US2197462A - Process and product relating to heteropolar compounds - Google Patents

Description

Patented Apr. 16, 1940 UNITED STATES PROCESS AND PRODUCT RELATING TO HETEBOPOLAR COMPOUNDS Franklin A. Bent, Berkeley, Calif" assignor to Shell Development Company, San Francisco, Calif., a corporation of Delaware No Drawing. Application December 27, 1937,

Serial No. 182.005

. 17 Claims.

The present invention relates to a' process for the preparation of, and products constituting, a lbroad class of heteropolar (polar-nonpolar) compounds ranging'from' neutral oil-soluble compounds to acidic or basic water-soluble compounds which have the common property of exhibiting a certain duo-nature. This duo-nature is manifested by an affinity on the one hand for lipins and by an affinity for water or inorganic substances on the other hand, caused by the simultaneous presence of lipophile and polar or lipophobe groups in the molecule.

More particularly, the invention concerns a process for the preparation of, and products relating to heteropolar compounds in which at least one lipophile radical is predominantly of aliphatic character, and more particularly to those compounds containing an aliphatic lipophile radical or radicals of highly branched structure.

Compounds of this type, although varying considerably with the nature and size of the lipophile and polar or lipophobe groups tend, in general, to cling tenaciously on metal and certain inorganic surfaces, to lower the surface tension of water or aqueous liquids when dissolved therein, etc., and consequently, are suited for numerous purposes where tenacity, wetting power, penetration, etc., are factors, such as, for example, in the lubricant, flotation, textile, leather, and many other industries.

An object of the present invention is to provide an improved method for the production of a superior class of heteropolar compounds having at least one lipophile radical, said lipophile radical having the structure hereinafter set forth. A

further object of the invention is to provide new a polar group are, in general, superior in many respects to similar heteropolar compounds in which the lipophile groups are normal. The

superior qualities of this class of heteropolar compounds, which include a much lower viscosity and effectiveness in smaller concentrations, are further increased if the radicals R and/or R are of a forked chain structure.

It is tound that this preferable type of compound may be economically prepared in accordance with the present improved method which consists essentially of the following four steps:

(1) Preparation of an alpha beta unsaturated ketone.

(2) Rearrangement of said alpha beta unsaturated ketone to the corresponding beta gamma unsaturated ketone.

(3) Hydrogenation of said beta gamma unsaturated ketone to form the corresponding saturated secondary alcohol.

(4) Reaction of said saturated secondary alcohol with a suitable reagent whereby there is attached to the molecule in lieu of the hydroxyl group a lipophoblc residue of an acid.

By an alpha beta unsaturated ketone is meant a ketone containing an ethylene linkage attached to the carbonyl group. These ketones contain a conjugated system of the structure By a beta gamma unsaturated ketone is meant a ketone containing an ethylene linkage attached to the carbonyl group through a methylene group. These ketones contain the structural grouping The alpha beta unsaturated ketones applicable in the present process may be designated by the general formula:

H g R; Bz-(: -(F=(IJ-CC:I I R: R: R4 R1 wherein R1 through R1 may be any member of the group consisting of hydrogen, aliphatic and .cyclo-parafiinic groups, with the provisions that C and or C be tertiary carbon at0m(s), and

Gil

that the sum of the carbon atoms in R1, 2 and a 'be not less than two. These applicable alpha beta unsaturated ketones, it is seen, contain at least seven carbon atoms. Examples of structures containimz mple R1, R2 and R3 radicals are Hr-CH:

at. cm

- CHECK! (came-c CHr-CH:

Moreover, R2 may be connected with R1 or Rs by one or more methylene groups to form a polymethylene ring structure, for example, containing the groupings.

CHa-CH: R|

Likewise compounds in which Re is connected to v R1 or R4 by one or more methylene groups are also applicable. Examples of this structure are a s c CHz-CH:

These applicable alpha beta unsaturated ketones, including their optical and stereo-isomers, constitute a class of unsaturated ketones diflering in several respects from other unsaturated ketones. One notable characteristic of these compounds is the ease with which they may be alkylated. Unsaturated ketones of other structure, such as mesityl oxide, ethyl nonenone gamma delta, 3-methyl-cyclohexadienyl-2, fi-acetone, etc., which are not allwlated under mild conditions are not applicable.

Unsaturated ketones of the desired structure may be prepared by any one of several known methods, the invention being independent of the mode of formation. One suitable method is through the condensation of ketones followed by dehydration of 'the resulting ketols. The reactions involved in the synthesis are illustrated by the case of the formation of 2, 4, 8-trimethylnonene-4-one-6 from methyl isobutyl ketone.

Am aliphatic, alicyclic orvaliphatic alicyclic ketone having a primary or secondary alpha carbon atom, such as, for example, methyl ethyl ketone, methyl isopropyl ketone, methyl cyclohexyl ketone, ethyl cyclopentyl ketone, cyclohexanone, cyclopentanone, alpha methyl cyclopentanone, etc., may be employed to form the starting material of my process. Any suitable catalyst such as CaCz, A1203, NaOCrHa, POCls, H2804, HCl, IIBr, HI, CaO, ThOz, ZnClz, Na, aluminum halide, organo magnesium halide, sodium pyrosulfate, sodamide, triphenyl aluminum, etc., may be used to accelerate the reaction. In most cases the two reactions proceed under the same conditions to yield the desired alpha beta unsaturated ketone directly. If under mild (usually alkaline conditions) the ketol is obtained, this may be easily dehydrated by heating with a little acid. In this method of preparation all theoretically possible condensation products are formed to a certain extent, their relative quantity being determined by the ketone, catalyst, and conditions used. Thus, for example,

when condensing methyl ethyl ketone with itself 3-methyl heptene-3-one-5, 3, 4-dimethyl hexene- 3-one-5, 3, 6, 'l-trimethyl nonadiene-3, 6-one-5, and 3, 4, l-trimethyl nonadiene-3, 6-one-5 may be isolated. With A1203 as a catalyst, for example, 3-methy1 heptene-3-one-5 is the predominant product, while with acid catalysts 3, 4-dimethyl-hexene-3-one-5 predominates. The alpha beta, alpha beta doubly unsaturated trimer which is also applicable may be separated from the reaction product by fractionation, although this step is not necessary.

Another and convenient method for preparing the desired alpha beta unsaturated ketones is through the condensation of a ketone of the above-mentioned class with an alpha substituted aldehyde. Any aldehyde having the structure Another method of producing the desired alpha beta unsaturated ketones is through the dehydration of the corresponding acyloins. This may be accomplished according to the scheme rearranges CH: CH:

If it is attempted to perform the reduction in accordance with accepted commercial hydrogenation methods, it is found that severe conditions are required and that the yields are then poor due to the simultaneous formation 'of considerable amounts of hydrocarbons and saturated ketone. Since the product is very impure, it must be subjected to a fractionation, usually under vacuum, to separate the desired secondary alcohol from the unreacted material, saturated ketones and hydrocarbons. This difllculty in hydrogenation is no doubt due to coniugation in the alpha beta unsaturated ketones,

On the other hand, the corresponding beta gamma unsaturated ketones undergo hydrogenation under more favorable conditions and in a cleancut manner to yield the corresponding secondary alcohols in excellent yields. The beta gamma ketones differ further from their corresponding alpha beta ketones in showing essentially no exalted molecular refractions and having lower melting points, boiling points, refractive indices and densities.

In accordance with the present invention, I therefore rearrange the alpha beta unsaturated ketone, regardless of source, to the corresponding beta gamma imsaturated ketone before effecting hydrogenation.

The tertiary carbon atoms (0* and/or C in the above-mentioned alpha beta unsaturated ketone structure counteract to a certain extent the tendency of the unsaturated bonds to conjugate, i. e., to form static alpha beta unsaturated ketones. This counteracting tendency manifests itself in the formation of an equilibrium mixture at alpha beta and beta gamma unsaturated ketone in which the beta gamma ketone content may range from traces to an appreciable amount depending upon the size and character of the radicals, R1, 2, 3, and 4. Although it usually requires a considerable time for equilibrium to become established under normal conditions, a few unsaturated ketones of the above structure equilibrate quite rapidly and therefore make the preparation of the pure alpha beta ketone difficult. It is to be understood, however, that the formation of an equilibrium mixture containing some beta gamma ketone instead of the pure alpha beta ketone does not detrimentally affect the applicability of these compounds in the present invention.

By subjecting the alpha beta unsaturated ketone (or an equilibrium mixture of alpha beta and beta gamma unsaturated ketone) to a fractional distillation at a rate not exceeding the rate of rearrangement, the lower boiling beta gamma unsaturated ketone may be continually removed causing the rearrangement to proceed to completion. This method of producing the desired beta gamma unsaturated ketone is quite simple and generally applicable to the ketones of the above-mentioned structure,

By simply fractionating in most cases the rearrangement takes place at too slow a rate, even at elevated temperatures, to be economically practical. This may be remedied, however, by the use of a small amount of a substance which catalyzes the rearrangement, i. e., increases the mobility of the system. It is found that alkali metal alkoxides in particular, such as the various alcoholates of sodium, lithium, potassium, aluminum, magnesium, etc., are suited. Other catalysts, such as alcoholic alkali and even mineral acid may sometimes be used.

Although the catalysts are usually effective in very small amounts, it is found that the rate of rearrangement is somewhat dependent upon the amount 01 catalyst present, being somewhat higher at catalyst concentration of about 3 to 5%. While the lower boiling alpha beta unsaturated ketones are conveniently rearranged at their normal boiling points, such high molecular weight unsaturated ketones as are unstable at their normal boiling points may be rearranged at a somewhat lower temperature by carrying out the rearrangement under a suitably diminished pressure.

As has been previously shown, the preparation of any desired alpha beta unsaturated ketone is usually accompanied by the formation of a small amount of other condensation products. .Since these products usually consist of isomeric alpha beta unsaturated ketones and alpha beta unsaturated ketones of different molecular weight they may beqearranged to their corresponding beta gamma unsaturated ketones in the same manner and are suitable for the preparation of valuable heteropolar compounds, However, since heteropolar compounds consisting of a single compound or a mixture of closely relatedisomers are in most cases far superior to any mixture of compounds, it is usually desirable to separate the various products before attaching the polar groups. This separation, which may be neglected if desired, may be efiected at any one of three stages in the preparation, namely, previous to the rearranging, during the rearranging, or after the hydrogenation. Since in the rearrangement step the'material is subjected to a slow fractionation, the separation is most conveniently carried out during this operation, it being 'merely necessary to collect the promptly as possible. Since, however, in the maof from 1 to of an active hydrogenation catalyst such as nickel, using about 500 lbs. per square inch pressure and a temperature of about 150 C. However, other conditions including temperatures from 60 C. to about 250 C., pres-.

sure from one to over IOU atmospheres, the use of solvents and a wide variety of catalysts may be resorted to. Vapor phase hydrogenation, although applicable in many cases, is not as practical as the liquid phase hydrogenation and therefore not preferred. Any traces of sulfur tending to poison the catalyst may be removed previous to hydrogenation by first subjecting the beta gamma unsaturated ketone to a treatment with copper hydrate, spent catalyst or some other suitable agent in the known manner.

It is seen that by the proper choice of the ketones, aldehydes or esters used as starting materials, the condensation catalysts employed,

any,- of the common polar groups, certain polar groups are more practical than others. For example, the polar groups Cl, Br, --I, SH, CN and NO: are not easily attached to the present lipophile groups and moreover form heteropolar compounds of very restricted utility. Likewise, the. unsaturated ketones contain the polar carbonyl group, and are in reality heteropolar compounds. Due to-the weakness of the polar group and the unfavorable balance of these compounds, they are, however, of practically no value as h'eteropolaragents. The secondary alcohols of the present'invention are likewise hateropolar compounds, since they contain the polar hydroxyl group. These compounds are of some utility as heteropolar agents.

By far the most important class of polar groups are those which may be considered as being derived from an acid. The polar groups of this class can be designated as polar or lipophobic residues of acids.

One class of heteropolar compounds readilyprepared according to the present invention consists of esters of phosphorus-containing acids. By phosphorus-containing acids I mean to include ortho, meta and pyrophosphoric acid, ortho phosphorous acid and hypophosphoric acid as well as these acids in which one or more oxygen atoms have been replaced by sulfur or selenium. By esters, I mean to include both neutral and acid esters, mixed esters and the acid halide esters.

These phosphorus-containing esters, in view of their excellent properties, may find application for numerous purposes such as, for example, agents preventing the spattering of oils, as ingredients in boring and cutting oils, as ingredients in rust removerand metal cleaners, as ingredients in insecticides, fungicides and the like, as agents to improve ore flotation, as detergents, as wetting, dispersing, and emulsifying agents, as corrosion inhibitors, as lubricants or addition agents to lubricants for extreme pressure lubrication, etc.

Of the phosphorus-containing esters, those containing sulfur, i. e., esters of thio acids of phosphorus, and more particularly, the esters of the ortho thio acids are endowed with particularly valuable properties.

Other classes of heteropolar compounds, having certain unusually desirable properties may be prepared from the present alcohols by reacting them with sulfating, sulfiting, sulfonating, or sulfinating agents, polybasic carboxylic acids, etc., and by ester interchange with the lower alkyl esters of boric, arsenic, arsenous, acids etc. For example, the alcohols may be reacted with sulfuric acid, sulfurous acid, naphthalene sulfonic acid, amido sulfonic acid, chlorsuli'onic acid, sulfurylchloride, organic sulfamic acids, amino sulfonic acid, amino sulfonates, imino disulfonic acid salts, citric acid, succinic acid, lower alkyl a but not limited by the following examples:

Erampie I Illustrating the rearrangement of a; simple alpha beta unsaturated ketone to the corresponding beta gamma unsaturated ketone.

Methyl propyl ketone is condensed with itself by refluxing over calcium carbide. The product consists of unreacted methyl propyl ketone and 4-methyl-nonene-4-one-6, with a small amount of isomeric alpha beta dimers and trlmers. After distilling oif the unreacted methyl propyl ketone, the condensation products are charged, along with about 1% of sodium ethoxide, into a suitable fractionating apparatus. The mixture is brought to boiling, held under total reflux for a few minutes, and then fractionated while maintaining the stillhead temperature below the boiling point .of the 4-methyl-nonene-4-one-6 (195.5 C. at 160 mm.) In the absence of a rearrangement catalyst, the fractionation will be very slow. The distillate consists essentially of 4-methyl-nonene- 3-one-6.

Upon the completion of the rearrangement and removal of the ten carbon unsaturated ketones, the stillhead temperature may be allowed to rise to the boiling point of the doubly unsaturated beta gamma, beta gamma trimer which may be collected separately. During this latter operation it is preferable to conduct the rearrangement and fractionation under a diminished pressure.

Example H Illustrating the relative ease of hydrogenation of a beta gamma unsaturated ketone as compared to an alpha beta unsaturated ketone.

A mixture consisting essentially of 77% 3-methyl-heptene-3-one-5 and 22% isomeric twelve carbon alpha beta, alpha beta doubly unsaturated ketones is hydrogenated in the liquid phase for 183 minutes at 500 lbs. per square inch pressure and at 151 C. to 175 C. using a nickel catalyst. The refractive index changes during hydrogenation from 1.456017/D to 1.4394-165/1) after which the reaction virtually ceases. The product is found to contain only 2.3% of alcohol, the remainder being saturated ketone and a small amount of hydrocarbon. Under more drastic conditions the yield of alcohol may be increased, but only at the expense of an increased yield of hydrocarbon.

The same mixture is subjected to a rearrangement treatment as above described, the dimer being collected separately. The dimer fraction, consisting essentially of 3-methyl-heptene-2- one-5 upon hydrogenation for 245 minutes at 500 lbs. per square inch pressure and at 149 to 200 C. using a nickel catalyst yields from 85 to 94% 3-methyl-heptanol-5.

Example 111 Illustrating the preparation of a material suitcooled mixture is slowly added a one-third molar quantity of POCla. After completion of the reaction, the pyridine salt is removed and the benzol solution washed with dilute hydrochloric acid and with water. After removing the benzol by evaporation or distillation, the neutral trialkyl phosphate remains.

In the above example, the product has the structural formula O:PE(OR)3 wherein R.

represents the branched chain secondary alcohol ester radical. The monoor dialkyl esters having the structures /OR 0=P=Ch and 0=P=(0B)r Cl or upon hydrolysis of the chlorine atoms on 0R), 0= and 0:1

(OH): OH

Illustrating the preparation of a material particularly suitable for imparting oiliness and high pressure characteristic to lubricants.

A quantity of 3,7,9-trimethyl undecanoL-B is converted to the aluminate by any of the known methods, as, for instance, by the metathetic reaction with aluminum ethoxide. The higher alcohol aluminate is dissolved in a suitable solvent, the solution cooled to about C. and there is slowly added thereto with stirring a CS2 solution containing a one-third molar equivalent of PSCla while maintainingthe temperature at approximately 10 C. After allowing time for the reaction to come to completion any unused PSCla and the A1013 are hydrolyzed and the hydrocarbon phase washed with water, filtered, and the product finally recovered by distilling off the solvent. This product and other products having the structure S=P::(OR)3 wherein R represents a secondary branched chain alkyl radical, are superior to the neutral esters of the type shown in Example Ill when used as addition agents in lubricants. The neutral thio esters of this type are notably less viscous and have superior solubility in most lubricants.

While I have found phosphorus-containing esters containing lipophile groups of a secondary and branched chain character to be superior heteropolar agents in many respects to such compounds containing other types oi. lipophile groups, it will be appreciated that not all of the lipophile groups need be of this structure. For some particular purposes the so-called "mixed esters have been found to be the more efiicient. While still realizing the advantages of one or two lipophile groups of the present invention, the properties of a heteropolar compoundof the type may be tempered to fit a particular need by the introduction of one or two lipophile groups of a difierent character, such as, for instance, a short chain alkyl group or groups to enhance the wetting power or solubility, a phenolic group or groups to control solubility or heat stability, etc. Suitable lipophile groups which may be used in conjunction with the present secondary branched lipophile group or groups of difierent character.

are then introduced by completing the reaction with a suflicient quantity of thesecond appropriate agent, such as, forexample, diethylene glycol, phenol, amyl mercaptan, etc. If it is desired to prepare a mixed neutral ester the last reagent yielding the desired lipophile group is preferably added in a moderate, excess.

The acid esters of thiophosphoric acid are for many purposes superior to the corresponding.

oxy esters. Their comparative structures are where X represents OH, SL, or 0L, L representing any lipophile group, and R. again representing a branched chain, secondary lipophile group. These acid esters of thiophosphoric acid may be prepared in a manner'analogous to that described for the acid ow-esters, by reacting PSCla with such an amount of alcohol as is suificient to form only the mono or di esters. as the case may require.

Example V Illustrating the preparation. of a dialkyl ester of dithiophosphoric acid.

A quantity of 3-methyl-heptanol-5 in excess I is added slowly and with stirring to a suspension of P285 in benzene or toluene, holding the temperature at preferably about 50 C. After the apparent completion of the reaction, the solution is refluxed for several hours. Upon removing the solvent by distillation the impure product remains as a residue. Bjaidessmall amounts of impurities from the P285 and excess alcohol, there exists a small amount of a compound having presumably the structure on where R represents the secondary branched chain lipophile radical. The main product, which has the structure may be recovered by any of the known purification methods. In the form of its alkali metal salts it is moderately water-soluble, capillary active and exerts a mild detergent action.

Example VI Ifllustrating the preparation of a trialkyl phospentanol-3, when converted to the sodium alcoholate and reacted with a one-third molar equivalent of PCla, according to the well known pro-.

cedure for preparing aikyl phosphites, yields an interesting and novel material having presumably the structure When reacting the alcohol directly with P613 without first converting to the alcoholate, a considerable quantity of acid ester chlorides are formed which on hydrolysis yield acid esters having the structure P= on \OR and appropriate esters with concentrated sulfuric acid, sulphur, etc., in the known manner, interesting compounds may be prepared having the in which R represents a lipophilegroup having at least in one instance the saturated, secondary, branched chain structure as hereinbefore described.

Acid heteropolar compounds find their widest application in the form of their salts. In such cases, a further means of adjusting the heteropolar compound to give the maximum emciency is through the proper choice of a salt-forming agent. While any of the salt-forming alkaline agents such as alkali and alkaline earth bases, alkyl amines, dialkylamines, trialkylamines, alkyl diamines, aryl amines, diarylamines, thio aryl amines, aryl hydrazines, aralkyl amines, certain pyridines, pyrol and alkaloid derivatives, etc., may be used, the properties of the heteropolar compounds are considerably affected by the character of the salt-forming cation and the proper choice of salt-forming agent is entirely dependent upon the use for which the heteropolar compound is designed. In the i'oregoing and in the claims when referring to a heteropolar compound" or an ester, which terms cover the acid as well as the neutral esters, I mean to include the various salts as well as the acid esters.

The above description is to beconstrued as illustrative only and not as limiting the invention. The different features of the invention are capable of wide variation, and such changes as are within the spirit of the invention are intended to be comprehended by the scope of the claims.

I claim as my invention:

1. In a process for the production of a heteropolar compound from an unsaturated ketone, the steps of rearranging an alpha beta unsaturated ketone to the isomeric beta gamma unsaturated ketone, hydrcgenating the beta gamma unsaturated ketone to a saturated secondary alcohol, and reacting said alcohol with a sulfating agent.

2. In a process for the production of a heteropolar compound from an unsaturated ketone, the steps of rearranging an alpha beta unsaturated ketone to the isomeric beta gamma unsaturated ketone, hydrogenating the beta gamma unsaturated ketone to a saturated secondary alcohol, and reacting said alcohol with P0013.

3. In a process for the production of a heteropolar compound from an unsaturated ketone, the steps of rearranging an alpha beta unsaturated ketone to the isomeric beta gamma unsaturated ketone, hydrogenating the beta gamma unsaturated ketone to a saturated secondary alcohol and reacting said alcohol with PSCla.

4. In a process for the production of a heteropolar compound from an unsaturated ketone, the steps of rearranging an alpha beta unsaturated ketone to the isomeric beta gamma unsaturated ketone, hydrogenating the beta gamma unsaturated ketone to a saturated secondary alcohol, and reacting said alcohol with an agent capable of attaching in lieu of the hydroxyl group a lipophobic residue of a thio-phosphorus-containing acid.

5. In a process for the production of a heteropolar compound from an unsaturated ketone, the steps of rearranging an alpha beta unsaturated ketone to the isomeric beta gamma unsaturated ketone, hydrogenating the beta gamma unsaturated ketone to a saturated secondary alcohol, and reacting said alcohol with an agent capable of attaching thereto in lieu of the hydroxyl group a lipophobic residue of a phosphorus-containing acid.

6. In a process for the production of a heteropolar compound from an unsaturated ketone, the steps of rearranging an alpha beta unsaturated ketone to the isomeric beta gamma unsaturated ketone, hydrogenating the beta gamma unsaturated ketone to a saturated secondary alcohol and reacting said secondary alcohol with an agent capable of attaching thereto in lieu of the .hydroxyl group a lipophobic residue of a sulfurcontaining acid.

7. In a process for the production of a heteropolar compound from an unsaturated ketone, the steps of. rearranging an alpha beta unsaturated ketone to the isomeric beta gam a unsaturated ketone, hydrogenating the beta gamma unsaturated ketone to a saturated secondary alcohol, and reacting said secondary alcohol with an agent capable of attaching thereto in lieu of the hydroxyl group a lipophobic residue of an acid of an element of the amphoteric group consisting of sulfur, phosphorus, silicon, arsenic and boron.

8. In a process for the production of a heteropolar compound from an unsaturated ketone, the steps of rearranging an alpha beta unsaturated ketone to the isomeric beta gamma unsaturated ketone, hydrogenating the beta gamma unsaturated ketone to a saturated secondary alcohol, and reacting said secondary alcohol with an agent capable of attaching thereto in lieu of. the hydroxyl group a lipophobic residue of an acid.

9. In a process for the production of a heteropolar compound from an unsaturated ketone, the steps of rearranging an alpha beta unsaturated ketone to the isomeric beta gamma unsaturated ketone, and hydrogenating the latter to a saturated secondary alcohol.

10. An ester of a dithio-phosphoric acid containing at least one branched chain aliphatic lipophile group attached by a secondary carbon atom to an oxygen atom which, in turn, is linked to a phosphorus atom.

11. An ester of a thio-phosphoric acid containing at least one branched chain aliphatic lipophile group attached by a secondary carbon atom to an oxygen atom which, in turn, is linked to a phosphorus atom.

12. An ester of a phosphorus acid containing at least one branched chain aliphatic lipophile group attached by a secondary carbon atom to an oxygen atom which, in turn, is linked to a phosphorus atom.

13. An ester of a phosphoric acid containing at least one branched chain aliphatic lipophile roup attached by a secondary carbon atom to an oxygen atom which, in turn, is linked to a phosphorus atom.

14. An ester of a thio phosphorus-containing acid containing at least one aliphatic lipophile group attached to phosphorus through oxygen by a secondary carbon atom which, in turn, is attached to at least one aliphatic group containing a forked chain.

15. An ester of a thio phosphorus-containing acid containing at -least one branched chain aliphatic lipophile group of at least seven carbon atoms attached by a secondary carbon atom to an oxygen atom which, in turn, is linked to a phosphorus atom.

16. An ester 01'. a phosphorus-containing acid containing at least one aliphatic lipophile group attached to phosphorus through oxygen by a secondary carbon atom which, in turn, is attached to at least one aliphatic group containing a forked chain.

17. An ester of a phosphorus-containing acid containing at least one branched chain aliphatic lipophile group of at least seven carbon atoms attached by a secondary carbon atom to an oxygen atom which, in turn, is linked to a phosphorus atom.

FRANKLIN A BENT.