Substituting one hydroxyl group into each of these residues, we obtain radicals of the type - CH 2.
On the chromophoreauxochrome theory (the nitro group being the chromophore, and the hydroxyl the auxochrome) it is necessary in order to explain the high colour of the metallic salts and the colourless alkyl and aryl derivatives to assume that the auxochromic action of the hydroxyl group is only brought strongly into evidence by salt formation.
By the action of phosphorus pentachloride, the hydroxyl group is replaced by chlorine.
By the entrance of amino or hydroxyl groups into the molecule dyestuffs are formed.
When heated with concentrated hydrochloric acid the amino group is replaced by the hydroxyl group and the phenolic eurhodols are produced.
The hydrogen of the hydroxyl group in phenol can be replaced by metals, by alkyl groups and by acid radicals.
The meta-nitrocompound, which is precipitated last, is then reduced, and the amino group so formed is replaced by the hydroxyl group by means of the Sandmeyer reaction.
It is convenient first to consider the effect of introducing one, two, or three hydroxyl (OH) groups into the - CH 3, > CH 2, and >CH groups, which we have seen to characterize the different types of hydrocarbons.
A second hydroxyl group may be introduced into the residues - CH 2.
A third hydroxyl group may be introduced into the - CH: 0 residue with the formation of the radical - C(OH) :0; this is known as the carboxyl group, and characterizes the organic acids.
An important class of compounds, termed amines (q.v.), results from the condensation of alcohols with ammonia, water being eliminated between the alcoholic hydroxyl group and a hydrogen atom of the ammonia.
This group may be considered as resulting from the fusion of a carbonyl (:CO) and a hydroxyl (HO-) group; and we may expect to meet with compounds bearing structural resemblances to the derivatives of alcohols and aldehydes (or ketones).
Considering derivatives primarily concerned with transformations of the hydroxyl group, we may regard our typical acid as a fusion of a radical R CO - (named acetyl, propionyl, butyl, &c., generally according to the name of the hydrocarbon containing the same number of carbon atoms) and a hydroxyl group. By replacing the hydroxyl group by a halogen, acid-haloids result; by the elimination of the elements of water between two molecules, acid-anhydrides, which may be oxidized to acid-peroxides; by replacing the hydroxyl group by the group. SH, thio-acids; by replacing it by the amino group, acid-amides (q.v.); by replacing it by the group - NH NH2, acid-hydrazides.
By transformations of the carbonyl group, and at the same time of the hydroxyl group, many interesting types of nitrogen compounds may be correlated.
The introduction of hydroxyl groups into the benzene nucleus gives rise to compounds generically named phenols, which, although resembling the aliphatic alcohols in their origin, differ from these substances in their increased chemical activity and acid nature.
The phenols more closely resemble the tertiary alcohols, since the hydroxyl group is linked to.
OH, in which we will assume the hydroxyl group to occupy position I, is converted into brombenzene, which is then converted into benzoic acid, C 6 1-1 5 -COOH.
These three acids yield on heating phenol, identical with the substance started with, and since in the three oxybenzoic acids the hydroxyl groups must occupy positions other than I, it follows that four hydrogen atoms are equal in value.
Soc. 61, p. 367): If the hydrogen compound of the substituent already in the benzene nucleus can be directly oxidized to the' corresponding hydroxyl compound, then meta-derivatives predominate on further substitution, if not, then orthoand paraderivatives.
Thus a double bond of oxygen, as in the carbonyl group CO, requires a larger volume than a single bond, as in the hydroxyl group - OH, being about 12.2 in the first case and 7.8 in the second.
The substitution of a hydrogen atom by the hydroxyl group generally occasions a rise in boiling-point at about Ioo°.
The most important auxochromes are the hydroxyl (- OH) and amino.
The amino group is more powerful than the hydroxyl, and the substituted amino group more powerful still; the repeated substitution of hydroxyl groups sometimes causes an intensification and sometimes a diminution of colour.
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.
The nitro group behaves very similarly to the hydroxyl group. The effect of varying the position of the nitro group in the molecule is well marked, and conclusions may be drawn as to the orientation of the groups from a knowledge of the crystal form; a change in the symmetry of the chemical molecule being often attended by a loss in the symmetry of the crystal.
Beckmann, Ber., 1886, 1 9, p. 9 8 9; 188 7, 20, p. 2580), yielding as final products an acid-amide or anilide, thus: RC(:N OH)R'-RC(OH) :NR' ---> As regards the constitution of the oximes, two possibilities exist, namely >C: NOH, or > C' ?, and the first of these is presumably correct, since on alkylation and subsequent hydrolysis an alkyl hydroxylamine of the type NH 2 OR is obtained, and consequently it is to be presumed that in the alkylated oxime, the alkyl group is attached to oxygen, and the oxime itself therefore contains the hydroxyl group. It is to be noted that the oximes of aromatic aldehydes and of unsymmetrical aromatic ketones frequently exist in isomeric forms. This isomerism is explained by the HantzschWerner hypothesis (Ber., 1890, 23, p. II) in which the assumption is made that the three valencies of the nitrogen atom do not lie in the same plane.
Thus, with the tolylphenylketoximes, one yields the anilide of toluic acid and the other the toluidide of benzoic acid, the former necessitating the presence of the phenyl and hydroxyl radicals in the syn position and the latter the tolyl and hydroxyl radicals in the syn position, thus: CH3 C6H4 C C6H5
-> CH3C6H5CONHC6H51 N OH Syn-phenyltolylketoxime CH3 C6H4 C C6H5 CH3C6H4NH000,H5 HO N A nti-tolylphenylketoxime In the case of the aldoximes, that one which most readily loses the elements of water on dehydration is assumed to contain its hydroxyl radical adjacent to the movable hydrogen atom and is designated the syn-compound.
Perfectly pure distilled sea-water dissociates, to an infinitesimal degree, into hydrogen (H) and hydroxyl (HO) ions, so that one litre of such water contains 1 X 10 7, or 1 part of a gram-molecule of either hydr010,000,000 gen or hydroxyl (a gramme-molecule of hydrogen is 2 grammes, or of hydroxyl 17 grammes).
In aqueous solutions, for instance, a few hydrogen (H) and hydroxyl (OH) ions derived from the water are always present, and will be liberated if the other ions require a higher decomposition voltage and the current be kept so small that hydrogen and hydroxyl ions can be formed fast enough to carry all the current across the junction between solution and electrode.
Thus the hydroxyl mentioned above decomposes into water and oxygen, and the chlorine produced by the electrolysis of a chloride may attack the metal of the anode.
At the electrodes, however, the small quantity of hydrogen and hydroxyl ions from the water are liberated first in cases where the ions of the salt have a higher decomposition voltage.
The water being present in excess, the hydrogen and hydroxyl are re-formed at once and therefore are set free continuously.
If the current be so strong that new hydrogen and hydroxyl ions cannot be formed in time, other substances are liberated; in a solution of sulphuric acid a strong current will evolve sulphur dioxide, the more readily as the concentration of the solution is increased.
In dilute solution such substances as hydrochloric acid and potash are almost completely dissociated, so that, instead of representing the reaction as HC1+KOH = KC1 d-H20, we must write The ions K and Cl suffer no change, but the hydrogen of the acid and the hydroxyl (OH) of the potash unite to form water, which is only very slightly dissociated.
The aldehyde group also reacts with phenyl hydrazine to form two phenylhydrazones; under certain conditions a hydroxyl group adjacent to the aldehyde group is oxidized and glucosazone is produced; this glucosazone is decomposed by hydrochloric acid into phenyl hydrazine and the keto-aldehyde glucosone.
To the extent of 4 to 6%, and rather less in the other species, is expelled only at a high temperature; it is therefore water of constitution, existing as basic hydrogen or as hydroxyl replacing fluorine.
How much of the hydrogen and oxygen are in the hydroxylic (OH) form cannot be absolutely stated, but from the study of the acetates at least three hydroxyl groups may be assumed.
The chlorine reacts with the caustic soda, forming sodium hypochlorite, and this in turn, with an excess of chlorine and at higher temperatures, becomes for the most part converted into chlorate, whilst any simultaneous electrolysis of a hydroxide or water and a chloride (so that hydroxyl and chlorine are simultaneously liberated at the anode) also produces oxygen-chlorine compounds direct.
Oxy-acids are carboxylic acids which also contain a hydroxyl group; similarly we may have aldehyde-acids, ketone-acids, &c. Since the more important acids are treated under their own headings, or under substances closely allied to them, we shall here confine ourselves to general relations.
Phosphorus chlorides give acid chlorides, Rï¿½COï¿½C1, the hydroxyl group being replaced by chlorine, and acid anhydrides, (Rï¿½CO) 2 0, a molecule of water being split off between two carboxyl groups.
Sir Edward Frankland,showed how it could be derived from, and converted into, ethane; and thus determined it to be ethane in which one hydrogen atom was replaced by a hydroxyl group. Its constitutional formula is therefore CH3ï¿½CH2.OH.
The diazo group takes up the para position with regard to the hydroxyl group, and if this be prevented it then goes into the ortho position.
HYDRATE, in chemistry, a compound containing the elements of water in combination; more specifically, a compound containing the monovalent hydroxyl or OH group. The first and more general definition includes substances containing water of crystallization; such salts are said to be hydrated, and when deprived of their water to be dehydrated or anhydrous.
As the hydroxyl groups in aurin correspond to the amino groups in pararosaniline, two of these in the latter compound must be in the para position.
The hydroxyl group is more reactive than in the phenols, the naphthols being converted into naphthylamines by the action of ammonia, and forming ethers and esters much more readily.
It is reduced by sodium in boiling amyl alcohol solution to "aromatic" tetrahydro-a-naphthol (reduction occurring in the ring which does not contain the hydroxyl group).
DIAZO COMPOUNDS, in organic chemistry, compounds of the type R N 2 X (where R = a hydrocarbon radical, and X = an acid radical or a hydroxyl group).
Hantzsch, Ber., This assumption also shows the relationship of the diazonium hydroxides to other quaternary ammonium compounds, for most of the quaternary ammonium hydroxides (except such as have the nitrogen atom attached to four saturated hydrocarbon radicals) are unstable, and readily pass over into compounds in which the hydroxyl group is no longer attached to the amine nitrogen; thus the syn-diazo hydroxides are to be regarded as pseudo-diazonium derivatives.
That of the alcohols, which only differ from the hydrocarbons by having a group OH, called hydroxyl, instead of H, hydrogen; these compounds, when derived from the above methane series of hydrocarbons, are expressed by the general formula C7,H27,+10H.
This is filtered, washed, and then fused with caustic soda, when the sulpho-group is replaced by a hydroxyl group, and a second hydroxyl group is simultaneously formed; in order to render the formation of this second group easier, a little potassium chlorate or sodium nitrate is added to the reaction mixture.
In the solution, therefore, there is now an excess of hydroxyl ions; consequently it has an alkaline reaction and the litmus turns blue.
Two lactic acids are known, differing from each other in the position occupied by the hydroxyl group in the molecule; they are known respectively as a-hydroxypropionic acid (fermentation or inactive lactic acid), CH 3 CH(OH) CO 2 H, ands-hydroxypropionic acid (hydracrylic acid), (q.v.), CH2(OH) CH 2 CO 2 H.
Those with the hydroxyl group in the benzene nucleus are prepared from the aminophenols by the Skraup reaction.
Only two are known containing the hydroxyl group in the pyridine nucleus, namely, carbostyril (a-oxyquinoline), which is formed by the reduction of ortho-aminocinnamic acid with ammonium sulphide (L.
ALCOHOLS, in organic chemistry, a class of compounds which may be considered as derived from hydrocarbons by the replacement of one or more hydrogen atoms by hydroxyl groups.
It is convenient to restrict the term to compounds in which the hydroxyl group is attached to an aliphatic residue; this excludes such compounds as the hydroxy-benzenes, naphthalenes, &c., which exhibit many differences from the compounds derived from the aliphatic alkyls.
Alcohols are classified on two distinct principles, one depending upon the number of hydroxyl groups present, the other on the nature of the remaining groups attached to the carbon atom which carries the hydroxyl group. Monatomic or monohydric alcohols contain only one hydroxyl group; diatomic, two, known as glycols; triatomic, three, known as glycerols; and so on.
Sodium or potassium dissolves in them with the formation of alcoholates, the hydrogen of the hydroxyl group being replaced by the metal.
The chlorides AsCl2CH3 and AsCl(CH3)2 as well as As(CH3)3 are capable of combining with two atoms of chlorine, the arsenic atom apparently changing from the tri- to the penta-valent condition, and the corresponding oxygen compounds can also be oxidized to compounds containing one oxygen atom or two hydroxyl groups more, forming acids or oxides.