CN110292950A - Copper-tetraethylethylenediamine uses it as the preparation method of the crocic acid of catalyst - Google Patents

Copper-tetraethylethylenediamine uses it as the preparation method of the crocic acid of catalyst Download PDF

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Publication number
CN110292950A
CN110292950A CN201810244954.5A CN201810244954A CN110292950A CN 110292950 A CN110292950 A CN 110292950A CN 201810244954 A CN201810244954 A CN 201810244954A CN 110292950 A CN110292950 A CN 110292950A
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reaction
catalyst
tetraethylethylenediamine
acid
copper
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徐开亮
施波
张小强
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Hede Chemistry (suzhou) Co Ltd
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Hede Chemistry (suzhou) Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/02—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0213—Complexes without C-metal linkages
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/16—Copper
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

The process route of synthesis crocic acid is to be synthesized using tetrachloroquinone as raw material with manganese dioxide or other strong-acid type oxidants mostly at present, and the quantity of three wastes that such process route generates is higher, unfriendly to environment.In order to solve problem above, the present invention proposes a kind of preparation method of crocic acid, due to the copper catalyst that can repeatedly apply of use, and solvent is made with water, and with dioxygen oxidation, compared with traditional handicraft, greatly reduce quantity of three wastes, have many advantages, such as it is environmentally protective, it is low in cost.

Description

Copper-tetraethylethylenediamine uses it as the preparation method of the crocic acid of catalyst
Technical field
The present invention relates to chemical industry synthesis fields, specifically, being related to copper-tetraethylethylenediamine, using copper-tetraethyl second two Preparation method of the amine as the crocic acid of catalyst is a kind of completely new, environment amenable preparation method.
Background technique
Crocic acid is a kind of important chemical intermediate, and purposes is very extensive.Crocic acid is used for bioanalysis neck now Domain is and the covalently bound near infrared fluorescent dye of biomolecule.Furthermore croconic acid dyes are a kind of novel near infrared absorptions Dyestuff due to stablizing row and fluorescence radiation performance with good photo-thermal, thus has with field of storage in optical recording potential Application value.
The process route of synthesis crocic acid is using tetrachloroquinone as raw material, with manganese dioxide or other strong-acid types mostly at present Oxidant synthesizes, and the defect of such process route clearly, first can generate in the production process of raw material tetrachloroquinone each For kind various kinds in chloro by-product, the environmental protection pressure that these impurity by-products are dealt with is quite big, while manganese dioxide or other strong Acid is compared as oxidant with catalysis oxidation, and dosage can be very big, inevitably generates a large amount of spent acid and manganate is miscellaneous Matter, these offal treatments are got up equally very intractable, are faced huge environmental protection pressure, therefore increasingly strict in environmental requirement, are advocated It leads the today for greatly developing environmental-friendly Green Chemistry, exploitation pollution is small, and environmental-friendly green chemistry process is imperative.
Summary of the invention
In view of this, the present invention provides a kind of environmentally protective synthetic method of crocic acid, due to can repeatedly applying for use Copper catalyst, and make solvent with water, and greatly reduce quantity of three wastes compared with traditional handicraft with dioxygen oxidation, have green The advantages that colour circle is protected, low in cost.
In order to realize that above-mentioned purpose of the invention, the present invention propose copper-tetraethylethylenediamine catalyst preparation method, Include the following steps:
By stannous chloride, tetraethylethylenediamine, water and methanol are that 3: 8: 1: 12 ratio sequentially adds reaction in mass ratio In kettle, being sufficiently stirred makes its Quan Rong, after be passed through oxygen and do not stir, duration of ventilation is controlled in 30-120mins, oxygen flow control System in 50-2000ml/min, after filter out solid, with acetone washing, be dried under reduced pressure 6-10hrs at 40-60 DEG C, what is obtained is purplish red Color powder is for copper-tetraethylethylenediamine catalyst.
In addition, the present invention also proposes the preparation method for the crocic acid for using copper-tetraethylethylenediamine as catalyst, packet Include following steps:
S1, by deionized water, rhodizonic acid is added sequentially to by 10: 1 mass ratio equipped with gas-guide tube, PH meter, stirring It in the reaction kettle of thermometer, is stirred at room temperature to solution and clarifies, copper-tetraethylethylenediamine of rhodizonic acid weight 10% is added Catalyst, after the deionized water solution of 10% sodium hydroxide of configured in advance is placed in charging spout；
S2 is warming up to 80-85 DEG C and is reacted and started dropwise addition hydroxide with air 3-5 times in oxygen decompression displacement system Sodium solution, control pH value controls reaction, about 30hrs end of reaction between 8-10 in HPLC in reaction process；
S3 is down to room temperature after the reaction was completed, filters off copper-tetraethylethylenediamine catalyst, and mother liquor washs one with a small amount of toluene It is secondary, water phase is separated, it is 3-5 that hydrochloric acid, which is acidified to PH, and 40-50 DEG C is concentrated under reduced pressure into residue to four times of left sides of rhodizonic acid quality 0-5 DEG C of stirred crystallization is down on the right side, filtering, and obtained solid drying, obtained yellow solid is crocic acid, using controlling in HPLC The purity of response measurement crocic acid, purity >=98% of crocic acid, yield >=80%；
In addition, removal process is as follows the invention further relates to copper-tetraethylethylenediamine catalyst recovery method: will The deionized water of 10 times of catalytic amounts is added in the copper filtered out-tetraethylethylenediamine catalyst, and rs for 24 hours is stirred at room temperature, and filters, gained Catalyst is dried under reduced pressure 5-10hrs at 40-50 DEG C and completes activation, repeated multiple times can apply.
The present invention replaces traditional manganese dioxide or strong using the copper catalyst that can be applied repeatedly, using oxygen as oxidant Acidic oxidation agent greatly reduces the discharge of all kinds of wastes, is very environmentally friendly process route, has complied with environmentally friendly green The development general orientation of colour chemistry, while being compared with traditional catalysis oxidation, the present invention uses synthesis under normal pressure, simultaneous reactions temperature Not high, reaction condition is mild, and operation is relatively simple, is very suitable to industrialized production.
Figure of description
Fig. 1 is crocic acid new technique for synthesizing route map.
The present invention that the following detailed description will be further explained with reference to the above drawings.
Specific embodiment
Case 1 is embodied
A kind of preparation method of crocic acid comprising following steps:
S1, copper-tetraethylethylenediamine catalyst preparation: by stannous chloride 1mol, tetraethylethylenediamine 2mol, water 30ml, methanol 500ml are sequentially placed into 2000ml round-bottomed flask, and fulling shake makes its Quan Rong, after be passed through oxygen and constantly shake Swing, be filled with 0.5mol oxygen into round-bottomed flask in 30mins, after filter out solid, with acetone washing, depressurized at 40 DEG C dry Dry 6hrs obtains about 460g aubergine powder, is for copper-tetraethylethylenediamine catalyst；
S2, by 200g deionized water, 21.4g rhodizonic acid (0.1mol) is added sequentially to equipped with gas-guide tube, PH meter, machine Tool stirs, and in the 500ml four-hole boiling flask of thermometer, is stirred at room temperature to solution and clarifies, and 2.2g copper-tetraethylethylenediamine catalysis is added Agent, after the deionized water solution 50ml of 10% sodium hydroxide of configured in advance is placed in dropping funel；
S3 three times with the air in oxygen decompression displacement system is warming up to 80-85 DEG C and reacts and start dropwise addition sodium hydroxide Solution, control pH value controls reaction, about 30hrs end of reaction between 8-10 in HPLC in reaction process；
S4 is down to room temperature after the reaction was completed, filters off copper-tetraethylethylenediamine catalyst, and mother liquor washs one with 20ml toluene It is secondary, water phase is separated, it is 3-5 that hydrochloric acid, which is acidified to PH, and 45-50 DEG C is concentrated under reduced pressure into residue about 90g, it is down to 0-5 DEG C of stirred crystallization, Filtering, obtained solid drying, obtains 11.4g yellow solid, and yellow solid is crocic acid, using control response measurement gram in HPLC The purity of ketone acid, purity >=98% of crocic acid, yield 80.3%；
Further, copper-tetraethylethylenediamine catalyst recovery method is as follows:
The copper filtered out in step S5-tetraethylethylenediamine catalyst is added to the deionized water of 10ml, is stirred at room temperature Rs for 24 hours, filtering, gained catalyst are dried under reduced pressure 5-6hrs at 40 DEG C and complete activation, repeated multiple times can apply.
The determination process of reaction condition in the preparation method of the above crocic acid is as follows:
The determination of catalyst amount:
In order to determine that copper-tetraethylethylenediamine catalyst optimum amount has carried out the experiment of 5 batches, the original substantially of experiment altogether Then it is exactly change copper-tetraethylethylenediamine catalyst dosage in the case where other experiment conditions are constant, is investigated with this to reality It tests as a result, such as yield, the influence in reaction time etc., 5 groups of experimental results are as shown in table 1.
Table 1: the reaction result under different catalysts dosage
From table 1 it follows that when reaction is carried out to about 35hrs, control is aobvious in HPLC when catalyst amount is 2.5% Show that raw material does not continue to convert, maintain 8% or so ever since, illustrates that the dosage of catalyst is on the low side, other reaction conditions are not In the case where change, reaction cannot carry out completely, therefore guarantee that reaction is gone on smoothly, and the dosage of catalyst should increase.
When copper-tetraethylethylenediamine catalyst dosage is 2.5%, adjusting reaction time, other reaction conditions are as above It states described in a kind of step S2-S4 of the preparation method of crocic acid, raw material residual volume is calculated using HPLC area normalization method, tie Fruit is as shown in table 2.
Reaction result under 2. catalyst amount 2.5% of table
Control-register number in HPLC Reaction time Raw material residual quantity (HPLC area normalization method)
1 4 82.4
2 8 66.7
3 12 50.3
4 16 34.2
5 20 20.5
6 24 14.1
7 28 9.6
8 32 8.7
9 36 8.4
10 46 8.0
11 60 7.8
12 72 7.8
When the dosage of catalyst is 5%, the case where reaction, is as shown in table 3, when controlling reaction in HPLC, when former residual quantity≤ When 1%, it is believed that reaction is completed, and according to situation is controlled in reaction, when reaction proceeds to 68hr, raw material remains 0.9%, it is believed that has reacted At.
Reaction result under 3. catalyst amount 5% of table
Control-register number in HPLC Reaction time Raw material residual quantity (HPLC area normalization method)
1 4 76.2
2 8 54.0
3 12 38.2
4 16 23.6
5 20 12.9
6 28 6.4
7 36 3.5
8 44 2.0
9 52 1.4
10 60 1.1
11 68 0.9
12 76 0.9
When catalyst amount 10%, response situation is as shown in table 4, there it can be seen that raw material is residual when reaction 30hrs 0.7% is stayed, reaction is completed, and is compared with the case where catalyst amount 5%, and not only the reaction time shortens dramatically, while raw material Residual is also lower, reacts more thorough.
Reaction result under 4. catalyst amount 10% of table
Control-register number in HPLC Reaction time Raw material residual quantity (HPLC area normalization method)
1 4 72.8
2 8 45.1
3 12 20.4
4 16 9.2
5 20 5.3
6 22 3.0
7 24 2.3
8 26 1.5
9 28 1.1
10 30 0.7
11 32 0.5
12 34 0.4
When catalyst amount 15%, response situation is as shown in table 5, there it can be seen that raw material is residual when reaction 28hrs 0.6% is stayed, reaction is completed, and is compared with the case where catalyst amount 10%, and the speed of initial reaction stage increased, but to instead The later period is answered to slow, there is no significant differences for reaction time and yield.
Reaction result under 5. catalyst amount 15% of table
Control-register number in HPLC Reaction time Raw material residual quantity (HPLC area normalization method)
1 4 69.4
2 8 42.1
3 12 18.5
4 16 9.4
5 20 5.1
6 22 2.6
7 24 1.4
8 26 1.0
9 28 0.6
10 30 0.4
11 32 0.3
12 34 0.3
When catalyst amount 20%, response situation is as shown in table 6, there it can be seen that raw material is residual when reaction 28hrs Stay 0.6%, reaction is completed, and reacts overall condition and 15% dosage has no significant difference.Under 6. catalyst amount 20% of table Reaction result
Control-register number in HPLC Reaction time Raw material residual quantity (HPLC area normalization method)
1 4 67.2
2 8 42.3
3 12 16.9
4 16 8.7
5 20 4.8
6 22 2.2
7 24 1.6
8 26 1.1
9 28 0.5
10 30 0.3
11 32 0.2
12 34 0.3
In conclusion the optimum amount of catalyst is 10%, this dosage lower reaction time, reaction yield and raw material are converted Rate is best, is reaction condition the most economic.The dosage of selection 5% is compared with 10% dosage, and the reaction time is too long, although The amount of catalyst has been lacked a bit, saves a little cost of material, but this is bound to cause the increase of energy consumption and cost of labor, if in conjunction with The condition of production, not only above-mentioned increased costs, can also seriously restrict production capacity, this absolutely loses more than gain, therefore optimal catalysis Agent dosage is the 10% of rhodizonic acid.
Catalyst is applied:
The concrete condition that catalyst is applied such as table 7 shows that the copper-tetraethylethylenediamine catalyst being embodied in case 1 is anti- 10 experiments have been carried out again, as can be seen from the table, are applied number with catalyst and are increased, react deadline and reaction yield It all decreases, if setting yield floating range as 5%, which can be Reusability 8 time；
7. catalyst of table apply under response situation
Catalyst access times Reaction time (hr) Yield (%)
1 28 80.3
2 28 80.2
3 28 79.6
4 29 78.5
5 30 78.2
6 31 77.3
7 33 77.1
8 34 76.4
9 37 75.1
10 41 73.2
The determination of reaction temperature:
Response situation under different temperatures is as shown in table 8, wherein 60-65 DEG C when do not react；Raw material about converts at 70-75 DEG C It is just no longer converted after 40%, illustrates that reaction temperature is too low, reaction can not carry out completely；It is reacted at 80-85 DEG C normal；90-95℃ Quickly, but late phase reaction slows Shi Fanying starting velocity, is primarily due to that temperature is higher, and catalyst later period activity deficiency is led Cause to react slack-off, 35hrs end of reaction, it is low that yield 76.2% with 80-85 DEG C compare not only yield, reaction slowly, the color of product Also normal yellow becomes sepia；100-105 DEG C due to reaction temperature height, early period, reaction speed was fast, but catalyst inactivation Also fast, starting material left 15% or so after 3hrs extend time response and no longer carry out due to catalyst inactivation.In conclusion best Reaction temperature be 80-85 DEG C.
Response situation under 8. different temperatures of table
The determination of residual quantity after precipitation:
Post-processing operation: being down to room temperature after the reaction was completed, filters off catalyst, and mother liquor washed once with 20ml toluene, separate Water phase, it is 3-5 that hydrochloric acid, which is acidified to PH, and 45-50 DEG C is concentrated under reduced pressure into residue about 90g, is down to 0-5 DEG C of stirred crystallization, is filtered, institute Solid drying is obtained, 11.4g yellow solid is obtained.Wherein the determination of amount of residue is very crucial, in order to investigate this factor, it is special into The experiments of 3 batches is gone, the amount of residue is 100g, 90g, 80g respectively after concentration, and continues to post-process, experimental result As shown in table 9, it is not difficult to find out from table, be concentrated into residue 100g, aqueous solvent residual quantity is too big, and the water solubility of product is very It is good, therefore yield is relatively low；, can be very little due to quantity of solvent in crystallization process when being concentrated into residue 80g, cause inorganic salts sodium chloride Precipitation mixes inside product, and the two is not readily separated, and causes product purity relatively low；And when being concentrated into 90g, the yield and purity of product Satisfactory effect is all reached.Influence of the amount of residue to product yield after table 9. is concentrated
Residual quantity (g) Product purity (HPLC external standard method) Yield (%)
100 98.7% 74.6%
90 98.1% 80.3%
80 92.4% 82.6%
The determination of recrystallization temperature:
It is well known that select different temperature all to have a major impact yield and product quality when recrystallization, this experiment The yield recrystallized under different temperatures and product quality have been investigated, it is specific as shown in table 10, it is clear that the dissolution of product in a solvent Degree increases as temperature increases, it is not difficult to find out that, best crystallization temperature is 0-5 DEG C from table.
Recrystallization situation under 10. different temperatures of table
Temperature (DEG C) Yield (%) Purity (%)
0-5 80.3 98.1
10-15 73.6 98.4
20-25 65.8 98.6
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously Limitations on the scope of the patent of the present invention therefore cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention Protect range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.

Claims (3)

1. bronze medal-tetraethylethylenediamine preparation method comprising following steps:
By stannous chloride, tetraethylethylenediamine, water and methanol are that 3: 8: 1: 12 ratio sequentially adds in reaction kettle in mass ratio, Being sufficiently stirred makes its Quan Rong, after be passed through oxygen and do not stir, duration of ventilation is controlled in 30-120mins, and oxygen flux control exists 50-2000ml/min, after filter out solid, with acetone washing, be dried under reduced pressure 6-10hrs at 40-60 DEG C, obtained amaranth flour End is for copper-tetraethylethylenediamine catalyst.
2. the method using copper-tetraethylethylenediamine of method of claim 1 preparation as catalyst preparation crocic acid, packet Include following steps:
S1, by deionized water, rhodizonic acid is added sequentially to by 10: 1 mass ratio equipped with gas-guide tube, PH meter, stirring and temperature It spends in the reaction kettle of meter, is stirred at room temperature to solution and clarifies, copper-tetraethylethylenediamine catalysis of rhodizonic acid weight 10% is added Agent, after the deionized water solution of 10% sodium hydroxide of configured in advance is placed in charging spout；
S2, with oxygen decompression displacement system in air 3-5 time, be warming up to 80-85 DEG C react and start dropwise addition sodium hydroxide it is molten Liquid, control pH value controls reaction, about 30hrs end of reaction between 8-10 in HPLC in reaction process；
S3 is down to room temperature after the reaction was completed, filters off copper-tetraethylethylenediamine catalyst, and mother liquor washed once with a small amount of toluene, point Water phase out, it is 3-5,40-50 DEG C of four times or so for being concentrated under reduced pressure into residue to rhodizonic acid quality, drop that hydrochloric acid, which is acidified to PH, To 0-5 DEG C of stirred crystallization, filtering, obtained solid drying, obtained yellow solid is crocic acid, is surveyed using control reaction in HPLC Measure the purity of crocic acid, purity >=98% of crocic acid, yield >=80%.
It further include following steps 3. preparing in the method for crocic acid as described in claim 2: the copper-tetraethyl that will be filtered out The deionized water of 10 times of catalytic amounts is added in ethylenediamine catalyst, and rs for 24 hours is stirred at room temperature, and filters, gained catalyst is at 40-50 DEG C Under be dried under reduced pressure 5-10hrs complete activation, repeated multiple times can apply.
CN201810244954.5A 2018-03-23 2018-03-23 Copper-tetraethylethylenediamine uses it as the preparation method of the crocic acid of catalyst Pending CN110292950A (en)

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Citations (2)

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Publication number Priority date Publication date Assignee Title
CN1615287A (en) * 2001-11-26 2005-05-11 纳幕尔杜邦公司 Process for preparing 3,3',5,5',6,6'-hexaalkyl-2,2'-biphenols, 3,3',4,4',5,5'-hexaalkyl-2,2'-biphenols and 3,3',4,4',5,5',6,6'-octaalkyl-2,2'-biphenols
CN103172506A (en) * 2013-03-21 2013-06-26 常州大学 Method for preparing croconic acid by using nanometer copper oxide as catalyst

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1615287A (en) * 2001-11-26 2005-05-11 纳幕尔杜邦公司 Process for preparing 3,3',5,5',6,6'-hexaalkyl-2,2'-biphenols, 3,3',4,4',5,5'-hexaalkyl-2,2'-biphenols and 3,3',4,4',5,5',6,6'-octaalkyl-2,2'-biphenols
CN103172506A (en) * 2013-03-21 2013-06-26 常州大学 Method for preparing croconic acid by using nanometer copper oxide as catalyst

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* Cited by examiner, † Cited by third party
Title
MASAHIRO NOJI等: "A New Catalytic System for Aerobic Oxidative Coupling of2-Naphthol Derivatives by the Use of CuCI-Amine Complex: A Practical Synthesis of Binaphthol Derivatives", 《TETRAHEDRON LETTERS》 *
孙彬彬: "含克酮酸类锂电子电池电解质的合成和性质研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 *

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Application publication date: 20191001