US2134711A - Production of nuclear alkyl derivatives of phenols - Google Patents

Description

Patented Nov. 1, 1938 PRODUCTION OF NUCLEAR ALKYL DERIVA- TIVES F PHENOLS No Drawing. Application September 25, 1935, Serial No. 42,158

10 Claims.

This invention relates to the production of chemical compounds suitable for use as detergents, foaming agents, wetting agents, and the like. It relates more particularly to a method of making products which are nuclear alkyl derivatives of phenol sulfonic acids in which the alkyl group contains at least 12 carbon atoms, more particularly 12 to 23 carbon atoms, and especially 14 to 19 carbon atoms.

According to. the present invention, an alkyl halide containing at least 12 carbon atoms (preferably 12 to 23, and especially 14 to 19, carbon atoms) is condensed with phenol or a cresol, preferably with the aid of a metal halide condensing agent, to produce the corresponding nuclear alkyl phenol, and the resulting alkyl phenol is sulfonated.

The alkyl phenol sulfonic acid compounds resulting from the process of the present invention, in the form of the free sulfonic acid or a salt thereof, correspond with the general formula A igjnam in which A represents hydrogen or a methyl group, R represents an alkyl hydrocarbon radical (which may be straight or branched, primary, secondary or tertiary) containing at least 12 carbon atoms (preferably 12 to 23, and especially 1 to 19 carbon atoms) and M represents hydrogen or a metal, particularly an alkali metal, or an ammonium or organic ammonium radical.

The said alkyl phenol sulfonic acid compounds are derivatives of phenol (hydroxybenzene) and of the cresols (1.2-,1.3-, and IA-methyl-hydroxybenzene) in which the alkyl hydrocarbon radical represented by R in the foregoing formula is directly linked to a nuclear carbon atom and in which the sulfonate group (represented in the foregoing formula by -SO2OM) is also directly linked to a nuclear carbon atom. For convenience they will be hereinafter referred to as alkyl phenol sulfonates, which term generically includes the phenol and cresol derivatives, in the form of the free acids or the salts. The alkyl phenol sulfonates preferably employed in accordance with the present invention are those in which the alkyl group contains a branched carbon chain, whether linked to the benzene nucleus by an end carbon atom (an alpha carbon atom) or an intermediate carbon atom (that is,

whether a primary, secondary or tertiary alkyl group).

The said alkylphenol sulfonates may be used instead of the usual soaps for scouring, cleaning, washing and toilet purposes as well as for other purposes for which ordinary soaps have heretofore been employed. They also may be employed in conjunction with ordinary soaps, since it has been found that the presence of the said alkyl phenol sulfonic acid compounds serves to prevent objectionable precipitates from forming in hard water or in acid treating baths or in salt baths. They have the further advantages of being in' general better wetting agents and more soluble than the usual soaps, and of leaving the washed goods with a soft feel. Inasmuch as the water solutions of said components in the form of their alkali metal salts are neutral in reaction, the latter may be safely used for the washing of delicate silks and other line fabrics as well as for personal toilet purposes.

The said alkyl phenol sulfonates are also valuable wetting agents useful in the textile and related fields and as insecticidal, fungicidal, emulsifying, dispersing and/or tanning agents.

The inventionwill be illustratedby the following specific examples in which the parts are by weight and temperatures are in degrees centigradel It will be understood by those skilled in the art that the scope of the invention is not limited to these specific examples.

Example 1.-Sodium cetyl phenol sulfonate A mixture of parts of cetyl chloride (prepared from commercial cetyl alcohol and boiling within the range of to 210 at 5 mm. pressure), 80 parts of phenol and 10 parts of anhydrous zinc chloride, while being agitated vigorously, is heated to a temperature of and then is maintained for 6 hours at a temperature of 175 to The reaction mixture is all-owed to cool, and the oil is decanted off and fractionally distilled in a vacuum. The fraction of the distillate boiling from to 250 at 5 mm. of mercury pressure is separately collected. The product, which comprises cetyl phenol, is a viscous oil which is partially solid at room temperature and completely solid at 5.

Example 2.--Sodium myristyl paral-cresol sulfonate hours. After cooling, myristyl-para-cresol is obtained from the mass by decantation, fractional distillation in a vacuum, andcollection of the fraction boiling from 175 to 235 at a pressure of 5 mm. of mercury. The product is a lightbrown viscous oil. An equal weight of 100% sulfuric acid is added to the product at a temperature of 10 to 25. The reaction mass is agitated while maintaining this temperature until a test portion is not turbid in dilute alkaline solution. After drowning in ice water, the solution is neutralized with aqueous sodium hydroxide'and evaporated to dryness.

Emample 3.-Sodium lauryl ph nol sulfonate A mixture of 185 parts of laury l chloride (prepared from commercial lauryl alcohol), 100 parts of phenol and 30 parts of zinc chloride (as a condensing agent) is heated with agitation at a temperature of 170 to 180 under a reflux condenser for 20 hours. The reaction mixture is allowed to cool and the oil which separates is decanted off and fractionally distilled in a vacuum. The fraction of the distillate boiling between 150" and 230 at 4 mm. pressure of mercury is separately collected. It consists chiefly of lauryl phenol in admixture with other alkyl phenols. To 20 parts of the lauryl phenol product thus obtained, there is slowly added with agitation 20 parts of sulfuric acid monohydrate,

and the mixture is maintained at a temperature of 30 to 35 for 3 hours or until the desired sulfonation is effected. The mass is diluted with 400 parts of water, and the solution thus obtained is neutralized with caustic soda and evaporated to dryness. The product thus obtained comprises a mixture of alkyl phenol sulfonates together with some sodium sulfate, of which a predominant compound is the sodium salt of lauryl phenol sulfonate having the probable formula:

CH BO:N8

OHi

that changes may be made in the processes hereinbefore described, without departing from the scope 'of the invention.

Thus, phenol, ortho-, meta-, or para-cresol or their mixtures may be employed.

Various alkyl halides containing at least 12 carbon atoms may be employed; as for example, chlorides and bromides of the saturated and unsaturated'hydrocarbons of the aliphatic class, including straight-chain and branched-chain monochlorides and monobromides in which the halogen atom is linked to an end carbon atom or an intermediate carbon atom. Those in which the hydrocarbon radical of the halide contains a branched carbon chain or which result in a product in which the radical represented by R in the foregoing formula contains a branched carbon chain are preferred.

The proportion of alkyl halide employed with respect to the phenol may vary; but preferably the proportion of alkyl halide employed with respect to the phenol is such that not more than two of the said alkyl radicals of the type represented by R in the foregoing formula are contained in the resulting alkyl phenol and preferably only one. Thus, at least 1.25 mols of phenol per mol. of alkyl halide is preferably employed in the condensation. A molar ratio as low as 1 .to 1, or even lower, may be employed, but the yield of the resulting alkyl phenol containing one alkyl radical of the said type represented by R will be less.

As condensing agents there may be employed anhydrous zinc chloride, anhydrous aluminum drous ferric chloride, zinc, zinc oxide, copper, magnesium, etc. During the condensation with zinc or zinc oxide, a zinc halide is probably formed and hence also with these substances the condensation appears to take place in the presence of a zinc halide. In general, anhydrous zinc chloride is preferably employed as thecon- (lensing agent since, on the whole, it gives more uniform products and better yields, as well as sulfonated products of superior color and quality. While the zinc chloride and other metal halide condensing agents mentioned have been referred to as anhydrous, it is noted that said condensing agents may be employed in partially hydrated condition containing small amounts of water, for instance such as are absorbed from the surrounding atmosphere or otherwise in commercial operation, but insuflicient to interfere with their action as condensing agents. Even when the zinc chloride contains an equal weight of water it functions as a'condensing agent; but such large amounts of water are preferably avoided.

The condensation may be carried out at various temperatures; for example, room temperature to the boiling point of the reaction mixture, or higher. Temperatures from about 60 to about 180 C., or to the somewhat higher refluxing temperatures, and especially above C.. are preferably employed with zinc chloride as the condensing agent.

The amount of condensing agent employed may vary. For example, in using zinc chloride as the condensing agent and a long-chain alkyl chloride about 5 to about 20 per cent of anhydrous zinc chloride, based on the weight of the alkyl chloride, is suflicient.

The time during which the condensation reaction of the alkyl halide and the phenol may be carried out also may be varied. In general the condensation of a long-chain alkyl chloride with phenol or a cresol is satisfactorily complete in about 1 hour at refluxing temperature (approximately 180 C.) or in about 3 to 6 hours at C., but is'continued for a longer time for best results in preparing a detergent. With zinc chloride as the condensing agent, the period of heating at refluxing temperature may be extended to 16 hours or more without seriously harming the quality or substantially decreasing the yieldof the alkyl phenol.

The-crude alkyl phenol resulting from the condensation is preferably purified, as for example, by fractional distillation at pressures not exceeding 30 mm., and the purified compound is preferably employed for sulfonation, when the product 'is to be employed as adetergent, in view of the resulting superior detergent properties.

As sulfonatingagents there may be employed adapted to form a neutral product.

sulfuric acids of various strengths (e. g., 66 B. sulfuric acid, sulfuric acid monohydrate, oleum) chlorsulfonic acid, etc.

The sulfonation may be carried out in the presence or absence of aninert organic solvent or diluent and in the presence or absence of a sulfonation assistant. As solvents or diluent there may be employed any inert organic, liquid which is not readily sulfonated, such as halogenated hydrocarbons of the aliphatic and aromatic series, as for example, carbon tetrachloride, dichlorethane, tetrachlorethane, dichlorbenzene, etc. As sulfonation assistants there may be employed the lower organic acids and/ or their anhydrides, as for example, acetic acid, acetic anhydride, etc.

The temperature at which the sulfonation is carried out may vary within wide limits. For example, temperatures as low as about C., and as high as about 140 C. may be employed. In general the more vigorous the sulfonating agent the lower is the preferred temperature. Ordinarily the completion of the sulfonation is carried out at atemperature in the neighborhood of about 25 to about 80 C. The ratio of sulfonating agent employed with respect to the alkyl phenol also may be varied. While the preferred amounts are given in the above examples, an amount of sulfuric acid or other sulfonating agent equivalent to from 1 to about 5 parts by weight of s'ulfuric acid monohydrate per part by weight of the alkyl phenol may be employed.

The extent to which the sulfonation is carried out may vary with the individual material being sulfonated and the use to be made of the sulfonated product. In general the extent of sulfonation of the alkyl phenol treated is such as to form chiefly the monosulfonic acid of the alkyl phenol, and to sulfonate impurities as well, if present.

The alkyl phenol sulfonates may be prepared in accordance with the present invention in the form of their free s'ulfonic acids or in the form of salts of metals (as for example, of the alkali metals) or of organic bases, or of ammonia, etc. The salts may be obtained in any suitable manner, for example, by reacting the sulfonated product, either in the crude form resulting from the sulfonation or in a purified form, with a metal oxide or hydroxide, ammonia or an organic base, or of a suitable salt of one of these, in an amount Among the bases, oxides and salts which may be combined with the sulfonated products to produce salts useful as detergents and otherwise are, for example, sodium, potassium and ammonium hydroxides; sodium, potassium and ammonium carbonates and bicarbonates; ammonia; magnesium oxide; ethylamine; pyridine; triethanolamine; propanolamines; butanolamines; diamino propanol; ethylenediamine; triethylene tetramine, etc.

The reaction mixtures resulting from the sulfonation of the alkyl phenol or cresol may also be directly employed for the formation of mixed products, as for example mixtures of salts of the alkyl phenol sulfonic acid and of other acids present in said reaction mixtures, which mixtures of salts are also useful as such. Thus, the sulfonation reaction mixture resulting from the treatment of the alkyl phenol or cresol with an amount of sulfonating agent in excess of that theoretically required to effect the desired degree of sulfonation may be treated with a suitable inorganic or organic base or basic salt (as for example, one of those mentioned) and the resulting mixture of the salt of the sulfonated alkyl phenol or cresol and the other inorganic and/or organic salt (as for example, sodium sulfate) may be jointly isolated from the reaction mixture and employed as such. If it is desired to produce a salt of the sulfonated alkyl phenol or cresol in a form substantially free from inorganic salts (for example, inorganic sulfates) this may be accomplished by taking advantage of the solubility of the salts of the sulfonated products in alcohol and other organic solvents. Thus a mixture of a salt of the sulfonated product and an inorganic sulfate, such as obtained by the processes of the above examples, may be extracted with alcohol, and the resulting extract may be evaporated to leave a residue of the purified salt of the sulfonated product.

The sulfonated products in the form of metallic salts or salts of inorganic bases are usually yel lowish to white, friable solids; and in the form of salts of organic bases vary from viscous oils to semi-solids to solids. In general, the salts are readily soluble in water and in aqueous (neutral, acid or alkaline) solutions to form solutions which are faintly colored brown or yellow, which are of a soapy nature and which form readily. Certain of the salts, such as the salts of the arcmatic monoamines and the aliphatic and arocondensing a member of the group consisting of phenol and its monomethyl derivatives with an alkyl halide containing at least 12 carbon atoms with the aid of a condensing agent, and sulfonating the resulting product.

I 2. A method of producing a nuclear alkyl derivative of a sulfonated phenol, which comprises forming a phenol compound containing a higher alkyl substituent by condensing a phenol compound of the group consisting of phenol and its monomethyl derivatives with an alkyl halide containing at least 12 carbon atoms in the presence of a metal halide condensing agent, the amount of alkyl halide not exceeding about that required to produce monoalkylation of the phenol compound and sulfonating the alkylated phenol compound.

3. A method of producing a nuclear alkyl derivative of a sulfonated phenol, which comprises condensing one mol of a phenol compound of the group consisting of phenol and its monomethyl derivatives with not more than one mol of a saturated open-chain aliphatic halide containing at least 12 carbon atoms with the aid of a zinc halide as a condensing agent, and sulfonating the resulting product.

4. A method of producing a nuclear alkyl derivative of a sulfonated phenol, which comprises forming a phenol compound containing a higher alkyl substituent by condensing a phenolcompound of the group consisting of phenol and its monomethyl derivatives with a saturated openchain aliphatic monohalide containing 12 to 23 carbon atoms with the aid of a condensing agent,

the amount of alkyl halide not exceeding about that required to produce monoalkylation of the phenol compound and sulfonating the alkylated phenol compound.

5. A method of producing a nuclear alkyl derivative of a sulfonated phenol, which comprises condensing one mol of a phenol compound of the group consisting of phenol and its monomethyl derivatives with not more than one mol of a saturated open-chain aliphatic monohalide containing 12 to 23 carbon atoms in the presence of a metal halide condensing agent, and sulfonating the resulting product.

6. A method of producing a nuclear alkyl derivative of a sulfonated phenol, which comprises condensing at least 1.25'mols of a phenol compound of the group consisting of phenol and its monomethyl derivatives with one mol of a saturated open-chain aliphatic monohalide containmg 14 to 19 carbon atoms with the aid of a zinc halide as a condensing agent, and sulfonating the resulting product.

7. A method of producing a nuclear alkyl derivative 'of a sulfonated phenol, which comprises condensing a member of the group consisting of phenol and its monomethyl derivatives with an alkyl chloride containing at least 12 carbon atoms with the aid of anhydrous zinc chloride, whereby the corresponding alkyl phenol compound is produced, and sulfonating said alkyl phenol compound.

8. A method of producing a nuclear alkyl derivative of a sulfonated phenol, which comprises condensing one mol of a phenol compound of the group consisting of phenol and its monomethyl derivatives with not more than one mol of an open-chain aliphatic chloride containing at least 12 .carbon atoms in a branched chain, with the aid of a metal halide condensing agent, whereby the corresponding alkyl phenol compound is produced, and sulfonating said alkyl phenol compound.

9. A method of producing a nuclear alkyl derivative of a sulfonated phenol, which comprises condensing at least 1.25 mols of a phenol compound of the group consisting of phenol and its monomethyl derivatives with one mol of an openchain aliphatic monochloride containing 14 to 19 carbon atoms in a branched chain, with the aid of anhydrous zinc chloride, whereby the corresponding alkyl phenol compound is produced, and sulfonating said alkyl phenol compound.

10. A method of producing a nuclear alkyl derivative of a sulfonated phenol, which comprises condensing one mol of phenol with not more than one mol of an alkyl mono-chloride containing 12 to 23 carbon atoms, with the aid of zinc chloride as a condensing agent, whereby the corresponding alkyl phenol is produced, and sulfonating said alkyl phenol.

LAWRENCE H. FLETT.