109 



ORGANIC BASES. 



ORGANIC BASES. 



110 



8 a powerful base, comparable only with caustic potash or soda. It 

 saponifies oils, precipitates metallic oxides from their salts, is not 

 volatile without decomposition, rapidly absorbs .carbonic acid and 

 water from the ah-, is itself crystalline, and forms crystalline salts with 

 acids, turns red litmus-paper blue, dissolves the cuticle, and, in short, 

 behaves as though it were an inorganic alkali. Ethylamine is a colour- 

 less, volatile liquid of sp. gr. 0'696 ; vapour density, 1'594; soluble hi 

 water in all proportions ; acts like ammonia upon solutions of metallic 

 salts, but, unlike ammonia, it dissolves recently-precipitated alumina. 

 Diethylamine is also colourless, volatile, inflammable, and caustic ; 

 boiling point, 134"6. Triethylamine resembles ethylamine and 

 diethylamine, and forms a beautiful orange-coloured crystalline salt 

 with bichloride of platinum, containing ( (C 4 H 5 ) 3 N, HC1, PtCl 2 ). 



So much for the general method of procuring the greater part of the 

 organic bases. Of course the iodide, and sometimes the bromide or 

 chloride, of any alcohol radical may be employed, the amines formed 

 containing that radical hi the place of the ethyl hi the example quoted. 

 Moreover a primary amine may be acted upon by the iodide of a 

 radical other than that it already contains, and the secondary amine 

 thus formed acted upon by the iodide of a third radical different from 

 either of the two existing hi it, and finally the tertiary amine thus 

 produced may be made to unite with the iodide of a fourth alcohol 

 radical, and an ammonium called into existence having the four equiva- 

 lents of hydrogen substituted by four different electro-positive radicals. 



This method is important, not only in producing new organic bases, 

 but as a means of ascertaining the constitution of an organic base after 

 its composition has been determined by organic analysis. For ob- 

 viously, if the base will only unite with one molecule of an alcohol 

 radical, it must be a tertiary monamine; if with two, a secondary 

 monamine ; if with three, a primary monamine. The process does 

 not, however, tell us hi all cases whether the unknown radical already 

 present in the body is monatomic, diatomic, or teratomic. The natural 

 bases conine and codeine have in this way been shown to be secondary 

 and tertiary monamines respectively, while nicotine, quinine, cincho- 

 nine, quinidine, brucine, and strychnine are either tertiary monamines 

 or tertiary diamines. 



The following organic bases, mostly formed by the above general 

 method, have already been mentioned hi this Cyclopaedia, but for 

 details concerning them, have been referred to the present article. 

 Thi'ir general properties are similar to those of the ethyl derivatives 

 fully described above ; their special characteristics will only therefore 

 be given. 



Methylamine (N, H,. C,H 3 ) is frequently met with in organic decom- 

 positions ; it is a gas, but may be condensed by a freezing mixture ; it 

 is inflammable, and at 55 Fahr. water dissolves 1150 times ita bulk. 

 i i\t has not been isolated in a pure state. Trimethytamine 

 (N(C,H,),) may often be recognised by ita odour hi the roe of her- 

 rings ; it boils at 41" Fahr. and ia inflammable. Tetramethylammonium, 

 hyd. ox. (N(C,H ? ),,O, HO), crystallises in deliquescent needles; ita 

 salts also crystallise well. ifetlti/l/ri'lhi//:tmmonium, hyd. ox. (NC,H V 

 (C 4 H,) 3 , 0, HO) ia crystalline; its salts are very soluble in water. 

 Prn/jytaminc (NH 2 C,,H,) has not been much studied. Ilntylamine 

 (NHjC.H,) ia a colourless liquid, lighter than water; boiling point 

 about 176* Fahr. ; it forma stable crystalline salts. Amylamine (NH,, 

 C lo H n ) boils at 203 Fahr. ; has a specific gravity of 0-7503, and is 

 inflammable. IXamytttmiiu (NH(C 10 H 11 ),) boila at 338 Fahr. Tri- 

 amylamine (N(C 10 H,.)j) boils at 494-6 Fahr., and much resembles 

 diamylamine. ifet/iyl-rt/iyl-amylamiiic (NC 2 H,C,H S C 10 H 11 ) is a colour- 

 less oil of agreeable aromatic odour ; boiling point, 275" Fahr. Jtiet/ii/l- 

 amylamine (N(C,H 5 ),C, H n ) boils at 309'2 Fahr., and with iodide of 

 methyl gives the iodide of methyl-dUthyl-amyl-ammanium. Tetramyl- 

 ammonium, hyd. ox. (N(C' 10 H n ),OHO) occurs hi deliquescent crystals. 

 Amyltrietlujlammtmium, hyd. ox. (N(C 10 H U ) (C,H 5 ),OHO) forms crys- 

 talline salts, but ia not crystalline itself. Tricetylamiiu (N(C 31 H M ) 3 ) 

 crystallises hi colourless needles; melting point, 102-2 Fahr. 

 lamint (N H 2 C,,H 5 ) distils between 356 and 374 Fahr. 



A second method of forming organic bases is by the reduction of 

 nitro-compounds. Many organic bodies suffer substitution of peroxide 

 of nitrogen for hydrogen, when they are acted upon by nitric acid. 

 The resulting nitro-compounds undergo a remarkable transformation 

 when subjected to the influence of nascent hydrogen, sulphuretted 

 hydrogen and other well-known reducing agents, NH, or H, taking 

 the place of NO, or O,. Thus benzole (C,,H ) yields nitrobenzole 

 (C,,H,NOJ on being acted upon by nitric acid ; and nitrobenzol fur- 

 nishes the organic base phenylamine (NH.C^HJ, or AMLIXE, on being 

 treated with sulphuretted hydrogen, thus : 



CijH.XO. + OH3 = NH 2 C lt H, + 4HO + 8, 



Xitrobenzol. Sulphuretted PhenyUmine. Water. Sulphur, 

 hydrogen. 



In a similar manner there have been formed totylamine (toluidine) 

 (N I f ,C,.H,) ; xylylamine (xylidine) (NH 2 C,.H ) ; cumylamine (cumidine) 

 <MM;,,H U ); and nap/itylamine, NH,(C IO H,)- Many derivatives of 

 these compounds have been formed by applying the substitutive pro- 

 cesses described under the first method : the following are the chief of 

 them. Mttlnjl-phenylamine (NHCjHjOJB,), a fragrant oil, boiling at 



377-6 Fahr. Ethyl-pTunylamiwi (NHC.HjC^Hj), sp. gr. 0'954 ; boiling 

 point 400 Fahr. Afethyl-ethyl-phtnylamine (NC 2 H 3 C 4 H S C 12 H 5 ) re- 

 sembles ethyl-phenylamine, but is not, like it, coloured blue by hypo- 

 chlorite of lime. Dietliylphenylamine (N (C 4 H S ) 2 C 12 H,), sp. gr. 0-939 ; 

 boiling point 416 Fahr. Ethyl-nitrophenylamine contains (NHC H 5 

 [C la H 4 NO,] ). Amyl-phenylamine (NHC^H^ C 12 H 5 ) is soluble iu 

 ether and boils at 496'4 Fahr. Methyl-amyl-phenylamine (N"C.,H 3 

 C 10 H,, C,,H 5 ) has an agreeable odour. Ethyl -amyl-phenylamine 

 (NC 4 H 5 C 10 H U C 12 H S ) boils at 503-6 Fahr. Diamyl-pkenylamiue 

 (NfCja^C.jH,,) boils between 527 and 536 Fahr. Cetyl-phenyla- 

 miiic (NHCj.Hj., C 12 H 5 ) crystallises in plates, is not soluble iu water, 

 and melts at 107'6 Fahr. IHcetyl-phenylamine (N (C^H^^C^H,) is 

 more fusible than cetylphenylamine. Triethyl-phenyl-ammonium, hyd. 

 ox. (N (C,H 5 ) 3 C 12 H S OHO) forms crystalline salts. Methyl-ethyl-amyl- 

 phenyl-ammonium hyd. ox. (N C 2 H 3 C 4 H 5 C 10 H U C 12 H 5 OHO) much 

 resembles the preceding organic base. Etkyl-tdylamine (NHC,H 5 , 

 C,,H,) is a colourless oil, sp. gr. 0-939, boiling point 422-6 Fahr. 

 Dii thyl-tolylamine (N (C.H,,)., C 14 H 7 ) boils at 444 Fahr. Triethyltolyl- 

 ammimium, hyd. ox. contains (N(C,H 5 ) 3 C 14 H, OHO). 



The third general method of producing organic bases is by the 

 decomposition of nitrogenous substances; the agents used being 

 destructive distillation, boiling with caustic potash, and, in a few cases, 

 oxidation ; other agents, also, are used in a few special cases. 



The destructive distillation of coal furnishes pyridine (N(C 10 H,)"'); 

 picoline (N (C^H,)"') ; lutidine (N (C,,^)'") ; collidine (N (C l(1 H )'") ; 

 leucoline (N (C 18 H,)'") ; lepidine (NO^H,)'") ; and cryptidine 

 (N(C 22 H U )'"). Methylamine, ethylamine, propylamine, butylamine, 

 amylamine, pyridine, picoline, lutidine, and collidine are contained in 

 Dippel's oil, a tarry matter obtained on destructively distilling bones. 

 Beans also, on the application of heat furnish a base named fabine. 

 Caustic potash converts the cyanates of methyl, ethyl, amyl, allyl, and 

 phenyl into methylamine, ethylamine, amylamine, allylainine, aud 

 phenylamine respectively. The compound ureas, whose formulas will 

 presently be given, suffer a similar splitting up by heating with potash, 

 ammonia being formed hi addition to the bodies just mentioned. 

 Soda-lime converts oonanthyl-aldehyd (C,,H 1 ,O 2 ) into trieaproylamiiu' 

 (N (C.jH^),). Baryta converts creatin into sarcosine (C H,NO,). 

 Brucine is converted by nitric acid into cacotheline (C 10 H !! . ! (NO 4 ),,N 2 O 10 ). 



Finally, many of the organic bases already noticed, are "formed 

 during the putrefaction and fermentation of organic bodies. 



The organic bases whose names and formula) are here appended, are 

 chiefly produced by the first general method. The cyanates of the 

 alcohol radicals are the agents used for acting upon the ammonia, and 

 no elimination of secondary product takes place. Moreover, they are 

 mostly diamines and ammoniums, the organic bases hitherto described 

 being all monamines. 



Urea . 



Ethyl-urea . 



Allyl-urea . 



Sulphallyl-urea 

 (thioinamine) 



Fhenjl-urea . 



(C,0,)" 



N, 



C.H. H N, 



C.H 5 II 



H 2 



(C 2 S 2 )" 

 C,U 5 II 



H, 



(C,0 2 )" 

 C,aH 5 I 

 II, 



(C 2 S 2 )" 

 Sulphophcnyl-urca C, 2 H 5 n 



Snlphallyl-pucnyl- 



C.H S ,C 12 H 5 N 



Dimethyl-urea 



Diethyl-urea 



(C a 2 )" 

 (C 2 H,) 2 



(C 2 2 )" 

 (C.H.), 



Diallyl-urca (sina- >Z"&> l*r 

 poline) . . ( U "=J2 ( N s 

 "a 



Diphenyl-urca !r ! , 5 /', 

 (flavinc) . . ti2"=>: 



Ethyl-allyl-urca 



(C,0 2 



Sulphethyl-allyl. <, c s >" , 

 urea . c * H c H s ? N a 



Azophenylaminc 



Ethyl-pipcryl-urca C 4 1I 5 H 5N 2 



(C 1S 



Nitrazophenylamine . . . 



Azonaphthylamine . . . 



Ethyl-plcalyl-ammonlom. hyd. ox. . 

 Ethyl-leucolyl-ammonium, hyd. ox. 

 Methyl-morphyl-ammonlum, hyd. ox. 

 Ethyl-codyl-ammonium, hyd. ox. . 

 Ethyl-qulnyl-ammonium, hyd. ox. . 



H 2 

 H 2 



