[ { "id": "authors:ymea5-ssk50", "collection": "authors", "collection_id": "ymea5-ssk50", "cite_using_url": "https://resolver.caltech.edu/CaltechAUTHORS:20151015-104931160", "type": "article", "title": "Evidence for Cyclohexyne and Cyclopentyne as Intermediates in the Coupling Reactions of Phenyllithium with 1-Chlorocyclohexene and 1-Chlorocyclopentene", "author": [ { "family_name": "Montgomery", "given_name": "Lawrence K.", "clpid": "Montgomery-L-K" }, { "family_name": "Scardiglia", "given_name": "F.", "clpid": "Scardiglia-F" }, { "family_name": "Roberts", "given_name": "John D.", "clpid": "Roberts-J-D" } ], "abstract": "Phenyllithium and 1-chlorocyclohexene and 1-chlorocyclopentene react at 150\u00ba in ether to form 1-phenylcyclohexene and 1-phenylcyclopentene, respectively. A 1:1 mixture of 1-chlorocyclohexene-2-^(14) and 1-chlorocyclohexene-6 ^(14)- with phenyllithium yielded 1-phenylcyclohexene-x-^(14)C which contained 23 % of the ^(14)C label in the 1-position. When 1-chlorocyclopentene-1-^(14)C was heated with phenyllithium, extensive rearrangement of the ^(14)C label occurred with 48.9, 36.2, and 14.9% of the ^(14)C distributed in the 1-,2-, and 5-positions of 1-phenylcyclopentene, respectively. The observed ^(14)C rearrangements which accompanied these nucleophilic substitution reactions are best rationalized in terms of an elimination-addition mechanism involving cycloalkyne intermediates.", "doi": "10.1021/ja01087a015", "issn": "0002-7863", "publisher": "American Chemical Society", "publication": "Journal of the American Chemical Society", "publication_date": "1965-05-01", "series_number": "9", "volume": "87", "issue": "9", "pages": "1917-1925" }, { "id": "authors:ev0mj-5ks58", "collection": "authors", "collection_id": "ev0mj-5ks58", "cite_using_url": "https://resolver.caltech.edu/CaltechAUTHORS:20151020-105559197", "type": "article", "title": "Small-Ring Compounds. XXVII. Nucleophilic Displacement Reactions of Some Halogen-substituted Phenylcyclobutenes", "author": [ { "family_name": "Kitahara", "given_name": "Yoshio", "clpid": "Kitahara-Yoshio" }, { "family_name": "Caserio", "given_name": "Marjorie C.", "clpid": "Caserio-M-C" }, { "family_name": "Scardiglia", "given_name": "Franco", "clpid": "Scardiglia-F" }, { "family_name": "Roberts", "given_name": "John D.", "clpid": "Roberts-J-D" } ], "abstract": "Nucleophilic substitution reactions of 1,1-difluoro-2,2-dichloro-3-phenylcyclobutene and 1.1-difluoro-2,4-dichloro-3-phenylcyclobutene with potassium hydroxide in ethanol and with plienyllithium have been found to proceed with rearrangement, and have led to preparations of some new cyclobutene and cyclobutone derivatives.", "doi": "10.1021/ja01497a031", "issn": "0002-7863", "publisher": "American Chemical Society", "publication": "Journal of the American Chemical Society", "publication_date": "1960-06-01", "series_number": "12", "volume": "82", "issue": "12", "pages": "3106-3111" }, { "id": "authors:7hk1d-wbj06", "collection": "authors", "collection_id": "7hk1d-wbj06", "cite_using_url": "https://resolver.caltech.edu/CaltechAUTHORS:20151021-080046202", "type": "article", "title": "Rearrangement in the Reaction of p-Halotoluenes with Potassium Anilide", "author": [ { "family_name": "Scardiglia", "given_name": "Franco", "clpid": "Scardiglia-F" }, { "family_name": "Roberts", "given_name": "John D.", "clpid": "Roberts-J-D" } ], "abstract": "In recent years it has been shown that alkali amides in liquid ammonia and refluxing piperidine and organolithium compounds react with non-activated aryl halides by the way of bensyne (I) intermediates.", "doi": "10.1021/jo01098a617", "issn": "0022-3263", "publisher": "American Chemical Society", "publication": "Journal of Organic Chemistry", "publication_date": "1958-04", "series_number": "4", "volume": "23", "issue": "4", "pages": "629-631" }, { "id": "authors:p9cjq-mtk77", "collection": "authors", "collection_id": "p9cjq-mtk77", "cite_using_url": "https://resolver.caltech.edu/CaltechAUTHORS:20151026-152654071", "type": "article", "title": "Reactions of non-activated aryl halides with nucleophilic agents induced by alkali amides in liquid ammonia", "author": [ { "family_name": "Scardiglia", "given_name": "Franco", "clpid": "Scardiglia-F" }, { "family_name": "Roberts", "given_name": "John D.", "clpid": "Roberts-J-D" } ], "abstract": "It has been shown that the reactions of nucleophiles with non-activated aryl halides, discovered by Bergstrom to be induced by alkali amides in liquid ammonia, proceed by way of a benzyne-type intermediate. The ease with which a given nucleophile can compete with amide ion does not appear to be a simple function of either its basic strength or nucleophilic character as measured in other reactions. Thus, the anions of a number of weak acids line up qualitatively in competitive power as follows: fluorenyl anion ~ anilide > thiophenolate ~ triphenylmethide > acetophenone enolate anion ~ phenylacetylide > phenolate > pyrrolate > alkoxides, iodide or cynaide. The results indicate benzyne to be a highly unstable entity.", "doi": "10.1016/0040-4020(58)80015-0", "issn": "0040-4020", "publisher": "Elsevier", "publication": "Tetrahedron", "publication_date": "1958", "series_number": "3", "volume": "3", "issue": "3", "pages": "197-208" }, { "id": "authors:06v13-at059", "collection": "authors", "collection_id": "06v13-at059", "cite_using_url": "https://resolver.caltech.edu/CaltechAUTHORS:20151026-152654372", "type": "article", "title": "Evidence for cyclohexyne as an intermediate in the coupling of phenyllithium with 1-chlorocyclohexene", "author": [ { "family_name": "Scardiglia", "given_name": "F.", "clpid": "Scardiglia-F" }, { "family_name": "Roberts", "given_name": "John D.", "clpid": "Roberts-J-D" } ], "abstract": "Elimination-Adition mechanisms involving \"benzyne\"-type (C_6H_4) intermediates have been established for the rearrangements which occur in the amination of non-activated aryl halides, high temperature alkaline hydrolysis of aryl halides and the coupling of phenyllithium with aryl halides. Wittig and Harboth have reported small yields of 1-phenylcyclohexene from the coupling of phenyllithium with 1-chlorocyclohexene and it appeared possible that this reaction might well proceed by way of cyclohexyne as an intermediate. Of interest in this connection is the report by Favorsky and Boshowsky that a cyclohyexne trimer (dodecahydrotriphenylene) is formed in the reaction of 1,2-dibromocyclohexene with sodium.", "doi": "10.1016/0040-4020(57)88011-9", "issn": "0040-4020", "publisher": "Elsevier", "publication": "Tetrahedron", "publication_date": "1957", "series_number": "4", "volume": "1", "issue": "4", "pages": "343-344" } ]