New Applications of Crown Ethers. II. Synthesis of 4′-Formylbenzocrown Ethers

Wada, Fumio; Hirayama, Hiroshi; Namiki, Hiroshi; Kikukawa, Kiyoshi; Matsuda, Tsutomu

doi:10.1246/bcsj.53.1473

Cited by 66 publications

(31 citation statements)

References 6 publications

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“…When DB18C6 was diformylated by the Smith modification [21] of the Duff reaction [22], a 1 : 1 mixture of anti and syn isomers 6 and 8 was obtained (Scheme 2) [23]. Their reduction to 7 and 9, respectively, conversion to the bis-malonates 4 and 10, and treatment of the mixture under modified Bingel-reaction conditions afforded the trans-1 ((AE)-1, 15%), trans-2 ((AE)-2, 1.5%), and trans-3, ((AE)-3, 20%) isomers, which were separated by flash chromatography on SiO 2 -H ( AcOEt/PhMe 1 : 1).…”

mentioning

confidence: 99%

Cyclophane-Type Fullerene-dibenzo[18]crown-6 Conjugates withtrans-1,trans-2, andtrans-3 Addition Patterns: Regioselective Templated Synthesis, X-Ray Crystal Structure, Ionophoric Properties, and Cation-Complexation-Dependent Redox Behavior

Bourgeois

Seiler

Fibbioli

et al. 1999

HCA

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mentioning

confidence: 99%

Cyclophane-Type Fullerene-dibenzo[18]crown-6 Conjugates withtrans-1,trans-2, andtrans-3 Addition Patterns: Regioselective Templated Synthesis, X-Ray Crystal Structure, Ionophoric Properties, and Cation-Complexation-Dependent Redox Behavior

Bourgeois

Seiler

Fibbioli

et al. 1999

HCA

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“…Reaction of dibenzo-18-crown-6 (DBC) with hexamethylenetetramine in the presence of trifluoroacetic acid gave bis(4'-fomylbenzo)-18-crown-6 (BFBC) according to the literature method. 30 After separation, BFBC was reduced by sodium borohydride to yield bis(4'-hydroxymethylbenzo)-18-crown-6 (BHMBC). Reaction of BHMBC with 2-(bromomethyl)naphthalene in the presence of metal sodium in DMF produced (2-naphthyl-derivative-benzo)-(4'-hydroxymethylbenzo)-18-crown-6 (Np-C-OH).…”

Section: Instrumentationmentioning

confidence: 99%

“…30 A mixture of dibenzo-18-crown-6 (DBC) (10.8 g, 0.03 mol), trifluoroacetic acid (0.21 mol) and hexamethylenetetramine (8.8 g, 0.02 mol) was stirred at 90 o C under nitrogen for 12 h. After the mixture was cooled, 50 ml of concentrated KOH and 200 ml of water were successively added. The product was precipitated as a brown solid.…”

Section: 31112-bis(4′-formylbenzo)-18-crown-6 (Bfbc)mentioning

confidence: 99%

Intramolecular triplet energy transfer in benzophenone-{crown ether}-naphthalene system

Xu¹,

Chen²,

Wu³

et al. 2003

Arkivoc

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Bichromophoric compound benzophenone-{crown ether}-naphthalene (Bp-C-Np) was synthesized and its photophysics was examined. Steady state and time-resolved spectroscopic measurements indicate that intramolecular energy transfer from the triplet state of the benzophenone chromophore to the naphthyl group in Bp-C-Np occurs with efficiency of ca. 33% and rate constant of ca. 3.3 × 10 5 s -1 . This long-distance triplet energy transfer is proposed to proceed via a through-bond exchange mechanism.

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“…4'-Formylbenzo-15-crown-5 10 was synthesized from benzo-15-crown-5 by Vilsmeier formylation according to the method described by Hyde et al [16] or by introduction of the carbonyl group with hexamethylenetetramine and trifluoroacetic acid according to Wada et al [17]. For the condensation with malononitrile or 2-amino-1,1,3-tricyanopropene cadmium iodide must be used as catalyst, according to Prajapati and Sandhu [18].…”

Section: ____________________________________________________________mentioning

confidence: 99%

Spacer-chromoionophores - polymethine dye substituted aza-crown ethers with increased complexation ability

Boila‐Göckel¹,

Junék

1999

J. prakt. Chem.

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Chromoionophores are crown ether derivatives, which contain a chromophoric group [1][2][3]. These functional dyes are of a great interest for analytical applications [4,5], especially in medical diagnostics and therapy. A great number of chromo-and also fluoroionophores, starting from aldehydes of N-phenyl-aza-15-crown-5 or N-phenyl-aza-18-crown-6 are described in the literature [6 -11]. Substitution of the aminic H-atom in aza-crowns leads to nitrogen-pivot lariat crowns, and it was shown that alkyl groups increase the binding strength of the metal complexes [12 -14]. The present paper deals with the synthesis of deeply colored polymethine crown ether derivatives and the influence of the electron acceptor properties of the side chain on the complexation, depending upon conjugation of the chromophore with the nitrogen of the aza-crowns. Abstract. Aromatic aldehyde derivatives of N-phenyl-aza-15-crown-5 2, N-phenyl-aza-18-crown-6 8, and benzo-15-crown-5 10 are condensed with malononitrile and 2-amino-1,1,3-tricyano-1-propene to give light yellow to orange colored crown ether derivatives 4, 5a, 9a, 11, and 12. 5a and 9a were acylated with ethyl chloroformate to give the magenta colored dyes 5b and 9b, respectively. By condensation of N-(4-nitrosophenyl)-aza-15-crown-5 3 with 2-amino-1,1,3-tricyano-1-propene the magenta dye 6a is obtained. Acylation of 6a with ethyl chloroformiate leads to the deep blue colored dye 6b. In these derivatives the nitrogen or oxygen atoms of the crown ethers are part of the chro-mophoric system and binding properties are affected. Further chromophoric derivatives of aza-crown ethers are stu-died in which these are separated from the chromophoric moiety by a spacer. N-(ω-chloroalkyl)-N-alkylanilines 14a -c were attached to aza-15-crown-5 13a and aza-18-crown-6 13b to yield the spacer crown ether derivatives 15a -c and 16a -c, respectively. The formylated spacer crown ether derivatives 17a -c and 18b were condensed with 2-amino-1,1,3-tricyano-1-propene to give the orange spacer-chromoionophores 19a -c and 20. In these crown ether derivatives the extended conjugation is interrupted by the spacer and good binding properties are obtained. The complex formation constants of the crown ether derivatives with Na + and K + are determined using 1 H NMR spectroscopy. dimeric malononitrile (2-amino-1,1,3-tricyanopropene), respectively, is a Knoevenagel condensation which occurs under mild conditions using piperidine as catalyst. The yellow colored chromoionophores 4 and 5a, showing UV/Vis absorption maxima at about λ max = 430 nm, are obtained with a quite good yield.13-(4-Nitrosophenyl)-1,4,7,10-tetraoxa-13-azacyclopentadecane 3 was as well prepared according to Dix and Vögtle [6]. With the dimeric malononitrile it afforded with good yield the magenta colored dye 6a (λ max = 524 nm, CH 3 CN).N-Phenyl-aza-18-crown-6 7 was synthesized according to Dix und Vögtle [6], and the corresponding aldehyde 8 similarly to the crown ether aldehyde 2 prepared by Vilsmeier formylation. Formation of side produc...

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New Applications of Crown Ethers. II. Synthesis of 4′-Formylbenzocrown Ethers

Abstract: 4′-Formylbenzo-15-crown-5, -18-crown-6, and bis(4′-formylbenzo)-18-crown-6 were conveniently synthesized in excellent yields by Smith modification of Duff reaction: formylation with hexamethylenetetramine and trifluoroacetic acid or methanesulfonic acid.

Cited by 66 publications

References 6 publications

Cyclophane-Type Fullerene-dibenzo[18]crown-6 Conjugates withtrans-1,trans-2, andtrans-3 Addition Patterns: Regioselective Templated Synthesis, X-Ray Crystal Structure, Ionophoric Properties, and Cation-Complexation-Dependent Redox Behavior

Cyclophane-Type Fullerene-dibenzo[18]crown-6 Conjugates withtrans-1,trans-2, andtrans-3 Addition Patterns: Regioselective Templated Synthesis, X-Ray Crystal Structure, Ionophoric Properties, and Cation-Complexation-Dependent Redox Behavior

Intramolecular triplet energy transfer in benzophenone-{crown ether}-naphthalene system

Spacer-chromoionophores - polymethine dye substituted aza-crown ethers with increased complexation ability

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