Q 2D { G & B1 Bc B Bh Br B; B1 Õ o { . æ B1 4? B. BK BN !c A G 2D … · 2015. 2. 2. · BK BN !c...
Transcript of Q 2D { G & B1 Bc B Bh Br B; B1 Õ o { . æ B1 4? B. BK BN !c A G 2D … · 2015. 2. 2. · BK BN !c...
-
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
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(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
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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
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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