CN104230800A - Preparation method of copper 8-hydroxyquinoline - Google Patents
Preparation method of copper 8-hydroxyquinoline Download PDFInfo
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- CN104230800A CN104230800A CN201410410410.3A CN201410410410A CN104230800A CN 104230800 A CN104230800 A CN 104230800A CN 201410410410 A CN201410410410 A CN 201410410410A CN 104230800 A CN104230800 A CN 104230800A
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- Prior art keywords
- copper
- quinoline
- oxine
- quinolinolate
- preparation
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- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- IURRXCRWRKQLGC-UHFFFAOYSA-N copper;quinolin-8-ol Chemical compound [Cu].C1=CN=C2C(O)=CC=CC2=C1.C1=CN=C2C(O)=CC=CC2=C1 IURRXCRWRKQLGC-UHFFFAOYSA-N 0.000 title abstract 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 87
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims abstract description 51
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 18
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- YXLXNENXOJSQEI-UHFFFAOYSA-L Oxine-copper Chemical compound [Cu+2].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 YXLXNENXOJSQEI-UHFFFAOYSA-L 0.000 claims description 44
- SXVRECLPTCOMIA-UHFFFAOYSA-N quinoline-8-sulfonic acid Chemical compound C1=CN=C2C(S(=O)(=O)O)=CC=CC2=C1 SXVRECLPTCOMIA-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000004080 punching Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004073 vulcanization Methods 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 12
- 239000005725 8-Hydroxyquinoline Substances 0.000 abstract 2
- 229960003540 oxyquinoline Drugs 0.000 abstract 2
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 238000002156 mixing Methods 0.000 description 5
- 238000012423 maintenance Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- -1 o-NP Chemical compound 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of copper 8-hydroxyquinoline, belonging to the technical field of organic synthesis. The preparation method comprises the following steps: (1) heating quinoline and fuming sulfuric acid to react, hydrolyzing to obtain quinolyl-8-sulfonic acid, and heating the quinolyl-8-sulfonic acid and solid sodium hydroxide to react to obtain 8-hydroxyquinoline; and (2) completely dissolve sodium hydroxide and the 8-hydroxyquinoline prepared in the step (1) in water, and adding anhydrous cupric sulfate to react to obtain the copper 8-hydroxyquinoline. The method is high in yield; and the prepared copper 8-hydroxyquinoline has the advantages of high purity, stable product quality and stable color, and is suitable for the high-end produce market.
Description
Technical field
The present invention relates to technical field of organic synthesis, especially a kind of synthetic method of oxinecopper.
Background technology
Copper 8-quinolinolate is yellow-green colour crystalline powder, and odorless, tasteless is non-volatile, and not deliquescence, at high temperature decomposes blackening, water insoluble and most of organic solvent.Main as biocide mildewcide; Agricultural chemicals, medical synthetic metals inhibiter; Agriculturally be used as sterilant, be also used as the mould inhibitor of rope, line, leather, vinyl plastics.
Conventional production method is mainly heated up in a steamer is obtained oxine (be called for short Ortho-Aminophenol method) by cyclisation, neutralization, water vapor punching for main raw material with Ortho-Aminophenol, o-NP, propenal, then copper 8-quinolinolate is obtained with oxine, copper sulfate for raw material carries out complex reaction, the copper 8-quinolinolate product purity low (about 97%) that this method is produced, product colour changes in time, quality is unstable, is not suitable for high-end product market.
Adopt aforesaid method to synthesize oxine in documents such as the synthesis technique of the oxinecoppers " design ", then with mantoquita Reactive Synthesis oxinecopper, the copper 8-quinolinolate product purity that aforesaid method obtains is all lower, and quality is unstable.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of preparation method of copper 8-quinolinolate, and method yield is high, and the copper 8-quinolinolate purity of preparation is high, constant product quality, and colour stable, is applicable to high-end product market.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
A preparation method for copper 8-quinolinolate, preparation method comprises the following steps:
(1) be hydrolyzed after quinoline and oleum reacting by heating and obtain quinoline-8-sulfonic acid, quinoline-8-sulfonic acid and solid sodium hydroxide reacting by heating obtain oxine;
(2) oxine prepared by sodium hydroxide and step (1) is dissolved in the water completely, adds cupric sulfate pentahydrate and be obtained by reacting copper 8-quinolinolate.
In step (1), the concentration of oleum is 65%.
In step (1), the temperature of reaction of quinoline and oleum is 130 ~ 150 DEG C, and the reaction times is 1 ~ 3 hour.
In step (1), the mass ratio of oleum and quinoline is 2 ~ 4:1, and the mass ratio of quinoline and water is 1:4 ~ 8.
In preferred step (1), the mass ratio of oleum and quinoline is 3:1, and the mass ratio of quinoline and water is 1:6.
Be cooled to 10 ~ 40 DEG C of filtrations after hydrolysis in step (1) and obtain quinoline-8-sulfonic acid, the mass ratio of quinoline-8-sulfonic acid and solid sodium hydroxide is 1:1.2 ~ 2.0, and the temperature of reaction of quinoline-8-sulfonic acid and solid sodium hydroxide 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 is 6 ~ 9, and water vapor punching is heated up in a steamer and obtained oxine.
In step (2), oxine, sodium hydroxide and water are warmed up to 40 ~ 90 DEG C to dissolve completely to oxine.
Drip cupric sulfate pentahydrate under 60 ~ 150r/min rotating speed, be cooled to 25 ~ 30 DEG C after completion of the reaction, filter, drying obtains copper 8-quinolinolate;
The mass ratio of oxine, sodium hydroxide and water is 100 ~ 150:20 ~ 50:1500, and the mass ratio of cupric sulfate pentahydrate and oxine is 80 ~ 120:125.
The mass ratio of preferred oxine, sodium hydroxide and water is 125:35.4:1500, and the mass ratio of cupric sulfate pentahydrate and oxine is 107.5:125.
Water vapor punching is heated up in a steamer in the solution referring to and directly passed into by steam containing oxine crude product, containing oxine and steam in the material steamed, obtains oxine after condensation layering.
Quinoline-8-sulfonic acid, structural formula is
Adopt the technical program first to prepare high purity (more than 99.5%) oxine, color is white solid, and long storage time color can not change; And containing a small amount of amino compound in the oxine that Ortho-Aminophenol method is produced, changes colour along with the time is deepened until become Vandyke brown gradually, also this reason just, the copper 8-quinolinolate color difference that two kinds of methods are produced, the copper 8-quinolinolate that the technical program is produced is not easy variable color, stay in grade.
The beneficial effect adopting technique scheme to produce is: the inventive method yield is high, and the copper 8-quinolinolate purity of preparation is high, constant product quality, and colour stable, is applicable to high-end product market.
The present invention is that raw material obtains oxine through oversulfonate, alkali fusion, neutralization with quinoline, then copper 8-quinolinolate is obtained with oxine, copper sulfate for raw material carries out complex reaction, the copper 8-quinolinolate product purity high (more than 99%) that this method is produced, product colour does not change in time.
Embodiment
Embodiment 1
A preparation method for copper 8-quinolinolate, preparation method comprises the following steps:
(1) synthesis of oxine
In the reactor of a band whipping appts, add the oleum of 750g65% (mass concentration), less than 100 degree drip 250g99% quinoline, are warmed up to 140 DEG C, and keep 2 hours, pour in 1500g water and be hydrolyzed, be cooled to 10 ~ 40 DEG C of filtrations, the 300g quinoline-8-sulfonic acid obtained, reacts at 345 DEG C with 450gNaOH, be neutralized to pH 6 ~ 9 with sulfuric acid after question response, water vapor punching is heated up in a steamer and is obtained oxine 125g.
(2) synthesis of copper 8-quinolinolate
In the reactor of a band whipping appts, add 125g8-hydroxyquinoline, 35.4g sodium hydroxide, 1500g water, be warmed up to 40 ~ 90 DEG C, after determining that oxine all dissolves, adjustment mixing speed, between 60 ~ 150r/min, adds 107.5g cupric sulfate pentahydrate, adds rear maintenance 1 hour, reaction terminates, cool to 25 ~ 30 degree, filter, after drying, obtain oxine copper products 150.5g.Product purity is 99.7%, granularity between 5 ~ 40um, yield is 99.3%.
Embodiment 2
A preparation method for copper 8-quinolinolate, preparation method comprises the following steps:
(1) synthesis of oxine
In the reactor of a band whipping appts, add the oleum of 500g65% (mass concentration), less than 100 degree drip 250g99% quinoline, are warmed up to 150 DEG C, and keep 2 hours, pour in 1000g water and be hydrolyzed, be cooled to 10 ~ 40 DEG C of filtrations, the 290g quinoline-8-sulfonic acid obtained, reacts at 330 DEG C with 435gNaOH, be neutralized to pH 6 ~ 9 with sulfuric acid after question response, water vapor punching is heated up in a steamer and is obtained oxine 120g.
(2) synthesis of copper 8-quinolinolate
In the reactor of a band whipping appts, add 120g8-hydroxyquinoline, 34g sodium hydroxide, 1500g water, be warmed up to 40 ~ 90 DEG C, after determining that oxine all dissolves, adjustment mixing speed, between 60 ~ 150r/min, adds 103.2g cupric sulfate pentahydrate, adds rear maintenance 1 hour, reaction terminates, cool to 25 ~ 30 degree, filter, after drying, obtain oxine copper products 144g.Product purity is 99.8%, granularity between 5 ~ 40um, yield is 99.0%.
Embodiment 3
A preparation method for copper 8-quinolinolate, preparation method comprises the following steps:
(1) synthesis of oxine
In the reactor of a band whipping appts, add the oleum of 1000g65% (mass concentration), less than 100 degree drip 250g99% quinoline, are warmed up to 130 DEG C, and keep 3 hours, pour in 2000g water and be hydrolyzed, cooling is filtered, and the 295g quinoline-8-sulfonic acid obtained, reacts at 360 DEG C with 442.5gNaOH, be neutralized to pH 6 ~ 9 with sulfuric acid after question response, water vapor punching is heated up in a steamer and is obtained oxine 123g.
(2) synthesis of copper 8-quinolinolate
In the reactor of a band whipping appts, add 123g8-hydroxyquinoline, 35.4g sodium hydroxide, 1500g water, be warmed up to 40 ~ 90 DEG C, after determining that oxine all dissolves, adjustment mixing speed, between 60 ~ 150r/min, adds 105.8g cupric sulfate pentahydrate, adds rear maintenance 1 hour, reaction terminates, cool to 25 ~ 30 degree, filter, after drying, obtain oxine copper products 147.8g.Product purity is 99.6%, granularity between 5 ~ 40um, yield is 99.1%.
Embodiment 4
A preparation method for copper 8-quinolinolate, preparation method comprises the following steps:
(1) synthesis of oxine
In the reactor of a band whipping appts, add the oleum of 65% (mass concentration), less than 100 degree drip 99% quinoline, are warmed up to 135 DEG C, and keep 3 hours, be poured into water hydrolysis, cooling is filtered, and the quinoline-8-sulfonic acid obtained, reacts at 350 DEG C with NaOH, be neutralized to pH 6 ~ 9 with sulfuric acid after question response, water vapor punching is heated up in a steamer and is obtained oxine.
The mass ratio of oleum and quinoline is 2.5:1, and the mass ratio of quinoline and water is 1:7;
The mass ratio of quinoline-8-sulfonic acid and solid sodium hydroxide is 1:1.8.
(2) synthesis of copper 8-quinolinolate
In the reactor of a band whipping appts, add oxine, sodium hydroxide, and water, be warmed up to 40 ~ 90 DEG C, after determining that oxine all dissolves, adjustment mixing speed is between 60 ~ 150r/min, add cupric sulfate pentahydrate, be retained to reaction after adding and terminate, cool to 25 ~ 30 degree, filter, after drying, obtain oxine copper products.
The mass ratio of oxine, sodium hydroxide and water is 110:40:1500, and the mass ratio of cupric sulfate pentahydrate and oxine is 80:125.
Embodiment 5
A preparation method for copper 8-quinolinolate, preparation method comprises the following steps:
(1) synthesis of oxine
In the reactor of a band whipping appts, add the oleum of 65% (mass concentration), less than 100 degree drip 99% quinoline, are warmed up to 140 DEG C, and keep 2 hours, be poured into water hydrolysis, cooling is filtered, and the quinoline-8-sulfonic acid obtained, reacts at 355 DEG C with NaOH, be neutralized to pH 6 ~ 9 with sulfuric acid after question response, water vapor punching is heated up in a steamer and is obtained oxine.
The mass ratio of oleum and quinoline is 3.5:1, and the mass ratio of quinoline and water is 1:5;
The mass ratio of quinoline-8-sulfonic acid and solid sodium hydroxide is 1:1.5.
(2) synthesis of copper 8-quinolinolate
In the reactor of a band whipping appts, add oxine, sodium hydroxide, water, be warmed up to 40 ~ 90 DEG C, after determining that oxine all dissolves, adjustment mixing speed, between 60 ~ 150r/min, adds cupric sulfate pentahydrate, adds rear maintenance 1 hour, reaction terminates, cool to 25 ~ 30 degree, filter, after drying, obtain oxine copper products.
The mass ratio of oxine, sodium hydroxide and water is 125:40:1500, and the mass ratio of cupric sulfate pentahydrate and oxine is 100:125.
Claims (10)
1. a preparation method for copper 8-quinolinolate, is characterized in that preparation method comprises the following steps:
(1) be hydrolyzed after quinoline and oleum reacting by heating and obtain quinoline-8-sulfonic acid, quinoline-8-sulfonic acid and solid sodium hydroxide reacting by heating obtain oxine;
(2) oxine prepared by sodium hydroxide and step (1) is dissolved in the water completely, adds cupric sulfate pentahydrate and be obtained by reacting copper 8-quinolinolate.
2. the preparation method of copper 8-quinolinolate according to claim 1, is characterized in that the concentration of oleum in step (1) is 65%.
3. the preparation method of copper 8-quinolinolate according to claim 1 and 2, it is characterized in that the temperature of reaction of quinoline and oleum in step (1) is 130 ~ 150 DEG C, the reaction times is 1 ~ 3 hour.
4. the preparation method of copper 8-quinolinolate according to claim 1 and 2, it is characterized in that the mass ratio of oleum and quinoline in step (1) is 2 ~ 4:1, the mass ratio of quinoline and water is 1:4 ~ 8.
5. the preparation method of copper 8-quinolinolate according to claim 4, it is characterized in that the mass ratio of oleum and quinoline in step (1) is 3:1, the mass ratio of quinoline and water is 1:6.
6. the preparation method of copper 8-quinolinolate according to claim 1 and 2, it is characterized in that cooling to 10 ~ 40 DEG C of filtrations after hydrolysis in step (1) obtains quinoline-8-sulfonic acid, the mass ratio of quinoline-8-sulfonic acid and solid sodium hydroxide is 1:1.2 ~ 2.0, and the temperature of reaction of quinoline-8-sulfonic acid and solid sodium hydroxide is 330 ~ 360 DEG C.
7. the preparation method of copper 8-quinolinolate according to claim 6, it is characterized in that the reaction of quinoline-8-sulfonic acid and solid sodium hydroxide in step (1) terminates after vulcanization acid for adjusting pH value is 6 ~ 9, and water vapor punching is heated up in a steamer and obtained oxine.
8. the preparation method of copper 8-quinolinolate according to claim 1, is characterized in that in step (2), oxine, sodium hydroxide and water being warmed up to 40 ~ 90 DEG C dissolves completely to oxine.
9. the preparation method of copper 8-quinolinolate according to claim 8, drips cupric sulfate pentahydrate under it is characterized in that 60 ~ 150r/min rotating speed, is cooled to 25 ~ 30 DEG C after completion of the reaction, and filter, drying obtains copper 8-quinolinolate;
The mass ratio of oxine, sodium hydroxide and water is 100 ~ 150:20 ~ 50:1500, and the mass ratio of cupric sulfate pentahydrate and oxine is 80 ~ 120:125.
10. the preparation method of copper 8-quinolinolate according to claim 9, is characterized in that the mass ratio of oxine, sodium hydroxide and water is 125:35.4:1500, and the mass ratio of cupric sulfate pentahydrate and oxine is 107.5:125.
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| CN201410410410.3A CN104230800B (en) | 2014-08-20 | 2014-08-20 | A kind of preparation method of copper 8-quinolinolate |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104710357A (en) * | 2015-03-13 | 2015-06-17 | 武汉瑞凯兴科技有限公司 | Synthetic method for 8-hydroxyquinoline |
| CN105622502A (en) * | 2016-02-29 | 2016-06-01 | 苏州艾缇克药物化学有限公司 | Synthesis method of 8-hydroxyquinoline |
| 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 |
| CN116789597A (en) * | 2023-06-30 | 2023-09-22 | 信诺立兴(沧州渤海新区)化工有限公司 | An efficient catalytic green process for the synthesis of quinoline derivatives |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4943983A (en) * | 1972-09-02 | 1974-04-25 | ||
| 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 |
| JPH0943983A (en) * | 1995-07-31 | 1997-02-14 | Mita Ind Co Ltd | Toner cartridge mounting device |
| 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 |
-
2014
- 2014-08-20 CN CN201410410410.3A patent/CN104230800B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4943983A (en) * | 1972-09-02 | 1974-04-25 | ||
| 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 |
| JPH0943983A (en) * | 1995-07-31 | 1997-02-14 | Mita Ind Co Ltd | Toner cartridge mounting device |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| KENYON G. DANIE等: "Organic copper complexes as a new class of proteasome inhibitors and apoptosis inducers in human cancer cells", 《BIOCHEMICAL PHARMACOLOGY》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104710357A (en) * | 2015-03-13 | 2015-06-17 | 武汉瑞凯兴科技有限公司 | Synthetic method for 8-hydroxyquinoline |
| CN105622502A (en) * | 2016-02-29 | 2016-06-01 | 苏州艾缇克药物化学有限公司 | Synthesis method of 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 |
| CN116789597A (en) * | 2023-06-30 | 2023-09-22 | 信诺立兴(沧州渤海新区)化工有限公司 | An efficient catalytic green process for the synthesis of quinoline derivatives |
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| CN104230800B (en) | 2016-08-24 |
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