CN105777630A - 8-hydroxyquinoline and preparation method thereof - Google Patents
8-hydroxyquinoline and preparation method thereof Download PDFInfo
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- CN105777630A CN105777630A CN201610210452.1A CN201610210452A CN105777630A CN 105777630 A CN105777630 A CN 105777630A CN 201610210452 A CN201610210452 A CN 201610210452A CN 105777630 A CN105777630 A CN 105777630A
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- Prior art keywords
- hydroxyquinoline
- preparation
- reaction reagent
- formic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms 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
- C07D215/20—Oxygen atoms
- C07D215/24—Oxygen atoms attached in position 8
- C07D215/26—Alcohols; Ethers thereof
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses 8-hydroxyquinoline and a preparation method thereof. The preparation method comprises the following steps: (1) preparing a reaction reagent A, namely, mixing ortho-aminophenol and o-nitrophenol; (2) preparing a reaction reagent B, namely, mixing formic acid and acrolein, and adding a zeolite molecular sieve into a mixed liquid of the formic acid and the acrolein; (3) heating the reaction reagent A to 95-100 DEG C, adding the reaction reagent B, enabling the component to react under a condition of constant-temperature stirring, filtering, and cooling the filtrate to the room temperature; and (4) neutralizing the filtrate obtained in the step (3) by using a 40% sodium hydroxide solution, filtering again, and performing reduced pressure distillation, thereby obtaining a final expected product, that is, 8-hydroxyquinoline. Compared with the prior art, the preparation method has the advantages of rapid reaction, gentle condition and high yield and is particularly applicable to industrial production.
Description
Technical field:
The present invention relates to biomedicine technical field, particularly a kind of 8-hydroxyquinoline and preparation thereof
Method.
Background technology:
8-hydroxyquinoline is a kind of important medical synthetic intermediate, its synthesis technique and spreading out
Biological preparation is one of focus of current field of medicaments, chemical field.8-hydroxyquinoline can
To be directly used as disinfectant, its derivant also has important function at medical domain, such as its halogen
It is the important source material of synthetic drug for derivant, itrated compound etc., and can be used as synthetic pesticide, dye
Material and the important intermediate of other functional materials.Additionally, 8-hydroxyquinoline or performance are excellent
Different metal ion chelation agent, is widely used in the metal in metallurgical industry and analytical chemistry
The fields such as element chemical analysis, photometric analysis, metal ion extraction and anti-corrosion of metal.Just
Owing to 8-hydroxyquinoline is in the important function in the field such as medical, industrial, its synthetic method possesses
High value.
At present, the preparation technology of 8-hydroxyquinoline mainly has 8-chloroquinoline Hydrolyze method, 8-amino quinoline
Quinoline Hydrolyze method, sulfonated alkali fusion method and Skraup synthetic method.Wherein, 8-chloroquinoline Hydrolyze method
And 8-quinolin-2-ylamine Hydrolyze method is low due to expensive starting materials, productivity, is unsuitable for industrial sector.
And sulfonated alkali fusion method on the one hand need with quinoline as reaction raw materials the resource-constrained of quinoline own,
On the other hand need to consume substantial amounts of soda acid in course of reaction, generation waste water easily causes environment more
Pollute, the application of sulfonated alkali fusion method of the drawbacks limit of these two aspects.
Skraup synthetic method is
Raw material, altogether a kind of synthetic method of hot preparation 8-hydroxyquinoline, it has raw material and is easy to get, synthesizes
The simple advantage of route.But, the method reaction the most easily slug, it is therefore necessary to reduce former
The mixing velocity of material, this causes the response time long to a great extent；Additionally, course of reaction is held
Tend to have by-product tar to produce, cause the reduction of reaction yield.Therefore, find one to react
The 8-hydroxyquinoline preparation method that journey is easily controlled, the response time is short, by-product is few still has
Highly important meaning
Summary of the invention:
For the deficiencies in the prior art, the invention provides the system of a kind of 8-hydroxyquinoline
Preparation Method.This method overcomes response time length, productivity in tradition 8-hydroxyquinoline synthetic method
The unmanageable defect of low, reaction condition, has and reacts simple, mild condition, conversion ratio height
Advantage, be especially suitable for 8-hydroxyquinoline batch production on industrial sector.
In order to solve above-mentioned technical problem, technical scheme includes following step:
(1) configuration reaction reagent A: o-aminophenol and onitrophenol are mixed with neighbour
Amino-phenol/onitrophenol mixed liquor；
(2) configuration reaction reagent B: by formic acid, acrylic aldehyde mixing, mix to formic acid/acrylic aldehyde
Close and liquid adds zeolite molecular sieve；
(3) reaction reagent A is heated to 95-100 DEG C, is subsequently adding reaction reagent B, permanent
React under temperature stirring condition, filter, filtrate is cooled to room temperature；
(4) by filtrate, again mistake described in 40% sodium hydroxide solution neutralization procedure (3)
Filter, decompression distillation, obtain final required product 8-hydroxyquinoline.
Preferably, o-aminophenol and ortho-nitrophenyl in the reaction reagent A of described step (1)
Phenol mol ratio is 1:1.5.
Preferably, zeolite molecular sieve and formic acid/acrylic acid mixed liquor quality in described step (2)
Ratio is 0.5:1.
Preferably, in described step (2), the mol ratio of formic acid and acrylic aldehyde is 2:1.
Preferably, in described step (3), the mol ratio of o-aminophenol and acrylic aldehyde is 1:3.
Preferably, in described step (3), the response time is 1-2h.
The method have the advantages that
The present invention is respectively configured as reaction reagent A and reaction reagent B, wherein reaction reagent B
In enough formic acid serve effect prediluted to acrylic aldehyde, increase effectively acrylic aldehyde instead
Answer the degree of scatter in solution, decrease side reaction and occur；Formic acid substitutes sulfur of the prior art
Acid or other mixed acid, save reagent and reduce reaction severe degree；Additionally, reaction
The addition of zeolite molecular sieve in reagent B, has been significantly greatly increased connecing of acrylic aldehyde and reaction reagent A
Contacting surface is amassed, and can not only reduce reaction severe degree, and shorten the response time.The present invention with
Prior art is compared, have be swift in response, advantage that mild condition, productivity are high, be especially suitable for
Commercial production.
Detailed description of the invention:
Technical scheme is further illustrated below in conjunction with embodiment.
Embodiment 1
(1) configuration reaction reagent A: by 1mol o-aminophenol and 1.2mol ortho-nitrophenyl
Phenol mixes, and prepares o-aminophenol/onitrophenol mixed liquor；
(2) configuration reaction reagent B: by 5mol formic acid, the mixing of 3mol acrylic aldehyde, to first
Adding zeolite molecular sieve in acid/acrylic aldehyde mixed liquor, zeolite molecular sieve mixes with formic acid/acrylic acid
Liquid mass ratio is 0.5:1；
(3) reaction reagent A is heated to 95-100 DEG C, is subsequently adding reaction reagent B, permanent
React 1h under temperature stirring condition, filter, filtrate is cooled to room temperature；
(4) by filtrate, again mistake described in 40% sodium hydroxide solution neutralization procedure (3)
Filter, decompression distillation, obtain final required product 8-hydroxyquinoline.
Test result indicate that yield is 87.2%.
Embodiment 2
(1) configuration reaction reagent A: by 1mol o-aminophenol and 1.5mol ortho-nitrophenyl
Phenol mixes, and prepares o-aminophenol/onitrophenol mixed liquor；
(2) configuration reaction reagent B: by 6mol formic acid, the mixing of 3mol acrylic aldehyde, to first
Adding zeolite molecular sieve in acid/acrylic aldehyde mixed liquor, zeolite molecular sieve mixes with formic acid/acrylic acid
Liquid mass ratio is 0.5:1；
(3) reaction reagent A is heated to 95-100 DEG C, is subsequently adding reaction reagent B, permanent
React 2h under temperature stirring condition, filter, filtrate is cooled to room temperature；
(4) by filtrate, again mistake described in 40% sodium hydroxide solution neutralization procedure (3)
Filter, decompression distillation, obtain final required product 8-hydroxyquinoline.
Test result indicate that yield is 95.6%.
Embodiment 3
(1) configuration reaction reagent A: by 2mol o-aminophenol and 3mol onitrophenol
Mixing, prepares o-aminophenol/onitrophenol mixed liquor；
(2) configuration reaction reagent B: by 8mol formic acid, the mixing of 6mol acrylic aldehyde, to first
Adding zeolite molecular sieve in acid/acrylic aldehyde mixed liquor, zeolite molecular sieve mixes with formic acid/acrylic acid
Liquid mass ratio is 0.5:1；
(3) reaction reagent A is heated to 95-100 DEG C, is subsequently adding reaction reagent B, permanent
React 1.5h under temperature stirring condition, filter, filtrate is cooled to room temperature；
(4) by filtrate, again mistake described in 40% sodium hydroxide solution neutralization procedure (3)
Filter, decompression distillation, obtain final required product 8-hydroxyquinoline.
Test result indicate that yield is 82.1%.
Embodiment 4
(1) configuration reaction reagent A: by 2mol o-aminophenol and 3mol onitrophenol
Mixing, prepares o-aminophenol/onitrophenol mixed liquor；
(2) configuration reaction reagent B: by 12mol formic acid, the mixing of 6mol acrylic aldehyde, to first
Adding zeolite molecular sieve in acid/acrylic aldehyde mixed liquor, zeolite molecular sieve mixes with formic acid/acrylic acid
Liquid mass ratio is 0.5:1；
(3) reaction reagent A is heated to 95-100 DEG C, is subsequently adding reaction reagent B, permanent
React 2h under temperature stirring condition, filter, filtrate is cooled to room temperature；
(4) by filtrate, again mistake described in 40% sodium hydroxide solution neutralization procedure (3)
Filter, decompression distillation, obtain final required product 8-hydroxyquinoline.
Test result indicate that yield is 94.1%.
Above-described embodiment is merely to illustrate detailed process equipment and the flow process of the present invention, but and unexpectedly
Taste the present invention and is had to rely on and climb the tree detailed process equipment and flow process could be implemented.The skill of this area
The present invention can reasonably be changed by art personnel without departing from the spirit and scope of the present invention
Enter, within the scope of also should be regarded as falling into protection scope of the present invention and disclosure.
Claims (7)
1. the preparation method of a 8-hydroxyquinoline, it is characterised in that comprise the following steps:
(1) configuration reaction reagent A: o-aminophenol and onitrophenol are mixed with neighbour
Amino-phenol/onitrophenol mixed liquor；
(2) configuration reaction reagent B: by formic acid, acrylic aldehyde mixing, mix to formic acid/acrylic aldehyde
Close and liquid adds zeolite molecular sieve；
(3) reaction reagent A is heated to 95-100 DEG C, is subsequently adding reaction reagent B, permanent
React under temperature stirring condition, filter, filtrate is cooled to room temperature；
(4) by filtrate, again mistake described in 40% sodium hydroxide solution neutralization procedure (3)
Filter, decompression distillation, obtain final required product 8-hydroxyquinoline.
The preparation method of 8-hydroxyquinoline the most according to claim 1, it is characterised in that:
In the reaction reagent A of described step (1), o-aminophenol and onitrophenol mol ratio are
1:1.5。
The preparation method of 8-hydroxyquinoline the most according to claim 1, it is characterised in that:
In described step (2), zeolite molecular sieve and formic acid/acrylic acid mixed liquor mass ratio are 0.5:1.
The preparation method of 8-hydroxyquinoline the most according to claim 1, it is characterised in that:
In described step (2), the mol ratio of formic acid and acrylic aldehyde is 2:1.
The preparation method of 8-hydroxyquinoline the most according to claim 1, it is characterised in that:
Preferably, in described step (3), the mol ratio of o-aminophenol and acrylic aldehyde is 1:3.
The preparation method of 8-hydroxyquinoline the most according to claim 1, it is characterised in that:
In described step (3), the response time is 1-2h.
7. the preparation method institute of a kind of 8-hydroxyquinoline according to any one of claim 1-6
The 8-hydroxyquinoline prepared.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610210452.1A CN105777630A (en) | 2016-04-05 | 2016-04-05 | 8-hydroxyquinoline and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610210452.1A CN105777630A (en) | 2016-04-05 | 2016-04-05 | 8-hydroxyquinoline and preparation method thereof |
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| CN105777630A true CN105777630A (en) | 2016-07-20 |
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| CN201610210452.1A Pending CN105777630A (en) | 2016-04-05 | 2016-04-05 | 8-hydroxyquinoline and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108191753A (en) * | 2018-02-24 | 2018-06-22 | 利尔化学股份有限公司 | A kind of preparation method of 5- chloro-8-hydroxyquinolines |
| CN108752271A (en) * | 2018-06-28 | 2018-11-06 | 江苏新瑞药业有限公司 | A kind of synthetic method of oxyquinoline |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4044011A (en) * | 1974-10-14 | 1977-08-23 | Produits Chimiques Ugine Kuhlmann | Process for the preparation of 8-hydroxyquinoline |
| CN86102086A (en) * | 1986-03-20 | 1987-10-07 | 柯保桂 | The preparation of oxine |
-
2016
- 2016-04-05 CN CN201610210452.1A patent/CN105777630A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4044011A (en) * | 1974-10-14 | 1977-08-23 | Produits Chimiques Ugine Kuhlmann | Process for the preparation of 8-hydroxyquinoline |
| CN86102086A (en) * | 1986-03-20 | 1987-10-07 | 柯保桂 | The preparation of oxine |
Non-Patent Citations (2)
| Title |
|---|
| 张珍明 等: "Skraup法合成8-羟基喹啉", 《精细石油化工》 * |
| 柳云骐 等主编: "《材料化学》", 28 February 2013, 中国石油大学出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108191753A (en) * | 2018-02-24 | 2018-06-22 | 利尔化学股份有限公司 | A kind of preparation method of 5- chloro-8-hydroxyquinolines |
| CN108191753B (en) * | 2018-02-24 | 2022-03-15 | 利尔化学股份有限公司 | Preparation method of 5-chloro-8-hydroxyquinoline |
| CN108752271A (en) * | 2018-06-28 | 2018-11-06 | 江苏新瑞药业有限公司 | A kind of synthetic method of oxyquinoline |
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Application publication date: 20160720 |