US3463781A - Dehydrogenation and cyclization of amines - Google Patents

Dehydrogenation and cyclization of amines Download PDF

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Publication number
US3463781A
US3463781A US530338A US3463781DA US3463781A US 3463781 A US3463781 A US 3463781A US 530338 A US530338 A US 530338A US 3463781D A US3463781D A US 3463781DA US 3463781 A US3463781 A US 3463781A
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Prior art keywords
catalyst
iodine
dehydrogenation
nitrogen
compounds
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US530338A
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English (en)
Inventor
William Hamilton Bell
John Dewing
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Imperial Chemical Industries Ltd
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Imperial Chemical Industries Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/08—Preparation by ring-closure

Definitions

  • This invention is a modification in or an improvement to the invention described in copending application S.N. 515,204, filed Dec. 20, 1965.
  • the said application relates to the dehydrogenation of nitrogenous compounds to form aromatic heterocyclic compounds containing nitrogen in the ring and especially to the dehydrogenation and cyclization of open chain compounds to form pyri dine or substituted derivatives thereof.
  • the present invention provides a vapour phase dehydrogenation process for the production of aromatic compounds having nitrogen in the ring which comprises heating a halogen with an aliphatic nitrogenous compound containing a sufficient number of carbon, nitrogen and hydrogen atoms in an appropriate arrangement to form the aromatic compound after dehydrogenation in the presence of oxygen and a catalyst comprising a compound of an alkali or alkaline earth metal.
  • aliphatic we wish to include open chain aliphatic and alicyclic compounds containing nitrogen in the ring, i.e. compounds which are saturated or only partially unsaturated thus permitting dehydrogenation to an aromatic compound. We do not wish to exclude the possibility of aromatic substituents being attached to the aliphatic part of such a compound.
  • a pre ferred halogen is iodine.
  • halogen and iodine we wish to include cases in which the halogen or iodine are formed in situ, e.g. sources of iodine which yield iodine under the reaction conditions.
  • the process of the present invention is especially applicable to the dehydrogenation of aliphatic nitrogenous compounds containing an open chain of carbon and nitrogen atoms, appropriate atoms in the chain having sufficient hydrogen atoms to permit cyclization to occur on dehydrogenation to form the aromatic compound.
  • preferred starting materials are exemplified by primary and secondary amines and imines having hydrogen atoms on the carbon or nitrogen atoms which take part in the formation of the cyclizing bond.
  • Compounds such as nitriles and isonitriles having five carbon atoms and no hydrogen atoms on the terminal carbon or nitrogen atom do not readily undergo cyclization.
  • the starting material contains one nitrogen atom then the product will usually be pyridine or a substituted 3,463,781 Patented Aug. 26, 1969 derivative thereof.
  • Simple starting materials with only five carbon atoms, one nitrogen atom and a sufllcient number of hydrogen atoms will form pyridine itself.
  • More complex starting materials will form substituted derivatives of pyridine.
  • the nitrogen atom is bonded to not more than two carbon atoms, since this eliminates the need for a cracking type reaction to occur or some rearrangement of groups around the nitrogen atom.
  • Suitable substituents which lead to the production of substituted pyridines may include for example, alkyl, halogen, hydroxyl or pyridyl radicals or combinations of these.
  • a-picoline is obtained and using appropriately substituted starting materials, compounds of the quinoline, isoquinoline or bipyridyl series may be obtained.
  • the substituent itself may undergo change for example dehydrogenation (e.g. an ethyl group may be converted to a vinyl group), or may be removed by a cracking reaction.
  • the starting compounds used herein may also be defined as primary, secondary or tertiary alkyl amines or alkyl alkylidene amines wherein the amines have at least 5 carbon atoms and each alkyl or alkylidene group therein has no more than 5 carbon atoms.
  • the starting materials may be formed in situ from suitable simpler precursors which together provide the required structure to form the aromatic heterocyclic compound after combination and dehydrogenation. Examples are provided by the use of aliphatic aldehydes and primary amines which condense to form imines, e.g. acetaldehyde and propylamine which. form ethylidene propylamine. Higher yields are obtained if the precursors are mixed before reacting with iodine although some desired product may be formed it the precursors and iodine are mixed together in the reaction vessel.
  • Temperatures should be high enough to maintain the reactants in the gaseous phase. Temperatures in the range 300 C. to 800 C. and preferably 350 C. to 650 C. are convenient. Outside this range yields decrease and difiiculties may be encountered with clogging of the apparatus or undesired side reactions.
  • the alkali or alkaline earth metal may be present as a solid, preferably carried on a support material, or it may be used in the molten form.
  • Oxygen may be present as air, as pure oxygen or as any other convenient source of oxygen.
  • Especially suitable alkali metals are lithium and potassium.
  • the catalyst preferably comprises a compound of silver and/ or rare earth metals including scandium and yttrium.
  • Compounds of the mixture of rare earth metals known as didymium may conveniently be used.
  • Didymium oxide for example has approximately the following composition, 45% La O 38% Nd O 11% Pr O 4% Sm O and 2% residuals.
  • Compounds of transition group metals may also be present.
  • transition group metal We mean a metal having an atomic number within the ranges 22-29, 40-46, 72-79 and 82-84 all inclusive.
  • a preferred transition metal is iron.
  • the catalyst is preferably supported on a carrier.
  • the carrier should preferably have a high ratio of surface area to weight. Examples of carriers are a-alumina, silica or pumice.
  • the ratio of iodine to starting material may vary within wide limits. Owing to the high cost of iodine it is desirable to use as small an amount of iodine as is consistent with an acceptable yield of product.
  • One advantage of thepresent invention is that the dehydrogenation may be carried out in the presence of only very small amounts of iodine, for example between 0.01 to 0.3 mole per mole of starting material, or lower or higher if desired.
  • the amount of oxygen required depends in general on in by a mixed stream of nitrogen and oxygen, the nitrogen and oxygen flow rates being varied so as to vary the mole ratios of iodine and oxygen to propylidene ethylamine.
  • the nitrogen/iodine flow rate was about 20 litres/hour and oxygen/iodine about 4 litres/hour giving a total gas the compound being dehydrogenated. Approximately flow of about 38 litres/hour.
  • stoichiometric amounts of oxygen may be used in ac-
  • the outgoing gas stream from the reactor was passed cordance with the number of hydrogen atoms which are through a heated tube, with a gas sampling point for gas in theory to be removed from the compound and oxidised liquid chromatography analysis, and then through a conto water.
  • 1 mole of ethylidene propylamine denser 1 mole of ethylidene propylamine denser.
  • the products were collected in two flasks of distheoretically requires 1.5 moles of oxygen for the contilled water. version into pyridine.
  • aqueous solution with washings of condenser etc. theoretical amount is conveniently used but this can be was analysed for pyridine by u.v. Yields of pyridine on lower or higher as required.
  • propylidene ethylamine were determined.
  • the reactor was a quartz tube of total length 2 ft, with a preheat section of length 8 ins.
  • the volume of the EXAMPLES 10-14 were designed to show the effect of reactor was approximately 200 mls. and of the catalyst 35 various support materials. Results are given for a and 7 approximately 100 mls. Propylidene ethylamine and A1 0 alone for comparison. Details are listed in Table II.
  • iodine were passed separately through the preheat section and mixed at the reaction temperature.
  • a catalyst was prepared consisting of 2.08 parts potassium bromide, 1.09 parts didymium chloride, 1.02 parts silver iodide on 100 parts of alumina.
  • the alumina pellets of A2 in. diameter were calcined at 900 C. for 24 hours before precipitation of the catalyst.
  • the alumina was impregnated with an aqueous solution containing the catalyst components in the form of soluble salts.
  • Insoluble catalysts were formed on the carrier by treatment with a suitable reagent.
  • silver iodide was formed by reacting silver nitrate with hydriodic acid.
  • the impregnated carrier was dried on a steam bath with continuous stirring and subsequently in a furnace at 550 C. for 5 hours.
  • a catalyst was prepared consisting of 2.08 parts potassium bromide, 1.09 parts didymium chloride, 1.02 parts silver iodide on 100 parts of pumice (22-30 mesh).
  • the pumice was impregnated with an aqueous solution containing the catalyst components in the form of soluble salts.
  • Insoluble catalysts were formed on the carrier by treatment with a suitable reagent.
  • silver iodide was formed by reacting silver nitrate with hydriodic acid.
  • the impregnated carrier was dried on a steam bath with continuous stirring and subsequently in a furnace at 550 C. for hours.
  • amine is a primary or secondary alkyl amine or an alkyl alkylidene amine derivable by condensation of an aldehyde with a primary amine.
  • the catalyst also includes at least one member of the group consisting of silver halides and the rare-earth metal halides.
  • the catalyst also includes at least one transition metal halide selected from the elements having an atomic number within the range 22 through 29, 40 through 46, 72 through 79, and 82 through 84.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Catalysts (AREA)
  • Pyridine Compounds (AREA)
US530338A 1965-03-19 1966-02-28 Dehydrogenation and cyclization of amines Expired - Lifetime US3463781A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB11769/65A GB1102221A (en) 1965-03-19 1965-03-19 Process for preparing pyridine or substituted pyridines
GB2258765 1965-05-27

Publications (1)

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US3463781A true US3463781A (en) 1969-08-26

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US (1) US3463781A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
BE (1) BE678107A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
GB (1) GB1102221A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
NL (1) NL6603488A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3532701A (en) * 1968-01-18 1970-10-06 Dow Chemical Co Vapor phase production of perchlorinated pyridine and cyanopyridines from cyano-substituted cyclobutanes and cyclobutenes
US3679688A (en) * 1970-04-23 1972-07-25 Union Oil Co Preparation of substituted pyridines
US4257967A (en) * 1978-11-01 1981-03-24 Toray Industries, Inc. Catalyst composition and method for oxidation of ethylene to ethylene oxide and method of catalyst manufacture

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3532701A (en) * 1968-01-18 1970-10-06 Dow Chemical Co Vapor phase production of perchlorinated pyridine and cyanopyridines from cyano-substituted cyclobutanes and cyclobutenes
US3679688A (en) * 1970-04-23 1972-07-25 Union Oil Co Preparation of substituted pyridines
US4257967A (en) * 1978-11-01 1981-03-24 Toray Industries, Inc. Catalyst composition and method for oxidation of ethylene to ethylene oxide and method of catalyst manufacture

Also Published As

Publication number Publication date
NL6603488A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1966-09-20
BE678107A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1966-09-19
GB1102221A (en) 1968-02-07

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