CHEMICALS
New Amides Are Highly Polar, Soluble Solvents, additives, and plasticizers are most likely uses of N,N-dimethyl derivatives of fatty acids A new series of fatty amides with unusual properties has been developed by C. P. Hall Co. of Illinois (C&EN, March 6, page 3 9 ) . Called Hallcomids, the compounds are A7,N-dimethyl amides of fatty acids having from six to 22 carbon atoms. They are highly polar and very soluble in a number of compounds, and should find use as solvents, additives, and plasticizers, according to Dr. V. P. Kuceski, director of research at the Chicago firm. Many different amides of the fatty acids have been made in the past. "So far as we know, though, no one is making these particular compounds commercially," Dr. Kuceski says. Apparently, chemists have not appreciated one key property of these amides: a higher polarity than almost any other organic compound that has the same ratio of carbon atoms to oxygen or nitrogen. The high polarity of the dimethyl amides stems from methyl groups which replace hydrogen atoms in the unsubstituted amide, Dr. Kuceski
says. The methyl groups seem to keep the amides from bonding to each other, thus allow the unshared electron pair to act more powerfully in hydrogen bonding and to exert other electromeric effects, such as polarizing —NCO— groups. As a result, the carbonyl group of the amides gives up electrons readily and attracts the electron-accepting groups of alcohols, phenols, sulfonamides, barbiturates, and other compounds with acidic hydrogens. Dissolve Water. The high polarity and solvent activity (or complexing ability) of the Hallcomids can be shown by comparing them with fatty acids and alcohols. By contrast with the latter compounds, the amides can dissolve large quantities of water—an unusual property for compounds with long alkyl chains. Coupling this dissolving power with miscibility in a broad range of solvents, the property takes on even more meaning. At room temperature, the amides mix completely with alcohols (up to C 4 ) , ethyl ether, acetone,
methylethyl ketone, ethyl acetate, petroleum ether, benzene, carbon tetrachloride, kerosine, mineral oil, oleic acid, and stearic acid, and dibutyl phthalate. Thus, the Hallcomids should be good couplers between polar and nonpolar systems as well as good co-solvents and solubilizers. Temperature has an unusual effect on the ability of the N,N-dimethyl amides to dissolve water, Dr. Kuceski points out. The compounds separate from solution when heated, as do polyoxyethylene glycols. Apparently, heat causes them to become less polar, thus decreasing hydrogen bonding. Lowering the temperature increases the polarizability. The Hallcomids are more basic than conventional amides. They are about five times as strong as unsubstituted amides when the two are compared as acetic acid solutions. This property plus their hydrogen bonding ability makes them unique solvents in phenolic or other slightly acidic systems. For instance, the amides form soluble complexes when they're added to hydroxybenzoic acid, fatty acids, phenol, or chloramphenicol. Physical properties include: • No unpleasant odors. • Low vapor pressure. • Light colors (to water white). • Stability to hydrolysis. • Alkali and acid resistance.
Rising temperature tlBcreases polarily, affects water .solubility of N,Mroethyl amides ±
20 . / 30, v 40; s
^ 60
Temperature* *>C+ -{ , ->;;/ r"'-:''
AMIDES PURIFIED. Hall purifies amide samples in this column prior to tests to determine chemical and physical constants 64
C&EN
MARCH
13, 1961
The Hallcomids also melt much lower than do ordinary unsubstituted amides. Unsubstituted oleamide, for example, melts at about 68° C , while A7,N-dimethyl oleamide melts near —8° C. The compound thus has the advantage of being an easily handled liquid instead of a solid that must be melted before being pumped or poured into other materials. Insect Repellents, Too. The amides have many potential uses, Dr. Kuceski feels. C. P. Hall has already started testing them as drug solvents, plasticizers, coupling and dispersing agents, stabilizer and antioxidant sol'ubilizers, foam stabilizers, deicers, lubricant additives, lubricants for space vehicles, corrosion inhibitors, and reaction solvents for high temperature work. Some of them seem
to be very good insect repellents. The company is currently producing IV,xV-dimethyl caprylamide-capramide, lauramide, stearamide, and oleamide. The compounds are available in 8-oz. samples and in technical and refined grades. Their market price is below $1.00 per pound. In the past, C. P. Hall (its parent company is located in Akron, Ohio) has been considered as a distributor to the rubber industry. T h e firm, however, is not a newcomer to the manufacturing field. Its products include plasticizers, pharmaceutical intermediates, antifoam and dispersing agents, detergents, emulsifiers, and fatty acid esters. And earlier this year, C. P. Hall introduced some high purity triglycerides for research and testing applications.
March 13, 1961
A SKILLED HAND IN CHEMISTRY... AT WORK FOR YOU
QUALITY means better performance To a great many industries, the name Metasap has meant a particularly high standard of quality for over 40 years. During that time the reliability of Metasap stabilizers, thickeners and lubricants, as well as agents for suspension and flatting, has been amply demonstrated. Listed below are some of the Metasap products. Write for our metallic soap booklet which covers the complete line .. . and feel free to consult us on new applications and developmental problems.
Readers' Information Service Use this handy self-mailer to obtain further information or literature. Simply mark the items desired, fill out the information requested, clip the coupon, fold, staple, and mail. (Please fill out coupon completely.)
Aluminum Stearate (Tri)
Company:
Aluminum Hydroxy Stearate
rr **•
Aluminum Stearate (mono) Aluminum Stearate (Di)
Name: O
Aluminum Palmitate
Barium Stearate
Street: City
Zone-
-State-
Calcium Stearate Lead Stearate
Your Title:
Lithium Stearate
Your Function (Check One): 1 • Corporate Management 2 • Technical Management 3 • Product Research 4 • Product Design & Development
Lithium Hydroxy Stearate 5• 6• 7Q 8•
Process Research Process Design & Development Production—Processing Purchasing
Magnesium Stearate Strontium Stearate Zinc Palmitate
Other (Specify)
Zinc Stearate
CLIP COUPON—Fold along this line—fasten (staple, tape, glue) MAIL
Your Industry:
1 •
Construction
2 •
Food & Kindred Products
3 • 4 • 5 •
Textile Mill Products Paper & Allied Products Printing, Publishing, etc.
6 • 7 n
Chemicals & Allied Products Plastics; Synthetic Resins
8•
Drugs
9 • 10 •
Soap, Detergents, Cosmetics Paints, Varnishes, etc. O D Other (Specify)
11 •
Petroleum Ref., Asphalts,
12 D 13 • 14 n 15 • 16 • 17 • 18 •
Rubber; Plastic Products Leather & Leather Products Stone, Clay, & Glass Products Primary Metal Industries Fabricated Metal Products Machinery & Equipment Transportation Equipment
19 n
Instruments
Lubricants
Metasap Division
NOPCO ^^P*TM NOPCO CHEMICAL COMPANY 6 0 Park Place, N e w a r k , N.J.
Plants: Harrison, NJ. • Carlstadt,N.J. Richmond, Calif. • Cedartown, Ga. London, Canada • Mexico, D.F. ,. Corbeil, France • Sydney, Australia Manufacturing Licensees Throughout the World
MARCH
1 3 , 19 6 1 . C & E N 6 5
