[ CAS No. 14920-87-7 ]

Name: 14920-87-7|Methyl 2,6-dichlorobenzoate|98%
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{[proInfo.proName]} (Synonyms:Methyl 2,6-dichlorobenzoate) ,{[proInfo.pro_purity]}

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Quality Control of [ 14920-87-7 ]

COA NMR CNMR HPLC LC-MS

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SDS Specification

Alternatived Products of [ 14920-87-7 ]

Product Details of [ 14920-87-7 ]

CAS No. :	14920-87-7	MDL No. :	MFCD01313701
Formula :	C₈H₆Cl₂O₂	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	HEYGSGDIWJDORA-UHFFFAOYSA-N
M.W :	205.03	Pubchem ID :	599542
Synonyms :	Methyl 2,6-dichlorobenzoate

Safety of [ 14920-87-7 ]

Signal Word:	Warning	Class:
Precautionary Statements:	P261-P305+P351+P338	UN#:
Hazard Statements:	H302-H315-H319-H335	Packing Group:
GHS Pictogram:

Application In Synthesis of [ 14920-87-7 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

Upstream synthesis route of [ 14920-87-7 ]
Downstream synthetic route of [ 14920-87-7 ]

[ 14920-87-7 ] Synthesis Path-Upstream 1~1

1
[ 14920-87-7 ]
[ 15258-73-8 ]

Yield	Reaction Conditions	Operation in experiment
95%	With zinc(II) tetrahydroborate In ethanol at 78℃; for 3 h;	Add 100 ml of absolute ethanol to the four-necked flask and heat to reflux.15 g of the raw material methyl 2,6-dichlorobenzoate was added to the ethanol.10 g of zinc borohydride was slowly added thereto, and the reaction was stirred at 78 ° C for 3 h.After the GC reaction was completed, the solvent was evaporated to dryness to obtain 12 g.2,6-dichlorobenzyl alcohol.The product yield was 95percent and the purity was 98percent.

Reference： [1] Patent: CN108794297, 2018, A, . Location in patent: Paragraph 0007; 0008; 0009

[ 14920-87-7 ] Synthesis Path-Downstream 1~49

1
[ 35409-97-3 ]
[ 124-41-4 ]
[ 14920-87-7 ]
[ 140-38-5 ]

Reference： [1]Collection of Czechoslovak Chemical Communications,1989,vol. 54,p. 1363 - 1369

2
[ 124-41-4 ]
[ 4659-45-4 ]
[ 14920-87-7 ]

Reference： [1]Walther, Hansjoerg; Schlunegger, Urs Peter; Friedli, Felix [Organic Mass Spectrometry, 1983, vol. 18, # 12, p. 572 - 575]

3
[ 17216-08-9 ]
[ 14920-87-7 ]
1-(2,6-dichlorophenyl)-3-(1,2,3,4-tetrahydro-1-oxo-2-naphthalenyl)-1,3-propanedione [ No CAS ]
1-(2-chloro-6-methoxyphenyl)-3-(1,2,3,4-tetrahydro-1-oxo-2-naphthalenyl)-1,3-propanedione [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
1: 43% 2: 20%	With sodium hydride In 1,2-dimethoxyethane for 6h; Heating;

Reference： [1]Arcoleo, Antonino; Abbate, Giovanni; Gottuso, Mario; Fontana, Giacomo; Giammona, Gaetano [Heterocycles, 1988, vol. 27, # 9, p. 2141 - 2152]

4
[ 17287-03-5 ]
[ 50-30-6 ]
[ 14920-87-7 ]

Yield	Reaction Conditions	Operation in experiment
69%	In ethyl acetate at 20℃; for 2h;

Reference： [1]Niedan; Schoeler [Chemosphere, 1997, vol. 35, # 6, p. 1233 - 1241]

5
[ 67-56-1 ]
[ 598-32-3 ]
[ 45739-20-6 ]
[ 201230-82-2 ]
[ 14920-87-7 ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 2,6-dichloro-benzenediazonium With Merrifield resin modified with piperazine In tetrahydrofuran at 0 - 25℃; Stage #2: methanol; 2-hydroxy-3-butene; carbon monoxide With palladium diacetate; trifluoroacetic acid at 40℃; for 2h;

Reference： [1]Braese, Stefan; Schroen, Maarten [Angewandte Chemie - International Edition, 1999, vol. 38, # 8, p. 1071 - 1073]

6
[ 616-38-6 ]
[ 50-30-6 ]
[ 14920-87-7 ]

Yield	Reaction Conditions	Operation in experiment
99%	With 1,8-diazabicyclo[5.4.0]undec-7-ene for 24h; Heating;
98%	With 1,8-diazabicyclo[5.4.0]undec-7-ene In acetonitrile at 160℃; for 0.4h; microwave irradiation;
97.5%	With 1,4-diaza-bicyclo[2.2.2]octane at 20 - 90℃; for 10h;	1; 1 1) 2,6-dichlorobenzoic acid (38.2g, 200mmol), dimethyl carbonate (305.6g) and triethylenediamine ( DABCO, 22.4 g, 200 mmol) was dissolved with stirring at room temperature. The temperature was raised to 90°C, and the reaction was maintained for 10 hours.2) After the reaction is completed, the heating is stopped, and the reaction is cooled to room temperature by itself. The solvent was evaporated under reduced pressure, and 152.8 g of water was added to the residual liquid, followed by vigorous stirring, followed by extraction with ethyl acetate. The ethyl acetate layer was washed successively with water, dilute hydrochloric acid (5%), saturated sodium bicarbonate and water, and the organic phase was dried and concentrated to obtain a colorless transparent oily liquid, namely methyl 2,6-dichlorobenzoate, weighing about 40 g , the yield is 97.5%, and the content is 98.680%

86%

With 1,8-diazabicyclo[5.4.0]undec-7-ene for 48h; Heating / reflux;

151 2,6-Dichlorobenzoic acid (5.00g, 26.2 mmol) was diluted in dimethylcarbonate (44 mL, 530 mmol). 1,8- Diazabicyclo[5.4.0]undec-7-ene (DBU) (3.91 mL, 26.2 mmol) was added last. The reacted was refluxed for 2 days. Upon cooling, the solution was diluted with ethyl acetate and water. The aqueous layer was removed and the organic layer was washed with water, 2N HCl (2 x's), sat. NaHC03 (2 x's), and twice with water. The organic layer was dried over sodium sulfate, filtered, and concentrated to yield 4.61g (86%) of the desired compound as a clear oil. ¹H NMR (CDC13) No.: 4.5 (s, 3H) , 7.28 - 7.38 (m, 3H) .

Reference： [1]Shieh, Wen-Chung; Dell, Steven; Repic, Oljan [Journal of Organic Chemistry, 2002, vol. 67, # 7, p. 2188 - 2191]
[2]Shieh, Wen-Chung; Dell, Steven; Repič, Oljan [Tetrahedron Letters, 2002, vol. 43, # 32, p. 5607 - 5609]
[3]Current Patent Assignee: WEISIPU NEW MAT SUZHOU CO LTD - CN114181076, 2022, A Location in patent: Paragraph 0022; 0035-0038; 0047-0050
[4]Current Patent Assignee: TAKEDA PHARMACEUTICAL COMPANY LIMITED - WO2005/99688, 2005, A2 Location in patent: Page/Page column 305

7
tetramethylammonium 2,6-dichlorobenzoate [ No CAS ]
[ 74-88-4 ]
[ 14920-87-7 ]

Yield	Reaction Conditions	Operation in experiment
	In acetonitrile at 30℃;
	In acetonitrile at 30℃;

Reference： [1]Kondo, Yasuhiko; Urade, Miyuki; Yamanishi, Yukari; Chen, Xinyu [Journal of the Chemical Society. Perkin Transactions 2 (2001), 2002, # 8, p. 1449 - 1454]
[2]Kondo, Yasuhiko; Urade, Miyuki; Yamanishi, Yukari; Chen, Xinyu [Journal of the Chemical Society. Perkin Transactions 2 (2001), 2002, # 8, p. 1449 - 1454]

8
[ 14920-87-7 ]
2,6-dichlorobenzohydrazide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
71%	With hydrazine hydrate In methanol at 79.85℃; for 8h;

Reference： [1]Wardell, Solange M.S.V.; Vasconcelos, Thatyana R. A.; De Souza, Marcus V. N.; Wardell, James L.; Low, John N.; Glidewell, Christopher [Acta Crystallographica, Section C: Crystal Structure Communications, 2006, vol. 62, # 10, p. o618-o624]

9
[ 14920-87-7 ]
[ 60933-65-5 ]
C₁₅H₁₆NSO₃Cl [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
92%	Stage #1: 2,6-dichlorobenzoic acid methyl ester; (R)-S-methyl-S-phenylsulfoximine With caesium carbonate; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl In toluene at 20℃; for 0.5h; Stage #2: In toluene at 135℃; for 1.5h; microwave irradiation; Further stages.;

Reference： [1]Harmata, Michael; Hong, Xuechuan [Synlett, 2007, # 6, p. 969 - 973]

10
[ 14920-87-7 ]
8-(2,6-dichlorophenyl)-5,6-dihydro-<1,2>dithiolo<1,5-b>naphtho<2,1-d><1,2>dithiole-10-S^IV [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: 20 percent / sodium hydride / 1,2-dimethoxy-ethane / 6 h / Heating 2: 22 percent / P₂S₅ / toluene / 2 h / Heating

Reference： [1]Arcoleo, Antonino; Abbate, Giovanni; Gottuso, Mario; Fontana, Giacomo; Giammona, Gaetano [Heterocycles, 1988, vol. 27, # 9, p. 2141 - 2152]

11
[ 14920-87-7 ]
8-(2-chloro-6-methoxyphenyl)-5,6-dihydro-<1,2>dithiolo<1,5-b>naphtho<2,1-d><1,2>dithiole-10-S^IV [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: 43 percent / sodium hydride / 1,2-dimethoxy-ethane / 6 h / Heating 2: 38 percent / P₂S₅ / toluene / 2 h / Heating

Reference： [1]Arcoleo, Antonino; Abbate, Giovanni; Gottuso, Mario; Fontana, Giacomo; Giammona, Gaetano [Heterocycles, 1988, vol. 27, # 9, p. 2141 - 2152]

12
[ 14920-87-7 ]
2,4-dichloro-3-methoxycarbonylbenzoic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With n-butyllithium; diisopropylamine In tetrahydrofuran	R.13 Reference Example 13 Reference Example 13 To a stirred solution of diisopropylamine (22 ml) in dry tetrahydrofuran (160 ml) cooled to 0° C. under an inert atmosphere was added n-butyl lithium (2.5M, 67 ml) dropwise. The solution was stirred for 30 minutes at 0° C., then added to a solution of methyl 2,6-dichlorobenzoate (26.62 g) in dry tetrahydrofuran (160 ml) cooled to -78° C. under an inert atmosphere. After 1.5 hours at this temperature the mixture was poured onto excess solid carbon dioxide and left to stand overnight. The solvent was evaporated in vacuo and the residue acidified with 2N hydrochloric acid. This was then extracted with ethyl acetate, dried over anhydrous magnesium sulphate and evaporated in vacuo to yield 2,4-dichloro-3-methoxycarbonylbenzoic acid (32.37 g) as a solid, NMR (DMSO D6) δ3.93 (3H,s), 7.70 (1H, d), 7.91 (1H,d).

Reference： [1]Current Patent Assignee: BAYER AG - US5489570, 1996, A

13
[ 14920-87-7 ]
[ 610-96-8 ]

Yield	Reaction Conditions	Operation in experiment
98%	With methanol; sodium hydroxide In water Electrolysis;

Reference： [1]Location in patent: scheme or table Gassmann, Joerg; Voss, Juergen [Zeitschrift fur Naturforschung, B: Chemical Sciences, 2008, vol. 63, # 11, p. 1291 - 1299]

14
[ 74-88-4 ]
[ 50-30-6 ]
[ 14920-87-7 ]

Yield	Reaction Conditions	Operation in experiment
76%	With potassium carbonate In N,N-dimethyl-formamide at 20℃; for 24h; Inert atmosphere;	methyl 2,4,6-trimethylbenzoate (S4) General procedure: To a 250 mL round bottom flask equipped with a stir barwere added 2,4,6-trimethylbenzoic acid (6.57 g, 40.0 mmol, 1 equiv), potassium carbonate (8.29g, 60.0 mmol, 1.5 equiv) and DMF (50 mL). Iodomethane (3.00 mL, 48.0 mmol, 1.2 equiv) wasslowly added to the reaction vessel and the resulting suspension was stirred vigorously at roomtemperature for 24 h. The reaction was poured onto 300 mL of H2O and extracted with 3 x 300mL portions of Et2O. The combined organic extracts were washed with 3 x 150 mL portions ofH2O and 2 x 150 mL portions of brine. The organic layer was dried over MgSO4, filtered, andconcentrated to dryness. The residue was purified by passing through a pad of silica eluting with1:1 EtOAc/hexanes to give methyl ester S4 (6.28 g, 35.2 mmol, 88% yield) as a pale yellow oil.Spectral data are in agreement with those previously published.4
70%	With sodium hydrogencarbonate; sodium sulfate In N,N-dimethyl-formamide at 20℃; Cooling with ice;

Reference： [1]White, Alexander R.; Wang, Leifeng; Nicewicz, David A. [Synlett, 2019, vol. 30, # 7, p. 827 - 832]
[2]Location in patent: experimental part Gassmann, Joerg; Voss, Juergen [Zeitschrift fur Naturforschung, B: Chemical Sciences, 2008, vol. 63, # 11, p. 1291 - 1299]

15
[ 14920-87-7 ]
[ 75-05-8 ]
[ 71463-50-8 ]

Yield	Reaction Conditions	Operation in experiment
67%	With lithium diisopropyl amide In tetrahydrofuran at -78 - 20℃; for 2h; Inert atmosphere;
	Stage #1: acetonitrile With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.75h; Stage #2: 2,6-dichlorobenzoic acid methyl ester In tetrahydrofuran; hexane at -78℃; for 0.5h; Stage #3: With methanol In tetrahydrofuran; hexane	151 n-Butyl lithium (20.1 mL, 32.2 mmol, 1.6M in hexanes) was added to THF (30 mL) and the solution was cooled to - 78 °C. Acetonitrile (1.7 mL, 32 mmol) was added dropwise and the reaction stirred at the temperature for 45 minutes. Methyl 2,6-dichlorobenzoate (1.00g, 4.88 mmol) was dissolved in 2 mL THF and added to the reaction mixture. The reaction stirred at -78 °C for 0.5 hr. The solution was quenched with methanol and warmed to room temperature. The material was diluted with water and 1N HC1. The solution was then extracted with Ethyl acetate, dried, and concentrated to give 1.08g of desired product at 85% purity. Material used as is in the next step. @H-NMR (CDC13) No.: 4. 0 (s, 2H) , 7.28 - 7. 40 (m, 3H) .

Reference： [1]Vogl, Michael; Brecker, Lothar; Kratzer, Regina; Nidetzky, Bernd [Chirality, 2012, vol. 24, # 10, p. 847 - 853,7]
[2]Current Patent Assignee: TAKEDA PHARMACEUTICAL COMPANY LIMITED - WO2005/99688, 2005, A2 Location in patent: Page/Page column 305-306

16
C₈H₆Br₂Cl₂O [ No CAS ]
[ 14920-87-7 ]

Yield	Reaction Conditions	Operation in experiment
	With water; sodium hydroxide at 20℃;

Reference： [1]Location in patent: experimental part Mayhoub, Abdelrahman S.; Talukdar, Arindam; Cushman, Mark [Journal of Organic Chemistry, 2010, vol. 75, # 10, p. 3507 - 3510]

17
[ 33486-90-7 ]
[ 14920-87-7 ]
[ 83-38-5 ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 1,3-dichloro-2-methoxymethylbenzene With N-Bromosuccinimide In tetrachloromethane for 2h; Irradiation; Reflux; Stage #2: With water; sodium hydroxide at 20℃;

Reference： [1]Location in patent: experimental part Mayhoub, Abdelrahman S.; Talukdar, Arindam; Cushman, Mark [Journal of Organic Chemistry, 2010, vol. 75, # 10, p. 3507 - 3510]

18
[ 33863-76-2 ]
[ 14920-87-7 ]

Reference： [1]Patent: US2012/28952,2012,A1

19
[ 1321613-01-7 ]
[ 74-88-4 ]
[ 14920-87-7 ]

Yield	Reaction Conditions	Operation in experiment
83%	With potassium carbonate; In N,N-dimethyl-formamide; at 20℃; for 2h;	H8) 2,6-Dichloro-benzoic acid methyl ester To a solution containing compound H7 (50 g, 0.26 mmol) and K2CO3 (53.8 g, 0.39 mmol) in DMF (200 mL) was added methyl iodide (75.9 g, 0.52 mmol). The mixture was stirred at ambient temperature for 2 h, poured into water (500 mL) and extracted with ethylacetate (2×500 mL). The combined ether layers were washed with water, brine, dried, filtered, and concentrated under reduced pressure to provide compound H8 (45 g, 83%) as a yellow oil, Rf=0.8 (petrolether: ethylacetate=10:1).

Reference： [1]Patent: US2012/28952,2012,A1 .Location in patent: Page/Page column 17

20
[ 14920-87-7 ]
[ 73183-34-3 ]
[ 1321613-04-0 ]

Yield	Reaction Conditions	Operation in experiment
53%	With 4,4'-di-tert-butyl-2,2'-bipyridine In n-heptane for 18h; Reflux;	A.A-49A A-49A) 2,6-Dichloro-4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-benzoicacid methyl ester Bis(pinacolato)diboron [Pin2B2] (44.8 g, 176 mmol), 4,4'-Di-tert-butyl-[2,2']bipyridinyl (120 mg, 0.44 mmol), and [Ir(COD)(OMe)]2 (147 mg, 0.22 mmol) were added to a solution of compound H8 (45 g, 0.22 mol) in heptane (500 mL). The reaction mixture turned from yellow to forest green to brick red within the first minute. The reaction mixture was heated to reflux for 18 h and then partitioned between ethyl acetate and water. The organic extracts were combined, dried over Na2SO4 and concentrated under reduced pressure. The solid residue was purified by chromatography on silica gel (PE: EtOAc=50:1, detected by boric indicator) to afford the title compound (A-49A) as a white solid (41.0 g, 53%). Rf=0.4 (petrolether: ethylacetate=20:1).

Reference： [1]Current Patent Assignee: C.H. Boehringer Sohn AG & Co. KG - US2012/28952, 2012, A1 Location in patent: Page/Page column 18

21
[ 14920-87-7 ]
[ 1402977-12-1 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: lithium diisopropyl amide / tetrahydrofuran / 2 h / -78 - 20 °C / Inert atmosphere 2: potassium phosphate; Candida tenuis xylose reductase; NADH / methanol / 24 h

Reference： [1]Vogl, Michael; Brecker, Lothar; Kratzer, Regina; Nidetzky, Bernd [Chirality, 2012, vol. 24, # 10, p. 847 - 853,7]

22
[ 67-56-1 ]
[ 83-38-5 ]
[ 14920-87-7 ]

Yield	Reaction Conditions	Operation in experiment
79%	With manganese(IV) oxide; caesium carbonate; 1,8-diazabicyclo[5.4.0]undec-7-ene; 1-butyl-3-methylimidazolium Tetrafluoroborate at 20℃; for 24h; Inert atmosphere;	4.2 General procedure for oxidative esterification of aldehydes General procedure: In a typical procedure, a capped vessel was charged with ionic liquid BmimBF4 (0.5 mL) and put under positive pressure of nitrogen. DBU (0.5 mmol) and Cs2CO3 (1.5 mmol) were added followed by the aldehyde (0.5 mmol) and MnO2 (1.5 mmol). The reaction mixture was stirred for a few minutes and alcohol (1.5 mmol) was added. The reaction mixture was stirred at ambient temperature for 24 h. The mixture was then filtered through a thin pad of silica, which was washed with ethyl acetate (30 mL). The filtrate was analyzed by TLC and 1H NMR and then concentrated under vacuum. The resulting residue was purified by flash chromatography on silica gel where needed.
75%	With urea-2,2-dihydroperoxypropane; hydrogen bromide; acetic acid at 20℃; for 10h;

Reference： [1]Chiarotto, Isabella; Feroci, Marta; Sotgiu, Giovanni; Inesi, Achille [Tetrahedron, 2013, vol. 69, # 37, p. 8088 - 8095]
[2]Khosravi, Kaveh; Khalaji, Kobra; Naserifar, Shirin [Journal of the Chinese Chemical Society, 2017, vol. 64, # 3, p. 303 - 309]

23
[ 14920-87-7 ]
1-(4-(4-(trifluoromethoxy)benzyl)phenyl)ethanone [ No CAS ]
C₂₃H₁₅Cl₂F₃O₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
47%	With sodium hydride In tetrahydrofuran at 20 - 80℃; for 18h;	10 Preparation and Characterization of Compounds of Formula (VI) 2.2 g of methyl 2,6-dichlorobenzoate was dissolved in 20 ml of dry tetrahydrofuran (THF)400 mg NaH,Then, 5 ml of a THF solution of 1.62 g of Intermediate A2 was added dropwise,Stirred at room temperature for 2h, and then heated to 80 ° C reflux 16h,Cooled to room temperature, the solvent was dried under reduced pressure,The residue was dissolved in 30 ml of dichloromethane,Washed with water, 1 M aqueous hydrochloric acid solution,The organic phase was washed with brine,Then dried over anhydrous sodium sulfate and the solvent was dried under reduced pressure,The residue was passed through a silica gel column using petroleum ether: ethyl acetate = 25: 1 (by volume)1.2 g of intermediate B3 (intermediate B3 as light yellow liquid) was obtained,The yield was 47%

Reference： [1]Current Patent Assignee: TSINGHUA UNIVERSITY (CHINA) - CN103787966, 2016, B Location in patent: Paragraph 0149-0151

24
[ 67-56-1 ]
[ 50-30-6 ]
[ 14920-87-7 ]

Yield	Reaction Conditions	Operation in experiment
	In thionyl chloride for 1h; Reflux;

Reference： [1]Frański, Rafał; Gierczyk, Błażej; Zalas, Maciej; Jankowski, Wojciech; Hoffmann, Marcin [Journal of Mass Spectrometry, 2018, vol. 53, # 5, p. 379 - 384]

25
[ 14920-87-7 ]
[ 232275-54-6 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: (1,5-cyclooctadiene)(methoxy)iridium(I) dimer; 4,4'-di-tert-butyl-2,2'-bipyridine / 20 h / 80 °C / Inert atmosphere; Schlenk technique 2: potassium peroxymonosulfate sulfate; water / acetone / 0.5 h / 20 °C / Inert atmosphere

Reference： [1]Shahzadi, Tayyaba; Saleem, Rahman S. Z.; Chotana, Ghayoor A. [Synthesis, 2018, vol. 50, # 21, p. 4336 - 4342]

26
[ 14920-87-7 ]
[ 25015-63-8 ]
[ 1321613-04-0 ]

Yield	Reaction Conditions	Operation in experiment
71%	With (1,5-cyclooctadiene)(methoxy)iridium(I) dimer; 4,4'-di-tert-butyl-2,2'-bipyridine at 80℃; for 20h; Inert atmosphere; Schlenk technique; regioselective reaction;	Borylation of Arenes; General Procedure General procedure: In a fume hood, an oven dried Schlenk flask equipped with a magnetic stirring bar was filled with N2 and evacuated (three cycles). Under N2 atmosphere [Ir(OMe)(COD)]2 (13.3 mg, 0.01 mmol, 1 mol%), 4,4-ditert-butyl-2,2′-bipyridyl (10.7 mg, 0.02 mmol, 2 mol%), and pinacolborane (HBPin) (436 μL, 384 mg, 3 mmol, 1.5 equiv) were added. The appropriate arene substrate (2 mmol, 1 equiv) was added via micropipette under N2 atmosphere. The Schlenk flask was closed and the reaction mixture was heated at 80 °C in an oil bath. The progress of reaction was monitored by GC-MS and TLC. Upon completion of reaction, Schlenk flask was cooled to r.t. and exposed to air. The contents of the flask were dissolved in CH2Cl2 (3-5 mL) and taken out in a round-bottomed flask. The volatile organics were removed under reduced pressure using a rotary evaporator. The crude product was purified by column chromatography (silica gel, hexanes-CH2Cl2 1:1).

Reference： [1]Shahzadi, Tayyaba; Saleem, Rahman S. Z.; Chotana, Ghayoor A. [Synthesis, 2018, vol. 50, # 21, p. 4336 - 4342]

27
[ 14920-87-7 ]
[ 15258-73-8 ]

Yield	Reaction Conditions	Operation in experiment
95%	With zinc(II) tetrahydroborate; In ethanol; at 78℃; for 3h;	Add 100 ml of absolute ethanol to the four-necked flask and heat to reflux.15 g of the raw material methyl 2,6-dichlorobenzoate was added to the ethanol.10 g of zinc borohydride was slowly added thereto, and the reaction was stirred at 78 C for 3 h.After the GC reaction was completed, the solvent was evaporated to dryness to obtain 12 g.2,6-dichlorobenzyl alcohol.The product yield was 95% and the purity was 98%.

Reference： [1]Patent: CN108794297,2018,A .Location in patent: Paragraph 0007; 0008; 0009

28
[ 67969-82-8 ]
[ 13755-29-8 ]
[ 14920-87-7 ]
3,3’‐oxybis(tert‐butylbenzene) [ No CAS ]
3,6‐di‐tert‐butyl‐9‐(2,6‐dichlorophenyl)xanthylium tetrafluoroborate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
46%	Stage #1: 3,3’‐oxybis(tert‐butylbenzene) With N,N,N,N,-tetramethylethylenediamine; sec.-butyllithium In hexane; cyclohexane at 20℃; for 4h; Inert atmosphere; Cooling with ice; Stage #2: 2,6-dichlorobenzoic acid methyl ester In hexane; cyclohexane at -78 - 20℃; for 12h; Inert atmosphere; Stage #3: tetrafluoroboric acid diethyl ether; sodium tetrafluoroborate Further stages;	3,6-Di-tert-butyl-9-mesitylxanthylium Tetrafluoroborate (3) General procedure: To a flame-dried 250 mL round-bottom flask under argon wereadded 4 (8.02 g, 28.4 mmol, 1 equiv), TMEDA (8.71 mL, 58.2mmol, 2.05 equiv), and anhydrous n-hexane (28 mL). Theresulting solution was cooled in an ice bath and sec-butyllithium(1.4 M solution in cyclohexane, 42.0 mL, 58.2 mmol, 2.05equiv) was added dropwise. The ice bath was removed and thereaction mixture was stirred at room temperature for 4 h. Thereaction was cooled to -78 °C and a solution of methyl 2,4,6-trimethylbenzoate (5.11 g, 28.7 mmol, 1.01 equiv) in anhydrousn-hexane (28 mL) was added slowly via cannula. After the addition,the mixture was allowed to slowly warm to room temperatureand stirred for 12 h. The reaction was quenched with water(25 mL) and the biphasic mixture was stirred vigorously for 30min. The mixture was diluted with Et2O (100 mL) and the layerswere separated. The organic layer was washed with water(2 × 150 mL) and brine (1 × 150 mL). The organic layer wastransferred to a 250 mL round-bottom flask equipped with astir bar. To the vigorously stirred solution was added conc. HCl(12 mL), resulting in a bright-yellow precipitate. The suspensionwas stirred vigorously for 30 min then diluted with water (150mL). The layers were separated and the organic layer wasextracted with water (3 × 150 mL or until the washings becomecolorless). To the combined aqueous layers was added solidNaBF4 (9.35 g, 85.2 mmol, 3 equiv), resulting in a bright-yellowprecipitate. The resulting suspension was extracted withdichloromethane (3 × 150 mL or until the washings become colorless).To the combined organic layers was added HBF4·Et2Ocomplex (3.46 mL, 28.4 mmol, 1 equiv). The solution wasswirled to achieve homogeneity then washed with water(1 × 100 mL) and aq. NaBF4 (1 M, 1 × 100 mL). The organic layerwas dried over solid NaBF4, filtered, and concentrated to dryness.The residue was purified by trituration with hexanes andfiltered. The solid was rinsed with n-pentane and dried in vacuoto give xanthylium 3 (10.6 g, 21.3 mmol, 75% yield) as a yelloworangesolid.

Reference： [1]White, Alexander R.; Wang, Leifeng; Nicewicz, David A. [Synlett, 2019, vol. 30, # 7, p. 827 - 832]

29
[ 14920-87-7 ]
3,3’‐oxybis(tert‐butylbenzene) [ No CAS ]
3,6‐di‐tert‐butyl‐9‐(2,6‐dichlorophenyl)‐10‐phenylacridin‐10‐ium tetrafluoroborate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1.1: N,N,N,N,-tetramethylethylenediamine; sec.-butyllithium / hexane; cyclohexane / 4 h / 20 °C / Inert atmosphere; Cooling with ice 1.2: 12 h / -78 - 20 °C / Inert atmosphere 2.1: acetic acid; triethylamine / dichloromethane / 12 h / 20 °C / Inert atmosphere; Darkness

Reference： [1]White, Alexander R.; Wang, Leifeng; Nicewicz, David A. [Synlett, 2019, vol. 30, # 7, p. 827 - 832]

30
[ 13755-29-8 ]
[ 24085-65-2 ]
[ 14920-87-7 ]
2,7‐di‐tert‐butyl‐9‐(2,6‐dichlorophenyl)xanthylium tetrafluoroborate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
31%	Stage #1: 4,4'‐oxybis(tert‐butylbenzene) With N,N,N,N,-tetramethylethylenediamine; sec.-butyllithium In hexane; cyclohexane at 20℃; for 4h; Inert atmosphere; Cooling with ice; Stage #2: 2,6-dichlorobenzoic acid methyl ester In hexane; cyclohexane at -78 - 20℃; for 12h; Inert atmosphere; Stage #3: sodium tetrafluoroborate Further stages;	3,6-di-tert-butyl-9-mesitylxanthylium tetrafluoroborate (3) General procedure: To a flame-dried 250 mL roundbottom flask under argon were added 4 (8.02 g, 28.4 mmol, 1 equiv), TMEDA (8.71 mL, 58.2mmol, 2.05 equiv), and anhydrous n-hexane (28 mL). The resulting solution was cooled in an icebath and sec-butyllithium (1.4 M solution in cyclohexane, 42.0 mL, 58.2 mmol, 2.05 equiv) wasadded dropwise. The ice bath was removed and the reaction mixture was stirred at roomtemperature for 4 h. The reaction was cooled to -78 C and a solution of methyl 2,4,6-trimethylbenzoate (5.11 g, 28.7 mmol, 1.01 equiv) in anhydrous n-hexane (28 mL) was addedslowly via cannula. After the addition, the reaction was allowed to slowly warm to roomtemperature and stirred for 12 h. The reaction was quenched with water (25 mL) and the biphasicmixture was stirred vigorously for 30 min. The mixture was diluted with 100 mL of Et2O and thelayers were separated. The organic layer was washed with water (2 x 150 mL) and brine (1 x 150mL). The organic layer was transferred to a 250 mL round bottom flask equipped with a stir bar.To the vigorously stirred solution was added conc. HCl (12 mL) resulting in a bright yellowprecipitate that slowly turned brown over the course of addition. The brown suspension wasstirred vigorously for 30 min then diluted with water (150 mL). The layers were separated, andthe organic layer was extracted with water (3 x 150 mL or until the washings become colorless).To the combined aqueous layers was added solid NaBF4 (9.35 g, 85.2 mmol, 3 equiv) resulting ina bright yellow precipitate. The resulting suspension was extracted with dichloromethane (3 x150 mL or until the washings become colorless). To the combined organic layers was added HBF4Et2O complex (3.46 mL, 28.4 mmol, 1 equiv). The solution was swirled to achieve homogeneitythen washed with water (1 x 100 mL) and aq. NaBF4 (1 M, 1 x 100 mL). The organic layer wasdried over solid NaBF4, filtered, and concentrated to dryness. The residue was purified bytrituration with hexanes and filtered. The solid was rinsed with n-pentane and dried in vacuo togive xanthylium 3 (10.6 g, 21.3 mmol, 75% yield) as a yellow-orange solid.

Reference： [1]White, Alexander R.; Wang, Leifeng; Nicewicz, David A. [Synlett, 2019, vol. 30, # 7, p. 827 - 832]

31
[ 24085-65-2 ]
[ 14920-87-7 ]
10‐benzyl‐2,7‐di‐tert‐butyl‐9‐(2,6‐dichlorophenyl)acridin‐10‐ium tetrafluoroborate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1.1: N,N,N,N,-tetramethylethylenediamine; sec.-butyllithium / hexane; cyclohexane / 4 h / 20 °C / Inert atmosphere; Cooling with ice 1.2: 12 h / -78 - 20 °C / Inert atmosphere 2.1: acetic acid; triethylamine / dichloromethane / 12 h / 20 °C / Inert atmosphere; Darkness

Reference： [1]White, Alexander R.; Wang, Leifeng; Nicewicz, David A. [Synlett, 2019, vol. 30, # 7, p. 827 - 832]

32
[ 541-73-1 ]
[ 14920-87-7 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1.1: n-butyllithium / hexane; tetrahydrofuran / 0.75 h / -78 °C / Inert atmosphere 1.2: 0.17 h / -78 °C / Inert atmosphere 2.1: potassium carbonate / N,N-dimethyl-formamide / 24 h / 20 °C / Inert atmosphere

Reference： [1]White, Alexander R.; Wang, Leifeng; Nicewicz, David A. [Synlett, 2019, vol. 30, # 7, p. 827 - 832]

33
[ 33486-90-7 ]
[ 14920-87-7 ]

Yield	Reaction Conditions	Operation in experiment
71%	With oxygen In water at 25℃; for 12h; Irradiation; Green chemistry;

Reference： [1]Jiang, Li-Ya; Ming, Jing-Jing; Wang, Lian-Yue; Jiang, Yuan-Yuan; Ren, Lan-Hui; Wang, Zi-Cheng; Cheng, Wen-Chen [Green Chemistry, 2020, vol. 22, # 4, p. 1156 - 1163]

34
[ 14920-87-7 ]
[ 1679-18-1 ]
C₁₄H₁₀Cl₂O₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
92%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; sodium carbonate In ethanol; water; toluene Inert atmosphere; Reflux;	5 The synthetic route of Intermediate 3 is as follows In a clean 250mL three-necked bottle, add 7.5g (47.8mmol) in sequence4-chlorophenylboronic acid, 0.46 g (0.4 mmol) of tetrakis (triphenylphosphine) palladium and 8.4 g of anhydrous sodium carbonate (79.6 mmol) were replaced with nitrogen gas three times to get rid of the air in the system.Add 100mL of mixed solvent (toluene: water: ethanol = 5: 1: 1 (V / V))And 8.2g (39.8mmol) of methyl 2,6-dichlorobenzoate, and stirred at room temperature for 10min. The system was moved to an oil bath, gradually heated to reflux and reacted overnight at reflux.After the reaction was completed, the heating was stopped and the reaction system cooled to room temperature by itself.The reaction solution was poured into about 200 mL of water, and extracted with dichloromethane.After drying the organic phase over anhydrous sodium sulfate, it is concentrated under reduced pressure,And further purified by column chromatography (350 mesh silica gel, eluent is petroleum ether:Dichloromethane = 20: 1 (V / V)), then 10.3g of light yellow oily liquid was obtained,The yield was 92%.

Reference： [1]Current Patent Assignee: WEISIPU NEW MATERIAL (SUZHOU) CO LTD - CN111056959, 2020, A Location in patent: Paragraph 0261-0265

35
[ 14920-87-7 ]
C₁₃H₆Cl₂O [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1.1: sodium carbonate; tetrakis(triphenylphosphine) palladium⁽⁰⁾ / toluene; water; ethanol / Inert atmosphere; Reflux 2.1: sodium hydroxide / water / Reflux 2.2: polyphosphoric acid / 4 h / 160 °C

Reference： [1]Current Patent Assignee: WEISIPU NEW MATERIAL (SUZHOU) CO LTD - CN111056959, 2020, A

36
[ 14920-87-7 ]
C₂₅H₃₀B₂O₅ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1.1: sodium carbonate; tetrakis(triphenylphosphine) palladium⁽⁰⁾ / toluene; water; ethanol / Inert atmosphere; Reflux 2.1: sodium hydroxide / water / Reflux 2.2: polyphosphoric acid / 4 h / 160 °C 3.1: tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; XPhos; potassium acetate / 1,4-dioxane / Inert atmosphere; Reflux

Reference： [1]Current Patent Assignee: WEISIPU NEW MATERIAL (SUZHOU) CO LTD - CN111056959, 2020, A

37
[ 14920-87-7 ]
C₄₃H₂₆N₆O [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 4 steps 1.1: sodium carbonate; tetrakis(triphenylphosphine) palladium⁽⁰⁾ / toluene; water; ethanol / Inert atmosphere; Reflux 2.1: sodium hydroxide / water / Reflux 2.2: polyphosphoric acid / 4 h / 160 °C 3.1: tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; XPhos; potassium acetate / 1,4-dioxane / Inert atmosphere; Reflux 4.1: sodium carbonate; tetrakis(triphenylphosphine) palladium⁽⁰⁾ / toluene; water; ethanol / Inert atmosphere; Reflux

Reference： [1]Current Patent Assignee: WEISIPU NEW MATERIAL (SUZHOU) CO LTD - CN111056959, 2020, A

38
[ 14920-87-7 ]
C₄₃H₂₈N₆ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 5 steps 1.1: sodium carbonate; tetrakis(triphenylphosphine) palladium⁽⁰⁾ / toluene; water; ethanol / Inert atmosphere; Reflux 2.1: sodium hydroxide / water / Reflux 2.2: polyphosphoric acid / 4 h / 160 °C 3.1: tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; XPhos; potassium acetate / 1,4-dioxane / Inert atmosphere; Reflux 4.1: sodium carbonate; tetrakis(triphenylphosphine) palladium⁽⁰⁾ / toluene; water; ethanol / Inert atmosphere; Reflux 5.1: iodine; acetic acid; hypophosphorous acid / 4 h / 120 °C / Inert atmosphere

Reference： [1]Current Patent Assignee: WEISIPU NEW MATERIAL (SUZHOU) CO LTD - CN111056959, 2020, A

39
[ 14920-87-7 ]
C₅₅H₃₄N₆ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 5 steps 1.1: sodium carbonate; tetrakis(triphenylphosphine) palladium⁽⁰⁾ / toluene; water; ethanol / Inert atmosphere; Reflux 2.1: sodium hydroxide / water / Reflux 2.2: polyphosphoric acid / 4 h / 160 °C 3.1: tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; XPhos; potassium acetate / 1,4-dioxane / Inert atmosphere; Reflux 4.1: sodium carbonate; tetrakis(triphenylphosphine) palladium⁽⁰⁾ / toluene; water; ethanol / Inert atmosphere; Reflux 5.1: n-butyllithium / tetrahydrofuran / 1.5 h / -78 - 20 °C / Inert atmosphere 5.2: 20 °C 5.3: Reflux

Reference： [1]Current Patent Assignee: WEISIPU NEW MATERIAL (SUZHOU) CO LTD - CN111056959, 2020, A

40
[ 14920-87-7 ]
[ 3900-89-8 ]
C₁₄H₁₀Cl₂O₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
89%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; sodium carbonate In ethanol; water; toluene at 20℃; Inert atmosphere; Reflux;	5 (Synthesis of Intermediate 3) The synthetic route of Intermediate 3 is as follows: In a clean 250mL three-necked bottle, add 7.5g (47.8mmol) of 2-chlorophenylboronic acid,0.46 g (0.4 mmol) of tetrakis (triphenylphosphine) palladium and 8.4 g of anhydrous sodium carbonate (79.6 mmol) were replaced with nitrogen three times to get rid of the air in the system.100 mL of a mixed solvent (toluene: water: ethanol = 5: 1: 1 (V / V)) and 8.2 g (39.8 mmol) of methyl 2,6-dichlorobenzoate were added, and stirred at room temperature for 10 min.The system was moved to an oil bath, gradually heated to reflux and reacted overnight at reflux.After the reaction was completed, the heating was stopped and the reaction system cooled to room temperature by itself.The reaction solution was poured into about 200 mL of water, and extracted with dichloromethane.After drying the organic phase over anhydrous sodium sulfate, it is concentrated under reduced pressure and further purified by column chromatography(350 mesh silica gel, eluent is petroleum ether: dichloromethane = 20: 1 (V / V)). After that, 10.0 g of light yellow oily liquid was obtained with a yield of 89%.

Reference： [1]Current Patent Assignee: WEISIPU NEW MATERIAL (SUZHOU) CO LTD - CN111057005, 2020, A Location in patent: Paragraph 0261-0265

41
[ 14920-87-7 ]
C₁₃H₆Cl₂O [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1: sodium carbonate; tetrakis(triphenylphosphine) palladium⁽⁰⁾ / toluene; water; ethanol / 20 °C / Inert atmosphere; Reflux 2: sodium hydroxide; water / Reflux 3: polyphosphoric acid / 4 h / 160 °C