ALONIC ACID

Figure 6 The change in TCE concentration vs. dose using A electron beam alone - 7-irradiation alone acid, ozone-electron beam and O ozone-7-irradiation. Note the departure from first-order behavior using the e-beam. 

CjHgO. M.p. 45—46 "C, b.p. ISS C. It occurs free in the roots of Angelica archangelica. When heated alone or with acids or alkalis it is converted to tigiic acid. (Z)-isomer. 

C2He04S, Et0)(H0)S02. Oily acidic liquid. Soluble in water and slowly hydrolysed by it to ethanol and sulphuric acid. Prepared by passing ethene into concentrated sulphuric acid or by heating ethanol and sulphuric acid. Gives ethene when heated alone, and diethyl sulphate when heated with ethanol at 140 C. Forms crystalline metallic salts which are soluble in water. 

Only chloric(III) acid, HCIO2, is definitely known to exist. It is formed as one of the products of the reaction of water with chlorine dioxide (see above). Its salts, for example NaClOj, are formed together with chlorates)V) by the action of chlorine dioxide on alkalis. Sodium chlorate(III) alone may be obtained by mixing aqueous solutions of sodium peroxide and chlorine dioxide ... 

The purple colour of this ion alone is a sufficient test for its presence addition of sulphuric acid and hydrogen peroxide discharges ihe colour. 

Porschke, D., Eigen, M. Cooperative nonenzymic base recognition. HI. Kinetics of the helix-coil transition of the oligoribouridylic oligoriboadenylic acid system and of oligoriboadenylic acid alone at acidic pH. J. Mol. Biol. 62 (1971) 361-381... 

Hydrolysis of Benzamide. When acid amides are hydrolysed, the corresponding acid and ammonia are formed. Consequently the hydrolysis, which is extremely slow with water alone, is hastened con-... 

It is found experimentally, however, that if benzene is treated with concen trated nitric acid alone, the yield of nitrobenzene is small. If, however, the nitric acid is first mixed with concentrated sulphuric acid, a high yield of nitrobenzene results. 

It is now applied more widely to include malonic acid derivatives, such as diethyl monoethyl-malonate, ethyl cyanacetate, etc. Various amines may be used as catalysts, and usually the most effective is piperidine (hexahydro-pyridine) a mixture of piperidine and pyridine, or pyridine alone, is also often used. 

As a general guide, however, it may be noted that the following have fairly easily recognisable odours methyl and ethyl formate methyl and ethyl acetate (apples) methyl and ethyl benzoate methyl salicylate (oil of winter-green) and ethyl salicylate methyl and ethyl cinnamate. (It is however usually impracticable to distinguish by odour alone between the methyl and ethyl esters of a particular acid.) Methyl and ethyl o. alate, and methyl and ethyl phthalate are almost odourless. Succinic and tartaric esters have faint odours. 

Benzene. Pure benzene (free in particular from toluene) must be used, otherwise the freezing-point is too low, and crystallisation may not occur with ice-water cooling alone. On the other hand, this benzene should not be specially dried immediately before use, as it then becomes slightly hygroscopic and does not give a steady freezing-point until it has been exposed to the air for 2-3 hours. Many compounds (particularly the carboxylic acids) associate in benzene, and molecular weights determined in this solvent should therefore be otherwise confirmed. 

II This dual tilling permits the absorption of both acid smd basic vapours which may be evolved. Thus an amine hydrochloride, which has been recrystallised from concentrated hydrochloric acid, may be readily dried in such a desiccator. If concentrated sulphuric acid alone were used, so much hydrogen chloride would be liberated that tlie pressure inside the desiccator would rise considerably, smd the rate of drying would be reduced. With sodium hydroxide present, however, the hydrogen chloride is removed, smd tho water is absorbed in the normal manner by the reagents but largely by the acid. 

Acetaldehyde (and other aldehydes containing at least one hydrogen atom in the a position) when treated with a small quantity of dilute sodium hydr oxide solution or other basic catalyst gives a good yield of aldol (p hydroxy-n-but3Taldehyde) (I), which readily loses water, either by heating the isolated aldol alone or with a trace of mineral acid, to form crotonaldehyde (II) ... 

Reaction with chlorosulphonic acid ( chlorosulphonyl-ation ). Sulphonamides. Many aryl hahdes, either alone or in chloroform solution, when treated with excess of chlorosulphonic acid afford the corresponding sulphonyl chlorides in good yield (compare Section IV.106) the latter may be readily converted into the aryl sulphonamides by reaction with concentrated ammonia solution or with sohd ammonium carbonate. 

The following give abnormal results when treated with chlorosulphonio acid alone, preferably at 50° for 30-60 minutes —fluobenzene (4 4 -difluorodiplienyl-sulphone, m.p. 98°) j iodobenzene (4 4 -di-iododiphenylsulplione, m.p. 202°) o-diclilorobenzene (3 4 3. -4 -tetrachlorodiphenylsulphone, m.p. 176°) and o-dibromobenzene (3 4 3 4 -tetrabromodiphenylsulphone, m.p. 176-177°). The resulting sulphones may be crystallised from glacial acetic acid, benzene or alcohol, and are satisfactory for identification of the original aryl halide. In some cases sulphones accompany the sulphonyl chloride they are readily separated from the final sulphonamide by their insolubility in cold 6N sodium hydroxide solution the sulphonamides dissolve readily and are reprecipitated by 6iV hydrochloric acid. 

The disadvantages attending the use of acetic anhydride alone are absent when the acetylation is conducted in aqueous solution according to the following procedure. The amine is dissolved in water containing one equivalent of hydrochloric acid, slightly more than one equivalent of acetic anhydride is added to the solution, followed by enough sodium acetate to neutralise the hydrochloric acid, and the mixture is shaken. The free amine which is liberated is at once acetylated. It must be pointed out that the hydrolysis of acetic anhydride at room temperature is extremely slow and that the free amine reacts much more readily with the anhydride than does the water this forms the experimental basis for the above excellent method of acetylation. 

By dropping au aromatic acid either alone or mixed with an aliphatic acid into a tube containing a thoria catalyst deposited on pumice and heated to 400-450°. This method is generally employed for the preparation of mixed aromatic - aliphatic ketones. Excess of the aUphatic acid is usually present since this leads to by-products which are easily separated and also tends to increase the yield of the desired ketone at the expense of the symmetrical ketone of the aromatic acid. Thus —... 

Quinoline may be prepared by heating a mixture of aniline, anhydrous glycerol and concentrated sulphuric acid with an oxidising agent, such as nitrobenzene. The reaction with nitrobenzene alone may proceed with extreme violence, but by the addition of ferrous sulphate, which appears to function as an oxygen carrier, the reaction is extended over a longer period of time and Is under complete control. 

The solid appears to be a mixture of the complexes CH,COOH.BF, and 2CH COOH.BF,. The latter appears to be a liquid and is alone soluble in ethylene dichloride the former is a solid. The solid moiioocetic acid complex is obtained by saturating an ethylene dichloride solution of acetic acid with boron trifluoride, filtering and washing the precipitate with the solvent it is hygroscopic and should be protected from moisture. It may be used as required 0-75 mol is employed with 0-26 mol of ketone and 0 6 mol of anhydride. 

The action of sulphuric acid alone upon acetone cyanohydrin affords a-methylacrylic acid. The methyl methacrylate polymers are the nearest approach to an organic glass so far developed, and are marketed as Perspex (sheet or rod) or Dialcon (powder) in Great Britain and as Plexiglass and Luciie in the U.S.A. They are readily depolymerised to the monomers upon distillation. The constitution of methyl methacrylate polymer has been given as ... 

The observation of nitration at a rate independent of the concentration and the nature of the aromatic means only that the effective nitrating species is formed slowly in a step which does not involve the aromatic. The fact that the rates of zeroth-order nitration under comparable conditions in solutions of nitric acid in acetic acid, sulpholan and nitromethane differed by at most a factor of 50 indicated that the slow step in these three cases was the same, and that the solvents had no chemical involvement in this step. The dissimilarity in the rate between these three cases and nitration with acetyl nitrate in acetic anhydride argues against a common mechanism, and indeed it is not required from evidence about zeroth-order rates alone that in the latter solutions the slow step should involve the formation of the nitronium ion. 

Thus, strong arguments against all of the obvious nitrating species acting alone can be found. However, as has been pointed out, the extent to which ions require solvation by nitric acid molecules in this medium is unknown, and such solvation would influence the apparent order with respect to the stoichiometric nitric acid. The possibility also exists that more than one mechanism of nitration, excluding nitrosation, is operative. 

Little is known quantitatively about substituent effects in the nitration of derivatives of azanaphthalenes. In preparative experiments 4-hydroxy-quinoline, -cinnoline, and -quinazoline give the 6- and 8-nitro compounds, but with nitric acid alone 4-hydroxyquinoline and 2,4-di-hydroxyquinoline react at With nitric acid, 4-hydroxycinnoline... 

As regards the nitration of these compounds in nitric acid alone,... 

The isocoumarin 151 is prepared by the intramolecular reaction of 2-(2-propenyDbenzoic acid (149) with one equivalent of PdCbjMeCN) . However, the (Z)-phthalide 150 is obtained from the same acid with a catalytic amount of PdjOAc) under 1 atm of Oi in DMSO, alone is remarkably efficient in reoxidizing Pd(0) in DMSO. The isocoumarin 151 is obtained by the reaction of 2-(l-propenyl)benzoic acid (152) under the same conditions[4], 2-Vinylbenzoic acid (153) is also converted into the isocoumarin 154, but not to the five-membered lactone) 167,170],... 

Carboxylic acids react with butadiene as alkali metal carboxylates. A mixture of isomeric 1- and 3-acetoxyoctadienes (39 and 40) is formed by the reaction of acetic acid[13]. The reaction is very slow in acetic acid alone. It is accelerated by forming acetate by the addition of a base[40]. Addition of an equal amount of triethylamine achieved complete conversion at 80 C after 2 h. AcONa or AcOK also can be used as a base. Trimethylolpropane phosphite (TMPP) completely eliminates the formation of 1,3,7-octatriene, and the acetoxyocta-dienes 39 and 40 are obtained in 81% and 9% yields by using N.N.N M -tetramethyl-l,3-diaminobutane at 50 in a 2 h reaction. These two isomers undergo Pd-catalyzed allylic rearrangement with each other. 

The alkyl derivatives of thiazoles can be catalytically oxidized in the vapor phase at 250 to 400°C to afford the corresponding formyl derivatives (21). Molybdenum oxide, V2O5, and tin vanadate are used as catalysts either alone or with a support. The resulting carbonyl compounds can be selectively oxidized to the acids. 

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