Ketimine

The ketimine 736 is prepared by the reaction of the imidoyl chloride 735 with organotin reagents[604,605]. 

An alternative method consists of the reaction of trichloroacetonittile [545-06-2] with a hydrocarbon and AlCl. A ketimine is formed which is hydroly2ed by treatment with potassium hydroxide iato the nittile and chloroform. The reaction proceeds with aromatics such as toluene and phenols (130). 

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). 

The treatment of 3-benzoyl-2-phenylisoxazolidine with strong base generated an aldehyde and a ketimine <74X1121). Under these conditions dimethyl 2-a-methoxyisoxazolidine-3,3-dicarboxylic acid (186) produced isoxazoline-2-carboxylic acid. Reaction of the monomethyl amide (187) gave the corresponding isoxazoline-2-carboxamide (Scheme 60). CD was used in the conformational studies <79X213). 

Also due to the high barrier of inversion, optically active oxaziridines are stable and were prepared repeatedly. To avoid additional centres of asymmetry in the molecule, symmetrical ketones were used as starting materials and converted to oxaziridines by optically active peroxyacids via their ketimines (69CC1086, 69JCS(C)2648). In optically active oxaziridines, made from benzophenone, cyclohexanone and adamantanone, the order of magnitude of the inversion barriers was determined by racemization experiments and was found to be identical with former results of NMR study. Inversion barriers of 128-132 kJ moF were found in the A-isopropyl compounds of the ketones mentioned inversion barriers of the A-t-butyl compounds lie markedly lower (104-110 kJ moF ). Thus, the A-t-butyloxaziridine derived from adamantanone loses half of its chirality within 2.3 days at 20 C (73JCS(P2)1575). 

Another route to a certain class of 6a-methoxypenicillanates (77TL3831) also probably involves the intermediacy of a 6-imino species. As shown in Scheme 46, 6/3-ketenimino intermediates are readily formed with penicillins having this kind of side chain. Chlorination followed by treatment with methoxide affords the 6a-methoxy-6/3-ketimine, probably involving the intermediates shown. 

Phenol-Blocked Isocyanate Prepolymer + Ketimine (PBIP)... 

The ketimine is an acetone-blocked diamine. The synthesis and applications of ketimines will be discussed later. The curing concept for the adhesive is shown in Fig. 7. Phenol-blocked prepolymers would normally unblock at approximately 150°C. However, an aliphatic diamine, generated by the hydrolysis of the ketimine to an aliphatic diamine and ketone as a result of exposure to the moisture in the air, is sufficient to cure the windshield adhesive at room temperature. 

Several blocked diamines or amino-alcohols are commercially available. The aldimine is an aldehyde-blocked diamine. The ketimine is a ketone-blocked diamine. The oxazolidine is a five-membered ring containing oxygen and nitrogen. The oxazolidine ring shown below is an aldehyde-blocked amino alcohol. The basic synthetic concepts of an aldimine, a ketimine, and an oxazolidine are shown below ... 

An example of the synthesis and curing reactions of a specific ketimine is shown below ... 

The ketimine of isophorone diamine is formed by reacting it with methyl isobutylketone, splitting off water in the process. When said ketimine is added to an isocyanate-terminated prepolymer based on IPDI, a semi-stable system is established with a pot life of several hours. The ketimine is a Schiff base and thus can react even in the absence of water. The complexities and advantages of this system are reviewed by Bock and Halpaap [75] ... 

Once the adhesive system is applied, water reacts preferentially with the more reactive ketimine, instead of with the slower reacting isocyanate. In the presence of water, the ketimine unblocks to reform the ketone and diamine. Once formed, the diamine will react quickly with the isocyanate to form a polyurea. 

Fluorinated heterodienophiles and heterodienes Diels-Alder reactions in which the dienophiles have perfluoroalkyl-substituted multiple bonds between carbon and a heteroatom are quite common Reported earlier were reactions of perfluoroketones, thiones, ketimines, thioesters, nitroso compounds, and nitriles [9] Examples of a-fluoroimines [107], co-hydroperfluorothioaldehydes [108], perfluorosulfines [109, IIO], and selenocarbonyidifluoride [III] (equations 89-92) have been reported recently... 

The acid-catalyzed reaction of acetophenone with acyclic secondary amines results in the formation of the expected enamine and a rearrangement product. The latter product arises from the transfer of one of the amino N-alkyl groups to the cnamine s carbon to produce a ketimine (53a). 

Iminium salts can be made in a number of ways such as protonation of enamines (7), alkylation of aldimines and ketimines (5,9), cleavage of a covalent bond in a... 

The alkylation of aldimines and ketimines as a method for obtaining iminium salts is now useful only for the preparation of iminium salts not accessible by any of the newer methods. The preparation of and 8 illustrates the conversion of ketimines to iminium salts (9,21). 

The infrared, ultraviolet and NMR spectra of /) -octahydro-7-quinoline were compared with the corresponding spectra of the N-ethyl and O-ethyl derivatives in order to determine whether it is in the enamine (64), enolimine (65), or ketimine (66) form. 

The photochemical rearrangement of enamides to vinylogous amides was described (65],652). Rearrangement of cyclopropyl ketimines to enamines with acid was applied to syntheses of myosamine, apoferrosamine, mesembrine, and desmethoxymesembrine (653-656). 

RR C=NLi) . They can be prepared in high yield either by the addition of an organolithium compound across the triple bond of a nitrile (equation (1)) or by lithiation of a ketimine (equation (2)). 

Petrow described the formation of 3-iminoketones from 3-keto-aldehydes and aniline. Cyclization in the presence of aniline hydrochloride and ZnCh smoothly provides the desired quinoline 26. Bis-imine 24 is the proposed intermediate that undergoes cyclization. The aldimine is more reactive than the ketimine toward cyclization thus, cyclization on the aldimine occurs. When the bis-imine is not formed, partial aniline migration can occur which results in mixtures of cyclized products. 

We have previously discussed that keto-aldehydes react with anilines first at the aldehyde carbon to form the aldimine. Subsequent condensation with another aniline formed a bis-imine or enamino-imine. The aniline of the ketimine normally cyclizes on the aldimine (24 —> 26). Conversely, cyclization of the aldimine could be forced with minimal aniline migration to the ketimine using PPA (30 —> 31). The use of unsymmetrical ketones has not been thoroughly explored a few examples are cited below. One-pot enamine formation and cyclization occurred when aniline 48 was reacted with dione 49 in the presence of catalytic p-TsOH and heat. Imine formation occurred at the less-hindered ketone, and cyclization with attack on the reactive carbonyl was preferred. ... 

The [4-1-3] cycloaddition has also been realized in acceptors containing a nitrogen atom. While a,/ -unsaturated aldimines, and structurally flexible ketimine such as (87), generally only undergo [3-1-2] cycloadditions (see Scheme 24), the ketimine (112), which is rigidly held in a cisoid conformation, does give exclusively the [4-1-3] adduct azepine (113). On the other hand, the steroidal imine (114) produces a quantitative yield of a 1 1 mixture of the [4-1-3] and [3-1-2] cycloadducts (115) and (116), respectively (Scheme 2.31) [36]. 

The synthesis of vinylaziridines through reactions between allylic carbenoid reagents and imines (i.e., Darzen-type reactions) was first reported by Mauze in 1980 [13]. Treatment of aldimines or ketimines 16 with gem-chloro(methyl)allyllithium (17) afforded N-substituted vinylaziridines 18 (Scheme 2.6). Similarly, 2,3-trans-N-diphenylphosphinyl-2-vinylaziridines 21 were prepared with good stereoselectivities (trans cis= 10 1 Scheme 2.7) by treatment of a-bromoallyllithium (20) with N-diphenylphosphinyl aldimines 19 in the presence of zinc chloride [14]. 

The anions of (/ )-a-sulfinyl ketimines undergo 1,4-addition to cyclic a./Tunsaturated esters and then cyclization to give predominately c/.v-fused annulation products243. These studies have been extended to include acyclic a,/l-unsaturated esters 24b,c. 

Metal derivatives of ketimine and aldimine compounds. D. F. Martin, Prep. Inorg. React., 1964,1, 59-75 (48). 

The insertion of alkynes into a chromium-carbon double bond is not restricted to Fischer alkenylcarbene complexes. Numerous transformations of this kind have been performed with simple alkylcarbene complexes, from which unstable a,/J-unsaturated carbene complexes were formed in situ, and in turn underwent further reactions in several different ways. For example, reaction of the 1-me-thoxyethylidene complex 6a with the conjugated enyne-ketimines and -ketones 131 afforded pyrrole [92] and furan 134 derivatives [93], respectively. The alkyne-inserted intermediate 132 apparently undergoes 671-electrocyclization and reductive elimination to afford enol ether 133, which yields the cycloaddition product 134 via a subsequent hydrolysis (Scheme 28). This transformation also demonstrates that Fischer carbene complexes are highly selective in their reactivity toward alkynes in the presence of other multiple bonds (Table 6). 

DFBP can be converted into difluorophenylketimine, which was used to prepare ketimine-modified PEEK at 180°C in NMP (Scheme 6.17).86 89 The soluble... 

Scheme 6.17 Synthesis of poly(ether ketone) via poly(ether phenyl ketimine).

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