US3666827A - Quaternary substituted hydrocarbons - Google Patents

Abstract

High molecular weight hydrocarbons containing from about 28 to 40 carbon atoms and from two to four gem-dimethyl units interspersed in an aliphatic chain are useful as lubricants and other functional fluids and have a wide liquid range, good thermal stability and resistance to the formation of sludge and other insoluble decomposition products due to oxidation at elevated temperatures.

Description

United States Patent Carlson et al.

[ 1 May 30, 1972 [54] QUATERNARY SUBSTITUTED HYDROCARBONS [72] Inventors: Emil H. Carlson, Kirkwood; William C. Hammann, Creve Coeur; Robert M. Schisla, Kirkwood, all of Mo.

[73] Assignee: Monsanto Company, St. Louis, Mo.

[22] Filed: Nov. 14, 1969 [21] Appl. No.: 877,043

{52] U.S. Cl ..260/676 [51] Int. Cl .C07c 9/00 [58] Field of Search ..260/676 [56] References Cited UNITED STATES PATENTS 3,576,898 4/1971 Blake et a1. ..260/676 OTHER PUBLICATIONS A Free Radical Method of Synthesis of Hydrocarbons with Quaternary Carbon Atoms in the Molecules, Chemical Abstracts, Vol. 64, 1966, p. 15774h., A. P. Meshcher, Yakov and E l. Erzyutova 260/677 Primary Examiner-Delbert E. Gantz Assistant Examiner-J. M. Nelson AttorneyNeal E. Willis, J. E. Maurer and Wayne R. Eberhardt [5 7] ABSTRACT High molecular weight hydrocarbons containing from about 28 to 40 carbon atoms and from two to four gem-dimethyl units interspersed in an aliphatic chain are useful as lubricants and other functional fluids and have a wide liquid range, good thermal stability and resistance to the formation of sludge and other insoluble decomposition products due to oxidation at elevated temperatures.

11 Claims, No Drawings QUATERNARY SUBS'IITU'IED HYDROCARBONS BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to saturated aliphatic hydrocarbon compounds interspersed with quaternary carbon atoms, and to functional fluids comprising these compounds.

2. Description of Prior Art The continuing development and improvement of high performance aircraft engines has created a continual demand for improved lubricants which are efficient over a wide range of operating temperatures and which are resistance to oxidation and thermal degradation. Jet aircraft engines in particular are found to operate with greater efficiency at high temperatures, and consequently the emphasis for jet engine lubricants has been on the development of improved high temperature properties. A

Aliphatic compounds have generally been considered as unsuitable for high temperature applications due to their tendency to oxidize and form insoluble, non-volatile gums and sludges as oxidation products.

Many ways have been proposed to improve the oxidation stability of aliphatic lubricants. Generally some improvement is obtained by merely incorporating known antioxidants into the lubricant composition. This technique extends the useful service life of the lubricant but the improvement is generally not sufficient to qualify these stabilized lubricants for extended service at elevated temperatures.

Rather than add stabilizers to the lubricant, a better ap proach is to modify the structure of the aliphatic compound so that thermal stability and oxidation resistance are inherent in the composition. Alternatively, if the oxidation rate is not reduced, a method to minimize the formation of sludges and gums produced by the oxidation would represent a major advance in the state of the art for this class of lubricants.

Accordingly, it is an object of the present invention to modify the structure of high molecular weight aliphatic compounds in order to minimize the effects of high temperature oxidation. Another object of this invention is to provide high molecular weight hydrocarbon structures which have not heretofore been known and which are therefore new compositions of matter. It is a further object of this invention to provide a novel branched aliphatic structure which is suitable for use as a lubricant at elevated temperatures and which does not fonn undesirable sludge and gum upon oxidation.

The compounds of this invention are unique structures distinguished from known prior art in that they contain from two to four gem-dimethyl units and a total of from about 28 to 40 carbon atoms. Compounds of this structure have not, to the best of Applicants knowledge, previously been prepared in substantially pure form nor have their unusual and desirable properties been recognized heretofore. Of approximately 150 hydrocarbons with quaternary carbon atoms reported in the prior art and in Handbook of Hydrocarbons, by S. W. Ferris, I955), no structures were found which had two or more gemdimethyl groups and a total of more than 28 carbon atoms. In fact only eight compounds were found to have more than 28 carbon atoms and none of these had more than one quatemary carbon. Only 16 structures were found to have two or more quaternary carbons and these had from 18 to 24 carbon atoms in the total structure.

Of the prior art compounds which bear a structural resemblance to the compounds of this invention, none were found to possess the physical properties required for functional fluid applications. The compound 3,3,6,6,9,9,l2,l2-octamethyl tetradecane, an example of the prior art most structurally similar to the compounds of this invention, is a solid at room temperature and is reported in the Handbook of Hydrocarbons to have a boiling point of about 320 C.

SUMMARY As a new composition of matter, the high molecular weight branched aliphatic hydrocarbons of this invention are those containing from about 28 to 40 carbon atoms and from two to four gem-dimethyl units interspersed in the aliphatic chain with from about four to eight carbon atoms between said units. These compounds correspond tothe following structure.

L is DESCRIPTION OF PREFERRED EMBODIMENTS The compounds of this invention are high molecular weight branched aliphatic hydrocarbons containing from two to about four gem-dimethyl quaternary carbon groups interspersed in the aliphatic chain with from about four to eight methylene groups between the quaternary carbon groups, the compounds having a total of at least about 28 carbon atoms and preferably from about 28 to 40 carbon atoms. Particularly preferred are the octamethyl alkanes having a total of 34 to 38 carbon atoms, and having four or five methylene groups separating the quaternary carbon groups.

In accordance with known chemical structural effects, aliphatic compounds containing quaternary carbons interspersed in the structure were expected to have improved oxidation stability over their linear analogs because of greater shielding of the methylene groups to radical attack by the gem-dimethyl groups, and because of an increase in the CH ICI-I ratio, the methyl groups being more oxidation resistant than the methylene groups. It was most surprising and unexpected, therefore, that oxidation tests indicated that in some instances the addition of quaternary carbon groups had an opposite afiect and actually increased the rate of oxidation of the aliphatic structures. It was also surprising and unexpected that even where the rate of oxidation was higher for the branched compounds of this invention, the products of oxidation did not form gums or sludges and the fluid remained clean. It was further discovered that many of the products of oxidation were sufi'iciently volatile to be swept from the fluid during use at elevated temperatures. The significance of these discoveries lay in the fact that the compounds of this invention could be employed as functional fluids at elevated temperatures with no disadvantage beyond consumption of the fluid due to oxidation. Whereas the linear analogs of the compounds of this invention quickly became dirty and thick with sludge, the quaternary carbon compounds of this invention remained fluid and clean.

The compositions of this invention are accordingly particularly well suited for use as functional fluids under conditions conducive to the oxidation of the fluid. Specifically, the fluids are well suited for use as lubricants and hydraulic fluids in an oxidizing environment such as exists when the fluids are exposed to air at elevated temperatures above about 400 F.

Some specific examples of the compounds encompassed by this invention are presented in the table below for purposes of illustration only, and the scope of the invention is not intended to be limited thereby.

TABLE I [Quaternary Carbon Compounds, Compositions and Physical Properties] Vapor pressure, F.

at mm. Hg T Compound Formula B.P., C./mm. 11.1 d 100 600 760 O F,

(a) 6,6,12,12,18,18-hexamethyltricosane Cz Hw 1ss/o.o2 1.4568 (b) 9,9,18,IB-tetraanethylhexacosane CsoHuz 180/0. 03 1.4528 0.8149 512 631 748 766 621 (c) 6,6,I1,ll,16,l6,21,21-octamethylhexaeosane CsiHvo 190l94/0.02 1.4570 0.8278 539 634 723 736 505 (d) 6,6,11.11,17,17,22,22-octamethylheptacosane C35H 1s9-194 0.03 1.4568 0.8230 537 644 742 757 610 (e) 6,6, ,11,18,18,23,23-0ctamethyloctacosane CaeHn 195-20010. 02 1.4575 0.8226 564 644 710 726 608 (l) 6,6 2,12,18,18,24,24-octamethylnonacosane C37H7a ()205/0.04 1.4587 554; 667 779 793 613 (g) 6,6,11,11,20,20,25,25-oct0methyltriacontane CasHn 1 15/0.02 -4580 0.8 51 573 647 712 721 612 (h) 6,6,12,12,21,21,27,27-octarnethyldotriacontane C uHe2 220225/0.03 1.4600 (i) Octacosane CasHsa 52% 032 7312 HS 66; (j) Pentatriacontane CssHrz X 590 701 809 824 (592 (k) l1,12 dioctyl-11-Inethyltricosane CmHsz 584 662 730 739 612 1 Property was not determined. B.P. is the boiling point at the given pressure. 725 is the refractive index eggs? C. 7 v

In the above table the thermal decomposition temperature and vapor pressure were' determined according to the procedure of Blake et aL, J. Chem. Eng. Data, 6, 87 (196i). In this procedure, the thermal stability is defined as the temperature at which the decomposition of the test material produced a pressure rise of 0.0 14 mm. Hg./sec.

Compounds (i), (j) and (k) are included in Table I as controls representative of normal and branched high molecular weight straight chain aliphatics of the prior art for comparison with the new compounds of this invention.

It is apparent from the data in Table I that the incorporation of gem-dimethyl units into an aliphatic compound generally decreases the thermal decomposition temperature and increases the vapor pressure of the compound. This is best seen by a comparison of the C compound ((1) and its linear analog compound (j). However, in spite of this effect, the physical properties of the new compounds of this invention are within a range generally suitable for high performance lubricants intended for service at temperatures in excess of 400 F.

Oxidation Tests The C i-L, compound (f) of the preceding table was selected as representative of the compounds of this invention and subjected to a severe oxidation test according to a circulatory oxidation test procedure as follows:

Ten milliliters of test fluid is charged to an oxidation chamber constructed of a glass tube of about 17 mm. 1. D. by 17% inches long. A glass agitator consisting of a hollow shaft and a slotted disc impeller extends to the bottom of the oxidation chamber and is driven by a reciprocating motor. The temperature of the test fluid during oxidation is controlled by immersing the lower part of the oxidation chamber in a constant temperature bath containing a silicon or other high temperature heat transfer fluid.

The agitator is designed to convey oxygen through the shaft down into the test fluid where it is dispersed into fine bubbles by the action of the slotted disc impeller.

Oxygen for the test is generated by an electrolytic cell at a rate sufficient to maintain a constant gas pressure in the oxidation chamber of approximately k to 1 inch water above atmospheric. Unused oxygen is collected and recirculated so that ultimately all the oxygen produced over a given period of time is consumed in the fluid. The amount of oxygen generated and consumed is determined by measuring the current flow to the electrolytic cell. The oxidative stability of the test fluid is proportional to the amount of oxygen consumed.

The circulatory oxidation test has been shown to provide accurate results and reproducibility of greater than 97 percent on small samples of test fluids. The C l-I compound described above was compared with n-C l-i straight-chain aliphatic, and with a O l-I branched compound (compounds (i) and (k) of Table I) which were selected as control compositions representative of the prior art. These materials were subjected to oxidation at 450 F. for a period of minutes,

0 with the results as given in Table II.

TABLE II OXIDATION TEST AT 45 0 F.

Power Equivalent Consumption g.O,/g. Appearance of Compound mfJmin. Fluid Oxidized Fluid C H 288/40 0.46 Lt. Yellow-Fluid H 32l/40 0.51 Dk. Solid n-C l-l 307/40 0.49 Dk. Viscous Fluid It is apparent from the above data that the C H- test fluid of this invention was slightly superior to the two control fluids in resistance to oxidation. More important, however, is the appearance of the sample after oxidation. Whereas the C ll aliphatic material became a dark viscous fluid, and the C H material became a dark solid, the C H- composition of this invention remained a light yellow and of a fluid viscosity. This indicates that while the two control fluids would no longer be useful as lubricants after exposure to this degree of oxidation, the fluid of this invention could still remain in service.

Lubrication Test The C i-I compound (g) of Table I above was selected as representative of the quaternary carbon compounds of this invention for a lubrication test wherein a standard 51-100 steel ball bearing was rotated on three flat, stationary discs of M-52 steel at 620 rpm. and 167 F. for one hour at 10 kg. applied load. The C 11 compound (k) described in the oxidation test above was known to be a good lubricant and was 'used as a control for this lubrication test. The lubricating ability of each test fluid was determined by measuring the average wear scar diameters on the ball after completion of the test. The results of the test were as follows:

C i-I test fluid, 0.40 mm. scar diameter C I-l control fluid, 0.48 mm. scar diameter The above data illustrate that the test fluid of this invention appears to have improved antiwear properties, an important property in lubricating compositions.

Mechanism of Oxidation The C i-I compound (d)' of 'Table I above was compared to its linear analog n-pentatriacontane, compound (j) of Table graphs of the oxidized and unoxidized material showed an increase in the amounts of the lower molecular weight components present in the eluate from the column. The fact that the initial oxidation products were detected on the vapor chromatograph testifies to the stability and volatility of these products. In comparison, the products of the initial oxidation of the n-C control fluid underwent rapid further oxidation and could not be detected on the vapor chromatograph. The stability of the oxidization products produced by the compositions of this invention is believed to contribute to the cleanliness of the oxidized fluid, and its resistance to the formation of the gums and sludges usually associated with the oxidation of aliphatics.

The preceding descriptions and test data are provided to illustrate the properties of the fluids encompassed by this invention, and to demonstrate their adaptability for use as lubricating compositions. Although the examples and data presented herein are for essentially pure quaternary substituted hydrocarbons, it is appreciated that these compounds may be used as mixtures in functional fluid applications, and such mixtures are considered to be within the scope of the present invention.

It is also considered to be within the scope of this invention to incorporate known additives with quaternary substituted hydrocarbons in order to improve specific properties for functional fluid applications. Included are for example load hearing additives, V.l. improvers, antioxidants, and anticorrosion agents. Specific additives useful for the desired result are Well known in the functional fluid art.

The following section describes one method whereby the novel fluids of this invention may be prepared, although the invention is not to be limited to any particular method of preparation. In the following discussion, the preparation of the intermediate chemical compositions is included for the information and edification of those who may wish to follow this as a suggested procedure. Where a standard published procedure was used to prepare a particular compound a reference to the procedure is substituted for a detailed description thereof. Preparation of the following specific compositions as typical examples of the compounds of this invention are included herein:

C I-l 6,6,12,12,18,1S-hexarnethyltriacosane C l-I 9,9,1 8,1 8-tetramethylhexacosane C 11 6,6,1 1,1 1,17,17,22,22-octamethylheptacosane C H 6,6,12,l2,18,l8,24,24-octamethylnonacosane C H 6,6,1 2,12,21,21,27,27-octarnethyldotriacontane PREPARATION OF COMPOUNDS Ethyl Isopropylidene Malonate (I). This ester was prepared by the procedure listed by Cope and Hancock, J. Am. Chem. Soc., 60, 2644 (1938).

Ethyl 1, l-Dimethylhexyl Malonate (II). A Grignard solution was prepared from l-bromopentane (151 g., 1 mole), magnesium tumings (24.3 g., l-gr-atom) and 1,200 ml. of absolute ether. The reagent was added to ethyl isopropylidene malonate (200 g., 1 mole) dissolved in 1,200 ml. of absolute ether containing cuprous iodide (5 g./mole of ester) over a 2 hour period with stirring. The reactants were stirred for 16 hours and heated for 1 hour at mild reflux. The addition product was decomposed with ice and dilute hydrochloric acid, the aqueous layer separated and washed several times with ether. The combined ether solutions were dried with anhydrous magnesium sulfate, concentrated on a steam bath and distilled to obtain the desired product, b.p. l28l32 (3.0 mm.), n 1.4359.

Anal. Calcd. for C l-1 0,: C, 66.6; H, 9.69. Found: C, 65.7; H, 10.16.

3,3-Dimethyloctanoic Acid (III). Ethyl 1,1-dimethylhexyl malonate (272 g., 1 mole) was added dropwise to a hot solution of potassium hydroxide (200 g., 3.5 moles) dissolved in 200 ml. of water over a period of 2 hours. The reactants were refluxed with stirring for 3 hours at 93, cooled, diluted with 200 ml. of water, and heated to collect 200 ml. of distillate which was mainly ethanol. Cold sulfuric acid 175 ml. of cone. H2SO /450 ml. of Water) was cautiously added to the saponified ester (4550), refluxed for 4 hours after acidification and cooled. The aqueous layer was separated, washed with benzene several times, the benzene extracts combined with the organic layer and dried over anhydrous magnesium sulfate. The benzene solution was concentrated on a steam bath and distilled to obtain the desired product, b.p. 104 1.0 mm.), n 2, 1.4355.

Anal. Calcd. for C H O C, 69.7; H, 11.70. Found: C, 70.0; H, l 1.40.

3,3-Dimethyl-1-octanol (IV). An ethereal solution of 75g. of the acid (III) was added to a stirred suspension of 20.3 g. of lithium aluminum hydride in 1,200 ml. of ether at a rate sufficient to cause gentle refluxing. After the addition had been completed, the mixture was stirred at room temperature for 14 hours, and heated under reflux for an additional 5 hours. Excess lithium aluminum hydride was decomposed by dropwise addition of cold water at ice-bath temperatures and the reaction mixture hydrolyzed with 10 percent sulfuric acid. The ether layer was removed, washed with water, 10 percent sodium bicarbonate, again with water and dried over anhydrous magnesium sulfate. The ether solution was concentrated on a steam bath and the concentrate distilled to yield the product as a colorless liquid, b.p. 72 (0.7 mm.), n 1.4378.

Anal. Calcd. for C H O: C,75.9; H,14.01. Found: C,75.8; H, 13.91.

l-Bromo-3,3-dimethyloctane (V). A mixture of 48 percent hydrobromic acid (240 g., 1.4 moles), concentrated sulfuric acid (62 g., 0.34 mole), and 3,3-dimethyl-1-octanol (87 g., 0.55 mole) was refluxed for 5 hours at 125. The cooled solution was diluted with water, filtered and the bromide layer separated. The crude bromide was washed once with 10 ml. of cold sulfuric acid, ml. of water and finally 100 ml. of a 10% sodium carbonate solution. The light brown oil was dried over anhydrous magnesium sulfate and distilled to yield the desired product, b.p. 69 (0.25 mm.), n 1,4575.

Anal. Calcd. for C I-l Br: C, 54.3; H, 9.57; Br, 36.1. Found: C, 54.2; H, 9.66; Br, 36.1.

3,3,9,9-Tetramethyl-l,l l-undecandioic Acid (VI). A Grignard solution prepared from 1,5-dibromopentane (230 g., 1 mole) and magnesium turnings (48.6 g., 2 g-atoms) dissolved in 1,200 ml. of absolute ether was added to ethyl isoropylidene malonate (440 g., 2 moles) dissolved in 1,200 ml. of absolute ether containing 10 g. of cuprous iodide over a period of 1 hour. After the addition, the dark brown reaction mixture was stirred for 12 hours at reflux, cooled and hydrolyzed. After distilling off the low boiling reaction products, the crude ester in the distillation pot was saponified and decarboxylated in the same manner as that described for 3,3-dimethyloctanoic acid. (III) Crude 3,3,9,9-tetramethyl- 1,1l-undecandioic acid was obtained and recrystallized from hexane to give a white crystalline solid, mp. 96-97.

Anal. Calcd. for C I-1, 0 C, 66.1; H, 10.36. Found: C, 66.2; H, 10.23.

3 ,3 ,9,9-Tetramethyl-l l 'l -undecandioyl Chloride (VII).

3,3,9,9-Tetramethyl-l,1l-undecandioic acid (41 g., 0.15-

mole) was added as a solid to excess thionyl chloride (71.4 g.,

0.6 mole) over a period of 40 minutes with stirring. After the final addition, the mixture was refluxed for 1.5 hours at 55, excess thionyl chloride removed by mild heating under vacuum, and the acid chloride distilled, b.p. l50152 (0.2 mm.)

6,6,1 1,1 1 ,17,17,22,22-Octamethy1-9, l9-heptacosandione (VIII). This diketone was prepared using the basic procedure described by Cason and Prout, J. Am. Chem. Soc., 66, 47 (1944). A Grignard solution was prepared from 1- bromo-3,3-dimethylocatane (77.5 g., 0.35 mole) and magnesium tumings (9.7 g., 0.4 gr-atom) in 600 ml. of anhydrous ether. Anhydrous cadmium chloride (40 g.,0.22 mole), was added to the decanted Grignard solution in a dry-nitrogen atmosphere at ice-bath temperature, stirred for 20 minutes, and allowed to warm to room temperature. The organocadmium reagent was refluxed for 3 hours, excess ether removed, and 150 ml. of benzene added as a reaction solvent. 3,3,9,9- Tetramethyl-l,1l-undecandioyl chloride (27 g., 0.09 mole) dissolved in 50 ml. of benzene was added at 68 at a controlled rate since the reaction was exothermic. The mixture was refluxed for 2 hours, poured onto a 10 percent solution of sulfuric acid and extracted with ether. The ether solutions were washed with water, a 5 percent sodium carbonate solution, a saturated sodium solution and dried over magnesium sulfate. The reaction products were concentrated on a steam bath and distilled to yield the desired product, b.p. 210-215 (0.2 mm. n"-" 1.4630,

Anal. Calcd. for C .,H,,,,O,: Found:

Anal. Calcd. for'C ,1-1,,O C, 80.1; H, 13.82. Found: C, 80.2; H, 13.56.

6,6,11,11,17,17,22,22-Octamethy1-(8)9,l8(19)-heptacosadiene (X). 6,6,l1,1 1,17,17,22,22-Octamethyl-9,19- hextacosandiol (20.5 g., 0.04 mole) was heated with anhydrous potassium bisulfate (6 g., 0.044 mole) at 150160 for 6 hours at reduced pressures (3-5 mm.). The reaction product was allowed to cool, decanted, and the potassium bisulfate washed several times with small portions of ether. The oil and extracts were combined and the ether evaporated. The residue was distilled to obtain the desired product, b.p. 205210 (0.1 mm.) n 1.4662.

Anal. Calcd. for C H C, 86.0; H, 14.02; M01. St. 488. Found: C, 86.4; H, 13.79; Mol. wt. 477.

6,6,1 1,1 l,17,17,22,22-Octamethylheptacosane (XI). 6,6,1 1,1 1,17,17,22,220ctamethy1(8)9,18(19)-heptacosadiene (13.8 g., 0.028 mole), methylcyclohexane (75 ml.), and 1 g. of 5 percent rhodium-on-carbon catalyst were heated to 180 in a 300 ml. bomb and rocked for 8 hours at a final pressure of hydrogen and reactants of 3,200 psi. The cooled reaction mixture was filtered free of catalyst, concentrated in vacuo, and the concentrate distilled under vacuum to yield the desired product, b.p. 189194 (0.03 mm.), n 1.4568, (1 0.8230.

Anal.

, 85.28, H, 14.72;Mo1. wt. 493.

Found:

Ethyl 4,4-dimethylpelargonate (X11). This ester was prepared according to the procedure described by R. Gaertner, J. Am. Chem. Soc., 73, 3934 (1951). A Grignard reagent prepared from l-bromo-3,3-dimethyloctane (442 g., 2.0 moles), magnesium turnings (49.5 g., 2.0 gr-atoms) and 2 liters of anhydrous ether was added to ethyl chlorocarbonate (1,080 g., 10 moles) in 2 liters of ether at 40 over a 4 hour period. The reactants were allowed to warm to room temperature, washed with a solution of ammonium chloride and excess ether removed in vacuo with mild heating followed by a double distillation to yield the desired product, b.p. 108 1.2 mm.), n 1.4302.

Anal.

Calcd. for CHI-1,602: C, 72.8; H, 12.22.

Found: C, 72.4; H, 12.01.

4,4-Dimethy1-1-nonanol (X111). Addition of an ethereal solution of 198 g. (0.93 mole) of ethyl 4,4-dimethylpelargonate to a stirred suspension of 33 g. of lithium aluminum hydride in 1,200 ml. of ether, followed by the procedure described for Compound (1V) to yield the produce as a colorless liquid, b.p. 109 1.0 mm.), n 1.4400.

Anal. Calcd. for C I-1 ,0; C, 76.7; H, 14.04. Found: C, 76.7; H, 14.17.

l-Bromo-4,4-dimethylnonane (XIV). A mixture of 48% hydrobromic acid (384 g., 2.24 moles), concentrated sulfuric acid (98 g., 1 mole) and 4,4-dimethy1-l-nonanol (152 g., 0.88 mole) was treated according to the procedure previously described for compound (V) to yield the desired product, b.p. 94 1.0 mm. n 1.4578.

Anal. Calcd. for C H Brz C, 56.2; H, 9.85; Br, 34.0. Found: C, 56.0; H, 10.13; Br 34.0.

6,6,12,12,18,l8,24,24-Octamethyl-10,20-nonocosanedione (XV). This diketone was obtained by means of the typical organocadmium-acid chloride reaction previously described for Compound (V111). A Grignard solution was prepared from l-bromo-4,4-dimethylnonane (82 g., 0.35 mole) and magnesium turnings (9.7 g., 4.0 gr-atom) in 600 ml. of anhydrous ether. The reaction was conducted according to the previously described proceedure to yield the product as a light yellow liquid, b.p. 225 (0.15 mm.), n), 1.4630.

Anal. Calcd. for C -,H, O,: C, 80.95; H, 13.22; Moi. wt. 549. Found: C, 80.94; H, 13.03; Mol. wt. 542.

6,6,12,12,18,] 8,24,24-0ctamethy1-10,20-nonacosanedio1 (XVI). This diol was obtained by means of the lithium aluminum hydride reduction previously described for Compound (IX). Addition of an ethereal solution (600 ml.) of 27 g. (0.05 mole) of 6,6,12,l2,18,l8,24,24-octamethyl-l0,20- nonacosanedione to a stirred suspension of 7.5 g. (0.2 mole) of lithium aluminum hydride in 600 ml. of ether, followed by the described procedures, and distillation of the residual oil gave a colorless liquid, b.p. 245 (0.07 mm.), n 1.4693.

Anal. Calcd. for C -,H ,O C, 80.4; H, 13.85 Mol. wt. 553. Found: C, 80.4; H, 13.88; M01 wt. 551.

6,6,12,12,18,18,24,24-Octamethyl-(9)10,19(20)- nonacosadiene (XVII). This mixture of diolefins, was obtained by means of the anhydrous potassium bisulfate dehydration previously described for Compound (X). Anhydrous potassium bisulfate (8.5 g., 0.06 mole) and 6,6,12, 12, l 8, l 8,24,24-octamethyl-10,20-nonacosanediol (26.3 g., 0.06 mole) was heated at -160 for 6 hours at reduced pressures (3-5 mm.). Work up of the reaction product by the described procedure and distillation of the residual oil gave a colorless liquid, b.p. 200205 (0.02 mm.); n 1.4660.

Anal. Calcd. for C H- C, 85.96; H, 14.04; mol. wt. 517. Found: C, 85.91; H, 14.02; mol wt. 523.

6,6,12,12,18,18,24,24-Octamethylnonacosane (XVIII). This hydrocarbon was obtained by means of the hydrogenation procedures previously described for Compound (XI). 6,6,12,12,18,18,24,24-Octamethy1-9 (l),19(20)- nonacosadiene (16.2 g., 0.03 mole), methylcyclohexane (75 ml.), and 1.2 g. of 5 percent rhodium-on-carbon were heated to 180 in a 300-ml. bomb and rocked for 8 hours at 3,200 psi. Work up of the reaction product by the described procedure and distillation of the residual oil gave a colorless liquid, b.p. 202-205 (0.04 mm.); n 1.4587.

Anal. Calcd. for C H C, 85.29; H, 14.70; mol. wt. 520.9. Found: C, 85.27; H, 14.72; mol. wt. 526.

6,6,12,12,2l,21,27,27-Octamethyl-10,23-

dotriaconanedione (XIX). This diketone was obtained by means of the organocadmium-acid chloride reaction previously described for Compound (V111). A Grignard solution was prepared from l-bromo-4,4-dimethylnonane (68 g., 0.29 mole) and magnesium tumings (8.1 g., 0.31 gr-atom) in 600 ml. of anhydrous ether. The reaction was conducted according to the previously described procedure to yield the product as a light yellow liquid, b.p. 210-218 (0.03 mm.) n 1.4635.

Anal. Calcd. for C,,,H ,,O,: C, 81.3, H, 13.30 Found: C, 81.4, H, 13.75

6,6,12,12,21,21,27,27-Octamethyl-l0,23 dotriacontanediol (XX). This diol was obtained by means of the lithium aluminum hydride reduction previously described for Compound (IX). Addition of an ethereal solution (600 ml.) of 29 g. (0.05 mole) of 6,6,12,12,21,21,27,27-0ctamethyI-l0, 23- dotriaconanedione to a stirred suspension of 10.g. (0.27 mole) of lithium aluminum hydride in 600 ml. of ether, followed by the described procedures and distillation of the residual oil gave colorless, semi waxy-like distillate, b.p. 245255 (0.05 mm.

Anal. Calcd. for C H O C, 80.73; H, 13.89; mol. wt. 595. Found: C, 80.60; H, 14.03; mol wt. 589.

Anal. Calcd. for C H C, 85.93; H, 14.07;mo1. wt. 559. Found: C, 8587; H, 14.04; mol wt. 566.

6,6,12,12,21,21,27,27-Octamethyldotriacontane (XXI).- This hydrocarbon was obtained by means of the hydrogenation procedures previously described for Compound (XI). 6,6,12,12,21 ,21 ,27,27-octamethyl-(9) l0,22(23)-diotriacontadiene (18.3 g., 0.032 mole), methycyclohexane (75 ml.),

and 1.2 g. of 5 percent rhodium on carbon were heated to in a 300-ml. bomb and rocked for 8 hours at 3,200 psi. Work up of the reaction product by the described procedure and distillation of the residual oil gave a colorless liquid, b.p. 220-225 (0.03 mm.); n 1.4600.

Anal. Calcd. for C H C, 85.32; H, 14.68; mol. wt. 563. Found: C, 85.37; H, 14.70; mol. wt. 552.

9,9,18,18-Tetramethy1-7,20hexacosanedione (XXIII). This diketone was obtained by means of the organocadmiumacid chloride reaction previously described in the preparation of Compound (VIII). A Grignard solution was prepared from l-bromohexane (65 g., 0.4 mole) and magnesium tumings (9.7 g., 0.4 gr-atom) in 600 ml. of anhydrous ether. Anhydrous cadmium chloride (40 g., 0.22 mole) was added and the reaction conducted according to the described procedure to yield a light yellow liquid product, b.p. 208 (0.3 mm.

Anal. Calcd. for C H O,: C, 79.93; H, 12.96. Found: C, 79.60; H, 12.68.

9,9,18,l8-Tetramethyl-7,20-hexacosanediol (XXIV). This diol was obtained by means of the lithium aluminum hydride reduction previously described in the preparation of Compound (IV). A solution of l 1.8 g. (0.31 mole) of lithium aluminum hydride in 600 ml. of anhydrous ether was stirred mechanically while 34.7 g. (0.077 mole) of 9,9,18,18- tetrarnethyl-7,20-hexacosanedione in 600 ml. of anhydrous ether was added at a rate sufficient to cause gentle refluxing. The previously described procedure was followed to yield the desired product, b.p. 210-215/0.02 mm., n 1.4675.

Anal.

Calcd. for c l-1, 0,; C, 79.2; H, 13.74. Found: C, 79.4; H, 13.65. Calcd. Mol wt. 454. Found, 448.

9,9,18,18,-Tetramethyl-(6)7,19(20)hexacosadiene (XXV). 9,9,18,18-Tetramethyl-7,20-hexacosanediol (28.5 g., 0.063 mole) was heated with anhydrous potassium bisulfate (9.4 g., 0.07 mole) at l50-160 for 6 hr. at reduced pressures (3-5 mm.). The reaction product was allowed to cool, decanted, and the potassium bisulfate washed several times with small portions of ether. The oil and extracts were combined and the ether evaporated. The residue was distilled to give the desired product, b.p. l78-l80/0.02 mm., n 1.4614.

Calcd. for C H C, 86.0; H, 13.96. Found: C, 85.8; H, 13.84. Calcd. M01. wt. 418. Found, 430.

9,9,18,IS-Tetramethylhexacosane (XXVI). 9,9,18,18- Tetramethyl-(6)7,19(20)-hexacosadiene (11.0 g., 0.0264 mole), methylcyclohexane (75 ml.), and 1.2 g. of 5 percent rhodium on carbon were heated to 180 in a 300 m1. bomb and rocked for 8 hours at a final pressure of hydrogen and reactants of 3,200 psi. The cooled reaction mixture was filtered, concentrated in vacuo, and the concentrate distilled under vacuum to yield the desired product, b.p. 180/0.03 mm., n 1.4528, d 0.8149.

Anal. Calcd. for C l-I C, 85.27; H, 14.72; Mol. wt. 422. Found: C, 85.60; H, 14.30; M01. wt. 430.

6,6,12,12,18,1S-Hexamathyltriacosane (XXVII 6,6,12,12,18,l8-Hexamethyl-(8)9,-l4( l5)-triacosadiene (4.0 g., 0.01 mole), methylcyclohexane (75 ml.), and 1.2 g. of 5 percent rhodium on carbon were heated to 180 in a 300 ml. bomb and rocked for 8 hours at 3,200 psi. Work up of the reaction product by the previously described procedure and distillation of the residual oil gave a colorless liquid product, b.p. l58/0.02 mm.; nfi, 1.4568.

Anal. Calcd. for C H C, 85.27; H, 14.72; mol. wt. 408.8. Found: C, 85.58; H, 14.37; mol wt. 404.

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

1. As a new composition, a quaternary substituted hydrocarbon corresponding to the structure are selected to provide a total of at least 28 carbon atoms in the structure.

2. A compound of claim 1 wherein n is four to six and x is two or three.

3. A compound of claim 2 wherein the total number of carbon atoms in the structure is from 34 to 38.

4. A composition of claim 1 wherein the hydrocarbon is 6,6,1 2,12,18,18-hexamethy1tricosane.

5. A composition of claim 1 wherein the hydrocarbon 9,9,1 8, 1 S-tetramethylhexacosane.

6. A composition of claim 1 wherein the hydrocarbon 6,6,11,1 1,16,16,21,21-0ctamethylhexacosane.

7. A composition of claim 1 wherein the hydrocarbon 6,6,1 1,1 1,17,17,22,22-octamethylheptacosane.

8. A composition of claim 1 wherein the hydrocarbon 6,6,1 1,11,l8,18,23,23-octamethyloctacosane.

9. A composition of claim 1 wherein the hydrocarbon 6,15,12,12,] 8, 18,24,24-octamethylnonacosane.

10. A composition of claim 1 wherein the hydrocarbon 6,6,1 1,1 1 ,20,20,25,25-octamethyltriacontane.

11. A composition of claim 1 wherein the hydrocarbon is 6,6,12,12,21,21,27,27-octamethyldotriacontane.

Claims (10)

1. 2. A compound of claim 1 wherein n is four to six and x is two or three.
2. 3. A compound of claim 2 wherein the total number of carbon atoms in the structure is from 34 to 38.
3. 4. A composition of claim 1 wherein the hydrocarbon is 6,6,12, 12,18,18-hexamethyltricosane.
4. 5. A composition of claim 1 wherein the hydrocarbon is 9,9,18, 18-tetramethylhexacosane.
5. 6. A composition of claim 1 wherein the hydrocarbon is 6,6,11, 11,16,16,21,21-octamethylhexacosane.
6. 7. A composition of claim 1 wherein the hydrocarbon is 6,6,11, 11,17,17,22,22-octamethylheptacosane.
7. 8. A composition of claim 1 wherein the hydrocarbon is 6,6,11, 11,18,18,23,23-octamethyloctacosane.
8. 9. A composition of claim 1 wherein the hydrocarbon is 6,6,12, 12,18,18,24,24-octamethylnonacosane.
9. 10. A composition of claim 1 wherein the hydrocarbon is 6,6,11, 11,20,20,25,25-octamethyltriacontane.
10. 11. A composition of claim 1 wherein the hydrocarbon is 6,6,12, 12,21,21,27,27-octamethyldotriacontane.