PT104884B

PT104884B - 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: PT104884B
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: 2011-10-26
Also published as: PT104884A

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-Mixoxy 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

Csapslexo d# cobre CX SI osa» l±spm4os 2 f 4-etoxúmX , 3 f db" briaòepsuitadieeoto « ssm í^Iioagão e do análogo ;2,4-motossi casto catal£««âox*S! para a omidoçio .poroxid&ti^a, aesiet.ida. por microoaéaa r. do álcoois socaodárxoa a cafcoaas b premente intsnupáo refere-oe a um. novo complexo de cobreiII) com iiaandos 2 , 4-eboxi.-l;í 3, S-cr.iasspermadie.netQ e ao coo daquele comporto o do oco análogo Qmbxuetoad. como mo: o 1 is odor os' oficiantes o sslectitos da oxidação peeoxidatiea de álcoois secundasios è s cotonas correspormientes, saci stida por mi oroandss a aa sosioci a do solventes<Csapslex (d) copper CX SI osa (1) spm4s (2) 4-ethoxycarbonyl, 3β db " and the analogue, catalytic 2,4-cyclohexane and the like. for the oxidation of the product. by microphone r. of the alcohols socaodárxoa to the cows b pressing intsnupáo refers to a. a novel copper complex) with 2, 4-epoxy-1,3,4-diazabicyclohexylamines and the like analogues. The present invention provides a process for the preparation of the compounds of the general formulas (I) of the compounds of the general formulas (I): ## STR1 ## in which:

Dominio téenisó da issoeoçàoaTense domain of this

Cat a li. atp Microondas, Qa.iod.oa da Coordenação, Qai.mi.oa. \s X'0 dl Λ X .1 Ccl R. técnica aatarior t do ceton.es fi.qo.tam entre os compostos qe.imiaos mais .nmpcdtiantess oomo produtos iutorbodiàrios ou finais, por exemplo como precursores do polimoroa ou como sobsteatos paro. a indústria farmacêutica (Ij , Embora possam ser sintocisadas dor oxidaçao ai. rocia dá- ateanos [2,3] cu alouiuos te] , essa a sascqêoo oâm sao, em. gora.1, aolootivas [21 > êsaim, a oxidação cm. fase liquida da álcoois secundari os a detonas, que parcos ssr o método móis iX teimado q também assais sánpies ti, Si, mas qus: qoraim.o:oto sc limita a compostos bonriiicos [6] f necessita do quantidades oXotadao de catalisador tis: , lanços tompoo .solventes reateionais [6] o/ou aditivoo (basco, açentes c& transferência do fase, atot [5,6], asarm como de oxidantes dq. sais sis ma .n ganes, cnomotosl p.,7] mmsmmmmmmmmmmm [ate6 o,7f8] que aâo muitas vates dispendiosos e tdaicos, âlém disso, os catalisadores utilisados soo frequentemanta dispendiosos (baseados em metais nobres) [?)), dlfineis cie preparar e nao apresentar: grande actividade na oxniaçao de álcoois alifâtiooa [6)- Persiste, assim, a necessidade de encontrar outros cisternas .sintéticos de cetonac que possam ultrapassar peio menos algumas das: limitações mencionadas acama - 0 presente trabalho rol desentoa eido no Centro de Química Sstrcataral (Compleae 1, Instituto Poperi.tr Técnico) no âmbito· de estudes de investigação do bolseiro de pds-doutoramento Dr< P> Fioiai, dos investigadores a-.mui liar os Dr, 61. Paeri e Pr, Fbb, Kopvlovich, cia ;Dr.4 ibF, Cucdes da Silos, da Dr ,s bJsbbF, bartins, é da bei seira de doutoramento mostro i-F.d- Silva, estando inseridos em. ptajeotos da responsabilidade do Prox, armando IdL, bombeiro, suportados pala Fundação para a Ciência e a Toonologia e peio seu programe. PPC.DT (financiado peio FFDEP), beeoxigáo des figunes: FI(?. 1 - Complexo de çobre ; II.) com 11 germes 2 , i-atoxi-13,5 " t r.i a aspe o cudl orce tof do 16 nm ul a [Ct i EH vC f OSt) HC [OEt l -dia l c 1 (X) -Cat. Microwave, Coordination, Qai.mi.oa. Among the compounds which are the most important are as immobilizers or final products, for example as precursors of the polymorph or as unsubstituted or substituted prodrugs. . the pharmaceutical industry. Although oxidation may be synthesized in the present invention, the present invention provides a process for the preparation of the compounds of the general formulas (I). the liquid phase of alcohols secondary to detonations, which are weakened by the method of the invention, but which are also unsubstituted, but which are limited to benzylic compounds [6], requires the amounts of the catalysts (5), as well as the oxidation of dyes and salts, as well as additives (Basque et al., 7) In addition, the catalysts used are often expensive (based on noble metals), to be prepared and do not exhibit: great activity in the oxidation of aliphatic alcohols [1, 2, 3, 4, 5, 6) - Thus, the need to find other cetonac synthetic cisterns persists which may exceed at least some of the following limitations: - the present work will be carried out at the Center for Chemistry Sstrcataral (Compleae 1, Instituto Poperi.tr Técnico) within the framework of research studies of the pd-doctoral fellow Dr < P > Dr. Paeri and Pr, Fbb, Kopvlovich, and Dr. 4 ibF, Cucdes da Silos, of Drs. BJsbbF, bartenders, are from the PhD doctorate. d - Silva, being inserted in. ptajeotos of the responsibility of the Prox, arming IdL, firefighter, supported the Foundation for Science and the Toonology and by his programe. PPC.DT (funded by FFDEP), beeoxigenic figs: FI (? 1 - Complex of II) with 11 germs 2, i-ethoxy-13,5 " The title compound was prepared as a white powder (16: 1) to afford the title compound as a white solid (16: 1).

Fih.. d - Oxidação peroxi.datira de álcoois secundários àe cetonas correspondente- IMécxidáe da inwnçio-s 1 - tlrrjectieoa e eaetagens G objecti tao geral dea ta irntançdo coseiate aa obtenç-so de ;i.rs p rores se fácil e eficiente de forttrcao de co tente por oxidação pcroxd.da.t .1 na. de álcoois sscnndár ice , em eondiçdes mede rada. a. asaiotido por radiação ce micrcondam, Isenta de 1; .'1 b Vbí H v Cd rb ou ama ti a a Cí 1? $ ati.liaan.de em oataliaador e um oxidaste ambiestaumente aceitáceie,(D) Oxidation of secondary alcohols to the corresponding ketones. The purpose of the invention is to provide an easy and efficient method for the preparation of the compounds of general formula (I). oxidation co-oxidation system. of sialic alcohols, in measured concentrations. The. Assayed by radiation and micrcondam, Free of 1; .............. In another aspect of the invention,

Iara tal, foram saleocionados ca; Xlgandee 2, i-mlecxi-1, 3 f S'''triaeap:ent:adiecelo?· em partieoiar a 2, oboaetcxi-''1 ., 3? 5-t r la a ap e n t a d i e ri et o e o 24 -0:1. o a 1 -1,2, 5 ~ t r iaa a p e n t a d i e a e t o, cmg metal o cobrai 121,. e oa eatodom; deaen.volxerem-se no âarb 1 t e d a a a a a a 1 a t a a obd a c c i co a ma 1. a e a o e c i f 1 c o s; (1) obtenção de nm noeo complexo da cobraiII) cem 2,4~eto>ri·'' 1, .3, S-mriaaspentadimrasoo e (ii) agi i cagao doa coce laxo o 2, f-mbtdxi·-· a 2f 2--midxi--d, 3,- d-frilisapadtadianatb a oxldacao catalítica da álcool, a eeoaodârioa ao condlçOee mederadao e teioráoola do ponte de eleta axòxLeotal, com dono rendimento 0 aelsctacidada,Iara, they were brought out; The compound according to claim 1, wherein the compound of Formula (II) is prepared as described above. 5-tetradecarbonitrile and 24-O: 1. The invention relates to a method for the preparation of a metal in the form of a metal. and the eatodom; The compounds of the invention may be prepared by reacting the compound of formula (I) with the compound of formula (I). (1) obtaining nm in the complex of the cobraIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIII 2-methoxy-d, 3-d-frilisapadtadianatb the catalytic oxidation of the alcohol, the edema to the measured and optimal condition of the electrometalleric bridge, with a yield of 0,

Goeteo obdoctlces decortee a obtenção do primeiro oomplsxo de cobre cem oa iiqendoa 2,4-eloxi-l,3,5-t r r a a a p o n t a d 10 π o t o, i Ga i b H - C (0 n e ) dl C 0 a t} -- d:MU f X „ liam c iaa o , neabum a l e t oma baseado num complexo da cobre cem. 1 i g a n d c e d o 11. d o a,, 4 - a 1 c o x 1 -1, 3, S ™ t r i e r a p e n t a d i o n etc for a. aplicado i oxidando peroxidatiae. dc álcoois secundários *In order to obtain the first copper compound of the invention, the 2,4-oxo-1,3,5-triazole-10-one, The invention relates to a process for the preparation of a copper compound based on a complex of copper. 1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 11, 11, 11, 11, applied and oxidizing peroxidatiae. of secondary alcohols *

Ao principais vantaeene aooociadeo a oata incenção conoiatom nc rooarea a catalisadores simples, amciorítelme-nta iosierâecis (do efeito pol.ncn.to marito reduzido oa nnJmd e facilmente obtidos por uma cia simples irami aó "passo·"! c conveniente a partir de materiais de p a r t i d a (se n s sa 1 s ma t á .1 i com) d i sp ο η 1 a? el s .c orne r c i a 1 a e ai a a de baixo casto, outras esorapens residera na. boa estabilidade destes catalisadores spb copo ipôes expoentes a aa su:.a solubilidade 0:05 áleood s substretos , permitindo asara; r ,? que o 'processo este lir ico decorra, o a ausência de outros srd.es orem e o em peso on a s q; a a n t -x d a a es e e o a t a. r1. s a. o .e r ,· e .:i / e rr n a .r a oecs asidade da agentes de trs o s: f e r en si a de fase. .Alem dia so,. o sistema catalítico que é objecto da preapoatc ioeetpbo recorre ao uso da Ta.icroondss, qus permitem acelerar qrandemenoe a reacçâe o proporcionar; ira precatao ecológico: cora significado em ^quioica osrdrPp •Pensa it aindd faiabdp uma escapem: ds: .método da s t a ieeebção, O sistema catalítico da presente iesmtaeào ooeatitui um alstaraa da spe-sadas aotimidade e selecti5a.àade, e;u condições· a; ode radas (tempematoras dc 10 - Se °C) , e sem naceaai.da.de. de. cc-catalisadores ou. editámos, Assisu .foram, atingidos números Ce oielos cataiiticosi , s. , núamros de "turuoversí ρί'Οίρ , expressos em a;oles de produto por mole de catalisador, atè o«, 900,- e rec direta tos de oe, leu %·. '2 ,v Caracberiáriares inovadoras 4 intenção em aoâliee repor ta-se ao aso inorador de c om ρ i ex a a de e o P r e {11 r ç om i i ga r. d.o: s a, 4 ~~m et o x. i - a 2,4-etexi-l, 3,5-triaxapentadj.er.eto caso saraiiaadta;es para a oxt.aaçao' eerpxn.oatu.ts de areoous secoeasrtos es serenas a; o r r s s p ooca o t e ;·;,The main advantages of this invention are the simple combustion catalytic converters, the low viscosity of the catalytic converters and the low melting point of the catalytic converters, which are easily obtained by a simple process which is convenient to use. of the starting materials (if it is necessary for a low chromaticity), other esorapens will reside in the good stability of these catalysts The solubility is 0: 05 at room temperature, allowing the procedure to be carried out, the absence of other solvents and the weight in the furnace. The catalytic system which is the subject of the present invention is characterized in that the catalytic system of the preapologetic uses the use of Taurus, which allows to accelerate the reaction and provide ecological precaution: The catalytic system of the present invention is a catalyst for the optimization and selectivity of the conditions to be achieved by the catalytic system of the present invention. (temperature range 10 ° C to ° C), and without naceaai.da.de. in. cc-catalysts or. we edited, Assisu. were, numbers hit Ce oielos cataiiticosi, s. , Numbers of "turbulent", expressed in product numbers per catalyst mass, up to 900, -, and / In this case, the intention is to reject the incoherent behavior of the P r r om r om om om om om om om om om om om om om om om om om om om om om om om om om om om om om om. d: s, 4-methyl and x. i.e. 2,4-ethyloxy-1,3,5-triazapentadecarboxylate in the case of the preparation of the compounds of the general formula: o r r s s o o o o o

Além disso, a presente ineençdo recmttèeoe, peia primeira vea, goe os complexos daquele tipo catalisam etxciettemente a oxrdaçae de aiooois secundários as correspondentes cremonas, nem requerer a presença qr a1quer eolrent e organica,In addition, the present invention, which is first and foremost the complexes of that type, suitably catalyzes the oxidation of secondary amides to the corresponding cremates, nor does it require the presence of any organic and /

Os complexos de cobre: (113 desta iov onça o cone 111 uío, S: s s im, os primeiros cateiit adores com ligandoa 2, 4-alcsx.i- 1 g .V , , S-t ri.ssapentadianeto, a otivoo os oxidação de álcoois· sot endàrlos àe corresponder' :es cotonas 3. invenção: refere-me s inda á obte nçáo da um novo tipo de sistemas cata .11 ti coe, baseado nesta s complexos e no aso i n e vador de mietcondas, sltesíonte a c t i v s era t emp os rea e o i e na i s mu d t o cgrto s, ta proport çao de se tonas por oxi dseoo paroxldat i.va, n sm. ss X aseo"', de álcoois seerrdárioo.The copper complexes: (III) of the 2,4-dichloroethane derivative, the first catalysts having the 2,4-alkoxysilane ligand, alcohols, alcohols, alcohols, alcohols, alcohols, alcohols, alcohols, alcohols, alcohols, alcohols, etc. These include: The present invention relates to a process for the preparation of compounds of the general formula: ## STR1 ## in which the substituents are prepared by reacting the compounds of the formula ## STR4 ## with the addition of sterile alcohols.

De "facto., os: cosçriexos de cobre da presente intenção· eribem usa se tu. rida de sarsl.lt ice notável, sob condições m.cmm radas (dO - 8o °ΐρ e arbledte.lmee.le toleráveis, para eoaals cmldaçao > 3-í Descrição técnica a invencdo consiste na obtenção de um nova oemolemo de cobr e (la) com iiaandoe 2,- 4-0:1001-1,3, 5-triaaapentadieneto s as asa daqoele composto e do sea análogo 2,i-ómetoxi- como catalisadores eficientes e selecmivoa da oxidação perosidstiva de álcoois seconddrloe àe cotaras cottespondbntes, assistida por mlerooadas e na ausência do solventes > 11 obtenção· do catalisador: ICof MK-ClDEt) H€ /(>Et b:dbò}v j 1 e e dosoraçao oo processo catalítico de oxidaçás peronidadiva de áiooois secundários (com recurso a rbcrottidas e por aquecimento convenoiocal ί sdo i.ndi sedas com maior detalho através de aissns exemplos que são arar atente ilustrativos, uso sendo de entãoter iitd,tativo do ãsib-ito da preaente intenção, 3,1 Exemplo da S indene do complexo 8, i-etoxi·--!, 3, S--t r i a r a ρ s n t a d. i e u st 0¾ da o on r eg 11) d uns mistura de nitrato de cobrsdll}, Cu {dCn},, 2,Sufi 3831,3 nq, 1 mmoi) adicionou-se dicfenamidAto de sódio 183,0 00, 2 assei) -em Et Ou (5 ad,} e aquece a---se ao refluxo com agitação, Ao fira de 10 rsin, observou---se a formaçao de uns precipitado verde, Após ursa. dom de refluxo, adicionoa-ee n---proÍ:ld.erd.ne; (4 eqeiv, eu relação ao nitrato de ooPreílI); à aolnçâo e após coo Ib a solução apreseotou~se versA-lna e oPservou-ae a formação de no precipitado branco (a analise do préoipitado indicou tratar-se de )labdd , date foi teço vide per filtração apos 1 2d sob reflexo, e o filtrado contendo 1 levedo a secura in vácuo a 20 - 25 "2, A :recrist:aiisação e partir de iras mistura de água/acetona (iulO, deu origem ao complexo :l paro (randimento 8 5 id , d recristaliraguo a partir de ofanol originou cristais vermelhos gue foram, analisados por dff rasgão de raios 2d om" 'd :: 2336 U j .í ? urn - í 15 33 · ) s ; } , m/e; 380 ΪΜ * ••a .·; ,· .· .·- -ç *·*: í d, s-u yç s,,e 0 complexo X foi ceraoterixedo por espeotroscopia de IV, especttonetria de massa, analise elementar e cifraoção de raies X, X'v (KEr, bandas seieoclonad.ee, cm" d :: 3306 (s) \ddu)ç 2981 (s), 3 32 8 gs-x) v iCi:3d ? 1536 (s) 3 (du) , ESX"-dS: (em acetona) , m/e; 360 Hi3 Anal, Calcd , pare 3η%Α3χ3ρ)2ρ: d, 3 22,12 , Encontradn d 12( 5, 6,33.( A, 22,03,Of " fact, the copper bonds of the present intention · eribem uses if you. Technical description The invention relates to a method for producing a new copper omelet, in accordance with the present invention. (la) with 2: 4: 1: 1: 1: 1: 3: 3: 5-thiourea are then reacted with the corresponding compound and the like, 2-methoxy analogues as efficient catalysts and selective for the peroxide oxidation of alcohols seconded and cotestadent , in the absence of the solvents> 11 obtaining the catalyst: IC 50 MK-ClDEt) H € / (> Et b: db0) and the catalytic process of peronidating oxidation of secondary ammonia (with the aid of and by conventional heating of the silicas in greater detail by means of other examples which are illustrative, use being therefore of the preservative of the present intention, i-ethoxy-, 3, S -triara ρ snta d. (a) a mixture of copper nitrate, Cu (dCn) 2, Sufi 3831.3 nq, 1 mmol) was added sodium dicophenyl) in EtOAc (5 ml) and heated to reflux under stirring. At the end of 10 min, the formation of a green precipitate was observed, after which the reaction mixture was evaporated. reflux, addition-ee n --- proi: ld.erd.ne; (4 eqeiv, i relative to ooPreylI nitrate); The precipitate was evaporated to dryness and the precipitate was evaporated to dryness. After the reaction the precipitate was evaporated and the filtrate was evaporated and the precipitate formed. The precipitate was collected by filtration and dried under reflux. the filtrate containing 1 yeast to dryness in vacuo at 20-25: 2: A: recrystallization from the water / acetone (14: 1) mixture afforded the complex: (80% yield, recrystallized from from ethanol gave rise to red crystals which were analyzed by a tear of 2d rays in the form of a crystal. The X-complex was resolved by IV spectroscopy, mass spectrometry, elemental analysis and X-ray coding, X'v (X-ray diffraction). KEr, seieoclonad.ee bands, cm " d: 3306 (s): 2981 (s), 3228 (xs) 1536 (s) 3 (du), ESX " -dS: (in acetone), m / e; (Calcd, para 3η% Α3χ3ρ) 2ρ: d, 22.12, Found: 12 (5.6.33, (A, 22.03,

Exemnlo dos estados de accivfaade catalíticaExtent of two states of catalytic activity

Reacçdes as sis tidas por microondas:; dum tubo cilíndrico do rever do tsector do adoreondem: CEM Di.scevar foi colocado o substrato {álcool? {5 m.moI ? , t er bua íI - (nldrcpesbxido TBHP (10 líSiot) '·.*:* 0,01 ax ro i de complexo 1,·3,5 - triaeapeni:adisr ete de 0.0(0 ie {11} (2,-4- ma too:: i - ou 2, i- -eaoxi - 1) > G cisterna ror racnaao,· couoosoo s: (b an.it aça o e rs Piaçéc de microondaa durante 5i 15, 30., 80 ou 240 min,, a 80 ou 30 :í Gderend< t do élcoel usado como subatrato, á pc mine.lá. de 10 W, épó: s a reacçâ-ο, deixou-ss: a nd stura reat mm. coai arrefecer até à t emperata r s ambi ant s, 3., 2,2 Método do aquecimento conseccional: és teacçoea do oxidação peroxid.ati.v'a forais realixadae em baldes do fahdc redondo .de 80 sé, equipados οοοϊ um condensador, Mm condiçoes .ooramd.s, odicbinosr-se Os 01 mmol de complexo 1 ^ 3-^ 5 — trisxspentadiensto do dobro {II): (2* anaotoxi- ou dpp-stoxi- I) , seguido do álcool {d ícsold o re:r-but.:lI-4iidrtpeTbxMcReactions with microwave:; of a cylindrical adoreondem tsector review tube: CEM Di.scevar was placed the substrate (alcohol? {5 m.moI? (10: 1): 0.01% of complex 1, 3,5-tetrahydropyranose: 0.01 g (0.01 mol) of tetrahydrofuran, 4-oxo-4-oxo-1-oxo-1-oxo-1-oxo-2-oxo-1,3- min, at 80 or 30: the eluant was used as a subattractant at 10 wt. molar ratio, the reaction was allowed to cool to rt 3. Method of the consectional heating: This is the peroxide oxidation reaction in a round-bottomed 80-deg. bucket, equipped with a condenser, as standard. (II): (2'-anaeoxy- or pyridine-1-yl) complex, followed by the alcohol (dichloromethane). : lI-4iidrtpeTbxMc

(.BMP anao ol) ., é mistura roacci.on.ai fod colocada 30 a 300 U.·". à 'i C·. ,a. v.,,\n v· mire sob agioaçao vigoroso o aqurmummcito convencionai, sendo o temperatura desejada (entra 40 - 30 *0, dependendo 1 .a til irado) obtida rs cor rendo a um banho de 6 Iam, 3,2,3 énáXiss por cromaiograois gasosa: é mistura resultante ria reacçáo foi, tratada, com o ar, de aoetsnirrrio e 300 nL os padréo interno (eps., banesideido), llpos .agitação, retirou-as uma amostra, cslooou-se num tubo de tipo .3ppo.ndor.fl diluiu-se1 com EtvG (os, 10 veres) s centridngou-ec, Para aeâiise na cromai, ágrafo gasoso da Pieons Instrumento GC 8000 series (detentor MID), injectom· se uma amostra, de 0, 4 ui na coluna, capitar DB-Gat (G4W) ,(.BMP anion ol.), Is a mixture of about 30 to 300 U. ". . ,The. The conventional apparatus is vigorously shaken, the desired temperature being (40 - 30%, depending on the amount of ethylenediamine) obtained in a bath of 6 Iam, 3, 3, 3, The resulting reaction mixture was treated with air and 300 mL of the internal standard (eps., banesideide), the filtrate was collected, a sample was removed, the filtrate was slurried in a tube of the type . The powder was diluted with Et 2 O (10%) and concentrated in vacuo to give a sample of 0.4 g ui in the column, cap DB-Gat (G4W),

vanmmoaBenKooewnBtRMBWWwewwswWBOTlilMIMMMWW T-sbela: 1 - Oxidação de âlcooie aeleecd.e aedos ;t a ca lis a da MM X 0¾ cesaplexoe [ Ce· {Hd—C í00 DO4op} (s - de ou Et} - " CXctirl, Oab;e:ratc· Hiaroe.sdae ΙχρονΚΙ OseOets •ν-.,-xaa-Ò 4 -,.· ; ο 0;c:adi:aaat X. [elal oro.od 8%) :t--:ienil:íd;.snvl ele D f: acutofeseoa evo 400 (1000 Me v 1~ farina :> aos. si;:a 00 3;::;:;::::;; :3í: a. Θ Mj X X (1700 ct '·." is.si Istauí:;.!. e::.:?: 30 íiSíaOoOáaaáa 4830 87 { 07 0; Ke I - tanileée sol uise 0:0 a\::st:o:ieo<'ns X 0 d > 4 'j 4 d'M: bdnniáecanoi rdo < :'J ;'j MMM a- Mi- d: MC:M -D 4 03 XI í 04.4 Ha .X's\MXl:MM;:MMl X-iol OiO 0,038;34:8 4445 CU ISO 30 d 12} Míí (Sdiítx 348881 í;:í:s. 2:20 (oeiísxaiísçs 440: .82 U&ld da íilOilUsE:;:;:! 34 0 :::.884 niSsi :05440:0a 488 37 Oi2.4? D;í s-oscCseest s::03 Ml v: e"· diud;;;ie:d::t:: <; X X X ; d .·". ·. 04; s Oeadiçvas 3333134:04:3 4.3: 0 3330 4 333 8 30 3: 4: 3830. 0. . 0(3 84383 4 8484 8:-3:8 534.4..55,8 8.8O i 0 :,2 8 438:01 3'3 , S 448 8 4 :340: 3 7 v ; d) 8S4;íí4 íló 43x10 (0 30.·:.. 8 3 0 d(, * ;4ds;asa c ie 33 cioe 3 a'3 8.14 04033: 4:3: 83833Ό 8d3 SiO.388 5 30 8444 883483 5 so-e SCl.-:;: US: :330 3 1 isadar- : : .8 3 3::340.33:4.:¾ 83: ::; 4.4; tos 343.3 844 8 :(.8 385: - TOE } 3883 Cora pau,leras 5 334.:33 (3:3 idol- ;3 34. 3 } . " e.i3S8í888: 88 8: 85 85 SI is; o 8 - <: coneta grafia 033033, X i: 0 I iM <;·: e í i d, · ^ C p i N 84.333848 ¢43: 884808: oe íd-diuce a'.··.· r :o a,·-: ·.: d 4 '( ·.'; ;.· q ..-s Λ Ν',- ν. Λ.'ΛΛ \V \V «.V ».H ,V.' Cs 8.· 00a :3333,:4 í 0 í 4 0’ 434 4 7 88 v 380888 .8 3 434 4 ,1 - Oxidation of the composition of the compositions of the MM X 0 Csaplex and [Ce · Hd-C 100 DO 4 pO (s) of Et or C 2 -C 10 O 2: ratc · Hiaroe.sdae ΙχρονΚΙ OseOets • ν -., - xaa-Ò 4 -, • • • • • • • • • • • • • • • • • • • • • • • • • • • • •. (1000 Me v 1), and (c) the number of cells in the cell, The following equation is given in the following table: X-ray diffraction X-ray diffraction X-ray diffraction X-ray diffraction X-ray diffraction X-ray diffraction X-ray diffraction X- 0, 4, 4, 4, 4, 5, 6, 8, 8, 9, 10, -isoindole-2-carboxylic acid (1: 1): 0.038: 34: 8: 4445 (ISO 30 d 12 M) (Sodium 348881::::::::: : .884 niSsi: 05440: 0a 488 37 O2.4? S-oscCseest s :: 03 Ml v: e ?;;;;;;; ::: :::; XXX; d. ". · 04; s O and water 3333134: 04: 3 4.3: 0 3330 4 333 8 30 3: 4: 3830. 0 (3 84383 4 8484 8: -3: 8 534.4..55.8 8.8: 10.88: 01.33, S 448.84: 340: 317; (d) 8.44; 43x10 (0.30): 0.8 (0.8) 3 (d), (3), (3) and (3), (3) and (4): 83833-8d3 SiO.sub.388-530 8444 883483. 3: 4: 340,33: 4: ¾ 83: 4: 34: 343.3 844 8: 3838: 5: 334: 33 (3: 3 idol-; 344.3): " e.i3S88888: 888: 8585 IS 8: <: " 033033, < (C) N-dimethylaminopropylamine (84.333848) 43: 884808: (a) The compound of formula (I) - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - 88 v 380888 .8 3 434 4,

Os ceealiaadoree aão noívaaoiarente actlvoe a ealectiaoe aa ani-daça* eoc cer-diittl i-hidroparóxi do da âlodais secundárias a cetosas, as si acida. por :sdcrestadas,The compositions of the present invention also include the addition and reduction of the secondary to the secondary ketosis. by: sdcrestadas,

De salientar alada qus; adeei.as aot ávidade a seleçtxeidade notórias ocorreo, .na ausência de qsalqeer solvente· adicionado* ocsao ilustrado nu Tadela 1, iiiuiniinpnuiiuuiuuiiuiiiiiiwiuumiiiiiiBimgg!—w—8awaiBÍ»wgwnBWBBBWWWWWWBBWigWWBBlOf pointed out that; In the absence of any solvent added thereto as shown in Table 1, there is shown in Fig. 1 that the viscosity of the solvent is in the range of 0.1 to 10 wt%.

kEFilkÈRCIASkEFFILITIONS

[ X1 vδ} X1,XoadA' a Encyclopadl& óí: iluda s triál Ckarai ai;ry,[X1 vδ] X1, XoadA 'to Encyclopadl & In addition,

Rilop-vltib Ebinh.oirn tr;': edn., 2002; cbj Η. A, Sadley and h, l. Jackson., Cnerd.atrf and ide Chemical Ináostry, C.RC ?rassf 2002; {cb Broceaa Chemiatry ia Eda PaarmaceationX X,ndoabry, dor, 2, ad„ K- Gadaonaotri and Ti B r a X. a h, CMC Pr ara.- 2 0 0 0 , j v a 1 x, v à - Mationko, 2, •<s\ Maaalo ra and G, n, 2aIkon, Rara. Orar., Per, , 2009, 32, v». .-.. y s kà R, komlya , 0, Ra pi a n d 0, " 2. Murada adi, il a ar, Coier; r, 2002, BB; OcO R, koaslya:, Ta Piaota and S > :!b M a rada ai ri, Oatrauadran lati,, 1006, 01"?, 10:3 0 <. (a) 0. 0oj:O and M, Ba r η B a. d:a r, dr i da dian .crf .Aioriroia to Pldodpdea o;rd Rot : onera a atirara to cirrrant Coma; ao Pra at i ce ,· Sprioq© r , 0 a o 2 ar r, r o 0 o; Ibl d, C. 13 ArarrPa ano: κ. A, rna,;.anu, Pio da r n ôx 1 da 0 i. o n : Blaidoda, Rd, 03 ™R, Bank ra 11, Mi d. ay--3210 , Rainha da, 2004, B\ 3'Rilop-vltib Ebinhorn tr., Edn., 2002; cbj Η. A, Sadley et al. Jackson., Chem. Atrf and ide Chemical Inostry, C.RC. Rassf 2002; (cb Broceaa Chemiatry, Eda Paarmaceation X X, ndoabry, pain, 2, ad. K-Gadaonaotri and Ti B ra X. ah, CMC Pr ara.- 2 0 0, jva 1 x, v a - Mationko, 2, • < s \ Maaalo ra and G, n, 2aIon, Rare. Pray., Per, 2009, 32, v. ... and s kà R, komlya, 0, Ra pi a n d 0, " 2. Surrounded by wall, Coier; r, 2002, BB; OcO R, koaslya :, Ta Piaota and S > (b): (a) (b). (a) 0. 0: 0 and M, Ba r η B a. d: a r, dr i da dian .crf. Aioriroia to Pldodpdea o; rd Rot: onera to throw to cirrrant Coma; to Sodium, Sodium, Sodium, and Sodium; Ibl d, C. 13 ArarrPa year: κ. A 1, 2, 3, 4, 5, 6, 7, or n: Blaidoda, Rd, 03 ™ R, Bank ra 11, Mi d. ay-3210, Queen of, 2004, B \ 3 '

Np(a;; E ' 0; - upariaii, 33 33· Croata, 03 .A . Rabiar-"Np (a ;; E '0; - upariaii, 33 33 · Croatian, 03.

Dirienhotner and 33 23 Ganerykayn, brrpsnomehal.çiffs 2009, 28, 310 0; (2) g, s, TraviB, P. G, hanrayaa and B, Bordan, 20 .Asa Cbao, Eoc,, 2002, 1,24, 3024; pai D, Εηΐχρ and C, rhang, Ji 0koy, Cda-o., 2001, €€, 4014; (dl 2, GkaríxOba, M, Ohtarko and 0,. Banjoy®, ΕρτΡοοο, 20013 3201; íe) PO u, 2 a tas, 2© t rob e d rr a Be o d,, 12 97 , 32, 2313, [Sj ;al I, E, Markd, P, 0. n r i a a, R. Taakaaaki, d, Mk Braan ana. C3 03 Er oh , Baier ao .i.aOn, 234, 2044; (dl D, Bogdai1 and Ml. lubaaOenica, ay aiait, 2 ooo, 1 1.11, [B:£a). S, Fargrsaan and A. Mi Aj jDO, •rot-raboslran lleir,, d 0 Í 'i 4 44, 0139; ptO ll, Hat haAno; A;, A· ΐΑΡΒηΟΑΟ , 0, drenar and 21 GásAon, 03 CA em, ,B:a:., , .Ibràin Ora na,, 1290, 2, 2423; £ c} RC h a k a: ab ar t y, P, 0 a r ma n, B, B a Ira, 1Dirienhotner and 33 23 Ganerykayn, brrpsnomehal.çiffs 2009, 28, 310; (2) g, s, Travi B, P.G., Hanrayaa and B, Bordan, 20Asa Cbao, Eoc., 2002, 1.24, 3024; parent D, Εηΐχρ and C, rhang, Jykoy, Cda-o., 2001, €€, 4014; (dl 2, Gokaroba, M, Ohtarko and Banjoy, ΕρτΡοοο, 20013 3201; (e) 2, 2, 3, 4, 5, 7, , I, E, Markd, P, 0. Nriaa, R. Taakaaaki, d, Mk Braanana. C3 03 Er oh, Baier et al., 234, 2044; (dl D, Bogdai1 and Ml. LubaaOenica, ayait, 2oo, 11.11, [B: a). S, Fargrsaan et al., Et al., Et al. I'm sorry, Hat haAno; A, A · ΐΑΡΒηΟΑΟ, 0, drain and 21 Gas, 03 AC in, B: a,. C c h h a k a: ab ar t y, P, 0 a r ma n, B, B a Ira, 1

Ghakravorty and B, kl Baa,· Jaorr, OPoa. 2009, 40, mrGhakravorty and B, kl Baa, Jaorr, OPoa. 2009, 40, mr

s · %.· · xV. V ΓΠ ίο) 00 Sinch, do baaria, M, Chibbar, 0, Kacr -and: b L, bad, Syn-db Corra-a η, , OOQG, 30, 3341; íb) 3b Ibnáoy and D, ;>.. Obtabl, Ccib. (lanaroa, , 2003, 32, 371, : 2: (a; ;.ív Pora.trna, r v rnraa noras ano .o, braner, rarr-ario^nrron, .1307, S3, 10887; (M 3b GnnrálóMrel lano;, 07 bu COarraelo, D:.> 0. dac-qaar rle aro 3 Cl d, barinaa. CO ec o u a Ca rs-o,, 2008, 1, 740, [3] (al !b Ootrsâ- and H , bar cr Ι , Ilidi; < BOú - :0 b 10 , 2008, 37, 20 30; b:b 0, Tornar οί, Ob b lcostr.ro. 00, cb Ãle oro a adro, M, 8 d a as an, Po D * íasb r oeio asa ο ib do: bvillO:, Obaan Cd :d· c; ·.- -:·> v -,y 2008, IX, 8; 28, LO.eboa, 11 do Coroo de 2010s ·%. · · xV. V ΓΠ ο 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00. (b) 3b Ibnay and D,; >. Obtabl, Ccib. (lanaroa), 2003, 32, 371: 2: 1, 3, 4, 5, 6, 8, 9, 10, (1), (2), (2), (3) and (4) and (4) , bar cr Ι, Ilidi; BO ί ί ί ί, BO, BO BO BO BO BO BO BO BO, 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 and in 2008, IX, 8, 28, LO, good, 11 of the Coroo. of 2010

Claims

A compound of formula (I) copper 111, or the coupler 2, d-otoed. c .1 v d '" to 0.1% by weight, but not by weight. H); 1 of his agronomist r; "Oratori ra to fall irada poa a roa. application of the catadtoadaroa to the:> aid of ad. section ssc \ '· 0>. P: ·!,; (I.e. , and in the case of a s a r c e s, of AIDS. < ,: 1 or. The apparatus according to claim 1, wherein the at least one of the polyolefins is selected from the group consisting of: acd-s. dvd a nal 0: a o r, 4 · Ό! ο a a i ~ - > of the o.caaaa; ··: sp O λ ', will be .0.00000, ·. and P o, i a a ρ i; -5.0 -S or a < r irra ca. ..., Λ.% Λ à. &Gt; .................... and the atrophy of the amino acid. CO 2 CO 2 CO 2 CO 2 CO 2 CO 2 CO c ad. 10 -is < i dC ·: 0 c d d 0 0 0 0 0 .b is 0 d O: Hello. c 1: 0 qa: icoor aclv cd: · or or or or or or or or or or or or or or or or: d d dodd hollow a a aa aa. o.o. with 0 to 3 to 3 coding: c o rt d o f the opll qaçoo de r O: r - fe ai: 1,1 ™ b 1. d r op > g at x ta C OOC; sugar or yes gives. only .: > > ' Ο Go ahead. , 17 of Dobadro of 771 ;,