New Derivatives of Isatoic Anhydride Offered Versatile intermediates have po tential in dye, agricultural, phar maceutical, and flavoring industries
DEVELOPERS. Dow's Dr. L. F. Sonnabend, Dr. J. D. Doedens, and Dr. Ε. Η. Rosenbrock discuss diphenyl oxide derivatives and structural formulas shown on board
switch much of its Midland phenol production to diphenyl oxide, used mainly in heat transfer as part of Dowtherm A, a eutectic mixture of 2 5 % diphenyl, 75% diphenyl oxide. Since the twenties, Dow has recycled di phenyl oxide, using the mass action effect to suppress excess production. But the price of phenol is now down to 13.5 cents per pound from 18 in 1961. The toluene oxidation process of Dow's three new plants is probably more efficient, and research has pro duced a multitude of promising deriv atives of the diphenyl oxide. The company is reluctant to say what percentage of Midland's 235 million pound-per-year phenol ca pacity can be shifted to diphenyl oxide simply by not recycling. However, even 10% would mean annual ca pacity of 23.5 million pounds. And the percentage might be as high as 50%. At this level, U.S. phenol ca pacity would drop by 118 million pounds per year, wiping out a large part of the difference between pro duction and capacity. Many Possibilities. Diphenyl ox ide reacts with formaldehyde and hy drochloric acid to yield chloromethylated derivatives. Functional groups range in number from zero to three. Or DPO can be halogenated, then ammonated or hydrolyzed to give de rivatives with reactive groups corres ponding to aniline or phenol. From these polyfunctional products many more can be made. Chloromethylated DPO reacts with many materials con taining active hydrogens. It can be self-polymerized, but gives off hydro chloric acid, undesirable in most uses.
Some of the derivatives give im proved properties to other condensa tion polymers, notably high tempera ture stability, chemical resistance, and light, stable colors. For instance, temperature stability of these poly mers is far better than that of bisphenol A, a diol used in epoxide resins and other systems. Another example would be Monsanto's five-ring polyphenyl ether used as a high tempera ture lubricant by the Air Force, though this material is made by a different process from different materials. The number of possible compounds and intermediates based on crystalline, low-melting DPO is large. Using just chloromethylated DPO, Dow has studied alcohols, amines, ethers, esters, mercaptans, and condensation prod ucts of aromatic compounds. There are many possible applica tions, especially as difunctional ma terials. The alcohols could be used as glycols or resin intermediates. Amines could be epoxy catalysts, part of alkyd resins. Esters might be used as plasticizers or as intermediates for transesterifications. The viscous mercaptans containing about 20% sul fur could be used as rubber accelerat ors. A crystalline carboxylic acid having a melting point over 300° C. could be used as a resin intermediate or dibasic acid. A very viscous, inert toluene reaction product could be used in gas chromatography or as a heat transfer fluid. Reaction products of chloromethylated DPO and phenol or tertiary butyl phenol are themselves low molecular weight polymers pos sibly useful as Novoloc or varnish resins.
Two new members of the isatoic an hydride family—the 6-chloro and the 6-nitro analogs—are being offered com mercially for the first time by Maumee Chemical Co., Toledo, Ohio. The two compounds have chemistry that parallels that of isatoic anhydride, are actually derivatives of p-chloroaniline and p-nitroaniline. Targets for the 6-chloro- and 6-nitroisatoic anhydrides are the dye, agricultural, pharmaceuti cal, and flavoring industries. Hydrolysis of 6-chloroisatoic anhy dride and its nitro analog give a ready source of 5-chloro- and 5-nitroanthranilic acids. This could be of particu lar interest to dye and pigment manu facturers. And, as forerunners of other 5-chloro and 5-nitroanthranilate esters and amides, these two new com pounds look especially promising as intermediates for agricultural chemi cals. Maumee first offered isatoic anhy dride as a development chemical in 1956. Since then use of IA has in creased considerably and it's now being used on a commercial basis. The isatoic anhydrides are potential parents of a large number of hetero cyclic compounds. Building Blocks. Benzoyleneureas or benzoylenethioureas could be pharmaceutical building blocks and thermally resistant nuclei. They result from the condensation of isatoic an hydride with the appropriate isocyanates or isothiocyanates. Substituted quinolines can be derived from isa toic anhydride and various active hy drogen compounds of the acetoacetic ester type. Isatoic anhydride also gives various anthranilamides, o-carboxycarbanilides, and benzanils in simple one-step reactions. By ring clo sure of these compounds, other nitro gen heterocyclics can be easily made. Isatoic anhydride reacts rapidly and almost quantitatively with methanol to give methyl anthranilate, an arti ficial grape flavor used widely in fla voring. This same type of reaction with thiols, amines, and phenols (which are largely responsible for of fensive household and industrial odors) makes the isatoic anhydride family excellent deodorant candidates OCT. 15, 1 9 6 2
C&EN
71
C&EN
COMMERCIAL CHEMICALS
PROGRESS REPORT
Companies added these products to their lines during the past four weeks Material Reinforced Teflon (Salox compounds)
Company
Allegheny Plastics, Inc. Coraopolis, Pa.
Luminescent plastic (Polylite)
American Polymer & Chemical Corp. Natick, Mass. Bauer Bros. Co. Springfield, Ohio
Nonelectric magnets Alumina ceramic substrates (Smooth-Strate) Hexyl acetate
Electro-Ceramics, Inc. Salt Lake City, Utah Enjay Chemical Co. New York, N.Y. Kaiser Aluminum & Chemical Sales, Inc. Oakland, Calif. Lithium Corp. of America New York, N.Y.
Aluminum ingot (Mark IV) Organolithiums Silica aerogel (Santocel 62)
Inorganic Chemicals division of Monsanto Chemical Co. St. Louis, Mo. Neville Chemical Co. Pittsburgh, Pa.
Indene derivatives Aryl mercaptan derivatives (2-isopropylethylphenolf 4-bromothiophenol) Fluorocarbon extrusions (Fluorosint)
Pitt-Consol Chemical Co. Library, Pa. The Polymer Corp. Reading, Pa.
Nonflammable coating (Stripcote Stik-Pruf) Plasticizer (Flexol NODP) Molding compounds (JMD-4701, JMD-4921, JMD-5501) Submicron thoria powder
Rubba, Inc. New York, N.Y. Union Carbide Chemicals Co. New York, N.Y. Union Carbide Plastics Co. New York, N.Y. Vitro Laboratories division of Vitro Corp. of America West Orange, N.J. Westlake Plastics Co. Lenni Mills, Pa.
Polycarbonate (Zelux)
Features and Uses Features reduced thermal expansion, low deformation resistance, and high heat transfer coefficient Clear, two-component plastic for luminescence in various colors depending on activator For removing tramp metal, rust particles, and foreign matter from materials b'eing processed For microminiature, thin-film, integrated circuitry operating up to 800° C. High boiling, oxygenated solvent for use in lacquers Casting ingot with minimum porosity and oxide levels, improved surface condition, and better mold-filling Developmental quantities of nine compounds for use in Grignard-type syntheses and polymerization reactions Test quantities to paint manufacturers to improve lacquers, varnishes, and coatings Developmental quantities for use in making insecticides, plastics, agricultural chemicals, and pharmaceuticals Developmental quantities for use in antioxidants, insecticides, pharmaceuticals, and resins Created from ceramics with Teflon binder having low thermal expansion rate and good resistance to deformation To protect spray booths and work areas from paint and adhesives To improve low temperature flexibility of vinyl and other resin systems Polypropylene compounds with built-in antistatic properties Developmental quantities of 400-A., 99.8% pure Th0 2 Transparent, high impact, heat resistant, and self-extinguishing material
Available in commercial quantities unless otherwise noted.
in many applications. For instance, powdered cleanser containing a small amount of isatoic anhydride quickly removes fishy odors from hands and utensils. Another promising application of high industrial importance stems from the fact that isatoic anhydride affords a convenient means of attaching an aminobenzoyl radical to most functional substrates. Cotton has been successfully 'anthranilated' to give a rot-proof fabric which retains the important property of "hand" with little or no loss of other desirable proper72
C&EN
OCT. 15, 1962
ties. Similar reactions with starch and other polysaccharides confer cationic properties to these otherwise neutral compounds. Other Potentials. And isatoic anhydride has other potentials, too. It releases carbon dioxide rather readily, and merits consideration as a blowing agent in elastomers and rigid plastics. A close derivative of isatoic anhydride, 4-ketobenztriazine, also falls in this category, releasing nitrogen at elevated temperatures. The 4-ketobenztriazine is an internally stabilized diazo compound which will couple under
the proper conditions, making it of interest to the textile printing and duplicating process fields. Chloro- and nitroketobenztriazines are easily obtained from the correspondingly substituted isatoic anhydrides. Another recent addition to Maumee's product line is N-methylisatoic anhydride. This compound readily gives dimethyl anthranilate, a flavor and odor component, and it will react much like isatoic anhydride to give a variety of N-methyl nitrogen heterocyclic systems, of interest in pharmaceutical research.
an
pound plasticizer specifically designed
for PVA emulsions! Eastman Plasticizer To demonstrate the effectiveness of Eastman Plas ticizer 135, its performance in each of nine differ ent commercial PVA emulsions was compared with that of one of the industry's standards, dibutyl phthalate. The following tests offered convincing proof that the new Eastman plasticizer is compara ble to dibutyl phthalate in all important respects. viscosity stability freeze-thaw resistance minimum film forming temperature film elongation film tensile strength aging characteristics and retention in PVA water spotting plasticizer loss in water adhesion to cellophane tack time bond strength
As a matter of fact, the only significant difference between Eastman Plasticizer 135 and dibutyl
phthalate is the $47.00 you save on every drum or the $3,320 you save on each 4,000 gallon tank wagon when you use this new plasticizer. Contact your Eastman representative or com plete and return the coupon for technical data and a sample of new Eastman Plasticizer 135.
J C j a s t m a i l
CHEMICAL PRODUCTS, INC.
CHEMICALS DIVISION, KINGSPORT, TENN , S u b s i d i a r y of Eastman Kodak
Π
Send Technical Data Sheet No. L-112
Π
Send working sample of Eastman Plasticizer 135
Company
NAME
.
POSITION COMPANY SALES OFFICES: Eastman Chemical Products, Inc., Kingsport, Ten nessee; Atlanta; Boston; Buffalo; Chicago; Cincinnati; Cleveland; Dallas; Detroit; Greensboro, North Carolina; Houston; New York City; Phila delphia; St. Louis. Western Sales Representative: Wilson & Geo. Meyer & Company, San Francisco; Los Angeles; Salt Lake City; Seattle.
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C & ΕΝ
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NEW CHEMICALS
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A new series of synthetic thermosetting monomer products is under development by A. E. Staley Mfg. Co., Decatur, 111. The series has potential application in reinforced plastics, building materials, and many other industrial uses, the company feels. Stapon monomers are currently in semicommercial production at the company's Decatur synthetic polymer pilot plant. The monomers contain functional ethylenic unsaturation, and are said to copolymerize readily with styrene, vinyl chloride, acrylate, and acrylonitrile monomers. Patent applications on the process for making the monomers are pending in the U.S. and several other countries. C 1
Liquid ketone peroxide, named Lupersol DNF, has been introduced by Lucidol division of Wallace & Tiernan Inc., Buffalo, N.Y. Its self-extinguishing feature and nonshock sensitivity are its most significant safety advantages, according to the company. It can be used for sprayup, layup, or room temperature curing of polyesters resins, the company adds. C2
Caloxol, a powerful desiccant which is said to prevent porosity caused by moisture in natural and synthetic rubber, has been introduced by Berkshire Chemicals, Inc., New York, N.Y. Among the advantages claimed by the company are easier handling, no settling, and less chance of spoilage by atmospheric moisture. C3
Strippable film to protect parts and materials for outdoor storage has been introduced by Johnson-March Corp., Philadelphia, Pa. Liqui-Tarp is said to offer waterproof protection for periods of u p to one year, with one application. The coating can reduce cost of storage, packaging, handling and shipping a variety of products in the metal working, chemical, paper and paper products, appliance, exporting, and industrial fields, the company says. C4
Large high purity, high density, single crystals of three refractory metals are now available from Westinghouse Electric Corp., Pittsburgh, Pa. Alloys, as well as single crystals, of 74
C&EN
OCT. 15, 196 2
molybdenum, tantalum, and niobium can be supplied, the company says. The large crystals were developed because of the need for more knowledge about the fundamental properties of refractory metals. C5
Liquid to control chrome contamination in electrocleaners and copper strikes has been introduced by Northwest Chemical Co., Detroit, Mich. Alkontrol L not only controls chrome but softens water in electrocleaners, the company claims. Only visual control is needed, the company adds. C 6
Silicone diffusion pump fluid is said to produce ultrahigh vacuum without refrigeration, according to the manufacturer Dow Corning Corp., Midland, Mich. Dow Corning 705 is chemically inert, nontoxic, clean, and resists gamma radiation, the company says. C7
Unsaturated polyester resin, CoRezyn 601, is available from Commercial Resins division of Interplastic Corp., St. Paul, Minn. After catalyzing with MEKP, the resin cures at room temperature to form clear, tack-free glossy surfaces with exceptional mar resistance, the company says. C8
Polyethylene of low density for very high speed extrusion coating is commercially available from Union Carbide Plastics Co., New York, N.Y. Bakélite DFD-0701 Natural 7 can be applied at speeds in excess of 1000 ft. per min. with good adhesion and low neck-in, Union Carbide says. C9
Tooling gel coats especially designed for reinforced plastic mold making have been introduced by Color division of Ferro Corp., Cleveland, Ohio. Formulated with resins that possess high heat distortion points, the gel coats are able to withstand repeated laminating cycles, Ferro says. C 10
Complete line of products for cadmium and zinc plating, including premixed brighteners, plating concentrates, purification agents, and wetting agents has been developed by Enthone, Inc., New Haven, Conn. Trade named Enthobrite, the line is
"HOW'S OUR SCRUB?"
CL-222 HAS THE BEST SCRUB YETS
N E W VINYL-ACRYLIC EMULSION I M P R O V E S PAINT S C R U B U P TO 2 0 %
CHEMICAL COMPANY Celanese Chemical Company, Dept. 754J 522 Fifth Avenue, New York 36, N.Y.
I'd like complete data on new CL-222. Please send Π technical literature Π sample Name Company
.
Address City
Zone
State
,
CL-222 is a completely new vinyl-acrylic emulsion from Celanese. A copolymer of high molecular weight, CL-222 has superior scrub resistance and high critical PVC. It is the result of extensive Celanese research in emulsion polymer technology. As an interior paint vehicle, CL-222 offers excellent scrub, pigment acceptability and color uniformity. It provides good leveling and flow and is compatible with reactive pigments. Films formed from CL-222 exhibit high tensile strength and elongation. AZI test methods indicate that paints properly formulated with CL-222 have excellent freeze-thaw and heat stability. Why not evaluate new CL-222 vinyl-acrylic emulsion for your self. The coupon will bring you full information. celanese® Celantse Chemical Company is a division of Colanoso Corporation of America. Canadian Affiliate: Canadian Chemical Company Limited, Montreal, Toronto. Vancouver Export Sales: Amcel Co., Inc., and Pan Amcel Co., Inc., 522 Fifth Avenue, New York 36, Ν. Υ.
said to incorporate the latest advances in brightener technology and present significant advantages in brightness, throwing power, efficiency, and econ omy. C 11
Improved ceramic media has been in troduced by Filtros Inc., East Roches ter, N.Y. The new media, designated Q-type porous ceramic, is said to op erate efficiently in temperatures u p to 1200° F . in filtering or diffusing hot gases and liquids. Special formula tions can be made for even higher temperatures, the company adds. C12
Gasket or sealing compound for ap plications u p to 400° F . is offered by Connecticut Hard Rubber Co., New
Haven, Conn. CHR Viton Sponge can be used where there is contact with corrosive fuels, oils, chemicals, acids, and solvents, the company says. C 13
Dry back adhesive-coated felt has been developed by American Felt Co., Glenville, Conn. AFCO No. FC-151 can be used in bonding felt to metal or other surfaces where toughness, flexibility, and resistance to heat and oil are important operating require ments, American Felt says. C 14
Further useful information, on keyed Chemical items men tioned is readily available . . .
Use handy coupon on page 78
October 15,1962
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.)
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