1
C 2 C 3 + 3 C C 3 DMC) C 3 C 3 C n C 2 C 3 DPC) C 3 A,, 2009, 51 (5), 336 341. 2
CD,DVD) C S ' ' ' C ' ' n 2 2 ' ' ' 3
Cl Cl + + C 2 catalyst 4
+ C 2 catalyst Sakai, T.; Tsutsumi, Y.; Ema, T. Green Chem. 2008, 10, 337. P + - 5
MX M = a, Li, K X = Cl,, I, CC 3, C, Ts, 1993, Endo. X Mg 1997, Yano. - Mg Al Mg 1999, Kaneda. [Zn 2 (py) 2 ] 2000, Kim. Al 3 3 2 1 1 2 2 1 1 2 X Cr X = Cl or 1995, Kruper. t Bu t Bu 2008, Zhang. t Bu 1 2 Cr Cl t Bu 2001, guyen. i(p 3 ) 2 Cl 2 /P 3 /Zn 2003, Li. t Bu e(c) 5 2005, Jiang. [( 5 -C 5 5 )u(c)( -dppm)mn(c) 4 ] [( 5 -C 5 Me 5 )u( -dppm)( -C) 2 Mn(C) 3 ] 2006, Man. 3 3 Al 2007, orth. p-methoxyphenol/dmap (1 : 1) 2003, Shi. ion exchange resin (D201) 2005, e naturally -amino acid 2007, Jiang. X 2004, Shi. Cr X t Bu a; n = 6, X = Cl b; n = 6, X = BF 4 c; n = 1, X = Cl n t Bu t Bu 2008, Lu. 4 + X - (X = or I) 2002, Caló Me BF 4 (BMImBF 4 ) 2001, Deng. X Me C n 2n+1 X = BF 4 CF 3 S 3, PF 6, 3 [C n -mim][x] 2003, Ikushima. C 2 3 MCM-41-TBD 2003, Sartori. f 3 P + I - (f = C 4 F 9 C 2 4, C 6 F 13 C 2 4, C 8 F 17 C 2 4 ; = Me, f) 2003, Sakakura. Cl 3 In Cl MCM-41 silica 2 (C 2 ) 3 nbu ZnCl 2 2006, Xia. 2 -C 3 6 -P + () 3 I - 2006, Sakakura. Me Cl Cl 2005, Varma. InCl 3 InCl 3 Me * * Bu 2008, Zhang. * 2007, e. PEG 6000 * Cl 2007, an. * Bu 3 P P 3 X X - = C l-, Mn(C) 5 -, Mn(C) 4 (P 3 ) - 2005, Lau. ZnCl 2 /[BMIm] (1:6) 2004, Xia. (CF 3 S 3 - ) 2 2007, Wong. PEG 6000 ( + Bu 3 -) 2 2006, e. X 2007, an. X PEG 6000 (P + Bu 3 - ) 2 2007, e. C C e C 2 n 6
+ C 2 + C 2 (C 2 ) 3 P + 1 2 3 7
(Et) 3 + 3 P C 3 C (Et) 3 P + - P + - DMF 8
Synthesis of Carbonate by P 3 Immobilized Catalysts Et Et Et + 1,2-Epoxyhexane 1 P Support C 2 Catalyst 1~5 (1.0 mol%) 90 o C, 1.0 MPa, 6h 2a : Toyonite P Bn Cl P P 3a : lica gel 4 5 a : alogen content of polymer : 1.0 mol%. b : eaction time : 7h.
8a + (C 2 ) 3 P + C 2 catalyst (1 mol%) 1 MPa, 90 ºC, 6 h organic inorganic hybrid catalyst 1: silica A (pore size : 19 nm) 2: silica B (pore size : 6 nm) 9a 3: Toyonite 4: alumina (%).(1.0 mol%).(0.5 mol%) 1 1a lica A 99 90 2 2a lica B >99 64 3 3a Toyonite 90 4 4a Alumina 52 5 b P 4 1 6 b (Et) 3 (C 2 ) 3 P 3 38 10
( 2 C) 3 P 1 2 3 ( 2 C) 3 P 1 2 3 C 2 C 2 ( 2 C) 3 P 1 2 3 C 2 ( 2 C) 3 P 1 2 3 11
(Toyonite) 155 15 m 60 nm Al Al Al Al Al Al Al Al Al SEM of Toyonite 12
13
8a (C 2 ) 3 P + + C 2 1 2 3 organic inorganic hybrid catalyst catalyst (1 mol%) 1 MPa, 90 ºC, 6 h 1: silica A (pore size : 19 nm) 3: Toyonite 9a a: 1 = 2 = 3 = b: 1 = 2 = 3 = p-me-c 6 4 c: 1 = 2 = 3 = p-f-c 6 4 d: 1 = 2 =, 3 = A 1 2 3 (%) Toyonite (%) a 1 1a 3 99 5 3a 90 2 1b (p-me-c 6 4 ) 3 >99 6 3b 44 3 1c (p-f-c 6 4 ) 3 96 7 3c 70 4 1d, 2 99 8 3d 55 (10.0 mmol), (1 mol%, 550 mg, 1 g 0.20 mmol), 1 MPa C 2 (1 MPa = 10, 90 o C, 50 ml, 6 14
Support (1.0 mol%) P + C 2 90 o C, 1.0 MPa lica gel (1%) lica gel (0.5%) Toyonite (1%) Toyonite (0.5%) (%): Amount of catalyst
(C 2 ) 3 P + 1.0 mol%, 1a + C 2 1 MPa, 90 o C 8 =, Me,, C 2 C 3, C 2 Cl, (C 2 ) 4 9 () (h) (%) a 1 (8a) 6 99 2 Me (8b) 6 99 3 C 2 C 3 (8c) 12 88 4 (8d) 6 86 5 C 2 Cl (8e) 20 85 6 -(C 2 ) 4 - (8f) 24 21 : 8 (10.0 mmol), (1a) (1 mol%, 550 mg, 1 MPa C 2, 50 ml. a. 0.2 mmol / 1 g), 16
(10.0 mmol), (1 mol%, 550 mg, 1 g 0.20 mmol), 1 MPa C 2 (1 MPa = 10, 90 o C, 50 ml, 6 17
8a (C 2 ) 3 P + + C 2 1.0 mol%, 1a 1 MPa, 90 o C, 7h 9a 18
(C 2 ) 3 P + + C 2 1.0 mol%, 1a 1 MPa, 90 o C, 6~20 h =, Me,, C 2 C 3, C 2 Cl 85 ~ 99% Sakai, T.; Tsutsumi, Y.; Ema, T. Green Chem. 2008, 10, 337-341. (P2008 296022A9) 19
C 2 20
22