Advanced Organic Chemistry/

Organic Synthesis CH 621

Ultrasound Assisted Organic
Synthesis (Sonochemistry)
Bela Torok
Department of Chemistry
University of Massachusetts Boston
Boston, MA
1
Ultrasonics/Sonochemistry - Historical Overwiev
Ultrasonics
- Ultrasounds (20-10 000 kHz)
- 1880 Piezoelectricity (Curie brothers)
- 1893 Galton
- 1912 TITANIC
- 1912 Behm(Echo technique)
- 1917 Langevin(Ultrasonic variation,
Icebergs, Submarines)
- 1945 Application in chemistry
2
Ultrasonics/Sonochemistry Basics
Frequency ranges of sound
3
Ultrasonics/Sonochemistry Basics
Sound transmission through a medium
4
Ultrasonics/Sonochemistry Acoustic Cavitation
Formation of an acoustic bubble
Bubble size and cavitation
dynamics
Transient cavitation
5
Ultrasonics/Sonochemistry Acoustic Cavitation
Acoustic cavitationin a homogeneous liquid
Suslick- ~4-5000 K
6
Ultrasonics/Sonochemistry Acoustic Cavitation
Acoustic cavitationin solid/liquid system
7
Acoustic cavitationin solid/liquid system
Ultrasonics/Sonochemistry Acoustic Cavitation
8
Ultrasonics/Sonochemistry Acoustic Cavitation
Acoustic cavitationin liquid/liquid system
9
Ultrasonics/Sonochemistry Sonochemical Effect
Specific ultrasonic effect ? Yes and No
No - another internal heating approach
Yes - The temperature dependence of E
A
of different reactions
could be significantly different change in selectivities
- Very effective mixing
- Cavitation
- Surface cleaning
10
Ultrasonics/Sonochemistry Experimental
Parameters
1. Acoustic frequency
Increasing frequency increasing energy
Theory - usually higher reaction rate
Real life optimum frequency as we have to balance
reactivity/selectivity
The effect is different for every reaction and general rule can not be
made.
11
Ultrasonics/Sonochemistry Sonochemical Effect
2. Acoustic power
Similar as frequency, however, the extent of increase is limited
Optimum
12
Ultrasonics/Sonochemistry Sonochemical Effect
3. Temperature
Cavitationbubbles energy of collapse
Pressure inside the bubble
In general lower temperature is better, but again there is an optimum
as higher temperature increases the probability of the cavitation
13
Ultrasonics/Sonochemistry Sonochemical Effect
4. External (static) pressure
Not quite clear, but in general higher pressure is better.
Role of particles (ultrafiltration)
14
Ultrasonics/Sonochemistry Sonochemical Effect
5. Gas
Polytropratio (=C
p
/C
v
), thermal conductivity, and solubility
Usually inert gases are the best (noble gases)
15
Ultrasonics/Sonochemistry Sonochemical Effect
6. Solvent
Should be as inert as possible, and stable toward ultrasounds
Sonolysisof the solvent
Usually high biolingpoint is preferred, but it is controversial
as diethylether is a good solvent in many applications.
16
Ultrasonics/Sonochemistry Experimental
Parameters
Intesityof collapse
Limit of transient cavitation
Primer and secondary reactions
Vapor pressure
Surface tension
Viscosity
Chemical reactivity
Solvent
Intesityof collapse
Primer and secondary reactions
The content of bubbles
Politropratio
Thermal conductivity
Chemical reactivity
solubility
Gas
Intesityof collapse
The content of bubbles
Total pressure
Solubility of gas
Static pressure
The content of bubbles, the
intensity of collapse
Secondary reactions
Vapor pressure of liquid
Themal activation
Temperature
The number of cavitation
phenomena in a unit volume
Size of the reaction zone Acoustic power
Change in the size of the bubbles Period of bubble collapse Acoustic frequency
Effect Physical parameter Experimental parameter
17
Ultrasonics/Sonochemistry Transducers
Galtonwhistle (physical)
Liquid whistle (physical)
Piezoelectric sandwich transcducer
Magnetostrictivetranscducer
18
Ultrasonics/Sonochemistry Reactors
19
Ultrasonics/Sonochemistry Applications
- Electronics industry (coating with metals)
- Therapy (surgery with ultrasounds), diagnostics
- Food industry
- Materials (metallurgy)
- Synthesis
- Environmental applications
20
Ultrasonics/Sonochemistry Synthesis
Applications in Organic Synthesis
1. Homogeneous Sonochemistry
- Aqueous medium
- Non-aqueous media
2. Heterogeneous Sonochemitsry
- Phase Transfer Catalysis
- Reactions with metals
- Heterogeneous Catalysis
3. Enzyme reactions
21
Ultrasonics/Sonochemistry Synthesis
H
2
O
H +

OH
2

H
2

OH
2

OH
2

O
0,5 O
2
+2 H
H +

OH
H
2
O
H
2
H
2
O
2
O + H
2
O
O
2
H
2
O
1.1. Aqueous sonochemistry
2 Br
Br
2
)
)
)
(2.8)
HOOC
COOH
COOH
COOH
(2.9)
OH
COOH
)
) )
COOH
1. Homogeneous sonochemistry
22
Ultrasonics/Sonochemistry Synthesis
1.2. Non-Aqueous sonochemistry
1. Homogeneous sonochemistry
23
Ultrasonics/Sonochemistry Synthesis
N
R'
+
I
-
R
Cl
3
CCOONa, CH
3
CN
R
N
R'
CCl
3
+
N
R'
CCl
3
R (2.14)
70-100 %
)
))
(2.15)
R
I
-
+
N
Me
tBuOK
R
N
Me
OtBu
R
N
Me
O
85-98 %
)
) )
91 - 98 %
R +
CH
3
COCH
3
, NaOH
))
)
N
Me
CH
2
C CH
3
O
N
Me
CH
2
C
CH
3
O
R
N
Me
+
I
-
R
(2.16)
1.2. Non-Aqueous sonochemistry
24
1.2. Non-Aqueous sonochemistry
Ultrasonics/Sonochemistry Synthesis
NMe
P
O
OEt
EtO
H
+
90 C, toluene
o
NHMe
P
O
EtO
EtO
Yield (%)
15 min 30 min 60 min 120 min
stirring 0 0 <5 37
sonication 12 32 67 82
25
1.2. Non-Aqueous sonochemistry
Ultrasonics/Sonochemistry Synthesis
Yield (%)
stirring 10-53
sonication 57-93
R R'
R"
O
O
+
R"
R' R
O
O
+
O
O
R"
R' R
26
1.2. Non-Aqueous sonochemistry
Ultrasonics/Sonochemistry Synthesis
)))
Mo(CO)
6
O
OH
OOH
+ +
+ +
OOH OO
O
2
+
+ H
OO
27
Ultrasonics/Sonochemistry Synthesis
2. Heterogeneous sonochemistry
2.1. Phase transfer catalysis
28
Ultrasonics/Sonochemistry Synthesis
2.1. Phase transfer catalysis
NaOH + CHCl
3
:CCl
2
Cl
Cl
74-99% 0.7-5h
+ CHCl
3
NaOH
TEBA
H CCl
2
H
H CCl
2
H
stirring 9 h 15%
sonication, 3h 83%
4.3 1
29
Ultrasonics/Sonochemistry Synthesis
2.1. Phase transfer catalysis
30
Ultrasonics/Sonochemistry Synthesis
2.2. Reactions with metals
R
R'
O + R"-Cl
Li
)))
R
R'
R"
OH
10-40 min 68-99%
+ R'-Cl
Li, THF
)))
72-99%
R
O
OLi
R
R'
O
31
Ultrasonics/Sonochemistry Synthesis
2.2. Reactions with metals
EtOOC
COOEt
K, toluene
))), 5 min
O
COOEt
83%
Zn, DMF
)))
R
F
-X + CO
2
R
F
COOH
35-77%
Zn, AcOH
)
)), 10 min
O
H
Me
Me
C
8
H
17
H
Me
Me
C
8
H
17
32
Ultrasonics/Sonochemistry Synthesis
2.3. Heterogeneous catalysis
33
Ultrasonics/Sonochemistry Synthesis
2.3. Heterogeneous catalysis
34
Ultrasonics/Sonochemistry Synthesis
2.3.
Heterogeneous
catalysis
35
Microwaves/Sonochemistry References
- http://www.shiga-med.ac.jp/chemistry/sonochemRes.html
- Luche, J . L., Synthetic Organic Sonochemistry, Plenum Press, 2001
- Suslick, K. S., Ultrasound: Its Chemical, Physical, and Biological Effects;
VCH, 1988.
- Mason, T. J ., Sonochemistry: Current Uses and Future Prospect in Chemical
and Industrial Processing, RSC, 1999
36