Synthesis of 1, 2, 4, 5, 7, 8-hexaoxonanes by iodine-catalyzed ...

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Russ Chem Bull (2009) 58: 335. doi:10.1007/s11172-010-0012-8 .... Commun., 2004, 2614; (b) J. Barluenga, M. Marco-Arias, F. Gonzalez-Bobes, A. Ballesteros, ...
Russian Chemical Bulletin, International Edition, Vol. 58, No. 2, pp. 335—338, February, 2009

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Synthesis of 1,2,4,5,7,8hexaoxonanes by iodinecatalyzed reactions of bis(1hydroperoxycycloalkyl) peroxides with ketals* A. O. Terent´ev, M. M. Platonov, I. B. Krylov, and G. I. Nikishin N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 119991 Moscow, Russian Federation. Fax: +7 (499) 135 5328. Email: [email protected] Iodinecatalyzed reactions of bis(1hydroperoxycycloalkyl) peroxides with ketals give, via replacement of two alkoxy groups, the cyclic peroxides, 1,2,4,5,7,8hexaoxonanes, in up to 82% yields. The cyclization is very sensitive to the solvent nature. Among MeCN, Et2O, THF, CHCl3, CH2Cl2, hexane, and MeOH, the best results were achieved with the first three solvents. Key words: peroxides, bis(1hydroperoxycycloalkyl) peroxides, 1,2,4,5,7,8hexaoxonanes, triperoxides, ketals, iodine.

1,2,4,5,7,8Hexaoxonanes (cyclic ninemembered triperoxides) have been of interest for over four decades as intermediate products for the synthesis of macrocyclic cycloalkanes and lactones by the Story thermolysis.1 Some lowmolecularweight triperoxides (e.g., acetone and ethyl methyl ketone derivatives) are widely used to initiate free radical processes in polymer synthesis.2 Acetone triperoxide and its close homologs are easily accessible and can be employed as explosives; for this reason, par ticular attention is given to the study of their properties and development of analytical methods for this class of cyclic peroxides.3 Hexaoxonanes can be obtained in three ways: acid catalyzed reactions of ketones with hydrogen peroxide,4 ozonolysis of unsaturated compounds,5 and condensation of bis(1hydroperoxyalkyl) peroxides with ketones.1e,6 The first two methods are not highly selective and are unsuit able for the synthesis of structures with bulky substituents. The use of the third method is restricted to a few ketones

that are reactive in this process. Recently,7 we have found that condensation of bis(1hydroperoxyalkyl) peroxides with ketals (both must be pure and dry) in the presence of BF3 or SnCl4 selectively gives triperoxides in high yields. Our new approach to the synthesis of 1,2,4,5,7,8 hexaoxonanes 1 involves iodinecatalyzed reactions of bis(1hydroperoxyalkyl) peroxides 2 with ketals 3 (Scheme 1). The remarkable feature of this reaction is that both alkoxy groups of ketals are replaced by peroxy groups under these conditions. This result was unexpected: previously,8 we have found that iodinecatalyzed reac tions of structurally related gembishydroperoxides 4 with ketals 3 in ether and THF yield 1hydroperoxy1´alkoxy peroxides 5 (i.e., only one alkoxy group is replaced). Apparently, the easier formation of ninemembered peroxide rings in this reaction compared to sixmembered ones is due to the lower ring strain in the former. The idea to combine iodine with hydroperoxides or hydrogen peroxide is very fruitful: in recent years, this

Scheme 1

* On the occasion of the 75th anniversary of the foundation of the N. D. Zelinsky Institute of Organic Chemistry of the Russian Academy of Sciences. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 333—336, February, 2009. 10665285/09/58020335 © 2009 Springer Science+Business Media, Inc.

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Terent´ev et al.

Scheme 2

Entries 1—3

combination has been successfully used in the synthesis of peroxides from carbonyl compounds9 and alkenes.10 The system I2—H2O2 is multipurpose in its reactivity: depending on the reaction conditions, H2O2 can act not only as a reagent for the formation of the fragment C—O—O but also as an iodine activator in iodoalkoxyla tion of alkenes11 and iodination of arenes,12 ketones,13 and alkynes;14 this system has also been employed for the Baeyer—Villiger oxidation of ketones into lactones.15 To examine the influence of the reaction conditions on the synthesis of hexaoxonanes, we obtained triperoxide 1a from bis(1hydroperoxycyclohexyl) peroxide 2a and 1,1dimethoxycycloheptane 3a. The conditions to be op timized were the molar ratio I2/2a, the reaction time, and the solvent nature; for comparison, we also synthesized peroxide 1a from cycloheptanone (Scheme 2, Table 1). To confirm the efficacy of ketals in the synthesis of triperoxides, we obtained triperoxide 1a from cyclo heptanone and bis(1hydroperoxycyclohexyl) peroxide (entries 1—3). The highest yields of the target peroxide were 43 and 44% in methanol and acetonitrile, respectively. In the reaction with cycloheptanone dimethyl ketal 3a in acetonitrile (entries 4—10), the yield of triperoxide 1a increased to 57—78%. Diethyl ether (entries 11, 12, and 17), THF (entry 18), and CH2Cl2 (entry 19) were also quite suitable for the synthesis of triperoxide 1a. Under analogous conditions, the yields of the target peroxide in chloroform and methanol (entries 21 and 22) did not exceed 58%. Under the conditions optimized for the synthesis of triperoxide 1a as an example (see Table 1), we obtained peroxides 1b—j by reactions of bis(1hydroperoxycyclo hexyl) peroxide (2a), bis(1hydroperoxycycloheptyl) per oxide (2b), and bis(1hydroperoxycyclododecyl) peroxide (2c) with 1,1dimethoxy4methylcyclohexane (3b), 4tertbutyl1,1dimethoxycyclohexane (3c), 2,2di methoxydecane (3d), 5,5dimethoxynonane (3e), and 4,4dimethoxy2,6dimethylheptane (3f) (Table 2). The yields of triperoxides 1 were 51—82%. Although the yields vary with the structures of the starting bis (1hydroperoxycycloalkyl) peroxides 2 and ketals 3, they are sufficiently predictable, which makes this reaction suit able for the synthesis of structurally related compounds.

Entries 4—22

Table 1. Influences of the molar ratio of the reagents, the reac tion time t, and the solvent nature on the yield of compound 1a in the reactions of cycloheptanone (entries 1—3) or its dimethyl ketal 3a (entries 4—22) with peroxide 2a (20—25 °C) Entry 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22

Solvent Et2O MeOH MeCN MeCN MeCN MeCN MeCN MeCN MeCN MeCN Et2O Et2O Et2O Et2O Et2O Et2O Et2O THF CH2Cl2 Hexane CHCl3 MeOH

I2/2a (mol/mol) 0.4 0.4 0.4 0.1 0.2 1.0 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.1 0.2 1 0.4 0.4 0.4 0.4 0.4

t/h

Yield of 1a (%)*

20 20 20 20 20 20 0.5 2 20 75 20 72 2 0.5 20 20 20 20 20 20 20 20

10 43 44 73 75 68 72 76 78 57 71 70 48 34 36 46 65 70 70 67 57 58

* With respect to the isolated product. Table 2. Yields of 1,2,4,5,7,8hexaoxonanes 1b—j Starting material

Product

Yield (%)*

2a + 3b 2a + 3c 2a + 3d 2a + 3e 2a + 3f 2b + 3b 2b + 3e 2c + 3b 2c + 3e

1b 1c 1d 1e 1f 1g 1h 1i 1j

67 51 77 82 68 53 54 69 64

* With respect to the isolated product.

1,2,4,5,7,8Hexaoxonanes

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R = Me (1b), But (1c); R1 = Me, R2 = (CH2)7Me (1d), R1 = R2 = Bun (1e), Bui (1f).

To sum up, we proposed a new route to 1,2,4,5,7,8 hexaoxonanes via iodinecatalyzed reactions of bis (1hydroperoxyalkyl) peroxides with ketals. The advan tages of our method include (1) convenient synthetic procedure, (2) easy isolation of the target product, (3) a small amount of byproducts, (4) use of nonhydrolyz able iodine (in contrast to the Lewis acids BF3 and SnCl4), and (5) high yields of hexaoxonanes. Experimental NMR spectra were recorded on Bruker AC200 and Bruker AM300 spectrometers (300.13 (1H) and 75.48 MHz (13C)) in CDCl3. For TLC, Silufol UV254 plates were used. Column chromatography was carried out on silica gel (63—200 mesh, Acros). Melting points were measured on a Kofler hot stage. Highpurity solvents (THF, MeOH, Et2O, MeCN, CHCl3, CH2Cl2, and hexane) were used freshly distilled. Highpurity I2, Na2S2O3, and Na2SO4 were employed. Bis(1hydroperoxy cycloalkyl) peroxides7 and ketals16 were prepared as described earlier.

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Synthesis of peroxide 1a (general procedure). Ketal 3a (0.086 g, 0.54 mmol) or cycloheptanone (0.061 g, 0.54 mmol) was added to a solution of bis(1hydroperoxycyclohexyl) peroxide 2a (0.13 g, 0.5 mmol) in the solvent (2 mL). Then I2 (0.0127—0.127 g, 0.05—0.5 mmol) was added with stirring (see Table 1). The reaction mixture was stirred at 20—25 °C for 0.5—72 h., diluted with hexane (20 mL), and washed with 5% aqueous Na2S2O3 (7 mL) and water (3×5 mL). The organic phase was dried over Na2SO4 and concentrated. The target peroxide was isolated by column chromatography on SiO2 (0.060—0.200 mm) with light petroleum—CH2Cl2 (4 : 1) as an eluent. Synthesis of peroxides 1b—j (general procedure). Ketal 3b—f (0.54 mmol) or cycloheptanone (0.061 g, 0.54 mmol) was added to a solution of peroxides 2a (0.13 g), 2b (0.145 g), or 2c (0.215 g) (0.5 mmol each) in MeCN (2a, 2b) or THF (2c) (2 mL). Then I2 (0.051 g, 0.2 mmol) was added with stirring. The reaction mixture was stirred at 20—25 °C for 24 h. Products 1b—h were isolated by pouring the reaction mixture into Et2O (15 mL) and light petroleum (15 mL). The organic phase was washed with 5% Na2S2O3 (~15 mL) (until it decolorized) and water (3×10 mL), dried with Na2SO4, and concentrated. Peroxides 1b—h were purified by column chro matography on SiO2 with light petroleum—CH2Cl2 (4 : 1) as an eluent. In the case of peroxides 1i,j, the reaction mixture was concentrated to 1/3 of its original volume and poured into cooled (~0 °C) MeOH (15 mL). The precipitate that formed was filtered off, washed with cooled MeOH (3×5 mL), and dried in vacuo (~1 Torr) at room temperature for 30 min. The yields of peroxides 1b—j are given in Table 2. 7,8,15,16,24,25Hexaoxatrispiro[5.2.5.2.6.2]pentacosane (1a), m.p. 53—54 °C (cf. Ref. 7: m.p. 53—54 °C). 1H NMR, δ: 1.33—1.96 (m, 30 H, CH2); 2.11—2.23 (m, 2 H, CH 2). 13 C NMR, δ: 22.7, 22.8, 25.5, 30.0, 30.6, 30.7, 32.7 (CH2); 107.6, 112.8 (C). 3Methyl7,8,15,16,23,24hexaoxatrispiro[5.2.5.2.5.2] tetracosane (1b), a viscous oil. 1H NMR, δ: 0.87—0.96 (m, 3 H, CH3); 1.03—1.93 (m, 27 H, CH, CH2); 2.07—2.29 (m, 2 H, CH2). 13C NMR, δ: 21.5, 22.7, 25.5, 28.5, 29.7, 30.5, 30.57, 30.63, 30.7, 30.9, 31.1, 31.67, 31.74 (CH, CH2, CH3); 107.56, 107.66 (C). Found (%): C, 64.34; H, 9.17. C19H32O6. Calcu lated (%): C, 64.02; H, 9.05. 3tertButyl7,8,15,16,23,24hexaoxatrispiro[5.2.5.2.5.2] tetracosane (1c), a viscous oil. 1H NMR, δ: 0.86 (s, 9 H, CH3); 1.02—1.94 (m, 27 H, CH, CH2); 2.19—2.38 (m, 2 H, CH2). 13 C NMR, δ: 22.7, 23.5, 23.7, 25.4, 25.5, 27.6, 29.0, 30.5, 30.6, 30.8, 32.3, 32.5 (s, CH2, CH3); 47.4 (CH); 107.6, 107.7, 108.1 (C). Found (%): C, 66.11; H, 9.93. C22H38O6. Calculated (%): C, 66.30; H, 9.61. 17Methyl17octyl7,8,15,16,18,19hexaoxadispiro [5.2.5.5]nonadecane (1d), a viscous oil. 1H NMR, δ: 0.80—0.95 (t, 3 H, CH3, J = 6.5 Hz); 1.20—1.95 (m, 37 H, CH2, CH3). 13C NMR, δ: 14.0 (CH ); 18.7, 22.7, 23.8, 25.6, 29.2, 29.4, 29.7, 3 30.4, 30.6, 30.65, 30.7, 30.8, 31.9, 33.8 (CH2, CH3); 107.55, 107.62, 109.3 (C). Found (%): C, 66.69; H, 10.36. C22H40O6. Calculated (%): C, 65.97; H, 10.07. 17,17Dibutyl7,8,15,16,18,19hexaoxadispiro[5.2.5.5] nonadecane (1e), a viscous oil. 1H NMR, δ: 0.78—0.97 (m, 6 H, CH3); 1.13—1.93 (m, 32 H, CH2). 13C NMR, δ: 14.0 (CH3); 22.8, 25.6, 25.8, 29.7, 30.3, 30.6, 30.9 (CH2); 107.5, 111.0 (C). Found (%): C, 65.43; H, 10.18. C21H38O6. Calculated (%): C, 65.25; H, 9.91.

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17,17Bis(2methylpropyl)7,8,15,16,18,19hexaoxadispiro [5.2.5.5]nonadecane (1f), a viscous oil. 1H NMR, δ: 0.84—1.11 (m, 12 H, CH3); 1.21—2.02 (m, 26 H, CH, CH2). 13C NMR, δ: 22.6, 22.75, 22.82, 23.1, 24.3, 24.6, 25.6, 29.7, 29.9, 30.7, 31.4, 38.6 (CH, CH2, CH3); 107.56, 111.2 (C). Found (%): C, 65.58; H, 10.05. C21H38O6. Calculated (%): C, 65.25; H, 9.91. 3Methyl7,8,16,17,25,26hexaoxatrispiro[5.2.6.2.6.2] hexacosane (1g), m.p. 53—55 °C. 1H NMR, δ: 0.81—0.97 (m, 3 H, CH3); 1.01—1.74 (m, 29 H, CH, CH2); 2.07—2.29 (m, 4 H, CH2). 13C NMR, δ: 21.5, 22.78, 22.81, 28.6, 29.7, 29.8, 29.88, 29.94, 30.0, 30.9, 31.2, 31.7, 31.8, 32.7, 32.86, 32.90, 33.0 (CH, CH2, CH3); 107.6, 112.6, 112.7 (C). Found (%): C, 65.75; H, 9.71. C21H36O6. Calculated (%): C, 65.60; H, 9.44. 19,19Dibutyl8,9,17,18,20,21hexaoxadispiro[6.2.6.5] henicosane (1h), a viscous oil. 1H NMR, δ: 0.80—0.97 (m, 6 H, CH3); 1.19—1.92 (m, 32 H, CH2); 2.07—2.22 (m, 4 H, CH2). 13C NMR, δ: 14.0 (CH ); 22.76, 22.81, 22.84, 25.8, 29.84, 3 29.87, 29.94, 30.0, 32.8, 32.9, 33.0 (CH2); 111.0, 112.5 (C). Found (%): C, 66.82; H, 10.53. C23H42O6. Calculated (%): C, 66.63; H, 10.21. 3Methyl7,8,21,22,35,36hexaoxatrispiro[5.2.11.2.11.2] hexatriacontane (1i), m.p. 145—147 °C. 1H NMR, δ: 0.84—0.99 (m, 3 H, CH3); 1.02—1.91 (m, 51 H, CH, CH2); 2.06—2.32 (m, 2 H, CH2). 13C NMR, δ: 19.3, 21.6, 22.0, 22.1, 22.2, 26.0, 26.1, 26.2, 26.6, 26.7, 28.6, 31.0, 31.2, 31.7, 31.8 (CH, CH2, CH3); 111.4, 111.6, 107.4 (C). Found (%): C, 70.64; H, 10.98. C31H56O6. Calculated (%): C, 70.95; H, 10.76. 29,29Dibutyl13,14,27,28,30,31hexaoxadispiro [11.2.11.5]hentriacontane (1j), m.p. 153—156 °C. 1H NMR, δ: 0.75—1.01 (m, 6 H, CH 3); 1.08—1.92 (m, 56 H, CH 2). 13C NMR, δ: 14.0 (CH ); 19.3, 22.0, 22.8, 22.8, 25.8, 26.0, 3 26.2, 26.6, 29.8 (CH2); 110.8, 111.4 (C). Found (%): C, 71.62; H, 11.44. C33H62O6. Calculated (%): C, 71.44; H, 11.26.

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Received September 8, 2008; in revised form December 18, 2008