14016-34-3

Basic information

• Product Name: Benzenamine, N-(2-methyl-1-propenylidene)-
• CAS NO: 14016-34-3
• Molecular Formula: C10H11N
• Molecular Weight: 145.204
• Mol File: 14016-34-3.mol
• Article Data: 5

Chemical Properties

• CAS DataBase Reference: Benzenamine, N-(2-methyl-1-propenylidene)-(CAS DataBase Reference)
• NIST Chemistry Reference: Benzenamine, N-(2-methyl-1-propenylidene)-(14016-34-3)
• EPA Substance Registry System: Benzenamine, N-(2-methyl-1-propenylidene)-(14016-34-3)

Safety Data

• Hazardous Substances Data: 14016-34-3(Hazardous Substances Data)

Upstream product

• 51942-54-2 3-phenyl-4,4-dimethyl-5-oxo-2-isoxazoline 
• 62-53-3 aniline 
• 46170-01-8 1-<1-(2-methyl)propenyl>benzotriazole 
• 50737-95-6 N-phenyl-isobutyrimidoyl chloride 
• 16666-80-1 triphenylphosphonio-1-methylethanide 
• 103-71-9 phenyl isocyanate 
• 4406-41-1 N-phenylisobutyramide 
• 598-26-5 dimethylketene 
• 2325-27-1 N-phenyltriphenyliminophosphorane 

Downstream Products

• 4406-41-1 N-phenylisobutyramide 
• 49633-47-8 2-methyl-1-oxo-1-(phenylamino)propan-2-yl acetate 
• 63086-83-9 2-Isopropyl-4,4-diphenyl-4H-3,1-benzothiazine 
• 127842-77-7 (2-Methyl-propenyl)-phenyl-carbamic acid methyl ester 
• 133850-91-6 3,3,3-tricarbonyl-4-isopropyl-1,2-diphenyl-3-(trifluoroacetoxy)-1-aza-3-ferra-2-cyclobutene-4-carboxylic acid-ethylester 
• 196872-02-3 2,2-bis(trifluoromethyl)-3,3-dimethyl-4-(dimethyliminio)-1-phenyl-aza-2-boratacyclobutane 
• 133850-86-9 tricarbonyl{{{1,2-η-1-(ethoxycarbonyl)-2-methyl-1-propenyl}phenylamino}phenylcarbene}iron(0) 
• 133850-85-8 tricarbonyl{(1,3,3α,4)-η-3-{(Z)-α-ethoxybenzylidene}-4-methyl-1-oxo-2-aza-1,4-pentanediyl}iron(0) 
• 58245-23-1 N-Phenyl-N'-p-toluolsulfonyl-isobutyramidin 
• 77971-07-4 4-Methyl-N-[2-methyl-1-phenylamino-prop-2-en-(Z)-ylidene]-benzenesulfonamide 
• 29172-31-4 N,N-Dimethyl-N'-phenylisobutyramidin 
• 120242-70-8 dimethyl 2',2'-dimethyl-5-oxo-1-phenyl-3',3'-dichlorospiro-3,4-dicarboxylate 
• 120242-67-3 dimethyl 2-isopropyl-1-methyl-5-chloropyrrole-3,4-dicarboxylate 
• 120242-69-5 dimethyl 2',2'-dimethyl-1-phenyl-3',3',5-trichloro-2,3-dihydrospiro-3,4-dicarboxylate 

Relevant articles and documents

Nitrile imines and nitrile ylides: Rearrangements of benzonitrile N-methylimine and benzonitrile dimethylmethylide to azabutadienes, carbodiimides, and ketenimines. chemical activation in thermolysis of azirenes, tetrazoles, oxazolones, isoxazolones, and oxadiazolones

Flash vacuum thermolysis (FVT) of 1-methyl-5-phenyltetrazole (5b), 2-methyl-5-phenyltetrazole (1b), and 3-methyl-5-phenyl-1,3,4-oxadiazol-2(3H)-one (3b) affords the nitrile imine (2b), which rearranges in part to N-methyl-N′-phenylcarbodiimide (7b). Another part of 2b undergoes a 1,4-H shift to the diazabutadiene (13). 13 undergoes two chemically activated decompositions, to benzonitrile and CH2=NH and to styrene and N 2. FVT of 2,2-dimethyl-4-phenyl-oxazol-5(2H)-one (16) at 400 C yields 3-methyl-1-phenyl-2-azabutadiene (18) in high yield. In contrast, FVT of 3,3-dimethyl-2-phenyl-1-azirene (21) at 600 C or 4,4-dimethyl-3-phenyl- isoxazolone (20) at 600 C affords only a low yield of azabutadiene (18) due to chemically activated decomposition of 18 to styrene and acetonitrile. There are two reaction paths from azirene (21): one (path a) leading to nitrile ylide (17) and the major products styrene and acetonitrile and the other (path b) leading to the vinylnitrene (22) and ketenimine (23). The nitrile ylide PhC -=N+=C(CH3)2 (17) is implicated as the immediate precursor of azabutadiene (18). FVT of either 3-phenylisoxazol- 5(4H)one (25) or 2-phenylazirene (26) at 600 C affords N-phenylketenimine (28). The nitrile ylide PhC-=N+=CH2 (30) is postulated as a reversibly formed intermediate. N-Phenylketenimine (28) undergoes chemically activated free radical rearrangement to benzyl cyanide. The mechanistic interpretations are supported by calculations of the energies of key intermediates and transition states.

Flash-vacuum Pyrolysis of N-Vinylbenzotriazoles: Formation of N-Phenylketenimines

A real time analysis of the flash-vacuum pyrolysis products of 1-vinyl-, 1-(2-methylprop-1-enyl)-, and 1-styryl-benzotriazole (3), (16), and (18) has been performed by tandem mass spectrometry.In the 500-700 deg C temperature range, these compounds lose nitrogen yielding the N-phenylketenimines (14), (17), and (19), respectively.At higher pyrolysis temperatures (3) gives indole (4) via isomerization of (14), whereas from (16) the secondary products of (17) are benzene and methacrylonitrile.In a preparative pyrolysis of (18) at 800 deg C 2- and 3-phenylindole (9) and (10) respectively, have also been detected.

Rapid Acid-catalysed and Uncatalysed Hydration of Ketenimines

The rates of hydration of a series of ketenimines (9) have been examined in water (μ 1.0; 25 deg) over the pH range 2-13.Three mechanisms of hydration to the amides (8) were noted: (a) general acid catalysis by proton transfer from H3O(1+) in the pH range 2-7 (giving kH3O(1+)/kD3O(1+) 2.65); (b) general acid catalysis by H2O at pH > 7 (where kH2O/kD2O = 4.8); (c) rate determining HO(1-) attack.The last mechanism was only shown by N-arylketenimines, e.g. (9e); other N-alkylketenimines continue to react by rate-determining proton transfer from water even at pH 13.This result is confirmed by the incorporation of just one deuterium when (9a) reacted in acidic or basic D2O, while the deuteriated ketenimine (9f) does not loose the label on the reaction in water.Substituent effects are parallel for reactions involving H(1+) transfer from H3O(1+) or H2O; the major effects are obtained on changing substituents at carbon (the protonation site).For example, replacement of C-H by C-Me reduces the reactivity by 10-20-fold, while replacement of C-Me by C-Ph reduces the rate of hydration by >100-fold.Ammonium ions also generally react with ketenimines by rate-determining H(1+) transfer to the ketenimine followed by trapping of the nitrilium ion formed by the free amine.Only with the strongest amine base studied (piperidine) does direct nucleophilic attack on the ketenimine compete.