CN114605375B - Synthetic method of 2-thiopheneacetic acid - Google Patents
Synthetic method of 2-thiopheneacetic acid Download PDFInfo
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- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
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Abstract
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a synthetic method of 2-thiopheneacetic acid. Thiophene is used as a raw material, an alkylating agent is used for carrying out Friedel-crafts alkylation reaction under the action of a sulfonic acid group functionalized ionic liquid as a catalyst, and a reactant is hydrolyzed and acidified to obtain the 2-thiophene acetic acid. The method has the advantages of cheap raw materials, simple process, less three wastes and high safety. The product has good quality and high yield, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a synthetic method of 2-thiopheneacetic acid.
Background
The 2-thiopheneacetic acid is an important organic synthesis intermediate, can improve the stability and the antibacterial activity by modifying the structure of the cephalosporium nucleus 7-aminocephalosporanic acid, has important function in the synthesis of cephalosporins, and is widely applied to the fields of medicines, pesticides, bactericides, herbicides, dye intermediates and the like.
At present, a plurality of methods for synthesizing 2-thiopheneacetic acid are reported, and the methods mainly comprise the following steps:
(1) Oxidation process
The patent CN102977073 discloses a method for preparing 2-thiopheneacetic acid by oxidizing 2-thiopheneethanol with chromium trioxide, which has low defect yield and complex recovery process of a large amount of chromium-containing wastewater. Patent CN104725345A discloses a method for preparing 2-thiopheneacetic acid by oxidizing 2-thiopheneethanol with TEMPO, which has high yield but has the defect that the recovery and reuse of TEMPO as a catalyst are complicated. Patent CN111560005A discloses a method for preparing 2-thiopheneacetic acid by catalyzing 2-thiopheneethanol with solid acid. The general disadvantages of the oxidation method are that the oxidation degree is difficult to control, byproducts are easy to generate, the oxidation process is a dangerous process with important supervision, and the construction investment and safety risk are large.
(2) Friedel-crafts reaction
Patent CN103467441 discloses a method for preparing 2-thiopheneacetic acid by using aluminum trichloride to catalyze the reaction of thiophene and methyl chloroacetate and further hydrolyzing. CN111205266 uses 2-chloroacetyl chloride and thiophene to obtain 2-chloroacetyl thiophene through Friedel-crafts acylation reaction, and then obtains 2-thiopheneacetic acid through Favorsky rearrangement. A common drawback of this route is that a large amount of aluminium-containing waste water is produced.
(3) Nitrile hydrolysis method
The patents CN103992302 and CN104327040 disclose methods of performing chloromethylation reaction using thiophene, hydrochloric acid and formaldehyde or paraformaldehyde, which have the disadvantages that the generated chloromethylthiophene has explosion hazard, and the subsequent steps use highly toxic trimethylsilyl cyanide or sodium cyanide, which is not suitable for industrial production. CN106518839 uses virulent acetone cyanohydrin to produce 2-thiopheneacetonitrile, which is then hydrolyzed to produce 2-thiopheneacetic acid. A common drawback of nitrile hydrolysis is the use of highly toxic cyanide compounds, which present a significant safety risk.
(4) Other methods
Patent CN1955174 discloses a method for catalytically synthesizing 2-thiopheneacetic acid from thiophene, red phosphorus and glyoxylic acid, but has the defect of generating a large amount of phosphorus-containing wastewater. Patent CN105906604 discloses a method, thiophene is condensed with diethyl malonate after chlorination and iodination, and finally hydrolysis and decarboxylation are carried out to prepare 2-thiopheneacetic acid, the yield is good, but the problem of recycling iodine-containing wastewater exists. CN110003167 uses 2-thiophenecarboxaldehyde and chloroacetate as raw materials to synthesize epoxy ester, and then 2-thiopheneacetic acid is obtained through hydrolysis, acidification, decarboxylation and oxidation. This process is complex, involves multiple synthesis and work-up steps, and yields of 2-thiopheneacetic acid are low. The document [ Li Guijie, et al, synthesis of 2-thiopheneacetic acid [ J ]. Synthetic chemistry, 2004 (04) ] uses 2-acetylthiophene to synthesize 2-thiopheneacetic acid methyl ester, and then hydrolyzes to generate 2-thiopheneacetic acid, and the route has the defects that a lead compound is used as a catalyst, and the requirement of boron trifluoride on reaction conditions is severe.
The methods have certain environmental threats and do not accord with the development trend of modern green chemistry.
Meanwhile, many chemical reactions, such as esterification, friedel-crafts reaction, chloromethylation reaction and the like, need catalysis in a strong acid environment, and most of the traditional methods for providing a strong acid environment, such as sulfuric acid, aluminum trichloride, phosphoric acid and other catalytic systems, have the problems of complex process and large amount of three wastes. Therefore, a method which has the characteristics of easily obtained raw materials, simple process and less three wastes and is suitable for large-scale industrial production of 2-thiopheneacetic acid is needed.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the method for synthesizing the 2-thiopheneacetic acid, which has the characteristics of easily obtained raw materials, simple process and less three wastes and is suitable for large-scale industrial production.
To achieve the above object. The invention comprises the following steps:
a synthesis method of 2-thiopheneacetic acid is characterized in that thiophene is used as a raw material, alkylation agent is used for carrying out Friedel-crafts alkylation reaction under the action of sulfonic group functionalized ionic liquid serving as a catalyst, and a reaction product is hydrolyzed and acidified to obtain the 2-thiopheneacetic acid.
The Friedel-crafts alkylation reaction product is hydrolyzed under the alkaline environment to generate 2-thiophene acetate, and the 2-thiophene acetate generates 2-thiophene acetic acid under the acidic environment.
The sulfonic acid group functionalized ionic liquid consists of an anion part and a cation part; wherein the anion part is sulfate radical, hydrogen sulfate radical, chloride ion, bromide ion, sulfonate radical, acetate radical, dihydrogen phosphate radical, trifluoroacetate radical, trifluoromethanesulfonate radical, hexafluorophosphate radical or tetrafluoroborate radical; the cationic moiety is optionally represented by the following structural formula,
Meanwhile, the sulfonic acid group functionalized ionic liquid can be prepared according to the records in the prior art, for example, the ionic liquid of the Showwen sulfonic acid type can be prepared according to the records in the research on the application of cellulose hydrolysis [ D ]. Tianjin university, 2012.
The alkylating agent is 2-chloroacetate.
Further, the method comprises the following steps:
(1) Alkylation reaction: uniformly mixing thiophene, 2-chloroacetate and sulfonic acid group functionalized ionic liquid, heating to 60-100 ℃, preferably 70-80 ℃ for reaction at 5-240 min, preferably 120-240 min, cooling to 30 ℃ after reaction, distilling at reduced pressure at the temperature, and sequentially distilling out unreacted raw materials and an intermediate 2-thiopheneacetic ester;
(2) Hydrolysis and acidification: mixing the obtained 2-thiopheneacetic ester with alkaline water, heating to reflux (about 100 ℃) for 5-240 min, adding acid into the reaction liquid, adjusting the pH value to 1-2, cooling, separating out and filtering to obtain 2-thiopheneacetic acid solid.
The reaction scheme (alkylating agent is exemplified by methyl 2-chloroacetate) is:
1) Alkylation reaction
(2) Hydrolytic acidification
The reaction scheme (alkylating agent is exemplified by methyl 2-chloroacetate) is:
the mass ratio of thiophene to 2-chloroacetate in the alkylation reaction is 0.5.
The raw materials and the residual catalyst in the kettle distilled by the reduced pressure of the alkylation reaction are recycled and reused
In the hydrolysis acidification, the mass ratio of the 2-thiophene acetate to the alkali is 1:1-1:2, preferably 1.1-1.2, and the reaction time is 5-240 min, preferably 30-90min.
The alkali used for hydrolytic acidification is NaOH, KOH, ca (OH) 2 、Ba(OH) 2 、Na 2 CO 3 Or K 2 CO 3 Preferably NaOH or KOH; the acid used is hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid or hydroiodic acid, preferably hydrochloric acidOr sulfuric acid.
The invention has the advantages and beneficial effects that:
the synthesis method has low raw material cost, synthesizes the 2-thiopheneacetic acid through Friedel-crafts alkylation under the action of the specific ionic liquid, has simple operation, avoids the use of extremely toxic cyanide, can reuse the catalyst for many times, has little environmental pollution, avoids the pollution problem of phosphorus and aluminum-containing wastewater in the prior scheme, also avoids the problem of difficult control of an oxidation method, has the product yield of more than 92 percent and the purity of more than 99 percent, and is favorable for industrial production.
The sulfonic acid group functionalized ionic liquid is used as a catalyst, and is used as a solvent and a catalyst simultaneously in an alkylation reaction process; firstly, the ionic liquid can fully dissolve raw materials when used as a solvent, and secondly, the ionic liquid is used as a catalyst to introduce a specific group sulfonic group in the ionic liquid into a system, so that a acidic catalysis environment is provided for the raw materials, the reaction process is simplified, and three wastes are reduced.
Detailed Description
The following examples are presented to further illustrate embodiments of the present invention, and it should be understood that the embodiments described herein are for purposes of illustration and explanation only and are not intended to limit the invention.
Example 1
50g of thiophene, 64.5g of methyl 2-chloroacetate and 100g of 1-propylsulfonic acid-3-methylimidazole hydrochloride ionic liquid are mixed and heated to 60 ℃ for reaction for 3 hours. Then the temperature is reduced to 30 ℃, and unreacted raw materials and the intermediate 2-thiopheneacetic acid methyl ester are sequentially distilled out by a reduced pressure distillation mode. Mixing 2-thiopheneacetic acid methyl ester with 131g of 20wt% NaOH solution, heating to reflux reaction for 60min, then adding 36% hydrochloric acid solution, adjusting the pH value of the solution to 1.5, then cooling to 0 ℃, and filtering to obtain the product 2-thiopheneacetic acid. The product purity is 99.0 percent, and the yield is 85.4 percent.
Example 2
Mixing 50g of thiophene, 64.5g of methyl 2-chloroacetate and 100g of 1-propylsulfonic acid-3-methylimidazole bisulfate ionic liquid, and heating to 80 ℃ for reaction for 3 hours. Then the temperature is reduced to 30 ℃, and unreacted raw materials and the intermediate 2-thiopheneacetic acid methyl ester are sequentially distilled out by a reduced pressure distillation mode. Mixing 2-thiopheneacetic acid methyl ester with 131g of 20wt% NaOH solution, heating to reflux reaction for 60min, then adding 36% hydrochloric acid solution, adjusting the pH value of the solution to 1.5, then cooling to 0 ℃, and filtering to obtain the product 2-thiopheneacetic acid. The product purity is 99.2 percent, and the yield is 92.1 percent.
Example 3
Mixing 50g of thiophene, 72.9g of 2-ethyl chloroacetate and 200g of 1-propylsulfonic acid-3-methylimidazole sulfate ionic liquid, and heating to 80 ℃ for reaction for 3 hours. Then the temperature is reduced to 30 ℃, and unreacted raw materials and the intermediate 2-thiophene ethyl acetate are sequentially distilled out by a reduced pressure distillation mode. Mixing 2-thiopheneacetic acid ethyl ester with 131g of 20wt% NaOH solution, heating to reflux reaction for 60min, then adding 36% hydrochloric acid solution, adjusting the pH value of the solution to 2, then cooling to 0 ℃, and filtering to obtain the product 2-thiopheneacetic acid. The product purity is 98.7%, and the yield is 86.3%.
Example 4
Mixing 50g of thiophene, 72.9g of ethyl 2-chloroacetate and 100g N-propylsulfonic acid pyridine bisulfate ionic liquid, and then heating to 100 ℃ for reaction for 2 hours. Then the temperature is reduced to 30 ℃, and unreacted raw materials and the intermediate 2-thiophene ethyl acetate are distilled out in sequence by a reduced pressure distillation mode. Mixing 2-thiopheneacetic acid ethyl ester with 131g of 20wt% NaOH solution, heating to reflux reaction for 60min, then adding 36% hydrochloric acid solution, adjusting the pH value of the solution to 1, then cooling to 0 ℃, and filtering to obtain the product 2-thiopheneacetic acid. The purity of the product is 99.0 percent, and the yield is 88.2 percent.
Example 5
Mixing 50g of thiophene, 72.9g of ethyl 2-chloroacetate and 50g N-propylsulfonic pyridine bisulfate ionic liquid, and heating to 80 ℃ for reaction for 3 hours. Then the temperature is reduced to 30 ℃, and unreacted raw materials and the intermediate 2-thiophene ethyl acetate are distilled out in sequence by a reduced pressure distillation mode. Mixing 2-thiopheneacetic acid ethyl ester with 183g of 20wt% KOH solution, heating to reflux reaction for 240min, adding 50% sulfuric acid solution, adjusting pH to 1.5, cooling to 0 deg.C, and filtering to obtain 2-thiopheneacetic acid product. The product purity is 98.0 percent, and the yield is 78.7 percent.
Example 6
Mixing 50g of thiophene, 129.1g of methyl 2-chloroacetate and 100g of N, N-trimethyl-N-propyl sulfonic ammonium hydrogen sulfate ionic liquid, and heating to 80 ℃ for reaction for 2 hours. Then the temperature is reduced to 30 ℃, and unreacted raw materials and the intermediate 2-thiopheneacetic acid methyl ester are sequentially distilled out by a reduced pressure distillation mode. Mixing 2-thiopheneacetic acid methyl ester with 250g 30wt% of Na2CO3 solution, heating to reflux reaction for 60min, adding 36% hydrochloric acid solution, adjusting pH to 1.5, cooling to 0 deg.C, and filtering to obtain 2-thiopheneacetic acid product. The product purity is 99.2 percent, and the yield is 70.2 percent.
Example 7
100g of thiophene, 64.5g of 2-methyl chloroacetate and 200g of N, N-trimethyl-N-propyl sulfonic acid ammonium hydrogen sulfate ionic liquid are mixed, and the mixture is heated to 80 ℃ to react for 2 hours. Then the temperature is reduced to 30 ℃, and unreacted raw materials and the intermediate 2-thiopheneacetic acid methyl ester are sequentially distilled out by a reduced pressure distillation mode. Mixing 2-thiopheneacetic acid methyl ester with 300g 30wt% K2CO3 solution, heating to reflux reaction for 60min, adding phosphoric acid solution, adjusting pH to 2, cooling to 0 deg.C, and filtering to obtain 2-thiopheneacetic acid product. The product purity is 98.4%, and the yield is 79.6%.
Example 8
Mixing 50g of thiophene, 64.5g of methyl 2-chloroacetate and 100g of 1-propylsulfonic acid-3-methylimidazole bisulfate ionic liquid, and heating to 80 ℃ for reaction for 3 hours. Then the temperature is reduced to 30 ℃, and unreacted raw materials and the intermediate 2-thiopheneacetic acid methyl ester are sequentially distilled out by a reduced pressure distillation mode. Mixing 2-thiopheneacetic acid methyl ester with 131g of 20wt% NaOH solution, heating to reflux reaction for 30min, adding 40% hydrobromic acid solution, adjusting the pH of the solution to 1.5, cooling to 0 ℃, and filtering to obtain the product 2-thiopheneacetic acid. The product purity is 98.5%, and the yield is 88.4%.
Example 9
50g of thiophene, 64.5g of methyl 2-chloroacetate and 100g of 1-butylsulfonic acid-3-methylimidazole trifluoroacetate ionic liquid are mixed and heated to 80 ℃ for reaction for 4 hours. Then the temperature is reduced to 30 ℃, and unreacted raw materials and the intermediate 2-thiophene methyl acetate are distilled out in sequence by a reduced pressure distillation mode. Mixing 2-thiopheneacetic acid methyl ester with 131g of 20wt% NaOH solution, heating to reflux reaction for 60min, then adding 36% hydrochloric acid solution, adjusting the pH value of the solution to 1, then cooling to 0 ℃, and filtering to obtain a product 2-thiopheneacetic acid product. The product purity is 98.2 percent, and the yield is 89.0 percent.
Example 10
Mixing 50g of thiophene, 64.5g of methyl 2-chloroacetate and 100g of 1-butylsulfonic acid-3-methylimidazole trifluoromethanesulfonate ionic liquid, and heating to 80 ℃ to react for 4 hours. Then the temperature is reduced to 30 ℃, and unreacted raw materials and the intermediate 2-thiopheneacetic acid methyl ester are sequentially distilled out by a reduced pressure distillation mode. Mixing 2-thiopheneacetic acid methyl ester with 142g 20wt% NaOH solution, heating to reflux reaction for 60min, adding 36% hydrochloric acid solution, adjusting pH of the solution to 1.5, cooling to 0 ℃, and filtering to obtain the product 2-thiopheneacetic acid. The product purity is 99.2 percent, and the yield is 85.3 percent.
Example 11
Mixing 50g of thiophene, 64.5g of methyl 2-chloroacetate and 100g of 1-propylsulfonic acid-3-methylimidazole bisulfate ionic liquid, and heating to 80 ℃ for reaction for 3 hours. Then the temperature is reduced to 30 ℃, and unreacted raw materials and the intermediate 2-thiopheneacetic acid methyl ester are sequentially distilled out by a reduced pressure distillation mode. Mixing 2-thiopheneacetic acid methyl ester with 131g of 20wt% NaOH solution, heating to reflux reaction for 60min, then adding 36% hydrochloric acid solution, adjusting the pH value of the solution to 1.5, then cooling to 0 ℃, and filtering to obtain the product 2-thiopheneacetic acid. The ionic liquid residue obtained by reduced pressure distillation was subjected to an experiment according to the procedure described in this example to prepare 2-thiopheneacetic acid, and the experimental results are shown in the following table.
Number of times of application | Purity of the product/%) | Yield/% |
1 | 99.2 | 92.1 |
2 | 99.1 | 91.7 |
3 | 99.0 | 91.8 |
4 | 99.2 | 91.5 |
5 | 99.0 | 91.0 |
Therefore, after the compound is applied for 5 times, the product purity is not influenced, and the product yield is kept at a higher level. The 2-thiopheneacetic acid catalyzed and synthesized by the sulfonic acid group ionic liquid has good cycle performance.
Claims (7)
1. A synthetic method of 2-thiopheneacetic acid is characterized in that: taking thiophene as a raw material, carrying out a Friedel-crafts alkylation reaction by using an alkylating agent under the action of a sulfonic group functionalized ionic liquid as a catalyst, and carrying out hydrolytic acidification on a reaction product to obtain 2-thiopheneacetic acid;
the sulfonic acid group functionalized ionic liquid consists of an anion part and a cation part; wherein the anion part is sulfate radical, bisulfate radical, chloride ion, bromide ion, sulfonate radical, acetate radical, dihydrogen phosphate radical, trifluoroacetate radical, trifluoromethanesulfonate radical, hexafluorophosphate radical or tetrafluoroborate radical; the cationic moiety is represented by any of the following structural formulas,
the alkylating agent is 2-chloroacetate.
2. A process for the synthesis of 2-thiopheneacetic acid according to claim 1, wherein: the Friedel-crafts alkylation reaction product is hydrolyzed under the alkaline environment to generate 2-thiophene acetate, and the 2-thiophene acetate generates 2-thiophene acetic acid under the acidic environment.
3. A process for the synthesis of 2-thiopheneacetic acid according to claim 1 or 2, wherein:
(1) Alkylation reaction: uniformly mixing thiophene, 2-chloroacetate and sulfonic acid group functionalized ionic liquid, heating to 60-100 ℃, reacting for 5-240 min, cooling to 30 ℃ after reaction, and distilling under reduced pressure to sequentially evaporate unreacted raw materials and an intermediate 2-thiopheneacetic ester;
(2) Hydrolysis and acidification: mixing the obtained 2-thiopheneacetic ester with alkaline water, heating to reflux reaction for 5-240 min, adding acid into the reaction solution, adjusting the pH value to 1-2, cooling, separating out and filtering to obtain 2-thiopheneacetic acid solid.
4. A process for the synthesis of 2-thiopheneacetic acid according to claim 3, wherein: the alkylation reaction is carried out in a way that the mass ratio of thiophene to 2-chloroacetate is 0.5.
5. A process for the synthesis of 2-thiopheneacetic acid according to claim 3, wherein: the raw materials and the residual catalyst in the kettle distilled by the alkylation reaction under reduced pressure are recycled and reused.
6. A process for the synthesis of 2-thiopheneacetic acid according to claim 3, wherein: in the hydrolysis acidification, the mass ratio of the 2-thiophene acetate to the alkali is 1:1-1:2, and the reaction time is 5-240 min.
7. A process for the synthesis of 2-thiopheneacetic acid according to claim 3, wherein: the alkali used for hydrolytic acidification is NaOH, KOH, ca (OH) 2 、Ba(OH) 2 、Na 2 CO 3 Or K 2 CO 3 (ii) a The acid used is hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid or hydroiodic acid.
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1998017639A1 (en) * | 1996-10-17 | 1998-04-30 | Smithkline Beecham Plc | Beta-thiopropionyl-amino acid derivatives and their use as beta-lactamase inhibitors |
CN102952114A (en) * | 2011-08-26 | 2013-03-06 | 中国科学院大连化学物理研究所 | Application of SO3H- functionalized ionic liquid serving as catalyst to synthesis of 2-acetylthiophene |
CN103467441A (en) * | 2013-09-23 | 2013-12-25 | 连云港宏业化工有限公司 | Synthetic method of 2-thiopheneacetic acid |
CN109721462A (en) * | 2017-10-30 | 2019-05-07 | 中国石油化工股份有限公司 | A method of preparing long-chain alkyl benzene |
CN110003167A (en) * | 2019-04-11 | 2019-07-12 | 青岛前线生物工程有限公司 | A kind of synthetic method of 2- thiophene acetic acid |
CN111205266A (en) * | 2020-01-17 | 2020-05-29 | 辽宁九华化工有限公司 | Synthetic method of 2-thiopheneacetic acid |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090326004A1 (en) * | 2008-06-03 | 2009-12-31 | Ranbaxy Laboratories Limited | Muscarinic receptor antagonists |
-
2020
- 2020-12-09 CN CN202011447929.0A patent/CN114605375B/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1998017639A1 (en) * | 1996-10-17 | 1998-04-30 | Smithkline Beecham Plc | Beta-thiopropionyl-amino acid derivatives and their use as beta-lactamase inhibitors |
CN102952114A (en) * | 2011-08-26 | 2013-03-06 | 中国科学院大连化学物理研究所 | Application of SO3H- functionalized ionic liquid serving as catalyst to synthesis of 2-acetylthiophene |
CN103467441A (en) * | 2013-09-23 | 2013-12-25 | 连云港宏业化工有限公司 | Synthetic method of 2-thiopheneacetic acid |
CN109721462A (en) * | 2017-10-30 | 2019-05-07 | 中国石油化工股份有限公司 | A method of preparing long-chain alkyl benzene |
CN110003167A (en) * | 2019-04-11 | 2019-07-12 | 青岛前线生物工程有限公司 | A kind of synthetic method of 2- thiophene acetic acid |
CN111205266A (en) * | 2020-01-17 | 2020-05-29 | 辽宁九华化工有限公司 | Synthetic method of 2-thiopheneacetic acid |
Non-Patent Citations (1)
Title |
---|
Iridium/f-ampha-catalyzed asymmetric hydrogenation of aromatic α-keto esters;Guoxian Gu等;《Org. Chem. Front.》;1209-1212 * |
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