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United States Patent (19) 11) Patent Number: 5,235,089 Woodbury Et Al

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United States Patent (19) 11) Patent Number: 5,235,089 Woodbury Et Al IIII O US0.05235089A United States Patent (19) 11) Patent Number: 5,235,089 Woodbury et al. 45 Date of Patent: Aug. 10, 1993 (54) PROCESS FOR THE PREPARATION OF 1240854 5/1967 Fed. Rep. of Germany . 3-CYANO-35,5-TRIMETHYLCYCLOHEXA- 3640306 6/1988 Fed. Rep. of Germany . NONE 1452374 8/1966 France . 75) Inventors: Richard P. Woodbury, Amherst; Jon 116038 7/1982 Japan. C. Thunberg, Milford; Steven P. OTHER PUBLICATIONS Van Kouwenberg, Auburn, all of Du Pont Material Safety Data Sheet (Apr. 20, 1990). N.H.; Walter B. Begonis, Reading, Chemical Abstracts 60:11885e, W. Kenneth Musker Mass. (1964). 73) Assignee: HampshireO Chemical Corp. Chemical Abstracts 103:758092, Sumitomo C hemical Lexington, Mass. 9 Co., Ltd. (1985). 21 Appl. No.: Primary Examiner-Joseph Paul Brust (21) Appl. No.: 843,867 Attorney, Agent, or Firm-Nields & Lemack 22)22 Filed:ed s Feb.eb. 27, 1992 57 ABSTRACT nt. C. O'ss' A process for the preparation of isophorone nitrile uti 58) Field of Search - - - 9 558/341 lizing solutions of lithium hydroxide or lithium cyanide, 8 4 to 0 0 0 & 88 & 0 P W 8 d 4 0 w 000 we w w solid LiOH or solid LiOHoH2O as a catalyst. The reac 56) References Cited tion is carried out under precisely controlled tempera U.S. PATENT DOCUMENTS ture conditions and cyanide feed rate profiles to main 4,299,775 1 1/1981 Dubreux ............................. 260/464 tain a reasonably constant concentration of non-reacted cyanide, thereby minimizing the formation of undesir 5,011,968 4/1991 Thunberg et al. .......... ... 55.8/341 able diisophorone, its nitrile derivative(s) and HCN E. 7: E. al. ...... - - - 2. polymers. A polyacidic acid can be used to acidify the y a 1 a - - - - - - - - - - - - - - - - batch, followed by filtration to remove the precipitated FOREIGN PATENT DOCUMENTS lithium salt of the acid, and vacuum distillation to re move liberated HCN and excess isophorone. The result GS 2A Art, Pa. on ing isophorone nitrile is obtained in high yield and with 0425806 9/1990 European Pat. Off. low impurity content. 0433615 10/1990 European Pat. Off. 1083871 5/1958 Fed. Rep. of Germany. 28 Claims, 2 Drawing Sheets U.S. Patent Aug. 10, 1993 Sheet 2 of 2 5,235,089 3 5 - B/N fil,3 se 2 -0- B/N#24 U l Z C2 O O O 2O 3O 4O 5O 6O 7O TIME (MIN) FIG. 2d - - - - - - TARGET RAMP - as us as a TARGETRAMP O 2O 4O 6O 8O TIME (MIN) 5,235,089 1. 2 Many of the conventional catalysts, and in particular, PROCESS FOR THE PREPARATION OF amine-generating catalysts, used in the isophorone ni 3-CYANO-3,5,5-TRIMETHYLCYCLOHEXANONE trile production can poison the metal catalysts used in the subsequent hydrogenation of isophorone nitrile to BACKGROUND OF THE INVENTION 5 IPDA, thereby significantly reducing catalyst life. It is Isophorone nitrile (IPN) or 3-cyano-3,5,5-trimethyl therefore advantageous and often necessary to eliminate cyclohexanone is a critical intermediate in the synthetic such catalysts from the product, such as by distillation. scheme to the diamine (IPDA) and finally to the diiso However, such additional process steps are labor inten cyanate (IPDI). Numerous prior art processes have sive and costly. In addition, important by-products of been developed to synthesize IPN. For example, U.S. 10 the base-catalyzed reaction of HCN and IPH include Pat. No. 4,299,775 to Dubreux discloses a two-phase diisophorone (dimer) and its conversion to cyano deriv process for the preparation of IPN by reacting isopho atives. For example, as described in the Journal of Or rone (IPH) with a cyanide in the presence of a catalytic ganic Chemistry, 42, (9), 1600-1607 (1977), the follow amount of a phase-transfer agent. The quaternary am ing reactions can occur: CH3 CH3 CH3 CH35CH CH3 CH3 base CH3 CH3 C-4- c bi O O O 1. 4. aidol condensation Michael addition of enolate a to of enolate c to carbon b carbon d O N CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 O HO CH3 O 2 3 (stereochemistry uncertain) monium catalysts are used as their chloride or bromide Isophorone itself contains many impurities. Upon salts; the chloride ion or bromide ion is exchanged for exposure to air, the product becomes yellow, which is cyanide ion and this cyanide ion is transferred from the believed to be a result of the apparent oxidation product water to the solvent layer via the well known phase of isophorone via direct addition of oxygen to the unsat transfer mechanism. urated site: German Patent No. 1,240,854 to Scholven-Chemie Thus, it is also advantageous to minimize the forma discloses a process for the preparation of IPN by react 45 tion of such impurities, of diisophorone, and of its HCN ing isophorone with hydrogen cyanide in the presence adducts. In addition, elimination of residual HCN and of a basic catalyst such as alkali cyanide, hydroxides or excess IPH from the resulting product is necessary. alcoholates. The catalyst is removed by washing with dilute nitric acid. SUMMARY OF THE INVENTION Japanese Laid-Open specification 61-33157 to Nip 50 The problems of the prior art have been solved by the pon Kagako K.K. discloses a process for the prepara instant invention, which provides a process for the tion of isophorone nitrile by reacting isophorone with preparation of isophorone nitrile utilizing lithium hy hydrogen cyanide in the presence of tetra-n-butylam droxide, lithium hydroxide monohydrate, lithium cya monium hydroxide, tetra-n-butylphosphonium hydrox nide, or solutions thereof, as a catalyst in accordance ide or benzyltrimethylammonium hydroxide. The re 55 with the following reaction: sulting reaction liquid is washed with water. However, acidic washing to remove catalyst pro duces an aqueous effluent saturated in isophorone and O O containing some cyanide. Disposal of such an effluent adds significantly to the cost of the product. CH3 + HCN - G CN European Patent Application 0433 615 discloses a CH3 CH3 CH3 CH3 method for producing 1,3,3-trimethyl-5-oxo-cyclohex CH3 ane-carbonitrile by the addition of hydrogen cyanide to isophorone isopborone Nitrile isophorone in the presence of lithium hydroxide as a catalyst, at temperature conditions of 100' to 160' C. 65 By carrying out the foregoing reaction under precisely U.S. Pat. No. 5,011,968 discloses a process for produc controlled catalyst concentration, temperature condi ing isophorone nitrile in the presence of a quaternary tions, and cyanide feed profiles, to maintain a reason ammonium hydroxide as a catalyst. ably constant concentration of non-reacted cyanide, the 5,235,089 3 4. formation of undesirable diisophorone and its nitrile conducted in the presence of catalyst at temperatures derivative(s) is minimized. A polyacidic acid can be below about 90° C. to accomplish the same object. used to acidify the batch, followed by filtration to re The quality of the isophorone and the concentration move the precipitated lithium salt of the acid, and vac of the lithium catalyst are important factors that must be uum distillation to remove liberated HCN and excess addressed in order to obtain the product in good yield. isophorone. The resulting isophorone nitrile is obtained Isophorone which has a yellow color and a high acidity in high yield and with low impurity content, and light does not produce good product. The exact effect of color. color is unknown, but high acidity tends to neutralize and thus destroy the catalyst. Accordingly, it is pre BRIEF DESCRIPTION OF THE DRAWINGS O ferred that the isophorone be distilled prior to reaction FIG. 1 is a diagram illustrating the process in accor with HCN. When good quality (i.e., low acidity) IPHis dance with the present invention; and used, the proper mole ratio of Li:HCN is between about FIG.2a is a graph showing the feed rate of HCN to >0.0025:1.00 and less than about 0.01:1.00; preferably the reaction system in accordance with one embodi about 0.005-0.01:1.00, most preferably about ment of the present invention, and FIG.2b is a graph of 15 0.0075-0.0080:1.00, especially where non-distilled HCN Temperature vs. Time. is used. Such mole ratios ensure that sufficient cyanide concentration is present at all times for the addition of DETAILED DESCRIPTION OF THE HCN to isophorone without the simultaneous presence INVENTION of free base which would catalyze the undesirable for In accordance with the process of the present inven 20 mation of diisophorone from IPH. A mole ratio of tion, which has as an object the preparation of isopho 0.005:1.00 may produce low yields due to neutralization rone nitrile in high yield and with low impurity content, of some of the catalyst by acidity in the IPH plus acidity free cyanide must be present at all times but in low in the HCN; thus, if this mole ratio is employed, the concentration in order to prevent the generation of free HCN should be distilled prior to the reaction. A mole LiOH, which results in the undesirable formation of 25 ratio greater than ~0.01:1.00 may cause dimerization of diisophorone and leads to formation of diisophorone IPH to occur. nitrile(s) and other high boilers. If the free cyanide Significant amounts of water must be avoided, as its concentration drops below a level equivalent to the presence results in reduced yields and increased forma amount of catalyst present (about 200 ppm) at any time tion of high boilers; hence, the lithium catalyst should during the reaction, diisophorone and diisophorone 30 be added as a solid or as a solution in an organic solvent.
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