DK175638B1 - Process for the synthesis of arylsulfonylalkylamides - Google Patents
Process for the synthesis of arylsulfonylalkylamides Download PDFInfo
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- DK175638B1 DK175638B1 DK198901279A DK127989A DK175638B1 DK 175638 B1 DK175638 B1 DK 175638B1 DK 198901279 A DK198901279 A DK 198901279A DK 127989 A DK127989 A DK 127989A DK 175638 B1 DK175638 B1 DK 175638B1
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- alkylamine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/15—Sulfonamides having sulfur atoms of sulfonamide groups bound to carbon atoms of six-membered aromatic rings
- C07C311/16—Sulfonamides having sulfur atoms of sulfonamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the sulfonamide groups bound to hydrogen atoms or to an acyclic carbon atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
- C07C303/38—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reaction of ammonia or amines with sulfonic acids, or with esters, anhydrides, or halides thereof
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Pyridine Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
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Abstract
Description
DK 175638 B1DK 175638 B1
Det er vigtigt, at disse plastificeringsmidler ikke nedbrydes med varmen. Inkorporering af plastificeringsmiddel foregår ved høje temperaturer (200-250 °C), dvs. at der ikke under anvendelsen deraf bør være en kilde til dannelse af sure produkter, som udøver risiko for at udvikle en misfarvning og på den 5 anden side skade de mekaniske egenskaber af de polymere (bristning af kæde). I europæisk patentansøgningsskrift nr. EP 7623 offentliggjort 6. februar 1980 omtales en fremgangsmåde til rensning af arylsulfonylalkylamid ved indvirkning af et alkaliskmiddel ved 200 °C til opnåelse af et termostabilt produkt. Man har nu fundet en fremgangsmåde, som gør det muligt at synte-10 tisere et arylsulfonylalkylamid, der er termostabilt og således direkte anvendeligt som plastificeringsmiddel i polyamider, uden at man behøver at anvende en fremgangsmåde til rensning, såsom f.eks. den, der er beskrevet i europæisk patentansøgningsskrift nr. 7623.It is important that these plasticizers do not break down with heat. The incorporation of plasticizer takes place at high temperatures (200-250 ° C), ie. that during its use there should not be a source of formation of acidic products which exerts a risk of developing a discoloration and, on the other hand, damaging the mechanical properties of the polymers (chain rupture). European Patent Application Publication No. EP 7623 published February 6, 1980 discloses a process for purifying arylsulfonylalkylamide by the action of an alkaline agent at 200 ° C to obtain a thermostable product. A process has now been found which makes it possible to synthesize an arylsulfonylalkylamide which is thermostable and thus directly usable as a plasticizer in polyamides, without the need for a method of purification, such as e.g. the one described in European Patent Application Serial No. 7623.
15 Den foreliggende opfindelse angår en fremgangsmåde til syntese af arylsulfonylalkylamid med formlen: 0- s< ' .s ........Λ..The present invention relates to a process for the synthesis of arylsulfonylalkylamide having the formula: 0- s <.s ........ Λ ..
20 hvor Ri betegner et hydrogenatom eller en C1-C10 alkylgruppe, R2 betegner en Cno alkylgruppe, og R3 betegner en eller flere identiske eller forskellige substituenter valgt blandt halogener og alkylgrupper med op til 5 carbonato-25 mer, ved reaktion mellem et arylsulfohalogenid og en alkylamin, hvilken fremgangsmåde er ejendommelig derved, at a) man bringer arylsulfohalogenidet i kontakt med et overskud af alkylaminWherein R 1 represents a hydrogen atom or a C 1 -C 10 alkyl group, R 2 represents a C 10 alkyl group, and R 3 represents one or more identical or different substituents selected from halogens and alkyl groups of up to 5 carbon atoms, by reaction between an aryl sulfohalide and a alkylamine, the process being characterized in that a) contacting the aryl sulfohalide with an excess of alkylamine
I DK 175638 B1 II DK 175638 B1 I
I II I
I og en vandig opløsning af et alkalisk middel, idet det alkaliske middel er i IAnd an aqueous solution of an alkaline agent, the alkaline agent being in I
I overskud i forhold til det anvendte arylsulfohalogenid, IIn excess of the arylsulfohalide used, I
I b) man fjerner vandet og alkylaminen ved destillation fra den under a) opnå- IIn b) the water and alkylamine are removed by distillation from the one obtained in (a)
HH
I 5 ede organiske fase, og IIn the 5th organic phase, and
I c) man fraseparerer arylsulfonylalkylamidet fra den under b) opnåede rest. IIn c) the arylsulfonylalkylamide is separated from the residue obtained under b). IN
I Skønt Ri og R2 kan være forskellige, anvender man med fordel produkter, iAlthough R 1 and R 2 may be different, products are advantageously used i
I 10 hvilket Ri og R2 er identiske, og blandt disse produkter foretrækker man så- IIn which R 1 and R 2 are identical, and among these products I-I prefer
I danne, i hvilke Ri og R2 ikke har mere end 3 carbonatomer. En anden familie IIn those in which R 1 and R 2 have no more than 3 carbon atoms. Another family I
af interessante produkter er den, i hvilken Ri betegner hydrogen, og R2 er en Iof interesting products is that in which R 1 represents hydrogen and R 2 is an I
I alkylgruppe indeholdende med fordel 2-6 carbonatomer, fortrinsvis 4. IPreferably in the alkyl group containing 2-6 carbon atoms, preferably 4. I
15 Blandt substituenteme på benzenkemen foretrækker man fluor, chlor, brom IAmong the substituents on the benzene core, fluorine, chlorine, bromine I are preferred
I og methyl. Kernen kan omfatte flere af disse substituenter samtidig, dvs. at II and methyl. The nucleus may comprise several of these substituents simultaneously, viz. that I
man kan have f.eks. en methylgruppe og et eller flere bromatomer eller også Ione can have e.g. a methyl group and one or more bromine atoms or also I
I en methylgruppe og et eller flere chloratomer. Særligt interessante produkter IIn a methyl group and one or more chlorine atoms. Particularly interesting products
I er sådanne, i hvilke R3 er hydrogen, dvs. den ikke-substituerede benzenker- IYou are those in which R 3 is hydrogen, i. the unsubstituted benzene- I
I 20 ne, Rier ligeledes hydrogen, og R2 er en alkylgruppe indeholdende 2-6 car- IIn 20 ne, R 10 is also hydrogen and R 2 is an alkyl group containing 2-6 car-I
I bonatomer.In bone atoms.
I Blandt disse produkter anvender man fortrinsvis N,n-butylbenzensulfonamid IAmong these products, N, n-butylbenzenesulfonamide I is preferably used
I med formlen: II of the formula:
I 25 II 25 I
I /F\_ s II / F \ _ s I
V \V-so2nV \ V-so2n
I ^Cfl2CH2CH2CH3 II ^ Cfl2CH2CH2CH3 I
I Arylsulfohalogenid-udgangsforbindelsen er et produkt med følgende formel: IIn the arylsulfohalide starting compound is a product of the following formula: I
3 DK 175638 B1 C^"sv *3 hvori R3 har samme betydning som tidligere anført, og X betegner et halogenatom. X betegner med fordel chlor og brom, fortrinsvis chlor. Alkylamin-5 udgangsforbindelsen er et produkt med følgende formel: . VRi HN .....- X- hvori Ri og R2 har den tidligere anførte betydning.Wherein R 3 has the same meaning as previously stated and X represents a halogen atom. X preferably represents chlorine and bromine, preferably chlorine. The alkylamine-5 starting compound is a product of the following formula: VRi HN .....-X- wherein R 1 and R 2 are as previously defined.
10 Reaktionen mellem arylsulfohalogenidet og alkylaminen er i alt væsentlighed total og nødvendiggør i teorien et mol halogenid per mol amin, man opnår et mol HX, som man omdanner med et alkalisk middel.The reaction between the arylsulfohalide and the alkylamine is essentially complete and, in theory, requires one mole of halide per mole of amine to obtain one mole of HX which is converted with an alkaline agent.
Man anvender fortrinsvis benzensulfochlorid, dvs. det produkt, i hvilket R3 er 15 hydrogen, og X er chlor, samt n-butylamin, dvs. det produkt, i hvilket Ri er hydrogen, og R2 er n-butyl.Preferably, benzenesulfochloride is used, i.e. the product in which R 3 is hydrogen and X is chloro, as well as n-butylamine, i. the product in which R 1 is hydrogen and R 2 is n-butyl.
Det er trin a) af største betydning at anvende et overskud af alkylamin, dvs. at man per mol halogenid anvender mere end et mol amin.Step a) is of the utmost importance to use an excess of alkylamine, i.e. more than one mole of amine is used per mole of halide.
2020
Dette overskud udtrykt i mol er med fordel 20 %, dvs. 1,2 mol amin per mol anvendt halogenid, fortrinsvis 5-15%. Man overskrider ikke opfindelsens rammer ved at anvende et større overskud; men ved reaktionens afslutning vil det være nødvendigt at recirkulere betydelige mængder af aminen.This excess expressed in moles is advantageously 20%, ie. 1.2 moles of amine per mole of halide used, preferably 5-15%. The scope of the invention is not exceeded by using a larger excess; but at the end of the reaction, it will be necessary to recycle substantial amounts of the amine.
I DK 175638 B1 II DK 175638 B1 I
I II I
I Man kan som alkalisk middel i vandig opløsning f.eks. anvende hydroxider,As an alkaline agent in aqueous solution, e.g. use hydroxides,
I carbonater, hydrogencarbonater og alkoholater af alkalimetaller og jprdalka- IIn carbonates, hydrogen carbonates and alcohols of alkali metals and jprdalka- I
I limetaller. Man anvender med fordel natriumhydroxid (natriumlud) eller kali- IIn adhesive numbers. Advantageously, sodium hydroxide (sodium liquor) or potassium I is used
I 5 umhydroxid, fortrinsvis natriumhydroxid. Skønt koncentrationen af natrium- IIn 5 µm hydroxide, preferably sodium hydroxide. Although the concentration of sodium I
hydroxid eller af kaliumhydroxid er uden betydning, er det bekvemt at anven- Ihydroxide or potassium hydroxide is of no importance, it is convenient to use
I de vandige opløsninger mellem 10 og 30 vægt-%. Den mængde alkalisk IIn the aqueous solutions between 10 and 30% by weight. The amount of alkaline I
I middel, der er nødvendig, er en funktion af mængden af sulfohalogenid, der IThe agent needed is a function of the amount of sulfohalide which I
I anvendes i a), idet det støkiometriske forhold er et ækvivalent alkalisk middel II is used in a), the stoichiometric ratio being an equivalent alkaline agent I
I 10 per et mol sulfohalogenid, dvs. at dersom man anvender kaliumhydroxid eller IIn 10 per one mole of sulfohalide, i.e. that if potassium hydroxide or I is used
natriumhydroxid behøver der deraf mindst ét mol per mol sulfohalogenid. Detsodium hydroxide thereof needs at least one mole per mole of sulfohalide. The
I er nødvendigt at anvende et overskud af alkalisk middel i forhold til den stø- IYou need to use an excess of alkaline agent relative to the support
kiometriske mængde, således som den er blevet defineret. Man anvender Ikiometric amount as defined. You use
I med fordel et molært overskud, der kan gå op til 10%, og som fortrinsvis be- IYou preferably have a molar excess which can go up to 10%, and preferably preferably
I 15 finder sig mellem 1 og 5%. Man overskrider ikke opfindelsens rammer ved at IIn 15 find themselves between 1 and 5%. The scope of the invention is not exceeded in that you
I anvende et stort overskud af natriumhydroxid; men fremgangsmåden vil blive IYou use a large excess of sodium hydroxide; but the procedure will be I
I kompliceret af store mængder af overskydende produkt, som skal bortskaf- IIn complicated by large quantities of excess product which must be disposed of
fes. Ifes. IN
I 20 Man kan arbejde kontinuert eller diskontinuert og ved at tilsætte arylsulfoha- II You can work continuously or discontinuously and by adding arylsulfoha- I
I logenidet, alkylaminen og den vandige opløsning af det alkaliske middel i en IIn the logenide, alkylamine and aqueous solution of the alkaline agent in an I
I vilkårlig rækkefølge eller for en del i en rækkefølge og for en anden del i en IIn random order or for one part in one order and for another part in one I
I anden rækkefølge. Den eneste betingelse, der skal respekteres, er at man IIn second order. The only condition to be respected is that you
ikke ødelægger arylsulfohalogenidet ved reaktion med det alkaliske middel. Idoes not destroy the arylsulfohalide by reaction with the alkaline agent. IN
I 25 Man kan f.eks. bringe arylsulfohalogenid i kontakt med alkylaminen og derpå IFor example, contacting aryl sulfohalide with the alkylamine and then I
I tilsætte det alkaliske middel. Man kan også hælde arylsulfohalogenidet i en IYou add the alkaline agent. One can also pour the arylsulfohalide into an I
omrørt blanding af det alkaliske middel i vandig opløsning og af alkylamin. Istirred mixture of the alkaline agent in aqueous solution and of alkylamine. IN
Man anvender udtrykket "omrørt blanding", fordi den alkaliske opløsning og IThe term "stirred mixture" is used because the alkaline solution and I
I alkylaminen i almindelighed ikke er blandbar, og ved omrøring opnår man en IIn general, the alkyl amine is immiscible and upon stirring an I is obtained
30 slags ustabil emulsion. Man kan ligeledes ifølge en anden variant indhælde I30 kinds of unstable emulsion. According to another variant one can also contain I
arylsulfohalogenid og den vandige opløsning af det alkaliske middel i alkyla- Iarylsulfohalide and the aqueous solution of the alkaline agent in the alkyl I
5 DK 175638 B1 minen med en let forsinkelse med hensyn til den alkaliske opløsning. Udtrykket "forsinkelse" henfører til antallet af mol alkalisk middel i forhold til antallet af mol arylsulfohalogenid.5 DK 175638 B1 mine with a slight delay with respect to the alkaline solution. The term "delay" refers to the number of moles of alkaline agent relative to the number of moles of aryl sulfohalide.
5 Det er inden for opfindelsen af afgørende betydning at have i kontakt et arylsulfohalogenid, en alkylamin, vand og et alkalisk middel, og man overskrider ikke opfindelsens rammer ved at anvende et vandfrit alkalisk middel og vand eller et vandfrit alkalisk middel og en alkylamin i vandig emulsion. Man kan anvende sulfohalogenid som det foreligger eller i opløsning i et opløsnings-10 middel, alkylaminen kan også være som den foreligger eller eventuelt i et opløsningsmiddel, f.eks. i toluen.It is essential within the invention to have in contact an arylsulfohalide, an alkylamine, water and an alkaline agent, and the scope of the invention is not exceeded by using an anhydrous alkaline agent and water or an anhydrous alkaline agent and an alkylamine in aqueous. emulsion. Sulfohalide may be used as it is or in solution in a solvent, the alkylamine may also be as it is or optionally in a solvent, e.g. in toluene.
Skønt trinnet a) kan gennemføres ved enhver temperatur og ethvert tryk under forudsætning af, at produkterne ikke nedbrydes, foretrækker man at ar-15 béjde ved omgivelsernes temperatur eller tæt ved omgivelsernes temperatur og ved atmosfæretryk eller ved et tryk tæt derved, på en sådan måde, at ha-logenidet er flydende og at aminen ligeledes er flydende. Dersom disse betingelser er umulige at forene, anbringer man sig i en tryk- og temperaturzone, hvori halogenidet er flydende, og aminen er gasformig. Disse betingelser 20 er med fordel en temperatur lavere end 150 °C og et tryk lavere end 5 bar relativt tryk.Although step a) can be carried out at any temperature and pressure provided that the products are not degraded, it is preferable to work at ambient temperature or close to ambient temperature and at atmospheric pressure or at a pressure close thereto, in such a manner. , that the halogenide is liquid and that the amine is also liquid. If these conditions are impossible to reconcile, one is placed in a pressure and temperature zone in which the halide is liquid and the amine is gaseous. These conditions 20 are advantageously a temperature lower than 150 ° C and a pressure lower than 5 bar relative pressure.
Man arbejder fortrinsvis ved atmosfæretryk og ved en temperatur tæt ved omgivelsernes temperatur, dvs. mellem 0 °C og 50 °C.Preferably, one operates at atmospheric pressure and at a temperature close to the ambient temperature, ie. between 0 ° C and 50 ° C.
2525
Varigheden af dette trin a) er uden betydning; men reaktionen er øjeblikkelig, og dens varighed er fastlagt af de praktiske betingelser knyttet til apparaturet og til de mængder, der skal håndteres.The duration of this step a) is immaterial; but the reaction is immediate and its duration is determined by the practical conditions attached to the apparatus and the quantities to be handled.
30 Denne varighed er i almindelighed i størrelsesordenen fra 15 minutter til nogle timer.30 This duration is generally in the range of 15 minutes to a few hours.
I DK 175638 B1 II DK 175638 B1 I
I II I
I Denne kontaktdannelse er en i sig selv kendt behandling og kan gennemfø- IThis contact formation is a treatment known per se and can be accomplished
I res i ethvert apparatur anvendt inden for de kemiske industri, man anvenderYou will find in any apparatus used in the chemical industry used
I med fordel apparatur, der lader sig omrøre. IAdvantageously, stirring apparatus. IN
I II I
I Når alle reaktionskomponenterne i dette trin a) er blevet bragt i kontakt, op- I retholder man med fordel reaktionsmediet under omrøring ved en temperaturWhen all of the reaction components of this step a) have been brought into contact, the reaction medium is advantageously maintained while stirring at a temperature.
mellem 20 °C og 100 °C, fortrinsvis 40 °C - 70 °C i en tidsperiode, der kan Ibetween 20 ° C and 100 ° C, preferably 40 ° C - 70 ° C for a period of time capable of
I variere fra nogle minutter til nogle timer, og som fortrinsvis befinder sig mel- IYou range from a few minutes to a few hours, and are preferably in the middle
I 10 lem en time og tre timer. Man går derpå videre med separeringen af det ved IFor 10 minutes one hour and three hours. You then proceed with the separation of it by I
I afslutningen af trin a) opnåede reaktionsmedium i en vandig fase og en or-At the end of step a), reaction medium obtained in an aqueous phase and an
ganisk fase, som i hovedsagen indeholder arylsulforylalkylamid, alkylamin og Iganic phase containing substantially arylsulforylalkylamide, alkylamine and I
I nogle procent vand. Denne separation af de to faser er en i sig selv kendt IIn some percent water. This separation of the two phases is one known per se
I behandling. IIn treatment. IN
I 15 II 15 I
Trinnet b) består i at fjerne vandet og alkylaminen fra denne organiske fase. IStep b) consists of removing the water and alkylamine from this organic phase. IN
I Det er fordelagtigt at gå videre med destillation. Man kan arbejde under va- II It is advantageous to proceed with distillation. You can work under va- I
I kuum eller op til nogle bar forudsat at man ikke overskrider den temperatur, IIn vacuum or up to some bar, provided that the temperature is not exceeded
I ved hvilken den organiske fase begynder at nedbrydes, eller at danne farve- IYou know where the organic phase begins to decompose, or to form color
H 20 de produkter eller nedbrydningsprodukter. Denne temperatur er sædvanligvis IH 20 the products or degradation products. This temperature is usually I
I lavere end 180 °C. Man arbejder med fordel mellem 130 °C og 170 °C. Man IAt lower than 180 ° C. It is advantageous to operate between 130 ° C and 170 ° C. Man I
I overskrider ikke opfindelsens rammer ved at arbejde ved en højere tempera- IYou do not exceed the scope of the invention by operating at a higher temperature
I tur; men man risikerer at nedbryde produkterne, således at det er mere en- IIn turn; but you risk breaking down the products so that it is more simple
kelte at arbejde ved lavere temperatur. Icold to work at lower temperature. IN
IIN
Behandlingens varighed er uden betydning, den er fastlagt ved de praktiske IThe duration of treatment is immaterial, it is determined by the practical I
I betingelser, der er knyttet til apparaturet og til de mængder af vand og alky- IIn conditions attached to the apparatus and to the quantities of water and alkali
lamin, der skal bortskaffes. Ilaminate to be disposed of. IN
30 Dette trin b) kan såvel som alle andre trin i den foreliggende opfindelse gen- IThis step b), as well as all other steps of the present invention, can be repeated
nemføres kontinuert eller diskontinuert. Når man har fjernet alt vandet og al- Iis carried out continuously or discontinuously. After removing all the water and all- I
7 DK 175638 B1 kylaminet opnår man en organisk rest i hovedsagen indeholdende det efterstræbte amid. Man gennemfører trinnet c) ved ethvert kendt middel til separering. Man anvender med fordel en destillation eller én eller flere såkaldte flash-afdampninger eller en afdampning fra en film eller fra et tyndt lag og 5 under vakuum betingelser.In the chylamine, an organic residue is obtained substantially containing the desired amide. Step c) is performed by any known means of separation. Advantageously, a distillation or one or more so-called flash evaporation or evaporation from a film or a thin layer and under vacuum conditions is used.
I de efterfølgende eksempler består afprøvningen for termisk stabilitet i, at man holder arylsulfonylalkylamidet i tre timer ved 250 °C under nitrogen. Farvningen ved afslutningen af testen bør være mindre end 250 Hazen. Pro-10 duktet er så anvendeligt som plastificeringsmiddel.In the following examples, the thermal stability test consists of holding the arylsulfonyl alkylamide for three hours at 250 ° C under nitrogen. The staining at the end of the test should be less than 250 Hazen. The product is as useful as plasticizer.
Man arbejder, når intet andet er anført, i en reaktor af glas forsynet med en om rører, med en termometerlomme, med en injektionsmekanisme til gennemskylning med nitrogen, med en opadstigende køler og med afkøling ved 15 hjælp af et bad af koldt vand eller koldt saltvand. Under destillationerne (trinnene b) og c)) opretholder man et dække af nitrogen over produkterne.Unless otherwise stated, one operates in a glass reactor equipped with a stirrer, with a thermometer pocket, with an injection mechanism for flushing with nitrogen, with an upward cooler and with cooling by means of a bath of cold water or cold. brine. During distillation (steps (b) and (c)), a cover of nitrogen is maintained over the products.
Eksempel 1 20 a) Man indhælder i løbet af 1 time og 30 minutter 3 mol benzensulfochlorid (C6H5SO2CI) i en blanding indeholdende 3,051 mol natriumhydroxid i vandig opløsning indeholdende 19,37 vægt-% og 3,3 mol n-butylamin (CH3CH2CH2CH2NH2). Reaktorens temperatur holdes ved 20 °C. Derpå hæver man denne temperatur til mellem 60 og 65 °C i timer. Efter dekantering , 25 opnår man 675 g af en organisk fase indeholdende 3 X 0,9959 mol N.n- butylbenzensulfonamid (C6H5SO2NHCH2CH2CH2CH3) (BBSA).Example 1 a) 3 moles of benzenesulfochloride (C6H5SO2Cl) are poured into a mixture containing 3.051 moles of sodium hydroxide in aqueous solution containing 19.37% by weight and 3.3 moles of n-butylamine (CH3CH2CH2CH2NH2) over 1 hour and 30 minutes. The temperature of the reactor is maintained at 20 ° C. This temperature is then raised to between 60 and 65 ° C for hours. After decantation, 675 g of an organic phase containing 3 X 0.9959 moles of N.n-butylbenzenesulfonamide (C6H5SO2NHCH2CH2CH2CH3) (BBSA) are obtained.
b) Man destillerer denne organiske fase for at fjerne vandet og n-butylaminet, idet man holder temperaturen i bunden af apparatet fra 20 til 145 °C under et 30 vakuum fra 740 til 01 mm Hg i 1 time.b) This organic phase is distilled to remove the water and n-butylamine, keeping the temperature at the bottom of the apparatus from 20 to 145 ° C under a vacuum of 740 to 01 mm Hg for 1 hour.
I DK 175638 B1 II DK 175638 B1 I
I II I
I c) Man destillerer under vakuum (0,5 mm Hg) den opnåede rest, og man op- I samler på denne måde 96% af det BBSA, der er indeholdt i den organiske I fase ved afslutning af trin a). Den termiske test viser en farvning på 50 Ha-I c) The resulting residue is distilled under vacuum (0.5 mm Hg) and thus 96% of the BBSA contained in the organic phase is collected at the end of step a). The thermal test shows a staining of 50 Ha
I zen. „II zen. "IN
I II I
I Eksempel 2 IIn Example 2 I
I Man går frem analogt med eksempel 1, med undtagelse af at temperaturen IOne proceeds analogously to Example 1, except that the temperature I
I under indhældning af benzensulfochloridet holdes ved 50 °C. De opnåede IDuring the pouring of the benzene sulfochloride is maintained at 50 ° C. They obtained I
I 10 resultater er identiske med eksempel 1. IIn 10 results are identical to Example 1. I
I Eksempel 3 IIn Example 3 I
a) Man indhælder 0,6 mol benzensulfochlorid i 3,3 mol n-butylamin, idet man Ia) 0.6 moles of benzenesulfochloride are contained in 3.3 moles of n-butylamine,
I 15 holder reaktoren ved 50 °C. Derpå indhælder man samtidig 3,051 mol natri- IAt 15, the reactor holds at 50 ° C. At the same time, 3.051 moles of sodium I are simultaneously contained
umhydroxid i form af en vandig opløsning med 19,37 vægt-% og 2,4 mol ben- Iumhydroxide in the form of an aqueous solution of 19.37% by weight and 2.4 mole of bone-I
I zensulfochlorid i løbet af 1 time og 30 minutter, idet reaktoren holdes ved 50 IIn zenesulfochloride over 1 hour and 30 minutes, keeping the reactor at 50 L
I °C. Man tilsætter 7 g vand for at skylle indhældningstragten for natrium- II ° C. 7 g of water are added to flush the sodium I pouring funnel
hydroxidet. Man opvarmer derpå reaktoren i 2 timer mellem 60 °C og 65 °C. Ihydroxide. The reactor is then heated for 2 hours between 60 ° C and 65 ° C. IN
20 I20 I
Efter dekantering opnår man 669 g af en organisk fase indeholdende 3 X IAfter decanting, 669 g of an organic phase containing 3 X I is obtained
I 0,9939 mol BBSA. IIn 0.9939 moles of BBSA. IN
b) Man destillerer analogt med eksempel 1. Ib) Distillate analogously to Example 1. I
I »iI »i
c) Man destillerer under et vakuum på 0,5 mm Hg den opnåede rest, og man Ic) Distillate the residue obtained under a vacuum of 0.5 mm Hg and I
opsamler på denne måde 95% af det BBSA, der er indeholdt i den organiske Iin this way collects 95% of the BBSA contained in the organic I
I fase ved afslutningen af trinnet a). Den termiske test viser en farvning på 50 IIn phase at the end of step a). The thermal test shows a staining of 50 l
Hazen. IHazen. IN
I 30 II 30 I
9 DK 175638 B19 DK 175638 B1
Eksempel 4Example 4
Man går frem analogt med eksempel 2, idet man dog anvender en reaktor . rustfrit stål, hvis bund er af typen 304 L, og hvori resten er af typen 316 L.You proceed by analogy with Example 2, however, using a reactor. stainless steel, the bottom of which is of type 304 L and the rest of which is of type 316 L.
5 Man opnår identiske resultater.5 Identical results are obtained.
Eksempel 5 a) Man indhælder i løbet af 30 minutter 3 mol benzensulfochlorid i 3,3 mol n-x 10 butylamin, idet reaktorens temperatur holdes ved 50 °C. Derpå indhælder man i løbet af 1 time og 30 minutter 3,15 mol natriumhydroxid i vandig opløsning med styrken 19,91%.Example 5 a) Three moles of benzenesulfochloride are poured into 3.3 moles of n-x 10 butylamine over 30 minutes, keeping the temperature of the reactor at 50 ° C. Then, in 1 hour and 30 minutes, 3.15 moles of sodium hydroxide in aqueous solution of 19.91% strength is poured.
Man skyller indhældningstragten for natriumhydroxid med 13,5 g vand. Man 15 opvarmer reaktoren mellem 60 og 70 °C i 2 timer. Efter dekantering opnår man 671,8 g af en organisk fase indeholdende 3 mol BBSA.The sodium hydroxide pouring funnel is rinsed with 13.5 g of water. The reactor is heated between 60 and 70 ° C for 2 hours. After decanting, 671.8 g of an organic phase containing 3 moles of BBSA is obtained.
b) Man afdestillerer vandet og aminen analogt med eksempel 1. Man konstaterer, at man har tabt 6,1% af den i trinnet b) anvendte masse under denne 20 destillation.b) The water and amine are distilled off by analogy to Example 1. It is found that 6.1% of the mass used in step b) has been lost during this distillation.
c) Man destillerer under vakuum (0,5 mm Hg) den opnåede rest, og man opsamler på denne måde 92% af det BBSA, der er indeholdt i den organiske fase ved afslutning af trinnet a). Den termiske test viser en farvning på 175 25 Hazen.c) The residue obtained in vacuo (0.5 mm Hg) is distilled off and 92% of the BBSA contained in the organic phase is collected at the end of step a). The thermal test shows a staining of 175 25 Hazen.
**
Eksempel 6 a) Man går frem analogt med eksempel 3, med undtagelse af at reaktoren 30 holdes ved 20 °C i stedet for 50 °C under de to behandlinger ved indhældning af reaktionskomponenterne. Man opnår efter dekantering 671,8 g af enExample 6 (a) Proceed analogously to Example 3, except that reactor 30 is maintained at 20 ° C instead of 50 ° C during the two treatments by pouring the reaction components. After decanting, 671.8 g of one is obtained
DK 175638 B1 IDK 175638 B1 I
10 I10 I
organisk fase indeholdende 3 X 0,998 mol BBSA. Iorganic phase containing 3 X 0.998 moles of BBSA. IN
b) Man afdestillerer vandet og aminen analogt med eksempel 1. Man konsta- Ib) The water and amine are distilled off by analogy to Example 1. One is constituted
terer at man har tabt 6,07% af massen under denne destillation. ,It is estimated that 6.07% of the mass has been lost during this distillation. .
c) Man destillerer under vakuum (0,5 mm Hg) den opnåede rest, og man op- Ic) Distillate the residue obtained under vacuum (0.5 mm Hg) and dissolve
samler 3 fraktioner svarende til foreløbig hoved portionen og efterløbet af de- Igathers 3 fractions corresponding to the provisional main portion and the aftermath of the I
stillationen (de anførte procenttegn er vægtprocent): Ithe position (the percentages indicated are by weight):
10 F1 = 4,9% IF1 = 4.9% I
F2 = 84,2% IF2 = 84.2% I
F3= 7,1% IF3 = 7.1% I
I kolben er tilbage 3,8% (procent af massen anvendt i trinnet c)). IIn the flask is left 3.8% (percent of the mass used in step c)). IN
1 15 I1 15 I
I Den termiske test på F2 svarer til en farvning lavere II The thermal test on F2 corresponds to a staining lower I
end 50 Hazen og 100 Hazen på F1 + F2 + F3. Ithan 50 Hazen and 100 Hazen on F1 + F2 + F3. IN
I Eksempel 7 IIn Example 7 I
IIN
I Man går frem analogt med eksempel 2 med undtagelse af, at man anvender IYou proceed by analogy with Example 2 except that you use
I 3,75 mol n-butylamin. Man opnår 702,6 g af en organisk fase indeholdende 3 IIn 3.75 moles of n-butylamine. 702.6 g of an organic phase containing 3 L are obtained
I X 0,9924 mol BBSA. Man opnår identiske resultater. IIn X 0.9924 mol BBSA. Identical results are obtained. IN
25 Eksempel 8 IExample 8 I
I Man går frem analogt med eksempel 2 med undtagelse af, at man anvender IYou proceed by analogy with Example 2 except that you use
3,15 mol n-butylamin. Man opnår 659,8 g af en organisk fase indeholdende 3 I3.15 moles of n-butylamine. 659.8 g of an organic phase containing 3 L are obtained
I X 0,9915 mol BBSA. Man opnår identiske resultater. IIn X 0.9915 mol BBSA. Identical results are obtained. IN
Claims (5)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8803447 | 1988-03-17 | ||
| FR8803447A FR2628739B1 (en) | 1988-03-17 | 1988-03-17 | PROCESS FOR THE SYNTHESIS OF ARYLSULFONYLALKYLAMIDE |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DK127989D0 DK127989D0 (en) | 1989-03-16 |
| DK127989A DK127989A (en) | 1989-09-18 |
| DK175638B1 true DK175638B1 (en) | 2005-01-03 |
Family
ID=9364346
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK198901279A DK175638B1 (en) | 1988-03-17 | 1989-03-16 | Process for the synthesis of arylsulfonylalkylamides |
Country Status (14)
| Country | Link |
|---|---|
| EP (1) | EP0333557B1 (en) |
| JP (1) | JPH024766A (en) |
| KR (1) | KR940010765B1 (en) |
| CN (1) | CN1020600C (en) |
| AT (1) | ATE101129T1 (en) |
| CA (1) | CA1307295C (en) |
| DE (1) | DE68912797T2 (en) |
| DK (1) | DK175638B1 (en) |
| ES (1) | ES2062055T3 (en) |
| FI (1) | FI90763C (en) |
| FR (1) | FR2628739B1 (en) |
| IE (1) | IE63494B1 (en) |
| NO (1) | NO170412C (en) |
| PT (1) | PT90025B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2084176T3 (en) * | 1991-09-05 | 1996-05-01 | Pharno Wedropharm Gmbh | DERIVATIVES OF AROMATIC SULFONAMIDES, THEIR USE AS INHIBITORS OF ENZYMES AND PHARMACEUTICAL COMPOSITIONS THAT CONTAIN THEM. |
| TW219358B (en) * | 1991-12-20 | 1994-01-21 | Hokuriku Pharmaceutical | |
| GB9625781D0 (en) * | 1996-12-11 | 1997-01-29 | Zeneca Ltd | Chemical process |
| JP5076682B2 (en) * | 2006-07-26 | 2012-11-21 | セントラル硝子株式会社 | Process for producing N- (bicyclo [2,2,1] hept-5-en-2-ylmethyl) -1,1,1-trifluoromethanesulfonamide |
| CN109369473A (en) * | 2018-09-19 | 2019-02-22 | 南通沃兰化工有限公司 | A kind of synthetic method of N-butylbenzenesulfonamide |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2833650A1 (en) * | 1978-08-01 | 1980-02-21 | Basf Ag | METHOD FOR PRODUCING THERMOSTABLE ARYLSULFONYLALKYLAMIDES |
| DE2941593A1 (en) * | 1979-10-13 | 1981-04-23 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING SULPHONAMIDES |
-
1988
- 1988-03-17 FR FR8803447A patent/FR2628739B1/en not_active Expired - Lifetime
-
1989
- 1989-02-20 CA CA000591539A patent/CA1307295C/en not_active Expired - Lifetime
- 1989-03-01 NO NO890864A patent/NO170412C/en not_active IP Right Cessation
- 1989-03-07 ES ES89400638T patent/ES2062055T3/en not_active Expired - Lifetime
- 1989-03-07 EP EP89400638A patent/EP0333557B1/en not_active Expired - Lifetime
- 1989-03-07 DE DE68912797T patent/DE68912797T2/en not_active Expired - Lifetime
- 1989-03-07 AT AT89400638T patent/ATE101129T1/en not_active IP Right Cessation
- 1989-03-15 JP JP1063399A patent/JPH024766A/en active Granted
- 1989-03-16 FI FI891256A patent/FI90763C/en not_active IP Right Cessation
- 1989-03-16 DK DK198901279A patent/DK175638B1/en not_active IP Right Cessation
- 1989-03-16 IE IE85889A patent/IE63494B1/en not_active IP Right Cessation
- 1989-03-16 PT PT90025A patent/PT90025B/en not_active IP Right Cessation
- 1989-03-17 KR KR1019890003358A patent/KR940010765B1/en not_active IP Right Cessation
- 1989-03-17 CN CN89101437A patent/CN1020600C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| FR2628739A1 (en) | 1989-09-22 |
| FI90763B (en) | 1993-12-15 |
| NO170412C (en) | 1992-10-14 |
| PT90025B (en) | 1994-05-31 |
| KR890014464A (en) | 1989-10-23 |
| NO170412B (en) | 1992-07-06 |
| DE68912797T2 (en) | 1994-06-01 |
| FR2628739B1 (en) | 1990-09-07 |
| FI90763C (en) | 1994-03-25 |
| EP0333557B1 (en) | 1994-02-02 |
| DE68912797D1 (en) | 1994-03-17 |
| DK127989A (en) | 1989-09-18 |
| KR940010765B1 (en) | 1994-11-11 |
| CN1020600C (en) | 1993-05-12 |
| ES2062055T3 (en) | 1994-12-16 |
| IE890858L (en) | 1989-09-17 |
| EP0333557A2 (en) | 1989-09-20 |
| ATE101129T1 (en) | 1994-02-15 |
| PT90025A (en) | 1989-11-10 |
| JPH024766A (en) | 1990-01-09 |
| DK127989D0 (en) | 1989-03-16 |
| CA1307295C (en) | 1992-09-08 |
| NO890864L (en) | 1989-09-18 |
| FI891256A (en) | 1989-09-18 |
| JPH0465063B2 (en) | 1992-10-16 |
| IE63494B1 (en) | 1995-05-03 |
| CN1037894A (en) | 1989-12-13 |
| FI891256A0 (en) | 1989-03-16 |
| EP0333557A3 (en) | 1990-10-17 |
| NO890864D0 (en) | 1989-03-01 |
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