[ CAS No. 2702-58-1 ] {[proInfo.proName]}

Name: 2702-58-1|Methyl 3,5-dinitrobenzoate|98%
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Product Details of [ 2702-58-1 ]

CAS No. :	2702-58-1	MDL No. :	MFCD00017016
Formula :	C₈H₆N₂O₆	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	POGCCFLNFPIIGW-UHFFFAOYSA-N
M.W :	226.14	Pubchem ID :	222067
Synonyms :

Safety of [ 2702-58-1 ]

Signal Word:	Warning	Class:	N/A
Precautionary Statements:	P280-P305+P351+P338	UN#:	N/A
Hazard Statements:	H302	Packing Group:	N/A
GHS Pictogram:

Application In Synthesis of [ 2702-58-1 ]

* 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.

Upstream synthesis route of [ 2702-58-1 ]
Downstream synthetic route of [ 2702-58-1 ]

[ 2702-58-1 ] Synthesis Path-Upstream 1~9

1
[ 2702-58-1 ]
[ 2999-46-4 ]
[ 5930-92-7 ]

Reference： [1] Journal of the Chemical Society, Perkin Transactions 1, 2000, # 6, p. 995 - 998

2
[ 2702-58-1 ]
[ 23218-93-1 ]

Yield	Reaction Conditions	Operation in experiment
88%	With diammonium sulfide In methanol for 5 h; Reflux	The solution of (NH₄)₂S²³ used for this reaction was prepared by adding a solution of Na₂S·9H₂O (15.00g, 62.47mmol) in 100mL of MeOH to a suspension of NH₄Cl (13.40g, 250.50mmol) in 100mL of MeOH and separating the solid material after 30min of stirring at room temperature. The resulting solution was added within 40min to a solution of 16 (6.20g, 27.42mmol) in 250mL of boiling MeOH and heated at reflux for 5h. After cooling down, the resulting precipitate of sulfur was filtered off and the pH was adjusted to 5 with 1M HCl and the solvent was removed under vacuum. The crude product was extracted with 250mL of AcOEt, washed with water, brine and dried over MgSO₄ and concentrated in vacuo. Purification by silica gel column chromatography (30percent acetone in hexane) afforded pure product 17 (4.73g, 88percent) as an orange solid. ¹H and ¹³C NMR data are in agreement with published data.²⁴ ¹H NMR (400MHz, acetone-d₆) δ: 7.93 (1H, dd, J 2.1, 1.4Hz, arom.), 7.71 (1H, t, J 2.2Hz, arom.), 7.67 (1H, dt J 2.2, 0.8Hz, arom.), 5.66 (2H, s, NH₂), 3.91 (3H, s, OMe). ¹³C NMR (100MHz, acetone-d₆) δ: 166.0, 151.1, 150.3, 133.1, 20.9, 112.2, 111.9, 52.8. R_f (30percent acetone/hexane) 0.37. MS(EI): m/z (percent)=197.1 (10), 196.1 (100, M⁺), 165.1 (33), 150.1 (20), 138.1 (8), 135.1 (22), 122.1 (35), 107.1 (17), 91.1 (23), 90.1 (10), 79.1 (8), 63.1 (20), 52.1 (9).

Reference： [1] Tetrahedron, 2016, vol. 72, # 27-28, p. 3809 - 3817
[2] Journal of Organic Chemistry, 1980, vol. 45, # 24, p. 4992 - 4993
[3] Journal of the Chemical Society, 1905, vol. 87, p. 1265
[4] Chemische Berichte, 1895, vol. 28, p. 597
[5] Recueil des Travaux Chimiques des Pays-Bas, 1921, vol. 40, p. 625
[6] Green Chemistry, 2012, vol. 14, # 8, p. 2289 - 2293

3
[ 2702-58-1 ]
[ 23218-93-1 ]

Reference： [1] Journal of the Chemical Society, 1905, vol. 87, p. 1265

4
[ 2702-58-1 ]
[ 78238-12-7 ]

Reference： [1] Australian Journal of Chemistry, 1981, vol. 34, # 6, p. 1319 - 1324
[2] MedChemComm, 2018, vol. 9, # 8, p. 1293 - 1304

5
[ 67-56-1 ]
[ 2702-58-1 ]
[ 99-34-3 ]
[ 78238-12-7 ]
[ 78238-13-8 ]

Reference： [1] Australian Journal of Chemistry, 1981, vol. 34, # 6, p. 1319 - 1324

6
[ 2702-58-1 ]
[ 76045-71-1 ]

Reference： [1] Australian Journal of Chemistry, 1981, vol. 34, # 6, p. 1319 - 1324

7
[ 2702-58-1 ]
[ 78238-14-9 ]

Reference： [1] Australian Journal of Chemistry, 1981, vol. 34, # 6, p. 1319 - 1324

8
[ 2702-58-1 ]
[ 14206-69-0 ]

Reference： [1] Australian Journal of Chemistry, 1981, vol. 34, # 6, p. 1319 - 1324

9
[ 2702-58-1 ]
[ 354512-22-4 ]

Reference： [1] ACS Medicinal Chemistry Letters, 2011, vol. 2, # 10, p. 735 - 740
[2] MedChemComm, 2018, vol. 9, # 8, p. 1293 - 1304

[ 2702-58-1 ] Synthesis Path-Downstream 1~88

1
[ 67-56-1 ]
[ 99-34-3 ]
[ 2702-58-1 ]

Yield	Reaction Conditions	Operation in experiment
99%	With thionyl chloride at 0 - 20℃;	1.1.60 Example 1.1.60: 3-(aminomethyl)-5-methoxy-N,N-dimethylaniline; SOCl2 (3.4 ml, 5.61g, 47.1 mmol, 5 eq) was added dropwise to a stirred solution of 3,5-dinitrobenzoic acid (2.0 g, 9.43 mmol, 1 eq, Aldrich) in 20 ml anhydrous MeOH at 0 0C under Ar. The reaction was stirred at 0 0C to room temperature overnight. The solvent was removed in vacuo, and the residue was dissolved in EtOAc. The organic layer was washed with saturated aqueous NaHCO3 (x2), water (x3), brine (xl), and dried over Na2SO4. The inorganics were filtered off, and the solvent was removed in vacuo yielding 2.12 g (9.38 mmol, 99% yield) of methyl 3,5-dinitrobenzoate.
98%	With Oxone In toluene at 60℃; for 48h; Green chemistry;
97%	With bis-(2-(1-adamantyl)ethyl) azodicarboxylate; triphenylphosphine In tetrahydrofuran; methanol at 20℃;

97%	With sulfuric acid for 5h; Reflux;	4.2.10. Methyl 3,5-dinitrobenzoate (16) To a stirred solution of 3,5-dinitrobenzoic acid (6.00g, 28.29mmol) in MeOH (100mL), conc. H2SO4 (3.0mL) was added dropwise and reaction mixture was heated at reflux for 5h. Completion of the reaction was followed by TLC (30% acetone in hexane). The solvent was removed under vacuum, and the crude product was extracted with AcOEt and the combined organic phases washed with water and then the pH was adjusted to 4 with NaHCO3. The organic fraction was washed with brine and dried over MgSO4. Product 16 obtained as a white solid after evaporation of the solvent was pure and no further purification was necessary (6.20g, 97%). 1H and 13C NMR data are in agreement with published data.22 1H NMR (400MHz, acetone-d6) δ: 9.17-9.15 (1H, m, arom.), 9.08-9.05 (2H, m, arom), 4.05 (3H, s, OMe). 13C NMR (100MHz, acetone-d6) δ: 164.0, 149.8, 134.4, 129.8, 123.2, 53.8. MS(EI): m/z (%)=226.1 (8, M+), 197.1 (7), 196.1 (72), 195.0 (100), 181.1 (18), 149.0 (31), 133.1 (13), 103.1 (8), 75.1 (48), 74.1 (23), 63.1 (7).
95%	With pyridine; N,N-dimethyl-formamide; chlorophosphoric acid diphenyl ester In dichloromethane 1.) 10 min, 2.) 1 h;
94%	With thionyl chloride for 3h; Ambient temperature;
94%	With sulfuric acid for 12h;
93%	With PhP(C₆H₄-p-(CH₂)2C₆F₁₃)2; bis(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)diazo dicarboxylate In tetrahydrofuran
90%	With N,N-bis[2-oxo-3-oxazolidinyl]phosphorodiamidic chloride; triethylamine In dichloromethane for 1h; Ambient temperature;
89%	With alumina methanesulfonic acid at 80℃; for 0.133333h; Microwave irradiation;	Representative Procedure for Preparation of Aromatic and Aliphatic Esters (Table 1) General procedure: In a typical reaction, AMA 2:3 (332 g, 0.6 mol), the corresponding carboxylicacid (1 mol), and alcohol (1.5-2 mol) were mixed in the provided reaction glass tubeequipped with a screw cap and magnetic agitation until a wet mixture was achieved.The reaction mixture was irradiated with microwaves (Anton Parr Monowave 300reactor) at 80 C for 8 min or 120 C for 20 min. On cooling, the mixture was diluted with dichloromethane (41 mL), filtered under gravity, and washed with dichloromethane;then the filtrate was washed with Na2CO3 (ss) and water. The organic layerwas dried over Na2SO4, filtered, and concentrated under reduced pressure to give theester.
60%	With thionyl chloride for 4h; Reflux;
	With hydrogenchloride
	With pyridine; benzenesulfonyl chloride
	With pyridine; p-toluenesulfonyl chloride
	With phosphorus pentoxide 1.) 0-5 deg C, 2.) reflux, 3 h; Yield given. Multistep reaction;
95 % Spectr.	With iron(III) sulfate; sulfuric acid for 2h; Heating;
	With sulfuric acid	II.A A. A. Preparation of Methyl 3,5-Dinitrobenzoate (I) STR10 In a 72-liter, round-bottomed flask equipped with mechanical stirrer and condenser were combined methyl alcohol (27.97 kg, 873 moles, 35.4 liters), 3,5-dinitrobenzoic acid (15 kg, 70.72 moles), and sulfuric acid (2.6 kg, 26.56 moles, 1.42 liters). The mixture was heated and stirred at reflux by means of a heating mantle for approximately 26 hours and then was allowed to cool to 25° (approximately 18 hours). The precipated solid was isolated by centrifugation (Tolhurst 12-in. centrifuge); each of the four loads collected was washed with methyl alcohol (4 liters). The wet solid was air dried for 16-18 hours to give 14.7 kg (92% of theory) of methyl 3,5-dinitrobenzoate (I). Tlc analysis (toluene/acetone/HOAc; 90/5/2; utilizing a plate marketed by Mallinckrodt under the trade designation ChromAR 7GF plate) showed the product to be homogenous and identical to an authentic sample.
	With sulfuric acid Reflux;
	With thionyl chloride for 4h; Reflux;
	With sulfuric acid for 5h; Reflux;	General procedure: Synthesis of triazoles: Substituted benzoic acid (0.01mol) in 0.2 mol of anhydrous methanol and 0.5 mL of conc. H2SO4 was added in a round bottom flask and then refluxed for 5 h. The resultant compound was confirmed by TLC (hexane:ethyl acetate) in the ratio 80:20 and then required compound was isolated by treating with NaOH. Then 0.01 mol of substituted methyl benzoate in 25 mL of ethanol was taken in a round bottom flask. The solution was refluxed for 4 h by adding 0.7 mL of 0.15 mol N2H4. The product was confirmed by TLC (hexane:ethyl acetate) in the ratio 80:20 and distilled off ethanol and it is cooled in ice water. The resultant compound was recrystallized with EtOH (78 % yield).

Reference： [1]Current Patent Assignee: PURDUE UNIVERSITY SYSTEM; COMENTIS, INC. - WO2009/42694, 2009, A1 Location in patent: Page/Page column 99
[2]Hou, Fei; Wang, Xi-Cun; Quan, Zheng-Jun [Organic and Biomolecular Chemistry, 2018, vol. 16, # 48, p. 9472 - 9476]
[3]Dandapani, Sivaraman; Newsome, Jeffery J.; Curran, Dennis P. [Tetrahedron Letters, 2004, vol. 45, # 35, p. 6653 - 6656]
[4]Pošta, Martin; Soós, Vilmos; Beier, Petr [Tetrahedron, 2016, vol. 72, # 27-28, p. 3809 - 3817]
[5]Garcia, T.; Arrieta, A.; Palomo, C. [Synthetic Communications, 1982, vol. 12, # 9, p. 681 - 690]
[6]Hosangadi, Bhaskar D.; Dave, Rajesh H. [Tetrahedron Letters, 1996, vol. 37, # 35, p. 6375 - 6378]
[7]González, Myriam; Alcolea, Pedro José; Álvarez, Raquel; Medarde, Manuel; Larraga, Vicente; Peláez, Rafael [International Journal for Parasitology: Drugs and Drug Resistance, 2021, vol. 16, p. 45 - 64]
[8]Dandapani, Sivaraman; Curran, Dennis P. [Tetrahedron, 2002, vol. 58, # 20, p. 3855 - 3864]
[9]Diago-Meseguer, J.; Palomo-Coll, A.L.; Fernandez-Lizarbe, J.R.; Zugaza-Bilbao, A. [Synthesis, 1980, # 7, p. 547 - 551]
[10]Fabian, Lucas; Gomez, Matias; Kuran, Juan A. Caturelli; Moltrasio, Graciela; Moglioni, Albertina [Synthetic Communications, 2014, vol. 44, # 16, p. 2386 - 2392]
[11]Cheng, Ya-Juan; Liu, Zhi-Yong; Liang, Hua-Ju; Fang, Cui-Ting; Zhang, Niu-Niu; Zhang, Tian-Yu; Yan, Ming [Molecules, 2019, vol. 24, # 10]
[12]Herre [Chemische Berichte, 1895, vol. 28, p. 597]
[13]Brewster; Ciotti [Journal of the American Chemical Society, 1955, vol. 77, p. 6214]
[14]Brewster; Ciotti [Journal of the American Chemical Society, 1955, vol. 77, p. 6214]
[15]Balasubramaniyan, V.; Bhatia, V. G.; Wagh, S. B. [Tetrahedron, 1983, vol. 39, # 9, p. 1475 - 1485]
[16]Xu; Liu; Chen; Ma [Synthetic Communications, 2001, vol. 31, # 14, p. 2113 - 2117]
[17]Current Patent Assignee: MALLINCKRODT PUBLIC LIMITED COMPANY - US4284620, 1981, A
[18]Meira, Cássio S.; dos Santos Filho, José Maurício; Sousa, Caroline C.; Anjos, Pâmela S.; Cerqueira, Jéssica V.; Dias Neto, Humberto A.; da Silveira, Rafael G.; Russo, Helena M.; Wolfender, Jean-Luc; Queiroz, Emerson F.; Moreira, Diogo R.M.; Soares, Milena B.P. [Bioorganic and Medicinal Chemistry, 2018, vol. 26, # 8, p. 1971 - 1985]
[19]Zhang, Niu-niu; Liu, Zhi-yong; Liang, Jie; Tang, Yun-xiang; Qian, Lu; Gao, Ya-min; Zhang, Tian-Yu; Zhang, Tian-yu; Yan, Ming [MedChemComm, 2018, vol. 9, # 8, p. 1293 - 1304]
[20]Kumar, Kottakki Naveen; Amperayani, Karteek Rao; Ummdi, V. Ravi Sankar; Parimi, Uma Devi [Asian Journal of Chemistry, 2019, vol. 31, # 5, p. 1077 - 1080]

2
[ 2702-58-1 ]
[ 23218-93-1 ]

Yield	Reaction Conditions	Operation in experiment
88%	With diammonium sulfide; In methanol; for 5h;Reflux;	The solution of (NH4)2S23 used for this reaction was prepared by adding a solution of Na2S·9H2O (15.00g, 62.47mmol) in 100mL of MeOH to a suspension of NH4Cl (13.40g, 250.50mmol) in 100mL of MeOH and separating the solid material after 30min of stirring at room temperature. The resulting solution was added within 40min to a solution of 16 (6.20g, 27.42mmol) in 250mL of boiling MeOH and heated at reflux for 5h. After cooling down, the resulting precipitate of sulfur was filtered off and the pH was adjusted to 5 with 1M HCl and the solvent was removed under vacuum. The crude product was extracted with 250mL of AcOEt, washed with water, brine and dried over MgSO4 and concentrated in vacuo. Purification by silica gel column chromatography (30% acetone in hexane) afforded pure product 17 (4.73g, 88%) as an orange solid. 1H and 13C NMR data are in agreement with published data.24 1H NMR (400MHz, acetone-d6) delta: 7.93 (1H, dd, J 2.1, 1.4Hz, arom.), 7.71 (1H, t, J 2.2Hz, arom.), 7.67 (1H, dt J 2.2, 0.8Hz, arom.), 5.66 (2H, s, NH2), 3.91 (3H, s, OMe). 13C NMR (100MHz, acetone-d6) delta: 166.0, 151.1, 150.3, 133.1, 20.9, 112.2, 111.9, 52.8. Rf (30% acetone/hexane) 0.37. MS(EI): m/z (%)=197.1 (10), 196.1 (100, M+), 165.1 (33), 150.1 (20), 138.1 (8), 135.1 (22), 122.1 (35), 107.1 (17), 91.1 (23), 90.1 (10), 79.1 (8), 63.1 (20), 52.1 (9).

Reference： [1]Tetrahedron,2016,vol. 72,p. 3809 - 3817
[2]Journal of Organic Chemistry,1980,vol. 45,p. 4992 - 4993
[3]Journal of the Chemical Society,1905,vol. 87,p. 1265
[4]Recueil des Travaux Chimiques des Pays-Bas,1921,vol. 40,p. 625
[5]Green Chemistry,2012,vol. 14,p. 2289 - 2293

3
[ 2702-58-1 ]
[ 23218-93-1 ]
3-hydroxyamino-5-nitro-benzoic acid methyl ester [ No CAS ]

Reference： [1]Journal of the Chemical Society,1905,vol. 87,p. 1265

4
[ 67-56-1 ]
[ 99-33-2 ]
[ 2702-58-1 ]

Yield	Reaction Conditions	Operation in experiment
98%	for 1h; Reflux;	4.5. 3,5-Dinitrobenzohydrazide (21) [22] Methyl 3,5-dinitrobenzoate was obtained in a 98% yield byrefluxing 3,5-dinitrobenzoyl chloride in MeOH for 1 h. Upon cooling,the precipitated product was filtered and washed with 1%NaOH. In the next step, hydrazine hydrate (80%, 0.94 g, 0.91 mL,15 mmol) was added dropwise into the solution of methyl 3,5-dinitrobenzoate (1.13 g, 5 mmol) in EtOH (20 mL) at 0 °C. The reactionmixture was stirred for 4 h at rt. Upon completion, theprecipitated product was filtered and washed with EtOH (10 mL)and Et2O (10 mL). The product was used without further purification.
87%	With triethylamine In tetrahydrofuran Reflux;
	With pyridine; benzene

	With pyridine In dichloromethane at -20℃; for 1h;
	at 0 - 5℃;
4.73 g	With N-ethyl-N,N-diisopropylamine for 1h; Cooling with ice;	34 Example 34: Methyl 3,5-dinitrobenzoate In methanol (100 mL) was dissolved 3,5-dinitrobenzoyl chloride and diisopropylethylamine (4.53 mL) was added thereto while cooling with ice. The reaction solution was stirred for 1 hour and then the solvent was distilled off. The resulting substance was diluted with ethyl acetate, sequentially washed with water and a saturated sodium chloride solution and dried over anhydrous magnesium sulphate before distillation of the solvent to give the titled compound (4.73 g) having the following physical properties. TLC: Rf 0.31 (hexane:ethyl acetate = 5:1).
2.19 g	With triethylamine In dichloromethane at 0℃; Inert atmosphere;	General Procedure of Derivatization General procedure: To a 50 mL round bottom flask with Et3N 12 mmol (1.21 g), CH3OH 1.2 equimolar (The amount of CH3OH depends on the number of acyl chloride groups contained in the substrate, 0.38 g CH3OH per acyl chloride group), CH2Cl2 10mL was added at 0°C. The acyl chloride 10 mmol was dissolved in CH2Cl2 5 mL and slowly added dropwise to the round bottom flask under N2 atmosphere through a syringe, the reaction mixture was maintained at -0°C, after completion of the reaction monitored by TLC, removed excess solvent, washed the residue with water 20 mL to obtain the crude product. The crude product was further purified by silica gel column chromatography (200-300 mesh), and n-hexane and ethyl acetate were used as eluents.

Reference： [1]Karabanovich, Galina; Němeček, Jan; Valášková, Lenka; Carazo, Alejandro; Konečná, Klára; Stolaříková, Jiřina; Hrabálek, Alexandr; Pavliš, Oto; Pávek, Petr; Vávrová, Kateřina; Roh, Jaroslav; Klimešová, Věra [European Journal of Medicinal Chemistry, 2017, vol. 126, p. 369 - 383]
[2]Wang, Chao; Yin, Shouchun; Chen, Senlin; Xu, Huaping; Wang, Zhiqiang; Zhang, Xi [Angewandte Chemie - International Edition, 2008, vol. 47, # 47, p. 9049 - 9052]
[3]Reichstein [Helvetica Chimica Acta, 1926, vol. 9, p. 802]
[4]Terpko, Marc O.; Heck, Richard F. [Journal of Organic Chemistry, 1980, vol. 45, # 24, p. 4992 - 4993] Komiyama, Makoto; Hirai, Hidefumi [Chemistry Letters, 1980, p. 1251 - 1254]
[5]Arrieta, A.; Garcia, T.; Palomo, C. [Synthetic Communications, 1982, vol. 12, # 14, p. 1139 - 1146]
[6]Wang, Shudong; Zhang, Lei; Jin, Yongsheng; Tang, Jin Hao; Su, Hua; Yu, Shichong; Ren, Haixiang [Asian Journal of Chemistry, 2014, vol. 26, # 8, p. 2362 - 2364]
[7]Current Patent Assignee: ONO PHARMACEUTICAL CO LTD - EP2762466, 2014, A1 Location in patent: Paragraph 0286
[8]Yu, Zhiqun; Yao, Hongmiao; Xu, Qilin; Liu, Jiming; Le, Xingmao; Ren, Minna [Phosphorus, Sulfur and Silicon and the Related Elements, 2021, vol. 196, # 8, p. 685 - 689]

5
[ 67-56-1 ]
[ 2702-58-1 ]
[ 99-34-3 ]
[ 78238-12-7 ]
[ 78238-13-8 ]

Reference： [1]Australian Journal of Chemistry,1981,vol. 34,p. 1319 - 1324

6
[ 67-56-1 ]
[ 83187-07-9 ]
[ 2702-58-1 ]
[ 85067-64-7 ]

Yield	Reaction Conditions	Operation in experiment
	With 2,6-dimethylpyridine at 80℃; for 48h; Yield given. Yields of byproduct given;

Reference： [1]Paquette,L.A.; Ohkata,K.; Jelich,K. [Journal of the American Chemical Society, 1983, vol. 105, p. 2800]

7
[ 67-56-1 ]
[ 83187-05-7 ]
[ 2702-58-1 ]
[ 85067-53-4 ]

Yield	Reaction Conditions	Operation in experiment
96%	With 2,6-dimethylpyridine at 125℃; for 96h; Yields of byproduct given;

Reference： [1]Paquette,L.A.; Ohkata,K.; Jelich,K. [Journal of the American Chemical Society, 1983, vol. 105, p. 2800]

8
[ 67-56-1 ]
3,5-Dinitro-benzoic acid (4aR,8aR)-(1,2,3,4-tetrahydro-4a,8a-propeno-naphthalen-9-yl) ester [ No CAS ]
[ 2702-58-1 ]
anti-11-methoxy<4.4.3>propella-2,4,12-triene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With 2,6-dimethylpyridine at 125℃; for 48h; Yield given. Yields of byproduct given;
	With 2,6-dimethylpyridine at 96℃; for 24h; Yield given. Yields of byproduct given;

Reference： [1]Paquette,L.A.; Ohkata,K.; Jelich,K. [Journal of the American Chemical Society, 1983, vol. 105, p. 2800]
[2]Paquette,L.A.; Ohkata,K.; Jelich,K. [Journal of the American Chemical Society, 1983, vol. 105, p. 2800]

9
[ 2702-58-1 ]
[ 2900-63-2 ]

Yield	Reaction Conditions	Operation in experiment
83%	With hydrazine hydrate monohydrate In ethanol at 0 - 20℃; for 4h;	Synthesis of compound (I). Synthesis of compound (I). A solution of methyl3,5-dinitrobenzoate (10 mmol, 2.2614 g) was added toa 100 mL round-bottom flask containing ethanol(40 mL) at 0°C. 80% hydrazine hydrate (30 mmol,1.82 mL) was added dropwise to this stirred solution.The resultant mixture was stirred for 4 h at RT. Uponcompletion of the reaction, the precipitated productwas filtered and rinsed thoroughly with 20 mL of ethanoland 20 mL of diethyl ether. The product acquiredwas employed without further purification [31].
	With hydrazine hydrate monohydrate
	With hydrazine hydrate monohydrate In methanol

	With hydrazine hydrate monohydrate In ethanol at 0 - 20℃; for 4h;	4.5. 3,5-Dinitrobenzohydrazide (21) [22] Methyl 3,5-dinitrobenzoate was obtained in a 98% yield byrefluxing 3,5-dinitrobenzoyl chloride in MeOH for 1 h. Upon cooling,the precipitated product was filtered and washed with 1%NaOH. In the next step, hydrazine hydrate (80%, 0.94 g, 0.91 mL,15 mmol) was added dropwise into the solution of methyl 3,5-dinitrobenzoate (1.13 g, 5 mmol) in EtOH (20 mL) at 0 °C. The reactionmixture was stirred for 4 h at rt. Upon completion, theprecipitated product was filtered and washed with EtOH (10 mL)and Et2O (10 mL). The product was used without further purification.Yield: 84% as a yellowish solid; mp 153-154 °C (lit. [22] mp155-157 °C). 1H NMR (300 MHz, DMSO) δ 10.50 (s, 1H, NH), 9.00 (d,J 2.1 Hz, 2H), 8.93 (t, J 2.1 Hz, 1H), 4.74 (s, 2H, NH2). 13C NMR(75 MHz, DMSO) δ 161.50,148.38,136.09,127.36,120.84. Anal. Calcdfor C7H6N4O5: C, 37.18; H, 2.67; N, 24.77. Found: C, 37.42; H, 2.68; N,24.32.
	With hydrazine hydrate monohydrate In ethanol at 70℃;
	With hydrazine In ethanol for 4h; Reflux;	General procedure: Synthesis of triazoles: Substituted benzoic acid (0.01mol) in 0.2 mol of anhydrous methanol and 0.5 mL of conc. H2SO4 was added in a round bottom flask and then refluxed for 5 h. The resultant compound was confirmed by TLC (hexane:ethyl acetate) in the ratio 80:20 and then required compound was isolated by treating with NaOH. Then 0.01 mol of substituted methyl benzoate in 25 mL of ethanol was taken in a round bottom flask. The solution was refluxed for 4 h by adding 0.7 mL of 0.15 mol N2H4. The product was confirmed by TLC (hexane:ethyl acetate) in the ratio 80:20 and distilled off ethanol and it is cooled in ice water. The resultant compound was recrystallized with EtOH (78 % yield).

Reference： [1]Çınar, Ercan; Çakmak, Reşit; Eyup, Basaran; Haşimi, Nesrin [Russian Journal of Bioorganic Chemistry, 2022, vol. 48, # 1, p. 143 - 152][Bioorg. Khim., 2022, vol. 48, # 01, p. 143 - 152]
[2]Dwivedi, D.K.; Agarwala, B.V.; Dey, A.K. [Bulletin des Societes Chimiques Belges, 1987, vol. 96, # 4, p. 431 - 436]
[3]Wang, Shudong; Zhang, Lei; Jin, Yongsheng; Tang, Jin Hao; Su, Hua; Yu, Shichong; Ren, Haixiang [Asian Journal of Chemistry, 2014, vol. 26, # 8, p. 2362 - 2364]
[4]Karabanovich, Galina; Němeček, Jan; Valášková, Lenka; Carazo, Alejandro; Konečná, Klára; Stolaříková, Jiřina; Hrabálek, Alexandr; Pavliš, Oto; Pávek, Petr; Vávrová, Kateřina; Roh, Jaroslav; Klimešová, Věra [European Journal of Medicinal Chemistry, 2017, vol. 126, p. 369 - 383]
[5]Meira, Cássio S.; dos Santos Filho, José Maurício; Sousa, Caroline C.; Anjos, Pâmela S.; Cerqueira, Jéssica V.; Dias Neto, Humberto A.; da Silveira, Rafael G.; Russo, Helena M.; Wolfender, Jean-Luc; Queiroz, Emerson F.; Moreira, Diogo R.M.; Soares, Milena B.P. [Bioorganic and Medicinal Chemistry, 2018, vol. 26, # 8, p. 1971 - 1985]
[6]Kumar, Kottakki Naveen; Amperayani, Karteek Rao; Ummdi, V. Ravi Sankar; Parimi, Uma Devi [Asian Journal of Chemistry, 2019, vol. 31, # 5, p. 1077 - 1080]

10
[ 4110-35-4 ]
[ 124-41-4 ]
[ 2702-58-1 ]

Reference： [1]Bulletin of the Chemical Society of Japan,1983,vol. 56,p. 1206 - 1213

11
[ 2702-58-1 ]
[ 99-34-3 ]

Yield	Reaction Conditions	Operation in experiment
90%	With sodium hydroxide In N,N-dimethyl-formamide for 0.5h; Ambient temperature;
86%	With potassium hydroxide In methanol at 35℃; for 0.0333333h;
85%	With lithium chloride In N,N-dimethyl-formamide for 0.166667h; Microwave irradiation; chemoselective reaction;

With water at 69.84℃;

Reference： [1]Khurana, J. M.; Sehgal, Arti [Organic Preparations and Procedures International, 1994, vol. 26, # 5, p. 580 - 583]
[2]Khurana, Jitender M.; Chauhan, Sushma; Bansal, Geeti [Monatshefte fur Chemie, 2004, vol. 135, # 1, p. 83 - 87]
[3]Location in patent: experimental part Wu, Xiao-Ai; Ying, Ping; Liu, Jun-Yang; Shen, Heng-Shui; Chen, Yue; He, Ling [Synthetic Communications, 2009, vol. 39, # 19, p. 3459 - 3470]
[4]Di Somma, Ilaria; Marotta, Raffaele; Andreozzi, Roberto; Caprio, Vincenzo [Organic Process Research and Development, 2012, vol. 16, # 12, p. 2001 - 2007]

12
[ 616-42-2 ]
[ 99-34-3 ]
[ 2702-58-1 ]

Yield	Reaction Conditions	Operation in experiment
94%	With toluene-4-sulfonic acid In benzene

Reference： [1]Hosangadi, Bhaskar D.; Dave, Rajesh H. [Tetrahedron Letters, 1996, vol. 37, # 35, p. 6375 - 6378]

13
[ 2702-58-1 ]
[ 64-17-5 ]
[ 618-71-3 ]

Yield	Reaction Conditions	Operation in experiment
84%	With indium; iodine for 32h; Heating;

Reference： [1]Ranu, Brindaban C.; Dutta, Pinak; Sarkar, Arunkanti [Journal of Organic Chemistry, 1998, vol. 63, # 17, p. 6027 - 6028]

14
[ 2702-58-1 ]
[ 7380-78-1 ]
[ 107106-76-3 ]
4-methyl-10-phenyl-9-(4-methoxyphenyl)-2,7-phenanthrenedicarboxylic acid diethyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
49%	With palladium diacetate; tetrabutylammomium bromide; potassium carbonate In N,N-dimethyl-formamide at 100℃; for 120h;

Reference： [1]Mandal, Ashis Baran; Lee, Gene-Hsiang; Liu, Yi-Hung; Peng, Shie-Ming; Leung, Man-kit [Journal of Organic Chemistry, 2000, vol. 65, # 2, p. 332 - 336]

15
[ 2702-58-1 ]
[ 42497-80-3 ]
[ 107106-76-3 ]
4-methyl-9-phenyl-10-(4-carbethoxyphenyl)-2,7-phenanthrenedicarboxylic acid diethyl ester [ No CAS ]

Reference： [1]Journal of Organic Chemistry,2000,vol. 65,p. 332 - 336

16
[ 2702-58-1 ]
[ 107106-76-3 ]
[ 501-65-5 ]
4-methyl-9,10-diphenyl-2,7-phenanthrenedicarboxylic acid diethyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
74%	With palladium diacetate; tetrabutylammomium bromide; tetra-(n-butyl)ammonium iodide; potassium carbonate In N,N-dimethyl-formamide at 100℃; for 72h;

Reference： [1]Mandal, Ashis Baran; Lee, Gene-Hsiang; Liu, Yi-Hung; Peng, Shie-Ming; Leung, Man-kit [Journal of Organic Chemistry, 2000, vol. 65, # 2, p. 332 - 336]

17
[ 2702-58-1 ]
[ 2999-46-4 ]
[ 5930-92-7 ]
Ethyl 7-methoxycarbonyl-5-nitro-2H-isoindole-1-carboxylate [ No CAS ]
Ethyl 5-methoxycarbonyl-7-nitro-2H-isoindole-1-carboxylate [ No CAS ]

Reference： [1]Journal of the Chemical Society. Perkin Transactions 1 (2001),2000,p. 995 - 998

18
[ 2702-58-1 ]
[ 2769-72-4 ]
tert-Butyl 7-methoxycarbonyl-5-nitro-2H-isoindole-1-carboxylate [ No CAS ]
tert-Butyl 5-methoxycarbonyl-7-nitro-2H-isoindole-1-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
1: 16% 2: 7%	With 1,8-diazabicyclo[5.4.0]undec-7-ene In acetonitrile at 20℃; for 6h;

Reference： [1]Murashima, Takashi; Tamai, Ryuji; Nishi, Keiji; Nomura, Kentaroh; Fujita, Ken-Ichi; Uno, Hidemitsu; Ono, Noboru [Journal of the Chemical Society. Perkin Transactions 1 (2001), 2000, # 6, p. 995 - 998]

19
[ 908094-01-9 ]
[ 99-34-3 ]
[ 2702-58-1 ]
[ 21434-37-7 ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 3,5-dinitrobenzoic acid With 1,3,5-trichloro-2,4,6-triazine; potassium carbonate In tetrahydrofuran; acetonitrile at 0℃; for 2.75h; Stage #2: diazomethane In diethyl ether at 0 - 20℃; for 12h;

Reference： [1]Forbes; Barrett; Lewis; Smith [Tetrahedron Letters, 2000, vol. 41, # 51, p. 9943 - 9947]

20
[ 50-00-0 ]
[ 2702-58-1 ]
[ 2002-24-6 ]
3-(2-hydroxy-ethyl)-1,5-dinitro-3-aza-bicyclo[3.3.1]non-6-ene-7-carboxylic acid methyl ester [ No CAS ]

Reference： [1]Russian Journal of Organic Chemistry,2000,vol. 36,p. 743 - 749

21
[ 2702-58-1 ]
[ 456-27-9 ]
3-nitro-5-(4-nitro-phenylazo)-benzoic acid methyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
24%	Stage #1: methyl 3,5-dinitrobenzoate With potassium borohydride In methanol; dimethyl sulfoxide at 0 - 3℃; for 0.666667h; Stage #2: 4-nitrobenzenediazonium tetrafluoroborate In methanol; dimethyl sulfoxide for 0.5h;

Reference： [1]Atroshchenko; Blokhina; Shakhkel'dyan; Grudtsyn; Gitis; Borbulevich; Blokhin; Kaminskii; Shishkin; Andrianov [Russian Journal of Organic Chemistry, 2000, vol. 36, # 5, p. 684 - 692]

22
[ 2702-58-1 ]
[ 24564-52-1 ]
3-(4-dimethylamino-phenylazo)-5-nitro-benzoic acid methyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
17%	Stage #1: methyl 3,5-dinitrobenzoate With potassium borohydride In methanol; dimethyl sulfoxide at 0 - 3℃; for 0.666667h; Stage #2: 4-(dimethylamino)benzenediazonium tetrafluoroborate In methanol; dimethyl sulfoxide for 0.5h;

23
[ 50-00-0 ]
[ 2702-58-1 ]
[ 56-40-6 ]
3-carboxymethyl-1,5-dinitro-3-aza-bicyclo[3.3.1]non-6-ene-7-carboxylic acid methyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
42%	Stage #1: methyl 3,5-dinitrobenzoate With potassium borohydride In tetrahydrofuran; water at 5 - 15℃; for 0.25h; Stage #2: formaldehyd; glycine In tetrahydrofuran; water

Reference： [1]Shakhkel'dyan; Nikiforova; Grudtsyn; Atroshchenko; Borbulevich; Efremov; Gitis; Moiseev; Alifanova; Chudakov; Kovalevskii [Russian Journal of Organic Chemistry, 2001, vol. 37, # 4, p. 583 - 591]

24
[ 587833-95-2 ]
[ 2702-58-1 ]

Yield	Reaction Conditions	Operation in experiment
60%	With hydrogenchloride In acetone

Reference： [1]Monk, Keith A.; Siles, Rogelio; Pinney, Kevin G.; Garner, Charles M. [Tetrahedron Letters, 2003, vol. 44, # 19, p. 3759 - 3761]

25
[ 99-34-3 ]
poly(styrene-co-divinylbenzene)-supported methyl sulfonate, loading rate of SO₃Me: ca. 4.0 mmol/g [ No CAS ]
[ 2702-58-1 ]

Yield	Reaction Conditions	Operation in experiment
97%	With potassium carbonate In acetonitrile for 5h; Heating;

Reference： [1]Yoshino, Tomonori; Togo, Hideo [Synlett, 2005, # 3, p. 517 - 519]

26
[ 17881-97-9 ]
[ 99-33-2 ]
[ 2702-58-1 ]

Yield	Reaction Conditions	Operation in experiment
90%	Stage #1: (hydroxymethyl)dimethylphenylsilane With potassium <i>tert</i>-butylate; tetramethylurea at 20 - 25℃; Stage #2: 3,5-dinitrobenoyl chloride With pyridine In tetrahydrofuran at 50℃; for 1.5h;

Reference： [1]Simov, Biljana Peric; Wuggenig, Frank; Mereiter, Kurt; Andres, Hendrik; France, Julien; Schnelli, Peter; Hammerschmidt, Friedrich [Journal of the American Chemical Society, 2005, vol. 127, # 40, p. 13934 - 13940]

27
[ 99-34-3 ]
[ 2702-58-1 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1: 87 percent / PhP(O)Cl₂; PCl₅ / 15 h / Heating 2: 94 percent / NaOCH₃ / 0 - 20 °C 3: 60 percent / HCl / acetone
	Multi-step reaction with 2 steps 1: 4-(N,N-dimethylamino)pyridinium chlorosulphite chloride / CH₂Cl₂ / 0.25 h / -20 °C 2: pyridine / CH₂Cl₂ / 1 h / -20 °C
	Multi-step reaction with 3 steps 1: triethylamine / CH₂Cl₂ / 0.5 h / Ambient temperature 2: triphenylphosphine dibromide / CH₂Cl₂ / 0.17 h / Ambient temperature 3: 2-oxo-3-trimethylsilyltetrahydro-1,3-oxazole / 0.25 h / Ambient temperature

	Multi-step reaction with 3 steps 1: triethylamine / CH₂Cl₂ / 0.5 h / Ambient temperature 2: triphenylphosphine dibromide / CH₂Cl₂ / 0.17 h / Ambient temperature 3: CH₂Cl₂ / 10 h / 10 °C
	Multi-step reaction with 2 steps 1: thionyl chloride / Reflux 2: 0 - 5 °C
	Multi-step reaction with 2 steps 1: thionyl chloride; sulfuric acid / 0.28 h / Inert atmosphere; Reflux 2: triethylamine / dichloromethane / 0 °C / Inert atmosphere

Reference： [1]Monk, Keith A.; Siles, Rogelio; Pinney, Kevin G.; Garner, Charles M. [Tetrahedron Letters, 2003, vol. 44, # 19, p. 3759 - 3761]
[2]Arrieta, A.; Garcia, T.; Palomo, C. [Synthetic Communications, 1982, vol. 12, # 14, p. 1139 - 1146]
[3]Aizpurua, Jesus Mari; Palomo, Claudio [Synthesis, 1982, # 8, p. 684 - 686]
[4]Aizpurua, Jesus Mari; Palomo, Claudio [Synthesis, 1982, # 8, p. 684 - 686]
[5]Wang, Shudong; Zhang, Lei; Jin, Yongsheng; Tang, Jin Hao; Su, Hua; Yu, Shichong; Ren, Haixiang [Asian Journal of Chemistry, 2014, vol. 26, # 8, p. 2362 - 2364]
[6]Yu, Zhiqun; Yao, Hongmiao; Xu, Qilin; Liu, Jiming; Le, Xingmao; Ren, Minna [Phosphorus, Sulfur and Silicon and the Related Elements, 2021, vol. 196, # 8, p. 685 - 689]

28
[ 2702-58-1 ]
[ 78238-12-7 ]

Reference： [1]Australian Journal of Chemistry,1981,vol. 34,p. 1319 - 1324
[2]MedChemComm,2018,vol. 9,p. 1293 - 1304

29
[ 2702-58-1 ]
[ 76045-71-1 ]

Reference： [1]Australian Journal of Chemistry,1981,vol. 34,p. 1319 - 1324

30
[ 2702-58-1 ]
[ 78238-14-9 ]

Reference： [1]Australian Journal of Chemistry,1981,vol. 34,p. 1319 - 1324

31
[ 2702-58-1 ]
[ 14206-69-0 ]

Reference： [1]Australian Journal of Chemistry,1981,vol. 34,p. 1319 - 1324

32
C₁₀H₁₂N₂O₆Si [ No CAS ]
[ 2702-58-1 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: triphenylphosphine dibromide / CH₂Cl₂ / 0.17 h / Ambient temperature 2: 2-oxo-3-trimethylsilyltetrahydro-1,3-oxazole / 0.25 h / Ambient temperature
	Multi-step reaction with 2 steps 1: triphenylphosphine dibromide / CH₂Cl₂ / 0.17 h / Ambient temperature 2: CH₂Cl₂ / 10 h / 10 °C

Reference： [1]Aizpurua, Jesus Mari; Palomo, Claudio [Synthesis, 1982, # 8, p. 684 - 686]
[2]Aizpurua, Jesus Mari; Palomo, Claudio [Synthesis, 1982, # 8, p. 684 - 686]

33
[ 2702-58-1 ]
[ 79883-94-6 ]

Yield	Reaction Conditions	Operation in experiment
85%	In methanol; ethanolamine	2.a a) a) Preparation of 3,5-dinitro-N-(2-hydroxyethyl)benzamide 750 g (3.32 moles) of methyl 3,5-dinitro benzoate are suspended in 2 liters of methanol in the presence of 222.7 g (3.65 moles) of ethanolamine. The reaction mixture is refluxed for 48 hours until the ester has disappeared. After 4 hours at room temperature, the crystalline product is filtered off, washed with 500 cm3 of methylene chloride, then dried in an oven at 60° C. in a vacuum for 4 hours. This procedure leads to the recovery of 718 g of product in a yield of 85% Melting point: 140° C. TLC (toluene/methyl ethyl ketone/formic acid (60/25/25) Rf: 0.5.

Reference： [1]Current Patent Assignee: GUERBET - US5043152, 1991, A

34
[ 2702-58-1 ]
[ 78238-13-8 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium methylate; sodium In methanol; ethyl acetate	Monomers: Methyl 3-methoxy-5-nitrobenzoate (7): Five (5) g (22 mmol) methyl 3,5-dinitrobenzoate (Aldrich) were suspended in 80 mL methanol (A.C.S. grade) and heated to reflux for app. 1 h under nitrogen, until a clear brown solution had formed. A simultaneously prepared sodium methoxide solution (prepared by portionwise addition of 0.76 g (33 mmol, 1.5 eq.) sodium to 10 mL methanol, the reaction flask was purged with nitrogen until all sodium had reacted) was added dropwise to the hot solution by syringe, each drop causing a deep red color. The reaction mixture was refluxed for an additional 15 h. After cooling to r.t., it was concentrated to dryness, the remaining brown-purple solid was taken up in 30 mL distilled water and acidified with 2 N HCl. The addition of ethyl acetate caused the present light orange solid to dissolve, phases were separated and extraction with ethyl acetate was repeated twice. The combined organic layers were washed with sat. aq. NaHCO3, with brine, then dried with MgSO4 and concentrated, leaving 3.7 g of a pale yellow solid. The crude product was purified by column chromatography (7:3 hexanes/ethyl acetate, Rf=0.6, UV; note: starting material coelutes but should be gone after the reaction time given) to afford 2.3 g (50%) of a light yellow solid. The procedure can be scaled up to 30 g starting material: depending on the course of the reaction, crude product material might be sufficiently pure to be carried on into the next step without further purification. mp 88-89° C. 2; 1H NMR (CDCl3) δ8.46 (dd, J1=1.5 Hz, J2=2.4 Hz, 1H), 7.92 (t, J1=2.4 Hz, J2=2.4 Hz, 1H), 7.88 (dd, J1=1.5 Hz, J2=2.4 Hz, 1H), 3.99 (s, 3H, OCH3), 3.95 (s, 3H, OCH3); 13C NMR (CDCl3) δ164.59, 160.00, 148.95, 132.37, 120.84, 116.36, 112.65, 56.02, 52.60.

Reference： [1]Current Patent Assignee: WARF (in: University of Wisconsin); UNIVERSITY OF WISCONSIN SYSTEM - US2004/116654, 2004, A1

35
[ 2702-58-1 ]
[ 865-34-9 ]
[ 78238-13-8 ]

Yield	Reaction Conditions	Operation in experiment
60%	In methanol Reflux; Inert atmosphere;
56%	Stage #1: methyl 3,5-dinitrobenzoate; lithium methanolate In methanol at 85℃; for 4h; Stage #2: With hydrogenchloride In methanol; water at 20℃;	1.1.60 methyl 3,5-dinitrobenzoate (1.5 g, 6.63 mmol, 1 eq) in 10 ml anhydrous MeOH under Ar was heated to reflux at 85 0C. LiOMe (1.0 M in MeOH, 13.3 ml, 13.3 mmol, 2 eq) was added to the refluxing solution. After 4 h the reaction was cooled to room temperature, and the mixture was adjusted to pH ~ 3 with concentrated HCl. The solvent was removed in vacuo and the residue was dissolved in EtOAc. The organic layer was washed with saturated aqueous NaHCO3 (x2), water (x3), brine (xl), and dried over Na2SO4. The inorganics were filtered off, and the solvent was removed in vacuo. Purification via flash chromatography yielded 0.7705 g (3.70 mmol, 56% yield) of methyl 3-methoxy-5-nitrobenzoate.
35%	In methanol for 12h; Reflux;

Reference： [1]Zhang, Niu-niu; Liu, Zhi-yong; Liang, Jie; Tang, Yun-xiang; Qian, Lu; Gao, Ya-min; Zhang, Tian-Yu; Zhang, Tian-yu; Yan, Ming [MedChemComm, 2018, vol. 9, # 8, p. 1293 - 1304]
[2]Current Patent Assignee: PURDUE UNIVERSITY SYSTEM; COMENTIS, INC. - WO2009/42694, 2009, A1 Location in patent: Page/Page column 99-100
[3]Cheng, Ya-Juan; Liu, Zhi-Yong; Liang, Hua-Ju; Fang, Cui-Ting; Zhang, Niu-Niu; Zhang, Tian-Yu; Yan, Ming [Molecules, 2019, vol. 24, # 10]

36
[ 2702-58-1 ]
[ 1949-55-9 ]

Yield	Reaction Conditions	Operation in experiment
99%	With palladium 10% on activated carbon; hydrogen In ethanol; ethyl acetate for 22h; Inert atmosphere;
92%	With palladium on activated charcoal; hydrogen In ethyl acetate for 72h;
67%	Stage #1: methyl 3,5-dinitrobenzoate With hydrogenchloride; 1,1,1,3',3',3'-hexafluoro-propanol; iron In water at 20℃; for 0.5h; Stage #2: With sodium hydrogencarbonate In water chemoselective reaction;	2. General Procedure for the Reduction of Nitro Compounds General procedure: The nitro compound (1 equiv), HFIP (10 equiv), Fe powder (5 equiv) were mixed in a tube. Then 2 N HCl aqueous solutions was added to the reaction mixture. After stirring at room temperature for 30 min, the reaction mixture was neutralized with sat. NaHCO3 (aq.) and extracted with EtOAc three times. The combined organic layers were washed with brine, dried over Na2SO4, filtered, and concentrated under reduced pressure. The resulting crude product was then purified by column chromatography on silica gel to furnish the desired amine product.

Reference： [1]Af Gennäs, Gustav Boije; Talman, Virpi; Aitio, Olli; Ekokoski, Elina; Finel, Moshe; Tuominen, Raimo K.; Yli-Kauhaluoma, Jari [Journal of Medicinal Chemistry, 2009, vol. 52, # 13, p. 3969 - 3981]
[2]González, Myriam; Alcolea, Pedro José; Álvarez, Raquel; Medarde, Manuel; Larraga, Vicente; Peláez, Rafael [International Journal for Parasitology: Drugs and Drug Resistance, 2021, vol. 16, p. 45 - 64]
[3]Chen, Xu-Ling; Ai, Bai-Ru; Dong, Yu; Zhang, Xiao-Mei; Wang, Ji-Yu [Tetrahedron Letters, 2017, vol. 58, # 37, p. 3646 - 3649]

37
[ 99-34-3 ]
[ 18107-18-1 ]
[ 2702-58-1 ]

Yield	Reaction Conditions	Operation in experiment
91%	In methanol; diethyl ether; toluene at 20℃; for 1h;

Reference： [1]Legouin, Beatrice; Gayral, Maud; Uriac, Philippe; Cupif, Jean-Francois; Levoin, Nicolas; Toupet, Loic; Van De Weghe, Pierre [European Journal of Organic Chemistry, 2010, # 28, p. 5503 - 5508]

38
[ 2702-58-1 ]
[ 3908-55-2 ]
[ 1260491-64-2 ]

Yield	Reaction Conditions	Operation in experiment
20%	Stage #1: methyl 3,5-dinitrobenzoate With caesium carbonate In dimethyl sulfoxide Stage #2: Trimethyl(methylthio)silane In dimethyl sulfoxide at 20℃; for 16h;

Reference： [1]Location in patent: scheme or table Qiao, Qi; Dominique, Romyr; Sidduri, Achyutharao; Lou, Jianping; Goodnow, Robert A. [Synthetic Communications, 2010, vol. 40, # 24, p. 3691 - 3698]

39
[ 67-56-1 ]
[ 2702-58-1 ]
[ 78238-13-8 ]

Yield	Reaction Conditions	Operation in experiment
97%	Stage #1: methanol With lithium at 0℃; Inert atmosphere; Stage #2: methyl 3,5-dinitrobenzoate Reflux; Inert atmosphere;