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USD 0.00
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Structure of 697-82-5 * Storage: {[proInfo.prStorage]}
* 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.
Reference:
[1] Chemistry - A European Journal, 2017, vol. 23, # 71, p. 17981 - 17991
2
[ 95-63-6 ]
[ 16308-92-2 ]
[ 700-13-0 ]
[ 496-78-6 ]
[ 2416-94-6 ]
[ 697-82-5 ]
[ 53957-33-8 ]
Reference:
[1] Chemistry - A European Journal, 2017, vol. 23, # 71, p. 17981 - 17991
3
[ 95-63-6 ]
[ 16308-92-2 ]
[ 6966-10-5 ]
[ 496-78-6 ]
[ 2416-94-6 ]
[ 697-82-5 ]
[ 53957-33-8 ]
Reference:
[1] Chemistry - A European Journal, 2017, vol. 23, # 71, p. 17981 - 17991
4
[ 95-63-6 ]
[ 16308-92-2 ]
[ 6966-10-5 ]
[ 496-78-6 ]
[ 2416-94-6 ]
[ 697-82-5 ]
[ 53957-33-8 ]
Reference:
[1] Chemistry - A European Journal, 2017, vol. 23, # 71, p. 17981 - 17991
5
[ 697-82-5 ]
[ 74-88-4 ]
[ 20469-61-8 ]
Reference:
[1] Chemical & Pharmaceutical Bulletin, 1981, vol. 29, # 10, p. 2825 - 2831
[2] Russian Journal of Organic Chemistry, 1993, vol. 29, # 4, p. 572 - 575[3] Zhurnal Organicheskoi Khimii, 1993, vol. 29, # 4, p. 682 - 686
[4] Tetrahedron Letters, 2007, vol. 48, # 8, p. 1337 - 1340
[5] Chemistry - A European Journal, 2014, vol. 20, # 29, p. 8904 - 8908
[6] Helvetica Chimica Acta, 2002, vol. 85, # 9, p. 2926 - 2929
[7] Pharmaceutical Chemistry Journal, 1994, vol. 28, # 5, p. 343 - 348[8] Khimiko-Farmatsevticheskii Zhurnal, 1994, vol. 28, # 5, p. 43 - 47
[9] Pharmaceutical Research, 1995, vol. 12, # 7, p. 983 - 992
[10] Patent: US4368150, 1983, A,
[11] Patent: US4476051, 1984, A,
[12] Phosphorus, Sulfur and Silicon and the Related Elements, 2010, vol. 185, # 3, p. 501 - 508
[13] Bioorganic Chemistry, 2018, vol. 80, p. 253 - 260
6
[ 697-82-5 ]
[ 616-38-6 ]
[ 20469-61-8 ]
Yield
Reaction Conditions
Operation in experiment
99%
at 180℃; for 1 h;
General procedure: General procedure for the alkylation of phenols with dimethyl carbonate. A 17-mL stainless steel high-pressure micro reactor was charged with 3 mmol of Mn2(CO)10, W(CO)6, or Co2(CO)8, 100 mmol of the corresponding phenol, and 300 mmol of dimethyl carbonate, and the reactor was hermetically closed and heated for 1 h at 180°C. The reactor was then cooled to room temperature and opened, and the mixture was filtered through a layer of alumina. Unreacted dimethyl carbonate was distilled off, and the residue was distilled under atmospheric or reduced pressure or recrystallized from ethanol. 1-Methoxy-2,3,5-trimethylbenzene. Yield 99percent, bp 84.5–85°C (7 mm). 13C NMR spectrum, δC, ppm: 11.60, 20.03, 21.38 (CH3); 110.52 (C6), 119.95 (C2), 124.92 (C4), 137.32 (C3), 137.54 (C5), 157.43 (C1). Found, percent: C 79.87; H 9.35. C10H14O. Calculated, percent: C 79.96; H 9.39.
Reference:
[1] Russian Journal of Organic Chemistry, 2015, vol. 51, # 3, p. 330 - 334[2] Methylation of Phenol and Its Derivatives with Dimethyl Carbonate in the Presence of Mn2(CO)10, W(CO)6, and Co2(CO)8, 2015, vol. 51, # 3, p. 330 - 334,5
7
[ 697-82-5 ]
[ 77-78-1 ]
[ 20469-61-8 ]
Reference:
[1] Liebigs Annalen der Chemie, 1984, vol. 1984, # 10, p. 1740 - 1745
[2] Chemische Berichte, 1915, vol. 48, p. 1713
8
[ 697-82-5 ]
[ 64-19-7 ]
[ 935-92-2 ]
[ 13038-87-4 ]
[ 20469-61-8 ]
[ 34649-27-9 ]
[ 109576-73-0 ]
Reference:
[1] Journal of Organic Chemistry USSR (English Translation), 1986, vol. 22, # 11, p. 2071 - 2078[2] Zhurnal Organicheskoi Khimii, 1986, vol. 22, # 11, p. 2306 - 2315
9
[ 79-21-0 ]
[ 697-82-5 ]
[ 935-92-2 ]
[ 700-13-0 ]
[ 13038-87-4 ]
[ 20469-61-8 ]
[ 34649-27-9 ]
Reference:
[1] J. Gen. Chem. USSR (Engl. Transl.), 1987, vol. 57, # 4, p. 819 - 826[2] Zhurnal Obshchei Khimii, 1987, vol. 57, # 4, p. 923 - 930
10
[ 20469-61-8 ]
[ 697-82-5 ]
[ 74-88-4 ]
[ 54344-92-2 ]
Reference:
[1] Patent: US4021574, 1977, A,
11
[ 697-82-5 ]
[ 54344-92-2 ]
Reference:
[1] Helvetica Chimica Acta, 2002, vol. 85, # 9, p. 2926 - 2929
[2] Pharmaceutical Research, 1995, vol. 12, # 7, p. 983 - 992
[3] Russian Journal of Organic Chemistry, 1993, vol. 29, # 4, p. 572 - 575[4] Zhurnal Organicheskoi Khimii, 1993, vol. 29, # 4, p. 682 - 686
[5] Chemistry - A European Journal, 2014, vol. 20, # 29, p. 8904 - 8908
[6] Bioorganic Chemistry, 2018, vol. 80, p. 253 - 260
12
[ 697-82-5 ]
[ 69877-38-9 ]
Reference:
[1] Pharmaceutical Research, 1995, vol. 12, # 7, p. 983 - 992
[2] Russian Journal of Organic Chemistry, 1993, vol. 29, # 4, p. 572 - 575[3] Zhurnal Organicheskoi Khimii, 1993, vol. 29, # 4, p. 682 - 686
[4] Chemistry - A European Journal, 2014, vol. 20, # 29, p. 8904 - 8908
With tert.-butylhydroperoxide; 3K(1+)*BO40W12(5-)*14H2O*4C3H3N4O2(1-)*2C3H4N4O2*3Cu(2+) at 60℃; for 0.133333h;
96%
With titanium superoxide; dihydrogen peroxide; acetic acid In water at 50℃; for 2h;
96%
With methylene blue In methanol; water at 35℃;
1; 2; 3; 4; 5; 6 Experimental series 5
In the fifth series 2,3,5-trimethylphenol (=2,3,5 TMP) (0.02 mol/L in a solvent mixture of methanol/water of 4/1 (vol/vol)) using air (10 bar, 1.35 mL/min) and at 35°C and different photosensitizers (0.9 mol%). (Flowrate 0.25 mL/min, tR = 16 min).
94%
With oxygen In water; acetonitrile at 40℃; for 1h; Green chemistry;
93%
With 5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrin; oxygen In chloroform; acetonitrile for 24h; Irradiation;
92%
With methylene blue In methanol; water at 20℃; for 0.266667h; Irradiation; Flow reactor;
88%
9 EXAMPLE 9
EXAMPLE 9 2,3,5-trimethylphenol was reacted in the same manner as in Example 8 to obtain 13.2 g of 2,3,5-trimethyl-p-benzoquinone. (Yield: 88 percent)
87.3%
With tert.-butylhydroperoxide at 100℃; for 14h;
85%
With dihydrogen peroxide In acetic acid at 20℃; for 5h;
85%
13 EXAMPLE 13
EXAMPLE 13 In manner analogous to Example 3, but employing 2,3,5-trimethylphenol in place of 2,3,6-trimethylphenol, there was obtained 2,3,5-trimethyl-p-benzoquinone in 85 percent yield.
76%
With 1,1,1,3',3',3'-hexafluoro-propanol; urea hydrogen peroxide adduct at 45℃; Sealed tube; Green chemistry;
73%
With H5PV2Mo10O40; oxygen In various solvent(s) at 25℃; for 4h;
69%
With dihydrogen peroxide; methyltrioxorhenium(VII) In water; carbonic acid dimethyl ester at 60℃;
65%
With dihydrogen peroxide; acetic acid In water at 40℃; for 24h;
55%
With oxygen; copper(l) chloride; lithium chloride In hexan-1-ol at 70℃; for 48h; Inert atmosphere;
51%
In acetic acid
4 EXAMPLE 4 STR8
EXAMPLE 4 STR8 500 mg of 2,3,5-trimethylphenol and 10 mg of RuCl3.3H2 O was reacted in 5 ml of acetic acid in the same manner as in Example 1, followed by the same treatment as in Example 1, whereby 100 mg of unreacted starting material and 230 mg (51% yield) of trimethylbenzoquinone was obtained.
47%
With sodium perborate In acetic acid at 50 - 60℃; for 4h;
41%
With dihydrogen peroxide In acetic acid
15%
With C116H78N8O2Pd2(4+)*4ClH2O4(1-); oxygen In acetonitrile for 0.666667h; Irradiation;
With hydrogenchloride; sodium nitrite at 0℃; Erhitzen des Reaktionsprodukts mit wss. H2O2 und wss. HCl;
With potassium nitrososulfonate
With trifluoroacetyl peroxide
72.0 % Chromat.
With phosphomolybdic acid hydrate; dihydrogen peroxide In acetic acid at 30℃; for 5h;
With dihydrogen peroxide In acetic acid at 20℃; for 12h;
With dihydrogen peroxide; methyltrioxorhenium(VII); 1-butyl-3-methylimidazolium Tetrafluoroborate at 40℃; for 6h;
95 % Chromat.
With dihydrogen peroxide; methyltrioxorhenium(VII) In water at 60℃; for 7h;
With hypocrellin B; hypocrellin A for 12h; Irradiation; Air condition;
With air
With dihydrogen peroxide In acetonitrile at 79.84℃; Green chemistry;
With (tetra-n-butylammonium)4H[γ-PW10V2O40]; dihydrogen peroxide In water; acetonitrile at 80℃; for 0.166667h; Green chemistry;
With dihydrogen peroxide In acetonitrile at 79.84℃; for 1h; Green chemistry;
With oxygen; copper(l) chloride In water; acetonitrile at 30℃; for 3h;
General procedure: To a solution of the respective phenol derivative (23f-k, 15.0 mg, 0.11 mmol, 1 equiv) in dry DMF (2.2 mL), K2CO3 (15.2 mg, 0.11 mmol, 1 equiv) was added and the mixture was stirred at room temperature for 30 min. Methyl iodide (31 mg, 0.22 mmol, 2 equiv) was added and the reaction mixture was stirred at room temperature overnight. The reaction was quenched by addition of water and the aqueous phase was extracted three times with EtOAc. The combined organic layers were dried over MgSO4 and the solvent was removed under reduced pressure. The crude product was purified by column chromatography on silica gel (cyclohexane/ethyl acetate 20:1).The pure products were obtained as pale yellow liquids.
In water; dimethyl sulfoxide;
(1) Synthesis of 2,3,5-trimethylanisole In 100 ml of DMSO were dissolved 10 g of 2,3,5-trimethylphenol and 10.4 ml of methyl iodide. Under ice-cooling, 5.6 g of 60% sodium hydride in oil was added, and the mixture was stirred at room temperature for 10 hours. After addition of water, the extraction with ether was carried out. The ether layer was washed with water and dried over anhydrous sodium sulfate. Removal of the solvent by distillation leaves the oily substance. Yield 12.9 g (quantitative)
In water; dimethyl sulfoxide;
(1) Synthesis of 2,3,5-trimethylanisole In 100 ml of dimethyl sulfoxide were dissolved 10 g of 2,3,5-trimethylphenol and 10.4 ml of methyl iodide and the solution was ice-cooled. To this solution was added 5.6 g of 60% oily sodium hydride and the mixture was stirred for 10 hours. Water was added and the resulting mixture was extracted with ether. The ether layer was washed with water and dried over anhydrous sodium sulfate. The solvent was then distilled off to give an oily substance. Yield 12.9 g (quantitative).
With potassium hydroxide; sodium acetate; trichlorophosphate; In N-methyl-acetamide; ethanol; water; benzene;
EXAMPLE 1 The following procedure is illustrative of the synthesis of compounds represented by formula I. A total of 500 g of 2,3,5-trimethylphenol were introduced into 1840 ml of ethanol and 184 ml of water and treated with 240 g of potassium hydroxide with gentle stirring. 626 Grams of methyl iodide were added to the resulting clear solution at 0-5 over a period of 30-45 minutes. The mixture was stirred for 2 hours at room temperature, subsequently stirred under reflex conditions at 60 for 12 hours, then treated with 5 liters of water and thoroughly extracted with a total of 6 liters of ether. The extract was washed first with 3 liters of 3-N sodium hydroxide, then twice with 1 liter portions of water, dried over sodium sulfate and evaporated under reduced pressure. The residual <strong>[20469-61-8]<strong>[20469-61-8]2,3,5-trimethylanisol</strong>e</strong> boiled at 88-90 /10 Torr after rectification. 184 Grams of phosphorus oxychloride were added dropwise over 20-30 minutes to 87.1 g of dimethylformamide while at 10-20 with stirring. As the addition neared completion the temperature rose to 25. 150 Grams of <strong>[20469-61-8]<strong>[20469-61-8]2,3,5-trimethylanisol</strong>e</strong> were added over 20 minutes while cooling at 10-20. The mixture was slowly heated up to a maximum of 115, stirred at 100 for 6 hours in order to complete the reaction, cooled, poured into 2 kg of ice/water (1:1) and, after the addition of 1500 ml of benzene, treated with 500 g of sodium acetate. The water phase which formed was separated after stirring for 1 hour and again extracted with 1000 ml of benzene. The combined benzene extracts were washed successively with 480 ml of 1.5-N hydrochloric acid and 500 ml of water, dried over sodium sulfate and filtered over 20 g of decolorizing carbon. The filtrate was evaporated under reduced pressure. The residual 2,3,6-trimethyl-p-anisaldehyde melted at 65-66 after recrystallization from hexane.
With potassium carbonate In N,N-dimethyl-formamide at 80℃; for 15h;
1
Reference Example 11,2,5-trimethyl-3-[(2-methylprop-2-en-1-yl)oxy]benzene1,2,5-trimethyl-3-[(2-methylprop-2-en-1-yl)oxy]benzene3-bromo-2-methylpropene (29.8 g, 221 mmol) was added to a mixture of DMF (130 mL) containing 2,3,5-trimethylphenol (25.0 g, 184 mmol) and potassium carbonate (50.9 g, 368 mmol), and the resulting mixture was stirred at 80° C. for 15 hours. After cooled to room temperature, the reaction solution was distributed using ethyl acetate and water. The organic layer was washed with saturated saline, and then dried using anhydrous magnesium sulfate. The solvent was removed under reduced pressure, and the obtained residue was purified by silica gel column chromatography (hexane-ethyl acetate 50:1 to 9:1) to give 33.6 g of the title compound (yield: 96%) as an oily product.1H-NMR (CDCl3): δ1.84 (3H, s), 2.14 (3H, s), 2.23 (3H, s), 2.27 (3H, s), 4.39 (2H, s), 4.94-4.99 (1H, m), 5.09-5.14 (1H, m), 6.52 (1H, s), 6.61 (1H, s).
96%
With potassium carbonate In N,N-dimethyl-formamide at 80℃; for 15h;
General procedure: General procedure for the alkylation of phenols with dimethyl carbonate. A 17-mL stainless steel high-pressure micro reactor was charged with 3 mmol of Mn2(CO)10, W(CO)6, or Co2(CO)8, 100 mmol of the corresponding phenol, and 300 mmol of dimethyl carbonate, and the reactor was hermetically closed and heated for 1 h at 180C. The reactor was then cooled to room temperature and opened, and the mixture was filtered through a layer of alumina. Unreacted dimethyl carbonate was distilled off, and the residue was distilled under atmospheric or reduced pressure or recrystallized from ethanol. 1-Methoxy-2,3,5-trimethylbenzene. Yield 99%, bp 84.5-85C (7 mm). 13C NMR spectrum, deltaC, ppm: 11.60, 20.03, 21.38 (CH3); 110.52 (C6), 119.95 (C2), 124.92 (C4), 137.32 (C3), 137.54 (C5), 157.43 (C1). Found, %: C 79.87; H 9.35. C10H14O. Calculated, %: C 79.96; H 9.39.
3-(2,3,5-trimethylphenoxy)phthalonitrile[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
86.97%
With potassium carbonate; In dimethyl sulfoxide; at 50℃; for 120h;Inert atmosphere;
General procedure: 10mmol <strong>[51762-67-5]3-nitrophthalonitrile</strong> (or 4-nitrophthalonitrile or 4,5-dichlorophthalonitrile) 10.44mmol (1.42g), 2,3,5-trimethylphenol and 30mmol (3.18g) anhydrous K2CO3 were added in 20mL anhydrous dimethylsulfoxide (DMSO). The reaction mixture was hold by stirring at 50?C for 5days under inert atmosphere. It was poured into cold water and a white colour with a grey solid precipitated. The obtained precipitate was filtered and washed using cold water and dried in the open air. The raw product was purified by column chromatography using silica gel eluting with CHCl3.
4-chloro-5-(2,3,5-trimethylphenoxy)phthalonitrile[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
55.7%
With potassium carbonate; In dimethyl sulfoxide; at 50℃; for 120h;Inert atmosphere;
General procedure: 10mmol 3-nitrophthalonitrile (or 4-nitrophthalonitrile or <strong>[139152-08-2]4,5-dichlorophthalonitrile</strong>) 10.44mmol (1.42g), 2,3,5-trimethylphenol and 30mmol (3.18g) anhydrous K2CO3 were added in 20mL anhydrous dimethylsulfoxide (DMSO). The reaction mixture was hold by stirring at 50?C for 5days under inert atmosphere. It was poured into cold water and a white colour with a grey solid precipitated. The obtained precipitate was filtered and washed using cold water and dried in the open air. The raw product was purified by column chromatography using silica gel eluting with CHCl3.
5-bromo-3-isopropyl-1H-pyrrolo[3,2-b]pyridine[ No CAS ]
5-bromo-3-isopropyl-1-(p-tolylsulfonyl)pyrrolo-[3,2-b]pyridine[ No CAS ]
[ 100-39-0 ]
1-benzyloxy-4-bromo-2,3,5-trimethyl -benzene[ No CAS ]
2-bromo-5-[2-(3-methylbutylidene)hydrazin-1-yl]pyridine[ No CAS ]
4-bromo-2,3,5-trimethyl-phenol[ No CAS ]
[ 590-86-3 ]
2-(4-(benzyloxy)-2,3,6-trimethylbenzyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With dmap; potassium carbonate; potassium penicillin V
6 Preparation of 4-[[3-isopropyl-1-(4-methylbenzenesulfonyl)pyrrolo[3,2-b]pyridin-5-yl]methyl]-2,3,5-trimethylphenol.
Into a 1L round-bottom flask was placed 2-bromo-5-hydrazinylpyridine (70 g, 372 mmol), ethanol (0.5 L), isovaleraldehyde (38.5 g, 447 mmol). The resulting solution was stirred for 1 h at 0° C., then concentrated to afford 55 g (58%) of 2-bromo-5-[2-(3-methylbutylidene)hydrazin-1-yl]pyridine as a yellow solid. Into a 1L round-bottom flask was placed 2,3,5-trimethylphenol (55.0 g, 404 mmol), CH3CN (400 mL), and NBS (57.5 g, 323 mmol). The resulting solution was stirred for 5 h at 0° C., then concentrated under reduced pressure, and treated with water (200 mL). The solids were collected by filtration, washed with 800 mL of water, and air dried to afford 75 g (86%) of 4-bromo-2,3,5-trimethylphenol as a white solid. Into a 1L round-bottom flask, was placed 2-bromo-5-[2-(3-methylbutylidene)hydrazin-1-yl]pyridine (55.0 g, 215 mmol), xylene (450 mL), ZnCl2 (58.5 g, 429 mmol). The resulting solution was stirred overnight at 130° C. The resulting solution was cooled to rt, extracted with EA (3*500 mL). The combined organic layers were washed with brine (3*500 mL) and concentrated under reduced pressure. The crude was purified via a silica gel column (EA/PE=1/2) to afford 34 g (66%) of 5-bromo-3-isopropyl-1H-pyrrolo[3,2-b]pyridine as a yellow solid. Into a 1L round-bottom flask was placed 4-bromo-2,3,5-trimethylphenol (75.0 g, 349 mmol), CH3CN (600 mL), K2CO3 (144.6 g, 1046 mmol), benzyl bromide (28.3 mL). The resulting solution was stirred for 20 h at room temperature, then diluted with EA (1L), and washed with water (3*500 mL). The organic layer was dried over anhydrous MgSO4. The solids were removed by filtration and the filtrate was concentrated under reduced pressure. The crude product was purified via silica gel column chromatography (PE) to afford 70 g of 1-(benzyloxy)-4-bromo-2,3,5-trimethylbenzene as a white solid. Into a 1L, 3-necked, round-bottom flask purged and maintained with an inert atmosphere of nitrogen, was placed 5-bromo-3-isopropyl-1H-pyrrolo[3,2-b]pyridine (34.0 g, 142 mmol), CH2Cl2 (520 mL), TsCl (54.2 g, 284 mmol), DMAP (347 mg, 2.84 mmol), DIEA (40.4 g, 313 mmol). The resulting solution was stirred overnight at room temperature, then was concentrated under reduced pressure. The crude product was purified via silica gel column chromatography (EA/PE=1/10) to afford 20 g of 5-bromo-3-isopropyl-1-(4-methylbenzenesulfonyl)pyrrolo[3,2-b]pyridine as a yellow solid. Into a 1L, 3-necked, round-bottom flask, purged and maintained with an inert atmosphere of nitrogen, was placed 1-(benzyloxy)-4-bromo-2,3,5-trimethylbenzene (70.0 g, 229 mmol), bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) methane (67.60 g, 252 mmol), Pd(t-Bu3P)2 (11.7 g, 22.9 mmol), KOH (23.2 g, 413 mmol), 1,4-dioxane (500 mL), water (20 mL). The resulting solution was stirred overnight at 80° C. The reaction mixture was cooled to room temperature, treated with water (200 mL), extracted with EA (3*200 mL). The combined organic layers were washed with brine (3*500 mL), dried over anhydrous MgSO4, the solids were removed by filtration and the filtrate was concentrated under reduced pressure. The crude product was purified via silica gel column chromatography (EA/PE=1/10) to afford 38 g of 2-[[4-(benzyloxy)-2,3,6-trimethylphenyl]methyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane as yellow oil.