Herbicidal composition containin dioxolane, dioxane, or dioxepane derivatives as antidote

IllllllllllllllllllllllllllllllllllllIllllllllllllllllllllllllllllllllllll USOOS] 16402.4

United States Patent [191

[11] [451

Dutka et a1.

[54]

HERBICIDAL COMPOSITION

[75] Inventors: Ferenc Dutka; Tamas Komives; Katalin Fodor, née Csorba; Attila

Manon; Aniké Csikés, née Gliick; Eva Osztheimer, all of Budapest;

Karoly l-lenger; Rébert Laborczy, both of Balaton?izfo; Zsuzsanna Réti, née Bosnyak; De1s6 Sebok, both of Veszprém; Jozsef Szabb'lcs, Balatonalrnadi; Elemér Tiimiirdi, Perernarton, all of Hungary

[73] Assignee: Magyar Tudomanvos Akademia

5,116,402

Date of Patent:

May 26, 1992

OTHER PUBLICATIONS

CONTAINING DIOXOLANE, DIOXANE, OR DIOXEPANE DERIVATIVES AS ANTIDOTE

Patent Number:

Thomson, Agricultural Chemicals, Book II Herbicides, pp. 73-75 (1983-1984 revision). Steinbeck, Karl, “Synthese von 2—Dihalogenmethyl-1, 3-dioxo1ancn und 2-Dihalogenmcthyl-1,3-dioxanen.” Chem. Berichte 112:2402-2412 ('79). Primary Examiner-Richard L. Raymond Assistant Examiner-S. Mark Clardy Attorney, Agent, or Firm-Keil & Weinkauf

[57]

ABSTRACT

The invention relates to a herbicidal composition which

' contains, besides binding, wetting, dispersing, emulsify

ing agents, solvents and/or surface-active substances,"

Kozponti Kemiai Kutato Intezete

herbicides as active agent of thiocarbamate, carbamate,

Nitrokemia Inartelenek

acid amide or urea type alone or in a combination, fur

Fuzfogyartelep, Budapest, Hungary

thermore as antidote a compound of the general for mula I

[211 Appl. No.: 333,737 Mar. 31, 1989 [221 Filed:

R1

[30]

1

\C/

Related U.S. Application Data

[631

on3

Continuation of Ser. No. 885,400, Jul. 18, 1986, aban doned, which is a continuation of Ser. No. 658,462, Oct. 9, 1984, abandoned, which is a continuation of Ser. No. 329,121, Dec. 9, 1981, abandoned.

wherein

R1 and R2, independently of each other, are hydro

gen, C1.6alky1, C2-6alkenyl, Clacyanoalkyl, C1.

Foreign Application Priority Data

éhaloalkyl, phenyl-cM-haloalkyl, phenyl, halogen

Hungary ............................ .. 2967/80

phenyl, CM-alkyl-phenyl, C1_4-alkoxyphenyl, fur

[51]

Int. Cl.5 ................... .. A01N 43/30; A01N 37/02;

R3 and R4, independently of each other, are hydro

[52]

U.S. Cl. ........................................ .. 71/88; 71/100;

[58]

Field of Search ................. .. 71/88, 100, 106, 111,

. 11, 1980 [HU]

A01N 37/18; A01N 47/28

71/106; 71/111; 71/118; 71/119; 71/120 71/118,119, 120

[561

References Cited U.S. PATENT DOCUMENTS 3,344,148 3,427,326

9/1967 2/1969

3,585,749

8/1970 Chamberlin et a1.

3,966,768

6/1976

Pawloski

4,154,595

5/1979

Walker

4,266,964

5/1981

. .. .. ... .. ..

Holmsen et a1.

4,294,764 10/1981

Rinehart ....... ..

4,322,240

3/1982

Teach

4,400,197

8/1983 Rinehart .

4,406,686

9/1983

..... .....

gen, CHg-alkyl, cza-haloalkyl, 'cza-cyanoalkyl,

C1.4-alkoxy-C2_4-alky1, C5.6-cyc1oalky1, phenyl-C1 4-alkyl, C3.4-alkeny1, phenyl-C3-4-alkenyl, di-C1_4 alky1amino¢C;_4-alkyl, hydroxy-Cz.6-a1kyl, furfu

ryl, tetrahydrofuri'uryl, C1.4-alkoxy-C2.4-a1koxy C2.4-alky1; R3 and R4, together, are C14-alky1ene, C4-alkenylene,

glucofuranosylene,

Dietrich ................................ .. 71/88 Dietrich ............ .. 71/88 .. . . . .. .. .. ..

furyl;

549/347 X . . . ..

549/347

. . . ..

71/88

....... .. 71/88 . 260/3409 R . . . . . . . . . , . ..

acetoxy-Cg-alkylene,

gen-Cg-alkylene; wherein the quantity of the anti dote lies between 0.01 and 15 parts by weight re

ferred to 1 part by weight of herbicidal agent, fur thermore the composition contains altogether 0.1 to 95 percent by weight of the herbicidal agents and the antidote.

71/88

71/88

Walker .................................. .. 71/88

C14

alkoxy-cg-alkylene, hydroxy-C3-alkylene, halo

33 Claims, No Drawings

5,116,402

2

' 1

alkyl group can be substituted by a halogen atom, a haloalkyl, alkoxy or alkyl group once or more times.

HERBICIDAL COMPOSITION CONTAINING

According to the invention the herbicidal composi tions contain the compound of the above formula I--

DIOXOLANE, DIOXANE, OR DIOXEPANE DERIVATIVES AS ANTIDOTE

wherein the meanings of R1 to R4 are as de?ned abo

ve——as antidote and herbicidal agent(s); the composition contains 0.01 to 15 parts by weight of the antidote per 1 No. 885,400, ?led on Jul. 18, 1986, which is a continua part by weight of herbicidal agent and consists of 0.1 to tion of Ser. No. 658,462, ?led on Oct. 9, 1984, which is 95 percentbased on the active agents of the composi a continuation of Ser. No. 329,121, ?led Dec. 9, 1981, all 10 tion. The compositions can be used for the detoxication abandoned. of thiocarbamate hefbicides, such as EPTC (S-ethyl The invention relates to herbicidal compositions con N,N-di-n-propyl-thiocarbamate), Butylate (S-ethyl taining aldehyde and ketone derivatives as antidotes as

This application is a continuation of application Ser.

N,N-di-isobutyl-thiocarbamate), Vemolate (S-n-pro pyl-N-,N-di-n-propyl-thiocarbamate), Pebulate (S-n propyl-N-butyl-N-ethyl-thiocarbamate), Molinate (S

well as to the use of these antidotes for the prevention of

damage to cultivated plants caused by herbicidal agents. For the more effective use of the herbicides an in

ethyl-N,N-hexamethy1ene-thiocarbamate),

crease in selectivity is necessary. Numerous herbicidal agents available on the market when used alone or in combination with other herbicidal agents are toxic to very different weeds in concentrations depending on the resistance of the weed. Their economical use, how

Cycloate

(S-ethyl-N-ethyl-N-cyclohexyl-thiocarbamate), Dial late (S-2,3-dichloro-ally-N,N-di-isopropyl-thiocarba mate), further on of carbamates, such as Barban (4

chloro-Z-butinyl-N-/3-chloro-phenyl/-carbamate),

of

amides, such as Acetochlor (2-ethyl-6-methyl-N

ever, is restricted and hindered, respectively, by the fact that when using them in such concentrations the culti vated plant also is damaged. The damage to the culti

ethoxy-methyl-chloro-acetanilide), Alachlor (2,6-dieth

yl-N-methoxy-methyl-chloro-acetanilide), Metolachlor

(6-ethyl-2-methyl-N-/2-methoxy-1-methyl-ethyl/

vated plant and its irregular development can lead to a

chloro-acetanilide) and of carbamide derivatives, such

signi?cant decrease in crop yields. This damaging effect

as

can be moderated, and perhaps eliminated with the help

Linuron

(3-/3,4-dichloro-phenyl/-l-methoxy-l

methyl-urea).

of herbicidal antidotes. Such antidotes and their use are

.

Independently from any concrete effect mechanism disclosed in the Hungarian patents Nos. 165,736, the advantage of the aldehyde and ketone derivatives of 173,775 and 174,487. The chemical character of the 30 the invention resides in the moderating or eliminating of compounds described in these patent applications fun the harmful effect of the herbicides on cultivated plants damentally differs from that of the compounds of the without decreasing the weed control effect. present invention. Further, in contrast to the antidotes The compounds of the above general formula can be described earlier which showed a positive effect only prepared by different methods depending on their char on a rather limited number of herbicide--cultivated acter according to the following examples.

plant combinations-the harmful effect of some herbi cides on cultivated plants can be decreased signi?cantly if the seed of the cultivated plant is treated with an

The synthesis of the compounds of the formula I can be carried out as follows: an oxo compound of the for mula II

antidote of the following formula I before planting/ sowing or if the antidote is added to the soil,

R2

45

wherein

R1 and R2, independently of each other, are hydro~

(11)

wherein R1 and R2 are as de?ned in formula I is admixed with a corresponding mono- or di-alcohol, respectively,

in benzene in stoichiometric ratio and it is re?uxed for several (4 to 11) hours. The formed water is continu ously removed from the system (with a Dean-Stark

gen, C1_6 alkyl, C2_6 alkenyl, C1_4cyanoalkyl, C1_6.

apparatus). As catalyst preferably 4-methyl-benzene

haloalkyl, phenyl-C1_4-haloalkyl, phenyl, halogen phenyl, C1.4-alkylphenyl, C1_4-alkoxyphenyl, fur

sulphonic acid is used for the preparation. The reaction product is separated by ?ltration or distillation depend

furyl;

ing on its character.

R3 and R4, independently of each other, are hydro

gen, C1_1g-alkyl, C2_4-haloalkyl, C2_4-cyanoalkyl,

The compounds of the formula I can also be prepared from compounds of the formula III

C1_4-alkoxy-C2_4-alkyl, C5_6—cycloalkyl, phenyl C1_4-alkyl, C3.4~alkenyl, phenyl-C3_4-alkenyl, di C1_4-alkylamino-C2_4-alkyl, furfuryl, tetrahydrofurfuryl,

R2

(in)

alkoxy-C2_4-a1kyl; R3 and R4, together, are C2_4-alkylene, C4-alkeny

lene, glucofuranosylene, ac'etoxy-Cg-alkylene, C1_4-alkoxy-C3’alkylene, hydroxy-Cg-alkylene, halogen-Cg-alkylene.

wherein R1 and R2 are as de?ned in the formula I, R5

and R6, however, stand for a C14 alkyl group being identical or different, so that any of them is reacted with

Among these substituents the alkyl group can be 65 a corresponding mono- or bivalent alcohol, in the pres ence of a catalyst, e. g. 4-methyl-benzene~sulphonic acid, straight-chain or branched-chain, the haloalkyl can at ‘reflux temperature. The product can be separated contain 1 to 4 ?uorine, chlorine or bromine atoms, the according to the method mentioned before. cyanoalkyl group contains at least a cyano group, the

5,116,402

3

Literature references mention different special and

4

phuric acid are added. It is heated at 60°-70° C. for two hours and after dilution with 60 ml of water it is ex tracted two times with 60 ml of chloroform. The chlo roformic phase is washed with water and sodium hy

general methods of preparing compounds of the general formulas II and III, e.g.:

Houben-Weyl: Methoden der organischen Chemz'e, IV. edition, Gerog Thieme Verlag, Stuttgart, volume V/3 (1962), pages 611-12, 616, 619; volume V/4 (1960), pages 163-170, 173, 175-182; volume Vl/3 (1965), pages 250-2, 256-9, 275-8, 286. Ullmarms Encyklopadie der technischen Chemz'e, Urban and Schwarzenberg, Munchen-Berlin, 3rd edition (1954), volume 5, page 319. D. P. Kaufman: J. Org. Chem. 29, 1956-60 (1964).

drogen carbonate, dried on magnesium sulfate, then the product is vacuum distilled after distilling off the chlo roform.

Boiling point: 98° C./9 Hgmm. EXAMPLE 7

Preparation of trichloro-acetaldehyde di-isoamyl acetal

A mixture of 5 g of chloral-hydrate, 10 g of isoamyl The following examples serve the illustration of the alcohol, 0.1 g of 4-methyl-benzene-sulphonic acid and essence of the invention without limiting the scope of 50 ml of benzene is kept at re?ux temperature and the the invention to these examples. 15 formed water is separated by means of a Dean-Stark EXAMPLE 1

apparatus. After a reaction time of 9 hours the benzene is washed with a sodium-hydrogen-carbonate solution ‘and water, dried on magnesium sulfate, then vacuum distilled.

Preparation of dichloro-acetaldehyde diethyl-acetal Into 95% ethanol kept at 25° chlorine gas is led until two phases are formed. The organic phase is dried on calcium carbonate, then distilled.

nDZO: 1.4519;

Boiling point: 107°-108" C./Hgmm

EXAMPLE 8

EXAMPLE 2

Preparation of trichloro-acetaldehyde dimethyl-acetal

Preparation of 2,3-dibromo-propionaldehyde

5 g of chloral hydrate, 30 ml of absolute methanol and 2.5 ml of concentrated sulphuric acid are kept at re?ux temperature for 10 hours, then the reaction mixture is distilled.

diethyl-acetal 7 g of l,Z-dibromo-propionaldehyde are added to a

mixture of 5 g of ortho-formic acid triethyl-ester and 10 ml of ethanol. The solution is re?uxed for 2 hours, 0 remains standing for a night, then it is vacuum-distilled.

Boiling point: 107° to 108° C./11 Hgmm.

Boiling point: 175°-l76° C. EXAMPLE 9

Preparation of trichloro-acetaldehyde-dibutyl-acetal

EXAMPLE 3

Into an apparatus supplied with a Dean-Stark water

Preparation of trichloro-acetaldehyde diamyl-acetal

separator 7 g of chloral hydrate, 10 g of butyl alcohol, 0.1 g of 4-methyl-benzene-sulph0nic acid and 50 ml of

A mixture of 5 g of chloral-hydrate, 10 ml of amyl alcohol, 0.1 g of 4-methyl-sulphonic acid and 50 ml of benzene is kept at re?ux temperature and the formed

benzene are weighed. The mixture is heated on a water

bath and the water separation is continued for 10 hours. The benzene is washed with water and sodium hydro gen carbonate, then distilled off and the product is vac

water is separated by means of a Dean-Stark apparatus. After a reaction time of 9 hours the benzene is washed with a sodium hydrogen carbonate solution and water, dried on magnesium sulfate, then it is vacuum-distilled.

uum distilled.

Boiling point: 104°~l05° C./3 Hgmm.

r1020: 1.4549.

EXAMPLE 10 EXAMPLE 4

Preparation of dichloro-acetaldehyde dimethyl-acetal

45

Preparation of Z-dichloro-methyl-1,3~dioxane 9 g of dichloro~acetaldehyde diethyl-acetal and 5 g of

propylene glycol are heated on a water-bath in the A mixture of 8 g of dichloro-acetaldehyde diethyl presence of 0.1 g of 4~toluene-sulphonic acid for 4 acetal, 30 ml of methanol and 0.1 g of 4-methyl-ben hours. The product is cleaned by vacuum distillation in zene~sulphonic acid is kept at re?ux temperature for 5 50 the presence of 0.3 g of potassium carbonate. hours, then distilled.

Boiling point: 78°-79° C./l5 Hgmm.

Boiling point: 167°-l68° C.

EXAMPLE 11

EXAMPLE 5

Preparation of

Preparation of trichloro-acetaldehyde diheptyl-acetal

2-(trichloro-methy1)-4-(hydroxymethyl)-dioxolane

A’mixture of 5 g of chloral hydrate, 12 g of heptanol, 0.1 g of 4-methyl-benzene-sulphonic acid and 50 mlof _

benzene is kept at re?ux temperature and the-formed water is separated by means of a Dean-Stark apparatus. Afater a reaction time of 9 hours the benzene is washed with a sodium hydrogen carbonate solution and water, dried on magnesium sulfate, then vacuum distilled. npzo: 1.4573.

vacuo.

Boiling point: 162'-164’ C. EXAMPLE‘IZ '

'

Preparation of

EXAMPLE 6

Preparation of Z-trichloromethyl-1,3-dioxane 21.6 g of chloral hydrate are admixed with 9.6 g of

propylene-glycol, then 16.8 ml of concentrated sul

A mixture of 16 g of chloral, 5 g of glycerine and 5 ml of concentrated sulphuric acid is,heated on a water-bath for 10 hours, then the reaction mixture is distilled in

65

trichloro-acetaldehyde-methyl-butyl-acetal 4 g of butyl alcohol, 0.1 g of 4-methyl-benzene-sul phonic acid and 50 ml of benzene are added to 10 g of 1-methoxy-2,2,2-trichloro-ethanol. The water separa

5

5,116,402

6

tion is continued in a Dean-Stark apparatus for 10 hours while heating the mixture on a water-bath. The benzene is washed with water and the aqueous solution of so

Preparation of dichloro-acetaldehyde didodecyl-acetal

dium hydrogen carbonate, dried on magnesium sulfate, distilled off and the product is cleaned by distillation in

A mixture of 5 g dichloro-acetaldehyde diethyl acetal, 30 g of dodecanol and 0.1 g of 4-methyl-benzene

EXAMPLE 19

vacuo.

sulphonic acid is heated on a water-bath for 5 hours,

Boiling point: 77°—78° C./4 Hgmm.

then distilled.

nDZO: 1.4783.

EXAMPLE 13

Preparation of bromoacetaldehyde diethyl-acetal

10

To a mixture of 10 g of vinyl acetate and 20 ml of

EXAMPLE 20

Preparation of dichloro-acetaldehyde dioctyl-acetal

carbon tetrachloride under cooling (temperature 10° C.) solution are added. 60 ml of ethanol are added to the

A mixture of 5 g of dichloro-acetaldehyde diethyl acetal, 25 g of octanol and 0.1 g of 4-methyl-benzene

mixture and it remains standing for 2 days. The organic phase is washed twice with 50 ml of water, then it is

then distilled.

10 ml of carbon tetrachloride and 18.5 g of bromide

sulphonic acid is heated on a water-bath for 5 hours,

11920: 1.4627.

distilled in vacuo.

Boiling point: 59°—6l° C./l5 Hgmm.

EXAMPLE 21

EXAMPLE 14

Preparation of

Preparation of trichloro-acetaldehyde dihexyl-acetal

2-(dichloro-methyl)-6-(acetoxy-methyl)-dioxolan

A mixture of 5 g of chloral hydrate, 11 g of hexane], A mixture of 5 g of 2-(dichloro-methyl)-4-(hydroxy 0.1 g of 4-methyl-benzene-sulphonic acid and 50 ml of 25 methyl)-dioxolan, 20 ml of acetic acid anhydride and 1 benzene is kept at re?ux temperature and the formed ml of concentrated sulphuric acid is heated on a water water is separated by means of a Dean-Stark apparatus. bath for 1 hour, then distilled in vacuo. After a reaction time of 9 hours the benzene is washed with a sodium hydrogen carbonate solution and water, dried on magnesium sulfate, then distilled in vacuo. 30

Boiling point: l8l°-l83° C./l9 Hgrnm. EXAMPLE 22

nDZO: 1.4562.

Preparation of

Z-(dichloro-methyl)-4-(hydroxy-methyl)-dioxolan

EXAMPLE 15

To a mixture of 5.5 g of 2-(trichloro-methyl)-4-(hy droxy-methyD-dioxolan and 30 ml of acetic acid under A mixture of 8 g of bromo-acetaldehyde diethyl 35 stirring 1.6 g of zinc dust are added within 30 minutes. acetal, 3 g of sodium-cyanide and 20 ml of dimethyl-sul After a further 15 minutes of stirring the reaction mix foxide is admixed at a temperature of 80° C. for 5 hours.

Preparation of cyan-acetaldehyde diethyl-acetal

ture is distilled. The reaction mixture is poured on 80 ml of water, then Boiling point: twice extracted with 50 ml of chloroform. The chloro 40 form extract is washed twice with 30 ml of water, dried on magnesium sulfate, then distilled in vacuo.

Boiling point: 97°-98° C./l0 Hgmm.

A mixture of 5 g of dichloro-acetaldehyde diethyl acetal, 30 ml of propanol and 0.1 g of 4-methyl-benzene sulphonic acid is heated on a water-bath for 5 hours, then distilled.

'

Boiling point: 2l0°-211° C.

EXAMPLE 23

Preparation of

2-(trichloro-methyl)-4-(methoxy-methyl)-dioxolan

EXAMPLE 16

Preparation of dichloro-acetaldehyde dipropyl-acetal

156‘-l57° C./l9 Hgmm.

45

A mixture of 5.5 gof Z-(trichloro-methyl)-4-hydroxy methyl)-dioxolan, 3 g of dimethyl-sulfate, 3 g of potas sium carbonate and 30 ml of water is admixed at room.

temperature for 4 hours. The mixture is extracted twice with 30 ml of chloroform, the extract is washed with 50 50 ml of water, then distilled.

Boiling point: l53°-l55° C./l8 Hgmm.

EXAMPLE 17

EXAMPLE 24

Preparation of trichloro-acetaldehyde diethyl-acetal

Preparation of dichloro-acet'aldehyde ethyl-hemi-acetal

5 g of chloral-hydrate, 40 ml of absolute ethanol and 55 A mixture of 6.1 g of dichloro-acetaldehyde, 2.3 g of 2.5 ml of concentrated sulphuric acid are kept on re?ux ethanol and 15 ml of benzene is left standing for a night, temperature for 10 hours, whereupon the reaction mix then distilled. ture is distilled.

Boiling point: l90°~l92° C.

Boiling point: l09°-ll0° C.

EXAMPLE 25

EXAMPLE 18 1

Preparation of 2-dichloromethyl-1,3-dioxolane

Preparation of 2,2,2-trichloro- l -(ethoxy-ethoxy)-ethanol

10 g of dichloroacetaldehyde diethyl-acetal and 3 g of A mixture of 7 g of chloral, 4.8 g of ethylene-glycol ethylene-glycol are heated in the presence of 0.1 g of 65 monoethyl-ether and 15 ml of benzene is left standing 4-methyl-benzene-sulphonic acid on a water-bath for 5 for a night at room temperature, then distilled. hours, whereupon the product is distilled in vacuo.

Boiling point: 187° C.

npzoz 1.4697.

5,116,402

7

8 EXAMPLE 32

EXAMPLE 26

Preparation of 2,2,2-trichloro-l-allyloxy-ethanol

A mixture of 4.5 g of l,l-dichloro-acetone, 3.7 ml of

ethylene glycol, 0.1 g of 4-methyl-benzene-sulphonic

A mixture of 7 g of chloral, 2.9 of allyl-alcohol and 15 5 acid and 30 ml of benzene is kept at re?ux temperature ml of benzene is left standing for a night at room tem for 9 hours while continuous water separation. The perature, then distilled. reaction mixture is washed with a sodium hydrogen n02‘): 1.4820. carbonate solution, dried on magnesium sulfate and distilled. EXAMPLE 27

Preparation of chloro-acetaldehyde dimethyl-acetal

10

EXAMPLE 33

To a mixture of 5 g of vinyl acetate and 20 ml of methanol acetone cooled on dry ice 5 g of dry chlorine gas are added, then it is left standing for a night at room

Preparation of 2-chloromethyl-dioxan A mixture of 4.7 g of chloro-acetaldehyde diethyl acetal, 9 g of propylene glycol and 0.05 g of 4-methyl

temperature. The reaction mixture is then poured onto 50 g of ice-water. The product is extracted with 30 ml of chloroform, the extract is washed with sodium hydro

benzene-sulphonic acid is heated for 9 hours on a water bath, then distilled in vacuo.

Boiling point: 71°—74° C./l4 Hgmrn.

gen carbonate solution and water, then dried on magne

sium sulfate and distilled. 20

Boiling point: 53°—54° C./l6 Hgmm.

Boiling point: 92°—94° C./27 Hgmm.

EXAMPLE 34

Preparation of

EXAMPLE 28

Z-(dichloro-methyl)-2-phenyl-1,3-dioxolan

Preparation of chloro-acetaldehyde diethyl-acetal

A mixture of 6 g of l,l-dichloro-acetophenon, 3.8 ml To a mixture of 5 g of vinyl acetate and 27 ml of 25 of ethylene glycol, 0.1 g of 4-methyl-benzene-sulphonic acid and 40 ml of benzene is kept at re?ux temperature ethanol acetone cooled on dry ice 5 g of dry chlorine for 11 hours and the formed water is continously sepa gas are added, then it is left standing for a night at room rated by means of a Dean-Stark apparatus. The reaction temperature. The reaction is poured onto 50 g of ice mixture is washed with a sodium carbonate solution, water. The product is extracted with 30 ml of chloro dried on magnesium sulfate and evaporated. The form, the extract is washed with a sodium hydrogen formed solid material is recrystallized from hexane. carbonate solution and water, then dried on magnesium sulfate and distilled.

Melting point: 59°-60" C.

‘

Boiling point: 53°-54° C./ 16 I-Igmm.

EXAMPLE 35

EXAMPLE 29

35

Preparation of a-chloralose A mixture of 4.5 g of glucose, 19 g of chloral, 20 ml of chloroform and 0.05 g of 4_methyl-benzene-sul phonic acid is kept at re?ux temperature for 7 hours and the formed water is separated by means of a Dean-Stark apparatus. The solvent is distilled off and the residue is

Preparation of 2-(bromo-methyl)-dioxolan 4.3 of bromo-acetaldehyde diethyl-acetal are heated in the presence of 10 g of ethylene glycol and 0.05 g of 4-methyl-benzene-sulphonic acid for 8 hours on a wa

ter-bath, whereupon the reaction mixture is distilled.

Boiling point: l73°-l74° C.

EXAMPLE 36 kept at 60° C. for 20 minutes. The sedimented material Preparation of bromo-acetaldehyd is ?ltrated and the pH value of the mother lye adjusted to 6.5 with sodium hydroxide. The separated precipitate 45 Into 80 ml of carbon tetrachloride solution of 43 g of vinyl acetate cooled with ice 60 ml of carbon tetrachlo~ is ?ltered. ride solution of 80 g of bromide are dropped so that the Melting point: l82°—l83° C. reaction mixture temperature does not rise above + 10° EXAMPLE 30 C. Then the reaction mixture is dropped to 3.8 mol of Preparation of B-chloralose 50 allyl alcohol cooled with salty ice at a temperature under + 10° C. After two-day standing the carbon tetra Under stirring 0.05 g of 4-methyl-benzene sulphonic chloride phase is washed with water, dried on anhy acid and 20 ml of chloroform are added to a mixture of drous sodium sulfate and after the evaporation of the 4.5 g of glucose and 19 g of choral. The mixture is solvent the obtained residue is distilled fractionally. heated to re?ux temperature and the formed water is Boiling point: 80”—82° C./l Hgmm, yield: 72.1% separated by means of a Dean-Stark apparatus. The 55 EXAMPLE 37 solvent is distilled off, then the mixture is kept at a temperature of 60° C. for 20 minutes. The separated Preparation of Z-dichloromethyl-Z-methyl-1,3-dioxolan material is ?ltered off.

'

Melting point: 231°—232° C. EXAMPLE 31

Preparation of Z-(dibromo-me'thyl)—dioxolan A mixture of 5.3 g of dibromo-acetaldehyde diethyl acetal, 7 g of ethylene glycol and 0.05 g of 4-methyl~ 65 benzene sulphonic acid is heated on a water-bath for 7 hours, then distilled in vacuo.

Boiling point: l02°-103° C./9 Hgmm.

8.0 g of 1,1-dichloroacetone are reacted with 6.7 ml

of ethylene~glycol in the presence of p-toluene-sul phonic acid catalyst in a water-separating system or by means of a water binding molecule-screen /A 4/, ?nally it is distilled/on a Vigreux column/.

Boiling point: 93°—94° C./2 Hgmm. Preparation of l,l-dichloroacetone used as starting material: To 14.5 g of acetone weighed into a round-bottom ?ask provided with a re?ux condenser linked with

5,1 16,402

11

12

TABLE I-continued 53

H

—CHCl2 Z-ethoxy-ethyl

2-ethOxy-ethyl

nD 1.4752

56 57

H H

—C1-1Cl2 3-methyl-n-butyl -CHCI2 cyclohexyl

B-methyl-n-butyl cyclohexyl

62° C./1 120' C./l

59

-CHCl1

H

cinnamyl

n D 1.6492

61 62

-CHC12 H

H diethylamino-ethyl -Cl-1Cl2 l-methyl-n-butyl

diethylamino-ethyl l-methyl-n-butyl

1.51 12 58' C./1

64

H

~—CHCl2 Z-cyano-ethyl

2-cyano-ethyl

n1) 1.4749

67

H

-CCl3

-CH;—CH2-

198-200’ C./740

68

--CHC12

H

_.CHZ_CH..

156-7‘ C./l9

'

cinnamyl

CHZOH 70 71 72 73 74

—CCl3 -CCl3 —CCl3 -'CHzBr —CCl3

H H H H H

heptyl

76 77

-CCl3 -—CCl3

H H

amyl

78

—CCl_;

H

methyl

butyl ethyl allyl

heptyl a-D-glycofuranosylene butyl methoxy-ethyl H

nD 1.4573 m.p.: 182-83‘ C. 104-5‘ C./3 llO-15° C./12 116° C.

amyl a-D-glycofuranosylene

n D 1.4549 m.p. 231-2’ C.

butyl

77-78‘ 0/4

81

"CCl3

H

hexyl

hexyl

nD 1.4562

82

-CH2Cl

H

methyl 5

methyl

53-54° C./16

83

—CHCl3

H

85 86 87

-CCl3 -CHZBr '-CCl3

H H H

_CHZ_CH_

methyl isopropyl i-amyl

181-83° C./l9

methyl isopropyl i-amyl

175-6’ C. 53-55’ C./3 nD 1.4519

The antidotes according to the invention and the 50 herbicidal agent, however, is brought before or after the sowing of the seed-corns onto the soil. Any of the antidotes according to the invention can prepared and used for practical purposes in any usual be used in connection with such herbicidal agents form. Thus emulsi?able liquids, emulsi?able concen which contain the herbicidal thiocarbamates, carba trates, wettable powders or granular preparation can be

compositions containing them, respectively, can be

prepared. As active agent it is suitable to use thiocarbamate

herbicides. The product containing the’agent, the anti dote and the carrier can be brought into the soil before or after the sowing of the seed-corns or the seeds to be sown can be treated with the product, .too. Another method is to form a product suitable for the treatment of

55 mates, acid amides or urea derivatives alone or in any

combination. The herbicidal activity can change in the case of the individual herbicidal agents and combina tions, respectively, and can depend to a certain degree on.those kinds of plants, too, on which the correspond ing herbicidal compound is used alone or in a combina

the soil or the seeds and the plants, respectively, with a

tion. With the use of any of the‘ antidotes according to the invention in every such case protection can be

corresponding liquid or solid carrier from partly the

reached against the activity of the chosen herbicidal

herbicidal agent, partly the protective agent according

agent or agent combination which would lead to a dam

to the invention separately and they are brought into 65 age of the cultivated plant. The effect of the products according to the invention the soil successively or 'on the seeds, plants to be were examined with seed treating and soil treating treated. That method can also be applied that the anti methods as follows. In the case of both methods 6 culti dote of the invention is brought onto the seeds, the

5,116,402

13

14

corresponding quantities of the stock solution of the herbicide(s) adjusted correspondingly and of the suit ably adjusted stock solution of any antidotes of the

vated plans and 15 weed-seeds each were planted into soil ?lled into 10X 10X 10 cm plastic vessels and pre pared depending on the mentioned two types of treat ment and the activity of the antidotes was examined in relation to several herbicides and cultivated and weed

invention which were to be examined were added to the

soil placed into the mixer. Into the thus-prepared soil ?lled into the experimen tal vessels the seeds of the examined herbaceous and latifoliate cultivated plants were put 2.5 cm deep. in order to ensure the favourable growth of the plants they

plants, respectively, while the humidity, light and tem perature were regulated.

Seed Treatment Examinations 10 g of seed-com are shaken with 50 mg of the anti dote according to the invention in a well-closing cut vessel until the substance coats the corns uniformly.

were watered correspondingly. The results are included in Table III.

TABLE III

The coating of the compounds onto the seeds can be furthered-if necessary-by adding acetone. The thus pretreated seeds are put into the soil placed in the above experimental vessels to which previously the herbicidal

Percental protection effect of antidotes against the damage of cultivated plants caused by herbicides Antidots

' agent was added uniformly so that in a suitable mixer a

Number

determined quantity of the herbicidal agent(s) was added to the soil from a suitably adjusted stock solution

of the herbicide(s).

20

The seeds were put 2.5 cm deep into the prepared soil and the vessels were watered in order to ensure the

positive plant growth correspondingly. The results are summarized in Table 11. 25

TABLE II Damage of maize caused by herbicides (7c) in the case of seeds treated with the antidote at 0.5% (A) and of untreated seeds (B)

Number of the compound

Butylaie Pebulate EPTC

15 29

26 47 65 7 23 50 36 2 55 11 64 43 3

Culti

Name

Quantity (kg/ha)

vated plant

Protection effect (%)

12

1.3

EPTC

6.3

Maize

82

25 33 45 58

3.6 0.4 2.1 0.35

EPTC EPTC EPTC EPTC

6.3 6.3 6.3 6.3

Maize Maize Maize Maize

24 5 39 48 63

1.3 1.1 1.6 1.1 0.9

EPTC EPTC EPTC EPTC EPTC

6.3 6.3 6.3 6.3 6.3

Maize Maize Maize Maize Maize

19 100 12 85 99 82 3O 78 100

6

0.7

Trlallaiex

3.0

Grain

s9

broom

Damage of the plants Used herbicide Name Quantity kg/ha

20 8 27

57 61 59 37 53 42 52

Herbicide

Quantity (kg/ha)

com

after 3 weeks (7:) A . B

8.1 5.7 6.6

5 5 8

48 47 42

EPTC EPTC

6.6 6.6

13 18

52 52

Barban EPTC EPTC EPTC Molinate EPTC EPTC

0.7 6.6 6.6 6.6 5.3 6.6 6.6

0 43 3 12 0 0 2

41 47 54 43 52 38 41

Vernolate EPTC EPTC EPTC Diallate Alachlor Cycloate EPTC EPTC Linuron EPTC EPTC EPTC

2.8 6.6 6.6 6.6 5.7 4.5 6.3 6.6 6.6 2.2 6.6 6.6 6.6

10 5 38 0 13 17 28 0 8 30 1 0 3

61 47 47 41 48 51

53 38 62 54 57 43 60

76

Pcbulate

5.7

17

56 '

70

EPTC

6.6

12

49

87 88 81 68 86 74

Butylate Mclinate Vernolate EPTC EPTC EPTC

8.1 5.3 2.8 6.6 6.6 6.6

16 13 21 3 18 17

61 53 62 50 39 46

71

EPTC

6.6

9

- 37

77 69 89

EPTC EPTC EPTC

6.6 6.6 6.6

12 8 0

46 37 59

*Benthiocarb: S-(4-chlorobenzyl)—N.N-diethyl-thiocarbamide EPTC = S~ethyl-N,N-di-n-propyl-thiocarbamate

35

45

50

55

22 62 14 45 1 18 72 60 30 46 17 4 19 32 16 49 83 34 9 28 66 56 10 73 54 82 41 84 13 44 85 75 51 31 35 67 38 80

1.1 0.8 0.8 1.1 0.9 0.45 0.35 0.65 2.3 0.45 0.4 1.4 0.3 0.45 2.7 2.2 1.1 0.4 0.3 0.5 1.2 1.2 0.9 0.7 0.8 0.9 0.45 0.75 3.2 0.6 0.75 1.2 1.4 3.0 1.6 0.25 0.95 0.8

EPTC EPTC EPTC EPTC EPTC Butylate EPTC EPTC EPTC EPTC EPTC EPTC EPTC EPTC EPTC EPTC EPTC EPTC EPTC Triallate EPTC EPTC EPTC EPTC EPTC EPTC EPTC EPTC EPTC EPTC EPTC EPTC Vemolate EPTC EPTC EPTC EPTC EPTC

6.3 6.3 6.3 6.3 6.3 8.9 6.3 6.3 6.3 6.3 6.3 6.3 6.3 6.3 6.3 6.3 6.3 6.3 6.3 8.4 6.3 6.3 6.3 6.3 6.3 6.3 6.3 6.3 6.3 6.3 6.3 6.3 6.5 6.5 6.5 6.3 6.3 6.3

Maize Maize Maize Maize Maize Maize Maize Maize Maize Maize Maize Maize Maize Maize Maize Maize Maize Maize Maize Maize Maize Maize Maize Maize Maize Maize Maize Maize Maize Maize Maize Maize Maize Maize Maize Maize Maize Maize

100 100 90 96 93 97 95 98 8 97 65 91 96 93 23 3 89 92 88 79 12 100 73 72 100 90 68 86 15 98 83 83 93 63 95 81 100 87

71 21 78

0.45 1.2 0.7

EPTC EPTC EPTC

6.3 6.3 6.3

Maize Maize Maize

77 87 81

XTriallate: S-Z.3.3-trichloro~allyl-N.N-diisopropyl-thiocarbamaie

Soil Treatment Examinations In the course of these examinations the product (con

taining herbicidal agent and antidote) according to the invention was admixed uniformly with the soil so that

In both the seed treatment and the soil treatment

examinations the herbicidal agent itself, combined with any antidote according to the invention, further for the

15

5,116,402

16

phytotoxicity establishment any antidote itself were _

used. The antidotes listed in Tables II and III did not de~ crease the weed-killing activity of the herbicidal agents ‘

beside the protection against the damage of the culti vated plants caused by herbicides. wherein

The damage of a cultivated plant species caused by a

R1 and R2, independently of each other, are hydro

herbicide or herbicidal combination can be prevented

by any of the antidotes according to the invention. 0 According to the invention the scope of cultivated

plants protectable against the damage caused by the

gen, C14, alkyl, C24 alkenyl, C1_4 cyanoalkyl, C14,

haloalkyl, phenyl-C1_4-haloalkyl, phenyl, halogen phenyl, C|.4-alkylphenyl, Ci_4-alkoxyphenyl or; and

herbicidal agent is not restricted to the cultivated plants

R3 and R4, together, are C2_4-alkylene, C4-alkeny

mentioned in the examples.

lene, acetoxy-Cg-alkylene, C1_4-alkoxy-C3-alky

The herbicidal agents usable in combination with the antidotes according to the invention are efficacious

lene, hydroxy-C3-alkylene or halogen-Cg-alkylene. 2. A herbicidal composition comprising an active thiocarbamate herbicide compound, and an antidotally

against a wide range of plant species; optionally the quantity to be used in order to reach the desired effect depends on the kind of the expected effect and the local conditions, too. In the products of the invention the common quantity of the herbicidal agent(s) and the antidote can be suit

effective amount of a compound of the formula I, as

de?ned in claim 1, where

R1 and R2, independently of each other, are hydro

gen, C_6-alkyl, C2_6—alkenyl, C1_4-cyanoalkyl,

C1_6-haloalkyl, phenyl-C1_4-haloalkyl, phenyl,

ably 0.1 to 95 percent by weight; besides, the composi

halogen-phenyl,

C1_4-alkylphenyl,

C1_4-alkox

tion can contain solid or liquid carriers being usual in 25 herbicidal products, eg kaolin, talcum and water, re spectively, or organic solvents or diluents, furthermore wetting agents or emulsifying agents and other usual additives.

R3 and R4, together, are C2_4-a1kylene, C4-alkeny

The following characterizing examples relate to the

3. The herbicidal composition of claim 2, where the active thiocarbamate is from the group consisting of

preparation of products ready for the suitable use of the compositions according to the invention.

lene, acetoxy-Cg-alkylene, C1_4-alkoxy-C3-alky lene, hydroxy-C3-alkylene, halogen-C3-alkylene. EPTC (S-ethyl-N,N-di-n-propyl-thiocarbamate), Butyl

-

ate (S-ethyl-N,N-di-isobutyl-thiocarbamate), Vernolate

EXAMPLE 39

Preparation of An Active Agent Concentrate

yphenyl or; and

35

90 parts by weight of a herbicidal active agent, 8 parts

(S-n-propyl-N-,N-di-n-propyl-thiocarbamate), Pebulate (S-n-propyl-N-butyl-N—ethyl-thiocarbamate), Molinate

(S-ethyl-N,N-hexamethylene-thiocarbamate), Cycloate

by weight of the protective agent according to the invention and 5 parts by weight of Tween 40 emulsi?er

(S-ethyl-N-ethyl-N-cyclohexyl-thiocarbamate), Dial late (S-2,3-dichloro-allyl-N,N-di-isopropyl-thiocarba mate), and Barban (4-chloro-2-butinyl-N(3-chloro

are admixed. From the thus-obtained concentrate a 40

phenyl)-carbamate).

stable and sprayable emulsion can be prepared by dilu tion with a necessary quantity of a solvent e.g. toluene and water.

EXAMPLE 40

4. A herbicidal composition comprising an active chloroacetanilide herbicide compound and an antidot ally effective amount of a compound of the formula I as

45

de?ned in claim 1, where R1 and R2, independently of each other, are hydrogen, C1-6-alkyl, C2_6-alkenyl,

55

Acetochlor (2-ethyl~6-methyl-N-ethoxy-methyl-chloro acetanilide), Alachlor (2,6-diethyl-N-methoxy-methyl

C1_4-cyanoalkyl, C1-6~haloalkyl, phenyl-C._4-haloalkyl, Preparation of An Emulsi?able Concentrate phenyl, halogenphenyl, C1_4-alky1phenyl, C1_4-alkoxy 10 parts by weight of a herbicidal active agent are phenyl; and dissolved in 25 parts by weight of xylene, then 2 parts R3 and R4, together, are C2_4-alkylene, C4-alkenyl, by weight of the antidote of the invention and 4 parts by 50 acetoxy-C3-alkylene, C1_4-alkoxy-C3-alkylene, hy weight of an emulsi?er are added. The thus-obtained droxy-Cg-alkylene or halogen-C3-alkylene. concentrate supplies-diluted with water--a stable, 5. The herbicidal composition of claim 4, where the sprayable emulsion. active chloroacetanalide is from the group consist of EXAMPLE 41

Preparation of a Wettable Powder

15 parts by weight of an active agent, 2 parts by weight of the antidote of the invention, 50 parts by weight of kaolin and 6 parts by weight of trimethylcet yl-ammonium-bromide are admixed and ground in a

chloro-acetaniide), Metolachlor' (6-ethyl-2-methyl-N (Z-methoxy-l-methyl-ethyl)-chloro-acetanilide). 6. A herbicidal composition comprising an active thiocarbamate herbicide compound and an antidotally effective amount of a compound of the formula I, as

de?ned in claim 1, wherein R1 is‘hydrogen, C1_4-alkyl

ball mill. The thus-prepared wettable powder can be or phenyl, and suspended in water and the suspension is sprayable. R3 and R4, together, are C2_4-alkylene, C4-alkeny What is claimed is: lene, acetoxy-Cg-alkylene, C|_4—alkoxy-C3-alky 1. A herbicidal composition comprising an active 65 lene, hydroxy-cg-alkylene or halogen-Cg-alkylene. amide, urea, thiocarbamate, carbamate herbicide com 7. A herbicidal composition comprising an active pound, and an antidotally effective amount of a hetero acetamide herbicide compound and an antidotally effec cyclic compound having formula I: tive amount of a compound of the formula I, as defined

5,1l6,402

17

phenyl, R2 is halogen-Ci_4-alkyl, and R3 and R4, together, are C2_4-alkylene, C4-alkeny

active compound is S-ethyl-N,N-di-n-propyl-thiocarba

lene, acetoxy-C3-alkylene, C1_4-alkoxy-C3-alky

mate.

lene, hydroxy-Cg-alkylene or halogen-Cg-alkylene.

19. The method of claim 15 wherein the crop plants are wheat, corn (maize), sun?ower, oilseed rape, sugar

8. A herbicidal composition comprising an active thiocarbamate herbicide compound and an antidotally

beets, barley, sorghum, rice, or soybeans.

effective amount of a compound of the formula I, as

20. The method of claim 15 wherein the crop plant is com (maize). 21. The method of claim 15, wherein the herbicidally

de?ned in claim 1, wherein R1 is hydrogen, C1_4-alkyl or phenyl,

18

17. The method of claim 15, wherein a herbicidally effective amount of the composition is incorporated in the soil after the soil has been seeded with crop seeds. 18. The method of claim 15, wherein the herbicidally

in claim 1, wherein R1 is hydrogen, C|_4-alkyl or

'

R2 is dichloromethyl, and

active compound is S-ethyl~N,N-di-n-propyl-thiocarba

R3 and R4,, together, are C2_4-alkylene, C4-alkeny

mate and the crop plant is corn. 22. A herbicidal composition comprising an active thiocarbamate herbicide compound and an antidotally effective amount of a compound having formula IV:

lene, acetoxy-C3-alkylene, C1_4-alkoxy-C3-alky lene, hydroxy-C3-alkylene or halogen-C3-alkylene. 9. A herbicidal composition comprising an active acetanilide herbicide compound and an antidotally ef fective amount of a compound of the formula I, as de

?ned in claim 1, wherein RX is hydrogen, C1_4-alkyl or

c

phenyl, R2 is dichloromethyl, and

‘

ClgCH

s

/

R3 and R4, together, are Cz_4-alkylene, C4-alkeny

lene, acetoxy-Cg-alkylene, C1_4-alkoxy-C3-alky lene, hydroxy-Cg-alkylene or halogen-Cg-alkylene. 10. A herbicidal composition comprising an active

23. A herbicidal composition comprising an active chloroacetanilide herbicide compound and an antidot 25

R1 is hydrogen, C1_4-alkyl, phenyl, R2 is dichloromethyl, R3 and R4 together are C2_4-alkylene.

24. A herbicidal composition comprising S-ethyl N,N-dipropylthiocarbamate and an antidotally effective amount of a compound having formula IV, and de?ned 30 in claim 22.

R1 is hydrogen, C1_4-alkyl, phenyl,

'

25. A herbicidal composition comprising Z-chloro-N

(2-ethyl-é-methylphenyD-N-ethoxymethyl

11. A herbicidal composition comprising an active chloroacetanilide herbicide compound and an antidot ally effective amount of a compound having formula I, as de?ned in claim 1, wherein

ally effective amount of a compound having formula IV, as de?ned in claim 22.

thiocarbamate herbicide compound and an antidotally effective amount of a compound having formula I, as de?ned in claim 1, wherein

acetamide

and an antidotally effective amount of a compound having formula IV, as de?ned in claim 22.

26. A herbicidal composition comprising S,N,N-tri 35

propylthiocarbamate and an antidotally effective amount of a compound having formula IV, as de?ned in claim 22.

R2 is dichloromethyl, 27. A herbicidal composition comprising S-ethyl R3 and R4 together are C2_4-alkylene. 12. A herbicidal composition comprising an active‘ N,N-diisobutyl-thiocarbamate and an antidotally effec thiocarbamate herbicide compound and an antidotally 40 tive amount of a compound having formula IV, as de effective amount of a compound having formula I, as

de?ned in claim 1, wherein

R1 is hydrogen, R2 is dichloromethyl, R3 and R4 are C1_4-alkoxy-C2_4-alkyl. 13. A herbicidal composition comprising an active chloroacetanilide herbicide compound and an antidot ally effective amount of a compound having formula I, as de?ned in claim 1, wherein

R1 is hydrogen, R2 is dichloromethyl, R3 and R4 are C1_4-alkoxy-C1_4-alkyl. 14. A method of selectively killing undesired weeds

growing among crop plants which comprises treating

?ned in claim 22.

28. A herbicidal composition comprising 2-chloro-N (2,6-diethylphenyD-N-methoxymethyl acetamide and an antidotally effective amount of a compound having formula IV, as de?ned in claim 22. 29. A method of selectively killing undesired weeds

growing among crop plants which comprises: incorpo rating into the soil in which the crops are to be grown

or applying directly onto the weeds, a herbicidally effective amount of the composition of claim 23, which 50 amount does not appreciably injure the crop plants. 30. A method of selectively killing undesired weeds

growing among crop plants which comprises: incorpo rating into the soil in which the crops are to be grown or applying directly onto the weeds, a herbicidally

crop seeds by coating them with the compound of for 55 effective amount of the composition of claim 24, which amount does not appreciably injure the crop plants. mula I, as de?ned in claim 1, using acetone to aid in 31. A method of selectively killing undesired weeds coating if necessary, prior to'planting the seeds in soil growing among crop plants which comprises: incorpo into which herbicides had previously been incorpo rating into the soil in which the crops are to be grown rated. or applying directly onto the weeds, a herbicidally 15. A method of selectively killing undesired weeds effective amount of the composition of claim 22, which growing among crop plants which comprises: incorpo amount does not appreciably injure the crop plants. rating into the soil in which the crops are to be grown 32. The method of claim 31, wherein the crop plants ‘ or applying directly onto the weeds, a herbicidally are corn (maize), barley, rice, sun?ower, sugarbeets, effective amount of the composition of claim 1, which sorghum, soybeans, oilseed rape, or wheat. 65 amount does not appreciably injure the crop plants. 33. The method of claim 31 wherein the crop plant is com (maize) and the herbicidally active agent is S 16. The method of claim 15, wherein the composition ethyl-N,N-di-n-propyl-thiocarbamate. is incorporated into the soil prior to the seeding of the soil.

t

t

it

i

l

UNITED STATES PATENT AND TRADEMARK OFFICE

CERTIFICATE OF CORRECTION PATENT NO.

: 5,116, 402

DATED

;Mayl26,

1992

_

WVENTOMS) zDUTKA, KOMIVES, FODOR, MARTON, CSIKOS, OSZTHEIMER, HENGER LABORCZY, RETI, SEBOK, SZABOLCS, TOMORDI

It is certified that error appears in the above-identified patent and that said Letters Patent is hereby

corrected as shown below:

’

Claim 24, col 18, line 29, delete "and" and insert therefor —-as——.

Signed and Sealed this Tenth Day ofAugust, 1993 Arrest:

MICHAEL K. KIRK

Arresting Officer

Acting Commissioner of Patents and Trademark: