13365-26-9|Dimethyl 3-nitrophthalate| Ambeed

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Quality Control of [ 13365-26-9 ] Purity: 99% SDS Specification

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Product Details of [ 13365-26-9 ]

CAS No. :	13365-26-9
Formula :	C₁₀H₉NO₆
M.W :	239.18
SMILES Code :	O=C(OC)C1=CC=CC([N+]([O-])=O)=C1C(OC)=O
MDL No. :	MFCD00017184
InChI Key :	MLQMIKSBTAZNBK-UHFFFAOYSA-N
Pubchem ID :	249912

Safety of [ 13365-26-9 ]

GHS Pictogram:
Signal Word:	Warning
Hazard Statements:	H302
Precautionary Statements:	P280-P305+P351+P338

Application In Synthesis of [ 13365-26-9 ]

* 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 [ 13365-26-9 ]

[ 13365-26-9 ] Synthesis Path-Downstream 1~35

1
[ 67-56-1 ]
[ 603-11-2 ]
[ 13365-26-9 ]

Yield	Reaction Conditions	Operation in experiment
100%		[0030] The synthesis of mIBX is readily accomplished from commercially available 3-nitrophtalic acid as follows: esterification of 3-nitrophtalic acid via the corresponding acid chloride to give nitrodiester (100%), which upon catalytic hydrogenation provides the aminodiester (100%). Diazotization is then performed, followed by iodination of the aminodiester to provide dimethyl 3-iodophthalate in about 91 % yield. This is followed by saponification, then acidification of dimethyl 3-iodophthalate to give 3-iodophthalic acid in about 93 % yield. 3-iodophthalic acid is then oxidized to form the water-soluble MIBX. This process is carried out using KBrO3 in 0.73H2SO4 at 55-60 C. as follows: KBrO3 (5 g, 30 mmol) is added in portions to a suspension of 3-iodophthalic acid (5 g, 17.1 mmol) in 70 ML of 0.73 M H2SO4 over a period of 20 minutes; The mixture is then maintained at 55-60 C. for 12 hours and the resulting clear orange solution is evaporated to yield an off-white solid, which is triturated with 30 ML of water at 0 C. for 2 hours and filtered to obtain a white solid.This is further triturated with hexane (100 ML) for 6 hours and filtered to give MIBX (3.9 g, 71%) as a white solid with a melting point of 258-260 C. The approximately 70% yield for the conversion of 3-iodophthalic acid to MIBX is the isolated yield of MIBX, with the actual conversion near quantitative as evident from monitoring the oxidation of 3-iodophthalic acid to MIBX by 1H NMR spectroscopy. Water-soluble MIBX is isolated as an analytically pure white solid.The synthesis of MIBX from 3-nitrophthalic acid is illustrated in . The physical properties of MIBX are as follows: mp 258-260 C.; IR (KBr), 3503 3469, 3050, 1708, 1631, 1588, 1369, 730, 700 cm-1; 1H NMR (D2O), 300 MHz): δ 8.35 (dd, J=7.9, 1.0 Hz, 1H), 8.09 (t, J=7.9 Hz, 1H), 7.94 (dd, J=7.9, 1.0 Hz, 1H); 13C NMR (D2O, 75 MHz): δ 125.5, 127.5, 132.5, 134.7, 137.0, 147.1 (ring carbons), 168.9, 172.9 (carbonyl carbons).
	With sulfuric acid;Reflux;	(1) Put 30 g of 3-nitrophthalic acid into a 500 ml reaction flask and add 300 ml of methanol (1:10, optionally 1:5 to 1:20, preferably 1:10 to 1:15). Sulfuric acid 30g (1:0.5-1:2, preferably 1:1) was warmed at reflux.(2) TLC monitoring, when the formation of the double esterification product exceeds the reduction of the raw material, the refluxing reaction is ended; below 50 C., the methanol is concentrated under reduced pressure to almost no fraction.(3) Add 200ml of water, control the temperature below 25C, add potassium carbonate to neutralize the pH to 7-8, and add 100ml of ethyl acetate to extract.The extract is concentrated and crystallized to obtain dimethyl 3-nitrophthalate, the aqueous layer is acidified to pH 4-5, stirred at room temperature for 2 hours, and the product is filtered to obtain methyl 3-nitro-2-carboxybenzoate (AM1). , Content more than 98%, yield more than 90%,Drying standby.

References: [1]Patent: US2004/30187,2004,A1 .Location in patent: Page 2; Sheet 1.
[2]Monatshefte fur Chemie,1900,vol. 21,p. 791.
[3]Patent: CN104876877,2018,B .Location in patent: Paragraph 0033; 0040-0043.

2
[ 13365-26-9 ]
[ 34529-06-1 ]

Yield	Reaction Conditions	Operation in experiment
100%	With hydrogen;palladium on activated charcoal; In methanol; under 2844.39 Torr;	[0030] The synthesis of mIBX is readily accomplished from commercially available 3-nitrophtalic acid as follows: esterification of 3-nitrophtalic acid via the corresponding acid chloride to give nitrodiester (100%), which upon catalytic hydrogenation provides the aminodiester (100%). Diazotization is then performed, followed by iodination of the aminodiester to provide dimethyl 3-iodophthalate in about 91 % yield. This is followed by saponification, then acidification of dimethyl 3-iodophthalate to give 3-iodophthalic acid in about 93 % yield. 3-iodophthalic acid is then oxidized to form the water-soluble MIBX. This process is carried out using KBrO3 in 0.73H2SO4 at 55-60 C. as follows: KBrO3 (5 g, 30 mmol) is added in portions to a suspension of 3-iodophthalic acid (5 g, 17.1 mmol) in 70 ML of 0.73 M H2SO4 over a period of 20 minutes; The mixture is then maintained at 55-60 C. for 12 hours and the resulting clear orange solution is evaporated to yield an off-white solid, which is triturated with 30 ML of water at 0 C. for 2 hours and filtered to obtain a white solid.This is further triturated with hexane (100 ML) for 6 hours and filtered to give MIBX (3.9 g, 71%) as a white solid with a melting point of 258-260 C. The approximately 70% yield for the conversion of 3-iodophthalic acid to MIBX is the isolated yield of MIBX, with the actual conversion near quantitative as evident from monitoring the oxidation of 3-iodophthalic acid to MIBX by 1H NMR spectroscopy. Water-soluble MIBX is isolated as an analytically pure white solid.The synthesis of MIBX from 3-nitrophthalic acid is illustrated in . The physical properties of MIBX are as follows: mp 258-260 C.; IR (KBr), 3503 3469, 3050, 1708, 1631, 1588, 1369, 730, 700 cm-1; 1H NMR (D2O), 300 MHz): δ 8.35 (dd, J=7.9, 1.0 Hz, 1H), 8.09 (t, J=7.9 Hz, 1H), 7.94 (dd, J=7.9, 1.0 Hz, 1H); 13C NMR (D2O, 75 MHz): δ 125.5, 127.5, 132.5, 134.7, 137.0, 147.1 (ring carbons), 168.9, 172.9 (carbonyl carbons).
93.7%	With palladium 10% on activated carbon; hydrogen; In methanol; for 16h;	(2) The <strong>[13365-26-9]dimethyl 3-nitrophthalate</strong> (239 mg, 1 mmol) obtained in the step (1) was dissolved in methanol (4 mL), and a catalytic amount of 10% Pd/C was added. Under the action of H2 (hydrogen balloon), after 16 hours of reaction, TLC detected the disappearance of <strong>[13365-26-9]dimethyl 3-nitrophthalate</strong>, Pd/C was removed by filtration, concentrated under reduced pressure, Drying a yellow solid (196 mg, yield 93.7%, HPLC purity 93.1%) is dimethyl 3-aminophthalate; by recrystallization or silica gel column chromatography, dimethyl 3-aminophthalate having a purity of ≥99% can be obtained.
90%	With palladium 10% on activated carbon; hydrogen; In ethanol;	(3) Synthesis of dimethyl 3-aminophthalate (compound 4) Dimethyl 3-nitrophthalate (18.1 g, 75.7 mmol) from step (2) was dissolved in 400 mL ethanol and 10% Pd/C (50% water, 1.8 g) was added. The reaction mixture was stirred overnight under a hydrogen atmosphere. The reaction mixture was filtered, and the filter cake was wash with ethanol. Ethanol was removed to give compound 4 as a yellow solid (14.2 g, 90%).

86%		5.40.2 3-Aminophthalic Acid Dimethyl Ester A mixture of 3:1 ethanol-conc. HCl (200 mL) was cooled to 0 C. and then 3-nitrophthalic acid dimethyl ester (15.0 g, 62.8 mmol) was added. Maintaining the cooling, tin chloride (70.8 g, 314 mmol) was added portionwise, over a period of 15 minutes. Following completion of the addition, the cooling bath was removed, and stirring proceeded at room temperature. After 2 hours, the mixture was neutralized by the addition of solid sodium bicarbonate, and the resulting mixture was extracted with ethyl acetate (3×150 mL) and the combined extracts were washed with water (5×250 mL), were dried (MgSO4) and evaporated, providing 11.3 g of the product as a yellow oil in 86% yield: 1H NMR (CDCl3) δ 3.84 (s, 3H), 3.86 (s, 3H), 5.20 (br, 2H), 6.78 (dd, J=8.5 Hz, J=1.0 Hz, 1H), 6.90 (dd, 1H, J=7.3 Hz, J=1.0 Hz, 1H), 7.24 (t, J=7.8 Hz, 1H).
86%		Step 2:[163] A mixture of 3:1 ethanol-conc. HCl (200 mL) was cooled to 0 0C and then 3- nitrophthalic acid dimethyl ester (15.0 g, 62.8 mmol) was added. Maintaining the cooling, tin (II) chloride (70.8 g, 314 mmol) was added portionwise, over a period of 15 min. Following completion of the addition, the cooling bath was removed and stirring proceeded at room temperature. After 2 h, the mixture was neutralized by the addition of solid sodium bicarbonate, and the resulting mixture was extracted with ethyl acetate (3 x 150 mL) and the combined extracts were washed with water (5 x 250 mL), were dried (MgSO4) and evaporated, providing 11.3 g of 3-aminophthalic acid dimethyl ester as a yellow oil, in 86% yield; 1H NMR (CDCl3) δ 3.84 (s, 3H), 3.86 (s, 3H), 5.20 (br, 2H), 6.78 (dd, J = 8.5 Hz, J = 1.0 Hz, IH), 6.90 (dd, IH, J = 7.3 Hz, J = 1.0 Hz, IH), 7.24 (t, J = 7.8 Hz, IH).
83%	With hydrogenchloride; In methanol; water;	REFERENCE EXAMPLE 102 Dimethyl 3-aminophthalate Dimethyl 3-nitrophthalate (18.0 g, 75.2 mmol) obtained in Reference Example 101 was dissolved in a mixture of concentrated hydrochloric acid (50.0 ml) water (250 ml) and methanol (25.0 ml), and an excess of zinc powder was added in portions. After completion of the reaction, the reaction mixture was filtered, and the filtrate was made basic with 25% aqueous ammonium hydroxide, and extracted with ethyl acetate. After the extract was washed with water and dried (MgSO4), the solvent was distilled off under reduced pressure. The residue was subjected to a column chromatography on a silica gel eluding with n-hexane-ethyl acetate (10:1, v/v) to give the title compound (13.1 g, 83%) as an oil. 1H-NMR (CDCl3) δ: 3.85 (3H, s), 3.86 (3H, s), 5.20 (2H, bs), 6.78 (1H, dd, J=8.4, 1.2 Hz), 6.90 (1H, dd, J=7.4, 0.8 Hz), 7.24 (1H, d, J=8.0 Hz).
18.1 g (87%)	With hydrogen;palladium-carbon; In ethyl acetate;	Methyl-3-amino-2-(methoxycarbonyl)benzoate To a solution of methyl-2-(methoxycarbonyl)-3-nitrobenzoate (23.8 g, 99.51 mmol) in ethyl acetate (200 ml) was added 10% Pd/C (1.8 g). The mixture was hydrogenated under 50 psi of hydrogen for 3 hours in a Parr Type Shaker. The mixture was filtered through Celite and the filtrate was concentrated in vacuo to yield an oil. The crude product was purified by flash chromatography (dichloromethane/ethyl acetate 95 to 5) to afford 18.1 g (87%) of the product as a brown oil: 1H NMR (CDCl3) δ7.22 (t, J=7.6 Hz, 1H), 6.90 (d, J=7.2 Hz, 1H), 6.79 (d, J=8.7 Hz), 5.07 (b, 2H), 3.85 (s, 3H), 3.83 (s, 3H).
	With hydrogen;palladium 10% on activated carbon; In methanol; at 20℃; under 2327.23 Torr;	Preparation of 3-amino-phthalic Acid Dimethyl Ester, 3 The compound 2 (205 g, 1.0 mol) was dissolved in 2 L of MeOH. Catalytic 10% Pd/C was added and the solution was hydrogenated under H2 (45 psi) on a Parr hydrogenation apparatus at room temperature overnight. Filtered through celite and evaporated to give a quantitative yield of 3-amino-phthalic acid dimethyl ester, 3. 1H NMR (300 MHz, DMSO-d6): 7.26 (t, J=7.33 Hz, 1H), 6.94 (d, J=8.34 Hz, 1H), 6.77 (d, J=8.33 Hz, 1H), 6.12 (s, 2H), 3.77 (s, 3H), 3.76 (s, 3H). 13C NMR: 51.51, 51.77, 110.50, 115.16, 118.56, 131.26, 133.16, 148.28, 167.12, 168.11.
	With palladium 10% on activated carbon; hydrogen; In acetone; at 20℃; under 3102.97 Torr; for 5h;	Dissolve Compound 1 (500mg) in acetone (30mL) solution, transfer to a hydrogenation reaction flask, add Pd / C (40mg, 10%), build a hydrogenation device, and react at 60psi for 5h at room temperature. , Remove the device, remove Pd / C by suction filtration, condense at low temperature by rotary evaporation, extract with ethyl acetate (30mLx3), combine the organic layers, wash once with saturated brine, add anhydrous magnesium sulfate to dry, and dry by suction filtration to obtain crude product. Column chromatography to obtain intermediate 2

References: [1]Journal of Heterocyclic Chemistry,1989,vol. 26,p. 1885 - 1886.
[2]Tetrahedron Letters,2002,vol. 43,p. 569 - 572.
[3]Patent: US2004/30187,2004,A1 .Location in patent: Page 2; Sheet 1.
[4]RSC Advances,2015,vol. 5,p. 48861 - 48867.
[5]Bioorganic and Medicinal Chemistry,2021,vol. 45.
[6]Patent: CN109970568,2019,A .Location in patent: Paragraph 0021; 0023; 0024; 0026.
[7]Bioorganic and Medicinal Chemistry Letters,2008,vol. 18,p. 285 - 288.
[8]Patent: US2018/134722,2018,A1 .Location in patent: Paragraph 0021.
[9]Patent: US2007/49618,2007,A1 .Location in patent: Page/Page column 66.
[10]Patent: WO2008/115516,2008,A2 .Location in patent: Page/Page column 49.
[11]Patent: US6407116,2002,B1 .
[12]Collection of Czechoslovak Chemical Communications,1955,vol. 20,p. 757,762.
[13]Journal of the American Chemical Society,1937,vol. 59,p. 2580,2581.
[14]Journal of the American Chemical Society,1909,vol. 31,p. 489.
[15]Journal of the Chemical Society C: Organic,1971,p. 3671 - 3673.
[16]Journal of the American Chemical Society,1992,vol. 114,p. 5141 - 5146.
[17]Journal of Medicinal Chemistry,2001,vol. 44,p. 1334 - 1336.
[18]Patent: US2003/96841,2003,A1 .
[19]Bioorganic and Medicinal Chemistry,2008,vol. 16,p. 1702 - 1720.
[20]Patent: US2009/98084,2009,A1 .Location in patent: Page/Page column 22.
[21]Patent: CN110746400,2020,A .Location in patent: Paragraph 0049; 0050.

3
[ 13365-26-9 ]
3,3'-azo-di-phthalic acid tetramethyl ester [ No CAS ]

References: [1]Journal of the American Chemical Society,1909,vol. 31,p. 489.

4
[ 13365-26-9 ]
[ 102928-38-1 ]

References: [1]Journal of Organic Chemistry,1950,vol. 15,p. 496,508.
[2]Tetrahedron Letters,2002,vol. 43,p. 569 - 572.
[3]Patent: WO2008/115516,2008,A2 .

5
[ 908094-01-9 ]
[ 603-11-2 ]
[ 13365-26-9 ]

References: [1]Journal of Heterocyclic Chemistry,1989,vol. 26,p. 1885 - 1886.
[2]Journal of the Chemical Society,1962,p. 1148 - 1157.
[3]Journal of the Chemical Society C: Organic,1971,p. 3671 - 3673.

6
[ 108030-46-2 ]
[ 762-42-5 ]
[ 13365-26-9 ]

References: [1]Chemical and pharmaceutical bulletin,1988,vol. 36,p. 481 - 487.

7
[ 108030-46-2 ]
[ 624-49-7 ]
[ 13365-26-9 ]
[ 131-11-3 ]

References: [1]Chemical and pharmaceutical bulletin,1988,vol. 36,p. 481 - 487.
[2]Chemical and pharmaceutical bulletin,1988,vol. 36,p. 481 - 487.

8
[ 13365-26-9 ]
[ 100-53-8 ]
[ 67666-76-6 ]

References: [1]Journal of Medicinal Chemistry,1978,vol. 21,p. 1035 - 1040.

9
[ 77-78-1 ]
3-nitro-phthalate sodium [ No CAS ]
[ 13365-26-9 ]

References: [1]Journal of the American Chemical Society,1909,vol. 31,p. 489.

10
[ 131-11-3 ]
[ 13365-26-9 ]
[ 610-22-0 ]

References: [1]Journal of Organic Chemistry,2001,vol. 66,p. 4356 - 4360.

11
[ 13365-26-9 ]
[ 6937-34-4 ]

References: [1]Tetrahedron Letters,2002,vol. 43,p. 569 - 572.

12
[ 603-11-2 ]
[ 13365-26-9 ]

Yield	Reaction Conditions	Operation in experiment
63%	With potassium carbonate; dimethyl sulfate; In water; acetone;	REFERENCE EXAMPLE 101 Dimethyl 3-nitrophthalate To a suspension of 3-nitrophthalic acid (25.5 g, 0.120 mol) and potassium carbonate (40.1 g, 0.289 mol) in acetone (500 ml), dimethyl sulfate (27.4 ml, 0.289 mmol) was added dropwise, and the reaction mixture was heated under reflux for 21 hours. The solvent was distilled off under reduced pressure, and the residue was combined with water and extracted with ethyl acetate. After the extract was washed with water and dried (MgSO4), the solvent was distilled off under reduced pressure. The residue was subjected to a column chromatography on a silica gel eluding with n-hexane-ethyl acetate (5:1, v/v) to give the title compound (18.0 g, 63%). Recrystallization from ethyl acetate yielded a colorless crystal having a melting point of 66.0 to 67.0 C. IR (KBr): 2955, 1738, 1630, 1613, 1574, 1541 cm-1. 1H-NMR (CDCl3) δ: 3.96 (3H, s), 4.03 (3H, s), 7.69 (1H, t, J=8.2 Hz), 8.32-8.42 (2H, m).

References: [1]Patent: US6407116,2002,B1 .
[2]Tetrahedron Letters,2002,vol. 43,p. 569 - 572.

13
[ 13365-26-9 ]
[ 52659-18-4 ]

References: [1]Journal of Medicinal Chemistry,2001,vol. 44,p. 1334 - 1336.
[2]Journal of the American Chemical Society,1909,vol. 31,p. 489.

14
[ 13365-26-9 ]
[ 247149-96-8 ]