Patent ES-8306989-A1 (ES)
Title: Aromatic and heterocyclic ether prodn. from halide
IPC: C07C43/20
Filed: 1982-02-15
Abstract: Ethers of formula (I) (where A completes a carbocyclic or heterocyclic aromatic ring which is either a monocyclic ring or part of a polycyclic ring which is at least partly aromatic and may have one or more substits.; R is (substd.) alkyl, alkenyl, alkynyl or benzyl of up to 12C) are produced by reacting (I) where OR is replaced by Cl, Br or I with an alcoholate M(OR)n (where M is an alkali(ne earth) metal and n is its valency) in the presence of a formate ester of formula R2.O.CO.H (where R2 is a (substd.) alkyl, alkenyl, alkynyl or benzyl gp. having up to 12C) and a cuprous salt under anhydrous and non-oxidising conditions. - The reaction is of general applicability and gives good yields in most cases. It is esp. useful for making methyl ethers. The catalyst is inexpensive and no expensive solvents or high pressures or temperatures are required. EPAB- EP--57321 B In a process for preparing a cpd. of formula (I) in which A is the residue of an aromatic ring forming the whole or part of a monocyclic or polycyclic, at least partially-aromatic, carbocyclic and/or heterocyclic ring system, opt. bearing one or more other substits. inert to the reactants here employed, and R is opt. substd. alkyl, alkenyl, alkynyl or benzyl with upto 12C atoms, an aromatic cpd. of formula (II) in which A is as above and X is Cl, Br or I, is reacted with an alcoholate Mn+(O-R)(-)n in which M is an alkali-or alkaline earth metal atom, n is the valency of M and R is as above. - The novelty is that the reaction is effected in the presence of a catalytically-effective amt. of an active catalyst mixt. comprising (i) a formic acid ester of an aliphatic organic alcohol of formula R2-O-CO-H in which R2 is an opt. substd. alkyl, alkenyl, alkynyl or benzyl gp of upto 12C atoms; and (ii) a cuprous salt; in a liq. medium which is a solvent for the catalyst mixt. and in which cpd. (II) is at least partially soluble, under anhydrous conditions and a non-oxidising atmosphere, to give the desired corresp. cpd (I). - The process is clean and reproducible giving usually good yields at temps. below 100 deg.C and ambient press. (18pp) GBAB- GB2089672 B Ethers of formula (I) (where A completes a carbocyclic or heterocyclic aromatic ring which is either a monocyclic ring or part of a polycyclic ring which is at least partly aromatic and may have one or more substits.; R is (substd.) alkyl, alkenyl, alkynyl or benzyl of up to 12C) are produced by reacting (I) where OR is replaced by Cl, Br or I with an alcoholate M(OR)n (where M is an alkali(ne earth) metal and n is its valency) in the presence of a formate ester of formula R2.O.CO.H (where R2 is a (substd.) alkyl, alkenyl, alkynyl or benzyl gp. having up to 12C) and a cuprous salt under anhydrous and non-oxidising conditions. - The reaction is of general applicability and gives good yields in most cases. It is esp. useful for making methyl ethers. The catalyst is inexpensive and no expensive solvents or high pressures or temperatures are required. (11pp) - GB2089672 B A process for the preparation of a compound of the general formula (VI) wherein A represents the residue of an aromatic ring forming the whole or a part of a monocyclic or polycyclic, at least partially-aromatic, carbocyclic and/or heterocyclic ring system, optionally bearing one or more other substituents inert to the reactants here employed, and R represents an optionally-substituted alkyl, alkenyl, alkynyl or benzyl group having up to 12 carbon atoms, which process comprises causing an aromatic compound of the general formula (II) wherein A is as defined above and X represents a chlorine, bromine or iodine atom, to react with an alcoholate of the general formula: in which M represents an alkali metal or an alkaline earth metal atom; n is the valency of M; and R is as defined above, in the presence of a catalytically-effective amount of an active catalyst mixture comprising: - (i) a formic acid ester of an organic alcohol having the general formula: R2-O-CO-H (V) in which R2 represents an optionally-substituted alkyl, alkenyl, alkynyl or benzyl group having up to 12 carbon atoms; and - (ii) a cuprous salt as hereinbefore defined; in a liquid medium which is a solvent for the catalyst mixture and in which the compound of formula II is at least partially soluble, under substantially anhydrous conditions and a non-oxidising atmosphere, to yield the desired corresponding compound of formula VI.t USAB- US4422955 A Halogen atoms attached to the nuclear C of an aromatic ring is substd. by -O-R, by reacting the substrate contg. the aromatic ring with alcoholate (M)n+(O-R)n- in the presence of a mixt. of a formic acid ester of an organic alcohol of formula R2-O-CO-H and a cuprous salt as catalyst. - The substrate contg. the aromatic ring is the whole or part of a partially or wholly aromatic substrate comprising a monocyclic-or polycycli-carbocyclic or -heterocyclic cpd. In the formulae, M is an alkali metal or alkaline earth metal; n is its valency; R is 1-12C alkyl, 3-12C alkenyl or alkynyl, or benzyl and R2 is an R gp. The catalyst is anhydrous and protected against oxidative breakdown. - The catalyst used esp. comprises cuprous bromide, and has mol.ratio of formic acid ester to cuprous salt of 0.1-0.6:0.6-0.1.  (9pp)t - US4495353 A Process for substituting a halogen atom attached to the nuclear C atom of an aromatic ring forming all or part of a partially or wholly aromatic monocyclic or polycyclic, carbocyclic or hetercyclic cpd. with a substit. of formula OR where R is 1-6C alkyl. - The cpd. (1 mole) is reacted with an alcoholate (0.9-10 mole) of formula Mn+(O-R-)n, where m is alkali metal atom of valency n, in the presence of a catalytic mixt. comprising (1) formic acid ester of an organic -alcohol (0.01-3 mole) of formula R2 O-CO-H, where R2 is 1-4C alkyl and (2) cuprous salt (0.01-3 mole. Reaction takes place in liq. medium which is solvent for the catalyst mixt. and in which the starting cpd. is at least partially soluble, under anhydrous conditions and in a nonoxidising atmos. Temp. is up to 120 deg. C.