Chapter 2 Green Chemistry
? 2.1 The concept of Green Chemistry
? 2.2 Promoting the development of Green
Chemistry
? 2.3 Atom Economy of chemistry reaction
? 2.4 Atom Economy and environmental
effects
? 2.5 Research area of green chemistry
? 2.6 Twelve principles of green chemistry
References
The concept of Green
Chemistry
Green Chemistry is
investigated world-widely
Countries and areas with Green
Chemistry investigation chapters
Noyori,Importance of Green Chemistry
Without Green
Chemistry,
chemical
manufacturing
will be unable to
survive into the
22nd century,
Green Chemistry
The connotation of
Green Chemistry
A deeper view of
Green Chemistry
Green Chemistry
is realizable
Green Chemistry
is different from
environmental
control
The connotation of Green
Chemistry
? Green chemistry is an active intercrossing
research area in the world,it deals with the
frontier of chemical research,
? The traditional ways of environmental
protection just bring us about temporary
solutions for environmental problems,while
Green Chemistry provides permanent cures,
The connotation of Green Chemistry
? Green Chemistry provides ways to reduce
or eliminate environmental pollution from
the beginning,which could have eternal
benefits,
? The principles of Green Chemistry could
and should be used to all domain of
chemistry and chemical engineering,
The connotation of Green Chemistry
?No pollution should be accompanied in
chemical processes,this is to say,
eliminate the potential of pollution before it
occurs,
?The realization of this goal means no
environmental control is needed,because
there will be no pollution,
The Goal of Green Chemistry,
The connotation of Green Chemistry
? Green Chemistry is the utilization of a set
of principles to reduce or eliminate the
use of hazardous materials in the design,
manufacture and use of chemicals,and
these chemicals should be economically
and environmentally benign,
? It deals also with the reduction and
elimination of the use of hazardous
materials in the design and use of
chemical processes,
Green Chemistry
The connotation of Green Chemistry
?Green Chemistry is the application of
chemical principles,chemical technologies
and chemical methods to all chemicals and
chemical processes to reduce or eliminate
the use of hazardous starting materials,
hazardous processes,hazardous target
products,hazardous auxiliary substances
(such as solvents,separation agents) in
the production and use of chemicals,
Green Chemistry
The connotation of Green Chemistry
?Hazardous or potentially hazardous
processes should also be reduced or
eliminated,
?By-products are expected to be avoided
as thoroughly as possible,and the
starting materials be utilized as
completely as possible,thus satisfying a
sustainable civilization,
Green Chemistry
The connotation of Green Chemistry
?Green chemistry is the science which
uses chemical principles and methods
to reduce or eliminate the use of
hazardous starting materials,catalysts,
solvents,reaction agents,target
products,by-products,etc.,which are
toxic or harmful to human beings and
environment,
?It is the chemistry which could reduce
and eliminate pollution from the very
beginning and cure pollution eternally,
Environment
&
resource
Simultaneously
give out
Green
Chemistry
Solution
Recyclable
economy
Sustainable
development
Cr
ise
s
Re
qu
ire
me
nt
Green
Chemistry
Green Chemistry
The connotation of
Green Chemistry
A deeper view of
Green Chemistry
Green Chemistry
is realizable
Green Chemistry
is different from
environmental
control
Green Chemistry is realizable
?The goal of green chemistry is to seek for
perfection(by overcoming difficulties),
?Synthesis efficiency is highly thought of in
green chemistry,
?Opposite opinions,it is difficult to
quantify the toxicity and harmfulness of a
substance to human beings and to
environment,
?Examples already realized give evidences
strongly to illustrate that green chemistry is
realizable,
?Relationship between structure and
properties —— gives us clue to predict the
harmfulness of substances,
?We could compare and select the most
favorable substance and method under
specified conditions,
Green Chemistry is realizable
Green chemistry way
Bring about a
temporary
solution
Treat the
existed waste
Treat waste
Provide a
permanent cure
Eliminate waste
from the origin
No waste
produced
Not need for
waste treatment
Traditional way
Waste produced
then treat
Fa
cin
g t
he
in
cre
as
ing
en
vir
on
me
nt
al
po
llu
tio
n
Green Chemistry
The connotation of
Green Chemistry
A deeper view of
Green Chemistry
Green Chemistry
is realizable
Green Chemistry
is different from
environmental
control
Deeper viewpoints on
Green Chemistry
? Scientific viewpoints,
? Green Chemistry concerns new research area
of chemistry,It rejuvenates the contents of
chemistry,
Environmentally benign
Starting materials,target products
High selectivity,atom economy
? Economical viewpoint,
? Green Chemistry provides fundamental
principles and techniques to utilize effectively
the starting materials(resources) and energy,
meanwhile the cost of the production is
reduced,thus satisfying the requirements of
sustainable development,
Deeper viewpoints on
Green Chemistry
? Environmental viewpoint,
? Green Chemistry provides new principles
and techniques to cut down pollution
originally and eternally,
Deeper viewpoints on
Green Chemistry
? 2.1 The concept of Green Chemistry
? 2.2 Promoting the development of Green
Chemistry
? 2.3 Atom Economy of chemistry reaction
? 2.4 Atom Economy and environmental
effects
? 2.5 Research area of green chemistry
? 2.6 Twelve principles of green chemistry
References
Why
2.2 Promoting the development
of Green Chemistry
Satisfying the
demand for
sustainable
development of
human society
Satisfying the
requirement
of science and
economy
Strongly develop green
chemistry to satisfy the
demand for sustainable
development of human society
Traditional
chemical
Industry
is accompanied
by unexpected
harm (3 aspects)
No other
alternatives
exist
Green
chemistry
is the unique
solution
Environment
&
resource
Simultaneously
give out
Green
Chemistry
Solution
Recyclable
economy
Sustainable
development
Cr
ise
s
Re
qu
ire
me
nt
Green
Chemistry
Satisfying the requirement for the
development of science and economy
Chemistry itself develops in accordance
with the change of resources and of the
social requirement,
It should also be renewed in methodology
and content,
Green chemistry appears,
?Scientifically,
?Chemical industry plays an important role in
the industrial ensemble
Britain,Germany,USA
?Chemical enterprises make great effects to
reduce their cost,and increase their cost by
treating the pollutants they produced,
?Green chemistry provides new ways which
could satisfy both the demands of chemical
production,
Satisfying the requirement for the
development of science and economy Economically
? 2.1 The concept of Green Chemistry
? 2.2 Promoting the development of Green
Chemistry
? 2.3 Atom Economy of chemistry reaction
? 2.4 Atom Economy and environmental
effects
? 2.5 Research area of green chemistry
? 2.6 Twelve principles of green chemistry
References
2.3 Atom Economy of Chemical
Reaction
Atom utilization Atom economy
of chemical
reaction
Increase
the conversion of
the reactants,
the selectivity
of the products
2.3.1,Atom utilization
The concept was used to quantify
the waste (by-products) formed
when a certain amount of target
product was manufactured in a
chemical reaction,
Roger A.Sheldon 1992
Atom
utilization =
=
The amount of target product formed
╳ 100%
The amount of all products
formed stoichiometrically
The amount of reactants used
The amount of target product formed
╳ 100%
Atom utilization
The two main characteristics of chemical
reaction with 100% atom utilization,
?The reactants could be fully utilized,and the
resource could be most possibly used
economically
?The waste could be minimized
原子利用率 = 目标产物的量
按化学计量式所得所有产物的量之和
=
目标产物的量
各反应物的量之和
╳ 100%
╳ 100%
Examples
Example 1, The preparation of epoxy-
ethane from ethylene more
Example 2,The preparation of epoxy-
propane more
Example 3,The synthesis of methyl
acrylate more
Example 1
The preparation of epoxy-ethane
Traditional way
CH2=CH2 + Cl2 +
H2O
ashsska ClCH2CH2OH + HCl
ashsska ClCH2CH2OH + Ca(OH)2 +
HCl
C2H4O + CaCl2 + 2H2O
CH2=CH2 + Cl2 + Ca(OH)2 C2H4O + CaCl2 + H2O aska
28 71 74 44 111 18 ashsska ashsska
44 ashsska
111+ 18 = 129
44
111+ 18 + 44 ╳ 100% =
44
28+ 71 + 74 ╳ 100% = 25% =
Disadvantages of the
traditional method
?1,The atom utilization could reach only 25%,
i.e.,1kg of target product / 3kg of wastes,
? 2,The reactant Cl2 is harmful,it erodes the
equipment and injures human beings,thus
demanding special equipment and special
protection measure,
? 3,Separation and purification processes are
necessary to obtain useful product,
If every step could obtain 100% selectivity
and 100% yield,then
Silver catalyst is used to convert ethylene directly to the
target molecule by using oxygen as the oxidant,which gives
100% atom utilization,
New greener way
CH2=CH2 + 1/2O2 ashsska
44
C2H4O
28 16 ashsska
44
0
ashsska 44 28+16 = ╳ 100% ╳ 100% =
44
ashsska 44 = 100%
? High atom economy (100%)
? Oxygen is safe to human beings and
to environment,
? No separation or purification is
needed,
Advantages of the
new greener method
If the selectivity of the reaction could reach 100%
Example 2
The preparation of epoxy-propane
ka
42 71 58 74 111 18 ashsska asha asha
asha
58 asha
111+ 18 = 129
58
111+ 18 + 58 ╳ 100% =
58
42+ 71 + 74
╳ 100% = 31%
C3H6O + CaCl2 + H2O CH3CH=CH2 + Cl2 + Ca(OH)2
=
Traditional way
Disadvantages of the
traditional method
?1,The atom utilization could reach only 31%,
i.e.,1kg of target product / 2kg of wastes,
? 2,The reactant Cl2 is harmful,it erodes the
equipment and injures human beings,thus
demanding special equipment and special
protection measure,
? 3,Separation and purification processes are
necessary to obtain useful product,
If every step could obtain 100% selectivity
and 100% yield,then
Direct oxidation catalyzed by titania-silica
New greener way
ka
42 34 58 18
ashsska asha
asha
C3H6O + H2O CH3CH=CH2 + H2O2 Ashs ska Titania- sillica
molecular sieve
ashsska
58
18 asha
58
58 + 18 ╳ 100% =
58
42 + 34
╳ 100% = 76% = a
The amount of target
product formed
? The atom utilization is high (76 %)
? The by-product----water is
environmentally benign,
? Hydrogen peroxide is safer than
chlorine to human beings and to
environment,
Advantages of the
new greener method
If the selectivity of the reaction could reach 100%
Problem?
CH3CH=CH2 + 1/2 O2 C3H6O
Example 3
The preparation of methyl acrylate
This process uses the by-
products from phenol industry
and acrylonitrile,acetone and
hydrocyanic acid
H3CCOCH3 HCN
Traditional way
Traditional way
held
CH3C(CN)(OH) CH3 CH3COCH3 + HCN Ahs ska
CH3OOC(CH3)C=CH2 + NH4HSO4 CH3OH,H2SO4
CH3COCH3+ HCN + CH3OH + H2SO4 CH3OOC(CH3)C=CH2 + NH4HSO4 AA
100+115
╳ 100% = =
a
58
a
27 32 98 100 115
100
115
╳ 100%
100
58+27+32+98
100
AA
AA AA = 46%
AA
Disadvantages of the
traditional method
?1,The atom utilization could reach only 46%,
i.e.,1kg of target product / 1kg of wastes,
? 2,The reactant HCN is harmful,it erodes the
equipment and injures human beings,thus
demanding special equipment and special
protection measure,
? 3,Separation and purification processes are
necessary to obtain useful product,
If every step could obtain 100% selectivity
and 100% yield,then
This process utilizes the by-product
propyne CH3C≡ CH from the dissociation
(e.g,Pyrolysis) of naphtha,and carbon
monoxide,
New greener way
Using palladium acetate Pd(OAc)2 as the
catalyst,developed in 90’s
New greener way
Pd(OAc)2
? The atom utilization is high (100 %)
? Carbon monoxide and methanol are
safer than hydrocyanic acid to
human beings and to environment,
? No waste produced
Advantages of the
new greener method
If the selectivity of the reaction could reach 100%
2.3.2 Atom economy of
chemical reaction
Definition,
The ratio of atoms appeared in the target
molecules to all the atoms of the reactants
The reaction with 100% atom utilization is
ideal atom economical reaction,
1991,Barry M,Trost
1996,The Presidential Green Chemistry
Challenge Award of USA
How to design
atom economical
reactions
如何设计
原子经济反应
Deficiency of the traditional
synthetic ways
A + B C ＋ D
wa
ste
Tar
ge
t
mol
ecu
le
For a target molecule C
If the traditional way is
A + B C + D
This process inevitably produces the by-product D,
which should be treated and could be considered as
waste,
Because this is the chemical reaction,if we want to
use this reaction,we could not avoid this dilemma,
Atomic economic
reactions
E + F C
Target
product
Thus we should design new atom economical
reactions as
E + F C
Advantages,all the atoms in the reactants E
and F entered in the target molecule C,making
the atom utilization be 100%,
No by-product formed
Thus,no waste for treatment
No pollution
Problem
? The types of organic reactions,
Please answer
? Which kinds are atomically economical?
Example
The synthesis of haloalkane
Atom economy,100%
No by-product
No pollution
The consumption of
resource is minimized。
3 moles target
molecules/1mole
by-product,Waste
resources and the
by-product is a
kind of pollutant
3ROH + PX3 ?
3RX + H3PO4
RX’ + NaX
?RX + NaX’
R’CH=CH2 + HX
? RX
1mole target
molecules/1mole
by-product，
Waste resources
and the by-
product is a kind
of pollutant
Use the natural resource
more efficiently,prolong
their lifetime,
Study on atomic
economic
reactions
Chiral
technique
All atoms
from
reactants
enter into
the target
molecule
All atoms from
reactants enter
into the target
molecule
stereo-
orientatedly
Facing the dried up of natural resource?
2.3.3 Increase the conversion of the
reactants and the selectivity of the
products as thoroughly as possible
Atom economy is necessary for a
reaction to not produce waste,but it is
not enough,
Low equilibrium conversion
Parallel reactions
? 2.1 The concept of Green Chemistry
? 2.2 Promoting the development of Green
Chemistry
? 2.3 Atom Economy of chemistry reaction
? 2.4 Atom Economy and environmental
effects
? 2.5 Research area of green chemistry
? 2.6 Twelve principles of green chemistry
References
2.4,Atom Economy and
environmental effects
2.4.1,Environmental factor
It is used to quantify the effects of
production process to the environment
Idea,All other compounds formed other
than the target product are considered to
be WASTE,
Roger A.Sheldon in 1992
Environmental
factor
E= The amount of waste The amount of
target product
The larger E The more waste formed
The more serious
the pollution
If the atom
Utilization=100%
E=0
The environmental factor
of several industries
Industries Production/t E
Petrol 106 ~ 108 ~ 0.1
Fundamental
Chemicals 104 ~10 6 1 ~ 5
Fine chemicals 102 ~ 1 04 5 ~ 50
Pharmacy 10 ~ 103 25 ~ 100
But the environmental pollution is
strongly associated with the harmful
performance of the waste,
2.4.2,Environmental quotient (EQ)
The E factor just gives the ratio of
the waste and the target product,
Environmental quotient
E-----Environmental factor
Q-----The extent of hazardousness of
the waste to the environment
obtained from the performance of the
waste in the environment,
EQ＝ E× Q
Chapter 2 Green Chemistry
? 2.1 The concept of Green Chemistry
? 2.2 Promoting the development of Green
Chemistry
? 2.3 Atom Economy of chemistry reaction
? 2.4 Atom Economy and environmental
effects
? 2.5 Research areas of green chemistry
? 2.6 Twelve principles of green chemistry
References
2.5 Research areas of green
chemistry
Designing safer and effective target molecules
Seeking for safer starting materials
Seeking for safer synthetic processes
Seeking for new safer conversion ways
Seeking for safer new reaction conditions
Gr
ee
ne
r,S
afe
r
2.5.1,Designing safer and effective
target molecules
The target molecule being safe is
prior to all considerations,and it
should also be effective,
The designing of safer chemicals is the use
of the relationship between molecular
structure and properties (structure-activity
relationship,SAR) and molecular
manipulation method to obtain molecules
with maximized desired functions and
minimized harmfulness,
Designing safer and effective
target molecules
In 1983,a seminar on the designing of safer
chemicals has been hold in Washington,
Designing safer and effective
target molecules It involves two aspects,
1,The designing of new safe and
effective molecules,
2,The designing of new safer and
effective molecules to replace
the molecules which existed
effective but not benign
We have more than 18,000
thousands of compounds up to
now,while 600 thousands of
new compounds appear every
year,
Designing safer and effective
target molecules
Designing safer and effective
target molecules
Traditio al ways of finding
an effectiv molecule,
Practical needs synthesis test
synthesis test
New molecular designing ways,
Trial and errors
Practical needs designing by SAR synthesis
Guided theoretically
test
Working desk+computer
+ventilation cupboard
Designing safer and effective
target molecules
2.5.2,Seeking for New starting
materials
Seeking new starting materials to
substitute the actually used hazardous
and poisonous materials
Example 1 Using CO2 to substitute phosgene
（ 光气 ） in the synthesis of polyurethane(聚氨酯 )
Example 2 Elimination the use of hydrocyanic
acid（ 氢氰酸 )
Example 3 The synthesis of adipic acid（ 己二
酸 ） using new safe starting materials
Eliminating the poisonous phosgene in
the synthesis of polyurethane
and polycarbonate
Example 1 Cl
C
Cl
O
Polycarbonate(聚碳酸酯 )
Phosgene is widely used for
the production of,
isocyanate (异氰酸酯 )
polyurethane(聚氨酯 )
Isocyanate is first synthesized by the reaction
of phosgene and amine,and then using
isocyanate to produce polyurethane,
Traditional way
按照化学
RNH2 + COCl2 RNCO + 2HCl
RNHCO2R1
The synthesis of isocynate
What kinds of functional group would
phosgene provide in a chemical reaction?
Which kind of compound could be
employed to substitute phosgene?
providing -CO group
Cl
C
Cl
O
Carbon dioxide is used to substitute
phosgene in the production of
isocyanate (providing carbonyl group)
The function of phosgene,providing -CO group
按照化学
RNH2 + CO2 RNCO + H2O
RNHCO2R1
New greener way
按照化学
The synthesis of isocyanate using CO2
C6H5NH2 + CO2 C6H5N(H)CO2H
C6H5N=C=O
–H2O
Aniline
按照化学
2CH3OH + COCl2 CH3OOCOOCH3 + 2HCl
2CH3OH + CO + ? O2 CH3OOCOOCH3 + H2O Catalyst
2CH3OH + CO2 CH3OOCOOCH3 + H2O
Thermodynamics,Catalyst,
Reaction conditions,temperature/pressure
The synthesis of di-methyl carbonate
Traditional way
New greener ways
The elimination of the use of HCN
(hydrocyanic acid) (hydrogen cyanide,
prussic acid) by changing the process
Example 2 C NH
Hexane dinitrile(己二腈 );
Series of methylpropenoic acid(甲基丙
烯酸系列 );
Series of intermediate chemicals such
as chelator / chelating agent(螯合剂 ),
methionine (蛋氨酸 ) etc,
Hydrocyanic acid HCN is widely
used for the production of,
The synthesis of sodium iminodi-acetate
(亚氨基二乙酸二钠 )
Traditional way
involves two steps,
按照化学
NH3 + 2CH2O + 2HCN
— ① NCCH2NHCH2CN
— ② + 2NaOH → NaO 2CCH2NHCH2 CO2Na + NH3
A new starting material
HOCH2CH2NHCH2CH2OH
(diethanolamine,二乙醇胺 ) is used
New greener way
Replacing HCN
The synthesis of adipic acid ( /hexanedioic acid
己二酸 ) and hexamethylene diamine (己二胺 )
CH2=CHCH=CH2 + HCN NCCH2CH2CH2CH2CN
HOOC(CH2)4COOH
H2N(CH2)6NH2
Traditional method
Replacing HCN
C6H12
The oxidation of Cyclo-hexane(环己烷 )
Oxidation
HOOC(CH2)COOH
The hydrocarbonylation of butadiene
CH2=CHCH=CH2 + 2CO + 2H2 OHC(CH2)4CHO
HN=CH(CH2)4CH=NH
H2N(CH2)6NH2 HOOC(CH2)COOH
O2
catalyst
2NH3 - 2H2O
2H2
New greener methods
Replacing HCN
The synthesis of phenyl acetic acid
C6H5CH2Cl +HCN C6H5CH2CN + HCl C6H5CH2COOH H2O
C6H5CH2Cl + CO C6H5CH2COOH
OH– / H2O
Traditional way
New greener way
Can we design another green way to
synthesize phenyl acetic acid with
ethylbenzene and oxygen as reactant?
C6H5CH2CH3 + O2 C6H5CH2COOH
If can’t,why?
Example 3
The synthesis of adipic acid by
changing starting material
Traditional way
Could anyone tell me the
disadvantages of this method
? Photochemical smog
? Depletion of ozone,
? Acid rain
Disadvantages of the
traditional method
The starting material (Benzene) is
hazardous (carcinogentic)
The release of nitrogen oxides which
are multifunctional pollutants
Use of heavy metals (cobalt)
Elimination of the use of solvent,the use of
hazardous benzene,the corrosive capacity
of hydrogen peroxide is not as severe as
nitric acid,no pollutants produced,
Kamzuhiko Sato,1998,Science,281:1646-1647
按照化学
H OO C
C OO H+ 4 H 2 O 2
Na 2 WO 4
[ C H 3 ( n - C 8 H 17 ) 3 N ]H S O 4
P h as e T r an sfer C ataly st
New greener method 1
The synthesis method is widened,
Drath and Frost,1990,1991
按照化学
O
O H
O H
O H
O H
OH
C OOH
O H
O H
O
H OOC
C OOH
P l a tniu m
c a ta l y s t
New greener method 2
Not only eliminate the use of benzene,
but also develop a new method to use
renewable biomass(glucose),
Using of renewable starting material
150 years ago,industrial
organic chemicals were all
derived from biomass
originated from plants
The use of biomass as starting material
for energy and chemicals production
regain much attention,because of its
renewability,
Coal Oil Natural gas Coal
Starting materials Biomass Industrial revolution
One kind of solar energy
Using of renewable starting material
Security and Energy Resources
Oil,30-50 years
Natural Gas,50-100 years
Coal,200-400 years
It must degenerate before it
could be effectively used,
Biomass,Starch (淀粉,amylum)
+ Lignin (木质素,lignine)
Lignin,164 billion ts /year
amount used <1.5%
Using of renewable starting material
Security and Energy Resources
Oil,30-50 years
Natural Gas,50-100 years
Coal,200-400 years
Examples
Using of renewable starting material
plants,trees,crops,grasses,aquatic
plants and their residues or waste
materials,
? 5 hundreds million tons of wheat straw;
? 10 million tons of rice bran;
? 10 million tons of corncob;
? 20 million tons of rice hull;
? 7 million tons of biogases;
Using of renewable starting material
about 2.8～ 3.5 hundreds million of tons
can be used as resource of energy,
/year In China,
The burning of straw:,waste of
resource while polluting
? The structure of lignin and its effect on
its degradation
? Orientated degradation to produce
directly useful chemicals
Using of renewable starting material
Fundamental scientific challenge,
Technical challenges,
? Continuous operation
? Separation of the products
Using of renewable starting material
Actual progresses
Cross
Agricultural waste (polysaccharides)
Naturally degradable polymer
Sichuan University,University of Science and
Technology,Shandong University,Chemical
Institute Academy of China,Guangzhou
Biomass
Animal feeds
Fuel
Chemicals
Using of renewable starting material
Haltzapple from Texas A & M university
1996,The presidential Green Chemistry Award
Converting biomass to fuel and chemicals
Direct liquation
Biomass
Liquid fuel &
chemicals
Indirect conversion
Gasification
C3-C4
Gases
Gas
fuel
CO + H2
Liquid fuel &
chemicals
Catalytic
conversion
Using of renewable starting material
Gasification reactor (fixed bed)
for biomass conversion
gasifier
purification
fan gas tank
Needed
By
Home
biomass,air
Gasification reactor (fluidized
bed) for biomass conversion
gasifier
biomass
tank
CO + 2H2=
CH3OH
reforming reaction bed
biomass
Gasification reactor (fluidized
bed) for biomass conversion
Gas
production：
150 M3/h
Operation
pressure：
1MPa
Heat capacity：
7 MJ/M3
Efficiency of
energy
conversion：
80%
Fast-
growing
bamboo
Fast-
growing
shrubs
Convert biomass to useful
products green chemically
将
生
物
质
转
化
为
化
学
化
工
原
料
开
发
新
资
源
实
现
资
源
持
续
利
用
Agricultural waste
Chemical research based on
energy resources
Biomass
Coal
Oil
Coal
Natural Gas
Chemistry
Treating
? CnH2n± x
? CH4
? C
Treating
? CnH2nOn
? C
? CO2
2.5.3,Seeking and designing
safer and effective synthetic routes
Ideal synthetic route
Paul A Wender 1996
the starting material used should be the
cheapest and most feasible;
the operation and manipulation should be
simple,safe and environmentally benign;
the reaction rate should be fast and the yield
of the target products,either natural or
designed by ourselves,should be as high as
possible,
? The synthetic route is a very important factor to
the benignity of a process,
? The integration of chemical reactions to make
the whole process benign,
? Computer aided designing of synthetic route
Designing proper synthetic route
Example,The synthesis of para-phenylene
diamine （对苯二胺,ursol ） from
nitrobenzene (硝基苯,mirbane oil)
The synthesis of para-phenylene
diamine from nitrobenzene
Let us analyze four possible routes in a
green chemistry viewpoint
Example
The synthesis of para-phenylene
diamine from nitrobenzene
Let us analyze four possible routes
in a green chemistry viewpoint
Route 1
NO
2
N H
2
N H C O C H
3
+ 3 F e + 6 H C l
- 3 F e C l
3
- 2 H
2
O
+ ( C H
3
C O )
2
O
- C H
3
C O O H
N H C O C H
3
NO
2
N H
2
NO
2
N H
2
N H
2
+ H N O
3
/ H
2
SO
4
- H
2
O
+ H
2
O / H
+
- C H
3
C O O H
+ 3 F e + 6 H C l
- 3 F e C l
3
- 2 H
2
O
?The amounts of reactants,1062
?Target molecule,108
?Waste,954
?Atom utilization,
The overall reaction
10%
按照化学
Route 2
NO
2
N H
2
N H C O C H
3
+ ( C H
3
C O )
2
O
- C H
3
C O O H
N H C O C H
3
NO
2
N H
2
NO
2
N H
2
N H
2
+ H N O
3
/ H
2
SO
4
- H
2
O
+ H
2
O / H
+
- C H
3
C O O H
R a n y N i c k e l c a ta l y ti c
h y d r o g e n a ti o n,- 2 H
2
O
R a n y N i c k e l c a ta l y ti c
h y d r o g e n a ti o n,- 2 H
2
O
The overall reaction
?The amounts of reactants,300
?Target molecule,108
?Waste,192
?Atom utilization,36%
按照化学
Route 3
NO
2
N H
O
NO
2
+ 1 / 2 O
2
/ O H
-
- H
2
O
NO
2
N H
2
N H
2
N H
2
+ N H
3
/ Me O H
+ 3 F e + 6 H C l
- 3 F e C l
3
- 2 H
2
O
C O N H
2
C O N H
2
-
The overall reaction
?The amounts of reactants,543
?Target molecule,108
?Waste,435
?Atom utilization,20%
按照化学
Route 4
NO
2
N H
O
NO
2
+ 1 / 2 O
2
/ O H
-
- H
2
O
NO
2
N H
2
N H
2
N H
2
+ N H
3
/ Me O H
c a ta l y ti c a l
h y d r o g e n a ti o n c a ta l y ze d
b y R a n y N i c k e l
- H
2
O
C O N H
2
C O N H
2
-
The overall reaction
?The amounts of reactants,162
?Target molecule,108
?Waste,54
?Atom utilization,67%
Aggregative analysis
From the viewpoint of atom economy,route
4 is the most favorable comparing to
others。
In routes 1 & 2,because of the protection of
-NH2 in nitration,one mole of acetic
anhydride is needed and 2 moles of acetic
acid are formed as waste,while in routes 3
& 4,the protection step was not needed,
Practical need,
great amount of possible routes
for
a giving target molecule,
Computer aided
designing of synthetic route
Corey and Bersohn,30 years ago
used computer to help designing
of synthetic route
30 ? 30× 30 ? 30 × 30× 30 ?
…… ?305 > 24 million routes
Computer aided
designing of synthetic route
e,g,If the synthesis of a compound needs
5 steps,and 30 methods are possible
for each step,thus we will have
The progress
of computation technology
Computer aided
designing of synthetic route
The progress
in computer science and technology
? Construction of a data base of chemical
reactions as complete as possible,
? Put forward our requirement
? Let the computer give us the possible
starting materials which could form the
target molecule
Te
ch
nic
al
Wa
y
Computer aided
designing of synthetic route
? Further search for the starting material
using the former starting material as the
target molecules…………
until the provided starting material is
needed
? Compare all possible routes,and choose
the most favorable one from the viewpoint
of economical and environmental effect,
Te
ch
nic
al
Wa
y
Computer aided
designing of synthetic route
2.5.4 Seeking for new conversion
methods
Catalytic plasma more
Electrochemical conversion more
Photo and other radiation conversion
more
Seeking for
unconventional conversion ways
The synthesis of gasoline from carbon
dioxide and natural gas(methane,甲烷 )
CO2 + CH4 2CO + 2H2 Gasoline → →
Nickel catalyst FT process
Changjiun Liu,Tianjing University
Traditional thinking up
CO2 + CH4 Gasoline
Catalyst & plasma
condition
Plasma,
breaking of the
reactant molecules
Catalyst,
forming of the
product molecules
Catalytic plasma
Using electrochemical ways
? Electricity can be used not only as an
energy supply for chemical reactions,it
could also affect chemical reaction in
different aspects and provide new ways
for it to occur,
? The following example will give us
some direct information,
Using electrochemical ways to eliminate the
use of hazardous starting materials and make
the reaction to occur at moderate conditions
Cyclization reaction
O
OM e
Br
C H
3
C H
3
OCH 3 C H 3
electr on /V it B 12
CH
3
OH
O
OH
C H
3
CH
3
C H
3
C H
3
O
The electro-synthesis of epoxy propane
Unfortunately,the selectivity of this route is not as
good as expected,and is not yet industrialized,
Using electrochemical ways
At the anode
H2O-NaCl
CH 3 C H C H 2 CH 3 C H
O H
C H 2
Cl
At the cathode
CH 3 C H
O H
C H 2
Cl
CH 3 CH C H 2
O
? The synthesis of hexafluoropropylene oxide
F2CH=CFCF3
PbO2/Steel/anode Steel/cathode
H2O-HOAc-HNO3
The conversion,65-75%,Selectivity,90%
This route has already been industrialized
by Hoechst Company
Using electrochemical ways
CF3CFCF2
O
Using electrochemical ways
? The synthesis of para-diphenylamine
from aniline by electrolysis
C6H5NH2
H2O-NH4I/Pt
NH3
I -NH2
NH2 -NH2
? The electrosynthesis of
hydrochinone(hydroquinone,hydroquinol)
At the anode
C6H6 +2 H2O + 6H+
At the cathode
OH
OH
O O
Using electrochemical ways
C6H6 + 2 H+ + 2e
?The cycle open reaction of dioxane (二恶烷 )
,O- or S-hetero cyclohexane (氧硫杂环已烷 )
use heavy metal catalyst traditionally,and
additional reactants are needed,
?Epling etc use light as the reacting agent to
realize these reaction and avoid the pollution
caused by heavy metals
Photo and other radiation conversion
S S
O
C H
3
S S
C H
3
O
hv
97%
94%
O
O
S
S
O
O
O
H
hv
hv
91%
2.5.5 Seeking for Safe and effective
reaction conditions
? Seeking for safe and effective catalyst
Loading of active component on suitable
support more
Replacing liquid acids by solid acids more
?Example 1
?Example 2
? Seeking for safe and effective reaction medium
Using supercritical fluid as reaction medium
more
Using water as reaction medium more
?Example 1（ hydroformylation of propylene）
Loading of active components
on suitable support
?Traditional Friedel-Crafts reactions,
hydrofluoric acid(氢氟酸 ),sulfuric acid(硫
酸 ),aluminium chloride(三氯化铝 ),boron
fluoride(三氟化硼,boron trifluoride) are
used as the catalysts,
The disadvantages,
? The operation must be done anhydrously
(water free),3 moles of hydrogen chloride
will be released when accounting water,
? The system is corrosive,strict operation
conditions must be controlled,
? Low selectivity because of the formation of
poly-alkyl-substituted products and other
isomers,
Loading of active components
on suitable support
? In acylation reactions(酰基化 )such as ordinary
acylation,the formylation of benzene(苯甲酰化 ),
sulfo-acylation(磺酰化 ),large amount of
aluminium chloride is needed becaues of the
complexity of the products,
? Finally,water must be added to release the
product molecule and thus releasing large
amount of hydrogen chloride as well as
chlorinated hydrocarbons as impurity,
Loading of active components
on suitable support
? The supported catalyst K10-AlCl3,prepared by
supporting AlCl3 on montmorilonite(蒙脱土,imvite)
shows activity as high as the conventional ones and
higher selectivity for the formation of mono-
alkylated product than the old ones,
? The supporting of ZnCl2 on montmorilonite (蒙脱
土,imvite) could also obtain a new kind of catalyst
for the Fridel-Crafts reactions,and this already
provides a new perspective for industrial application,
Loading of active components
on suitable support
Using solid acids to replace
liquid acids
Acidic clay(酸性白土 ),mixed chlorides,
molecular sieve(分子筛 ) etc,could be
used to replace liquid acids,
? （ 1）,Some inevitable barriers that could
not be overcome in homogeneous catalysis
could be lowered in a certain degree or totally
overcome,
? （ 2）,The temperature range could be
widened to 700-800K,and thus widening the
range of acid catalysis,
Example 1,The traditional Fridel-Crafts
acylation reaction,
Target product/Aluminium chlorode,1/3
C O C l
Cl
Cl
O
+
E n v i ro c a t E P Z G
140
0
C,2 4 h
The use of new catalyst Envirocata,EPZG to replace
AlCl3,the amount of catalyst could be reduced to 1/10 of the
traditional one,the amount of waste (HCl) is reduced to ?,
while the yield of the target product increased to 70%,and
the selectivity of the is increased,the amount of ortho-
substituted product is reduced to trace
Problem
Complete the reactions in
example 1,compare their
atom utilization and discuss
their advantages and
disadvantages,
Using supercritical fluid (scf.)
as reaction medium
? The characteristics of scf,
Cheap,safe and property adjustable,Scfs
show different property under different
conditions,we can adjust the supercritical
conditions to adjust its property until it
satisfy our needs for the reaction to occur,
Supercritical carbon dioxide,
? Tanko used SCF CO2 as the reaction medium for
the brome substitution reaction of alky-
substituted-aromatics,equivalent or higher yield
and selectivity were obtained,
? Chemical Institute of guangzhou,
? SCF CO2 was used as both the reaction medium
and reactant in the carbonylation（羰基化） of
olefin(烯烃 )
? SCF water
? SCF water + carbon dioxide
Using supercritical fluid (scf.)
as reaction medium
Bi-phase catalysis using
water as reaction medium
? Water-soluble complex compounds could
be used as catalyst,and then the reaction
takes place at the interface formed
between the water phase and the organic
phase of the reactants,
? Micelle could be provided by varying the
central atom and the ligand as well as the
use of surfacants,thus the interface could
be enlarged and the regional concentration
of the reactants could be increased,
? By varying the structure of the micelle,the
stero-structure of the product could also be
controlled,
Bi-phase catalysis using
water as reaction medium
? Thus,mild reaction conditions,high
activity and selectivity could be afforded
for and the separation of organic phase and
water phase becomes easy,Meanwhile,
environmental pollution could be avoided,
Bi-phase catalysis using
water as reaction medium
Example 2,The alkylation of benzene
with ethylene Forming ethyl benzene
? Traditional way,AlCl3,BF3,HF were
used as the catalysts
?Serious corrosion of the equipment
?Strict operation conditions
?Low yield
?Difficulties to eliminate HCl,RCl
?Difficulties of the separation of the catalyst and
the products
?Waste water
?Hazardous HF used
? The use of phosphorus ZSM –5 molecular
sieve overcomes the above shortcomings
Traditional way,Co-based catalyst,
high pressure is needed
Rh- or Pd-based water-soluble catalyst
Bi-phase catalysis
2.6 Twelve Principles
of Green Chemistry
1
3
5 7
9
11
2
4
6
8
10
12
1:It is better to prevent waste than to
treat or clean up waste after it is
formed
? Normal cost,
? starting material and reagent (intrinsic)
? the treatment and disposal of chemicals
? Large chemical companies in U.S.,
? expenditures on research and development
≈expenditures on environmental health and safety
? The costs of dealing with hazardous substances,either
through handling,treatment,or disposal,have continued to
increase substantially
1,It is better to prevent waste than to
treat or clean up waste after it is
formed
? A criterion that is often assessed to calculate the need or
desire for treatment or control of a chemical substance is
whether or not damage has been done by the generation
of waste,
? In many cases the,damage” is merely that substances
have been uselessly processed or transformed,costing
energy,money,time for separation from product,and
almost always requiring technology to get rid of them or
to render them innocuous,
1,It is better to prevent waste than
to treat or clean up waste after it is
formed
? One type of waste production that is both common and
often the most avoidable is starting material or reagent
that is unconverted,
? When one wastes starting material,one is paying for the
substance twice; once as a feedstock and again as a
waste and so one has achieved no utility from the
substance,More seriously,often the cost of waste
disposal may be many times the cost of the virgin starting
material,
? Thus,if possible,it is better to cut pollution from its origin
rather it is formed,
2,Synthetic methods should be
designed to maximize the
incorporation of all materials used
in the process into the final product
? The classic evaluation of the effectiveness
and efficiency of a synthesis is ―Yield‖,
? This ―Yield‖ totally ignores the use or
generation of any undesirable products
that are an intrinsic part of the synthesis,
? It is better to use atom economy to
evaluate synthesis ways,
? Atomically economy reactions
? Rearrangements
? By definition,a rearrangement reaction is a
reorganization of the atoms that make up the
―old‖ molecule,Thus all atoms in the
reactants are incorporated into the product,
? Addition reactions
? Because addition reactions add the elements
of the reactant to a substrate with total
inclusion (e.g,cycloadditions,bromination of
olefins),they are atomic economical,
2,Synthetic methods should be
designed to maximize the
incorporation of all materials used
in the process into the final product
? Non atomic economical reactions
?Substitution
? Because in this kind of reaction,one
group(the substituting group) displaces a
leaving group,the leaving group is
necessary a waste product of the reaction
that is not included in the final product
and therefore diminishes the atom
economy of the transformation,The exact
degree to which the reaction is non-atom
economical is dependent on the specific
reagents and substrates used,
2,Synthetic methods should be
designed to maximize the
incorporation of all materials used
in the process into the final product
?Elimination
? Elimination reactions transform the
substrate by reducing the atoms to
generate the final product,
? The eliminated atoms are lost as waste,
2,Synthetic methods should be
designed to maximize the
incorporation of all materials used
in the process into the final product
3,Wherever practicable,synthetic
methodologies should be designed
to use and generate substances that
possess little or no toxicity to human
health and the environment
? The fundamental basis of green chemistry is the
incorporation of hazard minimization or elimination
into all aspects of the design of the chemistry,
? Green chemistry recognizes that it is through the
skills and knowledge possessed by chemists that
today’s world can have the modern technological
advances that have come to be expected from the
scientific community in a way that is safe for
human health and the environment,
3,Wherever practicable,synthetic
methodologies should be designed to
use and generate substances that
possess little or no toxicity to human
health and the environment
? There are only two ways to minimize risk of harm of any
kind,
? Minimize the exposure
? A variety of forms could be taken,protective clothing,
engineering control,respirators etc,
? It is virtually impossible to control exposure without
increasing the cost of the process,
? Exposure controls can fail,and so ones risk increases
commensurately with that failure,
? Minimize the hazard
? The intrinsic characteristics that is not going to change and
therefore the risk will not increase spontaneously,
3,Wherever practicable,synthetic
methodologies should be designed to
use and generate substances that
possess little or no toxicity to human
health and the environment
? Multi-fold pragmatic reasons for necessarily
considering the hazard,
?It is impossible to control exposure without
increasing the cost of the process
?Exposure controls can fail and so ones risk
increases commensurately with that failure,
?We can consider
?We have no other choice
4,Chemical products should be
designed to preserve efficacy of
function while reducing toxicity
? Designing safer chemicals
Through the knowledge of the molecular
structure,chemists can obviously determine
quite a bit about the characteristics of the
compounds,
? Why it is possible to design safer chemicals?
Understanding of toxicity
Several approaches
Ways of designing safer
chemicals
If a certain reaction is essential for the
toxic mechanism to be carried out,a
structural change could be made to ensure
that the reaction could not take place,Of
course,any structural modifications would
ensure that the function and performance of
the molecule were still preserve,
If the mechanism is not known,looking for
the correlation existed between chemical
structure and the existence of toxic effect,
The functionality related to the toxic
effect would be avoided,minimized,or
eliminated to reduce or eradicate the
toxic end-point,
Minimizing the bio-availability
If a substance is toxic,yet can not reach
its target organ where its toxicity would
be manifested,then it is rendered
innocuous,
5:The use of auxiliary substances(e.g,
solvents,separation agents) should be
made unnecessary wherever possible
and innocuous when used
? Challenges facing the use of auxiliary substances
? auxiliary substances are generally used
? Concerns for solvents
? Effects of solvents on the environment
? How to eliminate auxiliary substance
? Supercritical fluids （超临界流体）
? Solventless（非溶剂化）
? Aqueous (水作溶剂 )
? Immoblized (固定化 )
6,Energy requirements should be
recognized for their environmental and
economical impacts and should be
minimized
? Energy is widely used in chemical industry
Energy generation and consumption has long
been known to include a major environmental
effect,
Chemistry and chemical transformation must
and do play a major role in capturing and
converting existing substances into energy as
well as converting existing sources of energy
into a form that is usable to society,
Is it in a sustainable situation?
Energy requirements should be
recognized for their environmental
and economical impacts and should
be minimized
? How energy is used in chemistry and chemical
industry?
? Pre-heating of the reaction mixture
? Accelerating the reaction rate with heat
? The need to control reactivity through cooling
? Separation energy requirement
? New forms of energy usage
? Microwaves
? Sonic
? Photochemical reaction and radiation promoted
reaction
Energy requirements should be
recognized for their environmental and
economical impacts and should be
minimized
? Optimizing the reaction conditions to minimize the
energy requirements
? In the past
The process engineer balance the energy
requirements
? Nowadays
The chemist who designs the reaction has the
greatest effect on what the energy requirements for a
given synthesis or manufacturing process are,
It is only through the design of the reaction
system that the inherent energy requirements can be
fundamentally changed,
7,A raw material or feed stock should be
renewable rather than depleting,wherever
technically and economically practicable
?The difference between ―renewable
resources ‖and ―depleting ones‖ is
described simply by ―time‖
? ―Depleting resources‖ are usually thought
of as the fossil fuels,
? Except for the fact that it would require millions
of years to occur,fossil fuels could be
accurately described as renewable inasmuch
as vegetation could once again be converted to
petroleum,Since this is not generally thought of
as practical,fossil fuels are considered
depleting,
7,A raw material or feed stock should be
renewable rather than depleting,wherever
technically and economically practicable
? One of the true depleting resources we have
is the Sun and solar power but that is again
subject to the criterion of time,Since the Sun
will last millions of years,it is often referred to
as an infinite supply of energy,although,
unlike fossil fuels,once it is exhausted it will
never be replenished,
7,A raw material or feed stock should be
renewable rather than depleting,wherever
technically and economically practicable
? Renewable feed-stocks are most often
associated with biological and plant based
starting materials,
? The term,however,can be equally applied to
substances that are easily regenerated within
time frames that are accessible to the human
lifetime,
? Carbon dioxide,methane
7,A raw material or feed stock should be
renewable rather than depleting,wherever
technically and economically practicable
8,Unnecessary derivations (blocking
group,protection/deprotection,
temporary modification of physical
/chemical processes)should be avoided
whenever possible
? Challenges faced by chemical synthesis and their
green chemical solutions
? Target molecules become more and more
complex;
? Stereo-control,effecting a reaction in the
presence of a labile functional group,molecular
modification,etc,
? Blocking/protecting groups
? Blocking,or protecting groups are used to
protect a sensitive moiety from the conditions
of the reaction,which may jeopardize the
functionality if it is left un protected,
? -OH,-NH2
8,Unnecessary derivations (blocking
group,protection/deprotection,
temporary modification of physical
/chemical processes)should be avoided
whenever possible
? Making salts
? It is common that certain substances need to be
formulated or blended with other substances in
order to effect their macro or performance
properties,such as viscosity,dispersability,vapor
pressure,polarizability,water solubility etc.,
8,Unnecessary derivations (blocking
group,protection/deprotection,
temporary modification of physical
/chemical processes)should be avoided
whenever possible
? Adding a functional group only to replace it
? Several reactive sites existed in a molecule
? Activate certain site
8,Unnecessary derivations (blocking
group,protection/deprotection,
temporary modification of physical
/chemical processes)should be avoided
whenever possible
9,Catalytic reagent (as selective as
possible) are superior to
stoichiometric reagents
With stoichiometric reactions,
?One of the starting material,A or B,is a limiting
reagent and therefore there will be unreacted
starting material left over even in a reaction with
100% yield,
?One or both of the starting materials are only
partially needed for the end-product and so the
balance of the molecules go to the waste stream; or
?Additional reagents are needed to carry out or
facilitate the reaction and those reagents will need
to be discarded in the waste stream when the
reaction is completed,
? The obvious effect of catalysis to facilitate
the reaction,
?Enhance the selectivity
?Minimize the energy costs
9,Catalytic reagent (as selective as
possible) are superior to
stoichiometric reagents
10,Chemical products should be
designed so that at the end of their
function they do not persist in the
environment and break down into
innocuous degradation products
? Persistent chemicals (such as
plastic)/persistent bioaccumulators
? Plastics Durability and long life were
required before
? Pesticides Organohologen structure
? Just as you design for function,consider
degradation as a function
? Designing for biodegradability
10,Chemical products should be
designed so that at the end of their
function they do not persist in the
environment and break down into
innocuous degradation products
11,Analytical methodologies need to be
developed to allow for real time,in-
process monitoring,and control prior to
the formation of hazardous subatances
? You can not control what you cannot measure
? Accurate and reliable sensors,monitors,and
analytical techniques are needed to asses the
hazards that are present in the process stream,
? In-process and in-real-time techniques(in situ) are
needed,
? Determine the completion of the reaction
12,Substances and the form of a
substance used in a chemical process
should be chosen so as to minimize the
potential for chemical accidents,including
releases,explosions,and fires
? Accident prevention should be
considered
? Consider the balance of the prevention
of both pollution and accidents
? The use of solids or low vapor pressure
substances
? The realization of,just-in-time” techniques
involve the generation and rapid
consumption of hazardous substances within
a contained process,
12,Substances and the form of a
substance used in a chemical process
should be chosen so as to minimize the
potential for chemical accidents,including
releases,explosions,and fires
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Pathway of Aromatic Bioysnthesis,J,Am,Chem,
Soc,1991,113:9361-9363,
17,朱清时, 化学的绿色化和绿色植物的化学转化,
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crystaLs,绿色化学第三届国际高级研讨会论文摘
要集,2000,104-108。
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the superstruture of narure cellulose and its
structural changes during biodegadation by STM
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摘要集,2000,109-120。
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要集,2000,163-167。
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要集, 2000,177-180。
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Synthesis,Chemical Review,1996,96(1):1-2
24,Barry M.Trost,The Atom Economy-A Search for
Synthesis Efficiency,Science 1991,254:1471-1477,
? 曾庭英、宋心琦，化学家应是“环境”的朋友 ——
介 绍绿色化学工艺，大学化学,1995,10（ 6）：
25-31。
? 刘昌俊，张悝，许根慧，催化等离子体合成燃料油
及与费耗合成的比较，第七届全国青年催化学术会
议论文集,1999,439-440。
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前沿，化学进展,1998,10（ 3）,265-272。
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化学进展,1998,10（ 2）,158-171。
29.Jocelyn Kaiser,Supercritical Solvent Comes Into
Its Own,Science,1996:158-171,
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D.C.,USA.2000.3
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for Synthetic Efficiency,Science,1991,254：
1471-1477,
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(June 19),32-35,
本章作业
? 1：简答。
绿色化学的目标、化学工业造成的危害,
风险试剂、生物质的种类、可再生资源
原子利用率、环境商、环境因子
? 2：为什么要大力发展绿色化学？
? 3：绿色化学及其与环境污染治理的异同。
? 4：什么是绿色化学品？怎样设计安全的化
学品。
? 5：举例说明原子经济反应是不产生污染的
必要条件。
? 6：试论计算机辅助绿色化学合成路线设计
的必要性和方法。
? 7：怎样在反应过程中使化学反应绿色化。
本章作业
? 8：自选一条目前使用的有机化学合成路线,
用绿色化学原理对其进行评价并设计一
条更佳的新路线。
? 9：简述绿色化学 12原则。
? 10：试论分析化学在绿色化学发展中的作为。
本章作业
? 2.1 The concept of Green Chemistry
? 2.2 Promoting the development of Green
Chemistry
? 2.3 Atom Economy of chemistry reaction
? 2.4 Atom Economy and environmental
effects
? 2.5 Research area of green chemistry
? 2.6 Twelve principles of green chemistry
References
The concept of Green
Chemistry
Green Chemistry is
investigated world-widely
Countries and areas with Green
Chemistry investigation chapters
Noyori,Importance of Green Chemistry
Without Green
Chemistry,
chemical
manufacturing
will be unable to
survive into the
22nd century,
Green Chemistry
The connotation of
Green Chemistry
A deeper view of
Green Chemistry
Green Chemistry
is realizable
Green Chemistry
is different from
environmental
control
The connotation of Green
Chemistry
? Green chemistry is an active intercrossing
research area in the world,it deals with the
frontier of chemical research,
? The traditional ways of environmental
protection just bring us about temporary
solutions for environmental problems,while
Green Chemistry provides permanent cures,
The connotation of Green Chemistry
? Green Chemistry provides ways to reduce
or eliminate environmental pollution from
the beginning,which could have eternal
benefits,
? The principles of Green Chemistry could
and should be used to all domain of
chemistry and chemical engineering,
The connotation of Green Chemistry
?No pollution should be accompanied in
chemical processes,this is to say,
eliminate the potential of pollution before it
occurs,
?The realization of this goal means no
environmental control is needed,because
there will be no pollution,
The Goal of Green Chemistry,
The connotation of Green Chemistry
? Green Chemistry is the utilization of a set
of principles to reduce or eliminate the
use of hazardous materials in the design,
manufacture and use of chemicals,and
these chemicals should be economically
and environmentally benign,
? It deals also with the reduction and
elimination of the use of hazardous
materials in the design and use of
chemical processes,
Green Chemistry
The connotation of Green Chemistry
?Green Chemistry is the application of
chemical principles,chemical technologies
and chemical methods to all chemicals and
chemical processes to reduce or eliminate
the use of hazardous starting materials,
hazardous processes,hazardous target
products,hazardous auxiliary substances
(such as solvents,separation agents) in
the production and use of chemicals,
Green Chemistry
The connotation of Green Chemistry
?Hazardous or potentially hazardous
processes should also be reduced or
eliminated,
?By-products are expected to be avoided
as thoroughly as possible,and the
starting materials be utilized as
completely as possible,thus satisfying a
sustainable civilization,
Green Chemistry
The connotation of Green Chemistry
?Green chemistry is the science which
uses chemical principles and methods
to reduce or eliminate the use of
hazardous starting materials,catalysts,
solvents,reaction agents,target
products,by-products,etc.,which are
toxic or harmful to human beings and
environment,
?It is the chemistry which could reduce
and eliminate pollution from the very
beginning and cure pollution eternally,
Environment
&
resource
Simultaneously
give out
Green
Chemistry
Solution
Recyclable
economy
Sustainable
development
Cr
ise
s
Re
qu
ire
me
nt
Green
Chemistry
Green Chemistry
The connotation of
Green Chemistry
A deeper view of
Green Chemistry
Green Chemistry
is realizable
Green Chemistry
is different from
environmental
control
Green Chemistry is realizable
?The goal of green chemistry is to seek for
perfection(by overcoming difficulties),
?Synthesis efficiency is highly thought of in
green chemistry,
?Opposite opinions,it is difficult to
quantify the toxicity and harmfulness of a
substance to human beings and to
environment,
?Examples already realized give evidences
strongly to illustrate that green chemistry is
realizable,
?Relationship between structure and
properties —— gives us clue to predict the
harmfulness of substances,
?We could compare and select the most
favorable substance and method under
specified conditions,
Green Chemistry is realizable
Green chemistry way
Bring about a
temporary
solution
Treat the
existed waste
Treat waste
Provide a
permanent cure
Eliminate waste
from the origin
No waste
produced
Not need for
waste treatment
Traditional way
Waste produced
then treat
Fa
cin
g t
he
in
cre
as
ing
en
vir
on
me
nt
al
po
llu
tio
n
Green Chemistry
The connotation of
Green Chemistry
A deeper view of
Green Chemistry
Green Chemistry
is realizable
Green Chemistry
is different from
environmental
control
Deeper viewpoints on
Green Chemistry
? Scientific viewpoints,
? Green Chemistry concerns new research area
of chemistry,It rejuvenates the contents of
chemistry,
Environmentally benign
Starting materials,target products
High selectivity,atom economy
? Economical viewpoint,
? Green Chemistry provides fundamental
principles and techniques to utilize effectively
the starting materials(resources) and energy,
meanwhile the cost of the production is
reduced,thus satisfying the requirements of
sustainable development,
Deeper viewpoints on
Green Chemistry
? Environmental viewpoint,
? Green Chemistry provides new principles
and techniques to cut down pollution
originally and eternally,
Deeper viewpoints on
Green Chemistry
? 2.1 The concept of Green Chemistry
? 2.2 Promoting the development of Green
Chemistry
? 2.3 Atom Economy of chemistry reaction
? 2.4 Atom Economy and environmental
effects
? 2.5 Research area of green chemistry
? 2.6 Twelve principles of green chemistry
References
Why
2.2 Promoting the development
of Green Chemistry
Satisfying the
demand for
sustainable
development of
human society
Satisfying the
requirement
of science and
economy
Strongly develop green
chemistry to satisfy the
demand for sustainable
development of human society
Traditional
chemical
Industry
is accompanied
by unexpected
harm (3 aspects)
No other
alternatives
exist
Green
chemistry
is the unique
solution
Environment
&
resource
Simultaneously
give out
Green
Chemistry
Solution
Recyclable
economy
Sustainable
development
Cr
ise
s
Re
qu
ire
me
nt
Green
Chemistry
Satisfying the requirement for the
development of science and economy
Chemistry itself develops in accordance
with the change of resources and of the
social requirement,
It should also be renewed in methodology
and content,
Green chemistry appears,
?Scientifically,
?Chemical industry plays an important role in
the industrial ensemble
Britain,Germany,USA
?Chemical enterprises make great effects to
reduce their cost,and increase their cost by
treating the pollutants they produced,
?Green chemistry provides new ways which
could satisfy both the demands of chemical
production,
Satisfying the requirement for the
development of science and economy Economically
? 2.1 The concept of Green Chemistry
? 2.2 Promoting the development of Green
Chemistry
? 2.3 Atom Economy of chemistry reaction
? 2.4 Atom Economy and environmental
effects
? 2.5 Research area of green chemistry
? 2.6 Twelve principles of green chemistry
References
2.3 Atom Economy of Chemical
Reaction
Atom utilization Atom economy
of chemical
reaction
Increase
the conversion of
the reactants,
the selectivity
of the products
2.3.1,Atom utilization
The concept was used to quantify
the waste (by-products) formed
when a certain amount of target
product was manufactured in a
chemical reaction,
Roger A.Sheldon 1992
Atom
utilization =
=
The amount of target product formed
╳ 100%
The amount of all products
formed stoichiometrically
The amount of reactants used
The amount of target product formed
╳ 100%
Atom utilization
The two main characteristics of chemical
reaction with 100% atom utilization,
?The reactants could be fully utilized,and the
resource could be most possibly used
economically
?The waste could be minimized
原子利用率 = 目标产物的量
按化学计量式所得所有产物的量之和
=
目标产物的量
各反应物的量之和
╳ 100%
╳ 100%
Examples
Example 1, The preparation of epoxy-
ethane from ethylene more
Example 2,The preparation of epoxy-
propane more
Example 3,The synthesis of methyl
acrylate more
Example 1
The preparation of epoxy-ethane
Traditional way
CH2=CH2 + Cl2 +
H2O
ashsska ClCH2CH2OH + HCl
ashsska ClCH2CH2OH + Ca(OH)2 +
HCl
C2H4O + CaCl2 + 2H2O
CH2=CH2 + Cl2 + Ca(OH)2 C2H4O + CaCl2 + H2O aska
28 71 74 44 111 18 ashsska ashsska
44 ashsska
111+ 18 = 129
44
111+ 18 + 44 ╳ 100% =
44
28+ 71 + 74 ╳ 100% = 25% =
Disadvantages of the
traditional method
?1,The atom utilization could reach only 25%,
i.e.,1kg of target product / 3kg of wastes,
? 2,The reactant Cl2 is harmful,it erodes the
equipment and injures human beings,thus
demanding special equipment and special
protection measure,
? 3,Separation and purification processes are
necessary to obtain useful product,
If every step could obtain 100% selectivity
and 100% yield,then
Silver catalyst is used to convert ethylene directly to the
target molecule by using oxygen as the oxidant,which gives
100% atom utilization,
New greener way
CH2=CH2 + 1/2O2 ashsska
44
C2H4O
28 16 ashsska
44
0
ashsska 44 28+16 = ╳ 100% ╳ 100% =
44
ashsska 44 = 100%
? High atom economy (100%)
? Oxygen is safe to human beings and
to environment,
? No separation or purification is
needed,
Advantages of the
new greener method
If the selectivity of the reaction could reach 100%
Example 2
The preparation of epoxy-propane
ka
42 71 58 74 111 18 ashsska asha asha
asha
58 asha
111+ 18 = 129
58
111+ 18 + 58 ╳ 100% =
58
42+ 71 + 74
╳ 100% = 31%
C3H6O + CaCl2 + H2O CH3CH=CH2 + Cl2 + Ca(OH)2
=
Traditional way
Disadvantages of the
traditional method
?1,The atom utilization could reach only 31%,
i.e.,1kg of target product / 2kg of wastes,
? 2,The reactant Cl2 is harmful,it erodes the
equipment and injures human beings,thus
demanding special equipment and special
protection measure,
? 3,Separation and purification processes are
necessary to obtain useful product,
If every step could obtain 100% selectivity
and 100% yield,then
Direct oxidation catalyzed by titania-silica
New greener way
ka
42 34 58 18
ashsska asha
asha
C3H6O + H2O CH3CH=CH2 + H2O2 Ashs ska Titania- sillica
molecular sieve
ashsska
58
18 asha
58
58 + 18 ╳ 100% =
58
42 + 34
╳ 100% = 76% = a
The amount of target
product formed
? The atom utilization is high (76 %)
? The by-product----water is
environmentally benign,
? Hydrogen peroxide is safer than
chlorine to human beings and to
environment,
Advantages of the
new greener method
If the selectivity of the reaction could reach 100%
Problem?
CH3CH=CH2 + 1/2 O2 C3H6O
Example 3
The preparation of methyl acrylate
This process uses the by-
products from phenol industry
and acrylonitrile,acetone and
hydrocyanic acid
H3CCOCH3 HCN
Traditional way
Traditional way
held
CH3C(CN)(OH) CH3 CH3COCH3 + HCN Ahs ska
CH3OOC(CH3)C=CH2 + NH4HSO4 CH3OH,H2SO4
CH3COCH3+ HCN + CH3OH + H2SO4 CH3OOC(CH3)C=CH2 + NH4HSO4 AA
100+115
╳ 100% = =
a
58
a
27 32 98 100 115
100
115
╳ 100%
100
58+27+32+98
100
AA
AA AA = 46%
AA
Disadvantages of the
traditional method
?1,The atom utilization could reach only 46%,
i.e.,1kg of target product / 1kg of wastes,
? 2,The reactant HCN is harmful,it erodes the
equipment and injures human beings,thus
demanding special equipment and special
protection measure,
? 3,Separation and purification processes are
necessary to obtain useful product,
If every step could obtain 100% selectivity
and 100% yield,then
This process utilizes the by-product
propyne CH3C≡ CH from the dissociation
(e.g,Pyrolysis) of naphtha,and carbon
monoxide,
New greener way
Using palladium acetate Pd(OAc)2 as the
catalyst,developed in 90’s
New greener way
Pd(OAc)2
? The atom utilization is high (100 %)
? Carbon monoxide and methanol are
safer than hydrocyanic acid to
human beings and to environment,
? No waste produced
Advantages of the
new greener method
If the selectivity of the reaction could reach 100%
2.3.2 Atom economy of
chemical reaction
Definition,
The ratio of atoms appeared in the target
molecules to all the atoms of the reactants
The reaction with 100% atom utilization is
ideal atom economical reaction,
1991,Barry M,Trost
1996,The Presidential Green Chemistry
Challenge Award of USA
How to design
atom economical
reactions
如何设计
原子经济反应
Deficiency of the traditional
synthetic ways
A + B C ＋ D
wa
ste
Tar
ge
t
mol
ecu
le
For a target molecule C
If the traditional way is
A + B C + D
This process inevitably produces the by-product D,
which should be treated and could be considered as
waste,
Because this is the chemical reaction,if we want to
use this reaction,we could not avoid this dilemma,
Atomic economic
reactions
E + F C
Target
product
Thus we should design new atom economical
reactions as
E + F C
Advantages,all the atoms in the reactants E
and F entered in the target molecule C,making
the atom utilization be 100%,
No by-product formed
Thus,no waste for treatment
No pollution
Problem
? The types of organic reactions,
Please answer
? Which kinds are atomically economical?
Example
The synthesis of haloalkane
Atom economy,100%
No by-product
No pollution
The consumption of
resource is minimized。
3 moles target
molecules/1mole
by-product,Waste
resources and the
by-product is a
kind of pollutant
3ROH + PX3 ?
3RX + H3PO4
RX’ + NaX
?RX + NaX’
R’CH=CH2 + HX
? RX
1mole target
molecules/1mole
by-product，
Waste resources
and the by-
product is a kind
of pollutant
Use the natural resource
more efficiently,prolong
their lifetime,
Study on atomic
economic
reactions
Chiral
technique
All atoms
from
reactants
enter into
the target
molecule
All atoms from
reactants enter
into the target
molecule
stereo-
orientatedly
Facing the dried up of natural resource?
2.3.3 Increase the conversion of the
reactants and the selectivity of the
products as thoroughly as possible
Atom economy is necessary for a
reaction to not produce waste,but it is
not enough,
Low equilibrium conversion
Parallel reactions
? 2.1 The concept of Green Chemistry
? 2.2 Promoting the development of Green
Chemistry
? 2.3 Atom Economy of chemistry reaction
? 2.4 Atom Economy and environmental
effects
? 2.5 Research area of green chemistry
? 2.6 Twelve principles of green chemistry
References
2.4,Atom Economy and
environmental effects
2.4.1,Environmental factor
It is used to quantify the effects of
production process to the environment
Idea,All other compounds formed other
than the target product are considered to
be WASTE,
Roger A.Sheldon in 1992
Environmental
factor
E= The amount of waste The amount of
target product
The larger E The more waste formed
The more serious
the pollution
If the atom
Utilization=100%
E=0
The environmental factor
of several industries
Industries Production/t E
Petrol 106 ~ 108 ~ 0.1
Fundamental
Chemicals 104 ~10 6 1 ~ 5
Fine chemicals 102 ~ 1 04 5 ~ 50
Pharmacy 10 ~ 103 25 ~ 100
But the environmental pollution is
strongly associated with the harmful
performance of the waste,
2.4.2,Environmental quotient (EQ)
The E factor just gives the ratio of
the waste and the target product,
Environmental quotient
E-----Environmental factor
Q-----The extent of hazardousness of
the waste to the environment
obtained from the performance of the
waste in the environment,
EQ＝ E× Q
Chapter 2 Green Chemistry
? 2.1 The concept of Green Chemistry
? 2.2 Promoting the development of Green
Chemistry
? 2.3 Atom Economy of chemistry reaction
? 2.4 Atom Economy and environmental
effects
? 2.5 Research areas of green chemistry
? 2.6 Twelve principles of green chemistry
References
2.5 Research areas of green
chemistry
Designing safer and effective target molecules
Seeking for safer starting materials
Seeking for safer synthetic processes
Seeking for new safer conversion ways
Seeking for safer new reaction conditions
Gr
ee
ne
r,S
afe
r
2.5.1,Designing safer and effective
target molecules
The target molecule being safe is
prior to all considerations,and it
should also be effective,
The designing of safer chemicals is the use
of the relationship between molecular
structure and properties (structure-activity
relationship,SAR) and molecular
manipulation method to obtain molecules
with maximized desired functions and
minimized harmfulness,
Designing safer and effective
target molecules
In 1983,a seminar on the designing of safer
chemicals has been hold in Washington,
Designing safer and effective
target molecules It involves two aspects,
1,The designing of new safe and
effective molecules,
2,The designing of new safer and
effective molecules to replace
the molecules which existed
effective but not benign
We have more than 18,000
thousands of compounds up to
now,while 600 thousands of
new compounds appear every
year,
Designing safer and effective
target molecules
Designing safer and effective
target molecules
Traditio al ways of finding
an effectiv molecule,
Practical needs synthesis test
synthesis test
New molecular designing ways,
Trial and errors
Practical needs designing by SAR synthesis
Guided theoretically
test
Working desk+computer
+ventilation cupboard
Designing safer and effective
target molecules
2.5.2,Seeking for New starting
materials
Seeking new starting materials to
substitute the actually used hazardous
and poisonous materials
Example 1 Using CO2 to substitute phosgene
（ 光气 ） in the synthesis of polyurethane(聚氨酯 )
Example 2 Elimination the use of hydrocyanic
acid（ 氢氰酸 )
Example 3 The synthesis of adipic acid（ 己二
酸 ） using new safe starting materials
Eliminating the poisonous phosgene in
the synthesis of polyurethane
and polycarbonate
Example 1 Cl
C
Cl
O
Polycarbonate(聚碳酸酯 )
Phosgene is widely used for
the production of,
isocyanate (异氰酸酯 )
polyurethane(聚氨酯 )
Isocyanate is first synthesized by the reaction
of phosgene and amine,and then using
isocyanate to produce polyurethane,
Traditional way
按照化学
RNH2 + COCl2 RNCO + 2HCl
RNHCO2R1
The synthesis of isocynate
What kinds of functional group would
phosgene provide in a chemical reaction?
Which kind of compound could be
employed to substitute phosgene?
providing -CO group
Cl
C
Cl
O
Carbon dioxide is used to substitute
phosgene in the production of
isocyanate (providing carbonyl group)
The function of phosgene,providing -CO group
按照化学
RNH2 + CO2 RNCO + H2O
RNHCO2R1
New greener way
按照化学
The synthesis of isocyanate using CO2
C6H5NH2 + CO2 C6H5N(H)CO2H
C6H5N=C=O
–H2O
Aniline
按照化学
2CH3OH + COCl2 CH3OOCOOCH3 + 2HCl
2CH3OH + CO + ? O2 CH3OOCOOCH3 + H2O Catalyst
2CH3OH + CO2 CH3OOCOOCH3 + H2O
Thermodynamics,Catalyst,
Reaction conditions,temperature/pressure
The synthesis of di-methyl carbonate
Traditional way
New greener ways
The elimination of the use of HCN
(hydrocyanic acid) (hydrogen cyanide,
prussic acid) by changing the process
Example 2 C NH
Hexane dinitrile(己二腈 );
Series of methylpropenoic acid(甲基丙
烯酸系列 );
Series of intermediate chemicals such
as chelator / chelating agent(螯合剂 ),
methionine (蛋氨酸 ) etc,
Hydrocyanic acid HCN is widely
used for the production of,
The synthesis of sodium iminodi-acetate
(亚氨基二乙酸二钠 )
Traditional way
involves two steps,
按照化学
NH3 + 2CH2O + 2HCN
— ① NCCH2NHCH2CN
— ② + 2NaOH → NaO 2CCH2NHCH2 CO2Na + NH3
A new starting material
HOCH2CH2NHCH2CH2OH
(diethanolamine,二乙醇胺 ) is used
New greener way
Replacing HCN
The synthesis of adipic acid ( /hexanedioic acid
己二酸 ) and hexamethylene diamine (己二胺 )
CH2=CHCH=CH2 + HCN NCCH2CH2CH2CH2CN
HOOC(CH2)4COOH
H2N(CH2)6NH2
Traditional method
Replacing HCN
C6H12
The oxidation of Cyclo-hexane(环己烷 )
Oxidation
HOOC(CH2)COOH
The hydrocarbonylation of butadiene
CH2=CHCH=CH2 + 2CO + 2H2 OHC(CH2)4CHO
HN=CH(CH2)4CH=NH
H2N(CH2)6NH2 HOOC(CH2)COOH
O2
catalyst
2NH3 - 2H2O
2H2
New greener methods
Replacing HCN
The synthesis of phenyl acetic acid
C6H5CH2Cl +HCN C6H5CH2CN + HCl C6H5CH2COOH H2O
C6H5CH2Cl + CO C6H5CH2COOH
OH– / H2O
Traditional way
New greener way
Can we design another green way to
synthesize phenyl acetic acid with
ethylbenzene and oxygen as reactant?
C6H5CH2CH3 + O2 C6H5CH2COOH
If can’t,why?
Example 3
The synthesis of adipic acid by
changing starting material
Traditional way
Could anyone tell me the
disadvantages of this method
? Photochemical smog
? Depletion of ozone,
? Acid rain
Disadvantages of the
traditional method
The starting material (Benzene) is
hazardous (carcinogentic)
The release of nitrogen oxides which
are multifunctional pollutants
Use of heavy metals (cobalt)
Elimination of the use of solvent,the use of
hazardous benzene,the corrosive capacity
of hydrogen peroxide is not as severe as
nitric acid,no pollutants produced,
Kamzuhiko Sato,1998,Science,281:1646-1647
按照化学
H OO C
C OO H+ 4 H 2 O 2
Na 2 WO 4
[ C H 3 ( n - C 8 H 17 ) 3 N ]H S O 4
P h as e T r an sfer C ataly st
New greener method 1
The synthesis method is widened,
Drath and Frost,1990,1991
按照化学
O
O H
O H
O H
O H
OH
C OOH
O H
O H
O
H OOC
C OOH
P l a tniu m
c a ta l y s t
New greener method 2
Not only eliminate the use of benzene,
but also develop a new method to use
renewable biomass(glucose),
Using of renewable starting material
150 years ago,industrial
organic chemicals were all
derived from biomass
originated from plants
The use of biomass as starting material
for energy and chemicals production
regain much attention,because of its
renewability,
Coal Oil Natural gas Coal
Starting materials Biomass Industrial revolution
One kind of solar energy
Using of renewable starting material
Security and Energy Resources
Oil,30-50 years
Natural Gas,50-100 years
Coal,200-400 years
It must degenerate before it
could be effectively used,
Biomass,Starch (淀粉,amylum)
+ Lignin (木质素,lignine)
Lignin,164 billion ts /year
amount used <1.5%
Using of renewable starting material
Security and Energy Resources
Oil,30-50 years
Natural Gas,50-100 years
Coal,200-400 years
Examples
Using of renewable starting material
plants,trees,crops,grasses,aquatic
plants and their residues or waste
materials,
? 5 hundreds million tons of wheat straw;
? 10 million tons of rice bran;
? 10 million tons of corncob;
? 20 million tons of rice hull;
? 7 million tons of biogases;
Using of renewable starting material
about 2.8～ 3.5 hundreds million of tons
can be used as resource of energy,
/year In China,
The burning of straw:,waste of
resource while polluting
? The structure of lignin and its effect on
its degradation
? Orientated degradation to produce
directly useful chemicals
Using of renewable starting material
Fundamental scientific challenge,
Technical challenges,
? Continuous operation
? Separation of the products
Using of renewable starting material
Actual progresses
Cross
Agricultural waste (polysaccharides)
Naturally degradable polymer
Sichuan University,University of Science and
Technology,Shandong University,Chemical
Institute Academy of China,Guangzhou
Biomass
Animal feeds
Fuel
Chemicals
Using of renewable starting material
Haltzapple from Texas A & M university
1996,The presidential Green Chemistry Award
Converting biomass to fuel and chemicals
Direct liquation
Biomass
Liquid fuel &
chemicals
Indirect conversion
Gasification
C3-C4
Gases
Gas
fuel
CO + H2
Liquid fuel &
chemicals
Catalytic
conversion
Using of renewable starting material
Gasification reactor (fixed bed)
for biomass conversion
gasifier
purification
fan gas tank
Needed
By
Home
biomass,air
Gasification reactor (fluidized
bed) for biomass conversion
gasifier
biomass
tank
CO + 2H2=
CH3OH
reforming reaction bed
biomass
Gasification reactor (fluidized
bed) for biomass conversion
Gas
production：
150 M3/h
Operation
pressure：
1MPa
Heat capacity：
7 MJ/M3
Efficiency of
energy
conversion：
80%
Fast-
growing
bamboo
Fast-
growing
shrubs
Convert biomass to useful
products green chemically
将
生
物
质
转
化
为
化
学
化
工
原
料
开
发
新
资
源
实
现
资
源
持
续
利
用
Agricultural waste
Chemical research based on
energy resources
Biomass
Coal
Oil
Coal
Natural Gas
Chemistry
Treating
? CnH2n± x
? CH4
? C
Treating
? CnH2nOn
? C
? CO2
2.5.3,Seeking and designing
safer and effective synthetic routes
Ideal synthetic route
Paul A Wender 1996
the starting material used should be the
cheapest and most feasible;
the operation and manipulation should be
simple,safe and environmentally benign;
the reaction rate should be fast and the yield
of the target products,either natural or
designed by ourselves,should be as high as
possible,
? The synthetic route is a very important factor to
the benignity of a process,
? The integration of chemical reactions to make
the whole process benign,
? Computer aided designing of synthetic route
Designing proper synthetic route
Example,The synthesis of para-phenylene
diamine （对苯二胺,ursol ） from
nitrobenzene (硝基苯,mirbane oil)
The synthesis of para-phenylene
diamine from nitrobenzene
Let us analyze four possible routes in a
green chemistry viewpoint
Example
The synthesis of para-phenylene
diamine from nitrobenzene
Let us analyze four possible routes
in a green chemistry viewpoint
Route 1
NO
2
N H
2
N H C O C H
3
+ 3 F e + 6 H C l
- 3 F e C l
3
- 2 H
2
O
+ ( C H
3
C O )
2
O
- C H
3
C O O H
N H C O C H
3
NO
2
N H
2
NO
2
N H
2
N H
2
+ H N O
3
/ H
2
SO
4
- H
2
O
+ H
2
O / H
+
- C H
3
C O O H
+ 3 F e + 6 H C l
- 3 F e C l
3
- 2 H
2
O
?The amounts of reactants,1062
?Target molecule,108
?Waste,954
?Atom utilization,
The overall reaction
10%
按照化学
Route 2
NO
2
N H
2
N H C O C H
3
+ ( C H
3
C O )
2
O
- C H
3
C O O H
N H C O C H
3
NO
2
N H
2
NO
2
N H
2
N H
2
+ H N O
3
/ H
2
SO
4
- H
2
O
+ H
2
O / H
+
- C H
3
C O O H
R a n y N i c k e l c a ta l y ti c
h y d r o g e n a ti o n,- 2 H
2
O
R a n y N i c k e l c a ta l y ti c
h y d r o g e n a ti o n,- 2 H
2
O
The overall reaction
?The amounts of reactants,300
?Target molecule,108
?Waste,192
?Atom utilization,36%
按照化学
Route 3
NO
2
N H
O
NO
2
+ 1 / 2 O
2
/ O H
-
- H
2
O
NO
2
N H
2
N H
2
N H
2
+ N H
3
/ Me O H
+ 3 F e + 6 H C l
- 3 F e C l
3
- 2 H
2
O
C O N H
2
C O N H
2
-
The overall reaction
?The amounts of reactants,543
?Target molecule,108
?Waste,435
?Atom utilization,20%
按照化学
Route 4
NO
2
N H
O
NO
2
+ 1 / 2 O
2
/ O H
-
- H
2
O
NO
2
N H
2
N H
2
N H
2
+ N H
3
/ Me O H
c a ta l y ti c a l
h y d r o g e n a ti o n c a ta l y ze d
b y R a n y N i c k e l
- H
2
O
C O N H
2
C O N H
2
-
The overall reaction
?The amounts of reactants,162
?Target molecule,108
?Waste,54
?Atom utilization,67%
Aggregative analysis
From the viewpoint of atom economy,route
4 is the most favorable comparing to
others。
In routes 1 & 2,because of the protection of
-NH2 in nitration,one mole of acetic
anhydride is needed and 2 moles of acetic
acid are formed as waste,while in routes 3
& 4,the protection step was not needed,
Practical need,
great amount of possible routes
for
a giving target molecule,
Computer aided
designing of synthetic route
Corey and Bersohn,30 years ago
used computer to help designing
of synthetic route
30 ? 30× 30 ? 30 × 30× 30 ?
…… ?305 > 24 million routes
Computer aided
designing of synthetic route
e,g,If the synthesis of a compound needs
5 steps,and 30 methods are possible
for each step,thus we will have
The progress
of computation technology
Computer aided
designing of synthetic route
The progress
in computer science and technology
? Construction of a data base of chemical
reactions as complete as possible,
? Put forward our requirement
? Let the computer give us the possible
starting materials which could form the
target molecule
Te
ch
nic
al
Wa
y
Computer aided
designing of synthetic route
? Further search for the starting material
using the former starting material as the
target molecules…………
until the provided starting material is
needed
? Compare all possible routes,and choose
the most favorable one from the viewpoint
of economical and environmental effect,
Te
ch
nic
al
Wa
y
Computer aided
designing of synthetic route
2.5.4 Seeking for new conversion
methods
Catalytic plasma more
Electrochemical conversion more
Photo and other radiation conversion
more
Seeking for
unconventional conversion ways
The synthesis of gasoline from carbon
dioxide and natural gas(methane,甲烷 )
CO2 + CH4 2CO + 2H2 Gasoline → →
Nickel catalyst FT process
Changjiun Liu,Tianjing University
Traditional thinking up
CO2 + CH4 Gasoline
Catalyst & plasma
condition
Plasma,
breaking of the
reactant molecules
Catalyst,
forming of the
product molecules
Catalytic plasma
Using electrochemical ways
? Electricity can be used not only as an
energy supply for chemical reactions,it
could also affect chemical reaction in
different aspects and provide new ways
for it to occur,
? The following example will give us
some direct information,
Using electrochemical ways to eliminate the
use of hazardous starting materials and make
the reaction to occur at moderate conditions
Cyclization reaction
O
OM e
Br
C H
3
C H
3
OCH 3 C H 3
electr on /V it B 12
CH
3
OH
O
OH
C H
3
CH
3
C H
3
C H
3
O
The electro-synthesis of epoxy propane
Unfortunately,the selectivity of this route is not as
good as expected,and is not yet industrialized,
Using electrochemical ways
At the anode
H2O-NaCl
CH 3 C H C H 2 CH 3 C H
O H
C H 2
Cl
At the cathode
CH 3 C H
O H
C H 2
Cl
CH 3 CH C H 2
O
? The synthesis of hexafluoropropylene oxide
F2CH=CFCF3
PbO2/Steel/anode Steel/cathode
H2O-HOAc-HNO3
The conversion,65-75%,Selectivity,90%
This route has already been industrialized
by Hoechst Company
Using electrochemical ways
CF3CFCF2
O
Using electrochemical ways
? The synthesis of para-diphenylamine
from aniline by electrolysis
C6H5NH2
H2O-NH4I/Pt
NH3
I -NH2
NH2 -NH2
? The electrosynthesis of
hydrochinone(hydroquinone,hydroquinol)
At the anode
C6H6 +2 H2O + 6H+
At the cathode
OH
OH
O O
Using electrochemical ways
C6H6 + 2 H+ + 2e
?The cycle open reaction of dioxane (二恶烷 )
,O- or S-hetero cyclohexane (氧硫杂环已烷 )
use heavy metal catalyst traditionally,and
additional reactants are needed,
?Epling etc use light as the reacting agent to
realize these reaction and avoid the pollution
caused by heavy metals
Photo and other radiation conversion
S S
O
C H
3
S S
C H
3
O
hv
97%
94%
O
O
S
S
O
O
O
H
hv
hv
91%
2.5.5 Seeking for Safe and effective
reaction conditions
? Seeking for safe and effective catalyst
Loading of active component on suitable
support more
Replacing liquid acids by solid acids more
?Example 1
?Example 2
? Seeking for safe and effective reaction medium
Using supercritical fluid as reaction medium
more
Using water as reaction medium more
?Example 1（ hydroformylation of propylene）
Loading of active components
on suitable support
?Traditional Friedel-Crafts reactions,
hydrofluoric acid(氢氟酸 ),sulfuric acid(硫
酸 ),aluminium chloride(三氯化铝 ),boron
fluoride(三氟化硼,boron trifluoride) are
used as the catalysts,
The disadvantages,
? The operation must be done anhydrously
(water free),3 moles of hydrogen chloride
will be released when accounting water,
? The system is corrosive,strict operation
conditions must be controlled,
? Low selectivity because of the formation of
poly-alkyl-substituted products and other
isomers,
Loading of active components
on suitable support
? In acylation reactions(酰基化 )such as ordinary
acylation,the formylation of benzene(苯甲酰化 ),
sulfo-acylation(磺酰化 ),large amount of
aluminium chloride is needed becaues of the
complexity of the products,
? Finally,water must be added to release the
product molecule and thus releasing large
amount of hydrogen chloride as well as
chlorinated hydrocarbons as impurity,
Loading of active components
on suitable support
? The supported catalyst K10-AlCl3,prepared by
supporting AlCl3 on montmorilonite(蒙脱土,imvite)
shows activity as high as the conventional ones and
higher selectivity for the formation of mono-
alkylated product than the old ones,
? The supporting of ZnCl2 on montmorilonite (蒙脱
土,imvite) could also obtain a new kind of catalyst
for the Fridel-Crafts reactions,and this already
provides a new perspective for industrial application,
Loading of active components
on suitable support
Using solid acids to replace
liquid acids
Acidic clay(酸性白土 ),mixed chlorides,
molecular sieve(分子筛 ) etc,could be
used to replace liquid acids,
? （ 1）,Some inevitable barriers that could
not be overcome in homogeneous catalysis
could be lowered in a certain degree or totally
overcome,
? （ 2）,The temperature range could be
widened to 700-800K,and thus widening the
range of acid catalysis,
Example 1,The traditional Fridel-Crafts
acylation reaction,
Target product/Aluminium chlorode,1/3
C O C l
Cl
Cl
O
+
E n v i ro c a t E P Z G
140
0
C,2 4 h
The use of new catalyst Envirocata,EPZG to replace
AlCl3,the amount of catalyst could be reduced to 1/10 of the
traditional one,the amount of waste (HCl) is reduced to ?,
while the yield of the target product increased to 70%,and
the selectivity of the is increased,the amount of ortho-
substituted product is reduced to trace
Problem
Complete the reactions in
example 1,compare their
atom utilization and discuss
their advantages and
disadvantages,
Using supercritical fluid (scf.)
as reaction medium
? The characteristics of scf,
Cheap,safe and property adjustable,Scfs
show different property under different
conditions,we can adjust the supercritical
conditions to adjust its property until it
satisfy our needs for the reaction to occur,
Supercritical carbon dioxide,
? Tanko used SCF CO2 as the reaction medium for
the brome substitution reaction of alky-
substituted-aromatics,equivalent or higher yield
and selectivity were obtained,
? Chemical Institute of guangzhou,
? SCF CO2 was used as both the reaction medium
and reactant in the carbonylation（羰基化） of
olefin(烯烃 )
? SCF water
? SCF water + carbon dioxide
Using supercritical fluid (scf.)
as reaction medium
Bi-phase catalysis using
water as reaction medium
? Water-soluble complex compounds could
be used as catalyst,and then the reaction
takes place at the interface formed
between the water phase and the organic
phase of the reactants,
? Micelle could be provided by varying the
central atom and the ligand as well as the
use of surfacants,thus the interface could
be enlarged and the regional concentration
of the reactants could be increased,
? By varying the structure of the micelle,the
stero-structure of the product could also be
controlled,
Bi-phase catalysis using
water as reaction medium
? Thus,mild reaction conditions,high
activity and selectivity could be afforded
for and the separation of organic phase and
water phase becomes easy,Meanwhile,
environmental pollution could be avoided,
Bi-phase catalysis using
water as reaction medium
Example 2,The alkylation of benzene
with ethylene Forming ethyl benzene
? Traditional way,AlCl3,BF3,HF were
used as the catalysts
?Serious corrosion of the equipment
?Strict operation conditions
?Low yield
?Difficulties to eliminate HCl,RCl
?Difficulties of the separation of the catalyst and
the products
?Waste water
?Hazardous HF used
? The use of phosphorus ZSM –5 molecular
sieve overcomes the above shortcomings
Traditional way,Co-based catalyst,
high pressure is needed
Rh- or Pd-based water-soluble catalyst
Bi-phase catalysis
2.6 Twelve Principles
of Green Chemistry
1
3
5 7
9
11
2
4
6
8
10
12
1:It is better to prevent waste than to
treat or clean up waste after it is
formed
? Normal cost,
? starting material and reagent (intrinsic)
? the treatment and disposal of chemicals
? Large chemical companies in U.S.,
? expenditures on research and development
≈expenditures on environmental health and safety
? The costs of dealing with hazardous substances,either
through handling,treatment,or disposal,have continued to
increase substantially
1,It is better to prevent waste than to
treat or clean up waste after it is
formed
? A criterion that is often assessed to calculate the need or
desire for treatment or control of a chemical substance is
whether or not damage has been done by the generation
of waste,
? In many cases the,damage” is merely that substances
have been uselessly processed or transformed,costing
energy,money,time for separation from product,and
almost always requiring technology to get rid of them or
to render them innocuous,
1,It is better to prevent waste than
to treat or clean up waste after it is
formed
? One type of waste production that is both common and
often the most avoidable is starting material or reagent
that is unconverted,
? When one wastes starting material,one is paying for the
substance twice; once as a feedstock and again as a
waste and so one has achieved no utility from the
substance,More seriously,often the cost of waste
disposal may be many times the cost of the virgin starting
material,
? Thus,if possible,it is better to cut pollution from its origin
rather it is formed,
2,Synthetic methods should be
designed to maximize the
incorporation of all materials used
in the process into the final product
? The classic evaluation of the effectiveness
and efficiency of a synthesis is ―Yield‖,
? This ―Yield‖ totally ignores the use or
generation of any undesirable products
that are an intrinsic part of the synthesis,
? It is better to use atom economy to
evaluate synthesis ways,
? Atomically economy reactions
? Rearrangements
? By definition,a rearrangement reaction is a
reorganization of the atoms that make up the
―old‖ molecule,Thus all atoms in the
reactants are incorporated into the product,
? Addition reactions
? Because addition reactions add the elements
of the reactant to a substrate with total
inclusion (e.g,cycloadditions,bromination of
olefins),they are atomic economical,
2,Synthetic methods should be
designed to maximize the
incorporation of all materials used
in the process into the final product
? Non atomic economical reactions
?Substitution
? Because in this kind of reaction,one
group(the substituting group) displaces a
leaving group,the leaving group is
necessary a waste product of the reaction
that is not included in the final product
and therefore diminishes the atom
economy of the transformation,The exact
degree to which the reaction is non-atom
economical is dependent on the specific
reagents and substrates used,
2,Synthetic methods should be
designed to maximize the
incorporation of all materials used
in the process into the final product
?Elimination
? Elimination reactions transform the
substrate by reducing the atoms to
generate the final product,
? The eliminated atoms are lost as waste,
2,Synthetic methods should be
designed to maximize the
incorporation of all materials used
in the process into the final product
3,Wherever practicable,synthetic
methodologies should be designed
to use and generate substances that
possess little or no toxicity to human
health and the environment
? The fundamental basis of green chemistry is the
incorporation of hazard minimization or elimination
into all aspects of the design of the chemistry,
? Green chemistry recognizes that it is through the
skills and knowledge possessed by chemists that
today’s world can have the modern technological
advances that have come to be expected from the
scientific community in a way that is safe for
human health and the environment,
3,Wherever practicable,synthetic
methodologies should be designed to
use and generate substances that
possess little or no toxicity to human
health and the environment
? There are only two ways to minimize risk of harm of any
kind,
? Minimize the exposure
? A variety of forms could be taken,protective clothing,
engineering control,respirators etc,
? It is virtually impossible to control exposure without
increasing the cost of the process,
? Exposure controls can fail,and so ones risk increases
commensurately with that failure,
? Minimize the hazard
? The intrinsic characteristics that is not going to change and
therefore the risk will not increase spontaneously,
3,Wherever practicable,synthetic
methodologies should be designed to
use and generate substances that
possess little or no toxicity to human
health and the environment
? Multi-fold pragmatic reasons for necessarily
considering the hazard,
?It is impossible to control exposure without
increasing the cost of the process
?Exposure controls can fail and so ones risk
increases commensurately with that failure,
?We can consider
?We have no other choice
4,Chemical products should be
designed to preserve efficacy of
function while reducing toxicity
? Designing safer chemicals
Through the knowledge of the molecular
structure,chemists can obviously determine
quite a bit about the characteristics of the
compounds,
? Why it is possible to design safer chemicals?
Understanding of toxicity
Several approaches
Ways of designing safer
chemicals
If a certain reaction is essential for the
toxic mechanism to be carried out,a
structural change could be made to ensure
that the reaction could not take place,Of
course,any structural modifications would
ensure that the function and performance of
the molecule were still preserve,
If the mechanism is not known,looking for
the correlation existed between chemical
structure and the existence of toxic effect,
The functionality related to the toxic
effect would be avoided,minimized,or
eliminated to reduce or eradicate the
toxic end-point,
Minimizing the bio-availability
If a substance is toxic,yet can not reach
its target organ where its toxicity would
be manifested,then it is rendered
innocuous,
5:The use of auxiliary substances(e.g,
solvents,separation agents) should be
made unnecessary wherever possible
and innocuous when used
? Challenges facing the use of auxiliary substances
? auxiliary substances are generally used
? Concerns for solvents
? Effects of solvents on the environment
? How to eliminate auxiliary substance
? Supercritical fluids （超临界流体）
? Solventless（非溶剂化）
? Aqueous (水作溶剂 )
? Immoblized (固定化 )
6,Energy requirements should be
recognized for their environmental and
economical impacts and should be
minimized
? Energy is widely used in chemical industry
Energy generation and consumption has long
been known to include a major environmental
effect,
Chemistry and chemical transformation must
and do play a major role in capturing and
converting existing substances into energy as
well as converting existing sources of energy
into a form that is usable to society,
Is it in a sustainable situation?
Energy requirements should be
recognized for their environmental
and economical impacts and should
be minimized
? How energy is used in chemistry and chemical
industry?
? Pre-heating of the reaction mixture
? Accelerating the reaction rate with heat
? The need to control reactivity through cooling
? Separation energy requirement
? New forms of energy usage
? Microwaves
? Sonic
? Photochemical reaction and radiation promoted
reaction
Energy requirements should be
recognized for their environmental and
economical impacts and should be
minimized
? Optimizing the reaction conditions to minimize the
energy requirements
? In the past
The process engineer balance the energy
requirements
? Nowadays
The chemist who designs the reaction has the
greatest effect on what the energy requirements for a
given synthesis or manufacturing process are,
It is only through the design of the reaction
system that the inherent energy requirements can be
fundamentally changed,
7,A raw material or feed stock should be
renewable rather than depleting,wherever
technically and economically practicable
?The difference between ―renewable
resources ‖and ―depleting ones‖ is
described simply by ―time‖
? ―Depleting resources‖ are usually thought
of as the fossil fuels,
? Except for the fact that it would require millions
of years to occur,fossil fuels could be
accurately described as renewable inasmuch
as vegetation could once again be converted to
petroleum,Since this is not generally thought of
as practical,fossil fuels are considered
depleting,
7,A raw material or feed stock should be
renewable rather than depleting,wherever
technically and economically practicable
? One of the true depleting resources we have
is the Sun and solar power but that is again
subject to the criterion of time,Since the Sun
will last millions of years,it is often referred to
as an infinite supply of energy,although,
unlike fossil fuels,once it is exhausted it will
never be replenished,
7,A raw material or feed stock should be
renewable rather than depleting,wherever
technically and economically practicable
? Renewable feed-stocks are most often
associated with biological and plant based
starting materials,
? The term,however,can be equally applied to
substances that are easily regenerated within
time frames that are accessible to the human
lifetime,
? Carbon dioxide,methane
7,A raw material or feed stock should be
renewable rather than depleting,wherever
technically and economically practicable
8,Unnecessary derivations (blocking
group,protection/deprotection,
temporary modification of physical
/chemical processes)should be avoided
whenever possible
? Challenges faced by chemical synthesis and their
green chemical solutions
? Target molecules become more and more
complex;
? Stereo-control,effecting a reaction in the
presence of a labile functional group,molecular
modification,etc,
? Blocking/protecting groups
? Blocking,or protecting groups are used to
protect a sensitive moiety from the conditions
of the reaction,which may jeopardize the
functionality if it is left un protected,
? -OH,-NH2
8,Unnecessary derivations (blocking
group,protection/deprotection,
temporary modification of physical
/chemical processes)should be avoided
whenever possible
? Making salts
? It is common that certain substances need to be
formulated or blended with other substances in
order to effect their macro or performance
properties,such as viscosity,dispersability,vapor
pressure,polarizability,water solubility etc.,
8,Unnecessary derivations (blocking
group,protection/deprotection,
temporary modification of physical
/chemical processes)should be avoided
whenever possible
? Adding a functional group only to replace it
? Several reactive sites existed in a molecule
? Activate certain site
8,Unnecessary derivations (blocking
group,protection/deprotection,
temporary modification of physical
/chemical processes)should be avoided
whenever possible
9,Catalytic reagent (as selective as
possible) are superior to
stoichiometric reagents
With stoichiometric reactions,
?One of the starting material,A or B,is a limiting
reagent and therefore there will be unreacted
starting material left over even in a reaction with
100% yield,
?One or both of the starting materials are only
partially needed for the end-product and so the
balance of the molecules go to the waste stream; or
?Additional reagents are needed to carry out or
facilitate the reaction and those reagents will need
to be discarded in the waste stream when the
reaction is completed,
? The obvious effect of catalysis to facilitate
the reaction,
?Enhance the selectivity
?Minimize the energy costs
9,Catalytic reagent (as selective as
possible) are superior to
stoichiometric reagents
10,Chemical products should be
designed so that at the end of their
function they do not persist in the
environment and break down into
innocuous degradation products
? Persistent chemicals (such as
plastic)/persistent bioaccumulators
? Plastics Durability and long life were
required before
? Pesticides Organohologen structure
? Just as you design for function,consider
degradation as a function
? Designing for biodegradability
10,Chemical products should be
designed so that at the end of their
function they do not persist in the
environment and break down into
innocuous degradation products
11,Analytical methodologies need to be
developed to allow for real time,in-
process monitoring,and control prior to
the formation of hazardous subatances
? You can not control what you cannot measure
? Accurate and reliable sensors,monitors,and
analytical techniques are needed to asses the
hazards that are present in the process stream,
? In-process and in-real-time techniques(in situ) are
needed,
? Determine the completion of the reaction
12,Substances and the form of a
substance used in a chemical process
should be chosen so as to minimize the
potential for chemical accidents,including
releases,explosions,and fires
? Accident prevention should be
considered
? Consider the balance of the prevention
of both pollution and accidents
? The use of solids or low vapor pressure
substances
? The realization of,just-in-time” techniques
involve the generation and rapid
consumption of hazardous substances within
a contained process,
12,Substances and the form of a
substance used in a chemical process
should be chosen so as to minimize the
potential for chemical accidents,including
releases,explosions,and fires
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本章作业
? 1：简答。
绿色化学的目标、化学工业造成的危害,
风险试剂、生物质的种类、可再生资源
原子利用率、环境商、环境因子
? 2：为什么要大力发展绿色化学？
? 3：绿色化学及其与环境污染治理的异同。
? 4：什么是绿色化学品？怎样设计安全的化
学品。
? 5：举例说明原子经济反应是不产生污染的
必要条件。
? 6：试论计算机辅助绿色化学合成路线设计
的必要性和方法。
? 7：怎样在反应过程中使化学反应绿色化。
本章作业
? 8：自选一条目前使用的有机化学合成路线,
用绿色化学原理对其进行评价并设计一
条更佳的新路线。
? 9：简述绿色化学 12原则。
? 10：试论分析化学在绿色化学发展中的作为。
本章作业
