Transformations of peroxide ozonolysis products of natural olefins by N-containing organic compounds in methanol

Abstract

Transformations of peroxide ozonolysis products of cyclic and acyclic natural olefins with different degrees of saturation by hydroxylamine and semicarbazide hydrochlorides were investigated.Ozonolytic cleavage of olefins is a convenient method of functionalizing compounds containing multiple bonds. Therefore, transformations of peroxide products of olefin ozonolysis are broadly used in preparative organic synthesis. They can be divided into two types, i.e., those occurring with retention of an oxidation level that is intermediate between a carbonyl and carboxylic acid (cleavage reaction) and with its transformation (reduction and oxidation reactions). In the middle of the twentieth century all these types of transformations of peroxide ozonolysis products were actively studied using a variety of reagents and thermal and photochemical degradation. However, in our opinion, N-containing organic compounds have seen limited use for these purposes and are represented in ozonolysis−reduction reactions by thiourea [1], tetracyanoethylene [2, 3], pyridine [4], tertiary amines [5], and amino-N-oxides [6]; in ozonolysis−cleavage reactions by triethylamine in combination with water [3] or acetic anhydride [7-9].The goal of our work was to study the reduction of peroxide ozonolysis products of cyclic and acyclic natural olefins with different levels of substitution by organic N-containing compounds of various nature in methanol and the isolation and identification of reduction products and subsequent transformations to N-and carboxyl-containing compounds that are promising for rational organic synthesis of α,ω-bifunctional synthons and compounds with potential pharmacological and biological activity.We studied di-[triglyceride of ricinic acid (1)]-and tri-[Δ 3 -carene (2) and (+)-α-pinene (3)]-substituted olefins using hydroxylamine and semicarbazide hydrochlorides as reagents.The use of hydroxylamine hydrochloride for transformation of peroxide products of olefin ozonolysis is limited to several examples. They were all carried out in methanol and resulted in the formation of aldehydes [10], an aldoxime [11,12], and an ester [13], depending on the nature of the substrates.Based on these examples, we proposed two probable schemes for forming an ester by treatment of peroxide ozonolysis products with hydroxylamine hydrochloride. The first pathway was aldehyde → aldoxime → nitrile → ester. An alternate pathway assuming dehydration of the methoxyhydroperoxide using an acid catalyst was also possible:

Chiral amide derivatives of ricinoleic acid and 3-hydroxynonanoic acid synthesis and cytotoxic activity

“…The oxidation was performed according to the published method (Takeda et al 1997), however, some modifications of this procedure were made. Preparation of the methyl esters of (R)-3-hydroxynonanoic acid (R-6) by ozonolysis of castor oil was previously described in literature, however, in all cases the product of that reaction was a mixture of compounds (Ishmuratov et al 2006(Ishmuratov et al , 2007(Ishmuratov et al , 2009.…”

“…In general, we obtained 24 chiral compounds eight of which are derivatives of RA (1-4), two dimethyl acetals of 3-hydroxynonanal (5) and 14 derivatives of 3hydroxynonanoic acid (6-12). It is worth mentioning that only the starting methyl esters of RA (R-1, S-1) and the methyl ester of (R)-3-hydroxynonanoic acid (R-6) have been fully spectrally and polarimetrically characterized so far (Odham and Samuelsen 1970;Ishmuratov et al 2006Ishmuratov et al , 2007Ishmuratov et al , 2009Jiang et al 2010;Kula et al 2014). Moreover, the compounds R-1 and S-1 were studied with regard to biological activity.…”

Transformations of peroxide products of olefins ozonolysis

“…These cycloolefi ns were in high yield and with high selectivity converted into ketoester 134 and diketone 136 [60]. However at the use of this reagent in the ozonolysis of cycloolefi ns with more complex structure, Δ 3 -carene 137 and (+)-α-pinene 139, both at room temperature and at boiling hydroxyiminoesters 138 and 140 were obtained [61]. ( The hydrazine derivatives (2,4-dinitrophenylhydrazine, hydrochlorides of phenylhydrazine, semicarbazide, thiosemicarbazide) are effective reducers of peroxide ozonolysis products in methanol providing carbonyl compounds and their derivatives [62].…”

“…The ozonolysis of castor oil 130a followed by the treatment with semicarbazide hydrochloride furnished a mixture of diester 53 (п = 7) and hydroxyester 131, 55:45. Note the increased chemoselectivity of the formation of hydroxyester 131, the precursor of the microcomponent of the human blood serum [63], in comparison with the reduction with hydroxylamine hydrochloride. By the treatment with the same reagent on the ozonolysis products of trisubstituted monoterpenes 137 and 139 the useful for the directional synthesis optically active ketoesters 155 and 156 were obtained in high yields [61].…”