Amine also

Amines also react with epoxides at the less substituted carbon atom. As a slightly more testing problem, suggest a synthesis of the alcohol (TM 165) whose derivatives are used in disinfectants ("phemeiide" etc.). 

Primary and secondary amines also react with epoxides (or in situ produced episulfides )r aziridines)to /J-hydroxyamines (or /J-mercaptoamines or 1,2-diamines). The Michael type iddition of amines to activated C—C double bonds is also a useful synthetic reaction. Rnally unines react readily with. carbonyl compounds to form imines and enamines and with carbo-tylic acid chlorides or esters to give amides which can be reduced to amines with LiAlH (p. Ilf.). All these reactions are often applied in synthesis to produce polycyclic alkaloids with itrogen bridgeheads (J.W. Huffman, 1967) G. Stork, 1963 S.S. Klioze, 1975). 

Amines also react with diacyl peroxides by nucleophilic displacement on the oxygen—oxygen bond forming an ion pair iatermediate (187) ... 

Phosgene reacts with a multitude of nitrogen, oxygen, sulfur, and carbon centers. Reaction with primary alkyl and aryl amines yield carbamoyl chlorides which are readily dehydrohalogenated to isocyanates. Secondary amines also form carbamoyl chlorides. 

AijAT-dicyclohexylcarhodiimide (DCC) also leads to essentially quantitative conversion of amic acids to isoimides, rather than imides (30,31). Combinations of trifluoroacetic anhydride—triethjlarnine and ethyl chi oroform a te—triethyl amine also result in high yields of isoimides (30). A kinetic study on model compounds has revealed that isoimides and imides are formed via a mixed anhydride intermediate (12) that is formed by the acylation of the carboxylic group of amic acid (8). 

Ethoxylation and Propoxylation. Ethylene oxide [75-21-8] or propylene oxide [75-56-9] add readily to primary fatty amines to form bis(2-hydroxyethyl) or bis(2-hydroxypropyl) tertiary amines secondary amines also react with ethylene or propylene oxide to form 2-hydroxyalkyl tertiary amines (1,3,7,33—36). The initial addition is completed at approximately 170°C. Additional ethylene or propylene oxide can be added by using a basic catalyst, usually sodium or potassium hydroxide. 

Primary fatty amines also add (Michael addition) to esters of acryUc acid, H2C=CHCOOH, methacrylic acid, H2C=C(CH2)COOH, or crotonic acid, CH2CH=CHC00H. Hydrolysis of the Michael ester forms an amphoteric surfactant. Crotonic acid can be used to form the amphoteric compound... 

As with the parent aromatic hydrocarbons, diarylamiaes based oa polycyclic aromatic amines also tead to be more harmful. Thus, /V-phenyl-2-naphthylamine [135-88-6] (PBNA) metaboli2es ia the body to produce small amouats of 2-aaphthylamiae, a known carciaogea (37). ACGIH has desigaated PBNA to be an "iadustrial substance suspect of carciaogenic potential for man."... 

The addition product, C QHgNa, called naphthalenesodium or sodium naphthalene complex, may be regarded as a resonance hybrid. The ether is more than just a solvent that promotes the reaction. StabiUty of the complex depends on the presence of the ether, and sodium can be Hberated by evaporating the ether or by dilution using an indifferent solvent, such as ethyl ether. A number of ether-type solvents are effective in complex preparation, such as methyl ethyl ether, ethylene glycol dimethyl ether, dioxane, and THF. Trimethyl amine also promotes complex formation. This reaction proceeds with all alkah metals. Other aromatic compounds, eg, diphenyl, anthracene, and phenanthrene, also form sodium complexes (16,20). 

Amines. Primary and secondary aUphatic amines also yield carbamates in the presence of excess amine or other acid acceptors such as inorganic bases. Aromatic primary and secondary amines and heterocycHc amines react similarly, although slowly. 

Both the equilibria and the enhancement of the coefficients can be improved by additives, of which sodium arsenite is the major one in use, but sodium hypochlorite and small amounts of amines also are effective. Sterically hindered amines as promoters are claimed by Say et al. (Chem. Eng. Prog., 80(10), 72-77 [1984]) to result in 50 percent more capacity than ordinary amine promoters of carbonate solutions. 

A number of aromatic amines also function as cross-linking agents. By incorporating the rigid benzene ring structure into the cross-linked network, products are obtained with significantly higher heat distortion temperatures than are obtainable with the aliphatic amines. 

AUcyl amines also react with NaN02 and aqueous acid, but no diazonium ions can be isolated. Rather, alcohols and alkenes are obtained, products that might result from decomposition of RN2 - If RN2 does indeed form in these reactions (and there is evidence that it may not), why is it so unstable compared to PhN2 ... 

IZV679,94RCB630,97MI3,97MI4,97MI14). Reactions of bis(aroyl)furoxans with amines also yield aminofurazans 181 (Scheme 106) (69JHC317). 

Nakagawa and coworkers reported a chiral ytterbium catalyst 34 which was prepared from l,l -(2,2 -bisacylamino)binaphthalene and Yb(OTf)3 in the presence of diisopro-pylethylamine by a method similar to that used for Kobayashi s chiral ytterbium reagent [52] (Scheme 1.65, Table 1.66). The amine also plays an important role in this reaction, because racemic cycloadducts were obtained without the tert-amine. Reduc-... 

Aliphatic primary amines also undergo the diazotization reaction in weakly acidic solution however the resulting aliphatic diazonium ions are generally unstable, and easily decompose into nitrogen and highly reactive carbenium ions. The arenediazonium ions are stabilized by resonance with the aromatic ring ... 

Amines remove the bulk of the H2S primary amines also remove the COj. Amine treating is not effective for removal of mercaptan. In addition, it cannot remove enough H2S to meet the copper strip corrosion test. For this reason, caustic treating is the final polishing step downstream of the amine units. Table 1-3 illustrates the chemistry of some of the important caustic reactions. 

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. 

Schmolukowski in 1917, a diffusion-controlled bimolecular reaction in solution at 25 °C can reach a value for th second-order rate constant k as high as 7 x 109 m 1s-1. Nitrosations of secondary aliphatic amines also have rates which are relatively close to diffusion control (see Zollinger, 1995, Sec. 4.1). 

Tertiary amines also depolymerize lithium alkyl tetramers and hexamers and can be used to trigger reactions with alkyl halides (Lepley, 1968). However, when triethylamine is used to initiate the butyl... 

The reaction of diazo compounds with amines is similar to 10-15. The acidity of amines is not great enough for the reaction to proceed without a catalyst, but BF3, which converts the amine to the F3B-NHR2 complex, enables the reaction to take place. Cuprous cyanide can also be used as a catalyst. The most common substrate is diazomethane, in which case this is a method for the methylation of amines. Ammonia has been used as the amine but, as in the case of 10-44, mixtures of primary, secondary, and tertiary amines are obtained. Primary aliphatic amines give mixtures of secondary and tertiary amines. Secondary amines give successful alkylation. Primary aromatic amines also give the reaction, but diaryl or arylalkyl-amines react very poorly. 

If an aliphatic amino group is to a COOR, CN, CHO, COR, and so on, and has an a hydrogen, treatment with nitrous acid gives not a diazonium salt, but a diazo compound Such diazo compounds can also be prepared, often more conveniently, by treatment of the substrate with isoamyl nitrite and a small amount of acid. Certain heterocyclic amines also give diazo compounds rather than diazonium salts. ... 

More general forms of this equation incorporating the ionisation potential of the amine also give a good degree of correlation with several aliphatic amines. 

IH of allenic amines also occurs in the presence of silver salts. IH of a-allenic amines proceeds in good yields in the presence of AgBp4 and provides a useful method for 3-pyrrolines synthesis via Endo-Trig processes (Eq. 4.93) [314]. 

The inorganic nitrite used as a corrosion inhibitor in aqueous alkylene glycol or polyoxyalkylene glycol solutions can be replaced with polyoxyalkylene amines [1263,1264]. Such polyoxyalkylene amines impart corrosion inhibition to the liquid in contact with the metal and the metal in contact with the vapors of the aqueous composition. Aqueous compositions containing the glycol and the polyoxyalkylene amine also exhibit a low foaming tendency. 

With chemical treatment, the natural surfactants in crude oil can be activated [1384]. This method has been shown to be effective for highly viscous crude oil from the Orinoco Belt that has been traditionally transported either by heating or diluting. The precursors to the surfactants are preferably the carboxylic acids that occur in the crude oil. The activation occurs by adding an aqueous buffer solution [1382,1383]. The buffer additive is either sodium hydroxide in combination with sodium bicarbonate or sodium silicate. Water-soluble amines also have been found to be suitable [1506]. 

Primary aliphatic amines and piperidine react even at room temperature, whereas secondary aliphatic amines require reflux temperature. Primary and secondary aromatic amines also require reflux temperature and A -methylimidazole as catalyst. 

By judicious choice of reaction conditions an acyclic Ni11 complex (784) could be isolated, which serves as a valuable starting material for the preparation of unsymmetrical and mixed metal complexes by subsequent reaction with various amines. Also, a symmetrical Schiff base macrocycle of larger size has been obtained as a minor byproduct upon condensation of (784) with 1,3-diaminopropane. The resulting Ni11 complex (785) is again bimetallic, although room to bind four metal ions is in principle available.1367... 

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