Nucleophilic reactions displacements

Bimolecular, nucleophilic-displacement reactions of sulfonic esters of carbohydrates have been reviewed.77,78 

6-tri-0-benzoyl-4-0-(2,3,4,6-tetra-0-benzoyl-a-D-galactopyrano-syl)-/3-D-allopyranoside in 68% yield.69 

The nucleophilic-displacement reactions of the 6- (Refs. 45 and 80), 6 - (Refs. 37, 45, and 80), and 4 - (Ref. 45) sulfonic derivatives of methyl /3-maltoside, the 6-sulfonates32,86 of /3-maltose, and the 6 -sulfonate46 of l,6-anhydro-/3-maltose have been reported. 

The selective replacement of hydroxyl groups in carbohydrates by chlorine has been achieved by the use of sulfuryl chloride.1,74,87,88 The reaction of sulfuryl chloride with maltose89,90 and methyl /3-maltoside24 has been studied. Treatment of maltose with sulfuryl chloride, initially for 2 h at — 70° and then processing at room temperature, gave, after methyl glycosidation and dechlorosulfation, a low yield 

Reaction of methyl /3-maltoside with 30 equivalents of methanesul-fonyl chloride inN,N-dimethylformamide for 8 days at 65° gave a mixture of methyl 3,6-dichloro-4-0-(6-chloro-6-deoxy-a-D-gIucopyrano-syl)-3,6-dideoxy-/3-D-allopyranoside (37), isolated in 46% yield as its tetraacetate (38), and methyl 3,6-dichloro-3,6-dideoxy-4-0-(4,6-di- 

The alkylation of primary nitramines with alkyl halides is of little preparative value for the synthesis of secondary nitramines. Such reactions often result in a mixture of N- and 0-alkylated products. The product distribution appears to be very dependent on the nature of the cation of the nitramine used, with silver salts ° favouring 0-alkylation and alkali metal salts usually giving A-alkylation as the predominant product. However, this is not always the case. 

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Nucleophilic Displacement Reactions. The presence of activating groups, eg, o,p mX.1.0 groups, makes aromatic fluorine reactive in nucleophilic displacement reactions. This has been demonstrated by deterrnination of the relative fluorine—chlorine displacement ratios from the reaction of halonitroben2enes with sodium methoxide in methanol (137) F is displaced 200—300 times more readily than Cl. 

Nucleophilic Displacement Reactions. The strong electron-withdrawing effect of a trifluoromethyl group activates ortho and para halogen toward nucleophilic attack. Such chlorine labiUty is utili2ed in the manufacture of crop control chemicals containing trifluoromethyl and nitro groups. 

The first commercial PPS process by Phillips synthesized a low molecular weight linear PPS that had modest mechanical properties. It was usehil in coatings and as a feedstock for a variety of cured injection-molding resins. The Phillips process for preparing low molecular weight linear PPS consists of a series of nucleophilic displacement reactions that have differing reactivities (26). 

O- Alkylation is comparable to A/-alkylation, but since the sodium salts are water-soluble it is most convenient to treat the phenol or naphthol in aqueous caustic solution with dimethyl sulfate or diethyl sulfate. These are comparatively expensive reagents, and therefore, alkoxy groups are introduced at a prior stage by a nucleophilic displacement reaction whenever possible. 

Rates of debromination of bromonitro-thiophenes and -selenophenes with sodium thio-phenoxide and sodium selenophenoxide have been studied. Selenophene compounds were about four times more reactive than the corresponding thiophene derivatives. The rate ratio was not significantly different whether attack was occurring at the a- or /3-position. As in benzenoid chemistry, numerous nucleophilic displacement reactions are found to be copper catalyzed. Illustrative of these reactions is the displacement of bromide from 3-bromothiophene-2-carboxylic acid and 3-bromothiophene-4-carboxylic acid by active methylene compounds (e.g. AcCH2C02Et) in the presence of copper and sodium ethoxide (Scheme 77) (75JCS(P1)1390). 

H-Azepine, 2-allyloxytetrahydro-Claisen rearrangement, 7, 508 3H-Azepine, 2-amino-acylation, 7, 511 effect of acidification, 7, 510 nucleophilic displacement reactions, 7, 514 synthesis, 7, 533, 535 3H-Azepine, 2-amino-7-bromo-synthesis, 7, 529 3H-Azepine, 2-anilino-ring inversion, 7, 495-499 structure, 7, 533... 

Imidazo[l,2-c]pyrimidine, 2,5,7-trichloro-nucleophilic displacement reactions, 5, 627 Imi dazo[ 1,2-a]pyrimidines pK, 3, 338 reactivity, 5, 627 synthesis, 5, 647 Imidazo[ 1,2-c]pyrimidines reactions, 5, 627 structure, 5, 610 synthesis, 5, 648-649 lmidazo[ 1,5-a]pyrimidines reactions, 5, 628 synthesis, 5, 649 lmidazo[l,5-6]pyrimidines synthesis, 5, 649-650 Imidazopyrrolopyridines bromination, 4, 506 lmidazo[4,5-6]quinoxaline nomenclature, 1, 22... 

H-Pyrido[3,2-c]azepine, 7-methoxy-nucleophilic displacement reactions, 7, 514 Pyridoazepines synthesis, 7, 535, 540 Pyridoazepinones synthesis, 7, 531 Py rido[2,1-a]benzazepin-6-one physiological properties, 7, 546 Py rido[ 1,2-a]benzimidazoles reactions, 6, 1041... 

Pyrimidine, I-alkyl-2-methyltetrahydro-C-thioacylation, 4, 807 Pyrimidine, 4-alkylsulfinyl-nucleophilie displaeement reaetions, 3, 97 Pyrimidine, 6-alkylsulfinyl-nucleophilic displacement reactions, 3, 97 Pyrimidine, 2-alkylsulfonyl-nueleophilie displaeement reactions, 3, 97 Pyrimidine, 4-alkylsulfonyl-nucleophilic displacement reactions, 3, 97 Pyrimidine, 6-alkylsulfonyl-nucleophilie displaeement reactions, 3, 97 Pyrimidine, alkylthio-dealkylation, 3, 95 desulfurization, 3, 95 oxidation, 3, 96 synthesis, 3, 135, 136 Pyrimidine, 2-alkylthio-aminolysis, 3, 96 hydrolysis, 3, 95 Prineipal Synthesis, 3, 136 Pyrimidine, 4-alkylthio-aminolysis, 3, 96 hydrolysis, 3, 95 Pyrimidine, 6-alkylthio-aminolysis, 3, 96 hydrolysis, 3, 95 Pyrimidine, 4-allenyloxy-rearrangement, 3, 93 Pyrimidine, 4-allyloxy-2-phenyl-rearrangement, 3, 93 Pyrimidine, 4-allynyloxy-rearrangement, 3, 93 Pyrimidine, 4-anilino-2,5,6-trifluoro-NMR, 3, 63 Pyrimidine, 2-aryl-pyrroleaeetic aeid from, 4, 152 Pyrimidine, arylazo-synthesis, 3, 131 Pyrimidine, 4-arylazo-reduetion, 3, 88... 

H-Pyrimido[l, 2-6]pyridazin-2-one, chloro-nucleophilic displacement reactions, 3, 343 2H-Pyrimido[l,2-6]pyridazin-2-one, 7-chloro-synthesis, 3, 354... 

Phase transfer catalysts were used for nucleophilic displacement reactions of activated leaving groups by hydroxyfurazanyl anions. For example, tetrachloro-pyrazine was found to react with hydroxyfurazans in benzene/Na2C03/tetraalkyl-ammonium salts giving products of mono- or disubstitution (Scheme 173) (94MI1). The course of the reaction depends on the ratio of the reactants and the nature of the ammonium salt. 

Intramolecular nucleophilic displacement reactions of aromatic nitro group by various nucleophiles include cydization reactions, which provide practical methods for the synthesis of a variety of heterocycles. 1 hope that the text of this review suggests a wide range of potential of this reaction in organic synthesis of various heterocycles. However, it is necessary to stress that some structural types described in this review could be prepared with similar, or even better yields by other methods. In spite of this, there are many heterocyclic systems for the synthesis of which the denitrocyclization strategy is a method of choice. 

Nucleophilic displacement reactions One of the most common reactions in organic synthesis is the nucleophilic displacement reaction. The first attempt at a nucleophilic substitution reaction in a molten salt was carried out by Ford and co-workers [47, 48, 49]. FFere, the rates of reaction between halide ion (in the form of its tri-ethylammonium salt) and methyl tosylate in the molten salt triethylhexylammoni-um triethylhexylborate were studied (Scheme 5.1-20) and compared with similar reactions in dimethylformamide (DMF) and methanol. The reaction rates in the molten salt appeared to be intermediate in rate between methanol and DMF (a dipolar aprotic solvent loiown to accelerate Sn2 substitution reactions). 

A quantitative study of the nucleophilic displacement reaction of benzoyl chloride with cyanide ion in [BMIM][PFg] was investigated by Eckert and co-workers [52]. The separation of the product, 1-phenylacetonitrile, from the ionic liquid was achieved by distillation or by extraction with supercritical CO2. The 1-phenylacetonitrile was then treated with KOH in [BMIM][PF6] to generate an anion, which reacted with 1,4-dibromobutane to give 1-cyano-l-phenylcyclopentane (Scheme 5.1-23). This was in turn extracted from the ionic liquid with supercritical CO2. These... 

As a demonstration of the complete synthesis of a pharmaceutical in an ionic liquid, Pravadoline was selected, as the synthesis combines a Friedel-Crafts reaction and a nucleophilic displacement reaction (Scheme 5.1-24) [53]. The allcylation of 2-methylindole with l-(N-morpholino)-2-chloroethane occurs readily in [BMIM][PF6] and [BMMIM][PF6] (BMMIM = l-butyl-2,3-dimethylimida2olium), in 95-99 % yields, with potassium hydroxide as the base. The Friedel-Crafts acylation step in [BMIM][PF6] at 150 °C occurs in 95 % yield and requires no catalyst. 

Interests in the phase transfer catalysis (PTC) have grown steadily for the past several years [68-70]. The use of PTC has recently received industrial importance in cases where the alternative use of polar aprotic solvents would be prohibitively expensive [71-74]. Thus, the potential application of the phase transfer catalyzed aromatic nucleophilic displacement reactions between phenoxide or thiophenoxide and activated systems has... 

Table 4 Phase Transfer Catalyzed Aromatic Nucleophilic Displacement Reaction...

Benzazepin-2-amines can be obtained by nucleophilic displacement reactions on a variety of substrates. For example, the benzazepin-2-amine 22 is formed by treating the thiolactam 21, obtained from the benzazepinone 20 with phosphorus pentasulfide in pyridine or triethylamine solution, with ammonia.61... 

With bromine monochloride at 0°C in a variety of solvents, 1 was converted into addition products, the product distribution being a function of solvent. A change in halogenating agent also altered the product ratio. (Scheme 4) Nucleophilic displacement reactions between these products and silver fluoride was found to cause preferential bromine substitution (83G149). 

The nucleophilic displacement reactions with azide, primary amines, thiols and carboxylatc salts arc reported to be highly efficient giving high (>95%) yields of the displacement product (Table 9.25). The latter two reactions are carried out in the presence of a base (DBU, DABCO). Radical-induced reduction with tin hydrides is quantitative. The displacement reaction with phenolates,61j phosphines,6M and potassium phthalimide608 gives elimination of HBr as a side reaction. 

Nucleophilic Displacement Reactions in Carbohydrates. Part III. Displacements with 1,2 5,6-Di-O-isopropylidene-3-O-toluene-p-sulphonyl-a-D-gulofuranose, J. S. Brimacombe, (Miss) P, A. Gent, and M. Stacey,/. Chem. Soc. C, (1968) 567-569. 

Most nitroquinoxalines have been made as precursors for quinoxalinamines. Moreover, the presence of a powerfully electron-withdrawing nitro group in the molecule will activate leaving groups (such as halogeno) toward all sorts of nucleophilic displacement reactions. 

Polymers for these conductive systems may be synthesised by a variety of means including Ziegler-Natta polymerisation or nucleophilic displacement reactions. The molecules tend to be rigid because of the need for them to possess extended conjugation. This lack of free rotation about carbon-carbon bonds within the molecule imposes a high energy barrier to solvation, thus making these molecules difficult to dissolve. This lack of solubility in turn... 

The photolysis of chlorinated aromatic compounds occurs by several processes which follow predictable routes 13). They frequently undergo photochemical loss of chlorine by dissociation of the excited molecule to free radicals or, alternatively, through a nucleophilic displacement reaction with a solvent or substrate molecule. Either mechanism is plausible, and the operation of one or the other may be influenced by the reaction medium and the presence of other reagents. 

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