US3064047A - N, n', n"-trisubstituted oxyaspartamides - Google Patents

Description

United States Patent Ofifice 3,054,047 Patented Nov. 13,, 1952 This'invention is-concerned with new and useful compounds and compositions containing them. More particularly, it is concerned with new and useful derivatives of oxyaspartic acid and gelled compositions containing them. Further, in the process of preparation of the new and useful derivatives of oxyaspartic acid, a number of new intermediates were prepared. Further objects of this invention are made obvious by the following disclosure.

The new and useful compounds of this invention are N,N,N-trisubstituted oxyaspartamides wherein each of the substituents is selected from the group consisting of alkyl containing from 1 to 18 carbon atoms, alkenyl containing from 3 to 18 carbon atoms and aralkyl containing from 7 to 10 carbon atoms, the total number of carbon atoms in said substituents being from 18 to 54, the groups on at least the amido nitrogen atoms being identical. Such N,N',N-trisubstituted oxyaspartamides may be represented by thefollowing formula:

RHNOCCHCHCONHR )11 ILHR in which the summation of the'carbon atoms in R,R' and R is from 18 to 54 and in which at least R and R are identical.

Those N,N,N"-trisubstituted oxyasparta-mides in which R,R' and R" are identical may be prepared by reacting a lower alkyl ester of epoxysuccinic acid with an amine selected from the group consisting of alkyl amines containing from 6 to 18 carbon atoms, aralkyl amines containing from 7 to 10 carbon atoms and alkenyl amines containing from 6 to 18 carbon atoms.

Those N,N,N"-trisubstituted oxyaspartamides in which at least R and R are identical may be prepared by reacting N,N'disubstitut=ed expoxysuccinarnides, wherein the substituents are selected from the group consisting of alkyl containing from 1 to 18 carbon atoms, alkenyl containing from 3 to 18 carbonatoms and aralkylcontaining from 7 to 10 carbon atoms, the substituents being identical, with an amine selected from the group consisting of. alkyl amines containing from 1 to 18 carbon atoms, alkenyl amines containing from 3 to 18 carbon atoms and aralkyl amines containing from 7 to 10 carbon atoms.

Such N,N'-disubstituted epoxysuccinamides may be represented by the following formula:

in which R and R are identical and are selected from the group consisting of alkykl containing from 1 to 18 carbon atoms, alkenyl containing from 3 to 18 carbon atoms and aralkyl containing from 7 to 10 carbon atoms.

It has been unexpectedly discovered that the N,N',N"- trisu-bstituted oxyaspartamides, described above, possess. the unique and desirable properties of a gelling agent. A gelling agent is a substance which, when admixed with liquid substance, converts the liquid substance to the solid phase of a colloidal solution as opposed to the sol, the liquid phase of a colloidal solution. In simple terms, the liquid is converted from a free-flowing state to a jellylike state. Gelling agents are particularly useful in converting free-flowing liquid products into a thickened or partially rigid state. A number of industrial applications of gelling agents are well known to those in the art. For example, various hydrocarbon oils may be thickened to 2 greases by the addition of a gelling agent. Liquid combustible alcohols, such as ethyl alcohol, and hydrocarbons, such as gasoline, may be gelled to a thickened, if not rigid state and used as fuels which are less hazardous than the liquid state.

As mentioned above, the new and useful compounds of this invention, i.e. N,N',N-trisubstituted oxyaspartamides, may be prepared from epoxysuccinic acid lower alkyl esters or N,N-disubstituted epoxysuccinamides by reaction With an alkyl, alkenyl or aralkyl amine. One mole.

of epoxysuccinic acid lower alkyl ester is reacted with atleast 3 moles of the selected amine. It is usually sufficient to contact the amine with the epoxysuccinic acid ester to' obtain the product. The reaction is preferably carried out at temperatures ranging from about 30 C. to about C. Temperature, however, does not appear to be critical, appreciable reaction being effected at temperatures as low as 0 and high as 200 C. Usually, for best result, a suitable solvent is employed, although a solvent is not always found necessary. Suitable solvents which may be employed are hydroxylated solvents, such as lower alkanols, for example, methanol, ethanol, pentanol, and glycols, for example, ethylene glycol, propylene glycol, diethylene glycol, dipropylene gylcol and other glycols. Liquid aromatic hydrocarbons, such as benzene and toluene, are also found to be suitable solvents. Generally, when a solvent is employed, it is preferred to maintain the reaction mixmm at the reflux temperature of the solvent. When anepoxysuccinic acid ester is employed, it is found that when the theoretically-required amount of the amine isemployed. When the amine is liquid, the amine may also be used as solvent for the reaction. The reaction mixture is usually agitated to obtain best results. The amine may be added to the ester in one portion, portionwise or dropwise with equivalent results being obtained. Product formation is almost instantaneous, but for best yields, heating and stirring is continued for from about 5 to 24 hours, depending on the amine and quantities of reagents employed. It is preferable but not essential, to carry out the reaction in an inert atmosphere such as a nitrogen gas atmosphere. The product is obtained by standard procedures such as evaporation of the reaction mixture at re-. duced pressure. The crude residue may berecrystallized from suitable solvents by standard procedurm. Suitable solvents are: ethyl acetate, dimethylformamide, acetonitrile dioxane, chloroform, heptane and other similar solvents. N,N'-disubstituted epoxysuccinarnides are treatedwith at least 1:1 molar ratio of an amine under substantially the same conditions as described in the reaction of epoxysuccinic acid esters. Excess amine may be employed-as mentioned above.

N,N-disubstituted epoxysuccinamides wherein the substituents are alkykl, alkenyl or aralkyl as described above may be prepared by reacting epoxysuccinic acid lower alkyl esters with an alkyl, aralkyl or alkenyl amine of suitable carboncontent. This is indeed an unexpected result, since it is expected that the epoxide linkage of epoxysuccinic acid esters would react before reaction with the ester groupings. This unexpected result is obtained by contacting one mole of the epoxysuccinic acid ester with up to 2.1 moles of the selected amine, but preferably with from about 2 to about 2.1 moles of the selected amine. The reaction is carried out in a hydroxylated solvent, such as lower alkanols, for example, methanol, ethanol, propanol and pentanol, and glycols, for example, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol and others. Temperature does not appear critical for this reaction. Temperatures or from about 20 C. to about the reflux temperature of the solvent may be employed with excellent yield of the product being obtained. Solvents need not be employed, but for best results it is preferred to carry out the reaction in a suitable solvent, particularly, when the amine boils at less than 40 C. The amine may be added in one portion, portionwise, or dropwise when liquid or dissolved in a solvent. For best results, it is preferred to add the amine in a portionwise or dropwise fashion. Solid amines are preferably dissolved in a solvent for such addition. The rate of addition should be such that about 0.25 mole of the amine is added over a period of time of from about 45 to 90 minutes. It is desirable to effect this reaction in an inert atmosphere, such as a nitrogen atmosphere. After cooling the reaction mixture the product is obtained by standard procedures, for example, by filtration of the reaction mixture. The solid products thus obtained may be further purified by standard procedures of recrystallization or used, in the crude form, in a preparation of the oxyaspartamides as described above. Suitable solvents for recrystallization are dioxane, chloroform, dimethylformamide, acetonitrile, lower alkanols and hydrocarbon solvents such as hexane, heptane, benzene and toluene. Alternatively, the N,N-disubstituted epoxysuccinamide may be converted in situ by addition of at least one mole of a selected amine employing the procedure described above to cor-responding trisubstituted oxyaspartamides.

Alternatively, N,N' disubstituted epoxysuccinamides may be prepared by the reaction of epoxysuccinyl chloride with appropriate primary and secondary amines of suitable carbon content. This process is generally familiar to those skilled in the art. For example, a 4 to 1 molar ratio of the amine is added to epoxysuccinyl chloride at a temperature of from about to about 50 C. The excess amine is employed to react with the hydrogen chloride formed. The product is obtained by washing the reaction mixture with water to dissolve the aminehydrochloride and then recrystallized from a suitable solvent as described above.

As previously mentioned, the above described N,N,N- trisubstituted oxyaspartamides are novel, valuable gelling agents. When these compounds are added to liquids, such as liquid hydrocarbons, hydrocarbon oils, alcohols, and liquid glyceride esters, the liquids are converted to the state of a reversible gel. Such compositions may be in the form of a non-fluid plastic paste or cream or may even be a viscous liquid consistency. Heretofore, gelled compositions have been subject to limitations, the most outstanding of which is the lack of stability, which results in a separation of the components. This is an insidious problem in the storage of commercial gelled compositions. The gelled compositions of this invention are found to be stable after storage at 30 to 35 C. for time periods up to 6 months, no noticeable separation of the components being noted.

Further advantage of the gelling agents of the present invention lies in the reversibility of the gelling action. When a pasty gel possesses the remarkable property of liquefying when shaken, stirred or otherwise physically agitated such a phenomenon is known as thixotropy. The gelled compositions of this invention are thixotropic gels since they do liquefy on physical agitation and, on standing, revert to a gel. Thixotropic gels may also be liquefied by ultrasonic, i.e. high frequency sound waves and by any means which produces internal mechanical stress. Gels may also be liquefied at elevated temperatures. The thixotropic gelling agents of this invention have particular value to the paint industry, wherein the maintenance of uniform oil-based paint compositions is a major difliculty. For example, the pigments and the vehicle, usually linseed oil, a glyceride ester, separate from the paint composition necessitating laborious time consuming procedures of agitating the paint to obtain a homogeneous composition. Frequently, the pigment is unequally distributed, resulting in different shades of color in the paint finish. The incorporation of the gelling agents of the present invention into paint compositions produces a gelled composition of uniform consistency which may be utilized in paint application. The gelled paint compositions are found as freefiowing and easily applicable as paints not gelled with oxyaspartamides with the added advantage of having stable, uniform distribution of the pigment and vehicle. Generally, it is preferred to incorporate from about 5% to about 15% by weight of a gelling agent of this invention in the linseed oil-paint although up to 25% by weight may be employed to produce thicker paint gels for special purposes.

Hydrocarbon oils, for example, lubricating oils may be converted to smooth thixotropic gels of increased heaviness which possess the properties of a lubricating grease. Further, hydrocarbons which are liquid under atmospheric conditions may be gelled to thixotropic compositions. For example, liquid hydrocarbons, such as hexane, heptane, and octane, as well as mixtures of such hydrocarbons, for example, gasoline, may be converted to thixotropic gels by incorporating into these liquids the N,N,N"- trisubstituted oxy-aspartamides of this invention. Usually, from about 5% to about 25% by weight of the present gelling agents is utilized in gelling lubricating oils and liquid hydrocarbons. Alcohols such as the lower alkanols for example, methanol and ethanol are also gelled at this same range of concentration. Gelled compositions of liquid hydrocarbons and alcohols are particularly useful as semi-solid fuels which are less hazardous than the corresponding liquid forms. These are useful in commercial canned heat products which are used for varied purposes, for example, outdoor cooking and emergency heating and lighting. The gelled compositions are prepared by adding the selected trisubstituted oxyaspartamide to the liquid and intimately mixing. A convenient method is addition of the gelling agent while the liquid is being stirred or otherwise agitated.

In general, those N,N',N"-trisubstituted oxyaspartamides of the following formula:

in which R, R and R" are selected from the group consisting of alkyl groups containing from 1 to 18 carbon atoms, alkenyl groups containing from 3 to 18 carbon atoms and aralkyl groups containing from 7 to 10 carbon atoms, and in which the summation of the carbon atoms of R, R and R" is from 18 to 54, are found to possess the valuable properties of thixotropic gelling agents. The preferred thixotropic gelling agents are those in which the summation of carbon atoms in R, R and R is from about 24 to about 36.

Gels made with the present gelling agents are found tobe highly stable over long periods of storage, no noticeablebreakdown of the gels being noted even after storage for from about three to six months.

The following N,N,N-trisubstituted oxyaspartamides' may be prepared from epoxysuccinic acid lower alkyl. esters and also from suitably N,N-disubstitutcd epoxysuccinamides by the respective procedures described above:

N,N', -trihexyloxyaspartamide N,N,N"-trioctadecyloxyaspartamide N,N',N"-trioctadecenyloxyaspartamide N,N,N"-tridecyloxyaspartamide N,N,N"-tribenzyloxyaspartamide N,N',N-trihexenyloxyaspartamide N,N',N"-tri (phenylbutyl -oxyaspartamide N,N,N"-tri (phenylethyl -oxyaspartamide N,N,N"-trioctyloxyaspartamide In addition, the following N,N',N"-trisubstituted oxyaspartamides have been prepared from corresponding N,N-disubstituted epoxysuccinamides by the procedure described above:

5. N,N-dimetyh1,N"-hexadecyloxyaspartamide N,N-dioctyl,N" benzyloxyaspartamide N,N-dioctyl,N"-decyloxyaspartamide N,N-dioctadecyl,N"-al-lyloxyaspartamide N,N'-bis (decyl) ,N"-benzyloxyaspartamide N,N-.dioctadecenyl-N"-methyloxyaspartamide N,N-diallyl-N"-octadecyloxyaspartamide N,N'-dihexadecylN' methyloxyaspartamide N,N'-dibenzyl-N"-octadecyloxyaspartamide N,N-di- (phenylbutyl) ,N-decyloxyaspartarnide N,Nbis (undecyl ,N"-octylox.'aspar-tamide N,N-dipropyl,N"-dodecyloxyaspartamide N,N4bis'( octenyl) ,N-dodecyloxyaspartamide For the preparation of the above compounds, the following N,N'-disubstituted epoxysuccinamides were prepared by reaction of epoxysuccinic acid lower alkyl esters and suitable aralkyl, alkyl and alkenyl amines as described above: I

N,N-dimethylep oxysuccin amide N,N'-bis( allyl epoxysuccinamide N,N-bis( octadecyl iep oxysuccinamide N,N'-bis( octadecenyl )ep oxysuccinamide N,N-dibenzylepoxysuccinamide N,N'-di-( phenylbutyl) ep oxysuccina'rnide N,N-bis decyl) epoxysuccinamide N,N'-di phenyl'ethyl epoxysuccinamide N,N'-bis-(hexadecy1)epoxysuccinamide N,N-dipropylep oxysuccinamide N,N-bis dodecyl epoxysuccin amide N,N'-bis (dodecenyl) ep oxysuccinarnide N,N'-bis (undecyl) epoxysuccinamide Epoxysuccinic acid lower alkyl esters may be prepared by reacting epoxysuccinic acid with an alkanol of from 1 to 5 carbon atoms in the presence of an esterification catalyst, such as sulfuric acid, by the method commonly employed in the art. Alternatively, these esters may be prepared by reacting an alkaline earth metal salt of epoxysuccinic acid, for example, barium or calcium epoxysuccinate, with at least a 2:1 molar ratio of the selected alcohol in the presence of equimolar quantities of sulfuric acid. Usually, a slight excess, approximately of sulfuric acid is employed, the excess being neutralized before isolation of the ester. The method of preparation may be as follows: The alkaline earth metal salt may be suspended in the desired alcohol and then concentrated sulfuric acid added or alternatively, the salt maybe treated with a mixture of the alcohol and concentrated. sulfuric acid. The temperature of the reaction mixture rises during the addition of sulfuric acid and is maintained at from about 40 C. to about 60 C. by the dropwise-addition of the acid and efiicient stirring. After the addition is completed,- heating and stirring is continued for about hours. Usually, excess alcohol is employed. From 100% to 200% excess of the theoretically required amount of the alcohol gives excellent yields of ester. After filtering the insoluble salts and distilling offexcess alcohol, the desired ester is obtained by distillation at reduced pressure. The crude esters may be employed in place of the purified esters in the production of the epoxysuccinamides and oxyaspartamides described above with equal ease. Epoxysuccinic acid may be produced by fermentation processes as described in US. Patent 2,674,561. The alkaline earth metal salts may be prepared-by reacting epoxysuccinic acid with alkaline earth metal compounds such as the carbonates, bicarbonates and hydroxides, in aqueous solution by' standard procedures.

The following examples are given by way of illustration and are not to be'construed'as limitations of this invention many variations of which are possible within the scope and spirit thereof.

EXAMPLE I Preparation of N,N-Dibenzyl-Epoxysuccinamide Five grams of methyl epoxysuccinate was suspended 50 ml. of methanol in a 200 ml. round-bottomed threenecked flask fitted with stirrer, dropping funnel, thermometer and CO -free nitrogen inlet. With stirring, 6.7 g. benzylamine dissolved in 20 ml. of methanol was added dropwise at 30 to 40 C. during /2 hour. The ester dissolved and the amide precipitated. After an additional 45 minutes of stirring at the same temperature the reaction was interrupted, filtered, and the residue washed with a little ice water. The crude yield was 4.5 g. of material. Recrystallization from dioxane gave white prisms, M.P. 178-180".

Elemental analysis.-Calcd. for C H N O C, 69.66; H, 5.85; N, 9.03. Found: C, 69.54; H, 5.81; N, 9.02.

EXAMPLE II N,N'-di(phenylethyl)-epoxysuccinamide and N,N'-di- (phenylbutyl)-epoxysuccinamide were prepared according to the procedure of Example I, employing phenylethylamine and phenylbutylamine, respectively in place of benzylamine.

EXAMPLE III Preparation of N,N'-Dipropyl-Epoxysuceinamide' EXAMPLE IV Preparation of N,N-B is-A llyl-Epoxysuccinamide A 500 ml. four-neckedround-bottomed flask fitted with stirrer, thermometer, dropping funnel, and CO -free nitrogen source was charged with 30.0 g. of methyl epoxysuccinate and m1. of propanol. Most of the methyl ester dissolved and 21.5 g. of allylamine was added dropwise during 80 minutesat 30 to 35 C. The amine was mixed with an equal volume of propanol' before addition. Precipitation of the amide began after about 50 minutes. Stirring was continued for 4 /2 hours after completing addition of the amine. The mixture was filtered and the residue 'washed with water and with l N hydrochloricv acid. In this way was obtained 24 g. of white crystals, M.P.- 218-220. Recrystallization from dioxane gave white crystals. Y

Elemental analysis.-Calcd. for C H N oz C, 57.15; H, 6.71; N, 13133; G, 22.83. Found: C, 56.94; H, 6.61; N, 13.09.

EXAMPLE V Preparation of N,N-Bis-Decyl-Epoxysuccinamide A 20.0 g. sample of methyl epoxysuceinate was suspended in 75 ml. of dry ethanol in 500 ml. four-necked, round-bottomed flask fitted with stirrer, thermometer, dropping funnel and CO -free nitrogen inlet. Most of the methyl ester dissolved as the mixtured was stirred and warmed to 35. Then 40 g. of decylamine was added dropwise' with stirring under nitrogen'at' 30 to 40 C. during 1% hours. The mixture was stirred an additional 5 hours under the same conditions. Filtration of the mix-- ture gave 42.4 g. of N,N'-bis-decyl-epoxysuccinamide.

Recrystallization from dioxanegave an analytical sample,-

M.P. -163 (dec.).

7 EXAMPLE VI Preparation of N,N'-Dimethyl-Epoxysuccinamide Five grams of methyl epoxysuccinate was added to 50 ml. of methanol and 8 grams of a 25% methyl amine solution was added dropwise to the mixture over a twelve minute period. A white solid began to separate almost immediately. After 2 hours of stirring the mixture was filtered and the solid product recrystallized from dioxane and from acetonitrile to white crystals, M.P. 238-240 C.

Elemental analysis gave the following results: Calcd. for C H N O C, 45.56; H, 6.37; N, 17.71. Found: C, 45.31; H, 6.31; N, 17.92.

EXAMPLE VII Preparation of N,N-Bis(ctadecyl) -Ep0xysnccinamide A 200 gram sample of ethyl epoxysuccinate was added to 200 ml. of ethanol and the mixture heated to reflux temperature while 74 g. of octadecylamine in 100 ml. of ethanol was added to the mixture dropwise with stirring over a period of 1 hour. Precipitation of the diarnide began shortly after addition of amine was begun. Heating and stirring of the reaction mixture was continued for eight hours. The mixture was filtered after cooling and the solid product obtained in 85% yield recrystallized from dimethylforamide and from dioxane to' give pure product M.P. 146147 C. Analysis for nitrogen gave a value of 4.50% (4.53% theoretical).

EXAMPLE VIII N,N-bis(octadecenyl)-epoxysuccinamide and N,N-dihexenylepoxysuccinamide were prepared according to the procedure of Example VII using octadecenylamine and hexenylamine and dipentyl epoxysuccinate.

EXAMPLE IX Preparation of N,N'-Bis(Hexadecyl)-Epoxysuccinamide EXAMPLES X-XIII Preparation of N,N-Bis( Undecyl)-Ep0xysuccinamide, N,

N -Bis( Oetyl -Epoxysuccinamid e; N ,N '-D inonylepoxysuccinam ide; and N,N'-Bis(Dodecyl)-Epoxysuccinamide These amides were prepared according to the procedure of Example V by reacting 0.125 mole of the corresponding amine with 0.25 mole of propyl epoxysuccinate or amyl epoxysuccinate. Excellent yield of the amides were obtained. The analytical data is tabulated in Table I.

TABLE I Melting Epoxysuccinamide point C H v N -b' t 1 168169.5 Calcd.-. 67.75 10.80 7. 90 M y) s 2 11%; n 1 169-171 alc 6.0 7. dmo y 160mm" (758.85 112.2; gg

un 162-164 alcd--- 1.18 1 N,N b1s( decyl) gon a 3 3 1kg 2 65 '-b' 1 162464 alcd-.- 2. 5 1 mdodecy) 01mm. 71.84 11.70 6. 34

All products were recrystallized from dioxane and/or chloroform.

8 EXAMPLE XIV Preparation of N,N,N"-Tridecyloxyaspartamide A 25 g. sample of methylepoxysuccinate was added to 200 ml. of ethanol in a 500 ml. round-bottomed flask. With stirring under nitrogen gas, g. of n-decylamine was added in one portion. The mixture was heated with stirring for 22 hours at 70-74 C. The waxy solid product was filtered and recrystallized from dimethylformamide to soft, white crystals, M.P. 119.5 120.5 C.

Elemental analysis gave the following result: Calcd. for C H N O C, 71.90; H, 12.25. Found: C, 71.52; H, 11.81.

EXAMPLE XV Preparation of N,N,N"-Trioctadecyloxyaspartamide In a 1 L. round-bottomed flask was added 20 g. of methylepoxysuccinate, 170 g. of octadecylamine and 500 ml. of dry methanol. The mixture was stirred vigorously at gentle reflux of the solvent. After 22 hours the mixture was cooled and filtered. The solid product was recrystallized from chloroform and from heptane to soft, white crystals, M.P. Ill-112 C.

Elemental analysis gave the following results: Calcd. for C58H117O2N3: N, 4.73- Found: N,

EXAMPLE XVI Preparation of N,N,N"-Tri0ctyloxyaspartamide A one liter, round-bottomed flask was charged with 24 g. of amyl epoxysuccinate, 200 ml. of dry ethanol and 48.4 g. of octylamine. The mixture was heated for 24 hours. It was then cooled and filtered. The solid product was recrystallized from dioxane and from chloroform to pure material, M.P. -122 C.

Elemental analysis gave the following results: Calcd. for C H N O C, 69.51; H, 11.88; N, 8.69. Found: C, 69.50; H, 12.03; N, 8.69.

EXAMPLES XVII-XXII Other N,N,N"-trisubstituted oxyaspartamides were prepared employing the procedure of Example )GV. These compounds are listed in Table II together with the starting compounds, solvents, times and temperatures employed.

TABLE II oxyaspartamide Epoxysuccinate Temp.

Amine .Solvent C.)

Trihex Methyl. n-Hexyl Trioctadecenyl- PropyL n-Octadec n l Trihenzyl Trihexenyl A Tri(phenylethyl) Methyl Phenylethyl.-. Pentanol. T)i(ph1e)nyldo PhenylbutyL- Methanol uty EXAMPLES XXIII-XXXVII Preparation of N,N',N"-Trisubstituted Oxyaspartamides From N,N'-Disubstituted Epoxysuccinamides EXAMPLE XXXVIII To a 1000 g. sample of a standard industrial oil paint (in this example, a lead-titanium pigment industrial paint,

available from the Metal and Thermite Corp, Rahway, NJ.) was added 50 g. of N,N,N"-tridecyl-oxyaspartamide. The mixture was thoroughly agitatexl by mechanical mixing or shaking. The resultant composition was less fluid than the original paint sample, but was as easily applicable. The thickened composition was readily applied to a prepared surface by the usual method of brushing with the production of an even paint-finish of uniform color.

A sample of the thickened paint composition was stored at room temperature for a period of three months after which no appreciable separation of the pigment or vehicle was noted. The composition was ready for application as described above without the necessity of prolonged stirring 10 EXAMPLE XLIII EXAMPLE XLIV Preparation of Lower Alkyl Epoxysuccinates A 1 mole sample of barium epoxysuccinate was susor shaking. A second sample of paint not containlng the 1 pended m 1 liter of methanol in a round-bottom flask to gelling agent mentioned above had to be stirred vigorously which was slowly added 1.1 moles of concentrated sulto provide a near homogeneous composition after storage furic acid. The mixture was stirred and refluxed for 5 for a similar period of time. hours and the mixture then was cooled. Powdered cal- TABLE III Molar Time ratio 01 Oxyaspartamlde Epoxysucclnamide Amine Solvents of heat- Temp. amine to ing C.) oxyas- (brs.) partammide N,N-dimethyl,N"=hexadeeyl 8 Reflux l. 1 1 N,N-diocty1.N-benzyl 10 Reflux 1. 1:1 N,N-dioctyl ,N-ddecyl 8 100-105 1. :1 N,N-dioctadecy1,N"-allyl- 5 40- 45 1. 5:1 N,N-bis( 1eeyl) ,N"-benzyl i 8 100-105 2: 1 N ,N bis (octadeeenyl) ,N'methyl.. Methyl. 6 30 1. 5:1 N,N'-diallyl,N-octadecyl N N Octadecyl... 8 120-125 1.1:1 N,N-dihexadecyl N'methyl Methyl 6 40 1.5:1 N,N-dibenzyl-N octadecyl OctadecyL- 12 100-105 1 :1 N,N-di-(phenylbuty1),N-decyl Decyl 10 90-95 1. l :1 N,N-bis(undeey1),N-octyl Octyl 10 Reflux 1. 2:1 N,N-dipropy1,N -oxtadecyl Octadecyl- 11 Reflux 1. 2 1 N,N'-bls(octenyl),N-dodecyl DodecyL 9 Reflux 1.1:1 N,N',N-trioctadecyl OctadeeyL- 13 125-130 1. 1:1 N ,N ,N-tridecyl Decyl 10 140 1. 5:1

EXAMPLE XXXIX The process of Example XXXVIII was repeated employing 100 g. of N,N',N"-tridecyloxyaspartamide with comparable results.

EXAMPLE XL The processes of Examples XXXVIII and XXXIX were repeated with the N,N',N-trisubstituted oxyaspartamides described in Examples XV through XXXVII with comparable results.

EXAMPLE XLI To a one-hundred gram sample of a light lubricating oil, S.A.E. 20, was added 5 g. of N,N,N"-tridecyloxyaspartamide and the mixture thoroughly agitated by stirring or shaking. The mixture thickened to a smooth, even grease which possessed excellent heavy-duty lubricating properties. The product was found to be unchanged after storage at room temperature for 3 months.

A second 100 g. sample of the oil was treated with g. of N,N,N"-tridecyloxyaspartamide in the same manner as above. The resultant product was thicker than the above product and as smooth and even. It is also found to have excellent lubricating properties.

The trisubstituted oxyaspartamides as described in the Examples XV through XXXVII were employed as described in this example with comparable results.

EXAMPLE XLII Ethanol was treated with 5% by weight of an N,N,N"-

trisubstituted oxyaspartamide as described in Examples 7 cium carbonate was then added and the mixture stirred for /2 hour, after which the temperature was increased to 60 C. The hot mixture was filtered, the filter washed several times with hot methanol and the methanol solutions combined. The methanol solution was stripped of alcohol at reduced pressure to obtain crystalline methylepoxy-succinate, M.P. 7275 C. in excellent yield.

The ethyl, propyl and amyl esters of epoxysuccinic acid were prepared in the same manner.

Alternatively, the same esters were prepared directly from succinic acid by standard procedures.

What is claimed is:

N,N,N"-trisubstituted B-hydroxy-aspartamide wherein each of the nitrogen substituents is selected from the group consisting of alkyl having from 1 to 18 carbon atoms, alkenyl having from 3 to 18 carbon atoms and aralkyl having from 7 to 10 carbon atoms, the total number of carbon atoms in said substituents being from 18 to 54, the groups on at least the amido nitrogen atoms being identical.

References Cited in the tile of this patent UNITED STATES PATENTS 2,200,220 Reppe et a1 May 7, 1940 2,404,714 Latham July 23, 1946 2,553,568 Finkelstein May 22, 1951 2,610,114 Fischer et al Sept. 7, 1952 2,671,064 Cowell et al Mar. 2, 1954 OTHER REFERENCES Beilstein: Page 319, vol. 18, Mainwork (1934). Uspekhi Khim., vol. 17, page 445 (1948).

Union Carbide-Peracetic Acid and Derivatives, P-57- 0216, copyright 1957, page 19.

Rittinger: Darstellung und Reaction von Glycidesaurenitrilen, page 2 (1957).