US2238940A - Condensation products from high molecular weight carbocyclic ketones - Google Patents

Description

Patented Apr. 22,1941

CONDENSATION PRODUCTS HIGH 'MOLECULAR WEIGHT OARBOCYCLIC KE- TONES Adrian Laverne Linch, Wilmington, Del., and Viktor Weinmayr, Pitman, N. J., assignors to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware No Drawing.

Application July 22, 1939,

Serial N0. 285,856

9 Claims.

This invention relates to the preparation of new and valuable organic compounds and more particularly to the preparation of the new condensation products which result from the condensation of aliphatic compounds of the class consisting of.paraflins and olefines and their derivatives, which contain an aliphatic chain of at least 2 carbon atoms, with highmolecular weight carbocyclic keto compounds in the presence of hydrofluoric acid.

While the condensation of certain carbocyclic compounds with alkyl compounds is known to take place in the presence of acid condensation agents such as concentrated sulfuric acid, phosphoric acid, aluminum chloride, zinc chloride, antimony chloride, etc., it is well known that many aromatic compounds can not be successfully alkylated with these reagents. Often the condensation fails to go at all with such reagents or undesirable side reactions take place which render the process inoperable from a commercial point of view. In the case of certain substituted aromatic compounds such as dimethoxydibenzanthrone, the ether groups are split of! when such reagents as sulfuric acid are employed at elevated temperatures.

It is an object of the present inventionto prepare new and valuable organic compounds by the alkylation of high molecular weight carbocyclic keto compounds with aliphatic compounds, containing an aliphatic chain of at least two carbon atoms, which new condensation products are valuable as dyestuffs, or for coloring materials such as petroleum hydrocarbon oils, hydrocarbon solvents and the like.

By the term high molecular weight carbocyclic keto compounds, we refer to those carbocyclic keto compounds containing at least four benzene rings. As examples of this class of high molecular weight keto compounds may be mentioned benzanthrone, benzanthraquinone, pyrenequinone, perylenequinone, pyranthrone, dibenzanthrone, meso-benzdianthrone, and their substitution derivatives, such as the nitro, halogen, alkyl, aralkyl, aryl, alkoxy, hydroxy, mercapto, sulione, sulfonic acid, amides, carboxylic acids, esters, amino, alkylamino and arylamino derivatives.

We have found that these high molecular weight aromatic keto compounds can be condensed with aliphatic compounds of the olefine and paraflln series which contain an aliphatic chain of at least 2 carbon atoms in the presence of hydrofluoric acid to give new alkyl Condensation products in which the alkyl groups are attached to the carbocyclic compound through a carbon to carbon linkage. The number of alkyl groups which maybe introduced into the ketonic compound may be controlled by the amount of alkylating agent employed and the conditions under which the condensation is carired out. The number of alkyl groups that may be introduced into the ketonic compounds also depends upon the character of the particular keto compound. We have found that from 1 to 6 alkyl groups can be introduced into the dibenzanthrone molecule. In the condensation the keto oxygen of the high molecular weight keto compound may be partially or entirely removed. Because of the high molecular weight of these compounds it has been impossible to determine whether an alkyl group replaces the ketonic oxygen or whether the keto group is reduced during the reaction being entirely removed or converted to a hydroxyl group. In certain instances where only one alkyl group is introduced into a keto compound that prior to condensation is vattable, the resulting product may no longer be vatta-ble. Where at least 6 carbon atoms have been introduced into the high molecular weight ketones by this process the resulting products show oil or solvent solubility. These aliphatic carbon radicals may appear as a single chain of 6 carbon atoms or as several chains of 2 or more carbon atoms. Where the alkylation of the high molecular weight carbocyclic ketone is carried to completion substantially all of the ketone is converted to an oil soluble compound. In general, the greater number of aliphatic groups introduced into the carbocyclic ketone molecule the greater the solubility of the resulting product in oils. The molecular weight of the aliphatic compound also has a maof incompletely alkylated product that is in-- soluble in benzene may be obtained. These products where they are still vattable dye in difierent shades than the original vat dyestufls and exhibit good fastness properties. The benzene soluble products resulting from this condensation exhibit a green color in concentrated sulfuric acid and when dissolved in solvents usually exand the like.

The following compounds illustrate the various types of aliphatic compounds of the olefine and paraffin series which may be'condensed with the high molecular weight carbocyclic ketones in hydrofluoric acid; amyiene, butylene, di-isobutylene, linoleic acid, cetene, diethyl ether, isopropyl ether, amyl BJCOhOLhBPtflDG, stearic acid, dimethyl stearylamine, caproamide. amyl benzene, dodecyl sulfate, trilauryl borate, acetone, butyraldehyde, etc. In the term aliphatic compounds, we include those aliphaticcompounds which may also carry an aromatic or cyclo aliphatic radical such as amyl benzene, diand triamyl benzenes, octyl cyclohexane, dodecyl benzene, etc.

The carbocyclic keto compound and the aliphatic compound are dissolved or suspended in hydrofluoric acid (the reactants may be mixed together in any order desired), and the reaction is carried out at temperatures varying from below C. to substantially the critical temperature of hydrofluoric acid. Temperatures of from 0 to 170 C. are preferred, for at temperatures below 0 C. the condensation proceeds very slowly and at temperatures above 170 C. undesirable side reactions take place with many of the compounds. The reaction may be carried out at atmospheric pressureif the temperatures employed are such that there is no appreciable loss of reactants. Superatmospheric pressures, however, are preferred due to the high vapor pressure of hydrofluoric acid at ordinary temperatures. While anhydrous hydrofluoric acid is preferred, aqueous solutions of this acid varying from the constant boiling mixture (36% hydrofluoric acid) to the anhydrous hydrofluoric acid may be used, depending upon the character of the other reactants. At concentrations below 50% hydrofluoric acid the condensation proceeds very slowly.

The amount of hydrofluoric acid based on the weight of the other reactants may be varied widely so long as suflicient hydrofluoric acid is employed to keep the reaction mass in a relatively fluid state. From 1 to 6 parts of hydrofluoric acid have been found to give good results. The reaction may be carried out in vessels made of any material capable of withstanding the mildly corrosive efiects of the hydrofluoric acid. When the hydrofluoric acid of concentrations of 60% or greater is employed "18-8 stainless steel, ordinary steel, nickel, Monel metal or copper autoclaves or other reaction vessels may be used. Where hydrofluoric acid of less than 60% concentration is employed, special alloys such as Electron metal should be used.

The time required for completing the condensation varies widely, depending upon the reactivity of the particular reactants and upon the temperatures employed. Usually about 41 hours is sufficient to complete the condensation, although, in some cases, a much longer time is required.

The following examples are given to illustrate the invention. The parts used are by weight:

Example 1 A steel autoclave equipped with agitation is charged with 110 parts of commercial anhydrous hydrofluoric acid, 18.2 parts Bz-l-nitrobenzanthrone and 30.5 parts isopropyl ether. The temperature is raised to 150 C. under autogenous pressure and held at that temperature four hours.

hibit a strong fluorescence, making them par- The mass is cooled to room temperature and discharged into 1000 parts ice and water. It is flltered, the cake is washed until the wash liquors are free of acid, and dried. The resulting redbrown powder may be separated into two frac tions as follows:

The crude powder is digested three timeswith boiling benzene, using approximately 180 parts of benzene for each digestion. 13.3 parts of a black insoluble material which contains 2.09% nitrogen remains undissolved. The benzene from the combined extracts is evaporated and the residue is extracted with 200 parts of petroleumether. 12.3 parts of a brown powder are obtained which melts at -126 C., has a molecular weight of 532 (by B. P. risein ethylene dichloride), contains 1.0% nitrogen, and gives a characteristic brick-red color in concentrated sulfuric acid.

Example 2 110 parts of anhydrous hydrofluoric acid, 23 parts of Bz-1,1'-dibenzanthronyl and 40.7 parts of isopropyl ether are charged into a nickel autoclave. It is sealed and heated to and held at that temperature four hours. It is then cooled to 0 C. and poured into 1000 parts of cold water. It is then filtered and the filter cake washed until free of acid. The black aggregate is dried and extracted with 150 parts of ligroin." The insoluble portion weighs 23 parts. Benzene solutions of this material are red by transmitted light and show a strong dark green fluorescence by reflected light. A separation of this insoluble portion intofractions may be affected as follows:

The insoluble product is thoroughly extracted with benzene, yielding 15 parts of the benzene insoluble material which shows a blue color in concentrated sulfuric acid. It has a melting point above 400 C. and does not vat in alkaline hydrosulfite.

On evaporation of the benzene extract, 7 parts of a second fraction are recovered. This material melts at C., shows a golden-brown color in concentrated sulfuric acid and a strong dark green fluorescence in hydrocarbon solvents.

Example 3 There are charged into a steel autoclave. cooled below room temperature, 116 parts of concentrated hydrofluoric acid, 23 parts dibenzanthrone, and 30.5 parts commercial isopropyl ether. The temperature is raised to 150 C. and the heating continued for four hours. It is then cooled and discharged onto approximately 1000 parts of ice and water. The suspension is filtered, washed to remove excess hydrofluoric acid and dried. The crude product is separated into two fractions by extracting with 350 parts of boiling benzene in two aliquot portions, 20.3 parts of benzene insoluble product which does not vat in alkaline hydrosulfite are isolated. By evaporating the benzene extract and triturating the residual tar with 150 parts of petroleum ether, 6.1 parts of a golden-brown powder are obtained. This fraction dissolves in benzene with a yellow color showing a strong, bright green fluorescence, and melts at 148-151 C.

Example 4 105 parts of anhydrous, liquid, hydrofluoric a c i d, 15 parts chlorinated dibenzanthrone (25.67% chlorine) and 30.5 parts commercial isopropyl ether are charged into a nickel autoclave. The condensation is run, and the product isolated essentially as described in Example 3. 9.7

parts of black, benzene insoluble material are iso lated which dissolves in concentrated sulfuricacid with a deep, greenish-blue color, does not vat in alkaline hydrosulflte, and contains 9.61% chlo- Example There are charged into a nickel pressure vessel, 110 parts of chilled, liquid, anhydrous hydrofiuoric acid, 10.6 parts of Bz-2-nitro-Bz-3-chloro-dibenzanthrone, and 10.2 parts of isopropyl ether. The condensation and isolation of the product are carried out essentially as described in Example 3. The product is obtained as a dark brown powder containing 3.77% chlorine, 2.73% total nitrogen and 2.67% amino nitrogen. It dissolves in sulfuric acid with a blue-green color, and gives an orange-red solution which is fluorescent in a dark-red shade in hot ortho dichlorbenzene.

Example 6 A steel autoclave equipped for agitation is charged with 114 parts of anhydrous hydrofluoric acid, 14.1 parts Bz-2-amino-dibenzanthrone, and 20.4 parts of isopropyl ether. The condensation is run for four hours at 150 C. and then the product is recovered as described in Example 3. A black powder is obtained and is separated into a benzene insoluble, and a benzene soluble fraction. 14.4 parts of product that is not soluble in benzene are obtained. It is not soluble in alkaline hydrosulfite, but dissolves in concentrated sulfuric acid with a bright blue-green color. 18 parts of a brown powder which melts at 298302, gives a dark green color in concentrated sulfuric acid, shows a dark-red fluorescence in benzene solution and contains 1.06% nitrogen are recovered from the benzene extract on evaporation.

Example 7 A chilled mixture of 113 parts of commercial anhydrous hydrofluoric acid, 8.7 parts 3,4-dimethyl meso-benzdianthrone and 12.35 parts isopropyl ether is poured into a nickel autoclave and run at 150 C. for four hours. The product is recovered form the reaction essentially as described in Example 3, or the excess hydrofluoric acid allowed to evaporate off. Purification by benzene extraction yields 2.5 parts of insoluble material. Evaporation of the benzene extract gives 8.0 parts of a benzene soluble product which has a melting point of 283 C. It gives a yellowish-brown color in concentrated sulfuric acid, does not yield a vat in alkaline hydrosulfite, and imparts to white petroleum oil an olive-green fluorescence.

Example 8 A mixture of 110 parts of nearly anhydrous hydrofluoric acid, parts of pyranthrone and 30.5 parts of reagent grade isopropyl ether is heated in a steel autoclave at 150 C. for four hours. The product is recovered in a manner similar to the process described in Example 3. 3.9 parts of this material are insoluble in benzene, and 8.7 parts of a fraction, melting at 183-195 C. and showing a bright, blue-green fluorescence in white petroleum oil, is soluble in benzene.

Example .9

A mixture of 5 parts of Bz-2-Bz-2'-dimethoxy dlbenzanthrone, 130 parts anhydrous hydrofluoric acid, and 20 parts of isopropyl alcohol is agitated in a steel autoclave at 30-6" C. for 26 hours. The reaction mixture is drowned in cold water, filtered and washed acid free with hot water. The wet cake is boiled out with dilute sodium hydroxide, filtered, washed and dried at 120 C. The product is somewhat soluble in hydrocarbon solvents in which it exhibits a green fluorescence.

Example 10 A high pressure type autoclave is charged with 110 parts of nearly anhydrous hydrofluoric acid, 14.6 parts of Bz-2,Bz-2-dimethoxy dibenzanthrone, and 20.3 parts commercial isopropyl ether. It is then sealed and heated for four hours at 125 C. After cooling the charge it is diluted with 1000 parts of ice and water, filtered and the filter cake washed with water until free of acid, and dried at C. The crude product is digested in 500 parts of boiling acetic acid, filtered hot and the filtrates chilled. A black crystalline product showing a reddish-blue color in concentrated sulfuric acid is obtained. The mother liquors are diluted with an equal volume of water and filtered. The residual tar is triturated with petroleum ether. A red-brown powder which dissolves readily in benzene to give a yellow solution possessing a strong, bright, yellow-green fluorescence and gives a blue-green color in sulfuric acid is isolated.

The product which does not dissolve in the hot acetic acid extraction is agitated with 510 parts of 96% sulfuric acid. The insoluble residue is filtered off and on slowly reducing the sulfuric acid concentration to 80% by diluting with water a product crystallizes out. This is filtered off, washed acid free and dried. This product when recrystallized from ortho-dichloro-benzene gives a. product which dyes cotton from a reddish-blue vat in. much bluer shades than the original Bz-2,Bz-2'-dimethoxy dibenzanthrone.

Example 11 Charge into a higher pressure autoclave equipped with agitation, 118 parts of nearly anhydrous hydrofiuoric acid, 13 parts of Bz-2,2'-dimethoxy dibenzanthrone, and 30.5 parts of isopropyl ether. The operation of the condensation and isolation of the product is carried out essentially as described in Example 3. 21.5 parts Example 12 parts of chilled anhydrous hydrofluoric acid, 26 parts of "stabilized leuco Bz-2,2-dimethoxy dibenzanthrone of U. S. P. 2,148,042 and 20.3 parts of isopropyl ether are charged into a nickel autoclave. The condensation is run at C. for four hours and the charge then worked up as described in Example 3. On benzene extraction of the crdude product a mate- .in methanol synthesis, etc.

rial is obtained which after recrystallization possesses properties similar to these described for Example 13 A mixture of 100 parts 01' commercial anhydrous hydrofluoric acid. 14.6 parts Bz-2,Bz-2'- dimethoxy dibenzanthrone, 42 parts of isopropyi ether, and 10 parts sodium meta-nitrobenzene sulionateis heated at 150 C. for four hours. The chargeis handled advantageously by following the procedure outlined in Example 3. 39 parts of crude material are obtained which on benzene extraction yields 7.76 parts insoluble material and 27.1 parts soluble fraction which is similar to that obtained in Examples 11 and 12. When the condensation is carried out at 130 C. or 170 C. there is substantially no variation in the character of the products obtained. The metallic composition of the autoclave likewise produces practically no variations. Copper, nickel and steels of various compositions produce substantially identical results.

The benzene insoluble fractions print cottonin dark grey shades which show good afllnity for the fiber. Oxidation produces olive-green prints which show good aflinity.

A variety of alkyl ethers may be condensed with isocyclic oxo-ring systems. For instance, diethyl ether may be condensed with Bz-2,Bz-2'-dimethoxy dibenzanthrone in concentrated hydrofluoric acid at 150 0., yielding a benzene soluble fraction which shows the characteristic yellowgreen fluorescence in hydrocarbon solutions, and a green color in concentrated sulfuric acid, and an insoluble fraction which dyes cotton from a reddish-blue vat in shades much bluer than Bz-2,Bz-2'-dimethoxy dibenzanthrone.

Example 14 110 parts of nearly anhydrous hydrofluoric acid, 11.8 parts Bz-2,Bz-2-dimethoxy dibenzanthrone, and 42.3 parts of iso-amyl alcohol are charged into a chilled autoclave which is then sealed and heated to 150 C., and held at that temperature for four hours. The product may be recovered by evaporating off the hydrofluoric acid and extracting the residue with benzene, or it may be recovered by'the procedure described in Example 3. A crude product is obtained which upon extracting with benzene-gives 6.2 parts of benzene insoluble material and 14.3 parts of benzene soluble product which exhibits a characteristicyellow fluorescence in hydrocarbons and a green color in concentrated sulfuric acid.

This condensation is applicable to a great variety of aliphatic,cyclo-aliphatic and aromatic alcohols; straight chain aliphatic alcohols from the reduction of natural fats and waxes, branched chain aliphatic alcohols obtained as by-products Benzyl alcohol and benzyl ether undergo condensation to yield similar products. Amyl mercaptan undergoes condensation with Bz-2,Bz-2'-dimethoxy-dibenzanthrone to give sulfur containing products.

Example 15 A steel autoclave is chilled and charged with 114 parts of commercial anhydrous hydrofluoric acid, 26 parts Bz-2,Bz-2'-dimethoxy dibenzanthrone and 43.4 parts n-butyraldehyde. The reaction and isolation of the product is carried out essentially as described in Example 3. A product is obtained which is separated into 4.3 parts of benzene insoluble material and 35 parts of benzene soluble product, which soluble product shows-a characteristic bright yellow-green fluorescence in hydrocarbons and a green color in concentrated sulfuric acid.

Isobutyraldehyde produces substantially identical results. Obviously other aldehydes such as heptaidehyde, eenanthic aldehyde. etc., may be used. A wide variety of aliphatic ketones may be reacted in the same manner. Acetone yields" approximately equal proportions of solvent solu ble and insoluble fractions. denses readily, and the benzene insoluble traction dyes cotton from a blue vat in shades which are extremely bluer than the dimethoxy dibenzanthrone started with. Hydroxy aldehydes such as sucrose give condensation products which show a yellow-green fluorescence in pyridine.

Example 16 113 parts of liquid. anhydrous hydrofluoric acid, 7.28. parts of Bz-2.Bz-2'-dimethoxy dibenzanthrone, and 29 parts of stearic acid (U. S. P.

Example 17 A mixture of 114 parts of commercial anhydrous hydrofluoric acid, 6.5 parts of Bz-2,Bz-2- dimethoxy dibenzanthrone, and 22 parts of dimethyl stearylamine upon heating to 150 C. under pressure for four hours as described in Example 3 yields 1.37 parts of a solvent insoluble product and 4.0 parts of a solvent soluble product.

Example 18 An autoclave is chilled and charged with parts of liquid, anhydrous hydrofluoric acid, 7.28 parts of Bz-2,Bz-2-dimethoxy dibenzanthrone, and 28.6 parts of amyl chloride. After sealing it is heated at C. for four hours. action mass is chilled and the hydrochloric acid pressure is carefully released. The residual hydrofluoric acid is evaporated oil or the reaction mixture is diluted with water, and the products isolated as described in Example 3. 5.9 parts oi. a benzene insoluble fraction which may be dissolved in pyridine, and 5.4 parts of benzene soluble material which contains only a trace of chlorine are separated from the crude condensation product.

The condensation is not limited to amyl chloride, but may be applied to a variety of alkyl and aralkyl chlorides, bromides and iodides. The reaction may be carried out with the inorganic esters of the aliphatic compounds such as sulfates, borates, silicates, phosphates, etc. For example, 29 parts of sodium dodecyl sulfate may be condensed with 7.28 parts of Bz-2,Bz-.2'-dimethoxy dibenzanthrone, to give a mixture of products of varying solubilities in hydrocarbon Benzaldehyde con- The resolvents. Trilauryl borate likewise produces a high yield of solvent soluble products.

Example 19 110 parts of nearly anhydrous hydrofluoric acid, 13 parts of Bz-2,Bz'-2'-dimethoxy dibenzanthrone and 20.8 parts of n-heptane, are reacted and the products isolated as described in Example 3. A product is obtained which yields 4.2 parts of benzene insoluble and 8.0 parts of benzene soluble product.

Other parafiins or mixtures of paraflins from ethane to the high molecular weight waxes as well as the oleflns may be employed in this reaction. For example, 7.28 parts of Bz-2,Bz-2' dimethoxy dibenzanthrone condenses with 24.3 parts deisobutylene, yielding 10.3 parts of benzene soluble product.

Alkyl substituted aromatic compounds are likewise capable of undergoing condensations with the aromatic keto compounds. For example, 22.1

parts of amyi benzene condenses with 7.28 parts of Bz-2,Bz-2-dimethoxy dibenzanthrone in 116 parts of anhydrous hydrofluoric acid at 150 C., to give, by the process of Example 3, 15.1 parts of a benzene soluble product which shows a molecular weight of 634 by boiling point rise in ethylene dichloride and 4.8 parts of a benzene insoluble product which dyes cotton in khaki shades from a dark red vat.

Example 20 Q 110 parts of commercial anhydrous hydroi'luoric acid, 15 parts dihydroxy dibenzanthrone methylene ether (prepared by the alkylation of furic acid and which dyes cotton in olive shades from a reddish-blue vat remains after extracting with benzene. 2.5 parts of benzene soluble material, melting at 185-212 are also obtained.

Example 21 140 parts of nearly anhydrous hydrofluoric acid, 39 parts of Bz-2,Bz-2'-dihydroxy dibenzanthrone, and 40.7 parts of isopropyl ether are heated in an autoclave at 150 C. for four hours, then cooled to room temperataure or below and diluted with 1000 parts ice and water. The resuiting product is filtered off, washed thoroughly and dried. A dark red powder is obtained which on extraction with benzene as described in Example 3 yields 37.9 parts of an insoluble fraction which dissolves in sulfuric acid with a brilliant green color and dyes cotton in olive green shades from a blue vat, and 8.1 parts of a benzene soluble fraction which imparts a characteristic yellow-green fluorescence to hydrocarbon solutions are obtained.

As an alternative method of purification, the following process may be employed. Dissolve parts of the crude reaction product in 380 parts of 96% sulfuric acid at 5-10 C. Agitate for 17 hours at room temperature; then run the solution into 1000 parts of ice. Filter, wash acid free and dry. Extract the dry material thoroughly with xylene. A black powder is obtained which dissolves in sulfuric acid with a blue color and which dyes in olive green shades from a blue vat.

3 parts of. a soluble product may be crystallized from the xylene extract which ha properties similar to the insoluble fraction, and in addition dissolves in orthodichlorbenzene to give dark green color.

Similar products are obtained when iso-amyl alcohol, isobutyraldehyde, methyl ethyl ketone, ethyl acetylene, etc., are employed. The stabilized leuco derivative of Bz-2,Bz-2'-dihydroxy dibenzanthrone (see U. 8. Appl. 209,990) may be employed in the same manner,

Example 22 109 parts of chilled, liquid anhydrous hydrofluoric acid, 26 parts of Bz-2,Bz-2'-dioxodibenzanthrone, and 20.5 parts of commercial isopropyl ether are heated in an autoclave at C. for four hours. After cooling the contents are discharged into a mixture of ice and. water. The products may be best recovered'and purifled by the process described in Example 3, The crude product is separated into 25.2 parts of solvent insoiubleproduct which dyes cotton in olive green shades from a bluish-red vat, and 5.2 parts of a benzene soluble fraction, which melts at 236-243 and dissolves in hydrocarbons with a red color and exhibiting a strong yellow-green fluorescence. q

In the above examples the chilling of the apparatus and the hydrofluoric acid at the time of charging the apparatus is done. as a safety measure only because of the high vapor pressure of the hydrofluoric acid at .ordinary temperatures, and thisstep is not an essential condition of the reaction.

Because anhydrous hydrofluoric acid is an excellent solvent for the high molecular weight carbocyclic ketones the condensation reaction involing these ketones proceeds smoothly, and since the hydrofluoric acid is remark-ably stable throughout the reaction range a minimum of undesirable decomposltion products are formed.

In general these new solvent soluble compounds exhibit fluorescence when acted upon by ultra violet light, as well as when acted upon by ordinary visible light and may therefore be used to produce color effects with invisible light.

/ As pointed out above the oil soluble fractions of the products produced with hydrofluoric acid exhibit desirable fluorescence in the oils making these products particularly suitable for coloring lubricating oils where a fluorescence is desirable. They may be employed with other dyes and the usual antioxidants, pourpoint depressants, viscosity index improvers, extreme pressure lubricant bases, sludge dispersing agents, inhibitors, etc., which may be employed in the preparation of commercial hydrocarbon oils, Similarly they may be employed in coloring gasoiines and other hydrocarbon fractions in conjunction with ignition control agents or other fuel modifiers.

These solvent soluble compounds may also be used for coloring resins, plastics, lacquers, cellulose acetate, regenerated cellulose, etc., where solvent soluble colors may be employed, particularly in obtaining novel or artistic color eifects.

We claim:

1. The products obtained by the condensation of a high molecular weight carbocyclic ketone containing a condensed ring system comprising at least four benzene rings in which the keto carbon atom is part of a quinoid grouping, with an aliphatic compound of the class consisting of those of the oleflne and paraflin series containing at least two carbon atoms, said condenaction being carried out in hydrofluoric acid of at least 36% concentration, said products being solids and readily soluble in cold concentrated sulfuric acid.

2. The products obtained by the condensation of a dibenzanthrone compound with an aliphatic compound of the class consisting of those of the olefine and parafiin series containing at least two carbon atoms, said reaction being carried out in hydrofluoric acid of at least 36% concentration, said products being solids and readily solube in cold concentrated sulfuric acid.

3. The products obtained by the condensation of Bz-2,Bz-2-dimethoxy-dibenzanthrone with an aliphatic compound of the class consisting of those of the olefine' and paraflln series containing at least two carbon atoms, said condensation being carried out in hydrofluoric acid of at least 36% concentration, said products being solids and readily soluble in cold concentrated sulfuric acid.

4. The products obtained by the condensation of a dibenzanthrone compound with an aliphatic compound containing at least three carbon atoms, said compound being of the class consisting of those of the olefine and parafiin series, the said condensation being carried out in hydrofluoric acid of at least 36% concentration, said products being solids and readily soluble in cold concentrated sulfuric acid.

5. The hydrocarbon oil soluble compounds obtained by the condensation of a high molecular weight carbocyclic ketone containing a condensed ring system comprising at least four benzene rings in which the keto carbon atom is part of a quinoid grouping, with an aliphatic compound of the class consisting of those of the olefine and paraffin series, said reaction being carried out in hydrofluoric acid of at least 36% concentration, said oil soluble compounds containing in the molecule at least 6 aliphatic carbon atoms comprising at least one aliphatic chain containing at least two carbon atoms, and being solids and readily soluble in cold concentrated sulfuric acid.

6. The hydrocarbon oil soluble compounds obtained by the condensation of a high molecular weight carbocyclic ketone containing a condensed ring system comprising at least 4 benzene rings in which the keto carbon atom is part of a quinoid grouping, with an aliphatic compound of the class consisting of those of the oleflne and paraflin series, said condensation being carried out in hydrofluoric acid oi at least 36% concentration, and said oil soluble compounds containing at least two aliphatic side chains, each of which contains at least three carbon atoms, and being solids and readily soluble in cold concentrated sulfuric acid.

7. The hydrocarbon oil soluble compounds obtained by the condensation of a dibenzanthrone compound with an aliphatic compound containing at least 6 carbon atoms, said condensation being carried out in hydrofluoric acid of at least concentration, said products being solids at normal atmospheric temperatures and readilr soluble in cold concentrated sulfuric acid.

8. The hydrocarbon oil soluble compounds obtained by the condensation of a dibenzanthrone compound with an aliphatic compound containing at least 5 carbon atoms in an aliphatic chain. said condensation being carried out in 'hydrofluoric acid of at least 50% concentration, said products being solids at normal atmospheric temperatures and readily soluble in cold concentrated. sulfuric acid.

9. The hydrocarbon oil soluble compounds obtained by the condensation of Bz-2,Bz-2-dlmethoxydibenzanthrone with an aliphatic compound containing at least 5 carbons in an allphatic chain, said condensation being carried out in hydrofluoric acid of at least 50% concentration, said oil soluble compounds being solids at normal atmospheric temperatures and dissolving in hydrocarbon oils to give characteristic yellow fluorescence and being readily soluble in cold concentrated sulfuric acid with a green color.

ADRIAN LAVERNE LINCH. VIKTOR WEINMAYR.