Патент USA US2403709код для вставки
Patented July 9, 1946 _ 2,403,709 RPATENT ‘UNITED ; STAT’ Es. I 2,403,709Lf, . OFFICE . ‘ PRODUCTION OF o?eAurofrnnoxinns ‘Frank H. Dickey,‘ bakland, andEdiward‘R. Bell, Norwalk, l0hio,vassignors'.to, Shell Develop ment Company, San Francisco, Calif., a C01‘? ’ poration of Delaware No Drawing. Application March;13, 17944, ~ . . . . Serial No. 526,333 . ' I __ '14 Claims. (01. 260-610) 1 . 2’. , pounds. For example, they, may be used as addi' The present invention relates to a novel process for the production of certain Organic peroxides, and more particularly pertains to ‘a. process“ for the production of organic peroxides in whicheach tives toiimprove the cetane value of Diesel engine cals, atmleast one of which is directly linked to‘ the polymerization of 'polymerizable unsaturated compounds including boththe’ conjugated .and fuels- Also, these‘. peroxides may be employed individually: or- inadmixtures with one another of the oxygen atoms of the .peroxyv (—,O—,-Oj-—‘) ~ 1., or with other'subs'tarices as catalysts. for various group is attached to like or diiferent'organicradb chemical reactions. ’ Thus, they [maybe used for its peroxy oxygen ‘atomvyia av tertiary. carbon; atom of aliphatic or alicyclio character, he. a thelnon-coniugated unsaturated polymerizable carbon atom which is directly'attached to‘three 10. other carbon atoms. Inone of its'more speci?c ‘ .~Any .metal salt of a tertiary organic hydro peroxide maybe used as one of the reagents in embodiments the invention provides a'proce'ss‘ for compounds: ' - - , , , . -, , theformation of dialkyl peroxides in which onev the process of the present invention.» A sub-class of compounds which fall within the above class peroxy oxygen atom via a tertiary carbon atom, 15 comprisesthe alkali metal and the alkaline earth of the alkyl radicals is directly attached to the while theother alkyl radical is attached to its‘ metal .salts of tertiary organic hydroperoxides. peroxy oxygen atom via a carbon atom, which may be primary, secondaryor tertiary, so that In thecase ofthe alkali ;metal salts, these reac tants' have the general formula the resulting dialkyl peroxide is either symmet rical or unsymmetrical. . . _ ' 20 class'of compounds comprising the metal salts of tertiary organic hydroperoxides, particularly the alkali metal and alkaline earth metal salts of tertiary organic hydroperoxides, may be formed . M.—'°'—°-B , . . whereinv vM represents an alkali metal, e. g. so dium, lithium or potassium, while R is a'tertiary organic grouping, i. e. an organic radical in'which the carbon atom. directly. attached to the. peroxy It has been discoveredby one of us that a novel 25 Qxygenatom'isfajlso directly linked to‘ three other carbon atoms. 'A group of. compounds which are by theinteraction of a tertiary organic hydro-, particularly suitable for use in the_process.of this peroxide, such as a saturated tertiary alkyl hydro-p‘ inventionrcomprises' the alkali metal salts ofsat peroxide, with a base (preferably a strong base)_. urated alkyl hydroperoxidesof the general for of the metal of which the ‘metal salt is desired.'_ For instance, it was found that an alkali metal‘, 30 mula " i" _. hydroxide,‘ e. g. sodium hydroxide or potassium hydroxide, may be reacted with tertiary butylv hydroperoxide to produce the I corresponding . 1vr-0—‘-o'-('J-R' alkali metal salt of this hydroperoxide._ Simi larly, the alkaline earth metal salts of the tertiary 35, wherein M is van alkali metal, e. g.’ sodium, potas alkyl hydroperoxides may be formed by reacting ' sium or lithium, and each Rrepresents a like or the tertiary hydroperoxide with an alkaline earth different saturated aliphatic radical, e. g. methyl, metal hydroxide, e. g. barium, calcium 'or'stron ethyL- n-propyl, isopropyl,v n-butyl,~ etc.’ radical. tium hydroxide. _ . ‘ . . The following are illustrative examples of such ' ' It has now been discovered that the ‘above and 40 métalsalts: sodium tertiary butyl peroxide, po other metal salts of tertiary organic hydroper tassium tertiary buty1 peroxidarsodium tertiary oxides, i. e. organic hydroperoxides in which the organic radical is directly attached to the peroxy radical via a tertiary carbon atom, may be reacted amyl peroxide, potassium tertiary amyl peroxide, barium salts of tertiary butyl hydroperoxide and monohalides, this interaction resulting in the sub stitution of the organic radical, of. the organic aluminum salts, of the above hydroperoxides are additional’ examples. These hydroperoxides may halide for the metal of the salt, thereby produc contain various organic and/or inorganic groups orradicals, such as aryl, aralkyl, alicyclic radi of; tertiary amyl hydroperoxide, and the like, and with organic halides, and particularly with alkyl 45 their higher homologues. Other metal salts, e. g. ing peroxides in which at least one of the radicals is of a tertiary character, .while the. other ,may be. either primary, secondary or tertiary depend ing on the particular organic halide employed. The symmetrical and asymmetrical organic per cals‘, as well as halogenatoms and the like, sub stituted for one-or more of the hydrogen atoms on the-various carbon atoms of the organic radical. . oxides formed according to the processof, the Although any organic halide may be used/as present invention are particularly useful com-1 .55 the, substance (which is reacted with the ;men-~ 2,403,709 tioned metal salts of the tertiary organic hydro peroxides, the process is especially suitable when applied to the use of saturated alkyl monohalides. These halides may be primary, secondary or ter tiary, the following being illustrative examples of such monohalogenated (i. e. mono?uorinated, monochlorinated, monobrominated or mono 4 etc. Also, ketones of the type of acetone, methyl ethyl ketone, etc., may be used. The dioxanes, such as dioxane, 2,5-dimethyl dioxane-1,4, 2,5 diethyl dioxane-L4, tetramethyl dioxane, etc are also a group of solvents which may be employed. Furthermore, at least in some cases, solvent mix tures of the type of ethyl alcohol and benzol, ethyl iodinated) derivatives of para?ins which may be reacted with the speci?ed metal salts: methyl alcohol and toluol, and isopropyl alcohol and amyl halides, and the like, and their homologues and analogues and suitable substitution products. peroxide, e. g. tertiary butyl hydroperoxide, may be taken and the metal salt thereof may be formed by reacting it with a metal hydroxide. For this purpose, the metal hydroxide may be benzol, are also suitable. halides, ethyl halides, n-propyl halides, isopropyl 10 The process of the invention may be executed in a variety of modes. A tertiary organic hydro halides, n-butyl halides, tertiary butyl halides, Another group of organic halides suitable for the production of the organic peroxides comprises the alicyclic halides, particularly the saturated alicyclic halides, e. g. cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. halides, as well as their substituted derivatives of the type in which employed per se or in solution, e. g. an aqueous solution, or in suspension. Furthermore, this re action may be conducted in the presence of a solvent in which the metal salt of the hydro peroxide is insoluble. The resulting metal salt one or more alkyl radicals are substituted for of the tertiary organic hydroperoxide is then re one or more of the hydrogen atoms of the poly methylene compound. Still another group com acted with an organic halide of the above-de?ned prises the aryl, aralkyl and alkaryl halides, the class. The last-mentioned reaction may be ef fected within a wide range of operating tempera halobenzenes, benzyl halides and tolyl halides being speci?c examples of the group. The process 25 tures, the optimum temperature depending on a of the present invention also includes the inter number of variables, e. g. the speci?creactants action of acyl halides with the metal salts of employed, the presence or absence of a solvent, the particular solvent used, etc. Generally, the tertiary organic peroxides. For instance, the reaction of acetyl chloride with sodium tertiary temperature will vary between about room tem butyl peroxidarwhen effected according to this 80 perature, e. g. 25° C. or even below, and the initial. process, yields sodium chloride and tertiary butyl boiling temperature of the mixture. It is some times preferred to employ relatively high operat peracetate. V "_ The organic peroxides of the class described ing temperatures, particularly in cases where the use of lower temperatures would prevent the herein are preferably formed, by interacting the organic halide with the metal salt of a tertiary 35 presence of a single phase system. With the organic hydroperoxide in the presence of a sol higher temperatures it may be desirable to em vent in which the/metal halide salts, which are formed as a by-product, are not appreciably soluble. It has been discovered that when the aforesaid reaction is conducted in the presence of such a solvent the yields of the desired organic peroxidearemuch higher as compared to those ploy superatmo'spheric pressures in order to keep the reaction products and solvent substantially in the liquid phase. The second reaction, i. e. the formation of the organic peroxides by the reaction of the organic halides with the metal salt of the speci?ed hydroperoxides, is generally con obtained when the reaction is effected in the ab ducted in the presence of the solvent. The pro sence. of the solvent. Besides the better yields portion of the solvent employed in this reaction obtainable, another. advantage in employing a 45 mixture will also depend ‘upon a number of variables such as the properties ofgthe particular solvent having the above characteristicsis that it provides a ready means for separating the solvent, the desirability of maintaining a single liquid phase, the temperature at which the re metal halide. salt. Thus, after the reaction has been completed, the salt may be ?ltered from the action is carried out, etc. Upon completion of the reaction mixture, or may be removed therefrom 50 reaction, the metal halide salt mayberemoved by water washing, and the desired organic per from the reaction mixture by ?ltration, washing, oxide may then be recovered, e. g. by distillation, decantation, centrifugation, etc. After washing from the remaining liquid mixture without the of the remaining liquid phase, the organic per inherent dif?culties of distilling a mixture con oxide may then be recovered from the remaining taining salt, such as the decomposition and cake organic phase, this recovery being preferably‘ ef ing of the salt on the heating surfaces of the fected by distillation. still,_etc. It is preferred to employ a solvent in The following examples illustrate the process which both of the reactants, i. e. the metal salt of the present invention, but are not to be con of the tertiary organic hydroperoxide and the strued as limitative in any sense. organic halide, are substantially or appreciably 60 Example I soluble. This maintains the reaction mixture in Approximately 1'75‘ parts by volume of a 60% a homogeneous state with only a single liquid solution of tertiary butyl hydroperoxide in phase. While the reaction may be carried out tertiary. butyl alcohol were dissolved in about 200 in a two-phase system, better results are gen .65 parts by volume of acetone. The solution was erally obtained when only one phase exists. cooled to a temperature of about 0° C., and ap The most suitable solvent for use in executing proximately 75 parts by volume of a 45% aqueous the process of the invention, besides being a non potassium hydroxide solution were then slowly solvent for the metal halide salt and at least a added to the ?rst solution. This resulted in the partial solvent for the organic reactants, should be substantially inert under the reaction condi 70 formation of a precipitate which was ?ltered at the above-mentioned temperature. The precipi tions. Particular compounds which are suitable to be employed in the present process include tate thus recovered was. washedtwice with small amounts of acetone, and then dried with ,air.. isopropyl alcohol, normal propyl alcohol, normal butyl alcohol, secondary butyl. alcohol, isobutyl An analysis of this precipitate showed‘ that itv alcohol, tertiary butyl alcohol, the amyl alcohols, 76 was potassium tertiary butyl peroxide. This 2,403,769“ my! _ per-tine having‘ the‘generallstructural rer crystalline salt was then‘ dissolved ‘in-_' a; mature consistingrof IOQ'partsY by volume ofjisopropyl bromide and ' 150‘ parts by volume of isopropyl alcohol. The reaction mixture'was allowed to stand for about 15 hours duringwhich- time it precipitated copious amounts" of; potassium bromide formed as a by-product' from the inter action of isopropyl bromide with the potassium‘ salt of tertiary butyl hydroperoxide, _ ' In like: manner many, other symmetricaliand" ,unsymmetrical organic peroxidesjin' which at‘ i _ 10.. least one of the organic radicals is attached to The mixture formed as a result of an interac the peroxy radical via- a tertiary carbon atom,~ tion of the above-mentioned reactants was washed repeatedly ‘with water, then with 9.25% aqueous sulfuric ‘acidsolution, and finally again may ‘be ‘formed. For example, the substances listed below may be reacted with each other to H: produce the organic peroxides listed: with water. vThe remaining organic phase was steam distilled to recoverseparately the fraction boiling at a temperature of about 81.5“ C. An analysis of this fraction showed that it Comprises isopropyl ‘tertiary butyl peroxide, the structural formulaof which is , 16‘ > ' Reactants Organic peroxide _ Sodium tertiary butyl peroxide and ethyl Ethyl tertiary butyl bromide. ' _ -. ‘ 'eroxide. Potassium tertiary ‘butyl peroxide and. n- ropyl ' 20~ n-propyl iodide. . . ‘ _ '‘ Potassium tertiary butyl peroxide and ter- ‘Di-tertiary tiary butyl chloride. sqdiugi tertiary emyl peroxide and ethyl" e ' - ' '7 ‘ ' peroxide. butyl‘ , _ ‘ ‘ Ethyl tertiary amyl , ‘ peroxi e. amyl Potassium tertiary amyl. peroxide and n'» Amyl-tertiary peroxide. amyl bromide. asymmetrical mixed dialkyl peroxide was identi?ed with the following properties: , ‘ tertiary 'butyl peroxide. ., ‘Also, instead of using'the alkali metal salts of the tertiary organic hydroperoxides, the desired organic peroxides may be formedby using the corresponding alkaline earth metal salts, je.fg.' Refractive index, nD2° ________________ __ 1.3862 Carbon_______’_per cent__ 63.4 (theoretical, 63.6)} Hydrogen ______ __do__'__ 12.2 (theoretical,'l2.l) Oxygen“ _____ __‘_d'o____ v2-1.4 (theoretical, 24.3)‘ 30 ~ barium salts, and even salts of other metals, such ‘ asthejaluminum salts of tertiary falkyl hydro-1 _ Molecular'weight____'____ 140 (theoretical, v132) peroxides. Example II ‘ _. . y We claim as‘our invention: > The sodium salt of tertiary [butyl hydroper-v 1. A process for the production of isopropyl ter-j oxide was formed by reacting tertiary‘ butyl hy-M 35 tiary butyl peroxide which comprises'contacting droperoxide with an aqueous 'sodiumhydroxide; solution at approximately ice temperature, the? precipitated, sodium salt being ?ltered, washed' and dried substantially in the same manner as that employed in the preceding example for the 40 recovery of the corresponding potassium salt, propyl alcohol, effecting ‘said contacting‘ at ‘sub-n The sodium tertiary butyl peroxide formed was then mixed with a solution consisting of isopropyl potassium bromide formed as a by-product, and bromide and isopropyl alcohol. Since the salt did from the remaining liquid phase. not dissolve completely in this solution, the mix the potassium salt of tertiary ‘butyl hydroperoxide ' with isopropyl bromide in the presence of i-s_o—> stantially ordinary temperaturesjand'for a pe-_' riod of time su?icient to effect'the formation of' isopropyl tertiary butyl peroxide, separating the distilling the isopropyl tertiary butyl peroxide 45 2. A process for the production of isopropyl ter- '. tiary butyl peroxide which comprises contacting ture was subjected ‘to distillation with total re fluxing for a period of about three hours. The the sodium salt of tertiary butyl hydroperoxide resulting mixture was then washed repeatedly; with isopropyl ‘bromide in the presence of iso with water, then with a 15% aqueous sulfuric acid " propyl alcohol, effecting said contacting under re- ‘ solution, and ?nally with water. .The organic 50 ?uxing conditions for a period of time sumcient phase thus separated was subjected to steam dis to effect the formation of isopropyl tertiary butyl tillation to recover a substantial yield of a frac peroxide, separating the sodium bromide formed as a by-product, and distilling the isopropyl ter tion boiling at about 81° C. This fraction, after washing and drying, had a. refractive index,. tiary butyl peroxide from the remaining liquid nD=°=1.3864, and was found to be isopropyl ter 55 phase. tiary butyl peroxide. 3. A process for the production of isopropyl tertiary butyl peroxide which comprises contact Example III ing an alkali metal salt of tertiary butyl hydro peroxide with isopropyl bromide in the‘ presence Instead of reacting the potassium salt of ter tiary butyl hydroperoxide with isopropyl bro 60 mide, the desired isopropyl-tertiary butyl per oxide can be produced by using the above-men tioned potassium salt and isopropyl chloride. This reaction, effected preferably in the presence of isopropyl alcohol employed asa. solvent for the 66 of isopropyl alcohol, effecting said contacting at a temperature at which ‘substantially a single liquid phase exists in the reaction zone, separat ing the alkali metal bromide formed as a by product, and distilling isopropyl tertiary butyl peroxide from the remaining liquid phase. 4. A process for the production of dialkyl per oxides which comprises contacting an alkali 'this interaction containing appreciable amounts metal salt of a tertiary alkyl hydroperoxide with of isopropyl tertiary butyl peroxide. an alkyl bromide in the presence of isopropyl 70 alcohol, effecting said contacting under tempera Example IV > ture and pressure conditions su?lcient to main tain a substantially single liquid phase in the re When the potassium salt of tertiary amyl hy action zone, separating the alkali metal bromide droperoxide is reacted‘with isopropyl bromide under conditions similar to those described in > formed as a by-product, and distilling the dialkyl Example I, the corresponding isopropyl tertiary. 76 peroxide from the remaining liquid phase. . reactants, causes the precipitation of potassium ' chloride, the organic phase formed as a result of 7 alkaline- earth metal salts. ofthe tertiary alkyl 5.‘ A process for the production of dialkyl peroxide which comprises contacting an alkali metal salt of a. tertiary alkyl hydroperoxide with an alkyl halide in the presence of an inert solvent in which the alkali metal halide salt is substan hydroperoxides with- a halo-substituted hydro carbon‘ vof- the group consisting of the alkyl, cyclo alkyl, monocyclic .aryl, monocyclic aralkyl and - monocyclic alkaryl halides... .9. . A process for the production of organic ‘pare tially insoluble, e?ecting said contacting under temperature and pressure conditions su?lcient to maintain a substantially single .liquid phase, re oxides whichr‘comprises reacting a compound of. recovering the dialkyl peroxide from the remain hydrocarbon.~v the group consisting. of- the alkali metal and alkaline earthametals'alts of the tertiary alkyl moving the alkali metal'halide salt thus .formed as a by-product from the reaction mixture, and 10' peroxides with‘ a. saturated monohalogenated ing liquid phase.v -' - ‘ . 6. A process forthe production of dialkyl per oxides which-comprises contacting an alkali metal , 10. A process. for the production ‘of. organic. peroxides which comprises reacting, a,v compound of the group consisting of the alkali metal and » salt of a tertiary alkyl hydroperoxide with an 15' alkaline » earth. metal salts of the tertiary alkyl alkyl monohalide in the presence of an inert peroxides with analkyl halide. solvent in which “the alkali metal halide salt is 11. A process for the- production of organic peroxides which comprises. reacting an- alkali metal salt of tertiary butyl hydroperoxide with substantially insoluble, removing the alkali metal halide salt formed as a by-product from the re . . I action mixture, and recovering the dialkyl per-' 20; a halo-substituted hydrocarbon of the group con sisting of the alkyl, cycloalkyl,‘ monocyclic aryl, oxide from the remaining reaction mixture. monocyclic aralkyl and >monocyclic alkaryl '7.‘ A process for the production of dialkyl per oxides which comprises contacting a compound 12. A process for the production of organic having the general structural formula 25 peroxides which comprises reacting an alkali ‘metal salt of tertiary butyl 'h'ydroperoxide with halides. . . an alkyl halide. wherein veach R is an alkylradical and M is an: element ofthe ' group consisting of alkali metals 30 and alkaline earth metals, with an alkyl mono-I halide in the presence of an inert solvent in which the metal halide salt is substantially i_-n—' ‘soluble, removing the metal halide salt formed as a ‘by-product from the reaction mixture, and. 35 recovering'the dialkyl peroxide from the remain ing reaction mixture. _ > ._ . __ 8. A process for the production of organic per oxides which comprises reacting a compound of the'group consisting of the alkali metal and. 40 I _ _ - _ ~13.'A process for. the production of organic peroxides which-comprises reacting an alkaline earth-metal salt of tertiary butyl hydroperoxide witha halo-substituted hydrocarbon of the group consisting of the alkyl, cycloalkyl, monocyclic aryl, monocyclic aralkyland‘monocyclic alkaryl halides.v . 7 __ v , . . . 14. A process for. the-production I0f_.0rganic peroxides whichcomprises reactingan alkaline earth metal saltof tertiary butyl hydroperoxide with an alkyl halide. K ' ' \ EDWARD 1i;R.DICKEY. BELL._ . ..