- Synthesis and enantiomer separation of 5-(1-(3,5-Dinitrobenzoylamino)pent-4-enyl)acenaphthene
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A new racemic (±) 5-(1-(3,5-dinitrobenzoylamino)pent-4-enyl)-acenaphthene was synthesized and successfully separated into enantiomers on chiral HPLC. The synthetic approach to the 5-(1-(3,5- dinitrobenzoylamino)pent-4-enyl)acenaphthene is via Friedel-Crafts acylation reaction to the acenaphthyl ring, α-H substituent reaction to the ketone, deoxidization reaction to the ketone and amidation reaction to the amidocyanogen. The chemical structure of this compound was characterized by FT-IR and 1H NMR.
- Xu, Chao,Luo, Wen-Feng,Li, Li-Jun,Yao, Shun,Song, Hang
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experimental part
p. 3923 - 3928
(2010/11/16)
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- Reduction of diaryl alkenes by hypophosphorous acid-iodine in acetic acid
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A mixture of 50% aqueous H3PO2 and I2 (in catalytic amount) in HOAc efficiently reduces aryl alkenes to the corresponding alkanes in high yield. Addition of acetic anhydride to the medium results in ring-acetylation (or N-acetylation in the case of amines). H3PO2 costs only one-fifth as much as hydriodic acid on a mole basis and one mole of H3PO2 produces four moles of HI, resulting in a 20-fold cost advantage for H3PO2/I2 over aqueous HI as a source of HI.
- Fry, Albert J.,Allukian, Myron,Williams, Allison D.
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p. 4411 - 4415
(2007/10/03)
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- Reaction of substituted 5-bromoacenaphthenes with the catalytic reduction system NiCl2-2,2'-bipyridyl (or 1,10-phenanthroline)-Zn
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Transformations of substituted 5-bromoacenaphthenes under the action of a catalytic reduction system NiCl2-2,2'-bipyridyl (or 1,10-phenanthrolyne)-Zn in DMF and DMA was studied. Two types of transformation are shown to be characteristic for the studied compounds: reductive coupling with formation of the corresponding 5,5'-biacenaphthenyl and halogen elimination with hydrogen replacing the halogen. Yields of the coupling products and that of dehalogenation are found to depend substantially on the nature of the substituents in the nanhfhalene ring.
- Adonin,Ryabinin,Starichenko
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p. 913 - 915
(2007/10/03)
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- Flash vacuum thermolysis of 5-(1-chloroethenyl)acenaphthene. A short synthesis of pyracylene and its bechaviour under high temperature conditions
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Flash vacuum thermolysis (FVT) of 5-(1-chloroethenyl)acenaphthene (4) has been found to give rise to pyracylene (1).Pure 1 can be isolated from the 1100 deg C pyrolysate by recrystallization at -20 deg C.The temperature conversion data reveal that 1 decomposes and rearranges at T 1000 deg C; acenaphthylene (11), 1-ethynyl- (23) and 3-ethynyl-acenaphthylene (24) have been identified.The formation of 23 and 24 indicates that 1 rearranges to the transient cyclopentacenaphthylene (20) via a single ring-contraction-ring-expansion mechanism under FVT conditions.The experimental data are supported by semiempirical AM1 calculations of the C14H8 potential energy surface.
- Sarobe, Martin,Flink, Simon,Jenneskens, Leonardus W.,Zwikker, Jan W.,Wesseling, Jolanda
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p. 2125 - 2132
(2007/10/03)
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- Kinetic Control and Locoselectivity in the Electrophilic Cleavage of Allylic Aluminum Compounds: Reactions of Acenaphthenylaluminum Reagents with Carbonyl Substrates
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The benzylic reagent 1-acenaphthenyldiisobutylaluminum, which is formed by the addition of diisobutylaluminum hydride to acenaphthylene, exhibits a 1H NMR spectrum at 25 deg C consistent with a C1-Al bond.At 110 deg C the carbon-aluminum bond undergoes configurational inversion, as evidenced by the magnetic equivalence of the cis and trans C2 protons.At -78 deg C this aluminum compound reacts with ketones to give, upon hydrolysis, 65-75percent of 3-(α-hydroxy-disubstituted methyl)-1,3-dihydroacenaphthylenes, which undergo acid-catalyzed isomerization to 3-(α-hydroxy-disubstituted methyl)acenaphthenes and which dissociate into acenaphthene and the ketone upon contact with Pd.On the other hand, the same reagents at 80-100 deg C lead to the formation of 75-85percent of 1-(α-hydroxy-disubstituted methyl)acenaphthenes.Similiar reactions with acyl chlorides (RCOCl, where R = Me, Et, Ph) and with Me3SiCl laed to 3-acylacenaphthenes and 1-(trimethylsilyl)acenaphthene, respectively.The stereochemically defined adduct of acenaphthylene and diisobutylaluminum deuteride, (cis-2-deuterio-1-acenaphthenyl)diisobutylaluminum diethyl etherate, is found to react with 9-fluorenone at 65 deg C to yield a 1:1 mixture of cis- and trans-2-deuterio-1-acenaphthenylcarbinols.Similarly, treatment of the same aluminum reagent with O2 gives a 1:1 mixture of cis- and trans-2-deuterio-1-acenaphthenols.The magnetically shielded C8 or ortho proton in the original aluminum adduct offers a valuable monitor of the extent of complexation at the C1-Al bond.The present findings demonstrate that electrophilic attack at the ortho position (leading to C3 substitution) in the kinetically controlled process, while rearrangement to C1 is thermodynamically determined.
- Eisch, John J.,Fichter, Kenneth C.
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p. 4631 - 4639
(2007/10/02)
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