Ammonia amines and

Reaction with ammonia and amines (Sec tion 20 14) Acyl chlorides react with am monia and amines to form amides A base such as sodium hydroxide is normally added to react with the hydrogen chio ride produced... 

Reaction with ammonia and amines (Section 20 14) Acid an hydrides react with ammonia and amines to form amides Two molar equivalents of amine are required In the example shown only one acyl group of acetic anhydride becomes incor porated into the amide the other becomes the acyl group of the amine salt of acetic acid... 

The reaction of ammonia and amines with esters follows the same general mech anistic course as other nucleophilic acyl substitution reactions (Figure 20 6) A tetrahe dral intermediate is formed m the first stage of the process and dissociates m the second stage... 

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

Nucleophilic ring opening of epoxides by ammonia (Section 16 12) The strained ring of an epoxide is opened on nucleo philic attack by ammonia and amines to give 3 ammo alcohols Azide ion also re acts with epoxides the products are p azido alcohols... 

Ammonia and amines undergo conjugate addition to a 3 unsaturated carbonyl compounds (Section 18 12) On the basis of this information predict the pnncipal organic product of each of the following reactions... 

Reactions with Ammonia and Amines. Acetaldehyde readily adds ammonia to form acetaldehyde—ammonia. Diethyl amine [109-87-7] is obtained when acetaldehyde is added to a saturated aqueous or alcohoHc solution of ammonia and the mixture is heated to 50—75°C in the presence of a nickel catalyst and hydrogen at 1.2 MPa (12 atm). Pyridine [110-86-1] and pyridine derivatives are made from paraldehyde and aqueous ammonia in the presence of a catalyst at elevated temperatures (62) acetaldehyde may also be used but the yields of pyridine are generally lower than when paraldehyde is the starting material. The vapor-phase reaction of formaldehyde, acetaldehyde, and ammonia at 360°C over oxide catalyst was studied a 49% yield of pyridine and picolines was obtained using an activated siHca—alumina catalyst (63). Brown polymers result when acetaldehyde reacts with ammonia or amines at a pH of 6—7 and temperature of 3—25°C (64). Primary amines and acetaldehyde condense to give Schiff bases CH2CH=NR. The Schiff base reverts to the starting materials in the presence of acids. 

Ammonia and amines add to acrylates to form P-aminopropionates, which add easily to excess acrylate to give tertiary amines. The reactions are reversible (33). 

Cyanuric fluoride is readily hydrolyzed to 2,4,6-thhydroxy-l,3,5-triaziae [108-80-5] (cyanuric acid). Cyanuric fluoride reacts faster with nucleophilic agents such as ammonia and amines than cyanuric chloride. 

Sodium Borohydride. Sodium borohydride [16940-66-2] is a thermally stable, white crystalline soHd that decomposes in vacuo above 400°C. The heat of formation is —192 kJ/mol (—45.9 kcal/mol). NaBH is hygroscopic and absorbs water rapidly from moist air to form a dihydrate that decomposes slowly to sodium metaborate and hydrogen. It is soluble in many solvents including water, alcohols, Hquid ammonia and amines, glycol ethers, and dimethyl sulfoxide. 

Aluminum chloride [7446-70-0] is a useful catalyst in the reaction of aromatic amines with ethyleneknine (76). SoHd catalysts promote the reaction of ethyleneknine with ammonia in the gas phase to give ethylenediamine (77). Not only ammonia and amines, but also hydrazine [302-01-2] (78), hydrazoic acid [7782-79-8] (79—82), alkyl azidoformates (83), and acid amides, eg, sulfonamides (84) or 2,4-dioxopyrimidines (85), have been used as ring-opening reagents for ethyleneknine with nitrogen being the nucleophilic center (1). The 2-oxopiperazine skeleton has been synthesized from a-amino acid esters and ethyleneknine (86—89). 

Ammonia, and Amines. Isopropanolamine is the product of propylene oxide and ammonia ia the presence of water (see Alkanolamines). Propylene oxide reacts with isopropanolamine or other primary or secondary amines to produce A/- and A/,A/-disubstituted isopropanolamines. Propylene oxide further reacts with the hydroxyl group of the alkanolamines to form polyether polyol derivatives of tertiary amines (50), or of secondary amines ia the presence of a strong base catalyst (51). 

The chlorosilanes are clear Hquids that should be treated as strong acids. They react readily with water to form corrosive HCl gas and Hquid. Liquid chlorosilanes and their vapors are corrosive to the skin and extremely irritating to the mucous membranes of the eyes, nose, and throat. The nitrogen-functional silanes react with water to form ammonia, amines, or amides. Because ammonia and amines are moderately corrosive to the skin and very irritating to the eyes, nose, and throat, silylamines should be handled like organic amines. Trimethylsilyl trifluoromethanesulfonate and trimethylsilyl iodide form very corrosive acidic products. 

Ammonia and Amine Complexes. In the presence of excess ammonia (qv), silver ion forms the complex ions Ag(NH3) 2 7 -g(NH3) 3. 

Reactions of ammonia and amines with carboxyUc acids result in the formation of a variety of products (47,48). Ammonium salts, RCOONH, are prepared with or without solvent, by reaction with anhydrous ammonia. Ammonium salts readily decompose to acid ammonium salts,... 

Salt Formation. Citric acid forms mono-, di-, and tribasic salts with many cations such as alkahes, ammonia, and amines. Salts may be prepared by direct neutralization of a solution of citric acid in water using the appropriate base, or by double decomposition using a citrate salt and a soluble metal salt. 

Additions. The addition reactions of ammonia and amines to the cyanamide nitrile group have been thoroughly studied (15). For optimum conditions, the reaction should be carried out ia an aqueous medium at about 140°C. Gradual addition of the cyanamide to the amine salt minimises dimerization. 

With Ammonia and Amines. Ethylene oxide reacts with ammonia to form a mixture of mono-, di-, and triethanolamines. Nitrogen is a stronger nucleophile than oxygen (59). A small amount of water is essential for the reaction (60). 

Nucleophilic substitution of the chlorine atom in 2-chloropyrazine and 2-chloroquinoxa-lines has been effected with a variety of nucleophiles, including ammonia and amines, oxygen nucleophiles such as alkoxides, sodium azide, hydrazine, sulfur containing nucleophiles, cyanide, etc., and reactions of this type are typical of the group (see Chapter 2.02). 

Reaction with ammonia and amines (Section 20.14) Acid anhydrides react with ammonia and amines to form amides. 

Nucleophilic acyl substitution (Sections 20.4, 20.6, and 20.12) Acylation of ammonia and amines by an acyl chloride, acid anhydride, or ester is an exceptionally effective method for the formation of carbon-nitrogen bonds. 

In the second major method of peptide synthesis the carboxyl group is activated by converting it to an active ester, usually a p-nitrophenyl ester. Recall from Section 20.12 that esters react with ammonia and amines to give fflnides. p-Nitrophenyl esters are much more reactive than methyl and ethyl esters in these reactions because p-nitrophenoxide is a better (less basic) leaving group than methoxide and ethoxide. Simply allowing the active ester and a C-protected amino acid to stand in a suitable solvent is sufficient to bring about peptide bond formation by nucleophilic acyl substitution. 

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