Magnesium pyridine

Dichlorobutane. Place 22-5g. of redistilled 1 4-butanediol and 3 ml. of dry pyridine in a 500 ml. three necked flask fitted with a reflux condenser, mechanical stirrer and thermometer. Immerse the flask in an ice bath. Add 116 g. (71 ml.) of redistilled thionyl chloride dropwise fix>m a dropping funnel (inserted into the top of the condenser) to the vigorously stirred mixture at such a rate that the temperature remains at 5-10°. When the addition is complete, remove the ice bath, keep the mixture overnight, and then reflux for 3 hours. Cool, add ice water cautiously and extract with ether. Wash the ethereal extract successively with 10 per cent sodium bicarbonate solution and water, dry with anhydrous magnesium sulphate and distil. Collect the 1 4-dichloro-butane at 55-5-56-5°/14 mm. the yield is 35 g. The b.p. under atmospheric pressure is 154 155°. 

Dissolve 57 g. of dry malonic acid in 92 5 ml. of dry P3rridine contained in a 500 ml. round-bottomed flask, cool the solution in ice, and add 57 g. (70 ml.) of freshly distilled n-heptaldehyde (oenanthol) with stirring or vigorous shaking. After a part of the aldehyde has been added, the mixture rapidly seta to a mass of crystals. Insert a cotton wool (or calcium chloride) tube into the mouth of the flask and allow the mixture to stand at room temperature for 60 hours with frequent shaking. Finally, warm the mixture on a water bath until the evolution of carbon dioxide ceases (about 8 hours) and then pour into an equal volume of water. Separate the oily layer and shake it with 150 ml. of 25 per cent hydrochloric acid to remove pyridine. Dissolve the product in benzene, wash with water, dry with anhydrous magnesium sulphate, and distil under reduced pressure. Collect the ap-nonenoic acid at 130-13272 mm. The yield is 62 g. 

Tetrahydrofurfuryl chloride. Place 204 g. (194 ml.) of freshly distilled tetrahydrofurfuryl alcohol (b.p. 177°) and 174 g. (178 ml.) of dry pyridine in a 1-litre three-necked flask, fitted with a dropping funnel, mechanical stirrer and thermometer. Cool in an ice bath, stir vigorously and add 250 g. (153 ml.) of freshly distilled thionyl chloride at the rate of 3-5 drops per second. A pasty crystalline mass begins to separate and the temperar ture commences to rise rapidly when one-third to one-half of the thionyl chloride has been added subsequently the mass largely redissolves and a dark brown liquid forms. Remove the ice bath when the addition is complete and stir the mixture for 3-4 hours. Pour the reaction product into a large separatory funnel and extract with seven 250 ml. portions of ether break up any lumps that may form with a glass rod. Remove the ether from the combined extracts by distillation, wash the residue with three 50 ml. portions of water, dry with anhydrous magnesium sulphate and distil under reduced pressure. The yield of tetrahydrofurfuryl chloride, b.p. 47-48°/15 mm., is 180 g. 

Iodine Acetaldehyde, acetylene, aluminum, ammonia (aqueous or anhydrous), antimony, bromine pentafluoride, carbides, cesium oxide, chlorine, ethanol, fluorine, formamide, lithium, magnesium, phosphorus, pyridine, silver azide, sulfur trioxide... 

Soum and Fontanillet prepared a living polymer of 2-vin yl pyridine using benzyl picolyl magnesium as the initiator. The values of were measured experimentally for polymers prepared with different concentrations of initiator and different initial concentrations of monomer. The results are given below calculate the theoretical molecular weights expected if polymerization proceeds completely from 100% predissociated initiator and compare the theoretical and experimental values ... 

Medroxyprogesterone acetate (74) is stmcturaHy related to and has been prepared from hydroxyprogesterone (39) (Fig. 10). Formation of the bis-ketal accomplishes the protection of the ketones and the required migration of the double bond. Epoxidation with peracetic acid produces a mixture of epoxides (75), with a predominating. Treatment of the a-epoxide with methyl magnesium bromide results in diaxial opening of the epoxide. Deprotection of the ketones provides (76), which is dehydrated to (77) by treatment with dilute sodium hydroxide in pyridine. Upon treatment with gaseous hydrochloric... 

Phenols. Phenols are unreactive toward chloroformates at room temperature and at elevated temperatures the yields of carbonates are relatively poor (< 10%) in the absence of catalysis. Many catalysts have been claimed in the patent Hterature that lead to high yields of carbonates from phenol and chloroformates. The use of catalyst is even more essential in the reaction of phenols and aryl chloroformates. Among the catalysts claimed are amphoteric metals or thek haUdes (16), magnesium haUdes (17), magnesium or manganese (18), secondary or tertiary amines such as imidazole (19), pyridine, quinoline, picoline (20—22), heterocycHc basic compounds (23) and carbonamides, thiocarbonamides, phosphoroamides, and sulfonamides (24). 

Production of cellulose esters from aromatic acids has not been commercialized because of unfavorable economics. These esters are usually prepared from highly reactive regenerated cellulose, and their physical properties do not differ markedly from cellulose esters prepared from the more readily available aHphatic acids. Benzoate esters have been prepared from regenerated cellulose with benzoyl chloride in pyridine—nitrobenzene (27) or benzene (28). These benzoate esters are soluble in common organic solvents such as acetone or chloroform. Benzoate esters, as well as the nitrochloro-, and methoxy-substituted benzoates, have been prepared from cellulose with the appropriate aromatic acid and chloroacetic anhydride as the impelling agent and magnesium perchlorate as the catalyst (29). 

P-o 3-ketal in 130 ml of glacial acetic acid and 130 ml of water is maintained at 80° for 30 min, poured onto ice, made alkaline with sodium hydroxide and extracted with methylene dichlofide. The extracts are washed once with water, dried over magnesium sulfate, filtered, and evaporated to a residue. A solution of this residue in 240 ml of pyridine and 120 ml of acetic anhydride is kept at room temperature for 1.25 hr and then poured into hydrochloric acid-ice water. The mixture is extracted with methylene dichloride and the methylene dichloride solution is washed until neutral, dried over magnesium sulfate and filtered. The filtrate is evaporated to dryness to yield 13 g. Crystallization from aqueous acetone yields 11.8 g (92%) mp 251-255° [ ]d —1° (dioxane). 

A-Homo-estra- Q>),2,Aa-triene-4, l-dione (45) from the l-ketal mono-dibromocarbene adduct (43b). A solution of monoadduct 17-ketal (43b 0.46 g) and dry pyridine (20 ml) is heated at reflux for 2 hr. After cooling the reaction mixture, the pyridine hydrobromide (0.1 g) is removed by filtration and the filtrate is concentrated under reduced pressure. The resultant gum is dissolved in ether and washed successively with water, ice-cold 4 N hydrochloric acid, water, 5% aqueous sodium bicarbonate solution, water, saturated salt solution and dried over anhydrous magnesium sulfate. Evaporation of the solvent at reduced pressure gives 3-bromo-4-methoxy-A-homo-estra-2,4,5(10)-trien-17-one (44 0.22 g) mp 158-162° after crystallization from ether. 

To a mixture of naphthyloxazoline 71 (4.31 g, 12.97 mmol) in pyridine (4 mL) was added activated copper (1.99 g). The mixture was heated to reflux for 24 h then was cooled to rt, diluted with CH2CI2 and washed with aqueous ammonia until the copper had been completely removed. The organic phase was washed with water then dried over anhydrous magnesium sulfate, filtered, and concentrated to afford the title compound as a tan solid. This material was used without further purification. 

Indolylmethyl)pyridine (106), 3 - (3 -indolylraethyl)pyridine (107), and 4-(3-indolylmethyl)pyridino (108) have recently beer prepared by the condensation of indole magnesium bromide with 2-3-, and 4-chloromethylpyridine, respectively. ... 

The importance of metal catalysis is suggested by the fact that exclusive 4-substitution of pyridine with alkyllithiums or alkyl-magnesium halides occurs when free metal is present exclusive 2-substitution otherwise occurs. 

Tliis iodine-magnesium exdiange can also be perfotnied widi beterocydic iodides, sudi as die functionalized pyridine 16 [21] ot die iodoutactl derivative 17 iSdieme 2.5) [22], In botli cases, tlie interniediate otganomagnesium reagent can... 

By oxidation with chromic acid, this is converted into cyclohexanone-3-carboxylic acid, in which the —CH. OH— group is converted into the —CO— group. This is converted into its ethyl ester and treated with magnesium methyl iodide, and the product, on hydrolysis, yields l-methyl-cyclohexane-l-ol-3-carboxylic acid, which is converted byhydro-bromic acid into 1-bromo-l - methyl - cyclohexane - 3 - carboxylic acid. When this is digested with pyridine, hydrobromic acid is eliminated and yields l-methyl-A -cyclohexane-3-carboxylic acid of the formula—... 

To a solution of 10 g of 2-N-methyl-aminoacetamido-3-o-chlorobenzoyl-5-ethylthiophene in 50 ml of pyridine are added 20 ml of benzene and 1.9 g of acetic acid. The resulting mixture is refluxed with stirring for 10 hours in a flask provided with a water-removing adaptor. The reaction mixture is concentrated, and the residue is extracted with chloroform. The chloroform layer is washed with water and then with a sodium hydrogen carbonate solution, then dried over magnesium sulfate. The chloroform is distilled off under reduced pressure, and toluene is added to the residue. Thus is precipitated white crystalline-5-o-chloropheny -7-ethyl-1 -methyi-1,2-dihydro-3H-thieno-[2,3-e] [ 1,4] diazepin-2-one, MP 105°C to 106°C. 

Preparation of 3-(N-Formyl-N-Methyl)-Aminopropyl Chloride 50 grams of 3-(N-formyl-N-methyl)-aminopropanol-1 obtained above is dissolved in a mixture of 100 ml of chloroform and 25 grams of pyridine. 40 grams of thionyl chloride is then slowly added while maintaining the temperature below 65°C. After 6 hours of refluxing, the mixture is washed with water, then with sodium bicarbonate solution and again with water and then dried over magnesium sulfate and the solvent distilled off in vacuo. Fractional distillation at 1 mm pressure yields substantially pure 3-(N-formyl-N-methyl)-aminopropyl chloride. 

The organic layer wasdried with anhydrous magnesium sulfate and then filtered. The solution was concentrated under vacuum at 30°C to 35°C until reduced to half of its original volume and then cooled to 5°C to allow the crystallization of the compound. Thus, the cake was filtered, washed with cool ethyl acetate, and dried under vacuum. Yield 74% (76.7 g) of phthalidyl ester of 2-(3 -trifluoromethylanilino)-pyridin-3-carboxylic acid, melting point 165°C to 167°C. 

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