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Chemical Structure| 13506-76-8
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Product Details of [ 13506-76-8 ]

CAS No. :13506-76-8 MDL No. :MFCD00007267
Formula : C8H7NO4 Boiling Point : -
Linear Structure Formula :- InChI Key :CCXSGQZMYLXTOI-UHFFFAOYSA-N
M.W : 181.15 Pubchem ID :16097
Synonyms :

Calculated chemistry of [ 13506-76-8 ]

Physicochemical Properties

Num. heavy atoms : 13
Num. arom. heavy atoms : 6
Fraction Csp3 : 0.12
Num. rotatable bonds : 2
Num. H-bond acceptors : 4.0
Num. H-bond donors : 1.0
Molar Refractivity : 47.19
TPSA : 83.12 Ų

Pharmacokinetics

GI absorption : High
BBB permeant : No
P-gp substrate : No
CYP1A2 inhibitor : No
CYP2C19 inhibitor : No
CYP2C9 inhibitor : No
CYP2D6 inhibitor : No
CYP3A4 inhibitor : No
Log Kp (skin permeation) : -6.87 cm/s

Lipophilicity

Log Po/w (iLOGP) : 0.75
Log Po/w (XLOGP3) : 0.75
Log Po/w (WLOGP) : 1.6
Log Po/w (MLOGP) : 0.84
Log Po/w (SILICOS-IT) : -0.47
Consensus Log Po/w : 0.69

Druglikeness

Lipinski : 0.0
Ghose : None
Veber : 0.0
Egan : 0.0
Muegge : 1.0
Bioavailability Score : 0.56

Water Solubility

Log S (ESOL) : -1.65
Solubility : 4.1 mg/ml ; 0.0226 mol/l
Class : Very soluble
Log S (Ali) : -2.07
Solubility : 1.52 mg/ml ; 0.00841 mol/l
Class : Soluble
Log S (SILICOS-IT) : -1.54
Solubility : 5.24 mg/ml ; 0.0289 mol/l
Class : Soluble

Medicinal Chemistry

PAINS : 0.0 alert
Brenk : 2.0 alert
Leadlikeness : 1.0
Synthetic accessibility : 1.78

Safety of [ 13506-76-8 ]

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

Application In Synthesis of [ 13506-76-8 ]

* 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.

  • Upstream synthesis route of [ 13506-76-8 ]
  • Downstream synthetic route of [ 13506-76-8 ]

[ 13506-76-8 ] Synthesis Path-Upstream   1~29

  • 1
  • [ 13506-76-8 ]
  • [ 75844-41-6 ]
Reference: [1] Journal fuer Praktische Chemie (Leipzig), 1985, vol. 327, # 5, p. 865 - 867
[2] Chemische Berichte, 1919, vol. 52, p. 1083
  • 2
  • [ 13506-76-8 ]
  • [ 3970-40-9 ]
Reference: [1] Tetrahedron Letters, 2010, vol. 51, # 50, p. 6646 - 6648
[2] Organic and Biomolecular Chemistry, 2018, vol. 16, # 30, p. 5416 - 5421
  • 3
  • [ 83-41-0 ]
  • [ 1975-50-4 ]
  • [ 13506-76-8 ]
  • [ 603-11-2 ]
Reference: [1] J. Gen. Chem. USSR (Engl. Transl.), 1990, vol. 60, # 10, p. 2118 - 2122[2] Zhurnal Obshchei Khimii, 1990, vol. 60, # 10, p. 2370 - 2374
[3] J. Gen. Chem. USSR (Engl. Transl.), 1990, vol. 60, # 10, p. 2118 - 2122[4] Zhurnal Obshchei Khimii, 1990, vol. 60, # 10, p. 2370 - 2374
[5] J. Gen. Chem. USSR (Engl. Transl.), 1990, vol. 60, # 10, p. 2118 - 2122[6] Zhurnal Obshchei Khimii, 1990, vol. 60, # 10, p. 2370 - 2374
  • 4
  • [ 83-41-0 ]
  • [ 13506-76-8 ]
YieldReaction ConditionsOperation in experiment
64% With oxygen; sodium hydroxide In ethanol at 65℃; for 24 h; Autoclave 1,2-dimethyl-3-nitrobenzene (453 mg, 3 mmol, 1.0 eq)Sodium hydroxide (0.9 g, 22.5 mmol, 7.5 eq)Was added to a 100 ml autoclave,Add ethanol 5ml;After charging oxygen three times,Passing oxygen gas (pressure 1.8MPa),In the oil bath temperature control 65 for 24 hoursAfter the reaction was diluted with methanol,Neutralization PH = 6-7,The solvent was removed under reduced pressure,After adding ethyl acetate, the mixture was dried and filtered.Separated by chromatography,1,2-dimethyl-3-nitrobenzene 47 mg (0.31 mmol)1,2-dimethyl-3-nitrobenzene conversion was 90percentTo give 350 mg (1.93 mmol) of 2-nitro-5-methylbenzoic acid,The yield was 64percent.
Reference: [1] Patent: CN106995374, 2017, A, . Location in patent: Paragraph 0121; 0122; 0123
[2] Journal of Organic Chemistry, 2018, vol. 83, # 15, p. 8092 - 8103
  • 5
  • [ 1885-76-3 ]
  • [ 13506-76-8 ]
Reference: [1] Helvetica Chimica Acta, 1960, vol. 43, p. 104 - 113
[2] Chemische Berichte, 1919, vol. 52, p. 1083
[3] Journal of Organic Chemistry, 1976, vol. 41, # 21, p. 3356 - 3359
  • 6
  • [ 40637-78-3 ]
  • [ 13506-76-8 ]
Reference: [1] Chemische Berichte, 1919, vol. 52, p. 1083
[2] Journal of Organic Chemistry, 1976, vol. 41, # 21, p. 3356 - 3359
  • 7
  • [ 83-41-0 ]
  • [ 1975-50-4 ]
  • [ 13506-76-8 ]
  • [ 603-11-2 ]
Reference: [1] J. Gen. Chem. USSR (Engl. Transl.), 1990, vol. 60, # 10, p. 2118 - 2122[2] Zhurnal Obshchei Khimii, 1990, vol. 60, # 10, p. 2370 - 2374
[3] J. Gen. Chem. USSR (Engl. Transl.), 1990, vol. 60, # 10, p. 2118 - 2122[4] Zhurnal Obshchei Khimii, 1990, vol. 60, # 10, p. 2370 - 2374
[5] J. Gen. Chem. USSR (Engl. Transl.), 1990, vol. 60, # 10, p. 2118 - 2122[6] Zhurnal Obshchei Khimii, 1990, vol. 60, # 10, p. 2370 - 2374
  • 8
  • [ 570-24-1 ]
  • [ 13506-76-8 ]
Reference: [1] Helvetica Chimica Acta, 1960, vol. 43, p. 104 - 113
  • 9
  • [ 124-38-9 ]
  • [ 41085-43-2 ]
  • [ 13506-76-8 ]
Reference: [1] Angewandte Chemie, 1966, vol. 78, p. 1062 - 1063
  • 10
  • [ 570-24-1 ]
  • [ 544-92-3 ]
  • [ 13506-76-8 ]
Reference: [1] Bulletin des Societes Chimiques Belges, 1969, vol. 78, p. 571 - 582
  • 11
  • [ 13506-76-8 ]
  • [ 41085-43-2 ]
YieldReaction ConditionsOperation in experiment
30% With 2.9-dimethyl-1,10-phenanthroline; oxygen; copper (I) acetate; silver sulfate; sodium bromide In dimethyl sulfoxide at 160℃; for 24 h; Schlenk technique Silak reaction tube equipped with a magnetic stirrer was charged with 6.2 mg of silver sulfate,36.3 mg of copper acetate, 12.5 mg of 2,9-dimethyl-1,10-o-phenanthroline,36.2 mg of 2-nitro-6-methylbenzoic acid and 30.9 mg of sodium bromide4 mL of dimethyl sulfoxide.The reaction was heated at 160 ° C for 24 hours in the presence of oxygen.After the reaction was completed, distilled water was added to quench the reaction,Extraction with ethyl acetate 3 times, each time 10mL,The combined organic phases are concentrated,13.0 mg of 2-nitro-6-methylbromobenzene was obtained in a yield of 30percent.
Reference: [1] Patent: CN107325002, 2017, A, . Location in patent: Paragraph 0118
[2] Organic and Biomolecular Chemistry, 2018, vol. 16, # 30, p. 5416 - 5421
[3] Journal of Organic Chemistry, 2016, vol. 81, # 7, p. 2794 - 2803
  • 12
  • [ 13506-76-8 ]
  • [ 54915-41-2 ]
YieldReaction ConditionsOperation in experiment
84% With hydrogenchloride In tetrahydrofuran EXAMPLE 28
Preparation of 2-methyl-6-nitrobenzyl alcohol.
To a 0° solution of 54.30 g (0.30 moles) of 2-methyl-6-nitrobenzoic acid in 500 ml of anhydrous tetrahydrofuran was added dropwise under a nitrogen atmosphere, 380 ml (0.38 moles) of a stock IM boran/THF solution at such a rate that the temperature did not exceed 5°.
Upon complete addition, the ice bath was removed, the solution allowed to stir at room temperature for 14 hours, heated to reflux for 4 hrs. and then cooled to 0° in an ice bath.
The reaction was quenched by the dropwise addition of 400 ml of 10percent hydrochloric acid, the solution heated to reflux on a steam bath for 0.5 hrs., the THF solvent distilled at atmospheric pressure and the insoluble precipitate extracted into methylene chloride.
The methylene chloride extracts were combined, washed with satd. sodium bicarbonate solution, dried (Na2 SO4) and the solvent removed in vacuo affording a reddish colored semi solid.
Purification was effected from 300 ml of carbon tetrachloride resulting in 41.35 g (84percent yield) of yellow flakes; mp 67°-8°.
Anal. calc'd. for C8 H9 NO3: C, 57.48; H, 5.43; N, 8.38. Found: C, 57.34; H, 5.42; N, 8.47.
30.5 g
Stage #1: With sodium tetrahydroborate In tetrahydrofuran
Stage #2: With dimethyl sulfate In tetrahydrofuran at 20℃; for 20 h;
Stage #3: With hydrogenchloride In tetrahydrofuran; water at 0℃; for 1 h;
Reference Production Example 150 (0903) To a mixture of 15.6 g of sodium tetrahydroborate and 200 ml of tetrahydrofuran, 50 g of 2-methyl-6-nitrobenzoic acid was added at room temperature. To the reaction mixture, 34 ml of dimethylsulfuric acid was added at 0°C, followed by stirring at room temperature for 20 hours. 5percent Hydrochloric acid (300 ml) was added at 0°C, followed by stirring for one hour. After extraction with ethyl acetate, the organic layer was washed with water, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain 30.5 g of 2-methyl-6-nitrobenzyl alcohol (C150A). 1H-NMR (CDCl3) δ (ppm): 7.71 (1H, d, J = 7.7 Hz), 7.49 (1H, d, J = 7.5 Hz), 7.36 (1H, t, J= 7.9 Hz), 4.71 (2H, d, J = 7.2 Hz), 2.62 (1H, t, J = 7.4 Hz), 2.56 (3H, s).
30.5 g
Stage #1: With sodium tetrahydroborate; dimethyl sulfate In tetrahydrofuran at 0 - 20℃; for 20 h;
Stage #2: With hydrogenchloride In tetrahydrofuran; water at 0℃; for 1 h;
Reference Production Example 84 (1485) At room temperature, 50 g of 2-methyl-6-nitrobenzoic acid was added to a mixture of 15.6 g of sodium borohydride and 200 ml of tetrahydrofuran. At 0° C., 34 ml of dimethylsulfuric acid was added to the reaction mixture, followed by stirring at room temperature for 20 hours. At 0° C., 300 ml of an aqueous 5percent hydrochloric acid solution was added, followed by stirring for 1 hour. After extraction with ethyl acetate, the organic layer was washed with water, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain 30.5 g of 2-methyl-6-nitrobenzyl alcohol. (1486) 1H-NMR (CDCl3) δ (ppm): 7.71 (1H, d, J=7.7 Hz), 7.49 (1H, d, J=7.5 Hz), 7.36 (1H, t, J=7.9 Hz), 4.71 (2H, d, J=7.2 Hz), 2.62 (1H, t, J=7.4 Hz), 2.56 (3H, s).
Reference: [1] Angewandte Chemie - International Edition, 2017, vol. 56, # 39, p. 11958 - 11962[2] Angew. Chem., 2017, vol. 129, # 39, p. 12120 - 12124,5
[3] Journal of Organic Chemistry, 2011, vol. 76, # 9, p. 3484 - 3497
[4] Patent: US3932407, 1976, A,
[5] Journal of Chemical Research, Miniprint, 2001, # 10, p. 1023 - 1055
[6] Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1996, p. 1699 - 1704
[7] Journal of Heterocyclic Chemistry, 1986, vol. 23, # 3, p. 897 - 899
[8] Patent: US31617, 1984, E1,
[9] Patent: WO2013/162072, 2013, A1, . Location in patent: Page/Page column 949; 950
[10] Patent: EP2927218, 2015, A1, . Location in patent: Paragraph 0903
[11] Patent: US2016/150787, 2016, A1, . Location in patent: Paragraph 1485-1486
[12] Synlett, 2017, vol. 28, # 14, p. 1724 - 1728
[13] Patent: WO2018/138692, 2018, A1, . Location in patent: Page/Page column 57
  • 13
  • [ 13506-76-8 ]
  • [ 54915-41-2 ]
YieldReaction ConditionsOperation in experiment
97% With hydrogenchloride In tetrahydrofuran EXAMPLE 10
Synthesis of 2-methyl-6-nitrobenzyl alcohol
A 100 mL round bottomed flask under dry argon was charged with 5 g of 2-methyl-6-nitrobenzoic acid which was dissolved in 60 mL of dry tetrahydrofuran.
To this solution was added slowly with cooling and stirring, 64.17 mL of a 1M solution of BH3.THF in THF.
The mixture was refluxed for 17 h then the reaction was slowly and carefully quenched with an excess of 10percent aqueous hydrochloric acid.
The THF was removed under vacuum and the residue was extracted with three 50 mL aliquots of methylene chloride.
The combined organic extracts were dried over anhydrous magnesium sulfate, filtered and the solvent removed.
The crude product was recrystallized from methylene chloride/pentane to give 4.95 g of yellowish crystals (97percent yield).
Reference: [1] Patent: US5200544, 1993, A,
  • 14
  • [ 13506-76-8 ]
  • [ 99548-56-8 ]
Reference: [1] Chemical Communications, 2005, # 44, p. 5583 - 5585
  • 15
  • [ 13506-76-8 ]
  • [ 74-88-4 ]
  • [ 61940-22-5 ]
YieldReaction ConditionsOperation in experiment
98% With potassium carbonate In N,N-dimethyl-formamide at 20℃; for 5 h; Step 1:
Methyl-(2-methyl-6-nitro)benzoate
Into a suspension of 100 g (552 mmol) of 2-methyl-6-nitrobenzoic acid, 114.4 g (828 mmol) of potassium carbonate in 500 mL of dimethylforamide was added dropwise 86 g (606 mmol) of iodomethane with stirring at ambient temperature.
After addition, the suspension was stirred for additional 5 hours.
The reaction mixture was then poured into water and extracted with ethyl acetate.
The organic layer was washed with water and brine and dried over anhydrous sodium sulfate.
Any solid was removed by filtration and the filtrate was concentrated to a 105.6 g of colorless oil as product in 98percent yield. 1H NMR (CDCl3) (300 MHz) δ 2.7 (s, 3H), 3.95 (s, 3H), 8.01 (d, 3JHCCH=8.6 Hz, 1H), 7.62 (dd, 3JHCCH=8.6 Hz, 3JHCCH=7.6 Hz, 1H), 7.8 (d, 3JHCCH=7.6 Hz, 1H)
10.80 g With potassium carbonate In butanone for 18 h; Reflux Step 1)
Synthesis of methyl 2-methyl-6-nitrobenzoate (2)
2-Methyl-6-nitrobenzoic acid (1; 10 g, 55.2 mol) was taken up in 200 mL of methyl ethyl ketone along with methyl iodide (17.2 mL, 276.0 mmol) and anhydrous potassium carbonate (38.1 g, 276.0 mmol).
The reaction mixture was stirred under reflux for 18 h.
It was then cooled to room temperature and filtered.
The filtrate was diluted with EtOAc (300 mL), washed with water (2*50 mL), brine, dried (Na2SO4) and concentrated under reduced pressure to afford 10.80 g of methyl 2-methyl-6-nitrobenzoate 2. MS (ESI) calcd for C9H9NO4: 195.05. found: 196 [M+H].
Reference: [1] Chemical Communications, 2005, # 44, p. 5583 - 5585
[2] Chemistry - A European Journal, 2009, vol. 15, # 24, p. 5956 - 5968
[3] Patent: US2011/251395, 2011, A1, . Location in patent: Page/Page column 15
[4] Patent: US2005/49253, 2005, A1, . Location in patent: Page/Page column 25-26
[5] Patent: US2005/54670, 2005, A1, . Location in patent: Page/Page column 27
[6] Patent: WO2010/77686, 2010, A1, . Location in patent: Page/Page column 125
[7] Patent: WO2010/77947, 2010, A1, . Location in patent: Page/Page column 103
[8] Patent: US2013/190309, 2013, A1, . Location in patent: Paragraph 0389; 0390
[9] Journal of the American Chemical Society, 2014, vol. 136, # 10, p. 3744 - 3747
  • 16
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  • [ 61940-22-5 ]
YieldReaction ConditionsOperation in experiment
88%
Stage #1: at 80℃; for 3.5 h;
Stage #2: With triethylamine In methanol at 20℃; for 3 h;
A mixture of commercial 2-methyl-6-nitrobenzoic acid (2.00 g, 11.0 mmol, 1 eq.) and thionyl chloride(9 mL) was stirred at 80 °C for 3.5 h. An excess of the thionyl chloride was distilled off under reducedpressure and the obtained residue was dissolved with CH2Cl2 (3 mL). The solution was addeddropwise to a methanol (6 mL) solution of triethylamine (2 mL) at 0 °C and stirred at roomtemperature for 3 h. Then, the solvent was distilled off under reduced pressure. Water was added to theobtained residue and the mixture was extracted three times with ethyl acetate. The organic layer wasdried with magnesium sulfate, filtrated and evaporated under reduced pressure. The crude productwas purified by silica column chromatography employing a mixture of n-hexane : ethylacetate (9 : 1) as eluent to obtain the desired product 13c.
Reference: [1] Synlett, 2017, vol. 28, # 14, p. 1724 - 1728
[2] Chemische Berichte, 1919, vol. 52, p. 1083
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  • [ 61940-22-5 ]
YieldReaction ConditionsOperation in experiment
91% at 20 - 100℃; for 2 h; Inert atmosphere Example 1Preparation of Methyl 2-Methyl-6-nitrobenzoateA mixture of 2-methyl-6-nitrobenzoic acid (300.0 g, 1.66 moles, from Acros Organics, Morris Plains, N.J.) and trimethyl orthoacetate (298.3 g, 2.48 moles, from Aldrich Chemicals, Milwauke, Wis.) was charged into a 3-L 3-necked flask at about 20-25° C. under nitrogen. The reaction mixture was gradually heated and the low-boiling point components generated during the reaction were distilled off to an internal temperature of 95-100° C. After 2 hours, the reaction mixture was cooled to 20-25° C. over 1-2 hours. After heptane (1.50 L, from Aldrich Chemicals) was charged into the reaction mixture over 1.0-1.5 hours, the reaction mixture was seeded with methyl 2-methyl-6-nitrobenzoate (0.5 g) when it became turbid. The suspension was cooled to 0-5° C. over 0.5-1 hour and kept at 0-5° C. for another 1.5-2 hours. The solid was collected by filtration under vacuum, washed with heptane (3x300 mL), and dried to a constant weight in a tray at 30-35° C. under a vacuum at 100-120 torr. The yield of methyl 2-methyl-6-nitrobenzoate was 292.0 g (91percent), based on 300.0 g of 2-methyl-6-nitrobenzoic acid. The product was found to have a purity of >99percent measured by HPLC based on area percentage, and a water content of <0.1percent measured by Karl Fisher titration.
91% at 20 - 100℃; for 2 h; Inert atmosphere [0116j A mixture of 2-methyl-6-nitrobenzoic acid (300.0 g, 1.66 moles, from Acros Organics, Morris Plains, NJ) and trimethyl orthoacetate (298.3 g, 2.48 moles, from Aldrich Chemicals, Milwaukee, WI) was charged into a 3-L 3-necked flask at about 20-25°C under nitrogen. The reaction mixture was gradually heated and the low-boiling point components generated during the reaction were distilled off to an internal temperature of 95-100°C. After 2 hours, the reaction mixture was cooled to 20-25°C over 1-2 hours. After heptane (1.50 L, from Aldrich Chemicals) was charged into the reaction mixture over 1.0-1.5 hours, the reaction mixture was seeded with methyl 2-methyl-6-nitrobenzoate (0.5 g) when it became turbid. The suspension was cooled to 0-5°C over 0.5-1 hour and kept at 0-5°C for another 1.5-2 hours. The solid was collected by filtration under vacuum, washed with heptane (3x300 mL), and dried to a constant weight in a tray at 30-35°C under a vacuum at 100-120 torr. The yield of methyl 2- methyl-6-nitrobenzoate was 292.0 g (9 1percent), based on 300.0 g of 2-methyl-6-nitrobenzoic acid. The product was found to have a purity of >99percent measured by HPLC based on area percentage, and a water content of <0.1percent measured by Karl Fisher titration.
91% at 95 - 100℃; for 2 h; Inert atmosphere [0191] A mixture of 2-methyl-6-nitrobenzoic acid (300.0 g, 1.66 moles, from Acros (0628) Organics, Morris Plains, NJ) and trimethyl orthoacetate (298.3 g, 2.48 moles, from Aldrich Chemicals, Milwaukee, WI) was charged into a 3-L 3-necked flask at about 20-25°C under nitrogen. The reaction mixture was gradually heated and the low-boiling point components generated during the reaction were distilled off to an internal temperature of 95-100°C. After 2 hours, the reaction mixture was cooled to 20-25°C over 1-2 hours. After heptane (1.50 L, from Aldrich Chemicals) was charged into the reaction mixture over 1.0-1.5 hours, the reaction mixture was seeded with methyl 2-methyl-6-nitrobenzoate (0.5 g) when it became turbid. The suspension was cooled to 0-5°C over 0.5-1 hour and kept at 0-5°C for another 1.5-2 hours. The solid was collected by filtration under vacuum, washed with heptane (3x300 mL), and dried to a constant weight in a tray at 30-35°C under a vacuum at 100-120 torr. The yield of methyl 2- methyl-6-nitrobenzoate was 292.0 g (91percent), based on 300.0 g of 2-methyl-6-nitrobenzoic acid. The product was found to have a purity of >99percent measured by HPLC based on area percentage, and a water content of
91% at 20 - 100℃; for 2 h; Inert atmosphere 10219] A mixture of2-methyl-6-nitrobenzoic acid (300.0 g,1.66 moles, from Acros Organics, Morris Plains, N.J.) and trimethyl orthoacetate (298.3 g, 2.48 moles, from Aldrich Chemicals, Milwaukee, Wis.) was charged into a 3-L 3-necked flask at about 20-25° C. under nitrogen. The reaction mixture was gradually heated and the low-boiling point components generated during the reaction were distilled off to an internal temperature of 95-100° C. After 2 hours, the reaction mixture was cooled to 20-25° C. over 1-2 hours. After heptane (1.50 L, from Aldrich Chemicals) was charged into the reaction mixture over 1.0-1.5 hours, the reaction mixture was seeded with methyl 2-methyl-6-nitrobenzoate (0.5 g) when it became turbid. The suspension was cooled to 0-5° C. over 0.5-1 hour and kept at 0-5° C. for another 1.5-2 hours. The solid was collected by filtration under vacuum, washed with heptane (3x300 mL), and dried to a constant weight in a tray at 30-35° C. under a vacuum at 100-120 ton. The yield of methyl 2-methyl-6-nitrobenzoate was 292.0 g (91percent), based on 300.0 g of 2-methyl-6-nitrobenzoic acid. The product was found to have a purity of >99percent measured by HPLC based on area percentage, and a water content of <0.1percent measured by Karl Fisher titration.

Reference: [1] Patent: US2011/87033, 2011, A1, . Location in patent: Page/Page column 10
[2] Patent: WO2015/175773, 2015, A1, . Location in patent: Paragraph 0116
[3] Patent: WO2015/175956, 2015, A1, . Location in patent: Paragraph 0191
[4] Patent: US2016/128981, 2016, A1, . Location in patent: Paragraph 0219
  • 18
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  • [ 13506-76-8 ]
  • [ 61940-22-5 ]
YieldReaction ConditionsOperation in experiment
91% at 95 - 100℃; for 2 h; 6.5.1. Preparation of Methyl 2-methyl-6-nitrobenzoate (0174) A mixture of 2-methyl-6-nitrobenzoic acid (300.0 g, 1.66 moles, from Acros Organics, Morris Plains, N.J.) and trimethyl orthoacetate (298.3 g, 2.48 moles, from Aldrich Chemicals, Milwaukee, Wis.) was charged into a 3-L 3-necked flask at about 20-25° C. under nitrogen. The reaction mixture was gradually heated and the low-boiling point components generated during the reaction were distilled off to an internal temperature of 95-100° C. After 2 hours, the reaction mixture was cooled to 20-25° C. over 1-2 hours. After heptane (1.50 L, from Aldrich Chemicals) was charged into the reaction mixture over 1.0-1.5 hours, the reaction mixture was seeded with methyl 2-methyl-6-nitrobenzoate (0.5 g) when it became turbid. The suspension was cooled to 0-5° C. over 0.5-1 hour and kept at 0-5° C. for another 1.5-2 hours. The solid was collected by filtration under vacuum, washed with heptane (3×300 mL), and dried to a constant weight in a tray at 30-35° C. under a vacuum at 100-120 ton. The yield of methyl 2-methyl-6-nitrobenzoate was 292.0 g (91percent), based on 300.0 g of 2-methyl-6-nitrobenzoic acid. The product was found to have a purity of >99percent measured by HPLC based on area percentage, and a water content of <0.1percent measured by Karl Fisher titration.
Reference: [1] Patent: US9272035, 2016, B2, . Location in patent: Page/Page column 28
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  • [ 10026-13-8 ]
  • [ 13506-76-8 ]
  • [ 61940-22-5 ]
Reference: [1] Patent: US2003/139451, 2003, A1,
  • 20
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  • [ 77-78-1 ]
  • [ 61940-22-5 ]
Reference: [1] Synthesis, 2007, # 7, p. 981 - 983
  • 21
  • [ 13506-76-8 ]
  • [ 6277-17-4 ]
YieldReaction ConditionsOperation in experiment
20% With 2.9-dimethyl-1,10-phenanthroline; oxygen; copper (I) acetate; silver sulfate; sodium iodide In dimethyl sulfoxide at 160℃; for 24 h; Schlenk technique Silak reaction tube equipped with a magnetic stirrer was charged with 6.2 mg of silver sulfate,21.8 mg of copper acetate, 12.5 mg of 2,9-dimethyl-1,10-o-phenanthroline,36.2 mg of 2-nitro-6-methylbenzoic acid and 45 mg of sodium iodide4 mL of dimethyl sulfoxide. Heat 160 ° C in the presence of oxygenReaction for 24 hours. After the reaction was completed, distilled water was added to quench the reaction,Extraction with ethyl acetate 3 times, each time 10mL,The combined organic phases were concentrated to give 10.5 mg of 2-nitro-6-methyl iodobenzene,The yield is 20percent.
Reference: [1] Journal of Organic Chemistry, 2016, vol. 81, # 7, p. 2794 - 2803
[2] Organic and Biomolecular Chemistry, 2018, vol. 16, # 30, p. 5416 - 5421
[3] Patent: CN107325002, 2017, A, . Location in patent: Paragraph 0118
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YieldReaction ConditionsOperation in experiment
1.2 g With palladium on activated charcoal; hydrogen In methanol at 20℃; for 2 h; Pd/C (150 mg) was added to a solution of 2-methyl-6-nitrobenzoic acid (1.5 g, 8.29 mmol) inCHOH (35 ml). The mixture was stirred at room temperature under H2 atmosphere for 2h.Then the mixture was filtered and concentrated to afford 1.2 g of the title compound as yellow solid. LCMS (ESI): calc’d for C8H9N02 [M+H]: 152, found: 152.
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