Amine with acid chlorides

It must further be mentioned that the acylation of alcohols, phenols, and amines with acid chlorides (and also anhydrides) is now frequently carried out in pyridine solution instead of according to the older Schotten-Baumann method (action of acid chloride in aqueous-alkaline suspension). The hydrogen chloride is fixed by the pyridine. 

Additional work was carried out by the GE group on optimization of the reaction yield and to eliminate unwanted linear oligomers [14], Three side reactions which interfere with synthesis of cyclics were identified reaction of the amine with acid chloride to form an acyl ammonium salt, followed by decomposition to an amide (Equation (3.2)) reaction with CH2CI2 to form a salt (Equation (3.3)) hydrolysis of the acid chloride, forming carboxylate via catalysis... 

Quantitative stoichiometric gas-solid or solid-solid (these at 0 °C) acylations of amines with acid chlorides are varied (Scheme 32). However, for a clean reaction the liberated hydrochloric acid has to be neutralized by an additional gaseous or solid base that may also be a second mole of the amine. The reactions are performed in an evacuated flask or in a ball-mill, respectively. There are only minimal losses of the amides or sulfonamides upon removal of the stoichiometric coproduct with water [91]. The solid-solid reactions can be turned into sustainable 100% yield processes with optimal atom efficiency by milling stoichiometric 1 1 1 mixtures of acid chloride, aniline derivative, and K2CO3... 

More information can be gained on the mechanism of the reaction if two separate experiments can be carried out with the mechanistic probe inserted at two different sites on the reagents. If we are studying a reaction between a nucleophile and an electrophile, it may be possible to make Hammett plots from the variation of substituents on both reagents. The acylation of amines with acid chlorides is an example. 

Amide formation. In the acylation of amines with acid chlorides, BuCH(Et)COONa is a useful scavenger for HCl. 

Substituted amides are formed by the reaction of amines with acid chlorides or anhydrides ... 

Acylation of alcohols or amines with acid chlorides in aqueous alkaline solution ... 

Anhydrides are formed from the reaction of acid chlorides with acids, and an ester is formed from the reaction of acid chlorides or anhydrides with alcohols. Amides may be formed by the reaction of ammonia or an amine with acid chlorides, acid anhydrides, or esters. The nitrogen atom of ammonia or an amine is a good nucleophile, and it attacks the acyl carbon of an acid derivative in a now familiar sequence (see 60 62) to give the amide. A typical example reacts... 

Amides can be synthesized by reaction of amines with acid chlorides, anhydrides, or esters. Acid chlorides can be prepared from carboxylic acids using thionyl chloride, SOCIj, oxalyl chloride (COCOj, or PCI5. 

Amides are readily prepared by acylation of ammonia and amines with acyl chlorides acid anhydrides or esters... 

Interfdci l Composite Membra.nes, A method of making asymmetric membranes involving interfacial polymerization was developed in the 1960s. This technique was used to produce reverse osmosis membranes with dramatically improved salt rejections and water fluxes compared to those prepared by the Loeb-Sourirajan process (28). In the interfacial polymerization method, an aqueous solution of a reactive prepolymer, such as polyamine, is first deposited in the pores of a microporous support membrane, typically a polysulfone ultrafUtration membrane. The amine-loaded support is then immersed in a water-immiscible solvent solution containing a reactant, for example, a diacid chloride in hexane. The amine and acid chloride then react at the interface of the two solutions to form a densely cross-linked, extremely thin membrane layer. This preparation method is shown schematically in Figure 15. The first membrane made was based on polyethylenimine cross-linked with toluene-2,4-diisocyanate (28). The process was later refined at FilmTec Corporation (29,30) and at UOP (31) in the United States, and at Nitto (32) in Japan. 

Primary cycloaUphatic amines react with phosgene to form isocyanates. Reaction of isocyanates with primary and secondary amines forms ureas. Dehydration of ureas or dehydrosulfuri2ation of thioureas results in carhodiimides. The nucleophilicity that deterrnines rapid amine reactivity with acid chlorides and isocyanates also promotes epoxide ring opening to form hydroxyalkyl- and dihydroxyalkylaniines. Michael addition to acrylonitrile yields stable cyanoethylcycloalkylarnines. 

Reaction of amines with acyl chlorides (Section 20.4) Amines are converted to amides on reaction with acyl chlorides. Other acylating agents, such as carboxylic acid anhydrides and esters, may also be used but are less reactive. 

Incorporation of extensive branching in the side chain similarly does not decrease pharmacologic activity. Reductive alkylation of aminoalcohol, 42, with isobutyraldehyde affords the amine, 43. Acylation of the amine with benzoyl chloride probably goes initially to the amide (44). The acid catalysis used in the reaction leads to an N to 0 acyl migration to afford iso-bucaine (45). ... 

Many of the reactions of amines are familiar from past chapters. Thus, amines react with alkyl halides in S 2 reactions and with acid chlorides in nucleophilic acyl substitution reactions. Amines also undergo E2 elimination to yield alkenes if they are first qualernized by treatment with iodomethane and then heated with silver oxide, a process called the Hofmann elimination. 

OH with acid chlorides and in turn may be converted to amides via reaction with primary amines. The conversion of N3P3C1 (NH2)2... 

The most important route to 1-acylaminoanthraquinones involves reaction of 1-aminoanthraquinone with acid chlorides in an organic solvent. Reaction of 1-aminoanthraquinone with benzoylchloride in nitrobenzene at 100 to 150°C affords 1-benzoylaminoanthraquinone, a yellow pigment which is registered as Colour Index Constitution No. 60515. The reaction may also be performed in the presence of a tertiary amine, which acts as a proton acceptor ... 

The direct A-nitration of secondary amines with acidic reagents is only possible in the case of substrates of low basicity. However, the presence of catalytic amounts of chloride ion in... 

Reductive methylation is achieved by the reaction of formaldehyde with ammonium chloride. It is carried out by heating the components at 100-120° and gives mono-, di- and trimethylamine in high yields (Eschweiler reaction) [312, 962]. No catalyst is needed part of the formaldehyde provides the necessary hydrogen while the other part is oxidized to formic acid. The same reaction can be applied to methylation of primary and secondary amines [962]. Reductive alkylation can also be accomplished by reducing mixtures of amines with acids which are first reduced to aldehydes (p. 171). 

Acid chlorides are very reactive, and they readily react with ammonia, primary amines, or secondary amines to form an amide. Figure 12-26 illustrates the reaction of an acid chloride with ammonia. Replacing one or two of the hydrogen atoms of ammonia with an organic group will result in an N-substituted amide. Tertiary amines react with acid chlorides to form a carboxylic acid and an ammonium salt. 

Abnova FISH probes and Dako FISH probes are labeled with fluorescein isothiocyanate (FITC) and Texas Red (sulforhod-amine lOI acid chloride) haptens, and the probe hybridization sites can be visualized with a BISH detection kit including anti-FITC and anti-Texas Red antibodies. 

The classes of compounds which are conveniently considered together as derivatives of carboxylic acids include the carboxylic acid anhydrides, acyl chlorides, esters, and amides. In the case of simple aliphatic and aromatic acids, synthetic transformations among these derivatives are usually a straightforward matter involving such fundamental reactions as ester saponification, formation of acyl chlorides, and the reactions of amines with acid anhydrides or acyl chlorides ... 

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