Structure of methyl (E)-2-cyano-2-(1-phenyl-4,5-dihydro-1H-tetrazol-5-ylidene)acetate

Zimmermann, H.; Gomm, M.; Wirth, U.; Fischer, M.; Lurz, Claus‐Jürgen; Saalfrank, Rolf W.

doi:10.1107/s0108270189008097

Cited by 5 publications

(4 citation statements)

References 1 publication

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“…A detailed investigation of the vinyl-azides 17 (X = NHR, Y = C(CN)CO 2 Me) revealed that, in this case, a 1,59-ring closure reaction strongly dominates over a 1,5-cyclization to afford tetrazolylidenes 20 (Scheme 6). [18][19][20][21][22][23][24][25] Scheme 7 presents a summary of the various heterocycles accessible from geminal vinyl-diazides.…”

Section: Geminal Amino Vinyl-azides As Synthetic Building Blocksmentioning

confidence: 99%

Roots: From carbenes to allenes and coordination polymers : Ever present never twice the same

Saalfrank

Maid

2005

Chem. Commun.

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The purpose of this Feature Article is to demonstrate that recognizing the similarities in different areas of chemistry allows the prediction of potential results in related fields. For instance, during our investigations of 2,2-diethoxyvinylidene-triphenylphosphorane we became interested in 2,2-diethoxydiazoethene. In order to obtain diazoethenes, we studied vinyl-diazonium salts and geminal vinyl-diazides as precursors. In the course of these investigations, we realized their synthetic potential to produce, via substituent-dependent 1,5-, 3,5-, or 1,5'-cyclization, a whole variety of heterocycles. However, more importantly, we became familiar with the chemistry of carbenes, which prompted an investigation of the carbene-like character of push-pull substituted allenes. Due to the ambiphilicity of their central carbon atom, they readily dimerized. Consequently, our strong interests in push-pull substituted allenes drew our attention to tetradonor substituted allenes, and as a result, we employed tetraethoxyallene as a synthetic equivalent to the fictitious malonic ester 1,1-/1,3-dianion synthon. This concept led to the synthesis of heterocumulenes and to the transallenation reaction to give allenecarboxanilides, which was further developed as a cumuhomologation for the synthesis of butatrienes via haloallenes from propargyl alcohols. The Diels-Alder reaction and intramolecular domino cyclization of multi-functional allenecarboxanilides yielded complex fused heteroarenes. Finally, the 1,5-cyclization of vinyl-azides, reported earlier, provided tetrazolylidene ligands, triggering our interest in supramolecular coordination chemistry, for example, the synthesis of one-, two- and three-dimensional coordination polymers.

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Section: Geminal Amino Vinyl-azides As Synthetic Building Blocksmentioning

confidence: 99%

Roots: From carbenes to allenes and coordination polymers : Ever present never twice the same

Saalfrank

Maid

2005

Chem. Commun.

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“…C 58,08 H 4,21 N 30,95 %. [ 13,14] Ansatz: 1,6 g (25 mmol) NaN3 und 6,1 g (25 mmol C n H9N50 2 (243,22) Ber. C 54,32 H 3,73 N 28,79 %,Gef.…”

Section: B) 45-d Ihydro-lh-tetrazol-5-ylideneunclassified

“…Cu---N(IOB) 257, 196 , (4) 145,1(6) C(2)-C(l 1) 154,1(7) C(4)-N (5) 136,6(5) C(3)-C(9) 141,2(7) N(5)-N (6) 136,8 (6) C(4)-N(8) 133,3(6) N(6)-N (7) 127,2(5) N(5)-C ( 15) 150,3(6) C(9)-N (10) 114,6(7) N(7)-N(8) 136,4(5) C (11)-C ( 13) 152,1 (7) C (11 )-C (12) 153,9(9) C(15)-C (16) 152,7 (7) C (11)-C ( 14) 154,0(8) C(15)-C (18) 151,4 (7) C (15) (4) 604 (3) 30(1) C (4) 1592 (3) -1775 (4) 1609 (4) 29(1) N (5) 2015 (3) -1934 (3) 2817 (3) 33(1) N (6) 1661 (3) -905 (4) 3388 (3) 42(1) N (7) 1050 (3) -185 (4) 2592 (3) 40(1) N (8) 991 (3) -685 (4) 1474 (3) 32(1) C (9) 2657(4) -3366 (5) 713 (4) 40(2) N ( 10) 3414 (4) -4011 (5) 768 (4) 61(2) C (11) 1003 (4) -3342(5) -1605 (4) 43(2) C (12) 2029 (5) -2959 …”

Section: Tab I Ausgewählte Bindungslängen [Pm] Vonunclassified

“…VI zu entnehmen. (11) Arbeitsweise: Zu einer Lösung von 0,200 g (1,0 mmol) Cu(0 A c)2 H20 in 40 ml wasserfreiem Methanol gibt man 0,486 g (2,0 mmol) 4,5-Dihydro-l//-tetrazol-5-yliden 2c (1) 0(1) 1462(2) -680 (4) 569 (3) 40(1) C (2) 2328 (3) -784 (6) 2 (4) 30(2) C (3) 2401 (3) -268(6) -1221 (4) 24(2) C (4) 1527 (3) 594 (5) -1902(4) 26(1) N (5) 558 (3) 977 (5) -1487(3) 29(1) N (6) -56 (3) 1871 (5) -2376(4) 37(1) N (7) 469 (3) 2074 (5) -3327(4) 38(1) N (8) 1469 (3) 1268 (5) -3064 (3) 29(1) C (9) 3446(4) -530(6) -1685(4) 33(2) N (10) 4293 (3) -804 (6) -1983 (4) 49(2) C (11) 2167 (3) 1106 (6) -4050 (4) 30(2) C d 2) 1761(3) 261 (7) -5095 (4) 38(2) C ( 13) 2404 (3) 95 (9) -6073 (4) 44(2) C (14) 3469(4) 740(6) -5951 (5) 43(2) C (15) 3851 (4) 1603 (7) -4900 (5) 44(2) C (16) 3212 (4) 1813 …”

Section: Kristallstrukturanalyse Von 5 [19]unclassified

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Verknüpfung koordinativ ungesättigter Kupfer(II)-Monomere via Cyano-versus Tetrazolyl-Donor/ Linkage of Coordinatively Unsaturated Copper(II) Monomers via Cyano versus Tetrazolyl Donor

Saalfrank

Harbig

Struck

et al. 1996

Zeitschrift Für Naturforschung B

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Reaction of a methanolic copper(II) acetate solution with tetrazolyl enol derivatives 2a (HL2) or 2b (HL3) leads to the formation of the corresponding 2D-coordination polymers 4 (^ [CuL^]) and 5 (^ [CuL2]), respectively. Single-crystal X-ray diffraction of the supramolecular species 4 and 5 established unequivocally the structures of the regioisomeric coordination polymers. On the contrary, reactions of 2c (HL4) with methanolic copper(II) acetate solution and 2b (HL3) with methanolic zinc(II) acetate solution yield mononuclear chelate complexes 11 ([CuL2]) and 12 ([ZnL2(MeOH)2]). The structures of 11 and 12 have been established by X-ray structure analysis. Einleitung A uf dem G ebiet der S upram olekularen C hem ie sind polym ere Ü bergangsm etallkom plexe als bio anorganische M odellsystem e [2], wie auch auf grund ihrer M aterialeigenschaften (Leitfähigkeit, M agnetism us) [3, 4], G egenstand zahlreicher U n tersuchungen. Besondere B edeutung kom m t dabei zw eidim ensionalen (2D ) System en m it kooperati ven Effekten zu. Ein E tappenziel au f dem Weg zu funktionellen supram olekularen M aterialien und N etzw erken ist die K onstruktion von pro g ra m m ier ten selbstorganisierenden System en [5]. Im Rahm en unserer Forschungsarbeiten berich teten w ir über die Synthese und röntgenographische C harakterisierung des neutralen 2D -K oordinationspolym eren3 [6] der allgem einen Zusam m ensetzung ^ [CuL^] [7] (H L 1 = 1, C u V 2 = 6), das ausge hend von K upfer(II)-acetat und dem verbrücken den Pyrrolidin-L iganden 1 [8] bequem zugänglich ist. Die Verknüpfung der aufgrund der beiden CN-Gruppen zw eizähnigen M onom ere 6 untereinander * Sonderdruckanforderungen an Prof. Dr. R. W. Saalfrank. sättigt die C u(II)-Zentren koordinativ ab, wobei sich das entsprechende K oordinationspolym er 3 bil det. Die koordinativ ungesättigten Interm ediate 6 CN R2 Cu(OAc)2 1,2 1 (HL1): X, Y, Z = CH2; R2 = OMe 2a (HL2): X = NR1; Y -Z = HT=N; R1 = CMe3; R2 = CMe3 2b (HL3): X = NR1; Y -Z = N2= N ; R1 = Ph; R2 = Me 2c (HL4): X = NR1; Y -Z = N2= N ; R1 = Ph; R2 = OMe 2d (HL5): X = NR1; Y -Z = N*=N; R1 = CMe3; R2 = OMe 4: (i[C u L 22]) 5: ( J [C uL32]) 11: ([CuL 2])0 9 3 9 -5 0 7 5 /9 6 /0 3 0 0 -0 3 9 9 $ 06.00

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Geminale Vinyldiazide, X. 3,3‐Diazido‐2‐cyanacrylsäure‐methylester: Synthese von Vinylaziden, 4,5‐Dihydro‐1H‐tetrazol‐5‐ylidenen, Oxazolen und N‐Cyaniminen

et al. 1991

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Reaction of methyl 3,3-diazido-2-cyanoacrylate (1) with amines 2 at -30°C yields aminovinyl azides 4. In the presence of equivalent amounts of triethylamine the vinyl azides 4 undergo 1,Y-ring closure to afford the triethylammonium salts 5. Treatment of 5 with hydrochloric acid gives the corresponding 4,5-dihydro-lH-tetrazo1-5-ylidene derivatives 6. In contrast thermolysis of 4 leads via azirines 7 to oxazoles 8. Reaction of vinyl diazide 1 with lysine and cystine, respectively, yields bis(viny1 azides) 9. Triethylamine-induced 1,5'-ring closure of 9 produces the bis(triethy1ammonium) salts 10, which can be transformed under acidic conditions into the corresponding bis(4,5-dihydro-lH-tetrazol-5-ylidene) derivatives 11. With methyl acrylate (

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Structure of methyl (E)-2-cyano-2-(1-phenyl-4,5-dihydro-1H-tetrazol-5-ylidene)acetate

Cited by 5 publications

References 1 publication

Roots: From carbenes to allenes and coordination polymers : Ever present never twice the same

Roots: From carbenes to allenes and coordination polymers : Ever present never twice the same

Verknüpfung koordinativ ungesättigter Kupfer(II)-Monomere via Cyano-versus Tetrazolyl-Donor/ Linkage of Coordinatively Unsaturated Copper(II) Monomers via Cyano versus Tetrazolyl Donor

Geminale Vinyldiazide, X. 3,3‐Diazido‐2‐cyanacrylsäure‐methylester: Synthese von Vinylaziden, 4,5‐Dihydro‐1H‐tetrazol‐5‐ylidenen, Oxazolen und N‐Cyaniminen

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