SI8811413A - Procedure for the production of acylated imidazoles and pyrazoles. - Google Patents

Procedure for the production of acylated imidazoles and pyrazoles. Download PDF

Info

Publication number
SI8811413A
SI8811413A SI8811413A SI8811413A SI8811413A SI 8811413 A SI8811413 A SI 8811413A SI 8811413 A SI8811413 A SI 8811413A SI 8811413 A SI8811413 A SI 8811413A SI 8811413 A SI8811413 A SI 8811413A
Authority
SI
Slovenia
Prior art keywords
carbon atoms
catalyst
zeolite
acid
aryl
Prior art date
Application number
SI8811413A
Other languages
Slovenian (sl)
Inventor
Helmut Lermer
Wolfgang Hoelderich
Toni Dockner
Hermann Koehler
Original Assignee
Basf Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE19873724035 external-priority patent/DE3724035A1/en
Application filed by Basf Ag filed Critical Basf Ag
Publication of SI8811413A publication Critical patent/SI8811413A/en

Links

Landscapes

  • Catalysts (AREA)

Abstract

Opisan je postopek pridobivanja aciliranih imidazolov in pirazolov s I, v kateri sta R 2 in R3 enaka ali različna in vsak lahko pomeni vodik, Ci-12-alkilni, Ci-12-alkenilni, Ci-i2alkoksilni, arilni, aralkilni ali alkilarilni ostanek, R4 pomeni vodik, Ci-12-alkilni, Ci-i2-alkenilni, arilni, aralkilni ali alkilarilni ostanek. R5 pomeni C1'12-alkilni, Ci-12-alkenilni, arilni, aralkilni ali karboksi ostanek. Postopek obsega reakcijo ustreznega imidazola ali pirazola s sredstvom za aciliranje s formulo V, 0 R3 - C - T kjer Y pomeni halogenidni, alkoksi, hidroksi, amidni in karboksi ostanek, pri temperaturi v plinasti fazi od 300 do 600 stopinj Celzija in od 50 do 300 stopinj Celzija v tekoči fazi, v prisotnosti zeolita kot kata- lizatorja.The process of obtaining acylated imidazoles is described and pyrazoles of I in which R 2 and R 3 are the same or different and each can be means hydrogen, C1-12 alkyl, C1-12 alkenyl, C1-12 alkoxy, an aryl, aralkyl or alkylaryl radical, R4 is hydrogen, C1-12 alkyl, C1-12 alkenyl, aryl, aralkyl or an alkylaryl residue. R5 is C1-12 alkyl, C1-12 alkenyl, an aryl, aralkyl or carboxy radical. Process comprises the reaction of the corresponding imidazole or pyrazole s an acylating agent of formula V, 0 R3 - C - T wherein Y is halide, alkoxy, hydroxy, amide and carboxy residue, at a gas phase temperature of 300 up to 600 degrees Celsius and 50 to 300 degrees Celsius in liquid phase, in the presence of zeolite as a catalyst.

Description

POSTUPAK ZA DOBIVANJE ACILOVANIH IMIDAZOLA I PIRAZOLAPROCEDURE FOR OBTAINING ACYLATED IMIDAZOLES AND PIRAZOLES

Ova prijava se odnosi na postupak za dobivanje acilovanih imidazola i pirazola direktnim acilovanjem odgovarajučih nesupstituisanih ili supstituisanih imidazola i pirazola sa sredstvima za acilovanje u prisustvu katalizatora.This application relates to a process for the preparation of acylated imidazoles and pyrazoles by directly acylating the corresponding unsubstituted or substituted imidazoles and pyrazoles with acylating agents in the presence of a catalyst.

Direktna C-acilovanja imidazola u Friedel-Crafts-ovim reakcijama nisu bila poznata odnosno smatralo se da tehnički nisu izvodljiva (A.R. Katritzky, G.W. Rees, Comprehensive Heterocyclic Chemistry, Vol. 5» str. 402 (1984)» Pergamon Press: K. Hoffmann, The Chemistrv of IIeterocyclic Compounds, Vol. b: Imidazole and its derivativss, Part I, str. 49 i str. 59 (1953) Interscience Publishers).Direct C-acylation of imidazole in Friedel-Crafts reactions was not known or considered technically not feasible (AR Katritzky, GW Rees, Comprehensive Heterocyclic Chemistry, Vol. 5 »P. 402 (1984)» Pergamon Press: K. Hoffmann , The Chemistry of IIeterocyclic Compounds, Vol. B: Imidazole and its derivatives, Part I, pp. 49 and 59 (1953) Interscience Publishers).

Zbog toga se moralo priči drugim moguinostima za ovo dobivanje, napr. primenjivalo se fotohemijsko prenestanje N-acetilimidazola (J.L. La Uattina et al., J. Org. Chem. Αθ» 897-8 (1983), ili reagovanje 4-formilimidazola sa Grinjarovim reagensom i narodna oksidacija (napr. R. Paul et al., J. Med. Chem. 28, 1704-16 (1985), ili hidrogenoliza 4-acilamino-5-metilizoksazola (SP 156 644, Pfizer).Therefore, there was a need to talk about other options for this, for example. the photochemical transfer of N-acetylimidazole (J. L. La Uattina et al., J. Org. Chem. Αθ »897-8 (1983)) or the reaction of 4-formylimidazole with Grignard reagent and folk oxidation (eg R. Paul et al. , J. Med. Chem. 28, 1704-16 (1985), or hydrogenolysis of 4-acylamino-5-methylisoxazole (SP 156 644, Pfizer).

Medjutim, ove metode su komplikovane i ne mogu se izvoditi u tehnickim razmerama (industrijskim razmerama).However, these methods are complicated and cannot be performed on a technical scale (industrial scale).

Takodje i jezgro pirazola nije pristupačno za FriedelCrafts-ovu reakciju acilovanja. Zbog toga su acilpirazoli dobivani uz priaenu komplikovanih postupaka, napr. reakcijom pirazol-3-karbonilhlorida sa benzolom (Frledel-Crafts-ova reakcija) ili sintezom pirazolovog jezgra iz odgovarajuče supstituisanih acikličnih polaznih jedinjenja (The Chemistry of Heterocyclic Compounds, Vol. 20, R.H. Hiley (izdavač), str. 117-124 (1967)).Also the pyrazole nucleus is not accessible to FriedelCrafts acylation reaction. Therefore, acylpyrazoles have been prepared by the use of complicated procedures, e.g. reaction of pyrazole-3-carbonyl chloride with benzene (Frledel-Crafts reaction) or synthesis of pyrazole nucleus from suitably substituted acyclic starting compounds (The Chemistry of Heterocyclic Compounds, Vol. 20, RH Hiley (publisher), pp. 117-124 (1967 )).

Do sada nije opisano tehnički interesantno direktno acilovanje na jezgru pirazola.So far, no technically interesting direct acylation to the pyrazole nucleus has been described.

Sada je nadjeno da se direktno C-acilovani imidazoli i pirazoli formula (i) i (II)It has now been found that directly C-acylated imidazoles and pyrazoles of formulas (i) and (II)

R5 0R 5 0

O/O /

R' 0 n u IIR '0 n in II

GMr

C-R (DC-R (D

R3 R 3

II

G- GG- G

II HII H

C h 7 C h 7

- R' (II)- R '(II)

R'R '

3 u kojima R IR mogu biti isti ili različiti i nezavisno jedan od drugog oznacavati H, alkil sa 1 do 12 atoma ugljenika, alkenil sa 1 do 12 atoma ugljenika, alkoksi sa 1 do 12 atoma ugljenika, aril, aralkil ili alkilarilostatke,3 in which R IR can be the same or different and independently of one another denote H, alkyl of 1 to 12 carbon atoms, alkenyl of 1 to 12 carbon atoms, alkoxy of 1 to 12 carbon atoms, aryl, aralkyl or alkylaryls.

R^ označava vodonik, alkil sa 1 do 12 atoma ugljenika, alkenil sa 1 do 12 atoma ugljenika, aril, aralkil ili alkilarilostatke,R4 denotes hydrogen, alkyl of 1 to 12 carbon atoms, alkenyl of 1 to 12 carbon atoms, aryl, aralkyl or alkylaryl residues,

r.....r .....

označava alkil.sa 1 do 12 atoma ugljenika, alkenil sa 1 do 12 atoma ugljenika, aril, aralkil, alkilaril ili karboksi-ostatke, dobivaju iz iaidazola odnosno pirazola formula (III) odnosnodenotes alkyl having 1 to 12 carbon atoms, alkenyl having 1 to 12 carbon atoms, aryl, aralkyl, alkylaryl or carboxy radicals, derived from iaidazole or pyrazole of formula (III) respectively

a u kojima R -R mogu oiti isti ili raziičiti i nezavisno jedan od drugog označavaju vodonik, alkil sa 1 do 12 atoma ugljenika, alkenil sa 1 do 12 atoma ugljenika, alkoksi sa 1 do 12 atoma ugljenika, aril, aailkil ili alkilaril-ostatke, pri čemi najmanje jedan od ovih ain which R-R may be the same or different and independently represent hydrogen, alkyl of 1 to 12 carbon atoms, alkenyl of 1 to 12 carbon atoms, alkoxy of 1 to 12 carbon atoms, aryl, aailkyl or alkylaryl radicals. whereby at least one of these a

ostataka R -R^ označava vodonik, iresidues R -R ^ denote hydrogen, i

R^ označava vodonik, alkil sa 1 do 12 atoma ugljenika, alkenil sa 1 do 12 atoma uugljenika, aril-, aralkilili alkilaril-ostatke, reakcijom 3a sredstvima za acilovanje formule (V) 0R 4 denotes hydrogen, alkyl of 1 to 12 carbon atoms, alkenyl of 1 to 12 carbon atoms, aryl-, aralkyl or alkylaryl radicals, reaction 3a by the acylating agents of formula (V) 0

IIII

R? - C - Y (V) u kojoj R ima gore dato značenje i Y označava halogenidni, alkoksi-, aciloksi-, hidroksi», amidni ili karboksi-ostatak,R ? - C - Y (V) in which R has the meaning given above and Y represents a halide, alkoxy, acyloxy, hydroxy, amide or carboxy radical,

Reakcija 2-metilimidazola sa anhidridom sirčetne kiseline do 4-acetil-2-metilimidazola u prisustvu zeolitskog katalizatora može se» na primer» predstaviti sledečom jednačinom sa formulama u prisustvu zeolitskih katalizatira.The reaction of 2-methylimidazole with acetic anhydride to 4-acetyl-2-methylimidazole in the presence of a zeolite catalyst can, for example, be represented by the following equation with the formulas in the presence of zeolite catalysts.

/Seolit// Seolite /

-p-p

-CH.COOH o-CH.COOH o

Analogna reakcija 4-metilimidazola daje uglavnom (večim delom) 5-acetil-4-netilimidazol, a pored toga takodje i 2-acetil-4-aetilimidazol.The analogous reaction of 4-methylimidazole yields (largely) 5-acetyl-4-nethylimidazole and in addition 2-acetyl-4-aethylimidazole.

Lledostaci poznatih visestepenih načina dobivanja su izbegnuti jronalaskon datim postupkom.The glaciers of known multi-step processes are avoided by the prior art.

elegantnoelegant

Za pronalaskom dati postupak pogodni heteroaromati su imidazoli i pirazoli gore datih formula (III) odnosno (IV), napr. imidazol, 2-metilimidazol» 1-metilimidazol, 4-aetilimidazol, 2-etil-4-metilimidazol, 4-n-butilimidazol, 2-izopropil imidazol, 2-izopropil-4-etilimidazol, 2,4-di-n-butilimidazol, 2-fenil-, 4-fenilimidazol, 4-benzilinidazol, pirazol, 3-m6tilpirazol, 3-n-butilpirazol, 3-izopropilpirazol, 4-fenilpirazol i 4-benzil-pirazol.The heteroaromatics suitable for the invention are imidazoles and pyrazoles of the above formulas (III) and (IV), e.g. imidazole, 2-methylimidazole »1-methylimidazole, 4-aethylimidazole, 2-ethyl-4-methylimidazole, 4-n-butylimidazole, 2-isopropyl imidazole, 2-isopropyl-4-ethylimidazole, 2,4-di-n-butylimidazole , 2-phenyl-, 4-phenylimidazole, 4-benzylinidazole, pyrazole, 3-methylpyrazole, 3-n-butylpyrazole, 3-isopropylpyrazole, 4-phenylpyrazole and 4-benzyl-pyrazole.

Kao sredstva za acilovanje za pronalaskom dati postupak mogu se primeniti poznata jedinjenja, napr. acetilhlorid, sirčetna kiselina, anhidrid sirčetne kiseline, metil-estar sirčetne kiseline, etil-estar sirčetne kiseline, amid sirčetne kiseline (acetamid), propionilhlorid, propionska kiselina, anhidrid pro^pionske kiseline, huterna kiselina, butirilhlorid, anhidrid buterne kiseline, izobuterna kiselina, izobutirilhlorid, anhidrid izobuterne kiseline, krotonska kiselina, anhidrid krotonske kiseline, izoprenska kiselina, vaierijanska kiselina, hlorid valerijanske kiseline, kapponska kiselina, estri kapronske kiseline, pivalinska kiselina, pivaloilhlorid, akrilna kiselina, metil-estar akrilne kiseline, netakrilna kiselina, efetri metakrilne kiseline, metil-estar penten-3-ove kiseline, metil-estar penten-2-ove kiseline, metil-estar penten-4-ove kiseline, sorbinska kiselina, metil-estar sorbinske kiseline, benzoeva kiselina, benzoilhlorid, metil-estar benzoeve kiseline, o-, m-, p-fluorbenzoeva kiselina, ο-, π-, p-fluorbenzoeve kiselina, o—, ρ-, ra-fluorbenzoilhlorid, o-, m-, p-hlorbenzoeva kiselina, o-, m-, p-metilbenzoeva kiselina, o-, m-, p-metilbenzoilklorid,, o-, a-, p-metoksibenzoeva kiselina, ο-, α-, p-metoksibenzoilhlorid, o-, m-, p-izopropilbenzoeva kiselina, ο-, π-, p-izopropil benzoilhlorid, 2,3-dimetil-, 2,3-digluor-, 2,3-dihlor-, 2,3dimetoksibenzoeva kiselina odnosno kloridi ovih kiselina, fenilsirčetna kiselina, fenilacetilhlorid, fenilacetanhidrid, cimetna kiselina, hlorid ciaetne kiseline, malonska kiselina, anhidrid aalonske kiseline, ftalna kiselina, anhidrid ftalne kiseline, tereftalna kiselina i tereftaloilhlorid.As the acylating agents of the present invention, known compounds may be used, e.g. acetyl chloride, acetic acid, acetic anhydride, acetic acid methyl ester, acetic acid ethyl ester, acetic acid amide (acetamide), propionyl chloride, propionic acid, propionic anhydride, butyric acid hydrochloride, butyrylhydride , isobutyryl chloride, isobutyric acid anhydride, crotonic acid, crotonic acid anhydride, isoprene acid, vaierian acid, valeric acid chloride, kapponic acid, capric acid esters, pivalic acid, pivaloyl chloride, acrylic acid, methyl acrylic acid, acrylic acid, methyl acrylic acid acids, pentene-3-acid methyl ester, pentene-2-acid methyl ester, pentene-4-acid methyl ester, sorbic acid, sorbic acid methyl ester, benzoic acid, benzoyl chloride, benzoyl ester acids, o-, m-, p-fluorobenzoic acid, ο-, π-, p-fluorobenzoic acid, o-, ρ-, ra-fluorobenzoyl chloride, o-, m-, ph lorbenzoic acid, o-, m-, p-methylbenzoic acid, o-, m-, p-methylbenzoyl chloride,, o-, a-, p-methoxybenzoic acid, ο-, α-, p-methoxybenzoyl chloride, o-, m -,, p-isopropylbenzoic acid, ο-, π-, p-isopropyl benzoyl chloride, 2,3-dimethyl-, 2,3-digluoro-, 2,3-dichloro-, 2,3-dimethoxybenzoic acid or chlorides of these acids, phenylacetic acid , phenylacetyl chloride, phenylacetic anhydride, cinnamic acid, cyanoic acid chloride, malonic acid, aalonic acid anhydride, phthalic acid, phthalic anhydride, terephthalic acid and terephthalyl chloride.

- G 7/-7- G 7 / -7

Kao katalizatori se u pronalaskom datom postupku upotrebljavaju zeoliti. Zeoliti su kristalni aluminosilikati, koji imaju jako uredjenu strukturu sa rigidnom trodimennzionalnom mreeom (resetkoa) tetraedara SiO^ ili AIO^, koji ou vezani preko zajednickih atoma kiseonika. Odnos atoma Si i Al u odnosu na kiseonik iznosi 1:2. Flektrovalanca tetraedra koji sactrži aluminijum uravnotežena je uklj uživanjem kat j ona u kristal, napr. ukljucivanjem alkalnog jona ili jona vodonika.Zeolites are used as catalysts in the invention. Zeolites are crystalline aluminosilicates, which have a highly ordered structure with a rigid three-dimensional network (reset) of SiO ^ or AIO ^ tetrahedrons, which are bonded via common oxygen atoms. The ratio of Si and Al atoms to oxygen is 1: 2. The aluminum-containing tetrahedral fluctuation of the tetrahedron is balanced by incorporating the cat into the crystal, e.g. by including an alkaline or hydrogen ion.

Pri torne je moguča izmena katj ona. Prostori izmedju tetraedara su pre dehidratacije posednuti od strane molekula vode koji se udaljavaju sušenjem odnosno kalciniranjem.It is possible to change the catheter. The spaces between the tetrahedra are saturated by water molecules, which are removed by drying or calcination before being dehydrated.

U zeolitima, umesto aluminijuma. mogu biti ugradjeni i drugi elementi, kao napr. Ga, Fe, Cr, V, As, Sb ili le, koji su ugradjeni u resetku, ili silicijum može biti zanenjen nekim drugim cetvorovalentnia elementom, kao sto is Ge, Ti, Zr,In zeolites, instead of aluminum. other elements can be incorporated, such as Ga, Fe, Cr, V, As, Sb, or le, which are embedded in the lattice, or silicon may be entangled by some other four-valent element, such as Ge, Ti, Zr,

Hf ·Hf ·

U saglasnosti sa njihovom strukturom zeoliti se mogu podeliti na različite grupe. Tako kod grupe mordenita zeolitnu strukturu grade lanci od tetraedara ili kod nabazitne grupe ovu strukturu obrazuju slojevi od tetraedara, dok se kod fau.jasitne grupe tetraedri rasporedjuju u poliedre, napr. u obliku kubooktaedra, koji su izgradjeni iz cetvoroclanih prstenova odnosno sestoclanih prstenova. Več prema vezivanju kubnih oktaedara, (cime nastaju prazni prostori (šupljine) i pore) razlikuju se zeoliti tipa A, L, Z ili Y.In accordance with their structure, zeolites can be divided into different groups. Thus, in the mordenite group, the zeolite structure is built by tetrahedral chains, or in the nasite group, this structure is formed by tetrahedral layers, while in the fau.asitic group the tetrahedra are arranged in polyhedra, e.g. in the form of cuboctahedra, which are constructed of four-membered rings or six-membered rings. According to the bonding of cubic octahedra, (thus creating empty spaces (cavities) and pores), zeolites of type A, L, Z or Y are distinguished.

Od katalizatora koji dalaze u obzir za primenu u pronalaskom datom postupku su pogodni napr. zeoliti iz mordenitne grupe ili zeoliti uskih pora tipa erionita odnosno chabasita ili zeoliti ______ r» - - ------** A ** tipa faujasita, napr. Υ-, X- ili L-zeoliti. U ovu grupu zeolita pripadaju takodje i takozvani ultrastabilni” zeoliti tipa faujasita, tj. dealuminirani zeoliti. Postupci za proizvodnju takvih zeolita su opisani u ”Catalysis by Zeolites, vol. 5 iz knige Studies in Surface Science and Catalysis, izd. E. Imelik et al., Slsevier Scientific Publishing Compl,Of the catalysts which are contemplated for use in the invention, the present process is suitable e.g. mordenite zeolites or narrow pores of the erionite or chabasite type pores or zeolites ______ r »- - ------ ** A ** of the faujasite type, e.g. Υ-, X- or L-zeolites. This group of zeolites also includes the so-called ultrastable "zeolites of the faujasite type, ie. dealuminated zeolites. Methods for producing such zeolites are described in ”Catalysis by Zeolites, vol. 5 from the book Studies in Surface Science and Catalysis, ed. E. Imelik et al., Slsevier Scientific Publishing Compl,

1980, 3tr. 203 i Crystal Structures of Ultra-stable Faujasites Advances in Chemistry Series i?r. 101, American Chemical Society Washington, DC, str. 226 i dalje (1971) i SAD patentni spis 4 512 961.1980, 3tr. 203 and Crystal Structures of Ultra-stable Faujasites Advances in Chemistry Series i? R. 101, American Chemical Society Washington, DC, p. 226 et seq. (1971) and US patent file 4 512 961.

Pogodno se primenjuju zeoliti tipa pentasila. Ovi imaju kao zajedai&ii strukturni zastavni deo petoclani prsten izgradjen od SiO, tetraedara. Oni su okarakterisani visokim odnosom SiO /Alo0-,* _kao - veličinama pora koje se nalaze izmedju veličina pora kod zeolita tipa i i zeolita tipa X ili 1.Pentasil type zeolites are conveniently applied. These have as a common and structural flag a five-membered ring constructed of SiO, tetrahedron. They are characterized by a high SiO / Al ratio of 0 -, * _k ao - pore sizes between pore sizes of type zeolites and type X or 1 zeolites.

Pr imeni jivi zeoliti .mogu iuati različite hemijske sastave, pogodni su, napr. alumino-, boro-, gvoždje-, berijlijum- , galijum__, hrom-, arsen-, antimon-, biznutsilikatni zeoliti ili njihove smese kao i alumino^, bero-, galijum-, gvoždjeger senatni zeoliti ili n j ili o ve oseše. Par ožit o su pogodni alumino-, boro- ili gvozdje-silikatni zeoliti tipa pentasila za primenu u pronalaskom datom postupku. Aluminosilikatni zeolit proizvodi se napr. iz nekog aluminijunovog jedinjenja, prvenstveno, iz Al(OH)^ ili ii.^SO/+)i jedne silicijumove komponente, prvenstveno visokodispergovanog silicijumdioksida u vodenom rastvoru amina, naročito u poliaminima kao sto su l,o-heksandiaminski ili 1,3-propandiaminski ili trietilentetraaminski rastvor sa dodatkom ili naužito bez dodatka alkalija ili zennih alkalija pri temperaturi od 100 do 220°C pod autogenin pritiskom· U to 3padaju takodje i izotaktiiki aeoliti dati ea EP 34 727. Dobiveni aluainosilikatni zooliti eadrŽe» ved prena izboru količina polaznih uaterija, odnos 3iC^/Aln0„ od 10 do 40000. Ovakvi aluainosilikatniNamed living zeolites. They can have different chemical compositions, they are suitable, for example. aluminum-, boron-, iron-, beryllium-, gallium__, chromium-, arsenic-, antimony-, biznutsilicate zeolites, or mixtures thereof, as well as alumino-, berro-, gallium-, iron-senate zeolites, or o f them. A couple of these are suitable alumina, boro- or iron-silicate zeolites of the pentasil type for use in the invention. Aluminosilicate zeolite is produced e.g. from an aluminum compound, preferably from Al (OH) ^ or ii. ^ SO / + ) and one silicon component, preferably highly dispersed silica in aqueous amine solution, especially in polyamines such as l, o-hexanediamine or 1,3- propandiamine or triethylenetetraamine solution, with or without the addition of alkali or zinc alkali at a temperature of 100 to 220 ° C under autogenin pressure · This also includes isotactic aeolites given ea EP 34 727. The obtained aluainosilicate zoolites in the eater are already available , ratio 3iC ^ / Al n 0 „from 10 to 40000. Such alluainosilicates

X. J?X. J?

seoliti aogu se sintotisati takodje i u etarskoa sedijusu kao sto je dietilenglikoldimstilotar, u alkoholnon medij umu, kao sto je aetanol, ili 1,4-butandiol ili u vodi.seolites may also be synthesized also in an ether sediment such as diethylene glycodimethylthiol, in an alcoholic medium such as aethanol, or 1,4-butanediol or in water.

Dorosilikatni zeolit sintetizira ee napr. pri 90 do 200 C pod autogenin pritiskom, tako sto se neko borno jedinjenje, napr. Ik^DO^, dogodi u reakciju aa nekim silicijuuovia jedi· njenjea, prvenstveno visokodianergovaniB silicijuu-diok3idoa, u vodenom rastvoru anina, naročito u rastvoru 1,6-hekaan· diaaina, ili 1,3-propandiarina ili trietilentetraacina aa ili naročito bez dodatka cikalij a ili a©naih alkalija. Takodje se pogodno rogu priaeaiti i izotaKticki borooilikatni zeoliti, koji su jroiavedeni prema .'d5 34 747. Takodje se nogu primeniti i dorosilikatni aeoliti, koji su iakristalisani iz otarskog rastvora, nar p. iz dietilonglikoldimetilstra ili iz aikoholnog rastvora, napr. iz Ι,ύ-ueksandiola, umesto iz vodenog rastvora aaiaa kao sto je napred pomenuto.Dorosilicate zeolite synthesizes ee e.g. at 90 to 200 C under autogenin pressure, such that some boron compound, e.g. Ik ^ DO ^ occurs in the reaction of aa with some silicon compounds, primarily high-energy silicon dioxide, in aqueous anine solution, especially in a solution of 1,6-hecaan · diaain, or 1,3-propanediarin or triethylenetetraacin aa or especially without addition cicalium or alkali. Also suitable is horn isotactic borooilicate zeolites, which have been reduced to .'d 5 34 747. Also dorosilicate aeolites, crystallized from otar solution, nar. from diethylonglycoldimethyl ester or from an aicholic solution, e.g. from Ι, ύ-uexandiol, instead of from the aqueous solution of aaiaa as mentioned above.

Gvozdjesilikatni seolit so dobiva napr. iz nekog jedinjenja gvoždja, prvenstveno iz ?eo(S0,)i nekog silicijuaovog jedinje· nja, prvenstveno visoko-Gisperggovanog silicijua-dioksida u vodeno« aiainakos rastvoru, naročito u rastvoru 1,6-heksandlamina» sa dodatkon ili bez dodatka alkalija ili z e cin ih alkalija pri 100 do 200°C pod autogenin pritiskon.The iron-silicate seolite is obtained eg. someone from compounds of iron, primarily from? e on (S0) and someone silicijuaovog jedinje · tion, primarily high-Gisperggovanog silicon dioxide-u-run "aiainakos a solution, narocito with a solution of 1,6-heksandlamina" dodatkon with or without additive or alkalis zinc alkali at 100 to 200 ° C under autogenic pressure.

U primenljive zeolite koji su bogati silicijumom (SiO^Al^ veči ili jednak 10) spadaju takodje i poznati ZSM tipovi kao R sto su Ferrierit i KU-1 kao i Silicalite , molekulsko sito, takozvani Siliča Polyaorph.Applicable silicon-rich zeolites (SiO ^ Al ^ greater than or equal to 10) also include known ZSM types such as R such as Ferrierite and KU-1 as well as Silicalite, a molecular sieve, the so-called Silica Polyaorph.

Tako proizvedeni aluaino-, boro- i gvoždjesillkatni zeoliti mogu se (posle njihovog izolovanja, sušenja pri 100 do loO°C, prvenstveno pri 110°, i posle kalciniranja pri 450 do 55O°G, prvenstveno pri 500°C) sa vezivnim sredstvom u odnosu 90:10 do 40:60 tož.^ preoblikovati u šipke ili tablete. Kao vezivni sredstva su pogodni različiti aluminijumoksidi, pogodno benit, amorfni aluminosilikati sa odnosno SiO^/Al^O^ od 25:75 do 90:5, prvenstveno 75:25» satia silicijuodioksid, pogodno visoko-dispergovani SiO , TiCo, smeše od visoko-disnergovanog ·ϋί0Λ i visoko-dismormovanog Al?0 kao i glina. nakon preoblikovanja ekstrudati ili briketi (presovani delovi) suše se pri 110°C/lo h i kalciniraju pri 500°C-/lb h.The aluainic, boron- and iron-silicate zeolites thus produced can be (after isolation, drying at 100 to loO ° C, preferably at 110 °, and after calcination at 450 to 55O ° G, primarily at 500 ° C) with a binder in ratio 90:10 to 40:60 lawsuit. ^ transform into bars or tablets. Suitable binders are various aluminum oxides, preferably benite, amorphous aluminosilicates with, respectively, SiO ^ / Al ^ O ^ from 25:75 to 90: 5, primarily 75:25 »satia silicon dioxide, suitably high-dispersed SiO, TiC o , mixtures of highly-dissociated · ϋί0 Λ and highly-dismembered Al ? 0 as well as clay. after transformation, extrudates or briquettes (pressed parts) are dried at 110 ° C / lo and calcined at 500 ° C- / lb h.

Dobro priaenljivi katalizator! se dobivaju takodje tako što se izolovan alumino- odnosno borosilikatni zeolit preoblikovan direktno posle sušenja i tek nakon preoblikovanja podvrgnut kalciniranju. Alumino- i borosilikatni zeoliti mogu se upotrebiti u čistom obliku, bez veziva, kao šipke ili tablete, pri čemu se kao sredstva za neprekidno presovanje ili peptiziranje mogu primeniti napr. etilceluloza, stearinska kiselina, škrob od kronpira, mravlja kiselina, oksalna kiselina, sirčetna kiselina, azotna kiselina, aconijak, silikoestri i grafit ili njihove smeseWell-liked catalyst! are also obtained by having the isolated alumina or borosilicate zeolite transformed directly after drying and subjected to calcination only after transformation. Aluminum and borosilicate zeolites can be used in pure, binder-free form, as rods or tablets, whereby they can be used, for example, as a continuous pressing or peptizing agent. ethylcellulose, stearic acid, potato starch, formic acid, oxalic acid, acetic acid, nitric acid, aconium, silicones and graphite or mixtures thereof

Ako se zeolit zbog tipa svog dobivanja ne nalazi u kataliticki aktivnom, kiselom H obliku, več u Ma-obliku, tada 33 ovaj može potpuno ili delimično prevesti u željeni 11-oblik uz primenu jonoizmenjivačke izmene, napr. aa j onima amonijuma, a zatim uz primenu kalciniranja ili tretiranjem sa kiselinama.If the zeolite, due to its type of preparation, is not in the catalytically active, acidic H form, but in the Ma form, then 33 may completely or partially translate it into the desired 11-form using an ion-exchange modification, e.g. aa j to those of ammonium, then by the application of calcination or by treatment with acids.

Ako pri pronalaskom Aatoj primeni zaolitnih katalizatora nastupi deaktiviranj e uslovi j eno izdvajanjem koksa, tada se preporučuje da se zeoliti regenerisu odvajanjem naslaga koksa sa vazduhon ϋ, pogocino pri ?CU smesom vazduh/l·!^ pri 400 do ovi zeoliti dobivaju svoju ,-rvobitnu aktivnost.If in finding Aatol the use of oolitic catalysts, the deactivation conditions caused by the separation of the coke occur, then it is recommended that the zeolites be regenerated by separating the coke deposits from the air ϋ, often at? CU with the air / l ·! ^ Mixture at 400 until these zeolites get their own, - rvobitnu activity.

Parcijalnim koksovanjem (predkoksovanjem) moguče je da se podesi aktivnost katalizatora za optimuni selektivnosti žaljenih reakcionih produkata.By partial coking (pre-coking) it is possible to adjust the activity of the catalyst to optimize the selectivity of the desired reaction products.

Da bi se postigli sto je moguče viša selektivnost, visok prinos kao i duža vremena stajanja, pogodno je da se zeoliti modificiraju. Pogodno nodificiranje katalizatora sastoji se u tone sto se, napr. neoblikovanim Ili preoblikovanim zeolitima dodaju metalne soli uz primenu izmene jona ili impregnacijom. Kao metali se upotrebljavaju alkalni metali, kao Li, K, Cs, zaanoalkalni metali, kao Mg, Ga, 3a, zemni metali lao 3, Al, Ga, prelazni metali, kao Cu, Zn, Cr, Mn,In order to achieve as high selectivity, high yield as possible and longer stand times, it is convenient for the zeolites to be modified. Suitable catalyst nodification consists of tonnes, e.g. untreated or transformed zeolites add metal salts by ion exchange or impregnation. The metals used are alkali metals, such as Li, K, Cs, zaanoalkalic metals, such as Mg, Ga, 3a, terrestrial metals lao 3, Al, Ga, transition metals, such as Cu, Zn, Cr, Mn.

Fe, Co, iii, W i Mo, plemeniti metali, kao Pd, Pt, Rb, Ir i retki metali (metali retkih zemalja) kao Ce, La, Pr, Hd,Fe, Co, iii, W and Mo, precious metals, such as Pd, Pt, Rb, Ir, and rare metals (rare earth metals) as Ce, La, Pr, Hd,

Svrsishodno se ovo dotiranje vrši tako što se preoblikovani žeoliti predloze u uzlaznoj cevi i pri 20 do 100°C preko njih propušta vodeni ili amonijacni rastvor halogenida ili nitrata prethodno pomenutog iaetala. Izmena jonova ovog tipa može se vršbti na vodonicnom, amonijumovog, alkalnom obliku zeolita* Jedna dalja mcgudnost nano senja jaetala na seolite data je time što se aeolitski aaterijal impregnira napr. 3a halogenidoa, nitratom ili oksidom prethodno pomenutog metala u vodenom, alkoholnom ili amonijacnom rastvoru. Kako nakon izmene jonova tako i nakon impregniranja mora se izvršiti najmanje jedno sušenje po šelji jednokratno kaleiniranj e.This purposeful dressing is done by proposing the transformed jellyites in an ascending tube and passing an aqueous or ammonia solution of the halides or nitrates of the aforementioned metal at 20 to 100 ° C. The exchange of ions of this type can be carried out on the hydrogen, ammonium, alkaline form of the zeolite * One further advantage of nanoscale deposition of eggs on seolites is given by impregnating the aolithic aaterial, e.g. 3a halide, nitrate or oxide of the aforementioned metal in aqueous, alcoholic or ammonia solution. After at least one ion exchange and after impregnation, at least one desiccant drying must be carried out on a one-off basis.

Jedan aogud način izvodjenja sastoji se ut torne Sto se napr. u vodi rastvori Ou(kO^),·, i 3 ili CoGO3)o k ό Ho0 ili CeOTOo), x όΗ„Ο ili La(rO,h a ό :’„0 ili C39G0o.One certain way of performing consists of a torque. in water dissolve Ou (kO ^), ·, and 3 or CoGO 3 ) o k ό H o 0 or CeOTOo), x όΗ „Ο or La (rO, ha ό: '„ 0 or C3 9 G0 o .

oa ovim rastvorom se izvesno vreme potapa preoblikovan ili neoblikovan zeolit, u toku perioda od oko 30 minuta. Eventualno zaostali rastvor se oslobodi od vode uparavanjen na rotacionom vakuum uparivašu. Zatim se natopljen zeolit osuši pri oko 150°C i pri 55O°C kalcinira. Ovaj proces potapanja može se preduzeti više puta jedno za drugim da bi se posti^ao zeljeni sadržaj metala.o This solution immerses the transformed or unformed zeolite for some time over a period of about 30 minutes. Any residual solution is released from the water by evaporation on a rotary evaporator. The soaked zeolite is then dried at about 150 ° C and calcined at 55 ° C. This immersion process can be undertaken several times in succession to achieve the desired metal content.

Takodje je mogude da se napravi napr. vodeni rastvor Go(N0372 ili amonijacni rastvor PdOiO^)^ i da se u tone uz mešanje u toku oko 24 sata izvrši suspendovanje čistih praškastih zeolita pri 40 do 100°C. Posle filtriranje, sušenja pri okol 150°G i kalciniranja pri oko 500°C tako dobiven zeolitni materijal se može dalje preradjivati sa ili bez vezivnog sredstva u šipke, pelete ili vrtložni materijal.It may also be possible to make e.g. aqueous solution of Go (NO 3 72 or ammonia solution PdOiO ^) ^ and suspend the pure powdered zeolites at 40 to 100 ° C in tones with stirring for about 24 hours. After filtration, drying at about 150 ° G and calcining at about 500 ° C, the zeolite material thus obtained can be further processed with or without a binder into rods, pellets or eddy material.

-----12-- Jonska izmena zeolita koji se nalazi u H-obliku ili amonijumovon obliku ili alkalnom obliku može se vršiti tako što se zeoliti u obliku šipki ili peleta predlože u koloni i preko njih provodi vodeni rastvor CoCNO^Jg ili amonijacni rastvor Pd(r;O-)9 pri lako povišenoj temperaturi izmedju 30 i 80°C u kružnom toku u toku perioda od 15 do 20 h. Potom se vrši ispiranje vodom, sušenje pri oko 150° i kalciniranje pri oko 550 0.----- 12-- Ion exchange of zeolite present in H-form or ammonium form or alkaline form can be effected by proposing column or pellet zeolites in a column and conducting an aqueous solution of CoCNO ^ Jg or ammonia solution of Pd (r; O-) 9 at a slightly elevated temperature between 30 and 80 ° C in a circular flow for a period of 15 to 20 h. It is then washed with water, dried at about 150 ° and calcined at about 550 °.

Kod nekih zeolita kojima je dotiran metal, napr. kod zeolita kojima je dotiran Pd, Cn, Ki, pogodno je izvršiti naknadni tretman sa vodonikom.For some zeolites that have been touched by metal, e.g. in the case of zeolites which have been doped with Pd, Cn, Ki, it is convenient to carry out subsequent treatment with hydrogen.

Jedna dalja nogučnost modifikova^ja sastoji se u torne što se preoblikovan ili neoblikovan zeolitni materijal podvrgava tretiranju sa kiselinama, kao što su sona, fluorovodonicna i fosforna kiselina, i/ili tretiranju sa vodenom parom. Pri torne se pogodno radi tako što sc zeoliti tretiraju u praškastom obliku sa 1 n fosfornon Jiselinom u toku 1 h pri 80°. Posle tretiranja ispira se vodom, osuši pri 110°C/l6 i kalcinira m pri 500°C/20 h. Prema jednom drugom načinu radazeoliti se tretiraju pre ili posle njihovog oblikovanja sa vezivnim sredstvima, napr. u toku 1 do 3 h pri temperaturama od 60 do 30°G sa 3$- do 25 tež- 5-nin, naročito 12 do 20 tez. % nim vodenim rastvorom sone kiseline. Zatim se tako trotiran zeolit ispira vodom, osuši i kalcinira pri 400 do 500°C.One further legibility of the modifiers consists in the fact that the transformed or unformed zeolite material is subjected to treatment with acids such as sona, hydrofluoric and phosphoric acid, and / or steam treatment. It is advantageous to treat the zeolites in powder form with 1 n phosphorone Yiselin for 80 hours at 1 ° C. After treatment, they are washed with water, dried at 110 ° C / 16 and calcined m at 500 ° C / 20 h. In another embodiment, radazeolites are treated before or after their formation with binders, e.g. during 1 to 3 h at temperatures from 60 to 30 ° G with 3 $ - up to 25 wt-5-nin, especially 12 to 20 weights. with aqueous hydrochloric acid. The triturated zeolite is then washed with water, dried and calcined at 400 to 500 ° C.

Jedan naročito pogodan oblik izvodjenja tretiranja kiselinom sastoji se u tone što se zeolitni materijal pre svog oblikovanja pri povišenoj temperaturi tretira flurovodonicnom kiselinom, koja se uopšte upotrebljava kao 0,001 n do 2 n, <“1·5 .· :One particularly advantageous form of acid treatment is the tonnes that the zeolite material is treated with hydrofluoric acid before its formation at elevated temperature, which is generally used as 0.001 n to 2 n, <“1 · 5. ·:

prvenstveno 0,05 η do 0,5 η fluorονodonicna kiselina, na priner, zagrevanjem uz refluksovanje u toku perioda vremena od 0,5 do 5 h, prvenstveno 1 do 3 h. Posle izolovanja, napr. odfiltriranjen i ispiranjem zeolitnog materijala, ovaj se suši svrsishodno pri temperaturana od 100 do l60°C i kalcinira pri temperaturama od 450° do 600°G, Prema jednom drugom pogodnom obliku izvodjenja ovog tretmana kiselinom zeolitni materijal se nakon svog oblikovanja tretira sa vezivnim sredstvom pri povišonoj temperaturi, svrsishodno pri temperaturama od 50°G do 90°G, prvenstveno 1 do 3 h sa sonom kiselinom, uopšte sa 3-25 tez. '-nom sonom kiselinom, prvenstveno sa 12-20 tez» G-noa sonom kiselinom. Zatim. se ovaj zeolitni materijal uopšte ispira i svrsishodno suši pri temperaturama od 100 do l6c°G i potom kalcinira pri temperaturama od 450°G do oOO°C. U datom slučaju je pogodno i sukcesivno tretiranje sa HF i HCI.preferably 0.05 η to 0.5 η fluorouric acid, per priner, by refluxing over a period of 0.5 to 5 h, preferably 1 to 3 h. After isolation, e.g. filtered and washed with the zeolite material, this material is dried expediently at a temperature of 100 to l60 ° C and calcined at temperatures of 450 ° to 600 ° G. According to another suitable form of acid treatment, the zeolite material is treated with a binder after its formation. elevated temperature, expediently at temperatures from 50 ° G to 90 ° G, preferably for 1 to 3 h with hydrochloric acid, generally from 3 to 25 wt. 's-sonic acid, preferably with 12-20 weights of G-noa acid. Then. this zeolite material is generally rinsed and purposely dried at temperatures of 100 to 16c ° G and then calcined at temperatures of 450 ° G to oOO ° C. In this case, successive treatment with HF and HCI is appropriate.

Prema jednom drugom načinu rada zeoliti se mogu modifikovati nanošenjem fosfornih jedinjenja, kao što su trimetilfosfIt, trimetoksifosfin, primarndig, sekundarnog ili tercijarnog natrijum-fosfata. Naročito pogodnom se pokazala obrada sa primarnim natrijum-fosfatom. Pri tome se ovi zeoliti u obliku šipki, tableta ili vrtloznog materijala natapaju vodenim rastvorom kaH^PO^, zatim osuše pri 110°C i klaciniraju pri 500°C.According to another mode of operation, zeolites can be modified by the application of phosphorous compounds such as trimethylphosphite, trimethoxyphosphine, primarndig, secondary or tertiary sodium phosphate. Particularly suitable is the treatment with primary sodium phosphate. These zeolites, in the form of bars, tablets or swirling material, are soaked in an aqueous solution of H 2 PO 4, then dried at 110 ° C and cloned at 500 ° C.

Pomenuti katalizatori mogu se prema želji upotrebiti u obliku šipki duzine 2 do 4 nm ili tableta sa prečnikom od 3 do 5 ena ili usitnjene materije sa velicinom delida od 0,1 do 0,5 mm ili vrtloznog materijala.Said catalysts may be optionally used in the form of rods of 2 to 4 nm in length or of tablets with a diameter of 3 to 5 nm or of a particulate matter having a particle size of 0.1 to 0.5 mm or a swirling material.

Reakcioni uslovi koji su po pravilima odabrani sa pronalaskom datu reakciju nalaze se kod pogodne reakcije u gasnoj fazi pri 3C0 do 600°C, prvenstveno 4.00 do 55O°C, i pri jednom opterečenju VKSV od 0,1 do 20 h “, pogodno 0,5 do 5 hl (g upotrebljene sneše/g katalisatora i sat). Ova reakcija raože se isvoditi u stalnom sloju ili vrtložnora sloju.The reaction conditions selected by the invention according to the invention are to be found in a suitable reaction in the gas phase at 3 ° C to 600 ° C, preferably 4.00 to 55 ° C, and at a single VKSV load of 0.1 to 20 h, preferably 0. 5 to 5 hl (g of sneeze / g of catalyst used and hour). This reaction can be carried out in a continuous layer or in a vortex layer.

iiedjutia, takodje je moguče da se ova reakcija izvodi u tieenoj fazi uz priaenu rada sa 3uspenzijora, prskanjem ili zidkom fazoa pri temperaturama izmedju 50 i u, pogodno izmedju 100 i 250' C i uz opterečenje g polazna materija : g katalizator - 100:1 do 5:1, pogodno 00:1 do 10:1.In addition, it is also possible for this reaction to be carried out in a sealed phase with the admixture of operation with a 3puspension, spraying or phasoid wall at temperatures between 50 and, preferably between 100 and 250 'C and with loading g starting material: g catalyst - 100: 1 to 5: 1, perfect 00: 1 to 10: 1.

Ovaj postupak se po pr?wilu izvodi pod normalnim pritiskom ili več prema isparijivosti polaznog jedinjenja pri snizenon pritisku ili pod povišenim pritiskom. Izvodjenje postupka se prvenstveno vrši kontinualno.This procedure is usually performed under normal pressure or already according to the volatility of the starting compound under reduced pressure or under elevated pressure. The procedure is primarily performed on a continuous basis.

Teško isparljive ili čvrste materije upotrebijavaju se u rastvorenom obliku, napr. u rastvoru u IH?, toluolu ili petroletru. U principu je moguče razblaživanje polazne materije sa takvim rastvaračima ili sa inertnim gasoviaa, kao sto su i<2» Ar, He ili sa vodenom parom.Hardly volatile or solids are used in dissolved form, e.g. in solution in 1H ?, toluene or petroleum ether. In principle, it is possible to dilute the starting material with such solvents or with inert gas such as <2 »Ar, He or with water vapor.

Nakon izvršene reakcije izoluju se stvoreni acilovani imidazoli ili pirazoli uz priaenu uobičajenih. postupaka, napr. destilacijom iz reakeione smeše; neproreagovane polazne materije se u datom slučaju vračaju nazad u reakciju.After the reaction is completed, the acylated imidazoles or pyrazoles isolated are isolated using the usual ones. procedures, e.g. by distillation from the reaction mixture; unreacted starting materials are then returned back into the reaction.

- ---Sledeči primeri bliže objašnjavaju ovaj pronalaaak- --- The following examples explain this invention more closely

ΊΊ3Γ1 J.ΊΊ3Γ1 J.

Reakcije u gasnoj i'.?.ai izvode se pod isoternnin uslovima u cevastom reaktoru (unutrašnji prečnik 2,5 “ca, dužina 20 ca, videti primer 1 i d); vendel, unutrašnji prečnik 0,6 cu, dužina 90 cm, videti primere 5 do li) u toku perioda od najmanje 6 h. Reakcioni produkti ou odvoj eni uobicajenim not odama i okarakterisani ,,οηοάη idG/l-Z3, hhh i odreci j ivan ja tačke topljenja, kvantitativno odredjivanje reakcionih .The reactions in the gas and '.? A and are carried out under isothermal conditions in a tubular reactor (internal diameter 2.5 "ca, length 20 ca, see example 1 and d); vendel, internal diameter 0.6 cu, length 90 cm, see examples 5 to li) over a period of at least 6 h. The reaction products are separated from the usual notes and characterized by οηοάη idG / l-Z3, hhh, and the melting point determinations, quantitative determination of the reaction.

pronukata i polaznin .ro-u.nmi vrši ss kronatografskia putem ili us primenu HPLC (tečne hronatohraf ije pod visokim pri-_ o 13 .s. O U ) · ovaj pronalaz..ro-u.nmi prodrugs and assays are performed by chronatography by or with the use of HPLC (liquid chronatohraphy at high pri-o 13 .s. U) · the present invention.

oljeni (prem ovo n or o na· lasku) katalizator! su:oily (prem this n or o · las) catalyst! are:

Katalizator ACatalyst A

Porosilikatni zeoiit termičkoj sintezi is 64.0 ZZo20n, 3000 g vodenog rastv > -ZPorosilicate zeoylite thermal synthesis is 64.0 ZZ about 20 n , 3000 g of aqueous solution> -Z

50:50 tež. $} pri 170°C pod sa mešanjem. Posle odfiltri reakcioni produkt se osuši i potom kaleinira pri 5OC°0/2i ti., a ..entasila dobiven je u hidro visoko-uispergovanog Si0o, 122 g ora i»o-neksadiacina (smeša nuto;eni~ pritiskom u autoklavu ran ju i ispiranja 'cristalni pri temperaturi od 100°C/21 £50:50 wt. $} at 170 ° C under stirring. After filtration, the reaction product is dried and then kaleinized at 5OC ° 0/2 and ti, and the .. entasil is obtained in hydro-high-dispersed Si0 o , 122 g ora and »o-nexadiacin (mixed by pressing in autoclave wounds and rinses' crystalline at 100 ° C / 21lb

Ovaj borosilikatni zeoiit se sastoji od 94*2 tež.This borosilicate zeoiite consists of 94 * 2 wt.

teztez

ss

Oblikovanjem sa od su ovog materijala su n osušene pri 110 ponočnim sredstvom za oblikovanje opravljene Sipkice dužine 2 an, koje h i kalcinirane pri 5OO°C/24- h.Forming with this material, n was dried at 110 midnight molding agent with a length of 2 an, h and calcined at 5 ° C / 24 h.

’ί ίο .- Katalizator'Ί ίο .- Catalyst

Katalizator 3 kn-Y zeolit u se dobiva vraskasto tako* ato se konercijalnu uobičajen i obliku sa Bobnuitom (u težinskoa oanosu 60:4.0) oblikuj ari ±10°0/ΐό k a sati ipkice ituaine 2 mu, koje se suse kalciniraju pri 500 CThe 3 kn-Y zeolite catalyst is obtained in a rounded manner so as to form a conventional cone with Bobnuit (60: 4.0 weight ratio), form ari ± 10 ° 0 / ΐό k hours and ituaine 2 mu, which are calcined at 500 C

Ove šipaice se 111,01 (uaseni odnos 1 *r oslobode od kloridnog 5 k ari 500°C. Sadrza izmenjuju sa 20 p-niu vodenim rastvorom : 15) pri 50 C. Zatim se ispiranjem j ona, 03V.še pri 110°C i kalciniraju j a is nosi 0,4-0 k.These rods are 111.01 (freeze ratio 1 * r freed from chloride 5 k in 500 ° C. The contents are exchanged with 20 p in aqueous solution: 15) at 50 C. Then they are rinsed, 03V at 110 °. C and calcine i and carries 0.4-0 k.

Katalizator CCatalyst C

Proizvodi se aluainosiiikatni zeolit tiu niasila ned kidroteruickin uslovi...u ,< polazeči od 650 g visoko--.i.se; 13 Ko0 u 10 kg vodenog rastvor »s» p) u autoklavu sa .Aluainosicicate zeolite tiu niasila ned kidroteruicin conditions are produced ... in, <starting from 650 g high--.i.se; 13 K o 0 in 10 kg of aqueous solution »s» p) in autoclave with.

au u o g e n m ;>r j.» i s c n i pri 150°C ovnnog 3i0~, 203 p Al„(SO,)a x /č Z J l,6neksadiar.ina (s^eša sanje;.;. Pošlo oukiltriranja i izpiranja kristalni roakcioni produkt se osuši pri 110°C/24 h a n. e η ✓J · > k.« i kalcinira pri 5OO°O/K4f’ H /j f» σ Π Q i? f Λ σ 3 O —’ «·* vi J. xju- / , θ U C <u · O .L \J qau uogenm;> r j. »eject at 150 ° C rams 3i0 ~, 203 p Al" (SO,) a x / h ZJ l, 6neksadiar.ina (s chesha dream;.;. the product is dried at 110 ° C / 24 ha n. e η ✓J ·> k. «and calcined at 5OO ° O / K4f 'H / jf» σ Π Q i? f Λ σ 3 O -' «· * vi J. xju- /, θ UC <u · O .L \ J q

3vnj aluminosilikatni zooiit χ ten. '> ilo09. Oblikovanjem sa /-i _>3vnj aluminosilicate zooiit χ tan. '> il o 0 9 . By formatting with / and _>

pouodnin uaterijalou sa oblikovanje od ovog materijala du proizvedene sipkice dužine k. um, koje su osušene pri 110°C/l6 h i kalcinirane pri 500°0/24. k.poodnin uaterijalou with the molding of this material for the produced rods of length k. um, which were dried at 110 ° C / 16 h and calcined at 500 ° 0/24. k.

Katalizator DCatalyst D

Katalizator D jo dobiven oblikovanjem aluminosilikatnog zeolita (uporediti katalizator 0) sa Soehaitom (težinski odnos 00:4.0) u sipkice dužine 2 na, koje su osušene pri . · -17.:- ..- :Catalyst D was obtained by molding the aluminosilicate zeolite (compare catalyst 0) with Soehaite (weight ratio 00: 4.0) into 2-length rods, which were dried at. · -17.:- ..-:

110°C/l6 h i kalcinirane pri 5OO°C/l6 h.110 ° C / l6 h and calcined at 5 ° C / l6 h.

Katalizator ECatalyst E

Za katalizator jo temeljno iznešan Ea-Y zeolitni izmenjen prema postupku H )9S0 i jedan borosilikatni videti katalizator P) u : sredstva za oblikovanje ;. Presovani delovi u obliku k i kalcinirani pri 500°C 16 h prah (sadržaj 0,07$ Ta) koji je opisanoLi sa katalizator d sa (k zeolit (za propis sa dobivanje uasenon odnosu 1:1 m uz dodatak oblikovan u sipkice duzine 2 un šipkica su sušeni pri IIC^C 16Ea-Y zeolite altered according to the process H) 9 S0 and one borosilicate catalyst P) in the form of: forming agents; Pressed parts in calcined form at 500 ° C 16 h powder (content $ 0.07 Ta) as describedLi with catalyst d with (k zeolite (for regulation with obtaining a ratio of 1: 1 m to ousenon with addition molded into rods 2 un the rods were dried at IIC ^ C 16

Primer 1 xri se smeša iaidazola, sirčetne kiseline i anhidrida sirčetne kiseline (nolski cd od 50 l/h pri 400 do 450°;; i preko katalizatora A, os 1:4:1,1) i sa strujom azota uz opterečenje od 1 h provodi keakcioni produkt se Prinos je 57 $ a selektivnost ondonzuje u staklenoj aparaturi, za 4-acetilimidazol iznosiExample 1 xri a mixture of iaidazole, acetic acid and acetic anhydride (zero cd from 50 l / h at 400 to 450 ° ;; and through catalyst A, axis 1: 4: 1,1) and with a nitrogen current with a load of 1 h is carried out by the reaction product The yield is $ 57 and the selectivity is donated in the glass apparatus, for 4-acetylimidazole is

56$. Prinos 4-a.cetiliridazola od teorijskog prinosa.$ 56. Yield of 4-a.cetiliridazole from theoretical yield.

odnosu na imidazol iznosi 32$ * j» 7 ν·· O prelative to imidazole is $ 32 * j »7 ν ·· O p

Smeša 2-netilimidazola, sirčetne kiseline (molski odno azota od 50 l/h pri 40C°C i uz ureko katalizatora A.A mixture of 2-nethylimidazole, acetic acid (50 l / h nitrogen mole at 40C ° C and urea catalyst A).

provodi sirčetne kiseline i anhidrida = 1:4:1) se. upari i sa strujom opterečenje od 1 . --- -IG 'Reakcioni produkt turi. Pri torne se dobiva selektivnosto od 35^ za 2 2-aiot il-4-acetilisidazola u odnosu na 2-netiliridas oe kondenzuje u staklenoj aparaumaac (pretvaranje) od 633 i -uet il-4-ac et iliuidaz ol. Pr inos iznosi 54a od teorijsko prinosa ol.conducts acetic acid and anhydride = 1: 4: 1) se. Pair with a current load of 1. --- -IG 'The reaction product of tours. In the case, a selectivity of 35 ^ for 2 2-aiol-4-acetylisidazole is obtained over 2-netiliridas which is condensed in a glass aparaumaac (conversion) of 633 and -uet il-4-ac et iliuidaz ol. The yield is 54a from the theoretical yield of ol.

Primeri 3-6Examples 3-6

Upari se smesa A-notili.midazola, anhidrida sirčetneThe mixture of A-notyl.midazole, acetic anhydride, was evaporated

kiseline i THF u molsko::: acids and THF in molar ::: oanosu 1:1:1 i prevodi -r-; oanosu 1: 1: 1 and translates -r-; eko katali- eco katali- satora satora datih u tabeli 1 given in Table 1 z , - . V V 4 C. 63 υ 1 z, -. V V 4 C. 63 υ 1 tabela l). Table l). Tabela Table 1: 1: Acet ilovani o j. Acet ilovani o j. - ο ύΐΐΐ - ο ύΐΐΐ ..silazola ..silazole pri- pri- kat a floor a - vre- temp. - temp. ..... ..... 1 a G — cl il 1 a G - cl il aliza proba* aliza proba * mer mer lisa lisa -ne -no tor tor tra- Γ^ΐ tra- Γ ^ ΐ /k “ί / k “ί Λ-retil- Ret-retil- U-acetil- U-acetyl- 5-acetil- 5-acetyl- 2-ace- 2-ace- jan j a jan j a i./.idasol i./.idasol a-netil- a-netil- 4-metil- 4-methyl- til-4- til-4- imidazol imidazole inidazol inidazole netil- netil- /h/ / h / /3/ / 3 / /3/ / 3 / /3/ / 3 / imidazc imidazc /5/ / 5 / 3 3 p p 6 320 6 320 t t 7 t <3 7 t <3 2> ,0 2>, 0 ,<-Q, 4 , <- Q, 4 16,3 16.3 3 3 n n 12 520 12 520 4 4 σ ω f f σ ω f f 19,6 19.6 19,1 19,1 20,6 20,6 4 4 a ii a ii 6 520 6 520 1 4p 1 4p 10,9 10.9 14,7 14.7 7,8 7.8 5 5 G Mr 6 520 6 520 4 4 14,2 14.2 1,24 1,24 10,9 10.9 5,2 5.2 6 6 D D 6 520 6 520 J J 17,7 17.7 13,6 13.6 14,3 14.3 10,1 10.1 * pr ob * pr ob a je a is sakupljana pr collected pr e ko 2 s e ko 2 s č·. u <1 « č ·. in <1 «

Primeri 7-9Examples 7-9

2-Hetiliaidazol js rcapovan sa sirdetnon kiselinoa. Reakciona smesa je razblažena sa TRP (videti tabelu 2).2-Hetiliaidazole was reconstituted with sirdetnone acid. The reaction mixture was diluted with TRP (see Table 2).

.Μ- ι??.Μ- ι ??

Tabela 2: Acetilovanje 2-netiliaidazolaTable 2: Acetylation of 2-netiliaidazole

pri- kata- prikata- vrene boil sirdetna te sirdetna te mper. F-ISV mper. F-ISV GC-analisa GC-analysis probe* rehearsals * ner liza- ner liza- tra- tra- kiselina: acid: 2-netil- 2-netil- 4-acetil- 4-acetyl- tor tor janja lambs 2-netil- 2-netil- inidazol inidazole -2-metil- -2-methyl- /h/ / h / iniaasoi: / TUF (aolar) iniaasoi: / TUF (aolar) /h*1// h * 1 / /;/ . /; /. iniaazol /d/ iniaazole / d /

7 7 A A 7 z · 1 · 6' /j, 7 z · 1 · 6 ' / j, 450 450 /. -f /. -f 42,5 42.5 O Oh G Mr i ?. ί · n +r u · j.· u i?. ί · n + r u · j. · u 1 4 1 4 Z 1 7 - » -t Z 1 7 - »-t r« 7 r « 7 r-> r-> 4 3:1:1 4 3: 1: 1 *r * r 7 c f °7 c f ° * probe sakupljane posle 1’ * samples collected after 1 ' .: · .: · Pr in Pr in eri 10 era 10 - 12 - 12 Inid Inid azol j: azole j: e posesan sa sird e possessed by sird • “ i · p • “i · p 'iselinon 'iselinon u nclaruou in nclaruou 1:2 1: 2 i reagovan preko razlic and reacted via vari - ustalis at or ustalis at or a (videti · a (See · Tabela 3: . Table 3:. Acetilovanje i.ai:. Acetylation i.ai:. as o k n as o k n pri- pri- kat a- floor a- _ vrene tene. _ boils. f' f' — ki v — f 'f' - which v - =analisa pr = analysis pr ner ner lisa- lisa- traj a- lasts- iuidazol iuidazole a-acetil- a-acetyl- tor tor n j a n j a iuidazol iuidazole /h/ /CG// h / / C G / Z'- / / -1 / Z'- / / -1 / /47 / 47 /5/ / 5 / 10 10 A A 6 450 6 450 •U j • U j 45,3 45,3 0,1 0.1 11 11 “Ί _? “Ί _? 6 45 0 6 45 0 7 7 44,3 44,3 0,2 0.2 12 12 fl L· fl L · 6 450 6 450 o o 44,4 44,4 0,1 0.1 * probe su * rehearsals are s a ku p1j ana posle s a ku p1j ana after ♦k. si · ♦ k. si ·

0000

2ό »6 17,62ό »6 17.6

9,3 /5/ s,i9.3 / 5 / s, i

O , uOh, u

11,011,0

Prinečri 13Bring 13

Pirazol se reaguje sa ekvinolarnon količinon anhidrida sirčetne kiseline u gasnoj fazi (videti tabelu 4).Pyrazole is reacted with an equinolarnone amount of acetic anhydride in the gas phase (see Table 4).

Tabela 4: Acetilovanie pirazola pri- kat a- vre ne tenprr. kTISV GC-analiz a pr obe *Table 4: Acetylation of pyrazoles in the case of hot tenprr. kTISV GC analysis a pr both *

r.er lisa- traja- . Ί ·· · ·Ί n χ·ί J piraaol a-acenl- C-acetil tor n ja piraaol pirazolr.er lisa- lasts-. Ί ·· · Ί n χ · ί J piraaol a-C-acetyl acenl- tor n ja piraaol pyrazole

/h/ / h / /°?7 / °? 7 /a-1/ /;;// a- 1 / / ;; / /5/ / 5 / /b/ / b / 13 G 2 13 G 2 / n / n 3 35,0 3 35.0 24,4 24.4 3,3 3.3 14 Λ 6 14 Λ 6 / Q Ci • > ; t j / Q Ci •>; t j > 2, o > 2, o 6,1 6,1 * nrobe su sakueli * nrobes are sakuel ana ?oelc ana? oelc '-9  '-9

-lir-lir

Claims (7)

PATENTNI ZAHTEVKIPATENT APPLICATIONS 1. Postopek pridobivanja aciliranih imidazolov in pirazolov s formulama I in II v katerih sta R2 in R3 enaka ali različna in neodvisno eden od drugega pomenita vodik, alkil z 1 do 12 atomi ogljika, alkenil z 1 do 12 atomi ogljika, alkoksil z 1 do 12 atomi ogljika, arilni, aralkilni ali alkilarilni ostanek,A process for the preparation of acylated imidazoles and pyrazoles of formulas I and II in which R 2 and R 3 are the same or different and independently represent hydrogen, alkyl of 1 to 12 carbon atoms, alkenyl of 1 to 12 carbon atoms, alkoxyl of 1 to 12 carbon atoms, an aryl, aralkyl or alkylaryl radical, R4 pomeni vodik, alkilni ostanek z 1 do 12 atomi ogljika, alkenilni ostanek z 1 do 12 atomi ogljika, arilni, aralkilni ali alkilarilni ostanek,R 4 represents hydrogen, an alkyl residue of 1 to 12 carbon atoms, an alkenyl residue of 1 to 12 carbon atoms, an aryl, aralkyl or alkylaryl residue, R5 pomeni alkil z 1 do 12 atomi ogljika, alkenilni ostanek z 1 do 12 atomi ogljika, arilni, aralkilni ali karboksi ostanek, označen s tem, da reagira petčlenski heteroaromat s formulo III oz. IV r3' x R1 R 5 represents alkyl of 1 to 12 carbon atoms, an alkenyl radical of 1 to 12 carbon atoms, an aryl, aralkyl or carboxy radical characterized in that it reacts a five-membered heteroaromatic of formula III or IV r3 ' x R 1 S /\T/ \ u (III) (IV) v kateri so R1 do R3 lahko enaki ali različni in neodvisno eden od drugega pomenijo vodik, alkilni ostanek z 1 do 12 atomi ogljika, alkenilni ostanek z 1 do 12 atomi ogljika, alkoksilni ostanek z 1 do 12 atomi ogljika, arilni, aralkilni ali alkilarilni ostanek, pri čemer vsaj eden od simbolov R1 do R3 pomeni vodik in R4 pomeni vodik, alkil z 1 do 12 atomi ogljika, alkenilni ostanek z 1 do 12 atomi ogljika, arilni, aralkilni ali alkilarilni ostanek, s sredstvom za aciliranje s formulo V (V) v kateri ima R5 zgoraj navedeni pomen in Y pomeni halogenidni, alkoksi, aciloksi, hidroksi, amidni in karboksi ostanek, v prisotnosti zeolita kot katalizatorja.S / \ T / \ u (III) (IV) in which R 1 to R 3 may be the same or different and independently represent hydrogen, an alkyl residue of 1 to 12 carbon atoms, an alkenyl residue of 1 to 12 carbon atoms , an alkoxyl radical of 1 to 12 carbon atoms, an aryl, aralkyl or alkylaryl radical, wherein at least one of the symbols R 1 to R 3 is hydrogen and R 4 is hydrogen, alkyl of 1 to 12 carbon atoms, an alkenyl radical of 1 to 12 carbon atoms, an aryl, aralkyl or alkylaryl radical having an acylating agent of formula V (V) in which R 5 is as defined above and Y is a halide, alkoxy, acyloxy, hydroxy, amide and carboxy radical in the presence of a zeolite as a catalyst. 2. Postopek po zahtevku 1, označen s tem, da kot katalizator uporabimo zeolit tipa pentasil.Process according to claim 1, characterized in that a pentasil-type zeolite is used as a catalyst. 3. Postopek po zahtevku 1, označen s tem, da kot katalizator uporabimo borove, železove ali alumosilikatne zeolite.Process according to claim 1, characterized in that boron, iron or alumosilicate zeolites are used as catalyst. 4. Postopek po zahtevku 1, označen s tem, da kot katalizator uporabimo zeolit tipa faujasit.Process according to claim 1, characterized in that a faujasite type zeolite is used as a catalyst. 5. Postopek po zahtevkih 1 do 4, označen s tem, da kot katalizator uporabimo zeolit, dotiran z alkalnimi, zemeljskoalkalnimi kovinami, kovinami redkih zemelj, prehodnimi kovinami in/ali fosfoijem.5. The process according to claims 1 to 4, characterized in that the zeolite is contacted with alkali, alkaline earth metals, rare earth metals, transition metals and / or phosphoium as the catalyst. 6. Postopek po zahtevku 5, označen s tem, da kot katalizator uporabimo zeolit, dotiran s cezijem.Process according to claim 5, characterized in that zeolite doped with cesium is used as a catalyst. 7. Postopek po zahtevku 5, označen s tem, da kot katalizator uporabimo zeolit, dotiran s Ce in/ali La.Process according to claim 5, characterized in that a zeolite doped with Ce and / or La is used as a catalyst.
SI8811413A 1987-07-21 1988-07-21 Procedure for the production of acylated imidazoles and pyrazoles. SI8811413A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19873724035 DE3724035A1 (en) 1987-07-21 1987-07-21 METHOD FOR PRODUCING ACYLATED IMIDAZOLES AND PYRAZOLES
YU141388A YU46984B (en) 1987-07-21 1988-07-21 PROCEDURE FOR OBTAINING ACYLATED IMIDAZOLES AND PYRAZOLES

Publications (1)

Publication Number Publication Date
SI8811413A true SI8811413A (en) 1996-12-31

Family

ID=25857780

Family Applications (1)

Application Number Title Priority Date Filing Date
SI8811413A SI8811413A (en) 1987-07-21 1988-07-21 Procedure for the production of acylated imidazoles and pyrazoles.

Country Status (2)

Country Link
HR (1) HRP931372A2 (en)
SI (1) SI8811413A (en)

Also Published As

Publication number Publication date
HRP931372A2 (en) 1996-08-31

Similar Documents

Publication Publication Date Title
JPS59206323A (en) Manufacture of phenol and acetone
JP4136867B2 (en) A new industrial synthesis of strontium ranelate and its hydrates
US4804758A (en) Preparation of 1,4-diazabicyclo[2.2.2]octanes
US4924000A (en) Preparation of acylated imidazoles
JPH01132587A (en) Production of 1, 4-diazabicyclo (2, 2, 2)-octane from piperadine
US5144061A (en) Preparation of alkenecarboxylic esters
SI8811413A (en) Procedure for the production of acylated imidazoles and pyrazoles.
US4943667A (en) Preparation of phenylethanols
JPS6125A (en) Manufacture of diene
JPS61289060A (en) Manufacture of 4-pentenoic acid ester
US5225602A (en) Phenylacetaldehydes and the preparation of phenylacetaldehydes
US4812593A (en) Preparation of bifunctional compounds
DE3883891T2 (en) Benzimidazole derivatives and process for their preparation.
JPS62167749A (en) Manufacture of nitrile
JPS62298581A (en) Manufacture of acylated heteroaromatic compound by use of zeolite
US4904806A (en) Preparation of tetrahydrofurans from butane-1,4-diols
HU202213B (en) Process for producing acylated imidazol- and pyrazol derivatives
JP2690480B2 (en) Novel 4-formyl tetrahydropyran
JPH11508901A (en) Method for producing methylamine compound
US4968831A (en) Preparation of α-ketocarboxylic esters
JP3965527B2 (en) Method for N-alkylation of pyrazole
US5008461A (en) Preparation of benzyl ketones
JP3465925B2 (en) Method for producing methylamines
CN1004132B (en) Method for esterification
JPH01311047A (en) Production of terminal olefinic unsaturated carboxylic acid