Methanol-insoluble product

Copolymerization reactions with p-methoxy-a-methylstyrene were also attempted at 0°C, and a methanol-insoluble product having an Mjj of 1600 was obtained over a period of 36 h. From the 250-MHz 1h-NMR spectrum, it was found that p-methoxy-a-methylstyrene was present in the polymer to the extent of 14%. 

The methanol-insoluble product was also upgraded relative to the starting coal. Its H/C ratio was 0.86, its sulfur and nitrogen levels were 0.8% and 1.2%, respectively, and it has fully pyridine soluble. 

The addition of a mixture of monomers and catalyst to a suspension of zinc chloride in benzene or heptane gives 56 and 77% yield, respectively, of methanol-insoluble product containing ca. 57 mole % of acrylonitrile in both cases. Extraction of the product from the reaction carried out in heptane gave 8% of a DMF-soluble fraction which contained 90.9 mole % acrylonitrile and 92% of a DMF-insoluble fraction which contained 52.8% acrylonitrile, close to the theoretical value for an equimolar copolymer. In addition, the reaction mixture gave a 3.9% yield of a methanol-soluble fraction which contained 28.5 mole % acrylonitrile. 

Figure 3. Percentage of methanol-insoluble product obtained during the reaction of 233.4 g of dry whey permeate and 90.3 mL of sulfuric acid in an enclosed reactor at 145 °C. Ammonia was injected after a reaction time of 21 minutes to increase the pH to 4.0.

NMR Studies. Several poly-1,4-DMC samples prepared by BF3-initiated polymerizations using CH2CI2 as a solvent were analyzed by 1H-NMR (300 MHz) and 13C-NMR (20 MHz) spectroscopy. These are identified as samples 13,16 and 22 in Table I. In addition to the methanol-insoluble products obtained by pouring the reaction mixtures into methanol, oligomeric products obtained by evaporating the mother liquors from the precipitation were also examined. In all cases, the methanol-soluble and methanol-insoluble fractions yielded very similar spectra. Consequently only the spectra of the methanol-insoluble products will be discussed. 

To obtain water-insoluble sorbitol copolyesters, 1,8-octanediol was used in place of a fraction of sorbitol in the monomer feed. Adipic acid, 1,8-octanediol, and sorbitol were copolymerized in the molar ratio 50 35 15 (Table 1, entry 2). The methanol-insoluble product had an Mw of 1.17x10. The solubility in water and THF of entry 1 and 2 products, respectively, is direct proof that they have few interchain crosslinks. Furthermore, 0.6- 1.0% w/v solutions of the products passed through 0.45 Um filters with complete recovery of the products which demonstrates the absence of microgels. This was shown by the fact that 99.9%wt of polymer was recovered when a known concentration of polymer solution was passed through the filter and the solvent was evirated. 

Preparation of 7-amino-3-chloro-3-cephem-4-carboxylic acid To a solution of 750 mg (1 55 mmol) of p-nitrobenzyl 7-amino-3-chloro-3-cephem-4-carboxylate hydrochloride in 20 ml of tetrahydrofuran and 40 ml of methanol was added a suspension of 750 mg of prereduced 5% palladium on carbon catalyst in 20 ml of ethanol and the suspension was hydrogenated under 50 psi of hydrogen at room temperature for 45 minutes. The catalyst was filtered and washed with THF and water. The filtrate and catalyst washes were combined and evaporated to dryness. The residue was dissolved in a water-ethyl acetate mixture and the pH adjusted to pH 3. The insoluble product was filtered and triturated with acetone. The product was then dried to yield 115 mg of 7-amlno-3-chloro-3-cephem-4-carboxylic acid. 

A mixture consisting of 22.7 g potassium o-bromobenzoate, 16.6 g 2,6-dichloro-3-methvlani-line, 12 ml N-ethylmorpholine, 60 ml diethylene glycol dimethyl ether, and 1.0 g anhydrous cupric bromide is heated in a nitrogen atmosphere at 145 C to 155°C for 2 hours. The reaction mixture is diluted with 60 ml diethylene glycol dimethyl ether and acidified with 25 ml concentrated hydrochloric acid. The acidic mixture is diluted with 100 ml of water and the liquid phase decanted from the insoluble oil. The insoluble oil is stirred with methanol and the crystalline N-(2,6-dichloro-3-methylphenyl)anthranilic acid which separates is collected and washed with methanol. The product, after recrystallization from acetone-water mixture melts at 248 C to 250°C. 

The flask contents are transferred to a separatory funnel, washed with 100 mL of water, 100 mL of saturated sodium chloride solution, and dried over anhydrous magnesium sulfate. The solvent is removed by rotary evaporator and the solid residue is triturated with three portions of cold (0-5°C) methanol (50 mL, then 20 mL twice). The insoluble product is filtered, air dried, and recrystallized from acetone to give as the first crop 3.0-3.4 g of the pure anti isomer (Notes 6, 7) mp (dec) > 250°C (Note 8). Additional crystallizations bring the yield to 4.6 g (22%). 

Solvents 1 and 2 are known to be good solvents for poly(methyl methacrylate) solvent 3 readily dissolves polystyrene.The solubility tests show that the radically polymerized sample is insoluble in all three solvents.The solubility isthusdifferentfrom that of both poly(methyl methacrylate) and polystyrene.The anionically polymerized product dissolves on warming in the acetone/methanol mixture and also in acetonitrile it is insoluble in cyclohexane/toluene.The solubility is thus similar to that of poly(methyl methacrylate). For the cationically initiated polymerization the product is only slightly soluble in acetone/methanol, insoluble in acetonitrile, but very readily soluble in cyclohexane/toluene.The solubility thus resembles that of polystyrene. 

Unlike the alternating copolymer, these high yield benzene-insoluble products were not completely soluble in acetone, but they were soluble in a mixture of acetone-benzene (2 1). However, unlike polystyrene, they were precipitated essentially completely when excess benzene was added to the acetone-benzene solutions. In contrast when excess benzene was added to a mixture of polystyrene and the alternating copolymer in an acetone-benzene solution, the copolymer precipitated and the polystyrene remained in the benzene-rich solvent. The polystyrene was recovered from this solution by adding excess methanol. 

Sample Preparation. Chemically polymerized 2-ethyl polyaniline, with reported molecular weight of 5000, was prepared by the method outlined by Leclerc et al. (15). Treatment of the insoluble product with ammonium hydroxide solution resulted in transforming the salt into the soluble EB form, which exhibited slight solubility in methanol. The soluble EB form of PANi is known to be readily protonated under acidic conditions, producing the highly insoluble ammonium salt form (16.17). In order to maintain the free amine base form in solution, it was necessary to synthesize the silica gel in the presence of a minimal amount of acid catalyst. 

Dissolve lg (0.005 mol) of l-chloro-2,4-dinitrobenzene in 5 ml of rectified spirit with warming and add a solution of 0.5 ml (0.005 mol) of 2-methyl-propane-1-thiol in 5 ml of rectified spirit containing 2 ml of 10 per cent aqueous sodium hydroxide. Heat under reflux for 10 minutes and decant the hot solution from any insoluble material into a clean conical flask. Allow the solution to cool, filter and recrystallise the sulphide twice from methanol. The product is obtained as yellow flakes, m.p. 75-76 °C the yield is 440 mg (35%). 

Hydrolysis A suspension of 1 g of the 6a,9a-difluoroprednisolone 17a,21-methylorthobutyrate in 10 cc of methanol is treated with 2 cc of a 2 N aqueous solution of oxalic acid and heated on a water bath at 40°-50°C for about 5-10 minutes and, afterwards, the mixture is concentrated under vacuum. The residue is then shaken with water, the insoluble product is filtered off and then dried. The solid material is recrystallized from acetone-ether and 6a,9a-difluoroprednisolone 17-butyrate is obtained, MP 193°-196°C. 

Ozonation of 2-Carboxy-4-nitro-N,N-dimethylaniline (I). The amine (2.10 grams, 10 mmoles) was dissolved in the appropriate solvents (200 ml methanol, ethyl acetate, or methylene chloride) and ozonized at 0°C with equimolar amounts of ozone quantitative absorption occurred. Near the end of the ozonation time, a precipitate formed. In ozonations in methanol this substance was identical with lactone III mp 176°-177°C, prepared according to Villiger (10). In the other solvents the insoluble product was the demethylated starting material, mp 265°-268°C (dec.) reported mp 263°-264°C (11). The mother liquor was evaporated, and the two compounds were separated by fractional crystallization. The results are shown in Table I. 

The Step 1 product (0.21 mmol) and (CF3S03)2Sn (0.9 mg) were introduced into a reaction vessel the mixture was shaken until uniform then heated for 3 hours at 180°C. The mixture was then separated by decantation into THF where 47.1 mg dissolved and 2.20 mg was insoluble. The THF-soluble portion was then redissolved in 3 ml THF and treated with diazomethane dissolved in 1 ml diethyl ether and stirred for 5 hours at ambient temperature. The mixture was concentrated and the residue divided into a methanol-soluble part (8.10 mg) and methanol-insoluble part (34.9 mg). The methanol-insoluble part was divided into a THF-soluble part (14.19 mg) and a THF-insoluble part (20.64 mg). The part that was insoluble in methanol but soluble in THF was identified as the product with a M of roughly 1.0 x 10 daltons. 

Solvent Composition. In Table III the solubilities of Illinois No. 2 after treatment with KOH and various protic solvents are given. Note that both the glycols and ethanol gave similar yields of extraction products both methanol and water result in large amounts of insoluble products. The superiority of alcohols compared to water for reduction and solubilization of coal also has been noted in acid ZnCl2 melt reductions (15). 

Phenol, the simplest and most important phenolic compound in industrial fields, is a multifunctional monomer for oxidative polymerization, and hence, conventional polymerization catalysts afford an insoluble product with uncontrolled structure. On the other hand, the peroxidase catalysis induced the polymerization in aqueous organic solvent to give a powdery polymer consisting of phenylene and ox-yphenylene units showing relatively high thermal stability (Scheme 2).5,6 In the HRP and soybean peroxidase (SBP)-catalyzed polymerization in the aqueous 1,4-dioxane, the resulting polymer showed low solubility the polymer was partly soluble in N,N-dimethylformamide (DMF) and dimethyl sulfoxide and insoluble in other common organic solvents.5 On the other hand, the aqueous methanol solvent af-... 

Anhydrous material, prepared by refluxing the hydrate with acetic anhydride and washing the insoluble product with dry ether, is used in methanol-pyridine for the oxidative coupling of terminal acetylenes to diynes. Mechanism. Review. ... 

---