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Structure of 491-11-2 * 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] Journal of Organic Chemistry, 1985, vol. 50, # 20, p. 3797 - 3806
[2] Journal fuer Praktische Chemie/Chemiker-Zeitung, 1998, vol. 340, # 6, p. 530 - 535
[3] Journal of the Chemical Society, 1926, p. 543[4] Journal of the Chemical Society, 1928, p. 628
[5] Patent: US5079257, 1992, A,
[6] Patent: WO2010/6086, 2010, A2, . Location in patent: Page/Page column 81-82
2
[ 491-11-2 ]
[ 74-88-4 ]
[ 28987-59-9 ]
Reference：
[1] Indian Journal of Chemistry, 1965, vol. 3, p. 397 - 401
[2] Chemistry - A European Journal, 2002, vol. 8, # 9, p. 2034 - 2046
3
[ 491-11-2 ]
[ 29242-84-0 ]
Reference：
[1] Chemistry - A European Journal, 2002, vol. 8, # 9, p. 2034 - 2046
[2] Journal of the Chemical Society, 1926, p. 543[3] Journal of the Chemical Society, 1928, p. 628
With copper(II) nitrate trihydrate In tetrahydrofuran at 50℃; for 4 h;
General procedure: A suspension of 2-methylphenol(18.5 mmol, 1.0 eq) and Cu(NO3)2.3H2O (27.7 mmol, 1.5 eq) in THF was stirred magnetically at 60°C or reflux for several hours. Then after the solvent was removed under vacuum, the mixture was extracted with EtOAc (3×30 mL). The combined organic layers were washed with brine (5mL), dried over anhydrous MgSO4 and concentrated under vacuum. The crude residue was purified by column chromatography to afford the product (67-90percent).
75%
With potassium hydrogensulfate; sodium perborate hexahydrate; sodium nitrite In neat (no solvent) for 0.0277778 h; Molecular sieve; Microwave irradiation
General procedure: Reactants such as sodium nitrite (12 mmol), with aromatic or heteroaromatic compound (10 mmol), KHSO4 (1 mmol), and SPB (1 mmol), were thoroughly mixed with silica gel and placed in MW oven. Reaction progress was monitored by thin-layer chromatography (TLC) until completion. The reaction mixture was then treated with NaHCO3 solution and extracted with ethyl acetate (30 mL). Final product was obtained by using the same workup steps as detailed in the preceding section. Sodium perborate/NaNO2/KHSO4-initiated nitration reactions with several other compounds also afforded corresponding nitroderivatives (Scheme 1) via both conventional and MW-assisted reactions.
Reference：
[1] Journal of Chemical Sciences, 2011, vol. 123, # 1, p. 63 - 67
[2] Arkivoc, 2014, vol. 2014, # 5, p. 64 - 71
[3] Research on Chemical Intermediates, 2018, vol. 44, # 10, p. 6023 - 6038
[4] International Journal of Chemical Kinetics, 2017, vol. 49, # 8, p. 622 - 632
[5] Helvetica Chimica Acta, 1963, vol. 46, p. 727 - 741
[6] Patent: WO2010/6086, 2010, A2, . Location in patent: Page/Page column 81-82
[7] International Journal of Chemical Kinetics, 2016, vol. 48, # 4, p. 171 - 196
[8] International Journal of Chemical Kinetics, 2017, vol. 49, # 8, p. 622 - 632
[9] Patent: DE143449, , ,
6
[ 28987-59-9 ]
[ 491-11-2 ]
Yield
Reaction Conditions
Operation in experiment
90.5%
at 110℃; for 15 h;
(3) with mechanical agitation,Drip funnel and reflux condenser in a 500m 1 three-necked flask,Add 99g content95percent 2-chloro-4-methoxy nitrobenzene solid,350 g of 20percent K0H solution and 3 g of PEG400,Stirring heating,Reflex at 110 ° CShould be about 15 hours,After the solid is completely dissolved,Plus hydrochloric acid,Precipitation of 2-chloro-4-hydroxy nitrobenzene,After filtration drying,To give 82.5 g of 2-chloro-4-hydroxy nitrobenzene as a yellow solid,Measured content of 95.2percentThe yield was 90.5percent.
Reference：
[1] Patent: CN105859559, 2016, A, . Location in patent: Paragraph 0036
7
[ 108-43-0 ]
[ 611-07-4 ]
[ 491-11-2 ]
Reference：
[1] Journal fuer Praktische Chemie/Chemiker-Zeitung, 1998, vol. 340, # 6, p. 530 - 535
[2] Synthetic Communications, 1996, vol. 26, # 20, p. 3783 - 3790
[3] Chemische Berichte, 1878, vol. 11, p. 1161
[4] Journal of the Chemical Society, 1931, p. 84
[5] Journal of the Chemical Society, 1925, vol. 127, p. 1602[6] Journal of the Chemical Society, 1926, p. 159
[7] Synthetic Communications, 1996, vol. 26, # 20, p. 3783 - 3790
[8] Chemistry - A European Journal, 2002, vol. 8, # 9, p. 2034 - 2046
8
[ 88-73-3 ]
[ 491-11-2 ]
[ 88-75-5 ]
Reference：
[1] Journal of Organic Chemistry, 1998, vol. 63, # 13, p. 4199 - 4208
9
[ 163685-01-6 ]
[ 491-11-2 ]
[ 1075-59-8 ]
Reference：
[1] Journal of the American Chemical Society, 1995, vol. 117, # 20, p. 5484 - 5491
10
[ 88-73-3 ]
[ 491-11-2 ]
[ 17802-02-7 ]
[ 88-75-5 ]
Reference：
[1] Journal of Organic Chemistry USSR (English Translation), 1991, vol. 27, # 6.2, p. 1149 - 1152[2] Zhurnal Organicheskoi Khimii, 1991, vol. 27, # 6, p. 1317 - 1320
11
[ 40140-91-8 ]
[ 491-11-2 ]
Reference：
[1] Journal of the Chemical Society, 1925, vol. 127, p. 1602[2] Journal of the Chemical Society, 1926, p. 159
[3] Journal of Organic Chemistry, 1985, vol. 50, # 20, p. 3797 - 3806
12
[ 825-41-2 ]
[ 16292-86-7 ]
[ 491-11-2 ]
[ 3163-07-3 ]
Reference：
[1] Journal of Organic Chemistry, 2011, vol. 76, # 15, p. 6356 - 6361
13
[ 541-73-1 ]
[ 491-11-2 ]
Reference：
[1] Patent: CN105859559, 2016, A,
14
[ 611-06-3 ]
[ 491-11-2 ]
Reference：
[1] Patent: CN105859559, 2016, A,
15
[ 108-43-0 ]
[ 163685-01-6 ]
[ 491-11-2 ]
Reference：
[1] Journal of the American Chemical Society, 1995, vol. 117, # 20, p. 5484 - 5491
16
[ 95-57-8 ]
[ 163685-01-6 ]
[ 491-11-2 ]
Reference：
[1] Journal of the American Chemical Society, 1995, vol. 117, # 20, p. 5484 - 5491
17
[ 767-00-0 ]
[ 163685-01-6 ]
[ 491-11-2 ]
Reference：
[1] Journal of the American Chemical Society, 1995, vol. 117, # 20, p. 5484 - 5491
18
[ 163685-01-6 ]
[ 108-95-2 ]
[ 491-11-2 ]
[ 21002-15-3 ]
Reference：
[1] Journal of the American Chemical Society, 1995, vol. 117, # 20, p. 5484 - 5491
With copper(II) nitrate trihydrate; In tetrahydrofuran; at 50℃; for 4h;
General procedure: A suspension of 2-methylphenol(18.5 mmol, 1.0 eq) and Cu(NO3)2.3H2O (27.7 mmol, 1.5 eq) in THF was stirred magnetically at 60C or reflux for several hours. Then after the solvent was removed under vacuum, the mixture was extracted with EtOAc (3×30 mL). The combined organic layers were washed with brine (5mL), dried over anhydrous MgSO4 and concentrated under vacuum. The crude residue was purified by column chromatography to afford the product (67-90%).
75%
With potassium hydrogensulfate; sodium perborate hexahydrate; sodium nitrite; In neat (no solvent); for 0.0277778h;Molecular sieve; Microwave irradiation;
General procedure: Reactants such as sodium nitrite (12 mmol), with aromatic or heteroaromatic compound (10 mmol), KHSO4 (1 mmol), and SPB (1 mmol), were thoroughly mixed with silica gel and placed in MW oven. Reaction progress was monitored by thin-layer chromatography (TLC) until completion. The reaction mixture was then treated with NaHCO3 solution and extracted with ethyl acetate (30 mL). Final product was obtained by using the same workup steps as detailed in the preceding section. Sodium perborate/NaNO2/KHSO4-initiated nitration reactions with several other compounds also afforded corresponding nitroderivatives (Scheme 1) via both conventional and MW-assisted reactions.
With nitric acid; In acetic acid; at 30℃; for 16h;
Synthesis of l-(tert-butoxycarbonyl) - 7 chloro- 5 methoxy-lH-indol-2-yl boronic acid is shown in Scheme 4. Meta- chlorophenol is nitrated with fuming nitric acid in acetic acid to yield 4- nitro-3- chlorophenol, compound 4-2. The phenol is methylated with dimethylsulfate and potassium carbonate in ethanol, producing compound 4-3, which is treated with vinyl Grignard reagent and cyclized to form the indole, compound 4- 4. Compound 4-4 is protected with Boc and then treated with lithium diispropylamide and triisopropylborate to produce the protected substituted boronic acid 4-6.
<strong>[491-11-2]3-chloro-4-nitrophenol</strong> (5.0 g, 28.8 mmol) was added to ethanol (50 ml) at 26 C and then iron powder (9.6 g,172.9 mmol) and acetic acid (10 mL) were added thereto. The solution was stirred at 80 C for 16 hours and then cooledto 15 C. The solution was concentrated and purified by column chromatography to give compound 134A (pale red solid,3.6 g, the yield was 88%).
With iron; trifluoroacetic acid; at 20℃; for 144h;
Step 1 Synthesis of 3-Chloro-4-(2,2,2-trifluoroacetylamino)phenol Iron (3.24 g, 58.00 mmol) was added to stirring TFA (200 mL). To this slurry was added 2-chloro-4-nitrophenol (10.0 g, 58.0 mmol) and trifluoroacetic anhydride (20 mL). This gray slurry was stirred at room temp. for 6 d. The iron was filtered from solution and the remaining material was concentrated under reduced pressure. The resulting gray solid was dissolved in water (20 mL). To the resulting yellow solution was added a saturated NaHCO3 solution (50 mL). The solid which precipitated from solution was removed. The filtrate was slowly quenched with the sodium bicarbonate solution until the product visibly separated from solution (determined was using a mini work-up vial). The slightly cloudy yellow solution was extracted with EtOAc (3*125 mL). The combined organic layers were washed with a saturated NaCl solution (125 mL), dried (MgSO4) and concentrated under reduced pressure. The 1H NMR (DMS O-d6) indicated a 1:1 ratio of the nitrophenol starting material and the intended product 3-chloro-4-(2,2,2-trifluoroacetylamino)phenol. The crude material was taken on to the next step without further purification.
EXAMPLE 8 Preparation of benzyl 3-chloro-4-nitrophenyl ether STR22 A mixture of <strong>[491-11-2]3-chloro-4-nitrophenol</strong> (10 g, 0.058 mole), benzyl bromide (11.8 g, 0.069 mole), and potassium carbonate (16 g, 0.116 mole) in acetone is stirred, heated at reflux temperature for 17 hours, cooled and filtered. The filtrate is concentrated in vacuo to give a solid residue which is recrystallized from absolute ethanol to give the title compound, mp 82-84.5 C., identified by elemental and NMR analyses.
With potassium hydroxide; In water; ethylene glycol;
1st stage: Preparation of 3-(beta-hydroxyethoxy)-4-nitrophenol To a solution, heated on a boiling water bath, of 0.3 mole of KOH in 22.5 ml of ethylene glycol, there is added portionwise 0.1 mole (17.3 g) of <strong>[491-11-2]3-chloro-4-nitrophenol</strong> and then 10 ml of dioxane. Heating is maintained for 11 hours. The phenate of the expected product is drained after the reaction medium has been cooled. It is then washed with dioxane and thereafter with ethanol, and finally dissolved in 100 ml of water. The expected product precipitates on acidification. When recrystallized from isopropanol, it melts at 167 C. Analysis of the product obtained gives the following results:
With potassium hydroxide; In 1-methyl-pyrrolidin-2-one; water; 2-hydroxyethanethiol;
1st stage: Preparation of 3-(beta-hydroxyethylthio)-4-nitrophenol 0.2 mole (34.7 g) of <strong>[491-11-2]3-chloro-4-nitrophenol</strong> in 20 ml of N-methylpyrrolidone is added to a solution, heated to 40 C., of 0.4 mole of KOH in 35 ml of thioethanol. The mixture is heated for 1 hour on a boiling water bath. The reaction medium is diluted with 400 ml of ice-cold water. After neutralization with acetic acid, the expected product crystallizes. When recrystallized from ethyl acetate, it melts at 161 C. Analysis of the product obtained gives the following results:
3-β-aminoethylamino-4-nitrophenol hydrochloride[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With hydrogenchloride; ethylenediamine; In ice-water;
REFERENCE EXAMPLE 8 Preparation of 3-beta-aminoethylamino-4-nitrophenol hydrochloride STR14 0.432 mol (75 g) of <strong>[491-11-2]3-chloro-4-nitrophenol</strong> is introduced into 282 ml of ethylenediamine and the reaction mixture is heated on a boiling waterbath for 13 hours. The cooled solution is then poured into 2.6 liters of ice-water to which 1.09 liters of hydrochloric acid (d=1.18) have been added. After the mixture has been cooled to -10 C. for a few hours, 3-beta-aminoethylamino-4-nitrophenol hydrochloride crystallises. It is filtered off with suction and washed with an ice-cold 2N hydrochloric acid solution and then with ethanol. After recrystallisation from water, the dried product melts, with decomposition, at a temperature above 260 C.
With hydrogenchloride; ammonia; In ethanol; water;
Preparation of 4-nitro 5-N-methylamino phenol 0.052 mole (9 g) of 3-chloro 4-nitro phenol is added to 90 cc of an aqueous solution of 40% monomethylamine. This solution is kept at 60 C. and then evaporated dry under vacuum. To the residue, 30 cc of hydrochloric acid (d=1.19) are added. The 4-nitro 5-N-methylamino phenyl hydrochloride is drained and washed with acetone to eliminate any reactant remaining. The hydrochloride (8.5 g) is treated with stirring with 50 cc of water to which has been added 1 cc of ammonia at 22 Be to release the 4-nitro 5-N-methylamino phenol. The product is filtered, washed with water, recrystallized in 30 cc of ethanol and dried under vacuum. It melts at 207 C.
Example 16; l-(4-Chloro-3-trifluoromethyl-pheny l)-3-{2-chloro-4-[2-(3-hydroxy- propylamino)-pyrimidin-4-yloxy]-phenyl}-urea i) 4-(3-Chloro-4-nitro-phenoxy)-2-methylsulfanyl-pyrimidine160 mg (6.34 mmol) 95% sodium hydride was given to a solution of 1.00 g (5.76 mmol) <strong>[491-11-2]3-chloro-4-nitrophenol</strong> in 15 ml DMF. Stirring was continued for 30 min. at room temperature. 925 mg (5.76 mmol) 4-chloro-2-methylsulfanyl-pyrimidine was added and the mixture heated to 800C for 16 h. The reaction mixture was evaporated, taken up with water and extracted with ethyl acetate. The organic phase was extracted with water, dried (sodium sulphate) and evaporated. The obtained material was dissolved in ethyl acetate and purified by chromatography over silica (ethyl acetate/n-heptane) to give 1.10 g (64%) 4-(3-chloro-4-nitro-phenoxy)-2- methylsulfanyl-pyrimidine. MS: 325.37 (ESI+), 323.33 (ESI-)eta-NMR(400Hz, [DfilDMSO): delta = 2.37(s, 3H, SCH3), 6.96(d, IH, 5-H- pyrimidine), 7.54(d, IH, 6-H-ArNO2), 7.87(s, IH, 2-H-ArNO2), 8.21(d, IH, 5-H- ArNO2), 8.59(d, IH, 6-H-pyrimidine).
With triethylamine; In dichloromethane; at 0℃; for 1h;
Synthesis of l-(tert-butoxycarbonyl)- 7-chloro5 -methoxy-lH-indol-2-yl boronic acid (Cpd.5-4) is shown in Scheme 5. Compound 4-2 is protected as the TBS ether, treated with vinyl Grignard reagent, and cyclized to yield compound 5-2. Boc protection is carried out, and introduction of the boronic acid is performed as described above, yielding compound 5-4.
(3) with mechanical agitation,Drip funnel and reflux condenser in a 500m 1 three-necked flask,Add 99g content95% 2-chloro-4-methoxy nitrobenzene solid,350 g of 20% K0H solution and 3 g of PEG400,Stirring heating,Reflex at 110 CShould be about 15 hours,After the solid is completely dissolved,Plus hydrochloric acid,Precipitation of 2-chloro-4-hydroxy nitrobenzene,After filtration drying,To give 82.5 g of 2-chloro-4-hydroxy nitrobenzene as a yellow solid,Measured content of 95.2%The yield was 90.5%.
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