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CAS No. : | 1484-12-4 | MDL No. : | MFCD00013431 |
Formula : | C13H11N | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | SDFLTYHTFPTIGX-UHFFFAOYSA-N |
M.W : | 181.23 | Pubchem ID : | 15142 |
Synonyms : |
|
Signal Word: | Danger | Class: | 9 |
Precautionary Statements: | P273-P280-P305+P351+P338 | UN#: | 3077 |
Hazard Statements: | H302-H318-H400 | Packing Group: | Ⅲ |
GHS Pictogram: |
* 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.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | Stage #1: acetyl chloride With aluminum (III) chloride In dichloromethane Stage #2: N-methylcarbazole In dichloromethane at 20℃; for 4h; | |
83% | With aluminum (III) chloride In carbon disulfide at 50℃; for 6h; | |
76% | Stage #1: acetyl chloride With aluminum (III) chloride In dichloromethane Stage #2: N-methylcarbazole In dichloromethane at 20℃; for 2.5h; Reflux; | 1,1'-(9-Carbazole-3,6-diyl)diethanone (5c). General procedure: A suspensionof AlCl3 (4.27 g, 32.10 mmol) in CH2Cl2 (35 ml) wascooled and treated with AcCl (1.72 ml, 24.07 mmol) inCH2Cl2 (8 ml). After a light-yellow mixture was formed, itwas cooled and treated by portionwise addition ofcarbazole 4 (1.34 g, 8.08 mmol), the mixture was stirredfor 1 h at room temperature and then refluxed for 1.5 h.The reaction mixture was poured into 15% hydrochloricacid (200 ml) with ice. The obtained gray-brownprecipitate was filtered off, washed with 5% hydrochloricacid, then with water to neutral pH, and recrystallized froma mixture of EtOH-CHCl3 with activated carbon. Yield1.52 g (75%), |
59% | With aluminium trichloride In nitrobenzene at 0 - 25℃; for 54h; | |
With carbon disulfide; aluminium trichloride | ||
With aluminum (III) chloride In 1,2-dichloro-ethane |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With 1,4-dioxane; nickel at 230℃; Hydrogenation; | ||
With palladium on activated charcoal; hydrogen at 120℃; for 48h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | With hydrogen bromide; dimethyl sulfoxide at 120℃; for 4.5h; | |
67% | With dimethyl sulfoxide; ethylene dibromide at 80℃; for 10h; | |
62% | With aluminum tri-bromide; bis-[(trifluoroacetoxy)iodo]benzene In acetonitrile at 23℃; |
47% | With N-Bromosuccinimide In acetonitrile at 0 - 25℃; for 20.5h; | |
With bromine; acetic acid | ||
With tetrachloromethane; N-Bromosuccinimide; dibenzoyl peroxide |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With nitric acid In acetic acid for 1h; | |
83% | With uronium nitrate In acetic acid for 20h; | |
57% | With aluminium trinitrate In acetonitrile at 50℃; regioselective reaction; |
45.3% | With nitric acid In water at 40 - 90℃; | Procedure for synthesis of 9-methyl-3-nitro-9H-carbazole (7) The suspension of 9-methyl-9H-carbazole (6, 55 mmol) in distillated water (100 mL) was stirred for 1hr at 40. 70% nitric acid(9ml) was added to this mixture and reaction temperature was raised each 10 per hour and retained at 80~90 for 3hrs. This mixture was cooled to room temperature and was filtered by vaccum. The reaction mixture was filtered through a filter paper and it was washed several times with distillated water and was dried at 55 in oven for 1 day. Ethyl acetate(40ml) and acetone(20ml) were added to crystal and were sonicated for 10 mins. After that, it was filtered and dried to obtain 9-methyl-3-nitro-9H-carbazole (7).Yield 45.3 %, Rf = 0.545 (2:1 n-hexane-ethyl acetate); 1H NMR(DMSO-d6, 400MHz): δH 9.125(d, J=2.0Hz, 1H), 8.367(d, J=7.6Hz, 1H), 8.314(dd, J=2.4, 8.8Hz, 1H), 7.721(d, J=9.2Hz, 1H), 7.674(d, J=8.4Hz, 1H), 7.571(t, J=7.6Hz, 1H), 7.318(t, J=7.4Hz, 1H), 3.922(s, CH3). |
With nitric acid; acetic acid | ||
With nitric acid; nitrobenzene at 10 - 20℃; | ||
With nitric acid; acetic acid at 60℃; | ||
With nitric acid In acetic acid for 1h; | 1.b The product obtained as described in step a) above (3.9 g; 0.022 mol) was dissolved in glacial acetic acid (70 ml). A mixture containing fuming nitric acid (1.05 ml) in glacial acetic acid (3.11 ml) was then added dropwise over 30 minutes. The solution thus obtained was stirred for a further 30 minutes. The reaction mixture was then poured into H2O and ice, stirred for 15 minutes and filtered. The residue thus obtained (4 g) was purified by flash chromatography, eluding with an 85/15 hexane/ethyl acetate mixture. The desired product (2.2 g) was thus obtained. 1H NMR (300 MHz, chloroform-d) δ ppm 3.92 (s, 3H), 7.27-7.51 (m, 3H), 7.54-7.63 (m, 1H), 8.15 (d, J=7.9 Hz, 1H), 8.40 (dd, J=8.9, 2.2 Hz, 1H), 9.01 (d, J=2.0 Hz, 1H). | |
With nitric acid; acetic acid for 1h; | 1.b b) 9-methyl-3-nitro-9H-carbazole; The product obtained as described in step a) above (3.9 g; 0.022 mol) was dissolved in glacial acetic acid (70 ml). A mixture containing fuming nitric acid (1.05 ml) in glacial acetic acid (3.11 ml) was then added dropwise over 30 minutes.The solution thus obtained was stirred for a further 30 minutes. The reaction mixture was then poured into H2O and ice, stirred for 15 minutes and filtered. The residue thus obtained (4 g) was purified by flash chromatography, eluting with an 85/15 hexane/ethyl acetate mixture.The desired product (2.2 g) was thus obtained. 1H NMR (300 MHz, chloroform-d) δ ppm 3.92 (s, 3 H), 7.27 - 7.51 (m, 3 H), 7.54 - 7.63 (m, 1 H), 8.15 (d, J = 7.9 Hz, 1 H)1 8.40 (dd, J = 8.9, 2.2 Hz, 1 H), 9.01 (d, J = 2.0 Hz, 1 H). | |
With nitric acid; acetic acid at 20℃; for 0.5h; | ||
2.5 g | With nitric acid; acetic acid In methanol at 0 - 20℃; for 16h; | 49.b Step b. . To a solution of 9-methyl-9H-carbazole (2.OOg, 11.05 mmol) in acetic acid (20 ml) was added HNO3 (1.39 g, 22.10 mmol) at 0°C. The reaction mixture was stirred at rt for 16 h. The resulting reaction mixture was poured in to ice cold water (100 ml) and the obtained solids were collected by filtration. The resulting solid was dried under vacuum yielding 9-methyl-3-nitro-9H-carbazole (2.5g,11.06 mmol). LCMS: Method C, 2.40 mi MS: ES+ 227.14. |
With hydrogenchloride; sodium nitrite; benzene | ||
With nitric acid; acetic acid |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With chlorosulfonic acid In dichloromethane at -5℃; for 2h; | |
With sulfuric acid; nitrobenzene |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With 5% rhodium-on-charcoal; trifluoroacetic acid at 50℃; for 19h; Green chemistry; regioselective reaction; | |
73% | With iron(III) chloride In chloroform at 20℃; for 0.5h; Inert atmosphere; | |
24% | With nitric acid In water; acetic acid |
With nitrosonium perchlorate; zinc 1) AcCN, 15 min, 2a) AcCN, RT, 20 min, 2b) 10 min, reflux; Yield given. Multistep reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With iodine In dimethyl sulfoxide at 100℃; for 8h; | |
With palladium on activated charcoal; trimethylbenzene |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
at 325℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
at 325℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | Stage #1: 9H-carbazole With sodium hydride In N,N-dimethyl-formamide at 0 - 20℃; for 0.5h; Stage #2: methyl iodide In N,N-dimethyl-formamide | 49.a Step a. To a solution of carbazole (3.OOg, 17.96 mmol) in DMF (25 ml) was added NaH (1.72 g, 71.85 mmol) portion wise at 0°C. The reaction mixture was stirred at rt for 30 mm. Methyl iodide (5.0g, 35.92 mmol) was added to the reaction mixture at 0°C. The reaction mixture was stirred at rt for 2 h. The resulting reaction mixture was poured into water (100 ml) and the obtained solids were collected by filtration. The resulting solid was dried under vacuum yielding 9-methyl-9H-carbazole (3 .3g, quantitative). This material was used directly for the next step without further purification. |
96% | With sodium hydride In N,N-dimethyl-formamide at 0 - 20℃; | |
95% | With sodium hydroxide In N,N-dimethyl-formamide at 2℃; for 4h; |
95% | With potassium hydroxide In dimethyl sulfoxide at 80℃; for 24h; | Synthesis of 9-methyl-9H-carbazole 3 1-Iodomethane (14.2 g, 100 mmol) and potassium hydroxide (33.9 g, 605.4 mmol) were added to asolution of carbazole (18.5 g, 101.1 mmol) in DMSO (200 mL) under stirring. The reaction mixture was stirred for 24 h at 80°C. The reaction was quenched with water. A white precipitate formed. Itwas filtered off, washed several times with water and pentane, and finally dried under vacuum. Itwas purified by filtration on a plug of silicagel using DCM as the eluent (17.37 g, 95% yield). |
95% | With sodium hydroxide In dimethyl sulfoxide at 20℃; for 5h; | 9-Methyl-9-carbazole (4d). A mixture of carbazole 4(1.0 g, 5.99 mmol) in DMSO (15 ml) and NaOH (0.48 g,12.00 mmol) was cooled and treated by the addition of MeI(1.28 g, 9.01 mmol) with stirring at room temperature for5 h. The mixture was then poured into ice water (100 ml).The obtained precipitate was filtered off, washed wih water(3×25 ml), and dried at reduced pressure over P2O5. Thecompound was used for the further synthetic steps withoutadditional purification. Yield 1.03 g (95%), white powder,mp 90-93°C (mp 90-92°C18). |
95% | Stage #1: 9H-carbazole With potassium hydroxide In N,N-dimethyl-formamide at 20℃; for 0.5h; Stage #2: methyl iodide In N,N-dimethyl-formamide at 20℃; for 12h; | |
95% | Stage #1: 9H-carbazole With sodium hydride In N,N-dimethyl-formamide at 0℃; for 0.5h; Stage #2: methyl iodide In N,N-dimethyl-formamide at 0 - 25℃; for 6h; | |
94% | Stage #1: 9H-carbazole With sodium hydride In N,N-dimethyl-formamide for 0.166667h; Stage #2: methyl iodide In N,N-dimethyl-formamide at 20℃; for 3h; | |
93.33% | Stage #1: 9H-carbazole With sodium hydride In N,N-dimethyl-formamide at 0℃; for 0.5h; Stage #2: methyl iodide In N,N-dimethyl-formamide at 20℃; for 5h; | |
93.33% | Stage #1: 9H-carbazole With sodium hydride In N,N-dimethyl-formamide at 0℃; for 0.5h; Stage #2: methyl iodide In N,N-dimethyl-formamide at 20℃; for 5h; | 1.1.3. Synthesis of 9-methylcarbazole (7) To a stirred solution of carbazole (6, 5.0 g, 0.025 mol, 1 equiv.) in N, N-dimethylformamide (20 mL) maintained at 0°C, NaH (0.028 mol, 1.1 equiv.) was carefully added in small portions and stirred for 30 min. To this reaction mass, methyl iodide (4.34 g, 0.0306 mol, 1.2 equiv.) was added and further stirred at room temperature for 5 h. Progress of the reaction was monitored on TLC. On completion, the reaction mixture was poured into ice cold water, and the solid precipitated was filtered and washed with cold water to yield a white solid compound 7. Yield: 93.33 %; M.P. 86-88 °C; FTIR (ATR, max, cm-1): 3048.18 (Ar-H Str.), 2953.18 (C-H Str. of CH3); 1H-NMR (400 MHz, CDCl3, ppm): 8.13 (d, J = 7.80 Hz, 2H, Ar-H), 7.50 (m, 2H, Ar-H), 7.43 (d, J = 8.2 Hz, 2H, Ar-H), 7.25 (m, 2H, Ar-H), 3.87 (s, 3H, N-CH3); 13C-NMR (100 MHz, CDCl3, ppm): 140.97, 125.63, 122.74, 120.27, 118.79, 108.38, 29.02 (N-CH3). |
92% | Stage #1: 9H-carbazole With sodium hydride In N,N-dimethyl-formamide at 20℃; for 0.5h; Stage #2: methyl iodide In N,N-dimethyl-formamide | |
92.5% | Stage #1: 9H-carbazole With potassium hydroxide In N,N-dimethyl-formamide at 20℃; for 0.666667h; Stage #2: methyl iodide In N,N-dimethyl-formamide at 20℃; for 12h; | |
91% | With potassium <i>tert</i>-butylate In diethyl ether for 1h; Ambient temperature; | |
89.6% | With sodium hydroxide In water; dimethyl sulfoxide at 90℃; | 2.5.3 N-methylcarbazole A mixed solution of 50% aqueous NaOH (12mL), DMSO (40mL) and carbazole (3.0g, 17.9mmol) was slowly added iodomethane (0.57mL, 19.8mmol) at room temperature. The mixture was stirred at 90°C overnight and then cooled to room temperature. After that, the brine was added to the mixture and the organic phase extracted with dichloromethane was dried over MgSO4. The solvent was removed and residue was purified by a column chromatography (silica gel, petroleum ether/DCM=10/1, v/v) to give 2.90g of yellow liquid (yield: 89.6%). 1H NMR (500MHz, CDCl3): δ 8.12 (d, 2H, J=10.0Hz), 7.46 (m, 4H), 7.25 (m, 2H), 0.86 (t, 3H, J=8.5Hz) ppm. |
87% | With potassium carbonate In N,N-dimethyl-formamide at 20℃; for 8h; | 1 Synthesis of Intermediate B; Carbazole (16.7 g, 100 mmol), iodomethane (18.5 g, 130 mmol) and K2CO3 (138 g, 1.0 mol) were dissolved in dimethylformamide (DMF) (500 ml), and the reaction mixture was stirred at room temperature for eight hours. After the reaction was terminated, a solid material was filtered out. The resultant solution was extracted three times with diethylether (300 ml). The collected diethylether layer was washed with excess distilled water, dried over MgSO4, filtered, and dried under a reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography to give intermediate B (15.8 g, yield: 87%). The structure of intermediate B was determined by 1H NMR. 1H NMR (CDCl3, 300 MHz) δ (ppm) 8.22 (d, 2H), 7.41 (d, 2H), 7.35-7.28 (m, 4H), 3.71 (s, 3H); 13C NMR (CDCl3, 100 MHz) δ (ppm) 140.5, 125.6, 122.5, 120.0, 118.7, 109.5, 29.5. |
86% | With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0 - 20℃; for 2.5h; | |
83% | With tetrabutylammonium tetrafluoroborate In N,N-dimethyl-formamide cathodic reduction at controlled potential; | |
82.3% | With sodium hydroxide In benzene for 2h; Ambient temperature; | |
80.3% | Stage #1: 9H-carbazole With 18-crown-6 ether; potassium hydroxide In toluene at 110℃; for 0.333333h; Stage #2: methyl iodide In toluene at 110℃; for 24h; | Procedure for synthesis of 9-methyl-9H-carbazole (6) KOH (3eq) and 18-crown-6 (0.1eq) were added to the suspension of 9H-carbazole (1, 119 mmol) in toluene and this mixture was heated with reflux for 20 mins. Iodomethane was added slowly to this mixture and entire mixture was heated with reflux at 110 for 24 hrs. This mixture was cooled to room temperature and was filtered by vaccum. The material was column chromatographed in silica gel using n-hexane/ethyl acetate (15:1) to get the 9-methyl-9H-carbazole (6) .Yield 80.3 %, Rf = 0.54 (5:1 n-hexane-ethyl acetate); 1H NMR(CDCl3, 400MHz): δH 8.088(d, J=6.8Hz, 2H), 7.464(t, J=7.6Hz, 2H), 7.374(d, J=8.0Hz, 2H), 7.223(t, J=7.4Hz, 2H), 3.809(s, 3H); 13C NMR(CDCl3, 100MHz) : δc 140.927, 125.622, 122.708, 120.255, 118.773, 108.375, 28.995. |
79% | With sodium hydride In N,N-dimethyl-formamide for 1h; Ambient temperature; | |
77% | With NaH In N,N-dimethyl-formamide | 9-methyl-9H-carbazole (1b) 9-methyl-9H-carbazole (1b) To a solution of carbazole (3.34 g, 20 mmol) in DMF (80 mL) at 0° C. was added NaH (0.72 g, 30 mmol). After heating at 80° C. for 1.5 h, iodomethane (3.4 g, 24 mmol) was added dropwise. The resulting mixture was kept at 80° C. overnight. After cooling down to 0° C., the reaction mixture was carefully quenched with water and extracted with ethyl acetate three times. The combined organic phase was washed with water and brine. Then the organic layer was dried over anhydrous sodium sulfate and the solvent was removed. The residue was purified by silica gel chromatography using petroleum ether and ethyl acetate as eluent (EA:PE=1:5) to afford methylated carbazole 1b (2.78 g) as yellow oil in 77% yield. 1H NMR (400 MHz, CDCl3) δ 8.08 (d, J=8.0 Hz, 2H), 7.46 (t, J=8.0 Hz, 2H), 7.36 (d, J=8.0 Hz, 2H), 7.22 (t, J=8.0 Hz, 2H), 3.79 (s, 3H). 13C NMR (400 MHz, CDCl3) δ 140.9, 125.6, 122.7, 120.2, 118.8, 108.4, 28.9. |
77% | Stage #1: 9H-carbazole With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0 - 80℃; for 1.5h; Stage #2: methyl iodide In N,N-dimethyl-formamide; mineral oil at 80℃; | [0099] To a solution ofcarbazole (3.34 g, 20 mmol) in DMF(80 mL) at 0° C. was added NaH (0.72 g, 30 mmol). Afterheating at 80° C. for 1.5 h, iodomethane (3.4 g, 24 mmol) wasadded dropwise. The resulting mixture was kept at 80° C.overnight. After cooling down to 0° C., the reaction mixturewas carefully quenched with water and extracted with ethylacetate three times. The combined organic phase was washedwith water and brine. Then the organic layer was dried overanhydrous sodium sulfate and the solvent was removed. Theresidue was purified by silica gel chromatography usingpetroleum ether and ethyl acetate as eluent (EA:PE=1:5) toafford methylated carbazole lb (2.78 g) as yellow oil in 77%yield. 1H NMR (400 MHz, CDCl3) δ 8.08 (d, J=8.0 Hz, 2H),7.46 (t, J=8.0 Hz, 2H), 7.36 (d, J=8.0 Hz, 2H), 7.22 (t, J=8.0Hz, 2H), 3.79 (s, 3H). 13C NMR (400 MHz, CDCl3) δ 140.9,125.6, 122.7, 120.2, 118.8, 108.4, 28.9. |
73% | Stage #1: 9H-carbazole With sodium hydride In N,N-dimethyl-formamide at 20℃; for 0.833333h; Stage #2: methyl iodide In N,N-dimethyl-formamide for 3h; | 1.a The synthesis of compound CNQ follows the following synthetic route: Step a,0.84 g of Compound 1 was dissolved in 10 mL of anhydrous DMF with vigorous stirring.Gradually add 0.25 g of NaH solid, add to completion over 20 minutes, and stir at room temperature for half an hour.After the reaction was completed, methyl iodide (0.72 g) was added dropwise to the reaction system, and after reacting for three hours,The reaction solution was poured into 200 mL of water, and a white solid was separated and filtered.Chromatographic column separation (silica gel 200-300 mesh, petroleum ether: dichloromethane = 100:1, v/v)Obtained colorless needle crystal compound 2 (661 mg, reaction yield: 73%) |
72% | Stage #1: 9H-carbazole With potassium hydroxide In acetone at 20℃; for 0.5h; Stage #2: methyl iodide In acetone at 20℃; | |
67% | Stage #1: 9H-carbazole With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0 - 20℃; for 1.25h; Inert atmosphere; Stage #2: methyl iodide In N,N-dimethyl-formamide; mineral oil at 0 - 20℃; for 0.5h; Inert atmosphere; | |
67% | Stage #1: 9H-carbazole With sodium hydride In tetrahydrofuran at 0 - 20℃; for 2h; Stage #2: methyl iodide In tetrahydrofuran for 20h; | |
With silver(l) oxide | ||
Stage #1: 9H-carbazole With sodium hydride In N,N-dimethyl-formamide at 20℃; for 0.5h; Stage #2: methyl iodide In N,N-dimethyl-formamide for 16h; | 1.a To a solution of carbazole (5 g; 0.030 mol) in dimethylformamide (50 ml) was added portionwise sodium hydride (60% suspension in mineral oil, 1.15 g; 0.030 mol) and the suspension obtained was stirred at room temperature for 0.5 hour. Iodomethane (1.43 ml; 0.030 mol) was then added dropwise. The suspension thus obtained was stirred for 16 hours and H2O was then added cautiously until precipitation was complete. The precipitate was collected by filtration under vacuum and dried in a vacuum oven. 5.3 g of the desired product were thus obtained and were used without further purification. 1H NMR (300 MHz, DMSO-d6) δ ppm 3.87 (s, 3H), 7.20 (t, J=7.5 Hz, 2H), 7.43-7.49 (m, 2H), 7.56-7.61 (m, 2H), 8.15 (d, J=7.5 Hz, 2H). | |
Stage #1: 9H-carbazole With sodium hydride In N,N-dimethyl-formamide at 20℃; for 0.5h; Stage #2: methyl iodide In N,N-dimethyl-formamide for 16h; Stage #3: With water In N,N-dimethyl-formamide | 1.a Example 1; Preparation of Compound 1 (RI=CH3, R2=CI, R3=R4=R5=R6=X=Y=H); a) 9-methyl-9/-/-carbazole; To a solution of carbazole (5 g; 0.030 mol) in dimethylformamide (50 ml) was added portionwise sodium hydride (60% suspension in mineral oil, 1.15 g; 0.030 mol) and the suspension obtained was stirred at room temperature for 0.5 hour, lodomethane (1.43 ml; 0.030 mol) was then added dropwise.The suspension thus obtained was stirred for 16 hours and H2O was then added cautiously until precipitation was complete. The precipitate EPO was collected by filtration under vacuum and dried in a vacuum oven.5.3 g of the desired product were thus obtained and were used without further purification.1H NMR (300 MHz, DMSO-Cf6) δ ppm 3.87 (s, 3 H), 7.20 (t, J = 7.5 Hz, 2 H), 7.43 - 7.49 (m, 2 H), 7.56 - 7.61 (m, 2 H), 8.15 (d, J = 7.5 Hz, 2 H). | |
With sodium hydride In N,N-dimethyl-formamide at 20℃; for 3h; | ||
With sodium hydride In N,N-dimethyl-formamide at 20℃; for 3h; | ||
With sodium hydride In N,N-dimethyl-formamide; mineral oil at 20℃; | ||
With potassium hydroxide In N,N-dimethyl-formamide at 20℃; for 13h; | ||
With potassium hydroxide In N,N-dimethyl-formamide at 20℃; for 13h; | ||
With potassium carbonate In acetone at 20℃; | ||
Stage #1: 9H-carbazole With sodium hydride In N,N-dimethyl-formamide Stage #2: methyl iodide In N,N-dimethyl-formamide | ||
With sodium hydride In N,N-dimethyl-formamide at 20℃; for 5h; | ||
With sodium hydroxide In N,N-dimethyl-formamide for 4h; | ||
With sodium hydride | ||
With sodium hydride In N,N-dimethyl-formamide at 20℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64% | With aluminum (III) chloride In chloroform at 20℃; for 0.75h; | |
50% | With aluminium trichloride In benzene at 25 - 30℃; for 24h; | |
50% | With aluminum (III) chloride In dichloromethane at 20℃; for 2h; Reflux; |
With zinc(II) chloride In dichloromethane at 20℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With trichlorophosphate; at 125℃; for 1h;Inert atmosphere; | The 3.00gN-methyl carbazole (16.55mmol) dissolved in 12mLDMF, then adding 3 ml phosphorus oxychloride. The reaction is heated to 125 C, under the protection of nitrogen, reaction 1h, is poured into a 60 ml, 20% solution of sodium acetate. The organic phase is extracted with ethyl acetate three times drying with anhydrous sodium sulfate. Subsequently reduced pressure to remove the solvent, the obtained crude product is used 200-300 item of thin separation of the silica gel column, eluent petroleum ether/ethyl acetate to 2:1, finally obtaining colorless solid about 2.86g, the yield is 82%. |
81% | With trichlorophosphate; at 0 - 130℃; for 5h; | A solution of DMF (25 mL) containing 9-methyl-9H-carbazole 3 (4.5 g, 25 mmol) was cooled to 0C.POC13 (2.3 mL) was slowly added at 0C and the solution was allowed to stir to room temperaturefor one hour. Then, the solution mixture was heated at 130C for 4 hours. After cooling, the solutionwas poured into ice water/aq. NaOH solution. Solvents were removed under reduced pressure.Water was added and the solution was extracted with chloroform several times. The organic phaseswere combined, dried over magnesium sulfate and the solvent removed under vacuum. Theresidue was purified by column chromatography (SiO2) using chloroform as the eluent (4.23 g, 81%yield). |
78.3% | With trichlorophosphate; In 1,2-dichloro-ethane; at 90℃; for 9h;Inert atmosphere; Cooling with ice; | A cooled flask in ice bath was added phosphoryl chloride (0.6mL, 5.9mmol) and anhydrous DMF (1.4mL, 17.7mmol) under nitrogen. This mixture was added 9-methyl-carbazole (0.98g, 5.4mmol, in 20mL sym-dichloroethane). After stirring for 1h, the reaction temperature was raised to 90C and kept for 8h. The mixture was cooled and poured into ice water and extracted with dichloromethane. The solvent was evaporated and the crude product was purified by column chromatography on silica gel (ethyl acetate/hexane, 1/10, v/v). A yellow solid was obtained (0.88g, 78.3%). 1H NMR (500MHz, CDCl3): delta 10.10 (s, 1H), 8.62 (s, 1H), 8.16 (d, 1H, J=11.5Hz), 8.01 (d, 1H, J=9.5Hz), 7.54 (t, 1H, J=8.0Hz), 7.47, (t, 2H, J=9.5Hz), 7.33, (t, 1H, J=9.5Hz), 4.34, (t, 2H, J=9.5Hz), 1.89 (m, 2H), 1.33 (m, 10H), 0.86, (t, 3H, J=9.0Hz) ppm. |
78% | With trichlorophosphate; at 80℃; for 4.5h;Cooling with ice; Inert atmosphere; | Step b,In an ice bath, slowly add dropwise to 905 mg of Compound 2 in anhydrous DMF (5 mL) under nitrogen.Phosphorus oxychloride (0.9 mL) was added and stirred vigorously for 0.5 hours. The reaction temperature was then heated to 80 C for 4 hours.After the reaction was completed, the brown reaction mixture was poured into a sodium acetate solution and extracted with ethyl acetate.Dry over anhydrous sodium sulfate, rotary distillation, column separation (silica gel 200-300 mesh, petroleum ether:Ethyl acetate = 70:1, v/v) gave a pale yellow powder 3 (710 mg, yield 78%) |
77% | After substitution with nitrogen, 8.0 g (50 mmol) of phosphoryl chloride was slowly added dropwise to 10 ml of DMF while cooling at 0C, and the mixture was stirred at room temperature for 1 hour. This was then cooled to 0C, and 5.4 g (30 mmol) ofN-methylcarbazole was dissolved in 13 ml of 1,2-dichloroethane and added dropwise thereto. The mixture was then heated to 90C over a period of 1 hour, and heated stirring was carried out for 8 hours. Upon completion of the reaction, 500 ml of water was added, the organic layer was extracted with dichloromethane, and the extracted organic layer was dried over anhydrous magnesium sulfate. After filtering out the anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure and the obtained crude product was purified by silica gel chromatography using a developing solvent (dichloromethane:hexane = 3:1 (volume ratio)), to obtain 4.8 g (23 mmol) of 3-formyl-9-methylcarbazole crystals. (Yield: 77%) · Measured values: 1H-NR4R (delta, CDCl3): 3.89 (3H, s), 7.30-8.1 (4H, m), 8.05 (1H, d), 8.15 (1H, d), 8.60 (1H, s), 10.10 (1H, s)· Calculated: C14H11NO: C, 80.36%; H, 5.30%; N, 6.69%, 0,7.65%.· Found: C, 80.3%; H, 5.36%; N, 6.74%; O, 7.60%. | |
75% | Vilsmeier-Haack reagent was freshly prepared by the careful addition of POCl3 (2 mL, 0.021 mol) in DMF (8 mL, 0.103 mol) at 0C with constant stirring. To this reaction mixture at 0C was added 9-methylcarbazole 7 (5.0 g, 0.0238 mol, 1 equiv.) that stirred initially for 30 min, and later slowly brought to RT and stirred for 2 h. Finally, the reaction temperature was raised to 60C and stirred for another 2 h. The reaction mixture was then poured into a sodium carbonate solution and stirring was continued at 90C for 2 h. After cooling to RT, the reaction mixture was suspended in water, extracted with dichloromethane (20 mL X 3 times), and the collective extracts were washed with water and dried over anhydrous sodium sulphate. The residue obtained after the in vacuo removal of dichloromethane was further recrystallized from ethanol to afford the desired compound 8 as off-white crystalline solid. Yield: 75 %; M.P. 74-76 C; FTIR (ATR, max, cm-1): 3022 (Ar-H Str.), 2993 (C-H Str. of CH3), 1684.01 (C=O Str.); 1H-NMR (400 MHz, CDCl3, ppm): 10.09 (s, 1H, CHO), 8.15 (d, 1H, J = 7.76 Hz, Ar-H), 8.02 (dd, 1H, J = 8.52 Hz, ArH), 7.53 (t, 1H, Ar-H), 7.45 (dd, 2H, J = 8.28 Hz, Ar-H), 7.34 (t, 1H, Ar-H), 3.88 (s, 3H, N-CH3); 13C-NMR (100 MHz, CDCl3, ppm): 191.80 (C=O), 144.51, 141.70, 128.54, 127.24, 126.76, 123.83, 122.99, 120.65, 109.11, 29.38 (N-CH3). | |
55% | With trichlorophosphate; at 0 - 80℃; for 4.5h; | 9-Methyl carbazole 2 (1.81 g, 10 mmol) was dissolved in dry DMF (20 ml) under anhydrous condition. It was cooled to 0 C, POCl3 (1.87 ml) was added drop wise for 30 min and stirring continued for 4 h at 80 C. After completion of reaction (TLC), the reaction mass was poured over crushed ice (50 g), basified with NaOH, extracted with chloroform and dried over anhydrous Na2SO4. Organic layer was concentrated and purified through silica gel column using chloroform as eluting solvent to yield product 3 (1.15 g). Yield: 55%; off white solid; mp: 76-78 C; IR (cm-1): 3035, 2704, 1685, 1626, 1591, 1570, 1050, 750; 1H NMR (300 MHz, DMSO-d6, delta in ppm): 3.91 (s, 3H, NCH3), 7.35 (t, 1H, J = 8.2 Hz, ArH), 7.40-7.60 (m, 3H, ArH), 7.98 (d, 1H, J = 8.2 Hz, ArH), 8.17 (d, 1H, J = 8.2 Hz, ArH), 8.60 (s, 1H, ArH), 10.10 (s, 1H, -CHO); m/z = 209.85 (m+1). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With potassium <i>tert</i>-butylate In N,N-dimethyl-formamide for 1h; Heating; | |
93% | With sodium t-butanolate In N,N-dimethyl-formamide for 1h; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 35% 2: 10% 3: 2% 4: 3% | In dichloromethane for 18h; Irradiation; | |
1: 10% 2: 3% 3: 2% 4: 35% | for 18h; Irradiation; | |
1: 35 % Chromat. 2: 10 % Chromat. 3: 3 % Chromat. 4: 2 % Chromat. | In dichloromethane for 18h; Irradiation; Quartz vessel; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 35% 2: 3% 3: 2% 4: 10% | In dichloromethane for 18h; Irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With chloro-trimethyl-silane In tetrahydrofuran; N,N-dimethyl-formamide at 60℃; for 1h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | Stage #1: N-methylcarbazole With trifluorormethanesulfonic acid; [bis(pyridine)iodine]+ tetrafluoroborate In dichloromethane at 0 - 20℃; for 40h; Stage #2: With sodium thiosulfate In dichloromethane | 21 A mixture of 308 mg (0.83 mmol, 2.5 eq.) of bis(pyridine)iodonium tetrafluoroborate (IPy2BF4) and 60 mg (0.33 mmol) of carbazole was added with 8 mL of dichloromethane under a nitrogen atmosphere, and further added dropwise with 29 μl (0.30 mmol, 1 eq.) of trifluoromethanesulfonic acid (TfOH) under a temperature condition of 0° C. Then, the resultant mixture was stirred under a nitrogen atmosphere at room temperature for 40 hours to obtain an orange-yellow reaction mixture (I). Subsequently, the excessive iodization reagent in the orange-yellow reaction mixture (I) thus obtained was decomposed with sodium thiosulfate (Na2S2O3). Thereafter, the aqueous layer was extracted with dichloromethane. After that, the collected organic phase was washed with sodium chloride, dried with sodium sulfate (Na2SO4), filtered, and concentrated to obtain a crude product (I) (143.9 mg). Then, the crude product (I) thus obtained was separated and purified by silica gel chromatography (hexane:EtOAc=5:1). Thereby, 3,6-diiodo-9-methylcarbazole expressed by the following general formula (96) was obtained (a yield of 133.0 mg and 93%). The obtained 3,6-diiodo-9-methylcarbazole was subjected to 13C NMR and 1H NMR measurements. FIG. 69 shows a graph obtained from the 13C NMR measurement, and FIGS. 70 and 71 show graphs obtained from the 1H-NMR measurements. These measurement results are shown below.1H NMR (CDCl3) d8.32 (d, J=1.6 Hz, 2H), 7.73 (d, J=8.6 Hz, 1.6 Hz, 2H), 7.17 (d, J=8.6 Hz, 2H), 3.80 (s, 3H);13C NMR (CDCl3) d139.69, 134.30, 129.00, 123.60, 110.45, 81.67. |
87% | With sodium nitrate; iodine; acetic acid at 30℃; for 21h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With 1,8-diazabicyclo[5.4.0]undec-7-ene at 90℃; for 7h; | |
97% | With 1,4-diaza-bicyclo[2.2.2]octane In N,N-dimethyl-formamide at 94 - 95℃; for 24h; | |
97% | With 1,4-diaza-bicyclo[2.2.2]octane at 90 - 95℃; for 24h; | 5 EXAMPLE 5 To a solution of carbazole (1.03 g, 6.16 mmol) in DMC (10 ML), DABCO (0.069 g, 0.62 mmol) is added and the resulting solution is heated to 90-95° C. for 24 h.The reaction is cooled to RT, and diluted with EtOAc (40 ML) and H2O (40 ML).The organic layer is separated and washed in sequence with H2O (50 ML), 10% aqueous citric acid (2*40 ML) and H2O (3*40 ML).The organic layer is dried over anhydrous Na2SO4, filtered and concentrated under vacuum to give 9-methylcarbazole (about 1.08 g, 97%) as a beige solid: 1H NMR (CDCl3) δ 8.06 (d, 2H), 7.43 (t, 2H), 7.31 (d, 2H), 7.20 (t, 2H), 3.71 (s, 3H); 13C NMR (CDCl3) δ 141.0, 125.7, 122.8, 120.3, 118.9, 108.5, 29.0; MS m/z 181 [M+1]+. |
95% | With magnesium oxide In N,N-dimethyl-formamide at 170℃; for 0.5h; Microwave irradiation; Green chemistry; | |
86% | With N,N,N,N,-tetramethylethylenediamine In N,N-dimethyl-formamide at 95℃; for 8h; | |
With 1,4-diaza-bicyclo[2.2.2]octane at 90 - 95℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With Me3FeLi; magnesium In tetrahydrofuran at 20℃; for 3h; | |
85% | With tetrabutylammomium bromide; sodium acetate In 1-methyl-pyrrolidin-2-one at 140℃; for 48h; | |
83% | With [(Me4Fe)MeLi][Li(Et2O)]2 In tetrahydrofuran at -40℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With aluminum oxide; silica gel; potassium carbonate In chloroform column chromatography; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68.3% | With aluminum (III) chloride In dichloromethane at 0 - 20℃; | |
59% | With bismuth(III) chloride In dichloromethane at 20℃; for 0.5h; | |
56% | With perchloric acid; triphenylphosphine In dichloromethane at 20℃; for 2h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | Stage #1: N-methyl-2-iodoaniline; 2-(trimethylsilyl)phenyl trifluoromethanesulfonate With cesium fluoride In acetonitrile at 20℃; for 10h; Stage #2: With tricyclohexylphosphine In acetonitrile at 100℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
43% | With Me4FeLi2; magnesium In tetrahydrofuran at 20℃; for 12h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 30% 2: 27% | With acetic acid In toluene at 80℃; for 8h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With potassium <i>tert</i>-butylate; ethylene glycol In dimethyl sulfoxide at 30℃; for 12h; Inert atmosphere; Green chemistry; | |
With tricyclohexylphosphine In acetonitrile at 100℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 38% 2: 25% 3: 19% | With calcium oxide at 500℃; for 0.666667h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With iodine; acetic acid; periodic acid In water at 80℃; for 3h; | 1 Synthesis of Intermediate C; Carbazole (2.433 g, 10 mmol) was added to an 80% acetic acid (100 ml), and iodine (I2) (1.357 g, 5.35 mmol) and ortho-periodinic acid (H5lO6) (0.333 g, 1.46 mmol) in a solid phase were added thereto. The reaction mixture was stirred at 80° C. under a nitrogen atmosphere for three hours. After the reaction was terminated, the reaction solution was extracted three times with ethylether (50 ml). The collected organic layer was dried over magnesium sulfate to evaporate a solvent. The resultant residue was purified by silica gel column chromatography to give intermediate C (2.61 g, yield: 85%). The structure of intermediate C was determined by 1H NMR. 1H NMR (CDCl3, 300 MHz) δ (ppm) 8.32 (s, 1H), 7.95 (d, 1H), 7.62-7.55 (m, 2H), 7.38 (d, 1H), 7.31-7.45 (m, 2H), 3.66 (s, 3H); 13C NMR (CDCl3, 100 MHz) δ (ppm) 141.5, 138.9, 129.2, 126.4, 124.9, 123.1, 122.3, 119.2, 118.8, 113.2, 108.5, 85.8, 30.5. |
With gold(III) chloride; N-iodo-succinimide In 1,2-dichloro-ethane at 20℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | In tetrahydrofuran at -40 - -30℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | With [bis(acetoxy)iodo]benzene; palladium diacetate In toluene at 20℃; for 2h; | |
71% | Stage #1: 2-(N-methylamino)-1,1'-biphenyl With palladium diacetate In toluene at 25℃; for 1h; Inert atmosphere; Stage #2: With [bis(acetoxy)iodo]benzene In toluene at 25℃; for 24h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 81% 2: 7% 3: 4% | With palladium diacetate; tricyclohexylphosphine tetrafluoroborate; sodium t-butanolate In toluene at 100℃; for 0.25h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 84% 2: 16% | With palladium diacetate; tricyclohexylphosphine tetrafluoroborate; sodium t-butanolate In toluene at 100℃; for 0.166667h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With bis(1,5-cyclooctadiene)nickel(0); (dimethoxy)methylsilane; tricyclohexylphosphine In toluene at 80℃; for 12h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With tin(IV) chloride; In dichloromethane; at 20℃; for 0.75h; | To a solution of 9-methyl-9H-carbazole (5.3 g, 29.7 mmol) in dichloromethane (100 mL) was added SnCl4 (5.14 mL, 44.6 mmol) followed by dichloromethyl methyl ether (4.03 mL, 44.6 mmol) at room temperature. After stirring for 45 min, the reaction mixture was quenched with 1N HCl (100 ml). The organic layer was separated, washed with water (20 mL), sat. NaHCO3 solution (20 mL), Brine solution (25 mL), dried over anhydrous sodium sulphate and rotary evaporated to dryness. Crude residue thus obtained was purified over silica gel column chromatography (Hexane: ethyl acetate, 99: 1) gave 9-methyl-9H-carbazole-3-carbaldehyde 2 (4.89 g, 80%) as pale green solid. m.p. 74 C 1H NMR (300 MHz, CDCl3) delta 9.90 (s, 1H), 8.28 (s, 1H), 7.93 (d, J = 7.7 Hz, 1H), 7.79 (d, J = 8.4 Hz, 1H), 7.42(t, J = 7.9 Hz, 1H), 7.26-7.14 (m, 3H), 3.65 (s, 3H). 13C NMR (75 MHz, CDCl3) delta 191.7, 144.3, 141.5, 128.3, 127.0, 126.6, 123.6, 122.8, 122.7, 120.4, 120.2, 109.0, 108.5, 29.2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With bis(1,5-cyclooctadiene)nickel (0); dimethylethylsilane In toluene at 130℃; for 14h; Inert atmosphere; chemoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | Stage #1: N-methylcarbazole With boron trichloride; Dimethyl-p-toluidine In dichloromethane at 20℃; for 16h; Inert atmosphere; Stage #2: 2,3-dimethyl-2,3-butane diol With triethylamine In dichloromethane at 20℃; for 0.5h; Inert atmosphere; | 34 Example 34 - Mono-Borylation of N-Me carbazole1 equiv. BCI3 0.95 equiv.20 °C, 30 min[00143] An oven dried 1 L round-bottomed flask cooled under N2, was charged withAICI3 (14.7 g, 1 10 mmol, 1 .1 equiv.) and N-Me carbazole (17.2 g, 95.0 mmol, 0.95 equiv.). This was then suspended in CH2CI2 (300 ml_) and A ,A/,4-trimethylaniline (18.8 ml_, 130 mmol, 1 .3 equiv.) was added. To the resulting solution was then added a solution of BCI3 (1 .0 M in CH2CI2, 100 ml_, 100 mmol, 1 equiv.). The reaction was stirred for 16 hours before being transferred over 45 minutes via a cannula under a positive pressure of N2 to a solution of pinacol (35.5 g, 300 mmol, 3 equiv.) in triethylamine (209 ml_, 1 .50 mol, 15 equiv.) contained in an oven dried 2 L round-bottomed flask, cooled under N2, with care taken not to allow any significant rise in reaction temperature. After washing the flask with CH2CI2 (2 x 25 ml_) the volatiles were removed in vacuo and the resulting beige solid purified by chromatography on silica gel eluting with a gradient of 0 - 20% EtOAc in petroleum ether 40/60 to give the desired compound (22.3 g, 72.6 mmol, 76%) as a pale yellow solid (M.p. 147 - 149 °C).1 H NMR (CDCI3): 8.60 (s, 1 H), 8.13 (d, J = 7.6 Hz, 1 H), 7.94 (dd, J = 1 .1 , 8.2 Hz, 1 H), 7.47 (ddd, J = 1 .1 , 7.1 , 8.2 Hz, 1 H), 7.39 (d, J = 8.1 Hz, 2 H), 7.25 (td, J = 1 .0, 7.4 Hz, 1 H), 3.84 (s, 3 H), 1 .40 (s, 12 H).13C NMR (CDCI3) : 143.1 , 141 .0, 132.2, 127.7, 125.7, 123.0, 122.5, 120.5, 1 19.3, 108.4, 107.8, 83.6, 29.1 , 24.9.11 B NMR (CD2CI2): 31 .1 (br s). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | Stage #1: N-methylcarbazole With aluminum (III) chloride; boron trichloride; Dimethyl-p-toluidine In dichloromethane at 20℃; for 16h; Inert atmosphere; Stage #2: 2,3-dimethyl-2,3-butane diol With triethylamine In dichloromethane at 20℃; for 0.5h; Inert atmosphere; | 24 Example 24 - Preparation of 3,6-Di(4A5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl)-9- methylcarbazole2.5 equiv. BCI32.75 equiv. AICI3 2.63 equiv. W,N,4-trimethylaniline20 °C, 30 min [00127] An oven dried 25 ml_ round-bottomed flask cooled under N2, was charged with AICI3 (1 17 mg, 0.880 mmol, 2.75 equiv.) and N-Me carbazole (58 mg, 0.320 mmol, 1 equiv.). This was then suspended in CH2CI2 (3 ml_) and A/,/V,4-trimethylaniline (121 μΙ_, 0.840 mmol, 2.625 equiv.) was added. To the resulting solution was then added a solution of BCI3 (1 .0 M in CH2CI2, 0.8 ml_, 0.800 mmol, 2.5 equiv.). The reaction was stirred for 16 hours before being transferred over 15 minutes via a cannula under a positive pressure of N2 to a solution of pinacol (227 mg, 1 .92 mmol, 6 equiv.) in triethylamine (1 .34 ml_, 9.60 mmol, 30 equiv.) contained in an oven dried 50 ml_ round-bottomed flask, cooled under N2, with care taken not to allow any significant rise in reaction temperature. After washing the flask with CH2CI2 (2 χ 25 ml_) the volatiles were removed in vacuo and the resulting beige solid purified by chromatography on silica gel eluting with a gradient of 10 - 20% EtOAc in hexane to give the title compound (84 mg, 0.194 mmol, 60%) as a pale yellow solid (M.p. 257 - 259 °C).[00128] Whilst this compound has been reported before the spectroscopic data was not.1 H NMR (400 MHz, CDCI3): δ 8.7 (2 H, s), 7.9 (2 H, dd, J = 8.3, 1 .0 Hz), 7.4 (2 H, d, J = 8.3 Hz), 3.9 (3 H, s), 1 .4 (24 H, s) 13C NMR (100 MHz, CDCI3) δ 143.1 , 132.1 , 127.9, 122.7, 107.8, 83.5, 29.1 , 24.9 11 B NMR (128 MHz, CDCI3) δ 31 .1vmax (liquid film)/crrf1 2979w (C-H), 2930w (C-H), 1625w, 1597w, 1468w, 1351 s (B-O), 1318m, 1258w, 1 145m, 1083wMS (ES+) m/z {%) 434 (100 [M + H]+), 352 (10 [M + H - C6^]+), 308 (5, [M + H - BPin], 264 (50); Calcd for C25H34B2N04F3 [M + H]+: 434.2669, found: m/z 434.2666. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | Stage #1: N-methylcarbazole; 2-chloro-1,3,2-benzodioxaborole In 1,2-dichloro-benzene for 0.5h; Inert atmosphere; Stage #2: 2,3-dimethyl-2,3-butane diol With triethylamine In 1,2-dichloro-benzene for 1h; | 39 Example 39: Preparation of 3,6-DH4A5 -tetrametlwll-1 ,3,2-dsoxaborojan-2-¥0-9- methvicarbazQge[00152] oven dried Schlenk tube equipped with a J. Young's tap under inert atmosphere CatBCI (30 mg, 1 .9x10"4 mol) was dissolved in 1 ml of anhydrous 1 ,2- dichlorobenzene followed by addition of 2,6-di-te/f-butylpyridine (52 μΙ, 2.3x10"4 mol), powdered AICI3 (33 mg, 2.5 x10"4 mol) and 9-methylcarbazole (16 mg, 8.8x10"5 mol). The reaction mixture was stirred for 30 minutes. Then Et3N (0.3 ml) and pinacol (69 mg, 5.8x10'4 mol) (in one portion) were added to the reaction mixture and stirred for 1 h. Volatiles were removed under vacuum and the product was purified by flash column chromatography on silica (eluent CH2CI2 : hexane = 3 : 1 to CH2CI2). Removal of the solvent yielded the desired product as white solid (28 mg, 73%).1 H NMR (CDCI3) δ: 8.7 (2 H, s), 7.9 (2 H, dd, J = 8.3, 1 .0 Hz), 7.4 (2 H, d, J = 8.3 Hz), 3.9 (3 H, s), 1 .4 (24 H, s).13C NMR (CDCI3) δ: 143.1 , 132.1 , 127.9, 122.7, 107.8, 83.5, 29.1 , 24.9.11 B NMR (CDCI3) δ: 31 .1 . |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | Stage #1: N-methylcarbazole; N,N-dimethyl-formamide With trichlorophosphate at 100℃; for 1h; Stage #2: With ammonia; iodine In water at 20℃; for 3h; regioselective reaction; | 4.2. Typical experimental procedure for the transformation of aromatics into aromatic nitriles with I2 and aq NH3 using the Vilsmeier-Haack reaction General procedure: To a flask containing 1,3,5-trimethoxybenzene (1009.1 mg, 6 mmol) were added POCl3 (1011.9 mg, 6.6 mmol) and DMF (1754.1 mg, 24 mmol) at 0 °C. After being stirred for 3 h at 40 °C, I2 (3045.7 mg, 12 mmol) and aq NH3 (12 mL, 28-30%) were added to the reaction mixture. The obtained mixture was stirred for 3 h at rt. After the reaction, the mixture was poured into aq satd Na2SO3 solution and extracted with CHCl3 (3×20 mL). The organic layer was dried over Na2SO4, filtered, and evaporated to provide almost pure 2,4,6-trimethoxybenzonitrile (1156.1 mg) in 99% yield. If necessary, it was recrystallized from a mixture of hexane and EtOAc (1:1). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With bis(tricyclohexylphosphine)nickel(II) dichloride; 1,1,3,3-Tetramethyldisiloxane; K3PO4 In toluene at 115℃; for 15h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
59% | With N-Bromosuccinimide; In dichloromethane; | 3-bromo-9-methyl-9H-carbazole (2b) To a solution of 1b (2.5 g, 13.8 mmol) in dichloromethane (80 mL) was added NBS (2.4 g, 13.8 mmol) portion-wise in an ice-water bath. After complete addition, the solution mixture was warmed to room temperature and stirred overnight. The resulting solution was washed with water and brine. The organic phase was dried over anhydrous sodium sulfate and the solvent was removed. The residue was purified by silica gel chromatography using ethyl acetate and petroleum ether (EA:PE=1:10) as eluent to afford 2b (2.11 g) in 59% yield. 1H NMR (400 MHz, CDCl3) delta 8.19 (d, J=2.0 Hz, 1H), 8.03 (d, J=8.0 Hz, 1H), 7.54 (dd, J=8.8 Hz, J=2.0 Hz, 1H), 7.50 (td, J=8.0 Hz, J=1.2 Hz, 1H), 7.39 (d, J=8.0 Hz, 1H), 7.27-7.22 (m, 2H), 3.82 (s, 3H). |
59% | With N-Bromosuccinimide; In dichloromethane; at 20℃;Cooling with ice; | [0101] To a solution of lb (2.5 g, 13.8 mmol) in dichloromethane (80 mL) was added NES (2.4 g, 13.8 mmol) portion-wise in an ice-water bath. Afier complete addition, the solution mixture was warmed to room temperature and stirred overnight. The resulting solution was washed with water and brine. The organic phase was dried over anhydrous sodium sulfate and the solvent was removed. The residue was purified by silica gel chromatography using ethyl acetate and petroleum ether (EA:PE=l:l0) as eluent to afford 2b (2.11 g) in 59% yield. 1H NMR (400 MHz, CDCl3) delta8.19 (d, J=2.0 Hz, 1H), 8.03 (d, J=8.0 Hz, 1H), 7.54 (dd, J=8.8 Hz, J=2.0 Hz, 1H), 7.50 (td, J=8.0 Hz, J=l.2 Hz, 1H), 7.39 (d, J=8.0 Hz, 1H), 7.27-7.22 (m, 2H), 3.82 (s, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | Stage #1: N-methylcarbazole With trichlorophosphate In N,N-dimethyl-formamide at 100 - 110℃; for 2h; Stage #2: With sodium acetate In water at 20℃; | |
Multi-step reaction with 2 steps 1: N-Bromosuccinimide / dichloromethane 2: n-butyllithium / N,N-dimethyl-formamide; water; tetrahydrofuran | ||
Multi-step reaction with 2 steps 1.1: N-Bromosuccinimide / dichloromethane / 20 °C / Cooling with ice 2.1: n-butyllithium / tetrahydrofuran / 1 h / -78 °C 2.2: -78 - 20 °C / Sealed tube |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With palladium diacetate; caesium carbonate; cesium pivalate; 1,2-bis-(dicyclohexylphosphino)ethane In toluene at 120℃; for 17h; Glovebox; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | With trifluorormethanesulfonic acid at 0 - 20℃; for 6h; Ionic liquid; Inert atmosphere; Schlenk technique; | 3,6-bis(1-(4-fluorophenyl)-3-phenylprop-2-ynyl)-9-methyl-9H-carbazole (6) General procedure: An oven-dried Schlenk tube was charged with (bmim)PF6 (4.0 mL) and N-methylimidazole (1 mmol). Propargyl alcohol (2.2 mmol) was added followed by triflic acid (0.1 mmol) under N2 atmosphere at 0 oC and the mixture was magnetically stirred at r.t. until completion (monitored by TLC). Once the reaction was over, the contents were cooled to r. t. and extracted with with EtOAc-Hexane (2:3 vol/vol) until the final extraction did not show a spot corresponding to the starting material or to the product. The combined organic extracts were washed with DI water, dried with MgSO4 and concentrated to give the crude product, which upon purification through column chromatography furnished the desired products. 3,6-bis(1-(4-fluorophenyl)-3-phenylprop-2-ynyl)-9-methyl-9H-carbazole (6): Brown solid, m.p. 121-123 °C, Yield: 72%. 1H NMR (500 MHz, CDCl3): δH 3.81 (s, 3H), 5.39 (s, 2H), 7.00 (t, J = 8.5 Hz, 4H), 7.25-7.49 (m, 18H), 8.11 (s, 2H) ppm. 13C NMR (125 MHz, CDCl3): δC 29.25, 42.98, 85.06, 90.70, 108.83, 115.32 (d, JCF = 21.2 Hz), 119.06, 122.73, 123.48, 125.94, 128.03, 128.27, 129.41 (d, JCF = 7.3 Hz), 131.69, 132.30, 138.32, 140.49, 161.69 (d, JCF = 243.3 Hz) ppm; 19F NMR (470MHz, CDCl3): δF -116.43 (m); IR (cm-1, CHCl3): ν 2953, 2926, 1600, 1504, 1489, 1321, 1267, 1226, 1157, 1095, 839, 808, 756; APCI-MS: 598 [M+H]+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With trifluorormethanesulfonic acid at 0 - 20℃; for 5.5h; Ionic liquid; Inert atmosphere; Schlenk technique; | 3,6-bis(1-(4-chlorophenyl)-3-phenylprop-2-ynyl)-9-methyl-9H-carbazole (7) General procedure: An oven-dried Schlenk tube was charged with (bmim)PF6 (4.0 mL) and N-methylimidazole (1 mmol). Propargyl alcohol (2.2 mmol) was added followed by triflic acid (0.1 mmol) under N2 atmosphere at 0 oC and the mixture was magnetically stirred at r.t. until completion (monitored by TLC). Once the reaction was over, the contents were cooled to r. t. and extracted with with EtOAc-Hexane (2:3 vol/vol) until the final extraction did not show a spot corresponding to the starting material or to the product. The combined organic extracts were washed with DI water, dried with MgSO4 and concentrated to give the crude product, which upon purification through column chromatography furnished the desired products. 3,6-bis(1-(4-chlorophenyl)-3-phenylprop-2-ynyl)-9-methyl-9H-carbazole (7): Light yellow solid, m.p. 224-226 °C, Yield: 83%. 1H NMR (500 MHz, CDCl3): δH 3.81 (s, 3H), 5.37 (s, 2H), 7.25-7.30 (m, 8H), 7.33 (d, J = 8.5 Hz, 4H), 7.42 (d, J = 8.5 Hz, 4H), 7.46-7.49 (m, 6H), 8.10 (d, J = 1.5 Hz, 2H); 13C NMR (125 MHz, CDCl3): δC 29.39, 43.29, 85.37, 90.51, 109.00, 119.78, 122.89, 123.57, 126.10, 128.20, 128.42, 128.80, 129.43, 131.83, 132.16, 132.68, 140.67, 141.25 ppm; IR (cm-1, CHCl3): ν 3051, 2929, 2879, 1597, 1573, 1489, 1323, 1249, 1153, 1089, 1014, 844, 796, 783, 754; APCI-MS: 631 [M+H]+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 49% 2: 17% 3: 9% | Stage #1: N-methylcarbazole; 1-(4-bromo-phenyl)-3-phenyl-prop-2-yn-1-ol With bismuth (III) nitrate pentahydrate at 20 - 70℃; Ionic liquid; Inert atmosphere; Schlenk technique; Stage #2: 1-(p-fluorophenyl)-2-heptyn-1-ol With bismuth (III) nitrate pentahydrate at 20 - 70℃; Inert atmosphere; Ionic liquid; Schlenk technique; | 3-(1-(4-bromophenyl)-3-phenylprop-2-ynyl)-9-methyl-6-(1-p-tolylhept-2-ynyl)-9H-carbazole (19) General procedure: The ionic liquid (4.0 mL) was charged into an oven-dried Schlenk tube under a nitrogen atmosphere and Bi(NO3)3·5H2O (10 mol%) was added, and upon sonication (for about 15 min) was dissolved in the IL. N-methylcarbazole (1 mmol) was then introduced into the Schlenk tube under a nitrogen atmosphere followed by the desired propargylic alcohol (1.1 mmol). The reaction mixture was magnetically stirred, initially at r. t. for about 10 minutes followed by stirring in a pre-heated oil bath at 70 °C, until completion (as monitored by TLC). Once the reaction was over, the contents were cooled to r. t. and the 2nd propargylic alcohol (1.1 mmol) was introduced followed by Bi(NO3)3·5H2O (10 mol%). The reaction mixture was magnetically stirred, initially at r. t. for about 10 minutes followed by stirring in a pre-heated oil bath at 70 °C, until completion (as monitored by TLC). Once the reaction was over, the contents were cooled to r. t. and extracted with with EtOAc-Hexane (2:3 vol/vol), until the final extraction did not show a spot corresponding to the starting material or to the product. The combined organic extracts were washed with DI water, dried with MgSO4 and concentrated to give the crude product, which upon purification through column chromatography furnished the desired products. 3-(1-(4-bromophenyl)-3-phenylprop-2-ynyl)-9-methyl-6-(1-p-tolylhept-2-ynyl)-9H-carbazole (19): Yellow liquid, Yield: 49%. 1H NMR (500 MHz, CDCl3): δH 0.92 (t, J = 7.5 Hz, 3H), 1.44-1.57 (m, 4H), 2.28 -2.32 (m, 2H), 2.29 (s, 3H), 5.12 (s, 1H), 5.35 (s, 1H), 7.09 (d, J = 8.0 Hz, 2H), 7.27-7.32 (m, 7H), 7.35-7.36 (m, 2H), 7.42-7.46 (m, 4H), 7.48-7.50 (m, 2H), 8.07 (d, J = 2.0 Hz, 1H), 8.08 (d, J = 2.0 Hz, 1H); 13C NMR (125 MHz, CDCl3): δC 13.71, 18.75, 21.03, 22.03, 29.21, 31.13, 42.83, 43.23, 81.45, 84.96, 85.21, 90.33, 108.57, 108.73, 119.49, 119.63, 120.63, 122.56, 122.92, 123.44, 125.70, 126.06, 127.68, 128.07, 128.27, 129.12, 129.68, 131.60, 131.67, 131.72, 133.50, 136.01, 140.33, 140.42, 140.47, 141.72 ppm; IR (cm-1, CHCl3): ν 3051, 2954, 2927, 2870, 2858, 1724, 1604, 1485, 1463, 1456, 1323, 1286, 1267, 1251, 1155, 1124, 1070, 1010, 912, 840, 802; APCI-MS: 634 [M+H]+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With trifluorormethanesulfonic acid at 0 - 20℃; for 6h; Ionic liquid; Inert atmosphere; Schlenk technique; | 3,6-bis(1-(4-bromophenyl)-3-phenylprop-2-ynyl)-9-methyl-9H-carbazole (8) General procedure: An oven-dried Schlenk tube was charged with (bmim)PF6 (4.0 mL) and N-methylimidazole (1 mmol). Propargyl alcohol (2.2 mmol) was added followed by triflic acid (0.1 mmol) under N2 atmosphere at 0 oC and the mixture was magnetically stirred at r.t. until completion (monitored by TLC). Once the reaction was over, the contents were cooled to r. t. and extracted with with EtOAc-Hexane (2:3 vol/vol) until the final extraction did not show a spot corresponding to the starting material or to the product. The combined organic extracts were washed with DI water, dried with MgSO4 and concentrated to give the crude product, which upon purification through column chromatography furnished the desired products. 3,6-bis(1-(4-bromophenyl)-3-phenylprop-2-ynyl)-9-methyl-9H-carbazole(8): Yellow solid, m.p. 228-230 °C, Yield: 86%. 1H NMR (500 MHz, CDCl3): δH 3.81 (s, 3H), 5.35 (s, 2H), 7.29-7.31 (m, 6H), 7.32-7.37 (m, 6H), 7.42-7.44 (m, 4H), 7.47-7.49 (m, 6H), 8.11 (d, J = 1.5 Hz, 2H); 13C NMR (125 MHz, CDCl3): δC 29.40, 43.37, 85.40, 90.41, 109.02, 119.80, 120.81, 122.89, 123.55, 126.11, 128.22, 128.43, 129.82, 131.76, 131.84, 132.08, 140.69, 141.80 ppm; IR (cm-1, CHCl3): ν 3049, 3020, 2954, 2926, 2900, 2873, 2856, 1597, 1485, 1400, 1321, 1251, 1153, 1070, 1010, 844, 794, 777, 754; APCI-MS: 720 [M+H]+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With trifluorormethanesulfonic acid at 0 - 20℃; for 4h; Ionic liquid; Inert atmosphere; Schlenk technique; | 3,6-bis(1-(4-methoxyphenyl)-3-phenylprop-2-ynyl)-9-methyl-9H-carbazole (9) General procedure: An oven-dried Schlenk tube was charged with (bmim)PF6 (4.0 mL) and N-methylimidazole (1 mmol). Propargyl alcohol (2.2 mmol) was added followed by triflic acid (0.1 mmol) under N2 atmosphere at 0 oC and the mixture was magnetically stirred at r.t. until completion (monitored by TLC). Once the reaction was over, the contents were cooled to r. t. and extracted with with EtOAc-Hexane (2:3 vol/vol) until the final extraction did not show a spot corresponding to the starting material or to the product. The combined organic extracts were washed with DI water, dried with MgSO4 and concentrated to give the crude product, which upon purification through column chromatography furnished the desired products. 3,6-bis(1-(4-methoxyphenyl)-3-phenylprop-2-ynyl)-9-methyl-9H-carbazole (9): Light yellow solid, m.p. 166-168 °C, Yield: 93%. 1H NMR (500 MHz, CDCl3): δH 3.76 (s, 6H), 3.78 (s, 3H), 5.36 (s, 2H), 6.85 (d, J = 8.5 Hz, 4H), 7.27-7.31 (m, 8H), 7.39 (d, J = 8.5 Hz, 4H), 7.48-7.50 (m, 6H), 8.12 (brs, 2H); 13C NMR (125 MHz, CDCl3): δC 29.32, 43.02, 55.41, 84.80, 91.44, 108.78, 114.03, 119.71, 122.87, 123.87, 126.03, 127.97, 128.34, 129.03, 131.82, 132.84, 134.93, 140.53, 158.47 ppm; IR (cm-1, CHCl3): ν 3053, 2997, 2953, 2931, 2904, 2833, 1608, 1583, 1508, 1489, 1463, 1442, 1325, 1301, 1247, 1174, 1155, 1107, 1033, 839, 804, 756; APCI-MS: 622 [M+1]+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | Stage #1: N-methylcarbazole; 1-(4-methylphenyl)-3-phenylprop-2-yn-1-ol With bismuth (III) nitrate pentahydrate at 20 - 70℃; Ionic liquid; Inert atmosphere; Schlenk technique; Stage #2: 1-(4-methoxyphenyl)-3-phenylprop-2-yn-1-ol With bismuth (III) nitrate pentahydrate at 20 - 70℃; Inert atmosphere; Ionic liquid; Schlenk technique; | 3,6-bis(1-(4-methoxyphenyl)-3-phenylprop-2-ynyl)-9H-carbazole (18) General procedure: The ionic liquid (4.0 mL) was charged into an oven-dried Schlenk tube under a nitrogen atmosphere and Bi(NO3)3·5H2O (10 mol%) was added, and upon sonication (for about 15 min) was dissolved in the IL. N-methylcarbazole (1 mmol) was then introduced into the Schlenk tube under a nitrogen atmosphere followed by the desired propargylic alcohol (1.1 mmol). The reaction mixture was magnetically stirred, initially at r. t. for about 10 minutes followed by stirring in a pre-heated oil bath at 70 °C, until completion (as monitored by TLC). Once the reaction was over, the contents were cooled to r. t. and the 2nd propargylic alcohol (1.1 mmol) was introduced followed by Bi(NO3)3·5H2O (10 mol%). The reaction mixture was magnetically stirred, initially at r. t. for about 10 minutes followed by stirring in a pre-heated oil bath at 70 °C, until completion (as monitored by TLC). Once the reaction was over, the contents were cooled to r. t. and extracted with with EtOAc-Hexane (2:3 vol/vol), until the final extraction did not show a spot corresponding to the starting material or to the product. The combined organic extracts were washed with DI water, dried with MgSO4 and concentrated to give the crude product, which upon purification through column chromatography furnished the desired products. 3,6-bis(1-(4-methoxyphenyl)-3-phenylprop-2-ynyl)-9H-carbazole (18): Yellow solid, m.p. 164-166 °C, Yield: 66%. 1H NMR (500 MHz, CDCl3): δH 2.30 (s, 3H), 3.76 (s, 3H), 3.77 (s, 3H), 5.36 (s, 1H), 6.85 (d, J = 8.5 Hz, 2H), 7.12 (d, J = 8.0 Hz, 2H), 7.27-7.30 (m, 8H), 7.37 (d, J = 8.0 Hz, 2H), 7.39 (d, J = 8.5 Hz, 2H), 7.48-7.50 (m, 6H), 8.11 (s, 1H), 8.13 (s, 1H); 13C NMR (125 MHz, CDCl3): δC 21.17, 29.30, 43.02, 43.46, 55.40, 84.80, 91.37, 91.45, 108.77, 114.03, 119.70, 119.75, 122.87, 123.86, 123.89, 126.02, 127.89, 127.95, 128.33, 129.03, 129.36, 131.82, 132.69, 132.82, 134.93, 136.39, 139.80, 140.51, 158.47 ppm; IR (cm-1, CHCl3): ν 3049, 3005, 2951, 2929, 2908, 2833, 1606, 1508, 1489, 1463, 1442, 1327, 1315, 1301, 1247, 1174, 1033, 835, 806, 754; APCI-MS: 606 [M+H]+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | With trifluorormethanesulfonic acid at 0 - 20℃; for 6h; Ionic liquid; Inert atmosphere; Schlenk technique; | 9-methyl-3,6-bis(3-phenyl-1-(thiophen-2-yl)prop-2-ynyl)-9H-carbazole (10) General procedure: An oven-dried Schlenk tube was charged with (bmim)PF6 (4.0 mL) and N-methylimidazole (1 mmol). Propargyl alcohol (2.2 mmol) was added followed by triflic acid (0.1 mmol) under N2 atmosphere at 0 oC and the mixture was magnetically stirred at r.t. until completion (monitored by TLC). Once the reaction was over, the contents were cooled to r. t. and extracted with with EtOAc-Hexane (2:3 vol/vol) until the final extraction did not show a spot corresponding to the starting material or to the product. The combined organic extracts were washed with DI water, dried with MgSO4 and concentrated to give the crude product, which upon purification through column chromatography furnished the desired products. 9-methyl-3,6-bis(3-phenyl-1-(thiophen-2-yl)prop-2-ynyl)-9H-carbazole (10): Light brown solid, m.p. 150-152 °C, Yield: 65%. 1H NMR (500 MHz, CDCl3): δH 3.82 (s, 3H), 5.60 (s, 2H), 6.93 (dd, J = 3.5, 5.0 Hz, 2H), 7.03 (dt, J = 1.5, 3.5 Hz, 2H), 7.18 (dd, J = 1.5, 3.5 Hz, 2H), 7.28-7.31 (m, 6H), 7.36 (d, J = 8.5 Hz, 2H), 7.49-7.52 (m, 4H), 7.60 (dt, J = 1.5, 8.5 Hz, 2H), 8.19 (d, J = 2.0 Hz, 2H); 13C NMR (125 MHz, CDCl3): δC 29.40, 39.42, 84.35, 90.45, 108.92, 119.74, 122.95, 123.53, 124.84, 125.03, 125.94, 126.77, 128.19, 128.36, 131.88, 132.20, 140.89, 147.20 ppm; IR (cm-1, CHCl3): ν 3101, 3066, 3055, 2929, 1597, 1489, 1469, 1427, 1359, 1321, 1251, 1155, 1026, 908, 885, 852, 837, 808, 786, 756; APCI-MS: 574 [M+H]+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With trifluorormethanesulfonic acid at 0 - 20℃; for 5h; Ionic liquid; Inert atmosphere; Schlenk technique; | 9-methyl-3,6-bis(1-phenylhept-2-ynyl)-9H-carbazole (11) General procedure: An oven-dried Schlenk tube was charged with (bmim)PF6 (4.0 mL) and N-methylimidazole (1 mmol). Propargyl alcohol (2.2 mmol) was added followed by triflic acid (0.1 mmol) under N2 atmosphere at 0 oC and the mixture was magnetically stirred at r.t. until completion (monitored by TLC). Once the reaction was over, the contents were cooled to r. t. and extracted with with EtOAc-Hexane (2:3 vol/vol) until the final extraction did not show a spot corresponding to the starting material or to the product. The combined organic extracts were washed with DI water, dried with MgSO4 and concentrated to give the crude product, which upon purification through column chromatography furnished the desired products. 9-methyl-3,6-bis(1-phenylhept-2-ynyl)-9H-carbazole (11): Light yellow liquid, Yield: 76%. 1H NMR (500 MHz, CDCl3): δH 0.93 (t, J = 7.5 Hz, 3H), 0.94 (t, J = 7.5 Hz, 3H), 1.45-1.51 (m, 4H), 1.54-1.60 (m, 4H), 2.30 -2.34 (m, 4H), 3.75 (s, 3H), 5.15 (s, 2H), 7.18-7.20 (m, 2H), 7.23-7.29 (m, 6H), 7.41-7.42 (m, 6H), 8.07-8.08 (m, 2H); 13C NMR (125 MHz, CDCl3): δC 13.82, 18.87, 22.18, 29.28, 31.26, 43.38, 81.44, 85.20, 108.60, 119.65, 122.86, 125.98, 126.57, 127.94, 128.53, 133.23, 140.43, 143.47 ppm; IR (cm-1, CHCl3): ν 3061, 3026, 2956, 2929, 2872, 2860, 1724, 1645, 1600, 1489, 1465, 1452, 1429, 1317, 1249, 1153, 1124, 908, 792; APCI-MS: 522 [M+H]+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With trifluorormethanesulfonic acid at 0 - 20℃; for 6h; Ionic liquid; Inert atmosphere; Schlenk technique; | 3,6-bis(1-(4-fluorophenyl)hept-2-ynyl)-9-methyl-9H-carbazole (12) General procedure: An oven-dried Schlenk tube was charged with (bmim)PF6 (4.0 mL) and N-methylimidazole (1 mmol). Propargyl alcohol (2.2 mmol) was added followed by triflic acid (0.1 mmol) under N2 atmosphere at 0 oC and the mixture was magnetically stirred at r.t. until completion (monitored by TLC). Once the reaction was over, the contents were cooled to r. t. and extracted with with EtOAc-Hexane (2:3 vol/vol) until the final extraction did not show a spot corresponding to the starting material or to the product. The combined organic extracts were washed with DI water, dried with MgSO4 and concentrated to give the crude product, which upon purification through column chromatography furnished the desired products. 3,6-bis(1-(4-fluorophenyl)hept-2-ynyl)-9-methyl-9H-carbazole (12): Yellow liquid, Yield: 70%. 1H NMR (500 MHz, CDCl3): δH 0.93 (t, J = 7.5 Hz, 6H), 1.43-1.50 (m, 4H), 1.54-1.60 (m, 4H), 2.30-2.33 (m, 4H), 3.78 (s, 3H), 5.13 (s, 2H), 6.95-6.98 (m, 4H), 7.29 (d, J = 9.0 Hz, 2H), 7.35-7.41 (m, 6H), 8.04-8.05 (m, 2H); 13C NMR (125 MHz, CDCl3): δC 13.81, 18.8, 22.18, 29.33, 31.22, 42.63, 81.27, 85.49, 108.74, 115.27 (d, JCF = 21.2 Hz), 119.55, 122.84, 125.95, 129.42 (d, JCF = 8.2 Hz), 133.11, 139.20 (d, JCF = 2.7 Hz), 140.49, 161.68 (d, JCF = 243.3 Hz) ppm; 19F NMR (470MHz, CDCl3): δF -116.90 (m); IR (cm-1, CHCl3): ν 2956, 2931, 2870, 2860, 1602, 1504, 1489, 1456, 1321, 1251, 1222, 1157, 844, 808, 771; APCI-MS: 558 [M+H]+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With trifluorormethanesulfonic acid at 0 - 20℃; for 5h; Ionic liquid; Inert atmosphere; Schlenk technique; | 9-methyl-3,6-bis(1-p-tolylhept-2-ynyl)-9H-carbazole (13) General procedure: An oven-dried Schlenk tube was charged with (bmim)PF6 (4.0 mL) and N-methylimidazole (1 mmol). Propargyl alcohol (2.2 mmol) was added followed by triflic acid (0.1 mmol) under N2 atmosphere at 0 oC and the mixture was magnetically stirred at r.t. until completion (monitored by TLC). Once the reaction was over, the contents were cooled to r. t. and extracted with with EtOAc-Hexane (2:3 vol/vol) until the final extraction did not show a spot corresponding to the starting material or to the product. The combined organic extracts were washed with DI water, dried with MgSO4 and concentrated to give the crude product, which upon purification through column chromatography furnished the desired products. 9-methyl-3,6-bis(1-p-tolylhept-2-ynyl)-9H-carbazole (13): Brown Liquid, Yield: 78%. 1H NMR (500 MHz, CDCl3): δH 0.93 (t, J = 7.5 Hz, 3H), 0.94 (t, J = 7.5 Hz, 3H), 1.44-1.51 (m, 4H), 1.54-1.60 (m, 4H), 2.31 (s, 6H), 2.29-2.33 (m, 4H), 3.75 (s, 3H), 5.12 (s, 2H), 7.09 (d, J = 8.0 Hz, 4H), 7.26 (d, J = 8.0 Hz, 2H), 7.29 (d, J = 8.0 Hz, 4H), 7.41 (d, J = 8.0 Hz, 2H), 8.06-8.07 (m, 2H) ; 13C NMR (125 MHz, CDCl3): δC 13.82, 18.89, 21.14, 22.18, 29.28, 31.28, 42.98, 81.65, 84.99, 108.54, 119.62, 122.89, 125.93, 127.81, 129.23, 133.39, 136.09, 141.42, 140.61 ppm; IR (cm-1, CHCl3): ν 3047, 3020, 2954, 2929, 2870, 2860, 1728, 1606, 1510, 1489, 1463, 1456, 1429, 1379, 1361, 1325, 1313, 1290, 1251, 1153, 1124, 1109, 1022, 802, 763; APCI-MS: 550 [M+H]+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With trifluorormethanesulfonic acid at 0 - 20℃; for 4.5h; Ionic liquid; Inert atmosphere; Schlenk technique; | 9-methyl-3,6-bis(1-p-tolylhept-2-ynyl)-9H-carbazole (5) General procedure: An oven-dried Schlenk tube was charged with (bmim)PF6 (4.0 mL) and N-methylimidazole (1 mmol). Propargyl alcohol (2.2 mmol) was added followed by triflic acid (0.1 mmol) under N2 atmosphere at 0 oC and the mixture was magnetically stirred at r.t. until completion (monitored by TLC). Once the reaction was over, the contents were cooled to r. t. and extracted with with EtOAc-Hexane (2:3 vol/vol) until the final extraction did not show a spot corresponding to the starting material or to the product. The combined organic extracts were washed with DI water, dried with MgSO4 and concentrated to give the crude product, which upon purification through column chromatography furnished the desired products. 9-methyl-3,6-bis(1-p-tolylhept-2-ynyl)-9H-carbazole (5): Yellow solid, m.p. 184-186 °C, Yield: 91%. 1H NMR (500 MHz, CDCl3): δH 2.31 (s, 6H), 3.79 (s, 3H), 5.37 (s, 2H), 7.12 (d, J = 8.0 Hz, 4H), 7.25-7.32 (m, 8H), 7.37 (d, J = 8.0 Hz, 4H), 7.48-7.51 (m, 6H), 8.13 (d, J = 1.0 Hz, 2H); 13C NMR (125 MHz, CDCl3): δC 21.18, 29.34, 43.49, 84.83, 91.37, 108.78, 119.81, 122.93, 123.94, 126.06, 127.91, 127.95, 128.34, 129.37, 131.86, 132.73, 136.40, 139.85, 140.56 ppm; IR (cm-1, CHCl3): ν 3049, 3020, 2953, 2924, 2872, 2858, 1724, 1597, 1508, 1489, 1467, 1442, 1325, 1313, 1267, 1251, 1153, 1124, 1070, 1022, 885, 835, 806, 756; APCI-MS: 590 [M+H]+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With trifluorormethanesulfonic acid at 0 - 20℃; for 4h; Ionic liquid; Inert atmosphere; Schlenk technique; | 3,6-bis(1,3-diphenylprop-2-ynyl)-9-methyl-9H-carbazole (4) General procedure: An oven-dried Schlenk tube was charged with (bmim)PF6 (4.0 mL) and N-methylimidazole (1 mmol). Propargyl alcohol (2.2 mmol) was added followed by triflic acid (0.1 mmol) under N2 atmosphere at 0 oC and the mixture was magnetically stirred at r.t. until completion (monitored by TLC). Once the reaction was over, the contents were cooled to r. t. and extracted with with EtOAc-Hexane (2:3 vol/vol) until the final extraction did not show a spot corresponding to the starting material or to the product. The combined organic extracts were washed with DI water, dried with MgSO4 and concentrated to give the crude product, which upon purification through column chromatography furnished the desired products. 3,6-bis(1,3-diphenylprop-2-ynyl)-9-methyl-9H-carbazole (4): Light yellow solid, m.p. 214-216 °C, Yield: 89%. 1H NMR (500 MHz, CDCl3): δH 3.80 (s, 3H), 5.41 (s, 2H), 7.20-7.33 (m, 15H), 7.48-7.52 (m, 9H), 8.14 (d, J = 1.5 Hz, 2H); 13C NMR (125 MHz, CDCl3): δC 29.35, 43.87, 85.00, 91.15, 108.83, 119.84, 122.92, 123.85, 126.13, 126.84, 128.01, 128.06, 128.35, 128.68, 131.85, 132.59, 140.59, 142.71 ppm; IR (cm-1, CHCl3): ν 3080, 3059, 3026, 1597, 1475, 1467, 1452, 1442, 1336, 1317, 1251, 1155, 1126, 1028, 914, 881, 798, 754; APCI-MS: 562 [M+H]+ |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With bis(1,5-cyclooctadiene)nickel (0); 1,3-bis(2,4,6-trimethylphenyl)4,5-dimethyl-1,3-dihydro-2H-imidazol-2-ylidene; diisopropopylaminoborane; sodium acetate In toluene at 180℃; for 18h; | |
89% | With bis(1,5-cyclooctadiene)nickel (0); 1,3-bis(adamantan-2-yl)imidazolin-2-yliden chloride; sodium t-butanolate In toluene at 160℃; for 18h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With triethylsilane; potassium <i>tert</i>-butylate In 1,3,5-trimethyl-benzene at 165℃; for 60h; Inert atmosphere; Glovebox; | 6.8 Experiments with C-N and C-S Heteroaryl Compounds at Elevated Temperatures Experiments were also conducted with C-N and C-S heteroaryl compounds. In the case of compounds comprising C-N bonds, reactivity appeared to be similar to that seen for C-O bonds, and it is reasonably expected that the wide ranging methods used for the latter will result in results in similar reactivity in the former: |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With indium(III) triflate In 1,2-dichloro-ethane at 20℃; for 8h; Inert atmosphere; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With indium(III) triflate In 1,2-dichloro-ethane at 20℃; for 8h; Inert atmosphere; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
61% | With triethylsilane; trifluoroacetic acid In dichloromethane at 20℃; for 24h; Inert atmosphere; chemoselective reaction; | N-Methylation of Aromatic Amines and N-Heterocycles; General Procedure General procedure: The N-containing substrate (1 mmol) and trioxane (270 mg, 3 mmol) were dissolved in CH2Cl2 (1.5 mL) under N2 atmosphere. To this solution were added TFA (0.75 mL) and Et3SiH (1.45 mL, 10 mmol). The reaction was monitored by TLC (eluent: see below). After 24 or 48 h (in case of incomplete conversion, after 24 h), aq 2 N NaOH (20 mL) solution was carefully added and the mixture was extracted with CH2Cl2 (3*20 mL). The combined organic layers were dried (MgSO4) and concentrated in vacuo and the residue was purified by flash column chromatography (FCC). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
49% | With triethylsilane; trifluoroacetic acid In dichloromethane at 20℃; for 48h; Inert atmosphere; chemoselective reaction; | N-Methylation of Aromatic Amines and N-Heterocycles; General Procedure General procedure: The N-containing substrate (1 mmol) and trioxane (270 mg, 3 mmol) were dissolved in CH2Cl2 (1.5 mL) under N2 atmosphere. To this solution were added TFA (0.75 mL) and Et3SiH (1.45 mL, 10 mmol). The reaction was monitored by TLC (eluent: see below). After 24 or 48 h (in case of incomplete conversion, after 24 h), aq 2 N NaOH (20 mL) solution was carefully added and the mixture was extracted with CH2Cl2 (3*20 mL). The combined organic layers were dried (MgSO4) and concentrated in vacuo and the residue was purified by flash column chromatography (FCC). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With 1,10-Phenanthroline; sodium hydride In benzene at 120℃; for 18h; Glovebox; Sealed tube; | |
67% | With 1,10-Phenanthroline; potassium <i>tert</i>-butylate In 1,3,5-trimethyl-benzene at 160℃; for 8h; Inert atmosphere; Green chemistry; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1.1: acetic acid / water; acetonitrile / 3 h / 20 °C 1.2: 0 - 20 °C 2.1: 1,10-Phenanthroline; potassium <i>tert</i>-butylate / 1,3,5-trimethyl-benzene / 8 h / 160 °C / Inert atmosphere; Green chemistry |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With silver hexafluoroantimonate; tris(2,4-di-tert-butylphenyl)phosphite gold(I) chloride In tetrahydrofuran at 20℃; for 0.25h; regioselective reaction; | |
60% | With tris(pentafluorophenyl)borate In 1,2-dichloro-ethane at 50℃; for 16h; Inert atmosphere; | |
51% | Stage #1: N-methylcarbazole With bis(benzonitrile)palladium(II) dichloride; sodium tetrakis[(3,5-di-trifluoromethyl)phenyl]borate; 2,6-bis((S)-4-isopropyl-4,5-dihydrooxazol-2-yl)pyridine In chloroform for 0.0833333h; Molecular sieve; Inert atmosphere; Stage #2: Methyl phenyldiazoacetate In chloroform at 30℃; for 5h; Molecular sieve; Inert atmosphere; |
19% | With [2,2]bipyridinyl; tetrakis(acetonitrile)copper(I) hexafluorophosphate In dichloromethane at 20℃; for 2h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With titanium(IV) isopropylate; bis(acetylacetonate)nickel(II); C29H40N2*ClH; sodium t-butanolate In toluene at 120℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | With sodium hydride In tetrahydrofuran Reflux; | Synthesis of (E)-9-methyl-3-styryl-9H-carbazole Cd2 To a suspension 9H-carbazole-3-carbaldehyde (445 mg, 2.28 mmol) andbenzyltriphenylphosphonium bromide 7 (987 mg, 2.28 mmol) in 100 mL dry THF was addedsodium hydride (1 g, 41.67 mmol). The solution was refluxed overnight. During reflux, the colorchanged from white to light yellow. The residue was quenched with water. The organic phaseswere combined, dried over magnesium sulfate and the solvent removed under reduced pressure.The residue was purified by column chromatography (SiO2) using DCM:pentane 1:1 as the eluent(454 mg, 74% yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With copper(II) sulfate In acetonitrile at 110℃; Inert atmosphere; | 9 Preparation of N-methylcarbazole-3-sulfonic acid phenyl ester N-methylcarbazole-3-sulfonic acid phenyl ester using the following steps: In a 1000 ml reaction vessel, 7.24 g of N-methylcarbazole, 19.14 g of copper sulfate, 11.95 g of a ligand (a C4-isocyanide compound) 4.41 g of iodonium diphenylborate tetrafluoroborate and 600 mL of acetonitrile were heated to 110 ° C under nitrogen. The reaction was followed by TLC, until the reaction mass disappeared. After the reaction, water was added to the system, and the product was extracted with ethyl acetate. After drying, the solvent was removed by rotary evaporator to give a crude product; The crude product was purified by column chromatography (petroleum ether: ethyl acetate = 10: 1) to obtain 11.51 g of N-methylcarbazole-3- Sulfonic acid phenyl ester with a yield of 85%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With sodium hydroxide In water; toluene for 5h; Reflux; chemoselective reaction; | 4.2. General Procedure for the Synthesis of 1b-7b and 11b. General procedure: A 100mL round-bottom flask was equipped with a magnetic stir bar and a reflux condenser. To xylene (10.0mL), tetradecyltrimethylammonium bromide (1.1mmol) and a heterocyclic compound (1.0mmol) were added, followed bya solution of NaOH 50% (5.0 mL). The mixture was stirred at reflux temperature for 2-18 h. After completion of thereaction, the mixture was air-jet cooled to 25 °C and TLC indicated the disappearance of the starting material. The reaction mix was treated with AcOEt (4 × 20 mL), and the organic phase separated and removed under reduced pressure. The residue was purified to analytical purity by column chromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89.8% | With aluminum (III) chloride In 1,2-dichloro-ethane at 0℃; Reflux; | 1.2 Example 1 Preparation of 1-(9-methyl-9H-carbazol-3-yl)-3-phenylprop-2-en-1-one (1): The second step, After cooling the reaction system to 0°C,A mixed solution of 0.06 mol of N-methyl carbazole and 25 mL of 1,2-dichloroethane was added dropwise with stirring.0.06 mol AlCl3 slowly warms to reflux temperature,TLC monitored until the end of the reaction; third step,Add the appropriate amount of water to the reaction system,Stir well and let it stand for liquid separation.The organic phase is washed with saturated sodium carbonate,Evaporate the solventGet the crude product; the fourth step,The crude product is recrystallized from absolute ethanol.1-(3-N-methyl-carbazolyl)-3-phenyl-propenone is obtained, |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | In n-heptane Inert atmosphere; UV-irradiation; | Carbazoles 4; General Procedure General procedure: Under an N2 atmosphere, substrate 3 (0.2 mmol) and 1,2-diiodobenzene(IV) (0.1 mmol) were placed in a dry glass tube. Heptane (10 mL) was added and the well-stirred mixture was irradiated under UV light(300 nm) until the reaction was complete (TLC monitoring). The solvent was removed in vacuo and the residue was purified by silica gelcolumn chromatography to afford the corresponding carbazole 4.9-Methyl-9H-carbazole (4a)Yield: 12.9 mg (71%); white solid; mp 91.5-92.5 °C. The yield of 4astarting from 3v was 6.7 mg (37%).1H NMR (400 MHz, CDCl3): δ = 8.11 (d, J = 7.8 Hz, 2 H), 7.49 (t, J = 7.6Hz, 2 H), 7.41 (d, J = 8.1 Hz, 2 H), 7.30-7.20 (m, 2 H), 3.87 (s, 3 H).13C NMR (151 MHz, CDCl3): δ = 141.11, 125.80, 122.89, 120.44,118.95, 108.55, 29.22.HRMS (ESI): m/z [M + H]+ calcd for C13H12N: 182.0964; found:182.0964. |
Multi-step reaction with 2 steps 1: n-heptane / 2 h / Inert atmosphere; UV-irradiation 2: n-heptane / 2 h / Inert atmosphere; UV-irradiation |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With 2,3-dicyano-5,6-dichloro-p-benzoquinone In ethyl acetate at 20℃; for 8h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | Carbazole (100 mg, 0.60 mmol),DMF (4 mL),Potassium tert-butoxide (201 mg, 1.8 mmol, 3 eq.) was added to the reaction flask in turn.After stirring at room temperature for 5 minutes, after the potassium tert-butoxide is uniformly dispersed,Slowly inject methyl trifluoroacetate (0.29 mL, 2.4 mmol, 4 eq.) into the reaction flask.After 10 hours of reaction, the TLC plate, the material points disappeared,That is, the reaction is complete and stirring is stopped.It is extracted twice with ethyl acetate and distilled water, and then washed with a saturated NaCI solution. The organic phase is combined, and the organic phase is dried over anhydrous magnesium sulfate. Carbazole (108 mg, yield 99%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With copper diacetate; palladium diacetate In N,N-dimethyl acetamide at 130℃; for 72h; Inert atmosphere; | 1 Example 1 The synthesis of N-methylcarbazole has the structural formula: Preparation method 4: In the reaction tube, 4.5 mg of palladium acetate, 109.0 mg of copper acetate, 45.5 mg of N-methyl-N-phenyl anthranilic acid and 2.0 mL of N,N-dimethylacetamide were added under a nitrogen atmosphere. . It was placed in a 130 ° C oil bath for 72 hours. The conventional treatment gave pure product 28.3 mg with a yield of 78%. |
71% | With copper diacetate; palladium diacetate In N,N-dimethyl acetamide at 130℃; for 72h; Inert atmosphere; chemoselective reaction; | |
65% | With pyridine In dimethylsulfoxide-d6 for 48h; Irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With sodium hydride In tetrahydrofuran at 20℃; for 3.5h; | General Procedure for Synthesizing Anthracene Based Emitters NaH (60% in mineral oil, 2.4 equiv.) Was added to the corresponding donor amine D1-D3 (1.2 equiv.) Dissolved in anhydrous THF (2 mL) and the mixture was allowed to stir for 30 minutes.9-Cyano-10-fluoroanthracene (1.0 equiv.) Was added and the mixture was stirred for 3 hours.The mixture was added to water (10 mL) and extracted with DCM (3 × 10 mL).The concentrated organic layer was purified by column chromatography using chloroform: hexane (v / v 1: 4).The resulting solid was further recrystallized from DCM / hexane mixture. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90.7% | With sodium ethanolate In ethanol; dimethyl sulfoxide for 0.05h; Cooling; | 1 Example 1 Preparation of 3-hydroxymethyl-9-methylcarbazole: In a dry 100 mL three-necked flask, 20 mL of DMSO, 84 mg (2.8 mmol) of paraformaldehyde, 285.8 mg (4.2 mmol) of sodium ethoxide, 2 mL of absolute ethanol, 2 mL of absolute ethanol, and 500 mg (2.8 mmol) were added thereto in an ice salt bath. N-methylcarbazole was dissolved in 5 mL of DMSO, and rapidly dropped into the reaction system. After reacting for 3 minutes, the reaction was terminated by dropwise addition of 3 drops of concentrated hydrochloric acid. Then, 30 mL of distilled water was added, and a solid was precipitated, suctioned, washed with water, and dried to obtain a crude product. The crude product was recrystallized from absolute ethanol to give a pure yellow solid. of 3-hydroxymethyl-9-methylcarbazole. The yield was 90.7%, |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With silver hexafluoroantimonate; tris(2,4-di-tert-butylphenyl)phosphite gold(I) chloride In tetrahydrofuran at 20℃; for 0.25h; regioselective reaction; |
Tags: 1484-12-4 synthesis path| 1484-12-4 SDS| 1484-12-4 COA| 1484-12-4 purity| 1484-12-4 application| 1484-12-4 NMR| 1484-12-4 COA| 1484-12-4 structure
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H317 | May cause an allergic skin reaction |
H318 | Causes serious eye damage |
H319 | Causes serious eye irritation |
H320 | Causes eye irritation |
H330 | Fatal if inhaled |
H331 | Toxic if inhaled |
H332 | Harmful if inhaled |
H333 | May be harmful if inhaled |
H334 | May cause allergy or asthma symptoms or breathing difficulties if inhaled |
H335 | May cause respiratory irritation |
H336 | May cause drowsiness or dizziness |
H340 | May cause genetic defects |
H341 | Suspected of causing genetic defects |
H350 | May cause cancer |
H351 | Suspected of causing cancer |
H360 | May damage fertility or the unborn child |
H361 | Suspected of damaging fertility or the unborn child |
H361d | Suspected of damaging the unborn child |
H362 | May cause harm to breast-fed children |
H370 | Causes damage to organs |
H371 | May cause damage to organs |
H372 | Causes damage to organs through prolonged or repeated exposure |
H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
Code | Phrase |
H400 | Very toxic to aquatic life |
H401 | Toxic to aquatic life |
H402 | Harmful to aquatic life |
H410 | Very toxic to aquatic life with long-lasting effects |
H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
Sorry,this product has been discontinued.
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