Name: 869114-68-1|tert-Butyl (6-bromonaphthalen-2-yl)carbamate|98%
Brand: Ambeed
SKU: A386984
Rating: 98 (40 reviews)

1
[ 869114-68-1 ]
[ 1131395-21-5 ]

Yield	Reaction Conditions	Operation in experiment
44%	Stage #1: 6-bromo-2-N-tert-butoxycarbonylaminonaphthalene With n-butyllithium In tetrahydrofuran; hexane at -70 - -50℃; for 1h; Inert atmosphere; Stage #2: With Triisopropyl borate In tetrahydrofuran; hexane at 20℃; Inert atmosphere; Stage #3: With hydrogenchloride In tetrahydrofuran; hexane; water at 20℃; for 0.333333h;	XXVI 8.73 ml n-butyllithium solution (1.6M in hexane) are added dropwise to 1.50 g tert. Butyl (6-bromo-naphthalen-2-yl)-carbamate in 15 ml anhydrous tetrahydrofuran under an argon atmosphere at -700C. The suspension is stirred for one hour at -500C, then 1.61 ml triisopropyl borate, dissolved in 10 ml anhydrous tetrahydrofuran, are added dropwise within 5 minutes. The suspension is slowly heated to ambient temperature, combined with 10 ml 1 N hydrochloric acid and stirred for 20 minutes at ambient temperature. The aqueous phase is saturated with common salt and the organic phase is separated off. The aqueous phase is extracted with ethyl acetate, and the combined organic phases are washed with saturated sodium hydrogen carbonate solution, dried on magnesium sulphate and evaporated down. The flask residue is chromatographed through a silica gel column with methylene chloride/methanol (98:2 to 95:5) as eluant. Yield: 590 mg (44 % of theory)Rf value: 0.42 (silica gel, methylene chloride/methanol = 95:5) Mass spectrum (ESI+): m/z = 288 [M+H]+

Reference： [1]Current Patent Assignee: C.H. Boehringer Sohn AG & Co. KG - WO2009/127723, 2009, A1 Location in patent: Page/Page column 138

2
[ 869114-68-1 ]
[ 73183-34-3 ]
[ 1312611-41-8 ]

Yield	Reaction Conditions	Operation in experiment
83%	With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH₂Cl₂; potassium acetate In 1,2-dichloro-ethane at 80℃; for 18h;
81%	With tetrakis(triphenylphosphine) palladium⁽⁰⁾; potassium acetate In 1,4-dioxane at 98℃; for 72h; Inert atmosphere;
58%	With potassium acetate In 1,4-dioxane at 110℃; for 8h; Inert atmosphere;	VII.VII-XV.VII-BM General Procedure VII-BMA mixture of compound VII-IB (1.5 g, 4.69 mmol), Bis(pinacolato)diborane (1.7 g, 7 mmol), Pd(PPh3)4 (265 mg, 0.234 mmol) and KOAc (3.9 g, 40.7 mmol) was dissolved in 30 mL of dioxane, the mixture was purged with nitrogen. Then the mixture was heated to reflux at 110° C. for 8 hrs under a nitrogen atmosphere. After the completion of reaction, the reaction mixture was cooled to r.t. and concentrated, the resulting residue was purified by column chromatography to afford compound VII-XVc (1 g, yield 58%).

Reference： [1]De Toledo, Ian; Grigolo, Thiago A.; Bennett, James M.; Elkins, Jonathan M.; Pilli, Ronaldo A. [Journal of Organic Chemistry, 2019, vol. 84, # 21, p. 14187 - 14201]
[2]Naumiec, Gregory R.; Cai, Lisheng; Lu, Shuiyu; Pike, Victor W. [European Journal of Organic Chemistry, 2017, vol. 2017, # 45, p. 6593 - 6603]
[3]Current Patent Assignee: BEIJING KAWIN TECHNOLOGY - US2011/152246, 2011, A1 Location in patent: Page/Page column 297

3
[ 5773-80-8 ]
[ 75-65-0 ]
[ 869114-68-1 ]

Yield	Reaction Conditions	Operation in experiment
93%	With diphenylphosphoranyl azide; triethylamine; In toluene; at 100℃; for 4h;	Diphenylphosphoryl azide (17.09 mL, 79 mmol) was added to a solution of 6- bromo-2-naphthoic acid (16.5 g, 65.7 mmol), triethylamine (18.32 mL, 131 mmol), and tert-butylalcohol (7.54 mL, 79 mmol) in toluene (225 mL) and stirred for 4 h at 100 C. The volatiles were removed by rotary evaporation and the residue taken up in EtOAc (500 mL) and washed with water and brine. A precipitate formed upon concentration which was isolated by filtration and washed with 1 : 1 Et20/Hex to give Example J.9gl (10.5 g). A second crop of less pure product was isolated upon concentration of the mother liquor (9.8 g); combined yield (93%). LC/MS (Cond. J2): RT = 3.44 min. LC/MS Anal. Calcd. for [M+Na Ci5H16BrN02: 345.02; found 345.03.
85%	With diphenyl phosphoryl azide; triethylamine; at 100℃;	Section VIIExample VII-IPreparation of Compound 201 and 202General Procedure VII-A6-Bromonaphthalene-2-carboxylic acid (VII-IA) (11 g, 44 mmol) in t-BuOH (50 mL) containing Et3N (4.86 g, 48 mmol) was treated with DPPA (13.2 g, 48 mmol) and stirred at 100 C. overnight. After cooling to r.t., the mixture was poured into water and extracted with EtOAc (100 mL×3), the organic layer was combined and washed with brine, dried over anhydrous sodium sulfate, concentrated in vacuo. The residue was purified on silica gel column chromatography, eluting by petroleum ether and ethyl acetate (7:1), to afford compound VII-IB (12 g, yield 85%).
	With diphenyl phosphoryl azide; triethylamine; at 80℃; for 16h;	Step 1 : tert-butyl-N-(6-bromo-2-naphthyl)carbamate To a cooled solution of <strong>[5773-80-8]6-bromonaphthalene-2-carboxylic acid</strong> (50 g, 0.2 mol) in t- butanol (350 ml.) triethylamine (30 g, 0.3 mol) was added slowly. Diphenylphosphoryl azide (60 g, 0.22 mol) was then added and the reaction mixture was stirred at 80C for 16 h. The mixture was allowed to cool to room temperature, then poured into saturated NaHC03 solution. The precipitate that had formed was filtered to give tert-butyl-N-(6- bromo-2-naphthyl)carbamate (65 g) which was used without further purification.

Reference： [1]Patent: WO2012/18325,2012,A1 .Location in patent: Page/Page column 155-156
[2]Patent: US2011/152246,2011,A1 .Location in patent: Page/Page column 254-255
[3]Patent: WO2015/7682,2015,A1 .Location in patent: Page/Page column 270

4
[ 869114-68-1 ]
[ 7499-66-3 ]

Yield	Reaction Conditions	Operation in experiment
66%	With hydrogenchloride; In methanol; at 20℃; for 4h;	General Procedure VII-SA flask was charged with VII-IB (5.5 g, 17.1 mmol) and HCl/MeOH (4M, 170 mL) was stirred at room temperature for 4 hrs. After the completion of reaction, the mixture was concentrated to afford 6-bromonaphthalen-2-amine (VII-Vd) (2.5 g, yield 66percent).

Reference： [1]Patent: US2011/152246,2011,A1 .Location in patent: Page/Page column 264

5
[ 869114-68-1 ]
[ 1312611-10-1 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: sodium carbonate / (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride / toluene; water / 4 h / Inert atmosphere; Reflux 2: hydrogenchloride / methanol / 2 h / 40 °C

Reference： [1]Current Patent Assignee: BEIJING KAWIN TECHNOLOGY - US2011/152246, 2011, A1

6
[ 869114-68-1 ]
[ 1312611-15-6 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: hydrogenchloride / methanol / 4 h / 20 °C 2: N-ethyl-N,N-diisopropylamine; HATU / dichloromethane / 20 °C

Reference： [1]Current Patent Assignee: BEIJING KAWIN TECHNOLOGY - US2011/152246, 2011, A1

7
[ 869114-68-1 ]
[ 1312609-13-4 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1: sodium carbonate / (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride / toluene; water / 4 h / Inert atmosphere; Reflux 2: hydrogenchloride / methanol / 2 h / 40 °C 3: N-ethyl-N,N-diisopropylamine; HATU / dichloromethane / 16 h / 20 °C

Reference： [1]Current Patent Assignee: BEIJING KAWIN TECHNOLOGY - US2011/152246, 2011, A1

8
[ 869114-68-1 ]
[ 1312611-42-9 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: potassium acetate / tetrakis(triphenylphosphine) palladium⁽⁰⁾ / 1,4-dioxane / 8 h / 110 °C / Inert atmosphere 2: trifluoroacetic acid / dichloromethane / 2 h / 20 °C

Reference： [1]Current Patent Assignee: BEIJING KAWIN TECHNOLOGY - US2011/152246, 2011, A1

9
[ 869114-68-1 ]
[ 1312611-43-0 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1: potassium acetate / tetrakis(triphenylphosphine) palladium⁽⁰⁾ / 1,4-dioxane / 8 h / 110 °C / Inert atmosphere 2: trifluoroacetic acid / dichloromethane / 2 h / 20 °C 3: N-ethyl-N,N-diisopropylamine; HATU / dichloromethane / 20 °C

Reference： [1]Current Patent Assignee: BEIJING KAWIN TECHNOLOGY - US2011/152246, 2011, A1

10
[ 869114-68-1 ]
[ 1312609-03-2 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 4 steps 1: potassium acetate / tetrakis(triphenylphosphine) palladium⁽⁰⁾ / 1,4-dioxane / 8 h / 110 °C / Inert atmosphere 2: trifluoroacetic acid / dichloromethane / 2 h / 20 °C 3: N-ethyl-N,N-diisopropylamine; HATU / dichloromethane / 20 °C 4: potassium phosphate / tetrakis(triphenylphosphine) palladium⁽⁰⁾ / toluene; water / 80 °C / Inert atmosphere

Reference： [1]Current Patent Assignee: BEIJING KAWIN TECHNOLOGY - US2011/152246, 2011, A1

11
[ 869114-68-1 ]
[ 1312611-05-4 ]
[ 1312611-06-5 ]

Yield	Reaction Conditions	Operation in experiment
56%	With sodium carbonate In water; toluene for 4h; Inert atmosphere; Reflux;	VII.VII-I.VII-C General Procedure VII-CTo a solution of compound VII-ID (240 mg, 0.61 mmol) in toluene (8 mL) was added aq. Na2CO3 (2 M, 1.53 mL), compound VII-IB (195 mg, 0.61 mmol), and Pd(dppf)Cl2 (27 mg, 0.03 mmol). The flask was purged with nitrogen and the mixture was heated at reflux for 4 hrs. The reaction was monitored by LCMS. Then the mixture was cooled to r.t. and extracted with EtOAc (100 mL×2), and washed with brine, the organic layer was dried over anhydrous Na2SO4, and concentrated in vacuo. The residue was purified by prep-TLC (EtOAc as eluent) to give compound VII-IE (200 mg, yield 56%). MS (ESI) m/z (M+H)+ 589.

Reference： [1]Current Patent Assignee: BEIJING KAWIN TECHNOLOGY - US2011/152246, 2011, A1 Location in patent: Page/Page column 255-256

12
[ 869114-68-1 ]
[ 1312611-05-4 ]
[ 1312611-07-6 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: sodium carbonate / (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride / toluene; water / 4 h / Inert atmosphere; Reflux 2: hydrogenchloride / methanol / 2 h / 50 °C

Reference： [1]Current Patent Assignee: BEIJING KAWIN TECHNOLOGY - US2011/152246, 2011, A1

13
[ 869114-68-1 ]
[ 1312611-08-7 ]
[ 1312611-09-8 ]

Yield	Reaction Conditions	Operation in experiment
42%	With sodium carbonate In water; toluene for 4h; Inert atmosphere; Reflux;	VII.VII-II.VII-H General Procedure VII-HA flask was charged with compound (400 mg, 1.136 mmol), compound VII-IB (366 mg 1.136 mmol), Pd(dppf)Cl2 (50 mg, 0.068 mmol) and aq. Na2CO3 (2 M, 2.8 mL, 5.68 mmol), toluene (10 mL). The flask was purged with nitrogen, after that, the mixture was heated under reflux for 4 hours. LCMS showed the reaction was completed. The mixture was cooled to r.t., extracted with EtOAc (50 mL×3), the combined extracts was dried over sodium sulfate, filtered and concentrated in vacuo to give the crude product. It was purified by prep-TLC to give compound VII-IIB as white solid. (260 mg, yield 42%).

Reference： [1]Current Patent Assignee: BEIJING KAWIN TECHNOLOGY - US2011/152246, 2011, A1 Location in patent: Page/Page column 258

14
[ 869114-68-1 ]
6-bromo-naphthalene-1,2-diamine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: nitric acid; acetic acid / 2.33 h 2: tin(II) chloride dihdyrate / methanol / 18 h / 70 °C
	Multi-step reaction with 2 steps 1: acetic acid; nitric acid 2: tin(II) chloride dihdyrate / methanol / 16 h / Reflux

Reference： [1]Current Patent Assignee: BRISTOL-MYERS SQUIBB CO - WO2012/18325, 2012, A1
[2]Current Patent Assignee: BASF SE - WO2015/7682, 2015, A1

15
[ 869114-68-1 ]
[ 1241377-72-9 ]

Yield	Reaction Conditions	Operation in experiment
100%	With nitric acid; acetic acid for 2.33333h;	J.9g2 Example J.9gl (5 g, 15.52 mmol) was diluted in acetic acid (50 mL) and fuming nitric acid (2.3 mL) was added dropwise over 20 min. The reaction was stirred for 2 h and the product, isolated by filtration, was partitioned between CH2C12 and sat'd aHC03 soln. The organic layer was concentrated to provide tert-butyl 6- bromo-l-nitronaphthalen-2-ylcarbamate 5.7 g (quant). LC/MS (Cond. J2): RT = 3.52 min. LC/MS Anal. Calcd. for [M+Na]+ Ci5H15BrN204: 390.02.; found 390.99.
	With nitric acid; acetic acid	11.2 Step 2: tert-butyl N-(6-bromo-1 -nitro-2-naphthyl)carbamate Step 2: tert-butyl N-(6-bromo-1 -nitro-2-naphthyl)carbamate To a cooled solution of the product of step 1 (65 g, 0.2 mol) in acetic acid (500 ml_), fuming nitric acid (40 ml.) was added slowly. The reaction mixture immediately turned to a dark red and a red precipitate formed within a few minutes. The mixture was then poured onto ice water. The precipitate was filtered and washed with water and oven- dried to give tert-butyl N-(6-bromo-1 -nitro-2-naphthyl)carbamate (102 g) which was used without further purification.

Reference： [1]Current Patent Assignee: BRISTOL-MYERS SQUIBB CO - WO2012/18325, 2012, A1 Location in patent: Page/Page column 156
[2]Current Patent Assignee: BASF SE - WO2015/7682, 2015, A1 Location in patent: Page/Page column 270

16
[ 869114-68-1 ]
[ 1241377-70-7 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1.1: nitric acid; acetic acid / 2.33 h 2.1: tin(II) chloride dihdyrate / methanol / 18 h / 70 °C 3.1: N-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline / dichloromethane / 6 h 3.2: 18 h / 60 °C

Reference： [1]Current Patent Assignee: BRISTOL-MYERS SQUIBB CO - WO2012/18325, 2012, A1

17
[ 869114-68-1 ]
3-[4-(trifluoromethoxy)phenyl]-7-vinylbenzo[e]benzimidazole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 5 steps 1: acetic acid; nitric acid 2: tin(II) chloride dihdyrate / methanol / 16 h / Reflux 3: 3 h / 80 °C 4: caesium carbonate / N,N-dimethyl-formamide / 16 h / 160 °C 5: (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride / toluene / 16 h / 100 °C
	Multi-step reaction with 5 steps 1: acetic acid; nitric acid 2: tin(II) chloride dihdyrate / methanol / 16 h / Reflux 3: 3 h / 80 °C 4: triethylamine; copper diacetate / pyridine; tetrahydrofuran / 24 h / 55 °C 5: (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride / toluene / 16 h / 100 °C