US2349798A - Metallo-organic compound and method of preparing the same - Google Patents

Description

T v UNITED STATE agents as starting Accordingly, an object oilthe inventionls to memes May 30, 1944 S PAT'ENT. OFFICE METALLO-ORGANIC COMPOUND AND METHOD F PREPABING THE SAME George B. Denison, Jr., Berkeley, and Arthur C. Ettling, Richmond, CaliL, assignors to Stand ard Oil Company of California, San Francisco, Calit. a corporation of Delaware No Drawing. Application May 21, 1940,

- Serial N0. 836,392

11 Claims. (61.26MB?) This invention relates to methods of preparing metal compounds of organic acids and involves,

as a preferred group, the preparation of metal salts of high molecular weight organic acids.

Methods utilized heretofore in the preparation of metal salts of high molecular weight organic acids have involved various difliculties. This is particularly true where metal salts of relatively weak bases, such as the alkaline earth metals and/or high molecular weight water-insoluble organic acids, are involved Often expensive raw materials have been required and extended purification methods were necessary to obtain the product of the desired purity and characteristics. For example, when salts of high molecular weight water-insoluble organic acids are prepared by double decomposition in the presence of an aqueous medium, various undesirable reaction products'are sometimes separable only after extended washing or other purification steps.

Additional dimculties have been encountered where the metallic compound of the high molecular weight organic acids is amorphous or has a high melting point. Ithas been found, for

,instance, that when water is present during preparation of such compounds, the salts tend to hold the water so intimately that it can be subsequently removed only by heating to such high temperatures as will partially decompose or-deteriorate the compound. The water formed by reaction of an hydroxide with an acidic hydro gen, as in some prior proposed methods of preparation, is found to introduce this diificulty and materially alter the solubility of the saltin organic solvent such as petroleum hydrocarbons. The

amount of water necessary to materially alter the solubility or other properties of these compounds is, in some instances, quite small.

provide an improved-method elf preparing metal compounds-of organic acids.

- 'Another-ob-ject oi the invention is to produce metal salts of high molecular weight organic acids by an improved process which gives ahigh yield of a product that is relatively free from inorganic salts and aqueous contaminations.

A further object is to provide a process which enables one to readily produce metal salts of very components in addition-to carbon, hydrogen and oxygen present in all organic acids.v The term high molecular weight organic acids is intended to designate acids having a .molecular weight more than approximately 100.

Example of acids which are to be regarded as organic acids within the meaning of this term, as herein u'sed, andwhich fall within the broad scope of the present invention comprise substituted acids of phosphorus containing an organic substituent, substituted sulfuric acids,

We have discovered that metal compounds 01 organic acids can be advantageously prepared by reacting, in a non-aqueous environment, a carbide of a metal and the organic acid. This process is particularly advantageous when applied to high molecular weight orhani Despit the fact that the high molecular weight organic acids are extremely weak and in general relatively unreactive, their metal saltshave been obtained in an anhydrous and relatively pure condition. High yields of the desired compounds have been obtained by using relatively cheap raw materials where other processes either gave a less desirable product or required more expensive rematerials.

c acids.'

substituted acids of arsenic, phenols, sulionic acids, carbocyclic carboxylic acids, and aliphatic carboxylic acids. Phenolic, compounds are acidic and are within the scope of the, invention, as willbe apparent from the remaining disclosure.

' The following comprise examples of substituted acids of phosphorus which may be used in the present process:

O n-o-i -on o Mouoeeteroiorthophosphorlcscid mm oi ortbophospborio acid R-P 4 on i Phosphcnomaoid Mono-ester of phosphonous acid P-OH Phosphlnous acid OH RP Phosphonic acid O O R ,Mono-ester of phosphonic acid POH R ii Phosphinlc acid In the above formulae, R may b alkyl, aryl, alkaryl, aralkyl or cyclic non-benzenoid groups.

Similarly, a corresponding series of substituted sulfurous or sulfuric acids or partially esterified sulfur-containing acids, such as sulfuric acid, are

contemplated as falling within the broad scope oi taining organic groups of alkyl, aryl, alkaryl, aralkyl or cyclic non-benzenoid types.

Additional examples of organic acids comprise carboxylic acids containing carbocyclic nuclei, e. g. aryl, alkaryl, aralkyl or cyclic non-benzenoid types. Examples of such acids comprise phenyl stearic acid, naphthenic acids, naphthoic acids, benzoic acid, and the like. The process is also applicable to high molecular weight aliphatic acids, such as stearic, palmitic, myristic, lauric and oleic acids.

The process of the invention is particularly suited for and finds a most useful application in the preparation of metal salts of water-insoluble phenols. Specific examples of suitable water-insoluble phenols comprise the alkyl phenols such as p-octyl phenol, p-lauryl (dodecyl) phenol and p-cetyl phenol.

It is understood that the process is applicable to the preparation of metal salts of other high p it is intended to designate acids conclaims to designate, generically, phenols which T5- are characterized by an acid group comprising one or more OH radicals directly attached to an aromatic nucleus. These phenols or phenolic compounds are represented generically by the.

type formula:

in which M is a metal; 12, w, x, y and z are selected from the group consisting of hydrogen, hydrocarbon, oxy and hydroxyl radicals; n is the valence of the metal;' and in which the phenolic radical preferably has an alkyl group containing more than four carbon atoms. The hydrocarbo 1 group above mentioned may be an alkyl, aryl, alkaryl, aralkyl or cyclic non-benzenoid group. By the term oxy radical hereinabove mentioned, it is intended to designate an hydroxyl group in which the hydrogen has been replaced by sterification, etherification, neutralization or the like.

As a specific example of a. phenol useful in the present process and a method of preparing the same, the following is given:

Phenol and a butene polymer, having an apparent molecular weight of 194 and obtained by polymerization of a mixture of butenes containing butene-1, butene-2, and isobutene, were mixed. To this mixture, containing 237 grams of phenol and 500 grams of the above-mentioned butene polymers, 140 cubic centimeters of 94%.sulfuric acid was added slowly with agitation. The temperature was kept below 65 F. during addition of the acid. The mixture was agitated for twohours after the addition of acid was completed and permitted to come to room temperature. The reaction product was then diluted with an equal volum of water and placed in a sealed autoclave where it was heated at 350 F. for an hour withagltation. The product was washed with water, 5% sodium carbonate solution and again with water in order to free it of sulfuric acid, sulfonates and unreacted phenol. A 93% yield of high molecular weight water-insoluble alkyl phenol having an acetyl number of '181 was obtained.

A second example of a method of preparing an alky1 phenol is as follows:

511 grams of crude cresylic acid, 900 grams of an olefin polymer containing an average of 14 carbon atoms per molecule and 475 grams of 98% sulfuric acid were utilized in preparing an alkyl cresol. The ingredients were mixed, the temperature controlled and the product washed as in the previous example. The reaction product was vacuum distilled at 10 millimeters and a 50 to cut separated. This portion of the distillate had a molecular weight of 291' and was used to prepare the calcium salt of the alkyl cresol described in the example hereinafter.

The above methods of preparing the alkyl phenols suitable for the purposes oi this invention are merely illustrative. For example, other con .The presence of the acetic acid facilitates temperature control and gives a softer, easier-handied reaction product.

As has been previously indicated, metal salts of high molecular weight organic acids can be advantageously prepared by directly reacting the acid with a carbide of a metal. Suitable metal carbides are those which react with water to form acetylene.

The following comprise illustrative examples of processes utilizing the principles of this invention for the preparation of monohydroxy phenols:

Example 1.247 grams of an alkylatedphenol having an apparent molecular weight of 247 were agitated for six hours at 500 F. with 64 grams of powdered calcium carbide. A gaseous reaction product containing acetylene was formed and removed. The product remaining in the reaction zone was a dark-colored brittle solid at room temperature and comprised acalcium salt of the alkylated phenol. 94% of the theoretical yield of calcium alkyl phenate was obtained as shown by an analysis of a sample of the reaction product freed from calcium carbide by filtration of its petroleum ether solution.

Example .2.685 gramsof an alkylated phenol having an apparent molecular weight of 290 were agitated for six hours at from approximately 500 F. to 540 F. with 90 grams of calcium carbide. A gas containing acetylene was formed and removed. The product remaining in the reaction zone was a dark-colored brittle solid at room temperature. A yield of calcium alkyl phenate, representing 96% of that theoretically possible, was obtained.

The reactions occurring in the examples above disclosed may be represented by the following equation:

. In the above equation, R represents an alkyl group but may be aryl, al'xaryl, aralkyl or cyclic non-benzenoid groups as heretofore explained. Likewise, the above react-ion is applicable to polyhydroxy phenols and to the preparation of phenates of polycyclic phenols in which the benzene ringsmay or may not be conjugated. The term "pheno or phenolic compounds is therefore used herein to designate generically compounds which contain one or more hydroxyl groups directly attached to an aromatic nucleus.

' Metal carbides other than calcium carbide give the above type reaction and may be utilized.

' analyzed as 9.5% calcium, and upon hydrolysis o! the salt 92% of the theoretical amount of pphenol phenol was recovered.

Example of phenols containing coniugated benzene rings-A similar reaction to the above was carried out using beta naphthol and an excess of ground calcium carbide. The. product was only moderately soluble in chloroform or any other common solvent. A portion of the product was extracted using chloroform and the solvent-free extract contained 10.5% calcium. Upon hydrolysis a 75% recovery of beta naphthol was obtained.

Example of a dihydroxy phenoL-Under conditions substantially the same as in the above, an excess of ground calcium carbide was reacted with 4-p-tertiary butyl catechol. Evidence of reaction was as above described. The product was extracted with chloroform to give a brilliant indigo solution which when freed of solvent analyzed as 8.6% calcium, and upon .hydrolysis yielded roughly 80% of an organic substance which ave, upon distillation, of p-tertiary butyl catechol. The product of the reaction is believed to be Example of trihydroxy phenoL- Under substantially the same conditions as in all of the above, ground calcium carbid and pyrogalloi were reacted. The some evidence of reaction was noted as in the other cases. The reaction product acne. This product was the calcium salt of the cyclohexyl phenol.

234 grams of an alkyl. cresol (molecular weight 291) and 25 grams of powdered calcium carbide Such other compounds comprise those metal car- .bldes which are known to react with water to yield acetylene. These metal carbides are herein termed acetylides and comprise the carbides of the alkali metals and alkaline earth metals, namely sodium, potassium, rubidium, cesium, lithium, magnesium, calcium. strontium and berium. To exemplify the reaction of these metal .carbides with phenolic compounds generically,

were heated at 530 F. with stirring for four hours. The product is a hard brittle solid; soluble in mineral oil, and comprises a calcium salt of the alkyl cresol.

By way of further illustration, a metal salt of a substituted organic acid of phosphorus was prepared by reaction with a metal carbide as follows:

Example 3.-To 267 grams of mono-cetyl phosphoric acid were added slowly and with agitation grams of finely powdered calcium carbide. The temperature was held at 200 F. and the addition of the carbide carefully controlled to avoid excess tendency to foam. The total time for completion of the reaction was one hour.- The product was freed Of excess calcium carbide by dissolving in diethyl ether, filtering and evaporating oil the ether. Analysis for calcium showed com-. plete conversion of the mono-cetyl phosphoric acid to calcium cetyl phosphate.

An example of the preparation of metal salts of carbocyclic carboxylic water-insoluble organic acids is as follows:

Example 4.To 684 grams of naphthenic acid obtained from a California fuel oil fraction were added 75 grams of powdered calcium carbide. The mixture was heated in a flask with a-stirrer calcium naphthenate obtained was soluble in mineral oil in all proportions, and in concentrations of 1 to 2% in oil did not materially increase the viscosity of the oil or cause gel formation. Calcium naphthenate prepared in an aqueous environment is soluble in oil in only comparatively small proportions and causes gel formation when added to lubricating oils in amounts as low as Any of th reactions herein disclosed may be carried out in the presence of a non-aqueous, inert solvent such as a hydrocarbon diluent like ously pointed out hereinbeiore. Certain of said high molecular weight'organic acids are watersoluble." However, the invention finds a most useful field of application in the preparation of metal salts of high molecular weight water-insoluble organic acids, particularly th'oseof the carbocyclic type. The invention is especially useful with compounds of the phenolic type.

Thisapplication is a continuation-in-part of our parent application Serial No. 233,326, filed October 4, 1938, for Methods of preparing metallo-organic compounds. Application Serial No. 233,327, filed October 4, 1938, for Composition of matter and method of preparing the same, is directed to the alkaline earth metal phenate species. While the character of the invention has been described in detail, and numerous examples of petroleum naphtha or mineral lubricating oil.

The presence of substantial quantities of water in the reaction zone should be avoided. The conditions under which the reaction is carried out may be altered materially, depending upon. the time allowed for the reaction and upon the materials being reacted. Atmospheric pressure is preferred but the invention'does not preclude the use of either sub-atmospheric or superatmos-- may be intimately contacted with the organic acid by agitation.

It has been observed that methyl alcohol tends to promote the reaction of calcium carbide with the high molecular weight alkyl phenols, and such an alcohol may be incorporated in the reaction zone.

The process of this invention has a number of advantages. It avoids the use of an aqueous solvent as a medium for effecting the reactions and, as previously noted, thereby precludes difllculties often encountered by reason of impurities or bydrolysis of the reaction product. One could not predict that the high molecular weight waterinsoluble phenols,,such as cetyl phenol, which are relatively stable and unreactive like hexyl resorcinol, would react with calcium carbide and ,Ithe like in non-aqueous media. Another advantage of the process is that acetylene rather than water is formed by the reaction of the two initial components and that this gas is easily removed without undue contamination or modification of the tinished product. This last featureis of particular utility in that the necessity for removing substantial amounts of reaction products comprising inorganic salts and/or water is avoided. Other ad an environment substantially free of water.

weight greater than approximately 100, as previ- 76 the preparation and application of the process given; this has been done by way of illustration only and with the intention that no limitation should be imposed upon the invention thereby. It will be apparent to those skilled in the art that numerous modifications and variations of the illustrative examples may be eiiected in the practice of the invention which is of the scope of the claims appended hereto.

We claim:

1. A process of preparing metal salts of phenols which comprises reacting an acetylide with a phenol in an environment substantially free of water, whereby said metal salt is formed in the reaction zone. w

2. A process as in claim 2, in which the reaction is carried out in the presence of an inert diluent.

3. A process as in claim 2, in which the reaction is carried out in the presence of a hydrocarbon solvent. 4. A process as in claim 2, in which the reaction is carried out hol.

5. A process of preparing ametal compound of a phenol which comprises directly reacting magnesium carbide with said phenol in an environment substantially free of water,'whereby said metalcompound and a gaseous reaction product are formed.

6. A process of preparing a metal compound of a polyhydroxy phenol which comprises directly reacting an acetylide with a polyhydroxy phenol in an environment substantially free of water, whereby said metal compound and a gaseous reac ion product are formed.

'7. A process of preparing a metal compound of a polynuclear phenol which comprises directly reacting an acetylide with a polynuclear phenol in an environment substantially free of water, whereby said metal compound and a gaseous reaction product are formed.

8. A process of preparing a metal compound of a water-insoluble phenol which comprises directly reacting an acetylide with said phenol in in the presence of methyl alcowhereby said metal compound and a gaseous react on product are formed. 9. A process of preparing a. metal compound of a water-insoluble phenol which comprises directly reacting magnesium carbide with said phenol in an environment substantially free oi water, whereby said metal compound and a gaseous reaction product are formed.

10. A process of preparing a metal compound of an alkylated phenol which comprises directly reacting magnesium carbide with a water-insoluble carbon-alkyiated phenol in an environment substantially free of water, whereby said metal compound and a gaseous reaction product are formed.

11. A process of preparing a metal compound of a water-insoluble acidic organic compound having a reactive hydrogen atom,which comprises reacting an acetylide with said water-insoluble acidic compound in an environment substantially free of water to replace said reactive hydrogen with the metal of said acetylide and to form a gaseous reaction product comprising acetylene, and recovering the metal compound formed by said reaction.

GEORGE H. DENISON, JR.

ARTHUR C. E'ITLING.

CERTIFICATE OF CORRECTION. Patent No. 2, h9,79 May'fiO, 19m.

- GEORGE H. DENISON, JR., ET AL.

It is hereby, certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 1;, sec- 0nd column, line 51+, claim 2, line 57, claim 5, and line k0, claimlp, for

the claim reference numeral "2" read -1--; and that the said Letters Petent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 25th day of July, A. D. 191m.

Leslie Frazer (Seal) Acting Commissioner of Patents.