US3622581A - Perinones - Google Patents

Abstract

10,22-DIOXODIBENZIMIDAZO (1, 2-B : 1'', 2''-B'') DIBENZO (DE: D'' E'')-P-DIOXINO (2, 3-G : 5, 6-G'') DIISOQUINOLINES AND ISOMERS ARE PREPARED, BEING USEFUL AS LUMINESCENT MATERIALS OR PHOSPHORS.

Description

United States Patent Primary Examiner-Donald G. Daus Anomey- Frank R. Ortolani ABSTRACT: 10,22-dioxodibenzimidazo (l, 2-b l, 2-b') dibenzo (de: d e)-p-dioxino (2, 3-g 5, 6-g') diisoquinolines and isomers are prepared, being useful as luminescent materials or phosphors.

Inventor Edward E. Jafie Union, NJ. Appl. No. 795,506 Filed Jan. 31, 1969 Patented Nov. 23, 1971 Assignee E. I. du Pont de Nemours and Company Wilmington, Del.

BERINONES 2 Claims, 2 Drawing Figs.

[1.8. CI. 260/282, 106/288, 252/301.2 R, 260/346.3, 260/578, 313/109 Int. Cl. C07d 57/02 0 PAIENTEDunv 23 197i IG.Z

mvsm"on EDWARD E. JAFFE flmfi 200 FlG.l

ATTORNEY TEMPERATURE PERINONILS This invention relates to organic phosphors which are excited by long wavelength ultraviolet light and respond with a bright red emission.

The luminescent materials commonly used as thin layers on the inside of fluorescent lamps, high-pressure mercury vapor lamps and sign tubings are generally referred to as fluorescent powders or phosphors. These are invariably inorganic in nature, and some of the best and most widely publicized are expensive. Under the circumstances, the possibility of utilizing organic compounds for similar purposes should be considered. Heretofore there has been no organic candidate which showed sufficient response under the conditions of use to render it of interest.

STATEMENT OF THE INVENTION The present invention provides novel diperinone compounds represented by the following structural formulas:

and

of is l0.22-diox- The compound The compounds of this invention exhibit fluorescence when excited by 2537A. radiation; the exciting radiation in the usual fluorescent lamps, and by the 3660A. radiation which constitutes an appreciable proportion of the emission within mercury vapor lamps. The'outstanding response of these new phosphors to excitation with 3660A. radiation, and the reddish color of the emitted light-desirable for "correcting" the color of mercury lamps-make these products of particular value for use as a component part of mercury vapor lamps. The phosphors also are useful in pigment form. Other useful applications of the discovery will occur to the artisan.

In the drawings:

FIG. lshows the fluorescent spectrum for a diperinone compound of the invention, having thereon a prior art spectrum for comparison purposes. The wave length of fluorescent emission is plotted against arbitrary intensity units, the spectrum indicated as A being that of a diperinone of this invention, and B being that for one of the best currently available red phosphors.

FIG. 2 shows a graph on which intensity of fluorescent emission in arbitrary units is plotted against temperature.

These new diperinone compounds of this invention are prepared by chemical techniques presently known to the artisan. Of the syntheses available, a preferred route is. schematically, as follows:

l. Naphthalic anhydride is sulfonated according to the method of Anselm and Zuckmayer (Ber. 32. 3283 1899)):

o o .0 0 0T 0 2. The 3-sulfonuphthalic anhydride thus prepared is converted to 3-hydroxynaphthalic anhydride by the method of Zollinger Helv. Chim. Acta 33,530 l950)):

3. The resulting anhydride product is then brominated by the method of Dziewonslti et al. (CA. 26. 5942( l932)):

4. The brominated product is condensed with o-phenylenediamine to perinone:

5. In the final reaction the diperinone derivative is prepared by an intermolecular; dehydrobromination of 2 mols of the perinone, thereby forming a compound of this invention, that is, one of compounds 1, II, and III hereinbefore identified.

The invention will be further described with the following specific example, in ,which the details are given by way of illus-. tration and not by way of limitation.

EXAMPLE A mixture of 2.93 parts (0.0l mols) of 3-hydroxy-4-bromonaphthalic anhydride, 1.08 parts (0.0l mols) of o-phenylene diamine and 210 parts of acetic acid is heated to reflux, and refluxing is continued for hours. During the refluxing a heavy yellow precipitate forms, which increases in amount as the refluxing proceeds. This product is isolated by filtration, and is washed with water until free of acid and finally dried. Yield is 3.2 parts (i.e. 87.7 percent of theoretical, assuming a product corresponding to the composition C l-l BrN O The melting point of a small sample of the hydroxybromoperinone crystallized from a large amount of hot acetic acid is 328 to 340 C., probably indicating a mixture of the compounds as shown in formulas Iv and V.

Analysis C. 59.20. H. 2.47; N. 7.67

Calculated for C ,,H.,BrN,O,:

. 4 C. 59.10; H. 2.84; N. 7.36

Found:

'A mixture of one part of the hydroxybromoperinone, one part of anhydrous potassium carbonate and 60 parts of dry nitrobenzene is heated to reflux and maintained at reflux temperature for 5 hours. During this operation any water which forms is permitted to escape from the reaction mixture. The

' hot mixture is filtered and the filter cake washed thoroughly with nitrobenzene, then successively with alcohol, water and again with alcohol. The yield of productis 0.23 parts (35.8 percent of theory, assuming a molecular weight of C H N. 0.). (In another example carried out in essentially the same manner, a yield of 50.2 percent is; obtained.) In still another experiment wherein some cupric acetate is included in the hydroxybromoperinone reaction mixture. the yield of product is about 36 percent.

The product is purified by recrystallization from acid as follows: Asolution of 2.63 parts of the pulverized dry product in 18.4 parts of l00'pe rce n,t sulfuric acid is prepared by stirring at a temperature not above C. After solution is complete, as judged by microscopic examination of a sample, the acid concentration is gradually lowered to 90 percent by dropwise addition of water, the rate being such as to maintain the temperature of the mixture below 10 C. throughout. The mixture is stirred for an additional hour at 10 C., and the precipitated sulfate of the desired product is filtered and thoroughly washed with 80 percent sulfuric acid. The sulfate filter cake is then hydrolyzed with ice and water, and the resulting diperinone compound isolated by filtration and washing free of acid to give 1.01 parts of red shade yellow solid. For analytical purposes 1.26 parts of the product is extracted twice with 450 parts of nitrobenzene and once with 570 parts of boiling N,N-dimethyl formamide. The purified sample does not melt up.to"4'00 C.

Analysis 7 Calculated forCgfluNiorz C, 76.00; H. 2.82; N, 9.86 Found: C. 75.04; H. 2.80; N. 9.95

A diperinone product prepared according to the general procedure of the example has been examined and tested. FIG. I shows a comparison of the fluorescent emission spectrum (A) of the product obtained with one of thebestcurrently available red phosphors'(y Eu,, VOl). (B) under excitation by relatively long ultraviolet radiation(3660A). Intensities are on a qualitative scale. Visual observation confirms the appreciably greater brightness of the product of this invention. It is concluded that such strong, deep red emission under excitation at 3660A. would render the product of this invention superior as a color-correcting phosphor when used for this purpose, for example on the inner surface of the outer envelope of high-pressure mercury vapor lamps, whereby the visual appearance of the resulting light would be changed from blue to yellowish while at the same time increasing the lumen output. FIG. 11 shows the relative intensity of the fluorescent emission spectrum of the product at temperatures up to 300 C. It will be noted that even though the intensity decreases by approximately 40 percent at 300 C. by comparison with that at C. as shown in FIG. 11 where the intensity of emission in arbitrary units is plotted versus temperature, it is still higher than that of Y Eu VO See FIG. 1, assuming that the emission intensity ofthe latter were constant throughout this temperature range. Consequently, the product of this invention would be expected to be a superior red phosphor for color-correction of discharge devices excited by light of 3660A. even at the higher temperature.

The product of this invention is a red-shade yellow material which is extremely insoluble in common organic solvents. When dispersed in an organic. vehicle, for example lithographic varnish, and drawn down on a support, it is a redshade yellow pigment which luminesces strongly upon stimulation by ultraviolet radiation. After exposure for 72 hours some darkening occurs, but most of the luminescence is still retained. Even after dilution of the dispersion with ZnO (1:100) some luminescence is observed on shining ultraviolet light on the extended dispersion.

While the invention has been described above with certain detail, it should be understood that changes can be made by the artisan. For example, in preparing diperinones other solvents, temperatures of reaction. and methods of purification. may be used in place of the corresponding condition set forth in the example. Also, although the perinone was made by condensation with o-phenylene diamine, it is obvious that the reaction is also applicable to condensation with other orthoor peridiamines. These would include 1,2- diaminonaphthalene, 2,3-diaminonaphthalene, l ,8-diaminonaphthalene, etc. These reactants as well as the aforementioned o-phenylene diamine, may be substituted by such groups as lower alkyl. lower alkoxy, halogen, etc. to produce correspondingly substituted diperinones.

What is claim is:

I. A diperinone compound having one of the structural formulas and 2. A red shade yellow compound having the structure given in claim 1 which luminesces upon stimulation by ultraviolet light. I

Claims (1)

1. 2. A red shade yellow compound having the structure given in claim 1 which luminesces upon stimulation by ultraviolet light.

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