Novel Alkylanthracenes Synthesis, Reductive Alkylation, and Reductive Polymerization

Bender, D.; Müllen, Kläus

doi:10.1002/cber.19881210626

Cited by 23 publications

(8 citation statements)

References 25 publications

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“…grade; 1,2-dichlorbenzene, CS 2 and chloroform (for spectroscopy), Fluka puriss. ; deuterochloroform, 99.8 % D, Cambridge Isotopes, 2,3,6,7-tetramethyl-anthracene, [34] 2,6-di-tert-butyl-anthracene; [35] thin-layer chromatography (TLC): POLYGRAMM SIL G/UV 254 plastic plates (CS 2 / hexane 3:1); column chromatography: silica gel H (for TLC), 5 ± 40 mm Fluka. …”

Section: Methodsmentioning

confidence: 99%

Efficient Preparation of Monoadducts of [60]Fullerene and Anthracenes by Solution Chemistry and Their Thermolytic Decomposition in the Solid State

2001

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The efficient preparation of monoadducts of [60]fullerene and seven anthracenes (anthracene, 1-methylanthracene, 2-methylanthracene, 9-methylanthracene, 9,10-dimethylanthracene, 2,3,6,7-tetramethylanthracene, and 2,6-di-tert-butylanthracene) by cycloaddition in solution is described. The seven mono-adducts of [60]fullerene and the anthracenes were characterized spectroscopically and were obtained in good yields as crystalline solids. The monoadducts of [60]fullerene and anthracene, 1-methylanthracene, 2-methylanthracene and 9,10-dimethylanthracene crystallized directly from the reaction mixture. The thermolytic decomposition at 180 degrees C of the crystalline monoadducts of [60]fullerene and anthracene, 1-methylanthracene, 9-methylanthracene and 9,10-dimethylanthracene all gave rise to the specific formation of a roughly 1:1 mixture of [60]fullerene and the corresponding antipodal bisadducts ("trans-1"-bisadducts) of [60]fullerene and the anthracenes. In contrast, the crystalline monoadducts of [60]fullerene and the anthracene derivatives 2-methylanthracene, 2,3,6,7-tetramethylanthracene and 2,6-di-tert-butylanthracene all decomposed to [60]fullerene and anthracenes (without detectable formation of bisadducts) upon heating in the solid state to temperatures of 180 to 240 degrees C. The formation of the antipodal bisadducts from thermolytic decomposition of crystalline samples of the monoadducts was rationalized by topochemical control.

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Section: Methodsmentioning

confidence: 99%

Efficient Preparation of Monoadducts of [60]Fullerene and Anthracenes by Solution Chemistry and Their Thermolytic Decomposition in the Solid State

2001

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“…grade; 1,2-dichlorbenzene, CS 2 , and CHCl 3 (for spectroscopy), Fluka puriss. ; CDCl 3 , 99.8% D, Cambridge Isotopes; 2,3,6,7-tetramethylanthracene, prepared according to Bender and Müllen [26]; 2,6-di(tert-butyl)anthracene, prepared according to Fu and Harvey [27]. [28], no absorption correction, structure solution with SHELXS86 [29], refinement on F 2 with SHELXL93 [30].…”

Section: Experimental Partmentioning

confidence: 99%

Regioselective `One-Pot' Synthesis of Antipodal Bis-adducts by Heating of Solid [5,6]Fullerene-C60-Ih and Anthracenes, Preliminary Communication

Duarte-Ruiz

Wurst

Kräutler

2001

HCA

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Antipodal (trans-1) Diels-Alder bis-adducts 3 and 7 ± 9 of [5,6]fullerene-C 60 -I h (1) with some anthracenes were prepared highly regioselectively by heating mixtures of the solid 1 and anthracene or of (one of) three alkyl-substituted anthracenes in the absence of solvents (Scheme 2). Other bis-cycloadducts were not detected, but lesser amounts of mono-cycloadducts 2 and 4 ± 6, respectively, were also formed. Heating of solvent-free mixtures of 1 and three other alkyl-substituted anthracenes did not result in a detectable amount of (antipodal) bis-cycloadducts. The antipodal bis-adduct 7 of 1 and of 1-methylanthracene was analyzed by X-ray crystallography. The preparative outcome of heating of anthracenes and solid 1 parallels the result of the heating of the corresponding crystalline mono-adducts of anthracenes and 1. Both approaches reveal a remarkably consistent dependence of the reaction upon the presence and position of alkyl substituents at the anthracene unit. The regioselective assembly of antipodal bis-adducts from anthracene(s) and 1 cannot be rationalized by their (inherent molecular) stability, but it indicates the crucial control of the lattice. Introduction. ± Fullerenes, the spherical C-molecules [1 ± 3], are fascinating targets of chemistry, which also have enriched several other areas of the natural sciences [4 ± 6]. The original synthetic interests concerned the preparation of a variety of uniformly (mono)functionalized fullerenes [4] [6 ± 8]. More recently, the regio-and stereoselectivity of multifunctionalization reactions of the fullerenes has become a central focus, for the purpose of exploiting the spherical and polyunsaturated nature of the fullerenes [5] [6] [9 ± 12]. Several elegant synthetic strategies were developed, among these, Diederichs method of tether-directed remote functionalization [5] [9] and the reversible template-directed activation of fullerenes, used by Hirsch, Rubin, and others [6c] [10] [12c] [13].The high symmetry and pronounced dienophilic reactivity of the electrophilic [5,6]fullerene C 60 (1) rendered 1 an attractive target for a variety of [4 2]-cycloaddition reactions, which were found to occur at one of the 30 equivalent (6,6)-bonds of 1 exclusively [5] [6]. Cyclic dienes, anthracenes, and other polycyclic aromatics proved to represent useful addends in mono-and multiple cycloaddition processes with C 60 [8] [12] [14]. The mono-adduct 2 (9',10'-dihydro[9,10]ethanoanthra [11',12': 1,9][5,6]fullerene-C 60 -I h ) of anthracene and of C 60 can easily be prepared

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“…9 However, the limitation of this method was the difficult preparation of 2,3-dialkyl-1,3-butadienes, which are usually synthesized by alkylation of the dianion of 2,3-dimethyl-1,3-butadiene with 1-halo-alkanes. 7 Indeed, Bates has reported the formation of this dianion by deprotonation of 2,3-dimethyl-1,3-butadiene with a mixture of n-butyllithium and potassium tert-butoxide in pentane. 10 To optimize the yield of Diels-Alder reaction, the resulting dienes must be purified by distillation.…”

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confidence: 99%

“…As bioreductible agents, they constitute potential substrates for the radical nucleophilic substitution (S RN 1 reaction). 6 In the anthraquinone series, the method of choice for the synthesis of dialkyl-substituted compounds 7,8 is the Diels-Alder reaction between 1,4-naphthoquinone and a 1,3-diene, followed by dehydrogenation of the obtained primary tricyclic adduct. 9 However, the limitation of this method was the difficult preparation of 2,3-dialkyl-1,3-butadienes, which are usually synthesized by alkylation of the dianion of 2,3-dimethyl-1,3-butadiene with 1-halo-alkanes.…”

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An Original One-Pot Synthesis of Dialkyl-Substituted Anthraquinones

Vanelle¹,

Terme²,

Maldonado³

et al. 1998

Synlett

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2,3-Bis(chloromethyl)-1,4-naphthoquinone reacts with primary nitroalkanes in a one-pot synthesis to give a series of anthraquinones bearing two n-alkyl substituents at C-2 and C-3 in good yields. The reaction is shown to proceed by two consecutive S RN 1 processes followed by base-promoted nitrous acid elimination, electrocyclic ring-closure and dehydrogenation. In comparison with the classical Diels-Alder reaction, the advantage of this route is the simplicity of starting-material preparation.Due to the presence of the quinone ring in numerous biologically active compounds 1,2 as well as to their use as auxiliaries in organic synthesis and in dye industry, 3,4 quinonoid compounds continue to attract interest. Quinones, and particularly anthracyclines such as adriamycin and daunorubicin, are effective in the palliative management of a wide variety of human malignancies. However, intrinsic and acquired drug resistance as well as undesired effects such as cumulative dosedependent cardiotoxicity 5 limit their clinical utilization. As bioreductible agents, they constitute potential substrates for the radical nucleophilic substitution (S RN 1 reaction). 6 In the anthraquinone series, the method of choice for the synthesis of dialkyl-substituted compounds 7,8 is the Diels-Alder reaction between 1,4-naphthoquinone and a 1,3-diene, followed by dehydrogenation of the obtained primary tricyclic adduct. 9 However, the limitation of this method was the difficult preparation of 2,3-dialkyl-1,3-butadienes, which are usually synthesized by alkylation of the dianion of 2,3-dimethyl-1,3-butadiene with 1-halo-alkanes. 7 Indeed, Bates has reported the formation of this dianion by deprotonation of 2,3-dimethyl-1,3-butadiene with a mixture of n-butyllithium and potassium tert-butoxide in pentane. 10 To optimize the yield of Diels-Alder reaction, the resulting dienes must be purified by distillation. 7In connection with our program directed toward the development of novel synthetic quinone congeners as anticancer agents, we report here a new and easy one-pot preparative method to produce dialkyl-substituted anthraquinones.2,3-Bis(chloromethyl)-1,4-naphthoquinone (1) was prepared by saturating a cooled solution of 1,4-naphthoquinone and aqueous formaldehyde in glacial acetic acid with dry hydrogen chloride, for 2 h, according to Thomson's procedure. 11 Nitroalkanes were commercially available or easily obtained in excellent yields (70-80 %) from primary amines by oxidation with m-chloroperbenzoic acid in refluxing 1,2-dichloroethane. 12 Treatment of the bis-chloride 1 (1 equiv) with the primary nitroalkanes (4 equiv) during 48 h, under standard S RN 1 reaction conditions (inert atmosphere, photostimulation) and in a phase-transfer system 13 (40 % tetrabutylammonium hydroxide in water and toluene), furnished 2,3-dialkylanthraquinones 5 in 52-70 % good yield. 14 As reported previously, 15 two consecutive S RN 1 processes led to the bis-C-alkylation product 2, which, in the presence of an anion excess, underwent double nitrous acid elimin...

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Novel Alkylanthracenes Synthesis, Reductive Alkylation, and Reductive Polymerization

Cited by 23 publications

References 25 publications

Efficient Preparation of Monoadducts of [60]Fullerene and Anthracenes by Solution Chemistry and Their Thermolytic Decomposition in the Solid State

Efficient Preparation of Monoadducts of [60]Fullerene and Anthracenes by Solution Chemistry and Their Thermolytic Decomposition in the Solid State

Regioselective `One-Pot' Synthesis of Antipodal Bis-adducts by Heating of Solid [5,6]Fullerene-C60-Ih and Anthracenes, Preliminary Communication

An Original One-Pot Synthesis of Dialkyl-Substituted Anthraquinones

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