DK152751B - METHOD FOR PREPARING N-ALKYLED OR N, N-DIALKYLED 2,6-DINITROANILINES - Google Patents
METHOD FOR PREPARING N-ALKYLED OR N, N-DIALKYLED 2,6-DINITROANILINES Download PDFInfo
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- DK152751B DK152751B DK338974AA DK338974A DK152751B DK 152751 B DK152751 B DK 152751B DK 338974A A DK338974A A DK 338974AA DK 338974 A DK338974 A DK 338974A DK 152751 B DK152751 B DK 152751B
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- dimethylaniline
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B43/00—Formation or introduction of functional groups containing nitrogen
- C07B43/02—Formation or introduction of functional groups containing nitrogen of nitro or nitroso groups
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Description
iin
DK 152751BDK 152751B
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Den foreliggende opfindelse angår en særlig fremgangsmåde til fremstilling af N-alkylerede og Ν,Ν-dialkylerede 2,6-dinitroaniliner, der er anvendelige som herbicider.The present invention relates to a particular process for the preparation of N-alkylated and Ν, Ν-dialkylated 2,6-dinitroanilines useful as herbicides.
5 De N-alkylerede og Ν,Ν-dialkylerede 2,6-dinitroani- linforbindelser, som fremstilles ved den her omhandlede, særlige fremgangsmåde, har formlen R1 R2 10 °2Ννν^\^Ν0? | (I) zThe N-alkylated and Ν, Ν-dialkylated 2,6-dinitroanil compounds prepared by the particular process of the present invention have the formula R1 R2 10 ° 2Ννν | (I) z
YY
15 hvor Y betyder C-^-C^-alkyl, halogen eller CF^, Z betyder hydrogen, halogen, C^-C^-alkoxy eller C^-C^-alkyl, der eventuelt er monosubstitueret med halogen eller C.-C4-1 -L ‘i -alkoxy, R betyder C^-Cg-alkyl, (ligekædet eller fortrins- 20 vis forgrenet), C^-Cg-cycloalkyl, C^-C^-alkyl, der er substitueret med halogen eller C^-C^-alkoxy, og R2 betyder hydrogen eller en af grupperne R^.Wherein Y is C --C C alkyl, halogen or CF ^, Z represents hydrogen, halogen, C ^-C ^ alkoxy or C ^-C ^ alkyl optionally monosubstituted with halogen or C--C-. C 4-1 -L 'in -alkoxy, R means C 1 -C 6 alkyl, (straight or preferably branched), C 1 -C 6 cycloalkyl, C 1 -C 4 alkyl substituted by halogen or C 1 -C 2 alkoxy and R 2 represents hydrogen or one of the groups R 2.
Som eksempler på ligekædede eller forgrenede alkyl-substituenter skal nævnes methyl, ethyl, n-propyl, iso-pro-25 pyl, n-butyl, t-butyl, n-pentyl, n-hexyl, 2-pentyl, 3-pen-tyl, sek.butyl, 1-ethylpropyl og lignende.Examples of straight or branched chain alkyl substituents include methyl, ethyl, n-propyl, iso-propyl, n-butyl, t-butyl, n-pentyl, n-hexyl, 2-pentyl, 3-pentyl tyl, sec.butyl, 1-ethylpropyl and the like.
Som eksempler på cycloalkylgrupper skal nævnes cyclobutyl-, cyclopentyl- og cyclohexylgrupper.Examples of cycloalkyl groups include cyclobutyl, cyclopentyl and cyclohexyl groups.
Eksempler på halogensubstituenter er fluor-, chlor-, 30 brom- og iodgrupper.Examples of halogen substituents are fluorine, chlorine, bromine and iodine groups.
Ved fremgangsmåden ifølge den foreliggende opfindelse fremstilles forbindelser med formel I sikkert og effektivt ved nitrering af de tilsvarende N-alkylerede aniliner med formlen II 35 2In the process of the present invention, compounds of formula I are safely and efficiently prepared by nitration of the corresponding N-alkylated anilines of formula II
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R1 R2 if (11) 5 SjX'-zR1 R2 if (11) 5 SjX'-z
YY
1 2 hvor R , R , Y og Z har den ovenfor anførte betydning, og W og V er hydrogen eller nitro med det forbehold, at W og 10 V ikke samtidig kan være nitro, og den her omhandlede fremgangsmåde er ejendommelig ved, at der anvendes et tre--komponentnitreringsmiddel indeholdende H20, H^SO^ og HNOg og med en sammensætning inden for de grænser, som i tripeldiagrammet på tegningen er gengivet grafisk ved 15 det trapez (A) , som er defineret ved hjørnepunkterne 1) 60% HN03, 8% H2S04 og 32% H20, 2) 50% HN03, 35% H2S04 og 15% H20, 3) 2% HN03, 68% H2S04 og 30% H20, 4) 2% HN03, 20% H2S04 og 78% H20, 20 og i en mængde svarende til 2,2-5,0 mol salpetersyre pr.12 where R, R, Y and Z have the meaning given above and W and V are hydrogen or nitro with the proviso that W and 10 V cannot simultaneously be nitro, and the process of the invention is characterized in that: a three-component nitrating agent containing H 2 O, H 2 SO 2 and HNOg and having a composition within the limits shown in the triple diagram of the drawing is graphically represented by the trapezoid (A) defined at the corner points 1) 60% HN03 , 8% H2SO4 and 32% H2O, 2) 50% H2O3, 35% H2SO4 and 15% H2O, 3) 2% H2O3, 68% H2SO4 and 30% H2O, 4) 2% H2O3, 20% H2SO4 and 78% H2O , And in an amount corresponding to 2.2-5.0 moles of nitric acid per liter.
mol N-alkyleret anilin, når W og V begge er hydrogen, og 1,2-4,0 mol salpetersyre pr. mol N-alkyleret anilin, når W eller V er nitro, og en temperatur i området 15-70°C, og at reaktionsblandingen denitroseres, når en N-nitrosofor-25moles of N-alkylated aniline when W and V are both hydrogen, and 1.2-4.0 moles of nitric acid per liter. mole of N-alkylated aniline when W or V is nitro, and a temperature in the range of 15-70 ° C, and the reaction mixture is denitrified when an N-nitrosophore
bindelse med formlen IIIcompound of formula III
0=N R1 ^N^ (HI) 30 ^ Δ0 = N R1 ^ N ^ (HI) 30 ^ Δ
YY
hvor R^", Y og Z har den ovenfor anførte betydning, er dan-35 net i reaktionsblandingen.wherein R ^, Y and Z have the meaning given above are formed in the reaction mixture.
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Fremstillingen af forbindelser med formlen I har hidtil konventionelt været gennemført ved nucleofil ombytningsreaktion mellem et passende substitueret 2,6-dinitro--1-halogenbenzen og en passende substitueret amin. Ombyt-5 ningsreaktionen har hidtil været gennemført ved opvarmning af reaktanterne, fortrinsvis i et aromatisk opløsningsmiddel, til 50-150°C.The preparation of compounds of formula I has heretofore been conventionally carried out by nucleophilic exchange reaction between an appropriately substituted 2,6-dinitro-1-halogenobenzene and an appropriately substituted amine. The exchange reaction has so far been carried out by heating the reactants, preferably in an aromatic solvent, to 50-150 ° C.
Fremstillingen af N-alkylerede 2,6-dinitroaniliner med formlen I i højt udbytte ved nitrering af N-alkylerede 10 aniliner har ikke hidtil været beskrevet i den kendte teknik. Kendte metoder til fremstilling af 2,6-dinitro-terti-ære aniliner, hvor begge N-substituenter er halogenalkyl, involverer nitrering med i det mindste et fem-dobbelt overskud af salpetersyre, som ved reaktionens begyndelse er 15 til stede i en koncentration på 50-90% og i en sådan mængde > at der ved reaktionens afslutning forekommer en syrekoncentration på 50%, i nærværelse af en katalytisk mængde af et materiale, der danner salpetersyrling eller nitrition.The preparation of N-alkylated 2,6-dinitroanilines of formula I in high yield by nitration of N-alkylated 10 anilines has not heretofore been described in the prior art. Known methods for preparing 2,6-dinitro-tertiary anilines, where both N-substituents are haloalkyl, involve nitration with at least a five-fold excess of nitric acid present at the beginning of the reaction at a concentration of 50-90% and in such an amount that, at the end of the reaction, an acid concentration of 50% occurs in the presence of a catalytic amount of a nitric acid or nitrite formation material.
20 Heller ikke den i US-patentskrift nr. 3.654.363 beskrevne fremgangsmåde er operabel, idet forsøg på nitre-ring af N-alkylerede eller Ν,Ν-dialkylerede xylidiner eller p-toluidiner ikke fører til de ønskede, nitrerede produkter. Den anvendte nitreringsblanding (51,7% H2SO^, 25 41,6% HN03, 6,8% H20) ligger imidlertid, som også vist på tegningen, langt uden for den sammensætning (trapezet A), som anvendes ved fremgangsmåden ifølge opfindelsen.The process described in U.S. Pat. No. 3,654,363 is not operable either, since attempts at nitration of N-alkylated or Ν, dial-dialkylated xylidines or p-toluidines do not lead to the desired nitrated products. However, the nitriding mixture used (51.7% H 2 SO 4, 41.6% HNO 3, 6.8% H 2 O), as also shown in the drawing, is far beyond the composition (trapezoid A) used in the process of the invention.
Det samme gælder (som vist på tegningen) for den nitreringsblanding, som anvendes ifølge Beilstein's 30 Handbuch der Organischen Chemie, 4. udg., bind 12, side 1010 (1929), med sammensætningen 18,3% HNO3, 8,4% H^O^, 73,5% H20. Denne blanding muliggør nitrering af Ν,Ν-dialky leret p-toluidin, men ikke af N-alkyleret xylidin, og er altså ikke generelt operabel. Specielt må det for-35 ventes, at denne stærkt fortyndede nitreringsblanding ikke vil muliggøre den dinitrering, som gennemføres ved den her omhandlede fremgangsmåde.The same applies (as shown in the drawing) to the nitriding mixture used according to Beilstein's 30 Handbuch der Organischen Chemie, 4th ed., Vol. 12, page 1010 (1929), having the composition 18.3% HNO3, 8.4% H O, 73.5% H2 O. This mixture enables nitration of Ν, dial-dialkylated p-toluidine, but not of N-alkylated xylidine, and is thus not generally operable. In particular, it is to be expected that this highly diluted nitration mixture will not enable the dinitration carried out by the process of the present invention.
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Fra DE-fremlæggelsesskrift nr. 1.207.397 kendes en nitreringsblanding/ som ligger tættere på den ved fremgangsmåden ifølge opfindelsen anvendte end de fra ovennævnte litteratursteder kendte. Den falder dog stadig uden 5 for det ved trapezet A på tegningen definerede område, således som det også er vist på tegningen. Karakteristisk for den fra nævnte DE-fremlæggelsesskrift kendte teknik er, at der er tale om nitrering af nitroaniliner. Det fremgår ikke, at den beskrevne fremgangsmåde også er anvende-10 lig til nitrering af (di)alkylerede nitroaniliner, langt mindre til ikke i forvejen mononitrerede, eventuelt alkylerede aniliner.DE Patent Specification No. 1,207,397 discloses a nitriding mixture / which is closer to that used in the process of the invention than those known from the above-mentioned literature sites. However, it still falls outside of the area defined by trapezoid A in the drawing, as also shown in the drawing. Characteristic of the technique known from the DE disclosure specification is that the nitroanilines are nitrated. It is not apparent that the described process is also applicable to nitration of (di) alkylated nitroanilines, much less to non-already mononitrated, optionally alkylated anilines.
Nitrering af N-alkylerede sekundære aniliner i højt udbytte i 2- og 6-stillingen uden forudgående blokering af 15 et resterende hydrogenatom på nitrogenatomet, f.eks. ved acylering, ville derfor være overraskende på baggrund af den kendte teknik.Nitration of high yield N-alkylated secondary anilines at the 2- and 6-positions without prior blocking of a residual hydrogen atom on the nitrogen atom, e.g. by acylation, would therefore be surprising in view of the prior art.
De foretrukne tre-komponentnitreringsmidler til anvendelse ved den her omhandlede fremgangsmåde er på teg- 20 ningen vist som et trapez (B), som er defineret ved hjørnepunkterne 1) 45% HNOg, 19% H2S04 og 36% H20, 2) 45% HN03, 36% H2S04 og 19% H20, 3) 20% HN03, 52% H2SC>4 og 28% H20, 4) 20% HN03, 27% H2S04 og 53% H20. Hver af disse værdier repræsenterer en reel vægtprocent, hvilket 25 også gælder i forbindelse med trapez A.The preferred three-component nitrating agents for use in the present process are shown in the drawing as a trapezoid (B) defined at the corner points 1) 45% HNOg, 19% H 2 SO 4 and 36% H 2 O, 2) 45% HNO 3 , 36% H2SO4 and 19% H2O, 3) 20% H2O3, 52% H2SO4 and 28% H2O, 4) 20% H2O3, 27% H2SO4 and 53% H2O. Each of these values represents a real weight percent, which is also true for trapezoid A.
Det optimale molantal salpetersyre pr. mol af forbindelsen II afhænger af den forbindelse, der skal nitre-res, og sammensætningen af det anvendte nitreringsmiddel.The optimal mole number of nitric acid per mole of compound II depends on the compound to be nitrated and the composition of the nitrating agent used.
Således nitreres forbindelserne med formlen II, hvori W og 30 V er hydrogen, under anvendelse af 2,2-5,0 mol salpetersyre pr. mol N-alkyleret anilin. Inden for dette brede område foretrækkes området 2,5-3,5 mol salpetersyre. Når W eller V er nitro, anvendes 1,2-4,0 mol salpetersyre pr. mol N-alkyleret anilin. Inden for dette område foretræk- 35 .Thus, the compounds of formula II wherein W and 30 V are hydrogen are nitrated using 2.2-5.0 moles of nitric acid per liter. moles of N-alkylated aniline. Within this broad range, the range of 2.5-3.5 moles of nitric acid is preferred. When W or V is nitro, 1.2-4.0 moles of nitric acid are used. moles of N-alkylated aniline. Within this range, 35.
kes det mere snævre omrade 1,5-2,5 mol salpetersyre.the narrower range is 1.5-2.5 moles of nitric acid.
DK 152751 β 5DK 152751 β 5
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Molforholdet mellem svovlsyre og N-alkyleret anilin/ som anvendes ved de her omhandlede nitreringer/ kan fordelagtigt ligge i området 1,5:1 - 15,0:1, fortrinsvis 2,0:1 - 10,0:1. På vægtprocentbasis svarer disse svovlsyre-5 mængder til ca. 30-70%, idet det foretrukne område er ca. 35-65%.The molar ratio of sulfuric acid to N-alkylated aniline / used in the nitrates of the present invention may advantageously be in the range of 1.5: 1 - 15.0: 1, preferably 2.0: 1 - 10.0: 1. On a weight percent basis these sulfuric acid amounts to approx. 30-70%, with the preferred range being approx. 35-65%.
Det har vist sig, at den i nitreringsblandingen forekommende mængde vand er en vigtig faktor ved fremgangsmåden ifølge opfindelsen og står i forbindelse med den op-10 timale temperatur. Reaktionsblandinger, som indeholder højere procentmængder vand kræver almindeligvis højere reaktionstemperaturer. Vandmængden i udgangsnitreringsblandin-gen kan være 15-78 vægtprocent af nitreringsblandingen. Der skal anvendes en· tilstrækkelig høj temperatur til omdan-15 nelse af al N-alkyleret mononitroanilin til N-alkyleret 2,6-dinitroanilin. Det har vist sig, at forbindelser med formlen II kan nitreres ved temperaturer i området 15-70°C. Temperaturer under 15°C har tilbøjelighed til at hindre fuldstændig dinitrering og anvendes derfor ikke. Tempera-20 turer over 70°C anvendes ikke, fordi reaktionen i så fald bliver for vanskelig at kontrollere. Reaktionen er ekso-term, og der kræves sædvanligvis afkøling til at holde temperaturen under den øvre grænse og fortrinsvis inden for det optimale område. Den optimale temperatur varierer af-hængigt af den anvendte N-alkylerede udgangsanilin og sammensætningen af nitreringsmidlet. Den almindeligvis foretrukne reaktionstemperatur ligger i området 35-60°C.It has been found that the amount of water present in the nitrating mixture is an important factor in the process of the invention and is associated with the optimum temperature. Reaction mixtures containing higher percentages of water generally require higher reaction temperatures. The amount of water in the starting nitration mixture can be 15-78% by weight of the nitriding mixture. A sufficiently high temperature must be used to convert all N-alkylated mononitroaniline to N-alkylated 2,6-dinitroaniline. It has been found that compounds of formula II can be nitrated at temperatures in the range of 15-70 ° C. Temperatures below 15 ° C tend to prevent complete dinitration and are therefore not used. Temperatures above 70 ° C are not used because in this case the reaction becomes too difficult to control. The reaction is exothermic and cooling is usually required to keep the temperature below the upper limit and preferably within the optimum range. The optimum temperature varies depending on the N-alkylated starting aniline used and the composition of the nitrating agent. The generally preferred reaction temperature is in the range of 35-60 ° C.
Når der arbejdes i temperaturområdet 15-70°C (fortrinsvis 35-60°C), kan nitreringen med blandet syre let kon-30 trolleres. Det har vist sig, at nitrering med koncentreret salpetersyre skal foretages under 10°C, da der ellers vil forekomme en ukontrolleret reaktion. Som følge af den forholdsvis simple kontrol, der kræves til blandede syrer, kræves der meget mindre kølekapacitet til dette system.When operating in the temperature range of 15-70 ° C (preferably 35-60 ° C), the nitriding with mixed acid can be easily controlled. It has been found that nitration with concentrated nitric acid must be carried out below 10 ° C, as otherwise an uncontrolled reaction will occur. Due to the relatively simple control required for mixed acids, much less cooling capacity is required for this system.
Hvis der opstar kraftafbrydelse eller -mangel, kan nitre-ring med blandet syre let foretages, men med koncentreret 35 6If a power failure or power failure occurs, mixed acid nitration can be easily performed, but with concentrated 35 6
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salpetersyre ville der sandsynligvis forekomme en eksplosion.nitric acid would probably cause an explosion.
Et andet karakteristisk træk ved nitrering med blandet syre er det lille overskud (0,50-1,50 mol) salpetersy-5 re, der er nødvendigt til fuldstændig omsætning. Med koncentreret salpetersyre kræves der i det mindste 5-10 mol. Omkostningerne og den potentielle risiko ved anvendelse af koncentreret salpetersyre ville være meget højere end ved anvendelse af blandet syre, hvor genvinding af salpetersyre 10 ikke er essentiel for processens økonomi.Another characteristic feature of mixed acid nitration is the small excess (0.50-1.50 mole) of nitric acid needed for complete reaction. With concentrated nitric acid, at least 5-10 moles are required. The cost and potential risk of using concentrated nitric acid would be much higher than using mixed acid, where recovery of nitric acid 10 is not essential to the economy of the process.
Ved fremgangsmåden ifølge opfindelsen kan den N--alkylerede anilin omsættes med nitreringsopløsningen i form af en væske, et faststof eller opløst i et indifferent opløsningsmiddel, såsom ethylendichlorid, chloroform, car-15 bontetrachlorid eller nitromethan. Ved gennemførelse af fremgangsmåden ifølge opfindelsen har det vist sig fordelagtigt at anvende en opløsning af den N-alkylerede anilin i ethylendichlorid, hvor forholdet mellem ethylendichlorid og forbindelsen II ligger i området ca. 3,0:1 -20 ca. 0,5:1, fortrinsvis 0,75:1, ml/g.In the process of the invention, the N - alkylated aniline can be reacted with the nitriding solution in the form of a liquid, solid or dissolved in an inert solvent such as ethylene dichloride, chloroform, carbon tetrachloride or nitromethane. In carrying out the process of the invention, it has been found advantageous to use a solution of the N-alkylated aniline in ethylene dichloride, wherein the ratio of ethylene dichloride to compound II is in the range of approx. 3.0: 1 -20 approx. 0.5: 1, preferably 0.75: 1, ml / g.
Tilsætningsmetoden er ikke en kritisk faktor. Nit-reringsmidlet kan sættes til udgangsforbindelsen II, eller forbindelsen II kan sættes til nitreringsmidlet afhængigt af den specielle situation.The method of addition is not a critical factor. The nitrating agent may be added to the starting compound II or the compound II may be added to the nitrating agent depending on the particular situation.
25 Produktet I kan isoleres efter endt nitreringsreak- tion, hvis der ikke er dannet nitrosoforbindelser. Reaktionens afslutning bestemmes ved konventionelle metoder såsom tyndtlagschromatografi eller ved NMR-spektroskopi. Det har imidlertid også vist sig, at det i tilfælde af forbin-30 delser med formlen II, hvor R er hydrogen, er yderst fordelagtigt at behandle reaktionsblandingen fra nitreringstrin-net yderligere med et denitroseringsmiddel, fortrinsvis en kombination af koncentreret saltsyre og sulfaminsyre. Herved forøges produktudbyttet med omtrentlig det forekommende 35 N-nitrosobiprodukt.The product I can be isolated after the nitration reaction is completed if no nitroso compounds are formed. The completion of the reaction is determined by conventional methods such as thin layer chromatography or by NMR spectroscopy. However, it has also been found that in the case of compounds of formula II wherein R is hydrogen, it is extremely advantageous to further treat the reaction mixture from the nitration step with a denitrifying agent, preferably a combination of concentrated hydrochloric acid and sulfamic acid. Hereby, the product yield is increased by approximately the occurring 35 N-nitrosoby product.
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Det har vist sig, at molforholdet mellem saltsyre og sulfaminsyre og tilstedeværende N-nitrosoforbindelse i hvert tilfælde skal være mindst 1:1. Molforholdet mellem saltsyre og N-nitrosoforbindelse skal fortrinsvis være 5 5:1-1,5:1. Molforholdet mellem sulfaminsyre og N-nitroso forbindelse er fortrinsvis 2:1. Temperaturen ved denitro-seringstrinnet kan ligge i området 20-100°C, fortrinsvis 80-100°C. Mens denitroseringstrinnet kan gennemføres ved atmosfæretryk, foretrækkes det at gennemføre dette trin 10 under tryk for at bevare saltsyren.It has been found that in each case the molar ratio of hydrochloric acid to sulfamic acid and the N-nitroso compound present must be at least 1: 1. The molar ratio of hydrochloric acid to N-nitroso compound should preferably be 5: 1-1.5: 1. The molar ratio of sulfamic acid to N-nitroso compound is preferably 2: 1. The temperature of the denitrification step may be in the range of 20-100 ° C, preferably 80-100 ° C. While the denitrification step can be carried out at atmospheric pressure, it is preferred to perform this step 10 under pressure to retain the hydrochloric acid.
Der kan også anvendes andre denitroseringsmidler såsom saltsyre og ferrochlorid ved den her omhandlede fremgangsmåde. Det foretrækkes imidlertid at anvende saltsyre og sulfaminsyre.Other denitrifying agents such as hydrochloric acid and ferrochloride may also be used in the process of this invention. However, it is preferred to use hydrochloric acid and sulfamic acid.
15 Den ifølge opfindelsen foretrukne metode gennemfø res sædvanligvis som en batch-proces. En kontinuert proces kan imidlertid også anvendes.The preferred method of the invention is usually carried out as a batch process. However, a continuous process can also be used.
Som eksempler på forbindelser, som let kan fremstilles ved den her omhandlede fremgangsmåde, skal nævnes: N-20 -(isopropyl)-3,4-dimethyl-2,6-dinitroanilin, N-n-propyl- -3,4-dimethyl-2,6-dinitroanilin, N-cyclohexyl-3,4-dimethyl--2,6-dinitroanilin, N-(2-butyl)-3,4-dimethyl-2,6-dinitroanilin, N-cyclopentyl-3,4-dimethyl-2,6-dinitroanilin, N--cyclobutyl-3,4-dimethyl-2,6-dinitroanilin, N-(2-butyl)-25 -3-isopropyl-4-methyl-2,6-dinitroanilin, N-(2-butyl)-4- -tert.buty1-2,6-dinitroanilin, N-(2-amyl)-3-sek.butyl-4--methyl-2,6-dinitroanilin, N-isopropyl-3,4-diethyl-2,6--dinitroanilin, N-3-pentyl-3,4-diethyl-2,6-dinitroanilin, N-(2-butyl)-3-chlor-4-methyl-2,6-dinitroanilin, N-(2-bu-30 tyl)-3-methoxy-4-methyl-2,6-dinitroanilin og N-(l-ethyl-propyl)-3,4-dimethyl-2,6-dinitroanilin.Examples of compounds that can be readily prepared by the process of this invention are: N-20 - (isopropyl) -3,4-dimethyl-2,6-dinitroaniline, Nn-propyl--3,4-dimethyl-2 , 6-dinitroaniline, N-cyclohexyl-3,4-dimethyl-2,6-dinitroaniline, N- (2-butyl) -3,4-dimethyl-2,6-dinitroaniline, N-cyclopentyl-3,4- dimethyl-2,6-dinitroaniline, N - cyclobutyl-3,4-dimethyl-2,6-dinitroaniline, N- (2-butyl) -25 -3-isopropyl-4-methyl-2,6-dinitroaniline, N - (2-butyl) -4- tert -butyl-2,6-dinitroaniline, N- (2-amyl) -3-sec-butyl-4-methyl-2,6-dinitroaniline, N-isopropyl-3 , 4-diethyl-2,6-dinitroaniline, N-3-pentyl-3,4-diethyl-2,6-dinitroaniline, N- (2-butyl) -3-chloro-4-methyl-2,6- dinitroaniline, N- (2-butyl) -3-methoxy-4-methyl-2,6-dinitroaniline and N- (1-ethyl-propyl) -3,4-dimethyl-2,6-dinitroaniline.
Som eksempler på forbindelser, hvor Y er CF^, skal nævnes: N-n-propyl-3~methyl-2,6-dinitro-4-(trifluormethyl)- -anilin, N-sek.butyl-3-methyl-2,6-dinitro-4-(trifluor-35 methyl)-anilin, 3-methyl-2,6-dinitro-N-3-pentyl-4-(tri-Examples of compounds where Y is CF 2 are: Nn-propyl-3-methyl-2,6-dinitro-4- (trifluoromethyl) -aniline, N-sec-butyl-3-methyl-2.6 -dinitro-4- (trifluoro-methyl) -aniline, 3-methyl-2,6-dinitro-N-3-pentyl-4- (tri
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Som eksempler på 2,6-dinitro-tertiære aniliner, der kan fremstilles ved fremgangsmåden ifølge opfindelsen, skal nævnes: 5 N-methyl-N-(2-chlorethyl)-3,4-dimethyl-2,6-dinitroanilin, N,N-di-(n-propy1)-a,a,a-trifluor-2,6-dinitro-p-toluidin, N-ethyl-N-butyl-a,a,a-trifluor-2,6-dinitro-p-toluidin, N,N-di-(n-propyl)-3,4-dimethy1-2,6-dinitroanilin, N,N-di- methy1-3,4-dimethyl-2,6-dinitroanilin, N,N-diethyl-3,4- -dimethyl-2,6-dinitroanilin, N-ethyl-N-butyl-3,4-dimethy1- -2,6-dinitroanilin, N-methyl-N-cyclohexyl-3,4-dimethyl- -2,6-dinitroanilin, N,N-diethyl-4-chlor-3-methyl-2,6-di- nitroanilin, N,N-dibutyl-3,4-dimethy1-2,6-dinitroanilin, N,N-di-(n-propyl)-4-chlor-3-methy1-2,6-dinitroanilin, N,N-15 -di-(n-propyl)-3-chlor-4-methy1-2/6-dinitroanilin/ N/N- -dimethyl-3-methyl-4-chlor-2,6-dinitroanilin, N-methyl-N- -ethyl-3,4-dimethy1-2,6-dinitroanilin, N,N-dimethyl-3,4-4 4 4 -dimethyl-α ,a ,a -trifluor-2,6-dinitroanilin, N,N-di- ethyl-3-chlo'r-4-methy 1-2,6-dinitroanilin, N,N-di-(n-pro-20 444 pyl)-3,4-dimethyl-a ,α ,a -trifluor-2,6-dinitroanilin, N,N-di-(n-propyl)-3-methoxy-4-methy1-2,6-dinitroanilin, 4 4 4 Ν,Ν-diethy1-3,4-dimethyl-a ,a ,a -trifluor-2,6-dinitroanilin, N,N-diethyl-3-methoxy-3-methyl-2,6-dinitroanilin, N,N-di-(n-propyl)-3-ethoxy-4-methy1-2,6-dinitroanilin, N,N-25 -di- (n-propyl) -3-butoxy-4-i-methy 1-2,6-dinitroanilin, N,N--bis-(2-chlorethyl)-3,4-dimethyl-2,6-dinitroanilin og N,N--bis-(2-chlorethyl)-4-methyl-2,6-dinitroanilin.Examples of 2,6-dinitro-tertiary anilines which can be prepared by the process of the invention are: N-methyl-N- (2-chloroethyl) -3,4-dimethyl-2,6-dinitroaniline, N, N-di- (n-propyl) -α, α, α-trifluoro-2,6-dinitro-p-toluidine, N-ethyl-N-butyl-α, α, α-trifluoro-2,6-dinitro p-toluidine, N, N-di- (n-propyl) -3,4-dimethyl-2,6-dinitroaniline, N, N-dimethyl-3,4-dimethyl-2,6-dinitroaniline, N, N-diethyl-3,4- -dimethyl-2,6-dinitroaniline, N-ethyl-N-butyl-3,4-dimethyl-2,6-dinitroaniline, N-methyl-N-cyclohexyl-3,4- dimethyl-2,6-dinitroaniline, N, N-diethyl-4-chloro-3-methyl-2,6-dinitroaniline, N, N-dibutyl-3,4-dimethyl-2,6-dinitroaniline, N , N-di- (n-propyl) -4-chloro-3-methyl-2,6-dinitroaniline, N, N-15-di- (n-propyl) -3-chloro-4-methyl-2/6 -dinitroaniline / N / N- -dimethyl-3-methyl-4-chloro-2,6-dinitroaniline, N-methyl-N- -ethyl-3,4-dimethyl-2,6-dinitroaniline, N, N-dimethyl -3,4-4,4 4-dimethyl-α, α, α-trifluoro-2,6-dinitroaniline, N, N-diethyl-3-chloro-4-methyl 1-2,6-dinitroaniline, N, N-di- (n-pro-444 arrow) -3.4 -dimethyl-α, α, α-trifluoro-2,6-dinitroaniline, N, N-di- (n-propyl) -3-methoxy-4-methyl-2,6-dinitroaniline, 4 4 4 Ν, Ν- diethyl -3,4-dimethyl-α, α, α-trifluoro-2,6-dinitroaniline, N, N-diethyl-3-methoxy-3-methyl-2,6-dinitroaniline, N, N-di- (n -propyl) -3-ethoxy-4-methyl-2,6-dinitroaniline, N, N-25-di- (n-propyl) -3-butoxy-4-i-methyl 1-2,6-dinitroaniline, N , N - bis- (2-chloroethyl) -3,4-dimethyl-2,6-dinitroaniline and N, N - bis- (2-chloroethyl) -4-methyl-2,6-dinitroaniline.
Nogle af de foretrukne metoder til fremstilling af 30 foretrukne dinitroaniliner beskrives i det følgende.Some of the preferred methods for preparing 30 preferred dinitroanilines are described below.
Ved en foretrukken metode til nitrering af N-(l--ethylpropyl)-3,4-dimethylanilin har det anvendte nitre-ringsraiddel et vandindhold på ca. 35-53 vægt-%, og anilinforbindelsen omsættes i en sådan mængde, at der fås et mol-35 forhold mellem salpetersyre og anilin på ca. 3,25:1 og et molforhold mellem svovlsyre og anilinforbindelse på ca. 2,25:1.In a preferred method for the nitration of N- (1- ethylpropyl) -3,4-dimethylaniline, the nitrating agent used has a water content of approx. 35-53% by weight, and the aniline compound is reacted in an amount to give a molar ratio of nitric acid to aniline of approx. 3.25: 1 and a mole ratio of sulfuric acid to aniline compound of approx. 2.25: 1st
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Omsætningen gennemføres under opretholdelse af en reaktions-temperatur på ca. 35-70°C. Reaktanterne blandes i et tidsrum på ca. 2 timer, idet reaktionsblandingens temperatur holdes i området ca. 35-70°C i ca. 1 time efter sammenblan-5 dingen. Derpå gennemføres denitrosering ved at sætte saltsyre og sulfaminsyre til blandingen, idet temperaturen holdes på 70-100°C i 1-6 timer, hvorefter det dannede N-(l--ethylpropyl)-2,6-dinitro-3,4-dimethylanilinprodukt udvindes .The reaction is carried out while maintaining a reaction temperature of approx. 35-70 ° C. The reactants are mixed for a period of approx. 2 hours keeping the temperature of the reaction mixture in the range of approx. 35-70 ° C for approx. 1 hour after mixing. Then, denitrosisation is carried out by adding hydrochloric acid and sulfamic acid to the mixture, keeping the temperature at 70-100 ° C for 1-6 hours, after which the N- (1-ethylpropyl) -2,6-dinitro-3,4-dimethylaniline product formed is extracted.
1Q Fremgangsmåden gennemføres fortrinsvis i ét ethylen- dichloridopløsningsmiddel, yderligere karakteriseret ved, at opløsningsmiddelforholdet udtrykt i ml ethylendichlorid pr. gram N-(l-ethylpropyl)-3,4-dimethylanilin ligger i området ca. 3,0:1,0 - 0,5:1,0, fortrinsvis fra ca. 0,75:1,0.The process is preferably carried out in one ethylene dichloride solvent, further characterized in that the solvent ratio expressed in ml of ethylene dichloride per ml. grams of N- (1-ethylpropyl) -3,4-dimethylaniline are in the range of approx. 3.0: 1.0 - 0.5: 1.0, preferably from ca. 0.75: 1.0.
15 Ved en foretrukken metode til 'nitrering af N-(2- -butyl)-3,4-dimethylanilin har nitreringsmidlet er vandindhold på ca. 40-53 vægt-%, og anilinforbindelsen omsættes i en sådan mængde, at der fås et molforhold mellem salpetersyre og anilinforbindelse på ca. 3,25:1 og et molfor-2o hold mellem svovlsyre og anilinforbindelse på ca. 2,25:1. Reaktionsblandingens temperatur holdes på ca. 50-70°C, mens reaktanterne blandes deri i et tidsrum på ca. 2 timer, hvorefter reaktionsblandingens temperatur holdes på ca.In a preferred method of nitrating N- (2-butyl) -3,4-dimethylaniline, the nitrating agent has a water content of approx. 40-53% by weight, and the aniline compound is reacted in an amount such that a molar ratio of nitric acid to aniline compound of approx. 3.25: 1 and a molo-2O ratio of sulfuric acid to aniline compound of approx. 2.25: 1st The temperature of the reaction mixture is kept at approx. 50-70 ° C while reacting the reactants therein for a period of approx. 2 hours, after which the temperature of the reaction mixture is kept at approx.
50-70°C i ca. 1 time efter endt sammenblanding. Denitrose-25 ring af blandingen gennemføres ved at tilsætte saltsyre og sulfaminsyre, idet temperaturen holdes på 70-100°C i 1-6 timer, hvorefter det derved dannede N-(2-butyl)-2,6-dinitro--3,4-dimethylanilinprodukt udvindes.50-70 ° C for approx. 1 hour after mixing is complete. Denitrification of the mixture is carried out by adding hydrochloric acid and sulfamic acid, keeping the temperature at 70-100 ° C for 1-6 hours, after which the N- (2-butyl) -2,6-dinitro-3 thus formed 4-dimethylaniline product is recovered.
Fremgangsmåden gennemføres fortrinsvis i et ethy-30 lendichloridopløsningsmiddel yderligere karakteriseret ved, at opløsningsmiddelforholdet udtrykt i ml ethylendichlorid pr. gram N-(2-butyl)-3,4-dimethylanilin ligger i området ca. 3,0:1,0 - ca. 0,5:1,0, fortrinsvis fra 0,75 til 1,0.The process is preferably carried out in an ethylene dichloride solvent further characterized in that the solvent ratio expressed in ml of ethylene dichloride per ml. grams of N- (2-butyl) -3,4-dimethylaniline are in the range of approx. 3.0: 1.0 - approx. 0.5: 1.0, preferably from 0.75 to 1.0.
Fremgangsmåden ifølge opfindelsen belyses nærmere 35 i de efterfølgende eksempler 1-38. I hvert tilfælde er de anførte dele og procenter på vægtbasis, medmindre andet er oThe process of the invention is elucidated in detail in the following Examples 1-38. In each case, the parts and percentages stated are by weight unless otherwise specified
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10 anført. I alle tilfælde isoleres slutproduktet ved tyndt-lagschromatografi og identificeres ved ultraviolet absorptions spektroskop! .10. In all cases, the final product is isolated by thin-layer chromatography and identified by ultraviolet absorption spectroscope! .
I nedenstående tabel I er angivet sammensætningen _ af de i eksemplerne 1-15, 25-31 og 33-38 anvendte nitre-5 ringsblandinger. Ved sammenligning med tegningen vil det ses, at de alle falder inden for de af trapezerne A og B afgrænsede områder.Table I below shows the composition of the nitriding mixtures used in Examples 1-15, 25-31 and 33-38. By comparison with the drawing, it will be seen that they all fall within the boundaries defined by trapezes A and B.
10 TABEL ITABLE I
Sammensætning af nitreringsblandinger _(vægtprocent)_Composition of nitrating mixtures _ (% by weight) _
Eksempel HNO3 ^2—4 —2— 1 31,93 34,37 33,71 2 35,84 37,16 27,0 1 o 3 33,82 35,07 31,0 4 31,61 32,79 35,6 5 29,26 30,34 40,4 6 ' 36,19 40,21 23,6 20 7 32,35 35,95 31,7 8 40,45 37,75 21,8 9 36,20 33,80 30,0 10 33,72 31,48 34,8 11 16,79 34,81 48,4 25 12 34,50 48,80 16,7 13 37,48 40,82 21,7 14 32,12 34,58 43,3 15 24,51 26,39 49,1 30 35 11Example HNO 3 → 2-4 -2-1 31.93 34.37 33.71 2 35.84 37.16 27.0 1 o 3 33.82 35.07 31.0 4 31.61 32.79 35, 6 5 29.26 30.34 40.4 6 '36.19 40.21 23.6 20 7 32.35 35.95 31.7 8 40.45 37.75 21.8 9 36.20 33.80 30.0 10 33.72 31.48 34.8 11 16.79 34.81 48.4 25 12 34.50 48.80 16.7 13 37.48 40.82 21.7 14 32.12 34, 58 43.3 15 24.51 26.39 49.1 30 35 11
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TABEL I (fortsat)TABLE I (continued)
Eksempel HNO-, §2—4 -2- 25 29,32 30,39 40/29 26 44/66 34,74 20,6 5 27 34,30 38,10 27,6 28 32,35 35,95 31,7 29 29,47 31,73 38,8 30 31,88 34,32 43,8 31 24,51 26,39 49,1 10 33 35,35 38,11 26,54 34 31,70 36,39 31,91 35 13,89 80,04 6,07 36 13,89 80,04 6,07 37 13,89 80,04 6,07 15 38 35,73 38,52 25,75 EKSEMPEL 1Example HNO, §2-4-2 25 29.32 30.39 40/29 26 44/66 34.74 20.6 5 27 34.30 38.10 27.6 28 32.35 35.95 31 , 7 29 29.47 31.73 38.8 30 31.88 34.32 43.8 31 24.51 26.39 49.1 10 33 35.35 38.11 26.54 34 31.70 36.39 31.91 35 13.89 80.04 6.07 36 13.89 80.04 6.07 37 13.89 80.04 6.07 15 38 35.73 38.52 25.75 Example 1
Nltrering af N- (1-ethylpropyl) -3,4-dimethylanilinNitration of N- (1-ethylpropyl) -3,4-dimethylaniline
Til en opløsning af blandet syre, fremstillet ved 20 tilsætning af 145,2 g (1,625 mol) 70,5%'s salpetersyre og 116,6 g (1,125 mol) 94,5%'s svovlsyre til 58,8 g vand, sættes i løbet af 2 timer ved 35°C en opløsning af 101,0 g (0,5 mol) 94,6%'s N-(1-ethylpropyl)-3,4-dimethylanilin i 143,5 ml ethylendichlorid. Reaktionstemperaturen holdes 25 på 35°C i 1 time, hvorpå den vandige fase adskilles. Den organiske fase vaskes successivt med 300 ml 5%'s natriumhydroxidopløsning og 300 ml vand. Den organiske opløsning tørres over vandfrit magnesiumsulfat, filtreres og koncentreres ved 70°C i vakuum, hvorved der fås 141,5 g råprodukt 30 indeholdende 117 g (82,6%) N-(1-ethylpropyl)-3,4-dimethyl--2,6-dinitroanilin og 14,2 g (10,0%) N-nitroso-N-(1-ethylpropyl ) -3 ,4-dimethy 1-2, 6-dinitroanilin. Det samlede udbytte af den ønskede 2,6-dinitroanilin er 92,6%.To a solution of mixed acid prepared by the addition of 145.2 g (1.625 mole) of 70.5% nitric acid and 116.6 g (1.125 mole) of 94.5% sulfuric acid to 58.8 g of water, a solution of 101.0 g (0.5 mole) of 94.6% N- (1-ethylpropyl) -3,4-dimethylaniline in 143.5 ml of ethylene dichloride is added over 2 hours at 35 ° C. The reaction temperature is maintained at 35 ° C for 1 hour, after which the aqueous phase is separated. The organic phase is washed successively with 300 ml of 5% sodium hydroxide solution and 300 ml of water. The organic solution is dried over anhydrous magnesium sulfate, filtered and concentrated at 70 ° C in vacuo to give 141.5 g of crude product containing 117 g (82.6%) of N- (1-ethylpropyl) -3,4-dimethyl-1 -2,6-dinitroaniline and 14.2 g (10.0%) of N-nitroso-N- (1-ethylpropyl) -3,4-dimethyl 1-2,6-dinitroaniline. The total yield of the desired 2,6-dinitroaniline is 92.6%.
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o EKSEMPEL 2-10 I disse eksempler er anført de resultater, som opnås ved nitrering af N-(1-ethylpropyl)-3,4-dimethylanilin, ved 35°C i reaktionsblandinger indeholdende salpetersyre 5 og svovlsyre i samme molforhold til udgangsmaterialet, men forskellige vandindhold. I alle tilfælde er de generelle reaktionsbetingelser de samme som' de i eksempel 1 anvendte.EXAMPLES 2-10 In these examples, the results obtained by nitration of N- (1-ethylpropyl) -3,4-dimethylaniline are listed at 35 ° C in reaction mixtures containing nitric acid 5 and sulfuric acid in the same molar ratio to the starting material, but different water content. In all cases, the general reaction conditions are the same as those used in Example 1.
I nogle tilfælde tilsættes udgangsmaterialet uden opløsningsmiddel, og reaktionsblandingerne ekstraheres derpå med 10 toluen eller xylen gg oparbejdes på sædvanlig måde. De fremkomne resultater er anført i den efterfølgende tabel II.In some cases, the starting material is added without solvent and the reaction mixtures are then extracted with 10 toluene or xylene gg worked up in the usual manner. The results obtained are set out in the following Table II.
15 20 25 30 3515 20 25 30 35
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14 EKSEMPEL· 11-1314 EXAMPLE · 11-13
Nitrering af N-(1-ethylpropyl)-3,4-dimethylanilinNitration of N- (1-ethylpropyl) -3,4-dimethylaniline
Af de efterfølgende eksempler fremgår det, at der ved nitrering af N-(l-ethylpropyl)-3,4-dimethylanilin ved 5 20-25°C i blandinger indeholdende hhv. 16,7%, 21,7% og 48,7% vand fås lave udbytter af både N-(1-ethylpropyl)--3,4-dimethyl-2,6-dinitroanilin og N-nitroso-N-(1-ethylpropyl )-3,4-dimethyl-2,6-dinitroanilin. Dette viser, at molforhold og vandindhold har indflydelse på udbytte og 10 produktsammensætning.The following examples show that by nitration of N- (1-ethylpropyl) -3,4-dimethylaniline at 5-20-25 ° C in mixtures containing respectively. 16.7%, 21.7% and 48.7% water, low yields of both N- (1-ethylpropyl) -3,4-dimethyl-2,6-dinitroaniline and N-nitroso-N- (1- ethyl propyl) -3,4-dimethyl-2,6-dinitroaniline. This shows that the mole ratio and water content have an influence on yield and product composition.
Den anvendte generelle fremgangsmåde er den samme som den i eksempel 1 anvendte. Der anvendes de i tabel III anførte mængder, idet der gås ud fra 4,86 g N-(1-ethylpropyl ) -3 , 4-dimethylanilin i 15 ml ethylendichlorid. I al-15 le tilfælde er tiIsætningstiden 2 timer og den efterfølgende reaktionstid 1 time.The general procedure used is the same as that used in Example 1. The amounts listed in Table III are used, starting from 4.86 g of N- (1-ethylpropyl) -3,4-dimethylaniline in 15 ml of ethylene dichloride. In all cases, the addition time is 2 hours and the subsequent reaction time is 1 hour.
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16 EKSEMPEL 14-1516 EXAMPLES 14-15
De i den følgende tabel IV anførte eksempler 14 og 15 viser indflydelsen af højere temperaturer og vandindhold på produktsammensætning og totaludbytte. De anvendte 5 generelle betingelser er de samme som de i eksempel 1 anvendte, med de angivne undtagelser. Forbindelserne er angivet i mol og gram.Examples 14 and 15 listed in the following Table IV show the influence of higher temperatures and water content on product composition and overall yield. The 5 general conditions used are the same as those used in Example 1, with the exceptions stated. The compounds are given in moles and grams.
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Eksempel 16Example 16
Denitrosering af råt nitreringsprodukt fra N-(1--ethylpropyl)-3,4-dimethylanilin Til en rå nitreringsopløsning bestående af 1550 g 5 2,6-dinitro-N-(1-ethylpropyl)-3,4-dimethylanilin og 340 g 2.6- dinitro-N-nitroso-N-(1-ethylpropyl)-3,4-dimethylanilin i 3700 ml ethylendichlorid sættes 212 g sulfaminsyre og 2850 ml 37,7%'s saltsyre. Blandingen tilbagesvales ved 80°C i 6 timer, der tilsættes 2 liter vand, og den vandige fase iso- 10 leres. Den vandige fase ekstraheres med 500 ml ethylendichlorid, og de organiske faser kombineres. De kombinerede organiske faser vaskes med 3 liter vand, den vandige fase isoleres, og ethylendichloridet fjernes under vakuum ved 68°C, hvorved der fås 1915 g produkt indeholdende 1820 g 2,6-dini-15 tro-N-(1-ethylpropyl)-3,4-dimethylanilin og mindre end 0,1% 2.6- dinitro-N-nitroso-N-(1-ethylpropyl)-3,4-dimethylanilin.Denitrification of Nitrating Crude Nitrating Product from N- (1-ethylpropyl) -3,4-dimethylaniline 2,6-dinitro-N-nitroso-N- (1-ethylpropyl) -3,4-dimethylaniline in 3700 ml of ethylene dichloride is added 212 g of sulfamic acid and 2850 ml of 37.7% hydrochloric acid. The mixture is refluxed at 80 ° C for 6 hours, 2 liters of water are added and the aqueous phase is isolated. The aqueous phase is extracted with 500 ml of ethylene dichloride and the organic phases are combined. The combined organic phases are washed with 3 liters of water, the aqueous phase is isolated and the ethylene dichloride removed in vacuo at 68 ° C to give 1915 g of product containing 1820 g of 2,6-dinitro-N- (1-ethylpropyl) -3,4-dimethylaniline and less than 0.1% of 2,6-dinitro-N-nitroso-N- (1-ethylpropyl) -3,4-dimethylaniline.
Eksempel 17-24Examples 17-24
De i den efterfølgende tabel V anførte eksempler på 20 denitrosering af rå nitreringsprodukter fra nitrering af N--(1-ethylpropyl)-3,4-dimethylanilin gennemføres under anvendelse af de i eksempel 16 beskrevne generelle betingelser.The examples of denitrification of crude nitration products from nitration of N - (1-ethylpropyl) -3,4-dimethylaniline in the following Table V are carried out using the general conditions described in Example 16.
De i tabel V anførte molforhold udtrykker molantal reagens pr. mol N-nitrosobiprodukt. I de fleste tilfælde gennemføres 25 reaktionen i autoklav.The molar ratios listed in Table V express the molar number of reagents per ml. mole of N-nitrosoby product. In most cases, the reaction is carried out in autoclave.
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Eksempel 25Example 25
Nitrering af N-(2-butvl)-3/4-dimethylanilinNitration of N- (2-butyl) -3 / 4-dimethylaniline
Til en opløsning af blandet syre, fremstillet ved tilsætning af 134,1 g (1,50 mol) 70,5%'s salpetersyre og 5 101,1 g (1,00 mol) 96,9.%'s svovlsyre til 87,2 g vand ved 50-55°^ sættes i løbet af 2 timer en opløsning af 92,3 g 95,9%'s N-(2-butyl)-3,4-dimethylanilin i 66,5 ml ethylendi-chlorid. Reaktionen holdes ved 55°C i yderligere 1 time,, hvorpå den vandige fase isoleres.To a solution of mixed acid prepared by adding 134.1 g (1.50 mole) of 70.5% nitric acid and 101.1 g (1.00 mole) of 96.9% sulfuric acid to 87 2 g of water at 50-55 ° over a solution of 92.3 g of 95.9% N- (2-butyl) -3,4-dimethylaniline in 66.5 ml of ethylene dichloride are added over 2 hours. . The reaction is kept at 55 ° C for a further 1 hour, after which the aqueous phase is isolated.
10 Den organiske fase vaskes successivt med 500 ml 5S's vandig natriumhydroxidopløsning og 500 ml vand. Den organiske fase tørres derpå over vandfrit magnesiumsulfat, filtreres og koncentreres ved 70°C under vakuum, hvorved der fås 130,0 g råprodukt indeholdende 100 g (75,5%'s udbytte) 2,6-15 -dinitro-N-(2-butyl)-3,4-dimethylanilin og 22,0 g (14,9%'s udbytte) 2,6-dinitro-N-nitroso-N-(2-butyl)-3,4-dimethylanilin. Det samlede udbytte af det ønskede 2,6-dinitroanilin-produkt er 90,4%.The organic phase is washed successively with 500 ml of 5S aqueous sodium hydroxide solution and 500 ml of water. The organic phase is then dried over anhydrous magnesium sulfate, filtered and concentrated at 70 ° C under vacuum to give 130.0 g of crude product containing 100 g (75.5% yield) of 2,6-15-dinitro-N- ( 2-butyl) -3,4-dimethylaniline and 22.0 g (14.9% yield) of 2,6-dinitro-N-nitroso-N- (2-butyl) -3,4-dimethylaniline. The total yield of the desired 2,6-dinitroaniline product is 90.4%.
20 Eksempel 26-28Example 26-28
De i tabel VI anførte eksempler på nitrering af N--(2-butyl)-3,4-dimethylanilin illustrerer indflydelsen af ni-treringsblandingens vandindhold på produktsammensætningen.The examples of nitration of N - (2-butyl) -3,4-dimethylaniline listed in Table VI illustrate the influence of the water content of the nitration mixture on the product composition.
Det vil sige, at anvendelsen af en blandet syre med større 25 vandindhold og lavere molforhold salpetersyre fører til procentvis lavere indhold af N-nitrosobiproduktforbindeIse.That is, the use of a mixed acid with greater water content and lower mole ratio of nitric acid leads to a percentage lower content of N-nitrosoby product compound.
I alle tilfælde anvendes den i eksempel 1 beskrevne generelle fremgangsmåde ved 35°C, idet der som udgangsmateriale tilsættes en opløsning af 4,53 g N-(2-butyl)-3,4-dime-30 thylanilin i 15 ml ethylendichlorid i løbet af 2 timer, hvorpå reaktionen holdes ved 35°C i yderligere 1 time.In all cases, the general procedure described in Example 1 is used at 35 ° C, adding as a starting material a solution of 4.53 g of N- (2-butyl) -3,4-dimethylaniline in 15 ml of ethylene dichloride over for 2 hours, then the reaction is kept at 35 ° C for an additional 1 hour.
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Eksempel 29-31Examples 29-31
De i tabel VII anførte eksempler illustrerer variationen af totaludbytte og produktsammensætning som følge af modifikationer i reaktionsblandingens vandindhold og tempe-5 ratur ved nitreringen af N-(2-butyl)-3,4-dimethylanilin.The examples given in Table VII illustrate the variation of total yield and product composition due to modifications in the water content and temperature of the reaction mixture in the nitration of N- (2-butyl) -3,4-dimethylaniline.
Disse resultater indikerer en foretrukken temperatur på ca.These results indicate a preferred temperature of approx.
50°C og et vandindhold på ca. 40% til nitrering af N-(2-butyl) -3, 4-dimethylanilin med den anførte støkiometri.50 ° C and a water content of approx. 40% for nitration of N- (2-butyl) -3,4-dimethylaniline with the stated stoichiometry.
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2424
Eksempel 32Example 32
Denitrosering af råt nitreringsprodukt fra N-(2- -butyl)-3,4-dimethylanilinDenitrification of Nitrating (N-(2-Butyl) -3,4-Dimethylaniline) Raw Nitrating Product
Til en opløsning af 30 g råt nitreringsprodukt inde-5 holdende 20,2 g 2,6-dinitro-N-(2-butyl)-3,4-dimethylanilin og 6,84 g 2,6-dinitro-N-nitroso-N-(2-butyl.)-3,4-dimethylanilin i 15 ml ethylendichlorid sættes 3,94 g sulfaminsyre og 9,84 g 37,6%'s saltsyre. Blandingen omrøres og opvarmes i 6 timer under tryk ved 80°C, hvorefter der tilsættes 20 ml vand, og 10 blandingens pH-værdi indstilles på 9-11 ved forsigtig tilsætning af en 50%'s vandig natriumhydroxidopløsning. Faserne henstilles til adskillelse, og det vandige lag fjernes.To a solution of 30 g of crude nitrating product containing 20.2 g of 2,6-dinitro-N- (2-butyl) -3,4-dimethylaniline and 6.84 g of 2,6-dinitro-N-nitroso N- (2-butyl.) - 3,4-dimethylaniline in 15 ml of ethylene dichloride is added 3.94 g of sulfamic acid and 9.84 g of 37.6% hydrochloric acid. The mixture is stirred and heated for 6 hours under pressure at 80 ° C, then 20 ml of water is added and the pH of the mixture is adjusted to 9-11 by careful addition of a 50% aqueous sodium hydroxide solution. The phases are allowed to separate and the aqueous layer is removed.
Det organiske lag vaskes med 20 ml vand, tørres over vandfrit magnesiumsulfat, filtreres og koncentreres under vakuum ved 15 70°C, hvorved der fås 28,2 g indeholdende 24,6 g (93%'s ud bytte) 2,6-dinitro-N-(2-butyl)-3,4-dimethylanilin og mindre end 0,1% 2,6-dinitro-N-nitroso-N-(2-butyl)-3,4-dimethylanilin.The organic layer is washed with 20 ml of water, dried over anhydrous magnesium sulfate, filtered and concentrated in vacuo at 70 ° C to give 28.2 g containing 24.6 g (93% yield) of 2,6-dinitro -N- (2-butyl) -3,4-dimethylaniline and less than 0.1% 2,6-dinitro-N-nitroso-N- (2-butyl) -3,4-dimethylaniline.
20 Eksempel 33Example 33
Der fremstilles en syreopløsning ved sammenblanding af 1,83 g vand, 6,83 g (0,0675 mol) 96,9%'s svovlsyre og 8,71 g (0,0975 mol) 70,5%'s salpetersyre. Til denne opløsning sættes en opløsning af 5,93 g (0,03 mol) N-2-butyl-3-chlor-4-25 -methylanilin i 4 g ethylendichlorid i løbet af 75 minutter ved 35-40°C. Blandingen opvarmes i 2,25 timer ved 40-45°C og i yderligere 0,75 time ved 55°C. Blandingen fortyndes med ethylendichlorid og vaskes med en fortyndet vandig natriumhydroxidopløsning til pH 10-11, vaskes med frisk vand, tør-30 res over magnesiumsulfat og filtreres. Efter filtrering fås 7,8 g olie. Ved tyndtlagschromatografi viser det sig, at denne olie indeholder én hovedkomponent og 3 bikomponenter.An acid solution is prepared by mixing 1.83 g of water, 6.83 g (0.0675 mole) of 96.9% sulfuric acid and 8.71 g (0.0975 mole) of 70.5% nitric acid. To this solution is added a solution of 5.93 g (0.03 mole) of N-2-butyl-3-chloro-4-25-methylaniline in 4 g of ethylene dichloride over 75 minutes at 35-40 ° C. The mixture is heated for 2.25 hours at 40-45 ° C and for another 0.75 hours at 55 ° C. The mixture is diluted with ethylene dichloride and washed with a dilute aqueous sodium hydroxide solution to pH 10-11, washed with fresh water, dried over magnesium sulfate and filtered. After filtration, 7.8 g of oil are obtained. By thin-layer chromatography, it appears that this oil contains one major component and three bicomponents.
Olien opløses i 20 ml ethylendichlorid, og opløsningen tilsættes 13 ml koncentreret saltsyre og 1 g sulfaminsyre.The oil is dissolved in 20 ml of ethylene dichloride and the solution is added with 13 ml of concentrated hydrochloric acid and 1 g of sulfamic acid.
35 Blandingen opvarmes under tilbagesvaling i 7 timer, og undersøgelse af en prøve ved tyndtlagschromatografi viser, at énThe mixture is heated at reflux for 7 hours and examination of a sample by thin layer chromatography shows that one
DK 152751 BDK 152751 B
OISLAND
25 af bikomponenterne i den oprindelige olie er forsvundet. Blandingen afkøles, og det vandige lag kastes bort. Det organiske lag vaskes med vand, tørres over magnesiumsulfat, filtreres og koncentreres, hvorved der fås 5,7 g olie. Den-5 ne olies hovedkomponent isoleres i ren tilstand ved væske-chromatografi og viser sig ved protonmagnetisk resonansspek-troskopi at være den ønskede N-(2-butyl)-2,6-dinitro-3—chlor--p-toluidin.Twenty-five of the bicomponents of the original oil have disappeared. The mixture is cooled and the aqueous layer is discarded. The organic layer is washed with water, dried over magnesium sulfate, filtered and concentrated to give 5.7 g of oil. The principal component of this oil is isolated in pure state by liquid chromatography and proves, by proton magnetic resonance spectroscopy, the desired N- (2-butyl) -2,6-dinitro-3-chloro-p-toluidine.
10 Eksempel 34Example 34
Der fremstilles en syreopløsning ved blanding af 2,55 g vand, 6,91 g 95,7%'s svovlsyre og 8,71 g 70,5%'s salpetersyre. Til denne opløsning sættes i løbet af ma. 2 timer en opløsning af 6,3 g N-2-butyl-4-tert.butylanilin i 19 ml 15 ethylendichlorid ved 33-37°C. Reaktionsblandingen omrøres i 1,5 time ved 40-45°C og i 1 time ved 50°C. Der tilsættes y-derligere 1,93 g 95,3%*s svovlsyre, og blandingen .omrøres i endnu 0,5 time ved 50°C. Undersøgelser viser, at .der ikke resterer uomsat N-2-butyl-4-tert.butvlanilin ellermononitro-20 derivat deraf i reaktionsblandingen. Blandingen alkøles, den organiske fase isoleres og vaskes med fortyndet vandig natriumhydroxidopløsning og derpå med vand. Til den organiske fase sættes derpå 13 ml koncentreret saltsyre og 1,0 g sul-faminsyre. Blandingen opvarmes under tilbagesvaling i 4 ti-25 mer, hvorpå den afkøles, og syrelaget kastes bort. Den organiske fase vaskes med vand og koncentreres, hvorved der fås 14,4 g olie. Denne olie anbringes på en søjle imed sili-cagel og elueres med toluen. Den hurtigst bevægende komponent ekstraheres fra silicagelen under anvendelse af irasthylenchlo-30 rid. Ekstrakten koncentreres, hvorved der fås 3,4 -g (mere end 38% af det teoretiske) gult faststof, som viser slig at være N-2-butyl-2,6-dinitro-4-tert.butylanilin.An acid solution is prepared by mixing 2.55 g of water, 6.91 g of 95.7% sulfuric acid and 8.71 g of 70.5% nitric acid. Add to this solution over the course of ma. 2 hours a solution of 6.3 g of N-2-butyl-4-tert-butylaniline in 19 ml of ethylene dichloride at 33-37 ° C. The reaction mixture is stirred for 1.5 hours at 40-45 ° C and for 1 hour at 50 ° C. An additional 1.93 g of 95.3% sulfuric acid is added and the mixture is stirred for another 0.5 hour at 50 ° C. Studies show that unreacted N-2-butyl-4-tert-butylaniline or mononitonitro derivative thereof remains in the reaction mixture. The mixture is cooled, the organic phase is isolated and washed with dilute aqueous sodium hydroxide solution and then with water. To the organic phase is then added 13 ml of concentrated hydrochloric acid and 1.0 g of sulphamic acid. The mixture is heated at reflux for 4 hours, then cooled and the acid layer discarded. The organic phase is washed with water and concentrated to give 14.4 g of oil. This oil is placed on a column against silica gel and eluted with toluene. The fastest moving component is extracted from the silica gel using irastylene chloride. The extract is concentrated to give 3.4-g (more than 38% of theory) yellow solid, which is shown to be N-2-butyl-2,6-dinitro-4-tert-butylaniline.
35 2635 26
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DK 152751BDK 152751B
Eksempel 35Example 35
Fremstilling af N-sec.butyl-2-nitro-3,4-dimethyl- anllin og N-sec.butyl-6-nitro-3,4-dimethylanilin 5,3 g (0,03 mol) N-sec.butyl-3,4-dimethylanilin op-5 løses i 10 ml dichlorethan og behandles forsigtigt med blandede syrer (6 ml koncentreret svovlsyre og 2,7 g koncentreret salpetersyre) ved 15-25°C. Efter endt tilsætning hældes blandingen ud i vand. Det organiske lag isoleres og renses ved søjlechromatografi på silicagel under anvendelse af he-10 xan som elueringsmiddel. Den forbindelse, der først elueres, er N-sec.butyl-2-nitro-3,4-dimethylanilin og identificeres ved sine NMR-og IR-spektre. Den anden forbindelse, der elueres, er N-sec.butyl-6-nitro-3,4-dimethylanilin, som også karakteriseres ved sit NMR-spektrum.Preparation of N-sec.butyl-2-nitro-3,4-dimethylanoline and N-sec.butyl-6-nitro-3,4-dimethylaniline 5.3 g (0.03 mole) of N-sec.butyl Dissolve -3,4-dimethylaniline in 10 ml of dichloroethane and treat gently with mixed acids (6 ml of concentrated sulfuric acid and 2.7 g of concentrated nitric acid) at 15-25 ° C. After the addition is complete, the mixture is poured into water. The organic layer is isolated and purified by column chromatography on silica gel using hexane as eluent. The first eluted compound is N-sec.butyl-2-nitro-3,4-dimethylaniline and is identified by its NMR and IR spectra. The other compound eluted is N-sec.butyl-6-nitro-3,4-dimethylaniline, which is also characterized by its NMR spectrum.
1515
Eksempel 36Example 36
Fremstilling af N-(1-ethylpropyl)-2,6-dinitro-3,4- -dimethylanilin N-(1-Ethylpropyl)-2-nitro-3,4-dimethylanilin frem-20 stilles analogt med den i eksempel 35 beskrevne fremgangsmåde, idet der i stedet for N-sec.buty1-3,4-dimethylanilin anvendes N-(1-ethylpropyl)-3,4-dimethylanilin. Den ønskede 2,6-dinitroforbindelse fremstilles i godt udbytte og renhed ved nitrering af 2-nitroforbindelsen under anvendelse af den 25 i eksempel 1 beskrevne metode.Preparation of N- (1-ethylpropyl) -2,6-dinitro-3,4- -dimethylaniline N- (1-Ethylpropyl) -2-nitro-3,4-dimethylaniline is prepared analogously to that described in Example 35 method, using N- (1-ethylpropyl) -3,4-dimethylaniline instead of N-sec.buty-3,4-dimethylaniline. The desired 2,6-dinitro compound is prepared in good yield and purity by nitration of the 2-nitro compound using the method described in Example 1.
Eksempel 37Example 37
Ved en metode svarende til den i eksempel 35 beskrevne fremstilles N-(1-ethylpropyl)-6-nitro-3,4-dimethylanilin, 30 idet der i stedet for N-sec.butyl-3,4-dimethylanilin anvendes N-(1-ethylpropyl)-3,4-dimethylanilin. 6-Nitroforbindelsen omdannes til N-(1-ethylpropyl)-2,6-dinitro-3,4-dimethylanilin under anvendelse af den i eksempel 1 beskrevne fremgangsmåde.By a method similar to that described in Example 35, N- (1-ethylpropyl) -6-nitro-3,4-dimethylaniline is prepared, using N- (N-sec.butyl-3,4-dimethylaniline instead). 1-ethyl-propyl) -3,4-dimethylaniline. The 6-nitro compound is converted to N- (1-ethylpropyl) -2,6-dinitro-3,4-dimethylaniline using the procedure described in Example 1.
3535
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2727
Eksempel 38Example 38
Der fremstilles en blandet syreopløsning ved tilsætning af 5/79 g (0,056 mol) 95,3%'s svovlsyre og 7,27 g (0,081 mol) 70,5%'s salpetersyre til 1,27 g vand. Til de 5 blandede syrer sættes under omrøring en opløsning af 6,15 g (0,025 mol) N,N-bis-(2-chlorethyl)-3,4-dimethylaniilin i 15 ml ethylendichlorid. Tilsætningen foretages i løbet af 90 minutter ved en temperatur på 35-40°C. Efter endt tilsætning omrøres blandingen i yderligere 2 timer ved 30-40°C. Det øv-10 re lag vaskes med portioner på hver 10 ml fortyndet natriumhydroxidopløsning og vand i den nævnte rækkefølge.. Den organiske opløsning tørres over vandfrit magnesiumsulfat og chromatograferes derefter på søjle af silicagel. fted elue-ring med benzen isoleres 3,73 g (44,5%) gult faststof, som 15 ved NMR-spektroskopi viser sig at være N,N-bis-(2-chlorethyl)--2,6-dinitro-3,4-dimethylanilin.A mixed acid solution is prepared by adding 5/79 g (0.056 mole) of 95.3% sulfuric acid and 7.27 g (0.081 mole) of 70.5% nitric acid to 1.27 g of water. To the 5 mixed acids is added, with stirring, a solution of 6.15 g (0.025 mol) of N, N-bis- (2-chloroethyl) -3,4-dimethylaniline in 15 ml of ethylene dichloride. The addition is made over 90 minutes at a temperature of 35-40 ° C. After the addition is complete, the mixture is stirred for an additional 2 hours at 30-40 ° C. The upper layer is washed with portions of each 10 ml of dilute sodium hydroxide solution and water in that order. The organic solution is dried over anhydrous magnesium sulfate and then chromatographed on a column of silica gel. eluted with benzene, 3.73 g (44.5%) of yellow solid is isolated, which, by NMR spectroscopy, is found to be N, N-bis- (2-chloroethyl) -2,6-dinitro-3 , 4-dimethylaniline.
20 25 30 3520 25 30 35
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