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Process for the production of substituted pyridine (b)

Assignee: Evonik Operations GmbH
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Filing: 1977-09-06
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Granted: 1979-10-02
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Expires: 1997-09-06
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Abstract

Abstract Pyridines substituted in the 2- and 3-positions by aromatic or heteroaromatic groups are prepared by reacting an aromatic or heteroaromatic substituted ketone which has at least one reactive methylene group adjacent to the keto group with an aliphatic oxo compound having a carbon to carbon ethylenic double bond on the carbon atom adjacent to the oxo group and ammonia in the presence of a dehydrating and dehydrogenating catalyst at a temperature of about 250° to 550° C.

Inventors

  • 👤 Helmut Beschke
  • 👤 Heinz Friedrich

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-11-09 07:34
CPC Classifications
C; C07; C07D; C07D213/00; C07D213/02; C07D213/04; C07D213/06; C07D213/22; C07D213/08; C07D213/09; C07D213/12

Claims Analysis

Total Claims: 19
Claim 1
Independent Claim 581 words
A process for the production of a pyridine having a substituent from the group consisting of an aromatic group and a heteroaromatic group in each of the 2-and 3-position which comprises catalytically reacting a ketone having an aromatic or heteroaromatic group on both sides of the keto group and also having at least one reactive methylene group adjacent to the keto group with an aliphatic oxo compound having a carbon to carbon ethylenic double bond on the carbon atom adjacent to the oxo group and ammona in the gas phase at a temperature from about 250° to 500° C. in the presence of a dehydrating and dehydrogenating catalyst which is either (1) a catalyst consisting essentially of oxygen containing compounds of Al,F, at least one of the elements B and Si and at least one element from the second and fourth groups of the periodic system selected from the group consisting of Mg,Ba,Zn,Sn and Zr, said catalyst having been prepared by heating in the presence of oxygen at a temperature of 600° to 800° C.: 1. aluminum, aluminum oxide or an aluminum compound convertible to the oxide at said temperature, 2. a compound of fluorine, said fluorine having been added as ammonium fluoride, ammonium hydrogen fluoride, hydrogen fluoride, fluoboric acid, fluosilicic acid, boron trifluoride, magnesium fluoborate, magnesium fluosilicate, zinc fluosilicate or barium fluosilicate, 3. boron, silicon, boric oxide, silica or a compound of boron or silicon convertible to the oxide at said temperature and 4. magnesium, zinc, tin, zirconium, magnesium oxide, zinc oxide, tin oxide or a compound of zirconium or barium convertible to the oxide at said temperature, the atomic ratio of Al to F being from 1000:25 to 1000:800 and the atomic ratio of Al to the total of (3) and (4) being from 1000:5 to 1000:200, the atomic ratio of the total of boron and silicon to the other element from the second and fourth group being between 1 to 10 and 10 to 1, (2) a catalyst having been prepared by heating at 600° to 800° C. in the presence of gaseous oxygen (1) aluminum metal, aluminum oxide or a compound of aluminum convertible to the oxide upon heating with gaseous oxygen at 600° C. to 800° C., (2) ammonium fluoride, hydrogen fluoride or a fluoride of an element of the second main group of the periodic system and (3) at least one element of the second main group of the periodic system, the oxide of said element or a compound of said element convertible to the oxide in the presence of gaseous oxygen at a temperature of 600° to 800° C., said catalyst consisting essentially of the elements Al, F, O and the element of the second main group of the periodic system being selected from the group consisting of Mg, Ca, Sr and Ba, and (3) a catalyst consisting essentially of the product obtained by treating with oxygen at a temperature of 550° to 1200° C., compounds of the elements Al, F and O and at least two other elements selected from the second, fourth, fifth and sixth groups of the periodic system, said two other elements being selected from the group consisting of Mg, Ba, Zr, Sn, Ti, P, Ta, Sb and S, the ratios of the elements being Al to F of between 1,000 to 10 and 1,000 to 800 and of Al to the elements of the second, fourth, fifth and sixth groups being between 1,000 to 5 and 1,000 to 200.
Claim 2
Dependent Claim 581 words
A process for the production of a pyridine having a substituent from the group consisting of an aromatic group and a heteroaromatic group in each of the 2-and 3-position which comprises catalytically reacting a ketone having an aromatic or heteroaromatic group on both sides of the keto group and also having at least one reactive methylene group adjacent to the keto group with an aliphatic oxo compound having a carbon to carbon ethylenic double bond on the carbon atom adjacent to the oxo group and ammona in the gas phase at a temperature from about 250° to 500° C. in the presence of a dehydrating and dehydrogenating catalyst which is either (1) a catalyst consisting essentially of oxygen containing compounds of Al,F, at least one of the elements B and Si and at least one element from the second and fourth groups of the periodic system selected from the group consisting of Mg,Ba,Zn,Sn and Zr, said catalyst having been prepared by heating in the presence of oxygen at a temperature of 600° to 800° C.: 1. aluminum, aluminum oxide or an aluminum compound convertible to the oxide at said temperature, 2. a compound of fluorine, said fluorine having been added as ammonium fluoride, ammonium hydrogen fluoride, hydrogen fluoride, fluoboric acid, fluosilicic acid, boron trifluoride, magnesium fluoborate, magnesium fluosilicate, zinc fluosilicate or barium fluosilicate, 3. boron, silicon, boric oxide, silica or a compound of boron or silicon convertible to the oxide at said temperature and 4. magnesium, zinc, tin, zirconium, magnesium oxide, zinc oxide, tin oxide or a compound of zirconium or barium convertible to the oxide at said temperature, the atomic ratio of Al to F being from 1000:25 to 1000:800 and the atomic ratio of Al to the total of (3) and (4) being from 1000:5 to 1000:200, the atomic ratio of the total of boron and silicon to the other element from the second and fourth group being between 1 to 10 and 10 to 1, (2) a catalyst having been prepared by heating at 600° to 800° C. in the presence of gaseous oxygen (1) aluminum metal, aluminum oxide or a compound of aluminum convertible to the oxide upon heating with gaseous oxygen at 600° C. to 800° C., (2) ammonium fluoride, hydrogen fluoride or a fluoride of an element of the second main group of the periodic system and (3) at least one element of the second main group of the periodic system, the oxide of said element or a compound of said element convertible to the oxide in the presence of gaseous oxygen at a temperature of 600° to 800° C., said catalyst consisting essentially of the elements Al, F, O and the element of the second main group of the periodic system being selected from the group consisting of Mg, Ca, Sr and Ba, and (3) a catalyst consisting essentially of the product obtained by treating with oxygen at a temperature of 550° to 1200° C., compounds of the elements Al, F and O and at least two other elements selected from the second, fourth, fifth and sixth groups of the periodic system, said two other elements being selected from the group consisting of Mg, Ba, Zr, Sn, Ti, P, Ta, Sb and S, the ratios of the elements being Al to F of between 1,000 to 10 and 1,000 to 800 and of Al to the elements of the second, fourth, fifth and sixth groups being between 1,000 to 5 and 1,000 to 200.
Claim 3
Dependent Claim 70 words
The process of claim 1 wherein the substituted pyridine has the formula ##STR4## where R 1 and R 2 are aromatic or heteroaromatic rings which are unsubstituted or substituted by halogen, alkyl or cyanogen, R 3 , R 4 and R 5 are hydrogen or lower alkyl and n is 0 or 1, the aromatic or heteroaromatic ketone has the formula ##STR5## and the oxo compound has the formula ##STR6##
Claim 4
Dependent Claim 28 words
The process of claim 2 wherein R 1 and R 2 are unsubstituted phenyl, pyridyl or thienyl groups or such groups substituted by halogen, lower alkyl or cyano.
Claim 5
Dependent Claim 24 words
The process of claim 3 wherein R 3 , R 4 and R 5 are hydrogen or alkyl with 1 to 2 carbon atoms.
Claim 6
Dependent Claim 11 words
The process of claim 4 wherein oxo compound (II) is acrolein.
Claim 7
Dependent Claim 50 words
The process of claim 2 wherein ketone (I) is dichlorodiphenyl-1,3-acetone, dimethyldiphenyl-1,3-acetone, dicyanodiphenyl-1,3-acetone, dipyridyl-1,3-acetone, dithienyl-1,3-acetone, diphenyl-1,3-acetone, benzyl phenyl ketone, benzyl pyridyl ketone, picolyl phenyl ketone or benzyl thienyl ketone and oxo compound (II) is methacrolein, crotonaldehyde, alkyl vinyl ketone having 1 to 2 carbon atoms in the alkyl group or 3-penten-2-one.
Claim 8
Dependent Claim 28 words
The process of claim 6 wherein ketone (I) is dibenzyl ketone, benzyl phenyl ketone or benzyl-2-pyridyl ketone and oxo compound (II) is acrolein, crotonaldehyde or methyl vinyl ketone.
Claim 9
Dependent Claim 11 words
The process of claim 7 wherein oxo compound (II) is acrolein.
Claim 10
Dependent Claim 16 words
The process of claim 7 wherein the process is carried out at 300° to 500° C.
Claim 11
Dependent Claim 14 words
The process of claim 2 wherein the reaction temperature is 300° to 500° C.
Claim 12
Dependent Claim 14 words
The process of claim 10 wherein the reaction temperature is 350° to 450° C.
Claim 13
Dependent Claim 22 words
The process of claim 2 wherein there is used 1 to 5 moles of oxo compound (II) per mole of ketone (I).
Claim 14
Dependent Claim 20 words
The process of claim 12 wherein there is used 1 to 20 moles of ammonia per mole of ketone (I).
Claim 15
Dependent Claim 18 words
The process of claim 13 wherein the reaction is carried out in the presence of an inert gas.
Claim 16
Dependent Claim 11 words
The process of claim 2 wherein the catalyst is aluminum silicate.
Claim 17
Dependent Claim 10 words
The process of claim 10 wherein the catalyst is (1).
Claim 18
Dependent Claim 10 words
The process of claim 10 wherein the catalyst is (2).
Claim 19
Dependent Claim 10 words
The process of claim 10 wherein the catalyst is (3).

References Cited (Backward Citations)

CA655703A Cited
US2877228A Cited
US2926074A Cited
US3932421A Cited
US3898177A Cited
US3960766A Cited
US3917542A Cited

USPTO Annuity & Maintenance Windows

Annuity Stage Window Opens Payment Deadline Surcharge Period Until Estimated Fee Status
3.5 Years (Year 4) 1982-10-01 1983-04-02 1983-10-02 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 1986-10-01 1987-04-02 1987-10-02 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 1990-10-01 1991-04-02 1991-10-02 $7700.00 Window Closed / Lapsed

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