CN104402812A - Synthetic method for pyridinecarboxylic acid - Google Patents
Synthetic method for pyridinecarboxylic acid Download PDFInfo
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- CN104402812A CN104402812A CN201410588924.8A CN201410588924A CN104402812A CN 104402812 A CN104402812 A CN 104402812A CN 201410588924 A CN201410588924 A CN 201410588924A CN 104402812 A CN104402812 A CN 104402812A
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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
- C07D213/60—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 with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/803—Processes of preparation
-
- 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
- C07D213/60—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 with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/80—Acids; Esters in position 3
Abstract
The invention discloses a synthetic method for pyridinecarboxylic acid. The method comprises the following steps: heating alkyl pyridine to 300 to 450 DEG C on a fixed bed, wherein alkyl pyridine all becomes steam after continuous heating for 3 hours; sufficiently reacting methylpyridine with ammonia, water vapor and oxygen and carrying out standing in a container for half an hour; adding titanium tetrachloride into gas for catalysis and waiting for 2 hours so as to obtain pyridinecarbonitrile; adding 1.2 g of ion-free water into the obtained pyridinecarbonitrile, carrying out stirring, heating the mixture to 40 to 70 DEG C, adding sodium hydroxide, carrying out stirring, heating the mixture to 80 to 95 DEG C and maintaining the temperature for 4 to 12 hours; and after completion of a reaction, cooling the mixture to 30 to 60 DEG C, carrying out filtering, then carrying out washing with ion-free water and carrying out drying to obtain 10 g of solid powder. According to the invention, the yield is 83.3%; the problem of environmental pollution in traditional methods is overcome; the yield is greatly improved; and the reaction can be carried out at normal temperature and normal pressure or at low pressure.
Description
Technical field
The invention belongs to organic chemical synthesis field, relate to a kind of synthetic method of pyridine carboxylic acid.
Background technology
The molecular formula of pyridine carboxylic acid is: C
5h
5nO
2.Structurally being all and having cried out lewis acid and lewis basic functionality, is typical heterocyclic amphoteric substance.Pyridine carboxylic acid series is widely used in medicine, chemical industry, food and life in, there is irreplaceable effect and value.Therefore scholar both domestic and external and expert have carried out large quantifier elimination to pyridine carboxylic acid synthesis.Pyridine carboxylic acid comprises a, B, 7 three kinds of isomer: picolinic acid, nicotinic acid and γ-picolinic acid.The method of conventional synthesis pyridine carboxylic acid is: catalytic gas phase oxidation method.Under it is high temperature, alkyl pyridine is vaporized, and mixes, be direct oxidation into pyridine carboxylic acid through catalyst bed with air and water vapour.The purity requirement of this method catalyzer to raw material is high, easily produces tar and toxic gas, causes environmental pollution.
Summary of the invention
In order to solve the problem of the easy generation environmental pollution existed in prior art, the invention provides a kind of pyridine synthesis formic acid method, with the method pyridine synthesis formic acid, avoid in traditional method the problem causing environmental pollution, substantially increase productive rate, and can react under normal temperature and pressure or low pressure.
Achieve the above object, the synthetic route of pyridine carboxylic acid of the present invention is:
The building-up process of the pyridine carboxylic acid that the present invention relates to comprises the following steps:
(1) alkyl pyridine of 12g is heated to 300-450 DEG C on a fixed bed, the continuous heating through 3 hours all becomes steam;
(2) methane pyridine vapor and ammonia, water vapour, oxygen fully reacts, and leaves standstill half an hour in a reservoir;
(3) titanium tetrachloride adding 5mol again in gas carries out catalysis, waits for the pyridine carbonitrile obtaining 0.85g after 2 hours;
(4) add in the pyridine carbonitrile obtained 1.2g deionized water then start stir, be warmed up to 40-70 DEG C, disposable add 0.08g hydroxide that, stir, be warmed up to 80-95 DEG C, insulation 4-12 hour.Terminate reaction, be cooled to 30-60 DEG C, filter, wash with the deionized water of 0.4g, dry to obtain the pressed powder of 10g.Productive rate: 83.3%.
Specific embodiments:
The alkyl pyridine of 12g is heated to 300-450 DEG C on a fixed bed, continuous heating through 3 hours all becomes steam. methane pyridine vapor and ammonia, water vapour, oxygen fully reacts, leave standstill half an hour in a reservoir, the titanium tetrachloride adding 5mol again in gas carries out catalysis, wait for the pyridine carbonitrile obtaining 0.85g after 2 hours. in the pyridine carbonitrile obtained, add 1.2g deionized water then start to stir, be warmed up to 40-70 DEG C, disposable add 0.08g hydroxide that, stir, be warmed up to 80-95 DEG C, insulation 4-12 hour.Terminate reaction, be cooled to 30-60 DEG C, filter, wash with the deionized water of 0.4g, obtain the pressed powder of 10g.Productive rate: 83.3%;
Example 1
The alkyl pyridine of 12g is heated to 300 DEG C on a fixed bed, continuous heating through 3 hours all becomes steam. methane pyridine vapor and ammonia, water vapour, oxygen fully reacts, leave standstill half an hour in a reservoir, the titanium tetrachloride adding 5mol again in gas carries out catalysis, wait for the pyridine carbonitrile obtaining 0.85g after 2 hours. in the pyridine carbonitrile obtained, add 1.2g deionized water then start to stir, be warmed up to 40 DEG C, disposable add 0.08g hydroxide that, stir, be warmed up to 80 DEG C, be incubated 4 hours.Terminate reaction, be cooled to 30 DEG C, filter, wash with the deionized water of 0.4g, obtain the pressed powder of 9.5g.Productive rate: 79.1%.
Example 2
The alkyl pyridine of 12g is heated to 350 DEG C on a fixed bed, continuous heating through 3 hours all becomes steam. methane pyridine vapor and ammonia, water vapour, oxygen fully reacts, leave standstill half an hour in a reservoir, the titanium tetrachloride adding 5mol again in gas carries out catalysis, wait for the pyridine carbonitrile obtaining 0.85g after 2 hours. in the pyridine carbonitrile obtained, add 1.2g deionized water then start to stir, be warmed up to 70 DEG C, disposable add 0.08g hydroxide that, stir, be warmed up to 85 DEG C, be incubated 6 hours.Terminate reaction, be cooled to 30 DEG C, filter, wash with the deionized water of 0.4g, obtain the pressed powder of 9.8g.Productive rate: 81.7%.
Example 3
The alkyl pyridine of 12g is heated to 450 DEG C on a fixed bed, continuous heating through 3 hours all becomes steam. methane pyridine vapor and ammonia, water vapour, oxygen fully reacts, leave standstill half an hour in a reservoir, the titanium tetrachloride adding 5mol again in gas carries out catalysis, wait for the pyridine carbonitrile obtaining 0.85g after 2 hours. in the pyridine carbonitrile obtained, add 1.2g deionized water then start to stir, be warmed up to 40 DEG C, disposable add 0.08g hydroxide that, stir, be warmed up to 80 DEG C, be incubated 12 hours.Terminate reaction, be cooled to 60 DEG C, filter, wash with the deionized water of 0.4g, obtain the pressed powder of 9.9g.Productive rate: 82.5%.
Claims (1)
1. a method for pyridine synthesis formic acid, is characterized in that:
(1) alkyl pyridine of 12g is heated to 300-450 DEG C on a fixed bed, the continuous heating through 3 hours all becomes steam;
(2) methane pyridine vapor and ammonia, water vapour, oxygen fully reacts, and leaves standstill half an hour in a reservoir;
(3) titanium tetrachloride adding 5mol again in gas carries out catalysis, waits for the pyridine carbonitrile obtaining 0.85g after 2 hours;
(4) add in the pyridine carbonitrile obtained 1.2g deionized water then start stir, be warmed up to 40-70 DEG C, disposable add 0.08g hydroxide that, stir, be warmed up to 80-95 DEG C, insulation 4-12 hour.Terminate reaction, be cooled to 30-60 DEG C, filter, wash with the deionized water of 0.4g, dry to obtain the pressed powder of 10g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410588924.8A CN104402812A (en) | 2014-10-28 | 2014-10-28 | Synthetic method for pyridinecarboxylic acid |
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| CN201410588924.8A CN104402812A (en) | 2014-10-28 | 2014-10-28 | Synthetic method for pyridinecarboxylic acid |
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| CN1134854A (en) * | 1995-01-24 | 1996-11-06 | 罗纳·布朗克纤维和树脂中间体公司 | Catalyst for oxidation of ammonia and method for prepn. of same |
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| CN104109116A (en) * | 2014-06-11 | 2014-10-22 | 浙江工业大学 | Process and device for one-step air catalytic oxidation synthesis of picolinic acid type compounds |
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Application publication date: 20150311 |