WO2013047162A1 - Procédé de fabrication de chlorure de chloroalkylsulfonyle - Google Patents

Procédé de fabrication de chlorure de chloroalkylsulfonyle Download PDF

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Publication number
WO2013047162A1
WO2013047162A1 PCT/JP2012/072960 JP2012072960W WO2013047162A1 WO 2013047162 A1 WO2013047162 A1 WO 2013047162A1 JP 2012072960 W JP2012072960 W JP 2012072960W WO 2013047162 A1 WO2013047162 A1 WO 2013047162A1
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chloride
formula
reaction
group
chloroalkylsulfonyl
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PCT/JP2012/072960
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English (en)
Japanese (ja)
Inventor
孝洋 北本
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東洋紡株式会社
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Priority to JP2013536135A priority Critical patent/JP6003896B2/ja
Publication of WO2013047162A1 publication Critical patent/WO2013047162A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof

Definitions

  • the present invention relates to an improvement in production technology of chloroalkylsulfonyl chloride useful as a synthetic intermediate for various organic compounds used as pharmaceuticals, agricultural chemicals, electronic materials and the like.
  • Chloroalkylsulfonyl chloride is widely used as a synthetic intermediate for various organic compounds used as pharmaceuticals, agricultural chemicals, electronic materials, and the like.
  • a method for producing chloroalkylsulfonyl chloride for example, 500 g of sodium isethionate is put in a container containing 315 mL of N, N-dimethylformamide (DMF) and 600 mL of dichloromethane, and 1216 g of thionyl chloride is added dropwise.
  • a method of synthesizing chloroethylsulfonyl chloride by reacting at ⁇ 60 ° C. is known (Patent Document 1).
  • the produced chloroethylsulfonyl chloride is isolated by distilling off the solvent after separating, washing and drying the reaction solution.
  • the chloroethylsulfonyl chloride obtained by the method described in Patent Document 1 has a low purity and the yield does not reach a sufficiently satisfactory level.
  • an object of the present invention is to provide a method for producing chloroalkylsulfonyl chloride, which can obtain chloroalkylsulfonyl chloride having high purity with good yield and good productivity.
  • the present inventor has obtained a good reaction solution even when DMF is not used as a solvent for the chlorination reaction of hydroxyalkyl sulfonate or the amount used is reduced to a catalytic amount. It was thought that the purity and yield of the target chloroalkylsulfonyl chloride could be improved by selecting a solvent capable of ensuring stirring and liquid separation. As a result of examining various solvents, it was found that a solvent having a predetermined structure satisfies the above-mentioned conditions, and if a solvent having the specific structure is used in the chlorination reaction, good stirring properties and liquid separation properties are ensured. While confirming that chloroalkylsulfonyl chloride can be obtained with high purity and good yield, the present invention was completed.
  • the method for producing the chloroalkylsulfonyl chloride of the present invention comprises the following formula (1): [HO— (CH 2 ) n —SO 3 ] ⁇ (1) (In formula (1), n is an integer of 1 or more) A hydroxyalkyl sulfonate formed from an anion represented by the formula (1) and an alkali metal or alkaline earth metal is reacted with a chlorinating agent to give the following formula (2): Cl— (CH 2 ) n —SO 2 —Cl (2) (In formula (2), n is an integer of 1 or more) Wherein the reaction is represented by the following formula (3):
  • m is an integer of 1 to 3, and when m is 2 or more, the plurality of R may be the same or different, and R is a halogen atom, —NO 2
  • R is a halogen atom, —NO 2
  • m is preferably 1 or 2
  • R is preferably one selected from halogen atoms.
  • at least one selected from the group consisting of thionyl chloride, phosphorus oxychloride, phosphorus pentachloride, phosphorus trichloride and sulfuryl chloride is used as the chlorinating agent, and the reaction is performed with the substituted benzene. It is carried out in a mixed solvent of a system solvent and N, N-dimethylformamide. At this time, the amount of the N, N-dimethylformamide used is preferably 0.8 mol or less with respect to 1 mol of the hydroxyalkyl sulfonate.
  • the reaction is preferably performed at a temperature lower than the boiling point of the substituted benzene solvent and 40 ° C. or higher.
  • the reaction includes a first step of introducing a first chlorine atom for one molecule of the hydroxyalkyl sulfonate, and two steps for one molecule of the hydroxyalkyl sulfonate. It is divided into a second step for introducing a chlorine atom, and a part of the chlorinating agent is added during the first step, and the remainder of the chlorinating agent is added during the second step.
  • the method for producing chloroalkylsulfonyl chloride of the present invention is represented by the following formula (1).
  • [HO— (CH 2 ) n —SO 3 ] ⁇ (1) (In formula (1), n is an integer of 1 or more) A hydroxyalkyl sulfonate formed from an anion represented by formula (1) and an alkali metal or alkaline earth metal is reacted with a chlorinating agent to form the following formula (2): Cl— (CH 2 ) n —SO 2 —Cl (2) (In formula (2), n is an integer of 1 or more) A chloroalkylsulfonyl chloride represented by the formula (1) is obtained.
  • the said reaction in this invention is a chlorination reaction which introduce
  • n is preferably 8 or less, more preferably 2 or more and 4 or less, still more preferably 2 or 3, and particularly preferably 2.
  • alkali metal or alkaline earth metal include lithium, sodium, potassium, calcium, magnesium, and the like. Among these, sodium is particularly preferable from the viewpoint of availability and cost.
  • the hydroxyalkyl sulfonate formed from the anion represented by the formula (1) and an alkali metal is, for example, HO— (CH 2 ) n —SO 3 —M (1-1) (In formula (1-1), M is an alkali metal, and n is the same as in formula (1)).
  • M is an alkali metal
  • n is the same as in formula (1).
  • the hydroxyalkyl sulfonate formed from the anion represented by the formula (1) and an alkaline earth metal is, for example, [HO— (CH 2 ) n —SO 3 ] 2 M (1-2) (In formula (1-2), M is an alkaline earth metal, and n is the same as in formula (1)). Indicated by
  • hydroxyalkyl sulfonate examples include sodium hydroxymethanesulfonate, sodium 2-hydroxyethane-1-sulfonate (sodium isethionate), sodium 3-hydroxy-1-propanesulfonate, and the like. These are all commercially available. In addition, only 1 type may be used for a hydroxyalkyl sulfonate, and 2 or more types may be used together.
  • reaction with the chlorinating agent is represented by the following formula (3)
  • m is an integer of 1 to 3, and when m is 2 or more, the plurality of R may be the same or different, and R is a halogen atom, —NO 2
  • R is a halogen atom, —NO 2
  • a substituted benzene solvent represented by represented by
  • m is preferably 1 or 2, and particularly preferably 1.
  • specific examples of the halogen atom represented by R include Cl, Br, F, I and the like.
  • Specific examples of the alkyl group represented by R 1 include a methyl group, an ethyl group, a propyl group, and a butyl group.
  • R is preferably one selected from halogen atoms, and Cl is more preferable.
  • the substituted benzene solvent preferably has a dipole moment as a whole molecule.
  • the molecule as a whole has a dipole moment.
  • each polar group has a relationship in which at least one polar group leaves a dipole moment, and more preferably a mutual dipole moment. It is good to have a relationship of strengthening each other.
  • the two polar groups R are ortho-position (1,2-position; 1,6-position) or meta-position (1,3-position). Or the 1,5-position) relationship, and when in the para-position (1,4-position), the polar groups R are preferably different from each other.
  • the substituted benzene solvent desirably has a high boiling point, and the boiling point is preferably 90 ° C. or higher, more preferably 100 ° C. or higher, and further preferably 110 ° C. or higher.
  • the reaction temperature can be set high, so that the reaction time can be shortened and productivity can be improved.
  • the substituted benzene solvent has a benzene ring structure, it generally has a relatively high boiling point as described above. If the boiling point of the substituted benzene solvent is too high, it is difficult to distill off the solvent when isolating the target chloroalkylsulfonyl chloride from the reaction solution after the reaction. It is preferably 250 ° C. or lower, more preferably 200 ° C. or lower.
  • the substituted benzene-based solvent is preferably liquid at room temperature so that it can be used as a solvent.
  • the melting point is preferably 30 ° C. or lower.
  • chlorobenzene bromobenzene, o-dichlorobenzene, and m-dichlorobenzene are more preferable, and chlorobenzene is particularly preferable.
  • the substituted benzene solvent may be used alone or in combination of two or more.
  • the amount of the substituted benzene solvent used is not particularly limited.
  • the weight ratio is preferably 0.8 times or more and 20 times or less, preferably 1.5 times or more, based on the hydroxyalkyl sulfonate. 10 times or less are more preferable, and 2 times or more and 5 times or less are more preferable. If the amount of the solvent is too large, the reaction capacity tends to increase and the productivity tends to decrease. On the other hand, if the amount of the solvent is too small, the stirrability during the reaction may deteriorate and the reactivity may decrease.
  • the chlorinating agent is not particularly limited.
  • phosphorus chlorinating agents such as PCl 5 , PCl 3 and POCl 3 ; sulfur chlorinating agents such as ClSO 3 H, SO 2 Cl 2 and SOCl 2 ;
  • COCl 2 , (COCl) 2 , ⁇ , ⁇ -dichloromethyl methyl ether, zirconium tetrachloride and the like can be mentioned.
  • SOCl 2 thionyl chloride
  • POCl 3 phosphorus oxychloride
  • PCl 5 phosphorus pentachloride
  • PCl 3 phosphorus trichloride
  • SO 2 Cl 2 sulfuryl chloride
  • SOCl 2 sulphated chloride
  • Thionyl is more preferred.
  • These chlorinating agents are generally commercially available. In addition, only 1 type may be used for a chlorinating agent and it may use 2 or more types together.
  • the amount of the chlorinating agent used is theoretically 2 mol with respect to 1 mol of the hydroxyalkyl sulfonate, preferably 2.05 mol or more, 3.0 mol or less, more preferably 2.1 mol or more, 2.5 moles or less.
  • the amount of chlorinating agent used is less than the theoretical amount, by-products such as olefination are likely to occur, and conversely, when the amount of chlorinating agent used is excessive, three or more hydroxyalkyl sulfonates per molecule. In any case, the by-product into which the chlorine atom is introduced is likely to be generated, and in any case, the purity and yield of the target chloroalkylsulfonyl chloride may be reduced.
  • the chlorinating agent in particular, one or more chlorinating agents selected from the group consisting of thionyl chloride, phosphorus oxychloride, phosphorus pentachloride, phosphorus trichloride and sulfuryl chloride, a catalytic agent that promotes the reaction.
  • thionyl chloride phosphorus oxychloride
  • phosphorus pentachloride phosphorus trichloride
  • sulfuryl chloride a catalytic agent that promotes the reaction.
  • N, N-dimethylformamide (DMF) in combination.
  • the reaction may be performed in a mixed solvent of the substituted benzene solvent and DMF.
  • the amount of DMF used is preferably 0.8 mol or less, more preferably 0.5 mol or less, still more preferably 0.2 mol or less, particularly preferably 1 mol of hydroxyalkyl sulfonate. Is 0.1 mol or less. If the amount of DMF used is within the above range, DMF can be reliably separated from the reaction solution by a liquid separation operation described later, and even if DMF remains in the reaction solution, the amount is very small. Therefore, the residual DMF does not cause decomposition of the target chloroalkylsulfonyl chloride during heating such as distillation, and the target product can be obtained with high purity and high yield. In the present invention, by using the substituted benzene solvent described above, sufficient stirring and liquid separation properties are ensured even if DMF is not used or the amount used is as small as the above range. be able to.
  • the reaction is preferably performed at a temperature lower than the boiling point of the substituted benzene solvent and 40 ° C. or higher.
  • the substituted benzene solvent is refluxed during the chlorination reaction, many kinds of by-products are likely to be generated, and as a result, the purity and yield of the target chloroalkylsulfonyl chloride may be lowered. Therefore, the upper limit of the chlorination reaction temperature is preferably less than the boiling point of the substituted benzene solvent, and specifically, may be set according to the boiling point of the substituted benzene solvent.
  • the boiling point of the substituted benzene solvent is Tbp (° C.)
  • it is preferably (Tbp-5) ° C., more preferably (Tbp-10) ° C., and still more preferably (Tbp-15) ° C.
  • the reaction temperature during the chlorination reaction is too low, the progress of the reaction slows down, so that it takes a long time to complete the reaction, which may impair the productivity. Therefore, the reaction should be performed at 40 ° C. or higher. Is preferable, more preferably 45 ° C. or higher, and still more preferably 50 ° C. or higher.
  • the chlorination reaction in the present invention includes, for convenience, a first step of introducing the first chlorine atom for one molecule of hydroxyalkyl sulfonate and a second chlorine atom for one molecule of hydroxyalkyl sulfonate.
  • the first step and the second step are performed substantially continuously.
  • the reaction temperature in the first step and the reaction temperature in the second step may be the same or different.
  • the reaction temperature in the second step is the reaction in the first step. It is preferable to set the temperature higher than the temperature.
  • the temperature difference between the reaction temperature of the first step and the reaction temperature of the second step is preferably 15 ° C. or higher and 100 ° C. or lower, more preferably 20 ° C.
  • reaction temperature in the second step higher than the reaction temperature in the first step the reaction temperature may be continuously increased as the reaction proceeds (elapse of reaction time), or the temperature is raised stepwise. You may make it do. In order to avoid complications, the latter is preferable, and it is preferable to raise the temperature in two stages.
  • the reaction time of the chlorination reaction may be appropriately set according to the reaction temperature and the like, but considering productivity, it is preferably 5 minutes to 48 hours, more preferably 10 minutes to 24 hours, More preferably, it is 10 minutes or more.
  • the order of charging and the method of the hydroxyalkyl sulfonate, the substituted benzene solvent, the chlorinating agent, and DMF used as necessary are not particularly limited.
  • the raw material other than the chlorinating agent that is, hydroxyalkyl sulfonate, substituted benzene solvent, and DMF if necessary
  • the method of adding the chlorinating agent to this mixture is safe. From this point, it is preferably adopted.
  • adding the chlorinating agent it is preferable to add a part of the chlorinating agent during the first step described above and to add the remainder of the chlorinating agent during the second step described above.
  • the chloroalkylsulfonyl chloride produced by the chlorination reaction can be isolated by appropriately adopting known methods. For example, an aqueous solution of an inorganic acid (hydrochloric acid, etc.) is added to the obtained reaction solution, washed and then separated to remove the aqueous layer in which DMF and the like are dissolved, and a solvent (substituted benzene solvent) is obtained from the obtained organic layer. ) Is distilled off under reduced pressure, and then the chloroalkylsulfonyl chloride, which is the target product, is separated by distillation. Washing and liquid separation can be performed a plurality of times as necessary. Conventionally, the liquid separation after the second time may deteriorate, but according to the present invention, good liquid separation can be ensured.
  • an inorganic acid hydrochloric acid, etc.
  • the purity of the chloroalkylsulfonyl chloride obtained by the production method of the present invention is usually 98.5% or higher, preferably 99.0% or higher, more preferably 99.5% or higher. This purity can be determined by, for example, gas chromatography analysis.
  • the above-described high-purity chloroalkylsulfonyl chloride can be obtained in a yield of preferably 75% or more.
  • the yield of chloroalkylsulfonyl chloride is more preferably 80% or more, and still more preferably 82% or more.
  • GC Gas chromatographic
  • Detector Hydrogen flame ionization detector
  • Column “DB-17 Column” manufactured by Agilent Technologies Column temperature: held at 50 ° C. for 5 minutes, then heated to 250 ° C. at 10 ° C./min, and held at 250 ° C. for 5 minutes
  • Carrier gas helium flow rate (pressure): 100 kPa
  • Example 1 the reaction in Example 1 and Example 2 is shown by the following scheme.
  • Example 1 Into a four-necked flask with an internal volume of 300 mL, 60.0 g of sodium isethionate, 3.0 g of DMF, and 120.0 g of chlorobenzene (boiling point 132 ° C.) were added, 48.2 g of thionyl chloride was added thereto, and by-product gases (SO 2 and HCl ) was generated. After raising the temperature to 80 ° C., 53.0 g of thionyl chloride was added dropwise over 8 hours, and the reaction was continued until generation of by-product gas was completed. During the reaction, the stirring property of the reaction solution in the flask was good.
  • Example 2 Contents sodium isethionate in a reaction can of 500L 92.0kg, DMF4.7kg, charged with chlorobenzene (boiling point 132 °C) 184.1kg, which in thionyl chloride 74.3kg added, the by-product gas (SO 2 and HCl) The temperature was raised while generating. After raising the temperature to 80 ° C., 81.2 kg of thionyl chloride was added dropwise over 8 hours, and the reaction was continued until generation of by-product gas was completed. During the reaction, the stirring of the reaction solution in the reaction kettle was good. Thereafter, the reaction solution was cooled to room temperature, washed with 8% hydrochloric acid, and then separated to obtain an organic layer.
  • Example 3 A 200 mL four-necked flask was charged with 20.0 g of sodium isethionate, 1.0 g of DMF, and 41.9 g of chlorobenzene. To this, 22.8 g of phosphorus oxychloride (POCl 3 ) was added to generate 120 by-product gas. The temperature was raised to 0 ° C., and the reaction was continued until generation of by-product gas was completed. Thereafter, the reaction solution was cooled to room temperature, washed with 8% hydrochloric acid and then separated, and the organic layer was washed again with 15% hydrochloric acid and separated. At this time, the liquid separation property was good twice.
  • POCl 3 phosphorus oxychloride
  • Example 4 A 200 mL four-necked flask was charged with 20.0 g of sodium isethionate, 1.0 g of DMF, and 40.3 g of chlorobenzene, and 30.9 g of phosphorus pentachloride (PCl 5 ) was added thereto, generating 95 by-product gas. The temperature was raised to 0 ° C., and the reaction was continued until generation of by-product gas was completed. Thereafter, the reaction solution was cooled to room temperature, washed with 8% hydrochloric acid, and then separated. At this time, the liquid separation was good. Then, the organic layer was distilled to obtain 7.9 g of 2-chloroethanesulfonyl chloride (yield 36%). The purity of this 2-chloroethanesulfonyl chloride by gas chromatography (GC) analysis was 99.4%.
  • GC gas chromatography
  • Example 5 Into a four-necked flask with an internal volume of 100 mL, 10.0 g of sodium isethionate, 1.0 g of DMF, and 20.3 g of chlorobenzene were added, and 18.6 g of phosphorus trichloride (PCl 3 ) was added thereto to generate 99 by-product gas. The temperature was raised to 0 ° C., and the reaction was continued until generation of by-product gas was completed. Thereafter, the reaction solution was cooled to room temperature, washed with 8% hydrochloric acid, and then separated. At this time, the liquid separation was good.
  • PCl 3 phosphorus trichloride
  • Example 6 Into a four-necked flask with an internal volume of 100 mL, 10.0 g of sodium isethionate, 0.5 g of DMF, and 20.0 g of chlorobenzene were added, and 18.2 g of sulfuryl chloride (SO 2 Cl 2 ) was added thereto to generate a by-product gas. The temperature was raised to 72 ° C., and the reaction was continued until generation of by-product gas was completed. Thereafter, the reaction solution was cooled to room temperature, washed with 8% hydrochloric acid, and then separated. At this time, the liquid separation was good.
  • SO 2 Cl 2 sulfuryl chloride

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  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de fabrication d'un chlorure de chloroalkylsulfonyle, par lequel un chlorure de chloroalkylsulfonyle de pureté élevée peut être obtenu avec un rendement élevé avec une productivité élevée. Ce procédé de fabrication d'un chlorure de chloroalkylsulfonyle est un procédé d'obtention d'un chlorure de chloroalkylsulfonyle par réaction d'un sel d'acide hydroxyalkyl sulfonique avec un agent de chloration. Dans le procédé, la réaction est effectuée dans un solvant benzène substitué qui est représenté par la formule (3).(Dans la formule (3), m représente un entier de 1-3 et lorsque m est 2 ou plus, les différentes fractions R peuvent être identiques ou différentes l'une de l'autre ; et la ou les fractions R représentent un ou plusieurs groupes polaires qui sont choisis parmi un atome d'halogène, un groupe -NO2, un groupe -CN, un groupe -C(=O)R1 et un groupe -C(=O)OR1. (A cet égard, R1 représente un groupe alkyle ayant 1-8 atomes de carbone)).
PCT/JP2012/072960 2011-09-26 2012-09-07 Procédé de fabrication de chlorure de chloroalkylsulfonyle WO2013047162A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016204096A1 (fr) * 2015-06-18 2016-12-22 タマ化学工業株式会社 Procédé de production de chlorure de pyridine-3-sulfonyle
CN116769493A (zh) * 2023-05-11 2023-09-19 大庆轩隆化工有限公司 一种驱油用石油烷基苯磺酸盐表面活性剂及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07285926A (ja) * 1994-02-23 1995-10-31 Shionogi & Co Ltd クロロアルキルスルホニルクロリドの製造方法
JP2002053497A (ja) * 2000-08-07 2002-02-19 Sumitomo Chem Co Ltd 酸クロル化物の製造方法
JP2005179325A (ja) * 2003-12-24 2005-07-07 Sumitomo Chemical Co Ltd スルホン酸クロリドの製造方法
WO2009118753A2 (fr) * 2008-03-07 2009-10-01 Usv Limited Procédé de préparation de chlorhydrate de naratriptane

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07285926A (ja) * 1994-02-23 1995-10-31 Shionogi & Co Ltd クロロアルキルスルホニルクロリドの製造方法
JP2002053497A (ja) * 2000-08-07 2002-02-19 Sumitomo Chem Co Ltd 酸クロル化物の製造方法
JP2005179325A (ja) * 2003-12-24 2005-07-07 Sumitomo Chemical Co Ltd スルホン酸クロリドの製造方法
WO2009118753A2 (fr) * 2008-03-07 2009-10-01 Usv Limited Procédé de préparation de chlorhydrate de naratriptane

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
EMIL H. WHITE ET AL.: "N-Nitroso Sultams: On the Direction of Approach of Nucleophiles to the Sulfonyl Group", THE JOURNAL OF ORGANIC CHEMISTRY, vol. 52, no. 11, 1987, pages 2162 - 2166, XP001107042, DOI: doi:10.1021/jo00387a008 *
KUANG HUA: "Synthesis of 2-(4-Aminosulfonylphenyl)-4H-1,2-thiazine-1-dioxide", CHEMICAL RESEARCH, vol. 13, no. 3, 2002, pages 47 - 49 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016204096A1 (fr) * 2015-06-18 2016-12-22 タマ化学工業株式会社 Procédé de production de chlorure de pyridine-3-sulfonyle
CN116769493A (zh) * 2023-05-11 2023-09-19 大庆轩隆化工有限公司 一种驱油用石油烷基苯磺酸盐表面活性剂及其制备方法

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