CHEMICALS with a molecular weight of 1 4 2 . 1 1 , melting point of 152° to 154° C , and is soluble in water, acetone, alcohol, and ethyl acetate. Pfizer has not outlined the precise fermentation procedure. Kojic acid was isolated b y K. Saito in 1907 from Aspergillus oryzae grown on steamed rice. Reactions O b t a i n e d . Acidic p r o p erties of the compound result from its nuclear hydroxyl group. I t is not precipitated b y the addition of aqueous or ammoniacal silver nitrate; neutral, basic, or arnrnoniacal lead acetate; mercuric chloride, tannin, phosphotungstic, or phosphomolybdic acids. Some of t h e hydroxyl group reactions are interesting. T r e a t m e n t w i t h diazomethane in ether solution gives a quantitative yield of 2-hydroxymethyl-5-methoxy-'y-pyrone. Reaction of kojic acid with phenacyl halides yields phenacyl ether. A n anomalous halide-containing c o m p o u n d is formed when kojic acid reacts w i t h the phenacyl halide in methanolic sodium methoxide. Treatment of this comp o u n d with water results in t h e plienacyl ether. Aliphatic Ether. It is reported that treatment of the acid with thionyl chloride results in a n excellent yield of 2-chloromethy r l-5-hydroxy-'y-pyrone. Its treatment with triphenylchlorometh.ane in pyridine is said t o yield the aliphatic ether. Two moles of triphenylchlorom e t h a n e were also reported to give the same product. Allyl kojate (2-hydroxymethyl-5-allyloxy-y-pyrone) has been prepared by treating kojic acid with allyl bromide and sodium methoxide in methanol. Various researchers h a v e prepared esters of kojic acid a n d acetic, benzoic, a n d phenylcarbamic acids. Acetylation with acetic a n h y d r i d e or acetyl chloride has usually yielded t h e diacetate. Treatment of kojic u n d e r FriedelCrafts acylation conditions is said to yield esters o£ the aliphatic hydroxyl group. Another investigator reported t h a t 6-benzoyl kojic acid may b e prep a r e d in a 40% yield.
Pfizer's five-man biochemical research and development team which developed fermentation process for producing commercial quantities of kojic acid. Donald A. Kita, research biochemist (left foreground), holds a beaker of kojic acid in its fermenting state and a vial of the pure crystalline material. Looking on are: Walter Nazarewicz, supervisor, pilot plant (right foreground), and (background, left to right) Andrew J. Schmitz, head, biochemical process development department; Don J. Badia, supervisor, pilot plant; and Sam C. Beesch, industrial microbiologist
Reactivity A r o u n d the Ring Pfizer's fermentation process yields another commercial product — kojic acid, a multifunctional pyrone -jv^ojic ACID, a multifunctional pyrone • " - discovered a half century ago by Japanese researchers, has been placed in production as another commercial fermentation chemical by Chas. Pfizer and Co. An acid weaker even than carbonic acid, kojic is reactive at every position and forms a n u m b e r of products with varied a n d important uses in industrial chemistry. Among them are m e t a l chelates, pyridones, pyridines, ethers, esters, azo dyes, aldehyde condensation products, halogen derivatives, Mannich bases, and the products of cyanoethylation. Kojic acid has also been found to possess some bacteriostatic action, inhibiting the growth of streptococci, staphylococci, and Sheigella paradysenteria. Metal C o m p l e x e s . Perhaps the most important property of kojic acid is its ability to form stable metal chelates at the 4- a n d 5-ring positions. Metal complexes or chelated metals are in current use as inhibiting agents, antioxidants, a n d as water softeners. Small quantities of chelating agents may have some use in the food and pharmaceutical industries for control2556
ling the action of trace metals. The acid has a good ultraviolet absorption curve. Allan J. Greene, director of commercial development for Pfizer, says that some dyes obtained from the compound possess fastness to light when applied to cotton, silk, a n d wool. Insoluble salts are formed with kojic acid a n d copper, iron, and zinc, a n d other salts and metal complexes have been prepared containing sodium,' barium, calcium, strontium, tin, mercury, and other metals. Kojic acid is a tan crystalline powder
Reduction Products Metal Complexes Esters, Ethers, Salts -
• Mannich Bases
11 J—CH2OH rf Y I
> Esters, Ethers, Halogen and Sulfur Derivatives, Amines
Pyridones, Pyridines Kojic acid, 5-hydroxy-2-(hydroxymethyl)-l,4-pyrone, is multifunctional and reactive at every position CHEMICAL
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IOTSEPIEEBSirEFLE pressure-sensitive adhesives foi
I B^^T
Homogeneous blends of rubber a n d resins in water,
gasketing m a t e r i a l s . . . for pressure-sensitive labels and
Dispersites m a y be diluted witli w a t e r . There are n o
wall coverings. T h e y can be applied by knife or roller
expensive inflammable solvencs. N o special p r e c a u -
coater, spray, or brush.
tions for prevention of fire or explosion are necessary.
W h a t e v e r your adhesive application there's an
W i t h a solids c o n t e n t of 7 0 to 75 per cent, shipping,
economical Dispersite® for i t . . . a n aggressive adhesive
handling, and storage costs are low.
that sticks a t a touch b u t which strips off cleanly.
Dispersite adhesives are being economically used o n a l l types o f pressure-sensitive t a p e s . . . f o r m a n y
For bulletin N C - 5 5 - 1 , a n d s a m p l e s of t a p e s using Dispersite a d h e s i v e s , w r i t e t o us on y o u r company l e t t e r h e a d .
D i v i s i o n o f Unlired S t a t e s R u b b e r CompaLnLj
I_I. MAUOATUCK NAVGATUCKJ I
NausJa-tuLck, C o n n e c t i c u t
JRTJBBER
B R A N C H E S : Akron • Boston . Charlotte • Chicago • LosAngeles • Memphis • iN'ewYork . Philadelphia • IN C A N A D A : Naugatuck Chemicals, Elmira. Ontario Rubber Chemicals • Synthetic Rubber •Plastics • Agricultural Chemicals • Reclaimed Rubber • Latices • Cable Address: Rubexport, N . Y. VOLUME
3 3,
NO.
24
•
•
•
JUNE
13,
1955
2557
CHEMICALS^
rA s I
IJisïalw^^mAPAHOE GHtWIMtSrnfÇr (2&ctjtd &cic& a& t&eae &e t&e tett&attA cv&y Scherir.g Cerp. Anderson Laboratories, Inc. Schieffelin & C o . Syntex, S . A .
Panogen, Inc. The Sherwin-Williams C o . HofFman-LaRoche Inc. Gedeon Richter, S . A . a n d m a n y others
Use A R A P A H O E f s r s p e c i a l CUSTOM SERVICES? • A R A P A H O E is remotely located at Boulder, Colorado. • This isolation is an important factor in the security considerations imposed by confidential or exclusive contract production. • Yet, being only 3 3 miles via Denver-Boulder Turnpike From Colorado's capitol city and commanding ample rail, trucking and airline services, the advantages of greater inspiration and efficiency induced by the high, dry, mountain-country atmosphere and of the home-town availability of the University of Colorado's outstanding Department of Chemistry, more than compensate for the brief time away from the large chemical centers. • A R A P A H O E ' s keynote in selecting equipment always has been and is flexibility. Range of services is not tied to present equipment . . . is not limited by it. Company has money and credit to buy according to the requirements of its undertakings. Why not turn to A R A P A H O E as a second plant in which to have those items produced with which, for one reason or another, you do not want to be bothered—yet over which you wish to keep exclusive control? Address your inquiry to Dept. *'D**
ARAPAHOE SPECIAL PRODUCTS, INC.
Fertilizer Combines High Nitrogen with Slow Release D u Pont's new fertilizer material, Uramite, releases adequate nitrogen for plants continuously and uniformly throughout the growing season, says company. I t combines a 3 8 % nitrogen content with a prolonged release-rate. Chemically, Uramite is a mixture of methylene ureas. Although almost completely water-insoluble, Uramite dissolves over a period of months at a rate conformable with moisture and temperature. T h e slow release rate of Uramite is of particular importance to professional growers of turf a n d ornamental plants, and D u Pont says it plans that initial supplies of Uramite will be marketed to these groups. CS 2
1970-128th Street · BOULDER, COLORADO Producers
of Special
Organic
Compounds
for rapid and precise measurement of pressure and vacuum
MB". A B S O U J T H AHE> D I F F E R E N T I A L
anometers
for industry • pilot plant and laboratory
T o cover the full range of pressure and vacuum measurements in the laboratory, pilot plant a n d industry, Emil Greiner offers its new Absolute and Differential Manometers. With these Manometers you c a n achieve either absolute or differential manometric measurements with unprecedented simplicity and high precision. Only a single reading is required t o obtain a precise measurement a u t o m a t i c a l l y corrected for ambient temperature a n d reduced to a height of mercury at 0° C. G10705A Range: 0-200 mm. (Glass only) ea. 29.50 G10705 Range: 0-200 mm. (with Stand) ea. 39.50 G10708 Range: 0-800 mm. (Glass only) ea. 39.50 G10709 Range: 0-800 mm. (with Stand) ea. 79.50
G10705 For More Complete information Write For "Constant Pressure and Vacuum Contra! Manual"
The Emil Greiner Co., Dept.223 20-26 N. Moore Street, New York 13, N. Y. Please send me Instant Pressure & Vacuum Control Manual. NAME
Condensation Yield. Treatment of kojic acid with paraformaldehyde and sodium carbonate in ethanol has resulted in an 8 1 % yield of 2,6-di-(hydroxymethyl) - 5 - hydroxy - y - pyrone. Condensation of kojic acid with acetald e h y d e gave a 5 3 % yield of t h e 6-ahydroxyethyl derivative. Cyanoethylation of the product has recently been reported. T h e nitrile was not isolated b u t was hydrolyzed directly to the acid which was obtained in an over-all 46% yield. Pfizer says that a characteristic reaction of gamma-pyrones is the substitution of the ether oxygen atom of the pyrone nucleus by nitrogen (ammonia or primary amines). It says that this type of reaction h a s been carried out with derivatives of kojic acid. Kojic acid has been reported to absorb four to six atoms of hydrogen depending on the catalyst a n d conditions of hydrogenation. However, other reports conflict as to t h e nature of the products obtained. CS 1
• Rubber Corp, of America is offering R C Plasticizer, BD-8 (butanediol dicaprylate). Compound is said to exhibit superior low temperature behavior, improved resistance to extraction, a n d to be compatible with many synthetic rubbers. CS 3 • Du Pont is offering a new 2-lb. package of Lignasan fungicide, blue stain control chemical for lumber. New package makes it easier t o prepare recommended concentration for lumber treatment and also reduces exposure to the chemical since no scooping or weighing is necessary. CS 4
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