US2927054A - Liquid dispersions of acetals of a sugar - Google Patents

Description

United States Patent LIQUID DISPERSIONS 0F ACETALS OF A SUGAR No Drawing. Application November 15, 1954 Serial No. 469,014

24 Claims. (Cl. 167-42) The invention is that of liquid dispersions comprising at least one substantially water-insoluble cyclic acetal of a sugar substantially homogeneously dispersed therein and at least one completely water-miscible, non-hydrocarbon organic dispersing agent or medium (e.g. a solvent) for the acetal contained in the dispersion in a concentration up to (i.e. including) the maximum-stably-suspendable-in-water concentration for the cyclic acetal in the dispersing agent or medium (e.g. the solvent) used.

By maximum-etably-suspendable-in-water concentration is meant the highest concentration of the waterinsoluble cyclic acetal of the sugar alone in the dispersing agent or medium, such as a solvent, used, at which the dispersion of the acetal in the dispersing medium (e.g. solvent) can be uniformly dispersed in water, for example, in a ratio of one quart of dispersion to one hundred gallons of water, and still give in the resulting aqueous medium a substantially stably dispersed suspension of the water-insoluble acetal.

Then, a substantially stably dispersed suspension of the water-insoluble cyclic acetal in water means a suspension in which all, or at least substantially all, of the acetal of the sugar dispersed in the water-miscible, non-hydrocar bon organic dispersing medium, .after such dispersion is uniformly distributed in water, goes into substantially colloidal suspension in the water or at least remains suspended in finely divided state in it for from at least an appreciable fraction of an hour to several hours or more, rather than'settling out readily and promptly, and with none or at worst only an insignificant amount of the acetal forming aggregates or clumps that separate on the surface of the water and/or the sides of the container. It is not precluded from this definition that some of the colloidally suspended or finely divided suspended particles gradually coalesce and form slightly larger particles, distinct from aggregates and clumps, some of which coalesced particles may collect on the bottom of the container.

Thus, the maximum-stably-suspendable-in-water concentration of any cyclic acetal of a sugar is its concentration in the water-miscible non-hydrocarbon dispersing agent or medium (e.g. an aliphatic solvent) used for it, above which the acetal separates or coagulates out. in aggregates or clumps on the surface of the water and/ or sides of the container when the dispersion of it in such medium is uniformly distributed in water.

More specifically the invention includes non-aqueous solutions of at least one water-insoluble cyclic acetal of a sugar dissolved in at least one completely Water-miscible, non-hydrocarbon aliphatic solvent for such acetal and with the acetal in a concentration not greater than its maximum-stably-suspendable-in-water concentration in the solvent used.

As a completely water-miscible, non-hydrocarbon aliphatic solvent there is included an aliphatic solvent other than a hydrocarbon and one that dissolves in, or

mixes with, water, at least in, for example, somewhere aqueous dispersion of the type described hereinbelow 2,927,054 Patented Mar. 1, 1960 about equal proportions to give a solution or at least a stable dispersion that does not separate into individual layers of water and solvent. The solvent is still completely water-miscible when it gives a solution or at least a stable and uniform dispersion that does not separate into layers, when the solvent and the water are mixed in the proportions in which they are containedin an and embraced by the invention.

The invention also includes the foregoing dispersions (e.g. solutions) which have dispersed (e.g. dissolved) in them in addition to the one or more water-insoluble cyclic acetal or acetals of a sugar, at least one other substantially water-insoluble, ether-linked derivative of a saccharide and selected from a benzyl ether of a sugar and a benzyl ether of a glycoside, and each in a concentration no greater than its respective maximum-stablysuspehdabledn-water concentration in the solvent used, as defined above. The same foregoing definition applies to a benzyl ether of a sugar or of a glycoside when the definition is read with either of them respectively replacing the acetal of a sugar in the definition.

By ether-linked derivative of a saccharide is meant, for example, a cyclic acetal of a sugar, such as results from condensation of a sugar with at least one aldehyde or ketone with the elimination of water (as by union of the oxygen of the carbonyl group of the aldehyde or ketone and the hydrogen from each of two hydroxyl groups of the sugar), as well as an aralkyl ether of a sugar, such as is obtained by condensation of an aralkyl halide (with or without substituent groups on the aryl nucleus) as a benzyl halide'with a metal salt of a sugar, such as sodium or disodium saccharate, or of a glucoside, with the elimination of the corresponding metal halide, e.g. sodium chloride, to give a benzyl sugar (or benzyl ether of a sugar) or a benzyl glucoside (or benzyl ether of a glucoside) with the term benzyl used broadly to include the benzene ring further unsubstituted or with at least one other substituent group on it, for example, one or more lower alkyl groups as methyl or ethyl.

The invention embraces also the substantially stable aqueous dispersions of (a) at least one water-insoluble cyclic acetal of a sugar, or of (b) at least one water-insoluble cyclic acetal of a sugar together with at least one substantially water-insoluble benzyl ether of a sugar and/or of a glycoside, which dispersions result when the foregoing water-dispersible, non-aqueous solutions are uniformly distributed, that is to say, dispersed, in water.

These substantially stable aqueous dispersions of Waterinsoluble cyclic acetals of a sugar, or of such acetals together with at least one benzyl ether of a sugar and/ or of a glycoside, are a significantly eifective part of the invention because at least of their advantageous utility manifested by their unusual sticker property. This is discussed more fully below.

Accordingly, an important embodiment of the inven tion embraces substantially uniform and stable aqueous dispersions of (a) water-insoluble cyclic acetals of a sugar, and (1)) such acetals together with at least one water-insoluble benzyl ether of the class consisting of benzyl ethers of a sugar and benzyl ethers of a glycoside; and in which dispersions the content of ether-linked derivative of a sugar is held stably dispersed in the aqueous medium by the dispersion or solution in it of at least one completely water-miscible dispersing agent for such ether-linked derivative of a saccharide included in the dispersion, and which dispersing agent is inert to such saccharide derivative other than as to its dispersing action on it.

In other words, the action of such dispersing agent for the ether-linked derivative of a saccharide is simply physical in nature in that it serves merely to disperse in water the desired quantity of such derivative, such as the water-insoluble cyclic acetal of a sugar, or derivatives, for example, such acetal together with a benzyl ether of a sugar or of a glycoside or both, without any change in chemical constitution of such derivative. At the same time the dispersing agent is itself completely miscible in the water and without any change in chemical constitution.

The dispersing agent for the ether linked derivative of a saccharide is completely water-miscible when it will dissolve in water or at least give a stable and uniform dispersio'n, from which the dispersing agent will not separate out when it is mixed with water in the same proportions that such agent and the water are to have to one another in an aqueous dispersion of an acetal of a sugar or of such acetal with a benzyl ether of a sugar or of a glycoside or both, of the type described herein and embraced by the invention. The expression dispersing agent is used here in its usual generic sense in the physical aspect as embracing both a solvent or solubilizing agent as Well as a substance that serves to hold another stably suspended in finely divided form in a liquid medium, in which such other substance is insoluble or incompletely soluble.

The sugars, of which the acetals alone or acetals and benzyl ethers are dispersed in the non-aqueous as well as aqueous dispersions of the invention, include any of the various sugars, such as a mono-saccharide sugar, as dextrose (glucose, grape sugar, or starch sugar), mannose, levulose (fructose, honey sugar, or fruit sugar), invert sugar, galactose, and the like, or a di-saccharide sugar as sucrose (cane sugar, beet sugar), lactose (milk sugar), or malto'se, or a tri-saccharide sugar as rafiinose, in addition to the various hexoses, or pentoses, for example, Xylose, or oligo-saccharides, and other sugars.

The water-insoluble cyclic acetal of a sugar can be a mono-(cyclic acetal) or di-( cyclic acetal) or other poly- (cyclic acetal), namely, one having two or more cyclic acetal rings on the same saccharide molecule, and either of the homogeneous type (i.e. having all cyclic acetal rings alike on the same molecule) or of the heterogeneous type (having difierent cyclic acetal rings on the same molecule) or mixed poly-(cyclic acetals) comprising a heterogeneous poly-(cyclic acetal).

Any such cyclic acetal of a sugar can be prepared by condensing the selected sugar by heating it, for example, under reflux, in presence of a catalytically effective amount of an acid acetalizatio'n catalyst such as a strong mineral acid or an acid-reacting salt or a mononuclear aromatic sulfonic acid, to the boiling point of, and with, a carbonyl group-containing, non-sugar aliphatic compound of the class consisting of (a) an aldehyde having at least three carbon atoms, (b) a ketone, (c) a halogensubstituted aldehyde having at least two carbon atoms, and (d) a halogen-substituted ketone.

The individual cyclic acetal rings are formed in the method of preparation of the cyclic acetals from the elimination of water in the reaction of the sugar with the aldehyde or aldehyde and ketone. This may be considered graphically as if occurring by the condensation of the oxygen of their carbonyl group with the hydrogen of each of two near hydroxyl groups of the sugar. These hydroxyl groups should be linked respectively to adjacent carbon atoms of the chain of carbon atoms of the sugar, or to carbon atoms separated from one another by an intervening carbon atom. Thereby, there are produced respectively fiveor six-membered cyclic acetal rings on the saccharide molecule.

Thus, the condensation of propionaldehyde with two hydroxyl groups of a sugar introduces the propylidene p,

into the saccharide molecule to form the cyclic acetal ring JO\ /H -$-O CzHu Similarly, the corresponding condensation with butyraldehyde introduces the butylidene group,

=(i'1-C H1 to form the cyclic acetal ring In each such cyclic acetal ring, the two carbon atoms linked to one another on the left hand side of the ring (as just illustrated) are part of the aliphatic carbon chain of the saccharide molecule.

Among the non-sugar, carbonyl group-containing aliphatic compounds that can be condensed along with any of the applicable sugars are aldehydes and ketones, saturated or unsaturated, and straight or branched chain, or cyclic, and unsubstituted or substituted with radicals or groups that are inert under the reaction conditions.

Suitable aliphatic aldehydes are saturated and openchain, and include propionaldehyde, n-butyraldehyde, isobutyraldeh yde, valeraldehyde, trimethylacetaldehyde (or pivaldehyde), the methyl pentanals as Z-methyl pentanall, capronaldehyde, the dimethyl butyraldehydes, trimethyl propionaldehyde, a heptaldehyde, 2-ethyl hexaldehyde, an octaldehyde, a nonaldehyde such as 2,5,5-trimethylhexaldehyde, and unsaturated aldehydes as crotonaldehyde, hexadienal, vinyl crotonaldehyde; and cyclic as cyclo'pentyl aldehyde; and the substituted lower and higher aldehydes, as halo-substituted such as chloral or bromal, or dichloropropionaldehyde; as well as reversible polymers of the aldehydes that form them, for example, trimers such as para-propionaldehyde and para-butyraldehyde.

Among the ketones are the aliphatic which comprise acetone, methyl ethyl ketone, the propyl and iso-propyl methyl ketones, the four butyl methyl ketones (e.g. methyl iso-butyl ketone), the methyl amyl ketones, the methyl hexyl ketones, and other open-chain ketones which also can be substituted such as the halo-ketones as chloracetone, and also the cyclic ketones as cyclopentano'ne, methyl cyclopentanone, dimethyl cyclobutanone, ethyl cyclobutanone, cyclohexanone, the alkylcyclohexanones as the technical mixture of ortho-, meta-, and para-methylcyclohexanone, and others.

An unusually advantageously eifective subgroup of dispersions of the invention, of the non-aqueous solutions as well as of the aqueous dispersions, is that wherein the cyclic acetal of the sugar is the mixed poly-(cyclic acetals) comprising a heterogeneous type of poly-(cyclic acetal) of the sugar. A particularly unusually advantageously useful group of these dispersions are those wherein the propylidene group is one of the cyclic acetal groups in the heterogeneous type of poly-(cyclic acetal) of a sugar. Thenan especially unusually advantageously useful type of these latter dispersions are those wherein the propylidene group is one of the cyclic acetal groups, and the butylidene is the other, in the heterogeneous type poly-(cyclic acetal) of a sugar. In these wherein the propylidene group occurs in the mixed poly-(cyclic acetals) of a sugar, the most strikingly effective are those in which the mixed poly-(cyclic acetal) results from the condensation of the sugar with the propionaldehyde (used to at least ten mole-percent) and some other aldehyde or ketone, as described above, in the presence of the acid aeetalizatitn catalyst, and remaining after removal of the catalyst and any water. introduced with it as well as the water formed during the condensation.

By mole-percent is meant the percentage that the number of moles of the particular reagent used, in this case the propionaldehyde, is of the total number of moles of the particular reagents referred to; or as in this case, the sum of the moles of propionaldehyde and moles of the other non-sugar, carbonyl group-containing aliphatic compound.

The. ratio of the propionaldehyde together with the other aldehyde or ketone used, to the sugar should be sufficient to yield mixed poly-(cyclic acetals) with the quantity of sugar used. This can readily be checked by preliminary laboratory tests. If too much sugar was used, that can be noted from the extent of residual sugar left after the propionaldehyde and other aldehyde or ketone has been consumed in the condensation.

It is advantageous for the total of the propionaldehyde and other aldehyde or ketone used to be a slight excess over that required to form cyclic acetal groups with all of the hydroxyl groups available for such condensation in the amount of the particular sugar used. That can be determined by easy control test involving check for any excess of the aldehyde or ketone used after all the sugar has gone from the solid state in the reaction mixture and the latter is uniformly liquid.

The preparation of the mixed poly-(cyclic acetals) of a sugar, comprising the heterogeneous type of such acetal, wherein one cyclic acetal ring has the propylidene group linked to its two oxygens and on the same saccharide molecule is the divalent residue of a difierent aliphatic, non-sugar aldehyde or ketone of the type described above, are illustrated by, but not restricted to the following examples: 7 Example 1.Sucr0se, propionaldehyde and butyraldehyde Into a steam-jacketed copper autoclave equipped with an agitator adapted to stir a heavy slurry there was charged 10.2 liters (8.33 kilos) of butyraldehyde. With' the agitator going there were, added 3.75 liters (2.72 kilos) of propionaldehyde, and while stirring vigorously twenty pounds (9.08 kilos) of sugar were mixed in. Forty grams of phenolsulfonic acid were then added and the autoclave was closed. While the agitator was going continuously, the temperature was allowed to rise, to about 50 C by the heat of the reaction itself without application of any external heat. After an hour, steam at atmospheric pressure was introduced into the steamjacket. The reaction was raised in that Way to about 97 C. while the pressure in the autoclave rose to a maximum of about twenty pounds per square inch.

In about four hours, after all of the solid sugar had reacted and thus no longer appeared in the reaction mixture, the reaction was complete. In that time, the pressure in the autoclave dropped to almost Zero. The reaction mixture then was cooled to about 50-60 C. and neutralized by stirring in forty grams of powdered sodium carbonate monohydrate. The neutral mixture was filtered and then concentrated in two stages; first, at atmospheric pressure to recover unreacted excess aldehyde, and then at reduced pressure, in this case twentythree inches of mercury, to remove the remaining butyraldehyde and water formed during the acetalization.

There remained as the yield twenty-seven pounds of a clear, light yellow, resinous product, soft enough to how readily while hot. The end product comprising the heterogeneous propylidene butylidene poly-(cyclic acetal) of the sugar is practically insoluble in water and in aliphatic hydrocarbons, for example, normal-heptane, mineral oil, and gasoline, and in chlorinated hydrocarbons such as carbon tetrachloride. The product is readily soluble in a large variety of other solvents, for example, lower alkyl alcohols such as lower alkanols as methanol, ethanol, normal-bntanol, with the solubility indicating a decrease as the moecular weight of the alkanol increased,

and lower alkyl polyhydric alcohols as ethylene glycol, also alkyl ketones such as acetone, methylethyl ketone, methylbutyl ketone, methylisobntyl ketone, and in lower alkylamines as monoisopropylamine, and also in mononuclear heterocyclic amines as pyridine.

Example 2.-Sucrose, propionaldehyde and heptaldehya'e 400 grams of fine granulated sugar, 200 grams (3.45

moles) of propionaldehyde, 200 grams (1.75 moles) of heptaldehyde, and 4 grams of toluene sulphonic acid were allowed to react while being agitated in a vessel provided with stirrer and reflux condenser. After one hour all of the sugar was in solution and temperature of the mixture reached 87 C. Then 4 grams of calcium carbonate, made into a slurry with a small amount of water, were stirred in to raise the pH to about 6, and the mixture was filtered, and the filtrate decolorized with decolorizing carbon, and its filtrate concentrated. The yield was 680 grams of product insoluble in water, soluble in ethanol, and even more readily soluble in methanol.

Example 3.--Sucr0se, propianaldehyde and crotonaldehyde 400 grams of sugar, 300 milliliters (242.0 grams or 4.17 moles) of propionaldehyde, 300 milliliters of croton aldehyde, and 4 grams of toluene sulphonic acid were processed as in Examples 1 and 2. The yield was 530 grams of product.

Example 4.Sucrose, acetone and pr'opionaldehyde 400 grams of sucrose, 200 milliliters of acetone, 200 millilters (2.78 moles) of propionaldehyde, and 4 milliliters of commercial 65% phenol sulphonic acid were stirred under reflux condenser, and heated by means of a water-bath held at to 90 C. The sugar gradually went into solution. After 3 hours, six grams of powdered sodium bicarbonate were added, and the stirring continued for five minutes. The heating bath was then removed, and 400 milliliters of 91% isopropyl alcohol were added, and the solution filtered. The filtrate solution was then treated with 10 grams of decolorizing carbon, filtered and concentrated by evaporation under reduced pressure of about 23 inches of mercury, and yielded'415 grams of clear, soft resinous product.

Example 5.Sugar, chloral and propionaldehyde 200 grams of sugar, 190 grams (1.29 moles) of chloral technical grade and 85 milliliters (1.06 moles) of propionaldehyde were stirred and heated together (without a catalyst) for three hours and five minutes, in a flask immersed in a bath having a starting temperature of 70 C. The bath was gradually heated to 92 C. over this time, thereby to avoid undue discoloration. The sugar gradually went into solution. Toward the end of the reaction, the remaining sugar dissolved rapidly and the heating of the solution was carefully controlled to avoid rapid darkening. As soon as all of the sugar had entered into the reaction as seen by the reaction mixtures becoming a practically homogeneous solution, 5 grams of powdered sodium bicarbonate were stirred in while the batch was still hot, to neutralize the; acidity produced. The product was diluted with 200 milliliters of methanol to permit filtration; the filtrate was decolorized with decolorizing carbon, filtered, and the resulting filtrate concentrated by evaporation. The product was a clear, brittle, water-insoluble resin; yield 260 grams. No deliberate separation addition of an acid catalyst was needed because this particular grade of chloral contained free hydrochloric acid.

Example 6.Sugar, cyclohexanone and propionaldehyde 200 grams of sugar, milliliters (121.85 grams or 2.09 moles) of propionaldehyde, 1 milliliter of boron trifiuoride etherate containing 7.6 to 7.8% boron, were reacted for 4 hours with stirring and refluxing over a bath held at 80 C. The reaction mixture was cooled diluted with 150 milliliters of acetone (throwing 41 grams of material out of solution), filtered, neutralized over anion exchange resin, and concentrated. The yield of clear resinous product was 316 grams, insoluble in water and in mineral oils; slightly soluble in normal-heptane and carbon tetrachloride, and soluble in methanol, ethanol, butanol, and acetone.

Example 7.Sugar, chloroacetone and propionaldehyde 200 grams of sugar, 150 milliliters of chloroacetone, 150 milliliters of propionaldehyde, 1 milliliter of boron t'rifluoride etherate (same as used in Example 6) were processed as in Example 6. The reaction in this case required about 2 hours.

Example 8.-Suga'r, Z-ethylhexaldehyde, propionaldehyde Example 9.-Glucse, butyraldehyde and propionaldehyde In a three-necked, round bottom flask equipped with stirrer and reflux condenser, there were mixed twentynine grams (0.5 mole) of propionaldehyde, 36 grams (0.5 mole) of butyraldehyde, 90 grams (0.5 mole) of anhydrous dextrose, and l milliliter of commercial phenol sulfonic acid (added last). The mixture was stirred Without: external heating for an hour, and then heated in a water-bath held at 6065 C. for three and one-half hours. The solution was then neutralized by stirring with 2 grams of calcium carbonate, while being heated in a water-bath held at 6570 C. The mixture was then cooled and filtered, and the filtrate concentrated, leaving the resinous solid product of the reaction.

Example 10.Galact0se, acetone and propionaldehyde A mixture of fifty-four grams of anhydrous galactose (0.3 mole), 20.1 grams of 95% propionaldehyde (0.33 mole), sixty five milliliters of acetone (excess) and 3 milliliters of commercial 65% phenolsulfonic acid (added last) was stirred under reflux condenser for four and one-half hours while being heated in a water-bath held at 75 to 80 C. Practically all the sugar had reacted after this time. The mixture was allowed to cool, and was dissolved in one hundred milliliters of methanol, and then neutralized by stirring at about 50 C. with three grams of powdered sodium bicarbonate. The mixture then was cooled, filtered with the aid of Celite, and the resulting filtrate was concentrated on the steam-bath under twenty-three inches of vacuum. The product, weighing 59.5 grams, was a clear, brown, fusible resin, very soluble in methanol, but only slightly soluble in water.

Other applicable Water-insoluble mixed poly-(cyclic acetals) include propylidene benzylidene sucrose, 1,2- isopropylidenel,6-benzylidene glucose, and others obtained by using in the various suitable procedures the proper selection of two different aldehydes or ketones, or an aldehyde and a ketone, of the types described here inabove and also below.

The type of applicable mono-(cyclic acetal) of a sugar is illustrated by, but not restricted to, the products of the following examples:

Example 11.Bazylidene sucrose (butyraldehyde acetal of sucrose) A mixture of 244 grams (2 mols) of butyraldehyde,

342 grams (1"mole) of granulated sugar, and 2 grams of phenolsulfonic acid was stirred on a steam-bath under a reflux condenser for four hours. The reaction mixture was then cooled to 50 C., 3 grams of powdered sodium carbonate added, and the mixture stirred until the pH rose to about 6. On standing, a gummy, water-soluble layer settled to the bottom. The clear upper layer was decanted and concentrated by heating on the steam-bath under 23 inches of vacuum. The resulting product, a clear viscous syrup, was water-insoluble, but soluble in most polar organic solvents.

Example 12.Proplyidene sucrose Two kilograms of granulated sugar, 2 liters of propionaldehyde, and 10 milliliters of a 6568% solution of phenolsulfonic acid were stirred together on the steambath at the boiling point of the aldehyde in a flask equipped with a refiux'condenser. The mixture gradually became homogeneous. After one and three-quarter hours, the solution was allowed to cool somewhat, and 10 grams of sodium bicarbonate were added. The mixture then was heated until no further evolution of carbon dioxide indicated neutralization. Heating was stopped. The product was then diluted by adding 2 liters of dry benzene, and the solution allowed to cool and, when cool, filtered and concentrated by evaporating ofi the benzene. 2.7 kilograms of clear, resinous product remained.

Example 13 Propylidene glucose was obtained from 2 kilograms of anhydrous glucose, 2.5 liters of propionaldehyde, and 20 grams of toluene sulfonic acid, reacted by the method of Example 12, in a yield of 2.45 kilograms.

Replacing the propionaldehyde by the equivalent amount of acetone gives 1,2-mono-isopropylidene glucose.

The water-insoluble homogeneous type of poly-(cyclic acetal) of a sugar is one in which its particular (cyclic) alkylidene or arylidene (for example, benzylidene or naphthylidene) groups are derived from a single aldehyde or ketone of the type described herein. In other words, it is such acetal in which all the cyclic acetal groups on the particular saccharide molecule are the same. Such poly-(cyclic acetal) of a sugar canbe obtained by using a sufficiently higher molar proportion of the sugar to introduce into it the desired possible number of like cyclic acetal rings, for example, by a process correspondingly similar to that of Examples 11 and 12.

Thus, for example, the di-(cyclic acetal) of any of the various sugars can be obtained, in general, by using 3 or 4 moles of the selected aldehyde or ketone instead of only 2 moles in the foregoing method of Examples 11 and 12. In many instances, the use of 3 moles yields a mixture of the monoand di-acetals, as occurs for example, with 3,5,5 trimethylhexaldehyde. The corresponding homogeneous poly-(cyclic acetals) are obtained by replacing the sucrose by fructose or glucose, or by some other sugar. Di-propylidene glucose, di-isopropylidene glucose, and other dialkylidene or diarylidene acetals of the same or other sugars are similarly prepared. Tri- (n-butylidene)-glucose and tri-(cyclic acetals) of other sugars are prepared similarly by using the correspondingly higher molar ratio of the aldehyde or ketone.

As the process goes on in the examples using sucrose and an aldehyde, some amount of the aldehyde cleaves some of the sucrose. Thus, the end products of such examples contain, along with the particular cyclic acetal of sucrose, amounts of such like acetals of fructose and glucose.

Then also, as sucrose can hydrolyze when heated in the presence of water and acid and thus go through inversion to fructose and glucose; and as water forms by the condensation in the process of making these cyclic 'acetals, some such inversion also can occur. As a result, the end products of the examples using sucrose may contain also comparatively minor amounts of such like acetals of fructose and glucose, due to such inversion.

Generally, the specific aldehyde or ketone used in any of the preceding examples can be replaced respectively in part or whole by about the same molal proportion of some other aldehyde or ketone of its same type or any other type of those described herein as applicable in preparation of the cyclic acetals, or by mixtures of any of them. Applicable aromatic aldehydes embrace particularly the mononuclear as well as the polynuclear type. Aside from the aldehyde group, these can be unsubstituted as in benzaldehyde, and the naphthaldehydes, or further nuclearly substituted as in the monoor poly-, e.g. di-halogenated 13,0- and p-chlorobenzaldehyde, o-bromobenzaldehyde, and 2,4-dichlorobenzaldehyde, and the nitro compounds as p-nitrobenzaldehyde, or monoor polyalkyl substituted as lower alkyl such as methyl, ethyl, propyl or isopropyl, as well as the mixed substituted with any compatiblesubstituents, for example, 2-chloro-4-nitrobenzaldehyde. Actually, the aromatic nucleus can have any other substituents or compatible combination of them, in addition to the aldehyde group,

so long as the resulting acetal of a sugar is still waterinsoluble. Other cyclic aldehydes as a heterocyclic aldehyde such as fnrfural are also included.

Cyclic ketones, whether monoor poly-nuclear, can be condensed similarly to give the corresponding acetals. Such ketones are exemplified by benzophenone, acetophenone, naphthaquinone, and the like, and these may be nuclearly substituted similarly to What is described above as to the aldehydes.

Because of the many different sugars that can be condensed with any one or more of the many different aldehydes and/or ketones of the type described, no upper limit can be placed on the number of carbon atoms in the applicable aldehyde or ketone. So far as presently indicated, those cyclic acetals of a sugar, having a total of not over fourteen carbon atoms in the group or groups, other than the sugar residue, joined to the single carbon linked to both oxygens of the cyclic acetal ring (briefly called the acetal ring-closing carbon) are generally applicable in the liquid dispersions of the invention. Those cyclic acetals of a sugar, wherein there is a total of not over nine carbon atoms in the non-sugar residue group or groups joined to the ring-closing carbon are especially effective in these dispersions.

The benzyl ethers of a sugar, already stated above as prepared by reacting an aralkyl halide such as a mononuclear benzyl halide with a metal, such as the sodium, salt of the selected sugar, are illustrated by, but not restricted to, the preparation of:

Example 14.-Benzyl sucrose A solution of 36 pounds of granulated sugar in 1.64 gallons (6.2 liters) of water was prepared by stirring and heating them together in a steam-jacketed kettle until the sugar completely dissolved. After cooling the solution to about 30 0., there was mixed rapidly with it a solution of 8.5 pounds of sodium hydroxide in 3 quarts (2.85 liters) of water, prepared by rapidly stirring the solid hydroxide in the water until it completely dissolved and allowing it to cool to 60 C. Then 25 pounds of benzyl chloride were added, and the mixture stirred while heating to 95-100 C. (by steam, at atmospheric pressure in the jacket), and the reaction continued until the benzyl chloride odor disappeared (about 5 hours).

The mixture was allowed to cool and settle and the lower aqueous layer discarded. The upper layer, de-

canted from some salt crystals, was 43.5 pounds of clear, pale yellow, soft sticky resin, insoluble in water, soluble in lower aliphatic alcohols, ketones and esters, and in aromatic hydrocarbons, but insoluble in aliphatic hydrocarbons and chlorinated solvents.

By replacing the benzyl chloride in Example 14 by the equivalent amount of some other (monoalkyl)benzyl or (polyalkyDbenzyl halide, for example, a (mono-loweralkyl)benzyl or (poly-lower-alkyDbenzyl chloride such as (monomethyl)benzyl or (dimethyl)benzyl or (trimethyl)benzyl chloride (e.g. .the mixed trimethylbenzyl isomers), or ethylbenzyl chloride, and the like, repeating the steps of that example, there are obtained respectively the corresponding water-insoluble other alkylbenzyl ethers of sucrose.

By replacing the specific sugar used in any of the Examples 1 through 14, and in any of the indicated modifications of them, by the equivalent Weight of any other sugar, and respectively repeating the steps of each such example, there result similarly following Examples 1 through 13 the respectively corresponding cyclic acetal of each such other sugar. Likewise, following Example 14, there results similarly the corresponding benzyl, or nuclearly substituted benzyl, ether of such other sugar. Only illustrative of such other applicable ethers of other sugars are the benzyl ethersof glucose, the benzyl ether of fructose, the (monomethyl)benzyl ether of sucrose, of glucose, and of fructose, the (dimethyl)- and the (trimethyl)benzyl ether of sucrose, of glucose, and of fructose, and the ethylbenzyl ether of sucrose, glucose and fructose, and others.

The glycosides, benzyl ethers of which can be an ingredient, along with the cyclic acetals of a sugar, in the non-aqueous and aqueous dispersions of the invention, include a true glycoside. That is to say, they include a glycoside, whose aglycon group is alkyl. as lower alkyl such as methyl, ethyl, propyl, and isopropyl, or is aralkyl as benzyl, or lower alkyl substituted benzyl, or is mononuclear any! as phenyl. Thus, only illustrative of these glycosides are such as the alpha or beta loweralkyl glycosides as alpha-methyl, alpha-ethyl, alpha (normal)propyl glucosides, alpha-ethyl fruc-toside, betaethyl mannoside, or the aralkyl glucoside as alpha-benzyl glucoside, or benzyl galactoside, or an aryl glycoside as phenyl arabinoside, and others like them.

The benzyl ethers of the glycosides are prepared, as illustrated by, but not restricted to, the following:

Example 15 .-Benzyl alpha-methyl glucoside 8.8 grams (0.22 mole) of sodium hydroxide Were dissolved in 20 milliliters of water. In the resulting sodium hydroxide solution there were dissolved, while stirring and warming, 38.8 grams (0.2 mole) of alpha-methyl glucoside. Then 25.2 grams (0.2 mole) of benzyl chloride were added and the mixture was stirred vigorously, while being heated for one and one-quarter hours in a water-bath at C. and for an additional 6 hours on a steam-bath. After cooling, the mixture separated into two layers, and salt crystallized out of the lower one. The mixture was then extracted with milliliters of benzene, and the benzene layer separated and concentrated. It yielded 39.2 grams of an oily, water-insoluble, resinous product, soluble in benzene and methanol.

By replacing the alpha-rnethyl glucoside of Example 15 by the equivalent amount of any other applicable true glycoside of the type exemplified above, and repeating generally the steps of that example, there are similarly obtained the corresponding benzyl ethers of the respective other glucosides.

Similarly, by replacing the benzyl chloride in Example 15, and in each of the just indicated modifications of it, by the equivalent amount of some other (monoalkyl)benzyl or (polyalkyl)benzyl halide, for example, a (mono-lower-alkyl)benzyl or (poly-lower-alkyl)benzyl chloride such as (monomethyDbenzyl or (dimethyl)- benzyl or (trimethyl)benzyl chloride (e.g. the mixed trimethylbenzyl isomers), or ethylbenzyl chloride, and the like, and repeating the steps of that example, there are obtained similarly the corresponding water-insoluble other alkylbenzyl ethers of each of those various glucosides respectively.

By correspondingly increasing the molal ratio of the reagent benzyl halide to the sugar in the method of Example 14, or to the glucoside in the method of Example 15','the corresponding poly benzyl ethers of sucrose and of any of the other sugars are obtained, such as di(methylbenzyl)sucrose and di(ethylbenzyl) sucrose, by following Example 14; and the corresponding lower alkylbenzyl ethers of the glucosides are obtained similarly by following Example 15.

Other similar ethers of any of these sugars and of these glucosides are obtained similarly by using more highly substituted benzyl halides as tetramethyland pentamethylbenzyl chloride. Still other such ethers are obtained by using a benzyl halide with some other compatible substituent inked to one or more of the nuclear carbons with or without a lower alkyl group linked to one or more other of the nuclear carbons. A benzyl halide with any compatible substituent can be used so long as the resulting benzyl ether is water-insoluble.

Any of the dispersions of the invention can include either as its sole ether-linked derivative of a saccharide ingredient or along with a cyclic acetal of a sugar, a socalled combined ether-linked derivative of a sugar, which derivative is referred to as combined because it is both a benzyl ether of a sugar as well as a cyclic acetal of a sugar. Such combined derivative results when a benzyl ether of a sugar with at least one available pair of etherifiable, adjacent hydroxyl groups is reacted, by the method of any of Examples 1 to 13, with one or more aldehyde or a ketone or both, to introduce at least one cyclic acetal group thereby to produce a combined cyclic acetal and ether of the sugar, for example, the butylidene acetal of the benzyl ether of sucrose.

The substantially uniform and stable non-aqueous dispersions of the invention are made by dispersing the selected water-insoluble acetal of a sugar, alone or along with at least another water-insoluble ether-linked derivative of a sugar, in at least one completely water-miscible dispersing agent for, and inert to, the ether-linked derivative of a sugar used.

Included among these applicable dispersing agents are the solvents, effective in varying degrees dependent on the specific ether-linked derivative of a sugar selected, and which solvents are completely water-soluble, generally lower aliphatic substances, straight or branched chain or cyclic, and having at least one of the elements oxygen and nitrogen. These solvents comprise alcohols carbonylgroup-containing compounds, ethers, and amines. The alcohols include the monohydric type having under five carbon atoms such as methyl, ethyl, n-propyl, isopropyl, and tertiary-butyl alcohols, and also acetyl carbinol (CH CO-CH OH), and also the polyhydric alcohols such as the glycols, ethylene and propylene glycols, butanediol-1,3 and butanediol-2,3 (beta butylene glycol), and butanediol-l,4 (tetra-methylene glycol). The carbonyl-group-containing type are illustrated by an amide such as formamide, the ketones, as exemplified by acetone, an aldehyde as acetaldehyde (so long as used at not too high a temperature), and the lower aliphatic acids such as formic, acetic (e.g. glacial), and the propionic acids.

The final, oxygen-containing class of solvents are the ethers which include the open-chain type as the glycol ethers such as carbitol (i.e. the mono-ethyl ether of diethylene glycol), methyl carbitol, and his beta- (ethoxyethyl) ether (i.e. diethyl carbitol"), and the cyclic type as diethylene oxide (or 1,4-dioxane and morpholine). The latter as a secondary amine (and also a cyclic amine) can be classed with the amines of the solvents, which embrace also the open-chain amines having under six carbon atoms as methyl-, ethyl-, propyl-, and butylamines, and tertiary-amylamine. The solubility in water of normal amylarnine is not high enough for it to be particularly applicable. Some applicable solvents have both the elements oxygen and nitrogen as seen in the amides as formamide and the cyclic secondary amines such as morpholine. The latter and dioxane exemplify the heterocyclic solvents.

The solutions of the invention are not limited to those wherein the water-insoluble ether-linked derivative of the saccharide is dissolved solely in a single solvent, but rather include also those in which a plurality of compatible solvents of the type already described as applicable, are mixed to form a joint solvent. Any two or more of the applicable solvents can be used as joint solvents, except that the acids should not be used jointly with any of the solvents having a nitrogen such as the amides and the amines because they would form addition salts with the aliphatic acids.

While some of the water-insoluble cyclic acetals of a sugar and other ether-linked derivatives of the saccharides involved herein are thick syrupy resinous products, for the most part these derivatives are resinous solids. As such resinous products they are found to exhibit a certain tackiness in some measure, which at least usually is more manifest when they are disintegrated into small particles, and varying in degree from derivative to derivative. Accordingly, these derivatives can be used, for example, when spread over certain surfaces to adhere to them and in turn to hold other materials close to those surfaces by adhering also to the other materials.

However, with but physical distribution such as mechanical disintegration, the extent of practical utilization of these water-insoluble cyclic acetals of a sugar and the other ether-linked derivatives of the saccharides for this property is extremely limited. This and other limitations are markedly overcome and the extent and more general utilization of these cyclic acetals alone or with the other derivatives are strikingly enhanced by using them in the form of stably dispersible-in-water, nonaqueous solutions of these water-insoluble, cyclic acetals alone or with the other ether-linked derivatives of saccharides in these completely water-miscible, aliphatic solvents having at least one of the elements oxygen and nitrogen and in a concentration no greater than the maximum-stably-suspendable-in-water concentration for the derivative in the solvent used for the solution, as embraced by the invention.

All of these ether-linked derivatives are not soluble equally in each of the possible solvents of the type described as applicable. One derivative may exhibit its highest maximum-stably-suspendable-in-water concentration in one of the solvents or in one class of them and its lowest maximum-stably-suspendable-in-water concentration in a second solvent and intermediate maximumstably-suspendable-in water concentrations with various other solvents respectively. Then another derivative might show its highest maximumstably-suspendable-inwater concentration with the solvent with which the first derivative showed its lowest maximum, and this other derivative might show its lowest maximum with some solvent with which the first derivative showed an intermediate maximum, and so on. For example, the maximunn stably-suspended-in-water concentration of the benzyl ether of sucrose in methanol is 25% by weight, whereas for the (mono)methylbenzyl ether of sucrose it is 40% by weight.

The maximum-stably-suspendable-in-water concentration for any applicable ether-linked derivative of a sugar in any of the completely water-miscible aliphatic solvents involved herein can readily be shown by a quick and easy test: The derivative is dissolved in a concentration of say 50% by weight in the selected solvent (or if not that soluble in it, then at its highest possible concentration in it). Then one milliliter of it is quickly and uniformly distributed in about a liter of well stirred water. If poor suspension and much clumping (on the water surface or sides of the beaker) occurs, enough solvent is added to part of the starting solution to reduce the concentration by 10% by weight and the test with one milliliter repeated with fresh water. If clumping again occurs, the concentration in the solvent is again reduced by 10% and the test repeated, and so on. If no clump- .ing occurs, part of the solution of the last higher concentration is diluted with sol-vent to reduce its concentration by only and the test repeated. If no clumping occurs, part of the solution of the next higher concentration is reduced in concentration by only 2 /2 by weight. However, if clumping occurred, then the solution tested is reduced in concentration by 2 /2-% by weight by the addition of solvent, and one milliliter so diluted is tested. As

previously defined when no, or no significant, clumping occurs, that is the maximum-stably-suspendable-in-watez concentration for that derivative in that solvent. Some non-clumping solutions of the invention are: (a) 327 grams of the mixed cyclic acetals comprising propylidene cyclohexylidene sucrose, as obtained by Example 6 above, and conveniently referred to as the propylidene cyclohexylidene cyclic acetals from sucrose, in 777 grams of methanol; (b) 450 grams of the cyclic acetals comprising propylidene sucrose, as obtained by Example 12.

above, and conveniently called the propylidene acetals from sucrose, in 1069 grams of methanol; and (c) 250 grams of benzyl alpha-methyl glucoside in 750 grams of methanol, or of ethanol, or acetone. 7

The solutions of the invention are very useful where stable, fine dispersions of a resinous, tacky substance is needed, as for a fiber binding agent in paper making, or as an assistant in flotation processes, and particularly effectively as a general sticker, for example, as the adhesive ingredient in pest control preparations such as pesticidal and insect repellent sprays, including fungicide, bactericide, and insecticide sprays. Thereby su'ch sprays are enabled to adhere more strongly and longer than otherwise to leaves, bark, fruit, and roots, as well as to the exposed parts of animals, and also to walls, andthus have had imparted to them enhanced resistance against being blown off by winds and washed off by rain. All of these various sprays just named conveniently are designated broadly as pest control preparations or pest control sprays.

An extensive variety of such pest control sprays, having incorporated in them one or more cyclic acetal of a sugar alone or together with at least one other of the ether-linked derviatives of a sugar (i.e. a benzyl ether of a sugar or of a glucoside), as embraced herein, can be prepared with some one or more of the different completely water-miscible solvents above described.

As an example, one hundred pounds of a 20 percent by weight solution of the mixed cyclic acetals comprising propylidene butylidene sucrose, as obtained by Example 1 above, and conveniently designated the propylidene butylidene acetals from sucrose, in methanol was prepared. A separate five pound portion of that solution was separately quickly uniformly distributed in each of several separate 100 gallons batches of water, while the water was being strongly agitated and after there had already been stirred into the water the ingredients, other than the propylidene butylidene cyclic acetals from sucrose, shown respectively in the following illustrative, but not restrictive, examples:

Example 16 Lbs. Parathion, i.e. 0,0 diethyl O p nitrophenylthiophosphate i Lead arsenate t 3 Lime 3 Benzene hexachloride (10% gamma) 2 Flotation sulphur 12 One pound of propylidene butylidene cyclic acetals from sucrose in 4 lbs. of methanal.

Example 17 Rotenone (4.9%) 3.3

One pound of propylidene butylidene cyclic acetals from sucrose in 4 lbs. of methanol,

14 Example 18 DDT, i.e. 2,2-bis(p-chlorophenyl) 1,1,1-trichloroethane, (50% wettable powder) One pound of propylidene butylidene cyclic acetals from sucrose in 4 lbs. of methanol.

Example 19 DDT (50% wettable powder) One pound of propylidene butylidene cyclic acetals from sucrose in 4 lbs. of methanal.

Zerlate, i.e. 76% Ziram, i.e. zinc diemethyldithiocarbonate -a 2 Example 20 Calcium arsenate 5.7

Spray lime 8 One pound of propylidene butylidene cyclic acetals from sucrose in 4lbs. of methanol.

Example 21 Ryania 4 Ultrawet (AtlanticRefining Co.) (i.e. sodium sulfonates of benzenes alkylated with a propylene polymer having from twelve to fifteen carbon atoms) One pound of propylidene butylidene cyclic acetals from sucrose in 4 lbs. of methanol.

Example 22 Methoxychlor, i.e. 1,1,1-trichloro-2,2-bis(p-methoxphenylJethene 2 One pound of propylidene butylidene cyclic acetals from sucrose in 4 lbs. of methanol.

Example 23 Methoxychlor (50% wettable powder) 2 Dithane, i.e. Z-78 zinc ethylene bis dithiocarbamate 2 One. pound of propylidene butylidene cyclic acetals from sucrose in 4 lbs. of methanol.

Example 24 Parathion (15% 'wettable powder) 2 One pound of propylidene butylidene cyclic acetals from sucrose i114 lbs. of methanoi.

Example 25 Parathion (15% wettable powder) 2 Dithane Z-78 2 One pound of propylidene butylidene cyclic acetals from sucrose in 4 lbs. of methanol.

, Example 26 Water gal1ons a 100 Sulfur (Stauifers magnetic) lbs. 5

One-half pound of the crotonylidene propylidene cyclic acetals from sucrose (as obtained by Example 2 above) in 1 /2 lbs. of methanol.

The respective solutions of the propylidene butylidene cyclic acetals from sucrose in methanol and crotonylidene propylidene cyclic acetals from sucrose in methanol, as used in the foregoing examples, and of any other cyclic acetals of a sugar alone or accompanied with some other ether-linked derivative of a sugar, here included, in methanol; or any of these cyclic acetals of a sugar alone cyclic acetals from sucrose) of a sugar.

15 or accompanied with any other of the already described benzyl ether derivatives in any other of the applicable solvents are marketable products. However, as with the solution used in Examples 16 through 25, each pound of derivative has to be accompanied by 4 pounds of solvent, or with 3 pounds of solvent as in Example 26. Also, since the maximum-stably-suspendable-in-water concentration of the butylidene acetals from sucrose (as obtained in Example 11) in methanol is 25% by weight of the final solution, and is the same for benzyl sucrose (the benzyl ether of sucrose), each pound of each of these two derivatives is accompanied by 3 pounds of methanol in the marketable solution.

Thus, for each pound of any cyclic acetal of a sugar dissolved in a solvent for it, for example, methanol, purchased by the user, he must pay not only for the three pounds of methanol but also for the freight on them and also on the container of the size required.

It has been found that these several additional costs can be reduced significantly by a further and distinctive feature of the invention. This feature enables carrying jointly dissolved in a given volume of solvent a total amount of at least two difierent solutes, namely, (1) a cyclic acetal of a sugar (e.g. the particular cyclic acetals of the specific sugar, as obtained in any one of the Examples 1 through 13), together with (2) one or more of (a) some different cyclic acetal of the same sugar, (b) any cyclic acetal of some other sugar, and (c) a benzyl ether of a sugar, or of a glucoside, or both; and without any clumping occurring when such solution of at least two solutes, namely, (a) and one or more of (b), is added to water, even though each of the at least two solutes is dissolved in thesolvent in an amount up to its respective maximum-stably-suspendable-in-water concentration (when each is separately dissolved in the solvent).

This distinctive modification of the solutions of the invention is illustrated by, but not restricted to, the following examples:

Example 27 The maximum-stably-suspendable-in-water concentration of the butylidene acetals from sucrose in methanol is 25% by weight (that is, 25 lbs. of these acetals from sucrose can be carried dissolved in 75 lbs. of methanol) before clumping becomes evident when the solution is mixed with Water. The same figures apply for benzyl sucrose and methanol. Yet when 25 lbs. of benzyl sucrose together with 25 lbs. of the butylidene acetals from sucrose are dissolved in 75 lbs. of methanol, no clumping occurs when this solution of a total of 50 lbs. of both of these ether-linked derivatives in 75 lbs. of methanol is uniformly distributed in water.

Thus, instead of a maximum of merely 25 of etherlinked derivative, by Weight, in solution, a total of 40% of derivatives, by Weight, is in solution. This is equivalent to one pound of ether-linked derivatives accompanied by only one and one-half pounds of methanol instead of by three pounds, and to a reduction of 37 /z% by Weight, and to 50% by volume, of solvent per pound of adhesive ether-linked derivative shipped. Reduced cost of production thus results from the smaller weight of solvent so required per pound of derivative, and also reduced container risk for the same output, and greater economy in handling and shipping.

The benzyl sucrose of Example 27 can be replaced by an amount, say, at least up to the maximum-stablysuspendable-in-water concentratin of some other benzyl sucrose or of any such benyl ether of some other sugar or of an alkyl or aryl or aralkyl glucoside, or of another water-insoluble cyclic acetal (other than the butylidene Likewise, the butylidene cyclic acetals from sucrose can be replaced by some other water-insoluble cyclic acetal of a sugar of the type herein involved. Some of such possible variations are illustrated by, but not restricted to, the following:

Example 28 The butylidene acetals from sucrose of Example 27 replaced by a mixed poly-(cyclic acetal) of sucrose comprising a heterogeneous type of poly-(cyclic acetal) of it: A 40% solution of benzyl sucrose alone in methanol when dispersed in water gave a very poor dispersion with clumping and large aggregates; so also did a 40% solution in methanol of the nonylidene propylidene cyclic acetals from sucrose. On the other hand, equal parts of each of these two methanol solutions added to one another and then this joint solution of them dispersed in water gave an excellent stable suspension, without any clumping.

Example 30 A solution of 40 pounds of the propylidene butylidene mixed poly-(cyclic acetals) from sucrose (comprising a heterogeneous type) in 60 pounds of methanol when dispersed in water gave a poor dispersion with clumping and aggregates; so also did a solution of 40 pounds of bis(methylbenzyl) sucrose in 60 pounds of methanol. However, a mixture of equal parts of these two methanol solutions upon being uniformly distributed in water, also gave an excellent uniformly stable dispersion, without any clumping. I

Example 31 The bis (methyl benzyl) sucrose of Example 30 replaced by a mixed poly-(cyclic acetals) from sucrose comprising the heterogenous type: A 40% solution in methanol of the nonylidene propylidene mixed poly-(cyclic acetals) from sucrose, on being uniformly distributed in water, gave a very poor dispersion. However, when it was combined with an equal volume of the Example 30 methanol solution of the propylidene butylidene cyclic acetals from sucrose, and this joint solution then was distributed uniformly in water, an excellent stable dispersion resulted.

Corresponding combinations can be made with other ether-linked derivatives of a sugar with the same or different solvents. Still other combinations can be composed. In some cases, as seen in Examples 30 and 31, the total amount of all different ether-linked derivatives in such solution containing at least two of them can exceed the sum of the separate amounts of the individual derivatives used when each is separately in solution in the same solvent at its own respective maximum-stablysuspendable-in-water concentration. Then also the number of individual ether-linked derivatives of a sugar dissolved in a single solvent or solution (if more than one solvent is used) is not limited to two. More than two can be used dependent at least on such conditions as the solvent capacity of the solvent or solvents used, viscosity, and effect of lowering of the temperature.

Any of the applicable completely water-miscible dispersing agents such as solvents, or compatible combinations of them, can be used with any water-insoluble cyclic acetal of a sugar alone or with any of the other mentioned ether-linked derivatives of a sugar so long as the solvent will give the desired concentration of the particular derivative or derivatives in solution. However, so far as presently studied, among the solvents the aliphatic alcohols are preferred because of their more general utility, and of them the monohydric particularly,

and of the latter methanol is preferred because of low cost and wider applicability.

There can be dispersed in the methanol or other lower aliphatic alcohol solvent, or in any of the other applicable solvents or dispersing agents or mixtures of any of them, a cyclic acetal of a sugar together with any number of other such acetals and ethers of a sugar and of a glycoside, as the selected dispersing medium can hold dispersed in it and yet remain fluid enough to be poured. While speeds-a :fluidity to permitpouring is desirable, it is notessential, Thus, the number so dispersed can'be as many as can be taken into solution as may be needed 'or'desiredgso long I as the resulting solution is stably dispersable in an aqueous medium. Even if some solution might solidify at a temperature ordinarily encountered in transportation, it is not critical but merely a temporary inconvenience. Such frozen dispersion easily-can be thawed out.

These solutions containing a cyclic acetal of a sugar and at least one of the other ether-linked derivatives of a saccharide and in a total concentration significantly over the maximuin-stably-suspendable-in-water concentration of one of the ether-linked derivatives in the solvent are more advantageously marketable products than those containing only one such derivative, in such applications where the presence of derivatives of at least two different chemical structures of ether-linked derivatives of a sugar does not matter and/or less solvent is desirable.

There can be prepared an extensive variety of pest control sprays (including pesticidal and insect repellent sprays such as fungicide, bactericide, insecticide, and other building, animal, and agricultural sprays) having dispersed in them a water-insoluble cyclic acetal of a sugar and at least one other water-insoluble, ether-linked derivative of the saccharides involved herein, and having the qualities and utility described in column 13, line 23 to column 13, line 28, above.

As an example, such-a concentrated solution has been prepared containing a total of three-quarters of a pound of water-insoluble ether-linked derivatives of a sugar per quart of solvent. Specifically three-eighths of a pound of the propylidene butylidene cyclic acetals from sucrose and the same weight of benzyl sucrose were jointly dissolved in a guart of methanol. The resulting solution is designated two derivatives in methanol in the succeeding examples. A quart ofthis concentrated solution of two derivatives was separately quickly uniformly distributed in each of a good number of separate 100 gallon batches of water, while the Water was being strongly agitated and after there had been stirred into it the other ingredients shown respectively in the following illustrative, but not restrictive, examples:

Example 32' DDT (50% wettable powder); lbs 1 /2 Dithane Z-78 lbs 2 Two derivatives in methanol", qts.. 1

Example 33 Methoxychlor (50% wettable powder) -lbs Dithane 1-78 lbs Two derivatives in methanol qts Example 34 Benzene hexachloride (6%). "lbs-.. 3 Two derivatives in methanol qts '1 Example 35 Dow C 1006 p-chlorophenyl p-chlorobenzene sulfonatelbs 1% Two derivatives in methanol qts 1 I Example '36 Du Pont EPN 300, its. ethyl-p-nitrophenylthionobenzene phosphate ..lbs /2 Two derivatives in methanol qts.... 1

Example 37 Dimite, i.e. di-(p-chlorophenyl')methyl carbinnl pts-.. 1 Two derivatives in methanolqts 1 Example 38 Staufler 'R-242, "ikep-chlorophenyl phenyl sulfone s" 2 Two derivatives in methanol qts-..' i l 7 i518 Example 39 DN-"I'l l the compound of 2-cyclohexyl-4,"6-dinitrophenol and dicyelohexylamine ...lbs 1% Two derivatives in methanol qts 1 7 Example 40 Parathion -lbs 0.8 Two derivatives in methanol qts.. 1

Example 41 Magnesium arsenate lbs 2 Two derivatives in methanol qts' '1 Example 42 Calcium arsenate lbs -4- Spray lime lbS...; "4 Two derivatives in methanol qts '1 i r Example 43 Parathion (15% Wettable powder) -.;lbs 1.6 Two derivatives in methanol ..qts 1 Example 44 Dieldrin contains not less than of 1,2,3,4, 10,10 hexachloro 6,7 epoxy l,4,4a,5,'6,7,8, 8a octahydro 1,4,5,8 dimethano naphthalene (25% wettable powder) lbs 1 Two derivatives in methanol qts 1 Example 45 Parathion (15% wettable powder) lbs 1;6 Magnetic sulfur lbs 4 Zinc sulfate (flakes) lbs -17 Lime lbs 8 Two derivativesin methanol 'qts l1 Example 46 l Benzene hexachloride (10% gamma) lbs -.2.4 Magnetic sulfur lbs 4 Zinc sulfate (flakes) lbs 7 Lime lbs 8 Two derivatives in methanol qts 1 Example 47 Benzene hexachloride (10% gamma) "lbs-.. 2.4 -DDT (50% wettable powder) lbs 2 Magnetic sulfur lbs 4 Zinc sulfate (flakes) ..lbs 7 Lime lbs 8 Two derivatives in methanol c qts 1 Example 48 V Dieldn'n (25% wettable powder) lbs- Magnetic sulfur lbs Zinc sulfate (flakes) lhs Lime 7 lhc Two derivatives in methanol c. qts

' Example 49 Dieldrin (25% wettablepowder) lbs 1 DDT (50% wettable powder) lbs 1 2 Magnetic sulfur lbs... 4 Zinc sulfate (flakes) lbs 7 Lime .lbs 8 Two derivatives in methanol -qts 1 Example 50 Benzene hexachloride 10% gamma) lbs 214 DDT (50% wettable powder) ..lbs 2 Two derivatives in methanol qtsj '1 Example 51 Dieldrin (25% wettable powder) lbs 1 DDT (50% wettable powder) 15s-, 2 Twodenivativesinrmethanol c-e e ;qts "1 Example 52 Lead arsenate bs 3 Spray lime lbs 3 -Magnetic 70 sulphur lbs 5 Two derivatives in methanol qts 1 water-insoluble cyclic acetal of a sugar, that is soluble in the solvent. Similarly, the benzyl sucrose can be replaced partly or wholly by any of the other ether-linked derivatives of the types described herein. Likewise, the methanolcan be replaced, in whole or in part, by any other of the applicable completely water-miscible applicable dispersing agents including any of the solvents described herein, for example, the lower aliphatic solvents V :for the derivatives employed, or any suitable mixture of these solvents.

The various spray compositions of these specific examples have been used in actual service trials on various foliage and found to show that the sticker ingredients, the single or jointly used water-insoluble ether-linked derivatives of the saccharides, were surprisingly efiective as well as non-phytotoxic (i.e. not injurious to the plants).

Comparative tests with simulated rainfall on leaves showed that the suspension of one pound of the propylidene butylidene mixed acetals from sucrose per 100 gallons of water, and of the three-quarters of a pound made up of equal parts of the benzyl sucrose and the propylidene butylidene mixed acetals from sucrose jointly in 100 gallons of water, to be thus far the optimum and advantageously preferred concentrations respectively for these two compositions as agricultural stickers. Each of the just noted suspensions can be used with its respective ether-linked derivative content within the range from about one-quarter pound to about two pounds, and preferably at about one and one-halfpounds, per 100 gallons of water. Other suspension compositions within the scope disclosed herein can be used with their content of ether-linked derivatives within about the same range.

However, the optimum for any other ether-linked derivatives, used singly or jointly, can readily be set by artificial rainfall test involving making an agricultural jspray using say lead arsenate and the selected sticker derivative and in varied'concentrations of the sticker, within the foregoing range, and spraying on leaves or slides and subjecting them to either a quarter inch or fivesixteenth of an inch of artificial rainfall and then determining the residual As O per square inch of leaf orslide.

The various spray compositions of the specific examples such as 32 through 41, 43, 46 and 48 showed advantageous resultswhen sprayed on certain vegetable plants and fruit trees, for example, on potatoes (Example 32), cucumbers (Ex. 33), beans (Ex. 41), peaches (Examples 34, 43, 46 and 48), and apples (Examples 35 through 40).

The various spray compositions of the individual Examples 32 through 52 include one quart of the solution designated two derivatives in methanol (described in column 17, line 35 hereof). As already indicated, the concentration of the two ether-linked derivatives of a sugar in individual spray compositions need not be confined to that obtained by use of one quart of this solution. In some cases, a lower volume of this solution can be used and in others higher, even as much as two quarts of the solution; For example, a highly effective dairy barn spray contained in 100 gallons: 16 lbs. Marlate 50 (i.e. 50% Methoxychlor), 1 lb. Lindane (wettable powder, gamma benzenehexachloride), 2 quarts of two derivatives in methanol, and balance water. Various sprays, have been used very satisfactorily on tomatoes, with different amounts from 1 to 2 quarts of two derivatives in methanol" and one quart of a 25% emulsion of DDT, three-quarters of a pint of nicotine sulfate (40%), and balance water to gallons.

Similarly, the content of the propylidene butylidene cyclic acetals from sucrose (dissolved in methanol) in the various Examples 16 through 25 can be varied over the range of from about oneeighth to about twice the concentration used in the examples. Corresponding range of variation applies with this derivative of sucrose replaced by some other heterogeneous type of acetals from sucrose.

The spray compositions of the Examples 17 through 25 gave highly beneficial results when sprayed on various vegetable plants, for example: on snap beans (Example 17), potatoes (Ex. 18), cabbage (Ex. 20), corn (Ex. 21

ganic insecticides. Thus, for example, different sprays were prepared using in each made up to one hundred gallons with water having dispersed in it in each of them one pound of the solution of propylidene butylidene cyclic acetals from sucrose in 4 lbs. of methanol, respectively (i) 5 lbs. of spray lime, (ii) 3 lbs of copper sulfate, (iii) 3 lbs. of copper sulfate and the sodium carbonate equivalent to 5 lbs. of spray lime, and (iv) 3 lbs. each of lime and lead arsenate and 12 lbs. of flotation sulfur.

Some fungicides included in sprays containing a waterinsoluble cyclic acetal of a sugar, for example, the propylidene butylidene cyclic acetals from sucrose indicated enhanced activity over that shown by them when used without such cyclic acetal.

Other than as pest control sprays, compositions embraced by the invention are effective as plant-growthenhancing sprays or dips. Such compositions are prepared generally by including with the dispersed waterinsoluble cyclic acetal of a sugar in an aqueous vehicle various suitable plant-growth-enhancing ingredients compatible with the acetal (alone or with a benzyl ether of a sugar and/or a glycoside) and the stability of its dispersion, Among such suitable ingredients are many different plant nutrients (inorganic and/or organic), es-

sential trace elements compounds, plant hormones, and the useful beneficial viruses (e.g. tomato bushy stunt virus). Insecticidal ingredients may also be included with them.

Thus, very beneficial results were obtained with the respectively noted vegetables in the following merely illustrative, and not restrictive, examples wherein the listed ingredients were used with the indicated volume of two derivatives in methane dispersed in water to make one hundred gallons:

Example 53 (Spray on potatoes) Example 56 'Tetraethyl pyrophosphate (20 pts 1 Two derivatives in methanol qts -1 Example 5 7 2,4-D .(i.e. dichlorophenoxyacetic acid) used in the low concentrations in which it serves as a plant hormone, in a spray containing one quart of"two derivatives in methanol.

In these several examples, the various ingredients can be replaced by others for the respectively same function and the proportions can be'varied, for example, as mentioned in relation to the earlier examples as to the cyclic acetals of a sugar. in such variations, 2,4,5-trichloroph'enoxy propionic acid can be used in fruit setting,

and naphthalene acetic acid or indole acetic acid can be in *one hundred gallons of water was applied to Fordhook "bush lima beans and to Arlington white spine cucumber seeds. In each case, the germination rate and growth rate of the seedlings to which this drench was applied exceeded that of the untreated seeds.

.Tom-atotransplantings immersed in a dip containing fourlpounds of lead arsenate and one quart of two de rivatives in methanol dispersed in one hundred gallons of water. showed enhanced development.

The various compositions of the invention are applicable in still other fields. Thus, improved adherence of asphalt resulted with crushed rockthatwas sprayed with an aqueous suspension containing from one to two quarts of two derivatives in niethanol'uniformly dispersed in one hundred gallons of water. A highly effective pressures'"ensitive tape results by depositing on a surface of the generally used transparent paper a fine layer of the mixture :of benzyl sucrose and the propylidene butylidene cyclic acetals from sucrose by applying a solution of them in methanol or other suitable solvent and letting the latter evaporate off. A highly etiecti-ve fiy-paper is prepared relatively similarly by suitable adjustment of proportions of the respective ether-linked derivatives of a saccharide used to, obtain the desired degree of tackiness.

This application is a continuation-impart of my copending application Serial No. 245,627, filed September 7,,1951, now abandoned.

While the invention hasbeen more specifically. described in relation to certain specific embodiments of it, it is understood that various modifications and substitutions can be made in them within the scope of the appended claims, which are intended also to cover equivalents of the various disclosed embodiments.

What is claimed is:

1. Aliquiddispersion comprising (A) homogeneously dispersed therein a water-insoluble ether-linked derii ative of a saccharide selected from the class consisting of (a) a cyclic acetal of a sugar which sugar has only such acetal substitution on its sugar entity and each of which acetalhas a total of from two through fourteen carbon atoms in the chain of its substituent other than the sugar residue linlted to the acetal ring-closing carbon, and (b) such cyclic acetal of a sugar'together with at least one member of the class consisting of (i) a benzyl ether of a sugar, and (ii) a benzyl ether of a glycoside whose aglycon group is one of the class consisting of a lower alkyl, the benzyl, a lower-alkyl benzyl, the phenyl, and a lower-alkyl phenyl radical; and (B) in quantity sufiicient to maintain such saccharide derivative content homogeneously dispersed, at least one completely water'- miscible non-hydrocarbon aliphatic dispersingagent for,

and inert to, the ether-linked derivative "of a saccharide content of the dispersion, which agent has at least one of the elements oxygen and nitrogen in its structure; the content of ether-linked derivative of a saccharide "being under that which exceeds its maximum-stably-suspendable-in-water concentration; said dispersion being uniformly miscible with water to yield therein a stable suspension of the water-insoluble saccharide derivative homogeneously dispersed inthe water.

2. A liquid dispersion comprising (a) the mixed poly- (cyclic acetals) of sucrose having only cyclic acetal substitution on its sugar entity and comprising the heterogeneous type of poly-(cyclic acetals) of sucrose and in which the propylidene group is one of the cyclic acetal groups and the butylidene group is the other and which mixed poly-(cyclic acetals) of sucrose are those resulting from the condensation of sucrose with propionaldehyde and butyraldehyde in the presence of an acid acetylization catalyst and with the propionaldehyde in the proportion of at least ten mole percent, and remaining after removal of the catalyst and any water introduced with it as well as the water formed during the condensation, said mixed poly-(cyclic acetals) of sucrose being substantially homogeneously dispersed in said liquid dispersion in a concentration under that which exceeds the maximum-stably-suspendable-in-water concentration of said cyclic acetals content, and (b) in quantity sufiicient to maintain the said cyclic acetals content homogeneously dispersed, at least one completely water-miscible, non-hydrocarbon aliphatic dispersing agent for, and inert to, said cyclic acetal content and having at least one of the elements oxygen and nitrogen in its structure; said dispersion being uniformly miscible with water to yield therein a stable suspension of said mixed poly-(cyclic acetals) of sucrose homogeneously dispersed in the water.

3. The liquid dispersion as claimed in claim 1, wherein there is a plurality of the water-insoluble ether-linked derivatives of a saccharide homogeneously dispersed therein and the content of each such derivative is below that which exceeds its respective maximum-stably-suspendable-in-water concentration.

4. A liquid dispersion comprising (a) both benzyl sucrose and the mixed poly-(cyclic acetals) of sucrose having only cyclic acetal substitution on its sugar entity and comprising the heterogeneous type of poly-(cyclic acetals) of sucrose and in which the propylidene group is one of the cyclic acetal groups and the butylidene group is the other and whichmixed poly-(cyclic acetals) of sucrose are those resulting from the condensation of sucrose with propionaldehyde and butyraldehyde in the presence of an acid acetylization catalyst and with the propionaldehyde in the proportion of at leastten mole percent, and remaining after removal of the catalystand any water introduced with it as well as the water formed during the condensation; said benzyl sucrose and mixed poly-(cyclic acetals) of sucrose being homogeneously dispersed in the liquid dispersion and each in a concentration under that which exceeds its respective maximum-stably-suspendable-in-water concentration; and (b) in quantity suflicient to maintain both said benzyl sucrose and mixed poly-(cyclic acetals) from sucrosehomogeneously dispersed, at least one completely water-miscible, non-hydrocarbon aliphatic dispersing agent for, andinert to, both said cyclic acetal and benzylsucrosecontent and having at least one of the elements oxygen and nitrogen in its structure; said dispersion being uniformly miscible with water to yield in it a stable suspension of both the benzyl sucrose and the mixed poly-(cyclic acetals) of sucrose homogeneously dispersed in the water.

5. A solution of water-insoluble ether linked'derivative of a saccharide selected from the class consisting of (a) a cyclic acetal of a sugar which sugarihas only such acetal substitution onits sugar entity and each-of "23' acetal has a total of from two through fourteen carbon atoms in the chain of its substituent other than the sugar residueqlinked to the acetal ring-closing carbon, (b) such cyclic acetal of a sugar together with at least one member of the class consisting of (i) a benzyl ether of a sugar, and (ii) a benzyl ether of a glycoside whose aglycon group is one of the class consisting of a lower alkyl, the benzyl, a lower-alkyl benzyl, the phenyl, and a lower-alkyl phenyl radical; said solution having each such derivative of a saccharide contained in it dissolved, in a concentration under that which exceeds its respective maximum-stably-suspendable-in-water concentration, in a quantity, sufficient to maintain the water-insoluble saccharide derivative content homogeneously dispersed therein, of at least one non-hydrocarbon aliphatic completely water-miscible solvent for and inert to such saccharide derivative and having at least one of the elements oxygen'and nitrogen in its structure; said solution beinguniformly miscible with water to yield therein a stable suspension of the water-insoluble saccharide derivative homogeneously dispersed in the water.

6. A solution of at least one water-insoluble cyclic acetal of a sugar which has only cyclic acetal substitution on its molecule and each of which acetal has a total of from two through fourteen carbon atoms in the chain .of its substituent other than the sugar residue linked to the acetal ring-closing carbon, each said cyclic acetal being in a concentration under that which exceeds its maximum-stably-suspendable-in-water concentration, dissolved in a quantity, sufficient to maintain such cyclic acetal content dissolved therein, of at least one completely water-miscible non-hydrocarbon aliphatic solvent for and inert to the cyclic acetal content and whose structure includes the element oxygen and lacks the element nitrogen; said solution being uniformly miscible with water to yield therein a stable suspension of the water-insoluble cyclic acetal homogeneously dispersed in water.

7. A solution of at least one water-insoluble cyclic acetal of a sugar which sugar has only such acetal substitution on its sugar entity and each of which acetal has a total of from two through fourteen carbon atoms in the chains of its substituent other than the sugar residue linked to the acetal ring-closing carbon, in'a concentration under that which exceeds its maximum-stably-suspendable-in-water concentration, dissolved in a quantity, suflicient to maintain such cyclic acetal content dissolved therein, oftat least one completely water-miscible nonhydrocarbon aliphatic solvent for and'inert to the cyclic acetal content and selectedlfrom the class consisting of the-glycolsand lower aliphatic alcohols having less than five carbon atoms; said solution being uniformly miscible with water to yield therein a stable suspension of the water-insoluble cyclic acetal homogeneously dispersed in water.

8. The solution as claimed in claim 7, wherein (a) the water-insoluble cyclic acetal content is the mixed poly-(cyclic acetals) of sucrose comprising the heterogeneous type of poly-(cyclic acetals) of sucrose and in which the propylidene group is one of the cyclic. acetal groups and the butylidene group is the other and which mixed poly-(cyclic acetals) of sucrose are those resulting from the condensation of sucrose with pro-pionaldehyde and butyraldehyde in the presence of an acid acetylization catalyst and with the propionaldehyde in the proportion of at least ten mole percent, and remaining after removal of the catalyst and any water introduced with it as well as the water formed during the condensation, and (b) the solvent is methanol.

9. The solution as claimed in claim 8, wherein the concentration of the water-insoluble cyclic acetals content is no greater than about twenty percent by weight.

1 0. A solution of at least one water-insoluble cyclic acetal of a sugar which has only cyclic acetal substitution onits molecule and each of which acetal has a total of from two through fourteen carbon atoms in the chain of its substituent other than the sugar residue linked to the acetal ring-closing carbon, and of a benzyl ether of a sugar, and each in a concentration under that which exceeds its respective maximum-stably-suspendable-inwater concentration, dissolved in a quantity, sufiicient to maintain such cyclic acetal and benzyl ether dissolved therein, of at least one completely water-miscible nonhydrocarbon aliphatic solvent for and inert to the acetal and the ether content and whose structure includes the element oxygen and lacks the element nitrogen; said solution being uniformly miscible with water to yield therein a stable suspension of the water-insoluble cyclic acetal homogeneously dispersed in water.

11. A solution of benzyl sucrose and the mixed poly- (cyclic acetals) of sucrose comprising the heterogeneous type of poly-(cyclic acetals) of sucrose and in which the propylidene group is one of the cyclic acetal groups and the butylidene group is the other and which mixed poly-(cyclic acetals) of sucrose are those resulting from the condensation of sucrose with propionaldehyde and butyraldehyde in the presence of an acid acetylization catalyst and with the propionaldehydein the proportion of at least ten mole percent, and remaining after removal of the catalyst and any water introduced with it as well as the water formed during the condensation; said ether and cyclic acetals being dissolved in at least one completely water-miscible non-hydrocarbon aliphatic solvent for and inert to them and selected from the class consisting of the glycols and the lower aliphatic alcohols having less than five carbon atoms and the quantity of said solvent being sufficient to maintain said ether and acetals dissolved therein, the concentration of each of them being under that which exceeds its respective maximum-stablysuspendable-in-water concentration, said solution being uniformly miscible with water to yield therein a stable suspension of both the benzyl sucrose and the mixed poly-(cyclic acetals) of sucrose homogeneously dispersed in the water.

12. The solution as claimed in claim 11, wherein the solvent is methanol.

13. The solution as claimed in claim 12, containing by weight about twenty-five parts each of the said mixed cyclic acetals and of the benzyl sucrose, and the balance to make up a total of one hundred parts is methanol.

14. An aqueous suspension comprising homogenously dispersed in water in stable suspension therein, and in a concentration under that which exceeds its respective maximum stably-suspendable-in water concentration, a water-insoluble ether-linked derivative of a saccharide selected from the class consisting of (a) a cyclic acetal of a sugar which sugar has only such acetal substitution on its sugar entity and each of which acetal has a total of from two through fourteen carbon atoms in the chain of its substituent other than the sugar residue linked to the acetal ring-closing carbon, (11) such cyclic acetal of a sugar together with at least one member of the class consisting of (i) a benzyl ether of a sugar, and (ii) a benzyl ether of a glycoside whose aglycon'group is one of the class consisting of a lower alkyl, the benzyl, a lower-alkyl benzyl, the phenyl, and a lower-alkyl phenyl radical; and uniformly dispersed in the water, in a quantity sufficient to maintain the water-insoluble saccharide derivative content homogeneously suspended therein, at least one completely water-miscible non-hydrocarbon aliphatic dispersing agent for and inert to such saccharide derivative content and having at least one of the elements oxygen and nitrogen in its structure.

15. The aqueous suspension as claimed in claim 14, wherein '(a) the water-insoluble cyclic acetal content is the mixed poly-(cyclic acetals) of sucrose comprising the heterogeneous type of poly-(cyclic acetals) of sucrose and in which the propylidene group is one of the cyclic acetal groups and the butylidene group is the other and resulting :from the condensation of sucrose with propionaldehyde and butyraldehyde in the presence of an acid acetylization catalyst and with the propionaldehyde in the proportion of at least ten mole percent, and remaining after removal of the catalyst and any water introduced with it as well as the water formed during the condensation, and (b) the solvent for the water-insoluble saccharide derivative content is aliphatic.

16. An aqueous suspension as claimed in claim 15, which comprises a benzyl ether of a sugar also in stable suspension in the water and the aliphatic solvent for the water-insoluble saccharide derivative content is a member of the class consisting of the glycols and lower aliphatic alcohols having less than five carbon atoms.

17. The aqueous suspension as claimed in claim 16, wherein the aliphatic solvent is methanol and the benzyl ether of a sugar is benzyl sucrose.

18. An aqueous pest control spray having water. as its aqueous vehicle and containing in it a pest controlling concentration of at least one suitable pest control agent and homogeneously dispersed in stable suspension in the water as sticker ingredient'for the spray a sulficient sticker concentration, under that which exceeds its maximum-stably-suspendable-in-water concentration, of the poly-(cyclic acetals) of sucrose comprising the heterogeneous type of poly-(cyclic acetals) of sucrose and in which the propylidene group is one of the cyclic acetal groups and the butylidene group is the other and which mixed poly-(cyclic acetals) of sucrose are those resulting from the condensation of sucrose with propionaldehyde and butyraldehyde in the presence of an acid acetylization catalyst and iwth the propionaldehyde in the proportion of at least ten mole percent, and

remaining after removal of the catalyst and any water introduced with it as well as the water formed during the condensation; and dissolved in the water, in quantity sufficient to maintain the cyclic acetal content homogeneously suspended in the water, at least one completely water-miscible aliphatic alcohol solvent for said cyclic acetal content and selected from the class consisting of the glycols and lower aliphatic alcohols having less than five carbon atoms; and the sucrose entity has only cyclic acetal substitution on it.

19. The aqueous pest control spray as claimed in claim 18, wherein also homogeneously dispersed in the Water is a quantity of benzyl sucrose about equal in Weight to that of the said mixed poly-(cyclic acetals) of sucrose and also under that which exceeds the maximum-stably- ,suspendable-in-water concentration for benzyl sucrose,

and the solvent is methanol.

20. An aqueous plant-growth-enhancing spray having water as its aqueous vehicle and containing in it a plantgrowth-enhancing concentration of at least one suitable plant-growth-enhancing agent and homogeneously dispersed in stable suspension in the water as sticker ingredient for the spray a suflicient sticker concentration, under that which exceeds its maximum-stably-suspendab]e-inwater concentration, of the poly-(cyclic acetals) of sucrose comprising the heterogeneous type of poly-(cyclic acetals) of sucrose and in which the propylidene group is one of the cyclic acetal groups and the butylidene group is the other and which mixed poly-(cyclicacetals) of sucrose are those resulting from the condensation of sucrose with propionaldehyde and butyraldheyde in the presence of an acid acetylization catalyst and with the propionaldehyde in the proportion of'at least ten mole percent, and remaining after removal of the catalyst and any water introduced with it as well as the water formed during the condensation; and dissolved in the water, in quantity suflicient to maintain the cyclic acetal content homogeneously suspended in the water, at least one completely water-miscible aliphatic alcohol solvent for said cyclic acetal content and selected from the class consisting of the glycols and lower aliphatic alcohols having less than five carbon atoms; and the sucrose entity has only cyclic acetalsubstitution onlit.

21. The aqueous plant-growth-enhancing ispray 'as claimed .in claim .20, wherein also homogeneously dispersed in the water is a quantity of benzyl sucrose about equal in weight to that of the said mixed poly-(cyclic acetals) of sucrose and also under that which exceeds the maximum-stably-suspendable-in water concentration for benzyl sucrose, and the solvent is methanol.

22. The method of preparing a liquid dispersion of Water-insoluble sticker adaptable to serve as the sticker ingredient of a spray selected from the class consisting of a pest control spray and a plant-growth-enhancing spray, which dispersion is uniformly miscible with water to yield therein a suitable suspension of its waterinsoluble sticker content homogeneously dispersed in the water and contains a total sticker content concentration higher than the maximum-stably-suspendable-inwater concentration of any individual sticker ingredient dispersed in it when used alone; which method comprises dissolving at least two water-insoluble ether-linked derivatives of a saccharide different from one another and which are members of the class consisting of (i) a cyclic acetal of a sugar having only cyclic acetal substitution on its sucrose entity and a total of from two to fourteen carbon atoms in the chain of thesubstituent other than the sugar residue linked to the acetal ringclosing carbon, (ii) a benzyl ether of a sugar, and (iii) a benzyl ether of a glycoside whose aglycon group is one of the class consisting of a lower alkyl, the benzyl, a lower-alkyl benzyl, the phenyl, and a lower-alkyl phenyl radical; and at least one of said ether-linked derivatives of a saccharide being a cyclic acetal of a sugar, and each such saccharide derivative being present in a concentration greater than one-half and under that which exceeds its respective maximum-stably-suspendable-in-water concentration, in at least one completely water-miscible aliphatic solvent for such saccharide'derivatives and which'has in its structure one of the elements oxygen and nitrogen.

23. The method as claimed in claim 22, wherein one of the water-insoluble derivatives of a saccharide is a benzyl ether of sucrose and the solvent is at least one aliphatic alcohol member of the class consisting of the glycols and the aliphatic alcohols having under five carbon atoms.

24. The method as claimed in claim 23, wherein the cyclic acetal of a sugar is the mixed poly-(cyclic acetals) of sucrose comprising the heterogeneous type of poly- (cyclic acetals) of sucrose and in which the propylidene group is one of the cyclic acetal groups andthe butylidene group is the other and which mixed poly-(cyclic acetals) of sucrose are those resulting from the condensation of sucrose with propionaldehyde and butyraldehyde in the presence of an acid acetylization catalyst and with the propionaldehyde in the proportion of at least ten mole percent, and remaining after removal of the, catalyst; and any water introduced with it as well as the water formed during the condensation, and the benzyl'ether of sucrose is benzyl sucrose, and the solvent is methanol.

References Cited in the file of this patent UNITED STATES PATENTS 1,444,257 Lillienfeld Feb. 6, 1923 2,104,491 McKinney Ian. 4, 1936 2,109,961 Karr Mar. 1, 1936 2,116,867 Kreimeier May 10, 1938 2,146,258 Goodhue Feb. 7, 1939 2,203,704 Stahly et al June 11, 1940 2,344,180 Stahly et a1 Mar. 14, 1944 2,385,553 Stahly et al Sept. 25, 1945 (Other references on following page) 7 UNITED STATES PATENTS Grifi'in Sept. 3, 1946 Fox Sept. 6, 1949 Shmidl June 6, 1950 FOREIGN PATENTS Great Britain Sept. 3, 1934 France May 3, 1905 OTHER REFERENCES 7 Berichte der Deutschen Chemischexi Gesellshaft, 51 (1918), pp. 324, 325; 57 (1924), p. 409; 65 (1932), p.

Wolfrom et -a1.: J.A.C.S., vol. 72, October 1950, pp. 4544 and 4545.

Berker et aL: Advances in Carbehydrate Chem," v01. 7, 1952, pp. 137-207 (p. 168 per-L).

UNITED STATES'P'ATENT OFFICE CERTIFICATE, OF CORRECTION 1, Patent No. 1 March 1, I 1960 Louis Lang It is hereby certified that error appears in the printed specification "hr the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 3, line 75, about a quarter of an inch after the formula insert a comma;' column 4, lines 6 and 18, about a half Inch after the structural formula in each occurrence insert a period; column 4, line 12, about a half inch after the structural formula insert a comma; column 5, line 75, for 'c'moecular" read 1a; molecular column 6, line 66, for "separation" readseparate column 11, line 12, for "inked" read linked lines 44 and 45, after "alcohols" insert a comma; column 13, line 5, for "2/ read 2/ column 15, line 68, for "concentrating??- read concentration line 69, for "benyl" read benzyl column 17 line 27, for "28" read 38 line 38, for "gallon" read gallons column 19, line 64, for "line 35 read lines 28 to 36 column 20, line 17, strike out "and", third occurrence; line 29,

for "to" read of column 25, line 33, for "iwth" read with Signed and sealed this 25th day of October 1960,,

(SEAL) Attest:

KARL H. AXLINE ROBERT C. WATSON Attesting Officer C li'ommissioner of Patents,

Claims (1)

1. A LIQUID DISPERSION COMPRISING (A) HOMOGENEOUSLY DISPERESED THEREIN A WATER-INSOLUBLE ETHER-LINKED DERIVATIVE OF A SACCHARIDE SELECTED FROM THE CLASS CONSISTING OF (A) A CYCLIC ACETAL OF A SUGAR WHICH SUGAR HAS ONLY SUCH ACETAL SUBSTITUTION ON ITS SUGAR ENTITY AND EACH OF WHICH ACETAL HAS A TOTAL OF FROM TWO THROUGH FOURTEEN CARBON ATOMS IN THE CHAIN OF ITS SUBSTITUENT OTHER THAN THE SUGAR RESIDUE LINKED TO THE ACETAL RING-CLOSING CARBON, AND (B) SUCH CYCLIC ACETAL OF A SUGAR TOGETHER WITH AT LEAST ONE MEMBER OF THE CLASS CONSISTING OF (I) A BENZYL ETHER OF A SUGAR, AND (II) A BENZYL ETHER OF A GLYCOSIDE WHOSE AGLYCON GROUP IS ONE OF THE CLASS CONSISTING OF A LOWER ALKYL, THE BENZYL, A LOWER-ALKYL BENZYL, THE PHENYL, AND A LOWER-ALKYL PHENYL RADICAL, AND (B) IN QUANITY SUFFICIENT TO MAINTAIN SUCH SACCHARIDE DERIVATIVE CONTENT HOMOGENEOUSLY DISPERSED, AT LEAST ONE COMPLETELY WATERMISCIBLE NON-HYDROCARBON ALIPHATIC DERIVATIVE AGENT OF, AND INERT TO, THE ETHER-LINKED DERIVATIVE OF A SACCHARIDE CONTENT OF THE DISPERSION, WHICH AGENT HAS AT LEAST ONE OF THE ELEMENTS OXYGEN AND NITROGEN IN ITS STRUCTURE, THE CONTENT OF ETHER-LINKED DERIVATIVE OF A SACCHARIDE BEING UNDER THAT WHICH EXCEEDS ITS MAXIMUM-STABLY-SUSPENDABLE-IN-WATER CONCENTRATION, SAID DISPERSION BEING UNIFORMLY MISCIBLE WITH WATER OF YIELD THEREIN A STABLE SUSPENSION OF THE WATER-INSOLUBLE SACCHARIDE DERIVATIVE HOMOGENEOUSLY DISPERSED IN THE WATER.