United States Patent [191 [11] 4,233,220 Kvita et a1. [45] Nov. 11, 1980 [54] IMIDYL-BENZENE-DICARBOXYLIC AND 3,465,002 9/ 1969 Bolhofer et a1. .............. .. 260/326.41 -'I“RICARBOXYLIC ACID DERIVATIVES 3,538,114 11/1976 l-limmele et a1. .. 260/326.5 FM 3,549,657 12/1970 Webster ......................... .. 260/326 A [75] Inventors: Vratislav Kvita, Muttenz; Roland 3,549,725 12/1970 Rose ........................ .. 260/326.5 FM Dar-ms, Therwil; Gerd Greber, 3,557,132 1/1971 Hermann et al. ........ .. 260/326.5 FM Binningen, all of Switzerland 3,660,408 5/1972 Ackerman ............... .. 260/326.5 FM 3,666,720 5/1972 Nield et a1. ................ .. 260/326 N [73] Assignee: Ciba-Geigy Corporation, Ardsley, ‘ 3,766,142 10/ 1973 Nield et a1. .............. .. 260/326.5 FM N.Y. 3,816,451 6/1974 Crovetti et a1. ......... .. 260/326.5 FM 3,878,224 4/1975 Matsui et a1. .................. .. 260/326 R [21] Appl. No.: 951,432 3,892,802 7/1975 Podesua et a1. .......... .. 260/326 A [22] Filed: Oct. 16, 1978 3,948,941 4/ 1976 Patton ............ .. .. 260/326.5 FM 3,979,393 9/1976 Kvita et a1. ................ .. 260/326 C Related US. Application Data 3,984,435 10/1976 Matsui et al. ...... .. .. 260/326.5 FM 4,043,986 8/1977 Gruffay et a1. ..... .. 260/47 UA [62] Division of Ser. No. 696,348, Jun. 15, 1976, Pat. No. 4,107,174 8/1978 Baumann et al. 260/326 N 4,132,716. , 4,126,619 11/1978 Darms et al. ...... .. 260/326 N [30] Foreign Application Priority Data 4,134,895 1/ 1979 Roth et a]. .................... .. 260/326.26 FOREIGN PATENT DOCUMENTS Jun. 18, 1975 [CH] Switzerland ....................... .. 7953/75 1594934 7/ 1970 France ......................... .. 260/326.5 FM [51] Int. 01.3 ................. .. c071) 403/02; com 405/02 [52] us. (:1. ........................ .. 260/326.26; 260/326 A; Primary Examiner—Mary C. Lee 260/326 c; 260/326 N; 260/326.27; Attorney, Agent, or Firm-Luther A. R. Hall 260/376.29; 260/326.41; 260/326.5 FM; [57] ABSTRACT 260/326.5 B; 260/326.5 c; 260/326.34; 526/236 New imidyl-benzene-dicarboxy1ic and -tricarboxy1ic [58] Field of Search .................... .. 260/326.4l, 326.34, acid derivatives, in particular S-maleimidyl-trimellitic 260/326.43, 326.5 FM, 326.26, 326 A, 326 C, acid derivatives and 3,S-bis-(maleimidyl)-phthalic acid 326 N derivatives, and a process for their manufacture are [56] References Cited described. These imidylbenzene-dicarboxylic and -tri carboxylic acid derivatives are suitable for the manufac U.S, 'PATENT DOCUMENTS ture of crosslinkable polymers, above all polycondensa 2,726,981 12/1955 Wolf et a1. ............... .. 260/326.5 FM tion and polymerization products, which are distin 2,962,504 l1/1960 Walker et a1. 260/326.5 FM guished by good processability and good solubility in 2,971,944 2/ 1961 Chow . .. 260/326.26 customary organic solvents. Imidyl compounds, ac 2,980,694 4/1961 Sauers ................... .. 260/ 326.26 cording to the definition, which have anhydride groups 3,039,860 6/1962 Andress et al. 260/326.41 can also be used as curing agents for optionally modi 3,078,228 2/ 1963 Smith . .. 260/326 A 3,397,210 8/ 1968 Michalowicz . 260/326.5 FM ?ed epoxide resins. 3,445,477 5/1969 Miiller et a1. .. 260/326 N 3,465,001 9/1969 Bolhofer et a1. .............. .. 260/326.41 4 Claims, No Drawings 4,233,220 1 IMIDYL-BENZENE-DICARBOXYLIC AND -TRICARBOXYLIC ACID DERIVATIVES in at least the stoichiometric amount with an anhydride This is a Divisional of application Ser. No. 696,348 of the formula III ?led on June 15, 1976, now US. Pat. No. 4,132,716, issued on Jan. 2, 1979. (in) The present invention relates to new imidyl-benzene dicarboxylic and -tricarboxy1ic acid derivatives and a process for their manufacture. C The new imidy]-benzene-dicarboxylic and -tricarbox II o ylic acid derivatives correspond to the formula I to give a compound of the formula IV [HOOC-A-CO-Nl-Ih-Z’ (IV) N Z wherein A and n have the meaning indicated under C | formula I and, when n: 1, Z’ denotes a radical of the 0 n formula 20 wherein A denotes‘ a radical of the formula COR4' 011mm and, when n=2, Z’ denotes a radical of the formula R1 and R2 independently of one another denote hydro gen, chlorine or bromine, n denotes the number 1 or 2 COR4' and, when n=‘l, Z denotes a radical of the formula COR4' R3OC COR4 wherein R4’ denotes a hydroxyl group, an unsubstituted COR4 phenoxy group or a substituted phenoxy group which is free from electronegative substituents, an alkoxy group and, when n=2, Z denotes a radical of the formula with l-l8 carbon atoms or a —O-M+ group, and, when R4’ represents a phenoxy or alkoxy group accord ing to the de?nition, R3’ denotes a hydroxyl group, an COR4 unsubstituted phenoxy group or a substituted phenoxy group which is free from electronegative substituents, an alkoxy group with 1-18 carbon atoms or a —O—M+ COR4, 45 group and, when R4’ represents a hydroxyl group, R3’ denotes a hydroxyl group or a phenoxy or alkoxy group R4denotes a hydroxyl group, an unsubstituted or substi according to the de?nition and, when R4’ represents a tuted phenoxy group, an alkoxy group with l-18 car —O-M+ group, R3’ denotes a —O-M+ group or a bon atoms or a --O—M+ group, or the two R4s con phenoxy or alkoxy group according to the de?nition jointly denote the —O- grouping and, when R4 repre 50 and M+ has the meaning indicated under formula I, sents an unsubstituted or substituted phenoxy group or subsequently cyclising the compound of the formula IV an alkoxy group with 1-18 carbon atoms, or the two and optionally converting the resulting compound of R4s conjointly represent -—O—, R3 denotes a chlorine the formula I into another derivative, according to the atom, a hydroxyl group, an unsubstituted or substituted definition, of the formula I. phenoxy group, an alkoxy group with 1-18 carbon 55 Preferably, A represents a radical of the formula atoms or a —O—M+ group and, when R4 represents a hydroxyl group, R3 denotes a hydroxyl group, an un substituted or substituted phenoxy group or an alkoxy group with l-l8 carbon atoms and, when R4 represents a —O*M+ group, R3 denotes a —O—M+ group, an unsubstituted or substituted phenoxy group or an alk oxy group with 1-18 carbon atoms and M+ denotes an and especially a radical of the formula -—CH—_—CH—-. If alkali metal cation, a trialkylammonium cation with R3, R3’, R4 or R4’ represent substituted phenoxy groups, 3-24, and especially 3-12, carbon atoms or a quaternary the latter are, in particular, phenoxy groups which are ammonium cation. 65 substituted by nitro groups or alkyl or alkoxy groups The new imidyl-benzene-dicarboxylic and -tricarbox with l or 2 carbon atoms or by halogen atoms, above all ylic acid derivatives can‘ be manufactured, according to chlorine or fluorine, such as the 2-, 3- or 4-nitrophenoxy the invention, by reacting an amine of the formula II group, the 2,4- or 3,5-dinitrophenoxy group, the 3,5 4,233,220 3 4 dichlorophenoxy group, 'the pentachlorophenoxy anhydride, 2,3-dibromomomaleic anhydride, 4- and group or the 2-methyl- or 2-methoxy-phenoxy group. 2-cyclohexene-1,2-dicarboxylic acid anhydride, 3,6 According to the de?nition, substituted phenoxy endomethylene-1,2,3,6-tetrahydrophthalic anhydride groups R3’ and R4’ are free from electronegative substit (nadic anhydride) and 3,6-endoxo-l,2,3,6-tetrahydroph uents, such as nitro groups or halogen atoms. End prod- 5 thalic anhydride. Nadic anhydride and, above all, ma ucts of the formula I, wherein R3 and/or R4 deote phe leic anhydride are preferably used. noxy groups which contain electronegative substituents The reaction of the amines of the formula II with the of this type, are appropriately manufactured-—as indi cated further below—from the corresponding anhy anhydrides of the formula III can be carried out in the drides, acid anhydrides or acid chloride-anhydrides or melt, by heating the reactants to temperatures of up to by trans-esteri?cation. about 150° C., or in an aqueous, aqueous-organic or Alkoxy groups R3, R3’, R4 or R4’ can be straight organic medium, in which case the reaction is appropri chain or branched. Examples which may be mentioned ately carried out at temperatures between about 0° C. are: the methoxy, ethoxy, n-propoxy, isopropoxy, n and 50° C., especially between about 15° C. and 25° C. butoxy, tert.butoxy, hexyloxy, octoxy, decyloxy, Appropriately, the anhydride of the formula III is dodecyloxy, tetradecyloxy and octadecyloxy group. employed in the stoichiometric amount or in a slight If R3, R3’, R4 or R4’ denote a —O-M+ group, M+ excess over the amine of the formula II, for example in represents, for example, the lithium, sodium, potassium, an up to about 20% molar excess. The reaction is advan trimethylammonium, triethylammonium, methyl-die tageously carried out in an organic medium. Organic thylammonium, tri-n-octylammonium, benzyltrime solvents which can be used are, above all, aprotic or thylammonium or tetramethylammonium cation. M+ ganic solvents. Examples of suitable aprotic organic preferably represents the sodium cation. solvents are: optionally chlorinated aliphatic or aro Compounds of the formula I wherein A represents matic hydrocarbons, such as benzene, toluene, methy the radical lene chloride, chloroform, carbon tetrachloride, 1,1,2 25 trichloroethane, 1,2-dichloroethylene and chloroben zene; aliphatic and cycloaliphatic ketones, such as ace tone, methyl ethyl ketone, cyclopentanone and cyclo hexanone; cyclic ethers, such as tetrahydrofurane, tet rahydropyrane and dioxane; cyclic amides, such as N .