60986-28-9

Upstream product

• 586-96-9 Nitrosobenzene 
• 104351-31-7 (3,3-Dimethyl-but-1-enylidene)-(2,6-dimethyl-phenyl)-amine 
• 119072-54-7 2,6-dimethylphenyl isonitrile 
• 15424-14-3 N-phenylbenzohydrazonoyl chloride 
• 62-53-3 aniline 
• 87-62-7 2,6-dimethylaniline 
• 607-92-1 2,6-dimethylformanilide 
• 622-37-7 Phenyl azide 
• 104351-37-3 N-(2,6-Dimethyl-phenyl)-3,3-dimethyl-butyrimidoyl chloride 
• 25347-93-7 N-(2,6-dimethylphenyl)-N’-phenylthiourea 

Downstream Products

• 13262-44-7 1-(2,6-dimethylphenyl)-3-phenylurea 

Relevant academic research and scientific papers

Electrochemical Synthesis of Carbodiimides via Metal/Oxidant-Free Oxidative Cross-Coupling of Amines and Isocyanides

This work discloses an electrochemical oxidative cross-coupling of amines with aryl and aliphatic isocyanides. In an undivided cell, the reaction proceeds without involving any transition-metal catalyst, oxidant, or toxic reagents providing carbodiimides in good yields, thereby circumventing stoichiometric chemical oxidants, with H2 as the only byproduct. Moreover, carbodiimides were in situ converted into unsymmetrical ureas in moderate to good yields using an electricity ON-OFF strategy.

Palladium-catalyzed cross-coupling reaction of azides with isocyanides

An efficient palladium-catalyzed cross-coupling reaction of azides with isocyanides is developed, providing a general synthetic route to unsymmetric carbodiimides with excellent yields. This method shows a broad substrate scope, including not only aryl azides, but also unactivated benzyl and alkyl azides. Furthermore, from readily available substrates, Pd-catalyzed coupling with a tandem amine insertion cascade to obtain unsymmetric trisubstituted guanidines has been achieved in a one-pot fashion.

β-diketiminato nickel imides in catalytic nitrene transfer to isocyanides

The β-diketiminato nickel(I) species [Me3NN]Ni(2-picoline) (1) serves as an efficient catalyst for carbodiimide (RN=C=NR′) formation in the reactions of a range of organoazides N3R with isocyanides R′NC. [Me3NN]Ni(CNR)2 (R = tBu, Ar (Ar = 2,6-Me2C6H3)) species provide carbodiimides RN=C=NAr′ upon reaction with Ar′N3 (Ar′ = 3,5-Me2C6H3). Nitrene transfer takes place via the intermediacy of nickel imides. Reaction of [MexNN]Ni(2-picoline) (x = 2 or 3) with Ar′N3 gives the new dinickel imides {[Me xNN]Ni}2(μ-NAr′) (4 (x = 3) and 5 (x = 2)) as deep purple, diamagnetic substances. The X-ray structure of {[Me 2NN]Ni}2(μ-NAr′) (5) features short Ni-N imide distances of 1.747(2) and 1.755(2) A along with a short Ni-Ni distance of 2.7210(3) A. These dinickel imides 4 and 5 react stoichiometrically with tBuNC to provide the corresponding carbodiimides tBuN=C=NAr′ in good yield. Azide transfer takes place upon reaction of 1 with TMS-N3 to give the square planar nickel(II) azide [Me3NN]Ni(N3)(2-picoline) (7). Stoichiometric reaction of dinickel dicarbonyl {[Me3NN]Ni} 2(μ-CO)2 with organoazides such as Ar′N 3 is sluggish, indicating that 1 is not an efficient catalyst for nitrene transfer from organoazides to CO to form isocyanates RN=C=O.

A greener synthetic protocol for the preparation of carbodiimide

A new and facile preparation of symmetrical and unsymmetrical 1,3-diaryl and aryl-alkyl carbodiimides via a dehydrosulfurisation of their corresponding thioureas is described. Herein, the classical method of oxidative desulfurisation of thiourea to carbodiimide involving toxic heavy metal oxides (HgO) has been replaced with an easily available, cost-effective and environmentally benign reagent, iodine. Simple reaction conditions, easy purification of the products and high yields are important attributes of the present methodology and perhaps the best alternative from a green chemistry perspective. The only limitation to this method however, is in the preparation of 1,3-dialkyl substituted carbodiimide.

1,2,3- and 1,2,4-triazolium salts, pyrazoles, and quinoxalines from diarylnitrilimines and isocyanides: A study of the scope

Formation of the four title compounds has been found to be strongly dependent on substituents: 1,2,3-Triazolium salts 6 do not arise from nitrilimines 2 that have an electron- acceptor attached to either the C- or the N-phenyl group. Likewise tert-butyl and aryl isocyanides do not afford this class of compounds; from the former isocyanide, dequaternization products 7 are obtained instead, whereas from the latter 1,2,4-triazolium salts 11 are formed. Compounds 11 with a tert-butyl group at the ring are unstable too, giving rise to triazoles 13. Pyrazole formation (analogues of 14) is completely suppressed when both tert-butyl and aryl isocyanides are used, whereas access to this ring system works best with sec-alkyl isocyanides (the influence of substituents of 2 being almost negligible in this case). Formation of quinoxalines 23 which arise from intermediary 1,2-diazets 22 by ring expansion is much favoured on employment of 2 that bears a donator substituent at the N-phenyl group, and under this premise ring closure to 22 is virtually independent on the nature of the isocyanide. Formation of 23 is not observed with 2 having acceptor groups.

Cycloaddition of N-Aryl-tert-butylketenimines to Both Nitrosobenzene and 2-Methyl-2-nitrosopropane

Reactions of the ketenimines 1a, b with nitrosobenzene (2a) do not give the appropriate 1,2-oxazetidines such as 3Aa,b, but produce small amounts of the benzoxazoles 4a, b and the 1,4-benzoxazines 5Aa, b.However, from 1a-c and the nitrosoalkane 2b the analogous compounds 5Ba-c and/or 3Ba-c are formed (depending on conditions); mixtures of 1d-f and 2b afford 3Bd-f only.The heterocycles 4 and 5 are believed to arise through the intermediary cycloadduct 14/14'.