Imine amidation

Small amounts of various phenolic side products that incorporate groups such as imines, amides, ethers, and ethanes into the networks also form. A number of these side products undergo further reactions which eventually lead to methylene linkages. Some side products generally remain in the networks even after heating at 205°C. 

REACTIONS OF DIHALOCARBENES WITH AMINES, IMINES, AMIDES AND RELATED COMPOUNDS... 

The most common preparations of amines on insoluble supports include nucleophilic aliphatic and aromatic substitutions, Michael-type additions, and the reduction of imines, amides, nitro groups, and azides (Figure 10.1). Further methods include the addition of carbon nucleophiles to imines (e.g. the Mannich reaction) and oxidative degradation of carboxylic acids or amides. Linkers for primary, secondary, and tertiary amines are discussed in Sections 3.6, 3.7, and 3.8. 

Table 6.29 Phosphoric acid-catalyzed imine amidation reactions.

Riant O, Mostefai N, Courmarcel J (2004) Synthesis 2004 2943 Rowland GB, Zhang H, Rowland EB, Chennamadhavuni S, Wang Y, Antilla JC (2005) Brpnsted acid-catalyzed imine amidation. J Am Chem Soc 127 15696-15697... 

This index is provided so that the reader might locate information about a particular complex of interest. It is organized as follows The first section contains the neutral binary complexes, followed by charged dimers, and then by larger complexes in the last section. Within each section, the complexes are ordered by the type of molecules contained. The order is as follows XH, YH2, ZH3, carbonyl, carboxyl, imine, amide, nitrile, alkyne, alkene, alkane, others. (X refers to any halogen F, Cl, Br, I Y to O, S, etc. and Z to N, P, etc.) Any alkylated or similar substitutions follow immediately after their parent group. 

Discussed in this chapter, for the most part, are documented cases where complexes derived fiom (one or more equivalents of) a Grignard or organolithium reagent, in combination with a copper(I) salt, have been used to add to an aldehyde, ketone, imine, amide or nitrile moiety. In the majority of examples, the key issue is one of stereocontrol. Hence, where available, data within the organocopper manifold versus those for other organometallic reagents are provided for comparison. 

Apart from phosphanes, typical systems used as chiral ligands in catalysis are alcohols, amines, amino alcohols and other N-functionalities including imines, amides and N-modificd carbonyl groups. Dicarbonyl compounds and their chirally modified equivalents such as dioximes or crown ethers, as well as sulfoxides, arsines, and cyclopentadienyl ligands with chiral side chains have been used. 

However, activation of 9 with N,N -carbonyldiimidazole (CDI) in tetrahydrofuran followed by treatment with 8 cleanly led to complete amidation. The activation reaction afforded the imidazoUde intermediate 17 which, upon reaction with 8, underwent facile amidation. The amidation reaction was accompanied by imine formation at the aldehyde end of the molecule to give imine-amide 18. This necessitated the use of excess 8 to ensure complete amidation. Several attempts to hydrolyze the imine to the aldehyde prior to coupling with 3 were met with only partial success but it was found that the imine could react efficiently with 5-fluorooxindole (3) to give desired free base 2 (Scheme 4.5). 

Phosphoranylideneaminoquinones, e.g. (20), have been prepared in good to excellent yields by the reaction of phosphines with [2,l]benzisoxazole-4,7-quinones, e.g. (19)." A safer alternative to the vinyl azide-based synthesis of (N-vinylimino)phosphoranes (21) has been reported (Scheme 1)." N-(AlkyIthiomethyl)iminophosphoranes (23) have been synthesised from the benzotriazole-substituted iminophosphorane (22) and used without isolation to provide routes to N-alkylthiomethyl-imines, -amides, and -ureas. Tetraazolyl-substituted ylides (25) and (26) are the products of the reaction of vinylphosphonium salts (24) with excess sodium azide." The novel 1,2-1 -azaphosphete (28), which is potentially antiaromatic, has been prepared by the reaction of the azide... 

NH+ in cations derived from aromatic azine systems and from imines Amides and related structure NH moieties in aromatic azole systems Protonated nitriles, R—C=NH... 

Therefore, the chemical modification of the tin dioxide surface during halide ion oxidation (Equations 10.1 and 10.2) is due to the reaction of hypohalogenous acid with the protein side-chains. Actually, during the process, two types of reaction occur i) the oxidation of sulfur atoms and ii) the substitution of the hydrogen (H) of some amine/imine/amide groups, i.e., oxidation and halogenation of the protein side-chains occurs. 

Oxidation of Amines to Aldehydes Imines, Amides, and Di-azo Compounds. jhe oxidation of amines by Mn02 can lead to various products according to the structure of the starting material. Thus the formation of imines (eq 44), formamides (eqs 45 and 46), and diazo compounds (eq 47) P have all been described. 

Treatment with N2 plasma introduces various chemical groups, such as amine, imine, amide, or nitrile, on the membrane surface, making it more hydrophilic and less liable to fouling (Kull et al. 2005). For example, after continuous operation in an SMBR for about 90 h, flux recoveries for plasma-treated PP membranes for 8 min were 62.9% and 67.8% higher than those for the virgin membrane after water and NaOH cleaning (Yu et al. 2007). 

SCHEME 11.53. Br0nsted acid-catalyzed imine amidation. 

The characteristic feature of this type of Cig-diterpenoid alkaloids is the presence of an oxygenated functionality at C-7. Like that of aconitine type, these alkaloids are also subdivided into amines, imines, amides, and iV,0-mixed acetals based upon the substitution pattern of the nitrogen. A total of 11 lycoctonine-type Ci9-diterpenoid alkaloids (32-42) have been obtained between 2009 and Feb. 2012. Compoxmds 32-35 possess a benzoyl ester moiety at C-18 with a variety of amide groups in the ortho position. Anthriscifoldine A (36) [30] and delphidenine (37) [39] are identical compounds reported by different research groups almost at the same time from D. anthriscifolium and D. densiflorum, respectively. 

In the absence of free water, pure sulfuric and phosphoric acids undergo self-ionization. Addition of water, as a proton receptor, promotes the dissociation of the acids. Polymers bearing basic sites, such as ether, alcohol, imine, amide, or... 

Block copolymers combing PBI with other types of macromolecular units have also been developed for superior membrane properties, as shown in Fig. 7.6. Two types of copolymers have been prepared, characterized, and evaluated as fuel cell electrolytes. One is the sulfcmated copolymer containing PBI and snUrmated polymer moieties for low temperature PEMs in both PEM fuel cells and direct methanol fuel cells (DMFCs) [123-126]. The other is the random copolymer containing PBI and poly(imine/ amide) moieties [127, 128]. For the sulfonated PBI copolymers, benzimidazole monomers... 

A monomethylplatinum complex with an 0,iV,P-tridentate ligand 33 is also obtained from the reaction of PtMe2(cod) with a compound having imine, amide, and phosphine groups in the molecule (Equation (13)). ... 

With the BF basis sets optimized for the bonds inclnding heteroatoms, we performed benchmark calcnlations for a test set of 12 molecules including alcohol, ketone, carbonic acid, carbonate, ester, ether, primary and secondary amine, imine, amide, and nitrile. As reference, the cc-pVTZ basis set was employed again. The numerical results are summarized in Table 6, while the number of functions in the various basis sets is collected in Table 7. 

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