Ammonia aniline synthesis

Another synthesis of azepines from azides involved the photolysis or thermolysis of aryl azides in the presence of nucleophiles. The photolysis of phenyl azide in diethylamine yielded (34%) 2-diethylamino-3/f-azepine (311) °. In the same manner 2-substituted azepines were obtained from phenyl azide and liquid ammonia, aniline and hydrogen sulphide . 

In 2013, Shimizu and co-workers first reported an additive-free Ni/Al203-catalyzed synthesis of primary amines from alcohols and ammonia (Scheme 27) [154]. The recovered catalyst could be reused at least twice without losing catalytic activity (1st, 88 %, 3rd, 89 %). Later in 2013, the authors extended the method to amination of alcohols with anilines and aliphatic amines (Scheme 27) [155]. In 2014, the Shimizu group also described a Ni/CaSi03-catalyzed amination reaction of alcohols with ammonia, anilines and aliphatic amines [156]. 

Chloroacetic acid can be esterified and aminated to provide useful chemical intermediates. Amphoteric agents suitable as shampoos have been synthesized by reaction of sodium chloroacetate with fatty amines (4,5). Reactions with amines (6) such as ammonia, methylamine, and trimethylamine yield glycine [66-40-6J, sarcosine [107-97-17, and carhoxymethyltrimethylammonium chloride, respectively. Reaction with aniline forms /V-phenylglycine [103-01 -5] a starting point for the synthesis of indigo (7). 

When arylhydrazones of aldehydes or ketones are treated with a catalyst, elimination of ammonia takes place and an indole is formed, in the Fischer indole synthesis,Zinc chloride is the catalyst most frequently employed, but dozens of others, including other metal halides, proton and Lewis acids, and certain transition metals have also been used. Microwave irradiation has been used to facilitate this reaction. Aniline derivatives react with a-diazoketones, in the presence of a... 

Guanidine dearranges less readily than urea and yidds ammonia and cyanamide as would be expected from the familiar method for its synthesis. If it is heated with aniline, the cyanamide shows no tendency to combine with that substance but combines with itself, as it does in the absence of aniline, to form melamine. 

The order in which the steps are performed is quite flexible. The synthesis of the antiandrogen dutasteride thus starts with the construction of the side chain at 17. The reaction of acid (44-1) with the aniline (46-1) poceeds to afford the amide (46-2). Ring A of the steroid is then opened to the corresponding keto-acid (46-3) with a concomitant loss of carbon 4 by means of the permanganate-periodate combination. Reductive alkylation with ammonia then affords the saturated lactam (46-4). 

Methylnitramine is produced when aniline reacts with tetryl in benzene solution, and when ammonia water or barium hydroxide solution acts upon dinitrodimethyloxamide. The structure of tetryl was first proved by its synthesis from picryl chloride and the potassium salt of methylnitramine. 

N,N -diarylglyoxaldihydrazonoyl dihalides (91), versatile intermediates for the synthesis of heterocyclic systems, reacted with KSeCN in ethanol at reflux to yield 2,2 -bi(4-aryl-4,5-dihydro-5-imino-l,3,4-selenadiazoles) (92) directly in good yield. Similarly, the reaction of the dihalides with selenourea and acylselenourea gave the biselenadiazoles in one step by elimination of ammonia or aniline. [94PS129]... 

The actual cyclisation stage is not as imponderable as it appears. The first step is the acid-catalysed equilibration between hydrazone 7.8 and ene hydrazine 7.10. The next step, which is irreversible, is a concerted electrocyclic reaction, forming a strong carbon-carbon bond, and breaking a weak nitrogen-nitrogen bond. The resulting imine 7.11 immediately re-aromatises by tautomerisation to aniline 7.12. Finally, acid-catalysed elimination of ammonia forms indole 7.9, reminiscent of the last step of the Knorr pyrrole synthesis (Chapter 2). 

Me3SnAr can also be synthesized by the photoinduced reaction of aryldiethylpho-sphate esters [42] or aryltrimethylammonium salts [43] with Me3Sn ions in liquid ammonia, in excellent yields (85-100%). These routes allow for the synthesis of arylstannanes in very good yields from inexpensive and commercially available phenols and anilines, which are easily converted to the corresponding phosphate esters and ammonium salts, respectively. 

Process Economics Program Report SRI International. Menlo Park, CA, Isocyanates IE, Propylene Oxide 2E, Vinyl Chloride 5D, Terephthalic Acid and Dimethyl Terephthalate 9E, Phenol 22C, Xylene Separation 25C, BTX, Aromatics 30A, o-Xylene 34 A, m-Xylene 25 A, p-Xylene 93-3-4, Ethylbenzene/Styrene 33C, Phthalic Anhydride 34B, Glycerine and Intermediates 58, Aniline and Derivatives 76C, Bisphenol A and Phosgene 81, C1 Chlorinated Hydrocarbons 126, Chlorinated Solvent 48, Chlorofluorocarbon Alternatives 201, Reforming for BTX 129, Aromatics Processes 182 A, Propylene Oxide Derivatives 198, Acetaldehyde 24 A2, 91-1-3, Acetic Acid 37 B, Acetylene 16A, Adipic Acid 3 B, Ammonia 44 A, Caprolactam 7 C, Carbon Disulfide 171 A, Cumene 92-3-4, 22 B, 219, MDA 1 D, Ethanol 53 A, 85-2-4, Ethylene Dichloride/Vinyl Chloride 5 C, Formaldehyde 23 A, Hexamethylenediamine (HMDA) 31 B, Hydrogen Cyanide 76-3-4, Maleic Anhydride 46 C, Methane (Natural Gas) 191, Synthesis Gas 146, 148, 191 A, Methanol 148, 43 B, 93-2-2, Methyl Methacrylate 11 D, Nylon 6-41 B, Nylon 6,6-54 B, Ethylene/Propylene 29 A, Urea 56 A, Vinyl Acetate 15 A. 

To determine the photoinduced structure, the orange crystals that were formed after irradiation of benzene solutions of 6-phenoxy-5,12-naphthacenequinone were used.46 It turned out that the elemental composition of the photoinduced form coincided with the ana-quinone composition. In addition, the interaction of 6-phenoxy-5,12-naphthacenequinone with ammonia and aniline in benzene resulted in the formation of compounds that were identified as derivatives of ana-naphthace-nequinone by the counter synthesis. The ana structure of the photoinduced form was supported by the similarity of the absorption spectrum of the ana form to the spectra of unsubstituted and 5-bromo derivatives of 6,12-naphthacenequinone46 as well as by the analysis of the IR spectra of initial and photoinduced forms of 6-phenoxy-5,12-naphthacenequinone. 4... 

What type of amine is C Do you expect it to be more or less basic than ammonia Than aniline What product do you expect from Hofmann elimination of C What significant absorptions might be seen in the IR spectrum of C What information can be obtained from the mass spectrum Plan a synthesis of D from benzene. 

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