112. Styrylpyrylium salts. Part XIV. Further study of the colour phenomenon associated with benzonaphtha- and dinaphtha-spiropyrans

Heilbron, I. M.; Heslop, Robert Norman; Irving, Francis

doi:10.1039/jr9330000430

Cited by 18 publications

(15 citation statements)

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“…The carbonyl carbon again forms an acid-catalyzed carbocation to eventually generate a styryl pyrilium salt. Similar styryl pyrilium salts of 2-hydroxy-1-naphthaldehyde by condensation with dibenzylketone (Dickinson, Heilbron, & O'Brien, 1928) and salicylaldehyde have been reported in the literature (Dickinson & Heilbron, 1927;Heilbronn, Heslop, & Irving, 1933). The proposed mechanism was also supported by the crystal structure of [3-(2,β-thiodimethylene)[2-(2-hydroxy)-1-benzylvinyl)]benzo pyrilium chloride] (5) which was obtained by the condensation of 4-tetrahydrothiopyranone and salicylaldehyde.…”

Section: Mechanism For the Formation Of 33′-azadimethylene Dibenzosupporting

confidence: 75%

Tumor suppressive activities of solvatochromic 3,3′‐azadimethylene dinaphthospiropyran in colon cancer model

et al. 2020

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Spiropyrans have been extensively investigated because of their thermo‐ and photochromic characteristics, but their biotherapeutic properties have not been explored much. We report anti‐proliferative properties of a novel 3,3′‐azadimethylene dinaphthospiropyran 11. Dibenzospiropyrans and dinaphthospiropyrans were synthesized by a simple and expedient method using acid‐catalyzed aldol condensation of salicylaldehyde and 2‐hydroxy‐1‐naphthaldehyde, respectively, with cyclic ketones. Together with structural elucidation by 2D NMR and X‐ray crystallography studies, we provide a putative mechanism for their formation. Compound 11 showed solvatochromism and exhibited altered spectral characteristics depending on the pH. In acidic conditions, 11 remains in open form, whereas upon alkalinization it reverts back to closed form. Based on the in vitro anti‐proliferative activity in H441, HCT‐116, MiaPaCa‐2, and Panc‐1 cancer cell lines, 11 was submitted to further investigation. It reduced HCT116 colonosphere formation and demonstrated induction of caspase cascade, suggesting apoptosis. In vitro proliferation assays also suggested that HCl and trifluoroacetate salts of 11 are more effective. Treatment of mice carrying HCT‐116 xenografts with 11 (5 µg/day, intraperitoneal for 3 weeks) suppressed tumor growth by 62%. Overall, the results reveal a new series of structurally complex, but relatively easy to synthesize molecules of which compound 11 represents a lead for anticancer development.

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Section: Mechanism For the Formation Of 33′-azadimethylene Dibenzosupporting

confidence: 75%

Tumor suppressive activities of solvatochromic 3,3′‐azadimethylene dinaphthospiropyran in colon cancer model

et al. 2020

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“…Some products which at first were believed to be coumarins132-134, 160,164-167 were later shown to be c h r o m o n e~, '~~,~~~, '~~ and in other cases the reverse was true. 71,146,167 Methods of distinguishing between chromones and coumarins are discussed in Chapter VIII, Section IV.…”

Section: General Methods Of Preparing Chromonesmentioning

confidence: 99%

“…Dann and I l l i~~g~'~ showed that when 3-aryloxypropenoic acids or ester: are treated at room temperature with 80% sulfuric acid, the product (146) i: identical with that prepared from the phenol (147), ethyl acetoacetate, and sul furic acid. Acetyl chloride containing a few drops of sulfuric acid causec cyclization of 3-(3-methoxyphenoxy)crotonic acid (145, R = H) to 7-methoxy.…”

Section: Condensation Of a Phenol With An Unsaturated Acid Or Estermentioning

confidence: 99%

“…2-methylchromone ( 148). 274 The coumarin (146) was also formed from the acic or ester (145) under the influence of phosphoric acid or hydrogen fluoride, bu the yields were lower than with sulfuric Its formation may involve thc oxonium (149) and carbenium ( Chromones are formed when di-or trichloropropenyl chlorides react with benzenoid compounds such as 1,3-dimethoxyben~ene~~~-~~* (see Chapter XIV, Section 11.2 for a more detailed account).…”

Section: Condensation Of a Phenol With An Unsaturated Acid Or Estermentioning

confidence: 99%

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General Methods of Preparing Chromones

Ellis¹

1977

Chemistry of Heterocyclic Compounds: A Series of Monographs

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“…Another interesting illustration of the necessity for planarity in the resonance hybrid is afforded by the diminishing tendency for thermochromism in the series XVI, = 2,3,4 (4,11,12). Here the five-membered ring (XVII, = 2) favors a flat structure5, whereas a puckered ring with more than five members (XVI, = 3) hinders it (XVIa).…”

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confidence: 99%

Steric Factors in Thermochromism of Spiropyrans and in Reactivities of Certain Methylene Groups

Koelsch¹

1951

J. Org. Chem.

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Substances whose visible light absorption changes markedly with temperature are said to be thermochromic. Dinaphthospiropyran (I) is a typical thermochromic compound and a representative of a group in which thermochromism is common1 (1). It forms colorless solutions in cold xylene, but when these solutions are heated to about 100°, they become purple, and the color deepens as the temperature is raised. The changes are reversible. The colored solutions are stable to air, to hydrogen, and to hydroquinone; but they are bleached by piperidine.Color development, obviously not caused by formation of free radicals, was first ascribed to the development of a quinoid compound (II) ( 2), but now a zwitterion (III) (3) is usually preferred. Bleaching by piperidine has been used as evidence against the quinoid structure, because quiñones are not ordinarilydecolorized by piperidine. Apparent parallelism in base strengths and thermochromic tendencies in a series of spiropyrans was believed to indicate the zwitterionic structure (4). Some basis for the contrary view has been found in the discovery that dipole moments of thermochromic spiropyrans do not change significantly with temperature (5), but in the absence of information as to concentration of colored substance in hot solutions, it appears that deductions based on physical properties of such solutions are apt to be misleading. SUMMARY Thermochromism, the reversible development of color which occurs when certain compounds are heated, appears to be caused in spiropyrans by partial ring opening. The colored substance derived from a spiropyran is a resonance hybrid of a quinoid and a zwitterionic form. Such thermochromism is inhibited by structural

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112. Styrylpyrylium salts. Part XIV. Further study of the colour phenomenon associated with benzonaphtha- and dinaphtha-spiropyrans

Cited by 18 publications

References 0 publications

Tumor suppressive activities of solvatochromic 3,3′‐azadimethylene dinaphthospiropyran in colon cancer model

Tumor suppressive activities of solvatochromic 3,3′‐azadimethylene dinaphthospiropyran in colon cancer model

General Methods of Preparing Chromones

Steric Factors in Thermochromism of Spiropyrans and in Reactivities of Certain Methylene Groups

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