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United States Patent Office 3,258,488 United States Patent Office Patented June 28, 1966 2 ether, xylene, toluene, tetralin, cumene and tetrahydro 3,258,488 DIBENZOADCYCLOHEPTENEDERIVATIVES furan, and compatible mixtures of such solvents. The Claude I. Judd, Mequon, and Alexander E. Drukker and reaction can be effected at room temperature or elevated John H. Biel, Milwaukee, Wis., assignors to Colgate temperatures, depending on the reactivity of the alkali Palmolive Company, a corporation of Delaware metal compound used in the process. The reaction is No Drawing. Filed Aug. 12, 1963, Ser. No. 301,658 substantially complete in 1 to 4 hours. Following ter 3 Claims. (C. 260-570.8) mination of the reaction the product can be isolated, if desired, but this is ordinarily not done since it can be This is a continuation-in-part of abandoned application used as present in the reaction mixture in the next step. Serial No. 21,610 filed April 12, 1960. 10 Reaction between the alkali metal salt of 5H-dibenzo This invention relates to novel chemical compounds ad-cycloheptene and the disubstituted aminoalkyl ha and processes of preparing the same. More particularly, lide can be effected by bringing the reactants together in a this invention is concerned with novel basic dibenZSu suitable inert high boiling liquid reaction medium such berene derivatives and processes of producing such com as dioxane, toluene, Xylene, ethyl ether, tetralin, cumene pounds. and tetrahydrofuran. The reaction mixture from the According to the present invention there are provided formation of the alkali metal 5H-dibenzo(a,d)-cyclo novel basic 5H-dibenzoad-cycloheptene derivatives of heptene can be used as the reactant and solvent source the formula to which the appropriate aminoalkyl halide reactant can be added. The reaction proceeds at room temperature 20 although slightly elevated temperatures can also be used. ( -> r,R About 3 to 20 hours is generally adequate to substan )-A-NC tially complete the reaction. After the reaction is ter R2 minated, the product can be recovered by filtering the re action mixture, distilling off the solvent and fractionally 25 distilling the high boiling base in vacuo. and acid addition and quaternary ammonium salts there Among the disubstituted aminoalkyl halides which can of, wherein A is a lower straight or branched alkylene be used in the reaction are dimethylaminoethyl chloride, advisably of 2 to 5 carbons, and R1 and R2 are the same diethylaminoethyl bromide, diphenylaminopropyl chlo or different members of the group consisting of hydrogen, ride, dibenzylaminoethyl chloride, dicyclohexylamino lower alkyls such as methyl, ethyl, propyl, isopropyl and ethyl bromide, piperidinopropyl chloride, morpholinoethyl butyl, aryl groups and particularly phenyl, aralkyl groups bromide, pyrrollidinoethyl chloride, 4-methylpiperazino and particularly phenyl-lower alkyl groups including ethyl chloride, quinuclidinobutyl chloride, N-methyl-N- benzyl, phenylethyl and phenylisopropyl, cycloalkyl benzylaminoethyl chloride and N-phenyl-N-benzylamino groups and particularly cyclohexyl and cyclopentyl, cyclo ethyl bromide. alkyl-lower alkyl groups such as cyclohexyl-methyl and Some of the compounds which are produced according cyclopentyl-ethyl and groups in which to this invention are: 5-(N-benzyl-N-methylaminoethyl)-5H-dibenzo(a,d). NR cycloheptene, represents a heterocyclic amino group such as morpholino, 5-(2-dimethylaminoethyl)-5H-dibenzoad pyrrolidino, piperidino, 1,2,3,4-tetrahydroquinolino, 1,2, 40 cycloheptene, 3,4-tetrahydroisoquinolino, N - lower alkyl - piperazino 5-(3-dibenzylaminopropyl)-5H-dibenzoad groups such as N-methylpiperazino, N-(hydroxy-lower cycloheptene, alkyl)piperazino groups such as 4-(beta-hydroxyethyl)- 5-(4-diphenylaminobutyl)-5H-dibenzoa,d- piperazino and N - aralkylpiperazino groups such as 4- , cycloheptene, (methylphenethyl)-piperazino and the quinuclidino group. 5-(2-piperidinoethyl)-5H-dibenzoad The compounds of this invention in which R1 and R2 cycloheptene, are both substituents can be produced by reacting an 5-(4-methylpiperazinopropyl)-5H-dibenzoa,d- alkali metal salt of 5H - dibenzo(a,d) cycloheptene with cycloheptene, the appropriate disubstituted aminoalkylhalide or disub 5-(quinuclidino)-5H-dibenzoad-cycloheptene, and tituted aminoalkyl para-toluenesulfonate. This process 5-4-(beta-hydroxyethyl)-piperazinopropyl-5H can be represented as follows: dibenzoad-cycloheptene. The compounds of the formula R3 ( ) R. 5 5 -M - X-A-N / >- A > R R4 wherein M is an alkali metal and particularly lithium, () sodium or potassium, X is a reactive halogen and par ticularly chlorine, bromine or iodine or the para-toluene in which A and Rs have the significance previously as sulfonate group. A has the significance previously as signed but Rs is not benzyl can be produced by subject signed and Rs and R4 have the same meaning as R1 ing the compounds of the formula and R but neither is hydrogen. 65 The alkali metal 5H - dibenzo(a,d) - cycloheptene Salt used as a reactant can be prepared by reacting 5H-di benzoad-cycloheptene with an alkali metal alkyl or aryl compound such as butyl lithium, phenyl lithium, propyl sodium and butyl potassium. The reaction is 70 readily effected by bringing the reactants together in an inert anhydrous liquid reaction medium Such as ethyl in which A and Rs have the assigned significance, but 3,258,488 3. 4. R is not benzyl, and p is phenyl, to catalytic cleavage The hydrolytic cleavage step is effected by bringing the of the benzyl group. Similarly, the compounds N-carbo-R5-oxy dibenzosuberene derivative into contact with an alkali hydroxide under conditions which effect hydrolysis of the carbo-R5-oxy group. The reaction me dium is desirably one in which the alkali carbonate, a by product of the reaction, is insoluble. Alcohols and glycols C2b such as ethylene glycol are particularly useful reaction media. A particularly suitable alkali hydroxide is barium hydroxide; however, sodium hydroxide or potassium hy can be subjected to catalytic cleavage to form the com O droxide may be employed. pounds After the hydrolysis is terminated, the reaction mixture can be diluted with water, filtered to remove the alkali carbonate, extracted with an immiscible solvent such as benzene and the benzene extracted with very dilute aque 5 ous hydrochloric acid. The acid extracts are then made >-A-NH. basic, the oil taken up in ether and the ether removed to give the product. in which A and b have the assigned significance. Some of the compounds produced in either of the above The catalytic reductive cleavage of the benzyl group acS ae is readily effected by adding the appropriate N-mono or 20 5-(3-aminopropyl)-5H-dibenzoadcycloheptene, dibenzyl dibenzosuberene derivative, either as the free 5-(2-aminopropyl)-5H-dibenzo(a,d) cycloheptene, base or the acid addition salt, to a solvent such as water 5-(2-aminoethyl)-5H-dibenzo(a,d) cycloheptene, or a lower alcohol, adding a catalyst such as palladium, 5-(2-methylaminoethyl)-5H-dibenzoa,d) cycloheptene, and hydrogen under pressure, as up to about 100 p.s.i. 5-(3-methylaminopropyl)-5H-dibenzoa,d] cycloheptene, The hydrogenation proceeds quickly and its progress can 25 and be measured by the hydrogen uptake. When the required 5-(2-phenylaminoethyl)-5H-dibenzo(a,d)cycloheptene. quantity of hydrogen is consumed, the reaction is ter Acid addition salts of the compounds of this invention minated. The reaction mixture is worked up in the con can be produced by contacting the dibenzosuberene deriv ventional manner. 30 atives with a suitable inorganic or organic acid such as The compounds of the formula hydrochloric, sulfuric, phosphoric, maleic, benzoic, tar taric, succinic, fumaric, methane sulfonic, and citric acid in a suitable solvent such as methanol, ethanol, isopro panol, ethyl acetate and acetonitrile. The salts form 35 readily at room temperature and can be separated by con ventional methods. These compounds, as the free bases and nontoxic acid addition salts thereof, are central stimulants and anti in which A and R3 have the significance previously as spasmodic agents in animals. The compounds thus can signed but R3 is not benzyl may alternatively be produced 40 be used in depression and mild gastrointestinal dis by reacting a compound of the formula turbances. For obtaining the described activities the compounds can be administered in combination with a suitable phar maceutical carrier and advisably in a unit dosage form such as a table or capsule. The oral route of adminis 45 tration is preferred. The compounds of this invention can also be used as with a chloroformate having the formula neutralizing agents and in the isolation of penicillin from O fermentation broths. cidor, 50 The following examples are presented to illustrate the in which R5 is a lower alkyl such as methyl, ethyl and preparation of compounds within the invention. propyl; phenyl or phenyl-lower alkyl such as benzyl and EXAMPLE I phenethyl, to produce a compound of the formula 5-(3-dimethylaminopropyl)-5H-dibenzoa,d) 55 cycloheptene ( > r, A 300 cc. three-neck round bottom flask was charged with a solution of 9.6 g. (0.05 mole) of dibenzosuberene in 75 cc. of tetrahydrofuran. The solution was covered with nitrogen, cooled in ice water and, while stirring, a 60 solution of 32 cc. of butyl lithium solution 15.4% (0.055 and subjecting said compound to hydrolytic cleavage. mole) in 50 cc. of ether was added dropwise in 15 min. In the first step of the process the chloroformate and A dark brown color developed and the solution was stirred the N-benzyl dibenzosuberene derivative are brought to for 4 hours at room temperature. Then there was added, gether in a suitable inert liquid reaction medium at a tem in 35 min., a solution of 6.1 g. (0.05 mole) of 3-dimethyl perature which induces the reaction. Benzene, toluene, 65 amino propylchloride in 30 cc. of ether. The dark color xylene and tetralin are representative reaction media disappeared and LiCl began to precipitate.
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