Modern Methods for the Epoxidation of - and -Pinenes, 3-Carene...
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Chemistry for Sustainable Development 16 (2008) 633691 633 Modern Methods for the Epoxidation of α- and β-Pinenes, 3-Carene and Limonene O. V. BAKHVALOV, V. V. FOMENKO a nd N. F. SALAKHUTDINOV Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences, Pr. Akademika Lavrentyeva 9, Novosibirsk 630090 (Russia) E-mail: [email protected] Abstract The present review is emphasized on chemical aspects of epoxidation, environmental safety of promising methods for processing such a renewable raw material as terpenes. Various epoxidizing systems are considered, first of all those allowing one to perform catalytic epoxidation of terpenes, as well as their prospective value for commercial introduction. The review has included the materials published within the period from 1988 to 2008. For the convenience of comparing various epoxidizing systems and of choosing optimum conditions for the process carrying out, all the data are listed to form common tables. Key words: terpen, epoxidation, green chemistry, renewable raw material, oxidation Contents Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 633 Some general laws for epoxidation of terpenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 634 Mechanisms for the interaction of terpenes with epoxidizing agents. Features of some epoxidation processes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 635 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 687 INTRODUCTION The epoxidation of olefins represents a con- venient way to activate and fuction alize them [15] which quite often serves as the first stage of various kinds of industrial production [69]. A plenty of works, including a number of the reviews performed for the last decade [3, 1012] devoted to this process are available from the literature. The authors of the monograph [10] considered epoxidation of alkenes in a partic- ularly academic theoretical aspect wherein ter- penes were out of consideration. There are transformations discussed in this book those proceed under the influence of individual agents enriched with active oxygen on olefins, instead of real epoxidizing systems. The review is useful for understanding the mechanisms of epoxidation, but it is less interesting from the standpoint of choosing the conditions in order to carry out a preparative synthesis of terpene epoxides. An extensive review [3] is devoted mainly to oxidation reactions of compounds from various classes. In the section devoted to the epoxidation, terpenes figured as initial com- pounds only for two reactions among several tens of reactions presented. The authors of [12] listed a number of catalytical epoxidation sys- tems including hydrogen peroxide. However, only one terpene was used among initial alk- enes. A similar approach is described also in a very brief review [11]. Nowadays the success in the field of fine organic synthesis of terpenoids is obvious. From the theoretical point of view it is quite possible that combining known methods of organic syn- thesis one could obtain almost any known or potentially interesting from the practical stand- point of view terpenoids. On the other hand, provided putting a question concerning profound
Transcript of Modern Methods for the Epoxidation of - and -Pinenes, 3-Carene...
Chemistry for Sustainable Development 16 (2008) 633�691 633
Modern Methods for the Epoxidation of ααααα- and βββββ-Pinenes,3-Carene and Limonene
O. V. BAKHVALOV, V. V. FOMENKO and N. F. SALAKHUTDINOV
Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences,Pr. Akademika Lavrentyeva 9, Novosibirsk 630090 (Russia)
E-mail: [email protected]
Abstract
The present review is emphasized on chemical aspects of epoxidation, environmental safety of promisingmethods for processing such a renewable raw material as terpenes. Various epoxidizing systems are considered,first of all those allowing one to perform catalytic epoxidation of terpenes, as well as their prospectivevalue for commercial introduction. The review has included the materials published within the period from1988 to 2008. For the convenience of comparing various epoxidizing systems and of choosing optimumconditions for the process carrying out, all the data are listed to form common tables.
Key words: terpen, epoxidation, green chemistry, renewable raw material, oxidation
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 633 Some general laws for epoxidation of terpenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 634Mechanisms for the interaction of terpenes with epoxidizing agents.
Features of some epoxidation processes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 635Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 687
INTRODUCTION
The epoxidation of olefins represents a con-venient way to activate and fuctionalize them[1�5] which quite often serves as the first stageof various kinds of industrial production [6�9].A plenty of works, including a number of thereviews performed for the last decade [3, 10�12]devoted to this process are available from theliterature. The authors of the monograph [10]considered epoxidation of alkenes in a partic-ularly academic theoretical aspect wherein ter-penes were out of consideration. There aretransformations discussed in this book thoseproceed under the influence of individualagents enriched with active oxygen on olefins,instead of real epoxidizing systems. The reviewis useful for understanding the mechanisms ofepoxidation, but it is less interesting from thestandpoint of choosing the conditions in order
to carry out a preparative synthesis of terpeneepoxides. An extensive review [3] is devotedmainly to oxidation reactions of compoundsfrom various classes. In the section devoted tothe epoxidation, terpenes figured as initial com-pounds only for two reactions among severaltens of reactions presented. The authors of [12]listed a number of catalytical epoxidation sys-tems including hydrogen peroxide. However,only one terpene was used among initial alk-enes. A similar approach is described also in avery brief review [11].
Nowadays the success in the field of fineorganic synthesis of terpenoids is obvious. Fromthe theoretical point of view it is quite possiblethat combining known methods of organic syn-thesis one could obtain almost any known orpotentially interesting from the practical stand-point of view terpenoids. On the other hand,provided putting a question concerning profound
634 O. V. BAKHVALOV et al.
processing of significant amounts of phytoge-nous raw material (for example, turpentines,by-produced in the manufacture of cellulose,or limonene by-produced in obtaining juices ofcitrus plants) the following disadvantages ofknown methods for the conversion of terpe-noids are revealed to be obvious:
1. A necessity to use great volumes of ex-pensive and frequently hazardous reagents inorder to perform the synthesis. These circum-stances cause, in particular, the formation ofhazardous and difficult to recover waste in theamounts several times exceeding the volumesof the obtained product [13].
2. Due to a low selectivity of the reactionsone should carry out a careful and expensivepreparation of reagents and/or separation ofcomplex mixtures of products.
3. A low yield of target products caused bymanifold reactivity of natural compounds.
Solving practical problems, chemists confronteither with one of these circumstances (for ex-ample, performing the process with a high se-lectivity is possible, but it demands high ex-penses and practically non-feasible, hazardousreactants) or with their combination when eventhe application of modern �laboratory� meth-ods of organic synthesis can not provide obtain-ing the products with a reasonable yield. As aresult we have an essential difference in the priceof the products of the general and fine organicsynthesis based on the one hand on the prod-ucts of petrochemistry, and on the other handon the products of dendrochemistry.
It is obvious that the development of �usu-al� non-catalytic methods of organic synthesisin the field of dendrochemistry cannot changethe situation developed. In this connection thecatalytic epoxidation of terpenes could be con-sidered to be one of the most promising direc-tions in the field of using a renewable phyto-genous raw material.
The present review considers the papers con-cerning the epoxidation of available naturallyoccurring terpenes (α- and β-pinenes, 3-careneand limonene) published within the period from1988 to 2008. During last decade, publicationsconcerning biochemical epoxidation of terpe-nes began to appear [14�20] those will be alsoconsidered below. However, the main attentionwill be given to chemical methods for epoxida-
tion. The effects of enantioselectivity and di-astereoselectivity of oxidizing systems under useare not discussed in the present work.
Our work is intended to help researchers andtechnologists in choosing from the literature datasome rational conditions for practical epoxida-tion of terpenes those are suitable for scalingthis process up to industrial synthesis of oxiranes.
SOME GENERAL LAWS FOR EPOXIDATION OF TERPENES
As much as 24, 41, 119 and 129 works, re-spectively, are devoted to the problems of thesynthesis of β-pinene, 3-carene, limonene andα-pinene epoxides in the literature. Such a ra-tio is to a certain extent reflecting the avail-ability of the terpenes listed their readiness forepoxidation and practical importance of ep-oxides obtained. The following order for theability of terpenes to be oxidized [21] is known:3-carene > α-pinene > limonene > β-pinene.
However, the data we have gathered dem-onstrate that the capability of terpenes to ex-hibit the formation of the oxirane cycle de-pends not only on the structure of an initial com-pound, but also on the conditions this reactionis carried out. An essential role is played, forexample, by the size of an attacking complex(a catalyst with an epoxidizing agent [22]), bythe nature of the epoxidizing agent [23], by sol-vent [24] and other conditions of the process.For example, for the epoxidation by t-BuOOHand cumene hydroperoxide the decrease in ac-tivity for both epoxidizing agents can be pres-ened by the following series: cyclohexene > li-monene > α-pinene > β-pinene > camphene.
The absolute values of the conversion levelin the reactions of t-BuOOH oxidation bycumene hydroperoxide [25] and by some otheroxidizers are presented in Table 1.
One can see that to establish a universal scalefor the reactivity of olefins in the reaction ofdouble bond oxidation with the formation ofoxiranes is impossible. Hence, the statementoccurring in the literature that the double bondin this cycle is much more reactive than a dou-ble bond in a chain or an isolated double bond[31] (which is caused by a somewhat lower en-tropy loss in a cyclic molecule) is valid only fora limited number of epoxidation variants. It is
MODERN METHODS FOR THE EPOXIDATION OF α- AND β-PINENES, 3-CARENE AND LIMONENE 635
contradicted, for example, in [32] where it wasdemonstrated that citral and linalool are readi-ly epoxidized, whereas the yield of α- andβ-pinene amounts to 15 % only.
The latter is caused by a spatial hindrancefor the attack of double bonds by a bulky diatomicMn complex. A surprising dependence of epoxida-tion results on the reaction conditions (mainly onthe nature of a polyoxomethylate catalyst underuse) has been demonstrated in [33], whose authorsobtained 8,9-epoxide from R(+)-limonene with theyield of 89 % under soft conditions. With the useof other catalysts the formation of this compoundunder direct epoxidation conditions either did notoccur or its yield in the mixture with others isomersdid not exceed 30�35 %.
A law manifested by the fact that the ep-oxidation rate increases in the presence of elec-tron accepting groups in the source of activeoxygen as well as of electron donating groupsin alkene [34, 35] is considered to be more uni-versal. It should exhibit in the cases when themechanism of electrophilic oxygen addition tothe double bond is realized. However, the worksconsidered in the review demonstrate a much
more complicated, ambiguous and not conclu-sively established picture of oxiranes forma-tion. Three types of mechanisms are consid-ered to be possible for epoxidation reactions suchas a catalytic oxygen transfer to the doublebond, a free-radical mechanism and a Prile-zhaev reaction for the case when it is performedwith peracids.
MECHANISMS FOR THE INTERACTION OF TERPENES
WITH EPOXIDIZING AGENTS.
THE FEATURES OF SOME EPOXIDATION PROCESSES
The reactions of active oxygen addition tothe double bonds of terpenes use to proceedboth in the presence of catalysts, and withoutthem. The catalysis can be of both homoge-neous and heterogeneous nature. Recently thereis a tendency to use the second variant is mainlyobserved, whose basic advantage consists in thepotentiality of a repeated use of a catalyst.A number of compounds (Tables 3�6) are usedas a source of active oxygen, but much moreoften the latter represents hydrogen peroxideor molecular oxygen (air) (Table 2).
TABLE 1
Comparative reactivity of some terpenes in the reaction of epoxidation
Epoxidation conditions Terpene Conversion Selectivity, % Yield, % Ref.
level, %
O2, Ni(acac)2, Me2CHCHO α-Pinene 100 93 � [26]
Limonene 100 81 �
3-Carene 97 90 �
O2, Ru complex containing α-Pinene 100 98 � [27]cymol and 1,2,4-triazepine, Limonene 100 91 �
Me2CHCHO 3-Carene 96 98 �
60 % H2O2, Al2O3 α-Pinene 69 [28]
Limonene 83
3-Carene 87
35 % H2O2, Me3ReO3, pyridine α-Pinene 100 86 80 [1]
Limonene 100 90 90
β-Pinene 98 89 82
O2, Co salen complex, α-Pinene 70 [29]
Me2CHCHO Limonene 54
3-Carene 48
β-Pinene 64
30 % H2O2, DCC, cationite α-Pinene 73 [30]
Limonene 64
β-Pinene 48
636 O. V. BAKHVALOV et al.
It should be noted that the contribution ofcatalytic processes with the use of molecularoxygen as an oxidizer increases in the order ofβ-pinene, 3-carene, limonene, α-pinene.
The discovery of the catalytic properties ofMe3ReO3 (ÌÒÎ) in the reactions of epoxidationbecame a remarkable milestone in this researchfield [12]. Many alkenes can be epoxidized inthe presence of this substance under the actionof hydrogen peroxide at a room temperature.
Rhenium being heptavalent in the compoundMe3ReO3, activates hydrogen peroxide throughthe formation of η2-peroxo species 1 and 2. Thestructure of compound 2 is confirmed by the dataof crystallographic analysis; the presence of spe-cies 1 and 2 is proved with the use of NMR spec-troscopic methods [12]. As complex compoundswith nitrogen-containing ligands are formed fromÌÒÎ its reactivity increases. In order to preventthese ligands from washing away the ÌÒÎ is in-troduced into the structure of a polyvinylpyri-dine resin [36] or its complex is incapsulated intopolystyrene [37]. Thus a heterogeneous catalyst isobtained suitable in order to use it repeatedly.
Aluminium oxide have appeared a quite goodcatalyst of epoxidation reaction, in particularbasic one as well as that obtained according tothe method of sol-gel technology [38]. Its cheap-ness, availability and ecological compatibility
have caused interest in detailed studies on potenti-alities of this catalyst application [39, 40]. The mech-anism proposed for epoxidation is as it follows:
Much the same technological parameters arereached with the use anhydrous hydrogen per-oxide and its) 60 % solution for epoxidation at60�70 îÑ. In the latter case the process requiresfor water evaporation from reaction the mix-ture using a Dyne�Stark apparatus. Alumini-um oxide can be used use three times, furtherwith the conservation or even increase in theselectivity of limonene epoxidation the conver-sion level is considerably reduced.
Complexes of transition metals with β-dike-tones are widespread epoxidation catalysts. Theauthors of [41] studied the mechanism and ki-netics for the epoxidation of alkenes in the pres-ence of Ni(acac)2, isobutyl aldehyde and mo-lecular oxygen (usual conditions for the cata-lysts mentioned). A simplified picture of pro-cess is presented below:
TABLE 2
Main components of the systems epoxidizing terpenes
Initial Overall number Number of publications whose authors use:
compound of publications catalysts H2O2 O2
β-Pinene 24 16 (67) 13 (54) 4 (17)
3-Carene 41 29 (71) 28 (68) 7 (17)
Limonene 119 97 (81.5) 46 (39) 24 (20)
α-Pinene 129 106 (82) 43 (33) 40 (31)
Note. The percentage with respect to the total number of publications is specified in brackets.
MODERN METHODS FOR THE EPOXIDATION OF α- AND β-PINENES, 3-CARENE AND LIMONENE 637
The authors of [41] have concluded that theepoxidation reaction occurs at a ratioaldehyde : alkene ≥ 2, whereas the first impor-tant stage is presented by aldehyde coordina-tion with the nickel complex. The role of thiscomplex consists in promoting the hydrogenatom abstraction from aldehyde and in theacceleration of oxidation reaction. From the afore-mentioned Figure one could see both radical andnon-radical reactions to occur within the cycle,however the authors of [41] considered the na-ture of the process to be radical one and basingon kinetic studies came to the conclusion, thatthe reaction rate of the process does not dependon the concentration of an initial substance.
Copper salts can operate as active oxidation(epoxidation) catalysts. The authors of [35] haveproposed a reactivity series for similar com-pounds those they have obtained through theoxidation of adamantine by molecular oxygenin the presence of acetaldehyde. The experi-ments which they carried out in order to findout the oxidation mechanism for substitutedtoluenes in the presence of Cu(OH)2, have dem-onstrated that there are reactive intermediatessuch as Cu3+�O
. or Cu4+=O formed. The data
obtained are mainly strengthening the case forradical mechanisms.
Compounds containing cobalt such as CoN-aY, Co(NO3)2, PW11Co, CoW12, Co phtalocya-nine [42] are also efficient catalysts in the pres-ence of oxygen and aldehyde. The authors ofthis work considered the epoxidation with Co2+
compounds is a free-radical process initiated bysuch adducts as Co3+�O�O. The latter react
with aldehydes, which results in 3RCO• radical
formation with the participation of oxygen ofat the final stage of the process.
Under the conditions specified the reactivi-ty with the repeated use is exhibited also bycobalt polyoxometallates, applied onto modifiedmesoporous silicate matrices. The nature of amatrix and its treatment influence the cata-lyst activity [43].
The greatest number of works (18 publica-tions) is devoted to the studies on the catalyticsystem based on Mn porphyrin. This system ismodified through the introduction of aromaticsubstituents into the positions 5, 10, 15, 20 ofthe porphyrin ring. The best results were ob-tained in the case of porphyrins with phenylsubstituents. The metal of the porhyryn com-plex is bound with axial ligands such as chlo-rine, acetyl group, nitrogen-containing com-pounds (N-alkylimidazole). A more complicatedtwo-phase system was also proposed with thereductive activation of oxygen [44] (Fig. 1).
The complication of porphyrin catalysts isexpressed also in the introduction of addition-al substituents (Scheme 1, structures 3�5).
Catalysts are also synthesized those have thestructures with the cavities located lower thanthe porphyrin ring plane wherein axial ligands(nitrogen-containing heterocycles) can be placed.These ligands could influence the results ofepoxidation [45].
The epoxidation mechanism hypothesized isdemonstrated in Scheme 2 [46].
Methods for immobilizing the catalysts underdiscussion are also proposed, for example, ontozeolite Y [47], polystyrene [48], modified SiO2 [49].All the modifications of Mn porphyrins are ableto catalyze to a greater or lesser extent the reac-tions of allyl oxidation of terpenes.
Alkene + 2H+ + 2e + O2 > Epoxide + H2O
Fig. 1. Schematic presentation of a catalytic system, whichillustrates the role of [Rh(C5Me5)bipyCl2] complex as aphase-transfer catalyst. C5Me5 � pentamethylpentadiene.
638 O. V. BAKHVALOV et al.
Scheme 1.
Scheme 2.
.
MODERN METHODS FOR THE EPOXIDATION OF α- AND β-PINENES, 3-CARENE AND LIMONENE 639
A catalytic system based on Fe porphyrin isof limited occurrence. This system was subject-ed to a detailed investigation by the authors of[50]. The role of the catalyst could consists, toall appearance, in the initiation of a chain re-action via hydrogen abstraction from terpeneand decomposition of the hydroperoxide orhydroperoxyl radicals formed from radicals 6and 7 and molecular oxygen.
The radicals form with porphyrins a cation-radical species according to the equation(P)Fe3+X + ROO(H) → (P)+
.Fe4+(=O)X + RO(H)
This intermediate species is considered to beresponsible for the epoxidation:(P)+
.Fe4+(=O)X + Alkene > (P)+
.Fe3+X + Epoxide
8
The authors of [51] have found out that withthe increase of electron donating effect of sub-stituents in the phenyl fragments of porphyrincomplexes their catalytic activity falls. They pro-posed the relationship ln k = 1.2168σ � 7.9968for Mn porphyrin complex, and the relationshipln k = 0.625σ � 8.2426 for Fe porphyrin com-plex, where k is a the reaction rate constant,and σ is the Hammet constant for a substituent.
Cobalt porphypin catalysts under aerobicconditions in the presence of aldehydes arecharacterized as universal ones: they are ableto oxidize alcohols, benzyl compounds, arenes,alkenes, alkanes [52, 53]. In this case the reac-tions proceed via cobalt oxo species similar tointermediate species 8. In the publications in-cluded in the aforementioned reviews, amongall the set of terpenes considered only limonenewas entered into reaction with the Co porphy-rin catalyst The authors investigated the influ-ence of the substituent nature in the aromaticfragments of porphyrins upon the results ofthe reaction and noted that electron donatingsubstituents cause an increase in the activityof catalysts. Aldehydes, especially 2-methyl-propanal, perform the function of reductiveoxygen activation.
The consideration of the features of metalporhyrin catalysts would be logically complet-ed with the comparison of their activities de-
pending on the nature of metal. This could beexpressed by the following order of conversionlevel values for α-pinene under the conditionsmentioned above [54]: TPPMn3+Cl > TPPCo3+Cl >TPPFe3+Cl > TPPCu2+ ≈ TPPNi2+ ≈ TPPZn2+ (TPPstanding for tetraphenylporphyrin).
The dependence presented is inherent in thefirst three members of the series and coincideswith that for the reactions of limonene epoxi-dation [55]. The authors of this paper have re-vealed the activation of limonene conversionwith the use t-BuOOH instead of NaOCl as anoxidizer and methylene chloride instead of ac-etonitrile and ethyl acetate as a solvent.
Manganese compounds are much more pref-erable than others also due to the cheapnessand non-toxicity of this metal.
A great many of works is devoted to metalporphyrins. Among several books a monograph[56] where one of the sections is devoted tothe epoxidation of alkenes (rather than terpe-nes) by some people metal porphyrins has a rel-evancy to the topic of the present review.
Another group of composite complex cata-lysts with transition metal as a central atom isformed by Mn- and Co-salen complexes (in thearticles for 2006�2007 they are referred to as�salophen complexes�). The mechanism of epoxi-dation by them is identical and similar to thatoccurring in the reaction of epoxidation by por-phyrins. To all appearance, during the oxidationa radical such as M�O�O
. is formed (it is demon-
strated by ESR method) to convert into an oxo-metallic intermediate species (salen) M=O whichtransfers oxygen to the double bond of olefin [57].
An epoxidizing agent depicted in the Schemeis typical alongside with PhIO4, NaIO4 and O2
for salen complexes (the use of hydrogen per-oxide is inefficient). Salen complex catalysts inthe reaction of epoxidation exhibit the follow-ing features:
1. Simultaneously with epoxidation the allyloxidation of terpenes and the formation ofalcohols and ketones are observed to occur.These processes are of free-radical nature.
640 O. V. BAKHVALOV et al.
2. The reductive activation of oxygen canbe realized with various carbonyl compounds.
3. The direction and results of the processare to a considerable extent depending on thestructure of a salen complex.
A number of immobilized salen complexeshave been obtained on Dowex MsCl [58], onmodified macroporous zeolites [59], on silica gel,polystyrene, MCM-41, montmorillonite (seeTables 3�6). In some of papers listed a com-parison of the results was carried out for theepoxidation with the use of immobilized salencatalysts and with the use of homogeneousmedia. The former variant resulted in improv-ing the manufacturability and selectivity of theprocess, as well as in growing the yield of ep-oxide, whereas the reaction rate and the pro-ductivity of catalyst decreased. The catalyst link-age with a support can be realized through imi-dazole or 1,4-phenylenediamine, as well as viathe incapsulation within the pores of zeolite.
Rather high activity in the epoxidation of someterpenes is exhibited by Mn complex with trim-ethyltriazacyclononane. The introduction of theoxalate buffer in the system prevents hydrogenperoxide from decomposition and allows one toepoxidize terminal double bonds successfully [11].
This catalyst can be immobilized onto silicagel [60]. The disadvantages of the catalystshould be considered to consist in its ability toinitiate the formation of diols, as well as cam-pholenic aldehyde (from α-pinene).
The selectivity of epoxidation for alkenes ofdifferent structure as well as mainly cyclic alk-enes and limonene as compared to α-pinene isinherent also in dioxomolibdenium complex cat-alysts, such as compounds 9�10à (Scheme 3).
In this case the reaction with α-pinene resultsin the formation of many by-products, too.
Several works were devoted to the combi-nation of Mo oxides with silicates. Worthy ofinterest is paper [61] whose authors combinedmesoporous silicates (MCM-41, SBA-15) andamorphous porous silicon dioxide with molyb-denum oxides in single-reactor synthesis andthen carried out comparative studies and testsof the samples obtained. All the varieties ofmolybdenum silicates almost equally catalyzethe reaction of limonene epoxidation with t-BuOOH, whereas in the case of using grindedgranules (especially precipitated silicon dioxide)the efficiency of catalysts grows in comparisonwith the mesoporous silicate samples.
Molybdenum carbonyl represents an interestingvariety of molybdenum catalysts. The compound isfixed on cross-linked polystyrene via an imidazoleor piperazine spacer (fragments 11 and 12).
Such catalysts demonstrate a high efficiencyunder repeated use. In this case the authors ofall the published works used t-BuOOH as anoxidizer (see Tables 3�6).
Binuclear Mn complex [LMnO3MnL](PF6)2 13described for the first time in 1988, to allappearance, is convenient in using for thetechnical purposes, for example, for bleachingspots; it is interesting from the theoreticalstandpoint due to an unprecedentedly small(2.296 Å) distance between Mn atoms inherentin this complex (to compare: the interatomicMn�Mn distance in the molecule Mn2(CO)10
amounts to 2.93Å).
Scheme 3.
MODERN METHODS FOR THE EPOXIDATION OF α- AND β-PINENES, 3-CARENE AND LIMONENE 641
TA
BLE 3
Mai
n c
onditio
ns
and r
esults
for
α-pin
ene
epox
idat
ion
No.
Epox
idiz
ing
Cat
alyst
Auxilia
ry re
agen
ts,
Ò,
î CR
eact
ion
Con
ver
sion
S
elec
tivity,
Yie
ld,
%Ref
.ag
ent
co-c
atal
yst
stim
e, h
leve
l, %
%
12
34
56
7
8
910
1
40%
M
eCO
OO
HPhas
e tr
ansf
erA
cid s
caven
ger
10�20
3�5
95
[79]
cata
lyst
2
35%
H
2O2
230
MTO
0.5
Pyri
din
e, 4
2 20
2.3
100
8
6 9
0[1
]
3
35%
H
2O2
200
[PW
4O24
](C
8H17
) 3N
CH
3 1.0
H2N
CH
2H2P
O3
2.0,
60
1 8
3 9
1 7
6[8
0]N
a 2W
O4
⋅2H
2O 3
.0,
NaO
H u
p t
o pH
4.2
4
50%
H
2O2
NaW
O4
QA
S10
0 94
94
[81]
5
30%
H
2O2
270
DCC 2
0, g
as� N
2 25
24
83
[82]
6
30%
H2O
2 12
0M
esop
orou
s hybri
d 55
5
up t
o 23
>99
~23
[83]
[(MeO
) 3SiC
H2]
2+ (M
e)4N
OH
+ N
aOH
+ H
2O2.7
mg p
er 1
mm
ol o
f ol
efin
7
1O
2M
e 2CH
CH
O 3
00 25
0.5
100
93
93[2
6]
2.0
8
O2
Pr
com
pou
nd, 1
mas
s %
MeC
H2C
HO
140
30�60
8 9
2 73
67
[84]
9
30% M
eCOOOH 1
10A
nhydro
us
MeC
OONa
154
25
2 8
2[8
5]
102
35%
H2O
2 20
00M
nSO
4 0.2
Me 4
NH
CO
3 10
0 25
3 5
3[6
9]
11
40 %
MeC
OOOH 1
0050
% N
aOH
up t
o pH
7 20
1.5
83
~100
~84
[86]
12
O2
Cu(O
H) 2 1
.0
25 1
710
0 84
84
[35]
300
13
O2
75
6 6
7[8
7]
1413
Co(
SM
eDPT)
2.0
642 O. V. BAKHVALOV et al.
TA
BLE 3
(Con
tinued
)
12
34
56
7
89
10
14
O2
4520
96
9793
[88]
4119
2.0
Zeo
lite
4À
15
MeC
OO
OH
89[8
9]
16
O2
Me 2
CH
CH
O 2
0025
6 9
797
94[9
0, 9
1]
2.4
Co
173
5%
H2O
2 17
025
327
[92]
100
R1 �
R12
, H
, var
ious
gro
ups
R13�R
15,
H, al
kyl, a
ryl, h
eter
oary
l
18
O2
Me 3
CCH
O 4
0025
4 9
595
90[9
3]
19
t-B
uO
OH
100
CuCl 2
(n-B
u) 4N
Br
2514
18
7814
[73]
204
O2
CoB
r 2 0
.15
Pyri
din
e50
22~5
3[7
5]
21
O2
Ni(ac
ac) 2,
bou
nd w
ith P
BI
Me 2
CH
CH
O 3
0025
410
088
88[9
4]
pol
ym
er
1.0
Ni
MODERN METHODS FOR THE EPOXIDATION OF α- AND β-PINENES, 3-CARENE AND LIMONENE 643
TA
BLE 3
(Con
tinued
)
12
34
56
7
89
10
22
15%
H2O
2 20
0M
ixtu
re o
f R
33+(P
W12
O40
)3-,
Gas
� N
2 7
02
92
[95]
wher
e R
=πC
5H5N
(CH
2)15M
e+ P
h3S
iOEt + M
e 2N
CH
(OCH
2Ph) 2 0
.5
23
OK
CO
HK
2CO
3 87
0 2
50.1
>98
[96]
(2K
HSO
5 +
KH
SO
4
+ K
2SO
4) 2
10
50
24
NaO
Cl 96
Pyri
din
e 04
or
25
3 8
1[9
7]
4-te
rt-B
u-p
yri
din
e 0.2
Bu
4NCl 0.8
gas
� N
2
M =
Mn(I
II)C
l 0.4
255
O2
Co2+
sal
en inco
rpor
ated
Me 2
CH
CH
O 3
00 2
04
82
[98]
into
pol
yan
ilin
e,6
mg p
er 1
mm
ol o
f ol
efin
26
O2
Na 2
CO
310
00.7
30
[72]
644 O. V. BAKHVALOV et al.
TA
BLE 3
(C
ontinued
)
12
34
56
78
910
276
NaC
lOG
as �
N2 or
Ar
702
9050
45
[9
9]
M =
Mn,
R1 = N
O2,
R2 = R
3=H
,
X = A
cO,
0.00
95 m
g p
er 1
mm
ol o
f ol
efin
28
Mes
opor
ous
mat
eria
l s
uch
as
700.5
4984
41
[7
6]
MCM
-41w
ith f
orm
ula
of
708
60.5
51 3
1SiO
2⋅x
TiO
2⋅n
S;
x =
0.000
1�0.5,
150
S i
s an
org
anic
com
pou
nd
29
30%
H2O
2 52
0M
eCO
OH
100
251
~10
[2
2]
16
307
MnA
lPO
-5 7
.065
1 2
6[1
00]
MODERN METHODS FOR THE EPOXIDATION OF α- AND β-PINENES, 3-CARENE AND LIMONENE 645
TA
BLE 3
(Con
tinued
)
12
34
56
78
910
31
30%
H2O
2 40
00M
nSO
4 10
00CO
(NH
2)2 20
8025
9 91
93 8
5[1
01]
NaH
CO
3 30
32
O2
Irra
dia
tion
with lig
ht
4016
30�33
[102
]
at 3
80nm
<λ
<75
0nm
0.2
33
PhIO
Mn
3+sa
len Cl 1.0
Gas
� N
2 or
Ar
2516
50�60
~36
20
[103
]
34
t-B
uO
OH
30
Mes
opor
ous
Ti-
MCM
-41
55 5
11
100
11
[104
]
or 3
0%
H2O
2 12
02.7
mg p
er 1
mm
ol o
f ol
efin
55 5
6
100
6
35
30%
H2O
2 10
00M
nSO
4 10
0.2
M N
aHCO
3 so
l.,25
16 54
[105
]
pH
8
36
O2
Fe 2
O3
1.0
Ben
zald
ehyde
2517
.5 10
090
90
[106
]
378
30%
H2O
2 52
0W
O3
1.7
H3B
O3
1.0
1.0
70 4
19
[107
]
NaO
H 4
.0
(C8H
17) 3M
eNH
SO
4 1.0
38
30%
H2O
2 12
025
1.5
>98
100
>98
[3
6]
150
mg p
er 1
mm
ol o
f ol
efin
646 O. V. BAKHVALOV et al.
TA
BLE 3
(Con
tinued
)
12
34
56
78
910
39
O2
Me 2
CH
CH
O 3
0825
0.5
100
98
98
[2
7]
0.15
409
60%
H2O
2 20
0A
l 2O
3 su
bac
idic
49
(C4H
9)2O
10
~77
4 6
9 [2
8]
Gas
� N
2
41
30%
H2O
2 52
0 2
5 0.25
10
97
10
[108
]
0.02
42
30%
H2O
2 20
0H
PO
4W2O
2(µ-
O2)
2(O
2)2�
20
3 3
0 9
8 2
9[1
09]
(n-C
6H13
) 4N
+ 1
.0 b
y W
43
Gas
� A
r �5... 0
210
0~9
392
�95
[110
]
44
O2
Ni(ac
ac) 2,
impre
gnat
edM
e 2CH
CH
O 2
20 2
516
100
26
26
[111
]
into
cla
y K
-10
(Cla
ynia
c)10
mg p
er 1
mm
ol o
f ol
efin
45
H2O
2⋅C
O(N
H2) 2
230
(MeC
O) 2O
230
25
3 78
[6
2]
10
0
467,
830
% H
2O2
160
WO
3⋅H
2O 2
.0N
a 3PO
4⋅1
2H2O
1.3
70
4 8
0[1
12]
(C8H
17) 3N
+M
e H
SO
4- 1.0
70
96 9
7
Gas
� N
2
477
1Ì
NaO
H 2
00 2
524
4
5[1
13]
+ H
2O2 10
0
48
30%
H2O
2 13
00K
HCO
3 20
0 2
5 83
[6
7]
DCC 2
00
MODERN METHODS FOR THE EPOXIDATION OF α- AND β-PINENES, 3-CARENE AND LIMONENE 647
TA
BLE 3
(Con
tinued
)
12
34
56
78
910
49
O2
Co,
CoC
l 2,
CrO
3, C
u c
omple
xes
65�90
4 5
4 [3
1]w
ith p
yri
din
e, b
enzp
yri
din
e,
pic
olin
e 1.0
50
O2
Me 2
CH
CH
O 3
00 25
4 9
3 9
286
[4
1]
1.0
51
O2
Alu
mop
hos
phat
es A
lPO-5
Ben
zald
ehyde
300
50
8 5
9 9
154
[114
]
and
AlP
O-3
6 w
ith subst
ituting
a par
t of
Al by M
n o
r Co
0.97
mg p
er 1
mm
ol o
f ol
efin
52
t-BuO
OH
150
55
24 6
3 13
8[1
15]
1.0
53
35%
H2O
2 15
0�10
1>
98~1
0098
[3
7]
1.0
54
O2
Co
on m
esop
orou
s SiO
2M
eCN
6024
3
18
0.5
[7
4]7.1
mg p
er 1
mm
ol o
f ol
efin
55
H2O
2 30
0Ti-
SB
A (
65)
� 5
73 m
esop
orou
s70
24~3
2~1
0035
[116
, 11
7]
SiO
2 (S
BA
-15)
gra
fted
with T
i10
mg p
er 1
mm
ol o
f ol
efin
648 O. V. BAKHVALOV et al.
TA
BLE 3
(C
ontinued
)
12
34
56
78
910
5610
t-B
uO
OH
160
Sam
e as
abov
e,80
24 9
110
091
[116
, 11
7]
14.3
mg p
er 1
mm
ol o
f ol
efin
57
H2O
2 10
0M
eCO
ON
H4
1325
24 5
2 7
137
[4
7]
built-
in t
o ze
olite
Y,
20 m
g p
er 1
mm
ol o
f ol
efin
581
1O
225
610
093
93
[8]
48
Me 3
CCH
O 2
49
LD
H-[
Mn(C
l)L]
Within
the
lam
inar
sol
id
such
as
hydro
talc
ite,
the
conte
nt
of M
n b
eing o
f 0.85
%,
27 m
g p
er 1
mm
ol o
f ol
efin
MODERN METHODS FOR THE EPOXIDATION OF α- AND β-PINENES, 3-CARENE AND LIMONENE 649
TA
BLE 3
(C
ontinued
)
12
34
56
78
910
59
NaI
O4
200
250.6
89
9383
[58]
on m
acro
por
ous
cation
ite
Dow
ex M
SC
l,M
n(s
alen
)Dow
ex 3
.8
60
O2
Co(
NO
3)2 2.0
Me 2
CH
CH
O 7
6024
5.5
99
9796
[4
2]
61
t-B
uO
OH
150
5530
�40
279.5
[118
]
Cat
alyst
im
mob
iliz
ed
onto
mes
opor
ous
mod
ifie
d
subst
rate
MCM
-41
1.0
62
Anhydro
us
Al 2O
3 neu
tral
, pH
790
4
7085
60 [3
9]
H2O
2 20
0
650 O. V. BAKHVALOV et al.
TA
BLE 3
(C
ontinued
)
12
34
56
78
910
637
2Ì
NaO
H5�
102�
3 95
83
79
[6
8]
up t
o pH
7.0�8.5
+ H
2O2 22
0
6412
[119
]
657
2Ì
NaO
H 1
50 2
5 1.5
~100
~70
~70
[120
]
+ H
2O2 15
0
66
C6H
5IO
25
8
91�92
[5
0]
TPPFeC
l, i
mm
obiliz
atio
n
onto
dex
trin
0.2 is
pos
sible
67
NO
3 ra
dic
al 2
5 ~6
0[1
21]
in a
n iner
t
gas
flo
w
68
100
% H
2O2
200
CF
3(CF
2)8C
O(C
F2)
6CF
3 5.0
Na 2
HPO
4 8
3 0.5
5
5[1
22]
Gas
� N
2
6912
MeC
OO
OH
[123
]
701
3O
2Ir
radi
ation
by a
mer
cury
- 2
5 8
~3
0[1
24]
disch
arge
lam
p
TPP is
tetr
aphen
yl-
por
phyri
nat
o 0.01
MODERN METHODS FOR THE EPOXIDATION OF α- AND β-PINENES, 3-CARENE AND LIMONENE 651
TA
BLE 3
(Con
tinued
)
12
34
56
78
910
71
NaC
lO 0
6 1
9[1
25]
1.0
72
t-B
uO
OH
150
5524
~25
15 4
[126
]
imm
obiliz
ed o
nto
mes
opor
ous
MCM
-41,
MCM
-48,
24 m
g p
er 1
mm
ol o
f ol
efin
73
30%
H2O
2M
nSO
4N
aHCO
325
52~7
9[1
27]
74
NaH
CO
3~9
0[1
28]
75
Na 2
CO
4(M
eCO
) 2O
, Q
AS,
US
[129
]
76
30%
H2O
2D
CC 2
0, K
HCO
3 20
2524
83
[130
]
77
NaO
Cl 11
025
100
88 8
8[1
31]
1.5
4-te
rt-B
u-p
yrid
ine
1.5
X =
NO
2, Y
= Z
= H
,
Mn(T
NPP)C
l 0.5
652 O. V. BAKHVALOV et al.
TA
BLE 3
(Con
tinued
)
12
34
56
78
910
78
KH
SO
5 17
5Q
AS 1
.5 2
510
096
96[1
32]
Mn(T
DCPP)C
l X
= Z
= C
l,
Y =
H 0
.5
79
t-B
uO
OH
100
124
[133
]
0.17
80
O2
HC
OO
Na,
pH
8 4
0[1
34]
2
.0
Cp=
η5 C5M
e 5
(PhCO
) 2O
100
3.3
MnTF
5PP 0
.03
81
O2
Cu(O
H) 2
2.0
25
1710
083
83[1
35]
300
MODERN METHODS FOR THE EPOXIDATION OF α- AND β-PINENES, 3-CARENE AND LIMONENE 653
TA
BLE 3
(Con
tinued
)
12
34
56
78
910
82
10%
H2O
2 25
00M
TO
1.0
25
2 7
0 5
0 3
5[1
36]
25
1 5
5 9
9 5
4
6.0
8314
O2
100
3 7
0~3
5 2
4[1
37]
Inca
psu
late
d into
zeo
lite
Y
1.4
mg p
er 1
mm
ol o
f ol
efin
84
O2
Co 4
(µ3-
O) 4
⋅(µ-
PhCO
2)4
⋅(4-
CN
py) 4
100
24 6
7~6
5
44[1
38]
com
ple
x w
ith c
ubic
str
uct
ure
0.32
85
t-BuO
OH
CpM
oO2C
l, ob
tain
ed i
n s
itu f
rom
55
6 4
2 2
0
8.5
[139
]CpM
o(CO
) 3Cl
and t
-BuO
OH
2.0
86
t-BuO
OH
Mo(
CO
) 5,
imm
obiliz
ed o
nto
76
910
010
010
0[1
40]
pol
yst
yre
ne
thro
ugh i
mid
azol
e sp
acer
,
40 m
g p
er 1
mm
ol o
f ol
efin
87
Air
25
8~2
6[1
41]
Phta
locy
anin
e co
mple
x 0
.7
88
t-BuO
OH
Mo(
CO
) 5,
imm
obiliz
ed o
nto
76
3 9
710
0 9
7[1
42]
pol
yst
yre
ne
thro
ugh p
iper
azin
e
spac
er 1
.1
89
O2
Mn p
hta
locy
anin
e co
mple
xM
e 2CH
CH
O[1
43]
654 O. V. BAKHVALOV et al.
TA
BLE 3
(Con
tinued
)
12
34
56
78
910
90
H2O
2Silan
ized
hig
h-d
isper
se[1
44]
MC
M-4
1 an
d M
CM
-48
with e
nhan
ced
cata
lytic
activity o
f N
b a
nd T
a
imm
obiliz
ed t
her
eon
91
O2
Me 2
CH
CH
O 2
00 2
510
�15
70
[2
9]
5.0
92
30%
H2O
2 20
0PhCO
OH
0.5
0
0.2
9874
73
[145
]
Mn(T
DCPP)C
l
X =
Z =
Cl,
Y =
H 0
.5
93
60%
H2O
2 25
0(H
4N) 6M
o 7O
24 �
(Bu
3Sn) 2
O 2
5 3
5997
57
[146
]
94
t-B
uO
OH
Oxom
olybden
um
81 [2
5]
inco
rpor
ated
into
cat
ionite
71
95
NaO
Cl
Mn
3+-t
etra
phen
ylp
orphyri
nPyri
din
e, 5
3[1
47]
conta
inin
g M
eCO
O g
roup
�
MODERN METHODS FOR THE EPOXIDATION OF α- AND β-PINENES, 3-CARENE AND LIMONENE 655
TA
BLE 3
(Con
tinued
)
12
34
56
78
910
96
30%
H2O
2 20
00.5
0
0.2
9874
73
[148
]
PhCO
OH
2.0
Mn(T
DCPP)C
l
X=
Z=
Cl,
Y =
H 0
.5
97
30%
MeC
OOOH
Na 2
CO
330
�35
1.5�
2 9
6[1
49]
98
15,1
6O
2
25 8
~50
[150
]
Lig
ht
with
λ >
350
nm
99
CO
(NH
2)2
⋅H2O
2 3
78
[6
2]
100
Air
Mn
3+(T
PP)
40
1
~53
[151
]
+R
h3+
(η5 -
C5M
e 5(b
ipy)C
l 2 1
.75
3.5
(C6H
5O) 2O
17
540
HCO
ON
a 35
Et 3
N u
p t
o pH
8.5
656 O. V. BAKHVALOV et al.
TA
BLE 3
(C
ontinued
)
12
34
56
78
910
101
10%
H2O
2 20
0M
TO
1.0
20 1
55
9854
[109
]
102
Air
Mn
3+(T
PP) w
ith 1
-met
hyl
imid
a-H
CO
ON
a40
8Epox
ide
[152
]
zole
as
an a
xia
l ligan
dco
nte
nt
in t
he
pro
duct
is e
qual to
100
%
10317
30%
H2O
2PhCO
ON
a up t
o pH
4.5
0 1
.3 9
592
87 [4
6]
~0.2
1041
830
% H
2O
2W
O3
⋅H2O
2.5
(C10
H22
) 3N
3.0
60 3
89[1
53]
or M
oO3, o
r H
2WO
4N
a 3PO
4⋅1
2H2O
1.6
Gas
� N
2
10519
O2
Me 3
CCH
O25
3 1
0096
96 [5
9]
Cat
alyst
is
inco
rpor
ated
into
mac
ropor
ous
zeol
ite,
Co
tota
l co
nte
nt
is 0
.29
%,
R1=
R2=
t-Bu, 13
.5 m
g p
er
1 m
mol
of
olef
in
106
O2
CoC
l 2 0
.5�1.0
60 4
48�55
3015
[154
]
107
H2O
2 22
0 0
20 26
4612
[6
0]
Mn-d
mta
cn
MODERN METHODS FOR THE EPOXIDATION OF α- AND β-PINENES, 3-CARENE AND LIMONENE 657
TA
BLE 3
(Con
tinued
)
12
34
56
78
910
108
t-B
uO
OH
150
SiO
2 co
nta
inin
g M
oCycl
ohex
ane
80
8
32 4
1
13[1
55]
in t
he
form
of iso
pro
pio
nat
e(C
4H9)
2O 2
5 8
0 2
4
44 3
4
15
Mo(
O-i
-Pr)
-SiO
2
109
20
298
�10
0[1
56]
12
0
110
O2 â
MeC
NM
e 2CH
CH
O 6
020
�80
[157
]
on c
onju
gat
ed
N-c
onta
inin
g p
olym
ers
111
Air
1M
Pa
Nan
osiz
ed TiO
2 7
0 3
5 4
1 14
[158
]
112
MeC
OO
OH
[159
]
113
Air
Mn a
nd F
e co
mple
xes
[5
1]
with t
etra
phen
ylp
oroh
yri
n
1142
0M
nA
lPO
-5H
2O 4
218
65
1 7
810
078
[160
, 161
]
9.3
mg p
er 1
mm
ol o
f ol
efin
pH
5.2
65
4 8
9 6
961
107
115
O2 â
MeC
NM
e 2CH
CH
O 2
00
65 1
59[1
62]
on c
onju
gat
ed
N-c
onta
inin
g p
olym
ers
1162
1H
2O2
in s
itu
MnSO
4CO
2, O
2, i
onic
5�20
3�5
75
83
62 [7
0]
liquid
658 O. V. BAKHVALOV et al.
TA
BLE 3
(Con
tinued
)
12
34
56
78
910
117
NaI
O4
in a
queo
us
25 2
.510
0 9
292
[163
]
med
ium
200
8
.4
118
Air
, 3
MPa
Mn
0.04
Al 0
.96P
O4-
36Ben
zald
ehyde
300
50 8
59
9154
[161
]
0.97
mg p
er 1
mm
ol o
f ol
efin
119
NaI
O4
in a
queo
us
25 3
100
9090
[164
]
med
ium
200
8.4
120
NaI
O4
in a
queo
us
252.5
93
94.6
88[1
65]
med
ium
200
10.8
1212
2H
2O2
in s
itu
MnSO
4 0.06
mol
. %A
nol
yte
� 2
MH
2SO
4,25
1.5
23 [7
1]
Cat
hol
yte
� 1
M N
aHCO
3,te
rt-b
uta
nol
, O
2
MODERN METHODS FOR THE EPOXIDATION OF α- AND β-PINENES, 3-CARENE AND LIMONENE 659
TA
BLE 3
(Con
tinued
)
12
34
56
78
910
122
MeC
OO
OH
MeC
OO
H[1
66]
30%
H2O
2N
aHCO
3
NaO
H
123
NaI
O4
in a
queo
us
2510
92
9386
[167
]
med
ium
200
9.4
inca
psu
late
d
in z
eolite
Yw
ith n
anop
ores
124
NaC
lO in a
queo
us
Bu
4NCl 0.8
25 3
81 [4
5]
med
ium
100
Gas
� N
2
Pyri
din
e 0.4
M =
MnCl
0.4
660 O. V. BAKHVALOV et al.
TA
BLE 3
(End)
12
34
56
78
910
125
t-B
uO
OH
5524
1254
6.5
[168
]
(5.5
M in d
ecan
e) 1
54
1.0
126
O2
[Bu
4N] 4H
[PW
11Co(
H2O
)O39
]M
e 2CH
CH
O 4
0025
2.0
9694
90 [4
3]on
mes
opor
ous
silica
te
mat
rice
s 0.6
12723
Anhydro
us
24%
H2O
2A
l 2O
3, 5
mg p
er 1
mm
ol o
f te
rpen
e77
632
6220
[3
8](s
ol. i
n e
thyl ac
etat
e)
200
128
O2
Me 2
CH
CH
O 5
0035
670
4733
[169
]
1 A
n a
ctiv
ity s
erie
s fo
r Ñî,
Fe,
Ìn,
Ni ac
etyal
ceto
nat
es is
pre
sente
d;
elec
tron
don
atin
g s
ubst
ituen
ts in a
cety
lace
tonat
es r
aise
the
activity o
f t
he
cata
lyst
.2 A
n ion
ic liq
uid
was
use
d a
s a
solv
ent
whic
h c
an b
e use
d r
epea
tedly
.3
Chir
al e
pox
ide
with e
e up t
o 58
% is
form
ed w
ith t
he
use
of
chir
al M
n c
omple
x.
4 The
reac
tion
mix
ture
con
tain
ed 4
6 %
of
ver
ben
one
and 2
1 %
of
epox
ide.
5 D
ata
conce
rnin
g t
he
epox
idat
ion o
f dod
ecen
e-1.
6 A
n a
lter
nat
ive
cata
lyst
is
the
com
ple
x t
win
ned
thro
ugh o
xygen
.7
An e
pox
idiz
ing a
gen
t is f
orm
ed i
n s
itu.
8 D
ata
conce
rnin
g t
he
epox
idat
ion o
f 3-
care
ne.
9 Epox
idat
ion w
ith d
istillin
g w
ater
out
of t
he
reac
tion
mix
ture
.10
Etc
hin
g o
f th
e ca
taly
st is
obse
rved
.11
Epox
ide
with e
nan
tiom
eric
exce
ss o
f 9
8 %
is
form
ed d
ue
to c
hir
al lig
and.
12 T
her
e ar
e no
spec
ific
dat
a in
the
abst
ract
con
cern
ing t
he
exper
imen
t.13
A
n a
lter
nat
ive
cata
lyst
is
O=
MoT
PP(O
Me)
.14
Co
can b
e use
d inst
ead o
f R
u.
15 I
ron c
omple
x c
ould
be
use
d,
too.
MODERN METHODS FOR THE EPOXIDATION OF α- AND β-PINENES, 3-CARENE AND LIMONENE 661
16 E
pox
ide
obta
ined
con
tain
s an
exce
ss o
f S-i
som
er u
p t
o 67
%.
17 T
he
stru
cture
of
cata
lyst
can
var
y w
ith r
espec
t to
subst
ituen
ts in t
he
ben
zene
rings, r
egar
din
g a
xia
l ligan
ds, r
egar
din
g b
onds
bet
wee
n t
he
aryl gro
ups.
18 D
ata
conce
rnin
g t
he
epox
idat
ion o
f cy
cloo
cten
e.19
Epox
ide
obta
ined
con
tain
s an
exce
ss o
f S iso
mer
up t
o 91
%.
20 S
olid
epox
idiz
ing a
gen
t su
ch a
s ac
etylp
erox
ybor
ate
on M
nA
lPO
-5 r
eact
s w
ith w
ater
to
pro
duce
ace
tic
acid
and h
ydro
gen
per
oxid
e.21
Hydro
gen
per
oxid
e is f
orm
ed f
rom
the
alkal
ine
solu
tion
of
ionic
liq
uid
con
tain
ing o
xygen
.22
Hydro
gen
per
oxid
e is f
orm
ed f
rom
NaH
CO
s, s
olution
con
tain
ing o
xygen
.23
Alu
min
ium
oxid
e ob
tain
ed v
ia s
ol-g
el m
ethod
and c
alci
nat
ed a
t 40
0 o Ñ
was
use
d.
Not
es. 1. N
um
ber
s in
the
form
ula
s of
epox
idiz
ing a
gen
ts,
cata
lyst
s, a
uxilia
ry r
eagen
ts d
esig
nat
e th
e dos
age
of t
hes
e co
mpou
nds
in m
ol. %
with r
espec
t to
ter
pen
e ex
cept
asot
her
wise
not
ed. 2. T
he
resu
lts
epox
idat
ion
are
char
acte
rize
d b
y t
he
conver
sion
lev
el f
or t
erpen
e, s
elec
tivity w
ith r
espec
t to
epox
ide
and t
he
yie
ld o
f ep
oxid
e; i
f on
e of
the
thre
e par
amet
ers
is n
ot s
pec
ifie
d in t
he
refe
rence
, it w
as c
alcu
late
d a
ccor
din
g t
o under
the
form
ula
: se
lect
ivity =
yie
ld/c
onver
sion
lev
el [78
]. 3. F
rom
sev
eral
res
ults
obta
ined
in
the
sam
e w
ork u
nder
clo
se c
onditio
ns, t
he
Tab
le d
emon
stra
tes
the
bes
t on
e. 4
. Som
e not
es a
re c
ause
d b
y t
he
fact
that
ther
e is s
omet
imes
no
exam
ple
in a
pat
ent
for
the
epox
idat
ion o
f te
rpen
e w
hic
h t
he
Tab
le is
dev
oted
to;
in t
his c
ase
the
Tab
le d
ispla
ys
the
epox
idat
ion p
aram
eter
s fo
r an
other
ter
pen
e pre
sente
d in t
his p
aten
t.
662 O. V. BAKHVALOV et al.
TA
BLE 4
Mai
n c
onditio
ns
and r
esults
for
lim
onen
e ep
oxid
atio
n
No.
Epox
idiz
ing
Cat
alyst
Auxilia
ry r
eagen
ts,
Ò,
î CR
eact
ion
Con
ver
sion
S
elec
tivity, %
Yie
ld,
%R
ef.
agen
tco
-cat
alyst
stim
e, h
level
, %
12
34
56
7
8
910
1H
2O2
⋅CO(N
H2)
2CF
3CH
(OH
)CF
3 14
10 2
5 7
100
88
88
[170
]
300
2 2
512
82 o
r>90
[171
]
100
or 2
30
31
F2+
H2O
+M
eCN
NaH
CO
3�10
0.02
35
[172
]
Gas
� N
2 0
35
4H
2O2
50
4[1
73]
5t-BuOOH
160
Ti-
SBA
(65
)-57
3 8
024
97
100
97
[117
]
mes
opor
ous
SiO
2 SBA
-15
gra
fted
with T
i
6O
2N
i(ac
ac) 2
Me 2
CH
CH
O 3
00 2
5 2.5
100
81
81
[2
6]
7O
2M
e 2CH
CH
O 2
00 2
5 3
100
[5
2]
X =
Z =
H, Y
= O
Me
Co(
II)T
PP-O
Me
5.0
MODERN METHODS FOR THE EPOXIDATION OF α- AND β-PINENES, 3-CARENE AND LIMONENE 663
TA
BLE 4
(Con
tinued
)
12
34
56
78
910
8O
2Co2+
com
ple
x w
ith
Me 2
CH
CH
O 2
00
2512
�14
~100
[174
][3
.2.1
]cry
pta
nd
and p
icra
te [Co(
L)](p
icra
te) 2
5.0
92
20
2
~100
[156
]
20
2+
4
100
or 2
00
10
30%
H2O
2 15
0PhCN
150
25
48
86
[82]
KH
CO
3 10
0
11
t-B
uO
OH
100
MoO
3-4S
iO2 0.1
50
12
~85
~100
~85
[23]
(mol
ybdos
ilic
ate)
12
30%
H2O
2 15
0M
TO
0.5
Pyri
din
e 12
25
11
96
98
94
[175
]
13
50%
H2O
2 20
0A
mber
lite
IR
A-9
00 in t
he
form
38
24
84
93
78
[80]
of V
entu
rello
anio
n P
W4O
243�
14
MeC
OO
OH
[176
]
15
60%
H2O
2 20
0A
s(C
4H9)
2Ph 1
.0N
a 2H
PO
4 5.0
~100
1
.5 7
9[1
77]
Gas
� N
2
16
See
Tab
le 3
, line
No. 1
07 5
8 8
1 4
7[6
0]
17
See
Tab
le 3
, line
No. 1
08 6
5 8
9 5
8[1
55]
81
86
70
18
~10
14 8
6[1
78]
22
0
664 O. V. BAKHVALOV et al.
TA
BLE 4
(Con
tinued
)
12
34
56
78
910
193
Gas
� A
r�5
4 8
7~1
0010
0[1
10]
0 1
100
~100
100
200
or 1
00
20
0�20
~12
[179
]
220
214
See
Tab
le 3
, line
No. 4
0 8
3[2
8] 2
2See
Tab
le 3
, line
No. 9
1 5
4[2
9, 1
80]
23
30%
H2O
2 50
0M
eCO
OH
100
25
0.25
59
81
48
[108
]
0.1
245
See
Tab
le 3
, line
No. 3
9
25 1.5
90�10
0 9
1[2
7]
25
8
90�10
0 3
7
25
30%
H2O
2 20
0M
g6A
l 2(O
H) 1
6CO
3⋅4
H2O
Ultra
sound
70
3
61[1
81]
(hydro
calc
ite)
0.94
26
NaI
O4
200
24
3
98�10
088
[182
]
24
3.5
83
95
79
12
(C4H
9)4N
Br
12
X =
Y =
Z =
H o
r
X =
Y =
Z =
Me
X =
AcO
O
MODERN METHODS FOR THE EPOXIDATION OF α- AND β-PINENES, 3-CARENE AND LIMONENE 665
TA
BLE 4
(Con
tinued
)
12
34
56
78
910
276
30%
H2O
2 50
0M
eCO
OH
100
25
0.25
59
81
48[2
2]
16
28
t-B
uO
OH
150
55
4 8
2 9
578
[183
]
29
30%
H2O
2 40
0Ca 1
0(PO
4)6(O
H) 2 (hydro
calc
ite)
65�70
838
[184
]
8 m
g p
er 1
mm
ol o
f ol
efin
30
NaI
O4
200
25
2468
[185
]
43
4.0
on p
olyst
yre
ne
31
See
Tab
le 4
, line
No. 2
3 2
5 1
72[3
2]
32
35%
H2O
2 30
Ti-
conta
inin
g M
CM
-41
70
750
�60
[186
]
1.27
% T
i
9.3
mg p
er 1
mm
ol o
f ol
efin
33
30%
H2O
2(n
-Bu
4N) 2
HP
2W
2O14
,
20 4
100
95
95[1
87]
fixed
onto
res
in A
mber
lyst
or o
nto
por
ous
SiO
2
666 O. V. BAKHVALOV et al.
TA
BLE 4
(Con
tinued
)
12
34
56
78
910
34
30%
H2O
2 41
00�20
...+
20 2
78 8
5 6
6[1
88]
25
0
18-c
row
n-6
4.0
Gas
� N
2
357
30%
H2O
2 10
0[γ
-1,2
-H2S
iV2W
10O
40]4�
×
× [(n-C
4H9)
4N+] 4
2
024
89
[33]
pol
yox
ovan
adom
etal
late
TBA
-1 5.0
36
O2
Hydro
talc
ite
conta
inin
g 8
0 6
55[1
89]
Mg,
Al, C
u,
Pd
37
See
Tab
le 3
, line
No.
5985
100
85
[58]
38
NaI
O4
Mn(T
PyP) fixed
onto
Ultra
sound
[190
]ch
loro
met
hyla
ted
pol
yst
yre
ne
39
See
Tab
le 3
, line
No.
5697
100
97
[116
, 117
]
40
35%
H2O
2 20
0K
5.5Na 1
.5[PW
10O
38Cu 4
(H2O
) 2]⋅
13H
2O ,
2
40[1
91]
mai
n p
has
e
[K10 (P
W9O
34) 2Cu
4(H
2O) 2]⋅
20H
2O ,
min
or p
has
e 0.1
41
35%
H2O
2 13
0M
TO
Pyri
din
e 20
or
20
6~9
0[1
]3-
cyan
opyri
din
e 20
42
See
Tab
le 3
, line
No. 4
492
82
75
[111
]
43
See
Tab
le 3
, line
No. 4
5 9
5[6
2]
44
60%
H2O
2 20
0N
a 2H
PO
4 5.0
~8
0 3
81
[24]
Gas
� N
2
45
See
Tab
le 3
, line
No. 4
8 8
5[6
7]
46
See
Tab
le 3
, line
No. 1
917
26
4
.5[7
3]
MODERN METHODS FOR THE EPOXIDATION OF α- AND β-PINENES, 3-CARENE AND LIMONENE 667
TA
BLE 4
(Con
tinued
)
12
34
56
78
910
478
O2
Me 3
CCH
O 3
1125
24 8
1[1
92]
N-m
ethylim
idaz
ole
51
in m
esop
ores
of
zeol
ite
X
13.5 m
g p
er 1
mm
ol o
f ol
efin
489
O2
Co-
sale
n w
ith a
chir
al lig
and
Me 3
CCH
O[1
93]
in m
esop
orou
s ze
olite
N-m
ethylim
idaz
ole
4910
See
Tab
le 3
, line
No. 5
2 9
0 71
for
R(+
)64
[115
]
83
for
S(�
)75
50
OK
CO
HN
aHCO
3 60
025
4.5
90
79
71[1
94]
ED
TA
~0.06
511
1H
ClO
2545
[195
]
from
TCIC
A
~
40
KO
H ~
110
52
See
Tab
le 3
, line
No. 5
7 2
110
021
[47]
53
See
Tab
le 3
, line
No. 5
460
24 3
0[7
4]
54
See
Tab
le 3
, line
No. 5
9 8
510
085
[58]
551
2See
Tab
le 3
, line
No. 5
8 9
5 9
388
[8]
56
See
Tab
le 3
, line
No. 6
2 7
0 9
063
[39]
57
[196
]
58
Anhydro
us
Al 2O
3 neu
tral
obta
ined
76 9
~95
[197
]H
2O2 20
0using s
ol-g
el m
ethod
59
See
Tab
le 3
, line
No. 1
06 4
3 4
318
.5[1
54]
668 O. V. BAKHVALOV et al.
TA
BLE 4
(Con
tinued
)
12
34
56
78
910
60
O2
Me 3
CCH
O 2
.525
2490
�95
55�60
~52
[59]
136
mg p
er 1
mm
ol o
f ol
efin
6113
See
Tab
le 3
, line
No. 6
150
�55
97
51
[118
]
62
PhIO
Mn(I
II)s
alen
Cl 1.0
Gas
� N
2 or
Ar
2525
47
26
[57]
63
H2O
2⋅C
O(N
H2)
2 22
0M
TO
20 0.4
52
[198
]
20 0.7
99
64
35%
H2O
2 12
025
1.5
79
[36]
MTO
in p
olyvin
ylp
ypri
din
e
with 2
5 %
lin
kag
e
65
See
Tab
le 3
, line
No. 4
220
0.5
>99
98
97
[109
]
66
See
Tab
le 3
, line
No. 8
2 4
1
92 9
3 85
.5
[105
, 136
]
4 2
98
86
84
67
See
Tab
le 3
, line
No. 9
3
82[2
5]
MODERN METHODS FOR THE EPOXIDATION OF α- AND β-PINENES, 3-CARENE AND LIMONENE 669
TA
BLE 4
(Con
tinued
)
12
34
56
78
910
6811
See
Tab
le 3
, line
No. 4
7[1
13]
69
See
Tab
le 3
, line
No. 5
0
77
93.5
72
[41]
7014
See
Tab
le 3
, line
No. 8
5 10
0
20
20[1
39]
71
See
Tab
le 3
, line
No. 6
8
72[1
22]
7215
See
Tab
le 3
, line
No. 2
193
�99
61�74
[94]
73
See
Tab
le 3
, line
No. 7
6 8
5[1
30]
74
See
Tab
le 3
, line
No. 5
42�
2.5
96�98
~100
9
8[3
7]
75
See
Tab
le 3
, line
No. 2
9 7
2[2
2]
761
6See
Tab
le 3
, line
No. 5
8 95
93
8
8[1
31]
77
See
Tab
le 3
, line
No. 7
9
100
[133
]
78
50%
H2O
2 15
0Phen
ol
40 2
2 86
92
7
9[1
99]
MeC
OO
Na
1.0
79
O2
Pr
com
pou
nd, 1
mas
s %
MeC
H2C
HO
150
30�60
4.5
94
81
76
[84]
80
See
Tab
le 3
, line
No. 1
10[1
57]
81
30%
NaO
Cl â
H2O
Com
ple
xes
of
Fe,
Mn,
Co
3
0 4
80
[200
]
t-B
uO
OH
100
with tet
raphen
ylp
orphyri
ne
(FeT
PP)C
l, (
MnTPP)C
l,
CoT
PP 0
.1
82[2
01]
Dim
ethylsulp
hon
ium
met
hylide
83
See
Tab
le 3
, line
No. 1
14 9
4 61
57
[16
0, 161
]
84
See
Tab
le 3
, line
No.
115
2
86
[162
]
85
See
Tab
le 3
, line
No.
117
92
71
65
[163
]
86
See
Tab
le 3
, line
No.
119
92
98
90
[164
]
87
See
Tab
le 3
, line
No.
123
89
10
0
89[1
67]
670 O. V. BAKHVALOV et al.
TA
BLE 4
(Con
tinued
)
12
34
56
78
910
88
t-BuO
OH
(5.5
Ì55
2434
84
28.5
[168
]
in d
ecan
e) 1
54
Bn =
C6H
5CH
2
1.0
89
See
Tab
le 3
, line
No. 1
2740
80
32[3
8]
90
See
Tab
le 3
, line
No. 1
2095
100
95[1
65]
9117
2546
94[2
02]
150
2.0
92
H2O
2[γ
-SiW
10O
34(H
2O) 2
]4�[2
03]
pol
yox
omet
alla
te
93
Hal
ogen
atio
n o
f lim
onen
e54
[204
]
by m
eans
of N
-bro
mos
ucc
inim
ide
with f
urt
her
tre
atm
ent
of b
rom
ohydri
nes
form
ed b
y t
he
mix
ture
of
Na 2
CO
3 � E
tOH
� H
2O
yie
lds
tran
s-1,
2-ep
oxylim
onen
e
941
830
% H
2O2
100
[γ-H
2SiV
2W10
O40
]4- (B
u4N
+) 4 5
.020
2495
9590
[65,
66]
9519
O2
Et 2
CH
CH
O 2
0030
2482
[205
]
93
R1 =
Me,
R2 =
4-m
ethox
yphen
yl,
Co(
II)c
alyx(4
)pyrr
ol 1
.0
MODERN METHODS FOR THE EPOXIDATION OF α- AND β-PINENES, 3-CARENE AND LIMONENE 671
TA
BLE 4
(Con
tinued
)
12
34
56
78
910
962
0t-
BuO
OH
25
4647
[206
]
or
150
2.0
97
Anhydro
us
Bas
ic A
l 2O
3 0.25
60
831
9730
[40]
H2O
2 (ð
-ð â
ÝÀ
)
200
982
1t-
BuO
OH
Me 2
-men
thyl-
Sn
2MoO
4(H
2O) 3
.5 1
.0 5
524
8589
76[2
07]
(5.5 Ì
in d
ecan
e)97
6866
150
99
O2
Mn c
omple
x w
ith m
eso-
Me 2
CH
CH
O 5
00
25 5
9299
91[2
08]
tetr
aphen
ylp
orphyri
n (
MnTPP)
100
t-B
uO
OH
110
Ti-
MCM
-41
(MCM
-41
2477
8162
[209
]
with g
raft
ed T
i (I
V)) 0
.002
% T
i
101
See
Tab
le 3
, line
No. 4
091
[210
]
102
NaI
O4
in H
2O 2
00
25 4
8710
087
[211
]
340
on m
ontm
orillo
nite
12.6
103
30%
H2O
2N
a 2W
O4
⋅2H
2O 2
.0(n
-C8H
17) 3N
+M
e25
�70
2.2
9864
63[2
12]
in p
hos
phat
e(
� 4H
SO
) 1.0
buff
er 1
500.1
M H
3PO
4
0.1
M N
aH2P
O4
Na 2
SO
4 5.0
104
t-B
uO
OH
9024
8690
77[2
13]
(3.2 M
in tol
uen
e)
120
4,4�
-met
hyle
ne-
bis(N
,N-d
igly
ci-
dyla
nilin
e; T
GM
DA
-Mo(
OEt)
5
50 m
g p
er 1
mm
ol o
f te
rpen
e
672 O. V. BAKHVALOV et al.
TA
BLE 4
(Con
tinued
)
12
34
56
78
910
105
3%
t-B
uOOH
V2O
5/TiO
2, 3
.4 m
g p
er 1
mm
ol60
1623
3.7
[214
]
in a
ceto
ne
800
of t
erpen
e
106
H2O
2 31
6[A
sO4{W
2O2(µ
-O2)
2(O2) 2
} 2][(n
-C6H
13) 4N] 3
Phas
e25
698
8886
[215
]tr
ansf
er
cata
lyst
Gàç
� N
2
107
Det
aile
d i
nves
tigat
ion o
f[2
16]
epox
idat
ion k
inet
ics
under
the
action
of
H2O
2 in
the
pres
ence
of P
W-a
mber
lite
10822
30%
H2O
2 10
020
2480
[217
]
[γ-1
,2-H
2SiV
2W10
O40]4
�,
imm
obiliz
ed o
n S
iO2
using 0
.005
% p
olyox
omet
alla
te
as a
bin
din
g a
gen
t10
970
% t
-BuO
OH
Mn c
omple
x w
ithte
trap
hen
yl-
30 4
80[5
5]
in H
2O 2
00por
phyri
n a
nd c
hlo
rine
as a
n a
xia
l ligan
dM
n(T
PP)C
l 0.1
MODERN METHODS FOR THE EPOXIDATION OF α- AND β-PINENES, 3-CARENE AND LIMONENE 673
TA
BLE 4
(Con
tinued
)
12
34
56
78
910
110
~4
% N
aIO
425
0.34
9494
88
[48]
in H
2O 2
00
20
Ultra
sound
0
.02
Tet
ra-(
4-pyri
dyl)por
phyri
n
imm
obiliz
ed o
nto
chlo
ro-
met
hyla
ted p
olyst
yre
ne
111
Air
MeC
HO
300
2514
100
[218
]
10
112
t-BuOOH
MoO
x,
inco
rpor
ated
2524
9493
87
[61]
(~6
M in
dec
ane)
into
gri
nded
SiO
2, 0
.62
% M
o
674 O. V. BAKHVALOV et al.
TA
BLE 4
(Con
tinued
)
12
34
56
78
910
113
Air
Me 2
CH
CH
O 2
4025
1260
9054
[219
]
45
Mn(s
alen
) im
mob
iliz
ed
onto
zeo
lite
SBA
-15
mod
ifie
d w
ith
sulp
huri
c ac
id
(SB
A-1
5-pr-
Mn(s
alen
))
27 m
g p
er 1
mm
ol o
f ol
efin
114
Anhydro
us
H2O
222
2286
8170
[220
]
in t
-BuO
H 4
28
× [H
PO
4{W
2O2(
µ-O
2)2(O
2)2}
]2� 8
.5 W
Pol
yox
omet
alla
teco
mple
x o
n m
odifie
d S
iO2
115
35%
H2O
2 20
0K
5.5N
a 1.5[P
W10O
38Cu 2
(H2O
) 2]⋅
13H
2O 0.2
240
96[2
21]
116
O2 blo
w-t
hro
ugh d
uri
ng 6
h[2
22]
at 8
0 o C
thro
ugh o
range
oil
conta
inin
g 0
.1 %
of
Pd o
n h
ydro
talc
ite
res
ults
in lim
onen
e co
nver
sion
lev
elof
abou
t 40
% w
ith t
he
sele
ctiv
ity
at a
bou
t 40
% w
ith r
espec
t to
epox
ides
117
(H2N
) 2CO
⋅H2O
225
0.08
75[2
23]
400
13
3
Hph
ox =
2-(2′
-hydro
xyphen
yl)ox
azol
ine
Mn(p
hox
) 2(C
H3O
H) 2ClO
4 6.7
MODERN METHODS FOR THE EPOXIDATION OF α- AND β-PINENES, 3-CARENE AND LIMONENE 675
TA
BLE 4
(End)
12
34
56
78
910
118
MeC
OO
OH
576
251.0
~80
~100
82[2
24]
Bin
ucl
ear
com
ple
x o
f M
n(I
V)
with 1
,4,7
-tri
met
hyl-
1,4,
7-tr
iaza
-cy
clon
onan
e (L
)
[Mn
2L2O
3](P
F6)
2 0.04
1192
330
% H
2O2
134
WO
3⋅H
2O/H
2O2�
H2O
�H
3O+ 1
.7M
eN+(n
-C8H
17) 3H
2PO
421
2 9
5 5
855
[225
]
12024
35%
H2O
2 27
Ti-
MCM
-41
sila
niz
ed w
ith
707
81
65
[226
]
hex
amet
hyld
isilaz
ane
11.6 m
g p
er 1
mm
ol o
f ol
efin
1 At
an e
levat
ed t
emper
ature
die
pox
ides
are
for
med
.2 A
n e
quim
olar
am
ount
of t
he
epox
idiz
ing a
gen
t re
sults
in t
he
form
atio
n o
f 1
,2-m
onoe
pox
ide,
wher
eas
dou
ble
am
ount
of t
he
epox
idiz
ing a
gen
t an
d t
riple
expos
itio
n is
stat
ed (
with n
o in
dic
atio
n o
f quan
tita
tive
par
amet
ers)
to
resu
lt in t
he
form
atio
n o
f die
pox
ides
.3 T
he
ratio
bet
wee
n m
ono-
and d
iepox
ides
dep
ends
to a
con
sider
able
exte
nt
on t
he
conditio
ns
and t
he
qual
ity o
f so
urc
e ep
oxid
e.4
Epox
idat
ion w
ith d
istillin
g w
ater
out
of t
he
reac
tion
mix
ture
.5
Ther
e is
also
a des
crip
tion
of o
ther
mod
ific
atio
ns
of t
he
cata
lyst
with t
he
char
acte
rist
ics
diffe
rent
from
the
pre
sente
d.
6 W
ith v
aryin
g t
he
conce
ntr
atio
n o
f hydro
gen
per
oxid
e fr
om 1
00 t
o 30
% t
he
conte
nt
die
pox
ides
dec
reas
es f
rom
47
to 2
2 %
.7
Only
8,9
-epox
ide
is f
orm
ed.
8 The
enan
tiom
eric
exce
ss o
f e
pox
ide
is 3
7 %
.9
The
cata
lyst
it
is u
sed f
or s
tere
osel
ective
oxid
atio
n.
10 T
he
sele
ctiv
ity f
or t
he
epox
idat
ion o
f R
-(+
)-isom
er is
71 %
, w
her
eas
for
the
epox
idat
ion o
f S-(
�)-
isom
er t
his v
alue
is e
qual
to
83 %
, w
hic
h, pro
bab
ly, co
uld
be
connec
ted w
ith d
iffe
rent
puri
ty o
f th
e re
agen
ts.
11 A
n e
pox
idiz
ing a
gen
t is f
orm
ed i
n s
itu.
12 T
he
dia
ster
eom
eric
exce
ss f
or o
ne
of t
he
isom
ers
of t
he
epox
ide
is e
qual
to
43 %
.
�
676 O. V. BAKHVALOV et al.
13 F
or a
non
-silan
ized
cat
alyst
just
the
sam
e re
sult is
obta
ined
as
for
a sila
niz
ed c
atal
yst
.14
An e
pox
idiz
ing a
gen
t is f
orm
ed i
n s
itu f
rom
CpM
o(CO
) 3Cl an
d t
-BuO
OH
.15
The
resu
lt d
epen
ds
on m
etal
and p
olym
er u
sed.
16 E
pox
ide
with t
he
dia
stre
omer
ic e
xce
ss o
f 43
% is
form
ed d
ue
to c
hir
al lig
and.
17 T
he
dia
ster
eom
eric
exce
ss o
f ep
oxid
e is e
qual
to
66 %
.18
99
% o
f th
e m
ixtu
re o
f ep
oxid
es is
pre
sente
d b
y 8
,9-i
som
er.
19 F
or R
-(+
) isom
er t
he
yie
ld is
less
, th
an f
or S
-(�)
isom
er.
20 T
he
dia
ster
eom
eric
exce
ss o
f ep
oxid
e is 3
3 %
.21
Top
lin
e: t
he
conver
sion
lev
el, se
lect
ivity, yie
ld f
or R
(+)-
l-m
onen
e; b
otto
m l
ine:
thos
e val
ues
for
S-(
�)-
lim
onen
e an
d t
he
val
ues
of
dia
ster
eom
eric
exce
ss o
f ep
oxid
es 5
-722
97
.5 %
of
the
mix
ture
of
epox
ides
is
pre
sente
d b
y 8
,9-e
pox
ylim
onen
e.23
The
conver
sion
of
olef
in o
ccurs
in a
tw
o-phas
e ca
taly
tic
syst
em w
ith t
he
key
rol
e of
WO
3.24
Epox
idat
ion c
arri
ed o
ut
in t
he
exce
ss o
f ol
efin
to
pre
ven
t tita
niu
m f
rom
was
hin
g a
way
. Sililat
ion k
eeps
the
sele
ctiv
ity w
ith a
n incr
ease
in t
he
conver
sion
lev
el.
MODERN METHODS FOR THE EPOXIDATION OF α- AND β-PINENES, 3-CARENE AND LIMONENE 677
TA
BLE 5
Mai
n c
onditio
ns
and r
esults
for
3-ca
rene
epox
idat
ion
No.
Epox
idiz
ing
Cat
alyst
Auxilia
ry r
eagen
ts,
Ò,
î CR
eact
ion
Con
ver
sion
S
elec
tivity, %
Yie
ld,
%R
ef.
agen
tco
-cat
alyst
stim
e, h
level
, %
12
3 4
5 6
7
8
910
150
% H
2O
2, 1
00K
2CO
3 30
0 �
512
�0
80
[227
]
150
2See
Tab
le 3
, line
No. 46
[112
]
31
,2See
Tab
le 3
, line
No. 1
04[1
53]
43
See
Tab
le 3
, line
No. 40
87
[28]
530
% H
2O2
160
WO
3⋅H
2O 2
00N
a 3PO
4 3.0
25
96
97
[228
]
QA
S ~
1.0
H2S
O4
up t
o pH
2.5
6See
Tab
le 3
, line
No. 5
3[3
7]
750
% H
2O2
150
Zn(
NO
3)2
⋅6H
2O60
�65
8
.5~1
00~7
8 7
8[2
29]
+ N
a 2W
O4
⋅2H
2O 6
30 4
40
8See
Tab
le 3
, line
No. 42
20
2
97
99
96
[109
]
950
% H
2O2
250
MeC
N 6
20
60 1
8 9
2[2
30]
Na 2
HPO
4 0.01
2
NaO
H ~
26
Gas
� N
2
1038.4
%
Na 2
CO
3 94
20
24
[231
]M
eCO
OO
H 1
10M
eCO
OO
H
NaO
H ~
26
Gas
� N
2
1150
% H
2O2
250
MeC
N 6
20
60 2
4[2
31]
Na 2
HPO
4 0.01
2
NaO
H ~
26
Gas
� N
2
678 O. V. BAKHVALOV et al.
TA
BLE 5
(Con
tinued
)
12
34
56
78
910
12t-
BuO
OH
(NH
4)2M
oO4
~0.08
NaO
H 5
0097
6~9
3[2
31]
Gas
� N
2
13See
Tab
le 3
, line
No. 9
1 4
8[2
9]
14See
Tab
le 3
, line
No. 3
770
5[1
07]
1560
% H
2O2
200
CF
3CO
CF
3 5.0
20 1
80
[232
]
Na 2
HPO
4 5
.020
21
>99
16See
Tab
le 3
, line
No. 4
925
22
70
25
17.5
[31]
20 9
79
18
14
17
80[1
45]
18See
Tab
le 3
, line
No. 7
20 5
97
90
87
[26]
19G
as �
Ar
�5
1
~100
[110
]
20See
Tab
le 3
, line
No. 3
920
1.5
[27]
21See
Tab
le 3
, line
No. 3
60 4
9
7 97
94
[80]
224
60%
H2O
2 20
0N
a 2H
PO
4 5.0,
20 2
1 8
1[2
4]
gas
� N
2
231
See
Tab
le 3
, line
No. 6
3 6
2 ~
55[6
8]
24O
2CoN
aYM
e 2CH
CH
O 7
6024
2.5
10
0 9
9
99[4
2]
Co(
NO
3)2 2
.024
3.0
2550
% H
2O2
150
PhO
H 1
000
MeC
OO
Na
1.0
60 1
2 9
6 9
5 91
[199
]
265
30%
H2O
2(T
BA
) 6[M
n(H
2O)B
W11
O39
]82
2�6
75�76
62�65
44�47
[234
]60
0�70
0(T
BA
) 5[B
W12
O40
]
MODERN METHODS FOR THE EPOXIDATION OF α- AND β-PINENES, 3-CARENE AND LIMONENE 679
TA
BLE 5
(Con
tinued
)
12
34
56
78
910
2730
% H
2O2
300
MeC
OO
NH
4 66
601.5
6857
39[2
35]
X =
Z =
Cl
[MnClT
DCPPyPH
]H2[PW
12O
40]×
× 4H
2O⋅3
MeO
H
28M
eCO
OO
HM
eCO
ON
a25
298
[236
]
2930
% H
2O
223
2493
.5[2
37]
301
See
Tab
le 3
, line
No. 4
722
[113
]
3110
% H
2O2
200
22 1
9892
90[2
38]
Fe(
TPFPP)C
l0.2
680 O. V. BAKHVALOV et al.
TA
BLE 5
(C
ontinued
)
12
34
56
78
910
3230
% H
2O2
420
MeC
OO
NH
4 23
25
3.5
100
6060
[239
]
Mn(T
F5P
P)C
l1.7
3350
% H
2O2
200
PW
4O24 o
n A
mber
lite
IRA
-900
38
24 5
597
53[8
0]
20 m
g p
er 1
mm
ol o
f te
rpen
e
34O
2Pr
com
pou
nd, 1
mas
s %
MeC
H2C
HO
150
30�60
4
95
8278
[84]
35A
nhydro
us
25
3035
[180
]
MeC
N
~5.0
366
30%
H2O
2 41
00�20
227
[188
]
150
8-cr
own-6
4.0
gas
� N
2
372
30%
H2O
2 53
0W
O3
⋅H2O
250
or
MoO
2 24
0 6
0 2
77[2
40]
85
2.4
H3P
O4
1.6
MODERN METHODS FOR THE EPOXIDATION OF α- AND β-PINENES, 3-CARENE AND LIMONENE 681
TA
BLE 5
(End)
12
34
56
78
910
3830
% H
2O2
Na 2
WO
4⋅2
H2O
2.0
MeN
+(í
-C8H
17) 3
25�70
4.0
9395
88[2
41]
in p
hos
phat
e� 4
HSO
1.0
buff
er0.1
M H
3PO
4
0.1
M N
aH2P
O4
Na 2
SO
4 5.0
3935
% H
2O
2M
eCO
ON
H4 4
0
2027
6542
27[4
9]
5,10
,15,
20-t
etra
kis(2
,6-d
i-
chlo
rophen
yl)-p
orphyri
nat
o-M
n(I
II)
[Mn(T
DCPP)C
l]10
3 m
g p
er 1
mm
ol o
f ol
efin
407
30%
H2O
2 13
4W
O3
⋅H2O
/ H
2O2�
H2O
�H
3O+1.
7M
eN+(n
-C8H
17) 3
21
385
100
85[2
25]
�
24
HPO
2.5
1 A
n e
pox
idiz
ing a
gen
t is f
orm
ed i
n s
itu.
2 Q
uan
tita
tive
dat
a ar
e pre
sente
d f
or t
he
epox
idat
ion o
f cy
cloo
cten
e.3
Epox
idat
ion w
ith d
istillin
g w
ater
out
of t
he
reac
tion
mix
ture
4 The
yie
ld is
pre
sente
d f
or p
uri
fied
epox
ide
in s
mal
l-sc
ale
exper
imen
t.5
The
reac
tion
dura
tion
dep
ends
on t
he
exce
ss o
f hydro
gen
per
oxid
e.6
70 %
of
initia
l te
rpen
e re
mai
n n
on-r
eact
ed.
7 The
conver
sion
of
olef
in o
ccurs
in a
tw
o-phas
e ca
taly
tic
syst
em w
ith t
he
key
rol
e of
WO
3.
682 O. V. BAKHVALOV et al.
TA
BLE 6
Mai
n c
onditio
ns
and r
esults
for
β-pin
ene
epox
idat
ion
No.
Epox
idiz
ing
Cat
alyst
Auxilia
ry r
eagen
ts,
Ò,
î CR
eact
ion
Con
ver
sion
S
elec
tivity, %
Yie
ld,
%R
efer
ence
agen
tco
-cat
alyst
stim
e, h
level
, %
12
3 4
5 6
7
8
910
11
See
Tab
le 3
, line
No. 3
7[1
07]
2See
Tab
le 3
, line
No. 1
84[7
9]
3(M
eCO
O) 4Pb
[242
]
4PhCN
KH
CO
3 49
20�25
120
74[2
43]
+ 5
0%
H2O
2 ~1
:1
5See
Tab
le 3
, line
No. 5
91[8
2]
6See
Tab
le 3
, line
No. 2
0 1
.298
83.5
82[1
]
7See
Tab
le 3
, line
No. 4
84[8
1]
8See
Tab
le 3
, line
No. 1
09[1
56]
9See
Tab
le 3
, line
No. 1
04[1
53]
10See
Tab
le 3
, line
No. 4
8 2
491
[67]
11See
Tab
le 3
, line
No. 5
027
8523
[41]
12See
Tab
le 3
, line
No. 9
472
[25]
69
13See
Tab
le 3
, line
No. 9
549
[147
]
141,
2See
Tab
le 3
, line
No. 4
6 70
4
80[1
12]
1535
% H
2O2
1000
MnSO
4 2.0
20
3
9778
76[2
44]
163
See
Tab
le 3
, line
No. 4
495
10.5
10[1
11]
174
See
Tab
le 3
, line
No. 6
390
5247
[68]
18A
nhydro
us
MeC
OO
H 1
00 25
0
.25
1470
10
[108
, 32]
H2O
2 52
0
0.1�0.2
MODERN METHODS FOR THE EPOXIDATION OF α- AND β-PINENES, 3-CARENE AND LIMONENE 683
TA
BLE 6
(End)
12
34
56
78
910
195
See
Tab
le 3
, line
No. 7
691
[130
]
20PhIO
100
Gas
� N
2 2
54
55[1
03]
5.0
21See
Tab
le 3
, line
No. 8
2 0
560
9054
[136
]
22See
Tab
le 3
, line
No. 8
30�60
583
4840
[84]
23See
Tab
le 3
, line
No. 1
2896
.763
.962
[169
]
24Epox
idat
ion o
f β-
pin
ene
[245
]at
the
1st
stag
e of
the
synth
esis
of p
erry
lic
aldeh
yde
1 D
ata
conce
rnin
g t
he
epox
idat
ion o
f 3-
care
ne.
2 A
n e
pox
idiz
ing a
gen
t is f
orm
ed in s
itu.
3 The
epox
idiz
ing a
gen
t is a
ir u
nder
a p
ress
ure
of
3 Ì
Pa.
4 The
conte
nt
of t
he
mai
n s
ubst
ance
in t
he
pro
duct
is
hig
her
than
99
%.
5 M
ethan
ol is
use
d a
s a
solv
ent
inst
ead o
f et
han
ol.
684 O. V. BAKHVALOV et al.
Thus, acetonitrile and PhCN could be con-sidered to represent solvents, activators.
Some fluoroorganic solvents such as hexaflu-oropropanol-2, trifluoroethanol, hexafluoroace-tone, fluorinated alkanes, amines, fluorinatedethers could be related to this kind of com-pounds, too. Such compounds are able to ep-oxidize terpenes either without additives, orwith small amounts of nonmetallic additives (seeTables 3�6). The authors of these publicationsexplain the �effect of fluorine� by physical fea-tures of fluorinated compounds, first of all bythe ability to form associates and hydrogenbonds, which results in the stabilization of in-termediate species responsible for the processof epoxidation as well as in the lowering ofenergy barriers of the reactions.
Phenol is proposed to be a solvent (activator),too [64]:
The ability of phenol molecules for aggrega-tion, from the standpoint of the authors of [64]determines the stabilization of the transition state.
The increasing attention of researchers isattracted by such a group of catalysts as poly-oxometallates. Their composition varies, but thepermanent components of the anionic parts of
Scheme 4.
The complex 13 exhibits weak catalyticproperties in the processes of oxidation-epoxi-dation. Nevertheless, the mechanism of epoxi-dation by this reagent has been studied in [22].Scheme 4 demonstrates the stages of epoxida-tion, beginning from operation (0) � the for-mation of proper catalyst. It turns out that com-pound 13 represents only a precursor of thecatalyst. The following conclusions are alsodrawn from the investigation [22]:
1. The most efficient method for using hy-drogen peroxide in the epoxidation process con-sists in a batching entering of the reagent intothe reaction medium.
2. Epoxidation proceeds according to themechanism that, as against the process of al-kanes oxidation by t-BuOOH, occurs withoutthe formation of radicals.
3. Epoxidation is the first-order reaction withrespect to the concentration of substance 13.
4. The epoxidation of alkene and the paral-lel oxidation of alkane proceed through differ-ent intermediate species.
The most widespread solvent used in thereaction of epoxidation is acetonitrile whichreacts with hydrogen peroxide to form peroxy-acetimidic acid. The latter can transfer the oxy-gen to the double bond. PhCN operates in a sim-ilar manner [62, 63].
MODERN METHODS FOR THE EPOXIDATION OF α- AND β-PINENES, 3-CARENE AND LIMONENE 685
A group of Chinese authors has proposeda modification of this method whereby the epoxi-dation is carried out within the cathodic cell of anelectrolyser generating hydrogen peroxide [70, 71]:
O2 + e� → �2O•
� �2 2 2 2 22O 2H O O H O + 2OH• + +����
����
� �2 2 2 2O 2H O 2 H O + 2OHe+ + ����
����
Using different catholyte compositions where-to oxygen was fed the researchers epoxidized anumber of compounds including α-pinene:
The authors consider the possibility of con-trollable dosing hydrogen peroxide fed into thereaction mixture to be the advantage of themethod. Unfortunately, the data presented in
the molecule are presented by tungsten, sili-con, hydrogen at a high content of oxygen.Tetabutylammonium cation is used as a counter-ion. It is established that polyoxometallates withthe mentioned set of chemical elements canprovide at 70 îÑ high yields of epoxides of var-ious olefins already with a double excess of15 % hydrogen peroxide solution. In case thatthe structure of polyoxometallate includes va-nadium the diastereoselectivity, stereospecific-ity and regioselectivity become unique [65]. Forexample, in the process of limonene epoxida-tion by polyoxometallate {[γ-SiW10O34(H2O)2]
4�}containing no vanadium the content of 8,9-ep-oxide amounts to 37 % only. In the beginningof the studies on V-containing polyoxometal-lates their active nucleus was considered to rep-resent VO�(µ-OH)2�VO [33, 65]. The authorsof the latest work described the structure ofthe active centre of the catalyst and have of-fered a cyclic mechanism for the epoxidationincluding five elementary processes [66].
Below one can see schematic diagrams forthe interaction between the main epoxidizingagent such as hydrogen peroxide and specialreagents (activators) those form in the reactionmedium a more effective generators of theactive oxygen, which active oxygen mainlycauses the reaction to proceed (Scheme 5).
Scheme 5.
Activator is carbodiimide [67].
The activator is presented by arylsulphonylic peracid, astronger epoxidizing agent as compared to perbenzoic acid [68].
The activators are manganese sulphate and salicylic acid[12]. The formation of �
4HCO (peroxomonocarbonate) is
proved using 13Ñ NMR technique [69].
686 O. V. BAKHVALOV et al.
the works mentioned do not allow one to esti-mate technological parameters of this scheme.
Two very efficient epoxidizing agents areknown such as dimethyldioxirane 14 and 5-hy-droperoxycarbonylphtalimide 16. Their action isdemonstrated in Schemes presented below. Inthe first case intermediate species 15 is pre-sented at the instant of limonene attack bycompound 14.
Judging from small number of publications,a wide application of compounds 14 and 16 isprevented by the complications in the synthe-sis of these epoxidizing agents.
Some authors studied parallel reactions of ter-penes epoxidation and their oxidation with the con-servation of the cyclohexane fragment. Regard-ing publications the latter direction was the mainone [72�74]. In this case researchers varied the con-ditions to aim at achieving the maximal yield ofverbenone [75] or campholenic aldehyde [76].
Let us consider in brief the publications de-voted to the biochemical epoxidation. In publi-cations [14, 15] the source of active oxygen ispresented by percarbonic acid or its ester ob-tained in situ from dimethylcarbonate in thepresence of hydrogen peroxide and immobi-lized lipase. Good yields of epoxides of α- andβ-pinene were achieved amounting to 85 and77 % at the temperature of 20 and 40 oC, re-spectively. However, the reactions of dimeth-ylcarbonate and lipase obtaining represent rath-
er complicated processes, whereas for the ep-oxidation a great amount of enzyme and a five-fold excess of 60 % hydrogen peroxide solutionsare used. The switching to immobilized lipase(Novozyme 435) and to hydrogen peroxide com-plex with urea [20] has allowed the researchersto lower essentially the consumption of the re-agents mentioned with achieving 95 % yield of2,3-epoxypinane. The authors of [16] carried outthe oxidation of R-(+)-α-pinene and S-(+)-li-monene using preparations based on cytochromeR 450cam. The selectivity of the processes andthe yield of epoxides was very low, and onecould consider a high (>95 %) diastereoselectivi-ty of the process to be the only achievement.
The authors of [17] investigated the syn-thesis of isonovalol:
From the authors� standpoint, compound 17 isof interest for the manufacture of fragrancecompounds. The biomass of Pseudomonas rho-desiae PF1 (biocatalyst) is cultivated on a nu-trient medium containing α-pinene. The enzyme-catalyzed stage of isonovalol 17 formation fol-lows after the synthesis of epoxide.
In the works [18, 19] the epoxidizing agentis presented by peroxyoctanoic acid which isformed in situ from an approximately equimo-lar amount of octanoic acid and hydrogen per-oxide in the presence of immobilized lipase.Toluene and water were used as solvents. Asmuch as ~65 % of terpene was consumed inthe presence of 7�8 mass % of the catalyst,150 mol. % (with respect to α-pinene) of 35 %hydrogen peroxide in the mixture during 3 hat a room temperature. The influence of manyfactors was investigated: the origin of lipase,its charge, the concentration of hydrogen per-oxide and the rate of its feeding into the reac-tion medium, the concentration of source oc-tanoic acid, and the temperature. The methoddescribed did not provide stable results; it ischaracterized by authors only as an alterna-tive one. Nevertheless, it is obvious that thedevelopment of biochemical methods for ep-oxidation is rather promising, since the syn-
MODERN METHODS FOR THE EPOXIDATION OF α- AND β-PINENES, 3-CARENE AND LIMONENE 687
thesis of many bioactive substances in the wild-life occurs through epoxide intermediate species.
In summary attention should be drawn toan original synthesis of two-layer membranes,those allow separating the racemic mixture ofchiral epoxides with a simultaneous formationof enantiomerically pure diols [77].
Particular conditions and results of the ep-oxidation reactions are presented in Tables 3�6.
CONCLUSION
The review of the literature concerning themethods for the epoxidation of terpenes indi-cates that there is unrelenting, but selectiveresearchers� interest in this reaction. So, if sixarticles and patents per year are on the aver-age devoted to the formation of the oxiranering in α-pinene and limonen, one or two pub-lications a year are devoted to similar modify-ing of β-pinene and 3-carene.
The overwhelming majority of the meth-ods for the epoxidation of the terpenes underconsideration are catalytic ones, which reflectsthe general tendency of chemical technologydevelopment. As main epoxidizing agents oneuses to apply hydrogen peroxide and oxygenthose yield for the most part environmentallycompatible by-products.
Despite of the abundance of methods forthe synthesis of epoxides, only few among themcould be considered to be a basis for the orga-nization of the process for the manufacture ofterpenoids. The present review elucidates thefollowing two reasons of such circumstances.First, the efficient catalysts are either inacces-sible due to scarcity (for example, methyltri-oxorhenium), or are complicated with respectto the structure and the methods of obtaining(for example, polyoxometallates). Second, thereare no rational flow sheets for the processingof epoxidation reaction mixtures presented inthe literature with the isolation of target prod-ucts and recycling of by-products. In this con-nection the published data allow only prelimi-nary planning of promising systems in orderto obtain either epoxide. To what extent couldthe reaction pathways chosen result in a tech-nological, economical, low-waste, environmen-tally compatible process one might found outonly in the studies concerning �tail� operations.
According to our opinion, the following sys-tems could be assigned to a number of promis-ing ones for use in the epoxidation of terpenes:
1. A number of combinations based on me-thyltrioxorhenium activated by any aromaticnitrogen-containing compound (pyridine, imi-dazole, etc.). With the use of this system theconversion level for different terpenes and theyield of epoxides amounts to 89�98 % in ho-mogeneous, immobilized and incapsulated formsunder the action of a small excess of 30�35 %hydrogen peroxide solution.
2. A system able to epoxidize a number ofterpenes in an aqueous organic solution of so-dium bicarbonate activated with catalyticamounts of manganese sulphate and salicylicacid. Polar solvents containing no halogens areused as an organic component of the medium.Such a system is cheap, readily available, com-patible with the environment, however it re-quires for a multiple excess of 30�35 % H2O2
solution as well as recycling of spent solutions.3. A system based on V2O3, which is attrac-
tive due to the simplicity of epoxidation pro-cedure and the availability of reagents. Thereaction occurs with a small excess of 30 %hydrogen peroxide solution in the presence ofsmall amounts of simple salts (mainly phos-phates and QAS), with moderate yields of ep-oxides. The universality of this system is notquite clear; the use for many terpenes is underpatenting, however, the examples are present-ed only for 3-carene and limonene.
4. The synthesis of α-pinene and limoneneepoxides with the yields of 90�98 % could becarried out with the help of Mn porphyrin cat-alysts activated with alkylimidazole or isobutylaldehyde. In this case the porphyrin cycle shouldcontain benzene or pyridine substituents. Sim-ple epoxidizing agents (such as water, hydro-gen peroxide, oxygen) are used. The main prob-lem arising in the use of this system consists inthe obtaining of a catalyst.
5. Unique positive results are produced withthe use of some catalytic systems based on poly-oxometallates. One could offer the examples ofα-pinene epoxidation catalyzed by polyoxomet-allate without vanadium, nevertheless withactivators (amines, silane derivatives, diben-zyl) and immobilized polyoxometallate contain-ing cobalt (the activator representing isobutyl
688 O. V. BAKHVALOV et al.
aldehyde). In both cases under very soft condi-tions the technological parameters amounted to90�96 %. The system under discussion was suc-cessfully used for 3-carene, too.
One should pay attention to the epoxidationin fluorinated solvents without catalysts. Suchterpene as α-pinene in perfluorohexane medi-um in the presence of iso-aliphatic aldehydereacts to result in the formation of an epoxidederivative with technological parameters of 90�95 % during 4 h at a room temperature in theflow of oxygen. Much better results underequally soft conditions were obtained for theepoxidation of limonene and 3-carene. Howev-er, the source of active oxygen in the first caseis presented urea complex with hydrogen per-oxide, whereas in the second case 60 % solu-tion of the latter is used.
Acknowledgements
Authors express sincere gratitude to theresearchers of the Novosibirsk Institute of OrganicChemistry, SB RAS, L. S. Filatova, N. N. Kud-ryavtseva and V. I. Bolshakova for great help insearching and gathering the literature.
LIST OF ABBREVIATIONS
QAS � quaternary ammonium saltDCC � dicyclohexyl carbodiimideRM � reaction mixtureÌÒÎ � methyltrioxorheniumUS � ultrasoundTCICA � trichloroisocyanuric acidMn(TPyP) � Mn tetrapyridineporphyrin
complexEDTA � ethylenediaminetetraacetic acidTBA � tetrabutylamineEA � ethyl acetate
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