Metal catalysts for selective formation of cyclic carbonates, process for preparing cyclic carbonate using the same and use of cyclic carbonate
09850223 ยท 2017-12-26
Assignee
Inventors
Cpc classification
C07D317/70
CHEMISTRY; METALLURGY
C07D317/44
CHEMISTRY; METALLURGY
B01J31/2295
PERFORMING OPERATIONS; TRANSPORTING
B01J2231/49
PERFORMING OPERATIONS; TRANSPORTING
International classification
C07D317/44
CHEMISTRY; METALLURGY
C07D317/70
CHEMISTRY; METALLURGY
Abstract
Provided are a novel metal catalyst for preparing cyclic carbonate, and a method for preparing cyclic carbonate using the same, and more particularly, a method for selectively preparing cyclic carbonate in a high yield and at a higher conversion rate as compared to the existing catalysts, using the metal complex including a ligand represented by Chemical Formula 1 below and a trivalent metal in Group 8 or Group 13 as a catalyst and using various structures of epoxide compounds and carbon dioxide as raw materials. In addition, provided are the prepared cyclic carbonate, and an electrolyte including the same: ##STR00001## in Chemical Formula 1, R.sup.1 is hydrogen, (C1-C20)alkyl or halogen; R.sup.2 is hydrogen, (C1-C20)alkyl, (C1-C20)alkoxy, halogen or nitro.
Claims
1. A metal complex comprising a ligand represented by Chemical Formula 1 below and a trivalent metal in Group 8 or Group 13: ##STR00043## in Chemical Formula 1, R.sup.1 is hydrogen, (C1-C20)alkyl or halogen; R.sup.2 is hydrogen, (C1-C20)alkyl, (C1-C20)alkoxy, halogen or nitro.
2. The metal complex of claim 1, wherein the metal complex is represented by Chemical Formula 2 below: ##STR00044## in Chemical Formula 2, M is Fe or Al; R.sup.1 is hydrogen, (C1-C20)alkyl or halogen; R.sup.2 is hydrogen, (C1-C20)alkyl, (C1-C20)alkoxy, halogen or nitro.
3. The metal complex of claim 2, wherein the metal complex is selected from the following structures: ##STR00045##
4. A method for preparing cyclic carbonate by reacting carbon dioxide with alkylene oxide using the metal complex of claim 1, as a catalyst.
5. The method of claim 4, wherein the alkylene oxide is represented by Chemical Formula 3 below, and the cyclic carbonate is represented by Chemical Formula 4 below: ##STR00046## in Chemical Formulas 3 and 4, R.sup.3a and R.sup.4a are each independently hydrogen, (C1-C10)alkyl, halo(C1-C10)alkyl or (C6-C12)aryl, and R.sup.3a and R.sup.4a may be linked via (C3-C5)alkylene with or without a fused ring to form a ring, wherein the formed ring may be further substituted with vinyl, (CH.sub.2).sub.aSiR.sup.11R.sup.12R.sup.13, oxiranyl or (7-oxa-bicyclo[4.1.0]heptane-3-yl)acetyl; R.sup.3b and R.sup.4b are each independently hydrogen, (C1-C10)alkyl, halo(C1-C10)alkyl or (C6-C12)aryl, and R.sup.3b and R.sup.4b may be linked via (C3-C5)alkylene with or without a fused ring to form a ring, wherein the formed ring may be further substituted with vinyl, (CH.sub.2).sub.aSiR.sup.11R.sup.12R.sup.13, 1,3-dioxolan-2-one-4-yl or (hexahydrobenzo[d][1,3]dioxol-2-one-5-yl)acetyl; R.sup.11 to R.sup.13 are each independently (C1-C10)alkyl or (C1-C10)alkoxy; and a is an integer of 1 to 5.
6. The method of claim 4, wherein the metal complex catalyst has an amount of 0.1 to 2.0 mol % relative to the alkylene oxide.
7. The method of claim 4, wherein an ammonium co-catalyst or an amine-based co-catalyst is further included.
8. The method of claim 7, wherein the ammonium co-catalyst or the amine-based co-catalyst has an amount of 0.1 to 10.0 mol % relative to the alkylene oxide.
9. The method of claim 8, wherein the ammonium co-catalyst is selected from the group consisting of tetrabutylammonium bromide (NBu.sub.4Br), tetramethylammonium bromide (NMe.sub.4Br), tetraethylammonium tetrafluoroborate (NEt.sub.4BF.sub.4), tetrapropylammonium bromide (NPr.sub.4Br), tetrahexylammonium chloride (N[(CH.sub.2).sub.5CH.sub.3].sub.4Cl), tetrapentylammonium bromide (N[(CH.sub.2).sub.4CH.sub.3].sub.4Br), tetraheptylammonium bromide (N[(CH.sub.2).sub.6CH.sub.3].sub.4Br), tetraoctylammonium bromide (N[CH.sub.2).sub.7CH.sub.3].sub.4Br), trimethyldodecylammonium chloride (CH.sub.3(CH.sub.2).sub.11N(CH.sub.3).sub.3Cl), trimethyltetradecylammonium bromide (CH.sub.3(CH.sub.2).sub.13N(CH.sub.3).sub.3Br), trimethylhexadecylammonium chloride (CH.sub.3(CH.sub.2).sub.15N(CH.sub.3).sub.3Cl), methyltrioctylammonium chloride (CH.sub.3N[(CH.sub.2).sub.7CH.sub.3].sub.3Cl), tetrabutylammonium fluoride (NBu.sub.4F), tetrabutylammonium chloride (NBu.sub.4Cl), tetrabutylammonium iodide (NBu.sub.4I), 1-butyl-3-methylimidazolium bromide ([bmim]Br), 1-butyl-3-methylimidazolium chloride ([bmim]Cl), and bis(triphenylphosphine)iminium chloride ([((C.sub.6H.sub.5).sub.3P).sub.2N]Cl, PPNCl), and the amine-based co-catalyst is selected from the group consisting of triethylamine (Et.sub.3N), 1,8-diazabicycloundec-7-ene (DBU), pyridine (C.sub.5H.sub.5N), and 4-dimethylaminopyridine (C.sub.7H.sub.10N.sub.2, DMAP).
10. The method of claim 4, wherein a reaction temperature is 25 to 120 C., and a reaction pressure is 1 to 10 bar.
11. The method of claim 4, wherein the reaction is a neat reaction.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1)
(2)
(3)
(4)
(5)
DETAILED DESCRIPTION OF EMBODIMENTS
(6) Hereinafter, a configuration of the present invention will be described in detail with reference to Examples. These Examples are provided only for assisting in the entire understanding of the present invention, and it will be obvious to those skilled in the art that the scope of the present invention is not construed to be limited to these examples.
(7) Commercially available reagents and carbon dioxide (99.99%) were used without further purification or drying. All reactions were performed in a 80 mL stainless steel reactor. .sup.1H NMR (400 MHz) and .sup.13C NMR (100 MHz) analyses were recorded on a Bruker Advance III HD spectrometer. The mass spectra were analyzed on a High Resolution Hybrid Tandem LC-MS/MS spectrometer.
[Preparation Examples 1 to 8] Preparation of Ligands 1a to 1h
(8) ##STR00012##
(9) Preparation of Compound B
(10) To a stirred solution of 2,2-dihydroxybenzophenone (Compound A, DHBP) (30 g, 140 mmol) in MeOH (300 mL), 4 equivalents of saturated ammonia (38 mL, 560 mmol) was added at ambient temperature, followed by stirring for 16 hours. As the reaction proceeded, since it was difficult to stir, methanol (300 mL) was additionally added during the stirring. The formation of Compound B was confirmed by .sup.1H NMR (in DMSO-d.sub.6). When the reaction was completed, yellow precipitate was filtered and washed with methanol to obtain Compound B as a yellow solid (26.7 g, 90% yield).
(11) .sup.1H NMR (400 MHz, DMSO-d.sub.6): 7.33-7.29 (m, 2H), 7.06-7.05 (d, 2H), 6.90-6.88 (d, 2H), 6.76-6.72 (br, 2H); .sup.13C NMR (100 MHz, DMSO-d.sub.6): 177.3, 132.4, 130.0, 117.8, 117.1; HRMS (ESI) m/z calculated for C.sub.13H.sub.12NO.sub.2 [H.sup.+]: 214.0868, found: 214.0867.
(12) Preparation of Compound C
(13) To a stirred mixture of the Compound B (20 g, 94 mmol) in methanol (200 mL), NaBH.sub.4 (6.4 g, 170 mmol, 1.8 equiv.) was added at ambient temperature, followed by stirring for 1 hour. Then, saturated HCl aqueous solution (24.3 ml, 28 mmol, 3 equiv.) was slowly added at 0 C., followed by stirring for 30 minutes. Solvent was evaporated thoroughly and the product was redissolved in ethanol. White solid (Na salt) was precipitated and removed with filtration. The ethanol solution was concentrated and CHCl.sub.3 was added to obtain a white solid. The white solid product was filtered to obtain Compound C (21.6 g, 91% yield).
(14) .sup.1H NMR (400 MHz, DMSO-d.sub.6): 10.32 (s, 2H), 8.65 (s, 3H), 7.32-7.29 (dd, 2H), 7.19-7.15 (m, 2H), 7.07-7.05 (dd, 2H), 6.83-6.79 (t, 2H), 5.87-5.86 (d, 1H); .sup.13C NMR (100 MHz, DMSO-d.sub.6): 155.0, 129.4, 128.4, 123.4, 118.8, 115.7, 47.4; HRMS (ESI) m/z calculated for C.sub.13H.sub.14NO.sub.2 [H.sup.+]: 216.1019, found: 216.1002.
(15) Preparation of Compound 1a
(16) To a methanol solution of the Compound C (4 g, 15.9 mmol), triethylamine (2.3 ml, 16.7 mmol, 1.05 equiv.) and salicylaldehyde (16.7 mmol, 1.05 equiv.) were added and stirred. The degree of reaction was monitored using .sup.1H NMR, and after 1 hour of the stirring, a prepared yellow solid was filtered and washed with methanol to obtain a compound 1a (84% yield).
Preparation Example 1: Compound 1a
(17) ##STR00013##
(18) .sup.1H NMR (400 MHz, DMSO-d.sub.6): 13.90 (s, 1H), 9.56 (s, 2H), 8.65 (s, 1H), 7.47-7.44 (dd, 1H), 7.34-7.30 (m, 1H), 7.14-7.08 (m, 4H), 6.89-6.84 (m, 4H), 6.82-6.78 (td, 2H); .sup.13C NMR (100 MHz, DMSO-d.sub.6): 164.8, 160.8, 154.8, 132.4, 131.8, 128.2, 128.1, 127.8, 118.8, 118.8, 118.5, 116.5, 115.3, 63.7; HRMS (ESI) m/z calculated for C.sub.20H.sub.18NO.sub.3 [H].sup.+: 320.1287, found: 320.1271.
(19) Preparation of Compound 1b
(20) Compound 1b (yellow solid, 87% yield) was obtained by performing the same method as the preparation method of Compound 1a except for using 5-nitrosalicylaldehyde (16.7 mmol, 1.05 equiv.) instead of using salicylaldehyde.
Preparation Example 2: Compound 1b
(21) ##STR00014##
(22) .sup.1H NMR (400 MHz, DMSO-d.sub.6): 15.15 (s, 1H), 10.02 (s, 2H), 8.94 (s, 1H), 8.51-8.50 (d, 1H), 8.07-8.04 (dd, 1H), 7.20-7.10 (td, 2H), 7.13-7.10 (dd, 2H), 6.89-6.87 (dd, 2H), 6.84-6.80 (td, 2H), 6.65-6.53 (d, 1H), 6.33 (s, 1H); .sup.13C NMR (100 MHz, DMSO-d.sub.6): 176.6, 165.9, 155.0, 134.5, 132.2, 129.2, 128.5, 124.5, 122.2, 119.1, 115.6, 114.0, 62.0; HRMS (ESI) m/z calculated for C.sub.20H.sub.17N.sub.2O.sub.5 [H.sup.+]: 365.1137, found: 365.1109.
(23) Preparation of Compound 1c
(24) To a methanol solution of the Compound C (4 g, 15.9 mmol), triethylamine (2.3 ml, 16.7 mmol, 1.05 equiv.) and 3,5-dichlorosalicylaldehyde (16.7 mmol, 1.05 equiv.) were added and stirred. The degree of reaction was monitored using .sup.1H NMR, and after 1 hour of the stirring, solvent was concentrated by evaporation, followed by recrystallization using chloroform to obtain Compound 1c (Yellow solid, 66% yield).
(25) ##STR00015##
Preparation Example 3: Compound 1c
(26) .sup.1H NMR (400 MHz, DMSO-d.sub.6): 15.34 (s, 1H), 9.87 (s, 2H), 7.58-7.57 (d, 1H), 7.51-7.50 (d, 1H), 7.17-7.11 (m, 4H), 6.87-6.85 (dd, 2H), 7.13-7.10 (dd, 2H), 6.83-6.79 (td, 2H), 6.31 (s, 1H); .sup.13C NMR (100 MHz, DMSO-d.sub.6): 164.4, 162.9, 154.9, 132.8, 130.5, 128.8, 128.4, 125.6, 124.3, 119.0, 117.5, 117.1, 115.5, 62.1; HRMS (ESI) m/z calculated for C.sub.20H.sub.16N.sub.1O.sub.3Cl.sub.2 [H.sup.+]: 388.0507, found: 388.0461.
(27) Preparation of Compound 1d
(28) Compound 1d (yellow solid, 59% yield) was obtained by performing the same method as the preparation method of Compound 1a except for using 5-fluorosalicylaldehyde (16.7 mmol, 1.05 equiv.) instead of using salicylaldehyde.
Preparation Example 4: Compound 1d
(29) ##STR00016##
(30) .sup.1H NMR (400 MHz, DMSO-d.sub.6): 13.58 (s, 1H), 9.57 (s, 2H), 8.63 (s, 1H), 7.42-7.38 (dd, 1H), 7.22-7.15 (td, 1H), 7.12-7.07 (m, 4H), 6.90-6.76 (m, 5H), 6.28 (s, 1H).
(31) Preparation of Compound 1e
(32) To a methanol solution of the Compound C (350 mg, 1.39 mmol, 1.0 equiv.), triethylamine (0.19 mL, 1.39 mmol, 1.0 equiv.) and 5-methoxysalicylaldehyde (1.39 mmol, 1.0 equiv) were added and stirred. The degree of reaction was monitored using .sup.1H NMR, and after 6 hours of the stirring, solvent was evaporated, and the obtained mixture was dissolved in ethyl acetate, and washed with water. The ethyl acetate solution was dried over magnesium sulfide, and solvent was evaporated, followed by recrystallization using chloroform and hexane to obtain Compound 1e (yellow solid, 88% yield).
Preparation Example 5: Compound 1e
(33) ##STR00017##
(34) .sup.1H NMR (400 MHz, DMSO-d.sub.6): 13.19 (s, 1H), 9.51 (s, 2H), 8.59 (s, 1H), 7.11-7.07 (m, 5H), 6.96-6.92 (dd, 1H), 6.82-6.75 (m, 5H), 6.28 (s, 1H), 3.70 (s, 3H).
(35) Preparation of Compound 1f
(36) Compound 1f (yellow solid, 73% yield) was obtained by performing the same method as the preparation method of Compound 1c except for using 5-methylsalicylaldehyde (16.7 mmol, 1.05 equiv.) instead of using 3,5-dichlorosalicylaldehyde.
Preparation Example 6: Compound 1f
(37) ##STR00018##
(38) .sup.1H NMR (400 MHz, DMSO-d.sub.6): 13.50 (s, 1H), 9.56 (s, 2H), 8.55 (s, 1H), 7.24 (s, 1H), 7.15-7.06 (m, 5H), 6.84-6.75 (m, 5H), 6.27 (s, 1H), 2.22 (s, 3H).
(39) Preparation of Compound 1g
(40) To a methanol solution of the Compound C (350 mg, 1.39 mmol, 1.0 equiv.), triethylamine (0.19 mL, 1.39 mmol, 1.0 equiv.) and 3,5-di-t-butylsalicylaldehyde (1.39 mmol, 1.0 equiv) were added and stirred. The degree of reaction was monitored using .sup.1H NMR, and after 6 hours of the stirring, solvent was evaporated, and the obtained mixture was dissolved in ethyl acetate, and washed with water. The ethyl acetate was dried over magnesium sulfide, and evaporated to obtain Compound 1g (yellow solid, 89% yield).
Preparation Example 7: Compound 1g
(41) ##STR00019##
(42) .sup.1H NMR (400 MHz, DMSO-d.sub.6): 14.45 (s, 1H), 9.44 (s, 2H), 8.65 (s, 1H), 7.32-7.28 (dd, 2H), 7.15-7.08 (m, 4H), 6.87-6.85 (dd, 2H), 6.82-6.78 (td, 2H), 6.36 (s, 1H), 1.39 (s, 9H), 1.32 (s, 9H); .sup.13C NMR (100 MHz, DMSO-d.sub.6): 166.1, 157.8, 154.8, 139.6, 135.6, 128.2, 128.0, 128.0, 126.5, 126.1, 118.8, 117.9, 115.3, 63.4, 34.6, 33.8, 31.3, 29.3; HRMS (ESI) m/z calculated for C.sub.28H.sub.34N.sub.1O.sub.3 [H.sup.+]: 432.2539, found: 432.2553.
(43) Preparation of Compound 1h
(44) Compound 1h (yellow solid, 73% yield) was obtained by performing the same method as the preparation method of Compound 1e except for using 3-t-butyl-5-nitrosalicylaldehyde (1.39 mmol, 1.0 equiv) instead of using 5-methoxysalicylaldehyde.
Preparation Example 8: Compound 1h
(45) ##STR00020##
(46) .sup.1H NMR (400 MHz, DMSO-d.sub.6): 15.14 (s, 1H), 10.07 (s, 2H), 8.92-8.89 (d, 1H), 8.40-8.39 (d, 1H), 7.94-7.93 (d, 1H), 7.21-7.17 (td, 2H), 7.13-7.11 (dd, 2H), 6.91-6.89 (dd, 2H), 6.86-6.82 (td, 2H), 6.32-6.31 (d, 1H), 1.34 (s, 9H); .sup.13C NMR (100 MHz, DMSO-d.sub.6): 177.7, 166.6, 155.0, 141.9, 133.2, 131.3, 129.4, 128.6, 124.5, 124.2, 119.1, 115.6, 113.5, 61.8, 34.8, 28.7; HRMS (ESI) m/z calculated for C.sub.24H.sub.25N.sub.2O.sub.5 [H.sup.+]: 421.1763, found: 421.1758.
[Examples 1 to 10] Preparation of Metal Complex
(47) ##STR00021##
[Example 1] Preparation of Metal Complex Fe-1a
(48) To a methanol mixture of the Compound 1a (300 mg, 0.94 mmol), FeCl.sub.3 (152 mg, 0.94 mmol, 1 equiv.) and triethylamine (285 mg, 2.82 mmol, 3 equiv.) were added and stirred for 12 hours. After the stirring was completed, a prepared brown solid was filtered and washed with methanol to obtain a metal complex Fe-1a (72% yield).
(49) UV-Vis [THF, nm (L mol.sup.1 cm.sup.1)]: 260 (sh, 40000), 342 (sh, 10000), 423 (7000). IR (KBr pellet, cm.sup.1): 3465, 3064, 3045, 2996, 2894, 1627, 1616, 1546, 1481, 1479, 1401, 1295, 1151, 1114, 1037, 887, 823, 755; HRMS (ESI) m/z calculated for [{C.sub.20H.sub.14FeN.sub.1O.sub.3}.sub.2+Na].sup.+: 767.05, found: 766.87; Anal. calculated for C.sub.40H.sub.28Fe.sub.2N.sub.2O.sub.6.2EtOH: C, 63.18; H, 4.82; N, 3.35. Found: C, 63.18; H, 5.05; N, 3.21. Crystal required for structural analysis through X-ray diffraction was obtained by slowly diffusing diethyl ether in saturated tetrahydrofuran (THF) solution of Fe-1a (
[Example 2] Preparation of Metal Complex Fe-1b
(50) A metal complex Fe-1b (85% yield) was obtained by performing the same method as the preparation of the metal complex Fe-1a except for using the Compound 1b instead of using the Compound 1a.
(51) UV-Vis [THF, nm (L mol.sup.1 cm.sup.1)]: 276 (30000), 346 (30000), 460 (sh, 6000). IR (KBr pellet, cm.sup.1): 3471, 3075, 3006, 2902, 1637, 1610, 1587, 1482, 1473, 1394, 1319, 1101, 1035, 954, 894, 846, 755; HRMS (ESI) m/z calculated for [{C.sub.20H.sub.13FeN.sub.2O.sub.5}.sub.2+Na].sup.+: 857.02, found: 856.80; Anal. Calculated for C.sub.40H.sub.26Fe.sub.2N.sub.4O.sub.10.2EtOH: C, 57.04; H, 4.13; N, 6.05. Found: C, 57.21; H, 4.27; N, 5.81. Crystal required for structural analysis through X-ray diffraction was obtained by slowly evaporating saturated benzene (THF) solution of Fe-1b (
[Example 3] Preparation of Metal Complex Fe-1c
(52) A metal complex Fe-1c (85% yield) was obtained by performing the same method as the preparation of the metal complex Fe-1a except for using the Compound 1c instead of using the Compound 1a.
(53) IR (KBr pellet, cm.sup.1): 3641, 3429, 3057, 3010, 2970, 2925, 2891, 1626, 1560, 1528, 1483, 1477, 1441, 1416, 1388, 1302, 1290, 1267, 1242, 1223, 1180, 1117, 1105, 1066, 1034, 970, 937, 889, 863, 802, 794, 775, 755.
[Example 4] Preparation of Metal Complex Fe-1d
(54) A metal complex Fe-1d (98% yield) was obtained by performing the same method as the preparation of the metal complex Fe-1a except for using the Compound 1d instead of using the Compound 1a.
(55) IR (KBr pellet, cm.sup.1): 3627, 3419, 3057, 3012, 2891, 1691, 1626, 1595, 1552, 1477, 1466, 1450, 1387, 1290, 1267, 1254, 1225, 1188, 1147, 1117, 1066, 1034, 985, 968, 937, 895, 860, 822, 756.
[Example 5] Preparation of Metal Complex Fe-1e
(56) A metal complex Fe-1e (77% yield) was obtained by performing the same method as the preparation of the metal complex Fe-1a except for using the Compound 1e instead of using the Compound 1a.
(57) IR (KBr pellet, cm.sup.1): 3430, 3055, 3006, 2935, 2900, 2835, 1626, 1610, 1547, 1477, 1450, 1388, 1348, 1290, 1267, 1196, 1161, 1112, 1071, 1031, 895, 823, 756.
[Example 6] Preparation of Metal Complex Fe-1f
(58) A metal complex Fe-1f (94% yield) was obtained by performing the same method as the preparation of the metal complex Fe-1a except for using the Compound 1f instead of using the Compound 1a.
(59) IR (KBr pellet, cm.sup.1): 3415, 3055, 3012, 2920, 2866, 1624, 1595, 1545, 1477, 1450, 1385, 1292, 1267, 1238, 1227, 1165, 1138, 1115, 1070, 1036, 893, 856, 825, 814, 754.
[Example 7] Preparation of Metal Complex Fe-1g
(60) A metal complex Fe-1g (93% yield) was obtained by performing the same method as the preparation of the metal complex Fe-1a except for using the Compound 1g instead of using the Compound 1a.
(61) IR (KBr pellet, cm.sup.1): 3060, 3002, 2958, 2904, 2870, 1622, 1597, 1558, 1539, 1477, 1450, 1412, 1388, 1361, 1301, 1255, 1219, 1173, 1116, 1070, 1036, 1011, 930, 916, 887, 847, 820, 800, 791, 752.
[Example 8] Preparation of Metal Complex Fe-1h
(62) A metal complex Fe-1h (82% yield) was obtained by performing the same method as the preparation of the metal complex Fe-1a except for using the Compound 1h instead of using the Compound 1a.
(63) IR (KBr pellet, cm.sup.1): 3417, 3062, 3006, 2958, 2908, 2870, 1633, 1595, 1566, 1502, 1481, 1450, 1442, 1419, 1392, 1311, 1288, 1267, 1244, 1200, 1180, 1153, 1117, 1068, 1036, 985, 926, 889, 845, 820, 800, 754.
[Example 9] Preparation of Metal Complex Al-1a
(64) To a tetrahydrofuran solution of Compound 1a (300 mg, 0.94 mmol), 2.0 M AlMe.sub.3 heptane solution (0.47 ml, 0.94 mmol, 1 equiv.) was added and stirred for 3 hours. After the stirring was completed, solvent was evaporated to be concentrated, and hexane was added to obtain a white solid. The white solid was filtered to obtain Al-1a (62% yield).
(65) .sup.1H NMR (400 MHz, DMSO-d.sub.6): 8.67 (s, 1H), 7.38 (m, 2H), 7.22 (d, 2H), 6.96 (t, 2H), 6.83 (d, 1H), 6.78 (t, 1H), 6.58 (m, 4H), 5.67 (s, 1H); .sup.13C NMR (100 MHz, DMSO-d.sub.6): 164.5, 163.4, 158.4, 134.8, 133.3, 130.1, 128.3, 127.7, 120.9, 120.1, 119.7, 117.1, 116.4, 76.3; UV-Vis [THF, nm (L mol.sup.1 cm.sup.1)]: 265 (33000), 273 (30000), 294 (13000), 337 (10000); IR (KBr pellet, cm.sup.1): 3056, 3029, 3008, 2969, 2923, 2886, 1633, 1606, 1554, 1482, 1457, 1405, 1311, 1294, 1274, 1240, 1214, 1186, 1151, 1132, 1116, 1076, 1035, 906, 894, 860, 835, 817, 794, 755; HRMS (ESI) m/z calculated for [{C.sub.40H.sub.28N.sub.2O.sub.6}+Na].sup.+: 709.15, found: 709.15. Anal. Calculated for C.sub.40H.sub.28Al.sub.2N.sub.2O.sub.6: C, 69.97; H, 4.11; N, 4.08. Found: C, 69.42; H, 4.26; N, 3.94. Crystal required for structural analysis through X-ray diffraction was obtained by slowly diffusing diethyl ether in saturated tetrahydrofuran (THF) solution of Al-1a (
[Example 10] Preparation of Metal Complex Al-1b
(66) A metal complex Al-1b (70% yield) was obtained by performing the same method as the preparation of the metal complex Al-1a except for using the Compound 1b instead of using the Compound 1a.
(67) .sup.1H NMR (400 MHz, DMSO-d.sub.6): 8.66 (s, 1H), 8.39 (s, 1H), 8.09 (dd, 1H), 7.07 (dd, 2H), 6.89 (td, 2H), 6.69 (d, 1H), 6.46 (dd, 2H), 6.41 (td, 2H), 5.46 (s, 1H); .sup.13C NMR (100 MHz, DMSO-d.sub.6): 171.6, 162.5, 160.2, 135.3, 130.4, 130.1, 128.8, 128.0, 127.4, 121.7, 119.6, 119.5, 114.4, 77.9, 67.0, 25.1; UV-Vis [THF, nm (L mol.sup.1 cm.sup.1)]: 249 (sh, 22000), 262 (19000), 278 (sh, 15000), 294 (13000), 325 (16000). IR (KBr pellet, cm.sup.1): 3060, 2989, 2981, 2910, 1650, 1602, 1565, 1488, 1394, 1336, 1303, 1209, 1130, 1101, 1045, 1035, 1014, 954, 904, 833, 800, 754, 692, 626; HRMS (ESI) m/z calculated for C.sub.20H.sub.14AlN.sub.2O.sub.5 [H].sup.+: 389.07, found: 389.07; Anal. Calculated for C.sub.20H.sub.13AlN.sub.2O.sub.5: C, 62.61; H, 4.60; N, 6.08. Found: C, 62.62; H, 4.69; N, 5.92. Crystal required for structural analysis through X-ray diffraction was obtained by slowly diffusing pentane in saturated tetrahydrofuran (THF) solution of Al-1a (
[Example 11] Preparation of Cyclic Carbonate Using Carbon Dioxide and Cyclohexene Oxide
(68) ##STR00022##
(69) To a 80 mL stainless steel reactor, 0.5 mol % catalyst, 2.5 mol % tetrabutylammonium bromide (NBu.sub.4Br), and 1 ml of cyclohexene oxide were charged. The reactor was charged and discharged with 5 bar of CO.sub.2 twice and finally charged with 10 bar of CO.sub.2. The reactor was sealed, followed by stirring at 100 C. to perform the reaction. After the reaction was completed, an aliquot of the reaction mixture was dissolved in CDCl.sub.3 and analyzed by .sup.1H NMR.
(70) Each catalyst, reaction time, and yield and selectivity of the products were shown in Table 1 below.
(71) TABLE-US-00001 TABLE 1 Reaction Time Yield Selectivity Entry Catalyst (h) (%) (I:II) 1 Fe-1a 2 45 >50:1 2 Fe-1a 8 83 23:1 3 Fe-1b 8 80 49:1 4 Fe-1c 8 89 20:1 5 Fe-1d 8 91 9:1 6 Fe-1e 8 75 8:1 7 Fe-1f 8 71 23:1 8 Fe-1g 8 87 2:1 9 Fe-1h 8 84 5:1 10 Al-1a 8 92 1.1:1 11 Al-1b 8 89 1.8:1
(72) It was observed from entry 1 and entry 2 that when the same catalyst was used, as the reaction time passes, the conversion rate was increased, and selectivity was slightly decreased, from which could be appreciated that a large amount of cyclic carbonate was present in the obtained product.
(73) In entry 3, the most excellent selectivity was exhibited in the same reaction time.
(74) It could be confirmed that entry 10 and entry 11 using aluminum metal complex had similar reactivity to the case of using iron metal complex; however, slightly decreased selectivity.
(75) Therefore, it could be appreciated that when the metal complex of the present invention including the ligand including three phenolate donors bonded to the trisubstituted carbon and the salicylidene moiety is used as the catalyst for the reaction of carbon dioxide and alkylene oxide, the cyclic carbonate could be selectively prepared with high conversion rate to alkylene oxide.
[Example 12] Preparation of Cyclic Carbonate
(76) Epoxide compounds 3-4 and 3-8 were prepared according to the method reported in document (Laserna, V.; Fiorani, G.; Whiteoak, C. J.; Martin, E.; Escudero-Adn, E.; Kleij, A. W. Angew. Chem., Int. Ed. 2014, 53, 10416).
(77) The cyclic carbonation was performed as follows.
(78) As shown in Table 2 below, the catalyst of the present invention, NBu.sub.4Br and 1 g or 1 ml of epoxide were charged in 80 mL stainless steel reactor. Fe-1b of Example 2 was used as the catalyst, and NBu.sub.4Br was used as the co-catalyst. The reactor was charged and discharged with 5 bar of CO.sub.2 twice and finally charged with 10 bar of CO.sub.2. The reactor was sealed, followed by stirring at 100 C. for predetermined time. After the reaction was completed, an aliquot of the reaction mixture was analyzed by .sup.1H NMR spectroscopy using CDCl.sub.3 as the solvent. The crude mixture was passed through the silica using 10:1 mixture of chloroform and ethyl acetate as an eluent to remove catalyst and ammonium salt. Solvent was removed under vacuum and target cyclic carbonate was obtained.
(79) All of prepared cyclic carbonates 1-1 to 1-10 were cis-selective and the NMR spectra thereof were the same as the previously reported NMR spectra (Cyclic carbonates 1-1 to 1-3, 1-5, 1-6 to 1-10: Laserna, V.; Fiorani, G.; Whiteoak, C. J.; Martin, E.; Escudero-Adn, E.; Kleij, A. W. Angew. Chem., Int. Ed. 2014, 53, 10416; Cyclic carbonate 1-4: Orsini, F.; Sello, G.; Bestetti, G. Tetrahedron: Asymmetry 2001, 12, 2961.).
(80) TABLE-US-00002 TABLE 2 Co- Catalyst catalyst Re- used used action Epoxide amount amount time Entry compound (mol %) (mol %) (h) 1
(81) 1) Compound 1-1:
(82) ##STR00033##
(83) Conversion rate 99%, Amount 1.25 g (91% Yield); .sup.1H NMR (400 MHz, CDCl.sub.3): 4.67-4.62 (m, 2H), 1.89-1.76 (m, 4H), 1.59-1.49 (m, 2H), 1.41-1.32 (m, 2H); .sup.13C NMR (100 MHz, CDCl.sub.3): 155.37, 75.75, 26.64, 19.04.
(84) 2) Compound 1-2:
(85) ##STR00034##
(86) Conversion rate 99%, Amount 1.14 g (90% Yield), mixture of diastereomers [see Angew. Chem., Int. Ed. 2014, 53, 10416.]; .sup.1H NMR (400 MHz, CDCl.sub.3): 5.76-5.66 (m, 2H), 5.05-4.96 (m, 4H), 4.78-4.60 (m, 4H), 2.34-2.09 (m, 5H), 2.03-1.94 (m, 1H), 1.82-1.51 (m, 5H), 1.38-1.27 (m, 2H), 1.21-1.11 (m, 1H); .sup.13C NMR (100 MHz, CDCl.sub.3): 155.19, 155.16, 140.95, 114.26, 113.96, 76.02, 75.66, 75.65, 75.15, 36.34, 33.89, 33.55, 31.67, 26.68, 25.79, 25.70, 25.06.
(87) 3) Compound 1-3:
(88) ##STR00035##
(89) Conversion rate 99%, Amount 0.94 g (77% Yield), mixture of diastereomers [see Angew. Chem., Int. Ed. 2014, 53, 10416.]; .sup.1H NMR (400 MHz, CDCl.sub.3): 4.76-4.73 (quint, 1H), 4.69-4.66 (quint, 1H), 4.65-4.58 (m, 2H), 3.53-3.51 (m, 18H), 2.30-2.04 (m, 4H), 1.80-1.76 (m, 1H), 1.70-1.47 (m, 4H), 1.41-1.07 (m, 8H), 0.97-0.87 (m, 1H), 0.63-0.58 (m, 4H); .sup.13C NMR (100 MHz, CDCl.sub.3): 155.31, 155.27, 76.45, 76.08, 76.07, 75.59, 50.64, 35.30, 33.97, 32.41, 32.10, 29.12, 28.84, 26.88, 26.03, 25.64, 25.05, 6.37, 6.25.
(90) 4) Compound 1-4:
(91) ##STR00036##
(92) Conversion rate 99%, Amount 1.42 g (94% Yield); .sup.1H NMR (400 MHz, CDCl.sub.3): 7.41-7.39 (dd, 1H), 7.36-7.28 (m, 2H), 7.21-7.19 (dd, 1H), 5.70-5.68 (d, 1H), 5.20-5.16 (quint, 1H), 3.00-2.92 (m, 1H), 2.72-2.66 (dt, 1H), 2.33-2.26 (m, 1H), 2.02-1.94 (m, 1H); .sup.13C NMR (100 MHz, CDCl.sub.3): 154.85, 138.30, 130.96, 129.93, 129.53, 128.84, 127.48, 75.78, 75.53, 27.27, 23.87.
(93) 5) Compound 1-5:
(94) ##STR00037##
(95) Conversion rate 99%, Amount 1.86 g (>99% Yield), mixture of diastereomers [see Angew. Chem., Int. Ed. 2014, 53, 10416.]; .sup.1H NMR (400 MHz, CDCl.sub.3): 4.92-4.69 (m, 2H), 4.63-4.16 (m, 3H), 2.44-2.35 (m, 1H), 2.21-1.86 (m, 2H), 1.82-1.69 (m, 2H), 1.67-1.24 (m, 2H); .sup.13C NMR (100 MHz, CDCl.sub.3): 154.75, 154.73, 154.67, 154.62, 154.58, 79.35, 79.14, 79.04, 79.02, 75.40, 75.23, 75.14, 75.04, 74.70, 74.64, 74.62, 67.61, 67.54, 67.37, 36.49, 36.36, 33.24, 33.09, 28.78, 28.45, 27.60, 26.39, 25.72, 25.10, 24.96, 21.00, 20.44, 19.64, 19.18.
(96) 6) Compound 1-6:
(97) ##STR00038##
(98) Conversion rate 99%, Amount 1.68 g (>99% Yield), mixture of diastereomers; .sup.1H NMR (400 MHz, CDCl.sub.3): 4.91-4.81 (m, 2H), 4.76-4.66 (m, 6H), 4.08-3.91 (m, 4H), 2.75-2.68 (m, 1H), 2.43-2.23 (m, 6H), 2.16-1.95 (m, 7H), 1.91-1.71 (m, 7H), 1.71-1.57 (4H), 1.49-1.07 (m, 3H); .sup.13C NMR (100 MHz, CDCl.sub.3): 174.02, 173.98, 173.21, 173.19, 154.93, 154.90, 154.77, 154.74, 154.72, 75.60, 75.55, 75.52, 75.19, 75.13, 74.99, 74.95, 74.75, 74.62, 68.20, 68.17, 68.06, 37.43, 37.41, 37.34, 37.24, 35.62, 32.17, 30.57, 30.51, 30.47, 29.43, 29.35, 29.32, 29.27, 29.25, 28.77, 28.74, 28.00, 26.17, 26.13, 25.42, 25.37, 25.34, 25.20, 25.17, 25.16, 25.12, 25.09, 22.37, 21.92, 21.87, 21.85, 21.44, 21.40; HRMS (ESI) m/z calculated for C.sub.16H.sub.20O.sub.8 [M+Na.sup.+]: 363.1056, found: 363.1075.
(99) 7) Compound 1-7:
(100) ##STR00039##
(101) Conversion rate 99%, Amount 1.36 g (95% Yield); .sup.1H NMR (400 MHz, CDCl.sub.3): 5.07-5.06 (m, 2H), 2.11-2.04 (m, 2H), 1.81-1.58 (m, 4H); .sup.13C NMR (100 MHz, CDCl.sup.3): 155.51, 81.92, 33.08, 21.53.
(102) 8) Compound 1-8:
(103) ##STR00040##
(104) Conversion rate 99%, Amount 1.40 g (94% Yield); .sup.1H NMR (400 MHz, CDCl.sub.3): 7.52-7.50 (dt, 1H), 7.44-7.40 (td, 1H), 7.37-7.31 (m, 2H), 6.01-5.99 (d, 1H), 5.46-5.42 (m, 1H), 3.40-3.39 (m, 1H); .sup.13C NMR (100 MHz, CDCl.sub.3): 154.84, 140.18, 136.58, 131.20, 128.37, 126.63, 125.74, 83.71, 79.89, 38.16.
(105) 9) Compound 1-9:
(106) ##STR00041##
(107) Conversion rate 99%, Amount 1.65 g (98% Yield); .sup.1H NMR (400 MHz, CDCl.sub.3): 5.20-5.19 (m, 2H), 4.24-4.21 (dd, 2H), 3.57-3.53 (m, 2H); .sup.13C NMR (100 MHz, CDCl.sub.3): 154.53, 80.18, 73.07.
(108) 10) Compound 1-10:
(109) ##STR00042##
(110) Conversion rate 99%, Amount 0.98 g (84% Yield). 0.9 ml of substrate was used. .sup.1H NMR (400 MHz, CDCl.sub.3): 4.84-4.78 (m, 2H), 1.99-1.86 (m, 4H), 7.84-1.74 (m 2H), 1.66-1.57 (m, 1H), 1.52-1.42 (m, 1H), 1.35-1.25 (m, 2H); .sup.13C NMR (100 MHz, CDCl.sub.3): 154.74, 79.91, 30.23, 30.00, 23.58.
(111) The metal complex according to the present invention is a metal complex having a novel structure and consisting of a ligand having three phenolate donors bonded to a trisubstituted carbon and a salicylidene moiety, and a trivalent metal in Group 8 or Group 13, which has a pre-organized bite angle ideal to accommodate a 6-coordinate metal center, such that an enhanced rigidity effect of a ligand skeleton itself of the present invention is exhibited.
(112) Therefore, the method for preparing cyclic carbonate from the reaction of alkylene oxide and carbon dioxide using the metal complex according to the present invention may increase selectivity by the pre-organized rigid metal complex so as to have the cis-binding site available for reducing the activation barrier of the reaction, thereby highly selectively preparing the cyclic carbonate with 90% or more of complete conversion rate to alkylene oxide.
(113) Further, the cyclic carbonate according to the present invention may be used as a solvent or an additive constituting an electrolyte in a lithium secondary battery to exhibit more stable and excellent electrolyte performance.