Preparative oxidation of cycloalkanes with O(3P) atoms: microwave discharge of carbon dioxide as a source of O(3P) atoms

Zadok, Elazar; Mazur, Yehuda

doi:10.1021/jo00132a060

Cited by 15 publications

(6 citation statements)

References 1 publication

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Microwave discharge methods generate O( 3 P), but often in the presence of other reactive species, such as O( 1 D), 1 O 2 , and O 3 . 8, 21,22 In developing the research problem on sulfoxide photochemistry, it was important to choose a system whose solution phase O( 3 P) reaction was well-studied. One such reaction previously studied in the condensed phase is that between O( 3 P) and styrene 3.…”

Section: Introductionmentioning

confidence: 99%

“…We sought to establish the mechanistic criteria to learn of a possible sulfoxide method to generate O( 3 P) atoms or an equivalent active oxygen species. Microwave discharge methods generate O( 3 P), but often in the presence of other reactive species, such as O( 1 D), 1 O 2 , and O 3 . ,, In developing the research problem on sulfoxide photochemistry, it was important to choose a system whose solution phase O( 3 P) reaction was well-studied. One such reaction previously studied in the condensed phase is that between O( 3 P) and styrene 3 . , Answers to questions about the formation of rearranged styrene byproducts, discussed in this study, have yielded encouraging lessons about the viability of sulfoxides 1 , 2 to produce O( 3 P) atoms.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Gauging the Significance of Atomic Oxygen [O(³P)] in Sulfoxide Photochemistry. A Method for Hydrocarbon Oxidation

Thomas

Greer

2003

J. Org. Chem.

View full text Add to dashboard Cite

A liquid-phase photolysis of 1,2-benzodiphenylene sulfoxide, 1, and dibenzothiophene sulfoxide, 2, was used to generate atomic oxygen [O(3P)] or an equivalent active oxygen species. The reaction for sulfoxide photodeoxygenation was similar to a microwave discharge method for generating O(3P) atoms in the condensed phase (Zadok, E.; Rubinraut, S.; Mazur, Y. J. Org. Chem. 1987, 52, 385-90). Sulfoxide photodeoxygenation is a potentially clean method for O(3P) production compared to the microwave discharge method. With Argon purging of the sulfoxide sample before photolysis, the method can preclude a secondary oxidation process involving molecular oxygen. Our study focused on the results of oxidation products in the reaction of styrene, 3, and on the dependence of substrates that provided an opportunity to vary the electronic and steric effects. The sulfoxide photochemistry is rationalized with the primary formation of O(3P) in which a charge-transfer interaction between O(3P) and substrate precedes oxidation. Functionalization of hydrocarbons takes place under mild photolysis conditions of 1 and 2, which leads to an interesting possibility for the synthetic use of atomic oxygen, O(3P). Alkanes give principally alcohols. Alkenes give principally epoxides and ketones. For comparison, hydroxyl radicals are more reactive and less selective toward hydrocarbons compared to O(3P) atoms. On the other hand, O(3P) atoms balance reactivity and selectivity and involve the oxidation of inert alkanes typically inaccessible to peracid, dioxirane, ozone, and singlet molecular oxygen chemistry. The findings from this study may be useful to those interested in generating high-value oxygenated compounds from readily available petroleum components.

show abstract

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Gauging the Significance of Atomic Oxygen [O(³P)] in Sulfoxide Photochemistry. A Method for Hydrocarbon Oxidation

Thomas

Greer

2003

J. Org. Chem.

View full text Add to dashboard Cite

show abstract

“…For each metal at least two different spin cases have been considered, the atomic ground-state spin and the product ground-state spin (referred to as the low-spin state). The basis sets and methods used are the same as in ref 5. The basis sets are of double-f to triple-f quality, including / functions on the metal and d functions on carbon.…”

Section: Scheme 11°omentioning

confidence: 99%

“…Both these factors influence the position of the crossing point between the two surfaces. (5) Blomberg, M. R. A.; Siegbahn, P. E. M.; Svcnsson, M. J. Phys. Chem.…”

Section: Scheme 11°omentioning

confidence: 99%

“…1990, 94, 8656. Reaction of 0(3P) with Cyclohexane Clusters. Hint for the Mechanism in the Liquid Phase Y. Rudich, S. Lifson, and R. Naaman* Department of Chemical Physics Weizmann Institute, Rehovot 76100, Israel Received May 5,1991 Investigations of gas-phase processes are commonly used to gain microscopic insight on the corresponding liquid-phase reactions.1…”

Section: Scheme 11°omentioning

confidence: 99%

See 1 more Smart Citation

Reaction of second-row transition-metal atoms with methane

Svensson¹,

Blomberg²,

Siegbahn³

1991

J. Am. Chem. Soc.

View full text Add to dashboard Cite

Versuche zur Regio‐ und Stereoselektivität der radikalischen Chlorierung von Cycloalkanen mit verschiedenen Halogenüberträgern und Wirt‐Gast‐Komplexen¹⁾

Schneider

Philippi

1984

Chem. Ber.

View full text Add to dashboard Cite

Die Regioselektivitat der Umsetzung von Iruns-l,4-Dimethylcyclohexan (1) mit (Dich1oriod)benzol (D), den meisten p-substituierten D-Derivaten wie auch rnit Chlor in Schwefelkohlenstoff ist z. B. durch R: = 10 charakterisiert, wahrend mit o-substituierten D-Verbindungen wie auch mit D (R = H) in Eisessig oder Wasser zwar ebenfalls genugend Umsatz, jedoch R: = 5 beobachtet wird. Tertiare Cyclohexyl-Radikale werden mit D ( R = H) iiberwiegend von der axialen Seite chloriert; o-Substitution in D oder der Ersatz von CCI, durch CS2 oder Benzol fiihrt zur Herabsetzung der Stereoselektivitat. Chlorierungen mit lodphenylderivaten, welche an eine Steroidmatrix gebunden sind, ergeben keine signifikante Anderung der Regioselektivitat, ebenso Reaktionen in Gegenwart von neu synthetisierten Azacyclophan-Salzen in Wasser, obwohl diese die verwendeten Kohlenwasserstoffe komplexieren und z. B. bei Tetralin die Hydrolyse der gebildeten Chloride weitgehend inhibieren. Dagegen laRt sich mit a-Cyclodextrin durch Komplexierung von 1 eine iiberwiegende Chlorierung an den primaren C -H-Bindungen erreichen. Die Synthesen und '3C-NMR-Verschiebungen der Azacyclophane werden beschrieben.The reaction of fruns-l,4-dimethylcyclohexane (1) with (dich1oroiodo)benzene (D), with most of the p-substituted D-derivatives, and with chlorine in carbon disulfide shows a regioselectivity of R: = 10; reactions with o-substituted D-compounds or with D (R = H) in acetic acid or water show appreciable conversion, but lower selectivities of R: = 5. Tertiary cyclohexyl radicals are chlorinated preferentially from the axial side with D (R = H); ortho-substituents in D, or replacement of CCI, by CS, or benzene lead to lower stereoselectivities. Chlorinations with iodophenyl derivatives, which are bound to a steroid matrix, exhibit no significant change in regioselectivity; the same is observed for reactions with chlorine in the presence of newly synthesized macrocyclic azacyclophane salts in water, although these form inclusion complexes with the hydrocarbons used and inhibit the hydrolysis of chlorides obtained from tetralin. a-Cyclodextrin, however, leads by selective complexation of 1 to selective chlorination of the primary C -H bonds. Syntheses and I3C NMR shifts of the azacyclophanes are described. Uber radikalische Halogenierungen von Paraffinen liegen zahlreiche Arbeiten vor2S3), welche sich in neuerer Zeit u. a. auf die Abhangigkeit der Regioselektivitat von S~l v e n s -~~~) und Konzen-trationseffekten6) sowie von der Art des Halogenier~ngsmittels~.~) und von Substituenten im Substrat 5 * 9 ) konzentrieren. Reaktionen an komplizierter gebauten alicyclischen Kohlenwasser-0 Verlag Chemie GmbH, D-6940 Weinheim, 1984 OOO9-2940/84/1010-3056 $ 02.50/0Versuche zur Regio-und Stereoselektivitat der radikalischen Chlorierung von Cycloalkanen 3057 stoffen, bei denen auch der stereochemische Ablauf genauer geklart werden konnte, wurden bisher selten untersucht 9 . 1 0 ) und erfordern die Anwendung neuer Analysenmethoden. In der vorliegenden Arbeit werden Chlorieru...

show abstract

Preparative oxidation of cycloalkanes with O(3P) atoms: microwave discharge of carbon dioxide as a source of O(3P) atoms

Cited by 15 publications

References 1 publication

Gauging the Significance of Atomic Oxygen [O(³P)] in Sulfoxide Photochemistry. A Method for Hydrocarbon Oxidation

Gauging the Significance of Atomic Oxygen [O(³P)] in Sulfoxide Photochemistry. A Method for Hydrocarbon Oxidation

Reaction of second-row transition-metal atoms with methane

Versuche zur Regio‐ und Stereoselektivität der radikalischen Chlorierung von Cycloalkanen mit verschiedenen Halogenüberträgern und Wirt‐Gast‐Komplexen¹⁾

Contact Info

Product

Resources

About

Preparative oxidation of cycloalkanes with O(3P) atoms: microwave discharge of carbon dioxide as a source of O(3P) atoms

Cited by 15 publications

References 1 publication

Gauging the Significance of Atomic Oxygen [O(3P)] in Sulfoxide Photochemistry. A Method for Hydrocarbon Oxidation

Gauging the Significance of Atomic Oxygen [O(3P)] in Sulfoxide Photochemistry. A Method for Hydrocarbon Oxidation

Reaction of second-row transition-metal atoms with methane

Versuche zur Regio‐ und Stereoselektivität der radikalischen Chlorierung von Cycloalkanen mit verschiedenen Halogenüberträgern und Wirt‐Gast‐Komplexen1)

Contact Info

Product

Resources

About

Gauging the Significance of Atomic Oxygen [O(³P)] in Sulfoxide Photochemistry. A Method for Hydrocarbon Oxidation

Gauging the Significance of Atomic Oxygen [O(³P)] in Sulfoxide Photochemistry. A Method for Hydrocarbon Oxidation

Versuche zur Regio‐ und Stereoselektivität der radikalischen Chlorierung von Cycloalkanen mit verschiedenen Halogenüberträgern und Wirt‐Gast‐Komplexen¹⁾