Allylic Rearrangements. XIX. Studies of the Ozonization of Allylic Systems<sup>1</sup>

Young, William G.; McKinnis, Art C.; Webb, Irving D.; Roberts, John D.

doi:10.1021/ja01206a042

Cited by 31 publications

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“…(CH3)3COCH2CH=CHCH2CH2CH=CHCH2OH As would be expected from a compound of this structure some formaldehyde is formed during ozonolysis (10). Furthermore, when the material is hydrogenated and then hydrolyzed one obtains some octanediol-1,8 as well as octanol-1.…”

Section: Methodsmentioning

confidence: 78%

“…Hydrogenation of (1,8-di-tert-butoxy-Ü,7-dimethyl-2, ß-ociadiene) fraction IV. Fraction IV (3.0 g., 10.65 mmoles) dissolved in absolute ethanol (60 ml.) was hydrogenated in the presence of Pt02 (50 mg.).…”

Section: Methodsmentioning

confidence: 99%

“…of ethyl acetate was ozonized at -80°in a stream of ozone delivered at the rate of approximately 0.6 mmole of ozone per minute, for 16 minutes. The ethyl acetate was removed at reduced pressure (10 mm. ), and the residue treated with hydrogen peroxide (10%).…”

Section: Methodsmentioning

confidence: 99%

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The Chemistry of Hydroperoxides. X. The Addition of Free Alkoxy Radicals to Conjugated Systems

Kharasch¹,

Arimoto²,

Nudenberg³

1951

J. Org. Chem.

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Many investigators (1), on the basis of indirect evidence, have postulated the formation of alkoxy (RO •) free radicals in the course of the decomposition of hydroperoxides by ferrous salts. Direct evidence of existence of such radicals in the aqueous phase has been obtained by carrying out the decompositions in the presence of butadiene and other olefins at 0°. The products identified are accounted for by reaction sequences of the type indicated in equations 1 to 4.Dimers A and B are formed in about 85 and 15% yields, respectively.The yields of dimers A and B vary somewhat with the nature of the hydroperoxide. With butadiene the best yield (85%) was obtained with ieri-butyl hydroperoxide. cx-Cumyl hydroperoxide and hydrogen peroxide gave 65% and 23% of the dimeric products, respectively. SUMMARY Free alkoxy radicals add to butadiene, isoprene, and chloroprene to give free radicals which then dimerize. The structures of these dimeric products have been established. Chicago 37, Illinois

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Section: Methodsmentioning

confidence: 78%

Section: Methodsmentioning

confidence: 99%

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The Chemistry of Hydroperoxides. X. The Addition of Free Alkoxy Radicals to Conjugated Systems

Kharasch¹,

Arimoto²,

Nudenberg³

1951

J. Org. Chem.

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“…Zwitterionic fragment can also interact with a hydroxy group located in a different (not α) position with respect to the double bond, provided that its position is appropriate for such interaction [11]. Ozonolysis of octahydronaphthalene 36 in methylene chloride at -78°C, followed by treatment with copper(II) acetate and FeSO 4 , led to the formation of macrolide antibiotic 37 [12] (Scheme 13).…”

Section: Mementioning

confidence: 99%

Ozonolysis of Unsaturated Carbonyl Compounds and Alcohols

et al. 2010

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“…Since conditions which might lead to overozonation were avoided, arabinose formation appeared to be an example of "abnormal ozonolysis" ofan allyliccompound, involving the rearrangement of an alkene-ozone reaction intermediate (2). In this connection Young et al (3) observed that allylic acetates were less prone to "abnormal ozonolysis" than their parent alcohols, while Milas and Nolan (4) claimed that some "abnormal ozonolyses" could be prevented by conducting ozonations in cold methanol. The mixture of l a and 2a, and their acetates (lb and 2b) were therefore ozonized under different conditions.…”

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confidence: 99%

Lengthening of tetrose and pentose carbon chains by vinylation reactions

Walton¹

1968

Can. J. Chem.

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Vinylation of 2,3 :4,5-di-0-isopropylidene-aldel~ydo-D-arabnoe gave a 1.3:1 mixture of 1,2:3,4-di-0-isopropylidene-6-heptene-L-gulo (and D-manno)-1,2,3,4,5-pentol (la and 20). Successive ozonolysis and hydrolysis of the mixture of l a and 2a gave D-glucose and D-mannose in a ratio of 1.4:1. Vinylation of 2,4-0-ethylidene-aldel~ydo-D-erythrose gave a 3.9:1 mixture of 1,3-0-ethylidene-5-hexene-L-ribo (and ~-lyxo)-1,2,3,4-tetrol (3a and 4a), which was degraded to form D-ribose and barabinose in a ratio of 4:l. The configuration of each of the C-vinyl compounds la, 2a, 3a, and 4a was assigned by degradation to the corresponding aldose.Canadian Journal of Chemistry. 46, 3679 (1968) A report from this laboratory described a new method of lengthening aldose carbon chains, which involved vinylation of an aldehydo sugar, ozonolysis of the product, and removal of hydroxyl protecting groups (I). Treatment of 2,3 :4,5-di-0-isopropylidene-aldeIzydo-D-arabinose with vinylmagnesium chloride gave a product which was resolved by gas-liquid partition chromatography (g.1.p.c.) into two components, A and B, in the ratio of 1.3 :l. The data obtained from elemental analysis, quantitative hydrogenation, and infrared spectroscopy were consistent with a di-O-isopropylidene-6-heptene-1,2,3,4,5-pent01 structure. The formation of monoacetates with acetic anhydride indicated the presence of a single hydroxyl group. Ozonolysis and deketalization of pure component A gave D-glucose' with a small proportion of an arabinose. Component A (fast moving on g.1.p.c.) was therefore 1,2:3,4-di-0-isopropylidene-6-heptene-L-gulo-1,2,3,4,5-pent01 (la). Similar degradation of component B (slow moving on g.1.p.c.) gave D-mannose,' with some arabinose. Hence component B was the D-manno epimer (2a).Similar methods were used to verify the structures of the 3-acetates (lb and 2b), which 'Degradations of mixed epimers on a preparative scale gave only D-sugars. Aldoses formed for configurational assignment were therefore assumed to be D-enantiomers, although they were identified only by chromatography.were resolved by gas-liquid partition chromatography (g.1.p.c.) into a fast-flowing component, C, and a slow-flowing component D. Since components C and D were degraded to D-glucose' and D-mannose,' respectively, C was the L-gulo epimer (lb) and D was the D-manno epimer (26).Preliminary experiments in which l a and 2a were ozonized in ethyl acetate, and then hydrogenated and deketalized, resulted in the formation of appreciable quantities of arabinose. Efforts were therefore directed to reducing the formation of this by-product. Since conditions which might lead to overozonation were avoided, arabinose formation appeared to be an example of "abnormal ozonolysis" ofan allyliccompound, involving the rearrangement of an alkene-ozone reaction intermediate (2). In this connection Young et al. (3) observed that allylic acetates were less prone to "abnormal ozonolysis" than their parent alcohols, while Milas and Nolan (4) claimed that some "abnormal ozonolyses" could ...

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Allylic Rearrangements. XIX. Studies of the Ozonization of Allylic Systems¹

Abstract: Ozonization of Allylic Systems 293 but are strongly dependent on degree of esterification, being highest for degree of esterification in the range 0.3 to 0.5. Enzyme-deesterified pectins form weaker ionic-bonded gels than do aciddeésterified pectins. Philadelphia, Pa.

Cited by 31 publications

References 0 publications

The Chemistry of Hydroperoxides. X. The Addition of Free Alkoxy Radicals to Conjugated Systems

The Chemistry of Hydroperoxides. X. The Addition of Free Alkoxy Radicals to Conjugated Systems

Ozonolysis of Unsaturated Carbonyl Compounds and Alcohols

Lengthening of tetrose and pentose carbon chains by vinylation reactions

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Allylic Rearrangements. XIX. Studies of the Ozonization of Allylic Systems1

Abstract: Ozonization of Allylic Systems 293 but are strongly dependent on degree of esterification, being highest for degree of esterification in the range 0.3 to 0.5. Enzyme-deesterified pectins form weaker ionic-bonded gels than do aciddeésterified pectins. Philadelphia, Pa.

Cited by 31 publications

References 0 publications

The Chemistry of Hydroperoxides. X. The Addition of Free Alkoxy Radicals to Conjugated Systems

The Chemistry of Hydroperoxides. X. The Addition of Free Alkoxy Radicals to Conjugated Systems

Ozonolysis of Unsaturated Carbonyl Compounds and Alcohols

Lengthening of tetrose and pentose carbon chains by vinylation reactions

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Product

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Allylic Rearrangements. XIX. Studies of the Ozonization of Allylic Systems¹