417 



GLYCOL. 



GLYCOL. 



418 



engaged, and the hqiud IB converted into a 8ohd white mass consisting 



of monosodium glycol, Na > 0.. By heating this compound with an 



H I 



additional equivalent of sodium to a temperature of 374 Fahr. another 

 equivalent of hydrogen is replaced by sodium the disodium glyco 



formed - 



Nitric acid oxidises glycol with great energy, with formation o 

 glyoxylic, glycolic, and oxalic acids. 



When glycol is fused with hydrate of potash, a large quantity ol 

 hydrogen gas is disengaged, and the residue consists principally o 

 oxalate of potash. Alcohol, under similar treatment, yields hydrogen 

 and acetate of potash : 



C *H*")o 



+ 2KOHO = 



+ 8K 



Glycol. 



Oialatc of potash. 



The action of pentachloride of phosphorus on glycol is very ener- 

 getic ; the products formed are hydrochloric acid, oxychloride of phos- 

 phorus, and chloride of ethylene. 



C 4 H 4 " 



2PC1, 



C 4 H 4 "C1, 



2PO,C1 3 



21IC1 



Glycol. Pentachloride Chloride of Oiychloride 

 of phosphorus. ethylene. of phosphorus. 



Chloride of ethylene is the true hydrochloric ether of glycol it stands 

 towards it in the same relation as chloride of ethyl to alcohol. 



Ethert of glycol. The ether of glycol is not formed by the ordinary 

 processes of etterification. When glycol is treated with chloride of 

 zinc, aldehyde is formed, and Wurtz was at first inclined to regard this 

 as the ether corresponding to glycol. The true ether is, however, 

 obtained by the action of notash on monohydrochlorate of glycol : 



C.H 4 0, 4- KC1 + 2HO 



KOHO 



Monochlorhydrate 

 of glycol. 



The action takes place with considerable energy, chloride of potassium 

 is formed, and a gas disengaged which is condensed by means ol 

 a freezing mixture to a very mobile liquid, boiling at 56 Fahr. Its 

 vapour density is 1'42. The calculated number is 1'52. 



It is isomeric with aldehyde, which it resembles in many respects. 

 It reduces ammoniacal nitrate of silver but unlike aldehyde, it forms 

 no crystalli&e compound with ammonia. By the action of penta- 

 chloride of phosphorus, glycolic ether yields chloride of ethylene, 



C.H.O, + PCI, 



Glycolic ether. 



PO.C1, + C.H.C1, 



Chloride of 

 ethylene. 



By the same treatment, aldehyde yields chloride of aldehydene. 

 Two mixed ethers, corresponding to the mixed ethers of Williamson 



/C 4 H 4 "1 \ 



have been obtained from glycol. The first, ethylglycol [ (C.H,) 1 0, ), 



\ H J / 

 is obtained by the action of iodide of ethyl on monosodium glycol : 



Na 



C 4 H 4 " ) 



C,H S I = (C.IIj) JO. 4- Nal 



Iodide of > - v - ' Iodide of 



ethyl. Ethylglycol. sodium. 



Monosodium 

 glycol. 



When monoethylglycol is treated with potassium, hydrogen is 

 liberated and a white solid mass formed, which, when treated with 

 iodide of ethyl, yields diethylglycd : 



C H 



4- C 4 H a I = KI 4- 



Iodide of 

 potassium. 



Diethylglycol. 



Diethylglycol is a colourless mobile liquid, with an agreeable ethereal 

 odour. Its sp. gr. is 07993, and its vapour density, 4-095 Theory 

 require* 4-085. Its boiling point is 254 Fahr. In this respect it 

 differs from acetal, with which it is isomeric, which boils at 217 Fahr 



Compound etturi of glycol. The compound ethers of the alcohoi 

 series are formed by the union of 



Alcohol + acid 2 at. Wiitcr. 

 as in the formation of acetic ether : 



c.11,,0, 4- C.II.O. JHO 



(C 4 ,H 3 0.,)} 



Acetic acid. 



Acetic ether. 

 In an analogous manner the compound ethers of glycol are derived 



ARTS ASD 801. DIV. VOL. IV. 



by the union of glycol + 2 at. acid 4 at. water, as in the forma- 

 tion of acetate of glycol : 



2C 4 H 4 0. 4HO = 



C 4 H 4 



Glycol. Acetic acid. 



Acetate of glycol. 



In saponifying, the compound ethers of alcohol assimilate 2 at. water 

 whilst the compound ethers of glycol assimilate 4 at. water. The 

 compound ethers of glycol are in general prepared by the action of the 

 iodide or bromide of ethylene on the corresponding silver salt. 

 C 1 H " 1 



Acetate of glycol (C 12 H 10 8 =, ( t H * Q ^ |0 4 ); is formed bythe action 



of iodide or bromide of ethylene on acetate of silver in the presence of 

 free acetic acid. It is a colourless neutral liquid, with a slight acetic 

 odour. It boils at 367 Fahr. It dissolves in 7 volumes of water 

 at 71 Fahr. 



C 4 H 4 " ) 

 Monoacetate of glycol (C S H 8 0,,= C 4 H 3 2 V 4 ). The preparation and 



properties of this body have been already described. It is also formed 

 when anhydrous acetic acid acts on glycol. When heated for some 

 time in a closed vessel with water, it is decomposed into glycol and 

 free acetic acid. 



JJutyrate of glycol (C M H 18 8 = ,^ jj Q \ f 0*) " f orme <J bythe action 

 of bromide of ethylene on butyrate of silver in the presence of free 

 butyric acid. The product of the action is treated with ether and the 

 ethereal solution distilled and rectified. Butyrate of glycol is a colour- 

 less liquid, with a somewhat butyric odour, boiling at about 464 Fahr. 

 and distilling without alteration. It is quite insoluble in water, but 

 completely so in alcohol and ether. 



Stearateof glycol (C, H 74 0, = |^ H ^ Q , J 4 ), obtained by the 



action of bromide of ethylene on stearate 01 silver, consists of brilliant 

 small laminae, fusible at 169 Fahr., and closely resembling stearin. 



Jienzoate of glycol (C M H 14 0,= $ H Q , j- 4 ) is prepared like the 



preceding ethers. It presents the form of colourless, right rhomboidal 

 prisms, which fuse at 153 Fahr., and distil without alteration at a 

 point beyond the ordinary range of the thermometer. 



Hydrochloric etheri of ylycol. The neutral hydrochloric ether 

 of glycol, and that which stands to glycol in the same relation as 

 chloride of ethyl to alcohol, is the oil of olefiant gas, or chloride of 

 ethylene C 4 H 4 C1,. It may be conceived as being derived from glycol 

 by the replacement of 2 eq. of peroxide' of hydrogen by 2 eq. chlorine. 

 From the constitution of glycol, it is evident that there may be an 

 ether intermediate between chloride of ethyleue and glycol, in 

 fact glycol in which one eq. of peroxide of hydrogen is replaced by 

 chlorine. The relation of these bodies may be seen from the scheme : 



C.H.- 

 H 



C 4 H 4 

 Cl 



Glycol. 



Chloride of 

 ethylene. 



Monochlorhydrate 

 of glycol. 



The body in question has been termed the chlorhydrin of glycol. 



It is formed by the action of hydrochloric acid on glycol, and is a 

 colourless liquid, boiling at 262 Fahr. By the action of potash it 

 jives oxide of ethylene. 



Chloracetine of glycol (C,H,C10 4 ). This body is formed by the con- 

 current action of hydrochloric acid and acetic acid on glycol. It is a 

 colourless liquid, heavier than water, and boiling at 293 Fahr., 

 without decomposition. It is intermediate between chloride of ethy- 

 lene and acetate of glycoL Its formation may be thus expressed : 



1 }o, 4- nci = (c 4 4 H,o a ) o a 4- 4HO 



' , Cl ) 



Glycol. Acetic acid. _ , 7> T~? , 



' Chloracetinj>f glycol. 



[t is also formed by the action of hydrochloric acid on monoacetate o 

 (booL 



It is decomposed by potash, with formation of acetate and chloride 

 of potassium. 



Chlorbutyrin of glycol and chlorbenzoin of glycol are compounds 

 quite analogous to this, and are prepared by similar methods. 



Sutyroacetate of glycol. This is glycol in which one atom of hydro- 

 ren is replaced by the radical acetyl, and another by butyryl. It in a 

 substance with a bitter pungent taste, heavier than water, and boiling 

 ,t 410 Fahr. It is formed by the action of chloracetin of glycol on 

 mtyrate of silver. 



C 4 H 4 " 

 C 4 H a O, 



a 



f TT " \ 



B<H 'i}o, = C 4 H*0, 4 4- AgCl 

 * C H II,0, ) 



Butyratc of 

 silver. 



Butyroacctate 

 of glycol. 



Chloride 

 of silver. 



Chloracetin 

 of glycol. 



t is evident that many such analogous compounds may be formed. 



