Aqueous Synthetic Methods

Non-aqueous synthetic methods have recently been used to assemble mesoporous transition metal oxides and sulfides. This approach may afford greater control over the condensation-polymerization chemistry of precursor species and lead to enhanced surface area materials and well ordered structures [38, 39], For the first time, a rational synthesis of mesostructured metal germanium sulfides from the co-assembly of adamantanoid [Ge4S ()]4 cluster precursors was reported [38], Formamide was used as a solvent to co-assemble surfactant and adamantanoid clusters, while M2+/1+ transition metal ions were used to link the clusters (see Fig. 2.2). This produced exceptionally well-ordered mesostructured metal germanium sulfide materials, which could find application in detoxification of heavy metals, sensing of sulfurous vapors and the formation of semiconductor quantum anti-dot devices. 

Another method that has great potential for the preparation of advanced prepregs and has been explored extensively requites fine powders. The reinforcing fibers are coated with fine particles of the resin and, when heated, the resin flows over the fiber. This method requites finely divided particles either in aqueous solution, in an inert volatile solvent, or as high dielectric material that can be charged and coated by electrostatic attraction to the fiber. Synthetic methods that make fine particles, similar to that described for PEEK (23), are needed. 

The diazo transfer reaction between p-toluenesulfonyl azide and active methylene compounds is a useful synthetic method for the preparation of a-diazo carbonyl compounds. However, the reaction of di-tert-butyl malonate and p-toluenesulfonyl azide to form di-tert-butyl diazomalonate proceeded to the extent of only 47% after 4 weeks with the usual procedure." The present procedure, which utilizes a two-phase medium and methyltri-n-octylammonium chloride (Aliquat 336) as phase-transfer catalyst, effects this same diazo transfer in 2 hours and has the additional advantage of avoiding the use of anhydrous solvents. This procedure has been employed for the preparation of diazoacetoacetates, diazoacetates, and diazomalonates (Table I). Ethyl and ten-butyl acetoacetate are converted to the corresponding a-diazoacetoacetates with saturated sodium carbonate as the aqueous phase. When aqueous sodium hydroxide is used with the acetoace-tates, the initially formed a-diazoacetoacetates undergo deacylation to the diazoacetates. Methyl esters are not suitable substrates, since they are too easily saponified under these conditions. 

Synthetic Method 1 6-(dimethylamino)-3-(N-acetyl-N-methylamino)-10-acetylphenothiazine 8a (procedure from US. Patent 4,652,643).5 A mixture of 9.0g of 6-(dimethylamino)-3-(methylamino)phenothiazin-5-ium chloride (Azure B), 150.0ml of acetic anhydride, and lO.Og of zinc dust was maintained at reflux temperature for approximately 4 hs. After the reaction mixture was cooled to ambient temperature, it was poured into ice water with stirring and 300ml of toluene was added. After stirring for approximately 30 min the toluene layer was separated and washed twice, once with tap water and once with saturated aqueous sodium chloride solution. The toluene was then distilled off at reduced pressure. The residue which remained was dissolved in ethyl acetate and separated into various components by subjecting the solution to column chromatography using silica gel as substrate. Elution with ethyl acetate yielded a white-colored solid. 

Synthetic Method 5 2-benzenesulfonyl-3-(p-carbethoxyanilino)pheno-thiazine (13o) (procedure from U.S. Patent 4,710,570).Sb To a warm, stirred solution of 1.8 g of dye 3-(4-carbethoxyphenylimino)-3//-pheno-thiazine in 50 ml of tetrahydrofuran was added 0.8 g of benzenesulfinic acid (obtained by adding dilute hydrochloric acid to an aqueous solution of benzenesulfinic acid sodium salt to cause precipitation of the free acid). After stirring 1 h at 40°C the solvent was evaporated off under reduced pressure. The yellowish solution was poured into water. The precipitate was filtered, washed repeatedly with distilled water and methanol. Recrystallization from methanol gave 1.9 g (76%) of the leuco dye 2-benzenesulfonyl-3-(4-car-bethoxyanilino)phenothiazine (13o) as a yellowish powder. 

Synthetic Method 7 l,9-dimethyl-4-acetarnido-8-diethylaminoimidazo-phenoxazine (31) (procedure from U.S. Patent 4,604,462). 12 A mixture of 10 g of l,3-diamino-7-diethylamino-8-methylphenoxazin-5-ium chloride (Brilliant Cresyl Blue), 50 ml of acetic anhydride, 10 g of zinc dust, and 10 ml of pyridine was maintained at 85 to 90°C for approximately 1 h. After cooling to room temperature, the reaction mixture was poured into a mixture of water and toluene and the resulting aqueous layer was discarded. The toluene solution was washed twice, first with water and then with... 

Mascarenas developed a synthetic method to 1,5-oxygen-bridged medium-sized carbocycles through a sequential ruthenium-catalyzed alkyne-alkene coupling and a Lewis-acid-catalyzed Prins-type reaction (Eq. 3.45). The ruthenium-catalyzed reaction can be carried out in aqueous media (DMF/H20 = 10 1).181... 

As described in this chapter, the sonochemical reduction technique appears to be a promising method for the preparation of various types of metal nanoparticles in an aqueous solution. By choosing more efficient organic additives, easily-reducible metal precursors, supports and templates with an appropriate role, more advanced functional nanoparticles could be synthesized successfully using the sonochemical reduction technique. In future, it is also possible to develop effective synthetic methods by combining the sonochemical method with other chemical methods. 

The first example of biphasic catalysis was actually described for an ionic liquid system. In 1972, one year before Manassen proposed aqueous-organic biphasic catalysis [1], Par shall reported that the hydrogenation and alkoxycarbonylation of alkenes could be catalysed by PtCh when dissolved in tetraalkylammonium chloride/tin dichloride at temperatures of less than 100 °C [2], It was even noted that the product could be separated by decantation or distillation. Since this nascent study, synthetic chemistry in ionic liquids has developed at an incredible rate. In this chapter, we explore the different types of ionic liquids available and assess the factors that give rise to their low melting points. This is followed by an evaluation of synthetic methods used to prepare ionic liquids and the problems associated with these methods. The physical properties of ionic liquids are then described and a summary of the properties of ionic liquids that are attractive to clean synthesis is then given. The techniques that have been developed to improve catalyst solubility in ionic liquids to prevent leaching into the organic phase are also covered. 

Lou and Zeng spotted the work of Park et al. and sought to improve on it by developing an aqueous synthetic route. In this method, water and sodium sulfate are added to freshly prepared tungstic acid and autoclaved at up to 200°C for up to 24 h (assuming saturated steam conditions, this corresponds to pressures of up to 15.5 bars). 

Cyclopropanation is an important synthetic method, and enantioselective catalytic reactions of olefins and diazoacetates provide access to valuable products with biological activity. In general, these reactions are conducted in anhydrous solvents and in several cases water was found to diminish the rate or selectivity (or both) of a given process. Therefore it came as a surprise, that the Cyclopropanation of styrene with (+)- or (-)-menthyl diazoacetates, catalyzed by a water-soluble Ru-complex with a chiral bis(hydroxymethyldihydrooxazolyl)pyridine (hm-pybox) ligand proceeded not only faster but with much Wgher enantioselectivity (up to 97 % e.e.) than the analogous reactions in neat THF or toluene(8-28 % e.e.) (Scheme 6.34) [72]. The fine yields and enantioselectivities may be the results of an accidental favourable match of the steric and electronic properties of hm-pybox and those of the menthyl-dizaoacetates, since the hydroxyethyl or isopropyl derivatives of the ligand proved to be inferior to the hydroxymethyl compound. Nevertheless, this is the first catalytic aqueous cyclopropanation which may open the way to other similar reactions in aqueous media. 

The direct alkylation of aminopyrazines is usually unsatisfactory as a synthetic method because it mainly takes place at the most basic ring nitrogen. However, 3,6-diamino-2,5-dicyanopyrazines are successfully alkylated by treatment with alkyl iodide or bromide in protic solvent in the presence of alkali such as NaOH in dimethylacetamide (DMA) to form bis(dialkylamino)pyrazines <1998DP(39)49>. Reaction of 2,6-diamino-3,5-diarylpyrazine with methylglyoxal in aqueous HCl-ethanol led to -alkylation but no formation of the expected bicyclic imidazolo[l,2- z]pyrazine <2001S768>. 

Of the various synthetic processes that are available, two are of most relevance in the present context - precipitation from aqueous solution and melt forming. These methods are used where it is not possible to produce adequate products directly from natural sources. This will be because there is no suitable mineral, due to the chemical nature of the product, of particle size and shape requirements, or to purity considerations. The other principal synthetic method in use for filler production is pyrolysis/combustion. This type of process in which the particles are formed in the gas phase is used where very small particles are required, such as with carbon blacks and some silicas. This type of filler is not widely used in thermoplastics and so these processes are not discussed in any detail here, although some information specific to the production of antimony oxide will be found later. 

The above synthetic methods for oxetane all involve formation of a new C—O bond. Cyclization by formation of a new C—C bond has been applied with compounds having benzylic or alkylic CH groups. Recent examples of this type of ring closure are the rearrangement of trans- 2,3-epoxycyclohexyl allyl ether by means of s-butyllithium and the dehydrochlorination of a-cyanobenzyl 2-chloroethyl ether with aqueous base and phase transfer catalyst (equation 86). Both reactions probably involve carbanion intermediates (76TL2115, 75MIP51300). 

Heck-, Suzuki- and Stille-type Couplings - The Heck reaction, palladium-catalysed coupling of aryl or vinyl halides with alkenes or alkynes, is an extremely useful synthetic method. Only recently have Heck reactions been performed in aqueous media, probably due to the perception that water must be carefully... 

A closely related synthesis utilizes alkynic epoxides, which add hydrogen sulfide in the presence of a base to form thiophenes in good yield. For example, when the epoxide (184) was stirred in an aqueous solution of barium hydroxide with slow addition of hydrogen sulfide gas, and the product extracted after neutralization with acetic acid, the substituted thiophene (186) was obtained in 60-70% yield (53ZOB1569). In these experiments R1 = Me or Et, R2 = H or Me and R3 = Ph. The same synthetic method was used to produce a thiophene having an optically active substituent, with relatively little racemization. In this case R1 = EtC HMe while R2 and R3 = H, but the yield was equivalent (73JOC2361). This reaction also undoubtedly proceeds via an intermediate (185), a structure related to a 1 -mercapto-1,3-butadiene. 

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