-butynyl phosphorothiolate as an amber liquid. As com
S-(4-chloro-2-butynyl) 0,0-diethyl phosphorothiolate in
to calculated values of 9.1% phosphorous and 4.1%
50 ml. of benzene, 2.2 grams (0.05 mole) of ethylarnine, 25 pared
nitrogen, it analyzed as 8.6% phosphorous and 4.5%
and 5.0 grams (0.05 mole) of triethylamine, the latter
nitrogen.
two being in 100 ml. of benzene. The mixture was stirred
EXAMPLE IX
at room temperature for 6 hours and then heated to 30°—
0,0-Diethyl S-(4-Allylamin0)-2-Butynyl
35° C. for 2 additional hours. The reaction product was
Phosphorodithioate
?ltered, and the ?ltrate was washed with water and 30
stripped to 110° C. ‘at 8 mm. pressure.
There was ob
0:11.50
tained 9.8 grams (74% of theory) of 0,0-diethyl S-(4
5
H
P'somoEoornN
ethylamino)-2-butynyl phosphorothiolate as an amber
liquid.
011150
EXAMPLE V
35
QO-Diethyl S-(4-Allylamino)~2-Butynyl
_
mole), of S-(4-chloro-2-butynyl) 0,0-.diethyl phosphorodi
t~l1ioate,‘2.9 grams (0.05 mole) of allylamine, 5.1 grams
(0.05 mole) 'oftriethylamine and 150 ml. of benzene.
Phosphorothz'lolat'e
023.0 0
CHZCH=CH¢
This mixture was heated with stirring at 30°—40° C. for 3
The reac
PSCHzGECCHaN.
c2350
CH2CH=CH1
A suitable reactor was charged with v13.7 grams (0.05,
40 hours and then re?uxed for 2 additional hours.
7H
U
tion product was ?ltered, and the ?ltrate was washed with
I
In the procedure'of Example IV, 2.9’grams (0.05 mole)
water and stripped to 110° C. at 3 mm. pressure. There
of allylamine was substituted for the ethylamine. The
was obtained 12 grams (82% of theory) of 0,0-diethyl
mixture was heated to. 30°—40 °’ C. for 5 hours, and at 60C‘
C.’ for 2 additional hours. The reaction product was 45
S-(4-al1ylarnino)-2-butynyl phosphorodithioate.
Worked up as in Example IV. A yield of 13.7 grams
EXAMPLE X_
(100% of theory) of QO-diethyl S-(4-allylamino).-2
'0,0'-Diethyl_ S-(4-Diallylamino)-2éButynyl
Phosphorodithz'oate
butynyl phosphorothiolate as an amber liquid.
v
_
EXAMPLE VI
0,0-Diethyl S-(4-Dimethylamina)-2-13utynylv
Phposphorodithioate
C2H5O
s
50
CH3
CH3
omoueom
PSCHzCECCHzN
rIntoya suitable reactor‘ was charged 8.0..grams (0.082
PSCHzCECCHzN/
0211.0 '
021E150 s
55
Into a suitable reactor was charged. 21.8 grams (0.08
mole) of S-(4-chloro-2-butynyl) 0,0-diethyl phosphoro
mole} of diallylamine, 8.3, grams ( 0.082‘ mole) of- triethyl
amine,v 21.8 grams (‘0.082 mole) of SV-(‘4-chlord-2-butynyl);
0,0-diethyl phosphorodithioate, and 100 ml. of'acetone.
This mixture was heated with stirring for 5 hours at re?ux.
dithioate in 100 ml. of benzene. 9.0 grams (0.2 mole) of
dimethylarnine was passed into the solution of 0°-10° C.,
The, reaction product was'stripped of acetone, and the
residue was” extracted with chloroform, washed with water
and the mixture was stirred at room temperature for 6 60 and stripped to 110° C. at 2 mm. pressure. A yield of
hours. The reaction mixture was then ?l'tered,'an'd the
21.3 grams (7.8% of theory) of 0,0-diethylS-(4-diallyl
?ltrate washed with water and stripped to 130° C. at
amino).-2-butynyl phosphorodithioate was obtained as
2 mm. pressure. There was obtained 13 grains (58% of
an amber liquid.
theory) of a viscous dark brown liquid which was identi
EXAMPLE XI
?ed as 0,0-diethyl_ S-(4-dimethylam‘ino)-2-butynyl phos- 65
0,0-Dz'ethyl S-(4-N-Para-Chloroanilino)-2-Butynyl
phorodithioate. Analysis showed 11.9% phosphorus'as
Phosphorothiolate
‘compared with a calculated value of 11.0% phosphorous.
EXAMPLE VII
O;O-Diethyl ‘ S-(4-N-Ethylanilino)~2-Butyhyl
Phosphorodithioate
\H.
.
70
02,1350
Cir-r50 s
P
/"
SCH-:CECCHzN
v/.'E[I
A ‘suitable reactor was charged with 10.2 grams (0.04
PSCHaQEQOHgrN'
02360
031150 vO
mole) of S-(4-ch1oro-2-butynyl) 0,0-diethyl phosphoroCgHg
75 thiolate, 5.1 grams (0.04 mole) of para-chloroaniline and.
3,080,273
6
5
EXAMPLE XVI
4.1 grams (0.04 moles) of triethylamine, the latter two
0,0-Diethyl S-(4-Para-Anisoyl)-2-Butynyl
in 100 ml. of toluene. The mixture was heated at 100°
C. for 6 hours. The reaction product was then ?ltered,
and the ?ltrate was washed with water and stripped to
120° C. at 2 mm. pressure.
Phosphorothiolate
021150
There was obtained 5 grams
s
H
(36% of theory) of 0,0-diethyl S-(N-para-chloroani
lino)-2-butynyl phosphorothiolate as a viscous amber
iquid.
In the procedure of Example XV, 6.1 grams (0.05 mole)
EXAMPLE XII
0,0-Diethyl S-(4-Diis0pr0pyiamino) -2-Butynyl
Phosphorothiolate
10 of anisidine was substituted for the aniline, and the mix
ture was re?uxed for 8 hours. The ?nal stripping was to
140° C. at 1 mm. A yield of 9.5 grams (44% of theory)
of 0,0-diethy1 S-(para-anisoyl)-2-butynyl phosphorothio
C2H5O O
011(0113):
\H
PsornoEoornN
late was obtained as a viscous amber liquid.
15
C2H50
CHWHQ:
A suitable reactor was charged with 5.1 grams (0.05
EXAMPLE’ XVII
0,0-Diethyl S- (4-Diethylamino) -2-Butynyl
mole) of each of diisopropylamine and triethylamine, and
150 m1. of chloroform.
Phosphorodithioate
There was then added 12.9 grams
(0.05 mole) of S-(4-chloro-2-butynyl) 0,0-diethyl phos
\H
PSCHsCECCHzN
phorothiolate with moderate cooling. The reaction mix
ture was heated at re?uxing temperature for 5 hours and
021150
then cooled. The reaction product was ?ltered, and the
?ltrate was washed with water and stripped to 120° C.
02115
A suitable reactor was charged with 20.3 grams (0.1
mole) of ammonium 0,0-diethyl phosphorodithioate in
at 1 mm. pressure.
A yield of 14 grams (87% of 25 200 ml. of acetone and 12.3 grams of 1,4-dichlorobutyne
2. The mixture was heated at re?uxing temperature for
phosphorothiolate was obtained as an amber liquid.
2 hours and then cooled. There was added 14.6 grams
theory) of 0,0-diethyl S-(4-diisopropy1amino)~2-butynyl
(0.2 mole) of diethylamine, and the resultant mixture
EXAMPLE XIII
0,0-Dicthyl S-(4-Di-n-Pr0pylamino)-2-Butynyl
Phosphorothiolate
(721150
0
was heated at re?uxing temperature for 10 hours. An
'30 orange precipitate formed and was ?ltered out after the
reaction mixture was cooled. The ?ltratewas stripped
of acetone and extracted with chloroform. The residue
was washed with water and stripped to 120° C. at 5 mm.
pressure. There was obtained 20.8 grams (68% of
CHzCHgCH;
\ I!
rsomozcoum
csHso
135
substituted for the diisopropylamine.
theory) of 0,0-diethyl S-(4-diethylamino)-2-butynyl
phosphorodithioate.
In the procedure of Example XII, di-n-propylamine'was
EXAMPLE XVIII
There was obtained
13.8 grams (86% of theory) of 0,0-diethy1 S-(4-di-n
propylarnino)-2-butynyl phosphorothiolate as an amber
liquid.
0,0-_Diethyl. S-(4-Ethoxycarbonylmethylamino)-2
40
-
Butynyl Phosphorodithioate
E
EXAMPLE XIV
0
0,0-Diethyl S-(4-Tert.-Butylamin0)-2-Butynyl
Phosphorothiolate
CHOO
25
021150
45
/H
0112000211;
A reactor was charged with 8.1 grams (0.082 mole) of
triethylamine and 5.6 grams (0.04 mole) of ethoxycar
bonylmethylamine in 100 m1. of benzene, and 10.8 grams
C2350
‘(0.04 mole) of S-(4-chloro-2-butyny1)70,0-diethyl phos
C (CHQQ
phorodithioate and stirred at room temperature for 30
In the procedure of Example XII, 3.7 grams (0.05
minutes. The mixture was then heated at re?uxing tem
mole) of tert.-butylamine was substituted of the diisopro 50 perature for 5 hours, after which it 'was ?ltered. The
pylamine. The reaction product was worked up in the
?ltrate was washed with water and stripped to 100° C. at
same manner except that the ?nal stripping was to 110° C.
1 mm. pressure. A yield of 9.2 grams (68% of theory)
at 1 mm. pressure.
A yield of 10.0 grams (68% of
theory) of 0,0-diethyl S-(4-tert.-butylarnino)~2-butynyl
phosphorothiolate was obtained as an amber liquid. Anal
ysis showed 11.31% phosphorus as against a calculated
of 0,0-diethyl S-(4-ethoxycarbonylrnethylamino)-2-bu
55
tynyl phosphorodithioate was obtained.
EXAMPLE XIX
0,0,-Diethyl S-(4-Ethoxycarbonylmethylamino)-2
value of 10.6% phosphorus.
\
EXAMPLE XV
Butyhyl Phosp'horothiolale
0,0-Diethyl S-(4-Anz'lino)-2~Butynyl Phosphorothiolate
CrHsO
O
\
H
il’SCHrCECCEhN
In the procedure of Example XVIII, 10.2 grams (0.04
65 mole) of thiolate was substituted for the dithioate.
Into a suitable reactor was charged 4.7 grams (0.05
mole) of aniline, 5.1 grams (0.05 mole) of triethylamine
and 150 ml. of benzene.
12.8 grams (0.05 mole) of S
There
was obtained 9.2 grams (68% of theory) of 0,0-diethyl
' S'- (4-ethoxycarbonylrnethylamino) -2-butyny1 phosphoro
thiolate.
.
EXAMPLE XX
(4-chloro-2-butynyl)-0,0-diethyl phosphorothiolate was
added, and the mixture was heated at 60°-65° C. for 10 70
hours. The reaction product was ?ltered, and the ?ltrate
.
O,O-Diisopr0pyl S-(4-Diethylamino)-2-Butynyl I
Phosphorothiolate
There was obtained 5.0 grams of 0,0-diethyl
S-(anilino)-2-butynyl phosphorothiolate as an amber
liquid.
7
p
.
’
.7
.
(CH3)2CHO\€ '
_
(OHzhOHO
'
' ‘
was washed with water and stripped to 130° C. at 1 mm.
pressure.
'
_
CaHu
_PSCH:_C.=_OCH:N
(11H:
3,080.2?8?
8
EXAMPLE xxrv
Into a suitable reactor'was charged 2.2 grams (0.03
mole) ofjdiethylamineand 3.0 grams (0.03 mole) of tri
(LO-methyl S-(4-Diethylmethylamino)-2-Butynyl
Phosphorothiolate, Methosulfate Salt
ethylamine in 100 ml. of benzene, and 8.6 grams (0.03
mole) of S-(4-chloro-2-butynyl) 0,0-diisopropy1 phos
(321150 0
phorothiolate. The procedure of Example XVIII was
followed. A yiel'd'of 9.2 grams (96% of theory) of 0,0
diisopropyl‘ Sl(4,-clieth_ylamino)-2-butynyl phosphorothio
late was obtained.
'
EXAMPLE XXI
O,'Q~.Diethyl S¢(4-Ethylamin0,):2:B1ztynyl
Phosphoradithioate
0-23.50 1s
l0.
)1
50° C. with a pump (2-4 mm. pressure). A yield of 9.4
grams (70% of theory) of the methosulfate salt was
:P'S-CHZGECGHSN
021150
A reaction ?ask protected by a calcium sulfate drying
tube was charged with 9.0 grams (0.0308 mole) of the
thiolate formed in Example'l and 3.94 grams (0.0308
mole) of methyl sulfate. The mixture was allowed to
stand overnight. A supernatant layer which formed was
decanted leaving a residual oil which was evacuated at
obtained.
> 0 2B:
EXAMPLE XXV
A reactor was charged with 2.6- grams (0.06 mole) of
ethylamine andi5_.0 grams (0.05 mole) ;of' triethylamine in
100 ml. of benzene, and 13.6 grams (0.05 mole) of S-(4 20
chloro-2-butynyl) ..0,0-diethyl phosphorodithioate. The
mixture was stirred at room temperature for 4 hours and
-4-[Qo-Diethoxyphosphinylthio]-2-Butynyl
Triethylammonium Iodide
CRHsO\ . OII
PsomoEo oumwoannn
then heated to re?uxing temperature for an additional
hour. ‘The reaction product was worked up in the manner
ofExample XVIII except that it was stripped .to 80° C. 25
‘In the procedure of Example XXIV, 6.2 grams (0.04
at 1 mm. pressure. .A yield of 4.0 grams (28.4% of
mole) of ethyl iodide was substituted for the sulfate.
theory) of 0,0-diethyl S-(4-_ethylamino)-.2~butynyl phos-.
There was obtained 11.2 grams (8.1% of theory) of the
phorodithioate waslobtained.
triethylammonium iodide.
EXAMPLE XXII
0,0-Diethyl S-(4-Piperidino)-2-Butynyl
Phosphorothiolate
0,0:Diethyl S-1E4-BiS-I(Z-Cyanoethylamino) ~2-Butynyl]
Phosphorodithioqte
C4350 9!’
EXAMPLE XXVI
3.0
CzHsO O
|
>iPSCHzCEC
CHzN:
CHZGHICN
\hsomozocmN
021150
:
A'suitable reactor was charged with 4.3 grams (0.05
mole) of piperidine and 5.1 grams (0.05 mole) of tri
‘ .OHZCHZCN
A‘suitable reactor was charged-with 3.7 grams (0.03
ethylamine in 100 ml. of chloroform. There was then
mole) of bis-(2-cyanoethyl) amine [and 3.0 grams (0.03 40 added 12.3 grams (0.05 mole) of S-(4-chloro-2-butynyl)
mole) of triethylamine in 100 ml. of'benzene, and then
0,0-diethyl phosphorothiolate in 50 ml. of chloroform,
8.2 grams (0.03 mole) of v,S-(4-ehloro'-2-butynyl) 0,0-di
and the, mixture was heated at re?uxing temperature for
ethyl phosphorodithioate was added. “The mixture was
4 hours. The reaction product was washed with water
heated at re?uxing temperature for 4 hours, and the re
and stripped to 110° C. at 3 mm. pressure. There was
:45
‘action product was ?ltered. The ?ltrate was washed with
obtained 10.5 grams (65% of theory)v of 0,0-diethyl
‘waterand strippedto'SO,“ C.'at f1 mm. pressure. There
S-(4-piperidino)-2-butynyl phosphorothiolate.
‘was obtained 6.1.,grams (56.6% of theory) of 0,,O-diethyl
When 4.5 grams (0.05 mole) of N-methylpiperazine
.Sj-.[4#bis+(2rcyanoethylamino)>2-butyny11
phosphorodi
‘thioate.
\
When 7.7; grams (0.03v mole_).of thiolatewas-substituted
was substituted for the piperidine, a yield of 9.5 grams
50
(59% of theory) of N-methyl N'-[diethoxyphosphino~
-thioyl-(2-butynyl)] piperazine was obtained.
for thewdithioate in the charge,.and the ?ltratewas stripped
EXAMPLE XXVII
~_o'f_~10.,Q-dietl1.yl. S:t4-bisr(2-¢yan0ethy1amin0)-2=butyny1]
N-Methyl N'- [Diethoxyphosphinothioylthio-(‘Z
Butynyl)] Piperazine
to90i°p (Spat 1rmm.-pressu_re,-=4.0.grams (39%.of, theory)
phosphorothiolate, was‘ obtained.
GaHsO S
EXAMPLE XXIII
0,0-Dietlzyl ‘S-(éMorpholinp)J-Butynyl
Phosphorothiolate
PsomozoornN'
N-.-OHa
CzHsO
60
'Into .a reactor was. charged 4.5 grams (0.05 mole) of
N-methylpiperazine, 5.1 grams (0.05 mole) of triethyl
amine, 13.7 grams (0.05 mole) of S-(4-chloro-2-butynyl)
0,0-diethyl phosphorodithioate and 100 ml. of chloro
021360
‘Into asuitable reactor was‘ charged 1'1.-6'g_rams‘ (0.044
-mole) of >S-(4-chloro=2-butynyl) 0,0-diethyl phosphoro
thiolate, 4.4 grams (0.05 mole) of morpholine, 5.1. grams
form. The mixture was heated at re?uxing temperature
65 for 8 hours and then cooled. The reaction product was
?ltered‘, and the ?ltrate was Washed with Water and stripped
to 110° C. at 3 mm. pressure. There was obtained 13.5
grams (80% of theory) of N-rnethyl N'-[-diethoxyphos
(0.05 mole) of triethyl'arnine and 100 ml. of acetone.
phinothioylthio-(Z-butynyl)] piperazine. Analysis showed
The mixture. was‘heated at re?uxing temperature for 8 70 9.2% phosphorus, 19.1% sulfur and 8.7% nitrogen as
hours, and the reaction product was worked up as in
‘compared with calculated values of 9.5% phosphorus,
Example 11 except that the ?nal stripping was to 100° C.
18.7%. sulfur and 7.6% nitrogen.
at 3 mm. pressure. A yield of 9.0 grams (‘67% of theory)
When.4.6, grams (0.05. mole) of piperidine is substituted
of 0,0-diethyl‘.S-(4-morpholino)~2-butynyl phosphoro~ "for'the'piperazine and the stripping pressure is 2 mm., a
thiolate wasiob‘tained.
- '
'
‘ ;
yield of 13.3 grams (83% of theory) of 0,0-diethyl
3,080,273
9
10
This latter mixture was heated at re?uxing temperature
for another 4 hour period, after which it was cooled,
?ltered and washed with fresh acetone. The acetone was
then stripped, and the residue was extracted with methyl
S~(4-piperidino)-2 - butynyl phosphorodithioate is ob
tained.
EXAMPLE XXVIII
0,0-Diez‘hyl S- (4-M0rph0lin0 ) -2-Butynyl
ene chloride.
Phosphorodilhioate
The extracts were washed with water and
stripped to 110° C. at 1 min. of pressure to yield 0,0
diethyl O-(4~diethylamino)-2-butynyl phosphorothionate
as an amber liquid.
021150
A suitable reactor was charged with 3.5 grams (0.04
10
mole) of morpholine, 4.1 grams (0.04 mole) of triethyl
amine and 150 ml. of chloroform. There was then add
ed 10.9 grams (0.04 mole) of S-(4-chloro-2-butynyl)
0,0-diethy1 phosphorodithioate, and the mixture was 15
heated at re?uxing temperature for 4 hours. The reac
EXAMPLE XXXH
O,O-Dit'sapr0pyl S-(4-M0rph0lin0) ~2-Butynyl
Phosphorothiolate
(CHQZOHO (I)
/
PSOHzOEOCHzN
\b
(CHalzCHO
A suitable reactor was charged with 2.6 grams (0.03
tion product was washed with water and stripped to 100°
C. A yield of 11.5 grams (89% of theory) of (LC-d1
mole) of morpholine and 3.0 grams (0.03 mole) of tri
ethyl S-(4-rnorpholino) - 2 - butynyl phosphorodithroate
ethylarnine in 75 ml. of benzene, and 8.6 grams (0.03
was obtained.
20
mole) of S-(4-chloro-2-butynyl) 0,0—diisopropyl phos~
EXAMPLE XXIX
phorothiolate. The mixture was heated at re?uxing tem
0,0-Diethyl S-(4-Diethylamino) - 2 - Bzttynyl Phospho
rothiolate, Oxalate Salt
C2H50\?PSGH2CECCH2N(C2H5)T(OOOH)2
perature for 5 hours, and the reaction product was worked
up as in Example II except that the ?nal stripping was to
110° C. at 1 mm. of pressure. There was obtained 8.3
25
grams (84% of theory) of 0,0-diisopropyl S-(4~morpho
vlino)-2-butynyl phosphorothiolate.
(32550
The same procedure was followed with a charge of 3.0
A suitable reactor, protected as in Example XXIV, was
gnams (0.03 mole) of triethylarnine, 3.5 grams (0.03
charged with 2.8 grams (0.0308 mole) of oxalic acid in
80 mole) of 3,5-dimethylmorpholine, 7.7 grams (0.03 mole)
.100 ml. of methanol and 9.0 grams (0.0308 mole) of the
of S-(4-chloro-2-butynyl) 0,0-diethyl phosphorothiolate
product of Example I in 100 ml. of methanol. The mix
and 75 ml. of benzene. With a ?nal stripping to 90° C. at 1
ture was shaken occasionally and allowed to stand over
mm. of pressure, the yield was 6.5 grams of 0,0-diethyl
night. A small precipitate which formed was ?ltered off,
S-[4-(3,S-dirnethylmorpholino)-2 - butynyl] phosphoro
and the solvent was removed from the ?ltrate under
thiolate.
Analysis showed 9.2% phosphorus and 4.4%
vacuum. A 100% yield of 0,0-diethyl S-(4-diethyl 35 nitrogen as compared with calculated values of 9.4%
amino)-2-butynyl phosphorothiolate, oxalate salt, was ob
phosphorus and 4.3% nitrogen.
tained as an amber oil.
EXAMPLE XXBGII
EXAMPLE XXX
0,0-Di(Methoxyethyl) S-(4-Diethylamino) - 2 - Butynyl 40
Phosphorodithioate
CH3O CzHlO
S
CzHu
02135
(CHs)2CHO O
\%s CHzCEC CHzN
CHsO C2H40
O,O-Diis0pr0pyl S-(4-Diethylamino)-2-Butynyl
Phasphorothiolate
PSCHzCEC CHzN
02115
45
(GHS)2CHO
C2115
A suitable reactor was charged with 2.2 grams (0.03
A suitable reactor was charged with 12.3 grams (0.1
mole) of 1,4-dichlorobutyne-2 in 150 ml. of acetone.
There was ‘added 24.6 grams (0.1 mole) of 0,0-di(rneth
mole) of diethylarnine and 3.0 grams (‘0.03 mole) of tri
ethylamine in 100 m1. of benzene, and 8.6 grams (0.03
oxyethyl) phosphorodithioic acid reacted with 10.1 grams
mole) of S-(4-ehloro-2-butynyl) 0,0-diisopropyl phos
(0.1 mole) of triethylamine. The mixture was heated at 50 phorothiolate. Following the procedure of Example
re?uxing temperature for 3 hours after which 14.6 grams
XVIII, a yield of 9.2 grams (96% of theory) of 0,0
(0.2 mole) of diethylamin'e was added with cooling. The
,diisopropyl S~(4-diethyla1nino) - 2 - butynyl phosphoro
resultant mixture was heated at re?uxing temperature
_-tl1iolate was obtained as ‘an amber oil.
for 4 hours. The reaction product was stripped of ace
The speci?c activity of individual compounds disclosed
The residue was extracted with methylene chlo
herein is enumerated below. At the outset it should be
‘ tone.
ride and washed with water. Stripping to ‘130° C. at 1
made clear that such data is merely exemplary, and that
min. of pressure yielded 17.2 grams of 0,0-di(rnethoxy
similar results are obtained by employing any of the
ethyl) S-(4-diethylarnino)-2 - butynyl phosphorodithi
other compounds within the scope of this invention. Sev
eral compounds were tested as systemic pesticides by im
voate.
60 mersing the excised stems of bean plants in diluted emul
EXAMPLE xxxr
_sions of the chemicals for three days. Leaves were then
0,0-Diethyl O-(4-Diethylamin0)-2-Butynyl
excised, infested with the selected insects, and the percent
Phosphorothionate
021150
s
C2115
\ ll
POCHzCECCHaN
ont-no/
CzHs
To a reactor charged with 10.5 grams (0.1 mole) of
4-chloro-2-butyne-1-ol in 100 ml. of acetone, there was
kill was noted after 48 hours.
‘ested against the two
spotted spider mite, emulsions containing 100 p.p.m. of
65 QO-diethyl S-(4~diethylamino) - 2 - butynyl phosphoro~
thiolate killed 100% of the test organisms.
A kill of
100% was also achieved with 100 ppm. concentrations
‘of 0,0-diethyl S-(4-niorpholino)-2-butynyl phosphoro
thiolate, 0,0-diethyl S-(4-dially1arnino)-2-butynyl phos~
added, with cooling and agitation, 18.9 grams (0.1 mole) 70 phorothiolate,
0,0-diethyl S- ( 4-dimethylamino ) ~2-butyny1
of 0,0-diethyl phosphorschloridothioate in 50 ml. of
acetone. This was followed by addition of 20.2 grams
phosphorothiolate, 0,0 - diethyl S - (4 - diallylamino-2~
‘butynyl phosphorodithioate, and 0,0-diethyl S-(4-allyl
(0.2 mole) of triethylarnine, and. the mixture was heated
amino)-2-butynyl phosphorothiolate. Systemic tests
l at re?uxing temperature {for 4 hours. It was then cooled,
>
and 7.3 grams (0.1 mole) of diethylarnine was added. 75 against the bean beetle showed 100% kill at a concentra
12
11'
tion of 0.63 ppm. with 0,0-diethyl S-(4-morpholino)-2
procedures. ' Thus, such a formulation can be further
butynyl phosphorothiolate.
diluted with a solid carrier of the dust type by a simple
mixing operation. Likewise, such a formulation can be
directlysuspended in water or can be further diluted
with an oil which upon mixing with water thereby forms
an oil-in-water emulsion containing the active ingredient.
The insecticidal effectiveness of the new compounds
was also demonstrated in contact tests on the mobile and
resting stages, as Well as on the ova, of the two-spotted
spider mite. Concentrations of .l% resulted in 100%
kill with such compounds as 0,0-diethyl S-(4-diethyl
amino)-2-butynyl phosphorodithioate, 0,0-diethyl S-.(4—
One further example of the utility of such a formulation
comprises the preparation by further dilution with a solid
diethylamino)-2-butynyl phosphoro-thiolate and 0,0-di
carrier of a wettable powder which upon admixture with
10 water prior to application forms a dispersion of the
active ingredient and the solid carrier in water.
Against yellow fever mosquito larvae, concentrations of
ethyl S-(4-dirnethylamino)-2-butynyl phosphorothiolate.
In the preparation of the above-described concentrates,
the active ingredient may comprise up to about 95% of
the concentrated formulation. To obtain 100 parts of a
phorothiolate, 0,0-diethyl S-(4-allylamino) - 2 - butynyl 15 ready to use liquid formulation, from 1 to 50 parts of
10 ppm. of the active ingredient gave 100% kill using
0,0-diethyl S-(4-dimethylamino)-2-butynyl phosphoro
thiolate, 0,0—diethyl S-(4-ethylamino)-2~butynyl phos
phosphorothiolate, 0,0-diethyl S - (4 - diethylamino)-2
a concentrate is admixed with from 50 to 99 parts of a
butynyl phosphorothiolate, and 0,0-diethyl S-(4-diallyl)
diluent or carrier. Although it is not intended that this
invention be limited to any speci?c proportions of active
Z-butynyl phosphorodithioate. The latter three com
pounds gave kills of 80, 90 and 100% respectively against
ingredient and adjuvant, it should be noted that ready to
thesarne insect at concentrations of 2.5 ppm.
2.0 use liquid formulations comprising from about 0.001 to
5% of the active ingredient based upon the weight of the
It will be understood that the terms “insect” and “in
formulation are preferred. Insuch liquid formulations
secticide” are used herein in their broad common usage
it is also preferred that the adjuvant comprise less than
to include spiders, mites, ticks and like pests which are
about 5% based upon the weight of the formulation.
not in the strict biological sense classed as insects. Thus,
the usage herein conforms to the de?nitions provided by .25 With ready to use solid formulations, the parts of con
centrate and diluent or carrier are substantially the same
Congress in Public Law 104, the “Federal Insecticide,
as de?ned for the liquids. However, in such solid formu
Fungicide and Rodenticide Act” of 1947, Section 2, sub
lations, the use of from about 2.5 to 25% of the active
section It, wherein the term “insect” is used to refer not
ingredient based upon the weight of the formulation is
only to those small invertebrate animals belonging mostly
to the class Insecta, comprising six-legged, usually winged 30 preferred. The percentage of adjuvant preferred in the
solids is substantially the same as in the liquid formu
forms, as beetles, bugs, bees, ?ies, and so forth, but also
to their allied classes of arthropods whose members are
Wingless and usually have more than six legs, as spiders,
mites, ticks, centipedes and wood lice.
For maximum effectiveness the active ingredients of
the present invention are admixed in insecticidally effec
tive amount with a insecticidal adjuvant. In order to
provide formulations particularly adapted for ready and
ef?cient application to insects using'conventional equip
ment, such formulations comprise those of both the liquid
and solid types as well as the “aerosol” type formula
tions.
Application may be directly to the insects to
the plant hosts, of such insect to soil or other media
used for growing plants.
In the pure state the active
lations.
It isalso intended that the term “adjuvant” includes
solid carriers of the type of pyrophyllite, talc, clay, dia
tomaceous earth, and the like; and various mineral pow
ders, such as calcium sulfate and the like, which act as a
dispersant, as a carrier, and in some instances perform
the function of a surface-active agent.
Another method of applying these insecticides is in
the form of a Water suspension. However, to obtain an
active aqueous suspension, there should be employed a
surface-active agent in su?icient amount to disperse and
suspend the active ingredient. Examples of such surface
active agents which can be employed in forming disper
ingredients may be too effective or too potent in some 45 sions include the soft or hard sodium or potassium soaps,
applications to have practical utility. For example, for
most effective protection, it is preferred to apply the
materials in intimate contact but thoroughly dispersed
on the surface to be protected. Therefore, the active in
gredients have incorporated therewith a relatively inert
surface-active agent or adjuvant as a dispersing medium.
Furthermore, such adjuvants have the effect of requiring
only minute quantities of said ingredients of some formu
tall oil, salts of the alkyl and alkylaryl sulfonates; alkyl
sulfates; alkylamide sulfonates, including fatty methyl
taurides; the alkylaryl polyether alcohols; the fatty acid
esters of polyhydric alcohols; the ethylene oxide addition
products of such esters; and the addition products of long
chain mercaptans and ethylene oxide. Still other surface
.active agents can be employed, the above merely showing
a representative list of the more common materials.
It should be pointed out that the formulations of this
lations to obtain effective protection. A further advan 55
invention may also include sticking or adhesive agents,
tage of so extending this material is to permit ?eld appli
cation by methods readily employed and still obtain effec
tively complete coverage of the material being protected.
Thus, the formulations of this invention comprise the
indicators and other active biocidal ingredients. Such
other ingredients may be supplementary insecticides,
fungicides, bacteriocides,hnematocides or selective herbi
above de?ned active ingredients and a suitable material 60 cides.
While the invention has been speci?cally described with
as an adjuvant, therefor. The important feature of the
invention is to provide an adjuvant such that upon the
regard to several embodiments, it is not thereby limited,
preparation of a formulation of a concentration appro
and it is to be understood that modi?cations and varia
priate for any particular application the adjuvant will be
tions thereof obvious to those skilled in the art may be
present to provide the proper type of contact with the
made without departing from the spirit or scope of the
material being protected. Thus, in one embodiment the 55 invention.
adjuvant can comprise a surface-active agent such as a
detergent, a soap, or other wetting agent. ‘Such a formu
_lation then comprises the active ingredient in combina
tion with a minor proportion of the surface-active agent 70
or adjuvant. Such a formulation is of practical merit
. because of its concentrated form and ease of transporta
tion, storage, and the like. Such a formulation lends
itself directly to further dilution with a diluent or carrier
What is claimed is:
l. A compound of the formula
R0 x
\N
PsomoEooHlY
R0
where R and R’ are selectedfrom the group consisting of
Without resorting to complicated mixing and blending. 75 “lower ‘allgyl andalkoxy substituted lower alkyl, X is-se
3,080,273:
13
,
,
lower alkyl and alkoxy substituted lower alkyl, X is se
amino.
lected from oxygen and sulfur, and Y is a di-lower acyclic
2. 0,0-diethyl S-(4-diethylamino)-2-butynyl phospho
‘
rothiolate.
amino.
10. A method of protecting plants from insects which
comprises treating the plant with a composition contain
ing, as an essential active ingredient, .a compound of the
formula
' 3. -0,0-diethyl S-'(4-diallylamino)-2,-butynyl phosphoro
thiolate.
'
i
4. 0,0-diethyl S-(4-dimethylamino) - 2 - butynyl phos
phorothiolate.
S. 0,0-diethyl S-(4-diethylamino)¢27butynyl phospho
rodithioate.
14
where R and R’ are selected from the group consisting of
lected from oxygen and sulfur, and Y is a di-lower acyclic
R0
6. 0,0-diethyl S4(4-morpholino)_-2-butynyl phosphoro
'
thiolate.
, ,_
7. A compound of the formula
X
,
\iix'omozoomr
10
.
no
where R and R’ are selected from the group consisting of
- lower alkyl and alkoxy substituted lower alkyl, X and X’
15 are selected from the group consisting of oxygen and
where R and R’ are selected from the group consisting
of lower alkyl and alkoxy substituted lower alkyl, X and
X’ are selected from the group-consisting of oxygen and 20
sulfur, and Y is selected from the group consisting of
sulfur, and Y is selected from the group consisting of
(1) heterocyclics of from 3 to 7 nuclear atoms and of
the formula —NLn where L is a ‘divalent chain of
2 to 6 members, said members consisting of l to 6
(l) heterocyclics of from 3 to 7 nuclear atoms and of
carbon atomsand 0 to 1 nitrogen atom,
(2) morpholino,
(3) quaternary ammonium‘ salt radicals, and
the formula ----NL,n where L is a divalent chain of v I
2 to 6 members, said members consisting of l to 6
25,
carbon atoms and 0 to 1 nitrogen atom,
(2) morpholino,
,
(3) quaternary ammonium salt radicals, and
30
where R" and R'” are selected from the group con
(4)
where R” and R’" are selected from the group con~
sisting of alkyl, alkenyl and alkynyl of l to 8 carbon
atoms, the monochloro derivatives of said alkyl,
alkenyl and alkynyl, alkoxy substituted lower alkyl,
cyano lower alkyl, hydroxy lower alkyl, alkoxycar
bonyl lower alkyl, cycloalkyl of 5 to 7 carbon atoms,
benzyl, phenyl, naphthyl, chlorophenyl, nitrophenyl
sisting of alkyl, alkenyl and alkynyl of 1 to 8 carbon
and alkoxyphenyl.
atoms, the monochloro derivatives of said alkyl, 35
11. A method of protecting plants from insects which
alkenyl and alkynyl, alkoxy substituted lower alkyl,
comprises treating the plant with a composition contain
cyano lower alkyl, hydroxy lower alkyl, alkoxycar
ing, as an essential active ingredient, a compound of the
bonyl lower alkyl, cycloalkyl of 5 to 7 carbon atoms,
formula
benzyl, phenyl, naphthyl, chlorophenyl, nitrophenyl
and alkoxyphenyl.
8. An insecticidal formulation comprising an insecti
cidal adjuvant and, as an essential active ingredient there
of, a compound of the formula
ROX
40
\"
PSCHzCECCHzY
where R and R’ are selected from the group consisting of
lower alkyl and alkoxy substituted lower alkyl, X is se
PX'OHaCEOCHzY
lected from oxygen and sulfur, and Y is a di-lower acyclic
R’O
amino.
12. A method of combatting mites which comprises
where R and R’ are selected from the group consisting of
treating the mites externally and the mite habitats with a
lower alkyl and alkoxy substituted lower alkyl, X and X’
are selected from the group consisting of oxygen and sul 50 composition containing, as an essential active ingredient,
a compound of the formula
fur, and Y is selected from the group consisting of
(1) heterocyclics of from 3 to 7 nuclear atoms and of
the formula —-NLn where L is a divalent chain of
PX'CHzCECCHaY
2 to 6 members, said members consisting of 1 to 6
carbon atoms and O to 1 nitrogen atom,
R’O
55
(2) morpholino,
where R and R’ are selected from the group consisting of
(3) quaternary ammonium salt radicals, and
lower alkyl and alkoxy substituted lower alkyl, X and X’
RI!
are selected from the group consisting of oxygen and sul
fur, and Y is selected from the group consisting of
60
(1) heterocyclics of from 3 to 7 nuclear atoms and of
the formula —NLn where L is a divalent chain of
where R" and R’” are selected from the group con
2 to 6 members, said members consisting of 1 to 6
sisting of alkyl, alkenyl and alkynyl of l to 8 car
carbon atoms and 0 to 1 nitrogen atom,
bon atoms, the monochloro derivatives of said alkyl,
alkenyl and alkynyl, alkoxy substituted lower alkyl,
cyano lower alkyl, hydroxy lower alkyl, alkoxycar 65
(2) morpholino,
(3) quaternary ammonium salt radicals, and
bonyl lower alkyl, cycloalkyl of 5 to 7 carbon atoms,
benzyl, phenyl, naphthyl, chlorophenyl, nitrophenyl
and alkoxphenyl.
9. An insecticidal formulation comprising an insecti
cidal adjuvant and, as an essential active ingredient there 70
of, a compound of the formula
30
v
A
75
(4)
R!!!
where R” and R’” are selected from the group con
sisting of alkyl, alkenyl and alkynyl of 1 to 8 carbon
atoms, the monochloro derivatives of said alkyl,
alkenyl and alkynyl, alkoxy substituted lower alkyl,
cyano lower alkyl, hydroxy lower alkyl, alkoxycar
1%
benzyl, phenyl, naphthyl, chlorophenyl, nitrophenyl
alkenyl and alkynyl, alkoxy substituted lower alkyl,
cyano lower alkyl, hydroxy lower alkyl, alkoxyear
and alkoxyphenyl.
bonyl lower alkyl, cycloalkyl of 5 to 7 carbon atoms,
bonyl lower alkyl, cycloalkyl of 5 to 7 carbon atoms,
benzyl, phenyl, naphthyl, chlorophenyl, nitrophenyl
13. A method of combatting insects which comprises
and alkoxyphenyl.
treating the insectsexternally and the insect habitats with
14. A method of combatting insects which comprises
treating the insects externally and the insects habitats with
a composition containing, as an essential active ingredi
ent, a compound of the formula
’
R0
'
'
a composition containing, as an essential active ingredient,
X
\{I’X'OHKJECCHrY
a compound of the formula
10
ROX
R50
where R and R’ are selected from the group consisting
of lower alkyl and alkoxy substituted lower alkyl, X and
R'O
X’ are selected from the group consisting of oxygen and
15 where R and R’ are selected from the‘ group consisting
sulfuryand Y is selected ‘from the group. consisting of
of lower alkyl and alkoxy substituted lower alkyl, X is
( 1) heterocyclics of from 3 to '7 nuclear atoms and
selected from oxygen and sulfur, and Y is a di-lower
of the formula ——NLn where L is a divalenttchain
acyclic amino.
of 2 to 6 members, said members consisting of 1 to
6 carbon atoms and 0 to 1 nitrogen atom,
(2) morpholino,
20
(3) quaternary ammonium salt radicals, and
25
(4)
References'Cited in the r?leof this patent
UNITED STATES PATENTS
2,648,696
Whetstone _.__,_,____,__.,__._ Aug. 11, 1953
2,706,194
Morris etral .... .._,_..t......_-,_ Apr. 12, 1955
72,841,517
Boon et a1. .__,.__.,_.._, ____ __ July 1,1958
where R" and R'" are selected from the group con
2,865,801
Baker ctal. _______ -_.___.. Dec. 23,1958
sisting of alkyl, alkenyl and alkynyl of 1 to 8 carbon
atoms, the monochloro derivatives of said alkyl,
2,906,661
Baker et al ________ __
2,960,429
Baketctal. .s___,__.r._v..,_._l_;Nov.,l-5, 1,960
,-_S,ept.?29,;l959
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