DE2016582A1 - - Google Patents

Description

The invention relates to improved chemiluminescent agents Compositions and methods of manufacture of chemiluminescent light. In particular, the invention relates to a further embodiment of the subject matter of Patent P 15 92 824.2.

The main patent is the implementation of oxalate esters with fluorescent substances and hydrogen peroxide in one Diluent and optionally in the presence of a catalyst described.

Surprisingly, it has now been found that superior chemiluminescence can be achieved by using aromatic oxalate esters with a high degree of reactivity towards hydrogen peroxide. This reactivity can be estimated with considerable accuracy using the HaAm * Lt sigma constants of the substituent groups on the displacing hay aromatic ehenol * The values of the Hamrnett sigma constants for a large number of

009842/1977 BAD ORIGINAL

can be found in the literature / "Cf. eg GBBariin and DD Perrin, Quart. Rev., 20, 75 (1966) J.

So far, however, the light output per unit volume (the light capacity) of oxalate ester chemiluminescence systems has been used by a considerable decrease in the ghemolusine ^ - efficiency (i.e. a reduction in the quantum yield) limited with increasing oxalate ester concentration. The light capacity is a main criterion for the usefulness of a hemoluminescence system, as that Light capacity the available light energy and finally the maximum brightness and useful life of the Li cn " emission determined. The light capacity L (in lumens, Hour.Liter "") with the brightness and the service life connected by the following relationships :.

OO

I d T / v

where means:

I the intensity in lumens T the time in hours V the volume of the system in liters

It can be shown that

I = 4.07 χ 10 ⁴ χ Q χ C χ Ρ

where means:

00984271-977

BATH ORIGINAL

Q is the chemiluminescence quantum yield (in. Einstein per mole Oxalate ester),

C is the oxalate ester concentration (in moles times liters), and

P a "photo-optical" constant representing perception of the human eye for the color of the emitted light.

From this equation it is clear that high light capacities require high quantum yields (Q) at high oxalate concentrations (G), and it is easy to do so can be seen why oxalate ester chemiluminescent systems used so far were limited in their light capacity. For example, at the high oxalate concentrations required for a high light capacity are required, low quantum yields are achieved, so that high light capacities are impossible was.

Surprisingly, this reduction has now been found that the introduction of a Carbalkoxysubstituenten in the aromatic part cinos Aryloxalats the loss of quantum yield, e.g. at zunehn & the Oxalatesterkonzentration occurs considerably verraiiicert enables high light capacity · the l: c:;. :: trationsbedingten sacrifices in The quantum yield achieved by carbalkoxy substitution is limited to substituted phenyloxylates for which the sum of the Hammett-Sigiua constants of the substituents is less than about 2.7. Carbalkoxyphenyl oxalate esters, which are additionally substituted by other electronegative substituents, co cia the sum of all sigma constants of the substituents between 1.4 and about 2.7, result in high quaternary yields at high oxalate concentrations, which means that light capacities of over

009842/1977

BATH ORIGINAL

-1

150 lumens times hours times liters can be achieved. Since the Carbalkoxy substituent which is essential for this result has a Hanmett sigma constant of about 0.4, must be the sum of the sigma constants of the other substituents, which is necessary to achieve high light capacities are at least about 1.0.

The general class of compounds for inventions: Purposes can be represented by the following formula:

Zq

wherein

X one or more electronegative substituents, i.e. substituents with a Hammett sigma constant such as defined above, is greater than 0, where chlorine and tri-

fluoromethyl groups are preferred,

Y is a carbalkoxy group,

Z represents a hydrogen atom, an alkyl group or an alkoxyalkyl group,

m, η and q. are integers having a value such that the Hammett sigma constant of the substituents X, Y and Z at each

009842/1977

Phenyl groups together are at least about ϊ., 4 to 2.7, where each m always has a value of at least 1, η represents the number O or a higher number, where however, particularly good results can be obtained with η = 1, and q is 0, 1, 2 or 3, and

ρ is an integer whose value is at least 1, •mean.

Xm can represent several different electronegative substituents. Perner can also use non-electronegative aryloxate Substituents such as alkyl radicals and para-alkoxy groups may be substituted, provided that only the sum of the Sigma constants of all substituents is at least about 1.4 to 2.7.

Compounds in which * η in the formula given above means at least 1 are new compounds according to the invention en.

The carbalkoxy substituent is in the preferred subgroup of the general class of compounds given above ortho to the phenolic oxygen when η is 1.

The preferred compounds are bis (2,4,5-trichloro-6-carbobutoxyphenyl) oxalate and bis (2,4,5-> triehlor-6-carbopentoxy ~ phenyl) oxalate.

The oxalate concentration in the reacting system can be in within a wide range of 0.01 m to 1.5 a. Preferably the concentration is 0.02 m to 0.3 m.

The production of Carballcoxyphenyldepivatön υοά Bis (Phenyl) -oxalateßtern, is by the two indicated belowon Hg-

000842/1977

BAD QpGlN ^ L

action equations explained. In many cases, the synthesis is expediently started by reacting a carboxyphenol with a reagent such as Cl ₂ »Br ₂ or MO to introduce the electronegative substituent. The conditions required for electronegative substitution will depend on the particular carboxyphenol and reagent. Two methods for chlorination are shown, namely “Method 1” for introducing chlorine in the meta position to the phenolic OH group and “Method 2” for introducing chlorine in the ortho and para position to OH. The 33 reactions are well known.

Manufacture of TCCPO

^COH method 2

Salicylic acid

HOCCH

II

COH

Method 1

Cl ₂

> 60 % smokers

H ₂ SO ₄

COH

Cl

III

BuOH

H ₂ SO ₄

OH 0

¹¹ 00 COBu ""

ciccc:

2-Hydroxy-3> 5,6-trichloro-benzoic acid (known).

009842/1977 BAD ORIGINAL

O O O \ ci It U ο π ■ ■ C 3u

Cl

Bis (2,4,5-trichloro-6-carboTdutoxyphenyl) oxalate (TCCPO) (new) *

Table I.

¹ Table I. Bis (2-caibalkoxy-3,4,6-tri-
chlorpheriyl) oxalate Sum of the sigma constants for substituent groups (with
Exception of a carbalkoxy group) Bis (3-carbalkoxy-2,4,6-tri- '
chlorophenyl) oxalate 1.28 Bis (4-carbalkoxy-2,3,6-
trichlorophenyl) oxalate 1.59 Bis (3,5-dicarbalkoxy-
2,4,6-trichlorophenyl)
oxalate 1.73 1.96

1.65

Bis (2,3-dicarbalkoxy-4,5, 6-tr ichlorphenyl) - oxalate

009842/1977

1.87 bis (2,4-dicarbalkoxy-3,5,6-trichlorophenyl) oxalate

1.73 bis (2,5-dicarbalkoxy-3,4,6-trichlorophenyl) oxalate

1.42 bia (2,6-dicarbalkoxy-3,4,5-trichlorophenyl) oxalate

1.96 bis (3-carbalkoxy-2,4,5,6-th trachlorophenyl) oxalate

1.65 bis (2-carbalkoxy-3,4,5,6-tetraehlorophenyl) oxalate

2,10 bisO-carbalkoxy- ^, 3,5..6-tetraehlorphenyl) oxalate

.28 bis (6-carbalkoxy-2,3,4-

trichlorophenyl) oxalate

1,28 bis (2,3-dicarbalkoxy-4,6-

dichlorophenyl) oxalate

.28 Bi3 ^, 6-dicarbalkoxy-2,4-

dic; ij.orphenyl) oxalate

1.65 Bib { 'λ s 3, 5-tricarbalkoxy-

4 _t 6-dichlorophenyl) oxalate

2.08 bis (5,4,5-tricarbalkoxy-

c , 6 ~ d.ichlorophenyl) -

oxalate

1.64 bis (2,4,6-tricarbalkoxy-3 t 5-dichlorophenyl) oxalate

1.6? Bia (3 ~ bromo-6-carbohexoxy ~ 2,4,5-trichlorophenyl) oxalate

1.3 C bis (3-bromo-2-carbethoxy-4,6-dichlorophenyl) oxalate

1.62 bis (2-carbethoxy-4,6-

dichloro-3-nitrophenyl) oxalate

1j30 bis / "2-carbomethoxy-4,6-dichloro-3- (trifluoromethyl) phenyl oxalate

0098A 2/1

1.52 bis (2-carbobutoxy-4,6 »

diohlor-3-cyanophenyl) oxalate

1.36 bis (2-earboctyloxy-4,5,6-

trichloro-3-ethoxyphenyl) oxalate

1.36 bis (2-carlDObutoxy-3,4,6-. ·

trichloro-5-ethoxyphenyl) ~ oxalate ·,.

1.21 bis (2-carbisopropoxy-3,4,6-

trichloro-5-methylphenyl) oxalate

1.57 bis (2-carbisopropoxy-4,6-

dichloro-5-octylphenyl) -. ■ oxalate

1.29 bis / ~ 2-carbometh.oxy-3,5,6-

trichloro-4- (1 »1» 3, ^v ) -tetramethylbutyl .-. 1) .phenyl_7-oxalate

1.28 bis [2- / ~ carbobis (trifluoromethyl) methoxy J- 3,4 »5,6-tetrafluorophenyl oxalate

1,36 bis (3,4,6-tribromo-2-

carbocyclohexoxyphenyl) oxalate

1.29 bis (2,4,5-tribromo-6-carboph.en.oxy-5 ~ liaxadecyl- ' phenyl) oxalate

Except for the fluorescent compounds mentioned in the main patent Further compounds can be found in "The Color Index", 2nd Edition, Vol. 2, The American Association of Textiles © Chemists and Colorists, 1956, pp. 2907-2923.

The preferred fluorescent compounds are 9> 10-bis (phenylethinyl) anthracene, 1-methoxy-9 _f 10-bls (phenylethiriyl) anthracene, 9,10-diphenylanthracene and perylene.

The concentration of the fluorescent substance in the reactant Sftem is generally from 0.0002 to 0.03 and preferably 0.001 up to 0.005.

009842/1977

BATH ORIGINAL

- ίο -

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 and phenols and their conjugate acids are preferred

Have pKa values between 1 to 6, measured in aqueous solution.

Some example fv.x 'tevo "~ - 3" 3 catalysts are sodium salicylate,' - vrubutylaniißonrumsalicylat, potassium salicylate, Te'trahexylaimjioniumbeuzoat and benzyl tr imethylammoniurc-chlorobenzoate as further catalysts are Dimagnesiumäthylendiamintetraacetat, Tetraäthylaismoniumstearat, Calciurastearat, magnesium hydroxide, calcium hydroxide, magnesium hydroxide. Lithium stearate, triethylamine, pyroline, piperidine, imidazole, and potash.

The influence: -; ■: -.- TeViirilter Kot-alysatorsn "vurce in detail at the bio; 2, 4. O ~ rr:? Hlorpkenyl) oxalate (? C? 0 '; raaktion examined» The Ρ, τα.ΐιΙ ^; -ί - · ν;, ^ are added to late- ■: V ^> ^r : * - u .. 'ui. I; j aiii-: ■■'! '■: ■ ;: ir. . ■ ;;: ο "ü.- · ■■ ■ 3: m i; 5ai; s .23: * · _{..;; A;} -.gierten acids ■ Lyrer: pK *; -.?.. . -..-.-,;, ··..:. _; & Α s ": ·:. 2 un .: 5, most useful. Ste.rx ^ i,. ^ C.oan yielded ungiirs" -ige Intensity a-time distribution _o ^ k; ■; ■. R; ■ />.; ^V , I weaker bases are at best only weak vii-krüaiii. R: r bases within the optimal basicity range there is an optimal conservation range. below the optimum the form of the decay curves is unfavorable, and at higher con ^ entratiovisn the light capacities decrease excessively - Systems found in ethyl bonzoate / alcohol solution mixtures that the optimal concentrations for N atrius ^ Hoyiat, Tetrabutyiammoniumsal-icyJ.at büw. Teträthylamironiusoer.Eoat lying in fo.l ^ cridari areas; 0.0001 to 0015; ■ ·., 0.0001 to 0.0003 iu u ::.; 0.0001 to 0.001 m .

Ö 0 3 η 4 2/1 9 7 7

BATH

Within these optimal concentration ranges. Gives an increase in the amount of base increased intensity and decreased lifespan, thereby reducing the selection of a desired one Lifespan within a range of 10 minutes to about 2 hours is made possible.

Tetrabutylammonium salicylate and sodium salicylate give approximately equivalent results in 75 # ethyl benzoate alcohol. In contrast, sodium salicylate in 75 $ Bichlorbenzol alcohol is considerably less effective, perhaps indicating a stronger ion-pairing in the less polar dichlorobenzene.

Salicylic acid, the systems with sodium or letrabutylammonium salicylate is added for buffering, as expected, counteracts the influence of the base, which leads to reduced Intensity and. increased service life. Salicylic acid flattens the performance curve of tetrabutylammonium phosphate systems away. It appears that combinations of salicylate salt and salicylic acid in suitable concentrations do the Effect of lower salicylate concentration alone can almost double. While such a buffering effect does not result in superior operating performance, buffers can be advantageous to the shelf life by reducing the influence of accidental acidic or basic Impurities or impurities that form through decomposition reactions »to further improve.

By adding tetrautylammonium perchlorate to a system that is catalyzed by low concentration of sodium salicyalt, the intensity _{9 increases} but not the quantum yield. In systems catalyzed by high concentration of sodium salicyalt, the intensity is further increased by means of , s; ität imä the duröh dB

009842 / 1Θ77 BATH

Curve-related performance but reduced. This is in direct contrast to an effect when used alone (see below), 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 0.03 m to 0.45 m concentration range in 0.03 m TOPO systems catalyzed with sodium salicylate. However, the performance ■ due to the shape of the curve decreases with increasing hydrogen peroxide concentration over approx. 0.075 m. The lack of any appreciable influence of the hydrogen peroxide concentration on the reaction suggests that hydrogen peroxide is not involved in a rate-limited step in the reaction. This also applies to related oxalyl chloride and bis (2 _f 4-dinitrophenyl) "oxalate chemiluminescent reactions, but was not to be expected for the less reactive TCPO system.

By adding TBAP, the quantum yield and the light capacity of the TCPO system are increased considerably. The higher the TCPO concentration, the more pronounced this effect of TBAP is. At a 3x10 m TCPO concentration, TBAP increases the quantum yield and thus the light

—2

capacity by 36 % and with a 3 »6 x 10 m concentration by 50 io. The intensity and the performance due to the shape of the curve are increased comparably. The use of higher TCPO concentrations is favorable, since the light capacity is proportional to the quantum yield and the TCPO concentration. TBAP is a superior catalyst for systems with a lifespan of 30-120 minutes.

Increasing the alcohol concentration in uncatalyzed TCPO-Athylbpnaoat-Syetemen affects the light

0098 ^ 2/1977 BAD ORIGINAL

capacity not essential. Surprisingly, the reaction proceeds at 25 fo 3-methyl-3-pentariol 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 ⁰ A ethyl benzoate 25 $ -3-methyl-3-pentanol system leads to a *. Increase in intensity and a shortening of the service life. A hydrogen peroxide concentration of 0.033 m gives a higher light capacity. Acetanilide salicylic acid and triphenylphosphine oxide reduce the life of the uncatalyzed alcohol system, but apparently not lead to a considerably better performance than the alcohol alone system, cesium and rubidium are indeed io Athylebenzoat- 25 # -3-methyl-3-pentanol practically insoluble in 70 , but are effective catalysts in stirred systems.

The optimum concentration of catalyst in the reacting system depends on the type of catalyst, but it is up generally in the range from 0 to 0.1 m and preferably from 0 to 0.01 m.

The concentration of HgOg in the reacting system is generally 0.01m to 10m. Preferably the Qfig concentration ranges from the same concentration as the oxalate concentration up to four times the concentration.

Organic solvents of various types are suitable as solvents for the chemiluminescent components. The solvents for the oxalate components are esters, aromatic hydrocarbons or chlorinated hydrocarbons.

BADORiAAi.

-H-

Of these solvents are ethyl benzoate, dibutyl phthalate and dimethyl phthalate are preferred.

Suitable solvents for the base-containing peroxide component are primary, secondary and tertiary alcohols, for example; Ethyl alcohol, hexyl alcohol, 2-AtIIyIlIeXyIaIkOhOl ₅ CyCiO-hexyl alcohols _r 2-octanol, pinacol, glycerine, 1,3-propylene glycol, tert-butanol and jS-methyl - ^ - pentanol.

The tertiary alcohols, e.g., tert-butyl alcohol, 3- ^ ethyl-3-pentanol and 3> 6-dimethyl-3-octanol and mixtures of phthalate esters and tertiary alcohols are preferred.

All of the alcohols and esters mentioned above can be used. Preference is given to dimethyl phthalate and / or tertiary alcohols applied.

With increasing temperature, the light intensity increases and the service life decreases. Above about -40 ^u C, however, the temperature for the light chemistry is riic ^>; > crucial. 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 (-30 and +150 ^u f)

Among the special advantages of bis (2,4,5-trichloro-6-carbo ~ butoxyphenyl.) oxalate (TCCPO) and bis (2,4,5-trichloro-6-carbopento;: y) oxalate (CPPO), which are the preferred phenyl oxalates for purposes of the invention include:

1. Higher light capacities.

2. Higher brightness in short-lived systems.

3. Longer-lived systems with lower light intensity.

009842/1977 BAD ORIGINAL

The invention is completed by the following examples explained in more detail

Quantitative iuminescence tests were carried out in the examples in a 1 cm deep 3 ml cylindrical quartz cuvette carried out, the vertical at the entry end of an already from

BGRoberts and ECHirt, Applied Spectroscopy, 21, 250 (1967) ^f ) ■

calibrated spectroradiometer fluorimeter described was arranged. The back of the cuvette was blackened to reduce reflection and a magnetic stirrer was arranged vertically behind the cuvette to achieve rapid mixing. In the cuvette, aliquots of standardized stock solutions a of oxalate ester, hydrogen, peroxide, fluorescent substance _f catalyst and solvent were combined as required using syringes made entirely of glass. In general, separate stock solutions of individual reactants were used, but in some experiments the oxalate ester and fluorescent substance were used in a single stock solution, or the hydrogen peroxide and. the catalyst combined in a single stock solution. No differences between these procedures were observed. In most of the experiments an LbV

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 it. The order of addition of the He-participants was not critical, but in general hydrogen peroxide and catalyst were added 2-last in this order. Care was taken door rapid mixing, the MischgeHchwindigkelt in the applied, rapid Eütorgeechwindigkeiten Eicht crucial

009842/1977

v / ar. The tests were not carried out in the thermostat, but Reactionstemperaturen were of 25 ° c + by the environment 1 ⁰ C-maintained.

With the help of a United Systems Corporation Digitec recorder, the intensity of a 5 in the section of the spectrum that was in the region of the spectral maxima was recorded as a function of dr> ^ time. The spectra were determined as indicated above and corrected for the decrease in intensity over time during the determination of the spectrum. The raw opral and integrity values were determined according to the information provided by

M.M. Rauhut, B.G. Roberts, and A.M.Semael, J »Am.Chem.Soc., 88, 3604 (1966)

processed by a Scientific Data 930 computer that was programmed with the values, which corrected ' Spectra absolute spectrally integrated intensities as a function of time and quantum readings were obtained.

Component solutions for practically usable chemiluminescent systems must be able to be stored for a long time without serious loss of light capacity. The oxalate ester system contains two chemical reactants, the ester and pulp peroxide, and therefore requires the storage of two separate component solutions which, when mixed, produce light. A fluororescent substance is also required for chemiluminescence and this must be contained in one of the two component solutions. ' Further, "at least one of the component solutions AUOH any further ingredients (e.g.., B <Catalyst), which aur lifetime control, zvr improvement in light capacity and ^ iv setting Lichtinteneitätabfalle required must.

009842/1977 BAD ORIGINAL

Purely a usable storage stability in a system component solution it is therefore necessary that the active ingredients of this component are not in the solvent React with each other and not with the container, and that reactive impurities are absent. "The result is clear Limitations on the preparation of the components. It is purely a high chemiluminescence efficiency with oxalate esters It is necessary that the ester has a high level of nucleophiles Degree is reactive. The ester-containing component must therefore generally be stored in a non-nucleophilic solvent that is free of nucleophilic additives or impurities. The purity requirements are considerable, since they are useful Ester bearing concentration have values as low as 0.02 m. As little as $ 0.01 of water, alkali, or other, nuoleophilic impurities are sufficient to in a 0.02 m Ester solution has light capacities as high as $ 25 to diminish.

Likewise, the hydrogen peroxide component solution must be free from traces of metal or other impurities that Decompose hydrogen peroxide. Since hydrogen peroxide oxidizes some organic fluororescent substances, it stands to reason that such fluorescent substances are stored in the Esiierkompomponent must, (on the other hand, non-oxidizable fluorescent substances and some additives can basically with the hydrogen peroxide component are combined).

Basic and nucleophilic catalysts, however, are on best stored in the hydrogen peroxide solution (neutral salts or niohtnucleophilic organic catalysts can basically be combined with the ester component).

For a useful shelf life of two components, a careful choice of the container material is also required. The first component, consisting of the oxalic ester and

000842/10 ??

BAO ORIOlNAt

Fluorescent substance solution must be kept in a container that contains the ester and the fluorescent substance not decomposed by surface catalysis or by the release of nucleophiles as a result of leaching by the solvent. For these reasons, soft glass is a poor material. Plastics, e.g. polytetrafluoroethylene or Polyethylene that is impervious to moisture are useful. The second component must also be in a container The hydrogen peroxide is not stored by surface catalysis or by the release of metal ions decomposed into the solution.

Accelerated shelf life siestas were conducted to test the shelf life of various chen.1 luminescent compounds. In this test that a 30-day long storage at 75 C ^Ü a least 2 Jafc e ^r- long storage, it is assumed in. Corresponds to room temperature. Therefore, solutions apply in which only relatively small losses in chemiluminescence quantum yield and light intensity or only relatively small changes during 30 days at 75 ° C apply. the Lybenff period occur, as sufficient storage bas tan ■. '.'".:. _o , Bai some tests the reaction silnehir.:r auo; tested by other · methods, the oxalester by infrared spectroscopy and. the hydrogen peroxide iodometrically.

In practice, the light output is a Chemiluminescent system by the absolute values for determines an intensity-time distribution. Many practical applications require a certain minimum intensity, which is given off during a certain minimum lifespan. Usually a superior Cheraolumineszenzsystera can be defined as a system that provides either the highest intensity during a required Lifespan or the required intensity

Q09S42 / ¹ 977

BAD OFMGJNAL

delivers over a longer service life. The practical one Intensity-lifetime-performance of a reaction is determined by the total integrated capacity and the form of the Intensity decay curve determined, as can easily be seen by comparing Figures 1, 2 and 3 «

The figures represent intensity-zJit diagrams for three different systems, all of which have a light capacity of 70 lumens times hours times liters "have * the areas among the three curves are equal (the area is proportional to the capacity), but it can be seen that the practical performances of the three systems differ considerably. Figure 1 shows the relationships in one typical system as it was previously available. It can be seen that for many applications a high proportion of the light remains unused. For example, if the brightness is 6 lumens is required, the usable life of the system is only 22 minutes and only the capacity that by the rectangular area. {. 1) is reproduced (16 lumens times hour ntal liter "*) is practically usable. The light with excessive intensity (area 2) or the light with low intensity (area 3) are outside the required - "power range. Of the available 70 lumens.

times the hour times the liter "that means 54 lumens times the hour

-1
Liters unused.

Figure 2, on the other hand, shows an extreme case in which the entire ' available light with a desired intensity of · \ ' 323 asb (30 foot-lamberts) for 15 minutes (area enclosed by dashed line) or from 108 asb (10 foot-lamberte) for 45 minutes (by ausegogane Line circumscribed area) is emitted, unä the total lightening capacity of 70 lumens times hours times liters for one AnweMimg can be used where a constant delivery is required, is. It is true that the kinetics of a chemical

009842/1877

Reaction do not expect it to follow the decay curve of Fi. · Delivers, but we want curve shapes that come as close as possible to it. An intensity-time distribution quota that comes close to this goal is shown in FIG. 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 delivers an intensity of 65 asb (6 foot lamberts) with twice as long a lifespan as curve 1 and 63 ? ° of the available light (49 lumens times hours times liters ■) are 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 intensity and time values that maximize this ratio for a given response should indicate the most advantageous intensity and life ranges for many practical applications (although there is no exact equivalence). A computer program was therefore developed to automatically determine these "characteristic performance values": I, 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, the time during which the intensity is higher than I ', and E_ the

C C

ratio of the largest rectangular intensity-time area to the total area. Since the absolute value of the light capacity is also a critical power factor, the computer program also provides: L the absolute light capacity

⁰ -1 4 ^He (lumens times hour times liter), the / largest rectangular intensity-time area corresponds _{f unc} χ i, _e äj_ absolute light capacity of the reaction at the time T (surface 1 and

Area 2 in Figure 3)

BAD OBtOINAt

-2T-

E3 emphasizes that a given preparation is considerable outside of their characteristic intensity and time values may be useful, and that the selection of a preparation best for a given application by comparing the performance requirements for that application with the actual Intensity-time diagram is done.

B β 1 s ρ i β 1 1

Oxalate structure correlation

Table II shows the chemiluminescence obtained with various oxalate esters under practically constant heating conditions compared. The oxalates were chosen so that they have the influence of a Ca-alkoxy substituent and further the influence of electronegative substitution on chemiluminescent light capacity demonstrate. From Table II it can be seen that TCGPO and BrTCCPO, the calcium alkoxy substituents and have sigma constant sums (including the carbalkoxy substituent) between approximately 1.4 and 2.7, significantly higher light capacities than the 'other oxalates. So with TCPO and BTCO, both of them Have sigra constant sums between 1.4 and 2.7, which but the carbalkoxy substituent is absent, relatively minor ones Light capacities achieved.

DCCEPO and DCPO, both of which have the required carbalkoxy substituents contain sigma constant sums below 1.4, result in relatively low light capacities. DNCBPO has a sigma constant sum greater than 2.7 and therefore has a relatively low light capacity. The experiments given in Table II do not provide optimized hemoluminescence conditions for the various oxalates, but still explain Ötrukturmerlciflale, on which it is necessary to achieve high lioht-. capacity matters.

j · '

Table II

■ 's! ^Zi ° ^ ~ I ^: ' ^: »' ^on Ox alate ster- Chemoluisiiieszgnz- Roakti or.en in_ Athylben.OS t (SB) -; 3- _- M_ £ thyl-3.-J'er: _i:

(KP) solution

Sys ten-gon_2: exitratior; en

_fc . '"" Cataly-

U χ a,>: t sum of ■ _R - " _t " - _{iv 0 r} ,, · ,,, + _F .-) vcpwh ^ε;

CrIgEa-Ii-On- Sol-> ne-tol- ^ ^v _c ^ ^ <.- - ^ ^. stanten ^e vans ^s vens ^ sator (a) (m) (10 e)

1.73 SB 75 MP 25 NaSaI 0.10 0.375 2.3 37.5

.LirtCCVO ' 2.12 SB 75 KP 1- ·, None 0.094 0.375 3.0

§ ... SCi: ..: - 2.93 DMP 100 - - TBAS 0.075 0.188 2.0 5.0

Φ -.- ICPO 1.59 EB 75 K? 2: NaSaI 0.030 0.075 3.0 12.5

"^ ₀ -D ₀ ⁰ 1.59 EB, 75 MP 2> NaSaI 0.060 0.150 2.0 15.0

1.67 ÜB 75 ^? i NaSaI 0.10 0.375 2.7 25.0 1.36 EB 75 MP Zj NaSaI 0.10 0.375 3.0 25.0 1.28 SB 75 HP 25 NaSaI 0.10 0.375 3.0 25.0

ction at

b) TfüPü = BisCa ^^ - trichloro-G-carbobutoxypheny-doxalate. MCBPO = bis (2,4-dinitro-6-carbobutoxvp: -. I ";; vi) o.salat.

TCPO β bis (2,4,5-trichlorophenyl) 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) oxalate.

N ;; - 3al = iatriurc salicylate; TBAS = tetrabutylammium salicylate. "K) I

Z \: 3 initially insoluble TCrO present. "cd.

calculate t _λ ^: · E3 = ethyl benzoate; DKP = diethyl phthalate; MP = 3-methyl-3-penta »iol.

Table II (cont.)

Oxalate

■ co

• as

CO

TCCPO
BrTCCPO

DUCBPO
TCPO

TCPO ^d
BTCO

DCCEPO
DGCPO

Lifespan (min.)

Quantum yield 102 ~ EiniMol * " ¹

15th

125

121 39

94 74

77

45

Light-

capacity} cum. Styles,

liter

6.04 5.8

1.5.

7.8

1.2 1.3

2.04 1.0

Intensity in asb. cm "(Pt. lbts. cm) as a radio _t tion time ^

2-10 30 60

Min, Min. Min, Min, Min.

861 441

(80) (41) (6.4)

11 67 101 69

(1.0) (6.2) (9.4) (6.4) (2.8)

151 96 74 (14) (8.9) (6.9). (2.2)

27 55 1) 33 ) ( 18th 7) ( 2.2 (2.5) (5, (3.1 1, 0.2) 82 61 7) 41 ) ( 24 2) _ (7.6) (5, (3.8 2, 45 52 8th) 23 ) ( 10 9) ( 2.2 (4 ^, 2) (4, (2.1 0, 0.2)

cn cn oo

Example 2

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

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

B: Comparison of systems that are 10 minutes brightest as well as comparison of systems using sodium salicylate.

C: Comparison of systems that are 6.5 hours brightest are.

D: Comparison of systems at -20 ^U C.

Example 3

The chemiluminescence of bis (2,4, S-trichloro-o-carbopentoxyphenyl) oxalate (CPPO) and of bis (2,4, S-trichloro-o-carbobutoxyphenyl) oxalate 'TCCPO) is compared in Table IV under the same reaction conditions. Pure the two connections very similar values are achieved for brightness and light capacity. However, CPPO is in dibutyl phthalate much more soluble (solubility more than 0.26 m at 25 ° C) than TCCPO (solubility about 0.07 m at 25 ° C). While so stable solutions of CPPO at 25 ° C with a concentration of 0.26 m can be obtained are solutions of

r, ■

f /

TCCPO with concentrations of more than 0.07 m at 25 ⁰ C are supersaturated and gradually secrete TCCPO. In terms of

the soluble Tceit is therefore preferred to CPPO over TGOPO,

BAD ORfQINAU

ix ' comparison of r <; 1 ': - »xalat Up to (2.4, DB? 75 5-carbob Tabel III. · entrations and To (2, 4, 6 -triehlor- EB 75 ϋβς-εβηζΓ utoxyphenyl) oxalate (TCCPO) sr. «Oxalate
(m) s _güri bumped Conditions ^a .V- , 5-trichlor ■ EB 75 ions under dsn respectively 0.10 (TCPO) in Cheaiolum :: EE 75 Cc-SoI -
vans ^b Sys teni-Kon 2 0.030 (m) (1O ⁵ BJ) Catalysis
sa tor A. EE. 75 MP BIa ta Iy
gate C 0.10 0.25 2.8 1,2b * - *. »■ A. DBP 75 MP 25th 2BAS 0.030 0.075 3.0 1, 00 B. ij ~ Oxalate 3 oil ve ns? έ
£ «& EB 75 MP 25th TBAS 0.060 0.375 2.3 37.5 co X * TCCPO EB 75 RV 25th NaSaI 0.10 0.075 3.0 12.5 O TCPO DCB 75 MP 25th NaSaI 0.030 0.150 2.0 15.0 O
33 TCCPO MP 25th NaSaI 0.10 0.25 2.8 1.25 2S Q L ' TCPO MP , 5 'I ¹ BAS 0.03 0.075 3.0 - i> ^f TCPO ^g MP 25th ϊϊ one 0.375 2.2 37.5 D * Tcopo MP 25th NaSaI 0.30 2.0 3.75 1 TCPO Sanctions at L5 ° C, except (i \ K
;! BPr Bibutvlrsiathalat: EB: Athvlbenzoat 25th TBAS o-dichlorobenzene and 20 % 1.1 , 1.3-tetra- ' TCCPO : DC ü: 80 % TCPO

yp; y; /
fckilor-2,2,3,3-tetrafluoropropane.

fBAS: tetrabutylaaimonium salicylate; NaSaI: sodium salicylate.
BPEA: 9,10-bis (phenylethinyljanthracene.

2 time required to emit 3/4 of the total licais
Beakiioaen at ~ i.0 ^u 0.
At the beginning insoluble r's TCPO available.

cn cn co ro

gabelle III (Ports.)

Conditional
worked Life
duration e Quanta
yield light
capacity , 3 intensity
dependency 10 '
• Min. in asb.
of the cm ¹ (ft.
Time lbts. cffi ") in Away- 400
Min. (Min.) / 102 ins.
Γ ¹ " ¹ ) ( / Lumens
Stde.
Liter* ■ 2
Min. 280
(26) 30th
Min. 60
Min. 120
Min. 180
Min. 5.4
(0.5) A. 126 15.2 452 516
(48) 129
(12) 194
(18) 161
(15) 86
(8.0) • 43
(4.0) - • A. 106 14.4 134 237
(22) 441 70
(6.5) 44
(4.1) 24
(2.2) - - B. 15th 6.04 180 861 (41) 69 - - - O (80) 96
(8.9) (6.4) - co
OO B. 39 7.8 72 151
(H) - 74 ■
(6.9) 24
(2.2) - - - to B. 94 1.2 22nd - 280
(26). - - - - 5.4
(0.5) co 0 126 1.5.2 452 516
(48) 84
(7.8) 194
(18). 161
(15) 86
(8.0) 43
(4.0) 5.2
(0.3) «« A G 158 - 11.2 104 90
(8.4) 30th
(2.8) 52.
(4.8) 31
(2.9) 17th
(1.6) 10
(0.9) - 2> ^f 580 > 2.5 > 76, 82
(7.5) 2.2
(0.2) 16
(1.5) .12
(1.1) 10
(0.9) (O ¹ , 6) - D ^f . - - *> * 5.4
(0.5) - - - -

Table IV Comparison of TCCPO and CPPO in dibutyl phthalate solution ^a

Intensity in asb. cm (foot lamberts cm * ") Lebens * - Quantenaus- Lichtkapa-TCCPO CPPO ρ _1n , _n f. _{n 19n 1ftn} duration of exploitation <»> W Min. Mn. mL Mn. Min. iin. <Vv (^ ^{2 setting} . (Lumen Min.) Mol " ¹ ) ^ t! R" ¹ )

0.1 - · 814 410 175 99 31 4.3 54.6 10.29 305.7 (75.6) (38.1) 06.3) (9.2) (2.9) (0.4 )

ο - 0.1 515 326 167 93 42 23 98.1 10.40 317.4 ο. (47.9) (30.3) 05.5) (8.6) (3.9) (2.1)

a) All experiments were performed at 25 ⁰ C. The formulations containing 0.1 m _L of the specified Esterg, anthracene 2.25 x 10-3m 9,10-bis (phenyläthinyl), 0.375 m H ₂ O _2, 1.25 x 10 "z. Htililt ii Li i lhlt 7

^ gg ,, 9, (pyy),, 375 ₂₂ ,

_ * Hatriumsalicylat in a Lösuiigsmittelmischung with 75 i 25 ° dibutyl phthalate and 7 »

cd 3-methyl-3-pentanol.

-j TPPO is bis (2,4,5-trichloro-6-carbopentoxyphenyl) oxalate.

· * »TCCPO is bis (2,4,5-trichloro-6-earbobutoxyphenyl) oxalate.

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

CX) N)

Example 4

The results of Ghemoltunin scenario reactions. with Bis (2,4-diohlor-3,5-dicarbobutoxyphenyl) oxalate (DODOPO) are summarized in (Table V. Bs can be seen that under suitable reaction conditions light capacities of at least 135 lumens χ hour χ liter ” can be.

Example 5

The chemiluminescence of TCCPO reactions in different Mixtures of solvents are compared in Table VI. Using four ester solvents will result in high Light capacities achieved - however, superior light capacities are achieved in dibutyl phthalate and methyl benzoate obtain.

Example 6

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

00S842 / 1977

BATH ORIGINAL

Table V Chemiluminescence of bis (2,4-dichloro-3 »5-dicarbobutoxyphenyl) oxalate (DCDG? O) ^a

DCDCPO KaSaI DBP EB MP intensity in asb. cm "(Pt.Lamberts cm) life- QY ^ L M (10 ⁴ m) * * * _duration b ^. ^ _ar;

■ - ² 10 50 60 120 / ^T 3/4} (Mol " ¹ / L ^ e-Min. Min. Min. Min. Min.

0.01 1.25 75 - 25 75 29 20 15 8.6 150.0 15.17 46.3

(7.0) (2.7) (1.9) (1.4) (0.8)

^ low intensity ^

436 180 72 30 12 50.3 4.42 135.0

(40.5) (16.7X6.7) (2.8) (1.1)

15 20 27 24 13 112.5 1.56 47.0 (1.4) (1.9) (2.5) (2.2) (1.2.). _%

220 115 51 20 7.5 48.2 2.57 77.3

»" (20.4) (10.7) (4.7) (1.9) (0.7)

*** a) B _e action of 0.00225 m 9,10-bis (phenyläthinyl) anthracene, 0.375M hydrogen peroxide, and the angege Hatriumsalicylat- (nasai) and DCDCPO concentration in the respective solvent mixture \ at 25 "C. DBP is dibutyl phthalate; EB is ethyl benzoate. ^

b) Time required to emit $ 75> of all light. . ,

c) Quantum yield based on the initial DCDCPO concentration. , q

d) Integrated light output per volume unit. 'S

O) cn OO

O 0.1 1.25 75 - 25th CD. 0.1 25th 75 25th 09 to G CD O ♦ ^ 0.1 2.5 - 75 25th 30th IO O 0.1 25th - 75 25th

Table VI TCCPO chemiluminescence in various solvents (a)

Sol-

Lichtkap ·, quantum life yield duration (10 * setting - ■ -ζ.

^Mo1 " ¹ > (mini)

Im. H. 1 "Intensity in asb. Cm" · (ft.lamb, cm ") as a function of time

30 2 10 30. 60 90 120

Lake. Min. Min_. Min min min min

Bibutylphthalstt

Ethyl benzoate Butyric lactone

*** butyl butyrate co

366.6 325.4 125.4 237.5

12.01

10.66

4.11

7.78

60.3 141.8

50.9 98.2

866 431 215 121 71

(131.7) (80.5) (40.1) (20) (11.2) (6.6)

79 166 136 137 128 104 79

(7.3) (15.4) (12.6) (12.7) (11.9) (9.7) (7.3)

173 181 99 42 18 6.5

(9.5) (16.1) (16.8) (9.2) (3, -9) (1.7) (0.6)

16 47 96 150 131 91 51

(1.5) (4.4) (8.9) (13.9) (12.2) (8.5) (4.7)

a) Reactions of 0.10 m bis (2,4,5-trichloro-6-carbobutoxyphenyl) oxalate (TCCPO), 0.00023 m 9.10 bis (phenylätlainyl) anthracene (BPEA), 0.375 m H ₂ O ₂ , and 1.25 χ 10 ~ 4 _m tetrabutylammonium salicylate (TBAS ;, in a solution containing 75 $> of the indicated solvent and 25 <$> 3-methyl-3TL thält

y ,
Contains 3-pentanol.

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

cn cn

OD

ro

Table VII Chemiluminescence from TCCPO systems in sibutyl phthalate ($ 75) and 3-kethyl

3-pentanol (25 %) ^&

"* ¹

"" ¹

Encryption / TCCPO J / BPEA_ / TBAS time: intensity in asbrcm "* ¹ (ft lbts cm.. '' ¹⁾ as a puncture
() ⁵ 4 ()

you

(m)

(10 ³ m) (10 ⁴ m)

(
the time (min.)

2 5 398
(37) 10 30th 60 120 180 475
(44.1) 646
(60) 355
(33) 204
(19) (3.6) 538
(50) 829 _#
(771 495
(46) 226
(21) 118
(11) 47
(4.4) 26th
(2.4) 1033
(96) 366
(34) 560
(52) 226
(21) 118
(11) 43
(4.0) 13th
(1.2) 520
(48.3) 420
(39) 280
(36) 194
(18) 161
(15) 86
(8.0) 43
(4.0) 549
(51) 463
(43)
603
(56) 344
(32) 269
(25) 161
(15) 37
(3.4) 6.5
(0.6) 560
(52)
667
(62) 549
(51) 409
(38)
527
(49) 291
(27)
151
(14) 91
(8.5)
6.5
(0.6) 646
(60) 441
(41) 53
(4.9)

1 0.075

2 0.1O ^e

3 O, 1O ^e

4 0.10

5 0.10

6 0.10

7 0.10

8 0.10

2.1

2.8

2.8

2.8

2.8

2.8 2.8

2.8

5.00

0.625

1.25

1.25

2.50

5.00 10.00

15.00

attempt

4th
S.
6th

T
8th

Lifetime b

(5? 3/4) (min.)

32 88 57 126 63

39 21

16

Table VII (cont.) '

Quantum yield (1O ² setting mole " ¹ )

Light capacity (lum. H. 1 ~ ¹ )

212 392 396 452 361

297 221

1-61

a) Veysucte with 0.25 m H ₂ O ₂ at 25 ° C. TCCPO is bis (2,4,5-trichloro-6-oarbobutoxyphenyl) oxaj BPjSA is 9> 10-bis (phenylethinyl) anthracene; TBAS is tetrabutylammonium salicylate. Emission of 75 % of the total light required time p) Qus & tenausbeate »based on the initial TCGPO concentration

d) divided light output per unit volume

e) 3PSy this experiment. ”TCCPO from a different production batch was used.

Is *

on co

N *

Example 7

This example shows the performance of the TCCPO chemiluminescence reaction in a solvent mixture aii3 Ethyl benzoate and 3 ~ methyl-3-pentanol shown. The results are listed in Table VIII.

Examples ■

In this example, TBAS is used as a catalyst for a TCCPO cbemoluminescence reaction in dichlorobenzene as solvent used. The results show Table IX, "above all the influence of the change in concentration." of the fluorescent substance can be seen.

Example 9

This example shows the influence of temperature on the TCCPO hemoluminescence reaction. The results are shown in Table X.

009842/1977

Table VIII

Chemiluminescence of TCCPO systems in ethyl frenzoate (75 %) and 3-methyl-

^ TCCPO J

3-pentanol (25 #)

^{a <}

. H O,

• DBAS salicylic

~ χ r 2 ² α acid time: (β) (ΙΟ? *) (S) (10 ⁴ m) ( ₁₀ 3 _m ) intensity in asb. cm (ft.lbts. cm ~). as puncture of time (min.)

10

60 120

0.10 0.10

cd 0.10

0.10 0.10

0.10 0.10 0.10 0.188

3.0

3.0

3.0

0.25 2.50

0.25 5.00

0.25 5.00

3.0 0.25 10.0 0 3.0 0.25 15.0 0 3.0 0.25 15.0 5.00 3.0 0.25 25.0 ^e 0 3.0 0.25 25.0 ^e 2.50 3.0 0.625 10.0 0

275 232 208 188 151 45

(25.5) (21.6) (19.3) 07.5) (H, 0) (4.2)

347 336 316 235 81

(32.2) (31.2) (29.4) (21.8) (7.5)

356 346 334 230 76 -

(33.1) (32.2) (31.0) (21.4) (7.1)

410 376 156

6.5 6)

(39.1) (38.1) (34.9) (14.5) (.0.6)

438 400 356 97 - <- 1, -1 -

(40.7) (37.2) (33.1) (9.0) (0.1)

419 386 347 83 - -

(38.9) (35.9) (32.2) (7.7)

797 669 434 <11 - -

(74.1) (62.2) (40.3) (1.0)

940 742 450 C 11

(87.4) (69.0) (41.8) (1.0)

502 352 .255 151 104 46

(46.6) (32.7) (23.7) (14.0) (9.7) (4.3)

(1.0)

OI CO Nd

Table VIII (Ports.)

Lifetime quantum yield ^c light capacity -

(T 3/4) (Kin.) (10 ^ Ein.-Mol -1) (Ium. H.Liter)

80.6 9.68 287.6

41.7 7.87 233.7

41.2 7.89 234.4

23.8. 5.87 174.5

19.3 4.85 144.0 19.0 4.65 138.2

ο 9.9 5.14 152.7

S 9.1 5.60 166.3

»92.7 5.10 284.4

NJ '

_ ». a) Tests at 25 ° C. TCCPO is bis (2,4,5-trichloro-6-carbobutoxyphenyl) oxalate} BPEA is σ * <o 9,10-bis (phenylethinyl) anthracene; TBAS is tetrabutylammonium salicylate; ι

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

c) Quaternary yield based on the initial TCCPO concentration.

d) Integrated light output per unit volume

e) sodium salicylate instead of TBAS.

ϊ IX

* - you i. . ? 1 σ ο ο ο 2 22 «ο 4th 6th

Influence of 9.10 ~ Bia (phanyl & thipyl) antbraeen (BPEA) on yBAS-catalyzed

^Ä in

* i * 5asfe * t «50 ash ti / 41 t3 / 4A

(ft.laaife *) .. (ft _f lamb.) (ftaaioi »,) (Min,) (Hin.)

5.0 1265 (117.3) 257 (23.9) 6.67 (0.62) 2 ^ 4 21 ^ 9 3.20 98.9

4.0 1169 (108.6) 252 (23.4) 6.78 (0.63) 2.9. 22.0 ^ ^, 15 96.2

3.0 1039 (96.6) 250 (23.2) 3.87 (0.36). 4.4 19.1 2.79 84.00

2.0 737 (68.0) 179 (16.6) 6.03 (0.56) 4.8, 19.3 1.94 57.6

1.0 55.5 (382) 7.9 (85) 0.22 (2.37) 4.2. ■,> 4.8 Q, B2 23.7

· ■■ ■ ■■ · - '

a) »eaktioften ύο» 0.10 »bis (2 _f 4,5-tri6iaor-6-earl>ol> utpacypJieo3r3.) © 3calst (fßßPO), 0.002» '

fwaaoAiiwasalicylat (fBAS) nad 0,20jb ¹ EjO ₂ i »50 5δ p-DioJil © 3? b # ö« ol-25 ^ ireon 214-255 ^ 5-peatanpI at 25 ° ß,

Tempe
rature
Cc) Life
duration b
(1 min.) Quanta
yield
1 Ci TP-i rta Influence of the temperatui Tabel ) (154) [ (38) 1C ) Min. a foot , 2) lambcrts -1 ν
CJZ j _ , 7) Mol. -1 light
capacity
+ Lumen.hour • on C (81) (53) 65 (6) . cm ~ (
Time Min. , D 60 Kin . - , 7) 40 3.6 3.55 Liter ^Ί (28) (22) ' 377 (35) 30th _ , D (4th , 6) 25th 19th 5.48 108 2 min. (18) PCCPO chemiluminescer.?; (13) 151 (14) (1 , 5) (2 , υ 13th 87 4.71 167 1657 (13) (8.4) 97 (9.0) 13th (8th / 5) 5 ¹ (1 O 162 3.59 144 87? (7.5) Intensity in asb
as a function of (3.6) 59 (5.5) 87 C 5 29 (1 -10 169 2.28 110 301 5 min. 30th (2.8) 55 (2 17th -21.5 585 2.50 70 194 409 27 (1 12th 76 140 570 16 , ο 81 237 140 90 39

to

a) Reactions of 0.1m bis (2,4,5-trichloro-6-carbobutoxyphenyl) oxalate (TCCPO), 0.0022m 9,10-bis (phenylethinyl) anthracene (BPEA), 0.375m H ₂ O ₂ , and O, OO375m latrium alicybe in 75 # ethyl benzoate — 25 $> J'-methyl-J-pentanol solution.

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

N * O

cn CXl OO Nd

saaaro: "■

Example 10

In this example the shelf life of

TCCPO and BEEA in dibutyl phthalate and in ethyl benzoate "

75 ⁰ C in a polytetrafluoroethylene container "up to

60 days "determined. This test represents an" accelerated

Lifetime test that of normal storage

of at least 2 years. The results ^tt

Table XI shows. *

Example 11

The shelf life of hydrogen peroxide solutions in 3-methyl-3-pentanol in the absence of a catalyst 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 shelf life for use in two-component hemoluminescent 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 Polytetrafluoräthylenbehälter, The results are summarized in Table XIV.

Example. 13th

As one component of a two-component Cnemolumii & eszeiiasystem a solution of 0.111 m TCCPO utid O, G £>: fL in BPEA made in dibutyl phthalate. The second component

009842/1977 BADORfGlNAU

consists of a solution of 2.5 m hydrogen perox '. 0.005 m TBAS in tert-butyl alcohol. The system is activated · ν <· Mixing 9 parts of the first () xalate) component with 1 part of the second (peroxide) component. The performance of the system is summarized in Table XV. Table XV also shows the performance of the system after 37 days of storage of the oxalate component in Po lyte trafluoroethylene (5 ml TEFLON ^ PEP ^ PiIm) at 50 ⁰ O given.

009842/1977 BAD ORIGINAL

Table X I.

The stability of TCCPO components in dibutyl phthalate and in ethyl benzoate when stored in polytetrafluoroethylene n b. 75 " C (167" F)

Qxalat- Storage- Quaten-, Lichtkapa- .. Lifespan ^c _c component ^a duration ^{yield b} city ο * / λ «n« '> ·

(Days) <J ° Ji ^ * · (in. Liter " ¹ ) , ■ ^ ^Ο ζ

A ^d 0 12.8 177 31

30 12.8 177 20.3

60 9.0 124 14.2

B ^d 1 11.6 161 22 '

SS- 30 10.0 138 18.7

S2: "r * ^'60 * 4.8 66.4 i .:: 10.2

I ^ 3 0 * 0 5.03 155.6 _{; ;} ■ ", 9.7

30 5.27 163.0-9.4

60 3.88 120.1 - "5.0

30 1.17 36.3: 6.7

's) ltpaponente A contains 0.0555m Bia (2,4, S-trichloro-e-carbobutoxyphenyl joxalate' (TCCPO) and 3,5 x10 ~ 3m 9,10-bis (phenylethinyl) anthraeae (BPEA) "in dibutyl phthalate; component B is essentially identical with the exception that it contains 1.6 % (w / v) CaCO3; component C contains 0.133m TCCPO and 4 × 10-3 m BPEA in ethyl benzoate

to) quantum yield, based on TCCPO. .., ^

c) Time required for the mission of 3/4 of the total light. ; 4) I ¹ ur hemoluminescence tests 5 parts by volume of stored oxalate component are mixed with 1st part - * freshly prepared peroxide component, which contains 0.700 m H ₂ Op ,. , 3, .O, x 10-3 m Tetrabutyip ammoixiumsalicylat (TBAS), and 3.0 X 10 "3 m salicylic acid in Ditöü'tylpht'halat contains .. ^

e) For chemiluminescence tests, 3 parts of the oxalate components with 1 part of freshly prepared Pexoxide component mixed, the 1.0 m H? 02 and 0.01 W sodium salioylate in Contains 3-methyl-3-pentene, uene. > ^^. .y

Table XI (Ports.) '

Intensity in aä

as a function of time (min.)

Experiment Oxalatkoiaponente ^a intensity in asb. cm "" (ft. Ibt. cm)

I 1 JL ^d 2eit: ] _ £ H) 2 £ __

667 (62) 280 (26) 269 (25) 258 (24) 215 (2ο) 20 (1.9)

1109 (103) 420 (39) 344 (34) 269 (25) 140 (13) .1.1 (0.1)

667 (62) 430 (40) 355 (33) 151 (14) 36 (3.3)

2 B ^d 667 (62) 366 (34) 355 (33) '269 (25) 140 (13) 3.44 (0.32)

753 (70) 366 (34) 301 (28) 204 (19) 10 (9.3)

Ι ο 538 (50) 280 (26) 440 (13) 34 (3.2) 3.2 (0.3)

X Ό '■ ■

§ 3 C ^e 915 (85) 796 (74) 430 (40) 80 (7.4) 11 (1.0)

J £ * 1076 (100) 775 (72) 570 (53) 30 (28) Ü '1485 (138) 915 (85) 52 (4.8)

• 248 (23) 172 (16) 69 (6.4) 7.75 (0.72) -

Table XII

Lagers tab ili tat von HgOg-NaSal ^ -Methyl ^ -pentanol-Komponsnteri. bi 75 "O in Teflon FEPR ^(a)

Coffiponete

NaSaI
(10 ⁴ m)

Storage time (days)

Intensity in asb. cm "" (ft. lambert cm ") as function of time (min.) 2min. 10 min. 30 min. 60 min. 120 min. 180 min. 240 min, 360min,

none

none

0.25

0.25

0.625

0.625

1.25

30th 0 30

0 30

0 30

28.5 (307) 20.8 (224) 12.1 (130) 7.9 (85) 4.3 (46) 2.7 (29) 1.7 (18) 0.7 (7.5)

163 (15.1) 131 (12.2) 81 (7.5) 54 (5.0) 32 (3.0) 22 (2.0)

586 (54.5) 321 (29.8) 147 (13.7) 83 (7.7) 40 (3.7) 23 (2.1)

359 (33.4) 204 (19.0) 123 (11.4) 74 (6.9) 39 (3.6) 25 (2.3)

669 (6272) 350 (32.5) 166 (15.4) 85 (7.9) 39 (3.6) 20 (1.9)

381 (35.4) 220 (20.4) 131 (12.2) 80 (7.4) 41 (3.8) 26 (2.4)

814 (75.6) 410 (38.1) 175 (16.3) 99 (9.2) 31 (2.9) 4.3 (0.4)

501 (46.6) 270 (25.1) 132 (12.3) 77 (7.2) 40 (3.7) 25 (2.3) 14 (1.3)

17 (1.6) 12 (1.1) 14 (1.3) 6.5 (0.6) 15 (1.4) 7.5 (0.7) 12 (1.1)
18 (1.7)

a) stored solutions contain: 1. 1.5m hydrogen peroxide (Η ₉ 0ο) and no sodium salicylate

(NaSaI) in 3-methyl-3-pentane61 (3M3P). 2. 1.5 m H ₂ ; 0 ₂ and 1 χ 10-4 m NaSaI in 3M3P. ι

3. 1.5 m H ₂ O ₂ and 2.5 x 10 ^-4 m nasai in 3M3P.

4. 1.5 m H ₂ O ₂ and 4.0 χ 10 ~ ⁴ m "NaSaI in 3M3P. Each solution in" technically distilled "3-methyl-3-pentanol (3M3P) is stored in Teflon containers at 75 ° C .Chera-luminescence tests are carried out at 25 C with preparations containing 0.1 mBis (2,4, S-trichloro-o-carbobutoxyphenyl) oxalate (TCCPO), 2.25 x 10-3m 9,10-bis (phenyläthinyl) anthracene, and 0.375 m H ₂ O ₂ as well as the NaSal concentration given in the table. Solvent consists of 75 # dibutyl phthalate and 25 * 3M3P.

b) Catalyst concentration in the overall system.

c) To the emission of 75% of the total. Light, required tent, a) Quaatsn yield, based on the initial TGGPO concentration Integrated light emission per volume unit

<7>

cn

Table XII (Ports.)

component

O CO OO

1
2
3 4

Storage time ^v 'T 3/4 (min.)

155.2 302.3 113.0 147.3

90.5 138.8

54.6 111.6 quantum yield ' (10 ^ setting Mol-1)

9.57

7.86 10.44

8.80 10.38

8.71 10.29 9.36

Light cap. ^ lm.h liter-1

284.2 240.0 310.3 268.5 308.3 265.7 305.7 285.7

Camp-

duration

(location)

Table XI II Storage stability of H ₀ Op - TBAS components at 50 ° C ^

Intensity in asb. cm "(ft. lamb, cm" ) as a function of the life

Time (min.) ■ __ duration

T 3/4.

2 min.

10 min. 30 min.

60 min.

120 min.

(c)
Quanta ^ · '

yield

Mole "')

kap .. (lm.h.

Liter " ¹ )

O 988 (91.8) 485 (45.1) 195 (18.1) 99 (9.2) 33 (3.1)

50 86.7 (933) 44.5 (479) 21.4 (230) 9.2 (99) 2.7 (29)

60 61.0 (656) 33.9 (365) 14.9 (160) 7.9 (85) 3.5 (38)

90 20.4 (220) 17.4 (187) 10.6 (114) 6.8 (73) 3.5 (38)

53.5

5.1.7
87.6

171.7

12.18

12.00

10.25

8.44

361.9 357.0 304.7 257.7

Y-4.

a) stored solution contains: 1.5 m hydrogen peroxide (H ₂ O ₂ ) and 5 x 10 m tetrabutylammonium

salicylate (TBAS) in 3-methyl-5-pentanol (semi-technically distilled)

Chemiluminescence tests are carried out at 25 ° C with preparations containing 0.1 m bis (2,4,5- ■ trichloro-6-carbobutoxyphenyl) oxalate, 2.25 10 ** 5 m 9,10-bis (phenyläthinyl) anthracene , 0.375 m H ₂ O ₂ and 1.25 χ 10 " ⁴ η TBAS, in 75 # Eastman White Label dibutyl phthalate (DBP) -25 fo 3-methyl

3-pentanol solvent mixture contain '

b) Time required to emit 75 9 »of the total light *

c) Quantum yield based on the initial TCCPO concentr.

d) Integrated light output per volume unit.

Table XIV Storage stability of 0.11 m TCCPO and 0.004 m BPEA in dibutyl phthalate

in Teflon FEP ^a

Storage quantum light capac. Life span ex- / ·. . duration ^c (days) te « ^

(10 ² settings
- ¹ )

Intensity in asb. cm "(ft. Ibt. cm ~) as puncture of time (min.)

1 min. 5 min. 10 min. 20 min. 30 min. 60 min. 120

0 10.12 300 41 37 8.82 269 44 64 9.98 296 37 96 8.45 254 33

990 (92) 473 (44) 398 (37) 344 (32)

581 (54) 387 (36) 334 (31) 301 (28)

667 (62) 452 (42) 398 (37) 334 (31)

646 (60) 495 (46) 441 (41) 355 (33)

280 (26) 107 (9.9)

269 (25) 118 (11.0)

280 (26) 101 (9.4)

280 (26) 56 (5.2)

a) Commercially available (Eastman) dibutyl phthalate. Pur chemiluminescence tests, 9 parts of the stored component are combined with 1 part of a peroxide component which contains 2.5 m HpO ₂ and tetrabutylammonium salicylate (0.005 m) in distilled tert-butanol.

b) Quantum yield based on TCOPO.

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

cry cn oo

T a b e 1 1 e XV

Performance of an S-Komoonenten-TCCPO-chemiluminescence-system Quanta
yield
10 ² settings Licbt-
capacity
Lm. B Intensity in asb
as a puncture 10 min. .cm "(ft.
currently lbt.om " ¹ ) Days
location Mole " ¹ Liter " ¹ 1 min. 398 (37)
334 (31) 30 min. 60 min. tion
at 50 ⁰ C 10.1
8.8 # \\ '
269 990 (92)
581 (54) 280 (26)
269 (25) 107 (9.9)
118 (11) 0
37

As mentioned above, substituted derivatives of bisphenyl oxalates can be obtained by a method hex \ _; .stollt with the two. Blotting methods are used. The preparation of these compounds is illustrated by Examples 14-17 below.

Example 14 bis (2,4, ^t 5-tricblor-6- _i ca, rbobutoxyphenyl) ox: ala.t (method 1 )

3,5,6-triochlorosalicylic acid (USA Patent No. 3,062,677): 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% smokers sulfuric acid is introduced chlorine gas for 24 hours, while the temperature is kept at 70 ⁰ C. The cooled solution is poured onto 2 kg of ice with thorough mixing, and the colorless solid is filtered off. There are 294 β (84 1 °) of the product of melting point 206 to 208 ° 0 - obtained (Lit ^"1, mp 203 205 ⁰ C.) Large productive may be recrystallized from aqueous ethanol, but this is probably unnecessary..

Butyl 3,5,6-trichlorosalicylate: 77 g (0.32 mol) 3,5,6-trichlorosalicylic acid and 50 g concentrated sulfuric acid are dissolved in 400 ml n-butanol. The reaction mixture. It is refluxed for 20 hours and then diluted with 2 liters of water. The organic phase is abgetr ". R.:i;-, taken up in 150 Kl Petroläthor, sweiinal v with 250: .. \ V / ater washed: .ur removal of starting materials and filtered ira vacuo for 8 hours to l 'evaporated dry, leaving 46.8 g (49 #) pale yellow crystal ::. Product from Schraoj ^ pimkt 33.5 "to 35.5 ⁰ C can be obtained.

0 Ü Π P i, I 1 9 7 7 BADiiORIiSINAL

3i3 (2,4,5 ~ trieblor »-6 - carbobutoxyphenyl) -axalate:

2 Ine solution of 201 g (0.67 mol) butyl «3,5» 6-trichlorosalicylate and 68 g (0.67 mol) triethylamine in 500 ml reagent-pure. Benzene is added with stirring to a solution of 4-7 g (0.37 mol) of oxalyl chloride in 75 BiI reagensreinem Benaol dropwise in 30 minutes at 25 ⁰ C. When the addition of the oxalyl chloride is complete, the reaction mixture becomes active

Stirred for 3 hours at 25 ⁰ C and then filtered to remove Iriäthylarainhydrocblarid. By evaporating the filtrate to a Sroekne and recrystallizing the residue three times from cyclohexane, 115 g (53 ° />) of white crystalline brodulct with a melting point of 120 to 123 ⁰ O are obtained.

Anal, calculated for G ₂₄ H ₂₀ Ol ₆ O ₉ ; 0 44.40? H 3.11? Cl 32.77 "gef"; C 44.61? H 3.21? 01 32.60.

Example 15 bis (2,4 ~ di ohlor ~ 3 ~ oarbohutoxypfaenyl) oxalate (method 2)

2 _J 6 ^ Dicblor * -3-hydroxybQnaoesäur0: The product is' produced according to the process which Zincke (T, Zincke, Ann. 261, 239 (1891)) has described for the production of triohlor "3-hydroxybenzoic acid", and from benzene

to 46 g (55 %) of crystalline product from melting point 110 to

115 ⁰ C recrystallized.

Anal. for O ₇ H ₄ Ol ₂ O ₃ : 0 40.611 H 1.95? 01 34.25 '. found ¹ O 40.14? H 1.95? 01 33.30,

Butyl 2,6-dichloro-3'-hydroxybenzoate: A solution of 24.0 ■■; (0.116 mol) 2,6-diochloro-3-hydroxybenzoic acid and 5 g of concentrated concentrated sulfuric acid in 125 ml of n-butanol are kept under liquid flow for 20 hours and cooled; and then diluted with 1.5 l of water. The organic phase is separated off, taken up in 100 ml Pui-ether, washed twice with 50 ml water each time, v \ "> v CaCl ₂ dried, filtered, 4 S-feunden under reduced .Vt.ick

009842/1977

at 30 ° C eir / concentrated and then 3 hours in vacuo at tfeiamnft, giving 22.1 g ($ 72) of a pale yellow flii: -: whose IR spectrum matches that expected for the desired product.

Bis (2,4-dicloro-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 pure reagent benzene at 25 ⁰ C with stirring in Stickstof '- atmosphere slowly over 5 minutes with 5.3 g (0.042; ■ /, oxalyl chloride · set before the Reaktionsmiccbung is stirred for one hour at 25 ⁰ C and then filtered Da3 Filtra.:. : 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 v / i. ·: is filtered off and four times from cyclohexane to 3.1 g (12.7? - ') white crystalline product from melting point 106 to 103' recrystallized.

Anal. boron. for C 24 _{H 22} Cl 1 O ₈ : C 49.68, H 3.82; Cl 24.44. Found. i C 49.50; H 3.80; Cl 24.00.

Example 16 bis (2 _? 4,5 ~ trichloro-6-carbopentoxyphenyl) oxalate (CPPO)

n-Pentyl-3,5,6-trichlorosalicylate: A solution of 48.3 g (0.20 moles) of purified 3,5,6-trichlorosalicylic acid, 200 ml n-pontyl alcohol and 4 g of concentrated sulfuric acid wire Refluxed for 24 hours. To remove the water from the reaction solution, a Dean-Stark-i'a.l applied. The cooled solution is poured into 250 ml of ice cream / wa? se, -

t
poured, and the mixture is stirred for 15 minutes Tang.

After adding 200 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 evaporator 'of the L sungsraittels a dark oil which was distilled at 128-134 ⁰ C / 0.1 mm 46 g of brown Flu .-. I ness is obtained. By renewed distillation at 140 ° c / 0.1 ..:.; 37.1 g (59 #) of product are obtained with infrared absorptions IvI 1,735 and 1,660 om " ¹ .

009842/1977 BADORfGINAL

J ι

SA

Anal. for C ₁₂ H ₁₅ Cl ₅ O ₃ : C 46, P_3; H 4.17; Cl 34.19 Measured values: C 46.46; H 4.42; Cl 34.25.

Bis (2, 4,5-tri'chlor-6-carbopentoxypbenyl) oxalate: 10.1 g (0.10 mol) of triethylamine are added dropwise to a. Solution of 31.2 g (0.10 mol) of n-pentyl-3,5,6-trichlorosalicylate and 6.1. Put g (0.05 mol) of oxal chloride in 350 ml of anhydrous benzene. The thick mixture is stirred at room temperature for 7 hours and filtered to remove the triethylamine hydrochloride. The solid is washed with 100 ml of benzene and the piltrate is evaporated at 60 ° C./50 mm. After dissolution of the remaining oil in 100 ml of hexane and cooling the solution obtained of melting point 76 to 84 ⁰ C 20.3 g (60 fo) of colorless _v "Peststoff. Recrystallization from 150 ml hexane yields 17.7 g of product of melting point 83 to 86 ⁰ C. Infrared absorption at 17.90 and 1735 cm "" ¹ .

Anal. for C ₂₆ H ₂₄ Cl ₆ O ₈ : C 46.08; H 3.55; Cl 31.46. Found: C, 46.42; H 3.61; H 31.51.

By evaporating the 100 ml of hexane filtrate from the first oxalate crystallization, 10.8 g of unchanged material are obtained Receive salicylate. The product yield based on

salicylate not recovered is 90 9 ^. I.

Example 17

In Table XVI below, values for the storage stability of hydrogen peroxide solutions containing salicylate catalysts are compiled. The solutions will: at 75 ⁰ C (167 ⁰ P) in polytetrafluorethylene TEFLON ® kept I ¹ SP-containers and periodically by iodometric titration for hydrogen peroxide content, as well as Obemo ~ i; tested .. iv / · performance in a TCPO standard reaction system. .

009842/1377

7j'j is g ^ fn ^ rjen that solutions of Natriumsa] icy] at UNOE Vasserütof-Tporoxid in tertiary butyl alcohol during one: lose · period of 80 days "at 75 ⁰ C 30 i <> dec originally η Ilyjroperoxirigehalts and keep the original lic / ^; - Ira-oa ^ itat practically ". The initial internalities decrease somewhat, the duration of the emission increases, but:; -, v / as suggests that the basicity decreases with the duration of the emission. It can be seen, however, that this Kor.r; or.: Rr: .c remains usable for more than 80 days at 75 ° 0. A significantly better chemiluminescence performance is achieved with a similar solution, the DimagnesiumäthylendiamintetraacetaT; contains, although the hydrogen peroxide loss is somewhat higher. Considerably higher losses of hydrogen peroxide and light capacity will for a solution of Wassei'atof: * - r> eroxid and sodium in 3-Metbyl-3-pentanol found "as fact indicates that close to 80 days at 75 ⁰ C of the useful stability limit. come. So: .v ... the intensities remain practically unchanged at 10 minutes after 55 days of storage. After 80 days of läi: er; i ..;.: However, the intensity halves at 10 minutes to 84aeb.cm "(7.8 foot lamberts cm"), and only $ 30 of the original amount remains Hydrogen peroxide back.

By adding 10 ° ß> methanol or ethanol to lower the freezing point to tert-alcohol-hydrogen peroxiu-tiatrium salicylate components, the stability of the component is considerably reduced, although a'Methanol-3,6-Dimethyloctanol-System after 42 days of storage remains usable. i; ine useful stability for solutions of V.'asserntoffperoxid and tetrabutylammonium 3-Kethyl - "- festgeotoi pontanol long at 33 days Storage at 75 ⁰ C."! τ.

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009842/1977 BAD ORIGINAL

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009842/1977
BATH ORIGINAL

Pussriots for Table XVI: ...

a. Poroxide components contain 0.75 m Hg (^ ^uriä ^ '^ ¹ ^ ^ri1 • I-iatrum salicylate (unless otherwise stated)

in said solvent. If additives are used, they are used in amounts of. 0.5 mg / ml added and · - are largely insoluble ^{even at 75 ° C.} MgpEDTA is dimagnesium ethyleneamine tetraacetate, · J3AGTA is 1,2-diaminocyclobexane tetraacetic acid. For hemoluminescence tests, 0.30 ml of peroxide component and 2.7 ml of a solution of 0.033 M bis (2,4,6-tri-chlorophenylethinyl) antbracene in ethyl benzoate are combined.

b. Iodometric titration. '

c. Quantum yield. . . .

G. Light capacity (total light output per liter).

e. Required to emit 3/4 of all light Time.

f. Instead of sodium salicylate. .

G. ILjOp concentration 0.39 m. For hemoluminescence tests 0.60 ml of peroxide solution with 2.4 ml of 0.0375 m bis (2,4,6-trichlorophenyl) oxalate (TGPO) and 0.00375 m 9,10-bis (phenylethinyl) anthracene in ethyl benzoate united.

/, '? / 1.9 7 7

Vi,

Example 18

The influence of different concentrations of sodium salicylate as a catalyst on the TCPO reaction is investigated. The results are shown in Table XVII. Sodium salicylate increases the brightness and improves the curve shape of the uncatalyzed reaction considerably. The potential catalyst concentration is close to 1 × 10 M sodium salicylate, with an intensity of at least 59-65 abs (5-6.0 foot lambert) being achieved for 43 minutes. The intensity can be further increased by using a higher catalyst concentration . At such concentrations, however, significantly lower light capacities and lifetimes are achieved

009842/1977

BATH ORIGINAL

Influence • the sodium salicylate concentration mj cm t 1/4 C. Table: e XVII OY ^e ) -r »entanol ⁿ from 0, TCPO in Lm. 7.5 (0.7). Tc Ti, -E (In the. (lm.b cm) (Min. ) on chemiluminescent zonz fcl.X. .22 (2.0) hl " ¹ ) ι- ¹ ) - >
65 (6) 99 Ethyl benzoate-3-methyl-? (10 a
st. Mole "1 Characteristic performance values 42 (3.9) ■; (Min) (Min) ■ M '; Sodium I _nfn ?
salicylate _{± n b #} 97 (9) 71 • 8.8 , 03 a I, asb.
cnT ¹ (ft. 59 (5.5) al 9 0.4 30th 24 63, BADO! (10 χ ^x "" 161 (15) 49 8.8 Liehtka- _lbt . _cm -1> 67 (6.2) 80 0 31 25th 5 ¹ 2 301 (28) 16 t 3/4 ^d 8.3 paz.Q
) hr.l- ' 89 (8.3) 56 0 ': ■ 45 34 61 I. none 452 (42) 4, 0 (Min) 7.6 81 "43- .0 54 37 57 Λ
j © .. 0.10 484 (45) 4, 4th 198 8.3 80 50 o '■ 64 49 ^? · 0.50 117 4.9 75 18th 0 51. 22nd 34 1.00 48 69 1.25 ^g 37 77 3.00 40 44 16

a. Responses from 0. o3o m TCPO, 0.075 m H _p 0 _? and 0.002 m ΒΡΞΑ in 80 vol .- ^ ethyl benzoate-20 YoI .- # 3-methyl-3-pentanol at 25 ° CT,. .

b. Maximum intensity. '. .

c. Mcbt decay time "from maximum to t / 4 maximum intensity. '. ■ -

d. Time required to emit $ 75> of all light.

e. Quantum yield based on TCPO. . _: , '

f. see text. . ■ '■■' ■.

G. 75 by volume of ^ ithylbenzoat ~ 25 vol .- # 3 Msthyl-3-per _J .tanol. '- · ■ ^;

Example 19

The influence of tetrabutylammonium salicylate (TBAS) on the uncatalyzed TCPO reaction is in two different lösungsmittelmischungan (75 i ° of ethyl benzoate --3-pentanol inetbyl 25 $ 3 ~ - 25 $ 3-methyl-3-pentanol and $ 75 ontbo-Dicblorbenzol) measured. The results are shown in Table XVIII. Sung-ethyl benzoate-3-methyl-3-pentanol-Lc) a very small TBAS concentration results of 1 χ 10 πι to a strong increase in the Lichtkapazitäx (65 ^c / °) but no substantial improvement of the curve shape or durability. However, by increasing the TBAS concentration, the intensity and the waveform efficiency are increased considerably, the lifetime is reduced and the light capacity is reduced to the level of the uncatalyzed reaction. It can be seen that there is an optimum TBAS concentration range (0.5 x 10 ~ ⁵ to 1.0 χ 10 ^-5 m). At TBAS concentrations above this range, the light capacity drops considerably to below the level of the uncatalyzed reaction. In ortho-dichlorobenzene - ^ - methyl - ^ - pentanol solution, TBAS produces a strong catalytic effect, which is similar to that in ethyltenzoate-3-methyl-3-pentanol. The optimal catalyst concentration is approximately 1 ^{× 10 -3} m TBAS.

009642/197?

Βα, Κ- 1 ti / 4 ^C
(Min) t3 / 4 ^d
(Min) (ίο *
Once.
Mol ~ ^T ) on 6.0) 99 198 8th, 8th 81 Taber XVIII 44 6.9 37 7, 6th 69 m T-CBD in ethylbene ζ , 3 44 (Min) E. Performance data • · 24 determined oat ^a I. salICj 25th 32 106 14, 4th 134 Ie 44 6.4 37 7, 3 66 43 22nd determined \ J1
vD 55 14th 25th 9, 9 84 the chemiluminescence of 0.03 51 3.3 17th 4, O 37 19th 0.4 30th LC ₀ (Im. LC,
H. 1 ~ ¹ ) h. 14th 53 7.8 24 7, 5 69 and dichlorobenzene 28 2.5 9.7 1, 6th 14th Characteristic O 29 I. Ii
ka 51 12th 16 6, O 56 24 1.3 3.4 O, 6th 5 O ' 47 24 Methyl benzoate-3-methyl-3-pentanol (75-25 44 16 17th 5, 3 50 ^T c
(Min) O 50 39 (In the.
ι " ¹ ) 65 O 46 39 t3 of tetrabutylammonium salicylate 269 J ·. Ic (ft._ ₁
_ί \ Ibt.cm ") __-
'in asb.ern " 219 O 56 35 63 592 7oiuji). 96 26th 90 W. * max in 570 7.5 (0.7) 26th 28 63 O O (10 * m) (ft.Ibt.
cm"') 549 30 (2.8 27 O 34 56 "ά ο
2 co A, In 473 105 (9.9 15th O 33 41 none 87 (8.1 17th —-Q-- - 37 37 1.0 118 (11.0 not 5.0 110 (10.2 too weak for measurement not CO 7.5 37. (3.4) 53 10.0 3tf, v (3.3) 50 10.0 51 (4.7) 29 Am none 10.0 o-Dicblobenzene-3-methyl-3-pentanol (75-25 Vol-90. 10.0 25.0 473 50.0 473 75.0 549 301 258

a. Reactions of 0.03 m TCPO, 0.003 m and 0.075 m BBA V ^ asserstoffperoxid at 25 ⁰ C. "b. Kaximalintensität.

c. light decay time from maximum to 1/4 maximum intensity.

d. Time required to emit 75 '# of all light.

e. Quantum yield., Based on TCPO.

ro ο

CT) Cn OO ro

Example 20

The influence of different catalysts that lead to one increased performance of the TCPO response is from the Tables 19 and 20 can be seen. The experiments are given in Table XIX and the results in Table XX. The results clearly show the control effect of these catalysts on light intensity life. Sodium salicylate is a superior catalyst for a cherai luminescence system with high light intensity and short life and tetrabutylammoniuraperchlorate is a superior catalyst for a long-lasting system. Tetrabutylammonium salicylate and tetraethylammonium benzoate also useful catalysts.

009842/1977

BAD OR (QtNAL

from TCPO-Ctoen-o "unineggeji ?!

«30

11.8 * 7.98 7.78 8.42 635 7th $ 2 9.47 14.40 1235 1 * 8.8

ag ».

«« 4

h . I.

il 84 74 72 78 CO «? 61 CO

88

U *

116

81

Q, ISO KA

0 · 05

S, O TBAP

HA

oats KA Uh ₉ οα

, 10 TBAS, | _t OO SA O 10 TBAS O, li§ NA SAL, i, 0 0.01 TBAS O, SO TiAP

EI (Ti) -

"811 (90) · 5-Μ · 5 -? (ΙΟ)

■ .3.0

. Ce X 10

73 .;

7> 5

Explanations (Table XIX)

"b. NA SAL: sodium alioylate, TBAS: tetrabutylammonium salicylate TBAP: tetrabutylammonium perchlorate SA: salicylic acid TEAB: tetraethylammonium benzoate

BTI4ATGB: Benzyldimethylammonium-2,3, ö-trichlorobenzoate

c. EB: ethyl benzoate 3-M-3-P: 3-methyl-3-pentanol 2-OGT .: 2-octanol t-BuOH: t-butyl alcohol ο-I) CB: ο-dichlorobenzene

009842/197

BATH ORIGINAL

Ver .u
search catalyst τabο lic 63 (5.9
50 (4.6) 15th V L ^f tem I ^h
Max 1 Tr
Nq.trium salicylate
(0.0015Om) i XX 21st 32 61 'Qg 78 2 Tetraethylammonium
benzoate (0.001 m) 26th 36 72 6.6 46 3 Tetrabutylammonium
salicylate (0.0005 m) Hochle istung - Chemiluminescent System 46 39 84 7.7 49 4th k I *
Tetrabutylammonium
perchlorate (0.05 m) i _c ^c 34 70 125 9.0 17th O'
O 5 151 (14) 49
62 74 11.2 co
OO 6th 118 (11) 45
46 72
71 8.0 44
36 (O
(D
Ή · 107 (9.9) 7.8
7.7 -Λ 103 (9.6) Benzyltrimethylammonium 63 (5.9)
2,3,6-triehlobenzoate
• (0.0015 mq) ITodium salicylate
(0.00125 m)

Sodium Salicylate 60 (5.6) 51 43 78 8.4 42
(0.00125 m) and salicylic acid (0.001 m).

Tetrabutylammonium 46 (4.3) 39 26 61 6.6 8.5

salioylate (0.001 m) and 'N3

Salicylic acid (0.05 m () "■ O

Tetrabutylammonium ^F - 37 (3.4) 44 24 69 7.6 44 Oi salicylate (0.001 m) OO

Table XX (cont.)

Try the catalyst

¹ O ⁰

Max

10

12th

13th

Sodium Salylate (0.00125 π) and Salicylic Acid (0.05 m)

Tetradtylammonium salicylate (0.0001 m)

Te trabuty! Ammonium perchlorate (0.008 n)

none 31 (2.9) 83 37

30 (2.8)

96 39

7.5 (0.7) 219

88

81

9.5

134 H, 4th

27 (2.5) 123 48 116 12.5

8.8

ίδ & ΐΚτ- ^ Ρϋ '; ^ SÄ ^v 't ^ Wi' «W '^< Si ^ ^w ' ^ Jte» ^; ^? i ⁱ äSi ^! 5 ^:) " ^l t? 'I * ^Ä ^

Attempt ~ Time? i ii ; &% as funle ^ iöu Uer 'Aa Ji -: ■ 1Qw M. K) 194 (18) 194 (18) H 5 ₉ 4 (@ ₉ i) 2.2 (0.2) O 1 204 (19) 172 (16) 86 (8). 5.2 (4 ^ 8) 65 (6) CT) . '■ "ι" ί 2 194 (18) 161 (15) 118 (11) 88 (8.2) 16 (1.5) 10W cn -, .- ■ 3 172 (16) 161 (15) 129 (12) 129 (12) 24 (2.2) 10w CX) «Γ 4th 161 (15) 118 (11) 140 (13) 71 (6.6) 48 (4.5) 5 118 (11) 97 (9.0) 87 (8.1) 74 (6.9) 38 (3.5) 10w ejft ' 6th 108 (10) 79 (7.3) 81 (7.5) 60 (5.6) 25 (2.3) 10w ♦ * ■ "■" 129 (12) 94 (8.7) 63 (5.9) 74 (6.9) 24 (2.2) IV 7th 98 (9.1) 87 (B | 1) 79 (7.3) '58 (5.4) • 41 6.8) ^r 2.2 (0.2). .!.> _β S ^ - 14ο (ΐ3) 96 (8.9) 73 (Wö) 50 (4.6) 44 (4.1) - 9 ',!%:. * -, ν ■ "■ '68 (6.3) 68 (6i3) 65 (6.0) 60 (5.6) ' 45 (4.2) 19 (1.8) YYY ⁵ IO ■ - '■' ■ * ; 172 (16) 129 (12.) 69 (6.4) 70 (6.1) 29 (2.2) 24 (2.2) ^ ϊι> · .ί ■ · ■■ - ■. 129 (12) 11B (11) 87 (8.1) 69 (6.41 "27 (i, 5) ^ ₁₂ ■ ■■■■ ■■ ■ · ■ ■ -. ' . '62 (5.8) 59 (5.5) 86 (8.0) 37 (3.4) 14 (1.3) 13 ■ '■ - ■■■ - ■ 45 (4.2) ^ "-" ■ w .'.- 'sC'i' V. .... ^. .... *

Footnotes Table 20

a. Reactions of 0.030 m Bia (2,4,6-trichlorophenyl) oxalate (TGPO), 0.003 m 9,10-bis (phenyläthinylanthrao <- .. ·. (BPEA) and 0.075 m H ₂ O ₂ in 75 percent by volume ethyl benzoate 25 percent by volume 3-methyl-3-pentanol (unless otherwise stated) at 25 ° C.

b. Numbers correspond to the numbers in the table

c. characteristic intensity, asb χ cm "" (foot lamberts cm ").

d. characteristic service life (minutes)

e. characteristic light capacity (lumen χ hour χ liter " ¹ )

f. Total light capacity (lumen χ hour χ liter ").

2 - 1

G. Quantum yield (10 Einstein χ mol ", based on

TCPO).
H. Maximum intensity, asb χ cm "(foot lamberts χ cm" ^! )

i. Response time in minutes

- 1 - 1

j. asb χ cm (foot lamberts cm)

k. 90% ethyl benzoate-10 Jt 3- ^w ethyl-3-pentanol

p. 75 i "ortho-dichlorobenzene-25 # 3-methyl-3-pentanol q. 90? 6. Ethyl enzoate-109t tert-butyl alcohol r. 0.036 m TCPO

9842/1977

BATH ORIGINAL

Claims (1)

Pat entan sayings wherein X electronegative substituents Y is a carbalkoxy group Z hydrogen atoms, alkylxaste, branched Alkyl radicals or alkoxyalkyl radicals, m, η and 4 integers with such a value that.3 the sum of the Hammett sigma constants of the substituents X, Y and Z on each phenyl group is between about t, 4 and 2.7, where m and r always have a value of at least 1, and ρ is an integer of at least 1. 2, bis (phenyl) oxalate derivative, characterized in that ρ denotes 1. 009842/1977 3. A compound according to claim 2, characterized in that fiele'ein bis (tricblor-6-carbalkoxyphenyl) oxalate, Bia (2,4, ^- trichloro-6-carbobutoxypbenyl) oxalate or bis (2,4,5-trichloro-6 -carbopentoxy) oxalate. 4. A compound according to claim 1 or 2, characterized in that that η has the value 1 and that the carbalkoxy group is is in the ortho-position to the oxalate oxygen. 5. Further training of the chemiluminescent combinations c ^ -r according to patent P 15 92 824.2, daduroh characterized that they are a compound of the formula X electronegative substituents, Y a carbalkoxy group, Z hydrogen atoms, alkyl radicals, branched alkyl radicals or alkoxyalkyl radicals, m, η and q integers with such a value that the sum of the Hammett sigma constants of the substituents X, Y and Z on each phenyl group * is at least about 1.4 to 2.7, where η is 0 or a deaf number and q is 0 , 1, 2 or is, and 009842/1977 BATH ORIGINAL ρ is an integer of at least 1, in combination with at least one of the others Components contains fluorescent substance, hydrogen peroxide or diluent. 6. Composition according to claim 5, characterized in that that it contains a bis (phenyl) oxalate ester derivative. 7. The composition according to claim 5, characterized in that it is a bis (2,4,5-trichloro-6-carboalkoxyphenyl) oxalate, Bis (2,4,5-trichloro-6-carbobutoxyphenyl) oxalate or bis (2,4,5-triobloro-6-carbopentoxypbenyl) oxalate contains. 8 # Composition according to claim 5 »characterized in that that it additionally contains a rate-controlling catalyst, which consists of a base, a basic Salt or a neutral salt. Peroxide component for a multicomponent chemolmninosa system, characterized in that it is hydrogen peroxide "and a basic ^ aIz, which is an anion of a carboxylic acid or a phenol with a bisotiation constant in water between about 1 χ 10 and 1 χ 10 and. contains a solvent. 10 «peroxide component according to claim 9» thereby marked; that they use tort.-alcohol or e'n as a solvent tert.-alcohol-Phthallateeter-Oemisoh contains «/ 0 0 9 8i 11 1 η 11. component for a membrane component chemiluminescence; naoh claim 5 »characterized in that its components are in a solid state. 12 .. Oxalate component for a multi-component Cbemolumineo ^. . '■: · System according to claim 5 »characterized in that it contains the oxalate ester and the fluorescent substance according to claim Ό and also a solvent that consists of esters, aromatic hydrocarbons or chlorinated hydrocarbons · 13. Composition according to claim 12, characterized in that that the solvent is a dialkyl phthalate, the alkyl groups of which have from about 1 to about 12 carbon atoms. H. Composition according to claim 5, characterized ".; O that it is 9» "' O-Bia (pbenyläthinyl; anthracene; 1 -Met; hc.xy-9» lO-bisiphenyläthinylianthracer., 9, lO-Diphersyl- Contains anthracene or perylene. 15. Further training of the process for generating Chemiluminescent light according to patent P 15 92 824.2, thereby characterized in that a compound of the 1Ύ 009842/1977 - .71 - wherein X electronegative substituents; Y is a carbalkoxy group; Z hydrogen atoms, alkyl radicals, branched Alkyl radicals or alkoxyalkyl radicals, m, η and q. integers with such a value that the sum of the Hammett sigma constants of Substituents X, Y and Z on each phenyl group are at least about 1.4 to 2.7, where η has the value O or a higher value, and 4 Qi 1, 2 or 5 let, and ρ is an integer of at least 1 with a fluorescent substance, hydrogen peroxide and a solvent mixes. 16. The method according to claim 151, characterized in that one also adds a speed-controlling catalyst, UmT consists of a base, a basic salt or a neutral salt. 17. The method according to claim 16, characterized in that that the rate-controlling catalyst e: base salt used in the hydrogen peroxide component, which is an anion of a carboxylic acid or a? . Phenol with a bissosilonic constant in water -Fi 1 between about 1 χ 10 and 1 χ 10 on west. 009842/1977 Blank page