Name: 875-79-6|1,2-Dimethyl-1H-indole|98%
Brand: Ambeed
SKU: A153109
Price: 13.0 USD
Availability: InStock
Rating: 99 (27 reviews)

1
[ 95-20-5 ]
[ 74-88-4 ]
[ 875-79-6 ]

Yield	Reaction Conditions	Operation in experiment
97%	Stage #1: 2-methyl-1H-indole With sodium hydride In N,N-dimethyl-formamide at 0℃; for 0.5h; Stage #2: iodomethane In N,N-dimethyl-formamide at 0 - 20℃; for 16h;
94%	Stage #1: 2-methyl-1H-indole With sodium hydride In tetrahydrofuran; mineral oil at 0 - 20℃; for 1.75h; Inert atmosphere; Stage #2: iodomethane In tetrahydrofuran; mineral oil at 0 - 20℃; Inert atmosphere;
94%	Stage #1: 2-methyl-1H-indole With sodium hydride In tetrahydrofuran; mineral oil at 0 - 20℃; for 1.75h; Inert atmosphere; Stage #2: iodomethane In tetrahydrofuran; mineral oil at 20℃; Inert atmosphere;

90%	With ammonia; natrium In diethyl ether
89%	Stage #1: 2-methyl-1H-indole With sodium hydride In tetrahydrofuran at 0℃; for 1h; Inert atmosphere; Stage #2: iodomethane In tetrahydrofuran at 20℃; Inert atmosphere;
87%	Stage #1: 2-methyl-1H-indole With sodium hydride In acetonitrile at 0℃; for 0.5h; Stage #2: iodomethane In acetonitrile at 0 - 20℃; for 16h;
85%	With sodium hydroxide In N,N-dimethyl-formamide at 20℃; for 0.333333h; Inert atmosphere;
84%	Stage #1: 2-methyl-1H-indole With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0 - 20℃; Inert atmosphere; Stage #2: iodomethane In N,N-dimethyl-formamide; mineral oil at 0 - 20℃; Inert atmosphere;
84%	Stage #1: 2-methyl-1H-indole With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0℃; for 0.5h; Inert atmosphere; Stage #2: iodomethane In N,N-dimethyl-formamide; mineral oil at 0 - 20℃; Inert atmosphere;
83%	Stage #1: 2-methyl-1H-indole With sodium hydride In tetrahydrofuran; mineral oil at 0 - 20℃; for 0.5h; Inert atmosphere; Stage #2: iodomethane In tetrahydrofuran; mineral oil at 0 - 20℃; for 4h; Inert atmosphere;	1,2-dimethyl-1H-indole (1c) To a stirred solution of 2-methylindole (1 equiv., 1.12 g, 8.5 mmol) in dry THF (20 mL), NaH (1.2 equiv., 0.41 g, 10.2 mmol) 60% dispersion in mineral oil was added portionwise under argon atmosphere at 0 °C. The reaction mixture was then warmed to room temperature and stirred for 30 min. After cooling again to 0 °C, MeI (1.2 equiv., 0.64 mL, 10.2 mmol) was added dropwise to the reaction mixture which was then warmed to room temperature and stirred for 4 hours. The reaction was quenched with water and the aqueous layer was extracted with DCM. The combined organic layers were washed with brine, dried over anhydrous Na2SO4 and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel using Pentane/EtOAc [98:02] as eluent, affording the expected compound as a white solid (83% yield, 1.02 g, 7.06 mmol). 1H NMR (400 MHz, CDCl3) 7.50 (d, J = 8.0 Hz, 1H), 7.24 (d, J = 8.0 Hz, 1H), 7.13 (ddd, J = 8.0, 7.0, 1.1 Hz, 1H), 7.05 (ddd, J = 8.0, 7.0, 1.1 Hz, 1H), 6.23 (s, 1H), 3.65 (s, 3H), 2.41 (d, J = 0.6 Hz, 3H). Data are consistent with reported literature values.
80%	Stage #1: 2-methyl-1H-indole With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0 - 20℃; Inert atmosphere; Stage #2: iodomethane In N,N-dimethyl-formamide; mineral oil at 0 - 20℃; Inert atmosphere;
75%	Stage #1: 2-methyl-1H-indole With sodium hydride In tetrahydrofuran for 1.5h; Inert atmosphere; Stage #2: iodomethane In tetrahydrofuran at 0℃; Inert atmosphere;	1,2-Dimethylindole This compound is known and has been characterised; Indole Naphthyridinones as Inhibitors of Bacterial Enoyl-ACP Reductases FabI and FabK. M. A. Seefeld, W. H.Miller, K. A. Newlander, W. J. Burgess, W. E. DeWolf, P. A. Elkins, M. S. Head, D.R. Jakas, C. A. Janson, P. M. Keller, P. J. Manley, T. D. Moore, D. J. Payne, S. Pearson,B. J. Polizzi, X. Qiu, S. F. Rittenhouse, I. N. Uzinskas, N. G. Wallis and W. F. Huffman,J. Med. Chem. 2003, 46, 1627-1635.To a solution of 2-methyl-1H-indole (377 mg, 2.88 mmol) in dry THF (10 mL) was added NaH (60% wt, 173 mg, 4.32 mmol). After stirring for 1.5 h, the solution was cooled to 0 °C and methyliodide (406 mg, 2.88 mmol) was added. The reaction was left to stir overnight and was quenched with sat. NH4Cl (50 mL). Following extraction with EtOAc (3 x 50 mL), the organic extracts were combined, dried over MgSO4, filtered and the solvent removed in vacuo by rotary evaporation to give the crude product. Purification by column chromatography gradient elution 0-4% EtOAc in Pet. ether gavethe product as an off-white solid (312 mg, 2.15 mmol, 75%)
73%	Stage #1: 2-methyl-1H-indole With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0 - 20℃; for 1.25h; Inert atmosphere; Stage #2: iodomethane In N,N-dimethyl-formamide; mineral oil at 0 - 20℃; for 0.5h;
70%	With thallium(I) ethanolate In benzene Heating;
68%	Stage #1: 2-methyl-1H-indole With sodium hydride In N,N-dimethyl-formamide at 20℃; for 1h; Inert atmosphere; Schlenk technique; Stage #2: iodomethane In N,N-dimethyl-formamide at 20℃;
59.8%	With potassium-t-butoxide In diethyl ether at 0℃; for 24h;
59.8%	With potassium-t-butoxide In diethyl ether at 0℃; for 24h;
58%	Stage #1: 2-methyl-1H-indole With sodium hydride In N,N-dimethyl-formamide; mineral oil at 20℃; for 0.5h; Inert atmosphere; Stage #2: iodomethane In N,N-dimethyl-formamide; mineral oil at 0 - 20℃; Inert atmosphere;
48%	Stage #1: 2-methyl-1H-indole With sodium hydride In N,N-dimethyl-formamide; mineral oil at -30℃; for 0.833333h; Stage #2: iodomethane In N,N-dimethyl-formamide; mineral oil at -30 - 20℃;	1 Example 1: Alkylation of bicyclic ring system pyrrole nitrogen (method A)General Scheme 1 :Preparation of intermediate i[00259] To a solution of 2-methyl-lH-indole (lg, 7.6 mmol) in DMF (300 mL), at -30 °C, was added NaH (60% in mineral oil, 365 mg, 9.12 mmol). The reaction mixture was stirred at -30 °C for 50 min, followed by the addition of iodomethane (0.515 mL, 8.36 mmol). The reaction mixture was stirred at -30 °C for 30 min and slowly allowed to warm up to room temperature. The reaction mixture was then stirred at room temperature overnight. The reaction was quenched by adding water (400 mL) and the mixture was extracted with DCM (3 x 100 mL). The organic layers were combined, washed with brine, dried over MgS04, filtered and concentrated under reduced pressure. The crude product was purified by silica gel flash chromatography (20-70% EtOAc in Hexanes) to give 1,2-dimethyl-lH-indole (529.9 mg, 48%). NMR (CDCI3 4OO MHz) δ 7.50 (d, 1H), 7.22 (d, lH), 7.15-7.1 1 (m, 1H), 7.07-7.05 (m, 1H), 6.23 (s, 1H), 3.60 (s, 3H), 2.39 (s, 3H).
30%	Stage #1: 2-methyl-1H-indole With sodium hydride In tetrahydrofuran at 0℃; for 0.333333h; Schlenk technique; Inert atmosphere; Stage #2: iodomethane In tetrahydrofuran at 0 - 20℃; Inert atmosphere; Schlenk technique;
	With diethyl ether; ammonia; natrium; iron nitrate (III)
	With potassium hydroxide 1.) acetone, 2.) room temp., 10 min; Yield given. Multistep reaction;
	With sodium hydride 1.) DMF, 0 deg C, 30 min, 2.) DMF, RT, 16 h; Multistep reaction;
	Stage #1: 2-methyl-1H-indole With sodium hydride In N,N-dimethyl-formamide; paraffin oil at 0℃; for 0.5h; Stage #2: iodomethane In N,N-dimethyl-formamide; paraffin oil at 0 - 20℃;
	Stage #1: 2-methyl-1H-indole With potassium hydroxide In N,N-dimethyl-formamide Stage #2: iodomethane In N,N-dimethyl-formamide at 20℃;
	With sodium hydride In N,N-dimethyl-formamide at 0℃; for 1h;
	With sodium hydride In tetrahydrofuran
	With sodium hydride In N,N-dimethyl-formamide Inert atmosphere;
	Stage #1: 2-methyl-1H-indole With sodium hydride In tetrahydrofuran; mineral oil at 0 - 20℃; for 0.5h; Stage #2: iodomethane In tetrahydrofuran-d8; mineral oil at 0 - 20℃;
	Stage #1: 2-methyl-1H-indole With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0℃; Inert atmosphere; Stage #2: iodomethane In N,N-dimethyl-formamide; mineral oil Inert atmosphere;
	Stage #1: 2-methyl-1H-indole With sodium hydride In dimethyl sulfoxide; mineral oil at 20℃; for 2h; Inert atmosphere; Stage #2: iodomethane In dimethyl sulfoxide; mineral oil for 2h; Inert atmosphere;
	With potassium hydroxide In dimethyl sulfoxide
	Stage #1: 2-methyl-1H-indole With sodium hydride In tetrahydrofuran for 0.5h; Darkness; Stage #2: iodomethane In tetrahydrofuran at 0 - 20℃; for 12h;	5.1.2 Synthesis of N-methylindole analogues 2a-i General procedure: To a solution of indoles 1a-i (10mmol) in dry tetrahydrofuran (THF; 25mL), NaH (30mmol) was added. After the mixture was stirred 30min, CH3I (30mmol) in 5mL THF was added dropwise under 0°C. The reaction mixture was stirred at room temperature for 12h in the dark. Then the reaction mixture was cooled to room temperature,diluted with 30mL saturated NH4Cl solution, and extracted with EtOAc (3×30mL). The organic layer dried over anhydrous MgSO4 and concentrated in vacuo. The pure products 2a-i was obtained by column chromatography on silica gel (Petroleum ether/EtOAc=20:1) with yield of 90%-99%.
	Stage #1: 2-methyl-1H-indole With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0 - 20℃; for 0.5h; Stage #2: iodomethane In N,N-dimethyl-formamide; mineral oil at 0 - 20℃;
	Stage #1: 2-methyl-1H-indole With sodium hydride In N,N-dimethyl-formamide at 0 - 20℃; for 0.5h; Inert atmosphere; Stage #2: iodomethane In N,N-dimethyl-formamide at 0 - 20℃; for 1h; Inert atmosphere;
	With potassium hydroxide In dimethyl sulfoxide at 20℃;
	Stage #1: 2-methyl-1H-indole With potassium hydroxide In N,N-dimethyl-formamide at 20℃; for 1.5h; Inert atmosphere; Schlenk technique; Stage #2: iodomethane In N,N-dimethyl-formamide at 0 - 20℃; Inert atmosphere; Schlenk technique;
	Stage #1: 2-methyl-1H-indole With sodium hydride In N,N-dimethyl-formamide; mineral oil at 20℃; Inert atmosphere; Cooling; Stage #2: iodomethane In N,N-dimethyl-formamide; mineral oil at 20℃; for 12h; Cooling; Inert atmosphere;
	Stage #1: 2-methyl-1H-indole With sodium hydride In N,N-dimethyl-formamide at 0℃; for 0.5h; Schlenk technique; Inert atmosphere; Stage #2: iodomethane In N,N-dimethyl-formamide at 0 - 20℃; Schlenk technique; Inert atmosphere;
	Stage #1: 2-methyl-1H-indole With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0 - 20℃; for 1.25h; Stage #2: iodomethane In N,N-dimethyl-formamide; mineral oil at 0 - 20℃; for 0.5h;
	Stage #1: 2-methyl-1H-indole With sodium hydride In N,N-dimethyl-formamide at 0 - 20℃; for 0.5h; Stage #2: iodomethane In N,N-dimethyl-formamide at 20℃;	2. General procedure for the synthesis of N-protected indoles from substituted indoles with alkylbromidesthe synthesis of N-methylindoles General procedure: To a stirred solution of indole 120 mg1 mmol in dry DMF (2.5 mL), NaH 64 mg1.6 mmol was addedslowly at 0. The reaction mixture was then warmed to room temperature and stirred for 30 min. After cooling to0 again, iodomethane 76 uL (1.2 mmol) was added dropwise. The reaction mixture was warmed to roomtemperature again and stirred overnight. The reaction was determined to be completed via TLC, the mixture wasquenched with water and the aqueous layer was extracted with ethyl acetate. The combined organic layer waswashed with saturated brine, dried over anhydrous Na2SO4 and concentrated under vacuum. The residue waspurified by flash column chromatography to give the corresponding N-methylindoles.

Reference： [1]Seefeld, Mark A.; Miller, William H.; Newlander, Kenneth A.; Burgess, Walter J.; DeWolf Jr., Walter E.; Elkins, Patricia A.; Head, Martha S.; Jakas, Dalia R.; Janson, Cheryl A.; Keller, Paul M.; Manley, Peter J.; Moore, Terrance D.; Payne, David J.; Pearson, Stewart; Polizzi, Brian J.; Qiu, Xiayang; Rittenhouse, Stephen F.; Uzinskas, Irene N.; Wallis, Nicola G.; Huffman, William F. [Journal of Medicinal Chemistry, 2003, vol. 46, # 9, p. 1627 - 1635]
[2]Caramenti, Paola; Nicolai, Stefano; Waser, Jerome [Chemistry - A European Journal, 2017, vol. 23, # 59, p. 14702 - 14706]
[3]Caramenti, Paola; Nandi, Raj Kumar; Waser, Jerome [Chemistry - A European Journal, 2018, vol. 24, # 40, p. 10049 - 10053]
[4]Davis, Paul D.; Neckers, Douglas C. [Journal of Organic Chemistry, 1980, vol. 45, # 3, p. 456 - 462]
[5]Klare, Hendrik F. T.; Oestreich, Martin; Ito, Jun-Ichi; Nishiyama, Hisao; Ohki, Yasuhiro; Tatsumi, Kazuyuki [Journal of the American Chemical Society, 2011, vol. 133, # 10, p. 3312 - 3315]
[6]Ciszewski, Lukasz W.; Durka, Jakub; Gryko, Dorota [Organic Letters, 2019, vol. 21, # 17, p. 7028 - 7032]
[7]Song, Xiaoning; Xu, Cong; Du, Dongxu; Zhao, Ziming; Zhu, Dongsheng; Wang, Mang [Organic Letters, 2017, vol. 19, # 24, p. 6542 - 6545]
[8]Xu, Xiu-Hua; Liu, Guo-Kai; Azuma, Ayaka; Tokunaga, Etsuko; Shibata, Norio [Organic Letters, 2011, vol. 13, # 18, p. 4854 - 4857]
[9]Dissanayake, Isuru; Hart, Jacob D.; Becroft, Emma C.; Sumby, Christopher J.; Newton, Christopher G. [Journal of the American Chemical Society, 2020, vol. 142, # 31, p. 13328 - 13333]
[10]Guillemard, Lucas; Jacob, Nicolas; Wencel-Delord, Joanna [Synthesis, 2020, vol. 52, # 4, p. 574 - 580]
[11]Chen, Min; Huang, Zhi-Tang; Zheng, Qi-Yu [Chemical Communications, 2012, vol. 48, # 95, p. 11686 - 11688,3]
[12]Barrios-Rivera, Jonathan; Xu, Yingjian; Clarkson, Guy J.; Wills, Martin [Tetrahedron, 2022, vol. 103]
[13]Hong, Xiaohu; Tan, Qitao; Liu, Bingxin; Xu, Bin [Angewandte Chemie - International Edition, 2017, vol. 56, # 14, p. 3961 - 3965][Angew. Chem., 2017, vol. 129, # 14, p. 4019 - 4023,5]
[14]Shafiee, A.; Sattari, S. [Synthesis, 1981, # 5, p. 389 - 390]
[15]Stahl, Timo; Muether, Kristine; Ohki, Yasuhiro; Tatsumi, Kazuyuki; Oestreich, Martin [Journal of the American Chemical Society, 2013, vol. 135, # 30, p. 10978 - 10981]
[16]Ji, Yuan-Zhao; Li, Hui-Jing; Zhang, Jin-Yu; Wu, Yan-Chao [Chemical Communications, 2019, vol. 55, # 79, p. 11864 - 11867]
[17]Ji, Yuan-Zhao; Li, Hui-Jing; Wang, Yi-Ruo; Wu, Yan-Chao; Zhang, Zheng-Yan [Advanced synthesis and catalysis, 2020]
[18]Taylor, James E.; Jones, Matthew D.; Williams, Jonathan M. J.; Bull, Steven D. [Organic Letters, 2010, vol. 12, # 24, p. 5740 - 5743]
[19]Current Patent Assignee: IRONWOOD PHARMACEUTICALS INC - WO2011/100359, 2011, A1 Location in patent: Page/Page column 70
[20]Klussmann, Martin; Lux, Marcel [Organic Letters, 2020]
[21]Potts; Saxton [Journal of the Chemical Society, 1954, p. 2641]
[22]Kikugawa, Yasuo; Miyake, Yuko [Synthesis, 1981, # 6, p. 461 - 462]
[23]Davis, Peter D.; Hill, Christopher H.; Lawton, Geoffrey; Nixon, John S.; Wilkinson, Sandra E.; et al. [Journal of Medicinal Chemistry, 1992, vol. 35, # 1, p. 177 - 184]
[24]Johansen, Michael B.; Kerr, Michael A. [Organic Letters, 2010, vol. 12, # 21, p. 4956 - 4959]
[25]Zhang, Hua; Liu, Dong; Chen, Caiyou; Liu, Chao; Lei, Aiwen [Chemistry - A European Journal, 2011, vol. 17, # 35, p. 9581 - 9585]
[26]Location in patent: scheme or table Sashidhara, Koneni V.; Kumar, Manoj; Sonkar, Ravi; Singh, Bhanu Shankar; Khanna; Bhatia, Gitika [Journal of Medicinal Chemistry, 2012, vol. 55, # 6, p. 2769 - 2779]
[27]Gong, Tian-Jun; Cheng, Wan-Min; Su, Wei; Xiao, Bin; Fu, Yao [Tetrahedron Letters, 2014, vol. 55, # 11, p. 1859 - 1862]
[28]Alford, Joshua S.; Davies, Huw M. L. [Journal of the American Chemical Society, 2014, vol. 136, # 29, p. 10266 - 10269]
[29]Lanke, Veeranjaneyulu; Bettadapur, Kiran R.; Prabhu, Kandikere Ramaiah [Organic Letters, 2016, vol. 18, # 21, p. 5496 - 5499]
[30]Singh, Rahulkumar Rajmani; Liu, Rai-Shung [Chemical Communications, 2017, vol. 53, # 33, p. 4593 - 4596]
[31]Yan, Guobing; Cao, Xihan; Zheng, Wanbin; Ke, Qiumin; Zhang, Jieyu; Huang, Dayun [Organic and Biomolecular Chemistry, 2017, vol. 15, # 28, p. 5904 - 5907]
[32]Qiao, Chang; Liu, Xiao-Fang; Fu, Hong-Chen; Yang, Hao-Peng; Zhang, Zhi-Bo; He, Liang-Nian [Chemistry - An Asian Journal, 2018, vol. 13, # 18, p. 2664 - 2670]
[33]Xia, Qinqin; Bao, Xiaodong; Sun, Chuchu; Wu, Di; Rong, Xiaona; Liu, Zhiguo; Gu, Yugui; Zhou, Jianmin; Liang, Guang [European Journal of Medicinal Chemistry, 2018, vol. 160, p. 120 - 132]
[34]Zhang, Jun; Torabi Kohlbouni, Saeedeh; Borhan, Babak [Organic Letters, 2019, vol. 21, # 1, p. 14 - 17] Lin, Dian-Zhao; Huang, Jing-Mei [Organic Letters, 2019, vol. 21, # 15, p. 5862 - 5866]
[35]Jeon, Jinwon; Ryu, Ho; Lee, Changseok; Cho, Dasol; Baik, Mu-Hyun; Hong, Sungwoo [Journal of the American Chemical Society, 2019] Jeon, Jinwon; Ryu, Ho; Lee, Changseok; Cho, Dasol; Baik, Mu-Hyun; Hong, Sungwoo [Journal of the American Chemical Society, 2019, vol. 141, # 25, p. 10048 - 10059]
[36]Yang, Liquan; Liu, Zhaoran; Li, Yujun; Lei, Ning; Shen, Yanling; Zheng, Ke [Organic Letters, 2019, vol. 21, # 19, p. 7702 - 7707]
[37]Medina-Mercado, Ignacio; Asomoza-Solís, Eric Omar; Martínez-González, Eduardo; Ugalde-Saldívar, Victor Manuel; Ledesma-Olvera, Lydia Gabriela; Barquera-Lozada, José Enrique; Gómez-Vidales, Virginia; Barroso-Flores, Joaquín; Frontana-Uribe, Bernardo A.; Porcel, Susana [Chemistry - A European Journal, 2020, vol. 26, # 3, p. 634 - 642]
[38]Duan, Shengguo; Zhang, Wan; Hu, Yuntong; Xu, Ze-Feng; Li, Chuan-Ying [Advanced Synthesis and Catalysis, 2020, vol. 362, # 17, p. 3570 - 3575]
[39]Nag, Ekta; Gorantla, Sai Manoj N. V. T.; Arumugam, Selvakumar; Kulkarni, Aditya; Mondal, Kartik Chandra; Roy, Sudipta [Organic Letters, 2020, vol. 22, # 16, p. 6313 - 6318]
[40]Gu, Xiaoting; Liang, Taoyuan; Wei, Wanxing; Zhang, Xiaoxiang; Zhang, Yingying; Zhang, Zhuan [Organic and Biomolecular Chemistry, 2021, vol. 19, # 47, p. 10403 - 10407] Guan, Rongqing; Zhao, He; Zhang, Min [Organic Letters, 2022, vol. 24, # 16, p. 3048 - 3052]
[41]Zhao, Yin; Li, Hongfang; Yin, Shan; Wu, Yandan; Ni, Guanghui [Synlett, 2022, vol. 33, # 7, p. 659 - 663]

2
[ 875-79-6 ]
[ 26216-93-3 ]

Yield	Reaction Conditions	Operation in experiment
98%	With hydrogen; tris(pentafluorophenyl)borane In ⁽²⁾H₈-toluene at 80℃; for 18h;
64%	With indium; ammonium chloride In ethanol Heating;
44%	With tetrabutylammonium borohydride In dichloromethane for 10h; Heating;

	With hydrogenchloride; zinc
	With hydrogenchloride; tin Hydrogenation;
	With 1,4-dioxane; copper oxide-chromium oxide at 170℃; Hydrogenation;
33 %Chromat.	With tris(pentafluorophenyl)borate; hydrogen In toluene at 80℃; for 18h;	5 The hydrogenation reaction according to the present invention 1,2-dimethylindole (58.7, 0.80 mmol), tris (pentafluorophenyl) borane (20.5 mg, 0.04 mmol) and toluene (3.0 ml) were added to a pressure resistant vessel under a nitrogen atmosphere.Thereafter, the interior of the pressure-resistant container was replaced with a crude hydrogen gas [H 2 (2.5 atm), CO (2.5 atm)] and heated at 80 ° C. for 18 hours. Using this reaction solution, the yield was determined from the peak area ratio of the starting material and the product by gas chromatography analysis (FID). As a result, 1,2-dimethylindoline was obtained in a yield of 33% by a hydrogenation reaction.
	With 1,4-dioxane; copper oxide-chromium oxide at 170℃; Hydrogenation;

Reference： [1]Location in patent: scheme or table Stephan, Douglas W.; Greenberg, Sharonna; Graham, Todd W.; Chase, Preston; Hastie, Jeff J.; Geier, Stephen J.; Farrell, Jeffrey M.; Brown, Christopher C.; Heiden, Zachariah M.; Welch, Gregory C.; Ullrich, Matthias [Inorganic Chemistry, 2011, vol. 50, # 24, p. 12338 - 12348]
[2]Pitts; Harrison; Moody [Journal of the Chemical Society. Perkin Transactions 1 (2001), 2001, # 9, p. 955 - 977]
[3]Wakamatsu, Takeshi; Inaki, Harumi; Ogawa, Akemi; Watanabe, Masako; Ban, Yoshio [Heterocycles, 1980, vol. 14, # 10, p. 1441 - 1444]
[4]v. Braun; Bayer; Blessing [Chemische Berichte, 1924, vol. 57, p. 400]
[5]Cockerill et al. [Journal of the Chemical Society, 1955, p. 4369,4372]
[6]Adkins; Coonradt [Journal of the American Chemical Society, 1941, vol. 63, p. 1563,1568]
[7]Current Patent Assignee: NIPPON SHOKUBAI CO LTD - JP2017/206474, 2017, A Location in patent: Paragraph 0052
[8]Current Patent Assignee: I.G. Farbenind. - DE623693, 1934, C [Fortschr. Teerfarbenfabr. Verw. Industriezweige, vol. 22, p. 333][Fortschr. Teerfarbenfabr. Verw. Industriezweige, vol. 22, p. 333]

3
[ 96-45-7 ]
[ 875-79-6 ]
[ 55107-83-0 ]

Yield	Reaction Conditions	Operation in experiment
91%	With iodine; potassium iodide In methanol; water Ambient temperature;
	With potassium iodide; iodine In methanol; water	21 EXAMPLE 21 EXAMPLE 21 To a stirred solution of 3.6 g 1,2-dimethylindole and 2.55 g 2-imidazolidinethione in 80 ml methanol is added a solution of 6.35 g iodine and 13 g potassium iodide in 50 ml water. After 1 hour at room temperature, the solution is concentrated in vacuo until crystals separate, then cooled and filtered. The precipitate is washed with water and ether and is recrystallized from alcohol to give 1,2-dimethyl-3-(2-imidazolin-2-ylthio)-indole hydriodide melting at 203°-205° (with decomposition).

Reference： [1]Nagarajan, K.; Arya, V. P.; Parthasarathy, T. N.; Shenoy, S. J.; Shah, R. K.; Kulkarni, Y. S. [Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 1981, vol. 20, # 8, p. 672 - 679]
[2]Current Patent Assignee: NOVARTIS AG; Novartis (w/o Sandoz) - US3954757, 1976, A

4
[ 2055-46-1 ]
[ 875-79-6 ]
[ 55107-80-7 ]

Yield	Reaction Conditions	Operation in experiment
65%	With iodine; potassium iodide In methanol; water Ambient temperature;

Reference： [1]Nagarajan, K.; Arya, V. P.; Parthasarathy, T. N.; Shenoy, S. J.; Shah, R. K.; Kulkarni, Y. S. [Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 1981, vol. 20, # 8, p. 672 - 679]

5
[ 95-20-5 ]
[ 74-88-4 ]
[ 3484-18-2 ]
[ 875-79-6 ]
[ 65136-45-0 ]

Reference： [1]Journal of the Chemical Society. Perkin transactions I,1990,p. 179 - 180
[2]Journal of the Chemical Society. Perkin transactions I,1990,p. 179 - 180

6
[ 10602-37-6 ]
[ 875-79-6 ]
[ 88848-25-3 ]

Yield	Reaction Conditions	Operation in experiment
44%	With acetyl chloride In benzene for 17h; Ambient temperature;

Reference： [1]Galiullina, T. N.; Abramenko, P. I. [Chemistry of Heterocyclic Compounds, 1983, vol. 19, # 12, p. 1306 - 1310][Khimiya Geterotsiklicheskikh Soedinenii, 1983, vol. 19, # 12, p. 1652 - 1656]

7
[ 875-79-6 ]
[ 950-81-2 ]
<4-Antipyryl-><1,2-dimethyl-3-indolyl->carbenium-tetrafluoroborate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
89%	With tetrafluoroboric acid In diethyl ether; dichloromethane for 0.5h;

Reference： [1]Akguen, Eyuep; Tunali, Mustafa [Archiv der Pharmazie, 1988, vol. 321, p. 9 - 11]

8
[ 875-79-6 ]
[ 950-81-2 ]
3,3'-Di(1,2-dimethyl-indolyl)-4-(4-antipyryl)methane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
67%	In methanol for 1h;

Reference： [1]Akguen, Eyuep; Tunali, Mustafa [Archiv der Pharmazie, 1988, vol. 321, p. 921 - 924]

9
[ 875-79-6 ]
[ 29582-31-8 ]
[ 78860-81-8 ]

Yield	Reaction Conditions	Operation in experiment
89%	In benzene for 10h; Heating;

Reference： [1]Sayed, G. H.; Elhalim, M. S. Abd [Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 1981, vol. 20, # 5, p. 424 - 426]

10
[ 875-79-6 ]
[ 74808-09-6 ]
[ 108894-45-7 ]

Yield	Reaction Conditions	Operation in experiment
83%	Stage #1: 1,2-dimethylindole; 2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl trichloroacetimidate In dichloromethane at -10℃; for 0.0833333h; Inert atmosphere; Stage #2: With tris(pentafluorophenyl)borate In dichloromethane at -10℃; Inert atmosphere;
59%	With 4 A molecular sieve; zinc(II) chloride In benzene for 0.833333h; Ambient temperature;

Reference： [1]Dubey, Atul; Tiwari, Ashwani; Mandal, Pintu Kumar [Journal of Organic Chemistry, 2021, vol. 86, # 12, p. 8516 - 8526]
[2]Schmidt, Richard R.; Effenberger, Gunther [Liebigs Annalen der Chemie, 1987, p. 825 - 832]

11
[ 875-79-6 ]
[ 33513-42-7 ]
[ 38292-40-9 ]

Yield	Reaction Conditions	Operation in experiment
95%	Stage #1: N,N-dimethyl-formamide With oxalyl dichloride at 0℃; for 1h; Stage #2: 1,2-dimethylindole In N,N-dimethyl-formamide at 20℃; for 5h; Stage #3: With sodium hydroxide In N,N-dimethyl-formamide at 100℃; for 0.166667h;	5.2.1. General procedure for syntheses of compounds (4a-k) General procedure: Oxalyl chloride (0.3 mL) was added in a drop-wise manner to cooled (ice-bath) DMF (3 mL) under stirring. The mixture was then stirred at 0 °C for 1 h. A solution of the substituted indole (4 mmol) in DMF (1.5 mL) was then added to the reaction mixture in a dropwise manner. The resulting mixture was stirred at room temperature for 5 h. A 2 N solution of sodium hydroxide (2 mL) was then added, and the mixture was heated at 100 °C for 10 min. The mixture was then cooled and extracted with ethyl acetate (3 X 50 mL). The organic layers were combined and washed with sequentially water and brine. The organics were dried (Na2SO4) and distilled to dryness to give the crude residue, which was purified by flash column chromatography using ethyl acetate/petroleum ether (3:1, v/v) as the eluent to give pure indole-3-carbaldehyde (4a-k).
91%	With trichlorophosphate at 20℃; for 2h;
63.37%	Stage #1: N,N-dimethyl-formamide With trichlorophosphate for 0.25h; Cooling with ice; Stage #2: 1,2-dimethylindole In N,N-dimethyl-formamide at 20℃; for 3h;	44.1 1) Synthesis of 44a Phosphorus oxychloride (633.54 mg, 4.13 mmol) was slowly added dropwise to DMF (302.04 mg, 4.13 mmol) under ice bath, and stirred for 15 min.1,2-dimethylindole (500 mg, 3.44 mmol) dissolved in 5 mL of DMF was slowly added dropwise, and then transferred to room temperature for 3 hours;After the reaction was completed, 5 mL of water was added, and a white solid appeared after shaking.Drying the solid after suction filtration is Compound 44a (378.2 mg)The yield was 63.37%.

	Yield given. Multistep reaction;
	With trichlorophosphate at 0℃; for 0.5h; Sealed tube;
	With trichlorophosphate at 0 - 40℃; for 1.16667h;

Reference： [1]Zheng, Jing; Deng, Lijuan; Chen, Minfeng; Xiao, Xuzhi; Xiao, Shengwei; Guo, Cuiping; Xiao, Gaokeng; Bai, Liangliang; Ye, Wencai; Zhang, Dongmei; Chen, Heru [European Journal of Medicinal Chemistry, 2013, vol. 65, p. 158 - 167]
[2]Seefeld, Mark A.; Miller, William H.; Newlander, Kenneth A.; Burgess, Walter J.; DeWolf Jr., Walter E.; Elkins, Patricia A.; Head, Martha S.; Jakas, Dalia R.; Janson, Cheryl A.; Keller, Paul M.; Manley, Peter J.; Moore, Terrance D.; Payne, David J.; Pearson, Stewart; Polizzi, Brian J.; Qiu, Xiayang; Rittenhouse, Stephen F.; Uzinskas, Irene N.; Wallis, Nicola G.; Huffman, William F. [Journal of Medicinal Chemistry, 2003, vol. 46, # 9, p. 1627 - 1635]
[3]Current Patent Assignee: ZHENGZHOU UNIVERSITY; ZHEJIANG UNIVERSITY - CN110156729, 2019, A Location in patent: Paragraph 0143-0146
[4]Downie, Ian M.; Earle, Martyn J.; Heaney, Harry; Shuhaibar, Khamis F. [Tetrahedron, 1993, vol. 49, # 19, p. 4015 - 4034]
[5]Rassu, Gloria; Curti, Claudio; Zambrano, Vincenzo; Pinna, Luigi; Brindani, Nicoletta; Pelosi, Giorgio; Zanardi, Franca [Chemistry - A European Journal, 2016, vol. 22, # 36, p. 12637 - 12640]
[6]Varlet, Thomas; Matišić, Mateja; Van Elslande, Elsa; Neuville, Luc; Gandon, Vincent; Masson, Géraldine [Journal of the American Chemical Society, 2021, vol. 143, # 30, p. 11611 - 11619]

12
[ 875-79-6 ]
[ 80906-24-7 ]

Yield	Reaction Conditions	Operation in experiment
95%	With hydrogen bromide; dimethyl sulfoxide In water; ethyl acetate at 60℃; for 0.25h;
68%	With N-Bromosuccinimide In tetrahydrofuran at 20℃; for 24h;	2.1.9. 3-Bromo-1,2-dimethylindole (9) To a stirred THF solution (60 mL) of compound 8 (2.18 g,15 mmol) at room temperaturewas slowly added N-bromosuccinimide (NBS) (3.0 g, 16.86 mmol). After the stirring was continued for 24 h, the mixture was poured into water slowly. After being extracted with ether, the organic layer was washed with water. Then the organiclayer was dried over anhydrous MgSO4, filtered, and concentrated.The crude product was purified by column chromatography on silica gel using petroleum ether as eluent to afford 2.3 g of compound 9 visible as a white solid with a 68% yield. 1H NMR (400 MHz, CDCl3): δ 2.45 (s, 3H, -CH3), 3.71 (s, 3H, -CH3), 7.15 (t,1H, J=7.26 Hz, phenyl-H), 7.21 (t,1H, J=7.42 Hz, phenyl-H), 7.26 (d,1H, J=7.59 Hz, phenyl-H), 7.49 (d, 1H, J=7.76 Hz, phenyl-H).
64%	With tetrabutylammomium bromide; sodium hydrogencarbonate; Selectfluor In toluene at 20℃; for 2h; Schlenk technique; regioselective reaction;	General procedure: 1-methyl-2-phenyl-1H-indole 1a (42 mg, 0.2 mmol), TBAB (71 mg, 0.22 mmol),NaHCO3 (16.8 mg, 0.2 mmol) and selectfluor (142 mg, 0.4 mmol ) were added to a Schlenk. After that 2 mL toluene was added to the mixture. The resulting mixture reacted at the room temperature for 2 h as monitored by TLC. The mixture was diluted with ethyl acetate(10 mL) and then evaporated. The residue was purified by flash chromatography on silica gel column (petroleum ether :ethyl acetate = 50:1) to afford 55.2 mg (96%) of 2a.

56%	With N-Bromosuccinimide In tetrahydrofuran at -0.16℃; for 20h;	Synthesis of 3-bromo-1,2-dimethylindole General procedure: To a stirred THF solution (100.0 mL) containingcompound 4a(1.50 g, 10.30 mmol) was slowly added 2.00 g N-bromosullirimide (11.40 mmol) at 273 K. The reactionmixture was stirred for 20 h, then was poured into sodium thiosulfate solutionand extracted with diethyl ether. The organic layer was dried, filtrated, andconcentrated. The residue was purified by column chromatography using petroleum ether as the eluent to give 1.20 g of 4a as light purple solid in 56%yield. 1H NMR (400 MHz, CDCl3, TMS): δ2.42 (s, 3H, -CH3), δ 3.67 (s, 3H, -CH3), 7.13-7.21 (m, 3H, phenyl-H),7.49 (d, 1H, phenyl-H, J =8.0 Hz)
50%	With N-Bromosuccinimide In N,N-dimethyl-formamide at 0℃; for 2h;	8 Example 8: Synthesis of 3-(Dicyclohexylphosphine)-1,2-dimethyl-1H-indole Dissolve 1,2-dimethyl-1H-indole (1.09 g, 7.50 mmol) in anhydrous dimethylformamide (15 mL). At 0°C, a solution (10 mL) of N-bromosuccinimide (1.40 g, 7.88 mmol) in dimethylformamide was added to the solution. After stirring for 2 hours, the mixture was poured onto crushed ice, and then dichloromethane and water were added. The organic layer was washed with a large amount of water and then concentrated. The concentrate was purified by flash silica gel column chromatography using ethyl acetate/hexane (1:20) as the eluent to obtain 3-bromo-1,2-dimethyl-1H-indole (0.84 g, 50 %).
42%	With ammonium bromide In methanol at -10 - 0℃; electrolysis at 40 mA/cm² with 4 F/mol on platinum anode, nickel cathode;
42%	With ammonium bromide In methanol at -10 - 0℃; electrolysis, amount of electricity 4 F/mol, current density 40 mA/cm²;
	With methylammonium tribromide
	With N-bromobutanimide
	With N-Bromosuccinimide In tetrahydrofuran at 20℃; for 0.5h;	3 Synthesis of 1,2-Dimethyl-3-bromoindole Dissolve 3g (1eq.) 1,2-dimethyl-indole in THF, stir at room temperature, then slowly add N-bromosuccinimide (NBS) (1.2eq.) in batches, continue to react at room temperature for 30 minutes and then stop the reaction. Dissolve the reaction product with ether, wash with saturated NaS2O3 and saturated NaHCO3, and collect the organic phase. The organic phase was dried with anhydrous MgSO4, filtered and evaporated in vacuo, it is separated by column chromatography, and the eluent is petroleum ether to obtain a white solid.
	With N-Bromosuccinimide In chloroform at 0℃; for 0.5h;

Reference： [1]Song, Song; Sun, Xiang; Li, Xinwei; Yuan, Yizhi; Jiao, Ning [Organic Letters, 2015, vol. 17, # 12, p. 2886 - 2889]
[2]Zheng, Chunhong; Pu, Shouzhi; Pang, Zhiyi; Chen, Bing; Liu, Gang; Dai, Yanfeng [Dyes and Pigments, 2013, vol. 98, # 3, p. 565 - 574]
[3]Shi, Leilei; Zhang, Dongmei; Lin, Riyuan; Zhang, Chun; Li, Xun; Jiao, Ning [Tetrahedron Letters, 2014, vol. 55, # 14, p. 2243 - 2245]
[4]Wang, Renjie; Pu, Shouzhi; Liu, Gang; Cui, Shiqiang; Li, Hui [Tetrahedron Letters, 2013, vol. 54, # 39, p. 5307 - 5310]
[5]Current Patent Assignee: HONG KONG POLYTECHNIC UNIVERSITY - CN113402553, 2021, A Location in patent: Paragraph 0123-0124
[6]Janda, Miroslav; Srogl, Jan; Holy, Petr [Collection of Czechoslovak Chemical Communications, 1981, vol. 46, # 12, p. 3278 - 3284]
[7]Janda, Miroslav; Srogl, Jan; Holy, Petr [Collection of Czechoslovak Chemical Communications, 1981, vol. 46, # 12, p. 3278 - 3284]
[8]Yagi, Kyoko; Irie, Masahiro [Bulletin of the Chemical Society of Japan, 2003, vol. 76, # 8, p. 1625 - 1628]
[9]Cheng, Hong-Bo; Qiao, Bin; Li, Hao; Cao, Jin; Luo, Yuanli; Kotraiah Swamy, Kunemadihalli Mathada; Zhao, Jing; Wang, Zhigang; Lee, Jin Yong; Liang, Xing-Jie; Yoon, Juyoung [Journal of the American Chemical Society, 2021, vol. 143, # 5, p. 2413 - 2422]
[10]Current Patent Assignee: BEIJING UNIVERSITY OF CHEMICAL TECHNOLOGY - CN113620940, 2021, A Location in patent: Page/Page column 20
[11]Wang, Miao; So, Chau Ming [Organic Letters, 2022, vol. 24, # 2, p. 681 - 685]

13
[ 26216-93-3 ]
[ 875-79-6 ]

Yield	Reaction Conditions	Operation in experiment
98%	With bis(1,5-cyclooctadiene)diiridium(I) dichloride In para-xylene at 130℃; for 20h; Inert atmosphere; Sealed tube;
94%	With ferrocene; tris(pentafluorophenyl)borate In toluene at 120℃; for 0.75h; Inert atmosphere; Schlenk technique; Glovebox;
75%	With N-hydroxyphthalimide In acetonitrile at 80℃; for 8h; Sealed tube;

75%	With N-hydroxyphthalimide In acetonitrile at 80℃; for 8h;	22 Synthesis of 1,2-Dimethylindole Into the reactor, 1,2-dimethylindoline (29.4mg, 0.2mmol), N-hydroxyphthalimide (6.6mg, 0.04mmol) and acetonitrile (3mL) were sequentially added, and then The reaction mixture was stirred in an air atmosphere at 80°C, and the reaction was monitored by TLC for 8 hours to complete. Then the reaction mixture was concentrated under reduced pressure, and the resulting residue was separated by column chromatography (ethyl acetate/petroleum ether as the eluting solvent, The volume ratio 1:40) was purified to obtain the target product 1,2-dimethylindole (21.8 mg, yield 75%).
72%	With [Ru(1,10-phenanthroline-5,6-dione)₃](PF₆)₂; oxygen; tetra-(n-butyl)ammonium iodide In acetonitrile at 25℃; for 24h;
34%	With tellurium In various solvent(s) at 120℃; for 48h;
	With dihydrogen peroxide In water at 45℃; for 24h; Green chemistry;

Reference： [1]Zhang, Deliang; Iwai, Tomohiro; Sawamura, Masaya [Organic Letters, 2020, vol. 22, # 13, p. 5240 - 5245]
[2]Maier, Alexander F. G.; Tussing, Sebastian; Schneider, Tobias; Flörke, Ulrich; Qu, Zheng -Wang; Grimme, Stefan; Paradies, Jan [Angewandte Chemie - International Edition, 2016, vol. 55, # 40, p. 12219 - 12223][Angew. Chem., 2016, vol. 128, p. 12407 - 12411]
[3]Chen, Weidong; Tang, Hao; Wang, Weilin; Fu, Qiang; Luo, Junfei [Advanced Synthesis and Catalysis, 2020, vol. 362, # 18, p. 3905 - 3911]
[4]Current Patent Assignee: NINGBO UNIVERSITY - CN111909074, 2020, A Location in patent: Paragraph 0086-0088
[5]Li, Bao; Wendlandt, Alison E.; Stahl, Shannon S. [Organic Letters, 2019, vol. 21, # 4, p. 1176 - 1181]
[6]Suzuki, Hitomi; Nakamura, Tohru [Journal of Organic Chemistry, 1993, vol. 58, # 1, p. 241 - 244]
[7]Llopis, Natalia; Gisbert, Patricia; Baeza, Alejandro; Correa-Campillo, Jara [Advanced Synthesis and Catalysis, 2022, vol. 364, # 6, p. 1205 - 1210]

14
[ 875-79-6 ]
[ 336-59-4 ]
[ 333755-06-9 ]

Yield	Reaction Conditions	Operation in experiment
93%	In 1,2-dichloro-ethane at 20℃; for 2h;

Reference： [1]Thomas; Wolak; Birge; Lees [Journal of Organic Chemistry, 2001, vol. 66, # 5, p. 1914 - 1918]

15
[ 26340-49-8 ]
[ 74-88-4 ]
[ 95-20-5 ]
[ 875-79-6 ]

Reference： [1]Synthetic Communications,2001,vol. 31,p. 947 - 951

16
[ 875-79-6 ]
[ 39581-32-3 ]

Yield	Reaction Conditions	Operation in experiment
90%	With MoO₅Et₃POMeOH In methanol; dichloromethane at 2℃; for 2h;
89%	With 2,2,6,6-tetramethyl-piperidine-N-oxyl; benzoic acid; copper dichloride In acetonitrile at 25℃; for 24h; regioselective reaction;
82%	With 5,6-bis(5-methoxythiophen-2-yl)pyrazine-2,3-dicarbonitrile; oxygen In 2,2,2-trifluoroethanol at 25℃; for 4h; Irradiation; chemoselective reaction;

81%	With dihydrogen peroxide; trichloroacetic acid In acetone for 2h;
81%	With sodium periodate; ruthenium(III) chloride trihydrate In acetonitrile at 20 - 70℃; for 24h; Schlenk technique;	2. The Typical Procedure for Ru-Catalyzed Oxidative Dearomatization of Indoles General procedure: A mixture of indole 1 (0.50 mmol), NaIO4 (107 mg, 0.50 mmol, 1.0 equiv) and RuCl3·3H2O (6.5 mg, 0.025 mmol, 5.0 mol%) in CH3CN (3 mL) was added into aSchlenk flask (25 mL) and stirred at room temperature. The mixture was stirred at 70 °C until the reaction was finished. Then the solvent was evaporated underreduced pressure and the residue was purified by column chromatography (petroleum ether/ethyl acetate 10:1 to 5:1).
70%	With pyridine; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; water; oxygen; silver nitrate; benzoic acid at 65℃; for 48h;
34%	With oxone; ethylenediaminetetraacetic acid; sodium hydrogencarbonate In water; acetone at 20℃; for 1.16667h;

Reference： [1]Altinis Kiraz, Christine I.; Emge, Thomas J.; Jimenez, Leslie S. [Journal of Organic Chemistry, 2004, vol. 69, # 6, p. 2200 - 2202]
[2]Kong, Yu-Bo; Zhu, Jia-Yi; Chen, Zheng-Wang; Liu, Liang-Xian [Canadian Journal of Chemistry, 2014, vol. 92, # 4, p. 269 - 273]
[3]Zhang, Chenhao; Li, Sanliang; Bureš, Filip; Lee, Richmond; Ye, Xinyi; Jiang, Zhiyong [ACS Catalysis, 2016, vol. 6, # 10, p. 6853 - 6860]
[4]Astolfi; Greci; Rizzoli; Sgarabotto; Marrosu [Journal of the Chemical Society. Perkin Transactions 2 (2001), 2001, # 9, p. 1634 - 1640]
[5]Zhou, Xiao-Yu; Chen, Xia; Wang, Liang-Guang; Yang, Dan; Li, Jin-Hui [Synlett, 2018, vol. 29, # 6, p. 835 - 839]
[6]Lin, Feng; Chen, Yu; Wang, Baoshuang; Qin, Wenbing; Liu, Liangxian [RSC Advances, 2015, vol. 5, # 46, p. 37018 - 37022]
[7]Aristeo-Dominguez, Alberto; Melendez-Rodriguez, Myriam; Castillo, Oscar R. Suarez; Contreras-Martinez, Yaneth M. A.; Suarez-Ramirez, Lizbeth; Trejo-Carbajal, Nayely; Morales-Rios, Martha S.; Joseph-Nathan, Pedro [Heterocycles, 2013, vol. 87, # 6, p. 1249 - 1267]

17
[ 875-79-6 ]
[ 78902-09-7 ]
[ 685514-70-9 ]

Reference： [1]Synthetic Communications,2004,vol. 34,p. 421 - 434

18
[ 875-79-6 ]
[ 372-31-6 ]
3-hydroxy-3-(1,2-dimethylindol-3-yl)-4,4,4-trifluorobutanoic acid ethyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
95%	With K-10 montmorillonite In toluene at 70℃; for 1h;
59%	With zinc(II) chloride In dichloromethane at 20℃; for 2h; Molecular sieve;	2.1. General General procedure: To a solution of paraformaldehyde (2.5 mmol), fluorine-containing β-ketoesters (0.5 mmol), and indole (0.5 mmol) in DCM (3.0 mL) were added acetic acid (50 mol %) and molecular sieves 4 Å (100 mg). The reaction mixture was stirred by magnetic stirrer at room temperature for about 2 h. The progress of reaction was monitored by TLC. After satisfactory conversion, the product was separated from molecular sieves by filtration. The solvent was removed in vacuum and the residue was purified on silica gel using ethyl acetate-hexane as eluent to afford the pure corresponding products.

Reference： [1]Abid, Mohammed; Toeroek, Bela [Advanced Synthesis and Catalysis, 2005, vol. 347, # 14, p. 1797 - 1803]
[2]Location in patent: experimental part Pang, Wan; Xin, Yong; Zhu, Shi-Fa; Jiang, Huan-Feng; Zhu, Shi-Zheng [Tetrahedron, 2011, vol. 67, # 34, p. 6334 - 6339]

19
[ 875-79-6 ]
[ 14204-27-4 ]
[ 340169-30-4 ]

Yield	Reaction Conditions	Operation in experiment
97%	With magnesium bromide In N,N-dimethyl acetamide at 90℃; for 0.75h;
	With indium(III) chloride In N,N-dimethyl-formamide at 100℃;	General procedure for the preparation of 5 from 4 and 2 General procedure: A mixture of 4 (10 mM), 2 (10 mM), InCl3 (20 Mol%) and DMF (20 ml) was heated at 100Cfor 5-6 h. The reaction mixture was monitored by TLC for the disappearance of 4. On completionof the reaction, the mixture was cooled to RT, diluted with the water (50 ml) and extractedwith ethyl acetate. The organic layer was separated, washed with a saturated solution of sodium hydrogen carbonate (10 ml) followed by brine (10 ml) and then dried with Na2SO4. The solventwas evaporated to obtain a residue which on purification by the silica gel column chromatography(hexane-ethyl acetate, 90:10) gave 5 (Table 3).

Reference： [1]Tudge, Matthew; Tamiya, Minoru; Savarin, Cecile; Humphrey, Guy R. [Organic Letters, 2006, vol. 8, # 4, p. 565 - 568]
[2]Praveen Kumar; Dathu Reddy; Venkata Ramana Reddy; Rama Devi; Dubey [Journal of Sulfur Chemistry, 2014, vol. 35, # 4, p. 356 - 361]

20
[ 875-79-6 ]
[ 74-85-1 ]
[ 19869-53-5 ]

Yield	Reaction Conditions	Operation in experiment
99%	In 1,4-dioxane at 90℃; for 6h;

Reference： [1]Zhang, Zhibin; Wang, Xiang; Widenhoefer, Ross A. [Chemical Communications, 2006, # 35, p. 3717 - 3719]

21
[ 875-79-6 ]
[ 7570-48-1 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: 79 percent / NaNO₃, H₂SO₄ / 1.) 0 deg C, 5h, 2.) RT, 12 h 2: H₂ / 10percent Pd/C / methanol / 2 h / 2068.6 Torr

Reference： [1]Kuyper, Lee F.; Baccanari, David P.; Jones, Michael L.; Hunter, Robert N.; Tansik, Robert L.; Joyner, Suzanne S.; Boytos, Christine M.; Rudolph, Sharon K.; Knick, Vince; Wilson, H. Robert; Caddell, J. Marc; Friedman, Henry S.; Comley, John C. W.; Stables, Jeremy N. [Journal of Medicinal Chemistry, 1996, vol. 39, # 4, p. 892 - 903]

22
[ 875-79-6 ]
[ 33022-90-1 ]

Yield	Reaction Conditions	Operation in experiment
80%	With trichlorophosphate In (2S)-N-methyl-1-phenylpropan-2-amine hydrate; N,N-dimethyl acetamide	R.5.1 (1) (1) Synthesis of 3-acetyl-1,2-dimethylindole To a solution of 6 moles of N,N-dimethylacetamide and cooled at 0° C., 1.5 moles of phosphorus oxychloride was added dropwise in 30 minutes with stirring. After further adding 1 mole of 1,2-dimethylindole thereto, the reaction was carried out at 85°-90° C. for 2 hours. Then, the reaction solution was poured into 2 liters of ice water. The reaction solution was made alkaline, extracted with 0.5 liter of ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and concentrated. The residue was recrystallized from ethyl acetate to give yellow crystals in yield of 80%.
	Multi-step reaction with 2 steps 1: dichloromethane / -50 - -22 °C 2: sodium acetate; water / 0.17 h / Reflux

Reference： [1]Current Patent Assignee: FUJIFILM HOLDINGS CORP. - US5359085, 1994, A
[2]Giles, Robert G.; Heaney, Harry; Plater, M. John [Tetrahedron, 2015, vol. 71, # 39, p. 7367 - 7385]

23
[ 875-79-6 ]
[ 6388-72-3 ]
[ 1009308-79-5 ]

Yield	Reaction Conditions	Operation in experiment
90%	With 5A molecular sieve In dichloromethane at 20℃; for 26h;
69%	In 2,2,2-trifluoroethanol at 80℃; for 4h;

Reference： [1]Fleming, Eimear M.; Quigley, Cormac; Rozas, Isabel; Connon, Stephen J. [Journal of Organic Chemistry, 2008, vol. 73, # 3, p. 948 - 956]
[2]Location in patent: experimental part Westermaier, Martin; Mayr, Herbert [Chemistry - A European Journal, 2008, vol. 14, # 5, p. 1638 - 1647]

24
[ 875-79-6 ]
[ 121-39-1 ]
rac-ethyl 3-(1,2-dimethyl-1H-indol-3-yl)-2-hydroxy-3-phenylpropanoate [ No CAS ]

Reference： [1]Chemistry - A European Journal,2008,vol. 14,p. 1638 - 1647

25
[ 875-79-6 ]
[ 1142926-54-2 ]

Yield	Reaction Conditions	Operation in experiment
94%	Stage #1: 1,2-dimethylindole With 1,4-diaza-bicyclo[2.2.2]octane; disulfur dichloride In chloroform at 20℃; for 48h; Inert atmosphere; Stage #2: With triethylamine In chloroform at 0℃; Inert atmosphere; Reflux;
94%	Stage #1: 1,2-dimethylindole With 1,4-diaza-bicyclo[2.2.2]octane; disulfur dichloride In chloroform at 20℃; for 48h; Inert atmosphere; Stage #2: With triethylamine In chloroform for 5h;	Method C General procedure: Disulfur dichloride (0.4 mL, 5 mmol) was added dropwise at-35 °C to a stirred solution of DABCO (1.12 g, 10 mmol) in chloroform(25 mL) under nitrogen. The mixture was stirred at r.t.for 1 h. 3-[(2-Methyl-1H-indol-1-yl)methyl]benzonitrile (12j,0.239 g, 1 mmol) in chloroform (5 mL) was added, and themixture was stirred at r.t. for 48 h under nitrogen. Triethylamine(1.4 mL, 10 mmol) was then added to the resultantmixture at 0 °C, the mixture stirred at r.t. for 2 h, heated atreflux for 3 h, filtered, and solvents evaporated. Purification viaflash column chromatography on silica gel (hexanes/CH2Cl2) toafford 3-{(3-thioxo-[1,2]dithiolo[4,3-b]indol-4(3H)-yl)methyl}-benzonitrile (14l) (0.277 g, 0.82 mmol, 82% yield) as orangecrystals; mp 190-191 °C.

Reference： [1]Location in patent: experimental part Konstantinova, Lidia S.; Lysov, Kirill A.; Amelichev, Stanislav A.; Obruchnikova, Natalia V.; Rakitin, Oleg A. [Tetrahedron, 2009, vol. 65, # 11, p. 2178 - 2183]
[2]Asquith, Christopher R. M.; Konstantinova, Lidia S.; Tizzard, Graham J.; Laitinen, Tuomo; Coles, Simon J.; Rakitin, Oleg A.; Hilton, Stephen T. [Synlett, 2019, vol. 30, # 2, p. 156 - 160]

26
[ 875-79-6 ]
[ 124-38-9 ]
[ 20357-15-7 ]

Yield	Reaction Conditions	Operation in experiment
95%	With dimethylaluminum chloride In hexane; toluene at 80℃; for 3h; Autoclave;	3.6. Typical procedure for the carboxylation of indoles (entry 1 in Table 1) General procedure: In a 50 mL autoclave equipped with a glass inner tube and a magnetic stirring bar were charged indole 1a (d 1.05; 125 mL, 1.00 mmol), Me2AlCl (1.0 M solution in hexane; 1.0 mL, 1.0 mmol), toluene (1.0 mL) under nitrogen atmosphere, and the apparatus was purged with CO2 by repeated pressurization and subsequent expansion, the final pressure being adjusted to 3.0 MPa. After the mixture was stirred at 80 °C for 3 h, the reactor was allowed to cool to room temperature and depressurized. The reaction mixture was quenched with 2 M HCl and the aqueous layer was extracted with ethyl acetate. The combined organic layer was extracted with 0.5M Na2CO3 and the extract was acidified by the addition of concentrated HCl to liberate the free carboxylic acid, which was extracted with ethyl acetate. The extract was dried over MgSO4 and evaporated to leave a residue, which was purified by column chromatography with chloroform-ethyl acetate (1:1) as an eluent to give acid 2a as crystals (168 mg, 96%). The carboxylation of other indoles was conducted by a similar procedure. The crude product was routinely purified by column chromatography using chloroform-ethyl acetate (1:1) or chloroform-ethyl acetate (1:1) containing 1% (v/v) of acetic acid as an eluent. See Tables 1 and 2 for the reaction conditions and product yields.
73%	With dimethylaluminum chloride In hexane; toluene at 20℃; for 3h; regioselective reaction;

Reference： [1]Nemoto, Koji; Tanaka, Shinya; Konno, Megumi; Onozawa, Satoru; Chiba, Masafumi; Tanaka, Yuuki; Sasaki, Yosuke; Okubo, Ryo; Hattori, Tetsutaro [Tetrahedron, 2016, vol. 72, # 5, p. 734 - 745]
[2]Location in patent: experimental part Nemoto, Koji; Onozawa, Satoru; Egusa, Naoki; Morohashi, Naoya; Hattori, Tetsutaro [Tetrahedron Letters, 2009, vol. 50, # 31, p. 4512 - 4514]

27
[ 875-79-6 ]
[ 19434-36-7 ]
[ 1184923-68-9 ]

Yield	Reaction Conditions	Operation in experiment
84%	With iron(III) chloride hexahydrate In toluene at 50℃; for 3h; Inert atmosphere;

Reference： [1]Li, Hongfeng; Yang, Jingyu; Liu, Yuanhong; Li, Yanzhong [Journal of Organic Chemistry, 2009, vol. 74, # 17, p. 6797 - 6801]

28
[ 875-79-6 ]
[ 19434-36-7 ]
[ 1184923-68-9 ]
[ 1184923-69-0 ]

Yield	Reaction Conditions	Operation in experiment
1: 40% 2: 36%	With zinc(II) chloride In toluene at 50℃; for 12h; Inert atmosphere;
1: 32% 2: 25%	With gold(III) chloride In toluene at 50℃; for 3h; Inert atmosphere;

Reference： [1]Li, Hongfeng; Yang, Jingyu; Liu, Yuanhong; Li, Yanzhong [Journal of Organic Chemistry, 2009, vol. 74, # 17, p. 6797 - 6801]
[2]Li, Hongfeng; Yang, Jingyu; Liu, Yuanhong; Li, Yanzhong [Journal of Organic Chemistry, 2009, vol. 74, # 17, p. 6797 - 6801]

29
[ 875-79-6 ]
[ 19434-36-7 ]
[ 1184923-69-0 ]

Yield	Reaction Conditions	Operation in experiment
49%	With hydrogenchloride In diethyl ether; toluene at 50℃; for 6h; Inert atmosphere;

Reference： [1]Li, Hongfeng; Yang, Jingyu; Liu, Yuanhong; Li, Yanzhong [Journal of Organic Chemistry, 2009, vol. 74, # 17, p. 6797 - 6801]

30
[ 875-79-6 ]
[ 26412-87-3 ]
[ 40801-93-2 ]

Yield	Reaction Conditions	Operation in experiment
92%	In dichloromethane at 40℃; for 4h; Large scale;	1 Example 1, Synthesis of MIS-OH. Py, compound of formula (2) 1, 2-Dimethylindole (1.00 kg, 6.88 mol, 1.00 eq) , sulphur trioxide pyridine complex (1.42 kg, 8.88 mol, 1.29 eq) and dichloromethane (6.7 kg) were mixed. The mixture was heated to 40 C and kept for 4 h at 40 C. The conversion reached 99.5% as determined by HPLC. If the value is not reached, then 0.03 eq of sulphur trioxide pyridine complex can be added and stirring can be continued at 40 C for 1 h. The reaction mixture was cooled down to 20 C to 30 C and was used for next step (based on the assumption of 100% yield, containing 2.09 kg of MIS-OH. Py, 6.88 mol). The structure was confirmed by1H NMR. The yield of example 1 and example 2 each was ca. 92 %.
	With pyridine for 1h; Inert atmosphere; Reflux;

Reference： [1]Current Patent Assignee: POLYPEPTIDE LABORATORIES AS - WO2018/64829, 2018, A1 Location in patent: Page/Page column 16; 17
[2]Location in patent: experimental part Isidro, Albert; Latassa, Daniel; Giraud, Matthieu; Alvarez, Mercedes; Albericio, Fernando [Organic and Biomolecular Chemistry, 2009, vol. 7, # 12, p. 2565 - 2569]

31
[ 875-79-6 ]
potassium ferrocyanide [ No CAS ]
[ 51072-84-5 ]

Yield	Reaction Conditions	Operation in experiment
98%	With 2C₂H₅NO₂Pd⁽²⁺⁾2Cl^(1-); copper diacetate In dimethyl sulfoxide at 130℃; for 6h;
95%	With oxygen; copper diacetate; palladium diacetate In dimethyl sulfoxide at 130℃; for 5h;
77%	With oxygen; copper diacetate; potassium carbonate In N,N-dimethyl-formamide at 110℃; for 4h; regioselective reaction;

Reference： [1]Chu, Hailiang; Guo, Mengping; Yi, Yanping; Wen, Yongju; Zhou, Lanjiang; Huang, Hongwei [Applied Organometallic Chemistry, 2017, vol. 31, # 9]
[2]Location in patent: scheme or table Yan, Guobing; Kuang, Chunxiang; Zhang, Yan; Wang, Jianbo [Organic Letters, 2010, vol. 12, # 5, p. 1052 - 1055]
[3]Location in patent: experimental part Khorshidi, Alireza [Chinese Chemical Letters, 2012, vol. 23, # 8, p. 903 - 906]

32
[ 875-79-6 ]
[ 882-33-7 ]
[ 340169-30-4 ]

Yield	Reaction Conditions	Operation in experiment
80%	With copper(l) iodide; oxygen In dimethyl sulfoxide at 110℃; regioselective reaction;	4.2. General procedure for chalcogenylation of azaheterocycles with dichalcogenides General procedure: A mixture of azaheterocycles 1 or 4 (0.20 mmol), dichalcogenides 2 (0.10 mmol), and CuI (0.020 mmol, 10 mol %) in DMSO (2.0 mL) was stirred at 110 °C under air atmosphere for 10-18 h until complete consumption of staring material as monitored by TLC. The solution was then cooled to room temperature, diluted with ethyl acetate (10 mL), washed with H2O (3×10 mL), dried over Na2SO4, filtered, and evaporated under vacuum. The crude product was purified by column chromatography on silica gel (eluting with PE/EA=25/1 to 4/1) to afford the desired products 3 or 5.

Reference： [1]Li, Zhen; Hong, Jianquan; Zhou, Xigeng [Tetrahedron, 2011, vol. 67, # 20, p. 3690 - 3697]

33
[ 5344-90-1 ]
[ 875-79-6 ]
[ 1312707-16-6 ]

Yield	Reaction Conditions	Operation in experiment
79%	With trifluoroacetic acid In 1,2-dichloro-ethane at 20 - 50℃; Inert atmosphere;	5.1.1. General procedure General procedure: To a solution of 1 (0.28 mmol, 0.040 g) and 2 (0.14 mmol, 0.017 g) in DCE (0.41 mL) was added TFA (0.041 mmol, 0.0031 mL) at rt. The resulting solution was stirred at 50 °C overnight. The reaction was quenched with saturated aqueous NaHCO3 (5.0 mL) and diluted with EtOAc (5.0 mL). The organic phase was washed with brine (10 mL), and then dried over Na2SO4. Solvent was removed using a rotary evaporator, and the residue was purified by silica gel chromatography (EtOAc/pentanes).

Reference： [1]Location in patent: experimental part Robertson, Forest J.; Kenimer, Bradshaw D.; Wu, Jimmy [Tetrahedron, 2011, vol. 67, # 24, p. 4327 - 4332]

34
[ 95-20-5 ]
[ 875-79-6 ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 2-methyl-1H-indole With sodium hydroxide In dimethyl sulfoxide Stage #2: methyl halide In dimethyl sulfoxide at 10 - 15℃; for 3h;
	Stage #1: 2-methyl-1H-indole With sodium hydride In N,N-dimethyl-formamide at 0 - 23℃; for 0.5h; Inert atmosphere; Stage #2: methyl halide In N,N-dimethyl-formamide at 0 - 23℃; Inert atmosphere;	General procedure for the Indole N-Aklylation (step c) In a dried RBF under argon, NaH (1.5 mmol) was added in anhydrous DMF (10 mL), the solution was cooled to 0 °C and indole (1.0 mmol) was added and the reaction was allowed to stir at RT for 30 min. The solution was then cooled again to 0 °C and appropriate alkyl halide (1.1 mmol) was added and the mixture was allowed to warm to RT and stirred at ambient temperature overnight. The solution was quenched with water (5 mL) and the product extracted with diethyl ether (3 x 20 mL) and then dried over anhydrous MgSO4 and concentrated under vacuum. The residue was then purified by flash chromatography using a CombiFlash instrument with a gradient from 100% Hexanes to 30% EtOAc in hexanes.
	Stage #1: 2-methyl-1H-indole With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0℃; for 1h; Stage #2: methyl halide In N,N-dimethyl-formamide; mineral oil at 0℃; for 18h;

Stage #1: 2-methyl-1H-indole With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0℃; for 0.5h; Inert atmosphere; Stage #2: methyl halide at 20℃;

Reference： [1]Location in patent: experimental part Mirskova; Levkovskaya; Kolesnikova; Perminova; Rudyakova; Adamovich [Russian Chemical Bulletin, 2010, vol. 59, # 12, p. 2236 - 2246]
[2]Gritzalis, Dimitrios; Park, Jaeok; Chiu, Wei; Cho, Hyungjun; Lin, Yih-Shyan; De Schutter, Joris W.; Lacbay, Cyrus M.; Zielinski, Michal; Berghuis, Albert M.; Tsantrizos, Youla S. [Bioorganic and Medicinal Chemistry Letters, 2015, vol. 25, # 5, p. 1117 - 1123]
[3]Marcum, Justin S.; Roberts, Courtney C.; Manan, Rajith S.; Cervarich, Tia N.; Meek, Simon J. [Journal of the American Chemical Society, 2017, vol. 139, # 44, p. 15580 - 15583]
[4]Kahar, Nilesh; Jadhav, Pankaj; Reddy, R. V. Ramana; Dawande, Sudam [Chemical Communications, 2020, vol. 56, # 8, p. 1207 - 1210]

35
[ 875-79-6 ]
[ 50-00-0 ]
[ 102660-41-3 ]

Yield	Reaction Conditions	Operation in experiment
42%	With copper(II) bis(trifluoromethanesulfonate); ethyl 4,4,4-trifluoroacetoacetate In dichloromethane at 20℃; for 2h; Molecular sieve;	2.1. General General procedure: To a solution of paraformaldehyde (2.5 mmol), fluorine-containing β-ketoesters (0.5 mmol), and indole (0.5 mmol) in DCM (3.0 mL) were added acetic acid (50 mol %) and molecular sieves 4 Å (100 mg). The reaction mixture was stirred by magnetic stirrer at room temperature for about 2 h. The progress of reaction was monitored by TLC. After satisfactory conversion, the product was separated from molecular sieves by filtration. The solvent was removed in vacuum and the residue was purified on silica gel using ethyl acetate-hexane as eluent to afford the pure corresponding products.

Reference： [1]Location in patent: experimental part Pang, Wan; Xin, Yong; Zhu, Shi-Fa; Jiang, Huan-Feng; Zhu, Shi-Zheng [Tetrahedron, 2011, vol. 67, # 34, p. 6334 - 6339]

36
[ 875-79-6 ]
[ 50-00-0 ]
[ 35896-48-1 ]
[ 1328934-53-7 ]

Yield	Reaction Conditions	Operation in experiment
56%	With acetic acid In dichloromethane at 20℃; for 2h; Molecular sieve;	2.1. General General procedure: To a solution of paraformaldehyde (2.5 mmol), fluorine-containing β-ketoesters (0.5 mmol), and indole (0.5 mmol) in DCM (3.0 mL) were added acetic acid (50 mol %) and molecular sieves 4 Å (100 mg). The reaction mixture was stirred by magnetic stirrer at room temperature for about 2 h. The progress of reaction was monitored by TLC. After satisfactory conversion, the product was separated from molecular sieves by filtration. The solvent was removed in vacuum and the residue was purified on silica gel using ethyl acetate-hexane as eluent to afford the pure corresponding products.

Reference： [1]Location in patent: experimental part Pang, Wan; Xin, Yong; Zhu, Shi-Fa; Jiang, Huan-Feng; Zhu, Shi-Zheng [Tetrahedron, 2011, vol. 67, # 34, p. 6334 - 6339]

37
[ 875-79-6 ]
[ 50-00-0 ]
[ 17587-22-3 ]
1-((2SR,3RS)-2-hydroxy-9-methyl-2-(1,1,1,2,2,3,3-heptafluoroprop-3-yl)-2,3,4,9-tetrahydro-1H-carbazole-3-yl)-2,2-dimethylpropan-1-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
47%	With acetic acid; In dichloromethane; at 20℃; for 2h;Molecular sieve;	General procedure: To a solution of paraformaldehyde (2.5 mmol), fluorine-containing β-ketoesters (0.5 mmol), and indole (0.5 mmol) in DCM (3.0 mL) were added acetic acid (50 mol %) and molecular sieves 4 Å (100 mg). The reaction mixture was stirred by magnetic stirrer at room temperature for about 2 h. The progress of reaction was monitored by TLC. After satisfactory conversion, the product was separated from molecular sieves by filtration. The solvent was removed in vacuum and the residue was purified on silica gel using ethyl acetate-hexane as eluent to afford the pure corresponding products.

Reference： [1]Tetrahedron,2011,vol. 67,p. 6334 - 6339

38
[ 875-79-6 ]
[ 50-00-0 ]
[ 372-31-6 ]
(2SR,3RS)-ethyl 2-hydroxy-9-methyl-2-(trifluoromethyl)-2,3,4,9-tetrahydro-1H-carbazole-3-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
50%	With acetic acid In dichloromethane at 20℃; for 2h; Molecular sieve;	2.1. General General procedure: To a solution of paraformaldehyde (2.5 mmol), fluorine-containing β-ketoesters (0.5 mmol), and indole (0.5 mmol) in DCM (3.0 mL) were added acetic acid (50 mol %) and molecular sieves 4 Å (100 mg). The reaction mixture was stirred by magnetic stirrer at room temperature for about 2 h. The progress of reaction was monitored by TLC. After satisfactory conversion, the product was separated from molecular sieves by filtration. The solvent was removed in vacuum and the residue was purified on silica gel using ethyl acetate-hexane as eluent to afford the pure corresponding products.

Reference： [1]Location in patent: experimental part Pang, Wan; Xin, Yong; Zhu, Shi-Fa; Jiang, Huan-Feng; Zhu, Shi-Zheng [Tetrahedron, 2011, vol. 67, # 34, p. 6334 - 6339]

39
[ 875-79-6 ]
[ 50-00-0 ]
[ 367922-07-4 ]
(2SR,3RS)-ethyl 2-(bromodifluoromethyl)-2-hydroxy-9-methyl-2,3,4,9-tetrahydro-1H-carbazole-3-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
63%	With acetic acid In dichloromethane at 20℃; for 2h; Molecular sieve;	2.1. General General procedure: To a solution of paraformaldehyde (2.5 mmol), fluorine-containing β-ketoesters (0.5 mmol), and indole (0.5 mmol) in DCM (3.0 mL) were added acetic acid (50 mol %) and molecular sieves 4 Å (100 mg). The reaction mixture was stirred by magnetic stirrer at room temperature for about 2 h. The progress of reaction was monitored by TLC. After satisfactory conversion, the product was separated from molecular sieves by filtration. The solvent was removed in vacuum and the residue was purified on silica gel using ethyl acetate-hexane as eluent to afford the pure corresponding products.

Reference： [1]Location in patent: experimental part Pang, Wan; Xin, Yong; Zhu, Shi-Fa; Jiang, Huan-Feng; Zhu, Shi-Zheng [Tetrahedron, 2011, vol. 67, # 34, p. 6334 - 6339]

40
[ 875-79-6 ]
3-deuterio-1,2-dimethyl-1H-indole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With water-d2 at 105℃; Inert atmosphere;
	With water-d2 at 105℃; Inert atmosphere;	Synthesis of 3-deutero-1,2-dimethylindole Freshly distilled 1,2-dimethylindole (1 g, 6.89 mmol) was dissolved in 1 mL of D2O, and the reaction mixture was heated to 105 °C overnight with very vigorous stirring. The organic compound was extracted with hexanes (3 × 5 mL) and driedover Na2SO4. The combined organic layer was concentrated using vacuum andthe desired product was purified by distillation from molecular sieves. 1H NMR (CDCl3, 400 MHz) analysis indicate that the product was 80% incorporated deuterium in the 3-position of indole. 1HNMR (400 MHz, CDCl3, 298 K) δ: 7.54 (d, J = 7.8, 1H, Ar-CH), 7.29-7.26 (m, 1H, Ar-CH),7.19-7.15 (m, 1H, Ar-CH), 7.10-7.06 (m, 1H, Ar-CH), 6.27-6.26 (m, 1H, Ar-CH), 3.67 (d, J =0.6 Hz, 3H, N-CH3), 2.44 (s, 3H, CH3); 13C{1H} NMR (101 MHz, CDCl3, 298 K) δ: 137.4, 136.8,127.9, 120.5, 119.6, 119.3, 108.8, 99.6, 99.4, 99.1, 29.4 (CH3), 12.8 (CH3).

Reference： [1]Munoz, Maria Paz; De La Torre, Maria C.; Sierra, Miguel Angel [Chemistry - A European Journal, 2012, vol. 18, # 15, p. 4499 - 4504]
[2]Dasgupta, Ayan; Babaahmadi, Rasool; Slater, Ben; Yates, Brian F.; Ariafard, Alireza; Melen, Rebecca L. [Chem, 2020, vol. 6, # 9, p. 2364 - 2381]

41
[ 875-79-6 ]
[ 53654-36-7 ]
[ 1383255-54-6 ]

Yield	Reaction Conditions	Operation in experiment
85%	With toluene-4-sulfonic acid In N,N-dimethyl acetamide at 20℃; for 8h;	4.2. General procedure for substrate scope (Table 2) General procedure: To a 2.5 dr vial equipped with a stir bar was added 5.13 mg of p-TsOH (0.030 mmol, 0.100 equiv), 351.3 mg of N-H-indole (3.00 mmol, 10.0 equiv), and 42.9 mg of 1 (0.300 mmol, 1.00 equiv). To this 1.5 mL of DMA was added via syringe. The vial was capped and was stirred for given time at room temperature. The crude mixture was purified with flash silica-gel column chromatography. (Note: In case of liquid nucleophiles, p-TsOH was added last.)

Reference： [1]Location in patent: scheme or table Pathak, Tejas P.; Osiak, Jaroslaw G.; Vaden, Rachel M.; Welm, Bryan E.; Sigman, Matthew S. [Tetrahedron, 2012, vol. 68, # 26, p. 5203 - 5208]

42
[ 875-79-6 ]
[ 62005-48-5 ]
[ 1353013-73-6 ]

Reference： [1]Journal of Organic Chemistry,2012,vol. 77,p. 6351 - 6357

43
[ 875-79-6 ]
[ 110-18-9 ]
[ 38292-40-9 ]

Yield	Reaction Conditions	Operation in experiment
72%	With C₄₈H₃₉N₃; oxygen; potassium iodide In water; acetonitrile for 48h; Irradiation;	1 The synthesis method of the 3-formaldehyde steroid compound of the present invention has the following synthetic route: Compound 1 (1 mmol) was weighed and dissolved in 5 mL of acetonitrile to dissolve KI (664 mg, 4 mmol) in 1 mL of water and 20 mg. CMP-CSU1, Add to a 25 mL reaction flask and add 300 μl of 2 with a pipette. The LED lamp was continuously illuminated for 48 hours under continuous oxygen supply. The solvent was evaporated to dryness and purified to give the corresponding product 3a (yield: 90%), 3b (yield: 66%), 3c (yield: 72%).
72%	With water; oxygen; potassium iodide In acetonitrile at 25℃; for 48h; Irradiation;
61%	With water; oxygen; rose bengal; potassium iodide In acetonitrile at 60℃; for 48h; Irradiation;

58%	With water; oxygen; potassium iodide In acetonitrile at 25℃; for 36h; Irradiation;
47%	With oxygen; copper dichloride In water; dimethyl sulfoxide at 120℃; for 4h;

Reference： [1]Current Patent Assignee: CENTRAL SOUTH UNIVERSITY - CN108250124, 2018, A Location in patent: Paragraph 0035-0040
[2]Zhang, Weijie; Tang, Juntao; Yu, Wenguang; Huang, Qiao; Fu, Yu; Kuang, Guichao; Pan, Chunyue; Yu, Guipeng [ACS Catalysis, 2018, vol. 8, # 9, p. 8084 - 8091]
[3]Li, Xiang; Gu, Xiangyong; Li, Yongjuan; Li, Pixu [ACS Catalysis, 2014, vol. 4, # 6, p. 1897 - 1900]
[4]Chen, Xiong; Feng, Xiao; Han, Songjie; Li, Chunzhi; Li, He; Li, Ziping; Liu, Xiaoming; Shao, Pengpeng; Xia, Hong [Journal of Materials Chemistry A, 2020, vol. 8, # 17, p. 8706 - 8715]
[5]Chen, Jianbin; Liu, Bin; Liu, Dongfang; Liu, Shan; Cheng, Jiang [Advanced Synthesis and Catalysis, 2012, vol. 354, # 13, p. 2438 - 2442]

44
[ 875-79-6 ]
[ 6314-97-2 ]
[ 72228-49-0 ]

Yield	Reaction Conditions	Operation in experiment
85%	With iron(III) chloride hexahydrate In para-xylene at 25℃; for 3h; stereospecific reaction;

Reference： [1]Yang, Qin; Wang, Liandi; Guo, Tenglong; Yu, Zhengkun [Journal of Organic Chemistry, 2012, vol. 77, # 18, p. 8355 - 8361]

45
[ 875-79-6 ]
[ 27200-79-9 ]
[ 1397587-42-6 ]

Reference： [1]Journal of Organic Chemistry,2012,vol. 77,p. 8355 - 8361

46
[ 875-79-6 ]
[ 57091-71-1 ]

Yield	Reaction Conditions	Operation in experiment
71%	With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; 5,6-bis(5-methoxythiophen-2-yl)pyrazine-2,3-dicarbonitrile; oxygen In water; acetonitrile for 17h; Irradiation; chemoselective reaction;
67%	With tris(bipyridine)ruthenium(II) dichloride hexahydrate; potassium phosphate tribasic trihydrate; water; oxygen In acetonitrile at 20℃; Irradiation;
67%	With potassium phosphate; oxygen; Rose Bengal lactone In water; N,N-dimethyl-formamide for 46h; Inert atmosphere; Irradiation;

5%

With oxone; ethylenediaminetetraacetic acid; sodium hydrogencarbonate In water; acetone at 20℃; for 1.16667h;

Reference： [1]Zhang, Chenhao; Li, Sanliang; Bureš, Filip; Lee, Richmond; Ye, Xinyi; Jiang, Zhiyong [ACS Catalysis, 2016, vol. 6, # 10, p. 6853 - 6860]
[2]Ji, Xiaochen; Li, Dongdong; Wang, Zhongzhen; Tan, Muyun; Huang, Huawen; Deng, Guo-Jun [European Journal of Organic Chemistry, 2017, vol. 2017, # 45, p. 6652 - 6659]
[3]Schilling, Waldemar; Zhang, Yu; Riemer, Daniel; Das, Shoubhik [Chemistry - A European Journal, 2020, vol. 26, # 2, p. 390 - 395]
[4]Aristeo-Dominguez, Alberto; Melendez-Rodriguez, Myriam; Castillo, Oscar R. Suarez; Contreras-Martinez, Yaneth M. A.; Suarez-Ramirez, Lizbeth; Trejo-Carbajal, Nayely; Morales-Rios, Martha S.; Joseph-Nathan, Pedro [Heterocycles, 2013, vol. 87, # 6, p. 1249 - 1267]

47
[ 875-79-6 ]
[ 22979-35-7 ]
[ 1204478-46-5 ]

Yield	Reaction Conditions	Operation in experiment
90%	With CuO/SiO₂ In dichloromethane at 20℃; for 15h; Inert atmosphere;
81%	With tris(pentafluorophenyl)borate In dichloromethane at 45℃; Inert atmosphere;	General Procedure b General procedure: Under a nitrogen atmosphere, the borane (10 mol%) was dissolved in CH2Cl2 (0.5 mL) and added to a CH2Cl2 solution (0.5 mL) of α-aryl α-diazoester (0.2 mmol). The heteroarene/indene/styrene (1.1 equiv.) was dissolved in CH2Cl2 (0.5 mL) and added to the reaction mixture dropwise. The reaction was heated at 45 °C for 18-24 h. All volatiles were removed in vacuo and the crude compound was purified via column chromatography using silica gel (Merck, 60 Å, 230-400 mesh particle size) and hexane/ethyl acetate as eluent.
80%	With [Rh₂([(3-phenyl-1,8-naphthyridin-2-yl)amino]carbonyl}ferrocene)₂(m-CH₃COO)₂][(BF₄)₂] In 1,2-dichloro-ethane at 20 - 60℃; for 24.5h; Inert atmosphere; Schlenk technique;

61%

With C₃₃H₂₈NNiO₃P In toluene at 0 - 100℃; for 24.3333h; Schlenk technique; Inert atmosphere; regioselective reaction;

Reference： [1]Fraile, Jose M.; Le Jeune, Karel; Mayoral, Jose A.; Ravasio, Nicoletta; Zaccheria, Federica [Organic and Biomolecular Chemistry, 2013, vol. 11, # 26, p. 4327 - 4332]
[2]Dasgupta, Ayan; Babaahmadi, Rasool; Slater, Ben; Yates, Brian F.; Ariafard, Alireza; Melen, Rebecca L. [Chem, 2020, vol. 6, # 9, p. 2364 - 2381]
[3]Sarkar, Mithun; Daw, Prosenjit; Ghatak, Tapas; Bera, Jitendra K. [Chemistry - A European Journal, 2014, vol. 20, # 50, p. 16537 - 16549]
[4]Nag, Ekta; Gorantla, Sai Manoj N. V. T.; Arumugam, Selvakumar; Kulkarni, Aditya; Mondal, Kartik Chandra; Roy, Sudipta [Organic Letters, 2020, vol. 22, # 16, p. 6313 - 6318]

48
[ 136-95-8 ]
[ 875-79-6 ]
1,2-dimethyl-3-(benzothiazol-2-yldiazenyl)-1H-indole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
79%	Stage #1: 2-amino-benzthiazole With acetic acid; propionic acid at -5 - 5℃; for 2h; Stage #2: With sulfuric acid; sodium nitrite at 0℃; for 2.5h; Stage #3: 1,2-dimethylindole With acetic acid; propionic acid at 0 - 5℃; for 2h;	Preparation of hetarylazoindole dyes General procedure: 2-Aminobenzothiazole (0.30 g, 2.0 mmol) was dissolved in hot glacial acetic acid/propionic acid mixture (2:1, 6.0 ml) and was rapidly cooled in an ice-salt bath to -5° C. The mixture was then stirred for 2 h. at 0-5 °C. The liquor was then added in portions during 30 min to a cold solution of nitrosyl sulfuric acid [prepared from sodium nitrite (0.15 g) and concentrated sulfuric acid (3 ml at 50 °C)]. The mixture was stirred for an additional 2 h at 0 °C. Excess nitrous acid was destroyed by the addition of urea. The resulting diazonium salt was cooled in salt/ice mixture. 2-methlyindole(0.26 g, 2.0 mmol) was dissolved in mixture of acetic acid/propionic acid solution (3:1, 8.0 ml) and cooled in salt/ice bath and then cold diazonium solution was added to this cooled solution by stirring in a dropwise manner. The solution was stirred at 0-5 °C for 2 h. and pH of the reaction mixture was maintained at 4-6 by simultaneous addition of saturated sodium carbonate solution.The mixture was stirred for a further 1 h at 5 °C. The resulting product was filtered, washed with water, dried and crystallized from ethanol mixture gave brown powder (yield: 0.29 g, 51%; m.p: 168-170 °C), FT-IR (KBr) νmax: 3345 (indole -NH), 3059 (aromatic C-H), 2969, 2920 (aliphatic C-H), 1605 (C=C) cm-1; 1HNMR (DMSO-d6/CDCl3): d 9.71 (b, indole -NH), 7.98 (1H,m), 7.37(1H,m), 7.30-7.15 (4H,m), 6.82 (2H,m), 2.36 (3H,s).Anal. Calcd. For C16H12N4S: C, 65.73; H, 4.14; N, 19.16; S, 10.97Found: C, 65.68; H, 4.19; N, 19.11; S, 10.92%.MS (m/z, 70 eV): 292.0 (M+), 277.0, 158.0, 130.0.

Reference： [1]Seferoǧlu, Zeynel; Kaynak, Filiz Betul; Ertan, Nermin; Ozbey, Suheyla [Journal of Molecular Structure, 2013, vol. 1047, p. 22 - 30]

49
[ 875-79-6 ]
[ 1747-60-0 ]
1,2-dimethyl-3-(6-methoxybenzothiazol-2-yldiazenyl)-1H-indole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80%	Stage #1: 6-methoxybenzothiazol-2-ylamine With acetic acid; propionic acid at -5 - 5℃; for 2h; Stage #2: With sulfuric acid; sodium nitrite at 0℃; for 2.5h; Stage #3: 1,2-dimethylindole With acetic acid; propionic acid at 0 - 5℃; for 2h;	Preparation of hetarylazoindole dyes General procedure: 2-Aminobenzothiazole (0.30 g, 2.0 mmol) was dissolved in hot glacial acetic acid/propionic acid mixture (2:1, 6.0 ml) and was rapidly cooled in an ice-salt bath to -5° C. The mixture was then stirred for 2 h. at 0-5 °C. The liquor was then added in portions during 30 min to a cold solution of nitrosyl sulfuric acid [prepared from sodium nitrite (0.15 g) and concentrated sulfuric acid (3 ml at 50 °C)]. The mixture was stirred for an additional 2 h at 0 °C. Excess nitrous acid was destroyed by the addition of urea. The resulting diazonium salt was cooled in salt/ice mixture. 2-methlyindole(0.26 g, 2.0 mmol) was dissolved in mixture of acetic acid/propionic acid solution (3:1, 8.0 ml) and cooled in salt/ice bath and then cold diazonium solution was added to this cooled solution by stirring in a dropwise manner. The solution was stirred at 0-5 °C for 2 h. and pH of the reaction mixture was maintained at 4-6 by simultaneous addition of saturated sodium carbonate solution.The mixture was stirred for a further 1 h at 5 °C. The resulting product was filtered, washed with water, dried and crystallized from ethanol mixture gave brown powder (yield: 0.29 g, 51%; m.p: 168-170 °C), FT-IR (KBr) νmax: 3345 (indole -NH), 3059 (aromatic C-H), 2969, 2920 (aliphatic C-H), 1605 (C=C) cm-1; 1HNMR (DMSO-d6/CDCl3): d 9.71 (b, indole -NH), 7.98 (1H,m), 7.37(1H,m), 7.30-7.15 (4H,m), 6.82 (2H,m), 2.36 (3H,s).Anal. Calcd. For C16H12N4S: C, 65.73; H, 4.14; N, 19.16; S, 10.97Found: C, 65.68; H, 4.19; N, 19.11; S, 10.92%.MS (m/z, 70 eV): 292.0 (M+), 277.0, 158.0, 130.0.

Reference： [1]Seferoǧlu, Zeynel; Kaynak, Filiz Betul; Ertan, Nermin; Ozbey, Suheyla [Journal of Molecular Structure, 2013, vol. 1047, p. 22 - 30]

50
[ 875-79-6 ]
[ 29927-08-0 ]
1,2-dimethyl-3-(5,6-dimethylbenzothiazol-2-yldiazenyl)-1H-indole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
78%		General procedure: 2-Aminobenzothiazole (0.30 g, 2.0 mmol) was dissolved in hot glacial acetic acid/propionic acid mixture (2:1, 6.0 ml) and was rapidly cooled in an ice-salt bath to -5 C. The mixture was then stirred for 2 h. at 0-5 C. The liquor was then added in portions during 30 min to a cold solution of nitrosyl sulfuric acid [prepared from sodium nitrite (0.15 g) and concentrated sulfuric acid (3 ml at 50 C)]. The mixture was stirred for an additional 2 h at 0 C. Excess nitrous acid was destroyed by the addition of urea. The resulting diazonium salt was cooled in salt/ice mixture. 2-methlyindole(0.26 g, 2.0 mmol) was dissolved in mixture of acetic acid/propionic acid solution (3:1, 8.0 ml) and cooled in salt/ice bath and then cold diazonium solution was added to this cooled solution by stirring in a dropwise manner. The solution was stirred at 0-5 C for 2 h. and pH of the reaction mixture was maintained at 4-6 by simultaneous addition of saturated sodium carbonate solution.The mixture was stirred for a further 1 h at 5 C. The resulting product was filtered, washed with water, dried and crystallized from ethanol mixture gave brown powder (yield: 0.29 g, 51%; m.p: 168-170 C), FT-IR (KBr) numax: 3345 (indole -NH), 3059 (aromatic C-H), 2969, 2920 (aliphatic C-H), 1605 (C=C) cm-1; 1HNMR (DMSO-d6/CDCl3): d 9.71 (b, indole -NH), 7.98 (1H,m), 7.37(1H,m), 7.30-7.15 (4H,m), 6.82 (2H,m), 2.36 (3H,s).Anal. Calcd. For C16H12N4S: C, 65.73; H, 4.14; N, 19.16; S, 10.97Found: C, 65.68; H, 4.19; N, 19.11; S, 10.92%.MS (m/z, 70 eV): 292.0 (M+), 277.0, 158.0, 130.0.

Reference： [1]Journal of Molecular Structure,2013,vol. 1047,p. 22 - 30

51
[ 875-79-6 ]
[ 6285-57-0 ]
1,2-dimethyl-3-(6-nitrobenzothiazol-2-yldiazenyl)-1H-indole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
66%	Stage #1: 2-amino-6-nitrobenzothiazole With acetic acid; propionic acid at -5 - 5℃; for 2h; Stage #2: With sulfuric acid; sodium nitrite at 0℃; for 2.5h; Stage #3: 1,2-dimethylindole With acetic acid; propionic acid at 0 - 5℃; for 2h;	Preparation of hetarylazoindole dyes General procedure: 2-Aminobenzothiazole (0.30 g, 2.0 mmol) was dissolved in hot glacial acetic acid/propionic acid mixture (2:1, 6.0 ml) and was rapidly cooled in an ice-salt bath to -5° C. The mixture was then stirred for 2 h. at 0-5 °C. The liquor was then added in portions during 30 min to a cold solution of nitrosyl sulfuric acid [prepared from sodium nitrite (0.15 g) and concentrated sulfuric acid (3 ml at 50 °C)]. The mixture was stirred for an additional 2 h at 0 °C. Excess nitrous acid was destroyed by the addition of urea. The resulting diazonium salt was cooled in salt/ice mixture. 2-methlyindole(0.26 g, 2.0 mmol) was dissolved in mixture of acetic acid/propionic acid solution (3:1, 8.0 ml) and cooled in salt/ice bath and then cold diazonium solution was added to this cooled solution by stirring in a dropwise manner. The solution was stirred at 0-5 °C for 2 h. and pH of the reaction mixture was maintained at 4-6 by simultaneous addition of saturated sodium carbonate solution.The mixture was stirred for a further 1 h at 5 °C. The resulting product was filtered, washed with water, dried and crystallized from ethanol mixture gave brown powder (yield: 0.29 g, 51%; m.p: 168-170 °C), FT-IR (KBr) νmax: 3345 (indole -NH), 3059 (aromatic C-H), 2969, 2920 (aliphatic C-H), 1605 (C=C) cm-1; 1HNMR (DMSO-d6/CDCl3): d 9.71 (b, indole -NH), 7.98 (1H,m), 7.37(1H,m), 7.30-7.15 (4H,m), 6.82 (2H,m), 2.36 (3H,s).Anal. Calcd. For C16H12N4S: C, 65.73; H, 4.14; N, 19.16; S, 10.97Found: C, 65.68; H, 4.19; N, 19.11; S, 10.92%.MS (m/z, 70 eV): 292.0 (M+), 277.0, 158.0, 130.0.

Reference： [1]Seferoǧlu, Zeynel; Kaynak, Filiz Betul; Ertan, Nermin; Ozbey, Suheyla [Journal of Molecular Structure, 2013, vol. 1047, p. 22 - 30]

52
[ 875-79-6 ]
[ 62-53-3 ]
[ 1542217-51-5 ]

Yield	Reaction Conditions	Operation in experiment
85%	Stage #1: aniline With hydrogenchloride; sodium nitrite In water at -0.16℃; for 1h; Stage #2: 1,2-dimethylindole With sodium carbonate In water; acetic acid; propionic acid at -0.16 - 20℃; for 2h;	1 2.2.1 Preparation of (E)-3-phenyldiazenyl-1,2-dimethyl-1H-indole (1) Aniline (0.18mL, 2.0mmol) was dissolved in concentrated HCl (1.5mL, % 36 w/w) and water (4.0mL). The solution was cooled in an ice-salt bath and a cold solution of NaNO2 (0.15g, 2mmol) in water (3.0mL) was added dropwise with stirring. The mixture was stirred for an additional 1h at 273K. Excess nitrous acid was destroyed by the addition of urea. The resulting diazonium salt was cooled in a salt/ice mixture. 1,2-dimethylindole (0.29g, 2.0mmol) was dissolved in a mixture of acetic acid and propionic acid solution (3.0 : 1.8mL) and cooled in an ice bath. Then, cold diazonium solution was added to this cooled solution by stirring in a dropwise manner. The solution was stirred at 273-278K for 1h. The pH of the reaction mixture was maintained at 4-6 by the simultaneous addition of saturated sodium carbonate solution. The mixture was stirred for a further 1h at room temperature. The resulting solid was filtered, washed with cold water, and then dried. Recrystallization from ethanol gave yellow crystals (0.425g, 85% yield; m.p: 125°C) FT-IR (KBr) max: 3055 (aromatic C-H), 2915 (aliphatic C-H), 1534, 1476,1446 (C=C), 1387 (N=N) cm-1; 1H NMR (DMSO-d6): δ 8.39 (dd, 1H, J1=7.80Hz, J2=1.11Hz), 7.82 (dd, 2H, J1=8.10Hz, J2=1.13Hz), 7.58 (d, 1H, J1=7.59Hz), 7.51 (t, 2H, J1=8.01Hz), 7.38 (t, 1H, J1=7.28Hz), 7.29 (td, 1H, J1=7.25Hz, J2=1.33Hz), 7.25 (td, 1H, J1=7.37Hz, J2=1.05Hz), 3.74 (s, 3H, -NCH3), 2.82 (s, 3H, -CH3), HRMS (M+) calcd for C16H16N3 250.1344; found, 250.1343.