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Description  |
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BACKGROUND OF THE INVENTION
German Offenlegungsschrift F107471Vb/120 describes the preparation of
compounds of Formula A by Equation 1. These compounds are disclosed to be
insecticides.
EQUATION 1
##STR1##
wherein X is H or Cl
Y is --OR, --SR or NR.sub.2 R.sub.3 ; and
R is an alkyl residue.
It has been demonstrated however, by several chemists that procedures like
that described in Equation 1 do not give compounds of Formula A [Frieder
W. Lichtenthaler, Chemical Reviews, 61, 612 (1961); and references cited
therein]. The compounds produced by this type of procedure have been shown
to have the structure described in Formula B.
##STR2##
In U.S. Patent 2,995,486 compounds such as
##STR3##
are taught to be useful as insecticides.
Numerous compounds have been disclosed within recent years which are active
herbicides; the need still exists, however, for herbicides which are more
active. The presence of undesired vegetation is very damaging to useful a
crop such as soybeans. In the current world situation, wherein food
shortages are acute, it is most important not to lose a significant
portion of a valuable crop such as soybeans. The presence of undesired
vegetation results in the loss of a significant portion of such a crop.
Thus, the need exists for a particularly effective herbicide which will
destroy as much of this unwanted vegetation as is possible without causing
significant damage to the desired crop, e.g. soybeans.
According to the instant invention, compounds have been discovered which
are highly active herbicides and yet cause minimal damage to certain
desired crops, e.g., cotton, soybeans and sugarbeets.
DESCRIPTION OF THE INVENTION
This invention relates to the novel compounds of Formula I and to
agricultural compositions containing them, and to the method of use of
these compounds as selective, as well as general, herbicides having both
pre- and post-emergence activity:
##STR4##
wherein X is oxygen or sulfur;
R.sub.1 is alkyl of 1-4 carbons, alkenyloxy of 3-4 carbons, phenyl,
alkylthio of 1-3 carbons, alkoxy of 1-4 carbons, alkoxy of 2-3 carbons
substituted with alkoxy of 1-3 carbons or with 1-3 chlorines or with one
bromine, NR.sub.11 R.sub.12, or phenoxy(optionally substituted with 1-3
chlorines or 1-3 bromines, 1-2 alkyls of 1-4 carbons, or with NO.sub.2);
R.sub.2 is alkyl of 1-6 carbons, alkenyl of 3-4 carbons or cycloalkyl of
C.sub.5 -C.sub.6 optionally substituted with one methyl.
R is alkyl of 1-4 carbons, cycloalkyl of 5-8 carbons, alkylcycloalkyl of
6-8 carbons, cycloalkylalkyl of 6-7 carbons, alkenyl of 3-4 carbons,
arylalkyl of 7-8 carbons, thienyl, naphthyl, biphenyl, or
##STR5##
R.sub.3 is hydrogen, chlorine, bromine, fluorine, nitro, methoxy, alkyl of
1-3 carbons;
R.sub.4 is hydrogen, alkyl of 1-3 carbons, chlorine, bromine, fluorine,
nitro, methoxy, --NR.sub.6 R.sub.7 (where R.sub.6 and R.sub.7 are
independently methyl or ethyl), CO.sub.2 R.sub.8 where R.sub.8 is alkyl of
1-3 carbons,
##STR6##
where R.sub.9 and R.sub.10 are independently hydrogen, methyl, or ethyl;
R.sub.5 is hydrogen, chlorine, bromine, fluorine, nitro, CF.sub.3, CN,
alkyl of 1-3 carbons, alkoxy of 1-3 carbons
##STR7##
provided that: (1) Only one of R.sub.3, R.sub.4, and R.sub.5 can be
NO.sub.2 at the same time;
(2) When R.sub.4 is
##STR8##
then R.sub.3 and R.sub.5 are H, Cl, or Br; (3) When R.sub.5 is other than
H, Cl, Br, or F, then R.sub.3 and R.sub.4 are H, Cl, Br, or F; and
(4) No more than two of R.sub.3, R.sub.4, or R.sub.5 can be alkyl C.sub.1
-C.sub.3, bromine or alkoxy at the same time.
R.sub.11 is, alkyl of 1-4 carbons, cycloalkyl of 5-6 carbons, hydrogen or
##STR9##
V is hydrogen, fluorine, chlorine, or nitro, T is hydrogen, fluorine,
chlorine, bromine, alkyl 1-3 carbons, or trifluoromethyl, and
M is hydrogen, chlorine, alkoxy of 1-3 carbons, or trifluoromethyl provided
that M and T are not simultaneously trifluoromethyl.
R.sub.12 is H, methoxy or alkyl of 1-4 carbons, provided that when R.sub.12
is methoxy R.sub.11 is hydrogen or methyl; and
R.sub.11 and R.sub.12 may also be taken together to form a bridge of the
structure
##STR10##
where n is 4-6 and W is H, methyl or ethyl.
Preferred in order of increasing activity and/or more favorable cost are
independently or in combination:
(1) Compounds of Formula I wherein X is oxygen;
(2) Compounds of Formula I wherein R is C.sub.1 -C.sub.4 alkyl or phenyl,
especially the compounds of 1);
(3) Compounds wherein R.sub.1 is C.sub.1 -C.sub.4 alkoxy or NR.sub.11
R.sub.12 wherein R.sub.11 and R.sub.12 are independently H or C.sub.1
-C.sub.4 alkyl, especially the compounds of (1);
R.sub.11 and R.sub.12 may also be taken together to form a bridge of the
structure
##STR11##
where n is 4-6 and W is H, methyl or ethyl; (4) Compounds of (3) wherein R
is C.sub.1 -C.sub.4 alkyl or phenyl;
(5) Compounds of (4) wherein R.sub.1 is alkoxy C.sub.1 -C.sub.4 ;
(6) Compounds wherein R.sub.2 is C.sub.1 -C.sub.4 alkyl, especially the
compounds of (1), (2), (3), (4), or (5).
Compounds of Formula I specifically preferred for their outstanding
activity and/or very favorable cost are:
1-methylethyl 2,2-dichloro-2-[(1-methylethoxy)phenylphosphinyl]acetate,
m.p. 42.degree.-44.degree. C.
1-methylpropyl 2,2-dichloro-2-[(1-methylethoxy)phenylphosphinyl]acetate.
1-methylethyl 2,2-dichloro-2-[(n-butoxy)phenylphosphinyl]acetate.
1-methylethyl 2,2-dichloro-2-[(1-methylethoxy)methylphosphinyl]acetate.
1-methylethyl 2,2-dichloro-2-[(ethoxy)methylphosphinyl]acetate.
1-methylethyl 2,2-dichloro-2-[(n-propoxy)phenylphosphinyl]acetate.
1-methylethyl 2,2-dichloro-2-[(ethoxy)ethylphosphinyl]acetate.
It is to be understood that all isomers of Formula I resulting from
asymmetry at the phosphorous and/or carbon atoms are included within the
scope of this invention.
METHODS OF PREPARATION
The compounds of Formula I can be prepared, as shown in Equation A, by
chlorination of compounds of Formula II with a metal hypochlorite in
aqueous media at a pH greater than seven, and a temperature between
0.degree. and 75.degree. C. U.S. Pat. No. 3,624,188 teaches a process for
chlorination of phosphonoacetates in a two phase system consisting: (1) of
an aqueous phase containing hypochlorite ion; and (2) an inert
water-immiscible organic solvent phase in which the chlorinated products
formed in the reaction are soluble to the extent of at least five percent
by weight. Examples of such solvents are carbon tetrachloride, chloroform
and sym-tetrachloroethane. It has been discovered that the compounds of
the instant invention may be prepared by chlorination of a compound of
Formula II with aqueous hypochlorite in the absence of a water-immiscible
organic solvent phase. This process is an improvement over the prior art
because it eliminates the need for the expensive and potentially toxic
chlorinated hydrocarbon organic solvent.
EQUATION A
##STR12##
wherein R-R.sub.2, and X are as previously defined.
Compounds of Formula I may also be prepared, as shown in Equation B, by
chlorination of compounds of Formula II with sulfuryl chloride or with
chlorine in the presence of actinic radiation as described in N. D.
Bodnarchuk, V. V. Malovik, and G. I. Derkach J. Gen. Chem. (USSR) 39,
1673-1677 (1968) [CA 71, 12452e (1968)]. These reactions may be carried
out either without solvent or with the addition of an appropriate inert
solvent such as, for example, chloroform, carbon tetrachloride, benzene,
or tetrachloroethane.
EQUATION B
##STR13##
wherein R-R.sub.2, and X are as previously defined.
The compounds of Formula II can be prepared, as shown in Equation C, by
reaction of a phosphite of Formula III with an .alpha.-haloacetate of
Formula IV as described in Organophosphorus Compounds--G. M. Kosolapoff,
John Wiley and Sons, Inc. New York 1950, pp. 121-123. The reaction may be
carried out at temperatures between 50.degree. and 175.degree. C., and
either with or without an added inert organic solvent such as benzene,
toluene, or xylene.
EQUATION C
##STR14##
wherein R-R.sub.2, and X are as previously defined Y is chlorine, bromine,
or iodine; and Z is an alkyl group of one to six carbons.
Compounds of Formula III can be prepared by a suitable modification of the
methods described in Organophosphorus Compounds--G. M. Kosolapoff, John
Wiley and Sons Inc., New York, 1950, pp. 180-210, and Organic Phosphorus
Compounds--Volume 4--G. M. Kosolapoff and L. Maier, John Wiley and Sons,
Inc., 1972, pp. 255-462.
Typical examples of suitable methods for preparing compounds of Formula III
are shown in Equations D, E, and F. The choice of the most suitable method
will depend upon the exact nature of the substituents R.sub.3 -R.sub.5,
and will be obvious to one skilled in the art.
EQUATION D
##STR15##
wherein R.sub.3 -R.sub.5, and Z are as defined above.
EQUATION E
##STR16##
wherein R.sub.3 -R.sub.5, Z and Y are as defined above.
EQUATION F
##STR17##
wherein R.sub.3 -R.sub.5, Z, and Y are as defined above.
Certain compounds of Formula 1 can also be prepared by the method described
in Equation G.
EQUATION G
##STR18##
wherein R, R.sub.2, X, and Z are as described above and B is an alkoxy,
alkylthio, or phenoxy radical; or NR.sub.11 R.sub.12 defined by R.sub.1.
The chlorination reaction depicted in Equation G may be carried out at
temperatures between 25.degree. and 150.degree. C. either with or in the
absence of an added inert organic solvent such as carbontetrachloride,
toluene, or chlorobenzene.
The second reaction in Equation G may be carried out at temperatures
between about -78.degree. and +80.degree. C. in inert organic solvents
such as diethylether, tetrahydrofuran, methylene chloride, or
carbontetrachloride. Suitable bases include trialkyl amines; N,N-dialkyl
anilines, metal alkoxides, and sodium hydride. An excess of trialkyl amine
may also be used in this reaction in place of the inert organic solvent.
The following examples specifically illustrate this invention. Unless
otherwise indicated, all parts are by weight and all temperatures in
.degree.C. Proton NMR data were obtained at 60 MH.sub.Z and ambient
temperature.
EXAMPLE 1
To a solution of 269 g of phenyl dichloro phosphine in 1.5 liters of
tetrahydrofuran at 0.degree.-10.degree., was added a solution of 180 g of
2-propanol and 310 g of triethylamine in 300 ml of tetrahydrofuran. After
stirring for 2 hours at room temperature, the mixture was filtered and the
filtrate concentrated in vacuo. The residue was distilled to give 209 g of
diisopropyl phenylphosphite as a colorless oil bp
62.degree.-63.degree./0.3 mm Hg.
NMR (CDCl.sub.3).delta.: 1.2-1.6 (m, 12.0H); 4.2-4.7 (m, 1.9H); 7.6-8.2 (m,
5.1H).
EXAMPLE 2
To 11.8 g of isopropyl bromoacetate was added 15.0 g of diisopropyl
phenylphosphite at 80.degree.-110.degree., while distilling off isopropyl
bromide. The reaction mixture was heated to 130.degree. over 30 minutes.
Volatile products were removed under 10 mm vacuum at 65.degree.. The yield
of 1-methylethyl 2[(1-methylethoxy)phenylphosphinyl]acetate was 18.8 g as
a colorless oil.
NMR (CDCl.sub.3).delta.: 1.1-1.6 (m, 12.1H); 3.2 (d, J=17 Hz, 1.7H);
4.6-5.4 (m, 1.8H); 7.7-8.5 (m, 5.3H).
EXAMPLE 3
A 5.25% commercial grade sodium hypochlorite solution (185 ml--Clorox.RTM.)
was cooled to 10.degree. and the pH adjusted to 9.0 with 1 N HCl solution.
To this solution, 15.0 g of 1-methylethyl
2[(1-methylethoxy)phenylphosphinyl]acetate was added at
10.degree.-15.degree. with vigorous stirring. The pH was kept between 9.0
and 9.5 by simultaneous addition of 1 N HCl solution (80 ml). The solution
was stirred an additional 15 minutes at 15.degree. then extracted with
methylene chloride. The methylene chloride solution was dried and stripped
to yield 17.0 g of 1-methylethyl
2,2-dichloro-2-[(1-methylethoxy)phenylphosphinyl]acetate as a light yellow
oil.
NMR (CDCl.sub.3).delta.: 1.3-1.7 (m, 12.3H); 5.0-5.6 (m, 1.8H); 7.7-8.6 (m,
4.9H).
Anal. Calc'd. for C.sub.14 H.sub.19 Cl.sub.2 O.sub.4 P: C, 47.61; H, 5.42;
Cl, 20.08.
Found: C, 47.21; H, 5.24, 47.05 4.98.
Cl, 20.44 20.38.
A sample of this oil slowly crystallized upon standing. It was
recrystallized from cyclohexane to give a white solid, m.p.
42.degree.-44.degree..
EXAMPLE 4
A solution of 20.4 g of 2-ethylbromobenzene in 50 ml of diethylether was
added dropwise to 2.7 g of magnesium turnings in a nitrogen atmosphere.
After the addition of the first 2 ml of this solution, 0.5 ml of
1,2-dibromoethane in 5 ml of diethylether was added to initiate the
reaction. After initiation the remainder of the addition was carried out
at 15.degree. over a 1 hour period. After standing an additional 1 hour,
the solution was filtered and added dropwise over 30 minutes to a solution
of 15.6 g of diethyl chlorophosphite in 50 ml of ether at -60.degree..
After standing an additional hour the solution was filtered and the salts
washed with petroleum ether. The filtrate was stripped and the residue
distilled to give 7.0 g of diethyl 2-ethylphenylphosphite, bp
65.degree./1.5 mm Hg.
NMR (CDCl.sub.3).delta.: 1.25 (t, 9H); 2.85 (q, 2H); 3.8 (m, 4H); 7.25-7.65
(m, 4H).
EXAMPLE 5
A solution of 176 ml of a 1.6 M solution of n-butyl lithium in hexane was
added under a nitrogen atmosphere to a solution of 26.2 g of
2-fluorobromobenzene in 300 ml of diethylether at -65.degree.. After
stirring an additional 90 minutes at -65.degree., 28.0 g of diethyl
chlorophosphite was added over a four minute period while holding the
temperature below -48.degree.. The reaction mixture was stirred at room
temperature for 60 hours then refluxed for 30 minutes. The reaction
mixture was then filtered and stripped to give an oil. Distillation
yielded 10.2 g of diethyl 2-fluorophenylphosphite, bp
75.degree.-79.degree./1.3 mm Hg.
NMR (CDCl.sub.3).delta.: 1.3 (t, 6H); 4.1 (m, 4H); 7.6 (m, 4H).
EXAMPLE 6
To 10.14 g of 1-methylethyl
2,2-dichloro-2-[(ethoxy)phenylphosphinyl]acetate at 60.degree. C. and
under a nitrogen atmosphere was added 6.24 g of phosphorus pentachloride
in 1 g portions over a 72 hour period. The mixture was stirred an
additional 48 hours after addition. Volatile reaction products were
distilled at 45.degree.-50.degree. C./0.75 mm Hg leaving 1-methylethyl
2,2-dichloro-2-[(1-chloro)phenylphosphinyl]acetate as a brown oil.
NMR (CDCl.sub.3).delta.: 1.3 (d, J=3.3H.sub.3, 6H); 5.2 (m, 1H); 7.4-8.4
(m, 5H).
EXAMPLE 7
A solution of 11.7 g of diethylamine in 100 ml of diethylether is added
dropwise to a solution of 27.1 g of 1-methylethyl
2,2-dichloro-[(1-chloro)phenylphosphinyl]-acetate in 200 ml of ether at
0.degree.. After stirring at room temperature for 1 hour, the solution is
washed with water and with 10% sodium bicarbonate solution, then dried
over MgSO.sub.4 and stripped to give a dark oil. The reaction product is
dissolved in n-butyl chloride, washed with water, contacted with activated
carbon, dried over MgSO.sub.4 and stripped to give substantially pure
1-methylethyl 2,2-dichloro-[(diethylamino)phenylphosphinyl]acetate.
Using suitable modifications, of the procedures described in the above
examples, the compounds of Formula I shown in Table 1 can be prepared.
TABLE 1
__________________________________________________________________________
##STR19##
R R.sub.1 X R.sub.2 N.sub.D
.nu.>co(cm.sup.-1)
__________________________________________________________________________
##STR20## CH.sub.3 O O
##STR21##
##STR22## (CH.sub.3).sub.2 CHO
O (CH.sub.3 CH.sub.2).sub.2 CH
1.5013(25.degree.)
##STR23## (CH.sub.3).sub.2 CHO
O C.sub.2 H.sub.5
1.5126(27.degree.)
1745
##STR24## (CH.sub.3).sub.2 CHO
O
##STR25##
1.5070(27.degree.)
1745
##STR26##
##STR27## O (CH.sub.3).sub.2 CH
##STR28## n-C.sub.6 H.sub.13 O
O C.sub.2 H.sub.5
##STR29## (CH.sub. 3).sub.2 CHO
O
##STR30##
1.5054(25.degree.)
##STR31## (CH.sub.3).sub.2 CHO
O
##STR32##
1.5121(25.degree.)
##STR33## (CH.sub.3).sub.2 CHO
S (CH.sub.3).sub.2 CH
1.5420(25.degree.)
##STR34## (CH.sub.3).sub.2 CHO
S
##STR35##
1.5382(25.degree.)
##STR36##
##STR37## O
##STR38##
1.5048(25.degree.)
##STR39## CH.sub.3 CH.sub.2 O
O CH.sub.2CHCH.sub.2
1.5315(26.degree.)
1770
##STR40## (CH.sub.3).sub.2 CHO
O
##STR41##
1.5243(25.degree.)
1760
##STR42## nC.sub.4 H.sub.9 O
O (CH.sub.3).sub.2 CH
1.5117(23.5.degree.)
1780
##STR43## n-C.sub.3 H.sub.7 O
O (CH.sub.3).sub.2 CH
1.5121(25.degree.)
1780
##STR44## (CH.sub.3).sub.2 CHO
O CH.sub.3 1.5190(28.degree.)
1770
##STR45## CH.sub.3 O O (CH.sub.3).sub.2 CH
1.5210(26.degree.)
1770
##STR46## CH.sub.3 CH.sub.2 O
O (CH.sub.3).sub.2 CH
1.5178(26.degree.)
1770
##STR47## CH.sub.3 CH.sub.2 O
O CH.sub.3 CH.sub.2
1.5240(26.degree.)
1780
##STR48## (CH.sub.3).sub.2 CHO
O
##STR49##
1.4950(26.degree.)
##STR50## CH.sub.3 S O (CH.sub.3).sub.2 CH
##STR51## (CH.sub.3).sub.2 CHS
O (CH.sub.3).sub.2 CH
##STR52## (CH.sub.3).sub.2 CHS
S (CH.sub.3).sub.2 CH
##STR53##
##STR54## O (CH.sub.3).sub.2 CH
mp 71.degree.-74.degree.
##STR55## CH.sub.3 O
##STR56##
##STR57## (CH.sub.3).sub.2 CHCH.sub.2 O
O
##STR58##
1.5052(25.degree.)
##STR59## (CH.sub.3).sub.3 CO
O (CH.sub.3).sub.2 CH
##STR60## C.sub.2 H.sub.5
O
##STR61##
##STR62##
##STR63## O (CH.sub.3).sub.2 CH
##STR64## CH.sub.3 O(CH.sub.2).sub.3 O
O (CH.sub.3).sub.2 CH
##STR65## ClCH.sub.2 CH.sub.2 O
O (CH.sub.3).sub.2 CH
##STR66## BrCH.sub.2 CH.sub.2 CH.sub.2 O
O
##STR67##
1.5359(25.degree.)
##STR68## Cl.sub.3 CCH.sub.2 O
O
##STR69##
##STR70##
##STR71## O (CH.sub.3).sub.2 CH
##STR72##
##STR73## O (CH.sub.3).sub.2 CH
##STR74##
##STR75## O (CH.sub.3).sub.2 CH
##STR76##
##STR77## O (CH.sub.3).sub.2 CH
##STR78##
##STR79## S (CH.sub.3).sub.2 CH
##STR80##
##STR81## O (CH.sub.3).sub.2 CH
##STR82##
##STR83## O (CH.sub.3).sub.2 CH
##STR84##
##STR85## O (CH.sub.3).sub.2 CH
1.5612(25.degree.)
##STR86## CH.sub.3 ONH O
##STR87##
##STR88##
##STR89## O
##STR90##
##STR91## (CH.sub.3).sub.2 N
O (CH.sub.3).sub.2 CH
##STR92## (nC.sub.4 H.sub.9).sub.2 N
O (CH.sub.3).sub.2 CH
##STR93## (CH.sub.3).sub.2 CHNH
O
##STR94##
##STR95##
##STR96## O (CH.sub.3).sub.2 CH
##STR97##
##STR98## O (CH.sub.3).sub.2 CH
1.5192(25.degree.)
##STR99##
##STR100## O (CH.sub.3).sub.2 CH
##STR101## [(CH.sub.3).sub.2 CH].sub.2 N
O (CH.sub.3).sub.2 CH
##STR102## (C.sub.2 H.sub.5).sub.2 N
O
##STR103##
##STR104##
##STR105## O (CH.sub.3).sub.2 CH
##STR106##
##STR107## O (CH.sub.3).sub.2 CH
##STR108## (CH.sub.3).sub.3 CNH
O (CH.sub.3).sub.2 CH
##STR109## (CH.sub.3).sub.2 N
S (CH.sub.3).sub.2 CH
##STR110## (CH.sub.3).sub.2 N
O
##STR111##
##STR112##
##STR113## O (CH.sub.3).sub.2 CH
##STR114##
##STR115## O (CH.sub.3).sub.2 CH
##STR116##
##STR117## O (CH.sub.3).sub.2 CH
##STR118##
##STR119## O (CH.sub.3).sub.2 CH
##STR120##
##STR121## O (CH.sub.3).sub.2 CH
##STR122##
##STR123## O (CH.sub.3).sub.2 CH
##STR124##
##STR125## O (CH.sub.3).sub.2 CH
##STR126##
##STR127## O (CH.sub.3).sub.2 CH
##STR128##
##STR129## O (CH.sub.3).sub.2 CH
##STR130##
##STR131## O (CH.sub.3).sub.2 CH
##STR132## CH.sub.3 CH.sub.2 O
O CH.sub.3 CH.sub.2
1.5223(27.degree.)
##STR133## CH.sub.3 CH.sub.2 O
O (CH.sub.3).sub.2 CH
1.5250(27.degree.)
##STR134## (CH.sub.3).sub.2 CHO
O (CH.sub.3).sub.2 CH
1.5169(27.degree.)
##STR135## (CH.sub.3).sub.2 CHO
O
##STR136##
1.5164(27.degree.)
##STR137## CH.sub.3 CH.sub.2 O
O (CH.sub.3).sub.2 CH
1.5349(25.degree.)
##STR138## CH.sub.3 CH.sub.2 O
O (CH.sub.3).sub.2 CH
1.5323(25.degree.)
##STR139## CH.sub.3 CH.sub.2 O
O (CH.sub.3).sub.2 CH
1.5442(25.degree.)
##STR140## (CH.sub.3).sub.2 CHO
O (CH.sub.3).sub.2 CH
1.5142(24.degree.)
1750
##STR141## (CH.sub.3).sub.2 CHO
O (CH.sub.3).sub.2 CH
1.5051(23.degree.)
1725
##STR142## (CH.sub.3).sub.2 CHO
O (CH.sub.3).sub.2 CH
1.5028(23.degree.)
1745
##STR143## (CH.sub.3).sub.2 CHO
O (CH.sub.3).sub.2 CH
1.4938(24.degree.)
1750
##STR144## CH.sub.3 CH.sub.2 O
O (CH.sub.3).sub.2 CH
1.5175(27.degree.)
1725
##STR145## (CH.sub.3).sub.2 CHO
O (CH.sub.3).sub.2 CH
##STR146## (CH.sub.3).sub.2 CHO
O (CH.sub.3).sub.2 CH
1.5148(22.degree.)
##STR147## (CH.sub.3).sub.2 CHO
O (CH.sub.3).sub.2 CH
##STR148## (CH.sub.3).sub.2 CHO
O (CH.sub.3).sub.2 CH
##STR149## CH.sub.3 CH.sub.2 O
O (CH.sub.3).sub.2 CH
1.5284(25.degree.)
##STR150## CH.sub.3 CH.sub.2 O
O (CH.sub.3).sub.2 CH
1.5018(25.degree.)
##STR151## CH.sub.3 CH.sub.2 O
O (CH.sub.3).sub.2 CH
1.5037(25.degree.)
##STR152## CH.sub.3 CH.sub.2 O
O (CH.sub.3).sub.2 CH
##STR153## CH.sub.3 CH.sub.2 O
O (CH.sub.3).sub.2 CH
1.5235(25.degree.)
##STR154## CH.sub.3 CH.sub.2 O
O (CH.sub.3).sub.2 CH
1.5238(25.degree.)
##STR155## CH.sub.3 CH.sub.2 O
O (CH.sub.3).sub.2 CH
1.5284(25.degree.)
##STR156## (CH.sub.3).sub.2 CHO
O (CH.sub.3).sub.2 CH
##STR157## (CH.sub.3).sub.2 CHO
O (CH.sub.3).sub.2 CH
##STR158## (CH.sub.3).sub.2 CHO
O (CH.sub.3).sub. 2 CH
##STR159## (CH.sub.3).sub.2 N
O (CH.sub.3).sub.2 CH
##STR160##
##STR161## O (CH.sub.3).sub.2 CH
##STR162## (CH.sub.3).sub.2 N
O (CH.sub.3).sub.2 CH
##STR163## CH.sub.2CHCH.sub.2 O
O (CH.sub.3).sub.2 CH
##STR164## NH.sub.2 O (CH.sub.3).sub.2 CH
##STR165##
##STR166## O (CH.sub.3).sub.2 CH
##STR167##
##STR168## O (CH.sub.3).sub.2 CH
##STR169## (CH.sub.3).sub.2 CHS
O (CH.sub.3).sub.2 CH
##STR170## (CH.sub.3).sub.2 N
S (CH.sub.3).sub.2 CH
##STR171## (CH.sub.3).sub.2 N
O (CH.sub.3).sub.2 CH
##STR172## (CH.sub.3).sub.2 N
O (CH.sub.3).sub.2 CH
CH.sub.3 (CH.sub.3).sub.2 CHO
O (CH.sub.3).sub.2 CH
1.4590(23.degree.)
1750
CH.sub.3 CH.sub.3 CH.sub.2 O
O (CH.sub.3).sub.2 CH
1.4587(22.5)
1770
C.sub.2 H.sub.5
CH.sub.3 CH.sub.2 O
O (CH.sub.3).sub.2 CH
1.4652(26.degree.)
1780
C.sub.2 H.sub.5
(CH.sub.3).sub.2 CHO
O (CH.sub.3).sub.2 CH
1.4612(26.degree.)
1780
(CH.sub.3).sub.3 C
CH.sub.3 O O
##STR173##
1.4757(22.degree.)
C.sub.2 H.sub.5
C.sub.2 H.sub.5
O
##STR174##
1.4585(22.degree.)
C.sub.2 H.sub.5
n-C.sub.4 H.sub.9 O
O
##STR175##
1.4611(22.degree.)
##STR176## C.sub.2 H.sub.5 O
O
##STR177##
1.5200(21.degree.)
CH.sub.3 (CH.sub.3).sub.2 N
O (CH.sub.3).sub.2 CH
##STR178## (CH.sub.3).sub.2 N
O (CH.sub.3).sub.2 CH
##STR179## CH.sub.3 O (CH.sub.3).sub.2 CH
##STR180## (CH.sub.3).sub.2 CHO
O (CH.sub.3).sub.2 CH
##STR181## (CH.sub.3).sub.2 CHO
O (CH.sub.3).sub.2 CH
##STR182## (CH.sub.3).sub.2 N
O (CH.sub.3).sub.2 CH
##STR183## (CH.sub.3).sub.2 CHO
O (CH.sub.3).sub.2 CH
##STR184## (CH.sub.3).sub.2 CHO
O (CH.sub.3).sub.2 CH
##STR185## (CH.sub.3).sub.2 CHO
O (CH.sub.3).sub.2 CH
##STR186## (CH.sub.3).sub.2 N
O (CH.sub.3).sub.2 CH
(CH.sub.3).sub.3 C
(CH.sub.3).sub.2 N
O (CH.sub.3).sub.2 CH
CH.sub.3 CH.sub.3 O (CH.sub.3).sub.2 CH
##STR187## (CH.sub.3).sub.2 CH
O (CH.sub.3).sub.2 CH
##STR188## (CH.sub.3).sub.2 N
O (CH.sub.3).sub.2 CH
(CH.sub.3).sub.3 C
(CH.sub.3).sub.2 CHS
O (CH.sub.3).sub.2 CH
##STR189## (CH.sub.3).sub.2 CHO
O
##STR190##
##STR191## (CH.sub.3).sub.2 CHO
O (C.sub.2 H.sub.5).sub.2 CH
##STR192## (CH.sub.3).sub.2 CHO
O
##STR193##
##STR194## (CH.sub.3).sub.2 CHO
O
##STR195##
##STR196## (CH.sub.3).sub.2 CHOCH.sub.2 CH.sub.2 CH.sub.2 O
O (CH.sub.3).sub.2 CH
##STR197## (CH.sub.3).sub.2 CHOCH.sub.2 CH.sub.2 O
O (CH.sub.3).sub.2 CH
##STR198## C.sub.2 H.sub.5 OCH.sub.2 CH.sub.2 CH.sub.2 O
O (CH.sub.3).sub.2 CH
##STR199## C.sub.2 H.sub.5 OCH.sub.2 CH.sub. 2 O
O (CH.sub.3).sub.2 CH
##STR200## CH.sub.3 OCH.sub.2 CH.sub.2 O
O (CH.sub.3).sub.2 CH
##STR201##
##STR202## O
##STR203##
1.4940(25.degree.)
##STR204##
##STR205## O
##STR206##
1.4941(25.degree.)
##STR207## CH.sub.3 OCH.sub.2 CH.sub.2 CH.sub.2 O
O
##STR208##
1.5059(25.degree.)
CH.sub.3 CH.sub.3 O O
##STR209##
1.4678(25.degree.)
C.sub.2 H.sub.5
CH.sub.3 O O
##STR210##
1.4665(25.degree.)
C.sub.2 H.sub.5
CH.sub.3 OCH.sub.2 CH.sub.2 CH.sub.2 O
O
##STR211##
1.4590(25.degree.)
##STR212## C.sub.2 H.sub.5 O
O (CH.sub.3).sub.2 CH
1.5080 1750
##STR213## (CH.sub.3).sub.2 CHO
O
##STR214##
C.sub.2 H.sub.5
(C.sub.2 H.sub.5).sub.2 N
O (CH.sub.3).sub.2 CH
1.4810
n-C.sub.4 H.sub.9
(C.sub.2 H.sub.5).sub.2 N
O (CH.sub.3).sub.2 CH
1.4717
CH.sub.3 (C.sub.2 H.sub.4).sub.2 N
O (CH.sub.3).sub.2 CH
1.4733
##STR215##
##STR216## O
##STR217##
m.p. 75.degree.-78.degree.
##STR218## C.sub.2 H.sub.5 O
O (CH.sub.3).sub.2 CH
1.5131 1750
##STR219## C.sub.2 H.sub.5 O
O (CH.sub.3).sub.2 CH
1.5181 1750
##STR220## C.sub.2 H.sub.5 O
O (CH.sub.3).sub.2 CH
1.5328
##STR221## C.sub.2 H.sub.5 O
O (CH.sub.3).sub.2 CH
1.5178 1745
##STR222## C.sub.2 H.sub.5 O
O (CH.sub.3).sub.2 CH
##STR223## (CH.sub.3).sub.2 CHO
O
##STR224##
##STR225## (CH.sub.3).sub.2 CHO
O
##STR226##
##STR227## (CH.sub.3).sub.2 CHO
O
##STR228##
__________________________________________________________________________
Useful formulations of the compounds of Formula I can be prepared in
conventional ways. They include dusts, granules, pellets, solutions,
emulsions, emulsifiable concentrates and the like. Many of these may be
applied directly. Sprayable formulations can be extended in suitable media
and used at spray volumes of from a few pints to several hundred gallons
per acre. High strength compositions are primarily used as intermediates
for further formulation. The formulations, broadly, contain about 1% to
99% by weight of active ingredient(s) and at least one of (a) about 0.1%
to 20% surfactant(s) and (b) about 5% to 99% solid or liquid diluent(s).
More specifically, they will contain these ingredients in the following
approximate proportions:
______________________________________
Percent by Weight
Active
Ingredient
Diluent(s)
Surfactant(s)
______________________________________
Emulsions, Solutions
(including Emulsifi-
able Concentrates)
5-50 40-95 0-15
Dusts 1-25 70-99 0-5
Granules and Pellets
1-95 5-99 0-15
High Strength
Compositions 90-99 0-10 0-2
______________________________________
Lower or higher levels of active ingredient can, of course, be present
depending on the intended use and the physical properties of the compound.
Higher ratios of surfactant to active ingredient are sometimes desirable,
and are achieved by incorporation into the formulation or by tank mixing.
Typical solid diluents are described in Watkins, et al., "Handbook of
Insecticide Dust Diluents and Carriers", 2nd. Edn., Dorland Books,
Caldwell, N.Y. The denser diluents are preferred for dusts. Typical liquid
diluents and solvents are described in Marsden, "Solvents Guide", 2nd.
Edn., Interscience, New York, 1950. Solution concentrates are preferably
stable against phase separation at 0.degree. C. "McCutcheon's Detergents
and Emulsifiers Annual", Allured Publ. Corp., Ridgwood, New Jersey, as
well as Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical
Publ. Co., Inc. New York, 1964, list surfactants and recommended uses. All
formulations can contain minor amounts of additives to reduce foam,
caking, corrosion, microbiological growth, etc.
The methods of making such compositions are well known. Solutions are
prepared by simply mixing the ingredients. Granules and pellets may be
made by spraying the active material upon preformed granular carriers or
by agglomeration techniques. See J. E. Browning, "Agglomeration", Chemical
Engineering, Dec. 4, 1967, pp. 147ff. and "Perry's Chemical Engineer's
Handbook", 4th. Edn., McGraw-Hill, N.Y., 1963, pp. 8-59ff.
For further information regarding the art of formulation, see for example:
H. M. Loux, U.S. Pat. No. 3,235,361, Feb. 15, 1966, Col. 6, Line 16 through
Col. 7, Line 19 and Examples 10 through 41.
R. W. Luckenbaugh, U.S. Pat. No. 3,309,192, Mar. 14, 1967, Col. 5 Line 43,
through Col. 7, Line 62 and Ex. 8, 12, 15, 39, 41, 52, 53, 58, 132,
138-140, 162-164, 166, 167, and 169-182.
H. Gysin and E. Knusli, U.S. Pat. No. 2,891,855, June 23, 1959, Col. 3 Line
66 through Col. 5, Line 17 and Examples 1-4.
G. C. Klingman, "Weed Control as a Science", John Wiley & Sons, Inc., New
York, 1961 pp. 81-96.
J. D. Fryer and S. A. Evans, "Weed Control Handbook", 5th Edn. Blackwell
Scientific Publications, Oxford, 1968, pp. 101-103.
EXAMPLE 8
Emulsifiable Concentrate
______________________________________
1-methylethyl 2,2-dichloro-2-
[(n-butoxy)phenylphosphinyl]-
acetate 25%
blend of oil soluble sulfonates and
polyoxyethylene ethers
6%
cumene range aromatic solvent
69%
______________________________________
The ingredients are combined and stirred with gentle warming to speed
solution. A fine screen filter is included in packaging operation to
insure the absence of any extraneous undissolved material in the product.
EXAMPLE 9
Pellets--Granules
______________________________________
1-methylethyl 2,2-dichloro-2-
(1-methylethoxy)phenylphosphinyl
acetate 15%
anhydrous sodium sulfate
10%
crude calcium ligninsulfonate
5%
sodium alkylnaphthalenesulfonate
1%
calcium/magnesium bentonite
69%
______________________________________
The ingredients are blended and moistened with about 12% water. The mixture
is extruded as cylinders about 3 mm diameter which are cut to produce
pellets about 3 mm long. These may be used directly after drying, or the
dried pellets may be crushed to pass a U.S.S. No. 20 sieve (0.84 mm
openings). The granules held on a U.S.S. No. 40 sieve (0.42 mm openings)
may be packaged for use and the fines recycled.
EXAMPLE 10
Emulsifiable Concentrates
______________________________________
1-methylethyl 2,2-dichloro-2-
[(1-methylethoxy)phosphinyl]acetate
36%
blend of oil soluble sulfonates and
polyoxyethylene ethers 8%
2-butoxyethanol 56%
______________________________________
The ingredients are combined and stirred until solution is effected. After
filtration, the liquid may be used directly in LV or ULV applications or
may be emulsified in water before spraying.
EXAMPLE 11
Granules
______________________________________
1-methylethyl 2,2-dichloro-2-
[(ethoxy)ethylphosphinyl]acetate
5%
preformed bentonite granules, 20-50
mesh 95%
______________________________________
The active ingredient is dissolved in isopropanol to make a 20% solution
which is then sprayed on the preformed granules as they are tumbled in a
double cone blender. After drying to remove solvent, the granules are
packaged.
Utility
The compounds of the present invention are useful for the control of
undesired vegetation. They can be used for the selective control of weeds
in crops, such as cotton, soybeans and sugarbeets, or wherever general
weed control is required, such as on industrial sites, railroad
rights-of-way and locations adjacent to croplands.
The precise amount of the compounds of the present invention to be used in
any given situation will vary according to the particular end result
desired, the use involved, the plant and soil involved, the formulation
used, the mode of application, prevailing weather conditions, foliage
density and like factors. Since so many variables play a role, it is not
possible to state a rate of application suitable for all situations.
Broadly speaking, the compounds of the invention are used at levels of
about 0.06 to about 15 kilograms per hectare. The lower rates in this
range will generally be selected for selective weed control in crops, on
lighter soils, soils low in organic matter content, or in situations where
maximum persistance is not necessary. In many situations it is
advantageous to incorporate these chemicals with the soil.
The compounds of the present invention may be combined with any other
herbicide and they are particularly useful in combination with herbicides
of the substituted urea, uracil or s-triazine types for controlling a
broad spectrum of weeds.
The following herbicidal compounds may be used in combination with the
compounds of the instant invention:
5-amino-4-chloro-2-phenyl-3(2H)-pyridazinone (Pyrazon)
2-chloro-4,6-bis(ethylamino)-s-triazine (Simazine)
2-chloro-4-(ethylamino)-6-(isopropylamino)-s-triazine (Atrazine)
2-chloro-4,6-bis(isopropylamino)-s-triazine (Propazine)
2-[[4-chloro-6-(ethylamino)-s-triazin-2-yl]amino]-2-methylproprionitrile
(Cyanazine)
4-amino-6-(1,1-dimethylethyl)-3-(methylthio)-1,2,4-triazin-5(4H)-one
(Metribuzin)
3-(3,4-dichlorophenyl)-1,1-dimethylurea (Diuron)
3-[p-(p-chlorophenoxy)phenyl]-1,1-dimethylurea (Chloroxuron)
1,1-dimethyl-3-(.alpha.,.alpha.,.alpha.-trifluoro-m-tolyl)urea
(Fluormeturon)
3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea (Linuron)
5-bromo-3-sec-butyl-6-methyluracil (Bromacil)
3-cyclohexyl-5,6-trimethyleneuracil (Lenacil)
2-chloro-1-(3-ethoxy-4-nitrophenoxy)-4-trifluoromethylbenzene
3-isopropyl-(1H)-2,1,3-benzothiadiazin-4(3H)-one, 2,2-dioxide (Bentazone)
1,1-dimethyl-4,4'-bipyridium ion (Paraquat)
2,4-dichlorophenoxy acetic acid and salts
5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid, sodium salts
(Blazer.RTM.)
Herbicidal activity of the subject compounds was discovered in a number of
greenhouse tests, as described below.
TEST A
Seeds of crabgrass (Digitaria spp.), barnyardgrass (Echinochloa crusgalli),
wild oats (Avena fatua), cassia (Cassia tora), morningglory (Ipomoea
hederacea), cocklebur (Xanthium spp.), sorghum, corn, soybean, rice, wheat
and nutsedge tubers were planted in a growth medium and treated
preemergence with the chemicals dissolved in a non-phytotoxic solvent. At
the same time, cotton having five leaves (including cotyledonary ones),
bush beans with the third trifoliate leaf expanding, crabgrass with two
leaves, barnyardgrass with two leaves, wild oats with one leaf, cassia
with three leaves (including cotyledonary ones), morningglory with four
leaves (including the cotyledonary ones), cocklebur with four leaves
(including the cotyledonary ones), sorghum with three leaves, corn with
three leaves, soybean with two cotyledonary leaves, rice with two leaves,
wheat with one leaf, and nutsedge with three-five leaves were sprayed.
Treated plants and controls were maintained in a greenhouse for sixteen
days, then all species were compared to controls and visually rated | | |
