Reaction of singlet oxygen with 4-methyl-2,3-dihydro-.gamma.-pyrans
4-methyl-1,3-dihydro-..gamma..-pyran (1) reacts with singlet molecular oxygen to yield both a dioxetane 2 and an allylic hydroperoxide 3, each of which is converted by heat into a single product stable under conditions of vapor chromatography. The product composition from 1 and from 1-4-d has been d...
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| Veröffentlicht in: | J. Am. Chem. Soc.; (United States) 1977-11, Vol.99 (24), p.7977-7986 |
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| container_issue | 24 |
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| container_title | J. Am. Chem. Soc.; (United States) |
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| creator | Frimer, Aryeh A Bartlett, Paul D Boschung, Andre F Jewett, John G |
| description | 4-methyl-1,3-dihydro-..gamma..-pyran (1) reacts with singlet molecular oxygen to yield both a dioxetane 2 and an allylic hydroperoxide 3, each of which is converted by heat into a single product stable under conditions of vapor chromatography. The product composition from 1 and from 1-4-d has been determined in benzene and in acetonitrile, the ratio 2/3 being 26 times greater in the latter solvent. The tritium kinetic isotope effects at the ..cap alpha..,..beta.., and ..gamma.. positions indicate that for both products in both solvents the transition state has a weakened H-C/sup ..gamma../ bond, a strengthened H-C/sup ..beta../ bond, and an H-C/sup ..cap alpha../ bond whose strength is not appreciably altered. Possible interpretations of these effects are discussed with respect to the detailed mechanism of attack of singlet oxygen on this enol ether, which is also compared with 4,4-dimethyl-1,3-dihydropyran (4). |
| doi_str_mv | 10.1021/ja00466a033 |
| format | Article |
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The product composition from 1 and from 1-4-d has been determined in benzene and in acetonitrile, the ratio 2/3 being 26 times greater in the latter solvent. The tritium kinetic isotope effects at the ..cap alpha..,..beta.., and ..gamma.. positions indicate that for both products in both solvents the transition state has a weakened H-C/sup ..gamma../ bond, a strengthened H-C/sup ..beta../ bond, and an H-C/sup ..cap alpha../ bond whose strength is not appreciably altered. Possible interpretations of these effects are discussed with respect to the detailed mechanism of attack of singlet oxygen on this enol ether, which is also compared with 4,4-dimethyl-1,3-dihydropyran (4).</description><identifier>ISSN: 0002-7863</identifier><identifier>EISSN: 1520-5126</identifier><identifier>DOI: 10.1021/ja00466a033</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><subject>400302 - Organic Chemistry- Isotope Effects- (-1987) ; BETA DECAY RADIOISOTOPES ; BETA-MINUS DECAY RADIOISOTOPES ; CHEMICAL REACTION KINETICS ; CRYOGENIC FLUIDS ; DEUTERIUM ; ELEMENTS ; FLUIDS ; HETEROCYCLIC COMPOUNDS ; HYDROGEN ISOTOPES ; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY ; ISOTOPE EFFECTS ; ISOTOPES ; KINETICS ; LIGHT NUCLEI ; NONMETALS ; NUCLEI ; ODD-EVEN NUCLEI ; ODD-ODD NUCLEI ; ORGANIC COMPOUNDS ; ORGANIC OXYGEN COMPOUNDS ; OXYGEN ; PYRANS ; RADIOISOTOPES ; REACTION KINETICS ; STABLE ISOTOPES ; TRITIUM ; YEARS LIVING RADIOISOTOPES</subject><ispartof>J. 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Am. Chem. Soc.; (United States)</title><addtitle>J. Am. Chem. Soc</addtitle><description>4-methyl-1,3-dihydro-..gamma..-pyran (1) reacts with singlet molecular oxygen to yield both a dioxetane 2 and an allylic hydroperoxide 3, each of which is converted by heat into a single product stable under conditions of vapor chromatography. The product composition from 1 and from 1-4-d has been determined in benzene and in acetonitrile, the ratio 2/3 being 26 times greater in the latter solvent. The tritium kinetic isotope effects at the ..cap alpha..,..beta.., and ..gamma.. positions indicate that for both products in both solvents the transition state has a weakened H-C/sup ..gamma../ bond, a strengthened H-C/sup ..beta../ bond, and an H-C/sup ..cap alpha../ bond whose strength is not appreciably altered. 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Am. Chem. Soc.; (United States)</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Frimer, Aryeh A</au><au>Bartlett, Paul D</au><au>Boschung, Andre F</au><au>Jewett, John G</au><aucorp>Harvard Univ., Cambridge, MA</aucorp><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Reaction of singlet oxygen with 4-methyl-2,3-dihydro-.gamma.-pyrans</atitle><jtitle>J. Am. Chem. Soc.; (United States)</jtitle><addtitle>J. Am. Chem. Soc</addtitle><date>1977-11-01</date><risdate>1977</risdate><volume>99</volume><issue>24</issue><spage>7977</spage><epage>7986</epage><pages>7977-7986</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><abstract>4-methyl-1,3-dihydro-..gamma..-pyran (1) reacts with singlet molecular oxygen to yield both a dioxetane 2 and an allylic hydroperoxide 3, each of which is converted by heat into a single product stable under conditions of vapor chromatography. The product composition from 1 and from 1-4-d has been determined in benzene and in acetonitrile, the ratio 2/3 being 26 times greater in the latter solvent. The tritium kinetic isotope effects at the ..cap alpha..,..beta.., and ..gamma.. positions indicate that for both products in both solvents the transition state has a weakened H-C/sup ..gamma../ bond, a strengthened H-C/sup ..beta../ bond, and an H-C/sup ..cap alpha../ bond whose strength is not appreciably altered. Possible interpretations of these effects are discussed with respect to the detailed mechanism of attack of singlet oxygen on this enol ether, which is also compared with 4,4-dimethyl-1,3-dihydropyran (4).</abstract><cop>United States</cop><pub>American Chemical Society</pub><doi>10.1021/ja00466a033</doi><tpages>10</tpages></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 0002-7863 |
| ispartof | J. Am. Chem. Soc.; (United States), 1977-11, Vol.99 (24), p.7977-7986 |
| issn | 0002-7863 1520-5126 |
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| recordid | cdi_crossref_primary_10_1021_ja00466a033 |
| source | ACS Publications |
| subjects | 400302 - Organic Chemistry- Isotope Effects- (-1987) BETA DECAY RADIOISOTOPES BETA-MINUS DECAY RADIOISOTOPES CHEMICAL REACTION KINETICS CRYOGENIC FLUIDS DEUTERIUM ELEMENTS FLUIDS HETEROCYCLIC COMPOUNDS HYDROGEN ISOTOPES INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY ISOTOPE EFFECTS ISOTOPES KINETICS LIGHT NUCLEI NONMETALS NUCLEI ODD-EVEN NUCLEI ODD-ODD NUCLEI ORGANIC COMPOUNDS ORGANIC OXYGEN COMPOUNDS OXYGEN PYRANS RADIOISOTOPES REACTION KINETICS STABLE ISOTOPES TRITIUM YEARS LIVING RADIOISOTOPES |
| title | Reaction of singlet oxygen with 4-methyl-2,3-dihydro-.gamma.-pyrans |
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