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[ CAS No. 1093418-75-7 ]

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Product Details of [ 1093418-75-7 ]

CAS No. :	1093418-75-7	MDL No. :	MFCD16877107
Formula :	C₈H₆BrIO₂	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	N/A
M.W :	340.94 g/mol	Pubchem ID :	-
Synonyms :

Safety of [ 1093418-75-7 ]

Signal Word:	Warning	Class:	N/A
Precautionary Statements:	P261-P264-P270-P271-P280-P301+P312-P302+P352-P304+P340-P305+P351+P338-P330-P332+P313-P337+P313-P362-P403+P233-P405-P501	UN#:	N/A
Hazard Statements:	H302-H315-H319-H335	Packing Group:	N/A
GHS Pictogram:

Application In Synthesis of [ 1093418-75-7 ]

* 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 [ 1093418-75-7 ]
Downstream synthetic route of [ 1093418-75-7 ]

[ 1093418-75-7 ] Synthesis Path-Upstream 1~3

1
[ 1093418-75-7 ]
[ 1261470-87-4 ]

Reference： [1] Organic Letters, 2018, vol. 20, # 17, p. 5190 - 5193

2
[ 1093418-75-7 ]
[ 1190360-23-6 ]

Reference： [1] Patent: KR2018/14985, 2018, A,

3
[ 1093418-75-7 ]
[ 1223434-15-8 ]

Yield	Reaction Conditions	Operation in experiment
90%	at 60℃; for 2 h;	Into a 250-mE round-bottom flask, was placed methyl 4-bromo-2-iodobenzoate (5.8 g, 17.01 mmol, 1.00 equiv), NMP (60 mE), CuCN (1.82 g, 20.45 mmol, 1.20 equiv). The resulting solution was stirred for 2 hours at 60° C. in an oil bath. The resulting solution was extracted with ethyl acetate (50 mEx2) and the organic layers combined. The resulting mixture was washed with Fe504 (aq.) (50 mEx2). The mixture was dried over anhydrous sodium sulfate. The residue was applied onto a silica gel colunm with ethyl acetate/petroleum ether (1/3). This resulted in 3.68 g (90percent) of methyl 4-bromo-2-cyanobenzoate as a white solid.
2.39 g	at 60℃; for 1 h;	[0363] Preparation Example 75: Preparation of methyl 4-bromo-2-cyanobenzoate[0364][0365] To a mixture of methyl 4-bromo-2-iodobenzoate (3.52 g) described in Preparation Example 74 and coppercyanide (1.16 g) was added N-methylpyrrolidone (21 mL), and the mixture was stirred at 60°C for 1 hr. The reactionmixture was cooled, a solution of saturated aqueous ammonium chloride solution and aqueous ammonia (1:1) wasadded, and the mixture was extracted with ethyl acetate. The organic layer was washed with a solution of saturatedaqueous ammonium chloride solution and aqueous ammonia (1:1), saturated aqueous ammonium chloride solution,and saturated brine. The organic layer was dried over sodium sulfate, and the solvent was evaporated to give the titlecompound (2.39 g).MS (ESI) m/z:240(M+H)+.

Reference： [1] Patent: US2018/215731, 2018, A1, . Location in patent: Paragraph 1118; 1120
[2] Patent: EP2565182, 2013, A1, . Location in patent: Paragraph 0363; 0364; 0365

[ 1093418-75-7 ] Synthesis Path-Downstream 1~31

1
[ 619-42-1 ]
[ 1093418-75-7 ]

Yield	Reaction Conditions	Operation in experiment
60%	Stage #1: 4-methoxycarbonylphenyl bromide With cadmium(II) chloride-N,N,N',N'-tetramethylethylenediamine; 2,2,6,6-tetramethylpiperidinyl-lithium In tetrahydrofuran; hexane at 20℃; for 2h; Inert atmosphere; Stage #2: With iodine In tetrahydrofuran; hexane Inert atmosphere; regioselective reaction;
60%	Stage #1: 4-methoxycarbonylphenyl bromide With 2,2,6,6-tetramethyl-piperidine; n-butyllithium; cadmium(II) chloride-N,N,N',N'-tetramethylethylenediamine In tetrahydrofuran; hexane at 0 - 20℃; Inert atmosphere; Stage #2: With iodine In tetrahydrofuran; hexane Inert atmosphere; chemoselective reaction;

Reference： [1]L'Helgoual'ch, Jean-Martial; Bentabed-Ababsa, Ghenia; Chevallier, Floris; Yonehara, Mitsuhiro; Uchiyama, Masanobu; Derdour, Aicha; Mongin, Florence [Chemical Communications, 2008, # 42, p. 5375 - 5377]
[2]Location in patent: experimental part Snegaroff, Katia; L'Helgoual'ch, Jean-Martial; Bentabed-Ababsa, Ghenia; Nguyen, Tan Tai; Chevallier, Floris; Yonehara, Mitsuhiro; Uchiyama, Masanobu; Derdour, Aicha; Mongin, Florence [Chemistry - A European Journal, 2009, vol. 15, # 39, p. 10280 - 10290]

2
[ 917-92-0 ]
[ 1093418-75-7 ]
[ 1257834-06-2 ]
[ 1257834-09-5 ]

Yield	Reaction Conditions	Operation in experiment
	With triethylamine In tetrahydrofuran at 20℃; Inert atmosphere;	34.1 Example 34; N-{4-[3-tert-Butyl-1-(6-methyl-2-oxo-1,2-dihydro-pyridin-3-yl)-isoquinolin-6-yl]-phenyl}-methanesulfonamide (I-48); step 1-; To a solution 150a (5.93 g, 17.4 mmol), Pd(PPh3)2Cl2 (610 mg, 870 mmol), CuI (0.331 g, 1.74 mmol) and THF (178 mL) was added TEA (14.1 g, 19.4 mL, 139 mmol). The reaction mixture was degassed with Ar and then 3,3-dimethylbut-1-yne was added to the mixture. The mixture was stirred at RT overnight then diluted with ether and washed with H2O. The organic extract was washed with 2N HCl and sat. AQ. NaHCO3, dried (Na2SO4), filtered and concentrated. The crude material was purified by SiO2 chromatography eluting with an EtOAc/hexane (0 to 10% EtOAc) to afford 150b. NMR indicated the product contained 10% of starting material.

Reference： [1]Current Patent Assignee: ROCHE HOLDING AG - US2010/311760, 2010, A1 Location in patent: Page/Page column 53-54

3
[ 135484-83-2 ]
[ 1093418-75-7 ]

Yield	Reaction Conditions	Operation in experiment
94%		Methyl 2-amino-4-brombenzoate (10 g, 43.47 mmol) is suspended in sulphuric acid 20% (200 mL) and obtained solution is cooled down to 0 C. Sodium nitrite (3.60 g, 52.16 mmol), dissolved in water (40 mL), is added dropwise between 0 C.-5 C. and the reaction mixture is stirred for further 40 minutes at this temperature. Afterwards a cooled solution (ca. 0 C.) of potassium iodide (14.43 g, 86.93 mmol) in water (40 mL) is added dropwise and the reaction mixture is stirred for 1 h at 5 C. The reaction mixture is poured onto ice-water and extracted with ethyl acetate. The organic layer is washed with water, 10% aq. sodium thiosulfate solution, brine, dried over Na2SO4 and concentrated in vacuo. Yield 94%.
81%		Into a 1000-mE 3-necked round-bottom flask, was placed <strong>[135484-83-2]methyl 2-amino-4-bromobenzoate</strong> (5.0 g, 21.73 mmol, 1.00 equiv), a solution of sulfuric acid (20%) (20 mE) in water (100 mE). This was followed by the addition of a solution of NaNO2 (1.8 g, 26.09 mmol, 1.20 equiv) in water (20 mE) dropwise with stirring at 00 C., after stirred 1 hour at 00 C. To this was added a solution of iodopotassium (7.21 g, 43.43 mmol, 2.00 equiv) in water (30 mE) dropwise with stirring at 00 C. The resulting solution was stirred for 1 hour at 00 C. in a water/ice bath. The reaction was then quenched by the addition of 200 mE of water/ice. The resulting solution was extracted with ethyl acetate (100 mEx3) and the organic layers combined. The resulting mixture was washed with brine (100 mExl). The residue was applied onto a silica gel colunm with ethyl acetate/petroleum ether (1/5). This resulted in 5.97 g (81%) of methyl 4-bromo-2-iodobenzoate as light yellow oil.
7.05 g		[0360] Preparation Example 74: Preparation of methyl 4-bromo-2-iodobenzoate[0361][0362] To <strong>[135484-83-2]methyl 2-amino-4-bromobenzoate</strong> (5.75 g) was added cooled 20% sulfuric acid (75 mL), sodium nitrite (2.07g) was added by small portions under ice-cooling, and the mixture was stirred at the same temperature for 40 min. ToEP 2 565 182 A142510152025303540455055this reaction mixture was added dropwise a solution of potassium iodide (8.3 g) in water (25 mL) under cooling to 5C,20% sulfuric acid (30 mL) was added, and the mixture was stirred at 5C for 2 hr. This reaction mixture was neutralizedwith 4N aqueous sodium hydroxide solution under ice-cooling, 10% aqueous sodium sulfite solution (45 mL) and sodiumchloride were added, and the mixture was extracted with ethyl acetate. The organic layer was washed with 10% aqueoussodium sulfite solution added saturated brine and saturated brine, dried over sodium sulfate, and the solvent wasevaporated. The obtained residue was purified by column chromatography (hexane:ethyl acetate) to give the title compound(7.05 g).

Reference： [1]Patent: US2016/75704,2016,A1 .Location in patent: Paragraph 0227-0228
[2]Patent: US2018/215731,2018,A1 .Location in patent: Paragraph 1118; 1119
[3]Patent: EP2565182,2013,A1 .Location in patent: Paragraph 0360; 0361; 0362
[4]Organic Letters,2018,vol. 20,p. 5190 - 5193

4
[ 1093418-75-7 ]
copper(l) cyanide [ No CAS ]
[ 1223434-15-8 ]

Yield	Reaction Conditions	Operation in experiment
90%	In 1-methyl-pyrrolidin-2-one; at 60℃; for 2h;	Into a 250-mE round-bottom flask, was placed methyl 4-bromo-2-iodobenzoate (5.8 g, 17.01 mmol, 1.00 equiv), NMP (60 mE), CuCN (1.82 g, 20.45 mmol, 1.20 equiv). The resulting solution was stirred for 2 hours at 60 C. in an oil bath. The resulting solution was extracted with ethyl acetate (50 mEx2) and the organic layers combined. The resulting mixture was washed with Fe504 (aq.) (50 mEx2). The mixture was dried over anhydrous sodium sulfate. The residue was applied onto a silica gel colunm with ethyl acetate/petroleum ether (1/3). This resulted in 3.68 g (90%) of methyl 4-bromo-2-cyanobenzoate as a white solid.
2.39 g	In 1-methyl-pyrrolidin-2-one; at 60℃; for 1h;	[0363] Preparation Example 75: Preparation of methyl 4-bromo-2-cyanobenzoate[0364][0365] To a mixture of methyl 4-bromo-2-iodobenzoate (3.52 g) described in Preparation Example 74 and coppercyanide (1.16 g) was added N-methylpyrrolidone (21 mL), and the mixture was stirred at 60C for 1 hr. The reactionmixture was cooled, a solution of saturated aqueous ammonium chloride solution and aqueous ammonia (1:1) wasadded, and the mixture was extracted with ethyl acetate. The organic layer was washed with a solution of saturatedaqueous ammonium chloride solution and aqueous ammonia (1:1), saturated aqueous ammonium chloride solution,and saturated brine. The organic layer was dried over sodium sulfate, and the solvent was evaporated to give the titlecompound (2.39 g).MS (ESI) m/z:240(M+H)+.

Reference： [1]Patent: US2018/215731,2018,A1 .Location in patent: Paragraph 1118; 1120
[2]Patent: EP2565182,2013,A1 .Location in patent: Paragraph 0363; 0364; 0365

5
[ 1093418-75-7 ]
[ 65094-22-6 ]
[ 1369842-52-3 ]

Yield	Reaction Conditions	Operation in experiment
73%	Stage #1: diethyl (bromodifluoromethyl)phosphonate With zinc In 1,4-dioxane at 60℃; for 3h; Inert atmosphere; Stage #2: With copper(l) iodide; 1,10-Phenanthroline In 1,4-dioxane at 20℃; for 0.5h; Inert atmosphere; Stage #3: methyl 4-bromo-2-iodobenzoate In 1,4-dioxane at 60℃; for 48h; Inert atmosphere;

Reference： [1]Feng, Zhang; Chen, Fei; Zhang, Xingang [Organic Letters, 2012, vol. 14, # 7, p. 1938 - 1941]

6
[ 1093418-75-7 ]
[ 79099-07-3 ]
C₁₇H₂₀BrNO₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
74%	With isopropylmagnesium chloride/lithium chloride complex In tetrahydrofuran at -70 - 20℃; for 1.08333h;	2 Step 2: Synthesis of Intermediate I-7.2 I-7.1 (9.42 g, 27.63 mmol) and tert-butyl 4-oxopiperidine-1-carboxylate (6.24 g, 30.40 mmol) in dry THF (200 mL) is cooled down to -70° C. Isopropylmagnesium chloride-lithium chloride complex (1.3 mol/L in THF, 23.38 mL, 30.40 mmol) is added dropwise and reaction mixture is stirred for further 20 minutes at this temperature, is allowed to come to r.t. and stirred for 45 minutes. The reaction mixture is quenched with water and extracted with ethyl acetate. The organic layer is washed with brine, dried over Na2SO4 and concentrated in vacuo. The crude residue is purified by flash column chromatography (petroleum ether:EtOAc=95:5 to 40:60) to provide I-7.2. Yield 74%, m/z 326,328 [M+H-tert-Bu]+, rt 1.09 min, LC-MS Method Z011_S03.

Reference： [1]Current Patent Assignee: C.H. Boehringer Sohn AG & Co. KG - US2016/75704, 2016, A1 Location in patent: Paragraph 0229-0230

7
[ 67-56-1 ]
[ 1133123-02-0 ]
[ 1093418-75-7 ]

Yield	Reaction Conditions	Operation in experiment
95%	With sulfuric acid; In water; at 80℃; for 1.5h;	To <strong>[1133123-02-0]4-bromo-2-iodobenzoic acid</strong> (9.0 g, 27.53 mmol) in methanol (50 mL) is added concentrated sulphuric acid (10 mL) and the reaction mixture is stirred for 90 minutes at 80 C. The reaction mixture is poured onto ice water, sodium hydrogen carbonate is added until a pH value of 7 is reached and the reaction mixture is extracted with ethyl acetate. The organic layer is washed with brine, dried over MgSO4, filtered and concentrated in vacuo. Yield 95%.

Reference： [1]Patent: US2016/75704,2016,A1 .Location in patent: Paragraph 0232-0233
[2]Organic and Biomolecular Chemistry,2017,vol. 15,p. 9680 - 9684

8
[ 1093418-75-7 ]
[ 191162-39-7 ]
C₁₇H₁₂BrNO₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
82%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In ethanol; water; toluene at 80℃;	8 Preparation of Compound 105-3 Compound 21-4 5g (28.90mmol), methyl 4-bromo-2-iodo-benzoate (methyl 4-bromo-2-iodobenzoate) 10.84g (31.79mmol), Pd (pph3) 43.34g (2.89mmol), Insert the K2CO3 11.98g (86.71mmol) into toluene, H2O, by ethanol 60mL, 12mL, 12mL wasrefluxed at 80 ° C. Ethyl acetate (Ethyl acetate) and was extracted with distilled water,to remove water and to give the title compound 105-3 8.11g (82%) was purified by column chromatography.

Reference： [1]Current Patent Assignee: LT SAMBO CO LTD - KR2016/52399, 2016, A Location in patent: Paragraph 0197-0200

9
[ 1093418-75-7 ]
(1-phenyl-1H-indol-3-yl)boronic acid [ No CAS ]
C₂₂H₁₆BrNO₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
78%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In 1,4-dioxane Reflux;	1 [Synthesis of 1-1`] Round bottom flask was charged with (1-phenyl-1H-indol-3-yl) boronic acid 83.70 g, methyl 4-bromo-2-iodobenzoate 100 g of 1,4-Dioxane was dissolved in 1200 ml K2CO3 (2M) and 450 ml Pd (PPh3) 4 was put 10.2 g was stirred under reflux. Check the reaction by TLC and the reaction was terminated after addition of water. After purification the organic layer was extracted with EA and filtered under reduced pressure to give the intermediate column 1-1` 93.2 g (yield: 78%).

Reference： [1]Current Patent Assignee: DONGJIN SEMICHEM CO.,LTD. - KR2015/132020, 2015, A Location in patent: Paragraph 0069-0072

10
[ 1093418-75-7 ]
[ 1365647-82-0 ]
C₂₂H₁₄BrNO₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
67%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; tri-tert-butyl phosphine; sodium t-butanolate In toluene Reflux;	Synthesis of A1-3 6.5 g of intermediate A1-2, methyl 4-bromo-2-iodobenzoate 11.7 g,4.5 g of t-BuONa, 1.2 g of Pd2(dba) 3, (t-Bu)3P 1.5 ml were dissolved in 150 ml of toluene, and the mixture was stirred under reflux. After completion of the reaction was confirmed by TLC, the organic layer was extracted with MC,After pressure filtration, the column was purified to obtain 8.83 g (yield 67%) of Intermediate A1-3

Reference： [1]Current Patent Assignee: DONGJIN SEMICHEM CO.,LTD. - KR2015/124924, 2015, A Location in patent: Paragraph 0077; 0082; 0083

11
[ 1093418-75-7 ]
[ 108-95-2 ]
2,4-diphenoxybenzoic acid methyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With copper(l) iodide; caesium carbonate In toluene at 130℃; for 16h; Inert atmosphere;

Reference： [1]Gonzalez-Gomez, Jose C.; Ramirez, Nieves P.; Lana-Villarreal, Teresa; Bonete, Pedro [Organic and Biomolecular Chemistry, 2017, vol. 15, # 45, p. 9680 - 9684]

12
[ 1093418-75-7 ]
[ 108-95-2 ]
[ 1016313-33-9 ]

Yield	Reaction Conditions	Operation in experiment
	With copper(l) iodide; caesium carbonate In toluene at 130℃; for 16h; Inert atmosphere;

Reference： [1]Gonzalez-Gomez, Jose C.; Ramirez, Nieves P.; Lana-Villarreal, Teresa; Bonete, Pedro [Organic and Biomolecular Chemistry, 2017, vol. 15, # 45, p. 9680 - 9684]

13
[ 1093418-75-7 ]
[ 1190360-23-6 ]

Reference： [1]Patent: KR2018/14985,2018,A

14
[ 1093418-75-7 ]
[ 98-80-6 ]
[ 191103-21-6 ]

Yield	Reaction Conditions	Operation in experiment
79.4%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In 1,4-dioxane; water; toluene for 12h; Reflux;	1-1 To a 1 L round bottom flask reactor were added 4-bromo-2-iodobenzoate (31.7 g, 93 mmol)Phenylboronic acid (20 g, 164 mmol),Potassium carbonate (26.4 g, 191 mmol),Tetrakis triphenylphosphine palladium (2.2 g, 2 mmol),80 mL of water, 150 mL of toluene and 150 mL of 1,4-dioxane are added, and the mixture is refluxed and stirred for 12 hours.After completion of the reaction, the reaction product was separated, and the organic layer was concentrated under reduced pressure. The resultant product was separated by column chromatography to obtain (21.5 g, 79.4%).

Reference： [1]Current Patent Assignee: HODOGAYA CHEMICAL CO LTD - KR2018/14985, 2018, A Location in patent: Paragraph 0390-0395

15
[ 1093418-75-7 ]
(4-bromo-2-iodophenyl)methanol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With diisobutylaluminium hydride In toluene at -78℃; for 2.5h; Inert atmosphere;

Reference： [1]Tang, Hai-Jun; Zhang, Yu-Feng; Jiang, Yi-Wen; Feng, Chao [Organic Letters, 2018, vol. 20, # 17, p. 5190 - 5193]

16
[ 1093418-75-7 ]
4-bromo-1-(2,2-difluorovinyl)-2-iodobenzene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1: diisobutylaluminium hydride / toluene / 2.5 h / -78 °C / Inert atmosphere 2: silica gel; pyridinium chlorochromate / dichloromethane / 2 h / 0 - 20 °C / Inert atmosphere 3: triphenylphosphine / 1-methyl-pyrrolidin-2-one / 0.17 h / 100 °C / Inert atmosphere

Reference： [1]Tang, Hai-Jun; Zhang, Yu-Feng; Jiang, Yi-Wen; Feng, Chao [Organic Letters, 2018, vol. 20, # 17, p. 5190 - 5193]

17
[ 1093418-75-7 ]
5-bromo-2,3-diphenyl-1-(trifluoromethyl)-1H-indene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 4 steps 1: diisobutylaluminium hydride / toluene / 2.5 h / -78 °C / Inert atmosphere 2: silica gel; pyridinium chlorochromate / dichloromethane / 2 h / 0 - 20 °C / Inert atmosphere 3: triphenylphosphine / 1-methyl-pyrrolidin-2-one / 0.17 h / 100 °C / Inert atmosphere 4: dicyclohexyl-(2′,4′,6′-triisopropyl-3,6-dimethoxy-[1,1′-biphenyl]-2-yl)phosphine; silver fluoride; dichloro(1,5-cyclooctadiene)palladium(II) / 1,4-dioxane / 12 h / 80 °C / Schlenk technique; Inert atmosphere; Sealed tube

Reference： [1]Tang, Hai-Jun; Zhang, Yu-Feng; Jiang, Yi-Wen; Feng, Chao [Organic Letters, 2018, vol. 20, # 17, p. 5190 - 5193]

18
[ 1093418-75-7 ]
[ 1261470-87-4 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: diisobutylaluminium hydride / toluene / 2.5 h / -78 °C / Inert atmosphere 2: silica gel; pyridinium chlorochromate / dichloromethane / 2 h / 0 - 20 °C / Inert atmosphere

Reference： [1]Tang, Hai-Jun; Zhang, Yu-Feng; Jiang, Yi-Wen; Feng, Chao [Organic Letters, 2018, vol. 20, # 17, p. 5190 - 5193]

19
[ 96-54-8 ]
[ 1093418-75-7 ]
methyl 4-bromo-2-(1-methyl-1H-pyrrol-2-yl)benzoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
81%	With N,N,N,N,-tetramethylethylenediamine; potassium carbonate In dimethyl sulfoxide at 20℃; Inert atmosphere; Irradiation; chemoselective reaction;

Reference： [1]Lee, Da Seul; Kim, Chung Soo; Iqbal, Naila; Park, Gyeong Su; Son, Kyung-Sun; Cho, Eun Jin [Organic Letters, 2019, vol. 21, # 24, p. 9950 - 9953]

20
[ 1093418-75-7 ]
C₂₄H₂₄BO₃P [ No CAS ]
[ 75-16-1 ]
C₂₇H₂₀BrOP [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: methyl 4-bromo-2-iodobenzoate; C₂₄H₂₄BO₃P With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In tetrahydrofuran; water Stage #2: methylmagnesium bromide In tetrahydrofuran Stage #3: With hydrogenchloride; acetic acid In water	9.1; 9.2; 9.3 1) Synthesis of Intermediate 43-1 Intermediate 1-2 reacted with methyl 4-bromo-2-iodobenzoate (CAS: 1093418-75-7) and potassium carbonate under a palladium catalyst to synthesize Intermediate 43-1. Intermediate 43-1 was confirmed by LC-MS. C26H18BrO3P: M+1 489.69. 2) Synthesis of Intermediate 43-2 (0464) Intermediate 43-1 reacted with a methyl magnesium bromide solution to synthesize Intermediate 43-2. Intermediate 43-2 was confirmed by LC-MS. (0465) C27H22BrO2P: M+1 489.60. (0466) 3) Synthesis of Intermediate 43-3 (0467) Intermediate 43-2 reacted under a hydrochloric acid catalyst to synthesize Intermediate 43-3. Intermediate 43-3 was confirmed by LC-MS. (0468) C27H20BrOP: M+1 471.34.

Reference： [1]Current Patent Assignee: Samsung Display (in: Samsung); SAMSUNG ELECTRONICS CO.,LTD. - US2019/375773, 2019, A1 Location in patent: Paragraph 0460-0471

21
[ 1093418-75-7 ]
dibenzo[b,e][1,4]dioxin-1-ylboronic acid [ No CAS ]
C₂₀H₁₃BrO₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
73%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium carbonate In tetrahydrofuran; water for 10h; Heating;	1 Compounds A1 to A10 of Table 1 below were prepared using the reaction of any one of Steps 1-1 to 1-4. General procedure: As a reactant, 1eq SM1 (boronic acid derivative) and 1.05eq SM2 (halogen-substituted compound) were added to tetrahydrofuran, followed by 2M potassium carbonate aqueous solution (30 vol. Ratio to THF).Tetrakistriphenyl-phosphinopalladium (2 mol%) was added thereto, followed by heating and stirring for 10 hours. After the temperature was lowered to room temperature and the reaction was terminated, the aqueous solution of potassium carbonate was removed to separate the layers. Compounds A1 to A10 were prepared by vacuum distillation after removal of the solvent.

Reference： [1]Current Patent Assignee: LG CHEM CO.,LTD. - KR2020/9979, 2020, A Location in patent: Paragraph 0197; 0203-0204; 0206

22
[ 174627-62-4 ]
[ 1093418-75-7 ]
methyl 5-bromo-2',6'-dimethoxy-4'-(2-methyloctan-2-yl)-[1,1'-biphenyl]-2-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
62%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; caesium carbonate In 1,2-dimethoxyethane; water at 110℃; for 0.75h; Inert atmosphere; Microbiological reaction;	Methyl 2',5,6'-trimethoxy-4'-(2-methyloctan-2-yl)-[1,10-biphenyl]-2-carboxylate(15) General procedure: Argon was bubbledthrough a mixture of boronic acid 13 [27] (1.43 g, 4.65 mmol), methyl 2-bromo-4-methoxybenzoate (14, 950mg, 3.88 mmol), and Cs2CO3 (5.06 g, 15.5 mmol) in DME/H2O (5:1, 10.5 mL of DME and 2.1 mL ofH2O) for 10 min. The Pd(PPh3)4 (448 mg, 0.39 mmol) catalyst was added to the mixture while argonbubbling was maintained through the mixture, and degassing was continued for an additional 5 min.The reaction mixture was microwaved with stirring at 110 C for 45 min in a Biotage apparatus [25].Then, the mixture was cooled to room temperature and filtered through a short celite pad. Volatileswere removed under reduced pressure, and Et2O was added. The ethereal solution was washed withwater and brine, dried over MgSO4, and concentrated under reduced pressure. Purification by flashcolumn chromatography on silica gel (10-30% EtOAc/hexane) gave 15 (1.4 g, 84% yield) as a yellow oil.

Reference： [1]Liu, Yingpeng; Ho, Thanh C.; Baradwan, Mohammed; Lopez-Alberca, Maria Pascual; Iliopoulos-Tsoutsouvas, Christos; Nikas, Spyros P.; Makriyannis, Alexandros [Molecules, 2020, vol. 25, # 3]

23
[ 1093418-75-7 ]
[ 78-84-2 ]
methyl 4-bromo-2-isobutyrylbenzoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
14%	With tert.-butylhydroperoxide; palladium diacetate; silver(l) oxide In water at 120℃; for 12h; Sealed tube;	19.A Step A. Methyl 4-bromo-2-isobutyrylbenzoate To a tube charged with methyl 4-bromo-2- iodobenzoate (1420 mg, 4.2 mmol) was added isobutyraldehyde (1201 mg, 17 mmol), Pd(OAc)2(94 mg, 0.4 mmol), Ag2O (1255 mg, 5.4 mmol) and an aqueous solution (70% w/w) of tert-butyl hydroperoxide (TBHP) (2681 mg, 21 mmol). The reaction mixture was degassed with nitrogen, sealed and heated with stirring at 120 C for 12 h. The reaction was cooled to room temperature, diluted with aqueous NaHCO3solution (50 mL) and extracted with ethyl acetate (100 mLx2). The combined organic extract washed with brine (20 mL), dried over Na2SO4, filtered, and concentrated. The residue was purified by silica column chromatography (gradient elution: 10- 30% EtOAc in heptane) to give the title compound as a white solid (167 mg, yield: 14%). LCMS (ES-API): mass calcd. for C12H13BrO3, 284.0; m/z found, 285.0 [M+H]+.1H NMR (400 MHz, CDCl3) d 7.83 (d, J = 8.31 Hz, 1H), 7.62 (dd, J = 1.96, 8.31 Hz, 1H), 7.42 (d, J = 1.96 Hz, 1H), 3.88 (s, 3H), 3.02 (spt, J = 6.89 Hz, 1H), 1.21 (d, J = 6.89 Hz, 6H) ppm.

Reference： [1]Current Patent Assignee: JOHNSON & JOHNSON INC - WO2020/212897, 2020, A1 Location in patent: Page/Page column 75; 126; 127

24
dibenzo[b,d]furan-1-yl-boronic acid [ No CAS ]
[ 1093418-75-7 ]
C₂₀H₁₃BrO₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
70.3%	With 3,6-dioxa-1,8-diaminooctane; palladium diacetate; sodium carbonate; tris-(o-tolyl)phosphine In water for 15h; Inert atmosphere; Reflux;	4.1 The synthesis method of compound 1-a is as follows: S1: Under the protection of nitrogen, compound A (5g, 212.01g/mol, 23.58mmol), Compound 1-e (1.1eq, 8.84g, 340.94g/mol, 25.94mmol) and sodium carbonate (2eq, 5g, 105.99g/mol, 47.16mmol) were added to ethylene glycol diamine ether (100g, 20 of compound A times the mass) and water (100g, 20 times the mass of compound A), After stirring and mixing, add tris(o-tolyl)phosphine (0.05eq, 0.36g, 304.37g/mol, 1.18mmol) and palladium(II) acetate (0.01eq, 0.05g, 224.51g/mol, 0.24mmol) , After heating to reflux for 15h, The organic phase was separated, washed with water, dried over anhydrous magnesium sulfate, and spin-dried to obtain a crude product. After the crude product was subjected to column chromatography, compound C (6.32g, yield 70.3%) was obtained.

Reference： [1]Current Patent Assignee: NANJING TOPTO SEMICONDUCTOR MATERIAL CO LTD - CN112552270, 2021, A Location in patent: Paragraph 0071; 0076-0078

25
[ 1133123-02-0 ]
[ 74-88-4 ]
[ 1093418-75-7 ]

Yield	Reaction Conditions	Operation in experiment
80%	With caesium carbonate In N,N-dimethyl-formamide at 20℃; for 16h;	A Synthesis of methyl 4-bromo-2-iodobenzoate I-1011 Cesium carbonate [534-17-8] (5.98 g, 18.35 mmol) and methyl iodide [74-88-4] (1.14 mL, 2.28 g/mL 1 l ddd i d l i f 4b 2 iodobenzoic ac reaction mixtu organic layer was concentrated in vacuo. The crude was purified by flash column 10 chromatography (silica; EtOAc in Heptane from 0/100 to 20/80). The desired fractions were collected and concentrated in vacuo to yield methyl 4-bromo-2-iodobenzoate I- 1011 (4.27 g, 80%) as a colorless oil

Reference： [1]Current Patent Assignee: JOHNSON & JOHNSON INC - WO2021/239885, 2021, A1 Location in patent: Page/Page column 52; 79

26
[ 1093418-75-7 ]
[ 19810-31-2 ]
[ 1068-55-9 ]
methyl 2-(2-(benzyloxy)acetyl)-4-bromobenzoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
82%	Stage #1: methyl 4-bromo-2-iodobenzoate; isopropylmagnesium chloride In tetrahydrofuran at -78 - 0℃; for 0.5h; Inert atmosphere; Stage #2: With zinc dibromide In tetrahydrofuran at 0℃; for 0.25h; Inert atmosphere; Stage #3: Benzyloxyacetyl chloride With tetrakis(triphenylphosphine) palladium⁽⁰⁾ In tetrahydrofuran at 60℃; for 2h; Inert atmosphere;	A Synthesis of methyl 2-(2-(benzyloxy)acetyl)-4-bromobenzoate I-1012 Isopropylmagnes was added drop15 1.47 mmol) in T at 0C for 30 mi 8] (367 mg, 1.61 min. 2-(Benzyloxy)acetyl chloride I-1009 (325 mg, 1.76 mmol) and tetrakis(triphenylphosphine)palladium (0) [14221-01-3] (86 mg, 0.073 mmol) were 20 added and the resulting mixture was stirred at 60C for 2h under nitrogen atmosphere. The reaction mixture was diluted with sat. aqueous NH4Cl and extracted with EtOAc. The organic layer was separated, dried (MgSO4), filtered and the solvents evaporated in vacuo. The crude product was purified by flash column chromatography (silica; DCM in heptane 0/100 to 100/0). The desired fractions were collected and concentrated 25 in vacuo to yield methyl 2-(2-(benzyloxy)acetyl)-4-bromobenzoate I-1012 (468 mg, 82%) as a yellow sticky solid

Reference： [1]Current Patent Assignee: JOHNSON & JOHNSON INC - WO2021/239885, 2021, A1 Location in patent: Page/Page column 52; 80

27
[ 1093418-75-7 ]
[ 108-24-7 ]
methyl 2-acetyl-4-bromobenzoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
83.92%	Stage #1: methyl 4-bromo-2-iodobenzoate With isopropylmagnesium chloride lithium chloride In tetrahydrofuran at -78℃; for 0.5h; Stage #2: acetic anhydride In tetrahydrofuran at -78 - 20℃; for 2h;	172 A 2.0M solution of isopropylmagnesium chloride in THF (35.19 mL, 70.37 mmol) was added dropwise at -78°C to a solution of methyl 4-bromo-2-iodobenzoate (21.81 g, 63.98 mmol) in THF (221.7 mL). After 30 minutes acetic acid acetyl ester (7.86 mL, 83.17 mmol) was added at the same temperature. After addition was complete, the reaction mixture was stirred at room temperature for 2 hours then it was quenched with a saturated aqueous solution of ammonium chloride and extracted three times with EtOAc. The combined organic phases were washed with brine, filtered and evaporated in vacuo. The residue was purified by column chromatography (KP-Sil silica gel, SNAP 750) eluting with a gradient of EtOAc in cyclohexane from 5% to 25% to give methyl 2-acetyl-4-bromobenzoate (13.8 g, 53.69 mmol, 83.92% yield) as a yellowish oil.1H NMR (400 MHz, DMSO-d6) ^ 2.52 (s, 3 H), 3.81 (s, 3 H), 7.72 - 7.76 (m, 1 H), 7.82 - 7.86 (m, 1 H), 7.88 (d, J = 1.76 Hz, 1 H). LC-MS (Method A): r.t. 0.98 min, MS (ESI) m/z = 257.14 and 259.07 [M+H]+.
83.92%	Stage #1: methyl 4-bromo-2-iodobenzoate With isopropylmagnesium chloride lithium chloride In tetrahydrofuran at -78℃; for 0.5h; Stage #2: acetic anhydride In tetrahydrofuran at -78 - 20℃; for 2h;	172 A 2.0M solution of isopropylmagnesium chloride in THF (35.19 mL, 70.37 mmol) was added dropwise at -78°C to a solution of methyl 4-bromo-2-iodobenzoate (21.81 g, 63.98 mmol) in THF (221.7 mL). After 30 minutes acetic acid acetyl ester (7.86 mL, 83.17 mmol) was added at the same temperature. After addition was complete, the reaction mixture was stirred at room temperature for 2 hours then it was quenched with a saturated aqueous solution of ammonium chloride and extracted three times with EtOAc. The combined organic phases were washed with brine, filtered and evaporated in vacuo. The residue was purified by column chromatography (KP-Sil silica gel, SNAP 750) eluting with a gradient of EtOAc in cyclohexane from 5% to 25% to give methyl 2-acetyl-4-bromobenzoate (13.8 g, 53.69 mmol, 83.92% yield) as a yellowish oil.1H NMR (400 MHz, DMSO-d6) ^ 2.52 (s, 3 H), 3.81 (s, 3 H), 7.72 - 7.76 (m, 1 H), 7.82 - 7.86 (m, 1 H), 7.88 (d, J = 1.76 Hz, 1 H). LC-MS (Method A): r.t. 0.98 min, MS (ESI) m/z = 257.14 and 259.07 [M+H]+.

Reference： [1]Current Patent Assignee: ANNEXON INC - WO2022/20244, 2022, A1 Location in patent: Page/Page column 199-200
[2]Current Patent Assignee: ANNEXON INC - WO2022/20244, 2022, A1 Location in patent: Page/Page column 199-200

28
[ 1093418-75-7 ]
[ 97-72-3 ]
methyl 4-bromo-2-(2-methylpropanoyl)benzoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
95.66%	Stage #1: methyl 4-bromo-2-iodobenzoate With isopropylmagnesium chloride lithium chloride In tetrahydrofuran at -78℃; for 0.25h; Stage #2: 2-Methylpropionic anhydride In tetrahydrofuran at -78 - 20℃; for 2h;	172 To a solution of methyl 4-bromo-2-iodobenzoate (1.0 g, 2.93 mmol) in THF (10 mL) cooled to -78°C, a 2.0M solution of isopropyl magnesium chloride in THF (1.61 mL, 3.23 mmol) was added. After 15 minutes, 2-methylpropanoic acid (2-methyl-1-oxopropyl) ester (0.63 mL, 3.81 mmol) was added dropwise at the same temperature and then the reaction mixture was stirred at room temperature for 2 h. The mixture was quenched with saturated ammonium chloride solution and extracted three times with EtOAc. The combined organic phases were washed with brine, filtered and evaporated in vacuo. The residue was purified by column chromatography (KP-Sil, SNAP 50g) eluting with a gradient of EtOAc in cyclohexane from 0% to 20% to give methyl 4-bromo-2-(2-methylpropanoyl)benzoate (800 mg, 2.806 mmol, 95.66% yield) as a white solid.1H NMR (400 MHz, DMSO-d6) δ 1.08 (d, J = 6.89 Hz, 6H), 3.13 (hept, J = 6.89 Hz, 1H), 3.79 (s, 3H), 7.74 (dd, J = 1.75, 0.67 Hz, 1H), 7.80 - 7.82 (m, 2H). LC-MS (Method A): r.t.1.16 min, MS (ESI) m/z = 285.1 and 287.1 [M+H]+.
95.66%	Stage #1: methyl 4-bromo-2-iodobenzoate With isopropylmagnesium chloride lithium chloride In tetrahydrofuran at -78℃; for 0.25h; Stage #2: 2-Methylpropionic anhydride In tetrahydrofuran at -78 - 20℃; for 2h;	172 To a solution of methyl 4-bromo-2-iodobenzoate (1.0 g, 2.93 mmol) in THF (10 mL) cooled to -78°C, a 2.0M solution of isopropyl magnesium chloride in THF (1.61 mL, 3.23 mmol) was added. After 15 minutes, 2-methylpropanoic acid (2-methyl-1-oxopropyl) ester (0.63 mL, 3.81 mmol) was added dropwise at the same temperature and then the reaction mixture was stirred at room temperature for 2 h. The mixture was quenched with saturated ammonium chloride solution and extracted three times with EtOAc. The combined organic phases were washed with brine, filtered and evaporated in vacuo. The residue was purified by column chromatography (KP-Sil, SNAP 50g) eluting with a gradient of EtOAc in cyclohexane from 0% to 20% to give methyl 4-bromo-2-(2-methylpropanoyl)benzoate (800 mg, 2.806 mmol, 95.66% yield) as a white solid.1H NMR (400 MHz, DMSO-d6) δ 1.08 (d, J = 6.89 Hz, 6H), 3.13 (hept, J = 6.89 Hz, 1H), 3.79 (s, 3H), 7.74 (dd, J = 1.75, 0.67 Hz, 1H), 7.80 - 7.82 (m, 2H). LC-MS (Method A): r.t.1.16 min, MS (ESI) m/z = 285.1 and 287.1 [M+H]+.

Reference： [1]Current Patent Assignee: ANNEXON INC - WO2022/20244, 2022, A1 Location in patent: Page/Page column 212-213
[2]Current Patent Assignee: ANNEXON INC - WO2022/20244, 2022, A1 Location in patent: Page/Page column 212-213

29
[ 33993-24-7 ]
[ 1093418-75-7 ]
methyl 4-bromo-2-(cyclopropanecarbonyl)benzoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
83.39%	Stage #1: methyl 4-bromo-2-iodobenzoate With isopropylmagnesium chloride lithium chloride In tetrahydrofuran at -78℃; for 0.5h; Stage #2: cyclopropanecarbonyl cyclopropanecarboxylate In tetrahydrofuran at -78 - 20℃; for 2h;	172 To a solution of methyl 4-bromo-2-iodobenzoate (1.6 g, 4.69 mmol) in THF (16.26 mL), a 2 M solution of isopropylmagnesium chloride in THF (2.58 mL, 5.16 mmol) was added dropwise at -78°C. After 30 minutes cyclopropanecarboxylic anhydride (0.67 mL, 6.1 mmol) was added at the same temperature. After addition was complete the reaction mixture was stirred at room temperature for 2 hours. It was then quenched with a saturated solution of ammonium chloride and extracted three times with EtOAc. The combined organic phases were washed with brine, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The residue was purified by column chromatography (KP silica gel, SNAP 340) eluting with a gradient of EtOAc in cyclohexane from 2% to 40% to give methyl 4-bromo-2-(cyclopropanecarbonyl)benzoate (1.108 g, 3.914 mmol, 83.39% yield) as a yellow oil.1H NMR (400 MHz, DMSO-d6) δ 1.05 - 1.14 (m, 4H), 2.40 (tt, J = 6.7, 5.5 Hz, 1H), 3.80 (s, 3H), 7.76 (dd, J = 8.2, 0.5 Hz, 1H), 7.80 - 7.89 (m, 2H). LC-MS (Method A): r.t.1.08 min. MS (ESI) m/z of product not observed due to poor ionization
83.39%	Stage #1: methyl 4-bromo-2-iodobenzoate With isopropylmagnesium chloride lithium chloride In tetrahydrofuran at -78℃; for 0.5h; Stage #2: cyclopropanecarbonyl cyclopropanecarboxylate In tetrahydrofuran at -78 - 20℃; for 2h;	172 To a solution of methyl 4-bromo-2-iodobenzoate (1.6 g, 4.69 mmol) in THF (16.26 mL), a 2 M solution of isopropylmagnesium chloride in THF (2.58 mL, 5.16 mmol) was added dropwise at -78°C. After 30 minutes cyclopropanecarboxylic anhydride (0.67 mL, 6.1 mmol) was added at the same temperature. After addition was complete the reaction mixture was stirred at room temperature for 2 hours. It was then quenched with a saturated solution of ammonium chloride and extracted three times with EtOAc. The combined organic phases were washed with brine, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The residue was purified by column chromatography (KP silica gel, SNAP 340) eluting with a gradient of EtOAc in cyclohexane from 2% to 40% to give methyl 4-bromo-2-(cyclopropanecarbonyl)benzoate (1.108 g, 3.914 mmol, 83.39% yield) as a yellow oil.1H NMR (400 MHz, DMSO-d6) δ 1.05 - 1.14 (m, 4H), 2.40 (tt, J = 6.7, 5.5 Hz, 1H), 3.80 (s, 3H), 7.76 (dd, J = 8.2, 0.5 Hz, 1H), 7.80 - 7.89 (m, 2H). LC-MS (Method A): r.t.1.08 min. MS (ESI) m/z of product not observed due to poor ionization

Reference： [1]Current Patent Assignee: ANNEXON INC - WO2022/20244, 2022, A1 Location in patent: Page/Page column 218-219
[2]Current Patent Assignee: ANNEXON INC - WO2022/20244, 2022, A1 Location in patent: Page/Page column 218-219

30
[ 1093418-75-7 ]
[ 411235-57-9 ]
methyl 2-(6-cyclopropyl-5-fluoro-1-oxospiro[3H-isoquinoline-4,1'-cyclopropane]-2-yl)acetate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With palladium (II) [1,1'-bis(diphenylphosphanyl)ferrocene] dichloride; caesium fluoride In 1,4-dioxane at 100℃; for 6h; Inert atmosphere;	100 Methyl 2-(6-cyclopropyl-5-fluoro-1-oxo-spiro[3H-isoquinoline-4,1'-cyclopropane]-2- yl)acetate: To a solution of methyl 2-(6-bromo-5-fluoro-1-oxo-spiro[3H-isoquinoline-4,1'- cyclopropane]-2-yl)acetate (200 mg, 0.61 mmol) and cyclopropylboronic acid (151 mg, 1.75 mmol) in 1,4-dioxane (2.0 mL) were added CsF (266 mg, 1.75 mmol) and Pd(dppf)Cl2 (43 mg, 0.06 mmol). The reaction mixture was stirred at 100 °C for 6 h. The reaction mixture was diluted with water (20 mL) and extracted with EtOAc (3 × 10 mL). The combined organics were washed with brine (10 mL), dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography.1H NMR (400 MHz, CDCl3): δ 7.84 (d, J = 8.0 Hz, 1H), 6.84-6.67 (m, 1H), 4.29 (s, 2H), 3.76 (s, 3H), 3.32 (s, 2H), 2.12-2.05 (m, 1H), 1.67-1.61 (m, 2H), 1.06-0.99 (m, 2H), 0.99-0.93 (m, 2H), 0.78-0.71 (m, 2H).

Reference： [1]Current Patent Assignee: DENALI THERAPEUTICS INC - WO2022/109268, 2022, A1 Location in patent: Paragraph 0510

31
[ 1093418-75-7 ]
trifluoro(vinyl)-λ4-borane potassium salt [ No CAS ]
methyl 4-bromo-2-vinylbenzoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With palladium (II) [1,1'-bis(diphenylphosphanyl)ferrocene] dichloride; caesium fluoride In 1,4-dioxane at 90℃; for 16h; Inert atmosphere;	Methyl 4-bromo-2-vinylbenzoate To a mixture of methyl 4-bromo-2-iodo-benzoate (6.0 g, 17.6 mmol), potassium vinyltrifluoroborate (2.4 g, 17.6 mmol), and CsF (8.0 g, 52.8 mmol) in 1,4- dioxane (100 mL) was added Pd(dppf)Cl2 (1.3 g, 1.76 mmol). The reaction mixture was stirred at 90 °C for 16 h. The reaction mixture was concentrated under reduced pressure. The residue was purified by silica gel column chromatography.1H NMR (400 MHz, CDCl3): δ 7.77 (d, J = 8.4 Hz, 1H), 7.72 (d, J = 2.0 Hz, 1H), 7.49-7.37 (m, 2H), 5.66 (d, J = 17.2 Hz, 1H), 5.41 (d, J = 10.8 Hz, 1H), 3.90 (s, 3H).

Reference： [1]Current Patent Assignee: DENALI THERAPEUTICS INC - WO2022/109268, 2022, A1 Location in patent: Paragraph 0209; 0288-0289

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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

Ghs Hazard Statements

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