* 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.
In a flask, the imine(3 g, 10 mmol) was dissolved in tetrahydrofuran(25 ml), followed by dropwise addition of chloromethyl ethyl ether(1.04 g, 11 mmol), the mixture was stirred under N2 at 40 °C for 18 h, and then ethyl ether(25 ml) was added to separate white solid, the solid was filtered and washed with ethyl ether, the white solid was dried under vacuum affording 2.2 g IMes*HCl in 65percent yield. 1H NMR(CDCl3, 400 MHz): δ 2.15(s, 12H), 2.33(s, 6H), 7.00(s, 4H), 7.70(s, 2H), 10.73(s, 1H); 13C NMR(CDCl3, 100 MHz): δ 17.6, 21.1, 124.8, 129.8, 130.7, 134.1, 139.2, 141.1.
65%
at 40℃; for 18 h; Inert atmosphere
In a flask, the imine (3.0 g, 10 mmol) was dissolved in tetrahydrofuran (25 ml), followed by dropwise addition of chloromethyl ethyl ether (1.04 g, 11 mmol), the mixture was stirred under N2 at 40 °C for 18 h, and then ethyl ether (25 ml) was added to separate white solid, the solid was filtered and washed with ethyl ether, the white solid was dried under vacuum affording 2.2 g IMes*HCl in 65percent yield. 1H NMR (CDCl3, 400 MHz): δ 2.15 (s, 12H), 2.33 (s, 6H), 7.00 (s, 4H), 7.70 (s, 2H), 10.73 (s, 1H); 13C NMR (CDCl3, 100 MHz): δ 17.6, 21.1, 124.8, 129.8, 130.7, 134.1, 139.2, 141.1.
48%
at 20℃; for 0.5 h; Inert atmosphere
Chloromethylethyl ether (0.300 g, 3.17 mmol) in THF (1 mL) was added to a solution of glyoxal-bis(2,4,6-trimethylphenyl)imine (0.900 g, 3.08 mmol) in THF (10 mL). After 30 min stirring under nitrogen at room temperature, a white solid precipitated, which was collected by suctionfiltration and recrystallized from n-hexane to yield product as a white powder (0.49 g, 48 percent).
Reference：
[1] Journal of Organic Chemistry, 2008, vol. 73, # 7, p. 2784 - 2791
[2] Tetrahedron Letters, 2012, vol. 53, # 7, p. 815 - 818
[3] Tetrahedron, 2012, vol. 68, # 38, p. 7949 - 7955
[4] Chemical Communications, 2011, vol. 47, # 5, p. 1559 - 1561
[5] Journal of Organometallic Chemistry, 2013, vol. 743, p. 44 - 48
[6] Tetrahedron, 1999, vol. 55, # 51, p. 14523 - 14534
[7] RSC Advances, 2015, vol. 5, # 37, p. 29022 - 29031
2
[ 50-00-0 ]
[ 56222-36-7 ]
[ 141556-45-8 ]
Yield
Reaction Conditions
Operation in experiment
66%
With hydrogenchloride In 1,4-dioxane; ethyl acetate at 0℃; for 2.5 h;
Charging a 1 L round bottom flask with methanol (500 mL), 2,4,6-trimethylaniline (97 mL, 689 mmol), glyoxal (40 wt percent solution in water, 38.8 mL, 313.5 mmol), and formic acid (1 mL).Stirring the resulting mixture for 3 hours at room temperature.Filtering the yellow precipitate formed, (1) Diagram D.Washing precipitate with cold methanol.Drying precipitate in vacuo overnight (91.0percent, 74.5 g, 313.5 mmol).Charging a 5 L round bottom flask with 1 (100 g, 342 mmol) and ethyl acetate (2000 mL).Cooling solution to 0° C.Charging a 500 mL Erlenmeyer flask with paraformaldehyde (13.35 g, 445 mmol) and HCl (4N in dioxane, 136.9 mL, 548 mmol,).Stirring this solution for 10 minutes then add it to the cooled solution of 1.Stirring the reaction mixture for a total reaction time of 2.5 hours.Collecting the beige precipitate formed by filtration.Drying the precipitate.Dissolving precipitate in 100 ml of dichloromethane.Adding Sodium bicarbonate (10.0 g) to the solution.Stirring the mixture for 1 hour or until the solution stopped bubbling.Filtering the solution to remove the solids.Precipitating the product with 100 ml of diethyl etherCollecting product by filtrationWashing product with etherDrying product in vacuo to yield IMes.HCl (2) as an off-white powder (66percent, 77.1 g, 226 mmol). 1H NMR (CDCl3, 400 MHz) δ 11.02 (s, 1H), 7.58 (s, 2H), 7.04 (s, 4H), 2.32 (s, 6H), 2.2 (s, 12H); 13C NMR (CDCl3, 400 MHz) δ 141, 139, 134, 130.5, 129.8, 124, 21, 17.8. Synthesis of 1,3-Bis(2,4,6-trimethylphenyl)imidazolium chloride (IMes.HCl, 2)A 1 L round bottom flask was charged with methanol (500 mL), 2,4,6-trimethylaniline (97 mL, 689 mmol), glyoxal (40 wt percent solution in water, 38.8 mL, 313.5 mmol), and formic acid (1 mL). The resulting mixture was allowed to stir for 3 hours at room temperature. The yellow precipitate (1) formed was filtered, washed with cold methanol and dried in vacuo overnight (91.0percent, 74.5 g, 313.5 mmol). A 5 L round bottom flask was charged with 1 (100 g, 342 mmol) and ethyl acetate (2000 mL). The solution was cooled to 0° C. A 500 mL Erlenmeyer flask was charged with paraformaldehyde (13.35 g, 445 mmol) and HCl (4N in dioxane, 136.9 mL, 548 mmol,). This solution was stirred for 10 minutes then added. The reaction mixture was stirred for a total reaction time of 2.5 hours. The beige precipitate formed was collected by filtration, dried and dissolved in 100 ml of dichloromethane. Sodium bicarbonate (10.0 g) was added to the solution and the mixture was stirred for 1 hour or until the solution stopped bubbling. The solution was then filtered to remove the solids and the product was precipitated with 100 ml of diethyl ether, collected by filtration, washed with ether, and dried in vacuo to yield IMes.HCl (2) as an off-white powder (66percent, 77.1 g, 226 mmol). 1H NMR (CDCl3, 400 MHz) δ 11.02 (s, 1H), 7.58 (s, 2H), 7.04 (s, 4H), 2.32 (s, 6H), 2.2 (s, 12H); 13C NMR (CDCl3, 400 MHz) δ 141, 139, 134, 130.5, 129.8, 124, 21, 17.8.
66%
With hydrogenchloride In 1,4-dioxane; ethyl acetate at 0℃; for 2.5 h;
Synthesizing of l,3-Bis(2,4,6-trimethylphenyl)imidazoliιim chloride (IMes HCI, 2) by:; Charging a IL round bottom flask with methanol (500 mL), 2,4,6- 5 trimethylaniline (97 mL, 689 mmol), glyoxal (40 wt percent solution in water, 38.8 mL,313.5 mmol), and formic acid (ImL).Stirring the resulting mixture for 3 hours at room temperature. Filtering the yellow precipitate formed, (1) Diagram D. Washing precipitate with cold methanol. 0 Drying precipitate in vacuo overnight (91.0percent, 74.5 g, 313.5 mmol).Charging a 5 L round bottom flask with 1 (100 g, 342 mmol) and ethyl acetate (2000 mL).Cooling solution to O0C.Charging a 500 mL Erlenmeyer flask with paraformaldehyde (13.35 g, 445 5 mmol) and HCl (4N in dioxane, 136.9 mL, 548 mmol,).Stirring this solution for 10 minutes then add it to the cooled solution of 1. Stirring the reaction mixture for a total reaction time of 2.5 hours. Collecting the beige precipitate formed by filtration. Drying the precipitate..0 Dissolving precipitate in 100 ml of dichloromethane.Adding Sodium bicarbonate (10.0 g) to the solution. Stirring the mixture for 1 hour or until the solution stopped bubbling. Filtering the solution to remove the solids. Precipitating the product with 100 ml of diethyl ether J5 Collecting product by filtrationWashing product with etherDrying product in vacuo to yield IMesηCl (2) as an off-white powder (66 percent, 77.1 g, 226 mmol). 1H NMR (CDCl3, 400 MHz) δ 11.02 (s, IH), 7.58 (s, 2H), 7.04 (s, 4H), 2.32 (s, 6H), 2.2 (s, 12H); 13C NMR (CDCl3, 400 MHz) δ 141, 139, 134, 130.5, 10 129.8, 124, 21, 17.8.; Synthesis of l,3-Bis(2,4,6-trimethylphenyl)imidazolium chloride (IMes-HCl, 2); A l L round bottom flask was charged with methanol (500 mL), 2,4,6- trimethylaniline (97 mL, 689 mmol), glyoxal (40 wt percent solution in water, 38.8 mL, 313.5 mmol), and formic acid (ImL). The resulting mixture was allowed to stir for 3 hours at room temperature. The yellow precipitate (1) formed was filtered, washed with cold methanol and dried in vacuo overnight (91.0percent, 74.5 g, 313.5 mmol). A 5 L round bottom flask was charged with 1 (100 g, 342 mmol) and ethyl acetate (2000 mL). The solution was cooled to O0C. A 500 mL Erlenmeyer flask was charged with paraformaldehyde (13.35 g, 445 mmol) and HCl (4N in dioxane, 136.9 mL, 548 mmol,). This solution was stirred for 10 minutes then added. The reaction mixture was stirred for a total reaction time of 2.5 hours. The beige precipitate formed was collected by filtration, dried and dissolved in 100 ml of dichloromethane. Sodium bicarbonate (10.0 g) was added to the solution and the mixture was stirred for 1 hour or until the solution stopped bubbling. The solution was then filtered to remove the solids and the product was precipitated with 100 ml of diethyl ether, collected by filtration, washed with ether, and dried in vacuo to yield IMesηCl (2) as an off-white powder (66 percent, 77.1 g, 226 mmol). 1H NMR (CDCl3, 400 MHz) δ 11.02 (s, IH), 7.58 (s, 2H), 7.04 (s, 4H), 2.32 (s, 6H), 2.2 (s, 12H); 13C NMR (CDCl3, 400 MHz) δ 141, 139, 134, 130.5, 129.8, 124, 21, 17.8.
Reference：
[1] Dalton Transactions, 2016, vol. 45, # 44, p. 17859 - 17866
[2] Chemical Communications, 2015, vol. 51, # 7, p. 1282 - 1284
[3] Patent: US7109348, 2006, B1, . Location in patent: Page/Page column 3; 5-7
[4] Patent: WO2008/36084, 2008, A1, . Location in patent: Page/Page column 4; 6; 7-8
[5] Journal of Organometallic Chemistry, 2007, vol. 692, # 24, p. 5390 - 5394
[6] Green Chemistry, 2018, vol. 20, # 5, p. 964 - 968
3
[ 50-00-0 ]
[ 56222-36-7 ]
[ 141556-45-8 ]
Reference：
[1] Organic Letters, 2017, vol. 19, # 10, p. 2750 - 2753
[2] Chemistry - A European Journal, 2007, vol. 13, # 25, p. 7195 - 7203
Reference：
[1] Journal of Organic Chemistry, 2001, vol. 66, # 23, p. 7729 - 7737
[2] Tetrahedron, 1999, vol. 55, # 51, p. 14523 - 14534
[3] Chemical Communications, 2011, vol. 47, # 5, p. 1559 - 1561
[4] Organic Syntheses, 2010, vol. 87, p. 77 - 87
[5] Tetrahedron, 2012, vol. 68, # 38, p. 7949 - 7955
[6] Journal of Organometallic Chemistry, 2013, vol. 743, p. 44 - 48
[7] Patent: US9403854, 2016, B2,
6
[ 56222-36-7 ]
[ 173035-10-4 ]
Reference：
[1] Journal of the American Chemical Society, 2003, vol. 125, # 9, p. 2546 - 2558
7
[ 56222-36-7 ]
[ 134030-21-0 ]
Yield
Reaction Conditions
Operation in experiment
95%
With hydrogenchloride; sodium cyanoborohydride In methanol at 20℃; for 20 h;
1[056] (b) with NaCNI3H3: A 300 mE round bottom flask was charged with 1,2-dimesityl ethylene diimine (3.8 g, 13 mmol), methanol (100 mE) and NaCNI3H3 (4.92 g, 78 mmol). Concentrated HC1 was added dropwise to maintain the pH below 4, and the reaction was stirred at room temperature for 20 hours (overnight). The solution was then diluted with 50 mE water, made basic with NaOH, and extracted thoroughly with CH2C12. The organic layer war dried over MgSO4, filtered and the solvent was removed in vacuo to yield 1 ,2-dimesityl ethylene diamine (95percent yield).
Reference：
[1] Inorganic Chemistry, 2011, vol. 50, # 24, p. 12338 - 12348
[2] Journal of Organic Chemistry, 2008, vol. 73, # 7, p. 2784 - 2791
[3] Journal of the American Chemical Society, 2016, vol. 138, # 15, p. 5044 - 5051
[4] Journal of Organic Chemistry, 2001, vol. 66, # 23, p. 7729 - 7737
[5] Journal of the American Chemical Society, 2000, vol. 122, # 34, p. 8168 - 8179
[6] Patent: US2016/237101, 2016, A9, . Location in patent: Paragraph 0056
[7] New Journal of Chemistry, 2017, vol. 41, # 3, p. 1057 - 1063
[8] Organic letters, 1999, vol. 1, # 6, p. 953 - 956
[9] Advanced Synthesis and Catalysis, 2009, vol. 351, # 1-2, p. 71 - 77
[10] Tetrahedron, 2010, vol. 66, # 40, p. 7988 - 7994
[11] Organometallics, 2010, vol. 29, # 19, p. 4339 - 4345
[12] Zeitschrift fur Anorganische und Allgemeine Chemie, 2011, vol. 637, # 7-8, p. 988 - 994
[13] Tetrahedron Letters, 2012, vol. 53, # 7, p. 815 - 818
[14] Tetrahedron, 2012, vol. 68, # 38, p. 7949 - 7955
[15] Organometallics, 2016, vol. 35, # 7, p. 943 - 949
With sodium tetrahydroborate; In tetrahydrofuran; methanol; at 0 - 20℃; for 3h;
General procedure: In a dry round bottom flask was added diimine 4 (1 mmol) and dissolved in dry THF and absolute MeOH (10 mL, ratio: 6/4). The solution cooled at 0 C and then NaBH4 (8 mmol) was added in portions within 1 hour. The reaction mixture was stirred at room temperature until the starting diimine was consumed, at which point the color of the solution turned into white. Then, a saturated aqueous solution of NH4Cl (10 mL) was added and the mixture was extracted with Et2O (3 x 10 mL). The solvent was removed under vacuum and the corresponding diamine was used without any further purification (Yields: 87-99%). N1, N2-bis(Dimesityl)ethane-1,2-diamine 5a7Yellowish oil (99% yield); deltaH (200 MHz, CDCl3) 6.96 (s, 4H, arom), 3.39 (s, 2H, NH), 3.26 (s, 4H, CH2), 2.40 (s, 12H, o-CH3), 2.34 (s, 6H, p-CH3); deltaC (50 MHz, CDCl3) 143.7, 131.7, 130.1, 129.8, 49.5, 20.9, 18.8; m/z (ESI) (%) 297.4 [(M+H)+, 100].
95%
With hydrogenchloride; sodium cyanoborohydride; In methanol; at 20℃; for 20h;pH < 4;
1[056] (b) with NaCNI3H3: A 300 mE round bottom flask was charged with 1,2-dimesityl ethylene diimine (3.8 g, 13 mmol), methanol (100 mE) and NaCNI3H3 (4.92 g, 78 mmol). Concentrated HC1 was added dropwise to maintain the pH below 4, and the reaction was stirred at room temperature for 20 hours (overnight). The solution was then diluted with 50 mE water, made basic with NaOH, and extracted thoroughly with CH2C12. The organic layer war dried over MgSO4, filtered and the solvent was removed in vacuo to yield 1 ,2-dimesityl ethylene diamine (95% yield).
With sodium tetrahydroborate; In ethanol; at 0℃;Reflux;
In a flask, the imine(1.3 g, 4.45 mmol) was suspended in ethyl alcohol(65 ml), then cooled to 0 C and sodium borohydride(3.36 g, 89 mmol) was added slowly, after stirring for 30 min, the mixture was reflux until the reaction solution was changed to colorless, the reaction was complete. The solution was cooled to room temperature, then aqueous saturated sodium chloride(12 ml) was added to stir for 30 min, after that, 50 ml water and 40 ml chloroform was added, organic phase was separated, washed with small amount of water, dried under anhydrous sodium sulfate, and then volatiles were removed under vacuum, yielding lightyellow oil. The oil was purged to next step, in the same flask, ammonium chlorite(261.9 mg, 4.9 mmol), and triethyl orthoformate(4 ml) was added, the mixture was stirred under N2 at 110 C overnight, then ethyl ether was added to separated yellow solid, filtered and then crystaled through dichloromethane and ethyl ether, affording 1.3 g yellow SIMes*HCl in 85% yield. 1H NMR(CDCl3, 400 MHz): delta 2.30(s, 6H), 2.40(s, 12H), 4.61(s, 4H), 6.97(s, 4H), 7.27(s, 2H), 9.16(s, 1H); 13C NMR(CDCl3, 100 MHz): delta 17.9, 21.0, 51.9, 129.9, 130.3, 135.0, 140.3, 160.1.
With sodium tetrahydroborate; In ethyl acetate; at 0℃;Reflux;
In a flask, the imine (1.3 g, 4.45 mmol) was suspended in ethyl alcohol (65 ml), then cooled to 0 C and sodium borohydride (3.36 g, 89 mmol) was added slowly, after stirring for 30 min, the mixture was heated to reflux until the color of the solution turn into colorless. Cool to room temperature, then aqueous saturated sodium chloride (12 ml) was added to stir for 30 min, after that, 50 ml water and 40 ml chloroform was added, then organic phase was separated, washed with small amount of water, dried under anhydrous sodium sulfate, and then volatiles were removed under vacuum, yielding light yellow oil. The oil was purged to next step. In the same flask, ammonium chlorite (261.9 mg, 4.9 mmol) and triethyl orthoformate (4 ml) was added, the mixture was stirred under N2 at 110 C overnight, then ethyl ether was added to separated yellow solid, filtered and then recrystallized by dichloromethane and ethyl ether, affording 1.3 g yellow SIMes·HCl in 85% yield.
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