CHEMICALS NEW REACTION:
Sugar +
Aroma tics +
R
HF
New Products
R
HF
water is still formed as a by-product, b u t the new chemical has a heterogeneous ring containing oxygen from t h e carbohydrate's carbonyl. A series of products in which the internal ratio of hydrophobic to hydrophilic parts varies widely can be prep a r e d by adjusting the sizes of the aromatic and the carbohydrate reactants. And, such aromatic derivatives as phenols can b e used to introduce functional groups into the structure.
H C
i
(HC0H)4 CH 2 OH CH 2 0H CH 2 0H
Sugars and Petroleum Unite W i t h HF as catalyst, carbohydrates a n d aromatics react, give n e w route to both old and new chemicals ACS T w o of the NATIONAL cheapest and most MEETING a b u n d a n t chemical raw materials—hyPetroleum dro c a rb o n s and Chemistry carbohydrates—can now be used together as a springboard to new or previously inaccessible compounds. Secret of the process is use of anhydrous hydrogen fluoride—workhorse catalyst of the petroleum and other industries—as a condensing agent. According t o UOP's Carl B. Linn, who developed the process, both his company and Corn Products Refining, also interested, plan to commercialize it and its products. Samples of some of the products resulting are now available, Linn told the Division of Petroleum Chemistry. Chemicals as diverse as detergents, petroleum additives, pharmaceuticals, plasticizers, resins, and germicides can b e made. Some of them gel hydrocarbons in low concentrations; the water soluble compounds are surface active.
132
84
C&EN
SEPT.
16.
1957
Here are some of the combinations that have been tried: toluene with cellulose, glucose, starch, and sucrose; ethylbenzene and glucose; o-xylene and glucose; dodecylbenzene with cellulose; phenol and starch; and 2,4-dimethylphenol with cellulose. HF is so reactive with many organic compounds that you might expect it to "chew u p " the relatively delicate carbohydrate. But surprisingly, its structure remains intact as its carbonyl carbon unites with the aromatic. W h e n carbohydrate polymers a r e used, the catalyst first reduces them to monomers; h e n c e , starch, cellulose, and glucose react similarly. Any given pair of reactants can give several pure products, d e p e n d i n g on ratios and conditions. For example, two moles of aromatic and one of carbohydrate will react to split out water, giving a product with both aromatic segments attached to the terminal carbon of the carbohydrate. On the other hand, t h e reaction can b e directed to give equimolecular amounts of the aromatic a^nd carbohydrate. In this case.
• Making t h e Chemicals. The carbohydrate and aromatic reactants are sealed in a stainless steel autoclave e q u i p p e d with a thermocouple well, pressure gage, and valve lines to bottom and top. A b a t h of dry ice cools the exothermic reaction. W h e n the reaction is complete, the product is separated from excess hydrogen fluoride and is purified. T h e process offers a convenient and economically practical route to the products resulting, according to Linn. T h e only method previously available for the preparation of materials of this type, developed by Hurd and Bonner under a Corn Products fellowship, was too expensive for commercial use. While U O P a n d Corn Products both expect t h e reaction products to be used commercially per se, they also see the chemicals in pure or crude state as intermediates for preparation of new compounds. Laboratory samples of two products of the n e w process are available on request to Corn Products. One, 1-deoxyl,l-di-(o-xylyl)-D-glucitol, is made from o-xylene and starch. It is stable to heat and alkali and appears to dehydrate in the presence of acids. A second, l-deoxy-l,l-di-(p-hydroxyphenyl)-D-glucitol, is made from phenol and starch. This compound is stable in alkali b u t is unstable to heat and acids. T h e r e is evidence that it might b e an intermediate for resin preparation. n
