Amine reactions with

The reaction of CO2 with organic amines (RR R N, ArNH2 R = H or aliphatic moiety, Ar = aromatic moiety) is of great interest as the aliphatic members have been used for up-taking CO2 from a gas stream or for synthetic purposes (3.8). The reactivity of amines with CO2 depends on the nature of the organic moiety they bear and the reaction conditions. In fact, under strictly anhydrous conditions, although tertiary aliphatic amines do not absorb CO2, aliphatic primary and secondary amines, as well as ammonia itself, react quickly with carbon dioxide to form the corresponding ammonium carbamates (3.8) which, in a few cases, have been fully characterized in the sohd state by X-ray diffraction [10, 11]. 

Aromatic amines hardly react with carbon dioxide because of their poorer basicity/nucleophilicity [12]. However, in the presence of suitable auxiliary strong bases (B), such as amidines or pentaalkylguanidine superbases, carbamate salts (BH)02CNRAr (R = H, alkyl) can be generated in solution, as revealed by spectroscopic and reactivity data [13]. It has been shown that even tributylamine may be effective if a suitable alkah metal salt is present in the reaction mixture in the latter case, the IV-arylcarbamate has been isolated as an alkali salt (3.10) [14, 15]. 

In a very few cases, a different reactivity has been observed. The Co-aminophosphane complex Co(NO)2[PhP(OCH2CH2)2NH]Cl reacted at 243 K with CO2 (0.1 MPa) to afford CoCl(NO)2[PhP(OCH2CH2)2N-C02H] [16, 17]. Dibenzylamine, Bn2NH (neat, or in heptane solution), also reacted with carbon 

Both mono- and dimeric iV-alkyl substituted carbamic acids have also been detected in solution [12, 18, 19]. At 293 K, under N2, the partial decomposition of the (BnNH3)02CNHBn salt, suspended in THF, was followed by IR 

The reaction of amines with CO2 to afford the corresponding carbamate has been the subject of extended kinetics studies [23]. In most cases, water was used as reaction medium, wherein hydrolytic processes forming hydrogencarbonate ((3.12)-(3.14)) can also occur and compete with carbamate 

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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). 

Naphthalimides are prepared from naphthaUc anhydride obtained from naphthalene-1,8-dicarboxyhc acid, ie, the oxidation product of acenaphthene or its derivatives, by reaction with amines. They are utilized for synthetic fibers such as polyesters. 

Reactions with Amines and Amides. Hydroxybenzaldehydes undergo the normal reactions with aUphatic and aromatic primary amines to form imines and Schiff bases reaction with hydroxylamine gives an oxime, reaction with hydrazines gives hydrazones, and reactions with semicarbazide give semicarbazones. The reaction of 4-hydroxybenzaldehyde with hydroxylamine hydrochloride is a convenient method for the preparation of 4-cyanophenol (52,53). 

The cychc haUdes can be converted to discrete substitution products by reaction with amines, alcohol, or alkylating agents. For example, (NPCl ) reacts with ammonia to form (NP(NH2)2)3 [13597-92-7] withy -NaOCgH CH to form (NP(OCgH4CH2)2)3 [27122-73-2] and with CH MgCl to form (NP(CH3)2)3 [6607-30-3]. Among the cychc members, the trimeric haUdes are the most inert toward substitution and tetrameric haUdes are the most active. 

The addition of alkyl haUdes to phosphines is analogous to the reactions with amines. Because primary phosphonium salts are highly dissociated, the reaction proceeds to the tertiary or quartemary salts. 

Reactions with amines at high temperatures under pressure lead to mixtures of dehydro-2-piperidinones (9) ... 

Reaction with Amines and Ammonia. Carbonates react with amines and ammonia to produce carbamates or ureas. This reaction can be used as an alternative route to producing carbamate pesticides. 

Reactivities of several chlorinated solvents, including chloroform, with aluminum, iron, and 2inc in both dry and wet systems have been deterrnined, as have chemical reactivities in oxidation reactions and in reactions with amines (11). Unstabilized wet chloroform reacts completely with aluminum and attacks zinc at a rate of >250 //m/yr and iron at <250 //m/yr. The dry, uiiinhibited solvent attacks aluminum and zinc at a rate of 250 )J.m/yr and iron at 25 ]lni / yr. 

Cyanuiic chloiide is a convenient piecuisoi to alkyl oi aiyl cyanurates by reaction with alcohols or phenols, or to substituted melamines by reaction with amines alkaline conditions ate employed in both cases and yields are generally high. 

The sulfonyl chloride group is the cure site for CSM and determines the rate and state of cure along with the compound recipe. It is less stable than the Cl groups and therefore often determines the ceiling temperature for processing. The optimum level of sulfonyl chloride to provide a balance of cured properties and processibiUty is about 2 mol % or 1—1.5 wt % sulfur at 35% Cl. It also undergoes normal acid chloride reactions with amines, alcohols, etc, to make useful derivatives (17). 

Where direct amination of chloro compounds has proved unsatisfactory, 4-alkoxy or 4-phenoxy intermediates have sometimes been used for reactions with amines or hydrazine. 

Halogeno-l-methyl-l,2,3-triazoles undergo substitution reactions with amines, but the 4-halogeno analogs do not. 5-Chloro-l,4-diphenyl-l,2,3-triazole with sodium cyanide in DMSO gives the cyano derivative (63JCS2032). 1-Substituted 3-chloro- and 5-chloro-l,2,4-triazoles both react with amines. 

Pyridinium chloride, N-(4-pyridyl)-hydrochloride quaternization, 2, 175 reactions with amines, 2, 241 Pyridinium chlorochromates as oxidizing agents, 2, 170 reactions, 2, 34 Pyridinium dichromate as oxidizing agent, 2, 170 Pyridinium l-dicyanomethylide... 

Clearly, the tertiaiy nature of the chloride would make an Sn2 mechanism highly unlikely. Furthermore, the nitro substituent is essential to the success of these reactions. Cumyl chloride itself undergoes elimination of HCl on reaction with amines. 

Later in the 20th century, Vompe and Stepanov delineated efficient procedures for the preparation of the so-called Zincke salts (e.g., 1) from pyridines and 2,4-dinitrochlorobenzene, involving, for example, reflux in acetone. Vompe and Lukes also noted that electron-donating substituents on the pyridinium ring of the Zincke salt retarded reaction with amines at the 2-position of the pyridinium ring, sometimes leading instead to attack at the C-1 position of the 2,4-dinitrobenzene ring, with displacement of the pyridine. 

In addition to their reactions with amines, Zincke salts also combine with other nitrogen nucleophiles, providing various A -substituted pyridine derivatives. Pyridine A -oxides result from the reaction with hydroxylamine, as exemplified for the conversion of Zincke salt 38 to the A -oxide 39 Reactions of Zincke salts with hydrazine, meanwhile, lead... 

Reactions with uncharged species such as amines, alcohols, and water offer frequent opportunities for investigations under pseudo-first-order conditions since many of these reagents are suitable solvents. However, the reactions with amines have often been investigated in alcohols and in non-hydroxylic solvents 27-29a have been found to follow second-order kinetics. 

The idea that hydrogen bonding, as a special ortho effect of the substrate, may be involved in the transition state of the reactions with amines was first proposed by Chapman et al. Attempting to test this hypothesis, Hawthorne investigated the hydrogen-isotope effect in the reaction of o- and p-chloronitrobenzene with... 

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