WO2003068377A1

WO2003068377A1 - Surfactant compounds and agrochemical compositions

Info

Publication number: WO2003068377A1
Application number: PCT/GB2003/000524
Authority: WO
Inventors: Edward George Scovell; Hanamanthsa Shankarsa Bevinakatti
Original assignee: Imperial Chemical Industries Plc
Priority date: 2002-02-11
Filing date: 2003-02-07
Publication date: 2003-08-21
Also published as: AU2003245683A1; GB0203104D0

Abstract

Surfactant compounds are of the general formula (I): R1R2X1-[Link]-R3 where: Link is a link moiety of the formula: -C-C-CO-; X1 is a nitrogen moiety, giving an amine, amine oxide, quaternary amine or betaine function; and R1 R2 and R3 have defined meanings but incorporate at least one polyhydroxy hydrocarbyl group and at least one C6 to C30 hydrocarbyl group. The compounds of the formula (I) can function as surfactants in agrochemical formulations, particularly as emulsifiers, wetting agents, dispersants, thickeners or solubilisers and, especially as adjuvants; or as and, especially for amino oxide or quaternary compounds, in personal care formulations or as fabric softeners. The compounds can be used as adjuvants particularly where the agrochemical is a plant growth regulator, herbicide, and/or pesticide, for example insecticides, fungicides, acaricides, nematocides, miticides, rodenticides, bactericides, molluscicides and/or a bird repellent. Particularly useful formulations include water soluble herbicide (s), particularly such as Glyphosate, Sulfosate, Glufosinate and Paraquat.

Description

SURFACTANT COMPOUNDS AND AGROCHEMICAL COMPOSITIONS

This invention relates to surfactant compounds, and particularly to compounds including amine functionality, to their synthesis by a route involving a Michaels reaction and to their use particularly as adjuvants in agrochemical formulations. The present invention provides compounds of the formula (I): R¹R²X¹-[ Link ]-R³ (I) where

Link is a linking group including a moiety of the formula: -C-C-CO-;

X-* is N; N⁺->0"; N⁺R4- where: R4- is C^ to CQ hydrocarbyl carrying an anionic substituent, particularly -CH2-COO^" ; or N⁺R^An^" where: R^ is C-_| to C20 hydrocarbyl, particularly alkyl, hydroxyalkyl, alkoxyalkyl or aralkyl; and An" is a charge balancing anion e.g. alkali metal or ammonium; R^ is polyhydroxy hydrocarbyl; hydroxy hydrocarbyl, particularly hydroxyalkyl; or hydrocarbyl; R² is H; hydrocarbyl, particularly alkyl, or alkoxyalkyl; hydroxy hydrocarbyl, particularly hydroxyalkyl, polyhydroxy hydrocarbyl; or

R² is a group of the formula: - [ Link ] R³, where Link is as defined above and R³ is as defined below; or R² together with the nitrogen atom of X^ and a carboxyl function on the group Link forms a 4, 5, 6 or 7 membered cyclic amide, which is Λ/-substituted with a group R^, where R^ is polyhydroxy hydrocarbyl, hydroxy hydrocarbyl, particularly hydroxyalkyl, or hydrocarbyl;

R³ is a group -NR⁷ R⁸; -(OA)_nNR⁹R¹ °; or -(OA)_nOR^{1 1} ; where each OA is independently an oxyalkylene group; each n is independently 0 or from 1 to 100; R⁷ is polyhydroxy hydrocarbyl, hydroxy hydrocarbyl, or hydrocarbyl;

R³ is H, polyhydroxy hydrocarbyl, hydroxy hydrocarbyl, hydrocarbyl or a group R¹ R²X¹ -[ Link ]- where R^"1 , R², X¹ and Link are as defined above; R⁹ hydrocarbyl; R¹⁰ hydrocarbyl or a group R¹ R²X¹-[ Link ]-(OA)_n- , where R¹ , R², X¹ ,

Link, OA and n are as defined above R11 hydrocarbyl; or R³ together with a carboxyl function on the group Link forms a 5, 6 or 7 membered cyclic imide, which is Λ/-substituted with a group R⁶, where R⁶ is as defined above; where: at least one of R^"1, R^, R^and R⁸ is polyhydroxy hydrocarbyl; and/or at least one of, and very desirably at least two of, R^ , R^, R⁷and R⁸ is hydroxy hydrocarbyl; and at least one of R² R⁵ , R⁶, R⁷, R⁸, R⁹, R¹⁰ and R¹¹ is C₆ to C30 hydrocarbyl. In particular, desirable compounds of the formula (I) include compounds of the formula (lla) to (lie):

R²²R²³N-CHR²⁰-CHR²¹-CO-NR²⁴R²⁵ (lla)

_R22_R23_N__CHR20__CHR21__CO(OA)_n OR^{1 1} (lib)

R²⁶N_LCHR²⁰-CHR²¹-CO-NR²⁷R²⁸]₂ (He) where OA, n and R^ ^ are as defined above in formula (I); and

R²0 and R ^ are each independently both H or one is H and the other is methyl R²² is polyhydroxy hydrocarbyl or hydroxy hydrocarbyl;

R²³ is H, a hydrocarbyl, or hydroxy hydrocarbyl, orpolyhydroxy hydrocarbyl; or both R²² and R²³ are hydroxy hydrocarbyl; R ⁴ is hydrocarbyl

R²⁵ is hydrocarbyl, or a group R²²R²³ N-CHR²⁰-CHR²¹-CO- where R²⁰, R²¹ , R²² and

R²³ are as defined above; R²⁶ is CQ to C30 hydrocarbyl; each R²⁷ is polyhydroxy hydrocarbyl or hydroxy hydrocarbyl; and each R²⁸ is H, hydrocarbyl, hydroxy hydrocarbyl or polyhydroxy hydrocarbyl.

Compounds of the formulae (lla) to (lie) can be considered as being derived from acrylic (R²^ and R²¹ both H), methacrylic (R²⁰ H and R²¹ methyl) and crotonic (R²⁰ methyl and R²¹ H) acids.

Further desirable compounds of the formula (I) are of the formulae (lid) to (llh):

where R^ , R² and R³ are as defined above for formula (I) and R³' is OH, OM, where M is a metal (possibly a fractional metal where its valence is greater than 1 ) or an ammonium group, OR' where R' is hydrocarbyl particularly C<_| to C₂₂ hydrocarbyl, particularly alkyl or alkenyl or, and particulalry, a group as defined for R³, usually the same as the other group R³.

Compounds of the formula (lid) and (lie) can be considered as being derived from maleic acid, those of the formula (llf), (llg) and (llh) from itaconic acid. Polyhydroxy hydrocarbyl groups are particularly polyhydroxy alkyl groups which desirably have a linear C4 to C7 chain and at least three hydroxyl groups directly bonded to chain carbon atoms. Such groups may include substituents, in particular, alkoxy groups e.g. by etherification of further hydroxyl groups or further polyhydroxy hydrocarbyl, e.g. polyhydroxy alkyl, group(s), but the group desirably includes at least three free hydroxyl groups including such hydroxyl groups on substituents of the basic chain. Particularly, each such group is an open chain tetratol, pentitol, hexitol or heptitol group or an anhydro e.g. cycloether anhydro, derivative of such a group. Especially desirably, such groups are residues of, or derived from, a sugar, particularly a monosaccharide such as glucose, fructose or sorbitol, a disaccharide such as maltose or palitose or a higher oligosaccharide. Where such residues are residues of, or derived from, oligosaccharide(s) they can be considered as open chain mono-saccharide derived groups or residues with saccharide or oligosaccharide substituents which may be cyclic or chains of cyclic residues. Particularly useful polyhydroxy hydrocarbyl groups are derived from glycoses and are of the formula: - CH₂ - (CHOI-O4 - CH₂OH, e.g. corresponding to residues from glucose, mannose or galactose. In this case the group -NR¹ R² is of the formula: -NR²-CH -(CHOH) -CH OH and the group is conveniently called a glycamine group. Most commonly such groups will be derived from glucose and the corresponding amines may be are called glucamines (as they will usually be made from glucose) or sorbitylamines (as they are no longer unsaturated). Strictly, such compounds are derivatives of 1-deoxyglycitols (and 1-deoxyglucitols) and can be referred to as 1-deoxyglycitylamines (and 1-deoxyglucitylamines) or as corresponding aminoglycitols (and aminoglucitols). It is particularly convenient that such groups are the residue of a reducing sugar, such as glucose, because the amines can be made by straightforward reductive alkylation reactions on ammonia or an amine precursor. The polyhydroxy hydrocarbyl group(s) is(are) present as or as part of the hydrophile. Thus, it will usually be desirable that the hydrophilicity of this group is not unduly reduced. The open chain form of such groups is typically the most hydrophilic form and will thus usually be the form desired. Groups including internal cyclic ether functionality can however be used, if desired, and may be obtained inadvertently if the synthetic route exposes the group to relatively high temperatures or other conditions which promote such cyclization.

The substituent R², on the nitrogen atom of X^ , can be a hydrocarbyl group (see further below) or it can be as defined for R^"* in which case the amine function provides two hydrophilic polyhydroxy hydrocarbyl groups. In this latter case, the two groups of the formula R^"! will often be (but need not be) the same, as it usually easier to make the symmetrical polyhydroxy hydrocarbyl substituted amine intermediate. R² can also be a group of the formula: - [ Link ] R³, where Link and R³ are as defined above, to give a "Y" shaped molecule.

The substituent groups can include hydroxy hydrocarbyl, particularly hydroxyalkyl, groups. Typically these groups have relatively short carbon chains e.g. from 2 to 6 C atoms, and specific examples incude 2- and 3-hydroxypropyl and, especially, 2-hydroxyethyl. Such groups are modestly hydrophilic, generally less hydrophilic than polyhydroxy hydocarbyl groups, and it is therefore desirably that where the compounds include no polyhydoxy hydrocarbyl group there are at least 2 hydroxy hydrocarbyl groups. In this case, it is convenient that both R^"* and R² hydroxy hydrocarbyl groups, particularly hydroxyalkyl, desirably both 2-hydroxyethyl, groups.

In the compounds of the formula (I), hydrocarbyl groups desirably have from 1 to 30, more usually from 1 to 22, carbon atoms, and are desirably alkyl, alkenyl, alkaryl, aryl or aralkyl groups. The compounds of the formula (I) include at least one hydrophobic hydrocarbyl group (which may be at least one of R², R⁵ , R⁶, R⁷, R⁸, R⁹, R¹⁰ and R^{1 1}) including from C₆, usually C₈ to C₃₀, more usually C-_|n to C₂ , desirably C-_| to C₂o. and especially from C^₂ to C^ carbon atoms. The hydrophobe groups usually inlcude at least one alkyl or alkenyl group. Such groups may be straight chain, branched or a mixture of straight chain and branched moieties. Hydrocarbyl groups may also be aralkyl groups, particularly C7 to C<_{| 2} aralkyl groups, such as benzyl, or alkyl phenyl groups e.g. a C₈ to C-_jg alkyl phenyl group and particularly 3-(linear alkyl) phenyl. Such groups can be derived from cardanols (3-alkyl phenols which can be extracted from cashew nut shells) which are readily biodegradeable compounds.

Other hydrocarbyl groups can be blocking groups (mainly used to keep the synthesis straightforward), as when they are lower e.g. C-_j to Cg, alkyl groups, particularly methyl or ethyl groups.

R² can also be a substituted alkyl group e.g. an alkoxy substituted alkyl group, particularly a C-_| to C alkyl group substituted with an alkoxy, particularly a C^ to C5 alkoxy and especially a methoxy, ethoxy or propoxy, group, so that the alkoxyalkyl group is particularly a 2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl, or 3-ethoxypropyl group. R² can also be an aralkyl group, particularly a Cγ to C-_{| 2} aralkyl group, such as a benzyl group.

Polyoxyalkylene chains are typically made up of oxyalkylene groups OA of the formula: -(C_mH₂mO)- where m is typically 2, 3 or 4, desirably 2 or 3, i.e. an ethylene oxide or propylene oxide group, and it may represent different groups down the alkylene oxide chain. Generally, it is desirable that the chain is a homopolymeric ethylene oxide chain. However, the chain may be a homopolymer chain of propylene glycol residues or a block or random copolymer chain containing both ethylene glycol and propylene glycol residues. The chain length of the polyalkylene oxide group, when present, i.e. the value of the index n, will generally be chosen to provide the desired properties in the intended product. Typically, where AO is oxyethylene n will usually be from 1 to 100, more usually 3 to 50, and where it AO is oxypropylene n will usually be from 1 to 50. Where the chain is a block or random copolymer of ethylene and propylene glycol residues the chain length chosen will typically correspond to the above ranges but numerically according to the proportion of oxyethylene and oxypropylene residues in the chain. Of course, numerical values of numbers of repeat units in the polyoxyalkylene chain are average values. As is common to surfactants containing a polyoxyalkylene chain, the higher the proportion of ethylene glycol residues, and the longer the polyethylene glycol chain, and the more hydrophilic the product. The group X¹ is a nitrogen atom which either has no further substituent (other than R¹ , R² and Link) or includes a substituent which makes the group a quaternary group, so that when X^ is a substituted nitrogen atom it can be an amine oxide group N- 0; a group N⁺R⁴ "; or N⁺R^ An". When X¹ is a group N⁺R^{4 "}, the group R⁴ is a C-j to CQ hydrocarbyl group carrying an anionic substituent (nominally carrying a balancing negative charge). Thus, typically R^{4 ~} is a carboxyalkyl group, particularly a -CH₂-COO" group forming a betaine structure, although other possibilities include, alkyl sulphate, alkyl sulphonate, alkyl phosphate and alkyl phosphonate groups. The precise charge status and the presence of other ions associated with such groups will depend mainly on the pH. At near neutrality, the compound is likely to exist mainly as the zwitterion, whereas remote from neutrality, the quaternary nitrogen and the anionic group in R⁴ may become associated with charge balancing ions. The charge balancing ions will usually be an alkali metal or onium (ammonium or amine onium) ion for the anionic, usually carboxyl, group and a halide, sulphate, phosphate or carboxylate ion for the amine function. When X^ is a group N⁺R^An", the group R^ is a C_| to C₂₂ hydrocarbyl, particularly an alkyl group and more usually a C-| to Cg or a C-J Q to C^g alkyl group, a C₂ to Cg hydroxy alkyl group, a (C-] to Cg)alkoxy (C-_| to Cg)alkyl group or a C7 to C-₎₂ aralkyl, particularly a benzyl, group. Where R^ is an alkyl group, it will most commonly be a C-_j to Cg alkyl, particularly methyl, group, although it may be a longer chain e.g. Cg to C30, particularly a Cg to C₂₂ alkyl, group and such a longer chain group will tend to act as a secondary hydrophobe. The anion group An^" is a charge balancing anion and can be any suitable counterion, for example mineral acid anions such as a halide, particularly chloride or bromide, sulphate or phosphate ion or a fatty carboxylate species.

The group Link is a group containing the moiety -C-C-CO-, which functions to connect the substituted amino group X^ R^ R² with the group R³. As such its precursor(s) provide suitable reactivity to enable the "linking" reactions but desiably do not include functionality that would interfere with the desired properties of the end products. As is described below, the precursors of the group Link are typically unsaturated acids or derivatives including the group: -C=C-CO-.

Acids including this moiety include acrylic acids such as acrylic, methacrylic and crotonic acids, maleic acid and itaconic acid and these acids or their derivatives can be used in synthesising compounds of the formula (I). Accordingly, group Link is particularly of the formula:

-CH(R²⁰)-CH(R²¹)-CO-, where R²⁰ and R² are each independently H or lower, particularly C_| to C4, alkyl especially methyl. Linking groups where both R^2u and R ^ are H, or where one of R²*-¹ and R²^ is H and the other is methyl, especially where R²^ is H and R²^ is methyl, are particularly useful. Thus very desirably, the link group is of one of the formulae: -CH₂-CH₂-CO-, -CH -CH(CH₃)-CO-, -CH(CH₃)-CH₂-CO-. Such groups are generally derived from acrylate, metfiacrylate or crotonate precursors. The group Link can also be structurally derived from maleic or itaconic acids and in these cases will include skeletal fragments having the structures -CH₂(COO-)-CH₂-COO- (from maleic acid) and -CH₂-CH(COO-)-CH₂-COO- (from itaconic acid). These fragments include two carboxyl functions which will may be derivitised with two groups for exapmle as in compounds of the formulae (lid) and (llf) above, or may be reacted with amino functions elsewhere in the molecule to give a cyclic amide (lactam) as in compounds of the formula (llg) above, or where a nitrogen containing group is linked between these carboxyl groups to give an N-substituted imido function as in compounds of the formula (lie) and (llh) above.

Where the group Link is derived from maleic or itaconic acid, the reagent includes two carboxyl functions. These functions can be free carboxyl groups, derivitised as esters amides or salts, linked to a group R³ or a group R³' or linked to other groups in the molecule to form cyclic amides or imides. We have observed that some compounds of the invention including a group -CONH- have low water solubility. We believe intramolecular hydrogen bonding involving the hydrogen atom on the amido nitrogen atom may contribute to this. Such low solubility may make the application of these compounds more difficult and it may thus be advantageous to reduce the opportunity for such hydrogen bonding by avoiding amides inlcuding such hydrogen atoms either by using a secondary amine or sterically hindered amine to make the amide or by using bis-amide compounds.

The compounds of the invention can be made by routes involving generally conventional synthetic steps.

The inclusion of the nitrogen containing function remote from the carbonyl group in Link can conveniently be carried out by a Michaels reaction between a primary or secondary amine and an α,β-unsubstituted carbonyl (usually carboxyl) compound. Compounds of the formulae (lla), (lib), and (lie) can thus be considered as derived from an acrylic acid, which may be acrylic acid as such, or an alkyl substituted acrylic acid, such as methacrylic or crotonic acid, or a reactive derivative of these acids. Generally, the Michaels reaction of a primary or secondary amine with such acrylic acids, or their carboxylic derivatives, is facile, although with chain substituted acids, such as methacrylic acid or crotonic acid, the Michaels addition is less favoured at relatively low reaction temperatures, probably because of steric hindrance by the substitiuent methyl groups. This generally makes it preferable to carry out the Michaels addition reaction before forming the amide. As the free carboxylic acids are likely to form a salt with the amine which may inhibit the Michaels reaction or may promote side reactions, it is generally desirable that a carboxyl derivative of the acid such as an ester with a lower, particularly a C-j to C4, alcohol, is used as the reagent in the Michaels reaction.

Thus, compounds of the formula (lla) can be made by reacting one mole of an amine R²²R²³NH with one mole of an acrylic ester of the formula CHR²⁰=CR²¹-CO-R where R²⁰, R²¹ , R²² and R²³ are as defined above for formula (lla) and R is a lower, particularly a C-_| to C4, alkyl group, under Michaels reaction conditions, followed by reaction of the intermediate amino-ester R²²R²³N-CHR²⁰-CHR²¹-CO-R with an amine of the formula HNR²⁴R²⁵ under amidation conditions, displacing alcohol ROH, if desired in the presence of an amidation catalyst. In principle, compunds of the formula (lla) can also be made by reacting an amine R² R²³NH with one mole of an acrylic amide of the formula CHR ⁽^=CR^2''-CONR²⁴R²^ under Michaels reaction conditions. However, the facile nature of the Michaels reaction can complicate manufacture of the amide intermediate unless a highly reactive derivative, such as the acid chloride, of the precursor acid is used, together with an amine HNR²⁴R²^, in its synthesis.

Similarly, compounds of the formula (lib) can be made by reacting an amino-ester of the formula R² R²³N-CHR²⁰-CHR²¹-CO-R, synthesised as described above, with an alcohol of the formula HO(OA)_nORl 1 , where OA, n and R^ 1 are as defined for formula (lib) above, under trans- esterification conditions. Alternatively, compounds of the formula (lib) can be made by reacting an ester of the formula CHR²⁰=CHR²¹-CO(OA)_nOR¹ with an amine of the formula R²²R²³NH, where R^ 1 , R²⁰, R²^ , R²² and R²³ are as defined above for formula (lib), under Michaels reaction conditions. The intermediate ester CHR^2υ=CHR²^-CO(OA)_nOR 1 ^ can be made by esterification of the corresponding precursor acid or a reactive derivative such as an acid chloride or a lower, particularly a C-_| to C4, alkyl ester, with an alcohol of the formula HO(OA)_nOR^{1 1}. Compounds of the formula (lie) can be made by reacting one mole of an amine: R²⁸NH₂ with two moles of an acrylic ester CHR^2u=CR^2''-COOR to form an amino-bis-ester of the formula R ⁸N-[CHR^2u-CHR²1-COOR]₂ under Michaels reaction conditions, and then reacting the amino- bis-ester with an amine of the formula -NR⁷R⁸, an amino substituted poolyalkoxylate of the formula -(OA)_nNR⁹R¹⁰; or an alcohol of the formula HO(OA)_nOR^{1 1} under amidation or trans- esterification conditions to make the compound of the formula (lie).

Alternatively, one mole of an amine: R²⁸NH can be reacted with two moles of an ester of the formula CHR²⁰=CR²¹-COO(OA)_nOR^{1 1} , or CHR²⁰=CR²¹-CO-(OA)_nNR⁹R¹⁰, under Michaels reaction conditions. The intermediate ester can be made by esterifying the corresponding precursor acid or a reactive derivative with an alochol of the formula HO(OA)_nOR^'' 1 , or H(OA)_nNR⁹RlO.

Compounds of the formula (lid) can be made by reacting a maleic acid derivative of the formula R³'θC-CH=CH-COR³ with an amine of the formula HNR R², where R¹ , R², R³ and R³' are as defined for compound (lid) above, under Michaels reaction conditions. The intermediate maleic acid derivative can be made by reacting maleic anhydride with a compound (amine or alcohol) of the formula HR³ and optionally (in either sequence) with a compound HR³'.

Compounds of the formula (lie) can be made by reacting an Λ/-R³ substituted maleimide with an amine of the formula HNR¹ R², where R¹, R² and R³ are as defined for compound (lid) above, under Michaels reaction conditions. The intermediate imide can be made by reacting maleic anhydride with an amine H2NR³ under amidation/imidation conditions.

Compounds of the formula (llf) can be made by reacting an itaconic acid derivative of the formula R³'θC-CH -CH(=CH )-COR³ with an amine of the formula HNR¹ R² , where R¹ , R², R³ and R³' are as defined for compound (llf) above, under Michaels reaction conditions. The intermediate itaconic acid derivative can be made from itaconic anhydride by methods anaogous to those for the maleic acid derivative as described above for compounds of the formul (lid).

Compounds of the formula (llg) can be made by an internal amidation reaction on compounds of the formula R NH-CH₂-CH(CH₂C0₂H)COR³ or a reactive derivative such as a lower, particularly a C1 to C4, alkyl ester, of the carboxylic acid. Such intermediate compounds can be made by reaction of an itaconic acid derivative of the formula CH₂=CH(CH₂C0₂R)COR³ , where R is as defined above in the synthetic routes to compounds of the formula (lla), with an amine R¹ NH2 under Michaels reaction conditions. The itaconic acid ester intermediate can be made by methods analogous to those described above to make the m.aleic acid derivative in the syntehsis of compounds of the formula (lid).

Compounds of the formula (llh) can be made by reacting an Λ/-R³ substituted itaconimide with an amine of the formula HNR¹ R², where R ¹ , R² and R³ are as defined for compound (lid) above, under Michaels reaction conditions. The intermediate imide can be made by reacting itaconic anhydride with an amine H2NR³ under amidation/imidation conditions.

The compounds of the invention can be used in a variety of end use applications, including in agrochemical formulations particularly as adjuvants, emulsifiers, wetting agents, dispersants, thickeners or solubilisers; and, especially for amino oxide or quaternary compounds, in personal care formulations or as fabric softeners.

The use in agrochemical formulations is particulary important and the invention accordingly includes agrochemical formulations incorporating compounds of the formula (I), particularly formulae (lla) to (llh), as adjuvants, emulsifiers, wetting agents, dispersants, thickeners or solubilisers, but particularly as adjuvants.

The invention specifically includes agrochemical compositions which include an agrochemically active compound and, particularly as an adjuvant, at least one compound of at least one of the formulae (I), particularly of one of the formulae (lla) to (llh). The invention further includes the use of compounds of any of the formulae (I), particularly (lla) to (llh), as agrochemical surfactants, particularly as adjuvants.

Surfactants of the formula (I) and particularly of the formulae (lla) to (llh) can be used (particularly as adjuvants) with a wide range of agrochemical active materials and specifically, the active component of the formulation may be one or more plant growth regulators, herbicides, and/or pesticides, for example insecticides, fungicides, acaricides, nematocides, miticides, rodenticides, bactericides, molluscicides and bird repellants. Specific examples of actives include: Herbicides: including water soluble, particularly non-selective, herbicides, more particularly phosphonomethyl glycines, especially as salts such as Glyphosate and Sulfosate {respectively the iso- propylamino and trimethylsulphonium salts of Λ/-phosphonomethyl glycine}; and phosphinyl amino acids such as Glufosinate {2-amino-4-(hydroxymethylphosphinyl) butanoic acid} particularly as the ammonium salt and bipyridinium compounds such as Paraquat {1 ,1'-dimethyl-4,4'-bipyridinium}; triazines such as Atrazine {6-chloro-Λ/-ethyl-N'-(1-methylethyl)-1 ,3,5-triazine-2,4-diamine, and Prometryn {/V,ΛP-bis(1-methylethyl)-6-(methyIthio)-1 ,3,5-triazine)-2,4-diamine}; substituted ureas such as Diuron {W-(3,4-dichlorophenyl)-Λ/,W-dimethylurea}; sulphonyl ureas such as metsulfuron-methyl {2-[[[[(4-methoxy-6-methyl-1 ,3,5-triazin-2-yl) amino]carbonyl]amino]sulfonyl]benzoate}, triasulfuron {2-(2-chloroethoxy)-Λ/-[[(4-methoxy-

6-methyl-1 ,3,5-triazin-2-yl)amino]carbonyl]benzenesulfonamide}, tribenuron-methyl {methyl 2-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-methylamino]carbonyl]amino]sulfonyl] benzoate} and chlorsulfuron {2-chloro-Λ/-[[(4-methoxy-6-methyl-1 ,3,5-triazin-2-yl) aminojcarbonyl] benzenesulfonamide}; pyridine carboxylic acids such as clopyralid {3,6-dichloropyridine-2-carboxylic acid}; aryloxy alkanoic acids such as 2,4-D {2,4-dichlorophenoxyacetic acid}; 2-(4-aryloxyphenoxy)propionic acids such as clodinafoppropargyl {prop-2-ynil (R)-2-[4-(5-chloro-3-fluoropyridinr-2-yloxy) phenoxyj-propionate}; and bis-carbamates such as Phenmedipham {3-[(methoxycarbonyl)amino]phenyl (3-methyl pfιenyl)carbamate}.

Fungicides: including thiocarbamates, particularly alkylenebis(dithiocarbamate)s, such as Maneb {[1 ,2- ethanediylbis-tcarbamodithiato] (2-)] manganese} and Mancozeb {[[1 ,2-ethanediyl- bis[carbamodithiato]](2-)]manganese mixture with [[1,2-ethanediylbis[carbamodithiatoj] (2-)]zinc}; strobilurins such as azoxystrobin {methyl (E)-2-[[6-(2-cyanophenoxy)-4-pyrimidinyl]oxy]- a-(methoxymethylene)benzeneacetate} and kresoxim-methyl {(E)-a-(methoxyimino)- 2-[(2-methylphenoxy)methyl]benzeneacetic acid methyl ester}; dicarboximides such as Iprodione {3-(3,5-dichlorophenyl)-Λ/-isopropyl-2,4-dioxo imidazolidine-1-carboxamide}; halogenated phthalonitriles such as 2,4,5,6-tetrachloro-1,3-dicyanobenzene; benzimidazoles such as Carbendazym {methyl benzimidazol-2-yl carbamate}; azoles such as Propiconazole {1-[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl-methyl- 1H-1,2,4-triazole}, and Tebuconazole {(RS)-1-p-chlorophenyl-4,4-dimethyl- 3-(1H-1 ,2,4-triazole-1-ylmethyl)-pentan-3-ol}; and inorganic fungicides such as Copper hydroxide {Cu(OH)2}; benzoyl ureas such as Diflubenzuron {N-[[(4-chlorophenyl)amino]carbonyrj-2,6-difluoro- benzamide)} and pyrethroid insecticides; and Acaricides including: tetrazines such as Clofentezine {3,6-bis(2-chlorophenyl)-1 ,2,4,5-tetrazine}. The compounds of the invention can be particularly effective as adjuvants for herbicides particularly water soluble, usually non-selective herbicides for example glyphosate types (N-phosphonomethyl glycines and their agrochemically acceptable salts), such as Glyphosate (the /so-propylamine salt of N-phosphonomethyl glycine) and Sulfosate (the trimethylsulphonium salt of N-phosphonomethyl glycine); glufosinate types (phosphinyl amino acids and their agrochemically acceptable salts) such as Glufosinate (2-amino-4-(hydroxymethylphosphinyl) butanoic acid, particularly as the ammonium salt); and bipyridinium types such as Paraquat (1,V-dimethyl-4,4'-bipyridinium). Such water soluble actives can be used as the sole active in for example in aqueous solutions or in water dispersible granules, but more usually, they will be used in combination with water insoluble or immiscible actives in multi active formulations. In particular, formulations can be made up using a water soluble (non-specific) herbicide such as Glyphosate, Sulfosate and/or Glufosinate, with a selective herbicide, such as a sulphonyl urea e.g. metsulfuron-methyl, pyridine carboxylic acid e.g. clopyralid, aryloxy alkanoic acids e.g. 2,4-D, substituted ureas e.g. diuron, or 2-(4-aryloxyphenoxy)propionic acids e.g. clodinafoppropargyl, and/or with an insecticide and/or fungicide. Generally, when used as adjuvants in agrochemical formulations, the compounds of and used in this invention can be added to agrochemical formulations as part of the tank mix (the formulation actually used for spraying) or can be included in pre-formulated products which usually take the form of concentrates, emulsifiable concentrates or solid dispersible granules. When added to tank mix compositions for spray formulations using current spray application rates, generally from 100 to 400 l(spray).ha"¹ (crop treated), usually about 300 I. ha"¹, the concentration of the active agrochemical is typically from about 0.05 to about 3%, more usually from 0.1 to about 0.5 and particularly about 0.2 % by weight of the spray formulation and the concentration of adjuvant will typically be 0.02 to about 2%, more usually 0.2 to about 1% and particularly about 0.1%. The weight ratio of active agrochemical to adjuvant is usually from 1 :5 to 10:1, more usually from 1:2 to about 4:1. These figures correspond to crop application rates of the active agrochemical generally in the range 300 to 4000 g.ha"¹ , more usually from 750 to about 2000 g.ha^"1 (the actual amount depending on the particular crop, agrochemical and effect desired). For low volume spraying, generally higher spray concentrations will be used, but the ratio of agrochemical to adjuvant will be within the ranges given above.

The surfactants of the formula (I) can be used as "built in" adjuvants in concentrate agrochemical formulations that are intended for dilution prior to use. In such concentrates, the concentration of active agrochemical is typically from about 5 to about 60%, more usually from 10 to 40% and the adjuvant concentration is from about 3 to about 50%, more usually from 5 to 30% by weight of the concentrate. The use as built in adjuvants in concentrates is particularly applicable for concentrates where the carrier is aqueous and the active is or includes one or more water soluble herbicides, such as Glyphosate, Sulfosate and Glufosinate.

As adjuvants the compounds of and used in this invention can provide faster effectiveness of agrochemicals especially water soluble herbicides, particularly of the glyphosate type, and can have significantly lower toxicity, particularly aquatic toxicity, than conventional adjuvants, particularly those based on fatty amine ethoxylates. The improved toxicity is also important when the compounds are used to provide other surfactant effects in agrochemical formulations.

Agrochemical formulations of the invention can be made up using surfactants of the formula (I) as adjuvants in a variety of formulation types including: i Water soluble liquids (aqueous dilutable solutions) in which water soluble agrochemical active(s) and surfactant(s) are dissolved in water and the formulation is diluted with water before use. Typically such formulations use concentrations within the ranges: agrochemical active : 100 to 500 g.l"¹ surfactant : 30 to 500 g.l"¹

The surfactant can be a mixture of compounds of the formula (I) and other, particularly non-ionic surfactants (see also below about mixtures).

Possible other components in such formulations include i antifoams, particularly polysiloxane antifoams, typically included at a concentration of from 0.1 and 10% by weight of the concentrate formulation; and ii viscosity modifiers : gums, e.g. xanthan gums, modified cellulose e.g. carboxy- methyl, -ethyl or -propyl cellulose, typically included at between 0.01 and 5% by weight of the concentrate formulation.

Such concentrate formulations can be made by simple mixing of the components. Conveniently this may be carried out by dissolving the agrochemical active(s) and the adjuvant surfactant(s) and any other components in water to give either a concentrate for subsequent dilution to end use concentrations or directly at end use concentration e.g. in the spray tank. Liquid concentrates, particularly emulsifiable concentrates, can include compounds of the formula (I). The amount of surfactant(s) used in such concentrates is typically from 1 to 30% by weight of the concentrate. Other surfactants such as non-ionic, amphoteric, cationic or anionic or combinations of such surfactants may be used together with compounds of the formula (I) (see also below about mixtures). In liquid concentrates, typically use concentrations are within the ranges: agrochemical active : 0.2 to 10% by weight (though with liquid agrochemicals, the concentration can be up to 90%); and surfactant : 1 to 20% by weight of the liquid concentrate. Liquid concentrate agrochemical formulations may also include: solvents such as monoethylene glycol, diethylene glycol, glycerol, (mono)propylene glycol, which, especially with propylene glycol, may also act as a humectant, typically in an amount from 5 to 500% by weight of the surfactants; oils, particularly vegetable or mineral oils, such as spray oils, typically in an amount from 5 to 500% by weight of the surfactants; salts, such as ammonium chloride and/or sodium benzoate, and/or urea as gel inhibition aids typically in an amount from 1 to 10% by weight of the formulation. Solid dispersible granules - the surfactant can be included in a granular agrochemical active formulation or itself be formulated as dispersible granules. Typically granules including agrochemical active contain from 1 to 80%, more usually from 1 to 30%, by weight of the granule of active. When included in granules containing an agrochemical active, the adjuvant typically forms from 5 to 50% by weight of the granule. The granules can include clathrates, particularly urea clathrates, in particular incorporating the compound of the formula (I). Such clathrates can be made by forming a co-melt, including the urea and surfactant, and cooling by e.g. spray cooling. Such clathrate solid granules will typically have a ratio of urea to surfactant adjuvant of from 1:2 to 5:1 by weight. Clathrates can be included in the agrochemical granules or and desirably formulated as a separate adjuvant granule which can be used by direct mixing with granular agrochemical active compositions. When the adjuvant is provided in separate granules from the active agrochemical, the mixing rate of adjuvant granules to agrochemical active granules will depend on the respective concentrations in the granules, but will usually be such as to give a ratio of adjuvant to agrochemical active within the ranges described above. In such granular formulations, other possible components of the granules include: binders, particularly binders which are readily water soluble to give low viscosity solutions at high binder concentrations, such as polyvinylpyrrolidone, polyvinylalcohol, carboxymethyl cellulose, gum arabic, sugars, starch, sucrose and alginates; diluents, absorbents or carriers such as carbon black, talc, diatomaceous earth, kaolin, aluminium, calcium and/or magnesium stearate, sodium tripolyphosphate, sodium tetraborate, sodium sulphate, sodium, aluminium or mixed sodium-aluminium silicates; and sodium benzoate; disintegration agents, such as surfactants, materials that swell in water, for example carboxymethyl cellulose, collodion, polyvinyl pyrrolidone and/or microcrystalline cellulose swelling agents; salts such as sodium and/or potassium acetate, sodium carbonate, bicarbonate and/or sesquicarbonate, ammonium sulphate and/or dipotassium hydrogen phosphate; wetting agents such as alcohol alkoxylates, particularly ethoxylates or ethoxylate/ propoxylates; dispersants such as sulphonated naphthalene formaldehyde condensates and acrylic copolymers; and antifoam agents, typically at a concentration of from 1 to 10 % by weight of the granule.

Spray formulations at application concentration, including surfactants of the formula (I), particularly as adjuvants, can be made up by diluting/dispersing the agrochemical active and the adjuvant in the spray liquid (usually water). Also concentrate forms of the agrochemical formulation can be used, for example: i liquid concentrate containing the agrochemical active and, particularly adjuvant, surfactant dissolved in water; ii liquid concentrate containing the agrochemical active dissolved or dispersed in a non- aqueous, water immiscible liquid, which may be an emulsifiable concentrate and may include a proportion of water, including an adjuvant surfactant; iii liquid concentrate containing the agrochemical active dissolved or dispersed in a non- aqueous, water miscible liquid and including an adjuvant surfactant; iv a solid granular concentrate of or containing the agrochemical active and optionally including an adjuvant surfactant, or the adjuvant surfactant can be provided separately for example as a solution in a solvent (water or a non-aqueous solvent) or a granule, particularly a urea adduct, containing the adjuvant.

Concentrated forms of the agrochemical active will typically be diluted from 10 to 10000, particularly 30 to 1000 times to generate the agrochemical spray for use.

Agrochemical formulations often include more than one surfactant either because surfactants are used in combination to achieve the desired effect or used to provide different effects. It is thus possible in this invention to use combinations of more than one surfactant of the formula (I) or to combine surfactant(s) of the formula (I) with other surfactants.

For adjuvancy, mixtures of adjuvant surfactants can be used and the invention includes agrochemical formulations including compounds of the formula (I) in combination with other adjuvant materials. Commonly such other adjuvants may be non-ionic surfactant adjuvants and examples include so-called hydrocarbyl, particularly alkyl, polysaccharides (generally more correctly described as oligosaccharides); hydrocarbyl, particularly alkyl, amine alkoxylates, particularly ethoxylates, linear or mono-branched alcohol alkoxylates, particularly ethoxylates; sorbitol fatty acid esters; sorbitan fatty acid esters; and ethoxylated sorbitan fatty acid esters. The proportion of compounds of the formula (I) and other adjuvants, particularly non-ionic surfactant adjuvant, (when used) is typically from 1 :5 to 10:1 , more usually from 1:1 to 5:1 by weight. The proportions and concentrations of adjuvants referred to above include both compound(s) of the formula (I) and other, particularly non-ionic surfactant adjuvants. Co-adjuvants, including ionic and/or inorganic materials, for example ammonium sulphate, may be included in adjuvant containing agrochemical formulations of the invention, particularly with non-ionic surfactant adjuvants, especially including those of the formula (I), optionally used in combination with other, particularly non-ionic, surfactant adjuvants.

Generally when other surfactants, especially non-ionic surfactants are used, the compound(s) of the formula (I) will be at least 25% and more usually at least 50% of the total surfactant used to provide the desired effect.

Other conventional components can be included in such formulations such as one or more oils e.g. mineral oil(s), vegetable oil(s) and alkylated vegetable oil(s) which are, typically C| to Cg, alkyl mono esters of vegetable oil fatty acids; solvents and/or diluents such as ethylene and/or propylene glycol or low molecular weight alcohols, which act to solubilise the formulation and/or to reduce the viscosity and/or to avoid or reduce dilution problems e.g. the formation of gels. In particular where non-aqueous, particularly those which are not miscible with or soluble in water, liquids are included e.g. as solvents for the agrochemical and/or in a concentrate to form an emulsion on dilution with water for spraying, other surfactants may be included as solubilisers and/or emulsifiers. Such materials will typically be chosen from anionic, cationic and/or non-ionic surfactants for their effectiveness in solubilisation and or emulsification. Such other surfactant components will, as with formulations using purely conventional surfactants, be used in amounts based on the desired effect. Other surfactants may also be included to improve wetting. Examples of such wetting agents include nonionic surfactants such as alcohol ethoxylates for example of Cg to C-15, particularly primary, alcohols, which may be linear or branched, particularly mono-branched, with from 5 to 30 moles of ethylene oxide; and alkoxylates of such alcohols particularly mixed ethoxylate/ propoxylates which may be block or random mixed alkoxylates, typically containing from 3 to 10 ethylene oxide residues and from 1 to 5 propylene oxide residues, particularly where the polyalkoxylate chain is terminated with propylene oxide unit(s); polyoxyethylene/polyoxypropylene copolymers, particularly block copolymers, such as the Synperonic PE series of copolymers available from Uniqema, and alkyl polysaccharides; anionic surfactants e.g. isethionates, such as sodium cocoyl isethionate, naphthalene sulphonic acids or sulphosuccinates. The amounts of wetting surfactants are typically similar to or the same as the levels typically used to provide adjuvant effects (see above).

The compounds of the formula (I) may be used in combination with non-surfactant materials, particularly solvents or solvation aids such as glycols such as monopropylene glycol and/or polyethylene glycol. The proportion of compounds of the formula (I) to such solvents or solvation aids, (when used) is typically from 1:5 to 10:1 , more usually from 1 :1 to 5:1 by weight.

The invention includes a method of treating vegetation by applying to plants and/or soil a composition including a surfactant of the formula (I) and an agrochemical according to the invention. The agrochemical may be one or more of the types of actives described above, particularly, one or more growth regulators, herbicides, and/or pesticides, for example insecticides, fungicides or acaricides. This method of the invention includes:

(i) a method of killing or inhibiting vegetation by applying a formulation which includes one or more growth regulators and/or herbicides and at least one compound of the general formula (I) as an adjuvant, and/or (ii) a method of killing or inhibiting plant pests by applying a formulation which includes one or more pesticides, for example insecticides, fungicides or acaricides, and at least one compound of the general formula (I) as an adjuvant.

Other additives can be included in agrochemical formulations of the invention including: inorganic salts such as ammonium chloride, calcium chloride and/or sodium benzoate and/or urea in an amount of from 0.01 to 1 % by weight of composition. antifoams which can be silicon based materials such as organopolysiloxanes, which are typically used in an amount from 0.1 to 10%, preferably 0.2 to 6% by weight of the surfactant; 0.01 to 5%, particularly 0.02 to 2% by weight of agrochemical concentrate and 0.0001 to 0.1% preferably 0.001 to 0.05% by weight of a spray formulation at end use dilution; viscosity modifiers, particularly gums such as xanthan gums; cellulose derivatives, such as carboxyl-methyl, -ethyl, or -propyl cellulose, typically used at from 0.01 to 5 wt % of a concentrated formulation; and other non surfactant materials such as stabilisers and/or anti-microbials, typically used at from 0.01 to 5 wt % of a concentrated formulation.

The following Examples illustrate the invention. All parts and percentages are by weight unless otherwise stated.

Materials

MPG mono-propylene glycol NMG Λ/-methylglucamine (A/-1-deoxyglucityl-Λ/-methylamine)

FAE1 Tallow amine ethoxylate - Atlas G-3780A ex Uniqema

Glyphosate glyphosate /so-propylamine salt

NB sprayed amounts of glyphosate are given as amounts of acid equivalent (a.e.)

Example SE1 3-(Λ/-1-deoxyglucityl-Λ/-methyl)aminopropionic acid Λ/-dodecyl amide Method a

Methyl acrylate (3.3 g; 38.5 mMol) was added to a solution of NMG (7.5 g; 38.5 mMol) in water (11.3 ml; the minimum amount needed to give a clear solution on stirring) and the mixture was stirred at ambient temperature. After about 1hour, monitoring the reaction mixture by thin layer chromatography indicated the absence of methyl acrylate (eluted with methanol: chloroform; 5:95 by vol) and the presence of the product (eluted with methanohchloroform; 20:80 by vol). The IR spectrum of the reaction mixture showed a peak at 1728 cm"¹ assigned to the ester group of the desired intermediate Michael reaction product and the H¹ NMR spectrum of the intermediate was consistent.

Dodecyl amine (7.12 g, 38.5 mMol) and K₂C0₃ (0.1 g, 2 mol%) were then added and the mixture changed to turbid viscous solution, the viscosity increasing with time. After stirring for about 2.5 hours, IR examination of a sample of the reaction mix showed the absence of the ester carbonyl band at 1728 cm"¹ and the appearance of an amide carbonyl band at 1648 cm^"1. The K₂Cθ3 was filtered off from the reaction mixture (although this was slow) and the mixture was dried at ambient pressure and temperature to give the title compound as a white sticky solid which had a consistent H¹ NMR spectrum.

The following compounds were made by the method of Synthesis Example SE1 Method a but using corresponding starting materials:

SE2 3-(Λ/-1-deoxyglucityl-Λ/-methyl)aminopropionic acid Λ/-octadecyl amide (the corresponding stearyl amide) SE3 3-(Λ/-1-deoxyglucityl-Λ/-methyl)aminopropionic acid Λ/-octadec-9-enyl amide (the corresponding oleyl amide) SE4 3-(A/-1-deoxygIucityl-Λ/-methyl)aminopropionic acid Λ/-octyl amide SE5 3-(Λ/-1-deoxyglucityl-Λ/-methyl)aminopropionic acid Λ/-2-ethylhexyl amide The reaction with the longer chain amines takes rather longer than with the dodecylamine used in Synthesis Example SE1 ; 4 to 4.5 hours with stearylamine and about 12 hours (overnight) with oleylamine.

Example SE1 3-(Λ/-1-deoxyglucityl-A/-methyl)aminopropionic acid Λ/-dodecyl amide Method b

Methyl acrylate (2.60g; 30 mMol) was added to a stirred suspension of NMG (4.86 g; 25 mMol) in MPG (30 ml) at ambient temperature. The stirred mixture was heated slowly and at about 70 to 75°C the mixture became clear and the IR spectrum of the reaction mix showed a peak at 1728 cm"¹ assigned to the ester group of the desired intermediate Michael reaction product. After stirring for 30 minutes at 75°C, the reaction mixture was cooled to 45°C and dodecyl amine (5.60 g, 30 mMol) was added the reaction mixture remaining clear. After stirring for a further 1.5 hours, the IR spectrum showed the formation of an amide carbonyl band at 1648 cm^"1. The final product was a light brown solid, which had a H¹ NMR spectrum consistent with the title above.

The following compound was also made by the method of Synthesis Example SE1 Method b but using octylamine as the amine.

SE4 3-(Λ/-1-deoxyglucityl-A/-methyl)aminopropionic acid Λ/-octyl amide.

Example SE6 3-(Λ/-1-deoxyglucityl-Λ/-methyl)aminopropionic acid dodecyl ester A suspension of lauryl (dodecyl) acrylate (4.8 g; 20 mMol), NMG (3.9 g; 20 mMol) and mono- propylene glycol (2.2 g; 20 wt%) was heated gradually and the reaction mixture became homogenous after 15 minutes at to 85 to 90°C. The progress of the reaction was monitored by TLC (eluting with chloroform to follow lauryl acrylate and methanohchloroform 40:60 by volume to follow the glucamine and the reaction product) and after 2 hours showed the absence of starting materials and indicated only the product. After removal of the diluent, 10.9 g of product was obtained as a white sticky solid having an ester carbonyl (1740 cm^"1) band in its IR spectrum. Example SE7 - Λ/A/-bis-{3-r(A/-1-deoxyglucityl-A/-methyl)carbonylamidolpropyl}-Λ/-dodecylamine (mixed with Λ/-{3-r(Λ/-1-deoxyglucityl-Λ/-methyl)carbonylamidolpropyl}-Λ/-dodecylamine ) Method a

An homogenous mixture of dodecyl amine (3.71 g; 20 mMol) and methyl acrylate (3.44 g; 40 mMol) was stirred at ambient temperature. The reaction was monitored by TLC (eluting with methanol: chloroform; 5:95 by volume) to follow the level of amine and after 22 hours the amine had disappeared. The TLC plates also showed the build up of the product (together with a minor spot which may be the 1 :1 adduct). The unreacted methyl acrylate was removed under vacuum to yield a crude product as a free flowing transparent liquid retaining an ester carbonyl band at 1740 cm^"1. The measured yield was 5.81 g, compared with the theoretical 7.15 g for a complete 1 :2 Michael addition, suggesting that the crude product was about one third of the bis-adduct title compound and two thirds mono-adduct.

This intermediate (5.81 g) was mixed with one equivalent NMG (3.96 g, 21.4 mMol), K₂COg (0.06 g, 0.4 mMol) and heated. At 140°C the reaction mixture melted, the temperature was then reduced to between 120 and 125°C and became homogenous after about 40 minutes. The reaction was monitored by IR for disappearance of the ester carbonyl band and the appearance of an amide carbonyl band at 1630 cm"¹. After 2 hours the speed of reaction had slowed markedly so a further aliquot of NMG (0.8 g; 4.1 mMol; ca 0.2 equivalents) was added. After 6 hours total reaction time IR monitoring showed that the reaction was complete. 10.3 g of a pale yellow liquid product was obtained.

Method b

An homogenous mixture of dodecyl amine (92.7 g; 0.5 Mol) and methyl acrylate (129.3 g; 1.5 Mol) was stirred at 85°C for 65 hours when IR and TLC analysis showed the reaction to be complete. Excess methyl acrylate was removed under vacuum to give quantitative yield of the crude product as a free flowing transparent liquid having an ester carbonyl UR band at 1740 cm-¹.

This intermediate (100 g ; 0.28 Mol) was mixed with two equivalents of NMG (109.08g, 0.56 M), K₂C0₃ (1.99g, 0.014M) and MPG (30.27g) and heated. At 130°C the reaction mixture became clear and the mixture was held at this temperature to enable reaction. The extent of reaction was monitored by IR for disappearance of the ester carbonyl band and the appearance of an amide carbonyl band at 1630 cm"¹. From time to time, partial vacuum was applied to strip off the methanol formed in the reaction. After 3 hours total reaction time, IR monitoring showed that the reaction was complete. 272.8 g of a yellow viscous liquid product was obtained which was diluted with water (60 g) to form a 70% active material (in a mixture of MPG and water). Example SE8 - Λ/Λ/-bis-{3-r(A/-1-deoxyglucityl-A/-methyl)carbonylamidolpropyl}-Λ/-octylamine (mixed with Λ/-(3-r(Λ/-1-deoxyαlucityl-Λ/-methyl)carbonylamidolpropyl}-Λ/-octylamine ) An intermediate ester amine was made by the method described in Example SE7 (method b) but using n-octyl amine (90.3 g, 0.7 Mol), instead of the dodecylamine used in Example SE7, and methyl acrylate (180.6 g, 2.1 Mol) to give 207.4 g of product (expected 211 g) retaining an ester carbonyl band at 1740 cm"¹ in its IR spectrum.

This intermediate (100.14 g; 0.33 Mol) was further reacted with 2 equivalents of NMG (129.37 g ; 0.664 Mol) as described in Example SE7 (method b) using K₂C03 (2.29 g; 0.7 Mol) as catalyst and MPG (30 g) as solvent. After 3.5 hours, the reaction was complete (as monitored by IR) to give the 285 g of clear yellow, viscous liquid product which was diluted with water (60 g) to form a 70% active material (in a mixture of MPG and water).

Application Example AE1

Compounds of the invention were tested for compatibility with glyphosate (/so-propylamine salt). Compounds SE1 and SE4 were heated to about 90°C and mixed with glyphosate solution (what amounts were used?). Both compounds showed positive compatibility with glyphosate despite low water solubility although compound SE1 produced quite a lot of foam.

Application Example AE2

This Example investigates the adjuvant properties of compounds of the formula (I) in glyphosate formulations were tested on flax, pea and Savoy cabbage {Sav C) and Italian Ryegrass {It R) as target crops. The application rate was 1080 g(a.e).ha"¹, with adjuvant at an application rate of 405 g.ha^"1 (75% of the normal application rate for adjuvants in such formulations of 540 g.ha"¹ ). The effectiveness of the formulations was by visual assessment of Growth Reduction (Gr Red) and Chlorosis/Necrosis (Chlor) 6 DAT with the values being reported in % (related to an untreated control = 0% effect). The results are set out in Table 2 below:

Table 2

Claims

Claims:

1 The present invention provides compounds of the formula (I):

R¹R²X¹-[ Link ]-R³ (I) where Link is a linking group including a moiety of the formula: -C-C-CO-;

X¹ is N; N⁺-»0"; N⁺R⁴" where: R^4" is C-_j to Cg hydrocarbyl carrying an anionic substituent; or N⁺R^An" where: R^ is C-\ to C₂Q hydrocarbyl, hydroxyalkyl, alkoxyalkyl or aralkyl; and An^" is a charge balancing anion; R¹ is polyhydroxy hydrocarbyl, hydroxy hydrocarbyl, or hydrocarbyl; R² is H; hydrocarbyl, or alkoxyalkyl; hydroxy hydrocarbyl; polyhydroxy hydrocarbyl; or

R² is a group of the formula: - [ Link ] R³, where Link is as defined above and R³ is as defined below; or R² together with the nitrogen atom of X¹ and a carboxyl function on the group Link forms a 4, 5, 6 or 7 membered cyclic amide, which is Λ/-substituted with a group R , where R^ is polyhydroxy hydrocarbyl or hydrocarbyl;

R³ is a group -NR⁷ R⁸ ; -(OA)_nNR⁹R¹⁰; or -(OA)_nOR^{1 1} ; where each OA is independently an oxyalkylene group; each n is independently 0 or from 1 to 100; R⁷ is polyhydroxy hydrocarbyl, hydroxy hydrocarbyl, or hydrocarbyl;

R⁸ is H, polyhydroxy hydrocarbyl, hydroxy hydrocarbyl, hydrocarbyl or a group R¹ R²X¹-[ Link ]- where R¹ , R², X¹ and Link are as defined above; R⁹ hydrocarbyl or hydroxy hydrocarbyl; R¹⁰ hydrocarbyl, hydroxy hydrocarbyl, or a group R¹R²X¹-[ Link ]-(OA)_n- , where R¹ , R², X¹ , Link, OA and n are as defined above; and R^{1 1} is hydrocarbyl; or

R³ together with a carboxyl function on the group Link forms a 5, 6 or 7 membered cyclic imide, which is Λ/-substituted with a group R⁸, where R⁸ is as defined above; where: at least one of R¹ , R⁶, R⁷and R⁸ is polyhydroxy hydrocarbyl; and/or at least one of R¹, R⁶, R⁷and R⁸ is hydroxy hydrocarbyl, and at least one of R², R⁶, R⁷, R⁸, R⁹, R¹0 and R^{1 1} is Cg to C₃₀ hydrocarbyl.

2 A compound as claimed in claim 1 of one of the formulae (lla), (lib) or (lie): R²²R²³N-CHR²0-CHR²¹-CO-NR²⁴R²⁵ (lla) _R22_R23_N__CHR20__CHR21__CO(OA)_n OR^{1 1} (Mb)

R²⁶N[CHR²⁰-CHR²¹-CO-NR²⁷R²⁸]₂ (lie) where OA, n and R^{1 1} are as defined above in formula (I); and

R²^ and R²¹ are each independently both H or one is H and the other is methyl;

R²² is polyhydroxy hydrocarbyl;

R²³ is H, a hydrocarbyl, or polyhydroxy hydrocarbyl; or both R²² and R²³ are hydroxy hydrocarbyl;

R²⁴ is hydrocarbyl;

R²⁵ is hydrocarbyl or a group R²²R²³ N-CHR²⁰-CHR²¹ -CO- where R²⁰,

R²¹ , R²² and R²³ are as defined above R²⁶ is Cg to C30 hydrocarbyl; each R²⁷ is polyhydroxy hydrocarbyl; and each R²⁸ is H, hydrocarbyl, or polyhydroxy hydrocarbyl.

A compound as claimed in claim 1 of one of the formulae (lid), (lie), (llf), (llg) or (llh):

R^Δ

where R¹ , R² and R³ are as defined above for formula (I) and R³' is OH, OM, where M is a metal (which may be a fractional metal where the metal valence is greater than 1 ) or an ammonium group, OR' where R' is alkyl, or alkenyl or a group as defined for R³. A compound as claimed in any one of claims 1 to 3 wherein at least one of R , R⁸, R and R⁸ is a polyhydroxy hydrocarbyl group. A compound as claimed in claim 4 wherein the polyhydroxy hydrocarbyl group is a groups derived from glucose. A compound as claimed in any one of claims 1 to 3 wherein at least one of R¹ , R^, R and R⁸ is a hydroxy hydrocarbyl group. A compound as claimed in claim 4 including at least one 2-hydroxyethyl group. A compound as claimed in any one of claims 1 to 7 wherein at least one of R², R^ , R6, R⁷, R⁸, R⁹, R¹⁰ and R^{1 1} is a C₁₀ to C₂ hydrocarbyl group. A compound as claimed in any one of claims 1 to 8 wherein the groups OA are ethylene oxy groups or a mixture of ethylene oxy and propylenoxy groups. A compound as claimed in any one of claims 1 to 8 wherein n is from 3 to 50.

An agrochemical composition of a compound as claimed in any one of claims 1 to 10 and at least one agrochemically active compound. An agrochemical composition as claimed in claim 11 wherein the at least one agrochemically active compound is or includes one or more plant growth regulators, herbicides, and/or pesticides and/or bird repellants. An agrochemical composition as claimed in either claim 11 or claim 12 wherein the at least one agrochemically active compound is or includes at least one water soluble herbicide. An agrochemical composition as claimed in claim 13 wherein the water soluble herbicide is or includes at least one phosphonomethyl glycine; at least one phosphinyl amino acid; and/or at least one bipyridinium compound. A method of treating vegetation by applying to plants and/or soil a composition as claimed in any one of claims 11 to 14. A method of killing or inhibiting vegetation by applying a formulation which includes one or more growth regulators and/or herbicides and at least one compound of the general formula (I) as defined in any one of claims 1 to 10 as an adjuvant. A method of killing plant pests by applying a formulation as claimed in any one of claims 10 to 14 which includes one or more pesticides and at least one compound of the general formula (I) as defined in any one of claims 1 to 10 as an adjuvant.