{"id":9135,"date":"2013-01-16T08:43:36","date_gmt":"2013-01-16T08:43:36","guid":{"rendered":"http:\/\/www.ch.imperial.ac.uk\/rzepa\/blog\/?p=9135"},"modified":"2013-02-14T08:06:37","modified_gmt":"2013-02-14T08:06:37","slug":"why-is-no-diphenyl-hydroxylamine-phnhoph-unknown","status":"publish","type":"post","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=9135","title":{"rendered":"Why is N,O-diphenyl hydroxylamine (PhNHOPh) unknown?"},"content":{"rendered":"
\n

If you search e.g.<\/em> Scifinder for N,O-diphenyl hydroxylamine (RN\u00a024928-98-1) there is just one literature citation, to a 1962 patent. Nothing else; not even a calculation (an increasing proportion of the molecules reported in Chemical Abstracts have now only ever been subjected to calculation, not synthesis).\u00a0A search of Reaxys also offers only one hit[1]<\/a><\/span> reporting one unsuccessful attempt in 1963 to prepare this compound.\u00a0Again, nothing else. Yet show this structure to most organic chemists, and I venture to suggest few would immediately predict this (unless they are experts on benzidine rearrangements).\u2021<\/sup><\/p>\n

\"PhNHOPh\"<\/p>\n

The eagle-eyed reader of this blog may have noticed my noting in previous posts that the benzidine rearrangement proper is normally promoted by double protonation<\/a>, and that reaction via<\/em>\u00a0monoprotonation<\/a> has a significantly higher barrier. So what are the corresponding predicted reaction barriers for PhNHOPh? I start in fact with catalytic monoprotonation. The calculations are at \u03c9B97XD\/6-311G(d,p)\/SCRF=water (closed shell) level.<\/p>\n\n\n\n\n\n\n\n\n
System<\/td>\nN-protonated<\/td>\nO-Protonated\u2021<\/sup><\/td>\n<\/tr>\n
Reactant<\/td>\n\u00a00.0<\/a><\/td>\n\u00a011.3
<\/a><\/td>\n<\/tr>\n
TS N-O<\/td>\n\u00a07.3<\/a><\/td>\n\u00a017.4<\/a><\/td>\n<\/tr>\n
\u03c0-complex<\/td>\n\u00a02.1<\/a><\/td>\n\u00a06.0<\/a>
<\/a><\/td>\n<\/tr>\n
TS C-C<\/td>\n\u00a04.8<\/a><\/td>\n\u00a013.2<\/a><\/td>\n<\/tr>\n
\u2021<\/sup>Relative to N-protonated reactant, in kcal\/mol.<\/small><\/td>\n<\/tr>\n<\/tbody>\n<\/table>\n

So it seems that even monoprotonation (on nitrogen) results in a very small \u0394G298<\/sub>\u2021<\/sup>\u00a0barrier to the formation of a\u00a0\u03c0-complex and its subsequent facile breakdown to form a C-C bond. I had noted in the earlier post that Ghigo and co-workers[2]<\/a><\/span>\u00a0had found that with diprotonated diphenyl hydrazine, the resulting \u03c0-complex has some open shell (biradical) character. The calculations reported here on the monoprotonated system are done as closed shell, but any biradical character this might have will only serve to even further reduce the barriers seen in the table. So we may confidently conclude that even monoprotonated N,O-diphenyl hydroxylamine will rapidly rearrange. A follow-up investigation for the diprotonated route hardly seems necessary!<\/p>\n

But here is a challenge: if one were able to prepare PhNHOPh in thoroughly deprotic conditions, might it be isolable? There is precedent; the keto form of phenol can indeed be isolated under such conditions.[3]<\/a><\/span>.<\/p>\n

Here are some intrinsic reaction coordinates to finish with. Firstly, for the formation of the\u00a0\u00a0\u03c0-complex from N-protonated precursor:<\/p>\n\n\n\n\n
\"PhNH2OPh-NO\"<\/a><\/td>\n<\/tr>\n
\u00a0\"PhNH2OPh-NO\"<\/td>\n\"PhNH2OPh-NOG\"\u00a0<\/td>\n<\/tr>\n<\/tbody>\n<\/table>\n

Once formed, the\u00a0\u00a0\u03c0-complex collapses readily<\/a> to the 4,4′-coupled biphenyl.\u00a0<\/p>\n\n\n\n\n
\"PhNH2OPh-pi2p\"<\/a><\/td>\n<\/tr>\n
\u00a0\"PhNH2OPh-pi2p\"<\/td>\n\"PhNH2OPh-pi2pG\"\u00a0<\/td>\n<\/tr>\n<\/tbody>\n<\/table>\n

There may be another pathway which collapses to the 1,1′-coupled biphenyl which I have not found yet. A [3,3] sigmatropic rearrangement converting the 4,4′ to the 1,1′-biphenyl is higher in energy, but still just about accessible thermally.<\/p>\n\n\n\n\n
\"PhNH2OPh-o2p\"<\/a><\/td>\n<\/tr>\n
\u00a0
\"PhNH2OPh-o2p\"<\/td>\n		\"PhNH2OPh-o2pG\"
\u00a0<\/td>\n<\/tr>\n<\/tbody>\n<\/table>\n

To end, here is a question. Could one systematically identify “gaps” in the distribution of known molecules; species which appear as if they should exist, but have never been reported? Of these, the majority will no doubt be absent from the record simply because they uninteresting. But some, as here, are absent because they are too unstable to exist, unless (extreme?) precautions are taken to remove the factors responsible for their instability (in this case, protons). Cyclobutadiene was one such famous example (stabilised by coordination to a metal). Certainly, computation nowadays can help identify conditions for how such molecules might be isolated.<\/p>\n

\n

\u2021<\/sup>In contrast, PhNHSPh (N-Phenylbenzenesulfenamide) is a well known species[4]<\/a><\/span>.<\/p>\n

References<\/h2>\n
  1. J.R. Cox, and M.F. Dunn, \"The chemistry of O,N-diarylhydroxlamines - I\", Tetrahedron Letters<\/i>, vol. 4, pp. 985-989, 1963. https:\/\/doi.org\/10.1016\/s0040-4039(01)90757-9<\/a>\n\n<\/li>\n
  2. G. Ghigo, S. Osella, A. Maranzana, and G. Tonachini, \"The Mechanism of the Acid\u2010Catalyzed Benzidine Rearrangement of Hydrazobenzene: A Theoretical Study\", European Journal of Organic Chemistry<\/i>, vol. 2011, pp. 2326-2333, 2011. https:\/\/doi.org\/10.1002\/ejoc.201001636<\/a>\n\n<\/li>\n
  3. B. Miller, \"Preparation of the Ketone Tautomer of a Phenol by a Cope Rearrangement<sup>1<\/sup>\", Journal of the American Chemical Society<\/i>, vol. 87, pp. 5515-5516, 1965. https:\/\/doi.org\/10.1021\/ja00951a064<\/a>\n\n<\/li>\n
  4. I. Brito, A. C\u00e1rdenas, A. Mundaca, M. L\u00f3pez-Rodr\u00edguez, and A. Reyes, \"2-Iodo-<i>N<\/i>-(2-nitrophenylsulfanyl)aniline\", Acta Crystallographica Section E Structure Reports Online<\/i>, vol. 64, pp. o1387-o1387, 2008. https:\/\/doi.org\/10.1107\/s1600536808019491<\/a>\n\n<\/li>\n<\/ol>\n\n<\/div> ","protected":false},"excerpt":{"rendered":"

    If you search e.g. Scifinder for N,O-diphenyl hydroxylamine (RN\u00a024928-98-1) there is just one literature citation, to a 1962 patent. Nothing else; not even a calculation (an increasing proportion of the molecules reported in Chemical Abstracts have now only ever been subjected to calculation, not synthesis).\u00a0A search of Reaxys also offers only one hit reporting one […]<\/p>\n","protected":false},"author":1,"featured_media":0,"comment_status":"open","ping_status":"open","sticky":false,"template":"","format":"standard","meta":{"_jetpack_newsletter_access":"","_jetpack_dont_email_post_to_subs":false,"_jetpack_newsletter_tier_id":0,"_jetpack_memberships_contains_paywalled_content":false,"_jetpack_memberships_contains_paid_content":false,"activitypub_content_warning":"","activitypub_content_visibility":"","activitypub_max_image_attachments":5,"activitypub_interaction_policy_quote":"anyone","activitypub_status":"","footnotes":"","jetpack_publicize_message":"","jetpack_publicize_feature_enabled":true,"jetpack_social_post_already_shared":true,"jetpack_social_options":{"image_generator_settings":{"template":"highway","default_image_id":0,"font":"","enabled":false},"version":2},"jetpack_post_was_ever_published":false},"categories":[4],"tags":[24,2651,157,2650,843],"ppma_author":[2661],"class_list":["post-9135","post","type-post","status-publish","format-standard","hentry","category-interesting-chemistry","tag-energy","tag-historical","tag-metal","tag-pericyclic","tag-reaction-mechanism"],"yoast_head":"\nWhy is N,O-diphenyl hydroxylamine (PhNHOPh) unknown? - Henry Rzepa's Blog<\/title>\n<meta name=\"robots\" content=\"index, follow, max-snippet:-1, max-image-preview:large, max-video-preview:-1\" \/>\n<link rel=\"canonical\" href=\"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=9135\" \/>\n<meta property=\"og:locale\" content=\"en_GB\" \/>\n<meta property=\"og:type\" content=\"article\" \/>\n<meta property=\"og:title\" content=\"Why is N,O-diphenyl hydroxylamine (PhNHOPh) unknown? - Henry Rzepa's Blog\" \/>\n<meta property=\"og:description\" content=\"If you search e.g. Scifinder for N,O-diphenyl hydroxylamine (RN\u00a024928-98-1) there is just one literature citation, to a 1962 patent. 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This reaction requires diprotonation to proceed readily, but we then discovered that replacing one NH by an O as in N,O-diphenyl hydroxylamine required only monoprotonation to undergo an equivalent facile rearrangement. So replacing both NHs by O to\u2026","rel":"","context":"In "Interesting chemistry"","block_context":{"text":"Interesting chemistry","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=4"},"img":{"alt_text":"","src":"","width":0,"height":0},"classes":[]},{"id":9018,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=9018","url_meta":{"origin":9135,"position":1},"title":"Hidden intermediates in the benzidine rearrangement. The monoprotonated mechanism.","author":"Henry Rzepa","date":"January 8, 2013","format":false,"excerpt":"Eagle-eyed footnote readers might have spotted one at the bottom of the post on the benzidine rearrangement. I was comparing the N-N bond lengths in crystal structures of known diprotonated hydrazines (~1.45\u00c5) with the computed N-N bond length at the start point of the intrinsic reaction coordinate for the [5,5]\u2026","rel":"","context":"In \"free energy barrier\"","block_context":{"text":"free energy barrier","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?tag=free-energy-barrier"},"img":{"alt_text":"Transition state between p-complex and N-N diprotonated diphenyhydrazine. 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Does\u2026","rel":"","context":"In "Interesting chemistry"","block_context":{"text":"Interesting chemistry","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=4"},"img":{"alt_text":"","src":"","width":0,"height":0},"classes":[]},{"id":9218,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=9218","url_meta":{"origin":9135,"position":4},"title":"Aromaticity in the benzidine-like \u03c0-complex formed from PhNHOPh.","author":"Henry Rzepa","date":"January 19, 2013","format":false,"excerpt":"The transient \u03c0-complex formed during the \"[5,5]\" sigmatropic rearrangement of protonated N,O-diphenyl hydroxylamine can be (formally) represented as below, namely the interaction of a six-\u03c0-electron aromatic ring (the phenoxide anion 2) with a\u00a0four-\u03c0-electron phenyl dication-anion pair 1. Can one analyse this interaction in terms of aromaticity? I showed previously that\u2026","rel":"","context":"In "Interesting chemistry"","block_context":{"text":"Interesting chemistry","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=4"},"img":{"alt_text":"pi-QTAIM","src":"https:\/\/i0.wp.com\/www.ch.imperial.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2013\/01\/pi-QTAIM.jpg?resize=350%2C200","width":350,"height":200},"classes":[]},{"id":23410,"url":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?p=23410","url_meta":{"origin":9135,"position":5},"title":"The small-molecule antiviral compound Molnupiravir: an exploration of its tautomers.","author":"Henry Rzepa","date":"March 14, 2021","format":false,"excerpt":"For obvious reasons, anti-viral molecules are very much in the news at the moment. Thus Derek Lowe highlights Molnupiravir which is shown as a hydroxylamine, the representation originating from the Wikipedia page on the molecule. I like stereocentres more clearly identified using eg R\/S notation and so I went to\u2026","rel":"","context":"In "Interesting chemistry"","block_context":{"text":"Interesting chemistry","link":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/?cat=4"},"img":{"alt_text":"","src":"https:\/\/i0.wp.com\/www.ch.ic.ac.uk\/rzepa\/blog\/wp-content\/uploads\/2021\/03\/molnupiravir-1024x639.jpg?resize=350%2C200&ssl=1","width":350,"height":200},"classes":[]}],"jetpack_likes_enabled":false,"authors":[{"term_id":2661,"user_id":1,"is_guest":0,"slug":"admin","display_name":"Henry Rzepa","avatar_url":"https:\/\/secure.gravatar.com\/avatar\/897b6740f7f599bca7942cdf7d7914af5988937ae0e3869ab09aebb87f26a731?s=96&d=blank&r=g","0":null,"1":"","2":"","3":"","4":"","5":"","6":"","7":"","8":""}],"_links":{"self":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/9135","targetHints":{"allow":["GET"]}}],"collection":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts"}],"about":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/types\/post"}],"author":[{"embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/users\/1"}],"replies":[{"embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fcomments&post=9135"}],"version-history":[{"count":35,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/9135\/revisions"}],"predecessor-version":[{"id":9167,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=\/wp\/v2\/posts\/9135\/revisions\/9167"}],"wp:attachment":[{"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fmedia&parent=9135"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fcategories&post=9135"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Ftags&post=9135"},{"taxonomy":"author","embeddable":true,"href":"https:\/\/www.ch.ic.ac.uk\/rzepa\/blog\/index.php?rest_route=%2Fwp%2Fv2%2Fppma_author&post=9135"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}