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Product Details of 2,4-Dichlorobenzoic acid

CAS No. :50-84-0
Formula : C7H4Cl2O2
M.W : 191.01
SMILES Code : C1=CC(=CC(=C1C(O)=O)Cl)Cl
MDL No. :MFCD00002414
InChI Key :ATCRIUVQKHMXSH-UHFFFAOYSA-N
Pubchem ID :5787

Safety of 2,4-Dichlorobenzoic acid

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H302-H315-H319-H335
Precautionary Statements:P261-P305+P351+P338

Application In Synthesis of 2,4-Dichlorobenzoic acid

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

  • Downstream synthetic route of [ 50-84-0 ]

[ 50-84-0 ] Synthesis Path-Downstream   1~12

  • 1
  • [ 611-03-0 ]
  • [ 50-84-0 ]
  • 2
  • [ 50-84-0 ]
  • [ 56621-89-7 ]
  • 2-chloro-4-(2-methoxy-pyrimidin-5-ylamino)-benzoic acid [ No CAS ]
  • 3
  • [ 50-84-0 ]
  • [ 201230-82-2 ]
  • [ 89-20-3 ]
  • [ 100-21-0 ]
  • [ 528-44-9 ]
  • [ 1967-31-3 ]
  • [ 74-11-3 ]
  • 4
  • [ 56882-52-1 ]
  • [ 50-84-0 ]
  • 5
  • [ 50-84-0 ]
  • [ 22808-73-7 ]
  • 4-(2,4-dichloro-benzoylsulfamoyl)-benzoic acid methyl ester [ No CAS ]
  • 6
  • [ 1004-38-2 ]
  • [ 50-84-0 ]
  • [ 830347-29-0 ]
  • 7
  • [ 53595-65-6 ]
  • [ 50-84-0 ]
  • [ 519055-62-0 ]
YieldReaction ConditionsOperation in experiment
59% In a round-bottom flask under N2 were introduced respectively 2,4-dichlorobenzoic acid (270 mg, 1.4 mmol), anhydrous THF (30 mL),DMF (4 drops) and oxalyl chloride (470 L, 5.6 mmol). The reaction mixture was stirred overnight at room temperature and then concentrated under reduced pressure. In a round-bottom flask under N2 were introduced respectively 5-bromothiophene-2-sulfonamide (300mg, 1.2 mmol), EtOAc (10 mL), Et3N (300 L, 3.2 mmol) and DMAP (2mg, 0.02 mmol). A solution of 2,4-dichlorobenzoyl chloride, previously prepared in dried toluene (10 mL), was added via a syringe over 15min. The mixture was stirred for 5 h at 55 C under N2, cooled to room temperature and quenched with 0.5 M aqueous HCl solution (40 mL).The resulting mixture was extracted with EtOAc (3 × 600 mL). The combined organic layers were dried over anhydrous MgSO4, filteredand concentrated under reduced pressure. The crude residue was purifiedby silica gel chromatography using DCM as eluent to afford 1k.Yield: 300 mg (59%); yellow solid; mp 114-116 C.1H NMR (400 MHz, CDCl3): = 9.07 (br s, 1 H), 7.74 (d, J = 6.0 Hz, 1 H),7.73 (d, J = 1.6 Hz, 1 H), 7.45 (d, J = 1.9 Hz, 1 H), 7.36 (dd, J = 8.4, 2.0 Hz,1 H), 7.13 (d, J = 4.1 Hz, 1 H).13C NMR (100 MHz, CDCl3): = 162.2, 139.5, 138.6, 136.0, 132.5,131.9, 130.7, 130.5, 129.3, 128.2, 123.3.
  • 8
  • [ 64-17-5 ]
  • [ 50-84-0 ]
  • [ 56882-52-1 ]
YieldReaction ConditionsOperation in experiment
With sulfuric acid; for 8h;Reflux; General procedure: A mixture of substituted benzoic acids (11a-g) (0.001M, 2.12g) and ethanol (20mL) were heated under reflux until the benzoic acid was dissolved in ethanol then few drops of concentrated H2SO4 was added to the mixture and reflux for 8h. The resulting mixture was cooled to room temperature and a saturated solution of sodium bicarbonate was added to the mixture to neutralise the benzoic acid. The precipitated product was filtered and washed with water and dried. The dried product was recrystallized with ethanol.
With sulfuric acid;Reflux; General procedure: To a stirred solution of different benzoic acids (6.42 mmol) in ethanol (3 mL) was added H2SO4 (0.1mL) and heated to reflux for 6-10 h. The reaction mixture was diluted with ethyl acetate followed by water. The organic layer was washed with saturated NaHCO3 followed by water and brine solution. The organic layer was dried over sodium sulphate, filtered and evaporated to obtain the respective ethyl benzoate derivatives.
With sulfuric acid;Reflux; General procedure: We added dense H2SO4 (0.098g, 1mmol) to a solution of substituted benzoic acid (5mmol) in dry ethyl alcohol (10mL). The mixture was heated under reflux until completion (as monitored via TLC), and the solvent was removed under reduced pressure. The residue was dissolved in ethyl acetate (50mL) and washed with 0.1M Na2CO3, brine, dried and concentrated, respectively. The crude products (intermediate 3) were used directly for the next step.
With sulfuric acid;Reflux; General procedure: The different organic acid (0.02 mol; 1a-o) was taken in 200 mL roundbottom flask. 20 mL absolute ethanol (99%) was added to the flask andstirred for ten minutes to homogenize the reaction contents. Later on, 2.5 mLconcentrated sulphuric acid, an activator, was added and reaction contents wererefluxed for 3-4 hours. Thin layer chromatography was the technique used tomonitor the completion of reaction by using 1:4 ratio of n-hexane and ethylacetate as mobile phase. After maximum completion, reaction mixture wastreated with 10% aqueous Na2CO3 (pH 9-10) to neutralize the reaction mixtureand to remove unreacted free acid. To get the pure esters, solvent extraction ofneutralized reaction mixture was performed by 50 mL of CHCl3 in a separatingfunnel for 3-4 times. After that CHCl3 layer was separated from the lowerdensity aqueous layer and was distilled by using rotary evaporator to acquireethyl esters.
With sulfuric acid;Reflux; General procedure: Aryl/aralkyl carboxylic acids (Ia-n) (0.032 mol)were homogenized in ethanol (99%, 30 mL) in a 250mL round bottom flask. Concentrated sulfuric acid(2.5 mL) was added in the mixture and set to reflux for3-5 h. TLC was developed for monitoring reactioncompletion. At maximum completion, the 10% aqueoussodium carbonate solution was poured to neutralizethe mixture up to pH of 9-10 after addition of 150mL distilled water. This step converted untreatedorganic acid and sulfuric acid into salts washed awayby aqueous layer. The esters were filtered or extractedby solvent extraction technique using 50 mL chloroformor diethyl ether from a separating funnel. Chloroform wasdistilled off to collect esters (IIa-n) [18, 19].
With sulfuric acid;Reflux; General procedure: (Un)Substituted benzoic acid (IVa-n) (0.02 mol) was refluxed with 60 mL EtOH for 4-5 h in the presence of conc. H2SO4 (1.25 mL) in around-bottom flask (250 mL). TLC plates were used to monitor the reaction. Excess distilled water (150 mL) was added after reaction completion and pH was adjusted to 8-10 by 20% aq. Na2CO3 solution. The product was collected through sequential extraction with CHCl3 (20 mL × 3). Chloroform was distilled off to collect the product. In some cases, the product was collected through filtration. Esters (Va-n) were used in further synthesis [18, 19].
With sulfuric acid; at 80℃; for 7h; General procedure: Taking 6a as an example, a mixture of benzoic acid (2.5 g,20.0 mmol), 4 mL sulfuric acid, and 50 mL ethanol was heated under reflux for 7 h (hour, h). After finishing the reaction, it was poured into water and extracted by ethylacetate, dried with anhydrous Na2SO4, and then the solventof the organic phase was evaporated under vacuum to give colorless liquid 4a. Then excess 80% N2H4·H2O and 15 mLof ethanol were added into the flask containing 4a, which was heated under reflux about 5 h. After the reaction was completed, it should be cooled into room temperature overnight and the white solid 5a was given after being filtered, washed with ethanol and dried in open air. Finally, 5a (1.4 g,8.0 mmol) was then subjected to substitution reaction with KOH (0.9 g, 15.6 mmol) and CS2(1.2 g, 15.0 mmol) togenerate intermediate 6a. At the same time, 6b-6m was synthesized by the methods described in the literature (Shi et al.2015; Du et al. 2013).

  • 10
  • [ 50-84-0 ]
  • [ 5292-39-7 ]
  • [ 652-12-0 ]
YieldReaction ConditionsOperation in experiment
72.05% In 5,5-dimethyl-1,3-cyclohexadiene; EXAMPLE 11 Into a 300 ml glass reactor equipped with a reflux condenser and a stirrer, and 50 g (0.207 mol) of the mixture (1:1) of the 3,4,5,6-tetrafluorophthaloyldifluoride and the 3,3,4,5,6,7- hexafluoro-1-[3H]-isobenzofuranone, 59.3 g (0.31 mol) of 2,4-dichlorobenzoic acid and 100 ml of xylene were charged, and the mixture was reacted at 150 C. for 12 hours with vigorous stirring. Then, the reaction mixture was separated by distillation to obtain 32.8 g of tetrafluorophthalic anhydride. The yield was 72.05%.
  • 11
  • [ 53595-65-6 ]
  • [ 50-84-0 ]
  • C10H9BrN2O2S2 [ No CAS ]
  • [ 519055-62-0 ]
YieldReaction ConditionsOperation in experiment
15%; 65% With dmap; 2-chloro-1-methyl-pyridinium iodide; triethylamine; In dichloromethane; at 20℃; for 1h; DCM (2.0 mL) was added to a 20 mL vial containing DMAP (3.81 mg, 0.031 mmol), 2-chloro-1-methylpyridin-1-ium iodide (0.191 g, 0.748 mmol), 2,4-dichlorobenzoic acid (0.119 g, 0.623 mmol), 5-bromothiophene-2-sulfonamide (0.302 g, 1.25 mmol) at rt. After stirring for 5 min, TEA (0.261 ml, 1.869 mmol) was slowly added to the reaction mixture. The reaction was stirred at rt for 1 h. The reaction solvent was concentrated under vacuum and the crude residue was taken up in ethyl acetate, washed with 1N HCl (1 mL), water, and brine. The ethyl acetate layer was separated, dried (Na2SO4), filtered and concentrated. The crude material was purified by silica gel flash column chromatography eluting with ethyl acetate in hexane from 0 to 30% to give the desired product (0.168 g, 65%) as colorless crystals: 1H NMR (499 MHz, CDCl3) δ 7.73 (d, J = 4.1 Hz, 1H), 7.71 (d, J = 8.5 Hz, 1H), 7.45 (d, J = 1.9 Hz, 1H), 7.36 (dd, J = 8.5, 1.9 Hz, 1H), 7.14 (d, J = 4.1 Hz, 1H).
  • 12
  • [ 62171-59-9 ]
  • [ 50-84-0 ]
  • 3-chloro-9,9-dimethyl-9,10-dihydrophenanthrene [ No CAS ]
 

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