Succinimides, addition

Micellar solutions of detergents such a sulfonates, phenolates and salicylates enhance the solubilizing properties of succinimide additives. For small concentrations of about 0.25% w/w sulfonate and 2.8% succinimide, a synergistic effect is observed, but for high sulfonate concentrations, the quantity of acid solubilized is less than that observed for succinimide alone (Bradley and Jaycock, 1972). A different mechanism exists for the solubilization of those weak acids and for strong acids. The different interaction between the amine groups in the polar head of a succinimide micelle and a weak acid (WH), and for a strong acid (SH), indicates that the weak acid is much better solubilized as ... 

Reaction of 1-morpholinocycloalkenes 16 (n = 3-8) with dimethyl(succinimido)sulfonium fluorosulfate ° gave an equimolar mixture of dimethyl(2-morpholinocyclohex-l-enyl)sul-fonium fluorosulfates 17 (n = 3-8) and succinimide. Addition of A,A-diisopropylamine to these mixtures in anhydrous acetonitrile at — 10°C gave in 36-60% yield colorless crystals which were shown to be pure e t/o-morpholino(succinimido)bicyclo[n.l.O]alkanes cis-lS (n = 3-8), on the basis of their HNMR, CNMR and IR spectra. If 17 (n = 8) is allowed to stand for 48 hours prior to addition of A.A -diisopropylethylamine, then 10% of cw-18 (n = 8)isaccompaniedby 39% ofthe trans-isomsr trans-lS n = 8). °Treatmentofthe isolated enaminosulfonium fluorosulfate 17 (n = 3) with succinimide in the presence of A,A-diiso-propylethylamine in anhydrous acetonitrile gave the same product. ... 

H30CIN3O1, Tetraethylammonium bromide-succinimide addition compound, 22, 793... 

In this work, we have evidenced the formation of a lamellar solid from the tribochemical reaction of a borated additive and a succinimide additive. The result is the formation of h-BN in the tribofilm. The tribofilm is mainly composed of an amorphous borate matrix containing highly-dispersed h-BN nanoparticles in the form of sheets less than 10 nm wide and 5 nm thick. The originality of this h-BN tribochemical reaction lies in the nature of the intermolecular reaction between the two additives. At the opposite, M0S2 formation fiom MoDTC is the result of intramolecular chemical reaction. 

In this work, we have evidenced the formation of a lamellar solid fiom the tribochemical reaction of a borated additive and a succinimide additive. The result is the formation of h-BN in the tribofilm. Results can be summarized as followed ... 

To avoid these problems, refiners commonly use additives called detergents" (Hall et al., 1976), (Bert et al., 1983). These are in reality surfactants made from molecules having hydrocarbon chains long enough to ensure their solubility in the fuel and a polar group that enables them to be absorbed on the walls and prevent deposits from sticking. The most effective chemical structures are succinimides, imides, and fatty acid amines. The required dosages are between 500 and 1000 ppm of active material. 

Detergent and dispersant additives sulfonates, thiophosphonates, phenates, salicylates more or less overbased, succinimides. 

The third family (c. in Figure 9.1) less widespread, derived from the alkylphenols, offers as with the succinimides several possibilities of modification to the ratio of hydrophilic and lipophilic groups. Mannich s reaction of the alkyl-phenols also provides additives for lubricating oils. 

The role of detergent additives is to maintain clean injectors so as to insure good distribution of diesel fuel in the cylinder. The structure of these compounds is similar to that of detergents for gasoline engine admission systems. Commercialized compounds are from the succinimide family (see Figure 9.1). 

Halogen-substituted succinimides are a class of products with important appHcations. /V-Bromosuccinimide [128-08-5] mp 176—177°C, is the most important product ia this group, and is prepared by addition of bromine to a cold aqueous solution of succinimide (110,111) or by reaction of succinimide with NaBr02 iu the presence of HBr (112). It is used as a bromination and oxidation agent ia the synthesis of cortisone and other hormones. By its use it is possible to obtain selective bromine substitution at methylene groups adjacent to double bonds without addition reactions to the double bond (113). 

The Bsmoc derivative is formed from the chloroformate or the A -hydroxy-succinimide ester. It is cleaved rapidly by a Michael addition with tris(2-aminoethyl)amine at a rate that leaves Fmoc derivatives intact. More hindered bases, such as A -methylcyclohexylamine or diisopropylamine, do not react with the Bsmoc group, but do cleave the Fmoc group, illustrating the importance of steric effects in additions to Michael acceptors. 

In a more recent study on 1,3-dipolar cycloaddition reactions the use of succi-nimide instead of the oxazolidinone auxiliary was introduced (Scheme 6.19) [58]. The succinimide derivatives 24a,b are more reactive towards the 1,3-dipolar cycloaddition reaction with nitrone la and the reaction proceeds in the absence of a catalyst. In the presence of TiCl2-TADDOLate catalyst 23a (5 mol%) the reaction of la with 24a proceeds at -20 to -10 °C, and after conversion of the unstable succinimide adduct into the amide derivative, the corresponding product 25 was obtained in an endojexo ratio of <5 >95. Additionally, the enantioselectivity of the reaction of 72% ee is also an improvement compared to the analogous reaction of the oxazolidinone derivative 19. Similar improvements were obtained in reactions of other related nitrones with 24a and b. 

Formal oxidation of pyrrolidine to the succinimide stage affords a series of compounds used as anticonvulsant agents for treatment of seizures in petit mal epilepsy. Knoevnagel condensation of benzaldehyde with ethyl cyanoacetate affords the unsaturated ester, 9. Conjugate addition of cyanide ion leads to the di-nitrile ester (10). Hydrolysis in mineral acid affords the succinic acid (11), presumably by decarboxylation of the intermediate tricarboxyllie acid. Lactamization with methylamine gives phensuximide (12). ... 

As we have seen previously, succinimides containing a quaternary carbon form the basis for a series of anticonvulsant drugs. In the course of research in this series, it was found that the inclusion of additional hetero atoms in the ring was quite compatible with anticonvulsive activity. We consider here the oxa-zolidinediones a discussion of the hydantoins is found later in this section. 

Pregnancy Category C drug and is used with caution during pregnancy. As with all anticonvulsants, when the succinimides are used with other CNS depressants (eg, alcohol, narcotic analgesics, and antidepressants), an additive CNS depressant effect may occur. 

The suspension may be warmed to dissolve the alkene more rapidly. (E)-Stilbene dissolves completely at ca. 65°. If the suspension is warmed, it must be cooled below 30° before proceeding further to prevent a vigorous reaction when the N-bromo-succinimide is added. The submitters recommend that the warm suspension be cooled under an atmosphere of nitrogen. If a volatile alkene is used, the mixture should be cooled prior to and during the addition of N-bromosuccinimide to prevent losses by evaporation. 

Dissolve 71 g. of P-methylnaphthalene in 460 g. (283 ml.) of A.B. carbon tetrachloride and place the solution in a 1 -litre three-necked flask equipped with a mechanical stirrer and reflux condenser. Introduce 89 g. of JV-bromosuccinimide through the third neck, close the latter with a stopper, and reflux the mixture with stirring for 16 hours. Filter ofiT the succinimide and remove the solvent under reduced pressure on a water bath. Dissolve the residual brown oil (largely 2-bromomethyl naphthalene) in 300 ml. of A.R. chloroform, and add it to a rapidly stirred solution of 84 g. of hexamine in 150 ml. of A.R. chloroform contained in a 2-litre three-necked flask, fitted with a reflux condenser, mechanical stirrer and dropping funnel maintain the rate of addition so that the mixture refluxes vigorously. A white solid separates almost immediately. Heat the mixture to reflux for 30 minutes, cool and filter. Wash the crystalline hexaminium bromide with two 100 ml. portions of light petroleum, b.p. 40-60°, and dry the yield of solid, m.p. 175-176°, is 147 g. Reflux the hexaminium salt for 2 hours with 760 ml. of 60 per cent, acetic acid, add 160 ml. of concentrated hydrochloric acid, continue the refluxing for 5 minutes more, and cool. Extract the aldehyde from the solution with ether, evaporate the ether, and recrystallise the residue from hot -hexane. The yield of p-naphthaldehyde, m.p. 69-60°, is 60 g. 

Usually, the diastereoselectivity in Michael additions is the one predicted by the Felkin-Anh model.57 However, it was discovered that in the case of the addition of highly hindered nucleophiles, as potassium phthalimide and succinimide, the major product has the opposite configuration to the one predicted by this model, because of the presence of steric hindrance interactions.58... 

Di-isopropyl phosphoroehloridate.3 Di-isopropyl hydrogen phosphite (0-1 mol.) is dissolved in dry carbon tetrachloride, and to the solution Y-chlorosuccinimide (0-1 mol.) is added in portions of 0-5 g., with shaking and occasional cooling. After the addition, the solution is cooled to — 5° and the precipitated succinimide filtered off. Carbon tetrachloride is removed from the filtrate by warming under reduced pressure, and the residual liquid is fractionated. Practically the whole of it boils at 94-95°/14 mm. Yield 17-5 g., 82 per cent. 

Many biotinylated succinimide esters are now available. Most of these variations alter the size of the spacer arm between the succinimide coupling group and the biotin. The additional spacers could facilitate avidin binding and, thus, may be critical for some applications (9). 

J0rgensen [111] and Vicario [112] independently described the conjugate addition of both triazole and tetrazole based nucleophiles to a,P-unsaturated aldehyde substrates as an alternative method for C-N bond formation. These reactions were catalysed by the diarylprolinol and imidazolidinone scaffolds with equal efficiency showing the complementarity and efficacy of both these catalyst architectures. In addition, Jprgensen has also shown succinimide to be an effective Michael donor (see Sect. 2.3.5 Scheme 49 for further details) [113]. 

The discovery of the sedative/hynoptic activity of derivatives of barbituric acid has led to very extensive dissections of that molecule. One outcome of this work is the realization that acylurea and acylamide derivatives often exhibit CNS depressant activity. A fair number of such molecules have been prepared that contain a succinimide or glutarimide pharmacophore. For example, Michael addition of cyanide to the stereochemically xmdefined cinnamate... 

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