DK143446B - PROCESS FOR THE PREPARATION OF ALFA-ANILINOCARBOXYLIC ACIDS AND / OR DERIVATIVES THEREOF - Google Patents

PROCESS FOR THE PREPARATION OF ALFA-ANILINOCARBOXYLIC ACIDS AND / OR DERIVATIVES THEREOF Download PDF

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DK143446B
DK143446B DK519671A DK519671A DK143446B DK 143446 B DK143446 B DK 143446B DK 519671 A DK519671 A DK 519671A DK 519671 A DK519671 A DK 519671A DK 143446 B DK143446 B DK 143446B
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reaction
tertiary amine
general formula
group
compound
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DK143446C (en
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D E Poel
H C Kelderman
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Shell Int Research
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C227/00Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/04Formation of amino groups in compounds containing carboxyl groups
    • C07C227/06Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
    • C07C227/08Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid by reaction of ammonia or amines with acids containing functional groups

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

Description

i ]i]

(19) DANMARK yp.aJ(19) DENMARK yp.aJ

(12) FREMLÆGGELSESSKRIFT ου 143446 B;(12) PRESENTATION WRITING ου 143446 B;

Dl REKTORATET FOR PATENT-OG VAREMÆRKEVÆSENETDl The Patent and Trademark Office

(21) Ansøgning nr. 519^/71 (51) IntCi.3 C 07 C 101/18 (22) Indleveringsdag 26. Okt. 1971 0 07 C 99/00 (24) Løbedag 2β. okt. 1971 (41) Aim. tilgængelig 29· apr. 1972 (44) Fremlagt 24. aug. 1981 (86) International ansøgning nr. “ (86) International indleveringsdag -(85) Videreførelsesdag ” (62) Stamansøgning nr. “(21) Application No. 519 ^ / 71 (51) IntCi.3 C 07 C 101/18 (22) Filing Day 26 Oct. 1971 0 07 C 99/00 (24) Race day 2β. October 1971 (41) Aim. available Apr 29 1972 (44) Posted Aug 24 1981 (86) International Application No. “(86) International Filing Day - (85) Continuation Day” (62) Master Application No. “

(30) Prioritet 28. okt. 1 97Ο, 7015842, NL(30) Priority Oct 28 1 97Ο, 7015842, NL

(71) Ansøger SHELL INTERNATIONALE RESEARCH MAATSCHAFPIJ N.V., Haag, NL.(71) Applicant SHELL INTERNATIONAL RESEARCH MAATSCHAFPIJ N.V., The Hague, NL.

(72) Opfinder Dirk Everard Poel, NL: Hendrik Cornells Keldertnan, NL.(72) Inventor Dirk Everard Poel, NL: Hendrik Cornells Keldertnan, NL.

(74) Fuldmægtig Plougmann & Vlngtoft Patentbureau.(74) Plougmann & Vlngtoft Patent Office.

(54) Fremgangsmåde til fremstilling af , alfa-anlllnocarboxylsyrer og/el= ler derivater deraf.(54) Process for the preparation of alpha-anillinocarboxylic acids and / or derivatives thereof.

Den foreliggende opfindelse angår en fremgangsmåde til fremstilling af oc-anilinocarboxylsyrer og/eller derivater deraf ved hvilken tø fremgangsmåde anilin eller en kernesubstitueret anilin omsættes Φ med en a-halogencarboxylsyre eller et derivat deraf.The present invention relates to a process for the preparation of o-anilinocarboxylic acids and / or derivatives thereof in which thaw process aniline or a nucleus substituted aniline is reacted Φ with an α-halo carboxylic acid or a derivative thereof.

-rf· rt (V) Eksempler på sådanne omdannelser kendes allerede. Normalt lader man ^ a-halogenearboxylsyren eller f.eks. en ester deraf reagere med et overskud af den pågældende anilin til binding af det ved omsætningen j£j dannede hydrogenhalogenid.-rf · rt (V) Examples of such transformations are already known. Normally, the alpha-halogenearboxylic acid or e.g. an ester thereof reacts with an excess of the relevant aniline to bind the hydrogen halide formed by the reaction.

2 U3A462 U3A46

Denne fremgangsmåde har imidlertid den ulempe, at reaktionen sæd= vanligvis forløber meget langsomt, og at der opnås utilfredsstil= lende udbytter. Der er derfor allerede gjort forsøg på at forbedre fremgangsmåden. Ifølge hollandsk patentansøgning nr. 6.717.715, eksempel II, erstattes den overskydende mængde af den pågældende anilin således med natriumbicarbonat. Også i dette tilfælde er imid= lertid den tid, der kræves til den beskrevne reaktion, nemlig omsæt= ningen af 3,4-dichloranilin med a-chlorpropionsyre, meget lang, og udbyttet lader meget tilbage at ønske. Dette er især tilfældet ved den direkte fremstilling af forbindelser, som let kan hydrolyseres, især estere af a-anilinocarboxylsyrer. Også andre baser, f.eks. cal= ciumoxid og magnesiumoxid, giver anledning til partiel forsæbning.However, this process has the disadvantage that the reaction usually proceeds very slowly and that unsatisfactory yields are obtained. Therefore, attempts have already been made to improve the method. According to Dutch Patent Application No. 6,717,715, Example II, the excess amount of the aniline in question is thus replaced with sodium bicarbonate. Also, in this case, however, the time required for the reaction described, namely the reaction of 3,4-dichloroaniline with α-chloropropionic acid, is very long and the yield leaves much to be desired. This is especially the case in the direct preparation of compounds which can be easily hydrolyzed, especially esters of α-anilinocarboxylic acids. Other bases, e.g. calcium = cesium oxide and magnesium oxide, give rise to partial saponification.

Det er naturligvis i disse tilfælde muligt at anvende en totrins= fremgangsmåde, idet man først fremstiller carboxylsyren og derefter fremstiller den ønskede tilsvarende ester ud fra carboxylsyren. Det kan endelig nævnes, at ansøgerne har opnået lave udbytter ved anven= delse af som base, idet indgår i en sidereaktion med a-halo= genatomet under dannelse af a-aminocarboxylsyren eller et derivat deraf.Of course, in these cases it is possible to use a two-step process, first preparing the carboxylic acid and then preparing the desired corresponding ester from the carboxylic acid. Finally, it can be mentioned that the applicants have obtained low yields by using as a base, part of a side reaction with the α-halo atom to form the α-aminocarboxylic acid or a derivative thereof.

Det har nu vist sig, at de ovennævnte ulemper undgås, og at de ønske= de forbindelser fås i højt udbytte ved en glat og generelt anvende= lig reaktion, når der som base anvendes en tertiær amin.It has now been found that the above disadvantages are avoided and that the desired compounds are obtained in high yield by a smooth and generally applicable reaction when using a tertiary amine as a base.

Opfindelsen angår således en fremgangsmåde til fremstilling af a-ani= linocarboxylsyrer og/eller derivater deraf med den almene formel IThe invention thus relates to a process for the preparation of α-ani-linocarboxylic acids and / or derivatives thereof of the general formula I

R1 A_iR1 A_i

<v ,)- KH-CH-T I<v,) - KH-CH-T I

l4 K3 K4 12 3 hvor hvert af symbolerne R , R og R betegner et hydrogen- eller halogenatom eller en alkyl-, halogenalkyl- eller alkoxygruppe, R4 betegner et hydrogenatom eller en alkylgruppe, Y betegner en carboxylgruppe eller et tilsvarende salt eller en tilsvarende estergruppe eller en tilsvarende carboxamidgruppe, som på nitrogenatomet kan være substitueret med én eller to carbonhydridgrupper, eller hvis nitrogenatom indgår i et cyclisk system, og X betegner et 3 14344614 K3 K4 12 3 wherein each of the symbols R, R and R represents a hydrogen or halogen atom or an alkyl, haloalkyl or alkoxy group, R4 represents a hydrogen atom or an alkyl group, Y represents a carboxyl group or a corresponding salt or a corresponding ester group or a corresponding carboxamide group which may be substituted on the nitrogen atom by one or two hydrocarbon groups or if the nitrogen atom is part of a cyclic system and X represents a

hydrogenatom eller en acylgruppe, ved hvilken fremgangsmåde en forbindelse med den almene formel IIhydrogen atom or an acyl group, by which process a compound of the general formula II

R1 EX>-ffi2 12 3R1 EX> -ffi2 12 3

hvor R , R og R har de ovenfor anførte betydning, omsættes med en forbindelse med den almene formel IIIwherein R, R and R are as defined above, reacted with a compound of general formula III

Hal-CH-YHal-CH-Y

IIIIII

R4 4 hvor Hal betegner et halogenatom, og R og Y har de ovenfor anførte betydninger, hvilken fremgangsmåde er ejendommelig ved, at reaktionskomponenterne med den almene formel henholdsvis II og III opvarmes i nærværelse af en tertiær amin til dannelse af en forbindelse med formlen I, hvor X betegner et hydrogenatom, hvorhos det vundne rå produkt med den almene formel I eventuelt underkastes en acyleringsreaktion efter fjernelse af hydrohalogenidet af den tertiære amin til dannelse af en forbindelse med formlen I, hvor X betegner en acylgruppe.R4 4 wherein Hal represents a halogen atom and R and Y have the meanings set forth above, characterized in that the reaction components of the general formulas II and III, respectively, are heated in the presence of a tertiary amine to form a compound of formula I, wherein X represents a hydrogen atom wherein the crude product of the general formula I obtained is optionally subjected to an acylation reaction after removal of the hydrohalide of the tertiary amine to form a compound of formula I wherein X represents an acyl group.

12 3 I de ovenfor viste formler I og II kan symbolerne R , R og R have ens eller forskellig betydning. Der opnås særdeles gode resultater, når mindst ét af disse symboler betegner et halogen- eller hydrogen= 1 2 3 atom. Fortrinsvis er R hydrogen, R halogen og R hydrogen, halogen, alkyl, halogenalkyl eller alkoxy. Halogenatomerne er f.eks. chlor, brom eller fluor; i reglen foretrækkes chlor og fluor. Med hensyn til alkyl- eller alkoxygrupperne foretrækkes almindeligvis sådanne grupper, som ikke indeholder mere end 10 carbonatomer, og især så= danne, som ikke indeholder mere end 6 carbonatomer, medens halogen= alkylgruppen fortrinsvis indeholder højst 6 carbonatomer, og som ha= logen ét eller flere chlor- og/eller fluoratomer. Alkyl-, halogen= alkyl- og alkoxygrupperne kan have forgrenet eller ligekædet struktur. Eksempler på særlig velegnede radikaler er H, Cl, F, methyl, ethyl, propyl, n-butyl, octyl, methoxy og trifluormethyl. Blandt alkyl= grupperne foretrækkes især methylgruppen.3 In formulas I and II shown above, the symbols R, R and R can have the same or different meaning. Very good results are obtained when at least one of these symbols represents a halogen or hydrogen = 1 2 3 atom. Preferably, R is hydrogen, R is halogen and R is hydrogen, halogen, alkyl, haloalkyl or alkoxy. The halogen atoms are e.g. chlorine, bromine or fluorine; as a rule, chlorine and fluorine are preferred. In the case of the alkyl or alkoxy groups, such groups which contain no more than 10 carbon atoms are generally preferred, and especially those which do not contain more than 6 carbon atoms, while the halogen = alkyl group preferably contains no more than 6 carbon atoms and which have one halogen. or more chlorine and / or fluorine atoms. The alkyl, halogen = alkyl and alkoxy groups may have branched or straight chain structure. Examples of particularly suitable radicals are H, Cl, F, methyl, ethyl, propyl, n-butyl, octyl, methoxy and trifluoromethyl. Among the alkyl = groups, the methyl group is particularly preferred.

143446 4143446 4

Eksempler på aniliner med den almene formel II, som er særlig vel= egnede til anvendelse som udgangsforbindelser, er de forskellige isomere monochlor- og dichioraniliner, f.eks. 2-, 3- og 4-chlor= anilin og 3,4- og 2,5-dichloranilin; fluor- og fluorchloraniliner, især 4-fluoranilin og 3-chlor-4-fluoranilin; samt methylchlor-, (trifluormethyl)-chlor- og methoxychloraniliner, f.eks. 2-methyl= -4-ehlor-, 4-methyl-3-chlor-, 3-trifluormethyl-4-chlor- og 2-me= thoxy-4-chloranilin (R^ = H; R^ = Cl eller E; R^ = H, Cl, CH^, CE^ eller OCH^). Eksempler på andre aniliner, der også kan anvendes, er bl.a. de isomere monomethyl- og dimethylaniliner samt det usub= sti tuerede anilin (R·^ = H; R^ = H eller CH^; R^ = H eller CH^). Især foretrækkes 4-chlor- og 4-fluoranilin, 2-methyl-4-chloranilin, 3-chlor-4-fluoranilin og, specielt, 3,4-dichloranilin.Examples of anilines of general formula II which are particularly suitable for use as starting compounds are the various isomeric monochloro and dichloro anilines, e.g. 2-, 3- and 4-chloro = aniline and 3,4- and 2,5-dichloroaniline; fluoro- and fluoro-chloro anilines, especially 4-fluoro-aniline and 3-chloro-4-fluoro-aniline; as well as methyl chloro, (trifluoromethyl) chloro and methoxychlor anilines, e.g. 2-methyl = -4-ehloro, 4-methyl-3-chloro, 3-trifluoromethyl-4-chloro and 2-methoxy-4-chloro aniline (R 2 = H; R 2 = Cl or E; R ^ = H, Cl, CH ^, CE ^ or OCH ^). Examples of other anilines that may also be used include the isomeric monomethyl and dimethylanilines as well as the unsubstituted aniline (R R = H; R ^ = H or CH CH; R ^ = H or CH ^). Particularly preferred are 4-chloro and 4-fluoro-aniline, 2-methyl-4-chloro-aniline, 3-chloro-4-fluoro-aniline and, in particular, 3,4-dichloro-aniline.

Yed fremgangsmåden ifølge opfindelsen bringes anilinen med den almene formel II til omsætning med en a-halogencarboxylsyre eller med et deraf afledt salt, en deraf afledt ester eller et deraf afledt carboxamid med den almene formel III, hvor Hal betegner et halogen= atom, f.eks. fluor, chlor eller brom. Særlig gode resultater opnås, når Hal er Cl eller Br, blandt hvilke chlor foretrækkes. Med hensyn til de andre symboler, R^ og T, i den almene formel III (og i den almene formel i) er R^ et hydrogenatom eller en alkylgruppe - med lige eller forgrenet kæde - som fortrinsvis indeholder højst 5 car= bonatomer. I reglen foretrækkes de relevante forbindelser, i hvilke R^ er hydrogen eller methyl, og sidstnævnte (R^ = methyl) har vist sig særlig fordelagtige.By the process of the invention, the aniline of general formula II is reacted with an α-halo carboxylic acid or with a salt derived therefrom, a derivative ester or a derivative carboxamide of the general formula III wherein Hal represents a halogen atom, f. eg. fluorine, chlorine or bromine. Particularly good results are obtained when Hal is Cl or Br, among which chlorine is preferred. With respect to the other symbols, R 1 and T, in general formula III (and in general formula i), R 1 is a hydrogen atom or an alkyl group - with straight or branched chain - preferably containing at most 5 carbon atoms. As a rule, the preferred compounds in which R 1 is hydrogen or methyl are preferred and the latter (R 2 = methyl) has been found to be particularly advantageous.

Som udgangsforbindelse med den almene formel III anvendes den rele= vante a-halogencarboxylsyre eller et salt afledt deraf, f.eks. et metalsalt såsom natriumsaltet eller et ammoniumsalt; en ester af en carboxylsyre, hvor T fortrinsvis betegner en alkoxycarbonylgruppe med forgrenet eller lige kæde med 1-10 carbonatomer i alkoxydelen; eller et carboxamid, hvor nitrogenatomet, om ønsket, bærer én eller to carbonhydridgrupper som substituenter, fortrinsvis en eller to alkylgrupper, som kan være ens eller forskellige, som kan have for= grenet eller lige kæde, og som indeholder højst 6 carbonatomer, el= ler et carboxamid, hvor nitrogenatomet indgår i et cyclisk system.As the starting compound of the general formula III, the relevant α-halo carboxylic acid or a salt derived therefrom is used, e.g. a metal salt such as the sodium salt or an ammonium salt; an ester of a carboxylic acid, wherein T preferably represents a branched or straight chain alkoxycarbonyl group having 1-10 carbon atoms in the alkoxy moiety; or a carboxamide wherein the nitrogen atom, if desired, carries one or two hydrocarbon groups as substituents, preferably one or two alkyl groups, which may be the same or different, which may have branched or straight chain and containing not more than 6 carbon atoms, or = For example, a carboxamide wherein the nitrogen atom is part of a cyclic system.

Som udgangsforbindelser foretrækkes esterne og carboxamiderne almin= deligvis frem for de tilsvarende frie syrer og deres salte, og især foretrækkes esterne. Det er særlig hensigtsmæssigt at gå ud fra en ester med den almene formel III, hvor Y er en alkoxycarbonylgruppe 5 143AA 6 med højst 4 carbonatomer i alkoxydelen, f.eks. methoxy-, ethoxy-, isopropoxy- eller n-butoxycarbonyl; ethoxycarbonylgruppen foretræk= kes, Mr der anvendes carboxamiderne, er det særlig hensigtsmæssigt at gå ud fra det relevante H-methyl- eller N,!T~dimethylderivat (Y = COMCHj eller C0N(CH^)2).As starting compounds, the esters and carboxamides are generally preferred over the corresponding free acids and their salts, and the esters are particularly preferred. It is particularly convenient to proceed from an ester of the general formula III wherein Y is an alkoxycarbonyl group 5 143AA 6 with a maximum of 4 carbon atoms in the alkoxy moiety, e.g. methoxy, ethoxy, isopropoxy or n-butoxycarbonyl; preferred to use the carboxamides, it is particularly convenient to use the appropriate H-methyl or N, T-dimethyl derivative (Y = COMCH 2 or CO (CH 2) 2).

Eksempler på egnede a-halogencarboxylsyrer og derivater deraf er cc-chlor- og a-brompropionsyre, de tilsvarende chlor- og bromeddike= syrer og deres salte, estere og amider, især ethylesterne og N-me= thyl- og Η,Ν-dimethylamiderne. Især foretrækkes ethylesteren af a= -chlorpropionsyre.Examples of suitable α-halo carboxylic acids and derivatives thereof are the cc-chloro and α-bromopropionic acids, the corresponding chloro and bromoacetic acids and their salts, esters and amides, in particular the ethyl esters and the N-me = methyl and Ν, dim-dimethylamides. . In particular, the ethyl ester of α = -chloropropionic acid is preferred.

Udgangsforbindelserne II og III kan anvendes i omtrentlig støk.ia= metriske mængder, men det foretrækkes i reglen at anvende et over= skud af forbindelsen med den almene formel III. Hensigtsmæssige molforhold mellem carboxylsyren eller derivatet deraf og anilinen ligger sædvanligvis mellem 1,2:1 og 3:1, fortrinsvis mellem 1,3:1 og 2,5:1 og især mellem 1,8:1 og 2,1:1. Højere molforhold, f.eks.The starting compounds II and III can be used in approximate amounts of metric amounts, but it is generally preferred to use an excess of the compound of the general formula III. Suitable mole ratios of the carboxylic acid or derivative thereof and the aniline are usually between 1.2: 1 and 3: 1, preferably between 1.3: 1 and 2.5: 1 and most preferably between 1.8: 1 and 2.1: 1. Higher mole ratios, e.g.

4:1 eller derover, er også mulige, men kan i nogle tilfælde føre til uønskede sidereaktioner og vil oven i købet kræve længere reak= tionstider. Den anvendte overskydende mængde, f.eks. af en ester, kan ofte med fordel tjene som opløsningsmiddel. Om ønsket kan man også anvende andre opløsningsmidler med dertil egnet kogepunkt, fortrinsvis polære og aprote opløsningsmidler og fortyndingsmidler, f.eks. dimethylformamid eller dimethyl- eller dlethylesteren af diethylenglycol. De nævnte opløsningsmidler og fortyndingsmidler og/eller den reaktionsdeltager, som anvendes i overskud, f.eks. en ester med formlen III, kan fjernes fra reaktionsblandingen på den sædvanlige måde, f.eks. ved destillation, og anvendes igen.4: 1 or more are also possible, but may in some cases lead to undesirable side reactions and will require longer reaction times. The excess amount used, e.g. of an ester can often advantageously serve as a solvent. If desired, other solvents having a suitable boiling point may also be used, preferably polar and aprotic solvents and diluents, e.g. dimethylformamide or the dimethyl or diethyl ester of diethylene glycol. Said solvents and diluents and / or the reactant used in excess, e.g. an ester of formula III may be removed from the reaction mixture in the usual manner, e.g. by distillation, and used again.

Ifølge opfindelsen skal omsætningen mellem forbindelserne II og III til dannelse af a-anilinocarboxylsyren og/eller derivatet deraf (I) udføres i nærværelse af en tertiær amin. Det hydrohalogenid, der frigøres under denne kondensation, HHal, bindes således til den ter= tiære amin under dannelse af det tilsvarende hydrogenhalogenid. Ege nede tertiære aminer er f.eks. aliphatiske, aromatiske og heterocyc= liske tertiære aminer, hvor substituenterne på nitrogenatomet kan være ens eller forskellige, samt acycliske og/eller cycliske tertiære aminer. Egnede substituenter, på nitrogenatomet er f.eks. alkyl, cyc~ lo alkyl, alkenyl, cycloalkenyl, aryl., aralkyl, alkaryl og alkylen.According to the invention, the reaction between compounds II and III to form the α-anilinocarboxylic acid and / or the derivative thereof (I) is to be carried out in the presence of a tertiary amine. Thus, the hydrohalide released during this condensation, HHal, binds to the tertiary amine to form the corresponding hydrogen halide. Lower tertiary amines are e.g. aliphatic, aromatic and heterocyclic tertiary amines where the substituents on the nitrogen atom may be the same or different, as well as acyclic and / or cyclic tertiary amines. Suitable substituents on the nitrogen atom are e.g. alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, aralkyl, alkaryl and alkylene.

6 1434466 143446

Desuden fean nitrogenatomet også indgå i et heteroaromatisk system, og der kan, om ønsket, også være inerte substituenter og/eller he= teroatomer til stede. Eksempler på substituenter på nitrogenatomet er ethyl, isopropyl, n-butyl, cyclohexyl, allyl, phenyl, benzyl, tolyl, pentamethylen og oxyethylen. Som egnede tertiære aminer kan således bl.a. nævnes de relevante trialkyl- og triallylaminer, ϋΓ,ΪΤ-dialkylaniliner, N-alkylpiperidiner og -morpholiner samt hetero= aromatiske aminer, såsom pyridin, picolinerne og quinolin.In addition, the nitrogen atom is also part of a heteroaromatic system and, if desired, inert substituents and / or heteroatoms may also be present. Examples of substituents on the nitrogen atom are ethyl, isopropyl, n-butyl, cyclohexyl, allyl, phenyl, benzyl, tolyl, pentamethylene and oxyethylene. Thus, as suitable tertiary amines, e.g. mention is made of the relevant trialkyl and triallylamines, ϋΓ, dial-dialkylanilines, N-alkylpiperidines and morpholines, and hetero-aromatic amines such as pyridine, picolines and quinoline.

Oparbejdningen af reaktionsblandingen bliver let, når der anvendes aliphatiske aminer, i hvilke hver af substituenterne på nitrogenato= met indeholder højst 6 carbonatomer, da hydrohalogenidsalte af ali= phatiske aminer med højst 6 carbonatomer i hver substituent let kan fjernes fra reaktionsblandingen og er lette at skaffe sig af med uden at forurene miljøet.Blandt aliphatiske aminer har tert.al= kyl- og -allylaminer med højst 4 carbonatomer pr. substituent vist sig at give særlig gode resultater. Det er fordelagtigt at anvende en amin, i hvilken substituenterne på nitrogenatomet er ens. For= trinlige resultater er opnået med f.eks. triethylamin og især tri= -n-butylamin og triallylamin. Især foretrækkes tri-n-butylamin.The processing of the reaction mixture becomes easy when aliphatic amines are used in which each of the substituents on the nitrogen atom contains no more than 6 carbon atoms, since hydrohalide salts of aliphatic amines with no more than 6 carbon atoms in each substituent can be easily removed from the reaction mixture and are readily obtained. get rid of it without polluting the environment. Among aliphatic amines have tert.al = cooling and allylamines with a maximum of 4 carbon atoms per minute. substituent has been found to give particularly good results. It is advantageous to use an amine in which the substituents on the nitrogen atom are the same. Preliminary results have been obtained with e.g. triethylamine and especially tri = -n-butylamine and triallylamine. In particular, tri-n-butylamine is preferred.

Det har vist sig, at den hastighed, med hvilken reaktionen forløber, almindeligvis er jo højere, jo mere basisk karakter, aminen har, og vice versa. Når der anvendes aminer med mindre basisk karakter, kan reaktionshastigheden, om ønsket, forøges ved, at temperaturen hæves.It has been found that the rate at which the reaction proceeds is generally the higher, the more basic the amine, and vice versa. When less basic amines are used, the rate of reaction may be increased, if desired, by raising the temperature.

Det anbefales derfor at vælge aminen og reaktionstemperaturen på en sådan måde, at omdannelsen forløber med rimelig hastighed. Alminde= ligvis er reaktionstemperaturen mindst 100°C og højst 175°C. Det er imidlertid ikke udelukket at anvende lavere temperaturer, f.eks. ved anvendelse af særlig reaktive reaktionsdeltagere, eller højere tem= peraturer. Det foretrækkes at arbejde ved temperaturer fra 120 til 160°C, især ved temperaturer fra 130 til 150°C. Reaktionen forløber i reglen let ved atmosfæretryk. I særlige tilfælde, f.eks. når der anvendes en lavtkogende amin såsom triethylamin, foretrækkes det at anvende overatmosfæriske tryk. Det er imidlertid også muligt at an= vende lavere tryk.Therefore, it is recommended to select the amine and the reaction temperature in such a way that the conversion proceeds at a reasonable rate. Generally = the reaction temperature is at least 100 ° C and at most 175 ° C. However, the use of lower temperatures, e.g. using particularly reactive reaction participants, or higher temperatures. It is preferred to operate at temperatures of 120 to 160 ° C, especially at temperatures of 130 to 150 ° C. The reaction usually proceeds easily at atmospheric pressure. In special cases, e.g. when a low boiling amine such as triethylamine is used, it is preferred to use over-atmospheric pressure. However, it is also possible to use lower pressure.

Det foretrækkes, at der ikke anvendes mere end den støkiometrisk nød= vendige mængde af den tertiære amin. En mængde, som er omtrentlig lig med eller lidt mindre end (f.eks. 5 molprocent mindre end) mængden af anilinen med den almene formel II, har almindeligvis vist sig at være 7 143446 tilstrækkelig. Ved anvendelsen af større mængder opnås i reglen ingen fordele. Hvis der imidlertid som reaktionsdeltager III anven= des den frie carboxylsyre (Y = COOH), anbefales det at anvende en tilsvarende større mængde af den tertiære amin.It is preferred that no more than the stoichiometric amount of the tertiary amine is used. An amount which is approximately equal to or slightly less than (e.g., 5 mole percent less than) the amount of the aniline of the general formula II has generally been found to be sufficient. Generally speaking, when using larger quantities, no benefits are obtained. However, if the free carboxylic acid (Y = COOH) is used as reaction participant III, it is recommended to use a correspondingly greater amount of the tertiary amine.

Ifølge en foretrukken udførelsesform for fremgangsmåden ifølge opfindelsen sættes den tertiære amin, eller i det mindste en del af den, lidt efter lidt til reaktionsblandingen under reaktionen. Det har nemlig vist sig, at der på denne måde kan opnås en højere omdannelsesgrad af anilinen med den almene formel II. Det er således muligt at gå ud fra en reaktionsblanding, som indeholder 10 - 30$ af den beregnede mængde af den tertiære amin og at tilsætte resten senere, dvs. under reaktionen, enten kontinuerligt eller portionsvis.According to a preferred embodiment of the process according to the invention, the tertiary amine, or at least part thereof, is added little by little to the reaction mixture during the reaction. Namely, it has been found that in this way a higher degree of conversion of the aniline of the general formula II can be obtained. Thus, it is possible to start from a reaction mixture containing 10 - 30 $ of the calculated amount of the tertiary amine and to add the residue later, ie. during the reaction, either continuously or portionwise.

Det har endvidere vist sig, at omsætningen forløber væsentlig hurti=' gere, hvis et salt af en tertiær amin er til stede allerede ved om= sætningens begyndelse; saltet virker da som katalysator. 3?ortrins= vis anvendes et hydrohalogenid, især et hydrohalogenid, som også dannes under reaktionen, f.eks. hydrochloridet af tri-n-butylamin, hvis der som udgangsmateriale anvendes en a-ehlorcarboxylsyre eller et derivat deraf og tri-n-butylamin som tertiær amin. En mængde på f.eks. 2-60 molprocent, beregnet på anilinen med den almene formel II, har i reglen vist sig at være særdeles hensigtsmæssig. Om ønsket kan der også anvendes større mængder, f.eks. op til 300 molprocent eller derover, beregnet på anilinen. Det forhold, at et salt af en tertiær amin er til stede allerede ved reaktionens begyndelse, hvil= ket også med fordel kan udnyttes i kombination med den ovennævnte gradvise tilsætning af aminen, fører især ved reaktionens begyndelse til en væsentlig højere omdannelse af anilinen. F.eks. er så meget som 80$ af anilinen blevet omdannet på halvdelen af den tid, som ville være nødvendig til opnåelse af samme omdannelse under i øvrigt de samme betingelser.Furthermore, it has been found that the reaction proceeds substantially faster if a salt of a tertiary amine is present already at the beginning of the reaction; the salt then acts as a catalyst. In three steps, a hydrohalide, especially a hydrohalide, which is also formed during the reaction, e.g. the hydrochloride of tri-n-butylamine, if starting material is used as an α-ehlorocarboxylic acid or a derivative thereof, and tri-n-butylamine as tertiary amine. An amount of e.g. 2-60 mole percent, calculated on the aniline of the general formula II, has generally been found to be very suitable. If desired, larger amounts may also be used, e.g. up to 300 mole percent or more, calculated on the aniline. The fact that a salt of a tertiary amine is present already at the beginning of the reaction, which can also be advantageously used in combination with the above gradual addition of the amine, leads especially to a significantly higher conversion of the aniline at the beginning of the reaction. Eg. For example, as much as $ 80 of the aniline has been converted in half the time that would be required to achieve the same conversion under otherwise the same conditions.

Til hindring af, at der sker oxidation af anilinen, kan det være hensigtsmæssigt at arbejde under udelukkelse af oxygen, f.eks. ved, at reaktionen udføres i en atmosfære af nitrogen eller en anden inert gas.To prevent oxidation of the aniline, it may be convenient to operate under the exclusion of oxygen, e.g. in that the reaction is carried out in an atmosphere of nitrogen or another inert gas.

Fremgangsmåden ifølge opfindelsen kan f.eks. udføres chargevis, kon= tinuerligt eller halvkontinuerligt.The method according to the invention can e.g. is performed batchwise, continuous or semi-continuous.

8 1434468 143446

Det vundne reaktionsprodukt kan oparbejdes på sædvanlig måde. Almin= deligvis fjerner man først hydrohalogenidet af den tertiære amin ved vaskning med vand, og derefter fjernes komponent III, som normalt anvendes i overskud, idet fjernelsen f.eks. foretages ved destillat tion. Eventuelle tilstedeværende mængder af uomdannet anilin (II) kan, efter fortynding med f.eks. toluen, udfældes i form af hydro= chloridet (ved indføring af den nødvendige mængde hydrogenchlorid), som derefter kan fjernes ved filtrering. Den på denne måde vundne opløsning af den ønskede forbindelse med den almene formel I kan, om ønsket, anvendes som sådan til yderligere omdannelser eller til direkte benyttelse; produktet kan også let skilles fra opløsningen, f.eks. ved, at opløsningsmidlet fjernes ved destillation.The reaction product obtained can be reprocessed in the usual manner. Almin = partially, the hydrohalide of the tertiary amine is first removed by washing with water, and then component III, which is normally used in excess, is removed. by distillation. Any amounts of unreacted aniline (II) present may, after dilution with e.g. toluene, precipitates in the form of the hydrochloride (by introducing the required amount of hydrogen chloride), which can then be removed by filtration. The solution thus obtained of the desired compound of general formula I may, if desired, be used as such for further conversions or for direct use; the product can also be easily separated from the solution, e.g. by removing the solvent by distillation.

De α-anilinocarboxylsyrer og/eller derivater deraf, som kan fremstilles ved fremgangsmåden ifølge opfindelsen, er bl.a. vigtige mellemprodukter til fremstilling af farmaceutiske produkter og især til fremstilling af kemikalier til bekæmpelse af uønsket plantevækst, eller forbindelserne selv kan have værdifulde herbicide egenskaber.The α-anilinocarboxylic acids and / or derivatives thereof which can be prepared by the process of the invention are, inter alia, important intermediates for the preparation of pharmaceutical products and especially for the manufacture of chemicals for controlling undesirable plant growth, or the compounds themselves may have valuable herbicidal properties.

Således er f.eks. α-anilinocarboxamider med den almene formel I, hvor Γ er en carboxamidgruppe med eller uden en substituent, sær= deles velegnede som aktive bestanddele i herbicider (jfr. hollandsk patentansøgning nr. 6.707.890).Thus, e.g. α-Anilinocarboxamides of general formula I, wherein Γ is a carboxamide group with or without a substituent, are particularly suitable as active ingredients in herbicides (cf. Dutch Patent Application No. 6,707,890).

Yed acylering af α-anilinocarboxylsyrerne og/eller derivaterne deraf med den almene formel I, fremstillet ved fremgangsmåden ifølge op= findelsen, fås de tilsvarende E-acylderivater med acylsubstituenten på· anilinonitrogenatomet. Disse derivater har fremragende herbicid virkning, således som det er beskrevet i hollandsk patentansøgning nr, 6.717.715. På grund af deres selektive herbicide egenskaber har de vist sig særlig velegnede til bekæmpelse af flyvehavre. lil anvendelse blandes en sådan forbindelse sædvanligvis med en bærer og/eller et overfladeaktivt middel. Der opnås fortrinlige resulta= ter, når den aktive bestanddel f.eks. er ethylesteren af a-(N~ben= zoyl-3,4-dichloranilino)-propionsyre, som fås på attraktiv måde ved omsætning af 3,4-dichloranilin med ethylesteren af a-chlorpro= pionsyre i nærværelse af tri-IT-butylamin ved fremgangsmåden ifølge den foreliggende opfindelse og efterfølgende benzoylering med ben= zoylchlorid.By acylating the α-anilinocarboxylic acids and / or derivatives thereof of general formula I prepared by the process of the invention, the corresponding E-acyl derivatives are obtained with the acyl substituent on the aniline nitrogen atom. These derivatives have excellent herbicidal activity, as described in Dutch Patent Application No. 6,717,715. Because of their selective herbicidal properties, they have proved particularly suitable for the control of oats. For use, such a compound is usually mixed with a carrier and / or a surfactant. Excellent results are obtained when the active ingredient e.g. is the ethyl ester of α- (N-ben = zoyl-3,4-dichloro anilino) propionic acid, which is attractively obtained by reaction of 3,4-dichloroaniline with the ethyl ester of α-chloro propionic acid in the presence of tri-IT-butylamine by the process of the present invention and subsequent benzoylation with benzyl chloride.

9 14344$9 14344 $

Fremgangsmåden ifølge opfindelsen belyses nærmere ved følgende ek= sempler:The process according to the invention is further illustrated by the following examples:

Eksempel 1.Example 1.

Fremstilling af ethyl-α-(3,4-dichloranilino)-propionat under anven= delse af tri-n-bntylamin).Preparation of ethyl α- (3,4-dichloroanilino) propionate using tri-n-benzylamine).

I en 250 ml*s trehalset rundbundet kolbe, som er udstyret med meka= nisk omrører, gastilledningsrør, termometer og tilbagesvalimgskøieh, opvarmes under nitrogenatmosfære en blanding af 54,6 g (0,4 mol) ethyl-a-chlorpropionat, 32,4 g (0,2 mol) 3,4-diehloranilin og 35,3 g (0,19 mol) tri-n-butylamin ved 145°C i 12,75 timer.In a 250 ml * s three-necked round bottom flask equipped with mechanical stirrer, gas supply tube, thermometer and reflux chamber, a mixture of 54.6 g (0.4 mole) of ethyl a-chloropropionate, 32.4 g, is heated. g (0.2 mole) of 3,4-diehloroaniline and 35.3 g (0.19 mole) of tri-n-butylamine at 145 ° C for 12.75 hours.

Blandingen afkøles derpå, og efter fortynding med 100 ml toluen vaskes den tre gange med hver gang 50 ml vand til fjernelse af det dannede tri-n-butylamin-liydrochlorid, Til slut tørres blandingen over natri=* umsulfat, og toluenet fjernes ved destillation.The mixture is then cooled and, after dilution with 100 ml of toluene, it is washed three times with 50 ml of water each time to remove the resulting tri-n-butylamine hydrochloride. Finally, the mixture is dried over sodium sulfate and the toluene is removed by distillation.

En analyse af det på denne måde vundne reaktionsprodukt ved gas-væskes -chromatografi viser, at 97,7 molprocent af 3,4-dichloranilinet er omdannet til det ønskede ethyl-a-(3,4~dichloranilino)~propionat m©d en selektivitet på 86,7 molprocent. Udbyttet er derfor 84,7$, be= regnet på anilinen.An analysis of the reaction product thus obtained by gas-liquid chromatography shows that 97.7 mole percent of the 3,4-dichloroaniline is converted to the desired ethyl α- (3,4-dichloroanilino) -propionate with selectivity of 86.7 mole percent. The yield is therefore $ 84.7, calculated on the aniline.

Eksempel 2-6.Examples 2-6.

Nedenstående tabel 1 angiver resultaterne af en række forsøg, som i visse henseender afviger fra den i eksempel 1 beskrevne fremgangs^ måde. Yderligere detaljer fremgår af tabellen.Table 1 below sets forth the results of a series of experiments which differ in certain respects from the procedure described in Example 1. Further details can be found in the table.

10 14344610 143446

Tabel ATable A

A = ethyl-oc-chlorpropionat B = 3,4-dichloranilin C = tri-n-butylaminA = ethyl oc-chloropropionate B = 3,4-dichloroaniline C = tri-n-butylamine

Eksempel Molforhold Reaktions= Tempe= 0mdannel= Selekti= Udbytte, nr. A B C tid, timer ratur, se (B), vitet beregnet °C molprocent (B), mol= på B, procent molpro= cent 2 1,2 1 1 6 155 89,9 78,6 70,6 5 1,38 11 6 155 93,7 87,9 82,4 4 2 1 1 8 145 92,9 90,1 83,7 5 2 1 la) 8. 145 96,0 89,7 86,1 6 2 1 lb) 6 145 94,4 90,0 85,0 a) 1/4 deraf tilsat ved begyndelsen og 3/4 kontinuerligt i løbet af 7 timer.Example Mole Ratio Reaction = Temp = 0mg = Selection = Yield, No. ABC time, hours rature, see (B), white calculated ° C mole percent (B), mole = on B, mole percent = cent 2 1.2 1 1 6 155 89.9 78.6 70.6 5 1.38 11 6 155 93.7 87.9 82.4 4 2 1 1 8 145 92.9 90.1 83.7 5 2 1 la) 8. 145 96 0 89.7 86.1 6 2 1 lb) 6 145 94.4 90.0 85.0 a) 1/4 thereof added at the beginning and 3/4 continuously over 7 hours.

b) 1/4 deraf tilsat i begyndelsen og 3/4 kontinuerligt i løbet af 4 timer; forsøget udførtes endvidere i nærværelse af 5 molprocent tilsat hydroehlorid af C (beregnet på B).b) 1/4 of it added initially and 3/4 continuously over 4 hours; the test was also carried out in the presence of 5 mole percent added hydrohloride of C (calculated on B).

Således viser f.eks. en sammenligning mellem eksempel 2 og eksempel 3, at et højere molforhold A:B forhøjer udbyttet. Endvidere medfører gradvis tilsætning af en del af aminen C under reaktionen en forøgelse af omdannelsen og udbyttet, således som det vil ses ved en sammen= ligning mellem eksempel 5 og eksempel 4. Eksempel 6, hvor hydro= chloridet af aminen C sættes til udgangsblandingen, viser endvidere, at der herved i løbet af kun 6 timer opnås omtrentlig samme resultat som i eksempel 5.Thus, e.g. a comparison between Example 2 and Example 3 that a higher molar ratio A: B increases the yield. Furthermore, the gradual addition of a portion of the amine C during the reaction results in an increase in the conversion and yield, as will be seen in a comparison between Example 5 and Example 4. Example 6 wherein the hydrochloride of the amine C is added to the starting mixture. further shows that, in just 6 hours, approximately the same result as in Example 5 is obtained.

Eksempel 7·Example 7 ·

Fremstilling af ethyl-cc- (3,4-dichloraniliro)-propionat (under an= vendelse af tri-n-butylamin).Preparation of ethyl cc- (3,4-dichloroaniliro) propionate (using tri-n-butylamine).

11 143446 I en 100 ml*s trehalset, rundmundet kolbe, som er udstyret med mag= netomrører, gastilledningsrør, termometer og tilbagesvalingskøler, opvarmes en blanding af 13,66 g (100 millimol) ethyl-a-chlorpropio= nat, 8,10 g (50 millimol) 3,4-dichloranilin, 5,55 g (25 millimol) tri-n-butylamin-hydrochlorid og 8,80 g (47,5 millimol) tri-n-butyl= amin i 4 timer ved 135°C under nitrogenatmosfære. Blandingen afkøles derefter, og efter fortynding med 25 ml toluen vaskes den med 25 ml vand til fjernelse af det dannede tri-n-butylamin-hydrochlorid.In a 100 ml * s three-necked, round-mouthed flask equipped with magnetic stirrer, gas conduit, thermometer and reflux condenser, a mixture of 13.66 g (100 millimoles) of ethyl-a-chloropropio = night, 8.10 g (50 millimoles) of 3,4-dichloroaniline, 5.55 g (25 millimoles) of tri-n-butylamine hydrochloride and 8.80 g (47.5 millimoles) of tri-n-butyl = amine for 4 hours at 135 ° C under nitrogen atmosphere. The mixture is then cooled and, after dilution with 25 ml of toluene, it is washed with 25 ml of water to remove the resulting tri-n-butylamine hydrochloride.

Til slut tørres blandingen over natriumsulfat.Finally, the mixture is dried over sodium sulfate.

En analyse af det på denne måde vundne reaktionsprodukt ved gas= -væske-chromatografering viser, at 85,3% af 3,4-dichloranilinet er blevet omdannet til det ønskede ethyl-oc-(3,4-dichloranilino)-pro= pionat med en selektivitet på 94,4 molproeent. Udbyttet er derfor 80,3%, beregnet på anilinen.An analysis of the reaction product thus obtained by gas = liquid chromatography shows that 85.3% of the 3,4-dichloroaniline has been converted to the desired ethyl oc- (3,4-dichloroanilino) propionate. with a selectivity of 94.4 mole percent. The yield is therefore 80.3%, calculated on the aniline.

Eksempel 8.Example 8.

Fremstilling af ethyl-cc-(3,4~dichloranilino)-propionat (under an= vendelse af triallylamin).Preparation of ethyl cc- (3,4-dichloroanilino) propionate (using triallylamine).

Analogt med det i eksempel 1 beskrevne opvarmes en blanding af 54,6 g (0,4 mol) ethyl-oc-chlorpropionat, 32,4 g (0,2 mol) 3,4-di= chloranilin og 25,4 g (0,185 mol) triallylamin ved 145°C i 12 timer under nitrogenatmosfære. Ved oparbejdningen anvendes 150 ml toluen.Analogous to that described in Example 1, a mixture of 54.6 g (0.4 mole) of ethyl o-chloropropionate, 32.4 g (0.2 mole) of 3,4-di = chloroaniline and 25.4 g ( 0.185 moles of triallylamine at 145 ° C for 12 hours under a nitrogen atmosphere. In working up, 150 ml of toluene is used.

I henhold til gas-væske-chromatografering er 68,9 molprocent af 3,4-dichloranilinet blevet omdannet med en selektivitet på 94,2%, svarende til et udbytte af det ønskede ethyl-a-(3,4-dichlQranilino)<= -propionat på 93,2% (beregnet på anilinen). Fremstillingen af N-benzoylderivatet udføres ved et særskilt forsøg, hvor 39,3 g (0,28 mol) benzoylchlorid sættes til opløsningen af det rå reaktionspro= dukt - efter fjernelse af det dannede triallylaminhydrochlorid og 100 ml toluen - i løbet af 20 minutter ved en temperatur på 120°C, og blandingen holdes derefter i 4 timer ved 120°C. Ben overskydende mængde benzoylchlorid, ethyl-2-chlorpropionat og N-toluen fjernes ved destillation under reduceret tryk, N-Benzoylderivatet fås på denne måde med en selektivitet på 95,3 molprocent ved en omdannelse på 96,0 molprocent.According to gas-liquid chromatography, 68.9 mole percent of the 3,4-dichloroaniline has been converted with a selectivity of 94.2%, corresponding to a yield of the desired ethyl-α- (3,4-dichloroanilino) <= propionate of 93.2% (calculated on the aniline). The preparation of the N-benzoyl derivative is carried out in a separate experiment where 39.3 g (0.28 mol) of benzoyl chloride is added to the solution of the crude reaction product - after removal of the resulting triallylamine hydrochloride and 100 ml of toluene - over 20 minutes at a temperature of 120 ° C and the mixture is then kept for 4 hours at 120 ° C. Bone excess amount of benzoyl chloride, ethyl 2-chloropropionate and N-toluene is removed by distillation under reduced pressure, the N-Benzoyl derivative thus obtained having a selectivity of 95.3 mol% at a conversion of 96.0 mol%.

Claims (3)

1. Fremgangsmåde til fremstilling af α-anilinocarboxylsyrer og/eller derivater deraf med den almene formel I t X f\_\' )-N-CH-Y I r2 R4 R3 12 3 hvor hvert af symbolerne R , R og R betegner et hydrogen- eller halogenatom eller en alkyl-, halogenalkyl- eller alkoxygruppe, R4 betegner et hydrogenatom eller en alkylgruppe, Y betegner en carboxylgruppe eller et tilsvarende salt eller en tilsvarende estergruppe eller en tilsvarende carboxamidgruppe, som på nitrogenatomet kan være substitueret med én eller to carbonhydridgrupper, eller hvis nitrogenatom indgår i et cyclisk system, og X betegner et hydrogenatom eller en acylgruppe, ved hvilken fremgangsmåde en forbindelse med den almene formel II 13 U3U6 R1 ™2 u R3 12 1 hvor R , R og R har de ovenfor anførte betydninger, omsættes med en forbindelse med den almene formel III Hal-CH-Y III R1 hvor Hal betegner et halogenatom, og R1 og Y har de ovenfor anførte betydninger, kendetegnet ved, at reaktipnskomponenterne med den almene formel henholdsvis II og III opvarmes i nærværelse af en tertiær amin til dannelse af en forbindelse med formlen I, hvor X betegner et hydrogenatom, hvorhos det vundne rå produkt med den almene formel I eventuelt underkastes en acyleringsreaktion efter fjernelse af hydrohalogenidet af den tertiære amin til dannelse af en føjr-bindelse med formlen I, hvor X betegner en acylgruppe.A process for the preparation of α-anilinocarboxylic acids and / or derivatives thereof of the general formula I X-N-CH-Y I R 2 R 4 R 3 12 3 wherein each of the symbols R, R and R represents a hydrogen or halogen atom or an alkyl, haloalkyl or alkoxy group, R4 represents a hydrogen atom or an alkyl group, Y represents a carboxyl group or a corresponding salt or ester group or a corresponding carboxamide group which may be substituted on the nitrogen atom by one or two hydrocarbon groups or if the nitrogen atom is part of a cyclic system and X represents a hydrogen atom or an acyl group, in which process a compound of the general formula II, wherein R, R and R have the above meanings, is reacted with a compound of the general formula III Hal-CH-Y III R1 wherein Hal represents a halogen atom and R1 and Y have the meanings set forth above, characterized in that the reaction type components having the general Formulas II and III, respectively, are heated in the presence of a tertiary amine to form a compound of formula I wherein X represents a hydrogen atom, wherein the crude product of general formula I obtained is optionally subjected to an acylation reaction after removal of the hydrohalide of the tertiary amine. forming a spring compound of formula I wherein X represents an acyl group. 2. Fremgangsmåde ifølge krav 1, kendetegnet ved, at der som tertiær amin anvendes en aliphatisk amin, hvori hver af substituenteme på nitrogenatomet indeholder højst 6 carbonatomer.Process according to claim 1, characterized in that as an tertiary amine an aliphatic amine is used, wherein each of the substituents on the nitrogen atom contains a maximum of 6 carbon atoms. 3. Fremgangsmåde ifølge krav 2, kendetegnet ved, at der som tertiær amin anvendes tri-n--butylamin. Fremgangsmåde ifølge et hvilket som helst af kravene 1 - 3^ kendetegnet ved, at den tertiære amijn eller i det mindste en del deraf lidt efter lidt sættes til reaktionsblandingen under reaktionen.Process according to claim 2, characterized in that tri-n-butylamine is used as tertiary amine. Process according to any one of claims 1 to 3 characterized in that the tertiary amine or at least a part thereof is added gradually to the reaction mixture during the reaction.
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US4246429A (en) * 1978-06-23 1981-01-20 Janssen Pharmaceutica, N.V. Novel α-amino-phenylacetic acid derivatives
US4266071A (en) * 1980-06-09 1981-05-05 Ciba-Geigy Corporation Process for the preparation of N-(1-alkoxycarbonylethyl)-2,6-dialkylanilines
US4260782A (en) * 1980-06-09 1981-04-07 Ciba-Geigy Corporation Process for the preparation of N-(1'-alkoxycarbonylethyl)-2,6-dialkylanilines

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SU422138A3 (en) 1974-03-30
BE774123A (en) 1972-04-19
CH572017A5 (en) 1976-01-30
YU39161B (en) 1984-08-31
CS160687B2 (en) 1975-03-28
PL85097B1 (en) 1976-04-30
ES396377A1 (en) 1974-12-16
NL168500B (en) 1981-11-16
NL7015842A (en) 1972-05-03
HU163937B (en) 1973-11-28
CA1022181A (en) 1977-12-06
FR2110057A5 (en) 1972-05-26
DE2153356A1 (en) 1972-05-04
YU259371A (en) 1982-05-31
DE2153356C2 (en) 1985-12-05
RO62243A (en) 1977-07-15
NL168500C (en) 1982-04-16
GB1342807A (en) 1974-01-03
JPS573669B1 (en) 1982-01-22
DK143446C (en) 1981-12-28
IT988549B (en) 1975-04-30

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