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CAS No. :20982-28-9 MDL No. :MFCD16883143
Formula : C11H12O4 Boiling Point : -
Linear Structure Formula :- InChI Key :-
M.W : 208.21 Pubchem ID :-
Synonyms :

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Application In Synthesis of [ 20982-28-9 ]

* 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 [ 20982-28-9 ]

[ 20982-28-9 ] Synthesis Path-Downstream   1~4

  • 1
  • [ 504-15-4 ]
  • [ 108-24-7 ]
  • [ 20982-28-9 ]
YieldReaction ConditionsOperation in experiment
100% at 100℃; for 2.5h; 39.1 Intermediate 395-chloro-7-(6-chloropyrimidin-4-yloxy)-2H-benzo[b][1.4]oxazin-3(4H)-one Step 1: 5-methyl-1,3-phenylene diacetate; 5.80 g (0.04 mol) 5-methylresorcin monohydrate, 20.0 mL (0.21 mol) acetic anhydride and 0.05 g 4-dimethylaminopyridine were stirred in 40.0 mL acetic acid for 2.5 h at 100° C. The reaction mixture was evaporated down i.vac. The residue was taken up in dichloromethane and washed with water. The organic phase was separated off, dried and evaporated down i.vac.Yield: 8.20 g (quantitative)ESI-MS: m/z=209 (M+H)+ Rt(HPLC): 3.79 min (method C)Rf: 0.6 (silica gel: PE/ethyl acetate=2:1)
99% With tin(IV) tetraphenylporphyrin perchlorate at 20℃; for 0.0833333h;
94% With triethylamine In dichloromethane at 0 - 20℃; for 60h; 69 Acetic acid 3-acetoxy-5-methyl-phenyl ester Preparation 69 Acetic acid 3-acetoxy-5-methyl-phenyl ester Acetic anhydride (22.6 mL, 0.24 mol) was added to an ice-cooled solution of 3,5-dihydroxytoluene (9.93 g, 0.08 mol) and triethylamine (56 mL, 0.40 mol) in dichloromethane (86 mL). The reaction mixture was warmed to room temperature and was stirred for 60 hours. Water (100 mL) was then added and the mixture was stirred vigorously for 3 hours. The organic layer was separated and the aqueous layer was re-extracted with dichloromethane (3*80 mL). The combined organic extracts were washed with brine (80 mL), dried over magnesium sulfate and concentrated in vacuo. The residue was purified by column chromatography on silica gel, eluding with ethyl acetate:pentane, 66:33, to afford the title compound as a colourless oil in 94% yield, 15.7 g. LRMS (APCI+): m/z [M+NH4]+ 226
90.5% In pyridine
90% for 12h; Ambient temperature;
With sodium acetate
With pyridine
In pyridine at 20℃; for 16h; 42 2',6'-Dihydroxy-4'-methylacetophenone To a solution of orcinol (30 g) in pyridine (240 mL) was added acetic anhydride (91 mL) at room temperature, and the mixture was stirred for 16 hours. The reaction mixture was concentrated under reduced pressure, and the residue was dissolved in ethyl acetate. The solution was washed with 1 mol/L hydrochloric acid, water, a saturated aqueous sodium hydrogen carbonate solution and brine successively, and dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure to give orcinol diacetate (43.7 g). To a suspension of aluminum chloride (19.3 g) in chlorobenzene (50 mL) was added a solution of orcinol diacetate (10 g) in chlorobenzene (8 mL) in a dropwise manner at 90°C, and the mixture was stirred at the same temperature for 1 hour. The reaction mixture was poured into 0. 5 mol/L hydrochloric acid cooled in ice, and the resulting mixture was stirred for 30 minutes. The mixture was extracted with ethyl acetate, and the extract was washed with water and dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure. To the residue was added n-hexane (100 mL), and the mixture was stirred at room temperature for 30 minutes. The insoluble material was collected by filtration and dried under reduced pressure to give the title compound (7.2 g).1H-NMR (CDCl3) δ ppm: 2.24 (3H, s), 2.7 (3H, s), 6.21 (2H, s), 8.8-9.85 (2H, br)
With triethylamine In dichloromethane at 0 - 20℃; for 50h; Intermediate 155-methylbenzene-l,3-diyl diacetate 5-methyl-l,3-benzenediol (2.0 g, 16.11 mmol) was dissolved in 20.0 ml of dichloromethane and TEA(11.23 ml, 81.0 mmol) was added. Then, at 0QC, acetic anhydride (4.56 ml, 48.30 mmol) was added and the reaction mixture was stirred at room temperature for 50 hours. After the addition of water (20.0 ml) the reaction mixture was stirred for 3 hours. The phases were then separated and the aqueous one was extracted with dichloromethane (2 times). The gathered organic phases were washed with brine, dried over sodium sulphate, filtered and evaporated to afford the title compound (3.33 g).1H-NM (400 MHz, CDCI3): δ ppm 6.83 (2H, br. s), 6.75 (1H, br. s), 2.39 (3H, s), 2.31 (6H, s); UPLC-MS: 0.67 min, 209 [M+H]+.
3.33 g With triethylamine In dichloromethane at 0 - 20℃; for 50h; 15 Intermediate 15 5-methylbenzene-1,3-diyl diacetate Intermediate 15 5-methylbenzene-1,3-diyl diacetate [0522] [0523] 5-methyl-1,3-benzenediol (2.0 g, 16.11 mmol) was dissolved in 20.0 ml of dichloromethane and TEA (11.23 ml, 81.0 mmol) was added. Then, at 0° C., acetic anhydride (4.56 ml, 48.30 mmol) was added and the reaction mixture was stirred at room temperature for 50 hours. After the addition of water (20.0 ml) the reaction mixture was stirred for 3 hours. The phases were then separated and the aqueous one was extracted with dichloromethane (2 times). The gathered organic phases were washed with brine, dried over sodium sulphate, filtered and evaporated to afford the title compound (3.33 g). [0524] 1H-NMR (400 MHz, CDCl3): δ ppm 6.83 (2H, br. s), 6.75 (1H, br. s), 2.39 (3H, s), 2.31 (6H, s); UPLC-MS: 0.67 min, 209 [M+H]+.
1.2 mg With pyridine at 20℃; for 24h; 1,3-O,O′-Diacetylorcinol (4). Orcinol (2, 1.4 mg), dissolved in pyridine (20 μL) was acetylatedwith acetic anhydride (20 μL) at room temperature. After 24 h the reaction was stopped byaddition of MeOH and the azeotrope formed by addition of C6H6 was dried under reducedpressure. The residue (1.2 mg) was purified by preparative TLC using CHCl3 as eluent to yield1,3-O,O′-diacetylorcinol (4, 1.2 mg). Compound 4 had: 1H NMR (500 MHz, in CDCl3), δ: 6.82(br s, H-4 and H-6), 6.73 (br s, H-2), 2.30 (s, Me-5), 2.19 (s, OAc-1 and OAc-2). ESIMS (+), m/z:247 [M + K]+ and 231 [M + Na]+.
With pyridine at 20℃; for 12h; 3.2.3. 5-(Bromomethyl)-1,3-phenylene diacetate (15) Orcinol (2 g, 0.016 mol) was dissolved in pyridine (80 mL), acetic anhydride (4.57 mL, 0.048 mol)was added thereto, and the mixture was stirred at room temperature for 12 h. Water was added tostop the reaction, and it was concentrated under reduced pressure after EtOAc extraction and MgSO4drying. The resulting mixture 12 (1.7 g, 0.008 mol) was dissolved in EtOAc (50 mL) withoutpurification, and N-bromosuccinimide (1.89 g, 0.01 mol) was added thereto and stirred at 60 °C for 2days. The reaction was terminated with water and EtOAc, and the organic layer was dried overMgSO4 and concentrated under reduced pressure. The resulting mixture was separated by columnchromatography (n-hexane:EtOAc = 5:1) to give compound 15 (1.19 g, 52%): 1H-NMR (500 MHz,CDCl3) δ 7.02 (d, J = 2.1 Hz, 2H), 6.86 (t, J = 2.1 Hz, 1H), 4.41 (s, 2H), 2.26 (s, 6H); 13C-NMR (125 MHz,CDCl3) δ 168.9, 515.1, 139.9, 119.7, 115.5, 31.9, 21.2; ESI-HRMS (M + H)+ m/z calcd for C11H12BrO4286.9919, found 286.9947.

Reference: [1]Current Patent Assignee: C.H. Boehringer Sohn AG & Co. KG - US2012/88755, 2012, A1 Location in patent: Page/Page column 72
[2]Tangestaninejad, Shahram; Habibi, Mohammad Hossein; Mirkhani, Valiollah; Moghadam, Majid [Synthetic Communications, 2002, vol. 32, # 9, p. 1337 - 1343]
[3]Current Patent Assignee: PFIZER INC - US2005/43300, 2005, A1 Location in patent: Page/Page column 47
[4]Steynberg, Jan P.; Ferreira, Daneel; Roux, David G. [Journal of the Chemical Society. Perkin transactions I, 1987, p. 1705 - 1712]
[5]Berrier, Christian; Jacquesy, Jean-Claude; Renoux, Alain [Bulletin de la Societe Chimique de France, 1987, # 1, p. 212 - 218]
[6]Desai; Mavani [Proceedings - Indian Academy of Sciences, Section A, 1949, vol. <A> 29, p. 269,270]
[7]Tsujihara, Kenji; Hongu, Mitsuya; Saito, Kunio; Kawanishi, Hiroyuki; Kuriyama, Kayoko; Matsumoto, Mamoru; Akira, Oku; Ueta, Kiichiro; Tsuda, Minoru; Saito, Akira [Journal of Medicinal Chemistry, 1999, vol. 42, # 26, p. 5311 - 5324]
[8]Current Patent Assignee: KISSEI PHARMACEUTICAL COMPANY LIMITED - EP1609798, 2005, A1 Location in patent: Page/Page column 64
[9]Current Patent Assignee: GLAXOSMITHKLINE PLC; AUTIFONY THERAPEUTICS LIMITED - WO2012/76877, 2012, A1 Location in patent: Page/Page column 67
[10]Current Patent Assignee: AUTIFONY THERAPEUTICS LIMITED; GLAXOSMITHKLINE PLC - US2013/267510, 2013, A1 Location in patent: Paragraph 0522-0524
[11]Masi, Marco; Zonno, Maria Chiara; Cimmino, Alessio; Reveglia, Pierluigi; Berestetskiy, Alexander; Boari, Angela; Vurro, Maurizio; Evidente, Antonio [Natural Product Research, 2018, vol. 32, # 13, p. 1537 - 1547]
[12]Baek, Dong Jae; Ki, Sung Hwan; Kim, Sang-Bum; Kim, Sanghee; Kim, Su Bin; Kwon, Yongseok; Lee, Joo-Youn; Lee, Taeho; Moon, Hong Seop; Oh, Yoon Sin; Park, Eun-Young; Park, Jeong-Eun [Molecules, 2020, vol. 25, # 11]
  • 2
  • [ 20982-28-9 ]
  • [ 1634-34-0 ]
YieldReaction ConditionsOperation in experiment
74% With aluminium trichloride In chlorobenzene at 90℃; for 1h;
66% With aluminum (III) chloride In chlorobenzene at 90℃; for 1h; 70 1-(2,6-Dihydroxy-4-methyl-phenyl)-ethanone Preparation 70 1-(2,6-Dihydroxy-4-methyl-phenyl)-ethanone A solution of the compound of Preparation 69 (10.12 g, 48.6 mmol) in chlorobenzene (10 mL) was added dropwise to a suspension of aluminium chloride (19.44 g, 145.8 mmol) in chlorobenzene (50 mL), warmed to 90° C., and the mixture was stirred for one hour. The reaction mixture was then cooled and was pipetted carefully onto a mixture of ice and 2M hydrochloric acid. The resulting mixture was extracted with ethyl acetate (3*200 mL) and the combined organic layers were washed with brine, dried over magnesium sulfate and concentrated in vacuo. The residue was purified by column chromatography on silica gel, eluding with pentane:ethyl acetate, 84:16, 80:20, 75:25 to afford the title compound as a yellow solid in 66% yield, 5.31 g. LRMS (APCI+): m/z [M+H]+ 167
Multi-step reaction with 2 steps 1: AlCl3 / 1.5 h / 145 - 150 °C 2: 85 percent aq. H2SO4 / 2 h / 20 °C
Multi-step reaction with 2 steps 1: AlCl3 / 140 - 150 °C 2: aqueous sulfuric acid
With aluminum (III) chloride In chlorobenzene at 90℃; for 1h; 42 2',6'-Dihydroxy-4'-methylacetophenone To a solution of orcinol (30 g) in pyridine (240 mL) was added acetic anhydride (91 mL) at room temperature, and the mixture was stirred for 16 hours. The reaction mixture was concentrated under reduced pressure, and the residue was dissolved in ethyl acetate. The solution was washed with 1 mol/L hydrochloric acid, water, a saturated aqueous sodium hydrogen carbonate solution and brine successively, and dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure to give orcinol diacetate (43.7 g). To a suspension of aluminum chloride (19.3 g) in chlorobenzene (50 mL) was added a solution of orcinol diacetate (10 g) in chlorobenzene (8 mL) in a dropwise manner at 90°C, and the mixture was stirred at the same temperature for 1 hour. The reaction mixture was poured into 0. 5 mol/L hydrochloric acid cooled in ice, and the resulting mixture was stirred for 30 minutes. The mixture was extracted with ethyl acetate, and the extract was washed with water and dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure. To the residue was added n-hexane (100 mL), and the mixture was stirred at room temperature for 30 minutes. The insoluble material was collected by filtration and dried under reduced pressure to give the title compound (7.2 g).1H-NMR (CDCl3) δ ppm: 2.24 (3H, s), 2.7 (3H, s), 6.21 (2H, s), 8.8-9.85 (2H, br)
With hydrogenchloride In hexane; chlorobenzene R.1.2 Reference Example 1 (2) Aluminum chloride (19.2 g) is heated at 90° C. in chlorobenzene (50 ml), and thereto is added dropwise a solution of orcinol diacetate (10 g) in chlorobenzene (8 ml) over a period of 35 minutes. After addition, the mixture is stirred at the same temperature for one hour, and cooled. The reaction mixture is poured into ice-10% hydrochloric acid (100 ml--100 ml), and the mixture is stirred for 30 minutes, and extracted with ethyl acetate (100 ml). The organic layer is washed with water, dried, and concentrated under reduced pressure. Hexane (100 ml) is added to the residue, and the mixture is stirred at room temperature for 30 minutes. The precipitates are collected by filtration, and dried to give 2',6'-dihydroxy-4'-methylacetophenone (5.9 g), m.p. 146-148° C.
Stage #1: 5-methylbenzene-1,3-diyl diacetate With aluminum (III) chloride In chlorobenzene at 90℃; for 1h; Stage #2: With hydrogenchloride In water; chlorobenzene Cooling with ice; Intermediate 16 l-(2,6-dihvdroxy-4-methylphenyl)ethanoneA solution of 5-methylbenzene-l,3-diyl diacetate (Intermediate 15, 3.33 g) in chlorobenzene (5.0 ml) was added dropwise to a suspension of AICI3 (6.40 g, 48.0 mmol) in chlorobenzene (15.0 ml). The reaction mixture was stirred at 90QC for 1 hour, then it was cooled down to room temperature and pipetted onto a mixture of ice and 2 M HCI aqueous solution (16 ml). Ethyl acetate was added, the two phases were separated. The organic one was washed 2 times with brine, then dried over sodium sulphate, filtered and evaporated. The residue obtained was purified by silica gel chromatography eluting with a gradient Cy-Hex/EtOAc from 100/0 to 70/30 followed by an isochratic 70/30, another gradient from 70/30 to 50/50 and another isochratic 50/50. This afforded the title compound (940 mg).1H-NM (400 MHz, DMSO-c/6): δ ppm 11.89 (2H, s), 6.22 (2H, s), 2.63 (3H, s), 2.19 (3H, s); UPLC-MS: 0.62 min, 167 [M+H]+.
940 mg With aluminum (III) chloride In chlorobenzene at 90℃; for 1h; 16 Intermediate 16 1-(2,6-dihydroxy-4-methylphenyl)ethanone Intermediate 16 1-(2,6-dihydroxy-4-methylphenyl)ethanone [0525] [0526] A solution of 5-methyl benzene-1,3-diyl diacetate (Intermediate 15, 3.33 g) in chlorobenzene (5.0 ml) was added dropwise to a suspension of AlCl3 (6.40 g, 48.0 mmol) in chlorobenzene (15.0 ml). The reaction mixture was stirred at 90° C. for 1 hour, then it was cooled down to room temperature and pipetted onto a mixture of ice and 2 M HCl aqueous solution (16 ml). Ethyl acetate was added, the two phases were separated. The organic one was washed 2 times with brine, then dried over sodium sulphate, filtered and evaporated. The residue obtained was purified by silica gel chromatography eluting with a gradient Cy-Hex/EtOAc from 100/0 to 70/30 followed by an isochratic 70/30, another gradient from 70/30 to 50/50 and another isochratic 50/50. This afforded the title compound (940 mg). [0527] 1H-NMR (400 MHz, DMSO-d6): δ ppm 11.89 (2H, s), 6.22 (2H, s), 2.63 (3H, s), 2.19 (3H, s); UPLC-MS: 0.62 min, 167 [M+H]+.

  • 4
  • [ 6153-39-5 ]
  • [ 20982-28-9 ]
YieldReaction ConditionsOperation in experiment
With acetic anhydride; In pyridine; ethyl acetate; (1) <strong>[6153-39-5]Orcinol monohydrate</strong> (50 g) is dissolved in pyridine (400 ml), and thereto is added acetic anhydride (133 ml), and the mixture is stirred at room temperature for 17 hours. The reaction mixture is concentrated under reduced pressure, and the resulting residue is dissolved in ethyl acetate (500 ml). The mixture is washed successively with 10% hydrochloric acid, water, a saturated aqueous sodium hydrogen carbonate solution, and a saturated aqueous sodium chloride solution, dried, and concentrated under reduced pressure to give orcinol diacetate (74 g). EI-MS (m/z): 208 (M+) NMR (CDCl3) delta:2.27 (6H, s), 2.35 (3H, s), 6.71 (1H, t, J=1.8), 6.80 (2H, m)
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