NO170412B - PROCEDURE FOR THE PREPARATION OF ARYLSULPHONYLALKYLAMIDE - Google Patents
PROCEDURE FOR THE PREPARATION OF ARYLSULPHONYLALKYLAMIDE Download PDFInfo
- Publication number
- NO170412B NO170412B NO890864A NO890864A NO170412B NO 170412 B NO170412 B NO 170412B NO 890864 A NO890864 A NO 890864A NO 890864 A NO890864 A NO 890864A NO 170412 B NO170412 B NO 170412B
- Authority
- NO
- Norway
- Prior art keywords
- alkylamine
- alkaline agent
- excess
- mol
- organic phase
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims 2
- 150000003973 alkyl amines Chemical class 0.000 claims abstract description 22
- -1 arylsulphonyl halide Chemical class 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 239000012074 organic phase Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 26
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 abstract description 9
- 239000004014 plasticizer Substances 0.000 abstract description 5
- IPRJXAGUEGOFGG-UHFFFAOYSA-N N-Butylbenzenesulfonamide Natural products CCCCNS(=O)(=O)C1=CC=CC=C1 IPRJXAGUEGOFGG-UHFFFAOYSA-N 0.000 abstract description 4
- 239000004952 Polyamide Substances 0.000 abstract description 4
- 229920002647 polyamide Polymers 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical group CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 150000004820 halides Chemical class 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- CSKNSYBAZOQPLR-UHFFFAOYSA-N benzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC=C1 CSKNSYBAZOQPLR-UHFFFAOYSA-N 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 238000010908 decantation Methods 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000004391 aryl sulfonyl group Chemical group 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- IYMAUEAFOBSGCY-UHFFFAOYSA-N benzene;sulfurochloridic acid Chemical compound OS(Cl)(=O)=O.C1=CC=CC=C1 IYMAUEAFOBSGCY-UHFFFAOYSA-N 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000010186 staining Methods 0.000 description 2
- 239000012258 stirred mixture Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Polyamides (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Pyridine Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Steroid Compounds (AREA)
Abstract
Description
Foreliggende oppfinnelse angår en fremgangsmåte for fremstilling av arylsulfonylalkylamid. The present invention relates to a method for the production of arylsulfonyl alkylamide.
Arylsulfonylalkylamidene er produkter som benyttes som myknere for polyamider, spesielt polyamidene 11 og 12. Det er viktig at disse myknere ikke nedbrytes i varme. Innarbeiding av mykneren skjer ved forhøyede temperaturer på 200 til 250°C, det vil si at under anvendelsen må de ikke vise seg som kilder for dannelse av sure produkter som kan utvikle en farving og på den annen side forringe polymerens mekaniske egenskaper (kjedebrudd). The arylsulfonyl alkylamides are products that are used as plasticizers for polyamides, especially polyamides 11 and 12. It is important that these plasticizers do not break down in heat. Incorporation of the plasticizer takes place at elevated temperatures of 200 to 250°C, that is to say that during use they must not prove to be sources for the formation of acidic products that can develop a coloring and, on the other hand, impair the polymer's mechanical properties (chain breakage).
EP-publ. 7623 beskriver en fremgangsmåte for rensing av arylsulfonylalkylamid ved virkning av et alkalisk middel ved 200°C for å oppnå et termostabilt produkt. EP publ. 7623 describes a process for the purification of arylsulfonylalkylamide by the action of an alkaline agent at 200°C to obtain a thermostable product.
Man har nu funnet en fremgangsmåte som tillater å syntetisere et termostabilt arylsulfonylalkylamid som således direkte kan benyttes som mykner i polyamider uten å måtte ty til en renseprosess som for eksempel i det nevnte EP 7623. A method has now been found that allows a thermostable arylsulfonylalkylamide to be synthesized which can thus be directly used as a plasticizer in polyamides without having to resort to a cleaning process as for example in the aforementioned EP 7623.
Foreliggende oppfinnelse angår således en fremgangsmåte for fremstilling av alkylsulfonylalkylamid med formelen: The present invention thus relates to a method for producing alkylsulfonyl alkylamide with the formula:
der Ri er et hydrogenatom eller en C^.^Qalkylgruppe, R2 er en Ci_ioalkylgruppe °fi R3 er en eller flere like eller forskjellige substituenter valgt blant halogen og alkyl ved opp til 5 karbonatomer, ved omsetning av et arylsulfonylhalogenid og et alkylamin, og denne fremgangsmåte karakteriseres ved at man: a) bringer arylsulfonylhalogenidet i kontakt med et overskudd på opp til 20 % og fortrinnsvis mellom 5 og 15 % av et where R 1 is a hydrogen atom or a C 1-4 alkyl group, R 2 is a C 1-10 alkyl group °fi R 3 is one or more identical or different substituents selected from halogen and alkyl at up to 5 carbon atoms, by reacting an arylsulfonyl halide and an alkylamine, and this method is characterized by: a) bringing the arylsulfonyl halide into contact with an excess of up to 20% and preferably between 5 and 15% of a
alkylamin og en vandig oppløsning av et alkalisk middel alkylamine and an aqueous solution of an alkaline agent
idet mengden alkalisk middel er et overskudd på opp til 10 % og fortrinnsvis mellom 1 og 5 <& > i forhold til mengden wherein the amount of alkaline agent is an excess of up to 10% and preferably between 1 and 5 <&> in relation to the amount
benyttet arylsulfonylhalogenid, used arylsulfonyl halide,
b) fjerner vann og alkylamin fra den organiske fase oppnådd under a) ved destillasjon; og c) separerer arylsulfonylalkylamidet fra den under b) oppnådde rest. b) removes water and alkylamine from the organic phase obtained under a) by distillation; and c) separates the arylsulfonylalkylamide from the residue obtained under b).
Selv om Ri og R2 kan være forskjellige, benyttes fordelaktig produkter der R^ og R2 er like og man foretrekker produkter der R^ og R2 ikke har mer enn 3 karbonatomer. En annen interessant produktfamilie er den der er hydrogen og R2 er alkyl med fortrinnsvis 2 til 6 karbonatomer, helst 4 karbonatomer. Although Ri and R2 may be different, products are advantageously used where R^ and R2 are the same and products where R^ and R2 do not have more than 3 carbon atoms are preferred. Another interesting product family is that where is hydrogen and R 2 is alkyl with preferably 2 to 6 carbon atoms, preferably 4 carbon atoms.
Blant substituentene på benzenkjernen foretrekkes fluor, klor, brom og metyl. Kjernen kan omfatte flere substituenter samtidig. Det vil si at man for eksempel kan ha en metylgruppe og et eller flere bromatomer eller eventuelt en metylgruppe og et eller flere karbonatomer. Av spesielt interessante produkter skal nevnes de der R3 er hydrogen, det vil si der benzenkjernen ikke er substituert, R^ også er hydrogen og R2 er en alkylgruppe med 2 til 6 karbonatomer. Among the substituents on the benzene nucleus, fluorine, chlorine, bromine and methyl are preferred. The core can comprise several substituents at the same time. That is to say, you can have, for example, a methyl group and one or more bromine atoms or possibly a methyl group and one or more carbon atoms. Particularly interesting products should be mentioned those where R3 is hydrogen, that is where the benzene nucleus is not substituted, R^ is also hydrogen and R2 is an alkyl group with 2 to 6 carbon atoms.
Blant produktene benyttes fortrinnsvis N.n-butylbenzen-sulfonylamid med formelen: Among the products, N.n-butylbenzenesulfonylamide with the formula is preferably used:
Arylsulfonylhalogenidet man går ut fra er et produkt med den følgende formel: der R3 har den samme betydning som ovenfor angitt og X betyr halogen. X betyr fortrinnsvis klor og brom og aller helst klor. Alkylaminet man går ut fra er et produkt med følgende formel: The starting point is the arylsulfonyl halide is a product with the following formula: where R3 has the same meaning as stated above and X means halogen. X preferably means chlorine and bromine and most preferably chlorine. The starting alkylamine is a product with the following formula:
der Ri og R2 har den samme betydning som ovenfor angitt. where Ri and R2 have the same meaning as indicated above.
Reaksjonen mellom arylsulfonylhalogenid og alkylamin er i det vesentlige total og nødvendiggjør teoretisk et mol halogenid pr. mol amin <p>g man oppnår derved et mol HX som transformeres med alkalisk middel. The reaction between arylsulfonyl halide and alkylamine is essentially total and theoretically requires one mole of halide per mol amine <p>g one mole of HX is thereby obtained, which is transformed with an alkaline agent.
Man benytter fortrinnsvis benzensulfonylklorid, det vil si det produkt der R3 er hydrogen og X er klor og n-butylamin, det vil si det produkt der Rj er hydrogen og R2 er n-butyl. Benzenesulfonyl chloride is preferably used, i.e. the product where R3 is hydrogen and X is chlorine and n-butylamine, i.e. the product where Rj is hydrogen and R2 is n-butyl.
I trinn 1 er det vesentlig å benytte et overskudd av alkylamin, det vil si at man for et mol halogenid benytter mer enn 1 mol amin. In step 1, it is essential to use an excess of alkylamine, that is to say that for one mole of halide, more than 1 mole of amine is used.
Dette mol overskudd kan godt være ca. 20 %, det vil si at man benytter 1,2 mol amin pr. mol benyttet halogenid og fortrinnsvis benytter man et overskudd på 5 til 15 %. Man går imidlertid ikke utenfor oppfinnelsens ramme ved å benytte et stort overskudd men ved slutten av reaksjonene er det så nødvendig å resirkulere vesentlige aminmengder. This mole surplus may well be approx. 20%, which means that 1.2 mol of amine is used per mole of halide used and preferably an excess of 5 to 15% is used. However, one does not go outside the scope of the invention by using a large excess, but at the end of the reactions it is necessary to recycle significant amounts of amine.
Som alkalisk middel i vandig oppløsning kan man for eksempel benytte hydroksyder, karbonater, hydrogenkarbonater eller alkoholater av alkali- og jordalkalimetaller. Man benytter fortrinnsvis natrium- eller kaliumhydroksyd, fortrinnsvis natriumhydroksyd. Selv om konsentrasjonen av natrium- eller kaliumhydroksyd er uten betydning er det vanlig å benytte vandige oppløsninger på mellom 10 og 30 vekt-56. Mengden nødvendig alkalisk middel er en funksjon av mengden benyttet sulfohalogenid under a), idet støkiometrien er en ekvivalent alkali pr. 1 mol sulfohalogenid, det vil si at hvis man benytter kalium- eller natriumhydroksyd må man benytte minst 1 mol pr. mol sulfohalogenid. Det er nødvendig å benytte et overskudd av alkalisk middel i forhold til den støkiometriske mengden slik den er definert. Man benytter fortrinnsvis et molart overskudd helt opp til 10 % og fortrinnsvis mellom 1 og 5 %. Man går ikke utenfor oppfinnelsens ramme ved å benytte et stort overskudd av hydroksydet men prosessen kompliseres ved store mengder som senere må fjernes. As an alkaline agent in aqueous solution, one can for example use hydroxides, carbonates, hydrogen carbonates or alcoholates of alkali and alkaline earth metals. Sodium or potassium hydroxide is preferably used, preferably sodium hydroxide. Although the concentration of sodium or potassium hydroxide is unimportant, it is common to use aqueous solutions of between 10 and 30 wt-56. The amount of alkaline agent required is a function of the amount of sulfohalide used under a), the stoichiometry being one equivalent of alkali per 1 mol sulfohalide, that is, if you use potassium or sodium hydroxide, you must use at least 1 mol per moles of sulfohalide. It is necessary to use an excess of alkaline agent in relation to the stoichiometric amount as defined. A molar excess of up to 10% and preferably between 1 and 5% is preferably used. One does not go outside the scope of the invention by using a large excess of the hydroxide, but the process is complicated by large amounts which must later be removed.
Man kan arbeide kontinuerlig eller diskontinuerlig og ved å tilsette arylsulfohalogenid, alkylamin og en vandig oppløs-ning av alkalisk middel i en hvilken som helst rekkefølge, delvis eller totalt. Den eneste betingelse som må overholdes er ikke å destruere arylsulfonylhalogenidet ved reaksjon med det alkaliske middel. For eksempel kan man bringe aryl-sulf onylhalogenidet i kontakt med alkylaminet og derefter tilsette det alkaliske middel. Man kan videre helle aryl-sulf onylhalogenidet i en omrørt blanding av alkalisk middel i vandig oppløsning og alkylaminet. Man benytter uttrykket "omrørt blanding" fordi alkalioppløsningen og alkylaminet vanligvis ikke er blandbare, idet man således omrører for å oppnå en slags ustabil emulsjon. I henhold til en annen variant kan man også helle arylsulfonylhalogenidet og den vandige alkalioppløsning i alkylaminet med en viss forsinkelse for alkalioppløsningen. Uttrykket "forsinkelse" gjelder antall mol alkalisk middel i forhold til antall mol arylsulfonylhalogenid. One can work continuously or discontinuously and by adding aryl sulfohalide, alkylamine and an aqueous solution of alkaline agent in any order, partially or totally. The only condition that must be observed is not to destroy the arylsulfonyl halide by reaction with the alkaline agent. For example, one can bring the arylsulfonyl halide into contact with the alkylamine and then add the alkaline agent. You can further pour the arylsulfonyl halide into a stirred mixture of alkaline agent in aqueous solution and the alkylamine. The term "stirred mixture" is used because the alkali solution and the alkylamine are usually not miscible, thus stirring to obtain a kind of unstable emulsion. According to another variant, one can also pour the arylsulfonyl halide and the aqueous alkali solution into the alkylamine with a certain delay for the alkali solution. The term "delay" refers to the number of moles of alkaline agent relative to the number of moles of arylsulfonyl halide.
Det er vesentlig ifølge oppfinnelsen å ha i kontakt et aryl-sulf onylhalogenid , et alkylamin, vann og et alkalisk middel, men man går ikke utenfor oppfinnelsens ramme ved å benytte vannfritt alkali og vann eller et vannfritt alkali og et alkylamin i vandig emulsjon. Man kan benytte et arylsulfonylhalogenid som sådant eller som en oppløsning i et opp-løsningsmiddel idet alkylaminet også kan være som sådant eller eventuelt i et oppløsningsmiddel som for eksempel toluen. It is essential according to the invention to have in contact an arylsulfonyl halide, an alkylamine, water and an alkaline agent, but one does not go outside the scope of the invention by using anhydrous alkali and water or an anhydrous alkali and an alkylamine in an aqueous emulsion. An arylsulfonyl halide can be used as such or as a solution in a solvent, the alkylamine can also be as such or optionally in a solvent such as toluene.
Selv om trinn a) kan skje ved en hvilken som helst temperatur og et hvilket som helst trykk forutsatt at produktene ikke dekomponeres, foretrekker man å arbeide ved omgiveles-temperatur eller nær denne og ved atmosfærisk trykk eller et trykk nær dette, slik at halogenidet er flytende og aminet også forblir flytende. Hvis disse betingelser er uforenelige kan man arbeide i en trykksone og ved en temperatur der halogenidet er flytende og aminet er gassformig. Disse betingelser er fortrinnsvis en temperatur under 150°C og et trykk under 5 bar relativt trykk. Although step a) can be carried out at any temperature and pressure provided that the products do not decompose, it is preferred to operate at or near ambient temperature and at or near atmospheric pressure so that the halide is liquid and the amine also remains liquid. If these conditions are incompatible, one can work in a pressure zone and at a temperature where the halide is liquid and the amine is gaseous. These conditions are preferably a temperature below 150°C and a pressure below 5 bar relative pressure.
Man arbeider fortrinnsvis ved atmosfærisk trykk og ved en temperatur nær omgivelsestemperatur, det vil si mellom 0 og 50° C. Varigheten for dette trinn a) er uten betydning men reaksjonen er øyeblikkelig og varigheten er fast ved de praktiske betingelser som er forbundet med apparatur og de mengder som manipuleres. One preferably works at atmospheric pressure and at a temperature close to ambient temperature, i.e. between 0 and 50° C. The duration of this step a) is unimportant but the reaction is instantaneous and the duration is fixed by the practical conditions associated with the apparatus and the quantities that are manipulated.
Reaksjonsvarigheten er vanligvis i størrelsesorden 15 minutter til noen timer. The reaction duration is usually in the order of 15 minutes to a few hours.
Denne kontakt er en i og for seg kjent operasjon og kan skje i en hvilken som helst apparatur som benyttes i den kjemiske industri og man benytter fortrinnsvis en omrørt apparatur. This contact is a known operation in and of itself and can take place in any apparatus used in the chemical industry and preferably a stirred apparatus is used.
Når alle reaktantene under trinn a) er bragt i kontakt opprettholdes fortrinnsvis reaksjonsmediet under omrøring ved en temperatur mellom 20 og 100°C og fortrinnsvis 40 og 70°C i et tidsrom som kan variere fra noen minutter til noen timer og som fortrinnsvis ligger mellom 1 og 3 timer. Man går derefter til en separering av reaksjonsmediet som oppnås ved slutten av trinn a) i en vandig fase og en organisk fase i det vesentlige inneholdende arylsulfonylalkylamid, alkylamin og noen prosent vann. Denne separering i to faser er en i og for seg kjent operasjon. When all the reactants under step a) have been brought into contact, the reaction medium is preferably maintained under stirring at a temperature between 20 and 100°C and preferably 40 and 70°C for a period of time which can vary from a few minutes to a few hours and which is preferably between 1 and 3 hours. The reaction medium which is obtained at the end of step a) is then separated into an aqueous phase and an organic phase essentially containing arylsulfonylalkylamide, alkylamine and a few percent water. This separation into two phases is an operation known in itself.
Trinn b) består i å fjerne vann og alkylamin fra den organiske fase ved destillasjon. Man kan arbeide under undertrykk eller ved noen bar forutsatt at man ikke over-skrider den temperatur ved hvilken den organiske fase begynner å brytes ned, eller er det begynner å danne seg farvede produkter eller dekomponeringsprodukter. Denne temperatur ligger vanligvis under 180°C.ø Fortrinnsvis arbeider man mellom 130 og 170° C. Man går ikke utenfor oppfinnelsen ramme ved å arbeide ved høyere temperatur men man risikerer å bryte ned produktene og det er videre enklere å arbeide ved lavere temperaturer. Step b) consists in removing water and alkylamine from the organic phase by distillation. You can work under negative pressure or at some bar provided that you do not exceed the temperature at which the organic phase begins to break down, or colored products or decomposition products begin to form. This temperature is usually below 180°C. Preferably you work between 130 and 170°C. You do not go outside the scope of the invention by working at a higher temperature, but you risk breaking down the products and it is also easier to work at lower temperatures.
Varigheten er uten viktighet, denne er fastlagt ved de praktiske betingelser forbundet med apparatur og den mengde og alkylamin som skal fjernes. The duration is unimportant, this is determined by the practical conditions associated with the equipment and the quantity and alkylamine to be removed.
Trinn b) kan på samme måte som de andre trinn ifølge oppfinnelsen gjennomføres kontinuerlig eller diskontinuerlig. Når man har fjernet vann og alkylamin oppnås en organisk rest i det vesentlige inneholdende det ønskede amid. Man gjennom-fører trinn c) ved destillasjon. Step b) can, in the same way as the other steps according to the invention, be carried out continuously or discontinuously. When water and alkylamine have been removed, an organic residue essentially containing the desired amide is obtained. Step c) is carried out by distillation.
I de følgende eksempler består termostabilitetsprøven i å holde arylsulfonylalkylamidet i 3 timer ved 250°C under nitrogen, farven ved slutten av prøven må være under 250 Hazen. Produktet er i dette tilfellet egnet som mykner. In the following examples, the thermostability test consists of keeping the arylsulfonyl alkylamide for 3 hours at 250°C under nitrogen, the color at the end of the test must be below 250 Hazen. In this case, the product is suitable as a softener.
Evis ikke annet er sagt arbeider man i en glassreaktor utstyrt med rørverk, termohylster, nitrogeninjektor, tilbakeløpskjøler og kjøleinnnretninger for vann- eller saltbad. Under destillasjonene i trinn b) og c) opprett-holdess et nitrogenteppe over produktene. Unless otherwise stated, one works in a glass reactor equipped with piping, thermowell, nitrogen injector, reflux cooler and cooling devices for water or salt baths. During the distillations in steps b) and c), a nitrogen blanket is maintained over the products.
Eksempel 1 Example 1
a) Man heller i løpet av 1 time og 30 minutter 3 mol benzensulfoklorid (C5H5SO2CI) i en blanding inneholdende a) Over the course of 1 hour and 30 minutes, 3 mol of benzene sulphochloride (C5H5SO2CI) is poured into a mixture containing
3,051 mol natriumhydroksyd i vandig 19,37 vekt-#-ig oppløsning og 3,3 mol n-butylamin (CH3CH2CH2CH2NE2). Reaktortemperaturen holdes ved 20°C. Derefter bringes temperaturen til mellom 60 og 65°C i løpet av 2 timer. Efter dekantering oppnås 675 g av en organisk fase inneholdende 3 X 0,9959 mol N,n-butylbenzensulfonamid (C6H5S02NHCH2CH2CH2CH3) (BBSA). 3.051 mol sodium hydroxide in aqueous 19.37 wt-#-ig solution and 3.3 mol n-butylamine (CH 3 CH 2 CH 2 CH 2 NE 2 ). The reactor temperature is kept at 20°C. The temperature is then brought to between 60 and 65°C within 2 hours. After decantation, 675 g of an organic phase containing 3 X 0.9959 mol of N,n-butylbenzenesulfonamide (C6H5SO2NHCH2CH2CH2CH3) (BBSA) are obtained.
b) Man destillerer denne organiske fase for å fjerne vann og n-butylamin og holder temperaturen derved fra 20 til 145°C b) This organic phase is distilled to remove water and n-butylamine and thereby keeps the temperature from 20 to 145°C
under et trykk fra 740 til 10 mmHg i en timeiunder a pressure from 740 to 10 mmHg for one hour
c) Man destillerer den oppnådde rest ved 0,5 mmHg og gjenvinner derved 96 % BBSA inneholdt i den organiske fase ved c) One distills the obtained residue at 0.5 mmHg and thereby recovers 96% of the BBSA contained in the organic phase at
slutten av trinn a). Den termiske prøve viser en farving på 50 Hazen. end of step a). The thermal test shows a coloring of 50 Hazen.
Eksempel 2 Example 2
Man arbeider som i eksempel 1 bortsett fra at under ihel-lingen av benzensulfonylklorid holdes temperaturen ved 50"C. Resultatene er identiske de som oppnås under eksempel 1. One works as in example 1 except that during the pouring of benzenesulfonyl chloride the temperature is kept at 50°C. The results are identical to those obtained in example 1.
Eksempel 3 Example 3
a) Man heller 0,6 mol benzensulfoklorid i 3,3 mol n-butylamin og holder reaktoren ved 50°C. Man heller derefter samtidig a) 0.6 mol of benzene sulphochloride is poured into 3.3 mol of n-butylamine and the reactor is kept at 50°C. You then pour at the same time
3,051 mol natriumhydroksyd i form av en vandig 19,37 vekt-56-ig oppløsning og 2,4 mol benzensulfonylklorid i løpet 1 time og 30 minutter idet reaktoren holdes ved 50° C. Man tilsetter 7 g vann for å spyle ihellingstrakten for NAOH. Man bringer derefter reaktoren til mellom 60 og 65°C i 3.051 mol of sodium hydroxide in the form of an aqueous 19.37 wt-56g solution and 2.4 mol of benzenesulfonyl chloride over the course of 1 hour and 30 minutes while the reactor is kept at 50° C. 7 g of water are added to flush the funnel for NAOH. The reactor is then brought to between 60 and 65°C i
løpet av 2 timer. Ef ter dekantering oppnås 669 g av en organisk fase inneholdende 3 X 0,9939 mol BBSA. within 2 hours. After decantation, 669 g of an organic phase containing 3 X 0.9939 mol BBSA are obtained.
b) Man destillerer som under eksempel 1. b) One distills as under example 1.
c) Man destillerer den oppnådde rest ved 0,5 mmHg og gjenvinner på denne måte 95 56 BBSA inneholdt i den c) The obtained residue is distilled at 0.5 mmHg and in this way the 95 56 BBSA contained in it is recovered
organiske fase ved slutten av trinn a). Den termiske prøve viser en farving på 50 Hazen. organic phase at the end of step a). The thermal test shows a coloring of 50 Hazen.
Eksempel 4 Example 4
Man arbeider som i eksempel 2 men benytter en reaktor av rustfritt stål der bunnen er av type 304 L og resten av type 316 L. Man oppnår identiske resultater. You work as in example 2, but use a stainless steel reactor where the bottom is of type 304 L and the rest of type 316 L. Identical results are obtained.
Eksempel 5 Example 5
a) Man heller i løpet av 30 minutter 3 mol benzensulfonylklorid i 3,3 mol n-butylamin idet reaktortemperaturen a) Over the course of 30 minutes, 3 mol of benzenesulfonyl chloride is poured into 3.3 mol of n-butylamine, with the reactor temperature
holdes ved 50°C. Derefter ihelles i løpet av 1 time og 30 minutter 3,15 mol 19,91 $-ig vandig natriumhydroksyd-oppløsning. kept at 50°C. Then, 3.15 mol of 19.91 µg aqueous sodium hydroxide solution are poured in during 1 hour and 30 minutes.
Innløpstrakten for natriumhydroksyd skylles med 13,5 g vann. Man bringer reaktoren til mellom 60 og 70°C i løpet av 2 timer. Efter dekantering oppnås 671,8 g av en organisk fase inneholdende 3 mol BBSA. The inlet funnel for sodium hydroxide is rinsed with 13.5 g of water. The reactor is brought to between 60 and 70°C within 2 hours. After decantation, 671.8 g of an organic phase containing 3 mol of BBSA are obtained.
b) Man destillerer vann og amin som under eksempel 1. Man fastslår at man har mistet 6,1 % av den under b) benyttede b) Water and amine are distilled as in example 1. It is determined that 6.1% of the amount used under b) has been lost
masse under denne destillasjon. mass during this distillation.
c) Man destillerer den oppnådde rest ved 0,5 mmHg og gjenvinner på denne måte 92 % BBSA inneholdt i den c) The obtained residue is distilled at 0.5 mmHg and in this way 92% of the BBSA contained in it is recovered
organiske fase ved slutten av trinn a). Den termiske prøve viser en farving på 175 Hazen. organic phase at the end of step a). The thermal sample shows a coloring of 175 Hazen.
Eksempel 6 Example 6
Man arbeider som i eksempel 3 bortsett fra at reaktoren holdes ved 20°C istedet for 50°C under de to ihellingstrinn for reaktantene. Efter dekantering oppnås 671,8 g av en organisk fase innholdende 3 X 0,998 mol BBSA. b) Man destillerer av vann og amin som under eksempel 1. Man fastslår at man har mistet 6,07 % vekt under destilla-sjonen . c) Man destillerer den oppnådde rest ved 0,5 mmHg og gjenvinner 3 fraksjoner tilsvarende forløp, masse og One works as in example 3, except that the reactor is kept at 20°C instead of 50°C during the two pouring steps for the reactants. After decantation, 671.8 g of an organic phase containing 3 X 0.998 mol BBSA is obtained. b) Water and amine are distilled as in example 1. It is determined that 6.07% weight has been lost during the distillation. c) One distills the obtained residue at 0.5 mmHg and recovers 3 fractions corresponding to course, mass and
efterløp av destillat der vekt-# er som følger: tailings of distillate where the weight # is as follows:
Fl = 4,9 * Fl = 4.9 *
F2 = 84,2 % F2 = 84.2%
F3 = 7,1 ^ F3 = 7.1 ^
Tilbake i ballongen forblir 3,8 % (beregnet på den i trinn c engasjerte vekt). Back in the balloon remains 3.8% (calculated on the weight engaged in step c).
Den termiske prøve på F2 viser en farving på under 50 Hazen og en farving på 100 Hazen for Fl + F2 + F3. The thermal test on F2 shows a staining of less than 50 Hazen and a staining of 100 Hazen for Fl + F2 + F3.
Eksempel 7 Example 7
Man arbeider som i eksmpel 2 bortsett fra at man benytter 3,75 mol n-butylamin. Man oppnår 702,6 g av en organisk fase inneholdende 3 X 0,9924 mol BBSA. Man oppnår identiske resultater. You work as in example 2 except that you use 3.75 mol of n-butylamine. 702.6 g of an organic phase containing 3 X 0.9924 mol BBSA is obtained. Identical results are obtained.
Eksempel 8 Example 8
Man arbeider som i eksempel 2 bortsett fra at man benytter 3,74 mol n-butylamin. Man oppnår 659,8 g av en organisk fase inneholdende 3 X 0,9915 mol BBSA. Man oppnår identiske resultater. You work as in example 2, except that you use 3.74 mol of n-butylamine. 659.8 g of an organic phase containing 3 X 0.9915 mol BBSA is obtained. Identical results are obtained.
Claims (2)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8803447A FR2628739B1 (en) | 1988-03-17 | 1988-03-17 | PROCESS FOR THE SYNTHESIS OF ARYLSULFONYLALKYLAMIDE |
Publications (4)
| Publication Number | Publication Date |
|---|---|
| NO890864D0 NO890864D0 (en) | 1989-03-01 |
| NO890864L NO890864L (en) | 1989-09-18 |
| NO170412B true NO170412B (en) | 1992-07-06 |
| NO170412C NO170412C (en) | 1992-10-14 |
Family
ID=9364346
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO890864A NO170412C (en) | 1988-03-17 | 1989-03-01 | PROCEDURE FOR THE PREPARATION OF ARYLSULPHONYLALKYLAMIDE |
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) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69116576T2 (en) * | 1991-09-05 | 1996-10-10 | Pharno Wedropharm Gmbh | AROMATIC SULPHONAMIDE DERIVATIVES, THEIR USE AS ENZYMINHIBITORS AND PHARMACEUTICAL COMPOSITIONS CONTAINING THESE COMPOUNDS |
| 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 |
Family Cites Families (2)
| 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 DE DE68912797T patent/DE68912797T2/en not_active Expired - Lifetime
- 1989-03-07 EP EP89400638A patent/EP0333557B1/en not_active Expired - Lifetime
- 1989-03-07 ES ES89400638T patent/ES2062055T3/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 DK DK198901279A patent/DK175638B1/en not_active IP Right Cessation
- 1989-03-16 PT PT90025A patent/PT90025B/en not_active IP Right Cessation
- 1989-03-16 IE IE85889A patent/IE63494B1/en not_active IP Right Cessation
- 1989-03-16 FI FI891256A patent/FI90763C/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 |
|---|---|
| DE68912797T2 (en) | 1994-06-01 |
| FI90763B (en) | 1993-12-15 |
| ATE101129T1 (en) | 1994-02-15 |
| DK127989D0 (en) | 1989-03-16 |
| FR2628739A1 (en) | 1989-09-22 |
| DK127989A (en) | 1989-09-18 |
| FI891256A (en) | 1989-09-18 |
| KR890014464A (en) | 1989-10-23 |
| PT90025B (en) | 1994-05-31 |
| DE68912797D1 (en) | 1994-03-17 |
| FI90763C (en) | 1994-03-25 |
| FR2628739B1 (en) | 1990-09-07 |
| NO890864D0 (en) | 1989-03-01 |
| DK175638B1 (en) | 2005-01-03 |
| CN1020600C (en) | 1993-05-12 |
| CN1037894A (en) | 1989-12-13 |
| EP0333557A3 (en) | 1990-10-17 |
| IE63494B1 (en) | 1995-05-03 |
| PT90025A (en) | 1989-11-10 |
| FI891256A0 (en) | 1989-03-16 |
| JPH0465063B2 (en) | 1992-10-16 |
| JPH024766A (en) | 1990-01-09 |
| IE890858L (en) | 1989-09-17 |
| EP0333557A2 (en) | 1989-09-20 |
| NO170412C (en) | 1992-10-14 |
| EP0333557B1 (en) | 1994-02-02 |
| ES2062055T3 (en) | 1994-12-16 |
| KR940010765B1 (en) | 1994-11-11 |
| NO890864L (en) | 1989-09-18 |
| CA1307295C (en) | 1992-09-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7169952B2 (en) | Process to prepare sulfonamides | |
| NO170412B (en) | PROCEDURE FOR THE PREPARATION OF ARYLSULPHONYLALKYLAMIDE | |
| KR100499981B1 (en) | Industrial process for the production of diphenyl sulfone compounds | |
| US4362893A (en) | Preparation of C-nitrosodiarylamines from diarylamines | |
| CA2174797C (en) | Cyanobenzenesulfenyl halide and process for preparation of 3-substituted benzisothiazole using the same | |
| EP0148145B1 (en) | Process for making nitrodiarylamines | |
| CA2025207C (en) | Process for the preparation of isothiazolinones | |
| JP4752300B2 (en) | Process for producing N-ethyl-N- (2-methylphenyl) -2-butenamide | |
| NO156610B (en) | Silanes. | |
| US5498798A (en) | 4-alkyl-3-chlorobenzenesulfinic acids, 4-alkyl-3-chlorobenzenesulfonylcarboxylic acids, 4-alkyl-3-chloroalkylsulfonylbenzenes and preparation thereof | |
| IE921523A1 (en) | Preparation of alkanesulfonamides | |
| US4996360A (en) | Preparation of arylsulfonyl (alkyl) amides | |
| SE405859B (en) | METHOD OF PRODUCING TERTIER PHOSPHINE OXIDES BY RELEASING FORMALDEHYDE AND HALOGEN WHEAT FROM DIHYDROXIMETHYLPHOSPHONIUM HALOGENIDES IN THE MELT | |
| US4978796A (en) | N-alkylpyrrolidone solvents for preparation of aromatic thiols | |
| CA2280442A1 (en) | Process for preparing benzyl carbazates | |
| EP0534347B1 (en) | A method for the preparation of N-ethylhydroxylamine hydrochloride | |
| JP2680906B2 (en) | Synthesis of N-chlorothio-sulfonamide | |
| JPH0687820A (en) | Method of preparing n-alkylsulfonamide | |
| KR20020056943A (en) | Process for the production of trifluoromethylacetophenones | |
| US7241924B2 (en) | Industrial process for the production of diphenyl sulfone compounds | |
| JPH10114729A (en) | Production of aminophenol | |
| JPH06321923A (en) | Production of 2-chlorobenzothiazole or 2-chloro- benzoxazole | |
| MXPA99007553A (en) | Procedure for obtaining bencilcarbaza | |
| JPS6144886A (en) | N-(2'-tetrahydrofuranyl)alkylbenzoic acid amide and manufacture | |
| JPH01213260A (en) | Production of bis(4-hydroxyphenyl)sulfide of high purity |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MK1K | Patent expired |