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Lllllllllliillilllllllllllliihiillllllllllllllllllllllllll llllllllllIIllIllllllllllllIIHIIllllllllllllllllllllllllllllllllllllllllll . US005208363A United States Patent [19] [11] Patent Number: 5,208,363 Crump et al. [45] Date of Patent: May 4, 1993 [54] PREPARATION OF AMINONITRILES 3,907,858 9/1975 Davis et a1. ....................... .. 558/346 3,925,448 12/1975 Tanier ................... .. 558/346 [75] Inv9nt9r$= B11199 K- Crumm Lake Jackson; 3,959,342 5/1976 Homberg et a1. ......... .. 558/346 Band A. W1lson, R1chwood, both of 3,988,360 10/1976 Gaudette et a1. .. 558/346 Tex. 4,022,815 5/1977 Schlecht 61 a1. 558/346 . 4,478,759 10/1984 Diatler C181. .. .558/346 [73] Asslgnee‘ “F D" @e'mcal Cmnpmy, 4,560,516 12/1985 Singer .......... ..' 558/346 M1d1and,M1¢h- 4,661,614 4/1987 M08161 61. .. 558/346 . 4,704,465 11/1987 Tannet et 111. ........ .. 558/346 [21] Appl' N°" 878’572 4,980,471 12/1990 Christiansen e181 ............ .. 544/384 [ 221 Fil e d: M “y 5’ 1992 OTHER PUBLICATIONS Related US. Application Data Stewart, et 81., J. Chem. Soc., pp. 3281-3285, (1940), [ 63 1 553333,?". _.Ma" _ “S” _ N° _ 597 , 625 , 0°‘ _ 15 , 199°’ V01.ChOh-HQO 62. Li, et aL, J. Chem. Soc., pp. 2596-2599, (1937), V01. 59. Céi5 .......................................... .. C07C5§33é2 Stewart, et 31“ J_ chem Soc” pp_ 27824737, (1933), n a O - . 6 . 6 3 . 6 . 0. vol. 60' I [58] Field of Search ....................................... .. 558/ 346 [56]‘ R f Cit‘ d Primary Examiner-Joseph Paul Brust e erences e U.s. PATENT DOCUMENTS :2] _ ‘ABS-“MCI f _ , e present 1nvent1on 1s a process or preparing 2,205,995 6/1940 Ulnch e181. ...................... .. 558/346 aminoacetonitdles or ethylenediamine tetraacetonimle 2,405,966 8/1946 Lode! ......... .. 558/346 . h f . l . d1 .h 2,407,645 9/1946 Bersworth ...... .. 558/346 ‘mmpilsmgt FS‘ePSO (64411111411188 ycoiomt 9W“ 2,731,490 1/1956 Barsky ....... .. 558/346 x an amme 111M118 at least 0118 p?mary amme group 01' 2,855,428 10/1958 Singer et a1. , .. 558/346 ethylenedlamme to form an mtermediate amine acetoni 2,860,164 11/ 1958 K1011 et a1. .... .. 558/346 X trile reaction product, (b) admixing the reaction prod 2,890,238 6/1959 Sexton ........... .. 558/346 x “ct ofstep (a) with formaldehyde and hydrocyanic acid such that each hydrogen on an amm' e nitrogen is re ’ ’ at?"ga“ “taile ' " ------ - placed by an acetonitrile group. The resulting 3,515,742 6/1970 Morgan 6181. .. 558/346 . t .t d1 d 1 h a“ . 3,644,444 2/1972 Popper et a1. 558/346 X amm°a°° 9m “5 “M39”, y as mm" gmups 3,679,729 7/1972 13661615 .......... .. 558/346 fully subsmuted “"111 acemmmle 81°11!” 3,714,223 1/1973 Godfrey 6161. 558/346 3,758,534 9/1973 Popper et a1. ..................... .. 260/429 28 Claims, N6 Drawings 5,208,363 1 2 nium hydroxide to achieve carboxymethylation of the PREPARATION OF AMINONITRILES amine. In Column 2, lines 48-51 of this patent, Kroll discloses previous reactions of glycolonitrile‘ with CROSS REFERENCE TO RELATED amines where reactions at primary amines are limited to APPLICATION reaction of the ?rst hydrogen on each nitrogen. This application is a continuation-in-part of applica SUMMARY OF THE INVENTION tion Ser. No. 597,625, ?led Oct. 15, 1990, now aban doned. The present invention is a process for preparing A'minonitriles are useful, for instance, in preparing amino acetonitriles comprising the steps of: (a) reacting aminocarboxylic acid compounds. For example, by contacting in a liquid aqueous reaction medium, at a ethylenediaminetetraacetonitrile can be hydrolyzed to basic pH and at a temperature of from about 0' C. to prepare ethylenediaminetetraacetic acid (EDTA). Pro about 70° C. glycolonitrile with an unsubstituted or cesses for the hydrolysis are known in the art, as exem inertly-substituted amine having at least one primary pli?ed by the teachings in U.S. Pat. Nos. 2,407,645; amine group to form an intermediate aminonitrile, (b) 2,164,781; and‘ 2,205,995. 15 placing the reaction product of Step (a) in a suitable Aminonitriles, also known as aminocarboxylic acid acidic liquid reaction medium at a temperature of from nitriles, have been prepared in a number of ways, often about 0” C. to about 90° C. and thereafter admixing it from certain amines reacted with certain carbonyl com with formaldehyde and hydrocyanic acid such that pounds, particularly formaldehyde and hydrocyanic each hydrogen on an amine nitrogen is replaced by an acid (hydrogen cyanide, HCN). For instance, U.S. Pat. acetonitrile group. No. 2,205,995 (Ulrich, et al.), a process involves a reac The insoluble, fully-substituted aminonitrile can be tion of certain amine salts with certain carbonyl com then saponi?ed using processes known in the art as pounds and hydrocyanic acid prepared from acidi?ed described in U.S. Pat. Nos. 2,407,645 (Bersworth), cyanide salts. Ethylenediaminetetraacetonitrile is 2,164,781 (Platz) and 2,205,995 (Ulrich) to form amino among the compounds prepared. Similarly, in U.S. Pat. 25 tetraacetic acid. No. 2,407,645, Bersworth discloses a process for prepar ing certain polycarboxylic amino acids from certain DETAILED DESCRIPTION OF THE aliphatic amines reacted with formaldehyde and an INVENTION alkali metal cyanide. In U.S. Pat. No. 4,855,428, Singer Amines suitable for the process of the invention are teaches yet another process in which certain amines are amines having at least one primary amine group. The fed into a reaction medium containing formaldehyde ' amines preferably have from about 2 to about 20 carbon and hydrocyanic acid. The medium is acidi?ed and atoms and preferably have at least about 2 amine remains liquid. In U.S. Pat. No. 3,424,783 Harper et al. groups, more preferably from about 2 to about 4 amine teach reacting an amine with formaldehyde and hydro groups. Of these amine groups, at least one is primary, cyanic acid in the presence of an aqueous slurry of 35 preferably at least 2 are primary, most preferably about acidic ionic exchange resin to produce certain aminoni 2 amine groups per molecule are primary amine groups. triles. In U.S. Pat. Nos. 3,463,805 and 3,515,742 Morgan et al. emphasize characteristics of adiabatic conditions The amine preferred for this process is ethylenedi in reacting certain amines with formaldehyde and hy amine (EDA), while other amines may be used. Amines drocyanic acid in the presence of certain acidic catalyst. are commercially available or may be prepared by pro More recently, in U.S. Pat. No. 4,478,759, Distler et al. cesses within the skill in the art such as by 1) the reac disclose a process for reacting certain nitrogen com tion of ammonia with alkyl halides (with and without pounds with formaldehyde and hydrocyanic acid in the catalysts), 2) catalytic amination of alcohols or amino presence of additional acids such that the pH is less than alcohols, or 3) catalytic reduction of nitriles. about 2 and temperatures are from about 10° C. to about 45 The amines are unsubstituted or inertly substituted, 70° C. The concentration of hydrocyanic acid is con that is, substituted with groups which do not undesir trolled carefully. In U.S Pat. No. 4,704,465 Lannert et ably interfere with the reaction steps of the invention. al. disclose a process for combining formaldehyde with Such inert substitution includes, for instance, hydroxy ethylenediamine under certain conditions. A two-stage alkyl groups, carboxylic acid groups, sulfonic acid process is taught in U.S. Pat. No. 4,560,516 (Singer). 50 groups, and phosphonic acid groups. However, substi Other disclosures of reactions of certain amines with tution is generally not desirable since the solubility in formaldehyde and hydrocyanic acid include, U.S. Pat. water may be increased. Increased solubility impairs Nos. 3,644,444 (Popper et al.); 3,679,729 (Daniels); isolation of the nitrile product. 3,714,223 (Godfrey et a1); 3,758,534 (Popper eta al.); and The amine is admixed with glycolonitrile which is 3,988,360 (Gaudette et al.). Additionally, formaldehyde commercially available and is obtained by the reaction and hydrocyanic acid are reacted with ammonia to of HCN with formaldehyde which is within the state of produce nitrilotriacetonitrile by processes such as those the art such as illustrated by U.S. Pat. Nos. 2,731,490 disclosed in U.S. Pat. Nos. 3,907,858 (Davis et al.); and 2,890,238. 3,925,448 (Lanier) and 3,959,342 (Homberg et al.). Preferred ratios of glycolonitrile to amine in the ?rst In some instances glycolonitrile (also known as step depend on the amine. For example, with ethylene glyconitrile and hydroxyacetonitrile) has been reacted diamine (EDA), the most preferred ratio isone mole of with amines. For instance, in U.S. Pat. No. 2,861,164 EDA to 1.9 to 2.0 moles of glycolonitrile. In the case of Kroll discloses certain carboxymethylations of certain diethylenetriamine, about 2.8 to 3.0 moles of glycoloni amines by reacting glycolonitrile with primary or sec trile are most preferably used with one mole of the ondary amines in an aqueous solution at temperatures 65 amine. In general, the amount of glycolonitrile used is greater than about 85° C. to the boiling point of the preferably less than or equal to an equivalent amount mixture in the presence of basic hydroxides of alkali based on primary and secondary amine nitrogens of the metals or alkaline earth metals or quaternary ammo amine. A primary amino group will accept one 5,208,363 3 4 glycolonitrile addition, but under the preferred condi least one secondary amine hydrogen remaining avail tions for the reaction a second acetonitrile group is not able for subsequent reaction.
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