Acenaphthenequinone, reactions

Development of the acenaphthenequinone reactions 12H(85)1869. Diels—Alder reactions of fluorinated alkynylphosphonates to give fluori-nated heterocyclic organophosphonates 13JFC(152)29. N,N-Dimethylformamide A multipurpose building block 12AG(E) 9226. 

Acenaphtheno[l,2-e][l,2,4]triazolo[4,3-h][l,2,4]triazine 747 was prepared (79AP147) by cyclizing 3-hydrazinoacenaphtheno[l,2-e][l,2,4]tria-zine 746 with formic acid. Reaction of 746 with sugars gave the hydrazones, which cyclized with iron(III) chloride to give 748 (93BCJ00). Similarly, the acetaldehyde derivative of 746 was cyclized to 748. The structure of 748 (R = Me) rather than 747 (R = Me) was deduced by unequivocal synthesis of the latter by condensation of acenaphthenequinone with 3,4-diamino[l,2,4]triazole (Scheme 155). 

Th are prqtar hy the conventional SchifF-base condensation of two equivalents of the draired 2,6-dialkyl substituted aniline with acenaphthenequinone. The pre-catalysts, formed by addition of the lipmds to (DME)NiBr2. The reactions were complete in aU cases in less than six hours, and ftie products are isolated by filtration or evaporation and washed with ether to yield desired catalyst pimirsors in quantitative yields. 

Diamino-4(3/f)pyrimidinones on reaction with a-diketones give (84JHC1537 85JHC1317) pyrimido[l,2- ][l,2,4]triazines 240. Similarly, the condensation of 2,3-diamino-4(3i/)pyrimidinones with cyclohexandi-one, 1,2-naphthoquinone, acenaphthenequinone, and phenanthraquinone gives the respective condensed pyrimidotriazines of general structure 241 (85JHC1317). 

The reaction sequence outlined in Scheme 20.30 for the preparation of the chlorinated enyne-allenes was successfully adopted for the synthesis of the C44H26 hydrocarbon 251 having a carbon framework represented on the surface of C60 (Scheme 20.50) [83]. Condensation of the monoketal of acenaphthenequinone (243) with the lithium acetylide 101 afforded the propargylic alcohol 244. On exposure to thionyl chloride, 244 underwent a cascade sequence of reactions as described in Scheme 20.30 to furnish the chloride 248. Reduction followed by deprotection produced 250 to allow a repeat of condensation followed by the cascade transformation and reduction leading to 251. 

The bismuth ylides, Ph3Bi=CHCOR, do not react with simple ketones and electron-rich olefins probably because of their relatively low electrophilic character. However, Ph3Bi=CHCOR reacts with a-keto esters [46, 67, 68], benzils [46, 67-69], orf/to-quinones [46, 67, 68], and acenaphthenequinone [70] to give epoxides, (9-arovl enolates, 3-hydroxytropones, and 3-hydroxyphenalenones, respectively, accompanied by the formation of Ph3Bi (Scheme 11). In particular, transposition and ring expansion reactions are of interest from a mechanistic point of view, since these reaction modes are unprecedented in ylide chemistry. 

A convenient route to pyridazine derivatives is found in the reaction of monohydrazones of 1,2-diketones with DMAD. The reaction of benzil monohydrazone with DMAD, for example, gives a mixture of products consisting of dimethyl 5,6-diphenylpyridazine-3,4-dicarboxylate (135), benzil dimethyl oxaloacetate ketazine (136) and benzil bisketazine (137). A similar reaction of acenaphthenequinone... 

Sequential SET desilylation has been used to generate a-amino radicals. The mechanistic and synthetic aspects of the reaction have been briefly surveyed.283 Thus irradiation of A, N- d i e t h y 11 r i m e t h y I si I yl meth y I a m i n e with acenaphthenequinone in acetonitrile or methanol produces 2-hydroxy-2-[(diethylamino)methyl]acenaphthylen-1-one.284... 

Wittg reaction of a bis-ylide with acenaphthenequinone 667 or dione 669 affords fused thiophene 668 <1997PS419> or 670 <1999BCJ1597>, respectively (Equation 38). 

This point illustrated by results of an investigation 166) of reactions of phenanthre-nequinone and acenaphthenequinone in the presence of oxygen. Major products in the presence of olefins were the dione-olefin 1 1 adducts (cf section IXA) with litle if any epoxide formed. Biacetyl remains the dione of choice for photoepoxidation. 

Fused acenaphthylene derivative was prepared (52%) by Westphal condensation (89H2369). The reaction of l-ethoxycarbonylmethyl-2,6-di-methypyridinium salt and acenaphthenequinone in the presence of dibut-ylamine gave quinolizinium salt 241. Intramolecular Claisen reaction of 241 occurred under the reaction conditions to afford cyclazinone 242, which was treated with HBr to yield 243. 

The reaction of biacetyl and dioxane was complex affording modest yields of 1,2-adduct, diketopinacol 63, acetyldioxane, and compound 91 whose origin is obscure. Benzil in diethyl ether furnished benzilbenzoin (63) a mixture from which no pure products were isolated was obtained with dioxane. A similar result was obtained with acenaphthenequinone and dioxane. Tetrachloro-o-benzoquinone and dioxane afford 20% of a 1,4-adduct analogous to 87 the remaining products were not characterized. 

The reaction of acenaphthenequinone monohydrazone (92) with diethyl ethynedicarboxylate in boiling tetrahydrofuran gave the fully unsaturated fused 1,4,5-oxadiazepine derivative (93) (12% yield), together with two other products (Equation (3)) <72IJC875>. 

Novel dicyano-functionalized spiropyrrolizidine (166 and 167) and spiropyrro-lidine (168 and 169) were synthesized in a regio- and stereoselective manner from the reaction of various arylidenemalononitriles (163) with nonstabilized azomethine ylides generated from isatin (155)/acenaphthenequinone (159) and proline (160)/ sarcosine (164)/N-phenylglycine (165). The reactions were carried out under both conventional heating and ultrasonic irradiation conditions (Scheme 8.53). In general, improvement in rates and yields were observed when the reactions were carried out under sonication compared with classical conditions (Rezaei et al. 2011). 

The reaction of l,2-bis(diphenylphosphino)ethane with substimted o-benzoquinones affords bis(6-hydroxycyclohexa-2,4-dienone) derivatives. Treatment of the same reagent with o-naphthoquinone, phenanthrenequinone and acenaphthenequinone gave the respective bis(diphenylphosphoryl)ethylidenes or diacenaphthylenone derivatives. On the other hand, p-quinones react with l,2-bis(diphenylphosphino)methane to yield the corresponding 4-hydroxycyclohexa-2,5-dien-l-ones. ... 

Using isatines instead of aromatic aldehydes in a related series of reactions carried out in glycerol resulted in the formation of spiro-fused indol-2-ones 110-112 and 165-167 with good yields (Scheme 98) [141]. The same type of reaction was also successfully performed xmder similar conditions using acenaphthenequinone or ninhydrine instead of isatines. 

A variety of substituted spiroacenaphthylene derivatives 39 were also synthesized in water from the one-pot multicomponent reaction of acenaphthenequinone (24), cyclic 1,3-diketone, and malononitrile/ethyl cyanoacetate 3 in the presence or absence of catalysts under reflux conditions (Scheme 21) [118,120,122,123]. 

Strained molecules based on naphthalene have been described.Lithiation of 1,8-di-iodonaphthalene and 5,6-dibromoacenaphthene and the subsequent cycloaddition reaction with acenaphthenequinone and pyracenequinone gives diols, which with HF yield the acenaphth[l,2-a]acenaphthalenes (289), (290), and (291). 

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