Patent Publication Number: US-3880859-A

Title: N-substituted-4-alkoxynaphthalimides

Description:
United States Patent Scheuermann et al.  
 I 1 N-SUBSTITUTED- -t- ALKOXYNAPHTHALIMIDES [75] Inventors: Horst Seheuermann, Ludwigshufen;  
 Peter-Matthias Hell, Frunkenthal. both of Germany [73] Assignee: Badische Anilin- &amp; Soda-Fabrik Aktiengesellschaft. Ludwigshufen (Rhine). Germany [22] Filed: May 30. I972 [21] Appl. No.: 258,060  
 [30] Foreign Application Priority Data June 3. I97] Germ-tin 2l27522 Sept. 24. I&#39;-)7| German M47706 {52] U.S. Cl 260/281; 8/I W; 260/242; 260/247! L; 260/2472 R&#39;. 260/268 TR; 260/270 B [Sll Int. Cl C07d 39/00 [58] Field of Search H 260/281; 252/3012 W [56] References Cited UNITED STATES PATENTS 123L495 2/l94l Eckcrs 260/28l 3.3l2.7(l6 4/1967 Rigterink 260/28l 3.330.834 7/1967 Senshu 260/28l 3.357.985 l2/l967 Fuchs et ul. 260/28l 3.367.937 2/[968 Fuchs et all 260/28I 3.502.678 3/l970 Fuchs 26U/28l FOREIGN PATENTS OR APPLICATIONS 45-774 5/1970 Japan 260/28l 45 367l lU/l970 Japan 260/28l 45-34438 5/]970 Jupun 26(l/28l Primary E.\&#39;uminerDonald G. Daus Auurney. Agent. or Firm-Johnston. Kcil. Thompson &amp; Shurtleff 4 Claims, N0 Drawings 1 N-SUBSTITUTED-S-ALKOXYNAPHTHALIMIDES The invention relates to compounds of the general formula (I):  
 in which R is substituted alkyl. unsubstituted or substituted cycloalkyl. aralkyl or heteroalkyl and R&#39; is alkyl or alkyl bearing alkoxy as a substituent.  
  Examples of substituted alkyls R are linear or branched groups of up to eight carbon atoms which may be interrupted by oxygen. NH or sulfur and may bear cyano, chloro, bromo. alkoxy. aroxy, carbalkoxy, carbamoyl, N-substituted carbamoyl arylamino, dialkylamino quaternary ammonium or tertiary sulfonium as substituents. Cycloalkyls R may bear alkyl as a substituent and aralkyls R may bear the substituents specified for alkyl and also N-suhstitutcd sulfonamido as substituents.  
  Hcteroalkyls may bear for example alkyl of one to four carbon atoms. cyano or carbalkoxy of up to five carbon atoms as substituents.  
 in particular R may be where Z is hydrogen alkanoyl of two to eight carbon atoms. acetyl bearing chloro. phenyl. hydroxy, phenoxy or methoxy as a substituent benzoyl, benzoyl bearing chloro, methyl or methoxy as substituent. thenoyl or a radical of the formula R NHCO- or R&#34;O- (O-z 5 R&#34; is methyl. ethyl, n-propyl, isopropyl. phenyl, chlorophenyl. dichlorophenyl or methylphenyl; R is alkyl of one to eight carbon atoms, alkoxyalkyl of three to six carbon atoms. cyclohexyl, benzyl, phenylethyl. or unsubstituted or substituted phenyl; A is hydrogen. methyl. phenyl or a radical of the formula CH- R; R is hydroxy. alkoxy of one to eight carbon atoms. Hmethoxyethoxy. fi-ethoxyethoxy, B-butoxyethosy. phcnoxy, phenosy bearing chloro methyl or methosy as substituents phenylmercapto. methoxyphenylmercapto or a radical of the formula R is alkyl of one to four carbon atoms or B-hydroxy c a oc a coma CEHAN CZHMJ.\ /O,  
 (T HNHWH Continued The following examples are also suitable: cyclohexyl,  
 mcthylcyclohexyl, cyclooctyl, henzyl. /3-phenylethyl,  
 p-cl&#39;ilorohcnzyl. p-mcthylbenzyl. p-ethylbenzyl, p  
 methoxybenzyl. p-carbomethoxyhenzyl and pcyanobenzyl, 2,4-dimethylhenzyl. Z-methyl-S-carhomethoxyhenzyl, p-carboxamidobenzyl, p-  
 sulfamidohenzyl and the radicals of the formulae:  
  I and the radicals: CH CH Moreover, for example radicals R containing sulfonium groups are suitable:  
 , C H SC and  NH s c 2 e Examples of counterions (anions) for the ammonium and sulfonium radicals are chloride, bromide. iodide, sulfate. methosulfate, ethosulfate, benzenesulfonate and toluenesulfonate.  
 The following are specific examples ofR&#39;: propyl, bu-  
  Radicals R which contain basic nitrogen and also the quaternized radicals derived therefrom are of particular significance. The following are given as examples:  
 B is alkyl of one to four carbon atoms or C H OH and X is methyl, ethyl, phenyl or henzyl,  
 tyl, butoxyethyl. ethoxyethyl and methoxyethyl and particularly methyl and ethyl.  
  in addition to those already specifically mentioned, the following radicals are suitable for Z, R, R, R and S for R methoxy. ethoxy. n-propoxy, isopropoxy. nbutoxy. isobutoxy, hexoxy and B-ethylhexoxy; for R and R&#34;: methyl. ethyl and butyl.  
  Compounds of the general formula (la) have special industrial importance:  
 in which Y is a nitrogenous alkylatable radical. a quaternized radical. a radical containing sulfonium groups or a radical of the formula:  
 in which Z is hydrogen. alkanoyl of two to eight carmay for example be carried out for the production of the new compounds. Hal is bromine or preferably chlorine.  
 mula (I). a compound of the formula (11):  
  on N 0 Hal may be reacted with an epoxide of the formula (III (III) in which D is hydrogen. methyl or phenyl in an alcohol of the formula: ROH in which R has the above meanings to form a compound of the formula:  
 OCH  
 l and the radical converted into a radical R.  
  In the reaction of the compound of the formula (II) with a large excess of up to 1009? of the epoxide of the formula (III) in an alcohol of the formula ROH. it is surprisingly often possible to exchange the halogen for OR simultaneously with the introduction of the radical wa ers-ea.  
  The reactions are known in principle and proceed analogously in comparable conditions. Details may be found in the Examples.  
  Parts and percentages in the following Examples are by weight unless otherwise specified.  
  )R O N O EXAMPLEI 28.7 parts of 4-methoxy-N-(B-hydroxyethoxy)- naphthalimide and 23.4 parts of p-toluenesulfochloride U are heated for 7 hours at from to C in 100 parts of o-dichlorobenzene and allowed to cool. 200 parts of methanol is added and the product is suction filtered. washed with methanol and recrystallized from toluene. 22.5 parts (74% of theory) of 4-methoxy-N- (B-chloroethoxy)-naphthalimide is obtained having a melting point of 190 to 192C.  
  4-methoxy-N-(B-hydroxyethoxyl-naphthalimide is prepared as follows: 24.8 parts of 4-chloro-N- hydroxynaphthalimide is suspended in 250 parts of methanol and then 30 parts of triethylamine is added. After heating for half an hour at 45 to 50C the whole is filtered and then 13.5 parts of ethylene oxide is passed into the filtrate at 50 to 60C. The whole is then heated under reflux for 6 hours and allowed to stand for 12 hours. The product is suction filtered. washed with methanol and dried. 19.5 parts (687! of theory) of a pale yellow compound is obtained which melts at from 183 to 185C.  
 EXAMPLE 2 16 parts of hydrogen bromide is passed into 180 parts of benzene and then 28.7 parts of 4 methoxy-N-(/3 hydroxyethoxyl-naphthalimide and 2 parts of pyridine are introduced. Whilst continuing to pass hydrogen bromide in. the suspension is stirred at to C for 6 hours, cooled and suction filtered, and the residue is suspended in 500 parts of water and neutralized with sodium carbonate. After suction filtration and drying. 32 parts (927: of theory) of 4-methoxy-N-(B- bromoethoxy)-naphthalirnide is obtained having a melting point of 166 to 168C. After the compound has been recrystallized from 90% acetic acid it melts at 167 to 169C.  
 EXAMPLE 3 A mixture of 350 parts of 4-methoxy-N-(B- bromoethoxy)-naphthalimide. 150 parts of chlorobenzcne and 42.5 parts of piperidine is heated for 7 hours at 80C, then cooled and the product is precipitated with petroleum ether and suction filtered. For further purification the filter cake is stirred into 1000 parts of water. again suction filtered and dried. After recrystallization from cyclohexane. 23.5 parts (66% of theory) of 4-methoxy-N-(B-piperidinoethoxy l-naphthalimide having a melting point of 126 to 128C is obtained.  
  In a manner analogous to Example 3. the following 4-methoxynaphthalimide derivatives are prepared:  
 and, after adding 54 parts of a 30&#39;?! solution of sodium methylate in methanol. is heated for nine hours at to C. The whole is allowed to cool, and the product suction filtered. washed with methanol and water. and recrystallized from ethanol. 145 parts (417: of theory) of 4-methoxy-N-(fi-morpholinoethoxy)-naphthalimide is obtained having a melting point of 149 to 150C.  
  4&#39;ch1oro-N-(B-morpholinoethoxy)-naphthalimide is prepared as follows.  
  40 parts of triethylamine is added to a mixture of 248 parts of 4-chloro-N-hydroxynaphthalimide and 300 parts of methanol and the whole is heated for half an hour at 45 to 50C and filtered. The filtrate has a mixture of 44 parts of ,B-morpholinoethyl bromide hydrobromide and 150 parts of methanol added to it gradually at 20 to 25C. The whole is heated under reflux for 12 hours and suction filtered after it has cooled. The product is washed with methanol and dried. The yield is 14.3 parts (40% of theory). It has a melting point of 138 to 140C. After the compound has been recrystallized from methyl glycol it melts at 141 to 143C.  
 EXAMPLE [3 16 parts of benzylamine is added to a suspension of 15 parts of 4-methoxy-N-( fi-bromoethoxy naphthalimide in 50 parts of chlorobenzene and the whole is heated for 5 hours at to C. and then e-c11 c11 -B o \\/N s o b t/H5 Example B Melting point a w sa 118 1; 122  
  r \i L, j 0 C 5 0 1 18 to 150C 6 41;] 80 to 81C 7 -NH-@ 158 to 1 10 0 8 4y 215 to 217% CH -c11 -OH 9 N 2 2 125 to 1260C c11 -c11 o11 c H 10 -N/ 2 5 63 to 66C c H 11 -N/ 9 11 to 117C EXAMPLE 12 S The compound described in Example 5 may also be 6 prepared as follows.  
  36.1 parts of 4-ch1oro-N-(B-morpholinoethoxy)- naphthalimide is suspended in 250 parts of methanol cooled. parts of water is added, the benzene phase is separated and 200 parts ofligroin is added to it. After stirring for one hour. the semicrystalline precipitate is suction filtered. suspended in 100 parts of water and acidified with 25 parts of concentrated hydrochloric acid. After stirring for 2 hours. the colorless crystalline precipitate is suction filtered and dried. I 1 parts of 4- methoxy-N-l B-benzylaminoethoxy )-naphthalimide hydrochloride (627: of theory) is obtained having a melting point of 233 to 235C.  
 EXAMPLE 14 306 parts of 4-chloro-N-(B-methoxyethoxy)- naphthalimide is suspended in 300 parts of methanol. 70 parts of a 30% solution of sodium methylate in methanol is added and the whole is heated at 60 to 65C for 6 hours. After cooling. the product is suction filtered, washed with methanol and water and the dried product is recrystallized from toluene. 19.8 parts (659? of theory) of 4-methoxy-N-(B-methoxyethoxy naphthalimide having a melting point of 183 to 184C is obtained.  
  The 4-chloro-N-( B-methoxyethoxy )-naphthalimide required as starting material is prepared as follows: 248 parts of 4-chloro-N-hydroxynaphthalimide is suspended in 400 parts of methanol and after 21 parts of triethylamine has been added the whole is heated for half an hour at 45 to 50C. The solution is filtered and 35 parts of ,B-methoxyethyl p-toluenesulfonate is dripped into the eluate. The whole is then heated for 10 hours under reflux. allowed to cool and the product which is deposited is suction filtered and washed with methanol. The yield is 22.0 parts (72% of theory). The compound melts at 95 to 97C.  
 EXAMPLE 7.7 parts of sodium is added to 250 parts of methyl glycol followed by 30.6 parts of 4-chloro-N-(B- methoxyethoxy)-naphthalimide. The solution is heated for thirteen hours at 90 to 110C. allowed to cool. poured into 1500 parts of water. neutralized with hydrochloric acid and stirred for another 2 hours. The product is suction filtered. washed with water and dried. For purification. the product is extracted with hot toluene and. after concentration of the extract. is suction filtered. 19.0 parts (627: of theory) of 4-(8- methoxyethoxy)-N-(B-methoxyethoxy)-naphthalimide having a melting point of 192 to 194C is obtained.  
 EXAMPLE 16 In a manner analogous to that described in Example 14. 32.0 parts of 4-chloro-N-lB-ethoxyethoxy)- naphthalimide is reacted The crude product is recrystallized from isopropanol. 16.0 parts (51% of theory) of 4methoxy-N-(B-cthoxyethoxy)-naphthalimide is obtained which has a melting point of 87 to 89C.  
  4-chloro-N-tB-cthoxyethoxy)-naphthalimide is obtained as described in Example 14 from 4-chloro-N hydroxynaphthalimide by reaction with ,B-ethoxyethyl p-toluenesulfonate. The compound melts at 68 to 71C.  
 EXAMPLE 17 70 parts of a 30% solution of sodium methylate in methanol is added to 36.8 parts of 4chloro-N-(B- phenoxyethoxy) naphthalimide which has been sus pended in 250 parts of methanol. The whole is heated for 6 hours at 60 to C and the cooled suspension is suction filtered and the product is washed with methanol and water. dried and recrystallized from butanol. 23.5 parts (65% of theory) of 4-methoxy-N-(B- phenoxyethoxyl-naphthalimide is obtained having a melting point of 133 to 134C.  
  4-chloro-N-( ,B-phenoxyethoxy )-naphtha1imide is obtained as follows: 40 parts of triethylamine is added to 49.5 parts of 4chloro-N-hydroxynaphthalimide in 600 parts of methanol and 48 parts of B-phenoxyethyl bromide is dripped in at 60 to 65C. After heating for three hours under reflux. the whole is cooled and the precipitate is suction filtered and dried. 54 parts (747r of theory) of 4-ch|oro-N-(B-phenoxyethoxy)- naphthalimide having a melting point of 159 to 161C is obtained.  
 EXAMPLE 18 50 parts of a 30% solution of sodium methylate in methanol is added to a suspension of 33.8 parts of 4- chloro-N-benzyloxynaphthalimidc in 120 parts of methanol. After the mixture has been heated for 5 hours at 65 to C it is cooled. 200 parts of water is added and it is acidified with glacial acetic acid. The precipitate is stirred for one hour. suction filtered. washed with water and methanol and dried followed by recrystallization from methyl glycol. 27.6 parts (83% of theory) of 4-methoxy-N-benzyloxynaphthalimide having a melting point of 161 to 162C is obtained.  
 EXAMPLE 19 33.8 parts of 4-chloro-N-benzyloxynaphthalimide is added to a solution of 9.2 parts of sodium in 150 parts of methyl glycol prepared at 60 to 70C and the mixtures is heated for nine hours at to C. After cooling. 300 parts of water is added and the whole is acidified with 50 parts of glacial acetic acidv The precipitate is suction filtered, washed with water and methanol. recrystallized from methyl glycol and dried. 27.1 parts of 4-B-methoxyethoxy-N-benzyloxynaphthalimide having a melting point of 200 to 201C is obtained.  
 EXAMPLE 20 54 parts of a 30% sodium methylate solution is added to 47 parts of 4-chloro-N-(pdiethylaminosulfonylbenzyloxy)-naphthalimide in 500 parts of methanol and the whole is then heated at the boil for six hours. Suction filtration is carried out after cooling and the filter cake is washed with methanol and water and dried. 41 parts of 4-methoxy-N-(pdiethylaminosulfonylbenzyloxyJ-naphthalimide having a melting point of 172 to 174C is obtained.  
  Analogously to Example 20. the following naphthalimide derivatives are obtained:  
  we N 0 con Example R Melting point /CH O 21 SO2N\ 168 to 169 c ca -CH -0a ca -ca -0a 22 SO2N 2 2 152 to 154C CH2CH2-OH 2 so a o 216 to 21 c 2 U 7 EXAMPLE 24 30 parts of ethyl acrylate is dripped at 60 to 70C into 287 parts of 4-mcthoxy-N-(B-hydroxyethyl)- naphthalimide in 150 parts of glacial acetic acid and the whole is then heated for 24 hours at 80 to 90C. The solvent is then distilled off at subatmospheric pressure and the residue is recrystallized from a small amount of methyl glycol. parts (529? of theory) of 4-methoxy-N-l [Bl ,8&#39;-carboethoxyethoxy )ethoxy naphthalirnide is obtained having a melting point of 134 to 137C.  
 EXAMPLE 25 46 parts of a solution of sodium methylate is added to 29 parts of 4-chloro-N-(1&#39;-methy1imidazolyl- [2&#39; )-methoxy )-naphtha1imide in 400 parts of methanol. The mixture is heated for 5 hours at 60 to 65C and cooled. The precipitate is suction filtered, washed with water and methanol and dried. 18 parts (63% of theory) of 4-mcthoxy-N-11&#39;-methy1imidazolyl-(2&#39;)- methoxy )-naphtha1imide having a melting point of 245 to 246C is obtained.  
  The 4-chloro compound is obtained in a yield of 7292 from 4-ch1oro-N-hydroxynaphthalimide and l-methyl- Z-chloromethylimidazole hydrochloride in the presence ofequimolar amounts of triethylaminc in solution in methanol. The compound melts at 176 to 178C.  
 EXAMPLE 26 40.5 parts of a 3091 solution of sodium methylate is added to a suspension of 283 parts of 4-ch1oro-N- lbenzimidazolyl-(Z&#39;))-methoxynaphthalimide in 100 parts of methanol and the whole is boiled for 5 hours. After cooling. the product is suction filtered. washed with methanol and water and recrystallized from odiehlorobenzcne. 19 parts (689? of theoryl of 4- methoxy-N-(benzimidazolyH2&#39;1) methoxynaphthalimide is obtained having a melting point of 188 to 190C.  
 EXAMPLE 27 4-methoxy-N-l l&#39;-phenylpyrazolyl-(4 )-methoxy)- naphthalimide is prepared by analogy to Example 26.  
 The compound is recrystallized from methyl glycol and then has a melting point of 192 to 194C.  
 EXAMPLE 28 30 parts of hydrogen bromide is passed into 300 parts of benzene and then 30.1 parts of 4-methoxy-N-(B- hydroxypropoxy)-naphtha1imide and 2 parts of pyridine are introduced by the method of Example 2. While continuing to pass in hydrogen bromide. the whole is heated for 24 hours at C. After cooling, the whole is filtered and the filtrate has 300 parts of petroleum ether added to it. The product precipitated is suction filtered. suspended in 500 parts of water, neutralized with sodium carbonate, suction filtered and dried. 32.5 parts (89% of theory) of 4-methoxy-N-(B- bromopropoxy)-naphtha1imide is obtained having a melting point of 127 to 129C.  
  The 4-methoxy-N-tB-hydroxypropoxy naphthalimide required as starting material is prepared analogously to Example 1 from 24.8 parts of 4ch1oro- N-hydroxynaphthalimide and 17.5 parts of propylene oxide. 20.2 parts (67% of theory) ofa pale yellow compound is obtained which melts at 168 to 170C.  
 EXAMPLE 29 A mixture of 36.4 parts of 4-methoxy-N-(B- bromopropoxy)-naphthalimide, 39 parts of piperidine and 100 parts of methyl glycol is heated at 80C for 9 hours, cooled. 500 parts of water and 50 parts of sodium chloride are added and the whole is allowed to stand for 5 hours. After decanting, the precipitiated product is washed with water and recrystallized from cyclohexane after drying. 24.5 parts (66% of theory) of 4-methoxy-N-(B-piperidinopropoxy)-naphtha1imide having a melting point of 101 to 103C is obtained.  
 EXAMPLE 30 2.5 parts of sodium is dissolved in parts of ethanol and then 1 1 parts of thiophenol and 35 parts of 4&#39; methoxy-N-(B-bromoethoxy)-naphthalimide are introduced. The mixture is heated for 10 hours under reflux. cooled. and the residue from suction filtration is washed with water and dried. The product is recrystallized from toluene. 17 parts (45% of theory) of 4- methox -N-( ,B-phenylmercaptoethoxy )-naphthalimide is obtained having a melting point of 109 to l 11C.  
 EXAMPLE 3 l As described in Example 30 4-methoxy-N-(B- hydroxyethylmercaptoethoxy)-naphthalimide is pre pared from 4-methoxy-N-lB-hromoethyl)naphthalimide and B-mercapto-ethanol. 34.7 parts of this com pound is dissolved in 500 parts of acetone and 25 parts of dimethyl sulfate is added. The mixture is heated for 5 hours at 60C, allowed to cool and suction filtered. The filter residue is dissolved in 250 parts of water and the filtered solution has 13.6 parts of zinc chloride added to it. After salting out with sodium chloride, the  
  14 EXAMPLE 33 8 parts of pyridine is added to 29 parts of 4methoxy- N-(B-bromoethoxy)-naphthalimide in lOO parts of chlorobenzene. The whole is then heated for 8 hours at 5 80 to 90C, allowed to cool, suction filtered. and the residue washed with petroleum ether and dried. 24 parts (67% of theory) of the compound of formula:  
 precipitate is suction filtered and dried. 382 parts 15 (72% of theory) of the compound of the formula:  
  K e k huil CH -LH CH OH OCH 9 ZnC 1 2 i is obtained having a melting point of 213 to 117C.  
 OCH 2 35 EXAMPLE 34 6.5 parts of dimethyl sulfate is dripped into [2 parts of 4methoxy-N-(B-morpholinoethoxyJ-naphthalimide Obtained which Ctmlilms 0f sodlum Chlorldfl in 150 parts of acetone and the whole is boiled for 5 hours allowed to cool suction filtered and the residue 3 EXAMPLE u washed with a small amount of petroleum ether and in Example 31 fi&#39;mcrcapmclhflnol 15 replaced y dried. l4 parts (77% of theory) of the compound of the ethyl thioglycolate. 4-methoxy-N-(B- f l carboethoxymcthylmercaptoethox )-naphthalimide being obtained. 38.9 parts of this compound is dissolved in 700 parts of acetone and parts of dimethyl sulfate is added and the whole is heated for 20 hours at 60C. After cooling. the precipitate is suction filtered. O-CH -CH N O CH 50&#39; e washed with acetone and dried. 35 parts (68% of the- L, 2 2 3 Ll ory) of a sulfonium salt is obtained having a melting O 5 point of 159 to 160C and the formula:-  
 O CH CH (EH3 2 i CH CO0C H OCH N O 3 9 CH SO is obtained. It melts at 201 to 203C. OCH 59 The following compounds may also he obtained by 3 the method of Example 34.  
 (3-H e N o C 5 Example R X Meltin point eit so to 167C Continued Example a x l-l+ :l Lint; enal 36 CH QCIIHQ-CHQ-OH 2 CH2 1:! CH2 CHE-OH ca so 202 to 205% CH2 CH2 I l c a ca so 180 to 182% 3 H ra i N ,8 Cn oH -l l u-cu l /2 zncl, 2  
  3 ?5 a 2- -l 39 0M CH2 1:1 cu 1/2 zncl on no on ca Hi 3 ca W 9 41 f CH2 CH2 I l c u 1/2 ZnCl EXAMPLE 42 Continued ltl.l parts of the compound described in Example Emmme R R1 is dissolved in lSll parts of o-dichlorobenzene and at l5llC 547 parts of dimethyl sulfate is gradually added. After the whole has been stirred for 2 hours at l50 to 41 160C, it is cooled and the precipitate is suction filtered and washed with acetone. 10 parts (727! of theory) of 45 the compound of the formula:  
  /&amp; cH so 9&#39; 2 LL 0 N O cu 7 J; 9 OCH 50 is obtained which melts at 290 to 29lC.  
  By methods analogous to those described in the foregoing Examples. the compounds characterized by the 51 c a oe u EXAMPLE 107 55 parts of a 30% solution of sodium methylate in methanol is added to a suspension of 45 parts of 4- chloro-N-(p-morpholinocarbonylbenzyloxyJ- naphthalimidc in 500 parts of methanol and the whole is boiled under reflux for ten hours. After cooling the whole is suction filtered. the residue washed with methanol and water and the dried product is recrystallized from methyl glycol. 25 parts of 4 methoxy-N-(p morpholinocarhonylbenzyloxy)-naphthalimide is obtained having a melting point of 198 to 200C.  
 EXAMPLE 108 36 parts of styrene oxide is gradually added at 50 to 60C to 25 parts of 4-ehloronaphthalhydroxyimide dissolved in 200 parts of methanol and 30 parts oftriethylamine at the said temperature. The mixture is stirred for 10 hours at 60C, allowed to cool. and the precipitate suction filtered and washed with methanol and wa ter. The product is recrystallized from hutanol and 24 parts (66% of theory ofa mixture of compounds of the formulae:  
  OCH -caa Q e 2 t cn oa O o o ocn is obtained which has a melting point of 146 to 148C.  
 EXAMPLE 109 A mixture of 35 parts of 4-methoxy-N-(B- hromocthoxyl-naphthalimide. 42 parts of 4- mcthylpyrazolc, 14 parts of potassium carbonate and 300 parts of chlorohenzene is heated for eighteen hours at 80 to 85C. The mixture is filtered while still hot, 200 parts of petroleum ether is added to the filtrate and the deposited precipitate is suction filtered. washed with water and recrystallized from ethanol. 27 parts (77% of theory] of 4-methoxy-N-(B-(4- methylpyrazolyl l J-ethoxy)-naphthalimide is obtained having a melting point of 155 to 157C.  
 EXAMPLE 1 10 The pyridine in Example 33 is replaced by 3- methylimidazole. 42 parts (987: of theory) of the salt 3) of the formula:  
  $01 1 e11 NSC e N OCH 3 is obtained. The compound melts at 240 to 241C with decomposition.  
  EXAMPLE 111 The corresponding imidazolium salt is obtained with 2,3-dimethylimidazole analogously to Example 33. The compound melts at 230 to 233C with decomposition.  
  EXAMPLE 112 35 parts of 4-methoxy-N-( B-bromoethoxy naphthalimide and 7.5 parts of thiourea have parts of ethanol added to them and the whole is heated for 30 hours under reflux, followed by suction filtration is obtained which has the melting point 238 to 240C.  
 EXAMPLE 113 365 parts of 4-methoxy-N-(0chloroacetyloxyethoxy)-naphthalimide is heated in 180 parts of chlorobenzene and parts of pyridine for 15 hours at 80 to 90C. Petroleum ether is added followed by decanting. The non-crystalline residue is heated with 500 parts of water at 50C. The solution is filtered. 15 parts of zinc chloride in 50 parts of water is added. and the product is salted out. 36 parts of a pyridinium salt is obtained which contains of sodium chloride; the compound has the formula:  
  OCHECI-LJDOC ca at q C 2 The 4-methoxy -N-( fi-chloroacetyloxyethoxy&#39; naphthalimide required as starting material is prepared as follows:  
  29 parts of 4-methoxy&#39;-N-(B-hydroxyethoxy)- naphthalimide and 8.8 parts of sodium hydrogen carbonate are suspended in 250 parts of chloroform and then 12 parts of chloroacety&#39;l chloride in 60 parts of chloroform is added at 20 to 22C. The mixture is stirred at 20 to 25C for 2 hours. another 2.5 parts of chloroacetyl chloride is added and the whole is stirred for 10 hours at 50C. The reaction mixture is then washed with water. the organic phase is evaporated in vacuo and the product which remains is recrystallized from benzene.  
  28 parts (78% of theory) is thus obtained with a melting point of 90 to 92C.  
 EXAMPLE 1 14 36 parts of a 3091 solution of sodium methy&#39;late is added to 292 parts of 4-chloro-N-B-hydroxyethoxynaphthalimide in 150 parts of methanol and this mixture is heated for 3 hours at 60 to 60C. cooled. suction filtered, the precipitate washed with methanol and dried. 22.1 parts (7771 of theory) of 4-methoxy-N-fihydroxyethoxynaphthalimide is obtained having a melting point of 194 to 195C.  
  4-chloro-Nfi-hydroxyethoxynaphthalimide tained as follows.  
  477 parts of triethanolamine is added to a suspension of 247.5 parts of 4-chloro-N-hy&#39;droxynaphthalimide in 1500 parts of water and then 132 parts of ethylene oxide is passed into this mixture at 40 to 50C. The whole is stirred for another 3 hours at 50 to 55C. The precipitate is suction filtered. washed with water and dried. followed by recrystallization from chlorobenzene. 198 parts (68% of theory) of 4-chloro-N-B- hydroxyethoxynaphthalimide is obtained having a melting point of 186 to 187C.  
 EXAMPLE 115 247.5 parts of 4 chloro-Nhydroxynaphthalimide is dissolved in a mixture of 3000 parts of methanol and 303 parts of triethy&#39;lamine. 132 parts of ethylene oxide is passed into this solution in the course of 2 hours at is ob- 45 to 50C. The whole is stirred for another 3 hours at 45 to 50C, cooled to 15 to 20C and the deposited precipitate is suction filtered. washed with methanol and dried. 191 parts (66.5% of theory) of 4-methoxy- Nfi-hydroxyethoxynaphthalimide is obtained having a melting point of 193 to 195C.  
 EXAMPLE 116 The procedure of Example 1 15 is followed but 3000 parts of ethanol is used instead of methanol. 216 parts (729? of theory) of 4-ethoxy-N-B-hydroxyethoxynaphthalimide having a melting point of 161 to 163C is obtained under otherwise identical conditions.  
 EXAMPLE 117 The procedure of Example 1 15 is followed but 3000 parts of methyl glycol is used instead of methanol. 205 parts (627! of theory) of 4-B-methoxycthoxy-N-B- hydroxyethoxynaphthalimide is obtained having a melting point of 180 to 181C.  
 EXAMPLE 118 The procedure of Example is followed but 174 parts of propylene oxide is used instead of ethylene oxide. 235 parts (78% of theory) of 4-methoxy-N-B- hydroxypropoxynaphthalimide is obtained having a melting point of 171 to 173C.  
 EXAMPLE 119 EXAMPLE 120 The procedure of Example 1 19 is followed but 31.5 parts of p-chlorobenzoyl chloride is used instead of benzoyl chloride. The product is recrystallized from chlorobenzenc. 51 parts (80% of theory) of the compound having the following formula and which melts at 166 to 168C is obtained:  
 EXAMPLE I21 1 part of concentrated sulfuric acid is added to a solution of 28.7 parts of 4-methoxy-N-B-hydroxyethoxynaphthalimide in 150 parts of acetic anhydride and the whole is stirred for 4 hours at 50 to 55C. The mixture is then poured onto ice. stirred for another hour. and the precipitate is suction filtered and dried. After recrystallization from xylene. 30 parts (91% of theory) of 4-methoxy-N-B&#39;acetoxyethoxynaphthalimide is obtained having a melting point of 160 to 161C.  
 EXAMPLE 122 I 0-CH -Cl-l -OC-CH -Cl o N o EXAMPLE 123 parts of phenoxyaeetyl chloride is added to 2817 parts of 4-methoxy-N-B-hydroxyethoxynaphthalimide in 100 parts of nitrobenzene and this mixture is heated for 3 hours at 100 to 1 10C. The nitrobenzene is then distilled off with steam. and the residue is suction filtered and stirred for 1 hour in 100 parts of methanol followed by suction filtration. drying and recrystallization from benzene. 24.5 parts (58% of theory) of the compound of the formula:  
 which melts at 174 to 175C is obtained.  
 EXAMPLE 124 The procedure of Example 123 is followed but 128 parts of isobutyryl chloride is used instead of phenoxyacetyl chloride. The product is recrystallized from toluene. 17.5 parts (4971 of theory) of the following compound is obtained which melts at 168 to 172C:  
  24 H 02 CH/ CH5 o-ca -c N 0 ocii EXAMPLE 125 7.4 parts of methyl isocyanate is added to 2817 parts of 4-methoxy-N43-hydroxyethoxynaphthalimide in 100 parts of toluene and the whole is stirred for 5 hours at 100 to l 10C. allowed to cool and the precipitate is suction filtered and recrystallized from chlorobenzene. parts (877: of theory) of the compound of the formula:  
  is obtained which melts at 176 to 178C.  
 EXAMPLE 126 The procedure of Example 125 is followed but 16.8 parts of phenyl isocyanate is used instead of methyl isocyanate. 33 parts (81% of theory) of the following compound is obtained which melts at 197 to 199C:  
  0 II e-ca -cii -oc-NH-c ii 0 N o ocii EXAMPLE 127 16.8 parts of phenyl isocyanate is added to 33.1 parts of 4-l3-methoxyethoxy-N-B-hydroxyethoxynaphthalimide in 120 parts of chlorobenzene at to C and the whole is stirred for another 5 hours at 100 to C. After cooling and suction filtration. the product is recrystallized from chlorobenzene. 37 parts (827: of  
 theory) of the compound of the formula:  
 is obtained which melts at 169 to 171C.  
 EXAMPLE 12s 1 part of concentrated sulfuric acid is added to 33.1 parts of d-B-methoxyethoxy-NB-hydroxyethoxynaphthalimide in 100 parts of acetic anhydride and this mixture is stirred for 3 hours at 45 to 50C. It is then poured onto ice and the precipitate is suction filtered and recrystallized from toluene. 34 parts (91% of theory) of the compound of the formula:  
 CH CH OCH is obtained. The compound melts at 139 to 140C.  
 EXAMPLE [29 24.8 parts of 4-chloro-N-hydrosynaphthalimide is 2 cipitate is suction filtered and recrystallized from toluenc. 33 parts (84% of theory) of the following compound is obtained which melts at 153 to 154C:  
 OCH  
 EXAMPLE 130 A mixture of 24.8 parts of 4-chloro-N- hydroxynaphthalimide. 30 parts of triethylamine. 300 parts of methanol and 45 epoxypropane is heated for 5 hours at 60 to 65C. cooled. suction filtered and recrystallized from toluene. 264 parts (67% of theory) of the compound having a melting point of 151 to 153C described in Example 129 is obtained.  
 EXAMPLE 131 The procedure of Example 130 is followed but 49.2 parts of 3-(4&#39;-methyl)-phenoxy-1.2-epoxypropane is used instead of 3-phenoxy-1.2-epoxypropane. The product is recrystallized from toluene. 336 parts 879 of theory) of the compound of the formula:  
 parts of 3-phenoxy-l.2-  
 OCH  
 is obtained. The compound melts at 179 to 180C.  
 EXAMPLE 132 20.3 parts of the compound described in Example 131 is dissolved in 120 parts of acetic anhydride. After 2 parts of concentrated sulfuric acid have been added the whole is stirred for 3 hours at 45 to 50C. poured onto ice and the precipitate is suction filtered and recrystallized from alcohol. 18 parts (805! of theory) of the compound of the formula:  
 OCH  
 is obtained. The compound melts at 89 to 90C EXAMPLE 133 7.2 parts of phenyl isocyanate is added to 20.3 parts of the compound described in Example 131 in 100 parts ofchlorobenzene at 90 to C. After stirring for 5 hours at 90 to C the precipitate is suction filtered and recrystallized from xylene. 23.2 parts (88% of theory) of the following compound is obtained which melts at 185 to 186C:  
 EXAMPLE 134 The procedure of Example is followed but 498 parts of 3-phen \&#39;lmereapto-l.lepoxypropane is used instead of 3-pheno\&#39; \&#39;-1.2-epoxypropane. The product is recrystallized from toluene. 25.4 parts (62% of theory) of the following compound is obtained which melts at 161 to 165C:  
  EXAMPLE l37 -CH -CH-cH -S The procedure of Example 135 is followed but 34.8 0 OH parts of 3-isopropoxy-l .Z-epoxypropane is used instead s of 3-ethoxy-1.2epoxypropane. The product is recrystallized from toluene. 25.8 parts 72% oftheory] of the compound of the formula:  
  It) CH -L;HCH OCH CH EXAMPLE 135 0 0 OH 3 30.6 parts of 3-ethoxy-l.2-epoxypropane is added to a mixture of 24.8 parts of 4-chloro-N- hydroxynaphthalimide. 30 parts of triethylamine and 300 parts of methanol and the whole is heated to 60 6 to 65C for 5 hours. cooled, suction filtered and recrys- 3 tallized from toluene. 27.2 parts (79% of theory) of the following compound which melts at 98 to 99C is obi b i d Th und melt at 78 to 79C, tained: 2U  
 EXAMPLE 138 17.2 parts of N-Z.3-epoxypropylmorpholine is added 2 1 2 5 to 24.8 parts of 4-chloro-N-hydroxynaphthalimide dis- 0 0 OH solved in a mixture of 250 parts of methanol and parts of triethylamine. After the whole has been stirred for 5 hours at to C. it is cooled, the precipitate is suction filtered, and the residue washed with methanol and dissolved in a mixture of parts of methanol CH and 36 parts of a 30% solution of sodium methylate. 3 After the solution has been heated for 3 hours at 65 to 70C it is cooled and the precipitate is suction filtered EXAMPLE I36 and recrystallized from toluene. 24 parts (62% of the- The procedure of Example is followed but 39 Cry) of the campound of formula: parts of 3-n-butoxy-l.2-epoxypropane is used instead is of 3-ethox -l.2-epoxypropane. The product is recrystallized from toluene. 25 parts (67% of theory) of the l compound having the formula (1J CHZ C|:H CHQ N\ o N 0 OH 0 CH CH CH 0c H 2&#39;, 2&#39; l 9 0 0H OCH 45 5 is obtained which melts at 129 to l3 lC.  
  In a manner analogous to that described in Examples 1 14 to 138. the compounds identified in the following is obtained which melts at 86 to 88C. 50 Table by their substituents are obtained:  
 OCH CH-OR I I N. O x  
 Example R R X 139 H Il.--C H H l lo H n-C H H 1 41 a c H 0c 2 H cu -(ontinued Exarrple R R1 X 168 H CH5 cn ogcl 9 cH CHQOQOCHE 7 cH cn s 3ocn l 171 H cH CH2N(CH3)2 172 H cH CH2N(C2H5)2 113 H CH CH N(C H H 17 H CH CH2N C2H4OH 175 H cH CH MC I-I OH) 176 H cH CHE-NO 7 -i 17I cocH cH c11 N H 178 cocH cH 011 -1050 f\ 179 cocH cH CH2-N\ /NH 180 H cH CH2 -NCN-CH) 181 cocH cH CHE-NLJN-CHD 2 18 001111011 cH c11 11 N 011 1 183 H cH CHE-N NC H OH 18 1 CONHC H CH 6 5 3 GHQ-N N-c H 0H 185 H cH CH2-N EXAMPLE I86 l3.2 parts ofmethyl chloroform-Lite is dripped at 5 to C into :1 mixture of 2817 parts of 4-methoxy-N-B- hydmxyethoxynuphthalimide 11nd 1115 parts of pyridine in I parts of methylene chloride. After stirring for 2 hours at 5 to l()C and for 5 hours at 25 to 30C 200 parts of water is added. The methylene chloride phase is separated shaken up twice with l N hydroehloric acid and water. dried and concentrated at suhatmospheric pressure The crystalline residue is recrys- 5 tullized from toluene, 3 l .8 parts (929? of theory of the following compound which melts at lo4 to C is obtained:  
  O H 9 H -c1-I -o-c-o :H N 0 EXAMPLE 187 The procedure of Example 186 is followed but 22.8 parts of cyelohexyl chloroformate is used instead of methyl chloroformate. The product is recrystallized from toluene. 3414 parts (83% of theory) olthe following compound which melts at 142 to 143C is obtained:  
  o n (&#39;)CH2CH2O-C-0-@ o N EXAMPLE 188 and with water. dried and concentrated at subatmospheric pressure. The residue is recrystallized from toluene. 35 parts (877! of theory) of the compound having the following constitution and which melts at 88 to 89C is obtained:  
 OCH  
 EXAMPLE 189 19.4 parts of methyl glycol chloroformate is added at phcnylethoxynaphthalimide and l 1.5 parts of pyridine in 150 parts ofmethylene chloride. The whole is stirred for another hour at 5 to C and 5 hours at to C. 200 parts of water is added. the methylene chloride phase is separated. shaken with l N hydrochloric acid and water. dried and concentrated under suhatmospheric pressure, The residue is recrystallized from toluene. 33 parts (71% of theory) of the following compound whieh melts at 132 to 134C is obtained:  
  CH OCli EXAMPLE 190 The procedure described in Example 188 is adopted but 21.9 parts of phenyl chloroformate is used instead of methyl chloroformatc. The product is recrystallized from toluene. 33.7 parts (807! of theory) ofthe following compound which melts at 182 to 183C is obtained:  
 OCH  
 5 to 10C to 36.3 parts of 4-methoxy-N-B-hydroxy-B- The following compounds are obtained analogously:  
 OCH  
 Example R Melting point CH O l 5 ll 9 -O-CH -C1 I-OCOCH 122 to 192 W 59 -O-CH -CHOC-OCH 10 -1 to 106 -ocri cn -oEf-0ca cri ocn 87 to 89 Continued Example R Melting point CH O at O a 2390a 0c H t T 9 l D OCH CHOCOC H 1A9 to 151 llt;  
 Y O CH CH OC OC H5 162 to 16} E? 97 -ocH cH -0c-oc I1&#39; 7h to 76 (EH3 O ll 198 -OCH -CH-OCCH CH OCH 7 to 99 CH O t 3 H 199 -0-cn -cH-0c-o@ 118 to 120 VI 200 -OCH -CH -OCOC H 1} to 156 We claim: B is alkyl of I to 4 carbon atoms taken as separate 1. A compound of the formula substituents or when taken together with the nitrogen atom may also form a heterocyclic ring se- 08 lectcd from the class consisting of O, 6 O pyrrolicldinium. piperidinium and imidazolinium,  
 \ and l l X is methyl. ethyl. phenyl or bcnzyl; and R is methyl or ethyl.  
 &#39; 2. A compound as claimed in claim 1 of the formula ngterein R is a radical selected from the class consisting l Hal OZ i l 1 e x K -Cl-[ CH-A -CH CHA -CH -CHN D B B 00113 wherein R is a radical selected from the class consisting of 9 i and CHZCHZ-N 5S CH2CH2 OCH3:  
  O I: in which: -CH CH OCOC H A is hydrogen or methyl; Hal is chlorine or bromine; 0 CH 0 Z is alkyl of 1 to 4 carbon atoms, benzoyl alkanoyl l l CH CHOCOC H of 2 to 8 carbon atoms, the radical R NHCO where R is methyl, ethyl. n-propyl isopropyl, phenyl, chlorophenyl dichlorophenyl or methyl- H phenyl, or the radical R&#34;OCO where R is CHZCH2 OC CSHS, alkyl of l to 8 carbon atoms. alkoxyalkyl of 3 to 6 carbon atoms cyclohexyl. bcnzyl. phenyl, chlorophenyl, methylphenyl or methoxyphenyl; D is hydrogen or methyl.  
 3. A compound as claimed in claim I of the formula wherein R is a member selected from the class consisting f