PT104884A

PT104884A - COMPLEX OF COPPER (II) WITH LIGANDS 2,4-ETOXY-1,3,5-TRIAZAPENTADIENETO AND ITS APPLICATION AND THE 2,4-METOXI ANALOGUE AS CATALYSTS FOR PEROXIDATIVE, MICROWAVE-ASSISTED AND NO SOLVENT-ADDED OXIDATION OF ALCOHOLS SECONDARY TO CETONAS.

Info

Publication number: PT104884A
Application number: PT10488409A
Authority: PT
Inventors: Maximilian N Kopylovich; Armando J L Pombeiro; Luisa M D R S Martins; Joao J R Frausto Da Silva; Jamal Lasri; Pawel J Figiel; Maria Fatima C Guedes Da Silva
Original assignee: Inst Superior Tecnico
Priority date: 2009-12-15
Filing date: 2009-12-15
Publication date: 2011-06-15
Also published as: PT104884B

Abstract

A INVENÇÃO REFERE-SE A UM NOVO COMPLEXO DE COBRE (II) COM LIGANDOS 2,4-ETOXI-1,3,5-TRIAZAPENTADIENETO, DE FÓRMULA [CU{NH=C(OET)NC(OET)=NH}2]1 E AO USO DAQUELE COMPOSTO E DO SEU ANÁLOGO 2,4-METOXI COMO CATALISADORES EFICIENTES E SELECTIVOS DA OXIDAÇÃO PEROXIDATIVA DE ÁLCOOIS SECUNDÁRIOS ÀS CETONAS CORRESPONDENTES, SEGUNDO O ESQUEMA REACCIONAL, ASSISTIDA POR MICROONDAS E SEM ADIÇÃO DE SOLVENTES.The invention relates to a novel copper (II) complex with 2,4-ETOXI-1,3,5-TRIAZAPENTADIENET LIGANDS, OF FORMULA [CU (NH = C (OET) NC (OET) = NH} 2] 1 and to the use of that compound and its 2,4-Methoxy analogue as efficient and selective catalysts of the peroxidation of secondary alcohols to the corresponding quenchs, according to the reactive scheme, assisted by microwaves and without addition of solvents.

Description

DESCRIÇÃODESCRIPTION

Complexo dé cobre{XX) o» Xigaudós 2 , ê^toxx^X , 3,5~ tria»a|»s«it:adi«bi&to e ««» aplicação & do smâlogo 2,4nmetoxi como ca-taiisedores para a oaidaçâo peroridativa, aaaiabida por máerooudas, da álcoois e&eundários a oetoaaa A preeente intenção refere.....se s ura úoxo complexo de coe r e (11) coai 11 gan do s 2,1 -· et ox i --1,3,5--1 r i a r ap e o t adi e n et o o ao uso daquele composto e do seu análogo 2, é-metoxi como catalisadores eficientes e solecriuos da oxidação pero ridativá de âlcoeis secar dá ri.os. às cetonas cor r e s p c ndente s , assistida por mi. cr condas e n a ausência de sol veov.es ,Copper Complex (XX) and Xapos; 2, Xapos; Xa, Xa, Xa, Xa, Xa and Xa. of the 2,4-methoxymethyl ester as catalysts for the peroridation and peroxidation of the alcohols and ammonia to the metal. The present intention refers to a further complex of (11) covalent bonds 2,1-dihydroxy-1, 3, 5-1, 4-ethoxy-2-oxo-1,3-dihydroxypropionate. give laugh to the ketones cor r e s p centes, assisted by me. crusts and n the absence of sun veov.es,

Domínio técnico da invenção:Technical field of the invention:

Catálise, ili o tocadas, Química de Coordenação, QuímicaCatalysis, Ili o touches, Chemistry of Coordination, Chemistry

Orgânica A técnica anterior:Organic The prior art:

As ostonas figuram: entre o a compostos químicos ma is importantes, come pr contos intermediários ou finais, por exemplo como precursores de polimos ou como substratos para a indústria farmacêutica [1], Embora possam ser sintetisadas por oxidação airecta de alcanos 12,3] ou «Ícones Γ2], estas roacçoes ndo são, em geral, seieof i vas [2] , Assim, a oxidação em fase liquida de álcoois secundários a cotonas, que pareço ser o método mais uri 1 irado e também o mau.s simples [3, 5] , mas que gera .Emento se limita a: compostos Penei licos íéj, necessita, de quantidades elesadas de eate.iisador [Sj , i.onqoc tempos rececionais [t] e/ou. ad.iti vos (bases, agentes de transferência de fase, etc,} [5,6], assim como de oxidarmos (e,g- sais de manganês, crome aos; [1,1] e solventes f êbV Qc, 7 , Ç ] que sâo muitas: coses dispendiosos e tóxicos. Além disso, os estairsadores oti limados são f r scgmnt ernen se dispen.diosos ibasoudoa em metais sobros;· íaj, difíceis do preparar e não apresentam grande ect i.viosoe na oxidação de álcoois aixfaticos [6], Persiste, assim, a necessidade de encontrar outros sistemas sintéticos de cetonas que possam ultrapassar pelo menos algumas das 1 imitações mencionadas acama> 0 presente trabalho foi. desenvolvido no Centro de Química Estrutural (Complexo X, instituto Superior Cécnion) no âmbito de estudos de investigação do bolseiro de pos-doutoramento Dr> tu Figiei, doa .tovestigadores auxiliares D:rv. âb Lasrl e Dr, d,d.. Kopyiorion, da Dm* PDF, Quedes da Silva, da Drb rsM,R.S, Martins, e da bolseira de doutoramento Mestre T,F.S.< Silva, estando rase ridos em. projactos da responsabilidade c (o Proít Rrmando CCS, Pomboiro. suportados poiã Eutoaç· ao pare a Ciência e a Tsen.0 Ipq i. a e: pelo seu programa DPCDF (financiado o ti o FEDER), Descrigâo das figuras: FIG. I - Complexo de cobreei!): com.. 1. i gano o a 2, i -ef oxi--· 1,1,5--'trierapeu:tadienetc:f de .formula [Cu i MH-<: (Ort} MC (Ont) Mb; [j (1> , FXQ, 2 “ oxidação beroXibaltva de âtceolS secundários âs c e t c na s co r r o s no n de n t e*Ostones are among the most important chemical compounds, such as intermediates or final compounds, for example as polymer precursors or as substrates for the pharmaceutical industry. [1] Although they may be synthesized by aerial oxidation of alkanes 12,3] or Thus, the liquid phase oxidation of alcohols secondary to cotones, which seems to be the most urified method and also the simple ones [2] 3, 5], but which generates an amount is limited to: penile compounds, and requires quantities of carrier [s], i.e., at receiver times [t] and / or. (bases, phase transfer agents etc.) [5,6], as well as the oxidation of manganese gates, [1,1] and solvents f (v) , Which are expensive and toxic. In addition, odor-free stabilizers are readily available in the form of low-cost metals which are difficult to prepare and do not exhibit great corrosion and oxidation of alcohols The present work was developed at the Center for Structural Chemistry (Complex X, Higher Technical Institute) in the field of chemistry and chemistry, with the aim of finding other synthetic ketone systems which may exceed at least some of the above mentioned immitations. In the scope of research studies of the postdoctoral fellow Dr > tu Figiei, donates the auxiliary researchers D: rv Lasrl and Dr, d, d .. Kopyiorion, Dm * PDF, Quedes da Silva, Drb rsM, RS , Martins, and the doctoral grant holder T, FS < Silva, being Projacts of responsibility and responsibility (the Prodrmando CCS, Pomboiro. Supported by Eucalyptus Science and Tsen. Ipq i. and (b) for its DPCDF program (financed by the ERDF), Description of the figures: FIG. I - Copolymer complex): with 1, 2-iodoxy-1,1,5-triazaheteradecetone of formula [Cu i MH- (1), (2), (2), (2), (2) and (b)

Dessorição d&. imiáúçã©; 1. Ob|^«tiyos' e v&ntagespa O crjecti vc geral desta invenção consiste na obnençao de un processo fácil e eficiente de formação de cetonas por oxidação pe roei da tira de álcoois secundários, em. condi, coes moderadas, assistido por radiação de microondas, isento de solventes ou aditivos e utilisando um catalisador e um orsdunte ambientaImente aceitáveis * vara tal, foram seieccionados os lloandcs 1, 4-eicoai-Ma, o·· trrarepermacieneto, em particular o 2, fmnetoxiri , 3, Õ~ trlasapentadianeto e o 2, 4~etox.i~.lj, 3* 5~trie.rapents:dieneton como metal o cobre MT), e os estudos deseηvοIveram-se no imbiio dos seguintes oMjeativos maia específicos:; tio obtenoeo da um: novo complexo de cobro Ml) com. 2,4-·af οχ 1 -.1,3, 5"trratapenradionero a çii.) aplicação dos oo:?splapos 2,4 me t com. ~ e a, 4 ~ e t oa 1 ~ 1,3, ã ··· t r í asa o a n t a d i en a to à ο κ i d a g â o catai leira de álcoois secundários em condições moderadas e toleráveis do ponto da vista ambientai, com. bons rendimento e eelectividade„Desorption d & imiauçã ©; The general purpose of this invention is to provide an easy and efficient process for the formation of ketones by oxidation by the secondary alcohol strip, In a preferred embodiment of the present invention, the present invention relates to a process for the preparation of a compound of the general formula: ## STR2 ## in which the conditions are set forth in the following Examples: 1, 4-ethylamino- , trimethoprim-cyanide and 2,4-ethoxyethyl-3Î²-triene triazines: dieneton as metal or copper MT), and the studies were carried out in the imitation of the following specific mays :; The title compound was prepared from the following compound (II): 2,4-difluorophosphate-1, 3, 5 " and at least 1 to 1.3% by weight of the secondary alcohols in moderate and environmentally tolerable conditions. good yield and efficacy "

Destes obj: estivos decorreu a obtenção dc primeiro complexo· de cobre com es 11 gandos 2, 4 -et cr i. ~ 1,3, 5 ~ triexaperMadi.eneto, [Cu{HH-C (GSt) DC{OEM MHbj 1. ãlám disso, nenrutm sistema baseado num complexo de cobre ecm ligãndos dc tipo 2, 4-a 1 eoxi"d., 3, S~tris eapentadreceto fofa aplicado à oxidação peroxidativa da álcoois secundários.From these objects was obtained the first complex of copper with 11 g of 2,4- 1, 3-hexadecyclohexanecarboxylate, [Cu (HH-C (GSt) DC (CH2) m NH2)], which is a complex based on a copper complex and type 2, 4-a and 1-d links. , 3, S-tris and 5-ethylhexanoate as applied to the peroxidation oxidation of the secondary alcohols.

As principal a vantagens associadas a esta invenção consistem no recurso a catalisadores simples, amo iam·, a imente toleráveis {de efeito poluente muito reco rido ou nulo; e facilmente obtidos por uma via simples {num. sc "passo") e conventente a partir de maternais de partida (seus sais metálicos) dl oponíveis comer c ia Imante e de beiro custo.,The main advantages associated with this invention are recourse to simple, tolerable and highly tolerable catalysts (with very high or no pollutant effect; and easily obtained by a single pathway (num. (" step ") and convent from maternal starting materials (their metal salts)

Dutras rasatage.ne residers na doo estabilidade destes catalisadores sob ooadiçoes emitentes e na sua solubilidade nos álcoois substratos, permitindo assim ir que o processo catalítico decorra oe ausência de outros aviventes e coo pequenas quantidades de catai isador, e ii) ei mi nar a necessidade de agentes de transferência de fase. ei em disso, o sistema catai 1 tico· qt jc é oblecto de pr esente invenção recorre ao uso de ra i or o o n u a s, r rue permitem acelerar gras-demente a reaegáo e proporcionam um processo ecológico com significado em "qu irai ca verde", Oonatituirrdo também, uma vantagem do método desta invenção.. 0 sistema cataiitios da presente invenção constitui um sistema de eievades sotividade e seaectividade, em. ocndiçoes moderadas (temperaturas de Sn - 2 0 °Dj , e sem. necessidade de co-caé ai is adores ou adi ticos, assim., for ara atingidos nameros de cicios catalíticos, a.e,, numeros ds ^turmover" (TOb), expressos em. moles de produto por mole de cateiisador> até ca, 100, e rendimentos de ca, ISO %, 2 v. CaraoterisPibáá inov&dor&s ê invenção era snáé.i.se reporta-se ae uso inces cor de complexos de oobteill; ocra 1 igaridos 2, i-metoxi·"· e 2,4-otoxi-1,3,5-tr.taS:apervtad.ienetc como cetalisadores para a oxidação peroxida 1iva de álcdois secundários ae cetonas c or r a s pcsoderi. t e s , êiém disso, a presente invenção reconte ce, pela primeira ver, que os complexos daquele tipo catalisara efdoientemente s oxidação de álcoois secundários as correspondentes cetonas» som requerer a presença de çnaiquer solvente oraàaico,Further residues are provided by the stability of these catalysts under the emissive emitters and their solubility in the substrate alcohols, thus allowing the catalytic process to take place and the absence of other solvents and with the small amounts of catalyst, and ii) of phase transfer agents. In addition, the catalyst system is obluded in the present invention by the use of ratios which allow for a greasy acceleration of the reaction and provide an ecological process with meaning in " green quot; " Also advantageous is the method of this invention. The catalyst system of the present invention is a system of selectivity and selectivity. (temperatures of about -20Â ° C), and without the need for additives or additives, thus, catalysts are attained, the numbers of the turmover (TOb), expressed as moles of product per milligram mass, to ca. 100, and yields of ca. 4%, 2%, etc. The inventor of this invention was reported in the use of complexes and 2,4-otoxy-1,3,5-trimethoxyethane as stabilizers for the peroxidation oxidation of salts secondary to ketones and or ketones. In addition, the present invention recounts, for the first time, that the complexes of that type catalyzed the oxidation of secondary alcohols to the corresponding ketones, requiring the presence of any orally cyclic solvent,

Os complexos do cobreiΓ1; desta i n ver: ç lo constituem, assàsp os psi o oiros catai is adores com ligandos 1 , i-alcoxi-1,2, a-r.r iasapeosaolenoto» activos oa oxidação de álcoois secundários As correspondentes cetonas, à ίηνοποΑ:θ refere--se alada à obtenção de os» coro tipo de sistemas cataiitices, baseado oestes complexos a no oso inovador de microcndes, aitamsnte estivo em tempos reaoeionais multo curtos, aa preparapão de cetonas per oxida cão peroxidat Iva:;. num sd "'passod, de álcoois secundários.Copper complexes; of the compounds of the present invention, and the oxidation of secondary alcohols. The corresponding ketones, as used herein, refer to - The present invention relates to the preparation of peroxidated peroxidation ketones and to the preparation of novel ketone peroxidation ketones. in a second step, of secondary alcohols.

De facto, os complexos de cobre da presente .invenção seibem uma aecívidade catalítica notáoe L f sob condições moderadas [aO --- «0 "'Cd e ambienta imente toleráveis, para aouala ec ida çSo* 3, Descrição técnica â invenção consiste na obtenção de an novo complexo de cobra111} com iigarados: 2> i-etoxi--·!» 3, t-Crrarapeecac.ieneto e ao oso daquele composto e do seu análogo 2, f-otetoxi--- coro catalisadores eficientes e seiestivos da oxidação peroxidative do álcoois secundários as cetonas corxespoodeatas, assistida por microondas e na ansência de aolventea» A obteoçoo do catalisador [Cu [KH=<l(0Et} PC COEt) :“N.sj ?j 1 e a descrição do processo catalítico de oxidação peroxidativa de álcoois secundários (oom recurso a miescondas e por aquecimento convencional) são indicadas coo maior detalhe através de alguns exemplos que são meramente riascraf ivos, não sendo de carácter limitativo do inbrto da presente invenção. 3 v 1 Exemp I o da S1 n t as e do c orno i e ao 2 , 4 - o r o xl - 3, , 3, 5 - •. r r a z a p o n r: a d i. o n e t o do cobre (II ) A uma mistura do nitrato de cobre (II) , Cu (duo , 2, zí-bC; (231,3 mg, 1 roo 1) adiclonoe-se dioianamidoto de sódio (89,0 mg, 2 mmol; em Et OH (o nu.·} e aqueceu-o o ao refina o com agitação.. Ao fie de 10 mire observou-se a formação de um precipitado verde, Após ama hora de refluxo, adioiocon-as n-prolilamina H equiv. em relação ao nitrato de cobre (II)} à solução e apõe ca . ih a solução apresentou-se vermelha e observou-se a formação de um precipitado branco fa análise dc precipitado indicou 'tratar-se de halldr} . nsta foi removido por filtração após X2h sob reflexo, e o filtrado contendo 1 levado â secura ir vácuo a 20 ··· 25 b::, A reeristalixaçáo a partir de uma ec st: ura do água/acetona (1c10) dou origem ao completo 1 puro (rendimento 85 8). A roer istal inação: n partir de etaroi originou cristais vermelhos que foram analisados por difraeção do raros X, O complexo 1 foi caraeterirado por espectroecoola de XV, ospectrometría de massa, análise elementar e difraeçáo de raios X> XV (XSr, bandas sei eco i coadas, em'A : 3536 (s) , 3326 (a) v(PH}; 2361 (s) , 2323 (m-x) v(Cil; ; 1603 (s) v(C>A); .1536 (s) ο (NH3 , ESI '"-Má (em scotona; , ?a. ts? 383 ΓΜ 1 ΚΓ, Anal, Caiod, para Cd d písCuPuOu í C, 37,94; K, 6,37; H, 2 2,12, Bncont rado C, 33, o, H, 6,31; X, 22,00. 3.2 Exemplo doo estudos de aot i virado catalítica 3,2,1 Aeaoçbes assistidas por so.oroondas: Pura tubo cil.indxi.co de pvre.x do reactor do mlorooódas CE3 Disoover foi colocado o. substrato (aicocti) {5 mm ο 1) , tsr~bociÍ'~· Mdropetbx.ido TBHe CIO mmol} o 0,01 mmol de complexo 1,3, 3-triaoapeof adieocto de cobre CU) (2, 4-metoai- ou 2, 4--00001-1), O sistema foi fechado, colocado 000 agitação e radiação de mi oro onda a durante 0, 15, 30, 00 eu 210 min,, a 50 o o 80 ';C, dependo do álcool usado como aufostrate, à potência de 10 b, Após a receção, deixou-se a mistura reaccioaai arrefecer até à tempera tiara ambiente, 1.2.2 Método de aquecimento eonmenciena1s 3a reacçdea de oxidação peroeidativa foram rea1iradas em daleoa de fundo redondo de 50 me equipados cem. um condensador, Em condições nerms rs, adicionou-se 0,01 mmol de complexo 1,3,5-cr 1 araoeriad 1 eneto de oobre(Xl) (2, i-metori- ou 2, 4.-etoxi-1) , seguido do álcool (5 mmrsl) e fsr-butil-hidroperexido TBBP (10 mmol) , A mistura reaoOlenai foi co) o ca da 30 a 322 min, eod agitação vigorosa e o qu coimar. 10 convenci o tal, sendo a temperatura desejada (entre 40 - 52 °C, dependendo do álcool uri 11.tacto obtida recorrendo a um banho de óleo. 3.2.3 Análise por cromamografia gasosa: A mistura rasei tente da réacção foi tratada com 5 mi de acetoai tri,lo O: 323 μ d de parir ào interno · e, g -, bentaloeido) , Ac os agitação, retirou··se orna amostra, colocoa-se num tubo de tipo .Eppenborf, diiuiu-se com EtsO (ca, 10 veres) e cenrrifegcu-sc, tara análise no cromatoarate gasoso da Fiscos Instruments TC 5200 series ;detestar FXD) , injsctoa-se ume amostrei de 0,4 ai na coluna capilar DB-524 (Jãb; >In fact, the copper complexes of the present invention have a catalytic activity not only under moderate conditions but also in conditions which are tolerable for the production and processing, in obtaining a new cobra complex111 with ligands: 2> i-ethoxy-3,3-tetradecyclohexanecarboxylic acid and to that of the compound and its 2-phenoxy analogue, which are efficient and selective catalysts of the peroxidative oxidation of the secondary alcohols, the ketones corxespoodeatas, assisted by microwaves and the solvents of the catalysts (Cu (KH = < 1 (OEt) PC COEt), and the description of the catalytic process of peroxidation oxidation of secondary alcohols (using condensers and by conventional heating) are set forth in greater detail by way of some examples which are merely cross-sectional, and are not limiting in character of the invention. 3 v 1 Example of S1 n t a nts and 2, 4 - r o xl - 3,, 3, 5 - •. rr a z a p o n r: a d i. (II) To a mixture of copper (II) nitrate, Cu (duo, 2, z) -b (231.3 mg, 1 mmol) was added sodium dioanamido (89.0 mg, 2 The residue was purified by flash chromatography on silica gel in EtOH (EtOAc) and heated to reflux with stirring. At the end of 10 min the green precipitate was formed. After a reflux time, adioiocon-as n-prolylamine The solution was red and the formation of a white precipitate was observed. The precipitate was collected by filtration and the filtrate was evaporated to dryness. was removed by filtration after X2h under reflux, and the filtrate containing 1 taken to dryness in vacuo at 20Â ° C 25Â ° C. Recrystallization from water / acetone (1c 10) gave complete yield 1 pure (yield 858). The title compound was obtained from red crystals which were analyzed by X-ray diffraction. Complex 1 was spectrocoated with XV spectrocoola, mass spectrometry, elemental analysis and X-ray diffraction > XV (XSr, known bands, in 'A: 3536 (s), 3326 (a) v (PH), 2361 (s), 2323 (mx) A), 1536 (s) δ (NH3, ESI '-Má (in Scotone, Î ± Î ±, Î², Î², Î², Î², 6.37; H, 2.12; Found: C, 33.0; H, 6.31; (5 mm ο 1), was added to the substrate (5 mm ο 1), followed by stirring at 50 DEG C. The reaction mixture was cooled to 0 DEG C., 01 mmol of 1,3,3-triazole complex of copper (CU) (2,4-methoxy- or 2, 4-00001-1) complex. The system was quenched, stirred, and irradiated for 1 hour. 0, 15, 30, 00 and 210 minutes at 50-80 ° C, depending on the alcohol used as the sample, at a power of 10 b. After reception, the reaction mixture was allowed to cool to room temperature, 1.2.2 Method of heating and cooling The peroxide oxidation experiments were carried out in a 50 m round bottomed flask equipped with 100 ml. In a similar manner was added 0.01 mmol of 1,3,5-bis-trifluoromethyl-1,3-diisopropylimidazole complex (XI) (2-methyl- or 2,4-ethoxy-1) , followed by alcohol (5 mmoles) and fsr-butylhydroperoxide TBBP (10 mmol). The reaction mixture was cooled to 30 to 322 min, vigorous stirring and quenching. The temperature of the reaction mixture was determined to be between 40 and 52Â ° C, depending on the alcohol obtained using an oil bath. 3.2.3 Analysis by gas chromatography: The crude reaction mixture was treated with ml of acetophenone were added to the sample, and the solution was placed in a tube of the Eppendorf type, diluted with EtsO (ca. 10 times) and concentrated in a gas chromatographic analysis of the Fiscos Instruments TC 5200 series, disinhibiting FXD), injected 0.4 μm of the DB-524 capillary column (Fig.

Tabela X ·~ Oxideçac de álcoois eeieccloEados catalisada pelos coaplexoe [Cu{bnXnlDR} HCXOR} -"ÍH} o] (R Be ou Et1 b5Oxidation of alcohols and cycloalkyls catalyzed by the coaplex [Cu (bnXnlDR) HCXOR] -]] (Rb or Etl b5

Catai< Subatrato a Siecoeasas teaps Produto paio j too ΪΤΟΓ se:Sá:U;e:sato 5 X Mc L" ssuiiát:rooi cio 3 0 a se te ::8s;.»’:a *00 puxa 100 i :i R;a“ ·t e aà 1* ç ano 1. sis 30 a as to fanou ;a B 3 0 : L ?8 i 8 2 n o;: i-Ooso seeaoos. s' ΐ ;'í\ 30 soei: sfcaroòa 2230 ré-nn 37 XH R- " -íól:'l:'l Ο X 0- nÉriloá saia Ó :P s;estof seona 20 • 20 i i Mu lotei IsCeaaoI aao 300 4 0* ·' Ó: n s 1 5; :: 81 Re icnças?'*::* •o prq 200 ORrccaasera: 300 pl 12' 90 Re adeaseaeni s> Í sft 240 8 turrares: ;s 210 ; 102 31η X-li Ud;. u‘ .·:.·κηΟηΟ;ίΟ^·:'ΐΟ·;1 a ia; 220 cisisraísaasas 22* ; 121 IV'?· Ma 2 naoeool si;:; 22 0 2~oct:.eas.oeu 42* 8* 10 2 í Condi coes reaccioásis; £ sasol cie aubst: setco '0,. 01 s*"ol. de: eat si is abar (2,1 2 tos. SCO SCO st natal 10 ssiucíi da T28> : .·' d agaU, a 20 OU * tàssaco be cisisc estou., i ti ess ·'·' ίή-η?:;:: :: a· notes da retesa. pae: no 1 e -lo o a t a 1 i. 2 snr . ereqcbaets UC ò-' -1-11 i-X' í-: τ' li 1 - 1¾ -1- c. > 11. *1X5 15 cãs por hecá Oaiaoís sstre pa ateias: ta 1 , Bssaacco ess eaelisea por o r ene. t: cg r a ti a a a a os a 1 00 2 da seles tleidade 2:0 tace as 0 5 coe os... 2 to; an a 11.1.1 s sd a a 0 f :>0 5 cedi (Cu 1 3 o* L esc scàeu: pát o) ,Catai < Subattract a Siecoeasas teaps Product paio j too ΪΤΟΓ se: S: U: e: sato 5 X Mc L " (a) (b), (b), (b), (b), (b), (b), (b) and (b) L-8 and 8 are not included in the invention. (s): â € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒ 1: 1: 0: 0: 0: 0: 0: 0: 0: 0: 0: 0: - - - - - - - - - - - - - - - - - - - - - - - - - - - - - Sols 240: 210; 102 31η X-1 Ud. 1, 2, 3, 4, 5, 6, 220 cisisraísaasas 22 *; The compound of formula (I) 22.22 ° C. Reactions Conditions; A solution as described above. 01 s * " ol. from: eat si is abar (2,1 2 SCO SCO st natal 10 ssiucíi da T28> g '; ::::::::::::::::::::::::::::::::::::::::::::::::::: . < RTI ID = 0.0 > 11. < / RTI > 15% by weight% by weight% by weight% by weight% by weight% by weight. 2: 11.1.1 s sd aa 0 f: > 0 5 cedi (Cu 1 3 o * s esc sc:

Os cataiisasicrec sáo notavelsaente séticos e seleoticos na ORidaçss por ter~buòil:~01dròperó;xi:dp: de álcoois secundários a cetoriasç assistida por rricroocds $.The compositions of this invention are particularly stable and selective in the compositions of the present invention, for example by the addition of secondary alcohols to the ketoriasis.

De sol isen ta r ainda que aque las aatividade e seientioidade notórias ocorres: ca ausência de qualquer sol censo adro i ocasoy octao ilustrado na Tabela 1, 9 [11 m Ollmantbs Fnoydiopedia of Industrial CneAd.stry, diiey~VCB, Weinheim, 6";í edn>, 1002; (b) R, A, BrG.ley and Η. 1, Jackren, Cbéaistry and the Chsjtical lAduStrv, CPC Press, 2002; ícl iroccsa Cnemieary ih the charriseeatical Incurstry. dal, 2, ecl, R, Gadamaaetti and 2, Braish, CEC Press, 2008, [2] (a[ Is, 1, katienko·, L, A, Mosoloea and G, F, ia: koo.Even though the aforementioned high activity and seineness occur in the absence of any sunspot census, which is illustrated in Table 1, it is clear that this is the case. 1002; (b) R, A, BrG.ley and Η. 1, Jackren, Cbaisaistry and the Chsjtical lAduStrv, CPC Press, 2002; The present invention relates to the use of the Invention. dal, 2, ecl, R, Gadamaaetti and 2, Braish, CEC Press, 2008, [2] (a [Is, 1, katienko, L, A, Mosoloea and G, F, ia: koo.

Puas, CAen , Aav., 2000, 7i 8, 211; (20 0, Koítiya, ; 3. XÍOji and Si-I, Murahaehi, CAe n; , Corar as, 2001, 65; i C; hl KdMiya, 1, Ha o ta. and S, I. Hnxahashi. Xe tsahedron Xect,, 1008, 33., 1 i. 031 < (a; 3, Toj o and M, Fernânder, ílaidation of Aicoi :cua to didaAndes and betones; A Snide to CurJ-ent Coxmot Fraetice, * iprlegar, 3ew y;; :rl, 2006; {ti d, Cl E, Arende and P, A< Sheidon, Podem Oaidadion .MetAocíd, £d, >J.. ~S<Puas, CAen, Aav., 2000, 768, 211; (20.0, Kotitia, 3. XiOji and Si-I, Murahaehi, CAe, Corar as, 2001, 65; i; KdMiya, 1, Ha ta and S, I. Hnxahashi, Xe tsahedron Xect , 1008, 33. 1, 031 (a), (3) and (4), Fernand, et al. (1990). , and (c), and (b), the expression of a compound of the formula (I)

Bacivaii, dl ley-vCH, vOninhein, 2004, 8 3 , [4] (a; M, G, Speriali, V. 31 Cesta, F,. A, Robles·"Bacivaii, dl ley-vCH, vOninhein, 2004, 8 3, [4] (a; M, G, Speriali, V. Basket, F, A, Robles · "

Onten.hefn.er and 0, V, Gnsetsiaya, Cxxxaaoseie 1 lias 2002, 28,· 3186; (0} B. R, Travls, κ, S, Rarayan and B, Borban, 2 , d:, Odes;, loc, , 20 02, .124 , 3824; ícd 0, Yang and C,Onten.hefn.er and 0, V, Gnsetsiaya, Cxxxaaoseie 1, 2002, 28, 3186; (0) B. R, Travls, κ, S, Rarayan and B, Borban, 2, d: Odes ;, 20,124, 3824;

Ohang, J. Org, Chem,, 2001, 86, 1814; (d; H, GkUMOtC, K, Ohtsuko and S< Banjoya, 2Ha:istt, 2003, 3101; (a). Μ, H, ί:Γ·: lates, Xe treAedron Leis:, ... 1393, 38, 2813, l:(a; X, E, Parlo, Pl R, G.iies, M, Trotara Kl, 3, Hl Br own and 0, ;1, DreO, ocience 1300, 234, 2044; Ibl D, Bogdas and Ml êalssdenlçr, Sánlett, 2000, 143, G, Ferguaon and ; 0, h, Ajjoa, T&rrakedros leras , 3, 44, 0 139; (h) G, FethenPerg , I,. Fe Idherg, B, ner and 2, Saseon, d, GÀéò, do c, , Pe x:k:xn ?mn s., 8, 2, 2429; (ol 0, C hak raias rty, i R Sarcah, B> Saha, ChaRrasorty and E. K, Das, Inor g. Cnea, 2009 , 48, 13 31 17} ía; o, Single M. Chana, M, Cnibbery J< Kaar and d. :L< Ead, Synth, Coonno.., 2000, 30., 3941; :(b) D, Panday and D, 0. Kotari. , Ox;i, d.. dommua,2 009, 32, 3 2 X,Ohang, J. Org. Chem., 2001, 86, 1814; (d) H, GkUMOtC, K, Ohtsuko and S <Banjoya, 2Ha: istt, 2003, 3101; (a) 2813, 1: X, E, Parlo, Pl R, G., M, Trotara Kl, 3, H. Br own and 0 ,; DreO, ocience 1300, 234, 2044; (H) G, FethenPerg, I, Fe Idherg, B, ner and 2 (Mg), Sánlett, 2000, 143, G, Ferguaon et al, Ajjoa et al. , Saseon, d, Géò, of the c,, Pe x: k: xn? Mn s, 8,2,2429; (ol 0, C hak Rays, i R Sarcah, B> Saha, ChaRrasorty and E. K , Ea, Synth, Coonno., 2000, 30., J.A., < / RTI > (B) D, Panday and D, 0. Kotari., Ox., D. Dommua, 2000, 32, 322,

ÍBjla) L. Paionbi, F, Bonadies and Ά. Seatti, Tei z a heoiron, 1097, 53... 158 67; {;;) Cl Gonrl lar---àrellnno? 0, PHIbbla) L. Paionbi, F, Bonadies and Ά. Seatti, Tez z a heoiron, 1097, 53 ... 158 67; Cl? 0, PH

Campal o; D, 2. Macqnarrie and 07 2L Ma rira a,Campal o; D, 2. Macquarie and 07 2L Ma rira a,

CnemCusCdern , 2008, 1; 746, (a) A, Corda and H. Ca roía3 Cânon Soc, Ran, , 20087 37 2090; (b) 1, Tonacnri 97 Kioasrro; d< d5 Ale a s and ro, MCnemCusCdern, 2008, 1; 746, (a) A, Rope and H. Cava3 Soc Cannon, Ran, 20087 37 2090; (b) 1, Tonacnri 97 Kioasrro; d < d5 Ale a s and ro, M

Br assa η, P, D ; Arlir o s i o and a, Mo r o i 1. lo, Cr e en Câ ew. , 2009; 11; 816,Br assa η, P, D; Array the s and o, Mo r o i 1. lo, Cr and en ew. , 2009; 11; 816,

Lisboa, 1.1 do Março de 2 010Lisbon, March 1.1, 2010

Claims

1. A method according to claim 1, 1 and κ ο of cob (11 f, with 1, 2, 4-epoxy), 2,5-triadapen: babiforefractions were obtained for the preparation of CoFbH- The compound of formula 1, the chordance of the compound of formula (1), (1) and (2) This is characterized by the application as catalysts for the oxidation of the secondary alcohols to the carcasses. Oxidation process but the aliphatic hydrocarbons are characterized by the use of the compound of the formulas 1, the analogue 2, 4, 4, 5, 4, 5, 6, 8, 10, 10, 10, 10, 10, 10, 10, 10, The method according to claims 3 and 2, characterized in that the application of the organic solvent to the organic solvent is carried out according to the invention. sur. i.-s hsdropa sdo ground as orsdante agent, Lisbon, March 11, 2010