AU592233B2 - Iminooxazolidine, process of preparation and method of use - Google Patents

Description

*1 AW2 S F Ref: 38645 S F Ref: 38645 FORM COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952 COMPLETE SPECIFICATION

(ORIGINAL)

FOR OFFICE USE: Complete Specification Lodged: Accepted: Published: Priority:

C

SC

c "C C 'r: r CC Related Art: Name and Address of Applicant: Stauffer Chemical Company 2 Nyala Farm Road Westport Connecticut, 06881-0850 UNITED STATES OF AMERICA Spruson Ferguson, Patent Attorneys Level 33 St Martins Tower, 31 Market Street Sydney, New South Wales, 2000, Australia Address for Service: c S c l i i i

C

C C Complete Specification for the invention entitled: Iminooxazolidines, Process of Preparation and Method of Use C e.'The following statement is a best method of performing it full description of this invention, known to me/us including the 5845/6 I In the case of pre-emergent testing (PES) the herbicide was PR-771 9/808 4 IMINOOXAZOLIDINES, PROCESS OF PREPARATION AND METBOD OF UJSE Abstract of the Invention An iminooxazoliidine having the formula Yn

NN

wherein X and Y are the same or different and are selected from the c group consisting of hydrogen, cyano, halogen, acyl, alkyl, alkylthio, t 5 haloalkyl, haloalkylthio, alkylsulfenyl, alkoxy, carboalkoxy-and haloc cc 0 alkoxy wherein the aLkyl groups have from 1 to 5 carbon atoms; least n is the integer 1 or 2; provided that uben Y is hydrogen, at leat oe Xisother than hydrogen; and R hydrogen or is a lower alkyl group having from 1 to 3 carbon atoms, preferably an ethyl group, and herbicidally effective salts C c thereof.

c PR-7719/8084 IMINOOXAZOLIDINES, PROCESS OF PREPARATION AND METHOD OF USE Background of the Invention The present invention relates to certain iminooxazolidine herbicide compounds, compositions, process of preparation and methods of use.

Herbicides have been used for many years by farmers, commercial agricultural companies and other industries in order to eliminate weed pests and thereby increase crop yields .of such staple crops as corn, soybeans, rice and the like.

There are a number of different types of herbicides presently sold commercially, and these fall into two general categories. The categories are pre-emergence and post-emergence herbicides. The pre-emergence herbicides are normally incorporated into or applied to the soil prior to the emergence of the weed plants from the soil, and the post-emergence herbicides are normally applied to plant surfaces after emergence of the weeds or other unwanted plants from the soil. Some herbicides are effective both as pre- and post-emergence herbicides. The iminooxazolidines of this invention fall into that category.

0 Description of the Invention It has now been discovered that certain iminooxazolidines have good herbicidal and plant growth regulating activity, when applied either pre- or post-emergence and used against annual and perennial grasses and broadleaf weeds.

20 -As used herein, the term "herbicide" means a compound or compo- S 'sition which adversely controls or modifies the growth of plants. By the :I term "herbicidally effective amount" is meant any amount of such compound or composition which causes an adverse modifying effect upon the growth of S* plants. By "plants" is meant germinant seeds, emerging seedlings and established vegetation, including roots and above-ground portions. Such controlling or modifying effects include all deviations from natural development, such as killing, retardation, defoliation, desiccation, regulation, stunting, tillering, leaf burn, dwarfing, and the like.

ii 1\ 2 The compounds of this invention are iminooxazolidines having the formula '-Yn xn -N 0

R

wherein X and Y are the same or different and are selected from the group consisting of hydrogen, cyano, halogen, acyl, alkyl, alkylthio, haloalkyl, haloalkylthio, alkylsulfenyl, alkoxy, carboalkoxy and haloalkoxy wherein the alkyl groups have from 1 to 5 carbon atoms; n is the integer 1 or 2; provided that when Y is hydrogen, at least one X is other than hydrogen; and R is hydrogen or a lower alkyl group having from 1 to 3 carbon atoms, preferably an ethyl group, and herbicidally effective salts thereof.

Ii I: i I I II I IC fC II I I I I I I i IE I

SII

IIICIIi I ii c (i i I The compositions of the invention comprise the aforementioned herbicide compounds, along with inert additives, as set forth more fully hereinbelow.

The method of the invention comprises the application to the locus where control is desired either the compound(s) or composition containing the compound(s) described herein.

Representative compounds falling within the scope of the formula 20 as set forth above include: 3-trifluoromethyl)phenyll imino-3-( oxazolidine 2-[N-(3-trifluoromethyl)phenyl limino-3-(3-cyano)phenyl-5-ethyl oxazolidine 2-[N-(4-chloro)phenyllimino-3-(3-cyano)phenyl-5-ethyl oxazolidine 2-[N-(4-chloro)phenyll imino-3-(3-trifluoromethyl phenyl-5-ethyl oxazolidine 2-tN-(4-chloro)phenyl imino-3-(4-chloro)phenyl-5-ethyl oxazolidine 2-[N-(3-trifluoronethyl )phenyl imino-3-(4-chloro)phenyl-5-ethyl-oxazolidine 1 il_

I

3 2-[N-(3,4-dichloro)phenyl] imino-3-( 3-trifluoromethyl)phenyl-5-ethyl oxazolidine 2-[N-(4-fluoro)phenyl]imino-3-(3-trifluoromethyl)phenyl-5-ethyl oxazolidine 4-bromo)phenyl]imino-3-(3-trifluoromethyl phenyl-5-ethyl oxazolidine The compounds set forth above have been found to have especially good herbicidal activity against perennial and annual grasses and broadleaf weed species when applied as post-emergent herbicides. They are also effective as pre-emergence herbicides.

L t r t r cr ttt t

L

t C c t C St t c C Preferred compounds are those wherein X is attached at the 3-position and n is 1, and Y is attached at the 3 or 4-position and n is also 1.

The foregoing, and other compounds, of the general formula set forth above can be prepared in accordance with the process of the invention which comprises: reacting a urea alcohol of the formula /H Yn d^ -N

CH

2

OH

CH

R

wherein l'i

::O

j "~i 3 X and Y are the same or different and are selected from the group consisting of hydrogen, cyano, halogen, acyl, alkyl, alkylthio, haloalkyl, haloalkylthio, alkylsulfenyl, alkoxy, carboalkoxy and halo- 20 alkoxy wherein the alkyl groups have from 1 to 5 carbon atoms; n is the integer 1 or 2; provided that when Y is hydrogen, at least.one X is other than hydrogen; and R is hydrogen or a lower alkyl group having from 1 to 3 carbon atoms, preferably an ethyl group, with a dehydrating agent to form an intermediate salt compound of the formula 1.

i I Yn HX N- Xn

IIP

CH

2

CH

R

wherein X, Y, n and R are as defined above and X' is halogen or other salt forming anion and reacting said salt compound with a base to form a compound of the formula Q n Xn

I

CH

2

CH

R

wherein X, Y, n and R are as previdusly defined.

The reaction sequence of the process of this invention can be represented as follows.

C C C C 9 C t CC C C

CCC

C C C C C C cC C cCac C t C C f rr p

C,

CC C C C C V C C C C tC

C

C C-

R

:4 j ai:; Yn Xn N H-X 0

CH

2 CH bas

I

dehydrating agent Yn

N

XnC C 0 ie iCH 2

-CH

\cR (c) The urea alcohol used as the starting material in the process of the invention can be made by reacting an anilino alcohol of the type described in comnonly assigned Application Serial No. 864,238 filed zf .i -~II Is~- ~maaau; mr 4'r1 -A nnnnn nn. n 4 -a men mfir in May 19, 1986, with an isocyanate, wherein the reaction is conducted at room temperature and for a period of time of about one hour. The anilino alcohol used to produce the starting urea alcohol compound of the process of this invention can in turn "be made by reacting a suitable aniline with an epoxide in a manner such as is also described in Application Serial No.

864,238.

The dehydrating agent used -to dehydrate the urea alcohol starting compound of this invention can be any of the conventionally known dehydrating agents, such as thionyl chloride, phosgene, phosphorus oxychloride, phosphorus pentoxide and the like. Then preferred dehydrating agent for use in the process of the invention is thionyl chloride.

The dehydrating agent is preferably used in excess when used for dehydration of the urea alcohol.

4 44 '~i5 4 44 44 4 444 4 4I~ 44 4 4 .4 4 44 44 1 4'.

44 4 44 44 4 t44 4 44 4'.

4 1~ The base which is used in -the second step of -the process of the invention serves to neutralize the intermediate salt form of the compound produced as a consequence of the dehydrating step.

The base can be any of a number of comtmonly known bases, including pyridine, triethylamine, sodium bicarbonate, sodium hydroxide, potassiLxn hydroxide and the like.

T1he preferred base for use in, the process of the invention is scdium hydroxide, although the choice of base is basically an economic factor.

The process of the invention is preferably carried out at atmospheric pressure, and at ambient temperature, which will vary depending upon the particular starting compounds used. Excessive temperature results in undesirable by-products being formed.

The time of the reaction will also vary according to the starting compounds and tlie temperatures used.

4444 C I (44'.

4411(4 4 4 4 25 4 1 4 4444 44~ 44 4 4 Typical emulsifvina qcwtznf-q nrin r F~ y 6 The intermediate salt compound can be isolated and has also been found to have herbicidal activity. Thus, if desired, the process can be interrupted after the dehydrating step.

The compounds of the invention can also be produced by reacting an anilino alcohol with an isocyanate in the presence of a suitable solvent and thionyl chloride, in accordance with the following sequence of steps, the preparation of 2-[N-(3-chloro-4-methyl) phenyl] imino-3-( 3-trioxazolidine, one of the compounds of the invention being represented.

CF

-NH

OH C1 CH CH 3 CH3 N=C=O

CH

2 CH2 solvent

SOC'

2 Ce t .r r HC1 ~/CH3

CH

2 Cl 1 o c c Vr cLg r t t Ct i" e c6 i t l 10 CF3l 0 \CH3 CH2 .NaHCO ether 0 L_1\ /CH 3 CH2 An intermediate compound produced during the course of the above reaction is the hydrochloride salt of the iminooxazolidine These intermediate salt compounds also have herbicidal activity and fall within the scope of this invention.

i r-ir:: i i-i 7 The examples below illustrate various methods of making the compounds of the invention, using a variety of starting materials. The products were identified by suitable analytical techniques, such as NMR, IR and MS.

EXAMPLE 1 Preparation of (3-Chloro-4-methyl)phenyl]imino-3-(3-trifluoronethyl )phenyloxazolidine A round-bottomed flask was obtained, equipped with an addition funnel and thermometer. Into this flask was combined 4.1 grams (0.018 mole) of 1-(3-trifluoromethyl)anilino-2-butanol, 3.0 g (0.018 mole) of 3-chloro-4-methylphenyl isocyanate in 20 milliliters (ml) of methylene chloride. This mixture was stirred for one hour then stripped of methylene chloride at 40 0 C. The residual was identified as 1-(3-trifluoromethyl)phenyl-1-(2'-hydroxy)butyl, 3-(3-chloro-4-methyl)phenyl urea.

LB t r r C C CCf C 15 11C t C C c C r f r20 t<CC C C C CC C C t" t lsct r C CL C c C t.

Thereafter, 25 ml of methylene chloride and 2.4 g thionyl chloride (0.02 mole) was added to the residual material. An exothermic reaction resulted and the reaction mixture was stirred for 0.5 hour, then allowed to cool. The methylene chloride was again stripped, and the residual material triturated with an ether/pentane mixture, yielding 6.5 g of a white solid material, which was identified by suitable analytical techniques.

Thereafter, 0.42 g of this material (0.001 mole) was combined with 0.1 g of a 50% solution of sodium hydroxide and 10 ml of methyl alcohol. The reaction mixture was then stirred at room temperature overnight, stripped, and subjected to a water work-up.

0.3 grams of the product was obtained, which was identified as such by suitable analytical techniques.

2t y~'r72tS ;CrC~ 21 n nrll 11 ff fin 8 EXAMPLE 2 Preparation of 2-[N-(4-Chloro)phenyl]imino-3-(3-trifluoromethyl)phenyloxazolidine hydrochloride grams of 1-(3-trifluoromethyl)anilino-2-butanol (0.0195 mole) was combined with 3 g of 4-chlorophenyl isocyanate (0.0195 mole) in 15 ml of toluene. The reaction mixture was then stirred and solids began to precipitate after about 1 hour. Thereafter, 10 additional ml of toluene were added and 2.6 g thionyl chloride (0.22 mole). The solids dissolved and the reaction mixture was stirred at room temperature overnight. IR analysis indicated that an HC salt was present, and therefore 25 ml of pentane was added. A dark layer separated, and the mixture was then I stirred at room temperature over the weekend, at which time solids precipitated. The solids were filtered, yielding 5.9 g of material, which I was identified by suitable analytical techniques.

f t t c F e C I te <C C C r t 15 r r I' y EXAMPLE 3 Preparation of 4-Chloro)phenyl imino-3-(3-trifluoromethyl)phenyl- 5-ethyl oxazolidine hydrochloride The same procedure as in the previous example was repeated, except that methylene chloride was used instead of toluene as a solvent.

After the thionyl chloride addition, an exotherm resulted with gas evolution, and the reaction mixture was stirred for one hour at room temperature. It was then stripped, and triturated in ether, yielding 6.8 g of material, which was identified by suitable analytical techniques.

EXAMPLE 4 Preparation of 2-[N-(4-Chloro)phenyl] imino-3- (3-trifluoromethyl )phenyloxazolidine i CCf C Cg (0.01 mole) of 4-chlorophenyl isocyanate was combined with 2.25 g (0.01 mole) of 1-(3-trifluoromethyl)anilino-2-butanol in 10 ml of methylene chloride. The reaction mixture was stirred for 2 hours and at the end of that time, 1.4 g (0.01 mole) of P 2 0 5 was added all in one portion. An exotherm resulted, and the the reaction mixture was stirred for 2 hours, then water, ether, and 100 ml of one molar NAOH was added. The phases were separated, and the aqueous phase was washed with ether, with brine, dried and stripped, yielding 3.1 g of material identified as the product compound by suitable analytical techniques.

9 EXAMPLE Preparation of 2-[N-(4-Fluoro)phenyl] imino-3-(3-trifluoromethyl )phenyloxazolidine 1.4 g (0.01 mole) of 4-fluorophenyl isocyanate was combined with 2.35 g (0.01 mole) of 1-(3-trifluoromethyi)anilino-2-butanol in 10 ml of toluene. The reaction mixture was stirred for 1 hour and at the end of that time, 1.8 g (0.011 mole) of POC1 3 in 5 ml methylene chloride was added all in one portion. The reaction mixture was stirred for 1 hour, then water, ether, and 100 ml of one molar NaOH was added. The phases were separated, and the aqueous phase was washed with ether, with brine, dried and stripped, yielding 3.5 g of material identified as the product compound by suitable analytical techniques.

EXAMPLE 6 Preparation of 2-[N-(4-cyano)phenyl] imino-3-(3-trifluoromethyl)phenyl-5-ethyloxazolidine hydrochloride salt *I10 A round-bottomed flask, fitted with a thermometer and addition funnel was charged with 2.3 g (0.01 mole) of 1-(m-trifluoromethyl)anilino- 2-butanol, 1.45 g (0.01 mole) of (4-cyano)phenyl isocyanate and 20 ml of methylene chloride. The reaction mixture was further processed as in the S previous example, yielding 3.2 g of a white solid material, which was identified as the hydrochloride salt of 2-[N-(4-cyano)phenyl]imino-3-(3- A number of other compounds were prepared in accordance with the same general techniques set forth in the previous examples and are set forth in Table 1 below.

I 1 TABLE I tjYn

N

0

KR

a-npdi. No.

t I~ L t tv C C C C C

CC

C C C CCC ~CC2c,

CC~

e~C C C C C CC CC C C C

CC*CC

C

CC

C C C C C 1~ x 3-CF 3 3-CF 3 3-cyano 3-cyano 4--Cl 3-CF 3 3-CF 3

S

3-CF 3 3-CF 3 3-CF 3 3-CF 3 3-CF 3 3-CF 3 3-CF 3 3-CF 3 3--CF 3 3-CF 3 3--CF 3 3-CF 3 3-CF 3 3-CF 3 3-CF 3 3-CF 3 3-CF 3 3-CF 3 3-CF 3 3-CF 3 3-CF 3 3-CF 3 3--CF 3 y 3-CF 3 4-Cl 4-Cl 3-CF 3 4-Cl 4-Cl 4-F 3, 4-Cl 4-F 4-Br 4-CN 4-CH 3 4-Br 3-Cl, 4-F 4-OCR 3 3-Cl, 4-CH 3 3-Cl 4-CF 3 4-ethoxycarbonyl 3-OF 3 4-F 4-CH 3

S

4-SOCH 3 2-F 3-OF 3 4-Cl 3-SCH 3 2,4-F 3-F 4-COCH3 hydrogen 4-CF 3 0

R

C

2

H

5

C

2

H

5

C

2

H

5

C

2 1t

C

2

H

5 C2H5

C

2

H

5

C

2

H

5

C

2

H

5 C2H5

C

2

H

5

C

2

H

5

H

C2H5

C

2

H

5

C

2

H

5

C

2

H

5

C

2

H

5

C

2

H

5

C

2

H

5

C

2

H

5

C

2

H

5

C

2

H

5

C

2

H

5 C2H 5

C

2

H

5

C

2

H

5 C2H5

C

2

H

5

C

2

H

5 nD 30 or m. P.

0 1.5645 1. 5680 1 .6145 1.5808 1 .6300 79-85 53-56 1.5675 1.5410 1. 5576 189-1 96 1. 5640 1. 61 55-60 amber oil amber oil amber oil amber oil amber oil 95-97 1. 5985 1.5885 1 .5690 64-66 1. 5935 46-49 1.5704 77-82 1. 5803 49-50 ~c irara~-; 11 A series of intermediate salt compounds vere also prepared1, n accordance with the general process as disclosed in Examples 5 and above. These compounds are set forth in Table II below.

TABLE 2 xz n

HU"

XnHC 0 apd. No.

I c

II

Ir I o et c 4* I E'it-

I

I t' ec Cr 4214 1 c 3-CF 3 3-CF 3 3-CF 3 3-CF 3 3-CF 3 3-CF 3 3-CF 3 3-CF 3 3-CF 3 3-CF 3 3-CF 3

S

3-CF 3 3-CF 3 3-CF 3 3-CF 3 3-CF 3 3-CF 3 3-CF 3 3-CF 3

Y

3-Cl, 4-CH3 4-Cl 4-Fl 4-CN 3-Cl, 4-Fl 4-OCR 3 3-Cl 4-CF 3 4-COOCR 2

CR

3 4-SCH3 4-Fl 4-OCH 3 2-Fl 3-CF 3 4-Cl 3-CR 3 2,4-Fl 3-Fl 4-COCH 3 hydrogen

R

C

2 H5

C

2

R

5

C

2 H5

C

2

H

5

C

2

R

5

C

2

R

5

C

2

H

5

C

2

H

5

C

2

R

5

C

2

R

5

C

2

R

5

C

2 H5

C

2 H5

C

2

H

5

C

2

R

5

C

2

H

5

C

2 9 5

C

2

R

5

C

2 1 5 np 30 or m.p. 0

C

109-112 125-127 139-141 120-124 138-140 135-138 118-120 124-127 124-125 128-130 125-127 125-127 124-125 116-119 100-105 ii:. '19 117-119 97-100 139-140 riiI i-: -,9~i .1 0' 12 The herbicidal activity of representative ones of the compounds of the invention are exhibited by means of tests in accordance with the following procedures.

EXAMPLE 7 Herbicidal Activity Tests This example offers additional herbicidal activity test data to show the effectiveness of the compounds of the invention against various wed species. The effect is observed by comparing the extent of weed control in test flats treated with the compounds against that occurring in t1 similar control flats. The soil used in these tests was a sandy loam soil from the Livermore, California area.

Also added to the soil was 17-17-17 fertilizer (N-P 2 0 5 20 on a weight basis), amounting to 50 ppm by weight with respect to the soil and 100 ppn Captan, a soil fungicide.

o The treated soil was then placed in flats which were 3 inches Z deep, 6 inches wide, and 10 inches long. The soil was tamped and leveled with a row marker to impress six rows across the width of the flat. The t test weeds were as follows: COMMON NAME SCIENTIFIC NME ABR S Broadleaf Weeds: A. annual morningglory Iooea purpurea PHBPU B. velvetleaf Abutilon theophrasti ABUTY C. mustard Brassica kaber SINAR D. curly dock Rumex crispus RUMCR c, Grasses: SD. yellow nutsedge Cyperus exculentus CYPES SE. foxtail Setaria p. SETV F. watergrass Echinochloa crusgalli ECHOG .i G. wild oat Avena fatua AVEFA Sufficient seeds were planted to produce several seedlings per inch in each row. The flats were then placed in a greenhouse maintained at 70 to 85°F (21 to 30°C) and watered daily by sprinkler.

-r i rrrr~a~ IIICPI_~-~---lii 13 In the case of pre-emergent testing (PES) the herbicide was applied to the soil after planting of the seeds, at a rate equivalent to the indicated amounts in the Table.

In post-emergent testing (POS) chemical application is made by spraying 12 days after planting. The spray solution is prepared by dissolving 60 mg of herbicide compound in 20 ml of acetone containing 1% Tween® 20 (polyoxysorbitan monolaurate), then adding 20 ml of water to the resulting solution. The solution is sprayed at 80 gallon/acre, resulting in a 4 lb/acre rate of chemical application.

In both instances, either pre- or post-emergent testing, approximately 12-14 days after treatment, the degree of weed control was estimated and recorded as percentage control compared to the growth of the same species in an untreated check flat of the same age. The rating scale ranges from 0 to 100%, where 0 equals no effect with plant growth equal to the untreated control, and 100 equals complete kill.

The results are listed in the Table below.

Ieo r 4r c* ut

SC.

SC CC Cf C C

EC

C' C

-I

,C

7:_ 14 TABLE 3 GREENHOUSE HERBICIDE TEST RESULTS Test Application Compound Rate Percent Injury No. (lb/A) Method SETVI ECHCG AVEFA PHBPU ABUTH SINAR RUCR CYPES 1 4.00 PES 100 75 25 10 25 95 at S' E 4, C t

CC

1 t

C

4; 4;4 4.00 2 4.00 4.00 3 4.00 4.00 4 4.00 4.00 4.00 4.00 6 4.00 4.00 7 4.00 4.00 8 4.00 4.00 9 4.00 4.00 4.00 4.00 11 4.00 4.00 12 4.00 4.00 13 4.00 4.00 14 4.00 4.00 4.00 4.00 16 4.00 4.00

POS

PES

POS

PES

POS

PES

POS

PES

POS

PES

POS

PES

POS

PES

POS

PES

POS

PES

POS

PES

POS

PES

POS

PES

POS

PES

POS

PES

POS

PES

POS

25 100 75 75 10 70 25 0 0 0 0 70 70 100 75 85 70 75 40 80 60 75 30 100 90 100 80 100 70 80 70 90 70 70 100 85 85 50 100 35 35 10 10 80 90 0 20 20 60 0 0 0 50 35 100 40 90 90 100 65 85 50 100 70 75 60 75 20 35 30 N 80 85 20 35 35 50 85 95 100 100 95 100 90 80 60 100 80 80 80 100 90 80 100 100 0 0 100 100 100 100 100

N

N

N

N

N

N

N

N

CC

A 4t 4 L 4 1 4 t

:I-

r TABLE 3 (continued) Test Application Compound Rate Percent Injury No. (ib/A) Method SE

T

VI ECHCG AVEFA PHBPU ABUTH SINAR RUMCR CYPES Ct C I CC 6 C C

C

B;e C CCt I C I t CC C C C CC C t ^C 17 4.00 PES 4.00 POS 18 4.00 PES 4.00 POS 19 4.00 PES 4.00 POS 20 4.00 PES 4.00 POS 21 4.00 PES 4.00 POS 22 4.00 PES 4.00 POS 23 4.00 PES 4.00 POS 24 4.00 PES 4.00 POS 4.00 PES 4.00 POS 26 4.00 PES 4.00 POS 27 4.00 PES 4.00 POS 28 4.00 PES 4.00 POS 29 4.00 PES 4.00 POS 30 4.00 PES 4.00 POS 31 4.00 PES 4.00 POS 32 4.00 PES 4.00 POS 33 4.00 PES 4.00 POS 100 80 100 60 95 10 100 90 100 100 100 90 100 85 100 80 100 80 100 85 100 95 100 30 100 95 100 85 100 20 100 90 100 70 100 80 80 30 95 100 85 85 90 85 85 50 85 50 85 60 100 80 100 90 40 20 100 85 90 60 80 50 100 80 100 60 100 50 20 60 100 90 100 100 90 40 40 80 90 80 100 100 90 80 100 100 40 60 100 80 80 80 80 50 100 60 95 100 80 80 100 100 90 80 80 100 80 80 100 100 95 95 95 100 100 95 100 100 90 90 50 100 80 80 95 100 90 80 90 100 90 90 90 100 80 90 95 100 100 100 50 100 80 80 95 100 90 90 100 100 80 80 60 100 90 90 90 100 80 80 N 0 N 0 N 0 N 0 N 0 N 0 N 0 N 0 N 0 N N 0 N N 0 N 0 N 0 N 0 N 0 N N 0 N 0 N 0 N 0 N 0 N 0 N 0 N 0 N N N N 0 N 0 N 0 N 0 $1 100 100 90 100 100 100 N 0 90 85 90 85 90 80 N 0 16 TABLE 3 (continued) Test Application Compound Rate Percent Injury No. (ib/A) Method SETVI ECHCG AVEFA PHBPU ABUTH SINAR RUMCR CYPES 34 4.00 PES 4.00 POS 4.00 PES 4.00 POS o 36 4.00 PES 4.00 POS f. I 1 C C c C CC r c c e c C E c c r c r r r i C C" I C f

C

C e 37 4.00 PES 4.00 POS 38 4.00 PES 4.00 POS 39 4.00 PES 4.00 POS 40 4.00 PES 4.00 POS 41 4.00 PES 4.00 POS 42 4.00 PES 4.00 POS 43 4.00 PES 4.00 POS 44 4.00 PES 4.00 POS 4.00 PES 4.00 POS 46 4.00 PES 4.00 POS 47 4.00 PES 4.00 POS 48 4.00 PES 4.00 POS 49 4.00 PES 4.00 POS N Not tested.

100 100 80 100 100 100 80 60 80 50 90 100 100 80 95 90 100 95 90 80 0 30 100 100 80 80 85 100 85 80 70 80 90 100 100 80 40 80 100 85 80 70 60 90 100 100 85 90 95 100 50 80 80 50 90 100 50 30 20 20 10 30 5 60 90 100 85 50 85 95 100 N N N N N N 100 90 80 90 90 100 100 80 80 90 100 100 100 50 95 100 100 80 30 70 80 80 100 85 70 50 50 90 50 30 80 80 100 85 70 60 50 100 95 50 30 80 80 100 85 60 100 95 100 80 60 60 100 100 100 100 100 80 90 90 100 95 80 60 60 85 100 100 85 90 90 100 100 80 60 90 85 100 20 20 40 40 100 5 10 5 10 50 100 100 85 100 90 100 100 85 80 100 100

LI

ft I C ft f tI C II I I q tIC I ft I C I 6* ICtI 1 II Cf I Cr C CII

CC

CI

C CIt C IC C C f I CC CCI C C I C C C C CC C C C CC C C C CC ~'C CCC C C I C I 17 METHODS OF APPLICATION The herbicidal compositions of the present invention are useful in controlling the growth of undesirable vegetation by pre-emergence or post-emergence application to the locus where control is desired, including pre-plant and post-plant soil incorporation as wll as surface application. The compositions are generally embodied in formulations suitable for convenient application. TIypical formulations contain additional ingredients or diluent carriers which are either inert or active. Examples of such ingredients or carriers are water, organic solvents, dust carriers, granular carriers, surface active agents, oil and water, wateroil emulsions, wetting agents, dispersing agents, and emulsifying agents.

The herbicidal formulations generally take the fonTi of dusts, emulsifiable concentrates, granules and pellets, or microcapsules.

A. DUSTS Dusts are dense powder compositions which are intended for application in dry form. Dusts are characterized by their free-flowing and rapid settling properties so that they are not readily windborne to areas where their presence is not desired. They contain primarily an active material and a dense, free-flowing, solid carrier.

Their performance is sometimes aided by the inclusion of a ting agent, and convenience in manufacture frequently demands the inclusion of an inert, absorptive grinding aid. For the dust compositions of this invention, the inert carrier may be either of vegetable or mineral origin, the wetting agent is preferably anionic or nonionic, and suitable absorptive grinding aids are of mineral origin.

_Z

Suitable classes of inert solid carriers for use in the dust compositions are those organic or inorganic powders which possess high bulk density and are very free-flowing. They are also characterized by low surface area and poor liquid absorptivity. Suitable grinding aids S are natural clays, diatomaceous earths, and synthetic mineral fillers derived from silica or silicate. Among ionic and nonionic wetting agents, the most suitable are the members of the group known to the art as wetting agents and emulsifiers. Although solid agents are preferred because of 18 ease of incorporation, some liquid nonionic agents are also suitable in the dust formulations.

Preferred dust carriers are micaceous talcs, pyrophyllite, dense kaolin clays, tobacco dust and ground calcium phosphate rock.

Preferred grinding aids are attapulgite clay, diatcitceous silica, synthetic fine silica and synthetic calcium and magnesiLu silicates.

Most preferred wetting agents are alkylbenzene and alkyl-naphthalene sulfonates, sulfated fatty alcohols, amines or acid amides, long chain acid esters of sodium isothionate, esters of sodium sulfosuccinate, c< sulfated or sulfonated fatty acid esters, petroleum sulfonates, sulfonated S~ vegetable oils, and ditertiary acetylenic glycols. Preferred dispersants S are methyl cellulose, polyvinyl alcohol, lignin sulfonates, polymeric alkylnaphthalene sulfonates, sodium naphthalenesulfonate, polymethylene bisnaphthalenesulfonate, and sodium-N-methyl-N-(long chain acid) taurates.

The inert solid carriers in the dusts of this invention are usually present in concentrations of from about 30 to 90 weight percent of the total composition. The grinding aid will usually constitute 5 to e, tr weight percent of the compositions, and the wetting agent will constitute from about 0 to 1.0 weight percent of the composition. Dust compositions 0 can also contain other surfactants such as dispersing agents in concentrations of up to about 0.5 weight percent, and minor amounts of anticaking and antistatic agents. The particle size of the carrier is usually in the range of 30 to 50 microns.

IB. EMULSIFIABLE CONCENTRATES SnEmulsifiable concentrates are usually solutions of the active materials in nonwater-miscible solvents together with an emulsifying agent. Prior to use, the concentrate is diluted with water to form a suspended emulsion of solvent droplets.

Typical solvents for use in emulsifiable concentrates include weed oils, chlorinated hydrocarbons, and nonwater-miscible ethers, esters, and ketones.

19 Typical emulsifying agents are anionic or nonionic surfactants, or mixtures of the two. Examples include long-chain alkyl or mercaptan polyethoxy alcohols, alkylaryl polyethoxy alcohols, sorbitan fatty acid esters, polyoxyethylene ethers with sorbitan fatty acid esters, polyoxyethylene glycol esters with fatty or rosin acids, fatty alkylol amide condensates, calcium and amine salts of fatty alcohol sulfates, oil soluble petroleum sulfonates, or preferably mixtures of these emulsifying agents.

Such emulsifying agents will comprise from about 1 to 10 weight percent of the total composition.

t I QI C C 9;

CC

CC

C C tC 9 C C Ir I Thus, emulsifiable concentrates of the present invention will consist of from about 15 to about 50 weight percent active material, about 40 to 82 weight percent solvent, and about 1 to 10 weight percent emulsifier. Other additives such as spreading agents and stickers can also be included.

C. GRANULES AND PELLETS Granules and pellets are physically stable, particulate compositions containing the active ingredients adhering to or distributed through a basic matrix of a coherent, inert carrier with microscopic dimensions.

A typical particle is about 1 to 2 millimeters in diameter. Surfactants are often present to aid in leaching of the active ingredient from the granule or pellet.

i.

t CC The carrier is preferably of mineral origin, and generally falls c within one of two types. The first are porous, absorptive, preformed granules, such as preformed and screened granular attapulgite or heat expanded, granular, screened vermiculite. On either of these, a solution of the active agent can be sprayed and will be absorbed at concentrations up to 25 weight percent of the total weight. The second, which are also suitable for pellets, are initially powdered kaolin clays, hydrated attapulgite, or bentonite clays in the form of sodium, calcium, or magnesium bentonites. Water-soluble salts, such as sodium salts, may also be present to aid in the disintegration of granules or pellets in the presence of moisture. These ingredients are blended with the active components to give mixtures that are granulated or pelleted, followed by drying, to yield formulations with the active component distributed uniformly i; throughout the mass. Such granules and pellets can also be made with to 30 weight percent active component, but more frequently a concentration of about 10 weight percent is desired for optimum distribution. The granular compositions 'of this invention are most useful in a size range of 1530 mesh.

The surfactant is generally a common wetting agent of anionic or nonionic character. The most suitable wetting agents depend upon the type of granule used. When preformed granules are sprayed with active material in liquid form the most suitable wetting agents are nonionic, liquid t" wetters miscible with the solvent. These are compounds most generally S known in the art as emulsifiers, and comprise alkylaryl polyether alcoh- S ols, alkyl polyether alcohols, polyoxyethylene sorbitan fatty acid esters, polyethylene glycol esters with fatty or rosin acids, fatty alkylol amide r' condensates, oil solution petroleum or vegetable oil sulfonates, or mixtures of these. Such agents will usually comprise up to about 5 weight percent of the total composition.

t When the active ingredient is first mixed with a powdered carrier and subsequently granulated, or pelleted, liquid nonionic wetters can still be used, but it is usually preferable to incorporate at the mixing I t-e stage one of the solid, powdered anionic wetting agents such as those pre- ,t viously listed for the wettable powders. Such agents will comprise from about 0 to 2 weight percent of the total composition.

i t c Thus, the preferred granular or pelleted formulations of this invention comprise about 5 to 30 percent by weight active material, about 0 to 5 weight percent wetting agent, and about 65 to 95 weight percent Sinert material carrier, as these terms are used herein.

O D. MICROCAPSULES Microcapsules consist of fully enclosed droplets or granules containing the active materials, in which the enclosing material is an 3: inert porous membrane, arranged to allow escape of the enclosed materials to the surrounding medium at controlled rates over a specified period.

bcapsulated droplets are typically about 1 to 50 microns in diameter.

i 1 li

L

L t C C~ C ~CC I

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C CCC C CC C C C~ C C~( r~.

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21 The enclosed liquid typically constitutes about 50 to 95% of the weight of the entire capsule, and may contain a small amount of solvent in addition to the active -materials.

Encapsulated granules are characterized by porous membranes sealing the openings of the granule carrier pores, trapping the liquid containing the active components inside for controlled release. A typical granule size ranges from 1 millimeter to 1 centimeter in diameter. In agricultural useage, the granule size is generally about 1 to 2 ml in dia- -meter. Granules formed by extrusion, agglomeration, or prilling are Useful in the present invention as well as -materials in their naturally occurring form. Examples of such carriers are vermiculite, sintered clay granules, kaolin, attapulgite clay, sawdust, and granular carbon.

Useful encapsulating materials include natural and synthetic rubbers, cellulosic materials, styrene-butadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyurethanes, and starch xanthates.

E. IN GENERAL Each of the above formulations can be prepared as a package containing the herbicide together with the other ingredients of the formulation (diluents, emulsifiers, surfactants, etc.). The formulations can also be prepared by a tank mix method, in which the ingredients are obtained separately and combined at the grower site.

In general, any conventional method of application can be used. The locus of application can be soil, seeds, seedlings, or the actual plants, as well as flooded fields. Post-emergent application is preferred. Du.sts and liquid compositions can be applied by the use of powder dusters, boom and hand sprayers, and spray dusters. The compositions can also be applied from airplanes as dusts and sprays because they are effective in very low dosages. In order to -modify or control the growth of germinating seeds or emerging seedlings, as a typical example, the dust and liquid compositions are applied to the soil according to conventional methods and are distributed in the soil to a depth of at least one-half inch below the soil surface. It is not necessary that the phytotoxic compositions be 22 admixed with the soil particles. Instead, these compositions can be applied merely by spraying or sprinkling the surface of the soil. The phytotoxic compositions of this invention can also be applied by addition to irrigation water supplied to the field to be treated. This method of application permits the penetration of the compositions into the soil as the water is absorbed therein. Dust compositions, granular compositions or liquid formulations applied to the surface of the soil can be distributed below the surface of the soil by conventional means such as discing, dragging or mixing operations.

The herbicide compositions can also be applied to the soil through irrigation systems. According to this technique, the compositions Irl Cr are added directly to irrigation water iimediately prior to irrigation of Cc the field. This technique is applicable in all geographical areas regardless of rainfall, since it permits supplementation of the natural rainfall at critical stages of plant growth. In a typical application, the concentration of the herbicide composition in the irrigation water will range from about 10 to 150 parts per million by weight. The irrigation water can be applied by the use of sprinkler systems, surface furrows, or floodinig. Such application is most effectively done before the weeds Z-1 germinate, either early in the spring prior to germination or within two days after cultivation of the field.

The amount of the present composition 4iich constitutes a herbicidally effective amount depends upon the nature of the seeds or plants to be controlled. The rate of application of active ingredient varies from about 0.01 to about 50 pounds per acre, preferably about 0.1 to about pounds per acre with the actual amount depending on the overall cost and the desired results. It will be readily apparent to one skilled in the art that compositions exhibiting lower herbicidal activity will require a higher dosage than more active compounds for the same degree of control.

All

Claims (9)

1. An iminooxazolidine having the formula n xn Y Xn: N "R wherein X and Y are the same or different and are selected from the group consisting of hydrogen, cyano, halogen, acyl, alkyl, alkylthio, haloalkyl, haloalkylthio, alkylsulfenyl, alkoxy, carboalkoxy and halo- S alkoxy wherein the alkyl groups have from 1 to 5 carbon atoms; n is the integer 1 or 2; provided that when Y is hydrogen, at least one X is other than hydrogen; and R is hydrogen or a lower alkyl group having from 1 to 3 carbon atoms, preferably an ethyl group, and herbicidally effective salts thereof.

2. The compound of Claim 1 wherein X is 3-trifluoromethyl, Y is

4-chloro and R is ethyl. 3. The compound of Claim 1 wherein X is 3-trifluoromethyl, Y is 4-fluoro and R is ethyl. 4. A method for controlling undesirable weed pests which comprises applying to the locus where control is desired an herbicidally effective amount of an iminooxazolidine having the formula Xn N -N A,, wherein 24 X and Y are the same or different and are selected from the group consisting of hydrogen, cyano, halogen, acyl, alkyl, alkylthio, haloalkyl, haloalkylthio, alkylsulfenyl, alkoxy, carboalkoxy and halo- alkoxy wherein the alkyl groups have from 1 to 5 carbon atoms; n is the integer 1 or 2; provided that when Y is hydrogen, at least one X is other than hydrogen; and R is hydrogen or a lower alkyl group having from 1 to 3 carbon atoms, preferably an ethyl group, and herbicidally effective salts thereof. i 10 r t r tt t K C" 4-chloro a 4-fluoro a

5. The method of Claim 4 wherein X is 3-trifluoromethyl, Y is nd R is ethyl.

6. The method of Claim 4 wherein X is 3-trifluoromethyl, Y is nd R is ethyl.

7. An herbicidally effective salt of an iminooxazolidine having a I N HX R---R the formul r r:-r r i Y. I i r ii t- wherein X and Y are the same or different and are selected from the group consisting of hydrogen, cyano, halogen, acyl, alkyl alkylthio, halo- alkyl, haloalkylthio, alkylsulfenyl, alkoxy, carboalkoxy and haloalkoxy wherein the alkyl groups have from 1 to 5 carbon atoms; n is the integer 1 or 2; provided that when Y is hydrogen, at least one X is other than hydrogen; and X is halogen or other salt forming anion; and R hydrogen or is a lower alkyl group having from 1 to 3 carbon atoms, and herbicidally effective salts thereof.

8. A process of the preparation of iminooxazolidines which com- prises reacting a urea alcohol of the formula 1 7 0 CH 2 OH CH "R wherein X and Y are the same or different and are selected from the group consisting of hydrogen, cyano, halogen, acyl, alkyl, alkylthio, haloalkyl, haloalkylthio, alkylsulfenyl, alkoxy, carboalkoxy and haloalkoxy wherein the alkyl groups have from 1 to 5 carbon atoms; n is the integer 1 or 2; provided that when Y is hydrogen, at least one X is other than hydrogen; and R is hydrogen or a lower alkyl group having from 1 to 3 carbon Satoms, preferably an ethyl group, with a dehydrating agent to form an intermediate salt compound of the formula; o Yn RX* N- CH 2 CH R wherein X, Y, n and R are as defined above and X° is halogen or other salt forming anion and reacting said salt compound with a base to form a compound of the formula CH 2 CH wherein n, X, Y and R are as previously defined.

9. The process of Claim 8 wherein said dehydrating agent is selected from the group consisting of thionyl chloride, phosgene, phosphorous oxycl{loride and phosphorus pentoxide. r 26 The process of Claim 8 wherein the base is selected from the group consisting of pyridine, triethylamine, sodium bicarbonate, sodium hydroxide and potassium hydroxide.

11. An iminooxazolidine substantially as hereinbefore described with reference to any one of the examples. DATED this SEVENTH day of OCTOBER 1987 Stauffer Chemical Company Patent Attorneys for the Applicant SrE SPRUSON FERGUSON t t rrr t Sr C (Ut t r;