Method of producing cyclic geminal bis-hydroperoxides

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing cyclic geminal bis-hydroperoxides from ketones with ring size C12-C15 used to produce 1,2,4,5-tetraoxanes having high anti-parasitic activity. Cyclic geminal bis-hydroperoxides can also be used as radical polymerisation initiators. The disclosed method of producing C12-C15 cyclic geminal bis-hydroperoxides involves reaction of corresponding C12-C15 cycloalkanones with hydrogen peroxide in the presence of boron trifluoride in an ether medium in molar ratio C12-C15 cycloalkanone:boron trifluoride:hydrogen peroxide equal to 1:0.8-1.2:7-12.

EFFECT: method enables to obtain C12-C15 cyclic geminal bis-hydroperoxides in a single step and simplifies and lowers the cost of the process, cuts reaction time, as well as labour, material- and power consumption when producing bis-hydroperoxides; method enables to obtain desired products with high output and high selectivity.

1 cl, 1 tbl, 8 ex

 

The present invention relates to the field of chemistry of organic peroxides, particularly to a method for producing a cyclic genialnyh of bishydroxy of ketones with the size of the loop With12-C15.

In recent years, manifested by increased interest in organic genialny bishydroxy and obtained on the basis of 1,2,4,5-tetraoxane due to high antiparasitic activity of these compounds [H.-S.Kim, Y.Shibata, Y.Wataya, K.Tsuchiya, A.Masuyama, M.Nojima. Synthesis and Antimalarial Activity of Cyclic Peroxides, 1,2,4,5,7-Pentoxocanes and 1,2,4,5-Tetroxanes. J. Med. Chem., 2604-2609, 42 (1999); J.L.Vennerstrom, H-N.Fu, W.Y.Ellis, A.L.Ager, J.K.Wood, S.L.Andersen, L.Gerena, W.K.Milhous. Dispiro-1,2,4,5-tetraoxanes: a new class of antimalarial peroxides. J. Med. Chem., 3023-3027, 35 (1992); C.W.Jefford. Peroxidic antimalarials. Adv. Drug Res., 271-320, 29 (1997); Y.Dong, H.Matile, J.Chollet, R.Kaminsky, J.K.Wood, J.L.Vennerstrom. Synthesis and Antimalarial Activity of 11 Dispiro-1,2,4,5-tetraoxane Analogues of WR 148999. 7,8,15,16-Tetraoxadispiro[5.2.5.2]hexadecanes Substituted at the 1 and 10 Positions with Unsaturated and Polar Functional Groups. J. Med. Chem., 1477-1480, 42, (1999)]. In addition, heme-bishydroxy are used as initiators for radical polymerization [SAV, Ashvagosha, Aotomotive, MLB, Dasatinib, Tuvolkov, Heikichi. The method of producing polymethyl methacrylate. RF patent 2352587 from April 20, 2009] and in the synthesis of esters of dicarboxylic acids [..Terent'ev, ..Platonov, A.V.Kutkin. A new oxidation process. Transformation of gembishydroperoxides into esters. Central European Journal of Chemistry, 207-215, 4 (2006)].

Genialny bishydroxy - derived the macrocyclic ketones are unlike their counterparts with an average size of the loop is significantly more hard-to-reach connections.

A method of obtaining 1,1-bishydroxycoumarin interaction cyclododecanone with hydrogen peroxide (H2About2) in acetonitrile in the presence of iodine as catalyst [K.Zmitek, .Zupan, S.Stavber, J.Iskra. The Effect of Iodine on the Peroxidation of Carbonyl Compounds. J. Org. Chem. 6534-6540, 72, (2007)]. The reaction is carried out for 24 hours at a temperature of 22°C, the yield of the target product is 60%.

The problem of using this method is moderate yield 1,1-bishydroxycoumarin, the use in the reaction expensive iodine and complicated procedure chromatographic purification of the target product from iodine, which cannot be separated traditional restoration sodium thiosulfate due to simultaneous recovery of bishydroxy to the ketone. Obtaining cyclic bishydroxy with the size of the loop With13-C15this method was not implemented.

Also known is a method of obtaining 1,1-bishydroxycoumarin interaction cyclododecanone with hydrogen peroxide in the environment of acetonitrile, as catalyzer used an oxide of rhenium Re2O7[.Ghorai, P.H.Dussault. Mild and Efficient Re(VII)-Catalyzed Synthesis of 1,1-Dihydroperoxides. Org. Lett. 4577-4579, 10, (2008)]. The reaction is carried out for 20 hours using 5% (mole.) Re2O7the yield of the target product is 95%.

A significant disadvantage of this method of having aetsa the use of expensive and hard-to-reach rhenium oxide. Cyclic genialny bishydroxy with the size of the loop With13-C15this method was not received.

1,1-Bishydroxycoumarin (cycle 13) was obtained only with the release of 26% response cyclodecanone with hydrogen peroxide in formic acid [.Dåsnes, .Ledaal. New Cyclotridecane Peroxides. Acta. Chem. Scand. 1906, 25, (1971)].

We have adopted a prototype two-stage method of obtaining genialnyh of bishydroxy C12-C15peroxidebased ketones through transforming them into ketals with subsequent interaction ketals with hydrogen peroxide, catalyzed by boron TRIFLUORIDE (BF3) [..Terent'ev, A.V.Kutkin, M.M.Platonov, Yu.N.Ogibin, G.I.Nikishin. A new method for the synthesis of bishydroperoxides based on a reaction of ketals with hydrogen peroxide catalyzed by boron trifluoride complexes. Tetrahedron Lett. 7359, 44, (2003); Aotivities, Avicodin, MLB, Sashanikova, Ungiven, Heikichi. "Synthesis of 1,1'-bishydroxy(cycloalkyl)peroxides by homogentisate 11-15-membered heme-bishydroxycoumarin in the presence of boron TRIFLUORIDE". WPI. AK. Sciences. Ser. Chem. 1182 (2005)]. Peroxidizable ketones were carried out in two stages: first, ketones by reaction with trialkylaluminium in the environment of methanol at the boiling was turned into ketals, which was then isolated and injected into catalyzed by boron TRIFLUORIDE reacts with hydrogen peroxide at a molar ratio ketal:boron TRIFLUORIDE 1:0,2 at room temperature, d is the query result after selection output 34-95% per ketal (output 28-80% in the calculation of the original cycloalkane) received cyclic genialny bishydroxy with the size of the loop With 12-C15. The total duration of the two-stage synthesis is in the range of 20-24 hours. For Genialnogo of bishydroxy with the size of the loop With15from cyclopentadecanone is the only method of its production (yield 28% (based on recovered cyclopentadecanone).

The disadvantage of this method is its two-phase process when receiving the target genialnyh of bishydroxy of ketones, the length of the process, and not a high yield of bishydroxy with the size of the loop With15.

The present invention is simpler and cheaper method of obtaining genialnyh of bishydroxy from cycloalkanones12-C15, reduce processing time, increase output bishydroxy with the size of the loop With15.

This object is achieved by the proposed method of obtaining cyclic genialnyh of bishydroxy12-C15from the corresponding cycloalkanones12-C15using hydrogen peroxide, boron TRIFLUORIDE and organic solvent - simple ether, the distinguishing feature of which is the fact that the relevant cycloalkanones12-C15directly subjected to interaction with peroksida hydrogen in the presence of boron TRIFLUORIDE in an environment of simple ether at a molar aspect] is the solution of zilouchian 12-C15:boron TRIFLUORIDE:hydrogen peroxide 1:0,8-1,2:7-12.

As a simple ether using diethyl ether or tetrahydrofuran.

The process of peroxidative cyclic ketones12-C15carried out at a temperature of 20-25°C for 8-10 hours with the yield of the target product 69-95% conversion of the ketone to 100% according to the following scheme:

To date the proposed single-stage method of obtaining genialnyh of bishydroxy of macrocyclic ketones using boron TRIFLUORIDE was not known.

It was first discovered properties of boron TRIFLUORIDE selectively catalyze the reaction of macrocyclic cycloalkanones12-C15with hydrogen peroxide to obtain genialnyh of bishydroxy that was obvious due to the presumed low selectivity peroxidative and the possibility of occurrence of rearrangements Bayer-Villiger (acid-catalyzed getting lactones). So, in [..Terent'ev, M.M.Platonov, A.V.Kutkin. A new oxidation process. Transformation of gem-bishydroperoxides in esters. Central European Journal of Chemistry. 207, 4, (2006)], it was shown that different in size cycle genialny bishydroperoxyde when heated in the lower alcohols in the presence of equimolar amount of boron TRIFLUORIDE is unstable and is converted into the esters of dicarboxylic acids. Also isostearate [J.D.McClure, ..Williams. Hydrogen Peroxide is Boron Trifluoride Etherate, a New Oxidizing Agent. J. Org. Chem. 24, 27, (1962)], in which the boron TRIFLUORIDE - hydrogen peroxide was used for the oxidation of ketones (by the reaction of Bayer-Villiger) with the formation of esters. The reaction takes place by joining only one molecule of hydrogen peroxide to the ketone, and then boron TRIFLUORIDE catalyzes the rearrangement Bayer-Villiger monohydroperoxide derived ketone. Thus, in the reaction conditions of this study, the reaction of ketones with hydrogen peroxide and boron TRIFLUORIDE, the second molecule of hydrogen peroxide is not attached to the ketone. Based on the above work, it was obvious that genialny bishydroxy can be sustained in the presence of boron TRIFLUORIDE.

Thus, the prior art was not obvious use of boron TRIFLUORIDE to obtain genialnyh of bishydroxy of ketones directly without intermediate reaction get ketals.

Significant difference between the proposed single-stage method of producing cyclic genialnyh of bishydroxy12-C15from that adopted for the prototype two-stage method is also an increased amount of introduced boron TRIFLUORIDE. In the proposed method, the ratio of cycloalkanes:boron TRIFLUORIDE is 1:0,8-1,2; in the prototype, the ratio is s ketal:boron TRIFLUORIDE is 1:0,2. It is precisely this difference in proportions is the key to obtain the cyclic genialnyh of bishydroxy12-C15the proposed one-step method and allowed to carry out the reaction with high yield and high selectivity.

The set of essential features of the proposed method - the process of obtaining cyclic genialnyh of bishydroxy12-C15from the corresponding cycloalkanones12-C15in the presence of boron TRIFLUORIDE in an environment of simple ether at a molar ratio zilouchian12-C15:boron TRIFLUORIDE:hydrogen peroxide 1:0,8-1,2:7-12 is allowed to conduct the process in a single stage with a high yield of the target product and its high selectivity.

The advantage of the proposed method is its single-stage process, as compared with the prototype of the proposed method avoids the stage of synthesis and selection of ketals and, consequently, allows to simplify and reduce the cost of the process, to reduce the reaction time, material, energy and labor receive bishydroxy. In addition, the proposed method allows to obtain the target products with high yield and high selectivity, especially with regard to obtaining bishydroxy with the size of the loop With15.

The invention is illustrated by the following example.

Primer. Synthesis of 1,1-bishydroxycoumarin

A mixture of cyclododecanone (0.91 g, 5 mmol) and 20 ml Et2O added dropwise over ~5 min to a stirred ethereal solution of H2O2(35 mmol; the concentration of H2O2~ 2.5 mol/l) and BF3·Et2O (0.71 g, 5 mmol) at 20-25°C. the Reaction mass is stirred for 8 h, then add 40 ml Et2O and finely divided NaHCO3(30 mmol), intensively stirred the resulting two-phase system 30 min, filtered, the filter cake washed with 20 ml Et2O. Distilled off the solvent and flash chromatography of the residue (gradient elution with a mixture of petroleum ether and Et2O increasing from 30 to 60% last) release 1.1-bishydroxycoumarin (1.102 g, 4.75 mmole), yield 95%. Colorless crystals. TPL 138-140°C (Et2O). An NMR spectrum1H (300 MHz, CDCl3), δ, ppm: 1.21-1.82 m (22N, CH2), 9.98-10.04 ush. C. (2N, UN).

Example 2. Synthesis of 1,1-bishydroxycoumarin.

Analogously to example 1 are as 1,1-bishydroxycoumarin, but the reaction is carried out in an environment of tetrahydrofuran. The yield of the target product is 95%.

Analogously to examples 1 and 2 receive 1,1-bishydroxycoumarin, 1,1-bishydroxycoumarin and 1,1-bishydroxycoumarin; the process conditions and the results of the synthesis are given in table (examples 3-8).

1. The method of obtaining cyclic genialnyh of bishydroxy12-C15from the corresponding cycloalkanones C12-C15using hydrogen peroxide, boron TRIFLUORIDE and organic solvent - simple ester, characterized in that the respective cycloalkanones12-C15directly subjected to interaction with hydrogen peroxide in the presence of boron TRIFLUORIDE in an environment of simple ether at a molar ratio zilouchian12-C15:boron TRIFLUORIDE:hydrogen peroxide 1:0,8-1,2:7-12.

2. The method according to claim 1, characterized in that as a simple ether using diethyl ether or tetrahydrofuran.



 

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