56921-01-8|Methyl 5-methyl-4-nitrothiophene-2-carboxylate| Ambeed

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Quality Control of [ 56921-01-8 ] Purity: 96% SDS Specification

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Product Details of [ 56921-01-8 ]

CAS No. :	56921-01-8
Formula :	C₇H₇NO₄S
M.W :	201.20
SMILES Code :	O=C(C1=CC([N+]([O-])=O)=C(C)S1)OC
MDL No. :	MFCD18642553
InChI Key :	QXIFGUCZQLEFBZ-UHFFFAOYSA-N
Pubchem ID :	268679

Safety of [ 56921-01-8 ]

GHS Pictogram:
Signal Word:	Warning
Hazard Statements:	H302-H315-H319-H335
Precautionary Statements:	P261-P264-P270-P271-P280-P301+P312-P302+P352-P304+P340-P305+P351+P338-P330-P332+P313-P337+P313-P362-P403+P233-P405-P501

Application In Synthesis of [ 56921-01-8 ]

* 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.

Downstream synthetic route of [ 56921-01-8 ]

[ 56921-01-8 ] Synthesis Path-Downstream 1~35

1
[ 19432-69-0 ]
[ 56921-01-8 ]

Yield	Reaction Conditions	Operation in experiment
67%	With sulfuric acid; nitric acid; at 0 - 5℃; for 0.5h;	Step 2: Production of methyl 4-nitro-5-methylthiophene-2-carboxylate To a solution of methyl 5-methylthiophene-2-carboxylate (40.8 g, 260 mmol) in conc. sulfuric acid (400 ml) was added dropwise under ice-cooling a solution of fuming nitric acid (16.5 ml, 391 mmol) in conc. sulfuric acid (100 ml) at an inside temperature not exceeding 5C. After the completion of the dropwise addition, the mixture was stirred under ice-cooling for 30 min and gradually poured into ice (1 kg). The precipitated solid was washed with water (500 ml x 6) and dried under reduced pressure to give methyl 4-nitro-5-methylthiophene-2-carboxylate (35.1 g, yield 67%). 1H-NMR(300MHz, δppm, CDCl3): 8.20(1H, s), 3.91 (3H, s), 2. 84 (3H, s).
44 - 67%	With sulfuric acid; nitric acid; at 0 - 5℃; for 0.5h;Product distribution / selectivity;	To a solution of methyl 5-methylthiophene-2-carboxylate (40.8 g, 260 mmol) in conc. sulfuric acid (400 ml) was added dropwise a solution of fuming nitric acid (16.5 ml, 391 mmol) in conc. sulfuric acid (100 ml) under ice-cooling in such a manner that the inside temperature did not exceed 5 C. After the completion of the dropwise addition, the mixture was stirred under ice-cooling for 30 min, and poured slowly into ice (1 kg). The precipitated solid was washed with water (500 ml×6) and dried under reduced pressure to give methyl 4-nitro-5-methylthiophene-2-carboxylate (35.1 g, yield 67%). 1H-NMR (300 MHz, δppm, CDCl3) 8.20(1H, s), 3.91(3H, s), 2.84(3H, s).; To a solution of methyl 5-methylthiophene-2-carboxylate (109 g, 700 mmol) in conc. sulfuric acid (850 ml) was added dropwise a solution of fuming nitric acid (31 ml, 738 mmol) in conc. sulfuric acid (150 ml) under ice-cooling in such a manner that an inside temperature did not exceed 5 C. After the completion of the dropwise addition, the mixture was stirred under ice-cooling for 30 min, and slowly poured into ice (2 kg). The precipitated solid was collected by filtration, washed with water (500 ml×6) and dried under reduced pressure to give methyl 4-nitro-5-methylthiophene-2-carboxylate (62 g, yield 44%). 1H-NMR (400 MHz, δppm, CDCl3) 8.20(1H, s), 3.91(3H, s), 2.84(3H, s).
	With sulfuric acid; nitric acid; at 0℃; for 0.5h;	A solution of concentrated HN03 (7.2 mL, 1 1 1.5 mmol) in concentrated H2S04 (20 mL) was added dropwise to the solution of methyl 5-methylthiophene-2-carboxylate (F-2) (13.4 g, 86.0 mmol) in concentrated H2S04 (30 mL) at 0C. The reaction mixture was stirred at 0C for 30 mins and poured into ice-water. The precipitate was filtered and washed with water. A solid was collected as the product (14.8 g).

	With sulfuric acid; nitric acid; In sulfuric acid; at 0℃; for 0.5h;	Methyl 5-methyl-4-nitrothiophene-2-carboxylate (F-3) A solution of concentrated HNO3 (7.2 mL, 111.5 mmol) in concentrated H2SO4 (20 mL) was added dropwise to the solution of methyl 5-methylthiophene-2-carboxylate (F-2) (13.4 g, 86.0 mmol) in concentrated H2SO4 (30 mL) at 0 C. The reaction mixture was stirred at 0 C. for 30 mins and poured into ice-water. The precipitate was filtered and washed with water. A solid was collected as the product (14.8 g).
2.90 g	With sulfuric acid; nitric acid; at 0℃; for 0.5h;	To a stirred and cooled (0 C) solution of methyl 5-methylthiophene-2-carboxylate (5.0 g, 32.010 mmol) in conc. H2504 (30 ml) was added fuming nitric acid (1.41 ml,33.616 mmol) and the reaction mixture was stirred at the same temperature for 30 minutes. The reaction mixture was poured slowly on crushed ice and precipitate thusobtained was filtered and washed with water. The compound obtained after drying was purified by silica gel column chromatography to yield 2.90 g of the title product as white solid. ESI-MS (m/z) 200 (M-H).
24.3 g	With sulfuric acid; nitric acid; at 0℃; for 0.25h;	[0511] Methyl 5-methylthiophene-2-carboxylate (25.8 g) was dissolved in 50 mL of cold concentrated sulfuric acid and the mixture was kept cooling in an ice bath. To this solution, a prepared solution of fuming nitric acid (14 mL) and concentrated sulfuric acid (40 mL) was added dropwise. After completion of the addition, the mixture was kept stirring for an additional 15 mm at 0 C. The reaction mixture was poured carefully into crushed ice and the solid was collected by filtration, then washed with water, and dried. The desired product (24.3 g) was used directly in the next synthetic step. ‘H NIVIR (400 MHz, CDCL3): (major isomer) ö: 2.84 (s, 3H), 3.91 (s, 3H), 8.20 (s, 1H) ppm. LC (method A): tR = 1.73 mi LC/MS (El) m/z. [M + H] 202.3.
243 g	With sulfuric acid; nitric acid; at 0℃; for 0.25h;	Methyl 5-methylthiophene-2-carboxylate (25.8 g) was dissolved in 50 mL of cold concentrated sulfuric acid and the mixture was kept cood in an ice bath. To this solution, a prepared solution of fuming nitric acid (14 mL) and concentrated sulfuric acid (40 mL) was added dropwise. After completion of the addition, the mixture was stirred for an additional 15 min at 0 C. The reaction mixture was poured carefully into crushed ice and the solid was collected by filtration, washed with water, and dried. The desired product (24.3 g) was used directly in the next synthetic step. NMR (400 MHz, CDCh): (major isomer) δ: 2.84 (s, 3H), 3.91 (s, 3H), 8.20 (s, 1H) ppm. LC (method A): = 1.73 min. LC/MS (EI) mlz: [M + H]+ 202.3.

References: [1]Journal of Medicinal Chemistry,2014,vol. 57,p. 7577 - 7589.
[2]Patent: EP1688420,2006,A1 .Location in patent: Page/Page column 131.
[3]Patent: US2006/167246,2006,A1 .Location in patent: Page/Page column 155; 161.
[4]Recueil des Travaux Chimiques des Pays-Bas,1933,vol. 52,p. 538,547.
[5]Patent: WO2011/79804,2011,A1 .Location in patent: Page/Page column 29.
[6]Patent: US2012/245178,2012,A1 .Location in patent: Page/Page column 16.
[7]Patent: WO2015/8234,2015,A1 .Location in patent: Page/Page column 33; 34.
[8]Patent: WO2017/35360,2017,A1 .Location in patent: Paragraph 0511.
[9]Patent: WO2017/35349,2017,A1 .Location in patent: Paragraph 0588.

2
[ 56921-01-8 ]
[ 100-52-7 ]
[ 42747-98-8 ]

Yield	Reaction Conditions	Operation in experiment
67%		Step 2: methyl 4-NITRO-5-F (E)-2-PHENVLETHENVLLTHIOPHENE-2-CARBOXVLATE; A solution (0.33 M) of <strong>[56921-01-8]methyl 5-methyl-4-nitrothiophene-2-carboxylate</strong> in MeOH, was treated with benzaldehyde (1.5 eq. ). The reaction mixture was heated to reflux and when it became a clear solution a catalytic amount of pyrrolidine (0.01 eq. ) was added. After 18 h at reflux additional pyrrolidine (0.01 eq. ) was added. The reaction was heated to reflux for 40 h. After cooling down, evaporation of the solvent gave a residue that was purified by flash chromatography on silica gel (1: 9 AcOEt/petroleum ether) to afford the title compound (67%) as a solid. H NMR (400 MHz, CDCl3, 300 K) 8 3.94 (s, 3H), 7.32 (d, J = 16.2 Hz, 1H), 7.4-7. 5 (m, 3H), 7.59 (d, J = 7.13 Hz, 2H), 8.12 (d, J = 16.2 Hz, 1H), 8.22 (s, 1H) ; MS (ES+) M/Z 290 (M+H) +.

References: [1]Patent: WO2005/23819,2005,A1 .Location in patent: Page/Page column 31.
[2]Synthesis,1973,p. 313 - 315.
[3]Recueil des Travaux Chimiques des Pays-Bas,1933,vol. 52,p. 538,547.

3
[ 24647-78-7 ]
[ 64-19-7 ]
[ 56921-01-8 ]

References: [1]Journal of the Chemical Society. Perkin transactions II,1980,p. 1331 - 1335.

4
[ 64-19-7 ]
[ 75735-43-2 ]
[ 56921-01-8 ]

References: [1]Journal of the Chemical Society. Perkin transactions II,1980,p. 1331 - 1335.

5
[ 56921-01-8 ]
[ 100-52-7 ]
[ 858848-58-5 ]