22802-67-1|Methyl 5-amino-2-methoxybenzoate| Ambeed

Structure of 22802-67-1

*Storage: {[sel_prStorage]}

*Shipping: {[sel_prShipping]}

4.5 *For Research Use Only !

{[proInfo.pro_purity]}

Cat. No.: {[proInfo.prAm]} Purity: {[proInfo.pro_purity]}

Change View

Size	Price	VIP Price	US Stock	Global Stock	In Stock
{[ item.pr_size ]}		Inquiry {[ getRatePrice(item.pr_usd,item.pr_rate,item.mem_rate,item.pr_is_large_size_no_price, item.vip_usd) ]}

US Stock: ship in 0-1 business day
Global Stock: ship in 5-7 days

{[ item.pr_size ]}

In Stock

- +

Please Login or Create an Account to: See VIP prices and availability

US Stock: ship in 0-1 business day
Global Stock: ship in 2 weeks

Quality Control of [ 22802-67-1 ] Purity: 97% SDS Specification

COA

Search for reports by entering the product batch number.
Batch number can be found on the product's label following the word 'Batch'.

NMR

Search for reports by entering the product batch number.
Batch number can be found on the product's label following the word 'Batch'.

CNMR

Search for reports by entering the product batch number.
Batch number can be found on the product's label following the word 'Batch'.

HPLC

Search for reports by entering the product batch number.
Batch number can be found on the product's label following the word 'Batch'.

LC-MS

Search for reports by entering the product batch number.
Batch number can be found on the product's label following the word 'Batch'.

1-2 Day Shipping
High Quality
Technical Support

Product Details of [ 22802-67-1 ]

CAS No. :	22802-67-1
Formula :	C₉H₁₁NO₃
M.W :	181.19
SMILES Code :	COC(=O)C1=C(OC)C=CC(N)=C1
MDL No. :	MFCD08458835
InChI Key :	PSCXCIPPRCFAAO-UHFFFAOYSA-N
Pubchem ID :	89843

Safety of [ 22802-67-1 ]

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

Application In Synthesis of [ 22802-67-1 ]

* 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 [ 22802-67-1 ]

[ 22802-67-1 ] Synthesis Path-Downstream 1~35

1
[ 1194-98-5 ]
[ 22802-67-1 ]
[ 151391-84-3 ]

References: [1]Journal of Medicinal Chemistry,1993,vol. 36,p. 4094 - 4098.

2
[ 34841-11-7 ]
[ 22802-67-1 ]

Yield	Reaction Conditions	Operation in experiment
100%	With hydrogen; palladium(II) hydroxide; In methanol; at 20℃;	A mixture of 263-1 (400 mg, 1.89 mmol) and Pd(OH)2 (200 mg) in MeOH (50 mL) was stirred under H2 atmosphere at room temperature overnight. When the reaction was completed, the mixture was filtered, and the filtrate was concentrated to give a crude product, which was purified by silica gel column chromatography (CH2Cl2/MeOH = 50/1) to afford b-263 (350 mg, 100% yield) as yellow oil.
95%	With water; ammonium chloride; zinc; In ethanol; for 3h;Heating / reflux;Product distribution / selectivity;	Methyl 2-methoxy-5-nitro-benzoate (300 mg), ammonium chloride (228 mg), and zinc (929 mg) were suspended in ethanol (10 ml) and water (0.5 ml), and the suspension was stirred under reflux for 3 hr. The reaction mixture was filtered, and the solvent was removed from the filtrate by distillation under the reduced pressure. A saturated aqueous sodium hydrogencarbonate solution was added to the residue, and the mixture was extracted with chloroform. The chloroform layer was washed with water and saturated brine and was dried over anhydrous magnesium sulfate. The solvent was removed by distillation under the reduced pressure, and the residue was purified by column chromatography with an acetone-chloroform system to give methyl 5-amino-2-methoxy-benzoate (244 mg, yield 95%). Methyl 5-amino-2-methoxy-benzoate (244 mg) and 5-methoxymethylene-2,2-dimethyl-[1,3]dioxan-4,6-dione (228 mg) were dissolved in 2-propanol (3 ml), and the solution was stirred at 100C for 15 hr. The solvent was removed by distillation under the reduced pressure, and the residue was washed with diethyl ether to give methyl 5-[(2,2-dimethyl-4,6-dioxo-[1,3]dioxan-5-ylidenemethyl)-amino]-2-methoxy-benzoate (248 mg, yield 55%).
	With hydrogen;palladium(II) hydroxide/carbon; In methanol; under 760.051 Torr; for 18h;	Step 1 :; Methyl 2-methoxy-5-nitrobenzoate 13-1 (6.21 g, 29.4 mmol) was suspended in MeOH (100 mL) and 20% Pd (OH) 2/C (500 mg) was added. The mixture was stirred under a hydrogen atmosphere (1 atm) for 18 h. The catalyst was removed by filtration and the solvent evaporated under reduced pressure to give a residue of compound 13-2 (5.256 g), which was used as such in step 2.

	palladium;	Combine methyl 2-methoxy-5-nitrobenzoate (13.3 g, 63 mmol) and methanol. Add 5% palladium-on-carbon (0.66 g). Hydrogenate on a pressure apparatus at 50 psi. After 17 hours, filter through celite to remove the catalyst and evaporate the filtrate in vacuo to give a residue. Combine the residue and dichloromethane and extract with water. Dry the organic layer over Na2SO4, filter, and evaporate in vacuo to give methyl 2-methoxy-5-aminobenzoate. Rf=0.18 (silica gel, ethyl acetate/methanol 1/1). Elemental Analysis calculated for C9H11NO3: C, 59.66; H, 6.12; N, 7.73. Found: C, 59.44; H, 6.04; N, 7.62.
	palladium;	Combine methyl 2-methoxy-5-nitrobenzoate (13.3 g, 63 mmol) and methanol. Add 5% palladium-on-carbon (0.66 g). Hydrogenate on a pressure apparatus at 50 psi. After 17 hours, filter through celite to remove the catalyst and evaporate the filtrate in vacuo to give a residue. Combine the residue and dichloromethane and extract with water. Dry the organic layer over Na2SO4, filter, and evaporate in vacuo to give methyl 2-methoxy-5-aminobenzoate. Rf=0.18 (silica gel, ethyl acetate/methanol 1/1). Elemental Analysis calculated for C9H11NO3: C, 59.66; H, 6.12; N, 7.73. Found: C, 59.44; H, 6.04; N, 7.62.
	palladium;	Combine methyl 2-methoxy-5-nitrobenzoate (13.3 g, 63 mmol) and methanol. Add 5% palladium-on-carbon (0.66 g). Hydrogenate on a pressure apparatus at 50 psi. After 17 hours, filter through celite to remove the catalyst and evaporate the filtrate in vacuo to give a residue. Combine the residue and dichloromethane and extract with water. Dry the organic layer over Na2SO4, filter, and evaporate in vacuo to give methyl 2-methoxy-5-aminobenzoate. Rf=0.18 (silica gel, ethyl acetate/methanol 1/1). Elemental Analysis calculated for C9H11NO3: C, 59.66; H, 6.12; N, 7.73. Found: C, 59.44; H, 6.04; N, 7.62.
	With hydrogen;5%-palladium/activated carbon; In ethyl acetate; under 1064.07 Torr; for 5h;	The 2-{2-methoxy-4-[6-methoxy-7-(N-methylcarbamoyl)quinolin- i5 4-yloxy]phenyl} acetic acid used as a starting material was prepared as follows :-A mixture of methyl 2-methoxy-5-nitrobenzoate (20.3 g), 5% platinum-on-carbon catalyst (1.5 g) and ethyl acetate (300 ml) was stirred under 1.4 atmospheres pressure of hydrogen for 5 hours. The catalyst was removed by filtration and the filtrate was evaporated. There was thus obtained methyl 5-amino-2-methoxybenzoate (17 g); 1H NMR: (CDCl3) 3.8420 (s, 3H), 3.89 (s, 3H), 6.86 (m, 2H), 7.19 (m, IH); Mass Spectrum: M+H+ 182.
	With hydrogen;platinum on carbon; In ethyl acetate; under 1064.07 Torr; for 5h;	A mixture of methyl 2-methoxy-5-nitrobenzoate (20.3 g), 5% platinum-on-carbon catalyst (1.5 g) and ethyl acetate (300 ml) was stirred under 1.4 atmospheres pressure of hydrogen for 5 hours. The catalyst was removed by filtration and the filtrate was evaporated. There was thus obtained methyl 5-amino-2-methoxybenzoate (17 g); 1H NMR: (CDCl3) 3.84 (s, 3H), 3.89 (s, 3H), 6.86 (m, 2H), 7.19 (m, 1H); Mass Spectrum: M+H+ 182.
	With hydrogen;palladium(II) hydroxide/carbon; In methanol; under 760.051 Torr; for 18h;	Methyl 2-methoxy-5-nitrobenzoate (6.21 g, 29.4 MMOL) was suspended in MEOH (100 mL) and 20% Pd (OH) 2/C (500 mg) was added. The mixture was stirred under a hydrogen atmosphere (1 atm) for 18 h. The catalyst was removed by filtration and the solvent evaporated under reduced pressure (5.256 g).
15 g	With palladium 10% on activated carbon; hydrogen; In methanol; under 3620.13 - 4137.29 Torr;	A solution of methyl 2-methoxy-5-nitrobenzoate (20.0g, 0.097 mol) in methanol (300 mL) and 10% Pd/C (5.0 g) was stirred under hydrogen atmosphere under 70-80 psi pressure in Parr apparatus for 4-5 h. The reaction mass was filtered and the obtained filtrate was concentrated to afford 15.0 g of desired product. 1H NMR (300 MHz, DMSO d6): δ 3.67 (s, 3H), 3.74 (s, 3H), 4.96 (br s, 2H), 6.75 (dd, J = 2.4 Hz, 1H), 6.85 (d, = 8.7 Hz, 1H), 6.92 (s, 1H); MS (m/z): 182.25 (M+H)+.
	palladium;	Combine methyl 2-methoxy-5-nitrobenzoate (13.3 g, 63 mmol) and methanol. Add 5% palladium-on-carbon (0.66 g). Hydrogenate on a pressure apparatus at 50 psi. After 17 hours, filter through celite to remove the catalyst and evaporate the filtrate in vacuo to give a residue. Combine the residue and dichloromethane and extract with water. Dry the organic layer over Na2SO4, filter, and evaporate in vacuo to give methyl 2-methoxy-5-aminobenzoate. Rf=0.18 (silica gel, ethyl acetate/methanol 1/1). Elemental Analysis calculated for C9H11NO3: C, 59.66; H, 6.12; N, 7.73. Found: C, 59.44; H, 6.04; N, 7.62.
	With hydrogen;5%-palladium/activated carbon; In methanol; under 2585.81 Torr; for 17h;	Combine methyl 2-methoxy-5-nitrobenzoate (13.3 g, 63 mmol) and methanol. Add 5% palladium-on-carbon (0.66 g). Hydrogenate on a pressure apparatus at 50 psi. After 17 hours, filter through celite to remove the catalyst and evaporate the filtrate in vacuo to give a residue. Combine the residue and dichloromethane and extract with water. Dry the organic layer over Na2SO4, filter, and evaporate in vacuo to give methyl 2-methoxy-5-aminobenzoate. Rf=0.18 (silica gel, ethyl acetate/methanol 1/1.). Elemental Analysis calculated for C9H11NO3: C, 59.66; H, 6.12; N, 7.73. Found: C, 59.44; H, 6.04; N, 7.62.
	palladium;	Combine methyl 2-methoxy-5-nitrobenzoate (13.3 g, 63 mmol) and methanol. Add 5% palladium-on-carbon (0.66 g). Hydrogenate on a pressure apparatus at 50 psi. After 17 hours, filter through celite to remove the catalyst and evaporate the filtrate invacuo to give a residue. Combine the residue and dichloromethane and extract with water. Dry the organic layer over Na2 SO4, filter, and evaporate invacuo to give methyl 2-methoxy-5-aminobenzoate. Rf =0.18 (silica gel, ethyl acetate/methanol 1/1). Elemental Analysis calculated for C9 H11 NO3: C, 59.66; H, 6.12; N, 7.73. Found: C, 59.44; H, 6.04; N, 7.62.
	palladium;	Combine methyl 2-methoxy-5-nitrobenzoate (13.3 g, 63 mmol) and methanol. Add 5% palladium-on-carbon (0.66 g). Hydrogenate on a pressure apparatus at 50 psi. After 17 hours, filter through celite to remove the catalyst and evaporate the filtrate in vacuo to give a residue. Combine the residue and dichloromethane and extract with water. Dry the organic layer over Na2 SO4, filter, and evaporate in vacuo to give methyl 2-methoxy-5-aminobenzoate. Rf =0.18 (silica gel, ethyl acetate/methanol 1/1). Elemental Analysis calculated for C9 H11 NO3: C, 59.66; H, 6.12; N, 7.73. Found: C, 59.44; H, 6.04; N, 7.62.
	palladium;	Combine methyl 2-methoxy-5-nitrobenzoate (13.3 g, 63 mrnol) and methanol. Add 5% palladium-on-carbon (0.66 g). Hydrogenate on a pressure apparatus at 50 psi. After 17 hours, filter through celite to remove the catalyst and evaporate the filtrate in vacuo to give a residue. Combine the residue and dichloromethane and extract with water. Dry the organic layer over Na2 SO4, filter, and evaporate in vacuo to give methyl 2-methoxy-5-aminobenzoate. Rf =0.18 (silica gel, ethyl acetate/methanol 1/1). Elemental Analysis calculated for C9 H11 NO3: C, 59.66; H, 6.12; N, 7.73. Found: C, 59.44; H, 6.04; N, 7.62.

References: [1]Tetrahedron,2008,vol. 64,p. 2772 - 2782.
[2]Chemical Communications,2019,vol. 55,p. 10392 - 10395.
[3]Patent: WO2021/178488,2021,A1 .Location in patent: Paragraph 00506; 00522.
[4]Advanced Synthesis and Catalysis,2010,vol. 352,p. 2463 - 2473.
[5]Patent: EP1724268,2006,A1 .Location in patent: Page/Page column 77; 85.
[6]Journal of the American Chemical Society,2019,vol. 141,p. 14239 - 14248.
[7]Journal of Medicinal Chemistry,1984,vol. 27,p. 1137 - 1141.
[8]Bioorganic and Medicinal Chemistry Letters,2007,vol. 17,p. 916 - 920.
[9]Bioorganic and Medicinal Chemistry Letters,2007,vol. 17,p. 3181 - 3186.
[10]Patent: WO2005/80388,2005,A1 .Location in patent: Page/Page column 67.
[11]Patent: EP946548,2002,B1 .
[12]Patent: US6194406,2001,B1 .
[13]Patent: US2001/34343,2001,A1 .
[14]Patent: WO2007/99326,2007,A1 .Location in patent: Page/Page column 146.
[15]Patent: US2009/76075,2009,A1 .Location in patent: Page/Page column 39.
[16]Patent: US6369074,2002,B1 .Location in patent: Example 20.
[17]Patent: WO2004/65367,2004,A1 .Location in patent: Page 159.
[18]Patent: WO2013/186692,2013,A1 .Location in patent: Page/Page column 67.
[19]Patent: US6316445,2001,B1 .
[20]Patent: EP1077942,2005,B1 .Location in patent: Page/Page column 17.
[21]Patent: US5998439,1999,A .
[22]Patent: US5932571,1999,A .
[23]Patent: US5922737,1999,A .

3
[ 22802-67-1 ]
[ 124-63-0 ]
[ 68256-19-9 ]

Yield	Reaction Conditions	Operation in experiment
	With hydrogenchloride; N-ethyl-N,N-diisopropylamine; In dichloromethane;	PREPARATION 41 2-Methoxy-5-methylsulfonamidobenzoic acid Combine <strong>[22802-67-1]methyl 2-methoxy-5-aminobenzoate</strong> (1.5 g, 8.3 mmol) and dichloromethane (25 mL). Cool in an ice bath. Add N,N-diisopropylethylamine (3.17 mL, 18.2 mmol) and methanesulfonyl chloride (0.71 mL, 9.1 mmol). After 30 minutes, warm to ambient temperature. After 4 hours, dilute the reaction mixture with dichloromethane and extract three times with a 1 M aqueous hydrochloric acid solution and then brine. Dry the organic layer over Na2SO4, filter, and evaporate in vacuo to give a residue. Chromatograph the residue on silica gel eluding with 3% methanol/dichloromethane/0.1% concentrated aqueous ammonia to give methyl 2-methoxy-5-methylsulfonamidobenzoate: mp; 82-83 C. Elemental Analysis calculated for C10H13NO5S: C, 46.32; H. 5.05; N, 5.40. Found C, 46.44; H, 4.96; N, 5.19.
	With pyridine;	(1) To a solution of <strong>[22802-67-1]methyl 2-methoxy-5-aminobenzoate</strong> (300 mg) and dry pyridine (3 ml), methanesulfonyl chloride (210 mg) is added dropwise with ice cooling and stirring, and the resultant mixture is stirred at room temperature for 1 hour. The reaction mixture is acidified with 6 N hydrochloric acid and shaken with methylene chloride. The organic layer is washed with water, dried over sodium sulfate, and evaporated under reduced pressure to remove the methylene chloride. The residue is chromatographed on a column of silica gel, which is eluted with methylene chloride--2% methanol/methylene chloride, and the elude is evaporated to remove the solvent. The residue is recrystallized from ethyl acetate/isopropyl ether to give methyl 2-methoxy-5-methanesulfonamidobenzoate (381 mg) as colorless prisms melting at 84 to 86 C. Anal. Calcd. for C10 H13 O5 NS 0.1/10H2 O: C,46.32; H,5.05; N,5.40; S,12.37. Found: C,45.77; H,5.14; N,5.30; S,12.32.
	With hydrogenchloride; N-ethyl-N,N-diisopropylamine; In dichloromethane;	Preparation 41 2-Methoxy-5-methylsulfonamidobenzoic Acid Combine <strong>[22802-67-1]methyl 2-methoxy-5-aminobenzoate</strong> (1.5 g, 8.3 mmol) and dichloromethane (25 mL). Cool in an ice bath. Add N,N-diisopropylethylamine (3.17 mL, 18.2 mmol) and methanesulfonyl chloride (0.71 mL, 9.1 mmol). After 30 minutes, warm to ambient temperature. After 4 hours, dilute the reaction mixture with dichloromethane and extract three times with a 1 M aqueous hydrochloric acid solution and then brine. Dry the organic layer over Na2SO4, filter, and evaporate in vacuo to give a residue. Chromatograph the residue on silica gel eluding with 3% methanol/dichloromethane/0.1% concentrated aqueous ammonia to give methyl 2-methoxy-5-methylsulfonamidobenzoate: mp; 82-83 C. Elemental Analysis calculated for C10H13NO5S: C, 46.32; H, 5.05; N, 5.40. Found C, 46.44; H, 4.96; N, 5.19.

With N-ethyl-N,N-diisopropylamine; In dichloromethane;

PREPARATION 41 2-Methoxy-5-methylsulfonamidobenzoic acid Combine <strong>[22802-67-1]methyl 2-methoxy-5-aminobenzoate</strong> (1.5 g, 8.3 mmol) and dichloromethane (25 mL). Cool in an ice bath. Add N,N-diisopropylethylamine (3.17 mL, 18.2 mmol) and methanesulfonyl chloride (0.71 mL, 9.1 mmol). After 30 minutes, warm to ambient temperature. After 4 hours, dilute the reaction mixture with dichloromethane and extract three times with a 1 aqueous hydrochloric acid solution and then brine. Dry the organic layer over Na2SO4, filter, and evaporate in vacuo to give a residue. Chromatograph the residue on silica gel eluding with 3% methanol/dichloromethane/0.1% concentrated aqueous ammonia to give methyl 2-methoxy-5-methylsulfonamidobenzoate: mp; 82-83 C. Elemental Analysis calculated for C10H13NO5S: C, 46.32; H, 5.05; N, 5.40. Found C, 46.44; H, 4.96; N, 5.19.

References: [1]Journal of Medicinal Chemistry,1984,vol. 27,p. 1137 - 1141.
[2]Patent: US6423704,2002,B1 .
[3]Patent: US4328155,1982,A .
[4]Patent: US6194406,2001,B1 .
[5]Patent: US6211199,2001,B1 .
[6]Journal of Medicinal Chemistry,2014,vol. 57,p. 793 - 816.

4
[ 180690-86-2 ]
[ 22802-67-1 ]

References: [1]Journal of Medicinal Chemistry,1993,vol. 36,p. 4094 - 4098.

5
[ 22802-67-1 ]
[ 13360-57-1 ]
[ 90763-20-5 ]

References: [1]Journal of Medicinal Chemistry,1984,vol. 27,p. 1137 - 1141.

6
[ 22802-67-1 ]
[ 108-24-7 ]
[ 79893-19-9 ]

Yield	Reaction Conditions	Operation in experiment
	In tetrahydrofuran; at 20℃;	Step 2:; The aniline 13-2 from step 1 (5.23 g) was dissolved in THF (50 mL) and acetic anhydride (2.984 g) was added. The mixture was stirred overnight at room temperature. The white suspension was concentrated under reduced pressure to a white paste, tert-butylmethyl ether (TBME, 20 mL) was added and while stirring, hexane (100 mL) was added slowly. The suspension was then stirred for an additional 2h and the solid collected by filtration. The product 13-3 was washed with hexane and dried. in air (6.372 g).
		The aniline from above (5.23 g) was dissolved in THF (50 mL) and acetic anhydride ( 2.984 g) was added. The mixture was stirred overnight at room temperature. The white suspension was concentrated under reduced pressure to a white paste, TERT- butylmethyl ether (TBME, 20 mL) was added and while stirring, hexane (100 mL) was added slowly. The suspension was then stirred for an additional 2h and the solid collected by filtration. The product was washed with hexane and dried in air (6.372 g).

References: [1]Journal of the American Chemical Society,2006,vol. 128,p. 12307 - 12313.
[2]Patent: WO2005/80388,2005,A1 .Location in patent: Page/Page column 68.
[3]Patent: WO2004/65367,2004,A1 .Location in patent: Page 159.

7
[ 22802-67-1 ]
[ 135-95-5 ]