- Integration of chemical catalysis with extractive fermentation to produce fuels
-
Nearly one hundred years ago, the fermentative production of acetone by Clostridium acetobutylicum provided a crucial alternative source of this solvent for manufacture of the explosive cordite. Today there is a resurgence of interest in solventogenic Clostridium species to produce n-butanol and ethanol for use as renewable alternative transportation fuels. Acetone, a product of acetone-n-butanol-ethanol (ABE) fermentation, harbours a nucleophilic α-carbon, which is amenable to C-C bond formation with the electrophilic alcohols produced in ABE fermentation. This functionality can be used to form higher-molecular-mass hydrocarbons similar to those found in current jet and diesel fuels. Here we describe the integration of biological and chemocatalytic routes to convert ABE fermentation products efficiently into ketones by a palladium-catalysed alkylation. Tuning of the reaction conditions permits the production of either petrol or jet and diesel precursors. Glyceryl tributyrate was used for the in situ selective extraction of both acetone and alcohols to enable the simple integration of ABE fermentation and chemical catalysis, while reducing the energy demand of the overall process. This process provides a means to selectively produce petrol, jet and diesel blend stocks from lignocellulosic and cane sugars at yields near their theoretical maxima.
- Anbarasan, Pazhamalai,Baer, Zachary C.,Sreekumar, Sanil,Gross, Elad,Binder, Joseph B.,Blanch, Harvey W.,Clark, Douglas S.,Dean Toste
-
-
Read Online
- Rh-Catalyzed Coupling of Aldehydes with Allylboronates Enables Facile Access to Ketones
-
We present herein a novel strategy for the preparation of ketones from aldehydes and allylic boronic esters. This reaction involves the allylation of aldehydes with allylic boronic esters and the Rh-catalyzed chain-walking of homoallylic alcohols. The key to this successful development is the protodeboronation of alkenyl borylether intermediate via a tetravalent borate anion species in the presence of KHF2 and MeOH. This approach features mild reaction conditions, broad substrate scope, and excellent functional group tolerance. Mechanistic studies also supported that the tandem allylation and chain-walking process were involved.
- Zhang, Kezhuo,Huang, Jiaxin,Zhao, Wanxiang
-
supporting information
(2022/02/21)
-
- Rhodium-Catalyzed Remote Isomerization of Alkenyl Alcohols to Ketones
-
We develop herein an efficient rhodium-catalyzed remote isomerization of aromatic and aliphatic alkenyl alcohols into ketones. This catalytic process, with a commercially available catalyst and ligand ([RhCl(cod)]2 and Xantphos), features high efficiency, low catalyst loading, good functional group tolerance, a broad substrate scope, and no (sub)stoichiometric additive. Preliminary mechanistic studies suggest that this transformation involves an iterative dissociative β-hydride elimination-migration insertion process.
- Dong, Wenke,Yang, Hongxuan,Yang, Wen,Zhao, Wanxiang
-
supporting information
(2020/02/28)
-
- ABE Condensation over Monometallic Catalysts: Catalyst Characterization and Kinetics
-
Herein, we present work on the catalyst development and the kinetics of acetone-butanol-ethanol (ABE) condensation. After examining multiple combinations of metal and basic catalysts reported in the literature, Cu supported on calcined hydrotalcites (HT) was found to be the optimal catalyst for the ABE condensation. This catalyst gave a six-fold increase in reaction rates over previously reported catalysts. Kinetic analysis of the reaction over CuHT and HT revealed that the rate-determining step is the C?H bond activation of alkoxides that are formed from alcohols on the Cu surface. This step is followed by the addition of the resulting aldehydes to an acetone enolate formed by deprotonation of the acetone over basic sites on the HT surface. The presence of alcohols reduces aldol condensation rates, as a result of the coverage of catalytic sites by alkoxides.
- Goulas, Konstantinos A.,Gunbas, Gorkem,Dietrich, Paul J.,Sreekumar, Sanil,Grippo, Adam,Chen, Justin P.,Gokhale, Amit A.,Toste, F. Dean
-
p. 677 - 684
(2017/02/26)
-
- Methods to produce fuels
-
The present disclosure generally relates to the catalytic conversion of alcohols into hydrocarbon ketones suitable for use as fuels. More specifically, the present disclosure relates to the catalytic conversion of a mixture of isopropanol-butanol-ethanol (IBE) or acetone-butanol-ethanol (ABE), into ketones suitable for use as fuels. The ABE or IBE mixtures may be obtained from the fermentation of biomass or sugars.
- -
-
Page/Page column 35-37
(2018/02/28)
-
- Catalytic alkylation of acetone with ethanol over Pd/carbon catalysts in flow-through system via borrowing hydrogen route
-
Consecutive alkylation of acetone with ethanol as model reactants was studied in order to obtain biomass based fuels by continuous processing of acetone-butanol-ethanol (ABE) mixture. Butanol, which can inevitably form as Guerbet side product in a self-aldol reaction of ethanol was not applied in our study as an initial component, in order to follow the complexity of the reaction mechanism. A flow-through reactor was applied with inert He or reducing H2 stream in the temperature range of 150-350°C. Efficient catalysts containing Pd and base (K3PO4 or CsOH) crystallites were prepared applying commercial activated carbon (AC) support. The catalyst beds were pre-treated in H2 flow at 350°C. Mono- or dialkylated ketones were formed with high yields and these products could be reduced only to alcohols over palladium.
- Novodárszki, Gyula,Onyestyák, Gy?rgy,Wellisch, ágnes Farkas,Pilbáth, Aranka
-
p. 251 - 257
(2016/07/06)
-
- Highly Efficient Oxidation of Secondary Alcohols to Ketones Catalyzed by Manganese Complexes of N4 Ligands with H2O2
-
The manganese complex Mn(S-PMB)(CF3SO3)2 was proven to be highly efficient in the catalytic oxidation of several benzylic and aliphatic secondary alcohols with H2O2 as the oxidant and acetic acid as the additive. A maximum turnover number of 4700 was achieved in the alcohol oxidation. In addition, the Hammett analysis unveiled the electrophilic nature of this manganese catalyst with N4 ligand. (Chemical Equation Presented).
- Shen, Duyi,Miao, Chengxia,Xu, Daqian,Xia, Chungu,Sun, Wei
-
supporting information
p. 54 - 57
(2015/07/28)
-
- 4-CH3CONH-TEMPO/Peracetic Acid System for a Shortened Electron-Transfer-Cycle-Controlled Oxidation of Secondary Alcohols
-
We have developed a 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) derivative catalyzed oxidation of secondary alcohols with peracetic acid as the oxidant, which was generated from H2O2 and acetic acid catalyzed by strongly acidic resins. The oxidation of alcohols proceeded well through a shortened electron-transfer cycle under metal-free conditions, avoiding the use of any other electron-transfer mediators such as halides. In addition, we demonstrated that the present system exhibited excellent efficiency under mild conditions for the oxidation of aromatic, aliphatic, and allylic secondary alcohols. Shortcut to ketones: The 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-derivative-catalyzed oxidation of secondary alcohols employing peracetic acid generated from H2O2 and acetic acid with strongly acidic resins proceeds through a shortened electron-transfer cycle without halide additives. The system not only exhibits excellent efficiency at room temperature but also has a wide substrate scope.
- Zhang, Shufang,Miao, Chengxia,Xia, Chungu,Sun, Wei
-
p. 1865 - 1870
(2015/06/23)
-
- Acetone alkylation with ethanol over multifunctional catalysts by a borrowing hydrogen strategy
-
Step by step alkylation of acetone (A) with ethanol (E) in a ratio of 1: 2 was investigated. A fixed bed flow-through reactor system was used at a total pressure of 21 bar and in the temperature range of 150-350 °C in inert He or a reducing H2 medium. Following the hydrogen borrowing methodology, two types of catalysts were prepared; using neutral activated carbon (AC) and alkaline hydrotalcite (HT) supports, namely 5 wt% Pd/AC in the presence of alkaline additives (10, 20 and 30 wt% KOH or 20% K3PO4); 9 wt% Cu/HT and 5 wt% Pd/HT. The catalysts were activated in a H2 flow at 350 °C. Different yields of mono- or dialkylated ketones were observed. In a hydrogen medium over the same catalyst systems the ketone products could be reduced to alcohols. In this study the Pd/HT catalyst seems to be the most promising for fuel production based on biomass fermentation.
- Onyestyák, Gy.,Novodárszki, Gy.,Barthos,Klébert, Sz.,Wellisch, á. Farkas,Pilbáth
-
p. 99502 - 99509
(2015/12/04)
-
- Direct α-alkylation of ketones with alcohols in water
-
The direct α-alkylation of ketones with alcohols has emerged as a new green protocol to construct C-C bonds with H2O as the sole byproduct. In this work, a very simple and convenient Pd/C catalytic system for the direct a-alkylation of ketones with primary alcohols in pure water is developed. Based on this catalytic system, aqueous mixtures of dilute acetone, 1-butanol, and ethanol (mimicking ABE fermentation products) can be directly transformed into C5-C11 or longer-chain ketones and alcohols, which are precursors to fuels.
- Xu, Guoqiang,Li, Qiong,Feng, Jiange,Liu, Qiang,Zhang, Zuojun,Wang, Xicheng,Zhang, Xiaoyun,Mu, Xindong
-
p. 105 - 109
(2014/03/21)
-
- Aerobic oxidation of secondary alcohols using NHPI and iron salt as catalysts at room temperature
-
Aerobic oxidation of various alcohols has been accomplished by using a novel catalytic system, N-hydroxyphthalimide (NHPI) combined with Fe(NO 3)3·9H2O. Secondary alcohols, especially benzylic and aliphatic alcohols, were smoothly transformed into corresponding ketones with up to 92% yields at room temperature under one atmosphere pressure of oxygen. The influences of reaction conditions such as solvent, different metal catalyst, catalyst loading and the structure of alcohols on the promotion effect were studied. And a possible radical mechanism for the oxidation of secondary alcohols in Fe(NO3)3·9H 2O/NHPI/O2 system was proposed.
- Zhao, Hanqing,Sun, Wei,Miao, Chengxia,Zhao, Quanyi
-
-
- METHOD FOR THE PURPOSE OF A CATALYTIC CONDENSATION OR COUPLING
-
The invention relates to a method for catalytically condensing organic compounds containing at least one oxo and/or hydroxyl function into CH acidic compounds and/or coupling said organic compounds to the CH acidic compounds in the presence of a catalyst which comprises an active carbon substrate provided with a metal. The method is suitable in particular for generating higher alcohols, aldehydes, ketones, and/or alkanes as well as mixtures thereof.
- -
-
Paragraph 0215-0222
(2014/12/09)
-
- METHOD TO CONVERT FERMENTATION MIXTURE INTO FUELS
-
The present disclosure provides methods to produce ketones suitable for use as fuels and lubricants by catalytic conversion of an acetone-butanol-ethanol (ABE) fermentation product mixture that can be derived from biomass.
- -
-
Page/Page column 73-74
(2013/02/27)
-
- Conversion of biomass-derived butanal into gasoline-range branched hydrocarbon over Pd-supported catalysts
-
For production of gasoline-range branched hydrocarbon from butanal, Pd catalysts supported on different metal oxides were applied. Among the prepared catalysts, Pd/ZrO2 showed the complete butanal conversion with the formation of C7-to-C9 branched hydrocarbon (75% yield). Additionally, the ratios of O/C and straight-chain to branched hydrocarbon (n-C/br-C) were found to be 0.005 and 0.17, respectively. This indicates that an adequate combination of Pd dispersion and amphoteric ZrO2 character promoted hydrodeoxygenation, C-C coupling and isomerization reactions. Consequently, both Pd dispersion and acid-base properties of supports are suggested to play a pivotal role in producing gasoline-range hydrocarbon at a high yield.
- Kim, Sung Min,Lee, Mi Eun,Choi, Jae-Wook,Suh, Dong Jin,Suh, Young-Woong
-
scheme or table
p. 108 - 113
(2012/03/10)
-
- Tandem catalytic triple-bond cleavage of alkyne in association with aldehyde, alkene, and water
-
In this tandem reaction the carbon-carbon triple bond of an alkyne is catalytically cleaved in association with aldehyde, al-kene, and H2O under catalyst mixtures of Rh(I), 2-amino-3-picoline, primary amine, and acid. The reaction starts with chelation-assisted hydroacylation of the alkyne with an aldehyde. The retro-Mannich-type fragmentation of the resulting ,α,β-unsaturated ketimine by an amine and acid affords a ketimine and an aldimine, which is trapped by an alkene and give ketones after hydrolysis. Georg Thieme Verlag Stuttgart.
- Cha, Kyung-Mi,Jo, Eun-Ae,Jun, Chul-Ho
-
scheme or table
p. 2939 - 2942
(2010/01/21)
-
- Mild and recyclable hypervalent iodine system for oxidation of alcohols
-
A simple and mild system for oxidation of primary and secondary alcohols to corresponding aldehydes and ketones has been developed using 4,4′-bis (dichloroiodo) biphenyl in combination with tetraethylammonium bromide (TEAB) at room temperature. Facile recovery and recyclability of the oxidant is reported. Copyright Taylor & Francis Group, LLC.
- Telvekar, Vikas N.,Herlekar, Omkar P.
-
p. 859 - 863
(2007/10/03)
-
- Ruthenium-catalyzed isomerization of alkenol into alkanone in water under irradiation of microwaves
-
Ruthenium catalyzed isomerization of alkenol into alkanone through a migration of C-C double bond was performed in water under irradiation of microwaves. When the reaction was performed in deuterium oxide instead of water, the trail of the migration was shown by H-D exchange reaction. Copyright
- Ishibashi, Kenichi,Takahashi, Masaaki,Yokota, Yutaka,Oshima, Koichiro,Matsubara, Seijiro
-
p. 664 - 665
(2007/10/03)
-
- Semivolatile and volatile compounds in combustion of polyethylene
-
The evolution of semivolatile and volatile compounds in the combustion of polyethylene (PE) was studied at different operating conditions in a horizontal quartz reactor. Four combustion runs at 500 and 850°C with two different sample mass/air flow ratios and two pyrolytic runs at the same temperatures were carried out. Thermal behavior of different compounds was analyzed and the data obtained were compared with those of literature. It was observed that α,ω-olefins, α-olefins and n-paraffins were formed from the pyrolytic decomposition at low temperatures. On the other hand, oxygenated compounds such as aldehydes were also formed in the presence of oxygen. High yields were obtained of carbon oxides and light hydrocarbons, too. At high temperatures, the formation of polycyclic aromatic hydrocarbons (PAHs) took place. These compounds are harmful and their presence in the combustion processes is related with the evolution of pyrolytic puffs inside the combustion chamber with a poor mixture of semivolatile compounds evolved with oxygen. Altogether, the yields of more than 200 compounds were determined. The collection of the semivolatile compounds was carried out with XAD-2 adsorbent and were analyzed by GC-MS, whereas volatile compounds and gases were collected in a Tedlar bag and analyzed by GC with thermal conductivity and flame ionization detectors.
- Font, Rafael,Aracil, Ignacio,Fullana, Andrés,Conesa, Juan A.
-
p. 615 - 627
(2007/10/03)
-
- Development of new iron catalysts for the tandem isomerization-aldol condensation of allylic alcohols
-
(bda)Fe(CO)3 and (COT)Fe(CO)3 are shown to be excellent catalysts for the tandem isomerization-aldol reaction of allylic alcohols with aldehydes and to significantly increase the scope of this aldolization process, especially, in the
- Uma, Ramalinga,Gouault, Nicolas,Crévisy, Christophe,Grée, René
-
p. 6187 - 6190
(2007/10/03)
-
- Efficient isomerization of allylic alcohols to saturated carbonyl compounds by activated rhodium and ruthenium complexes
-
A range of readily available rhodium complexes of the general structures Rh(PPh3)3+ PF6- and RhX(PPh3)3 (X = H, Me, Ph) have been prepared and used in situ for the isomerization of allylic alcohols to their corresponding saturated carbonyl compounds. The isomerization of octen-3-ol, selected as a model, yielded octan-3-one in good yield. This reaction has been extended to the corresponding ruthenium complexes of the general structures [RuCl(PPh3)3]+ PF6-, RuXCl(PPh3)3 and RuX2(PPh3)3 (X = H, Me, Ph). It is noteworthy that many of these complexes have not been employed previously for this isomerization. The scope and efficiency of the process has been demonstrated by four representative complexes [RhH(PPh3)3, RuH2(PPh3)3, RuPh2(PPh3)3, RuCl(PPh3)3+ PF6-] with a wide variety of allylic alcohols. The reaction of primary allylic alcohols in the presence of RuCl(PPh3)3+ PF6- in methanol yields aldehydes protected as their methyl acetals. Deuterium labelling experiments are in agreement with a 1,3-hydride shift mechanism.
- Uma, Ramalinga,Davies, Maxwell K.,Crevisy, Christophe,Gree, Rene
-
p. 3141 - 3146
(2007/10/03)
-
- From allylic alcohols to saturated carbonyls using Fe(CO)5 as catalyst: Scope and limitation studies and preparation of two perfume components
-
The direct conversion of allylic alcohols to saturated carbonyls, using Fe(CO)5 as a catalyst, offers good synthetic potential. Mono-, di- and even trisubstituted alkenes bearing various alkyl, aryl and electronwithdrawing groups on the allylic system give good to excellent yields of rearranged products. Limitations occur mainly with polyunsaturated derivatives. This reaction was applied to a short and efficient synthesis of cyclamen aldehyde and foliaver.
- Cherkaoui, Hassan,Soufiaoui, Mohammed,Grée, René
-
p. 2379 - 2383
(2007/10/03)
-
- From allylic alcohols to aldols via a novel, tandem isomerization-condensation catalyzed by Fe(CO)5
-
Allylic alcohols react with aldehydes, in the presence of catalytic amounts of Fe(CO)5 and under irradiation, to give mainly aldol products. A small amount of ketone resulting from the classical isomerization process is also isolated. This new aldol-type reaction is a complete atom economy process occurring under neutral conditions.
- Crévisy, Christophe,Wietrich, Marina,Le Boulaire, Virginie,Uma, Ramalinga,Grée, René
-
p. 395 - 398
(2007/10/03)
-
- One-pot dialkylation of allylphenylsulfide induced by aminoalkoxides- activated NaNH2. Application to the synthesis of unsymmetrical ketones
-
It is shown that the activation of NaNH2 by sodium aminoalkoxides, leading to new superbases, induced an efficient one-pot dialkylation of allylphenylsulfide. The regioselectivity of the reaction (α,α' vs α,γ) was found as strongly dependent on the nature of the alkyl halide. As an application, α,γ dialkylated products were efficiently converted Into the corresponding unsymmetrical ketones.
- Choppin, Sabine,Gros, Philippe,Fort, Yves
-
p. 9261 - 9268
(2007/10/03)
-
- Mammalian exocrine secretions. XII: Constituents of interdigital secretions of bontebok, Damaliscus dorcas dorcas, and blesbok, D. d. phillipsi
-
In addition to the nine compounds identified in the interdigital secretion of the bontebok, Damaliscus dorcas dorcas, in a previous study, 76 compounds belonging to different compound types, were identified in the interdigital secretions of the bontebok and the blesbok, D. d. phillipsi. These compounds include alkanes, alcohols, aldehydes, ketones, fatty acids, terpenoids, γ-lactones, an isopropyl ester, long-chain hydroxyesters, 2- substituted pyridines, phenols, steroids, and dimethylsulfone. No qualitative differences were found between secretions from the two sexes or from animals from different habitats. Although no attempt was made to correlate territorial behavior or other behavioral phenomena with the qualitative composition of interdigital secretions from individual animals, available information seems to indicate that quantitative differences probably do not have a major semiochemical function. Only two species of bacteria, Bacillus brevis and Planococcus citreus, were found in the interdigital pouches of male and female members of the two subspecies, regardless of the habitat of the animals. B. brevis synthesized, among other unidentified constituents, (Z)-3-penten-2-ol, 2-hexanone, 2-octanone, 2-nonanone, tetradecanoic acid, pentadecanoic acid, heptadecanoic acid, octadecanoic acid, (Z)-9-hexadecenoic acid, and isopropyl hexadecanoate in vitro, while P. citreus produced, among others, the γ-lactones dodecan-4-olide and (Z)-6-dodecen-4-olide, which is one of the major constituents of the interdigital secretions of both subspecies. Some components of the interdigital secretions are not present in the interdigital glandular tissue, and the possibility is discussed that these compounds could be produced by microbiological activity in the interdigital pouch.
- Burger,Nell,Spies,Le Roux,Bigalke,Brand
-
p. 2057 - 2084
(2007/10/03)
-
- Mild, racemization free cleavage of ketone SAMP-hydrazones with oxalic acid - Recycling of the chiral auxiliary
-
Cleavage of ketone SAMP-hydrazones 1a-f with a saturated aqueous oxalic acid solution gives the corresponding ketones 2a-f in excellent yields and with high enantiomeric purity (ee = 90 - 99%). The chiral auxiliary SAMP is recovered from the aqueous phase in good yield (85%) and with unchanged enantiomeric purity. This racemisation free cleavage procedure is compatible with functionalities sensitive to oxidative cleavage conditions, such as ozonolysis, or to strong acids.
- Enders, Dieter,Hundertmark, Thomas,Lazny, Ryszard
-
p. 721 - 722
(2007/10/03)
-
- STEREOCHEMICAL ASSIGMENT BY MASS SPECTROMETRY. DOUBLE BOND GEOMETRICAL ISOMERS OF 3,5-DIALKYLCYCLOHEXYLIDENE ACETIC ACID ESTERS AND 3-ALKYL-2-ALKENOATES
-
Mass spectrometry is best physical method for the configurational assignment of E- and Z-3,5-dialkylcyclohexylidene acetic acid esters 1 and E- and Z-3-alkyl-2-alkenoates 2.The homoallylic cleavage resulting in the loss of the C-3 and C-5 alkyl groups from 1 and of the two δ-alkyls from 2 is a stereospecific process: the loss of the group which is adjacent to the carbonyl is significantly preferred.The stereospecifity of this fragmentation is interpreted in terms of a hidden hydrogen transfer preceding the carbon-carbon bond cleavage.
- Merksammer, Israel,Mandelbaum, Asher
-
p. 775 - 780
(2007/10/02)
-
- NOVEL SYNTHESIS OF INTERNAL ALKENYLDIALKYLBORANE BY THE REACTION OF 1-HALO-1-ALKENYLDIALKYLBORANE WITH GRIGNARD REAGENT.
-
To synthesize internal alkenyldialkylboranes, coupling reactions were carried out by using 1-halo-1-alkenyldialkylboranes and Grignard reagents. Hydrogen peroxide oxidation and protonolysis with acetic acid of the reaction product revealed that internal (E)-alkenyldialkylborane was formed in 60-90% yield.
- Arase,Hoshi,Masuda
-
p. 209 - 213
(2007/10/02)
-
- A NEW SYNTHESIS OF KETONES FROM 1,2-DIMETHOXYETHENYLLITHIUM, ORGANOBORANES, AND ALKYL FLUOROSULFONATES
-
The reaction of alkyl fluorosulfonates with lithium 1,2-dimethoxyethenyltrialkylborates readily prepared from organoboranes gives corresponding ketones in good yields.
- Yogo, Toshinobu,Koshino, Junji,Suzuki, Akira
-
p. 1059 - 1060
(2007/10/02)
-
- OXIDATIVE DESULFONYLATION. PHENYL VINYL SULFONE AS A KETENE SYNTHETIC EQUIVALENT
-
α-Sulfonyl carbanions undergo oxidative desulfonylation to form ketones upon treatment with molybdenum peroxide MoO5*Py*HMPA (MoOPH) in THF at -78 deg C.
- Little, R. Daniel,Myong, Sun Ok
-
p. 3339 - 3342
(2007/10/02)
-
