- I -

HERPICIPES

The present invention relates to the use of certain compounds as herbicides. In particular, the invention relates to the herbicidal use of a series of 1 ,2-dihydro- 1 ,3,5-tria?ines. Compounds according to the invention are known and have been used in various pharmaceutical applications. For example, GB 1053113 and GB 1053307 disclose diamino-l,2-dihydro-l,3,5-triazines and their use as hypotensives, vasodilators and CNS agents and GB-A-831252 and GB-A- 1270831 disclose similar compounds as bactericide or anti-malarial agents. The preparation of these and similar compounds is disclosed in the documents mentioned above and in US 2,976,288, US 3,105,074, US 3,660,394, US 3,682,912, US 3,723,429 and GB-A-1297273.

More recent work described in US 5,300,503 has demonstrated that members of this series of compounds have insecticidal activity, especially against the larvae of Lepidoptera and Coleoptera insects.

However, the present inventors have made further investigations of 1,2-dihydro- 1,3,5- triazines and have found that certain members of the family have activity as herbicides. This finding would certainly not have been expected from the previously known activities of the compounds in this series, particularly since US 5,300,503 suggests that the compounds would be useful as insecticides for treating crops. Indeed, the authors of that document actually examined their test plants for phytotoxic effects and no such effects were reported.

Therefore, in a first aspect of the present invention, there is provided the use of a compound of general formula la or lb:

la lb wherein:

R ¹ and R ² are each, independently, hydrogen; C,-C ₆ alkyl, optionally substituted with OH or halo; or C ₂ -C ₆ alkenyl, optionally substituted with OH or halo; or R ¹ and R ² together

form a 3 to 8 membered cycloalkyl or cycloalkenyl ring either of which may optionally be substituted with C-- alkyl, C ₂ -Q _. alkenyl, OH or halo;

R ³ is a straight or branched chain C C ₂ o alkyl, C ₂ -C ₂₀ alkenyl or C ₂ -C ₂ o alkynyl group, any of which may optionally be substituted with one or more substituents independently selected from: halo, OR ⁶ , COR ⁶ , COOR ⁶ , CONR ⁶ R ⁷ , NR ⁶ COR ⁷ , NR ⁶ R ⁷ , NR ⁶ SO ₂ R ⁷ , SR ⁶ , SOR ⁶ , SO ₂ R ⁶ ,

OCOR ⁶ , N ₃ , NO ₂ , cyano, SOzNRV, C=NOR ⁶ , CSNRV, NR ^δ CON R ⁷ R ^7' , OCO ₂ R ⁶ ,

OCONR ⁶ R ⁷ , NR ⁶ CO ₂ R ⁷ , NR ⁶ CON R ⁷ R ^7' or a group X each R ⁶ , R ⁷ and R ⁷ is independently selected from hydrogen, a group X or C ₁ -C ₁₂ alkyl, C ₂ -Cι ₂ alkenyl or C ₂ -C| ₂ alkynyl, any of which may be substituted by a group X, OH or halo; alternatively, R ⁶ and R ⁷ may together form a 3 to 7 membered carbocyclic or heterocyclic ring;

X is benzyl, phenyl, a 3 to 8 membered cycloalkyl, cycloalkenyl or saturated or unsaturated heterocyclic ring, or a fused ring system containing up to four 3 to 8 membered rings; the rings of the fused system may be cycloalkyl, cycloalkenyl, phenyl or saturated or unsaturated heterocyclic rings or a combination of these; the group X may optionally be substituted with one or more substituents selected from cyano, halo, SO ₂ NR ⁸ R ^8' , NO ₂ , C C ₈ alkyl, C ₂ -C ₈ alkenyl, C ₂ -C ₈ alkynyl, C _r C ₈ haloalkyl, C ₂ -C ₈ haloalkenyl, C ₃ -C ₈ cycloalkyl, phenyl, phenyl(Cι-C ₈ alkyl)-, phenyl(C ₂ -C ₈ alkenyl)-, phenyl(C ₂ -C ₈ alkynyl)-, substituted phenyl(C,-C ₈ alkyl)-, substituted phenyl(C ₂ -C ₈ alkenyl)-, substituted phenyl(C ₂ -C ₈ alkynyl)-, OR ⁸ ,

COR ⁸ , COOR ⁸ , CONR ⁸ R ^8' , NR ⁸ R ^8' , SR ⁸ , SOR ⁸ , SO ₂ R ⁸ , C,-C ₈ alkyl-OR ⁸ , C ₂ -C ₈ alkynyl-OR ⁸ or C ₂ -C ₈ alkenyl-OR ⁸ or, where appropriate, oxo or imino; substituents on substituted phenyl(alkyl), phenyl(alkenyl) and phenyl(alkynyl) groups are selectd from halo, Ci- s alkyl, cyano or Ci- alkoxy; each R ⁸ is, independently, hydrogen, C C ₈ alkyl or C ₂ -C ₈ alkenyl, C ₂ -C ₈ alkynyl, C ₃ -C ₈ cycloalkyl, phenyl or benzyl, any of which may, where appropriate, be substituted with cyano, halo, NH ₂ , SO ₂ NH ₂ , NO ₂ , oxo, imino, Cι-C ₈ alkyl, C ₂ -C ₈ alkenyl, Cι-C ₈ haloalkyl, C ₂ -C ₈ haloalkenyl or phenoxy(C C ₄ alkyl)-;

R ³ may also be a group -Z-Q, wherein Z is R ¹⁰ , R ¹⁰ -Y-Y-R ¹⁰ , R ^,0 -Y-O-Y-R ¹⁰ , R ¹⁰ -NHCO-Y-CONH-R ¹⁰ , R ^,0 -Y-R ¹⁰ , R ¹⁰ -O-R ¹⁰ , R ^,0 -O-R ^,0 -O-R' ⁰ , R ¹⁰ -S-R ¹⁰ αr R ¹⁰ -NR ^{1 I} -R ^, °;

R ¹⁰ and R ⁿ are each C1-C20 alkylene or C ₂ -C ₂ o alkenylene; Y is a divalent linking group derived from benzyl, phenyl, a 3 to 8 membered cycloalkyl, cycloalkenyl or saturated or unsaturated heterocyclic ring, or a fused ring system containing up to four 3 to 8 membered rings; the rings of the fused system may be cycloalkyl, cycloalkenyl, phenyl or saturated or unsaturated heterocyclic rings or a combination of these; the group Y may optionally be substituted with one or more substituents selected from cyano, halo, SC>2NR R ^8' , NO ₂ , C,-C ₈ alkyl, C ₂ -C ₈ alkenyl, C ₂ -C ₈ alkynyl, d-C ₈ haloalkyl, C ₂ -C ₈ haloalkenyl, C ₃ -C ₈ cycloalkyl, phenyl, phenyl(C C ₈ alkyl)-, phenyl(C ₂ -C ₈ alkenyl)-, phenyl(C ₂ -C ₈ alkynyl)-, OR ⁸ , COR ⁸ , COOR ⁸ , CONR ⁸ R ^8' , NR ⁸ R ^8" , SR ⁸ , SOR ⁸ , SOjR ⁸ , C,-C _β alkyl-OR ⁸ , C ₂ -C ₈ alkynyl-OR ⁸ or C ₂ -C ₈ alkenyl-OR ⁸ or, where appropriate, oxo or imino; wherein R ⁸ is as defined above;

Q is a group of general formula Ha or lib:

Ha lib wherein R ¹ and R ² are as defined above and R ⁴ and R ⁵ are as defined below; alternatively, R ³ may be a group R ¹⁰ -W(R ¹⁰ Q) ₂ ; wherein W is as defined above for Y except that it is a divalent rather than a divalent linking group; each of R ⁴ , R ^4' , R ⁵ and R ^5' is, independently, hydrogen, CO ₂ R ⁹ , COR ⁹ , CONR ⁹ R ⁹ , CO ₂ X, COX, SO ₂ X or CONHX; each R ⁹ and R ^9* is, independently, hydrogen, Cι-C ₈ alkyl, C ₂ -C» alkenyl, C _r C ₈ haloalkyl or C ₂ -C ₈ haloalkenyl and X is as defined above; or a tautomer, salt, metal complex or other derivative thereof; as the active ingredient in a herbicidal composition.

It will be understood that when at least one of R ⁴ and R ⁴ and at least one of R ^s and R ⁵ is hydrogen, the compounds of general formula la and lb are tautomers of one another.

There are, in addition, other possible tautomers of compounds of formulae la and lb and the tautomeric form adopted may depend upon the substituents on the molecule, the physical environment in which the molecule exists or, indeed, other factors.

As used herein, the term "Ci- alkyl" refers to a straight or branched saturated hydrocarbon chain having up to 6 carbon atoms. Examples of these groups include methyl, ethyl, n-propyl, iso-propyl, t-butyl and n-hexyl. The terms "C,-C ₂ o alkyl" and "d-C ₈ alkyl" should be construed in a corresponding manner.

As used herein "C2-C6 alkenyl" refers to straight or branched hydrocarbon chain having up to 6 carbon atoms and at least one double bond. Examples of such groups include ethenyl, 1-propenyl and 2-hexenyl. References to "C ₂ -C ₂ o alkenyl" and "C ₂ -C ₈ alkenyl" should be construed in a corresponding manner.

As used herein "C2- alkynyl" refers to straight or branched hydrocarbon chain having up to 6 carbon atoms and at least one triple bond. Examples of such groups include ethynyl, 1-propynyl and 2-hexynyl. References to "C ₂ -C ₂₀ alkynyl" and "C ₂ -C ₈ alkynyl" should be construed in a corresponding manner.

As used herein the term "halo" includes fluoro, chloro, bromo and iodo. Herbicidally acceptable salts of the compounds include salts of a mineral acid, for example, a salt of a haloacid (such as a hydrochloride, hydrobromide or hydroiodide) or of phosphoric, hexafluorophosphoric, nitric, sulphuric tetrafluoroboric or carbonic acid. Other herbicidally acceptable salts are salts of organic acids, for example acetic, trifiuoroacetic, maleic, malonic, oxalic, gluconic, succinic, fumaric, butyric, mandelic, tartaric, citric, salicylic, sorbic, lactic or sulphonic (such as p-toluenesulphonic, 1,5-naphthylidenesulphonic or camphorsulphonic) acid or fatty acids. Saccharin salts have also proved to be useful compounds in many cases. Salts of the compounds of the present invention are, indeed, particularly important as salt formation can, in some cases, significantly affect the herbicidal activity of the compounds.

Metal complexes include complexes with, for example, copper, silver, iron(II), iron(m), nickel or zinc although compounds of formulae la and lb will also form complexes with many other metals. Heterocyclic rings are preferably 5- or 6-membered rings containing one or more of the same or different heteroatoms (especially nitrogen, oxygen or sulphur). Examples of heterocyclic ring systems include furan, pyrrole, thiophene, imidazole, oxazole and triazoles

(such as 1,2,4-triazole) and their partially and fully saturated analogues, pyrimidine and triazines (such as l,2-dihydro-l,3,5-triazine).

The fused ring system may be an aromatic ring system such as naphthalene, anthracene and phenanthrene as well as partially saturated systems such benzocyclohexane and fully saturated systems such as dicyclohexane, tricyclohexane, norbornane and adamantane.

Alternatively, the fused ring system may contain fused heterocyclic rings or carbocyclic rings fused to heterocyclic rings. Examples of this type of ring system include benzimidazole, benzofuran, benzopyrrole, quinoline and benzopyrrolidone.

The compounds of formulae la and lb are active against a broad range of weed species including monocotyledonous and dicotyledonous species. They show some selectivity towards certain species; they may be used for example as selective herbicides in rice, maize and cereals, particularly wheat, and also in some broad leaf crops such as sugar beet.

The compounds of the present invention are suitable for use in herbicidal compositions which may be either for pre-emergence or post-emergence application. Therefore, in a second aspect of the present invention, there is provided a herbicidal composition comprising a compound of general formula la or lb together with a herbicidally acceptable diluent or carrier.

The compounds of formulae la and lb may be applied directly to the plant (post-emergence application) or to the soil before the emergence of the plant (pre-emergence application). However, the best activity has been obtained when they are applied post-emergence.

As already mentioned above, the herbicidal activity of the compounds is particularly surprising in view of the work carried out by the authors of US 5,300,503. In this document, various compounds were tested against tobacco budworm on chickpea plants and against cabbage looper on pinto bean plants and the test plants were subsequently examined for phytotoxic effects. However, no indication of any phytotoxicity is given in US 5,300,503 which suggests to the reader that the compounds were not observed to be phytotoxic. This is particularly surprising given that the authors of the prior art document appear to be using doses of the compounds similar to those which have been found by the present inventors to be herbicidally active.

Specific examples of compounds of formulae la or lb having herbicidal activity are listed in Tables I to HI. In Tables I to HI, where there are two substituents given for R ⁴ or R ⁵

(for example when R ⁴ or R ^s is (MeCO ₂ ) ₂ ), this indicates that the compound is of formula

Ib(i), Ib(ii) or Ib(iii) in which neither of the pair R ⁴ or R ⁴ or the pair R ⁵ or R ⁵ (as appropriate) is hydrogen.

In Tables I to DI, the following abbreviations are used:

Me methyl i-Pr isopropyl

Et ethyl n-Bu n-butyl n-Pr n-propyl t-Bu t-butyl

Q ¹ refers to tautomers of general formula:

Q refers to tautomers of general formula:

Table I relates to compounds having the general formulae Ia(i) and Ib(i):

Ia(i) Ib(i) in which R ¹ , R ² , R ⁴ and R ⁵ are as defined in general formulae la and lb; m is an integer from 0 to 20; and

R ²⁰ is halo, OR ⁶ , COR ⁶ , COOR ⁶ , CONR^ ⁷ , NR ⁶ COR ⁷ , NR ⁶ R ⁷ , NR ⁶ SO ₂ R ⁷ , SR ⁶ , SOR ⁶ ,

SO ₂ R ⁶ , OCOR ⁶ , N ₃ , NO ₂ , cyano, SOjNRV, C=NOR ⁶ , CSNRV, NR ⁶ CON R ⁷ R ^7' , OCO ₂ R ⁶ ,

OCONR ⁶ R ⁷ , NR ⁶ CO ₂ R ⁷ , NR ⁶ CON R ⁷ R ^7' , a group X or an optionally substituted C,-C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₃ -C ₈ cycloalkyl or (C ₃ -C ₈ cycloalkyl)C ₁ -C ₈ alkyl group, wherein the optional substituents are chosen from COR ⁶ , COOR ⁶ , OR ⁶ , cyano, halo, oxo, SO ₂ R ⁶ , CONR ⁶ R ⁷ or a group X; (wherein R ⁶ , R ⁷ and X are as defined in general formulae la and lb).

TABLE I

I

I

Table I contd.

Comp. Salt m R ⁴

1.47 1.48 HBr 1.49 1.50 1.51 I 52

1.53

1.54 1.55

I

I

R ¹ m -.-» R»

Me Me H Me Me H Me Me H Me Me H Me Me H Me Me H Me Me H Me Me H Me Me H

CΛ Me Me H

<_*-> Me Me H Me Me H O Me Me H I

CΛ Me Me H Me Me H Me Me H Me Me H Me Me H ro 3 Me Me H Me Me H Me Me H Me Me H Me Me H Me Me H Me Me H Me Me H Me Me H Me Me H

COO-n-Pr H H

COOCH ₂ C _β H _B H H

N-p thalimido H H

N-phthalimido H H

N-phlhalimido H H

N(COMe)C _β H.

COO-(2-CF ₃ -C _β H ₄ ) H H

COO(4-CF ₃ 0-C _β H ₄ ) H H en COOCH(Me) ₂ H H

COO(2-CI-4-CF ₃ -C _β H ₃ ) H H

-Α ethynyl H H

COO(cyclohexyl) H H

COOCH ₂ (4-α-C _β H ₄ ) H H

CΛ COOCH ₂ (4-F-C ₆ H ₄ ) H H

COO(4-CF ₃ -C _β H ₄ ) H H

4-(3-CF ₃ -C _β H )pipβrazin-1-yl H H

N(COMe)-C _β H _B H H ro CH=CH ₂ H H

3 0(CO)C _β H _B H H

0(CO)NHC _β H ₅ H H

COOCH ₂ (2,4-dμF-C _β H ₃ ) H H

C

COOCH ₂ (4-F-C _β H ₄ ) H H

I t

R ⁵

COOCH ₂ (2,θ- μF-C _β H ₃ ) H H

CH(CH ₃ )CONH(2,β-dl-F-C _β H ₃ ) H H

CH(CH ₃ )CONH(3,5-di-CI-C _β H ₃ ) H H

CH(CH ₃ )CONH(2,β- i-CI-C _β H ₃ ) H H

COO-μpr H H

Adamantyt-CO H H

4,4-dimethylpent-2-yl H H

0(CO)Me H H triphenylphosphonium bromide H H

COOEt H H

COOEt H H cyclohexyl H H

(Z-1-methoxy-2-ethoxycart)oπyl- H H UJ vinyl)

CΛ

CN H H

CN H H vinyl H H

1.3-Dioxan-2-yl H H rv_» 0(CO)Me H H

0(CO)Et H H

0(CO)-n-Pr H H

OMe H H

OEt H H

O-n-Pr H H

OCH ₂ CH=CH ₂ H H

0(CO)C,H _B H H

0(CO)OMe H H

0(CO)OEt H H 0(CO)OC _β H _β H H

Table I contd.

Salt m

Me Me 6 0(CO)OCH ₂ C _β H ₅ H H Me Me OH H H Me Me 0(CO)Me H H Me Me 0(CO)Et H H Me Me 0(CO)-n-Pr H H Me Me OMe H H Me Me OEt H H Me Me O-n-Pr H H Me Me OCH ₂ CH=CH ₂ H H Me Me 0(CO)C _β H _B H H Me Me 0(CO)OMe H H Me Me 0(CO)OEt H H -t-> Me Me 0(CO)OC _β H _β H H i Me Me 0(CO)OCH ₂ C _β H ₅ H H Me Me 9 OH H H Me Me 9 0(CO)Me H H Me Me 9 0(CO)Et H H Me Me 9 0(CO)-n-Pr H H Me Me 9 OMe H H Me Me 9 OEt H H Me Me 9 O-n-Pr H H Me Me 9 OCH ₂ CH=CH ₂ H H Me Me 9 0(CO)C _β H _B H H Me Me 9 0(CO)OMe H H Me Me 9 0(CO)OEt H H Me Me 9 0(CO)OC _β H _B H H Me Me 9 0(CO)OCH ₂ C _β H _B H H Me Me 11 OH H H Me Me 11 0(CO)Mθ H H

XXXXXX X XXI I IXXXXIII I III X IIIIX

XXIXXX X XII I XXIXXIXX X XII X XXXXX

CO CO CO CO CO O O O O CO CO CO O

Φ ^9 49 49 Φ 49 49 Φ Φ 49 ^9 Φ 49 49 49 49 49 49 ^9 49 49 Φ 49 49 49 49 49 49 49

222222222222222222222222 22222

Φ Φ Φ Φ Φ Φ φ Φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ

22222222222222222222222222222

_» n W <D _N ( ₀ β _O τ _' (M < ^, . * !S β t; S 2 O *- N β cM CM CM CM CM CM CM CO CO C CO C CO C CO O 'J J- 'J π CM CM CM CM CM CM CM CM CM CM CM CM CM -M CM CM -M C CM CM

σ

I

I I I IIII X X X X XX I XXXX X X XXI X X

X X X XXII X X I X XX X XXXI X X XXX X X

E ι- -»- ι- CM CM CM O O O O O ι- CM CM CM CO CO CM CM

49 Φ 49 49 49 Φ Φ Φ 49 Φ 49 ^9 49 Φ Φ Φ I Φ Φ Φ Φ

2222222222222 222 P 2222 f. 2 £ I υ υ

£ i*. υ I υ

I υ

Φ Φ Φ Φ Φ Φ φ φ φ Φ φ φ Φ φ Φ Φ Φ Φ x Φ Φ Φ Φ Φ

2222222222222222 P 2222 2

Table II relates to compounds of general formulae Ia(ii) and Ib(ii):

in which R ¹ , R ² , R ⁴ and R ⁵ are as defined in general formulae la and lb;

L ¹ is H, C.-C ₆ alkyl, C ₂ - alkenyl, -C* alkynyl, C,-C ₆ haloalkyl, halo, OR ⁶ , COR ⁶ , COOR ⁶ , CONR ⁶ R ⁷ , NR ⁶ COR ⁷ , NR ⁶ R ⁷ , NR ⁶ SO ₂ R ⁷ , SR ⁶ , SOR ⁶ , SO ₂ R ⁶ , OCOR ⁶ , N ₃ , NO ₂ , cyano, SO ₂ NR ⁶ R ⁷ , CSNR^ ⁷ , NR ⁶ CON R ⁷ R ^7' , OCO ₂ R ⁶ , OCONRV, NR ⁶ CO ₂ R ⁷ , NR ⁶ CONR ⁷ R ^7' or a group X; and each of L ² to L ⁶ independently represents hydrogen, cyano, halo, SO ₂ NR ⁸ R ⁸ , NO ₂ , C[-C ₈ alkyl, C ₂ -C ₈ alkenyl, C ₂ -C ₈ alkynyl, C C ₈ haloalkyl, C ₂ -C ₈ haloalkenyl, C ₃ -C ₈ cycloalkyl, phenyl, phenyl(C|-C ₈ alkyl)-, phenyl(C ₂ -C ₈ alkenyl)-, phenyl(C ₂ -C ₈ alkynyl)-, substituted phenyl(Cι-C ₈ alkyl)-, substituted phenyl(C ₂ -C ₈ alkenyl)-, substituted phenyl(C ₂ -C ₈ alkynyl)-, OR ⁸ , COR ⁸ , COOR ⁸ , CONR ⁸ R ^8" , NR ⁸ R ⁸ , SR ⁸ , SOR ⁸ SO ₂ R ⁸ , C,-C ₈ alk l-OR ⁸ , C ₂ -C ₈ alkynyl-OR ⁸ or C ₂ -C ₈ alkenyl-OR ⁸ (wherein R ⁶ , R ⁷ , R ⁸ and suitable substituents for phenyl groups are all as defined for general formulae la and lb); or, alternatively, two groups L ² to L ⁶ may together form a further saturated or unsaturated carbocyclic or heterocyclic ring.

In Table π, Compound π.34, the sub-structure:

is as follows:

TABLE π

L ¹

H H H H H H H H

H H H I H H H

H H H

H H H H H H H H

/15671

X I I I I IXXIIX X X I I X

x x x x xxx* XI xxx x i x xx xx xxi xx

1ι X X x x x xxx * XX xl φx i x x ix xx ϋxx xx

E

X X X X X XXXXXX XXX X X X XX XX XXX XI

Φ Φ Φ Φ Φ Φ Φ φ Φ φ φ φ φ -*^ 4M φ Φ φ Φ Φ φ Φ Φ Φ φ Φ

2 2 2 2 2 222222 22-^.^ 2 2 22 22 222 22

Φ m Φ (p m qj cø αj qj QJ Ql αV ID ID ID O flJ V 0 (0 V O V- W W W W

2 2 2 2 2 222222 222 2 2 2 22 22 222 22

O

Ic § x xxx XXX XXXXX X XIXXXXXXXXXX X I

^C § X X XI II XXIIIX X I IIIIXXIIII XX

"~ι x x x x ϋ o o o δ ϋ o P ϋ x δ 11 δ x x x δ I x x x

^• J x x x xx ixx m x i n xxii ώ-nxδx x δ

i II- δδxxii nx I δ x δ δ δ x x x x δ x J ^x P

I

9 I υ II

I

°x xδδxxxin x x x i δ δ 11 δ x δ x § δ x

1ι m x xx x δ o o o o o o δ δ δ o x x ^x " o x

^x I | i2ffiϋjxx χxι xx

M Φ Φ _« -__-- _» φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ

K 2 22«" 22222222 2 - _S 2222222222222

_• » Φ Φ Φ Φ ^™ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ Φ Φ Φ Φ Φ t~ 2222X22222222 2 22222222222222

0 - C10M n lo-iVoIiOβΦiα N loβioOioOβro- Noβno ^ι c ⁿ o O offlffl ^{β β} fflOss- ⁽ s. (s>) ^* * ιsn ^β NN ^β ^ ^β n

xxxxxxxxxxx

O O

I I I IXXIX X IIXXXI P φ υ O φ y,ιnι XXIIII

2 2

^j i x x xxii i III I I ZtLlLIL UL U. |xιι

I I I IIIII X XXIXXIX X IU.U.χχχχχχXϋδ

~ ^j X θ I 2 ~ Tt3Tl 2IXXX I IULU.XXIXXIIII

°o §χ uoiiiiii I I u o. IU.1 u.xιnδ δ

x x x I|ΣZOI ∑∑SILU.|Z iϋu-»-ϋϋ ϋ-i-iϋϋi

X I I III^X I XXI r. ^ ^. ^ ^. ^. ^ -. _m mi - . i 'ml B O O tD

III X X XXXX 22222

Ψ4 Φ Φ Φ Φ φ φ φ Φ Φ Φ Φ φ φ Φ Φ φ φ φ Φ φ φ φ φ φ φ Φ φ

K 222222222222222-2222222222 222

—~ Φ φ φ φ φ Φ Φ φ φ Φ Φ Φ Φ Φ φ φ φ Φ φ Φ Φ φ Φ Φ Φ Φ Φ

K 2222222222222222222222222 222

α m mmmmmoou moωoυδδoooo co x xxxxxxxx xxxxxxxxxxx

_ 0 -- CM CO «-r -O CO I«_ 00 0.0 --- CM CO -J IO O N g ^β t- CM co -* ι co " β o co co co co 00 co 00 co co co co o) co o> a a) co α α> α α o o o o α α o

R ² L ⁴ R ⁴ R ^§

H H

H H H H H H σσ H H

N. H H Λ H H H c JO: H ro H H H H

r _rΛ π

5 ^" 53 ro 33

Table m relates to compounds of general formulae Ia(iϋ) and Ib(iii):

Ia(ui) Ib(ϋi) in which R ¹ , R ² , R ⁴ and R ³ are as defined form general formulae la and lb; L ² to L* are as defined for general formulae Ia(ϋ) and Ib(ii) above; n is an integer of 0 to 20;

W is Cι-C« alkyl or Cr alkenyl, either of which may optionally be substituted with halogen or cyano;

V is O, S, NH, N(C,-C ₄ )alkyl or N(C ₃ -C,)cycloalkyl; and p is 0 or 1.

≡ ≡ ≡ z o o -> M M M M N W M W M N ___, L- m. -- -- -- -~ -~ -- -'. -. ,- [~_ er, r, ___. ώ M --. P

I III III I X x X X co CD CD GO 00 000009 00 CD 00 x CD CD σ> o 01

∑ ∑∑ ∑ ∑ ∑ ∑ z ∑ ∑ ∑ ∑ Σ φ φ φ φ φ φ φ φ φ φ φ - Σ t~ Σ f Σ ^ Σ jp Σ jp Σ fb Σ { Σ (p Σ ^p Σ (Q Φ Φ

<-» <__ __- B uα CD OB t- u β αiu u M μ _) (_ u w w M C* ->

O

I

• I I I I I I I I I I I I c f5) I ■ I I i i

I

_•__

O O O O O O O CO O CO O O O O O O O O O O O O O O O O O O O O <

z _^ -- ι i >» ι ιι=xxxιι = ιιιϊDftτ>ε5ι J 5 ι ^~ ,

X II I III r-

XXXXIXIIII II IIl llllXIII I IIII r-_

rn rπ πj X II I x o OO 3^

O O O

πj rπ πi I II II I III II I I II I I o O g 30,

O O O

- 92 - 9SI/960ΛV

S_.SZ0/S6aθ/XDcI

■β xxxxxxxi I XI II _{I I} II _XIX xxxx xxx χ OP _χ

^* -« ιιιιιιιιιιιιιιιι nι _II1I t _III1 S

^xxxx xxxxιxιxxιιxx ι ιιιxx ι

δ xι|| ι

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Although the compounds of general foπnulae la and lb have, as a class, been found to be active as herbicides, some of the compounds are particularly active.

Preferred compounds include those in which, independently or in any combination:

R ¹ and R ² are each, independently, methyl or ethyl or R ¹ and R ² together form a cyclopentyl or cyclohexyl ring optionally substituted with a methyl group;

R ³ is C,-C, ₅ alkyl optionally substituted with halo, OR ⁶ , COR ⁶ , COOR ⁶ , SR ⁶ , NR ⁶ R ⁷ , OCOR ⁶ or a group X as defined for general formulae la and lb;

R ⁶ and R ⁷ are each, independently, hydrogen, Ci- alkyl, C ₂ -C6 alkenyl or a group X as defined for general foπnulae la and lb; Compounds which have particularly good herbicidal activity include: compounds in which R ³ is Cι-C _l2 alkyl optionally substituted with halo, OR ⁶ , COR ⁶ , COOR ⁶ , SR ⁶ , OCOR ⁶ or a group X as defined for general formulae la and lb;

R ⁶ is hydrogen, methyl, ethyl, n-propyl, isopropyl, ethenyl or 1-propenyl;

X is phenyl, cyclohexyl, cyclohexenyl, pyridyl or a fused aromatic or non-aromatic carbocyclic ring system; preferred optional substituents for X include cyano, halo, nitro, C.-C ₈ alkyl, C ₂ -C ₈ alkenyl, C,-C ₈ haloalkyl, C ₂ -C ₈ haloalkenyl, C ₃ -C ₈ cycloalkyl, phenyl, ρhenyl(Cι-C ₈ alkyl), phenyl(C ₂ -C ₈ alkenyl), OR ⁸ , COR ⁸ , COOR ⁸ , SR ⁸ , C C ₈ alkylOR ⁸ or C ₂ -C ₈ alkenylOR ⁸ ; other particularly preferred compounds include: compounds of general formula Ia(i) or Ib(i) in which m is from 1 to 3 and: when m is 1, R ²⁰ is a C ₁ -C ₄ alkyl group substituted with a phenyl group or with a phenyl group having from 1 to 5 substituents chosen from halo or C C ₄ alkyl; when m is 2, either R ²⁰ is a C ₁ -C ₄ alkyl group substituted with a phenyl group or with a phenyl group having from 1 to 5 substituents chosen from halo or Cι-C ₄ alkyl or R is a phenyl group having from 1 to 5 substituents chosen from halo or C*-C ₄ alkyl; when m is 3, R ²⁰ is a phenyl group having from 1 to 5 substituents chosen from halo or C1-C4 alkyl; compounds of general formula Ia(ϋ) or Ib(ii) in which L ² to L ⁶ are hydrogen, halogen or C ₁ -C4 alkyl; and compounds of general formula Ia(ϋi) or Ib(iii) in which n is 2 or 3, V is O and L to L are hydrogen, halogen or C1-C4 alkyl.

Specific examples of particularly preferred compounds include:

l-[6-(3,4,5-trimemoxvphenoxy)hexyloxy]-2,2---d__methy^ triazine (Compound 111.67, Example 1); l-[10-hydroxydecyloxy]-2,2- _imethyl-4,6-diamino-l,2- dihydro-l,3,5-triazine (Compound 28, Example 2); 1 -[2-(2,4-dichlorophenyl)prop- 1 -yloxy]-2,2-dimethyl-4,6-diamino- 1 ,2-dihydro- 1 ,3,5-triazine

(Compound 1.64, Example 3);

1 -[ 1 -(2,6-dichlorophenyl)ethoxy] -2,2-dimethyl-4,6-diamino- 1 ,2-dihydro- 1 ,3 ,5-triazine

(Compounds H.57-II.65, Examples 4 and 6); l-[2-cMoro-3,6-d_fluorobenzyloxy]-2,2-dimethyl-4,6-diamino-l ,2-dihydro-l,3,5-tria2ine (Compounds EL 100 and π.101 , Example 5); l-[3-(4-bromophenoxy)-propoxy-]-2,2-dimethyl-4,6-diarnino-l, 2-dihydro-l,3,5-triazine

(Compound m.105, Example 8); l-[3-(2,4,5-tricUorophenoxy)-propoxy-]-2,2-dimethyl-4,6-diai nino-l,2*<iihydro-l,3,5-triazine

(Compound m.72, Example 9); l-[6^(3,4,5-_r___nethoxyphenoxy)hexyloxy]-2,2-dimethyl-4,6-b is-(acetamido)- 1 ,2-dihydro-

1,3,5-triazine (Example 10);

1 -( 10-Hydroxydodecyloxy)-2,2-dimethyl-4,6-diamino- 1 ,2-dihydro- 1 ,3,5-triazine hydrobromide (Example 11); l-[3* 4-bromophenoxy)-propoxy]-2,2-dimethyl-4,6-diamino- 1 ,2-dihydro- 1 ,3,5-triazine (Compound m.105);

1 -[3-(2-<thoxvphenoxy)propoxy]-2,2-dimethyl-4,6-diamino- 1 ,2- dihydro- 1 ,3,5-triazine

(Compound DI.10); l-[l-(2,4-dicUorophenyl)ethoxy]-2,2-dimethyl*4,6^diammo-l,2- dihydro-l,3,5-triazine

(Compound π.66); 1 -[2,6-dichloroberizyloxy]-2,2-d_methyl-4,6-diamino- 1 ,2-dihydro- 1 ,3,5-triazine (Compound π.67); l-[l-(3,4-dichlorophenyl)ethoxy]-2,2-dimethyl-4,6-diamino-l, 2-dihydro-l,3,5-triazine

(Compound π.68);

1 -[ 1 -(2,6-dichlorophenyl)prop- 1 -yloxy]-2,2-dimethyl-4,6-diamino- 1 ,2-dihydro- 1 ,3,5-triazine (Compound π.71);

1 -[2-(2,4-dichlorophenyl)prop- 1 -yloxy]-2,2-dimethyl-4,6-diamino- 1 ,2-dihydro- 1 ,3,5-triazine

(Compound 1.64);

1 -[2-(2,4^cMorophenyl)ethoxy]-2,2-dimethyl-4,6-diamino- 1 ,2-dihydro- 1 ,3,5-triazine

(Compound 1.65);

H2-cMoro-6-fiuorobenzyloxy]-2,2--<_timethyl-4,6-^

(Compound H92); l-[2,6HMuorobenzyloxy]-2,2-d_methyl-4,6-diaπύno-l^- Khydro-l,3,5-tri__zine (Compound

l-[2,4,6-trimethylbenzyloxy]-2,2-*dimetoyl- ,6-- tiaπM^

(Compound D 94); l-[2-(2,6- lichlorophenyl)ethoxy]-2,2-dimethyl-4,6-diaπ-ino-l,2-^ihydr o-l,3,5-triazine (Compound 1.73); l-[2-(2,4,6^trimethylphenyl)ethoxy]-2,2* iimethyl- ,6-<_iamino- 1 ,2-dihydro- 1 ,3,5-triazine

(Compound 1.74);

1 -[2-(2,3-dichlorophenyl)ethoxy]-2,2-dimethyl-4,6-diamino- 1 ,2-dihydro- 1 ,3 ,5-triazine

(Compound 1.75); l-[2,3,4,5,6-pentafluorobenzyloxy]-2,2Hiimethyl-4,6-dianώι o- 1,2-dihydro- 1 ,3,5-triazine

(Compound π.99); l-[2,6-dimemylben2yloxy]-2,2-dimethyl*4,6-diammo-^ _^ π.102); l-[2-(2,4-difluorophenyl)ethoxy]-2,2-dimethyl-4,6-diamino- 1 ,2-dihydro- 1 ,3,5-triazine (Compound 1.76); l-[2-(4-isopropylbenzyl)prop- 1 -yloxy]-2,2-dimethyl-4,6-diamino- 1 ,2-dihydro- 1 ,3,5-triazine

(Compound 1.77); l-[2-(2,4-difluorophenyl)prop- 1 -yloxy]-2,2-<limethyl-4,6-diamino- 1 ,2-dihydro- 1 ,3,5-triazine

(Compound 1.78); l-[2-(2-cMoro-6-fluorophenyl)ethoxy]-2^-dimethyl-4,6-diamino - 1 ,2-dihydro- 1 ,3,5-triazine

(Compound 1.79);

1 -[ 1 -(2*<Woro^-fluorophenyl)ethoxy]-2,2- iimethyl-4,6-diamino- 1 ,2-dihydro- 1 ,3,5-triazine

(Compound π.103); l-[ 1 -(2,6-difluorophenyl)ethoxy]-2,2-dimethyl-4,6-diamino- 1 ,2-dihydro- 1 ,3,5-triazine (Compound π.104); l-[ 1 -(2,6-dimethylphenyl)ethoxy]-2,2-dimethyl-4,6-diamino- 1 ,2-dihydro- 1 ,3,5-triazine

(Compound π.105);

1 -(2-(2,6*<lifluorophenyl)etlιoxy]-2,2- _imethyl-4,6-ωamino- 1 ,2-dihydro- 1 ,3,5-triazine

(Compound 1.80); l-[2-phenoxyethoxy]-2^-dimethyl-4,6-diamino- 1 ,2-dihydro- 1,3,5-triazine (Compound

l-[l-(2,3-dicωorophenyl)ethoxy]-2,2*^methyl- ,6- Uarmno-l,2- ulιyd_ro-l,3,5-triazine

(Compound π.106);

1 - [ 1 -(2,5-dichlorophenyl)ethoxy ]-2,2-dimethyl-4,6-diamino- 1 ,2-dihydro- 1 ,3,5-triazine

(π.107); l-[2-(2,6- licMorophenyl)prop-l-yloxy]-2,2-dimemyl-4,6-diamino-l,2-dihy dro-l,3,5-triazine (Compound 1.83) l-[ l-(3,5-dichlorophenyl)ethoxy]-2,2-dimethyl-4,6-diamino- 1 ,2-dihydro-l ,3,5-triazine

(Compound π.108); l-[3-isopropyl-6-methylbenzyloxy]-2,2- limethyl-4,6^diamino- 1 ,2-dihydro-l ,3,5-triazine

(Compound π.6); l-[8-(4-methoxyphenoxy)octyloxy]-2,2-d_methyl- ,6-di.unino-l,2-dihydro-l,3,5-triazine

(Compound m.28); l-[3-(4-ethyl-6-propen-3-ylphenoxy)propoxy]-2,2-dimethyl* ,6-diamino-l,2* i_hyc_ro-l,3,5- triazine (Compound m.42); l-[3-(4-acetyl-6-propen-3-ylphenoxy)propoxy]-2,2-dime yl-4,6-diamino-l,2-dihydτo-l,3,5- triazine (Compound ϋl.43); l-[ 10-(2-ethoxycarbonylphenoxy)decyloxy]-2^- iimethyl-4,6-diamino- 1 ,2-dihydro- 1 ,3 ,5- triazine (Compound m.46); l-[3-(4-cUoro-^propylphenoxy)propoxy]-2,2- limemyl-4,6^--inino- 1 ,2-dihydro- 1 ,3,5- triazine (Compound IQ.50); l-[3-(4-eΛyl-6-propylphenoxy)propoxy]-2,2--*dimethyl^

(Compound DI.51); l-[3-(4-chlorophenyl)propoxy]-2,2-dimethyl-4,6-diamino- 1 ,2-dihydro- 1 ,3,5-triazine

(Compound 1.5); l-[3-(4-methoxyphenyl)propoxy]-2,2-dimethyl-4,6-diamino- 1 ,2-dihydro- 1 ,3,5-triazine (Compound 1.7); l-[3-(4-n-propyloxycaΛonylphenyl)propoxy]-2,2* hmethyl-4,6-κiiamino-l,2-dihydro-l,3,5- triazine (Compound III.54);

l-undecyloxy-2,2- limethyl-4,6-α_amino-l,2- iihydro-l,3,5-triazine (Compound 1.22); l-[3-(3,4^c orophenyl)prop-l-yloxy]-2,2-<iimeΛyl^

(Compound 1.44); l-[10-proρanoyldecyloxy] ]-2^-dimethyl 6κϋamino-l,2-dihydro-l,3,5-triazine (Compound 1.48); l-[3-(4-me±oxyphenoxy)propoxy]-2^-dimemyM,6^ammo-l,2-dihydr o-l,3,5-triazine (Compound 111.92) and their salts and derivatives.

As already mentioned above, the salts or metal complexes of the compounds of the present invention may be significantly different in their herbicidal activity from the parent compounds.

Some of the compounds of formulae la and lb are new and, therefore, in a third aspect of the invention there is provided a compound of general formula Ia(i) or Ib(i) as defined above, provided that:

R ²⁰ is not H, hydroxy, Q, OQ, trifluoromethylphenyl, 4-chlorophenyl, 2,3- dichlorophenyl, 3,4-dichlorophenyl, 2,4,5-trichlorophenyl, methoxyphenyl, chloro, NR^ ⁷ , phenylhaloalkyl or (halo phenyl)alkenyl; when R ¹ and R ² are both methyl, R ²⁰ is not phenyl, phenylalkenyl, cyclohexyl, 2,3- dichlorocyclohexyl, pyrid-4-yl or CHCICOOH; and when m is 1, R ²⁰ is not cyclohexenyl. to a further aspect of the invention, there is provided a compound of formula Ia(ii) or

Ib(ii), provided that: when one of L ² to L ⁶ is hydrogen, trifluoromethyl, nitro, phenyl, alkoxy, cyano, methyl, phenoxy, phenyl, Q-CH ₂ -phenyl or Q-CH ₂ -phenoxy, the others of L ² to L ⁶ are not all hydrogen; when L is hydrogen and one of L ² to L ⁶ is chloro, the others of L ² to L ⁶ are not all hydrogen; when R ⁴ and R ⁵ are both H or (MeCO) ₂ , then none of L ² and L ³ or L ³ and L ⁴ or L ⁴ and L ^s together form -CH=CH-CH=CH-, naphtho or -O-CH ₂ -O-CH ₂ -O-; when R ¹ and R ² are both methyl, R ⁴ and R ⁵ are both hydrogen and L ² is other than chloromethyl, then no two of L ³ to L ⁶ are chosen from chloro, bromo or alkoxy; and when L ³ is chloro or nitro, then L ⁴ is not methyl.

In a further aspect of the invention, there is provided a compound of fomula Ia(iii) or Ib(iii) as defined above, provided that: none of L ² to L ⁶ is cyclohexyl; no two of L ² to L ⁶ form a group -CH=CH-CH=CH-; L ⁴ is not nitro; when n is other than 1, V is O and R ⁴ and R ⁵ are both hydrogen, then L ² , L ⁴ and L ⁵ are not all chloro; when n is 2, L ² and L ⁴ are not both chloro; when n is 2 and V is O, L ³ and L ⁴ are not both chloro; when n is 2, L ³ and L ⁵ are not both methyl; when n is 2 and L ³ is methyl, L ⁴ is not chloro; when n is 3 and L ⁴ is hydrogen, L ³ and L ⁵ are not both methyl; when n is 3 and V is NH, L ² and L ⁴ are not both chloro; when n is 3, L ² and L ⁵ are not both alkyl; and when n is 2 or 3 and four of L ² to L ⁶ are hydrogen, the other of L ² to L ⁶ is not halo or

COOR ⁸ .

In particular, compounds which are new include from Table I: 1.4, 1.8, 1.9, 1.10, 1.11, 1.12, 1.13, 1.14, 1.15, 1.16, 1.17, 1.18, 1.41, 1.42, 1.45, 1.46, 1.48, 1.52, 1.54, 1.56, 1.57, 1.63, 1.64, 1.65, 1.66, 1.68, 1.69, 1.70, 1.71, 1.72 and 1.173 to 1.303; from Table II: π.4, π.5, π.7, π.8, π.ιo, π.π, π.ιs, π.19, π.20, π.27, π.36, π.42, π.49, π.51, π.52, π.55, π.56, π.79, π.80, π.81, π.86 and H.87 to H.156; from Table HI: m.ι, m.2, m.3, m.6, m.7, m.8, m.9, m.10, m.11, .12, m.13, m.u, m.15, m.i6, m.i7, m.i8, m.19, m.20, m.21, m.22, m.23, m.24, m.25, m.26, m.27, m.28, m.29, m.30, m.3i, m.32, m.34, m.35, m.36, m.37, m.38, m.39, m.40, m.41, m.42, m.43, m.44, m.45, m.46, m.47, m.48, m.49, m.50, m.51, m.52, m.54, m.55, m.56, m.57, m.58, m.59, m.6θ, m.6i, m.62, m.63, m.64, m.65, m.66, m.67, m.68, m.69, m.70, m.76, m.86, m.87, m.89, m.90, m.92, m.93, m.94, m.95, m.96, m.97, m.98, m.99, m.i04, m.io9, m.110, m.111, m.112, m.113, m.ιi4, m.115, m.ιi6, m.117, m.ιi8

Many of the compounds of the present invention are known and may be prepared by methods identical or similar to those described in any of the following documents: GB831252, US3105074, GB945159, DE1813243, DE1934120, DE1963759, DE1965941, DE1965925, DE1965711, DE1957769, GB1250531, DE2107905, DE2116252, US3660394, US3682912 US5300503 or US4496549. Any modifications needed to the method in order to prepare analogues of the compounds disclosed in these documents would be well within the scope of those skilled in the art of synthetic organic chemistry.

However, in summary, compounds of general formulae la and lb or their tautomers wherein R and R are other than hydrogen, may be prepared from compounds of general formula la or lb wherein R ⁴ and R ⁵ are hydrogen by reaction with a compound of general formula LU.:

R ¹² -L m wherein R is as defined for R ⁴ and R ⁵ except that it is not hydrogen and L is a leaving group such as halo, particularly chloro or bromo.

Compounds of general formula la or lb in which R ⁴ and R ⁵ are both hydrogen may be prepared by the reaction of a compound of general formula IV:

rv wherein R and R are as defined in general formulae la and lb, or a salt thereof with a compound of general formula V:

R ³ -L V wherein R is as defined in general formulae la and lb and L is as defined above for general formula m. The reaction will typically be carried out in a polar solvent such as methanol, ethanol or N,N-dimethylformamide.

Compounds of general formula V are readily available or may be prepared by methods known to those skilled in the art.

Compounds of general formula TV may be prepared from compounds of general formula VI:

VI wherein R ¹ and R ² are as defined in general formulae la and lb, by catalytic hydrogenolysis using a catalyst such as palladium or platinum and will typically be conducted at room temperature and pressure in an alcoholic solvent.

Compounds of general formula VI may be prepared by reaction of a compound of formula VH:

vπ or one of its tautomers with a carbonyl compound of general formula Vm:

vm wherein R ¹ and R ² are as defined in general formulae la and lb. The reaction proceeds favourably under acidic conditions at the reflux temperature of the solvent used, which will often be an excess of the carbonyl compound of formula Vm, sometimes in mixture with an alcoholic solvent such as methanol or ethanol.

Carbonyl compounds of general formula Vm are readily available or may be synthesised by methods known to those skilled in the art.

The compound of general formula Vπ may be prepared by the reaction of O-benzylhydroxylamine with dicyandiamide, both of which are readily available. In an alternative approach, a compound of formula DC:

R ³ -ONH ₂ IX wherein R ³ is as defined above for general formulae la and lb, may be used in place of O-benzylhydroxylamine in the initial reaction with dicyandiamide and the product reacted with a compound of general formula V under the conditions described above to give the desired product of general formula la or lb in which R ⁴ = R ⁵ = H.

The rate of application of the compounds of the invention will depend on a number of factors including, for example, the particular compound of general formulae la or lb which is used, the identity of the plants whose growth is to be inhibited, the formulations selected for use and whether the preparation is to be applied for foliage or root uptake. As a general guide, an application rate of from 0.001 to 20 kilograms per hectare of the compound of general formula la or lb is suitable while from 0.025 to 1 kilogram per hectare, particularly 0.125 to 1 kilogram per hectare, may be preferred.

The compounds of the present invention may be applied to the plant alone but, s mentioned above, they will more usually be formulated as a herbicidal composition containing a herbicidally acceptable diluent or carrier. The diluent may be a solid or liquid diluent.

The compositions may be either dilute preparations, which are ready for immediate use, or concentrated preparations, which must be diluted before use, usually with water.

Preferably the compositions contain from 0.01% to 90% by weight of the active ingredient(s). Dilute compositions ready for use preferably contain from 0.01 to 2% of active ingredients), while concentrated compositions may contain from 20 to 90% of active ingredients), although from 20 to 70% is usually preferred.

Solid compositions may be in the form of granules, or dusting powders wherein the active ingredients are mixed with a finely divided solid diluent, e.g. kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia, Fuller's earth and gypsum. They may also be in the form of dispersible powders or grains, comprising a wetting agent to facilitate the dispersion of the powder or grains in liquid. Solid compositions in the form of a powder may be applied as foliar dusts.

Liquid compositions may comprise a solution or dispersion of the active ingredients in water optionally containing a surface-active agent, or may comprise a solution or dispersion of the active ingredient(s) in a water-immiscible organic solvent which is dispersed as droplets in water.

Surface-active agents may be of the cationic, anionic, or non-ionic type or mixtures thereof. Examples of cationic agents include quaternary ammonium compounds (e.g. cetyltrimethylammonium bromide). Suitable anionic agents are soaps; salts of aliphatic mono ester of sulphuric acid, for example sodium lauryl sulphate; and salts of sulphonated aromatic compounds, for example sodium dodecylbenzenesulphonate, sodium,calcium, and ammonium lignosulphonate, butylnaphthalene sulphonate, and a mixture of the sodium salts of

diisopropyl and trϋsopropylnaphthalenesulphonic acid. Suitable non-ionic agents are the condensation products of ethylene oxide with fatty alcohols such as oleyl alcohol and cetyl alcohol, or with alkylphenols such as octyl- or nonyl- phenol (e.g. Agral 90) or octyl-cresol. Other non-ionic agents are the partial esters derived from long chain fatty acids and hexitol anhydrides, for example sorbitan monolaurate; the condensation products of the partial ester with ethylene oxide; the lecithins; and silicone surface active agents (water soluble surface active agents having a skeleton which comprises a siloxane chain e.g. Silwet L77). A suitable mixture in mineral oil is Atplus 41 IF.

In some cases, the formulation may affect the herbicidal activity of the compound and, in the present case, it has been found that compositions containing polyethylene glycol and silicone surface active agents are particularly effective. Examples of such compositions would contain from about 0.5 to 5%, more usually 1.5 to 2.5%, polyethylene glycol (typically PEG 200) and from 0.05 to 2%, more usually 0.1 to 1% of an adjuvant such as that sold under the trade mark Atplus 204). Aqueous solutions or dispersions may be prepared by dissolving the active ingredient(s) in water or an organic solvent optionally containing wetting or dispersing agent(s) and then, when organic solvents are used, adding the mixture so obtained to water optionally containing wetting or dispersing agent(s). Suitable organic solvents include, for example, ethylene dichloride, isopropyl alcohol, propylene glycol, diacetone alcohol, toluene, kerosene, methylnaphthalene, the xylenes and trichloroethylene.

Compositions for use in the form of aqueous solutions or dispersions are generally supplied in the form of a concentrate containing a high proportion of the active ingredients, and the concentrate is then diluted with water before use. The concentrates are usually required to withstand storage for prolonged periods and after such storage, to be capable of dilution with water to form aqueous compositions which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment. Concentrates conveniently contain 20-90%, preferably 20-70%, by weight of the active ingredients. Dilute compositions ready for use may contain varying amounts of the active ingredients depending upon the intended purpose; amounts of 0.01% to 10.0% and preferably 0.1% to 2%, by weight of active ingredients are normally used.

A preferred form of concentrated composition comprises finely divided active ingredient which has been dispersed in water in the presence of a surface-active agent and a

suspending agent Suitable suspending agents are hydrophilic colloids and include, for example, polyvinylpyirolidone and sodium carfooxymethylcellulose, and the vegetable gums, for example gum acacia and gum tragacanth. Preferred suspending agents are those which impart thixotropic properties to, and increase the viscosity of the concentrate. Examples of preferred suspending agents include hydrated colloidal mineral silicates, such as montmorillonite, beidelϋte, nontronite, hectorite, saponite, and saucorite. Bentonite is especially preferred. Other suspending agents include cellulose derivatives and polyvinyl alcohol.

The compositions of the invention may comprise, in addition to one or more compounds of formula la or lb, one or more additional compounds which possess biological activity, for example herbicides, fungicides, insecticides (optionally with an insecticide synergist) and plant growth regulators. The other compound will most usually be another herbicide which may be any herbicide not having the formula la or lb. It will generally be a herbicide having a complementary action in the particular application. Examples of useful complementary herbicides include:

A. benzo-2, 1 ,3-thiadiazin-4-one-2,2-dioxides such as bentazone;

B. hormone herbicides, particularly the phenoxy alkanoic acids such as MCPA, MCPA-thioethyl, dichlorprop, 2,4,5-T, MCPB, 2,4-D, 2,4-DB, mecoprop, trichlopyr, fluroxypyr, clopyralid, and their derivatives (eg. salts, esters and amides);

C. 1,3 dimethylpyrazole derivatives such as pyrazoxyfen, pyrazolate and benzofenap;

D. Dinitrophenols and their derivatives (eg. acetates) such as dinoterb, dinoseb and its ester, dinoseb acetate; E. dinitroaniline herbicides such as dinitramine, trifluralin, ethalflurolin, pendimethalin, oiyzalin; F. arylurea herbicides such as diuron, flumeturon, metoxuron, neburon, isoproturon, chlorotoluron, chloroxuron, linuron, monolinuron, chlorbromuron, daimuron, methabenzthiazuron; G. phenylcarbamoyloxyphenylcaibamates such as phenmedipham and desmedipham; H. 2-phenylpyridazin-3-ones such as chloridazon and norflurazon;

I. uracil herbicides such as lenacil, bromacil and terbacil;

J. triazine herbicides such as atrazine, simazine, aziprotryne, cyanazine, prometryn, dimethametryn, simetryne, and terbutryn; K. phosphorothioate herbicides such as piperophos, bensulide, and butamifos; L. thiocarbamate herbicides such as prosulfocarb, cycloate, vemolate, molinate, thiobencarb, butylate ^* , EPTC ^* , tri-allate, di-allate, esprocarb, tiocarbazil, pyridate, and dimepiperate; M. l,2,4-triazin-5-one herbicides such as metamitron and metribuzin; N. benzoic acid herbicides such as 2,3,6-TBA, dicamba and chloramben; O. anilide herbicides such as pretilachlor, butachlor, alachlor, propachlor, propanil, metazachlor, metolachlor, acetochlor, and dimethachlor; P. dihalobenzonitrile herbicides such as dichlobenil, bromoxynil and ioxynil; Q. haloalkanoic herbicides such as dalapon, TCA and salts thereof; R. diphenylether herbicides such as lactofen, fiuroglycofen or salts or ester thereof, nitrofen, bifenox, aciflurofen and salts and esters thereof, oxyfluorfen, fomesafen, chlomitrofen and chlomethoxyfen; S. aryloxyphenoxypropionate herbicides such as diclofop and esters thereof such as the methyl ester, fluazifop and esters thereof, haloxyfop and esters thereof, quizalofop and esters thereof and fenoxaprop and esters thereof such as the ethyl ester;

T. cyclohexanedione herbicides such as alloxydim and salts thereof, sethoxydim, cycloxy dim, tralkoxydim, and clethodim; U. sulfonyl urea herbicides such as chlorsulfuron, sulfometuron, metsulfuron and esters thereof; bensulfuron and esters thereof such as DPX-M6313, chlorimuron and esters such as the ethyl ester thereof pirimisulfuron and esters such as the methyl ester thereof,

2-[3-(4-memoxy-6-π_ethyl- l,3,5--ri_-zin-zyl)-3-methylureido-sulphonyl) benzoic acid esters such as the methyl ester thereof (DPX-L5300) and pyrazosulfuron; V. imidazolidinone herbicides such as imazaquin, imazamethabenz, imazapyr and isopropylammonium salts thereof, imazethapyr,

W. arylanilide herbicides such as flamprop and esters thereof, benzoylprop-ethyl, diflufenican;

X. amino acid herbicides such as glyphosate and glufosinate and their salts and esters, sulphosate and bialaphos;

Y. organoarsenical herbicides such as monosodium methanearsonate (MSMA);

Z. herbicidal amide derivative such as napropamide, propyzamide, caibetamide, tebutam, bromobutide, isoxaben, naproanilide and naptalam;

AA. herbicidal triketones such as sulcotrione;

AB. miscellaneous herbicides including ethofumesate, cinmethylin, difenzoquat and salts thereof such as the methyl sulphate salt, clomazone, oxadiazon, bromofenoxim, barban, tridiphane, flurochloridone, quinclorac, dithiopyr and mefanacet;

AC. Examples of useful contact herbicides include : bipyridylium herbicides such as those in which the active entity is paraquat and those in which the active entity is diquat;

* These compounds are preferably employed in combination with a safener such as dichloπnid.

The invention will now be illustrated by the following examples. Characterising data for the compounds described in the examples and other compounds of foπnulae la and lb can be found in Table IV below. In the examples and Table IV, the following abbreviations are used:

NMR Nuclear magnetic resonance spectroscopy; (measured in δ ppm from TMS standard in d* DMSO at 270 MHz unless stated otherwise)

In the NMR data, s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet, br (or b)

= broad; M. Pt. or m.p. Melting Point;

MS Mass Spectrum

FAB Fast Atom Bombardment (positive ion unless stated otherwise)

El Electron Ionisation decomp. decomposed DMF NN-dimethylfoπnamide;

DMSO Dimethylsulfoxide

Example 1: Preparation of l-(6-(3,4^-trimethoxyphenoxy)hexyloxy)-2,2-dimethyl- 4,6-diamino-l^-dihydro-l _t 3,5-triazine hydrobromide (hydrobromide salt of Compound

Step a O-Benzylhydroxylamine hydrochloride (25.0g) and dicyandiamide (13.17g) were dissolved in industrial methylated spirits (85ml) with warming and stirring and the resulting solution was heated at reflux for 3 hours. The mixture was then concentrated under reduced pressure to leave an oily residue. The residue was mixed with water (500ml) and basified with 6N sodium hydroxide solution. A benzyloxydiguanide base separated. This solidified on cooling as a crystalline white solid. The solid was filtered from the reaction mixture and washed with water. Step b

To a solution of benzyloxydiguanide (21.3g) in industrial methylated spirits (81.3ml) was added concentrated hydrochloric acid (17.62ml) followed by acetone (81.3ml). The resulting mixture was heated at reflux for 3 hours and then concentrated under reduced pressure to leave a solid. The solid was triturated with acetone to leave 1 -benzyloxy-2,2-dimethyl-4,6-diamino- 1 ,2-dihydro- 1 ,3,5-triazine hydrochloride. Step c

1 -Ber-zyloxy-2,2-dimethyl-4,6-diamino- 1 ,2-dihydro- 1 ,3,5-triazine hydrochloride (16.0g) was dissolved in a mixture of ethanol (250ml) and water (150ml). 10% Palladium on charcoal (384mg) was added and the resulting mixture was hydrogenated at room temperature and atmospheric pressure. After filtering the reaction mixture through "HYFLO" the filtrate was concentrated under reduced pressure to leave a solid. The solid was recrystallised from ethanol to leave l-hydroxy-2,2-dimethyl-4,6-diamino-l,2-dihydro- 1,3,5-triazine hydrochloride (3.2g) as a white solid. Step d

To a solution of 3,4,5-trimethoxyphenol (3.7 lg) in N,N-dimethylformamide (30ml) was added potassium carbonate (2.8g). The resulting suspension was stirred under nitrogen for 30 minutes. 6-Bromohexan-l-ol (3.65g) was added to the suspension and the resulting mixture was heated at 100°C for 1 hour. Most of the NN-dimethylformamide was removed under vacuum. The residue was partitioned between diethyl ether and water, the aqueous layer separated and washed with further diethyl ether. The combined diethyl ether fractions were

washed with brine, dried over magnesium sulphate and the solvent evaporated to give a brown oil. This was purified by chromatography on silica, eluting with ethyl acetate:hexane 2:1, to yield 6-(3,4,5-trimethoxyphenoxy)hexan-l-ol (3.7g). Step e To a cooled solution of 6-(3,4,5-trimethoxyphenoxy)hexan-l-ol (3.7g) in diethyl ether

(30ml) at 5°C was added phosphorus tribromide (1.76g) dropwise. The resulting mixture was stirred with cooling for 1.5 hours after which it was neutralised with sodium bicarbonate solution. The organic layer was separated and the aqueous layer was extracted with diethyl ether (2x30ml). The combined extracts were dried (magnesium sulphate) and filtered. The filtrate was concentrated under reduced pressure to leave l-bromo-6-(3,4,5- trimethoxyphenoxy)hexane (2.2g) as an oil. Step e

To a warm solution of l-hydroxy-2,2- limemyl-4,6-d_iimmo-l,2-dihydro-l,3,5-triazine hydrochloride (1.22g) in ethanol (50ml) was added a solution of sodium hydroxide (0.24g) in ethanol (20ml). The solid which precipitated was filtered off and the filtrate was evaporated under reduced pressure to leave a solid. This solid was suspended in N,N-dimethylformamide (40ml) and l-bromo-6-(3,4,5-trimethoxyphenoxy)hexane (2.2g) added. Mild heating resulted in the formation of a yellow solution. The solution was heated for 30 minutes after which it was concentrated under reduced pressure to leave the title compound (3.056g) as a brown gum.

»H ΝMR (d« DMSO): 1.2-1.8(14H,m); 3.5(3H,s); 3.7(6H,s); 3.8-3.9(4H,m); 6.15(2H,s)ppm.

Example 2: Preparation of l-(10-hydroxydecyloxy)-2 2-dimethyl-4,6-diamino-l,2- dihydro-l^^-triazine hydrobromide (Compound L28) To a warmed solution of 1 -hyciroxy-2,2-* ____nethyl- ,6-diaπ-ino- 1 ,2-dihydro-

1,3,5-triazine hydrochloride (3.34g, prepared as in Example 1) in ethanol (100ml) was added a solution of sodium hydroxide (0.655g) in ethanol (50ml). The solid which precipitated was filtered off and the filtrate was evaporated under reduced pressure to leave a solid. This solid was suspended in N,N-dimethylfoπnamide (50ml) and 1-bromodecan-l-ol (4.1g) added. The mixture was warmed gently and the reaction mixture turned yellow. The mixture was then heated at 80°C for 30 minutes after which it was concentrated under reduced pressure to leave the title compound as yellow gum (4.28g).

»H NMR (d«DMSO):l.l-1.7(22H,m); 3.7-3.9(2H,br s); 4.3(2H,m); 7.9(lH,d);

8.5(lH,d); 8.7(lH,br s)ppm.

Example 3: Preparation of l-[2-(2,4-dichlorophenyl)prop-l-yloxy]-2^-dimethyl-4,6- diamino-l^-dihydro-l^-triazine hydrochloride (Compound 1.64)

Step a

Tetrabutylammonium hydrogen sulfate (31.23g) was added to a stirred solution of sodium hydroxide (7.36g) in water (92ml) (slight exotherm). A mixture of methyl 2,4- dichlorophenylacetate (10.06g) and methyl iodide (26.13g) in dichloromethane (92ml) was added with vigorous stirring to the resulting solution. After 4 hours, the dichloromethane and aqueous layers were separated, and the former was concentrated in vacuo until almost all of the solvent had been removed. Diethyl ether (150ml) was added, the resulting precipitate was filtered off, and the filtrate was concentrated to give methyl 2-(2,4-dichlorophenyl)propanoate (8.97g, 84% yield) as an oil. Step b

Methanol (28.4ml) was added dropwise over 70 minutes to a stirred mixture of methyl 2-(2,4-dichlorophenyl)propanoate (8.97g) and sodium borohydride (3.6 lg) in refluxing tetrahydrofuran (100ml) (90-95 °C bath temperature). Vigorous effervescence was observed. After a further 40 minutes heating, the reaction mixture was allowed to cool then dilute hydrochloric acid was added, whereupon a white precipitate formed. The supernatant was decanted off, concentrated under reduced pressure, and re-combined with the precipitate. Water was added to the resulting material and it was extracted with rert-butyl methyl ether. The extracts were combined, washed with water, dried over magnesium sulfate and concentrated in vacuo to give 2-(2,4-dichlorophenyl)propan-l-ol (7.56g, 97% yield) as an oil. Step e

Diethyl azodicarboxylate (6.6 lg) was added to a stirred solution of 2-(2,4- dichlorophenyl)propan-l-ol (7.00g), triphenylphosphine (9.96g) and N-hydroxyphthalimide (5.54g) in tetrahydrofuran (150ml). The solution quickly went dark red and then faded to a yellow colour (see E Grochowski and J Jurczak, Synthesis, 1976, 682). After about 20 minutes the volatiles were stripped off under reduced pressure. The resulting yellow solid was triturated with a 1 : 1 mixture of hexane and tert-butyl methyl ether (150ml) and filtered off, and the filtrate was concentrated to give a yellow oil (15.23g). This yellow oil was twice

chromatographed on columns of silica gel using a 1 : 1 mixture of hexane and fcrt-butyl methyl ether as eluent to give N-2-(2,4-dichlorophenyl)prop-l-yloxyphthalimide as a white solid (9.925g, 83% yield), 1H NMR (CDC1 ₃ , 270MHz) 1.46 (3H, d), 3.76 (IH, sextet), 4.22 (IH, dd), 4.41 (IH, dd), 7.24 (IH, m), 7.38 (2H, m), 7.74 (2H, m), 7.81 (2H, m) ppm. Step d

Ethanol (30ml) and hydrazine hydrate (0.609g) were added successively to N-2-(2,4- dichlorophenyl)prop-l-yloxyphthalimide (4.260g) and the resulting mixture was stirred and heated under reflux. After about 45 minutes, the reaction mixture was allowed to cool and concentrated hydrochloric acid (3.05ml) was added, and the mixture was again heated briefly to reflux and allowed to cool. A solid appeared, and this was filtered off and washed with ethanol. The filtrate was concentrated in vacuo, the further quantities of solid which formed during concentration again being filtered off and discarded. Diethyl ether (100ml) was added to the resulting oil and, on standing, a white solid crystallised. This was filtered off and dried to give O-2-(2,4-dichlorophenyl)prop-l-yl hydroxylamine hydrochloride (2.672g, 86% yield) as a white crystalline solid, Η NMR (CDC1 ₃ , 270MHz) 1.14 (3H, d), 3.43 (m), 4.06 (IH, dd), 4.13 (IH, dd), 7.40 (2H, m), 7.56 (IH, d), 10.80 (2H, s) ppm. Step e

A mixture of O-2-(2,4-dichlorophenyl)prop-l-yl hydroxylamine hydrochloride (2.672g) and dicyandiamide (0.962g) in ethanol (30ml) was heated with stirring under an atmosphere of nitrogen for 3 hours, then allowed to cool. Gaseous hydrogen chloride was bubbled through the resulting mixture for 3 minutes, then diethyl ether (100ml) was added and hydrogen chloride was passed through the solution for a further 2 minutes. A white solid precipitated and was filtered off and dried. It was dissolved in water and treated with a solution of potassium carbonate (2.8g) in water (10ml) until the mixture reached pHl 1, and was then extracted with chloroform. The chloroform solution was dried over magnesium sulfate and concentrated in vacuo to give l-[2-(2,4-dichlorophenyl)prop-l-yloxy]biguanide as a clear gum (1.735g, 55% yield), Η NMR (CDC1 ₃ , 270 MHz) 1.25 (3H, d), 3.18 (IH, sextet), 3.87 (IH, dd), 3.98 (IH, dd), 7.20 (2H, d), 7.35 (IH, d) ppm, and 2 broad peaks centred at 4.48 and 5.25 ppm. Step f

Acetone (100ml) and concentrated hydrochloric acid (0.47ml) were added successively to l-[2-(2,4-dichlorophenyl)prop-l-yloxy]biguanide (1.735g) (precipitate forms)

and the resulting mixture was heated at 80 °C with stirring for 5 hours under a nitrogen atmosphere. On cooling, white crystals formed and these were filtered off and dried to give the title compound (1.065g, 49% yield) as a white crystalline solid, with characterising data as in Table IV.

Example 4: Preparation of l-[l-(2,6-dichlorophenyl)ethoxy]-2^-dimethyl-4,6-diamino- l,2-dihydro-l,3,5--triazine hydrochloride (Compound US7) Step a l-(2,6-Dichlorophenyl)ethanol (prepared by treatment of 2,6-dichlorobenzaldehyde with methylmagnesium chloride) was converted into N- l-(2,6-dichlorophenyl)- ethoxyphthalimide using N-hydroxyphthalimide, triphenylphosphine and diethyl azodicarboxylate under the conditions described for the preparation of a related compound in Example 1. The product was a white crystalline solid, melting point 133-4 °C, Η NMR (CDClj, 270MHz) 1.95 (3H, d), 6.10 (IH, q), 7.17 (IH, t), 7.30 (2H, d), 7.75 (4H, m) ppm. Step b

N-l-(2,6-Dichlorophenyl)ethoxyphthalimide was treated successively with hydrazine hydrate and concentrated hydrochloric acid in the same way as described for a related compound in Example 1 to give O-2-(2,6-dichlorophenyl)prop-l-yl hydroxylamine hydrochloride as a white crystalline solid, Η NMR (dβ-DMSO, 270MHz) 1.63 (3H, d), 5.90 ( IH, q), 7.40 ( IH, dd), 7.50 (2H, m) ppm. Step e

A mixture of O-2-(2,6-dichlorophenyl)prop-l-yl hydroxylamine hydrochloride (6.0g) and dicyandiamide (2.5g) in ethanol (25ml) was heated under reflux for 2 hours and allowed to cool. Water and a solution of potassium carbonate (3.5g) in water were added successively, and the resulting mixture was extracted with ethyl acetate. The extracts were combined and washed with water and brine, dried over magnesium sulfate and concentrated to give a viscous yellow oil (6.2g). This oil was taken up in acetone (400ml) and concentrated hydrochloric acid (1.9ml) was added. The resulting clear solution was heated under reflux for 9 hours, during which time a white solid precipitated. The reaction mixture was allowed to cool and the solid was filtered off, washed with acetone and dried to give the title compound (4.63g, 51% yield) as a white solid, with characterising data as in Table IV.

Example 5: Preparation of l-[2-cl_doro-3,6-difluorobenzyloxy]-2^-dimethyI-4,6- diamino-l^-dihydro-l^-triazine hydrobromide (Compound H.100)

Dowex 1-X8 (Cl) standard grade ion exchange resin, particle size 0.300-0.850mm, (20ml) was loaded into a glass column and washed with a 4% aqueous solution of sodium hydroxide (100ml) and then with deionised water until the eluent was neutral. A solution of l-hydroxy-2,2-dimethyl- ,6-diammc l^-dihydreHl,3,5-triazine hydrochloride (1.60g, prepared as described in Example 1) in deionised water was applied to the column and eluted through with deionised water (100ml). The aqueous solution collected was freeze-dried to give l-hydroxy-2^-dimemyl-4,6-diamino-l^-dihydro-l,3,5-triazine as the free base, a white powder ( 1.20g, 92% yield), melting point 205 °C (decomposition). A solution of this dihydrotriazine (0.157g) in methanol (2.5ml) was added to 2-chloro-3,6-difluorobenzyl bromide (0.266g) in a glass tube and the resulting mixture was shaken thoroughly. DMF (4ml) was added, and the mixture was heated at 90-100 °C for 3 hours, during which time methanol was allowed to evaporate off. The mixture was left to cool and the volatiles were stripped off under reduced pressure. Deionised water (5ml) was added and a solid precipitated. The mixture was washed with ethyl acetate, leaving the solid in the aqueous layer. The aqueous layer and solid were concentrated to give the title compound (0.366g, 92% yield) as a white powder, with characterising data as in Table TV.

Example 6: Preparation of l-[l-(2,6^chlorophenyi)ethoxy]-2^-dijnethyl-4,6-diamino- l,2-dihydro-l,3,5-triazine, acetic add salt (Compound IL58)

Triethylamine (1.93g) was added to a solution of l-[l-(2,6-dichlorophenyl)ethoxy]- 2,2-dimethyM,6-diami_QCHl^-dihydro-1 .5-rri_-zine hydrochloride from Example 4 (l.OOg) in water (250ml). The resulting mixture was stirred for an hour (white solid began to appear) and then allowed to stand overnight The precipitated solid was filtered off and dried to give l-[H2,6-dichlorophenyl)ethoxy]-2,2-dimethyl-4,6-diam_no-l,2- dihydro-l,3,5-triaz_n as the free base (0.741g), a white solid, with data as in Table TV. Glacial acetic acid (0.10g) was added to a stirred solution of the free base (0.55 lg) in tetrahydrofuran (10ml). The resulting mixture was stirred for an hour, allowed to stand overnight, then filtered to remove a small quantity of precipitate. The filtrate was concentrated in vacuo to give a sticky solid which, on trituration with diethyl ether, became granular. This was filtered off and dried to give the title compound as a white solid, with data as in Table IV.

Example 7: Preparation of the butyric acid salt of l-(lϋ-Hydroxydecyloxy)-2^- dύnethyM,6* Uamino-l^-dihydro-1^ -triazine (Compound 31)

Step a l-( 10-Hydroxyde«yloxy)-2,2-___methyl-4,6-diamino- 1 ,2-dihydro-l ,3,5-triazine hydrobromide from Example 2 (4.0g) in deionised water (50ml) was added to a column of ion exchange resin (Dowex 1-8X™, 70 ml), prewashed with sodium hydroxide until basic, and then water until neutral). The column was eluted with water (750ml) until the fractions were neutral. The aqueous solution obtained was freeze dried to give the free base as a white powder (2.17g), mpt 105- 108° C. Mass spectrum: MH+ = 313 (FAB) Step b

The free base (0.2g) was suspended in water and butyric acid (0.056g) added. The mixture was stirred at room temperature for 1 hour and then concentrated under reduced pressure. Excess water was removed by drying over P ₂ O ₅ in vacuo to give the salt (0.035g). Η NMR (d« DMSO): 1.15-1.70 (m,22H); 3.30 (m, 2H), 3.80 (bs,2H) ppm.

Example 8: Preparation of l-[3-(4-bromophenoxy)-propoxy-]-2^-dimethyl-4,6- diamino-l,2-dihydro-l,3,5-triazine (Compound m.105) l-Hydroxy-2^-dimethyl-4,6-diam o-l,2-dihydro-1 _^ 3,5-triazine free base (0.485g) was suspended in dry DMF ( 10ml) and 3-(4-bromophenoxy)-propyl bromide ( 1.0g) was added. The mixture was heated to approximately 80° C for 2 hours, during which time a yellow solution was obtained. The DMF was removed in vacuo to leave the crude product as an orange solid. This was triturated with ethyl acetate to remove excess bromide, and then recrystallised from water to remove unreacted l-hydroxy-2,2-dimethyl-4,6-diamino-l,2- dihydro- 1 ,3,5-triazine, giving the pure product as a cream solid (0.48g).

Η NMR (c DMSO): 1.20-1.60 (bs,6H); 2.0-2.20 (m, 2H); 4.0 (m,4H); 6.90 (d,2H); 7.40 (d,2H), 8.00 (s,lH); 8.60 (s,lH); 8.70 (s,lH) ppm. Mass spectrum: MH+ = 369 (FAB)

Example 9: Preparation of l-[3-(2,4 _r 5-tricUorophenoxy)-propoxy-]-2_2-dimethyI-4,6- diammo-l,2-dihydro-l,3,5-triazine (Compound HI.72) l-Hydroxy-2,2* limemyW,6-di_unino-l^-d_ ydro-l,3,5-_ri__zine free base (1.34g) was suspended in dry DMF (25ml) and 3-(2,4,5-trichlorophenoxy)-propyl bromide (3.0g) was added. The mixture was heated to approximately 80° C for 2 hours, during which time a yellow solution was obtained. The DMF was removed in vacuo to leave the crude product contaminated with l-hydroxy-2,2-dimemyl* ,6-diamino-l^-dihydro-l,3,5-triazine, as a white solid.

The crude product was purified by reverse phase chromatography. A Varian Mega Bond ELUT C18™ reverse phase column was washed with water, and then the crude product (0.05g) in water (1ml) was applied to the column. The column was then washed with water containing 1% acetic acid (50ml), followed by water containing 70% acetonitrile and 1% acetic acid (100ml). The pure product was isolated by freeze drying the appropriate fractions, as a white solid (0.34g). ^l H NMR (d« DMSO): 1.30 (bs,6H); 2.10 (bs,2H); 4.00 (t,2H); 4.18 (t,2H); 7.45 (s.lH); 7.78 (s,lH) ppm.

Example 10: Preparation of l-[6-(3,4^-trimethoxyphenoxy)hexyloxy]-2^-dimethyI-4,6- bis-(acetamido)-l _t 2-dihydro-l^^-triazine. l-[6-(3,4,5-Trimethoxyphenoxy)hexyloxy]-2^-dimemyl-4,6-diam o-l,2-dihydro-

1,3,5-triazine (0.2g) was heated with acetic anhydride (6ml) on a steam bath, with stirring, for approximately 30 minutes. The solvent was then removed in vacuo and the crude product purified by vacuum filtration through silica gel, eluting with ethyl acetate to give the product as a colourless gum (0.150g). Η NMR (d* DMSO): 1.40-1.60 (bs, 4H); 1.70 (s,6H); 1.70-1.84 (m, 4H); 2.15 (s,3H); [2.25 (s) + 2.35 (s)](3H); 3.75 (s,3H); 3.85 (s,6H); 3.90-4.00 (m, 4H); 6.15 (s,2H) ppm. Mass spectrum MH+ = 508 (FAB)

Example 11: Preparation of l-(12-Hydroxydodecyloxy)-2^-dimethyl-4,6-diamino-l^- dihydro-l,3,5-triazine hydrobromide (Compound 1.84). l-Hydroxy-2,2-d_jnethyl* ,6-di_imino-l,2-dihydro-l,3,5-triazine free base (liberated from 1.72g of the hydrochloride, as in Example 1), was suspended in dry DMF (50ml) and

12-bromododecan-l-ol (2.35g) was added. The mixture was heated and stirred at 80° C for 3 hours. The DMF was removed in vacuo and the resultant gum was triturated with acetone. The grey solid, l-hydroxy-2,2-dimethyl-4,6-d-Lamko-l^-dihydro-l,3,5-triazine , was filtered. The filtrate was concentrated under reduced pressure to leave a yellow liquid, which was then washed with chloroform and then acetone to remove unreacted bromide, to give the product as a whitish-yellow solid. This was shown by NMR to contain 45% of the starting 1-hydroxy- 2,2-dimemyl-4,6-diamώo-l,2-dihydro-l,3,5-triazine, and was used directly for testing. Η NMR (a DMSO): 1.20-1.40 (m,26H); 3.40 (t,2H); 3.80 (bs,2H); 4.30 (t,lH) ppm.

TABLE IV

Ul

Table IV contd.

in

Table IV contd.

Ul Ul

Table IV contd.

Ul o.

Table IV contd.

U

Table IV contd.

Table IV contd.

Ul

10

Table IV contd.

σ. o

Table IV contd.

σ. I

Table IV contd.

Table IV contd.

c/ c w.

σ.

CO x

ro

In the following biological examples, the test compounds were applied to a variety of plants. The plants which were included in the tests are shown in Table V below together with the abbreviations which appear in the tables of results.

IΔELEV

EXAMPLE 12 This Example illustrates the herbicidal properties of compounds according to d e invention.

The herbicidal activity of the compounds was tested as follows: Each chemical was formulated by dissolving it in an appropriate amount, dependent on d e final spray volume, of a solvent surfactant blend which comprised 78.2 gm litre of Tween 20 and 21.8 gm litre of Span 80 adjusted to 1 litre using methylcyclohexanone. Tween 20 is a Trade Mark for a surface-active agent comprising a condensate of 20 molar proportions of ethylene oxide with sorbitan laurate. Span 80 is a Trade Mark for a surface-active agent comprising sorbitan mono-laurate. If the chemical did not dissolve, the volume was made up to 5cm ³ with water, glass beads were added and this mixture was then shaken to effect dissolution or suspension of the chemical, after which the beads were removed. In all cases, the mixture was then diluted with water to the required spray volume of 30cm ³ . The sprayed aqueous emulsion contained 4% of die initial solvent surfactant mix and the test chemical at an appropriate concentration.

The spray compositions so prepared were sprayed onto young pot plants (post-emergence test) at a spray volume equivalent to 1000 litres per hectare.

Damage to plants was assessed 13 or 20 days after spraying by comparison with untreated plants, on a scale of 0 to 9 where 0 is 0% damage, 1 is 1-5% damage, 2 is 6-15% damage, 3 is 16-25% damage, 4 is 26-35% damage, 5 is 36-59% damage, 6 is 60-69% damage, 7 is 70-79% damage, 8 is 80-89% damage and 9 is 90-100% damage. The designation "-" indicates that a compound was not tested against the indicated species.

The results of the tests are given in Table VI below where Compound Number refers to the numbers given id Tables I to IE and DA indicates the number of days after application at which the assessment was made.

SUBST.TUTE SHEET (RULE 26)

EXAMPLE 13 Further compounds were tested using a method similar to that of Example 3 above except that: a wider variety of plants was used including crops as well as weeds; die damage to plants was assessed in all cases 13 days after spraying; and plants were sprayed at a volume equivalent to 400 Utres per hectare. The results of the experiment are set out in Table VH below where Comp. No. refers to the compound number of Tables I to LU.

TABLE Vπ

C cΛ

CD

rπ

X rπ

σ>

H con

__σ c ro 3

-4

CD a c —:I m

CO

l\3

3

Table VH contd.

Comp. App. BV BN GM ZM OS TA PA MI CA GA AR EH PO IH AT XT AP AM R SH SV BP PD EC CE No Rate

-0

Si

— . m &

r

00 O

co

rπ ro