The conversion of 3-methyl-4-benzyl-4-chloro-2-pyrazolin-5-one 10b was catalyzed by a mixture of potassium fluoride and alumina to give
syn-(methyl, benzyl)bimane 6 (62%) without detectable formation of the
anti isomer, A6 [a 1 : 1 mixture (87%) of the isomers 6 and A6 was obtained when the catalyst was potassium carbonate]. In a similar reaction
syn-(methyl,carboethoxymethyl)bimane 7 (15%) with the
anti isomer A7 (36%) was obtained from 3-methyl-4-carboethoxymethyl-4-chloro-2-pyrazolin-5-one 10c .
syn-(Methyl, β-acetoxyethyl)bimane 8 (70%) was obtained from 3-methyl-4-β-acetoxyethyl-4-chloro-2-pyrazolin-5-one 10d (potassium carbonate catalysis) and was converted by hydrolysis to
syn-(methyl, β-hydroxyethyl)bimane 9 (40%). Acetyl nitrate (nitric acid in acetic anhydride) converted
anti-(amino,hydrogen)bimane 11 to
anti-(amino,nitro)bimane 15 (91%),
anti-(methyl,hydrogen)bimane 13 to
anti-(methyl,nitro)(methyl,hydrogen)bimane 16 (57%), and degraded
syn-(methyl,hydrogen)bimane 12 to an intractable mixture. Treatment with trimethyl phosphite converted
syn-(bromomethyl,methyl)bimane 17 to
syn-(dimethoxyphosphinylmethyl,methyl)bimane 18 (78%) that was further converted to
syn-(styryl,methyl)bimane 19 (29%) in a condensation reaction with benzaldehyde. Treatment with acryloyl chloride converted
syn-(hydroxymethyl,methyl)bimane 20 to its acrylate ester 21 (22%). Stoichiometric bromination of
syn-(methyl,methyl)bimane 1 gave a monobromo derivative that was converted in
situ by treatment with potassium acetate to
syn-(acetoxymethyl,methyl)(methyl,methyl)bimane 47 . N-Amino-μ-amino-
syn-(methylene,methyl)bimane 24 (68%) was obtained from a reaction between the dibromide 17 and hydrazine. Derivatives of the hydrazine 24 included a perchlorate salt and a hydrazone 25 derived from acetone. Dehydrogenation of
syn-(tetramethylene)bimane 26 by treatment with dichlorodicyanobenzoquinone (DDQ) gave
syn-(benzo,tetramethylene)bimane 27 (58%) and
syn-(benzo)bimane 28 (29%). Bromination of the bimane 26 gave a dibromide 29 (92%) that was also converted by treatment with DDQ to
syn-(benzo)bimane 28 . Treatment with palladium (10%) on charcoal dehydrogenated 5, 6, 10, 11-tetrahydro-7
H,9
H-benz [6, 7] indazol [1, 2a]benz[g]indazol-7,9-dione 35 to
syn-(α-naphtho)bimane 36 (71%). The bimane 35 was prepared from 1,2,3,4-tetrahydro-1-oxo-2-naphthoate 37 by stepwise treatment with hydrazine to give 1,2,4,5-tetrahydro-3
H-benz[g]indazol-3-one 38 , followed by chlorine to give 3a-chloro-2,3a,4,5-tetrahydro-3
H-benz[g]indazol-3-one 39 , and base. Dehydrogenation over palladium converted the indazolone 34 to 1
H-benz[
g] indazol-3-ol 36 . Helicity for the hexacyclic
syn-(α-naphtho)bimane 36 was confirmed by an analysis based on molecular modeling. The relative efficiencies (RE) for laser activity in the spectral region 500–530 nm were obtained for 37
syn-bimanes by reference to coumarin 30 (RE 100): RE > 80 for
syn-bimanes 3, 5, 18 , and μ-(dicarbomethoxy)methylene-
syn-(methylene,methyl)bimane 22 : RE 20–80: for
syn-bimanes 1,2,4,20,24,26 , and μ-thia-
syn-(methylene,methyl)bimane 50 : and RE 0-20 for 26
syn-bimanes. The bimane dyes tended to be more photostable and more water-soluble than coumarin 30. The diphosphonate 18 in dioxane showed laser activity at 438 nm and in water at 514 nm. Presumably helicity, that was demonstrated by molecular modeling, brought about a low fluorescence intensity for
syn-(α-naphtho)bimane 36 , Φ0.1, considerably lower than obtained for
syn-(benzo)bimane 28 , Φ0.9.
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