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United States Patent Office 2,763,643 United States Patent Office Patented Sept.2,763,643 18, 1956 1. 2 will take place within the range of about 25 to 120° C. 2,763,643 Examples of preferred solvents are the nitro and nitrile compounds such as nitrobenzene, nitromethane, nitro AZACYCLOHEPTANE COMPOUNDS AND ethane, 1-nitropropane, acetonitrile and benzonitrile. METHODS FOR PREPARING THEM If the precipitate that forms from the aforesaid reaction Richard F. Tislow, Richard de Vere Huber, and Julius is large, the reaction mixture is chilled with ice-water and Diamond, Philadelphia, Pa., assignors to American then treated with a large volume of relatively low boiling Home Products Corporation, New York, N. Y., a cor ketone, Such as acetone or methyl-ethylketone. If little poration of Delaware or no precipitate forms, the reaction mixture is treated No Drawing. Application September 3, 1954, lo with a relatively non-polar solvent such as diethylether, Serial No. 454,195 heptane or benzene. Surprisingly, an excellent granular product is obtained by adding the reaction mixture gradu 9 Claims. (CI. 260-239) ally to the non-polar solvent, rather than using the re This invention relates to azacycloheptane compounds lis verse procedure. and more particularly to bis-quaternary salts comprising The desired product obtained as a precipitate is sepa said heterocyclic rings. rated from the reaction mixture, washed with non-polar The compounds of the invention fall within the follow Solvent and dried. If further precipitation is sought, the ing general formula: product may be recrystallized from a mixture of a low 20 boiling alcohol of 1 to 5 carbon atoms and low boiling -- - - ketone having 3 to 6 carbon atoms, ether, or hydrocarbon Solvent being used additionally if the crystallization takes & N-alk-ST:i. A place too slowly. !---4, S--- The azacycloheptane reactant may be prepared as dis wherein closed in Diamond and Bruce Patent No. 2,666,050, dated XY.sm 25 Jan. 12, 1954, and in their applications Ser. Nos. 400,136. :---1 and 403,448 filed respectively on Dec. 23, 1953 and represents an azacycloheptane ring, R1 represents a lower jan. 11, 1954. Application Ser. No. 400,136 teaches the alkyl, preferably methyl, "alk' indicates a divalent alkyl method for making 4-arylazacycloheptanes having also ene radical of 4 to 12 carbon atoms and A stands for 30 in the 4-position either hydrogen, -CONH2, -COOH, a pharmacologically non-toxic anion. Suitable salts of or -COO alkali metal. the free bases may comprise the bromides, iodides, nitrates, To make the 4-arylazacycloheptanes of application Ser. sulphates or salts of the lower aliphatic carboxylic acids. No. 400,136 one utilizes the corresponding 4-aryl-4-cyano Actually any acid may be used which is known to be azacycloheptane whose general formula is shown in the pharmacologically safe. above mentioned patent and which is made as shown by 3. 5 reactions 1, 2 and 3 therein. The cyano substituent is With regard to the azacycloheptanering represented hydrolyzed by, known procedures to form the amide or above, it may be more specifically illustrated by the -CONH2 radical. Alternatively, the amide may be structure -' , formed by reacting the 4-cyano compound with a higher alcohol and a base, as for example heptanol and potas R R. R. 40 sium hydroxide at a temperature of about 160 C. C.H.--CH-) To obtain the carboxylic acid radical, -COOH in place : /.N of the cyano group, the reaction with alcohol and base CH-CH-cfi, as above described is carried out at a higher temperature, wherein R2 and R3 stand for hydrogen or a lower alkyl, 45 in the neighborhood of 200°C. If the 4-amide compound while R4 represents either hydrogen, cyano, -COO. lower is reacted with an alkali metal hydroxide alone, the alkali alkyl, -COO. alkali metal, -CO lower alkyl, -CONH2, metal carboxylic acid salt will form. Should one merely -COOH or -O-CO"lower alkyl. wish to remove the cyano substituent, the 4-cyano com The compounds of the invention are pharmacologically pound may be heated at about 250° C. in the presence of useful in the veterinary or human field in that they have 50 alkali metal hydroxide and water. By another procedure, been found to possess curare-like, musicle-relaxing action one may decyanate, the azacycloheptane by reacting the among other pharmacological actions. Thus, in com corresponding 4-cyano compound with an alkali-metal pounds where R4 represents hydrogen, a ganglionic stimul amide in the presence of an inert organic solvent of the lating action has also been noted. Compounds showing hydrocarbon type such as hexane or benzene, or their the strongest curare-like action are those where R2 and 55 higher homologues. R3 stand for hydrogen with R4 representing an ester of The 4-acyloxy azacycloalkanes of application Ser. No. the -COO-lower alkyl type, and with the alkylene chain 403448 may be prepared from the corresponding 4-cyano having from 4 to 10 carbon atoms. - compounds of Patent No. 2,666,050 described previously. The compounds may be prepared by heating the aza Thus, the cyano compound is subjected to decyanation as cycloheptane with an alkylene dihalide preferably using 60 above described and the decyanated product is then reacted a molar ratio of at least 2:1 azacycloalkane to halide. with a tetra lead salt of a lower aliphatic carboxylic acid, It has been found that substantial yields may be with the reaction being carried out in the presence of the achieved if the reaction takes place in a solvent and if corresponding aliphatic acid. As an example, the reaction. the solvent medium is highly polar, having a high dielec to replace the cyano radical with the acyloxy radical tric constant or dipole moment under standard conditions. 65 -O-CO-CH3 is carried out using lead tetra-acetate (20° C.) of about 2.5 Debye units or greater. The dielec in the presence of acetic acid as a solvent, the temperature tric constant should be about 10 (epsilon) or greater and of reaction being in the neighborhood of about 80 to preferably from about 15 to 40 when measured under 85 C. standard conditions. Additionally the highly polar sol The following examples disclose the invention in vent should have a boiling point above about 70° C. since 70 specific detail. It should be clearly understood that the the reaction goes best and with the greatest yield within. examples are merely for illustration and are not to be. the range of about 70 to 100° C. although the reaction construed as limitative of the invention. 2,768,643 3 4. EXAMPLE 1. EXAMPLE 4. 1,4-bis-(4-cyano-1-methyl-4-phenyl-azacycloheptane 1,5-bis-(1-methyl-4-phenyl-azacycloheptane-onium)- onium)-tetramethylene dibromide pentamethylene dibromide - 5 1-methyl-4-phenyl-azacycloheptane 2.0 g. (0.011 4-cyano-1-methyl-4-phenyl - azacycloheptane, 2.6 g. mole) and 1,5-dibromopentane, 1.2 g. (0.0050 mole) in (0.012 mole), 1,4-dibromobutane, 1.1 g. (0.0050 mole), 8 m. of benzonitrile were heated at 100° C. for about and nitromethane, 8 ml, were mixed and heated at 100 3 hours. White crystals appeared after first 5 minutes. C. for 6 hours. The product was precipitated by the After cooling to room temperature, it was treated addition of dry ether. After trituration with ether, it 0 with acetone with stirring, filtered, and washed on the was crystallized by dissolving in a hot mixture of acetone filter with acetone and ether. This gave a white solid and methanol (minimum), evaporating and cooling. product that was recrystallized from a mixture of acetone The desired product melted at 226-28° C. (decomposi- and methanol (minimum) and melted at 238-239 C. tion). Analysis.-C31H48N2Br2: Analysis.-C32H44N4Br2: 5 - - -- Nitrogen,percent Bromine,percent Nitrogen, Bromine, -a-worm------ - - percent percent Caled----------------------------------------- 4.61 26.3 Found---------------------------------------- 4.85 - 26.6 Caled----------------------------------------- 8.68 24.8 20 Found---------------------------------------- 3.96 24, 8 EXAMPLE 5 1,6-bis-(1-methyl-4-phenyl-azacycloheptane-onium)- EXAMPLE 2 hexamethylene dibromide and dinitrate 1,5-bis-(4-cyano-1-methyl-4-phenyl-azacycloheptane- 25 methyl-4-phenylazacycloheptane, 1.9 g (0.019 (Englicientiocher mole), 1,6-dibromohexane, 1.2 g (0.0050 mole), and nitrobenzene 3.0 ml, were mixed and heated at 100° C. 4-cyano-1-methyl-4-phenyl - azacycloheptane, 2.6 g. for 1.5 hours. After cooling, the thick mass was mixed (0.012 mole), 1,5-dibromopentane, 1.2 g (0.0050 mole), well with acetone to disperse the crystals and filtered, and nitrobenzene, 8 ml, were mixed and heated at 100° 30 The solid was washed and dried under ether for 4 days. C. for 6 hours. After cooling in an ice-bath, acetone, The desired product melted at 200-202°C. 15 ml, was added with stirring. The solid, after filter- Analysis.-C32H5ON2Br2: ing, was triturated well with dry ether and dried at 50 C. The desired product melted at 205-210° C. It may Nitrogen, Bromine, be recrystallized from acetone and methanol (minimum). 35 percent percent Analysis.-C33H46N4Br2: Calcd--...-- 4.52 25.8 Found------ 4.64 23.9 Nitrogen, Bromine, percent percent 40 Silver nitrate, 0.55 g. (0.0032 mole), in 10 ml. of distilled water was added dropwise with stirring to 1.0 g. (0.0016 Sisir:::::::::::::::::::::::::::: S- 33 mole) of 1,6-bis-(4-phenyl-1-methylazacycloheptane: - - - - onium)-hexamethylene dibromide in 25 mi. of distilled water at room temperature. After stirring 15 minutes EXAMPLE 3 more, the mixture was filtered. The water of the clear 4 filtrate was removed under a pressure of 10 mm.
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