Home Cart 0 Sign in  

[ CAS No. 103-88-8 ]

{[proInfo.proName]}
Cat. No.: {[proInfo.prAm]}
2D
Chemical Structure| 103-88-8
Chemical Structure| 103-88-8
Structure of 103-88-8 *Storage: {[proInfo.prStorage]}

Quality Control of [ 103-88-8 ]

Purity: {[proInfo.showProBatch.pb_purity]}

Related Doc. of [ 103-88-8 ]

SDS

Product Details of [ 103-88-8 ]

CAS No. :103-88-8MDL No. :MFCD00000092
Formula :C8H8BrNOBoiling Point :353.4°C at 760 mmHg
Linear Structure Formula :-InChI Key :N/A
M.W :214.06Pubchem ID :7683
Synonyms :

Computed Properties of [ 103-88-8 ]

TPSA : 29.1 H-Bond Acceptor Count : 1
XLogP3 : - H-Bond Donor Count : 1
SP3 : 0.13 Rotatable Bond Count : 1

Safety of [ 103-88-8 ]

Signal Word:WarningClassN/A
Precautionary Statements:P261-P305 P351 P338UN#:N/A
Hazard Statements:H315-H319-H335Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 103-88-8 ]

  • Downstream synthetic route of [ 103-88-8 ]

[ 103-88-8 ] Synthesis Path-Downstream   1~8

  • 1
  • [ 103-88-8 ]
  • [ 74-88-4 ]
  • [ 50438-47-6 ]
YieldReaction ConditionsOperation in experiment
90% (ii) N-(4-Bromophenyl)-N-methylacetamide Sodium hydride (101.5 mg, 2.33 mmol) (55% in paraffin liquid) was added to a solution of 249 mg (1.16 mmol) of the title compound produced in step (i) of Reference Example 7 in N,N-dimethylformamide (2.5 ml), and the mixture was stirred at room temperature for 30 min. Thereafter, methyl iodide was added, and the mixture was stirred at room temperature for 1 hr. The reaction was stopped by adding a saturated aqueous sodium hydrogencarbonate solution, and the reaction solution was extracted with ethyl acetate. The organic layer was washed with water and saturated brine in that order, was dried over anhydrous sodium sulfate, and was filtered. The filtrate was concentrated under the reduced pressure, and the residue was purified by column chromatography on silica gel (hexane : ethyl acetate = 2 : 1) to give 239 mg (yield 90%) of the title compound. 1H-NMR (400 MHz, CDCl3) delta: 1.88 (3H, s), 3.24 (3H, s), 7.08 (2H, d, J = 8.5 Hz), 7.54 (2H, d, J = 8.5 Hz). MS (FAB+) m/z: 227 (M+ + 1).
74% N-(4-Bromophenyl)-7V-methyl-acetamide (62) EPO [103-88-8]4-bromoacetanilide (1.0 g, 4.67 mmol) in DMF (5 mL) is added dropwise to a suspension of sodium hydride (224 mg, 5.61 mmol, 60% dispersion in mineral oil) in DMF (5 mL) at 0C. After stirring 1 h at 0C, iodomethane (349 mul, 5.61 mmol) is added and the reaction mixture warmed to RT and stirred 16 h. The reaction is quenched with water (15 mL) and extracted into EtOAc (3 x 15 mL); the combined organic phases are then dried over Na2SO4 and reduced in vacuo. Purification by column chromatography (40% EtOAc in heptane) gives the title compound. Yield: 780 mg (74%).LC/MS tr 1.17 min. MS(ES+) m/z 230, 228 (M+H
74% Synthesis of Compound 318lambdaf-(4-Bromophenyl)-lambda''-methyl-acetamide (62)[103-88-8]4-bromoacetanilide (1.0 g, 4.67 mmol) in DMF (5 mL) was added dropwise to a suspension of sodium hydride (224 mg, 5.61 mmol, 60% dispersion in mineral oil) in DMF (5 mL) at 0C. After stirring 1 h at 0C, iodomethane (349 mul, 5.61 mmol) was added and the reaction mixture warmed to RT and stirred 16 h. The reaction was quenched with water (15 mL) and extracted into EtOAc (3 x 15 mL); the combined organic phases were then dried over Na2SO4 and reduced in vacuo. Purification by column chromatography (40% EtOAc in heptane) gave the title compound.Yield: 780 mg (74%).LCZMS f1. 1.17 min.MS(ES+) m/z 230, 228 (M+H).
74% JV-(4-Bromophenyl)-7V-methyl-acetamide (62); EPO [103-88-8]4-bromoacetanilide (1.0 g, 4.67 mmol) in DMF (5 mL) is added dropwise to a suspension of sodium hydride (224 mg, 5.61 mmol, 60% dispersion in mineral oil) in DMF (5 mL) at 0C. After stirring 1 h at 0C, iodomethane (349 mul, 5.61 mmol) is added and the reaction mixture warmed to RT and stirred 16 h. The reaction is quenched with water (15 mL) and extracted into EtOAc (3 x 15 mL); the combined organic phases are then dried over Na2SO4 and reduced in vacuo. Purification by column chromatography (40% EtOAc in heptane) gives the title compound. Yield: 780 mg (74%). LC/MS fr 1.17 min. MS(ES+) m/z 230, 228 (M+H).
74% Synthesis of Compound 318; yV-(4-Bromophenyl)-7V-methyl-acetamide (62); [103-88-8]4-bromoacetanilide (1.0 g, 4.67 mmol) in DMF (5 mL) is added dropwise to a suspension of sodium hydride (224 mg, 5.61 mmol, 60% dispersion in mineral oil) in DMF (5 mL) at 0C. After stirring 1 h at 0C, iodomethane (349 mul, 5.61 mmol) is added and the reaction mixture warmed to RT and stirred 16 h. The reaction is quenched with water (15 mL) and extracted into EtOAc (3 x 15 mL); the combined organic phases are then dried over Na2SO4 and reduced in vacuo. Purification by column chromatography (40% EtOAc in heptane) gives the title compound. Yield: 780 mg (74%).LC/MS ;r 1.17 min. MS(ES+) m/z 230, 228 (M+H).

  • 2
  • [ 64-19-7 ]
  • [ 106-40-1 ]
  • [ 103-88-8 ]
YieldReaction ConditionsOperation in experiment
98% General procedure: A mixture of carboxylic acid (1 mmol) and TAPC (0.5 mmol, 0.17 g) was grinded at room temperature for 1 min. Then amine (1mmol) was added to the reaction mixture and grinding was continued at the sametemperature for the specified time (Table 2). The progress of the reaction wasmonitored by TLC. After completion of the reaction, H2O (10 mL) wasadded to the reaction mixture and filtered. The product was recrystallized fromEtOH/H2O to afford the pure product.
96% With poly(4-vinylpyridine) perchlorate; In neat (no solvent); at 20℃; for 0.3h; General procedure: The substrate (alcohol, phenol or amine; 1.0 mmol) was treated with Ac2O (2.0 mmol) in the presence of P(4-VPH)ClO4 (50 mg) at room temperature under solvent-free conditions and magnetic stirring. After completion of the reaction as indicated by TLC, the mixture was diluted with Et2O (25 ml) and the catalyst allowed to settle down. The supernatant ethereal solution was decanted off, the catalyst washed with Et2O (2 ml) and the combined ethereal solution concentrated under vacuum to afford the product, identical(mp, IR, 1H and 13C NMR, and GC-MS) to an authentic sample of acetylated product. The recovered catalyst was dried at 50 C under vacuum for 2 h. The recovered catalyst, after drying, was reused for four more consecutive acetylation reactions of benzyl alcohol (1.0 mmol) affording 96, 96, 94, and 94% yields, respectively, in 22, 23, 23, and 25 min (Scheme 2).
  • 3
  • [ 59862-55-4 ]
  • [ 103-88-8 ]
YieldReaction ConditionsOperation in experiment
97% With 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphinane-2,4,6-trioxide; In tetrahydrofuran; ethyl acetate; at 70℃; for 2h;Inert atmosphere; To a solution of ketoxime (0.01 mol) in THF (10 mL) was added T3P (15 mol %, 50% soln in EtOAc) and the resulting reaction mixture was stirred at reflux for 1-4 h under nitrogen atmosphere. When the reaction was completed as confirmed by TLC, the solvent was removed under vacuum and the residue was diluted with water (20 mL). The product was extracted with ethyl acetate (2 × 20 mL) and the combined organic phase was washed with saturated NaHCO3 solution (1 × 10 mL) and brine. The organic phase was dried over anhydrous Na2SO4. The solvent was removed under reduced pressure to afford the desired amides in good purity.
33% With phthalic anhydride; zinc trifluoromethanesulfonate; In acetonitrile; at 50℃;Inert atmosphere; General procedure: Oxime 1 (1.0 mmol, 1.0 equiv), Zn(OTf)2 (73.7 mg, 0.2 mmol, 0.2 equiv) and o-phthalic anhydride (15.0 mg, 0.1 mmol, 0.1 equiv) were dissolved in 1.0 mL CH3CN at rt under nitrogen atomesphere and stirred until the complete consumption of the oxime monitored by TLC analysis. The mixture was evaporated and the residue was purified on flash column chromatography with petroleum ether/ethyl acetate (5:1~2:1) as eluent to afford the desired amide 2.
  • 4
  • [ 103-84-4 ]
  • [ 614-76-6 ]
  • [ 103-88-8 ]
YieldReaction ConditionsOperation in experiment
4%; 94% With N-Bromosuccinimide; chloro-trimethyl-silane; In acetonitrile; at 20℃; for 1h; General procedure: To a solution of 4-bromoanisole (200.8 mg, 1.09 mmol, 1.0 equiv) in acetonitrile (2 mL) was added N-chlorosuccinimide(NCS) (158.3 mg, 1.19 mmol, 1.1 equiv) at rt to give a slightly cloudy mixture. Chlorotrimethylsilane (TMSCl) (14 muL, 0.11 mmol, 0.1 equiv) was then added drop-wise to the reaction mixture. Within a few minutes, the reaction mixture became clear pale yellow solution. The mixture continued to stir at rt for 1 h and was diluted with hexane. The biphasic mixture was concentrated on a rotary evaporator to a crude white solid-oil mixture. This mixture was taken up in hexane and filtered through a short plug of SiO2 and eluted with 5-10% EtOAc-hexane solution. The clear filtrate was concentrated to obtain a mixture of 4-bromo-2-chloro-1-methoxybenzene (2a-Cl) and 2,4-dichloro-1-methoxybenzene (2a-diCl) 237.0 mg (88% of 2a-Cl and 11% of 2a-diCl,based on NMR ratio 2a-Cl: 2a-diCl = 7.1: 1.0; as a pale yellow solid).
  • 5
  • [ 99-90-1 ]
  • [ 103-88-8 ]
YieldReaction ConditionsOperation in experiment
93% With hydroxylamine hydrochloride; water; Thiamine hydrochloride; In 1,4-dioxane; at 90℃; for 0.5h; General procedure: A mixture of ketone 1 (2 mM), hydroxylamine hydrochloride (3 mM) and thiamine hydrochloride (0.4 mM) was taken in 10mL dioxane:H2O (9:1) in a round-bottom flask and heated at 90 C for specific time (30-90 min). The progress of the reaction was monitored using thin layer chromatography (tlc). After completion of the reaction, the reaction flask was cooled to room temperature. The residue was taken in ethyl acetate (30 ml), washed with water (2x15 ml), brine (1x15 ml) and the organic layer was dried (anhyd. Na2SO4). The resulting ethyl acetate solution was concentrated and the desired amides 2 (75-95% yield) are obtained by recrystallization from ethanol.
90% With mesitylenesulfonylhydroxylamine; In acetonitrile; at 20℃; for 8h; General procedure: To a round bottom flask, equipped with a magnetic stirring bar, was added ketone 1 (0.5 mmol, 1.0 equiv.) and acetonitrile (2 mL) at room temperature. To this stirred solution, freshly prepared O-(Mesitylsulfonyl)hydroxylamine 2 (2.0 equiv.) was added. The reaction mixture was stirred for the specified duration and temperature. The progress of the reaction was monitored by TLC. After completion, the reaction mixture was diluted with ethyl acetate (10 mL) and washed with a saturated aqueous NaHCO3 solution (3 x 5 mL). The combined organic layer was washed with brine solution and dried over anhydrous Na2SO4. Solvent was removed under reduced pressure to get the crude product. The reaction that required elevated temperature was stirred first at room temperature for 2 hours after addition of MSH and then heated at 70 C for the specified time.
88% With hydroxylamine hydrochloride; In acetonitrile;Reflux; General procedure: Ketones (1 mmol) and hydroxylamine hydrochloride (0.0694g,1 mmol) were dissolved in CH3CN (10 mL) and stirred for 10 - 15 min. The complex (CS-SalBr-Zn-L) (10 mol%) were added tothe reaction flask. The reaction mixture was heated under reflux for specific time (3e7 h). After completion, the reaction mixture was cooled to room temperature and the catalyst was removed by filtration. The filtrate was treated with ethyl acetate (3 10 mL).The combined organic layers were treated with saturated brine solution and dried over anhydrous sodium sulphate. The removal of solvent yields crude product, which after purification by column chromatography over Silica gel (100e200 mesh), afforded the desired products.
  • 6
  • [ 75-36-5 ]
  • [ 106-40-1 ]
  • [ 103-88-8 ]
YieldReaction ConditionsOperation in experiment
99% (i) N-(4-Bromophenyl)acetamide Triethylamine (0.65 ml, 4.65 mmol) was added to a solution of 200 mg (1.16 mmol) of 4-bromoaniline in tetrahydrofuran (2 ml), and the mixture was stirred at room temperature for 5 min. Acetyl chloride (0.165 ml, 2.33 mmol) was added thereto, and the mixture was stirred at room temperature for 17 hr. The reaction was stopped by adding a saturated aqueous sodium hydrogencarbonate solution, and the reaction solution was extracted with ethyl acetate. The organic layer was washed with water and saturated brine in that order, was dried over anhydrous sodium sulfate and was filtered. The filtrate was concentrated under the reduced pressure, and the residue was purified by column chromatography on silica gel (chloroform: methanol = 20: 1) to give 249 mg (yield 99%) of the title compound.
94% To a stirred solution of 4-bromoaniline (30 g, 174 mmol) in dichioromethane (150 mL) was added triethylamine (73.53 mL, 523 mmol) at 0 C and the mixture was stirred for 15 mm. To this mixture was added acetyl chloride (19.12 g, 240mmol) dropwise and the mixture was stirred at room temperature overnight. The reaction was quenched by addition of water (100 mL). The organic layer was separated, washed with brine solution (100 mL), dried over sodium sulfate, and concentrated under reduced pressure to afford N-(4-bromophenyl)acetamide (35 g, 94% yield): ?H NMR (400 MHz, DMSO-d6) oe 10.05 (s, 1 H), 7.55 (d, J 9.2 Hz, 2H), 7.46 (dd, J= 2 Hz, 6.4 Hz, 2 H), 2.05 (s, 3 H).
94% With hydroxyapatite supported copper(I) oxide; In acetonitrile; at 50℃; for 0.166667h; General procedure: To a mixture of amine (1 mmol), acetyl chloride (1 mmol)in acetonitrile (5 mL) were added hydroxyapatite -Cu2O(0.1 g) under air atmosphere. The reaction mixture wasrefluxed at 50 C for an appropriate time. The progress ofthe reaction was monitored through TLC. Upon completionof the reaction, the reaction mixture was cooled toroom temperature and filtered. The residue was washedwith water followed by EtOAc (3 × 10 mL). The productwas obtained after the removal of solvent under reducedpressure followed by crystallization from pet ether orEtOAc:pet ether or passing through column of silica andelution with EtOAc:pet ether.
89% With potassium carbonate; In dichloromethane; at 20℃; for 3h; To the solution of 4-bromoaniline (46) (2.5 g, 14.5 mmol, 1equiv.) and potassium carbonate (6.05 g, 43.78 mmol, 3 equiv.) indichloromethane (50 mL) was added acetyl chloride (1.55 mL, 2equiv.). The solution was stirred at ambient temperature until TLCshowed the consumption of the starting material. Acetyl chlorideand DCM were evaporated under reduced pressure at 45 C. Waterwas added to dissolve the salt in the residue. The residue mixturewas filtered and washed with DCM. The product (47) was driedunder vacuum to give a light grey solid (2.78 g, 89%) which wasdirectly used in the next step without further purification.Rf 0.22 (EA/Hexane 1: 1); 1H NMR (400 MHz, CDCl3)d 7.49e7.34 (m, 4H), 7.17 (s, 1H), 2.17 (s, 3H).
46% With triethylamine; In dichloromethane; at 0℃; for 2h; Step 56a: N-(4-bromophenyl)acetamide (Compound 0601-150)To the solution of 4-bromoaniline (6.3 g, 63.7mmol) in CH2C12 (50 mL) was added acetyl chloride (3.75 g, 47.7 mmol) and TEA (7.4 g, 73.4 mmol) at 0 C, stirred for 2 hours.The reaction mixture was washed with water, brine , dried over Na2S04, filtered, and concentrated under reduced pressure to give the title compound 0601-150 (3.6 g, 46%>) as a brown solid. LCMS: 214 [M+l]+; 1H NMR (400 MHz, DMSO-d6). delta 2.05 (s, 3H), 7.46(d, J= 8.8 Hz, 2H), 7.57 (d, J= 8.8 Hz, 2H), 10.12 (s, 1H).
46% With triethylamine; In dichloromethane; at 0℃; for 2h; Step 56a: N-(4-bromophenyl)acetamide (Compound 0601-150)[0434]To the solution of 4-bromoaniline (6.3 g, 63.7 mmol) in CH2Cl2 (50 mL) was added acetyl chloride (3.75 g, 47.7 mmol) and TEA (7.4 g, 73.4 mmol) at 0 C., stirred for 2 hours. The reaction mixture was washed with water, brine, dried over Na2SO4, filtered, and concentrated under reduced pressure to give the title compound 0601-150 (3.6 g, 46%) as a brown solid. LCMS: 214 [M+1]+; 1H NMR (400 MHz, DMSO-d6). delta 2.05 (s, 3H), 7.46 (d, J=8.8 Hz, 2H), 7.57 (d, J=8.8 Hz, 2H), 10.12 (s, 1H).
46% With triethylamine; In dichloromethane; at 0℃; for 2h; CH2Cl2 (50mL) solution of 4-bromo-aniline (6.3g, 63.7mmol) in concentrated solution, with the addition of acetyl chloride (3.75g, 47.7mmol) and TEA the (7.4g, 73.4mmol) at 0 , 2 hours with stirring did. The reaction mixture was washed with water, brine, dried over Na2SO4, filtered and concentrated in vacuo to give the title compound 0601-150 as a brown solid (3.6g, 46%).
46% With triethylamine; In dichloromethane; at 0℃; for 2h; To the solution of 4-bromoaniline (6.3 g, 63.7mmol) in CH2C12 (50 mL) was addedacetyl chloride (3.75 g, 47.7 mmol) and TEA (7.4 g, 73.4 mmol) at 0 C, stirred for 2hours. The reaction mixture was washed with water, brine, dried over Na2SO4, filtered, and concentrated under reduced pressure to give the title compound 0601-150 (3.6 g, 46%) as a brown solid. LCMS: 214 [M+lf?; ?H NMR (400 MI-Tz, DMSO-d6). 2.05 (s, 3H), 7.46 (d, J 8.8 Hz, 2H), 7.57 (d, J 8.8 Hz, 2H), 10.12 (s, 1H).
46% With triethylamine; In dichloromethane; at 0℃; for 2h; To the solution of 4-bromoaniline (6.3 g, 63.7 mmol) in CH2Cl2 (50 mL) was added acetyl chloride (3.75 g, 47.7 mmol) and TEA (7.4 g, 73.4 mmol) at 0 C., stirred for 2 hours. The reaction mixture was washed with water, brine, dried over Na2SO4, filtered, and concentrated under reduced pressure to give the title compound 0601-150 (3.6 g, 46%) as a brown solid. LCMS: 214 [M+1]+1H NMR (400 MHz, DMSO-d6). delta 2.05 (s, 3H), 7.46 (d, J=8.8 Hz, 2H), 7.57 (d, J=8.8 Hz, 2H), 10.12 (s, 1H).
With triethylamine; In dichloromethane; at 20℃; General procedure: 1.607g was added to a 100mL round bottom flask with a magnetic stir bar.15.0 mmol of toluidine, 50.0 mL of CH 2 Cl 2 and 4.170 mL, 30.0 mmol of Et 3 N,Finally, 1.273 mL, 18.0 mmol of acetyl chloride was added, and the reaction mixture was stirred at room temperature with a magnetic stirrer;TLC showed that after the consumption of p-toluidine was completed, the reaction was quenched with 100 mL of saturated NaHCO3 solution.It was then extracted 3 times with 100.0 mL of CH 2 Cl 2 and the combined organic phases were washed twice with 50 mL of brine.The solid obtained by distilling off the organic solvent was washed with a 5:1 mixture of petroleum ether/ethyl acetate to give a white solid p-methylacetanilide;
5.8 g With triethylamine; In dichloromethane; at 20℃;Cooling with ice; Inert atmosphere; 4-Bromoaniline (5.0 g, 29.1 mmol, CAS: 106-40-1) was dissolved in 80 mL of dichloromethane and 8.1 mL of triethylamine was added. After cooling in an ice water bath, acetyl chloride (2.74 g, 34.9 mmol) was slowly added dropwise under the protection of argon. After the addition was completed, the mixture was allowed to warm to room temperature and stirred overnight.Add 80 mL of water, extract three times with DCM, combine the organic phases, and wash three times with saturated brine.Dry over anhydrous sodium sulfate and remove the solvent by rotary evaporation in vacuo.Purification by silica gel column chromatography gave Intermediate E23-1 (5.8 g).

Reference: [1]Patent: EP1970377,2008,A1.Location in patent: Page/Page column 39
[2]Patent: WO2015/6100,2015,A1.Location in patent: Page/Page column 183
[3]Journal of the Iranian Chemical Society,2016,vol. 13,p. 231 - 241
[4]European Journal of Medicinal Chemistry,2018,vol. 158,p. 593 - 619
[5]Journal of Medicinal Chemistry,2014,vol. 57,p. 6642 - 6652
[6]Research on Chemical Intermediates,2012,vol. 38,p. 77 - 89
[7]Patent: WO2011/130628,2011,A1.Location in patent: Page/Page column 193
[8]Patent: US2013/102595,2013,A1.Location in patent: Paragraph 0433; 0434
[9]Patent: JP2015/187145,2015,A.Location in patent: Paragraph 0375
[10]Patent: WO2018/85342,2018,A1.Location in patent: Page/Page column 39
[11]Patent: US2020/78364,2020,A1.Location in patent: Paragraph 0128
[12]Gazzetta Chimica Italiana,1874,vol. 4,p. 341
    Jahresbericht ueber die Fortschritte der Chemie und Verwandter Theile Anderer Wissenschaften,1875,p. 317
[13]Organic Letters,2003,vol. 5,p. 1265 - 1267
[14]Organic Letters,2010,vol. 12,p. 1212 - 1215
[15]Advanced Synthesis and Catalysis,2010,vol. 352,p. 632 - 636
[16]Synlett,2012,vol. 23,p. 2749 - 2752
[17]Advanced Synthesis and Catalysis,2014,vol. 356,p. 3325 - 3330
[18]Organic Letters,2017,vol. 19,p. 2006 - 2009
[19]Journal of Organic Chemistry,2018,vol. 83,p. 11978 - 11986
[20]Patent: CN109081800,2018,A.Location in patent: Paragraph 0027; 0029; 0030; 0031; 0042
[21]Chemical Communications,2019,vol. 55,p. 5475 - 5478
[22]Patent: CN110041333,2019,A.Location in patent: Paragraph 0236-0239
  • 8
  • [ 59862-55-4 ]
  • [ 103-88-8 ]
YieldReaction ConditionsOperation in experiment
89% With oxalyl dichloride; at 0 - 20℃; for 2h; General procedure: Polystyrene-supported phosphine oxide (10.4 mg, 2.5 mol%), (E)-1-Phenylethan-1-one oxime 1a (67.5 mg, 0.5 mmol) and HFIP (2 mL) were added to a 10-mL glass vessel containing a magnetic stirring bar. Then, oxalyl chloride (64.8 mg, 0.5 mmol) was added at 0 C. The mixture was stirred at room temperature for 2 h. After completion of the reaction (indicated by TLC), the catalyst was removed by filtration and the solvent was removed under reduced pressure. The crude material was purified by silica gel column using PE/EtOAc as the eluent to afford the desired product 2a in 99% yield.
88% With titanium cation-exchanged montmorillonite; In benzonitrile; at 90℃; for 18h;Inert atmosphere; General procedure: A typical procedure for the Beckmann rearrangement of 1 by Ti4+-mont is as follows. Ti4+-mont (0.10 g) was placed in a reaction vessel, followed by addition of benzonitrile (5 mL) and 1 (1 mmol). The reaction mixture was vigorously stirred at 90 C under Ar for 3 h. After the reaction, the mixture was centrifuged, and the supernatant was analyzed by GC with naphthalene as an internal standard to determine the conversion and yield.
86% With carbon tetrabromide; Eosin Y; N,N-dimethyl-formamide; In acetonitrile; at 20℃; for 16h;Irradiation; Inert atmosphere; Green chemistry; General procedure: A mixture of ketoxime 1 (1.0 mmol), CBr4 (2.0 equiv), eosin Y (2 mol%), DMF (20 mol%) and MeCN (3 mL) was taken in a hot oven dried round bottom flask and irradiated with green LEDs under a nitrogen atmosphere. After completion of the reaction as indicated by TLC, it was quenched with saturated aqueous sodium hydrogen carbonate (10 mL) and extracted with ethyl acetate (3 × 10 mL). The organic phase was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to yield the crude product, which was purified by silica gel column chromatography (EtOAc-hexane) to give the corresponding amide 2 in high yield. All the products are known compounds and were characterized by comparison of their mp, TLC, 1HNMR, 13C NMR and MS data with authentic samples obtained commercially or prepared byliterature methods.
72% With iron(III) chloride; silver hexafluoroantimonate; In 1,2-dichloro-ethane; at 80℃; for 24h; General procedure: To an oven-dried 20 mL vial containing FeCl3 (24.3 mg,0.15 equiv), was added a solution of oxime (1 mmol) in DCE (10mL) and the mixture was stirred until FeCl3 was completely dissolved(10-15 min). To this solution was added AgSbF6 (154.6mg, 0.45 equiv), then the vial was capped and put into mechanicalshaker at 80 C for 24 h. The mixture was filtered throughCelite with CH2Cl2 (100 mL) and concentrated to give a residue,which was purified by silica flash chromatography usinghexanes and ethyl acetate in appropriate combination based onthe Rf of the desired product.
With 7,7-dichlorocyclohepta-1,3,5-triene; In acetonitrile; at 80℃;Schlenk technique; Inert atmosphere; In a 50 ml three neck round bottom flask,After adding 0.214 g of p-bromoacetophenone oxime and 8 mg of 1,1-dichloroheptatriene,Even a ball condenser,On schlenk,Suction and ventilation 3 times,N2 system to maintain the atmosphere,Then 10 ml of acetonitrile was added,Stirring and heating to 80 reflux reaction,The reaction was followed by liquid chromatography (after the sample was added a small amount of acetic acid in the sampleEster dilution):3h when the conversion of raw materials 22%24h fully converted raw materials,Acetylacetophenone target product selectivity of> 98%.After the reaction was completed, the solvent was distilled off under reduced pressure,By rapid preparative chromatography,Pure acetyl p-methylaniline was obtained,White solid.

Historical Records

Related Functional Groups of
[ 103-88-8 ]

Bromides

Chemical Structure| 621-38-5

[ 621-38-5 ]

3-Bromoacetanilide

Similarity: 0.97

Chemical Structure| 119430-40-9

[ 119430-40-9 ]

N-(3,5-Dibromophenyl)acetamide

Similarity: 0.95

Chemical Structure| 50438-47-6

[ 50438-47-6 ]

N-(4-Bromophenyl)-N-methylacetamide

Similarity: 0.92

Chemical Structure| 614-76-6

[ 614-76-6 ]

2-BroMoacetanilide

Similarity: 0.92

Chemical Structure| 25462-66-2

[ 25462-66-2 ]

N-(2,5-Dibromophenyl)acetamide

Similarity: 0.90

Amines

Chemical Structure| 621-38-5

[ 621-38-5 ]

3-Bromoacetanilide

Similarity: 0.97

Chemical Structure| 119430-40-9

[ 119430-40-9 ]

N-(3,5-Dibromophenyl)acetamide

Similarity: 0.95

Chemical Structure| 50438-47-6

[ 50438-47-6 ]

N-(4-Bromophenyl)-N-methylacetamide

Similarity: 0.92

Chemical Structure| 614-76-6

[ 614-76-6 ]

2-BroMoacetanilide

Similarity: 0.92

Chemical Structure| 25462-66-2

[ 25462-66-2 ]

N-(2,5-Dibromophenyl)acetamide

Similarity: 0.90

Aryls

Chemical Structure| 621-38-5

[ 621-38-5 ]

3-Bromoacetanilide

Similarity: 0.97

Chemical Structure| 119430-40-9

[ 119430-40-9 ]

N-(3,5-Dibromophenyl)acetamide

Similarity: 0.95

Chemical Structure| 50438-47-6

[ 50438-47-6 ]

N-(4-Bromophenyl)-N-methylacetamide

Similarity: 0.92

Chemical Structure| 614-76-6

[ 614-76-6 ]

2-BroMoacetanilide

Similarity: 0.92

Chemical Structure| 25462-66-2

[ 25462-66-2 ]

N-(2,5-Dibromophenyl)acetamide

Similarity: 0.90

Amides

Chemical Structure| 621-38-5

[ 621-38-5 ]

3-Bromoacetanilide

Similarity: 0.97

Chemical Structure| 119430-40-9

[ 119430-40-9 ]

N-(3,5-Dibromophenyl)acetamide

Similarity: 0.95

Chemical Structure| 50438-47-6

[ 50438-47-6 ]

N-(4-Bromophenyl)-N-methylacetamide

Similarity: 0.92

Chemical Structure| 614-76-6

[ 614-76-6 ]

2-BroMoacetanilide

Similarity: 0.92

Chemical Structure| 25462-66-2

[ 25462-66-2 ]

N-(2,5-Dibromophenyl)acetamide

Similarity: 0.90