GB765881A - Improvements in or relating to 2-butylamines and intermediates therefor - Google Patents

Improvements in or relating to 2-butylamines and intermediates therefor

Info

Publication number
GB765881A
GB765881A GB14598/54A GB1459854A GB765881A GB 765881 A GB765881 A GB 765881A GB 14598/54 A GB14598/54 A GB 14598/54A GB 1459854 A GB1459854 A GB 1459854A GB 765881 A GB765881 A GB 765881A
Authority
GB
United Kingdom
Prior art keywords
hydroxy
butanone
methylphenyl
methoxyphenyl
cresol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
GB14598/54A
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Labaz Sanofi NV
Original Assignee
Labaz Laboratoires SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Labaz Laboratoires SA filed Critical Labaz Laboratoires SA
Publication of GB765881A publication Critical patent/GB765881A/en
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
    • C07C215/46—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
    • C07C215/48—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains not further substituted by hydroxy groups
    • C07C215/54—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains not further substituted by hydroxy groups linked by carbon chains having at least three carbon atoms between the amino groups and the six-membered aromatic ring or the condensed ring system containing that ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/54—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
    • C07C217/56—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains not further substituted by singly-bound oxygen atoms
    • C07C217/62—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains not further substituted by singly-bound oxygen atoms linked by carbon chains having at least three carbon atoms between the amino groups and the six-membered aromatic ring or the condensed ring system containing that ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/69—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to carbon-to-carbon double or triple bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
    • C07D317/50—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to atoms of the carbocyclic ring

Abstract

Disubstituted butanones of the general formula: <FORM:0765881/IV(b)/1> (wherein Ar1 represents a p-hydroxyphenyl and Ar2 a phenyl radical, which radicals may be further substituted by at least one hydroxy, methoxy, alkyl, halo, amino or methylenedioxy substituent) are manufactured by condensing a mono-substituted a : b -unsaturated butenone Ar2-CH = CH-CO-CH3 with a phenol Ar1H by heating the reactants together, first in the presence of an organic peroxide type catalyst at 80-90 DEG C., then in the presence of a Friedel-Crafts type catalyst at substantially 100 DEG C., and finally above 110 DEG C. The desired product may be separated by fractional distillation followed by crystallization, and may be converted by amination to the corresponding butylamine of the general formula <FORM:0765881/IV(b)/2> When Ar2 in this product contains a p-methoxy group, this may be subsequently demethylated, and the resulting diphenolic butylamine may be isolated by fractional precipitation with a caustic alkali solution (e.g. in an amount sufficient to adjust the pH of the reaction mixture to 6.6-8.6), and may be converted to its hydrohalide by treatment under substantially dry conditions with a dry gaseous hydrogen halide. The diphenolic butylamines are useful as hypotensive agents, and some of their monomethyl ethers as anti-extrasystolic agents. In examples: (1) benzoyl peroxide is added to anisalacetone and o-cresol in toluene at 80-90 DEG C., the temperature is raised to 100 DEG C. and sulphuric acid added, and finally the mixture is boiled and then poured into sodium carbonate solution, and the toluene layer is separated and fractionally distilled to isolate 4-(41-methoxyphenyl) - 4 - (411 - hydroxy - 311 - methylphenyl)-butanone - 2 (recrystallized from a mixture of benzene and cyclohexane) and some 4-(41-methoxyphenyl) - - (211 - hydroxy - 311 - methylphenyl) - butanone - 2; (2) benzalacetone similarly yields 4 - phenyl - 4 - (41 - hydroxy-31 - methylphenyl) - butanone - 2; (3) 4 - (p-methoxyphenyl) - 4 - (p - hydroxyphenyl)-butanone-2 is similarly prepared from anisalacetone and phenol, 4-(21-chlorophenyl)-4-(411-hydroxy - 311 - methylphenyl) - butanone - 2 from o - chlorobenzalacetone and o - cresol, 4-(41 - hydroxy - 31 - methoxyphenyl) - 4 - (411-hydroxy - 311 - methylphenyl) - butanone - 2 from vanillalacetone and o - cresol, 4 - (31 : 41-dimethoxyphenyl) - 4 - (411 - hydroxy - 311-methoxyphenyl) - butanone - 2 from veratrylideneacetone and o - cresol, and 4 - (31 : 41-methylenedioxyphenyl) - 4 - (411 - hydroxy - 311-methylphenyl) - butanone - 2 from piperonalacetone and o - cresol; (4) 4 - (41 - methoxyphenyl) - 4 - (411 - hydroxy - 311 - methylphenyl)-butanone - 2 is heated with ammonium formate with subsequent hydrolysis of the resulting formylamino compound, to produce 4-(41-methoxyphenyl) - 4 - (411 - hydroxy - 311 - methylphenyl) - butylamine - 2; the products of (2) and (3) are similarly converted to the corresponding amines; (5) the first product of (4) is heated under pressure with conc.HCl and the reaction mixture is fractionally precipitated with caustic soda solution to isolate 4-(41-hydroxyphenyl) - 4 - (411 - hydroxy - 311 - methylphenyl) - butylamine - 2, which is converted into its hydrochloride by reacting dry HCl gas with the dry amine; other methoxy-containing products of (4) similarly yield 4 : 4-bis-(p-hydroxyphenyl) - butylamine - 2. Reference is also made to the condensation of p-dimethylaminobenzalacetone with o-cresol, to hydrogen fluoride, boron fluoride and aluminium chloride as Friedel-Crafts catalysts, and to the use of ammonia and hydrogen and of formamide for the amination step.
GB14598/54A 1953-05-18 1954-05-18 Improvements in or relating to 2-butylamines and intermediates therefor Expired GB765881A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
BE765881X 1953-05-18

Publications (1)

Publication Number Publication Date
GB765881A true GB765881A (en) 1957-01-16

Family

ID=3880053

Family Applications (1)

Application Number Title Priority Date Filing Date
GB14598/54A Expired GB765881A (en) 1953-05-18 1954-05-18 Improvements in or relating to 2-butylamines and intermediates therefor

Country Status (2)

Country Link
BE (1) BE520042A (en)
GB (1) GB765881A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0028682A2 (en) * 1977-07-04 1981-05-20 Astra Läkemedel Aktiebolag Intermediates useful at the preparation of compounds having anti-depressive or tranquilizing activity

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0028682A2 (en) * 1977-07-04 1981-05-20 Astra Läkemedel Aktiebolag Intermediates useful at the preparation of compounds having anti-depressive or tranquilizing activity
EP0028682A3 (en) * 1977-07-04 1981-08-05 Astra Läkemedel Aktiebolag Intermediates useful at the preparation of compounds having anti-depressive or tranquilizing activity

Also Published As

Publication number Publication date
BE520042A (en)

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