IMIDA

Another class of herbicides, the imida zolines, was discovered at American Cyanamid in the early 1980s. Extensive research has led to the development of four commercial compounds imazapyr, imazamethahenz-methyl, imazethapyr, and imazaquin (see Table 5). Like the sulfonylureas, the imidazolines are extremely active at low rates. 

Many of the surfactants made from ethyleneamines contain the imidazoline stmcture or are prepared through an imidazoline intermediate. Various 2-alkyl-imidazolines and their salts prepared mainly from EDA or monoethoxylated EDA are reported to have good foaming properties (292—295). Ethyleneamine-based imida zolines are also important intermediates for surfactants used in shampoos by virtue of their mildness and good foaming characteristics. 2- Alkyl imidazolines made from DETA or monoethoxylated EDA and fatty acids or their methyl esters are the principal commercial intermediates (296—298). They are converted into shampoo surfactants commonly by reaction with one or two moles of sodium chloroacetate to yield amphoteric surfactants (299—301). The ease with which the imidazoline intermediates are hydrolyzed leads to arnidoamine-type stmctures when these derivatives are prepared under aqueous alkaline conditions. However, reaction of the imidazoline under anhydrous conditions with acryflc acid [79-10-7] to make salt-free, amphoteric products, leaves the imidazoline stmcture essentially intact. Certain polyamine derivatives also function as water-in-oil or od-in-water emulsifiers. These include the products of a reaction between DETA, TETA, or TEPA and fatty acids (302) or oxidized hydrocarbon wax (303). The amidoamine made from lauric acid [143-07-7] and DETA mono- and bis(2-ethylhexyl) phosphate is a very effective water-in-od emulsifier (304). 

Pyridine-2-carbaldoxime, TEA, H2O, dioxane. The 2-(l-methyl-2-imida-zolyl)phenyl group is not removed under these conditions. ... 

Tire condensation method (Section II,A,1) applied for 1,2,4-thiadia-zolium salts and phenylsubstituted imidazoles leads to the thia-tetraazaful-valenes 91 and 92 (70TL481). Moreover, 2,4,5-tris(ethylsulfanyl)imida-zolium chloride was converted to the unsymmetrical heterofulvalene 93 by a self-condensation reaction in the presence of potassium carbonate and elemental iodine (85PS223) (Scheme 37). 

Although the first ionic liquid expressly categorized as being task-specific featured the incorporation of the function within the cation core, subsequent research has focused on the incorporation of functionality into a branch appended to the cation [11]. In this fashion, a number of task-specific ionic liquids built up from 1-methyl- and 1-butylimidazole have been prepared, produced by means of the reaction between these imidazoles and haloalkanes also incorporating a desired functional group (Scheme 2.3-1). Bazureau has used this approach to prepare imida-... 

The first reaction pathway for the in situ formation of a metal-carbene complex in an imidazolium ionic liquid is based on the well loiown, relatively high acidity of the H atom in the 2-position of the imidazolium ion [29]. This can be removed (by basic ligands of the metal complex, for example) to form a metal-carbene complex (see Scheme 5.2-2, route a)). Xiao and co-workers demonstrated that a Pd imida-zolylidene complex was formed when Pd(OAc)2 was heated in the presence of [BMIMjBr [30]. The isolated Pd carbene complex was found to be active and stable in Heck coupling reactions (for more details see Section 5.2.4.4). Welton et al. were later able to characterize an isolated Pd-carbene complex obtained in this way by X-ray spectroscopy [31]. The reaction pathway to the complex is displayed in Scheme 5.2-3. 

Coelenterazine emits chemiluminescence when dissolved in dimethyl sulfoxide (DMSO) or dimethylformamide (DMF) containing a trace amount of base. It also emits bioluminescence in aqueous media in the presence of a coelenterazine luciferase, such as Renilla luciferase or Oplophorus luciferase. In both cases, the luminescence reactions require molecular oxygen. The capability of coelenterazine to produce luminescence is attributed to the presence of the imida-zopyrazinone structure in the molecule. 

Coelenterazine (A) is oxidized into dehydrocoelenterazine (D) by MnC>2 in a mixed solvent of ethanol and ether (Inoue et al., 1977b). Dehydrocoelenterazine (C26H19O3N3) can be obtained as dark red crystals. It does not have the capability of chemiluminescence. The ultraviolet absorption spectrum (Fig. 5.6) shows its absorption maxima at 425 nm (e 24,400) and 536 nm (g 12,600) in ethanol. An addition of NaOH significantly increases the 536 nm peak at the expense of the 425 nm peak. Dehydrocoelenterazine can take a tautomeric structure of quinone type (not shown), in which the phenolic proton on the 2-substituent is shifted onto the N(7) of the imida-zopyrazinone ring. Dehydrocoelenterazine can be readily reduced to... 

Mechanical Saali Malta WXB Trp WHtiCP Imida OullidiB SinglaH Double ... 

N,N-disubstituierte N -Phenyl-harnstoffe werden dagegen mit sehr guten Ausbeuten ausschlieBlich zu sek. Aminen reduziert z.B. erhalt man aus 1-Anilinocarbonyl-imida-zol 70% d.Th. N-Methyl-anilin neben 92% d.Th. Imidazol2. 

Preparation of Specifically Labeled Samples of 5-Amino-1 -(P-D-ribofuranosyl)imida-... 

Renneberg, D. and P.B. Dervan. Imida-zopyridine/pyrrole and hydroxybenzimi-dazole/pyrrole pairs for DNA minor groove recognition. /. Am. Chem. Soc. 2003, 125, 5707-5716. 

In 2004, Bolm et al. reported the use of chiral iridium complexes with chelating phosphinyl-imidazolylidene ligands in asymmetric hydrogenation of functionalized and simple alkenes with up to 89% ee [17]. These complexes were synthesized from the planar chiral [2.2]paracyclophane-based imida-zolium salts 74a-c with an imidazolylidenyl and a diphenylphosphino substituent in pseudo ortho positions of the [2.2]paracyclophane (Scheme 48). Treatment of 74a-c with t-BuOLi or t-BuOK in THF and subsequent reaction of the in situ formed carbenes with [Ir(cod)Cl]2 followed by anion exchange with NaBARF afforded complexes (Rp)-75a-c in 54-91% yield. The chela-... 

Fig. 2. PO consumption rate obtained by adding various imida2x>lium salt cocatalyste at 115 C (a) OMImBF4, (b) EMImPF4, (c) BMImBF4, (d) EMbnCl, (e) EMbnBF4, (f) BMImCl, (g) HMbnCl, md (h) cat. only. Polymerization conditions catalyst = 0.1 g, initiator (PPG-750) = 70 g, and imida lium salt = 1 mmol.

Tertiary amines have been prepared in good yield by a repetitive generation of imida-zolides and subsequent reduction with borane/dimethylsulfide, 1361 as the following examples show ... 

A selective, mild, and facile reduction of aromatic and aliphatic carboxylic acid imida-zolides to primary alcohols is described in reference [33]. The reaction proceeds in water, water/dioxane or water/tetrahydrofuran solution at room temperature with 2-5 molar equivalents of NaBH4 in about 1 h. 

The following example illustrates an etherification[3],[4] of an alcohol using the imida-zolide of a sulfonic acid. 

The following is an example for a sequential one-pot epoxide formation/nucleophilic opening process using (S)-4-(benzyloxy)-l,2-butanediol, iV-(p-tohienesulfonyl)-imida-zole, and 2-lithio-l,3-dithiane ... 

Gajda et al. have produced a number of zinc imidazole complexes with substituted imida-... 

Combinatorial solid-phase synthetic methodologies have been used extensively in drug development [8]. A new solid-phase synthesis of 2-imidazolidones has been discovered by Goff, based on a domino aminoacylation/Michael addition reaction [9]. Thus, when immobilized amine 10-26 (HMPB-BHA resin) was treated with phenylisocyanate in the presence of triethylamine, a smooth formation of 2-imida-zolidone took place. Acid-catalyzed removal from solid phase provided 10-27 in good yield (Scheme 10.6). 

Synthetic routes to the various classes of azacycl[3.2.2]azines generally follow along very similar lines to the above. For example, l-azacycl[3.2.2]azines (imida/o[ 5,1,2-tv/] indolizines), 356, may be obtained by the [8+2] cycloaddition... 

Rasmussen, G. J., Bundgaard, H., Prodrugs of peptides 15. 4-Imida-zolidinone prodrug derivatives of enkephalines to prevent aminopep-tidase-catalyzed metabolism in plasma and absorptive mucosae, Int. J. 

The solvent-free preparation of 1,2,3-trisubstituted imidazolidin-4-ones from aldehydes and N-substituted a-amino acid amides has been reported by Pospisil and Potacek (Scheme 6.202) [365], The general procedure simply involved heating equimolar mixtures of the aldehyde and amine building blocks under open-vessel micro-wave irradiation for 5 min at 200 °C. After cooling to room temperature, the imida-zolidin-4-one products were purified by flash chromatography. 

The antitrichomonal compound l-methyl-5-nitro-2-(2 -pyrimidyl)imida-zole (97 R = Me, R2 = pyrimid-2-yl) has been shown to be metabolized to the corresponding acetamide (118 R1 = Me, R2 = pyrimid-2-yl, R3 = Me) in both rats and humans (74JPS293). The acetamide (118 R1 = Me, R2 = pyrimid-2-yl, R3 = Me) was also produced synthetically by reduction of a solution of the nitroimidazole (97 R1 = Me, R2 = pyrimid-2-yl) in acetic acid with zinc powder and subsequent treatment of the aminoimidazole (96 R1 = Me, R2 = pyrimid-2-yl) in situ with acetic anhydride to give the acetamide (118 R = Me, R2 = pyrimid-2-yl, R3 = Me) (4%) (74JPS293). 

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