1

2

O

+

CO2

O O

OCH3OH

HOOH

H3CO OCH3

O

OH

O O

OCH3

CH3OHHO

CH3

CH3CO

O

nDMC)

DPC)A

CO2

, , 2009, 51 (5), 336 341.

OO

O

R

CD,DVD)

R’COOH

S

R

R' OO

OHR

O

O

OR' R'

R’OHR’NCO

N OO

R'

RO O

OR'

n

HOR’OH

R’NH2

R’NH 2

NH

NH

OR' R'

NH

R' O

OOH

R

3

Cl Cl

O

+HO

OHO

O

O

+ CO2catalyst

R O

OO

O

R4

Sakai, T.; Tsutsumi, Y.; Ema, T. GreenChem. 2008, 10, 337.

+ CO2catalyst

R O

OO

O

R

SiO O O

P+

Br-

5

6

MX M = Na, Li, K

X = Cl, Br, I, OCOCH3,CN, OTs, 1993, Endo.

MgO1997, Yano.

MgO

AlO

Mg

-

1999, Kaneda.

[ZnBr2(py)2]2000, Kim.

N

N N

NCr

X

X = Cl or O

1995, Kruper.

tBu O

tBu

N N

O tBu

tBu

Cr

Cl

R1 R2

2001, Nguyen.

tBu O

tBu

N N

O tBu

tBu

Cr

X

Nn

N

N

a; n = 6, X = Clb; n = 6, X = BF4c; n = 1, X = Cl

2008, Zhang.

Ni(PPh3)2Cl2/PPh3/Zn2003, Li.

Re(CO)5Br2005, Jiang.

[( 5-C5H5)Ru(CO)( -dppm)Mn(CO)4][( 5-C5Me5)Ru( -dppm)( -CO)2Mn(CO)3]

2006, Man.

R3

O

R1N

N O

R3

R1

Al

R2

R2

X

R3

O

R1N

NO

R3

R1

Al

R2

R2

XO

2007, North.

n-Bu4N+X-(X = Br or I)2002, Caló

Rf3RP+I -(Rf = C4F9C2H4,

C6F13C2H4, C8F17C2H4;R = Me, Rf)

2003, Sakakura.

NPh3P PPh3 XX- = Cl-, Mn(CO)5-,Mn(CO)4(PPh3)-

2005, Lau.

N NMen-Bu

BF4

(BMImBF4)

2001, Deng.

N NMe CnH2n+1

X = BF4CF3SO3, PF6, NO3

X

[Cn-mim][X]

2003, Ikushima.

N

NH

Me

RH

HCl

Cl

InCl3

InCl3

ClCl3In

2005, Varma.

NNMe OH Br

2008, Zhang.

ZnCl2/[BMIm]Br (1:6)

2004, Xia.

N NN

NReCO

OH2COCO

(CF3SO3-)2

N

Br

2007, Wong.

N

N

N

OH

O SiO

OO MCM-41silica

MCM-41-TBD

CH23

2003, Sartori.

SiO2 (CH2)3 N N nBu

Br

ZnCl22006, Xia.

SiO2-C3H6-P+(n-Bu)3I -2006, Sakakura.

PEG6000(N+Bu3Br-)22006, He.

PEG6000(P + Bu3Br -)22007, He.

N N

NBu

N N

NPEG6000Bu

Br Br

2007, He.

N

N

**

*

**

Cl

2007, Han.

N N

H H

nX X

2007, Han.p-Methoxyphenol/DMAP (1 : 1)

2003, Shi.

N N

OH HO

2004, Shi.

ion exchange resin(D201)2005, He

naturally -amino acid2007, Jiang.

N N RR

O O

2008, Lu.

+ CO2R O

OO

O

R

Si(CH2)3P+

OOO

R1

R2

R3Br –

+ CO2R O

OO

O

R

7

(EtO)3Si Br + Ph3PCH3CN

(EtO)3Si P+Ph

PhPh

Br-

OH OH OH

O

O

O

Si P+Ph

PhPh

Br-

DMF8

Synthesis of Carbonate by PPh3 Immobilized Catalysts

O

n-Bu

O O

n-Bu

O

CO290 oC, 1.0 MPa, 6h

+

Catalyst 1~5(1.0 mol%)

1,2-Epoxyhexane

P PhPh P PhPhPh Br Bn Cl

OO

OSi P

Ph

PhPhBr

2a : Toyonite

3a : Silica gel 4 5S

uppo

rt

EtOEtO

EtOSi P

Ph

PhPhBr

1

a : Halogen content of polymer : 1.0 mol%.b : Reaction time : 7h.

+

8a 9a

CO2catalyst (1 mol%)

1 MPa, 90 ºC, 6 h n-Bu O

OO

O

n-Bu

Si(CH2)3P+

OOO

PhPh

PhBr –

1: silica A(pore size : 19 nm)2: silica B(pore size : 6 nm)

3: Toyonite4: alumina

organic–inorganic hybrid catalyst

(%).(1.0

mol%).(0.5

mol%)1 1a Silica A 99 902 2a Silica B >99 643 3a Toyonite 904 4a Alumina 525b PPh4Br 16b (EtO)3(CH2)3SiPPh3Br 38 10

O O O

Si

PR3

R1

R2n-Bu

O

Br

OH

(H2C)3

CO2

O O O

Si

PR3

R1

R2

Br

O

n-Bu

OH

(H2C)3

O O O

Si

PR3

R1

R2 O

O

O

n-Bu

Br

O

H

(H2C)3

O O O

Si

PR3

R1

R2 OO

O

n-Bu

Br

OH

(H2C)3

CO2

CO2

11

(Toyonite)

••• 155 15 m• 60 nm••

••

SEM of Toyonite

AlO

SiO

AlO

SiO Al

O SiO Al

AlOSiOAl O

Si OAl O

SiO

AlO

SiO

AlO

O OSi

O

OO

OO O O O

OO

O

O

O

O

OO Si Si

O

HH H H H HH

H

HH H

12

13

+

8a 9a

CO2catalyst (1 mol%)

1 MPa, 90 ºC, 6 h n-Bu O

OO

O

n-Bu

Si(CH2)3P+

OOO

R1

R2

R3Br –

1: silica A(pore size : 19 nm)3: Toyonite

a: R1 = R2 = R3 = Phb: R1 = R2 = R3 = p-Me-C6H4c: R1 = R2 = R3 = p-F-C6H4d: R1 = R2 = Ph, R3 = n-Bu

organic–inorganic hybrid catalyst

A R1R2R3 (%) Toyonite (%)a

1 1a Ph3 99 5 3a 902 1b (p-Me-C6H4)3 >99 6 3b 443 1c (p-F-C6H4)3 96 7 3c 704 1d n-Bu, Ph2 99 8 3d 55

(10.0 mmol), (1 mol%, 550 mg, 1 g 0.20 mmol), 1 MPa CO2 (1 MPa = 10 , 90 oC, 50 mL

, 6 14

O

n-Bu+ CO2

90oC, 1.0 MPaO O

n-Bu

OOO

OSi P

Ph

PhPhBr

Sup

port

(1.0 mol%)

Silica gel (1%)

(%): Amountof catalyst

Silica gel (0.5%)

Toyonite (1%)

Toyonite (0.5%)

: 8 (10.0 mmol), (1a) (1 mol%, 550 mg, 0.2 mmol / 1 g), 1 MPa CO2, 50 mL . a .

(R) (h) (%)a

1 n-Bu (8a) 6 992 Me (8b) 6 993 CH2OCH3 (8c) 12 884 Ph (8d) 6 865 CH2Cl (8e) 20 856 -(CH2)4- (8f) 24 21

O

R+ CO2

1 MPa, 90 oC

O

OR

O

R = n-Bu, Me, Ph, CH2OCH3, CH2Cl, (CH2)4

Si(CH2)3P+

O

O

O

Ph

Ph

Ph

Br –

1.0 mol%, 1a

8 9

16

(10.0 mmol), (1 mol%, 550 mg, 1 g

0.20 mmol), 1 MPa CO2 (1MPa = 10 , 90 oC, 50 mL

, 6

17

O

n-Bu+ CO2

1 MPa, 90 oC, 7h

O

On-Bu

OSi(CH2)3P+

O

O

O

Ph

Ph

Ph

Br –

1.0 mol%, 1a

8a 9a

18

Sakai, T.; Tsutsumi, Y.; Ema, T. Green Chem. 2008, 10, 337-341.(P2008 296022A9)

O

R+ CO2

1 MPa, 90 oC, 6~20 h

O

OR

O

R = n-Bu, Me, Ph, CH2OCH3, CH2Cl

Si(CH2)3P+

O

O

O

Ph

Ph

Ph

Br –

1.0 mol%, 1a

85 ~ 99%

19

SiO O O

O

RCO2

R

OO

O

20

22