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Observations on the synthesis of photochromic naphthopyrans

Observations on the synthesis of photochromic naphthopyrans
Observations on the synthesis of photochromic naphthopyrans
1-Naphthol reacts with 1,1-diarylprop-2-yn-1-ols 5a,b, under alumina catalysis, by two pathways to give the photochromic naphtho[1,2-b]pyrans 6a,b, together with the propenylid-enenaphthalenones 7a,b, representatives of a new class of merocyanine dyes. With 2-methyl-1-naphthol, formation of the photochrome is suppressed; the only products are merocyanines 7c,d. The cyclocondensation of 2-naphthol with 5a,b proceeds much more efficiently, to give the naphtho[2, 1 b]pyrans 14a,b. Pyran formation is not suppressed from either 1-bromo- or 1- (4-methoxyphenyl)-2-naphthol; reaction with 5a,b merely results in expulsion of the C-1 substituent. An alternative pathway supervenes in the reaction of 1-methyl-2-naphthol with 5a to give the benz[e]indanone 17, the constitution of which was determined by X-ray crystallography. Reaction of the 1,3,3-triarylpropynols 19a,b with 1-naphthol affords the naphthopyrans 20 together with merocyanines 21, whilst the isomeric pyrans 23 are efficiently produced from 2-naphthol. The configuration of merocyanines 7a and 21 a was unequivocally established by X-ray crystallography.
heterocycles, naphthopyran, rearrangements, photochromism, dyes, cross-coupling reactions, claisen rearrangements, convenient synthesis, stable carbocations, natural-products, cations, derivatives, catalysis, behavior
1434-193X
1220-1230
Gabbutt, Christopher D.
d57acd39-7728-473a-81c6-82dfc71a30da
Heron, B. Mark
2f65af97-0fdc-40e5-904d-5db8765b2e82
Instone, Alicia C.
9bf3a57b-27bd-4304-adf9-54a3237e0504
Thomas, David A.
ea198ebf-4f71-4b64-ac1d-a139e6cf900d
Partington, Steven M.
115a114c-dfd8-4f38-b8e2-3ebb5b2498d3
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Gelbrich, Thomas
42309d69-eaf1-4bb7-ba2e-db61f338e370
Gabbutt, Christopher D.
d57acd39-7728-473a-81c6-82dfc71a30da
Heron, B. Mark
2f65af97-0fdc-40e5-904d-5db8765b2e82
Instone, Alicia C.
9bf3a57b-27bd-4304-adf9-54a3237e0504
Thomas, David A.
ea198ebf-4f71-4b64-ac1d-a139e6cf900d
Partington, Steven M.
115a114c-dfd8-4f38-b8e2-3ebb5b2498d3
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Gelbrich, Thomas
42309d69-eaf1-4bb7-ba2e-db61f338e370

Gabbutt, Christopher D., Heron, B. Mark, Instone, Alicia C., Thomas, David A., Partington, Steven M., Hursthouse, Michael B. and Gelbrich, Thomas (2003) Observations on the synthesis of photochromic naphthopyrans. European Journal of Organic Chemistry, 2003 (7), 1220-1230. (doi:10.1002/ejoc.200390176).

Record type: Article

Abstract

1-Naphthol reacts with 1,1-diarylprop-2-yn-1-ols 5a,b, under alumina catalysis, by two pathways to give the photochromic naphtho[1,2-b]pyrans 6a,b, together with the propenylid-enenaphthalenones 7a,b, representatives of a new class of merocyanine dyes. With 2-methyl-1-naphthol, formation of the photochrome is suppressed; the only products are merocyanines 7c,d. The cyclocondensation of 2-naphthol with 5a,b proceeds much more efficiently, to give the naphtho[2, 1 b]pyrans 14a,b. Pyran formation is not suppressed from either 1-bromo- or 1- (4-methoxyphenyl)-2-naphthol; reaction with 5a,b merely results in expulsion of the C-1 substituent. An alternative pathway supervenes in the reaction of 1-methyl-2-naphthol with 5a to give the benz[e]indanone 17, the constitution of which was determined by X-ray crystallography. Reaction of the 1,3,3-triarylpropynols 19a,b with 1-naphthol affords the naphthopyrans 20 together with merocyanines 21, whilst the isomeric pyrans 23 are efficiently produced from 2-naphthol. The configuration of merocyanines 7a and 21 a was unequivocally established by X-ray crystallography.

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More information

Published date: 2003
Keywords: heterocycles, naphthopyran, rearrangements, photochromism, dyes, cross-coupling reactions, claisen rearrangements, convenient synthesis, stable carbocations, natural-products, cations, derivatives, catalysis, behavior

Identifiers

Local EPrints ID: 19954
URI: http://eprints.soton.ac.uk/id/eprint/19954
ISSN: 1434-193X
PURE UUID: 3b085db3-db40-4854-96bc-8de3823495b0

Catalogue record

Date deposited: 24 Feb 2006
Last modified: 15 Mar 2024 06:20

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Contributors

Author: Christopher D. Gabbutt
Author: B. Mark Heron
Author: Alicia C. Instone
Author: David A. Thomas
Author: Steven M. Partington
Author: Thomas Gelbrich

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