GB712762A - Preparation of substituted benzoic acids - Google Patents

Preparation of substituted benzoic acids

Info

Publication number
GB712762A
GB712762A GB19147/51A GB1914751A GB712762A GB 712762 A GB712762 A GB 712762A GB 19147/51 A GB19147/51 A GB 19147/51A GB 1914751 A GB1914751 A GB 1914751A GB 712762 A GB712762 A GB 712762A
Authority
GB
United Kingdom
Prior art keywords
prepared
compounds
toluenesulphonyl
radical
aminobenzoate
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
GB19147/51A
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.)
Pharmacia and Upjohn Co
Original Assignee
Upjohn Co
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 Upjohn Co filed Critical Upjohn Co
Publication of GB712762A publication Critical patent/GB712762A/en
Expired legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00Carboxylic acid amides
    • C07C233/01Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/12Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by halogen atoms or by nitro or nitroso groups

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Compounds of the general formula <FORM:0712762/IV (b)/1> wherein R1 represents hydrogen or an alkyl, aryl, aralkyl or cycloalkyl radical, n is 0 or an interger from 1 to 7 inclusive, Z represents hydrogen or an arylsulphonyl, aralkylsulphonyl, alkylsulphonyl or cycloalkylsulphonyl radical, and R represents an alkyl, alkoxymethyl, aryloxymethyl, aralkoxymethyl, dialkoxymethyl or acyloxymethyl radical, are prepared by mixing a solution of a metal dichromate in an aqueous acid with a solution of a compound of the general formula <FORM:0712762/IV (b)/2> where R1, n, Z and R have the above significance, in a substantially water-immiscible organic liquid which is inert under the reaction conditions. The reactants may be mixed, e.g. with vigorous agitation, at a temperature between about - 10 DEG C. and about 30 DEG C. The organic liquid may be an aromatic or halo-aromatic hydrocarbon, e.g. benzene, toluene or chlorobenzene, or may be chloroform. Acids which may be used are inorganic acids, e.g. sulphuric or phosphoric acid, and aliphatic acids, e.g. acetic, propionic or butyric acid, or mixtures of aliphatic acids, or mixtures of aliphatic and inorganic acids may be used. Metal dichromates which may be used in the reaction are the dichromates of the heavy metals and sodium, potassium, calcium and magnesium dichromate. The reaction mixture may contain at least two equivalent weights of metal dichromate for each molar weight of hydroxy compound. The aqueous solution of dichromate may contain from about 4 to about 9 mols. of metal dichromate per litre. The ester residue may be a methyl, ethyl, n-propyl, n-butyl, t-butyl, amyl, lauryl, iso-propyl, dodecyl, phenyl, tolyl, xylyl, cyclohexyl or benzyl ester. The esters prepared by the above method, i.e. when R1 represents an alkyl, aryl, aralkyl or cycloalkyl radical, can be converted to the free acids, i.e. when R1 represents hydrogen, by treatment with alkali. The radical Z may be an o or p-toluenesulphonyl, benzenesulphonyl, naphthalenesulphonyl, methanesulphonyl, alpha-toluenesulphonyl or cyclohexylsulphonyl radical. The arylsulphonyl radicals may contain inert substituents, e.g chlorine or bromine or the nitro radical. The arylsulphonyl radical may be split off to form the corresponding free amine by treatment with hydrogen bromide in an aliphatic acid medium and in the presence of a bromine acceptor by the method described in Specification 676,037. The free amines can be converted to the arylsulphonyl compounds by reaction with arylsulphonyl halides in the presence of alkali. In the examples, the following compounds are prepared: diethyl N1-(N-(3-acetoxy-2-ketopropyl) - N - (p - toluenesulphonyl) - p - aminobenzoyl) - l - glutamate, ethyl N - (3,3 - diethoxy - 2 - ketopropyl) - N - (p - nitrobenzenesulphonyl) - p - aminobenzoate, ethyl N-(3,3 - diethoxy - 2 - ketopropyl) - p - aminobenzoate, ethyl N - (3,3 - diethoxy - 2 - ketopropyl) - N - (p - toluenesulphonyl) - p - aminobenzoate, diethyl N1 - (N - (3,3 - diethoxy - 2-ketopropyl) - p - aminobenzoyl) - l - glutamate, diethyl - N1 - (N - (3,3 - diethoxy - 2 - ketopropyl) - N - (p - toluenesulphonyl) - p - aminobenzoyl) - l - glutamate and diamyl N1-(N - 3,3 - dibutoxy - 2 - ketopropyl) - N - (betanaphthalenesulphonyl) - p - aminobenzoyl - l-glutamate. The Specification refers to a number of additional compounds which may be prepared by the process referred to above, and the starting compounds from which these additional compounds may be prepared. Specifications 671,532, 675,383 and 676,037 are referred to. Substituted amino-benzoate compounds of the general formula <FORM:0712762/IV (b)/3> wherein R represents an alkyl, aryl, aralkyl or or radical, R1 represents an alkyl radical and Z and n have the significance indicated above, are prepared by reacting a compound of the general formula <FORM:0712762/IV (b)/4> with a 1,2-epoxypropyl compound of the formula <FORM:0712762/IV (b)/5> tertiary amine. Compounds of the above general formula wherein R1 represents hydrogen may be prepared by hydrolysing the carboxylic ester groups. Diethyl N1-(N-(3-acetoxy-2-hydroxypropyl) - N - (p - toluenesulphonyl)-p - aminobenzoyl - l - glutamate is prepared by reacting diethyl N1-(N-(p-tolyenesulphonyl)-p - aminobenzoyl - l - glutamate and glycidol in the presence of pyridine. Substituted amino-benzoate compounds of the general formul <FORM:0712762/IV (b)/6> wherein R and R1 represent alkyl radicals and n and Z have the significance indicated above, are prepared by reacting a compound of the general formula <FORM:0712762/IV (b)/7> with a 1,2-epoxyalkane of the formula <FORM:0712762/IV (b)/8> preferably in the presence of a tertiary amine. Compounds of the above general formula wherein R1 represents hydrogen are prepared by hydrolysing the carboxylic ester groups. Diethyl N1 - (N - (p - toluenesulphonyl) - p-aminobenzoyl)-l-glutamate is prepared by reacting N - (p - toluenesulphonyl) - p - aminobenzoyl chloride and diethyl l-glutamate hydrochloride in the presence of triethylamine. Ethyl N - (3,3 - diethoxy - 2 - hydroxypropyl)-N - (p - nitrobenzenesulphonyl) - p - aminobenzoate is prepared by reacting ethyl N-(p-nitrobenzenesulphonyl) p-aminobenzoate and 1,2 - epoxy - 3,3 - diethoxypropane in the presence of pyridine. Ethyl N - (3,3 - diethoxy - 2 - hydroxypropyl)-p-aminobenzoate is prepared by reacting ethyl-p-aminobenzoate and the diethyl acetal of 2,3-oxidopropanol in the presence of pyridine. Ethyl N - (3,3 - diethoxy - 2 - hydroxypropyl)-N - (p - toluenesulphonyl) - p - aminobenzoate is prepared by reacting ethyl p-aminobenzoate and the diethyl acetal of 2,3-oxidopropanol as above and then adding p-toluenesulphonyl chloride. N - (3 - alkyl - 2,3 - diketopropyl) - N - (p-toluenesulphonyl) - p - aminobenzoate compounds are prepared by oxidizing the compounds of the general formula <FORM:0712762/IV (b)/9> wherein R represents an alkyl radical containing more than one carbon atom, Z represents the p-toluenesulphonyl radical and n and R1 have the significance indicated above, with selenium dioxide. These compounds may be condensed with 2,4,5 - triamino - 6 - hydroxypyrimidine to form compounds related to folic acid having an alkyl substituent on the pterine nucleus.
GB19147/51A 1950-08-19 1951-08-14 Preparation of substituted benzoic acids Expired GB712762A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US712762XA 1950-08-19 1950-08-19

Publications (1)

Publication Number Publication Date
GB712762A true GB712762A (en) 1954-07-28

Family

ID=22100330

Family Applications (1)

Application Number Title Priority Date Filing Date
GB19147/51A Expired GB712762A (en) 1950-08-19 1951-08-14 Preparation of substituted benzoic acids

Country Status (1)

Country Link
GB (1) GB712762A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4309559A (en) 1977-12-24 1982-01-05 Fbc Limited Sulphonamides useful as pesticides

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4309559A (en) 1977-12-24 1982-01-05 Fbc Limited Sulphonamides useful as pesticides

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