Ketimines epoxidation

Other modifications of the polyamines include limited addition of alkylene oxide to yield the corresponding hydroxyalkyl derivatives (225) and cyanoethylation of DETA or TETA, usuaHy by reaction with acrylonitrile [107-13-1/, to give derivatives providing longer pot Hfe and better wetting of glass (226). Also included are ketimines, made by the reaction of EDA with acetone for example. These derivatives can also be hydrogenated, as in the case of the equimolar adducts of DETA and methyl isobutyl ketone [108-10-1] or methyl isoamyl ketone [110-12-3] (221 or used as is to provide moisture cure performance. Mannich bases prepared from a phenol, formaldehyde and a polyamine are also used, such as the hardener prepared from cresol, DETA, and formaldehyde (228). Other modifications of polyamines for use as epoxy hardeners include reaction with aldehydes (229), epoxidized fatty nitriles (230), aromatic monoisocyanates (231), or propylene sulfide [1072-43-1] (232). 

C. Reactions not involving P=0 or P=S Groups.—Enamine phosphine oxides (45) have been prepared by the addition of amines to 1-alkynyl-phosphine oxides, and the reactions of their anions with various electrophiles have been reported. - With ketones a Wittig-type reaction leads to the formation of a/3-unsaturated ketones, in 53—70% yield, while with epoxides cyclopropyl ketimines are formed. A Diels-Alder reaction of l-phenyl-A -phospholen-l-oxide (46) with 1,4-diacetoxybutadiene has been used in the preparation of l-phenyl-benzo[/>]phosphole (47), as... 

Oxazolines can be obtained by the Lewis acid catalyzed epoxide ring opening of glycidic esters or amides (e.g., 118) with acetonitrile . Oxazolidines are available from the palladium-catalyzed cycloaddition of vinyl epoxides with imines <00H885> or the samarium-promoted reaction of ketimines (e.g., 120) with unfunctionalized... 

Epoxidation of both aldimines and ketimines is possible. Most oxaziridines formed are stable compounds, especially aldimines containing aromatic substituents, and 2-sulfonyl-and 2-sulfamyl oxaziridines5. Generally, /V-sulfonyloxaziridines are isolated as stable crystalline solids. Certain compounds are widely used in synthetic organic chemistry as oxygen-transfer reagents (15-17). 

Whitesell and Whitesell" have tabulated some of the many types of electrophilic reagents that C-al-kylate metallated imines. These are potent nucleophiles and undergo substitution reactions even with weakly electrophilic species such as epoxides and oxetanes. Lithiated ketimines and aldimines have been frequently used in reactions with alkylating agents containing latent 2-keto (or aldehydo) groupsor 3-keto (or aldehydo) groups. ... 

Mika and Tanaka also suggested that if reaction (10) occurs, then the retardation effect caused by maleic and phthalic acids, ketones and esters may be attributed to formation of imides, ketimines and amides. The inhibition caused by dioxane, tetrahydrofuran and diisopropyl ethers may be attributed to the fact that the (R2NH HX) reacts with ethers to yield a complex, thereby preventing the epoxides from reacting. This would be expected because the four, five and six member rings are better hydrogen donors than three component epoxy rings. 

Diketones can also be prepared by the reaction of lithiated ketimines with epoxides to give, after acid hydrolysis, 1,4-ketols, which are usually not isolated because of their ready dehydration, but are oxidized by Jones reagent to 1,4-diketones. 

Diones. Alkyl aryl ketones (1) can be converted into acyl-a, a -dichloro-alkyl ketones (2) by conversion to a ketimine (a) followed by chlorination with NCS in CCU ct,o-dichloro ketojtes (2) are obtained on hydrolysis. When treated with sodium methoxide in methanol 2 is converted into a mixture of the isomers 3 and 4 (probably through an epoxide intermediate). Both isomers are converted into a-aryl-l,2-diones (5) on acid hydrolysis. Overall yields vary from 72 to 84% when all intermediates are isolate, but are somewhat higher when the reaction is carried out as a one-pot operation. ... 

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