Acid tertiary amines

Acetoiicetyliition Reactions. The best known and commercially most important reaction of diketene is the aceto acetylation of nucleophiles to give derivatives of acetoacetic acid (Fig. 2) (1,5,6). A wide variety of substances with acidic hydrogens can be acetoacetylated. This includes alcohols, amines, phenols, thiols, carboxyHc acids, amides, ureas, thioureas, urethanes, and sulfonamides. Where more than one functional group is present, ring closure often follows aceto acetylation, giving access to a variety of heterocycHc compounds. These reactions often require catalysts in the form of tertiary amines, acids, and mercury salts. Acetoacetate esters and acetoacetamides are the most important industrial intermediates prepared from diketene. 

Manufacture and Uses. Acetoacetic esters are generally made from diketene and the corresponding alcohol as a solvent ia the presence of a catalyst. In the case of Hquid alcohols, manufacturiag is carried out by continuous reaction ia a tubular reactor with carefully adjusted feeds of diketene, alcohol, and catalyst, or alcohol—catalyst blend followed by continuous purification (Fig. 3). For soHd alcohols, an iaert solvent is used. Catalysts used iaclude strong acids, tertiary amines, salts such as sodium acetate [127-09-3], organophosphoms compounds, and organometaHic compounds (5). 

The Leuckart reaction uses formic acid as reducing agent. Reductive alkylation using formaldehyde, hydrogen, and catalyst, usually nickel, is used commercially to prepare methylated amines. These tertiary amines are used to prepare quaternary ammonium salts. 

Sulfonic acid strong acids Carboxylic acid weak acids Tertiary amine weak bases Quaternary amine strong bases Aminediacetic acid complex formers... 

The electrophilic character of sulfur dioxide does not only enable addition to reactive nucleophiles, but also to electrons forming sulfur dioxide radical anions which possess the requirements of a captodative" stabilization (equation 83). This electron transfer occurs electrochemically or chemically under Leuckart-Wallach conditions (formic acid/tertiary amine - , by reduction of sulfur dioxide with l-benzyl-1,4-dihydronicotinamide or with Rongalite The radical anion behaves as an efficient nucleophile and affords the generation of sulfones with alkyl halides " and Michael-acceptor olefins (equations 84 and 85). 

In the case of esters from, for example, neopentylglycol, pentaerythrite, and trimethylolpropane with fatty acids, tertiary amines, such as triethanol amine, together with a mixture of fatty acids, improve the efficiency [74]. 

One of the exciting results to come out of heterogeneous catalysis research since the early 1980s is the discovery and development of catalysts that employ hydrogen peroxide to selectively oxidize organic compounds at low temperatures in the liquid phase. These catalysts are based on titanium, and the important discovery was a way to isolate titanium in framework locations of the inner cavities of zeolites (molecular sieves). Thus, mild oxidations may be run in water or water-soluble solvents. Practicing organic chemists now have a way to catalytically oxidize benzene to phenols alkanes to alcohols and ketones primary alcohols to aldehydes, acids, esters, and acetals secondary alcohols to ketones primary amines to oximes secondary amines to hydroxyl-amines and tertiary amines to amine oxides. 

Amino acids labeled with DNS-C1 were determined using the Ru(bpy)32+ CL reaction after HPLC separation with a reversed-phase column [104, 105], DNS derivatives are expected to produce intense CL owing to their secondary and tertiary amino groups. The detection limit for DNS-Glu was 0.1 pM (2 pmol/ injection). Although underivatized amino acids could be detected by Ru(bpy)32+ CL, the DNS derivatives showed improved detection limits by three orders of magnitude [105], An approach to convert primary amines to tertiary amines was also reported [106], In this method, divinyl sulfone (DVS) was used for a cycloaddition reaction of primary amines (Fig. 19). The DVS derivatives after HPLC separation were sensitively detected (e.g., detection limits for propylamine and 3-aminopentane were 30 and 1 pmol, respectively). 

The living character of the ring opening metathesis polymerization described earlier in this review enables a simple preparation of functionalized norbornene-based monoliths. Adding one more in situ derivatization step that involves functional norborn-2-ene and 7-oxanorborn-2-ene monomers that react with the surface-bound initiator, the pores were provided with a number of typical functional groups such as carboxylic acid, tertiary amine, and cyclodextrin [58,59]. 

Eschweiler-Clarke modification org chem A modification of the Leuckart reaction, involving reductive alkylation of ammonia or amines (except tertiary amines) by formaldehyde and formic acid. esh,vTl-3r klark. mad-o-fo ka-shon ... 

Reaction With Amine Acid Salts. A reaction which appears to be less well-appreciated Is the ready condensation of some amlnoplasts with simple amines to selectively generate secondary and tertiary amine linked condensates (Scheme 7). Even In the presence of excess ammonia or primary amine, crosslinked products 13 (plus, conceivably, a trisubstituted product) which contain more highly substituted secondary (and tertiary) amines predominate over 12 (H). These particularly stable, high crosslink density products form with simple amine or diamine acid salts under unexpectedly mild, even room temperature conditions (6). 

Ethane (crit. temp., upper layer, 39.8) LCST, 38.1 n-Heptane Cyclohexane Decalin Tetralin Paraffin waxes Paraffinic oils Naphthenic oils Higher alcohols (Cf. Figure Fourteen Amides Five primary Amines Six secondary Amines Three tertiary Amines m-Aminobenzoic acid (m.p. 174)... 

Yields primary amines with tertiary alkyl groups. Satisfactory for alkenes and alcohols that give a tertiary carbocation in strong acid (see Section 24-3B). 

The Hinsberg test, which can distinguish primary, secondary, and tertiary amines, is based upon sulfonamide formation. In the Hinsberg test, an amine is reacted with benzene sulfonyl chloride. If a product forms, the amine is either a primary or secondary amine, because tertiary amines do not form stable sulfonamides. If the sulfonamide that forms dissolves in aqueous sodium hydroxide solution, it is a primary amine. If the sulfonamide is insoluble in aqueous sodium hydroxide, it is a secondary amine. The sulfonamide of a primary amine is soluble in an aqueous base because it still possesses an acidic hydrogen on the nitrogen, which can be lost to form a sodium salt. 

Descriptors (Acyclic + Phosphoric acids + Tertiary amines) (Model 75)... 

The most conspicuous property of aliphatic amines, apart from their fishy smell, is their high basicity, which usually precludes N-alkylations under acidic reaction conditions (last reaction, Scheme 6.3). Hence, alkylation of amines with tertiary alkyl groups is not usually possible without the use of highly stabilized carbocations which can be formed under basic reaction conditions. Rare exceptions are N-alkyla-tions of amines via radicals (Scheme 4.2), copper-catalyzed propargylations (Scheme 6.3), and the addition of amines to some Michael acceptors and allyl palladium or iridium complexes. Better strategies for the preparation of tert-alkylamines include the addition of Grignard reagents to ketone-derived imines [13] or the reduction of tert-alkyl nitro compounds. 

The most commonly used oxidant for selenium compounds is H202. " The oxidation procedure normally involves addition of 30% H2O2 to a THF or preferably dichloromethane solution of the selenide at 0 °C. The oxidation proceeds chemoselectively and, thus, many potentially oxidizable functional groups such as alkenes, sulfides, amines, sulfoxides, tertiary alcohols, esters, lactones, nitriles and carboxylic acids remain intact. Several selenoxides including (36) and (37) were isolated by this method. ... 

Hydroboration. Thexylborane stabilized as the triethylamine complex is not useful for hydroboration, because 2,3-dimethyl-2-butene is displaced with formation of RBH2-N( 2145)3. However, TBDA is a useful reagent for hydroboration and for various reductions. Thus it reacts with 1-octene to form di- -octylthexylborane in quantitative yield. It is comparable to thexylborane-THF for reduction of aldehydes and ketones. Carboxylic acids are reduced to the corresponding alcohol. 10-Undecenoic acid is reduced selectively to undecanoic acid (90% yield). Tertiary amides are reduced very rapidly to f-amines. Acid chlorides and nitriles are reduced very slowly. 

After acid hydrolysis (quaternary ammonium ions are inert) and neutralization with sodium carbonate no amine could be detected. The polymer cannot contain free amine or tertiary ammonium ions. The only two reasonable alternatives to the zwitterionic mode of propagation can be ruled out. 

In a small test tube or centrifuge tube add 50 mg of the amine, 200 mg of benzenesulfonyl chloride, and 1 mL of methanol. Over the hot sand bath or a steam bath heat the mixture to just below the boiling point, cool, and add 2 mL of 6 M sodium hydroxide. Shake the mixture for 5 min and then allow the tube to stand for 10 more min with occasional shaking. If the odor of benzenesulfonyl chloride is detected, warm the mixture to hydrolyze it. Cool the mixture and acidify it by adding 6 M hydrochloric acid, dropwise, and with stirring. If a precipitate is seen at this point the amine is either primary or secondary. If no precipitate is seen, the amine is tertiary. 

Oxidation of amines.1 Tertiary amines are oxidized by this reagent (2 equivalents) to amides in 70-95% yield. The oxidation of secondary amines is less selective amides are obtained in 35-50% yield accompanied by carboxylic acids and esters. 

Complexes of organotin with amidines have been found to be excellent catalysts for the preparation of polyurethane foams, which do not have the disadvantage of any amine odor and, in addition, delayed onset of the isocyanate-hydroxyl reaction An example of a mercapto-delayed organotin catalyst is 2,2,4,4-tetrakis(alkyl)- l,3,2,4-dithia-stannetane.55 Amine salts of amino acids, tertiary amino acids, and tertiary amino acid-nitrile compositions, have been found to be effective as delayed action catalysts for polyurethane synthesis. They are particularly effective when used in combination with an organometallic compound, such as an organotin. ... 

Primary amines can also be synthesized by alkylaton of ammonia. Haloalkanes react with amines to give a corresponding alkyl-substituted amine, with the release of a halogen acid. Such reactions, which are most useful for alkyl iodides and bromides, are rarely employed because the degree of alkylation is difficult to control. If the reacting amine is tertiary, a quaternary ammonium cation results. Many quaternary ammonium salts can be prepared by this route with diverse R groups and many halide and pseudohalide anions. 

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