Transformation of Carbon Dioxide
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Transcript of Transformation of Carbon Dioxide
Trend in CO2 emissions from fossil fuel combustion Global change in CO2 emissions (2004-2005)
Top-10 emitting countries in 2005 World CO2 emissions by sector
CO2 EMISSIONS FROM FUEL COMBUSTION (2007 Edition)
Typical Transformations of Carbon Dioxide
一般意义上来说,可以将 CO2 看成是碳酸酐,可以很好的与碱性物质发生反应,比如, CO2 与格式试剂在低温下就可以发生反应,同样也可以与水、醇盐、氨基等发生加成反应,生成相应的羧酸根。
CO2
O
O
A
B+
-O
AO
B
A BNucleophiles(H2O, ROM, R2NH, RMgX,....)
LnM
OY
X
O
LnM
OY
X
O
X Y
alkene, alkyne,diene,allene, O2.....
Ir, Rh, Ni,Nb, Rh, Fe, Pd, Mo,等金属都可以与CO2络合。
JACS. 1977, 99, 2391.JACS.1983, 105, 5914.
Chem. Ber. 1977, 110, 2213.
Organometal l i cs, 1994, 13, 407- 409
Chem. Commun. 1981, 1145.
JACS, 1985, 107, 2985JACS. 1984, 106, 2732-2733JACS. 1986, 108, 2286.Organometallics 1990,9, 1337
Inorg. Chem. 1992,31,4481.
O
Cu
CO
CH3
LL=
N NAr Ar
Ar=2,6-(i-Pr)2C6H3
Organometallics, 2004, 23, 1191-1193
CO2 与金属形成络合物
Rh
P(tBu)2
P(tBu)2
H
Cl
KH / H2Rh
P(tBu)2
P(tBu)2
H
H
CO2 Rh
P(tBu)2
P(tBu)2
H
OCOH
Organometallics 1996, 15, 1839-1844Organometallics 1988, 7, 13-15
N
iPr2P PiPr2IrH
H
H
JACS, 2009, 131, 14168-14169
氢化
CO2 + H2 + HN(CH3)2
RuCl2[P(CH3)3]4
scCO2N O + H2O
JACS, 1994, 116, 8851-8852JACS, 1996, 118, 344-355
超临界 CO2 应用
CO2 形成五元金属杂环
R + CO2Ni(cod)2(1 equiv)
DBU(2 equiv),0oC
H+
COOHR
+ CO2Ni(cod)2(1 equiv)
DBU(2 equiv),0oC Ni OO
DBUDBU
D+
COOH
D (95% D)
RNi(cod)2
2 DBUR
NiDBU DBU
CO2
irreversible
R
Ni OO
DBUDBU
+
ONi
O
R DBU
DBUCOOH
R
kinetically favored
JOC, 1999, 64, 3975-3978
CO2, Ni(0)
ligand
Ni
O
O
R-M RCOOM
PhCO2, Ni(cod)2
DBU, THF, 0oC Ni OO
NiPh
PhO
O
Ph
Ph
COOH
COOH
+
hydrolysis Me2Zn
Ph
CO2Me
CO2Me
ArZn
CO2Me
Ph
Ph+
Ph
Ph
CO2Me
OOZnR
Ni
ROO
Ni
R2Zn
RZnOOC R
R=Me
MeOOC COOMe
R=Ph
JACS, 2001, 123, 2895-2896
OL, 2005, 7, 195-197
CO2 形成五元金属杂环
OL, 2003, 15, 2599-2601
R
R'
TiOiPr
OiPr
CO2
TiO
O
OiPrOiPr
R
R'
1,E+
2,H+
COOHR
R' E
EJOC, 2003, 1157-1171
CO2 形成 6 元金属杂环
R1 R1 + CO2
Ni(0)
Tertiary phosphine O
O
R1
R1
R1
R1
R1 R1
Ni(0)Ni
R1
R1
R1R1
Ni
O
O
R1 R1
R1
R1CO2
O
NiO R1
R1 R1
R1
O
O
R1
R1
R1
R1
BCSJ, 1980, 53, 3329-3333Macromolecules, 1993, 26, 4840-4844Macromolecules, 1995, 28, 1312-1315Macromolecules, 1995, 28, 1356-1359Macromolecules, 1994, 27, 1289-1290
R
R
(0)Ni
CO
OO
Ni
O
R
R
R R
ONi
R
R
R
RO
O
R
R
R
R
O
PhOO
+ CO2(1 atm)
cat(5 mol%)
NMP,100oC PhOOO
O
1 2
PhOO
+ M+PhO
OM+
X- OM
XPhO
CO2 O
XPhO
OM
O
PhOOO
O
CO2 + M+X- OX
O-
PhOO
PhO
OM
O
OX
PhOOO
O
JOC, 1993, 58, 6198-6202
与环氧形成五元环
Yield up to 100%
JACS, 2001, 123, 11498-11499
Al , Cr, Co, Zn, Sn, Ni, Ru, Cu, Mn, 等金属都可以催化该反应,离子液体,四级铵盐等也可以很好的催化该反应。
J. Mol. Catal. A: Chem. 2004, 210, 31.J. Mol. Catal. A: Chem. 2002, 186, 1.Organometallics 2004, 23, 924.J. Org. Chem. 2003, 68, 1559.J. Am. Chem. Soc. 2004, 126, 3732.Inorg. Chem. 2004, 43, 4315.BCSJ.1996, 69, 2885.New J. Chem. 2001, 25, 639.Chem. Commun.2003, 896.Tetrahedron Lett. 2004,45, 8307.J. Org. Chem. 2005, 70, 7882.Green Chem. 2004, 6, 613.Org. Lett. 2002, 4,2561.Org. Lett. 2002, 4,2561.Chem. Commun. 2003, 2042.Chem. Eur. J. 2006, 12, 1004.J. Mol. Catal. A: Chem.2005, 226, 199.Organometallics,, 2004, 23, 6025.
与环氧形成五元环
O
+ CO2
catalystO O
* *
O
X
orO
CO2+catalyst
OO
* *
O
X
CHO PCHCPO PPC
Coates, ACIE, 2004, 43, 6618-6639Darensbourg, Coord. Chem.Rev, 1996, 153, 155-174
CO2与环氧合成高聚物的反应中,五元碳酸酯是最常见的副产物。五元碳酸酯相对于高聚物来说,是热力学产物,可以通过以下几个途径提高高聚物的生成的比例:1,催化剂2,温度(温度越低,越有利高聚物的生成)3,CO2的压力4,环氧的浓度5,抑制解聚6,催化剂中有多个结合位点(双金属有利形成高聚物)一般来说,五元碳酸酯都是由金属醇盐进攻邻位的碳酸盐形成的。
与环氧形成高聚物
Zn, Cr, Al, Co, La, Mn, 等金属可以催化 CO2 形成高聚物。
Macromolecules 1995, 28, 7577.JACS. 2000, 122, 12487.JACS. 2005, 127, 3031.Macromolecules 2005, 38, 6251.ACIE. 2003, 42, 5484.JACS. 2005, 127,10869.ACIE. 2004, 43, 3574.JACS. 2006, 128, 1664.JACS. 2005,127, 14026.JACS. 2002, 124,6335.Macromolecules 2005, 38,4089.J. Polym. Sci., Part A: Polym.Chem. 2003, 41, 3549.
与环氧形成高聚物
CO2 和 N- 杂环丙烷的反应
HN
+ CO2
Bu4NX or M+X-
solventO NH
O
Bu4NX = Bu4NBr yield =95% M+X- = LiBr Yield= 74%
HN
+ CS2
THF, rt, 24hS NH
STBAB
yield = 94%
Tetrahedron letters, 2003, 44, 7889-7891
N
R+ CO2
solventO N
O
R
Ts
TsLiBr
Tetrahedron letters, 2004, 45, 1363-1365Org. Lett., 2004 .6,. 2301-2304
2R1R2NH + CO2
Ionic liquid
base,170oC R2R1N NR1R2
O
+ H2O
Angew. Chem. Int. Ed. 2003, 42, 3257 – 3260
利用 CO2 合成尿素及异氰酸酯
RNH2 + CO2 + R'OH
Bu2SnO
Me2C(OR')2
200oC RHN OR'
O
Chem. Commun., 2001, 2238–2239
L
HN OMe
O
HN OMe
O
Yield=83% yield =49
利用 CO2 合成氨基甲酸酯
Green chem, 2004, 6, 524-525
NH2
NH2
+ CO2MeOH, 150oC
6hHN
NH
O
+ H2O
Green Chem, 2003, 5, 340-342
R NH2 +R1
OHR2 +
CuClCO2
NO
RO
R2R1
Ionic liquids
R1
OHR2 +
CuClCO2
OO
O
R2R1
Ionic liquids
JOC, 2004, 67, 16-21JOC, 2004, 69, 391-394JOC, 2005, 70, 7376-7380
R1
NHR3R2 + CO2
Pd(OAc)2
toluene, 50oCO
N
O
R2R1
R3
CO2 合成五元杂环
BO
O
+ CO2
[Rh(OH)(cod)]2 dppe, CsF
dioxane,60oCCOOH
LnRh Ar
LnRh(I)
ArB(OR)2
CO2insertion
ArLnRhO
O
ArO
OLnRh
ArB(OR)2
Ar(RO)2BO
O
JACS, 2006, 128, 8706-8707
R'R3Sn CO2
Pd(Ph3)4+
THF,70oCR'
O
O
R3Sn
major
R'O
O
R3Sn+
minor
PdSnR3
Pd SnR3
CO2O
O
Pd SnR3
SnR3
Pd(PPh3)4
Pd
O
O
R3Sn
JACS, 1997, 119, 5057-5058
利用 CO2 合成有机羧酸
CO2 芳基化
ONaCO2(加压)
OH
COONaH+
OH
COOH
ONa
CO2
络合
O-Na+
O
O
O
COONaH
OH
COONaH+OH
COOH
Kolbe-schmitt反应
JACS, 2002, 124, 11379-11391
CL, 2003, 43, 454-455
Yield= 20-34%
CL, 2002, 102-103
TMS
OTf+ +R'2NH CO2
KF(2 equiv)18-crown-6(2 equiv)
THF, 0oC
NR'2
COOH
R'2NH
CO2
R'2N
H
OC
O
-+
COO-
R'2N
H+
NR'2
COOH
OL, 2008, 10, 3485-3487
CO2 合成六元环
Bu3Sn
R
R
Cl+ + CO2
10% PdCl2(PhCN)2 20% PBu3
70oC, 48h
R
O
O
R
+ Bu3SnCl
Organometallics, 2000, 19, 1458-1460
基于 CO2 的串联反应
RCOOH + R1NH2 + R2CHO + R3NC R
O
R1
R2 HN
O
R3
R1NH2 + R2CHO R2 NR1
RCOOH
R3NC
N+R2 R1
H
C-
N+
R3
O-O
R
R O
O NHN
R2
R1
R3
O
NR
-O
R1
R2
NR3 H+
R N
O
R1
R2 HN
O
R3
R2NH2
R3CHOR3 N
R2
R1OH + CO2
O O-
O
R1
R4NC
N+R3 R2
H
C-
N+
R4
O-O
OR1
O O
O NHN
R3
R2
R4
R1
O N
O
R2
R3 HN
O
R4R1
R2NH2 R3CHOR1OH+CO2 ++ + R4NC O N
O
R2
R3 HN
O
R4R1
JOC, 1998, 63, 867-871
Ugi 反应
转化图
H2
HCOOHDMF
H2
O
RO
O
O
R
OR
*
R
O O
O
*n
R2R1N NR1R2
O
NH
O
O
R'ArRHN OR'
O
NH2
CN
NH
NH
O
O
NR'R
NO
R O
R'
NO
R O
R1
RCOOH
R
COOHR
R1
X R2 X
R1
O
O
O
O R2
n
NR'2
COOH
TMSTfO
Bu3Sn
RR
Cl
R
O
O
R
CO2