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Upstream product

• 18039-42-4 5-Phenyl-1H-tetrazole 
• 1199-02-6 5-phenyl-3H-[1,3,4]oxadiazol-2-one 
• 622-34-4 1-phenylcyanamide 
• 5378-52-9 phenyl-1H-tetrazole 
• 56476-95-0 2-phenyl-2H-tetrazole 
• 18039-42-4 5-phenyl-2H-1,2,3,4-tetrazole 
• 508191-77-3 3-phenylsydnone 
• 103-85-5 monophenylthiourea 

Downstream Products

• 17813-57-9 N,N-diethyl-N'-phenylguanidine 

Relevant academic research and scientific papers

Dehydrogenative desulfurization of thiourea derivatives to give carbodiimides, using hydrosilane and an iron complex

Dehydrogenative desulfurization of thiourea derivatives (RNHC(S)NHR′) has been achieved, to give carbodiimides (RNCNR′), in the reaction with hydrosilane and (η5-C5H5)Fe(CO) 2Me. The obtained carbodiimide reacted with (η5-C 5H5)Fe(CO)(SiR3) formed in the reaction to give an N-silylated η2-amidino iron complex, which was isolated and then characterized by X-ray analysis.

Bond-shift isomers: The co-existence of allenic and propargylic phenylnitrile imines

We discovered a 1,3-dipolar species co-existing in two different structures. Photolysis of matrix-isolated 5-phenyltetrazole generates two forms of phenylnitrile imine: propargylic and allenic. They are not resonance structures but correspond to different energy minima, representing bond-shift isomers. These distinct species were characterized spectroscopically and confirmed by calculations up to the CASSCF(14,12) theory level.

Photolysis and Pyrolysis of Phenyltetrazoles: Formation of Phenylcarbodiimide, N-Phenylnitrile Imine, Phenylnitrene, Indazole, and Fulvenallene

Photolysis of 1-phenyltetrazole 2b at either 193 or 266 nm in a Ne matrix as well as flash vacuum pyrolysis (FVP) of the same compound with isolation of the products in Ne matrix generate phenylcarbodiimide PhN=C=NH 6 very efficiently as the principal product in an almost pure state. Minor amounts of phenyl azide 8 and 1-azacyclohepta-1,2,4,6-tetraene 10, the product of ring expansion of phenylnitrene, are also formed, and the amounts of both substances increase as a function of photolysis time. The photolysis of 2-phenyltetrazole 1b in a Ne matrix at 266 nm for 0.5 min generates the allenic N-phenylnitrile imine PhN=N(+)=CH(–) 3b, absorbing strongly and cleanly at 2021 cm–1 in the IR spectrum. At longer photolysis times peaks ascribed to phenyl azide, phenylnitrene, 1-azacycloheptatetraene, and phenylcarbodiimide 6 become prominent. FVP of 2-phenyltetrazole yields indazole 15 as the major product together with a small amount of phenylcarbodiimide 6. Indazole formation is ascribed to cyclization of the nitrile imine in the ground state. It is not formed on FVP of 1-phenyltetrazole in agreement with the computational result that the thermodynamically most favourable path for rearrangement of the putative N-phenylimidoylnitrene 5b yields phenylcarbodiimide 6 rather than phenylnitrile imine 3b. Further pyrolysis of indazole affords a minor yield of fulvenallene 18.

A method of manufacturing a carbodiimide compound

PROBLEM TO BE SOLVED: To provide a novel method that can efficiently produce a carbodiimide compound without using substances that are harmful, hazardous, expensive, or difficult to obtain.SOLUTION: The method of producing a carbodiimide compound includes converting a thiourea compound having a specific structure to a carbodiimide compound having a specific structure in the presence of at least one of an iron compound and a molybdenum compound.

Sydnone photochemistry: Direct observation of earl's bicyclic lactone valence isomers (oxadiazabicyclo[2.1.0] pentanones), formation of carbodiimides, reaction mechanism, and photochromism

The matrix photolyses of 3-phenyl-, 3-pyridyl, and 3,4-diphenylsydnones 16, 19, and 22 were investigated by matrixisolation infrared spectroscopy. The formation of the neutral, bicyclic lactone valence isomers postulated by Earl - the oxadiazabicyclo[2.1.0]pentanones exo-17 and exo-20 - was clearly observed in the first two cases and is also likely in the case of exo-23 (C=Oabsorptions in the IR at 1881, 1886, and 1874 cm -1, respectively). The efficient photodecomposition of sydnones to carbodiimides RN=C=NR0 (18, 21, and 24) and CO2 was established in all three cases. The formation of benzonitrile 27 and azacycloheptatetraene 29 in the matrix photolysis of diphenylsydnone 22 is indicative of diphenylnitrile imine PhCNNPh 26 as an intermediate (2340 cm -11). Neither bicyclic lactones nor carbodiimides have been observed previously in sydnone photochemistry. A general reaction mechanism for the formation of carbodiimides, nitrile imines, and photochromism is put forward. CSIRO 2014.

Nitrile imines: Matrix isolation, IR spectra, structures, and rearrangement to carbodiimides

The structures and reactivities of nitrile imines are subjects of continuing debate. Several nitrile imines were generated photochemically or thermally and investigated by IR spectroscopy in Ar matrices at cryogenic temperatures (Ph-CNN-H 6, Ph-CNN-CH317, Ph-CNN-SiMe323, Ph-CNN-Ph 29, Ph3C-CNN-CPh334, and the boryl-CNN-boryl derivative 39). The effect of substituents on the structures and IR absorptions of nitrile imines was investigated computationally at the B3LYP/6-31G level. IR spectra were analyzed in terms of calculated anharmonic vibrational spectra and were generally in very good agreement with the calculated spectra. Infrared spectra were found to reflect the structures of nitrile imines accurately. Nitrile imines with IR absorptions above 2200 cm -1 have essentially propargylic structures, possessing a CN triple bond (typically PhCNNSiMe323, PhCNNPh 29, and boryl-CNN-boryl 39). Nitrile imines with IR absorptions below ca. 2200 cm-1 are more likely to be allenic (e.g., HCNNH 1, PhCNNH 6, HCNNPh 43, PhCNNCH317, and Ph3C-CNN-CPh334). All nitrile imines isomerize to the corresponding carbodiimides both thermally and photochemically. Monosubstituted carbodiimides isomerize thermally to the corresponding cyanamides (e.g., Ph-N=C=N-H 5 Ph-NH-CN 8), which are therefore the thermal end products for nitrile imines of the types RCNNH and HCNNR. This tautomerization is reversible under flash vacuum thermolysis conditions.