3,205,257 United States Patent Office Patented Sept. 7, 1965 2 diols one can mention ethylene glycol, propylene glycol, 3,205,257 tetramethylene diol, decamethylene diol, pentamethylene BES9-(2-CYANOALKYL)FLUOREN-9.YLALKANE COMPOUND diol, hexamethylene diol, and the like. In producing the Henry E. Fritz, South Charleston, and David W. Peck, bis(9-fluorenyl)alkanes the concentration of diol in the Charleston, W. Va., assignors to Union Carbide Corpo charge can vary from about 0.1 mole or less to about 10 ration, a corporation of New York moles or more, per mole of fluorene compound charged, No Drawing. Fied Sept. 10, 1962, Ser. No. 222,694 with from about 0.5 to about 2.0 mole of diol per mole of 5 Caims. (CI. 260-465) fluorene compound being preferred. AS Stated above, an alkali metal hydroxide, such as This invention relates to novel fluorene derivatives. O lithium hydroxide, sodium hydroxide, potassium hydrox More particularly, this invention relates to bis9-(sub ide, and the like, is employed as a catalyst in producing stituted alkyl)fluoren-9-ylalkanes of the formula: the bis(9-fluorenyl)alkanes, with potassium hydroxide be ing preferred. The amount of alkali metal hydroxide used can vary from about 0.1 mole or less to about 1.0 5 mole or more per mole of fluorene compound charged, with from about 0.2 to about 0.5 mole of alkali metal hy -N droxide per mole of fluorene compound being preferred. ZCHRCH CnH2n CHCERZ, The reaction of diol with fluorene is conducted at a tem wherein it is an integer having a valve of from 2 to 10 perature of from about 175 C. or lower to about 275 C. and preferably from 2 to 6; Z is a cyano radical, a or higher, with temperatures of from about 220 C. to -COOR radical, or a -CHNHR2 radical; R is a hy about 250 C. being preferred. drogen atom or a methyl radical; R is a hydrogen atom, The bis(9-fluorenyl)alkane is readily recovered from an alkali metal atom, or an alkyl radical having from 1 the reaction mixture by slurrying the reaction mixture to about 10 carbon atoms; and R2 is a hydrogen atom or with water to dissolve unreacted diol and the alkali an alkanoyl radical having from 1 to about 5 carbon atoms 25 metal hydroxide and then filtering the insoluble bis(9- in the alkyl radical thereof. Thus, the compounds of fluorenyl)alkane from the aqueous slurry. If desired, this invention are novel bis9-(2-cyanoalkyl)fluoren-9- the bis(9-fluorenyl)alkane can be further purified by yl)alkanes; bis 9 - (2 - carboxyalkyl)fluoren-9-ylalkanes washing with water or methanol, or by recrystallization and their alkali metal salts or alkyl esters; bis(9-(N-alka from an organic solvent, for example, 1,4-dioxane. noyl-3-aminoalkyl)fluoren-9-ylalkanes; and bis(9 - (3- 30 Reaction of the bis(9-fluorenyl)alkane with a cyanoal aminoalkyl)fluoren-9-ylalkanes. kene such as acrylonitrile or methacrylonitrile produces The novel carboxyl and amino compounds of this in the bis9-(2-cyanoalkyl)fluoren-9-ylalkanes having the vention are useful in themselves as monomers for the formula: formation of new polymers, such as polyesters, polyam ides, and the like; while the cyano compounds are use ful as intermediates for the production of polymerizable monomers. For example, the cyano derivatives of this invention can be hydrolyzed to form dicarboxylic acids which are useful in the production of polyesters or poly NC CHRc?, CnH2n CHCHRCN amides. The cyano derivatives can also be hydrogenated 40 wherein in and R are as previously defined. As examples in the presence of an alkali metal alkanoate to produce N of these compounds one can mention 1,2-bis(9-(2-cyano aikanoylamino derivatives which can be hydrolyzed to ethyl)fluoren - 9-ylethane, 1,4-bis(9-(2-cyanoethyl)fluo form an amine derivative useful in the production of poly ren - 9-yl)butane, 1,10-bis(9-(2-cyanoethyl)fluoren-9-yl) amides, polyureas, and the like. decane, 1,2-bis(9-(2-cyanopropyl)fluoren-9-yl)ethane, 1, The novel bis9-(substituted alkyl)fluoren-9-ylalkanes 10-bis9-(2-cyanopropyl)fluoren - 9-ydecane, and the of this invention are all readily produced from the bis(9- like. fluorenyl)alkanes of the formula: As indicated, the bis(9-(2-cyanoalkyl)fluoren-9-yl alkanes are produced by the cyanoalkylation of a bis(9- fluorenyl)alkane with a cyanoalkene such as acrylonitrile or methacrylonitrile. The cyanoalkylation can be carried 50 out at from about 10° C. to about 50° C., preferably from about 20° C. to about 35° C., in the presence of a solvent for the bis(9-fluorenyl)alkane, for example, benzene, (U) (UO dioxane, pyridine, acetonitrile, tert-butyl alcohol, etc. wherein n is as previously defined. The bis(9-fuorenyl) The mole ratio of cyanoalkene to bis(9-fluorenyl)alkane alkanes are produced by reacting a fluorene with a diol in 5 5 can vary from about 0.5:1 or less to about 5:1 or more, the presence of an alkali metal hydroxide as a catalyst. with ratios of from about 2:1 to about 3:1 preferred. By the term "fluorene' is meant both fluorene and fluo The cyanoalkylation is assisted by a basic catalyst, such rene compounds which are substituted on the aromatic as the oxides, hydroxides, alkoxides, hydrides, cyanides, rings with alkyl, aryl, alkaryl, aralkyl, alkoxy, aryloxy, or amides of sodium or potassium. Quaternary ammo alkaryloxy, and aralkoxy radicals having up to 10 carbon 60 nium hydroxides such as benzyltrimethylammonium hy toms. As examples of suitable fluorene compounds, one droxide are particularly preferred as catalysts. In gen can mention fluorene, 1-methylfluorene, 2-methylfluo eral, the basic catalysts are employed in the cyanoalkyla rene, 3-methylfluorene, 4-methylfluorene, 5-methylfluo tion reaction in an amount varying from about 0.5 to rene, 6-methylfluorene, 7-methylfluorene, 8-methylfluo about 10 weight percent, based upon the cyanoalkene, with rene, 2-hexylfluorene, 2-phenylfluorene, 2-(1-naphthyl) from about 1 to about 5 weight percent preferred. Al fluorene, 2-(2-methylphenyl)fluorene, 2-benzylfluorene, though the reactants can be charged in any order, it is 2 - methoxyfluorene, 2 - phenoxyfluorene, 2-(2-methyl preferred to gradually add the cyanoalkene to a stirred phenoxy) fluorene, 2-benzyloxyfluorene, and the like. mixture of catalyst, bis(9-fluorenyl)alkane and solvent. The diols employed to produce the bis(9-fluorenyl)al The bis(9-(2-cyanoalkyl)fluoren-9-ylalkanes are solids kanes are represented by the formula HOCH26p 70 which can be recovered from the reaction mixture by wherein n is as defined above. As examples of suitable filtration. Additional bis 9-(2-cyanoalkyl)fluoren-9-yl) 3,205,257 4. alkane can be recovered from the filtrate by admixing procedures known to those skilled in the art, such as re the filtrate with water, whereupon the bis 9-(2-cyano fluxing the selected acid and alcohol in the presence of alkyl)fluoren-9-ylalkane dissolved in the filtrate precipi an acid catalyst, for example, p-toluene sulfonic acid, to tates out and can be recovered by filtration. The bis(9-(2- produce the ester, which is recovered by conventional cyanoalkyl)fluoren-9-ylalkane can then be purified by procedures. conventional procedures. The bis(9 - (N-alkanoyl-3-aminoalkyl)fluoren-9-yl)al The bis(9-(2-carboxyalkyl)fluoren-9-ylalkanes and the kanes of this invention have the formula: alkali metal salts and alkyl esters thereof of this inven tion have the formula: 10 RéNHCHCHRó?,YYYYX C.H. HCHRCH-NHCR wherein n and R are as previously defined and R3 is an Riooc CHR off, C.E. CHCHRCOOR1 5 alkyl radical of from 1 to 5 carbon atoms. As examples wherein n, R and Rare as defined above. of these compounds one can mention 1,2-bis 9-(N-acetyl As examples of the novel dicarboxylic acids one can 3-aminopropyl)fluoren-9-yl)ethane, 1,4-bis(9-(N-acetyl-3- mention 1,2-bis(9-(2-carboxyethyl)fluoren-9-ylethane, 1, aninopropyl)fluoren-9-yl)butane, 1,10-bis(9-(N-acetyl-3- 4-bis(9-(2-carboxyethyl)fluoren-9-yl-butane, 1,10-bis 9 aminopropyl)fluoren-9-ylethan, 1,2-bis9-(N-valeryl-3- (2-carboxyethyl)fluoren-9-yl) decane, 1,2-bis(9-(2-carbox 20 aminopropyl)fluoren-9-yl)ethane, 1,2-bis 9-(N-acetyl-3- ypropyl)fluorei - 9-yl)ethane, 1,10-bis(9-(2-carboxypro amino-2-methylpropyl)fluoren-9-ylethane, and the like. pyl)fluoren-9-yl) decane, and the like. These dicarboxyic The bis 9 - (N-alkanoyl-3-aminoalkyl)fluoren-9-ylal acid compounds are readily produced by the hydrolysis of kanes of this invention are produced, for example, by hy the corresponding bis(9-(2-cyanoalkyl)fluoren-9-yl)al drogenation of a mixture of a bis(9-(2-cyanoalkyl)fluoren kane compound or by the reaction of an alkali metal 9-yllalkane, an alkanoic acid anhydride and an alkali acrylate or alkali metal methacrylate with a bis(9-fluor metal alkanoate in contact with hydrogenation catalyst. enyl)alkane followed by acidification of the resulting di The alkanoic acid anhydrides suitable for use in pro alkali metal salt. ducing the bis(9-(N-alkanoyl-3-aminoalkyl)fluoren-9- The hydrolysis of the bis 9-(2-cyanoalkyl)fluoren-9-yl) ylalkanes of this invention are the anhydrides of lower alkane to form the bis(9-(2-carboxyalkyl)uuoren-9-y 30 alkanoic acids such as acetic acid, propionic acid, butyric alkane can be conducted by methods known to those acid, pentanoic acid, and the like. In this reaction, the skilled in the art for the hydrolysis of the nitrile group. mole ratio of acid anhydride to bisD9-(2-cyanoalkyl) It is preferred, however, to reflux the bis9-(2-cyanoalkyl) fluoren-9-yl)alkane can vary from about 0.5:1 or less to fluoren-9-yllalkane in admixture with water, acetic acid, about 4:1 or higher, with mole ratios of from about 1:1 and hydrobromic acid, there being at least four moles of 3 5 to about 2:1 preferred. water and at least two moles of hydrobromic acid per mole The alkali metal alkanoate employed is preferably the of bis(9-(2-cyanoalkyl)fluoren-9-yl)alkane in the charge. alkali metal salt of the alkanoic acid whose anhydride As indicated above, the bis(9-(2-carboxyalkyl)fluoren is employed during the hydrogenation reaction. The 9-ylalkane also can be produced by reacting an alkali alkali metal salts can be the lithium, sodium, potassium, metal acrylate or alkali metal methacrylate with a bis(9- rubidium, or cesium salts of the alkanoic acid. As ex fluorenyl)alkane in the presence of an alkali metal hy amples of suitable alkali metal alkanoates one can men droride as a catalyst. The mole ratio of alkali metal tion lithium acetate, sodium acetate, potassium acetate, acrylate or alkali metal methacrylate to bis(9-fluorenyl) rubidium acetate, cesium acetate, sodium propionate, so alkane in the charge can vary from about 1:1 to about 5:1, dium butyrate, sodium valerate, and the like. In gen with a mole ratio of from about 2:1 to about 3:1 preferred. eral, the alkali metal alkanoates are present in the re The alkali metal hydroxide is employed in an amount 45 action mixture in an amount varying from 5 to 100 varying from about 0.1 to about 5 weight percent, based Weight percent based on the bis(9-(2-cyanoalkyl)fluoren upon alkali metal acrylate or alkali metal methacrylate, 9-ylalkane, with from 10 to 30 weight percent pre with from about 0.5 to about 3 weight percent preferred. ferred. The reaction is conducted at a temperature of from about The hydrogenation catalyst can be any of the Raney 150° C. to about 350° C., with a temperature of from metal catalysts known to the art, with Raney nickel being about 190° C. to about 290 C. preferred. The immediate preferred. The catalyst is employed in amounts vary products of this process are the dialkali metal salts of the ing from 2 to 40 weight percent, based on the bis(9-(2- (bis(9-(2-carboxyalkyl)fluoren-9-yl)alkanes such as the cyanoalkyl)fluoren-9-ylalkane, with amounts of from 10 lithium, Sodium, potassium, rubidium or cesium salts. to 30 percent being preferred. The hydrogenation is These dialkali metal salts are readily acidified by methods carried out at hydrogen pressures varying from 40 to known to those skilled in the art to produce the corre 100 p.S.i.g., or more, with pressures of from about 50 sponding bis 19-(2-carboxyalkyl)fluorene-9-ylalkane. to about 75 p.S.i.g. being preferred, and at reaction tem The bis(9-(2-carboxyalkyl)fluoren-9-yl)alkanes are wa peratures of from about 25° C. to about 100° C., with ter-insoluble solids. Thus, they can be isolated from the temperatures of from about 30° C. to about 80° C. being reaction mixture from either of the foregoing processes 60 preferred. by the addition of water and filtration of the aqueous mix The bis9-(3-aminoalkyl (fluoren-9-ylalkanes of this ture. invention are represented by the formula: The bis(9-(2-carboxyalkyl)fluoren-9-ylalkanes ae readily converted to their alkyl esters, of the formula: 65 N/ HNCHCHRCHYYYYX CnH2n CHCHRCHNH R4 OO CCHRCH CnH2n CH2CHRCOOR4 70 wherein in and Rare as previously defined. As examples wherein in and R are as previously defined and R4 is an aminopropyl)fluoren-9-yl)ethane,of these novel diamines one can 1,4-bis(9-(3-aminopromention 1,2-bis(9-(3- alkyl radical containing from 1 to 10 carbon atoms, such pyl)fluoren-9-yl)butane, 1,10-bis(9-(3-aminopropyl)fluo as methyl, ethyl, propyl, isopropyl, butyl, hexyl, 2-ethyl ren-9-ylldecane, 1,2-bis(9-(3-amino - 2-methylpropyl) hexyl, decyl and the like. The esters can be produced by fluoren-9-yl)ethane, and the like. 3,205,257 5 6 The bis9-(3-aminoalkyl)fluoren-9-ylalkanes of this Microanalysis.-Calculated for C6H3N2: C, 87.78%; invention are readily produced by hydrolysis of the bis(9- H, 6.54%; N, 5.68%. Found: C, 87.73%; H, 6.78%; (N-alkanoyl-3-aminoalkyl)fluoren-9-ylalkanes of the in N, 5.89%. vention. The hydrolysis can be accomplished by methods EXAMPLE V known to those skilled in the art, such as by heating in 5 contact with a mixture of aqueous sodium hydroxide 1,5-bis(9-(2-cyanoethyl)fluoren-9-yl)pentane and methanol at a temperature of from about 150° C. to Employing apparatus and procedures similar to those 250° C. described in Example III, 30 grams of 1,5-bis(9-fluorenyl) Ths bis(9-(3-aminoalkyl)fluoren-9-yl alkanes can also pentane (produced in a manner similar to that described be produced by reduction of the bis(9-(2-cyanoalkyl) O in Example I by reacting fluorene with 1,5-pentane diol fluoren-9-ylalkanes of this invention, such as by the in the presence of potassium hydroxide) were reacted with lithium aluminum hydride reduction of the bis(9-(2- 16 grams of acrylonitrile to produce 26 grams of 1,5-bis cyanoalkyl)fluoren-9-ylalkanes. 9-(2-cyanoethyl)fluoren-9-yl pentane which, after re The following examples are illustrative: crystallization from methanol, melted at 120-121 C. 5 Microanalysis.-Calculated for C3H4N2: C, 87.61%; EXAMPLE I H, 6.76%; N, 5.53%. Found: C, 88.01%; H, 6.69%; N, 1,2-bis(9-fluorenyl)ethane 5.65%. A three-liter rocker autoclave was charged with 332 EXAMPLE VI grams of fluorene, 500 grams of ethylene glycol, and 85 1,6-bis(9-(2-cyanoethyl)fluoren-9-ylhexane grams of potassium hydroxide. The autoclave was 20 Employing apparatus and procedures similar to those sealed, pressured to 25 p.s.i.g. with air and heated at 220 described in Example III, 34 grams of 1,6-bis(9-fluorenyl) C. for 20 hours while agitating by rocking. The auto hexane were reacted with 16 grams of acrylonitrile to clave was cooled, opened and the contents were removed produce 31 grams of 1,6-bis9-(2-cyanoethyl)fluoren-9- and slurried in 1 liter of water. After filtration from 25 yl) hexane which, after recrystallization from methanol, the aqueous slurry, washing with water and then with melted at 125.5-126.5 C. methanol and drying, the 1,2-bis(9-fluorenyl)ethane pro Microanalysis.-Calculated for Cahn: C, 87.66%; duced weighed 157 grams and melted at 228-229.5 C. H, 6.96%; N, 5.38%. Found: C, 87.38%; H, 6.90%; EXAMPLE II N, 5.57%. 1,6-bis(9-fluorenyl) hexane 30 EXAMPLE VII Employing apparatus and procedures similar to those 1,2-bis(9-(2-carboxyethyl)fluoren-9-yl)ethane disclosed in Example I, 166 grams of fluorene, 70 grams A mixture of 300 grams of 1,2-bis(9-(2-cyanoethyl) of 1,6-hexanediol and 42.5 grams of potassium hydroxide fluoren-9-yl)ethane, 750 grams of acetic acid and 750 were reacted at 210-220 C. for 4 hours to produce 143 grams of aqueous 48 percent hydrobromic acid as catalyst grams of 1,6-bis(9-fluorenyl) hexane. After recrystalliz was refluxed vigorously for 4 days. After filtration from ing from a mixture of isopropanol and dioxane the 16 the reaction mixture, washing with water and recrystal bis(9-fluorenyl) hexane melted at 109-109.5° C. lization from dioxane, there were obtained 277 grams of 1,2-bis 9-(2 - carboxyethyl)fluoren - 9 - ylethane which EXAMPLE I melted at 285-287 C. 1,2-bis(9-(2-cyanoethyl)fluoren-9-yl)ethane 40 Microanalysis.-Calculated for CH3O4: C, 81.27% To a charge containing 36 grams of 1,2-bis(9-fluorenyl) H, 5.98%. Found: C, 81.02%; H, 6.09%. ethane, 750 cc. of dioxane and 10 cc. of a 32 percent The structure of the 1,2-bis(9-(2-carboxyethyl)fluoren solution of benzyltrimethylammonium hydroxide in meth 9-yl)ethane was further confirmed by infrared spectros anol as a catalyst, there were slowly added 20 grams of Copy. acrylonitrile with stirring. The temperature of the reac In a similar manner, 1-2-bis(9-(2-carboxypropyl) tion mixture rose from 27 C. to 37 C. After cooling fluoren-9-yl)ethane is produced by substituting, 1,2-bis to 29° C. and stirring for another 2 hours, an additional 9-(2-cyanopropyl)fluoren-9-yl)ethane for 1,2-bis(9-(2- 10 cc. of the benzyltrimethylammonium hydroxidemeth cyanoethyl)fluoren-9-ylethane. anol solution and 20 grams of acrylonitrile were added. 50 EXAMPLE VIII The reaction mixture was filtered and the solid 1,2-bis(9- 1,4-bis(9-(2-carboxyethyl)fluoren-9-ylbutane (2-cyanoethyl)fluoren-9-yl)ethane was recovered, which, after recrystallization from dioxane, weighed 26 grams Employing apparatus and procedures similar to those and melted at 275-277 C. described in Example VII, 10 grams of 1,4-bis(9-(2- Microanalysis.-Calculated for C4H23N2: C, 89.94%; 55 cyanoethyl)fluoren-9-yl)butane, 200 milliliters of acetic H, 6.03%; N, 6.03%. Found: C, 89.95%; H, 6.10%; acid and 200 milliliters of aqueous 48 percent hydro N, 6.20% bromic acid were refluxed for 16 hours to produce 8 grams The structure of the 1,2-bis(9-(2-cyanoethyl)fluoren of 1,4-bis(9-(2-carboxyethyl)fluoren-9-yl)butane which, 9-yl)ethane was further confirmed by infrared spectros after recrystallization from isopropanol, melted at 261 COpy. 60 263 C. In a similar manner, 1,2-bis(9-(2-cyanopropyl)fluoren Microanalysis.--Calculated for C6H4O4: C, 81.48%; 9-yl)ethane is produced by substituting methacrylonitrile H, 6.45%. Found: C, 81.49%; H, 6.51%. for acrylonitrile. EXAMPLE X EXAMPLE IV 65 I,5-bis(9-(2-carboxyethyl)fluoren-9-yl)pentane 1,4-bis(9-(2-cyanoethyl)fluoren-9-yl)butane Employing apparatus and procedures similar to those Employing apparatus and procedures similar to those described in Example VII, 10 grams of 1,5-bis(9-(2-cyano described in Example III, 40 grams of 1,4-bis(9-fluorenyl) ethyl)fluoren-9-yl)pentane, 200 milliliters of acetic acid butane (produced in a manner similar to that described and 200 milliliters of aqueous 48 percent hydrobromic in Example I by reacting fluorene with 1,4-butane diol in 70 acid were refluxed for 16 hours to produce 10 grams of the presence of potassium hydroxide) were reacted with 1,5-bis(9-(2-carboxyethyl)fluoren - 9 - ylpentane which, 16 grams of acrylonitrile to produce 34 grams of 1,4- after recrystallization from a cyclohexane-benzene-iso bis(9-(2-cyanoethyl)fluoren-9-yl)butane which, after re propanol mixture, melted at 180-181° C. crystallization from an isopropanol-benzene mixture, Microanalysis.-Calculated for C3H26O4: C, 81.58%; melted at 181 C-132 C. H, 6.66%. Found: C, 81.34%; H, 6.69%. 3,205,257 7 3. EXAMPLE X In a similar manner 1,2-bis(9-(N-acetyl-3-amino-2- methylpropyl)fluoren-9-yl)ethane is produced by substi 1,6-bis(9-(2-carboxyethyl) fluoren-9-ylhexane tuting 1,2-bis 9-(2-cyanopropyl)fluoren-9-yl)ethane for Employing apparatus and procedures similar to those 1,2-bis(9-(2-cyanoethyl)fluoren-9-yl)ethane, and 1,2-bis described in Example VI, 10 grams of 1,6-bis(9-(2-cyano (N-valeryl-3-aminopropyl)fluoren-9-ylethane is produced ethyl)fluoren-9-ylhexane, 200 milliliters of acetic acid, 5 by substituting valeric anhydride for acetic anhydride and and 200 milliliters of aqueous 48 percent hydrobromic sodium valerate for sodium acetate. acid were refluxed for 16 hours to produce 10 grams of 1,6-bis(9-(2-carboxyethyl)fluoren - 9 - ylhexane which, EXAMPLE XIV after recrystallization from isopropanol, melted at 218 O 1,2-bis(9-(3-aminopropyl)fluoren-9-yl)ethane 21.9° C. A rocker autoclave was charged with 10 grams of 1,2- Microanalysis.--Calculated for CHO: C, 81.69%; bis 9 - (N-acetyl - 3 - anninopropyl)fluoren-9-ylethane, 8 H, 6.86%. Found: C, 81.75%; H, 7.11%. grams of sodium hydroxide, 10 grams of water and 200 EXAMPLE X milliliters of methanol. The autoclave was sealed and 5 heated at 196-205 C. for 10 hours while agitating the 1,2-bis(9-(2-carboxyethyl)fluoren-9-yl)ethane reaction mixture by rocking. The autoclave was cooled, 1,2-bis(9-(2-carboxyethyl)fluoren-9-yl)ethane is pro opened and the contents were poured into 750 milliliters duced by reacting 1,2-bis(9-fluorenyl)ethane with potas of water, whereupon 1,2-bis(9-(3-aminopropyl)fluoren-9- sium acrylate in the presence of potassium hydroxide at yl)ethane precipitated, which, after filtering and drying, about 300° C. to produce the dipotassium salt of 1,2- 20 Weighed 6 grams. After recrystallization from cyclohex bis(9-(2-carboxyethyl)fluoren-9-yl)ethane and acidifying ane the 1,2-bis(9-(3-aminopropyl)fluoren - 9 - ylethane the reaction mixture with aqueous hydrochloric acid to finelted at 208-210 C. liberate the free acid. Microanalysis.--Calculated for CHN: C, 86.4%; In a similar manner, 1,2-bis 9-(2-carboxypropyl)fluo H, 7.7%; N, 5.9%. Found: C, 86.0%; H, 7.5%; N, ren-9-ylethane is produced by substituting potassium 6.0%. methacrylate for potassium acrylate. The structure of the 1,2-bis(9-(3-aminopropyl)fluoren 9-yl)ethane was further confirmed by infrared spectros EXAMPLE XII COpy. 1,6-bis 9-(N-acetyl-3-aminopropyl)fluoren-9-ylhexane In a similar manner, 1,2-bis(9-(3-amino-2-methyl 30 propyl)fluoren-9-yl)ethane is produced by substituting 1,2- A hydrogenating vessel was charged with 10 grams of bis-(N-acetyl-3-amino - 2 - methylpropyl)fluoren-9-yl) 1,6-bis(9-(2-cyanoethyl)fluoren-9-ylhexane, 100 grams ethane for 1,2-bis(9-(N-acetyl-3-aminopropyl)fluoren-9- of acetic anhydride, 2 grams of Sodium acetate and about yl)ethane. 3 grams of neutra Raney nickel catalyst. The hydrogen What is claimed is: erator was sealed, pressured to 59.5 p.S.i.g. with hydrogen 35 1. A bis-9-(2-cyanoalkyl)fluoren-9-yl)alkane of the and heated at 80° C. for 6 hours, over which time the formula: hydrogen pressure decreased to 52 p.s.i.g. The hydro generator was cooled, opened, and the contents were fil tered to remove the Raney nickel. The filtrate was added to 500 milliliters of water, whereupon the 1,6-bis(9-(N- 40 acetyl-3-aminopropyl)fluoren-9-ylhexane produced pre - cipitated. After filtration and recrystallization from hex NC ..., CnH2nOl.O CHCRCN ane-isopropanol mixture, it weighed 10 grams and melted wherein n is an integer having a value of from 2 to 10 at 176-179 C. After two additional recrystallizations and R is a member selected from the group consisting of from a hexane-isopropanol mixture the 1,6-bis(9-(N-ace hydrogen and methyl. tyl-3-aminopropyl)fluoren-9-ylhexane melted at 177 2. 1,2-bis(9-(2-cyanoethyl)fluoren-9-yl)ethane. 180° C. 3. 1,4-bis(9-(2-cyanoethyl)fluoren-9-yl)butane. Microanalysis.--Calculated for CH40ON: C, 32.4%; 4. 1,5-bis(9-(2-cyanoethyl)fluoren-9-yllpentane. H, 7.9%; N, 4.6%. Found: C, 82.4%; H, 8.0%; N, 5. 1,6-bis(9-(2-cyanoethyl)fluoren-9-ylhexane. 4.2%. EXAMPLE XI References (Cited by the Examiner 1,2-bis(9-(N-acetyl-3-aminopropyl)fluoren-9-yl)ethane UNITED STATES PATENTS 1,836,940 12/31 Sibley ------260-570.8 Employing apparatus and procedures similar to those 2,195,289 3/40 Sheldricket al. ------260-558 described in Example XII, 10 grams of 1,2-bis(9-(2-cyano 2,516,098 7/50 Bambas ------260-562 ethyl)fluoren-9-yl)ethane, 100 grams of acetic anhydride, 2,546,762 3/51 Long ------260-562 2 grams of Sodium acetate and about 3 grams of Raney 2,572,510 10/51 Allen et al. ------260-465.5 nickel catalyst were hydrogenated at 35-45 C. for 5 2,590,079 3/52 Abel et al. ------260-570.8 hours to produce 9 grams of 1,2-bis(9-(N-acetyl-3-amino 60 2,656,388 10/53 Schultz ------260-570.8 propyl)fluoren-9-ylethane, which, after recrystallization 2,779,780 1/57 Middleton ------260-466.5 from dioxane, melted at 267.5-269.5° C. 2,969,389 1/61 Kundiger et al. ----- 260-515 Microanalysis.-Calculated for CH4NO: C, 82.0% 2,971,980 2/61 Tinsley ------260-515 H, 7.2%; N, 5.0%. Found: C, 81.8%; H, 7.1%; N, 4.7%. 65 CHARLES B. PARKER, Primary Examiner. UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3, 205, 257 September 7, 1965 Henry E. Fritz et al.

It is hereby certified that error appears in the above numbered pat correctedent requiring below. correction and that the said Letters Patent should read as Column 1, 1ine 70, for "HOCnH2ng p" read -- HOCH2OH --; column 3, line 30, for 'bis (9-(2-carboxyalkyl) uuoren - 9-yl)' read - - b is 9 - (2-carboxyalkyl) fluoren - 9-yl) -- ; column 4, line 19, for "aminopropyl) fluoren -9-yl ethan' read -- aminopro - pyl) fluoren - 9-yl) decane - -; column 5, line 49, for "hydroxidemeth-' read - - hydroxide-meth - - -; column 6, 1ine 24, for '1,6-bis 19-(2-cyanoethyl) fluoren -9-" read -- 1,6-bis (9-(2- cyanoethyl) fluoren - 9 - - -; line 74, for "C37H26O4" read - - C37H36O4 - ; column 7, 1ine 48, for "C38H40ON2" read - - C42H48N2O2 Signed and sealed this 10th day of May 1966. (SEAL) At test :

ERNEST W. SWIDER EDWARD J. BRENNER Attesting Officer Commissioner of Patents