A Simple Synthetic Method for Tetraaza[3.3.3.3]meta- and paracyclopanes by Alkylation of<i>N</i>-Substituted Trifluoroacetamide

Shinmyozu, Teruo; Shibakawa, Nobuhiko; Sugimoto, Kenichi; Sakane, Hiroko; Takemura, Hiroyuki; Sako, Katsuya; Inazu, Toshiyuki

doi:10.1055/s-1993-26038

Cited by 20 publications

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“…Their physical data were identical to those already reported. 5 In the present reaction, no higher oligomer, such as a hexamer (cf., Scheme 1, 4, n = 3) 5,7-10 was obtained. As previously discussed, direct coupling of 1,4-bis[(trifluoroacetylamino)methyl]benzene with 1,4-bis(bromometh-…”

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confidence: 75%

“…2 Thus, it would be interesting to reveal the details of the unique photoproperties of the diazacyclophane system. Although the diaza[3 2 ]cyclophane 11 has been prepared by Shinmyozu et al, 5 the yield was quite low. 6 Thus, it is highly desirable to establish an efficient synthetic route to the azacyclophane system.…”

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confidence: 99%

“…Conventionally, there are two methodologies for the construction of diaza[3 2 ]cyclophane as shown in Scheme 1; (i) cyclization of amide-activated diamine 1 and xylylene dihalide 2 (path a) 5,7,8 and (ii) coupling of 4-toluenesulfonamide (Ts-amide) or cyanamide 5 with xylylene dihalide 2 (path b). 9-11 Among these procedures, the Tsamide methods (Scheme 1, path a, R = Ts; path b, R = Ts) have been used as practical routes to the diaza[3 2 ]cyclophane skeleton 3, 7,10 while the others (Scheme 1, path a, R = COCF 3 , PO(OEt) 2 ; path b, R = CN) resulted in the formation of higher oligomers 4 rather than the desired diaza[3 2 ]cyclophane 3.…”

mentioning

confidence: 99%

“…9-11 Among these procedures, the Tsamide methods (Scheme 1, path a, R = Ts; path b, R = Ts) have been used as practical routes to the diaza[3 2 ]cyclophane skeleton 3, 7,10 while the others (Scheme 1, path a, R = COCF 3 , PO(OEt) 2 ; path b, R = CN) resulted in the formation of higher oligomers 4 rather than the desired diaza[3 2 ]cyclophane 3. 5,[7][8][9][10][11] The Ts-amide methods are thus effective for preparing the Ts-amide derivative of diaza[3 2 ]cyclophane. However, absorption of the aromatic Ts-amide chromophores overlaps with that of the diaza[3 2 ]cyclophane chromophore thus preventing evaluation of the photoproperties of the aza[3 2 ]cyclophane system.…”

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A Convenient Synthesis of Trifluoroacetamide Derivatives of Diaza[3₂]cyclophanes and Triaza[3₃]cyclophanes

Okamoto¹,

Takemura

Satake³

2008

Synthesis

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The diaza[3 2 ]cyclophane skeleton has been constructed by the bis-N-alkylation of 1,4-bis [(4-nitrophenylsulfonylamino)methyl]benzene with 1,4-bis(halomethyl)benzene in the presence of sodium hydride. The 4-nitrophenylsulfonyl (Ns) amides in the bridge chains of the cyclophane were effectively deprotected by sodium ethanethiolate and the resulting free amine moieties were reprotected as the trifluoroacetamide under mild conditions to afford 3,7-bis(trifluoroacetyl)-3,7-diaza-1,5(1,4)-dibenzenacyclooctaphane in 26% overall yield. This Ns-amide method has also been applied for the preparation of a higher homologue, the trifluoroacetamide derivative of triaza[3 3 ]cyclophane, 3,5,7-tris(trifluoroacetyl)-3,7,10-triaza-1,5(1,3,5)-dibenzenabicyclo[3.3.3]undecaphane, in 18% overall yield. Thus, the present procedure provides a convenient synthetic route to azacyclophane derivatives possessing trifluoroacetamide groups in the bridge chains.Cyclophanes possessing nitrogen atoms in their bridge chains have been of photochemical interest because they sometimes display different reactions than those of the corresponding carbon-bridged analogues or nonbridged chromophores. [1][2][3][4] We have recently disclosed that diaza[3 2 ]cyclophane 11 afforded an interesting octahedrane cage upon photoirradiation, while the corresponding carbon-bridged analogue, [3 2 ]cyclophane, was almost inert under the same conditions. 2 Thus, it would be interesting to reveal the details of the unique photoproperties of the diazacyclophane system. Although the diaza[3 2 ]cyclophane 11 has been prepared by Shinmyozu et al., 5 the yield was quite low. 6 Thus, it is highly desirable to establish an efficient synthetic route to the azacyclophane system.Conventionally, there are two methodologies for the construction of diaza[3 2 ]cyclophane as shown in Scheme 1; (i) cyclization of amide-activated diamine 1 and xylylene dihalide 2 (path a) 5,7,8 and (ii) coupling of 4-toluenesulfonamide (Ts-amide) or cyanamide 5 with xylylene dihalide 2 (path b). 9-11 Among these procedures, the Tsamide methods (Scheme 1, path a, R = Ts; path b, R = Ts) have been used as practical routes to the diaza[3 2 ]cyclophane skeleton 3, 7,10 while the others (Scheme 1, path a, R = COCF 3 , PO(OEt) 2 ; path b, R = CN) resulted in the formation of higher oligomers 4 rather than the desired diaza[3 2 ]cyclophane 3. 5,7-11 The Ts-amide methods are thus effective for preparing the Ts-amide derivative of diaza[3 2 ]cyclophane. However, absorption of the aromatic Ts-amide chromophores overlaps with that of the diaza[3 2 ]cyclophane chromophore thus preventing evaluation of the photoproperties of the aza[3 2 ]cyclophane system. Additionally, deprotection of the Ts-amide moieties required severe conditions, such as Birch reduction conditions or a highly acidic medium. 7,10 Thus, a simple synthetic route is needed for the construction of an azacyclophane possessing bridge nitrogen substituents that display no absorption band in the absorption region of the azacyclophane chromophore (>25...

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confidence: 75%

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confidence: 99%

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confidence: 99%

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confidence: 99%

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A Convenient Synthesis of Trifluoroacetamide Derivatives of Diaza[3₂]cyclophanes and Triaza[3₃]cyclophanes

Okamoto¹,

Takemura

Satake³

2008

Synthesis

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“…During this reaction, the authors isolated products of 2:2, 3:3 and the desired 4:4 cyclization. The use of p-phenylenebistrifluoroacetamide offers a more facile and practical synthetic method to prepare the cyclophanes and allows the preparation of these macrocycles in gram quantities (Scheme 26) [64].…”

Section: Macrocyclic Compounds Formed By Six New Bondsmentioning

confidence: 99%

One‐step syntheses of macrocyclic compounds: A short review

Krakowiak

Izatt

Bradshaw

2001

Journal of Heterocyclic Chem

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Macrocyclic ligands have been prepared by various one-step cyclooligomerization processes. This short review covers one-step cyclization reactions involving the formation of four to twenty or more new covalent bonds. The new macrocycles reviewed include cyclophanes, biscrown ethers, cryptands, macrolides, cage compounds, calixarenes, homocalixarenes, cucubiturils, and supercryptands all prepared by one-step syntheses.

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Syntheses of Macrocyclic Compounds Possessing Fluorine Atoms in Their Cavities: Structures and Complexation with Cations

Takemura¹,

Kariyazono

Yasutake

et al. 2000

Eur. J. Org. Chem.

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A Simple Synthetic Method for Tetraaza[3.3.3.3]meta- and paracyclopanes by Alkylation ofN-Substituted Trifluoroacetamide

Cited by 20 publications

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A Convenient Synthesis of Trifluoroacetamide Derivatives of Diaza[3₂]cyclophanes and Triaza[3₃]cyclophanes

A Convenient Synthesis of Trifluoroacetamide Derivatives of Diaza[3₂]cyclophanes and Triaza[3₃]cyclophanes

One‐step syntheses of macrocyclic compounds: A short review

Syntheses of Macrocyclic Compounds Possessing Fluorine Atoms in Their Cavities: Structures and Complexation with Cations

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A Simple Synthetic Method for Tetraaza[3.3.3.3]meta- and paracyclopanes by Alkylation ofN-Substituted Trifluoroacetamide

Cited by 20 publications

References 0 publications

A Convenient Synthesis of Trifluoroacetamide Derivatives of Diaza[32]cyclophanes and Triaza[33]cyclophanes

A Convenient Synthesis of Trifluoroacetamide Derivatives of Diaza[32]cyclophanes and Triaza[33]cyclophanes

One‐step syntheses of macrocyclic compounds: A short review

Syntheses of Macrocyclic Compounds Possessing Fluorine Atoms in Their Cavities: Structures and Complexation with Cations

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A Convenient Synthesis of Trifluoroacetamide Derivatives of Diaza[3₂]cyclophanes and Triaza[3₃]cyclophanes

A Convenient Synthesis of Trifluoroacetamide Derivatives of Diaza[3₂]cyclophanes and Triaza[3₃]cyclophanes