Catalysis in Organic Synthesis
有机催化组
Group Members
Xu Jie (Prof., Dr., Group Head)
Wang Fudong
(Professor)
Zheng Changtu (Associate Professor)
Liu Jing (Associate Professor ,MS)
Zhang Wei (Research Associate, MS)
Li Decai (Research Associate)
Sun Caixia (Assistant Researcher, MS)
Zhao Hongmei (Assistant Researcher)
研究队伍
徐
杰（教授,博士,组长）
王复东（研究员）
郑长土（副研究员）
刘
菁（副研,硕士）
张
伟（助研,硕士）
李德才（助研）
孙彩霞（研实员,硕士）
赵红梅（研实员）
Post Graduate Students
Mr. Wang Feng
（王
峰）
Mr. Wu Wenhai
（吴文海）
Mr. Zhou Lipeng
（周励鹏）
Mr. Gao Xiaohan
（高霄汉）
Ms. Lu Fang
（路
Ms. Wei Yin
（魏
Assistant members
Ms. Zhangshoue
( 张守娥)
Ms. Wanglijuan (王丽娟)
Ms. Zhaoqiuli
(赵秋丽)
Mr. Dongkunpeng(董坤鹏)
芳）
音）
Ms. Zhou Xiaoshuang (周晓霜）
Ms. Wang Meihan
（王美函）
Ms. Zhu Dan
（朱
丹）
Advisor of The Group
Prof. Liao Shijian
Prof. Xu Yun
(廖世健)
（徐
筠）
Group Members
Prof. Xu jie
Research Fields


Catalytic Hydrogenation and Oxidation
Advanced Polymer Materials for Spacecraft Applications
 Catalytic Synthesis of Halo-Containing Organic Chemicals
 Advanced Materials in Catalysis
Research Subjects (1)
 Catalytic hydrogenation

Cyclohexene from benzene

Cyclopentene from dicyclopentadiene
Research Subjects (2)
 Catalytic oxidation

Cyclohexanone from cyclohexane

p-Hydroxybenzaldehyde from p-cresol

1,5-Glutaldehyde from cyclopentadiene
Research Subjects (3)

Advanced Polymer Materials for Spacecraft Applications

National 863-2 Program

Polyimide Sheet and Polyimide Film
Research Subjects (4)
 Catalytic Synthesis of Fluoro-Containing Organic Compounds


Fluoro-Containing Pyridine Derivatives

2-Chloro-5-trifluoromethyl pyridine

2,3-Dichloro-5-trifluoromethyl pyridine
Fluoro-Containing Benzene Derivatives
 3,5-Bis (trifluoromethyl) aniline
 2,6-Dichloro-4-trifluoromethyl aniline
 2,3,5,6-Tetrafluorobenzoic acid
 2,3,5,6-Tetrafluorobenzyl alcohol
Research Subjects (5)
 Catalytic Synthesis of Chloro-Containing Organic Compounds

Chloro-Containing Pyridine Derivatives
 2-Chloro-5-chloromethyl pyridine
 2-Chloro-5-trichloromethyl pyridine
 2,3-Dichloro-5-trichloromethyl pyridine

Chloro-Containing Benzene Derivatives
 2,3,5,6-Tetrachloro-1,4-dicyanobenzene
 4-trichloromethyl aniline
Research Subjects (6)

Other processes and products

Catalytic Synthesis of cis-2,6-Dimethylpiperazine

Comprehensive Application of

Adamantane and Its Derivatives

Synthesis and Application and C5 fine chemicals

Catalytic
Dechlorination
C5 Factions
of
Polychlorobiphenyls
(PCBs) in Transformer Oil

Catalytic Hydrogenation of Oil for Arsenical Removing
Research Subjects (7)

Catalysts and catalytic materials

Nanoscale metal particles and its oxide catalysts

Catalyst
for
cyclopropanation
1,1-dichloro-4-methyl-1,3-pentadiene

Catalysts for arsenical removing

Catalyst for selective chlorination

Catalyst for selective hydrogenation

Catalyst for selective oxidation

Catalyst for decomposition of formic acid
of
Main Instruments

100ml Hastlloy equipment
for heterogeneous catalytic
fluorination and chlorination

100ml fixed-bed heterogeneous catalytic equipments for
hydrogenation and oxidation

2000ml Parr (U.S) Monel alloy autoclave

600ml Parr (U.S) Monel alloy autoclave

300ml autoclave ( 30.0Mpa, 350C)

500ml autoclave ( 30.0Mpa, 300C)

HP-4890 gas chromatograph (U.S)

Shimadzu(Japan) liquid chromatograph

Equipment for BET surface area measurement
Patents and publications

Patents（1999-2000）：9
including 7 accepted applications
申请中国专利：
1 甲酸气相催化脱水制备高纯一氧化碳的方法
2 一种氟灭酸的制备方法
3 一种脱砷催化剂
4 一种阻燃的金属盐/聚酰亚胺复合材料
5 一种 2-（4-羟基苯氧基）丙酸丁酯的合成方法
6 一种高收率催化合成金刚烷的方法
7 一种合成 2-氯-5-三氟甲基吡啶的方法
授权中国专利
８卤代烃催化加氢脱卤反应，
授权日：990206，证书号：44156。
９纳米尺寸氮化镁的合成方法， 授权日：990702，证书号：45985。

Publications ( 1999-2000 ): 26
Including 10 Publications in International Journals
1 Journal of Molecular Catalysis A: Chemical , 149, 119-123,1999
2 Synth.React.Inorg.Met.-Org. Chem., 29(2), 289-296, 1999
3 Applied Catalysis A:General, 183, 81-84, 1999
4 Journal of Molecuar Catalysis A:Chemical, 142,147-152, 1999
5 Journal of Materials Science, 34, 5601-5604, 1999
6 Journal of Applied Polymer Science, 75, 384-389, 2000
7 Applied Catalysis A: General, 192, 247-251, 2000
8 Reactive & functional polymers, 44，65-69 , 2000
9 Reactive & Functional Polymers, 45, 55-59, 2000
10 Journal of Molecular Catalysis A: Chemical 157 , 253-259, 2000
Catalytic Chlorination and
Fluorination of Aromatic
Compounds
Scheme of catalytic chloro-fluorination apparatus
Preparation of (trifluoromethyl)pyridine derivatives
CF3
N
CH3
N
Compound 1
Yield: 75%
Cl2+HF
Cl
Cat.
CF3
Compound 2
Yield: 60%
Cl
N
Cl
Cl

Useges of The Compounds:
Compound 1: Key intermediates of Herbicide (Fluazifop-butyl);
Compound 2: Key intermediates of Herbicide ( Gallant).
Processes of Synthesis of pyridine derivatives

The energy of bond dissociation
C-F bond 453.6 Kj/mol.;
C-Br bond 281.4 Kj/mol.;

C-Cl bond 340.2 Kj/mol.;
C-I bond 222.6 Kj/mol.
Synthesis of 2-Chloro-5-trifluoromethyl pyridine
CH3
[Cl2]
N
Cat.
Cl
CF3
CCl3
[HF]
N
Cat.
Cl
Yield of Chlorination 94%;
Yield of Fluorination 80%.
N
Cl

Synthesis of 2,3-Dichloro-5-trifluoromethyl pyridine
CCl3
CF3
CCl3
HF
Cl2
Cat.
N
Cl
Yield of Chlorination75%;

Cat.
N
Cl
N
Cl
Cl
Cl
Yield of Fluorination80%.
Advanced Processes for Synthesis of the pyridine derivatives

Developing Catalysts System for Chlorination

No Cokes Produced in the Processes
Preparation of (trifluoromethyl) benzene
and fluoro-benzene derivatives

Reactions
CH3
CF3
Xn
Cl2+HF
Xn
Cat.
X = NO2, CF3, Cl, F, CN, COCl etc.,

Catalytic Synthesis of 4-Chloro-trifluorobenzene
CCl3
CF3
[HF]
Cat.
Cl
Cl
n = 1-5

Catalytic Synthesis of 2,6-Dichloro-4-trifluoromethyl aniline
Cl
F3C
NH2
Cl2
F3C
NH2
Cat.

Cl
Catalytic Synthesis of Pentafluorobenzonitrile
CN
CN
CN
Cl2
Cl
Cl
Cat.
Cl
Cl
(F)
F
F
Cat.
F
F
F
Cl

Catalytic Synthesis of Tetrafluoro terephthalonitrile
CN
CN
Cl2
CN
Cl
Cl
Cat.
Cl
Cl
CN
CN
(F)
Cat.
F
F
F
F
CN
Catalytic hydrogenation
and oxidation
Selective Hydrogenation of Benzene

Principle of the Reaction
Product
H2
Cat.
Byproduct

Reaction conditions and Results
Conditions: T= 120-180C,
Results:
P=3.0-10.0Mpa;
Conversion for benzene
Selectivity for cyclohexene

70%;
50%.
Developments

The method for preparing catalysts with nano-particle

The method for preparing ultrafine carrier
Selective Hydrogenation of Cyclopentadiene

Principle of the Reaction
Product
H2
Cat.
Byproduct

Reactions Conditions and Results
Conditions:
Results:

T= 20-50C, P=0.1Mpa;
Conversion for Cyclopentadiene
＞95%
Selectivity for cyclopentene
＞95%
Development

The new catalyst with higher activity and selectivity;
100
95
90
85
80
75
70
65
60
55
50
45
40
35
30
25
20
15
10
5
0
0
50
100
150
200
250
300
350
400
450
100
95
90
85
80
75
70
65
60
55
50
45
40
35
30
25
20
15
10
5
0
selectivity (%)
composition (%)
cpd
cpe
cpa
selectivity
500
cpd
cpe
cpa
selectivity
100
95
90
85
80
75
70
65
60
55
50
45
40
35
30
25
20
15
10
5
0
0
50
100
150
200
250
300
350
400
450
100
95
90
85
80
75
70
65
60
55
50
45
40
35
30
25
20
15
10
5
0
500
time (min)
Catalytic Selective Hydrogenation of Cyclopentadiene
selectivity (%)
composition (%)
time (min)
Catalytic selective oxidation of cyclohexane

Principle of the Reaction
O
OH
Air or O2
+
Cat.

Conditions and Results
Conditions: T=150-180C, P=0.5-1.0Mpa;
Results:
Conversion ( Cyclohexane)30.6%. Total Selectivity
83.1%
Distribution of Products:
Cyclohexanone
50.7%
Cyclohexanol

32.4%
Developments

Discovering a new catalyst system for selective oxidation with higher
activity and selectivity;

Shorter reaction time.
Scheme of catalytic oxidation reaction apparatus
p-hydroxybenzaldehyde from p-cresol

Principle
Air or O2
CH2OH + HO
CHO
Conditions:
T=60-100C, P=0.1-0.5Mpa;
Results:
Conversion ( p-cresol)
Selectivity(p-hydroxybenzaldehyde)
≥98%;
≥90%.
HO


CH3
HO
Cat.
Conditions and Results
Development

Designing a new catalyst system for selective oxidation with higher activity
and selectivity

Easily separation of catalyst from reaction mixing system
Utilization of C5 Fraction
from Cracking Process
Resources of C5 fraction



Resources of C5 fraction from cracking process
 All the world in 1981:
8.0millian ton per year;
 China in 1998:
0.6millian ton per year.
Analysis of C5 fraction from cracking process
 More than 41 kinds compounds :
With boiling point in the range of –88C -170C;
 About 11 kinds compounds with the contents in C5 above
2.5%, including:
dicyclopentadiene 2.0-5%;
cyclopentadiene
12-20%.
Amount of dicyclopentadiene from C5 fraction in China:
About 400 (kt/a)
Partial application of C5 fraction

Separation and reaction of dicyclopentadiene from C5 fraction
C5Áó·Ö
Ë«»· Îì ¶þ
Ï©»ì ºÏ Îï
¼Ó
ÈÈ»ØÁ÷
ÕôÁó»ò¾«Áó
Ç°Áó·Ö
´ÖË«»· Îì ¶þÏ©
¾«Ë«»· Îì ¶þÏ©
½â¾Û·´ Ó¦

¼õѹÕôÁó
»· Îì ¶þÏ©
Application and reaction of Dicyclopentadiene
 Synthesis of tetradicyclopentadiene by hydrogenation
 Obtaining cyclopentadiene by degradation
 Other products
Some products from dicyclopentadiene

Cyclo-C5 products
ËÄÇâË«»· Îì ¶þÏ©
½â¾Û
Çâ
¼Ó
»· Îì ¶þÏ©
Ë«»· Îì ¶þÏ©
Çâ
Ñ¡Ôñ¼Ó
Çâ
¼Ó
Òì¹¹ »¯
½ð¸ÕÍé
1-äå´ú ½ð¸ÕÍé
»· Îì Ï©
»· Îì Íé
È¡´ú
³É
¼Ó
2-äå´ú ½ð¸ÕÍé
äå´ú »· Îì Íé
1-½ð¸ÕÍé ´¼
2-½ð¸ÕÍé ´¼
2-½ð¸ÕÍé °·
È¡´ú
1-½ð¸ÕÍé °·
»· Îì °·
»· Îì ´¼
»· Îì ͪ
Improvement for Application of dicyclopentadiene

Separations of dicyclopentadiene and cyclopentadiene from C5
fraction


Separation of dicyclopentadiene
Yield of dicyclopentadiene:
Purity of dicyclopentadiene:
85%;
83-95%;
Cyclopentadiene from dicyclopentadiene
Yield of cyclopentadiene:
80-88%;
Purity of cyclopentadiene:
95-98%;

Catalytic Synthesis of Adamantane

Hydrogenation and Isomerization of dicyclopentadiene
Product(1)
H2
Cat.
Cat.
Byproduct
Results:
Purity of product(1) 99%;
Yield of product (1)
95%;
Product(2)
Purity of product(2) 99%
Yield of product(2)
55%
Catalytic selective oxidation for
Synthesis of 1,5-glutaldehyde from Cyclopentene

Principle
OH
+
O + OHC(CH2)3CHO
OH

Conditions and Results
Conditions:
Results:

T=20-100C,
P=0.1-0.5Mpa;
Conversion
≥98%;
Selectivity(1,5-glutaldehyde)
≥60%.
Development
Designing a new catalyst system for selective oxidation
Advanced Polymer Materials
and Application
Object materials:
Thermoplastic polyimides
Advantages:









Lightweight Excellent
Cut Through Resistant
Abrasion Resistant
High Temperature Resistant
Not Brittle When Cold
Lower Flammability
Minimal Smoke Generation
Solvent Resistance
Excellent Electrical Properties
Reaction Formula
O
O
O
O
C
C
C
C
O
O + H2N
Ar
Ar' NH2
N
C
C
C
C
O
O
O
O
Dianhydrides:
O
C
C
C
CH3
O
C
H 2N
NH2
O
O
O
O
C
CH3
O
n
Diamines:
O
O
Ar'
N
Ar
S
H 2N
O
NH2
O
O
C
O
O
O
O
O
C
C
C
O
H2N
O
O
C
C
C
C
O
O
O
O
NH2
NH2
H2 N
Table 1. Properties of Polyimide Sheet
Property Type
Property Measured
Test Result
Glass Transition
Temperature (Tg oC)
260-270 oC
Thermal
Temperature of 5%
Lose Weight, oC
Mechanics
Flammability
500-540 oC
Tensile Strength , Mpa
145 Mpa
Compress Strength , Mpa
130 Mpa
Charpy Impact, KJ/m2
100 KJ/m2
Limited Oxygen Index ,%
46
Table 2.Properties of Polyimide Film
Property Type
Property Measured
Glass Transition Temperature
Thermal
(Tg oC)
Temperature of 5%
Lose Weight, oC
Test Result
260-297 oC
515 oC
Mechanics
Tensile Strength , Mpa
192 Mpa
Flammability
Limited Oxygen Index, %
41
Electrical Properties
Dielectric Constant 1000Hz
3.0-3.2
Publications: Preparation and Characteristcs of Nonflammable Polyimide Materials
J. Applied Polmer Science Vol. 75, 384-389 (2000)
Patents:
1.一种缩聚型高分子/纳米 SiO2 阻燃复合材料的制备方法
2.一种阻燃的金属盐/聚酰亚胺复合材料
Catalytic Hydrogenolysis
Of PCBs-Containing
Transformer Oil
Dechlorination of PCBs-containing oil

Catalytic reaction
[H]
Cln
Clm
Cat.

800
700
700
600
600
Amount ( ug/g )
800
500
400
300
500
400
300
200
200
100
100
Peak No.( 16.0 hour )
113
106
99
92
85
78
71
64
57
50
43
36
29
22
15
8
113
106
99
92
85
78
71
64
57
50
36
29
22
15
8
43
Peak No.( 0.0 hour )
1
0
0
1
Amount ( ug/g )
Results for dechlorination of PCBs
Effect of the dechlorination time on PCBs
The changes of the content in the oil with time
PCBs脱除
3500
5000
4000
TCl(ug/g)
TPCBs 量(ug/g)
3000
3000
2000
2500
2000
1500
1000
500
1000
0
0
1 2 3
4 5 6 7 8 9 10 11 12 13 14 15 16 17
Time (小时)
(A)
(A) PCBs content ;
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17
Time (小时)
(B)
(B)
Cl inPCBs content.
Publications:
Reactive &Functional Polymer, 44 (2000) ,65-69,
Active catatyst for the hydrodechlorinatio of perchlorobenzene