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Chemical Structure| 64152-09-6 Chemical Structure| 64152-09-6

Structure of 64152-09-6

Chemical Structure| 64152-09-6

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Product Details of [ 64152-09-6 ]

CAS No. :64152-09-6
Formula : C9H7NO6
M.W : 225.16
SMILES Code : COC(=O)C1=C(C=CC(=C1)C(O)=O)[N+]([O-])=O
MDL No. :MFCD09026978

Safety of [ 64152-09-6 ]

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

Application In Synthesis of [ 64152-09-6 ]

* 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 [ 64152-09-6 ]

[ 64152-09-6 ] Synthesis Path-Downstream   1~2

  • 1
  • [ 20587-30-8 ]
  • methyl 5-[bis(acetyloxy)methyl]-2-nitrobenzoate [ No CAS ]
  • [ 64152-09-6 ]
YieldReaction ConditionsOperation in experiment
35.2 parts (56.1%) With sulfuric acid; acetic acid; In dichloromethane; acetic anhydride; (a) To a stirred and cooled (0 C.; 2-propanone/dry ice) solution of 54.4 parts of <strong>[20587-30-8]methyl 5-methyl-2-nitrobenzoate</strong> in 405 parts of acetic anhydride and 394 parts of acetic acid were added dropwise 110 parts of sulfuric acid and portionwise 83.6 parts of chromium(VI)oxide. Stirring was continued for 1/2 hour at 0-10 C. and overnight at room temperature. The reaction mixture was poured into ice-water and the whole was treated with dichloromethane. The precipitate which formed, was filtered off, washed with 2,2'-oxybispropane and dried in vacuo at 80 C., yielding 30.2 parts (48.1%) of product. The dichloromethane layer was separated and extracted with a sodium hydrogen carbonate solution and the aqueous extract was acidified with HCl 2N. The precipitate was filtered off and treated similarly as before, yielding an additional 5 parts (8.0%) of product. Total yield: 35.2 parts (56.1%) of 2-nitro-1,5-benzenedicarboxylic acid, 1-methyl ester; mp. 197.5 C. (interm. 60). From the dichloromethane layer there was also obtained methyl 5-[bis(acetyloxy)methyl]-2-nitrobenzoate; mp. 102.3 C. (interm. 61).
  • 2
  • [ 20587-30-8 ]
  • [ 64152-09-6 ]
YieldReaction ConditionsOperation in experiment
With chromium(VI) oxide; periodic acid; In acetonitrile; at 20℃; Example 141 : 2-(4-(5,6-Dichloro-1 H-benzo[d1imidazol-2-yl)benzamido)-5-(4-(4- fluorobenzyl)piperidine-1-carbonyl)benzoic acidMethod 3In a 1 L round-bottomed flask, to a mix of periodic acid (41.9 g, 184 mmol) and methyl 5- methyl-2-nitrobenzoate (8.97 g, 46.0 mmol) in 500 ml of acetonitrile, Cr03 (0.919 g, 9.19 mmol) was added portionwise and the mix was stirred overnight at RT. About 200 ml of isopropanol were cautiously added to destroy Cr03 and the mix was stirred for 2 h at RT; the inorganic solids were eliminated by filtration, then the solvent was evaporated under vacuum. The residue was partitioned between diluted HCI and AcOEt; the organic phase was further washed with brine, dried on Na2S04 and evaporated; the resulting solid was washed with DCM to afford 7.68 g of crude 3-methoxycarbonyl-4-nitrobenzoic acid (74.2% yield) as a white solid. To a suspension of this compound (0.6 g, 2.66 mmol) in dry DCM (50 ml), oxalyl dichloride (0.338 ml, 4.00 mmol) was added in one portion at room temperature; 3 drops of DMF were also added and the mixture was heated at 50C for 2 h. Volatile fractions were removed under vacuum to obtain methyl 5-chlorocarbonyl-2-nitrobenzoate as a pale yellow solid, which was resuspended in dry THF (40 ml); TEA (0.439 ml, 3.15 mmol) was added at room temperature followed by 4-(4-fluorobenzyl)piperidine (0.609 g, 3.15 mmol). The reaction was stirred overnight at the same temperature. Volatile fractions were evaporated under vacuum and the crude compound was portioned between ethyl acetate and a 2M aqueous solution of HCI. The organic phase was separated, dried (NaS04), filtered and evaporated under vacuum to afford a crude that was purified by flash chromatography (silica, hexane:EtOAc 4:6) to afford methyl 5-(4-(4-fluorobenzyl)- piperidine-1-carbonyl)-2-nitrobenzoate (0.756 g, 71.9% yield) as a white foam. A mixture of this compound (756 mg, 1.9 mmol) and 10% Pd/C (53 mg) in 50 ml of 1 :1 methanol/ ethyl acetate mixture was hydrogenated at 30 psi in a Parr apparatus overnight. The mixture was filtered through a Celite pad and evaporated to obtain methyl 2-amino-5-(4- (4-fluorobenzyl)piperidine-1-carbonyl)benzoate (660 mg, 94% yield) as a white foam.A mixture of 4-(5,6-dichloro-1 H-benzo[d]imidazol-2-yl)benzoic acid (199 mg, 0.648 mmol) and SOCI2 (2 ml, 27.4 mmol) was stirred at 70C for a total of 5 h. SOCI2 was evaporated completely, the residue was resuspended in 10 ml of dry THF, methyl 2-amino-5-(4-(4- fluorobenzyl)piperidine-1-carbonyl)benzoate (200 mg, 0.540 mmol) and DMAP (79 mg, 0.648 mmol) were added, and the mix was refluxed overnight. The mix was diluted with methanol and the precipitate was collected, then washed with aqueous K2C03, aqueous HCI, water, and finally with ethyl ether. After drying 272 mg (76%) of methyl 2-(4-(5,6- dichloro-1 H-benzo[d]imidazol-2-yl)benzamido)-5-(4-(4-fluorobenzyl)piperidine-1-carbonyl)- benzoate were obtained. This compound was dissolved in 20 ml of THF and 10 ml of MeOH, 6 N NaOH (274 muIota, 1.65 mmol) was added and the solution was heated to 70C for 3 h. The mixture was filtered through a Celite pad, then poured into acidic water; the precipitate was collected, washed with plenty of water and with MeOH. After drying, 138 mg (52%) of the title compound were obtained as an off-white solid, mp. > 200.1 H-NMR (300 MHz, DMSO-d6, 353K), delta ppm : 12.14 (br.s, 1 H), 8.73 (d, 1 H), 8.36 (m, 2H), 8.14 (m, 2H), 8.07 (d, 1 H), 7.86 (s, 2H), 7.67 (dd, 1 H), 7.22 (dd, 2H), 6.97-7.15 (m, 2H), 3.87-4.21 (m, 2H), 2.82-3.10 (m, 2H), 2.59 (d, 2H), 1.85 (br.s, 1 H), 1.66 (m, 2H), 1.09-1.34 (m, 2H); MS, m/z = 645.03 [MH]+
 

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