Abstract
This chapter introduces the nitrile imine 1,3-dipole, examining the history behind its discovery and the core spectroscopic characteristics associated with the species. The different resonance forms available to nitrile imines can often complicate their characterisation, however appropriate interrogation of data such as UV-Vis, IR and NMR spectra may elucidate the core properties of the dipole. Substitution on either terminus of this typically highly reactive intermediate can also improve stability, enabling the isolation of some nitrile imines at room temperature.
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References
Huisgen R, Seidel M, Sauer J, McFarland J, Wallbillich G (1959) Communications: the formation of nitrile imines in the thermal breakdown of 2,5-disubstituted Tetrazoles. J Org Chem 24:892–893
Huisgen R, Sauer J, Sturm HJ (1958) Acylierung 5-substitutierter Tetrazole zu 1.3.4-oxdiazolen. Angew Chemie 70:272–273
Huisgen R, Sauer J, Sturm HJ, Markgraf JH (1960) Ringöffnungen der Azole, II. Die Bildung von 1.3.4-oxdiazolen bei der Acylierung 5-substituierter Tetrazole. Chem Ber 93:2106–2124
Huisgen R, Sauer J, Seidel M (1961) Ringöffnungen der Azole, VI. Die Thermolyse 2.5-disubstituierter Tetrazole zu Nitriliminen. Chem Ber 94:2503–2509
Huisgen R, Sauer J, Seidel M (1960) Ringöffnungen der Azole, IV. Die Synthese von 1.2.4-Triazolen aus 5-substituierten Tetrazolen und Carbonsäure-imidchloriden. Chem Ber 93:2885–2891
Huisgen R, Sturm HJ, Seidel M (1961) Ringöffnungen der Azole, V. Weitere Reaktionen der Tetrazole mit elektrophilen Agenzien. Chem Ber 94:1555–1562
Huisgen R, Grashey R, Seidel M, Knupfer H, Schmidt R (1962) 1.3-Dipolare Additionen, III. Umsetzungen des Diphenylnitrilimins mit Carbonyl und Thiocarbonyl-Verbindungen. Justus Liebigs Ann Chem 658:169–180
Huisgen R, Seidel M, Wallbillich G, Knupfer H (1962) Diphenyl-nitrilimin und seine 1.3-dipolaren additionen an alkene und alkine. Tetrahedron 17:3–29
Huisgen R, Grashey R, Seidel M, Wallbillich G, Knupfer H, Schmidt R (1962) 1.3-Dipolare Additionen, II. Synthese von 1.2.4-Triazolen aus Nitriliminen und Nitrilen. Justus Liebigs Ann Chem 653:105–113
Huisgen R, Grashley R, Knupfer H, Kunz R, Seidel M (1964) 1.3-Dipolare Cycloadditionen, VI. Anlagerung der Nitrilimine an Azomethine und Isocyanate. Chem Ber 97:1085–1095
Huisgen R, Grashey R, Aufderhaar E, Kunz R (1965) 1.3-Dipolare Cycloadditionen, XIII. Additionen der Nitrilimine an Oxime. Azine und andere CN-Doppelbindungen. Chem Ber 98:642–649
Huisgen R, Aufderhaar E, Wallbillich G (1965) 1.3-Dipolare Cycloadditionen, XVI: Zur Bildung von 1.4-Dihydro-tetrazinen aus Nitriliminen; 1.4-Diphenyl-1.4-dihydro-1.2.4.5-tetrazin und isomere Verbindungen. Chem Ber 98:1476–1486
Huisgen R, Knupfer H, Sustmann R, Wallbillich G, Weberndörfer V (1967) 1.3-Dipolare Cycloadditionen, XXVII. Zur Anlagerung des Diphenylnitrilimins an nichtkonjugierte Alkene und Alkine; Sterischer Ablauf, Orientierung un Substituenteneinfluß. Chem Ber 100:1580–1592
Clovis JS, Eckell A, Huisgen R, Sustmann R, Wallbillich G, Weberndörfer V (1967) 1.3-Dipolare Cycloadditionen, XXVIII. Diphenylnitrilimin und arylkonjugierte alkene. Chem Ber 100:1593–1601
Huisgen R, Sustmann R, Wallbillich G (1967) 1.3-Dipolare Cycloadditionen, XXIX. Orientierungsphänomene bei der Anlagerung von Nitriliminen an α.β-ungesättigte Carbonester, Vinyläther und Enamine. Chem Ber 100:1786–1801
Eckell A, Huisgen R, Sustmann R, Wallbillich G, Grashey D, Spindler E (1967) 1.3-Dipolare Cycloadditionen, XXXI. Dipolarophilen-Aktivitäten gegenüber Diphenylnitrilimin und zahlenmäßige Ermittlung der Substituenteneinflüsse. Chem Ber 100:2192–2213
Huisgen R, Weberndörfer V (1967) 1.3-Dipolare Cycloadditionen, XXVI. Intramolekulare Stabilisierung bei einem N-Trinitrophenylnitrilimin. Chem Ber 100:71–78
Clovis JS, Eckell A, Huisgen R, Sustmann R (1967) 1.3-Dipolare Cycloadditionen, XXV. Der Nachweis des freien Diphenylnitrilimins als Zwischenstufe bei Cycloadditionen. Chem Ber 100:60–70
Oh LM (2006) Synthesis of Celecoxib via 1,3-Dipolar Cycloaddition. Tetrahedron Lett 47:7943–7946
Lim RKV, Lin Q (2011) Photoinducible bioorthogonal chemistry: a spatiotemporally controllable tool to visualize and perturb proteins in live cells. Acc Chem Res 44:828–839
Delaittre G, Goldmann AS, Mueller JO, Barner-Kowollik C (2015) Efficient photochemical approaches for spatially resolved surface functionalization. Angew Chemie Int Ed 54:11388–11403
Huisgen R (1963) 1,3-Dipolar cycloadditions. past and future. Angew Chemie Int Ed English 2:565–598
Caramella P, Houk KN (1976) Geometries of nitrilium betaines. The clarification of apparently anomalous reactions of 1,3-dipoles. J Am Chem Soc 98:6397–6399
Bock H, Dammel R, Fischer S, Wentrup C (1987) Nitrile imines RC = N(+) − N(−) − Si(CH3)3: optimization of gas phase synthesis and assignment of their photoelectron spectra. Tetrahedron Lett 28:617–620
Wong MW, Wentrup C (1993) Structure of nitrilimine: allenic or propargylic? J Am Chem Soc 115:7743–7746
Bégué D, Qiao GG, Wentrup C (2012) Nitrile imines: matrix isolation, IR spectra, structures, and rearrangement to carbodiimides. J Am Chem Soc 134:5339–5350
Caramella P, Gandour RW, Hall JA, Deville CG, Houk KN (1977) A derivation of the shapes and energies of the molecular orbitals of 1,3-dipoles. Geometry optimizations of these species by MINDO/2 and MINDO/3. J Am Chem Soc 99:385–392
Granier M, Baceiredo A, Huch V, Veith M, Bertrand G (1991) X-ray crystal structure and reactivity of an N-Phosphonio-substituted nitrilimine: a stable electrophilic nitrilimine. Inorg Chem 30:1161–1162
Hiberty PC, Leforestier C (1978) Expansion of molecular orbital wave functions into valence bond wave functions. A simplified procedure. J Am Chem Soc 100:2012–2017
Moffat J (1979) The isomers of diazomethane. J Mol Struct 52:275–280
Thomson C, Glidewell C (1983) An ab initio study of the relative stabilities of the isomers of CH2N2 and SiH2N2. J Comput Chem 4:1–8
Kahn SD, Hehre WJ, Pople JA (1987) Hartree-fock descriptions of 1,3-dipoles. Zwitterions, 1,3-diradicals, or hypervalent species? J Am Chem Soc 109:1871–1873
Guimon C, Khayar S, Gracian F, Begtrup M, Pfister-Guillouzo G (1989) HeI photoelectron and theoretical study of the gas phase flash pyrolysis of tetrazole and analysis of CN2H2 energy hypersurface. Chem Phys 138:157–171
Hiberty PC, Ohanessian G (1982) Comparison of minimal and extended basis sets in terms of resonant formulas. application to 1,3 dipoles. J Am Chem Soc 104:66–70
Kawauchi S, Tachibana A, Mori M, Shibusa Y, Yamabe T (1994) Molecular structures and relative stability of SiH2N2 and CH2N2 isomers. J Mol Struct 310:255–267
Maier G, Eckwert J, Bothur A, Reisenauer HP, Schmidt C (1996) Photochemical fragmentation of unsubstituted Tetrazole, 1,2,3-triazole, and 1,2,4-triazole: first matrix-spectroscopic identification of nitrilimine HCNNH. Liebigs Ann 1041–1053
Goldberg N, Fiedler A, Schwarz H (1994) Gas-phase generation and characterization of nitrileimine, HCNNH: a new, stable isomer of diazomethane. Helv Chim Acta 77:2354–2362
Kiselev VG, Cheblakov PB, Gritsan NP (2011) Tautomerism and thermal decomposition of tetrazole: high-level ab initio study. J Phys Chem A 115:1743–1753
RÃos-Gutiérrez M, Domingo LR (2019) The carbenoid-type reactivity of simplest nitrile imine from a molecular electron density theory perspective. Tetrahedron 75:1961–1967
Granier M, Baceiredo A, Dartiguenave Y, Dartiguenave M, Menu MJ, Bertrand G (1990) Synthesis and reactivity of stable phosphorus-substituted nitrilimines. X-ray crystal structure of C-[bis (diisopropylamino) thioxophosphoranyl]-N-[bis (diisopropylamino) phosphanyl] nitrilimine. J Am Chem Soc 112:6277–6285
Réau R, Veneziani G, Dahan F, Bertrand G (1992) A straightforward synthesis of nitrilimines; X-ray crystal structure of a nitrilimine stabilized by non-heteroatom substituents. Angew Chemie Int Ed English 31:439–440
Fauré J-L, Réau R, Wong MW, Koch R, Wentrup C, Bertrand G (1997) Nitrilimines: evidence for the allenic structure in solution, experimental and ab initio studies of the barrier to racemization, and first diastereoselective [3 + 2]-cycloaddition. J Am Chem Soc 119:2819–2824
Emig N, Gabbaï FP, Krautscheid H, Réau R, Bertrand G (1998) The azide-nitrilimine analogy in aluminum chemistry. Angew Chemie Int Ed 37:989–992
Arthur M-P, Baceiredo A, Fischer J, De Cian A, Bertrand G (1992) Substitution reactions at nitrilimine skeletons. Synthesis (Stuttg) 43–45
Uhl W, Hannemann F, Saak W, Wartchow R (1999) Diazomethane derivatives bearing dialkylaluminium or dialkylgallium substituents—the isomeric diazomethane and nitrile imine structures realized by the different coordination behavior of aluminium and gallium. Eur J Inorg Chem 1999:771–776
Nunes CM, Reva I, Fausto R, Bégué D, Wentrup C (2015) Bond-shift isomers: the co-existence of allenic and propargylic phenylnitrile imines. Chem Commun 51:14712–14715
Herges R (1994) Organizing principle of complex reactions and theory of coarctate transition states. Angew Chemie Int Ed English 33:255–276
Bégué D, Wentrup C (2014) Carbenic nitrile imines: properties and reactivity. J Org Chem 79:1418–1426
Nunes CM, Reva I, Rosado MTS, Fausto R (2015) The Quest for carbenic nitrile imines: experimental and computational characterization of C-amino nitrile imine. European J Org Chem 7484–7493
Sieber W, Gilgen P, Chaloupka S, Hansen H-J, Schmid H (1973) Tieftemperaturbestrahlungen von 3-Phenyl-2H-azirinen. Helv Chim Acta 56:1679–1690
Meier Hansruedi, Heinzelmann Willy, Heimgartner H (1980) Direct detection of diphenylnitrilimine in the photolysis of 2,5-diphenyltetrazole. Chimia (Aarau) 34:504–506
Meier Hansruedi, Heinzelmann Willy, Heimgartner H (1980) Inter- and intramolecular trapping reactions of photochemically generated diarylnitrilimines. Chimia (Aarau) 34:506–508
Toubro NH, Holm A (1980) Nitrilimines. J Am Chem Soc 102:2093–2094
Csongár C, Leihkauf P, Lohse V, Tomaschewski G (1984) Photochemistry of aryl-substituted 2H-Tetrazoles I. Direct spectroscopic detection of diarylnitrilimines. Zeitschrift für Chemie 24:96–97
Csongár C, Leihkauf P, Lohse V, Siegmund M, Tomaschewski G (1985) Photochemistry of aryl-substituted 2 H-tetrazoles III. IR spectroscopic detection of diarylnitrilimines. Zeitschrift für Chemie 25:106–107
Csongár C, Leihkauf P, Lohse V, Tomaschewski G (1985) Photochemistry of diarylsubstituted 2H-tetrazoles II, The influence of the substituents on the absorption properties of diarylnitrilmines. J für Prakt Chemie 327:96–102
Leihkauf P, Lohse V, Csongár C, Siegmund M, Tomaschewski G (1987) Photochemistry of diaryl-substituted 2H-tetrazoles V. On the influence of the substituents on the C = N-Valence vibrations of diaryl-substituted nitrilimines. Zeitschrift für Chemie 27:371–372
Leihkauf P, Lohse V, Csongár C, Tomaschewski G (1985) Photochemistry of aryl-substituted 2H-tetrazoles IV. and Sydnone II. Flash photolysis of diaryl nitrilimines. Zeitschrift für Chemie 25:266–267
Bhattacharyya K, Ramalah D, Das PK, George MV (1987) Flash photolysis studies of nitrile imines and related intermediates photogenerated from sydnones and tetrazoles in fluid solutions. J Photochem 36:63–84
Wentrup C, Flammang R (1998) Studies of reactive intermediates using matrix and gas-phase techniques. J Phys Org Chem 11:350–355
Wentrup C, Fischer S, Maquestiau A, Flammang R (1985) Nitrile imines: thermal generation, direct observation, and subsequent trapping. Angew Chemie Int Ed English 24:56–57
Nunes CM, Araujo-Andrade C, Fausto R, Reva I (2014) Generation and characterization of a 4π-electron three-membered ring 1H-diazirine: an elusive intermediate in nitrile imine-carbodiimide isomerization. J Org Chem 79:3641–3646
von Locquenghien KH, Réau R, Bertrand G (1991) The first nitrogen NMR spectroscopic study of nitrile imides (Nitrilimines). J Chem Soc, Chem Commun 1192–1193
Zheng S-L, Wang Y, Yu Z, Lin Q, Coppens P (2009) Direct observation of a photoinduced nonstabilized nitrile imine structure in the solid state. J Am Chem Soc 131:18036–18037
Castan F, Baceiredo A, Bigg D, Bertrand G (1991) Synthesis and reactivity of stable silyl-substituted nitrilimines. J Org Chem 56:1801–1807
Bertrand G, Wentrup C (1994) Nitrile imines: from matrix characterization to stable compounds. Angew Chemie Int Ed English 33:527–545
Leue C, Reau R, Neumann B, Stammler H-G, Jutzi P, Bertrand G (1994) Preparation of mono- and bis(germyl) nitrilimines from germylenes and stannyl diazo derivatives. Organometallics 13:436–438
Sicard G, Baceiredo A, Bertrand G (1988) Synthesis and reactivity of a stable nitrile imine. J Am Chem Soc 110:2663–2664
Müller E, Disselhoff H (1933) Über die Einwirkung von natrium auf aliphatische diazoverbindungen. Naturwissenschaften 21:661
Müller E, Disselhoff H (1934) Studies on diazomethanes I. Justus Liebig’s Ann der Chemie 512:250–263
Müller E, Kreutzmann W (1934) Studies on diazomethanes II. Justus Liebig’s Ann der Chemie 512:264–275
Müller E, Ludsteck D (1954) Studies on diazomethanes III: preparation of isodiazomethane and its rearrangement to diazomethane. Chem Ber 87:1887–1895
Müller E, Ludsteck D (1955) Studies on diazomethanes V: reactive behavior of diazomethyllithium. Chem Ber 88:921–933
Müller E, Rundel W (1957) Studeis on diazomethanes IX. Another recent synthesis of diazomethane and isodiazomethane. Chem Ber 90:2673–2678
Müller E, Kästner P, Rundel W (1965) Studies on diazomethanes XXII: The structure of isodiazomethane. Chem Ber 98:711–714
Müller E, Kästner P, Beutler R, Rundel W, Suhr H, Zeeh B (1968) Studies on diazomethanes XXVI isodiazomethan = knallsäureamid = N-isocyanamin. Justus Liebigs Ann Chem 713:87–95
Müller E, Beutler R, Zeeh B (1968) Studies on diazomethane XXVIII bang acid amide: the double tautomer of diazomethane. Justus Liebigs Ann Chem 719:72–79
Beutler R, Zeeh B, Müller E (1969) Studies on diazomethanes XXIX. Reactions with the tautomeric diazomethyl anion. Chem Ber 102:2636–2639
Boche G, Lohrenz JCW, Schubert F (1994) Lithio-diazomethane and lithio-(trimethylsilyl) diazomethane: theoretical and experimental studies of their structures, reactions and reaction products. Tetrahedron 50:5889–5902
Müller E, Rundel W (1956) Studies on diazomethanes VI: reaction of diazoethane with methyllithium. Chem Ber 89:1065–1071
Baceiredo A, Igau A, Bertrand G, Menu MJ, Dartiguenave Y, Bonnet JJ (1986) Phosphinocarbene-phosphaalkene rearrangement and intramolecular wittig-like reaction involving a phosphorus vinyl ylide. J Am Chem Soc 108:7868–7869
Menu MJ, Crocco G, Dartiguenave M, Dartiguenave Y, Bertrand G (1988) Reactivity of Rh(PMe3)4Cl with lithium derivatives of phosphorus-substituted diazomethanes. First evidence for a transient nitrogen-transition-metal nitrile imine. X-ray structure of [cyclic] (PMe3)2RhNBuNCHP (N-iso-Pr2)2. Organometallics 7:2231–2233
Boche G, Harms K, Marsch M, Schubert F (1994) {6 Lithio(trimethylsilyl)diazomethane 2 Lithio[4,5-bis(trimethylsilyl)triazene]·7 Diethyl Ether}: the first X-ray structure analysis of a lithiated diazoalkane. Chem Ber 127:2193–2195
Reau R, Veneziani G, Bertrand G (1992) Formation of nitrilimines and diazo compounds from lithiated and stannyl diazo derivatives: scope and mechanism. J Am Chem Soc 114:6059–6063
Castan F, Baceiredo A, Bertrand G (1989) A distillable C- and N-silylated nitrile imine. Angew Chemie Int Ed English 28:1250–1251
Arthur MP, Goodwin HP, Baceiredo A, Dillon KB, Bertrand G (1991) Synthesis of stable boryl-substituted diazomethane and nitrilimines. Organometallics 10:3205–3210
Chu J, Kefalidis CE, Maron L, Leng X, Chen Y (2013) Chameleon behavior of a newly synthesized scandium nitrilimine derivative. J Am Chem Soc 135:8165–8168
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Jamieson, C., Livingstone, K. (2020). Nitrile Imines and Their Properties. In: The Nitrile Imine 1,3-Dipole. Springer, Cham. https://doi.org/10.1007/978-3-030-43481-6_1
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