10323-39-4|4-Bromo-2-tert-butylphenol| Ambeed

Structure of 4-Bromo-2-tert-butylphenol
CAS No.: 10323-39-4

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Quality Control of [ 10323-39-4 ] Purity: 95% SDS Specification

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Product Details of [ 10323-39-4 ]

CAS No. :	10323-39-4
Formula :	C₁₀H₁₃BrO
M.W :	229.11
SMILES Code :	OC1=CC=C(Br)C=C1C(C)(C)C
MDL No. :	MFCD00192645
InChI Key :	IKMJSWBFODAWTC-UHFFFAOYSA-N
Pubchem ID :	97068

Safety of [ 10323-39-4 ]

GHS Pictogram:
Signal Word:	Warning
Hazard Statements:	H302+H312+H332-H315-H319
Precautionary Statements:	P261-P264-P270-P271-P280-P301+P312+P330-P302+P352+P312+P362+P364-P304+P340+P312-P305+P351+P338+P337+P313-P501

Computational Chemistry of [ 10323-39-4 ] Show Less

Physicochemical Properties

Num. heavy atoms	12
Num. arom. heavy atoms	6
Fraction Csp3	0.4
Num. rotatable bonds	1
Num. H-bond acceptors	1.0
Num. H-bond donors	1.0
Molar Refractivity	55.43
TPSA ? Topological Polar Surface Area: Calculated from Ertl P. et al. 2000 J. Med. Chem.	20.23 Å²

Lipophilicity

Log P_o/w (iLOGP)? iLOGP: in-house physics-based method implemented from Daina A et al. 2014 J. Chem. Inf. Model.	2.64
Log P_o/w (XLOGP3)? XLOGP3: Atomistic and knowledge-based method calculated by XLOGP program, version 3.2.2, courtesy of CCBG, Shanghai Institute of Organic Chemistry	3.87
Log P_o/w (WLOGP)? WLOGP: Atomistic method implemented from Wildman SA and Crippen GM. 1999 J. Chem. Inf. Model.	3.45
Log P_o/w (MLOGP)? MLOGP: Topological method implemented from Moriguchi I. et al. 1992 Chem. Pharm. Bull. Moriguchi I. et al. 1994 Chem. Pharm. Bull. Lipinski PA. et al. 2001 Adv. Drug. Deliv. Rev.	3.46
Log P_o/w (SILICOS-IT)? SILICOS-IT: Hybrid fragmental/topological method calculated by FILTER-IT program, version 1.0.2, courtesy of SILICOS-IT, http://www.silicos-it.com	3.17
Consensus Log P_o/w? Consensus Log P_o/w: Average of all five predictions	3.32

Water Solubility

Log S (ESOL):? ESOL: Topological method implemented from Delaney JS. 2004 J. Chem. Inf. Model.	-4.0
Solubility	0.0228 mg/ml ; 0.0000994 mol/l
Class? Solubility class: Log S scale Insoluble < -10 < Poorly < -6 < Moderately < -4 < Soluble < -2 Very < 0 < Highly	Moderately soluble
Log S (Ali)? Ali: Topological method implemented from Ali J. et al. 2012 J. Chem. Inf. Model.	-3.99
Solubility	0.0233 mg/ml ; 0.000102 mol/l
Class? Solubility class: Log S scale Insoluble < -10 < Poorly < -6 < Moderately < -4 < Soluble < -2 Very < 0 < Highly	Soluble
Log S (SILICOS-IT)? SILICOS-IT: Fragmental method calculated by FILTER-IT program, version 1.0.2, courtesy of SILICOS-IT, http://www.silicos-it.com	-3.89
Solubility	0.0294 mg/ml ; 0.000128 mol/l
Class? Solubility class: Log S scale Insoluble < -10 < Poorly < -6 < Moderately < -4 < Soluble < -2 Very < 0 < Highly	Soluble

Pharmacokinetics

GI absorption? Gatrointestinal absorption: according to the white of the BOILED-Egg	High
BBB permeant? BBB permeation: according to the yolk of the BOILED-Egg	Yes
P-gp substrate? P-glycoprotein substrate: SVM model built on 1033 molecules (training set) and tested on 415 molecules (test set) 10-fold CV: ACC=0.72 / AUC=0.77 External: ACC=0.88 / AUC=0.94	No
CYP1A2 inhibitor? Cytochrome P450 1A2 inhibitor: SVM model built on 9145 molecules (training set) and tested on 3000 molecules (test set) 10-fold CV: ACC=0.83 / AUC=0.90 External: ACC=0.84 / AUC=0.91	Yes
CYP2C19 inhibitor? Cytochrome P450 2C19 inhibitor: SVM model built on 9272 molecules (training set) and tested on 3000 molecules (test set) 10-fold CV: ACC=0.80 / AUC=0.86 External: ACC=0.80 / AUC=0.87	No
CYP2C9 inhibitor? Cytochrome P450 2C9 inhibitor: SVM model built on 5940 molecules (training set) and tested on 2075 molecules (test set) 10-fold CV: ACC=0.78 / AUC=0.85 External: ACC=0.71 / AUC=0.81	No
CYP2D6 inhibitor? Cytochrome P450 2D6 inhibitor: SVM model built on 3664 molecules (training set) and tested on 1068 molecules (test set) 10-fold CV: ACC=0.79 / AUC=0.85 External: ACC=0.81 / AUC=0.87	Yes
CYP3A4 inhibitor? Cytochrome P450 3A4 inhibitor: SVM model built on 7518 molecules (training set) and tested on 2579 molecules (test set) 10-fold CV: ACC=0.77 / AUC=0.85 External: ACC=0.78 / AUC=0.86	No
Log Kp (skin permeation)? Skin permeation: QSPR model implemented from Potts RO and Guy RH. 1992 Pharm. Res.	-4.95 cm/s

Druglikeness

Lipinski? Lipinski (Pfizer) filter: implemented from Lipinski CA. et al. 2001 Adv. Drug Deliv. Rev. MW ≤ 500 MLOGP ≤ 4.15 N or O ≤ 10 NH or OH ≤ 5	0.0
Ghose? Ghose filter: implemented from Ghose AK. et al. 1999 J. Comb. Chem. 160 ≤ MW ≤ 480 -0.4 ≤ WLOGP ≤ 5.6 40 ≤ MR ≤ 130 20 ≤ atoms ≤ 70	None
Veber? Veber (GSK) filter: implemented from Veber DF. et al. 2002 J. Med. Chem. Rotatable bonds ≤ 10 TPSA ≤ 140	0.0
Egan? Egan (Pharmacia) filter: implemented from Egan WJ. et al. 2000 J. Med. Chem. WLOGP ≤ 5.88 TPSA ≤ 131.6	0.0
Muegge? Muegge (Bayer) filter: implemented from Muegge I. et al. 2001 J. Med. Chem. 200 ≤ MW ≤ 600 -2 ≤ XLOGP ≤ 5 TPSA ≤ 150 Num. rings ≤ 7 Num. carbon > 4 Num. heteroatoms > 1 Num. rotatable bonds ≤ 15 H-bond acc. ≤ 10 H-bond don. ≤ 5	1.0
Bioavailability Score? Abbott Bioavailability Score: Probability of F > 10% in rat implemented from Martin YC. 2005 J. Med. Chem.	0.55

Medicinal Chemistry

PAINS? Pan Assay Interference Structures: implemented from Baell JB. & Holloway GA. 2010 J. Med. Chem.	0.0 alert
Brenk? Structural Alert: implemented from Brenk R. et al. 2008 ChemMedChem	0.0 alert: heavy_metal
Leadlikeness? Leadlikeness: implemented from Teague SJ. 1999 Angew. Chem. Int. Ed. 250 ≤ MW ≤ 350 XLOGP ≤ 3.5 Num. rotatable bonds ≤ 7	No; 1 violation:MW<2.0
Synthetic accessibility? Synthetic accessibility score: from 1 (very easy) to 10 (very difficult) based on 1024 fragmental contributions (FP2) modulated by size and complexity penaties, trained on 12'782'590 molecules and tested on 40 external molecules (r² = 0.94)	1.47

Application In Synthesis of [ 10323-39-4 ]

* 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.

Downstream synthetic route of [ 10323-39-4 ]

[ 10323-39-4 ] Synthesis Path-Downstream 1~35

1
[ 106-41-2 ]
[ 1139-52-2 ]
[ 10323-39-4 ]

References: [1]Journal of the American Chemical Society,1951,vol. 73,p. 3179,3181.
[2]Journal of the American Chemical Society,1951,vol. 73,p. 3179,3181.

2
[ 106-41-2 ]
[ 115-11-7 ]
[ 10323-39-4 ]

Yield	Reaction Conditions	Operation in experiment
90%	Dowex 50WX8 sulphonic acid; at 80℃; for 30h;	(a) 2-tert-butyl-4-bromophenol 80.00 g (426.0 mmol) of 4-bromophenol and 8.00 g of Dowex 50WX8 sulphonic acid resin are mixed in a 250 ml three-necked flask.. The mixture is heated to 80 C. and a stream of isobutylene is passed through for 30 hours.. The reaction mixture is cooled and the residue is purified by passing through a silica column eluted with a mixture composed of 95% dichloromethane and of 5% heptane. 88.00 g (90%) of the expected compound are collected in the form of a yellow oil. 1H NMR (CDCl3) delta1.38 (s, 9H), 4.79 (s, 1H), 6.55 (d, 1H, J=8.4 Hz), 7.16 (dd, 1H, J=8.4/2.4 Hz), 7.35 (d, 1H, J=2.4 Hz).
	In n-heptane; dichloromethane;	(a) 2-tert-butyl-4-bromophenol 80.00 g (426.0 mmol) of 4-bromophenol and 8.00 g of Dowex 50WX8 sulphonic acid resin are mixed in a 250 ml three-necked flask. The mixture is heated to 80 C. and a stream of isobutylene is passed through for 30 hours. The reaction mixture is cooled and the residue is purified by passing through a silica column eluted with a mixture composed of 95% dichloromethane and of 5% heptane. 88.00 g (90%) of the expected compound are collected in the form of a yellow oil. 1 H NMR (CDCl3) delta 1.38 (s, 9H), 4.79 (s, 1H), 6.55 (d, 1H, J=8.4 Hz), 7.16 (dd, 1H, J=8.4/2.4 Hz), 7.35 (d, 1H, J=2.4 Hz).

References: [1]Patent: US6346546,2002,B1 .Location in patent: Page column 29.
[2]Journal of Medicinal Chemistry,1995,vol. 38,p. 4993 - 5006.
[3]Journal of the American Chemical Society,1949,vol. 71,p. 1966.
[4]Patent: US6103762,2000,A .

3
[ 88-18-6 ]
[ 10323-39-4 ]

Yield	Reaction Conditions	Operation in experiment
98%	With tetra-N-butylammonium tribromide; In dichloromethane; at 23℃; for 2h;	General procedure: A solution of NBu4Br3 (1.0 eq) in CH2Cl2 (~5 mL per mmol NBu4Br3) was added immediately to a solution of a phenole 1 (1.0 eq) in CH2Cl2 (~ 5 mL per mmol 1). The reaction mixture was stirred at 23 C for 2 h. The solvent was removed under reduced pressure (12 mbar, 40 C). Water (5.0 mL) was added to the residue and the aqueous layer was extracted with Et2O (3 * 10 mL). The organic layer was separated and dried (MgSO4). The organic solvent was removed under reduced pressure (14 mbar, 40 C) to leave an oily residue, which was purified by adsorption chromatography (SiO2, CH2Cl2).
95%	With tetrabutyl ammonium tribromide; In dichloromethane; at 0 - 20℃; for 2h;	Step 1 4-Bromo-2-(tert-butyl)phenol (9a) To a stirred mixture of 2-(tert-butyl)phenol (20 g, 133 mmol) in anhydrous DCM (200 mL) was added tetrabutyl ammonium tribromide (64.3 g, 133 mmol) at 0C and the solution was stirred at rt for 2 h. The mixture was concentrated under reduced pressure and the residue was taken up in Et2O. The solution was washed by brine three times, dried over Na2SO4, filtered and concentrated under reduced pressure to give compound 9a (36.6 g, 95%) as an oil.
95%	With tetra-N-butylammonium tribromide; In dichloromethane; at 0 - 20℃; for 2h;	Preparative Example P9Step 1 : 4-Bromo-2-(tert-butyl)phenol (P9a)To a stirred mixture of 2-(fert-butyl)phenol (20 g, 133 mmol) in dry DCM (200 mL) was added tetrabutyl ammonium tribromide (64.3 g, 133 mmol) at 0C and the solution was stirred at rt for 2 h, concentrated and redissolved in Et20, washed by brine (3 x), dried over Na2S0 , filtered and concentrated to give compound P9a (36.6 g, 95%) as an oil.

90%	With bromine; In carbon disulfide; at 0℃; for 14h;	2-tert-Butylphenol (40 g, 266 mmol) was dissolved in carbon disulfide (50 mL), and bromine (42.6 g, 266 mmol) was slowly added thereto over 2 hours using a dropping funnel while stirring at 0 C. After allowing the reaction to proceed for 12 hours, the solvent was removed using a rotary vacuum evaporator. The residue was distilled under a reduced pressure at 65-68 C to obtain Compound 1 (yield: 90%).
89%	With tetra-N-butylammonium tribromide; In chloroform; at 20℃; for 1h;	2-tert-Butyl-phenol (5 g, 0.033 mol) was dissolved in CHCI3 (100 mL) and magnetically stirred at room temperature. To this solution was added a solution of Tetrabutyl ammonium tribromide (16.05 g, 0.033 mol) in CHC13 (100ML). The resulting yellow solution was allowed to stir at room temperature for 1 hour. The reaction was quenched with a 5% solution of sodium thiosulfate (200 mL). The biphasic mixture was stirred for 15 min. The organics were separated and concentrated. The residue was dissolved in EtOAc (100 mL) and washed with water (2 x 100 mL) and brine (1 x 100ML). The organics were dried over Na2SO4, filtered and concentrated. The residue was purified by flash chromatography (silica gel) eluting with 3% EtOAc in Hexanes. The result was a clear oil (6.8 g, 89%) 'H NMR (CDCl3) : 51. 39 (s, 9H), 4.95 (s, 1H), 6.59 (d, J= 8.5 Hz 1H), 7.19 (d, J= 8. 5 Hz, 1H), 7.24 (s, 1H).
89%	With tetra-N-butylammonium tribromide; In chloroform; at 20℃; for 1h;	2-tert-Butyl-phenol (5 g, 0.033 mol) was dissolved in CHCl3 (100 mL) and magnetically stirred at room temperature. To this solution was added a solution of Tetrabutyl ammonium tribromide (16.05 g, 0.033 mol) in CHCl3 (100 mL). The resulting yellow solution was allowed to stir at room temperature for 1 hour. The reaction was quenched with a 5% solution of sodium thiosulfate (200 mL). The biphasic mixture was stirred for 15 min. The organics were separated and concentrated. The residue was dissolved in EtOAc (100 mL) and washed with water (2×100 mL) and brine (1×100 mL). The organics were dried over Na2SO4, filtered and concentrated. The residue was purified by flash chromatography (silica gel) eluting with 3% EtOAc in Hexanes. The result was a clear oil (6.8 g, 89%). 1H NMR (CDCl3): delta 1.39 (s, 9H), 4.95 (s, 1H), 6.59 (d, J=8.5 Hz 1H), 7.19 (d, J=8.5 Hz, 1H), 7.24 (s, 1H).
89%	With tetrabutylammomium bromide; In chloroform; at 20℃; for 2h;	Step 1 : 4-Bromo-2-(ferf-butvnphenol (P7a) To a solution of 2-(rerf-butyl)phenol (30.0 g, 200 mmol) in CHCI3 (600 mL) was added tetra- n-butyl ammonium tribromide (121 g, 250 mmol) and the solution was stirred for 2 h at rt, concentrated and the crude product was partitioned between Et20 and water. The organic layer was washed sequentially with 1 M HCI twice and brine twice. The organic layer was separated and dried over MgS04, concentrated and purified by CC (PE/EA = 7/1) to give compound P7a (39.9 g, 89%) as a colorless solid.
88%	With tetrabutylamonium tribromide; In methanol; dichloromethane; for 1h;Product distribution / selectivity;	Example 47 (2S)-1-F (5R)-5-((4-CARBOXNZ-2-TERT-BUTYLPHENOXY)-METHYL)-L-PROLYL}-PYRROLIDINE-2- carbonitrile Example 47A 4-Bromo-2-tert-butyl-phenol 2-tert-Butylphenol (2.03 g, 13.51 mmol) was dissolved in the mixture of 60 mL OF CHACIA and 40 ML OF MEOH, then tetrabutylamonium tribromide (7.82 g, 16.22 mmol) was added. After one hour, the mixture was concentrated in vacuo and the residue was taken up in ether. The ether solution was washed with IN HCl (2X) and brine (1X), then dried with NaS04. The solution was then concentrated in vacuo and the residue was purified by silica gel chromatography (10% ETOAC/HEXANE) to give the titled bromophenol (2.72 g, 88%). MS (ESI) m/z-227 (M+H)-.
88%	With tetra-N-butylammonium tribromide; In methanol; dichloromethane; for 1h;	EXAMPLE 47A 4-Bromo-2-tert-butyl-phenol 2-tert-Butylphenol (2.03 g, 13.51 mmol) was dissolved in the mixture of 60 mL of CH2Cl2 and 40 mL of MeOH, then tetrabutylamonium tribromide (7.82 g, 16.22 mmol) was added. After one hour, the mixture was concentrated in vacuo and the residue was taken up in ether. The ether solution was washed with 1N HCl (2) and brine (1), then dried with NaSO4. The solution was then concentrated in vacuo and the residue was purified by silica gel chromatography (10% EtOAc/Hexane) to give the titled bromophenolbromophenol (2.72 g, 88%). MS (ESI) m/z -227 (M+H)-.
88%	With tetra-N-butylammonium tribromide; In chloroform; for 0.0833333h;	4-hrorno-2-tert-hutylphenol was prepared according to a procedure described by Berthelot and al. (Can. J. Chem, 1989, 67, 2061-2066). To a solution of 2-tert-butyiphenol (154 mL, immol, 1 eq.) in chloroform (5 rnL) was added a solution of TBABr3 (482 rng, I rnrnol, leq.) in chloroform (5rnL). The orange solution became colorless within 5 minutes. A solution of 5% sodium thiosulfate was added (15 mU. The organic layer is extracted with chloroform (2x2,0 mL), washed with water until pH=7, and evaporated. The crude oil is then diluted in diethyl ether (50 rnL) and washed with water again (2x20 rnL). The organic layer is then dried over Ca2SO4 and concentrated to dryness to afford a yellow solid (201 rng, 88%), nip= 101C. No further purification is needed. ?H NMR (400 MHz, CHLOT{OFORM-d) 8 ppm i.38(s,9 H), 4.96 (s, 1 H), 6.58 (d, J=8.37 Hz, I H), 7.15 tdd, J=8.37, 2.41 Hz. I H), 7.34 (d, ,J::241 Hz, I 1-i).
82%	With tetra-N-butylammonium tribromide; In methanol; dichloromethane; at 20℃; for 1h;	Example 63-(7-tert-Butyl-3-oxo-2,3-dihydro-benzofuran-5-yl)-1H-pyridin-2-one (I-1) step 1-To a solution of 30a (4.20 mL, 27.34 mmol) in MeOH (80 mL) and DCM (120 mL) was added tetrabutylammonium tribromide (15.66 g, 32.48 mmol). After stirring for 1 h at RT, the reaction was concentrated. The residue was diluted with Et2O. The organic layer was washed sequentially with 1N aq. HCl solution, brine, dried (Na2SO4), filtered and concentrated. The crude residue was purified by SiO2 chromatography eluting with an EtOAc/hexane gradient (5 to 10% EtOAc) to afford 5.13 g (82%) of 30b as a pale yellow oil.
	With N-Bromosuccinimide; In acetonitrile; at 0 - 20℃; for 4h;	N-bromosuccinimide (580 g) was gradually added to a solution of 2-(tert-butyl)phenol (489 g) in acetonitrile (4000 ml) while cooling on ice. After stirring for 4 hours at below 20C, ether (3000 ml) was added and the reaction mixture was washed twice with water. The organic layer was dried over anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure to yield a crude product of the title compound (746 g) as a light yellow oil.1H-NMR(CDCl3)delta(ppm) 1.20(9H,s), 6.55(1H,d,J=8.4Hz), 7.15(1H,dd,J=8.4Hz,2.0Hz), 7.34(1H,d,J=2.0Hz)
	With N-Bromosuccinimide; In acetonitrile; at 20℃; for 16h;	To a solution of 2-tert-butylphenol (25.0 g, 166.4 mmol) in acetonitrile (150 mL) was added N-bromosuccinimide (30.0 g, 168.5 mmol), and the mixture was stirred at room temperature for 16 hr. Petroleum ether (150 mL) was added to the reaction mixture, and the mixture was stirred at 0C for 1 hr. The precipitated white solid was filtered, and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane:ethyl acetate 95: 5 - 90: 10) to give the title compound as a yellow oil. This was used for the next reaction without further purification. 1H NMR (300 MHz, CDCl3) delta 7.35 (d, J=2.7Hz, 1H), 7.16 (dd, J=8.3, 2.3Hz, 1H), 6.55 (d, J=8.3Hz, 1H), 4.99 (s, 1H), 1.38 (s, 9H).
	With hydrogen bromide; acetic acid; In water; dimethyl sulfoxide; at 1 - 40℃; for 1h;	step 1 Production of 4-bromo-2-tert-butylphenol 2-tert-Butylphenol (24.7 g) was dissolved in acetic acid (220 mL) and 48% hydrobromic acid (110 mL), and dimethyl sulfoxide (110 mL) was added dropwise under ice-cooling. After stirring the mixture at room temperature for 1 hr, the reaction mixture was neutralized with water and sodium hydrogencarbonate (257 g) and extracted with diethyl ether. The obtained diethyl ether layer was washed successively with saturated aqueous sodium hydrogencarbonate solution, water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was evaporated to give the title compound (41.6 g) as a colorless oil.
	With N-Bromosuccinimide; In acetonitrile; Petroleum ether;	Example 9 2-tert-Butyl-4-bromophenol To a solution of 2-tert-butylphenol (250 g, 1.67 mol) in CH3CN (1500 mL) was added NBS (300 g, 1.67 mol) at room temperature. After addition, the mixture was stirred at room temperature overnight and then the solvent was removed. Petroleum ether (1000 mL) was added, and the resulting white precipitate was filtered off. The filtrate was concentrated under reduced pressure to give the crude 2-tert-butyl-4-bromophenol (380 g), which was used without further purification.
	With bromine; In dichloromethane; for 1.25h;	Step 1: 4-bromo-2-(tert-butyl)phenol:To a solution of 2-(tert-butyl)phenol (5 ml, 32.6 mmol) in DCM (30 ml) was added bromine (1 .67 ml; 32.6 mmol) slowly during 15 min. The solution was stirred for 1 h and then concentrated in vacuo. The product was obtained as a red-brown liquid (8.40 g) which was used without further purification. 1H NMR (500 MHz, CDCI3): 7.35 (1 H, d), 7.17-7.15 (1 H, dd), 6.55-6.54 (1 H, d), 4.77 (1 H, br s), 1 .38 (9H, s).
380 g	With N-Bromosuccinimide; In acetonitrile; at 20℃;	To a solution of 2-tert-butylphenol (250 g, 1.67 mol) in CH3CN (1500 mL) was added NBS (300 g, 1.67 mol) at room temperature. After addition, the mixture was stirred at room temperature overnight and then the solvent was removed. Petroleum ether (1000 mL) was added, and the resulting white precipitate was filtered off. The filtrate was concentrated under reduced pressure to give the crude 2-tert-butyl-4-bromophenol (380 g), which was used without further purification.
96%Chromat.	With ammonium metavanadate; perchloric acid; tetrabutylammomium bromide; dihydrogen peroxide; In chloroform; water; at 20℃; for 0.0833333h;	General procedure: NH4VO3 (5 mol%) and H2O2 (200 mol%) were placed in a flask. After complete dissolution of the catalyst, TBAB (3 mmol) was added and the mixture was stirred at room temperature. Then, Et2O (10 ml) and aromatic substrate (1 mmol) were added to the mixture. Finally, by slow drip, 1 ml of 1N HClO4 solution was added. After adding the acid, the colour of the reaction changed from yellow to red due to the formation of oxomonoperoxovanadium. Conversion was followed by TLC and determined by GC. The phases were separated and the aqueous phase was extracted with CH2Cl2 (15 ml x3). The organic phases were pooled, washed with brine, dried over Na2SO4 and filtered. The solvent was removed under reduced pressure and the resulting crude product was purified by column chromatography with Hex:AcOEt.
	With tetrabutylammomium bromide; sodium thiosulfate; In chloroform; at 20℃; for 1h;	3.1: 4-bromo-2-tert-butylphenol 47 g (98 mmol) of tetrabutylammonium bromide are added portionwise to a solution of 15 ml (98 mmol) of 2-tert-butylphenol in 300 ml of chloroform. The reaction medium is stirred at room temperature for 1 hour and then hydrolyzed by addition of 300 ml of a saturated aqueous sodium thiosulfate solution and extracted with dichloromethane. The organic phases are collected, washed with water, dried on magnesium sulfate and then filtered and evaporated. The crude residue obtained is taken up in diethyl ether and the remaining inorganic salts precipitate. The medium is filtered and the ether phase is washed with a saturated sodium chloride solution, dried on magnesium sulfate, filtered and evaporated 22 g (100%) of 4-bromo-2-tert-butylphenol are obtained in the form of a light yellow oil.

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[23]Patent: US2010/81658,2010,A1 .Location in patent: Page/Page column 31-32.
[24]Journal of Medicinal Chemistry,2014,vol. 57,p. 9776 - 9795.
[25]Journal of Medicinal Chemistry,2014,vol. 57,p. 9776 - 9795.
[26]Journal of medicinal chemistry,1971,vol. 14,p. 789 - 792.
[27]Patent: EP1391451,2004,A1 .Location in patent: Page 108.
[28]Patent: EP2202223,2010,A1 .Location in patent: Page/Page column 59.
[29]Patent: US2007/197512,2007,A1 .Location in patent: Page/Page column 58.
[30]Patent: US2011/98311,2011,A1 .
[31]Patent: WO2012/69852,2012,A1 .Location in patent: Page/Page column 81-82.
[32]Tetrahedron,2012,vol. 68,p. 9954 - 9961,8.
[33]Bioorganic and medicinal chemistry letters,2012,vol. 22,p. 6587 - 6590,4.
[34]Chemistry - A European Journal,2013,vol. 19,p. 7510 - 7522.
[35]Patent: US2015/231142,2015,A1 .Location in patent: Paragraph 0530.
[36]Tetrahedron Letters,2016,vol. 57,p. 5644 - 5648.
[37]Patent: US2017/342040,2017,A1 .Location in patent: Paragraph 0240.

4
[ 100-97-0 ]
[ 10323-39-4 ]
[ 153759-58-1 ]

References: [1]Journal of Organic Chemistry,2006,vol. 71,p. 1825 - 1836.
[2]European Journal of Organic Chemistry,2017,vol. 2017,p. 639 - 645.
[3]Journal of the American Chemical Society,2010,vol. 132,p. 15390 - 15398.
[4]Journal of Organic Chemistry,1994,vol. 59,p. 1939 - 1942.

5
[ 50-00-0 ]
[ 10323-39-4 ]
[ 1168-48-5 ]

References: [1]Journal of Organic Chemistry,1994,vol. 59,p. 7785 - 7792.

6
[ 10323-39-4 ]
[ 100-44-7 ]
[ 33839-12-2 ]

Yield	Reaction Conditions	Operation in experiment
583 mg		To a solution of <strong>[10323-39-4]4-bromo-2-tert-butylphenol</strong> (CAS: 10323-39-4; 500 mg) in DMF (5 mL) was added NaH (114 mg) and the reaction mixture was stuffed for 10 minutes at rt. Then,benzylchloride (290 mg) was added and the reaction mixture was stuffed for 2 hours at rt. The mixture was poured on 30 mL 10% aqueous NH4C1 solution and 30 mL EtOAc and the layers were separated. The aqueous layer was extracted a second time with 30 mL EtOAc. The organic layers were washed with 30 mL brine, dried over Mg504, filtered and concentrated in vacuo. The residue was purified by silica gel chromatography eluting with a gradient of n-heptane inethyl acetate (100/0 to 80/20) to give the title compound as a colorless solid (583 mg. MS (mlz):318 [Mf?.

References: [1]Journal of medicinal chemistry,1971,vol. 14,p. 789 - 792.
[2]Patent: WO2017/37146,2017,A1 .Location in patent: Page/Page column 152.

7
[ 10323-39-4 ]
[ 18162-48-6 ]
[ 171365-80-3 ]

References: [1]Journal of Medicinal Chemistry,1995,vol. 38,p. 4993 - 5006.

8
[ 50-00-0 ]
[ 10323-39-4 ]
[ 124-40-3 ]
4-Bromo-2-tert-butyl-6-dimethylaminomethyl-phenol [ No CAS ]

References: [1]Zeitschrift fur Naturforschung, B: Chemical Sciences,1995,vol. 50,p. 1859 - 1868.

9
[ 10323-39-4 ]
[ 22157-91-1 ]
[ 216976-23-7 ]

References: [1]Bulletin of the Chemical Society of Japan,1998,vol. 71,p. 2393 - 2402.

10
[ 10323-39-4 ]
[ 612-14-6 ]
C₂₈H₃₂Br₂O₂ [ No CAS ]

References: [1]Organic Preparations and Procedures International,1999,vol. 31,p. 328 - 332.

12
[ 10323-39-4 ]
nickel-aluminium-alloy [ No CAS ]
aq.-ethanolic NaOH [ No CAS ]
[ 88-18-6 ]

References: [1]Journal of the American Chemical Society,1949,vol. 71,p. 1966.

Yield	Reaction Conditions	Operation in experiment
		Purification by flash chromatography (silica, 2% ethyl acetate in hexane) yielded the title compound as a clear, light yellow oil. PMR (CDCl3):d 1.38 (9H, s), 4.79 (1H, s), 6.54 (1H, d, J=8.5 Hz), 7.16 (1H, dd, J=8.5, 2.5 Hz), 7.35 (1H, d, J=2.5 Hz).

14
[ 10323-39-4 ]
[ 74-88-4 ]
[ 14804-34-3 ]

References: [1]Journal of the Chemical Society. Perkin Transactions 1 (2001),2001,p. 588 - 598.
[2]Chemistry - A European Journal,2013,vol. 19,p. 7510 - 7522.

15
[ 50-00-0 ]
[ 10323-39-4 ]
[ 108-00-9 ]
[ 627090-15-7 ]

References: [1]Dalton Transactions,2003,p. 3082 - 3087.
[2]Macromolecules,2012,vol. 45,p. 5387 - 5396.

16
[ 50-00-0 ]
[ 10323-39-4 ]
[ 153759-58-1 ]

References: [1]Science China Chemistry,2014,vol. 57,p. 107 - 113.
[2]Tetrahedron Letters,2005,vol. 46,p. 3829 - 3830.
[3]Tetrahedron,2012,vol. 68,p. 9954 - 9961,8.

17
[ 3587-60-8 ]
[ 10323-39-4 ]
1-[(benzyloxy)methoxy]-4-bromo-2-(tert-butyl)benzene [ No CAS ]

References: [1]Helvetica Chimica Acta,2005,vol. 88,p. 936 - 949.

18
[ 10323-39-4 ]
bromo-tris-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane [ No CAS ]
2-(tert-butyl)-4-[tris(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silyl]phenol [ No CAS ]

References: [1]Helvetica Chimica Acta,2005,vol. 88,p. 936 - 949.

19
[ 10323-39-4 ]
bromo[tris(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl)]silane [ No CAS ]
2-(tert-butyl)-4-[tris(3,3,4,4,5,5,6,6,7,7,8,8,9,10,10,10-heptadecafluorodecyl)silyl]phenol [ No CAS ]

References: [1]Helvetica Chimica Acta,2005,vol. 88,p. 936 - 949.

20
[ 67-56-1 ]
[ 201230-82-2 ]
[ 10323-39-4 ]
[ 39778-63-7 ]

References: [1]Journal of Medicinal Chemistry,2006,vol. 49,p. 3520 - 3535.

21
[ 10323-39-4 ]
[ 10605-40-0 ]
[ 945527-87-7 ]

Yield	Reaction Conditions	Operation in experiment
84%		Compound 1 (2.7 g, 12 mmol) was dissolved in tetrahydrofuran (100 mL) under a nitrogen atmosphere, and tert-BuLi (14.5 g, 1.7 M pentane solution) was added thereto using a syringe while stirring at -78 C. The reaction was allowed to proceed at -78 C. for 2 hours, and chloro(3-chloropropyl)dimethylsilane (4.639 g, 27.1 mmol) was added to the reaction mixture using a syringe. The resulting solution was slowly warmed to room temperature over 2 hours, 150 mL of water was added thereto, and stirred for 4 hours. The resulting solution was extracted with ethyl acetate. The separated organic layer was dried over anhydrous magnesium sulfate, and filtered. The solvent was removed from the filtrate using a rotary vacuum evaporator, and the residue was purified by column chromatography using a 1:20 mixture of ethyl acetate and hexane, to obtain 2-tert-butyl-4-(3-chloropropyl)dimethylsilylphenol (yield: 84%). IR (KBr): 3533 (OH) cm-1. 1H NMR (CDCl3): delta 7.41 (s, 1H, m-H), 7.22 (dd, J=7.6 Hz, 1.2 Hz, 1H, m-H), 6.68 (d, J=7.6 Hz, 1H, o-H), 4.85 (s, 1H, OH), 3.52 (t, J=7.2 Hz, 2H, CH2Cl), 1.81 (m, 2H, CH2CH2CH2), 1.45 (s, 9H, tert-BuCH3), 0.86 (m, 2H, CH2Si), 0.30 (s, 6H, CH3) ppm. 13C {1H}NMR (CDCl3): delta 154.94, 135.23, 132.47, 132.09, 129.12, 116.14, 48.08, 34.67, 29.68, 27.81, 13.86, -2.72 ppm. HRMS (FAB): m/z calculated ([M]C15H25ClOSi) 284.1363. found 284.1363.

References: [1]Journal of the American Chemical Society,2007,vol. 129,p. 8082 - 8083.
[2]Patent: US2014/249323,2014,A1 .Location in patent: Paragraph 0143.

22
[ 952579-61-2 ]
[ 10323-39-4 ]
C₂₄H₃₀FNO₃ [ No CAS ]

References: [1]Bioorganic and Medicinal Chemistry Letters,2007,vol. 17,p. 5558 - 5562.

23
[ 10323-39-4 ]
[ 945527-91-3 ]

References: [1]Journal of the American Chemical Society,2007,vol. 129,p. 8082 - 8083.
[2]Patent: US2014/249323,2014,A1 .

24
[ 10323-39-4 ]
C₂₈H₅₂NO₂Si⁽¹⁺⁾*Cl^(1-) [ No CAS ]

References: [1]Journal of the American Chemical Society,2007,vol. 129,p. 8082 - 8083.

25
[ 10323-39-4 ]
[ 847943-49-1 ]

References: [1]Journal of Medicinal Chemistry,2006,vol. 49,p. 3520 - 3535.

26
[ 10323-39-4 ]
[ 854607-38-8 ]

References: [1]Journal of Medicinal Chemistry,2006,vol. 49,p. 3520 - 3535.

27
[ 10323-39-4 ]
3-tert-Butyl-4-[(2R,5S)-5-((S)-2-cyano-pyrrolidine-1-carbonyl)-pyrrolidin-2-ylmethoxy]-benzoic acid; compound with trifluoro-acetic acid [ No CAS ]

References: [1]Journal of Medicinal Chemistry,2006,vol. 49,p. 3520 - 3535.

28
[ 10323-39-4 ]
[ 66737-88-0 ]