AU642052B2 - Heterocyclic dione derivatives as pesticides and plant growth regulators - Google Patents

Description

OPI DATE 26/05/92 AOJP DATE 09/07/92 APPLN. ID 87442 91 PCT NUMBER PCT/EP91/02014 INTERNA. TREATY (PCT) (51) International Patent Classification 5 (11) International Publication Number: WO 92/07837 C07D 265/02, A01N 43/72 Al C07C 205/59 (43) International Publication Date: 14 May 1992 (14.05.92) (21) International Application Number: PCT/EP91/02014 (72) Inventor: LEE, Shy-Fuh 228 Carbonera Avenue, Sunnyvale, CA 94086 (US).

(22) International Filing Date: 23 October 1991 (23.10.91) (74) Agent: SANDOZ LTD.; Lichtstrasse 35, CH-4002 Basle

(CH).

Priority data: 604,708 25 October 1990 (25.10.90) US (81) Designated States: AT (European patent), AU, BE (European patent), BR, CA, CH (European patent), CS, DE (71)Applicant (for AT only): SANDOZ-ERFINDUNGEN (European patent), DK (European patent), ES (Euro- VERWALTUNGSGESELLSCHAFT M.B.H. [AT/ATI; pean patent), FR (European patent), GB (European pa- Brunner Strasse 59, A-1235 Vienna tent), GR (European patent), HU, IT (European patent), JP, KR, LU (European patent), NL (European patent), (71) Applicant (for DE only): SANDOZ-PATENT-GMBH [DE/ PL, SE (European patent), SU DE]; Humboldtstrasse 3, D-7850 Lrrach (DE).

(71) Applicant (for all designated States except AT DE): SAN- Published DOZ LTD. [CH/CH]; Lichtstrasse 35, CH-4002 Basle With international search report.

(CH).

a L- (54) Title: HETEROCYCLIC DIONE DERIVATIVES AS PESTICIDES AND PL 'NT GROWTH REGULATORS (57) Abstract The present invention concerns substituted 3,5-dioxo-3,4,5,6-tetrahydrooxazines as herbicides, processes and intermediates for their preparation, compositions containing them and their use as herbicides and acaricides.

I

See back of page WO 92/07837 PC/E9~1/02014

A

HETEROCYCLIC DIONE DERIVATIVES AS PESTICIDES AND PLANT GROWTH REGULATORS The present invention concerns substituted 3,5-dioxo-3,4,5,6tetrahydrooxazines as herbicides, processes and intermediates for their preparation, compositions containing them and their use as herbicides and acaricides.

USP 4,695,673 describes a wide range of acylated 1,3-dicarbonyl compounds and their use as herbicides but makes no reference to' or suggestion of the 3,5-dioxotetrahydrooxazine ring characterizing the compounds of the present invention.

More particularly, the invention concerns compounds of formula I

R

1

R

4

R

R2 0N R3 R6 wherein, each of R 1

R

2 and R 3 is independently hydrogen, Ci.-alkyl, carboxyl,

C

1 .alkoxycarbonyl, phenyl or phenyl substituted by one to three groups as R, or Ri and R 2 together form a C3- 6 alkylene bridge

R

4 is hydrogen, Ci.galkyl, ClI 0 alkylcarbonyl, C 1 -salkoxycarbonyl,

C(O)NR

7

R

8 Cl.alkylsulphonyl, P(O)-(0R 9 2

R

7

P(O)-OR

9 benzoyl or a cation.

R is C 1 alkyl optionally substituted by 1 to 6 halogen atoms, Ci.

8 alkoxy optionally substituted by 1 to 6 halogen atoms, Cisgalkylcarbonyl, Cl-palkoxycarbonyl, NR7R, OnS(O),.Rio, NR 7

SO

2 Rs, halogen, cyano or nit:

R

5 is C 1 .,.alkoxy substituted by 1 to 6 halogen atoms; R6 is hydrogen or selected from the meanings given for R; each of R 7 and RB is independently hydrogen or C-.salkyl;

R

9 is Ci-ealkyl;

R

10 is C 1 alkyl optionally substituted by 1 to 6 halogen atoms; n is 0 or 1; n' is 0, 1 or 2; provided that when R1, R 2 and R 3 are methyl, R4 and R 6 are hydrogen and R is nitro, R 5 is not difluoromethoxy.

In the above definitions, halogen is conveniently selected from chloro, bromo and fluoro, Ci.-alkyl moieties, preferably have 1 to 4 carbon atoms.

Each of R 1 Rz and R3 is preferably hydrogen, C 1 -4alkyl especially hydrogen or C 1 3 alkyl.

R conveniently signifies C1.,alkyl optionally substituted with WO 92/07837 WO 9207837PCr/EP91/02014 halogen, 1 .4alkyl, halogen or nitro. It is preferably methyl,

CF

3 Cl.

3 alkylsulfonyl, C 1 3 alkylsulfonyloxy, chioro, bromo or nitro.

R

5 is preferably fluoroalkoxy, more preferably OCF 3

R

6 is preferably hydrogen, C 1 4 alkyl, C 1 4alkoxy, bromo, chioro; it is more preferably hydrogen, methoxy or chioro.

R

4 is conveniently hydrogen, C 1 4 alkcyl, C 4 alkylcarbonyl, benzoyl,

C

1 A4alkylsulfonyl or a cation. It is preferably hydrogen, methyl, ethyl, t-butylcarbo-nyl, isobutylcarbonyl, benzoyl or methylsulfonyl. As a cation

R

4 is preferably an alkali metal such as Na 4

K

4 Li' or an Amnmonium cation.

Examples of particularly preferred substituents are for R, and R 2 each a) H, C 1 A4alkyl, phenyl or phenyl substituted by one to three groups as R b) H, C1-4alkyl phenyl or phenyl substituted by one to three groups as R C) H, C 1 3 alkyl d) H, CH 3 e) C 1 3 alkyl

R

3 a) Cl-ealkyl C) CH 3

CAH

R

4

H

R a) N0 2 Cl, CF 3 b) NO 2 Cl c) N0 2 R5- OCF 3 R6 H Combinations of these substituent meanings are especially preferred.

A particularly preferred single compound is 2,6,6-trimethyl.4- (4-trifluoromethoxy-2-nitrobenzyl)-2H-1,2-oxazine-3,5-(4H,6H)-dione.

The compounds of the present invention of formula I are new substances which can be prepared by methods analogous to methods ktsown in the art, such as those described in European Patent Application EP 186,117 and references cited therein. More particularly, they can be obtained by, for example: rearranging an enol ester of formula (II) 0 1I

R

2 R wherein R 1

R

2

R

3 R, R 5 and R6 are as previously defined to give a compound of formula I wherein R 4

H.

This rearrangement is conveniently effected by reacting the compound WO 92/07837 pCr/Ep91/02014

I

3 of formula II with a cyanide source and a moderate base.

For example, the reaction may be carried out in the presence of a catalytic amount of a source of cyanide anion and/or hydrogen cyanide, together with a molar excess, with respect to the enol ester, of a moderate base. The reaction is conveniently carried out in a solvent which is inert under the reaction conditions, e.g. 1,2-dichloroethane, toluene, acetonitrile, methylene chloride, ethyl acetate, dimethylformamide (DMF) and methyl isobutyl ketone (MIBK). In general, depending on the nature of the reactants and the cyanide source, the rearrangement may be conducted at temperatures up t: about 80-C. In some cases, for instance when there is a possible problem of excessive by-product formation, the temperatures should be kept at about 40*C maximum.

Preferred cyanide sources are alkali metal cytoide sch as sodium and potassium cyanide; cyanohydrins of methyl alkyl ketones having from 1-4 carbon atoms in the alkyl groups, such as acetone or methyl isobutyl ketone cyanohydrins; cyanohydrins of benzaldehyde or of C 2

-C

5 aliphatic aldehydes such as acetaldehyde, propionaldehyde, etc., cyanohydrins; zinc cyanide; tri(lower alkyl) silyl cyanides, notably trimethyl silyl cyanide; and hydrogen cyanide itself. Among cyanohydrins the preferred cyanide source is acetone cyanohydrin. The cyanide source Is used in an amount up to about 50 mole percent based on the enol ester. Generally about 1-10 mole of the cyanide source is preferred.

By the term "moderate base" is meant a substance which acts as a base yet whose strength or activity as a base lies between that of strong bases such as hydroxides (which could cause hydrolysis of the enol ester) and that of weak bases such as bicarbonates (which would not function effectively). Moderate bases suitable for use in this reaction include both organic bases such as tertiary amines and inorganic bases such as alkali metal carbonates and phosphates. Suitable tertiary amines include trialkylamines such as triethylamine, trialkanolamines such as triethanolamine, and pyridine. Suitable inorganic bases include potassium carbonate and trisodium phosphate. The base is used in an amount of from about 1 to about 4 moles per mole of enol ester, preferably about 1.3-2 moles per mole.

When the cyanide source is an alkali metal cyanide, particularly potassium cyanide, a phase transfer catalyst may be included in the reaction. Particularly suitable phase transfer catalysts are the Crown ethers.

Compounds of formula I where R4 is other -than hydrogen can be prepared by reacting a compound of formula I wherein R 4 is hydrogen with either a) the group R 40 -OH and a catalyst, or b) the group R4o-Q and a moderate base, wherein Q is a halogen atom, to give a compound of formula I where R 40 is the desired substituent.

WO 92/07837 PCT/EP91/02014 The above reaction a) is carried out in the presence of a catalyst such as concentrated sulfuric acid. The reaction is conveniently carried out in a solvent which is also the reactant such as methanol, and at an elevated temperature.

The above reaction b) is carried out in the presence of a moderate base such as triethylamine or pyridine and conveniently at RT or below.

The compounds of formula I may be recover ed from the reaction mixture in which they are formed by working up by established procedures.

The compounds of formula II may be prepared by reacting a compound of formula III R2III with a compound of formula IV

R

Hal

IV

R

6 This reaction is carried out in the presence of a base such as triethylamine, potassium carbonate, pyridine, preferably triethylamine and i an inert solvent such as dichloromethane, acetonitrile, toluene, tetrahydrofuran, dimethylformamide. The reaction is conveniently carried out at RT or below.

The remaining compounds of formula II may be prepared analogously.

The compounds of formula III are new and also form part of the invention.

They may be prepared by decarboxylating a compound of formula V R2 R20

V

3 wherein R 20 is alkoxy, especially ethoxy or methoxy and R 1

R

2 and R 3 are as defined above. The reaction may be carried out at elevated temperatures e.g. 80-90' and in an inert solvent such as e.g. wet dimethylsulfoxide.

The compounds of formula V may be prepared analogously to known methods e.g. according to the following reaction scheme.

WO 92/07837PC'E9/24 PCr/EP91/02014

R

3 NHOC (RjR 2 C0R 20

VI

/a)

CIOCCH

2

COR

20

VII

R

3 NOC (R 1

R

2 C0R 2 o

COCH

2

COR

20

VIII

V

Reaction may be carried out in an inert solvent such as dichioromethane and aqueous ether and in the presence of a base such as triethylamine or sodium carbonate at RT.

Reaction may be carried out in an inert solvent such as toluene benzene or tetrahydrofuran in the presence of a base such as sodium methoxide or sodium hydride.

The remaining starting materials and reagents employed~ in the process described herein are either known or, insofar as they are not known, may be produced in a maniner analogous to the processes described herein or to known processes [cf for compounds VI Kornowski et.al. Bull. Soc. Chim France 1966(2)683].

The compound 2 -nitro trif luoromethoxy -banzoic acid is new.arlal The k mpounds of this invention wherein RA is H can have four structural turmulae because of tautomerism as illustrated as follows: 0 0H I5

R

3

R

6 IC R 2 A N 14 WO 92/07837 PCT/EP91/02014 It will of course be readily appreciated that where R, is other than hydrogen such compounds may exist in forms Ib, Ic and Id or as mixtures of these forms.

The novel compounds of formula I are useful for the control of weeds, using pre- and/or post-emergent treatments. Compounds of formula I are also useful as plant growth regulators (PGRs) and acaricides. The compounds can be applied in the form of dusts, granules, solutions, emulsions, wettable powders, flowables and suspensions. Application of a compound of the present invention as herbicides is made according to conventional procedure to the weeds or their locus using an herbicidally effective amount of the compounds, usually from about one-tenth or less to ten pounds per acre. The application of a compound of the present invention to the "locus" of the weed includes application to the seeds, the plant (weed) or parts of the plant, or the soil.

Application of a compound of the present invention as an acaricide is made according to conventional procedure to the site of infestation using an acaricidally effective amount of the compound, usually 100 g/ha to 1 kg/ha.

The term "herbicide," as used herein, refers to an active ingredient which modifies the growth of plants because of phytotoxic or plant growth regulating properties so as to retard the growth of the plant or damage the plant sufficiently to kill it.

Compounds of the present invention, when applied as either post or pre-emergents, demonstrate high levels of herbicidal activity on broadleaf, grass and sedge weeds. They also exhibit selectivity in wheat, corn, cotton, some varieties of soybean and in some cases, rice.

In the use of the compounds of formula I for combatting weeds and acari, a compound of formula I, or mixtures thereof, can conveniently be employed as compositions in association with acceptable diluent(s) for application to the weed, acari or their loci. Such compositions also form part of the present invention.

Methods of preparing suitable formulations which can be used with a compound of the present invention are described in the literature along with suitable liquid and solid carriers, such as in U.S. Patent 4,192,669 and 4,163,661, which are incorporated herein by reference. The optimum usage of a compound of the present invention is readily determinable by one of ordinary skill in the art using routine testing such as greenhouse testing and small plot testing.

Suitable formulations contain from 0.01 to 99% by weight of active ingredient, from 0 to of surfactant and from 1 to 99.99% of solid or liquid diluent(s). Higher ratios of surfactant to active ingredient are sometimes desirable and are achieved by incorporation into the formulation or by tank mixing. Application forms of a composition generally contain between 0.01 and 25% by weight of active ingredient. Lo!er or higher WO 92/07837 PCT/EP91/02014 levels of active ingredient can, of course, be present depending on the intended use, the physical properties of the compound and the mode of application. Concentrate forms of a composition intended to be diluted before use generally contain between 2 and 90%, preferably between 5 and 81% by weight of active ingredient.

Useful formulations of the compounds of formula I include dusts, granules, suspension concentrates, wettable powders, flowables and the like. They are obtained by conventional manner, e.g. by mixing a compound of formula I with the diluent(s) and optionally with other ingredients.

Alternatively, the compounds of formula I may be used in micro-encapsulated form.

The compounds of formula I can be combined with a cyclodextrin to make a cyclodextrin inclusion complex for application to the weed, acari or their loci.

Agriculturally acceptable additives may be employeid in the herbicidal compositions to improve the performance of the active ingredient and to reduce foaming, caking and corrosion, for example.

"Surfactant" as used herein means an agriculturally acceptable material which imparts emulsifiability, spreading, wetting, dispersibility or other surface-modifying properties. Examples of surfactants are sodium lignin sulfonate and lauryl sulfate.

"Diluent" as used herein meaias a liquid or solid agriculturally acceptable material used to dilute a concentrated material to a usable or desirable strength. For dusts or granules it can be e.g. talc, kaolin or diatomaceous earth, for liquid concentrate forms for example a hydrocarbon such as xylene or an alcohol such as isopropanol, and for liquid application forms e.g. water or diesel oil.

The compositions of this invention can also comprise other compounds having biological activity, e.g. compounds having similar or complementary acaricidal or herbicidal activity for broadspectrum weed control or compounds having antidotal, fungicidal, insecticidal or insect attractant activity.

The following examples are provided to illustrate the practice of the present invention. Temperature is given in degrees Centigrade. RT means room temperature. Parts and percentages are by weight.

WO 92/07837PC/91/24 PCF/EP91/02014 EXAMPLE 1 Preparation of 2,6, 6 -trimethyl (2 -nitro -4 -trifluoromethoxybenzoyl) 2H-l ,2-oxazine-3.,5 (4H, 6H) -diane (Formula I R 1

-R

2

-R

3

-CH

3 R4-Rr,-H; R-N0 2

RS-OCF

3 Compound No. 1) 71.4 g of 2,6,6-trimethyl-5-(2-nitro-4-trifluoromethoxybenzoyloxy) 6H-l,2-oxazine-3-one is dissolved in 300 ml of acetonitrile and 49 ml of triethylamine. To this solution, cooled in a water bath, is added 3.2 ml of acetone cyanohydrin. The resulting solution is stirred at under nitrogen, overnight. The reaction mixture is concentrated to a syrup and the syrup is portioned between 400 ml of water and 150 ml of dichloro.

methoxy. The combined extracts are washed with 2N HCl, brine, dried and evaporated to dryness to give oily residue. The crude product is then crystallized from ethanol to yield 2,6,6-trimetbyl-4- (2-nitro-4-Lrifluoromethoxybenzoyl)-2H-l,2-oxazine-3,5(4H, 6H)-dione, m.p. 73-75.5o* Proceeding analogously to Example 1 the following compounds of formula I are obtained.

TA BLE A 2_ W RA R5 96 1 CH 3

CH

3

CH

3 H N0 2 4-OCF 3 H 73-75.5* 2 CH 3

CH

3

CH

3 H Cl 4-OCHF 2 H 95-97* EXAMPLE 2 Preparation of 2 -nitro -4 trif luoromethoxybenzonitrile To a stirred solution of 64.30 g of 2 -nitro -4 -trif luoromethoxyaniline (Zhur, Obshchei. iKhim 31, 915-24 (1961)) in 72 ml of concentrated hydrochloric acid and 190 ml of water, cooled to 0* is added dropwise over min. a solution of 20.0 g of sodium nitrite in 75 ml of water. After stirring at 0*C for an additional 45 mini., the diazonium salt solution is added dropwise, in portions, over 75 min. to a stirred solution of 82.69 g of potassium cyanide and 46.62 g of cupric sulfate in 400 ml of water at 60-65 0 C. The gray-greenish mixture is stirred and heated at 60-65*C for an additional 30 min and then allowed to cool to r.t. The mixture is filtered through celite and the precipitate is washed with dichloromethane (3 x 200 ml). The dichloromethane washings are used to extract the aqueous solution. The combined extracts are washed with water, brine, dried and evaporated to dryness to gi~ie an toily residue which is chromatographed on silica gel to give 31.44 g tf 2 -nitro triPfluoromethoxybenzonitrile.

WO 92/07837 PC1'/EP9I/02014 EXAMPLE 3 Preparation of 2-nitro-4-trifluoromethoxy benzoic acid A stirred solution of 40.96 g of 2-nitro-4-trifluorobenzonitrile in ml of concentrated sulfuric acid and 125 ml of water is refluxed for hrs. The reaction mixture is cooled and diluted with 200 ml of cold water.

The aqueous supernatant is decanted from the brown cryustalline gum. The crystalline gum is dissolved in ether and extracted with 0.5 N sodium hydroxide solution. The combined basic aqueous solution is cooled and acidified with concentrated hydrochloric acid and then extracted with ether. The combined extracts are dried and evaporated to dryness to give crystalline 2-nitro-4-trifluoromethoxyboenzoic acid m.p. 119*C.

EXAMPLE 4 Preparation of2,6,6-trimethyl-5-(2-nitro-4-trifluoromethoxybelzoyloxy)-6H-l,2-oxazine-3-one (Formula II R 1

-R

2

-R

3

-CH

3

RA-R

6 H; R-N0 2

R

5

-OCF

3 A stirred solution of 43.98 g of 2-nitro-4-trifluoromethoxybenzoic acid in 100 ml of thionyl chloride is refluxed for 2 hrs and then concentrated to dryness to give oily 2 -nitro -4 -trif luoromethoxybenzoyl chloride. To a stirred solution of 27.53 g of 2,6,6-trimethyl-2H-l.2oxazine-3,5C4H, 6H)-dione and 35 ml (25/mm) of triethylamine in 290 ml of dichloromet'nane, cooled '4n an ice bath, under nitrogen, is added dropwise a solution of 2-nitro-4-trifluoromethoxybenzoyl chloride in 100 ml of dichloromethane. After stirring at O'C at r. t. for 2 hrs. the reacttion mixture is diluted with 150 ml of dichloromethane and the solution is washed with water, brine, dried and evaporated to dryness to give 2,6,6- 2,,-rmty--2nto4tilooehoyezyoy-H12oaie3 one.

Claims (9)

1. A compound of formula I R R4 R 2 0 N 0 I R6 wherein, R 3 R each of R 1 R 2 and R 3 is independently hydrogen, C,.ealkyl, carboxyl, Cl,.alkoxycarbonyl, phenyl or phenyl substituted by one to three groups as R, or R, and R 2 together form a C 3 -Galkylene bridge R 4 is hydrogen, C..alkyl, C 1 alkylcarbonyl, Cl-salkoxycarbonyl, C(0)NR7RG, CI-ealkylsulphonyl, P(0)-(OR) 2 R 7 P(Q)-0R 9 benzoyl or a cation; R is CI..alkyl optionally substituted by 1 to 6 halogen atoms, C.-8- alkoxy optionally substituted by 1 to 6 halogen atoms, C.,Salkyl- carbonyl, C 1 -ealkoxycarbonyl, NR7R 8 0,S(0)nRIo, NR 7 S0 2 R 8 halogen, cyano or nitro; R 5 is Cl-aalkoxy substituted by 1 to 6 halogen atoms; Re is hydrogen or sel-cted from the meanings given for R; each of R 7 and Ra is independently hydrogen or C 1 -ealkyl; R 9 is Cl-ealkyl; R 10 o is Cl-Balkyl optionally substituted by 1 to 6 halogen atoms; n is 0 or 1; n' is 0, 1 or 2; provided that when RI, R 2 and R3 are methyl, R, and R are hydrogen and R is nitro, R 5 is not difluoromethoxy.

2. A compound according to Claim 1 wherein each of R 1 R 2 R 3 is selected from hydrogen or Cl- 4 alkyl; R is selected from C 1 -4alkyl optionally substituted with chloro, bromo, or fluoro, -(0)n-S(0)n,-CI-4alkyl, halogen or nitro; R 5 is fluoroalkoxy; R6 is selected from hydrogen, C 1 ,.4alkyl, C 1 4 alkoxy, bromo, chloro; R 4 is selected from H, C,.4alkyl, C4.alkylcarbonyl, benzoyl, C1-4alkyl- sulphonyl or a cation.

3. A compound according to Claim 2 wherein each of RI, R 2 and R 3 is selected from H, C 1 .alkyl R4 is H; R is selected from N02, Cl, CF 3

4. A compound according to Claim 3 wherein RI, R 2 and R 3 are each methyl, R 4 and R are each hydrogen, R is nitro and R 5 is OCF 3 j I' -11 A pesticidal composition comprising the compound of formula I as defined in any one of Claims 1 to 4, in association with an agriculturally acceptable carrier.

6. A method of controlling weeds comprising applying to the weeds or their locus herbicidally effective amount of a compound of formula I as defined in any one of Claims 1 to 4.

7. A method of controlling acari comprising applying to the acari or their locus an acaricidally effective amount of a compound of formula I as defined in any one of Claims 1 to 4. B.

8. A process for preparing a compound of formula I as defined in Claim 151 which comtprises a) rearranging an enol ester of formula (II) E II R 2 B,,0, 3 wherein R 1 R 2 R 3 R, R 5 and R 6 are as defined in Claim 1 to give a compound of formula I wherein R 4 is H b) when R 4 is other than hydrogen reacting a corpound of formula I wherein R 4 is hydrogen with either a) the group R 40 "OH and a catalyst, or b) the group R 4 0-Q and a moderate base, wherein Q is a halogen atom, to gil-e a compound of formula I where R 4 0 is the desired substituent. 930730,p:\oper\dab,87442mpe, 12 I I

9. Compounds of formula I or processes for their preparation, substantially as hereinbefore described with reference to the Examples. DATED this 30th day of July, 1993 Sandoz Ltd. By Its Patent Attorneys DAVIES COLLISON CAVE S S *5 S.. S S S S S S S S S S S S S S S. "A T q30M3,p:vpcr\dab,87442Jpc.13 INTERNAIONAL SEARCH REPORT PCT/EP 91/02014 1. CASIFICATION OF SUBJECT MATTER Of seval classification smrs apply, Indicate allit According to International Patent Cassfication (EMC or to both National asification and IPC Int.C1. 5 C07D265/O2; A01N43/72; C07C205/59 II. FIELDS SEARCHED inimum Documentation Swed 7 ha Classification SY9ten Casslficatuc. Symbols Int.Ci. 5 C07D A 01N ;C07C Documentation Searchof other than Minimum Documentation to the Extent that such Documents ane Included in the Fields Searchedm DL DOCUMENTS CONSIDEOED TO BE RELEVANT 9 CraeOM Citation of Document, 1 lwth indication, where appropriate, of the relevant passapae1 Relevant to aim No.U3 A EP,A,0 090 262 (STAUFFER CHEMICAL COMPANY) 5 1-8 October 1983 1 see claims A EP,A,0 186 117 (STAUJFFER C~HEMICAL COMPANY) 2 1,8 July 1986 cited in the applicz.don see claims PX EP,A,O 394 889 (SANVJZ AG) 31 October 1990 1-8 see page 9, table A, Cpd. 22 and claims Special categories of cited documents 10 'r later document published after the intenationail date or priority date and not In conflict with the application but 'k document defining the g~eneral state of the art which Is no cited to understand the principle or theory underlying the considered to be of particular reeace invention Or' earlier document but published on or after the international 'r document of partlilar renace; the claimed linetion filing date cannot be considered novel or cannqt be considered to IV' document which may throw doubts on priority clm(s) or involve an inventive step which Is cited to establish the publication date of another Or' document of paidatlar Mnce; the clairod Inventiou citation or other special reason (as specified) canot be considered to Involve an Inventive step wo--n the document referring to an oral disclosure, use, wthibition or document Is combined with one or more other such vocu- other meum eas such combination being obvious to a person sklled document published prior to the International filing date but in=kArt later than the priority date claimed W& document member of the same patent family IV. CERTIFICATION Date of the Actual Compistlon of the Internatiota Search Date of Mailing of this International Search Report JANUARY 1992 27. 01. 92 Int.",zational Searching Authorit Signature of Authorized OMfce EUROPEAN PATENT OFFCE C HOU LY J. cQ4$ J bt.C'k 7

11. tCrPIAM6I laed WWI 000- IMS) -,r ANNEX TO THE INTMZNATIONAL SEARCH REPORTP ON INTERNATIONAL PATENT APPLICATION NO. ~P9102014 SA 52436 71his annex Eaus the patent family members relating to the patent documents ekted in the abovequotioued irdesuational warth report. The members me us contained in the European Patent Office EDP file on Thbe Eurea Ptent Office is in no way liable for them particulars whaich aft nurdy iven. for the purpon of information. 15/0 1/92 Patnt document Publication IPatent immily Publication cited hi searet nv~rt date mebef dote EP-A-0090262 05-10-83 AU-B- 560068 26-03-87 AU-A- 1276883 29-09-83 CA-A, 1217204 27-01-87 JP-C- 1461556 14-10-88 JP-A- 58130451 21-10-83 JP-B- 63007534 17-02-88 US-A- 5006162 09-04-9 1 US-A- 4780127 25-10-88 EP-A-0186117 02-07-86 AU-B- 592069 04-01-90 AU-A- 5133585 26-06-86 JP-A- 61171449 02-08-86 US-A- 4695673 22-09-87 EP-A-0394889 31-10-90 AU-A- 5377190 01-11-90 CA-A- 2015242 25- 10-90 CN-A- 1046900 14-11-90 JP-A- 2295905 06-12-90 2- 95905-- 90-