EP0000208B1 - Verfahren zur Herstellung von Imidazolen - Google Patents

Verfahren zur Herstellung von Imidazolen Download PDF

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Publication number
EP0000208B1
EP0000208B1 EP78200001A EP78200001A EP0000208B1 EP 0000208 B1 EP0000208 B1 EP 0000208B1 EP 78200001 A EP78200001 A EP 78200001A EP 78200001 A EP78200001 A EP 78200001A EP 0000208 B1 EP0000208 B1 EP 0000208B1
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EP
European Patent Office
Prior art keywords
parts
acid
catalyst
starting material
per hour
Prior art date
Legal status (The legal status 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 status listed.)
Expired
Application number
EP78200001A
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German (de)
English (en)
French (fr)
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EP0000208A1 (de
Inventor
Toni Dr. Dockner
Anton Frank
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BASF SE
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BASF SE
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Filing date
Publication date
Priority claimed from DE19772729017 external-priority patent/DE2729017A1/de
Priority claimed from DE19772728976 external-priority patent/DE2728976A1/de
Priority claimed from DE19772733466 external-priority patent/DE2733466A1/de
Application filed by BASF SE filed Critical BASF SE
Publication of EP0000208A1 publication Critical patent/EP0000208A1/de
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Publication of EP0000208B1 publication Critical patent/EP0000208B1/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members

Definitions

  • the invention relates to a new process for the preparation of imidazoles by reacting carboxylic acids with 1,2-diamines or by reacting 2-imidazolines at temperatures from 300 to 600 ° C. in the presence of zinc oxide or a mixture of zinc oxide and aluminum oxide as catalysts.
  • the process according to the invention provides imidazoles in a good yield and purity in a simpler and more economical way. Although no additional hydrogen is added, formation of tarry polymers, deposits on the catalyst and a rapid decrease in catalyst activity are not observed. The addition of hydrogen is not necessary nor expedient. In comparison to the catalysts of the known processes, the catalysts according to the invention are cheaper, easier to regenerate and are not significantly poisoned during a longer period of operation.
  • procedure a) In addition to the end product, in the case of procedure a), the only essential by-product is the imidazoline which is homologous to the end product.
  • the imidazoline can be used for a number of syntheses or can be recycled and dehydrated to give the endimidazole by a dehydrogenation process, advantageously procedure b).
  • procedure a) according to the invention thus provides a substantially higher yield of reusable end products or of end product I, based on the same amount of starting material 11. All of these advantageous properties are surprising with regard to the prior art.
  • the starting materials II and III are reacted with one another in a stoichiometric amount or each in excess to one another, advantageously in a ratio of 1 to 5, preferably 1 to 1.1, moles of starting material II per mole of starting material 111.
  • Preferred starting materials II, III and IV and accordingly preferred end products 1 are those in the formulas R ', R 2 , R 3 and R 4 can be the same or different and each have an alkyl radical with 1 to 18 carbon atoms, in particular with 1 to 87 carbon atoms , an alkenyl radical with several or in particular a double bond and with 2 to 18, preferably 3 to 18, in particular 4 to 8 carbon atoms, an aralkyl radical with 7 to 12 carbon atoms, a cycloalkyl radical with 5 to 7 carbon atoms or a phenyl radical or a hydrogen atom.
  • the abovementioned radicals can also be substituted by groups which are inert under the reaction conditions, for example alkyl groups or alkoxy groups each having 1 to 4 carbon atoms.
  • Suitable starting materials III are: benzoic acid, phenylacetic acid; Acrylic acid, formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, tetracosanoic acid, hexacosanoic acid, linoleic acid, linolenic acid, ricinoleic acid, erucic acid, myristic acid, arachic acid, behenic acid, oleic acid, elaidic acid, caproic acid, oenanthic acid, pelargonic acid, 3.5-trimric acid acid, capric acid acid, capric acid acid, capric acid acid 2-ethylpentene (2) acid (1), undecanoic acid, lauric acid, palmitic acid, stearic acid, 2-ethylhexane carboxylic acid, a-ethyl butyric acid, methacrylic acid, crotonic acid, isocrotonic acid, Tiglinic acid
  • starting materials IV come e.g. in question: in 2-position, 4-position or 5-position single or in 2 of these positions the same or different double or in these 3 positions the same or different triple by the methyl, ethyl, allyl, crotyl, propyl , Isopropyl, butyl, isobutyl, pentyl, sec.-butyl, tert.-butyl, hexyl, heptyl, octyl, oleyl, n-undecen- (11) -yl- (1) -, Nonyl, decyl, octadecyl, benzyl, phenyl group substituted 2-imidazolines, unsubstituted 2-imidazoline; in 2-position, 4-position or 5-position single or in 2 of these positions identical or different twice or in these 3 positions identical or different triple by the methyl, ethyl, allyl, crotyl, propyl, is
  • the reaction is at a temperature of 300 to 600 ° C, advantageously from 350 to 500 ° C, in the case of procedure a) preferably from 400 to 450 ° C, in the case of procedure b) preferably from 400 to 480 ° C, without pressure or under pressure, in the case of procedure b) advantageously from 1 to 50 bar, carried out continuously or batchwise.
  • the reaction mixture also serves as a solution medium; if appropriate, organic solvents which are inert under the reaction conditions and advantageously do not form an azeotrope with water, e.g. aliphatic hydrocarbons such as petroleum ether or ligroin can be used.
  • Organic solvents include those with a boiling point above 120 ° C, suitably above 140 ° C, e.g. appropriate gasoline fractions from 120 to 160 ° C, preferred.
  • Zinc oxide alone or a mixture of zinc oxide and aluminum oxide advantageously in a ratio of zinc to aluminum such as 1 to 50, preferably 8 to 10, gram atoms of zinc per gram of aluminum, and from 0.1 to 1, preferably from 0.2 to, are used as the catalyst 0.4 gram atom of zinc is used per mole of starting material II or IV.
  • aluminum oxide e.g. a and y alumina in question.
  • Zinc compounds which give zinc oxide under the reaction conditions can also be used, e.g. an aluminum oxide impregnated with zinc chloride or zinc sulfate. Substances or mixtures of substances containing this oxide can also be used instead of aluminum oxide, e.g.
  • the catalyst can be carrier-free or can also be applied to a carrier, advantageously in an amount of 1 to 18 percent by weight of catalyst, based on the carrier.
  • the aforementioned aluminum compounds can simultaneously serve in the form of the AI z 0 3 contained therein as a catalyst component and for the zinc oxide as a carrier.
  • Suitable carriers are silicic acid compounds such as silicates, for example montmorillonite, Florida earth, quartz, asbestos; precipitated silica, silica gel, diatomaceous earth; Titanium dioxide, zirconium dioxide, tin dioxide, activated carbon; Alkaline earth metal sulfates or alkaline earth metal phosphates, for example the calsium or barium salts; or corresponding mixtures of the aforementioned carrier materials.
  • the preparation of the supported catalysts is carried out by the customary methods, for example by applying the zinc compound and, if appropriate, the aluminum compound to the support, drying and calcining, for example between 400 and 1200 ° C. in a reducing, oxidizing or inert atmosphere.
  • the carrier can also be impregnated and dried in its desired geometric shape with a solution of the zinc compound alone or the zinc and aluminum compound, for example an aqueous solution of zinc sulfate and optionally aluminum sulfate.
  • the support material can also be kneaded with the zinc compound and, if appropriate, the aluminum compound and water, brought into the desired shape, dried and calcined at a temperature of 400 to 1200 ° C.
  • the particle size of the catalysts is preferably from 0.05 to 7, in particular 2 to 4 millimeters.
  • the shape can be any, e.g. in pill, cylinder or strand form, spherical or granular. Pore volumes of 0.05 to 1 milliliter per gram, specific surfaces of 1 to 300 square meters per gram and bulk densities of 0.4 to 2.1 grams per milliliter are preferred for the supported catalyst. It is also possible to use pipes covered with catalyst or mesh-like supports.
  • the catalysts on the support are preferably in the form of chips or spheres in the fluidized bed used, with catalyst particles having particle sizes of 0.005 to 3 mm, in particular 0.1 to 1 mm, preferably 0.2 to 0.4 mm, being used expediently.
  • the layer height of the catalyst bed in the fluidized state is advantageously 30 to 2,000 millimeters, in the case of procedure b) in particular 60 to 80 millimeters, or is expediently chosen so that the residence times of the starting materials II in the catalyst layer are from 0.01 to 20, preferably from 5 to 10 seconds.
  • the reaction can be carried out as follows:
  • the liquid or expediently vaporous starting materials II and III in the case of mode a), expediently in a mixture with inert gases such as nitrogen, are passed over the catalyst or catalyst on the support in a fixed bed at the reaction temperature.
  • the liquid or vaporous starting material IV is expediently mixed with inert gases, e.g. Nitrogen, passed at the reaction temperature over the catalyst or catalyst on the support in a fixed bed.
  • the reaction mixture emerging in vapor form from the reactor is then optionally dedusted in a cyclone and condensed in a cooled receiver.
  • the end product is expediently separated off by fractional distillation.
  • the end product can also be obtained by recrystallization or reprecipitation from suitable solvents, e.g. with toluene, dimethylformamide or dilute acids, e.g. with formic acid.
  • the starting materials are reacted in a fluidized bed at the reaction temperature.
  • the supported catalyst or catalyst can be used by inert gas, a mixture of starting material II and III and inert gas or the starting mixture alone or in the case of procedure b) a mixture of starting material IV and inert gas as a fluidized bed gas at normal pressure or reduced or elevated pressure in a fluidized bed being held.
  • the total amount or a partial amount of starting material II and III or a partial amount of starting material IV can be introduced into the fluidized bed reactor separately from the fluidized bed gas.
  • the diamine II and the carboxylic acid 111 can also be mixed; the salts formed in this way are expediently kept liquid in a heated storage vessel and metered into an evaporator which is connected upstream of the fluidized bed reactor.
  • starting material IV can also be kept liquid in a heated storage vessel and metered into an evaporator which is connected upstream of the fluidized bed reactor.
  • a weak stream of nitrogen advantageously from 5000 to 50000 parts by volume of nitrogen per hour, is advantageously passed through the evaporator.
  • the vaporized salts or, in the case of procedure b), the vaporized starting material IV are passed through the catalyst bed together with the nitrogen stream.
  • the concentration of the starting material IV in the inert gas is advantageously 0.1 to 50 percent by volume.
  • the method according to the invention can be carried out in a simple or subdivided, open or closed fluidized bed system with and without flowing dust circulation.
  • reactors implementation, process variants and reaction conditions of the fluidized bed process, reference is made to Ullmann's Encyclopedia of Industrial Chemistry, Volume 1, pages 916 ff. The reaction mixture is worked up in the aforementioned manner.
  • the imidazoline is advantageously metered in liquid into the evaporator, the vapors are passed through the vortex reactor in a nitrogen stream and then condensed.
  • the reaction mixture can also be purified by distillation or crystallization.
  • the imidazoles 1 which can be prepared by the process of the invention are valuable starting materials for the production of dyes, crop protection agents, textile auxiliaries, catalysts for polyurethanes and epoxy resins, surface-active agents and pharmaceuticals, e.g. the corresponding nitroimidazoles.
  • Imidazoles I are used as catalysts for polymerization reactions and aldol condensations. With regard to the use, reference is made to the referenced publications and Ullmann's Encyclopedia of Industrial Chemistry, Volume 8, page 499.
  • the parts listed in the following examples are parts by weight.
  • the parts by weight relate to the parts by volume like kilograms to liters.
  • 120 parts of 1,2-diaminoethane are mixed with 120 parts of acetic acid at 38 ° C. with stirring and cooling.
  • the ethylenediamine monoacetate solidified below 35 ° C to a crystalline mass, above this temperature it remains liquid.
  • 200 parts of this mixture are dosed per hour from a storage vessel into a horizontal quartz evaporator heated to 300 ° C and the steam together with 5000 parts by volume of nitrogen per hour are passed through the vortex reactor heated to 350 ° C.
  • the vortex reactor is an electrically heated quartz tube that sits vertically on the evaporator and is sealed at the bottom with a melted quartz frit.
  • the quartz tube is half-filled with 200 parts of a catalyst composed of 90 percent by weight zinc oxide and 10 percent by weight aluminum oxide (crown size 0.1 to 0.3 mm).
  • the residence time in the catalyst zone in the fluidized state is 3.5 seconds.
  • the vapors leaving the reactor are condensed and fractionally distilled.
  • 55.8 parts (41% of theory, based on converted diamine II) of 2-methylimidazole, bp 15 158 ° C., mp 145 ° C. and 59.6 parts (42.5% of theory, based on converted diamine) are obtained per hour 11) 2-methylimidazoline, bp 15 115 ° C, mp 103 ° C.
  • the conversion is 98.7 percent, based on diamine II.
  • the yield remained constant even after 300 hours of operation.
  • Example 1 The fluidized bed reactor described in Example 1 is fed from two separate storage vessels, which are located on the horizontal quartz evaporator, with 100 parts of acetic acid (vessel 1) and 100 parts of ethylenediamine (vessel 2) together with 5,000 parts by volume of nitrogen per hour.
  • acetic acid e.g., acetic acid
  • ethylenediamine e.g., ethylenediamine
  • Example 2 Analogously to Example 1, 71.3 parts (52.1% of theory, based on converted diamine 11) of 2-methylimidazole, mp 145 ° C., are obtained per hour.
  • the turnover is 98.6 percent, based on diamine II.
  • the yield remained constant even after 300 hours of operation.
  • An electrically heated tubular reactor is filled with 10 mm long and 4 mm thick cylindrical fillers (200 parts) consisting of 90 percent by weight zinc oxide and 10 percent by weight aluminum oxide.
  • This fixed bed reactor sits vertically on a quartz evaporator.
  • 100 parts of 1,2-diaminoethane, 100 parts of acetic acid are evaporated every hour in a quartz evaporator at 300 ° C. and the vapors are passed through the reactor heated to 400 ° C. together with 5,000 parts by volume / hour of nitrogen.
  • 66.4 parts (48.3% of theory, based on converted diamine II) of 2-methylimidazole, mp 145 ° C., are obtained per hour. The conversion is 97.9%, based on diamine 11. The yield remained constant even after 300 hours of operation.
  • Example 7 Analogously to Example 7, 200 parts of 4-methylimidazoline per hour are dehydrated at 400 ° C. in a nitrogen stream of 5,000 parts of N 2 / hour. Analogously to Example 8, 171 parts (91.7% of theory, based on converted diamine 11) of 4-methylimidazole, mp 45 ° C., are obtained per hour. The conversion is 95.5 percent, based on the reacted starting material IV. The yield remained constant even after 300 hours of operation.
  • molten 1-phenylimidazoline per hour 100 parts are metered from a heated metering vessel into a horizontal quartz evaporator heated to 300 ° C.
  • the vapors are passed together with 5,000 parts by volume of N 2 per hour through a fluidized bed reactor heated to 400 ° C.
  • the vortex reactor is an electrically heated quartz tube that sits vertically on the evaporator and is sealed at the bottom with a melted quartz frit.
  • the quartz tube is half-filled with 200 parts of a catalyst composed of 90 percent by weight zinc oxide and 10 percent by weight aluminum oxide (grain size 0.1 to 0.3 mm).
  • the residence time in the catalyst zone in the fluidized state is 3.5 seconds.
  • the height of the catalyst zone in the vortex state is 80 mm.
  • the vapors leaving the reactor are condensed and fractionally distilled. 69.5 parts per hour are obtained (76% of theory, based on converted starting material IV) 1-phenylimidazole with a boiling point (2 mbar) 110 to 112 ° C in addition to 7.3 parts of unreacted 1-phenylimidazoline with a melting point of 45 ° C.
  • the turnover is 92.7 percent, based on the reacted starting material IV.
  • the yield remains constant after 72 hours of operation.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
EP78200001A 1977-06-28 1978-06-01 Verfahren zur Herstellung von Imidazolen Expired EP0000208B1 (de)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
DE19772729017 DE2729017A1 (de) 1977-06-28 1977-06-28 Verfahren zur herstellung von imidazolen
DE2729017 1977-06-28
DE19772728976 DE2728976A1 (de) 1977-06-28 1977-06-28 Verfahren zur herstellung von imidazolen
DE2728976 1977-06-28
DE19772733466 DE2733466A1 (de) 1977-07-25 1977-07-25 Verfahren zur herstellung von imidazolen
DE2733466 1977-07-25

Publications (2)

Publication Number Publication Date
EP0000208A1 EP0000208A1 (de) 1979-01-10
EP0000208B1 true EP0000208B1 (de) 1980-04-30

Family

ID=27187232

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78200001A Expired EP0000208B1 (de) 1977-06-28 1978-06-01 Verfahren zur Herstellung von Imidazolen

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EP (1) EP0000208B1 (enrdf_load_stackoverflow)
JP (1) JPS5416472A (enrdf_load_stackoverflow)
DE (1) DE2857617D1 (enrdf_load_stackoverflow)
IT (1) IT1096577B (enrdf_load_stackoverflow)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3009633A1 (de) * 1980-03-13 1981-09-24 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von 2-imidazolinen
DE3009631A1 (de) * 1980-03-13 1981-09-24 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von imidazolen
DE3009605A1 (de) * 1980-03-13 1981-10-01 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von imidazolen
JPS6019007A (ja) * 1983-07-12 1985-01-31 Kurita Water Ind Ltd 凝集剤
DE4209847A1 (de) * 1992-03-26 1993-09-30 Basf Ag Verfahren zur Herstellung von 4-substituierten Imidazolen
JP2002255941A (ja) * 2001-03-02 2002-09-11 Koei Chem Co Ltd イミダゾール化合物の製造法
EP2082717A1 (en) 2008-01-28 2009-07-29 Merz Pharma GmbH & Co. KGaA Titration package
WO2018090199A1 (zh) * 2016-11-15 2018-05-24 广东莱佛士制药技术有限公司 一种异佛尔酮的制备方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2226057A (en) * 1936-06-20 1940-12-24 Soc Of Chemical Ind Process for dehydrogenating heterocyclic bases
US2847417A (en) 1956-07-13 1958-08-12 Houdry Process Corp Preparation of imidazole compounds
US2991965A (en) * 1959-03-23 1961-07-11 Mag Craft Corp Pallet
NL6915693A (enrdf_load_stackoverflow) 1968-10-29 1970-05-04

Also Published As

Publication number Publication date
JPS6123791B2 (enrdf_load_stackoverflow) 1986-06-07
IT1096577B (it) 1985-08-26
IT7824769A0 (it) 1978-06-20
EP0000208A1 (de) 1979-01-10
JPS5416472A (en) 1979-02-07
DE2857617D1 (en) 1980-06-12

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