CA1065311A - Organotin sucrose compounds - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Organo-tin sucrose compounds and processes for their production are provided herein. In such organo-tin sucrose compounds three of the tetrava-lent tin valences are carbon-tin bonds and the fourth is other than a carbon-tin bond. Such compounds exhibit pesticidal and herbicidal activity of the types comparable to the corresponding parent compounds lacking the sucrose residue but with greatly improved water solubility and higher activity per mole of tin.

Description

~)65311 This invention relates to biocidally active organo-tin sucrose com-pounds which are carboxylic acid esters of biocidally active organo-tin com-pounds wlth sucrose.
A number of biocidally active organo-tin compounds have been developed in recent years for a variety of pesticidal or herbicidal applica-tions limited by their poor water solubility, low vapor pressure or both.
Accordingly, it is an ob~ect of one aspect of the present invention to provide organo-tin compounds having pesticidal or herbicical activity to-gether with improved water solubility.
An object of another aspect of this invention is to provide such organo-tin compounds which may be used to provide agricultural compositions useful in controlling the growth of undesired plant or animal pests.
An ob~ect of a further aspect of this invention is to provide such organo-tin compounds which may be used to provide improved antifouling paints.
An object of an additional aspect of this invention is to provide such organo-tin compounds which may be used to provide a composition and me-thod for controlling mites.
An ob~ect of still another aspect of this invention is to provide such organo-tin compounds which may be used to provide a composition and method for controlling the growth of aquatic weeds.
Briefly, by a broad aspect o~ this invention, an organo-tin sucrose compound is provided of the formula:

10~53~.~

cOO-sucrose x LcooJ p ~H2~ n [S]mSnRlR2R3 in which the tetravalent tin atom has only three tin-carbon bonds cnd wherein X is:

~ ~ ¦ or ¦¦ ;

m is O or l;
p is O when m is 1 and p is 1 when m is O;
n is O or an integer from 1 to 6 with the proviso that, when m is 1, n is an integer from 1 to 6; and at least two of Rl, R2 and R3 are each alkyl of 1 to 8 carbon atoms, cycloalkyl of 3 to 8 carbon atoms or aliphatic aryl or aralkyl of 6 to 10 ring carbon atoms;
j when m is 1 or when m and n are both O, one of ¦ Rl, R2 and R3 is the acyl radical of an inorganic mineral ¦ acid or of a hydrocarbon; carboxylic or sulfonic acid; and 20 I when m is O or when m is 1 and n is said integer, all Il of Rl, R2 and R3 have the above-indicated values.

,! ~

10~531~
According to another aspect of this invention an or~ano-tin sucrose compound is provided having tne gen~rdl formula:
foo- sucrose rl l LcooJ p [CH2~-n-rS]m- SnRlR2R3 in which sucrose represents a sucrose residue, X repre-sents H2 ~ or CH -, CH2 - CH -m is O or 1, p is O when m is 1 and p is 1 when m is O;
n is O or an integer from 1 to 6 with the proviso that, when m is 1, n is an integer from 1 to 6; and Rl,R2 and R3, which may be the same as or different from one another, are groups such that the tin atom has three tin-carbon bonds and one bond which is not a tin-carbon bond. Thus, in the case when n is O, p is 1 and n is O or in the case where p is O, m is 1 and n is an integer, Rl,R2 and R3 all re-present the same or different organic groups so that thetin atom forms its three tin-carbon bonds with carbon atoms : of the groups Rl,R2 and R3. When n is an integer, m is O
and p is 1, however, two of Rl, R2 and R3 represent organic groups as above and the other Rl,R2 and R3 represents an inorganic moiety or an organic moiety, where the organic group is attached to the tin atom by other than a tin-carbon bond.

A
It ~O~S311 By variants of this invention, m = 0 and p = 1; or n = 0 or an in-teger from 2 to 6; or n = 3 or 4; or n = 0.
By another variant, alkyl is butyl, and by a further variant, cycloalkyl i9 cyclohexyl.
By still other variants, hydrocarbon aryl is phenyl, and hydrocar-bon aralkyl is benzyl.
By another variant, at least two of Rl, R and R3 have the same values, while in yet another variant, R = R = R ~
By still another variant, one of Rl, R and R3 is the aryl radical of an inorganlc mineral acid.
By a still further variant, one of R , R and R is the acyl radical of a hydrocarbon carboxylic sulfonic acid of 1 to 8 carbon atoms.
By a further variant, the acyl radical is p-toluene sulfonate.
By yet other specific variants, the compound is (n-butyl)3-SnOCOC6H4COO-sucrose; (phenyl)3-SnOCOC6H4COO-sucrose; (cyclo-C6Hll)3-SnOCOC6 H4COO-sucro~el; ((n-butyl)3-SnOCOCH2CH2COO-sucrose; (phenyl)3-SnOCOCH2CH2COO-sucrose; sucrose-ococ6H4coo(cH2)3sn~enyl)2Br; or (phenyl)3SnSCH2COO-SUcrse-- 4 a -~OtjS;~ll j `
The organo-tin co~pounds of aspects of this invention have shown bio-cidal activity. Thus, amongst the compounds of aspects of this inven-tion one can find fungicidal, algicidal, miticidal, herbi-cidal and bactericidal activity. The activities are often, per unit weight of tin, much higher than the activities of currently used organo-tin compounds. In addition, the presence of a sucrose residue appears to render the com~
pounds more water soluble than many currently used organo-tin compounds.
The organo-tin sucrose compounds of aspects o~ this invention and in particular those in which m and n are O, can be prepared in good yields by relatively si ple and direct reaction processes. The product is a mixture of compounds which differ in the position of attachment of the oxygen atom to the sucrose residue and in the number of tin-containing groups attached to the sucrose residue. The mixtures can be refined or purified to give a pure product - but this is expensive an~ since this mixture appears to be biocidally effective, the mixture is usually satisfactory.
The use of the single formula:

COO-sucrose rl 1 LCool ~H~ nLS]m SnRlR2~3 herein is therefore to be construed as embracing the mix-tures noted above.

~ 5-The compounds in which m and n are both zero and p is 1 are preferred since they are usually simpler to prepare and have better bactericidal properties than those in which m is O, n is an integer from 1 to 6 and p is l, and so the sucrose residue is directly linked via a tin-carbon bond to the tin atom. When n is an integer and p is 1, it is preferred that n be from 2 to 6 and most preferred that n be 3 or 4, since the intermediates corresponding to the case where n is 3 or 4, and parti-cularly 3, are readily available.
The nature of the groups Rl,R2 and R3 is,as noted~bove,dependent upon the requirement that the tin atom in the organo-tin sucrose compound have three covalent tin-carbon bonds. Organo-tin compounds where there are other than three tin-carbon bonds appear to have less effective biocidal properties.
Those of the groups Rl,R2 and R3 which are attached by carbon-tin bonds to the tin atom are organic groups such as alkyl, cycloalkyl groups, aryl and/or alkaryl groups.
The alkyl group is desirably one which contains from 1 to 12 carbon atoms and it may be a straight or branched alkyl group; more preferably, the alkyl group contains 1 to 8 carbon atoms and especially good results seem to be given when the alkyl group contains 4 carbon atoms, e.g. an n-butyl ~06S3il group so that if all three groups Rl,R2 and R3 represent alkyl groups, together they contain about 12 carbon atoms which seem to give best results. Suitable alkyl groups include but are not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec.-butyl and tert.-butyl;
butyl is preferred. Contemplated alkyl equivalents are alkyl groups bearing one or more substituents, e.g., halogen atoms or lower alkoxy, e.g. methoxyethyl, chloro-methyl, methoxybutyl and bromoethyl.
The cycloalkyl group is desirably one containing from 3 to 8 carbon atoms. Suitable cycloalkyl groups include but are not limited to cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl, optionally substituted, e.g., by alkyl or alkenyl of up to 4 carbon atoms to form cyclo-alkylalkyl or cycloalkylalkenyl, e.g., cyclopropylmethyl;
cyclohexyl is preferred.
The aryl group is desirably a hydrocarbon aryl group of 6 - 10 ring carbon atoms preferably phenyl or naphthyl and especially phenyl. Aralkyl is aryl substi-tued by lower alkyl as defined herein, preferably benzyl.
If one of the groups Rl,R2 and R3 is attached byother than a tin-carbon bond to the tin atom, that group ~an be in an inorganic moiety or an organic moiety where the organic portion is linked through other than a carbon atom to the tin atom, i.e. an acyl group.

In the case where one of R , R and R represents an inorganic acyl moity, the acyl group is preferably of an inorganic mineral acid; suitable examples include but are not limited tothe halogen atoms e.g. bromine or chlorine atoms, an inorganic salt group e.g. a nitrate or phosphate, or one valence of an oxygen or sulphur atom. In the case where one of R , R and R
represents an organic acyl moiety, the acyl group is preferably of a hydro-carbon carboxylic or sulfonic acid of 1-15 carbon atoms, preferably alkanoly, aroyl, alkanesulfonyl or arylsulfonye of 1-8 carbon atoms; suitable examples include but are not limited to the acyl radicals of formic, acetric, propion-ic and butyric acids; of methane, ethane, propane and butane sulfonic acid;and of benzene, toluene and xylene sulfonic acid. Preferred organic acyl groups are the acetate and p-toluene sulfonate.
These residues R , R and R can be unsubstituted or can carry one or two simple substituents, examples of which are lower alkyl groups, e.g.
methyl and ethyl groups, halogen atoms, e.g. chlorine atoms, lower alkoxy groups, e.g. methoxy or ethoxy, or amino groups e.g. dimethylamino groups.

The group X is preferably:

~ or FH2 ~

.~ .

106S31~

~since the compounds in which X is:
CH -CH -while being capable of being made in a fashion similar to compounds where X is ~ or f~2-tend to be more difficult to prepare since the products are somewhat oily.
The compounds in which m is 1 and p is O can in some circumstances be advantageous in that their synthesis can be relatively simple.
The compounds in which n and m are zero and p is 1, can be prepared by condensing sucrose with an anhydride having the general formula:

/ CO

\CO /
in which X is as defined above ~o~S3~1 to give a sucrose ester of the general formula:

COO-sucrose COOH

in which X and sucrose are as defined above, followed by reacting the sucrose ester with an organo-tin hydroxide or its corresponding oxide of the general formula:
RlR2R3SnOH or (RlR2R35n)20 in which Rl, R2 and R3 are as defined above.

In the first stage of this reaction, the two reagents can be dissolved in an inert, aprotic solvent e.g. dimethyl formamide, the resulting ester being apparently mixtures including several 1:1 adducts and some 2:1 adducts together with some free sucrose. In the second step of the reaction which involves the use of the expensive organo-tin com-pound, the reaction proceeds in high yields, often as high as 85%.
To prepare the compounds in which n is an integer, m is O and p is 1, the sucrose ester e.g. ¦ sucrose phtha-late is initially prepared and then that ester is converted to a metal salt, e.g. the sodium salt which is usually the cheapest and most readily available, and reacted with an organo-tin compound having the general formula:
Ph~ Sn [CH~ n Br in which n is as defined above and Ph represents a phenyl group, .;.~

1~;5;~1 to give a compound of the formula:

COO-sucrose COO ~H3 nsnph3 in which X, sucrose, n and Ph are as defined above.
In this compound, the bond between the tin atom and a carbon atom of the aryl (phenyl) group is more sen-sitive to attack by halogen atoms than the bond between the10 tin atom and the carbon atom of the linking alkylene group, so that this compound can be converted by reaction with a halogen, e-g.; bromine, in solution in, for example, methyl alcohol, at low temperatures to give the following compound according to the invention:

X COO-sucrose ( 2)nSnPh2Br.
This bromine substituted compound can be hydrolysed, if desired, to eliminate the brominf atom and give the follow-ing compound according to one aspect o~ this invention:

¦ /COO-sucrose X \ ~ O.
COO (CH2 ) nSnPh2 in which X, Ph, sucrose and n are as defined above.

At 10653~1 Compounds in which m i9 1 and p is 0 can be prepared by reacting an ester having the general formula:
R R R SnS(CH2) COOR
in which Rl, R2 and R3 are as defined above, n i8 1-6 and R is an alkyl group e.~. methyl with sucrose.
The reaction can be conducted in a solvent e.g. dimethylformamide by hesting in the presence of an alkali catalyst, e.g. potassium carbonate.
Some organo-tin sucrose compounds of aspects of this inv ention have been found to have good miticidal activity, some to have fungicidal activity, some to have algicidal activity, some to have herbicidal activity and some to have bactericidal activity. The organo-tin sucrose compounds of aspects of this invention are also safe to use in spraying onto crops either in powder or liquid formulations because when exposed to sunlight or present in soil, the compound is believed to decompose to a safe inorganic tin com-pound and not to produce long-term pollution.
The biocidally active organo-tin sucrose compounds of aspects of this invention can be used in essentially the same manner as corresponding prior art compounds lacking the sucrose moiety in the molecule and variations in the non-sucrose portion of the molecule appear to have generally the same effect or biocidal activity a~ i8 known for the prior art compounds, e.g., see U.S. Patent No. 3,264,177.

i - 12 -106S3~1 Preferred rates for application of the compounds of aspects of this invention to foliage, stems and fruit of living plants range from 0.01 to 106 kilograms of active ingre-dient per hectare. More preferred rates are in the range S of 1 to 10,000 kilograms per hectare and the most preferred rates are in the range of 10 to 1,000 kilo-grams per hectare. The optimum amount within this range depends upon a number of variables which are well known to those skilled in the art of plant protection. These vari-ables include but are not limited to the disease to be con-trolled, weather conditions expected, the type of crop, stage of development of the crop and the interval between applications. Applications within the range given may need to be repeated one or many more times at intervals of 1 to 60 days.

The compounds of aspect~ of this invention can be applied in a variety of formulations, including wettable powders, dusts, suspensions, emulsifiable concentrates, solutions, granules, pellets, etc. Concentrates can also be prepared for use by formulators in further processing near the point of use. The formulations will include one or more bio-cidally active compounds of aspects of this invention and can include surface-active agents, solid or liquid diluents and other materials as required to produce the desired formulation.

~5311 The surface-active agents act as wetting, dispersing and emulsifying agents which assist dispersion of the active material in the spray, and which improve wetting of waxy foliage and the like by the spray. The surfactants can in-clude the same anionic,nOn-ionic and cationic agents as have been used heretofore in similar biocidal compositions. A
detailed list of such agents may be found in "Detergents and Emulsifiers Annual," (John W. McCutcheon, Inc.).
Anionic and non-ionic surfactants are preferred.
kmong the anionic surfactants, preferred ones are alkali and alkaline earth salts of alkylarylsulfonic acids, e.g.
decylbenzenesulfonates and alkylnaphthalenesulfonates, dialkyl sodium sulfosuccinate esters, sodium lauryl sulfate, sodium N-methyl-N-oleyltaurate, sodium dodecyldiphenyl ether disulfonate, partial phosphate esters of alkyl and alkylphenyl polyethyleneoxyethanols, and the oleic acid ester of sodium isothionate. Preferred non-ionic surfac-tants include alkylphenyl polyethylene glycol ethers, poly-oxyethylene derivatives of sorbitan fatty esters and long-chain alcohols and mercaptans, as well as polyoxyethyleneesters of fatty acids.
Preferred dispersants are alkali and alkaline earth salts of lignosulfonic acids, salts of polymerized alkylaryl-10~531i sulfonates, e.g. those sold under the Trade Marks "caxad" and"Darvan" (sodium slats of polymerized alkyl napthaline sulfonic acids, or of polymerized substitu-ted acyl alkyl sulfonic acid, of R.T. Vanderbrit Co.) as well as methylcellulose, polyvinyl alcohol and the like.

Surfactants are present in compositions of aspects of this invention in amounts up to 20~ by weight based on the total weight of the resulting composition. When larger amounts of surfactant are desired, as for improved wetting of, spreating on or penetration into foliage, mixing in the spray tank is usually preferable for convenience.
Powder and dust preparations can be made by blending the active in-gredient, with or without surfactant, with finely divided solids, e.g. talcs, natural clays, pyrophyllite, diatomaceous earth; flours e.g. walnut shell, wheat, redwood, soya bean and cotton seed; or inorganic substances e.g. mag-nesium carbonate, calcium carbonate, calcium phosphate, sodium silicoalumin-ate, sulfur and the like. The choice of a particular diluent is based on consideration of the physical and chemical properties required of the product, the chemical and physical properties and concentration of the active ingredi-ent, and the use for which the formulation is intended. The compositions are made by thoroughly blending the active ingredient with the diluent and other additives. Usually a grinding step, as in a hammer mill or fluid ener-8Y mill, in included. The particles in dust and powder preparations are pre-ferably less than 50 micron3 in average diameter. With compounds which are highly water insoluble, improved activity may be obtained with still finer grinding.

~' ~ - - 15 -106S31~
Preferred wettable powder formulations will contain 40% or more active ingredient together with sufficient sur-factant and inert dil~ent to permit dispersion in water for spray application. Compositions intended for dust applica-tion will generally contain less than 50~ active ingredient.
Powdered compositions can be converted to granulesby adding a liquid, treating mechanically, and usually drying. Mechanical devices such as granulating pans, mixers and extruders can be used. Compaction devices can be used even without a liquid in the mixture. Water soluble binders, e.g, inorganic salts, urea, ligninsulfonates, methyl cellulose, other water soluble polymers and the like, can be included in these particulate formulations in amounts up to 25%
by weight of the finished granule or pellet. Such materials~
also aid in disintegration of the pellet and release of the active ingredient under field conditions. Alternatively, a melt, solution or suspension of the active ingredient can be sprayed on the surfact of preformed granules of clay, ver-miculite, corn cob and the like. Surfactants may also be included in formulations of the latter type.
Solution formulations can be prepared in suitable solvents. All solution formulations can be used for direct low-volume applications. For such use, all that is required is practical solubility and stability of the active ingredient in the chosen solvent. An important sub-class of solution ~ 5'~

` ` . lA ~ ,~" `, lO~S3~1 formulations is emulsifiable concentrates. For these, a water-immisible solvent is required as well as surfactant to help form and stabilize the final aqueous emulsion in which the biocide is applied. It is preferred that the active ingredient in solution formulations remain totally dissolved at 0C or as low a storage temperature as can reasonably be expected to occur for prolonged periods. In order to insure this, co-solvents, which may be water-miscible, may also be included in the formulations.
Suspension formulations can be made in water, organic solvents or in mixtures of water and water-miscible organic solvents in which the active ingredient has a solubility under 0.1%. The preparations usually include, in addition to the active ingredient and liquid carrier, suf-facts, viscosity control agents and other moidfiers. They are prepared by grinding the components in a sand mill, roller mill or pebble mill, preferably until the average particle size is under 20 microns. It is entirely practical, and in some instances biologically advantageous, to grind until a major proportion of active ingredient is 2 microns in diameter or smaller. Hydrocarbon and other flammable carriers should have boiling points above'~ 125C for safety in handling. Suspensions in hydrocarbons are suitable for ex-tension in spray oils and, by inclusion o~ a suitable emul-sifying agent, may also be made sprayable from water.

10~5311 Organic liquids suitable for preparation of solutions, suspensionsand emulsifiable concentrates of the compounds of aspects of this invention include alcohols, glycols, Cellosolves, (the Trade Mark for mono-and dialkyl ethers of ethylene glycol and their derivatives, of Union Carbide Corporation), carbitols, ethers, ketones, esters, sulfamides, amides, sulfoxides, sulfones, paraffinic hydrocarbons, aromatic hydrocarbons and halogenated hydrocarbons.
Choice of a liquid is dictated by the solubllity of the active compound to be used and whether a suspension or solution is desired. The class of compounds represeuted by broad aspects of the present invention is variable in solubili-ty characteristics, so it is not possible to generalize in the use of particu-lar solvents for particular purposes.
All compositions intended for spray use can contain minor amounts of additives to reduce foam, inhibit corrosion, prevent claying, reduce cak-ing, etc. a~ the conditions of uge may dictate. The conditions of need for an use of of such additives are generally known in the art.
The compositions of a~pects of the invention can contain, in addi-tion to the active ingredient of this invention, conventional insecticides, miticide~, bactericides, nematicides, fungicides or other agricultural chemi-cal~ e.g. fruit set agents, fruit thinning compounds, fertilizer ingredient~
ant the like, 50 that the compositions can serve useful purposes in addition to the biocital activity of the compounds of aspects of this invention.

~hi - 18 -1~65311 Examples of organo-tin sucrose compounds according to aspects of this invention are given below in Table 1. Many of these com-pounds have been tested for their biocidal activities and the results are also given below:

COMPOUND No .
(n-butyl)3SnOCOC6H4COO-sucrose (phenyl)3SnOCOC6H4COO-sucrose 2 (cyclo-c6Hll)3snococ6H4coo-sucrose 3 (n-butyl)3SnOCOCH2CH2COO-sucrose 4 (phenyl)3SnOCOCH2CH2COO-sucrose S
sucrose-OCOC6H4COO(CH2)3Sn(phenyl)2Br 6 (phenyl)3 SnSCH2COO - sucrose 7 The compounds were first tested against the fungi which commonly grows on paint coatings, both inside and outside buildings. There are 16 fungi which appear to be most fre-quently found:
A~ternaria aZternata (syn. tenuis);AspergiZtus fZa~us;
AspergiZtus ver8ico Zor;
Aureobasidium puZZuZans;
CZadosporium herbarum;

;, .

~065311 Cur~u~ria geicutata;
DendryphieZZa 6aZ*na;
Pus~rium o~yspor~m;
PaeciZomyce~ ~ariot*i;
Penic*ZZium e~pansum;
PeniciZZiu~ purpurogenum;
PestaZotia ~acrotricha;
Phoma vioZacea;
Stachybotry~ atra;
StemphyZium dentriticum; and Trichoderma ~iride.

'. The compounds of aspects of this invention were tested for their effectiveness against these 16 fungi by dissolving the compounds in turn in Cellosolve (Trade Mark for ethylene glylcol mono-ethyl ether) and incorporating the solution into a Czapek-Dox agar medium at 100, 10 and 1 ppm by weight. After - hardening7 the agar plate was inoculated with spore sus-pensions of the 16 fungi and incubated at 25C for ten days.
Spore germination was then counted; the results are listed in Table 2 together with the results for tributyltin oxide used as a control.

. -20-1()653~1 TA~LE 2 Compound Number of fungi showing inhibition of spore germination (max.16) s 1 l ~1 10 ~
.
oxide ..

* inactive against - As can be seen from Table 2, most of the compounds show very high activities. The high activity at the 1 ppm level of some of the compounds is remarkable considering the much lower tin content of these co.mpounds compared with standard organo-tin biocides, e.g. the tributyltin oxide.
.Compounds 1 and 5 were tested for fungicidal activity in a polyvinyl acetate copolymer emulsion paint having the following composition:

10~5311 Tloxide RCR (the Trade Mark of a brand of titanium dioxide) . . .. . . . . . . . . . . . . . . . 34.2 sodium hexametaphosphate (4% solution) . . . . . . . . . . . . ~ . . . . . . . 1.3 Celadol M450 (4Z solution) (Trade Mark ~ . . . . . . . 8.5 water . . . . . . . . . . . . . . . . . . . . . . . . 25.6 Vinamul N6815 (Trade Mark ~ . . . . . . . 30.4 Various concentrations of the two compounds as well as various concentrations of Amical 48 (Trade Mark for a commercial fungicidal) as a con-trol were incorporated into this emulsion paint at the pigment dispersion10 stage. The emulsions, including a further control emulsion containing no fungicide, were brushed onto plaster covered glass boiling tubes and allowed to dry. One set of painted tubes was tested as made while a second set was tested after 200 hours of artificial weathering according to British Standard BS 3900,F3.
Fungicidal testing was started by inoculating coated tubes with a suspension of mixed fungal spores in 0.01% Tween 80 solution (Trade Mark for a polyoxyethyle derivative of fatty acid partial esters of sorbital anhydrides of Altas Chemical Industries) containing not less than 10 spores/ml.
The fungal species employed were:
Alternaria alternata, Aureobasidium pullulans, Cladosporium herbarum, Paecilomyces variotii, Penicillium expansum, and Stemphylium dendriticum.

106S3~1 Inoculated tubes were kept under conditions designed to promote controlled condensation on paint surfaces and incubated for four weeks. Fungal growth present on painted tubes after this time was assessed by examination through a stereoscopic ~icroscope and rated on a 0-5 scale where 0 = no growth and 5 = overall growth.
In addition, all emulsions were stored for four weeks at 37C and then examined for color, odor and rheology defects.
10 All of the emulsions appear to have satisfactory storage properties; no adverse color, odor and rheology changes were apparent after storage. The results of the fungicidal tests are listed in Table 3.

.
CompoundAmount Fungal Growth Assessment (ppm) as made after 200 h. artificial weathering 20 controlnone 4 3-4 Amical 48* 0.25 1 Amical 48 0.5 0 Amical 48 1.0 0 0 . .

' ~ ~ ~

_. _ Another established application of organo-tin com-pounds is in anti-fouling paints; the marine alga Enteromorpha is considered to be mainly involved in the fouling of ships' hulls.l Compounds of aspects of the invention were tested against Enteromorpha in sea water modified with algal nutrients at concentrations of 1 to 0.1 ppm; the results are listed in Table 4.

1 0 .

~ ;

+ = effective - = not effective 2S As can be seen from the above,many of the organo-tin sucrose compounds of aspects of this invention are remarkably active algicides. For comparative purposes, the minimum concentration A~

lO~S311 at which the commercially used tributyltin oxide and tributyl-tin fluoride are effective in these tests is 0. 3 ppm. The algicidally active sucrose compounds in Table 4 are therefore at least thre~ times more active, even though these sucrose compounds have considerably less than half the tin content of the commercial biocides as shown in Table 5. At a U.S. price in early March, 1977 of over S10,000 per ton for tin, the economic savings of higher activity per tin atom can be sig-nificant.

Compound % Sn .
tributyltin oxide 39.8 tributyltin fluoride 38.4 (butyl)35nOCOC6H4COO-sucrose 15.2 (phenyl)3SnOCOC6H4COO-sucrose 14.1 Current technology produces anti-fouling paints with prolonged biocidal effectiveness by incorporation of the biocide into a polymer to ensure very slow release of the - active material. The poly-functional nature of the sucrose compounds of aspects of this invention ives them the ability to be readily incorporated into polymers.

, l , `` iO6S311 The anti-bactericidal properties of organo-tin sucrose compounds of aspects of this invention were tested by growing the bacteria both on agar plates and in a liquid culture;
the results are given in Table 6.

S

CompoundEscherichi Saccharomyces Micrococcus C li cerevisiae dentifrificans Conc. Inhib. Conc. Inhib. Conc. Inhib.
(ppm) (~) (ppm) (%) (ppm~ (%) 1 2 84 100 8 100 0.25 100 15 1 83 23 8 ~ ~ 100 As can be seen above, only very low concentrations of the compounds are required to supress the growth of ~ M.denitrificans. ~he minimùm concentration for inhibition may he even less, since 0.25 ppm was the lowest concentra-tion tested.
Some compounds of a8pects of this invention, especially compounts 1 and 3, have been found to be effective miticides. ~hey were tested by the leaf dip method as set out in Table 7 and compared with conventional miticides much as Dibrom and Tedion. As can be seen from these results, Compounds 1 and 3 were highly effective.

A~i T.~ L~ ? 10~3~1 Organism Compound Dose Percentage . (ppm)Effectiveness

2 Spot Mite 3 40 100 (Tetranychus urticae Koch) 1 40 100 Dibrom 10 39 Mite Egss 3 40 100 (Tetranychus urticae Koch) 1 40 96 Tedion 2.5 100 .

Compounds 1, 2 and 3 ~ of aspects of this invention were tested for their effect against various weeds and crops both for pre-emergence and post-emergence effects. It was found that -compound 3 had no noticeable effect at a dose of 33 gm cm~2; this indicates a lack of phytotoxicity which is important for the use of the compounds as miticide on vege-tation. Compounds 1 and 2, on the other hand, were found 20to have certain selective effects on weeds and crops and so appear useful as selective herbidies. For example, com-pounds 1 and 2 have no effect on rice, but do have a high degree of toxicity to, for example, wild oats.
Compounds 1 and 2 haYe also been found to exercise a useful degree of control over the growth of aquatic weeds when present in water at a dose of 2 ppm. They are at least as effective as copper sulphate against aquatic weeds and are also potentially less toxic to aquatic animals, for example, fish, than copper sulphate.

106S3~1 Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. The following preferred specific embodiments are, therefore, to be construed as merely illustrative.

In the following Examples, the temperatures are set forth uncor-rected in degrees Celsius; unless otherwise indicated, all parts and percentages are by weight. The values obtained in elemental analyses are within commonly accepted limited of error. All new products give the expected parent peaks in the mass spectra, and the expected absorption peaks in NMR and IR.

Example 1 A. Preparation of phthalic half ester of sucrose An excess of phthalic anhydride was heated with sucrose in solution in dimethylformamide at a temperature of 60C for S hours. The reaction proceded as in the fol-lowing reaction scheme:

[~ O + sucrose ~ o- sucro=e Titration of the resulting ester compound I with stan-dard alkali showed that the ester had the composition of one acid group/molecule.
Analysis Calculated for 1:1 adduct: C 48.98~; H 5.3~;
Found: C 46.6%; H 4.8%;
Characteristic features of I.R
.
OH region 3400 cm~l, -ICl- 1710 cm~l.
o B. Preparation of organo-tin compound The ester I prepared above was reacted with triphenyl-tin hydroxide or bis(triphenyltin) oxide in solution in-benzene at 50~C for 3/4 of an hour to give the compound in15 a yield of 83~ by weight, based on the weight of starting organo-tin compound:

~ C - O-sucrose ~11--0-SnPH3.

Analysis Calculated: C 54.4%; H 4.7%;
Found: C 54.6~; H 4.8%.

Characteristic features of I.R.
-OH region 3350 cm~l, (a) 1730 cm~l -6- (typical of organic esters), O
(b) -C- 1640 cm~l, ll (typical of carboxylate O group attached to tin), Ph 730, 695 cm~l.

Example 2 The ester I prepared in part A of Example 1 was re-acted with bis(tri-_-butyltin) oxide in solution in benzene . at 40 to 50C for 3/4 of an hour to give the product:

1l (a) O;sucrose ~ C O-Sn(butyl)3 Analysis Calculated: C 49.29%; H 6.7%;
Found: C 50.78%; H 7.00%.

106S31~

Characteristic features of I.R.
OH region 3350 cm~l, (a) 1725 cm-l, - lCI-O
(b) -C- 1630 cm~l.
o Example 3 The phthalic half ester of sucrose prepared as described in part A of Example 1 was treated with sodium hydroxide to give the sodium salt and the latter was re-acted with excess Ph3Sn(CH2)3Br in dimethylformamide at 50C for 3 days to give the compound:

C O-sucrose II
C (CH2 ) 3SnPh3 Analysis Calculated: C 54.95%; H 5.2%;
Found: C 54.6%; H 5.2%.

10~5311 Characteristic features of I.R.
OH region 3350 cm~l, 1720 cm~l.
O
Ph 925, 690 cm~l.
This compound II was then dissolved in methyl alcohol and reacted at 50C with bromine to giYe the compound:

CO-sucrose ~h III
ICl --- O(CH2)3lnBr O Ph AnalysiS
Calculated: C 47.5%; H 4.64%;
Found: C 46.8%; H 5.29%.

Characteristic features of I.R.

OH region 3350 cm~l.
~C- 1720 cm~l.
O
Ph 730, 695 cm~l.
(ObserYed reduction in comparatiYe intensity of phenyl absorption to carbonyl absorbtion).
This compound III can be hydrolysed, if so desired, to give the compound:

_ , _ ~ O(Ch~)33n 1 -O

Example 4 A. Preparation of succinate half ester of sucrose This material was prepared in a manner similar to that described in part A of Example 1 for the phthalate half ester, i.e. a 5:1 mixture of succinic anhydride:

sucrose was heated at 60C in dimethyl formamide for 5 hours:
~0 I O + sucrose - > HOOCCH2CH2 -C - O-sucrose.

CH2 C~
~O

Titration of the product indicated that it had a composition intermediate between a 1:1 and 1:2 structure.

B. Preparation of organotin derivatives of the succinate O
Il 11 ~ he compound: ~u3SnOCCH2CH2C-O-sucrose was prepared using reaction conditions similar to those described for the phthalate derivative, the compound being obtain in a yield 106S31~

of 75% by weight based on the weight of the startins organo-tin compound.
Analysis Calculated for 1:1 compound: C 46.96%; H 7.10~;
Found: C 45.95%; H 7.20%.
Characteristic features of I.R.
C=O at 1730 cm~l 1640 cm~
OH 3400 cm~l Example 5 Ili1 In a similar manner, the compound: Ph3SnOCCH2CH2CO-sucrose was prepared in a yield of 84%.
Analysis C34H4QO14Sn Calculated; C 51.6%; H 5.1%;
Found: C 51.4~; H 4.7%.
Characteristic features of I.R.
C=O 1730 cm~l, 1640 cm~
OH 3400 cm~l Ph 690 cm~l, 730 cm~l.
Example 6 Other Derivatives of Phthalate Half Ester In a similar manner, the tricyclohexyl tin derivative:

ll C O-sucrose O - o-sn(c6Hll) was prepared in a yield of 80%.

10~;5311 Analysis C38H5814Sn Calculated: C 53.2%; H 6.6%;
Found: C 53.1%; H 6.6%.
Characteristic features of I.R.
C=O at 1730 cm~l, 1640 cm~
OH at 3400 cm-l.

Example 7 Methyl-S-triphenylstannylthioglycollate (2.0 g, 4.4 mmole) was dissolved in 15 ml dimethylformamide and heated with sucrose (4.5 g, 13.2 mmole) in 45 ml dimethylformamide and potassium carbonate (0.04 g) at 50~55C for two hours.
The solution was poured into cyclohexane and the lower layer washed with several portions of cyclohexane until the majority of the dimethylformamide had been removed.
The resulting semi-solid was extracted with chloroform and the solvent removed, The purification procedure (cyclohexane wash, chloroform extraction)was repeated to leave 1.2 g solid which was found to consist of some unreacted sucrose and a mixture of substituted products.
- Analysis C32H58O12SSn:
Calculated: C 50.20%; H 4.97%;
Found: C 51.42%; H 5.58%.

10~531~
The preceding examples can be repeated with similar success by substituting the generically or specifically described components and/or operating conditions of this invention for those used in the preceding examples.

Claims (24)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. An organo-tin sucrose compound of the for-mula:

in which the tetravalent tin atom has only three tin-carbon bonds and wherein X is:

, or ;

m is 0 or l;
p is 0 when m is 1 and p is 1 when m is 0;
n is 0 or an integer from 1 to 6 with the proviso that, when m is 1, n is an integer from 1 to 6; and at least two of R1, R2 and R3 are each alkyl of 1 to 8 carbon atoms, cycloalkyl of 3 to 8 carbon atoms or aliphatic aryl or aralkyl of 6 to 10 ring carbon atoms;
when m is 1 or when m and n are both 0, one of R1, R2 and R3 is the acyl radical of an inorganic mineral acid or of a hydrocarbon; carboxylic or sulfonic acid; and when m is 0 or when m is 1 and n is said integer, all of R1, R2 and R3 have the above-indicated values.

2. A compound according to Claim 1, wherein m = 0 and p = 1.

3. A compound according to Claim 2, wherein n is 0 or an integer from 2 to 6.

4. A compound according to Claim 3, wherein n is 3 or 4.

5. A compound according to Claim 3, wherein n is 0.

6. A compound according to Claim 1, wherein alkyl is butyl.

7. A compound according to Claim 1, wherein cycloalkyl is cyclohexyl.

8. A compound according to Claim 1, wherein aliphatic aryl is phenyl.

9. A compound according to Claim 1, wherein aliphatic aralkyl is benzyl.

10. A compound according to Claim 1, wherein at least two of R1, R2 and R3 have the same values.

11. A compound according to Claim 10, wherein R1 = R2 = R3.

12. A compound according to Claim 1, wherein one of R1, R2 and R3 is the acyl radical of an inorganic mineral acid.

13. A compound according to Claim 1, wherein one of R1, R2 and R3 is the acyl radical of a hydrocarbon carboxylic or sulfonic acid of 1 to 8 carbon atoms.

14. A compound according to Claim 13, wherein said acyl radical is p-toluene sulfonate.

15. A compound according to Claim 1, (n-butyl)3SnOCOC6H4COO-sucrose.

16. A compound according to Claim 1, (phenyl)3SnOCOC6H4COO-sucrose.

17. A compound according to Claim 1, (cyclo-C6H11)3SnOCOC6H4COO-sucrose.

18. A compound according to Claim 1, (n-butyl)3SnOCOCH2CH2COO-sucrose.

19. A compound according to Claim 1, (phenyl)3SnOCOCH2CH2COO-sucrose.

20. A compound according to Claim 1, sucrose-OCOC6H4COO(CH2)3Sn(phenyl)2Br.

21. A compound according to Claim 1, (phenyl)3SnSCH2COO-sucrose.

22. A process for preparing an organo-tin sucrose compound of the for-mula:

in which the tetravalent tin atom has only three tin-carbon bonds and wherein X is:

, or ;

m is 0 or l;
p is 0 when m is 1 and p is 1 when m is 0;
n is 0 or an integer from 1 to 6 with the proviso that, when m is 1, n is an integer from 1 to 6; and at least two of R1, R2 and R3 are each alkyl of 1 to 8 carbon atoms, cycloalkyl of 3 to 8 carbon atoms or aliphatic aryl or aralkyl of 6 to 10 ring carbon atoms;

when m is 1 or when m and n are both 0, one of R1, R2 and R3 is the acyl radical of an inorganic mineral acid or of a hydrocarbon; carboxylic or sulfonic acid; and when m is 0 or when m is 1 and n is said integer, all of R1, R2 and R3 have the above-indicated values.

which comprises: (a) condensing sucrose with an anhydride having the general formula:

in which X has the above-indicated values to form a sucrose ester of the general formula:

and (b) reacting said sucrose ester with an organo-tin hydroxide or its corresponding oxide of the formula:
R1R2R3SnOH or (R1R2R3Sn)2O

in which R1, R2 and R3 have the above-indicated values to form an organo-tin sucrose compound in which n is 0, m is 0 and p is 1.

23. A process according to Claim 22, further comprising: reacting the resultant product with an organo-tin compound of the formula Ph3Sn(CH2)nBr wherein is an integer of 1 to 6 and Ph is phenyl to form a compound of the formula:

24. A process according to Claim 23, further comprising halogenating the resultant product to form a corresponding compound wherein one of R1, R2 and R3 is halogen.