- Tris(3,5-dimethylpyrazolyl)methane copper(I) complexes featuring one disubstituted cyanamide ligand
-
The complexes [Cu{HC(3,5-Me2pz)3}(NCNR2)][BF4] (1–8; R2 = Me2 1, Et2 2, C5H10 3, C4H8O 4, C4H8 5, C3H
- Melekhova, Anna A.,Novikov, Alexander S.,Dubovtsev, Alexey Yu.,Zolotarev, Andrey A.,Bokach, Nadezhda A.
-
-
Read Online
- A New General Synthesis of N-Mono- and N-Di-substituted 2-Aminothiazoles
-
Solutions of α-mercapto-ketone anions, generated from O-ethyl S-2-oxoethyl dithiocarbonates and piperidine, react with cyanamides to give 2-aminothiazoles with substituents on the heterocycle or the exo-nitrogen atom.
- Brown, Michael D.,Gillon, David W.,Meakins, G. Denis,Whitham, Gordon H.
-
-
Read Online
- Accelerated degradation of methyl iodide by agrochemicals
-
The fumigant methyl iodide (Mel, iodomethane) is considered a promising alternative to methyl bromide (MeBr) for soil-borne pest control in high-cash-value crops. However, the high vapor pressure of Mel results in emissions of a significant proportion of the applied mass into the ambient air, and this may lead to pollution of the environment. Integrating the application of certain agrochemicals with soil fumigation provides a novel approach to reduce excessive fumigant. emissions. This study investigated the potential for several agrochemicals that are commonly used in farming operations, including fertilizers and nitrification inhibitors, to transform Mel in aqueous solution. The pseudo-first-order hydrolysis half-life (t1/2) of Mel was ～ 108 d, while the transformation of Mel in aqueous solutions containing selected agrochemicals was more rapid, with t1/2 1/2 1/2 of Mel was 1/2 > 300 h).
- Zheng, Wei,Papiernik, Sharon K.,Guo, Mingxin,Yates, Scott R.
-
-
Read Online
- Effects of Ionizing Radiation on Cyanamide and Dimethylcyanamide
-
Irradiation of the pure title compounds and a range of dilute solid solutions produces a range of matrix-isolated radicals, identified by their EPR spectra.These include electron-loss centres, HN.CN and (Me2N.CN)+, and electron capture centres HNC(H)N.- and Me2N..The former is a tautomer of the parent anion and the latter is formed by loss of CN-.In aqueous alkali glasses, the radical anion .N2CO3- is thought to be formed by addition of O.- to CN22-.
- O'Connell, Aidan B.,Chandra, Harish,Mishra, Shuddhodan P.,Hasegawa, Akinori,Symons, Martyn C. R.
-
-
Read Online
- Selenium-nitrogen bond formation by ring expansion: Synthesis of the 1,4,2-diselenazine ring system, fragmentation to a 1,2-diselenete and reactions to yield 1,4-diselenin derivatives
-
1,3-Diselenolium cation salt 1 reacts with ammonia and iodine to afford the novel 1,4,2-diselenazine system 6 (40% yield) which fragments to yield dimethylcyanamide 8 and diselenin 9, presumably via intermediate 1,2-diselenete 7, which is trapped with dimethyl acetylenedicarboxylate to yield the cycloadduct 10.
- Yoshida, Shimon,Bryce, Martin R.,Chesney, Antony
-
-
Read Online
- TETRAHYDROFURO[3,4-C]ISOQUINOLINES AS INHIBITORS OF PDE4
-
The compounds of a certain formula 1, in which R1, R2 and R3 have the meanings as given in the description, are novel effective inhibitors of phosphodiesterase type 4.
- -
-
Page/Page column 22
(2018/04/27)
-
- A allyl uncle amine compound by one-step synthesis method of cyano uncle amine compound (by machine translation)
-
The invention relates to a one-step synthesis of amine compound allyl unclecyano uncle amine compounds, which belongs to the technical field of organic synthetic method. The method specific synthetic process is as follows: in the airtight reaction environment, to the anhydrous organic solvent is added in the cyanogen bromide, under protection of inert gas, and then added dropwise to the solution in the allylic and high yield amine compound, to obtain allyl uncle amine compound concentration is 0.8 - 1 mol/L solution, at room temperature the reaction 16 - 24 hours later, after column chromatography separation and purification, to obtain a corresponding cyano uncle amine compound. The method to get rid of the expensive deallylation use of the catalyst, the synthesis step is less, raw materials are easy, cheap, mild reaction conditions, the operation is simple, easy to craft and industrialization. Yield 50% - 80% between. (by machine translation)
- -
-
Paragraph 0052-0060
(2017/09/01)
-
- Synthesis of Cyanamides from Cyanogen Bromide under Mild Conditions through N-Cyanation of Allylic Tertiary Amines
-
Cyanamides were selectively formed through a one-step nucleophilic substitution reaction of allylic tertiary amines with cyanogen bromide. Because of the mild reaction conditions and good yields of the reaction, as well as the commercial availability of the starting materials, this new method represents a valuable tool for the synthesis of cyan-amides through an N-deallylation reaction and an N-cyanation reaction in one pot.
- Liang, Honggang,Bao, Lingxiang,Du, Yao,Zhang, Yiying,Pang, Siping,Sun, Chenghui
-
supporting information
p. 2675 - 2679
(2017/10/06)
-
- Novel and facile transformation of N,N-disubstituted glycylamides into corresponding cyanamides by using pentavalent iodine reagents in combination with tetraethylammonium bromide
-
Novel and facile transformation of N,N-disubstituted glycylamides into corresponding cyanamides using pentavalent iodine reagents and tetraethylammonium bromide is discussed. The advantages of this system are use of non toxic reagents, shorter reaction times and moderate to good yields. Georg Thieme Verlag Stuttgart.
- Chaudhari, Kiran H.,Mahajan, Ulhas S.,Bhalerao, Dinesh S.,Akamanchi, Krishnacharya G.
-
p. 2815 - 2818
(2008/02/12)
-
- Comparative studies for selective deprotection of the N-arylideneamino moiety from heterocyclic amides: Kinetic and theoretical studies
-
The kinetics, product analysis and theoretical studies for selective deprotection of N-arylideneamino pyridone, pyrimidinone and triazinone systems were carried out. Their reactivities were compared with each other and with related compounds previously studied. This reaction represents an efficient, clean and general synthetic procedure for the protection and selective synthesis of potential biologically active pyridines, pyrimidines and triazines and their derivatives.
- George, Bobby J.,Dib, Hicham H.,Abdallah, Mariam R.,Ibrahim, Maher R.,Khalil, Nasser S.,Ibrahim, Yehia A.,Al-Awadi, Nouria A.
-
p. 1182 - 1192
(2007/10/03)
-
- Process for producing dimethylcyanamide
-
Cyanogen chloride and dimethylamine are reacted in a water/organic solvent system. The organic solvent is immiscible with water. After the completion of reaction, the water-immiscible organic solvent is distilled away from the reaction product solution to carry out the subsequent synthesis of 1,1,3,3-tetramethylguanidine in an aqueous system.
- -
-
-
- Synthesis and trapping of transient 1,2-diselones to yield 1,4-diselenin derivatives: Calculated structures of 1,2-diselones, 1,2-diselenetes and their sulfur analogues
-
Two conceptually different routes to transient 1,2-diselones are reported: 1) via ring fragmentation of the 1,4,2-diselenazine system 6, and 2) by the tributylphosphane-induced depolymerisation of the shelf-stable organoselenium polymer 15. Evidence for the intermediacy of 1,2-diselone species 7 and 16 is provided in both cases by in situ trapping with dimethyl acetylenedicarboxylate (DMAD) to yield 1,4-diselenin derivatives. The route via 15 is especially expedient and trapping of 16 is efficient. Subsequent reactions of adduct 17 afford [1,2-ethanediylbis(diphenylphosphane)][5,6- bis(methoxycarbonyl)-1,4-diselenin-2,3-dithiolato]nickel(IV) (20). Theoretical calculations at Hartree-Fock (HF) and Moller-Plesset electron- correlated levels (MP2) suggest that the cyclic 1,2-diselenete structure 7c is significantly more stable than the acyclic 1,2-diselone structure 7a. For the bicyclic system 16, the difference in energy between the cyclic and acyclic structures is considerably reduced due to the conformational rigidity imposed by the fused 1,3-dithiole ring. In contrast, the acyclic structures of the 1,2-dithione analogues 13a and 25a are computed to be more stable than their corresponding cyclic 1,2-dithiete structures 13c and 25c.
- Chesney, Antony,Bryce, Martin R.,Yoshida, Shimon,Perepichka, Igor F.
-
p. 1153 - 1159
(2007/10/03)
-
- Preparation and characterisation of N,N-disubstituted 2-amino-selenazoles
-
As a result of checking suited methods for preparing N,N-disubstituted 2-amino-selenazoles 14 as a nearly unknown class of highly reactive selenazoles a simple route starting from N,N-disubstituted selenoureas 12 has been elaborated and used for the synthesis of a series of these compounds. The necessary selenium-containing starting compounds 12 are available from N,N-disubstituted cyanamides 18 and hydrogen selenide.
- Keil, Dietmar,Hartmann, Horst
-
p. 169 - 184
(2007/10/03)
-
- Thermolysis of Polyazapentadienes. Part 11. Concerted and Free Radical Mechanisms in 2-Aza Enone and 2-Aza Enthione Pyrolyses: Crystal and Molecular Structures of 3-Dimethylamino-1-p-tolyl-2-azaprop-2-en-1-one and 3-Dimethylamino-1-phenyl-2-azaprop-2-ene-1-thione
-
Flash vacuum pyrolysis of the dimethylamino-azapropenones (7)-(9) and -azapropenethione (12) gives nitriles and amides (or thioamide) in yields of ca. 30percent by an electrocyclisation-ring cleavage mechanism.This is a minor pathway for the triarylazapropenones (14) and (15) for which homolytic cleavage of the C-N bond gives rise to the major products.The X-ray crystal structures of (10) and (12) show that the conjugated systems are almost planar in the s-Z conformation, as required for the electrocyclic ring closure.
- Blake, Alexander J.,McNab, Hamish,Murray, M. Elizabeth-Ann
-
p. 589 - 595
(2007/10/02)
-
- Preparation, structure, and bonding of Mo2(OCH2CMe3)6(μ-η 1,η2-NCNMe2)
-
Hydrocarbon solutions of Mo2(OCH2-t-Bu)6(M≡M) and R2NCN (R = Me, Et) react to give a compound of formula Mo2(OCH2-t-Bu)6(μ-R2NCN). A single-crystal X-ray diffraction study shows that cyanamide bridges the two molybdenum atoms parallel to the M-M vector. Pertinent bond distances are Mo-Mo = 2.449 (1) A?, C≡N = 1.333 (4) A?, Mo-O (terminal) = 1.91 (average) A?, Mo1-C = 2.014 (4) A?, and Mo2-N = 2.134 (3) A?. 1H NMR studies show the molecule is fluxional at room temperature, involving a turnstile-type motion of three terminal alkoxide ligands. The nature of bonding of the cyanamide ligand to the dimetal center has been investigated by Fenske-Hall calculations on the model system Mo2(OH)6(μ-H2NCN). Extensive rehybridization of H2NCN occurs upon interaction with the dimetal center allowing the cyanamide to act as a donor to both metals. Reduction of the H2NCN in this compound takes place via back-bonding into the a′ π* orbital of cyanamide. The reduction of the H2NCN is suggestive of a model for the reaction pathway of RCN with W2(O-t-Bu)6 leading to carbyne and nitride formation.
- Chisholm, Malcolm H.,Huffman, John C.,Marchant, Nancy S.
-
p. 1073 - 1080
(2008/10/08)
-
- FORMATION OF DIALKYLAMINOACETONITRILE FROM N,N-DIALKYLAMIDES IN AN RF PLASMA
-
An unprecedented transformation of N,N-dimethylamides into dimethylaminoacetonitrile (1) by passing through a 13.56 MHz gaseous discharge was found.Diethylaminoacetonitrile (2) was similarly given from N,N-dimethylformamide.
- Yajima, Tatsuhiko,Tsuchiya, Atsuhiko,Tezuka, Meguru
-
p. 4177 - 4178
(2007/10/02)
-
- Reactive Nitrogenous Molecules from Meldrum's Acid Derivatives, Pyrrole-2,3-diones, and Isoxazolones
-
Flash vacuum pyrolysis of 5-(aminomethylidene)-2,2-dimethyl-1,3-dioxane-4,6-diones (Meldrum's acid derivatives) 12 gives 4-hydroxyquinolines/4-quinolones 15 or 3-enaminoacroleins 22 in good to excellent yields.Intermediate (aminomethylene)ketenes and imidoylketenes are directly observed and their transformation into product 22 monitored by low-temperature IR spectroscopy.Imidoylketenes are also formed and observed upon thermal CO extrusion from pyrrole-2,3-diones 16.Isocyanoamines and fulminates are generated by pyrolysis of hydrazono- or oximino-Meldrum's acid derivatives 32 and 39, monitored by IR spectroscopy, and found to rearrange to cyanamides and cyanates, depending on substituents.The thermal reactions of isoxazol-5(4H)-ones and Meldrum's acid derivatives are compared and discussed.
- Briehl, Horst,Lukosch, Adelheid,Wentrup, Curt
-
p. 2772 - 2779
(2007/10/02)
-
- 2-(N,N-Disubstituted Amino)thiazoles with Electron-withdrawing Groups at Position 5: Prepaeation and Investigation on Structural Features
-
A convenient procedure for preparing N-mono- and NN-di-substituted cyanamides from cyanogen bromide has been developed.N,N-Disubstituted thioureas, obtained from the cyanamides, were condensed with α-bromo-α-cyanoketones to give 5-cyano-2-(N,N-disubstituted amino)thiazoles and with α-bromo-ketones to give 2-(N,N-disubstituted amino)thiazoles.Substitution in the latter products afforded 5-trifluoroacetyl- and 5-nitro-2-(N,N-disubstituted amino)thiazoles; nitration is greatly facilitated by the presence of a 4-aryl group.The average values of the barriers of rotation of the barriers to rotation of the 2-NR2 groups (ΔG298) in the 5-substituted thiazoles were established by variable temperature 1H n.m.r. spectrometry to be 57.4 kJ mol -1 (5-NO2), 56.2 (5-COCF3), and 51.5 (5-CN).I.r. examination showed that the 5-trifluoroacetyl compounds adopt one rotational form preferentially; this is probably the carbonyl O,S-syn-conformation.
- Birkinshaw, Timothy N.,Gillon, David W.,Harkin, Shaun A.,Meakins, G. Denis,Tirel, Malkom D.
-
p. 147 - 153
(2007/10/02)
-
- Conversion of Triazaphospholes into Diazaphospholes by Acetylene Addition/Nitrile Elimination
-
Acetylene di- and (less easily) monocarboxylic esters replace nitriles from the 4,5-position of 1,2,4,3-triazaphosphole rings to give carboxyl derivatives of 1,2,3-diazaphospholes, presumably by a cycloaddition/cycloreversion mechanism.In cases with a mobile N-substituent alternatively the loss of N2 seemed feasible, but was normally not observed. - Keywords: Dicoordinate Phosphorus, Azaphospholes, Cycloaddition, Cycloreversion, NMR Spectra
- Schmidpeter, Alfred,Klehr, Hubert
-
p. 1484 - 1487
(2007/10/02)
-
- The Dehydration of Ureas by Two-Phase Dichlorocarbene Reaction, a Synthetic Access to Substituted Cyanamides
-
A wide variety of N,N-disubstituted ureas are dehydrated in the CHCl3/NaOH catalytic two-phase system under mild conditions.The sequence of urea-transamidation and dehydration thus offers a profitable approach to aprotic cyanamides.Among various tested PT-catalysts tertiary amines prove to be the most efficient and favourable ones.Tertiary amines may also be used advantageously in the transformation of carboxylic amides and thioamides to the corresponding nitriles.The application of the same technique is less suitable in the case of N-mono-substituted ureas, N,N'-disubstituted ureas as well as N(dialkylaminomethylidene)ureas, because consequent reactions of the primarily formed cyanamides predominate.Problems concerning the dehydration mechanism are elucidated in terms of HMO-perturbation theory.
- Schroth, W.,Kluge, H.,Frach, R.,Hodek, W.,Schaedler, H. D.
-
p. 787 - 802
(2007/10/02)
-
- 1,2,3,5-Tetrazinones and Zwitterionic 1,2,4-Triazolin-3-ones
-
Treatment of 2-arylazo-1,1-dimethylguanidines (1) with phosgene yields the novel 1,2,3,5-tetrazinones (2), together with isomeric dipolar triazolinones (4); both types of product decompose to give nitrogen, dimethylcyanamide, and aryl isocyanate.
- Baydar, Ahmet E.,Boyd, Gerhard V.,Lindley, Peter F.,Walton, Adrial
-
p. 225 - 226
(2007/10/02)
-
- 1-Iodoacetylenes. Part 2. Formation Constants of their Complexes with Lewis Bases
-
Formation constants of the complexes of 1-iodoacetylenes (1)-(8) with Lewis bases (9)-(15) have been measured in solution by i.r. spectrophotometry.The stoichiometry of the complexes, the influence of the solvent on the equilibrium position, the existence of linear free energy relationships in the series of iodinated Lewis acids RI, where R=I, Br, Cl, CN, and CCX, and the relation between i.r. frequency shifts and stability constants are discussed.With any electron donor, 1-iodoacetylenes form less stable complexes than those formed by iodine cyanide.With hard bases, iodocyanoacetylene (8) and ethyliodopropiolate (7) give complexes wich are, respectively, more stable than and as stable as those with iodine; however, iodine complexes with soft bases are more stable.This is rationalized, in terms of empirical acidity scales, by the necessity to correlate the thermodynamic and spectroscopic properties of the RI complexes by a double scale equation.
- Laurence, Christian,Queignec-Cabanetos, Michele,Wojtkowiak, Bruno
-
p. 1605 - 1610
(2007/10/02)
-
- The Chemistry of a 1,3,4-Thiadiazin-6-one
-
2-Dimethylamino-5-phenyl-1,3,4-thiadiazin-6-one (2), the first representative of this ring system, undergoes thermal fragmentation to yield benzonitrile, dimethylcyanamide, and 2-dimethylamino-5-phenyl-1,3,4-thiadiazole; its reaction with 1-diethylaminopropyne results in a mixture of adducts, the 1H-pyridazin-4-one (7) and the 5H-pyridazin-4-one (10).
- Baydar, Ahmet E.,Boyd, Gerhard V.,Lindley, Peter F.
-
p. 1003 - 1004
(2007/10/02)
-
- ZUR DEPROTONIERUNG VON CHLOROMETHYLENIMINIUMCHLORIDEN
-
Deprotonation of chloromethyleniminium chlorides (1, 13) leads to cis-trans-isomeres 1,2-diamino-1,2-dichloro-ethenes (3a, 3b resp. 14a; 14b); their reactivity is described.
- Boehme, Horst,Sutoyo, Paulus
-
p. 1671 - 1674
(2007/10/02)
-
