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Chemical Structure| 2142-69-0 Chemical Structure| 2142-69-0

Structure of 2'-Bromoacetophenone
CAS No.: 2142-69-0

Chemical Structure| 2142-69-0

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Product Citations

Product Citations

Bashar, Noorul ; Kundu, Bidyut Kumar ; Pozdeev, Anton S ; Jiang, De-en ; Sun, Yujie ;

Abstract: Aryl radicals serve as essential intermediates in contemporary organic synthesis, facilitating diverse carbon−carbon and carbon-heteroatom bond-forming reactions under mild conditions. Aryl halides, widely available and frequently employed as precursors for photocatalytic aryl radical generation, typically require with strong reducing capabilities to overcome their high reduction potentials. Herein, we report an innovative approach for the photocatalytic generation of aryl radicals using an organic photocatalyst 5,5′-bis((4-methoxyphenyl)ethynyl)-2,2′-bibenzo[d]thiazole (dBAP) that leverages the proton-coupled electron transfer (PCET) mechanism. This strategy allows the selective generation of aryl radicals at the ortho and para positions of aryl halides bearing PCET handles, despite dBAP’s intrinsic reducing power being insufficient for direct electron transfer to the aryl halides, in contrast to the prevalent approaches. Mechanistic investigations highlight the role of PCET in lowering the activation barrier for aryl radical formation, enabling efficient C−H, C−C, and C−B bond-forming reactions with high regioselectivity and functional group tolerance. This work underscores the potential of PCET-driven photocatalysis using organic as a sustainable and versatile platform for expanding the synthetic utility of aryl radicals under ambient conditions.

Purchased from AmBeed: ; ; ; ; ; ; ; ; ; ; ; 99-91-2

Alternative Products

Product Details of [ 2142-69-0 ]

CAS No. :2142-69-0
Formula : C8H7BrO
M.W : 199.04
SMILES Code : C1=CC=CC(=C1C(C)=O)Br
MDL No. :MFCD00000067
InChI Key :PIMNFNXBTGPCIL-UHFFFAOYSA-N
Pubchem ID :75060

Safety of [ 2142-69-0 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H302-H315-H319-H332-H335
Precautionary Statements:P261-P280-P305+P351+P338

Computational Chemistry of [ 2142-69-0 ] Show Less

Physicochemical Properties

Num. heavy atoms 10
Num. arom. heavy atoms 6
Fraction Csp3 0.12
Num. rotatable bonds 1
Num. H-bond acceptors 1.0
Num. H-bond donors 0.0
Molar Refractivity 44.34
TPSA ?

Topological Polar Surface Area: Calculated from
Ertl P. et al. 2000 J. Med. Chem.

17.07 Ų

Lipophilicity

Log Po/w (iLOGP)?

iLOGP: in-house physics-based method implemented from
Daina A et al. 2014 J. Chem. Inf. Model.

1.87
Log Po/w (XLOGP3)?

XLOGP3: Atomistic and knowledge-based method calculated by
XLOGP program, version 3.2.2, courtesy of CCBG, Shanghai Institute of Organic Chemistry

2.28
Log Po/w (WLOGP)?

WLOGP: Atomistic method implemented from
Wildman SA and Crippen GM. 1999 J. Chem. Inf. Model.

2.65
Log Po/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.

2.52
Log Po/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

2.83
Consensus Log Po/w?

Consensus Log Po/w: Average of all five predictions

2.43

Water Solubility

Log S (ESOL):?

ESOL: Topological method implemented from
Delaney JS. 2004 J. Chem. Inf. Model.

-2.89
Solubility 0.257 mg/ml ; 0.00129 mol/l
Class?

Solubility class: Log S scale
Insoluble < -10 < Poorly < -6 < Moderately < -4 < Soluble < -2 Very < 0 < Highly

Soluble
Log S (Ali)?

Ali: Topological method implemented from
Ali J. et al. 2012 J. Chem. Inf. Model.

-2.28
Solubility 1.06 mg/ml ; 0.0053 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

-3.59
Solubility 0.0512 mg/ml ; 0.000257 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

No
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.

-5.9 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

2.0
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<1.0
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)

1.11

Application In Synthesis of [ 2142-69-0 ]

* 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 [ 2142-69-0 ]

[ 2142-69-0 ] Synthesis Path-Downstream   1~26

  • 1
  • [ 2142-69-0 ]
  • [ 4637-24-5 ]
  • [ 16732-66-4 ]
  • 1,5-bis(2-bromophenyl)pyrazole [ No CAS ]
  • 2
  • [ 2142-69-0 ]
  • [ 216019-28-2 ]
  • 1-(3'-isopropyl[1,1'-biphenyl]-2-yl)-1-ethanone [ No CAS ]
  • 3
  • [ 2142-69-0 ]
  • [ 26767-16-8 ]
YieldReaction ConditionsOperation in experiment
100% With pyridine; selenium(IV) oxide; at 100℃; for 2h; 8.3 g (75 mmoles) of selenium dioxide were added to 10 g (50 mmoles) of 2'- bromoacetophenone dissolved in 20 ml of pyridine; the mixture was left under magnetic stirring at 100C for 2 hours. After control in TLC and LC-MS, the mixture was filtered to eliminate the selenium and the pyridine was removed at reduced pressure. The residue was acidified with diluted HCl and extracted with ethyl acetate; the phases were then separated; the aqueous phase was re- extracted twice with ethyl acetate. The organic phases were joined and washed with water and a saturated solution of NaCl. After anhydrification on sodium sulfate, filtration and evaporation of the solvent at reduced pressure, 11.4 g of the desired product (50 mmoles) were obtained, as a cream-coloured solid. The raw product thus obtained was used for the subsequent reaction. Quantitative yield. LC-MS [M+H] = 229.
87% With pyridine; selenium(IV) oxide; at 120℃; for 18h;Inert atmosphere; Into a 250-mL 3-necked round-bottom flask purged and maintained with an inert atmosphere of nitrogen, was placed a solution of l-(2-bromophenyl)ethan-l-one (10 g, 50.24 mmol, 1.00 equiv) in pyridine (80 mL). This was followed by the addition of Se02 (22 g, 198.27 mmol, 3.95 equiv). The resulting solution was stirred for 18 h at 120 C in an oil bath. The reaction mixture was cooled to room temperature. The solids were filtered out. The resulting mixture was concentrated under vacuum. The residue was dissolved in 100 mL of water. The resulting mixture was washed with 2x50 mL of ethyl acetate. The pH value of the aqueous layer was adjusted to 1-2 with hydrogen chloride (4 mol/L). The resulting solution was extracted with 3x80 mL of ethyl acetate and the organic layers combined and dried over anhydrous sodium sulfate. The solids were filtered out. The resulting mixture was concentrated under vacuum. This resulted in 10 g (87%) of 2-(2- bromophenyl)-2-oxoacetic acid as yellow oil. MS (ESI) m/z 230 ([M + H]+)
With pyridine; selenium(IV) oxide; at 90 - 110℃; for 5h; General procedure: The substituted alpha-keto acids were prepared from oxidation of corresponding methyl ketones with SeO2 (Scheme 1). Methyl ketones (5 mmol), SeO2 (6 mmol), 20 mL of pyridine were added in a 50 mL round-bottom flask. The reaction mixture was stirred at 110 oC for 1 h, and under 90 oC for another 4 h. The desired products were isolated by silica-gel column chromatography.
  • 4
  • [ 2142-69-0 ]
  • [ 40138-17-8 ]
  • [ 1149344-89-7 ]
  • 5
  • [ 67-56-1 ]
  • [ 2142-69-0 ]
  • [ 700-46-9 ]
YieldReaction ConditionsOperation in experiment
17% With di-tert-butyl peroxide; copper(l) chloride; at 120℃; for 6.0h; General procedure: 2'-Bromoacetophenone (1a) (100.0 mg, 0.5mmol), benzyl alcohol (5a) (325.0mg,1.5mmol), CuCl (5.0mg, 0.05mmol), DTBP (365.0mg, 1.25 mmol), and 25% aqueous ammonia (0.5 mL) were placed in a thick-walled Pyrex screw-captube(25mL), and the tube was capped and the mixture heated in an oil bath at 120 C with stirring for 6 h. After the reaction mixture was cooled to room temperature, the workup and isolation of the products were essentially similar to the procedure above-mentioned. Compound 3a was obtained as white solid in 65% (71.5 mg, 0.33 mmol), and the GC analysis of the reaction mixture disclosed the formation of 3a in 66% GC yield.
  • 6
  • [ 50-00-0 ]
  • [ 2142-69-0 ]
  • [ 700-46-9 ]
YieldReaction ConditionsOperation in experiment
49% With ammonia; copper(l) chloride; In 1-methyl-pyrrolidin-2-one; water; at 80℃; for 12.0h;Sealed tube; General procedure: 2'-Bromoacetophenone (1a) (100.0 mg, 0.5 mmol), benzaldehyde (2a) (58.0 mg, 0.55 mmol), CuCl (5.0 mg, 0.05 mmol), 25% aqueous ammonia (0.5 mL), and NMP (0.5 mL) were placed in a thick-walled Pyrex screw-cap tube (25 mL) under air atmosphere, and the tube was capped and the mixture was heated in an oil bath at 80 C with stirring for 12 h. After the reaction mixturewas cooled to room temperature, the crude reaction mixture was extracted with EtOAc for three times (3.0 mL 3). After removal of volatiles under a reduced pressure, the residue was diluted with CH2Cl2 (4.0 mL) and then n-docosane (62.1 mg, 0.2 mmol) was added as an internal standard for GC analysis. After GC and GCeMS analyses of the reaction mixture, volatiles were removed under a reduced pressure, and the residue was then subjected to silica gel column chromatography [eluting with petroleum ether and then with a mixture of petroleum ether and ethyl acetate (100:1e50:1)] to afford 4-methyl-2-phenylquinazoline (3a) (69.6 mg, 0.32 mmol, 63%) as white solid. The GC analysis of the reaction mixture disclosed the formation of 3a in 65% GC yield.
  • 8
  • [ 1025707-93-0 ]
  • [ 2142-69-0 ]
  • C13H14O2 [ No CAS ]
  • 9
  • [ 1025707-93-0 ]
  • [ 2142-69-0 ]
  • [ 1537903-28-8 ]
  • 11
  • [ 2142-69-0 ]
  • [ 15016-42-9 ]
  • [ 1542123-80-7 ]
  • 12
  • [ 2142-69-0 ]
  • [ 5460-32-2 ]
  • [ 1184772-51-7 ]
YieldReaction ConditionsOperation in experiment
80% With potassium tert-butylate; palladium diacetate; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; In toluene; at 80℃; for 2h;Schlenk technique; Inert atmosphere; Compound 1 was mixed with with aryliodide 2c (132.0 mg, 0.50 mmol), ortho-bromoacetophenone 1a (109.4 mg, 0.55 mmol), Pd(OAc)2 (2.2 mg, 2 mol%), xantphos (11.6 mg, 4 mol%), tBuOK (72.9 mg, 0.65 mmol), and dry toluene (4 mL)at 80 C for 45 min. Silica-gel column chromatography (20g, petroleum ether/ethyl acetate, 85:15 to 80:20) furnished the title compound 3ac (155 mg, 92%) as yellow solid, recrystallized the solid with dichloromethane/hexane, mp 74-76 C [TLCc ontrol (petroleum ether/ethyl acetate 90:10), Rf(1a)0.55, Rf(2c)0.45, and Rf(3ac) 0.20, UV detection]. IR (MIR-ATR, 4000-600 cm1): νmax2956, 2923,2852, 1697, 1587, 1512, 1463, 1422, 1259, 1154, 1140, 1025, 791, 757, 678 cm1. 1HNMR (CDCl3, 400 MHz): d7.57 (d, 1H, J7.8 Hz, Ar-H), 7.35-7.15 (m, 3H,Ar-H), 6.78 (d, 1H, J8.7 Hz, Ar-H), 6.76 (dd, 1H, J8.7 and 1.9 Hz, Ar-H),6.74 (d, 1H. J1.9 Hz, Ar-H), 4.15 (s, 2H, ArCOCH2), 3.83 (s, 3H, ArOCH3),3.82 (s, 3H, ArOCH3) ppm. 13C NMR (CDCl3, 100 MHz): 201.8 (s, Ar-C=O),148.9 (s, Ar-C), 148.1 (s, Ar-C), 141.4 (s, Ar-C), 133.5 (d, Ar-CH), 131.4 (d, Ar-CH),128.6 (d, Ar-CH), 127.2 (d, Ar-CH), 125.8 (s, Ar-C), 121.9 (d, Ar-CH), 118.6(s, Ar-C), 112.7 (d, Ar-CH), 111.2 (d, Ar-CH), 55.8 (q, 2C, 2ArOCH3), 49.0 (t, Ar-COCH2) ppm. HR-MS (ESI) m=z calculated for [C16H7916 BrO3][MH]:335.0277; found 335.0294. [C16H8116 BrO3][MH]: 337.0259; found 337.0274.
  • 13
  • [ 2142-69-0 ]
  • [ 34800-90-3 ]
  • C20H17BrN2O [ No CAS ]
YieldReaction ConditionsOperation in experiment
69.3% In ethanol;Reflux; General procedure: solutionof acid hydrazide (0.01 mol) and appropriate benzaldehyde/acetophenone (0.01 mol) in ethanol was refluxed for 5-6 h. The precipitated title compounds were then filtered off, washed with water and recrystallized from ethanol.
  • 14
  • [ 2142-69-0 ]
  • [ 1521-41-1 ]
  • N-(2-acetylphenyl)-3,4-dimethoxybenzamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
34% With copper(l) iodide; potassium carbonate; N,N`-dimethylethylenediamine; In toluene; at 110℃; for 24h;Schlenk technique; Inert atmosphere; Molecular sieve;Catalytic behavior; General procedure: The following compounds were synthesized based upon reported literatureprocedure2 under our optimized cross-coupling conditions. An oven-dried round-bottom flaskwith a Teflon stir bar was charged with amide (2.0 equiv, 1.00 mmol), CuI (20 mol%, 0.10mmol), base (2 equiv, 1.00 mmol), and 200 mg activated 4 Å molecular sieves. The roundbottomflask was sealed with a rubber septum, evacuated and refilled with nitrogen (thissequence was performed three times). Under nitrogen, 2’-bromoacetophenone (1.0 equiv, 0.50 mmol), N, N’- dimethylethylenediamine (40 mol%, 0.2 mmol), and toluene (3 mL) were eachadded via syringe. The round-bottom flask was then placed in a preheated oil bath at 110 C. Thereaction was heated with stirring for 24 h until TLC showed completion of the reaction. Thecrude of reaction obtained was cooled to room temperature. Toluene was removed under vacuothen water (5 mL) was added to the reaction mixture. The biphasic mixture was extracted withethyl acetate (3x15 mL). The organic extracts were collected, dried over anhydrous sodiumsulfate, filtered, and concentrated in vacuo to remove solvent. The product was purified bycolumn chromatography on silica gel (100-200 mesh) with EtOAc/hexane system, to afford thecorresponding N-ketoarylamides.
  • 15
  • [ 2142-69-0 ]
  • [ 180092-32-4 ]
  • 16
  • [ 2142-69-0 ]
  • [ 95-92-1 ]
  • [ 103935-10-0 ]
  • 17
  • [ 871231-45-7 ]
  • [ 2142-69-0 ]
  • 1-(3'-hydroxy-[1,1'-biphenyl]-2-yl)ethan-1-one [ No CAS ]
  • 18
  • [ 2142-69-0 ]
  • [ 5900-59-4 ]
  • [ 148182-95-0 ]
YieldReaction ConditionsOperation in experiment
54% O-bromoacetophenone 1a (119.4 mg, 0.12 mmol) was sequentially added to a 25 mL round bottom flask as described in Example 1,0.6 mmol), dimethylsulfoxide (3 mL) and iodine (152 mg, 0.6 mmol) were added and the mixture was stirred under heating at 110 ° C for 3 h, then cooledBut to room temperature, 2d (68.2 mg, 0.4 mmol), CuBr (11.5 mg, 0.08 mmol) and K2CO3 (221 mg, 1.6 mmol)The reaction was stirred at room temperature for 5h, then heated and stirred at 100 for 3h. After the reaction was completed, saturated chlorination was added to the reaction vesselThe reaction was quenched with ammonium chloride and extracted with dichloromethane. The combined organic phases were washed with deionized water and saturated sodium chloride solution,Sodium drying. Filtration, spin-drying, separation through a silica gel column (petroleum ether / ethyl acetate = 2/1, v / v)3-Chloroindole [2,1-b] quinazoline-6,12-dione 3k (61 mg, 54percent).
  • 19
  • [ 2142-69-0 ]
  • [ 175883-62-2 ]
  • 1-(4'-methoxy-3'-methyl-[1,1'-biphenyl]-2-yl)ethan-1-one [ No CAS ]
  • 20
  • [ 2142-69-0 ]
  • [ 197223-39-5 ]
  • 2′-(3,5-di-tert-butylphenyl)acetophenone [ No CAS ]
  • 21
  • [ 2142-69-0 ]
  • [ 197223-39-5 ]
  • bis[2-(3,5-di-tert-butylphenyl)benzoyl]methane [ No CAS ]
  • 23
  • [ 2142-69-0 ]
  • [ 89226-13-1 ]
  • tert-butyl N-[(4-phenylthiazol-2-yl)methyl]carbamate [ No CAS ]
YieldReaction ConditionsOperation in experiment
70% In ethanol; at 20℃; for 16h; A solution of 2-bromoacetophenone (1.99 g, 10 mmol) and tert-butyl (2-amino 2-thioxoethyl)carbamate (1.90 g, 10 mmol) in EtOH (50 mL) was stirred at room temperature for 16 h. The solution was evaporated and the resulting residue diluted in water (25 mL) and extracted with EtOAc (2 x 25 mL). The combined extracts were dried and evaporated affording a pale yellow solid. Recrystallisation from MeCN (13 mL) led to colourless solid (2.03 g, 70%). M/z 235 (M+H-tBu)+.
  • 24
  • [ 2142-69-0 ]
  • [ 1671-88-1 ]
  • 6-(2-bromophenyl)-3-(pyridin-2-yl)-7H-pyrido[2,1-d][1,2,4]triazolo[4,3-b][1,2,5]triazepin-8-ium iodide [ No CAS ]
  • 26
  • [ 2142-69-0 ]
  • [ 872366-63-7 ]
  • C15H9BrFNO3 [ No CAS ]
 

Historical Records

Technical Information

Categories

Related Functional Groups of
[ 2142-69-0 ]

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