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Structure of 88-05-1 * 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 Fluorine Chemistry, 1988, vol. 40, p. 147 - 170
2
[ 39066-42-7 ]
[ 88-05-1 ]
[ 93832-46-3 ]
[ 92885-17-1 ]
[ 1682-20-8 ]
Reference：
[1] Journal of Fluorine Chemistry, 1985, vol. 28, p. 357 - 360
3
[ 88-05-1 ]
[ 576-83-0 ]
Reference：
[1] Chemistry - A European Journal, 2018, vol. 24, # 55, p. 14622 - 14626
[2] Journal of Organic Chemistry, 1977, vol. 42, p. 2426 - 2431
4
[ 88-05-1 ]
[ 24006-09-5 ]
Yield
Reaction Conditions
Operation in experiment
54%
Stage #1: With hydrogenchloride In water at -5℃; for 0.75 - 0.833333 h; Stage #2: With sodium nitrite In water for 1 - 1.25 h;
A 3.0 L, 3-neck round bottom flask equipped with a mechanical stirrer and an addition funnel was charged with concentrated hydrochloric acid (0.125 L) and deionized water ( 0.100 L ). The solution was cooled to -5 0C in an ice/salt water bath, and 2,4,6-trimethylaniline (70 niL, 0.50 mol, 1.0 equiv.) was added dropwise over 30 minutes; during this time a white precipitate formed. The mixture was stirred for an additional 15-20 minutes before 52.5 mL of a 9.5 M aq. solution of sodium nitrite (70 mL, 0.50 mol, 1.0 equiv. ) was added dropwise over 30^45 minutes. The resulting brown solution was allowed to stir for 30 minutes before a 3.3 M solution of stannous chloride dihydrate in 1 : 1 concentrated HChH2O (0.455 L, 1.5 mol, 2.5 equiv.) was added over 4 hours with vigorous stirring. (Upon addition of the stannous chloride solution a thick light orange slurry had formed which sometimes caused seizure of the mechanical stirrer. Addition small amounts of deionized water helped to facilitate stirring again.) The mixture was allowed to warm to room temperature and stirred vigorously for 16 hours. The mixture was cooled to 0 0C for 1 hour before filtering through a fine porosity glass fritted buchner funnel, and the collected orange solid washed with brine and diethyl ether. This orange solid was added to a 2-L round-bottom charged with 10 M NaOH(aq) (1.0 L) and diethyl ether (0.700 L) and cooled to -5 0C. Once nearly all of the solid had dissolved (ca. 1 h), the organic layer was removed, and the aqueous layer extracted with diethyl ether (2 x 0.400 L). The combined organic fractions were dried over Na2SO4, filtered into a flame-dried 2.0 L round-bottom flask, placed under an atmosphere of N2(g), cooled to 0 0C, and treated with 4 M HCl in 1 ,4-dioxane (0.125 L). A white precipitate formed, was collected by vacuum filtration, washed with diethyl ether, and recrystalized from 200 proof EtOH to afford the title compound (50 g, 0.27 mol, 54percent) as a white powder. 1H NMR (400 MHz, DMSO) δ 9.57 (3H, s, br, NH, varies), 6.89 (s, 2H), 2.33 (s, 6H), 2.21 (s, 3H); 13C NMR (100 MHz, DMSO) δ 138.06, 136.20, 135.01, 129.17, 20.54, 17.95; IR <n="56"/>(thin film) v 3294, 3002, 2964, 2911, 2680, 1564, 1513, 1481, 852, 825, 753 cm"1; HRESI+/TOF-MS calcd for C9Hi5N2+ [M]+ 151.1230, found 134.0921 for aniline anion radical (134.0975).
45%
Stage #1: With hydrogenchloride; sodium nitrite In water at -4 - 0℃; for 0.5 h; Stage #2: With hydrogenchloride; tin(II) chloride hydrate In water at 20℃; Stage #3: With sodium hydroxide In water at 15℃;
General procedure: To a mixture of concentrated HCl (50 mL) and water (40 mL) was added 2,6-dimethylaniline (24.2 g, 0.2 mol) under vigorous stirring. The resulting mixture was cooled to −4 °C, and a solution of NaNO2 (15.2 g, 0.22 mol) in water (30 mL) was added dropwise to maintain temperature below 0 °C. After addition of the sodium nitrite solution, the reaction mixture was stirred for 30 min. A solution of stannous dichloride hydrate (112.8 g, 0.5 mol) in 160 mL of 6 mol/L hydrochloric acid was added over a period of 1.5 h, during which the temperature of the reaction mixture was maintained below 5 °C. The yellowish slurry was allowed to stand overnight at room temperature and stirring was continued for another 22 h. And then the mixture was cooled by ice-water for 1 h. The pale yellow tin complex salt was collected by filtration, dried on the funnel and washed with brine (50 mL), and ether (2×50 mL). The dry complex salt was stirred in water (100 mL), and slurry was stirred vigorously while it was treated with 10 mol/L NaOH (100 mL). The temperature of the mixture was maintained below 15 °C. The crude hydrazine was extracted from the mixture with ether (2×200 mL), and the etheral solution was washed with water (200 mL) and dried over Na2SO4. The dried etheral solution was diluted with ether to 500 mL. The diluted solution was treated with 4.8 mol/L HCl in 1,4-dioxane (50 mL) until precipitation of the hydrazine hydrochloride was complete. The filtered hydrochloride was washed with ether (50 mL), dried over Na2SO4, and recrystallized from ethanol to afford 2,6-dimethylphenylhydrazine hydrochloride salt as colorless crystals 21.9 g in 63percent yield.
According to method Cl, dichloroethane (2.23 mL) was added to a schlenk flask charged with 2,4,6-trmethylaniIine (1.64 mL, 11.66 mmo.) and triethyl orthoformate (0.97 mL, 5.83 mmol). The tube was evacuated until solvent began to bubble and then sealed and heated with stirring to 120 0C for 24 hours. The reaction mixture was then cooled, added to toluene (50 mL) and then brought to reflux. While still hot, the precipitate was collected by vacuum filtration, washed with toluene (5 mL) and dried in vacuo to afford 1,3-dimesitylimidazolnium chloride (0.89 g, 45percent) as a light peach powder. [0054] The filtrate was allowed to sit overnight to allow for precipitation of λ^/V'-dimesitylformamidine hydrochloride. The precipitate was collected by vacuum filtration, washed with hexanes (5 mL) and dried in vacuo to afford /V/λ/'-dimesitylformamidine hydrochloride (0.65 g, 35percent) as colorless crystals. Method C2: Dichloroethane (1.9 mL, 25 mmol, 5 equiv) was added to a Schlenk flask charged with the aniline (10 mmol, 2 equiv) and triethyl orthoformate (0.83 mL, 5 mmol, 1 equiv). The tube was evacuated until solvent <n="21"/>began to bubble, then sealed under static vacuum and heated to 120 °C for 24- 36 hours. The reaction mixture was then cooled to room temperature. Unreacted substrates were then removed in vacuo. The residue was triturated with acetone or hot toluene, and the product was collected by vacuum filtration, washed with excess solvent and dried in vacuo, providing pure product as a colorless powder (85-95percent). Upon sitting overnight, the formamidine hydrochloride precipitated from the filtrate; l,3-Bis(2,4,6-trimethylphenyl)-imidazoIin.um chloride (Ib) was prepared according to methods A2 (92percent), B2 (49percent), and C2 (45percent). in 24 hours. The product was collected as a white solid after trituration with boiling toluene. The NMR data are in accordance with those reported, (A. J. Arduengo III et al. Tetrahedron 1999, 55, 14523-14534.)
(A) 3-Bromo-2,4,6-trimethylaniline Concentrated hydrochloric acid (80 ml) is cooled in an ice-water bath to 5 C. 2,4,6-Trimethylaniline (13.5 g) is added over a period of 20 minutes with vigorous stirring while keeping the temperature below 15 C. The thick slurry is cooled to 3 C. and 16.8 g of bromine in 80 ml of concentrated hydrochloric acid is added over a period of 25 minutes. The slurry is heated in a water bath for one hour and then cooled in an ice bath for one hour. The reaction mixture is then filtered and the salt is washed with three 50 ml portions of cold distilled water. After drying, the crude product is dissolved in 600 ml of distilled water, treated with 3.0 g of Darco and filtered on a Hyflo-bed to give a solution. Neutralization with concentrated ammonium hydroxide gives a milky solution from which the product solidifies upon cooling to 10 C. After refrigeration for about 16 hours, the tan product is filtered, washed with cold distilled water and dried under vacuum for about 16 hours to give 12.0 g of the title compound, melting point 34.0-35.0 C.
A 3.0 L, 3-neck round bottom flask equipped with a mechanical stirrer and an addition funnel was charged with concentrated hydrochloric acid (0.125 L) and deionized water ( 0.100 L ). The solution was cooled to -5 0C in an ice/salt water bath, and 2,4,6-trimethylaniline (70 niL, 0.50 mol, 1.0 equiv.) was added dropwise over 30 minutes; during this time a white precipitate formed. The mixture was stirred for an additional 15-20 minutes before 52.5 mL of a 9.5 M aq. solution of sodium nitrite (70 mL, 0.50 mol, 1.0 equiv. ) was added dropwise over 30^45 minutes. The resulting brown solution was allowed to stir for 30 minutes before a 3.3 M solution of stannous chloride dihydrate in 1 : 1 concentrated HChH2O (0.455 L, 1.5 mol, 2.5 equiv.) was added over 4 hours with vigorous stirring. (Upon addition of the stannous chloride solution a thick light orange slurry had formed which sometimes caused seizure of the mechanical stirrer. Addition small amounts of deionized water helped to facilitate stirring again.) The mixture was allowed to warm to room temperature and stirred vigorously for 16 hours. The mixture was cooled to 0 0C for 1 hour before filtering through a fine porosity glass fritted buchner funnel, and the collected orange solid washed with brine and diethyl ether. This orange solid was added to a 2-L round-bottom charged with 10 M NaOH(aq) (1.0 L) and diethyl ether (0.700 L) and cooled to -5 0C. Once nearly all of the solid had dissolved (ca. 1 h), the organic layer was removed, and the aqueous layer extracted with diethyl ether (2 x 0.400 L). The combined organic fractions were dried over Na2SO4, filtered into a flame-dried 2.0 L round-bottom flask, placed under an atmosphere of N2(g), cooled to 0 0C, and treated with 4 M HCl in 1 ,4-dioxane (0.125 L). A white precipitate formed, was collected by vacuum filtration, washed with diethyl ether, and recrystalized from 200 proof EtOH to afford the title compound (50 g, 0.27 mol, 54%) as a white powder. 1H NMR (400 MHz, DMSO) delta 9.57 (3H, s, br, NH, varies), 6.89 (s, 2H), 2.33 (s, 6H), 2.21 (s, 3H); 13C NMR (100 MHz, DMSO) delta 138.06, 136.20, 135.01, 129.17, 20.54, 17.95; IR <n="56"/>(thin film) v 3294, 3002, 2964, 2911, 2680, 1564, 1513, 1481, 852, 825, 753 cm"1; HRESI+/TOF-MS calcd for C9Hi5N2+ [M]+ 151.1230, found 134.0921 for aniline anion radical (134.0975).
45%
General procedure: To a mixture of concentrated HCl (50 mL) and water (40 mL) was added 2,6-dimethylaniline (24.2 g, 0.2 mol) under vigorous stirring. The resulting mixture was cooled to -4 C, and a solution of NaNO2 (15.2 g, 0.22 mol) in water (30 mL) was added dropwise to maintain temperature below 0 C. After addition of the sodium nitrite solution, the reaction mixture was stirred for 30 min. A solution of stannous dichloride hydrate (112.8 g, 0.5 mol) in 160 mL of 6 mol/L hydrochloric acid was added over a period of 1.5 h, during which the temperature of the reaction mixture was maintained below 5 C. The yellowish slurry was allowed to stand overnight at room temperature and stirring was continued for another 22 h. And then the mixture was cooled by ice-water for 1 h. The pale yellow tin complex salt was collected by filtration, dried on the funnel and washed with brine (50 mL), and ether (2×50 mL). The dry complex salt was stirred in water (100 mL), and slurry was stirred vigorously while it was treated with 10 mol/L NaOH (100 mL). The temperature of the mixture was maintained below 15 C. The crude hydrazine was extracted from the mixture with ether (2×200 mL), and the etheral solution was washed with water (200 mL) and dried over Na2SO4. The dried etheral solution was diluted with ether to 500 mL. The diluted solution was treated with 4.8 mol/L HCl in 1,4-dioxane (50 mL) until precipitation of the hydrazine hydrochloride was complete. The filtered hydrochloride was washed with ether (50 mL), dried over Na2SO4, and recrystallized from ethanol to afford 2,6-dimethylphenylhydrazine hydrochloride salt as colorless crystals 21.9 g in 63% yield.
2-methyl-5-nitro-N,N'-bis-(2,4,6-trimethylphenyl)-pyrimidine-4,6-diamine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With triethylamine; In acetonitrile;
EXAMPLE 4 2-Methyl-5-nitro-N,N'-bis-(2,4,6-trimethylphenyl)-pyrimidine-4,6-diamine A mixture of <strong>[13162-43-1]2-methyl-5-nitro-4,6-dichloropyrimidine</strong> (0.513 g, 2.47 mmol) in 6 ml of acetonitrile was treated with 2,4,6-trimethylaniline (0.333 g, 2.46 mmol) and triethylamine (1 ml) and stirred at room temperature for 4 hours. The mixture was quenched with water and extracted with ethyl acetate. The organic layer was washed with brine, dried and concentrated to give 0.622 g of bright yellow solid. The solid was purified through silica gel column chromatography to give (6-chloro-2-methyl-5-nitro-pyrimidin-4-yl)-(2,4,6-trimethylphenyl) amine and the title compound. 1 H NMR (CDCl3) for 6-(chloro-2-methyl-5-nitro-pyrimidin-4-yl)-(2,4,6-trimethylphenyl)amine 6 2.16 (s, 6H), 2.33 (s, 3H), 2.43 (s, 3H), 6.95 (s, 2H), 8.79 (s, 1H) ppm. 1 H NMR (CDCl3) for 2-methyl-5-nitro-N,N'-bis-(2,4,6-trimethylphenyl)-pyrimidine-4,6-diamine: d 2.11 (s, 3H), 2.22 (s, 12H), 2.33 (s, 3H), 6.96 (s, 4H), 10.44 (s, 2H) ppm.
With triethylamine; In acetonitrile;
EXAMPLE 4 2-Methyl-5-nitro-N,N'-bis-(2,4,6-trimethylphenyl)-pyrimidine-4,6-diamine A mixture of <strong>[13162-43-1]2-methyl-5-nitro-4,6-dichloropyrimidine</strong> (0.513 g, 2.47 mmol) in 6 ml of acetonitrile was treated with 2,4,6-trimethylaniline (0.333 g, 2.46 mmol) and triethylamine (1 ml) and stirred at room temperature for 4 hours. The mixture was quenched with water and extracted with ethyl acetate. The organic layer was washed with brine, dried and concentrated to give 0.622 g of bright yellow solid. The solid was purified through silica gel column chromatography to give (6-chloro-2-methyl-5-nitro-pyrimidin-4-yl)-(2,4,6-trimethylphenyl) amine and the title compound. 1H NMR (CDCl3) for 6-(chloro-2-methyl-5-nitro-pyrimidin-4-yl)-(2,4,6-trimethylphenyl)amine delta 2.16 (s, 6H), 2.33 (s, 3H), 2.43 (s, 3H), 6.95 (s, 2H), 8.79 (s, 1H) ppm. 1H NMR (CDCl3) for 2-methyl-5-nitro-N,N'-bis-(2,4,6-trimethylphenyl)-pyrimidine-4,6-diamine: delta 2.11 (s, 3H), 2.22 (s, 12H), 2.33 (s, 3H), 6.96 (s, 4H), 10.44 (s, 2H) ppm.
5-[(2,4,6-Trimethylphenyl)amino]-3-methyl-1-(1-ethylpropyl)-1,2,4-triazine-6(1H)-one[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
83%
With trifluoromethanesulfonic acid anhydride; In tetrahydrofuran; hexane; dichloromethane; ethyl acetate;
Part D To a solution of the triazine dione product from above (198 mg, 1 mmol) in CH2 Cl2 (5 mL) was added trifluoromethanesulfonic anhydride (0.19 mL, 1.1 mmol) and <strong>[108-75-8]2,4,6-collidin</strong>e (0.15 mL, 1.1 mmol). The resulting reaction mixture was stirred at room temperature for 30 min., then 2,4,6-trimethylaniline (162 mg, 1.2 mmol) in 5 mL of THF was added followed by addition of <strong>[108-75-8]2,4,6-collidin</strong>e (0.15 mL, 1.1 mmol). The resulting reaction mixture was stirred at room temperature for 1 hr, at which time TLC showed complete reaction. The reaction mixture was partitioned between water and CH2 Cl2. The organic layer was dried (Na2 SO4), filtered and evaporated in vacuo. The residue was purified by column chromatography on silica gel using EtOAc/hexane (1:9) to afford 260 mg of the title compound (83% yield). mp=133-135 C. 1 H NMR (300 MHz, CDCl3): delta7.89 (br s, 1H); 6.94 (s, 2H); 4.72 (m, 1H); 2.31 (s, 3H); 2.19 (s, 9H); 1.9-1.7 (m, 4H); 0.85 (t, 6H, J=7.32 Hz). Mass Spec. (NH3 --CI): Calc. (M+H)+=315, Obs. (M+H)+=315.
With trifluoroacetic acid; In trifluoroethanol; at 90℃; for 48h;
To a solution of 2,4-dichlorothieno[2,3-phiyrimidine (805 mg, 3.94 mmol), TFA (0.91 mL, 11.82 piunol) in TFE (1 1 mL) was added 2,4,6-trimethylaniline (0.15 mg, 1.1 mmol) in a sealed tube. The reaction was stirred at 90 0C for 2 d. Reaction mixture was diluted with CH2Cl2 and washed with saturated NaHCO3 (3 x 20 mL). The combined organic layers were washed with brine, dried over Na2SO4, filtered and concentrated in vacuo. The crude product was purified by HPLC to afford the product as a white solid (43.4 mg, 36percent):1H NMR (DMSO, 300 MHz) delta 2.08 (s, 6H), 2.27 (s, 3H), 6.97 (s, 2H), 7.69 (d, J = 6.0 Hz, IH), 7.78 (d, J = 6.0Hz, IH), 9.68 (s, IH).
With n-butyllithium; diisopropylamine; In tetrahydrofuran; hexane; at -78 - 20℃;
To a solution of diisopropylamine (5.45 mL, 38.4 mmol) in THF (15 mL) is added at 0C n- butyllithium (24 mL, 1.6M in hexane). The mixture is stirred for 15 min at O9C and then cooled to -78C. 2,4,6-trimethylaniline (3.77 mL, 26.85 mmol) is added at this temperature. After stirring for 10 min, <strong>[2252-37-1]2-bromo-6-fluoro-benzoic acid</strong> (2.8 g, 12.78 mmol) in THF (10 mL) is added at -78 C. The reaction mixture is allowed to reach room temperature and is stirred overnight, concentrated, acidified to pH 1 with 10 % aqueous HCI and extracted with ethyl acetate. The organic phase is dried over Na2SO4 and evaporated in vacuo. The residue is <n="20"/>triturated with hexane, and the solid is filtered off and dried in vacuo to yield 2-bromo-6- (2,4,6-trimethyl-phenylamino)-benzoic acid as a brownish solid. ESI-MS: 334.3 [M + H]+; rt = 6.01 min.
2-Bromo-6-(2,4,6-trimethyl-phenylamino)-benzoic acidTo a solution of diisopropylamine (5.45 ml_, 38.4 mmol) in THF (15 mL) is added at 0C n- butyllithium (24 mL, 1.6M in hexane). The mixture is stirred for 15 min at O9C and then cooled to -78C. 2,4,6-trimethylaniline (3.77 mL, 26.85 mmol) is added at this temperature. After stirring for 10 min, <strong>[2252-37-1]2-bromo-6-fluoro-benzoic acid</strong> (2.8 g, 12.78 mmol) in THF (10 mL) is added at -78 C. The reaction mixture is allowed to reach room temperature and is stirred overnight, concentrated, acidified to pH 1 with 10 % aqueous HCI and extracted with ethyl acetate. The organic phase is dried over Na2SO4 and evaporated in vacuo. The residue is triturated with hexane, and the solid is filtered off and dried in vacuo to yield 2-bromo-6- (2,4,6-trimethyl-phenylamino)-benzoic acid as a brownish solid. ESI-MS: 334.3 [M + H]+; rt = 6.01 min.
at 120℃; for 24h;Product distribution / selectivity;
According to method Cl, dichloroethane (2.23 mL) was added to a schlenk flask charged with 2,4,6-trmethylaniIine (1.64 mL, 11.66 mmo.) and triethyl orthoformate (0.97 mL, 5.83 mmol). The tube was evacuated until solvent began to bubble and then sealed and heated with stirring to 120 0C for 24 hours. The reaction mixture was then cooled, added to toluene (50 mL) and then brought to reflux. While still hot, the precipitate was collected by vacuum filtration, washed with toluene (5 mL) and dried in vacuo to afford 1,3-dimesitylimidazolnium chloride (0.89 g, 45%) as a light peach powder. [0054] The filtrate was allowed to sit overnight to allow for precipitation of lambda^/V'-dimesitylformamidine hydrochloride. The precipitate was collected by vacuum filtration, washed with hexanes (5 mL) and dried in vacuo to afford /V/lambda/'-dimesitylformamidine hydrochloride (0.65 g, 35%) as colorless crystals. Method C2: Dichloroethane (1.9 mL, 25 mmol, 5 equiv) was added to a Schlenk flask charged with the aniline (10 mmol, 2 equiv) and triethyl orthoformate (0.83 mL, 5 mmol, 1 equiv). The tube was evacuated until solvent <n="21"/>began to bubble, then sealed under static vacuum and heated to 120 C for 24- 36 hours. The reaction mixture was then cooled to room temperature. Unreacted substrates were then removed in vacuo. The residue was triturated with acetone or hot toluene, and the product was collected by vacuum filtration, washed with excess solvent and dried in vacuo, providing pure product as a colorless powder (85-95%). Upon sitting overnight, the formamidine hydrochloride precipitated from the filtrate; l,3-Bis(2,4,6-trimethylphenyl)-imidazoIin.um chloride (Ib) was prepared according to methods A2 (92%), B2 (49%), and C2 (45%). in 24 hours. The product was collected as a white solid after trituration with boiling toluene. The NMR data are in accordance with those reported, (A. J. Arduengo III et al. Tetrahedron 1999, 55, 14523-14534.)
With toluene-4-sulfonic acid; In toluene; for 12h;Reflux;
General procedure: A reaction mixture of 2-acetylquinoline (1.71 g, 10.0 mmol), 2,6-dimethylaniline (1.21 g, 10.0 mmol), p-toluenesulfonic acid (0.20 g), and toluene (60 mL) was refluxed for 12 h. The solvent was rotary evaporated and the resulting solid was eluted with petroleum ether on an alumina column. The second eluting part was collected, concentrated to give a yellow solid and L1 was obtained in 72% yield.
With tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate; DavePhos; In toluene; at 85℃;Inert atmosphere;
General procedure: Compound 8 (7.5 mmol), 9a-c (10.5 mmol), Pd2dba3 (0.19 mmol), 2'-(dicyclohexyl phosphino)-N,N-dimethylbiphenyl-2-amine (0.75 mmol) and NaOtBu (10.5 mmol) were weighed in a 50 mL RB flask and dry toluene (20 mL) was added and flushed with argon for 15 min. Subsequently the reaction mixture was stirred at 85 C overnight, cooled to room temperature, diluted with EtOAc and filtered through a pad of celite and concentrated to obtain a dark brown solid which was flash chromatographed on silica gel eluting with 30% EtOAc in hexanes.
With pyridinium trifluroacetate; at 110℃; for 0.333333h;
General procedure: A 25 ml flask was charged with oxadiazole (2 mmol), primary amine (2.2-4.0 mmol), and protic ionic liquid (2 g). The mixture was stirred at 110 C and monitored by TLC until oxadiazole was not detected unless otherwise stated. The reaction mixture was diluted with CH2Cl2 (15 ml), followed by washing twice with H2O (10 ml×2), from which protic ionic liquid could be recovered by rotavapor and recrystallization. The organic layers were dried over anhydrous Na2SO4, filtered, and evaporated under reduced pressure to give crude product, which was purified by column chromatography on silica gel with CH2Cl2/MeOH to give 1,2,4-triazole.
With potassium carbonate; In N,N-dimethyl-formamide; at 20℃;
General procedure: Compound 5 was dissolved in anhydrous DMF (10mL) in the presence of anhydrous K2CO3 (2eq), followed by the addition of appropriate substituted phenol (1.1eq) or substituted phenylamine (1.1eq). The reaction mixture was stirred at room temperature overnight. The solvent was removed under reduced pressure, and water (20mL) was added. Extracted with ethyl acetate (2×10mL), and the organic phase was washed with saturated sodium chloride (10mL), and dried over anhydrous Na2SO4 to give the corresponding crude product, which was purified by flash column chromatography (EtOAc : petroleum ether=1:1) to afford compounds 6[21].
N-mesityl-5-phenyl-3-pyrazole carboxamide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
54.9%
With O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate; triethylamine; In N,N-dimethyl-formamide; for 4 - 10h;Reflux; Inert atmosphere;
A solution of acid 4 (0.09 g, 0.47 mmol) in dry DMF (2 mL) treated sequentially with amine (5a-i, 6a-e and 7a-h; 0.517 mmol)and triethylamine (0.94 mmol) was stirred under a N2 atmosphere for 15 min, later TBTU (0.56 mmol) was added and reaction mixture refluxed for 4-10 h. The reaction mixture was quenched with aq satd NH4Cl solution (10 mL). After 10 min, it was diluted withCHCl3 (2 10 mL) and washed with water (10 mL), NaHCO3 solution(10 mL) and brine (10 mL). The organic layers were dried over anhydrous sodium sulfate, evaporated and the residue purified by column chromatography using 30% ethyl acetate in pet. ether to afford corresponding amides 8a-i, 9a-e and 10a-h.
4,5,6-trichloro-N-(2,4,6-trimethylphenyl)-2-pyrimidinamine[ No CAS ]
2,5,6-trichloro-N-(2,4,6-trimethylphenyl)-4-pyrimidinamine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
0.15 g; 3.15 g
With N-ethyl-N,N-diisopropylamine; In 1,4-dioxane; at 55℃; for 16h;Inert atmosphere;
Example A3 a)<strong>[1780-40-1]2,4,5,6-<strong>[1780-40-1]tetrachloropyrimidine</strong></strong> (0.0134 mol), 1,4-dioxane (30 ml), 2,4,6-trimethyl aniline (0.0134 mol), and N,N-bis(1-methylethyl)ethanamine (0.0136 mol) were added to a flask under argon and stirred at 55 C for 16 hours. The solvent was evaporated, and the residue was dissolved in CH2Cl2, then purified by column chromatography over silica gel (eluent: CH2Cl2/hexane 1/4, and 1/2). The desired fractions were collected and their solvent was evaporated, yielding 0.15 g 4,5,6-trichloro-N-(2,4,6-trimethylphenyl)-2-pyrimidinamine (interm. 6) and 3.15 g 2,5,6-trichloro-N-(2,4,6-trimethylphenyl)-4-pyrimidinamine (interm. 7).
2,6-bis(mesitylamino)-4-methylpyridine-3-carbonitrile[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
68%
With zinc(II) oxide; In 1-methyl-pyrrolidin-2-one; at 180℃; for 4h;
2,4,6-trimethyaniline 9.0ml (64.16 mmol), and NMP in 0.8ml, <strong>[875-35-4]2,6-dichloro-4-methylnicotinonitrile</strong>3g (16,04 mmol) and zinc oxide were added and 1530mg, the oil bath temperature was raised to 180 It was. While the produced water was removed during the reaction was heated and stirred for 4 hours in 180 C . Then, cooling to 80 , and the reaction solution was added dropwise over 30 minutes in the water 1000ml, and then cooled to room temperature and filtered. Washing the obtained crystals to give the objective compound in a dry, 4.2g (68% yield)
68%
With zinc(II) oxide; In 1-methyl-pyrrolidin-2-one; at 180℃; for 4h;
2,4,6-trimethyaniline 9.0ml (64.16 mmol), and NMP in 0.8ml, <strong>[875-35-4]2,6-dichloro-4-methylnicotinonitrile</strong> 3g (16,04 mmol) and zinc oxide 1530mg was added, and the The oil bath was heated to 180 C .While the produced water was removed during the reaction was stirred for 4 hours in 180 C heating.After that, it cooled to 80 ,Was added dropwise to the reaction solution to 1000ml of water over 30 minutes was filtered and cooled to room temperature.Washing the obtained crystals,To obtain a compound of a dry object and 4.2g (68% yield).
(S)-N-mesityl-1-tritylaziridine-2-carboxamide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
85%
General procedure: To a suspension of corresponding amine (3 mmol) in anhydrous CH2Cl2 (10 mL) at -10 C trimethylaluminum (3 mmol) was added dropwise under a nitrogen atmosphere. The reaction mixture was warmed to 25 C and stirred for 1 h. After this time, the reaction mixture was again cooled to -10 C and <strong>[75154-68-6]methyl (2S)-N-tritylaziridine-2-carboxylate</strong> 1 (1 mmol) was added dropwise in anhydrous CH2Cl2 (5 mL). The resulting mixture was stirred at room temperature for the indicated time. Then, the reaction was cooled to 0 C and carefully quenched with aqueous satd NaHCO3 and extracted with Et2O (3Chi10 mL), the combined organic layers were dried over MgSO4, filtered and the solvents were removed under reduced pressure. The crude products were purified by flash chromatography on silica gel (AcOEt/hexane 1:4).
N1,N2-bis(4-isopropoxy-2,6-dimethylphenyl)ethylene-1,2-diamine[ No CAS ]
N1-(2,4,6-trimethylphenyl)-N2-(4-isopropoxy-2,6-dimethylphenyl)ethane-1,2-diamine[ No CAS ]
[ 134030-21-0 ]
Yield
Reaction Conditions
Operation in experiment
Sodium borohydride (3.8 g, 5 mmol) was added to a 100 ml jar.The resulting yellow solid was subsequently added to contain three imine compounds (7.0 g, 1 mmol)And tetrahydrofuran (30ml). Stir at room temperature and add 10 ml of methanol in three batches.The reaction produces hydrogen and exotherm. The reaction was stirred at room temperature for about 5 h. The TLC plate (25% ethyl acetate/n-hexane) was used to judge whether the reaction reached the end point. The color of the solution gradually changed from yellow to pale yellow. After the reaction was completed, 50 ml of water was added to stop the reaction, followed by the addition of 30 ml of methylene chloride. The mixture was washed three times in a separatory funnel and the pale yellow solution was removed. After drying over anhydrous sodium sulfate, the solvent was removed on a rotary evaporator to give a viscous mass. Three pale gray liquid amine compounds were isolated on a silica gel column: 1,2-bis(1,3,5-trimethylphenyl)-ethylendiamine, 1-(1,3,5- Trimethylphenyl)-2-(4-isopropoxy-2,6-dimethylphenyl)- ethylenediamine, 1,2-bis(4-isopropoxy-2,6-di Methylphenyl) ethylenediamine.Purified 1-(1,3,5-trimethylphenyl)-2-(4-isopropoxy-2,6-dimethylphenyl)-ethylendiamine dissolved in 10 ml of methanol and 3 ml of water Then, 1.0 ml of concentrated hydrochloric acid was titrated in a cold bath to give off white gas and a large amount of heat was emitted. The resulting white solid product was filtered, washed and dried under reduced pressure to give 0.7 g of the hydrochloride salt of ethylenediamine as a white solid.
N-(2-(cyclohexylamino)-2-oxo-1-phenylethyl)-N-mesityl-2,4-dimethylthiazole-5-carboxamide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
16%
General procedure: The aldehyde (0.8 equivalent) and amine (0.7 equivalent) were dissolved in methanol (2.0 mL) and stirred for two to 3 h depending upon the starting material. The acid (100 mg, 1 equivalent) and isocyanide (0.7 equivalent) were added in the reaction mixture and further stirred. The reaction mixture was monitored using TLC analysis.Water (4 mL) was added upon completion of the reaction.The resulted solid was filtered off and dissolved in ethyl acetate(10 mL), washed with water (2 3 mL) and dried over sodium sulphate. The crude product was purified using silica gel column chromatography. The ethyl acetate:hexane (6:4) solvent system was used for the purification of these compounds.
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