Synthesis and uses of alkyl hydroperoxides and dialkyl peroxides

Sheldon, Roger A.

doi:10.1002/9780470771730.ch6

Cited by 20 publications

(22 citation statements)

References 109 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…These and other minor components, z l l , z13, z14 and z15, can be considered as polarityrelated factors at this point. Since these latent variables are expressed in terms of original descriptors as shown in Eqn (2), Eqn (5) can be transformed into a substantially similar equation to Eqn (4). There are two descriptors ( P A and O X ) encoding bulk in nature on the surface in Eqn (4).…”

Section: Training Data Set Modelingmentioning

confidence: 99%

Quantitative structure—property relationships for auto‐ignition temperatures of organic compounds

Suzuki

1994

Fire and Materials

View full text Add to dashboard Cite

Quantitative structureproperty relationship techniques were applied to develop a predictive method for autoignition temperatures of a wide range of organic molecules, ioeludmg hydrocarbons, alcohols, phenols, ethers, aldehydes, ketones, acids, amines, esters and halogenated compounds. Multivariate linear regression models in terms of easily available molecular descriptors or intrinsic molecular properties such as critical pressure, parachor, atomic charges, etc were p r o m . Principal component analysis on the set of descriptors employed uncovered the significant contributions of the polarity-related factors to auto-ignition temperatures. For the majority of the 250 compounds over an auto-ignition temperature range of 170-6WC, good agreement between observed and calculated autoignition temperatures was confirmed. The method could be useful for assessing the flammability of new compounds.

show abstract

Section: Training Data Set Modelingmentioning

confidence: 99%

Quantitative structure—property relationships for auto‐ignition temperatures of organic compounds

Suzuki

1994

Fire and Materials

View full text Add to dashboard Cite

show abstract

“…1 (Figure 1), has received considerable attention. [6,7] In the last few years, the most significant progress in this field of research has originated from transition metal catalyzed oxidations [8] Ϫ transformations which utilize active oxygen compounds, such as hydrogen peroxide, [9,10] peroxo compounds, [10,11] or molecular oxygen [12] as primary oxidants. In spite of their high oxidation potentials, these reagents, if used alone, are sur- Figure 1.…”

Section: Introductionmentioning

confidence: 99%

(Schiff‐base)vanadium(V) Complex‐Catalyzed Oxidations of Substituted Bis(homoallylic) Alcohols − Stereoselective Synthesis of Functionalized Tetrahydrofurans

et al. 2003

View full text Add to dashboard Cite

Keywords: Oxidation / Tetrahydrofuran / Catalysis / Asymmetric synthesis / Vanadium Vanadium(V) complexes 4 have been prepared from tridentate Schiff-base ligands 3 and VO(OEt) 3 . All vanadium(V) compounds were characterized (IR, UV/Vis, and 51 V NMR spectroscopy, and in selected examples by X-ray diffraction analysis) and were applied as oxidation catalysts for the stereoselective synthesis of functionalized tetrahydrofurans 2 starting from substituted bis(homoallylic) alcohols 1 (mono-or trisubstituted C−C double bonds). Oxidation of secondary or tertiary 1-alkyl-, 1-vinyl-, or 1-phenyl-substituted 5,5-dimethyl-4-penten-1-ols under optimized conditions [TBHP as primary oxidant and 1,2-(amino)indanol-derived vanadium(V) reagent 4g as catalyst] provided 2,5-cis-configured tetrahydrofurans in synthetically useful yields and diastereoselectivities (22−96% de). On the other hand, trans-disubstituted oxolanes (62%−96 de) were obtained from oxidations of 2-or 3-alkyl-and 2-or 3-phenyl-substituted 5,5-dimethyl-4-penten-1-ols bis(homoallylic) alcohols. Treatment of 4-penten-1-ols (i.e. substrates with monosubstituted olefinic π-bonds) with TBHP and catalytic amounts of vanadium(V) complex 4g furnished trans-disubstituted tetrahydrofurans as major products (20−96% de), no matter whether an alkyl or a phenyl substituent was located in position 1, 2, or 3 of the alkenol chain. The mechanism of this reaction has been investigated in detail. Based on re-

show abstract

“…A probable oxidation product could be an epoxide formed at the double bond in the 13,14-position, which is more susceptible to epoxidation than the double bond in 7,8position (13). Such an epoxide would be an electrophile and therefore would be likely to react with nucleophilic 1 Abbreviations: 15-HPA, methyl 15-hydroperoxyabietate; 16-HPDA, methyl 15-hydroperoxydehydroabietate; FCA, Freund's complete adjuvant; El, electron impact; m-CPBA, m-chloroperbenzoic acid; FCAT, Freund's complete adjuvant test; CCET, cumulative contact enhancement test; pet., white petrolatum; 15-DAP, bis(methyl dehydroabietate-15-yl) peroxide. (e) bis(methyl dehydroabietate-15-yl) peroxide; (f) methyl 15-hydroperoxydehydroabietate; (g) methyl 13,14(a)-epoxyabietate;…”

Section: Introductionmentioning

confidence: 99%

“…Cross-reactivity between different haptens can take place when the haptens form complete antigens that have identical or very similar epitopes which make them react with the same T-lymphocytes (15). Epoxides of abietic acid are interesting from a mechanistic point of view since it is possible that the hydroperoxide 15-HPA could yield an epoxide in the 13,14-position before it reacts to form the complete antigen (16)(17)(18)(19).…”

Section: Introductionmentioning

confidence: 99%

Contact Allergy to Resin Acid Hydroperoxides. Hapten Binding via Free Radicals and Epoxides

Gäfvert¹,

Shao²,

Karlberg³

et al. 1994

Chem. Res. Toxicol.

View full text Add to dashboard Cite

For a better understanding of the mechanisms of contact allergic reactions, the patterns of cross-reactivity between different resin acid oxidation products were studied. The 13,14(alpha)-epoxide and the 13,14(beta)-epoxide of abietic acid and 15-hydroperoxydehydroabietic acid (15-HPDA) were shown in experimental sensitization studies to be contact allergens. Cross-reactivity was observed between the alpha- and beta-epoxides and also between the epoxides and the previously identified rosin allergen 15-hydroperoxyabietic acid (15-HPA). This indicates that 15-HPA may form an epoxide which then reacts with skin protein to generate the complete antigen. 15-HPA and 15-HPDA cross-reacted as well. This can be explained by the formation of similar alkoxy radicals from both hydroperoxides which further react with skin protein. Cross-reactivity patterns of the resin acid oxidation products indicate that 15-HPA may react with skin proteins either as a radical or as an epoxide, thus generating different antigens. The presence in rosin of the epoxides of abietic acid was also studied. The beta-epoxide was detected in gum rosin. Moreover, the epoxides elicited reactions in rosin-allergic individuals. Thus, the 13,14(beta)-epoxide of abietic acid was identified as a new, important rosin allergen.

show abstract

Synthesis and uses of alkyl hydroperoxides and dialkyl peroxides

Cited by 20 publications

References 109 publications

Quantitative structure—property relationships for auto‐ignition temperatures of organic compounds

Quantitative structure—property relationships for auto‐ignition temperatures of organic compounds

(Schiff‐base)vanadium(V) Complex‐Catalyzed Oxidations of Substituted Bis(homoallylic) Alcohols − Stereoselective Synthesis of Functionalized Tetrahydrofurans

Contact Allergy to Resin Acid Hydroperoxides. Hapten Binding via Free Radicals and Epoxides

Contact Info

Product

Resources

About