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Chemical Structure| 121-71-1
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Product Details of [ 121-71-1 ]

CAS No. :121-71-1 MDL No. :MFCD00002298
Formula : C8H8O2 Boiling Point : -
Linear Structure Formula :- InChI Key :LUJMEECXHPYQOF-UHFFFAOYSA-N
M.W : 136.15 Pubchem ID :8487
Synonyms :
m-Hydroxyacetophenone
Chemical Name :3'-Hydroxyacetophenone

Calculated chemistry of [ 121-71-1 ]      Expand+

Physicochemical Properties

Num. heavy atoms : 10
Num. arom. heavy atoms : 6
Fraction Csp3 : 0.12
Num. rotatable bonds : 1
Num. H-bond acceptors : 2.0
Num. H-bond donors : 1.0
Molar Refractivity : 38.66
TPSA : 37.3 Ų

Pharmacokinetics

GI absorption : High
BBB permeant : Yes
P-gp substrate : No
CYP1A2 inhibitor : Yes
CYP2C19 inhibitor : No
CYP2C9 inhibitor : No
CYP2D6 inhibitor : No
CYP3A4 inhibitor : No
Log Kp (skin permeation) : -6.14 cm/s

Lipophilicity

Log Po/w (iLOGP) : 1.34
Log Po/w (XLOGP3) : 1.39
Log Po/w (WLOGP) : 1.59
Log Po/w (MLOGP) : 1.12
Log Po/w (SILICOS-IT) : 1.68
Consensus Log Po/w : 1.42

Druglikeness

Lipinski : 0.0
Ghose : None
Veber : 0.0
Egan : 0.0
Muegge : 1.0
Bioavailability Score : 0.55

Water Solubility

Log S (ESOL) : -1.94
Solubility : 1.57 mg/ml ; 0.0115 mol/l
Class : Very soluble
Log S (Ali) : -1.78
Solubility : 2.28 mg/ml ; 0.0167 mol/l
Class : Very soluble
Log S (SILICOS-IT) : -2.13
Solubility : 1.02 mg/ml ; 0.00746 mol/l
Class : Soluble

Medicinal Chemistry

PAINS : 0.0 alert
Brenk : 0.0 alert
Leadlikeness : 1.0
Synthetic accessibility : 1.0

Safety of [ 121-71-1 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P280-P305+P351+P338 UN#:N/A
Hazard Statements:H302 Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 121-71-1 ]

* 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 [ 121-71-1 ]
  • Downstream synthetic route of [ 121-71-1 ]

[ 121-71-1 ] Synthesis Path-Upstream   1~77

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Reference: [1] Journal of Natural Products, 1998, vol. 61, # 6, p. 821 - 822
  • 2
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  • [ 100-39-0 ]
  • [ 34068-01-4 ]
YieldReaction ConditionsOperation in experiment
98% With potassium carbonate; potassium iodide In acetone for 24 h; Heating / reflux 3-Hydroxyacetophenone (136.15 g, 1 mol), potassium carbonate (414.63 g, 2 mol), KI (33.2 g, 0.2 mol), and benzyl bromide (171.04 g, 1 mol) were dissolved in acetone and the reaction mixture was refluxed while stirring for 24 hours, followed by washing with brine. The reaction mixture was extracted with ethyl acetate, the extract was dried over anhydrous magnesium sulfate, concentrated, and the resulting residue was purified by column chromatography (ethyl acetate: hexane = 1: 3) to obtain 1-(3-benzyloxyphenyl) ethanone (221.8 g, yield 98 percent) in an oil state. 1H NMR (200MHz, CDC13): No. 7.59-7.53 (m, 2H), 7.44-7.33 (m, 6H) 7.19 (m, 1H), 5.11 (s, 2H), 2.6 (s, 3H).
69% With potassium carbonate; potassium iodide In acetone at 70℃; for 20 h; [00470] To a stirred solution of 3-hydroxy acetophenone (1 g, 7.35 mmol) in acetone (25 mL) under inert atmosphere were added potassium iodide (244.1 mg, 1.47 mmol), potassium carbonate (2.02 g, 14.70 mmol) and benzyl bromide (1.5 g, 8.82 mmol) at RT. The reaction mixture was heated at 70 °C and stirred for 20 h. The progress of the reaction was monitored by TLC. After completion of the reaction, the volatiles were evaporated under reduced pressure and the residue was diluted with water (30 mL) and extracted with EtOAc (2 x 30 mL). The combined organic extracts were washed with water (25 mL), dried over sodium sulfate, filtered and concentrated under reduced pressure to obtain the crude product. The crude product was purified by silica gel column chromatography [Eluent: 7percent EtOAc/Hexanes] to afford l-(3- (benzyloxy)phenyl)ethanone (1.6 g, 69percent) as a colorless liquid. 1H NMR (400 MHz, DMSO-d6): δ 7.55-7.51 (m, 2H), 7.45-7.25 (m, 7H), 5.16 (s, 2H), 2.55 (s, 3H).
51% With potassium carbonate In DMF (N,N-dimethyl-formamide) at 60℃; for 72 h; To a stirred solution of 3'-hydroxyacetophenone (LEQ) and benzyl bromide (1.5 eq) in dry DMF under N2, solid K2CO3 (2 eq) was added in one portion. The reaction mixture was stirred at 60° C for 3 days, then cooled down to room temperature. Most of the DMF was distilled off under reduced pressure. The residue was taken up in EtOAc and washed with 1N HC1, H20, Brine and dried (NA2SO4). Evaporation of the solvent under reduced pressure afforded a brown oil which was about a 1: 1 mixture of the starting material and the desired product. The latter was isolated by chromatography on silica gel (ETOAC/HEXANES, 1 : 1) affording the desired 3'-benzyloxy acetophenone (51percent). See for example: Schmidhammer, H.; Brossi, A. R Org. Chem. 1983, 48, 1469. TLC (silica gel, Ethyl acetate/hexanes 1: 2, vanillin stain): Rf= 0.58, orange brown (Rf starting material= 0.28). APOS;H NMR (CDCL3, 300MHZ) : 7.6-7. 1 (9H, m), 5.11 (2H, s, CH2PH) ; 2.59 (3H, s, CH3).
Reference: [1] Patent: WO2005/100303, 2005, A1, . Location in patent: Page/Page column 45
[2] Patent: US5716984, 1998, A,
[3] Patent: US5817693, 1998, A,
[4] Pesticide Science, 1996, vol. 47, # 2, p. 125 - 130
[5] Chemical and Pharmaceutical Bulletin, 1986, vol. 34, # 2, p. 496 - 507
[6] Australian Journal of Chemistry, 2003, vol. 56, # 5, p. 489 - 498
[7] Journal of Organic Chemistry, 2014, vol. 79, # 15, p. 7122 - 7131
[8] Patent: WO2015/191630, 2015, A1, . Location in patent: Paragraph 00470
[9] Patent: WO2004/48365, 2004, A1, . Location in patent: Page 58
[10] Journal of Organic Chemistry, 1994, vol. 59, # 5, p. 1058 - 1066
[11] Chemical and Pharmaceutical Bulletin, 1999, vol. 47, # 2, p. 226 - 240
[12] Journal of Medicinal Chemistry, 2004, vol. 47, # 1, p. 14 - 17
[13] Bioorganic and Medicinal Chemistry Letters, 2005, vol. 15, # 4, p. 1061 - 1064
[14] Journal of Agricultural and Food Chemistry, 2006, vol. 54, # 24, p. 9135 - 9139
[15] Bioorganic and Medicinal Chemistry Letters, 2008, vol. 18, # 16, p. 4661 - 4665
[16] Journal of Enzyme Inhibition and Medicinal Chemistry, 2011, vol. 26, # 5, p. 643 - 648
[17] Organic Process Research and Development, 2007, vol. 11, # 5, p. 825 - 835
  • 3
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  • [ 34068-01-4 ]
YieldReaction ConditionsOperation in experiment
86% With potassium carbonate; triethylamine In acetone EXAMPLE 1
3-Benzyloxyacetophenone
A mechanically stirred mixture of 1 kg. (7.35 mole) of 3-hydroxyacetophenone, 1.035 kg. (7.5 mole) anhydrous potassium carbonate and 0.945 kg. (7.5 mole) of benzylchloride in 4.1 of acetone was heated at reflux for 24 hours after which 0.1035 kg. (0.75 mole) portion of potassium carbonate and 0.0945 kg. (0.75 mole) portion of benzylchloride were added and refluxing continued.
This addition was repeated after 72 hours of refluxing and refluxing continued for 96 hours.
The reaction was cooled, filtered and the filtrate concentrated on a rotovapor.
The filtrate was then treated with 0.202 kg. (2.0 mole) triethylamine and stirred overnight.
The reaction was diluted with 1 liter ether and filtered.
The filtrate was evaporated and the residue distilled to yield 1.429 kg. (86percent) of the title compound as an oil.
BP 160° C. (0.3 torr).
IR (CHCl3) 1695, 1605, 1595, 1493 and 1433 cm-1.
PMR (CDCl3) δ2.52 (s, CH3), 5.03 (s, CH2) and 7.0-7.7 (m, Ph).
Reference: [1] Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1988, p. 2491 - 2500
[2] Journal of Medicinal Chemistry, 1992, vol. 35, # 16, p. 3045 - 3049
[3] Tetrahedron Letters, 2007, vol. 48, # 26, p. 4627 - 4630
[4] Chemical and Pharmaceutical Bulletin, 1995, vol. 43, # 5, p. 738 - 747
[5] Bioorganic and Medicinal Chemistry, 2005, vol. 13, # 5, p. 1537 - 1544
[6] Journal of the American Chemical Society, 1953, vol. 75, p. 4469,4471
[7] Synthetic Communications, 1994, vol. 24, # 19, p. 2749 - 2756
[8] Patent: WO2006/67416, 2006, A1, . Location in patent: Page/Page column 37
[9] Patent: WO2006/67412, 2006, A1, . Location in patent: Page/Page column 35
[10] Patent: US4360700, 1982, A,
[11] Chemical Biology and Drug Design, 2013, vol. 81, # 4, p. 545 - 552
[12] Patent: US2109458, 1936, ,
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Reference: [1] Journal of the American Chemical Society, 2004, vol. 126, # 23, p. 7359 - 7367
  • 5
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  • [ 7732-18-5 ]
  • [ 584-08-7 ]
  • [ 100-44-7 ]
  • [ 34068-01-4 ]
Reference: [1] Patent: US4404222, 1983, A,
[2] Patent: US4407819, 1983, A,
  • 6
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  • [ 34068-01-4 ]
  • [ 30992-63-3 ]
Reference: [1] Patent: US5248685, 1993, A,
  • 7
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  • [ 100-51-6 ]
  • [ 34068-01-4 ]
Reference: [1] MedChemComm, 2015, vol. 6, # 12, p. 2146 - 2157
  • 8
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  • [ 605-65-2 ]
  • [ 34068-01-4 ]
Reference: [1] Analytical chemistry, 1980, vol. 52, # 12, p. 1815 - 1820
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  • [ 30992-63-3 ]
Reference: [1] Patent: US5248685, 1993, A,
  • 10
  • [ 14452-30-3 ]
  • [ 121-71-1 ]
YieldReaction ConditionsOperation in experiment
95% With water; ethylene glycol; potassium hydroxide; copper dichloride In dimethyl sulfoxide at 120℃; for 24 h; Inert atmosphere General procedure: To a test tube containing a magnetic bar was added aryl halide (1.0 mmol), CuCl2 (13.4 mg, 0.1 mmol), KOH (336 mg, 6.0 mmol), ethylene glycol(12 μL, 0.2 mmol), and DMSO/H2O (1.0 mL/0.5 mL). After flushing with argon, the mixture was stirred in a preheated oil bath at 120 °C for 24 h. After cooled to ambient temperature, the reaction mixture was distributed in aqueous HCl (5 percent) and ethyl acetate. The organic layer was washed with water and brine, dried over anhydrous MgSO4, and concentrated under vacuum. The crude product was further purified by column chromatography (EtOAc/n-Hexane) to provide the phenols.
72% With copper(I) oxide; caesium carbonate; toluene-4-sulfonic acid In water at 140℃; for 24 h; Sealed tube General procedure: A mixture of Cu2O (Sigma-Aldrich, 99.99percent purity, 0.147 mmol), Cs2CO3 (2.94 mmol),distilled water (0.2 mL), aryl halide (1.47 mmol) and p-toluenesulfonic acid (TsOH) solution(0.3 mL, 2.45 mol/dm3) were added to a reaction vial and a screw cap was fitted to it. Thereaction mixture was stirred under air in a closed system at 120 C for 24 h, following whichthe heterogeneous mixture was cooled to room temperature and diluted with dichloromethane.The combined organic extracts were dried with anhydrous Na2SO4 and the solvent wasremoved under reduced pressure. The crude product loaded into the column using minimalamounts of dichloromethane and was purified by silica-gel column chromatography to affordthe N-arylated product. The identity and purity of products was confirmed by 1H and 13CNMR spectroscopic analysis.
Reference: [1] Journal of the American Chemical Society, 2016, vol. 138, # 41, p. 13493 - 13496
[2] Bulletin of the Korean Chemical Society, 2015, vol. 36, # 12, p. 2833 - 2840
[3] European Journal of Organic Chemistry, 2014, vol. 2014, # 2, p. 315 - 318
[4] European Journal of Organic Chemistry, 2014, vol. 2014, # 2, p. 315 - 318
[5] Synlett, 2016, vol. 27, # 12, p. 1814 - 1819
[6] European Journal of Organic Chemistry, 2011, # 36, p. 7288 - 7293
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YieldReaction ConditionsOperation in experiment
88.3%
Stage #1: With sulfuric acid In water at 45 - 50℃; for 0.5 h;
Stage #2: With water; urea; sodium nitrite In water at 0 - 5℃; for 0.5 h;
Stage #3: With sulfuric acid In 5,5-dimethyl-1,3-cyclohexadiene; water at 90℃; for 2 h;
In the reactor,Add 590g of water,270g mass fraction of 98percent concentrated sulfuric acid,135 g (1 mol) of 3-aminoacetophenone prepared by S2 was added thereto at a controlled temperature of 45 to 50 ° C,Insulation stirring 0.5h,Control the temperature at 0 ~ 5 ,Dropping sodium nitrite solution (sodium nitrite 77g and 190g water preparation,The mass fraction is 28.8percentAll drops),After the addition is completed,Add 2.8g of urea,Insulation diazotization reaction 0.5h,After completion of the reaction was added to the reaction solution from xylene,Water and concentrated sulfuric acid mixture of hydrolyzate (380g of xylene, 80g of water and 16g concentrated sulfuric acid),Heated to 90 hydrolysis reaction,Nitrogen release,Reflux 2h,After the completion of the hydrolysis reaction was cooled to 10 ~ 15 ,Insulation stirring 0.5h,filter,Washed,Dried to give pale yellow powder 3-hydroxyacetophenone 120g,The yield was 88.3percentThe tested melting point of 95-98 ;
80%
Stage #1: With sodium nitrite In water at 20℃; Milling; Green chemistry
Stage #2: at 80℃; for 0.5 h; Neutral conditions; Green chemistry
General procedure: Aniline (1mmol, 0.095mL), silica sulfuric acid (0.75g) and sodium nitrite (1.7mmol, 0.12g) were ground in a mortar with a pestle for a few minutes to obtain a homogeneous mixture. Then, four drops of water were gradually added and the mixture was ground for 10min to give phenyl diazonium silica sulfate. Five drops of water were added to phenyl diazonium silica sulfate (1mmol) and the resulting mixture was simply blended and then placed into a covered petri dish. Then, the petri dish was placed in an oven at 60°C for 15min. After that, the reaction mixture was diluted with EtOAc (15mL) and filtered after vigorous stirring. The residue was extracted with EtOAc (2×10mL) and the combined organic layer was dried over anhydrous Na2SO4. The solvent was evaporated under reduced pressure to afford the crude product. Further purification was performed by flash column chromatography and the pure phenol was obtained in 81percent (0.076g).
Reference: [1] Patent: CN106242957, 2016, A, . Location in patent: Paragraph 0030; 0037; 0044
[2] Tetrahedron, 2017, vol. 73, # 49, p. 6954 - 6961
[3] Journal of the Chemical Society, 1936, p. 1649,1651
[4] Journal of the Chemical Society, 1945, p. 646,655
[5] Journal of the American Chemical Society, 1932, vol. 54, p. 1114,1116
[6] Pr.S.Dakota Acad., 1945, vol. 25, p. 64
[7] Journal of the American Chemical Society, 1945, vol. 67, p. 2089,2090
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  • [ 586-37-8 ]
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YieldReaction ConditionsOperation in experiment
76% With 1-N-ferrocenylmethyl benzimidazole tagged polymer In N,N-dimethyl-formamideReflux General procedure: A mixture of aryl methyl ether (1 mmol) and [FemMerBenz]Al2Cl7 (200 mg, 0.96 mol percent) in DMF (5 mL) was refluxed in an oil bath. After completion of the reaction as monitored by the TLC, the reaction mixture was cooled and filtered. The filtrate was poured into water (20 mL) and extracted with ethyl acetate (3 20 mL). The combined organic layers were dried over Na2SO4. Evaporation of the solvent followed by column chromatography over silica gel using ethyl acetate/ petroleum ether (1:4 v/v) afforded pure O-demethylated product, which was characterized by spectral methods.
Reference: [1] Synlett, 2010, # 11, p. 1651 - 1656
[2] Tetrahedron, 2006, vol. 62, # 17, p. 4201 - 4204
[3] Tetrahedron Letters, 2012, vol. 53, # 47, p. 6361 - 6366,6
[4] Journal of Organic Chemistry, 1995, vol. 60, # 3, p. 739 - 741
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YieldReaction ConditionsOperation in experiment
92% With tin(IV) chloride In dichloromethane at 0℃; for 0.0333333 h; General procedure: SnCl4 (10 mol percent) was addedto a stirred solution of THP/MOM ethers (1 mmol) in CH2Cl2 (5 mL) at 0 C. TLCmonitoring, the reaction mixture was poured into 10percent aqueous Na2CO3solution and extracted with CH2Cl2. The combined organic layer was washedwith brine solution, dried with anhyd. Na2SO4 and concentrated in vacuo toafford the corresponding alcohol or phenol, which was purified by silica gelcolumn chromatography with hexane–EtOAc eluent to obtain the products 1–19 in excellent yield (90–98percent).
Reference: [1] Tetrahedron Letters, 2014, vol. 55, # 27, p. 3683 - 3687
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  • [ 121-71-1 ]
YieldReaction ConditionsOperation in experiment
90% With tin(IV) chloride In dichloromethane at 0℃; for 0.0333333 h; General procedure: SnCl4 (10 mol percent) was addedto a stirred solution of THP/MOM ethers (1 mmol) in CH2Cl2 (5 mL) at 0 C. TLCmonitoring, the reaction mixture was poured into 10percent aqueous Na2CO3solution and extracted with CH2Cl2. The combined organic layer was washedwith brine solution, dried with anhyd. Na2SO4 and concentrated in vacuo toafford the corresponding alcohol or phenol, which was purified by silica gelcolumn chromatography with hexane–EtOAc eluent to obtain the products 1–19 in excellent yield (90–98percent).
Reference: [1] Tetrahedron Letters, 2014, vol. 55, # 27, p. 3683 - 3687
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Reference: [1] Journal of the American Chemical Society, 2016, vol. 138, # 41, p. 13493 - 13496
[2] Journal of the American Chemical Society, 2006, vol. 128, # 33, p. 10694 - 10695
[3] Angewandte Chemie - International Edition, 2018, vol. 57, # 7, p. 1968 - 1972[4] Angew. Chem., 2018, vol. 130, p. 1986 - 1990,5
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YieldReaction ConditionsOperation in experiment
99% at 200 - 220℃; for 0.5 h; Microwave irradiation; Inert atmosphere General procedure: To a microwave tube was added alkyl aryl ether (1.0 mmol) and 1-n-butyl-3-methylimidazolium bromide (0.65 g, 3.0 mmol). The reaction tube was flushed with argon and then was irradiated at 20 W for the designated time period with air-flow cooling to prevent overheating (power control mode). After cooled to room temperature, the reaction mixture was acidified with 1 NHCl solution and extracted with ethyl acetate (3 × 15 mL). The combined organic layer was washed with water and brine, and dried over anhydrous MgSO4 and the solvent was evaporated under vacuum. Purification of the crude product by column chromatography (ethyl acetate in n-hexane)afforded the desired product.
Reference: [1] Bulletin of the Korean Chemical Society, 2013, vol. 34, # 1, p. 174 - 178
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Reference: [1] Journal of the American Chemical Society, 2016, vol. 138, # 41, p. 13493 - 13496
[2] Organic Letters, 2012, vol. 14, # 14, p. 3688 - 3691
[3] Angewandte Chemie - International Edition, 2018, vol. 57, # 7, p. 1968 - 1972[4] Angew. Chem., 2018, vol. 130, p. 1986 - 1990,5
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YieldReaction ConditionsOperation in experiment
42% With Candida albicans CCT 0776 In water at 30℃; for 144 h; Resolution of racemate; Enzymatic reaction General procedure: On a preparative scale, 200mg of substrate were added to a 250mL Erlenmeyer flask containing 45g of C. albicans in beads in 40mL of water. After 45min (complete kinetic resolution), the beads were removed and rinsed with ether, after which 12g of L. brevis wet cells were added to the remaining liquid phase. The crude reaction was extracted with ethyl acetate (three times), and the organic layer was dried over anhydrous sodium sulfate. The solvent was removed by rotary evaporator, and the product was obtained after purification by silica gel chromatography using hexane/ethyl acetate as the mobile phase. White solid. Mp: 117–119°C; 87percent yield. MS m/z (rel. intensity percent): 138 (M+, 51), 123 (48), 120 (15), 95 (100), 77 (41), 65 (15), 43 (17). 1H NMR (500MHz, DMSO-d6) δδ=1.28 (d, J=6.5Hz, 3H), 4.62 (q, J=6.5Hz, 1H), 5.05 (s, 1H), 6.59–6.61 (m, 1H), 6.73–7.77 (m, 2H), 7.09 (t, J=7.5Hz, 1H), 9.24 (s, 1H). 13C NMR (125MHz, DMSO-d6) δδ=26.42, 68.49, 112.65, 113.83, 116.42, 129.35, 149.49, 157.63. [α]20D=+32[α]D20=+32 (c 1.0, MeOH) 99percent ee. The ee was determined by HPLC analysis (eluent hexane/2-propanol 98:2, flow rate 0.5mLmin−1) with a 215nm UV detector tR=10.49min [(R)-enantiomer]; tS=12.49min [(S)-enantiomer]
Reference: [1] Tetrahedron Asymmetry, 2016, vol. 27, # 9-10, p. 404 - 409
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Reference: [1] Journal of Organic Chemistry, 2009, vol. 74, # 4, p. 1781 - 1784
[2] Tetrahedron Letters, 1996, vol. 37, # 2, p. 153 - 156
[3] Tetrahedron Letters, 1991, vol. 32, # 49, p. 7207 - 7210
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  • [ 118-93-4 ]
  • [ 99-93-4 ]
YieldReaction ConditionsOperation in experiment
38% With (difluoroboryl)dimethylglyoximatocobalt(II) bis(acetonitrile); water; 3-cyano-1-methylquinolinium cation In acetonitrile at 20℃; for 5 h; Inert atmosphere; Irradiation; Green chemistry 1-methyl-3-cyanoquinoline salt as a photosensitizer, Cobalt oxime complex 2 as a cobalt catalyst, 5mL of acetonitrile was added 2.69 mg (1 × 10 -2 mmol) photosensitizer and 2.80 mg (6 × 10 -3 mmol) cobalt catalyst, Replacing the atmosphere with Ar atmosphere And then Add 0.2 mmol of acetophenone (R1 is COCH3, R2, R3, R4 are independently H) and 2 mmo 1 H20.. Room temperature, high pressure mercury lamp irradiation5h. After the reaction was completed, the H2 production was detected by GC (TCD) and the conversion of benzene by GC (FID), And then separated by column. Nuclear magnetic hydrogen Spectrum and mass spectrometry identified the product as 2'- hydroxyacetophenone, 3-hydroxyacetophenone and 4-hydroxyacetophenone. Acetophenone conversion is 58percent, Yields of 2'-hydroxyacetophenone, 3-hydroxyacetophenone and 4-hydroxyacetophenone were 38percent, 6percent and 14percent, respectively The rate is 56percent
Reference: [1] Patent: CN107324975, 2017, A, . Location in patent: Paragraph 0112-0113
[2] Journal of Physical Chemistry A, 1997, vol. 101, # 45, p. 8402 - 8408
[3] Tetrahedron Letters, 2005, vol. 46, # 45, p. 7729 - 7732
[4] Chemical Communications, 2006, # 9, p. 1012 - 1014
[5] Chemistry - A European Journal, 2010, vol. 16, # 47, p. 13995 - 14006
[6] Chinese Journal of Catalysis, 2015, vol. 36, # 7, p. 1086 - 1092
[7] Journal of the American Chemical Society, 2016, vol. 138, # 32, p. 10080 - 10083
[8] Catalysis Letters, 2015, vol. 145, # 4, p. 1014 - 1021
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YieldReaction ConditionsOperation in experiment
71% at 95℃; for 24 h; Schlenk technique General procedure: Ferric sulfate hydrate (I, 8 molpercent), glacial acetic acid (5 mL) and the alkyne (1 - 2 mmol) were introducedinto a 50 mL Schlenk tube, equipped with an air condenser, and the mixture kept under stirring at 95 °C or120 °C, until consumption of the substrate or no further conversion, as evidenced by TLC or GC. Uponcooling, the supernatant solution was poored into water and the residue washed twice with diethyl ether.After extraction with diethyl ether ( 2), the combined organic layers were washed with a saturated aqueoussolution of sodium bicarbonate and then water until neutrality. Alternatively, the crude from the reactions ofsubstrates featuring hydroxyl or carbonyl groups, as for 12, 15, 20 and 22, was obtained by removing aceticacid under vacuum, in order to reduce loss of material during biphasic extraction. The products were purified
Reference: [1] Tetrahedron Letters, 2014, vol. 55, # 9, p. 1608 - 1612
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Reference: [1] Synthetic Communications, 2009, vol. 39, # 11, p. 1949 - 1956
[2] Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 2007, vol. 46, # 11, p. 1893 - 1895
[3] Bulletin des Societes Chimiques Belges, 1952, vol. 6, p. 599,605
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Reference: [1] Angewandte Chemie - International Edition, 2013, vol. 52, # 13, p. 3672 - 3675[2] Angew. Chem., 2013, vol. 125, # 13, p. 3760 - 3763,4
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  • [ 99-06-9 ]
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  • [ 7765-97-1 ]
Reference: [1] Journal of Organic Chemistry, 1983, vol. 48, # 9, p. 1550 - 1552
[2] Journal of Organic Chemistry, 1983, vol. 48, # 9, p. 1550 - 1552
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Reference: [1] Synlett, 2004, # 4, p. 631 - 634
[2] European Journal of Organic Chemistry, 2018, vol. 2018, # 29, p. 3974 - 3981
[3] Organic Letters, 2016, vol. 18, # 9, p. 2184 - 2187
[4] Tetrahedron Letters, 2013, vol. 54, # 33, p. 4414 - 4417
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YieldReaction ConditionsOperation in experiment
18 %Chromat.
Stage #1: With ferredoxin reductase; ferredoxin; 4-methylphenyl phosphate synthase; P450 monooxygenase; nicotinamide adenine dinucleotide phosphate; nicotinamide adenine dinucleotide; ATP; magnesium chloride; manganese(ll) chloride; alcohol dehydrogenase; aldehyde dehydrogenase In aq. buffer at 30℃; for 2 h; Enzymatic reaction
Stage #2: With phosphohydrolase In aq. buffer at 30℃; for 2 h; Enzymatic reaction
General procedure: Unless specified otherwise, all enzymatic assays were carriedout in 100 μL of 50 mM Tris·HCl buffer (pH 8.0) at 30 °C for 2 h, and thefinal concentration of each enzyme was 10 μM. Methanol (3× volume) wasadded to quench reactions. Precipitated proteins were removed by centrifugationat 20,000 × g for 10 min and the supernatants were used as LC-MSsamples. For reactions catalyzed by CreHI, the reaction mixture contained1 mM substrate, 20 mM MgCl2, 2 mM MnCl2, 2 mM ATP, and purified CreHand CreI. For CreJEF activity toward phosphorylated compounds (2′–9′), theCreHI reactions were used to generate the phosphorylated substrates. Next,CreJ, CreE, and CreF together with 3 mM NADPH were added into the individualpost-CreHI reaction mixture.For one-pot chemomimetic alkylphenol oxidation reactions, the reactionmixtures contained CreHI, CreJEF, and the two optional enzymes CreG (with2 mM NAD+) and CreC (with 2 mM NADP+), 1 mM substrate 2–7, and necessarycofactors, including 20 mM MgCl2, 2 mM MnCl2, 2 mM ATP, and 3 mMNADPH. After incubation at 30 °C for 2 h, CreD was added into each of theone-pot mixtures, followed by another 2-h incubation at 30 °C.
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[4] Patent: CN106242957, 2016, A,
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YieldReaction ConditionsOperation in experiment
43.9% at 0 - 20℃; for 18 h; Inert atmosphere EXAMPLE 65[0285] This example describes the synthesis of 3-(2-hydroxypropan-2-yl)phenol, which is an intermediate of a compound of Formula (I), in an embodiment of the invention.[0286] To a solution of l-(3-hydroxyphenyl)ethanone (7.4 g, 54 mmol) in anhydrous THF (300 niL) at 0 0C was added a solution of methyl magnesium chloride (40 mL, 119 mmol) in THF slowly through a syringe under nitrogen. The reaction mixture was stirred at room temperature for 18 h. Thin layer chromatography (TLC) indicated about 30percent of starting material remained. The reaction mixture was refluxed for 2 h and TLC indicated most of starting material was consumed. The reaction mixture was cooled to 0 0C and quenched with saturated aqueous NH4Cl (2OmL), followed by IM HCl (12OmL). The aqueous solution was extracted with EtOAc (50mLχ3). The combined organic phase was washed with brine (200mLχ2), dried over Na2SO4, concentrated under reduced pressure, and purified by silica gel column chromatography using ethyl acetate/petrol ether (10percent to about 25percent) as eluant to obtain (3.6 g, 43.9percent) as a yellow solid. 1H NMR: δ 1.59(s, 3H), 6.74- 6.76(m, J=8Hz, IH), 6.99-7.01(d, J=8Hz, IH), 7.08(d, J=2Hz, IH), 7.20-7.24(m, J=16Hz, IH).
Reference: [1] Patent: WO2010/120698, 2010, A1, . Location in patent: Page/Page column 86-87
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[2] Journal of Organic Chemistry, 1983, vol. 48, # 9, p. 1550 - 1552
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Reference: [1] Patent: US4460800, 1984, A,
[2] Patent: US4460800, 1984, A,
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[2] Journal of the American Chemical Society, 2006, vol. 128, # 24, p. 8087 - 8094
[3] Tetrahedron, 2007, vol. 63, # 23, p. 4990 - 4999
[4] Chemische Berichte, 1957, vol. 90, p. 1120,1124
[5] Chemische Berichte, 1961, vol. 94, p. 26 - 38
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[2] Bioorganic and Medicinal Chemistry Letters, 2010, vol. 20, # 22, p. 6840 - 6844
[3] Bioorganic and Medicinal Chemistry, 2002, vol. 10, # 3, p. 675 - 683
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YieldReaction ConditionsOperation in experiment
83% at 0 - 20℃; for 1.5 h; General procedure: To a solution of 4’-methoxypropiophenone (328 mg, 2.0 mmol) in ethanol/triethyl orthoformate (2 mL/8 mL) was added 70percent perchloric acid (173 μL, 2.0 mmol), followed by addition of thallium(III) p-tosylate (1.44 g, 2.0 mmol) at 0 °C. The reaction mixture was stirred for 1.5 h between 0 °C and room temperature. The solvents were evaporated off under reduced pressure, and the residue was dissolved in methylene chloride (20 mL). The white precipitate was filtered off, and the resulting yellow solution was poured into saturated NaHCO3 solution (30 mL) and extracted with methylene chloride (3 × 20 mL). The combined organic layers were dried over anhydrous MgSO4, filtered, and concentrated in vacuo. The residue was purified by vacuum distillation using a Kugelrohr apparatus to give 4g (391 mg, 94percent) as a colorless liquid.
Reference: [1] Journal of the Korean Chemical Society, 2017, vol. 61, # 3, p. 125 - 128
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Reference: [1] Patent: CN105461655, 2016, A, . Location in patent: Paragraph 0031; 0032
  • 72
  • [ 121-71-1 ]
  • [ 506-59-2 ]
  • [ 105601-04-5 ]
YieldReaction ConditionsOperation in experiment
56%
Stage #1: With magnesium sulfate In methanolMolecular sieve; Reflux
Stage #2: With sodium cyanoborohydride In methanolReflux
A mixture of 27.23 gram 3-hydroxyacetophenone (0.2 mol), 3.60 gram dimethylamine hydrochloride (0.4 mol), 10 gram activated molecular sieve (3A) and 10 gram dry MgSO4 is refluxed in dry methanol for 1-2 hours. Then, 18.85 gram NaCNBH3 is added to reaction mixture and the mixture is refluxed for additional 18-20 hours. After hot filtration of reaction mixture, methanol is distilled out under vacuum and the residue thus obtained is dissolved in water (250 mL). The content is acidified with conc. HCI to pH 1 and extracted with ethyl acetate (3x100 mL). The aqueous solution is basified to pH 8-9 using NaHCO3() and extracted with ethyl acetate (5x100 mL). Combined ethyl acetate extracts are washed with water dried over MgSO4 and concentrated under reduced pressure to give thick oil. This oil is dissolved in isopropyl ether (120 mL) under heating and allowed to cool to 0 °C. The crystalline solid obtained is filtered at the Buchner funnel under vacuum and dried in oven at 60°C to give the product as a light yellow crystalline solid. Yield obtained: 56.0percent. Purity by HPLC: 99percent. Mass spectrometry: peak at mlz 166 (M+1). 1H-NMR data in CD3OD: ö 1.34 (d, 3H), 2.17 (s, 6H), 3.22 (q, IH), 6.63-6.68 (m, IH), 6.69-6.79 (m, 2H), 7.10 (t, IH).
56%
Stage #1: With magnesium sulfate In methanolMolecular sieve; Reflux
Stage #2: With sodium cyanoborohydride In methanol for 17 h; Reflux
A mixture of 27.23 g 3-hydroxyacetophenone (0.2 mol) (1),3.60 g dimethylamine hydrochloride (0.4 mol), 10 g activatedmolecular sieve (3 Å) and 10 g dry MgSO4 was refluxed in drymethanol for 1–2 h. Then, 18.85 g NaCNBH3 was added to reactionmixture and the mixture was refluxed for additional 18–20 h. Afterhot filtration of reaction mixture, methanol was removed underreduced pressure and the residue thus obtained was dissolved inwater (250 mL). The content was acidified with concd HCl to pH1 and extracted with ethyl acetate (3 100 mL). The aqueous solutionwas basified to pH 8–9 using NaHCO3(s) (i.e., solid NaHCO3)and extracted with ethyl acetate (5 100 mL). Combined ethylacetate extracts were washed with water dried over MgSO4 andconcentrated under reduced pressure to give thick oil. This oilwas dissolved in isopropyl ether (120 mL) under heating andallowed to cool to 0 C. The crystalline solid obtained was filteredand dried to obtain a light yellow crystalline solid. Yield obtained:56.0percent. Purity by HPLC: 99percent. Mass spectrometry: peak at m/z 166(M+1)+. 1H NMR data in CD3OD: d 1.34 (d, 3H, ACHACH3), 2.17(s, 6H, CH3ANACH3), 3.22 (q, 1H, ANACHACH3), 6.63–6.68 (m,1H, Ar-H), 6.69–6.79 (m, 2H, Ar-H), 7.10 (t, 1H, Ar-H).
Reference: [1] Patent: WO2014/129990, 2014, A1, . Location in patent: Page/Page column 8; 9
[2] Bioorganic and Medicinal Chemistry, 2014, vol. 22, # 19, p. 5141 - 5154
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Reference: [1] Patent: CN107417574, 2017, A,
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[2] Chemistry Letters, 2017, vol. 46, # 5, p. 740 - 743
[3] Chemistry Letters, 2017, vol. 46, # 5, p. 740 - 743
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Reference: [1] Patent: EP2927218, 2015, A1, . Location in patent: Paragraph 0849
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Reference: [1] Pesticide Science, 1998, vol. 54, # 3, p. 223 - 229
  • 77
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YieldReaction ConditionsOperation in experiment
100% With potassium carbonate In acetone at 20 - 55℃; for 5 h; Heating / reflux 3-O- ( (N-ethyl, methyl) carbamoyl) acetophenone (7); Acetone (1000ml) was charged in a flask equipped with a reflux condenser and mechanical stirrer. 3'-Hydroxyacetophenone (G) (125g, 0. 919mol) was added with stirring at ambient temperature. This gave a yellow clear coloured solution. Potassium carbonate (381g, 2. 757mol, 3eq) was added in one lot followed by addition of ethyl methyl carbamoyl chloride (EMCC, 167.5g, 1 : 379mol, 1. 5eq) also in one lot. Acetone (250ml) used to rinse the addition funnel was added to the reaction. The reaction mixture was then heated to reflux (55°C). After 4 hours, potassium carbonate (25.5g, 0. 18mol, 0. 2eq) was added in one lot followed by acetone (92ml, 0.74 volumes). One hour after this addition, potassium carbonate (12.75g, 0. 09mol, 0. leg) was added in one lot. The reaction mass was allowed to cool to about 35°C and filtered though a sintered funnel under vacuum. The solid was discarded and the mother liquor was concentrated to obtain crude ketone (7) as a red coloured liquid. Yield: 229g, 112.74percent. HPLC purity: 96.71percent. Sulphated ash: 0. 4percent.'H NMR: 8 1.41-1. 56 (2 x t, 3H, N-CH2CH3), otilde; 2.6 (s, 3H, COCH3), 8 3.00 and 3.09 (2 x s, 3H, N-CH3), 8 3.38-3. 53 (2 x q, 2H, N-CH2CH3), 8 7.32 (d, 1H, Ar-H), 8 7.46 (t, 1H, Ar- H), 8 7.69 (s, 1H, Ar-H), 8 7.78 (d, 1H, At-H).
100% With potassium carbonate In acetone for 4 h; Reflux To a solution of compound 1 (5.11 g, 38 mmol) in acetone (100 mL) was added K2CO3 (10.44 g,76 mmol) and compound 2 (7.20 g, 58 mmol) subsequently. Then the solution was heated to reflux for4h. After the reaction solution was cooled to r.t., it was filtered and washed with acetone (30 mL 3).Then the filtrate was concentrated under reduced pressure and purified via column chromatography(CH2Cl2/MeOH = 40:1 to 20:1 v/v) to afford light yellow oil (Yield: 100percent). 1H-NMR (500 MHz,Chloroform-d): 7.79 (d, J = 8.0 Hz, 1H, Ar-H), 7.69 (s, 1H, Ar-H), 7.47 (t, J = 7.5 Hz, 1H, Ar–H), 7.3 (d,J = 2.5 Hz, 1H, Ar–H), 3.50 (dq, J = 7.5, 14.5 Hz, 2H, –CH2CH3), 3.08 (d, J = 42.5 Hz, 3H, –NCH3),2.59 (s, 3H, –COCH3), 1.27 (dt, J = 7.0 Hz, J = 7.0 Hz, 3H, –CH2CH3).
99% at 95℃; To a solution of triethyl amine (910 mL, 4.55 vol) was added, N-ethyl-N-methyl carbomyl chloride (182 g, 1.5 mol) and 3-hydroxy acetophenone (200 g, 1.47 mol). The mixture was stirred at 95 °C for 10-15 h. The reaction mixture was extracted with CH2Cl2 (1000 mL), washed with 0.5 N sodium hydroxide solution (2× 2000 mL), dried over Na2SO4 and distilled under vacuum to obtain product as brownish color. The product was analyzed by HPLC, ESI-MS and 1H NMR oil (321.74 g 99percent isolated yield, purity >98percent, bp 337.9 °C) ESI-MS found 221.1 (M+). 1H NMR (CDCl3, 300 MHz, ppm) δ 7.80-7.67 (m, 1H), 7.69 (s, 1H), 7.48-7.42 (m, 1H), 7.35-7.27 (m, 1H), 3.52-3.38 (m, 2H), 3.08-3.00 (s, 3H, 2 rotamers), 2.60 (s, 3H), 1.28-1.13 (m, 3H).
99% at 95℃; for 15 h; General procedure: To a solution of triethyl amine (910mL, 4.55 vol) were added N-ethyl methyl carbomyl chloride (182g, 1.5mol) and 3-hydroxy acetophenone (200g, 1.47mol). The mixture was then stirred at 95°C for 10–15h. The reaction mixture was extracted with CH2Cl2 (1000mL), washed with 0.5M NaOH solution (2×2000mL), dried over Na2SO4, and distilled under vacuum to obtain a brown oil (321.74g 99percent isolated yield) ESI-MS found 221.1 (M+). 1H NMR (CDCl3, 300MHz, ppm) δ 7.80–7.67 (m, 1H), 7.69 (s, 1H), 7.48–7.42 (m, 1H), 7.35–7.27 (m, 1H), 3.52–3.38 (m, 2H), 3.08–3.00 (d, J=25.5Hz, 3H), 2.60 (s, 3H), 1.28–1.13 (m, 3H). 1H NMR data are in good greement with those reported in literature.20
90% With potassium carbonate In acetone at 60℃; for 12 h; Weigh accurately about 10g 7.4mmol 3-hydroxyacetophenone, dissolved in 180mL acetone solution, Was dissolved with stirring, was added 10.3g of potassium carbonate powder is about 7.6mmol, approximately 8.9g was slowly added dropwise 7.5mmol Of N- methyl, N- ethyl chloride, a small amount of air bubbles, to be stable after the reaction, 60 ° C Back Stream, TLC detection, 12h after the reaction was stopped, cooled, filtered and the filtrate evaporated to dryness and saturated NaHCO3 The solution was diluted with ethyl acetate and the organic phase was extracted, the extract is washed with water, dried over anhydrous sodium sulfate, Filtered and concentrated under reduced pressure to give an oil, to give a colorless oily compound S3717.1g, yield 90percent
89%
Stage #1: With sodium hydride In tetrahydrofuran at 20℃; for 0.333333 h; Inert atmosphere
Stage #2: for 5 h; Inert atmosphere
Sodium hydride (180 mg, 7.5 mmol, prewashed with n-pentane to remove mineral oil) was suspended in dry THF (80 mL). Under a stream of Ar 3'-hydroxyacetophenone (3, 234 mg, 1.7 mmol) was added and the mixture was stirred for 20 min at rt. Ethyl(methyl)carbamic chloride (2, 310 μL, 322 mg, 2.7 mmol) was dissolved in dry THF (20 mL) and added to the reaction mixture, which was stirred for 5 h. The reaction was quenched by addition of NaOH (1.1 M, 40 mL) and extracted with EtOAc (3x 20 mL). The combined organic phase was washed with NaOH (1.1 M, 20 mL), dried over Na2SO4 and concentrated under reduced pressure to give 3-acetylphenyl ethyl(methyl)carbamate (4) as yellow oil (337 mg, 1.52 mmol, 89percent): υmax 2973, 2935, 1716, 1683, 1587, 1476, 1426, 1396, 1357, 1258, 1191, 1151 cm-1; 1H NMR (DMSO) 7.84-7.80 (m, 1H), 7.66 (bs, 1H), 7.54 (t, 1H, J=8.1), 7.42-7.39 (m, 1H), 3.42 (q, 1H, J=6.9, 1 rotamer), 3.32 (q, 1H, J=7.2, 1 rotamer), 3.04 (s, 1.5H, 1 rotamer), 2.91 (s, 1.5H, 1 rotamer), 2.59 (s, 3H), 1.20 (t, 1.5H, J=7.2), 1.11 (t, 1.5H, J=6.9); 13C NMR (DMSO) 197.7, 153.9 (1 rotamer), 153.8 (1 rotamer), 152.0, 138.5, 130.1, 127.3 (1 rotamer), 127.3 (1 rotamer), 125.5, 121.8, 44.0, 34.4 (1 rotamer), 34.1 (1 rotamer), 27.3, 13.5 (1 rotamer), 12.7 (1 rotamer); GC-MS (EI): tret 13.02, m/z (relative intensity [percent]): 221 (8), 121 (5), 95 (4), 86 (100), 58 (54); HRMS (ESI): MH+ found 222.1120, C12H16NO3+ requires 222.1130.
82.8%
Stage #1: for 0.0833333 - 0.166667 h;
Stage #2: at 95℃; for 5 h; Heating / reflux
Stage #3: With sodium hydroxide In dichloromethane; water
3-0- ( (N-ethyl, methyl) carbamoyl) acetopbenone (7); In a clean and dry 21 4-neck flask was charged triethylamine (593ml) and 3'- hydroxyacetophenone (6) (130g). This reaction mixture was stirred for 5-10 minutes to obtain a clear solution. Then ethyl methyl carbamoyl chloride (EMCC, 34.8g) was added. The reaction mixture was heated to reflux (95°C) and maintained at 95°C for 5 hours. After every 1 hour, the progress of the reaction was monitored by TLC and further EMCC (34. 8g) was added. After 5 hours, TLC showed the absence of starting material (6) and the reaction mixture was cooled to 25-30°C. The reaction mixture was filtered through a sintered funnel and the retained solid was washed with triethylamine (25ml). The filtrate was taken up for triethylamine distillation under vacuum at 50°C, remaining traces of triethylamine were removed at high vacuum (lOmbar). DCM (650ml) was added to the oil so obtained. The DCM layer was washed with 10percent NaOH solution (w/v) (2 x 650ml), washed with demineralized water until the pH of the aqueous layer was between 7-8, dried over NazSO4, and concentrated to dryness to obtain the product (7). Yield: 175g, 82. 8percent.

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