The resulting compound, nickel carbonyl, which was described to the Chemical Society in 1890, is both formed and decomposed within a very moderate range of temperature, and on this fact he based a successful process for the extraction of nickel from its ores.
The carbonyl group is not ketonic in character since it yields neither an oxime nor hydrazone.
Compounds containing the group - CH: O are known as aldehydes (q.v.), while the group >C: O (sometimes termed the carbonyl or keto group) characterizes the ketones (q.v.).
By the action of hydroxylamine or phenylhydrazine on aldehydes or ketones, condensation occurs between the carbonyl oxygen of the aldehyde or ketone and the amino group of the hydroxylamine or hydrazine.
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).
By transformations of the carbonyl group, and at the same time of the hydroxyl group, many interesting types of nitrogen compounds may be correlated.
Thus from the acid-amides, which we have seen to be closely related to the acids themselves, we obtain, by replacing the carbonyl oxygen by chlorine, the acidamido-chlorides, R CC1 2 NH 2, from which are derived the imido-chlorides, R CC1:NH, by loss of one molecule of hydrochloric acid.
The carbonyl oxygen may also be replaced by the oxime group,: N OH; thus the acids yield the hydroxamic acids, R C(OH): NOH, and the acid-amides the amidoximes, R C(NH 2): NOH.
A larger and more important series of condensations may be grouped together as resulting from the elimination of the elements of water between carbonyl (CO) and methylene (CH 2) groups.
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.
It is equal to the sum of the thermal effects of the aldehyde and carbonyl groups.
Thus oxygen varies according as whether it is linked to hydrogen (hydroxylic oxygen), to two atoms of carbon (ether oxygen), or to one carbon atom (carbonyl oxygen); similarly, carbon varies according as whether it is singly, doubly, or trebly bound to carbon atoms.
The principal chromophores are the azo, -N = N -, azoxy, = N 2 O, nitro, - N02, nitroso, - NO, and carbonyl, = CO, groups.
The carbonyl group by itself does not produce colour, but when two adjacent groups occur in the molecule, as for example in the a-diketones (such as di-acetyl and benzil), a yellow colour is produced.
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 .
Hofmann and Schotensack decompose a mixture of phenol (3 molecules) and sodium carbonate (4 mols.) with carbonyl chloride at 140-zoo° C. When 90% of the phenol has distilled over, the residue is dissolved and hydrochloric acid added, any phenol remaining is blown over in a current of steam, and the salicylic acid finally precipitated by hydrochloric acid.
Nascent hydrogen reduces them to primary alcohols, and phosphorus pentachloride replaces the carbonyl oxygen by chlorine.
It is readily polymerized, small quantities of hydrochloric acid, zinc chloride, carbonyl chloride, &c. converting it, at ordinary temperatures, into paraldehyde, (C 2 H 4 0) 3, a liquid boiling at 124° C. and of specific gravity oï¿½998 (15° C.).
00 2 H 5, is formed by the addition of well-cooled absolute alcohol to phosgene (carbonyl chloride).
Carbonyl chloride (phosgene), COC1 2, was first obtained by John Davy (Phil.
Chromic acid converts it into phosgene (carbonyl chloride, COC1 2).
On oxidation, the molecule is split at the carbonyl group and a mixture of acids is obtained.
Sodium amalgam reduces them to secondary alcohols; phosphorus pentachloride replaces the carbonyl oxygen by chlorine, forming the ketone chlorides.
-The diketones contain two carbonyl groups, and are distinguished as a or I.
This was burnt mouth-down in the oven., and the ashes on the ground reduced the red haematite to black magnetic oxide of iron; some traces of carbonyl in the ash helped to rearrange the magnetite as a brilliant mirror-like surface of intense black.
Urea chlorides are formed by the action of carbonyl chloride on ammonium chloride (at 400° C.), or on salts of primary amines.
It reacts with carbonyl compounds, giving semi-carbazones, and in consequence is frequently used for characterizing such substances.
Alkyl ureas are formed by the action of primary or secondary amines on isocyanic acid or its esters: [[Conh+Nh2r= R Nhc0nh]] 2 i [[Conr+Nhr 2 =Nr 2 Co Nhr]]; by the action of carbonyl chloride on amines: COC12+2NHR2=C0(NR2)2+2HC1; and in the hydrolysis of many ureides.
Those containing more than one acyl group are formed by the action of carbonyl chloride on acid amides: COC1 2 +2CH 3 Conh 2 = Co(NHCOCH3)2+2HC1.
1888 , 14, p. 44 1); by the action of carbon dioxide on monobrombenzene in the presence of sodium; by condensing benzene And carbonyl chloride in presence of aluminium chloride, the benzoyl chloride formed being subsequently hydrolysed; and similarly from benzene and chlorformamide: C6H6 +Cl Conh 2 = Hc1 -C6h,CONH2, the benzamide being then hydrolysed.
Baeyer and Villiger assume for the configuration of the salts of carbonyl compounds the arrangement > C: 0 < whilst, W.
Rend., 1908, 147, p. 1046) obtains it by heating thoria in a current of carbonyl chloride.
18 95, p. 945) has obtained metallic nickel from the Canadian mattes by first roasting them and then eliminating copper by the action of sulphuric acid, the product so obtained being then exposed to the reducing action of producer gas at about 350° C. The reduced metal is then passed into a "volatilizer" and exposed to the action of carbon monoxide at about 80° C., the nickel carbonyl so formed being received in a chamber heated to 180-200° C., where it decomposes, the nickel being deposited and the carbon monoxide returned to the volatilizer.
Nickel carbonyl, however, is extremely poisonous.
Nickel carbonyl, Ni(CO) 4, is obtained as a colourless mobile liquid by passing carbon monoxide over reduced nickel at a temperature of about 60° C. (L.
The vapour of nickel carbonyl burns with a luminous flame, a cold surface depressed in the flame being covered with a black deposit of nickel.
It is prepared by the action of carbonyl chloride on dimethyl aniline in the presence of aluminium chloride: COC12+2C6H5N(CH3)2=2HC1+CO[C6H4N(CH3)2]2.
Pyrocatechin readily condenses to form heterocyclic compounds; cyclic esters are formed by phosphorus trichloride and oxychloride, carbonyl chloride, sulphuryl chloride, &c.; whilst ortho-phenylenediamine, o-aminophenol, and o-aminothiophenol give phenazine, phenoxazine and thiodiphenylamine.
It is also decomposed by carbonyl chloride (Besson, loc. cit.).
Of great interest are the carbonyl compounds.
Other reactions which introduce carboxyl groups into aromatic groups are: the action of carbonyl chloride on aromatic hydrocarbons in the presence of aluminium chloride, acid-chlorides being formed which are readily decomposed by water to give the acid; the action of urea chloride Clï¿½COï¿½NH 2, cyanuric acid (CONH) 3, nascent cyanic acid, or carbanile on hydrocarbons in the presence of aluminium chloride, acid-amides being obtained which are readily decomposed to give the acid.