PT104713A - COPPER COMPLEXES (II) WITH HYDROPHILIC C-FUNCTIONALIZED SCORPIONATES AND THEIR APPLICATION AS CATALYSTS OF PEROXIDATIVE OXIDATION OF CYCLO-HEXANE IN ENVIRONMENTALLY TOLERABLE CONDITIONS, IN PARTICULAR IN AQUEOUS ENVIRONMENT - Google Patents

Abstract

The invention relates to novel copper (II) complexes with methacrylic acid (1) and (2), and to the use of those compounds as catalysts of peroxide oxidation OF THE CYCLE-HEXANE TO CYCLOHEXANOL AND CYCLOHEXANONE, ACCORDING TO THE REACTIONAL SCHEME (I), WITH HIGH SELECTIVITY, CARRIED OUT IN SOFT AND ENVIRONMENTALLY TOLERABLE CONDITIONS, IN PARTICULAR IN AQUATIC MEDIUM.

Description

(II) with ligand ® epoorpioates and hydrophilic catalysts as catalysts and peroxidative oxidation of cyclohexane under conditions which are tolerable, especially in aqueous solution. hydroxylated hydroxyalkyl and hydroxylated hydroxyalkyl esters, on the methyl carbon atom, and the use of catalysts of the peroxyacetic oxidation of hydrogen peroxide under ambient conditions are essentially water soluble, in particular in aqueous medium,

Caxspp do Idreuio

Catalysis * Chemistry in Aqueous Environment, Qdlmro: Coordination, Chemistry Qrgâniea

BACKGROUND OF THE INVENTION

Further studies have led, in our laboratory, to the discovery of catalysts & (b) oxidation-partial processes of cyclic alcohols, based on the use of iron (III) -chromium hydroxide hydroxides (11) and aqueous hydroxyl complexes of these metals, 2.1, of a heterometallic Fe / Cu / Co complex [31, of metal oxides of groups 5 and 6, of vanadium complexes [5-11.1, iron [? 9], or (12-151 or copper [7,8,16,17], we have been looking for new types of more homogeneous catalysts that are more likely to be in the environment and that are more likely to yield better (ii) to try to improve the reaction conditions of catalytic systems in order to become more active and economically viable, increasing yields and / or selectivity as well as being environmentally tolerable (with a view to eliminating the need for organic solvents). The development of these studies resulted in the invention being analyzed as a result of post-doc work Dr. Maria M., Dr. Guedes da Silva and Dr. G, M. Míshra, and a PhD from Master T. F, S. Silva and Lic, Riccardo Wanke at the Center for Structural Chemistry ,. Complex I, Higher Technical Institute and in the Department of Chemical Engineering of the Higher Institute of Engineering of bísboa, within the scope of projects under the responsibility of Prof, A.JVL. Pombeiro funded by the PECDT program (supported by the ERDF) of the Foundation for Technology and Technology,

Description of the. The general object of this invention is to provide new aqueous transition metal complexes which are active catalysts of the partial oxidation process of o-cyclohexane: under mild and environmentally tolerable conditions , in an attempt to establish new " green " catalytic systems " (good yield is selectivity) for that reaction.

As such, the chloroform ligands functional on the methyl carbon atom of the 2,2,2-tris (X-pyrazolyl) ethane or 2,2,2-tris (1-yl) (II), and the studies have been carried out within the scope of the following more specific methods; (i) obtaining new copper (IX) complexes with aqueous soluble C-functional tris (1-pyrazolyl) methanes and (ii) applying such complexes to the catalytic oxidation of cyclohexane under mild and environmentally tolerable. (ambient temperature, atmospheric pressure and aqueous solution of hydrogen peroxide, green oxidation which only produces water as a by-product) with good yield and seismicity,

From these obj@ctn.voss, obtain the first copper cortices with the ligands 2α, 2-tis (1-pyrazolyl) efcanol and 2,2,2-tris (1-pyrazolyl) ethylmethanesulphonate, CpCl 3 (HOCH 3 C (p) 3) J 1 (p -tololol) and [CuClc (CH2) 2 OCH3 C (pz) 3] 2, respectively.

As well as being the first compounds in which a 2,2,2-tris (1-pyrazolyl) ethanol or 2,2,2- 2-tri (1-pyrazolyl) ethylbenzenesulfonate to a copper center present, as an important advantage over the usual oxidation catalysts of high water solubility. This characteristic is of major importance with respect to their applications as catalysts or precursors: of catalyst in pure aqueous medium (absence of any organic solvent) [18.1. * The scope of the establishment of new industrial catalytic systems: for the oxidation of arcane # acceptable from the environmental point of view, The obtaining of these compounds may still have biological significance (namely as inorganic models) given. the known [relevance] of copper complexes in natural systems "

Other advantages of this patent are recourse to. catalysts readily obtained by a simple and convenient route (from their commercially available metal salts) with very low or no polluting effect (eg, both catalysts act in water without requiring the presence of an organic solvent) # constituting a system of high activity and safety, at room temperature and normal pressure, and without the need for coca talisabores or additives. Thus, numbers of catalytic cycles # i.e. # numbers of " fcurnover " (TOH), 4 mol of product per mole catalyst, to ca, 1.3 x 1.0 " and overall conversions, based on cyclohexane, of ca, 23:%.

Moreover, no copper complex with hydrophilic phosphorous ligands of the 2 ', 2,2-tris (1-pyrazolyl) ethanoyl or 2,2,2-tris (X-pyrosolyl) ethylmethanesulfonate type was applied to the peroxidation oxidation of the epoxy-hexane The interest of the theme is justified by the relevance of the faneionalisation of alleans to the use of natural sources of organic matter which are abundant, relatively inexpensive (but which, owing to their reactive inertia, are mainly used for exploring only the its energy content) by converting it into value-added organic products, and {li). In view of the important applications of the cyclohexanol / cyclohexanone mixture (intermediates in the manufacture of adipic acid, Nylon-6,8 ', polyamide-6, urethane foams, flour-forming agents. Lubricating additives 120]),

Aelatively to known synthetic processes, we can refer to the case of adipic acid (intermediate in the production of Nylon-β, i '): which is industrially produced in two phases; oxidation of cyclohexane and a cyclohexanol / cyclohexanone mixture which is then oxidized to adipic acid [2 Da]. In the first step, the cyclone-hexane is oxidized by the dioxygen from the air to a temperature above ISO ° C at ca. 12-18 in the presence of a soluble catalyst such as naphthalenate or cobalt acetate. The oxidation reaction is carried out with a low conversion (usually between 3 and 3%) to increase the selectivity (70-80%) (DuPont process) [21]. requiring repeated recycling of cyclohexane feed. Ά the formation of by-products is another difficulty of the process, and the need has been recognized; to find more effective alternative systems under mild operating conditions *

The limitations of the above systems are difficulties which the present invention seeks to mitigate in some way. In fact, our catalytic systems under consideration have several advantages over, for example, the industrial oxidation process of cyclohexane, i > superior effectiveness, selectivity yield and smoother and environmentally tolerable operating conditions,

Other advantages over the usual chemical processes include (i) the simplicity of the processes (in a single step) and (i) the use of relatively inexpensive, accessible catalysts and raw materials with a very low polluting effect or null

The catalysts of this invention are also advantageous over those previously tested for said oxidation reaction by action of hydrogen peroxide, since in addition to the more active and seieactive ones, they exhibit greater structural simplicity and eliminate the need to use organic solvents. In fact, the catalysts of the invention under analysis are most in agreement with the values of catalytic numbers, catalysts, for example, obtained for the catalyst (COCH2) ) 2 2 [1.8 x W4 in cycle oxidation · &quot; hexanoate complexes than the CC-Î ± 1Î ± 1 β1 β1 or β-SCg, Î ± 2 complexes in the oxidation of cyclohexane by hydrogen peroxide (maximum TONs of 43 and 32, respectively) ) or that the compound of CuCl3 (CuIHePz). In addition, yields are also appreciably higher than those of said relational complexes (maximum yield of 4%) or [CaaC [[] Cu (Kc (prb) gj <21 s (maximum yield of 2.times.%), The catalysts of the invention under analysis exhibit higher TQN values than those presented by other catalysts based on iron (III) hydroxides (221), or those exhibited by various other copper catalytic systems, in particular with Salen, ethoxycarbonyl or phthalocyanine [23]. The novel Invention Caractristins The invention in the present study reported the novel use of copper (IX) complexes with c-functio- nized 2.2, 2'-tris (1-pyroxyl) steroid or 2,2,2'-tris (Xa 2) as catalysts in the presence of a compound of formula (I). peroxidase oxidation of cyclohexane to cyclohexanol and cyclohexanone &gt;

In addition, the present invention recognizes, for the first time, that complexes of that type (water soluble) efficiently catalyze the partial oxidation of cyclohexane without requiring the presence of any organic solvent,

The copper complexes (I 11 of this invention thus constitute the first catalysts with C 1-6 functional cis-1-pyrazole dimethyl, 2,2,2-tris (X-pyrazolyl) ethane or 2,2,2- tris (1-pyrazolyl) -ethyl-methanesulfonaphthyridine, which are active in the peroxidation oxidation of the cyclohexane, the copper compounds of the present invention exhibit a remarkable catalytic activity under environmentally tolerable moderate conditions for such particle oxidation and the complex [CuCl; (CH 2 SO 3 OC 3 Cl 2)] exhibits the high activity reported up to now reported for a catalytic scorpionate catalyst for the peroxidative oxidation of cyclohexane A: a: 3: 0,

In addition, the copper complexes themselves comprise the Xanthomers 22: 1, 2-tris (1-pyrrololyl) ethanol or 2,2 :, 2-tris (1-pyridazin-2-yl) methanesulfonyl methanesulfonate (c) Technical description The invention consists in obtaining new copper (II) complexes with tri (1-pyrazolyl) methanesulphonates. and in the use of such complexes as catalysts of the peroxy oxidation of hexane-hexane and hexane-hexanol, performed under mild and environmentally tolerable conditions, in good yield and in The description of the catalytic oxidation process of the sky-hexane is given in more detail: by way of some examples which show that the catalytic oxidation process of the hexane-hexane is shown in greater detail. are merely illustrative, are of the imitative character of the scope of the present invention.

Examples A; Preparation of the copper (11) complexes with the tri (1-pyrazole) ligands 2,2'-tris (1-pyrazolyl) ethanol or I-1, 2-tris

Alj [CuCI s (HOCHaC (pz) i) 1 A comes. To a solution of anhydrous copper (II) chloride (118 æg, 0.875 mmol) in tetrahydrofuran (TKFS (25 mL) was added an equimolar amount of CH2 Cl2) (108 mg, 0.01 mmol) The dark green solution was stirred under reflux for 6 hours. To the final solution was concentrated by evaporation and, after addition of n-pentane, a green solid precipitated which was isolated by (100 mg, 85% yield) The suitable excipients for x-ray diffraction were obtained by dissolving the solid in methanol and addition of ether The solubility tests of this compound (2%) of the title compound were prepared as described in Example 1. To a solution of anhydrous copper (XI) chloride (54 g) (40 mL, 0.40 mmol) in MeOH (50 mL) was added an equimolar amount of CrOSO4 OCmO (pz) 3 (140 mg, 0.397 mmol) in THF (20 mL). The solution was stirred under reflux for 3 hours, then concentrated by evaporation and, after addition of n-butanol, gave a green solid. The solid was evaporated. isolated by filtration, washed several times with n-pentane and dried in vacuo (44 mg, yield 80%). The crystals suitable for X-ray diffraction. were obtained by dissolving the ether solid in methanol. The solubility tests of this compound revealed that it is soluble in water (8: 2: 1 and 14 mg / m 3)

Oa complexes X and 2 were characterized by X-ray as well as X-ray spectroscopy, X-ray diffraction, elemental analysis and X-ray diffraction. Their crystallographic data as well as their selected length and connection angles are given in Tables 1 and 2, respectively,

Table. 1-erythropoietic data for the compounds ICu (ROCPbC (pz) s 1 is (CuCl 2 (GH; * 802C) C (pz h) 2. (B) (a) (b) (b) (b) (b) (b) (b) (b) (b) 13.02: 8 (5) 18/7943 (18) c (k) 16/7628 (11) 10.2236 (10) β (98 98585 (6) (Ab 1253.0 (17) 1703, (Mg / mb Coefficient of 1,677 1,745 absorption (mm; F000); 1528 224 Beflerdes 17189/4202 11150 (Mg / mb) / 3119 collected / rHiint) ~ 0.0444] IR (int) - 0.0833] single final R indices 5. ·: ~ 0.0422 RI - 0.0438 Q &gt; 20 (X) Ri - 0.0627,%? / RI ss0.0810, wR2 totals = 0.1213 0.0870

Table 2 - CampTlimentúZ (Â °) and angles of Xi.g & ggr (*) selected for the compounds [(CbCliCHOCHxCi ^^^ j)) 1 and iCuCXs (CHaSC ^ OCHiC (zz) 31.2.2.1

Table of contents

Cul-Cli 2.364 (12) 2.2400 (11) Cul-Ci2 2.2574 (11) 2.2380 (12) cui-eir - 2.699 (12) Cu-Mil 2.040 (3) 2.023 (i) CU-H14 2.244 (3) 2.002 (3) cui-m-1.937 (3) ... Angles of N14-Cu.l ligation - N.ll 84.08 (12) 85.66 (14) } MII-Cul-Ci1 105.38 (9) 169.23 (10) H11-CeI-Clt 91.99 (10) 83.53 (10) M1-4 -Cu 1- <112 107.06 ( 9 91.32 (10) Ml: 1-Cul-Cl2 166.89 (11) 176.52 (10) G11-Cu1-C12 91.63 (5) 93.91 (5) Mle-Cui-Cli (4) C12-C11-C12-C10-C7-C7-C7-C10- Cu1-C12-Cu1 f ... 94.23 (4)

Examples Oxide of the cyclohexane to cyclohexanol and cyclohexanone with hydrogen peroxide and using the alkalisers 1 and 2,

Bi) ba. The reactions of the oxidation are carried out in Schlenk type tubes and under inert atmosphere, Em. Under normal conditions, 0.010 mmol of catalyst (complex I or 2) in 2.5 mt of acetonitrile was dissolved. From this solution, the sample was removed in the required volume to give the desired oxidant molar / catalyst ratios, and adrciono-u-se. to another, 50010.01: reaction flask with a volume of acetonitrile such that the total volume in the final solution was 3 ML, 5.00 mmol (0.50 mL <1 mol) was added. 30% aqueous hydrogen peroxide solution and still cyclohexane 5.00 mmol (0.54 mL) in that order. The reaction was maintained with stirring at room temperature and normal pressure for 8 hours. At the end of the reaction, for analysis of the products, the organic phase was ex. The reaction mixture was stirred for 10 minutes and then samples (1 μl) of the crude product were added. The reaction mixture was stirred at room temperature for 1 hour. organic phase; which were: xnjectsdas on the chromatograph &gt; The TOH values were calculated using a calibration curve obtained from known values of the hexelohexanone and cielo-hexanol products: and the internal standard (cycloheptanone),

Blank assays were also carried out under the same conditions, but without the copper complex, and no oxidation product was detected. Typical results are shown in Table 3.

Table 3 - catalytic activity of the complexes 1 and 2 in the oxidation pero.xi.dat iva. of hexane. &quot; T0Hh Catalyst Cyclohexanol CA) Cyclohexanone Total 73 8 81 tâ "¢ 10 8 18 to 1.7 t 1.2 188 2æ 18 5 23 selected, Typical conditions: Cdhx (8 rool); HCl: (3.0 mL); (ε% Oζ) / n (CHH 5 5 5H₂O)) / n (catalyst) -10; of total furnace (moles of product per mole of catalyst), and cyclohexanol cyclohexanone. The absence of HCMs is reported by Ha (O) - (2). The absence of organic solvents and oxidation reactions were realized? in Schl &amp;amp;amp;amp;amp; and amp; 0.010 mmol of catalyst (complex t or 2) in 2.5 ml of water was dissolved. A sample of the required volume was withdrawn in such a way as to obtain the desired oxo-molar ratio / catalyst , and reacted with a further Schlenk flask with a volume of water such that the total volume in the final solution was 3 mL. 5.00 mmol (G, 100 mL of an aqueous solution of The reaction mixture was stirred at room temperature and under normal pressure for 6 hours, at the end of the reaction, for analysis of the reaction mixture. The organic phase was extracted by adding 5.5 ml of diethyl ether and 9.0 μl of cycloheptathione (internal standard). The obtained mixture was stirred for 10 minutes and then samples were taken (1, 1 L) was added to the organic phase which was isolated in the chromatograph. (eielo-hexanone and cyclohexanol) and the internal standard (cyclohepfcanone) *

Blank assays were also carried out under the same reaction conditions, but without the copper scorpienate complex, no oxidation product having been detected. Ma (table 3 typical results are given.

The catalysts are highly selective in the formation of cyclohexanol, while the cyclohexanone is usually obtained in a relatively low amount, but the cyclohexane complex is the best catalyst in the oxidation of cyclohexane to cyclohexanoyl (major product) was added to the cyclohexanone cycle, after an optimum reaction time of 6 hours, catalytic tests (TON) of 186 moles of products / catalyst mole

It should also be noted that catalysts exhibit a remarkable viscosity in the absence of organic solvent (eg, acetonitrile) as shown in Table 1. This behavior was favored by the good solubility of these catalysts in allowing the catalytic system to operate in the peroxide medium of hydrogen, without the need of addition of any organic solvents. ft MA Eopylovich, A.M. Kiriilbv, Baev, A.JIL, Bombeiro, J. Mol. Cat. A. mm, 206, 163.

[2] Ά. JL. Pobebet M, H. Kopylovieh, A.M. Ririllov, PT 103033, mm.

[3] A.J.L. Pombeiro, A.M., Eirillov, Μ.N .. Kopylovieh, V.b.

Kokosay, D. S, Nesterov, PT 103526, 266 ?, [4.1. J.L., Pombeiro, J.A. j. Frausto da Silva, JiA.L, Silva, M-V. Kíriliava, P.M. Reis: A.M. Kirillov, A.F. Word, Patent PT 103350, 20061 iSl P.M. Reis, J.A.L. Silva, O ', U.R, F. da Silva, A. J.L.

Pombeir C Chexn. Commun. 2000, 1845.

[6i A.J, L. Pombeiro, Jid.E.P, da Silva, Y. Fujiwara, J.A.L. Silva, P.M., Heis, A. F. Word, WO 2004/037416 A3, 2004, [7] A, J.L. Pojnbeí.ro, A.M. Ririllov, M.N. Kopylovieh, M.V. lirilidta, d- Banhlça, da. Silva, U.S. Patent No. 103225, 2006, U.S.A., U.S.P. M v D .. R, S-Martins, BXhB.A, Joy, Pombeiro, Adv. Syxith. Cat., 2601, 350, 706.

14 |: 9j A. Ο · 1 = - Porabei ro, L.IkD.R.S. Martins, S. C. B. A. Alegria, M., Silva, Pat. PT 104153, 2008. | G.S. Mishra. T. F. S . Silva, L. M, D.R. S. Martins, A.J.L. et al., J. Med. Chem. Soc., 2, 11S, 11 (7), 1217. A-3-P-Porabei ro, L.M.D.R.S. Martins ·, T.F.S. Silva, G. S. Mishra. Patent PT1G4447, 2 <30f (date of prior: March 20, 2009) &gt; Q2] E.C.B.A, Joy, Μ, V, Kirillova, hM, D.R.S. Martins, A, J. Porabei, Appl. Ca t, At General, 2007, 317, 43. (13H, 3h). Pom.be.iro, L.M.D.R.S. Martins, B. C &lt; B, A. Alegria, M.V. Kirillova, PT 103733, 2808. Γ14] g.S. Mishra, E.C., B. Alegria, L.M.D.H.S, Martins, 0 '. J. Frausto et al., A, &lt; 1.1. Firefighter: 3. Moi, Catai Ar Chem., 2008, 285, 92, [15] a, J.L. Fireman, I., M., D.R.S. Martins, E.C.B.A. Joy. G. S-Mishra, J.J. Fraústo da Silva, PT 104197, 2008, [ISj δ) A.M. Ririllov, M.N. Kopylovich, Μ, V, Kirillova, E.Y., Karabaob, 1L M. F.C, G, da Silva, Α, Υί, Β, poitfoeiro, áciv. Synth. Cat., 2000, 348, 159. b) A &gt; M. Kirillov, M. N., Kopylovich, M..V. Kirillova, M. Haukka, M.F.C.G, da Silva, A.J.L., Porabeiro, Chem. iM., 2000, M, 434S, c) C. Nioola, 7. Y. Karabach, A.M. Kirillov, M. Monari, L, Pandolfo, C. Pettinari, A.J.L, Fireman, Inerg. Chem., 2007, 46, 221.

[17j A.J.L. Fireman, A, M. Kirillov, M.N. Kopylovich, M.y. Kirillova, M. Haukka, M.F.C.G. da Silva, PT 103225, 2006.

ClSj a) C &lt; Pettinari, E. Pettinari, Coord. Chem. Rev., 2005, J 4, 525; (c) C. Pettinari, C. Santini, Comp. J. Chem., Chem. 1, eds. 31A, McC.leverty and T.GL Meyor, Flsevier, Oxford, 2004, Cap &amp;

[1S] a) J. 0. R. Bradado da Silva, R., J. P ♦ Wxiixama, Biological History & Mission of the FCl &amp; nbB &quot; -hm Taorciamc

Full is Try of Life, Clarendon Press, Oxford, 19¾. b] Suit Lippard, JM Berg, Principles of Bioinformatics Chemistry, Unity Science Books, Miil Yalley Science, USA, 2994. (c) W. Kaim, B. Schwederski, Sioinorganic Chemistry: Xnorganic Blems in Chemistry (Oxford, 2001). The use of the method of the present invention is based on the invention of the present invention, which is incorporated herein by reference in its entirety.

CataiyTic Activation and Functionalisation of Light

Al kanes, eds. B, D.D; rrouane, J. Haber, F. ΐwewewewewe,, Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Rib Ribΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐΐ Ei: nandi, Mlalytxc Activation of Dioxygen by Metal Supplements, Eluwer Acaderrdc Publ., Dordrecht, Holca, 2932dl CJía, T. Kit Amura, Y. Fnjiw & 34, 633. and A. A, B. Shiv, GV B, Shul pin, Chei Rev., 2899, 97, 2879. The Acivat ion of Radiation and Homogeneous Catalytic Oxidation, eds. Barton, AE Martell, DT Sawyer, Flenum Press, New York, 1993,

Pl:] U. Sobadbardfe, Wik, Caibabaib, Lifi Spinace, &lt; tb &gt; 1993, 10, 713.

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Lisbon, August 7, 2009

Claims (2)

X &gt; Copper palladium ΓΧ 1) 100 liqandor aacorpionaios. hydrophilic, characterized by the presence of tri-type acids (pirasol i. 1) in solid form. bags in the carbon atom of the formula: (I) rel. Xo ·) and [CaClâ,,: Câ, â, Hâ, â,ƒ); 3 - 1 - 2 - Preparation of the preparation of the slice of the slice according to claim 1 in which: XX X-III-III. miatara, and the air is one hundred. The title compound was prepared as an anhydride, and BOCl: bC (cc); in ana i.d.a4 &lt; a y ou 1 mo i a r a n, in t a t i n t i n t i n t i n t i n t i n t; pi. Q reflex reflex. 6 hours, - storage of the powder; and the addition of pectant to the scratching by filtration, which results in drying and drying. xrr vacuum., Pr ocess of crepsr; network of comporto cc fc; emulates 2 cc to the pig. With the addition of 1 to the pigs, srura, air to tone. agitation appears up to: chlorate of the work ΠX) anhydrous CMsSOpXCMdlps; , the reaction mixture was quenched with methanol / methanol / tetrahydrofuran in 2: 5: 1 volumetric flask, at reflux for 5 hours, followed by ethanol precipitation by addition of potassium hydroxide. salted by miltration, and vaccinated and killed by vacuum. 4. A composition according to any one of claims 1 to 5, wherein the amount of the compound of formula (I) according to any one of claims 1 to 5, wherein the compound of formula (I) is in the form of a compound of formula (I). hexanol in hexane: by the addition of an aqueous solution of the Hep, in acetonitrile at 20 ° C, gives Compound 1 and 2 according to claims 1 and 2, characterized by their application as catalysts of the oxidation of the cellulose to the cyclohexane to the cyclohexane. the oxidation of the aqueous solution. cp HPP, at room temperature. auarp.oa sa .1 wins or races, Cc 2010 ce colho