CS272750B1 - Method of 2-ethyl-6-methyl-n-/1-methoxy-2-propyl/chlorethanilide - Google Patents
Method of 2-ethyl-6-methyl-n-/1-methoxy-2-propyl/chlorethanilide Download PDFInfo
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(57) Risásnie sa týká spceobu pripravy herbicidu motolachloru nydrogenačnou al~. kyláciou 2-etyl-G-metyl-anilínu metcxypropanónora v prostredi l-mstcxy~2-propanolu ako rozpúšťadla/ v přítomnosti platinového hydrogonačného katalyzátora a kyseliny cblůrovodikovej ako protonového katalyzátora.v množstva 6;1 až 27% bmotnostných v přepočte na použitý 2-ětyl-6-metylanilín a reakcíou výsledného produktu, ktorý po izolócii použitého platinového hydrogenačnóho katalyzátora, vody, rozpúáťadla a nezreagovaného metoxypropanónu pozgetáva z 2-styl-S-metyl-N-/l'-metoxy-2^-propyl/anil£nu a z 2-etyl-S-motýl N-/1. -metoxy-2'-propyl/anilín hydrochloridů/ s chloracetylchloridom v molárnom pomere lsl,'l až 2 v prostredi inertného organického rozpúáťadla vybraného zo skupiny zahrňujúcej alifatické; cykloalifatické a aromatické uhlovodíky. Kyselina chlorovodíková ako protonový katalyzátor sa. róožo použiť v plynnej forms alebo absorbovaná v l-metoxy-2-přopanole, v zmosi l-metcxy-2-propanolu a 2-etyl-6-motylanilinu alebo v zmesi l-motoxy-2-propanoju, 2-etyl-G-ijotylanilinu a motoxypropanonu. Co^ť chlorovodíka vzniknutó£ ho v stupni chloracetylácie sa može vracať do procesu hydrpgonačnoj alkylácio 2-etyl-S-metylanilinu’metoxypropanonom ako protonový katalyzátor.(57) Risásnia concerns the method for the preparation of motolachlor herbicide by nitrogensation α1. by acylation of 2-ethyl-G-methyl-aniline with methoxypropanone in 1-methoxy-2-propanol as solvent / in the presence of a platinum hydrogenation catalyst and hydrochloric acid as a proton catalyst in an amount of 6% to 27% by weight based on the 2- Methyl-6-methylaniline and reacting the resulting product, which after isolation of the used platinum hydrogenation catalyst, water, solvent and unreacted methoxypropanone, zombies from 2-style-S-methyl-N- (1'-methoxy-2H-propyl) aniline and 2-ethyl-S-butterfly N- / 1. -methoxy-2'-propyl (aniline hydrochloride) with chloroacetyl chloride in a molar ratio of ls1, 1 to 2 in an inert organic solvent selected from the group consisting of aliphatic; cycloaliphatic and aromatic hydrocarbons. Hydrochloric acid as the proton catalyst is. can be used in gaseous forms or absorbed in 1-methoxy-2-propanol, in a mixture of 1-methoxy-2-propanol and 2-ethyl-6-motylaniline or in a mixture of 1-methoxy-2-propanoyl, 2-ethyl-G- ijotylaniline and motoxypropanone. The hydrogen chloride produced in the chloroacetylation stage can be recycled to the process by 2-ethyl-5-methylaniline-methoxypropanone hydronic acid alkylation as a proton catalyst.
CS 272760CS 272760
272 750 (11) (13) Bl (51) Int. C1.S 272 750 (11) (13) Bl (52) Int. C1. WITH
C 07 C 233/07OJ C 07 C 233/07
CS 272 750 BlCS 272 750 Bl
Vynález se týká sposobu přípravy 2-etyl-6-mstyl-N-/lř-mstoxy-2/,-propyl/ chlóracatanilidu, ktorý je známy ako herbicid pod všeobecným názvtfm metolachlor.The present invention relates to a process for the preparation of 2-ethyl-6-Mstyle N / L R -mstoxy-2 /, propyl / chlóracatanilidu, known as the generic názvtfm herbicide metolachlor.
□o známe, že 2-atyl-6-metyl-N-/r-metoxy-2‘-prcpyl/ chlóracetanilid je možné připravit reakciou 2-etyl-6-mstyl-N-/l'-motoxy-ž'-propyI/ anilinu s chloracetylačným činidlem ako je anhydrid alebo halogenid kyseliny chlóroctovej /CS 169·841/.We know that 2-ethyl-6-methyl-N- (1'-methoxy-2'-propyl) chloroacetanilide can be prepared by reaction of 2-ethyl-6-methyl-N- (1'-hydroxy-1'-propyl) (aniline with a chloroacetylating agent such as chloroacetic anhydride or halide) (CS 169 · 841).
Východiskový 2-etyl-6-metyl-N-/l’-metoxy-2'-prt>pyl/ anilín je možné připravit kondenzéciou 2-etyl~6-m3tylanilínu s metoxypropanónom a súčasnou alebo následnou hydrogenácíou vznikajúceho 2-etyl-S-metyl-N-/l’-metoxy-2,-propylidón/anilínu v prostředí rozpúštadla v přítomnosti platinového /US 4200 451, DE 2 328 340/, paládlového /CS 163 841/ alebo mecinatochroraitého /PV 9575-87/ hydrogenačného katalyzátora a v přítomnosti protonového katalyzátora ako je kyselina sírová /OE 2 328 340, US 4200 451, CS 169 841, PV· 393-89/, kyselina octová /CS 219 855/; 2-metyl-5-etylanilin hydrochlorid/ 2-metyI-6-etylanilin semihydrogénsulfát/ 2-metyl-6-etylanilin trihydrogénfoafát, 2-metyl-6-etyl-N-/lz-mstoxy-2r-propyl/ anilín hydrochlorid,’ 2-metyl-6-etyl-N-/I/-mstoxy-2*-propyl/ anilin dihydrogénsulfát, 2-metyl-6-etyl-N-/l'-metoxy-2''-propyl/ anilin di-/trihydrogénfosfát /PV 4257-88/, kyselina trihydrogénfosforečná alebo kyselina chlorovodíková použitá v množstve 0,5 až 6/0 % hmotnostných vzhíadom na použitý 2-etyI-5-metylanilín /AO 4265-88, AO 4258-88/ AO 4259-88/ AO 393-89/, 2 uvedených protonových katalyzátorov sa z prevádzkového hladiska javi nejvýhodnejšim kyselina chlůrovodiková/ ktorá v3ak v mnažstvéch 0/5 až 5/0 % hmotnostných vzhíadom na použitý 2-etyl-S-nietylanilin nezabezpečuje žiadtfci a technicky možný stupeň konverzie, vyžaduje si dlhšiu reakčnú dobu, připadne použitie vačSich množstviev platinového hydrogenačného katalyzátora. Nevyhnutné je přitom dbát, aby použitý protonový katalyzátor bol vysoko čistý z toho dovodu/ aby sa do hydrogenačného procesu.nevrtášali inhibitory hydrogenačnýoh katalyzátorov/ najma iony tažkých kovov. Po skončeni hydrogenácie je čaet výsledného 2-etyl-6-metyl-N-/l,-metoxy-2r-propyl/ anilinu naviazaná na pritomnú kyselinu vo formě kvartérnej soli; pričom eú známe viaceré epfcsoby jej využitia, připadne izolácie. V AO 4259-88 a AO 393-89 sa navrhuje recyklácia izolovanej kvartérnej soli ako protonového katalyzátora do ňalšleho cyklu hydrogenačnoj alkylácie. Významnou nevýhodou týchto risšení je/ že v dSsledku korózíe technologického zariadenia dochádza postupné k zvýšeniu koncentrácia tažkých kovov v prctonovom katalyzátore, čo vedle k zniženiu aktivity hydrogenačného katalyzátora v 3al5om cykle a k jeho vyššej spotřebo alebo k predlžovaniu reakčnej doby. Pódia DE 2 328 340 je možné postupovat tak, žo sa přidáním trietylaminu k reakčnej zmesi kyselina použitá ako protonový katalyzátor vyzráža vo formě trietylamóniovej soli, ktorá sa odfiltruje. Nevýhoda tohoto riešenia spočiva v tom, že trietylamin.je nevyhnutné regenerovat pomocou vodného roztoku anorganickej bázy, čo je spojené e tvorbou odpadových vad so značným obsahom solí. Sposob podía US 4 200 451 spočiva v tom, že výsledná raakčná zmes z hydrogsnačnej alkylácie sa priamo destiluje za vákua bez izolácie kyseliny sírovej použitej vo funkcii protonového katalyzátora. Nadostatkom tohoto postupu je, žs kyselina sírová posobí pri teplote destilácie ako sulfonačné činidlo, čim dochádza k stratám na žíadanom produkte. Postupovat je možné napokon i tak, že po zahuštěni výslsdnej reakčnej zmesi z hydroganačnaj alkylácie a po oddělení hornej vrstvy.reakčného produktu podía AO 4259-88 alobo AO 393-89 sa 3podná vrstva kvartérnej soli už Sálej nespracováva ale sa zlikviduje napr. spálením, čo však tiež zvyšuje prevádzková náklady a znižuje stupeň využitia východiskových surovin.The starting 2-ethyl-6-methyl-N- (1'-methoxy-2'-propyl) aniline can be prepared by condensation of 2-ethyl-6-m 3 -tylaniline with methoxypropanone and simultaneous or subsequent hydrogenation of the resulting 2-ethyl-S- methyl-N- / l-methoxy-2, -propylidón / aniline in a solvent in the presence of a platinum / US 4 200 451, DE 2328340 /, a palladium / 163,841 CS / or mecinatochroraitého / PV 9575-87 / hydrogenation catalyst, and the presence of a proton catalyst such as sulfuric acid (OE 2 328 340, US 4200 451, CS 169 841, PV · 393-89), acetic acid (CS 219 855); 2-methyl-5-ethylaniline hydrochloride / 2-methyl-6-ethylaniline semihydrogénsulfát / 2-methyl-6-ethylaniline trihydrogénfoafát, 2-methyl-6-ethyl-N / L of -mstoxy 2-propyl R / aniline hydrochloride , '2-methyl-6-ethyl-N / I / 2 * -mstoxy-propyl / aniline dihydrogen sulphate, 2-methyl-6-ethyl-N / l-methoxy-2''- propyl / aniline di - (trihydrogenphosphate) (PV 4257-88), trihydrogenphosphoric acid or hydrochloric acid used in an amount of 0.5 to 6/0% by weight, based on the 2-ethyl-5-methylaniline used (AO 4265-88, AO 4258-88 / AO 4259 -88 (AO 393-89), the above-mentioned proton catalysts are most preferably from the operational point of view hydrochloric acid (which, however, in amounts of from about 4% to about 5% by weight with respect to the 2-ethyl-S-diethylaniline used) the conversion step, requiring a longer reaction time, or the use of multiple amounts of platinum hydrogenation catalyst. It is essential to ensure that the proton catalyst used is of high purity in order to prevent hydrogenation catalyst inhibitors (especially heavy metal ions) being drilled into the hydrogenation process. After completion of the hydrogenation of the resulting Căetu 2-ethyl-6-methyl-N- / l-methoxy-2-propyl R / aniline acid bound to present as a quaternary salt; where a number of ways of its use are known, or isolation. AO 4259-88 and AO 393-89 propose recycling of the isolated quaternary salt as a proton catalyst to the next cycle of hydrogenation-alkylation. A significant disadvantage of these solutions is that, due to the corrosion of the process equipment, the heavy metal concentration in the pratone catalyst is gradually increased, which in addition to decreasing the activity of the hydrogenation catalyst in the 3 < 5 > According to DE 2 328 340, by adding triethylamine to the reaction mixture, the acid used as the proton catalyst is precipitated in the form of the triethylammonium salt, which is filtered off. The disadvantage of this solution is that triethylamine is necessary to be regenerated by means of an aqueous solution of an inorganic base, which is associated with the formation of waste defects with a high salt content. A method according to US 4 200 451 is that the resulting reaction mixture from hydrogenated alkylation is directly distilled under vacuum without isolation of the sulfuric acid used as proton catalyst. A shortcoming of this procedure is that the sulfuric acid acts as a sulfonating agent at the distillation temperature, resulting in losses on the desired product. Finally, after concentrating the resulting reaction mixture from the hydrogenation alkylation and separating the upper layer of the reaction product according to AO 4259-88 or AO 393-89, the 3-layer quaternary salt layer is no longer processed but discarded e.g. incineration, which also increases operating costs and reduces the degree of utilization of the raw materials.
Uvedenými postupmi vyrobený výsledný 2-etyl-6-motyl-N-/l'-metaxy-<i'-propyl/ anilin sa před Salšim spracovanim na 2-atyl-6-metyl-N-/l'-metoxy-2*-prcpyl/ chlóracetanilid reakciou ε chloracetylačným činidlom destiluje za·vákua, čím vzrastajú invsetičnó náklady a spotřeba energii.The resulting 2-ethyl-6-methyl-N- (1'-metaxyl-1'-propyl) aniline prepared by the above procedures was treated with 2-aryl-6-methyl-N- (1'-methoxy-2 *) before Salsi. -propyl / chloroacetanilide reacts with a chloroacetylating agent to distil under vacuum, increasing the cost of invasion and energy consumption.
Reakciu 2-etyl-S-metyl-N-/l,-metoxy-2/-propyl/ anilinu s chloracetylačným činidlom, najma chlóracetylchloridom, za účelom pripravy 2-atyl-S-metyl-N-/l’-metcxy-2z-propyl/ chlóracetanilídu je možné uskutečňovat buá v přítomnosti alebo v nepřítomnosti anorgaCS 272 750 Bl nickej bázy ako sú hydroxidy,' uhličitany alebo hydrogénuhličitany alkalických kovov, ale bo alkalických zemin vo vodnom alebo v bezvodom prostředí /US 4 200 451, CS 227 535, CS 169 841/. Významnou nevýhodou týchto sposobov je, žs pri nich vznikajú velké množstvá od pádových solí v tuhej formě alebo vo formě vodných roztokov, čo zhoršuje ekologická charakteristiky procesu. Tento problém zdanlivo rieši použitie organických báz ako je trietylamin, pyridin a niektoré dalšie /CS 169 841/, pri kíorom je však zase nevyhnutná regenerácia použitej organickej bózy. Reakciu je možné uskutočniť aj bez akceptora pri nej vznikajúceho chlorovodíka v inertnom organickom rozpúštadle tak, že sa plynný chlorovodík zachytává vo-vode. Reakcia 2-etyl-6-metyI-N-/lí’-metoxy-2‘’-propyl/ anilinu s chlóracatylchloridom v přibližné ekvimolárnych množstvách prebieha však relativné pomaly, vyžaduje si dlhšiu reakčnú dobu a je sprevádzaná nežiadúcou tvorbou vačšich množstiev živičnatých produktov. Tento nedostatek čiastočne odstraňuje spósob podlá CS 226 439 založený na reakcii izolovaného 2-etyl-6-metyl-M-/l'-metoxy-2'-prQpyl/ anilinu s chloracetyichloridom použitým v 1 až 19 násobnom molárnom přebytku·, pričom chlóracetylchlorid plni v procese i úlohu rozpúštadla. Oeho nevýhodou je, že pri nom reakcia nemá jednoznačný priebeh. Vzniká pri nom velké množstvo vediajšieho produktu 2-etyl-6-metyl-N-/l,-chlór-2,-propyl/-chlóracetanilidu, ktorý sa nedá od reakčného produktu oddělit, čo má za-nás-ledok nižší výtažek produktu pri nevyhovujúcej kvalitě.The reaction of 2-ethyl-S-methyl-N- / l-methoxy-2 / propyl / aniline chloracetylačným agent, especially chloroacetyl chloride, to prepare a 2-Allyl-S-methyl-N- / l-methoxy-2 z- propyl / chloroacetanilide can be carried out either in the presence or in the absence of inorganic bases such as alkali metal hydroxides, carbonates or bicarbonates or alkaline earths in aqueous or non-aqueous media / US 4 200 451, CS 227 535 , CS 169 841 /. A significant disadvantage of these processes is that they generate large amounts of fall salts in solid or aqueous solutions, which compromises the ecological characteristics of the process. The use of organic bases such as triethylamine, pyridine and some others (CS 169 841) seems to solve this problem, but regeneration of the used organic base is necessary in the case of sulfur. The reaction can also be carried out without the acceptor formed therein in an inert organic solvent by trapping the hydrogen chloride gas in water. The reaction of 2-ethyl-6-methyl-N- / L d '-methoxy-2''- propyl / aniline chlóracatylchloridom in approximately equimolar amounts, however, occurs relatively slowly, requiring a long reaction time and is accompanied by the undesirable formation of relatively large amounts of resin products . This drawback is partially remedied by the method of CS 226 439 based on the reaction of isolated 2-ethyl-6-methyl-N- (1'-methoxy-2'-propyl) aniline with chloroacetyl chloride used in a 1- to 19-fold molar excess, with chloroacetyl chloride filling. in the process also the role of the solvent. The disadvantage is that the reaction does not have a clear course. It generates by a large amount of by-product 2-ethyl-6-methyl-N- / l-chloro-2-propyl / -chlóracetanilidu that can not be separated from the reaction product, resulting in us-lower-Ledok extract the product unsatisfactory quality.
Uvedené nedostatky v rozhodujúcom rozsahu odstraňuje spbsob přípravy 2-etyl-6-metyl· -/lf-rr,etoxy-2'-propyl/chlóracetanilidu hydrogenačnou alkyláciou 2-etyl-6-metylanilinu metoxypropanonom v molárnom pomere 1 i 1,1 až 2 v proetredi l-metoxy-2-propanolu ako rozpúštadla,'· v přítomnosti platinového hydrogenačného katalyzátora a kyseliny chlorovodíkové j ako protonového katalyzátora pri teplote 20 až 100 °C a tlaku vodíka 0,1 až 7,0 MPa, připadne s vracanlm použitého hydrogenačného katalyzátora, l-metoxy-2-propanolu a nezreagovaného metoxypropanónu izolovaných z výslednej reakčnej zmesi,'do dalšieho cyklu hydrogenačnej alkylácie a reakciou získaného 2-etyl“6-mQtyl-N-/l'-ráotoxy-2'-propyl/anilinu s chlóracstylchloridom pri teplote od 70 °C do varu reakčnej zmesi pod spatným chladičom podlá vynálezu. Podstata vynálezu spočívá v tom, že v stupni hydrogenačnej alkylácie 2-etyl-6-metylanilinu metoxypropanonom sa kyselina chlorovodíková ako protonový katalyzátor použije v množstve 6,1 až 27 % hmotnostných v přepočte na použitýThe shortcomings of the screen the material removed spbsob 2-Ethyl-6-methyl; - / l f -RR, ethoxy-2-propyl / chloroacetanilide hydrogenation alkylation of 2-ethyl-6-methylaniline metoxypropanonom in a 1 to 1.1 and 2 in a 1-methoxy-2-propanol environment as a solvent, in the presence of a platinum hydrogenation catalyst and hydrochloric acid as a proton catalyst at a temperature of 20 to 100 ° C and a hydrogen pressure of 1 to 7.0 MPa, optionally hydrogenation catalyst, 1-methoxy-2-propanol and unreacted methoxypropanone isolated from the resulting reaction mixture, to the next cycle of hydrogenation alkylation and reaction of the obtained 2-ethyl-6-methyl-N- (1'-rotoxyxy-2'-propyl) aniline with chloroacetyl chloride at a temperature of from 70 ° C to the reflux of the reaction mixture according to the invention. The invention is based on the fact that in the hydrogenation alkylation step of 2-ethyl-6-methylaniline with methoxypropanone, hydrochloric acid is used as a proton catalyst in an amount of 6.1 to 27% by weight, based on the
2-etyI-6-metylanilín a výsledný reakčný produkt, ktorý po izolácii použitého platinového hydrogenačného katalyzátora, vody, rozpúštadla a nezreagovaného metoxypropanonu pozostáva z 2-etyl-6-metyl~N-/l/-metoxy-2*-propyl/ anilínu a z 2»etyl-6»metyl~ -N-/1 -metoxy»2*-propyl/ anilinu hydrochloridu sa bez dalších čiotiacich operácii nechá reagovat s cblóracatyXchloridora v prostrodi inertného organického rozpúštadla v molárnom pomers 1 : 1,1· až 2, Ako inertně organické rozpúštadlo aú vhodné alifatické,’ cyklcalifatické a aromatické uhlovodíky ako heptán, oktán, cýklohexán, zmesi uhlovodikov v benzinových frakciách, výhodné s teplotou varu v rozmedzí 30 až 110 °c; benzén, toluén.2-ethyl-6-methylaniline and the resulting reaction product which, after isolation of the used platinum hydrogenation catalyst, water, solvent and unreacted methoxypropanone, consists of 2-ethyl-6-methyl-N- (1H - methoxy-2'-propyl) aniline to 2-ethyl-6-methyl--N- (1-methoxy-2'-propyl) aniline hydrochloride is reacted without further purification operations with chloroborohydride in an inert organic solvent in a molar ratio of 1: 1.1 · 2 to 2, Suitable inert organic solvents are suitable aliphatic, cyclcaliphatic and aromatic hydrocarbons such as heptane, octane, cyclohexane, hydrocarbon mixtures in gasoline fractions, preferably boiling in the range of 30 to 110 ° C; benzene, toluene.
Oe výhodné; ak sa kyselina chlorovodíková použije v plynnej formě,' alebo absorbovaná v l-metoxy-2-propanole,' v zme3i l-metoxy-2-propanolu a 2-etyl-6-metylanilínu alebo v zmesi 1-metoxy-2-propanolu, 2-etyl-6-metylanilinu a metoxypropanónu· Cast bezvodého chlorovodíka vznikajúceho v stupni reakcie zmesi 2-etyl-6~raetyl-N-/l -metoxy-2z-propyl/ anilinu a jeho hydrochloridu s chlóracetylchloridom je výhodné vracat do procesu hydrogenačnsj alkylácie 2-etyl-6-metylanilínu metoxypropanonom ako protonový katalyzátor. Ostatný vznikajúci plynný chlorovodík je možné použit-na pripravu koncentrovanéj chlórovodíkovej kyseliny absorpciou· vo vodě alebo priamo plnit do tlakových fliaš. Spósob podlá vynálezu je možné uskutočňovat diskontinuitne, kontinuitne alebo tak, že stupeň hydrogenačnej alkylácie sa vedie diskontinuitne a stupen chlóracetylácie kontinuitne. Pri kontinuitnom vedeni chlóracetylácie je možné postupovat například tak, že sa zmes 2-styl-6-metyl-N-/l*-metoxy-2/-propyl/anilinu a jeho hydrochloridu a chlóracetylchlorid súčasne dávkujú· do reaktora vynriateho na reakčnú teplotu, skladajúceho sa z jedného až troch stupňov zapojených do kaskády. 2-etyl-6-metyl“N-/l’-metoxy-N-/l*-metoxy—2ř-pro3 CS 272 750 81 pyl/ chlóracetanilid sa izoluje z výslednej reakčnej zmesi odpařením rozpúšťadla, premytim vodou a/alebo vodným roztokom alkália pri teplote až do 30 °C a pračístenim destiláciou.Oe preferred; when the hydrochloric acid is used in gaseous form or absorbed in 1-methoxy-2-propanol, in a mixture of 1-methoxy-2-propanol and 2-ethyl-6-methylaniline or in a mixture of 1-methoxy-2-propanol, 2-ethyl-6-methylaniline and methoxypropenoate · Cast anhydrous hydrogen chloride generated in the reaction mixture of step 2-ethyl-6-raetyl N / l-methoxy-2-propyl z / aniline and the hydrochloride with chloroacetyl chloride is preferably returned to the process hydrogenačnsj alkylation of 2-ethyl-6-methylaniline with methoxypropanone as a proton catalyst. The other hydrogen chloride gas produced can be used to prepare concentrated hydrochloric acid by absorption in water or directly filled into pressurized bottles. The process according to the invention can be carried out discontinuously, continuously or in such a way that the hydrogenation alkylation step is carried out discontinuously and the chloroacetylation step continuously. Continuous chloroacetylation may be carried out, for example, by adding a mixture of 2-style-6-methyl-N- (1'-methoxy-2 ) -propyl] aniline and its hydrochloride and chloroacetyl chloride simultaneously to a reactor at room temperature. consisting of one to three stages involved in a cascade. 2-ethyl-6-methyl "N / l-methoxy-N / l * 2-methoxy--pro3 ° E 272 750 81 propyl / chloroacetanilide was isolated from the resulting reaction mixture by evaporation of the solvent, washing with water and / or water alkali solution at a temperature of up to 30 ° C and addition by distillation.
Sposob podlá vynálezu má viaceré významné výhody v porovnaní so známými sposobmi. Použitie chlórovodíkovej kyseliny ako protonového katalyzátora v stupni hydrogenačnej alkylácie v množstve 6?1 až 27,0 % hmotnostných v přepočte na použitý 2-etyl-6-metyl-anilin umožňuje neočakávane zvýšit stupeň konverzie reagujúcich zložiek a tým i čistotu produktu pri skrátení doby reakcie a zniženi množstva potřebného platinového hydrogenačného katalyzátora. Použitie zmesi 2-etyl-5-metyI-N-/l'-metoxy-2'-propyI/anilinu a jeho hydrochloridu do reakcie s chlóracetylchloridom umožňuje vypuetit investičně, energeticky i prevádzkove náročná operéciu vákuovaj destilácie rsakčného produktu predtým zbaveného použitého platinového hydrogenačného katalyzátora a prchavých podielov ktoré tvoři voda, l-metoxy-2-propanol a nezreagovaný mstoxypropanón a afaktívnejšie využit vstupné suroviny, pri získaní produktu o vysokej čistotě.The method according to the invention has several significant advantages over the known methods. The use of hydrochloric acid as the proton catalyst in the hydrogenation alkylation step of 6-1 to 27.0% by weight, based on the 2-ethyl-6-methyl-aniline used, unexpectedly increases the degree of conversion of the reactants and hence the purity of the product while reducing reaction time and reducing the amount of platinum hydrogenation catalyst required. The use of a mixture of 2-ethyl-5-methyl-N- (1'-methoxy-2'-propyl) aniline and its hydrochloride in reaction with chloroacetyl chloride enables the investment, energy and operationally demanding operation of vacuum distillation of the reaction product previously deprived of used platinum hydrogenation catalyst. and the volatile constituents consisting of water, 1-methoxy-2-propanol and unreacted mstoxypropanone, and more efficiently utilizing the feedstock, to obtain a high purity product.
Příklad 1Example 1
Do 750 ml teflonového autoklávu s magnetickým miešadlom sa předložilo 60,0 g 2-etyl-5-metylanilínu, 49/0 g metoxypropanónu, 90 g l-metoxy-2-propanolu, 17,5 g nasýteného roztoku chlórovodíka v l-metoxy-2-propanole a 300 mg platinového katalyzátora s obsahom 3 % platiny na aktivnom uhli. Zmes sa hydrogonovala pri 55 °C a tlaku 3 MPa počas 3 hodin.A 750 ml Teflon autoclave with a magnetic stirrer was charged with 60.0 g of 2-ethyl-5-methylaniline, 49/0 g of methoxypropanone, 90 g of 1-methoxy-2-propanol, 17.5 g of a saturated solution of hydrogen chloride in 1-methoxy- 2-propanol and 300 mg of platinum catalyst containing 3% platinum on activated carbon. The mixture was hydrogenated at 55 ° C and 3 MPa for 3 hours.
Po ukončenej reakcii sa zmes ochladila? platinový katalyzátor sa odfiltroval a z filtrátu sa oddestilovala reakčná voda, nezreagovaný metoxypropanón a l-metoxy-2-propanol. Získaná zmes obsahujúca 74?4 % hmotnostných 2-etyl-6-metyl-N-/lJ-metoxy-y2*-propyl/anilínu a 25,6 js hmotnostných 2-etyl-6~metyl~N-/l'-metoxy-2'-propyl/ani-lín hydrochloridu sa spolu so 180 ml toluénu preniesla do banky opatrenej miešadlom,’ teplomarom a prikvapkávacim lievlkom. Za chladenia sa pri 20 až 30 °C dávkoval chlóracetylchlorid? v množstve 100,3 g. Potom sa zmes vyhriala do refluxu, pri ktorom sa udržiavala 1 hodinu, ksdy vývin chlórovodíka skončil. Prebytočný nezreagovaný chlóracetylchlorid sa spolu s toluénom oddestiloval za zníženého tlaku. K destilačnérau zvyšku sa přidal toluén a 5 %-ný roztok hydroxidu sodného tak? aby sa pH reakčnej zmesi udržiavalo na 8. Zmes sa miešala pri 60 °C.After completion of the reaction, the mixture was cooled. the platinum catalyst was filtered off and the reaction water, unreacted methoxypropanone and 1-methoxy-2-propanol were distilled off from the filtrate. The resulting mixture of 74? 4% by weight of 2-ethyl-6-methyl-N- / L J -Methoxy-yl-propyl 2 * / js aniline and 25.6 by weight of 2-ethyl-6-methyl-N- / L ' The methoxy-2'-propyl / aniline hydrochloride, together with 180 ml of toluene, was transferred to a flask equipped with a stirrer, a thermometer and an addition funnel. Chloroacetyl chloride was metered in with cooling at 20-30 ° C? in an amount of 100.3 g. The mixture was then heated to reflux and maintained for 1 hour whenever the evolution of hydrogen chloride ceased. Excess unreacted chloroacetyl chloride, along with toluene, was distilled off under reduced pressure. Toluene and 5% sodium hydroxide solution were added to the distillation residue. to maintain the pH of the reaction mixture at 8. The mixture was stirred at 60 ° C.
Po premyti vodou sa organická vrstva ochladila? oddělila?’ vysušila a za vákua zahustila. Produkt sa predestiloval pri 144 °C/3,4 Pa. Získalo sa 117?5 g /93 ?3 % teorie/ 2-etyl-6-motyl-N-/l,-metoxy-2 -propyl/ chlpracetanilidu.After washing with water, the organic layer was cooled? separated? ' dried and concentrated under vacuum. The product was distilled at 144 ° C / 3.4 Pa. Yield: 117? 5 g / 93? 3% of theory / 2-ethyl-6-BUTTERFLY N / l-methoxy-2-propyl / chlpracetanilidu.
Plynný*chlorovodík? vznikajúcí pri reakcii sa odaberal z hornej časti spatného chladiče a odvádzal-sa do absorpcie v l-metoxy-2-propanole za vzniku nasýteného roztoku /s obsahom 20?8 % hmotnostných chlorovodíka při 20 °C/. Zvyšná časť chlórovodika sa absorbovala vo voda.* Hydrogen chloride? The reaction resulting from the reaction was removed from the top of the bad condenser and was taken up in 1-methoxy-2-propanol to give a saturated solution (containing 20-8% hydrogen chloride at 20 ° C). The remainder of the hydrogen chloride was absorbed into water.
Zmes toluénu a chlóracetylchloridu z destilácie sa použila v nasledujúcom cykle chlóracetylácie.A mixture of toluene and chloroacetyl chloride from the distillation was used in the next chloroacetylation cycle.
Přiklad 2Example 2
Roztok připravený zo 60?0 g 2-8tyl-6-metylanilinu a 130 g l-metoxy-2-propanolu sa sýtil 15?0 g plynného chlorovodíka. Potom sa zmes preniesla do hydrogaňačného autoklávu, přidalo sa 52?9 metoxypropanónu a 350 mg platinového katalyzátora s obsahom platiny 3 % na aktivnom uhli ako nosiči.·Zmes sa hydrogenovala 3?5 hodiny pri 60 °C a tlaku 2 MPa.A solution prepared from 60.0 g of 2-8-ethyl-6-methylaniline and 130 g of 1-methoxy-2-propanol was saturated with 15.0 g of hydrogen chloride gas. The mixture was then transferred to a hydrogenation autoclave, 52-9 methoxypropanone and 350 mg of platinum catalyst containing 3% platinum on activated carbon were added, and the mixture was hydrogenated at 60 ° C and 20 bar for 3-5 hours.
Po ukončenej hydrogenácii sa platinový katalyzátor odsál a z filtrátu sa pri zniženom tlaku oddastilovalo rozpúšťadlo. Po ochladeni destilačný zvyšok zkryštalizoval. Obsahoval 106,1 g zmesi o zložení 7,9 % hmotnostných 2-etyl-6-metyl-N-/l'-metoxy-2#-prGpyl/anilinu a 9z,l % hmotnostných 2-etyl-5-metyl-N-/l‘-raatoxy-2,~prapyl/_anilin hydrochloridu.After the hydrogenation was complete, the platinum catalyst was aspirated and the solvent was distilled off under reduced pressure. After cooling, the distillation residue crystallized. It contained a mixture of 106.1 g of the composition of 7.9% by weight of 2-ethyl-6-methyl-N- / l-methoxy-2 # -prGpyl / aniline 9Z, l% by weight of 2-ethyl-5-methyl-N - / ' raatoxy-2, ~ prapyl / _anilin hydrochloride.
K zmesi 3a přidalo 300 ml toluénu, pričom sa destilačný chladič vyměnil za spatný. K suspenzi! sa za miešania a chladenia dávkovalo 100,3 g chlóracetylchloridu počas 30 minút a zmes sa refluxovala ešte 1 hodinu. Potom sa oddestiloval nezreagovaný chlóracetylchloCS 272 750 31 rld spolu s častou toluénu čim sa zmes zahustila na polovičný objem. Po ochladení sa zahuštěná reakčná zmes prsmývala 10 %-ným uhličltanom sodným a vodou. Z organickéj vrstvy sa oddestiloval toluén za zníženého tlaku 13 kPa. Produkt 2-Qtyl-S-mstyl-M-/lz-inetoxy-2r-propyl/-chlóracetanilid destiloval pri 142 °C/3 Pa v množstve 116,8 g /92·,7 % teorie/ Část plynného chlorovodika unikajúceho z reakčného priestoru pri chloracetylácii sa odvádzala a absorbovala v zmssí 2-otyl-S-metylanilinu a l-mstoxy-2-propanolu tak) aby sa ziskal roztok potrebnej koncentrácie do nasledujúceho etupna hydrogonačnej alkylácie. Zvyšný chlorovodík ea absorboval vo vodě.To mixture 3a was added 300 ml of toluene, while the distillation condenser was replaced with a bad condenser. To the suspension! 100.3 g of chloroacetyl chloride were metered in with stirring and cooling for 30 minutes and the mixture was refluxed for a further 1 hour. Thereafter, unreacted chloroacetylchloride was distilled off, along with some toluene, and the mixture was concentrated to half volume. After cooling, the concentrated reaction mixture was washed with 10% sodium carbonate and water. Toluene was distilled off from the organic layer under reduced pressure of 13 kPa. The item-2-S-Qtyl Mstyle-M / l of -inetoxy-propyl R 2 / -chlóracetanilid distilled at 142 ° C / 3 mbar in an amount of 116.8 g / 92 · 7% of theory / HCl gas escaping portion it was removed from the reaction space during chloroacetylation and absorbed in a mixture of 2-otyl-S-methylaniline and 1-methoxy-2-propanol so as to obtain a solution of the necessary concentration until the next stage of the hydrogenation alkylation. The remaining hydrogen chloride ea absorbed in water.
Příklad 3Example 3
V zmesi 50,0 g 2-etyl-S-metylanilinu a 131 g l-metoxy-2-propanolu sa absorbovalo 5,0 g plynného chlorovodika. Po přidaní 47,0 g metoxypropanónu a 120 mg platinového katalyzátore na aktivnom uhlí o s obsahom platiny 5 % ca zmes- hydrogonovala pri 40 °C a tlaku vodíka 7,0 MPa po dobu 3,5 hodin.5.0 g of hydrogen chloride gas were absorbed in a mixture of 50.0 g of 2-ethyl-S-methylaniline and 131 g of 1-methoxy-2-propanol. After the addition of 47.0 g of methoxypropanone and 120 mg of platinum-on-carbon catalyst with a platinum content of 5% c and the mixture was hydrogenated at 40 ° C and a hydrogen pressure of 7.0 MPa for 3.5 hours.
Po ukončenej hydrcgonácii sa zmes ochladila, platinový katalyzátor sa odfiltroval a filtrát sa zahustil, nakoniec za vékua. Dostilačný zvyšok v množstva H8,l g představoval zmes o zložení 59,'1 % hmotnostných 2-etyl-5-motyi-N-/l‘’-metoxy~2'-propyl/ anilinu aAfter complete hydrogenation, the mixture was cooled, the platinum catalyst was filtered off and the filtrate was concentrated, finally under vacuum. A sufficient residue in an amount of H8.1 g was a mixture of 59.1% by weight of 2-ethyl-5-methyl-N- (1'-methoxy-2'-propyl) aniline, and
40.9 % hmotnostných 2-etyl-S-metyl-N-/l/-metoxy“2’-propyl/anllin· hydrochloridu. K zmasi sa přidalo 150 ml cyklohexánu a za miešania 3a z prikvapkávacieho lievika přidával chlóracetylchlorid v množstve 57,7 ge Teplota reakčnej zmesi 3a chladoníra udržiavala pri 30až 40 °c.40.9% by weight of 2-ethyl-S-methyl-N / L / methoxy "2'-propyl / anllin · HCl. 150 ml of cyclohexane were added to the mixture, and 57.7 g of chloroacetyl chloride was added from a dropping funnel with stirring 3a . The temperature of the reaction mixture 3a was maintained at 30-40 ° C.
Po vydávkovani chlóracetylchloridu 3a reakčná zrae3 vyhriola do refluxu,' ktorý sa udržiaval ešte 2 hodiny.· Po ukončeni vývinu chlorovodika so z reakčnej zmesi najskSr oddostiiovala třetina toluénu spolu s nezreagovoným chlóracetylchloridom a po ochladení sa premývala vodou a roztokom uhličitanu sodného. Po oddestilováni rozpúšťadla destiloval za vá· kua produkt pri t. v. 148 °c/4 Pa. získalo sa il7,7 g /93,4 % teorie/ 2-etyl-G-metyl-N-/l’-matoxy-2/-propyl/-chlór0cetanilidu ako bledožltej viskóznoj· kvapaliny. Plynný chlorovodík, ktorý sa pri chloracetylácii uvolňoval, sa odvádzal zčásti na adsorbciu do roztoku 2-etyl-S-metylanllinu v l-motoxy-2-propanols a zvySok sa absorboval vo vodě.After the chloroacetyl chloride 3a was dispensed, the reaction mixture 3 was heated to reflux for 2 hours, and after completion of the evolution of hydrogen chloride, one third of the toluene together with the unreacted chloroacetyl chloride was de-aerated from the reaction mixture and washed with water and sodium carbonate solution. After distilling off the solvent, the product was distilled under vacuum at a temperature of 148 ° C / 4 Pa. 17.7 g (93.4% of theory) of 2-ethyl-N-methyl-N- (1'-methoxy-2 ) -propyl) -chloroacetanilide were obtained as a pale yellow viscous liquid. Hydrogen chloride gas released during chloroacetylation was partially removed for adsorption into a solution of 2-ethyl-5-methylaniline in 1-hydroxy-2-propanols and the remainder absorbed in water.
Příklad 4Example 4
Zmes 50,0 g 2-ctyl-6-metylanilínu, 131 g 1-metoxy-2-propanolu, 45,0 g metoxypropanánu a 22b mg platinového katalyzátora 3 nooičora aktivnym uhlím a obsahom 3 % platiny sa · nasýtila 3 3)7 g plynného chlorovodika. Teplota zmesi přitom vystúpila na 40 °C. Zmes sa ihnoS preliala do teflonového autoklávu s magnetickým tniešadlom a hydrogenovala ea po dobu 3,5 hodiny pri 50 °c a tlaku vodika 5,0 MPa. Roakčná zmes sa po ukončenej hydrogonácii ochladila, platinový katalyzátor sa odfiltroval, filtrát sa zahustil, nakoniec za vákua. Oeetilačný zvyšok v množstvo 93,7 g tvořilo zmes 2-otyl-B-metyl-N»/l'-motoxy-2‘-propyl/ anilinu a ž-otyl-O-metyl-N-Zl^-mstoxy-S^-propyl/ anilín hydrochloridu.A mixture of 50.0 g of 2-ctyl-6-methylaniline, 131 g of 1-methoxy-2-propanol, 45.0 g of methoxypropanane and 22b mg of platinum catalyst 3 activated carbon and containing 3% platinum was saturated 3 3) 7 g hydrogen chloride gas. The temperature of the mixture rose to 40 ° C. The mixture was poured into a Teflon autoclave with a magnetic entrainer and hydrogenated for 3.5 hours at 50 ° C and 50 psi hydrogen pressure. The annual mixture was cooled after completion of the hydrogenation, the platinum catalyst was filtered off, the filtrate was concentrated, finally under vacuum. The impurity of 93.7 g was a mixture of 2-otyl-B-methyl-N '/ 1'-motoxy-2'-propyl / aniline and 2-otyl-O-methyl-N-Z1-m-methoxy-5'-methyl-N'. -propyl / aniline hydrochloride.
Zmas sa preniosla do banky opatrenej spatným chladičom, prikvapkávacim lievikom a teplomerom, Ako rozpúšťadlo sa použilo 250 ml benzínováj frakcie s teplotou varu 80 až 110 UC. □o reakčnej zmesi sa dávkoval chlóracstylchlorid v calkovom množstve 55)2 g boz chladenia tak, že sa teplota suspenzie zvyšovala samovolné na 50 °G, Po ukončenom dávkováni 3a zmes vyhriala pri teplotě refluxu počas 2 hodin) kedy vývin chlárovodika skončil. Zvyšok sa ochladil, premýval 5 % roztokom hydroxidu sodného a vodou. Potom so oddsstilovalo rozpúšťadlo) nakoniec za vákua. Zvyšok sa podrobil vákuovej destiiácii, 2-etyl-S-motyl-M-/l,~ -metoxy-2'-propyl/-chlóracetanllid destiloval pri 142 °C/3 Pa. ZÍ3kal so vo výtažkuConfuse the preniosla to a flask equipped with a condenser, dropping funnel and thermometer was used as the solvent benzínováj 250 ml fractions with a boiling point of 80 to 110 □ C. In the reaction mixture was dosed chlóracstylchlorid in an amount Calková 55) 2 g Boz cooling by The temperature of the suspension was raised spontaneously to 50 ° C. After completion of 3a dosing, the mixture was heated at reflux temperature for 2 hours) when the evolution of hydrogen chloride was complete. The residue was cooled, washed with 5% sodium hydroxide solution and water. Then the solvent was distilled off) finally under vacuum. The residue was subjected to vacuum distilling off the 2-S-ethyl-N- motyl / l ~ methoxy-2-propyl / -chlóracetanllid distilled at 142 ° C / 3 mbar. He glared in the extract
134.9 g /95)2 % teorie/.134.9 g (95) 2% of theory.
Z chlóracotylácio uvolňovaný reakčný chlorovodík sa odoberal v hornej častí spatného chladiča a absorboval sa v reakčnej zmasi do nydrogenačnej alkylácie.The reaction hydrogen chloride released from the chloro-acetylation was removed at the top of the bad condenser and absorbed in the reaction mixture to nitrogens alkylation.
Claims (3)
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| CN109280012A (en) * | 2017-07-19 | 2019-01-29 | 山东侨昌化学有限公司 | A kind of uninanned platform isopropyl methoxalamine intermediate 2- ethyl -6- methyl-N-(1 '-methoxyl group -2 '-propyl) aniline method |
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