DE2004316A1 - Perinons - Google Patents

Description

^ Haita-Ä, Brauns ': - ^: \ r ^{,:' -:.} ■ / ■ -,

Munich & e, PBreanauerate 28 ";.;_:; ^ - \ 3Ov January. 1970

ι ./BB Ρ0ΗΦ ds iBMOims mo il _f Delaware (Y

Ferinones

The invention relates to organic phosphors which "by Long-wave fltraviolet light are stimulated and with address a bright red emission-i -—- ■ -. ■ -

The luminescent materials, which are usually used as thin layers on the inside of fluorescent lamps, high pressure mercury vapor lamps and sign tubings, are commonly referred to as fluorescent powders or phosphors. These are invariably inorganic in nature, and some of the best and most widely used are costly. In these circumstances, the possibility of using organic compounds for similar purposes should be considered. So far, there has been no organic representative of such compounds which showed sufficient sensitivity under the conditions of use to make it interesting.

009840/2216 '

1699-Κ

The invention relates to new diperinones of the following Structural formulas:

-Z-

009840/2216

2Q04316

The compound of formula I is 10,22-Dioxodibenzimidazo-

(i, 2-b: 1 ^l , 2 ^I -b ') - dibenzo- (de: d'e ^l ) -p-dioxino- (2 _f 3-gi5 _f 6-g ¹ ) -diifloquinoline.

The compounds of the invention give fluorescence when

ο
they by radiation of 2537 A, the excitation radiation in conventional fluorescent lamps, and by the radiation of

1699-Κ.

3660 X, which represents a significant part of the emission from mercury vapor lamps. The excellent sensitivity of these new phosphors to excitation by radiation of 3660 A and the ^! . The reddish color of the imitated light, which is suitable for "correcting" the color of mercury lamps, makes these products particularly valuable for use as a component of mercury vapor lamps. The phosphors are too

suitable in pigment form. Others will be apparent to those skilled in the art useful applications of the invention.

Give in the drawings

Fig. 1 shows the fluorescence spectrum for a diperinone compound the invention with the prior art spectrum on top for comparison purposes, where the wavelengths of the fluorescence emission are against arbitrary intensity units are plotted and where the spectrum labeled A is the spectrum of a diperinone according to the invention and B the spectrum of one of the best currently available iroten Represent phosphors and

Fig. 2 is a graph in which the intensity

«The fluorescence emission is plotted in arbitrary units against the temperature, again.

These new diperinone compounds of the invention are prepared by chemical methods presently known to those skilled in the art manufactured. Of the available syntheses, a preferred route is shown schematically below:

009840/2216 original

S99-E

ζ Ό Naphthalic acid eaY ^ & ^ Ia is aaaob äesr Methods of 'Anselin and Zuokiaayer salicyl, art' (Bericfete 32, 3283 (1899));

V ⁰ S, / ⁰

(2) The 3-sulfonaphtbalinic acid anhydride which is divided in this way is made by / the method of Zollinger (HeIv. OMk. Acta 33 530 (Ί950)) in 3-hydroxynaphthalene acid anhydride convicted?

(3) The anhydride product obtained is then processed by the method von Dziewonski et al (CA. 26, 5942 (1932)) - "brominated:

T 5. τ

0 9840/2216 originally inspected

1699-1

(4) ϊ & β brominated product, is brominated with o-phenylenediamine and perinone :

Br

(5) In the final reaction, the diperirion derivative is thrown through intermolecular dehydrobromination of two moles of perinone to form a compound of the invention, i. one of the above-mentioned compounds I, II and III prepared.

The invention is further described by the following specific example, the details being given only serve for explanation and not limitation.

example

A mixture of 2.93 parts (0.01 mol) of 3-hydroxy-4-bromonaphthalic anhydride, 1.08 parts (0.01 moles) of o-phenylenediamine and 210 parts of acetic acid are refluxed. heated, and the reflux treatment is for 5-3 / 4 Hours continued. Forms during the reflux treatment

009840/2218

ORIGINAL ΙΝ9ΡΪ

_{: Λ} ■ ν. ? Ο0431Β

.see a heavy yellow precipitate, "the edge of which rises as the reflux treatment progresses." The product is filtered off and "washed until it is acid-free, old: water and finally dried * the yield" is 3 * 2 Parts (ie 87 _f 7? S of the theoretical value, where-a product is _{assumed to correspond to the additive: O ^ jQHqBrIi 2} Og). The melting point of a small sample of the hydroxy bromperinone, which crystallized from a large amount of hot acetic acid, is at 328 to 340 ⁰ G and possibly represents one of the compounds given in formulas IY and V. A

Analysis - "- .. ■■■■■ '· - .. ■.;

Calcd for C ₁₈ H ₉ BrN ₂ O ₂ : C 59.20 H 2.47 N 7.67 found i 0 59.10 H 2.84 N 7.36

3 in a mixture of 1 part of Hydroxybromperinons, -1 part of anhydrous potassium carbonate and 60 parts of dry nitrobenzene is heated to reflux temperature and kept at the reflux temperature for 5 hours. During this process, any water that has formed can escape from the reaction mixture. The hot mixture is filtered and the filter cake is washed thoroughly with nitrpbenzene, then subsequently with alcohol, water and again with alcohol. The product yield is 0.23 parts (35t8 i "theory, with a molecular weight of C * gH | gN * Öv suppose is). In another example, which was carried out in practically the same manner, a yield of 50.2 i "was obtained. In another experiment, in which some copper (II) acetate was added to the hydroxybromoperinone reaction mixture , the product yield is about 36%.

\ "- - - 0RiGINAL JMQPECTED

001840/2110 ■ '■. *** - " -

1699-Κ £

The product is purified by recrystallization from acid as follows: A solution of 2.63 parts of the pulverized dry product in 18.4 parts of sulfuric acid # 100 is made by stirring at a temperature not exceeding 10 ⁰ C. After complete dissolution, as judged by microscopic examination of the sample, the acid concentration is lowered gradually to 90 i "by dropwise addition of water, the addition rate is such that the temperature of the mixture is kept continuously below 10 ^0C. ■ the mixture is stirred for a further 1/4 hour at 10 ⁰ C, and the precipitated sulfate of the desired product is filtered off and washed thoroughly with 80 # sulfuric acid. The sulfate filter cake is then hydrolyzed with sis and water and the resulting diperinone compound is filtered off and washed free of acid to give 1.01 parts of a reddish yellow pest. For analytical purposes, 1.26 parts of the product are washed twice with 450 parts of nitrobenzene and once with 570 parts of boiling N, N'-dimethylformamide. The cleaned sample does not melt up to 400 ^° C

analysis

calc .: for C ₃₆ H ₁₆ N ₄ O ₄ : C 76.00 H 2.82 N 9.86 · found: C 75.04 H 2.80 N 9.95 "

A diperinone prepared according to the general procedure of Example was tested and investigated. Pig. 1 shows a comparison of the fluorescence emission spectrum A of the product obtained with the spectrum of one of the best currently available red phosphors \

q αοο 1O4 dae ait B is designated, under the suggestion of relative

009840/2216

1699-Κ Ο

long-wave ultraviolet rays (3660 A). The intensive " actions relate to a qualitative measure. suelle '' observations confirm the considerably larger Brightness of the product according to the invention. It's closed conclude that this strong deep red emission under excitation at 5660 A as a product of the invention. color-correcting phosphor makes superior when it is used for this purpose, for example on the inner surface of the outer KUIe of high pressure mercury vapor lamps is used, thus reducing the visible appearance of the obtained Light changes from blue to yellowish over, while at the same time the lumen output increases. Pig. 2 j

shows the relative intensity of the spectrum m Fluoreszerizemissions- of the product at temperatures up to 300 C. ⁰ It can be seen that even though the intensity at 300 ⁰ C in comparison with the value at 100 ⁰ C drops to about $ 40, as is ouch Pig. 2, in which the emission intensity is plotted against the temperature in arbitrary units, it is even higher than that of the Yq 9o ^Eu o ίο — 4 'cf. 1, it being assumed that the emission intensity of the latter compound was constant in this temperature range. Thus, the product of the invention is expected to be a superior red phosphor for color correction of discharge devices, even at 3660 Å by light. * έ the higher temperature is excited. ,

The product of the invention is a red shaded yellow material which is extremely insoluble in common organic solvents. If it is dispersed in an organic carrier, e.g. a lithographic varnish, and applied to a base ₃ , it is a red-tinged yellow pigment that, when excited by ultra-

- '' - '■ ^-:.:.' ■■ - ■■ ■■ 9

0098AO / 2218

1699-K "

strongly luminescent violet rays. After 72 hours Some darkening occurs after exposure, but most of the luminescence is still retained. Even after diluting the dispersion with ZnO in a ratio of 1: 100, the ultraviolet light illuminates the stretched dispersion observed a certain luminescence.

Although the invention has been described in certain details above it is clear that changes can be made by those skilled in the art. For example, can other solvents in the production of diperinones,

■ JP reaction temperatures and cleaning methods instead of the corresponding conditions given in the example can be used. Furthermore, it goes without saying that although the perinone by condensation with o-phenylenediamine was produced, the reaction can also be used for condensation with other o- or peri-diamines is. These include, for example, 1,2-diaminonaphthalene, 2,3-diaminonaphthalene, 1,8-diaminonaphthalene and the like. These reactants and the above-mentioned o-phenylenediamine can be substituted with groups e.g. lower alkyl, lower alkoxy and / or halogen radicals and the like, in order to produce correspondingly substituted diperinones

A.

- 10 -

009840/2216

Claims (2)

.169SMC January 30, 1970 Claims 1 * diperinone compound with one of the following structural formulas: - 11 - " 009840/2216 1699-K Ρ004316 2. Process for the preparation of new diperinone compounds according to claim "1, characterized in that 3-hydroxy-4-broin-naphthalic anhydride with a ortho- or peri-diamine, consisting of o-phenylenediamine, 1,2-diaminonaphthalene, 2,3-diaminonapthalene and / or 1,8-diaminonaphthalene, which optionally may be substituted by lower alkyl, lower alkoxy or halogen groups, and that - 12 - 009840/2216 1699-Κ _ <ß the thus precipitated hydroxybroraperinone product (or the products) is isolated and washed, and the isolated product in a suitable Solvent is condensed. 3 · Use of the diperinone compounds according to claim 1 as luminescent material for fluorescent lamps. - 13 - 0098A0 / 2216 Blank page