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12 Principles of Green Chemistry
7. USE OF RENEWABLE FEEDSTOCKS: A raw material or feedstock should be renewable whenever technically and economically practical.
8. REDUCE DERIVATIVES: Unnecessary derivatization should be minimized or avoided when possible, because such steps require additional reagents and generate waste.
9. CATALYSTS: Catalysts (as selective as possible) are superior to excess reagents.
10. DESIGN FOR DEGRADATION: Chemical products should be designed so that at the end of their function, they break down into harmless products and do not persist in the environment.
11. REAL-TIME ANALYSIS FOR POLLUTION PREVENTION: Methods need to be in-place to allow real-time monitoring and control prior to the formation of hazardous substances.
12. INHERENTLY SAFER CHEMISTRY FOR ACCIDENT PREVENTION: Chemical processes should be designed to minimize the potential for chemical accidents, including releases, explosions, and fires.
1. PREVENTION: It is better to prevent waste than to treat or clean up waste after it has been created.
2. ATOM ECONOMY: Methods should be designed to maximize the use of all materials used in the process into the final product.
3. LESS HAZARDOUS CHEMICAL SYNTHESIS: Wherever practical, methods should be designed to use and generate substances that possess little or no toxicity to people or the environment.
4. DESIGNING SAFER CHEMICALS: Chemical products should be designed to effect their desired function while minimizing their toxicity.
5. SAFER SOLVENTS AND AUXILIARIES: The use of auxiliary substances (e.g., solvents or separation agents) should be made unnecessary whenever possible and harmless when used.
6. DESIGN FOR ENERGY EFFICIENCY: The economic and environmental impact of the energy requirements of chemical processes should be recognized. When possible, processes should be conducted at ambient temperature and pressure.
Anastas, P. T.; Warner, J. C. Green Chemistry: Theory and Practice, Oxford University Press: New York, 1998, p.30
1. PREVENTION: It is better to prevent waste than to treat or clean up waste after it has been created.
5. SAFER SOLVENTS AND AUXILIARIES: The use of auxiliary substances (e.g., solvents or separation agents) should be made unnecessary whenever possible and harmless when used.
3
Pollution Prevention Hierarchy
Prevention & Reduction
Recycling & Re-use
Treatment
Disposal
Incre
asin
g
gre
en
ness
5
INDUSTRIAL WASTE
Industry Ratio Byproducts/Products
Oil Refining <0.1Bulk Chemicals 1 – 5Fine Chemicals 5 – 50Pharmaceuticals 25 – 100+
6
Solventless reactions, why not ?!
Milk turnes sour and shaking of milk gives cheese, dried milk can be kept unaltered. Similarly dried meat can be stored for a long time, whereas meat soup rapidly putrefies on standing.
10
Quantitative Solvent-Free
Organic Reactions
How ?
Solid-Solid Liquid-Solid Gas-Solid Liquid-Liquid …
11
Quantitative Cascade Condensations of o-Phenylenediamines and 1,2- Dicarbonyl Compounds without Producing Wastes
Ar
ArN
N
N
N
OH
N
N COOH
O
H
N
N
O
O
H
H
N
N
N
N
H
H
N
NN
N
H
H
N
N O
N
H
NH2
O
H
N
N O
N NH2
O O
H
H
NH2
NH2
Gerd Kaupp, M. Reza Naimi-Jamal, Eur. J. Org. Chem. 2002, 8, 1368-1373.
13
Quantitative synthesis of benzo[a]phenazin-5-ol (5).
Condensation of o-phenylenediamine with 2-hydroxy-1,4-naphthoquinone
16
Condensation of o-phenylenediamine with alloxane hydrate
The solid-state reaction of o-phenylenediamines 1a and 13 with alloxane hydrate 20
Condensation of o-phenylenediamine with parabanic acid
Reaction of o-phenylenediamine (1a) with parabanic acid (21).
21
Waste-Free and Facile Solid-State Protection of Diamines, Anthranilic Acid, Diols and Polyols with Phenylboronic Acid
G. Kaupp, M. R. Naimi-Jamal, V. A. Stepanenko, Chem. Eur. J. 2003, 9, 4156-4161.
22
Quantitative synthesis of 3 from a stoichiometric melt
Quantitative solid-state synthesis of 5 by ball-milling
23
Quantitative solid-state synthesis of 7 in a ball-mill
Quantitative solid-state synthesis of 9 in a ball-mill
24
Quantitative solid-state synthesis of 15 in a ball-mill
Quantitative solid-state synthesis of 11 and its use as a protected reagent
25
Quantitative solid-state synthesis of heteropropellanes 17
Quantitative solid-state reaction of mannitol with phenylboronic acid
26
Unidirectional photoisomerization of cis-3,3’-bis(diphenyl hydroxymethyl) stilbene in inclusion complex crystals
Ph
Ph
OH
OH
Ph
PhPhPh
OH OH
PhPh
21
h
solid
guest
guest
Koichi Tanaka, Takaichi Hiratsukaa , Shigeru Ohba, M. Reza Naimi-Jamal and Gerd Kaupp, J. Phys. Org. Chem. 2003, 16, 905-912.
28
Tribochemical decontamination of hazardous and non-disposable wastes
G. Kaupp, M. R. Naimi-Jamal , H. Ren and H. Zoz, "Environmentally Protecting Reactive Milling", Chemie Technik 2002, 31(6), 58-60.
31
Some inorganic reactions in the Simoloyer® CM01-2l
G. Kaupp, M. R. Naimi-Jamal, H. Ren, H. Zoz, in: Advanced technologies based on self-propagating and mechanochemical reactions for environmental protection, 2003, Chapter 6, Transworld Research Network, The Interuniversity Consortium Chemistry for the Environment.
32
Figure 2: pilot-set-up of a high energy ball mill (Simoloyer® VS01a) with air/inert carrier gas-cycle and separation/classification system
Figure 1: a 2 L horizontal high energy ball-mill (Simoloyer® CM01-2l) with vacuum and inert-gas loading, operation and unloading.
33
Some organic reactions scaled up to 200 g batches in the Simoloyer CM01-2l
G. Kaupp, J. Schmeyers, M. R. Naimi-Jamal, H. Zoz, H. Ren, Chem. Engin. Sci. 2002, 57, 763-765.
1:1-complex
34
Solvent-Free Knoevenagel Condensations and Michael
Additions with Quantitative Yield
G. Kaupp, M. R. Naimi-Jamal, J. Schmeyer, Tetrahedron 2003, 59, 3753-3760.
35
Quantitative Reaction Cascades of Ninhydrin in the Solid State
Gerd Kaupp, M. Reza Naimi-Jamal, Jens Schmeyers, Chem. Eur. J., 2002, 8(3), 594-600.
41
Mechanochemical Solvent-Free and Catalyst-Free One-Pot Synthesis of Pyrano[2,3-d]Pyrimidine-2,4(1H,3H)-Diones with Quantitative Yields
a Yields refer to conversion yields. b isolated yield
S. Mashkouri , M. R. Naimi-Jamal , Molecules 2009, 14, 474-479
49
Sodium Tetraalkoxyborates: Intermediates for the Quantitative Reduction of Aldehydes and Ketones to Alcohols through Ball Milling with NaBH4
M. R. Naimi-Jamal, J. Mokhtari, M. G. Dekamin and G. Kaupp Eur. J. Org. Chem. 2009, 3567–3572
50
Regiospecific reduction of α,β-unsaturated aldehydes
Specific and stereoselective solvent-free reduction
51
Kneading Ball-Milling and Stoichiometric Melts for the Quantitative Derivatization of Carbonyl Compounds with Gas–Solid Recovery
J. Mokhtari, M. R. Naimi-Jamal, H. Hamzeali, M. G. Dekamin, G. Kaupp, ChemSusChem 2009, 2, 248 – 254
Melt reactions for the solvent-free preparation of phenylhydrazones.
Solvent-free kneading ball-milling of 1 with 4.
52
Sustainable Synthesis of Aldehydes, Ketones or Acids from Neat Alcohols Using Nitrogen Dioxide Gas, and Related Reactions
Benzylic Primary Alcohols
56
Oxidation of solid long-chain primary alcohols with NO2 gas
Stoichiometry of the gas–solid oxidation of 12 with NO2 ; NO and excess NO2 equilibrate with N2O3.
13 is obtained in 95% yield upon vacuum evaporation of the gas mixture including the nitric acid.
59
Oxidative Deprotection of Benzylic Silyl Ethers to
Their Corresponding Carbonyl Compounds Using
Nitrogen Dioxide/Dinitrogen Tetroxide Gas
Iran University Science & Technology
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5 C6H5
C6H5
CH3
CH3
Entry Substrate R' Time(h) Yield(%)
1
2
3
4
5
Oxidative deprotection of TMS ethers in CH2Cl2 and THP ethers in CHCl3 with N2O4/charcoal
0.2
0.5
1
1
0.25 95
95
98
95
96
R"
TMS
TMS
TMS
TMS
TMS
TMS
TMS
THP
THP
THP
THP
THP
THP
6
7
8
9
10
11
12
13
4-MeOC6H5
4-MeC6H5
4-ClC6H5
4-NO2C6H5
4-MeOC6H5
4-MeC6H5
4-NO2C6H5
H
H
H
H
H
H
H
H
H
0.5 96
0.2 99
3 90
8 96
0.5 98
3.5 70
2.5 90
3 85
Long reaction times
Low yields of the products
Tedious work-up
Use of expensive reagents
Some reagents are not available commercially and difficult
procedure for preparation of theirs
Use of solvent and catalyst
Drawbacks of Methods
62
Yield )%(
T (min) Gas (bar)
Product Substrate Entry
60 15 0.2 1
80 15 0.4 2
100 15 0.6 3
CH2OSiMe3
CH2OSiMe3
CH2OSiMe3
CHO
CHO
CHO
Indicate of Value of NO2 / N2O463
R1
OSiMe3
R1
O
R2R2
solvent-free, rt
R1 = H, Me, PhR2 = H, o-,p-Me, m,p-MeO, o-,p-Cl, o-Br, p-F, o-,m-,p-NO2
1 mmol
NO2 / N2O4 (5.8 mmol)
up to 100%
2,4-Dinitrophenyl hydrazine
OSiMe3 H
O
solvent-free
NO2 / N2O4 (5.8 mmol)
rt, 5 min, 100 %
1 mmol
66
m.p.°)C(
Yield (%)
T )min(
Product Substrate Entry
liq. 100 5 1
liq. 100 5 2
liq. 100 5 3
45 100 10 4
12 100 60 5
47 100 5 6
42 100 60 7
56 100 420 8
103 100 60 9
liq. 100 10 10CH2CHO
O2N CHO
CH2OSiMe3
O2N O2N
CHO
CH2OSiMe3
NO2 NO2
CHO
Cl CH2OSiMe3 Cl CHO
CH2OSiMe3
Cl Cl
CHO
CH2OSiMe3Me Me CHO
CH2OSiMe
3
Me Me
CHO
CH2OSiMe3 CHO
CH2OSiMe3O2N
MeO
MeO
CHOCH2OSiMe3MeO
MeO
(CH2)2OSiMe3
67
Yield(%)
T )min(
Product Substrate Entry
100 5 1
80.48 5 2
100 10 3
100 60 4
59 60 5
100 420 6
CH2OSiMe3CHO
CH2CHO
CH2OSiMe3
NO2 NO2
CHO
CH2OSiMe3
O2N O2N
CHO
CH2CHO
CH2OSiMe3
O2N O2N
CHO
(CH2)2OSiMe3
(CH2)2OSiMe3
68
m.p.°)C(
Yield (%)
T )min(
Product Substrate Entry
liq. 100 30 1
liq. 100 60 2
45 100 60 3
49 100 30 4
136 100 60 5
48 100 60 6
CH3
O
CH3
OSiMe3
CH3
OSiMe3
NO2
CH3
NO2
O
CH3
OSiMe3
Br
CH3
Br
O
OSiMe3
Ph Ph
O
OSiMe3
O2N
PhO2N
Ph
O
OSiMe3
F
PhF
Ph
O
69
Investigation of the Mechanism
The oxidation of primary and secondary benzylic silyl ethers
were performed as gas-solid reactions.
Apart from the aldehydes or ketones, nitrous acids such as NO,
N2O3, HONO and HONO2 are formed.
70
FT-IR data reveals that there are :
excess NO2 (ν = 2918, 2891, 1629, 1598, 752 cm-1),
excess N2O4 (ν = 1743, 1261, 825, 750 cm-1),
HONO2 (ν = 1740, 1392 broad, 855 cm-1) in gas-phase.
FT-IR spectroscopy reveals no trace of NO, HONO and N2O3 .
HONO (ν = 1699, 1640, 1265, 853, 791 cm-1)
NO (ν = 1876, 1835 cm-1)
N2O3 (ν = 1835,1655, 1305, 773 cm-1)
73
FT-IR spectroscopy from liquid-phase of reaction exhibits the
anymore peaks in ν = 1473, 1369, 823, 729 cm-1.
These peaks could be for Me3Si-O-SiMe3 or Nitrat compound.
NO, HONO and N2O3 are not present in liquid-phase.
76
Gas chromatogram from liquid phase of p-Chlorobenzyl silyl ether.
2.743 min
9.370 min
Me3Si-O-SiMe3
CH2ONO2Cl
Cl CH2
OSiMe32 h
GC-MS from liquid phaseNO2 / N2O4 (5.8 mmol)
1 mmol 77
CH3 CH2ONO2
HH
H H
CH3H
OHH
HH
Me CH2
OSiMe33 h
NMR from liquid phaseNO2 / N2O4 (5.8 mmol)
1 mmol 80
Cl
OSiMe3NO2 / N2O4
Cl
O SiMe3
NO
OO2N
Cl
ONO2 Me3SiONO
A
+
B
Cl
O NO
OH
H
- HONO
Cl
H
O
A
3 HONO HONO2 2 NO H2O
NO
+ +
++H2O 3 NO2 2 HONO2
B
N2O3
2 Me3SiONO Me3SiOSiMe3 NO NO2+ +
83
Gerd Binnig (left) and Heinrich Rohrer (right) who were awarded the Nobel Prize for their invention of the scanning tunneling microscope.
86
9.5 μm AFM images of Ninhydrin on its (100)-cleavage plane at 0.1 mm distance from a crystal of o-phenylenediamine on it after the times given, showing the formation of small craters that grow gradually. The z-scale is 50 nm, the direction of preference runs along the [001]-direction (the scan direction was changed after 210 min).
89
9.5 μm AFM topographies on the (10–1)-face of Ninhydrin at 0.1 mm distance from a flat crystal of o-phenylenediamine on it; (a) fresh; (b) after 2 min (phase rebuilt); (c) after 15 min; (d) after 60 min (phase transformed).
90
9.5 µm AFM topographies on the (1–10)-face of Ninhydrin at 0.5 mm distance from a flat crystal of o-phenylenediamine on it; (a) fresh; (b) after 15 min (phase rebuilt); (c) after 2 h; (d) after 4 h (phase transformed).
91
Stereoscopic face model for the crystal packing of Ninhydrin with (1–10) horizontal on top and (–110) horizontal at the bottom, showing the steep double layers. All hydrogen bonds are drawn.
92
11 µm AFM surfaces on (010) of a-cinnamic acid after 365 nm irradiation: (a) fresh; (b) and (b’) after 30 min, b’ is a 3 µm scan; (c) after 2 times 45 min; (d) after 90 min continuously; the orientation of the crystal varied slightly, but the c-axis was always cut by the parallel fissures and ridges at an angle of 40 ° (crystallographic cleavage plane direction: 39°); the Z-scale covers 10 nm in (a) and 100 nm in (b), (c), (d).
UV-Irrdiation of a-Cinnamic Acid
93
9 mm AFM surface of a-cinnamic acid after 6 months daylight irradiation in a Pyrex vessel under Ar through two additional window glass plates showing fence-like features along the cleavage plane direction.
G. Kaupp and M. Haak, Mol. Cryst. Liq. Cryst., 1998, 313, 193.
94
16 µm AFM topographies after nanoscratching on (110) of Thiohydantoin at various directions by reference to the long crystal axis showing anisotropic molecular migrations; the applied force was 0–400 µN in (a) and (b); and 0–1000 µN in (c) and (d).
N
N
S
OH
H(P21/c)
Anisotropic Molecular
Migrationnot only by chemical reactions but also by
mechanical load:
„Nanoscratching“
95
Geometric conditions for the mechanical tests with the verticalforce of the indenter as applied to the (110)-face of thiohydantoin.
96
New Solid State Mechanism:derived from AFM studies
• Phase Rebuildinglong range anisotropic molecular migrations
• Phase Transformationformation of product phase
• Crystall Disintegration
provides fresh reactive surfaces
97