Sodium hydride acetate

Glycerol Acetic anhydride, hypochlorites, chromium(VI) oxide, perchlorates, alkali peroxides, sodium hydride... 

Similarly, hydantoins can be arylated at N-3. For example, treatment of 5,5-diphenyIhydantoin (4), R = R = Cg (phenytoin), with -tolyUead triacetate in the presence of sodium hydride and a catalytic amount of copper(II) acetate (37) gives compound (7). 

The final variation of the Feist-Benary furan synthesis encompasses reactions of 1,3-dicarbonyls with 1,2-dibromoethyl acetate (52). For example, treatment of ethyl acetoacetate (9) with sodium hydride followed by addition of 52 at 50°C yields dihydrofuran 53. The product can be easily converted into the corresponding 2-methyl-3-furoate upon acid catalyzed elimination of the acetate, thus providing another strategy for the synthesis of 2,3-disubstituted furans. 

Low yields of 5-acyl-2,3-dihydropyrrolo[2,l-Z ]oxazoles (37) were obtained by treatment of 2-acyl-5-nitropyrrole (35) with ethylene oxide. Better yields are reported starting from hydroxy derivative 36a or its acetate 36b using sodium hydride in THE The presence of an acyl group at the position 2 was found necessary for the cyclization (Scheme 5) (71JCS(C)2554). 

In a similar scheme, acylation of 2-methoxynaphthalene gives ketone, 15. This is then converted to the acetic acid by the Wilgerodt reaction. Esterification, alkylation of the carbanion (sodium hydride methyl iodide), and finally saponification affords naproxen (17). The intense current effort on nonsteroid antiinflammatory agents and acrylacetic acids in particular make... 

Carbethoxycyclooctanone (40 g, 0.2 mole) dissolved in 50 ml of dry benzene is added to the stirred sodium hydride over about 30 minutes at room temperature. The mixture is stirred an additional hour at room temperature to complete the formation of the sodium salt. Methyl iodide (284 g, 2.0 mole, a 10-fold excess) is added to the stirred solution over 1 hour and the stirring at room temperature is continued for 20-24 hours. The reaction mixture is poured cautiously into 500 ml of 3 aqueous acetic acid, and the aqueous solution is extracted three times with 100-ml portions of benzene. The combined benzene extracts are washed three times with water and dried over anhydrous magnesium sulfate. Benzene and excess methyl iodide are removed under reduced pressure (rotary evaporator) and the residue is distilled. 

Benzhydryl 3Sodium hydride, 24 mg (4B mg of a 50% suspension of NaH in mineral oil, which has been washed with hexane to remove the oil), is added. When hydrogen evolution has ceased, 126 mg dimethyl sulfate is added. The solution is stirred for one hour at room temperature,diluted with 100 ml benzene and washed six times with water the last wash is made to pH B, if necessary, by adding sodium bicarbonate. The solution is dried over MgS04, filtered and evaporated, leaving benzhydryl 3eluting with 25 1 chloroform-ethyl acetate. 

Methyl-5-methoxy-3-mdolyl acetic acid Sodium hydride... 

Pyrrolidone is first reacted with sodium hydride, then with ethyl chloroacetate to give ethyl 2-OXO-1 -pyrrolidine acetate. 

A suspension of 30 g of sodium hydride in benzene (30 ml) was added dropwise to 52 g of 8-chlorodibenzo[b,f] thiepin-10(11 H)-one dissolved in dimethylformamide (800 ml), and the mixture was heated at 100°C for 2 hours. To this, there were added 68 g of 2-dimethylamino-ethyl chloride, and the mixture was heated at 60°C for 39 hours. The reaction mixture, after cooled, was poured into ice-water, and the solution was extracted with ethyl acetate. The ethyl acetate layer, after washed with water, was extracted with 10% hydrochloric acid, when oil was precipitated. The aqueous layer, in which oil was precipitated, was washed with ether, made neutral with concentrated sodium hydroxide solution and then extracted with ethyl acetate. The ethyl acetate layer was washed with water, dried over magnesium sulfate, and concentrated to give oil, which was allowed to stand to provide solid. The solid was washed with petroleum ether and recrystallized from cyclohexane to yield 42.5 g of 8melting point 90°C to 91°C. Male-ate as colorless needle, melting point 204°C to 204.5°C. 

Notable examples of general synthetic procedures in Volume 47 include the synthesis of aromatic aldehydes (from dichloro-methyl methyl ether), aliphatic aldehydes (from alkyl halides and trimethylamine oxide and by oxidation of alcohols using dimethyl sulfoxide, dicyclohexylcarbodiimide, and pyridinum trifluoro-acetate the latter method is particularly useful since the conditions are so mild), carbethoxycycloalkanones (from sodium hydride, diethyl carbonate, and the cycloalkanone), m-dialkylbenzenes (from the />-isomer by isomerization with hydrogen fluoride and boron trifluoride), and the deamination of amines (by conversion to the nitrosoamide and thermolysis to the ester). Other general methods are represented by the synthesis of 1 J-difluoroolefins (from sodium chlorodifluoroacetate, triphenyl phosphine, and an aldehyde or ketone), the nitration of aromatic rings (with ni-tronium tetrafluoroborate), the reductive methylation of aromatic nitro compounds (with formaldehyde and hydrogen), the synthesis of dialkyl ketones (from carboxylic acids and iron powder), and the preparation of 1-substituted cyclopropanols (from the condensation of a 1,3-dichloro-2-propanol derivative and ethyl-... 

We now tum our attention to the C21-C28 fragment 158. Our retrosynthetic analysis of 158 (see Scheme 42) identifies an expedient synthetic pathway that features the union of two chiral pool derived building blocks (161+162) through an Evans asymmetric aldol reaction. Aldehyde 162, the projected electrophile for the aldol reaction, can be crafted in enantiomerically pure form from commercially available 1,3,4,6-di-O-benzylidene-D-mannitol (183) (see Scheme 45). As anticipated, the two free hydroxyls in the latter substance are methylated smoothly upon exposure to several equivalents each of sodium hydride and methyl iodide. Tetraol 184 can then be revealed after hydrogenolysis of both benzylidene acetals. With four free hydroxyl groups, compound 184 could conceivably present differentiation problems nevertheless, it is possible to selectively protect the two primary hydroxyl groups in 184 in... 

Singlet oxygen [Oxygen, singlet], 51 Sodium acetate [Acetic acid, sodium salt], 33,49,66 Sodium azide, 109 Sodium hydride, 20 Sodium thiosulfate (Thiosulfuric acid (HjSj03), disodium salt], 120 Squalene [2,6,10,14,18,22 Tetracosa-... 

Reaction of 1,3-dicarbonyl compounds with IVJV-dimethylformamide dimethyl acetal followed by malonamide in the presence of sodium hydride gives 5,6-disubstituted 1,2-dihydro-2-oxopyridine-3-carboxamides, whereas reaction of the intermediate enamines with cyanothioacetamide or cyanoacetamide in the presence of piperidine provides 2-thioxopyridine-3-carboxamides and 4,5-disubstituted l,2-dihydro-2-oxopyridine-3-carboxamides, respectively <95S923>. P-Enaminonitriles 14 react with p-ketoesters and alkyl malonates, in the presence of stoichiometric amounts of tin(IV) chloride, to afford 4-aminopyiidines 15 and 4-amino-2-pyridones 16 <95T(51)12277>. 

Nalliah et al. (202,203) developed a novel entry to protopine alkaloids from a protoberberine. 13-Oxotetrahydroberberine (ophiocarpinone) metho salt (291) was reduced with zinc in 30% acetic acid to afford a new type of the protopine analog 401 (Scheme 74) (202). On the other hand, 291 gave 13-oxoallocryptopine (402) via the hydroperoxide on exposure to air in the presence of sodium hydride and potassium iodide in dimethoxyethane (203). 

Thiadiazole 50b was also acylated when treated with acetic acid in the presence of sodium hydride to give the thiadiazole 96 (Equation 26) <2004ZNB366>. 

Ethyl sulfate Flammable liquids Fluorine Formamide Freon 113 Glycerol Oxidizing materials, water Ammonium nitrate, chromic acid, the halogens, hydrogen peroxide, nitric acid Isolate from everything only lead and nickel resist prolonged attack Iodine, pyridine, sulfur trioxide Aluminum, barium, lithium, samarium, NaK alloy, titanium Acetic anhydride, hypochlorites, chromium(VI) oxide, perchlorates, alkali peroxides, sodium hydride... 

The key step in Hu s synthesis of 51 was cyclization of 50 by heating with copper(I) iodide and sodium hydride in DME, followed by a 10% aqueous ammonia work-up. Intermediate 50 was prepared via Michael addition of ethyl acetamidocyano acetate to the appropriate chalcone followed by acid-catalyzed ring closure [42,43]. 

Sodium Hydride-Sodium (-amyl oride-Nickel acetate... 

Sodium hydride-Sodium r-amyl oxide-Nickel acetate (NiCRA, 10, 365)... 

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