Name: 135-77-3|1,2,4-Trimethoxybenzene|95%
Brand: Ambeed
SKU: A767549
Price: 7.0 USD
Availability: InStock
Rating: 97 (32 reviews)

1
[ 50-00-0 ]
[ 135-77-3 ]
[ 30038-32-5 ]

Yield	Reaction Conditions	Operation in experiment
99%	With trifluorormethanesulfonic acid In acetonitrile at 0 - 20℃; for 1h;
99%	With 1-methyl-3-(propyl-3-sulfonyl)imidazolium trifluoromethanesulfonate In neat (no solvent) at 40℃; for 0.5h; Green chemistry;	General procedure for triarylmethanes and diarylalkanessynthesis General procedure: A mixture of aldehyde 2 (1.0 mmol), aromatic compound 1(2.0 mmol) and BAILs (0.2 mmol) was stirred at 40∘C for the desired time. The reaction was monitored by thin layer chromatography(TLC). After the completion of the reaction, 1 ml of water was added into the reaction mixture, and the target compound was obtained though simple filtration. The pure ionic liquids got by drying the filtrate were reused for another cycle. Synthesis route is listed in Scheme 2.
	With sulfuric acid; acetic acid

Reference： [1]Wilsdorf, Michael; Leichnitz, Daniel; Reissig, Hans-Ulrich [Organic Letters, 2013, vol. 15, # 10, p. 2494 - 2497]
[2]Wang, Ailing; Zheng, Xueliang; Zhao, Zhuangzhi; Li, Changping; Cui, Yingna; Zheng, Xuefang; Yin, Jingmei; Yang, Guang [Applied Catalysis A: General, 2014, vol. 482, p. 198 - 204]
[3]Werber [Annali di Chimica, 1959, vol. 49, p. 1898,1912]

2
[ 91-01-0 ]
[ 135-77-3 ]
diphenyl(2,4,5-trimethoxyphenyl)methane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
100%	With o-benzenedisulfonimide In neat (no solvent) at 20℃; for 1.5h;	1 4.2.9 Diphenyl(2,4,5-trimethoxyphenyl)methane (6a) General procedure: General procedure for di- and triaryl (and heteroaryl) methane 4-14 syntheses: A mixture of alcohol 2 (1.0 mmol) or styrene 15, aromatic compound 3 (mmol as in Table 3) and o-benzenedisulfonimide (1, 10 mol%, 0.022 g) was stirred at rt (or under heating, as reported in Table 3) in a vial until TLC, GC and GC-MS analyses shown the almost complete conversion of 2 (or 15). The reaction mixture was then treated with CH2Cl2/H2O (1:1, 20 mL). The aqueous phase was extracted with CH2Cl2 (2×20mL). The combined organic extracts were dried with Na2SO4 and concentrated under reduced pressure. The crude residue was purified by column chromatography (silica gel, PE/AcOEt or PE/Acetone or PE/EE).
85%	With 2C₂H₆O₂*ZnCl₂ at 90℃; for 1h;	10 Example 2 25mL round bottom flask, followed by adding 336mg (2.0mmol) 1,2,4- trimethoxyBenzene and 368mg (2.0mmol) benzhydrol, was added 1.04g (4.0mmol) [EG] 2 [ZnCl2] magnetic stirrer, oil bath controlled at temperature 90 stirring, thin layer chromatography monitoring the progress of the reaction, the reaction 1h after the reaction was stopped. Based on 1 mole of the electron-rich aromatic compound is a standard, DES ([EG] 2 [ZnCl2]) in an amount of 2 mol, the amount of diaryl methanol is 1 mol, the reaction temperature was 90 deg.] C, the reaction time was 1h. After treatment, after cooling to room temperature was added 10mL distilled water and extracted with 10mL ethyl acetate, [EG] 2 [ZnCl2] dissolved in the aqueous phase, the product was dissolved in ethyl acetate layer was separated, the ethyl acetate layer was washed with saturated brine time, dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure, followed by column separation and purification, to give a white solid, yield 85%
	With hydrogenchloride; ethanol

Reference： [1]Barbero, Margherita; Cadamuro, Silvano; Dughera, Stefano; Rucci, Marta; Spano, Giulia; Venturello, Paolo [Tetrahedron, 2014, vol. 70, # 9, p. 1818 - 1826]
[2]Current Patent Assignee: DALIAN UNIVERSITY - CN105237362, 2016, A Location in patent: Paragraph 0058; 0059; 0060; 0061
[3]Szeki [Chemische Berichte, 1923, vol. 56, p. 2468]

3
[ 1070-62-8 ]
[ 135-77-3 ]
[ 92865-60-6 ]
5-oxo-5-(2,4,5-trimethoxy-phenyl)-valeric acid ethyl ester [ No CAS ]

Reference： [1]Journal of the American Chemical Society,1955,vol. 77,p. 598,600

4
[ 2832-19-1 ]
[ 135-77-3 ]
chloro-acetic acid-(2,4,5-trimethoxy-benzylamide) [ No CAS ]

Reference： [1]Gazzetta Chimica Italiana,1930,vol. 60,p. 777,778

5
[ 6301-54-8 ]
[ 135-77-3 ]
2-[1]naphthyl-2-(2,4,5-trimethoxy-phenyl)-propane [ No CAS ]

Reference： [1],vol. 2,p. 8
Chemisches Zentralblatt,1926,vol. 97,p. 1984

6
[ 135-77-3 ]
[ 25808-30-4 ]
2-methylamino-1-(2,4,5-trimethoxy-phenyl)-ethanone [ No CAS ]

Reference： [1]Patent: US2683743,1950,

7
[ 135-77-3 ]
[ 14227-14-6 ]

Yield	Reaction Conditions	Operation in experiment
100%	With Nitrogen dioxide In dichloromethane in the dark; -78 deg C, 2 min; RT, 15 min;
98%	With tert.-butylnitrite In dichloromethane at 20℃; for 6h;
95%	With tert.-butylnitrite In acetonitrile at 20℃; for 1h;	15 This is achieved by the following steps 1 mmol of 1,2,4-trimethoxybenzene was added to the reaction flask, and dissolved in 2 mL of acetonitrile. 145 uL of t-butyl nitrite was added, and the mixture was stirred at room temperature for 1 hour. After the reaction was completed, the mixture was removed by a rotary evaporator. The organic solvent was subjected to column chromatography to give the product nitro product. The reaction yield was 95%

93%	With 3-(ethoxycarbonyl)-1-(5-methyl-5-(nitrosooxy)hexyl)pyridin-1-ium bis(trifluoromethanesulfonyl)imide at 20℃; for 2h; Ionic liquid;	General procedure for the synthesis of products (1b-30b) General procedure: To a Schlenk tube were added arene (1 mmol) and TS-N-IL (1.3 mmol). Then the tube was stirred at room temperature under air for the indicated time until complete consumption of starting material as monitored by TLC analysis. After the reaction was finished, the reaction mixture was extracted with ethyl acetate (3 20 mL). The combined extracts were washed with aqueous NaHCO3, dried over anhydrous Na2SO4 and evaporated in a rotary evaporator under reduced pressure. The crude product was purified by filtration through a column chromatography on silica gel employing ethyl acetate-hexane mixture to afford the desired product. The purity of the compound was confirmed by NMR and mass analysis, vide infra.
88%	With cerium(IV) ammonium nitrate supported on silica In dichloromethane for 0.25h; Ambient temperature;
86.8%	With nitric acid; acetic acid at 20℃; for 12h; Inert atmosphere;
85%	With nitric acid; acetic acid at 0℃; for 4h; Inert atmosphere;
81%	With nitronium tetrafluoborate In 1,2-dimethoxyethane at -50℃;
76%	With 1,1,1,3',3',3'-hexafluoro-propanol; tetrabutylammonium nitrite In acetonitrile at 20℃; for 0.833333h; Electrochemical reaction; Inert atmosphere; Green chemistry;
63%	With nitric acid; acetic acid at 20℃; for 0.166667h;
46%	With ammonium cerium (IV) nitrate; sodium hydrogencarbonate In acetonitrile at 20℃; for 0.166667h; Inert atmosphere;
	With nitric acid; acetic acid
	Multi-step reaction with 2 steps 1: aluminium chloride; carbon disulfide 2: glacial acetic acid; concentrated nitric acid

Reference： [1]Rathore; Bosch; Kochi [Tetrahedron, 1994, vol. 50, # 23, p. 6727 - 6758]
[2]Sahana, Tuhin; Mondal, Aditesh; Anju, Balakrishnan S.; Kundu, Subrata [Angewandte Chemie - International Edition, 2021, vol. 60, # 38, p. 20661 - 20665][Angew. Chem., 2021, vol. 133, # 38, p. 20829 - 20833]
[3]Current Patent Assignee: CHINESE ACADEMY OF SCIENCES - CN108530242, 2018, A Location in patent: Paragraph 0075-0077
[4]Chaudhary, Renu; Natarajan, Palani; Rani, Neetu; Sakshi; Venugopalan, Paloth [Tetrahedron Letters, 2019]
[5]Grenier, Jean-Luc; Catteau, Jean-Pierre; Cotelle, Philippe [Synthetic Communications, 1999, vol. 29, # 7, p. 1201 - 1208]
[6]Nepali, Kunal; Kumar, Sunil; Huang, Hsiang-Ling; Kuo, Fei-Chiao; Lee, Cheng-Hsin; Kuo, Ching-Chuan; Yeh, Teng-Kuang; Li, Yu-Hsuan; Chang, Jang-Yang; Liou, Jing-Ping; Lee, Hsueh-Yun [Organic and Biomolecular Chemistry, 2015, vol. 14, # 2, p. 716 - 723]
[7]González, Myriam; Ovejero-Sánchez, María; Vicente-Blázquez, Alba; Medarde, Manuel; González-Sarmiento, Rogelio; Peláez, Rafael [Journal of Enzyme Inhibition and Medicinal Chemistry, 2021, vol. 36, # 1, p. 1029 - 1047]
[8]Dwyer; Holzapfel [Tetrahedron, 1998, vol. 54, # 27, p. 7843 - 7848]
[9]Blum, Stephan P.; Nickel, Christean; Schäffer, Lukas; Karakaya, Tarik; Waldvogel, Siegfried R. [ChemSusChem, 2021, vol. 14, # 22, p. 4936 - 4940]
[10]Chan, Bryan K.; Ciufolini, Marco A. [Journal of Organic Chemistry, 2007, vol. 72, # 22, p. 8489 - 8495]
[11]Gupta, Vijay; Rao, V. U. Bhaskara; Das, Tamal; Vanka, Kumar; Singh, Ravi P. [Journal of Organic Chemistry, 2016, vol. 81, # 13, p. 5663 - 5669]
[12]Schueler [Archiv der Pharmazie, 1907, vol. 245, p. 267,271]
[13]Bargellini; Madesani [Gazzetta Chimica Italiana, 1931, vol. 61, p. 684,691]

8
[ 135-77-3 ]
[ 23149-33-9 ]

Yield	Reaction Conditions	Operation in experiment
100%	With iodine; silver trifluoroacetate In dichloromethane at 0℃; for 8h;
99%	With N-iodo-succinimide; trifluoroacetic acid In acetonitrile at 20℃; for 0.1h;
99%	With N-iodo-succinimide In acetonitrile at 20℃; for 16h; Inert atmosphere; Schlenk technique;

99%	With N-iodo-succinimide In acetonitrile at 20℃; for 2h;	1 Example 1: Synthesis of Iodo 1,2,4-trimethoxybenzene (3, see Figure 1) A solution of 1,2,4-trimethoxybenzene was dissolved in 25 ml of anhydrous acetonitrile. NIS (10 · Ommol) was added and the reaction was stirred at room temperature for 2 hours. The TLC reaction was terminated TheAdd 30 ml of water, ethyl acetate extraction (30mL χ 3), the organic phase, washed with saturated brine, dried over anhydrous sodium sulfate, filtered, concentrated, column chromatography to obtain white solid iodine 1,2,4 Trimethoxybenzene 2.90 g, yield 99%
95%	With N-iodo-succinimide In acetonitrile at 20℃; for 4h;
83%	With sulfuric acid; dihydrogen peroxide; iodine at 50℃; for 4h;
80%	With iodine; urea hydrogen peroxide adduct; 3-butyl-1-methyl-1H-imidazol-3-ium hexafluorophosphate at 50℃; for 4h;
72%	With iodine; mercury(II) oxide In dichloromethane for 7h; Ambient temperature;
58%	With iodine; urea hydrogen peroxide adduct at 45℃; for 17h;
	With methanol; iodine; mercury(II) oxide
	With ethanol; iodine; mercury(II) oxide at 50℃;
	With ethanol; iodine; mercury(II) oxide at 50℃;
	With poly(4-vinylpyridine)-supported peroxodisulfate; iodine In acetonitrile for 5h; Heating;
	With 1-butyl-3-methylimidazolium hydrogen sulfate In acetonitrile at 20℃; regioselective reaction;

Reference： [1]Lee, Chia-Lin; Huang, Chi-Huan; Wang, Hui-Chun; Chuang, Da-Wei; Wu, Ming-Jung; Wang, Sheng-Yang; Hwang, Tsong-Long; Wu, Chin-Chung; Chen, Yeh-Long; Chang, Fang-Rong; Wu, Yang-Chang [Organic and Biomolecular Chemistry, 2011, vol. 9, # 1, p. 70 - 73]
[2]Castanet, Anne-Sophie; Colobert, Françoise; Broutin, Pierre-Emmanuel [Tetrahedron Letters, 2002, vol. 43, # 29, p. 5047 - 5048]
[3]Noble, Adam; Roesner, Stefan; Aggarwal, Varinder K. [Angewandte Chemie - International Edition, 2016, vol. 55, # 51, p. 15920 - 15924][Angew. Chem., 2016, vol. 128, # 51, p. 16152 - 16156,5]
[4]Current Patent Assignee: HARBIN INSTITUTE OF TECHNOLOGY - CN106588854, 2017, A Location in patent: Paragraph 0013
[5]Carreno, M. Carmen; Garcia Ruano, Jose L.; Sanz, Gema; Toledo, Miguel A.; Urbano, Antonio [Tetrahedron Letters, 1996, vol. 37, # 23, p. 4081 - 4084]
[6]Pavlinac, Jasminka; Zupan, Marko; Stavber, Stojan [Synthesis, 2006, # 15, p. 2603 - 2607]
[7]Location in patent: experimental part Pavlinac, Jasminka; Laali, Kenneth K.; Zupan, Marko; Stavber, Stojan [Australian Journal of Chemistry, 2008, vol. 61, # 12, p. 946 - 955]
[8]Orito; Hatakeyama; Takeo; Suginome [Synthesis, 1995, # 10, p. 1273 - 1277]
[9]Pavlinac, Jasminka; Zupan, Marko; Stavber, Stojan [Organic and Biomolecular Chemistry, 2007, vol. 5, # 4, p. 699 - 707]
[10]Meerwein; Hofmann; Schill [Journal fur praktische Chemie (Leipzig 1954), 1940, vol. <2> 154, p. 266,281]
[11]Hughes; Neill; Ritchie [Australian Journal of Scientific Research, Series A: Physical Sciences, 1950, vol. <A> 3, p. 497,500]
[12]Hughes; Neill; Ritchie [Australian Journal of Scientific Research, Series A: Physical Sciences, 1950, vol. <A> 3, p. 497,500]
[13]Tajik, Hassan; Mohammadpoor-Baltork, Iraj; Rasht-Abadi, Hassan Rafiee [Synthetic Communications, 2004, vol. 34, # 19, p. 3579 - 3585]
[14]Location in patent: experimental part Tajik, Hassan; Parsa, Fatemeh [Asian Journal of Chemistry, 2011, vol. 23, # 1, p. 465 - 466]

9
[ 135-77-3 ]
[ 99-61-6 ]
[ 54921-75-4 ]

Yield	Reaction Conditions	Operation in experiment
98%	With niobium pentachloride In dichloromethane at 0 - 20℃; for 24h;	Condensation Reaction of Aldehydes with Arenes in the Presence of NbCl5 as Acid Catalyst; General Procedure General procedure: A suspension of aldehyde (1 mmol) and NbCl5 (1 mmol) in DCM (5mL) was stirred at 0 °C. Then, arene (2.2 mmol) was added. The reac-tion was allowed to reach room temperature. The end of the reactionwas monitored via TLC. Next, the reaction mixture was quenchedwith saturated Na2CO3 solution (15 mL) and extracted with Et2O (3 × 20 mL). The organic layer was washed with brine, dried over an-hydrous MgSO4 , filtered, and concentrated. The residue was purifiedby flash column chromatography (silica gel; hexane-EtOAc, 9.5:0.5 to8:2 v/v) to afford the pure compounds. All obtained products werecharacterized by their spectroscopic data [ 1 H, 13 C, and 19 F NMR, IR, MS(EI)].
95%	With PEG-400 at 50 - 60℃; for 2h; Green chemistry;	General procedure for the synthesis of triarylmethanederivatives (3a-j) General procedure: To a 50 mL round bottomed flask, 1,3-dimethoxybenzene (1a, 2 mol), benzaldehyde (2a, 1 mol) and PEG-400 (15 mL) were successively added and then the mixture was magnetically stirred at 50-60 °C for the appropriate time specified in Scheme-I. The progress of the reaction was monitored by thin-layer chromatography (TLC) (ethyl acetate:hexane, 3:7). After completion of the reaction, the crude mixture was worked up in ice-cold water. The product that separated out was filtered and the filtrate was evaporated to remove water, leaving behind polyethylene glycol. The same polyethylene glycol was utilized to synthesize further triarylmethanederivatives. The resulting product, though seen as a single compound by TLC, was further purified by passing it over a column of silica gel (60-120 mesh) using ethyl acetate:hexane (3:7) as an eluent to afford the analytically pure compound,4,4'-(phenylmethylene)bis(1,3-dimethoxy-benzene) (3a). All other compounds 3b-j were synthesized according to the same experimental procedure.
	With hydrogenchloride; acetic acid

Reference： [1]Baviera, Giovanni S.; Donate, Paulo M.; Matias, Alexandre A.; Previdi, Daniel; Rodrigues, Shirley M. M. [Synthesis, 2019, vol. 51, # 23, p. 4498 - 4506]
[2]Revaprasadu; Sampath; Harika [Asian Journal of Chemistry, 2016, vol. 28, # 3, p. 473 - 478]
[3]Szeki [Chemische Berichte, 1911, vol. 44, p. 1479]

10
[ 135-77-3 ]
[ 555-16-8 ]
[ 54921-89-0 ]

Yield	Reaction Conditions	Operation in experiment
100%	With o-benzenedisulfonimide at 130℃; for 0.25h;
99%	With air; iodine In toluene at 20℃; for 72h;
98%	With niobium pentachloride In dichloromethane at 0 - 20℃; for 24h;	Condensation Reaction of Aldehydes with Arenes in the Presence of NbCl5 as Acid Catalyst; General Procedure General procedure: A suspension of aldehyde (1 mmol) and NbCl5 (1 mmol) in DCM (5mL) was stirred at 0 °C. Then, arene (2.2 mmol) was added. The reac-tion was allowed to reach room temperature. The end of the reactionwas monitored via TLC. Next, the reaction mixture was quenchedwith saturated Na2CO3 solution (15 mL) and extracted with Et2O (3 × 20 mL). The organic layer was washed with brine, dried over an-hydrous MgSO4 , filtered, and concentrated. The residue was purifiedby flash column chromatography (silica gel; hexane-EtOAc, 9.5:0.5 to8:2 v/v) to afford the pure compounds. All obtained products werecharacterized by their spectroscopic data [ 1 H, 13 C, and 19 F NMR, IR, MS(EI)].

97%	With trifluorormethanesulfonic acid In acetonitrile at 0 - 20℃; for 24h;
95%	With silica-supported sodium hydrogen sulfate at 115℃; for 3h; Inert atmosphere; Neat (no solvent);
94%	With 1-methyl-3-(propyl-3-sulfonyl)imidazolium trifluoromethanesulfonate In neat (no solvent) at 40℃; for 0.5h; Green chemistry;	General procedure for triarylmethanes and diarylalkanessynthesis General procedure: A mixture of aldehyde 2 (1.0 mmol), aromatic compound 1(2.0 mmol) and BAILs (0.2 mmol) was stirred at 40∘C for the desired time. The reaction was monitored by thin layer chromatography(TLC). After the completion of the reaction, 1 ml of water was added into the reaction mixture, and the target compound was obtained though simple filtration. The pure ionic liquids got by drying the filtrate were reused for another cycle. Synthesis route is listed in Scheme 2.
	With hydrogenchloride; acetic acid

Reference： [1]Barbero, Margherita; Cadamuro, Silvano; Dughera, Stefano; Magistris, Claudio; Venturello, Paolo [Organic and Biomolecular Chemistry, 2011, vol. 9, # 24, p. 8393 - 8399]
[2]Location in patent: experimental part Jaratjaroonphong, Jaray; Sathalalai, Supaporn; Techasauvapak, Prapapan; Reutrakul, Vichai [Tetrahedron Letters, 2009, vol. 50, # 44, p. 6012 - 6015]
[3]Baviera, Giovanni S.; Donate, Paulo M.; Matias, Alexandre A.; Previdi, Daniel; Rodrigues, Shirley M. M. [Synthesis, 2019, vol. 51, # 23, p. 4498 - 4506]
[4]Wilsdorf, Michael; Leichnitz, Daniel; Reissig, Hans-Ulrich [Organic Letters, 2013, vol. 15, # 10, p. 2494 - 2497]
[5]Location in patent: experimental part Leng, Yixin; Chen, Fang; Zuo, Li; Duan, Wenhu [Tetrahedron Letters, 2010, vol. 51, # 17, p. 2370 - 2373]
[6]Wang, Ailing; Zheng, Xueliang; Zhao, Zhuangzhi; Li, Changping; Cui, Yingna; Zheng, Xuefang; Yin, Jingmei; Yang, Guang [Applied Catalysis A: General, 2014, vol. 482, p. 198 - 204]
[7]Szeki [Chemische Berichte, 1911, vol. 44, p. 1479]

11
[ 135-77-3 ]
[ 100-52-7 ]
[ 54921-86-7 ]

Yield	Reaction Conditions	Operation in experiment
99%	With 1-methyl-3-(propyl-3-sulfonyl)imidazolium trifluoromethanesulfonate In neat (no solvent) at 40℃; for 0.5h; Green chemistry;	General procedure for triarylmethanes and diarylalkanessynthesis General procedure: A mixture of aldehyde 2 (1.0 mmol), aromatic compound 1(2.0 mmol) and BAILs (0.2 mmol) was stirred at 40∘C for the desired time. The reaction was monitored by thin layer chromatography(TLC). After the completion of the reaction, 1 ml of water was added into the reaction mixture, and the target compound was obtained though simple filtration. The pure ionic liquids got by drying the filtrate were reused for another cycle. Synthesis route is listed in Scheme 2.
95%	With boron trifluoride diethyl etherate In dichloromethane at 20℃; for 0.0833333h;
93%	With o-benzenedisulfonimide at 130℃; for 3.5h; neat (no solvent);

90%	With air; iodine In toluene at 20℃; for 72h;
90%	With niobium pentachloride In dichloromethane at 0 - 20℃; for 24h;	Condensation Reaction of Aldehydes with Arenes in the Presence of NbCl5 as Acid Catalyst; General Procedure General procedure: A suspension of aldehyde (1 mmol) and NbCl5 (1 mmol) in DCM (5mL) was stirred at 0 °C. Then, arene (2.2 mmol) was added. The reac-tion was allowed to reach room temperature. The end of the reactionwas monitored via TLC. Next, the reaction mixture was quenchedwith saturated Na2CO3 solution (15 mL) and extracted with Et2O (3 × 20 mL). The organic layer was washed with brine, dried over an-hydrous MgSO4 , filtered, and concentrated. The residue was purifiedby flash column chromatography (silica gel; hexane-EtOAc, 9.5:0.5 to8:2 v/v) to afford the pure compounds. All obtained products werecharacterized by their spectroscopic data [ 1 H, 13 C, and 19 F NMR, IR, MS(EI)].
65%	With aminosulfonic acid at 120℃; for 6h;	10 Example 10.Synthesis of 1,1 '- (phenylmethyl) bis (2,4,5-trimethoxybenzene): In a round bottom flask, 1 mmol (0.103 ml) of benzaldehyde, 4 mmol of 1,2,4-trimethoxybenzene and 0.1 mmol of sulfamic acid were added, followed by heating in an oil bath to 120 ° C under magnetic stirring for 6 hours.The oil bath was removed and the temperature was lowered to room temperature. The catalyst was filtered off and the mother liquor was concentrated by rotary evaporator. The residue was extracted with petroleum ether as eluent and chromatographed on silica gel.Pure triarylmethane was obtained in 65% isolated yield. The NMR data of the compound are as follows:
	With ethanol; sulfuric acid
	With hydrogenchloride; acetic acid

Reference： [1]Wang, Ailing; Zheng, Xueliang; Zhao, Zhuangzhi; Li, Changping; Cui, Yingna; Zheng, Xuefang; Yin, Jingmei; Yang, Guang [Applied Catalysis A: General, 2014, vol. 482, p. 198 - 204]
[2]Babu, B. Madhu; Thakur, Pramod B.; Nageswara Rao; Santosh Kumar; Meshram [Tetrahedron Letters, 2014, vol. 55, # 11, p. 1868 - 1872]
[3]Barbero, Margherita; Cadamuro, Silvano; Dughera, Stefano; Magistris, Claudio; Venturello, Paolo [Organic and Biomolecular Chemistry, 2011, vol. 9, # 24, p. 8393 - 8399]
[4]Location in patent: experimental part Jaratjaroonphong, Jaray; Sathalalai, Supaporn; Techasauvapak, Prapapan; Reutrakul, Vichai [Tetrahedron Letters, 2009, vol. 50, # 44, p. 6012 - 6015]
[5]Baviera, Giovanni S.; Donate, Paulo M.; Matias, Alexandre A.; Previdi, Daniel; Rodrigues, Shirley M. M. [Synthesis, 2019, vol. 51, # 23, p. 4498 - 4506]
[6]Current Patent Assignee: HIGH NEW TECH RESEARCH CENTER OF HENAN ACADEMY OF - CN107674048, 2018, A Location in patent: Paragraph 0041; 0042
[7]Erdtman [Svensk Kemisk Tidskrift, 1938, vol. 50, p. 68,70]
[8]Szeki [Chemische Berichte, 1911, vol. 44, p. 1479]

12
[ 135-77-3 ]
[ 90-02-8 ]
2''-Oxy-2.4.5.2'.4'.5'-hexamethoxy-triphenylmethan [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
74%	With 1-methyl-3-(propyl-3-sulfonyl)imidazolium trifluoromethanesulfonate In neat (no solvent) at 40℃; for 8h; Green chemistry;	General procedure for triarylmethanes and diarylalkanessynthesis General procedure: A mixture of aldehyde 2 (1.0 mmol), aromatic compound 1(2.0 mmol) and BAILs (0.2 mmol) was stirred at 40∘C for the desired time. The reaction was monitored by thin layer chromatography(TLC). After the completion of the reaction, 1 ml of water was added into the reaction mixture, and the target compound was obtained though simple filtration. The pure ionic liquids got by drying the filtrate were reused for another cycle. Synthesis route is listed in Scheme 2.
	With hydrogenchloride; acetic acid

Reference： [1]Wang, Ailing; Zheng, Xueliang; Zhao, Zhuangzhi; Li, Changping; Cui, Yingna; Zheng, Xuefang; Yin, Jingmei; Yang, Guang [Applied Catalysis A: General, 2014, vol. 482, p. 198 - 204]
[2]Szeki [Chemische Berichte, 1911, vol. 44, p. 1479]

13
[ 135-77-3 ]
[ 75-36-5 ]
[ 1818-28-6 ]

Yield	Reaction Conditions	Operation in experiment
89%	With aluminium trichloride In dichloromethane at 10℃; for 1h;
83%	With choline chloride * 2ZnCl₂ In neat (no solvent) at 70℃; for 0.5h; Green chemistry;	General procedure for aromatic ketone compounds synthesis General procedure: A mixture of electron-rich arenes a (2.0 mmol), acylation reagent b ((2.0 mmol)and catalytic solvent DES [ChCl][ZnCl 2 ] 2 (2.0 mmol) were added and stirred in a25 mL round-bottomed ask at 70 C for the desired time. The reaction procedurewas monitored by TLC and recorded the experimental phenomena. Aftercompletion of the reaction, 10 mL of water and 10 mL of ethyl acetate wereadded to the mixture and then cooled to room temperature, collecting the productand solvent from the organic phase and water, respectively. The organic phase waswashed with saturated sodium hydrogen carbonate solution and saturated brinesuccessively, then evaporated under high vacuum to give the target compound. PureDES was obtained by drying sufciently in a vacuum, and it could be reused foranother cycle.
81%	With aluminum (III) chloride In dichloromethane at 10℃; for 1h;

60%	With 1,1,1,3',3',3'-hexafluoro-propanol at 20℃; for 5h; Inert atmosphere;
	With aluminium trichloride
	With carbon disulfide; aluminium trichloride
	With aluminium trichloride In diethyl ether

Reference： [1]Hoegberg, Thomas; Bengtsson, Stefan; Paulis, Tomas de; Johansson, Lars; Stroem, Peter; et al. [Journal of Medicinal Chemistry, 1990, vol. 33, # 4, p. 1155 - 1163]
[2]Jin, Xiaojun; Wang, Ailing; Cao, Hongyu; Zhang, Shujia; Wang, Lihao; Zheng, Xueliang; Zheng, Xuefang [Research on Chemical Intermediates, 2018, vol. 44, # 9, p. 5521 - 5530]
[3]Location in patent: scheme or table Bello, Murilo Lamim; Chiaradia, Louise Domeneghini; Dias, Luiza Rosaria Sousa; Pacheco, Leticia Kramer; Stumpf, Taisa Regina; Mascarello, Alessandra; Steindel, Mario; Yunes, Rosendo Augusto; Castro, Helena Carla; Nunes, Ricardo Jose; Rodrigues, Carlos Rangel [Bioorganic and Medicinal Chemistry, 2011, vol. 19, # 16, p. 5046 - 5052]
[4]Vekariya, Rakesh H.; Aubé, Jeffrey [Organic Letters, 2016, vol. 18, # 15, p. 3534 - 3537]
[5]Hattori [Acta Phytochimica, 1932, vol. 6, p. 131,152] Kuroda; Matsukuma [Scientific Papers of the Institute of Physical and Chemical Research (Japan), 1932, vol. 18, p. 51,58][Chemisches Zentralblatt, 1932, vol. 103, # I, p. 2169]
[6]Reigrodski; Tambor [Chemische Berichte, 1910, vol. 43, p. 1965] Bargellini; Avrutin [Gazzetta Chimica Italiana, 1910, vol. 40 II, p. 349][Gazzetta Chimica Italiana, 1913, vol. 43 I, p. 165,167 Anm.]
[7]Hardegger,E. et al. [Helvetica Chimica Acta, 1964, vol. 47, p. 1996 - 2017]

14
[ 533-73-3 ]
[ 77-78-1 ]
[ 135-77-3 ]

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2008,vol. 18,p. 4380 - 4384
[2]Bioorganic and Medicinal Chemistry Letters,2017,vol. 27,p. 2397 - 2400
[3]Justus Liebigs Annalen der Chemie,1935,vol. 515,p. 23,28

15
[ 75-77-4 ]
[ 135-77-3 ]
[ 92669-98-2 ]

Yield	Reaction Conditions	Operation in experiment
96%	Stage #1: 1,2,4-trimethoxy-benzene With n-butyllithium; N,N,N,N,-tetramethylethylenediamine In tetrahydrofuran at 0℃; for 1.5h; Inert atmosphere; Stage #2: chloro-trimethyl-silane In tetrahydrofuran for 0.5h; Inert atmosphere;	1.1 Under argon protection, 23.8 mmol of 1,2,4-trimethoxybenzene (Compound 1) was dissolved in 80 ml of tetrahydrofuran, 47.6 mmol of tetramethylethylenediamine (TMEDA) was added dropwise to the stirred mixture, cooling to 0 °C, 28.5 mmol of n-butyllithium was added dropwise, and after 1.5 hours of reaction, 35.7mmol added dropwise trimethylsilyl chloride (TMSCl), the reaction 30min, quenched with saturated ammonium chloride, ethyl acetate was extracted three times, dried over anhydrous sodium sulfate and separated by column chromatography (volume ratio of ethyl acetate to petroleum ether 1:50), preparation of 1,2,4-trimethoxy-3-trimethylsilyl-benzene (Compound 2) in 96% yield.
96%	Stage #1: 1,2,4-trimethoxy-benzene With n-butyllithium; N,N,N,N,-tetramethylethylenediamine In tetrahydrofuran at 0℃; for 1.5h; Inert atmosphere; Stage #2: chloro-trimethyl-silane In tetrahydrofuran for 0.5h; Inert atmosphere;	1.1 under protection of argon, the 23.8 mmol 1,2,4-trimethoxybenzene (compound 1) dissolved in 80 ml in tetrahydrofuran, stirring adds by drops 47.6 mmol tetramethyl ethylenediamine (TMEDA), lowering the temperature to 0 °C, dropwise 28.5 mmol n-BuLi, reaction 1.5 hours, dropping 35.7 mmol trimethylchlorosilane (TMSCl), reaction 30 min, saturated ammonium chloride quenching, ethyl acetate extraction three times, adding anhydrous sodium sulfate drying, and column chromatography (ethyl acetate with petroleum ether of volume ratio of 1:50), made 1, 2, 4 - trimethoxy -3 - trimethyl silicon-based - benzene (compound 2), yield 96%.
96%	Stage #1: 1,2,4-trimethoxy-benzene With n-butyllithium; N,N,N,N,-tetramethylethylenediamine In tetrahydrofuran at 0℃; for 1.5h; Inert atmosphere; Stage #2: chloro-trimethyl-silane In tetrahydrofuran for 0.5h;	1.1; 2.1; 3.1 Step 1 Under argon atmosphere, 23.8 mmol of 1,2,4-trimethoxybenzene (compound 1) was dissolved in 80 ml of tetrahydrofuranWas added dropwise 47 · 6mmol tetramethylethylenediamine (TMEDA) was added dropwise with stirring, cooled to 0 ° C, was added dropwise 28 · 5mmol n-butyllithium, the reaction 1.5 hours after the dropwise addition of 35.7mmol trimethylchlorosilane (TMSC1) for 30 min, quenched with saturated ammonium chloride, extracted three times with ethyl acetate, dried over anhydrous sodium sulfate, and separated by column chromatography (volume ratio of ethyl acetate to petroleum ether 1:50) 1,2,4-Trimethoxy-3-trimethylsilyl-benzene (Compound 2) was obtained in a yield of 96%

96%	Stage #1: 1,2,4-trimethoxy-benzene With n-butyllithium In tetrahydrofuran at 0℃; for 2h; Stage #2: chloro-trimethyl-silane In tetrahydrofuran for 1h;	2.1 Preparation of Trimethyl (2,3,6-trimethoxyphenyl) silane (8): To solution of compound 7 (10.0 g, 59.49 mmol) in THF (50 mL) n-BuLi (2.5 M,65.44 mmol) was added at 0. The mixture was stirred for 2 hours. TMSCl (7.1 g,65.38 mmol) was added to the mixture. After 1 hour of stirring, the system wasquenched with saturated NH4Cl and extracted with EtOAc. The organic layer waswashed with saturated aqueous brine, and dried over anhydrous Na2SO4. The organicphase was concentrated by vacuum and purified by column chromatography,affording 8 as a colorless liquid (13.7 g, 96%): Rf (100 % Petroleum ether) 0.2; IR(CCl4)νmax: 2950, 2831, 1460, 1242, 1085, 856 cm-1; 1H NMR (400 MHz, CDCl3) δ6.89 (d, J = 8 Hz, 1H), 6.55 (d, J = 8 Hz, 1H), 3.83 (s, 3H), 3.82 (s, 3H), 3.74 (s, 3H),0.35 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 158.6, 154.6, 147.0, 121.2, 114.4, 105.4,60.9, 56.3, 55.6, 1.4; HRMS (ESI+) m/z: [M+H]+ calcd for C12H20NaO3Si, 241.1254;found, 241.1258.
91.2%	Stage #1: 1,2,4-trimethoxy-benzene With n-butyllithium In diethyl ether; hexane at -10 - 20℃; Inert atmosphere; Stage #2: chloro-trimethyl-silane In diethyl ether; hexane at -10℃; Inert atmosphere;
	With n-butyllithium; N,N,N,N,-tetramethylethylenediamine 1.) hexanes, room temp., 16 h 2.) 0 deg C; Yield given. Multistep reaction;
	With n-butyllithium; N,N,N,N,-tetramethylethylenediamine 1.) ethyl ether, hexane, r.t., 24 h, 2.) r.t., 4 h; Multistep reaction;
84 % Chromat.	Stage #1: 1,2,4-trimethoxy-benzene With n-butyllithium In cyclohexane for 0.166667h; Stage #2: chloro-trimethyl-silane In hexane; cyclohexane

Reference： [1]Current Patent Assignee: NORTHWEST UNIVERSITY (CHINA) - CN107032973, 2017, A Location in patent: Paragraph 0049-0050
[2]Current Patent Assignee: NORTHWEST UNIVERSITY (CHINA) - CN107032974, 2017, A Location in patent: Paragraph 0050; 0051
[3]Current Patent Assignee: NORTHWEST UNIVERSITY (CHINA) - CN107043386, 2017, A Location in patent: Paragraph 0054; 0058; 0062; 0066; 0070; 0074; 0078
[4]Yu, Tao; Shu, Xin; Yang, Kewu; Hu, Xiangdong [Synlett, 2018, vol. 29, # 12, p. 1617 - 1621]
[5]Location in patent: experimental part Alves, Ana P. L.; Junior, Jose Augusto B. C.; Slana, Glaucia B. A.; Cardoso, Jari N.; Wang, Qiang; Lopes, Rosangela S. C.; Lopes, Claudio C. [Synthetic Communications, 2009, vol. 39, # 20, p. 3693 - 3709]
[6]Crowther, G. P.; Sundberg, Richard J.; Sarpeshkar, Ashok M. [Journal of Organic Chemistry, 1984, vol. 49, # 24, p. 4657 - 4663]
[7]Cabiddu, Salvatore; Contini, Liliana; Fattuoni, Claudia; Floris, Costantino; Gelli, Gioanna [Tetrahedron, 1991, vol. 47, # 44, p. 9279 - 9288]
[8]Slocum; Dumbris, Seth; Brown, Scott; Jackson, Gina; LaMastus, Roslyn; Mullins, Elwood; Ray, Jonathan; Shelton, Phillip; Walstrom, Amy; Wilcox, J. Micah; Holman [Tetrahedron, 2003, vol. 59, # 41, p. 8275 - 8284]

16
[ 696-63-9 ]
[ 135-77-3 ]
[ 18113-18-3 ]

Reference： [1]Synthesis,1983,p. 751 - 755

17
[ 13330-65-9 ]
[ 124-41-4 ]
[ 135-77-3 ]

Reference： [1]Tetrahedron,1982,vol. 38,p. 3687 - 3692

18
[ 135-77-3 ]
[ 18113-18-3 ]

Reference： [1]Synthesis,1980,p. 638 - 640
[2]Tetrahedron,1982,vol. 38,p. 3687 - 3692
[3]Tetrahedron,1982,vol. 38,p. 3687 - 3692
[4]Tetrahedron,1982,vol. 38,p. 3687 - 3692

19
[ 135-77-3 ]
[ 79-03-8 ]
[ 3904-18-5 ]

Yield	Reaction Conditions	Operation in experiment
96%	With aluminum (III) chloride In dichloromethane at 5 - 20℃; for 1.5h; Large scale;	1.1; 2.1 1. Preparation of 2,4,5-trimethoxy-1-phenyl ethyl ketone 10 kg of 1,2,4-trimethoxybenzene, 6.5 kg of propionyl chloride, 55 kg of dichloromethane were put into the reaction kettle, stirred and cooled to 5 ° C, and 9 kg of aluminum trichloride was added in 4 portions.Each time aluminum trichloride was added to keep the temperature below 20 ° C, the reaction was stirred at room temperature for 1.5 hours.After the concentration of the reaction product was stabilized by TLC, the mixture was discharged to 40 kg of ice, and the oil and water layers were separated by stirring, and the oil layer was washed once with 20 liters of water. Combine the washing liquid and the water layer,Extract twice with 10 liters of dichloromethane, then wash the resulting extract once with 10 liters of water.The washed extract and the oil phase after washing are combined.Dry with 2.5 kg of sodium hydroxide for 1 hour, add 2.5 kg of anhydrous sodium sulfate, filter out the solid,Evaporate the dichloromethane in a water bath (recovery of 64 kg of dichloromethane), and crystallize at room temperature.The product obtained by filtration was 12.8 kg, and the yield was 96%.
80%	With aluminium trichloride In dichloromethane at 10℃; for 1h;
80%	With choline chloride * 2ZnCl₂ In neat (no solvent) at 70℃; for 0.5h; Green chemistry;	General procedure for aromatic ketone compounds synthesis General procedure: A mixture of electron-rich arenes a (2.0 mmol), acylation reagent b ((2.0 mmol)and catalytic solvent DES [ChCl][ZnCl 2 ] 2 (2.0 mmol) were added and stirred in a25 mL round-bottomed ask at 70 C for the desired time. The reaction procedurewas monitored by TLC and recorded the experimental phenomena. Aftercompletion of the reaction, 10 mL of water and 10 mL of ethyl acetate wereadded to the mixture and then cooled to room temperature, collecting the productand solvent from the organic phase and water, respectively. The organic phase waswashed with saturated sodium hydrogen carbonate solution and saturated brinesuccessively, then evaporated under high vacuum to give the target compound. PureDES was obtained by drying sufciently in a vacuum, and it could be reused foranother cycle.

With aluminium trichloride In carbon disulfide

Reference： [1]Current Patent Assignee: CHENGDE PETROLEUM COLLEGE - CN110128248, 2019, A Location in patent: Paragraph 0044-0047; 0054-0057
[2]Hoegberg, Thomas; Bengtsson, Stefan; Paulis, Tomas de; Johansson, Lars; Stroem, Peter; et al. [Journal of Medicinal Chemistry, 1990, vol. 33, # 4, p. 1155 - 1163]
[3]Jin, Xiaojun; Wang, Ailing; Cao, Hongyu; Zhang, Shujia; Wang, Lihao; Zheng, Xueliang; Zheng, Xuefang [Research on Chemical Intermediates, 2018, vol. 44, # 9, p. 5521 - 5530]
[4]Hardegger,E. et al. [Helvetica Chimica Acta, 1964, vol. 47, p. 1996 - 2017]

20
[ 135-77-3 ]
[ 141-75-3 ]
[ 2020-73-7 ]

Yield	Reaction Conditions	Operation in experiment
80%	With choline chloride * 2ZnCl₂ In neat (no solvent) at 70℃; for 0.583333h; Green chemistry;	General procedure for aromatic ketone compounds synthesis General procedure: A mixture of electron-rich arenes a (2.0 mmol), acylation reagent b ((2.0 mmol)and catalytic solvent DES [ChCl][ZnCl 2 ] 2 (2.0 mmol) were added and stirred in a25 mL round-bottomed ask at 70 C for the desired time. The reaction procedurewas monitored by TLC and recorded the experimental phenomena. Aftercompletion of the reaction, 10 mL of water and 10 mL of ethyl acetate wereadded to the mixture and then cooled to room temperature, collecting the productand solvent from the organic phase and water, respectively. The organic phase waswashed with saturated sodium hydrogen carbonate solution and saturated brinesuccessively, then evaporated under high vacuum to give the target compound. PureDES was obtained by drying sufciently in a vacuum, and it could be reused foranother cycle.
1.5 g	With aluminium trichloride In carbon disulfide Ambient temperature;

Reference： [1]Jin, Xiaojun; Wang, Ailing; Cao, Hongyu; Zhang, Shujia; Wang, Lihao; Zheng, Xueliang; Zheng, Xuefang [Research on Chemical Intermediates, 2018, vol. 44, # 9, p. 5521 - 5530]
[2]Kuroyanagi; Fukushima; Yoshihira; et al. [Chemical and Pharmaceutical Bulletin, 1980, vol. 28, # 10, p. 2948 - 2959]

21
[ 18113-18-3 ]
[ 77-78-1 ]
[ 135-77-3 ]

Reference： [1]Journal fur praktische Chemie (Leipzig 1954),1985,vol. 327,p. 808 - 822

22
[ 135-77-3 ]
[ 151-50-8 ]
[ 4107-65-7 ]

Reference： [1]Tetrahedron,1977,vol. 33,p. 779 - 786

23
[ 135-77-3 ]
[ 42926-52-3 ]
[ 3185-93-1 ]

Reference： [1]Phytochemistry,1968,vol. 7,p. 647 - 649

24
[ 135-77-3 ]
[ 123-38-6 ]
[ 5556-78-5 ]

Yield	Reaction Conditions	Operation in experiment
56.7%	Stage #1: 1,2,4-trimethoxy-benzene With n-butyllithium In tetrahydrofuran; hexane at 5 - 10℃; for 1.25h; Inert atmosphere; Stage #2: propionaldehyde With N,N,N,N,-tetramethylethylenediamine In tetrahydrofuran; hexane at 5 - 10℃; Inert atmosphere;	4.1.9. (E)-1,2,4-trimethoxy-3-(prop-1-en-1-yl)benzene (1) 1,2,4-trimethoxybenzene (1b) (3.0 g, 18 mmol) and 60 mL dry THFwere placed in a 100 mL three-mouth flask with a magnetic stirrer underthe nitrogen protection. After the mixture was cooled down to 5 C, the2.5 M solution of n-BuLi in hexane (19.7 mL, 49.2 mmol) was addeddropwise (over 15 min), and stirring was continued at 5-10 C. An hourlater, TMEDA (2.5 mL, 16.3 mmol) and propionaldehyde (1.9 mL, 26.7mmol) were then added dropwise (over 20 min) to the reaction mixtureat 5-10 C. After the completion of the reaction (TLC monitoring), thereaction was quenched with 3 mL H2O. The solvent was removed in avacuum under pressure, and the residue obtained was treated with 60mL EtOAc and 20 mL 1 N HCl. The organic phase was collected, and theaqueous phase was extracted with 60 mL EA. Organic phases werecombined, dried over anhydrous MgSO4, filtered, concentrated inreduced pressure, and purified on silica gel column chromatography(Pet. Ether/EtOAc, v/v = 20:1) to obtain 2.3 g (10.2 mmol; yield:56.7%) 1-(2,3,6-trimethoxyphenyl)propan-1-ol (1a).
	(i) nBuLi, hexane, (ii) /BRN= 506010/; Multistep reaction;
1.8 g	Stage #1: 1,2,4-trimethoxy-benzene With n-butyllithium In hexane for 1h; Stage #2: propionaldehyde With N,N,N,N,-tetramethylethylenediamine In hexane for 0.166667h; Further stages.;

Reference： [1]Zhang, Jian; Mu, Keman; Yang, Peng; Feng, Xinqian; Zhang, Di; Fan, Xiangyu; Wang, Qiantao; Mao, Shengjun [Bioorganic Chemistry, 2021, vol. 115]
[2]Shulgin [Journal of medicinal chemistry, 1966, vol. 9, # 3, p. 445 - 446]
[3]Poplawski; Lozowicka; Dubis; Lachowska; Witkowski; Siluk; Petrusewicz; Kaliszan; Cybulski; Strzalkowska; Chilmonczyk [Journal of Medicinal Chemistry, 2000, vol. 43, # 20, p. 3671 - 3676]

25
[ 135-77-3 ]
[ 541-41-3 ]
ethyl 2,3,6-trimethoxybenzoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
96%	Stage #1: 1,2,4-trimethoxy-benzene With n-butyllithium In tetrahydrofuran at 0 - 20℃; for 3h; Inert atmosphere; Stage #2: chloroformic acid ethyl ester In tetrahydrofuran at 0 - 20℃; for 3h; Inert atmosphere;	4.1.21. Ethyl 2,3,6-trimethoxybenzoate (35) 1,2,4-Trimethoxybenzene 30 (82.30 g, 0.49 mol) was dissolved with mechanical stirring in anhydrous THF (1.2 L) and then cooled to 0 °C. n-Butyllithium (210 mL, 2.5 M, 0.53 mol) was added dropwise over a 1-h period and the reaction mixture was allowed to warm to rt. After 2 h, the mixture was cooled to 0 °C and then transferred via a cannula into a solution of ethyl chloroformate (200 mL, 2.1 mol) in THF (500 mL). The resulting mixture was stirred at rt for a 3-h period. Standard ethereal workup, followed by chromatography (elution with H/E, 1:1), afforded 112.90 g (96%) of benzoate 35 that was homogeneous by TLC analysis (H/E, 1:1, Rf30=0.41, Rf35=0.22): 1H NMR (400 MHz) δ 1.38 (t, 3H, J=7.1 Hz), 3.78 (s, 3H), 3.83 (s, 3H), 3.89 (s, 3H), 4.41 (q, 2H, J=7.1 Hz), 6.60 (d,1H, J=9.0 Hz), 6.88 (d, 1H, J=9.0 Hz); 13C NMR (100.6 MHz) 14.3 (q), 56.3 (q), 56.6 (q), 61.4 (t), 61.5 (q), 106.4 (d), 114.2 (d), 119.6 (s), 146.9 (s), 146.9 (s) [note: the preceding signals overlap], 150.5 (s), 166.0 (s) ppm; IR (film) 2938, 2838, 1732 cm-1; MS (m/z) 240 (M+).
	With n-butyllithium 1.) THF, RT, 1 h, 2.) THF, RT, 1 h; Multistep reaction;

Reference： [1]Location in patent: experimental part Majetich, George; Zhang, Yong; Tian, Xinrong; Britton, Jonathan E.; Li, Yang; Phillips, Ryan [Tetrahedron, 2011, vol. 67, # 52, p. 10129 - 10146]
[2]Carreno, M. Carmen; Garcia Ruano, Jose L.; Toledo, Miguel A.; Urbano, Antonio [Tetrahedron Asymmetry, 1997, vol. 8, # 6, p. 913 - 921]

27
[ 2832-19-1 ]
[ 135-77-3 ]
[ 64-19-7 ]
ZnCl₂ [ No CAS ]
chloro-acetic acid-(2,4,5-trimethoxy-benzylamide) [ No CAS ]

Reference： [1]Gazzetta Chimica Italiana,1930,vol. 60,p. 777,778

28
[ 135-77-3 ]
[ 33513-42-7 ]
[ 5556-86-5 ]

Yield	Reaction Conditions	Operation in experiment
89%	With n-butyllithium In diethyl ether for 2h; Heating;
78%	Stage #1: 1,2,4-trimethoxy-benzene With n-butyllithium In diethyl ether for 2h; Heating; Stage #2: N,N-dimethyl-formamide In diethyl ether for 2h; Heating;
68%	Stage #1: 1,2,4-trimethoxy-benzene With n-butyllithium In diethyl ether; hexane for 2h; Heating; Stage #2: N,N-dimethyl-formamide In diethyl ether; hexane for 2h; Heating; Stage #3: With hydrogenchloride for 1h;

68%	Stage #1: 1,2,4-trimethoxy-benzene With n-butyllithium In diethyl ether for 2h; Heating; Stage #2: N,N-dimethyl-formamide In diethyl ether for 2h; Heating; Further stages.;
68%	Stage #1: 1,2,4-trimethoxy-benzene With n-butyllithium In diethyl ether; hexane for 2h; Heating; Stage #2: N,N-dimethyl-formamide In diethyl ether; hexane for 2h; Heating; Further stages.;
61%	Stage #1: 1,2,4-trimethoxy-benzene With n-butyllithium In diethyl ether; hexane at -10 - 20℃; Inert atmosphere; Stage #2: N,N-dimethyl-formamide In diethyl ether; hexane at -10℃; Inert atmosphere;
42.9%	Stage #1: 1,2,4-trimethoxy-benzene With n-butyllithium In tetrahydrofuran; hexane at -60 - -40℃; Inert atmosphere; Stage #2: N,N-dimethyl-formamide In tetrahydrofuran; hexane at -60 - -40℃; for 2h; Inert atmosphere;	5.1.15 2,3,6-Trimethoxybenzaldehyde (42) n-Butyl lithium in hexane 45mL (2.5M, 0.11mol) was added dropwise to a solution of 1,2,4-trimethoxybenzene 41 (16.8g, 0.10mol) in anhydrous THF (160mL) at-60°C under a nitrogen atmosphere (about 30min). A white precipitate was formed and temperature raised to-50°C. After completion of adding n-Butyl lithium, the reaction mixture was stirred additionally for 1.5h between-40°C and -60°C. Then, anhydrous DMF (8.7g, 0.12mol) was added dropwise at-60°C. During this addition, white precipitate was disappear. The mixture was allowed to stir at-40°C for 2h (monitored by TLC), then cautiously quenched with saturated NH4Cl solution and followed by stirring at room temperature for another 30min. The reaction was extracted with EtOAc (3×150mL) and saturated NH4Cl solution (250mL). The total organic layer was washed with brine (3×150mL), dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure to obtain a crude residue, which was subjected to flash chromatography on silica gel (petroleum ether/dichloromethane/ethyl acetate, 9:1:1-7:1:1-6:1:1) to afford 8.4g of 42 as a light yellow solid. Yield: 42.9%. Mp 28.2-28.5°C (lit [69]. mp 20°C). TLC: Rf=0.55 (1:1 EtOAc/hexanes). 1H NMR (600MHz, Chloroform-d) [41] δ 10.42 (s, 1H), 7.06 (d, J=9.1Hz, 1H), 6.62 (d, J=9.1Hz, 1H), 3.89 (s, 3H), 3.82 (s, 3H), 3.82 (s, 3H). 13C NMR (151MHz, Chloroform-d) δ 189.80, 154.93, 152.14, 146.87, 119.74, 119.21, 106.46, 62.08, 56.79, 56.28. HRMS (+ESI) 197.0809 [M+ H]+, 219.0627 [M+ Na]+ (calcd. for C10H13O4+ 197.0808 and C10H12O4Na+ 219.0628).

Reference： [1]Meyer, Axel; Kirschning, Andreas [Synlett, 2007, # 8, p. 1264 - 1268]
[2]Shen, Gang; Wang, Mingwen; Welch, Timothy R.; Blagg, Brian S. J. [Journal of Organic Chemistry, 2006, vol. 71, # 20, p. 7618 - 7631]
[3]Andrus, Merritt B.; Meredith, Erik L.; Hicken, Erik J.; Simmons, Bryon L.; Glancey, Russell R.; Ma, Wei [Journal of Organic Chemistry, 2003, vol. 68, # 21, p. 8162 - 8169]
[4]Andrus, Merritt B.; Meredith, Erik L.; Simmons, Bryon L.; Sekhar, B. B. V. Soma; Hicken, Erik J. [Organic Letters, 2002, vol. 4, # 20, p. 3549 - 3552]
[5]Andrus; Meredith; Sekhar [Organic letters, 2001, vol. 3, # 2, p. 259 - 262]
[6]Location in patent: experimental part Alves, Ana P. L.; Junior, Jose Augusto B. C.; Slana, Glaucia B. A.; Cardoso, Jari N.; Wang, Qiang; Lopes, Rosangela S. C.; Lopes, Claudio C. [Synthetic Communications, 2009, vol. 39, # 20, p. 3693 - 3709]
[7]Bai, Yajun; He, Xirui; Bai, Yujun; Sun, Ying; Zhao, Zefeng; Chen, Xufei; Li, Bin; Xie, Jing; Li, Yang; Jia, Pu; Meng, Xue; Zhao, Ye; Ding, Yanrui; Xiao, Chaoni; Wang, Shixiang; Yu, Jie; Liao, Sha; Zhang, Yajun; Zhu, Zhiling; Zhang, Qiang; Zhao, Yuhui; Qin, Fanggang; Zhang, Yi; Wei, Xiaoyang; Zeng, Min; Liang, Jing; Cuan, Ye; Shan, Guangzhi; Fan, Tai-Ping; Wu, Biao; Zheng, Xiaohui [European Journal of Medicinal Chemistry, 2019, vol. 183]

29
[ 6136-93-2 ]
[ 135-77-3 ]
[ 14470-07-6 ]

Reference： [1]Organic Preparations and Procedures International,2004,vol. 36,p. 135 - 140

30
[ 135-77-3 ]
[ 16033-71-9 ]
[ 913621-93-9 ]

Yield	Reaction Conditions	Operation in experiment
97%	Stage #1: 1,2,4-trimethoxy-benzene With n-butyllithium In diethyl ether for 2h; Heating; Stage #2: methyloxirane In diethyl ether for 0.583333h; Heating;
52%	Stage #1: 1,2,4-trimethoxy-benzene; methyloxirane In tetrahydrofuran at 40℃; for 2h; Stage #2: With n-butyllithium In tetrahydrofuran; hexane at 20℃; for 1h;	2 Example 2 - Synthesis of compound 2 Propylene oxide (8.3 g, 142.8 mmol) is added dropwise to a solution of 1,3,4- trimethoxybenzene (6.0 g, 35.7 mmol) in THF (100 mL) at 40°C. The reaction mixture ismaintained at this temperature for 2 hours and then cooled to room temperature. A solution ofn-BuLi in hexane (1.6 M, 17.1 mL, 14.4 mmol) is added dropwise and the reaction mixture is then stirred at room temperature for 1 hour. The excess base is neutralized by adding saturated aqueous NH4C1 solution (20 mL) and the mixture is extracted 3 times with 50 mL of ethyl acetate. The organic phases are combined, dried over Na2SO4 and concentrated. The residue ispurified by column chromatography on silica gel (hexane/EtOAc: 10/1) to isolate compound 2 in the form of a pale yellow oil (4.2 g, 52% yield).The 1H NMR spectra and mass spectra are in accordance with the expected structure.
	With n-butyllithium In diethyl ether

Reference： [1]Shen, Gang; Wang, Mingwen; Welch, Timothy R.; Blagg, Brian S. J. [Journal of Organic Chemistry, 2006, vol. 71, # 20, p. 7618 - 7631]
[2]Current Patent Assignee: L'OREAL SA - WO2016/92074, 2016, A1 Location in patent: Page/Page column 27; 28
[3]Current Patent Assignee: UNIVERSITY OF KANSAS - US2006/89495, 2006, A1 Location in patent: Page/Page column 14

31
[ 135-77-3 ]
[ 942-54-1 ]
2,4,5,4'-tetramethoxy-α-methyldesoxybenzoin [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
42%	With PPA; Polyphosphoric acid (PPA); at 75℃; for 6h;	Formation of 2,4,5,4'-tetramethoxy-alpha-methyldesoxybenzoin. To a mixture of 2-(p-methoxyphenyl)propionic acid (0.20 g, 1.11 mmol) and polyphosphoric acid (5 gm), 1,3,4-trimethoxy benzene (0.186 g, 1.11 mmol, 0.166 ml) was added. The mixture was allowed to heat to 75 C. while stirring for 6 hours. TLC (30% ErOAc:Hexane) and gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS) analyses confirmed the presence of two major products with MU values of 24.68 and 25.01 (ratio 1:4). Chromatography on silica column (30% EtOAc:Hexane) allowed the isolation of the two products. Product MU 24.92 was isolated as a crystalline low melting solid. NMR data and GC-MS data confirmed the above structure. A 42% and 11% yield was obtained for products MU 25.01 and MU 24.68 respectively.

Reference： [1]Patent: US2005/222248,2005,A1 .Location in patent: Page/Page column 17

32
[ 135-77-3 ]
anti-(η³-methallyl)Fe(CO)4BF4 [ No CAS ]
[ 2883-98-9 ]

Reference： [1]Organic Preparations and Procedures International,1991,vol. 23,p. 133 - 138

33
4-ethoxycarbonylthiazole-2-yl isocyanate [ No CAS ]
[ 135-77-3 ]
[ 185105-98-0 ]

Yield	Reaction Conditions	Operation in experiment
70%	With tin(IV) chloride In chlorobenzene at 100℃; for 3h;	4 EXAMPLE 4; Production of 2-[N-(2,4,5-trimethoxybenzoyl)amino]-4-ethoxycarbonyl-1,3-thiazole First, 300 mg (1.5 mmol) of 4-ethoxycarbonyl-1,3-thiazole-2-isocyanate, 255 mg (1.5 mmol) of 1,2,4-trimethoxybenzene, and 3 mL of chlorobenzene were mixed. Then, 262 µL (2.3 mmol) of tin chloride (IV) was added to the mixture. The temperature of the mixture was raised to 100°C, and the mixture was stirred for three hours. The reaction solution was cooled, was mixed with 2 mL of ethanol, and was stirred. A precipitated crystal was filtered out and was washed with a small amount of ethanol to yield 388 mg (1.1 mmol) of the title compound, where the yield was 70%. 1H-NMR (DMSO-d6) ς (ppm) : 1.31(t, 3H), 3.77(s, 3H), 3.91(s, 3H), 4.01(s, 3H), 4.29(q, 2H), 6.85(s, 1H), 7.40(s, 1H), 8.09(s, 1H), 11.65(s, 1H)

Reference： [1]Current Patent Assignee: MITSUI CHEMICALS,INC. - EP1489073, 2004, A1 Location in patent: Page 11

34
[ 135-77-3 ]
[ 98-88-4 ]
[ 36897-00-4 ]

Yield	Reaction Conditions	Operation in experiment
92%	With aluminum (III) chloride In dichloromethane at 0℃; for 6h;
85%	With choline chloride * 2ZnCl₂ In neat (no solvent) at 70℃; for 0.5h; Green chemistry;	General procedure for aromatic ketone compounds synthesis General procedure: A mixture of electron-rich arenes a (2.0 mmol), acylation reagent b ((2.0 mmol)and catalytic solvent DES [ChCl][ZnCl 2 ] 2 (2.0 mmol) were added and stirred in a25 mL round-bottomed ask at 70 C for the desired time. The reaction procedurewas monitored by TLC and recorded the experimental phenomena. Aftercompletion of the reaction, 10 mL of water and 10 mL of ethyl acetate wereadded to the mixture and then cooled to room temperature, collecting the productand solvent from the organic phase and water, respectively. The organic phase waswashed with saturated sodium hydrogen carbonate solution and saturated brinesuccessively, then evaporated under high vacuum to give the target compound. PureDES was obtained by drying sufciently in a vacuum, and it could be reused foranother cycle.
78%	With VNU-1 In nitrobenzene at 120℃; for 0.166667h; Microwave irradiation;

54%	With 1,1,1,3',3',3'-hexafluoro-propanol at 20℃; for 5h; Inert atmosphere;
1.02 g	With aluminum (III) chloride In dichloromethane at 0℃; for 6h; Inert atmosphere;	2.1. 2,4,5-trimethoxybenzophenone (7) 2,4,5-Trimethoxybenzophenone (7) was synthesized according to the published method.1 To anice-cooled solution (0 °C) of 1,2,4-trihydroxybenzene 6 (1.07 g, 8.48 mmol) in tetrahydrofuran (28mL) were added sodium hydride (60% dispersion in oil, 1.70 g, 42.4 mmol) and dimethyl sulfate (4.05mL, 42.4 mmol). The reaction mixture was warmed to room temperature and was stirred under anargon atmosphere for 16 h. The reaction mixture was then evaporated and extracted with ethyl acetate.The organic layer was washed with brine, dried over sodium sulfate, filtered, and concentrated invacuo. The crude product was purified by silica gel column chromatography using hexane/ethyl acetate (19:1), to give 1,2,4-trimethoxybenzene (1.37 g, 96%) as a viscous oil. To an ice-cooled (0 °C)solution of benzoyl chloride (0.455 mL, 3.92 mmol) and aluminium chloride (0.523 g, 3.92 mmol) indichloromethane (10 mL) was added dropwise a solution of 1,2,4-trimethoxybenzene (0.659 g, 3.92mmol) in dichloromethane (3 mL). The resulting mixture was stirred under an argon atmosphere for 6h at 0 °C. The reaction was quenched by the addition of a 0.5 M aqueous solution of hydrogenchloride, and the aqueous layer was extracted with dichloromethane. The organic layer was washedwith brine, dried over sodium sulfate, filtered, and concentrated in vacuo. The crude product waspurified by silica gel column chromatography using chloroform, to give 2,4,5-trimethoxybenzophenone (7) (1.02 g, 96%) as a yellow solid.Compound 7: 1H NMR (500 MHz, CDCl3): 7.74 (2H, d, J = 7.5 Hz), 7.49 (1H, t, J = 8.0 Hz), 7.38 (2H,dd, J = 8.0, 7.5 Hz), 7.00 (1H, s), 6.53 (1H, s), 3.92 (3H, s), 3.81 (3H, s), 3.62 (3H, s).

Reference： [1]Kamino, Shinichiro; Ichikawa, Hayato; Wada, Shun-ichi; Horio, Yuka; Usami, Yoshihide; Yamaguchi, Takako; Koda, Toshiki; Harada, Aki; Shimanuki, Kazusa; Arimoto, Masao; Doi, Mitsunobu; Fujita, Yoshikazu [Bioorganic and Medicinal Chemistry Letters, 2008, vol. 18, # 15, p. 4380 - 4384]
[2]Jin, Xiaojun; Wang, Ailing; Cao, Hongyu; Zhang, Shujia; Wang, Lihao; Zheng, Xueliang; Zheng, Xuefang [Research on Chemical Intermediates, 2018, vol. 44, # 9, p. 5521 - 5530]
[3]Doan, Tan L. H.; Dao, Thong Q.; Tran, Hai N.; Tran, Phuong H.; Le, Thach N. [Dalton Transactions, 2016, vol. 45, # 18, p. 7875 - 7880]
[4]Vekariya, Rakesh H.; Aubé, Jeffrey [Organic Letters, 2016, vol. 18, # 15, p. 3534 - 3537]
[5]Kodama, Takeshi; Ito, Takuya; Dibwe, Dya Fita; Woo, So-Yeun; Morita, Hiroyuki [Bioorganic and Medicinal Chemistry Letters, 2017, vol. 27, # 11, p. 2397 - 2400]

35
[ 121-43-7 ]
[ 135-77-3 ]
[ 380430-67-1 ]

Reference： [1]Synthetic Communications,2009,vol. 39,p. 3693 - 3709

36
[ 135-77-3 ]
[ 79-22-1 ]
[ 60241-75-0 ]

Yield	Reaction Conditions	Operation in experiment
94.4%	Stage #1: 1,2,4-trimethoxy-benzene With n-butyllithium In tetrahydrofuran at -10 - 25℃; for 2.16667h; Inert atmosphere; Stage #2: methyl chloroformate In ethanol at -10 - 20℃; for 16h; Inert atmosphere;	1.1 (1) Preparation of methyl 2,3,6-trimethoxybenzoate Accurately weigh 1,2,4-trimethoxybenzene (16.3 g, 96.7 mmol) in a 250 mL dry clean double-necked round bottom flask, place the magnetons, add 150 mL of anhydrous tetrahydrofuran, and dissolve by magnetic stirring. The reaction system was protected with nitrogen and stirred at -10 ° C in a cold ethanol bath for 10 minutes to maintain the internal temperature at -10 °C. 50.3 mL (2 mol/L) of n-butyllithium was slowly added to the reaction system. At this time, the reaction liquid gradually changed from pale yellow to milky white. After the end of the addition, the reaction system was transferred to room temperature (25 ° C) and the reaction was stirred for 2 hours. Then, the mixture was further stirred and stirred in a cold ethanol bath at -10 ° C for 10 minutes to maintain the internal temperature at -10 ° C. Methyl chloroformate (10.6 mL, 138.6 mmol) was slowly added dropwise, and the reaction solution gradually became clarified. After the end of the addition, the mixture was transferred to room temperature and the reaction was stirred for 16 hours. After the reaction was completed by TLC, the reaction mixture was poured into 100 mL of ice water, and the mixture was extracted with ethyl acetate (3 mL), and the organic phase was combined and dried over anhydrous sodium sulfate for 20 min. Solid 23.1g, silica gel (200-300 mesh) column chromatography, developing solvent:The petroleum ether/ethyl acetate (20/1, V/V) was purified to give a pure product (20.6 g, yield: 94.4%).
55%	Stage #1: 1,2,4-trimethoxy-benzene With n-butyllithium In diethyl ether; hexane at -10 - 20℃; Inert atmosphere; Stage #2: methyl chloroformate In diethyl ether; hexane at -10℃; Inert atmosphere;

Reference： [1]Current Patent Assignee: GUANGZHOU YAOBEN JUNAN PHARMACEUTICAL TECH - CN110156739, 2019, A Location in patent: Paragraph 0039-0043
[2]Location in patent: experimental part Alves, Ana P. L.; Junior, Jose Augusto B. C.; Slana, Glaucia B. A.; Cardoso, Jari N.; Wang, Qiang; Lopes, Rosangela S. C.; Lopes, Claudio C. [Synthetic Communications, 2009, vol. 39, # 20, p. 3693 - 3709]

37
[ 135-77-3 ]
[ 459-57-4 ]
[ 1195735-76-2 ]

Yield	Reaction Conditions	Operation in experiment
98%	With niobium pentachloride In dichloromethane at 0 - 20℃; for 24h;	Condensation Reaction of Aldehydes with Arenes in the Presence of NbCl5 as Acid Catalyst; General Procedure General procedure: A suspension of aldehyde (1 mmol) and NbCl5 (1 mmol) in DCM (5mL) was stirred at 0 °C. Then, arene (2.2 mmol) was added. The reac-tion was allowed to reach room temperature. The end of the reactionwas monitored via TLC. Next, the reaction mixture was quenchedwith saturated Na2CO3 solution (15 mL) and extracted with Et2O (3 × 20 mL). The organic layer was washed with brine, dried over an-hydrous MgSO4 , filtered, and concentrated. The residue was purifiedby flash column chromatography (silica gel; hexane-EtOAc, 9.5:0.5 to8:2 v/v) to afford the pure compounds. All obtained products werecharacterized by their spectroscopic data [ 1 H, 13 C, and 19 F NMR, IR, MS(EI)].
97%	With air; iodine In toluene at 20℃; for 72h;
92%	With 1-methyl-3-(propyl-3-sulfonyl)imidazolium trifluoromethanesulfonate In neat (no solvent) at 40℃; for 1h; Green chemistry;	General procedure for triarylmethanes and diarylalkanessynthesis General procedure: A mixture of aldehyde 2 (1.0 mmol), aromatic compound 1(2.0 mmol) and BAILs (0.2 mmol) was stirred at 40∘C for the desired time. The reaction was monitored by thin layer chromatography(TLC). After the completion of the reaction, 1 ml of water was added into the reaction mixture, and the target compound was obtained though simple filtration. The pure ionic liquids got by drying the filtrate were reused for another cycle. Synthesis route is listed in Scheme 2.

Reference： [1]Baviera, Giovanni S.; Donate, Paulo M.; Matias, Alexandre A.; Previdi, Daniel; Rodrigues, Shirley M. M. [Synthesis, 2019, vol. 51, # 23, p. 4498 - 4506]
[2]Location in patent: experimental part Jaratjaroonphong, Jaray; Sathalalai, Supaporn; Techasauvapak, Prapapan; Reutrakul, Vichai [Tetrahedron Letters, 2009, vol. 50, # 44, p. 6012 - 6015]
[3]Wang, Ailing; Zheng, Xueliang; Zhao, Zhuangzhi; Li, Changping; Cui, Yingna; Zheng, Xuefang; Yin, Jingmei; Yang, Guang [Applied Catalysis A: General, 2014, vol. 482, p. 198 - 204]

38
[ 135-77-3 ]
[ 104-88-1 ]
[ 1190880-27-3 ]

Yield	Reaction Conditions	Operation in experiment
99%	With niobium pentachloride In dichloromethane at 0 - 20℃; for 24h;	Condensation Reaction of Aldehydes with Arenes in the Presence of NbCl5 as Acid Catalyst; General Procedure General procedure: A suspension of aldehyde (1 mmol) and NbCl5 (1 mmol) in DCM (5mL) was stirred at 0 °C. Then, arene (2.2 mmol) was added. The reac-tion was allowed to reach room temperature. The end of the reactionwas monitored via TLC. Next, the reaction mixture was quenchedwith saturated Na2CO3 solution (15 mL) and extracted with Et2O (3 × 20 mL). The organic layer was washed with brine, dried over an-hydrous MgSO4 , filtered, and concentrated. The residue was purifiedby flash column chromatography (silica gel; hexane-EtOAc, 9.5:0.5 to8:2 v/v) to afford the pure compounds. All obtained products werecharacterized by their spectroscopic data [ 1 H, 13 C, and 19 F NMR, IR, MS(EI)].
91%	With 1-methyl-3-(propyl-3-sulfonyl)imidazolium trifluoromethanesulfonate In neat (no solvent) at 40℃; for 0.5h; Green chemistry;	General procedure for triarylmethanes and diarylalkanessynthesis General procedure: A mixture of aldehyde 2 (1.0 mmol), aromatic compound 1(2.0 mmol) and BAILs (0.2 mmol) was stirred at 40∘C for the desired time. The reaction was monitored by thin layer chromatography(TLC). After the completion of the reaction, 1 ml of water was added into the reaction mixture, and the target compound was obtained though simple filtration. The pure ionic liquids got by drying the filtrate were reused for another cycle. Synthesis route is listed in Scheme 2.
90%	With silica supported o-benzenedisulfonimide at 20℃; for 1.25h; neat (no solvent);

88%

With air; iodine In toluene at 20℃; for 72h;

Reference： [1]Baviera, Giovanni S.; Donate, Paulo M.; Matias, Alexandre A.; Previdi, Daniel; Rodrigues, Shirley M. M. [Synthesis, 2019, vol. 51, # 23, p. 4498 - 4506]
[2]Wang, Ailing; Zheng, Xueliang; Zhao, Zhuangzhi; Li, Changping; Cui, Yingna; Zheng, Xuefang; Yin, Jingmei; Yang, Guang [Applied Catalysis A: General, 2014, vol. 482, p. 198 - 204]
[3]Barbero, Margherita; Cadamuro, Silvano; Dughera, Stefano; Magistris, Claudio; Venturello, Paolo [Organic and Biomolecular Chemistry, 2011, vol. 9, # 24, p. 8393 - 8399]
[4]Location in patent: experimental part Jaratjaroonphong, Jaray; Sathalalai, Supaporn; Techasauvapak, Prapapan; Reutrakul, Vichai [Tetrahedron Letters, 2009, vol. 50, # 44, p. 6012 - 6015]

39
[ 135-77-3 ]
[ 1122-91-4 ]
[ 1195735-78-4 ]

Yield	Reaction Conditions	Operation in experiment
98%	With air; iodine In toluene at 20℃; for 72h;
96%	With trifluorormethanesulfonic acid In acetonitrile at 0 - 20℃; for 24h;
96%	With niobium pentachloride In dichloromethane at 0 - 20℃; for 24h;	Condensation Reaction of Aldehydes with Arenes in the Presence of NbCl5 as Acid Catalyst; General Procedure General procedure: A suspension of aldehyde (1 mmol) and NbCl5 (1 mmol) in DCM (5mL) was stirred at 0 °C. Then, arene (2.2 mmol) was added. The reac-tion was allowed to reach room temperature. The end of the reactionwas monitored via TLC. Next, the reaction mixture was quenchedwith saturated Na2CO3 solution (15 mL) and extracted with Et2O (3 × 20 mL). The organic layer was washed with brine, dried over an-hydrous MgSO4 , filtered, and concentrated. The residue was purifiedby flash column chromatography (silica gel; hexane-EtOAc, 9.5:0.5 to8:2 v/v) to afford the pure compounds. All obtained products werecharacterized by their spectroscopic data [ 1 H, 13 C, and 19 F NMR, IR, MS(EI)].

Reference： [1]Location in patent: experimental part Jaratjaroonphong, Jaray; Sathalalai, Supaporn; Techasauvapak, Prapapan; Reutrakul, Vichai [Tetrahedron Letters, 2009, vol. 50, # 44, p. 6012 - 6015]
[2]Wilsdorf, Michael; Leichnitz, Daniel; Reissig, Hans-Ulrich [Organic Letters, 2013, vol. 15, # 10, p. 2494 - 2497]
[3]Baviera, Giovanni S.; Donate, Paulo M.; Matias, Alexandre A.; Previdi, Daniel; Rodrigues, Shirley M. M. [Synthesis, 2019, vol. 51, # 23, p. 4498 - 4506]

40
[ 93-51-6 ]
[ 135-77-3 ]
[ 1219118-18-9 ]

Yield	Reaction Conditions	Operation in experiment
70%	With [bis(acetoxy)iodo]benzene; acetic acid at 20℃; for 3h; regioselective reaction;
69%	With N-methyl-N,N,N-triethylammonium methylsulfate In methanol; 1,1,1,3',3',3'-hexafluoro-propanol at 50℃; Electrolysis;
55%	With ammonium peroxydisulfate In acetonitrile at 23℃; for 18h; Irradiation;

53%	With 3-Methylbenzo<b>thiophene sulfoxide; trifluoroacetic anhydride In dichloromethane at -40 - 20℃; for 2.25h; Inert atmosphere;
48%	With 1,1,1,3',3',3'-hexafluoro-propanol; periodic acid In N,N-dimethyl-formamide at 20℃; for 0.5h;	12 General procedures General procedure: To a solution of phenol A (0.2 mmol) and phenol or arene B (0.3 mmol, 1.5 equiv.) in HFIP (1 mL) at room temperature, was added H5IO6 (2.50 M solution in DMF, 0.1 mmol, 0.5 equiv) dropwise in 10 min. The resulting mixture was stirred at room temperature for 0.5 h. The reaction mixture was concentrated in vacuo.The crude residue was purified by column chromatography on silicagel (eluent: n-hexane/EtOAc) to afford the product.
32%	With selenium(IV) oxide for 1h; Reflux;	1 Example 1 2-Hydroxy-2′,3,4′,5′-tetramethoxy-5-methylbiphenyl (1) The reaction was carried out according to GP1 with 200 mg (1.45 mmol, 1.0 eq.) of 4-methylguaiacol and 243 mg (1.45 mmol, 1.0 eq.) of 1,2,4-trimethoxybenzene in 4 mL of HFIP and with addition of 80 mg (0.72 mmol, 0.5 eq.) of selenium dioxide. The reaction time was one hour. After extraction and removal of the solvent, the product mixture obtained was purified by means of column chromatography on silica gel 60 using 5:1 (cy:EE) as eluent. The product was obtained as a pale yellow, highly viscous oil. (0064) Yield: 139 mg (0.45 mmol, 32%) (0065) 1H-NMR (400 MHz, CDCl3): δ [ppm]=2.33 (s, 3H), 3.81 (s, 3H) 3.86 (s, 3H), 3.91 (s, 3H), 3.94 (s, 3H), 5.98 (bs, 1H), 6.65 (s, 1H), 6.69 (s, 1H), 6.71 (s, 1H), 6.85 (s, 1H) (0066) 13C-NMR (101 MHz, CDCl3): δ [ppm]=21.32, 5615, 56.29, 56.60, 57.44, 98.56, 111.37, 115.12, 118.70, 123.53, 125.34, 129.03, 141.02, 143.73, 147.89, 149.71, 150.47 HRMS (ESI, pos.mode): m/z 5 [M+Na+]: calculated: 327.1208. found: 327.1212.
50 %Chromat.	With N-methyl-N,N,N-triethylammonium methylsulfate; 1,1,1,3',3',3'-hexafluoro-propanol at 50℃; Electrolysis;

Reference： [1]Morimoto, Koji; Sakamoto, Kazuma; Ohnishi, Yusuke; Miyamoto, Takeshi; Ito, Motoki; Dohi, Toshifumi; Kita, Yasuyuki [Chemistry - A European Journal, 2013, vol. 19, # 27, p. 8726 - 8731]
[2]Kirste, Axel; Elsler, Bernd; Schnakenburg, Gregor; Waldvogel, Siegfried R. [Journal of the American Chemical Society, 2012, vol. 134, # 7, p. 3571 - 3576]
[3]Eisenhofer, Anna; Hioe, Johnny; Gschwind, Ruth M.; König, Burkhard [European Journal of Organic Chemistry, 2017, vol. 2017, # 15, p. 2194 - 2204]
[4]He, Zhen; Perry, Gregory J. P.; Procter, David J. [Chemical Science, 2020, vol. 11, # 7, p. 2001 - 2005]
[5]Gao, Peng-Cheng; Chen, Huan; Grigoryants, Vladimir; Zhang, Qiang [Tetrahedron, 2019, vol. 75, # 13, p. 2004 - 2011]
[6]Current Patent Assignee: EVONIK INDUSTRIES AG - US2016/340281, 2016, A1 Location in patent: Paragraph 0061-0066
[7]Kirste, Axel; Schnakenburg, Gregor; Stecker, Florian; Fischer, Andreas; Waldvogel, Siegfried R. [Angewandte Chemie - International Edition, 2010, vol. 49, # 5, p. 971 - 975]

41
[ 2024-83-1 ]
[ 135-77-3 ]
[ 78-84-2 ]
[ 1206906-61-7 ]

Yield	Reaction Conditions	Operation in experiment
77%	Stage #1: veratronitrile; 1,2,4-trimethoxy-benzene; isobutyraldehyde With sulfuric acid In dichloromethane at 20℃; for 0.75h; Cooling; Stage #2: With ammonium hydroxide; ammonium chloride In dichloromethane; water Cooling with ice;

Reference： [1]Location in patent: experimental part Glushkov, Vladimir A.; Stryapunina, Olga G.; Gorbunov, Alexey A.; Maiorova, Olga A.; Slepukhin, Pavel A.; Ryabukhina, Sandra Ya.; Khorosheva, Elena V.; Sokol, Valentina I.; Shklyaev, Yurii V. [Tetrahedron, 2010, vol. 66, # 3, p. 721 - 729]

42
[ 135-77-3 ]
[ 882-33-7 ]
1,2,4-trimethoxy-5-phenylsulfanylbenzene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
92%	With dipotassium peroxodisulfate In trifluoroacetic acid at 20℃; for 16h;
63%	With tetrabutylammonium tetrafluoroborate In acetonitrile at 20℃; for 6h; Electrochemical reaction;	Electrosynthesis of phenyl (2,4,6-trimethoxyphenyl)sulfane. General procedure: To a reaction undivided cell was added 1,3,5-trimethoxybenzene(0.2 mmol), ArSSAr (0.2 mmol), n-Bu4NBF4 (0.1 mmol) and 10 mlMeCN under air atmosphere. The electrolytic cell was equippedwith a platinum plate electrode (5 mm × 5 mm × 0.1 mm) as theanode and a nickel plate (15 mm × 10 mm × 0.5 mm) as the cathode(Fig. S1 available online at stacks.iop.org/JES/168/015501/mmedia).The mixture was stirred at room temperature for 6 h. After thereaction was finished, the solvent was evaporated under reducedpressure. The crude product was purified by flash chromatographyon silica gel using petroleum ether and ethyl acetate as the eluent(100:0-100:5).
45%	With copper(l) iodide; oxygen In N,N-dimethyl-formamide at 120℃; for 24h;

40%	With ammonium peroxydisulfate; [Ir(dF(CF₃)ppy)₂(dtbpy)]PF₆ In acetonitrile at 25℃; for 6h; Irradiation; Inert atmosphere;	General procedure for C-H sulfenylation General procedure: In a 5 mL snap vial with magnetic stirring bar, the arene (0.1 mmol, 1.0 equiv), the aryl disulfide(2.0 equiv), (NH4)2S2O8 (1.7 equiv) and (Ir[dF(CF3)ppy]2(dtbpy))PF6 (0.002 mmol, 0.02 equiv)were added. Dry CH3CN (2.0 mL) were added under N2 and the mixture was degassed by“pump-freeze-thaw” cycles (×3) via a syringe needle. This reaction mixture was irradiatedthrough the plane bottom side of the snap vial using a 455 nm LED under nitrogen at 25 °C. Thereaction progress was monitored by GC analysis. After 6 h to 24 h of irradiation, the reactionmixture was transferred to separating funnel, diluted with ethyl acetate and washed with 15 mLof water. The aqueous layer was washed three times (3 × 15 mL) with ethyl acetate. Thecombined organic phases were dried over MgSO4, filtered and concentrated in vacuum.Purification of the crude product was achieved by flash column chromatography using petrolether/ethyl acetate as eluent.
35%	With ferric(III) bromide In N,N-dimethyl-formamide at 145℃; for 60h;

Reference： [1]Prasad, Ch Durga; Balkrishna, Shah Jaimin; Kumar, Amit; Bhakuni, Bhagat Singh; Shrimali, Kaustubh; Biswas, Soumava; Kumar, Sangit [Journal of Organic Chemistry, 2013, vol. 78, # 4, p. 1434 - 1443]
[2]Wang, Xin-Xing; Chen, Cheng; Shi, Hai-Zhu; Zhang, Guo-Wei; Tang, Yu; Zhang, Chun-Gu; Wu, Ming-Yu; Feng, Shun [Journal of the Electrochemical Society, 2021, vol. 168, # 1]
[3]Location in patent: experimental part Zhang, Shouhui; Qian, Pengcheng; Zhang, Manli; Hu, Maolin; Cheng, Jiang [Journal of Organic Chemistry, 2010, vol. 75, # 19, p. 6732 - 6735]
[4]Das, Amrita; Maity, Mitasree; Malcherek, Simon; König, Burkhard; Rehbein, Julia [Beilstein Journal of Organic Chemistry, 2018, vol. 14, p. 2520 - 2527]
[5]Location in patent: experimental part Zhang, Manli; Zhang, Shouhui; Pan, Changduo; Chen, Fan [Synthetic Communications, 2012, vol. 42, # 19, p. 2844 - 2853]

43
[ 22809-37-6 ]
[ 135-77-3 ]
[ 1268333-97-6 ]

Yield	Reaction Conditions	Operation in experiment
99%	With aluminum (III) chloride In dichloromethane at -10 - 20℃;	1.1 6 ml (40 mmol) of 1 ,2,4-trimethoxybenzene are introduced into 80 ml of dry CH2CI2 and the mixture is cooled to -10°C with stirring. 6-Bromohexanoyl chloride (6.2 ml, 40 mmol) dissolved in 20 ml of CH2CI2 is then added dropwise. AICI3 (5.6 g, 42 mmol) is progressively introduced in small portions into the reaction mixture. The reaction is maintained with stirring for 8h with a return to ambient temperature. The reaction mixture is then poured onto ice (200 ml) and acidified to pH 1 using HCI. The mixture is stirred until it returns to ambient temperature, 1 h. After evaporation of the CH2CI2, the mixture is extracted with AcOEt, and the organic phases are separated, dried over MgSO4, filtered and evaporated. The residue is subjected to flash chromatography over S1O2 with a gradient of pure heptane to heptane-AcOEt 50-50. The pure fractions are evaporated to obtain 13.6 g (yield = 99%) of crystals. TLC SiO2 (heptane-ACOEt 70-30) Rf = 0.5; 1H NMR (CDCI3) : 7.41 (s, 1 H), 6.50(s, 1 H), 3.95(s, 3H), 3.91 (s, 3H), 3.87(s, 3H), 3.43(t, 2H, J = 6.76 Hz), 2.98(t, 2H, J = 6.32 Hz), 1 .91 (m, 2H), 1 .71 (m, 2H), 1 .51 (m, 2H).

Reference： [1]Current Patent Assignee: PIERRE FABRE PARCIPATIONS - WO2011/27289, 2011, A1 Location in patent: Page/Page column 16-17

44
benzyl N-[(4-methoxyphenyl)(p-tolylsulfonyl)methyl]carbamate [ No CAS ]
[ 135-77-3 ]
C₂₄H₂₆O₆S [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
92%	With tris(pentafluorophenyl)borate In dichloromethane at 40℃; for 2h; Inert atmosphere; regioselective reaction;	4.2. General Procedure for the B(C₆F₅)₃-Catalyzed Friedel-Crafts alkylation reactions of activated arenes with α-amidosulfones General procedure: To a solution of equimolar quantities of the α-amidosulfones (1 mmol) and electron-rich arenes or heteroarenes (1 mmol) in dichloromethane (4 mL) at room temperature was added B(C6F5)3 (5 mol %) as a solid under a purge of nitrogen. Then the temperature slowly rises to 40 °C and stirred the reaction mixture for appropriate time. The reactions were monitored by TLC. After completion of the reaction (monitored by TLC), the reaction mixture was diluted with dichloromethane (5 mL), washed with water (5 mL), and followed by brine (5 mL). The organic layers were collected, dried over Na2SO4 and evaporated in rotavapour. The crude compound was purified by column chromatography (hexanes-ethyl acetate (3:1)) to afford the corresponding Friedel-Crafts products.