[ CAS No. 2100-42-7 ] {[proInfo.proName]}

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2D 3D

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Quality Control of [ 2100-42-7 ]

COA NMR CNMR HPLC LC-MS

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Product Details of [ 2100-42-7 ]

CAS No. :	2100-42-7	MDL No. :	MFCD00008356
Formula :	C₈H₉ClO₂	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	QMXZSRVFIWACJH-UHFFFAOYSA-N
M.W :	172.61	Pubchem ID :	246724
Synonyms :

Safety of [ 2100-42-7 ]

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

Application In Synthesis of [ 2100-42-7 ]

* 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 [ 2100-42-7 ]
Downstream synthetic route of [ 2100-42-7 ]

[ 2100-42-7 ] Synthesis Path-Upstream 1~4

1
[ 150-78-7 ]
[ 2100-42-7 ]
[ 51560-21-5 ]
[ 25245-35-6 ]

Reference： [1] Organic Process Research and Development, 2003, vol. 7, # 1, p. 98 - 100

2
[ 2100-42-7 ]
[ 76-05-1 ]
[ 90064-48-5 ]

Yield	Reaction Conditions	Operation in experiment
47%	With hexamethylenetetramine In tetrahydrofuran at 90 - 95℃; for 2 h;	To a mixture of compound 4 (1.0 g, 5.79 mmol) and hexamethylenetetramine (893mg, 6.37 mmol) in THF, TFA (12.89 mg, 113 mmol) was added slowly. The reactionmixture was then refluxed for 2 hours. After that, the hot reaction liquid was pouredinto ice and its pH was adjusted to 7 with NaHCO3 powder. The mixture was extractedwith ethyl acetate and the organic phase was collected, washed with brine, dried overNa2SO4, and concentrated under reduced pressure to get the reaction crude. Thereaction crude was then purified with silica gel to give 543 mg compound 5 as a whitesolid in 47 percent yield.

Reference： [1] Journal of Organic Chemistry, 1993, vol. 58, # 27, p. 7906 - 7912
[2] Bioorganic and Medicinal Chemistry Letters, 2017, vol. 27, # 1, p. 72 - 76
[3] Journal of the American Chemical Society, 2008, vol. 130, # 49, p. 16786 - 16790

3
[ 100-97-0 ]
[ 2100-42-7 ]
[ 90064-48-5 ]

Reference： [1] Marine Drugs, 2012, vol. 10, # 5, p. 1103 - 1125
[2] Patent: WO2018/157800, 2018, A1, . Location in patent: Paragraph 0420-0421

4
[ 2100-42-7 ]
[ 1073339-07-7 ]

Reference： [1] Chemistry - A European Journal, 2014, vol. 20, # 19, p. 5573 - 5579
[2] Patent: WO2015/82592, 2015, A2,

[ 2100-42-7 ] Synthesis Path-Downstream 1~21

1
[ 2100-42-7 ]
[ 90064-46-3 ]

Reference： [1]European Journal of Organic Chemistry,1998,p. 335 - 348
[2]Acta Chemica Scandinavica (1947),1958,vol. 12,p. 537,542
[3]Helvetica Chimica Acta,1948,vol. 31,p. 525,535

2
[ 77-78-1 ]
[ 615-67-8 ]
[ 2100-42-7 ]

Reference： [1]Helvetica Chimica Acta,1948,vol. 31,p. 525,535

3
[ 150-78-7 ]
[ 2100-42-7 ]

Yield	Reaction Conditions	Operation in experiment
100%	With 1-(chloromethyl)-4-fluoro-1,4-diazoniabicyclo-[2.2.2]octane bis(tetrafluoroborate); sodium chloride In acetonitrile at 20℃; for 113h;
95%	With 1,4-diaza-bicyclo[2.2.2]octane; N-chloro-succinimide In dichloromethane at 20℃;
95%	With 1,4-diaza-bicyclo[2.2.2]octane; 1,3-Dichloro-5,5-dimethyl-2,4-imidazolidinedione In dichloromethane at 25℃; for 1h;	3 Synthesis of compound 2c In a 25mL reaction tube,Add p-dimethoxybenzene (0.5 mmol),1,3-dihalo-5,5-dimethylhydantoin (0.55mmol),triethylenediamine (0.025 mmol) and dichloromethane (2 mL),Stir at 25°C for 1 hour,After the reaction is completed,concentrate,The product 2c was isolated by column chromatography (95%).

93%	With N-chloro-succinimide; iron(III) chloride In acetonitrile for 0.5h;
92%	With aluminum(III) oxide; sodium hypochlorite; (salen)Mn(III) In dichloromethane at 20℃; for 0.5h;
90%	With N-chloro-succinimide; ammonium cerium (IV) nitrate In neat (no solvent) at 20℃; for 1.5h; Green chemistry; chemoselective reaction;	General procedure for synthesis of 2,4-dibromo-1-methoxy-3,5-dimethylbenzene(2b) in ball-milling. General procedure: 1-Methoxy-3,5-dimethylbenzene(100mg, 0.73 mmol), N-Bromosuccinimide (NBS,260 mg,1.46 mmol) and one ball (5 mmdiameter, stainless steel) were transferred to a milling jar (10 mL, stainlesssteel). The ball-milling operation was performed and the progress of reaction was monitored by TLC/1H NMR.[1]After completion, the reaction mixture was transferred into 30 mL ethyl acetate and cooled at 0 °C. The product was isolated as filtrate upon paper filtration and waste succinimide as precipitate. The resulting filtrate were concentrated in vacuo to isolate 250 mg (yield: 85%) of 2b as colourless powder. To test the efficiency in large scale, the reaction was also performed for the mono-bromination of 1-methoxy-3,5-dimethylbenzene in 1.3 g scale for 1 h and the product was isolated in 87% yield.[1] The milling apparatus was stopped and small portion of the sample was collected from the reaction jar to study either TLC/ proton NMR. Following, the reaction was started again andthis operation time was excluded for reporting the reaction timing.
90%	With N-chloro-succinimide; ammonium cerium (IV) nitrate In neat (no solvent) at 20℃; for 1.5h; Milling; Green chemistry; regioselective reaction;
85%	With chloro-trimethyl-silane; bis-[(trifluoroacetoxy)iodo]benzene In dichloromethane at 20℃; for 18h; Inert atmosphere;
84%	With 3-(dichloroiodo)pyridine In dichloromethane at 20℃; for 24h; Inert atmosphere;	General procedure for chlorination of 1,4-dimethoxybenzene 18 using (dichloroiodo)arenes 1,4-Dimethoxybenzene 18 (0.250 mmol) was added to a solution of (dichloroiodo)arene (0.300 mmol) indichloromethane (2 mL). The reaction was stirred at room temperature for 24 h. After completion of thereaction, 5% aqueous Na2S2O3 (5 mL) was added, and the mixture was extracted with dichloromethane. The organic phase was dried over anhydrous Na2SO4 and concentrated under reduced pressure. Purification byshort column chromatography (hexane-ethyl acetate = 10 : 1) afforded analytically pure mono-chlorinationproduct 19.2-Chloro-1,4-dimethoxybenzene (19):39 Reaction of 1,4-dimethoxybenzene 18 (35 mg, 0.250 mmol) accordingto the general procedure afforded product 19 (47-84%), isolated as a yellow oil; 1H NMR (500 MHz, CDCl3): d6.96 (d, J 3.0 Hz, 1H), 6.86 (d, J 9.0 Hz, 1H), 6.77 (dd, J 9.0 Hz, 3.0 Hz, 1H), 3.85 (s, 3H), 3.76 (s, 3H).
82%	With ammonium iodide; toluene-4-sulfonic acid; 3-chloro-benzenecarboperoxoic acid; lithium chloride In tetrahydrofuran at 20℃; for 12h; Green chemistry; regioselective reaction;	NH₄I catalytic chlorination of electron-rich aromatic compounds;typical procedure General procedure: Anisole (0.5 mmol), TsOH∘H2O (0.6 mmol), mCPBA (75%, 0.6 mmol), NH4I (0.05 mmol) and LiCl (1.0 mmol) were added to THF (5 mL). The mixture was stirred at r.t. for 12 h. Then H2O (10 mL), sat. aq Na2S2O3(4 mL), and sat. aq Na2CO3 (4 mL) were added. The mixture was extracted with CH2Cl2 (3 × 10 mL) and the combined organic layers were dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The residue was purified on a silica gel plate (20 : 1hexane-EtOAc) to afford a yellow oil product of 4-chloroanisole 64 mg(91%).
78%	With [bis(acetoxy)iodo]benzene; sodium chloride for 0.5h;
71%	With hydrogenchloride; tert.-butylhydroperoxide In methanol for 6h; Heating;
71%	With hydrogenchloride; tert.-butylhydroperoxide In methanol Heating;
71%	With hydrogenchloride; 2,3-dicyano-5,6-dichloro-p-benzoquinone In [D₃]acetonitrile; lithium hydroxide monohydrate at 24.84℃; for 4.7h; Inert atmosphere; Irradiation; Sealed tube;
71%	With N-chloro-succinimide; dimethyl sulfoxide In chloroform at 25℃; for 12h; Schlenk technique;	25 Example 25: Preparation of 2-chloro-1,4-dimethoxybenzene (Compound 25) Take a 25 mL Schlenk reaction tube, add 69.1 mg of 1,4-dimethoxybenzene, 79.8 mg of N-chlorosuccinimide, 7 μL of dimethyl sulfoxide, and 2 mL of chloroform, and stir for 12 hours at 25°C.After the reaction, the solvent was removed by rotary evaporation and column chromatography was separated to obtain 61.3 mg of 1-chloro-2,4-dimethoxybenzene with a yield of 71%.
70%	With potassium peroxomonosulfate; potassium chloride In lithium hydroxide monohydrate; acetonitrile at 20℃;
65%	With benzyltrimethylammonium tetrachloroiodate In dichloromethane for 20h; Ambient temperature;
34%	With benzyltrimethylammonium tetrachloroiodate In dichloromethane at 20℃; Inert atmosphere;	2-Chloro-1,4-dimethoxybenzene (4f) Following the procedure of Kajigaeshi et al. [5], a solution of 1,4-dimethoxybenzene (9, 414 mg, 3.00 mmol, 1.0 equiv) in CH2Cl2 was treated with Bn(Me)3N+ICl4- (1.30 g, 3.00 mmol, 1.0 equiv) and stirred overnight at room temperature. The reaction mixture was diluted with H2O and extracted three times with EtOAc. The combined organic layers were dried over MgSO4 and concentrated under reduced pressure. The residue was purified by flash column chromatography on silica gel yielding 4f (174 mg, 1.00 mmol, 34%) as yellow oil. TLC (hexane/ethyl acetate 20:1) Rf 0.31; IR (ATR) 3003 (w), 2948 (w), 2836 (w), 1581 (w), 1496 (s), 1461 (m), 1438 (m), 1271 (m), 1213 (s), 1180 (m), 1039 (s), 882 (m), 797 (m), 735 (s) cm-1; UV-vis (CH2Cl2) max (log ) 294 (3.56), 230 (3.78) nm.
	With sulfuryl dichloride; chloroform
	With N-chlorotriethylammonium chloride In trifluoroacetic acid Ambient temperature; further reagent: N-chloropiperidine; Yield given;
	With 1-chloro-piperidine In trifluoroacetic acid at 21℃;
70.8 %Spectr.	With 1,1'-ditetradecyl-3,3'-methylene-4-diimidazolin-2,2'-diylidene palladium(IV) tetrachloride; tetra-n-propyl ammonium chloride In chloroform-d1 at 25℃; for 8h; Inert atmosphere;
67 %Chromat.	With iodobenzene; toluene-4-sulfonic acid; 3-chloro-benzenecarboperoxoic acid; lithium chloride In tetrahydrofuran at 20℃; for 24h;	A typical procedure for the catalytic chlorination of electron-rich aromatic compounds: General procedure: To THF (4mL), anisole (0.3mmol, 32mg), TsOH·H2O (0.3mmol, 57.1mg), mCPBA (75%, 0.3mmol, 69mg), PhI (0.12mmol, 25mg) and LiCl (0.36mmol, 16mg) were added. The mixture was stirred at r.t. for 24h. Then H2O (10mL), sat.aq. Na2S2O3 (4mL), and sat. aq. Na2CO3 (4mL) were added. The mixture was extracted with CH2Cl2 (3×10mL) and the combined organic layer was dried over anhydried Na2SO4, filtered, and concentrated under reduced pressure. The residue was purified on silica gel plate (hexane/EtOAc=20/1) to give the yellow oil product of 4-chloroanisole 35mg (90%).
	In 1,2-dichloro-ethane	1-25 Using 2,5-dimethoxychlorobenzene and nitric acid as raw materials, 4-chloro-2,5-dimethoxynitrobenzene was synthesized through a microreactor. The selected solvent is dichloroethane, the concentration of 2,5-dimethoxychlorobenzene (chloride) is 30%, the concentration of nitric acid is 70%, the feed ratio is 1.3 equivalents, and the feed temperature is 30°C. The reaction temperature is 60°C, the reaction residence time is 60s, and the liquid holding capacity of the microreactor is 200mL, as summarized in Table 1:

Reference： [1]Syvret, Robert G.; Butt, Kathleen M.; Nguyen, Tung P.; Bulleck, Victoria L.; Rieth, Ryan D. [Journal of Organic Chemistry, 2002, vol. 67, # 13, p. 4487 - 4493]
[2]Hu, Lanping; Huang, Weichun; Wang, Yang; Wu, Zheng-Guang; Xu, Haiyan; Zhu, Guanghua; Zhu, Yueping; Zi, You [RSC Advances, 2022, vol. 12, # 12, p. 7115 - 7119]
[3]Current Patent Assignee: UNIV NANTONG - CN114292153, 2022, A Location in patent: Paragraph 0034-0037
[4]Tanemura, Kiyoshi; Suzuki, Tsuneo; Nishida, Yoko; Satsumabayashi, Koko; Horaguchi, Takaaki [Chemistry Letters, 2003, vol. 32, # 10, p. 932 - 933]
[5]Hirano; Yakabe; Monobe; Morimoto [Canadian Journal of Chemistry, 1997, vol. 75, # 12, p. 1905 - 1912]
[6]Bose, Anima; Mal, Prasenjit [Tetrahedron Letters, 2014, vol. 55, # 13, p. 2154 - 2156]
[7]Bose, Anima; Mal, Prasenjit [Tetrahedron Letters, 2015, vol. 55, # 13, p. 2154 - 2156]
[8]Granados, Albert; Jia, Zhiyu; del Olmo, Marc; Vallribera, Adelina [European Journal of Organic Chemistry, 2019, vol. 2019, # 17, p. 2812 - 2818]
[9]Yoshimura, Akira; Nguyen, Khiem C.; Nemykin, Victor N.; Zhdankin, Viktor V. [Arkivoc, 2017, vol. 2018, # 2, p. 40 - 49]
[10]Min, Zhu; Ying-Guo, Fang [Journal of Chemical Research, 2014, vol. 38, # 4, p. 197 - 199]
[11]Karade; Tiwari; Huple; Siddiqui [Journal of Chemical Research, 2006, # 6, p. 366 - 368]
[12]Barhate, Nivrutti B.; Gajare, Anil S.; Wakharkar, Radhika D.; Bedekar, Ashutosh V. [Tetrahedron Letters, 1998, vol. 39, # 35, p. 6349 - 6350]
[13]Barhate, Nivrutti B.; Gajare, Anil S.; Wakharkar, Radhika D.; Bedekar, Ashutosh V. [Tetrahedron, 1999, vol. 55, # 36, p. 11127 - 11142]
[14]Ohkubo, Kei; Fujimoto, Atsushi; Fukuzumi, Shunichi [Chemistry - An Asian Journal, 2016, vol. 11, # 7, p. 996 - 999]
[15]Current Patent Assignee: PEKING UNIVERSITY - CN112573978, 2021, A Location in patent: Paragraph 0184-0186
[16]Tamhankar; Desai; Mane; Wadgaonkar; Bedekar [Synthetic Communications, 2001, vol. 31, # 13, p. 2021 - 2027]
[17]Kajigaeshi, Shoji; Shinmasu, Youichi; Fujisaki, Shizuo; Kakinami, Takaaki [Chemistry Letters, 1989, p. 415 - 418]
[18]Wang, Tao; Rabe, Patrick; Citron, Christian A.; Dickschat, Jeroen S. [Beilstein Journal of Organic Chemistry, 2013, vol. 9, p. 2767 - 2777]
[19]Castelfranchi; Borra [Annali di Chimica, 1953, vol. 43, p. 293,294a, 295]
[20]Smith, John R. Lindsay; McKeer, Linda C. [Tetrahedron Letters, 1983, vol. 24, # 30, p. 3117 - 3120]
[21]Smith, John R. Lindsay; McKeer, Linda C.; Taylor, Jonathan M. [Journal of the Chemical Society. Perkin transactions II, 1989, p. 1529 - 1536]
[22]McCall, A. Scott; Wang, Hongwang; Desper, John M.; Kraft, Stefan [Journal of the American Chemical Society, 2011, vol. 133, # 6, p. 1832 - 1848]
[23]Li, Ting-Ting; Xu, Cui; Xiang, Chang-Bin; Yan, Jie [Chinese Chemical Letters, 2013, vol. 24, # 6, p. 535 - 538]
[24]Current Patent Assignee: LILY HOLDING CO LTD - CN111960947, 2020, A Location in patent: Paragraph 0021-0028

4
[ 102102-20-5 ]
[ 765-48-0 ]
[ 25419-06-1 ]
[ 2100-42-7 ]

Reference： [1]Journal of the Chemical Society. Perkin transactions II,1989,p. 1529 - 1536
[2]Journal of the Chemical Society. Perkin transactions II,1989,p. 1529 - 1536

5
[ 615-67-8 ]
[ 74-88-4 ]
[ 2100-42-7 ]

Reference： [1]Magnetic Resonance in Chemistry,1990,vol. 28,p. 315 - 317

6
[ 2100-42-7 ]
[ 76-05-1 ]
[ 90064-48-5 ]

Yield	Reaction Conditions	Operation in experiment
47%	With hexamethylenetetramine; In tetrahydrofuran; at 90 - 95℃; for 2.0h;	To a mixture of compound 4 (1.0 g, 5.79 mmol) and hexamethylenetetramine (893mg, 6.37 mmol) in THF, TFA (12.89 mg, 113 mmol) was added slowly. The reactionmixture was then refluxed for 2 hours. After that, the hot reaction liquid was pouredinto ice and its pH was adjusted to 7 with NaHCO3 powder. The mixture was extractedwith ethyl acetate and the organic phase was collected, washed with brine, dried overNa2SO4, and concentrated under reduced pressure to get the reaction crude. Thereaction crude was then purified with silica gel to give 543 mg compound 5 as a whitesolid in 47 % yield.

Reference： [1]Journal of Organic Chemistry,1993,vol. 58,p. 7906 - 7912
[2]Bioorganic and Medicinal Chemistry Letters,2017,vol. 27,p. 72 - 76
[3]Journal of the American Chemical Society,2008,vol. 130,p. 16786 - 16790

7
[ 102102-20-5 ]
[ 150-78-7 ]
[ 765-48-0 ]
[ 25419-06-1 ]
[ 2100-42-7 ]

Reference： [1]Journal of the Chemical Society. Perkin transactions II,1989,p. 1529 - 1536

8
[ 150-78-7 ]
[ 2100-42-7 ]
[ 25245-35-6 ]

Reference： [1]Journal of Organic Chemistry,1994,vol. 59,p. 6233 - 6244
[2]Journal of the Chemical Society. Perkin Transactions 2 (2001),1998,p. 59 - 70
[3]Journal of the Chemical Society. Perkin Transactions 2 (2001),2001,p. 1516 - 1521

9
[ 2100-42-7 ]
[ 98546-13-5 ]

Yield	Reaction Conditions	Operation in experiment
	With chlorosulfonic acid

Reference： [1]Farrar,W.V. [Journal of the Chemical Society, 1960, p. 3063 - 3069]

10
2.5-dimethoxy-benzenediazonium-⁽¹⁾-chlorozincate [ No CAS ]
[ 18113-18-3 ]
[ 2100-42-7 ]

Reference： [1]Justus Liebigs Annalen der Chemie,1947,vol. 557,p. 237,240

11
[ 2100-42-7 ]
[ 10224-66-5 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: (i) Na, benzene, (ii) /BRN= 2046890/ 2: H₂ / Pd / methanol

Reference： [1]Ehrhart,G. [Chemische Berichte, 1963, vol. 96, p. 2042 - 2046]

12
[ 2100-42-7 ]
[ 55-21-0 ]
[ 135-45-5 ]

Yield	Reaction Conditions	Operation in experiment
98%	With potassium phosphate; [(π-allyl)Pd(tBuBrettPhos)]OTf In <i>tert</i>-butyl alcohol at 110℃; for 16h; Schlenk technique; Inert atmosphere; Sealed tube;
98%	With potassium phosphate; [(π-allyl)Pd(tBuBrettPhos)]OTf In <i>tert</i>-butyl alcohol at 110℃; for 1.5h; Schlenk technique; Inert atmosphere;	6 Arylation of Benzamide with 1-Chloro-2,5-Dimethoxybenzene General procedure: A dry Schlenk tube is charged with 7.8 mg (0.015 mmol, 1.5 mol %) of [(allyl)Pd(tBuBrettPhos)]OTf, 145 mg (1.20 mmol, 1.20 equiv) of benzamide, and 297 mg (1.40 mmol, 1.40 equiv) of powdered K3PO4. The tube is evacuated and backfilled with nitrogen. This evacuation/backfill cycle is repeated two additional times. 1-Chloro-2,5-dimethoxybenzene (143 μL, 1.00 mmol, 1.00 equiv) is added followed by 2 mL of anhydrous t-BuOH. The tube is placed in a preheated (110° C.) oil bath and the contents are stirred vigorously. The tube is then sealed and aged in the oil bath for 90 min. The tube is then removed from the oil bath and the contents are allowed to cool to ambient temperature. The reaction mixture is diluted with 5 mL EtOAc and 5 mL of H2O. The organic phase is removed and the aqueous is extracted two additional times with 5 mL portions of EtOAc. The organic extracts are combined, dried (MgSO4), filtered, and concentrated in vacuo. The residue is chromatographed on silica gel with 10% EtOAc/hexanes as the eluent to give 252 mg (0.98 mmol, 98%) of the N-benzoyl-2,5-dimethoxyaniline as a light orange viscous oil.
97%	With potassium phosphate; C₄₃H₅₉NO₂PPd⁽¹⁺⁾*CH₃O₃S^(1-) In <i>tert</i>-butyl alcohol at 110℃; for 1.5h; Inert atmosphere;

94%	With potassium phosphate; t-BuBrettPhos; water; palladium diacetate In <i>tert</i>-butyl alcohol at 110℃; for 1.5h; Inert atmosphere;
94%	With potassium phosphate; C₄₄H₅₉F₃NO₅PPdS In <i>tert</i>-butyl alcohol at 110℃; for 24h; Inert atmosphere;	7 General Procedure for Arylation of Primary Amides General procedure: An oven-dried, resealable tube equipped with a magnetic stir bar and Teflon septum was charged with OTf-tBuBrettPhos precatalyst (9.1 mg, 1 mol %), K3PO4 (297 mg, 1.40 mmol, 1.40 eq), aryl halide (1.00 mmol, 1.00 eq) and amide (1.20 mmol, 1.20 eq) if they are solids. The tube was sealed and evacuated and backfilled with argon. This process was repeated three times. Then the aryl halide and amide were added if they are liquids, followed by tBuOH (2 mL). The reaction was heated at 110° C. and monitored by thin-layer chromatography or gas chromatography, observing the disappearance of aryl halide. After completion, the reaction was cooled to room temperature and diluted with ethyl acetate and water. The phases were separated and the aqueous phase was back extracted with ethyl acetate (2×5 mL). The combined organic phases were dried over sodium sulfate, concentrated via rotary evaporation and the crude product was purified by column chromatography. See FIG. 17.

Reference： [1]Deangelis; Gildner, Peter G.; Chow, Ruishan; Colacot, Thomas J. [Journal of Organic Chemistry, 2015, vol. 80, # 13, p. 6794 - 6813]
[2]Current Patent Assignee: JOHNSON MATTHEY PLC - US9777030, 2017, B2 Location in patent: Page/Page column 58; 68; 69; 74; 75; 76
[3]Bruno, Nicholas C.; Buchwald, Stephen L. [Organic Letters, 2013, vol. 15, # 11, p. 2876 - 2879]
[4]Location in patent: experimental part Fors, Brett P.; Dooleweerdt, Karin; Zeng, Qingle; Buchwald, Stephen L. [Tetrahedron, 2009, vol. 65, # 33, p. 6576 - 6583]
[5]Current Patent Assignee: MASSACHUSETTS INSTITUTE OF TECHNOLOGY - US2013/331566, 2013, A1 Location in patent: Paragraph 0058; 0300

13
[ 68470-59-7 ]
[ 2100-42-7 ]
[ 109838-85-9 ]
[ 1365546-39-9 ]

Reference： [1]Beilstein Journal of Organic Chemistry,2011,vol. 7,p. 1570 - 1576

14
[ 100-97-0 ]
[ 2100-42-7 ]
[ 90064-48-5 ]

Reference： [1]Marine Drugs,2012,vol. 10,p. 1103 - 1125
[2]Patent: WO2018/157800,2018,A1 .Location in patent: Paragraph 0420-0421

15
[ 150-78-7 ]
[ 2100-42-7 ]
[ 51560-21-5 ]
[ 25245-35-6 ]

Reference： [1]Organic Process Research and Development,2003,vol. 7,p. 98 - 100

16
[ 2100-42-7 ]
[ 608-44-6 ]
[ 20103-10-0 ]
[ 824-69-1 ]
[ 123-31-9 ]
[ 615-67-8 ]

Yield	Reaction Conditions	Operation in experiment
0.019 g; 0.048 g; 0.096 g; 0.105 g; 1.17 g	With aluminum (III) chloride; sodium chloride; In melt; at 150 - 185℃; for 0.116667h;	Substrate 7 (1.73 g, 10.0 mmol) was added to the melt of anhydrous AlCl3 (8.54 g,64.0 mmol) and NaCl (1.87 g, 32.0 mmol) with vigorous stirring at 150 C, the temperature of the mixture was increased to 180-185 C and maintained for 7 min. Then, the mixture was cooled to room temperature, and diluted with 10% aqueous HCl (60 mL) and distilled water (60 mL). The reaction products were extracted with AcOEt (5×20 mL), the combined extracts were washed with saturated aqueous NaCl (3×15 mL) and dried with Na2SO4, the solvent was evaporated at reduced pressure, the residue was subjected to chromatography on a column with SiO2. The elution with the mixture of hexane-acetone (9 : 1) gave 2,5-dichlorohydroquinone (14) (0.096 g, 29%), colorless crystals, m.p. 168-170 C, identical to commercial product (Alfa Aesar). 1H NMR (CDCl3), delta: 5.57 (br.s, 2 H, 2 OH); 7.03 (s, 2 H, H(3),H(6)). 13C NMR (CDCl3), delta: 115.0 (C(3), C(6)); 119.9 (C(2),C(5)); 145.7 (C(1), C(4)). 1H NMR (DMSOd6), delta: 6.92 (s, 2 H,H(3), H(6)); 9.75 (s, 2 H, 2 OH). 13C NMR (DMSOd6), delta: 117.0(C(3), C(6)); 118.3 (C(2), C(5)); 145.9 (C(1), C(4)). The elution with the mixture of hexane-acetone (8 : 1) gave2,6dichlorohydroquinone (15) (0.048 g, 14%), colorless crystals,m.p. 163-165 C (Ref. 42: 164 C). IR (CDCl3), nu/cm-1: 3601,3549, 2925, 2861, 1499, 1450, 1336, 1304, 1270, 1237, 1194,1175, 1039. 1H NMR (CDCl3), delta: 5.35 (br.s, 1 H, C(1) OH);5.45 (br.s, 1 H, C(4) OH); 6.81 (s, 2 H, H(3), H(5)). 13C NMR(CDCl3), delta: 115.6 (C(3), C(5)); 121.9 (C(2), C(6)); 142.8 (C(1));148.8 (C(4)). 1H NMR (DMSOd6), delta: 6.75 (s, 2 H, H(3), H(5));9.24 (br.s, 1 H, C(1) OH); 9.57 (br.s, 1 H, C(4) OH). 13C NMR(DMSOd6), delta: 115.4 (C(3), C(5)); 123.2 (C(2), C(6)); 141.7(C(1)); 150.8 (C(4)).The elution with the mixture of hexane-acetone (7 : 1) gave2,3dichlorohydroquinone (16) (0.019 g, 6%), colorless crystals,m.p. 142-144 C (Ref. 43: 144 C). 1H NMR (DMSOd6), delta:6.76 (s, 2 H, H(5), H(6)); 9.25 (s, 2 H, 2 OH). 13C NMR(DMSOd6), delta: 115.3 (C(5), C(6)); 119.0 (C(2), C(3)); 147.3(C(1), C(4)).The elution with the mixture of hexane-acetone (5 : 1) gave2chlorohydroquinone (12) (1.17 g, 81%), colorless crystals,m.p. 101-102 C, identical to commercial product (Alfa Aesar).1H NMR (DMSOd6), delta: 6.56 (dd, 1 H, H(5), J = 9.1 Hz,J = 2.8 Hz); 6.71 (d, 1 H, H(3), J = 2.8 Hz); 6.77 (d, 1 H, H(6),J = 9.1 Hz); 9.01 (br.s, 1 H, C(1) OH); 9.21 (br.s, 1 H, C(4)OH). 13C NMR (DMSOd6), delta: 114.8 (C(5)); 116.1 (C(6)); 117.3(C(3)); 119.6 (C(2)); 145.6 (C(1)); 150.3 (C(4)).The elution with the mixture of hexane-acetone (4 : 1) gavehydroquinone (13) (0.105 g, 50%), colorless crystals, m.p.170-172 C, identical to commercial product (Alfa Aesar).1H NMR (CDCl3), delta: 4.45 (br.s, 2 H, 2 OH); 6.72 (s, 4 H, H(2),H(3), H(5), H(6)). 13C NMR (CDCl3), delta: 116.1 (C(2), C(3),C(5), C(6)); 149.4 (C(1), C(4)). 1H NMR (DMSOd6), delta: 6.56(s, 4 H, H(2), H(3), H(5), H(6)); 8.56 (s, 2 H, 2 OH). 13C NMR(DMSOd6), delta: 115.7 (C(2), C(3), C(5), C(6)); 149.8 (C(1), C(4)).

Reference： [1]Russian Chemical Bulletin,2016,vol. 65,p. 993 - 1003
Izv. Akad. Nauk, Ser. Khim.,2016,p. 993 - 1003,11

17
[ 1122-17-4 ]
[ 2100-42-7 ]
[ 608-44-6 ]
[ 20103-10-0 ]
[ 32741-27-8 ]
[ 824-69-1 ]
[ 14918-69-5 ]
[ 15012-64-3 ]
[ 123-31-9 ]
[ 615-67-8 ]

Yield	Reaction Conditions	Operation in experiment
1%; 3%; 42%; 5%; 2%; 2.5%; 10%; 20%	With aluminum (III) chloride; iron(III) chloride; sodium chloride; In melt; at 150 - 185℃; for 0.166667h;	General procedure: A mixture of substrate 7 (1.38 g, 8.0 mmol) and anhydride 9 (2.67 g, 16.0 mmol) was added to the melt of anhydrous AlCl3 (8.54 g, 64.0 mmol), NaCl (1.87 g, 32.0 mmol) and anhydrous FeCl3 (1.30 g, 8.0 mmol) with vigorous stirring at 150 C, the temperature of the mixture was increased to 180-185 C and maintained for 10 min. Then, the reaction mixture was cooled to room temperature, treated with 10% aqueous HCl (60 mL), and allowed to stand for 12 h. The product formed was separated, washed with hot (55-60 C) water (10×40 mL), dried to the constant weight, and subjected to chromatography on a column with SiO2. The elution with the mixture of hexane-benzene (10 : 1) gave compound 2 (0.066 g, 2.5%), the elution with the mixture of hexane-benzene (4 : 1) gave compound 1 (0.99 g, 42%), the elution with benzene gave compound 10 (0.045 g, 2%) identical to the sample described above. The combined acidic mother liquor and washing water (460 mL) were extracted with AcOEt (6×50 mL), the combined extracts were washed with saturated aqueous NaCl (3×50 mL), and dried with Na2SO4. The solvent was evaporated at reduced pressure, the residue was subjected to chromatography on a column with SiO2. The elution with the mixture of hexane-acetone (9 : 1) gave compound 14 (0.057 g, 5%), the elution with the mixture of hexane-acetone (8 : 1) gave compound 15 (0.034 g, 3%), the elution with the mixture of hexane-acetone (7 : 1) gave compound 16 (0.011 g, 1%), the elution with the mixture of hexane-acetone (5 : 1) gave compound 12 (0.232 g, 20%), and the elution with the mixture of hexane-acetone (4 : 1) gave compound 13 (0.07 g, 10%) identical to the sample described above.

Reference： [1]Russian Chemical Bulletin,2016,vol. 65,p. 993 - 1003
Izv. Akad. Nauk, Ser. Khim.,2016,p. 993 - 1003,11

18
[ 1122-17-4 ]
[ 2100-42-7 ]
[ 32741-27-8 ]
[ 14918-69-5 ]
[ 15012-64-3 ]

Yield	Reaction Conditions	Operation in experiment
1: 54% 2: 1% 3: 7%	With aluminum (III) chloride; sodium chloride In melt at 150 - 175℃; for 0.116667h;	Cycloacylation of 2-chlorohydroquinone dimethyl ether (7). General procedure: A mixture of substrate 7 (1.38 g, 8.0 mmol) and anhydride 9 (2.67 g, 16.0 mmol) was added to the melt of anhydrous AlCl3 (8.54 g, 64.0 mmol) and NaCl (1.87 g, 32.0 mmol) with vigorous stirring at 150 °C, the temperature of the mixture was increased to the values given in Table 1 and maintained for the indicated time. Then, the reaction mixture was cooled to room temperature, diluted with 10% aqueous HCl (50 mL), and was allowed to stand for 12 h. The product formed was separated, washed with hot (55-60 °C) water (10×40 mL), dried to the constant weight, and subjected to chromatography on a column with SiO2. The elution with the mixture of hexane-benzene (10 : 1)gave 2,3,6,7tetrachloro5,8dihydroxy1,4naphthoquinone (2)(0.013-0.079 g, 0.5-3%), Rf 0.65 (benzene-hexane (4 : 1)), redneedles, m.p. 256-258 °C (Ref. 45: 258 °C). IR (CDCl3), ν/cm-1:3400-2250 (αOH), 1627 (C=O, C=C), 1568 (C=C), 1405.1H NMR (CDCl3), δ: 12.88 (s, 2 H, 2 αOH). 13C NMR (CDCl3),δ: 109.2 (C(4a), C(8a)); 139.1 (C(2), C(3), C(6), C(7)); 167.2(C(1), C(4), C(5), C(8)). MS, m/z (Irel (%)): 327/329/331/333/335 [M + 1]+ (58), 326/328/330/332/334 [M]+ (100), 292/294/296/298 [M - Cl + 1]+ (20), 291/293/295/297 [M - Cl]+ (61),257/259//261 [M - 2Cl + 1]+ (5), 256/258//260 [M - 2Cl]+ (17).The elution with the mixture of hexane-benzene (4 : 1) gave2,3,6trichloro5,8dihydroxy1,4naphthoquinone (1) (1.01-1.43 g,43-61%), Rf 0.48 (benzene-hexane (4 : 1)), red needles,m.p. 174-176 °C (Ref. 24: 174-176 °C). IR (CDCl3), ν/cm-1:3350-2200 (αOH), 1628 (C=O, C=C), 1566 (C=C), 1493,1401. 1H NMR (CDCl3), δ: 7.45 (s, 1 H, H(7)); 12.31 (s, 1 H,C(8) OH); 12.74 (s, 1 H, C(5) OH). 13C NMR (CDCl3), δ: 109.6(C(8a)); 110.8 (C(4a)); 130.6 (C(7)); 137.5 (C(6)); 141.5 (C(3));142.5 (C(2)); 159.6 (C(5)); 162.8 (C(8)); 174.4 (C(1)); 175.2(C(4)). MS, m/z (Irel (%)): 293/295/297/299 [M + 1]+ (13), 292/294/296/298 [M]+ (100), 258/260/262 [M - Cl + 1]+ (11), 257/259/261 [M - Cl]+ (14), 223/225 [M - 2Cl + 1]+ (15), 222/224[M - 2Cl]+ (18).The elution with benzene gave 2,3dichloro5,8dihydroxy1,4naphthoquinone (10) (0.124-0.207 g, 6-10%), Rf 0.30(benzene-hexane (4 : 1)), red needles, m.p. 194-196 °C (from1,4dioxane) (Ref. 10: 192 °C, Ref. 18: 198-199 °C). IR(CDCl3), ν/cm-1: 3400-2250 (αOH), 1625 (C=O, C=C), 1571(C=C), 1403. 1H NMR (CDCl3), δ: 7.33 (s, 2 H, H(6), H(7));12.34 (s, 2 H, 2 αOH). 13C NMR (CDCl3), δ: 110.4 (C(4a),C(8a)); 131.1 (C(6), (C(7)); 142.9 (C(2), (C(3)); 161.1 (C(5),(C(8)); 177.2 (C(1), (C(4)). MS, m/z (Irel (%)): 259/261/263[M + 1]+ (59), 258/260/262 [M]+ (100), 257/259/261 [M - 1]+(45), 224/226 [M - Cl + 1]+ (19), 223/225 [M - Cl]+ (22), 222/224 [M - Cl - 1]+ (17).The elution with the mixture of benzene-acetone (1 : 1)gave 2,5dichloro4,7dihydroxy3hydroxycarbonylinden1one(11) (0.024-0.065 g, 1.5-4%), Rf 0.50 (hexane-acetone (1 : 1))reddish yellow needles, m.p. >350 °C. IR (KBr), ν/cm-1: 3377(OH), 3214 (OH), 3280-2150 (COOH), 2923, 2853, 2361, 1698(C=O), 1681 (C=O), 1619 (C=C), 1572, 1438, 1385, 1302, 1288,1240, 1181, 1163, 1143, 1047, 1032, 881, 777, 743. 1H NMR(DMSOd6), δ: 6.02 (br.s, 1 H, C(4) OH); 6.95 (s, 1 H, H(6));10.77 (br.s, 1 H, C(3) COOH); 16.00 (s, 1 H, C(7) OH). 13C NMR(DMSOd6), δ: 111.3 (C(7a)); 122.7 (C(6)); 123.8 (C(3a)); 131.8(C(2)); 134.1 (C(5)); 142.8 (C(3)); 143.0 (C(4)); 151.0 (C(7));166.9 (COOH); 185.3 (C(1)). MS (EI, 15 eV), m/z (Irel (%)):275/277/279 [M + 1]+ (31), 274/276/278 [M]+ (100), 273/275/277 [M - 1]+ (26). Found (%): C, 43.76; H, 1.50; Cl, 25.53.C10H4Cl2O5. Calculated (%): C, 43.67; H, 1.47; Cl, 25.78.

Reference： [1]Novikov; Balaneva; Shestak; Anufriev, V. Ph.; Glazunov [Russian Chemical Bulletin, 2016, vol. 65, # 4, p. 993 - 1003][Izv. Akad. Nauk, Ser. Khim., 2016, # 4, p. 993 - 1003,11]

19
[ 1122-17-4 ]
[ 2100-42-7 ]
[ 32741-27-8 ]
[ 14918-69-5 ]
2,5-dichloro-4,7-dihydroxy-3-hydroxycarbonylinden-1-one [ No CAS ]
[ 15012-64-3 ]

Yield	Reaction Conditions	Operation in experiment
1: 51% 2: 2% 3: 9.5% 4: 3%	With aluminum (III) chloride; sodium chloride In melt at 150 - 195℃; for 0.0833333h;	Cycloacylation of 2-chlorohydroquinone dimethyl ether (7). General procedure: A mixture of substrate 7 (1.38 g, 8.0 mmol) and anhydride 9 (2.67 g, 16.0 mmol) was added to the melt of anhydrous AlCl3 (8.54 g, 64.0 mmol) and NaCl (1.87 g, 32.0 mmol) with vigorous stirring at 150 °C, the temperature of the mixture was increased to the values given in Table 1 and maintained for the indicated time. Then, the reaction mixture was cooled to room temperature, diluted with 10% aqueous HCl (50 mL), and was allowed to stand for 12 h. The product formed was separated, washed with hot (55-60 °C) water (10×40 mL), dried to the constant weight, and subjected to chromatography on a column with SiO2. The elution with the mixture of hexane-benzene (10 : 1)gave 2,3,6,7tetrachloro5,8dihydroxy1,4naphthoquinone (2)(0.013-0.079 g, 0.5-3%), Rf 0.65 (benzene-hexane (4 : 1)), redneedles, m.p. 256-258 °C (Ref. 45: 258 °C). IR (CDCl3), ν/cm-1:3400-2250 (αOH), 1627 (C=O, C=C), 1568 (C=C), 1405.1H NMR (CDCl3), δ: 12.88 (s, 2 H, 2 αOH). 13C NMR (CDCl3),δ: 109.2 (C(4a), C(8a)); 139.1 (C(2), C(3), C(6), C(7)); 167.2(C(1), C(4), C(5), C(8)). MS, m/z (Irel (%)): 327/329/331/333/335 [M + 1]+ (58), 326/328/330/332/334 [M]+ (100), 292/294/296/298 [M - Cl + 1]+ (20), 291/293/295/297 [M - Cl]+ (61),257/259//261 [M - 2Cl + 1]+ (5), 256/258//260 [M - 2Cl]+ (17).The elution with the mixture of hexane-benzene (4 : 1) gave2,3,6trichloro5,8dihydroxy1,4naphthoquinone (1) (1.01-1.43 g,43-61%), Rf 0.48 (benzene-hexane (4 : 1)), red needles,m.p. 174-176 °C (Ref. 24: 174-176 °C). IR (CDCl3), ν/cm-1:3350-2200 (αOH), 1628 (C=O, C=C), 1566 (C=C), 1493,1401. 1H NMR (CDCl3), δ: 7.45 (s, 1 H, H(7)); 12.31 (s, 1 H,C(8) OH); 12.74 (s, 1 H, C(5) OH). 13C NMR (CDCl3), δ: 109.6(C(8a)); 110.8 (C(4a)); 130.6 (C(7)); 137.5 (C(6)); 141.5 (C(3));142.5 (C(2)); 159.6 (C(5)); 162.8 (C(8)); 174.4 (C(1)); 175.2(C(4)). MS, m/z (Irel (%)): 293/295/297/299 [M + 1]+ (13), 292/294/296/298 [M]+ (100), 258/260/262 [M - Cl + 1]+ (11), 257/259/261 [M - Cl]+ (14), 223/225 [M - 2Cl + 1]+ (15), 222/224[M - 2Cl]+ (18).The elution with benzene gave 2,3dichloro5,8dihydroxy1,4naphthoquinone (10) (0.124-0.207 g, 6-10%), Rf 0.30(benzene-hexane (4 : 1)), red needles, m.p. 194-196 °C (from1,4dioxane) (Ref. 10: 192 °C, Ref. 18: 198-199 °C). IR(CDCl3), ν/cm-1: 3400-2250 (αOH), 1625 (C=O, C=C), 1571(C=C), 1403. 1H NMR (CDCl3), δ: 7.33 (s, 2 H, H(6), H(7));12.34 (s, 2 H, 2 αOH). 13C NMR (CDCl3), δ: 110.4 (C(4a),C(8a)); 131.1 (C(6), (C(7)); 142.9 (C(2), (C(3)); 161.1 (C(5),(C(8)); 177.2 (C(1), (C(4)). MS, m/z (Irel (%)): 259/261/263[M + 1]+ (59), 258/260/262 [M]+ (100), 257/259/261 [M - 1]+(45), 224/226 [M - Cl + 1]+ (19), 223/225 [M - Cl]+ (22), 222/224 [M - Cl - 1]+ (17).The elution with the mixture of benzene-acetone (1 : 1)gave 2,5dichloro4,7dihydroxy3hydroxycarbonylinden1one(11) (0.024-0.065 g, 1.5-4%), Rf 0.50 (hexane-acetone (1 : 1))reddish yellow needles, m.p. >350 °C. IR (KBr), ν/cm-1: 3377(OH), 3214 (OH), 3280-2150 (COOH), 2923, 2853, 2361, 1698(C=O), 1681 (C=O), 1619 (C=C), 1572, 1438, 1385, 1302, 1288,1240, 1181, 1163, 1143, 1047, 1032, 881, 777, 743. 1H NMR(DMSOd6), δ: 6.02 (br.s, 1 H, C(4) OH); 6.95 (s, 1 H, H(6));10.77 (br.s, 1 H, C(3) COOH); 16.00 (s, 1 H, C(7) OH). 13C NMR(DMSOd6), δ: 111.3 (C(7a)); 122.7 (C(6)); 123.8 (C(3a)); 131.8(C(2)); 134.1 (C(5)); 142.8 (C(3)); 143.0 (C(4)); 151.0 (C(7));166.9 (COOH); 185.3 (C(1)). MS (EI, 15 eV), m/z (Irel (%)):275/277/279 [M + 1]+ (31), 274/276/278 [M]+ (100), 273/275/277 [M - 1]+ (26). Found (%): C, 43.76; H, 1.50; Cl, 25.53.C10H4Cl2O5. Calculated (%): C, 43.67; H, 1.47; Cl, 25.78.

Reference： [1]Novikov; Balaneva; Shestak; Anufriev, V. Ph.; Glazunov [Russian Chemical Bulletin, 2016, vol. 65, # 4, p. 993 - 1003][Izv. Akad. Nauk, Ser. Khim., 2016, # 4, p. 993 - 1003,11]

20
[ 2100-42-7 ]
[ 150-78-7 ]

Yield	Reaction Conditions	Operation in experiment
82%	With boron nitride In isopropyl alcohol at 20℃; for 15h;	4 Example 4 In the reactor, 100 mg of 2,5-dimethoxychlorobenzene, 30 mg of boron-nitrogen carbon photocatalyst, and 3 ml of isopropanol were added, and the reaction was stirred at room temperature for 15 hours. After the reaction was completed, the mixture was extracted with ethyl acetate. The phase was dried, filtered, and the solvent was evaporated under reduced pressure to give a crude product, which was purified by column chromatography eluting with 50:1 of petroleum ether-ethyl acetate as solvent to obtain 65.6 mg 2,5- A white solid of methoxybenzene with a yield of 82%.

Reference： [1]Current Patent Assignee: FUZHOU UNIVERSITY - CN108440236, 2018, A Location in patent: Paragraph 0022

21
[ 21524-34-5 ]
[ 2100-42-7 ]
[ 1070663-76-1 ]

Yield	Reaction Conditions	Operation in experiment
68.6%	Stage #1: 2,4,6-triisopropyl-1-bromobenzene With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Inert atmosphere; Stage #2: 2,5-dimethoxy-4-chloro-benzene In tetrahydrofuran at -80 - -10℃; for 10h; Stage #3: With iodine In 2-methoxy-2-methylpropane at -10℃; for 6h;	5.A; 5.C Step A A fully dried 1-L four-necked flask purged with nitrogen was charged with 2,4,6-triisopropylbromobenzene (a1) (93.5 g, 330 mmol) and tetrahydrofuran (450 ml). After cooling to -78° C. under a nitrogen atmosphere, a hexane solution of 15 mass % of n-butyllithium (197.3 g, 462 mmol) was added dropwise thereto over 1 hour. The mixture was then aged at -78° C. for 1 hour, so that a liquid a was prepared. In another fully dried 300-mL four-necked flask purged with nitrogen, 1-chloro-2,5-dimethoxybenzene (a2) (22.7 g, 132 mmol) was dissolved in tetrahydrofuran (120 ml), so that a liquid b was prepared. The liquid b was continuously added to the liquid a over 1 hour, such that the internal temperature was maintained at about -80° C. (reaction temperature A). The mixture was gradually heated to a temperature of -10° C. and aged for 8 hours, so that a yellow transparent liquid was obtained. Iodine (67.0 g, 264 mmol) was dissolved in tert-butyl methyl ether (200 ml) in advance, and the tert-butyl methyl ether solution of iodine was slowly added dropwise to the liquid obtained in the step A at -10° C. Then, the mixture was stirred as it was for 6 hours. The organic layer was washed twice with 250 ml of an aqueous solution of 10 mass % of sodium hydrogen sulfite, then washed with 250 ml of pure water, and dried over anhydrous magnesium sulfate. After evaporating the solvent under reduced pressure, recrystallization was performed from a mixed solvent of acetic acid and methanol (1:1). The resulting crystals were rinsed with cold methanol and dried under reduced pressure to obtain 2-iodo-3,6-dimethoxy-2',4',6'-triisopropyl-1,1'-biphenyl (iodine intermediate) (42.3 g, 90.5 mmol, 68.6%). In the measurement by gas chromatography, the purity was 99% or more. (Identification data of Biaryl-I) Melting point: 199 to 200° C. 1H NMR (500.15 MHz, CDCl3): δ 0.99 (d, J=6.9 Hz, 6H), 1.17 (d, J=6.9 Hz, 6H), 1.31 (d, J=6.9 Hz, 6H), 2.36 (septet, J=6.9 Hz, 2H), 2.95 (septet, J=6.9 Hz, 1H), 3.65 (s, 3H), 3.89 (s, 3H), 6.80 (d, J=8.9 Hz, 1H), 6.89 (d, J=8.9 Hz, 1H), 7.04 (s, 2H); 13C NMR (125.76 MHz, CDCl3): δ 23.6, 24.0, 24.5, 30.8, 34.1, 55.5, 56.8, 96.4, 109.2, 110.0, 120.7, 135.9, 136.2, 145.7, 148.2, 152.3, 152.5.

Reference： [1]Current Patent Assignee: NIPPON CHEMICAL INDUSTRIAL CO LTD - US2022/169667, 2022, A1 Location in patent: Paragraph 0136-0138

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P337	If eye irritation persists:
P338	Remove contact lenses, if present and easy to do. Continue rinsing.
P340	Remove victim to fresh air and keep at rest in a position comfortable for breathing.
P341	If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing.
P342	If experiencing respiratory symptoms:
P350	Gently wash with plenty of soap and water.
P351	Rinse cautiously with water for several minutes.
P352	Wash with plenty of soap and water.
P353	Rinse skin with water/shower.
P360	Rinse immediately contaminated clothing and skin with plenty of water before removing clothes.
P361	Remove/Take off immediately all contaminated clothing.
P362	Take off contaminated clothing and wash before reuse.
P363	Wash contaminated clothing before reuse.
P370	In case of fire:
P371	In case of major fire and large quantities:
P372	Explosion risk in case of fire.
P373	DO NOT fight fire when fire reaches explosives.
P374	Fight fire with normal precautions from a reasonable distance.
P376	Stop leak if safe to do so. Oxidising gases (section 2.4) 1
P377	Leaking gas fire: Do not extinguish, unless leak can be stopped safely.
P378
P380	Evacuate area.
P381	Eliminate all ignition sources if safe to do so.
P390	Absorb spillage to prevent material damage.
P391	Collect spillage. Hazardous to the aquatic environment
P301 + P310	IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician.
P301 + P312	IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell.
P301 + P330 + P331	IF SWALLOWED: Rinse mouth. Do NOT induce vomiting.
P302 + P334	IF ON SKIN: Immerse in cool water/wrap in wet bandages.
P302 + P350	IF ON SKIN: Gently wash with plenty of soap and water.
P303 + P361 + P353	IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower.
P304 + P312	IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell.
P304 + P340	IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing.
P304 + P341	IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing.
P305 + P351 + P338	IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing.
P306 + P360	IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes.
P307 + P311	IF exposed: call a POISON CENTER or doctor/physician.
P308 + P313	IF exposed or concerned: Get medical advice/attention.
P309 + P311	IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician.
P332 + P313	IF SKIN irritation occurs: Get medical advice/attention.
P333 + P313	IF SKIN irritation or rash occurs: Get medical advice/attention.
P335 + P334	Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages.
P337 + P313	IF eye irritation persists: Get medical advice/attention.
P342 + P311	IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician.
P370 + P376	In case of fire: Stop leak if safe to Do so.
P370 + P378	In case of fire:
P370 + P380	In case of fire: Evacuate area.
P370 + P380 + P375	In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion.
P371 + P380 + P375	In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion.
Storage
Code	Phrase
P401
P402	Store in a dry place.
P403	Store in a well-ventilated place.
P404	Store in a closed container.
P405	Store locked up.
P406	Store in corrosive resistant/ container with a resistant inner liner.
P407	Maintain air gap between stacks/pallets.
P410	Protect from sunlight.
P411
P412	Do not expose to temperatures exceeding 50 oC/ 122 oF.
P413
P420	Store away from other materials.
P422
P402 + P404	Store in a dry place. Store in a closed container.
P403 + P233	Store in a well-ventilated place. Keep container tightly closed.
P403 + P235	Store in a well-ventilated place. Keep cool.
P410 + P403	Protect from sunlight. Store in a well-ventilated place.
P410 + P412	Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF.
P411 + P235	Keep cool.
Disposal
Code	Phrase
P501	Dispose of contents/container to ...
P502	Refer to manufacturer/supplier for information on recovery/recycling

Physical hazards
Code	Phrase
H200	Unstable explosive
H201	Explosive; mass explosion hazard
H202	Explosive; severe projection hazard
H203	Explosive; fire, blast or projection hazard
H204	Fire or projection hazard
H205	May mass explode in fire
H220	Extremely flammable gas
H221	Flammable gas
H222	Extremely flammable aerosol
H223	Flammable aerosol
H224	Extremely flammable liquid and vapour
H225	Highly flammable liquid and vapour
H226	Flammable liquid and vapour
H227	Combustible liquid
H228	Flammable solid
H229	Pressurized container: may burst if heated
H230	May react explosively even in the absence of air
H231	May react explosively even in the absence of air at elevated pressure and/or temperature
H240	Heating may cause an explosion
H241	Heating may cause a fire or explosion
H242	Heating may cause a fire
H250	Catches fire spontaneously if exposed to air
H251	Self-heating; may catch fire
H252	Self-heating in large quantities; may catch fire
H260	In contact with water releases flammable gases which may ignite spontaneously
H261	In contact with water releases flammable gas
H270	May cause or intensify fire; oxidizer
H271	May cause fire or explosion; strong oxidizer
H272	May intensify fire; oxidizer
H280	Contains gas under pressure; may explode if heated
H281	Contains refrigerated gas; may cause cryogenic burns or injury
H290	May be corrosive to metals
Health hazards
Code	Phrase
H300	Fatal if swallowed
H301	Toxic if swallowed
H302	Harmful if swallowed
H303	May be harmful if swallowed
H304	May be fatal if swallowed and enters airways
H305	May be harmful if swallowed and enters airways
H310	Fatal in contact with skin
H311	Toxic in contact with skin
H312	Harmful in contact with skin
H313	May be harmful in contact with skin
H314	Causes severe skin burns and eye damage
H315	Causes skin irritation
H316	Causes mild skin irritation
H317	May cause an allergic skin reaction
H318	Causes serious eye damage
H319	Causes serious eye irritation
H320	Causes eye irritation
H330	Fatal if inhaled
H331	Toxic if inhaled
H332	Harmful if inhaled
H333	May be harmful if inhaled
H334	May cause allergy or asthma symptoms or breathing difficulties if inhaled
H335	May cause respiratory irritation
H336	May cause drowsiness or dizziness
H340	May cause genetic defects
H341	Suspected of causing genetic defects
H350	May cause cancer
H351	Suspected of causing cancer
H360	May damage fertility or the unborn child
H361	Suspected of damaging fertility or the unborn child
H361d	Suspected of damaging the unborn child
H362	May cause harm to breast-fed children
H370	Causes damage to organs
H371	May cause damage to organs
H372	Causes damage to organs through prolonged or repeated exposure
H373	May cause damage to organs through prolonged or repeated exposure
Environmental hazards
Code	Phrase
H400	Very toxic to aquatic life
H401	Toxic to aquatic life
H402	Harmful to aquatic life
H410	Very toxic to aquatic life with long-lasting effects
H411	Toxic to aquatic life with long-lasting effects
H412	Harmful to aquatic life with long-lasting effects
H413	May cause long-lasting harmful effects to aquatic life
H420	Harms public health and the environment by destroying ozone in the upper atmosphere

[ CAS No. 2100-42-7 ] {[proInfo.proName]}

Quality Control of [ 2100-42-7 ]

Related Doc. of [ 2100-42-7 ]

Product Details of [ 2100-42-7 ]

Safety of [ 2100-42-7 ]

Application In Synthesis of [ 2100-42-7 ]

[ 2100-42-7 ] Synthesis Path-Upstream 1~4

[ 2100-42-7 ] Synthesis Path-Downstream 1~21

Precautionary Statements-General

Prevention

Response

Storage

Disposal

Physical hazards

Health hazards

Environmental hazards

Inquiry