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CAS No. :54811-50-6 MDL No. :MFCD01310823
Formula : C8H7IO2 Boiling Point : -
Linear Structure Formula :- InChI Key :LLVYMVJLXNNRND-UHFFFAOYSA-N
M.W : 262.04 Pubchem ID :9856531
Synonyms :

Safety of [ 54811-50-6 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P261-P305+P351+P338 UN#:N/A
Hazard Statements:H302-H315-H319-H335 Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 54811-50-6 ]

* 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 [ 54811-50-6 ]

[ 54811-50-6 ] Synthesis Path-Downstream   1~7

  • 1
  • [ 118-90-1 ]
  • [ 54811-50-6 ]
YieldReaction ConditionsOperation in experiment
95% With N-iodo-succinimide;palladium diacetate; In 4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran; N,N-dimethyl-formamide; 19.1 2-Iodo-6-methylbenzoic acid To a solution of 2-methylbenzoic acid (50 g, 0.36 mol) in DMF (800 mL) was added Pd(OAc)2 (8 g, 0.036 mmol) and NIS (80 g, 0.36 mol). Then the reaction mixture was heated to 100 C. for 1.5 h. The reaction was monitored by TLC. When the starting material was consumed, the reaction mixture was cooled, concentrated in vacuo to remove the excess solvent. The residue was dissolved in DCM (500 mL), washed with brine (2*200 mL), dried by Na2SO4, filtered, concentrated and purified by silica gel chromatography, eluting with PE/EA=5:1 to give the title compound (92 g, 95%) as a white solid. LCMS (ESI+): m/z 263 (M+H)+, Rt: 1.90 min.
92% With N-iodo-succinimide;palladium diacetate; In N,N-dimethyl-formamide; at 100℃; for 17h; To a solution of <strong>[118-90-1]o-toluic acid</strong> (2.00 g, 14.7 mmol) in dry DMF (60 mL) under an atmosphere of nitrogen was added /V-iodosuccinimide (3.64 g, 16.2 mmol) followed by Pd(OAc)2 (0.330 g, 1.47 mmol). The resulting reaction mixture was heated to 100 "C and stirred for 17 hours. Upon cooling to room temperature the reaction was diluted with water (100 mL) and EtOAc (150 mL), the layers were separated and the aqueous layer was extracted with EtOAc (2 x 100 mL), the combined organics were washed with water (100 mL), brine (100 mL), water (100 mL), brine (100 mL), dried ( gS04), filtered and concentrated in vacuo to give the title compound (157) (3.56 g, 92% yield) as a brown oily solid; 1H IMMR (400 MHz, CDCI3) delta 7.69 (d, J = 7.9 Hz, 1 H), 7.21 (d, J = 7.6 Hz, 1 H), 7.02 (t, J - 7.8 Hz, 1 H), 2.44 (s, 3H). LCMS Method C: rt 5 36 min.
92% With N-iodo-succinimide; palladium diacetate; In N,N-dimethyl-formamide; at 100℃; for 17h;Inert atmosphere; To a solution of <strong>[118-90-1]o-toluic acid</strong> (2.00 g, 14.7 mmoi) in dry D F (60 mL) under an atmosphere of nitrogen was added A/-iodosuccinimide (3.64 g, 16.2 mmol) followed by Pd(OAc)2 (0.330 g, 1.47 mmoi). The resulting reaction mixture was heated to 100 C and stirred for 17 hours. Upon cooling to room temperature the reaction was diluted with water (100 mL) and EtOAc (150 mL), the layers were separated and the aqueous layer was extracted with EtOAc (2 x 100 mL), the combined organics were washed with water (100 mL), brine (100 mL), water (100 mL), brine (100 mL), dried (MgS04), filtered and concentrated in vacuo to give the title compound {157) (3.56 g, 92% yield) as a brown oily solid; 1H N R (400 MHz, CDCi3) delta 7.69 (d, J = 7.9 Hz, 1 H), 7.21 (d, J = 7.6 Hz, 1 H), 7.02 (t, J = 7.8 Hz, 1 H), 2.44 (s, 3H). LC S Method C: rt 5.36 min
84% With N-iodo-succinimide; palladium diacetate; In N,N-dimethyl-formamide; at 100℃; for 2h;Inert atmosphere; A mixture of 2-methylbenzoic acid (10.0 g, 73.5 mmol), N-Iodosuccinimide (16.0 g, 73.5 mmol) and palladium diacetate (1.6 g, 7.35 mmol) in N,N-dimethylformamide (160 ml) was stirred at 100C for 2 hours under nitrogen atmosphere. TLC showed the reaction was complete. The cooled reaction mixture was allowed to cool to room temperature and partitioned between ethyl acetate (300 ml) and water (500 ml). The organic layer was collected, and the aqueous layer was extracted with ethyl acetate (100 ml x2). The combined organic layers were washed with brine (200 ml), dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give 2- iodo-6-methylbenzoic acid (16 g, yield 84%) as yellow solid which was used in next step directly without further purification.1H NMR (400 Hz, CDCl3): delta 2.29 (s, 3H), 7.06 (t, J = 8.0 Hz, 1H), 7.27 (d, J = 7.6 Hz, 1H), 7.67 (d, J = 8.0 Hz, 1H). Chemical Formula: C8H7IO2; Molecular Weight: 262.04;
69% With [bis(acetoxy)iodo]benzene; iodine; palladium diacetate; In N,N-dimethyl-formamide; at 100℃; for 24h;Sealed tube; General procedure: In a flame-dried 100 mL round-bottom flask, benzoic acid starting material (16.4 mmol, 1.0 equiv.), palladium acetate (0.05 equiv.), iodobenzene diacetate (1.5 equiv.), and iodine (1.5 equiv.) were dissolved in anhydrous DMF (40 mL) under atmospheric air. The flask was then sealed with a septum and the reaction mixture was stirred at 100 C for 24 h. The reaction mixture was cooled to room temperature, diluted with ethyl acetate, and then washed with 0.5 N HCl (420 mL). The organic phase was washed with brine, dried over Na2SO4, and concentrated in a rotary evaporator. The residue was purified by column chromatography on silica gel (3 : 1 hexane/EtOAc) to give the desired iodinated product.
With sodium chloride; iodine; sodium thiosulfate; acetic acid;palladium diacetate; In water; Example 5 Into the same reactor as in Example 1 were charged 50 mg of palladium acetate, 0.3 g of <strong>[118-90-1]o-toluic acid</strong>, 0.28 g of iodine, 0.13 g of periodic acid, 10 ml of acetic acid and 1 ml of water. The mixture thus obtained was heated with stirring at 70 C. for 4 hours. After completion of the reaction, the reaction mixture was cooled and poured into water, and the objective product was extracted with ethyl acetate. After separation into layers, the organic layer was washed successively with aqueous solution of sodium thiosulfate and saturated aqueous solution of sodium chloride and dried over anhydrous magnesium sulfate. By distilling off the solvent under reduced pressure, there was obtained a crude product of the objective compound. The same 400 MHz-NMR analysis as in Example 1 revealed that rate of formation of the objective 2-iodo-6-methylbenzoic acid was 50%. Regioselectivity of iodination into the 2-position was 100%.
With sodium chloride; sodium acetate; Iodine monochloride; sodium thiosulfate; acetic acid;palladium diacetate; Example 6 Into the same reactor as in Example 1 were charged 50 mg of palladium acetate, 0.3 g of <strong>[118-90-1]o-toluic acid</strong>, 3 g of sodium acetate, 0.36 g of ICl and 11 ml of acetic acid. The mixture thus obtained was heated with stirring at 100 C. for 10 hours. After completion of the reaction, the acetic acid was distilled off under reduced pressure, and the residue was extracted with ethyl acetate. The organic layer was washed successively with aqueous solution of sodium thiosulfate and saturated aqueous solution of sodium chloride and dried over anhydrous magnesium sulfate. By distilling off the solvent under reduced pressure, there was obtained a crude product of the objective compound. The same 400 MHz-NMR analysis as in Example 1 revealed that rate of formation of the objective 2-iodo-6-methylbenzoic acid was 60%. Regioselectivity of iodination into the 2-position was 100%.
With N-iodo-succinimide; sodium chloride; sodium thiosulfate;palladium diacetate; In dimethylsulfoxide-d6; N,N-dimethyl-formamide; Example 14 Into the same reactor as in Example 1 were charged 5 mg of palladium acetate, 0.3 g of <strong>[118-90-1]o-toluic acid</strong>, 0.5 g of N-iodosuccinimide and 11 ml of DMF. The mixture thus obtained was heated with stirring at 100 C. for 6 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and poured into water, and the objective product was extracted with ethyl acetate. The mixture was separated into layers, the organic layer was washed successively with aqueous solution of sodium thiosulfate and aqueous solution of sodium chloride and dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure to obtain a crude product. A part of the crude product was dissolved in DMSO-d6 and analyzed by 400 MHz-NMR. As the result, rate of formation of the objective 2-iodo-6-methylbenzoic acid was found to be 79%. Regioselectivity of iodination into the 2-position was 100%.

  • 2
  • [ 54811-50-6 ]
  • [ 103440-55-7 ]
YieldReaction ConditionsOperation in experiment
50% With thionyl chloride In methanol; 4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran 19.2 19.2 19.2 Methyl 2-iodo-6-methylbenzoate To a solution of 2-iodo-6-methylbenzoic acid (80 g, 0.31 mol) in DCM (700 mL) was added SOCl2 (55 g, 0.46 mol) dropwise at 0° C. After addition, the reaction mixture was stirred at reflux for 2 hours. The solvent was removed in vacco. The residue was added dropwise to MeOH (100 mL) at 0° C. The mixture was then refluxed overnight. The solvent was evaporated under reduce pressure. The residue was purified by silica gel chromatography eluting PE/EA=70:1 to give the title compound (43 g, 50%) as a white solid. LCMS (ESI+): m/z 277 (M+H)+, Rt: 2.17 min.
Multi-step reaction with 2 steps 1: SOCl2 / 2 h / Heating 2: 3 h / Heating
Multi-step reaction with 2 steps 1: oxalyl dichloride / dichloromethane / 20 °C 2: 20 °C
  • 4
  • [ 4389-50-8 ]
  • [ 54811-50-6 ]
YieldReaction ConditionsOperation in experiment
79% A solution of <strong>[4389-50-8]2-amino-6-methylbenzoic acid</strong> (1601) (106.5 g, 705 mmol) in H2O (200 mL) was cooled to 0 - 5 0C, con. HCl (250 mL) was added slowly. The solution was stirred for 15 min at 0-5 0C. A solution of sodium nitrite (58.4 g, 6.85 mol) in H2O (120 mL) was added dropwise at 0-5 0C, and the resulting mixture was stirred for 30 min. Then above solution was added to a solution of KI (351 g, 2.11 mol) in H2O (200 mL), and the resulting mixture was stirred at RT for 16 h. The solution was poured into ice water (2000 mL) and extracted with ethyl acetate (3 x 1000 mL). The combined organic layer was washed with aqueous NaOH (15%, 3 x 200 mL). The aqueous layer was acidified to PH = 1, and extracted with ethyl acetate (3 x 1000 mL). The combined organic layer was dried over <n="81"/>Na2SO4 and filtered. The filtrate was concentrated in vacuo to afford the desired product, 2-iodo-6-methylbenzoic acid (1602) (145 g, 79% yield) as a yellow solid
General procedure: To a suspension of <strong>[4389-50-8]2-amino-6-methylbenzoic acid</strong> (G-1) (20.0 g, 132.0 mmol, 1.0 eq) in H2O (55 mL) at 0-5 C., conc. HCl (36.5%, 64 mL, 749 mmol, 5.7 eq) is added slowly. After stirring for 15 min, the mixture is added dropwise to a solution of sodium nitrite (12.02 g, 174.0 mmol, 1.32 eq) in H2O (36 mL) at 0-5 C., and the resulting mixture is stirred for 1 h. The resulting solution is then added to a solution of KI (60.5 g, 364.5 mmol, 2.76 eq) in H2O (150 mL) at 0-5 C. The reaction mixture is allowed to warm to RT and stirred at RT overnight. The mixture is extracted with ethyl acetate (3×100 mL). The combined organic layers are washed with water (2×100 mL), dried over anhydrous Na2SO4 and filtered. The filtrate is concentrated in vacuo and the residue is purified by flash column chromatography on silica gel (0-20% ethyl acetate-petro ether) to afford the product, 2-iodo-6-methylbenzoic acid (G-2).
[00773] Compound Si was prepared according to Method G. It was thencoupled to 3-amino-pyrazine-2- carboxylic acid using Method D to prepare compound 52. ESI-MS m/z: 454.3 [M+H]t [00736] To a suspension of <strong>[4389-50-8]2-amino-6-methylbenzoic acid</strong> (G-1) (20.0 g, 132.0 mmol, 1.0 eq) in H20 (55mL) at 0-5 C, conc. HC1 (36.5 %, 64 mL, 749 mmol, 5.7 eq) is added slowly. After stirring for 15 mm, the mixture is added dropwise to a solution of sodium nitrite (12.02 g, 174.0 mmol, 1.32 eq) in H20 (36 mL) at 0-5 C, and the resulting mixture is stirred for 1 h. The resulting solution is then added to a solution of KI (60.5 g, 364.5 mmol, 2.76 eq) in H20 (150 mL) at 0-5 C. The reaction mixture is allowed to warm to RT and stirred at RT overnight. The mixture is extracted with ethyl acetate (3 x 100 mL). The combined organic layers are washed with water (2 x 100 mL), dried over anhydrous Na2SO4 and filtered. The filtrate is concentrated in vacuo and the residue is purified by flash column chromatography on silica gel (0-20% ethyl acetate-petro ether) to afford the product, 2-iodo-6- methylbenzoic acid (G-2).
With hydrogenchloride; potassium iodide; sodium nitrite; In water; at 0 - 40℃; for 20h; (3) Synthesis of 2-iodo-6-methylbenzyl chloride[55-3] (hereinafter referred to as a compound [55-3]) To a suspension of <strong>[4389-50-8]2-amino-6-methylbenzoic acid</strong> (2.01 g) in water (4 mL) was added concentrated hydrochloric acid (5 mL) at 0C. To the mixture were added a solution of sodium nitrite (1.19 g) in water (3 mL) and a solution of potassium iodide (7.18 g) in water (5 mL) at 0C. After warmed up to room temperature, the mixture was stirred for 20 hours. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The obtained organic layer was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The obtained residue was dissolved in tetrahydrofuran (30 mL), and to the mixture was added boranedimethylsulfide complex (9.0 mL) at room temperature, and the mixture was heated at reflux for 2 hours. Methanol and water were added to the reaction mixture, and the mixture was extracted with ethyl acetate. The obtained organic layer was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The obtained residue was dissolved in dimethylsulfoxide (20 mL). To the mixture was added cyanuric chloride (2.70 g) at 0C, and the mixture was stirred at 0C for 30 minutes. Water was added to the reaction mixture, and extracted with hexane. The obtained organic layer was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure to give the titled compound (2.28 g) as a yellow solid. 1H-NMR (400 MHz, CDCl3) delta: 7.73 (1H, d, J = 8.1 Hz), 7.16 (1H, d, J = 7.3 Hz), 6.90 (1H, t, J = 7.8 Hz), 4.81 (2H, s), 2.52 (3H, s).
[00590] To a suspension of <strong>[4389-50-8]2-amino-6-methylbenzoic acid</strong> (C-i) (20.0 g, 132.0 mmol, 1.0 eq) in H20 (55 mL) at 0-5 C, conc. HC1 (36.5 %, 64 mL, 749 mmol, 5.7 eq) is added slowly. After stirring for 15 mm, the mixture is added dropwise to a solution of sodium nitrite (12.02 g, 174.0 mmol, 1.32 eq) in H20 (36 mL) at 0-5 C, and the resulting mixture is stirred for 1 h. The resulting solution is then added to a solution of KI (60.5 g, 364.5 mmol, 2.76 eq) in H20 (150 mL) at 0-5 C. The reaction mixture is allowed to warm to RT and stirred at RT overnight. The mixture is extracted with ethyl acetate (3 x 100 mL). The combined organic layers are washed with water (2 x 100 mL), dried over anhydrous Na2SO4 and filtered. The filtrate is concentrated in vacuo and the residue is purified by flash column chromatography on silica gel (0-20% ethyl acetate - petro ether) to afford the product, 2-iodo-6- methylbenzoic acid (C-2).
With hydrogenchloride; potassium iodide; sodium nitrite; In water; at 0 - 20℃; for 15h; Amino acid 101 is converted to iodo acid 102 by treatment with 5 N hydrochloric acid, sodium nitrite and potassium iodide, warming the reaction mixture from 0 C. to room temperature and continuing to stir the reaction for 15 hours. lodo acid 102 is treated with oxalyl chloride in methylenechloride at room temperature to produce the iodo acidchloride 103, which is converted to the correspondingmethyl ester 104 upon reaction with methanol at room temperature.

  • 5
  • [ 67-56-1 ]
  • [ 54811-50-6 ]
  • [ 103440-55-7 ]
YieldReaction ConditionsOperation in experiment
76% Stage #1: methanol; 2-iodo-6-methylbenzoic acid With diazomethyl-trimethyl-silane In diethyl ether; dichloromethane at 0℃; for 0.75h; Inert atmosphere; Stage #2: With hydrogenchloride In diethyl ether; dichloromethane; water 15.b A solution of 2-iodo-6-methylbenzoic acid {157) (2.50 g, 9.54 mmol) in DCM (30 mL) and methanol (8 mL.) under an atmosphere of nitrogen was cooled to 0 °C and trimethylsilyldiazomethane (2.0 M in diethyl ether, 9.54 mL, 19.1 mmol) was added dropwise. The reaction was stirred at 0 °C for 45 minutes and then quenched with 2 M aq. HCI (50 mL). DCM (150 mL) was added to the quenched reaction and the layers were separated. The aqueous layer was extracted with DCM (100 mL), the organics were combined and washed with sat. aq. NaHC03 (100 mL), water ( 100 mL), brine (100 mL), dried (MgS0 ), filtered and concentrated in vacuo to give a yellow oil. The crude product was purified by silica gel chromatography (BiotageIsolera, 40 g Si Cartridge, 0-20% EtOAc in petroleum benzine 40-60 °C) to give the title compound (158) (2.00 g, 76% yield) as a colourless oil; 1H NMR (400 MHz, CDCI3) 6 7.65 (ddd, J = 7.9, 1.0, 0.5 Hz, 1 H), 7.19 - 7.15 (m, 1 H), 6.99 (t, J = 7.8 Hz, 1 H), 3.95 (s, 3H), 2.33 (s, 3H). LCMS Method C: rt 6.08 min; m/z 277.0 [M+Hf.
  • 6
  • [ 54811-50-6 ]
  • [ 18107-18-1 ]
  • [ 103440-55-7 ]
YieldReaction ConditionsOperation in experiment
76% Stage #1: 2-iodo-6-methylbenzoic acid; diazomethyl-trimethyl-silane In methanol; dichloromethane at 0℃; for 0.75h; Inert atmosphere; Stage #2: With hydrogenchloride In methanol; dichloromethane 15.b Methyl 2-iodo-6-methylbenzoate (158) A solution of 2-iodo-6-methylbenzoic acid (157) (2.50 g, 9.54 mmoi) in DCM (30 mL) and methanol (8 mL) under an atmosphere of nitrogen was cooled to 0 °C and trimethylsilyldiazomethane (2,0 M in diethyl ether, 9.54 mL, 19.1 mmol) was added dropwise. The reaction was stirred at 0 °C for 45 minutes and then quenched with 2 M aq. HCI (50 mL). DCM (150 mL) was added to the quenched reaction and the layers were separated. The aqueous layer was extracted with DCM (100 mL), the organics were combined and washed with sat. aq. NaHC03 (100 mL), water (100 mL), brine (100 mL), dried (MgS04), filtered and concentrated in vacuo to give a yellow oil. The crude product was purified by silica gel chromatography (Biotage I solera, 40 g Si Cartridge, 0-20% EtOAc in petroleum benzine 40-60 °C) to give the title compound (158) (2.00 g, 76% yield) as a colourless oil; H NMR (400 MHz, CDCI3) δ 7.65 (ddd, J = 7.9, 1.0, 0.5 Hz, 1 H), 7.19 - 7.15 (m, 1 H), 6.99 (t, J = 7.8 Hz, 1 H), 3.95 (s, 3H), 2.33 (s, 3H). LCMS Method C: rt 6.08 min; m/z 277.0 [M+H]+.
  • 7
  • [ 54811-50-6 ]
  • [ 74-88-4 ]
  • [ 103440-55-7 ]
YieldReaction ConditionsOperation in experiment
63% With potassium carbonate In N,N-dimethyl-formamide at 20℃; 80.4 4. Step- Synthesis of meth l 2-iodo-6-meth lbenzoate A mixture of 2-iodo-6-methylbenzoic acid (5.6 g, 21.4 mmol), iodomethane (2.5 ml, 40.1 mmol) and potassium carbonate(5.0 g, 35.9 mmol) in N,N-dimethylformamide (40 ml) was a stirred at room temperature overnight. TLC showed the reaction was complete. The reaction mixture was partitioned between ethyl acetate (50 ml) and water (50ml). The organic layer was collected, and the aqueous layer was extracted with ethyl acetate (100 ml x2). The combined organic layers were washed with brine (200 ml), dried over anhydrous sodium sulfate, and concentrated under reduced pressure to afford a crude residue which was purified by silica gel flash chromatography (eluted with 5% ethyl acetate in hexane) to afford methyl 2-iodo-6- methylbenzoate (3.8 g, yield 63%) as white solid. LC_MS: (ES+): m/z 277.0 [M+H]+. tR = 2.863 min.1H NMR (400 Hz, CDCl3): δ 2.35 (s, 3H), 3.97 (s, 3H), 7.01 (t, J = 8.0 Hz, 1H), 7.20 (d, J = 7.6 Hz, 1H), 7.67 (d, J = 8.0 Hz, 1H). Chemical Formula: C9H9IO2; Molecular Weight: 276.07;
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