Fischer found that the enzyme "invertase," which is present in yeast, attacks methyl-d-glucoside but not methyl-l-glucoside.
Its methyl derivatives yield the corresponding carboxylic acids when oxidized by potassium permanganate.
Many organic compounds of boron are known; thus, from the action of the trichloride on ethyl alcohol or on methyl alcohol, ethyl borate B(OC2H5)3 and methyl borate B(OCH 3) 3 are obtained.
It is formed by reducing diortho-dinitrodiphenyl with sodium amalgam and methyl alcohol, or by heating diphenylene-ortho-dihydrazine with hydrochloric acid to 150° C. It crystallizes in needles which melt at 156° C. Potassium permanganate oxidizes it to pyridazine tetracarboxylic acid.
By passing the vapour of this compound through a red-hot tube, it yields the isomeric a0- pyridylpyrrol, the potassium salt of which with methyl iodide gives a substance methylated both in the pyridine and pyrrol nuclei.
By distillation over lime, the methyl group is removed from the pyridine ring, and the resulting a- pyridyl-Nmethylpyrrol gives i-nicotine on reduction.
Anisol, phenyl methyl ether, C 6 H 5.
Pechmann, Ber., 18 9 5, 28, p. 857); by distilling anisic acid (paramethoxy benzoic acid) with baryta or by boiling phenyl diazonium chloride with methyl alcohol.
Meta-aminophenol is prepared by reducing metanitrophenol, or by heating resorcin with ammonium chloride and ammonia to 200° C. Dimethyl-meta-aminophenol is prepared by heating meta-aminophenol with methyl alcohol and hydrochloric acid in an autoclave; by sulphonation of dimethylaniline, the sulphonic acid formed being finally fused with potash; or by nitrating dimethylaniline, in the presence of sulphuric acid at 0° C. In the latter case a mixture of nitro-compounds is obtained which can be separated by the addition of sodium carbonate.
It is the methyl ester of a neutral body colchicein, which may be obtained in white acicular crystals.
7-trihydroxyxanthone, is found in the form of its methyl ether (gentisin) in gentian root; it is obtained synthetically by condensing phloroglucin with hydroquinone carboxylic acid.
Notwithstanding these errors, the value of the " ethyl theory " was perceived; other radicals - formyl, methyl, amyl, acetyl, &c. - were characterized; Dumas, in 1837, admitted the failure of the etherin theory; and, in company with Liebig, he defined organic chemistry as the " chemistry of compound radicals."
From similar investigations of valerianic acid he was led to conclude that fatty acids were oxygen compounds of the radicals hydrogen, methyl, ethyl, &c., combined with the double carbon equivalent C2.
The molecular weights were the same as in use to-day.) This connecting link, C2, was regarded as essential, while the methyl, ethyl, &c. was but a sort of appendage; but Kolbe could not clearly conceive the manner of copulation.
The existence of only one acetic acid, methyl chloride, and other monosubstitution derivatives - until the experimental proof by L.
Henry started with methyl iodide, the formula of which we write in the form CI a H b H c H d.
The same methyl iodide gave with potassium cyanide, acetonitril, which was hydrolysed to acetic acid; this must be C(Coch) a H b H c H d.
By continuing the introduction of methyl groups we obtain three series of homologous hydro carbons given by the general formulae CnH2,i 4.2, CnH2n, and CnH2n 2, each member differing from the preceding one of the same series by CH 2.
By introducing a methyl group we may obtain CH 3.
From n-butane we may derive, by a similar substitution of methyl groups, the two hydrocarbons: (I) CH 3 CH 2 CH 2 CH 2 CH 3, and (2) CH 3.
We notice that they may be differentiated as follows: (r) is built up solely of methyl and CH 2.
Moreover, while methylamine, dimethylamine, and trimethylamine increase in basicity corresponding to the introduction of successive methyl groups, phenylamine or aniline, diphenylamine, and triphenylamine are in decreasing order of basicity, the salts of diphenylamine being decomposed by water.
Kane; methylethyl ketone and methyl-n-propyl ketone suffer similar condensations to s-triethylbenzene and s-tri-n-propylbenzene respectively.
An analogous synthesis is that of dihydro-m-xylene from methyl heptenone,(CH 3) 2 C:CH (CH2)2.CO CH3.
We may here mention the synthesis of oxyuvitic ester (5-methyl-4-oxy-I-3-benzene dicarboxylic ester) by the condensation of two molecules of sodium acetoacetic ester with one of chloroform (Ann., 1883, 222, p. 249).
This compound is converted by chlorine water into octachloracetylacetone (3) by methyl alcohol into the ester of dichlormalonic acid and tetrachioracetone (4); whilst ammonia gives dichloracetamide (5) (Th.
Bamberger opposed Claus' formula on the following grounds: - The molecule of naphthalene is symmetrical, since 2.7 dioxynaphthalene is readily esterified by methyl iodide and sulphuric acid to a dimethyl ether; and no more than two mono-substitution derivatives are known.
In the second group, we may notice the application of litmus, methyl orange or phenolphthalein in alkalimetry, when the acid or alkaline character of the solution commands the colour which it exhibits; starch paste, which forms a blue compound with free iodine in iodometry; potassium chromate, which forms red silver chromate after all the hydrochloric acid is precipitated in solutions of chlorides; and in the estimation of ferric compounds by potassium bichromate, the indicator, potassium ferricyanide, is placed in drops on a porcelain plate, and the end of the reaction is shown by the absence of a blue coloration when a drop of the test solution is brought into contact with it.
In general, isomers boil at about the same temperature, as is shown by the isomeric esters CH1802: Methyl octoate..
In the aromatic compounds there is no regularity between the increments due to the introduction of methyl groups into the benzene nucleus or side chains; the normal value of 20 0 -21° is exhibited, however, by pyridine and its derivatives.
This is shown in the case of the chloracetic acids: According to van 't Hoff the substitution of chlorine atoms into a methyl group occasions the following increments: The introduction of chlorine, however, may involve a fall in the boiling-point, as is recorded by Henry in the case of the chlorinated acetonitriles: NC CH 3.
Referring to the esters C9H1802 previously mentioned, it is seen that the highest boilingpoints belong to methyl octoate and octyl formate, the least symmetrical, while the minimum belongs to amyl butyrate, the most symmetrical.
A similar depression is presented by methyl alcohol (67°) and methyl ether (-23 °) Among the aromatic di-substitution derivatives the ortho compounds have the highest boiling-point, and the meta boil at a higher, or about the same temperature as the para compounds.
158.6 calories; this means that the replacement of a hydrogen atom by a methyl group is attended by a constant increase in the heat of combustion.
The same difference attends the introduction of the methyl group into many classes of compounds, for example, the paraffins, olefines, acetylenes, aromatic hydrocarbons, alcohols, aldehydes, ketones and esters, while a slightly lower value (157.1) is found in the case of the halogen compounds, nitriles, amines, acids, ethers, sulphides and nitro compounds.
Normal values of K were given by nitrogen peroxide, N204, sulphur chloride, S 2 C1 21 silicon tetrachloride, SiC1 4, phosphorus chloride, PC1 3, phosphoryl chloride, POC1 31 nickel carbonyl, Ni(CO) 4, carbon disulphide, benzene, pyridine, ether, methyl propyl ketone; association characterized many hydroxylic compounds: for ethyl alcohol the factor of association was 2.74-2.43, for n-propyl alcohol 2.86-2.72, acetic acid 3.62 -2.77, acetone 1 .
To Jaeger is due the determination of the topic parameters of certain haloid-derivatives, and, while showing that the morphotropic effects closely resemble those occasioned by methyl, he established the important fact that, in general, the crystal form depended upon the orientation of the substituents in the benzene complex.
The hydroxyl group also resembles the methyl group in its morphotropic effects, producing, in many cases, no change in symmetry but a dimensional increase in one direction.
Willstatter (Ber., 1900, 33, p. 1164) obtained this acid by the action of a methyl alcoholic solution of ammonia on dibrompropylmalonic ester at 140° C., the diamide formed being then hydrolysed either by hydrochloric acid or baryta water: CH 2 CBr(C02H) 2 CH 2.
SALICYLIC ACID (ortho-hydroxybenzoic acid), an aromatic acid, C 6 H 4 (OH)(CO 2 H), found in the free state in the buds of Spiraea Ulmaria and, as its methyl ester, in gaultheria oil and in the essential oil of Andromeda Leschenaultii.
Methyl Salicylate, C,H 4 (OH) CO 2 CH 31 found in oil of wintergreen, in the oil of Viola tricolor and in the root of varieties of Polygala, is a pleasant-smelling liquid which boils at 222° C. On passing dry ammonia into the boiling ester, it gives salicylamide and dimethylamine.
It is a liquid, smelling like fusel oil and boiling at 108.4° C. Methyl ethyl carbinol, CH 3 C 2 H 5 CHOH, is the secondary alcohol derived from nbutane.
By the direct action of hydroxylamine on a methyl alcohol solution of mesityl oxide in the presence of sodium methylate a hydr oxylamino - ketone, diacetone hydroxylamine, (CH 3) 2 C(Nhoh) CH20OCH3,is formed.
ACETOPHENONE, or PHENYL-METHYL KETONE, C8H8O or C6H5CO.CH3, in chemistry, the simplest representative of the class of mixed aliphatic-aromatic ketones.
It is reduced by nascent hydrogen to the secondary alcohol C6H5.CH.OH.CH3 phenyl-methyl-carbinol, and on oxidation forms benzoic acid.
Acetonyl-acetophenone, C6H5.CO.CH2.CH2.CO.CH3, is produced by condensing phenacyl bromide with sodium acetoacetate with subsequent elimination of carbon dioxide, and on dehydration gives aa-phenyl-methyl-furfurane.
Nucleic acid is at present of unknown constitution; decomposition products are: phosphoric acid, uracil or 2.6-dioxy-pyrimidin,1 cytosin or 2-oxy-6-amino-pyrimidin, thymin (nucleosin) or 2.6-dioxy-5-methyl pyrimidin hypoxanthin 1 or 6-oxypurin, xanthin or 2.6-dioxypurin, adenine or 6 amino-purin, guanine or 2amino-6-oxypurin, pentoses (l-xylose), laevulinic acid, ammonia, etc. The nucleic acids vary with the source of the proteids, there being considerable differences in chemical composition.
This last substance may be reduced to mesoporphyrin, C34H3804N4, which by further reduction gives haemopyrrol, C 8 11 13 N, possibly methyl-propyl-pyrrol or butyl-pyrrol.
43) has found that solutions of diphenylamine in methyl cyanide possess an excess of pressure-producing particles and yet are non-conductors of electricity.