CN104230800B - A kind of preparation method of copper 8-quinolinolate - Google Patents
A kind of preparation method of copper 8-quinolinolate Download PDFInfo
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- CN104230800B CN104230800B CN201410410410.3A CN201410410410A CN104230800B CN 104230800 B CN104230800 B CN 104230800B CN 201410410410 A CN201410410410 A CN 201410410410A CN 104230800 B CN104230800 B CN 104230800B
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- quinoline
- copper
- hydroxyquinoline
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- water
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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
- C07D215/30—Metal salts; Chelates
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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The invention discloses the preparation method of a kind of 8 copper quinolinates, belong to technical field of organic synthesis.Preparation method comprises the following steps: after (1) quinoline and oleum add thermal response, hydrolysis obtains quinoline 8 sulfonic acid, and quinoline 8 sulfonic acid and solid sodium hydroxide add thermal response and prepare 8 oxyquinolines；(2) 8 oxyquinolines prepared by NaOH and step (1) are dissolved completely in water, add anhydrous cupric sulfate reaction and obtain 8 copper quinolinates.The inventive method yield is high, and 8 copper quinolinate purity of preparation are high, constant product quality, colour stable, it is adaptable to high-end product market.
Description
Technical field
The present invention relates to technical field of organic synthesis, the synthetic method of a kind of copper 8-hydroxyquinolinate.
Background technology
Copper 8-quinolinolate is yellow green crystalline powder, and odorless, tasteless is non-volatile, not deliquescence, at high temperature
Decompose blackening, water insoluble and most of organic solvents.It is mainly used as biocide mildewcide；Agricultural chemicals, medicine close
Become metal inhibitor；Agriculturally be used as bactericide, also serve as rope, line, leather, vinyl plastics anti-
Mould dose.
Conventional production method is mainly led to o-aminophenol, o-nitrophenol, methacrylaldehyde for primary raw material
Cross cyclisation, neutralization, water vapour punching evaporate and obtain 8-hydroxyquinoline (be called for short o-aminophenol method), then with 8-
Oxyquinoline, copper sulphate are that raw material carries out complex reaction and obtains copper 8-quinolinolate, the 8-that the method produces
Copper quinolinate product purity low (about 97%), product colour changes in time, and quality is unstable,
It is not suitable for high-end product market.
Employing said method synthesis 8-hydroxyquinoline in documents such as " the synthesis technique designs of copper 8-hydroxyquinolinate ", then with
Mantoquita is synthesized copper 8-hydroxyquinolinate, and the copper 8-quinolinolate product purity that said method obtains is the most relatively low, and quality is not
Stable.
Summary of the invention
The technical problem to be solved in the present invention is to provide the preparation method of a kind of copper 8-quinolinolate, method yield
Height, the copper 8-quinolinolate purity of preparation is high, constant product quality, colour stable, it is adaptable to high-end product
Market.
For solving above-mentioned technical problem, the technical solution used in the present invention is:
A kind of preparation method of copper 8-quinolinolate, preparation method comprises the following steps:
(1) after quinoline and oleum add thermal response, hydrolysis obtains quinoline-8-sulfonic acid, and quinoline-8-sulfonic acid is with solid
Body NaOH adds thermal response and prepares 8-hydroxyquinoline；
(2) 8-hydroxyquinoline prepared by NaOH and step (1) is dissolved completely in water, adds five
Brochanite reaction obtains copper 8-quinolinolate.
In step (1), the concentration of oleum is 65%.
In step (1), quinoline is 130～150 DEG C with the reaction temperature of oleum, and the reaction time is 1～3
Hour.
In step (1), the mass ratio of oleum and quinoline is 2～4:1, the mass ratio of quinoline and water be 1:4～
8。
Preferably in step (1), the mass ratio of oleum and quinoline is 3:1, and quinoline with the mass ratio of water is
1:6。
Step (1) is cooled to 10～40 DEG C after hydrolysis and is filtrated to get quinoline-8-sulfonic acid, quinoline-8-sulfonic acid
It is 1:1.2～2.0 with the mass ratio of solid sodium hydroxide, quinoline-8-sulfonic acid and the reaction of solid sodium hydroxide
Temperature is 330～360 DEG C.
In step (1), the reaction of quinoline-8-sulfonic acid and solid sodium hydroxide terminates after vulcanization acid for adjusting pH value and is
6～9, water vapour punching evaporates and obtains 8-hydroxyquinoline.
8-hydroxyquinoline, NaOH and water are warmed up to 40～90 DEG C to 8-hydroxyquinoline by step (2)
It is completely dissolved.
Drip cupric sulfate pentahydrate under 60～150r/min rotating speeds, be cooled to 25～30 DEG C after completion of the reaction, filter,
It is dried to obtain copper 8-quinolinolate；
The mass ratio of 8-hydroxyquinoline, NaOH and water is 100～150:20～50:1500, five water sulfuric acid
Copper is 80～120:125 with the mass ratio of 8-hydroxyquinoline.
Preferably the mass ratio of 8-hydroxyquinoline, NaOH and water is 125:35.4:1500, five water sulfuric acid
Copper is 107.5:125 with the mass ratio of 8-hydroxyquinoline.
Water vapour punching evaporates and refers to directly be passed through in the solution containing 8-hydroxyquinoline crude product by steam, the thing steamed
Containing 8-hydroxyquinoline and steam in material, after condensation layering, obtain 8-hydroxyquinoline.
Quinoline-8-sulfonic acid, structural formula is
Using the technical program first to prepare high-purity (more than 99.5%) 8-hydroxyquinoline, color is white
Solid, long storage time color will not change；And containing few in the 8-hydroxyquinoline that o-aminophenol method produces
Amount amino compound, changes colour over time is gradually deepened until becoming dark brown, the most just this
Individual reason, the copper 8-quinolinolate color difference that two kinds of methods are produced, the 8-hydroxyl that the technical program produces
Copper 8-hydroxyquinolinate is not easy variable color, stay in grade.
Use and have the beneficial effects that produced by technique scheme: the inventive method yield is high, the 8-of preparation
Copper quinolinate purity is high, constant product quality, colour stable, it is adaptable to high-end product market.
The present invention obtains 8-hydroxyquinoline for raw material through sulfonation, alkali fusion, neutralization with quinoline, then with 8-
Oxyquinoline, copper sulphate are that raw material carries out complex reaction and obtains copper 8-quinolinolate, the 8-that the method produces
Copper quinolinate product purity is high (more than 99%), and product colour changes the most in time.
Detailed description of the invention
Embodiment 1
A kind of preparation method of copper 8-quinolinolate, preparation method comprises the following steps:
(1) synthesis of 8-hydroxyquinoline
In the reactor of a band agitating device, add the oleum of 750g65% (mass concentration),
Less than 100 degree dropping 250g99% quinoline, are warmed up to 140 DEG C, and keep 2 hours, pour in 1500g water
Hydrolysis, is cooled to 10～40 DEG C of filtrations, and the 300g quinoline-8-sulfonic acid obtained, with 450gNaOH at 345 DEG C
Reaction, is neutralized to pH 6～9 with sulfuric acid after question response, and water vapour punching evaporates and obtains 8-hydroxyquinoline
125g。
(2) synthesis of copper 8-quinolinolate
In the reactor of a band agitating device, add 125g8-oxyquinoline, 35.4g NaOH,
1500g water, is warmed up to 40～90 DEG C, after determining that 8-hydroxyquinoline all dissolves, adjust speed of agitator 60～
Between 150r/min, adding 107.5g cupric sulfate pentahydrate, keep 1 hour after adding, reaction terminates, fall
Temperature, to 25～30 degree, filters, obtains 8-hydroxyquinoline copper products 150.5g after drying.Product purity is
99.7%, granularity is between 5～40um, and yield is 99.3%.
Embodiment 2
A kind of preparation method of copper 8-quinolinolate, preparation method comprises the following steps:
(1) synthesis of 8-hydroxyquinoline
In the reactor of a band agitating device, add the oleum of 500g65% (mass concentration),
Less than 100 degree dropping 250g99% quinoline, are warmed up to 150 DEG C, and keep 2 hours, pour in 1000g water
Hydrolysis, is cooled to 10～40 DEG C of filtrations, and the 290g quinoline-8-sulfonic acid obtained, with 435gNaOH at 330 DEG C
Reaction, is neutralized to pH 6～9 with sulfuric acid after question response, and water vapour punching evaporates and obtains 8-hydroxyquinoline
120g。
(2) synthesis of copper 8-quinolinolate
In the reactor of a band agitating device, add 120g8-oxyquinoline, 34g NaOH, 1500g
Water, is warmed up to 40～90 DEG C, after determining that 8-hydroxyquinoline all dissolves, adjust speed of agitator 60～
Between 150r/min, adding 103.2g cupric sulfate pentahydrate, keep 1 hour after adding, reaction terminates, fall
Temperature, to 25～30 degree, filters, obtains 8-hydroxyquinoline copper products 144g after drying.Product purity is 99.8%,
Granularity is between 5～40um, and yield is 99.0%.
Embodiment 3
A kind of preparation method of copper 8-quinolinolate, preparation method comprises the following steps:
(1) synthesis of 8-hydroxyquinoline
In the reactor of a band agitating device, add the oleum of 1000g65% (mass concentration),
Less than 100 degree dropping 250g99% quinoline, are warmed up to 130 DEG C, and keep 3 hours, pour in 2000g water
Hydrolysis, cooling filtration, the 295g quinoline-8-sulfonic acid obtained, with 442.5gNaOH 360 DEG C of reactions, treat
Being neutralized to pH 6～9 with sulfuric acid after completion of the reaction, water vapour punching evaporates and obtains 8-hydroxyquinoline 123g.
(2) synthesis of copper 8-quinolinolate
In the reactor of a band agitating device, add 123g8-oxyquinoline, 35.4g NaOH,
1500g water, is warmed up to 40～90 DEG C, after determining that 8-hydroxyquinoline all dissolves, adjust speed of agitator 60～
Between 150r/min, adding 105.8g cupric sulfate pentahydrate, keep 1 hour after adding, reaction terminates, fall
Temperature, to 25～30 degree, filters, obtains 8-hydroxyquinoline copper products 147.8g after drying.Product purity is
99.6%, granularity is between 5～40um, and yield is 99.1%.
Embodiment 4
A kind of preparation method of copper 8-quinolinolate, preparation method comprises the following steps:
(1) synthesis of 8-hydroxyquinoline
In the reactor of a band agitating device, the oleum of addition 65% (mass concentration), 100
Dripping 99% quinoline below Du, be warmed up to 135 DEG C, and keep 3 hours, be poured into water hydrolysis, cooling is filtered,
Quinoline-8-the sulfonic acid obtained, with NaOH 350 DEG C of reactions, is neutralized to pH with sulfuric acid after question response and exists
6～9, water vapour punching evaporates and obtains 8-hydroxyquinoline.
Oleum is 2.5:1 with the mass ratio of quinoline, and quinoline is 1:7 with the mass ratio of water；
Quinoline-8-sulfonic acid is 1:1.8 with the mass ratio of solid sodium hydroxide.
(2) synthesis of copper 8-quinolinolate
In the reactor of a band agitating device, add 8-hydroxyquinoline, NaOH, and water, heat up
To 40～90 DEG C, after determining that 8-hydroxyquinoline all dissolves, adjust speed of agitator 60～150r/min it
Between, add cupric sulfate pentahydrate, keep after adding to reaction terminating, cool to 25～30 degree, filter, be dried
After obtain 8-hydroxyquinoline copper products.
The mass ratio of 8-hydroxyquinoline, NaOH and water is 110:40:1500, cupric sulfate pentahydrate and 8-hydroxyl
The mass ratio of base quinoline is 80:125.
Embodiment 5
A kind of preparation method of copper 8-quinolinolate, preparation method comprises the following steps:
(1) synthesis of 8-hydroxyquinoline
In the reactor of a band agitating device, the oleum of addition 65% (mass concentration), 100
Dripping 99% quinoline below Du, be warmed up to 140 DEG C, and keep 2 hours, be poured into water hydrolysis, cooling is filtered,
Quinoline-8-the sulfonic acid obtained, with NaOH 355 DEG C of reactions, is neutralized to pH with sulfuric acid after question response and exists
6～9, water vapour punching evaporates and obtains 8-hydroxyquinoline.
Oleum is 3.5:1 with the mass ratio of quinoline, and quinoline is 1:5 with the mass ratio of water；
Quinoline-8-sulfonic acid is 1:1.5 with the mass ratio of solid sodium hydroxide.
(2) synthesis of copper 8-quinolinolate
In the reactor of a band agitating device, add 8-hydroxyquinoline, NaOH, water, be warmed up to
40～90 DEG C, after determining that 8-hydroxyquinoline all dissolves, adjust speed of agitator between 60～150r/min,
Adding cupric sulfate pentahydrate, keep 1 hour after adding, reaction terminates, and cools to 25～30 degree, filters, dry
8-hydroxyquinoline copper products is obtained after dry.
The mass ratio of 8-hydroxyquinoline, NaOH and water is 125:40:1500, cupric sulfate pentahydrate and 8-hydroxyl
The mass ratio of base quinoline is 100:125.
Claims (6)
1. the preparation method of a copper 8-quinolinolate, it is characterised in that preparation method comprises the following steps:
(1) after quinoline and oleum add thermal response, hydrolysis obtains quinoline-8-sulfonic acid, and quinoline-8-sulfonic acid is with solid
Body NaOH adds thermal response and prepares 8-hydroxyquinoline；
Cooling to 10～40 DEG C after hydrolysis and be filtrated to get quinoline-8-sulfonic acid, quinoline-8-sulfonic acid aoxidizes with solid hydrogen
The mass ratio of sodium is 1:1.2～2.0, the reaction temperature of quinoline-8-sulfonic acid and solid sodium hydroxide be 330～
360℃；
It is 6～9 that the reaction of quinoline-8-sulfonic acid and solid sodium hydroxide terminates after vulcanization acid for adjusting pH value, and water steams
Vapour punching evaporates and obtains 8-hydroxyquinoline；
(2) 8-hydroxyquinoline prepared by NaOH and step (1) is dissolved completely in water, by 8-
Oxyquinoline, NaOH and water are warmed up to 40～90 DEG C and are completely dissolved to 8-hydroxyquinoline, 60～
Drip cupric sulfate pentahydrate under 150r/min rotating speed, be cooled to 25～30 DEG C after completion of the reaction, filter, be dried
To copper 8-quinolinolate；
The mass ratio of 8-hydroxyquinoline, NaOH and water is 100～150:20～50:1500, five water sulfuric acid
Copper is 80～120:125 with the mass ratio of 8-hydroxyquinoline.
The preparation method of copper 8-quinolinolate the most according to claim 1, it is characterised in that step (1)
The concentration of middle oleum is 65%.
The preparation method of copper 8-quinolinolate the most according to claim 1 and 2, it is characterised in that step
Suddenly in (1), the reaction temperature of quinoline and oleum is 130～150 DEG C, and the reaction time is 1～3 hour.
The preparation method of copper 8-quinolinolate the most according to claim 1 and 2, it is characterised in that step
Suddenly in (1), the mass ratio of oleum and quinoline is 2～4:1, and quinoline is 1:4～8 with the mass ratio of water.
The preparation method of copper 8-quinolinolate the most according to claim 4, it is characterised in that step (1)
Middle oleum is 3:1 with the mass ratio of quinoline, and quinoline is 1:6 with the mass ratio of water.
The preparation method of copper 8-quinolinolate the most according to claim 1, it is characterised in that 8-hydroxyl
The mass ratio of quinoline, NaOH and water is 125:35.4:1500, cupric sulfate pentahydrate and 8-hydroxyquinoline
Mass ratio is 107.5:125.
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| CN104710357A (en) * | 2015-03-13 | 2015-06-17 | 武汉瑞凯兴科技有限公司 | Synthetic method for 8-hydroxyquinoline |
| CN105622502B (en) * | 2016-02-29 | 2018-03-09 | 苏州艾缇克药物化学有限公司 | A kind of synthetic method of 8 oxyquinoline |
| CN105777629A (en) * | 2016-03-31 | 2016-07-20 | 苏州华道生物药业股份有限公司 | Production process for 8-hydroxyquinoline |
| CN107573284A (en) * | 2017-09-05 | 2018-01-12 | 刘正信 | A kind of preparation method of 8 oxyquinoline |
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| CS213023B1 (en) * | 1980-08-28 | 1982-03-26 | Ivanka Malkova | Method of preparation of 8-chinolinole and cupric salts thereof |
| CS241829B1 (en) * | 1984-09-28 | 1986-04-17 | Karel Pastalka | Isolation method of 8 quinoline |
| CN101830793A (en) * | 2010-05-13 | 2010-09-15 | 中科院广州化学有限公司 | Method for preparing hydroxyl-substituted phenylacetic acid compound |
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| JPS4943983A (en) * | 1972-09-02 | 1974-04-25 | ||
| JPH0943983A (en) * | 1995-07-31 | 1997-02-14 | Mita Ind Co Ltd | Toner cartridge mounting device |
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Patent Citations (3)
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|---|---|---|---|---|
| CS213023B1 (en) * | 1980-08-28 | 1982-03-26 | Ivanka Malkova | Method of preparation of 8-chinolinole and cupric salts thereof |
| CS241829B1 (en) * | 1984-09-28 | 1986-04-17 | Karel Pastalka | Isolation method of 8 quinoline |
| CN101830793A (en) * | 2010-05-13 | 2010-09-15 | 中科院广州化学有限公司 | Method for preparing hydroxyl-substituted phenylacetic acid compound |
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