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GB2078215A - N-(4-pyridylmethyl)benzamides and Their Production - Google Patents

N-(4-pyridylmethyl)benzamides and Their Production Download PDF

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GB2078215A
GB2078215A GB8116144A GB8116144A GB2078215A GB 2078215 A GB2078215 A GB 2078215A GB 8116144 A GB8116144 A GB 8116144A GB 8116144 A GB8116144 A GB 8116144A GB 2078215 A GB2078215 A GB 2078215A
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acid
substituted
carbon atoms
substituted acid
sulfonylamino
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D213/00Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/36Radicals substituted by singly-bound nitrogen atoms
    • C07D213/40Acylated substituent nitrogen atom
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P25/00Drugs for disorders of the nervous system
    • A61P25/20Hypnotics; Sedatives

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  • Biomedical Technology (AREA)
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  • Neurosurgery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Pyridine Compounds (AREA)

Abstract

Compounds of the formula <IMAGE> where X and Y, which may be the same or different, are hydrogen, halogen, hydroxyl, nitro, linear or branched alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, dialkylamino having 1 to 4 carbon atoms, acylamino having 1 to 4 carbon atoms, sulfonylamino, phenyl, trifluoromethyl and phenylsulfonylamino, which are neuroleptic agents, particularly useful in therapeutics, are prepared by formation of the amide group.

Description

SPECIFICATION N-(4-Pyridylmethyl)-Benzamides and Their Production This invention relates to a method for the industrial production of N-(4-pyridylmethyl)benzamides, which are very powerful as neuroleptic agents, thus making them particularly useful in therapeutics.
These compound are of the formula:
where X and Y, which may be the same or different, are hydrogen, halogen, hydroxyl, nitro, linear or branched alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, dialkylamino having 1 to 4 carbon atoms, acylamino (e.g. alkanoylamino) having 1 to 4 carbon atoms, sulfonylamino, phenyl, trifluoromethyl or phenylsulfonylamino.
The method of the invention comprises the following operations: 1) reacting a substituted acid of the formula
where X and Y have the aforesaid meanings, with 4-aminomethyl-pyridine of the formula:
in the presence of a condensing agent in a suitable solvent and at temperatures between -800C and the boiling point of the solvent itself; 2) removing the solid by-products by filtration upon completion of the reaction; 3) evaporating the solvent to dryness, and 4) crystallizing the residue formed by the desired product in a suitable solvent.
If desired, the product may subsequently be converted into a salt, for example by treatment with an acid.
With the exception of the compound in which X and Y are methyl groups in the 3- and 5positions, the compounds of formula (I) and their physiologically acceptable acid addition salts are novel compounds.
In the compounds of formula (I), Y is preferably a hydrogen atom and Xis preferably a hydroxy, dialkylamino, alkanoylamino, sulfonylamino or phenyl sulfonylamino group, which may for example be in the 4-position. A particularly preferred group of compounds is those in which Y is a hydrogen atom and X is a hydroxy, dimethylamino, acetamido, sulfonylamino or phenylsulfonylamino group in the 4position.
The compounds of formula (I) may be formulated for use in conventional manner, for example with one or more pharmaceutical carriers.
Some examples which do not limit the scope of this invention are given below.
Example 1(X=3-CH,; Y=5-C H3) A mixture of 7.5 g (0.05 moles) of 3,5-dimethyl-benzoic acid, 5.4 g (0.05 moles) of 4aminomethylpyridine and 100 ml of methylene chloride is placed in a two-neck flask with a capacity of 250 ml, fitted with a thermometer, a calcium chloride tube, an ice bath and magnetic stirring. When the mixture is at 20C a solution of 10.3 g (0.05 moles) of dicyclohexylcarbodiimide in 25 ml of methylene chloride is added portionwise and while stirring. Stirring is maintained between 0 and 50C for 2 hours and the temperature is then allowed to rise until it reaches room temperature, leaving the reaction proceed under stirring overnight. The dicyclohexylurea formed is filtered and washed with two portions of 25 ml of methylene chloride each.The filtrate, together with the washing liquids, are evaporated to dryness and the solid residue is crystallized from ethyl acetate. The N-(4-pyridylmethyl)3,5-dimethylbenzamide has a m.p.=1 05-1060C.
Analysis Calculated for C1sH16N2o C: 74.97; H: 6.71; N: 11.65 Found C: 74.85; H: 6.70; N: 11.65 Example 2 (X=3-CH3; Y=H) Operation is as in the preceding example, using 0.05 moles of m-toluic acid and acetonitrile as a solvent. M.p.=1 04-1 050C (dimethylformamide-water).
Analysis Calculated for C14H,4N20 C: 74.31; H: 6.23; N: 12.38 Found C: 74.50; H: 6.19; N: 12.35 Example 3 (X=4-But; Y=H) Operation is as in Example 1, using 0.05 moles of 4-tertbutylbenzoic acid and tetrahydrofuran as solvent. M.p.=1 29-1 300C (benzene).
Analysis Calculated for C'7H20N20 C: 76.08; H: 7.51; N: 10.44 Found C: 75.81; H: 7.24; N: 10.15 Example 4 (X=4-CH3S; Y=H) Operation is as in Example 1, using 0.05 moles of 4-thiomethoxybenzoic acid. M.p.=1 50- 1 520C (ethanol-water).
Analysis Calculated for C14H,4N20S C: 65.10; H: 5.46; N: 10.84; S: 12.41 Found C: 65.19; H: 5.23; N: 10.61; S: 12.21 Example 5 (X=Y=H) Operation is as in Example 1, using 0.05 moles of benzoic acid. M.p.=1 14-11 60C (ethanolwater).
Analysis Calculated for C13H'3N20 C: 73.58; H: 5.66; N: 13.20 Found C: 73.23; H: 5.71; N: 13.40 Example 6 (X=4-CH3; Y=H) Operation is as in Example 1, using 0.05 moles of p-toluic acid. M.p.=1 30-1 31 OC (water).
Analysis Calculated for C14H14N20 C: 74.31; H: 6.23; N: 12.38 Found C: 74.09; H: 6.22; N:12.21 Example 7 (X=2-CH3; Y=H) Operation is as in Example 1, using 0.05 moles of o-toluic acid. M.p.=1 46-1 480C (water).
Analysis Calculated for C14H'4N20 C: 74.31; H: 6.23; N: 12.38 Found C: 74.08; H: 6.31; N: 12.49 Example 8 (X=4-OCH3; Y=H) Operation is as in Example 1, using 0.05 moles of anisic acid. M.p.=l 38-140"C (water).
Analysis Calculated for C14H14N202 C: 69.57; H: 5.85; N: 11.45 Found C: 69.40; H; 5.80; N: 11.56 Example 9 (X=4-OH; Y=H) Operation is as in Example 1, using 0.05 moles of 4-hydroxybenzoic acid. M.p. 2600C (dimethylformamide-water).
Analysis Calculated for Ca3H12N202 C: 68.40; H: 5.29; N: 12.27 Found C: 68.46; H: 5.15; N: 12.14 Example 10 (X=4-NO2; Y=H) Operation is as in Example 1, using 0.05 moles of 4-nitrobenzoic acid. M.p.=1 98-2000C (ethanol-water).
Analysis Calculated for C13H1,N303 C: 60.69; H: 4.31; N: 16.33 Found C: 60.42; H: 4.18; N: 16.06 Example 11 (X=4-N(CH3)2; Y=H) Operation is as in Example 1, using 0.05 moles of 4-dimethylaminobenzoic acid. M.p.=206- 2070C (dimethylformamide-water).
Analysis Calculated for C1sH,7N30 C: 70.56; H: 6.71; N: 16.45 Found C: 70.31; H: 6.48; N: 16.22 Example 12 (X=4-CH3CONH;Y=H) Operation is as in Example 1, using 0.05 moles of 4-acetylaminobenzoic acid. M.p.=233- 2350C (water).
Analysis Calculated for C,5H,5N302 C: 66.89; H: 5.61; N: 15.60 Found C: 66.70; H: 5.34; N: 15.48 Example 13 (X=4-SO2NH 2;Y=H) Operation is as in Example 1, using 0.05 moles of 4-sulfamoylbenzoic acid. M.p.=235-2370C (water).
Analysis Calculated for C,3H,3N303S C: 53.60; H: 4.49. N: 14.42; S: 10.90 Found C: 53.74; H: 4.61; N: 14.61; S: 10.64 Example 14 (X=4-C6H5; Y=H) Operation is as in Example 1, using 0.05 moles of 4-phenylbenzoic acid. M.p.=l 93-194"C (methanol-water).
Analysis Calculated for CrgH,6N20 C: 79.14; H: 5.59; N: 9.71 Found C: 79.10; H: 5.74; N: 9.59 Example 15 (X=4-CI; Y=H) Operation is as in Example 1, using 0.05 moles of 4-chlorobenzoic acid. M.p.=l 33--1 340C (dimethylformamide-water).
Analysis Calculated for C,3H,1N20CI C: 63.31; H: 4.46; N: 11.36 Cl: 14.36 Found C: 63.29; H: 4.61; N: 11.12; Cl: 14.44 Example 16 (X=3-CI; Y=H) Operation is as in Example 1, using 0.05 moles of 3-chlorobenzoic acid. M.p.=88-900C (ethanol-water).
Analysis Calculated for C13H11N20CI C: 63.31; H: 4.46; N: 11.36; Cl: 14.36 Found C: 63.19; H: 4.51; N: 11.16; Cl: 14.63 Example 17 (X=2-CL; Y=H) Operation is as in Example 1, using 0.05 moles of 2-chlorobenzoic acid. M.p.=98-990C (ethanol-water).
Analysis Calculated for C13H11N20CI C: 63.31; H: 4.46; N: 11.36; Cl: 14.36 Found C: 63.12; H: 4.56; N: 11.16; Cl: 14.46 Example 18 (X=Y=3,5-Cl2) Operation is as in Example 1, using 0.05 moles of 3,5-dichlorobenzoic acid. M.p.=1 44-1 460C (dimethylformamide-water).
Analysis Calculated for C13H1oN2ocl2 C: 55.51; H: 3.55; N: 9.96; Cl: 25.26 Found C: 55.42; H: 3.36; N: 10.07; Cl: 25.54 Example 19 (X=4-F; Y=H) Operation is as in Example 1, using 0.05 moles of 4-fluorobenzoic acid. M.p.=88--90"C (ethylacetate-petroleum ether).
Analysis Calculated for C13H11N20F C: 67.82; H: 4.85; N: 12.17 Found C: 67.73; H: 4.79; N: 11.89 Example 20 (X=4-CF3; Y=H) Operation is as in Example 1, using 0.05 moles of 4-trifluoromethylbenzoic acid. M.p.=1 67-1 690C (methanol) Analysis Calculated for C14H11N20F3 C: 60.00; H: 3.92; N: 10.00 Found C: 60.27; H: 4.25; N: 10.05 Example 21 (X=4-C6H5-SO2NH; Y=H) Operation is as in Example 1, using 0.05 moles of 4-phenylsulfonylaminobenzoic acid.
M.p.=1 80-181 OC (ethyl acetate).
Analysis Calculated for C19H17N303S C: 62.11; H: 4.66; N: 11.43; S: 8.72 Found C: 62.22; H: 4.60; N: 11.45; S: 8.96 Pharmacological Studies The product of Example 1 of this patent application has evidenced a pharmacological activity spectrum similar to that of neuroleptics. characterized by a reduction in motile activity which is accomplished by loss of reactivity as the dose is increased and by cataleptic immobilization at even higher doses. For this reason, the measurement selected for comparing the potency of the products of the examples of this patent application was the reduction in motile activity at a standardized dose for all of them.
Acute Toxicity Swiss l.C.R. albino mice were used. The products were administered intraperitoneally and the observation time was 72 hours, following which the death rate was evaluated in the different batches, calculating the LD50 from these data. The results obtained are given in the following table.
Product of Example LD50Fi.p.) mg/kg 1 266 2 271 3 114.7 4 259.3 5 417.8 6 364.4 7 510 8 345.7 9 1,277.7 Product of Example LD50fi.p.) mg/kg 10 350 11 300 12 1,333.8 13 1,314.1 14 15 16 219 17 18 113 19 339.1 20 21 > 1,500 Reduction in Motile Activity Swiss I.C.R. albino mice were used. The products were administered intraperitoneally at the dose of 72 mg/kg, motile activity control measurements having been taken previously. Fresh motile acitivity measurements are taken thirty minutes after administration of the products and when compared with the control measurements they enable us to calculate the percentage of reduction in motile activity. All the measurements were taken with an automatic actinometer supplied by the Panlab company, taking at least six control measurements for each product and six measurements after administering the product, calculating the reduction in motile activity from the difference between the corresponding averages. The results obtained are given in the following table.
Product % Reduction in Motile of Activity at the Dose Example of 72 mglkg (i.p.) 1 99.6 2 97.5 3 97.5 4 87.6 5 6 56.3 7 90.4 8 72.9 9 98.3 10 85.1 11 93.6 12 99.8 13 90.2 14 15 95.3 16 99.2 17 18 19 97.6 20 21 98.7

Claims (33)

Claims
1. N-(4-pyridylmethyl)-benzamides of the general formula:
where X and Y, which may be the same or different, are hydrogen, halogen, hydroxyl, nitro, linear or branched alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms,dialkylamino having 1 to 4 carbon atoms, acylamino having 1 to 4 carbon atoms, sulfonylamino, phenyl, trifluoromethyl or phenylsulfony!amino, (excluding the compound in which X and Y represent methyl in positions 3 and 5), and the physiologically acceptable acid addition salts thereof.
2. Compounds as claimed in claim 1 in which Y is a hydrogen atom.
3. Compounds as claimed in claim 1 or claim 2 in which X is hydroxy, dialkylamino, alkanoylamino, sulfonylamino or phenylsulfonylamino.
4. Compounds as claimed in claim 1 in which Y is a hydrogen atom and X is a hydroxy, dimethylamino, acetamido sulfonylamino or phenylsulfonylamino group in the 4-position.
5. A compound as claimed in claim 1, said compound being the product of any one of Examples 2 to 21.
6. A pharmaceutical composition comprising a compound as claimed in claim 1 together with one or more pharmaceutical carriers.
7. a method for the industrial production of N-(4-pyridylmethyl)-benzamides of the general formula
where X and Y, which may be the same or different, are hydrogen, halogen, hydroxyl, nitro, linear or branched alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, dialkylamino having 1 to 4 carbon atoms, acylamino having 1 to 4 carbon atoms, sulfonylamino, phenyl, trifluoromethyl, and phenylsulfonylamino, which comprises: 1) reacting a substituted acid of the general formula:
where X and Y have the aforesaid meanings, with 4-aminomethylpyridine of the formula:
in the presence of a condensing agent in a suitable solvent and at temperatures between -800C and the boiling point of the solvent itself; 2) removing the solid by-products by filtration upon completion of the reaction; 3) evaporating the solvent to dryness, and 4) crystallizing the residue formed by the desired product in a suitable solvent.
8. a method according to claim 7 in which dicyclohexylcarbodiimide is used as condensing agent.
9. A method according to claim 7 or claim 8 in which the solvent used is methylene chloride.
10. A method according to claim 7 or claim 8 in which the solvent used is acetonitrile.
11. A method according to claim 7 or claim 8 the solvent used is tetrahydrofuran.
12. A method according to any one of claims 7 to 11 in which the substituted acid is 3,5dimethylbenzoic acid.
1 3. a method according to any one of claims 7 to 11 in which the substituted acid is m-toluic acid.
14. A method according to any one of claims 7 to 11 in which the substituted acid is 4-tertbutylbenzoic acid.
1 5. A method according to any one of claims 7 to 11 in which the substituted acid is 4thiomethoxybenzoic acid.
1 6. A method according to any one of claims 7 to 11 in which the substituted acid is benzoic acid.
1 7. A method according to any one of claims 7 to 11 in which the substituted acid is p-toluic acid.
1 8. A method according to any one of claims 7 to 11 in which the substituted acid is o-toluic acid.
19. A method according to any one of claims 7 to 11 in which the substituted acid is anisic acid.
20. A method according to any one of claims 7 to 11 in which the substituted acid is 4hydroxybenzoic acid.
21. A method according to any one of claims 7 to 11 in which the substituted acid is 4nitrobenzoic acid.
22. A method according to any one of claims 7 to 11 in which the substituted acid is 4dimethylaminobenzoic acid.
23. A method according to any one of claims 7 to 11 in which the substituted acid is 4acetylaminobenzoic acid.
24. A method according to any one of claims 7 to 11 in which the substituted acid is 4sulfamoylbenzoic acid.
25. A method according to any one of claims 7 to 11 in which the substituted acid is 4phenylbenzoic acid.
26. A method according to any one of claims 7 to 11 in which the substituted acid is 4chlorobenzoic acid.
27. A method according to any one of claims 7 to ii in which the substituted acid is 3chlorobenzoic acid.
28. A method according to any one of claims 7 to 11 in which the substituted acid is 2chlorobenzoic acid.
29. A method according to any one of claims 7 to 11 in which the substituted acid is 3,5dichlorobenzoic acid.
30. A method according to any one of claims 7 to 11 in which the substituted acid is 4fluorobenzoic acid.
31. A method according to any one of claims 7 to 11 in which the substituted acid is 4trifluoromethylbenzoic acid.
32. A method according to any one of claims 7 to 11 in which the substituted acid is 4phenylsulfonylaminobenzoic acid.
33. A method as claimed in any one of claims 7 to 32 in which the product is subsequently converted into a salt.
GB8116144A 1980-06-23 1981-05-27 N-(4-pyridylmethyl)-benzamides and their production Expired GB2078215B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
ES492686A ES8200663A1 (en) 1980-06-23 1980-06-23 N-(4-pyridylmethyl)benzamides and Their Production

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GB2078215A true GB2078215A (en) 1982-01-06
GB2078215B GB2078215B (en) 1984-06-06

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JP (1) JPS5732266A (en)
CH (1) CH651298A5 (en)
DE (1) DE3122700A1 (en)
ES (1) ES8200663A1 (en)
FR (1) FR2485008A1 (en)
GB (1) GB2078215B (en)
PT (1) PT73147B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0077534A3 (en) * 1981-10-15 1984-03-07 Chugai Seiyaku Kabushiki Kaisha Benzamide derivatives, a process for preparing the same, and pharmaceutical compositions containing the same
US4595780A (en) * 1984-01-06 1986-06-17 Shionogi & Co., Ltd. Sulfonamido-benzamide derivatives
US7388018B2 (en) 2003-09-18 2008-06-17 Basf Aktiengesellschaft 4-Piridinylmethylsulphonamide derivatives as fungicidal plant protein agents

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9300083D0 (en) * 1993-01-05 1993-03-03 Roussel Lab Ltd Chemical compounds

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1073961A (en) * 1964-04-22 1967-06-28 Far Eastern Detailers Ltd Pyridine derivatives and their preparation
NL7416176A (en) * 1973-12-26 1975-06-30 Upjohn Co PROCESS FOR PROMOTING THE PRODUCTION OF ENDOGENIC PROSTAGLANDINS BY MAMMALS, AND PROCESS FOR THE PREPARATION OF PREPARATIONS FOR USE THEREIN.
DE2417763A1 (en) * 1974-04-11 1975-10-30 Bayer Ag CARBON ACID AMIDE, THE PROCESS FOR THEIR MANUFACTURING AND THEIR USE AS A MEDICINAL PRODUCT
DE2428673A1 (en) * 1974-06-14 1976-01-02 Bayer Ag CARBON ACID AMIDE, THE PROCESS FOR THEIR MANUFACTURING AND THEIR USE AS A MEDICINAL PRODUCT

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0077534A3 (en) * 1981-10-15 1984-03-07 Chugai Seiyaku Kabushiki Kaisha Benzamide derivatives, a process for preparing the same, and pharmaceutical compositions containing the same
US4595780A (en) * 1984-01-06 1986-06-17 Shionogi & Co., Ltd. Sulfonamido-benzamide derivatives
US7388018B2 (en) 2003-09-18 2008-06-17 Basf Aktiengesellschaft 4-Piridinylmethylsulphonamide derivatives as fungicidal plant protein agents

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Publication number Publication date
ES492686A0 (en) 1981-06-01
FR2485008A1 (en) 1981-12-24
DE3122700A1 (en) 1982-04-22
PT73147A (en) 1981-07-01
GB2078215B (en) 1984-06-06
PT73147B (en) 1982-07-16
CH651298A5 (en) 1985-09-13
ES8200663A1 (en) 1981-06-01
JPS5732266A (en) 1982-02-20

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