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Morpholine Derivatives, Pharmaceutical Compositions

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Morpholine Derivatives, Pharmaceutical Compositions Europâisches Patentamt O 027 695 19 European Patent Office (JÎ) Publication number: Office européen des brevets Bl EUROPEAN PATENT SPECIFICATION @ Date of publication of patent spécification: 12.10.83 @ Int. Cl.3: C 07 D 265/30, A 61 K 31/535 ®* —. Apphcat.cn, number:u 80303473.5onon0/,„c //C07 D303/22, C07C93/1 4, @ Date offiling: 02.10.80 C07D265/32, C07C1 03/1 27 (54) Morpholine derivatives, pharmaceuticai compositions containing them and processes for their préparation. (30) Priority: 20.1 0.79 GB 7936502 (73) Proprietor: JOHN WYETH & BROTHER LIMITED Huntercombe Lane South Taplow Maidenhead Berkshire, SL6 0PH (GB) @ Date of publication of application: 29.04.81 Bulletin 81/17 (72) Inventor: White, Alan Chapman 5 Sherbourne Drive (45) Publication of the grant of the patent: Windsor Berkshire (GB) 12.10.83 Bulletin 83/41 Inventor: Edington, Edwin Trevor 112, Broom Hill Cookham Berkshire (GB) @ Designated Contracting States: AT BE CH DE FR IT LI LU IML SE (74) Representative: Brown, Keith John Symons et al, c/o John Wyeth & Brother Limited Huntercombe (56) References cited: Lane South GB - A - 1 336 732 Taplow Maidenhead, Berkshire SL6.0PH. (GB) GB- A- 1 452 701 US - A - 2 835 669 US - A - 2 997 469 US-A-3 112311 The file contains technical information submitted after the application was filed and not included in this specification Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1 ) European patent convention). Courier Press, Leamington Spa, England. This invention relates to morpholine derivatives, to processes for their preparation and to pharmaceutical compositions containing them. Various morpholine derivatives have been described previously as having pharmacological properties. For example, U.S. Specification 2,997,469 discloses inter alia 2-phenyl or substituted phenylmorpholines, e.g. 2-(m-hydroxyphenyl)-3-methylmorpholine, which are stated to be stimulants of the central nervous system. Similar type of activity is disclosed for the 2-phenyl or substituted phenyl-5,6-dimethyl or tetramethylmorpholines of U.S. Specification 3,112,311. U.K. Specification No. 1,336,732 discloses 2-phenyl or alkoxy substituted phenylmorpholines such as 2-phenyl-5,5-dimethyl- morpholine which apparently has convulsant properties. U.S. Specification 2,835,669 discloses 2- phenyl or substituted phenyl-3-phenyl or lower alkylmorpholines, such as 2-phenyl-3-methyl- morpholine which are stated to cause deferring or tiring. All the above mentioned morpholines of the prior art bear a single substituent (phenyl or substituted phenyl) in the 2-position of the morpholine ring. The present invention provides novel morpholine derivatives of the general formula (I) and their pharmaceutically acceptable acid addition salts. In this formula R' represents lower alkyl; R2 represents hydrogen, lower alkyl, benzyl, (lower)alkoxymethyl or a lower alkanoyl group; R3 represents hydrogen, lower alkyl or phenyl; R4, R5 and RS are independently hydrogen or lower alkyl and R7 is hydrogen, lower alkyl, lower alkenyl, lower alkynyl, phenyl(lower)alkyl, 2-tetrahydrofurylmethyl or cycloalkylmethyl. The term "lower" as used herein means that the radical referred to contains up to 6 carbon atoms. The radical preferably contains up to 4 carbon atoms. For example when any of the groups R1, R2, R3, R4, R6, R6 and R7 is a lower alkyl group the radical may be, for example, methyl, ethyl, propyl or butyl. When R7 is lower alkenyl or lower alkynyl suitable groups include, for example allyl, 2-methyl-2-propenyl, 3- methylbut-2-enyl and propynyl. When R7 is cycloalkylmethyl the group is preferably cyclopropylmethyl or cyclobutylmethyl. When R7 is phenyl(lower)alkyl the group can be, for example benzyl or phenethyl. When R2 is a lower alkanoyl group it is preferably acetyl, propionyl or butyryl. When R2 is a (lower)alkoxymethyl group it is preferably a methoxymethyl group. In a preferred group of compounds of general formula I, R' is an ethyl group, R2 is hydrogen, R3 is hydrogen or lower alkyl (e.g. methyl), R4, R5 and RS are hydrogen and R7 is lower alkyl (e.g. methyl). Particularly preferred compounds are 2 - ethyl - 2 - (3 - hydroxyphenyl) - 4,6 - dimethyl- morpholine and pharmaceutically acceptable acid addition salts thereof, especially in the form of diastereoisomers of configuration corresponding to that of the 2 - ethyl - 2 - (3 - hydroxyphenyl) - 4,6 - dimethylmorpholine hydrobromide having the melting point of about 222° to 226°C. It is believed that such diastereisomers have the 2R*, 6S* configuration. The compounds of the invention can be prepared by reduction of a compound of general formula (II) wherein R1, R2, R3, R4 and R7 are as defined above, (where R5 is as defined above) and (where RS is as defined above) with the proviso that at least one of X and X' is oxo, and if desired converting a free base of general formula (I) into a pharmaceutically acceptable acid addition salt thereof. The compound of general formula (II) can be reduced with, for example, a hydride transfer agent (e.g. lithium aluminium hydride). Preferably in the compound of formula (II), Once a compound of general formula (I) has been prepared it may be converted into another compound of general formula (I) by methods known per se. For example, a compound in which R7 is lower alkyl, lower alkenyl, lower alkynyl, phenyl(lower)alkyl, 2-tetrahydrofurylmethyl or cycloalkylmethyl may be prepared by "N-alkylating" a compound in which R7 is hydrogen. By "N- alkylating" is meant introducing on to the nitrogen atom of the morpholine ring a lower alkyl, lower alkenyl, lower alkynyl, phenyl(lower)alkyl, 2-tetrahydrofurylmethyl or cycloalkylmethyl radical. In one method of carrying out the "N-alkylating" process a compound of general formula I in which R7 is hydrogen is reacted with a halide of general formula where R7' is lower alkyl, lower alkenyl, lower alkynyl, phenyl(lower)alkyl, 2-tetrahydrofurylmethyl or cycloalkylmethyl and Hal is a halogen atom, in the presence of an acid acceptor such as an alkali metal carbonate (e.g. potassium carbonate), preferably in solution in an organic solvent. Alternatively the compound of general formula (I) in which R7 is hydrogen may be alkylated by reductive alkylation i.e. by treatment with an aldehyde and hydrogen in presence of a hydrogenation catalyst. A preferred method of cycloalkyl-methylating involves reacting the N-unsubstituted compound with a cycloalkylcarbonyl chloride to give an intermediate N-carbonyl cycloalkyl compound which may be reduced with, for example, a hydride transfer agent. A compound of general formula (I) in which R2 is a hydrogen atom can be obtained from a corresponding compound in which R2 is lower alkyl, lower alkoxymethyl or benzyl by splitting off the ether group in known manner, e.g. by treating the lower alkyl or benzyl ether with hydrogen bromide or boron tribromide, by treating the lower alkyl ether with diisobutylaluminium hydride or by subjecting the benzyl ether to hydrogenolysis or by treating the (lower) alkoxymethyl ether with dilute acid. Similarly a compound of general formula (I) in which R7 is benzyl may be hydrogenolysed to a compound of general formula (I) in which R7 is hydrogen which, if desired may then be "alkylated" as hereinbefore described. Compounds in which R7 is lower alkyl, particularly methyl may also be dealkylated to compounds in which R7 is hydrogen, e.g. by reaction with ethyl-, phenyl-, vinyl- or 2,2,2- trichloroethyl-chloroformate followed by removal of the resulting N-substituent with, for example, dilute acid or zinc and acetic acid or basic conditions as appropriate. A compound of general formula (I) in which R2 is hydrogen can be acylated (e.g. with acetic anhydride) to give a corresponding compound in which R2 is a lower alkanoyl radical. Two or more of the above mentioned processes for interconverting the compounds of general formula (I) may, if desired, be carried out consecutively. In some instances it may be necessary to protect one or more of the functional groups on the molecule while reaction occurs at another functional group and then subsequently remove the protecting group or groups. The preferred compound of general formula (II) is one in which X represents oxo and This compound may be prepared by cyclisation of a haloamide of general formula (III) wherein R1, R3, R4, R6 and R7 are as defined above, R2' is lower alkyl, (lower)alkoxymethyl or benzyl, and Z is bromo or chloro. If desired the R2 group [lower alkyl, (lower)alkoxymethyl or benzyl] in the resulting amide of general formula (II) may be converted into another R2 group (hydrogen or acyl) by selection of a suitable method from the methods described above in connection with the interconversion of the R2 group in compound I. Again, if desired, an amide of formula (II) where R4 is hydrogen may be alkylated to give an amide where R4 is lower alkyl e.g. by reaction with a lower alkyl halide to presence of a strong base. Examples of strong bases are given hereinbelow. The cyclisation of the haloamide of general formula (III) may be carried out with a basic agent such as an alkali metal hydride or alkali metal hydroxide. The haloamide is preferably prepared by condensing an @-halo acid halide of general formula (IV) where R3, R4, and Z are as defined above and Z1 is chloro or bromo with an aminoalcohol of general formula (V) where R1, R2', R6 and R7 are as defined above.
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