Patent GB-836740-A (GB)
Title: Coumarin derivatives and their production
Filed: 1957-04-25
Abstract: The invention comprises a 4-hydroxy coumarin of the formula <FORM:0836740/IV (b)/1> in which A stands for a radical which with the a -pyrone ring forms a 1,2-benzo-pyrene (coumarin) ring, R1 stands for alkyl and R2 stands for an alkyl aryl radical, or <FORM:0836740/IV (b)/2> is combined to form a hydroaromatic or heterocyclic radical, and a process for the preparation of compounds having said formula wherein A and R1 have the meanings set out above and R2 stands for aryl, or <FORM:0836740/IV (b)/3> is combined to form a hydroaromatic or heterocyclic radical, which comprises reacting at an elevated temperature a 4-hydroxy-coumarin of the formula <FORM:0836740/IV (b)/4> with a compound of the formula <FORM:0836740/IV (b)/5> in which A, R1 and R2 are as defined above. The reaction may be effected in an inert organic solvent, e.g. formic acid, acetic acid, propionic acid, chlorobenzene and tetrahydronaphthalene, with or without the addition of condensing agents, e.g. sulphuric acid, zinc chloride, phosphoric acid, aluminium chloride and phosphorus pentoxide, or by heating the components in the melt with or without the addition of condensing agents.  Reaction temperatures in the range 50-250 DEG  C. and preferably 100-150 DEG  C., may be employed.  Examples describe the preparation of 3 - (a  - phenyl - ethyl) - 4 - hydroxy - coumarin, 6 - chloro - 3 - (a  - phenylethyl) - 4 - hydroxy - coumarin, 3 - (a  - phenylethyl) - 4 - hydroxy - coumarin, 3 - (a  - phenyl - propyl) - 4 - hydroxy - coumarin, 3 - (a  - tetrahydronaphthyl) - 4 - hydroxy - coumarin, 7 - chloro - 3 - (a  - tetrahydronaphthyl) - 4 - hydroxy - coumarin, 7 - methyl - 3 - (al.a  - tetrahydronaphthyl) - 4 - hydroxy - coumarin, 6 - methyl - 3 - (al.a  - tetrahydronaphthyl) - 4 - hydroxy - coumarin, 7 - methoxy - 3 - (al.a  - tetrahydronaphthyl) - 4 - hydroxy - coumarin, 3 - (a  - indanyl) - 4 - hydroxy - coumarin, 3 - (a  - phenyl - ethyl) - 4 - hydroxy - coumarin, 3 - (a  - phenyl - n - propyl) - 4 - hydroxy - coumarin, 3 - (a  - p - tolyl - n - propyl) - 4 - hydroxy - coumarin, 3 - (a  - p - chlorophenyl - n - propyl) - 4 - hydroxy - coumarin, 7 - methyl - 3 - (a  - phenyl - n - propyl) - 4 - hydroxy - coumarin, 3 - (a  - phenyl - n - butyl) - 4 - hydroxy - coumarin, 3 - [a  - (4 - isopropylphenyl) - ethyl] - 4 - hydroxy - coumarin, 3 - [a  - (4 - ethyl - phenyl) - n - propyl] - 4 - hydroxy - coumarin, 3 - al.a  - tetralyl - 4 - hydroxy - coumarin, 7 - methyl - 3 - (al.a  - tetralyl) - 4 - hydroxy - coumarin, 7 - methoxy - 3 - (al.a  - tetralyl) - 4 - hydroxy - coumarin, 3 - [a  - (p - tolyl) - propyl] - 4 - hydroxy - coumarin, 3 - [a  - phenyl - n - butyl] - 4 - hydroxy - coumarin, 3 - [a  - (p - tolyl) - n - butyl] - 4 - hydroxy - coumarin, 3 - [a  - (p - anisyl) - n - butyl] - 4 - hydroxy - coumarin, 3 - [a  - (p - tolyl) - n - pentyl] - 4 - hydroxy - coumarin, 3 - [a  - (p - isopropyl - phenyl) - ethyl] - 4 - hydroxy-coumarin, 3 - [a  - (p - isopropyl - phenyl) - n - propyl] - 4 - hydroxy - coumarin, 3 - [a  - (p - ethyl - phenyl) - ethyl] - 4 - hydroxy - coumarin, 3 - [a  - ethyl - phenyl - n - propyl] - 4 - hydroxy - coumarin, 3 - [a  - (31,41 - dimethyl - phenyl) - ethyl] - 4 - hydroxy - coumarin, 3 - [a  - (31,41 - dimethyl - phenyl) - n - propyl] - 4 - hydroxy - coumarin, 3 - [a  - (p - fluor - phenyl) - ethyl] - 4 - hydroxy - coumarin, 3 - [a  - (p - fluor - phenyl) - n - propyl] - 4 - hydroxy - coumarin, 3 - [a  - (p - diphenylyl) - ethyl] - 4 - hydroxy - coumarin, 7 - methyl - 3 - (a  - phenyl - ethyl) - 4 - hydroxy - coumarin, 7 - methyl - 3 - [a  - (p - ethyl - phenyl)-n - propyl] - 4 - hydroxy - coumarin, 7 - methyl - 3 - [a  - (p - anisyl) - n - propyl] - 4 - hydroxy - coumarin, 3 - [a  - (31,41 - tetramethylene - phenyl) - ethyl] - 4 - hydroxy - coumarin, 3 - [a  - (31,41 - trimethylene - phenyl) - ethyl] - 4 - hydroxy - coumarin, 3 - [a  - (31,41 - trimethylene - phenyl) - propyl - 4 - hydroxy - coumarin, 3 - [a  - (21,51 - dimethyl - phenyl) - ethyl] - 4 - hydroxy - coumarin, 3 - [a  - (21,51 - dimethyl - phenyl) - propyl] - 4 - hydroxy - coumarin, 3 - [a  - (21,41 - dimethyl - phenyl) - propyl] - 4 - hydroxy - coumarin, 3 - [a  - (4 - phenoxy - phenyl) - ethyl]- 4 - hydroxy - coumarin, 3 - [a ,g  - diphenyl - propyl] - 4 - hydroxy - coumarin, 3 - [a  - (31 - acenaphthyl) - ethyl] - 4 - hydroxy - coumarin, 3 - [a  - (p - propyl - phenyl) - ethyl] - 4 - hydroxy - coumarin, 3 - [a  - (p - propyl - phenyl) - propyl] - 4 - hydroxy - coumarin, 3 - [a  - (p - cyclohexyl - phenyl) - ethyl] - 4 - hydroxy - coumarin, 3 - [a  - (p - cyclohexyl - phenyl) - propyl] - 4 - hydroxy - coumarin, 3 - [a  - (31,41 - methylene - dioxy - phenyl) - propyl] - 4 - hydroxy - coumarin, 3 - (a  - 41 - chloro - phenyl - ethyl) - 4 - hydroxy - coumarin, 3 - (a  - 41 - methoxy - phenyl - propyl) - 4 - hydroxy - coumarin, 3 - (a  - phenyl - propyl) - 4 - hydroxy - coumarin, 7 - methyl - 3 - (a  - phenyl - propyl) - 4 - hydroxy-coumarin, 7 - chloro - 3 - (a  - phenyl - propyl) - 4 - hydroxy - coumarin, 3 - (a  - p - tolyl - propyl) - 4 - hydroxy - coumarin, 7 - methyl - 3 - (a  - p - tolyl - propyl) - 4 - hydroxy - coumarin, 3 - (a  - p - chloro - phenyl - propyl) - 4 - hydroxy - coumarin, 3 - (a  - phenyl - n - pentyl) - 4 - hydroxy - coumarin, 3 - (phenyl - cyclohexylmethyl) - 4 - hydroxy - coumarin, 3 - (a  - phenryl d  - methyl - pentyl) - 4 - hydroxy - coumain-, 3 - (a  - phenyl - b  - methyl - propyl) - 4 - hydroxy - coumarin and 3-(a -phenyl-g -methyl-butyl)-4-hydroxy-coumarin.ALSO:A rodenticidal composition comprises a 4-hydroxy-coumarin of the general formula <FORM:0836740/VI/1> in which A stands for a radical which with the a -pyrene ring forms a 1,2-benzopyrone (coumarin) ring, R1 stands for alkyl and R2 stands for aryl, or <FORM:0836740/VI/2> is combined to form a hydroaromatic or heterocyclic radical, and a solid or liquid carrier.  The compounds may be employed in aqueous solutions as salts of alkali metals or of organic amines, e.g. the sodium salt, triethylamine salt, cyclohexylamine salt, and dicyclohexyl-amine salt.  Illustrative compounds are 3-(a -phenylethyl) - 4 - hydroxy - coumarin, 3 - [a  - (p - chlorophenyl) - propyl] - 4 - hydroxy - coumarin and 3 - [a  - (21 - furyl) - ethyl] - 4 - hydroxy - coumarin.