4-Toluenesulfonic acid monohydrate

Triethyl 1,1,2-ethanetricarboxylate 4-Toluenesulfonic acid monohydrate Lithium aluminum hydride Sodium hydroxide... 

The organic modification of LDHs is an inevitable step in the process of polymer nanocomposites preparation. Therefore, the intercalated anions are important to the dispersion of LDHs and the resulting fire properties. Zammarano et al. [98] examined the effect of two organic modifiers, 3-aminobenzenesulfonic acid (ABS) and 4-toluenesulfonic acid monohydrate (TS), on the structure and properties of epoxy/LDH composites. Because of their reactivity with epoxy, ABS-modified LDHs (LDH-ABS) had better dispersion than LDH-TS. As a result, epoxy/LDH-ABS showed a greater reduction in PHRR (51%) than epoxy/LDH-TS at the same LDH loading. 

Isobutyraldehyde, allyl alcohol, p-cymene, and p-toluenesulfonic acid monohydrate were purchased from Aldrich Chemical Company, Inc., and used as received. 

Cinnamaldehyde dimethylacetal is prepared by the method used to prepare the corresponding diethylacetal. A mixture of 66.0 g. (0.5 mole) of Aldrich Chemical Company, Inc.), 100 g. (1.06 mole) of trimethyl orthoformate (Eastman Organic Chemicals), 450 ml. of anhydrous methanol (J. T. Baker Chemical Company), and 0.5 g. ofp-toluenesulfonic acid monohydrate (Fisher Scientific Company) is stirred at room temperature for 24 hours. At the end of this time the alcohol is removed with a rotary evaporator and the residue is distilled to give 81-83 g. (91-93%) of cinnamaldehyde dimethylacetal, b.p. 93—96° (0.2 mm.). 

A good commercial grade of />-toluenesulfonic acid monohydrate, m.p. 104-106°, was used. 

In a 2-1. flask fitted with a total-reflux, variable-take-off distillation head is placed a solution of 53 g. (0.472 mole) of dihydroresorcinol (Note 1), 2.3 g. of -toluenesulfonic acid monohydrate and 250 ml. of absolute ethanol in 900 ml. of benzene. The mixture is heated to boiling and the azeotrope composed of benzene, alcohol, and water is removed at the rate of 100 ml. per hour. When the temperature of the distilling vapor reaches 78° (Note 2), the distillation is stopped and the residual solution is washed with four 100-ml. portions of 10% aqueous sodium hydroxide which have been saturated with sodium chloride. The resulting organic solution is washed with successive 50-ml. portions of water until the aqueous washings are neutral and then concentrated under reduced pressure. The residual liquid is distilled under reduced pressure. The yield of 3-ethoxy-2-cyclohexenone (Note 3), b.p. 66-68.5°/0.4 mm. or 115-121°/11 mm., Mq 1.5015, is 46.6-49.9 g. (70-75%). 

Bisethylenedioxypregn-5-ene. Method A. A mixture of progesterone (10 g), freshly distilled ethylene glycol (80 ml) and benzene (350 ml) is slowly distilled for 15 min to remove traces of water. p-Toluenesulfonic acid monohydrate (0.3 g) is added and the mixture is heated under reflux with stirring for 5 hr with a water separator. Saturated sodium bicarbonate solution is added to the cooled mixture and the benzene layer is separated. The organic layer is washed twice with water, dried and evaporated in vacuo. The residue is crystallized twice from acetone-methanol to give 4.15 g (32%) of bisketal, mp 178-181°. 

An improved yield of ketal is obtained by heating a solution of 2 g of progesterone in 16 ml of ethylene glycol and 70 ml of toluene containing 65 mg of / -toluenesulfonic acid monohydrate at reflux for 4 hr. The yield of bisethy-lene ketal is 1.34 g (67%), mp 178-182°. 

Testosterone. 3,3-Ethylenedioxyandrost-5-en-17 -ol (1 g) is dissolved in anhydrous acetone (50 ml), p-toluenesulfonic acid monohydrate (50 mg) is added and the mixture is heated under reflux for 14 hr. Concentration of the resulting solution to a small volume (10 ml) and precipitation with water gives a quantitative yield of slightly impure testosterone (0,87 g, 100%), mp 147-151°. Recrystallizatioii from ether furnishes the pure product of mp 152-154° [ ]d 109° (CHCI3). 

Androst-4-ene-3,l7-dione 3-Ethylene Thioketal A solution of androst-4-ene-3,17-dione (1.42 g, 5 mmoles) in acetic acid (20 ml) is treated with ethanedithiol (0.47 g, 5 mmoles) and a solution of 0.45 of p-toluenesulfonic acid monohydrate in acetic acid (5 ml). After 1 hr at room temperature, the pale yellow solution is poured into water and the resulting suspension is extracted with chloroform. The chloroform solution is washed with water, 5 % sodium hydroxide solution and water, dried (Na2S04) and evaporated. Chromatography of the resulting oil (1.93 g) over silica gel yields androst-4-ene-3,17-dione bisethylene thioketal, mp 173-175° [0.16 g, eluted with petroleum ether-benzene (1 2)] and androst-4-ene-3,17-dione 3-ethylene thioketal, mp 173-176° [1.38 g (76%), eluted with benzene-ethyl acetate (19 1)]. 

Methoxypregna-3,5-dien-20-oned A solution of progesterone (0.3 g) dissolved in 5 ml of 2,2-dimethoxypropane-dimethylformamide (1 1) is treated with p-toluenesulfonic acid monohydrate (8 mg) and 0.1 ml of methanol and then heated under reflux for 3.5 hr. The cooled solution is neutralized with 45 mg of sodium bicarbonate, dissolved in 200 ml of ice water, stirred for 0.5 hr and filtered. The enol ether thus obtained (0.29 g, 92%) is purified by crystallization from acetone-methanol containing a trace of pyridine mp 135-160° [a]o —61° (CHCI3). 

AT-Di- N-pyrwlidinyI)-androsta-3,5, 6-tnen-ll-one. A mixture of and-rost-4-ene-3,ll,17-trione (1.5 g, 0.005 mole), benzene (20 ml), pyrrolidine (1.67 ml) and p-toluenesulfonic acid monohydrate (10 mg), is heated under reflux with stirring, a graduated trap being used to collect the water produced from the reaction. Two molar eq of water are collected during 3.5 hr. 

The hydration of 5-amino-3-cyano-l-(2,6-dichloro-4-trifluoromethylphenyl)-4-ethynylpyrazole was performed with p-toluenesulfonic acid monohydrate in acetonitrile (2 h, room temperature) to give the corresponding 4-acetyl derivative. An alkyl substituent at the triple bond decreases the rate of hydration the conversion of 5-amino-3-cyano-l-(2,6-dichloro-4-trifiuoromethylphenyl)-4-(prop-l-yn-l-yl) pyrazole to the 4-propanoylpyrazole was completed after 18 h (98INP9804530 99EUP933363). 

A mixture of cyclohexanone (11.8 g, 0.12 mole), ethylene glycol (8.2 g, 0.13 mole), /j-toluenesulfonic acid monohydrate (0.05 g), and 50 ml of benzene is placed in a 250-ml round-bottom flask fitted with a water separator and a condenser (drying tube). The flask is refluxed (mantle) until the theoretical amount of water (approx. 2.2 ml) has collected in the separator trap. The cooled reaction mixture is washed with 20 ml of 10 % sodium hydroxide solution followed by five 10-ml washes with water, dried over anhydrous potassium carbonate, and filtered. The benzene is removed (rotary evaporator) and the residue is distilled, affording l,4-dioxaspiro[4.5]decane, bp 65-67713 mm, 1.4565-1.4575, in about 80% yield. 

A 250-ml round-bottom flask is charged with a mixture of cyclohexanone (14.7 g, 0.15 mole), morpholine (15.7 g, 0.18 mole), and / -toluenesulfonic acid monohydrate (0.15 g) in 50 ml of toluene. The flask is fitted with a water separator and a condenser and is brought to reflux (mantle). The separation of water begins immediately and the theoretical amount (2.7 ml) is obtained in about 1 hour. Without further treatment, the reaction mixture may then be distilled. After removal of the toluene at atmospheric pressure, the product is obtained by distillation at reduced pressure, bp II8-I207IO mm, 1.5122-1.5129, in about 75% yield. 

Preparation of 17a-Hydroxyprogesterone 3,20-Bis-(Ethylene Keta/J A solution was prepared containing 50.0 g of 17a-hydroxyprogesterone in 1,000 ml of ben2ene, 100 ml of ethylene glycol and 2.5 g of p-toluenesulfonic acid monohydrate. This mixture was re-... 

Preparation of 11-Keto-6 -Methy progesterone 3,20-Bis-(Ethylene Ketal) A mixture of 5 g of 11-keto-6(3-methylprogesterone (Spero et al, 7. Am. them. Soc., 78, 6213 (1956)], 503 ml of benzene, 26 ml of ethylene glycol, and 0.152 g of p-toluenesulfonic acid monohydrate was stirred and heated under reflux for 22 hours while water was removed by means of a water trap. The reaction mixture was then cooled to 30°C, 0.4 ml of pyridine was added, and stirring was continued for 10 minutes. 

Polycondensation At room temperature, 0.4% mass of Sn(II) chloride dihydrate (SnCl2-2H20) and 0.4% mass of p-toluenesulfonic acid monohydrate (p-TSA) are introduced into the mixture. The mixture is heated to 180°C under mechanical stirring. The pressure is reduced stepwise to reach 13 mbar, and file reaction is continued for 20 h. The reaction system becomes gradually viscous, and a small amount of L-lactide is formed and refluxed through the reflux condenser. At file end of the reaction, the flask is cooled down, file product is dissolved in chloroform and subsequently precipitated into diethyl ether. The resulting white fibrous solids are filtered and dried under vacuum (average yield 67%). 

Thiol protection, 59, 190 Thiono esters, reaction with ethyl isocyanoacetate, 59,187 Thionyl chloride, 55, 27 Thiophenol, 55, 122 58, 144 Thorium dodecanedioate, 56,110 Toluene, 56, 86 58,125 p-Toluenesulfonates, reaction with organo-cuprates, 55,112 p-Toluenesulfonic acid, 58, 57, 63 p-Toluenesulfonic acid, monohydrate, 56,44... 

R)-(-)-Methyl 3-hydroxybutanoate Butyric acid, 3-hydroxy-, methyl ester, D-(-)- (8) Butanoic acid, 3-hydroxy-, methyl ester, (R)- (9) (3976-69-0) p-Toluenesulfonic acid monohydrate (8) Benzenesulfonic acid, 4-methyl-, monohydrate (9) (6192-52-5)... 

Treatment of the 2,5-dihydro-l,2,5-thiadiazole 1,1-dioxide 69 with/>-toluenesulfonic acid monohydrate affords the ring-opened phenylethyl sulfamide 70 (Equation 9) <2004BMC6249>. 

Cycloalkanones were reacted with diethyl aminomethylenemalonate (13) in boiling toluene or xylene in the presence of dichloroacetic acid or p-toluenesulfonic acid monohydrate under nitrogen or argon for 2.5-7 days, and under a water separator, to give N-( 1 -cycloalkenyDaminomethy-lenemalonates (275, R = R1 = —(CH,)n—, n = 6-10) (88EUP270494). 

Anilines, bis(2-amino-4-chlorophenyl)disulfide, naphthylamine, 2- and 3-aminopyridines, 2-aminopyrimidines, 2-, 3-, 5-, 6-, 7-, and 8-aminoquino-lines, 6-aminocoumarin, and 2-aminopyrazine were reacted in the absence or presence of a solvent (ethanol, toluene) with ethyl orthoformate and isopropylidene or 4-heptylidene malonates to give alkylidene (het)aryl-aminomethylenemalonates (442, R = R2 = Me, Pr) in 32-100% yields [69BRP1147759 75USP3907798 88JAP(K)239269]. p-Toluenesulfonic acid monohydrate was sometimes applied as catayst. 

In the reaction of A-methylaniline, ethyl orthoformate, and Meldrum s acid (421) in the presence of p-toluenesulfonic acid monohydrate at 100°C for 2 hr, then for 3 days at ambient temperature, (jV-methyl-TV-phenylamino)methylenemalonate (443) was obtained in 41% yield (69BRP1147759). 

H) [a]D -64.1° (CHCI3), c 1.0). The optical purity of this adduct was 95% as determined by 200 MHz 1H NMR spectroscopy and GC analysis (capillary column PEG, 0.25 mm x 25 m, purchased from Gaskuro Kogyo Company, Ltd. in Japan) after conversion to the corresponding chiral acetal as follows A solution of the adduct, (2R,4R)-(-)-pentanediol (1.2 equiv, obtained from Wako Pure Chemical Industries), triethyl orthoformate (1.2 equiv), and p-toluenesulfonic acid monohydrate (as a 5 mM solution) in dry benzene is stirred at ambient temperature for 3 hr. The mixture is poured into saturated sodium bicarbonate and the product is extracted with ether. The... 

Benzyl alcohol (8) Benzenemethanol (9) (100-51-6) p-Toluenesulfonic acid monohydrate (8) Benzenesulfonic acid,... 

A continuous procedure for the alkylation of mesitylene and anisole with supercritical propene, or propan-2-ol in supercritical carbon dioxide, with a heterogeneous polysiloxane-supported solid acid Deloxan catalyst has been reported giving 100% selectivity for monoalkylation of mesitylene with 50% conversion at 250 °C and 150 bar by propan-2-ol in supercritical carbon dioxide. p-Toluenesulfonic acid monohydrate has been demonstrated as an efficient catalyst for the clean alkylation of aromatics using activated alkyl halides, alkenes or tosylates under mild conditions. Cyclohexene, for example, reacts with toluene to give 100% cyclohexyltoluenes (o m p-29 18 53) under these circumstances. 

METHOD 2. A mixture of 170 g of piperidine, 220 g of cyclohexylamine, and 750 ml of benzene is azeotropically distilled until the evolution of H2O stops, then vacuum distill to get cyclohexenyl-piperidine. p-toluenesulfonic acid monohydrate (190 g) in 250 ml of PhMe is heated under a water trap until all the H2O is removed, then add a solution of 165 g of cyclohexyl-piperidine in 500 ml of Et20, with cooling, to keep temp at 0°. A solution of 1 mole of PlMgBr (made from 157 g of PhBr and 24 g of Mg) in 750 ml of Et20 is added (still holding the temp at 0° to 5°). The mixture is stirred for an additional 30 min... 

Catalysts were "Fascat 4100 a soluble tin catalyst supplied by M T Chemical said to be 95% HgC Sn(0)0H and p-toluenesulfonic acid monohydrate (p-TSA, Lancaster). 

The cyanohydrin initially formed is unstable and readily reconverted to the starting 6-methoxy-l-tetralone on evaporation of the extracts unless slight acidity of the solution is maintained by addition of a trace amount of p-toluenesulfonic acid monohydrate. As this acid is relatively insoluble in methylene chloride, it should be added directly to the flask used for evaporation of the solvent. 

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