Ethanol reaction with

The A -oxide reactions in quinazoline 3-oxide are, however, modified to a certain extent by the aforementioned properties. Thus, whereas it can be reduced to quinazoline with phosphorus trichloride or iron and ferrous sulfate in ethanol, reactions with alkali, acetic anhydride, and benzoyl chloride in the presence of cyanide result in ring fission (Scheme 4). 

Air (NB) Collection in ethanol reaction with concentrated HCl and zinc dust react with sodium salt of 1,2-naphtho-quinone-4 sulfonic acid at pH 8.0 extraction with CCl concentration separation by paper chromatography extraction of fractions with CCl ... 

A variation of the malonic ester synthetic uses a P-keto ester such as 116. In Section 22.7.1, the Claisen condensation generated P-keto esters via acyl substitution that employed ester enolate anions. When 116 is converted to the enolate anion with NaOEt in ethanol, reaction with benzyl bromide gives the alkylation product 117. When 117 is saponified, the product is P-keto acid 118, and decarboxylation via heating leads to 4-phenyl-2-butanone, 119. This reaction sequence converts a P-keto ester, available from the ester precursors, to a substituted ketone in what is known as the acetoacetic acid synthesis. Both the malonic ester synthesis and the acetoacetic acid synthesis employ enolate alkylation reactions to build larger molecules from smaller ones, and they are quite useful in synthesis. 

Hydroxy- and 4-ethoxy-3,4-dihydro-3-phenyl-2(lH)-quinazolinones as well as their thione analogs exhibit pseudobasic properties and may easily be condensed with 0-, N-, and C-nucleophiles (CH acids) by elimination of water or ethanol. Reactions with 0-, N-, and doubly activated C-nucleophiles (e. g. acetylacetone) may be effected by simply heating the components, while with the less reactive C-nucleophiles (monoketones) HCl must be used as catalyst. - E 4-Ethoxy-3,4-dihydro-3-phenylquinazolin-2(lH)-one dissolved in refluxing acetone, treated with a little coned. HCl, and refluxing continued 1 hr. 4-acetonyl-3,4-dihydro-3-phenylquinazolin-2(lH)-one. Y 71%. F.e. s. K. Lempert and P. Gyulai, Tetrahedron 26, 3443 (1970). 

The Mannich Reaction involves the condensation of formaldehyde with ammonia or a primary or secondary amine and with a third compound containing a reactive methylene group these compounds are most frequently those in which the methylene group is activated by a neighbouring keto group. Thus when acetophenone is boiled in ethanolic solution with paraformaldehyde and dimethylamine hydrochloride, condensation occurs readily with the formation of... 

The success of the Bart reaction when applied to nuclear- substituted anilines is often much affected by the pH of the reaction-mixture. Furthermore, the yields obtained from some m-substituted anilines, which under the normal conditions are usually low, arc considerably increased by the modifications introduced by Scheller, and by Doak, in which the diazotisation is carried out in ethanolic solution followed by reaction with arsenic trichloride in the presence of a cuprous chloride or bromide catalyst. 

The independent preparation of potassium phthabmide (from a solution of phthalimide in absolute ethanol and potassium hydroxide in 75 per cent, ethanol) may be avoided in many cases by boiling phthalimide with the halide in the presence of anhydrous potassium carbonate. The N-substituted phthalimide (I) is frequently cleav with difficulty this is often facilitated by reaction with hydrazine hydrate to give an intermediate product, which is easily decomposed by hydrochloric acid to 3deld the insoluble hydrazide of phthaUc acid (II) and the primary amine (III) ... 

In another attempt to achieve efficient coordination, we have used a strongly chelating diamine (4.43) in the Mannich reaction with 4.39 (Scheme 4.12). The reaction was performed in aqueous ethanol, producing 4.44-2HC1 in 64% yield. 

Reaction with h (1.5 mmol) [or Br2], supported salt (1.5 mmol), alkene (0.625 mmol), in 5 ml of ethanol-free CHCia at room tem-... 

When 1 2 dibromodecane was treated with potassium hydroxide m aqueous ethanol it yielded a mixture of three isomenc compounds of molecular formula CioHi9Br Each of these compounds was converted to 1 decyne on reaction with sodium amide m dimethyl sulfoxide Men tify these three compounds... 

Reactions with Alcohols, Mercaptans, and Phenols. Alcohols add readily to acetaldehyde in the presence of trace quantities of mineral acid to form acetals eg, ethanol and acetaldehyde form diethyl acetal [105-57-7] (65). Similarly, cycHc acetals are formed by reactions with glycols and other polyhydroxy compounds eg, ethylene glycol [107-21-1] and acetaldehyde give 2-methyl-1,3-dioxolane [497-26-7] (66) ... 

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). 

Trifluoromethanesulfonic acid is miscible in all proportions with water and is soluble in many polar organic solvents such as dimethylformamide, dimethyl sulfoxide, and acetonitrile. In addition, it is soluble in alcohols, ketones, ethers, and esters, but these generally are not suitably inert solvents. The acid reacts with ethyl ether to give a colorless, Hquid oxonium complex, which on further heating gives the ethyl ester and ethylene. Reaction with ethanol gives the ester, but in addition dehydration and ether formation occurs. 

Iron hahdes react with haHde salts to afford anionic haHde complexes. Because kon(III) is a hard acid, the complexes that it forms are most stable with F and decrease ki both coordination number and stabiHty with heavier haHdes. No stable F complexes are known. [FeF (H20)] is the predominant kon fluoride species ki aqueous solution. The [FeF ] ion can be prepared ki fused salts. Whereas six-coordinate [FeCy is known, four-coordinate complexes are favored for chloride. Salts of tetrahedral [FeCfy] can be isolated if large cations such as tetraphenfyarsonium or tetra alkylammonium are used. [FeBrJ is known but is thermally unstable and disproportionates to kon(II) and bromine. Complex anions of kon(II) hahdes are less common. [FeCfy] has been obtained from FeCfy by reaction with alkaH metal chlorides ki the melt or with tetraethyl ammonium chloride ki deoxygenated ethanol. 

A number of chemiluminescent reactions may proceed through unstable dioxetane intermediates (12,43). For example, the classical chemiluminescent reactions of lophine [484-47-9] (18), lucigenin [2315-97-7] (20), and transannular peroxide decomposition. Classical chemiluminescence from lophine (18), where R = CgH, is derived from its reaction with oxygen in aqueous alkaline dimethyl sulfoxide or by reaction with hydrogen peroxide and a cooxidant such as sodium hypochlorite or potassium ferricyanide (44). The hydroperoxide (19) has been isolated and independentiy emits light in basic ethanol (45). 

The speed of the reaction depends both on the metal and on the alcohol, increasing as electropositivity iacreases and decreasiag with length and branching of the chain. Thus sodium reacts strongly with ethanol, but slowly with tertiary butyl alcohol. The reaction with alkaU metals is sometimes carried out ia ether, ben2ene, or xylene. Some processes use the metal amalgam or hydride iastead of the free metal. Alkaline earth metals and aluminum are often covered with an oxide film which hinders the reaction. 

Polyphosphoric acid, P2O5, POCl, and PCl are suitable phosphorylatiag agents. Reaction of an alkyl sulfate with sodium pyrophosphate has also been reported for preparation of alkyl pyrophosphates (77). In general, phosphorylation leads to a mixture of reaction products that are sold without further separation. Thus, when lauryltri(ethyleneoxy)ethanol reacts with 0.3 mol of P2O5 at 50°C and is neutralized with 50% aqueous NaOH, the reaction mixture contains the foUowiag products ... 

Manufacture. Ethyl chloride undergoes reaction with alkah cellulose in high pressure nickel-clad autoclaves. A large excess of sodium hydroxide and ethyl chloride and high reaction temperatures (up to 140°C) are needed to drive the reaction to the desked high DS values (>2.0). In the absence of a diluent, reaction efficiencies in ethyl chloride range between 20 and 30%, the majority of the rest being consumed to ethanol and diethyl ether by-products. 

Nitrobenzotrichloride is also obtained in high yield with no significant hydrolysis when nitration with a mixture of nitric and sulfuric acids is carried out below 30°C (31). 2,4-Dihydroxybenzophenone [131 -56-6] is formed in 90% yield by the uncatalyzed reaction of benzotrichloride with resorcinol in hydroxyHc solvents (32) or in benzene containing methanol or ethanol (33). Benzophenone derivatives are formed from a variety of aromatic compounds by reaction with benzotrichloride in aqueous or alcohoHc hydrofluoric acid (34). 

Another appHcation of 4-chlorophenol is in the synthesis of a dmg, ethyl a, a-dimethyl-4-chlorophenoxy acetate [637-07-0] (60), used as a cholesterol-reducing agent. This synthesis involves reaction with acetone and chloroform, followed by ethanol esterification. 

The effect of water on the equbibrium constant for the reaction of 1 mol of ethanol, 1 mol of acetic acid, and 23 moles of water has been iavestigated. This mixture has an equbibrium constant of 3.56, compared with 3.79 for the reaction with anhydrous materials (7,37). 

Ethyl Chloride. Previously a significant use for industrial ethanol was the synthesis of ethyl chloride [75-00-3] for use as an intermediate in producing tetraethyllead, an antiknock gasoline additive. Ethanol is converted to ethyl chloride by reaction with hydrochloric acid in the presence of aluminum or zinc chlorides. However, since about 1960, routes based on the direct addition of hydrochloric acid to ethylene or ethane have become more competitive (374,375). 

In some instances a carbon-carbon bond can be formed with C-nucleophiles. For example, 3-carboxamido-6-methylpyridazine is produced from 3-iodo-6-methylpyridazine by treatment with potassium cyanide in aqueous ethanol and l,3-dimethyl-6-oxo-l,6-dihydro-pyridazine-4-carboxylic acid from 4-chloro-l,3-dimethylpyridazin-6-(lH)-one by reaction with a mixture of cuprous chloride and potassium cyanide. Chloro-substituted pyridazines react with Grignard reagents. For example, 3,4,6-trichloropyridazine reacts with f-butyl-magnesium chloride to give 4-t-butyl-3,5,6-trichloro-l,4-dihydropyridazine (120) and 4,5-di-t-butyl-3,6-dichloro-l,4-dihydropyridazine (121) and both are converted into 4-t-butyl-3,6-dichloropyridazine (122 Scheme 38). 

Reduction of indolenines with sodium and ethanol gives indolines. The pentachloropyr-role, obtained by chlorination of pyrrole with sulfuryl chloride at room temperature in anhydrous ether, was shown by spectroscopic methods to have an a-pyrrolenine (2H-pyrrole) structure (222). It is necessary, however, to postulate that it is in equilibrium with small but finite amounts of the isomeric /3-pyrrolenine form (3//-pyrrole 223), since pentachloropyrrole functions as a 2-aza- rather than as a 1-aza-butadiene in forming a cycloadduct (224) with styrene (80JOC435). Pentachloropyrrole acts as a dienophile in its reaction with cyclopentadiene via its ene moiety (81JOC3036). 

Analogous to the oxidation of hydrazones to azo compounds, A-unsubstituted pyrazolidines are oxidized to A -pyrazolines. For example, the blcyclic pyrazolidine (415) when treated with silver oxide yields the pyrazoline (416) (65JA3023). Pyrazolidine (417) is transformed into the perchlorate of the pyrazolium salt (411) by reaction with mercury(II) acetate in ethanol followed by addition of sodium perchlorate (69JOU1480). 

In all cases so far investigated, including a useful direct reaction with ketones, the methoxydienyl salt is substituted at the 5-position and not at the alternative 1-position. The Fe(CO)a group can conveniently be removed from many of these adducts by the action of ferric chloride in ethanol. ... 

Reactions with NaBH4 go smoothly in water, ethanol or 2-propanol water reacts with NaBH4 but the system can be stabilized by the addition of alkali ethanol also reacts slowly with the hydride and 2-propanol not at all ... 

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