CN108164410B - Method for synthesizing cinnamic acid under catalysis of water-soluble calixarene phenolate - Google Patents
Method for synthesizing cinnamic acid under catalysis of water-soluble calixarene phenolate Download PDFInfo
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- CN108164410B CN108164410B CN201810004635.7A CN201810004635A CN108164410B CN 108164410 B CN108164410 B CN 108164410B CN 201810004635 A CN201810004635 A CN 201810004635A CN 108164410 B CN108164410 B CN 108164410B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/377—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
- C07C51/38—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups by decarboxylation
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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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0229—Sulfur-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0214
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/083—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid anhydrides
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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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
Abstract
The invention relates to a method for synthesizing cinnamic acid by catalyzing water-soluble calixarene phenolate, which belongs to the technical field of organic compound preparation. The calixarene phenolate of the invention is calix [ n ]]Arene (n =4,6, 8) sulfonic acid and thiacalix [ 4%]Aromatic sulfonic acid, NaOH, KOH and Na2CO3 K2CO3The amount of calixarene sodium (potassium) phenolate formed by the reaction is 5-10% of the mass of benzaldehyde substances, wherein the mass ratio of benzaldehyde to acetic anhydride is 1: 1-1: 4, the reaction temperature is 140-170 ℃, and the reaction time is 1-2 hours. The mass ratio of the benzaldehyde to the malonic acid is 1: 1-1: 4, the reaction temperature is 120-150 ℃, and the reaction time is 1-2 hours. The reaction process does not produce waste gas, waste water, waste residue and other industrial three wastes, is a green chemical process, and reduces the pollution to the environment. After reaction, the product and the catalyst are easily separated. The method has the advantages of simple process, high yield, environmental friendliness and low cost, and is suitable for industrial production.
Description
Technical Field
The invention relates to the field of organic catalysis, in particular to a method for catalytically synthesizing cinnamic acid by using water-soluble calixarene phenolate as a catalyst.
Background
The invention relates to a catalytic reaction of water-soluble calixarene phenate.
Calixarenes are a class of macrocyclic oligomers formed from multiple phenols linked at the 2,6 positions by methylene groups. Various functional groups can be introduced into the phenolic hydroxyl group and the para position of the calixarene to prepare various calixarene derivatives, so that the calixarene derivatives can be more widely applied. Calixarenes, however, are insoluble in water and are limited in certain chemical reactions. The upper edge and the lower edge of the aromatic hydrocarbon are chemically modified, so that the water solubility of the aromatic hydrocarbon can be improved, and the application range of the calixarene is expanded. The first preparation of water-soluble calixarene derivatives was reported in 1984: arduini A, Pochini A, Reverberi A, et al J Chem Soc Chem Commun, 1984, 981, which introduces sulfonic acid group and its salt at the para-position of phenolic hydroxyl group to improve the water solubility of calixarene, and is applied in various fields.
Due to sulfonic acid group (-SO)3H) Has strong acidity, can be used as an acid catalyst in organic synthesis, and has the advantages of easy separation, easy recovery, recyclable use and the like.
Cinnamic acid is also known as cinnamic acid, has a chemical name of 3-phenyl-2-acrylic acid, is an important organic chemical raw material and an organic synthetic intermediate, and is widely used as a raw material for fine chemical products such as medicines, pesticides, spices, food additives, photosensitive resins and the like. In the pharmaceutical industry, the intermediate of cinnamylphenyl piperazine can be used for synthesizing medicaments for treating coronary arteriosclerosis, cerebral thrombosis and other diseases, and can also be used for preparing medicaments for resisting infection, cancer, vasodilating agents, anti-ulcer agents, treating hypoglycemia and the like.
At present, a plurality of methods for synthesizing cinnamic acid are provided, mainly including a Perkin method, a Knoevenagel method, a benzaldehyde-vinyl ketone method, a benzaldehyde-acetone method, a benzaldehyde-acetic acid method and the like. Wherein, the Perkin and Knoevengel reactions are both prepared under the catalysis of weak base, and the catalyst of the Perkin reaction is strong base and weak acid salt (such as potassium carbonate, potassium acetate and the like); while the Knoevenagel reaction is carried out under the catalysis of weak base (amine, pyridine and the like), the catalysts are difficult to separate from reactants and products and cannot be recycled.
If the water-soluble calixarene containing sulfonic acid group is treated by alkali, the generated water-soluble calixarene phenolate has weak alkalinity, and is expected to be applied to weak base catalytic reaction instead of the catalyst, and at present, no report is found about the application of the weak alkaline water-soluble calixarene phenolate in the catalytic reaction.
Disclosure of Invention
The invention aims to provide a weakly alkaline water-soluble calixarene phenolate which is mainly a phenol sodium salt and a phenol potassium salt, is used as a catalyst for Perkin and Knoevenagel reaction, and is used for catalytically synthesizing cinnamic acid under different conditions. The technical scheme is as follows:
1, preparation of water-soluble calixarene sodium phenolate and potassium phenolate: see FIG. 1
2, preparation of water-soluble thiocalixate sodium salt and potassium salt: see FIG. 2
3 Perkin reaction to prepare cinnamic acid: see fig. 3 and 4
4 Knoevenagel reaction to prepare cinnamic acid: see fig. 5, 6.
Description of the drawings: FIG. 1 is a diagram showing the preparation of water-soluble calix [4] arene phenol sodium salt and phenol potassium salt, the preparation of water-soluble calix [6] arene phenol sodium salt and phenol potassium salt, the preparation equations of water-soluble calix [8] arene phenol sodium salt and phenol potassium salt, FIG. 2 is a diagram showing the preparation equations of water-soluble thiocapx [4] arene phenol sodium salt and phenol potassium salt catalyzing a Perkin reaction to prepare cinnamic acid, water-soluble calix [6] arene phenol sodium salt and phenol potassium salt catalyzing a Perkin reaction to prepare cinnamic acid, water-soluble calix [8] arene phenol sodium salt and phenol potassium salt catalyzing a Perkin reaction to prepare cinnamic acid, FIG. 4 is a diagram showing the preparation equations of water-soluble thiocapx [4] arene phenol sodium salt and phenol potassium salt catalyzing a Knoevogell reaction to prepare cinnamic acid, and FIG. 5 is a diagram showing the preparation equations of water-soluble calix [6] arene phenol sodium salt and phenol potassium salt catalyzing a Knoeveagel reaction to prepare cinnamic acid, The formula chart of cinnamic acid prepared by reacting water-soluble calix [8] arene phenol sodium salt with phenol potassium salt in a Knoevenagel catalysis reaction, and the formula chart of cinnamic acid prepared by reacting water-soluble thiocapx [4] arene phenol sodium salt with phenol potassium salt in a Knoevenagel catalysis reaction is shown in figure 6.
The invention specifically comprises the following contents:
preparation of calixarene sodium (potassium) phenolate, taking a fixed amount of calix [4]]Cup (6)]Cup (8)]Or a thiocup [4]]Dissolving aromatic sulfonic acid in small amount of water, adding a certain amount of saturated Na2CO3(K2CO3) And (3) adjusting the pH of the solution to be 9-10, adding a certain amount of anhydrous methanol, standing until a large amount of white precipitates appear, and performing suction filtration to obtain the corresponding calixarene sodium (potassium) phenolate.
Calixarene sodium (potassium) phenolate catalyzes the Perkin reaction. Putting the newly steamed benzaldehyde and acetic anhydride into a three-necked bottle, adding water-soluble calixarene sodium (potassium) phenolate, magnetically stirring, heating to 170 ℃, reacting for 1-2 h, filtering to remove the catalyst, and adding 10% Na2CO3Adjusting the pH of the solution to be 9-10, extracting the water phase twice by using 10mL of ethyl acetate, adsorbing impurities in the water phase by using a small amount of activated carbon, performing suction filtration, adjusting the pH of the filtrate to be 3-4 by using concentrated hydrochloric acid, separating out a large amount of white crystals, performing suction filtration, drying, weighing, and calculating the yield.
Catalytic Knoevenagel reaction of calixarene sodium (potassium) phenolate newly distilled benzaldehyde and dried malonic acid are placed in a three-mouth bottle, and water-soluble phenol sodium (potassium) phenolate is addedUniformly stirring calixarene sodium (potassium) phenolate by magnetic force, heating to 130 ℃, reacting for 1-2 h, filtering to remove the catalyst, and adding 10% Na2CO3Adjusting the pH of the solution to be 9-10, extracting the water phase twice by using 10mL of ethyl acetate, adsorbing impurities in the water phase by using a small amount of activated carbon, performing suction filtration, adjusting the pH of the filtrate to be 3-4 by using concentrated hydrochloric acid, separating out a large amount of white crystals, performing suction filtration, drying, weighing, and calculating the yield.
The invention has the advantages that: the calixarene sodium (potassium) phenolate can be repeatedly used, and the calixarene sodium (potassium) phenolate can be directly repeatedly used, and if the yield is reduced, the calixarene sodium (potassium) phenolate can be reused through simple purification treatment.
The calixarene sodium (potassium) phenolate provided by the invention comprises the following components: calix [4], calix [6] and calix [8] arenepholate sodium (potassium) salts, thiocalix [4] arenepholate sodium (potassium) salts; in the Perkin reaction, the dosage of the catalyst is 5-10% of the mass of benzaldehyde, and the mass ratio of benzaldehyde to acetic anhydride is 1: 1-1: 4; the heating temperature is 140-170 ℃, and the reaction time is 1-2 h; in the Knoevenagel reaction, the dosage of the catalyst is 5-10% of the mass of benzaldehyde substances, and the mass ratio of benzaldehyde to malonic acid is 1: 1-1: 4; the reaction temperature is 140-170 ℃, and the reaction time is 1-2 h.
The invention has the advantages that the catalyst can be directly filtered and separated, the used calixarene phenolate can be recycled for a plurality of times, the cost is lower, the method is suitable for industrial production, no pollution is discharged, and the method is a typical environment-friendly process.
Detailed Description
The first embodiment is as follows:
cup [4]]Catalyzing Perkin reaction by aromatic phenol sodium salt to synthesize cinnamic acid: a round-bottomed flask was charged with 1.5 ml (15 mmol) of freshly distilled benzaldehyde, 4.0 ml (42 mmol) of acetic anhydride and 0.69 g of cup [4]]The aromatic phenol sodium salt is provided with a condenser pipe and a thermometer and is stirred by magnetic force. After reacting at 170 ℃ for 2 h, the catalyst was removed by filtration and the reaction mixture was washed with 10% Na2CO3Adjusting the pH value of the solution to 9, extracting the water phase twice by 10mL of ethyl acetate, adsorbing impurities in the water phase by using a small amount of activated carbon, performing suction filtration, adjusting the pH value of the filtrate to = 3-4 by using concentrated hydrochloric acid, separating out a large amount of white crystals, performing suction filtration, drying and weighing, and obtaining the yield of 62.6%.
Example two:
cup [6]]Catalyzing Perkin reaction by aromatic phenol sodium salt to synthesize cinnamic acid: a round-bottomed flask was charged with 1.5 ml (15 mmol) of freshly distilled benzaldehyde, 4.0 ml (42 mmol) of acetic anhydride and 1.04g of cup [6]]And (3) placing aromatic phenol sodium salt on a condenser pipe and a thermometer, and magnetically stirring. Reacting at 160 deg.C for 2 hr, filtering to remove catalyst, and adding 10% Na2CO3Adjusting the pH of the solution to 9, extracting the water phase twice by 10mL of ethyl acetate, adsorbing impurities in the water phase by using a small amount of activated carbon, performing suction filtration, adjusting the pH of the filtrate to = 3-4 by using concentrated hydrochloric acid, separating out white crystals, performing suction filtration, drying and weighing, wherein the yield is 55.0%.
Example three:
cup [8]Catalyzing Perkin reaction by aromatic phenol sodium salt to synthesize cinnamic acid: a round-bottomed flask was charged with 1.5 ml (15 mmol) of freshly distilled benzaldehyde, 5.7 ml (60 mmol) of acetic anhydride and 1.38 g of cup [8]]And (3) placing aromatic phenol sodium salt in a condenser pipe, a thermometer and carrying out magnetic stirring. After the reaction was completed at 150 ℃ for 2 hours, the catalyst was removed by filtration and the residue was washed with 10% Na2CO3Adjusting the pH of the solution to 10, extracting the water phase twice by 10mL of ethyl acetate, adsorbing impurities in the water phase by using a small amount of activated carbon, performing suction filtration, adjusting the pH of the filtrate to = 3-4 by using concentrated hydrochloric acid, separating out a large amount of white crystals, performing suction filtration, drying and weighing, wherein the yield is 51.5%.
Example four:
thiocup [4]]Catalyzing Perkin reaction by aromatic phenol sodium salt to synthesize cinnamic acid: a round bottom flask was charged with freshly distilled benzaldehyde 1.5 ml (15 mmol), acetic anhydride 4.0 ml (42 mmol) and 0.74 g of thiocup [4]]And (3) placing aromatic phenol sodium salt on a condenser pipe and a thermometer, and magnetically stirring. Heating to 140 deg.C, reacting for 2 hr, filtering to remove catalyst, and adding 10% Na2CO3Adjusting the pH of the solution to 10, extracting the water phase twice by 10mL of ethyl acetate, adsorbing impurities in the water phase by using a small amount of activated carbon, performing suction filtration, adjusting the pH of the filtrate to = 3-4 by using concentrated hydrochloric acid, separating out white crystals, performing suction filtration, drying and weighing, wherein the yield is 44.7%.
Example five:
cup [4]]Synthesizing cinnamic acid by catalyzing Perkin reaction with aromatic phenol potassium salt: a round-bottomed flask was charged with 1.5 ml (15 m) of freshly distilled benzaldehydemol), 4.0 ml of acetic anhydride (42 mmol) and 0.78 g of cup [4]]Aromatic phenol potassium salt, a condenser tube and a thermometer are arranged, and magnetic stirring is carried out. Heating to 170 deg.C, reacting for 0.5 h, filtering to remove catalyst, and adding 10% Na2CO3Adjusting the pH of the solution to 9, extracting the water phase twice by 10mL of ethyl acetate, adsorbing impurities in the water phase by using a small amount of activated carbon to obtain colorless liquid, performing suction filtration while the water phase is hot, adjusting the pH of the filtrate to = 3-4 by using concentrated hydrochloric acid, separating out a large amount of white crystals, performing suction filtration, drying and weighing, wherein the yield is 31.4%.
Example six:
cup [6]]Synthesizing cinnamic acid by catalyzing Perkin reaction with aromatic phenol potassium salt: a round-bottomed flask was charged with 1.5 ml (15 mmol) of freshly distilled benzaldehyde, 5.7 ml (60 mmol) of acetic anhydride and 1.18 g of cup [6]]Aromatic phenol potassium salt, a condenser tube and a thermometer are arranged, and magnetic stirring is carried out. Heating to 170 deg.C, reacting for 1 hr, filtering to remove catalyst, and adding 10% Na2CO3Adjusting the pH of the solution to 9, extracting a water phase twice by 10mL of ethyl acetate, adsorbing impurities in the water phase by using a small amount of activated carbon to obtain a colorless liquid, performing suction filtration, adjusting the pH of a filtrate to = 3-4 by using concentrated hydrochloric acid, separating out white crystals, performing suction filtration, drying and weighing, wherein the yield is 55.0%.
Example seven:
cup [8]Synthesizing cinnamic acid by catalyzing Knoevenagel reaction with aromatic phenol potassium salt: a round-bottom flask was charged with 1.5 ml (15 mol) of freshly distilled benzaldehyde, 4.7 g (45mmol) of malonic acid and 1.58 g of cup [8]]Aromatic phenol potassium salt. A condenser tube and a thermometer are arranged, and magnetic stirring is carried out. Reaction at 130 ℃ for 1 h, then filtering to remove the catalyst, adding 10% Na2CO3Adjusting the pH value of the solution to 10, extracting the water phase twice by 10mL of ethyl acetate, adsorbing impurities in the water phase by using a small amount of activated carbon, performing suction filtration, adjusting the pH value of the filtrate to = 3-4 by using concentrated hydrochloric acid, separating out white crystals, performing suction filtration, drying and weighing, wherein the yield is 58.0%.
Example eight:
thiocup [4]]Synthesizing cinnamic acid by catalyzing Knoevenagel reaction with aromatic phenol potassium salt: a round bottom flask was charged with freshly distilled benzaldehyde 1.5 ml (15 mol), malonic acid 4.7 g (45mol) and thiocup 0.84 g [4]]Aromatic phenol potassium salt. A condenser tube and a thermometer are arranged, and magnetic stirring is carried out. Heating to 130 deg.C, and reactingAfter 2 h, the catalyst was removed by filtration and treated with 10% Na2CO3Adjusting the pH value of the solution to 10, extracting the water phase twice by 10mL of ethyl acetate, adsorbing impurities in the water phase by using a small amount of activated carbon, performing suction filtration, adjusting the pH value of the filtrate to = 3-4 by using concentrated hydrochloric acid, separating out white crystals, performing suction filtration, drying and weighing, wherein the yield is 62%.
Claims (5)
1. A method for synthesizing cinnamic acid by catalyzing water-soluble calixarene phenol sodium salt or sylvite is characterized by comprising the following steps: using water-soluble calixarene phenol sodium salt or sylvite as a catalyst to catalyze benzaldehyde and malonic acid to perform Knoevenagel reaction or catalyze benzaldehyde and acetic anhydride to perform Perkin reaction, wherein the reaction is heterogeneous reaction, filtering to remove the catalyst after the reaction is finished, and using 10% Na2CO3Adjusting the pH value of the solution to be alkalescent, extracting twice by using 10mL ethyl acetate, taking a lower-layer water phase, adsorbing impurities by using a small amount of activated carbon, performing suction filtration, adjusting the pH value of a filtrate to be = 3-4 by using concentrated hydrochloric acid, separating out a large amount of white crystals, performing suction filtration, drying, weighing, calculating the yield, and repeatedly using the catalyst.
2. The method of claim 1, wherein: the water soluble calixarene phenol sodium salt or potassium salt catalyst is prepared by calix [ n]Arene (n =4,6, 8) sulfonic acid and thiacalix [ 4%]Aromatic sulfonic acid and Na2CO3、K2CO3And reacting NaOH and KOH solution, adjusting the pH value of the solution to 9-10, and then recrystallizing in anhydrous methanol to obtain the catalyst.
3. The method of claim 1, wherein: in the Perkin and Knoevenagel reaction, the dosage of the catalyst is 5-10% of the dosage of the benzaldehyde substance.
4. The method of claim 1, wherein: in the Perkin reaction, the mass ratio of benzaldehyde to acetic anhydride is 1: 1-1: 4; the heating temperature is 140-170 ℃, and the reaction time is 1-2 h; in the Knoevenagel reaction, the mass ratio of benzaldehyde to malonic acid is 1: 1-1: 4; the heating temperature is 120-150 ℃, and the reaction time is 1-2 h.
5. The method according to claim 1 or 2, characterized in that: the calixarene sodium salt or sylvite is directly recycled for a plurality of times through simple purification treatment, and the calixarene sodium salt or sylvite purification treatment step comprises: washing with acetone and diethyl ether, concentrating, and drying.
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| CN109096091A (en) * | 2018-08-27 | 2018-12-28 | 上海华堇生物技术有限责任公司 | The preparation method of cinnamic acid |
| CN109942379A (en) * | 2019-04-11 | 2019-06-28 | 辽宁石油化工大学 | It is a kind of water solubility p-t-butyl or calixarenes phenol potassium (sodium) salt new synthetic method |
| CN110054554B (en) * | 2019-05-16 | 2022-12-30 | 辽宁石油化工大学 | Method for synthesizing 4-phenyl-3-butenone |
| CN111733192B (en) * | 2020-07-03 | 2021-12-03 | 湖北大学 | Novel enzyme catalysis method for preparing cinnamic acid from cinnamaldehyde and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101433861A (en) * | 2008-12-19 | 2009-05-20 | 天津工业大学 | Application of calixarene derivative in potassium salt participative phase-transfer catalytic reaction |
| CN102633624A (en) * | 2012-03-22 | 2012-08-15 | 湖北远成药业有限公司 | Method for preparing methylcinnamic acid |
| CN104058952A (en) * | 2014-06-09 | 2014-09-24 | 青岛东方循环能源有限公司 | Preparation method of cinnamic acid |
| CN104140367A (en) * | 2014-07-17 | 2014-11-12 | 天宁香料（江苏）有限公司 | Microwave synthesis method for cinnamic acid and application of cinnamic acid in essence |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101433861A (en) * | 2008-12-19 | 2009-05-20 | 天津工业大学 | Application of calixarene derivative in potassium salt participative phase-transfer catalytic reaction |
| CN102633624A (en) * | 2012-03-22 | 2012-08-15 | 湖北远成药业有限公司 | Method for preparing methylcinnamic acid |
| CN104058952A (en) * | 2014-06-09 | 2014-09-24 | 青岛东方循环能源有限公司 | Preparation method of cinnamic acid |
| CN104140367A (en) * | 2014-07-17 | 2014-11-12 | 天宁香料（江苏）有限公司 | Microwave synthesis method for cinnamic acid and application of cinnamic acid in essence |
Non-Patent Citations (1)
| Title |
|---|
| 杯芳烃磺酸的应用新进展;王晓梅等;《辽 宁 石 油 化 工 大 学 学 报》;201702;第３７卷(第１期);第1-3页 * |
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