"Green Photochemistry" Solar Photooxygenations with concentrated Sunlight 1 Michael Oelgemöller...
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Transcript of "Green Photochemistry" Solar Photooxygenations with concentrated Sunlight 1 Michael Oelgemöller...
"Green Photochemistry""Green Photochemistry"Solar PhotooxygenationsSolar Photooxygenations
with concentrated with concentrated SunlightSunlight
1
Michael OelgemöllerMichael OelgemöllerChristian Jung, Jürgen Ortner, Elmar Christian Jung, Jürgen Ortner, Elmar
Zimmermann, Oliver Suchard, Jochen MattayZimmermann, Oliver Suchard, Jochen Mattay
"Back to the Roots""Back to the Roots"
2
sun, O2
Sens.
OO
Günther Otto Schenck (Heidelberg, ca. 1947)Giacomo Ciamician (Bologna, ca. 1910)
Martin Demuth (Mülheim, ca. 1995)Hans-Dieter Scharf (Almería, 1992)
sun, O2
Sens.O CHO O OHO
RoofsRoofs
H.D. Roth Angew. Chem. Int. Ed. Engl. 1989, 28, 1193.
M. Demuth et al. Pure Appl. Chem. 1998, 70, 2167.H.-D. Scharf et al. Angew. Chem. Int. Ed. Engl. 1994, 33, 2009.
3
Solar Reactors at the German Aerospace CenterSolar Reactors at the German Aerospace Center
latitude: 50o51' N, 70 m above sea level - direct sunshine: 1500 h/a - direct insolation: 850 kWh/m2a
Parabolic Trough Facility for Organic Parabolic Trough Facility for Organic Photochemical Synthesis (PROPHIS)Photochemical Synthesis (PROPHIS)
CF: 32Aperture: max. 32 m2
Scale: 35-120 l
Compound Parabolic Collector (CPC)Compound Parabolic Collector (CPC)
CF: ca. 1Aperture: 3 m2
Scale: 35-60 l
Flat-Bed (PlexiglasFlat-Bed (Plexiglas© © or Makrolonor Makrolon©©, , Prof. Demuth, Mülheim / Ruhr)Prof. Demuth, Mülheim / Ruhr)
CF: 1Aperture: 1.5 m2
Scale: 20-25 l
Laboratory-Scale Parabolic Trough Laboratory-Scale Parabolic Trough Reactor Reactor
CF: 15Aperture: 0.2 m2
Scale: 0.2-1 l
Cologne 10.10.1995, 12:00 AM (calc.)
met
hyl
ene
blu
e
rose
ben
gal
S
200 300 400 500 600 700 800 900 1000
0.0
2.0x10-6
4.0x10-6
6.0x10-6
8.0x10-6
1.0x10-5
Wavelength [nm]
Ep
[m
olh
m-2s-1
nm-1]
extraterrestrial irradiance
Solarchemical Model-ReactionsSolarchemical Model-Reactions
4juglone
sunlight, 1O2
Rose Bengal
OH
OH
O
OH O
+1. sun, 1O2
OH OH OH OH
HO
2. Na2SO3
citronellol
1O2= 0.86
SSE0.54
1O2= 0.35
SSE0.37
O
O
OH
frenolicin B (R = Pr)kalafungin (R = Me)
O
O
O
R O
O
OH
K1115A(AP-I inhibitor)
Pr
CO2H
OH
OOH
nocardione A
O
O
O
O
OH
juglomycin A
OO
OH
O
O
urdamycinone B
OH
OOH
OHOHO
• versatile key-intermediate
Model Reaction I: Photooxygenation to JugloneModel Reaction I: Photooxygenation to Juglone
h
Rose Bengal
OH
OH
O
OH O
+ 1O2
lamp: 70-88%
500 g = 57.70 Euro 5 g = 94.50 Euro(165 times)
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• valuable target compound
• good yields with artificial light on multigram scales
(M. Oelgemöller et al. Tetrahedron 2006, 62, 1467.)
• thermal syntheses suffer from low yields, poor selectivity
and reproducibility and aggressive conditions
Sensitox®MB on Ion MB on Ion Exchange ResinExchange Resin
diol [g] Rose Bengal [g]
i-PrOH [ml] mirror area [m2]
time [h] yield [%] photons [mol]
1-2 0.1 200 0.2 3-8 65-79 2.3-7.4
Holographic mirrorHolographic mirror(550±140 nm)(550±140 nm)
sun, i-PrOH
Rose Bengal
OH
OH
O
OH O
+ 1O2
M. Oelgemöller et al. Green Chem. 2005, 7, 35.
Solar Chemical Reactions: August 2003Solar Chemical Reactions: August 2003
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conversion: 100%conversion: 100%yield: 79%yield: 79%after 3hafter 3h
Aluminum mirrorAluminum mirror
sun, i-PrOH
Rose Bengal
OH
OH
O
OH O
+ 1O2
Solar Chemical Reactions: August 2005Solar Chemical Reactions: August 2005
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conversions: >80%conversions: >80%yields: >60%yields: >60%after 4hafter 4h
M. Oelgemöller et al. Green Chem. 2006, submitted.
diol [g] Sensitizer [g]
i-PrOH [ml] mirror area [m2]
time [h] yield [%] photons [mol]
2 0.05-0.1 250 0.2 4 65-72 2.0-2.8
24 g diol
3000 ml i-PrOH
conversion: 48%
after ca. 11 h
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Model Reaction II: Photooxygenation of CitronellolModel Reaction II: Photooxygenation of Citronellol
+1. h, 1O2
OH OH OH OH
HO
2. Na2SO3
H+
O
rose oxidecitronellol lamp (MeOH): 35% 60%
9 kg = 127.70 Euro 1 kg = 157.65 Euro(11 times)
• valuable target compound
• good yields with artificial light on multigram scales
(G. Ohloff et al. Angew. Chem. 1961, 73, 578.)
• thermal syntheses difficult and much more expensive
Symrise (Holzminden, Germany): ca. 100 t/a
small scale large scale
25 kg citronellol 200 kg citronellol
75 kg MeOH 600 kg MeOH
3 lamps à 2000 W 6 lamps à 2000 W
2 days 1.5 - 2 days
10 kg rose oxide 70 kg rose oxide
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Solar Chemical Reaction: September 2002Solar Chemical Reaction: September 2002
M. Oelgemöller et al. Green Chem. 2005, 7, 35.
conversion: 100%conversion: 100%ratio: 45:55ratio: 45:55ca.ca. 2.5 h 2.5 h
PROPHISPROPHIS
+1. h, 1O2
OH OH OH OH
HO
2. Na2SO3
H+
O
rose oxidecitronellol ratio: 45% 55%54%
(99%)
conversions: 100%perfect insolation: 7 hpoor insulation: ca. 30 h
CPCCPC (40 l)
conversions: 100/65%perfect insolation: 12 hpoor insulation: 33 h
horizontal tube reactorhorizontal tube reactor (25 l)
conversions: 100%perfect insolation: 15 hpoor insulation: 30 h
Flat-bedFlat-bed(21 l)
PROPHIS PROPHIS (80 l)
conversion: 100%perfect insolation (Sep.): 2.5 hpoor insulation (Oct.): n.o.
vertical tube reactorvertical tube reactor (20 l)
conversions: 100/65%perfect insolation: 13 hpoor insulation: 33 h10 vol-% citronellol in isopropanol, 0.5 g rose bengal / l isopropanol
+1. h, 1O2
OH OH OH OH
HO
2. Na2SO3
04:00 08:00 12:00 16:00 20:000
200
400
600
800
1000
Time (CESR)I g
(51o ) [
W m
-2]
14.7.2003 12.9.2002 12.9.2000
04:00 08:00 12:00 16:00 20:000
200
400
600
800
1000
Time (CESR)
I n [W
m-2]
14.7.2003 12.9.2002 12.9.2000
PROPHISPROPHIS CPC/Flat-bed/tube reactorsCPC/Flat-bed/tube reactors
direct radiation only(direct normal irradiance In)
direct and diffuse radiation(global horizontal irradiance Ig51O)
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Solar Chemical Campaign: September/October 2002Solar Chemical Campaign: September/October 2002
"On the arid lands there will spring up industrial
colonies without smoke and without smokestacks,
forests of glass tubes will extend over the plains, and
glass buildings will rise everywhere; inside of these will
take place the photochemical processes that hitherto
have been the guarded secret of the plants, but have
been mastered by human industry which will know how
to make them bear even more abundant fruit than nature,
for nature is not in a hurry and mankind is."
(Giacomo Ciamician Science 1912, 36, 385.)
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FundingFunding