Imidates, with ammonia amines

Pyrylium cations form pyridines with ammonia and pyridinium salts with primary amines (B-82MI 505-02). For example, 2,4,6-triphenylpyrylium cation (261 Z=0) yields 2,4,6-triphenylpyridine with ammonia, the corresponding 1-methylpyridinium salt with methylamine, and pyridine 1-arylimines with phenylhydrazine. Xanthylium ions (210), where ring opening cannot readily occur, form adducts (262) with ammonia, amines, amides, ureas, sulfonamides and imides. Similar adducts (e.g. 263) are formed by benzo[( ]pyrylium ions. 

PINNER REACTION. Formation of imino esters (alkyl imidates) by addition of dry hydrogen chloride to a mixture of a nitrile and an alcohol. Treatment of alkyl imidates with ammonia or primary or secondary amines affords amidines. while treatment with alcohols yields ortho-esters. 

Conversion of acid derivatives into amines with the loss of the carbonyl group can be done in i.-ious ways. In Chapter 40 we recommended either the Curtius rearrangement or the Hofmann tejradation (p. 1073). The Hofmann degradation is easier starting with an ester. We convert into . imide with ammonia and treat with bromine in basic solution. The N-bromo derivative forms a afcene by a-elimination that rearranges to an isocyanate. 

To minimize the formation of fuhninating silver, these complexes should not be prepared from strongly basic suspensions of silver oxide. Highly explosive fuhninating silver, beheved to consist of either silver nitride or silver imide, may detonate spontaneously when silver oxide is heated with ammonia or when alkaline solutions of a silver—amine complex are stored. Addition of appropriate amounts of HCl to a solution of fuhninating silver renders it harmless. Stable silver complexes are also formed from many ahphatic and aromatic amines, eg, ethylamine, aniline, and pyridine. 

Thionyl imide, HNSO, is a thermally unstable gas, which polymerizes readily. It can be prepared by the reaction of thionyl chloride with ammonia in the gas phase. Organic derivatives RNSO have higher thermal stability, especially when R = Ar. The typical synthesis involves the reaction of a primary amine or, preferably, a silylated amine with thionyl chloride. A recent example is the preparation of FcNSO (Fc = ferrocenyl) shown in Eq. 9.8. In common with other thionylimines, FcNSO readily undergoes SO2 elimination in the presence of a base, e.g., KO Bu, to give the corresponding sulfur diimide FcNSNFc. 

As in 10-55 hydrazides and hydroxamic acids can be prepared from carboxylic esters, with hydrazine and hydroxylamine, respectively. Both hydrazine and hydroxylamine react more rapidly than ammonia or primary amines (the alpha effect, p. 445). Imidates, RC(=NH)OR, give amidines, RC(=NH)NH2. Lactones, when treated with ammonia or primary amines, give lactams. Lactams are also produced from y- and 5-amino esters in an internal example of this reaction. 

The preparation of N-alkyl imides by exchange reaction of an imide with an alkyl amine was documented [104] well before the application of this chemistry to the preparation of polyimides [105], see Scheme 30. Although no experimental details are provided, the initial reaction of pyromellitimide with p,p-methylene dianiline in NMP takes place at reflux temperatures to apparently yield a poly(amic amide). Subsequent heating of this intermediate at elevated temperatures ( 300 °C) provides the desired polyimide with evolution of ammonia. The final polyimide is quoted to be thermally and chemically stable, however, no mechanical properties are given. 

This reaction, similar in scope and mechanism8S2 to 0-52, can be carried out with ammonia or primary or secondary amines.853 However, ammonia and primary amines can also give imides, in which two acyl groups are attached to the nitrogen. This is especially easy with cyclic anhydrides, which produce cyclic imides.854... 

Cyclic anhydrides of dibasic acids react with ammonia and certain amines to give cyclic imides, such as phthalimide (97%) and a-ethyl-glutarimide (85%). Aqueous ammonia, ammonium carbonate, and dry ammonia gas have been used. 2-Aminopyridine and phthalic anhydride react at 180° to yield N-(2 pyridyl)-phthalimide (76%). t-Butylphthali-mide is made by the action of phthalic anhydride on /-butylurea at 200-240°. The use of alkylureas in this reaction is general. ... 

Intramolecular cyclization of 2-aminoethanesulfonyl halides gives 1,2-thiazetidine 1,1-dioxides ((3 sultams), as exemplified in the synthesis of 429. ° Treatment of 2-halosulfonylethanoyl halides with ammonia or primary amines yields 1,2-thiazetidin-3-one 1,1-dioxides, which are mixed sulfonic-carboxylic imides 430. A 3-imino derivative has also been obtained. ... 

Although a variety of primary and secondary amines can be utilized as nitrogen nucleophiles, amina-tion of allylic substrates with ammonia has been reported to be unsuccessful. Therefore, bis(p-methoxy-phenyDmethylamine, sodium p-toluenesulfonamide or sodium azide have been utilized instead of ammonia. In the presence of a palladium catalyst, imides, such as phthalimide, react with allylic esters with the exception of geranyl and linalyl acetates. 0-Geranyl- and 0-linalyl-isourea derivatives, however, reacted with phthalimide giving the expected -allylic phthalimides in 65% and 71% yields, respectively. ... 

Acylation of nitrogen compounds by imidic esters. It was mentioned above that synthesis of amidines from orthoesters proceeds through imidic esters, so that both classes of compound are normally treated together in reviews.819-821 Accordingly, also, it is, of course, possible to use imidic ester hydrochlorides as usually prepared from nitriles and to treat these with ammonia or amines.820 Care must be taken, however, with primary amines lest the imido group be also exchanged for the residue from the amine, particularly at higher temperatures ... 

The polymeric imide could then be reacted with primary amines or ammonia to form ammonium salts for a subsequent reactions with a carboxylic acid in the presence of a coupling reagent. It could then be converted to amides or functionalized as a uranium salt for use as polymer-supported peptide coupling. In addition, the anhydride was also reacted with di(2-pyrldyl)methylamine and formed a recoverable palladium catalyst for cross-coupling reactions that could take place in water. 

Radovic et al. (1996) investigated the effects of nitriding the surface on adsorption from solution. Reacting with ammonia at elevated temperatures introduced pyridine functional groups on carbon. Reaction at 200 °C forms amides, imides, imines, amines, and nitriles while reaction at 250 °C results in bonding of ammonia to the carbon double bonds (Vinke et al., 1994). The effects of nitriding (at 250 °C) were similar to that of oxidation. Nitriding also hindered the adsorption of benzoate and aliphatic anions, oxalate, and fumarate. 

Acidity of Amides, Imides, and Sulfonamides Characteristic Reactions Reaction with Water Hydrolysis Reaction with Alcohols Reactions with Ammonia and Amines Reaction of Acid Chiorides with Salts of Carboxylic Acids Interconversion of Functional Derivatives Reactions with Organometallic Compounds 18.10 Reduction... 

Lactones and anhydrides each react with ammonia or amines to give nitrogen derivatives. In some cases, lactones are converted to lactams and anhydrides to imides. In these cases, hydrolysis will open the ring and generate an amino acid (see... 

IV. Ammoniiun salts of carboxylic adds, aldehyde-ammonias, amides, imides, nitriles. Acyl derivatives of bases (JV-substituted amides). Hydrazines, semicarbazide, hydroxyl-amine, their salts and carbonyl derivatives. Condensation products of aldehydes with ammonia or amines. 

Dicarboxylic acids may react twice with the amine nitrogen of ammonia or of a primary amine. This sequence gives rise to imides, the nitrogen analogs of cyclic anhydrides (cf. p. 854). 

Cyanopyridazines add ammonia, primary and secondary amines and hydroxylamine to give amidines or amidoximes. Substituted amides, thioamides and carboximidates can be also prepared. With hydrazine, 3-pyridazinylcarbohydrazide imide is formed and addition of methylmagnesium iodide with subsequent hydrolysis of the imine affords the corresponding pyridazinyl methyl ketone. 

OL,, -Trinitro-Propionaldehyde methyl imide ( 03,7,7-Trinitro-Propyliden]-methyl-amine). CH3.N CH.CH(N02).CH(N02)2 mw 206.14 N 27.19% white crysts. V sol in acet si sol in w insol in eth. Prepn is by reacting a,j3 J3-trinitro-propionaldehyde suspended in ammonia with an excess of methylammonium chloride. The imide is recovered by acidifying the mixt with HC1... 

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