CS267385B1 - Method of 2,6-dialkyl-n-/1-methoxy-2-propyl/anilines preparation - Google Patents
Method of 2,6-dialkyl-n-/1-methoxy-2-propyl/anilines preparation Download PDFInfo
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- CS267385B1 CS267385B1 CS884269A CS426988A CS267385B1 CS 267385 B1 CS267385 B1 CS 267385B1 CS 884269 A CS884269 A CS 884269A CS 426988 A CS426988 A CS 426988A CS 267385 B1 CS267385 B1 CS 267385B1
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- methoxy
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- propanol
- hydrogenation
- platinum
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- 238000000034 method Methods 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 150000001448 anilines Chemical class 0.000 title description 5
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims abstract description 86
- 239000003054 catalyst Substances 0.000 claims abstract description 78
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 78
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 74
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 39
- 230000029936 alkylation Effects 0.000 claims abstract description 34
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 34
- CUZLJOLBIRPEFB-UHFFFAOYSA-N 1-methoxypropan-2-one Chemical compound COCC(C)=O CUZLJOLBIRPEFB-UHFFFAOYSA-N 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 239000011541 reaction mixture Substances 0.000 claims abstract description 19
- 238000004821 distillation Methods 0.000 claims abstract description 16
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 8
- 239000006185 dispersion Substances 0.000 claims abstract description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 26
- 238000009835 boiling Methods 0.000 claims description 12
- JJVKJJNCIILLRP-UHFFFAOYSA-N 2-ethyl-6-methylaniline Chemical compound CCC1=CC=CC(C)=C1N JJVKJJNCIILLRP-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 238000004062 sedimentation Methods 0.000 claims description 7
- 238000005292 vacuum distillation Methods 0.000 claims description 7
- UGHAORLKXOZCCG-UHFFFAOYSA-N aniline phosphoric acid Chemical compound OP(O)(O)=O.OP(O)(O)=O.NC1=CC=CC=C1 UGHAORLKXOZCCG-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- -1 2,6-diethylaniline methoxypropanone Chemical compound 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N 2-propanol Substances CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 241000269350 Anura Species 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 238000000605 extraction Methods 0.000 claims 1
- 238000002203 pretreatment Methods 0.000 claims 1
- 238000001953 recrystallisation Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000004476 plant protection product Substances 0.000 abstract description 2
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- 150000001450 anions Chemical class 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000003039 volatile agent Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- VNKYTQGIUYNRMY-UHFFFAOYSA-N methoxypropane Chemical compound CCCOC VNKYTQGIUYNRMY-UHFFFAOYSA-N 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Riešenie sa týká spósobu pripravy 2,6 dialkyl-N-(l’-metoxy-2’-propyl)aniIínov, v ktorých alkylové skupiny móžu byť rovnaké alebo rózne a znamenajú metyl alebo etyl, hydrogenačnou alkyláciou příslušných 2,6-dialkylanilínov metoxypropanónom v prostředí 1-metoxy2-propanolu a v přítomnosti trihydrogénfosforečnej kyseliny ako protónového katalyzátora a platinového hydrogenačného katalyzátora. Výsledná reakčná zmes, z ktorej sa připadne najprv oddělí platinový hydrogenačný katalyzátor, sa zbaví rektifikáciou vody vo formě jej azeotropných zmesí s metoxypropanónom a l-metoxy-2-propanoIom, ďalšou rektifikáciou sa z nej oddělí l-metoxy-2-propanol, z heterogénneho destilačného zvyšku sa oddělí horná vrstva reakčného produktu, pričom spódná vrstva, pozostávajúca z disperzie platinového hydrogenačného katalyzátora v protónovom katalyzátore alebo z protónového katalyzátora, zriedená l-metoxy-2-propanolom a připadne doplněná čerstvým platinovým hydrogenačným katalyzátorem a/alebo čerstvým protónovým katalyzátorem a z reakčnej zmesi připadne oddělený platinový hydrogenačný katalyzátor samotný alebo doplněný čerstvým katalyzátorem a l-metoxy-2-propanol sa vracajú do ďalšieho cyklu hydrogenačnej alkylácie. Riešenie je možné využiť v chemickom priemysle pri výrobě chemických prostriedkov na ochranu rastlín.The present invention relates to a process for the preparation of 2,6 dialkyl N- (1'-methoxy-2'-propyl) anions in which the alkyl groups may be the same or and are methyl or ethyl, hydrogenated by alkylation of the corresponding 2,6-dialkylanilines methoxypropanone in 1-methoxy-2-propanol and in the presence of trihydrogenphosphate acid as proton catalyst and a platinum hydrogenation catalyst. The resulting reaction mixture will be added first separating the platinum hydrogenation catalyst, it is rectified in the form of its water azeotropic mixtures with methoxypropanone and 1-methoxy-2-propanoyl, by further rectification from which 1-methoxy-2-propanol is separated from heterogeneous distillation residue is separated off the reaction product layer, the bottom layer, consisting of a platinum hydrogenation dispersion catalyst in the proton catalyst or a proton catalyst, diluted with 1-methoxy-2-propanol and added supplemented with fresh platinum hydrogenation catalyst and / or fresh proton catalyst and fall out of the reaction mixture a separate platinum hydrogenation catalyst alone or supplemented with fresh catalyst and 1-methoxy-2-propanol is recycled another cycle of hydrogenation alkylation. Solution can be used in the chemical industry for the production of chemical plant protection products.
Description
Vynález sa týká spósobu přípravy 2,6-dialkyl-N-(l’-metoxy-2’-propyl)anilinov. Uvedené zlúčeniny sú medziproduktami na výrobu chemických prostriedkov na ochranu rastlín.The invention relates to a process for the preparation of 2,6-dialkyl-N- (1'-methoxy-2'-propyl) anilines. Said compounds are intermediates for the production of chemical plant protection products.
2,6 dialkyl N (Γ alkoxy-2'-propyl)anilíny sú už dlhšie známe z patentovej litcratúry (US 2 387 071, US 2 759 943). Pripraviť ich možno napr. reakciou 2,6-dialkylanilínov s 2-halogén-l-alkoxypropánom (US 3 937 730). Iný známy spósob ich přípravy je založený na kondenzácii 2,6-dialkylanilínov s alkoxyproponó' nom a súčasnej alebo následnej hydrogenácii výsledného 2,6-dialkyl-N-(l’-alkoxy-2’-propylidén)anilínu (azometín) (US 3 937 730, US * 4 022 611). Známe je tiež, že takýto typ hydrogenačnej alkylácie sa uskutečňuje v přítomnosti protonového katalyzátore a hydrogenačného katalyzátore ne báze vzácných kovov (US 4 200 451), bez přítomnosti rozpúšťedla (US 4 200 451, DE 2 328 340) elebo v prostředí rozpúšťedla (BE 810 763, CS 219 856). Protonový katalyzátor jednak urýchíuje kondenzačnú reakciu 2,6-dialkylanilínu s alkoxypropanónom a jednak aktivuje hydrogenačný katalyzátor na báze vzácného kovu pri paralelné prebiehajúcej hydrogenácii azometínu. Hydrogenačné katalyzátory na báze vzácných kovov, napr. paládia alebo platiny, sa totiž v priebehu hydrogenácie dezaktivujú účinkom katalyzátorových jedov, ako sú napr. rožne polymérne látky, dusíkaté zlúčeniny, vrátane amínov a nukleofilné ióny. Z literatury je známe, že pri hydrogenačnej alkylácii 2,6-disubstituovaných anilínov alkoxypropanónmi je možné ako protonový katalyzátor použiť kyselinu octovú a ako rozpúšťadlo etylalkohol (CS 219 856). Významnou nevýhodou tohoto nešenia je, že výsledná reakčná zmes okrem reakčného produktu obsahuje viaceré zložky s nízkou teplotou varu ako je kyselina octová, etylalkohol, voda, nezreagovaný metoxypropanón a jeho hydrogenáciou vzniklý l-metoxy-2-propanol a připadne i octan etylový. Keďže uvedené zložky majú blízké teploty varu a naviac navzájom tvoria niekofko azeotropných zmesí, nie je možné ich účinné rozdelenie a opátovné využitie, čo zdražuje celý proces a spósobuje i problémy súvisiace - s iikvidáciou takýchto odpadov.2,6 dialkyl N- (Γalkoxy-2'-propyl) anilines have been known for a long time from the patent literature (U.S. Pat. No. 2,387,071, U.S. Pat. No. 2,759,943). They can be prepared e.g. by reacting 2,6-dialkylanilines with 2-halo-1-alkoxypropane (US 3,937,730). Another known process for their preparation is based on the condensation of 2,6-dialkylanilines with alkoxyproponone and the simultaneous or subsequent hydrogenation of the resulting 2,6-dialkyl-N- (1'-alkoxy-2'-propylidene) aniline (azomethine) (US 3 937 730, U.S. Pat. No. 4,022,611). It is also known that this type of hydrogenation alkylation is carried out in the presence of a proton catalyst and a hydrogenation catalyst not based on noble metals (US 4,200,451), in the absence of a solvent (US 4,200,451, DE 2,328,340) or in a solvent medium (BE 810 763, CS 219 856). The proton catalyst, on the one hand, accelerates the condensation reaction of 2,6-dialkylaniline with alkoxypropanone and, on the other hand, activates the noble metal hydrogenation catalyst during the parallel hydrogenation of azomethine. Noble metal hydrogenation catalysts, e.g. palladium or platinum, are deactivated during hydrogenation by the action of catalyst poisons, such as e.g. various polymeric substances, nitrogen compounds, including amines and nucleophilic ions. It is known from the literature that acetic acid can be used as a proton catalyst and ethyl alcohol as a solvent in the hydrogenation alkylation of 2,6-disubstituted anilines with alkoxypropanones (CS 219 856). A significant disadvantage of this solution is that the resulting reaction mixture contains, in addition to the reaction product, several low-boiling components such as acetic acid, ethyl alcohol, water, unreacted methoxypropanone and its hydrogenation formed 1-methoxy-2-propanol and optionally ethyl acetate. Since these components have close boiling points and, in addition, form azeotropic mixtures with one another, their efficient separation and reuse is not possible, which makes the whole process more expensive and also causes problems associated with the disposal of such wastes.
Uvedené nedostatky odstraňuje spósob přípravy 2,6-dialkyl-N-(l’-metoxy-2’-propyl)anilí» nov všeobecného vzorca IThe process for the preparation of 2,6-dialkyl-N- (1'-methoxy-2'-propyl) anilines of the formula I overcomes these drawbacks.
R1 R 1
kde R' a R2 sú rovnaké alebo rózne a znamenajú metyl alebo etyl, hydrogenačnou alkyláciouwherein R 1 and R 2 are the same or different and represent methyl or ethyl, by hydrogen alkylation
CS 267 385 B1CS 267 385 B1
2,6-dialkylanilínov všeobecného vzorca II2,6-dialkylanilines of general formula II
kde R’ a R2 majú už uvedený význam, metoxypropanónom v prostředí l-metoxy-2propanolu a v přítomnosti trihydrogénfosforečnej kyseliny ako protónového katalyzátora a platinového hydrogenačného katalyzátora podl’a vynálezu. Jeho podstata spočívá v tom, že výsleddná reakčná zmes, z ktorej sa připadne najprv oddělí platinový hydrogenačný katalyzátor, sa zbaví rektifikáciou vody vo forme jej azeotropných zmesí s metoxypropanónom a l-metoxy-2-propauolom, ďalšou rektifikáciou sa z nej oddělí l -metoxy-2-propanol, z heterogénneho destilačného zvyšku sa oddělí horná vrstva reakčného produktu, pričom spodná vrstva, pozostávajúca z protonového katalyzátora, připadne z disperzie platinového hydrogenačného katalyzátora v protónovom katalyzátore, zriedené l-metoxy-2-propanolom a připadne doplněná čerstvým protonovým katalyzátorem, a/alebo čerstvým platinovým hydrogenačným katalyzátorem, z reakčnej zmesi připadne oddělený platinový hydrogenačný katalyzátor samotný alebo doplněný čerstvým katalyzátorem a 1-metoxy-2-propanol sa vracajú do ďalšieho cyklu hydrogenačnej alkylácie.wherein R 1 and R 2 are as defined above, methoxypropanone in the presence of 1-methoxy-2-propanol and in the presence of trihydrogenphosphoric acid as proton catalyst and platinum hydrogenation catalyst according to the invention. Its essence is that the resulting reaction mixture, from which the platinum hydrogenation catalyst is first separated, is freed by rectification of water in the form of its azeotropic mixtures with methoxypropanone and 1-methoxy-2-propauole, further rectification separates 1-methoxy. -2-propanol, the upper layer of the reaction product is separated from the heterogeneous distillation residue, the lower layer consisting of a proton catalyst, optionally of a dispersion of a platinum hydrogenation catalyst in a proton catalyst, diluted with 1-methoxy-2-propanol and optionally supplemented with fresh proton catalyst, and / or fresh platinum hydrogenation catalyst, optionally a separate platinum hydrogenation catalyst alone or supplemented with fresh catalyst from the reaction mixture, and 1-methoxy-2-propanol are returned to the next hydrogenation alkylation cycle.
Trihydrogénfosforečná kyselina, použitá ako protonový katalyzátor, reaguje s východzím 2,6-dialkylanilínom za vzniku 2,6-dialkylanilín trihydrogénfosfátu. S postupujúcou hydrogenačnou alkyláciou 2,6-dialkylanilínu metoxypropanónom na 2,6-dialkyl-N-(1’-metoxy-2’ -propyllanilín prechádza uvedená sol’ na 2,6-dialKyl-N-(r-metoxy-2’-propyl)anilín di-(trihydrogénfosfát), pričom obidve tieto soli majú vlastnosti protónového katalyzátora. Výsledná reakčná zmes pozostáva teda z l-metoxy-2 -propanolu, ktorý sa dodává do procesu ako rozpúšťadlo a okrem toho v určitém množstve vzniká v procese vedfajšou hydrogenáciou metoxypropanónu, ďalej z reakčnej vody využitej ako rozpúšťadlo, z přebytečného metoxypropanónu, z 2,6-dialkyl-N-(r-metoxy-2’-propyl)anilín di-(trihydrogénfosfátu), z čiastočne dezaktivovaného platinového hydrogenačného katalyzátora na aktívnom uhlí ako nosiči a z reakčného produktu, ktorým je příslušný 2,6-dialkyl-N-( 1 ’-metoxy-2’-propyl)anilín.Trihydrogenphosphoric acid, used as a proton catalyst, reacts with the starting 2,6-dialkylaniline to form 2,6-dialkylaniline trihydrogen phosphate. As the hydrogenation alkylation of 2,6-dialkylaniline with methoxypropanone to 2,6-dialkyl-N- (1'-methoxy-2'-propylaniline), the salt is converted to 2,6-dialkyl-N- (r-methoxy-2'- propyl) aniline di- (trihydrogen phosphate), both of which have proton catalyst properties, so that the resulting reaction mixture consists of 1-methoxy-2-propanol, which is fed to the process as a solvent and, in addition, formed in a minor amount by secondary hydrogenation. methoxypropanone, further from the water of reaction used as solvent, from excess methoxypropanone, from 2,6-dialkyl-N- (r-methoxy-2'-propyl) aniline di- (trihydrogen phosphate), from the partially deactivated platinum hydrogenation catalyst on activated carbon as carriers and from the reaction product which is the corresponding 2,6-dialkyl-N- (1'-methoxy-2'-propyl) aniline.
Pri príprave 2,6-dialkyl-N-(l’-metoxy-2’-propyl)anilínov všeobecného vzorca I spósobom podl’a vynálezu je možné postupovať tak, že po skončení hydrogenačnej alkylácie sa platinový hydrogenačný katalyzátor odfiltruje alebo sa nechá usadit' v autokláve, připadne v sedimentačnej nádobě a reakčná zmes sa spracuje bezIn the preparation of 2,6-dialkyl-N- (1'-methoxy-2'-propyl) anilines of the formula I according to the invention, the platinum hydrogenation catalyst can be filtered off or allowed to settle after the hydrogenation alkylation has ended. in an autoclave, optionally in a sedimentation vessel, and the reaction mixture is worked up without
CS 267 385 Bl filtrácie spolu s jemnými podielmi platinového hydrogenačného katalyzátora. V obidvoch prípadoch sa potom z reakčnej zmesi odstráni rektifikáciou voda vo forme jej azeotropných zmesi s metoxyjiropanónom a 1 meloxy-2 pro panolom (azeotropná zmes vody s nietoxypropanónom obsahuje 40 % hmot, vody a vrie pri 93 °C, azeotropná zmes vody s l-metoxy-2 -propanolom obsahuje 48,5% hmot, vody a vrie pri 96 °C) a ako ďalšia frakcia čistý l-metoxy-2-propanol s teplotou varu 119 až 121 °C. Z heterogénneho destilačného zvyšku sa odčerpá horná vrstva, z ktorej sa vákuovou destiláciou získá reakčný produkt, ktorým je příslušný 2,6CS 267 385 B1 filtration together with fine portions of a platinum hydrogenation catalyst. In both cases, water is then removed from the reaction mixture by rectification in the form of its azeotropic mixtures with methoxyjiropanone and 1 meloxy-2 for panel (azeotropic mixture of water with non-oxypropanone containing 40% by weight of water and boiling at 93 ° C, azeotropic mixture of water with l- methoxy-2-propanol contains 48.5% by weight of water and boils at 96 ° C) and as a further fraction pure 1-methoxy-2-propanol with a boiling point of 119-121 ° C. The upper layer is drained from the heterogeneous distillation residue, from which the reaction product, corresponding to 2.6
-dialkyl-N-iT-metoxy-2’-propyl)anilin, pričom predná francia, pozostávajúca z l-metoxy-2 -propanolu a zvyškov nezreagovaného 2,6-dialkylanilínu sa vracia do ďalšieho cyklu hydrogenačnej alkylácie, Spodná vrstva destilačného zvyšku, pozostávajúca z protonového katalyzátora alebo z jemnej disperzie malých množstiev platinového hydrogenačného katalyzátora v protónovom katalyzátore sa po zriedení l-metoxy-2-propanolom a prípadnom doplnění čerstvým protonovým katalyzátorem vracia do ďalšieho cyklu hydrogenačnej alkylácie. Odfiltrovaný platinový hydrogenačný katalyzátor zriedený l-metoxy-2-propanolom alebo jeho suspenza, usadená v autokláve alebo v sedimentačnej nádobě, tvoriacom asi 2,5 % objemu celej reakčnej zmesi, sa po prípadnom doplnění čerstvým katalyzátorem vracia do ďalšieho cyklu hydrogenačnej alkylácie. Z oddestilovanej zmesi vody, metoxypropanónu a l-metoxy-2 -propanolu sa rektifikáciou pri atmosférickom tlaku získá čistý l-metoxy-2-propanol. Z procesu regenerovaný l-metoxy-2-propanol sa vracia do ďalšieho cyklu hydrogenačnej alkylácie ako rozpúšťadlo, alebo sa katalytickou hydrogenáciou spracuje na metoxypropanón.-dialkyl-N-N-methoxy-2'-propyl) aniline, the front francise, consisting of 1-methoxy-2-propanol and unreacted 2,6-dialkylaniline residues being returned to the next cycle of hydrogenation alkylation, the lower layer of the distillation residue, consisting of a proton catalyst or a fine dispersion of small amounts of a platinum hydrogenation catalyst in a proton catalyst is returned to the next hydrogenation alkylation cycle after dilution with 1-methoxy-2-propanol and optional addition of fresh proton catalyst. The filtered platinum hydrogenation catalyst diluted with 1-methoxy-2-propanol or a suspension thereof, settled in an autoclave or in a sedimentation vessel constituting about 2.5% by volume of the total reaction mixture, is returned to the next hydrogenation alkylation cycle, optionally supplemented with fresh catalyst. Pure 1-methoxy-2-propanol is obtained from the distilled-off mixture of water, methoxypropanone and 1-methoxy-2-propanol by rectification at atmospheric pressure. The 1-methoxy-2-propanol recovered from the process is returned to the next hydrogenation alkylation cycle as a solvent, or processed to methoxypropanone by catalytic hydrogenation.
Postupovať je možné aj tak, že po skončení hydrogenačnej alkylácie sa reakčná zmes vo forme suspenzie přečerpá z autoklávu do destilačného kotlá, kde sa z nej najprv oddestiluje voda vo forme uvedených azeotropných zmesi a ako ďalšia frakcia čistý l-metoxy-2-propanol, z hornej vrstvy destilačného zvyšku sa vákuovou destiláciou získá reakčný produkt a spodná vrstva, zložená zo zmesi platinového hydrogenačného a protonového katalyzátora sa po zriedení l-metoxy-2-propanolom a prípadnom doplnění čerstvým platinovým hydrogenačným alebo protonovým katalyzátoroin vracia do ďalšieho stupňa hydrogenačnej alkylácie.It is also possible to proceed by pumping the reaction mixture in the form of a suspension from the autoclave to a distillation vessel after completion of the hydrogenation alkylation, where water is first distilled off in the form of the azeotropic mixtures and pure 1-methoxy-2-propanol as a further fraction. The upper layer of the distillation residue is vacuum distilled to give the reaction product and the lower layer, consisting of a mixture of platinum hydrogenation and proton catalyst, is returned to the next hydrogenation alkylation step after dilution with 1-methoxy-2-propanol and optional addition of fresh platinum hydrogenation or proton catalyst.
Významnou výhodou spósobu přípravy 2,6-dialkyl-N-(l’-metoxy-2’-propyl)anih'nov všeobecného vzorca I podl’a vynálezu v porovnaní so znýmymi spósobmi je jeho vysoká hospodárnosť najma z hl'adiska využitia platinového hydrogenačného katalyzátora, protonového katalyzátora a 1-metoxy-2-propanolu ako rozpúšťadla, pri vysokých výťažkoch a čistotě produktu a nepomerne menšom množstve odpadovv.A significant advantage of the process for the preparation of 2,6-dialkyl-N- (1'-methoxy-2'-propyl) animines of the general formula I according to the invention in comparison with the known processes is its high economy, especially from the point of view of the use of platinum hydrogenation. of catalyst, proton catalyst and 1-methoxy-2-propanol as solvent, in high yields and product purity and disproportionately less waste.
Nasledujúce příklady ilustrujú, ale neobmedzujú predmet vynálezu.The following examples illustrate but do not limit the scope of the invention.
Příklad 1Example 1
Z reakčnej zmesi, pripravenej hydrogenačnou alkyláciou 2-metyl-6-etylanilínu metoxyppropanónom, pozostávajúcej z 36,0 g 2-metyl -6-etyl-N-(r-metoxy-2’-propyí)anilínu, 0,1 g 2metyl-6-etylanilínu, 2,7 g metoxypropanónu, 49,6 g l-metoxy-2-propanolu, 3,2 g vody, 1,5 g 2-metyl-6-etyl-N-(l’-metoxy-2’-propyl)anilín di(trihydrogénfosfátu) sa odfiltroval použitý platinový hydrogenačný katalyzátor na aktívnom uhlí (80 mg s obsahom platiny 5 %). Z filtrátu sa odstránila reakčná voda a nezreagovaný metoxypropanón s časťou l-metoxy-2-propanolu rektifikáciou pri teplote 93 až 118 °C na hlavě kolony. Ďalšiu frakciu s teplotou varu 118 až 121 °C tvořil bezvodý l-metoxy-2-propanol, pričom po připojení vakua sa oddestilovali ďalšie podiely l-metoxy-2-propanolu. Destilovač zvyšok sa počas rektifikácie rozdělil na dve vrstvy. Horná vrstva sa podrobila vákuovej destilácii, pričom predné podiely tvoriace zmes 1 -metoxy-2-propanolu, 2-metyl-6-etylanilínu a časti 2-metyl-6-etyl-N-(l’-metoxy-2’-propyl)anilínu sa vrátili do ďalšieho cyklu hydrogenačnej alkylácie. Hlavná frakcia 2-metyl -6-etyl-N-(T-metoxy-2’-propyl)anilínu vydestilovala pri 88°C/3,7Pa v množstve 34,0 g. Spodná vrstva obsahujúca protonový katalyzátor v množstve 1,5 g sa rozpustila bez ochladenia v 7,5 g l-metoxy-2-propanolu a vrátila sa do ďalšieho cyklu hydrogenačnej alkylácie. Z odfiltrovaného platinového hydrogenačného katalyzátora sa časť (20 %) oddělila na regeneráciu a zvyšok po doplnění čerstvým katalyzátorem sa vrátil do ďalšieho stupňa hydrogenačnej alkylácie.From a reaction mixture prepared by hydrogenation alkylation of 2-methyl-6-ethylaniline with methoxypropropanone, consisting of 36.0 g of 2-methyl-6-ethyl-N- (r-methoxy-2'-propyl) aniline, 0.1 g of 2-methyl- 6-ethylaniline, 2.7 g methoxypropanone, 49.6 g 1-methoxy-2-propanol, 3.2 g water, 1.5 g 2-methyl-6-ethyl-N- (1'-methoxy-2 ' -propyl) aniline di (trihydrogen phosphate) the used platinum hydrogenation catalyst was filtered off on activated carbon (80 mg with a platinum content of 5%). The water of reaction and unreacted methoxypropanone with a portion of 1-methoxy-2-propanol were removed from the filtrate by rectification at 93-118 ° C at the top of the column. Another fraction with a boiling point of 118-121 ° C was anhydrous 1-methoxy-2-propanol, while further portions of 1-methoxy-2-propanol were distilled off after applying a vacuum. The distillation residue was divided into two layers during rectification. The upper layer was subjected to vacuum distillation, the front portions being a mixture of 1-methoxy-2-propanol, 2-methyl-6-ethylaniline and a portion of 2-methyl-6-ethyl-N- (1'-methoxy-2'-propyl). of aniline were returned to the next hydrogen alkylation cycle. The main fraction of 2-methyl-6-ethyl-N- (T-methoxy-2'-propyl) aniline was distilled off at 88 ° C / 3.7 Pa in an amount of 34.0 g. The lower layer containing 1.5 g of proton catalyst was dissolved without cooling in 7.5 g of 1-methoxy-2-propanol and returned to the next hydrogenation alkylation cycle. A portion (20%) of the filtered platinum hydrogenation catalyst was separated for regeneration and the residue, after addition of fresh catalyst, was returned to the next hydrogenation alkylation step.
Příklad 2Example 2
Reakčná zmes připravená hydrogenačnou alkyláciou 2-metyl-6-etylanilínu metoxypropanónom rovnakého zloženia ako v příklade 1 sa ochladila a umiestnila v sedimentačnej nádobě, kde sa nechala sedimentovať počas 5 hod. Usadený platinový hydrogenačný katalyzátor sa odpustil a horná číra vrstva sa podrobila vákuovej destilácii. Pri tlaku 2,7 kPa a teplote do 100 °C vydestilovali prchavé podiely obsahujúce vodu, metoxypropánom a 1 -metoxy-2-propanol. Táto zmes sa potom rozdělila na rektifikačnej kolóne pri atmosférickom tlaku na azeotropné zmesi s teplotou varu 93 až 118 °C a bezvodý l-metoxy-2-propanol s teplotou varu 118 až 121 °C. Destilačný zvyšok zložený zo zmesi l-metoxy-2-propanolu, 2-metyl-6-etylanilínu a časti 2-metyl-6-etyl-N-(T-metoxy-2’ -propyl)anilínu sa vrátil do ďalšieho cyklu hydrogenačnej alkylácie. Oddestilovaním prchavých podielov zahuštěná reakčná zmes sa rozdělila na dve fázy. Spodná viskózna fáza pozostávajúca z protonového katalyzátora a jemnej disperzie zvyškov nesedimentovaného platinového hydrogenačného katalyzátora sa vypustila do l-metoxy-2-propanolu a po doplnění čerstvým protonovým katalyzátorem sa použila v ďalšom cykle hydrogenačnej alkylácie. HorThe reaction mixture prepared by hydrogenation alkylation of 2-methyl-6-ethylaniline with methoxypropanone of the same composition as in Example 1 was cooled and placed in a sedimentation vessel, where it was allowed to settle for 5 hours. The settled platinum hydrogenation catalyst was discarded and the upper clear layer was subjected to vacuum distillation. Volatiles containing water, methoxypropane and 1-methoxy-2-propanol were distilled off at a pressure of 2.7 kPa and a temperature of up to 100 ° C. This mixture was then separated on a rectification column at atmospheric pressure into azeotropic mixtures boiling at 93-118 ° C and anhydrous 1-methoxy-2-propanol boiling at 118-121 ° C. The distillation residue, consisting of a mixture of 1-methoxy-2-propanol, 2-methyl-6-ethylaniline and part of 2-methyl-6-ethyl-N- (T-methoxy-2'-propyl) aniline, was returned to the next hydrogenation alkylation cycle. . The reaction mixture, concentrated by distilling off the volatiles, was divided into two phases. The lower viscous phase consisting of the proton catalyst and a fine dispersion of non-sedimented platinum hydrogenation catalyst residues was discharged into 1-methoxy-2-propanol and, after addition of fresh proton catalyst, used in the next hydrogenation alkylation cycle. Hor
CS 267 385 Bl ná fáza destilačného zvyšku sa podrobila vákuovej destilácii. Prvé podiely, pozostávajúce zo zmesi l-mctoxy-2-propanolu, 2-metyl-6-etylanilánu a 2-inetyl-6-etyl-N-(í’-metoxy-2’-propyl)a nil inu sa vrátili <l<> ďalšieho cyklu hydro genačnej alkylácie a ako hlavná Irakcia sa vydestilovala 2-metyl-6-etyl-N-(r-metoxy-2’-piOpyl)anilín s teplotou varu 129 až 131 C/ 1,33 kPa. Použitý platinový hydrogenačný katalyzátor oddělený v sedimentačnej nádobě, sa po doplnění čerstvým katalyzátorem použil v ďalšom cykle hydrogenačnej alkylácie.The white phase of the distillation residue was subjected to vacuum distillation. The first portions, consisting of a mixture of 1-methoxy-2-propanol, 2-methyl-6-ethylanilane and 2-methyl-6-ethyl-N- (1'-methoxy-2'-propyl) and niline, were returned. 2> methyl-6-ethyl-N- (r-methoxy-2'-propyl) aniline with a boiling point of 129-131 ° C / 1.33 kPa was distilled off as the main hydrogenation alkylation cycle. The platinum hydrogenation catalyst used, separated in a sedimentation vessel, was used in the next hydrogenation alkylation cycle after replenishment with fresh catalyst.
Příklad 3Example 3
Reakčná zmes připravená hydrogenačnou alkyláciou 2-nietyl-6-etylanilinu metoxypropanónom rovnakého zloženia ako v příklade 1 sa zbavila prchavých podielov a rozpúšťadla rektifikáciou postupem opísaným v příkladu I. Destilačný zvyšok obsahoval dve fázy. Horná vrstva sa bez ochladenia přečerpala na vákuovú destiláciu, kterou sa získal 2-inetyl-6-etyl-N-(l’metoxy-2’-propyl)anilín. Spodná viskózna fáza pozostávajúca z disperzie platinového hydrogenačného katalyzátora na aktívnom uhlí ako nosiči s obsahom platiny 5 % v protonovém katalyzátore sa rozpustila za horúca v přebytku 1-metoxy-2-propanolu na 2%-nú koncentráciu a po doplnění čerstvého protónového a platinového hydrogenačného katalyzátora sa použila v ďalšom cykle hydrogenačnej alkylácie.The reaction mixture prepared by hydrogenation alkylation of 2-methyl-6-ethylaniline with methoxypropanone of the same composition as in Example 1 was stripped of volatiles and solvent by rectification as described in Example I. The distillation residue contained two phases. The upper layer was pumped without vacuum distillation to give 2-methyl-6-ethyl-N- (1'-methoxy-2'-propyl) aniline. The lower viscous phase consisting of a dispersion of a platinum hydrogenation catalyst on activated carbon as a support containing 5% platinum in a proton catalyst was dissolved hot in excess of 1-methoxy-2-propanol to a concentration of 2% and after addition of fresh proton and platinum hydrogenation catalyst. was used in the next hydrogen alkylation cycle.
Příklad 4Example 4
Reakčná zmes připravená hydrogenačnou alkyláciou 2-metyl-6-etylanilínu metoxypropanónom rovnakého zloženia ako v příklade 1 sa z autoklávu premiestnila do sedimentačnej nádoby, kde sa nechal usadit’ platinový hydrogenačný katalyzátor. Číra zmes sa potom dekantovala a zahustila oddestilovaním vody, metoxypropanónu a l-metoxy-2-propanolu. K destiiačnému zvyšku rozdělenému na dve fázy sa přidalo za miešania a bez ochladenia 0,75 ml vody. Viskózna fáza protónového katalyzátoraThe reaction mixture prepared by hydrogenation alkylation of 2-methyl-6-ethylaniline with methoxypropanone of the same composition as in Example 1 was transferred from the autoclave to a sedimentation vessel where a platinum hydrogenation catalyst was allowed to settle. The clear mixture was then decanted and concentrated by distilling off water, methoxypropanone and 1-methoxy-2-propanol. To the distillation residue divided into two phases, 0.75 ml of water was added with stirring and without cooling. Viscous phase of a proton catalyst
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS884269A CS267385B1 (en) | 1988-06-20 | 1988-06-20 | Method of 2,6-dialkyl-n-/1-methoxy-2-propyl/anilines preparation |
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| CS884269A CS267385B1 (en) | 1988-06-20 | 1988-06-20 | Method of 2,6-dialkyl-n-/1-methoxy-2-propyl/anilines preparation |
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| CS267385B1 true CS267385B1 (en) | 1990-02-12 |
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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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Cited By (1)
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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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| CS426988A1 (en) | 1989-06-13 |
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