FREE BOOKS

Author's List




PREV.   NEXT  
|<   67   68   69   70   71   72   73   74   75   76   77   78   79   80   81   82   83   84   85   86   87   88   89   90   91  
92   93   94   95   96   97   98   99   100   101   102   103   104   105   106   107   108   109   110   111   112   113   114   115   116   >>   >|  
, formulated with an open chain, there is little to surmise beyond the change of position of a CO- group. But alternative formulae have been proposed. Thus the tetracetate is a derivative to be reckoned with in the problem. It is formed under conditions which preclude constitutional changes within the unit groups. The temperature of the main reaction is 30 deg.-40 deg., the reagents are used but little in excess of the quantitative proportions, and the yields are approximately quantitative. If now the derivative is formed entirely without the hydrolysis the empirical formula C_{6}H_{6}O.(OAc)_{4} justifies a closed-ring formula for the original viz. CO<[CHOH]_{4}>CH_{2}; and the preference for this formula depends upon the explanation it affords of the aggregation of the groups by way of CO-CH_{2} synthesis. The exact relationship of the tetracetate to the original cellulose is somewhat difficult to determine. The starting-point is a cellulose hydrate, since it is the product obtained by decomposition of the sulphocarbonate. The degree of _hydrolysis_ attending the cycle of reactions is indicated by the formula 4 C_{6}H_{10}O_{5}.H_{2}O. It has been already shown that this degree of hydrolysis does not produce molecular disaggregation. If this hydrate survived the acetylation it would of course affect the empirical composition, i.e. chiefly the carbon percentage, of the product. It may be here pointed out that the extreme variation of the carbon in this group of carbohydrate esters is as between C_{14}H_{20}O_{10} (C = 48.3 p.ct.) and C_{14}H_{18}O_{9} (C = 50.8 p.ct.) i.e. a tetracetate of C_{6}H_{12}O_{6} and C_{6}H_{10}O_{5} respectively. In the fractional intermediate terms it is clear that we come within the range of ordinary experimental errors, and to solve this critical point by way of ultimate analysis must involve an extended series of analyses with precautions for specially minimising and quantifying the error. The determination of the acetyl by saponification is also subject to an error sufficiently large to preclude the results being applied to solve the point. While, therefore, we must defer the final statement as to whether the tetracetate is produced from or contains a partly hydrolysed cellulose molecule, it is clear that at least a large proportion of the unit groups must be acetylated in the proportion C_{6}H_{6}O.(OAc)_{4}. It has been shown that by the method of Franchimont a higher proportion o
PREV.   NEXT  
|<   67   68   69   70   71   72   73   74   75   76   77   78   79   80   81   82   83   84   85   86   87   88   89   90   91  
92   93   94   95   96   97   98   99   100   101   102   103   104   105   106   107   108   109   110   111   112   113   114   115   116   >>   >|  



Top keywords:

tetracetate

 
formula
 

hydrolysis

 

proportion

 

cellulose

 

groups

 
empirical
 
degree
 

hydrate

 
product

quantitative

 

original

 

derivative

 

formed

 

preclude

 

carbon

 

pointed

 

intermediate

 
fractional
 

partly


esters

 

hydrolysed

 

carbohydrate

 

extreme

 
variation
 

higher

 
saponification
 

subject

 

sufficiently

 
acetyl

determination

 

minimising

 

quantifying

 

produced

 

results

 

statement

 
applied
 

specially

 

precautions

 

ultimate


analysis

 

critical

 

ordinary

 

experimental

 
errors
 
involve
 

method

 

acetylated

 
Franchimont
 

analyses