Methanol Hydroquinone

The points R have to be on a straight line terminating in the composition of the methanol hydroquinone clathrate (A) in equilibrium with a-hydroquinone at 25°C. The point B roughly corresponds to the composition of the clathrate obtained by Palin and Powell24 when crystallizing hydroquinone from methanol points between A and B form a continuous range of solid solutions in equilibrium with liquid phases whose compositions lie on the curve CE. It is found that the equilibrium clathrate has a composition corresponding to y — 0.474 at 25°C. 

Hydroquinone can be deterrnined spectrophotometricaHy at 292 nm in methanol after a sample is evaporated to dryness to remove the interference of acrolein. An alternative method is high performance Hquid chromatography on 10-p.m LiChrosorb RP-2 at ambient temperature with 2.0 mL/min of 20%(v/v) 2,2,4-trimethylpentane, 79.20% chloroform, and 0.80 % methanol with uv detection at 292 nm. 

Reactions with Organic Compounds. Tetrafluoroethylene and OF2 react spontaneously to form C2F and COF2. Ethylene and OF2 may react explosively, but under controlled conditions monofluoroethane and 1,2-difluoroethane can be recovered (33). Benzene is oxidized to quinone and hydroquinone by OF2. Methanol and ethanol are oxidized at room temperature (4). Organic amines are extensively degraded by OF2 at room temperature, but primary aHphatic amines in a fluorocarbon solvent at —42°C are smoothly oxidized to the corresponding nitroso compounds (34). 

The reaction mixture was removed from the vessel and distilled at a pressure of 30-60 mm, and a bath temperature of 30°C to 50°C until the methanol had all been removed. The extremely viscous tarry residue remaining in the still pot was given a very crude distillation, the distillate boiling at B2°C to 1 32°C/2 mm. In an attempt to purify this distillate by a more careful distillation, 5.3 g of a liquid distilling from 53°C to 150°C/5 mm was collected. At this point, much solid sublimate was noted not only in this distillate but in the condenser of the still. 7 g of the solid sublimate was scraped out of the condenser of the still. Recrystallization of the sublimate from ethyl acetate containing a small amount of petroleum ether gave beautiful crystals melting at 175°C to 177°C (5 g). Infrared analysis confirmed that this compound was hydroquinone (9% conversion). 

Stage B Preparation of 17j -HydroxyEstra-4,9,11-Trien-3-one — 3 g of 17/3-benzoyloxy-estra-4,9,11 -trien-3-one, obtained as described in Stage A are dissolved in 15 cc of methanol. 0.03 g of hydroquinone is added, and the mixture Is taken to reflux while bubbling in nitrogen. Then 1.2 cc of 11% methanolic caustic potash is added and reflux is maintained for three hours, after which the reaction product Is acidified with 0.36 cc of acetic acid. 

In another study, uniform composite polymethyl-methacrylate/polystyrene (PMMA/PS) composite particles in the size range of 1-10 fim were prepared by the seeded emulsion polymerization of styrene [121]. The PMMA seed particles were initially prepared by the dispersion polymerization of MMA by using AIBN as the initiator. In this polymerization, poly(7V-vinyl pyrolli-done) and methyl tricaprylyl ammonium chloride were used as the stabilizer and the costabilizer, respectively, in the methanol medium. Seed particles were swollen with styrene monomer in a medium comprised of seed particles, styrene, water, poly(7V-vinyl pyrollidone), Polywet KX-3 and aeorosol MA emulsifiers, sodium bicarbonate, hydroquinone inhibitor, and azobis(2-methylbu-... 

Cadmium phthalocyanine (PcCd) is prepared from phthalonitrile and cadmium filings58 and under high pressure starting from phthalonitrile, hydroquinone and cadmium(II) nitrate in methanol.80... 

Fig. 5. Determination of the composition of the equilibrium clathrate of hydroquinone and methanol at 25°C with the aid of -propanol as an auxiliary solvent. The figure at the bottom illustrates the method used for determining the position of the side CA of the three-phase area A CD.

Methanol clathrates, 2, 20 in hydroquinone, 7 Methyl alcohol, barrier force of internal rotation, 381... 

The most important host for clathrates is hydroquinone. Three molecules, held together by hydrogen bonding, make a cage in which one molecule of the guest fits. Typical guests are methanol (but not ethanol), SO2, CO2, and argon (but not neon). 

A strong acceptor TCNE undergoes [2+2] rather than [4+2] cycloaddition reactions even with dienes. 1,1-Diphenylbutadiene [20] and 2,5-dimethyl-2,4-hexadiene (Scheme 5) [21] afford mainly and exclusively vinyl cyclobutane derivatives, respectively. In the reactions of 2,5-dimethyl-2,4-hexadiene (1) the observed rate constant, is greater for chloroform solvent than for a more polar solvent, acetonitrile (2) the trapping of a zwitterion intermediate by either methanol or p-toluenethiol was unsuccessful (3) radical initiators such as benzyl peroxide, or radical inhibitors like hydroquinone, have no effect on the rate (4) the entropies of activation are of... 

Clay-supported heteropoly acids such as H3PW12O40 are more active and selective heterogeneous catalysts for the synthesis of MTBE from methanol and tert-butanol, etherification of phenethyl alcohols with alkanols, and alkylation of hydroquinone with MTBE and tert-butanoi (Yadav and Kirthivasan, 1995 Yadav and Bokade, 1996 Yadav and Doshi, 2000), and synthesis of bisphenol-A (Yadav and Kirthivasan, 1997). 

Reductive activation of the quinone shown in Scheme 7.9 and incubation in methanol afforded a complex mixture of products consisting mainly of head-to-tail coupling at C-5 or C-7 (Scheme 7.10). Minor reactions involve transfer of H2 from the hydroquinone to the ene-imine (internal redox reaction) and methanol trapping. The structures of the dimers and trimers in Scheme 7.10 were derived from H-NMR,... 

The results of the methanolic solvolysis study shown in Fig. 7.15 reveals that nucleophilic attack on the cyclopropyl quinone methide by methanol affords the pyrido[1,2-a]indole (73 ppm) and azepino[l,2-a]indole (29ppm) trapping products. Initially, nucleophilic attack on the cyclopropane ring affords the hydroquinone derivatives (see Scheme 7.17) that oxidizes to the quinones upon aerobic workup. 

Another class of DNA alkylating agents, the Mitomycins, proved to be most promising in clinical trials. Among these, mitomycin C, shown in Fig. 6.1, exhibits significant anti-tumor activity. Its mechanism of activation consists of a complex bioreductive process. The first step is the reduction to hydroquinone, followed by a loss of methanol. This reaction fa-... 

An interesting observation reported in Table XLIX is the increase in the hydroquinone/catechol ratio from 1.44 to 1.99 when the dielectric constant of the medium is decreased from 58.9 to 39.2 by addition of methanol to water. A similar increase in the hydroquinone/catechol ratios was also observed in phenol hydroxylation catalyzed by TS-1 (266) in dioxane-water and tert-butyl alcohol-water mixtures. The para/ortho ratio increased nearly 10-fold when 10% dioxane was added to water. Similarly, the para/ortho ratio more than doubled (1.3-3.0) when 10% tert-butyl alcohol was added to water. An opposite trend, namely, a decrease in the para/ortho ratio from 1.4 to 0.6, was observed when 10% formamide (s = 108) was added to water. Because of geometric constraints in the MFI pores, catechol is expected to be formed more easily on the external surface of TS-1 crystallites than in the pores (91). Hydroquinone, less spatially demanding, can form in the TS-1 channels. A greater coverage of the hydrophobic... 

The BASF route started from hydroquinone, which was converted to 2,5-dihydroterephthalic acid by a Kolbe-Schmitt reaction. One mole of this acid was treated with two moles of an arylamine, both components being in the form of a suspension in aqueous methanol. This was added to a small amount of a solution of vanadium(III) chloride and sodium chlorate. Gentle heating gave a 95% yield of 2,5-bis(arylamino)benzo-l,4-quinone-3,6-dicarboxylic acid. Ring closure to the trans-quinacridonequinone took place in the presence of concentrated sulphuric acid at 60-80 °C. This was then reduced to the required crude pigment by zinc or aluminium powder in caustic soda under pressure,in an aluminium chloride/urea melt or by the use of a sulphuric acid/polyphosphoric acid mixture. 

Although reduction of quinones is usually a detoxication pathway, there are examples such as mitomycin C in which the hydroquinone is more toxic than the quinone as shown in Figure 5.12 and this may increase the susceptibility of cancers that express high levels of NQO. In this case, the reduction of the quinone leads to the loss of methanol, which is the first step in the activation of this anticancer agent (20). 

The polymers used in this study were prepared by a nucleophilic activated aromatic substitution reaction of a bisphenate and dihalo diphenyl sulfone ( ). The reaction was carried out in an aprotic dipolar solvent (NMP) at 170°C in the presence of potassium carbonate (Scheme 1) (5,6). The polymers were purified by repeated precipitation into methanol/water, followed by drying to constant weight. The bisphenols used were bisphenol-A (Bis-A), hydroquinone (Hq) and biphenol (Bp). Thus, the aliphatic character of Bis-A could be removed while retaining a similar aromatic content and structure. The use of biphenol allows an investigation of the possible effect of extended conjugation on the radiation degradation. 

The hydroquinone process was developed by BASF [12]. Hydroquinone-2,5-di-carboxylic acid is prepared by a modified Kolbe-Schmidt synthesis from hydroquinone and carbon dioxide. Subsequent reaction with arylamine in an aqueous-methanolic suspension in the presence of an aqueous sodium chlorate solution and a vanadium salt affords the product in good yield ... 

Palladium(O) forms a complex with quinone that is now electron rich and can be protonated to give hydroquinone and palladium(II). The latter can start a new cycle via a carbomethoxy species after reaction with methanol and CO (c.f. reaction (6), Figure 12.4). Thus we have formally switched from a hydride initiator to a carbomethoxy initiator species. Addition of quinone to a nonactive or moderately active palladium system is a diagnostic tool that tells us whether zerovalent palladium is involved as an inactive state. Likewise, one might add dihydrogen to a system to see whether palladium(II) salts need to be converted to a hydride to reactivate our dormant catalyst. 

The electrolysis apparatus for the polymerization is illustrated in Figure 2, which is characterized by a single cell without a partition membrane between the electrodes. In poor solvents of poly(phenyleneoxide) s such as methanol and acetonitrile, the polymer was deposited on the electrode, i.e. passivation of the electrode occured. Dichlo-romethane, nitrobenzene, and hydroquinone dimethyl ether were selected as the solvents because both the polymer and a supporting electrolyte dissolved in them and they were relatively stable under electrolysis conditions. 

Note Inhibited with 35-45 ppm hydroquinone monomethyl ether to prevent polymerization during storage and transport (Acros Organics, 2002). Commercial grades may contain the following impurities acetone and acetonitrile (300-500 ppm), acetaldehyde and propionaldehyde (300-500 ppm), acrolein, methanol, isopropanol and hydrogen cyanide (300-500 ppm) (NICNAS, 2000)... 

AI3-00040, see Cyclohexanol AI3-00041, see Cyclohexanone AI3-00045, see Diacetone alcohol AI3-00046, see Isophorone AI3-00050, see 1,4-Dichlorobenzene AI3-00052, see Trichloroethylene AI3-00053, see 1,2-Dichlorobenzene AI3-00054, see Acrylonitrile AI3-00072, see Hydroquinone AI3-00075, see p-Chloro-rrr-cresol AI3-00078, see 2,4-Dichlorophenol AI3-00085, see 1-Naphthylamine AI3-00100, see Nitroethane AI3-00105, see Anthracene AI3-00109, see 2-Nitropropane AI3-00111, see Nitromethane AI3-00118, see ferf-Butylbenzene AI3-00119, see Butylbenzene AI3-00121, see sec-Butylbenzene AI3-00124, see 4-Aminobiphenyl AI3-00128, see Acenaphthene AI3-00134, see Pentachlorophenol AI3-00137, see 2-Methylphenol AI3-00140, see Benzidine AI3-00142, see 2,4,6-Trichlorophenol AI3-00150, see 4-Methylphenol AI3-00154, see 4,6-Dinitro-o-cresol AI3-00262, see Dimethyl phthalate AI3-00278, see Naphthalene AI3-00283, see Di-rj-butyl phthalate AI3-00327, see Acetonitrile AI3-00329, see Diethyl phthalate AI3-00399, see Tributyl phosphate AI3-00404, see Ethyl acetate AI3-00405, see 1-Butanol AI3-00406, see Butyl acetate AI3-00407, see Ethyl formate AI3-00408, see Methyl formate AI3-00409, see Methanol AI3-00520, see Tri-ocresyl phosphate AI3-00576, see Isoamyl acetate AI3-00633, see Hexachloroethane AI3-00635, see 4-Nitrobiphenyl AI3-00698, see IV-Nitrosodiphenylamine AI3-00710, see p-Phenylenediamine AI3-00749, see Phenyl ether AI3-00790, see Phenanthrene AI3-00808, see Benzene AI3-00867, see Chrysene AI3-00987, see Thiram AI3-01021, see 4-Chlorophenyl phenyl ether AI3-01055, see 1.4-Dioxane AI3-01171, see Furfuryl alcohol AI3-01229, see 4-Methyl-2-pentanone AI3-01230, see 2-Heptanone AI3-01231, see Morpholine AI3-01236, see 2-Ethoxyethanol AI3-01238, see Acetone AI3-01239, see Nitrobenzene AI3-01240, see I idine AI3-01256, see Decahydronaphthalene AI3-01288, see ferf-Butyl alcohol AI3-01445, see Bis(2-chloroethoxy)methane AI3-01501, see 2,4-Toluene diisocyanate AI3-01506, see p,p -DDT AI3-01535, see 2,4-Dinitrophenol AI3-01537, see 2-Chloronaphthalene... 

Benzenediol, see Hydroquinone p-Benzenediol, see Hydroquinone Benzeneformic acid, see Benzoic acid Benzene hexachloride, see Lindane Benzene hexachloride-a-isomer, see a-BHC Benzene-crs-hexachloride, see p-BHC Benzene-y-hexachloride, see Lindane a-Benzene hexachloride, see a-BHC p-Benzene hexachloride, see p-BHC 6-Benzene hexachloride, see 8-BHC y-Benzene hexachloride, see Lindane frans-a-Benzene hexachloride, see p-BHC Benzene hexahydride, see Cyclohexane Benzene methanoic acid, see Benzoic acid Benzene methanol, see Benzyl alcohol Benzene tetrahydride, see Cyclohexene Benzenol, see Phenol... 

High pressure liquid chromatography (HPLC) was used for the quantitative measurement of quinones and hydroquinones in the cultures. 20 pi of supernatant were injected in a Merck-Hitachi HPLC system 655A-12 equipped with a 4.6 x 250 mm Nucleosil C18 column (5 pm, RP 18). The system was run at a flow rate of 1 ml min-1 with a methanol/water gradient (10 to 20% methanol in 15 min, then 20 to 100% methanol in 5 min). The UV detector was operated at 281 nm or 275 nm to follow the reduction of quinones 13 and 14, respectively (37). 

---