{"@context":{"@vocab":"https://cir.nii.ac.jp/schema/1.0/","rdfs":"http://www.w3.org/2000/01/rdf-schema#","dc":"http://purl.org/dc/elements/1.1/","dcterms":"http://purl.org/dc/terms/","foaf":"http://xmlns.com/foaf/0.1/","prism":"http://prismstandard.org/namespaces/basic/2.0/","cinii":"http://ci.nii.ac.jp/ns/1.0/","datacite":"https://schema.datacite.org/meta/kernel-4/","ndl":"http://ndl.go.jp/dcndl/terms/","jpcoar":"https://github.com/JPCOAR/schema/blob/master/2.0/"},"@id":"https://cir.nii.ac.jp/crid/1361699995930222464.json","@type":"Article","productIdentifier":[{"identifier":{"@type":"DOI","@value":"10.1016/j.jphotochem.2006.06.017"}},{"identifier":{"@type":"URI","@value":"https://api.elsevier.com/content/article/PII:S1010603006003339?httpAccept=text/xml"}},{"identifier":{"@type":"URI","@value":"https://api.elsevier.com/content/article/PII:S1010603006003339?httpAccept=text/plain"}}],"dc:title":[{"@value":"New facets in the photochemistry and thermal reaction of 2,2-diphenylmethylenecyclopropane"}],"description":[{"notation":[{"@value":"Abstract   Photochemistry and thermal reaction of 2,2-diphenylmethylenecyclopropane  1a  have been reinvestigated to make their mechanistic refinement. A new finding in the photochemistry of  1a  is the detection and isolation of cyclobutene  7 . While fragmentation and 1,3-carbon (C) shift is responsible for previously reported photoproducts, 1,1-diphenylethylene  3  and diphenylmethylenecyclopropane  2a , respectively, a new pathway is required to explain the formation of cyclobutene  7 . A mechanism involving the 1,2-C shift (Scheme 3, arrow b) followed by 1,2-hydrogen (H) shift is proposed. In the thermal reaction of  1a,  on the other hand, a trimethylenemethane type of species is shown to be a common intermediate for degeneracy, rearrangement from  1a  to  2a , and formation of indene  5 . In the photochemistry of  1a , intervention of cyclobutylidene  8  is strongly supported by circumstantial evidences provided by steady-state and laser flash photolytic investigations. Further experiments designed to independently generate cyclobutylidene  8  showed the methylenecyclopropane/cyclobutene branching ratio  (1a / 7 ) to be in the range between 0 and 1.7, which is much lower than the value of 4.0 for parent cyclobutylidene. Nevertheless, the relative efficiency of 1,2-shift pathway to generate  8  is shown to be as high as 17–47% compared to 1,3-C shift to give  2a  at the early photochemical stage of  1a ."}]}],"creator":[{"@id":"https://cir.nii.ac.jp/crid/1381699995930222464","@type":"Researcher","foaf:name":[{"@value":"Yasutake Takahashi"}]},{"@id":"https://cir.nii.ac.jp/crid/1381699995930222467","@type":"Researcher","foaf:name":[{"@value":"Takurou Sakakibara"}]},{"@id":"https://cir.nii.ac.jp/crid/1381699995930222466","@type":"Researcher","foaf:name":[{"@value":"Takahisa Tominaga"}]},{"@id":"https://cir.nii.ac.jp/crid/1381699995930222465","@type":"Researcher","foaf:name":[{"@value":"Makoto Inaba"}]},{"@id":"https://cir.nii.ac.jp/crid/1381699995930222468","@type":"Researcher","foaf:name":[{"@value":"Hideo Tomioka"}]}],"publication":{"publicationIdentifier":[{"@type":"PISSN","@value":"10106030"}],"prism:publicationName":[{"@value":"Journal of Photochemistry and Photobiology A: Chemistry"}],"dc:publisher":[{"@value":"Elsevier BV"}],"prism:publicationDate":"2007-01","prism:volume":"185","prism:number":"2-3","prism:startingPage":"253","prism:endingPage":"262"},"reviewed":"false","dc:rights":["https://www.elsevier.com/tdm/userlicense/1.0/","https://www.elsevier.com/legal/tdmrep-license"],"url":[{"@id":"https://api.elsevier.com/content/article/PII:S1010603006003339?httpAccept=text/xml"},{"@id":"https://api.elsevier.com/content/article/PII:S1010603006003339?httpAccept=text/plain"}],"createdAt":"2006-08-09","modifiedAt":"2025-10-19","relatedProduct":[{"@id":"https://cir.nii.ac.jp/crid/1360004233563374208","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"Microwave discharge electrodeless lamps (MDEL)"}]}],"dataSourceIdentifier":[{"@type":"CROSSREF","@value":"10.1016/j.jphotochem.2006.06.017"},{"@type":"OPENAIRE","@value":"doi_dedup___::d7849a6929afafb2bf5b75915ed1ce5b"},{"@type":"CROSSREF","@value":"10.1039/c1pp05059a_references_DOI_BHrDMXruqWANl8HUa3DDOQAEiBN"}]}