Tertiary amines substitution

Enaminones. Tertiary amines substituted by a carbonyl group at the P-position undergo dehydrogenation to enaminones when treated with the Pd(ll) complex (1 equiv.) and triethylamine (2 equiv.) in acetonitrile (equation 1). 

Dexedrine dexamphetamine, dexetimide [ban, inn, usan] (benzetimide [inn] benzetimide hydrochloride [usan]) is a tertiary amine substituted piperidine, a MUSCARINIC cholinoceptor ANTAGONIST and ANTIPARKINSONIAN AGENT. It iS the (i)-form, the pharmacologically more active enantiomer. The (R)-form is levetimide. 

Treatment with a deficient quantity of chlorobis(cyclooctene)rhodium(I) dimer (Scheme 3) after 12 h gave a shell of rhodium near the surface. With excess reagent after 4 days the rhodium was incorporated uniformly. Cyclopentadienyltitanium catalysts bound to 2% and 20% cross-linked macroporous polystyrenes had uniform titanium distribution when initially functionalized by chloromethylation (22). Surface binding of Pd from (PhCN)2PdCl2 on 2% cross-linked, tertiary amine-substituted polystyrene was found by X-ray photoelectron spectroscopy (2S). 

It was important to find to what extent the relationships concern the real ACECs being cured with standard hardeners in the presence of accelerators, e.g. tertiary amines and tertiary amine substituted phenols. To start with, the addition of ACECs (Table 8) with model hardeners 3-cyclohexene-l-carboxylic acid and aniline was studied. 

In 2013, Kang and Kim expanded the substrate scope of [l,5]-hydride transfer/ eyelization reactions to ortho tertiary amine substituted benzylidene aeetones 17 (Seheme 4.10). Quinidine-derived primary amine C2 was found to be the optimal catalyst to activate the o,p-unsaturated ketone group. An array of poly-eyelie tetrahydroquinolines 18 was delivered in satisfaetory yields with high level of diastereo- and enantioseleetivity (up to 97% yield, 19 1 dr and 92% ee). 

As a further extension, the Kim group very recently developed the aerobic oxidation and [l,5]-hydride transfer/cyclization sequence starting from readily available ortho tertiary amine substituted cinnamyl alcohols 24 (Scheme 4.12). The tetrapropylammonium perruthenate (TPAP) was identified as the competent catalyst for the initial aerobic oxidation of the allylic alcohols. The synthetically useful tetrahydroquinoline derivatives 25 were prepared in moderate yields and high level of enantioselectivity. 

On the other hand, the Gong group reported the enantioselective [l,5]-hydride transfer/cyclization reaction between ortho tertiary amine substituted aromatic keto esters 33 and aromatic amines 34 catalyzed by chiral bisphosphoric acid (1 ,1 )-C8, developed in their own group (Scheme 4.16). In this reaction, the in situ formed a-imino esters 36 act as the hydride acceptors, allowing the efficient synthesis of cyclic aminals 35 in high stereoselectivity (up to 14 1 dr, 90% ee). 

MAZEEN Surfactants are a group of tertiary amines substituted with two or more polyoxyethylene groups attached to the nitrogen. These products are essentially cationic in nature however, with increasing ethylene oxide content, these products become nonionic in character. 

In 2013, Gong et al. reported a relay catalytic domino hydroamination-redox reaction, which was able to directly assemble tertiary amine substituted 3-en-l-yne derivatives and anilines into the corresponding cyclic aminals by using a gold(i) complex and an achiral phosphoric acid." By using a chiral phosphoric acid, the authors have developed an enantioselective version of this reaction. As shown in Scheme 7.32, the reaction of l-(2-ethynylphenyl)pyrrolidine and p-anisidine in the presence of a catalytic combination of a chiral phosphoric acid and Ph3PAuNTf2 led to the... 

The three nitrogen mustards HN-1, HN-2 and HN-3 (Scheme 1.2) are tertiary amines substituted with 2-chloroethyl groups similar to sulfur mustard. As free bases they are low volatility liquids, generally with poor stability, but form more stable water soluble solid hydrochloride salts. They were partially developed as CW agents during the 1930s but there has been no confirmed use. In WWII Germany produced 2000 tons of HN-3 the USA produced approximately 100 tons of HN-1 in a pilot plant. The most important of the N-mustards is HN-3,... 

A relay catalytic hydroamination/redox reaction for the synthesis of cyclic aminals 83 from tertiary amine-substituted 3-en-l-yne derivatives 81 and various aniline derivatives 82 was recently developed by Gong and coworkers (Scheme 12.40) [43]. The gold carbene complex [(IPrlAuNTfj] and TfOH were found to be optimal cocatalysts for this cascade reaction. In their preliminary studies, the authors found that this reaction could be carried out in a highly enantioselective manner, despite that 2 equiv. of an expensive chiral phosphoric acid are required. Interestingly, the diastereoselectivity for a particular substrate appears to be independent of the catalyst or ee. This suggests that the enantioselectivity may result from the ring-closure step, rather than the hydride shift step. 

Derivatives with 3-nitrophthalic anhydride. 3-Nitrophthalic anhydride reacts with primary and secondary amines to yield nitro-phthalamic acids it does not react with tertiary amines. The phthalamic acid derived from a primary amine undergoes dehydration when heated to 145° to give a neutral A -substituted 3-nitrophthalimide. The phthalamic acid from a secondary amine is stable to heat and is, of course, soluble in alkali. The reagent therefore provides a method for distinguishing and separating a mixture of primary and secondary amines. 

Benzenesulphonyl chloride reacts with primary and secondary, but not with tertiary, amines to yield substituted sulphonamides (for full discussion, see Section IV,100,3). The substituted sulphonamide formed from a primary amine dissolves in the alkaline medium, whilst that produced from a secondary amine is insoluble in alkali tertiary amines do not react. Upon acidifying the solution produced with a primary amine, the substituted sulphonamide is precipitated. The reactions form the basis of the Hinsberg procedure for the separation of amines see Section IV,100,(viii) for details. Feebly basic amines, such as o-nitroaniline, react slowly in the presence of allcali in such cases it is best to carry out the reaction in pyridine solution see Section IV,100,3. ... 

Secondary and tertiary amines are named as N substituted derivatives of primary amines The parent primary amine is taken to be the one with the longest carbon chain The prefix N is added as a locant to identify substituents on the ammo nitrogen as needed... 

The preparation of amines by the methods described m this section involves the prior synthesis and isolation of some reducible material that has a carbon-nitrogen bond an azide a nitrile a nitro substituted arene or an amide The following section describes a method that combines the two steps of carbon-nitrogen bond formation and reduction into a single operation Like the reduction of amides it offers the possibility of prepar mg primary secondary or tertiary amines by proper choice of starting materials... 

Michael condensations are catalyzed by alkaU alkoxides, tertiary amines, and quaternary bases and salts. Active methylene compounds and aUphatic nitro compounds add to form P-substituted propionates. These addition reactions are frequendy reversible at high temperatures. Exceptions are the tertiary nitro adducts which are converted to olefins at elevated temperatures (24). 

Fluoroaromatics are produced on an industrial scale by diazotization of substituted anilines with sodium nitrite or other nitrosating agents in anhydrous hydrogen fluoride, followed by in situ decomposition (fluorodediazoniation) of the aryldiazonium fluoride (21). The decomposition temperature depends on the stabiHty of the diazonium fluoride (22,23). A significant development was the addition of pyridine (24), tertiary amines (25), and ammonium fluoride (or bifluoride) (26,27) to permit higher decomposition temperatures (>50° C) under atmospheric pressure with minimum hydrogen fluoride loss. 

Primary and secondary amines readily give alkylaminomethanols the latter condense upon heating or under alkaline conditions to give substituted methyleneamines (59). With ammonia, the important industrial chemical, hexamine, is produced. Tertiary amines do not react. 

This reaction can also be utili2ed to prepare functionali2ed initiators by reaction of butyUithium with a substituted 1,1-diphenylethylene derivative. For example, polymers end functionali2ed with primary amine, tertiary amine, phenol, and bis(phenol) groups have been prepared in essentiaUy quantitative yield by using the reaction of butyUithium with the corresponding substituted (or protected) 1,1-diphenylethylene (87). 

Sequential substitution reactions which transform alcohols into a family of primary, secondary, and tertiary amines. 

N -Heterocyclic Sulfanilamides. The parent sulfanilamide is manufactured by the reaction of A/-acetylsulfanilyl chloride with excess concentrated aqueous ammonia, and hydrolysis of the product. Most heterocycHc amines are less reactive, and the condensation with the sulfonyl chloride is usually done in anhydrous media in the presence of an acid-binding agent. Use of anhydrous conditions avoids hydrolytic destmction of the sulfonyl chloride. The solvent and acid-binding functions are commonly filled by pyridine, or by mixtures of pyridine and acetone. Tertiary amines, such as triethylamine, may be substituted for pyridine. The majority of A/ -heterocycHc sulfanilamides are made by simple condensation with A/-acetylsulfanilyl chloride and hydrolysis. 

Methyl bromide slowly hydrolyzes in water, forming methanol and hydrobromic acid. The bromine atom of methyl bromide is an excellent leaving group in nucleophilic substitution reactions and is displaced by a variety of nucleophiles. Thus methyl bromide is useful in a variety of methylation reactions, such as the syntheses of ethers, sulfides, esters, and amines. Tertiary amines are methylated by methyl bromide to form quaternary ammonium bromides, some of which are active as microbicides. 

Tertiary amines form a further important class of catalytic hardeners. For example, triethylamine has found use in adhesive formulations. Also of value are the aromatic substituted tertiary amines such as benzyldimethylamine and dimethyldiaminophenol. They have found uses in adhesive and coating applications. A long pot life may be achieved by the use of salts of the aromatic substituted amines. 

In recent years there has been some substitution of TDI by MDI derivatives. One-shot polyether processes became feasible with the advent of sufficiently powerful catalysts. For many years tertiary amines had been used with both polyesters and the newer polyethers. Examples included alkyl morpholines and triethylamine. Catalysts such as triethylenediamine ( Dabco ) and 4-dimethyla-minopyridine were rather more powerful but not satisfactory on their own. In the late 1950s organo-tin catalysts such as dibutyl tin dilaurate and stannous octoate were found to be powerful catalysts for the chain extension reactions. It was found that by use of varying combinations of a tin catayst with a tertiary amine... 

Another type of bifunctional catalysis has been noted with a,cn-diamines in which one of the amino groups is primary and the other tertiary. These substituted diamines are from several times to as much as 100 times more reactive toward imine formation than similar monofunctional amines. This is attributed to a catalytic intramolecular proton transfer. 

Electrochemical fluonnation ot N,N dialkylammo-substituted carboxylic acids as their methyl esters produces the analogous perfluonnated tertiary amine carboxylic acid derivatives in 18-30% yields as well as cyclic amine ethers [JOO]... 

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