- Synthesis, characterization and biological studies of a sterically hindered symmetrical nitrogen donor ligand and its metal complexes
-
A new sterically hindered Schiff base ligand (SN-NNDMB) was synthesized from meso-1,2-diphenyl ethylenediamine (meso-stien) and 4-N,N′-dimethylaminobenzaldehyde. Its structure was determined by single-crystal X-ray diffraction data. The crystal structure of the organic ligand was found to be triclinic, space group P-1 with a = 6.1407(8) ?, b = 8.8372(12) ?, c = 12.0006(15) ?, α = 103.882(7)°, β = 95.325(8)°, γ = 91.082(7)°, F(0 0 0) = 254, Dc = 1.253 Mg/m3, μ = 0.571 mm?1, R = 0.0399, and wR = 0.1019. Co, Ni, Cu and Zn complexes of SN-NNDMB were also prepared and characterized by elemental analysis, IR-, mass-, NMR- and electronic- spectra, magnetic moment, molar conductance, powder XRD, and TGA. The obtained results show that the Schiff base ligand acts as a bidentate, coordinated through the azomethine nitrogen atoms. According to the biotest such as Antimicrobial, DNA binding, DNA cleaving, Anti-tubercular, Anticancer, and SOD-like activity, the compounds showed better activity after chelation. The Cu(II)-SN-NNDMB complex showed the highest bioactive potential amonst the analyzed compounds.
- Arish, D.,Bhuvanesh, N.,Kumaresan, S.,Shiju, C.
-
-
- Chemoselective Photoredox Synthesis of Unprotected Primary Amines Using Ammonia
-
Unprotected α-amino carbon radicals are produced as novel intermediates via a transformation that merges acid-promoted N-H imine generation and chemoselective photocatalytic single-electron reduction. Coupling ammonia and aldehydes/ketones allows the generation of primary amines under mild conditions without the need for protecting groups. The key intermediate can be efficiently transformed into primary (di)amines by a formal dimerization, reductive amination via hydrogen atom transfer, and arylation through radical-radical coupling.
- Rong, Jiawei,Seeberger, Peter H.,Gilmore, Kerry
-
supporting information
p. 4081 - 4085
(2018/07/15)
-
- Novel riboflavin-inspired conjugated bio-organic semiconductors
-
Flavins are known to be extremely versatile, thus enabling routes to innumerable modifications in order to obtain desired properties. Thus, in the present paper, the group of bio-inspired conjugated materials based on the alloxazine core is synthetized using two efficient novel synthetic approaches providing relatively high reaction yields. The comprehensive characterization of the materials, in order to evaluate the properties and application potential, has shown that the modification of the initial alloxazine core with aromatic substituents allows fine tuning of the optical bandgap, position of electronic orbitals, absorption and emission properties. Interestingly, the compounds possess multichromophoric behavior, which is assumed to be the results of an intramolecular proton transfer.
- Richtar, Jan,Heinrichova, Patricie,Apaydin, Dogukan Hazar,Schmiedova, Veronika,Yumusak, Cigdem,Kovalenko, Alexander,Weiter, Martin,Sariciftci, Niyazi Serdar,Krajcovic, Jozef
-
-
- A New, Short, and Stereocontrolled Synthesis of C2-Symmetric 1,2-Diamines
-
The previously unknown 5-spirocyclohexylisoimidazole has been made efficiently and simply by reaction of ammonia, glyoxal hydrate, and cyclohexanone. It is a very useful precursor for the diastereocontrolled synthesis of many C2-symmetric 1,2-diamines, a class which is important for the generation of a variety of C2-symmetric reagents and catalysts for enantioselective synthesis.
- Vemula, Rajender,Wilde, Nathan C.,Goreti, Rajendar,Corey
-
p. 3883 - 3886
(2017/07/26)
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- Synergistic copper-TEMPO catalysis of intermolecular vicinal diamination of styrenes
-
A copper-catalyzed, 2,2,6,6-tetramethyl piperidine N-oxy radical-assisted intermolecular diamination of styrenes with N-fluorobenzenesulfonimide has been developed. The current protocol proved amenable to a diverse array of styrenes via cascade radical addition to readily afford synthetically useful aromatic vicinal diamines with exclusive diastereoselectivity.
- Weng, Shiue-Shien,Hsieh, Kun-Yi,Zeng, Zih-Jian,Zhang, Jia-Wei
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p. 670 - 673
(2017/01/25)
-
- Enantio- and Diastereoselective Nitro-Mannich Reaction of α-Aryl Nitromethanes with Amidosulfones Catalyzed by Phase-Transfer Catalysts
-
A high-yield, highly diastereo- and enantioselective nitro-Mannich reaction of α-aryl nitromethanes with amidosulfones catalyzed by a novel chiral phase-transfer catalyst, bearing multiple H-bonding donors, derived from quinine was developed. A variety of α-aryl nitromethanes and amidosulfones were investigated; and the corresponding products were obtained in excellent yields with excellent diastereo- and enantioselectivities (up to 99% yield, > 99:1 dr and >99% ee). As a demonstration of synthetic utility, the resulting β-nitroamines could be converted to corresponding meso-symmetric and optically pure unsymmetric anti-1,2-diarylethylenediamines.
- Lu, Ning,Li, Ruxu,Wei, Zhonglin,Cao, Jungang,Liang, Dapeng,Lin, Yingjie,Duan, Haifeng
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p. 4668 - 4676
(2017/05/12)
-
- A (±)-1, 2-diphenyl ethylene diamine preparation method (by machine translation)
-
This invention relates to a kind of (±)-1, 2-diphenyl ethylene diamine preparation method. The 1, 2-disubstituted phenyl b [...] , hydrazine hydrate, formic acid, sodium formate, ammonium formate, ammonium formate-triethylamine a in the system as a hydrogen source, in the 20 °C -100 ° C lower, using Raney nickel as the catalyst, activated carbon as a catalyst, in a polar solvent to obtain the catalytic reduction of (±)-1, 2-diphenyl ethylene diamine. The raw material sources of this invention are simple, cheap, safe production process, the process flow is short, mild reaction conditions, low cost, environment-friendly and the like, is extremely suitable for industrial production. (by machine translation)
- -
-
Paragraph 0031-0034
(2017/01/19)
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- Lipase-catalyzed desymmetrization of meso-1,2-diaryl-1,2-diaminoethanes
-
The synthesis and enzyme-catalyzed desymmetrization of meso-1,2-diaryl-1,2- diaminoethanes have been investigated. A family of aromatic meso-1,2-diamines, containing different substitution patterns in the aromatic ring, was first prepared and then desymmetrized enantioselectively using lipases as biocatalysts. Selective alkoxycarbonylation of one of the amino groups was achieved using allyl carbonates, isolating the corresponding allyl monocarbamates with moderate to high enantiomeric excess at 45 C. Candida antarctica lipase types A (CAL-A) and B (CAL-B) displayed the best activities and stereopreferences, with a dramatic influence being observed depending on the diamine structure. Non substituted and para-substituted aryldiamines led to the formation of allyl carbamates with good enantiomeric excess, using CAL-A for the less hindered substrates and CAL-B for the more hindered ones. On the other hand meta- and ortho-derivatives afforded low or negligible conversions and selectivities, respectively.
- Mendez-Sanchez, Daniel,Rios-Lombardia, Nicolas,Garcia-Granda, Santiago,Montejo-Bernardo, Jose,Fernandez-Gonzalez, Alfonso,Gotor, Vicente,Gotor-Fernandez, Vicente
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p. 381 - 386
(2014/04/03)
-
- NOVEL RUTHENIUM COMPLEX AND PROCESS FOR PRODUCING OPTICALLY ACTIVE ALCOHOL COMPOUND USING SAME AS CATALYST
-
The present invention provides: a novel ruthenium complex which has excellent catalytic activity with respect to reactivity in the reduction of a multiple bond, in particular, in the asymmetric reduction of a carbonyl compound, enantioselectivity, etc.; a catalyst which comprises the ruthenium complex; and a process for producing optically active compound, in particular, an optically active alcohol compound, using the catalyst. The ruthenium complex has a ruthenacyclic structure. The catalyst is a catalyst for asymmetric reduction which comprises the ruthenium complex.
- -
-
Paragraph 0076
(2014/03/21)
-
- Enantioseparation of 1-arylethanols via a supramolecular chiral host consisting of N-(2-naphthoyl)-l-aspartic acid and an achiral diamine
-
A supramolecular chiral host consisting of N-(2-naphthoyl)-l-aspartic acid (L-1) and meso-1,2-diphenylethylenediamine (2) is effective in enantioseparation of 1-arylethanols (up to 96% ee with 100% inclusion ratio). Here we report three different methods to prepare the inclusion crystals and discuss the chiral recognition mechanism on the basis of X-ray crystallography results.
- Kodama, Koichi,Kanno, Ayaka,Sekine, Eriko,Hirose, Takuji
-
experimental part
p. 1877 - 1882
(2012/04/23)
-
- Visible light mediated homo- and heterocoupling of benzyl alcohols and benzyl amines on polycrystalline cadmium sulfide
-
The oxidative coupling of sp3 hybridized carbon atoms by photocatalysis is a valuable synthetic method as stoichiometric oxidation reagents can be avoided and dihydrogen is the only byproduct of the reaction. Cadmium sulfide, a readily available semiconductor, was used as a visible light heterogeneous photocatalyst for the oxidative coupling of benzyl alcohols and benzyl amines by irradiation with blue light. Depending on the structure of the starting material, good to excellent yields of homocoupling products were obtained as mixtures of diastereomers. Cross-coupling between benzyl alcohols and benzyl amines gave product mixtures, but was selective for the coupling of tetrahydroisoquinolines to nitromethane. The results demonstrate that CdS is a suitable visible light photocatalyst for oxidative bond formation under anaerobic conditions.
- Mitkina, Tatiana,Stanglmair, Christoph,Setzer, Wolfgang,Gruber, Michael,Kisch, Horst,Koenig, Burkhard
-
supporting information; experimental part
p. 3556 - 3561
(2012/06/01)
-
- A synthesis of the pseudopterosin A-F aglycone
-
The synthesis of the pseudopterosin A-F aglycone from 3-methylcatechol features (a) the use of asymmetric Ireland-Claisen and aryl Claisen rearrangements to install three of the four stereocentres present in the molecule and (b) an A→AB→ABC annulation strategy using ring-closing metathesis and cationic cyclisation reactions as the key steps.
- Cooksey, John P.,Kocienski, Philip J.,Schmidt, Arndt W.,Snaddon, Thomas N.,Kilner, Colin A.
-
supporting information
p. 2779 - 2785,7
(2020/07/31)
-
- Design, synthesis, and biological evaluation of imidazoline derivatives as p53-MDM2 binding inhibitors
-
Three series of novel imidazoline derivatives were designed, synthesized, and evaluated for their p53-MDM2 binding inhibitory activities, and anti-proliferation activities against PC3, A549, KB, and HCT116 cancer cell lines. Five of the tested compounds showed enhanced p53-MDM2 binding inhibitory potency and anti-proliferation activities in comparison with that of Nutlin-1. Flow cytometric analysis indicated that compound 7c, one of the most potent p53-MDM2 binding inhibitors with a Ki value of 0.6 μM, showed its ability to arrest cell cycle progression.
- Hu, Chunqi,Li, Xin,Wang, Weisi,Zhang, Lei,Tao, Lulu,Dong, Xiaowu,Sheng, Rong,Yang, Bo,Hu, Yongzhou
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p. 5454 - 5461
(2011/10/30)
-
- Diastereo- and enantioselective syntheses of C2-symmetric 1,n-diamines by nucleophilic addition to dialdehyde-SAMP-hydrazones
-
Different protected C2-symmetric 1,n-diamines (R,R)- or (S,S)-4 and 8 can be prepared in high diastereo- and enantiomeric purity by nucleophilic 1,2-addition of organocerium reagents to the CN double bond of bis-SAMP-hydrazones (S,S)-2a-c. The chiral starting materials are readily available by reaction of dialdehydes with the enantiopure hydrazine 1-amino-2-methoxymethylpyrrolidine (SAMP). Reductive NN bond cleavage of the hydrazines (R,R,S,S)- or (S,S,S,S)-3 and 7 afforded the title compounds (de 72-98%, ee 96-98%). The novel entry for the asymmetric synthesis of N-protected C2-symmetric diamines presented here is highly flexible, as both the distance of the amino functions and the introduced residues R can be varied.
- Enders, Dieter,Meiers, Michaela
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p. 2542 - 2560
(2007/10/03)
-
- Reductive coupling of aromatic oxims and azines to 1,2-diamines using Zn-MsOH or Zn-TiCl4
-
The reduction of aromatic aldoxims and azines with Zn in the presence of MsOH or TiCl4 afforded N,N′-unsubstituted 1,2-diamines in one-step. The reductive coupling with Zn-MsOH gave meso 1,2-diamines selectively, whereas dl 1,2-diamines were fo
- Kise, Naoki,Ueda, Nasuo
-
p. 2365 - 2368
(2007/10/03)
-
- Organic chemistry: Preparative synthesis of the Corey chiral controller for enantioselective dihydroxylation of olefins
-
A five-step synthesis of both enantiomers of 1,2-di(2,4,6-trimethylbenzylamino)-1,2-diphenylethane, i.e., Corey (R,R)- and (S,S)-controllers for enantioselective dihydroxylation of olefins by osmium tetroxide, starting from α,α'-diphenylglyoxime, has been developed. The key operations in the synthesis are the optical resolution of intermediate rac-1,2-diamino-1,2-diphenylethane into two enantiomers using only (R,R)-tartaric acid and the subsequent enhancement of the enantiomeric purity to >98% by crystallizations of the corresponding Schiff's bis-bases. Analysis of the enantiomeric purity of the controllers can be easily performed using 1H NMR spectra of their salts with (R)-α-methoxy-α-(trifluoromethyl)phenylacetic acid (Mosher R-acid).
- Lapitskaya,Pivnitsky
-
-
- A simplified synthesis of (±)-1,2-Diphenyl-1,2-diaminoethane (1) from benzaldehyde and ammonia. Revision of the structures of the long-known intermediates 'hydrobenzamide' and 'amarine'
-
A new pathway for the simple, stereocontrolled and economical synthesis of (±)-1 from benzaldehyde is described. The structures of two intermediates (Scheme 1) have been revised to those shown in Scheme 2.
- Corey,Kuehnle, Florian N. M.
-
p. 8631 - 8634
(2007/10/03)
-
- Intramolecular imine cross-coupling in dibenzylidine sulfamides: Synthesis of unsymmetrical 1,2-diaryl ethanediamines
-
Intramolecular reductive cross-coupling of unsymmetrical dibenzylidene sulfamides generates the corresponding cyclic sulfamides in good yield. These intermediates are readily converted to the free, unsymmetrical 1,2-diaryl ethanediamines.
- Pansare, Sunil V.,Malusare, Mahesh G.
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p. 2859 - 2862
(2007/10/03)
-
- Convenient Routes to Symmetrical Benzils and Chiral 1,2-Diaryl-1,2-diaminoethanes, Useful Controllers and Probes for Enantioselective Synthesis
-
Pathways for the diastereoselective preparation of chiral 1,2-diaryl-1,2-diaminoethanes from ArCOOH, ArCHO or ArBr are described.
- Corey, E. J.,Lee, Duck-Hyung,Sarshar, Sepehr
-
-
- Synthesis of Nitrogen-Containing Macrocycles with Reductive Intramolecular Coupling of Aromatic Diimines
-
Reductive intramolecular coupling of aromatic diimines is an effective method for the synthesis of a variety of nitrogen-containing macrocycles. 1,4-Diazacrown ethers 3 were effectively synthesized by intramolecular coupling of bis(imino ethers) 9 promoted by electroreduction (method A) or chemical reduction with zinc powder (method B) in the presence of methanesulfonic acid.In spite of the formation of macrocycles, the yields of 3 were relatively high.This can be explained by the formation of proton-bridged intermediates 14, in which intramolecular hydrogen bonds are formed between hydrogen and oxygen atoms of diiminium salts.Method B was more effective in the formation of 1,4-diaza-12-crown-4 derivatives 3 (n = 1) due to the template effect of Zn(2+).Optically active macrocyclic bislactones 4 were synthesized stereoselectively by reductive intramolecular coupling of bis(imino esters) 20 with zinc powder (method B).The high stereoselectivity is explained by considering proton-bridged intermediate 23.The resultant compounds 4 were transformed to optically active 1,2-diarylethylenediamines 7.Various sizes of macrocyclic bislactams 5 were synthesized by reductive intramolecular coupling of bis(imino amides) 26 with zinc powder (method B).Reduction of 5 gave the corresponding macrocyclic polyamines 6.
- Kise, Naoki,Oike, Hideaki,Okazaki, Eiichi,Yoshimoto, Masami,Shono, Tatsuya
-
p. 3980 - 3992
(2007/10/02)
-
- Stereochemical Studies of N,N'-Diacetyl-N,N'-dimethyl-1,2-diamino-1,2-diphenylethanes and their Mono- and Di-thio Analogues by NMR and CD Spectroscopy and by Molecular Mechanics Calculations
-
The R*,R* and R*,S* diastereomers of N,N'-diacetyl-N,N'dimethyl-1,2-diamino-1,2-diphenylethane and their mono- and di-thio analogues (1-6) have been studied by 1H and 13C NMR spectroscopy and by empirical force-field calculations (MMP2-85).The NMR spectral data (chemical shifts, coupling constants and NOE) clearly show that all compounds exist in the anti conformation with the Z,Z configuration for the (thio)amide groups.The same result is obtained by the force-field calculations.Four of the compounds (2, 3, 4 and 6) are chiral and have been resolved into enantiomers by chromatography on triacetylcellulose.The CD spectra of the first eluted enantiomers of 4 and 6 could be reasonably well reproduced by calculations based on minimum energy geometries for the S,S enantiomers, whereas no agreement could be reached for 2 and 3.This agrees with the results of the force-field calculations, which predict one predominant conformer for each of 4 and 6, but significant amounts of two rotamers (both anti ZZ) for each of 2 and 3.
- Chiara, Jose Luis,Petrova, Rumyana,Simeonov, Mario,Spassov, Stefan L.,Khan, Agha Zul-Quarnain,Sandstroem, Jan
-
p. 555 - 562
(2007/10/02)
-
- Use of α-Bromo Oxime Ethers in the Synthesis of 1,2-Diamines
-
Oxime ethers 1 react with ammonia and primary amines to give α-amino oxime ethers.The reaction of α-bromo oxime ethers with sodium azide affords α-azido oxime ethers.Hydrogenolysis of the azido compounds using 5percent palladium on calcium carbonate as catalyst yields the α-amino oxime ethers.The reaction of α-azido oxime ethers with lithium aluminum hydride gives 1,2-ethanediamine derivatives.The reaction of azido oxime ether 13 with LiAlH4, and subsequently the reaction of the resulting mixture of the diamines 14 and 15 with phosgene, preferably gives cis-4-pentyl-5-methyl-2-imidazolidone (16) indicating that the reduction of 13 proceeds in a stereoselective manner to furnish mainly the syn-1,2-ethanediamine 15. Key Words: Oxime ethers / α-Azido oxime ethers / α-Amino oxime ethers / 1,2-Ethanediamines
- Shatzmiller, Shimon,Bercovici, Sorin
-
p. 1005 - 1010
(2007/10/02)
-
- Stereoisomeric Dichloroplatinum(II) Complexes, Part I: Synthesis
-
Various erythro- and threo-configurated dichloroplatinum(II) complexes were synthesized with the hydroxy group located in either the 2-, 3-, or 4-position of the phenyl ring (38-40).The diastereoisomeric 1-(3-
- Mueller, Richard,Gust, Ronald,Klement, Ulrich,Schoenenberger, Helmut
-
p. 2381 - 2389
(2007/10/02)
-
- 211. Scope and Limitations of the Reductive Coupling of Aromatic Aldimine Derivatives with Formation of 1,2-Diarylethylenediamine Units, Using Low-Valent Titanium Reagents
-
Besides the adducts from lithium amides to aromatic aldehydes, iminium salts, aminals, and N-silylimines of aromatic aldehydes are coupled by the black suspension obtained from TiCl4 and Mg turnings in tetrahydrofuran (THF).The 1,2-diarylethylenediamines with tertiary and primary amino groups thus obtained are formed with no or only moderate diastereoselectivity (products 4a-d (Scheme 2) and 5a-e (Scheme 3), respectively); the amine component may contain a strained ring or additional heteroatoms as in azetidin, bis(2-metoxyethyl)amine piperazine, morpholine, and thiomorpholine (products 6a-e; Table 1).By an in-situ procedure, ethylenediamines and propane-1,3-diamines with two secondary amino groups are cyclized with aromatic aldehydes to give exclusively trans-diaryl-substituted piperazine and perhydro-1,4-diazepine derivatives (products 7a-f; Table 2).Enantiomerically pure monocyclic trans,cis-5-alkyl-2,3-diaryl-piperazines and diazabicyclononanes and -decanes are obtained by employing suitable diamines prepared from the amino acids (S)-alanine, (S)-phenylalanine, (S)-proline, and from (S,S)- or (R,R)-cyclohexane-1,2-diamine, respectively (products 11a-i, 7e; Table 4).The configurations of all products are derived from the high-field NMR spectra, some of which are discussed in detail (Figs. 1 and 2, Tables 3 and 5); all new compounds are fully characterized by their physical data.Depending upon the structure of the components employed, the yields of purified products range from as low as 7percent to essentially quantitative.
- Betschart, Claudia,Schmidt, Beat,Seebach, Dieter
-
p. 1999 - 2021
(2007/10/02)
-
- 208. Aminierende reduktive Kupplung aromatischer Aldehyde mit niedervalenten Titan-Reagenzien zu 1,2-Diarylethylendiaminen
-
In a novel McMurry-type one-pot reaction, aromatic aldehydes and secondary amines are coupled to give the N,N,N',N'-tetralkyl-1,2-diarylethylendiamines 1-22 (Table 3).To this end, a lithium dialkylamide is added to an aromatic aldehyde to give the adduct B which is then treated with 1 equiv. of TiCl4 to yield a coloured suspension of a reagent synthetically equivalent to a iminium salt (C/D in Scheme 4).After treatment with a low-valent Ti reagent which is prepared by reduction of TiCl4 with either K or, preferably, Mg, the coupling products are isolated in 23 to 81 percent yield as a 1:1 mixture of the diastereoisomers (meso- and rac-form).These are separated either by chromatography or by crystallization and characterized.
- Betschart, Claudia,Seebach, Dieter
-
p. 2215 - 2231
(2007/10/02)
-
- ALKYLATION OF SCHIFF BASES BY HALIDES OF THE PROPARGYL TYPE
-
The alkylation of N-diphenylmethylenebenzylamine with 3-bromo-1-propyne and 1-bromo-2-pentyne under the conditions of phase-transfer catalysis was investigated.It was established that the process takes place unambiguously, and the yield of the primary γ-a
- Remizova, L. A.,Shustrova, T. A.,Favorskaya, I. A.
-
p. 888 - 890
(2007/10/02)
-
- ASYMMETRIC REDUCTION OF ACETOPHENONE WITH CHIRAL REAGENTS FROM LITHIUM TETRAHYDROALUMINATE AND CHIRAL 1,2-DIOL OR DIAMINE AS STUDIED BY ALUMINUM-27 NUCLEAR MAGNETIC RESONANCE
-
Asymmetric reduction of acetophenone with chiral reagents from lithium tetrahydroaluminate and (1S,2S)-1,2-diphenylethanediol or (1S,2S)-N,N'-diethyl-1,2-diphenylethanediamine in the presence or absence of added ethanol is studied by aluminum-27 NMR spectroscopy.
- Yamashita, Junzo,Tomiyama, Shigemi,Hashimoto, Harukichi,Kitahara, Keiichi,Sato, Hisao
-
p. 749 - 752
(2007/10/02)
-
- Thermal Rearrangements and Nucleophilic Ring Cleavage of cis-2,3-Dihydro-2,3-diphenyl-1H-1,4-diazepines
-
Thermolysis of cis-2,3-dihydro-2,3-diphenyl-1H-1,4-diazepine (c2a) at 150 deg C in 5>bromobenzene solution affords quantitatively 2,3-diphenylpyridine (4a) via ring contraction and loss of one mole of ammonia.In striking contrast, on heating a 5>bromobenzene solution of cis-2,3-dihydro-2,3,6-triphenyl-1H-1,4-diazepine (c2b) to 140 deg C loss of C7H8 occurs resulting in the formation of 2,5-diphenylpyrimidine (5b) in 70percent yield.Mechanisms are proposed in order to rationalize these surprising ring contractions.Piperidine in methanol cleaved the ring of c2a*H+ producing meso-1,2-diphenyl-1,2-ethanediamine (12) and 1,3-dipiperidinopropenylium perchlorate (13).
- Quast, Helmut,Seidenspinner, Hubert-Matthias,Stawitz, Josef
-
p. 1230 - 1236
(2007/10/02)
-
- ALKYLATION OF N-BENZYLIDENEBENZYLAMINE BY HALIDES OF THE PROPARGYL TYPE
-
The alkylation of N-benzylidenebenzylamine by halides of the propargyl type under the conditions of interphase catalysis was investigated.It was established that the yield of the γ-acetylenic amine 1-phenyl-1-amino-3-butyne under these conditions amounts to only 5-10 percent, while diphenylethylenediamine is formed with yields of 20-25 percent.Propargylation of N-benzylidenebenzylamine gives a satisfactory yield when the reaction is carried out through the preliminary stage of metallation with observance of the temperature conditions (-70 deg C).
- Mostamandi, A.,Remizova, L.A.,Pavlenkova, A.L.,Favorskaya, I.A.
-
p. 850 - 852
(2007/10/02)
-
- METALLATION OF BENZYLIDENEBENZYLAMINE
-
The reactions of benzylidenebenzylamine with methyllithium and lithium diethylamide were investigated by GLC.Products with different structures from condensation of the azomethine are formed: Cyclic 2,4,5-triphenyl-3-benzylimidazolidine and noncyclic dibenzylidene-1,2-diphenylethylenediamine.Investigation of the effects of the solvent, temperature, and ratio of reagents on the reaction made it possible to obtain conditions for synthetic application of the 1,3-diphenylazaallyllithium, obtained by metallation of benzylidenebenzylamine, in reactions with alkyl halides, carbon dioxide, carbonyl compounds, and phenyl isocyanate.These conditions involve a temperature between -60 and -70 deg C and an equimolar ratio between the reagents.
- Gracheva, R. A.,Potapov, V. M.,Sivov, N. A.,Sivova, L. I.
-
p. 1963 - 1970
(2007/10/02)
-
- Reactions of Trimethylsilyl Cyanide and N-(Trimethylsilyl)diphenylmethyleneamine with Nitrones and Thermal Decompositions of Their Adducts
-
Trimethylsilyl cyanide (1) and N-(trimethylsilyl)diphenylmethyleneamine (2) reacted with α-aryl-N-phenylnitrones to afford the corresponding 1:1 adducts 4 and 5 respectively.Thermal decomposition of 4 in refluxing xylene gave azoxybenzene, stereoisomers of 2,3-diarylsuccinonitriles, α-aminonitriles and/or benzanilides, whose yields depended on the nature of substituents on phenyl group of 4.On heating in benzene 5 afforded a mixture of azoxybenzene and meso-N,N'-bis(diphenylmethylene)-1,2-diarylethylenediamines.On the other hand, reactions of 1 and 2 with N-(diphenylmethylene)aniline N-oxide or N-(9-fluorenylidene)aniline N-oxide did not give the corresponding 1:1 adducts, but instead compounds arising from thermal decomposition of initial 1:1 adducts were directly obtained.The reaction of 1 with N-(p-diethylaminophenyl)-α-phenylnitrone leading to the corresponding α-imino nitrile is also described.
- Tsuge, Otohiko,Urano, Satoshi,Iwasaki, Takahiko
-
p. 485 - 489
(2007/10/02)
-
- Novel Reductive Cleavage of Benzaldehyde and Benzophenone N-Benzhydrylimines with Sodium in Dry Dioxane
-
The reaction of sodium with benzaldehyde N-benzhydrylimines in dry dioxane followed by protonation gives three products characterised as diphenylmethane, benzylbenzhydrylamine and dl-1,2-diphenyl-1,2-diaminoethane.Similar treatment of benzophenone N-benzhydrylimine leads to diphenylmethane and benzhydrylamine.
- Giri, B. P.
-
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