Synthesis of asymmetrical N,N′-disubstituted N,N′-dinitromethylenediamine

Conclusions Syntheses are reported for asymmetric N,N-disubstituted N.N-dinitromethylenediamines by the Mannich reaction from N-nitroalkylamines, formaldehyde, and 2-fluoro-2,2-dinitro-ethylamine in methanol or ethanol.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 721–723, March, 1989.     

N,N,N′-Tri­methyl­ethyl­enediammonium dichloride

The title compound, C₅H₁₆N₂²⁺·2Cl⁻, was isolated as a by-product from the reaction between trimethylethyl­enedi­amine and germanium tetrachloride in the presence of triethyl­amine. The asymmetric unit contains two cations, one in the gauche and the other in the trans conformation; these conformations are stabilized by hydrogen-bonding interactions between the N—H moieties and the chloride anions.     

Zur Phosphorylierung von N,N-Dimethylharnstoff mit POCl3, N,N-Dimethylbiuretophosphat

On the Phosphorylation of N,N-Dimethylurea with POCl₃. N,N-Dimethylbiuretophosphate (H₃C)₂NCONH₂ and POCl₃ in a molar ratio of 4:1 are allowed to react in liquid SO₂. After evaporation of SO₂ remains a viscous liquid which crystallizes 8–10 days later. The alkaline hydrolysis of the crystals leads to [(H₃C)₂NCONHCONHP(O)O₂]^?, which is precipitated from the cold concentrated solution by gaseous ammonia. The biuret group is produced by the action of primary formed upon (CH₃)₂NCONH₂ in the viscous reaction liquid.     

Iodide, azide, and cyanide complexes of (N,C), (N,N), and (N,O) metallacycles of tetra- and pentavalent uranium

In contrast to the neutral macrocycle [UN*(2)(N,C)] (1) [N* = N(SiMe(3))(3); N,C = CH(2)SiMe(2)N(SiMe(3))] which was quite inert toward I(2), the anionic bismetallacycle [NaUN*(N,C)(2)] (2) was readily transformed into the enlarged monometallacycle [UN*(N,N)I] (4) [N,N = (Me(3)Si)NSiMe(2)CH(2)CH(2)SiMe(2)N(SiMe(3))] resulting from C-C coupling of the two CH(2) groups, and [NaUN*(N,O)(2)] (3) [N,O = OC(═CH(2))SiMe(2)N(SiMe(3))], which is devoid of any U-C bond, was oxidized into the U(V) bismetallacycle [Na{UN*(N,O)(2)}(2)(μ-I)] (5). Sodium amalgam reduction of 4 gave the U(III) compound [UN*(N,N)] (6). Addition of MN(3) or MCN to the (N,C), (N,N), and (N,O) metallacycles 1, 4, and 5 led to the formation of the anionic azide or cyanide derivatives M[UN*(2)(N,C)(N(3))] [M = Na, 7a or Na(15-crown-5), 7b], M[UN*(2)(N,C)(CN)] [M = NEt(4), 8a or Na(15-crown-5), 8b or K(18-crown-6), 8c], M[UN*(N,N)(N(3))(2)] [M = Na, 9a or Na(THF)(4), 9b], [NEt(4)][UN*(N,N)(CN)(2)] (10), M[UN*(N,O)(2)(N(3))] [M = Na, 11a or Na(15-crown-5), 11b], M[UN*(N,O)(2)(CN)] [M = NEt(4), 12a or Na(15-crown-5), 12b]. In the presence of excess iodine in THF, the cyanide 12a was converted back into the iodide 5, while the azide 11a was transformed into the neutral U(V) complex [U(N{SiMe(3)}SiMe(2)C{CHI}O)(2)I(THF)] (13). The X-ray crystal structures of 4, 7b, 8a-c, 9b, 10, 12b, and 13 were determined.     

Iron-catalyzed olefin cis-dihydroxylation using a bio-inspired N,N,O-ligand

Nature has evolved enzymes that carry out the cis-dihydroxylation of C=C bonds in the biodegradation of arenes in the environment. These enzymes, called Rieske dioxygenases, have mononuclear iron centers coordinated to a 2-His-1-carboxylate facial triad motif that has emerged as a common structural element among many nonheme iron enzymes. In contrast, olefin cis-dihydroxylation is conveniently carried out by OsO4 and related species in synthetic procedures. To develop more environmentally benign strategies for carrying out these transformations, we have designed Ph-DPAH [(di-(2-pyridyl)methyl)benzamide], a tridentate ligand that mimics the facial N,N,O site of the mononuclear iron center in the Rieske dioxygenases. Its iron(II) complex has been found to catalyze olefin cis-dihydroxylation almost exclusively and with high H2O2 conversion efficiency on a wide range of substrates. and 18O labeling experiments suggest the participation of an FeV oxidant.     

Gravimetrische Phosphorbestimmung mit N,N,N′,N′-Tetrakis-(2-hydroxybutyl)-äthylendiammoniumdiperchlorat

This reagent forms a sparingly soluble precipitate, [C₁₈H₄₀O₄N₂H₂]₃[P(Mo₃O₁₀)₄]₂ in presence of phosphate and molybdate in hydrochloric acid solution. The precipitate is well suitable for a gravimetric determination of phosphorus (factor 0.013190). Standard deviation was ± 0.3 mg for 93.94 mg and ± 0.6 mg for 1174,2 mg of precipitate. Fe, Mn, Cr, Co and Ni do not interfere up to a 500-fold excess.     

Coordination of lanthanide triflates and perchlorates with N,N,N',N'-tetramethylsuccinamide

Compounds formed from the reaction of N,N,N',N'-tetramethylsuccinamide (TMSA) with trivalent lanthanide salts possessing the poorly coordinating counteranions triflate (CF3SO3-) and perchlorate (ClO4-) have been prepared and examined. Structural features of these Ln-TMSA compounds have been studied in the solid phase by thermogravimetric analysis, infrared spectroscopy, and, in selected cases, by single-crystal X-ray diffraction and in solution by infrared spectroscopy. Eight-coordinate compounds, [Ln(TMSA)4]3+, derived from coordination of four succinamide ligands to the metal ion could be formed with all lanthanides examined (Ln = La, Pr, Nd, Eu, Yb, Lu). Structural analyses by single-crystal X-ray diffraction were performed for the lanthanide triflate salts Ln(C8H16N2O2)4(CF3SO3)3: Ln = La, compound 1, monoclinic, P2(1)/n, a = 11.0952(2) A, b = 19.2672(2) A, c = 24.9759(3) A, beta = 90.637(1) degrees, Z = 4, Dcalcd = 1.586 g cm-3; Ln = Nd, compound 2, monoclinic, C2/c, a = 24.6586(10) A, b = 19.3078(7) A, c = 11.1429(4) A, beta = 90.450(1) degrees, Z = 4, Dcalcd = 1.603 g cm-3; Ln = Eu, compound 3, monoclinic, C2/c, a = 24.4934(2) A, b = 19.3702(1) A, c = 11.1542(1) A, beta = 90.229(1) degrees, Z = 4, Dcalcd = 1.617 g cm-3; Ln = Lu, compound 5, monoclinic, C2/c, a = 24.2435(4) A, b = 19.6141(2) A, c = 11.2635(1) A, beta = 90.049(1) degrees, Z = 4, Dcalcd = 1.626 g cm-3. X-ray analysis was also carried out for the perchlorate salt: Ln = Eu, compound 4, triclinic, P1, a = 10.9611(2) A, b = 14.6144(3) A, c = 15.7992(2) A, alpha = 106.594(1) degrees, beta = 91.538(1) degrees, gamma = 90.311(1) degrees, Z = 2, Dcalcd = 1.561 g cm-3. In the presence of significant amounts of water, 7-coordinate compounds with mixed aquo-TMSA cation structures [Ln(TMSA)3(H2O)]3+ (Ln = Yb) and [Ln(TMSA)2(H2O)3]3+ (Ln = La, Pr, Nd, Eu, Yb) have been isolated with structural determinations by single-crystal X-ray diffraction obtained for the following species: Yb(C8H16N2O2)3(H2O)(CF3SO3)3, compound 6, monoclinic, P2(1)/n, a = 8.9443(3) A, b = 11.1924(4) A, c = 44.2517(13) A, beta = 93.264(1) degrees, Z = 4, Dcalcd = 1.735 g cm-3; Yb(C8H16N2O2)3(H2O)(ClO4)3, compound 7, monoclinic, Cc, a = 19.2312(6) A, b = 11.1552(3) A, c = 19.8016(4) A, beta = 111.4260(1) degrees, Z = 4, Dcalcd = 1.690 g cm-3; Yb(C8H16N2O2)2(H2O)3(CF3SO3)3, compound 8, triclinic, P1, a = 8.6719(1) A, b = 12.2683(2) A, c = 19.8094(3) A, alpha = 75.815(1) degrees, beta = 86.805(1) degrees, gamma = 72.607(1) degrees, Z = 2, Dcalcd = 1.736 g cm-3. Unlike in the analogous nitrate salts, only bidentate binding of the succinamide ligand to the lanthanide metal is observed. IR spectroscopy studies in anhydrous acetonitrile suggest that the solid-state structures of these Ln-TMSA compounds are maintained in solution.     

Darstellung und Eigenschaften von N,N-Dialkyl-allylaminoboran-Addukten und N,N-Dimethyl-aminopropylboran

Synthesis and Properties of N,N-Dialkyl-allylaminoboranes and N,N-Dimethylaminopropylborane Complexes of the type H₃B ← NR₂(CH₂CH?CH₂) (R?CH₃ I , C₂H₅ II ) are formed by reaction of Li[BH₄] with dialkylallylammonium salts. By addition of AlCl₃ I can be transformed into the chelate-stabilized N,N-dimethyl-aminopropylborane III . The i.r.-, ¹H, ¹³C-n.m.r. and mass-spectra of I – III are reported and discussed.     

Ab initio calculations of nitrogen oxide reactions: formation of N2O2, N2O3, N2O4, N2O5, and N4O2 from NO, NO2, NO3, and N2O

Ab initio computational methods were used to obtain Delta(r)H(o), Delta(r)G(o), and Delta(r)S(o) for the reactions 2 NO <=> N(2)O(2) (I), NO+NO(2) <=> N(2)O(3) (II), 2 NO(2) <=> N(2)O(4) (III), NO(2)+NO(3) <=> N(2)O(5) (IV), and 2 N(2)O <=> N(4)O(2) (V) at 298.15 K. Optimized geometries and frequencies were obtained at the CCSD(T) level for all molecules except for NO, NO(2), and NO(3), for which UCCSD(T) was used. In all cases the aug-cc-pVDZ (avdz) basis set was employed. The electronic energies of all species were obtained from complete basis set extrapolations (to aug-cc-pV5Z) using five different extrapolation methods. The [U]CCSD(T)/avdz geometries and frequencies of the N(x)O(y) compounds are compared with literature values, and problems associated with the values and assignments of low-frequency modes are discussed. The standard entropies are compared with values cited in the NIST/JANAF tables [NIST-JANAF Thermochemical Tables, J. Phys. Chem. Ref. Data Monograph No. 9, 4th ed. edited by M. W. Chase, Jr. (American Chemical Society and American Institute of Physics, Woodbury, NY, 1988)]. With the exception of I, in which the dimer is weakly bound, and V, for which thermodynamic data appears to be lacking, the calculated standard thermodynamic functions of reaction are in good agreement with literature values obtained both from statistical mechanical and various equilibrium methods. A multireference-configuration interaction calculation (MRCI+Q) for I provides a D(e) value that is consistent with previous calculations. The combined uncertainties of the NIST/JANAF values for Delta(r)H(o), Delta(r)G(o), and Delta(r)S(o) of II, III, and IV are discussed. The potential surface for the dissociation of N(2)O(4) was explored using multireference methods. No evidence of a barrier to dissociation was found.     

Zinkkomplexe eines neuen N,N, O‐Liganden

Zinc Complexes of a New N, N, O Ligand The tridentate ligand N, N(2‐dimethylaminoethyl)‐3, 5‐di‐tert.‐butyl‐salicylaldimine ( L H) results from the corresponding salicylic aldehyde and N, N‐dimethyl ethylenediamine. With zinc salts it forms the mononuclear halide complexes [ L ZnCl ˙ CH₃OH] ( 1 ) and [ L ZnI ˙ CH₃OH] ( 2 ) and the presumably polymeric acetate [ L ZnOCOCH₃] ( 3 ). With diethyl zinc and diphenylphosphoric acid it yields the phosphate complex [ L Zn‐OPO(OPh)₂ ˙ CH₃OH] ( 4 ). The coordination of the complexes, which is between trigonal bipyramidal and square pyramidal, and the character of the five donors in the phosphate complex represent the transition state of a hydrolytic substrate cleavage in a zinc enzyme.     

EFFECT OF N,N,N’,N’-TETRAALKYL TEREPHTHALAMIDE ON NON-ISOTHERMAL CRYSTALLIZATION KINETICS OF POLYPROPYLENE

The effect of N,N,N＇,N＇-tetraalkyl terephthalamide （TATA） on the non-isothermal crystallization and melting characteristics ofpolypropylene （PP） was studied. The addition of TATA can lead to the formation ofβ-crystal PP. With the increase in TATA concentration the degree of crystallinity for β-crystal PP increased significantly, and that for a-crystal PP decreased, which indicated that TATA effectively induced the formation of β-crystal PP. WAXD also revealed the existence of β-crystal PP after the introduction of TATA into PP. PP containing TATA crystallized at a temperature range of 5-10℃ higher than that of pure PP, and the half-crystallization time （t1/2） and Avrami exponent （n） of PP at the same cooling rate were decreased by the addition of TATA, indicating that TATA influenced the crystallization rate and crystallization growth mode of PP. The rate constant of crystallization of PP containing TATA （Zc） was larger than that of pure PP, which further indicated that the crystallization of PP was accelerated by the addition of TATA.     

Oligodentate P,N ligands: N,N,N',N'-tetrakis(diphenylphosphanyl)-1,3-diaminobenzene complexes of rhodium, nickel and palladium

The oligodentate P,N ligand N,N,N',N'-tetrakis(diphenylphosphanyl)-1,3-diaminobenzene reacts with two equivalents of [{Rh(mu-Cl)(COD)}(2)], [NiBr(2)(DME)] or [PdCl(2)(NCMe)(2)](COD = 1,5-cyclooctadiene, DME = dimethoxyethane) in dichloromethane to give the tetranuclear complex [1,3-{cis-Rh(COD)(mu-Cl)(2)Rh(PPh(2))(2)N}(2)C(6)H(4)](1) or the dinuclear complexes [1,3-{cis-NiBr(2)(PPh(2))(2)N}(2)C(6)H(4)](2) and [1,3-{cis-PdCl(2)(PPh(2))(2)N}(2)C(6)H(4)](3), respectively. Compounds 1-3 were characterised by NMR ((1)H, (13)C, (31)P) and IR spectroscopy. The molecular structure of 2 and 3 shows the formation of a bis-chelate complex with M-P-N-P four-membered rings (M = Pd, Ni). An N,N,N',N'-tetrakis(diphenylphosphanyl)-1,3-diaminobenzene/Pd(OAc)(2) mixture was used for the copolymerisation of carbon monoxide with ethene or ethylidenenorbornene. Compound 1 was employed as catalyst in the hydrogenation of styrene.     

N,N’-二苯基-N,N’-二(9,9-二甲基芴-2-基)-9-己基-(4,4’-二胺基苯基)咔唑的合成方法及表征

以2,7-二溴咔唑为原料经过N-烷基化、Suzuki偶联反应、Buchwald-Hartwig偶联反应合成了有机发光二极管(OLED)空穴传输材料N,N’-二苯基-N,N’-二(9,9-二甲基芴-2-基)-9-己基-(4,4’-二胺基苯基)咔唑,利用NMR、IR和熔点等分析方法对产物结构进行了表征,并通过TG、UV-Vis及荧光光谱研究了物质的热稳定性和光学性能。     

N,N,N-三甲基-2-萘基季铵盐的合成

以2-萘胺和碘甲烷为原料,首次合成了N,N,N-三甲基-2-萘基季铵盐,其结构经1H NMR,IR和MS表征。     

Binding N2, N2H2, N2H4, and NH3 to transition-metal sulfur sites: modeling potential intermediates of biological N2 fixation

In the quest for low-molecular-weight metal sulfur complexes that bind nitrogenase-relevant small molecules and can serve as model complexes for nitrogenase, compounds with the [Ru(PiPr(3))('N(2)Me(2)S(2)')] fragment were found ('N(2)Me(2)S(2)'(2-)=1,2-ethanediamine-N,N'-dimethyl-N,N'-bis(2-benzenethiolate)(2-)). This fragment enabled the synthesis of a first series of chiral metal sulfur complexes, [Ru(L)(PiPr(3))('N(2)Me(2)S(2)')] with L=N(2), N(2)H(2), N(2)H(4), and NH(3), that meet the biological constraint of forming under mild conditions. The reaction of [Ru(NCCH(3))(PiPr(3))('N(2)Me(2)S(2)')] (1) with NH(3) gave the ammonia complex [Ru(NH(3))(PiPr(3))('N(2)Me(2)S(2)')] (4), which readily exchanged NH(3) for N(2) to yield the mononuclear dinitrogen complex [Ru(N(2))(PiPr(3))('N(2)Me(2)S(2)')] (2) in almost quantitative yield. Complex 2, obtained by this new efficient synthesis, was the starting material for the synthesis of dinuclear (R,R)- and (S,S)-[micro-N(2)[Ru(PiPr(3))('N(2)Me(2)S(2)')](2)] ((R,R)-/(S,S)-3). (Both 2 and 3 have been reported previously.) The as-yet inexplicable behavior of complex 3 to form also the R,S isomer in solution has been revealed by DFT calculations and (2)D NMR spectroscopy studies. The reaction of 1 or 2 with anhydrous hydrazine yielded the hydrazine complex [Ru(N(2)H(4))(PiPr(3))('N(2)Me(2)S(2)')] (6), which is a highly reactive intermediate. Disproportionation of 6 resulted in the formation of mononuclear diazene complexes, the ammonia complex 4, and finally the dinuclear diazene complex [micro-N(2)H(2)[Ru(PiPr(3))('N(2)Me(2)S(2)')](2)] (5). Dinuclear complex 5 could also be obtained directly in an independent synthesis from 1 and N(2)H(2), which was generated in situ by acidolysis of K(2)N(2)(CO(2))(2). Treatment of 6 with CH(2)Cl(2), however, formed a chloromethylated diazene species [[Ru(PiPr(3))('N(2)Me(2)S(2)')]-micro-N(2)H(2)[Ru(Cl)('N(2)Me(2)S(2)CH(2)Cl')]] (9) ('N(2)Me(2)S(2)CH(2)Cl'(2-) =1,2-ethanediamine-N,N'-dimethyl-N-(2-benzenethiolate)(1-)-N'-(2-benzenechloromethylthioether)(1-)]. The molecular structures of 4, 5, and 9 were determined by X-ray crystal structure analysis, and the labile N(2)H(4) complex 6 was characterized by NMR spectroscopy.     

Concise access to N9-mono-, N2-mono- and N2,N9-di-substituted guanines via efficient Mitsunobu reactions

Guanine poses several problems to the synthetic chemist owing to its polyfunctional nature and poor solubility. Over the past few decades, synthetic guanines have found applications as anti-cancer and anti-viral agents. Coupled with the ever-growing interest in designer PNAs and G-quartets, simple and efficient synthetic routes to novel guanines would be of significant benefit. We herein report that, upon simple protection and/or activation step(s), the guanine precursor 2-amino-6-chloropurine is rendered an excellent substrate for Mitsunobu chemistry, furnishing, after subsequent hydrolytic dechlorination and appropriate deprotection step(s), the desired N9-mono-, N2-mono- or N2,N9-di-substituted guanines in excellent yields (≥80%). Importantly, we demonstrate that N9-functionalization proceeds with very good N9/N7 regioselectivity and with complete inversion of stereochemistry.     

N,N′-Bis(trimethylsilylmethyl)thiocarbamide and N,N′-Bis(trimethylsilylmethyl)-λ6-thiocarbamide S,S-Dioxide

N,N′-Bis(trimethylsilylmethyl)-λ⁶-thiocarbamide S,S-dioxide was synthesized by oxidation of N,N′-bis(trimethylsilylmethyl)thiocarbamide with hydrogen peroxide. The synthesized dioxide is a less active reducing agent than previously studied S,S-dioxides of organosilicon thiocarbamides in which the silicon atom is separated from the thiocarbamide fragment by a -CH₂CH₂CH₂- bridge.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 6, 2005, pp. 912–914.Original Russian Text Copyright © 2005 by Vlasova, Grigor’eva, Voronkov.     

N,N′-bis(2-Vinyloxyethyl)carbodiimide

Previously unreported N,N-bis(2-vlnyloxyethyl)carbodiimide was synthesized by the reaction of N,N -bis(2-vinyloxyethyl)thiourea with yellow mercuric oxide in CH₂Cl₂ at room temperature.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1897–1898, August, 1990.     

Reaktionen von (−)-Ephedrin bzw. (+)-Norpseudoephedrin und Derivaten mit N,N-Dimethylacetamid-dimethylacetal und N,N,-Dimethylformamid-dimethylacetal

Summary The reactivity of (–)-ephedrine (2) and (+)-norpseudoephedrine (3) towards the amidacetals1 a/b has been studied. Both2 and3 were acetylated resp. formylated at first at the amino group. Nevertheless, derivatives of2 and3 possessing a trisubstituted amino group react with1 a in a [3.3] sigmatopic rearrangement toortho substituted dimethylcarbamoylmethyl derivatives. By subsequent reduction with lithiumaluminiumhydride the aromatic compounds8,13, and18 with two aminoethyl groups are easily available. In contrast to these results1 b did not furnish any rearrangement products.

     

Ethylenediamine-N,N,N′,N′-tetrakis(methylenephosphonic) acid as complexing agent

Metal derivatives of ethylenediamine-N,N,N′,N′-tetrakis(methylenephosphonic) acid (EDTMP, H₈L) with some bivalent ions—Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Pb(II) have been isolated in various stoichiometric ratios from aqueous medium. Electronic spectra indicate them to be six-coordinated. EPR studies of Cu(II) complexes show that they are tetragonally elongated. Magnetic moments of M₄L derivatives are very low due to antiferromagnetic exchange interactions, but the moments go on increasing for M₃Na₂L and M₂Na₄L and are normal for MNa₆L derivatives, due to isolation of paramagnetic centres by diamagnetic sodium ions. IR spectra and thermal stability of the complexes have also been studied.