CS267073B1 - A method for preparing aryloxyalkanecarboxylic acids - Google Patents

A method for preparing aryloxyalkanecarboxylic acids Download PDF

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CS267073B1
CS267073B1 CS869793A CS979386A CS267073B1 CS 267073 B1 CS267073 B1 CS 267073B1 CS 869793 A CS869793 A CS 869793A CS 979386 A CS979386 A CS 979386A CS 267073 B1 CS267073 B1 CS 267073B1
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catalyst
compounds
oxygen
amount
acids
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CS979386A1 (en
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Juraj Ing Tuleja
Milan Ing Csc Hronec
Zuzana Ing Csc Cvengrosova
Jan Prof Ing Drsc Ilavsky
Stefaneing Csc Truchlik
Anna Ing Tulejova
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Tuleja Juraj
Hronec Milan
Cvengrosova Zuzana
Ilavsky Jan
Stefaneing Csc Truchlik
Anna Ing Tulejova
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Abstract

Riešenie sa týká spósobu pripravy aryloxyalkánkarboxylových kyselin oxidáciou aryloxyalkoholov kyslíkom alebo kyslík obsahujúcim plynom vo vodno-alkalickom prostředí pri teplote 50 až 110 °C a tlaku 0,1 až 1,0 MPa v přítomnosti katalyzátora, ktorým je paládium nanesené v množstve 2 až 8 % hmot. na anorganickom nosiči, aktivované zlúčeninami mangánu alebo kobaltu samotnými alebo v kombinácii so zlúčeninami kadmia, alebo kombináciami zlúčenin bizmutu so zlúčeninami zinku, pričom množstvo katalyzátora vztiahnuté na aryloxyalkohol je 0,5 až 20 % hmot. a množstvo aktivátora 10~5 až 10"^ molu zlúčeniny kovu na 1 mól aryloxyalkoholu. Riešenie je možné využiť v chemickom priemysle.The solution relates to a method for preparing aryloxyalkanocarboxylic acids by oxidizing aryloxyalcohols with oxygen or an oxygen-containing gas in an aqueous-alkaline environment at a temperature of 50 to 110 °C and a pressure of 0.1 to 1.0 MPa in the presence of a catalyst, which is palladium deposited in an amount of 2 to 8 wt. % on an inorganic support, activated by manganese or cobalt compounds alone or in combination with cadmium compounds, or by combinations of bismuth compounds with zinc compounds, wherein the amount of catalyst relative to the aryloxyalcohol is 0.5 to 20 wt. % and the amount of activator is 10~5 to 10"^ mole of metal compound per 1 mole of aryloxyalcohol. The solution can be used in the chemical industry.

Description

Vynález sa týká sposobu přípravy aryloxyalkánkarboxylových kyselin oxidáciou aryloxyalkoholov kyslíkom alebo kyslík obsahujúcim plynom vo vodno-alkalickom prostředí za přítomnosti katalyzátora.The present invention relates to a process for the preparation of aryloxyalkanecarboxylic acids by the oxidation of aryloxyalcohols with oxygen or an oxygen-containing gas in an aqueous-alkaline medium in the presence of a catalyst.

Fenoxyoctové kyseliny sú hodnotné medziprodukty a majú hospodářsky význam ako herbicidy. Dóležitú skupinu herbicídov tvoria fenoxyoctové kyseliny substituované na benzénovom jadre, ako napr. 2-metyl-4-chlórfenoxyoctové kyselina, 2,4-dichlór-fenoxyoctová kyselina a 2-(2-metyl-4-chlórfenoxy)-propánkarboxylová kyselina. Tieto zlúčeniny sa technicky pripravujú zahrievaním příslušných fenolov s kyselinami (monochlóroctovou alebo 2-chlórpropiónovou) v přebytku vodného roztoku hydroxidu sodného. Pri tomto postupe je však nutné pracovat s prebytkom príslušnej kyseliny, ktorá sa znehodnotí pri izolácii produktu.Phenoxyacetic acids are valuable intermediates and are of economic importance as herbicides. An important group of herbicides are phenoxyacetic acids substituted on the benzene nucleus, such as e.g. 2-methyl-4-chlorophenoxyacetic acid, 2,4-dichlorophenoxyacetic acid and 2- (2-methyl-4-chlorophenoxy) propanecarboxylic acid. These compounds are technically prepared by heating the corresponding phenols with acids (monochloroacetic or 2-chloropropionic) in excess aqueous sodium hydroxide solution. In this procedure, however, it is necessary to work with an excess of the appropriate acid, which is degraded when the product is isolated.

Z ekologického hXadiska sú výhodnéjšie oxidačně postupy, ^ri ktorých sa příslušný alkohol oxiduje vzduchom alebo kyslíkom v přítomnosti Pd/C, resp. Pt/C katalyzátorov vo vodno-alkalickom prostředí. Obsah platinových kovov na nosiči sa mění v rozmedzí 2,5 až 10 % hmot. (Ioffe I. I. Nikolsev Ju. T., Brodskij M. S.: Kinetika i kataliz. 1, 125 /1960/; SU 130 510) . Nevýhodou tohoto postupu je, že pri použití katalyzátorov typu Pt/C reakcia je málo selektívna, pričom prebieha oxidačně štiepenie za vzniku příslušného fenolu a 003. Ďalšou nevýhodou je, že sa musí používat čerstvo připravený katalyzátor, musí sa pracovat s nízkou koncentráciou fenoxyetanolu a pri opátovnom použití katalyzátora prudko klesá výtažok fenoxyoctovéj kyseliny (Ioffe I. I. Nikolaev Ju. T., Suchareva G. A. Ž. fiz. chim. 42, 266 /1968/) . *From an ecological point of view, oxidation processes are more preferred in which the corresponding alcohol is oxidized with air or oxygen in the presence of Pd / C and Pd / C, respectively. Pt / C catalysts in aqueous-alkaline medium. The content of platinum metals on the support varies between 2.5 and 10% by weight. (Ioffe I. I. Nikolsev Ju. T., Brodskij M. S .: Kinetics and Cat. 1, 125 (1960); SU 130 510). The disadvantage of this process is that when using Pt / C catalysts the reaction is not very selective, the oxidative cleavage takes place to give the corresponding phenol and 003. Another disadvantage is that a freshly prepared catalyst must be used, a low concentration of phenoxyethanol must be used and re-use of the catalyst sharply decreases the yield of phenoxyacetic acid (Ioffe II Nikolaev Ju. T., Suchareva GA Ž. fiz. chim. 42, 266 (1968)). *

V GB 1 590 614 je opísané použitie samotného paládia ako katalyzátora oxidácie monoalkyl, resp. monoalkylaryléterov polyetylénglykolu alebo polypropylénglykolu alebo ich zmesi, chemicky značné odlišných od jednoduchých substituovaných fenyl-2-hydroxyetyléterov, resp. fenyl-2-hydroxy-l-metyléterov.GB 1 590 614 describes the use of palladium alone as a catalyst for the oxidation of monoalkyl and monoalkylaryl ethers of polyethylene glycol or polypropylene glycol or mixtures thereof, chemically significantly different from simple substituted phenyl-2-hydroxyethyl ethers, respectively. phenyl 2-hydroxy-1-methyl ethers.

Predmetom EP 73 545 je spósob přípravy éterkarboxylátov oxidáciou éteralkoholov s 88percentnou konverziou, avšak v přítomnosti zmesi Pt a Pd katalyzátora.EP 73 545 relates to a process for the preparation of ether carboxylates by oxidation of ether alcohols with 88% conversion, but in the presence of a mixture of Pt and Pd catalyst.

Výrazné zvýšenie aktivity a selektivity katalyzátora sa uvádza v DE 2 851 788, podlá ktorého sa oxidácia aryloxyetanolov uskutečňuje v přítomnosti Pt alebo Pd katalyzátora dopovaného aktivátormi, kterými sú zlúčeniny olova alebo bizmutu samotné alebo v kombinaci! s kadmiom, resp. jeho zlúčeninami.A significant increase in the activity and selectivity of the catalyst is disclosed in DE 2 851 788, according to which the oxidation of aryloxyethanes is carried out in the presence of a Pt or Pd catalyst doped with activators which are lead or bismuth compounds alone or in combination. with cadmium, resp. its compounds.

Teraz sa zistilo, že aryloxyalkánkarboxylové kyseliny všeobecného vzorca IIt has now been found that aryloxyalkanecarboxylic acids of formula I

(I) v ktorom R znamená vodík alebo metyl a R1 a R4 sú rovnaké alebo rožne a znamenajú vodík, chlór alebo metyl, je možné pripraviť oxidáciou aryloxyalkoholov všeobecného vzorca II(I) in which R represents hydrogen or methyl and R 1 and R 4 are the same or various and represent hydrogen, chlorine or methyl, can be prepared by oxidation of aryloxyalcohols of general formula II

(II) v ktorom R, R , R majú už uvedený význam, kyslíkom alebo kyslík obsahujúcim plynom vo vodno-alkalickom prostředí pri teplote 50 až 110 °C, tlaku 0,1 až 1,0 MPa v přítomnosti katalyzátora, kterým je paládium nanesené v množstve 2 až 8 % hmot, na anorganickom nosiči podlá vynálezu. Podstata vynálezu spočívá v tom, že paládium je aktivované zlúčeninami mangánu alebo kobaltu samotnými alebo v kombinácii so zlúčeninami kadmia, alebo kombináciou zlúčenín(II) in which R, R, R are as defined above, with oxygen or an oxygen-containing gas in an aqueous-alkaline medium at a temperature of 50 to 110 ° C, a pressure of 0.1 to 1.0 MPa in the presence of a palladium-supported catalyst in an amount of 2 to 8% by weight, on the inorganic carrier according to the invention. The essence of the invention is that palladium is activated by manganese or cobalt compounds alone or in combination with cadmium compounds, or by a combination of compounds

CS 267 073 Bl bizmutu so zlúčeninami zinku. Množstvo katalyzátora vztiahnuté na aryloxyalkc. ' e 0,5 * -5 -4 - až 20 i hmot, a množstvo aktivátorov 10 až 10 molu zlúčeniny kovu na 1 mol aryloxyalkoholu.CS 267 073 B1 bismuth with zinc compounds. Amount of catalyst based on aryloxyalk. 0.5 to -5% by weight, and the amount of activators are 10 to 10 moles of the metal compound per mole of aryloxyl alcohol.

Ako nosič sa m8že použit aktivně uhlie alebo CaCOj. Aktivátory sa přidávájú ku katalyzátoru Pd/nosič vo forme vodných roztokov, resp. roztokov zriedených kyselin, z ktorých v přítomnosti zásad vzniknú příslušné nerozpustné zlúčeniny.Activated carbon or CaCO 3 can be used as a carrier. The activators are added to the Pd catalyst / support in the form of aqueous solutions, resp. solutions of dilute acids from which the corresponding insoluble compounds are formed in the presence of bases.

Oxidácia podlá vynálezu sa uskutočňuje v přítomnosti alkálií, napr. NaOH, KOH ale aj Na2CO3, K2CO3· Množstvo alkálií sa volí tak, že na 1 mól oxidáciou vzniknutéj -COOH skupiny sa přidá 0,5 až 5 mólov, s výhodou 1 až 3 moly alkálie.The oxidation according to the invention is carried out in the presence of alkalis, e.g. NaOH, KOH but also Na 2 CO 3 , K 2 CO 3 · The amount of alkali is chosen by adding 0.5 to 5 mol, preferably 1 to 3 mol, of alkali per 1 mol of oxidation-formed -COOH group.

Koncentrácia oxidovaného aryloxyalkoholu sa volí tak, aby vznikajúca aryloxyalkánkarboxylová kyselina zostávala počas reakcie rozpustná v reakčnom prostředí a nevypadávala ako tuhá fáza. Vhodné sú koncentrácie od 5 do 30 % hmot.The concentration of oxidized aryloxyalcohol is chosen so that the resulting aryloxyalkanecarboxylic acid remains soluble in the reaction medium during the reaction and does not appear as a solid phase. Concentrations of 5 to 30% by weight are suitable.

Výhoda spósobu podlá vynálezu spočívá v tom, že na aktiváciu, Pd-katalyzátora možno použit bežne dostupné zlúčeniny.The advantage of the process according to the invention is that commercially available compounds can be used to activate the Pd catalyst.

mangánu (Mn/NO,/o . 6 H,0, MnCl, . 4 H,0, MnSO. . 7 H„0),manganese (Mn / NO, / o . 6 H, 0, MnCl,. 4 H, 0, MnSO.. 7 H „0),

Z z £ z ty z kobaltu (Co/N03/2 . 6 H2O, CoCl2 . 6 H2O, CoS04 . 7 H2O), kadmia (CdCl2, Cd/NO3/2 . 4 H2O, CdSO4), bizmutu (Bi/NO3/3 . 5 H2O, BiClj), zinku (ZnCl2, ZnSO4 . 7 H2O, Zn/NO3/2 . 6 H2O).Of the £ of the cobalt (Co / N0 3/2. 6H 2 O, CoCl second 6H 2 O, CoS0 fourth 7H 2 O), cadmium (CdCl 2, Cd / NO 3 / second 4 H 2 O, CDSO 4), bismuth (Bi / NO 3/5. 3 H 2 O, BiClj), zinc (ZnCl 2, ZnSO fourth 7H 2 O, Zn / NO 3 / second 6 H 2 O) .

Použitím aktivátorov Pd-katalyzátora podlá vynálezu sa výrazné skráti reakčný čas oproti tomu, ked sa použije Pd-katalyzátor bez aktivátorov a dosiahne sa vysoká selektivita a životnost Pd-katalyzátora. S takto aktivovaným Pd-katalyzátorom je naviac možné pracovat pri nízkom tlaku kyslíka a vysokej koncentrácii oxidovaného aryloxyalkoholu v násadě .By using the Pd-catalyst activators according to the invention, the reaction time is significantly shortened compared to using a Pd-catalyst without activators and a high selectivity and service life of the Pd-catalyst is achieved. In addition, it is possible to work with the Pd catalyst thus activated at low oxygen pressure and a high concentration of oxidized aryloxyl alcohol in the batch.

Uvedené příklady ilustrujú, ale neobmedzujú predmet vynálezu.The following examples illustrate but do not limit the scope of the invention.

Příklad 1Example 1

Do 100 ml miešaného poloprietokového reaktora z nehrdzavejúcej ocele, opatřeného meračom teploty, prívodom a odvodom plynu, vonkajším plášťom na ohřev reaktora sa nadávkovalo 0,65 gramov katalyzátora (aktivně uhlie s obsahom 5 % hmot. Pd), 1 ml kyslého roztoku Mn/NO3/2 . . 6 H2O s obsahom 0,015 g Mn/NO3/ . 6 H2O, 50 ml 2,7 N NaOH a 15,2 g 2-metylfenoxyetanolu.0.65 grams of catalyst (activated carbon with 5% w / w Pd), 1 ml of acidic Mn / NO solution were metered into 100 ml of a stirred stainless steel semi-flow reactor equipped with a temperature meter, gas inlet and outlet, outer jacket for heating the reactor. 3/2. . 6 H 2 O containing 0.015 g Mn (NO 3 ). 6 H 2 O, 50 ml of 2.7 N NaOH and 15.2 g of 2-methylphenoxyethanol.

Po vypudení vzduchu z reakčnej nádoby kyslíkom sa zaplo miešanie a reakčná zmes sa zahriala na 80 °C. Pri tejto teplote sa zavádzal do reakčnej zmesi kyslík pri tlaku 0,2 MPa. Priebeh reakcie sa kontroloval v pravidelných intervaloch analýzou obsahu kyslíka v odplyne a reakcia sa ukončila, ked už nedochádzalo k spotřebovávanou kyslíka ~-180 min. Po ukončení reakcie sa za tepla odfiltroval z reakčnej zmesi katalyzátor a filtrát sa okyslil 2N roztokom kyseliny chlorovodíkovéj na pH = 1.After expelling air from the reaction vessel with oxygen, stirring was started and the reaction mixture was heated to 80 ° C. At this temperature, oxygen was introduced into the reaction mixture at a pressure of 0.2 MPa. The progress of the reaction was checked at regular intervals by analyzing the oxygen content of the off-gas and the reaction was terminated when there was no more oxygen consumption ~ -180 min. After completion of the reaction, the catalyst was filtered off from the reaction mixture while hot, and the filtrate was acidified with 2N hydrochloric acid solution to pH = 1.

Po odfiltrovaní a vysušení koláča sa získalo 15,6 g bielej kryštalickej látky, v ktoréj sa GLC analýzou stanovilo 0,4 % hmot, o-krezolu, 1,4 % hmot, nezreagovaného 2-metylfenoxyetanolu a 95,7 % hmot. 2-metylfenoxyoctovej kyseliny. Výťažok 2-metylfenoxyoctovej kyseliny představuje 90 % teorie.After filtration and drying of the cake, 15.6 g of white crystals were obtained, in which 0.4% by weight of o-cresol, 1.4% by weight, unreacted 2-methylphenoxyethanol and 95.7% by weight were determined by GLC analysis. 2-methylphenoxyacetic acid. The yield of 2-methylphenoxyacetic acid is 90% of theory.

Claims (1)

SOCIALISTICKÁ I POPIS VYNÁLEZU REPUBLIKA (19> K AUTORSKÉMU OSVEDtENIU 267 074 (11) CQ r> o rv toSOCIALISTIC AND DESCRIPTION OF THE INVENTION THE REPUBLIC (19> TO COPYRIGHT CERTIFICATE 267 074 (11) CQ r> o rv to FEDERÁLNÍ úřadPRO VYNÁLEZY (75) Autor vynálezu (54) (21) PV 39-87.K (22) Přihlášené 04 oi 87 (40) Zverejnené 12 05 89(45) Vydané 14 12 90 (13) B1 (51) Int. Cl? F 16 K 11/00A 61 M 5/32 SMIGÁŇ PETER RNDr. CSC., BRATISLAVA, PECHAN ZDENĚK RNDr. CSc., BRNO, ŠMIGÁŇOVÁ ALENA, BRATISLAVA Miniatúrny preplachovací trojcestný kohút (57) Miniatúrny preplachovací trojcestnýkohút je určený pre biochemické a podobnélaboratória, najma pre prácu v anaeróbnomprostředí. Rieši manipuláciu s inertnýmiplynmi, napr. zmesou oxid uhličitý - vodík,alebo anaerobizovanými roztokmi, leh převoddo kultivačných skúmaviek alebo nádob, po-případě rozplúovanie roztokov. V plášti ko-húta sú vytvořené přívod v tvare vnútornéhokónického zábrusu s kuželovitosťou 6:100 nanasadenie injekčnej striekačky a dva vývodyv tvare vonkajšieho kónického zábrusu s ku-želovitosťou 6:100 na nasadenie injekčnýchihiel.FEDERAL OFFICE FOR INVENTIONS (75) Author of Invention (54) (21) PV 39-87.K (22) Registered 04 oi 87 (40) Published 12 05 89 (45) Published 14 12 90 (13) B1 (51) Int. Cl? F 16 K 11 / 00A 61 M 5/32 SMIGÁŇ PETER RNDr. CSC., BRATISLAVA, PECHAN ZDENEK RNDr. CSc., BRNO, ŠMIGÁŇOVÁ ALENA, BRATISLAVA Miniature flush three-way cock (57) The miniature flush three-way cock is designed for biochemical and similar laboratories, especially for work in anaerobic environment. It solves the handling of inert gases, for example carbon dioxide-hydrogen, or anaerobized solutions, easily transferred to culture tubes or containers, if necessary, by dissolving solutions. An inner-conical inlet with a 6: 100 taper of the syringe and two outlets in the shape of an external conical cone with a spur of 6: 100 for injection molding are formed in the co-hull shell.
CS869793A 1986-12-22 1986-12-22 A method for preparing aryloxyalkanecarboxylic acids CS267073B1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102180789A (en) * 2011-03-25 2011-09-14 山东潍坊润丰化工有限公司 Method for preparing aryloxycarboxylic acid technical

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102180789A (en) * 2011-03-25 2011-09-14 山东潍坊润丰化工有限公司 Method for preparing aryloxycarboxylic acid technical

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