Double chlorides of composition CoC1 2 NH 4 C1.6H 2 O; CoC1 2 SnCl 4.6H 2 0 and CoC1 2.2CdC1 2.12H 2 O are also known.
The pentammine nitrito salts are known as the xanthocobalt salts and have the general formula [NO 2 Co (NH 3) 3]X2.
ALLANTOIN, C 4 H 6 N 4 O 3 or CO Q `, the NH-CO diureide of glyoxylic acid.
Grimaux by heating one part of glyoxylic acid with two parts of urea for ten hours at ioo° C.: 2CO(NH 2) 2 + CH(OH) 2 Oooh = 3h 2 O + C4H6N403.
The dihydro derivatives are most probably those compounds which are formed in the condensation of acidyl derivatives of acetone, with urea, guanidine, &c. Tetrahydropyrimidines are obtained by the action of amidines on trimethylene bromide: Br(CH 2) 3 Br+C 6 H 5 C (:NH) NH 2 = 2HBr+C 4 H 7 N 2 (C 6 H 5) .
N:CH N N:C(CH3) N NH CO NH ' 'CH :CH CH NH2 C :CH C CH 3 CH :CH 0 Pyrimidine Cyanmethine Uracil
It yields a silver salt which with ethyl iodide forms benzimido-- ethyl ether, C 6 H 5 C: (NH) ï¿½OC 2 H 5, a behaviour which points to.
The silver salt as being derived from the tautomeric imidobenzoic acid, C 6 1-1 5 C: (NH) -OH (J.
The secondary and tertiary amides of the types (RCO) 2 NH and (RCO) 3 N may be prepared by heating the primary amides or the nitriles with acids or acid anhydrides to 200° C. Thiamides of the type R.
Boron fluoride also combines with ammonia gas, equal volumes of the two gases giving a white crystalline solid of composition BF 3 NH 3 i with excess of ammonia gas, colourless liquids BF 3.2NH 3 and BF 3.3NH 3 are produced, which on heating lose ammonia and are converted into the solid form.
It can also be prepared by heating borimide B2(NH)31 or by heating boron trioxide with a metallic cyanide.
Borimide B 2 (NH) 3 is obtained on long heating of the compound B 2 S 3.6NH 3 in a stream of hydrogen, or ammonia gas at 115-120° C. It is a white solid which decomposes on heating into boron nitride and ammonia.
35, p. 7), who regard it as NO 2 -CH(CN) CO NH 2.
Dibromcotinine on hydrolysis yields oxalic acid, methylamine and 0-methyl pyridyl ketone: C10H10Br2N20+3H20+0= H2C204-ECH 3 NH 2 +C 5 H 4 N 000H 3 +2HBr; whilst dibromticonine yields methylamine, malonic acid and nicotinic acid: C10H8Br2N202+ 4H20=CH 3 NH 2 +CH 2 (CO 2 H) 2 +C 5 H 4 N CO 2 H+2HBr, or if heated with zinc and caustic potash, methylamine and pyridyl-ay-dioxybutyric acid.
The following formulae are important: N - CH C =CH/ - CH CH2 CH CH C/ NH CH / N CH2 N / N / N% CH CH H3C CH2 N-fl-Pyridylpyrrol, a0-pyridylpyrrol, nicotine.
OH NH 2 (1.3),and dimethyl meta-aminophenol,C 6 H 4.
Silberrad (Ber., to be a dihydro HC NH N --> 1V NH CH.
Hofmann), CS 2 +2NH 3 -->NH 2.
Carbon bisulphide combines with primary amines to form alkyl dithiocarbamates, which when heated lose sulphuretted hydrogen and leave a residue of a dialkyl thio-urea, CS 2 +2R NH 2 - R NH CSS NH 3 RCS(NHR)2+H2S; or if the aqueous solution of the dithiocarbamate be boiled with mercuric chloride or silver nitrate solution, a mustard oil (q.v.) is formed, R.NH CSS NH3R+HgC12-Hg(R NH CSS)2->2RNCS-}-HgS+H2S.
Rouge de Ruthene, Ru 2 (OH) 2 C1 4 (NH 4) 7, is obtained from ammonia and ruthenium sesquichloride at 40° C., the product being purified by crystallization from ammonia.
NH 2; secondary, R2: NH; and tertiary, R3: N; the oxamines, R 3 N :0, are closely related to the tertiary ammonias, which also unite with a molecule of alkyl iodide to form salts of quaternary ammonium bases, e.g.
Thus with hydroxylamine aldehydes yield aldoximes, R CH: N OH, and ketones, ketoximes, R 2 C: N OH (see Oximes), while phenyl hydrazine gives phenylhydrazones, R 2 C:N NH C 6 H 5 (see Hydrazones).
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.
OH; R.CO Cl; (R.CO)20; R.CO SH; acid; acid-chloride; acid-anhydride; thio-acid; R CO NH 2 i R CO NH NH2.
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.
By replacing the chlorine in the imido-chloride by an oxyalkyl group we obtain the imido-ethers, R C(OR') :NH; and by an amino group, the amidines, R C(NH 2): NH.
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.
Aniline, C 6 H 5 NH 2, monomethyl aniline, C 6 H 5 NH CH 3, and dimethyl aniline, C 6 H 5 N(CH 3) 2, are in increasing order of basicity.
Thus in the tri-substitution derivatives six isomers, and no more, are possible when two of the substituents are alike; for instance, six diaminobenzoic acids, C 6 H 3 (NH 2) 2 000H, are known; when all are unlike ten isomers are possible; thus, ten oxytoluic acids, C 6 H 3 -CH 3.
The diaminobenzene resulting from two of these acids is the ortho-compound; from three, the meta-; and from one the para-; this is explained by the following scheme: CH NH, NH, NH., IAO NH, N / NH HooCCNH, Cooh Nh, W.
Syntheses of the Benzene Ring.-The characteristic distinctions NH NH, r.-NH, [[Cooh Cooh, _ + Nh2 Nh, H., Cooh]] x x x Tri.
The compounds so obtained, alicyclic-,-tetrahydronaphthylamine and alicyclic-atetrahydronaphthol, closely resemble f3-aminodiethylbenzene, C 6 H 4 (C 2 H C 2 H 4 NH 2, and 3-oxydiethylbenzene,C 6 H 4 (C 2 H 5) C2H40H.
If a-naphthylamine and a-naphthol be reduced, the hydrogen atoms attach themselves to the non-substituted half of the molecule, and the compounds so obtained resemble aminodiethylbenzene, C 6 H 3 NH 2 (C 2 H 5) 21 and oxydiethylbenzene, C 6 H 3.
The three primary members are furfurane, thiophene and pyrrol, each of which contains four methine or CH groups, and an oxygen, sulphur and imido (NH) member respectively; a series of compounds containing selenium is also known.
N=CHN=N N = CH NH N = CH?NH Triazole.
Typical formulae are (R denoting 0, S or NH): Isomers are possible, for the condensation may be effected on the two carbon atoms symmetrically placed to the hetero-atom; these isomers, however, are more of the nature of internal anhydrides.
In the case of the amines he decides in favour of the formulae H2C: NH3 2C NH2 H 3 C. NH CH3 H primary, secondary, tertiary.
(- NH 2) groups.
Jacobson, Lehrbuch der organischen Chemie; Richter-Anschutz, Organische Chemie (I I th ed., K 2 S04 K2 S04 (NH 4) 2 SO 4 =o% SO 4 = coo FIG.
PYRROL, C 4 H 5 N or C 4 H 4 NH, an organic base found in coaltar and Dippel's oil.
'Bell, ' Ber., 1880, 13, p. 877); by distilling calcium pyroglutaminate: HO 2 C' CH(NH 2)'CH 2 'CH 2 'CO 2 H = C 4 H 4 NH+ C02+2H20 (L.
Zinc dust and hydrochloric acid reduce pyrrol to pyrrolin (dihydropyrrol), C 4 H 6 NH, a liquid which boils at 90° C. (748 mm.); it is soluble in water and has strongly basic properties and an alkaline reaction.
The chlorine atom in this compound is replaced by the cyano-group, which is then reduced to the CH 2 NH 2.
Knorr, by the action of ammonia on aceto-acetic ester, obtained (3-imidobutyric ester, which with nitrous acid yields a-isonitroso-(3-imidobutyric ester, CH 3 C(:NH) C(:N OH) CO 2 C 2 H 5.
He also found that diaceto succinic ester reacts with compounds of the type NH 2 R(R = H, CH 3, OH, NHC 6 H 5, &c.) to form pyrrol derivatives CH3 CO CH CO 2 R, C(CH3) :C C02R A NH 2 R -?- - RN(CH 3 CO CH CO 2 R C(CH3) :C C02R By using compounds of the type NH 2 R and acetophenone acetoacetic ester C 6 H 5 CO CH 2.
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.
It behaves as a powerful reducing agent, and on hydrolysis with dilute mineral acids is decomposed into formaldehyde and hydroxylamine, together with some formic acid and ammonia, the amount of each product formed varying with temperature, time of reaction, amount of water present, &c. This latter reaction is probably due to some of the oxime existing in the form of the isomeric formamide HCO NH 2.
Wallach (Ann., 1900, 312, p. 171) has shown that the saturated cyclic ketones yield oximes which by an application of the Beckmann reaction are converted into isoximes, and these latter on hydrolysis with dilute mineral acids are transformed into acyclic amino-acids; thus from cyclohexanone, e-amidocaproic acid (e-leucine) may be obtained: CH2" C NOH C CH 2 CH 2 7: ?12?CH2 CH2 NH /CH2 CH2 C02H CH2', An ingenious application of the fact that oximes easily lose the elements of water and form nitriles was used by A.
It is also prepared by heating ammonium nitrite (or a mixture of sodium nitrite and ammonium chloride): NH 4 NO 2 =2H20+N21 by heating a mixture of ammonium nitrate and chloride (the chlorine which is simultaneously produced being absorbed by milk of lime or by a solution of sodium hydroxide): 4NH4N03+2NH4C1=5N2 +C1 2 +12H 2 O; by heating ammonium dichromate (or a mixture of ammonium chloride and potassium dichromate): (NH4)2Cr207 = Cr203+4H20+ N2; by passing chlorine into a concentrated solution of ammonia (which should be present in considerable excess): 8NH3+3C12=6NH4C1-F-N2; by the action of hypochlorites or hypobromites on ammonia: 3NaOBr-+2NH 3 =3NaBr+3H 2 OH-N 2; and by the action of manganese dioxide on ammonium nitrate at 180-20o° C. It is also formed by the reduction of nitric and nitrous oxides with hydrogen in the presence of platinized asbestos at a red heat (G.
The reactions are represented as (I) N2+3H2+2C0 -1-2H 2 0=2H CO 2 NH 4 (Ammonium formate).