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*Nited States Patent C ’ Patented Aug.- 12, 1969

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*Nited States Patent C ’ Patented Aug.- 12, 1969 3,461,160 *nited States Patent C ’ Patented Aug.- 12, 1969 1 2 HNO3 is introduced into the reaction system as an 3,461,160 I aqueous solution. Optionally, an organic solvent (dioxane, PREPARATION OF DICARBOXYLIC ACIDS acetic acid, tetrahydrofuran, Z-nitropropane, or nitrocy Eugene Dennis Wilhoit, Orange, Tex., assignor to E. I. du Pont de Nemours and Company, Wilmington, Del., a clohexane) can be introduced into the reaction system. The corporation of Delaware preferred organic solvents in this process are dioxane and No Drawing. Filed Apr. 28, 1966, Ser. No. 545,833 acetic acid. In the synthesis of higher molecular weight di Int. Cl. C07c 51/20, 51/32 carboxylic acids (those containing 10-18 carbon atoms, US. Cl. 260-533 13 Claims for example) it is preferred, but not necessary, that an or ganic solvent be present to ensure that all materials are '10 maintained in the liquid phase. Usually when lower molec ABSTRACT OF THE DISCLOSURE ular weight ole?ns are employed as the starting material, A process for the oxidation of cyclic ole?ns to dicar organic solvents are not required. boxylic acids such as 1,12-dodecanedioic acid which com The amount of HNO3, H2O, vanadium element, and prises contacting the ole?ns in a liquid phase reaction sys osmium element present is expressed in terms of the rela tem comprising aqueous nitric acid and a catalyst which tive weights of each in the reaction system, based upon is a combination of osmium and vanadium at a tempera 100 parts. Organic starting materials and products, or ture in the range 50 to 150° C. with an oxygen pressure in ganic solvents, and any other material present (such as the a range of 1-7 atmospheres. remainder of the compound in which the catalysts were introduced, if not introduced as the element itself) do not form part of this calculation. The amount of ole?n and This invention relates to dicarboxylic acids, and more solvent employed is expressed as parts per 100 parts of the particularly, to a process for the preparation of dicarbox system mentioned above. ylic acids from cyclic ole?ns. HNO, can comprise 10-70 parts (by weight) of the above-mentioned 100 part system, preferably 25-50 parts Dicarboxylic acids are useful in the manufacture of 25 synthetic resins, plasticizers, and industrial chemicals. The thereof. The amounts of vanadium and osmium, expressed prior art teaches that cyclic ole?ns may be oxidized to di as the amount of the element present, are vanadium, 0.01 carboxylic acids directly in low yield. Since the low yield 07 part, preferably 0.1-0.5 part; and osmium, 0.01-5.0 might have been due to the complexity of the reaction, parts, preferably 0.5-2.5 parts. Thus the relative amount of water is 24-90 parts. Should the presence of an organic the art further teaches that it is desirable to conduct the 30 oxidation in multiple stages so as to afford greater control solvent be desirable, the amount thereof can be varied of the products formed. widely, depending upon the particular reaction system. The process of the present invention provides a simple With the preferred organic solvent, dioxane, generally no one-step high-yield method for the production of dicar more than 100 parts of dioxane are present. It may be de sirable to add to the reaction system dicarboxylic acids, boxylic acids from cyclic ole?ns, which consumes only 35 small amounts of HNO3. The reduction products of HNO3 such as adipic acid, to increase the solubility of the organic formed in this process (nitric oxide and nitrogen dioxide) materials, For example, due to cosolubility effects, cyclo can, by reaction with oxygen in the presence of water, be hexene seems to be more soluble in an aqueous solution regenerated to HNO3. of adipic acid than in water alone. The process of the present invention comprises oxi 40 The relative amount of ole?n present in the process of dizing cyclic mono-, di-, or polyole?ns in a liquid-phase this invention at any given point should be controlled, system comprising HNO3 and osmium-vanadium catalyst. whether a batch or continuous method is employed. In The presence of an organic solvent (for the dicarboxylic either event, slow continuous admission of ole?n is pre acid product) is optional. Such a solvent is desirable when ferred, so that there is never present at any point during the process more ole?n than osmium on a molar basis. the product is of limited solubility in water. This process, 45 for example, can be employed to oxidize substituted or Should an excess of ole?n be present, a reaction with unsubstituted cyclic monoole?ns to the corresponding di HNO3 would probably ensue, with diminution of yield. basic acid. Likewise, cyclic diole?ns can be oxidatively The heat of reaction can be better controlled with a slow ruptured at each ole?nic bond to form two dibasic acids admission of ole?n. of lower molecular weight and can also be ruptured at one 50 The process of this invention can be carried out as a ole?nic bond to form unsaturated diacids. , batch-type operation or in a continuous manner. Illustrative of cyclic ole?ns useful as starting materials A typical continuous process useful in this invention in the process of this invention are those containing up to comprises feeding aqueous HNO3 (and, optionally, an 18 carbon atoms, for example, cyclohexane, cycloheptene, organic solvent) and the ole?n into a stirred, heated re cyclooctene, cyclononene, cyclodecene, cycloundecene, 55 action mixture described above. An aqueous solution com cyclododecene, cyclohexadiene, 1,5-cyclooctadiene, 3 prising mainly HNO3 and dibasic acid(s) is drawn from methylcyclohexene, 4-methylcyclohexene, 4-vinylcyclohex the reactor. If the aqueous solution is sufficiently concen one, B-methylcyclooctene, 3-methylcyclodecene, 3-methyl trated in dicarboxylic acid, the solution can be cooled, if cyclododecene, and cis-4-cyclohexene-l,Z-dicarboxylic necessary, to 50-70" C. to precipitate out the dicarboxylic acid. 60 acid product(s). The solid product is separated by ?ltra The vanadium-osmium system can be supplied to the re tion and the aqueous ?ltrate is recycled. The aqueous ?l action mixture in any one of a number of forms. For ex trate can optionally be concentrated in a still prior to re ample, either osmium or vanadium can be introduced as cycling. the element itself, an oxide of the element, or a salt con When the process of the present invention is conducted taining the element. It is immaterial in which of the above 65 on a batch basis, it is generally preferred that ole?n be forms osmium and vanadium are supplied to the reaction introduced into a stirred aqueous solution of HNO3 and system, since oxidation occurs at once on making up the osmium-vanadium catalyst (and organic solvent, if any), reaction ssytem as described herein. Illustrative of the the solution being held at reaction temperature. Ole?n and chemical forms in which the catalysts can be introduced osmium can optionally be premixed prior to addition of are osmium (as the element), OsO4, vanadium (as the 70 acid. element), V204, V205, and NH4VO3 (ammonium vana The temperature, time, and composition of the reaction date), I<2[OSO4(OH)2]. system are interrelated, and a degree of latitude is avail 3,461,160 3 4 able in selecting these process variables. The temperature and a portion of the solution was analyzed by liquid of the process can be in the range 50—150° C. The pre chromatography (see table for relative weights of reac~ ferred temperature range is 60—120° C. tants and yield of major products based on amount of The process of this invention can optionally be carried ole?n charged). From the remainder of the solution, di out in the presence or absence of oxygen. Pressures of 5 basic acid products were then isolated by crystallization oxygen of up to several hundred p.s.i. can be employed in and identi?ed. this process. Conveniently maintained oxygen pressures The amount of gaseous product (N2 and N20) not use are in the range from about 1-7 atmospheres, i.e., up to ful in regeneration of HNO3 corresponded to the consump about 100 psi. Air can be employed as the source of tion of 0.15 gram of HNO3 per mole of adipic acid pro oxygen in this process. In this event the oxygen pressure 10 duced. referred to herein is the partial pressure of oxygen in air. Examples II-X The presence of oxygen (as the element or as air) over the ole?n oxidation process incorporates the advantage of The procedure of these examples was that of Example regenerating HNO3 in situ simultaneously with the ole?n I, except for modi?cation as noted in the Table. The total volume of the aqueous solution of HNO3, osmium and oxidation. By applying oxygen pressure to the oxidation 15 system, NO is very rapidly converted to N02, which sub vanadium varied between 20 and 40 ml. Note that in Ex sequently reacts with H2O to form HNO3. Since the major amples II, V, and VI dioxane was present, in Example off-gases from the ole?n oxidation of this process are NO IX 2-nitropropane was employed, and in Example X ace tic acid was present. and N02, applying oxygen to the system thus sharply re Example XI duces the amount of off-gas from the reactor. This meth 20 od of operation, therefore, has the advantage of requiring Dioxane (10 ml.) and 2 ml.
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