101-61-1Relevant articles and documents
Polyethylene Glycol (PEG-400) as Methylene Spacer and Green Solvent for the Synthesis of Heterodiarylmethanes under Metal-Free Conditions
Kumar, Rahul,Rawat, Deepa,Adimurthy, Subbarayappa
, p. 3499 - 3507 (2020)
Polyethylene glycol 400 (PEG-400) has been employed as a green, biodegradable solvent as well as methylene spacer for the one-pot synthesis of heterodiarylmethanes under metal-free conditions. PEG-400 is used for the dimerization of both symmetrical and unsymmetrical fused heterocycles and arenes as methylene spacer. The reaction was facilitated by (diacetoxyiodo)benzene (PIDA) as an oxidant. This reaction proceeds without transition metal, base, ligand, and under additive-free conditions involving the coupling of sp3 and sp2-hybridized carbon atoms. The method is applicable for variety of heterocycles such as imidazopyridines, imidazothioazoles, imidazobenzothiozoles, indolizines, indole, 1-methyl-1H-indole, N,N-dimethylaniline and trimethoxybenzene. Good to excellent yields and applicability to gram-scale synthesis demonstrate the potential scope of the process for commercial/industrial applications.
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Doebner
, p. 813 (1879)
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Lemoult
, (1902)
Light-promoted N,N-dimethylation of amine and nitro compound with methanol catalyzed by Pd/TiO2 at room temperature
Zhang, Lina,Zhang, Yan,Deng, Youquan,Shi, Feng
, p. 14514 - 14521 (2015)
A series of TiO2 supported nano-Pd catalysts (Pd/TiO2) were prepared and used for the N,N-dimethylation of different amines and nitro compounds with methanol under UV irradiation at room temperature. A wide range of N,N-dimethyl amines were one-pot synthesized with up to 98% by applying aliphatic secondary amines, aromatic primary amines, aliphatic primary amines and aromatic nitro compounds as starting materials. It is noteworthy that up to 90% yield of 4-chloro-N,N-dimethylaniline was obtained by adjusting the Pd loadings on the TiO2 and the dehalogenation reaction was inhibited. Finally, a reaction mechanism is discussed, involving PhN = CH2 and PhNHCH3 as reaction intermediates.
Novel formaldehyde-mediated dimerization reaction of n-alkyl-1-naphthylamine derivatives under mild/neutral conditions; application to synthesis of naphthylamine-derived macrocycles
Takahashi, Hiroyasu,Hashimoto, Yuichi,Nagazawa, Kazuo
, p. 2305 - 2313 (2001)
The dimerization reaction of N-methyl-1-naphthylamine (1) with formaldehyde is described. Reaction of 1 with formaldehyde under mild/neutral conditions gave bis-4-(1-N-methylaminonaphthyl)methane (2) in high yield as a single dimerization product. This formaldehyde-mediated aromatic condensation reaction is chemo- and regio-selective, and it takes place particularly with N-monoalkyl-1-naphthylamines as substrates. The novel naphthylamine-derived macrocyclic compounds 1,6,28,33-tetraaza-[6.1.6.1]paranaphthalenophane (13a) and 1,13-diaza[13,1]paranaphthalenophane (12c) were synthesized by application of this formaldehyde-mediated mild/neutral condensation reaction as the key step.
Kinetics and mechanism of the reactions of amine boranes with carbenium ions
Funke, Marcus-A.,Mayr, Herbert
, p. 1214 - 1222 (1997)
The kinetics of the reactions of trialkylamine boranes and pyridine boranes with benzhydryl cations have been determined photometrically. Second-order rate laws are obeyed, first-order with respect to amine borane concentration and first-order with respect to carbocation concentration. As for other reactions of carbocations with neutral nucleophiles, the rates of these reactions are only slightly affected by solvent polarity. The structure-reactivity relationships and kinetic isotope effects are in accord with a polar mechanism proceeding through a transition state where the migrating hydride is partly bound to the entering carbon and to the leaving boron atom. The rate constants correlate linearly with the electrophilicity parameters E. of the carbenium ions. It is therefore possible to use the linear free enthalpy relationship logk2 = s(E+N) for determining nucleophilicity parameters N for the amine boranes and to compare their hydride-donating abilities with those of other non-charged hydride donors (silanes, germanes, stannanes, and dihydropyridines).
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Carter,Moulds,Riley
, p. 1305,1309, 1310 (1937)
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Photochemical Reaction of Diaryliodonium Salts with Dimethylaniline
Bi, Yubai,Neckers, Douglas C.
, p. 1139 - 1142 (1992)
A solution of 4,4'-dimethyldiphenyl iodonium tettrafluoroborate and N,N-dimethylaniline in acetonitrile is irradiated by UV light to give iodotoluene, toluene, 4,4'-methylenebis(N,N-dimethylaniline), crystal violet, methyl violet. KEY WORDS: 4,4'-dimethyldiuphenyl iodonium salt; N,N-dimethylaniline; 4,4'-methylenebis(N,N-dimethylaniline); crystal violet; methyl violet.
Stopped-flow Kinetic Study of the Formation and Decay of the 4,4'-(Dimethylamino)diphenylmethane Radical Cation in Aqueous Solution
Aravindan, Ponnu,Maruthamuthu, Pichai,Dharmalingam, Periasamy
, p. 2743 - 2750 (1995)
The oxidation kinetics of 4,4'-(dimethylamino)diphenylmethane (DMADPM) by Ce(IV), by the oxoanions, MnO4(1-) and Cr2O7(2-), by peroxides, namely, peroxomonosulfate, peroxodisulfate and H2O2, and by halogens viz., Cl2, Br2 and I2, to the radical cation, DMADPM.(1+) along with further oxidation to the product monocation DMADPM(1+) have been studied by the stopped-flow technique.The first- and second-stage oxidations have been followed by monitoring the formation and decay of DMADPM.(1+) via the absorption at 610 nm.Both formation and decay of DMADPM.(1+) obey total second-order kinetics, first-order each with respect to or .(1+)> and .The effects of pH and temperature have also been investigated on the formation and decay of DMADPM.(1+) and the kinetic and transition-state parameters have been evaluated and discussed with suitable reaction mechanisms.DMADPM.(1+) was converted back into the DMADPM by the following reducing agents; ascorbic acid, dithionite, metabisulfite, sulfite and thiosulfate.The rate constants for these reactions were estimated.The experimentally determined rate constants for the oxidative electron-transfer reactions were correlated theoretically using Marcus theory and the observed and calculated rate constants show good agreement.
Full N,N-Methylation of 4,4′-Methylenedianiline with Dimethyl Carbonate: A Feasible Access to 4,4′-Methylene bis(N,N-Dimethylaniline)
Qiu, Zegang,Wang, Kunjie,Li, Zhiqin,Li, Tao,Bai, Jinhao,Yin, Chanjuan,Ye, Xiushen,Liu, Haining
, (2018)
The full N,N-methylation of 4,4′-methylenedianiline (MDA) with dimethyl carbonate (DMC) was investigated. The yield of the major product 4,4′-methylene bis(N,N-dimethylaniline) (MBDMA) reached as high as 97% over NaY catalyst at 190°C for 6 h. The catalyst could be used for two more times with acceptable MBDMA yields higher than 90%. The main by-products were identified as three N-methylated derivatives. Surprisingly, the formation of the N-methoxycarbonylation product was extremely restrained, which could be produced in high yields of 98% on zinc acetate catalyst. Furthermore, the reaction pathway to the major product MBDMA was proposed. Finally, a feasible synthetic route of 4,4′-methylene bis(N,N-dimethylaniline) (MBDMA) was established, featuring a high yield, mild reaction conditions, and simple operations.
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Cohn
, p. 564 (1900)
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An experimental and theoretical study on the preparation of 4,4′-methylene-bis(N,N-dimethylaniline) in ionic liquid
Wang, Yun
, p. 276 - 280 (2016)
The reaction of N,N-dimethylaniline with tetrachloromethane in ionic liquid was found to give 4,4′-methylene-bis (N,N-dimethylaniline) in considerable yield. The ionic liquid was prepared from N,N-dimethylaniline which is also the one of raw materials for the preparation of 4,4′-methylene-bis (N,N-dimethylaniline), and acts as both solvent and catalyst in the reaction. Mild reaction conditions, enhanced rates, improved yields, and reagents' reactivity which is different from that in conventional organic solvents are the remarkable features observed in ionic liquids. In addition, the results of calculations are in good accordance with the experimental outcomes.
HYDRIDE TRANSFER REACTIONS OF MICHLER'S HYDRIDE WITH DIFFERENT ?-ACCEPTORS
Zaman, Khan. M.,Nishimura, Norio,Yamamoto, Shunzo,Sueishi, Yoshimi
, p. 309 - 315 (1994)
The hydride transfer reactions of 4,4'-bis(dimethylaminophenyl)methane (Michler's hydride) with p-benzoquinones were studied.The rate of formation of Michler's Hydrol Blue was followed spectrophotometrically.The second-order rate constants and the activation parameters were estimated.The formation of a charge-transfer complex was observed at low temperatures.Stable and unstable paramagnetic species formed during the reactions were assigned by ESR spectroscopy.The observed kinetic behaviour and the stoichiometry were in line with those previously obtained for the systems involving Leuco Crystal Violet, Leuco Malachite Green and Leuco Bindshedler's Green.Hence the reaction is considered to proceed according to the so-far accepted multi-step mechanism.However, when tetracyano-p-quinodimethane or tetracyanoethylene was used as a ?-acceptor, a comparatively stable radical ion pair was formed as a result of a one-electron transfer, followed by the gradual formation of Michler's Hydrol Blue.The kinetic behaviour and the stoichiometry of the reaction were examined, together with the enhanced kinetic effects of added triethylamine.A modified mechanism for these systems is proposed.The role of cyanomethylenes was found to be essentially different from that of p-benzoquinones, and therefore ?-acceptors are divided into two groups of cyanomethylenes and p-benzoquinones.
Additive-free selective methylation of secondary amines with formic acid over a Pd/In2O3 catalyst
Benaissa, Idir,Cantat, Thibault,Genre, Caroline,Godou, Timothé,Pinault, Mathieu
, p. 57 - 61 (2022/01/19)
Formic acid is used as the sole carbon and hydrogen source in the methylation of aromatic and aliphatic amines to methylamines. The reaction proceeds via a formylation/transfer hydrogenation pathway over a solid Pd/In2O3 catalyst without the need for any additive.
Electro-oxidative C(sp2)-H/O-H cross-dehydrogenative coupling of phenols and tertiary anilines for diaryl ether formation
Tang, Hongyang,Smolders, Simon,Li, Yun,De Vos, Dirk,Vercammen, Jannick
, p. 3925 - 3930 (2021/06/18)
The formation of diaryl ethers is generally achievedviatransition metal catalyzed etherification reactions (Ullmann, Chan-Lam, Buchwald-Hartwig) with prefunctionalized aryl halide substrates at elevated temperatures. Herein, we report a protocol for electrochemical C(sp2)-H/O-H cross-dehydrogenative coupling of phenols and tertiary anilines to synthesize diaryl ethers. The C(sp2) H/O-H coupling product can be obtained under metal- and oxidant-free conditions at room temperature in moderate to excellent yield (up to 83% yield) with high regioselectivity (>99% forpara-substitution) and with a broad substrate scope (22 examples).
Nitrosoarene-catalyzed regioselective aromatic C-H sulfinylation with thiols under aerobic conditions
Chatterjee, Indranil,Patel, Sandeep,Pradhan, Suman
supporting information, p. 5054 - 5057 (2020/05/18)
Aromatic amines and (hetero)arenes, such as indoles and pyrroles, are regioselectively sulfinylated under mild aerobic conditions using nitrosoarenes as a redox-catalyst. The nitrosoarene is involved in the electron transfer process with arenes to generate a crucial arene radical cation intermediate for C-H sulfinylation. The present methodology requires no directing group, can be scaled up easily and is applicable for the late-stage functionalization of drug molecules and natural products with high regioselectivity.
