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4 ‘2,398,685 Patented Apr. 16, 1946 ‘UNITED ‘Sm-Es PATENT‘ OFFICE _ 2,898,685 PRODUCTION OF AGYCLIC KETONES , ' ~Harry Louis Yale and George W. Hearne, Berkeley, Calif., asaignors to Shell Development . ,Company, San Francisco, Calii'., a corporation of Delaware No Drawing. Application January 29, 1944,‘ Serial No. 520,340‘ _ ‘ 12 Claims. . (01. 260-597) ‘ stage operation. In the single-stage mode of ‘ _ operation, the ole?n may be' reacted ‘with the This invention relates to the production of , acyclic ketones from ole?ns. More particularly, oxygen-containing mercuric salt under condi- Y the invention relates to a method for preparing acyclic ketones which comprises reacting a non tertiary ole?n containing more than three carbon - tions such that the ‘ole?n-mercuric salt complex is decomposed to form a ketone and a mercurous atoms with an oxygen-containing mercuric salt. It has been found that non-tertiary acyclic may be accomplished, for example, by carrying salt substantially as soon as it is formed. This out the reaction at a temperature which’ is at or ole?ns having more than three carbon atoms may be converted economically and in good yields to above the decomposition temperature of the ‘said ‘ole?n-mercuric salt complex. In this ‘embodi ment of the invention a quantityof ole?n may-be ketones, including the hitherto relatively unavail able vinyl-type ketones . passed into or contacted with a solution of an (RE-CH=CH:) ' ' oxygen-containing mercuric salt contained in a _ suitable reaction chamber at a temperature which which are useful as solvents and in a wide variety 15 is approximately-the boiling or re?ux tempera- ' ture of the said solution, the ketone product being separated by suitable means from the gases leav > said ole?nsiby treatment with an oxygen-con taining mercuric salt. The nature of the reaction ing the said reaction chamber. Better yields and‘ which occurs is dependent upon the type of ole?n a superior product are obtained in most cases, employed as a starting material. When an alpha 20 however, when the process is carried out in two stages. When employing the two-stage mode of ole?n of the type described is reacted with an operation, a quantity of ole?n or of ole?n-con oxygen-containing mercuric salt, the ole?n is converted to the vinyl-type ketone of correspond taming gas may be contacted with a neutral or acid solution of an oxygen-containing mercuric ing structure. However, when an ole?n is used compound contained in a suitable reaction ves in which the carbon-carbon double bond does not of other industrial applications, by oxidizing the involve a terminal carbon atom, as in a beta ‘ sel, the temperature being maintained at a level olenn, a saturated ketone is produced. These re actions may be represented by the following equa which‘is substantially below the decomposition tions in which alpha-butylene and beta-butylene named as representative ole?ns: , . so temperature of the ole?n-mercuric compound complex. When the desired amount of the said oxygen-containing mercuric compound has beenv . convertedv to the complex, an oxygen-containing acid may be added, if desired, and the tempera ture of the reaction mixture raised to a tempera cnigon=cni+2ngisol+zmsol ' and - CHaCH=CHCHs+2HgBOc+HsO 'o—-* him which is above the decomposition tempera- _ 35 ture of the complex, thereby e?ecting its decom cmgcnionwnisowngiso, position and forming a ketone and a quantity of an oxygen-containing mercurous compound. The ketone product may then be separated from Y Although the above represent the net reactions 4 the reaction mixture by any desired means, as-by , occurring'when a normal butylene is treated with 40 distillation. - The above-described procedure maybe carried a reagent comprising mercuric sulfate and water under suitable conditions of operation, it appears 7 out in a batch, intermittent or continuous man ner. when a batch operation is desired the ole?n that the reaction occurs in two steps, in the ?rst may be added to the oxygen-containing mercuric ' ‘of which the mercuric sulfate reacts with the butylene to form a butylene-mercuric sulfate 45 compound contained in a suitable reaction ves- ‘ sel in substantially the same fashion as described complex. This complex is then broken down under the conditions of the reaction to form a ketone, sulfuric acid and mercurous sulfate. vIin the‘ case of beta-butylene, the reactions for these " ‘steps may be represented as follows: _' above. when operating as a continuous process, however, a stream of ole?n or of ole?n-containing gas may be continuously passed concurrently or countercurrently to a stream of the ongen-con taining-mercuric-salt reagent in'a suitable re action chamber or absorption tower. In single stage operation the reaction may be carried out in the presence oi an oxygen-containing acid and _ It'is therefore possible to'carry out the process of l g the invention as either a single-stage or a two- ,5‘ ate. temperature which is. suiiiciently high to ' a 8,898,685 e?'ect the decomposition of the olefin-mercuric heptadienes and the like. These compounds salt complex substantially as soon as it is formed. _may be substituted with non-interfering sub stituent groups such as the ether, halogen, hydroxyl, carbonyl and ester groups. The ole The ketone product may then be continuously withdrawn from the reactor and purified by dis. tillation, While the mercurous compound which ?ns may be used singly or in combination is formed together with the ketone by-the'de with each other. They may be used as pure composition of the said complex may be contin one?ns or in admixture with non-interfer uously withdrawn as a sludge, separated from the. ing substances, e. g. the paraffin hydrocarbons, acid, decomposition products, etc.,'with which it . nitrogen, etc. The process is thus adapted to the may be contaminated and reconverted by suitable 10 utilization of commercial ole?n fractions con means to the oxygen-containing mercuric com taining in addition to ole?ns substantial amounts pound which is used as a starting material. The ' mercuric compound as well as any ‘unreacted ole?n which may be recovered'from the reaction of paramn hydrocarbons and, in some cases, ni trogen. ' The structure of the product formed is de- - chamber may be added to the fresh feed and 35 pendent upon the nature of the ole?n used. In recycled. _ - " ‘ When carrying out the reaction continue in two stages, the vole?n may be continuously . general alpha-type ole?ns (RCH2CH=CH2) yield vinyl ketones contacted with the mercuric salts-containing re ’ RCCH=CH2 agent at a temperature at which the ole?n-mer 80 curic salt complex‘ is stable. This step may be together with small amounts of saturated di ketones carried out with’ or without the addition of oxy (i gen-containing acid. The mixture containing ' ) (Rb-L0H.) I or ‘o ' "the ole?n-mercuric salt complex may then be passed continuously into a second reactor where 26 while other non-tertiary 'ole?ns yield either one A an acid may be added, ‘if desired, and the decom position of the complex effected by heating the or both of two ketones of isomeric structure de mixture to a temperature which is equal to or pending upon the operating conditions. Thus, greater than the decomposition temperature of an ole?n having the structure RCH=CHCI-h the said complex. The resulting ketone and 80 when treated with a mercuric salt in accordance mercurous-salt-contalning sludge maybe sepa with the process of the present invention may yield either ' ' ‘ rately withdrawn from the reaction chamber and recovered as indicated hereinabove. A preferred method of executing the process of the invention may be illustrated by that which may be employed in omdizing beta-butylene to - methyl ‘ethyl ketone. In accordance with this O O ' apicmcm or ,Romgom or a mixture of these two isomers. . A variety of mercuric salts may be used in exe cuting the process of the present invention. Suitable salts comprise in general the mercuric furic acid and‘mercuric sulfate at ‘a temperature 60 ‘salts of the oxygen-containing acids such as sul of about 20° C. to about 70° (2., but preferably furic acid, acetic acid, nitric acid, phosphoric between about 50° C. and about 60° C. and at ' acid and the like. Mercuric sulfatc'represents a such a rate that the beta-butylene is substan preferred member of this group, although mer tially completely absorbed. When the mercuric curic nitrate, mercuric phosphate, mercuric ace sulfate content of the solution has been substan 45 tate, mercuric formate, mercuric propionate, tially completely converted to the beta-butylene mercuric chloro acetate, etc.,'may also be used. mercuric sulfate complex, as indicated by the These salts may be used singly or in combination characteristic color change of. the solution and by with each other. If desired, they may be pre the failure of the solution to absorb further pared insitu by adding an acid to an appropriate .quantities of beta-butylene, the temperature of 50 mercuric salt such as mercuric oxide or mercuric the reactionmixture is increased to about 100° carbonate, thereby converting the said compound C., thereby effecting the decomposition of the to the‘ desired salt. The amount of mercuric salt olefin=mercuric~ sulfate complex and forming to be used is dependent upon the amount of ole methyl ethylyjketone and mercurous sulfate. ?n which it is desired to convert to the corre The methyl ethyl lretone may then be separated 55, sponding ketone. In general, it is preferable to from the mixture by any suitable means, as by use an amount of mercuric salt which represents manner of operation a stream of .beta-butylene may be contacted with a mixture of aqueous sul distillation. ' , . > The process of the invention may be applied with suitable modi?cations to the oxidation of an excess of from about 25% to about 50% over that theoretically required to combine with the olefin. As indicated hereinabove, the mercuric a wide variety of ole?ns. Suitable ole?ns are 60 salt is converted during the course of the reac tion to the corresponding mercurous salt which more than there carbon atoms. Representative is recovered \as a sludge from the reaction mix ole?nswhich may be converted to the corre ture. The mercurous salt content of the said sponding ketones by the process of theinvention sludge may be converted to the mercuric salt by are, for - example, :alpha-butylene (butene-l), 65 any one of several methods known heretofore to beta-butylene ,(butene-Z) ,. pentene-l, pentene-2, the prior art. The mercurous salt may be con > hexene-l, hexene-2, hexene-3, i-methylwpen verted to the corresponding mercuric salt, for in generarnon-tertiary acyclic ole?ns having. tone-‘l, 4'-methyl-pentene-2, 3-methyl-butene-l, 3-methyl-pentene-l,,4-methyl-hexene-l, li-ethyl hexane-‘o1, 4.-methyl hexene-2, 4-ethyl-hexene-2, 3,-methyl-hexene-l, a-ethyl-hexene-l, S-methyl hexane-'1, 5-methyl-7hexene-2, 5-methyl-hexene 3, the no _ octenes, th ' tiary~ heptenes, the non-tertiary nonetertiary nonenes and decenes, buta'diéneftbe'pentadienes, the hcxadienes, the example, by electrolytic oxidation, by heating ‘ with nitric acid, by treating with chlorine gas 70 in the presence of acid, etc. The re-oxidized mercuric salt may then be used to convert a fresh quantity of ole?n to ketone. Although as indicated hereinabove the process of the invention may usually be executed without 76 the addition of an acid to the reaction mixture, . it may be desirable in some cases to carry out the reactions, particularly .the decomposition of- the ole?n-mercuric salt addition compound, in a‘ re . 3 eflectively executed at atmospheric pressure. 11 7desired, however, subatmospheric orsuperatmos- . pheric pressures may be employed. Operating at elevated pressures, i. e‘. pressures of between about 50 lbs. per sq. in. and about 300 lbs. per sq. in., action medium to which an acid has been added. If an acid is used, it should be an'oxygen-con _ taining acid of suflicient strength to prevent the ' may be advantageous in some instances, as where _ phosphoric acid or, in general, any organic or type of apparatus which is adapted'to batch or continuous one-stage or two-stage operation and it is desired to effect the complete and rapid ab hydrolysis of the mercuric salt and to eii'ect the sorption in the mercuric salt reagent of a par decomposition of the ole?n-mercuric salt com ticular ole?n which is in the gaseous state at the plex under the conditions of the reaction. Suit able acids are the relatively strong oxygen-con 10 temperature of reaction. ‘ The process. may be carried out in any suitable taining mineral acids such as sulfuric, nitric, or inorganic oxygen-containing acid of su?lcient which is provided with suitable means for main talning the reaction mixture at the desired tem- strength to result in the formation of a reaction ' medium having a pH of less than about 4. 1 Such perature level. The equipment should be of such a nature as to effect intimate contact between the ole?n and the mercuric salt reagent. This may acids include acetic acid, bromacetic. acid, butyric acid, chloracetic acid, citric acid, formic acid, iso butyric acid, oxalic acid, phosphoric acid, phos phorous acid, propionic acid, sulfanilic acid, sul be accomplished in batch operation by bubbling furous acid, valeric acid and the like. These acids 20 a quantity. of the gaseous ole?n through the said reagent and in continuous operation by passing may be used singlyT or in combination with each a stream of the ole?n concurrently or, counter other and may or may not correspond to the . currently to a stream of the said mercuric salt ‘ mercuric salt used. The acid may. if desired, be introduced as the acid anhydride and converted ‘ , reagent in a suitable absorption tower. to the corresponding acid by reacting it with the 25 The ketone product may be separated from the reaction‘ mixture in any desired manner as by water- content of the mixture. In many cases, - distilling " it‘ together with relatively small sulfuric acid in a concentration ofirom about amounts of water or solvent and subsequently‘ 0.1% to about 25.0%, preferably about 0.25% to separating the ‘desired ketone from the contami - about 5.0% represents a particularly desirable acid medium in which to carry out the process of 80 nating materials by any suitable. means vas by fractional distillation, .salting out, etc. The mer I the invention. curous salt, which is usuallycontaminated with small amounts of free mercury, may be with It is generally preferred to carry out the re 7 action in aqueous medium. However, if desirable drawn as a sludgefrom the reaction vessel. The mercurous salt may then be ‘converted to the desired mercuric salt as indicated hereinabove. or necessary because of the nature of the reac tants used a mutual solvent, e. g. acetone, may be added to promote the solution or absorption of the ole?n in the reaction mixture. Suitable The process of the invention is illustrated by the following examples, wherein the amounts of _ solvents are those which will not cause deleteri ous side reactions to take place and which may the reactants are given in parts by weight. be readily separated from the reaction products. ' The temperature at which the process is car Example 1 A stream of beta-butylene (butene-2) ried out is variable depending upon the nature of was ‘ passed into a stirred suspension comprising about 5 of mercuricsulfate and about 22 parts u the reactants, and upon whether the process is carried out in one or two stages. If vcarried out or a 1.8% aqueous solution oi’ sulfuric acid at such as a single-stage process, i. e; one in which the 45 a rate thatthe absorption of the beta-butylene ole?n-mercuric salt complexis decomposed sub was substantially complete, the temperature be stantially as n as formed, the temperature em ployed may advantageously be a temperature _ ing maintained at about 55° 0. As the gas was absorbed, theoriginal yellow color of the suspen sion slowly changed to white‘. when the suspen sion had become uniformly white in color, the which is approximately the boiling temperature of the reaction mixture. Where the reaction is carried out in aqueous medium at atmospheric pressure, this temperature will be about 100° C. Where, however, the process is carried out in two stages, the temperature of operation of the ?rst ' stage, _i. erthat stage in which'the cloth: is re temperature was slowly raised to 100° 0. Decom position of the beta-butylene-mercuric sulfate complex'occurred at this temperature and the methyl ethyl ketone distilled out of the reaction mixture as the water-methyl ethyl ketone azeo acted with the mercuric ‘salt to form an ole?n mercuric salt complex, should be substantially be- ' trope. Additionpf salt to this distillate resulted ' in the separation .of the methyl ethyl ketone low the decomposition temperature of the. said > complex. with most ole?ns a temperature-range of between about 20° 0. and about 70° 0., prefer ably between about 50° 0. and about 60° 0., rep ’ resents a suitable temperature range. After the‘ conversion of the ole?n to the ole?n-mercuric salt ‘complex is substantially complete, the tempera - product. ' Example II A quantity of beta-butylene was reacted-with a mixture comprising about 1 part of mercuric acetate and about 4 parts of a 2.84% aqueous so- ' luti'on‘ of acetic acid substantially as described‘in Example I. Distillation of the reaction product ture may be raised in the second stage of the process to a level at, which the said complex is . - resulted in the separation'of methyl ethyl ketone together with a small amount of acetaldehyde. 1 unstable and decomposes to form the desired ke tone together with a quantity of mercurous salt. __ Example, 111 This is in general a temperature of between about 90° 0._ and about 105° 0., preferably a tempera 70 Beta-butylene was reacted with a sulfuric ac solution oi mercuric acetate using the procedure .ture which is approximately equal to the reflux .or boiling temperature of the reaction mixture, ’ described in Example I. The product, i. e. the methyl ethyl ketone, was distilled from the re e. g. a temperature of, about 1100' 0., when the re- ' action mixture as the ‘water-methyl ethyl vketone action is carried out in aqueous medium. 2 WW'OPB‘ ' ' ' f The process of the invention may usually be sea ethyl iretone which comprises.forming aninter , Beta=buty1ene was reacted with an aqueous ni tric acid solution of mercuric nitrate substantial» ly in the manner described in Example I. The reaction in this case gave approximately equal amounts of methyl ethyl ,ketone and diacetyl to gether with a small amount of acetaldehyde. ing the said butene-2 at a temperature of be tween about 50° C. and about 60° C. with men curic sulfate in an aqueous acid medium con taining from about ‘0.5% to about 5.0% of sul furic acid and subsequently heating the acid mix ture containing the said complex to a tempera ture of about 100° 0., thereby effecting its de ‘ Example V Pentene-2 was reacted with an aqueous sulfuric acid solution of mercuric sulfate in the manner described in Example I. In this case a mixture of methyl-n-propyl ketone and di-ethyi ketone was separated from the product distilling from the reaction-vessel. mediate mercury-containing compound by react ‘ composition and forming the desired methyl eth yl ketone. 3. A process for the production of methyl ethyl ketone which comprises contacting at a tempera ture of between about/i0" C. and about ‘20° C. ' beta-butylene with a quantity of a reagent com Example VI prising mercuric sulfate and dilute sulfuric acid But'adiene was reacted with an aqueous sulfuric acid solution of mercuric sulfate as described in furic acid thereby forming ‘a butylene-mercuric sulfate addition compound, and subsequently containing between about 0.5% and 5.0% of sui Example I to give methyl vinyl ketone together 20 heating the said addition compound in an acid with small amounts of diacetyl as reaction prod ucts. _ Example W1‘ A mixture of about 14 parts of hexane-l. and about 65 parts of a 1.74% aqueous solution of sulfuric acid was heated to a temperature of about 55° C. until the formation of the hexene-l mercuric sulfate addition product was substan‘ medium at a temperature sufficiently high to ef fect ‘the decomposition of the said addition com _ pound and the formation of the desired methyl ethyl ketone. ‘ a. A process for the production of methyl vinyl ketone which comprises forming a. butylene-mer ouric sulfate complex by contacting alpha-bu ty’lene with a quantity of mercuric sulfate in an aqueous acid medium containing from about 0.5% product at 100° C. resulted in the separation of 30 to about 5.0% of sulfuric acid at a temperature of tially complete. Decomposition of the addition propyl vinyl ketone together with'a small amount of acetyl, butyryl. Example VIII between about 50° C. and about 60° C., subse quently decomposing the said complex and form ing the desired ketonc by heating the said com plex in the said aqueous acid medium at a tem Oxidation of octane-1 under conditions similar 35 perature which is substantially equal to the boil to those described in Example VH resulted in the ing temperature of the latter. ' ' recovery of pentyl vinyl ketone and acetyl hexoyl. Example IX 5. A process for the production of methyl vinyl ketone which comprises reacting butene-l at a temperature of between about 40° C. and about Butene-l was passed into a sulfuric acid solu= 70° C. with a mixture of mercuric sulfate and di tion of mercuric sulfate maintained at a temper lute sulfuric acid containing from about 0.5% ature of about 55° ‘C. until- the absorption of the and 5.0% of sulfuric acid, thereby forming a butene and the formation of the butene-mercuric butene=mercuric sulfate addition product, and sulfate addition compound were substantially subsequently heating the said addition product in . complete. The temperature of the reaction mix 45 the said acid solution to a temperature of about ture was then raised to about 100° C. in order to 100° C. in order to decompose the said addition decompose the addition compound and form methyl vinyl ketone. Example X A stream of beta-butylene was passed into a mixture‘ comprising about four parts of water and one part of mercuric acetate, no added acid being present. When absorption of the beta-bu tylene was complete, the temperature of the mix turewas increased to 100° C., thereby hydrolyz ing the beta-butylene-mercuric acetate complex. ~ Methyl ethyl ketone was separated as a product from the reaction ‘mixture. product and form the desired methyl vinyl ke tone. ‘ ~ ~ 6. A process for the productionof methyl vinyl ketone which comprises oxidizing beta-butylene with a mixture comprising an oxygen-containing mercuric salt and an acid solution having a sul furic acid content of from about 0.5% to 5.0%. 7. A. process for the production of methyl vinyl 55 ketone fromalpha-butylene which comprises con tacting the said alpha-'butylene at a reaction tem_ perature with an oxidizing mixture comprising an oxygen-containing mercuric salt in a solution of sulfuric acid having a sulfuric acid content of We claim as our invention: 60 from about 0.5% to 5.0%. , 1. A process for the production or methyl ethyl ’ 8. A process for preparing acyclic monoketones ketone from butene-i2 which comprises reacting at a‘ temperature of between about 50° C. and ' about 60° C. the said butene-2 with mercuric ace“ A from a normal butylene which comprises react ing the butylene at a reaction temperature with an oxygen-containing mercuric salt in an aque tate in an acid medium which contains between 65 ous solution of sulfuric acid having a sulfuric about 0.5% and about 5.0% of sulfuric acid there acid concentration of from 0.5% to 5%. by forming an addition product between the said butene-Z‘ and the mercuric compounds present in the said acid medium, and subsequently raising r 9. A process for producing acyclic monoketones which comprises oxidizing an acyclic ole?ne hav ing more than three carbon atoms and containing ' the temperature of the said acid medium to a 70 only one unsaturated linkage consisting of a dou ' temperature which is approximately its boiling ble bond between two carbon‘ atoms ‘each having temperature in order to effect the decomposition at least one hydrogen atom directly attached of the said complex and the formation of methyl thereto, witha mixture comprising an oxygen ethyl ketone. ‘ containing mercuric salt andlgan aqueous solution 2. A process for oxidizing butcher-2 to methyl 75 of an unison-containing acid having an acid . 5 9,898,685 ‘ strength correspondingtothatoi' anaqueousso lutlon of sulfuric acid having a sulfuric acid'con centration of 0.5% to 5%. 10. A process for the production of an aliphatic monoketone which comprises maintaining an 5 aqueous acidic mixture oi’ a mercuric salt at a‘ temperature in the range of 40° C. to 70° 0., add ing an open-chain olefin having more than three sisting of a double bond‘ between two carbon - atoms each having at least one hydrogen atom directly attached thereto, with an aqueous acidic mixture of a. mercury salt in such proportion ' that thevmercury salt is present in an amount corresponding to a 25% to 50% excess over the amount theoretically required to react with all of the olefin. ‘ ' two carbon atoms each having at least one hy ‘ 12. A_ process for the production or propyl vinyl ketone which comprises reacting hexene-l at a temperature of between about 50° C. and about drogen atom directly attached thereto, to said 60° C. with a quantity of mercuric sulfate in an carbon atoms and containing only one unsatu- ‘ rated linkage consisting of a double ‘bond between‘ aqueous mercury salt solution in an amount ni su?icient to combine withall or the mercury salt. -then raising the temperature of reactionto about a 100° C. and recovering an aliphatic ketone from the reaction'mixture. / . 11. A process for the production of an aliphatic monoketone which comprises reacting an open chain ole?n having more than three carbon atoms and containing" only one unsaturated linkage con aqueous acid medium containing from about 0.5% to about 5.0% of sulfuric acid, thereby forming a hexene-l-mercuric sulfate addition product, and subsequently heating the said addition prod uct in the said acid solution to a temperature of about 100° C. to decompose the said addition product and form the desired propyl vinyl ketone. , : HARRY LOUIS YALE. GEORGE W. HEARNE.