WO1998013341B1

WO1998013341B1 - Hydroxybenzophenone derivatives as herbicides

Info

Publication number: WO1998013341B1
Application number: PCT/EP1997/005210
Authority: WO
Filing date: 1997-09-23
Publication date: 1998-06-18
Anticipated expiration: 1999-03-27

Abstract

The invention relates to hydroxybenzophenone derivatives of formula (I), wherein R?1, R2, R3, R4, R5, R6, R7 and R8¿ are as defined in the description, and to their use as herbicides.

Claims

AMENDED CLAIMS

[received by the International Bureau on 8 May 1998 (08.05.98); original claim 4 amended; remaining claims unchanged (8 pages)]

R!5 represents halogen, optionally halogenated methyl; or

R!6 represents straight- or branched- chain alkyl containing up to six carbon atoms; Het represents a five membered aromatic heterocyclic ring containing from one to three ring nitrogen atoms which is attached to the -CH(RIO)- group via one of the ring nitrogen atoms ; X represents oxygen or sulphur; and m represents the values 0,1, or 2; or an agriculturally acceptable salt thereof .

2. A method according to claim 1 wherein the locus is an area used, or to be used for the growing of crops and the hydroxybenzophenone derivative is applied at an application rate of from about 0.01 to about 4.0kg/ha.

3. A composition comprising a hydroxybenzophenone derivative as defined in claim 1 with the proviso that when R^ represents 2-trifluoromethyl; R², R^ and R⁷ each represent hydrogen; R^ represents methyl and R^ and R> each represent methoxy, R^ does not represent methyl; or an agriculturally acceptable salt thereof, in association with an agriculturally acceptable diluent or carrier and/or surface active agent.

4. A hydroxybenzophenone derivative of formula (I) as defined in claim 1 or an agriculturally acceptable salt thereof, with the proviso that:

(a) when R¹ represents nitro it is located at the 2-position of the phenyl ring and that at least one of R² and R- represents halogen, R^S(0)_m-, or straight- or branched- chain halogenated alkyl containing up to four carbon atoms ;

(b) when each of R² to R^ and R⁸ represent hydrogen and R⁷ represents methyl, R¹ is not

2-SOMe, 2-S0 Me or 2-S- (4-methylphenyl) ;

(c) when R² , R³ , R⁵ , R⁶ and R⁸ each represent hydrogen and R^ and R⁷ each represent methyl, R¹ is not 2-SMe; (d) when R1 represents 2-CF3 and each of R² to R^ and R⁸ represent hydrogen, R⁷ is not chloro or hydroxy;

(e) when R¹ represents 2-CF3. R , R³ , R⁴, R⁷ and R⁸ each represent hydrogen and R^ represents chloro, R^ is not methoxy;

(f) when R¹ represents 2-CF3 and R² , R³ , R⁴, R5 , R⁷ nd R⁸ each represent hydrogen, R^ is not hydroxy;

(g) when R¹ represents 2-CF3; R² , R³ , R⁵ and R⁸ each represent hydrogen and R^> represents methoxy, R^ is not hydrogen or methyl;

(h) when R¹ represents 2-CF3; R², R³ , R⁵ , R⁶ and R⁸ each represent hydrogen and R⁴ represents methyl, R⁷ is not methoxy; (i) when R¹ represents 2-CF3; R² , R³ and R⁷ each represent hydrogen; R^ represents methyl and

R5 and R^ each represent methoxy, R⁸ is not methyl ;

(j) when R¹ represents 3-CF3 or 4-CF3; R² , R³, R⁵, R⁷ and R⁸ represent hydrogen; R⁶ represents methoxy, R^ is not hydrogen or methyl; (k) when R¹ represents 3-CF3; R²,R³,R⁷ and

R⁸ represent hydrogen; R⁵ and R^ each represent methoxy, R^ is not hydrogen; (1) when R¹ represents 3-CF₃; R² , R³ , R⁴ ,

R5 , R⁷ and R⁸ each represent hydrogen, R^ is not hydroxy; - -

(m) when R¹ represents 3-CF3; R² , R³ , R⁵ , R⁶ and R⁸ each represent hydrogen; R⁷ represents CH₃, R⁴ is not hydrogen

(n) when R¹ represents 4-CF3; R² , R³ , R⁵ , R⁶ and R⁸ represent hydrogen; R⁷ represents ethyl, R is not hydrogen;

(o) when R¹ represents 4-CF3; R², R³ , R⁶ and R⁸ represent hydrogen; R^ and R⁷ represent butyl, R^ is not methyl; (p) when R! represents 4-S-benzyl, 4-

S0₂benzyl, 4-S-ethyl or 4-Sθ2βthyl; R² , R³ , R⁴, R⁶ and R⁸ represent hydrogen; in which one or two of the groups R^ and R⁷ is not a halogen;

(q) when each of R , R³ , R⁵ , R⁷ , and R⁸ represent hydrogen; R⁴ represents methyl; R^ represents methoxy, R^ is not 4-SO-butyl;

(r) when each of R² , R³ , R⁶ , R⁷ and R⁸ represent hydrogen; R⁴ and R^each represent methyl, R¹ is not 4-SOMe; (s) when R! represents 4-SOMe or 4-Sphenyl;

R², R³ , R⁶ and R⁸ represent hydrogen; R^ and R⁷ represent butyl, R⁴ is not hydrogen or methyl; (t) when R¹ represents 4-SMe; R² , R³ , R⁴, R^ , R⁷ and R⁸ each represent hydrogen, R^ is not S-Me or butyl;

(u) when R¹ represents 4-Sθ2Me; R² , R³ , R⁴ , R5, R⁷ and R⁸ each represent hydrogen, R^ is not hydroxy;

(v) when R¹ represents 4-Sphenyl; R² , R³ , R5,R6, R7 _an_ R8 each represent hydrogen, R⁴ is not methyl;

(w) when R¹ represents chloroethylsulphonyl; R² , R³ , R⁴ , R⁵ , R⁷ and R⁸ each represent hydrogen; R^ is not hydroxy or methoxy; (x) when R¹ represents

3-isopropylsulphonamido; R² , R³ , R^ , R⁷ and R⁸ each represent hydrogen; R^ represents methoxy, R⁴ is not methyl; -52-

(y) when R¹ represents NHCθ2Et; R , R³ , R⁵ and R⁷ each represent hydrogen; R⁴ represents methyl, one of the two groups R^ and R⁸ is not methoxy or fluorine; (z) when R¹ represents NHC02Et; R² , R³ , R⁵ ,

R^ and R⁷ each represent hydrogen; R⁴ represents methyl, R⁸ is not fluorine;

(aa) when R¹ represents 4-CF3; R , R³ , R⁵ , R° and R⁸ each represent hydrogen; R⁷ represents fluorine; R⁴ is not hydrogen or methyl;

5. A compound according to claim 4 in which R¹ is straight- or branched- chain haloalkyl containing up to four carbon atoms; or R9s(0)_m- wherein m is as defined in claim 4 and R^ is straight- or branched- chain alkyl containing up to four carbon atoms .

6. A compound according to claim 4 or 5 in which R⁴ represents hydrogen.

7. A compound according to claim 4, 5 or 6 in which at least one of R⁵ , R> , R⁷ and R⁸ represents halogen.

8. A compound according to any one of claims 4 to 7 in which one or two of the groups R5, R6, R⁷ and R⁸ are not hydrogen.

9. A compound according to claim 4 in which:

R! represents C1-C3 alkyl containing at least two halogen atoms, -3(0)^9 (wherein R^ represents C1-C3 alkyl), -CH(R¹⁰) -S (0)_m-R⁹ (wherein R⁹ represents C1-C3 alkyl or phenyl, and R!0 represents hydrogen or methyl) , NO2 or R¹⁴S0₂N(R¹⁰)- (wherein R¹⁴ and R¹⁰ represent Cl- C3 alkyl) ; R² and R³ independently represent C1-C3 optionally halogenated alkyl, hydrogen, halogen, C1-C3 optionally halogenated alkoxy or -S(0)_mR⁹ (wherein R⁹ represents C1-C3 alkyl) ; R⁴ represents hydrogen, C1-C3 alkyl, R⁹Sθ2~

(wherein R⁹ represents C1-C3 alkyl or phenyl optionally substituted by one to five halogen, methyl or Rl⁴S(0)_m- groups wherein R^- represents C1-C3 alkyl), R⁹C(0)- (wherein R⁹ represents C1-C3 alkyl or phenyl optionally substituted by one to five halogen or C1-C3 alkyl groups), R¹⁰C(O)CH2- (wherein R¹⁰ represents phenyl optionally substituted by one or more halogen or C1-C3 alkyl groups) , or methyl substituted by -XR^- wherein R^-6 represents C1-C3 alkyl;

R5 , R6 and R⁷ independently represent hydrogen, halogen, hydroxy, C1-C3 alkoxy or R¹⁶S(0)_m- wherein R¹⁶ represents C1-C3 alkyl; and R⁸ represents hydrogen or halogen.

10. A compound according to claim 4 in which the para-position of the phenyl ring is occupied by R² which represents hydrogen, halogen or C1-C3-haloalkyl .

11. A compound according to claim 4 in which the ortho-position of the phenyl ring is occupied by R^ which represents -S(0)_rn-R⁹ (wherein R⁹ represents C1-C3-alkyl) ,

-CH(R¹⁰) -S(0)_m-R⁹ (wherein R⁹ represents C1-C3- alkyl or phenyl and R^O represents hydrogen or methyl), or R¹⁴Sθ2 (R¹⁰) - (wherein R¹⁰ and R¹⁴ represent C1-C3 alkyl) .

12. A compound according to claim 4 in which: -

R⁴ represents hydrogen; - -

R5 , R6 and R⁷ represent hydrogen, halogen, hydroxy, R¹⁶S(0)_m-, R¹³ , straight- or branched- chain optionally halogenated alkoxy containing up to four carbon atoms, straight- or branched- chain alkyl containing up to six carbon atoms which is substituted by one or more ORI^ groups, -NO2, cyano, or R¹⁰R¹²NSO2-; and

R⁸ is as defined for R^ excluding hydroxy.

13. A compound according to claim 4 having one or more of the following features : - R¹ represents MeS(0)_m- or -CF3. R² , R⁴ and R⁸ each represent hydrogen; R³ represents hydrogen or -CF3 ; R represents hydrogen, halogen, hydroxy or methoxy;

R^ represents hydrogen or MeS(0)_m-; and R⁷ represents hydrogen, halogen or methyl.

14. A process for the preparation of a hydroxybenzophenone derivative of formula (I) as defined in claim 4 which comprises : -

(a) reacting a compound of general formula (II) :

wherein R⁴ , R⁵ , R⁶ , R⁷ and R⁸ are as defined in claim 4 and Y represents a leaving group, with an organometallic reagent of formula (III) : -55-

wherein R^, R² and R³ are as defined in claim 4 and M is a metal;

(b) reacting a compound of general formula (Ha) :

OR⁴

(Ha) wherein R⁴, R^ , R6 , R⁷ and R⁸ are as defined in claim 4 and M represents a suitable metal or metal halide, with a compound of formula (Ilia) :

(Ilia) wherein R^, R² and R³ are as defined in claim 4 and Y is a leaving group;

(c) where R⁴ represents hydrogen and R^, R² , R³ , R⁵ , R⁶, R⁷ and R⁸ are defined in claim 4, de-etherification of the corresponding compound of formula (I) in which R⁴ represents R^³ ;

(d) where R⁴ represents R⁹S02 and R¹, R² , R³ , R⁵ , R⁶, R⁷, R⁸ and R⁹ are defined in claim 4, the sulphonation of the corresponding compound of formula (I) in which R⁴ represents hydrogen with a sulphonyl chloride of formula R⁹S02C1 wherein R⁹ is as defined in claim 4;

(e) where R⁴ represents R¹⁰C (0)C (R¹⁰) (R¹²) - in which R¹, R² , R³ , R⁵ , R⁶ , R⁷ , R⁸, R¹⁰ and R¹² are defined in claim 4, the alkylation of the corresponding compound of formula (I) in which R⁴ represents hydrogen with a compound of formula (IV) :

R¹⁰C(O)C(R¹⁰) (R¹²)-Z (IV) in which R¹^ and R^² are defined in claim 4 and Z represents halogen;

(f) where m is one or two, the oxidation of the corresponding compound of formula (I) in which m is zero or one; optionally followed by the conversion of the compound of formula (I) thus obtained into an agriculturally acceptable salt thereof.