"geraniol"

"kinetic study and mechanism"

Bibliographic Information

Kinetics and re action mechanism of the controlled oxidation of some industrial alcohols by
haloamines. Prabhu, D. V. Department of Chemistry, Wilson College (University of Mumbai),
Mumbai, India. Journal of the Indian Chemical Society (2007), 84(11), 1135-1139. Publisher: Indian
Chemical Society

Abstract

A kinetic study of the controlled oxidn. of perfumery alcs., geraniol, 1-Ph ethanol and benzyl alc. by
Chloramine T in alk. medium and Chloramine B in acidic medium has been carried out in the temp. range
30 °C to 50 °C. The oxidn. was monitored in the micellar phase using sodium dodecyl sulfate. The oxidn.
rate increases with alc. concn. but decreases with the concn. of the oxidising reagent and varies linearly
with the concn. of the metal ion catalysts used. The thermodn. activation parameters have been calcd.

Bibliographic Information

Oxidation of primary alcohols by quinolinium dichromate. A kinetic probe. Nongkynrih, I.;

Dkhar, J. C.; Kharpuria, E.; Mahanti, M. K. Department of Chemistry, North-Eastern Hill University,
Shillong, India. Oxidation Communications (2007), 30(1), 82-87. Publisher: SciBulCom Ltd.,
Abstract

The oxidn. of primary alcs. by quinolinium dichromate, in acid medium, gave the corresponding
aldehydes. The reaction was first order in each - substrate, oxidant and acid. The mechanistic pathway
involved the formation of a cyclic chromate ester, which underwent decompn., in the rate-detg. step, to
give the product.

Bibliographic Information

An integrated process: Ester synthesis in an enzymatic membrane reactor and water sorption.
Trusek-Holownia, Anna; Noworyta, Andrzej. Chemical and Biochemical Processes, Wroclaw University
of Technology, Wroclaw, Pol. Journal of Biotechnology (2007), 130(1), 47-56. Publisher: Elsevier
B.V.,

Abstract

In the case of such reactions as ester synthesis, water is produced during the reaction. Because these
reactions are carried out in hydrophobic solvents an addnl. (water) phase in the system must not be
allowed, i.e. the concn. of water satn. in the org. solvent should not be exceeded. In such a case, the
reaction kinetics and product equil. concn. undergo undesirable changes because of the partition coeff. of
the components and hampered process of product sepn. Hence, removal of the water produced in the
reaction dets. whether the process is successful or not. For this purpose, the integrated process with
water sorption in the column with mol. sieves was applied. Integration of the process of synthesis and
dehydration of a reaction phase, in which a biocatalyst is suspended and not dissolved as in water solns.,
requires holding up of the catalyst in the reactor before directing the stream of reaction mixt. to
dehydration process. This hold-up and a possibility of multiple use of the catalyst may be accomplished
by using a sepg. barrier, e.g. an ultrafiltration membrane or by permanent fixing of the catalyst to the
matrix, e.g. a polymeric membrane. The efficiency and activity of a biocatalyst (lipase CAL-B)
immobilized on a polymer membrane by sorption and chem. binding, were detd. A subject of study was
the synthesis of geranyl acetate, one of the most known arom. compd. A hydrophobic (polypropylene)
matrix was shown to be a much better carrier in the reactions performed in an org. solvent than a
hydrophilic (polyamide) membrane being tested. The reaction kinetics of geranyl acetate synthesis with
the use of geraniol and acetic acid as substrates, was described by the equation defining the "Ping-Pong
Bi Bi" mechanism that was related addnl. to the inhibition of a substrate (acetic acid). The following
consts.
of kinetic equation were obtained k'3 = 0.344 mol g-1 h1, KmA = 0.257 mol l-1, KmG = 1.629 and KiA =
0.288 for the native enzyme and vmax,Gel = 111.579 mol l-1 h1, KmA = 0.255 mol l-1, KmG = 1.91 mol l-
1, KiA = 0.238 mol l-1 for the one immobilized by sorption on a polypropylene membrane. Half-life time of
the native enzyme activity was 204 h and stability of the immobilized prepn. was 70 h. With respect to the
reaction kinetics and stability of the native enzyme and immobilized prepn., from both types of membrane
bioreactor more attractive appears to be the one in which the membrane is used not as a catalyst layer
but only as a barrier that immobilizes the native enzyme within the bioreactor vol. When an integrated
process proceeds, the method to collect water in the sorption column during the process, appeared to
work very well. The reaction proceeded with a very high efficiency (after 120 h α = 98.2% for native
enzyme and 83.2% for immobilized enzyme) and due to low water concn. in the system (≈ 0.000%
vol./vol.) the second phase was not created.

Bibliographic Information

Olefin epoxidation with hydrogen peroxide catalyzed by lacunary polyoxometalate [γ

-SiW10O34(H2O)2]4-. Kamata, Keigo; Kotani, Miyuki; Yamaguchi, Kazuya; Hikichi, Hiro; Mizuno,
Noritaka. Core Res. Evolutional Sci. Technol. (CREST), Japan Sci Technol. Agency (JST), 4-1-8
Honcho, Kawaguchi, Saitama, Japan. Chemistry--A European Journal (2007), 13(2), 639-648.
Publisher: Wiley-VCH Verlag GmbH & Co. KGaA, CODEN: CEUJED ISSN: 0947-6539. Journal written
in English. CAN 146:316397 AN 2007:75043 CAPLUS (Copyright (C) 2007 ACS on SciFinder (R))

Abstract

The tetra-n-butylammonium (TBA) salt of the divacant Keggin-type polyoxometalate [TBA]4[γ -

SiW10O34(H2O)2] (I) catalyzes the oxygen-transfer reactions of olefins, allylic alcs., and sulfides with
30% aq. hydrogen peroxide. The neg. Hammett ρ + (-0.99) for the competitive oxidn. of p-substituted
styrenes and the low value of (nucleophilic oxidn.)/(total oxidn.), XSO = 0.04, for I-catalyzed oxidn. of
thianthrene 5-oxide (SSO) reveals that a strongly electrophilic oxidant species is formed on I. The
preferential formation of trans-epoxide during epoxidn. of 3-methyl-1-cyclohexene demonstrates the steric
constraints of the active site of I. The I-catalyzed epoxidn. proceeds with an induction period that
disappears upon treatment of I with hydrogen peroxide. 29Si and 183W NMR spectroscopy and CSI
mass spectrometry show that reaction of I with excess hydrogen peroxide leads to fast formation of a
diperoxo species, [TBA]4[γ -SiW10O32(O2)2] (II), with retention of a γ -Keggin type structure. Whereas
the isolated compd. II is inactive for stoichiometric epoxidn. of cyclooctene, epoxidn. with II does proceed
in the presence of hydrogen peroxide. The reaction of II with hydrogen peroxide would form a reactive
species (III), and this step corresponds to the induction period obsd. in the catalytic epoxidn. The steric
and electronic characters of III are the same as those for the catalytic epoxidn. by I. Kinetic,
spectroscopic, and mechanistic investigations show that the present epoxidn. proceeds via III.

Bibliographic Information
 Effect of Internal Diffusion in Supported Ionic Liquid Catalysts: Interaction with Kinetics.
Mikkola, Jyri-Pekka; Waern, Johan; Virtanen, Pasi; Salmi, Tapio. Laboratory of Industrial Chemistry,
Process Chemistry Centre, Abo Akademi University, Abo-Turku, Finland. Industrial & Engineering
Chemistry Research (2007), 46(12), 3932-3940. Publisher: American Chemical Society, CODEN:
IECRED ISSN: 0888-5885. Journal written in English. CAN 146:464064 AN 2006:1221417
CAPLUS (Copyright (C) 2007 ACS on SciFinder (R))

Abstract

Kinetics and mass transfer for supported ionic liq. catalysts (SILCAs) were studied for complex catalytic
hydrogenations of unsatd. aldehydes. The system can be characterized as a gas-liq.-liq.-solid system,
where gaseous hydrogen and an unsatd. aldehyde, citral, diffuse from mol. solvent to a thin layer of ionic
liq. contg. the catalytically active species, metallic Pd nanoparticles. The intrinsic kinetics was detd. at
353-423 K (80-150°) and pressures of 10 to 50 bar. A kinetic model was proposed that predicts exptl.
concn. data successfully. In order to obtain more understanding about the importance of mass-transfer
and diffusion limitations for these processes, a no. of models describing the concn. profiles of the
reactants in the catalysts were developed. The reaction-diffusion models revealed important insight into
the potential limiting phenomena for this type of reaction systems.

Bibliographic Information

Solvent effects in liquid-phase reactions. II. Kinetic modeling for citral hydrogenation.
Mukherjee, Samrat; Vannice, M. Albert. Department of Chemical Engineering, Pennsylvania State
University, University Park, PA, USA. Journal of Catalysis (2006), 243(1), 131-148. Publisher:
Elsevier Ltd., CODEN: JCTLA5 ISSN: 0021-9517. Journal written in English. CAN 145:489409 AN
2006:935263 CAPLUS (Copyright (C) 2007 ACS on SciFinder (R))

Abstract

The initial liq.-phase reaction to hydrogenate any of the three unsatd. bonds in the citral mol. can be
described by a Langmuir-Hinshelwood (LH) mechanism that assumes that mol. citral and H atoms are the
two most abundant reaction intermediates. It was applicable with each of the eight solvents studied;
however, a wide range of values was obtained for the two adsorption equil. consts. contained in the
optimized rate equation, Kcit and KH2. Regarding the rate of overall citral disappearance, four possible
solvent effects-mass transfer limitations, liq.-phase H2 soly., liq.-phase nonideality, and competitive
solvent adsorption - were evaluated in detail to see whether one of them could account for the 3-fold
variation in turnover frequency and possibly decrease the variation in adsorption equil. consts. Using the
Weisz-Prater criterion established the absence of mass transfer limitations, using H2 concn. provided no
benefit, and including thermodn. activity coeffs. for citral gave only minimal benefit. However, introducing
solvent adsorption into the site balance equation revealed that a narrow range exists for a single apparent
rate const. that is applicable for all of the solvents, makes the KH2 values essentially invariant, and
reduces the range of Kcit values to a factor of 7. Kinetic studies at three temps. gave adsorption equil.
consts. that provided consistent, meaningful values for the enthalpy and entropy of adsorption for citral,
H2, and the solvent. Consequently, this is the best single explanation for the obsd. kinetic behavior.
Finally, individual rates of formation were calcd. for the unsatd. alc. (geraniol and nerol) vs. the partially
satd. aldehyde (citronellal) and the proposed LH model, either including or excluding competitive solvent
adsorption, was able to describe each rate simultaneously using the same optimized adsorption equil.
consts. Including the solvent in the rate expression again showed that a single set of apparent rate
consts.
can exist that simultaneously describe the three reactions. Thermodn. consistency of the adsorption
equil. consts. for citral, H2, and the solvent was obtained in all cases.
Bibliographic Information

Inverse temperature dependence due to catalyst deactivation in liquid phase citral hydrogenation
over Pt/Al2O3. Maeki-Arvela, Paeivi; Kumar, Narendra; Eraenen, Kari; Salmi, Tapio; Murzin, Dmitry
Yu. Process Chemistry Centre, Abo Akademi University, Turku/Abo, Finland. Chemical Engineering
Journal (Amsterdam, Netherlands) (2006), 122(3), 127-134. Publisher: Elsevier B.V., CODEN:
CMEJAJ ISSN: 1385-8947. Journal written in English. CAN 145:473412 AN 2006:904460
CAPLUS (Copyright (C) 2007 ACS on SciFinder (R))

Abstract

Citral hydrogenation was studied over a Pt/Al2O3 catalysts in cyclohexane and in 2-pentanol. Several
kinetic trends, which were correlated to catalyst deactivation, were achieved. Accumulation of trans
isomers in both citral and in unsatd. alcs. was visible under deactivating conditions. The further
hydrogenation of citronellal was nearly totally inhibited due to catalyst deactivation, whereas nerol,
geraniol and citronellol formation were enhanced at higher temps. and pressures. The main unusual
kinetic phenomena in citral hydrogenation in 2-pentanol were, first, a max. obsd. in the initial
hydrogenation rates as a function of temp. caused by catalyst deactivation and, second, a min. in citral
conversion after prolonged reaction times. The reason for these unusual kinetic phenomena is
decarbonylation reaction occurring during hydrogenation, i.e. formation of CO, which was confirmed by
temp. programmed desorption of geraniol from a reduced Pt/Al2O3 catalyst.

Bibliographic Information

New Insights into the Mechanism of Palladium-Catalyzed Allylic Amination. Watson, Iain D. G.;
Yudin, Andrei K. Davenport Research Laboratories, Department of Chemistry, University of Toronto,
Toronto, ON, Can. Journal of the American Chemical Society (2005), 127(49), 17516-17529.
Publisher: American Chemical Society, CODEN: JACSAT ISSN: 0002-7863. Journal written in English.
CAN 144:128517 AN 2005:1208245 CAPLUS (Copyright (C) 2007 ACS on SciFinder (R))

Abstract

A comparative study into palladium-catalyzed allylic amination of unsubstituted aziridines and secondary
amines was carried out. The use of NH aziridines as nucleophiles favors formation of valuable branched
products in the case of aliph. allyl acetates. The regioselectivity of this reaction is opposite to that obsd.
when other amines are used as nucleophiles. Study provides evidence for the palladium-catalyzed
isomerization of the branched (kinetic) product formed with common secondary amines into the thermodn.
(linear) product. But the branched allyl products obtained from unsubstituted aziridines do not undergo
the isomerization process. Crossover expts. indicate that the isomerization of branched allylamines is
bimol. and is catalyzed by Pd0. The reaction has significant solvent effect, giving the highest branched-
to-linear ratios in THF. This finding can be explained by invoking the intermediacy of σ -complexes,
which is consistent with NMR data. The apparent stability of branched allyl aziridines towards palladium-
catalyzed isomerization is attributed to a combination of factors that stem from a higher degree of s-
character of the aziridine nitrogen compared to other amines. The reaction allows for regio- and
enantioselective incorporation of aziridine rings into appropriately functionalized building blocks. The
resulting methodol. addresses an important issue of forming quaternary carbon centers next to nitrogen.
The new insights into the mechanism of palladium-catalyzed allylic amination obtained in this study
should facilitate synthesis of complex heterocycles, design of new ligands to control branched-to-linear
ratio, as well as abs. stereochem. of allylamines.
Bibliographic Information

Biocatalysis using lipase encapsulated in microemulsion-based organogels in supercritical

carbon dioxide. Blattner, Christian; Zoumpanioti, Maria; Kroener, Juergen; Schmeer, Georg; Xenakis,
Aristotelis; Kunz, Werner. Institut fuer Physikalische und Theoretische Chemie, Universitaet
Regensburg, Regensburg, Germany. Journal of Supercritical Fluids (2006), 36(3), 182-193.
Publisher: Elsevier B.V., CODEN: JSFLEH ISSN: 0896-8446. Journal written in English. CAN
144:106692 AN 2005:1165640 CAPLUS (Copyright (C) 2007 ACS on SciFinder (R))

Abstract

Lipases from Candida antarctica and Mucor miehei were encapsulated in lecithin water-in-oil (w/o)
microemulsion-based organogels (MBG). These gels were formulated with either hydroxypropylmethyl
cellulose (HPMC) or gelatin. The esterification of lauric acid and 1-propanol catalyzed by these MBGs
was examd. in supercrit. carbon dioxide (scCO2; 35 ° C, 110 bar) as solvent for the substrates. The
results were compared to those obtained with the ref. substrate solvent isooctane. It turned out that the
initial rates of this model reaction in scCO2 were higher than those obsd. in the ref. system. Various
parameters affecting the biocatalysis such as pressure, alc. and acid chain length, and gel compn. were
investigated. Kinetic studies showed that the ester synthesis catalyzed by the immobilized C. antarctica
lipase occurs via a Ping Pong Bi Bi mechanism in which only inhibition by excess of alc. was identified.
Values of all kinetic parameters were detd. In addn., expts. on the reusability of these gels in scCO2
were carried out and the state of water within the organogel was examd. with the help of differential
scanning calorimetry. The present study shows that biocatalysis using MBGs in scCO2 is a promising
alternative to other bioconversion processes.

Bibliographic Information

Enantioselective epoxidation of allylic alcohols by a chiral complex of vanadium: An effective

controller system and a rational mechanistic model. Zhang, Wei; Basak, Arindrajit; Kosugi, Yuji;
Hoshino, Yujiro; Yamamoto, Hisashi. Department of Chemistry, The University of Chicago, Chicago,
IL, USA. Angewandte Chemie, International Edition (2005), 44(28), 4389-4391. Publisher: Wiley-
VCH Verlag GmbH & Co. KGaA, CODEN: ACIEF5 ISSN: 1433-7851. Journal written in English. CAN
143:306086 AN 2005:683217 CAPLUS (Copyright (C) 2007 ACS on SciFinder (R))

Abstract

Epoxy alcs. are prepd. enantioselectively in 24-91% yields and in 92-97% ee by oxidn. of either (E)- or
(Z)-disubstituted and trisubstituted allylic alcs. with aq. tert-Bu hydroperoxide (TBHP) in the presence of
catalysts generated from oxovanadium triisopropoxide and bishydroxamic acids I [R = Ph2CH, Ph3CCH2,
(3,5-Me2C6H3)2CH]. Aq. TBHP is an effective oxidant for the epoxidn. reactions; the use of anhyd.
TBHP does not increase either the enantioselectivities or yields of epoxidn. reactions. Epoxidn. reactions
can be performed at either 0° or room temp. without significant losses in enantioselectivity if the
substrates react slowly at -20°. Small allylic alcs. such as (E)- and (Z)-crotyl alcs. undergo stereo- and
enantioselective epoxidns. using cumene hydroperoxide as the oxidant in the presence of oxovanadium
triisopropoxide and I [R = Ph2CH, Ph3CCH2, (3,5-Me2C6H3)2CH]. PhCH(OH)CH:CH2 undergoes
kinetic resoln. with aq. TBHP in the presence of oxovanadium triisopropoxide and I (R = Ph2CH) to yield
(R)-PhCH(OH)CH:CH2 in 95% ee and epoxy alc. II in 93% ee.
 O R

N
OH
HO
OH
N O Ph

O R I H II

Bibliographic Information

Remarkable Substituent Effects on the Oxidizing Ability of Triarylbismuth Dichlorides in Alcohol

Oxidation. Matano, Yoshihiro; Hisanaga, Teppei; Yamada, Hisatsugu; Kusakabe, Shingo; Nomura,
Hazumi; Imahori, Hiroshi. Department of Molecular Engineering, Graduate School of Engineering,
Kyoto University, Nishikyo, Kyoto, Japan. Journal of Organic Chemistry (2004), 69(25), 8676-8680.
Publisher: American Chemical Society, CODEN: JOCEAH ISSN: 0022-3263. Journal written in English.
CAN 142:114195 AN 2004:973496 CAPLUS (Copyright (C) 2007 ACS on SciFinder (R))

Abstract

Substituent effects on the oxidizing ability of triarylbismuth dichlorides were examd. by intermol. and
intramol. competition expts. on geraniol oxidn. in the presence of DBU. The oxidizing ability of the
dichlorides increases with increasing electron-withdrawing ability of the para substituents, and by
introduction of a Me group at the ortho position of the aryl ligands attached to the Bi. The intermol. and
intramol. H/D kinetic isotope effects obsd. for the competitive oxidn. of p-bromobenzyl alcs. indicate that
the rate-detg. step involves C-H bond cleavage. Several primary and secondary alcs. were oxidized
efficiently under mild conditions by the combined use of newly developed organobismuth(V) oxidants and
DBU.

Bibliographic Information

Highly selective, recyclable epoxidation of allylic alcohols with hydrogen peroxide in water
catalyzed by dinuclear peroxotungstate. Kamata, Keigo; Yamaguchi, Kazuya; Mizuno, Noritaka.
Core Research for Evolutional Science and Technology (CREST), Japan Science and Technology
Agency, Kawaguchi, Japan. Chemistry--A European Journal (2004), 10(19), 4728-4734. Publisher:
Wiley-VCH Verlag GmbH & Co. KGaA, CODEN: CEUJED ISSN: 0947-6539. Journal written in English.
CAN 142:6068 AN 2004:873380 CAPLUS (Copyright (C) 2007 ACS on SciFinder (R))

Abstract

The highly chemo-, regio-, and diastereoselective and stereospecific epoxidn. of various allylic alcs. with
only one equiv. of hydrogen peroxide in water can be efficiently catalyzed by the dinuclear
peroxotungstate, K2[{W(=O)(O2)2(H2O)}2(µ -O)]⋅ 2H2O (I). The catalyst is easily recycled while
maintaining its catalytic performance. The catalytic reaction mechanism including the exchange of the
water ligand to form the tungsten-alcoholate species followed by the insertion of oxygen to the carbon-
carbon double bond, and the regeneration of the dinuclear peroxotungstate with hydrogen peroxide is
proposed. The reaction rate shows first-order dependence on the concns. of allylic alc. and dinuclear
peroxotungstate and zero-order dependence on the concn. of hydrogen peroxide. These results, the
kinetic data, the comparison of the catalytic rates with those for the stoichiometric reactions, and kinetic
isotope effects indicate that the oxygen transfer from a dinuclear peroxotungstate to the double bond is
the rate-limiting step for terminal allylic alcs. such as 2-propen-1-ol (1a).

Bibliographic Information

Micelle-Hosted Palladium Nanoparticles Catalyze Citral Molecule Hydrogenation in Supercritical

Carbon Dioxide. Meric, Pascal; Yu, Kai Man K.; Tsang, Shik Chi. Surface and Catalysis Research
Centre, School of Chemistry, University of Reading, Whiteknights, Reading, Berkshire, UK. Langmuir
(2004), 20(20), 8537-8545. Publisher: American Chemical Society, CODEN: LANGD5 ISSN: 0743-
7463. Journal written in English. CAN 141:367612 AN 2004:694308 CAPLUS (Copyright (C)
2007 ACS on SciFinder (R))

Abstract

Metal particles on micelles were used as catalysts in hydrogenation of org. mols. in the presence of
fluorinated surfactant and water in supercrit. carbon dioxide (scCO2). Direct visual evidence of formation
of metal microemulsions and the mechanism by which metal located in the soft micellar assemblies
affects the reaction selectivity are presented. The Pd nanoparticles were incorporated into
perfluorohydrocarboxylate anionic micelles in scCO2 in a stainless steel batch reactor at 40° in a 150 bar
CO2/H2 mixt. Homogeneous dispersion of the microemulsion contg. Pd nanoparticles in scCO2 was
obsd. through a sapphire window of the reactor at W0 ratio (molar water-to-surfactant ratio) of 2 - 30. The
micelle assemblies as metal catalyst nanocarriers were evaluated for product selectivity. The
hydrogenation of citral, which contains three reducible groups (aldehyde, double bonds at the 2,3-position
and the 6,7-position) was studied. An unusually high selectivity toward citronellal (a high regioselectivity
toward the redn. of the 2,3-unsatn.) was obsd. in scCO2. When the reaction was carried out in a
conventional liq. or vapor phase over the same reaction time, total hydrogenation of the two double bonds
was achieved. The high kinetic reluctance for double bond hydrogenation of the citral mol. at the
hydrophobic end (the 6,7-position) is due to the unique micelle environment that is in close proximity to
the metal surface in scCO2, which guides a head-on attack of the mol. toward the core metal particle.

Bibliographic Information

Scope, kinetics, and mechanistic aspects of aerobic oxidations catalyzed by ruthenium

supported on alumina. Yamaguchi, Kazuya; Mizuno, Noritaka. Department of Applied Chemistry,
School of Engineering, The University of Tokyo, Tokyo, Japan. Chemistry--A European Journal
(2003), 9(18), 4353-4361. Publisher: Wiley-VCH Verlag GmbH & Co. KGaA, CODEN: CEUJED ISSN:
0947-6539. Journal written in English. CAN 140:4715 AN 2003:788357 CAPLUS (Copyright (C)
2007 ACS on SciFinder (R))

Abstract

The Ru/Al2O3 catalyst was prepd. by modification of the prepn. of Ru(OH)3⋅ nH2O. The present
Ru/Al2O3 catalyst has high catalytic activities for the oxidns. of activated, nonactivated, and heterocyclic
alcs., diols, and amines at 1 atm of mol. O. Also, the catalyst could be reused seven times without a loss
of catalytic activity and selectivity for the oxidn. of benzyl alc. A catalytic reaction mechanism involving a
Ru alcoholate species and β -hydride elimination from the alcoholate was proposed. The reaction rate
has a first-order dependence on the amt. of catalyst, a fractional order on the concn. of benzyl alc., and a
zero order on the pressure of mol. O. These results and kinetic isotope effects indicate that β -
elimination from the Ru alcoholate species is a rate-detg. step.

Bibliographic Information
 Cu(ii)-nitroxyl radicals as catalytic galactose oxidase mimics. Dijksman, Arne; Arends, Isabel W.
C. E.; Sheldon, Roger A. Laboratory for Biocatalysis and Organic Chemistry, Department of
Biotechnology, Delft University of Technology, Delft, Neth. Organic & Biomolecular Chemistry (2003),
1(18), 3232-3237. Publisher: Royal Society of Chemistry, CODEN: OBCRAK ISSN: 1477-0520.
Journal written in English. CAN 140:16455 AN 2003:709470 CAPLUS (Copyright (C) 2007 ACS
on SciFinder (R))

Abstract

Results from Hammett correlation studies and primary kinetic isotope effects for the CuCl-TEMPO
catalyzed aerobic benzyl alc. oxidns. are inconsistent with an oxoammonium based mechanism. We
postulate a copper-mediated dehydrogenation mechanism, in which TEMPO regenerates the active
Cu(ii)-species. This mechanism is analogous to that obsd. for galactose oxidase and mimics thereof.

Bibliographic Information

Linalool to geraniol/nerol isomerization catalyzed by (RO)3VO complexes: studies of kinetics and

mechanism. Semikolenov, V. A.; Ilyna, I. I.; Maksimovskaya, R. I. Boreskov Institute of Catalysis,
Novosibirsk, Russia. Journal of Molecular Catalysis A: Chemical (2003), 204-205 201-210.
Publisher: Elsevier Science B.V., CODEN: JMCCF2 ISSN: 1381-1169. Journal written in English.
CAN 140:59784 AN 2003:697990 CAPLUS (Copyright (C) 2007 ACS on SciFinder (R))

Abstract

Highly selective catalytic system {(RO)3VO+[(Bu)4N+]OH} for the process of linalool to geraniol + nerol
isomerization within the temp. range of 413-513 K is reported. Using the 51V NMR spectroscopy, compn.
and reactivity of vanadium complexes formed in the catalytic system were investigated. Mononuclear
vanadium complexes (RO)3-n(R'O)nVO, where RO-linalyl and R'O-geranyl/neryl ligands, n=0, 1 and 2,
are active in the isomerization reaction. The reaction of the ligand {linalool/(geraniol+nerol)} exchange is
very fast and reversible, the equil. const. of this reaction was estd. The rate detg. step of the
isomerization process is the rearrangement of the coordinated to vanadium linalyl- to geranyl/neryl
ligands which, probably, proceeds via redn.-oxidn. mechanism. The isomerization of linalool is a
reversible reaction and two isomers (geraniol and nerol) are formed by the parallel routs. The equil.
const. of the linalool/(geraniol+nerol) as well as geraniol/nerol isomerization slightly depends on temp.
The reaction rate is of the first-order on linalool, geraniol and nerol concns. The kinetic scheme and
mechanism of linalool to geraniol+nerol isomerization are suggested.

Bibliographic Information

Epoxidation of Allylic Alcohols with TiO2-SiO2: Hydroxy-Assisted Mechanism and Dynamic

Structural Changes During Reaction. Beck, C.; Mallat, T.; Baiker, A. Swiss Federal Institute of
Technology, Institute for Chemical- and Bioengineering, ETH Hoenggerberg, Zurich, Switz. Catalysis
Letters (2003), 88(3-4), 203-209. Publisher: Kluwer Academic/Plenum Publishers, CODEN: CALEER
ISSN: 1011-372X. Journal written in English. CAN 139:245575 AN 2003:426562 CAPLUS
(Copyright (C) 2007 ACS on SciFinder (R))

Abstract

Epoxidn. of allylic alcs. and cyclohexene with TBHP and titania-silica aerogels contg. 1 and 5 wt% TiO2
has been studied. For the oxidn. of geraniol and cyclohexenol, the regio- and diastereoselectivities and
kinetic data indicate an OH-assisted mechanism involving a dative bond between the OH group and the
Ti site. This mechanism is disabled in the oxidn. of cyclooctenol due to steric hindrance. The moderate
regio- and diastereoselectivities of the aerogels, compared with those of TS-1 and the homogeneous
model Ti(OSiMe3)4, are attributed to the presence of non-isolated Ti sites and to a "silanol-assisted"
mechanism, according to which model the allylic alc. is anchored to a neighboring SiOH group instead of
the Ti-peroxo complex. Kinetic anal. of the initial transient period revealed rapid catalyst restructuring
during the first few turnovers. A feasible explanation is the breaking of Si-O-Ti linkages of the carefully
predried aerogels by water or TBHP, resulting in active Ti sites with remarkably different catalytic
properties.

Bibliographic Information

Oxygen Transfer from Sulfoxides: Selective Oxidation of Alcohols Catalyzed by

Polyoxomolybdates. Khenkin, Alexander M.; Neumann, Ronny. Department of Organic Chemistry,
Weizmann Institute of Science, Rehovot, Israel. Journal of Organic Chemistry (2002), 67(20), 7075-
7079. Publisher: American Chemical Society, CODEN: JOCEAH ISSN: 0022-3263. Journal written in
English. CAN 137:352596 AN 2002:667570 CAPLUS (Copyright (C) 2007 ACS on SciFinder (R))

Abstract

Benzylic, allylic, and aliph. alcs. are oxidized to aldehydes and ketones in a reaction catalyzed by Keggin-
type polyoxomolybdates, PVxMo(12-x)O40-(3+x) (x = 0, 2), with DMSO as a solvent. The oxidn. of
benzylic alcs. is quant. within hours and selective, whereas that of allylic alcs. is less selective. Oxidn. of
aliph. alcs. is slower but selective. Further mechanistic studies revealed that, for H3PMo12O40 as a
catalyst and benzylic alcs. as substrates, the sulfoxide is in fact an oxygen donor in the reaction.
Postulated reaction steps as detd. from isotope-labeling expts., kinetic isotope effects, and Hammett plots
include (a) sulfoxide activation by complexation to the polyoxometalate and (b) oxygen transfer from the
activated sulfoxide and elimination of water from the alc. The mechanism is supported by the reaction
kinetics.

Bibliographic Information

Efficient and Selective Aerobic Oxidation of Alcohols into Aldehydes and Ketones Using
Ruthenium/TEMPO as the Catalytic System. Dijksman, Arne; Marino-Gonzalez, Arturo; Mairata i
Payeras, Antoni; Arends, Isabel W. C. E.; Sheldon, Roger A. Laboratory for Organic Chemistry and
Catalysis Department of Biotechnology, Delft University of Technology, Delft, Neth. Journal of the
American Chemical Society (2001), 123(28), 6826-6833. Publisher: American Chemical Society,
CODEN: JACSAT ISSN: 0002-7863. Journal written in English. CAN 135:180370 AN 2001:446655
CAPLUS (Copyright (C) 2007 ACS on SciFinder (R))

Abstract

The combination of RuCl2(PPh3)3 and TEMPO affords an efficient catalytic system for the aerobic oxidn.
of a variety of primary and secondary alcs., giving the corresponding aldehydes and ketones in >99%
selectivity in all cases. The Ru/TEMPO system displayed a preference for primary vs secondary alcs.
Results from Hammett correlation studies (ρ = -0.58) and the primary kinetic isotope effect (kH/kD = 5.1)
for the catalytic aerobic benzyl alc. oxidns. are inconsistent with either an oxoruthenium (O:Ru) or an
oxoammonium based mechanism. Therefore, a hydridometal mechanism, involving a RuH2(PPh3)3
species as the active catalyst is postulated. TEMPO acts as a hydrogen transfer mediator and is either
regenerated by oxygen, under catalytic aerobic conditions, or converted to TEMPH under stoichiometric
anaerobic conditions.
Bibliographic Information

Mouse alcohol dehydrogenase 4: kinetic mechanism, substrate specificity and simulation of

effects of ethanol on retinoid metabolism. Plapp, B. V.; Mitchell, J. L.; Berst, K. B. Department of
Biochemistry, The University of Iowa, Iowa City, IA, USA. Chemico-Biological Interactions (2001),
130-132(1-3), 445-456. Publisher: Elsevier Science Ireland Ltd., CODEN: CBINA8 ISSN: 0009-2797.
Journal written in English. CAN 135:30646 AN 2001:259618 CAPLUS (Copyright (C) 2007 ACS
on SciFinder (R))

Abstract

Mouse ADH4 (purified, recombinant) has a low catalytic efficiency for ethanol and acetaldehyde, but very
high activity with longer chain alcs. and aldehydes, at pH 7.3 and temp. 37°C. The obsd. turnover nos.
and catalytic efficiencies for the oxidn. of all-trans-retinol and the redn. of all-trans-retinal and 9-cis-retinal
are low relative to other substrates; 9-cis-retinal is more reactive than all-trans-retinal. The redn. of all-
trans- or 9-cis-retinals coupled to the oxidn. of ethanol by NAD+ is as efficient as the redn. with NADH.
However, the Michaelis const. for ethanol is about 100 mM, which indicates that the activity would be
lower at physiol. relevant concns. of ethanol. Simulations of the oxidn. of retinol to retinoic acid with
mouse ADH4 and human aldehyde dehydrogenase (ALDH1), using rate consts. estd. for all steps in the
mechanism, suggest that ethanol (50 mM) would modestly decrease prodn. of retinoic acid. However, if
the Km for ethanol were smaller, as for human ADH4, the rate of retinol oxidn. and formation of retinoic
acid would be significantly decreased during metab. of 50 mM ethanol. These studies begin to describe
quant. the roles of enzymes involved in the metab. of alcs. and carbonyl compds.

Bibliographic Information

A novel chitosan derivative to immobilize α -L-rhamnopyranosidase from Aspergillus niger for

application in beverage technologies. Spagna, G.; Barbagallo, R. N.; Casarini, D.; Pifferi, P. G.
Food Biotechnology Group from the Department of Horticulture, Floriculture, Arboriculture and
Agroindustrial Technology (DOFATA), University of Catania, Catania, Italy. Enzyme and Microbial
Technology (2001), 28(4-5), 427-438. Publisher: Elsevier Science Ireland Ltd., CODEN: EMTED2
ISSN: 0141-0229. Journal written in English. CAN 134:339824 AN 2001:163317 CAPLUS
(Copyright (C) 2007 ACS on SciFinder (R))

Abstract

α -L-rhamnopyranosidase (Rha, EC 3.2.1.40) is an enzyme of considerable importance to food technol.

in increasing the aroma of wines, musts, fruit juices and other beverages. The aim of this research is the
immobilization of the Rha contained in a com. prepn. already used in the winemaking industry. The
immobilization supports tested were chitin, chitosan and derivatized chitosan, diethylaminoethyl chitosan
(DE-chitosan) never previously used for this type of application. Particularly, on DE-chitosan, the Rha
was adsorbed and cross-linked with various bifunctional agents (glutaraldehyde, diepoxyoctane,
suberimidate and carbodiimide), whose best results (immobilization yields and activity) were obtained with
carbodiimide (EDC) that allowed a redn. in the involvement of the enzyme amine groups that are probably
important in catalytic mechanism. In addn., the use of rhamnose and a succinimide (NHS) during
crosslinking enhanced the action of the EDC and so increased the immobilization yield and activity. The
immobilized Rha retained the kinetic parameters (Km and Vmax) of the free enzyme and increased
stability. Moreover, this biocatalyst allowed an increase in the aroma in a model wine soln. contg.
glycosidic precursors with a marked redn. in specificity toward tertiary monoterpenols as compared to the
free enzyme.
Bibliographic Information

Oxidation of alcohols by quinolinium dichromate. A kinetic study. Nongkynrih, Irona; Kharpuria,

Evarisa; Dkhar, John C.; Mahanti, Mahendra K. Department of Chemistry, North-Eastern Hill
University, Shillong, India. Oxidation Communications (2000), 23(3), 399-407. Publisher: Bulgarian-
English Academic Publishing House, PublishScieSet, CODEN: OXCODW ISSN: 0209-4541. Journal
written in English. CAN 134:17222 AN 2000:763051 CAPLUS (Copyright (C) 2007 ACS on
SciFinder (R))

Abstract

The oxidn. of alcs. (primary, secondary and allylic) by quinolinium dichromate, in acid medium, gave the
corresponding carbonyl products. The dependence of rate coeffs. on acidity, and kinetic isotope effects
support a mechanism in which the rate-detg. step involved the decompn. of a cyclic chromate ester in an
electrocyclic manner involving six electrons. Being a Hueckel type system (4n + 2), this was an allowed
process.

Bibliographic Information

Inhibition of Escherichia coli porphobilinogen synthase using analogs of postulated

intermediates. Jarret, Caroline; Stauffer, Frederic; Henz, Matthias E.; Marty, Maurus; Luond, Rainer
M.; Bobalova, Janette; Schurmann, Peter; Neier, Reinhard. Institute of Chemistry, University of
Neuchatel, Neuchatel, Switz. Chemistry & Biology (2000), 7(3), 185-196. Publisher: Elsevier
Science Ltd., CODEN: CBOLE2 ISSN: 1074-5521. Journal written in English. CAN 133:27942 AN
2000:207755 CAPLUS (Copyright (C) 2007 ACS on SciFinder (R))

Abstract

Background: Porphobilinogen synthase is the second enzyme involved in the biosynthesis of natural
tetrapyrrolic compds., and condenses two mols. of 5-aminolevulinic acid (ALA) through a nonsym.
pathway to form porphobilinogen. Each substrate is recognized individually at two different active site
positions to be regioselectively introduced into the product. According to pulse-labeling expts., the
substrate forming the propionic acid sidechain of porphobilinogen is recognized first. Two different
mechanisms for the first bond-forming step between the two substrates have been proposed. The first
involves carbon-carbon bond formation (an aldol-type reaction) and the second carbon-nitrogen bond
formation, leading to an iminium ion. Results: With the help of kinetic studies, we detd. the Michaelis
consts. for each substrate recognition site. These results explain the Michaelis-Menten behavior of
substrate analog inhibitors: they act as competitive inhibitors. Under std. conditions, however, another
set of inhibitors demonstrates uncompetitive, mixed, pure irreversible, slow-binding or even quasi-
irreversible inhibition behavior. Conclusions: Anal. of the different classes of inhibition behavior allowed
us to make a correlation between the type of inhibition and a specific site of interaction. Analyzing the
inhibition behavior of analogs of postulated intermediates strongly suggests that carbon-nitrogen bond
formation occurs first.

Bibliographic Information

An integrated process: ester synthesis in an enzymatic membrane reactor and water sorption.
Trusek-Holownia Anna; Noworyta Andrzej Wroclaw University of Technology, Team of Chemical and
Biochemical Processes, Norwida 4/6, 50-373 Wroclaw, Poland. anna.trusek-holownia@pwr.wroc.pl
Journal of biotechnology (2007), 130(1), 47-56. Journal code: 8411927. ISSN:0168-1656. Journal;
Article; (JOURNAL ARTICLE) written in English. PubMed ID 17434222 AN 2007257421 MEDLINE
(Copyright (C) 2008 U.S. National Library of Medicine on SciFinder (R))

Abstract

In the case of such reactions as ester synthesis, water is produced during the reaction. Because these
reactions are carried out in hydrophobic solvents an additional (water) phase in the system must not be
allowed, i.e. the concentration of water saturation in the organic solvent should not be exceeded. In such
a case, the reaction kinetics and product equilibrium concentration undergo undesirable changes because
of the partition coefficient of the components and hampered process of product separation. Hence,
removal of the water produced in the reaction determines whether the process is successful or not. For
this purpose, the integrated process with water sorption in the column with molecular sieves was applied.
Integration of the process of synthesis and dehydration of a reaction phase, in which a biocatalyst is
suspended and not dissolved as in water solutions, requires holding up of the catalyst in the reactor
before directing the stream of reaction mixture to dehydration process. This hold-up and a possibility of
multiple use of the catalyst may be accomplished by using a separating barrier, e.g. an ultrafiltration
membrane or by permanent fixing of the catalyst to the matrix, e.g. a polymeric membrane. The
efficiency and activity of a biocatalyst (lipase CAL-B) immobilized on a polymer membrane by sorption
and chemical binding, were determined. A subject of study was the synthesis of geranyl acetate, one of
the most known aromatic compound. A hydrophobic (polypropylene) matrix was shown to be a much
better carrier in the reactions performed in an organic solvent than a hydrophilic (polyamide) membrane
being tested. The reaction kinetics of geranyl acetate synthesis with the use of geraniol and acetic acid
as substrates, was described by the equation defining the "Ping-Pong Bi Bi" mechanism that was related
additionally to the inhibition of a substrate (acetic acid).
The following constants of kinetic equation were obtained k(3)(')=0.344 mol g(-1)h(-1), K(mA)=0.257 mol
l(-1), K(mG)=1.629 and K(iA)=0.288 for the native enzyme and v(max,Gel)=111.579 mol l(-1)h(-1),
K(mA)=0.255 mol l(-1), K(mG)=1.91 mol l(-1), K(iA)=0.238 mol l(-1) for the one immobilized by sorption
on a polypropylene membrane. Half-life time of the native enzyme activity was 204 h and stability of the
immobilized preparation was 70 h. With respect to the reaction kinetics and stability of the native enzyme
and immobilized preparation, from both types of membrane bioreactor more attractive appears to be the
one in which the membrane is used not as a catalyst layer but only as a barrier that immobilizes the
native enzyme within the bioreactor volume. When an integrated process proceeds, the method to collect
water in the sorption column during the process, appeared to work very well. The reaction proceeded
with a very high efficiency (after 120 h alpha=98.2% for native enzyme and 83.2% for immobilized
enzyme) and due to low water concentration in the system ( approximately 0.000% v/v) the second phase
was not created.