Patent GB-813758-A (GB)
Title: Improvements in the production of polyhydroxy ethers having an action similar to curare
Filed: 1956-09-17
Abstract: The invention comprises polyhydroxy cyclooctane ethers of the general formula <FORM:0813758/IV (b)/1> wherein R represents an aliphatic radical, and the preparation thereof by treating with dilute mineral acid an ether of the general formula <FORM:0813758/IV (b)/2> wherein R has the above significance, and by treating with an aqueous organic per-acid an ether of the general formula <FORM:0813758/IV (b)/3> wherein R has the above significance.  The dilute mineral acid may be dilute sulphuric or phosphoric acid, e.g. 2N sulphuric acid, in which case a temperature of 70 DEG  to 90 DEG  C. may be employed. Suitable per-acids are performic, peracetic and perbenzoic acids. In the examples: 2-methoxycyclo-octanol-(1)-glycerine ether is prepared by treating 2-methoxycyclooctanol glycide ether with 2N sulphuric acid and by treating 1-allyloxy-2-methoxy-cyclooctane with performic acid. Cyclo-octane ethers of the general formula <FORM:0813758/IV (b)/4> wherein R represents an aliphatic radical, are prepared: (1) by reacting 1,2-epoxycyclooctane with glycerine-alpha-monochloro (or bromo)-hydrin to form the corresponding halogenohydrin monoether of cyclo-octaine-diol-(1,2) which is then treated with alkali and then etherified as required, or (2) by reacting 1,2-epoxycyclo-octane with the required alcohol ROH such as methanol, propanol, allyl alcohol, benzyl alcohol or cyclohexanol to form a cyclooctane ether of the formula <FORM:0813758/IV (b)/5> reacting this compound with an epihalogenohydrin such as epichlorhydrin to form an ether containing a halohydrin group, and treating this compound with alkali.  In the examples: (1) 2 - methoxycyclo - octanol - 1 - (gamma - chlor - beta - hydroxypropyl) ether is prepared by reacting epichlorhydrin and alpha-methoxycyclo-octanol in the presence of boron trifluoride and is then converted into 2-methoxy-cyclo-octanolglycide ether by reacting with aqueous sodium hydroxide; and (2) 2-hydroxycyclo - octanol - (1) - glycerine monochlorhydrin ether is prepared by reacting 1,2-epoxycyclooctane with glycerine-alpha-monochlorhydrin in the presence of boron fluoride etherate, this compound is converted into 2-hydroxycyclooctanol - (1) - glycide ether by reacting with aqueous sodium hydroxide.  Cyclo-octane ethers of the general formula <FORM:0813758/IV (b)/6> wherein R represents an aliphatic radical, are prepared (1) by reacting the mono-allyl ether of cyclo-octane-1,2-diol, preferably in the form of an alkali metal derivative thereof, with an alkylating agent such as a methyl, ethyl, propyl, allyl, benzyl or cyclohexyl halide, or with ethylene oxide; (2) by reacting the alkali metal derivative of a monoether of cyclo-octane-1,2-diol of the formula <FORM:0813758/IV (b)/7> wherein R has the above significance, with an allyl halide such as an allyl bromide; (3) by reacting the mono-propinyl ether of cyclo-octane-1,2, if desired in the form of its alkali metal derivative, with the required alkylating agent to form a cyclo-octane diether of the formula <FORM:0813758/IV (b)/8> wherein R has the above significance, and partially hydrogenating the double bond, e.g. using finely-divided palladium as the catalyst; and (4) by reacting an alkali metal salt of mono-ether of cyclo-octane-1,2-diol of the formula <FORM:0813758/IV (b)/9> wherein R has the above significance, with a propargyl halide such as propargyl bromide, and partially hydrogenating the resulting cyclo-octane diether of the formula in (3) by the method of (3). In an example 1-allyloxy-2-methoxy-cyclo-octane is prepared by reacting the sodium salt of alpha-methoxycyclo-octanol with allyl bromide, and by reacting the sodium salt of alpha-allyloxycyclo-octanol with methyl chloride.  Specification 806,297 is referred to.