Ca(OH)2＋CO2===CaCO3↓＋H2O 2Na＋2H2O===H2＋2NaOH 2NaOH＋CO2===Na2CO3＋H2O CaCO3＋2HCl===CaCl2＋H2O＋CO2↑ Na2CO3＋2HCl(过量)===2NaCl＋H2O＋CO2↑
△
H2CO3
H2O＋CO2↑
Na2CO3＋HCl(少量)===NaCl＋NaHCO3
高温
CaCO3
CaO＋CO2↑
CaCO3＋H2SO4===CaSO4＋H2O＋CO2 4Al＋3O2===2Al2O3 Fe＋H2SO4===FeSO4＋H2↑ Zn＋H2SO4===ZnSO4＋H2↑ Mg＋2HCl===MgCl2＋H2↑ Fe＋CuSO4===Cu＋FeSO4 2Al＋3CuSO4===Al3(SO4)3+3Cu Cu＋2AgNO3=Cu(NO3)2＋2Ag
△
2Cu＋O2
2CuO
2Zn＋O2===2ZnO
第 1 页,共 14页
2F2＋2H2O===4HF＋O2 F2＋2NaCl===2NaF＋Cl2 F2＋2NaBr===2NaF＋Br2 F2＋2NaI===2NaF＋I2
点燃
H2＋Cl2
2HCl
Mg＋2H 2O===Mg(OH) 2＋H 2↑ Mg＋Br2===MgBr2
熔融
Mg＋TiCl4
Ti＋2MgCl2
BaCl2＋Na2SO4=BaSO4↓＋2NaCl CaCl2＋Na2CO3=CaCO3＋2NaCl
高温
2CuO＋C
△
2Cu＋CO2↑
2Na＋O2
Na2O2
4Na＋O2=2Na2O 2Na2O2＋2H2O=4NaOH＋O2↑ 2Na2O2＋2CO2=2Na2CO3＋O2 3Fe＋4H2O(g)=Fe3O4＋4H2↑ 2Al＋2Na(OH)2H2O=2NaAlO2＋3H2↑ CaO＋H2O===C a ( O H )2 F e 2 O 3 ＋ 6 H C l = 2F eC l 3 ＋ 3 H 2 O
第 2 页,共 14页
Al2O3＋6HCl===2AlCl3＋3H2O Al2O3＋2NaOH=2NaAlO2＋H2O 2Al(OH)3===Al2O3＋3H2O 2Fe(OH)3===Fe2O3＋3H2O 2Cl2＋2Ca(OH)2===CaCl2＋Ca(ClO)2＋2H2O Cl2＋2NaOH===NaCl＋NaClO＋H2O
光照
2HClO
2HCl＋O2
Cl2＋H2O=HCl＋HClO HCl＋AgNO3=AgCl↓＋HNO3
放电
N2＋O2 2NO＋O2=2NO2
2NO
Si＋2NaOH＋H2O=Na2SiO3＋2H2 SO2＋CaO=CaSO3 SO2＋2NaOH=Na2SO3＋H2O Si＋2F2=SiF4 SO2＋2H2S=3S＋2H2O
第 3 页,共 14页
OMe
X X OMe X
Br
Br HO B OH X N F X B N F X
Br N B Br F F Br N
Br
Pd(0)
X
Non-fluorescent
Pd(OAc) 2,O2
R2
brightly-fluorescent
O
R1
+
NO 2
R1 AIBN,NaCO 3
R2 O
C-N Bond Cleavage for C-C Bond Formation
O O R N O O
O R
H
N N
O N R
2
NN H R-N H N N N-R
N HN N N R-N-H N
N
H
N N
H-N-R
N
O O
[L],R=Me,Bu
[L],R=Me,Bu
N H N N R [L],R=Me,Bu
第 4 页,共 14页
Me N N O Me O O H H N N Me R3
Me R3 Me O
Ba
Me N N ph
Me O
ph
Fig.26. Structure of the derivatives [Ba(Q)2(pmdien)(H2O)]
Me N N O Me O N N ph Me N N N Me R3
Me R3 Me O
Ba
Me N
Me O
ph
R3=nPe,tBu
I N
O O
1)Azole,Cs2CO3 Pd(OAc)2,PPh3,Cul 2)NaOMe,MeOH 8
O OMe
Z
9 Z=NMe,49% Z=S,65%
Scheme3.
F3C
O
n n
R
CF3
n
R
CF3 CF3
cat, CuCl
n
第 5 页,共 14页
NH2
path"a"
NH2
N:
NH H N N
N
H N H N H N
N
[O] -H2O
7a 6 [O] pbth"b" 2c
N
N
9a
10
NH H N N N
[O] -H2O
N N
H N
9a
N
Scheme1 a) (i) (ii)
H 2N OH OH H 2N H 2N O NH2
(iv) iii
O H OH NH2 NH2 OH
OH HO NH2
M OH NH2 NH2 NH 3+ -O -O
M ONH3 + NH3 +
MZ+ with z =1,2(except Be2+)
N Ph N O O O Me N Pe n N Ph Ph N N Me nPe N Ph O Sr O O O Sr nPe Me N N O Ph Ph N N O O nPe O O nPe Me N
MZ+ with>=3,Be2+
Me
Pe n
Me
Fig.21.Structure of the derivative (imH2)2[Sr2(Qnpe )6]
第 6 页,共 14页
O O
O O Ga O Ga
O O
Ga
O O O Ga O O O
O O O Ga O O O
Ga
O N
CH 3
O N
CH3 O O N
O N
CH3
N R
O
PhCNO
Ph N O
N R
+
Ph
N R
O
p substrate
rxn
p
1.remove solvent p product separation
pruduct 2.add heptane and CH3 CN
1.rem
ove solvent (2.regeneration) 3.add substrate solution p:polymer-supported phosphine catalyst/reagent
第 7 页,共 14页
CNOH
O
Au3+
OH
1
NH 2
a,b
H R1 c N NH2 O
2
H R1 d N NH2 H N R1 N H F NO2 O
e
R1 N F N NO 2
f
R1 N N
R2 NH NO2
g
R1 N N
R2 NH NH2
h
R1 N N N
R2 N O H
i
R1 N N N
R2 N O R3
j
R1 N N N
R2 N O R3
R2 O N OC Z R1 O
R2
O
catalyst 4-Mes-DHPB
N S
N N Z
R1
O
55~94% e.e. (Z=OR3,Me)
第 8 页,共 14页
O
OH
Vitamin B12
O
NHR
OH NHR N O N O
c-acid
R3
O HN
d-acid
R2 N R2 I
R2 R1
R3-NH-NH 2
I2
N
NaHCO3
R1
N
R1 R1= alkyl,aryl,heteroaryl,ferrocenyl
R2=H,methyl,phenyl R3=alkyl,aryl
R3 23examples 40-95%yields
O R R N+ R O H N +H H O O O O O R O O O O H N +H H 4ClO4- O O O O O O O
O O
O O
n
N+
n
H N+H H O O
n
O O O O
H+ N
R
R N+
n
O
4ClO4-
R
R
O O H N +H H O O
logk1 up to 9.39 D -A complex R=H ,R+R=CH=CH;n=0.1
logk2 up to 3.30 D-A-D complex
第 9 页,共 14页
3500 3000 2500 2000
F G B D
If
1500 1000 500 0 -500
200 300 400 500 600 700 800
λ /nm
第 10 页,共 14页
1200 1000 800 600 400 200 0 200 300 400 500 600 700
B D E
If
800
λ/nm
第 11 页,共 14页
E
500
400
DTG/uq/min
300
200
100
0
3000
4000
5000
6000
7000
8000
TG/uq
E
300 250
DTG/uq/min
200 150 100 50 0 -100 -80 -60 -40 -20 0
DTA/uV
第 12 页,共 14页
E
300
250
DTG/ug/min
200
150
100
50
0 0 20 40 60 80 100
t/min
第 13 页,共 14页
3500 3000 2500 2000
F G B D E
If
1500 1000 500 0 -500 200 300 400 500 600 700 800
λ /nm
第 14 页,共 14页
Ca(OH)2＋CO2===CaCO3↓＋H2O 2Na＋2H2O===H2＋2NaOH 2NaOH＋CO2===Na2CO3＋H2O CaCO3＋2HCl===CaCl2＋H2O＋CO2↑ Na2CO3＋2HCl(过量)===2NaCl＋H2O＋CO2↑
△
H2CO3
H2O＋CO2↑
Na2CO3＋HCl(少量)===NaCl＋NaHCO3
高温
CaCO3
CaO＋CO2↑
CaCO3＋H2SO4===CaSO4＋H2O＋CO2 4Al＋3O2===2Al2O3 Fe＋H2SO4===FeSO4＋H2↑ Zn＋H2SO4===ZnSO4＋H2↑ Mg＋2HCl===MgCl2＋H2↑ Fe＋CuSO4===Cu＋FeSO4 2Al＋3CuSO4===Al3(SO4)3+3Cu Cu＋2AgNO3=Cu(NO3)2＋2Ag
△
2Cu＋O2
2CuO
2Zn＋O2===2ZnO
第 1 页,共 14页
2F2＋2H2O===4HF＋O2 F2＋2NaCl===2NaF＋Cl2 F2＋2NaBr===2NaF＋Br2 F2＋2NaI===2NaF＋I2
点燃
H2＋Cl2
2HCl
Mg＋2H 2O===Mg(OH) 2＋H 2↑ Mg＋Br2===MgBr2
熔融
Mg＋TiCl4
Ti＋2MgCl2
BaCl2＋Na2SO4=BaSO4↓＋2NaCl CaCl2＋Na2CO3=CaCO3＋2NaCl
高温
2CuO＋C
△
2Cu＋CO2↑
2Na＋O2
Na2O2
4Na＋O2=2Na2O 2Na2O2＋2H2O=4NaOH＋O2↑ 2Na2O2＋2CO2=2Na2CO3＋O2 3Fe＋4H2O(g)=Fe3O4＋4H2↑ 2Al＋2Na(OH)2H2O=2NaAlO2＋3H2↑ CaO＋H2O===C a ( O H )2 F e 2 O 3 ＋ 6 H C l = 2F eC l 3 ＋ 3 H 2 O
第 2 页,共 14页
Al2O3＋6HCl===2AlCl3＋3H2O Al2O3＋2NaOH=2NaAlO2＋H2O 2Al(OH)3===Al2O3＋3H2O 2Fe(OH)3===Fe2O3＋3H2O 2Cl2＋2Ca(OH)2===CaCl2＋Ca(ClO)2＋2H2O Cl2＋2NaOH===NaCl＋NaClO＋H2O
光照
2HClO
2HCl＋O2
Cl2＋H2O=HCl＋HClO HCl＋AgNO3=AgCl↓＋HNO3
放电
N2＋O2 2NO＋O2=2NO2
2NO
Si＋2NaOH＋H2O=Na2SiO3＋2H2 SO2＋CaO=CaSO3 SO2＋2NaOH=Na2SO3＋H2O Si＋2F2=SiF4 SO2＋2H2S=3S＋2H2O
第 3 页,共 14页
OMe
X X OMe X
Br
Br HO B OH X N F X B N F X
Br N B Br F F Br N
Br
Pd(0)
X
Non-fluorescent
Pd(OAc) 2,O2
R2
brightly-fluorescent
O
R1
+
NO 2
R1 AIBN,NaCO 3
R2 O
C-N Bond Cleavage for C-C Bond Formation
O O R N O O
O R
H
N N
O N R
2
NN H R-N H N N N-R
N HN N N R-N-H N
N
H
N N
H-N-R
N
O O
[L],R=Me,Bu
[L],R=Me,Bu
N H N N R [L],R=Me,Bu
第 4 页,共 14页
Me N N O Me O O H H N N Me R3
Me R3 Me O
Ba
Me N N ph
Me O
ph
Fig.26. Structure of the derivatives [Ba(Q)2(pmdien)(H2O)]
Me N N O Me O N N ph Me N N N Me R3
Me R3 Me O
Ba
Me N
Me O
ph
R3=nPe,tBu
I N
O O
1)Azole,Cs2CO3 Pd(OAc)2,PPh3,Cul 2)NaOMe,MeOH 8
O OMe
Z
9 Z=NMe,49% Z=S,65%
Scheme3.
F3C
O
n n
R
CF3
n
R
CF3 CF3
cat, CuCl
n
第 5 页,共 14页
NH2
path"a"
NH2
N:
NH H N N
N
H N H N H N
N
[O] -H2O
7a 6 [O] pbth"b" 2c
N
N
9a
10
NH H N N N
[O] -H2O
N N
H N
9a
N
Scheme1 a) (i) (ii)
H 2N OH OH H 2N H 2N O NH2
(iv) iii
O H OH NH2 NH2 OH
OH HO NH2
M OH NH2 NH2 NH 3+ -O -O
M ONH3 + NH3 +
MZ+ with z =1,2(except Be2+)
N Ph N O O O Me N Pe n N Ph Ph N N Me nPe N Ph O Sr O O O Sr nPe Me N N O Ph Ph N N O O nPe O O nPe Me N
MZ+ with>=3,Be2+
Me
Pe n
Me
Fig.21.Structure of the derivative (imH2)2[Sr2(Qnpe )6]
第 6 页,共 14页
O O
O O Ga O Ga
O O
Ga
O O O Ga O O O
O O O Ga O O O
Ga
O N
CH 3
O N
CH3 O O N
O N
CH3
N R
O
PhCNO
Ph N O
N R
+
Ph
N R
O
p substrate
rxn
p
1.remove solvent p product separation
pruduct 2.add heptane and CH3 CN
1.rem
ove solvent (2.regeneration) 3.add substrate solution p:polymer-supported phosphine catalyst/reagent
第 7 页,共 14页
CNOH
O
Au3+
OH
1
NH 2
a,b
H R1 c N NH2 O
2
H R1 d N NH2 H N R1 N H F NO2 O
e
R1 N F N NO 2
f
R1 N N
R2 NH NO2
g
R1 N N
R2 NH NH2
h
R1 N N N
R2 N O H
i
R1 N N N
R2 N O R3
j
R1 N N N
R2 N O R3
R2 O N OC Z R1 O
R2
O
catalyst 4-Mes-DHPB
N S
N N Z
R1
O
55~94% e.e. (Z=OR3,Me)
第 8 页,共 14页
O
OH
Vitamin B12
O
NHR
OH NHR N O N O
c-acid
R3
O HN
d-acid
R2 N R2 I
R2 R1
R3-NH-NH 2
I2
N
NaHCO3
R1
N
R1 R1= alkyl,aryl,heteroaryl,ferrocenyl
R2=H,methyl,phenyl R3=alkyl,aryl
R3 23examples 40-95%yields
O R R N+ R O H N +H H O O O O O R O O O O H N +H H 4ClO4- O O O O O O O
O O
O O
n
N+
n
H N+H H O O
n
O O O O
H+ N
R
R N+
n
O
4ClO4-
R
R
O O H N +H H O O
logk1 up to 9.39 D -A complex R=H ,R+R=CH=CH;n=0.1
logk2 up to 3.30 D-A-D complex
第 9 页,共 14页
3500 3000 2500 2000
F G B D
If
1500 1000 500 0 -500
200 300 400 500 600 700 800
λ /nm
第 10 页,共 14页
1200 1000 800 600 400 200 0 200 300 400 500 600 700
B D E
If
800
λ/nm
第 11 页,共 14页
E
500
400
DTG/uq/min
300
200
100
0
3000
4000
5000
6000
7000
8000
TG/uq
E
300 250
DTG/uq/min
200 150 100 50 0 -100 -80 -60 -40 -20 0
DTA/uV
第 12 页,共 14页
E
300
250
DTG/ug/min
200
150
100
50
0 0 20 40 60 80 100
t/min
第 13 页,共 14页
3500 3000 2500 2000
F G B D E
If
1500 1000 500 0 -500 200 300 400 500 600 700 800
λ /nm
第 14 页,共 14页