DE2329779A1 - CHEMILUMINESCENT COMPOSITIONS - Google Patents

Description

The invention relates to chemiluminescent compositions, in particular a combination of ingredients used in the Reaction with a hydroperoxide has a quantum yield, a maximum intensity and a total yield of chemiluminescent light give results that are significantly greater than the results obtained with chemiluminescence methods using conventional methods Chemiluminescent compositions achieved. The term "chemiluminescent light" as used herein stands for electromagnetic radiation with wavelengths between about 330 m / U and about 850 m / U,

- 2 309881/1091

The invention relates in particular to the use of special fluorescent compounds, namely aromatic, chlorine, Bromine, fluorine atoms or low molecular weight alkyl groups substituted bis-phenylethinyl hydrocarbons in combination with certain oxalic acid-like compounds to achieve chemiluminescent light.

The aim of the invention is to provide a chemiluminescent composition provide which, when mixed with a hydroperoxide, gives a higher quantum yield and leads to a higher maximum light intensity.

Another object of the invention is the provision of storable chemiluminescent compositions and / or the use of this chemiluminescent composition in a chemiluminescent reaction.

A chemiluminescent reactant is any compound which enters into a chemical reaction that produces chemiluminescent light.

The term "Chemilumineszenzreaktionsbestandteil", as used herein, refers to a mixture that results in a chemiluminescent reaction when they

1) with the others required in the method according to the invention Reaction participants is implemented or

2) when placed in the appropriate physical environment.

The term "fluorescent compound" as used herein refers to a compound which fluoresces upon a chemiluminescent reaction or a compound which forms a fluoroessential compound upon a chemiluminescent reaction.

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The general mechanism for the chemiluminescent reaction can be divided into three levels:

1. Luminous compound + oxidizing agent> key intermediate

2. Key Compound + Fluorescent Compound ■ ■ Fluorescent compound in the excited singlet state

3. Fluorescent compound in the excited singlet state ^ Fluorescent compound + radiation.

In step 1) a chemiluminescent material usually reacts with an oxidizing agent to form a substance called a key intermediate. In of stage 2) the key intermediate or decomposes undergoes another reaction to form a fluorescent compound which is in an excited singlet state is present. In step 3) the fluorescent compound emits radiation in the excited singlet state. However, the decomposition products are not given. The exact nature of the key intermediate has not been determined. Theoretically, the fluorescent compound is only through an energy transfer due to the decomposition of the Key intermediate chemical energy released is electronically stimulated and as such should not be decomposed will. It has been found, however, that the fluorescent compounds are subject to decomposition in all known cases. Thus, since the fluorescent compound is required as the light emitting material, there is no other lighting effect more possible if the entire fluorescent compound is decomposed, although the key intermediate product is still undecomposed may be present. Thus, for the maximum utilization of the chemical energy of stage 2) it is essential that a sufficient amount of the fluorescent compound is present is. This is however due to the solubility of the fluorescence

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compound in the solvent system and the stability of the Material restricted. Although highly effective fluorescence compounds are known, so far no material of this type with great solubility and stability has been found. Consequently the fluorescent compound can be the limiting factor of the chemiluminescent reaction described above, since it is not always possible to dissolve a sufficient amount of a highly effective fluorescent compound in the system to use the maximum possible chemical energy released.

In Belgian patent specification No. 703 586 it is stated that that 9,10-bis (phenyläthinyl) -anthracene and other phenyläthinylanthracene represent good fluorescent compounds which are more effective than the corresponding compounds without Phenylethinyl substituents.

It has been found that those substituted with chlorine, bromine, fluorine atoms or low molecular weight alkyl groups are substituted with phenylethinyl aromatic compounds are more effective fluorescent compounds that exist in the solvent system the chemiluminescence reaction are more soluble.

These compounds can therefore be present in larger concentrations and thus in larger quantities, which results in the maximum Utilization of the chemical energy released during the chemiluminescence reaction becomes possible.

The substituted bis (phenylethinyl) anthracenes used according to the invention are strong yellow fluorescent compounds. Thus, these compounds are very useful Fluorescent compounds represent for the chemiluminescent system, since the eye is most sensitive to yellow light.

The typical solvents that are a necessary component of a chemiluminescent reaction using the invention

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appropriate chemiluminescent combination can be used, include the common simple ester solvents, such as diethyl phthalate, dibutyl phthalate, ethyl acetate, octyl acetate, Dimethyl adipate, triethyl phosphate, tricresyl phosphate, ether / Ester solvents such as 2-methoxyethyl acetate and ether solvents, v / ie 1,2-dimethoxyethane, ethylene carbonate, 1,2-dibutoxyethane (i.e. dibutyl cellosolve), propylene carbonates and dibutyl carbitol. Typical ether solvents are Tetrahydrofuran and dioxane. It should be noted that other solvents other than ethers or esters were also used v / can ground, such as benzene, xylene, toluene, chlorobenzene, tetrachloroethane, fluorocarbons, polychlorinated Polyphenyls and the like. Mixtures of these solvents can also be used. The specified list the solvents which can be used are intended, however, not to limit the invention.

The combination according to the invention contains an ester of an oxalic acid type as an essential chemiluminescent component Acid as described in U.S. Patent No. 3,597,362. Accordingly, include those to be used according to the invention Esters of oxalic acids Esters of the following general formula:

_o- c -Vc / -ο- R,

in the FL and FU are aliphatic or aromatic groups and η is zero or an integer from 1 to 9. The groups R>. and R _? Alkyl groups such as hexafluoro-2-propyl groups, aryl groups such as phenyl groups or naphthyl groups, substituted aryl groups such as chlorophenyl groups, trifluoromethylphenyl groups, formylphenyl groups, nitrophenyl groups

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groups, methoxyphenyl groups, dinitrophenyl groups, pyridylphenyl groups or sulfophenyl groups, heterocyclic groups, such as pyridyl groups or substituted heterocyclic groups Groups such as methylpyridyl groups, chloropyridyl groups, Acetoxypyridyl groups, formylpyridyl groups, carboxypyridyl groups, Methoxyfuryl groups, dimethylaminotetrahydrofuryl groups or sulfofuryl groups or unsaturated alkyl groups, like vinyl groups.

According to the invention, the oxalic acid-type esters are used acid

(a) An ester of an oxalic acid-like acid with an alcohol, which has an ionization constant in water of greater

-10
than 1.3 x 10 or

(b) a vinyl ester of an oxalic acid.

In a similar way, according to a preferred embodiment, the alcohol is an aromatic alcohol which contains a substituent with a positive Hammet ¹ see <o -4. Preferred esters of oxalic acids are 3is (substituted phenyl) oxalate, such as bis (2-nitrophenyl) oxalate, bis (2,4-dinitrophenyl) oxalate, bis (2,6-dichloro-4- nitrophenyl) oxalate, bis (3-trifluoromethyl-4-nitrophenyl) oxalate, bis (2-methyl-4,6-dinitrophenyl) oxalate, bis (1,2-dimethyl-4,6-dinitrophenyl) oxalate, bis (2,4-dichlorophenyl) oxalate, bis (2,5-dinitrophenyl) oxalate, bis (2-formyl-4-nitrophenyl) oxalate, bis (pentachlorophenyl) oxalate, bis - (1,2-dihydro-2-oxo-1-pyridyl) -glyoxal, bis-N-phthalmidyloxalate, bis- (2,4,6-trichlorophenyl) oxalate and compounds of the above type, the carbalkoxy groups, for example carbbutoxy groups or have carbalkoxy groups on the phenyl ring, v.'ie bis (2,4,5-trichloro-6-carbobutoxyphenyl) oxalate and bis (2,4,5-trichloro-6-carbopentoxyphenyl) oxalate.

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■ - 7 -

The hydroperoxide used in the inventive method in the inventive combinations can be any of suitable peroxide compound. It can be seen that hydrogen peroxide or a solution of this compound can be used as this compound is the preferred peroxide compound. The hydrogen peroxide used can be obtained from anhydrous hydrogen peroxide compounds, such as the perhydrate of urea (Urea peroxide), the perhydrate of pyrophosphate compounds (sodium pyrophosphate peroxide), the perhydrate of Histidine (histidine peroxide) or sodium perborate. Another. Form in which the anhydrous hydrogen peroxide in the Composition can be introduced is an anhydrous solution of hydrogen peroxide in a suitable solvent, such as ether, an ester, an aromatic hydrocarbon, etc., i.e. a material which is a suitable Represents a diluent for the composition used according to the invention. If you can use hydrogen peroxide If you want, you can replace this compound with any suitable compound which liberates Yfassstoffperoxid.

-5 The peroxide concentration can be about 15 molar to about 10 molar,

preferably about 2 molar to about 10 molar. The according to the invention Esters can be used as solids or by admixture with a suitable solid peroxide reactant or in a suitable diluent or can be added directly to one of the peroxide reactants containing solution are dissolved.

Typical diluents which can be added in addition to the diluent required according to the invention, are materials that do not react with a peroxide such as hydrogen peroxide and with an oxalic acid ester.

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Although the addition of water to * develop the chemiluminescent light is not required, according to certain embodiments of the invention, water can be used as a diluent or partial diluents are used. The term "water" like as used herein, it also includes water-forming compounds such as hydrates. In addition, however, one or more Diluents can be used together with or in place of the water, provided that the peroxide used at least in part in the combination of the diluent (s) is soluble, e.g. in an amount of at least 1/10 g EUOp / liter. of the diluent · In the following Examples of additional diluents or solvents that can be used according to the invention are given:

Non-cyclic or cyclic ethers, such as diethyl ether, diemyl ether, Diphenyl ether, anisole, tetrahydrofuran, dioxane and the like, esters such as ethyl acetate, propyl formate, amyl acetate, Dimethyl phthalate, diethyl phthalate, methyl benzoate and the like. and aromatic hydrocarbons such as benzene, xylene or toluene.

Although it is only necessary to contain phenylethinyl groups Using fluorescent compounds in the compositions according to the invention can, if desired, also other fluorescent compounds are additionally added, e.g. to change the color of the emitted light.

As compounds of this kind, together if desired used with the substituted phenylethinyl compound can be, you can - very generally speaking - use those compounds that are not easy with the invention The peroxide used, such as hydrogen peroxide, does not react and also in contact with the oxalic acid ester to none Lead reaction. Typical fluorescent compounds that can be added according to the invention are compounds that have a spectral emission between 330 m / u and 850 m / u

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and which are at least partially soluble in any of the above-identified diluents, if used. Compounds of this type are conjugated polycyclic aromatic compounds that have at least three condensed Have rings, such as anthracene, substituted anthracene, benzanthracene, phenanthrene, substituted phenanthrene, Naphthacene, substituted pentacenes and the like. Typical Substituents for these compounds are phenyl radicals, low molecular weight alkyl groups, chlorine atoms, bromine atoms, cyano groups, Alkoxy groups with 1 to 16 carbon atoms and other substituents of this type which do not have a disturbing influence exert on the photogenerating reaction of the present invention.

It was found that the molar concentrations (Mol / Ltr. of the diluent) of the main components of the new combination according to the invention can vary considerably. It it is only necessary that the constituents are present in a concentration that is sufficient to achieve chemiluminescence sufficient. The molar concentration of the anhydride, the amide or the ester of oxalic acid is in

_7 a range of at least about 10 to 5 molar, preferably

_ ■ *
wise in the range of 10 to about 1 molar, while the fluorescent compound with a molar concentration im

-5 -4 -1

Range from about 10 to 5> preferably 10 to 10 m is present and that water or the other diluent must be present in sufficient amount to at least to enable a partial solution of the reaction participants participating in the chemiluminescence reaction. Although no upper limit is known on the concentration of oxalate used in the reaction, it has been ■: found the response to be within the specified range runs more effectively. The ester can be used simultaneously either as the sole diluent or as an adjuvant diluent to serve.

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- ίο -

The constituents of the composition according to the invention can can be mixed in a single step or the individual ingredients can be mixed together one after the other.

Although the chemiluminescent reaction according to the invention does not normally require a specific order to adhere to when adding the individual components of the chemiluminescent composition according to the invention, it has been found that the fluorescent compound is preferably already present in the reaction mixture at this point in time should be, as the last ingredient is added, which is necessary for the chemical reaction and the associated chemical reaction to take place Release of chemical energy is required.

The wavelength of the light emitted by the chemiluminescent reaction of the compositions of the invention, i. the color of the emitted light can be changed by adding one or more energy transfer agents (fluorescent compound), like the known fluorescent compounds described in detail above, changed v / ground.

The wavelength of the light emitted by the composition of the invention varies depending on the particular one fluorescent compound used in the reaction.

In addition, it has been found that a superior chemiluminescence intensity is obtained than that of cheniluminescence causing final mixture is kept at a temperature between about -40 and 75 ° C, preferably between 0 and 50 ° C. The temperature is not critical, however, and the chemiluminescent composition according to the invention is sensitive to these ranges not restricted.

In addition, one uses in the composition and in the method of using it when one has optimal chemiluminescent Light intensity aims at a base in an amount

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which is sufficient to give vim a basic pH. However the preferred longer lifetimes are achieved under approximately neutral conditions. It can be any suitable Base that does not interfere with the reaction of the chemiluminescent composition according to the invention can be used

This includes a wide variety of organic and inorganic Bases such as sodium hydroxide, potassium tert-butoxide, Sodium ethylate, sodium methylate, ammonium hydroxide, tetrabutylammonium hydroxide and triphenyl methylate. Lewis bases including pyridine, triethylamine or quinoline and as preferred bases sodium salicylate and sodium benzoate.

Although basic catalysts are generally preferred with oxalic acid esters and amides, acidic catalysts are particularly preferred for the compounds described in Canadian Patent No. 895,309.

The life and the intensity of the chemiluminescent light can be determined by the use of certain regulating agents e.g. by adding a base to the chemiluminescent Composition can be controlled. Both the strength and the concentration of the base are vpn in this context critical importance.

In particular, the advantages achieved by incorporating a catalyst, as described in the Belgian patent 703 586 is known, can be achieved according to the invention by Using an ionized salt that has a cation such as

(a) an organic quaternary cation, e.g. an ammonium cation or an arsenic or phosphorus-containing quaternary Cation or

(b) an alkali metal ^{cation with an atomic weight above about 22} > 30 9 881/1091

having, the salt of the cation preferably in one soluble in organic solvents and should have the property of forming cation aggregates when it is used with the Ester of oxalic acid and a hydroperoxide is reacted. One of the advantages is based on the fact that, When using the ionized salt, using an excess amount of the chemiluminescent agent and thus can achieve a higher quantum yield in contrast to systems in which no such accelerator is used so that these systems are limited to a much lower maximum concentration of the chemiluminescent agent are, whereby the total quantum yield of the chemiluminescent light gain more than you would lose.

Furthermore, it is within the scope of the invention to use one or more retarders at the same time, either alone or together to be used with one or more of the above-mentioned accelerators in the composition according to the invention. By Using the above-mentioned accelerators it is possible to obtain a greater total concentration of the chemiluminescent agent to use, while at the same time it would be possible to use a retarder which would lengthen the time while the high intensity light in the chemiluminescent reaction is being developed. Retarders of this type are described and included in Belgian patent 703 586 e.g. a compound such as oxalic acid.

In addition, the compositions of the invention can contain a gelling agent to form chemiluminescent compositions with a self-supporting structure as described in US Pat. No. 3,671,450.

The following examples are intended to explain the invention further without, however, restricting it.

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example 1

It has been determined that the loss of efficiency of the Chemiluminescence with increasing oxalate concentration partly a consequence of the quenching of the fluorescence by the unreacted Is oxalate. Thus, part of the energy available for light emission is passed through this process radiationless deactivation will be lost. The fluorescence efficiency was used to determine the extent of this loss different fluorescent compounds at different oxalate concentrations in oxalate-containing chemiluininescent Compositions determined. The results obtained are summarized in Table I below and show that 1-chlorine, 10-bis (phenyl äthinyl) anthracene (abbreviated as 1-C1-BPEA), 2-chloro-9,10-bis- (phenyläthinyl) -anthracene (2-Cl-BPEA), 1,5-dichloro-9,10-bis (phenyläthinyl) -anthracene (1,5-DCBPEA), 1,8-dichloro-9,10-bis (phenylethinyl) -anthracene (1,8-DCBPEA), 2,3-dichloro-9,10-bis (phenyläthinyl) -anthracene (2,3-DCBPEA) and 5,12-bis (phenylethinyl) tetracene (5,12-EPET) significantly are more stable to the quenching of fluorescence by bis (2,4,5-trichloro-6-carbopentoxyphenyl) oxalate (CPPO). However, the efficiencies of chemiluminescence are with 5,12-bis- (phenyläthinyl) -tetracene (5,12-BPET) at concentrations of bis (2,4,5-trichloro-6-carbopentoxyphenyl) oxalate (CPPO) of more than 0.1 mol / ltr. lower than with bis (phenylethinyl) anthracene (BPEA), as the tetracene is destroyed in the chemiluminescence reaction.

From the fluorescence quenching investigations, which are given in the table, it can be seen that methyl-9 _f 10-bis- (phenyläthinyl) -anthracene surprisingly resistant to the quenching of fluorescence by bis- (2,4,5-trichloro-6- carbopentoxyphenyl) oxalate (CPPO) and thus represent the superior fluorescent compounds in chemiluminescent compositions containing oxalate ester.

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Examples 2 and 3 *

A comparison of the chemiluminescence in bis- (2,4, S-carbopentoxyphenylJ-oxalate (CPPO) of 9,10-bis (phenylethinyl) anthracene (BPEA) and 1,5-dichloro-9,10-bis (phenylethinyl) anthracene (1,5-DCBPEA) is given in Table II below. As can be seen from the emission intensities is, even with an oxalate concentration of 0.1 mol / Ltr « more light is developed if 1, ^ - dichloro-P / jiO-bis-C-phenylethinyl) anthracene is used (1,5-DCBPEA) is used. The results also show that a maximum light output with a Concentration of 1,5-dichloro-9,10-bis (phenylethinyl) -anthracene (1,5-DCBPEA) of 2 10 m is achieved. The considerably greater luminous efficacy with 1,5-DiChIOr-S, 10-bis- (phenyläthinyl) -anthracene (1,5-DCBPEA) can be easily recognized at higher concentrations. As from the table II, Experiment 6, 0.195 M bis (2,4,5-trichloro-6-carbopentoxyphenyl) oxalate (CPPO) and 1.8 10 "^ m 1,5-dichloro-9,10-bis (phenylethinyl) anthracene (1,5-DCBPEA) an amount of light of 462 lm »hours ·!" "And a A quantum yield of 0.075 Einstein / mole was achieved.

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O CD OO 00

Anthracenes

DPA *

BPEA *

1-MBPEA 2-MEBPEA 1,5-DCBPEA 1,8-DCBPEA 2,3-DCBPEA 1-Cl-BPEA 2-Cl-BPEA

I. 0.10m 0.20m at different CPPO 0.05m 0.10m ¹ 0.20m 0 b_ TABEL 0.494 0.352 Fo / F values ^c 1.38 1.49 2.10 preparation of anthracenes 0.594 0.502 0.25m 1.19 1.31 1.69 , 25m Fluorescent 0.701 0.552 0.349 1.20 1.38 1.76 2.12 Quantum L and tetracenes by CPPO ^a 0.688 0.624 0.464 1.10 1.27 1.40 1.83 prey Fluorescence quantum yield 0.937 0.914 0.507 1.04 1.05 1.06 1.94 0.738 Concentrations as 0.902 0.913 0.607 1.15 1.10 1.11 1.44 0.847 0.05m 0.866 0.868 0.909 1.04 1.08 1.09 1.07 0.979 0.536 0.640 0.582 0.866 1.06 1.11 1.22 1.01 0.872 0.678 0.578 0.511 0.907 1-08 1.15 1.30 1.05 0.973 0.803 0.559 1.27 1.00 0.793 0.485 1.37 0.94 0.926 0.710 0.991 0.665 0.899 0.670 0.616

Tetracenes

5,6,11,12-tetraphenyl- (rubrene) *

5.12-BPET *

0.583 0.495 0.454 0.387 0.335 1.74

0.715 0.715 0.673 0.649 0.628 1.14

1.51 .1.28
1.10 1.05

2323779

- 16 TABLE I (continued)

Footnotes:

a The solutions contained 2.0 10 mol fluorescent compound per liter of dibutyl phthalate with the exception of 2,3-DCBPEA that in a concentration of 5 x 10 "m and 1-Cl-BPEA and 2-Cl-BPEA that in a concentration 3 x 10 m were available. The excitation wavelength was 497 mn for rubrics and 429 nm for all others Fluorescent compounds.

b CPPO = bis (2,4,5-trichloro-6-carbopentoxyphenyl) oxalate.

c F is the fluorescence quantum yield and

Fo is the fluorescence quantum yield in the absence of CPPO.

* Known connections.

DPA = 9f10-diphenylanthracene BPEA = 9,10-bis (phenylethinyl) anthracene

1-MBPEA = 1-methoxy-9, iO-bis (phenylethinyl) anthracene 2-MEBPEA = 2-methyl-9, iO-bis (phenylethyinyl) anthracene 1,5-DCBPEA = 1,5-dichloro-9,10-bis (phenylethinyl} -anthracene 1,8-DCBPEA β 1,8-dichloro-9,10-bis (phenylethinyl) anthracene 2,3-DCBPEA = 2,3-dichloro-9,10-bis (phenylethinyl) anthracene 1-Cl-BPEA = 1-chloro-9, iO-bis (phenylethinyl) anthracene 2-Cl-BPEA = 2-chloro-9, iO-bis (phenylethinyl) anthracene

5,12-BPET = 5,12-bis (phenylethinyl) tetracene.

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TABLE II Chemiluminescence from CPPO and 1,5-DCBPEA systems

Final concentration intensity in apostilb / cm (ft.Ibt.cm " ¹ ) 'depending on the

^{Zit (Wed)}

Exp.CPPO (m) * DCBPEA ^{time (min>)} . : (1)

(m «10 ⁵ ) * 2 10 20 30 60 90 120 150 l80 210 240

l ^b 0.080 1.6 279.8 204.4 150.6 118.4 68.86 45.19 33.36 24.75 20.44 17.22 13.99 254 10.1

(26) (19) (14) (11) (6.4) (4.2) (3.1) (2.3) (1.9) (1.6) (1.3)

2 0.150 1.5 344.3 226.0 172.2 150.6 107.6 83.93 65.64 51.65 40.89 33.36 27.98 370 7.8

co (32) (21) (16) (14) (10) (7.8) (6.1) (4.8) (3.8) (3.1) (2.6) ο

⁴⁰ 3 0.180 2.1 408.9 312.0 247.5 204.4 118.4 75.32 45.19 25.82 12.91 - 382 6.8

^ (38) (29) (23) (19) (H) (7.0) (4.2) (2.4) (1.2)

C 4 ^C 0.180 1.8 495.0 398.1 290.5 236.7 129.1 75.32 44.12 25.82 15.06 8.61 5.38 412 7.3

- (46) (37) (27) (22) (12) (7.0) (4.1) (2.4) (1.4) (0.8) (0.5)

<° 5 0.195 1.8 279.8 193.7 l6l, 4 139.9 118.4 93.61 76.40 61.33 48.42 37.66 26.90 422 6.9

(26) (18) (15) (13) (11) (8.7) (7.1) (5.7) (4.5) (3.5) (2.5)

6 ^C 0.195 1.8 408.9 290.5 236.7 182.9 129.1 92.53 65.64 44.12 29.05 17.22 10.76 462 7.5

(38) (27) (22) (17) (12) (8.6) (6.1) (4.1) (2.7) (1.6) (1.0)

(1) Amount of light NJ (lm.h / ltr. CO

(2) Quantum yield - ι CD (Einstein / Mol · 10 " ^d ) ^ 3

TABLE II (continued):

Footnotes:

a The reactions were carried out in 75 % dibutyl phthalate, 20 % dimethyl phthalate and 5 % tert-butanol. The hydrogen peroxide concentration was 0.375 m, while sodium salicylate was present in a concentration of 1.25 10 ".

-k

b The sodium salicylate concentration was 1.0 10 m.

-4

c The sodium salicylate concentration was 2.0 10 m.

* See footnote in TABLE I.

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Examples 4 and 5

In this example, the effectiveness of the inventive Fluorescent compound at constant concentration of the oxalate compound and varying concentration of the Fluorescent compounds examined. The results obtained are summarized in Tables III and IV below. In Table III the oxalate concentration was kept at 0.01 m, while in Table IV this concentration Was 0.21 m.

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TABLE III

Effect of the concentration of 1,8-DCBPEA * on the chemiluminescence efficiency at a CPPO ^a concentration of 0.10 m .

1,8-DCBPEA quantum. Light T.75 ^d intensity in apostilb / cm (ft.lbt./cm) depending on _{mx 10} 3 yield ⁰ amount of time (min.)

^{x 10} 2 10 30 60 120 180 240

406.73 301.3 181.8 85.00 37.66 24.75 20.44 (37.8) (28.0) (16.9) (7.9). (3.5) (2.3) (1.9)

462.7 347.5 205.5 95.76 41.96 30.13 22.60 ru

(43.0) (32.3) (19.1) (8.9) (3.9) (2.8) (2.1)

513.2 372.2 218.4 96.84 43.04 27.98 23.67 (47.7) (34.6) (20.3) (9.0) (4.0) (2.6 ) (2.2)

481.0 355.1 202.3 89.31 39.8l 24.75 19.37 (44.7) (33.3) (18.8) (8.3) (3.7) (2.3) (1.8)

539.1 415.3 216.3 93.61 41.96 29.05 20.44

(50.1) (38.6) (20.1) (8.7) (3.9) (2.7) (1.9) ¹ ^

495.0 365.8 191.5 79.62 33.36 19.37 15.06 co (46.0) (34.0) (17.8) (7.4) (3.1) (1, 8) (1,4) -J

309881 / 7.94
6.80 13.13
12.73 385
358 146
126 O 5.67 15.33 438 410 14.32 414 603 3.40 14.38 429 302 2.27 10.88 329 120

TABLE III (continued):

Footnotes:

a The chemiluminescent composition contained 0.10 m bis (2,4,5-trichloro-6-carbopentoxyphenyl) oxalate (CPPO), 1.56 χ 10 m sodium salicylate, 0.375 m H ₉ O ₉ and 1,8-dichloro -9,10-bis (phenyläthinyl) -anthracene (1,8-DCBPEA) in the specified concentrations in a solvent,
that of 75 % dibutyl phthalate, 20 % dimethyl phthalate and
-5 % tert-butanol.

b quantum yield in Einstein / mole c amount of light in lm «hours / ltr. d see footnote d to TABLE IV.

* 1,8-DCBPEA m 1,8-dichloro-9,10-bis- (phenyläthinyD-

anthracene.

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TABLE IV

Effect of the concentration of 1,8-DCBPEA * on the chemiluminescence efficiency at a CPPO ^a concentration of 0.21 m

1,8-DCBPEA quantum _b light T.75 ^d intensity in apostilb / cm (ft.lbt / cm) as a function of m χ lo ^ yield amount of time (min.)

^x 10 ² 2 10 30 60 120 l80 240

CO
O
to 7.94 7.76 478 1881 / 6.80 7.74 457 O
CO 5.67 7.70 463 4.53 5.97 363 3.40 5.89 369 2.27 4.11 261

359.4 262.5 l6l, 4 121.6 83.93 55.95 25.82 (33.4) (24.4) (15.0) (11.3) (7.8) (5.2 ) (2.4)

416.4 305.6 163.7 145.3 96.84 61.33 39.81 (38.7) (28.4) (18.0) (13.5) (9.0) (5.7 ) (3.7) «

454.1 321.7 202.3 150.6 96.84 58.10 34.43 (42.2) (29.9) (18.8) (14.0) (9.0) (5.4 ) (3.2)

413.2 299.1 181.8 132.3 77.47 30.13 11.84 (38.4) (27.8) (16.9) (12.3) (7.2) (2.8 ) (1.1)

501.4 337.9 200.1 146.3 67.79 23.67 6.46 (46.6) (31.4) (18.6) (13.6) (6.3) (2.2 ) (0.6)

485.3 324.9 184.0 108.7 21.52 '2.152 1.08 CO (45.1) (30.2) (17.1) (10.1) (2.0) (0.2) (0.1) ^ j

TABLE IV (continued): Footnotes:

a The chemiluminescent composition contained 0.21 m bis (2,4,5-trichloro-6-carbopentoxyphenyl) oxalate (CPPO), 1.56 χ 10 m sodium salicylate, 0.375 m H ₂ O ₂ and 1,8-dichloro -9,10-bis (phenyläthinyl) -anthracene (1,8-DCBPEA) in the specified concentrations in a solvent which consisted of 75 ⁰ A dibutyl phthalate, 20 % dimethyl phthalate and 5 % tert-butanol.

b quantum yield in Einstein / mole c amount of light in lm »h / ltr

d Time (minutes) required to emit 75% of the total amount of light.

* 1,8-DCBPEA = 1,8-dichloro-9, iO-bis (phenylethinyl) ~

anthracene

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Example 6

2 monochlorosubstituted bis (phenylethinyl) anthracenes were examined in this example. 2-chloro-9, iQ-bis (phenylethinyl) anthracene (2-Cl-BPEA) was used at two concentrations of bis (2,4,5-trichloro-6-carbopentoxyphenyl) oxalate (CPPO), namely 0.10 m and 0.21 m, respectively, and the results obtained are shown in Table V below summarized. The investigation of 1-chloro-9,10-bis (phenylethinyl) -anthracene (1-Cl-BPEA) in 0.10m CPPO is in Table VI below and in 0.21m CPPO in Table VII summarized.

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TABLE V
Chemiluminescent effect of 2-Cl BPEA ^a

2-Cl BPEA CPPO NaSaI light? Quan- T.75 ^e intensity in apostilb / cm (ft.Ibt./cm)

. πι m m xlO amount depending on the time (min.)

yield ⁰

10 30. 60 90 120 l80 210

0.005 0.10 1.56 118 11.9 118 336.8 302.1 267.9 178.6 111.9 66.7 30.1 17.2

_ω (31.3) (28.1) (21.9) (16.6) (10.1) (6.2) (2.8) (1.6)

S 0.005 0.10 1.56 157 15.2 116 355.08 311.0 271.1 18l., 8 113.0 67.8 31.2 17.2

co (33.3) (28.9) (25.2) (16.9) (10.5) (6.3) (2.9) (1.6)

- * 0.007 ^b 0.10 1.56 131 11.2 106 326.0 283.0 265.8 l87.2 117.3 68.9 28.0 11.0

H (30.3) (26.3) (21.7) (17, D (10.9) (6.1) (2.6) (1.3)

S 0.007 ^b 0.10 1.56 121 13.9 101 327.1 285.1 26l, 5 181.9 116.2 66.7 28.0 '11.0

- (30.1) (26.5) (21.3) (17.1) (10.8) (6.2) (2.6) (1.3)

0.005 0.21 5.0 703 11.0 106 761.0 660.7 107.8 236.7 159.2 101.1 50.6 26.9

(71.0) (61.1) (37.9) (22.0) (H, 8) (9.7) (1.7) (2.5)

0.005 0.21 5.0 682 10.6 111 758.6 631.8 386.3 227.0 153.9 101.1 50.6 26.9

(70.5) (59.0) (35.9) (21.1) (H, 3) (9.1) (.1.7) (2.5)

0.007 ^b 0.21 5.0 686 10.7 108 677.9 587.5 385.2 217.5 175.1 117.38 50.6 22.6

(63.0) (51.6) (35.8) (23.0) (16.3) (10.9) (1.7) (2.1)

0.007 ° 0.21 5.0 730 11.1 112 713.1 617.6 108.9 258.2 182.9 123.7 57.0 28.0

: (66.3) (57.1) (38.0) (21.0) (17.0) (11.5) (5.3) (2.6)

TABLE V (continued):

Footnotes;

a The chemiluminescent compositions contained 0.21 m bis (2,4,5-trichloro-6-carbopentoxyphenyl) oxalate (CPPO), 0.375 m H ₃ O ₂ and sodium salicylate (NaSaI) and 2-chloro-9,10- bis (phenylethinyl) anthracene. (2-Cl-BPEA). in the specified concentrations in a solvent mixture of 75 % dibutyl phthalate, 20 % dimethyl phthalate and 5 % tert-butanol.

"b When standing dropped the fluorescent compound from the ver used oxalate solution, so that the solutions were heated to release the fluorescent compound, after which the solutions were cooled to room temperature before being mixed with the promotor ·

d ^ VgI. the footnotes b, c and d of TABLE IV.

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TABLE VI

Effect of the concentration of 1-Cl-BPEA on the chemiluminescent effect in 0.10 ei CPPO ^a _;

Conc. Light- quantum- _fa ^{T.75 d} intensity in apostilb / cra (ft.lbt / cm)

1-Cl BPEA quantity yield as a function of time (min.)

0.005 569 17.9 98

ο 0.005 552 17.3 97 CO OD CX)

0.005 552 17.3 0.006 577 17.9 0.006 541 . 16.8 0.007 574 18.0 0.007 523 15.5 0.008 535 16.8 0 «008 522 16.4

o 0.006 541> 16.8 99

2 10 30th 60 90 120 180 I. 444.4
(41.3) 415.3
(38.6) 376.6
(35.0) 253.9
(23.6) 149.6
(13.9) 87.1
(8.1) 39.8
(3.7) IVJ
—I
I. 442.2
(41.1) 409.9
(38.1) 366.9
(34.1) 243.2
(22.6) 142.0
(13.2) 85.0
(7.9) 37.7
(3.5) 431.5
(40.1) 404.6
(37.6) 375.5
(34.9) 262.5
(24.4) 157.1
(14.6) 92.5
(8.6) 39.8
(3.7) 403.5
(37.5) 378.7
(35.2). 352.9
(32.8) 243.2
(22.6) 144.2.
(13.4) 85.0
(7.9) 38.7 *
(3.6) 423.9
(39.4) 390.6
(36.3) 373.3
(34.7) 272.2
(25.3) 162.5
(15.1) (95.8
(8.9) 40.9
(3.8) 404.6
(37.6) 371.2
(34.5) 347.5
(32.3) 244.2
(22.7) 142.0
(13.2) 83.9
(7.8) 36.6
(3.4) 368.0
(34.2) 350.8
(32.6) 341.1
(31.7) 252.9
(23.5) 154.9
(14.4) 91.5
(8.5) 38.7
(3.6) 370.1
(34.4) 344.3
(32.0) 338.9
(31.5) 249.6
(23.2) 119.4
(11.1) 87.1
(8.1) 35.5
(3.3)

101 368.0 350.8 341.1 252.9 154.9 91.5 38.7 £ J

(34.4) (32.0) (31.5) (23.2) (11.1) (8ll) (3 ^ 3)

TABE LLE V I (continued):

Footnotes:

a The chemiluminescent compositions contained 0.10 m bis (2,4,5-trichloro-6-carbopentoxyphenyl) oxalate (CPPO), 0.375 m H ₃ O ₂ , 1.56 χ ΙΟ " ⁴ m sodium salicylate and l-chlorine -9,10-bis (phenyläthinyl) -anthracene (1-Cl BPEA) in the specified concentrations in a solvent mixture of 75 % dibutyl phthalate, 10 % dimethyl phthalate and 5 % tert-butanol.

c ( Compare footnotes b, c and d of TABLE IV.

309881/1091

TABEL VII Quanta
yield ⁰ T.75 d 2 on the Chemiluminescent 30th 60 90 120 180 240 957.6
(89.0) Intensity in apostilb / cm (ft.Ibt./cm)
depending on the time (min.) 577.8
(53.7) 313.1
(29.1) 172.2
(16.0) 97.9
(9, D 40.9
(3.8) 21.5
(2.0) Conc.
1-Cl-BPEA Effect of the concentration of the fluorescent compound
cence behavior of 1-Cl-BPEA in 0.21 m CPPO ⁸ 12.9 81 952.3
(88.5) 10 557.4
(51.8) 304.5
(28.3) 173.2
(16.1) 95.8
(8.9) 39.8
(3.7) 23.7
(2.2) m light
lot 12.6 72 914.6
(85.0) 875.9
(81.4) 602.6
(56.0) 363.7
(33.8) 214.1
(19.9) 124.8
(11.6) 51.6
(4.8) 26.9
(2.5) 0.005 14.4 92 903.8 852.2
(79.2) 580.0
(53.9) 346.5
(32.2) 204.4
(19.0) 120.5
- (11.2) 49.5
(4.6) 25.8
t2.4) 0.005 840 13.9 91 855.4
(79.5) 849.0
(78.9) 552.0
(51.3) 340.0
(31.6) 210.9
(19.6) 122.7
(11.4) 49.5
(4.6) 25.8
(2.4) 0.007 819 13.9 98 871.6
(81.0) 816.7
(75.9) 503.6
(46.8) 320.6
(29.8) 213.0
(19.8) 138.8
(12.9) 61.3
(5.7) 30.1
(2.8) 0.007 920 13.7 107 776.9
(72.2) 0.008 884 746.7
(69.4) 0.008 883 886

a The chemiluminescent compositions contained 0.21 m (bis- (2,4, S-trichloro-ö-carbo- ^ω pentoxyphenyD-oxalate, 0.375 m H ₃ O ₂ , 5 x 10 "^ m sodium salicylate and 1-chloro-9, 10-bis- ^ (phenyläthinyl) -anthracene (1-Cl-BPEA) in the specified concentrations in a solvent mixture of 75 % dibutyl phthalate, 20 % dimethyl phthalate and 5 % tert-butanol

c) cf. the footnotes b, c, d of TABLE IV.
d

example

In this example, a number of fluorescent compounds were analyzed for their optimal concentrations examined. It can be seen that the monochloro-9,10-bis (phenylethinyl) anthracene compounds, compared to the best known fluorescent compound 9,10-bis- (phenyläthinyl) -anthracene (BPEA) lead to very good results. The results obtained are as follows Table VIII summarized:

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TABLE VIII

Comparison of different fluorescent compounds in chemical light systems that contain 0.21 in CPTO ^{a '}

Fluorescence _{(1) (2) light} _ quantum intensity in apostilb / cm (ft.Ibt./cm) compound ⁰ quantity yield ⁰ as a function of time (min.)

10 30 60 90 120 180 290

ω BPEA 2.25 5.0 248 3.91 602 473 172 52.7 21.5 10.8 4.30

2 (56) (44) (16) (.4.9) (2.0) (1.0) (0.4)

<£ 1-Cl-BPEA 8.0 5.0 883 13.9 850 774 549 344 215 118 49.5 25.8

_> (79) (72) (51) (32) (20) (11) (4.6) (2.4)

Γΐ 2-Cl-BPEA 5.0 5.0 682 dO, 6 763 635 387 226 I5I 101 5Oj6 26.9

° (71) (59) (36) (21) (14) (9.4) (4.7) (2.5)

- * 1,8-DCBPEA 7.9 1.56 188 7.8 355 258 I61 II8 - 83.9 55.9 25.8

(33) (24) (15) (11) (7.8) (5.2) (2.4)

1,5-DCBPEA 1.8 2.00 462 7.5 408 290 I83 129 92.5 65.6 29.0 10.8

(38) (27) (17) (12) (8.6) (6.1) (2.7) (1.0)

(1) Concentration of the fluorescent compound CO (m «103), ^ j

(2) NaSaI ₁ concentration ^ co (ra-lO ⁴ ) ·,

TABLE VIII (continued):

Footnotes:

a The chemiluminescent compositions contained 0.21 m bis (2,4,5-trichloro-6-6arbopentoxyphenyl) oxalate (CPPO), 0.375 m H ₂ O ₂ and sodium salicylate (NaSaI) and the fluorescent compound in the specified concentrations in one Solvent mixture of 75 % dibutyl phthalate, 20 % dimethyl phthalate and 5 % tert-butanol.

b. The fluorescent compounds used were: BPEA ■ 9,10-bis (phenylethinyl) anthracene 1-Cl-BPEA »1-chloro-9,10-bis (phenylethinyl) anthracene 2-Cl-BPEA = 2-chloro-9,10-bis (phenylethinyl) anthracene

1,8-DCBPEA = 1,8-dichloro-9,10-bis (phenylethinyl) anthracene

1,5-DCBPEA * 1,5-dichloro-9,10-bis- (phenyläthinyl) -anthracene,

c See footnote b of TABLE IV. d See footnote c of TABLE IV.

309881/1091

Example 8

Production of 1 "-Fluoro-9 _> 1Q-bis (phenylethinyl) - 'anthracene

A mixture of 4.5 g of 1-fluoroanthraquinone (0.02 mol), 1.04 g of lithium amide (0.045 mol) and 4.1 g (0.04 mol) of phenylacetylene was refluxed in 100 ml of toluene for 24 hours. Neutralization with acetic acid and evaporation of the toluene under reduced pressure gave a tarry material which solidified upon stirring with petroleum ether. The infrared spectrum of this solid was consistent with a mixture of the expected diol and lithium acetate. This product was dissolved in 200 ml of dimethylformamide and mixed with 18.0 g of tin (II) chloride dihydrate. The material was then stirred at room temperature for 24 hours after which the brown solid formed was filtered off, washed with water and dried to give 6.2 g (78 %) of crude 1-fluoro-9,10-bis (phenylethinyl) anthracene received.

This material resulted in the “treatment with hydrogen peroxide in the presence of bis (2,4,5-triohlor-6-carbopentoxyphenyl) oxalate (CPPO) to a green chemiluminescence emission. The color of the chemiluminescent emission was similar to that under comparable conditions with 9,10-bis (phenylethinyl) anthracene (BPEA) obtained.

309881/1091

Example 9

Production of 1,4,5,8-tetrachloro-9,10-bis (phenyläthinyl) anthracene

A 1 liter creased morton flask was charged with a slurry of 34.6 g (0.1 mol) 1,4,5,8-tetrachloroanthraquinone and 30.6 g (0.3 mol) phenylacetylene in 500 ml anhydrous dioxane. Then 6.9 g (0.3 mol) of lithium amide were added and the mixture was heated to reflux. The initially yellow slurry turned brown and eventually turned gray with continued refluxing. After refluxing for 96 hours, approximately 200 ml of the solvent had distilled off. The cooled reaction mixture was hydrolyzed with 400 ml of water containing 16.1 g of NH ^ Cl. A brown tar was separated from the hydrolysis mixture by decanting. Washing the tar with hexane gave a solid. Boiling this solid in acetone resulted in an off-white solid which was filtered off, washed with acetone and dried to give 42.6 g of crude 1,4,5,8-tetrachloro-9,10-bis- (phenylethinyl) - anthra-9,10-diol, melting point 272 to 276 ° C. (decomposition) (yield 77 % of theory). The infrared spectrum of this product was consistent with the intended product. The crude diol was recrystallized from 1400 ml of toluene to give 25.8 g (61%) of purified material F - 284-286 ° C obtained (decomposition, softening from 260 ⁰ C).

A mixture of 1.0 g (0.0044 mol) of tin (II) chloride and 1.0 g (0.0018 mole) 1,4,5,8-tetrachloro-9,10-bis (phenylethinyl) -anthra-9,10-diol was stirred for 1 hour in 50 ml of refluxing chloroform. After cooling down and Filtering off gave a clear, red-orange fluorescent solution. After the addition of 100 ml of hexane, it fell into place

30988 1/1091

pale pink colored solid, which was filtered off. Evaporation of the filtrate gave a red solid which was collected, washed with methanol and dried to give 0.20 g of crude 1,4,5,8-tetrachloro-9 _? i0-bis- (phenyläthinyl) -anthracene received. The infrared spectrum of this product was consistent with the structure of the desired product.

About 10 mg of the product was dissolved in 7.5 ml of 0.133 M bis (2,4,5-trichloro-6-carbopentoxyphenyl) oxalate (CPPO) in dibutyl phthalate. By adding 2.5 ml of 1.5 m H ₂ O ₂ and 0.0005 m sodium salicylate in a mixture of 80 % dimethyl phthalate and 20 % tert-butanol, a red-orange colored chemiluminescent radiation was produced.

309881/1091

Claims (8)

PATENT CLAIMS: Chemiluminescent composition that develops chemiluminescent light with a hydroperoxide, thereby marked that they (1) * an ester of an oxalic acid of the formula: 0 / ON I ₁ -OC -W _n - 0 - R, in which R ^ and Rp aliphatic or aromatic groups and η is zero or an integer from 1 to 9, (2) a fluorescent compound comprising one formed by fluorine atoms, chlorine atoms, bromine atoms or low molecular weight Bis (phenylethinyl) anthracene substituted by alkyl groups and (3) contain an organic solvent, the ingredients being present in such concentrations are that when the composition is reacted with hydrogen peroxide, chemiluminescent radiation develops will. 2. Composition according to claim 1, characterized in that the chemiluminescent compound is a bisester which is oxalic acid. 30988 1/109 1 3. Composition according to claim 2, characterized in that that the ester comprises an ester formed from oxalic acid and a phenol, the phenol being a —10 ionization constant in water greater than 1.3 x 10 having, 4. Composition according to claim 3, characterized in that that the bis (substituted phenyl) oxalate is bis (2,4,5-trichloro-6-carbopentoxyphenyl) oxalate is. 5. Composition according to claim 2, characterized in that the bisphenyl ester substituted with C arbalkoocy groups is. 6. Composition according to claim 1, characterized in that the fluorescent compound is a monochloro or a dichloro derivative of 9,10-bis (phenylethinyl) anthracene is. 7. Composition according to claim 6, characterized in that the fluorescent compound 1,5-Dlchlor-9,10-bis (phenyläthinyl) anthracene, 1,8-dichloro-9,10-bls- (phenyläthinyl) -anthracene, 2,3-dichloro-9,1O-bis (phenyläthinyl) -anthracene, i-chloro-g ^ iO-bis-iphenyläthinylJ-anthracene or Is 2-chloro-9,1O-bis (phenylethinyl) anthracene. 8. Composition according to claim 1, characterized in that that the fluorescent compound 2-methyl-9,10-bis (phenyläthinyl) anthracene is. 309881/1091