DE2016582C2 - Bis (phenyl) oxalate ester derivatives - Google Patents

Description

where the sum of the Hammett sigma constants of the substituents, X, Y and Z on each fhenyl group is between about 1.4 and 2.7

2. Bis (2,4 ^ -trichloro-6-carbobutoxyphenyl) oxalate.

3. BisCAS-trichloro-o-carbopentoxypheny-oxalate.

In DE-PS IS 92 824 a chemiluminescent composition of a) a keto compound with at least two adjacent carbonyl groups, b) a hydroperoxide or a hydroperoxide-providing compound, C) a fluorescent compound with a spectral emission between 330 and 1400 millimicrons and d) amindesi a diluent described as the keto compound (A) bis (2,4-dini trophenyl) oxalate, (B) bis (2,4,6-trinitrophenyl) oxalate, (C) bis (4-cyanophenyl) oxa! at, (D) bis (4-acetylphenyl) - oxalate, (E) bis (4-phenylphenyl) oxalate or (F) bis (isopropyl) oxalate. According to DE-PS 17 92 774, chemiluminescent compounds are used as chemiluminescent compounds in the case of corresponding chemiluminescent compositions Bistriphenylacetoxalic anhydride, diacetoxalic anhydride, dilaurinoxalic anhydride or bis-H-methoxybenzoeoxalic anhydride are used. From DE-PS17 95 795 it is known that bis (1,2-dihydro-2-oxo- l-pyridyl) -glyoxal is particularly suitable as a chemiluminescent compound in chemiluminescent compositions. One of the most effective chemiluminescent compounds to date is bis (2,4,6-trichlorophenyl) oxalate, which is described in Example 18 of DE-OS 15 92 824.

The chemiluminescent reaction of the known compositions still leaves something to be desired. The object of the invention is therefore to create new chemiluminescent compounds with particularly strong Chemiluminescence and this object are now achieved according to the invention by the new bis (phenyl) oxalate ester derivatives that emerge from the claims.

It has been found that the introduction of a carbalkoxy substituent into the aromatic part of an aryloxalate considerably reduces the disruptive loss of quantum yield which occurs with increasing concentration of such a luminescent compound, so that high light capacities can be achieved. This diminishing tion of the concentration-related loss of quantum yield is due to bis (phenyl) oxalate ester derivatives specified type, in which the sum of the Hammett sigma constants of the substituents is less than about 2.7. Carbalkoxyphenyl oxalate esters which are additionally substituted by other electronegative substituents so that the sum of all sigma constants of the substituents between about 1.4 and 2.7, high quantum yields at high oxalate ester concentrations, which leads to light capacities

of over 150 lumens times hours times liters '' can be achieved. Since the carbalkoxy substituent to which this result is essential has a Hammett sigma constant of about 0.4, the sum of the sigma constants of the other substituents must be at least about 1.0.

The bis (phenyl) oxalate ester derivatives of the invention of the formula given in claim 1 are in conventional chemiluminescent compositions are used. Such compositions add up for example from DE-PS 15 92 824 mentioned at the beginning or the corresponding DE-OS, wherein Instead of the keto compounds there, however, a bis (phenyl) oxalate ester derivative according to the invention is used. Except for a keto compound, a hydroperoxide, a fluorescent compound and a Diluent, a catalyst customary for such systems can also be present. Preference is given to those bis (phenyl) oxalate ester derivatives of the general formula given in which η denotes Has the value 1 and the carbalkoxy group is in the ortho position to the oxalate oxygen. Particularly preferred compounds of this type are mentioned in claims 2 and 3.

The Oxulutkon / cntrulion in the reacting system can vary within certain limits from 0.01 to 1.5 mol. It is preferably 0.03 to 0.3 mol.

The preparation of the bis (phenyl) oxalate ester derivatives according to the invention is illustrated by the two reaction equations given below and takes place according to methods known per se. In many cases, the synthesis is expediently started by reacting a carboxyphenol with a reagent for introducing the electronegative substituent, such as Cl ₂ , Br ₂ or HNO ₃ . The conditions required for this depend on the particular carboxyphenol and the reagent. Method 1 is suitable, for example, for introducing chlorine in the meta position to the phenolic OH group, while method 2 can be used to introduce chlorine in the ortho and para position to the phenolic OH group. The preparation of bis (2,4,5-tricWor-6-carbobutoxyphenyl) oxalate, namely a compound according to the invention, which is abbreviated to TCCPO in the following, proceeds as follows:

COH

Salicylic acid
I.

Method 2

Cl ₂

Il

HOCCH ₃

COH

Method 1
Cl ₂

60% smokers
H ₂ SO ₄

BuOH

OH H Cl COBu

H ₂ SO ₄

2-hydroxy-3,5,6-trichlorobenzoic acid

OO

HII

ClCCCl

Et ₃ N
ΦΆ

IV

Cl

Bis (2,4,5-trichloro-6-carbobutoxyphenyl) oxalate (TCCPO)

Examples of further compounds according to the invention are shown in Table I below, in the accompanying 50 also the sum of the sigma constants for the substituents with the exception of the respective carbalkoxy group is specified.

Table I. link Sigma consiint "

BisQ-bromo-o-carbohexoxy ^ AS-trichloropheny-oxalate Bis (3-bromo-2-carbethoxy-4,6-dichlorophenyl) oxalate bis (2-carbethoxy-4,6-dichloro-3-nitrophenyl) oxalate Bist2-carbomethoxy-4,6-dichloro-3- (trifluoromethyl) phenyl] oxalate Bis (2-carbobutoxy-4,6-dichloro-3-cyanophenyl) oxalate bis (2-carboocty! Oxy-4,5,6-trichloro-3-ethoxyphenyl) oxalate Bis (2-carbobutoxy-3,4,6-trichloro-5-ethoxyphenyl) oxalate bis (2-carbisopropoxy-3,4,6-trichloro-5-methylphenyl) oxalate

1.67
1.30
1.62
1.38
1.52
1.36
1.36
1.21

continuation Connection sigma constant Bis (2-carbisopropoxy-4,6-dichloro-5-octylphenyl) oxalate 1.57 Bis [2-carbomethoxy-3,5,6-trichloro-4- (1.1.3,3-tetramethylbutyl-1) phenyl] oxalate 1.29 Except for the fluorescent compounds mentioned in DE-PS 15 92 824 and the corresponding DE-OS

It is also possible to use other compounds, as can be seen, for example, from "The Color Index", 2nd edition, Vol. 2, The American Association of Textile Chemists and Colorists, 1956, pages 2907-2923. The preferred fluorescent compounds are 9,10-bis (phenylethynyl) anthracene, 1-methoxy-9,10-bis (phenylethynyl) anthracene, 9,10-diphenylanthracene and perylene. Your concentration in the reacting System is generally from 0.0002 to 0.03 and preferably from 0.001 to 0.005.

Catalysts suitable for the purposes of the invention are basic catalysts, for example Amines, hydroxides, alkoxides, carboxylic acid salts and phenol salts. Salts of carboxylic acids are preferred and phenols whose conjugate acids have ρKa values between 1 and 6, measured in aqueous solution. Some examples of preferred catalysts are sodium carbonate, teirabutylammonium sulfate, calcium salicylate, tetrahexylammonium benzoate, and benzyltrimethylammonium m-chlorobenzoate. As a further catalyst gates are dimagnesium ethylenediaminetetraacetate, tetraethylammonium stearate, calcium stearate, magnesium stearate, calcium hydroxide, magnesium hydroxide, lithium stearate, triethylamine, pyridine, piperidine, imidazole and Mention potassium trichlorophenoxide. In general, bases with conjugated acids whose pKa values are between about 2 and 5 appear most useful. Stronger bases result in unfavorable intensity-time distribution curves and weaker bases are only weakly effective at best. For bases within the opti- paint basicity range there is an optimal concentration range. At base concentrations below At the optimum, the shape of the decay curves is unfavorable, and at higher concentrations the light capacities drop excessively. Systems made from bis (2,4,6-tricL »orphenyI) oxalate (TCPO) have around 9,10-bis (phenylethinyl) anthracene (BPEA) in ethyl benzoate / alcohol solvent mixtures optimal concentrations for Sodium salicylate, tetrabutylammonium salicylate and tetraethylammonium benzoate in the ranges 0.0001 to 0.015 moles, 0.0001 to 0.0008 moles and 0.0001 to 0.001 moles.

Within these optimal concentration ranges, increasing the amount of base results in increased intensity and decreased lifespan, thereby allowing the selection of a desired lifespan within a Spans from 10 minutes to about 2 hours. Tetrabutylammonium salicylate and sodium salicylate give approximately equivalent results in 75% ethyl benzoate alcohol. In contrast, sodium salicylate is 75% di-

chlorobenzene alcohol is considerably less effective, which may indicate stronger ion pairing in the less polar dichlorobenzene. Salicylic acid, which is added to systems with sodium or tetrabutylammonium salicylate for buffering, counteracts the influence of the base, which leads to reduced intensity and increased service life. Salicylic acid flattens the performance curve of tetrabutylammonium salicylate systems. Combinations of salicylate salt and salicylic acid in suitable concentrations seem to have the effect a lower salicyate concentration alone to be able to almost double. While such a puttering effect does not result in superior operating performance, buffers can be beneficial in reducing storage by reducing the influence of accidental acidic or basic impurities or contaminants that form through disintegration reactions, to be further improved. The addition of tetrabutylammonium perchlorate to a system that is reduced by sodium salicylate in lower

Concentration is catalyzed, increases the intensity, but not the quantum yield. In systems that go through If sodium salicylate is catalyzed in high concentrations, the intensity is further increased by TBAP However, the light capacity and the performance due to the shape of the curve are reduced. This is in direct contrast to its effects when used on its own. Triphenylphosphine oxide has little effect on salicylate catalyzed systems.

The hydrogen peroxide concentration has a very small effect on the service life of light capacities in the concentration range from 0.03 to 0.45 mol in systems catalyzed with sodium salicylate Contains 0.03 moles of TCPO. However, the waveform performance decreases with increasing hydrogen peroxide concentration above about 0.075 mole. The lack of any appreciable influence of the hydrogen peroxide concentration on the reaction suggests that hydrogen peroxide was not

is involved in the determining step of the reaction. This also applies to related oxalyl chloride and Bis (2,4-dinitrophenyl) oxalate chemiluminescent reactions, but is for the less reactive TCPO system not to be expected.

With the addition of TBAP, the quantum yield and the light capacity of the TCPO system become considerable elevated. The higher the TCPO concentration, the more pronounced this effect of TBAP is. At a

TCPO concentration of 3 x 10 ^"2 moles increased TBAP the quantum yield and the light capacity by 36% and at a concentration of 3.6 x 10 ^-2 mol to 50%. The intensity and caused by the waveform efficiency can be increased compared Using higher concentrations of TCPO is beneficial because the light capacity is proportional to the quantum yield as well as the concentration of TCPO. TBAP is a superior catalyst for systems with a lifespan of 30 to 120 minutes.

Ä5 The increase in alcohol concentration in uncatalyzed TCPO ethyl benzoate systems affects the Light capacity does not matter much. Surprisingly, the reaction proceeds with 25% 3-methyl-3-pentanol slower than with 10% 3-methyl-3-pentanol. The curve shape is relatively unfavorable, but the uncatalyzed 25% alcohol system is apparently useful for long-lived systems. Without the addition of basic

Catalysts, an increase in the hydrogen peroxide concentration in the 75% ethyl benzoate-25% -3-methyl-3-pentanol system leads to an increase in the intensity and a shortening of the service life. One Hydrogen peroxide concentration of 0.033 mol gives a higher light coupling. Acetanilide. Salicylic acid and Triphenylphosphine oxide reduce the life of the uncatalyzed alcohol system, but apparently lead does not perform significantly better than the alcohol system alone. Are cesium and rubidium chloride although practically insoluble in 70% ethyl benzoate-25% -3-methyl-3-pentanol, they are effective catalysts in stirred systems.

The optimal catalyst concentration in the reacting system depends on the type of catalyst that is located but generally in the range from 0 to 0.1 moles and preferably from 0 to 0.01 moles.

The concentration of fyOj in the reacting system is generally 0.01 to 10 moles. Preferably it is sufficient the HjOj concentration from the same concentration as the oxalate concentration up to four times the concentration.

Organic solvents are various as solvents for the chemiluminescent components Kind of suitable. The solvents for the oxalate components are esters, aromatic hydrocarbons or chlorinated hydrocarbons. Of these solvents, ethyl benzoate, dibutyl phthalate and dimethyl phthalate are preferred. Suitable solvents for the base-containing peroxide component are primary, secondary and tertiary alcohols such as ethyl alcohol, hexyl alcohol, 2-ethylhexyl alcohol, cyclohexyl alcohols, 2-octanol, pinacol, glycerine, 1,3-propylene glycol, tert.-butanol and 3-methyl-3- pentanol. The tertiary alcohols like tert-Butylaikohoi, J-Methyi-3-pentanoi and 3,0-Dimethyi-3-octanoi, and mixtures of Fhihaiaiesicni and tertiary alcohols are preferred. All of the alcohols and esters mentioned above can be used. However, preference is given to using dimethyl phthalate and / or tert-alcohols.

With increasing temperature, the light intensity increases and the service life decreases. Above about -40 ⁰ C, the temperature of the light emission is not decisive. The oxalates according to the invention are superior to all previously known oxalates at all temperatures. The preferred operating range is between about -34 and +66 ⁰ C.

The particular benefits of bis (2,4,5-irichloro-6-carbobutoxyphenyl) oxalate (TCCPO) and bis (2,4,5-trichloro-6-carbopentoxyphenyl) oxalate (CPPO) include:

1. Higher light capacities.

2. Higher brightness in short-lived systems. j. Longer-lived systems with lower light intensity.

The invention is illustrated by the following exemplary embodiments.

In the examples, quantitative luminescence tests were carried out in a 1 cm deep 3 ml cylindrical quartz cuvette which calibrated spectroradinometer fluorimeter described was arranged. The back of the cuvette was towards the Reflcktionsverrnindening blackened and a magnetic stirrer was arranged vertically behind the cuvette to achieve rapid mixing. In the cuvette, aliquots of standardized Stock solutions of oxalate ester, hydrogen peroxide, fluorescent substance, catalyst and solvent Needs combined using syringes made entirely of glass. Generally were separate Stock solutions of individual reactants were used, however in some experiments the oxalate ester and the fluorescent substance were used in a single stock solution, or the hydrogen peroxide and the catalyst combined in a single stock solution. No differences were observed between these procedures. In most of the experiments a solvent mixture containing an alcohol was used, and the alcohol component of the mixture was only used for stock solutions of hydrogen peroxide and catalyst, since oxalate esters react slowly with alcohol and fluorescent substances are poorly soluble in them are. The order in which the reactants were added was not critical, but in general hydrogen peroxide and catalyst were added last in that order. It was made for a quick mix taken care of, the mixing speed was not critical at the rapid agitation speeds used. The experiments were not carried out in thermostats, but the environment did react Maintain a temperature of 25 ° C ± 1 ° C.

With the help of a conventional recording device, the intensity of a 5 nm section of the spectrum, the was in the region of the spectral maxima, recorded as a function of time. The spectra were as determined above and with regard to the decrease in intensity with time during the determination of the Corrected the spectrum. The raw spectral and intensity decay values were determined in accordance with the information in J. Am. Chem. Soc. 88, 3604 (1966) processed by a computer that was programmed with the calibration values, whereby corrected spectra were obtained absolute spectrally integrated intensities as a function of time and quantum yields.

Component solutions for practically usable chemiluminescence systems have to be without for a long time serious loss of light capacity can be stored. The oxalate ester system contains two chemical ones Reactants, the ester and hydrogen peroxide, and therefore requires the storage of two separate component solutions which produce light when mixed. A fluorescent substance is also required for chemiluminescence, and this must be contained in one of the two component solutions. Furthermore must at least one of the component solutions also contain any other constituents (e.g. catalyst) that are used to control the service life, improve the light capacity and adjust the light intensity decrease in intensity are required.

For usable storage stability in a system component solution, it is therefore necessary that the active constituents of this component in the solvent do not react with one another or with the container.

ren, and that reactive impurities are absent. This results in numerous limitations for the preparation of the components. For oxalate esters to have high chemiluminescence efficiency, it is necessary that the ester is highly reactive towards nucleophiles. The ester-containing component must therefore in one non-nucleophilic solvents are stored that are free from nucleophilic additives or impurities is. The purity requirements are considerable, since the usable ester bearing concentration is so low Have values like 0, G2 moles. Quantities as small as 0.01% water, alkali or other nucleophilic impurities are sufficient to reduce the light capacity in a 0.02 molar ester solution by amounts as high as 25%. Likewise, the hydrogen peroxide component solution must be free from traces of metal or other contaminants genes that decompose hydrogen peroxide. Because hydrogen peroxide makes some organic fluorescent substances oxidized, it is evident that such fluorescent substances must be stored in the ester component. Non-oxidizable fluorescent substances and some additives can, however, in principle be combined with the hydrogen peroxide component. Basic and nucleophilic catalysts, on the other hand, are best stored in the hydrogen peroxide solution

is (neutral salts or non-nucleophilic organic catalysts can in principle work with the ester component be united).

Careful selection of the container material is also necessary for usable storage stability of the two components. The first component, which consists of the oxalate and fluorescent solution, must be in must be kept in a container which does not allow the ester and the fluorescent substance to be exposed to surface catalysis or decomposed by the release of nucleophiles as a result of leaching by the solvent. From these For reasons, soft glass is a poor material. Plastics, such as polytetrafluoroethylene or polyethylene, which are used for Moisture impermeable are useful. Likewise, the second component must be kept in a container that does not contain hydrogen peroxide by surface catalysis or by releasing metal clays decomposed into the solution.

Accelerated shelf life tests were carried out to test the shelf life of various chemiluminescent compounds. These tests assume a 30 day long Storage at 75 ° C corresponds to storage at room temperature for at least 2 years. Therefore apply Solutions in which only relatively small losses in chemiluminescence quantum yield and light intensity or only relatively small changes in service life occur over 30 days at 75 ° C, as having sufficient shelf life. In some tests, the reactants were also tested by other methods, the oxal ester by infrared spectroscopy and the hydrogen peroxide by iodometry.

In practice, the light output of a chemiluminescence system is determined by the absolute values determines an intensity-time distribution. For example, many practical applications require a certain minimum intensity that is emitted during a certain minimum service life. Usually an over- A general chemiluminescent system can be defined as a system that has either the highest intensity over a required lifetime or the required intensity over a longer lifetime supplies. The practical intensity-life performance of a reaction is integrated through the whole Light capacity and the shape of the intensity decay curve are determined as by comparing FIGS. 1, 2 and 3 can be easily seen.

The figures represent intensity-time diagrams for three different systems, all of which have a light capacity of 70 lumens times hours times liters " ^1. The areas under the three curves sin <i are equal (the area is proportional to the light capacity), es However, it can be seen that the practical performances of the three systems differ considerably. Fig. 1 shows the relationships in a typical system as previously available. It can be seen that for many applications a high proportion of the light remains unused For example, if a brightness of 6 lumens is required, the useful life of the system is only 22 minutes and only the light capacity, which is represented by the rectangular area (1) (16 lumens times hours times liters "'), can be used in practice. The light with excessive intensity (area 2) or the light with low intensity (area 3) are outside the required performance range. Of the available 70 lumens times hours times liters " ¹ , 54 lumens times hours times liters" ¹ remain unused.

Fi g. 2, on the other hand, shows an extreme case in which all available light is emitted with a desired intensity of 323 asb for 15 minutes (area circumscribed by a dashed line) or of 108 asb for 45 minutes (area circumscribed by a solid line), and the total light capacity of 70 lumens by hour by liter " ^{1 can be used} for an application in which a constant output is required. It is true that the kinetics of a chemical reaction cannot be expected to follow the decay curve of Fig. 2 provides, however, curve shapes are desired which come as close as possible to it. An intensity-time distribution quota that approximates this goal is shown in FIG. 3 shown. It can be clearly seen that curve 3 is superior to curve 1. Even if both reactions produce the same total amount of light, curve 3 provides an intensity of 65 asb with twice as long a lifespan as curve 1 and 63% of the available light (49 lumens times hours times liters " ¹ ) is within the usable rectangular area.

A comparison of curves 1 to 3 shows that the ratio of the largest rectangular area to the total decay area is apparently a useful criterion for an effective curve shape. Furthermore, the values for intensity and time which bring this ratio to a maximum for a reaction should provide clues for the most beneficial intensity and life ranges for many practical applications (although not an exact Equivalence exists). Therefore a computer program for the automatic determination of this characteristic was developed see power values developed: / “the intensity for which the ratio of the rectangular intensity-time area (area 1 in Fig. 3) to the total intensity-time area has the maximum; T _c , the time during which the intensity is greater than / _c , and E _{c is} the ratio of the largest rectangular intensity-time cells to the total area. Since the absolute value of the light capacity is also a critical power factor, da delivers. «· -

Calculation program also: L _{c is} the absolute light capacity (in lumens times hour times liter " ¹ ), which corresponds to the largest rectangular intensity-time area, and L _{1 is} the absolute light capacity of the reaction up to time T ₍ (area 1 u-.id Area 2 in Fig. 3).

Example 1 Oxalate structure correlation

In Table II, the chemiluminescence obtained with various oxalate esters is under practically constant Reaction conditions compared. The oxalates were chosen to have the effect of a carbalkoxy substituent and also the influence of electronegative substitution on chemiluminescent light capacity demonstrate. From Table II it can be seen that TCCPO and BrTCCPO contain the carbalkoxy substituents and Have sigma constant sums (including the carbalkoxy substituent) between approximately 1.4 and 2.7, result in significantly higher light capacities than the other oxalates. So with TCPO and BTCO, the both sigma constants have sums between 1.4 and 2.7, but those have the carbalkoxy substituent absent, achieved relatively low light capacities.

DCCEPO and DCPO, both of which contain the required carbalkoxy substituent, but sigma constant sums below 1.4 result in relatively low light capacities. DNCBPO has a sigma consistency sum of more than 2.7 and therefore has a relatively low light capacity.

Table II

Comparison of oxalate ester chemiluminescence reactions in ethyl benzoate (EB) -3-methyl-3-pentanoi

(MP) solution ")

System concentrations

Oxalate ^b ) Sum of Life Solution % 75 Solution •% Kataly Oxalate H ₂ O ₂ BPEA Kataly Τ "; Sigma con duration middle") 75 middle sator ⁰ ) sator stants ^e ) (Min.) 100 Co (Mole) (Mole) (10 ³ moles) (10 ⁴ Mo!> 'Λ, TCCPO 1.73 EB 75 MP 25th NaSaI 0.10 0.375 2.3 37.5 BrTCCPO 2.12 EB 75 MP 25th None 0.094 0.375 3.0 - 'S DNCBPO 2.93 DMP 75 - - TBAS 0.075 0.188 2.0 5.0 TCPO (comparison) 1.59 EB 75 MP 25th NaSaI 0.030 0.075 3.0 12.5 TCPO ^d ) (comparison) 1.59 EB 75 MP 25th NaSaI 0.060 0.150 2.0 15.0 1% BTCO (comparison) 1.67 EB MP 25th NASA! 0.10 0.375 2.7 25.0 DCCEPO 1.36 EB MP 25th NaSaI 0.10 0.375 3.0 25.0 DCCPO 1.28 EB MP 25th NaSaI 0.10 0.375 3.0 25.0 V- Table H (continued) , 5-1
^: ~ ^ Oxalate ^b ) Quanta Light capacity, intensity in asb ■ cm " ¹ as a function the Zeu yield Lutn. i ·. ';
•1
Ϊ 10 ² settings
MoP ¹ Hours.
Liter " ¹ 2 min. 10 min . 30 min. 60 min. 120
Min.

TCCPO 15 6.04 180

BrTCCPO 125 5.8 167

DNCBPO 121 1.5 34

TCPO (comparison) 39 7.8 72

TCPO ^d ) (comparison) 94 1.2 22

BTCO (comparison) 74 1.3 42

DCCEPO 77 2.04 62

DCCPO 45 1.0 31

69
101

74

33
41
23

69

24

18th
24
10

30th

2.2 2.2

^a ) Reaction at 25 ° C.

^b ) TCCPO = bis (2,4,5-trichloro-6-carbobutoxyphenyl) oxalate; DNCBPO = bis (2,4-dinitro-6-carbobutoxyphenyl) oxa] at TCPO = bis (2,4,5-trichloropheny!) Oxalate; DCCEPO = bis (2,4-dichloro-6-carbethoxyphenyl) oxalate;

DCCPO = bis (2,4-dichloro-3-carbobutoxyphenyl) oxalate; BTCO = bis (3-butoxy-2,4,6-trichlorophenyl) oxalaL

^c ) NaSai - sodium salicylai; TBAS = tetrabatylararnonium acylate.

^d ) Initially insoluble TCPO present. ^c ) calculated

^s ) EB = ethyl benzoate; DMP = dimethyl phthalate; MP = S-methyl-S-pentanol.

Example 2

In this example, TCCPO is compared to TCPO under conditions that are most favorable for each connection. The conditions are given below. The results are shown in Table ΠΙ.

A: Comparison of systems with the highest light capacity and comparison of systems using TBAS catalysts.

B: Comparison of systems that are lightest for 10 minutes and comparison of systems using sodium salicylate ίο C: Comparison of systems that are 6.5 hours brightest.

D: Comparison of systems at -20 ⁰ C. Example 3

The chemiluminescence of bis (2 _> 4 ^ -trichloro-6-carbopentoxyphenyl) oxalate (CPPO) and bis (2,4,5-trichloro-6-carbobutoxyphenyl) oxalate (TCCPO) is compared under the same reaction conditions in Table IV. Very similar values for brightness and light capacity are achieved for the two compounds. CPPO, however, is much more soluble in dibutyl phthalate (solubility more than 0.26 mol at 25 ° C) than TCCPO (solubility about 0.07 mol at 25 ° C). So while stable solutions of CPPO at 25 ° C with a Concentration of 0.26 mol can be obtained are solutions of TCCPO with concentrations of more than 0.07 mol at 25 ° C supersaturated ur * S gradually secrete TCCPO. Regarding the solubility is therefore CPPO preferred over TCCPO

45

see table III (continued)

55

60

65

Conditional
worked Life
duration')
(Min.) Quanta
yield
(10 ² settings
MoI " ¹ ) Light capacity
(Lumen
Stde.
Liter " ¹ ) intensity
2
Min. in asb
10
Min. • cm ¹ in
30th
Min. Dependence on the
60 120 180
Min. Min. Min. 86 43 Time
400
Min. A. 126 15.2 452 516 280 194 161 24 - 5.4 A. 106 14.4 134 237 129 70 44 - - - B. 15th 6.04 180 861 441 69 - - - - B. 39 7.8 72 151 96 74 24 - - - B. 94 1.2 22nd - - - - 86 43 - C. 126 15.2 452 516 280 194 161 17th 10 5.4 C. 158 11.2 104 90 84 52 31 10 6.5 3.2 D ^r ) 580 > 2.5 > 76.3 32 30th 16 12th - - - D ^r ) - - - 5.4 2.2 - - -

Table III of bis (2,4,5-trichloro-6-carbobutoxyphenyl) oxalate (TCCPO) Oxalate Solution % the cheapest % Kataly 1 H ₂ O ₂ BPEA ^d ) fei Kataly 25th comparison Chemiluminescent reactions under medium ¹ ') sator *) and bis (2,4,6-trichlorophenyl) oxalate % sator (TCPO) in System concentrations Co- Conditions *) (Mole) (10 ³ MoI) (10 ⁴ MoI) Conditional TCCPO DBP 75 solution-oriented 25th TBAS 0.25 2.8 1.25 } worked TCPO (comparison) EB 75 middle) 25th TBAS Oxalate 0.075 3.0 1.00 30th TCCPO EB 75 MP 25th NaSaI 0.375 2.3 37.5 A. TCPO (comparison) EB 75 MP 25th NaSaI (Mole) 0.075 3.0 12.5 ;; A. TCPO «) (comparison) EB 75 MP 25th NaSaI 0.10 0.150 2.0 15.0 35 B. TCCPO DBP 75 MP 25th TBAS 0.030 0.25 2.8 $ 1.25 B. TCPO (comparison) EB 75 MP 25th None 0.10 0.075 3.0 B. TCCPO EB 75 MP 25th NaSaI 0.030 0375 2a 37.5 ί: C. TCPO (comparison) DCB 75 MP 25th TBAS 0.060 0.30 2.0 3.75 40 C. MP 0.10 D ^f ) MP 0.030 D ^r ) 0.10 0.03

^a ) Reactions at 25 ° C with the exception of ( ^f ).

°) DBP: dibutyl phthalate; EB: ethyl benzoate; DCB: 80% c-dichlorobenzene and 20% l, l, l ^ -tetrachloro-2A3 ^ -tetrafluoropropane.

^c ) TBAS: tetrabutylammonium sicylate; NaSaI: sodium salicylate

^d ) BPEA: 9,10-bis (phenylethyl) anthracene.

^e ) Time required to emit 3/4 of the total light. ^r ) Reactions at -20 ° C

*) At the beginning insoluble TCPO present.

Table IV Comparison of TCCPO and CPPO in dibutyl phthalate solution *)

TCCPO
(Mole) CPPO
(Mole) Intensity in asb
2 10
Min min 410
326 • cm ¹
30th
Min. 60
Min. 120
Min. 180
Min. Lifetime ¹ ")
(»3/4, min.) Quanta
yield
(ΙΟ ^{2 settings}
ΜοΓ ¹ ) light
capacity
(Lumen
Stde.
Liter " ¹ ) 0.1 0.1 814
515 175
167 99
93 31
42 4.3
23 54.6
98.1 10.29
10.40 305.7
317.4

*) All experiments were carried out at 25 ° C. The preparations contained 0.1 mol of the specified ester, 2.25 × ^{10 "3} mol of 9,10-bis (phenylethynyl) anthracene, 0.375 mol of H ₂ O ₂ , 1.25 × 10 ~ ⁴ MoI sodium salicylate in a solvent mixture with 75% dibutylphthalate and 25% S-methyU-pentanol.TPPO is bis (2,4,5-trichloro-6-carbopentoxyphenyl) oxalate TCCPO is bis (2,4,5-trichloro- 6-carbobutoxyphenyl) oxalate

^b ) Time required to emit 3/4 of the total light.

Example 4

The results of chemiluminescent reactions with bis (2,4-dichloro-3,5-dicarbobutoxyphenyl) oxalate (DCDCPO) are summarized in Table V. It can be seen that, under suitable reaction conditions, light capacities of at least 135 lumens χ hour χ liter ^-1 can be achieved.

Example 5

The chemiluminescences of TCCPO reactions in various solvent mixtures are in Table VI compared. High light capacities are obtained with four ester solvents, but superior light capacities are obtained in dibutyl phthalate and methyl benzoate.

Example 6

The influence of a change in the concentration of the catalyst tetrabutylsmmonium salicylate (TBAS) on the TCCPO chemiluminescence reaction in a solvent mixture of dibutyl phthalate and 3-methyl-3-pentanol is illustrated in this example. The results are shown in Table VII.

Table V Chemiluminescence of bis (2,4-dichloro-3,5-dicarbobutoxyphenyl) oxalate (DCDCPO) *)

DCDCPO NaSaI DBP EB MP Intensity in ι 10 isb -cm " ¹ as 60 72 30th 120 Life QV) Light- Function of Min. Time Min. 27 24 Min. duration ¹ ") capacity (Mole) <\ 0 ^A mol) % % % 2 30th 51 20th (Π / 4 (10 ² (Lumen Min. 29 Min. 15th 8.6 Min.) Once. Stde. [low intensity] Mole " ¹ ) Lit. " ¹ ) 0.01 1.25 75 _ 25th 75 20th 180 150.0 15.17 46.3 0.1 1.25 75 - 25th 20th 12th 0.1 25th 75 - 25th 115 13th 50.3 4.42 0.1 2.5 - 75 25th 436 7.5 112.5 1.56 135.0 0.1 25th - 75 25th 15th 48.2 2.57 47.0 220 77.3

10 15th 20th 25th 30th

40 45 50 55

60

65

25th 30th

40 45 50 55 60 65

*) Reaction of 0.00225 mol of 9,10-bis (phenylethynyl) anthracene, 0.375 mol of hydrogen peroxide, and the specified Sodium salicylate (NaSal) and DCDCPO concentration in the respective solvent mixture at 2S ° C. DBP is dibutyl phthalate; EB is ethyl benzoate.

^b ) Time required to emit 75% of the total light

^c ) Quantum yield based on the initial DCDCPO concentration.

^d ) Integrated light output per unit volume.

Table VI TCCPO chemiluminescence in various solvents ¹¹ )

IU
solvent Dibutyl phthalate Light cap., Quanta Life Intensity in asb 2 • cm " ¹ as a function of time 60 90 120 Ethylbenzene yield duration*) Min. Min. Min. Min. U ULJ X UUXVlOil Im - h - Γ ¹ (10 ² settings Γ3 / 4 30th 866 10 30th 121 71 - IS ²⁰ butyl butyrate ΜοΓ ¹ ) (Min.) Lake. 166 Min. Min. 128 104 79 366.6 12.01 60.3 1417 173 431 215 42 18th 64 325.4 10.66 141.8 79 47 136 137 131 91 51 125.4 4.11 50.9 102 181 99 237 ^ 7.78 98.2 16 96 150

^a ) Reactions of 0.10 mol of bis (2,4,5-trichloro-6-carbobutoxyphenyl) oxaJate (TCCPO), 0.00023 mol of 9,10-bis (phenylethynyl) anthracene (BPEA), 0.375 molH ₂ O ₂ , and 1.25 x 10 " ⁴ moles of tetrabutylammonium salicylate (TBAS), in a solution containing 75% of the specified solvent and 25% 3-methyl-3-pentanol

^b ) Time required to emit 3/4 of the total light.

Table VH Chemiluminescence from TCCPO systems in dibutyl phthalate (75%) and 3-methyl-3-pentanol (25%) ^a )

attempt

Intensity in asb ■ cm " ¹ as a function of time (min.)

(10 ³ MoI) (10 ⁴ MoI) 2 5 10 30 60 120

[TCCPO] [BPEAl TBAS

(Mole)

180

1 0.075 2.1 5.00 2 0.10 ') 2.8 0.625 3 0.10 ^e ) 2.8 1.25 4th 0.10 2.8 1.25 5 0.10 2.8 2.50 6th 0.10 2.8 5.00 7th 0.10 2.8 10.00 8th 0.10 2.8 15.00

Life
duration ¹¹ ) Quanta
yield') Lichtka
capacity (Γ3 / 4)
(Min.) (10 ² settings
ΜοΓ ¹ ) (Ium ■
Mr') 32 5.5 212 88 13.2 392 57 13.3 396 126 15.2 452 63 12.1 361 39 10.0 297 21 7.4 221 16 5.4 161

475 398 355 204 39 - -

538 646 495 226 118 47 26

1033 829 560 226 118 43 13

520 366 280 194 161 86 43

549 420 344 269 161 37 6 ,:

560 463 409 291 91 - -

667 603 527 151 6.5 - -

646 549 441 53 - - -

·) Experiments with 0.25 mol of H ₂ O ₂ at 25 ° C. TCCPO is bis (2,4,5-trichloro-6-carbobutoxyphenyl) oxalal; BPEA is 9,10-bis (phenylethynyl) anthracene; TBAS is tetrabutylammonium salicylate.

^b ) Time required to emit 75% of the total light.

^c ) Quantum yield based on the initial TCCPO concentration.

^d ) Integrated light output per unit volume.

^e ) TCCPO from a different production batch was used for these tests.

Example 7

This example shows the performance of the TCCPO chemiluminescent reaction in a solvent mixture of ethyl benzoate and 3-methyl-3-pentanol. The results are shown in Table VIII.

Example 8

In this example, TBAS is used as a catalyst for a TCCPO chemiluminescent reaction in dichlorobenzene used as a solvent. The results are shown in Table IX, from which the influence of the change in the concentration of the fluorescent substance can also be seen.

Example 9

This example shows the influence of temperature on the TCCPO chemiluminescence reaction. the Results are shown in Table X.

Table VIII Chemiluminescence of TCCPO systems in ethyl benzoate (75%) and 3-methyl-3-pentanol (25%) ')

[TCCPO] [BPEA] H ₂ O ₂ TPAS Salicylic
acid Intensity in asb
the time (min.) • cm ¹ as a function Le
bens
duration") Quan
tenaus
booty ¹ =) Light box
pa / itäl (Mole) (ΙΟ ³ M-ji) (Mole) (10 ⁴ moles) (10 ³ moles) 2 5 10 30th 60 120 180 (Γ3 / 4)
(Min.) (I0 ²
Fin et (him
h - I ^-1 I. MoP ¹ )

0.10

3.0

0.10 3.0

0.25 2.50 0.25 5.00

232 208 188 151 45 11 80.6 9.68 287.6 336 316 235 81 - - 41.7 7.87 233.7

0.10 3.0 0.25 5.00 0 356 346 334 0.10 3.0 0.25 10.0 0 421 410 376 0.10 3.0 0.25 15.0 0 438 400 356 0.10 3.0 0.25 15.0 5.00 419 386 347 0.10 3.0 0.25 25.0 ') 0 797 669 434 0.10 3.0 0.25 25.0 ') 2.50 940 742 450 0.188 3.0 0.625 10.0 0 502 352 255

230

156

97

83

- 6.5- -

41.2 7.89 234.4 23.8 5.87 174.5 19.3 4.85 144.0 19.0 4.65 138.2 9.9 5 _v i4 152 _; 7th 9.1 5.60 1663

104 46 - 92.7 5.10 284.4

") Tests at 25 ° C. TCCPO is bis (2,4,5-trichloro-6-carbobutoxyphenyl) cj; alat; BPEA is 9,1O-bis (phenylethynyl) anthracene; TBAS is tetrabutylammonium salicylate;

^b ) Time required to emit 75% of the total light.

^c ) Quantum yield based on the initial TCCPO concentration.

^d ) integrated light output per volume unit. ^c ) Sodium salicyate instead of TBAS.

Table IX Influence of 9,10-bis (phenylethynyl) anthracene (BPEA) on TBAS-catalyzed TCCPO chemiluminescence ")

in dichlorobenzene

Ver [BPEA]

search

(Moles x 10 ³ )

/, = 5 asb /, = 50 asb rl / 41/3/4 A

(Min.) (Min.)

Quantum luminous efficacy capacity

(X 10 ² )

2 3 4th 6th

5.0 4.0 3.0 2.0 1.0

1263 257 6.67 2.4 21.9 3.20 1169 252 6.78 2.9 22.0 3.15 1039 250 2.87 4.4 19.1 2.79 737 179 6.03 4.8 19.3 1.94 382 85 2.37 4.2 ι λ α
1% ο 0.82

98.9

96.2

84.00

57.6

23.7

^a ) Reactions of 0.10 mol of bis (2,4,5-trichloro-6-carbobutoxyphenyl) oxalate (TCCPO), 0.002 mol of tetrabutylammonium salicylate (TBAS) and 0.20 mol of H ₂ O ₂ in 50% o-dichlorobenzene-25 % Freon 214-25% 3-MeUiyI-3-pentano! at 25 ° C.

Table X Influence of temperature on TCCPO chemiluminescence ")

temperature Life Quanta Light capacity intensity in asb. cm" ¹ as a function currently 60 min. duration ¹¹ ) yield ( ⁰ C) (1 min.) (10 ² settings (Ium · h ·! "') 2 min. 5 min. 10 min. 30 min. _ Mole " ¹ ) - 40 3.6 3.55 108 1657 409 65 _ 51 25th 19th 5.48 167 872 570 377 13th 29 13th 87 4.71 144 301 237 151 87 17th 0 162 3.59 110 194 140 97 55 12th -10 169 2.28 70 140 90 59 27 -21.5 585 2.50 76 81 39 30th 16

11th

") Reactions of 0.1 mol of bis (2,4,5-trichloro-6-carbobutoxyphenyl) oxalate (TCCPO), 0.0022 mol of 9,1O-bis (phenylelhinyl) anthracene (BPEA), 0.375 mol of H ₂ Oj, and 0.00375 moles of sodium salicylate in 75% ethyl benzoate 25% 3-methyl-3-pentanol solution.

^b ) Time required to emit 3/4 of the total light.

Example IO

In this example, the shelf life of TCCPO and BPEA in dibutyl phthalate and in ethyl benzoate at 75 ° C. in a polytetrafluoroethylene container is determined for up to 60 days. This test represents an accelerated service life test, which corresponds to normal storage of at least 2 years. The result Table XI shows the results.

Example 11

The shelf life of hydrogen peroxide solutions in 3-methyl! -3-pentanol in the absence of a KaU-IS lysators and in the presence of sodium salicylate (NaSaI) or tetrabutylammonium salicylate as a catalyst is given in Tables XII and XIII. It is found that these components have sufficient storage stability for use in two-component chemiluminescent systems.

Example 12

In this example, the shelf life of TCCPO with BPEA will be explained in a Dibutylphthalatlösungsmittel at 50 ⁰ C in a polytetrafluoroethylene container. The results are summarized in Table XIV.

Example 13

A solution of 0.111 mol TCCPO and 0.0031 mol BPEA in dibutyl phthalate is prepared as one component of a two-component Cheraolumir & szenz system. The second component consists of a solution of 2.5 mol of hydrogen peroxide and 0.005 mol of TBAS in tert-butyl alcohol. The system is activated by mixing 9 parts of the first (oxalate) component with 1 part of the second (peroxide) component. The performance of the system is summarized in Table XV. In Table XV, the performance of the system is also specified in the oxalate component polytetrafluoroethylene at 50 ⁰ C after 37 days storage storage.

Table XI

trafluoroethylene Oxalate at 75 ' ¹ C Quanta light Life Intensity in asb. cm ' 667 5 .) 10 as a function 30 60 Ver kcmpo- camp yield ¹ ') capacity duration ⁰ ) the time (min. 1109 search nente *) duration (10 ² settings (In · liter " ¹ ) (Γ3 / 4 min.) 1 667 280 269 20th 215 20 (Days) ΜοΓ ¹ ) 667 420 344 140 1.1 A ^d ) 12.8 177 31 753 430 355 258 36 - 1 0 12.8 177 20.3 538 366 355 269 140 3.44 30th 9.0 124 14.2 915 366 301 151 10 - B ") 60 11.6 161 22nd 280 140 269 3.2- 2 1 10.0 138 18.7 796 430 204 11 - 30th 4.8 66.4 10.2 34 C) 60 5.03 155.6 9.7 80 3 0

30 5.27 163.0 9.4 1076 775 570 30 - -

60 3.88 120.1 5.0 1485 915 52 - -

30 1.17 36.3 6.7 248 172 69 7.75 - -

^a ) Component A contains 0.0555 mol of bis (2,4,5-trichloro-6-carbobutoxyphenyl) oxalate (TCCPO) and 3.5 x 10 " ³ mol of 9,10-bis (phenylethynyl) anthracene (BPEA) in dibutyl phthalate ; Component B is identical with the exception that it contains 1.6% (w / v) CaCO ₃ ; component C contains 0.133 mol TCCPO and 4 x 10 " ³ mol BPEA in ethyl benzoate.

^b ) Quantum yield based on TCCPO.

^c ) Time required to emit 3/4 of the total light.

⁴ > For chemoium invasion test, 5 parts of stored Oxslatkponente are with! Partly mixed freshly made peroxidioraponent containing 0.700 moles H ₂ O ₂ , 3.0 x 10 " ³ moles of tetrabutylammonium salicylate (TBAS) and 3.0 x 10 ^-3 moles of saicylic acid in dibutyl phthalate

^e ) For chemiluminescence tests, 3 parts of the oxalate components are mixed with 1 part of freshly prepared peroxide component which contains 1.0 mol of H ₂ O ₂ and 0.01 mol of sodium salicylate in 3-methyl-3-pentanol

Table XII Storage stability of r ^ Oj-NaSalO-MethylO-pentanol components at 75 ⁰ C in polytetrafluoroethylene ¹ )

Compo NaSaI ") camp Intensity in ) 10 asb ' cm ' as a function 180 the Time camp Quantum light nent duration (Min. duration ¹ ) exercise ^d ) cape.') (10 ⁴ MoI) (Days) 2 224 30th 60 120 29 240 360 Γ3 / 4 (10 ^J settings (In the · 131 22nd (Min.) Mole " ¹ ) hl "') 1 none 0 307 321 130 85 46 23 18th 7.5 155.2 9.57 284.2 none 30th 163 204 81 54 32 25th 17th 12th 302.3 7.86 240.0 2 0.25 0 586 350 147 83 40 20th 14th 6.5 113.0 10.44 310.3 0.25 30th 359 220 123 74 39 26th 15th 7.5 147.3 8.80 268.5 3 0.625 0 669 4iö 166 85 39 4.3 12th - 90.5 10.38 308.3 0.625 30th 381 270 131 80 41 25th 18th - 138.8 8.71 265.7 4th 1.25 0 8i4 Ί75 99 3i - - 54.6 ! 0.29 305.7 1.25 30th 501 132 77 40 14th - 111.6 9.36 285.7

") stored solutions contain:

1. 1.5 moles of hydrogen peroxide (H ₂ O ₂ ) and no sodium salicylate (NaSaI) in 3-methyl-3-pentanol (3M3P).

2. 1.5 mol H ₂ O ₂ and 1 x 10 ' ⁴ mol NaSaI in 3M3P.

3. 1.5 moles H ₂ O ₂ and 2.5 X 10 " ⁴ moles NaSaI in 3M3P.

4. 1.5 moles H ₂ O ₂ and 4.0 x 10 " ⁴ moles NaSaI in 3M3P.

Each solution in technically distilled 3-methyl-3-pentanol (3M3P) is stored in the container at 75 ° C. Chemiluminescence tests are carried out at 25 ° C with preparations containing 0.1 mol of bis (2,4,5-trichloro-6-carbobutoxyphenyl) oxalate (TCPO), 2.25 x 10 " ³ mol of 9,10-bis ( phenylethynyl) anthracene and 0.375 mol H ₂ O ₂ as well as the NaSal concentration given in the table.The solvent consists of 75% dibutyl phthalate and 25% 3M3P.

^b ) Catalyst concentration in the overall system.

^c ) Time required to emit 75% of the total light.

^d ) Quantum yield based on the initial TCCPO concentration.

^e ) Integrated light output per volume unit.

35

Table XIII Storage stabilities of H ₂ O ₂ - TBAS components at 50 ⁰ C)

40

50

60 65

Storage duration Intensity in asb ■ cm 'as a function of time Lifespan ⁶ ) (min.)

(Days) 2 10 30 60 120 Γ3 / 4 (min.)

Quantum yield ⁰ ) light cap. ^d ) (10 ² settings MoP ¹ ) ( ^{Imh Γ 1} )

0 988 '485 195 99 33 53.5 12.18 361.9 30th 933 479 230 99 29 51.7 12.00 357.0 60 656 365 160 85 38 87.6 10.25 304.7 90 220 187 114 73 38 171.7 8.44 257.7

") Stored solution contains: 1.5 MoI hydrogen peroxide (H ₂ O ₂₎ and 5 x 10 ~ ⁴ mol of tetrabutylammonium salicylate (TBAS) in 3-methyl-3-pentanol (distilled semi-industrial).

Chemiluminescence tests are carried out at 25 ° C. with preparations containing 0.1 mol of bis (2,4,5-trichloro-6-carbobutoxyphenyi) oxalate, 2.25 × 10 " ³ mol of 9,10-bis (phenylethynyl) anthracene, 0.375 Moles of H ₂ O ₂ and 1.25 x 10 " ⁴ moles of TBAS, contained in 75% dibutyl phthalate (DBP) 25% S-methyl-S-pentanol solvent mixture.

^b ) Time required to emit 75% of the total light

^c ) Quantum yield based on the initial TCCPO concentration.

^d ) Integrated light output per unit volume.

Table XIV Storage stability of 0.11 mol and 0.004 mol TCCPO BPEA in dibutylphthalate at 50 ⁰ C in polytetrafluoroethylene Storage time quantum light capac. ^{Lifespan 0} ) Intensity in asb · cm "'as a function of time (min.)

yield ¹¹ )

(Days) Ί0 ^{2 settings} (Im ■ h ■ Γ ¹ ) (Γ3 / 4, min.) 1 5 10 20 30 60 120

.Viol " ¹ )

10 0 37 64 96

15th

^a ) Commercially available dibutyl phthalate. For chemiluminescence tests, 9 parts of the stored component with 1 part! a peroxide component combined, the 2.5 mol of H ₂ O ₂ and tetrabutylammonium salicylate (0.005 mol) in distilled tsri.-SuSsnc! snthsU.

^b ) Quantum yield based on TCCPO.

2Q ^c ) Time required to emit 3/4 of the total light.

Table XV

Performance of a 2-component TCCPO chemiluminescence system

10.12 300 41 990 473 398 344 8.82 269 44 581 387 334 301 9.98 296 37 667 452 398 334 8.45 254 33 646 495 441 355

280 107 269 118 280 101 280 56

25th Days
storage Quanta
yield Light capacity Intensity in asb - cm "'as a function currently 60 min. at 50 ⁰ C (10 ² settings mole " ¹ ) (lm-h · I " ¹ ) 1 min. 10 min. 30 min. 107 30th O 10.1 301 990 398 280 118 37 8.8 269 581 334 269 35 Example 14
B <s (2,44-trichloro-6-garbobutoxyphenyl) oxalate

S.S.o-trichlorosalicylic acid (US-PS 30 62 877): In a solution of 300 g (1.45 mol) of 3,5-dichlorosalicylic acid and 37.5 mg of iodine in 400 ml of 65% strength fuming sulfuric acid is passed in chlorine gas for 24 hours while the temperature is kept at 70 ^° C. The cooled solution is, with good mixing, to 2 kg egg? poured, and the colorless Feskioff is filtered off. 294 g (84%) of the product with a melting point of 206 to 208 ° C. are obtained. Large amounts of product can be recrystallized from aqueous ethanol, but this is likely to be unnecessary. ButylO.So-trichlorosalicylate: 77 g (0.32 mol) 3,5,6-trichlorosalicylic acid and 50 g concentrated sulfuric acid are dissolved in 400 ml of n-butanol. The reaction mixture is refluxed for 20 hours and then diluted with 2 liters of water. The organic phase is separated off, taken up in 150 ml of petroleum ether, twice washed with 250 ml of water, filtered to remove starting materials and evaporated to dryness in vacuo for 8 hours, whereby 46.8 g (49%) of pale yellow crystalline product with a melting point of 33.5 to 35.5 ° C can be obtained.

see above bis (2,4,5-trichloro-6-carbobutoxyphenyl) oxalate: A solution of 201 g (0.67 mol) of butyl 3,5,6-trichlorosalicylate and 68 g (0.67 mol) of triethylamine in 500 ml of reagent-grade benzene is stirred with a solution of 47 g (Ο37 mol) oxalyl chloride in 75 ml reagent-grade benzene added dropwise in 30 minutes at 25 ° C When the addition of the oxalyl chloride is complete, the reaction mixture is stirred for 3 hours at 25 ° C. and then for Removal of triethylamine hydrochloride filtered. By evaporating the filtrate to dryness and three times Recrystallization of the residue from cyclohexane gives 115 g (53%) of white crystalline product with a melting point of 120 to 123.degree.

Anal, calcd .: for C ₂₄ H ₂₀ Cl ₆ O ₈ : C 44.40; H 3.11; Cl 32.77. get: C, 44.61; H 3.21; Cl 32.60.

Example 15 Bis (2,4-dichloro-3-caibubutoxyphenyl) oxalate

2,6-dichloro-3-hydroxybenzoic acid: The product is prepared according to the process described in Ann. 261,239 (189 X) is described for the preparation of trichloro-3-hydroxybenzoic acid, and recrystallized from benzene to give 46 g (55%) of crystalline product with a melting point of 110 to 115 ° C.

Anal, calc .: TUrC ₇ H ₄ CI ₂ O ₁ : C 40.61; H 1.95; Cl 34.25.
Found: C 40.14; H 1.95; Cl 33.30.

Butyl 2,6-dichloro-3-hydroxybenzoate: A solution of 24.0 g (0.16 mol) 2,6-dichloro-3-hydroxybenzoic acid and 5 g concentrated sulfuric acid in 125 ml n-butanol is taken for 20 hours Maintained reflux, cooled and then diluted with 1.5 liters of water. Taken up in 100 ml of petroleum ether, washed twice with 50 ml water, dried over CaCl _2, the organic phase is separated, filtered, concentrated for 4 hours under reduced pressure at 3O ⁰ C and then evaporated 3 hours in vacuo at 50 ⁰ C to give 22.1 g (72%) of a pale yellow liquid are obtained, the IR spectrum of which agrees with the expected spectrum for the desired product.

Bis (2,4-dichloro-3-carbobutoxyphenyl) oxalate: A solution of 22.1 g (0.084 mol) of butyl-2,6-dichloro-3-hydroxybenzoic acid and 8 g (0.080 mol) of triethylamine in 150 ml of reagent grade Benzene is slowly admixed with 5.3 g (0.042 mol) of oxalyl chloride at 25 ° C. with stirring in a nitrogen atmosphere over the course of 5 minutes. The reaction mixture is stirred for one hour at 25 ° C. and then filtered. The filtrate is evaporated for 3 hours under reduced pressure at 40 ^° C., whereby a mixture of a yellow crystalline solid and a dark brown liquid is obtained as residue. The crude crystalline product is filtered off and recrystallized four times from cyclohexane to 3.1 g (12.7%) white crystalline product of melting point 106 to 108 ⁰ C.

Anal. For C ₂₄ H ₂₂ Cl ₄ O ₈ : C 49.68; H 3.82; Cl 24.44.

r? .f .: C 49.50; H 3.80; Cl 24.00.

Example 16
Bis (2,4,5-trichloro-6-carbopentoxyphenyl) oxalate (CPPO)

n-Pentyl-SSo-trichlorosalicylate: A solution of 48.3 g (0.20 mol) of purified 3,5,6-trichlorosalicylic acid, 200 ml of n-pentyl alcohol and 4 g of concentrated sulfuric acid is refluxed for 24 hours. A Dean-Stark trap is used to remove the water from the reaction solution. The cooled solution is poured into 250 ml of ice / water and the mixture is stirred for 15 minutes. After adding 20 ml of hexane, the organic layer is separated off, washed twice with 50 ml of water each time and dried over anhydrous sodium sulfate. After evaporation of the solvent, a dark oil is obtained, the distillation of which at 128 to 134 ° C./0.1 mm gives 46 g of brown liquid. Another distillation at 140 ^° C./0.1 mm gives 37.1 g (59%) of the product, infrared absorptions at 1735 and 1660 cm " ¹ .

Anal, calc .: TUrC ₁₂ H ₁₃ Cl ₃ O ₃ : C, 46.23; H 4.17; Cl 34.19.

Found: C, 46.46; H 4.42; Cl 34.25.

Bis (2,4,5-trichloro-6-carbopentoxyphenyl) oxalate: 10.1 g (0.10 mol) of triethylamine are added dropwise to a

; 'i solution of 31.2 g (0.10 mol) of n-pentyl-S.S.o-trichlorosalicylate and 6.1 g (0.05 mol) of oxal chloride in 350 ml of water

\ l given free benzene. The thick mixture is stirred at room temperature for 7 hours and removed to remove

tion of the triethylamine hydrochloride filtered. The solid is washed with 100 ml of benzene and the filtrate

• \ _t is evaporated at 60 ° C / 50 mm. After dissolving the remaining oil in 100 ml of hexane and cooling the

20.3 g (60%) of colorless solid with a melting point of 76 to 84 ° C. are obtained in the solution. Recrystallize ms

$ 150 ml of hexane provides 17.7 g of product with a melting point of 83 to 86 ° C. Infrared absorption at 1790 and 1735 cm " ¹ .

&

$ Anal, Calcd .: door C ₂₆ H ₂₄ Cl ₆ O _8: C, 46.08; H 3.55; Cl 31.46.

p Found: C, 46.42; H 3.61; Cl 31.51.

j | _: By evaporating the 100 ml of hexane filtrate from the first oxalate crystallization, 10.8 g of unchanged

H salicylate obtained. The product yield based on unrecovered salicylate is therefore 90%.

I example 17

ρ The following Table XVI gives values for the storage stability of hydrogen peroxide solutions containing salicylate

Containing H catalysts. The solutions are stored in polytetrafluoroethylene containers at 75 ° C

Ui stored and regularly by iodometric titration for hydrogen peroxide content, as well as for 'chemolumi-

^ nescence performance tested in a TCPO standard response system.

g It is found that solutions of sodium salicylate and hydrogen peroxide in tert-butyl alcohol during

| η lose only 30% of the original hydroperoxide content over a period of 80 days at 75 ° C and the original

j | practically retained borrowed light capacity. It is true that the initial intensities drop somewhat, the duration of the emission

However, Jy increases, which suggests that the basicity decreases with storage time. But it is to be

II hen that this component remains useful for more than 80 days at 75 ° C. A much better chemolumif · ?. nescence performance is achieved with a similar solution containing dimagnesium ethylenediaminetetraacettate, H although the hydrogen peroxide loss is somewhat higher. Considerably higher losses of hydrogen peroxide and

ζΐ Light capacity will be required for a solution of hydrogen peroxide and sodium salicylate in 3-methyl-3-pentanol

| i found, which indicates that 80 days at 75 ° C come close to the useful stability limit. So lead

Although the intensities at 10 minutes after 55 days of storage practically unchanged after 80 days

l | long storage, however, the intensity is halved at! 0 minutes to 84 asb · cm " ¹ , and only 30% of the remains

»15

hydrogen peroxide originally present.

By adding 10% methanol or ethanol to lower the freezing point to tert-alcohol-water-

Substance peroxide sodium salicylate components will significantly reduce the stability of the component, though a Methano "i-3,6-Diinethyloctanoi-Systeine remains usable after 42 days of storage

5 Stability is observed for solutions of hydrogen peroxide and tetrabutylanunonium salicylate in 3-methyl-3-pentanoI

found after storage for 33 days at 75 ° C

Table XVI

10

15th

20th

25th

30th

40

45

Chemiluminescence of hydrogen peroxide salicylate components stored at 75 ° C in polytetrafluoroethylene containers ³⁾

Peroxide component camp loss QY- ^c ) light 1 3/4 ^e ) Intensity in asb ■ cm 'as (Additives) solvents duration % (1O ² egg is. capacity (Min.) Function of the response time (min.) (Days) H ₂ O ₂ ") ΜοΓ ¹ ) ilmh-r ¹ ) 1 5 10 30 60

1) t-butyl alcohol

2) t-butyl alcohol
(Mg-EDTA)

3) 3-methyl-3-pentanoI

4) 3-methyl-3-pentanol
(DACTA)

5) 3-methyl-3-pentanol
(9: 1) +

6) 3-methyl-3-pentano!
(Tetrabutylammo-

sodium salicylate

[0.006 mol]) ^r )

7) 3-methyl-3-pentanol
(Tetrabutylammonium salicylate
[0.0025 mol]) '*)

8) 2-ethylhexanol-1

9) So-dimethyloctanO-ol ⁺ methanol (9: 1)

55 80

55 80

0 55 80

55 80

0 34

0 33

C 31

0 30 55

C 17 42

20 30

23 38

53 70

56 66

22nd

40

21

71 97

11 53

7.2 73 6.8

7.4 9.4

6.6 6.7 5.2

8.5 8.6

6.6 2.6

3.2 3.4

7.3 6.7

6.4

6a

2.6

64.4 45.4

248 204 140

195 194

280 183 129

151 73

280 237

183 215

172 140

140 183

194 194 118

161 151

129 108

95 88

132 127

108 99

172

172

74 40

118 161

118 97

118 95

172

161

84

63 41

172 172 94 60

84 83

97 97

118 118 72 62

94 75 41

33

/ I

51

60 83

6.5 27 19

67 26

65 86

61 34

52 51 23

6.5 -

Footnotes to Table XVl:

55

60

^a )

Peroxide components contain 0.75 mol of H ₂ O ₂ and 0.015 mol of sodium salicylate (unless otherwise stated) in the solvent mentioned. When additives are used, they are added in amounts of 0.5 mg / ml and are largely insoluble even at 75 ° C. Mg ₂ EDTA is dimagnesium ethylenediaminetetraacetate; DACTA is 1,2-diaminocyclohexanetetraacetic acid. For chemiluminescence tests, 0.30 ml of the peroxide component, 2.7 ml of a solution of 0.033 mol of bis (2,4,6-trichlorophenylelhinyl) anthracene in ethyl benzoate are combined. Iodometric titration. Quantum yield.

Light capacity (total light output per liter). Time required to emit 3/4 of all light. Instead of sodium salicylate.

H ₂ O2 concentration 0.39 m. For chemiluminescence tests, 0.60 ml peroxide solution with 2.4 ml 0.0375 mol bis (2,4,6-trichlorophenyl) oxalate (TCPO) (comparison) and 0, 00375 m 9,10-bis (phenylethynyl) anthracene combined in ethyl benzoate.

example

The influence of different concentrations of sodium salicylate as a catalyst on the TCPO reaction (Comparison) is being investigated. The results are shown in Table XVII. Sodium salicylate increases the brightness

The optimal catalyst concentration is close to 1 X 10 ^-3 moles of sodium salicylate, with an intensity of at least 59-65 abs for 43 minutes. The intensity can be increased by using a higher concentration of catalyst. increase. At such concentrations, however, considerably lower light capacities and lifetimes are achieved

Table XVII

Influence of the sodium salicylate concentration on chemiluminescence of 0.03 mol TCPO in ethyl benzoate-3-methyl-3-pentanoP)

sodium I _m J) r 1/4 °) / 3/4 ^d ) QY ^e ) Light- Characteristic performance values ¹ ) LC _C LC ₁ salicylate in asb (Min.) (Min.) (10 ² EUiSt capacity (In the· Om- (10 ³ X cm " ¹ ΜοΓ ¹ ) (In the· / "Asb Tc Ti E h-Γ ¹ ) hr ¹ ) Mole) hr ¹ ) cm " ¹ (min.) (min.) (%)

None 0.10 0.50 1.00

65 97 161 301 452 484

99

71

49

Ki 4.0 4.4

198 117 48 37 40 16

8.8 8.8 8.3 7.6 8.3 4.9

81 80 75 69

77 44

219 80 56 43 50 18th

30th 31 45 54 64 51

24 25th 34 37 49 22nd

63 51

61 57 68 34

Example 19

The influence of tetrabutylammonium salicylate (TBAS) on the uncatalyzed TCPO reaction (comparison) is shown in two different solvent mixtures (75% ethyl benzoate - 25% 3-methyl-3-pentanol and 75% ortho-dichlorobenzene - 25% 3-methyl-3- pentanol). The results are shown in Table XVIII. In ethyl benzoate / 3-methyl-3-pentanol solution a very small TBAS concentration of IXlO " ⁴ mol leads to a strong increase in the light capacity (65%), but no significant improvement in the curve shape or service life. By increasing the TBAS- Concentration, however, the intensity and waveform efficiency are significantly increased, the lifetime decreased, and the light capacity decreased to the level of the uncatalyzed reaction. It can be seen that there is an optimal range of TB AS concentration (0.5 X 10 ^-3 to 1, 0x10 " ^J moles). At TBAS concentrations above this range, the light capacity drops considerably to below the level of the uncatalyzed reaction. In ortho-dichlorobenzene / S-methylO-pentanol solution, TBAS produces a strong catalytic effect, which is similar to that in ethyl benzoate / 3-methyl-3-pentanol. The optimal catalyst concentration is approximately 1 x 10 ^-3 m TBAS.

Table XVIlI

Influence of tetrabutylammonium salicylate on chemiluminescence of 0.03 mol TCPO in ethyl benzoate ¹ ) and dichlorobenzene

Bu ₁ N- / ^b 1 in
'mar I' " / 1/4 ^C ) ι 3/4 ^d ) QY ^e ) 65 99 198 8.8 light Characteristic performance data (Min.) T ₁ E. LC _C (Im ■ LC, (Im ■ salicylate asb · cm " ¹ (min.) (Min.) (I0 ² 269 32 106 14.4 cape. (Min.) (%) h-Γ ') h-Γ ') (I0 ⁴ m) Once. 592 14th 25th 9.9 (In the- I ₁ . in ΜοΓ ¹ ) 570 7.8 24 7.5 ' h-Γ ¹ ) asb 219 cm ' ¹ 96 0.4 30th 24 63 A. In ethyl benzoate / 3-methyl-3-pentanol (75-25 % By volume). 26th 0 29 39 90 None 81 7.5 27 0 47 39 63 1.0 134 30th 0 50 35 56 5.0 84 105 7.5 69 87

Reactions of 0.030 mol of TCPO (comparison), 0.075 mol of H ₂ O ₂ and 0.002 mol of BPEA in 80% by volume of ethyl benzoate / 20% by volume

3-methyl-3-pentanoI at 25 ° C.

Maximum intensity. Light decay time from maximum to 1/4 maximum intensity. Time required to emit 75% of all light. Quantum yield based on TCPO.

vg>. "ftxt.

75% by volume ethyl benzoate / 25% by volume 3-methyl-3-pentanoI.

continuation

BotN J ₁₁₁ *) in r IM "=) t2J4 ^a ) Q.Y.CJ Light- Characteristic leisiur Tc 7} ! gs data ') IC, (Im ■ salicylate asb -cm " ¹ (Min.) (Min.) (10 ² cape. (Min.) (Min.) hl "') (10 * m) Once (In the- I _c in E LCc ( ΜοΓ ¹ ) hr ¹ ) asb (%) h - Γ cm ^l

A. In ethyl benzoate / 3-methyl-3-pentanol (75-25% by volume).

10.0 549 12 16 6.0 56 118 15 0 46 26 41

10.0 473 16 17 5.3 50 110 17 0 56 28 37

B. In o-dichlorobenzene-S-methyl-S-pentanol (75-25% by volume). None too weak for measurement

10.0 473 6.9 37 7.6 69 37 44 0 34 24 53

10.0 473 6.4 37 7.3 66 36 43 0 33 22 50

25.0 5 * 9 3.3 17 4.0 37 51 19 0 37 14 29

50.0 301 2.5 9.7 1.6 14 not determined

75.0 258 1.3 3.4 0.6 5.3 not determined

^a ) Reactions of 0.03 Mo! TCPO (comparison), 0.003 mole BPEA and 0.075 mole hydrogen peroxide at 25 ° C.

^b ) maximum intensity.

°) Light decay time from maximum to 1/4 maximum intensity. ^d ) Time required to emit 75% of the total light ') Quantum yield based on TCPO.

Example 20 30th

The influence of various analyzers, which lead to a high performance of the TCPO reaction (comparison), can be seen from Tables 19 and 20. The experiments are in Table XIX and the results in Table XX specified. The results z «. , clearly show the control effect of these catalysts on the light intensity lifetime. Sodium salicylate is a superior catalyst for a chemiluminescent system with high Light intensity and short life and tetrabutylammonium perchlorate is a superior catalyst for a long-lasting system. Tetrabutylammonium salicylate and tetraethylammonium benzoate are also useful catalysts.

Table XIX (10 ² settings
Μ0Γ ¹ ) IC (Im-
hl " ¹ ) System composition
Catalyst ¹¹⁰ ) solvent ¹¹ )
(10 ² mol) (vol .-%) EB ^ 90) -3-M-3-P (10) [TCPO]
(Mol · 10 ² ) [H ₂ O ₂ ]
(Mole ■ 10 ² ) [BPEA]
(Mol · 10 ² ) 40 6.58 61 0.150 NA SAL EB (75) -3-M-3-P (25) 3.0 7.5 2.8 45 7.71 72 0.10 TEAB EB (75) -3-M-3-P (25) 3.0 7.5 3.0 9.04 84 0.05 TBAS EB (90) -3-M-3-P (10) 3.0 7.5 3.0 Intensity-lifetime-performance of TCPO chetaoluminescence 11.24 125 5.0 TBAP EB (90) -t-BuOH (10) 3.6 7.5 3.0 JU Ver
search 7.98 74 0.15 BTMATCB EB (75) -3-M-3-P (25) 3.0 7.5 3.0 1 7.78 72 0.125 NA SAL EB (75) -3-M-3-P (25) 3.0 7.5 3.0 2 8.42 78 0.125 NA SAL,
0.1 SA EB (75) -3-M-3-P (25) 3.0 7.5 3.0 55 3 6.55 61 0.10 TBAS,
5.00SA o-DCB (75) -3-M-3-P (25) 3.0 7.5 3.0 4th 7.63 69 0.10TBAS EB (75) -3-M-3-P (25) 3.0 7.5 3.0 5 9.47 88 0.125 NA SAL,
5.0SA EB (75) -3-M-3-P (25) 3.0 7.5 3.0 60 6th 14.40 134 0.01 TBAS EB (75) -3-M-3-P (25) 3.0 7.5 3.0 7th 12.53 116 0.80 TBAP 3.0 7.5 3.0 8th 65 9 10 11th 12th

β 13 8.8 81 - EB (75) -3-M-3-P (25) 3.0 7.5 3.0

Explanations (Table XIX)

^b ) NASAL: sodium salicylate

TBAS: tetrabutylammonium salicylate TBAP: tetrabutylammonium perchlorate SA: salicylic acid TEAB: tetraethylammonium benzoate BTMATCB: Benzyltrimethylammonium ^ S ^ -trichlorobenzoate

^c ) EB: ethyl benzoate 3-M-3-P: 3-methyl-3-pentanol 2-OCT .: 2-octanol L-BuOH: t-butyl alcohol o-DCB: o-dichlorobenzene

Table XX
High-performance chemiluminescence system ' ¹ )

Run ¹¹ ) Catalyst

Q *)

1 sodium aicyial *) 151 (0.00150 mol)

2 tetraethylammonium benzoate Π 8 (0.001 moles)

3 tetrabutylammonium salicylate 107 (0.0005 mol)

4 tetrabutylammonium 103 perchlorate (0.05 mol)

5 Benzyltrimethylammonium 63 2,3,6-trichlorobenzoate

(0.0015 moles)

6 sodium salicylate 63 (0.00125 mole) 50

7 sodium salicylate 60 (0.00125 mol) and

Salicylic acid (0.001 mol)

8 tetrabutylammonium salicylate 46 (0.001 mol) and salicylic acid

(0.05 mol)

9 tetrabutylammonium 37 salicylate ") (0.001 mol)

10 sodium salicylate 31 (0.00125 mol) and salicylic acid (0.05 mol)

11 tetrabutylammonium salicylate 30 (0.0001 mol)

12 tetrabutylammonium 27 perchlorate (0.008 mol)

13 none 7.5 Table XX (continued)

32
36
39
70
31

45
46

43

26th

61
72
84
125
74

72
71
78

61

6, ö

7.7

9.0

IU

8.0

7.8
7.7

8.4

6.6

20 46

49
17th
38

44
36

42

8.5

44 24 69 7.6 44 83 37 88 9.5 7.4 96 39 134 14.4 22nd 123 48 116 12.5 12th 219 24 81 8.8 60

Experiment *) Intensity as a function of time (min.)

5 10

30th

60

120

1 194 194 86 5.4 10 w 1Ow 2 204 172 118 5.2 1Ow 1Ow 3 194 161 129 88 2.2 4th 172 161 140 129 65 1Ow 5 161 118 87 71 16 1Ow 6th 118 97 81 74 24 108 79 63. 60 48 7th 129 94 79 74 38

19th

continuation Intensity as 98 function the time (min.) 30th 60 120 Attempt ⁶ ) 5 140 10 20th 58 25th 2.2 68 87 73 50 24 - 8th 172 96 65 60 41 19th 9 129 68 69 70 44 24 10 62 129 87 69 45 27 11th 118 86 37 29 14th 12th 59 45 13th

Footnotes table Reactions of 0.030 mol of bis (2,4,6-trichlorophenyl) oxalate (TCPO) (comparison), 0.003 mol of 9,10-bis (phenylethynylanthra-

cen (BPEA) and 0.075 mol H2O2 in 75 percent by volume ethyl benzoate / 25 percent by volume J-methyl-3-pentanoi (if not otherwise specified) at 25 ° C.

Numbers correspond to the numbers in the table Characteristic intensity, asb x cm "'. Characteristic lifetime (minutes). Characteristic light capacity (lumen x hour x liter ' ¹ ). Total light capacity (lumen x hour x liter " ¹ ). Quantum yield (10 ² Einstein x Mol " ¹ , based on TCPO). Maximum intensity, asb x cm ' ¹ . Response time in minutes.

asb x cm " ¹ .

90% ethyl benzoate / 10% 3-methyl-3-pentanol.

75% ortho-dichlorobenzene / 25% S-methyW-pentanol.

90% ethyl benzoate / 10% tert-butyl alcohol.

0.036 m TCPO.

1 sheet of drawings

20th

Claims (1)

Patent claims: 1. Bis (phenyl) oxalate ester derivatives of the general formula O O wherein
15th X represents chlorine, bromine, nitro, cyano or trifluoromethyl, Y is a carbalkoxy group with 1 to 8 carbon atoms in the alkoxy moiety, Z represents hydrogen, alkyl or alkoxy, m fik stands at least 1, r- stands for at least 1 and q stands for 0 or 1,