BE686610A - - Google Patents

Description

  

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  "method, reagents and compositions for
 EMI1.1
 1'aüte: nti.an of a ch1miolum1nescencc "

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The present invention is. relating to new compositions, new reactions and the efficient conversion of chemical energy into light energy or
 EMI2.1
 we light with the help of such compositinne. By "light" is meant herein electromagnetic radiation at wavelengths between 350 m and 1400 mu, the normal visible part of the spectrum.

   However, by choosing suitable compositions, it is also possible to obtain radiation in the ultraviolet part and in the infrared part of the spectrum.
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  To enpendrar Je la 4v;: ai.: Re starting from chemical energy, that is to say producing a cr.i.rr, ialm; .inescer: ce, we are continually looking for compositions which, when i: ! They are reacted, substantially prior to .'ir; tension and duration I the ernrion struggles.ineusc to oppose:, er.t to compositions chimiolun, 3nesceni, ;; = r '; Jfiau <;;> and . to the reactions of these known compositions. It \;:; \ .. viur, t that an efficient, brilliant and lcnuure composition would be interesting to be used in an,. (;; 1: ijoo ;; ii, iis ae signaling, to illuminate certain areas etc ...



  Since some tCIl.p ::; we know t. "binds oxalyl chloride combined with aqueous hydrogen peroxyùc (3) and a fluorescent compound hear a: iuu.lùre whose cu- r '\ i;) a:> t t.rJ: short (from l 'order u'about 8;'. 30 sec <;:.; and do: rt the insert is of little practical use. These reactions are on the other hand viti ureus8s and: rrr, er uses .

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  It should be known that the mechanisms of light prouuction ch s c ente are f; .ftl included at a point
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 as it is; it is now impossible to predict the structures
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 res capable of establishing the property of chemilun, inescerce, Ce fliit r: 1; 1.T!., f'L. (: nt ii111wtr ('par la St.': 'iC C1L "composas pht & lilynr': J, '.'Ju., Jont. Some - chim, ioluu, inescenrs and of which you: e: r, e are not fiir, n. Î3crliurtoae, i3u11.



  China, yrance, 11 vSEil (1950) ¯7.
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  The present invention relates to a composition
 EMI3.5
 chemo, read,: ine5cent and a method of using such a composition not to obtain a rer.cter:, ent iav6 during the conversion of chemical energy into light, pcndùnt ui, 1> zps of prolonged time and with a higher intensity than that obtained with chill compositions, ioluminc5C'er.-
 EMI3.6
 your previous ones.
 EMI3.7
 The present invention has to do with a chemuminescent composition which can be used for obtaining it by a simple and inexpensive process. the present invention relates to a ct5i ^, iolur..i.nescent reagent which is stable for a long period of time sanding and which can be used for long periods of time;

  aite er, reaction for obier. '.' - T! sah chemiluminescent light.
 EMI3.8
 object of the present invention is er.
 EMI3.9
 a chemical reagent which, when used in the presence of a fluorescent compound, produces ciWu.iolu7, inescent light.



  (found only the objectives of the present inver.- tir ..,: <; t; 1;> LLein, is by the ffi6l & nrc due: (i ur. co;,. poscs of formula nuivaitte: A-CG-a .CJ-A, é = t, 5 xw; W # may be 6! Or different from, is (û) 1i ?, where! \ Tkr # s, = l jpc uryle substitutes or :: on,: .âfy3e substituted or not, liv2is1 "tCyCiic; ue cat: the pyriuyif, luryle, acr.i.:inyle, ht.rocyclic substituted or a! Kyle in5turÓ radical:

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 - 4 -
 EMI4.1
 (b) -OCOIZ1 where R is an alkyl or cycloalkyl radical or unsubstituted, aryl, heterocyclic or unsaturated alkyl;

   
R2
 EMI4.2
 or (c) -nez, 3 where at least one of R 2 and R is an electron-reactive substituent with a value of sii7ii, za spreads to environment 0.7, the other substituent being hydroeene , an alkyl, aryl, aralkyl or alternatively R2 and R3 together with nitrogen form a heterocyclic group which may contain oxygen, sulfur or a keto group, X is (CO) n where n is an integer from 0 to 9 or a group
 EMI4.3
 wherein m is an integer from 0 to 4, Y is equal or different and is hydrogen, chlorine, bromine, fluorine, a phenyl, alkyl or alkoxy radical and Z is an alkyl radical or substituted phenyl; (2) a hydroperoxide or a compound producing it;

   (3) a fluorescent compound except in the case where the compound A-CC-X-CO-A is itself a fluorescent compound or when the reaction product is a fluorescent compound; (4) a diluent and, if desired (5) water, and, if desired, (6) an acidic or basic catalyst.



   The following oxalic acid anhydrides are ue
 EMI4.4
 new composta chimiolun, inescei, is ae fürr.ule:
0 00 0 "" "" RCOCCOCR '
 EMI4.5
 wherein R and Rt are the following substituents: aryle- rcthyl, diarylmethyl, triarylffiethyl, alkyluryl, alkoxyaryl, sulfoaryl, carboxyaryl, arylaryl or aryloxyaryl

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 EMI5.1
 where typical aryl substituted substituents include the following radicals: methoxyphenyl, dimrthoxyphenyl, trim6thoxyphenyl, ttrarllethoxyphenyl, pentarnethoxyphc3-nyl, alkylphenyl and polyalkylphenyl.
 EMI5.2
 



  For obtaining the optimum and preferred results, when A is -OR, it is of critical importance that the
 EMI5.3
 ester reagent either (l) an ester of an alcohol or a phenol
 EMI5.4
 characterized by an acidic ionization constant in water
 EMI5.5
 higher b 1.3 x 1C-10 or (2) a vinyl ester of an acid of oxalic type having the structural formula given pivy 1: to; ut.

   I must. note that said acid ionization constant (dt'nr 1,: ei <u) can be t; t.aai.e in tf1re5 of the value of sipn, ac Hi,; 0tt of a substituted alcohol or not (usually der. ". ^ t: oß: rocatic5); in this case the value of s10; 18 of '; ür: v.fE't.û is. greater than 0 (positive) for the undergone 'StitU0Pt u'u:': substitute alcohol which is curcted by a cons; i,;, ie c'i.Jr, 1 ±,;. t.ion 'd s-period <-1re' ': 1 10 . consc.r.tG c'ioni; .tion higher acid, 3 .0 '' C \ ;: \:,:, f ':' 5 can also Otrc prepared from a h> 'i, ira; y> 1--n.in;

   or LI'a h-hyuroxy v.:.idc such as ti- hya roxyplt \ .. ,, 1 j,, \ 0. it r m'ai;, 1.; e ue oxulic type, which is --n3 'according to the j; re = ei> the invention, is ur. rttice d'l'ivé une a: .. ine parer.tc, (3t :::;. c.u'f \ .the strong way 61 cctroniJCôt1 'le) and / or another J0rlv ±. zot .. (j parent 5ub: 3titu in this way and defined (H.fW 1 (> present mtuoirc coiiii4f '"' being a which t <ortt- 'or Ci ^ r'.? 'C5:" w ± acs substituting (', Lt: Ci..ront! T; .tt.i attracting the' lectrorta enough to make the ilihyùruçéne úUIJ5ti- d ('' rivt '' t1Z () tf 1 tl.4é) wr.ir.ü and / or l (, / :. (nYl1ro.'ùr.f 'su itst: .c .; j it at least also ..ci- that la.-ii: ro> <rii ine quar.d we make the comparison in cc.x <ùiti <,;> i pr - ;, ii <; uc; ,, er, 1 sintiluires, corr., e in a solvent CO "r.l1.H x¯;. '' y :. 4 Read the present invention.

   Co ;;. ::. C ue derived examples: s

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 nitrogenous substituted as indicated above and more acidic than 4-nitroaniline include amides,
 EMI6.1
 inddes, sulfonamides, inidazoles and anilines, the latter having a sufficient number of electronegative substituents to provide the number necessary for the sum
 EMI6.2
 constants (siginu values) of substituents to roughly equalize the value of the constant of a nitro group (ie 0.7).
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  The preferred oxalic type audit according to the present invention can be chosen from IH, from the sulfonyl att.ides C y; .0 OI! '::. C 16Hs <o CH' the N-riitero-a : ,,, - des con "u, e Y, C2H les a 5 -N-CH3 les: J1: idù c6to or i.fdno substitutes, utcracycli, ues entrusted
 EMI6.4
 Typical compounds in which X is the
 EMI6.5
 group: / (Y) mz son, v c6H -0-alky or aryl Ïl% lc if C-00-aikyle or aryl c 0 or c 6 il. ## j'o (ponte) yor, t) 65 f * '! - # "

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 EMI7.1
 The hydroperoxide used in the composition and diinrs the procedure (j following, the present in '/ pntion can @% re any; ue. Cr:, pos comprising utt group cartlct.ér1sti .. that of a uy ;: rcl> cra: cyde, conoee hydrogen peroxide H202 'a ii "tîr> r; ytr; .t;

   of alkyl '1CO :. or an O'l''oxy acid (R-CO-COH) Corrane lr: a, - ::? r:, xyde ue t, -ta;,> t ucidc y; 1: rberiiolque.



  C (> penuLtit, if di-t-iutyl puroxide rlzi-it pas darà: 3 les cor, (1 4vionj tic rac: Lian in ilcàliii or ani-, ycirH medium. The pcrcxy {: e ("! 1., d ,. éirc used = -> OU5 for: .. c {sodium puroxy or sodium ierba-ite in üqueuze solution so as to obtain a solution of hydrogen peroxide. Although ig presence of water is necessary for obtaining the c} tirttio- him..inescence, in certain forces of realization of the
 EMI7.2
 present invention, the peroxide which is used can be obtained
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 held off (ire cor7, po -, (ts of anhydrous hydrogen peroxide, such as urea perhydrate (turCa3 peroxide, pyrophosphate perhydrate (sodium pyrophosphate peroxide),
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 Histidine pyrohydrate (histidine peroxide) or sodium perborate.
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  The concentration of the peroxide can vary from about 0.01 to 100 to 100; and it had been diluted before or ôi> r-às ie,. ('1 <.n :('. Compound 1; 4r, er <tor of Mon.H: rc can be 1 *,, 1 nr -1;> e aolidc or en) !. t ': launches with an active pcroxyuc: .J "). D {;:,;, irapri' or da: .8 an appropriate diluent or 12 ;;:; r .c5 ri he had tire di S50; J; c-4irect., ctit in a so-: t.;. JA {) fJ. .. r .; z;:. a :, '. the r' <" 1Cl 1} .. croxj '"; 1 (\.
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  ..this.' ! 111; ./. typical t5 M \ t: cpux 'Fl rte rul: i5 seli tpjs i't .... ":.'. -.vue 'aii peroxide cc ;;.', \: àP peroxide hyl.1rorene and.! 1f 'r ". "i; or. more dummy ..!, with anhydride, J, 'e3; .cz 1,; p of acid xc, iue.
 EMI7.7
 i ', f.; on1. ù0nr..j (read J.'eau is a 1 "11, oC'1 .: Cv: CG: iûT'i3 v1 lu; 1'f? çFlCûi3t1 .I light from G71iu0itt: tit, CCt (in c <: rt.ainc5

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 embodiments of the present invention it is.
 EMI8.1
 of course, water can also be used as a minor part of the diluent.



   If the reaction medium contains an acid in sufficient quantity to obtain a strong acid pH of less than about 3, water or an alcohol (such as anhydrous ethyl alcohol) is required for the reaction medium. 'getting 1.1' a reaction
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 of chemilun.innAscence oj> th, <ale and if water is a partial diluent, it may be present in an amount up to 70% of the total percentage in the diluent. Gold: however prefers lower percentages of water.



   Further, when using the oxalic acid or ester which allows optimum and preferred light intensity to be obtained, according to the present invention, a base should be used in an amount sufficient to produce a basic pH. Any suitable base can be used which does not adversely affect the composition and the process according to the present invention.
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  However, in the case of hÓt6rocyclic uvides containing an [alpha] -keto croup like
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 EMI8.5
 we obtain <jc3 ['Ónul \ .dt8 pref6rl: n tjstaM des corù1t.1ons, l.tci <: es.



  I \ Vç ius ccc, rt; ' due this Gri4 1 (15 UC1di! G cut. j.y8em. a reiàciion of 1, àuiraiicei ,, ent to give Hou h a MSt.or 'OXti.'ia1vH of pyriJyle corr, r, e indicated below,
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 With these amides, water or alcohol should not be present. Those are. amides or esters derived from the following compounds: 2-hydroxypyridine, 2-hydroxyquinoline, 4-hydroxypyridine, 4-hydroxyquinoline and the like. It is clear that the resulting ester also provides chemiluminescence under acidic conditions.
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  (... where the light producer is reacting under conditions close to the m'utralito or alkalinity (b ;; sici14) a pfi greater than about 4.5, we have found It is surprising that the reaction medium may be anhydrous, however, that there is #, iL t 0.002 /; to L% 1 of water.



  We see:> this a large variety of organic and inorganic bases, typically banks> following:. Rt..s the butoxy- of t <J ";" 1, .l, dl'O of pot-. siutn, 1 '>? Lhoxy <1 = sodium, odïua, .ryuroxy.c: ammonium thoxide, tetrabutyl lI.l hyuroxy: ur.cnium or t.riphcnyï nieLh ide ci rl;: r, rc: bases ae Lewis na; amtm: in iri4Li; ; 1;> 1 ;; ine or lu r, uin: c; * rle.



  ('n rlV.:>1yf une (", rat <te variety of acts ür; G: a3. <ylC3, tyli.lt?Itl1'rlt..t <"': following acids: aci003 alkane Si.tii '5: ll; tlüf, comr .. \.' 3 9aC'C: CW \ ', thC1r; e 3U l f'oniltE: 1 l': ,, c: .. utitanc 5 \ .11 roni (;. .c, butane sulfonic acid and the like; aromatic i Buii0r7jGiiwE3 acids such as benzene acid a: .i''c: nir; ure, para-toluene sulfonic acid, phônyï au;.! (5n :; tje, and anQlO ;; ue: 3; l'3ciac:, ri ... '. xxG: "ïCt'i.iluf' '. m1craux COlI'wW: chio- hydric acid, i'aci 'te nitric, aciu' suijuric and acid pyroFaaaspï: orici: e Lewis acids notwl,: 1ent trichloride <i'abin, ir; 1> ax etc ..; perchloric aciae, boron trifluoride ; acicx'n ort: ur.ophosphorús as> pnunylphosphoni- acid
 EMI9.3
 that and the like, etc ...
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  , P cox <pos6s fluoré scc-ntG er.visacé uar.3 le present n.6: r.oi] c Hont r.ord.J1'ùux and can be defined broadly cotr. ^ S G1 #>; = ; .. z <; ux which does not leave G pd'3 1; .icilaeii.eno in contact

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 peroxide used according to the present invention, such as hydrogen peroxide; likewise, they do not readily react on contact with an aliphatic anhydride, ester or amide of oxalic acid.

   Typical suitable fluorescent compounds which can be used according to the present invention are those which exhibit spectral emission in the range between 330 millimicrons and 1400 millimeters and which are at least partially soluble in any of the aforesaid diluents, if one is used. these diluents, Panni these composas include aromatic compounds
 EMI10.1
 conjugated ptl4rFyychqus comprising at least 3 fused fU5jS nuclei such as anthracenc, substituted, bnrrarû '= actne, phenanthrene, çh # ;, m, substituted hrno, supper, nuphtacdne ;; Ub5t.itu,' "le pentacere, substituted pastuc <5nr and the like.

   We can. cite h "tcrocyclic compounds such as tL't! ';, iJht'l1yl porphine, z4lric-t' - traphulriyl porphine and di.'t16nylisobcnzofurünr.e.



  Typical substituents for all of these compounds are phnyl, lower alkyl, chlorine, bromo, cy 3 to C 16 and other analogous substituents which do not interfere with the contemplated light-generating reaction. ge in this memo.



   Many other fluorescent compounds exhibiting the properties given above are well known in the art.
 EMI10.2
 technical. Many such compounds are coinpLeiia, described in "Fluorescence and Phosphorescence", by Peter Pringsheim, Interscience Publishers, Inc., New York, N.Y.



    1949.



   It should be noted, however, that although a fluorescent compound is necessary for obtaining light, the fluorescent compound is not necessary for obtaining.

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 EMI11.1
 (.a I't'ctG., l.Oïi chemical and. la.: tr; t. '. UT of chemical energy. t't'insi, n <) r =, <en, pie, a cïlzluialurrin anhydride (cnt commo l '6 [l1ydr-iae ox.lïr; ue of 9-crboxy - LC: -piÉ: ny7. anLiirucéne re r; 5; j; iiiét, j: i> :; ¯tEY cocpo .rL fluorescent 36par6 to get it- ', iQrz' -.1: ':;' '1: r,.: \;' ,. 'r'r', "',, 1. ,, <,. rioi '! s of oxalic acid:' â, Â 4: cy:.;:; .r ;. ,, .- a, .r.; '.' .. 'Cd i-càrboxyàcridin, 12 ). xLa-¯.r; àt> r # i; e-2-c; jrboxyliçu, (3) anthr a.cW s-.1- acid
 EMI11.2
 C,>: "'\ (1xyl (\ u.:, T¯:

   E4t the l.,) - bis (, - c.:.rooxyphenyl)i50bcf1zofu- 1's'sâlTi ±) rX7: 3 C) 11; 3tFtS that the C0ICt! N \ .riltior.1; t0i3: "f; S ( moles pur Aluro fur .zxiuf.nt) des coi> j. <> to: years! Ídjeurs de lu con, po: 3ition 110J "" "Ü. ('= ¯14C'ti: .dy in j, resoei; 1 t:. '' 'M''i "e can, carier cnnsi- tel'11' .; f"; ti:., A is enough 'Uf¯' the CC) flitt7; siu. Dolent in concentra- '' .j.a7tl. ^ .; iÎâi .: tzawE ': vOL7r 1' okJt.f! Nticr 3 lu ctÜwlo1um.1mwccnce.



  Cn ne cr <rï <SL c'1CUl1e llrdte IOI ':' XÍf "le A 1 ;. concentration cc 'an11y1rio (,, .. ;; t <1" or wl1ioe' .i, ttt''1 = uses dHII5 the rcucticn.



  .; f4't: ct.t:.: 8 'tJ:' 11G ', (10) r, sj.: iIL.iOr. Ljrj> il7t? de lu pre->: e;, i>; .e: = :. atzï h.piiquc utiïi:; ctinn of two phases li'tui- df'5: 'Ûpd1' ('; 1 <Î': lt $ a single recij> iei; 1, where one phase confides. the -, rouucteii.- ae lUI1, ièrc following- the prú5cntc itiveiillati eL
 EMI11.3
 1 ';, area p :, :), ^ S, t7rit the J'r [) xY <1c; 1'lItrO (; GnE', one and. The; .-, '0. getting a fluorescent composa. In this elm; 1t ... on, 1 <, r (Jetior <takes place; the interface comprises P'2t, .r 'phases.

   A typical (. ': CCSi.> IH is, the use of a splu: .i0n ue prouucueur Je 1ua = ir: rc and d'veent fluore8-:;.:.,> F; i ,. J :: 'l; .yl phi.ala 1..ee ;. a:'. T \ ':' aqueous ut.ion and of i;, 1 .:. <;, - Jo .1 t yu: ' Of ': J. (:. il c: t; tre aans 1 ..: (' "wax of the present ixtr: a; '.,. C ;. vw:.: Ier other cofbinisofiS of solvünts mis- ciolc ;; ..:;; .t, here <ller imnziscibles, ('po9ition chitftiolumincscent-e following, the prc; - sch! <c) nvcnt.icn which realizes the ethissiou of light by chinio-

 <Desc / Clms Page number 12>

 luminescence when mixing the ingredients of the composition, can be carried out in a single mixing stage or in a succession of stages of (the separate ingredients.



   Therefore, alternative compositions can be prepared which can be stored for a period of time and which can be mixed with the final ingredient at the time when it is desired to achieve chemiluminescent illumination. For example, such a composition would comprise an oxalic acid anhydride and a fluorescent compound without a diluent.



  Another example would be a composition comprising an oxalic acid anhydride, ester or amide, a fluorescent agent and a perborate but without a diluent. Still another composition would be a composition comprising an anhydride, ester or amide of oxalic acid, a fluorescent compound and a diluent but without a peroxide compound,
The wavelength of the light emitted by chemiluminescent of the compositions according to the present invention i.e. the color of the light emitted can be modified by the addition of one or more energy transfer agents. (fluorescent agents) such as the known fluorescent compounds discussed at length above.



   Although in the method of obtaining light by chemiluminescence according to the present invention, it is normally not necessary to use a specific order of succession of steps when adding the individual ingredients of the composition. According to the present invention, it has been found (1) that each of the above objectives is met to a greater degree, unexpectedly, when the peroxide compound is added and mixed with the other necessary ingredients before mixing all those. here between them, (2) street in the embodiment involving water and where the mixture is alkaline,

   

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 EMI13.1
 water must not be added in substance before the reaction
 EMI13.2
 essential chirnioluminescent tif.
 EMI13.3
 According to the prescribed invention, described in
 EMI13.4
 present memory, an intense 1st light is generated and the Light Unions last approximately 16 to 60 times
 EMI13.5
 longer than those of the aqueous compositions con-
 EMI13.6
 naked and. described;: aI1; rït = JrhtrWrit, contains the chloride of oxalyl.



  The ex'.Tfpes <;;;; i,;> ni- are 4A.7t.ir ::? If to illustrate the advocated ln '!,;': '... 1 (, "' .'t, lion to limit it.



  ED l ',:': 3.



  : '';:. '1 i.:Î?T":;l .11': s' oxaliz acid; .u0 prepared to achieve LÀ> ;, - wF:; ¯n: v .zrrztc c. - ;: e: on are as follows: s dL -: 1. ' Hie bj ::; - lt.l'1ph (.rJyl ;; \ :! t, i'1ue) ox <11ic.
 EMI13.7
 
 EMI13.8
 he. ii īi, ¯: 1 m, i i, e, j 1: ,, c> J # 1 qu e - <; x ;: i 1 <#ue
 EMI13.9
 
 EMI13.10
 "*: 2: Ttt," i '.: <. Ulitu! ^. 1.lük? R> :; 3ctUC.
 EMI13.11
 
 EMI13.12
 1j .cï, ïl: .. 'i'. ± 'b i ::.; - (/..-JlH t: .hnxyn.:; N;, W-1que) oxali (iUe
 EMI13.13
 
 EMI13.14
 1 x c-'j;!. "O''s";. "CL" 1 <'uii dcr; r6 ite ehii.if'. '. UnrLr .-' c'f.ce; -ôferé and the cix > j <c :? 'ù "present in or # re' UT, JCi'r0 ac 3LabiH <thermal <ju 'nn j> rofére, Ce- pen'.u.nt. If cc <r.pcsôs" n'i to "D" inclusive . , <; n !. are. all; ? up. '. i''T.'urs.:')! :): ;;. res COI "P05Ó5 taken .tU, us,; rçl cov.;, <e the anhydride" rF.I'-iU '.; - ..:'. <lir; ue.

 <Desc / Clms Page number 14>

 
 EMI14.1
 



  EXAMPLE I.



  About 3 mg of compound A is added to 5 ml of 1 mg solution of 9 <10-diphenylanthracene and 0.2 $ ml of water.
 EMI14.2
 in 1,2-dimethoxyethane (glyme) maintained at a temperature
 EMI14.3
 zero of? 5-30 C, uses no peroxide. No chemiluminescence is observed.



  KXEMPLR the r.



  Approximately 5 µl of compound A is added to 5 ml of x.w¯ir <! of 1 mg of 9, .tC-diprmsx; f, Lrr, ^ ceria, 0.25 ml of water and C, ..: t,: 1. ! '! * aciQp rr.Fthne: .uit'cr; .c; u <to: <;, 5 of 1., 2-dimé.haxyétnane 1: ;; .. =: 1 n; .i> held to a tûmp6ratu. reaction of Z5-0 'G.



  C "I; - / tl '' :: U5..sc no peroxide. On:, '(jb, 1r've no chemilur, i n # kG: ei :: e.
 EMI14.4
 



  In the tests described below, the peroxides
 EMI14.5
 Ul!: B6s are:
 EMI14.6
 a, hydrogen peroxide. 112 (12 acid 91 b, perbenzoic acid 5C; OOH 0 c. benxcylf peroxide;.: 1JGG ,, Vhi1 ci d. peroxylauriuc acid C .H Ô0Qhl e # peroxide da di-L-1> UL> ' lV C11 << t :: OC + fig io hy <iropuroxy; ie d <; tt> vtylù llj "i0Gli
 EMI14.7
 X i ',, ", i, c, On 1 <jouLe About ¯4 1> jj of compound a to 5 ml of solu" 3on of 1 m of 1? Adirshr> -r, yiaf.ït; sc: ne, 5.2 ± 1 ml of water (<1: .. J '! ht:' ix) and 0.5 ml of aqueous peroxide of OrènfJ il 90 ,, - li: T8'1xjvi: ea) d "ns of i, 2-dimetrinx; t = t¯r, P ipiyne) maintent urr:, c; r, inr-tCtax Q ae reaction ae ïiu 25" C. We add neither, .ei \: e nor OM3; J.

   Strong blue light! ' ') 5t f.'lit86 during. piupieurs "'i'.r2Llte $ when we add 1 <' compound A to the polu- 'wicr; * We get a strong chemolumnc9ceDce when o; i r.'

 <Desc / Clms Page number 15>

 
 EMI15.1
 add no water and also when the peroxide is, of it 2 0
 EMI15.2
 anhydrous or aqueous Il 2 .'i 30.



  1. ;; PI is added lifJproximutivcII.ent 3 me of compound A 5 fl dl'l,;.;) 1 ',' cr \ 1 ('1.' Jr: ':), J Od iphenyl <orlthrCi cene and 0.3 ml of hyurrof peroxide, anhydrous cone in American iµl yme held at a reaction tenip4raLide of 10 to 15 C. A strong blue light is (! put on for several iriiriutes.



  F; XF: "PL 3.
 EMI15.3
 



  Add approximately 3 mg of compound A
 EMI15.4
 5 ml of a solution of 1 m of 9,10-dii: rnylzrnthrucira and 0.2 ml of methanesulfonic acid and 0.): .. 1 of anhydrous hydrofine esteroxycium in now leaked glynx3. a reaction temperature of 25-30OCt No chemiluminescence is observed. Ceperidztnt, a strong shiny blue lurr.ière is pewter for about 15 to 20 minutes when added
 EMI15.5
 0.3 ml of water to the solution. In the reaction, water can
 EMI15.6
 be reniplzicée with anhydrous ethyl alcohol (absolute).



  10. x.;!.: PL the; Ji '! Lipproximliti vel; .ent 3 ml of compound A to 5 ml of a solution of 1 mg of 9,10-diph <'- nylnthracenc, 0.2 mil of aci' ta, c. 8ulfonics, 0.25 ml of water and about 15 mr of hydroc: i> ty! 'C1>, y: <M of t-butyl (peroxide ".f") tiaiis of 1, .lylne Mtlntcnu A ..ne temperature of rhlct lon osa 25 A <) 0 "C. It does not boon" * rvc purunr chemiluntinescence.



  The results idcntit'h! TVPC îes reroxyn aulv.'tnts: b, c, u, e, ft 1;> ue.9 r''oultatp 1 <irnii. L7a3: avoe the peroxy- of f '1.11 ..'.,.; Rrs reaction of 50C. he ;.; a strong c! .1d 0 lUII.i r. nccr. (; e) (: t./t<,,;I 5 A 2 <> 1;, ifiu: .vi; quahd the peroxide "a" (:; u!; oit) ect uLiiJxil. u. when compounds A, Dom C or D are, trt.iliàLs; b. when compound A is Ut: i.li8 with r'ubrène

 <Desc / Clms Page number 16>

 in place of 9,10-diphenylanthracene; vs. when compound A is used with rubrene or with 9,10-diphenylanthracene at 60 C.



   EXAMPLE 5.



   Approximately 3 mg of compound A is added to 5 ml of a solution of 1 mg of 9,10-diphenylanthracene, 0.2 g of KOH and 0.3 ml of anhydrous hydrogen peroxide in anhydrous glyme while maintaining the mixture. reaction temperature 25-300C. A very bright chemiluminescence is observed which lasts 5 to 10 minutes.



   Essentially similar results are obtained with the following peroxides a, b, c, d, f. It should be noted that the peroxide "e" fails to produce chemiluminescence,
The addition of 1-2 ml of water to the emitting solution abruptly stops the chemiluminescence.



   Thus, under alkaline conditions, the presence of a substantial amount of water prevents the chemiluminescent reaction, EXAMPLE 6.



   Approximately 3 mg of compound A is added to
5 ml of a solution of 1 mg of 9,10-diphenylanthracene, 0.3 ml, of water, 0.2 g of KOH and about 15 mg of t-butyl hydroperoxide in glyme while the temperature of the reaction - tion is maintained at 65-70 C. No chemiluminescence is observed.



   The result is the same when using "H" peroxide.



   Thus, the conclusion based on Experiments 5 and 6 can be drawn as follows: (1) even small.; .... units of water present under the conditions of alkalinity preventing the chemiluminescence reaction if addition of water

 <Desc / Clms Page number 17>

 precedes the addition of the anhydride to the reaction mixture; (2) However, if water is added after addition of the anhydride to the reaction mixture, substantial amounts of water are required to stop the chemiluninescence reaction.



  EXAMPLE 7.
 EMI17.1
 



  First, 1 ing of 9) 10-diphdnylanthracane is added followed by approximately 4 ml of compound t, to a solution of 4 ml of hydrofuran, 6 ml of water, 3.0 ml of aqueous hydrogen peroxide. 90% and Ot2 ml of methane sulfonic acid,
 EMI17.2
 Blue light and Gmise when adding coinpoGé A to the reaction mixture
 EMI17.3
 i.'XI =; AâfI, F 8 ..



  The light emission of 3 ml of a solution of bia (triphenylacetic anhydride) Oxali (iue 5 # 67 x 10 ":; molar, of hydrogen peroxide 0, C5 molar and 9,10- di .picsnyi.catt nrarne 5 x 1C) -I molar in anhydrous dimethyl phthalate is measured quantitottivonent with a spectrof.uorirrrzrc. It is observed that the emission of light continues for a period of time exceeding 30 minutes. minutes and that the intensity of the light remains at half of its maximum value for a period of approximately 7 minutes. The yield or quantum efficiency of the system based on the moles of anhydrides used is calculated and measured.
 EMI17.4
 turns out to be eral at about 11.8 x 3Q 'sir = stein mole -1.



  This yield compares favorably with
 EMI17.5
 Qutlltic light yields shown for prior known reactions involving chemiluminescence related to the reaction of the luudnol-hydroxy system to sodium salt which has been shown. that the quantum rei; of .et; t corresponds sr? x x 10-3 eills, eit. mole -1 ('I. Brenner, Liu11. $ oc. Chim. Belcùs, 62, 569 (1953) .. on

 <Desc / Clms Page number 18>

 replaces bis (triphenylacetic) oxalic anhydride with oxalyl chloride under the above conditions, less than half as much light is obtained, the intensity remains greater than half of its maximum value for less than 2 minutes and transmission essentially ceases after about 5 minutes.

   Thus, the mixed carboxylic acid and oxalic acid anhydrides are significantly superior to oxalyl chloride in life and light emission.



   This example corresponds to example 1 given more
 EMI18.1
 âmM;:! <1uf that no water is obtained and the reaction is carried out in this case at 20 C.
 EMI18.2
 



  I? XF:; f 1.r ", We measure the quantum yield of chemilun.ines- cencu of the anhyddde bis (triphenylacetique) -oxalic-hydrorene-diph4nylunLhracene peroxide system using a spheroid diometer-fluorimeter The stoppered glass cell used for the measurements contains 3 ml of solution, is 1 cm thick and has a magnetic stirrer for stirring.

 <Desc / Clms Page number 19>

 
 EMI19.1
 



  TABL ";> .: 1. rRCaUC4 ...." îI DS CHI: ICI.L '; - n "SC7'.CE.
 EMI19.2
 



  : ,, wrinkle bï- Ferxy'e 9, I0-di, hery3- 'Renden.e: f- & n- Ir.t-ensite Ar.hvdridebis- Fe-oxy ie 9, 10-diphenyl- tiue-Ei-' st.ein / lur.lr.euse (tri ;, h.:r.ylê:ic."::- t th: rdr ", - re ar.ht.:-acene t.ir:ue - EL'stin / lu :: -. ir: euse tÍr; ue} OxalÍ (1Ue x, ': â iE.' .. mole / 1 òlvant T: ï718 a'anhvdrUe :: '., -, XÍ.léde 1..4t = e V4 1 ue) oxali, ue r.cle / 1 n-ole / 1 oiv.nl; ..,. ber n-.ir.ues r: .clc /: 'l;, ... t.rt Ir.ir.ut.es - ------ ¯¯¯¯¯¯¯¯¯¯¯¯¯ - '"' X- = ',, -.> - ##### d. A 5 s'? X ¯¯, .- .... ¯ .......------.,. = HLa: 3 i:: h¯r: .e .., 3 x lfl G, C7 34 (2) .... 9 * x: "O-2 G f 25 x -0-3 ben ..:. Re - ::, ::. T, L: .te de O.19 x O-2 0.11 volure <3} 4..94xIO-; x 0.25 1 x le3 ie: .â. '. ai: C ".t: x4state¯..e of .1.tu3 x 10 -2 six 11 (3), 94x10 xx 0.25 ix to ir .. t :: vi {b -! .. by vobxme)
 EMI19.3
 În * .sité ---: -. Grows does not reach read. --lzârt value X, ,, 1, ..,:, .- + i-zer¯sjié àzcroîsse:

   n.ar <.ittelr..re 1Jn '1 \ lê.l: "t va eur ..axn.d fmf.' .- -: Ti. ^. ter.sity; .. crazsse: n: zr: teir .r .sn; üarL; e sn alear., axilr.a. a.¯ ^ .aire car.s ". 0 .., .-., ....., .. i 1 .... '6C "" "" "' e r .....- .... tl>. '0'> l ..;: ') .... return the, Lx.Ii.lC ^. ix ^ rCÏiL..lïf.' ".,. 4L. 83 '' 'l't "\' '' '' '' '' '; 11" u c ..- .. e..ce..tI ...... e.' ". ' -......... o. " a.:! O .... ¯oJ. : '' '' '.. 4 ..- .., ... e Ó "" ", .1 .., ...... 10,.; .. <: 1.': -" OXlr > .ale .. 'll. -'-, 1.1¯, ..... ë.lre ... ar.s water, Bir. ':;' .. 1 tcute e;, za., N, àii nas j = s it has 4tô .Hr'er $ :; e: ir.et.e :; "the sclution er. Raiscn water. tcute 10 not z ^ # '.. i ..' ^ â ..,. â :, 5 ^ tilQW2i 'ra, S..I: Il. de Ia ït: =' ¯en excellent.
 EMI19.4
 

 <Desc / Clms Page number 20>

 



   Example 9 indicates that a highly efficient chemiluminescent system can be obtained using bis- anhydride.
 EMI20.1
 (triphenyl, ic.etic) -oxali (read (cfr. n (1) of the table above, n (1) corresponding to example 9 above), and that the chemiluminescence yield can be improved. in certain compositions by the addition of water (n (3) containing water compared to n (2) without water).



   EXAMPLE 10.



   The preparation of esters of oxalic acid and the experiments in which these esters are examined for
 EMI20.2
 determine the chemilumineacence are shown in the following table,
To obtain the data in Table II, the following tests are carried out:
A. Approximately 3 to 5 mg of the compound are added
 EMI20.3
 to be tested 6 5 ral of a solution of about 1 ml of 910-diphth: - nylanthracun (DPA) and 0.2 ml of anhydrous H 2 O 3 in anhydrous 1,2 - dimthoxythnnc maintained at 25 C bzz, B. Approximately 3 If 5 ml of the test compound are added 1 \ 5 ml of the shot suspension; of KOH (DPA) 02 (1 pellet) and 0.2 ml of anhydrous ff2t72 in 1.11-si; .:;. anhydrous oxyethane maintained at 25 C.



   C. We operate as for the test except that we add
 EMI20.4
 approximQttvecnt 0.1 ml of water before addition of the compound under test.



  D. Approximately 3 if 5 m * is added to the compound ± 4 test <; r to 5 ml of a solution of about 1 m of (I) P;%) dr.s of 1.,? .- din; thoxyf> thane containing 5% water at 25 C. One adds 1n, ... ú- diatemont about 5 mg of Ua202 "E. We add approximately 5% of the cO;>. p050 to be tested at 5 me. ml of a solution of 1 m of (DPA) and 0.2 .1 of CH3503Il in., 2-dimdthoxythane containing 5 of water

 <Desc / Clms Page number 21>

 and maintained at 25 ° C. About 0.5 ml of 30% H2O2 is immediately added.



   F. Approximately 3 to 5 mg of the test compound is added to 5 ml of a solution of 1 mg of (DPA) and 0.2 ml.
 EMI21.1
 and 0.2 ml 90% H 2 O 2 in 1,2-dir 1-thoxyethane and kept at 25 ° C. This constitutes an acidic medium.



   G. Approximately 3 to 5 mg of the test compound is added to 5 ml of anhydrous dimethyl phthalate containing
 EMI21.2
 . mi from (3PA), U, 2 rr.l from Kat! 50% aqueous and 0.2 riel of 1,122% 90%. This constitutes an alkaline medium.



   H. Approximately 3 to 5 mg of the compound to be tested is added to 1 mg of fluorescein, 0.2 ml of 90% hydrogen peroxide and 0.2 ml of 50% aqueous potassium hydroxide in 5 ml of solvent. .



   I. The reaction is carried out at H except that 0.2 ml of 5% aqueous potassium hydroxide is used.



   J. The procedure is as in H except that 0.2 ml of aqueous sodium carbonate at 10 ,,
 EMI21.3
 K. The procedure is as in H except that no base is used.
 EMI21.4
 



  These qualitative intensities are basic: as the reaction of oxalyl chloride, peroxide ú hydra / "ene C01: ddó- rr = e as strong ±!, (5), i> in the present report, and by- In particular in Table II, other abbreviations are used, namely K) Q medium; i1j * low; "" 1; trcn weak, barely visible, the dependence on: Hlt, the "dune of life" of the shir "io-lumineccpnce usually obtained Q619A of several times that which one can obtain with the system based on a chloride. {a 'oxalyl and a peroxide ci' hydri '{' 8lJ'J.



  EXr;: PLE3 1.1 TO: i,.



  The experiments described in examples il 1>;, ii, ciu- f; l \ "e: .em :; are ef4lectudr> coml, c les; xp4riences r (> spectiVt5

 <Desc / Clms Page number 22>

 described in Example 10. The compounds to be tested are oxamides.



   EXAMPLE 11.
 EMI22.1
 



  The amide is 2,2f, J, t-tetranitrooxanilide and when tests A and B are carried out, light is only obtained during test B as shown in Table VIII. This compound is strongly electron-negatively substituted on nitrogen,
EXAMPLE 12.
 EMI22.2
 



  The amide is 1: N, N'-bis (phunylsulfonyl) oxanilide and, in the case of tests A, B, F and G, the light is only obtained during tests B and G while does not succeed. not to obtain light during the tests and G shown in Table VIII illustrates this. This compound is strong
 EMI22.3
 pubMitué electronically on nitrogen and light is only obtained in an alkaline medium (B and G). The intensity and lifespan of this type of compound are unexpectedly greater than those of the following other "amides"
 EMI22.4
 Read the present invention and represent a distinctive and substantial addition to the basic "amide" system described generally herein.



   EXAMPLE 13.
 EMI22.5
 



  The amide is bis (4-nitraphtulyl) oxamida. As regards tests A, B and F, assay F carried out in an acidic medium does not make it possible to obtain light, the test carried out in a practically neutral medium makes it possible to obtain very weak light while the test B carried out in an alkaline medium makes it possible to obtain light, as shown in Table VIII. The derivative in question is a derivative of oxalic acid
 EMI22.6
 substitutes strongly for electronefstively on nitrogen.



  EXMMPLK Here the amide is di-1.-imidazolyl lyoxal, is a compound of strong electronically substituted oxalic acid, ('nt.

 <Desc / Clms Page number 23>

   nitrogen and exhibited very low light production in run A and light production in run B, as shown in Table II. Again, the preferred results are obtained in an alkaline medium.
 EMI23.1
 nu t: water 11, the compound 12 provides light 1) whose intensity and lifespan are greater than those of compounds 11, 13 and 14,
 EMI23.2
 KXKMPLKS 15 if 31.



   The higher amide used in Example 12 is tested by proceeding as described in H, I, J and K, using different solvents as diluent and using various concentrations of alkali. The operating modes., H to K respectively are as shown above.



   In Examples 15 to 19 and 27, the procedure is as in
 EMI23.3
 H. The KOH at 50 ', 0' provides a fold corresponding to an alcr: Li; high.



   In Examples 20, 25 and 28, the procedure is as described in I.



   In Examples 21, 26 and 29, the procedure is as described in J.



   In Examples 22, 23, 24, 30 and 31, we proceed as in K.



   In Example 15, only
 EMI23.4
 tetrahydrolrene.



  In Example 16, only dinitithylsul1'oxyctc is used.



  During the example 17 we use uniquer;, ent ethaner. in example 18 we only use
 EMI23.5
 l 'acôtvnit..ri1 ('.



  During examples 19, 20, 21 and 22 we urilize
 EMI23.6
 only 1,2-dimethoxyethane.

 <Desc / Clms Page number 24>

 



   In Example 23 1,2-dimethoxyethane and water are used in a ratio of 4: 1.



   In Examples 24, 25 and 26, 1,2-dimethoxyethane and dimethyl phthalate were used in a ratio of 1: 0.



   In Examples 27, 28, 29 and 30, only dimethylformamide is used.



   In Example 31, dimethylformamide and water are used.



   It should be noted that Example 18 illustrates the only system where chemiluminescence is obtained using a pH corresponding to high alkalinity and that the solvent which is used is acetonitrile which is characterized by an order. very high polarity.



   Procedures I and J typically illustrate the preferred pH range in an alkaline medium. By. elsewhere, these Procedures I and J illustrate the use of essentially different types of bases, i.e., potassium hydroxide (KOH) and sodium carbonate (Na2CO3).



   Procedure K illustrates a pH greater than 7.



   Table X given later illustrates the results of Examples 15 to 31. The effect of the change in solvent and the decrease in base strength on the compound used in Example 12 is shown in Table III.

 <Desc / Clms Page number 25>

 
 EMI25.1
 ï;.: -: t \ U 11 ..,; :: s1i! 7tlc. tl '. ce c-L;, ir; 11; .i! lejce: .ce ±> ..:.:. ;;; ri; t ..- 1xdlir: ues ..
 EMI25.2
 



  TESTS
 EMI25.3
 ABC Il F (J. t: h j ... i (XL <,. 2 2 (1 '"O)"'.; '-' 2+ "2 2 -. KCH t: 2 H 0 cq 50 H cx..l'.e 1 "", at 1 ç. 1: 4. y: 1 <, '-'-' 1. ± ii 1 j ox ':' i? = t '.', = <. , -nit.rc -: '. hryie li K 1.1: FI Î 1 Omlt> À é <iC u-.', ..- sir, irjp'4 - ': ylle ec <;:. ç. x. z (;> r 'i' ir;.; - M 1.1:.:. 5 v cxë.l lof 'cc 2, It- J o- r 3 ri t.ro! ht! 1yl c 1.1 M? l K iI; 1 V oxaliie, the h-cy (': 1. (":]' [.1 / LY 1 ('1 ±":.: Î.l'. "K VI oXila1..e of # -icéLylj ,:. it, yle '1: J:.: K tl 1.1 iJ oxil; = ii, u + 3 -. <' t ':: cxy-4-f' .- y; rh ('yle = .j; j j. = s, ir;. # VV Vm <:> ;;; 1 1,; <; of 1, -pl; é.r, yl?, hi # 'r.>. l IJ T. 'K Il lfl o>: i; 1 z. T dr à, 2-j. Li ";. J; 1? R, <'; 1 I N r; X o>: i: 1 t;. 1, u (,, =, 2 -, 1, qh: ..?; Il 1: 1 H,> 1 o;:;: .i;.: <, C <-> rh.yl, <! Î j iil i y. lr., flt?> j, 1 ', ".

   Vo ": il 11 lili c>:.: Î; ::. R this 4-c .. 't.;.:. Xy: .h'r: yle il ti: Ii 1: li' 1 1 1 xà ; at 1 t. t. P,; ui. '! hyl- K VJ iRI Îi; OY ox; alz; e ée di-l-? ro; .yle ti 1, lY?, 2', 1;,! + '-; [t.;.;.;. îit.r # <;;: i; iliàr = tl li "" 1 "t't b' .... (", h: "1 -". '. "1)'" "" l {d "". Il 1 b: ir. {J + -r.Ï1.rC ';): 1U, lyl) ox ;;;. Id ('?> 1 tl XVm di-li: .idù7 '' 'lyl: -iyox? <l? "lfl
 EMI25.4
 XIX Ù-é> cylh j <u rcxj / 1 =;:. i ::; t? A The compounds Ili, I ',', V, V3 e; 'v'I73 comes out this r.-. : .-. ux con-ro'-fs and are part of the present invention xi.

   E.flG <iiffé; 'Cn', "5 li: .Y: i 'v'. '.:".:. I' .1; .ii'i ±: '. vs; ii = -.: ':! "-.; - L:' tS ficIsj.M: .C3cT1 {rc,: ..; lP;. .., T: .i. fert-tc ;; 1 # :: :: Cßâ.;: El.î :: S. S: #;> 1.

 <Desc / Clms Page number 26>

 
 EMI26.1
 i II: uL: '11U 111 Qualitative chil.ÍoluIr.inocence assays on tl, fi'-bis- (phenylsulfonyl) oxar> ilide
 EMI26.2
 Test Chiit.iolumenes- n Hssai anlvant (s cer.ce 15 Ei ttzw; ydro: irnne lo li aitr, thylu.r Uxy N i7 EI éthnnol il .13 H ac: toricril li - 4 Minutes i9 il .J .., 2-ùimvthoxy0th..de tl 20 to, 2-ùim ±, thoxyàùi; ur; ig - 9 ffi1nuus 2 * J .lJ /.- dimt, hoxYI1 ..!, .. d1e M - 95 ..i: Ut. 0S then. 'Tf- 5 ..' 1 "
 EMI26.3
 
<tb> hours
<tb>
 
 EMI26.4
 ; 2 K., 2-dir., ThoxyéL'slr, o M 1) K à, 2-ùi; <. ÔLhaxyéih,; <ne shot and water (41) 1.



  24 K 1,2-di6thoxythne and. (.lZri.GLiyl; iiliX.s.1 * rW (1: 9);, rJ 1, L, i ..:., '411.t.:tÎlUfy ,: :: lirrl4 ", 0 e ii: r .. 'thylnilt,.; Le (1: 9)') 6 J 2,2-àia, àihoxy4uhane Nd 26 J 1,2-din.hoxyhne et. àinlta, hylt'.lLaLe (1: 9) 27 H nim .rtüy.i'or:.,; xn, iue 28 1 azmttrylt'oru; a: r, iàe ii - 3 ::, j.nut; es 2Q J V7.IL (: i.'lylÎOri: .i. til. 1 (E ':.: - 25 1; ii;: uies then' ..- 5 1/2
 EMI26.5
 
<tb> hours
<tb>
 
 EMI26.6
 30 K l1Ín. (1 thy l for "i.I;: Íde!,: C 31 K ù3.rr.rahyl.'or ;;:., Ide ..e
 EMI26.7
 
<tb> and <SEP> water <SEP> (4: 1)
<tb>
 
 EMI26.8
 N.B .., a. letters, '1, M Si (: Iifiert rspûcives.'n:: weak and: .. oyenne. b. Rôàciion er, ;;. ilieu h> Jii':. i, jài, i;. c. Or: obsc ; rve 'dnc àt: i>, ii; rC 1.1':. rt ::. I ': t ..; I, Ol'éi, t; 13 j. ;;: ..... t j.3 ** 3;. ':' L, ute: 3, h.ür: \. I 04. 1. * o ", ((.. '; r, 1 c crtc:' .; f.; O-

 <Desc / Clms Page number 27>

 
 EMI27.1
 1 1 <iiàe 1. i0.

   Du: 'de de vie .il .: the lutftiëre; the most 1'; i.l.l <; ru: .P.i.Si.7Li 2 ii j- hours. d. uiludon with 10 ml t; i '..' t.,. 1: li.e't ', i70Y, y.': L't7i1S1G 'produces a weak r'.l: a: r ± :, i ';:, 1 :: itl; .r,, 1 <;, 2 1 ;; 1 ù>, .'.- rbo: .te xo, iiijue to L0µ1 produces. t. lof,.,} 2.UI..i ':: r ,: utj.ilLt: tv: ... t. : .. cyer: rte pendant. 2 nlinutcss, Co: r.:; C indicates the ti.4blcu III, on Klitâ (: Tlt les l:; ú: .i; cu.1 'r.:utLs in t.en.'. In inl-eil. ei de du1'c de vie with ca ,: ct :: ¯, ct; te ridique à, .0; di:.; de :; sv.v:; rt: s polar (see by üxe1.plc, examples 21 (t "1; <;).: '± 1 o -... r0e Je via Je la iu:;, 1 & re rournic by 1 (1 ii, t;' - b # <;. i .Jr; yia.mit.onyi) oxaniiide is much more: r "'l.ûc than that pure fourhic 1C oxa- chloride
 EMI27.2
 lyle.
 EMI27.3
 



  Cn obuGrvc de lu lutr, i4Tc: ct 'r, teT, identical sit,'. The last ccrr.; 7o:, arlt i. (, Joust to 5) '::;' (: I:,.: Chill , i (; u, ire5CCl1t is. the 11,? 1 '-bi 5 (j; h: "i, yl sa 1 ion) .l) oXanj. i 1 di, (", U le; 7r: roxyc: ay: rcy: c 'or the (',; 'O..Jiph: r.yl; ... t..hr; c0:; u. "bd, lu CtlIviL?, Ul, .ji: 4.3 ccriCe pst obt, + a; iu <-, ci; lCi '; UC is. 1't5r': 1; t: de i: .te: ïii of the rôàciifs. ii; c; ji ;;, 5 * #,> , ir: <# ce>; cc iou; .i, 1; ['Oit' le: ':,: P-bis (ph.1nyl- "" 14'0 "1., 1) /" 0 "" '1' "01 'If' the proxy.t--: i ': .j ..; r <ij, 3 ;; e" (0 "the curbonThe scuic A> (, 1 and. La:; lOI" (?. '.', C (ri.f; est -1;.:. 5 11S.C c ,, .. c I tcr., P (';' ', r .. :: 1E: ; C 1'31. '"Ia 1S'G, 1:., .. G; O).

   La chin, iol ... l: 1.i- lf ^ .C ± 'I ::: \ ....... L "..1 <:. L'S: i. Obi; erN', 1 < , e: "ie:; t; .CC d '.". IU aoT: L lob q.'ê4tt, itê j.;> .i 1cindrc lu CCT.CC:.wi':aLit)T ..'. ; ,, .., iüCl.,. e it pro .. voque ..iz. :: cubi.iiL 'tic 1' <;:, iJc utili3t. Le: 'C! t.pluC6: .. e !. of j, <; r <.,;. iy:; c .i ';. y.ii "<: j.éxc ii 9' pir uivcrn,; <;: c>;.; yJ <; x cotni. ie le per- rJ {rC ': ":] \ C \ l: .jfl'.r' (; l'rc .1 \ .. f .; l '; ir ù VL5 ..; t:" (i ; ': ïûe: j COHU.lC J..e pa .. i ::. jiC # 1>: 4ia. (1;, :) Co: .Civt', itilyltrC) r (; 'C3? "J. .: E 'of tO \ At, yl0 Ut the acitt (-' 2 ': t: ... C i ;; 4C gives u;' .. ar.l ': .. OT.i.. .1.C 'C: Jl :: ajc) iLla.rU; (; f: i'lCc: r.,: Iâktrt.iÉa l'd <5 ;; 1 described- clrl tiWlt..u He with d: tox, .li.t-1- "of 2,1, -1, iir, iircpia, [nyL <;. 0 ::

   observe a chi;:. io- lU.; .. lf.; j (; lè1): .. n3'e ;; r, cnint strong 1l.i: T.4lti.wt ', that the,: eri, 1 <; r

 <Desc / Clms Page number 28>

 
 EMI28.1
 compound added to the chir system, .io:, urt.ir.esce :, c is 1 ox.l.te of Z, 4-dicitrophJnyl or peroxide (itîiydror¯ùr4c or 9, -LO- diphenylanthracene.



  ,: v fm w; n ü. , '3.
 EMI28.2
 



  The test /, described in Table II, is carried out with
 EMI28.3
 2.1 * oxalate .. dinitrophny.e at 3 different temperatures,
 EMI28.4
 retort follows
 EMI28.5
 1'hm}:, \ U IV.
 EMI28.6
 



  Ten, y; rature Chii., iolixii, iaescexce C observed 0!;. oye: ine; her.t. weak 25 j1 ', oyeI, r.m, er.t strong
 EMI28.7
 
<tb> 65 <SEP> strong
<tb>
 
 EMI28.8
 thus, the chii.-iolutriincscence is observed in an i? '1.! fitnG of ion; extended perature EllI'li? l.1. 34.



  The assay described in Table II was performed with oxzilut, 3 \ .6 2, II'-dini troph.5nyl in the following solvents using 4 sodium to the pluce of 9,10-diphylanthracne.



  'ri' '/ ..! v.
 EMI28.9
 



  ; 01 v.nt <? H3 .... i olu,> tJ1l> scl'T: ca 100> J d'euu liulle 95; d 1 tou - 5> 1 from to, 2-ùlm, Ett> oxy, 'ii ;;: ne Trôs 1': iiàe 75; j (water -.5, from 1,2-uim, lLt; oxyàLi ; .. r, e l-'hible 5C ") Ci 'c ... u -5 (:, .. of i, 2-diml, hoxyht <ne.,. oYl.) nne 25 ;; of u .... u ..75 of i, 2-.ui ;; tct.hcxyj! .ne Low
 EMI28.10
 1, Insi, we observe 1 <.. cl: 1; .. iolu;., Inesc; i, ce c, a;: â There qlwhtitê d 1 (HiU prosente utLeir, i about 95 of the total e .la
 EMI28.11
 solution.

 <Desc / Clms Page number 29>

 
 EMI29.1
 



  HX.'PLH 35 ..



  Tests A and C described in Table II were carried out with 2,4-III oxalate: itrophryle using various peroxides in place of hyurene peroxide. The results are shown in Table VI. l ', a iil. "<inU VI.
 EMI29.2
 



  Peroxide 55ai R Test C Hydrogen peroxide mOrl.; U1.! N.Ent strong medium ily4àroperoxyc4, ue i-1>, Jiyle weak l;: OJf: 1: 1 "E.'1..G'11t '.
 EMI29.3
 
<tb> strong
<tb>
 
 EMI29.4
 P, oxide ue ui-t-bu1: .yl zero zero acid per10 ', ll'iliUC very weak very weak Peroxydl1 of 1; r; .zm% ie i, ulle zero
 EMI29.5
 dnzi, we observe Clil.iu3. () Li.lu.j.IIOSCGI.ce quoe ;, d le peroxide; filyara ^ W is rel; .plrzC (. by a hy; a: orero: c;, üe: ..



  I ".r a peré-ciae in the cr system, Ü.iolu: .ir.escent t4ll: t in the presence that in the absence of water. We i10; .. :: BrVt: none Cfv.G. LaL.lIa: FuC .: ii (. 't. ciu, .rJ en u Li1 iS8; eg, 11-bJ.e ... enL a di ,, "1kyl peroxide or a dinryl peroxide. . f'i.:; - 6 Or. Hi'fcct-ue ues;,. estre # ltLszal: 7.W 3, '. VfS) OrC, ciilv on the ß .. ^, i, Cat.i: c hil..io.J.ur..ind5ccr, t oxi; 1; .ae of 2,4-d! .f: it.rophnyle-, peroxide a:, ura, Lr .-. 9 C-uiyht '. r.yl, ntjr '; c: Ite (IJ; -A) in solution o.ú, t, G ci .. 1ht ..: uto ue til, t: .i; L: lyi <tU;. oyen of a 1 "ü.Ot1 (; Gre lPCt.l10rnot0H.útr'0.

   The t <'5u], td% S ti <t5 1..C33Ut's:. ^ A are. rl: sun., 5 at trLi .i "E: 4ut Vil,

 <Desc / Clms Page number 30>

 
 EMI30.1
 1 :::. : u t .. uor.rc-es relative to the chix :: iolu'.ir, 0scer: ce, êu systèn: e oxalate de bis (2,4-dir'itror-hénrle} (:: # yÎ-. ¯ ¯¯¯¯¯¯. ¯ rr'OXLT, ē 4: JC. "O i: T: E '- ¯ and, solutifii, <a; .s a1m; thyl phthalate
 EMI30.2
 ..- ,, {f C}>, C (i-1 C. t 3 1 b T "'' 't -'" 1- 'oer +? e:., :: .. ura U. n- C 'D "' city of l 1- 0 (..- - ¯ - ;;, lge'i '4 J'hi rr.cx. Tj ..lX 2: .Sīt'ln T' ... bt '' Z13: .clel ... oeL ...,.: -. J ... oi 1! Irls X '(7 Mjp "" x 1lW' '"-' '; r' '' e1 '-1 u.,.



  ¯¯¯ 1 .. ',' -, - ', .. OJE' x ............., \ J -.... LC =, 8g x O -4 ', , T. 1! 2 & r.t 48 (! 3002 13.9 C, 12% 1.11 x ït7 CI, 1- C: 0 11 13 C, 1l8 13.2 1.47 1.11 x iO-3 C, l 90 "11.5 0.121 12.2 1.36 1.11 x .ïQ- 'O, 1 90 11.5 0.121 12.2 1.36 1.11 x 1C? 0.1 90 n 30 0.028 10.2 1.13
 EMI30.3
 1.11 x 10-3 L, if 9 0 59 0, 0 ijci 10.0 i, 13.



  1.1i x ic-3 (Î, 1 90 1t 23 0.052 10.5 1.17 i, il x 1.0-3 (', 01. Tr 6 0.312 12.3 1.37 ,, i; x' r - 3 c, 5 450 "26 O, G40 8.1 o, go 1.11 x C-3 C, 1.90 G, 5 x 10-2 21 0, C62 11.2 1.24 1, ... .1 10-3 if 0 2.5 x .10 z 12 0.108 12.2 Zt3 1.11 xl0 "3 C, I oc 10, Cx 10¯? 6 (1, 2GO 10,2 bzz 1 x 3¯0 -2 fi, 1 10 i: =. '. 2ra 4 3.05 7.4 7.4
 EMI30.4
 at. DPA (', iC-a: ī.:, F>: yIiLL: ¯c.c'r, i: 5 x 10' mole per liter b "t 4 i I ï'.X = t (, f" ": n :, .. r :( 'j: l5 -ur u., I ir.'. r.it ', j ..;, a u.ae:' '' J1: ,, 111U (: u quarter, ùe pa value. "âXl1..ae c. 1, '= value;: ;; 1-1: le do 1 t sI:,' -!:., (, a: a..w ii 1 , i è - erdse.

 <Desc / Clms Page number 31>

 
 EMI31.1
 



  . '. u to:>;. <a;: a VII' 1ui pt't "cè.:; c, or 'v'i que l'cffi- c = / cii, t u. <- L !. o!:!. ui.Lc ... ct.t. uievuc de a chi: .. iol.i :: Gseef.ce (rei.d <;; .. ini <js:. ±, tlq, ae 3 ) is, csset, iàe12ei, .ei> t ,,. aii.Lenue i ,, ome to ane cor.c '. ::. L:'; tt.io! t <,. od4r6J, <; 1,1 <Jlev ± c Hfl the oxalt.e of 2,4- dinirop '.' '' Ï.ylf, .u, .tu '; .Il .j :: l;: ¯>, c (jae the increase - sei: .ert of 1; <ccr.ccntr .... tion of hydrogen peroxide led to a decreasing efficiency of sYI3tè ... C 'ciii;:> ioLwi.ii, esc; iiL.



  By \ .Iillrur5, ce t-ablëau '.,' They have re that the addiMon of water: tU c, .zr4C-e no n .... ni: re 51! Nific <ttlve l'eiiicacir , E or efficiency of the sy; Lé: xe chi ::: ol:, ur.ir.e:;> c8: .t. (, ep l.el Ürt, it sen.bic that of .juii; tiL ± = of water crossed:> 5, .rc :; co:, J.11.: 3and. a zcceleration created, i: : ;; i1r.l .. tie the reiiction of c.il.ioljt., ir.cscet: c <!.



  'tu tt.'. bic'au .VII qui pr.'cc, or. see that the useful life tcirps (t 4 'r! ....));) ut 0trc oH5si co ;; ri que n: i.r.u! .CH or passar 1 hour, 1 h vo 101.1..15.

 <Desc / Clms Page number 32>

 
 EMI32.1
 



  TL = ', rLt VIn.



  Data cox: cerr: .a, the chioiur.ir.escence of the toxalatp system. of bis (2,4-air.itrsr:. 'r: yl) i3:'.) peroxide C: a ',. Z'Ut¯ :. - azei: t ii ".: fr: ± '. ^ W2: 3t in S0111u.?C :: aans eu phté: leite 4e Ùii't :: Vl2.
 EMI32.2
 



  Fluorescent 1..1. l b le '), "prt .., .. + t."' '' 'e / "j'",; + 1.



  Fluoresceii 'L "ut: \ .en ... é, ...... (.... <-' .. ......", Go "..C .... ,, - "'' '1'yne à;, ole 4 n: ax mé1X' lairbert .J. '' '' Stei. '' O" P-- 1C "...- i '+; cr 1pe ilole .1. 4 irax ". 8 re lai7, bert x (, C: 43" .'-; ..'- C .. r - ..! ...



  -:?:. Suxrer ', .ix ", -4 5s5 13 8 3 22 3.22 Calcof1uor J. 1 13.0 3, CO 3, CO jÓur.e 6-G t, x. 1.0-'" 4.5 13JOO 3, co 3, co Calcofluor d 13.0 3.80 yellow 7-G 4.1 10-4 3.0 13.0 3.80 3.80 jaiine 7-G 4.1 9, lG-diFhér.y1- 9 ,! C-ciirhenyl- 5 x 10 'i' 4.0 3.0 7.40? S4 '
 EMI32.3
 at. il:. = ';.: 1 x 10-2 r.': f)] e 1-1 peroxide s :: -: i: ro e er.e: G, l 1 # ole 1 b, t ¯4 Iftïx: C - .cr,;:):> r. ": - 1..115 to have the intensity .the .luixiére lH: C.: '015se au C:' tIFsrL es ,,: V: , 1 ± '1Fr i #, i = ,; 1;:. I = the c. 1 <lX' = v;> 1> ur ... xialc de ïsir.;. Er.-iL = light é , .ï:; ed Co1o! "è..r: 't vel, du; z.r.: .. cricur. Cy, .r., ": 7.id Co.

 <Desc / Clms Page number 33>

 



   The information given in Table VIII shows that a variety of fluorescent compounds can be used as fluorescent agents for the chemiluminescent system comprising oxalic ester and hydrogen peroxide.

 <Desc / Clms Page number 34>

 
 EMI34.1
 



  Given to 1. chir ioluc, 1 # escer; ce da syst4, ne chlorjrc 4'oxalyl = (2,4-dinitrophenyl) oxilate in scluti "! 1 d'ns eu:;. '¯ (Jl <-e from toï: .. 't :: ^ l
 EMI34.2
 : é4ctif t I T 1 f Tienùe,>; nt- Radiation capacity Type Kole 1 - t i ± 1; Î n - :. é.1X. , T>;.,;> 'E' x C Einstein 1 x 10 .-. Ln. ¯., Loti. :, lr.sel!;. l., () ¯C: '1nsteln t; hioF¯re ctox: .lyl lai s3 5 o, 66 Ghlorùre C' ox;: ..: lyl 1.11xlO '2 or 5.1 0.66 Ci; la : ure d 'oxalyl lx 10-2 Fluorescer. ce abrupt stop e :. èe5t.r "ct.:. or. ce lt [; er.t florescent LÀ190 1.1 x 10-3 13 0.118 13.2 147 ::.: î'0 1 x io-2 4 J05 7.4 7 , 4
 EMI34.3
 at. li 202: 0.1 mol 1 i 9.1, n-diphenylntnracz-ile:

   5 x 10-4 mole 1 "b. U 4 - '1 Max - te.ps annealed so that the light intensity dk ± b1n to a quarter of its maximum value. C. = R value, .-. Xia, .ale 'e the ii.tcrsitc of the ï: as, iazre er.ise.

 <Desc / Clms Page number 35>

 
 EMI35.1
 



  ! '"-:' .: P:,: ';' 7.



    a solution uer: viror U, 2 t; '. acid anhydride, iC, tii; vs'r.yl- (), i0-di :: yc: rtc> rt ".r, ¯c4r.z ..:, Gr: ic; .raxyli (, ue çtNrvJ e..viron ... 0 1:.: <the tetr.rtyàra: urt = r.rtc: (wc-, lv, .r, t), we add BrGYi: 'UT iC x, 1 Ùlt.tr: es <? Ilion quuucGCro # lM # pTox} soatic, Cn ob) \. :: 'v,. \: 1 (;:' :, 1,. ;;; ,,;. Û 1-. i ', u.'% lE.lt "'F.lt:tv',. '.:' '1):'" 3 'Or. t'jouLe ta, C noDjLion uc suc i;> i; I 9 , <'. 0-'G; i.chloro- ^ uz'bcrt;': ... G-ij.r "r: yi9yi'cS;, aytt, T'C;.: .. îr.lGi: : C d; H. :) ('nviron 0 1: .1' .le r ir ;;, y; z. ^ Cli ui "ûlilla at about 10; <, 1 of a: ïCfi, ti tiürv .. .gueuse 1 li aia; = sodium ariocia. We cscrvc a.: wi6sicn / Je lUi., i0ro bleU! -violct \ tfJ. ûaIr.pxc 3ii llluciro in outft! the j11 <:. ente inversion when using a bi; t4ot-t; rmrc d'ocide} d'ur, dilâyttro; athra.-
 EMI35.2
 last supper.
 EMI35.3
 



  :; .i ..i,.; ..., P lÎ% Q solution ue ..., 0 t tt 9 ,,, C-iJir. (T- / it..roph.nyl- Qxycc.ri3trty ':.,. O cii;: ;; lr.yI. ',: Utiiity = tra; a :: ßrtrtcëz: E ù.n, s;:'; O ml of 1> htu.;, ie 1.10 6Â.t: i4t7i, Lt. (3 est. Cf '1T..lyt ü, L. ::, 1 of ft: r'GX'tlf.' 'D tsyc: ru, Trt. X in rantc> ïte rie ù.ts: trtrïy7.et It IÜ ù'v4u .



  Now. Observe an orb t: .. ission of lu;:. L (:, û 1.1 (.u (: qui uure or.ü- tents. - ,. ucar: d one prucôue following, the ri: ce example using 4 ml a:,. 'Y',,: J1que iJ <1ue: .. xi x, nl; ire instead of water, lrt '; r, i.d5ior. ..the moon is, more ir.:.er:r: i :; ure- ii.oins long-
 EMI35.4
 time.
 EMI35.5
 he:. ; , bi! ':. ? -n 1 h y: ro-2-oxp -! .- p yr '. vL 1. - J. ' - ''
 EMI35.6
 

 <Desc / Clms Page number 36>

 
 EMI36.1
 Pr, p.1r: 'tt Í ("\ n: 2-hydroxypyriJine (4.76 t', 0.05 mole) dried by distillation & 6otropic with benzene is dissolved in 150 nil of 3., 2-d Distilled fresh methoxysthane To the aritated solution are added 2.22%, 1 (G, 025 mole) oxalyl chloride and 5, D5 (0.05 mole) of the trir: ttry * arine.

   After stirring for 1 hour, the liquid is evaporated to dryness in vacuo and the residue is heated with 2 portions of 25 μl of chlorofonyl to obtain 7.5 ae white solid. The product is dissolved in benzine to obtain 2.76 th D7,. () Of criotuux blunca PF 164 - 1? 4 C (d) Analysis for Ci? 1I6N204 Cllcu16: C: 5g, (? 2 ;; Lit 3.3ù> 5; Xi 11.47 Found 0: 59.06 rit 3.31 Jj 1 ;: lâ, L6> 5 Absorption bands in '4einrraroui-, e ttcr; s la rarior, du - co , úÓtcr'lhiratil ') t1 in nujol: 1742) 1712, 1672 cm.



  )> 1X, 1, ji;) ±], 1.1 4 ....



  The esoals iiiontr6a in Table 1 are performed as
 EMI36.2
 follows:
 EMI36.3
 A, B and C are done by proceeding ... the the 4 .-, Czo way that for A, 3
 EMI36.4
 and C in Example 10.
 EMI36.5
 



  L. Approximately 3 to 5 ml of the compound to be tested are added to 5 z: 1 of a solution of ... m of (DPA) and 0.2 ixl of CH3803H d.:.s of J, 2- dimlthaxythane will contain 5 water and maintained at 259C.



  About 0.5 ml ue -, i2o2 to 3 (.,.
 EMI36.6
 



  Qualitative intensities are based on
 EMI36.7
 oxalyl chloride, the reaction of peroxyce othY \ 1rol..me being considered strong.



  The qualitative tests relating to the chi ;;, 1 <lar, 1- nescencc of the compound are indicated in the table; t which is:

 <Desc / Clms Page number 37>

   TABLER X.
 EMI37.1
 is 1 2c3ih ciro2-cxn-.1- ricl te :, h'o1wl. rvalctia
 EMI37.2
 Various reagents 11) \ I1,.;. Nati on Example Pi: rnxyde Other 5Kiàiitô See n - - reactants. z
 EMI37.3
 
<tb> II <SEP> A <SEP> Anhydrous <SEP> Medium <SEP> Long
<tb>
<tb> H2O2
<tb>
 
 EMI37.4
 II B H20Z KOH Fuiblo
 EMI37.5
 
<tb> II <SEP> C <SEP> H2O2 <SEP> H2O <SEP> Medium <SEP> Long
<tb>
 
 EMI37.6
 II L ll0 (30 $) il0 High Medium
 EMI37.7
 1: Y1: ": PLH t? ¯.



  Infrared study of rÚ # ranter <? Tjt acid catalysis of bisl, .d, hyüro -.?.- oxo-1-pyrilyl) lyoxal to form 1 nxalaLe biG (-2-pyriuyle} A stock solution of bis (1,2-dihydro-2-oxo-1-pyridyl) r, lyoxal 5.8 x 10 2 molar in triethyl phosphate is prepared and the infrared spectrum of the solution is determined in the region of 1900 to 1500 cm- 1. In aliquots of 0.75 ml of the stock solution containing
 EMI37.8
 nant 10.7 mp; (4.3 x 105 mole) of glyoxal, 6y7. (D, 6 x 10 "'mole) of methanesulphonic acid, 1.6 µl (2.9 x 10-5 mole) of phosphoric acid are added respectively. and 7141 (8.6 x 10 ** mole) of hydrochloride quo (37; n) acid and the infrared spectrum of the three solutions is determined in the region of 1900 to 1500 cm-1 for terminal "f3f there was a roast.



   The results of the experiment show that the
 EMI37.9
 bands characteristic of bis (x, 2-dihydro-2-oxo-1-pyridyl) clyoxàl at J. '71 ê3 1719 and 1680 cir, -1 in solution in triùthyl phosphate are diniiriut-e- lentiiiciât during l addition of the acids and reveal the appearance of a band at 16 cin-it this band being attributed to the formation of 2-pyridyl oxene-late. The percent conversion of the N-acyl compound to the O-acyl coMposite is from 41% to 30% in the case of catalysis by ...ethanesulfonic acid and 5% in the case of. phosphoric and chlorhy acids,

 <Desc / Clms Page number 38>

 drique after 9 minutes of elapsed time.



   An infrared spectroscopic study of the reaction. tion described in Example 42 and the strong chemiduminescence obtained in the presence of methane sulfonic acid as shown in Table XI of Example 41 lead to the conclusion that bis (l, 2-dihydro-2-oxo-1-pyridyl) glyoxal undergoes an acid catalyzed rearrangement to provide bis (2-pyridyl) oxalate prior to the chemiluminescence reaction. This last compound which produces chemiluminescence by reacting with H2O2 in the presence of a fluorescent agent.



   EXAMPLE 43.



   The quantitative evaluation of the cc chemilunrinescent of bis (1,2-dihydro-2-oxo-1-pyridyl) glyoxal, shown in Table XI, is carried out as follows: a. The reagents dissolved in dimethyl phthalate are. mixed in a quartz cell fitted with a magnetic stirrer. The order of mixing is as follows: glycoxal, 9,10-diphenylanthracene, methanesulfonic acid, hydrogen peroxide. The reaction mixture contains 0.001 mol per liter of bis (1,2-dihydro-2-oxo-1-pyridyl) glyoxal,
6 x 10-4 mole per liter of 9,10-diphenylanthracene, 3.3 x
10-4 mol per liter of methane sulfonic acid and 0.1 mol per liter of hydrogen peroxide.

   The strong chemiluminescent light is measured by a radiometer-spectrophotometer at 25 C. b, Part b is done in the same way as experiment A except that a higher concentration is used, 0.01 mole per liter of bis (1,2-dihydro-2-oxo-1-pyridyl) glyoxal. vs. Part c takes place in the same way as experiment B except that a higher concentration is used, 3.3 x
10-3 moles per liter of methane sulfonic acid. d. Part d takes place in the same way as Experiment B except that 0.1 mole per liter of phosphoric acid is used instead of methane sulfonic acid.

 <Desc / Clms Page number 39>

 
 EMI39.1
 



  T.L J x.



  The effect of :: cidcs S: J: - le rer; de :: (> rt QuantiC'ue de la chir..5ohu;: ir.escence and on the radiating capacity of the biF (1.2-3ihY : -0 - CX01-vr {] vl) rlvoxa] e so] ution dar.s le htal., Te fe di ;;. <Iih; .1e.
 EMI39.2
 



  Ex. IV Glyoxal Concentration Report. t ¯i Max * Rendez.ent Capacity p,. 1-1) molar acid 4 max cuart.ique de radia- "'. L o .... 1.' Cide mo e I j (mole 1-1 1 x10) 4 (aC1.úe. 4 / ( min) (eirstein t .. 10r. n tI .... X10 ester) mole-J..x 10 (eir.s: .ein ii. a ------ 3.3 - 2.0 12 , 9 1-1 1.3 x 1.I41hàce sulfo # ic o, ooio 3.3 0.33 2, C 12.9 1.3 b:.: Tttar.e sulfcni-ue 0.0100 3.3 0.033 5, 0 2.3 2.3 sulfonic 0.0100 33.0 0.330 <1.0 16.9 16.9 d Phosphoric (% 55) 0.0100 1000.0 10.00 4.0 2.1 2.1
 EMI39.3
 x The time required for 1 Density of light to decrease to a quarter of its value. xx Berrésee the càracilé * of the Cr.ir system, .ioiz: .iz3escez.t to emit a visible light by chemilumir: escer: ce.

 <Desc / Clms Page number 40>

 



   EXAMPLE 44.



   The chemiluminescence of bis (1,2-dihydro-2-oxo-1-pyridyl) glyoxal is qualitatively studied in five solvents or solvent mixtures in the presence of three different fluorescent agents or fluorescent agents. The results are shown. in Table XII.



   In parts A 'and G' of this example, approximately 3 to 5 mg of the test compound are added to 5 ml of a solution of about 1 mg of DPA and 0.2 ml of anhydrous H2O2 in the solvent. anhydrous indicated maintained at 25 C.



   In parts B 'and H' of this example, approximately 3 to 5 mg of the test compound are added to 5 ml of a suspension of 1 mg of DPA, 0.2 g of KOH (1 pellet) and 0.2 ml of anhydrous H2O2 in the indicated anhydrous solvent maintained at 25 C.



   Part C 'of this sample is carried out as run A' except that approximately 0.1 ml of water is added before the addition of the test compound.



   In parts D 'E' and I 'of this example, approximately 3 to 5 g of the test compound are added in 5 ml of a solution of 1 mg of DPA and 0.2 ml of CH3SO3H in the indicated solvent maintained at 25 ° C. 0.2 ml of 98% H2O2 is immediately added.



   Part J 'takes place like run A' except that 30% aqueous H2O2 is used.



   Part L 'is carried out like test B' except that 30% aqueous H2O2 is used.



   Part K 'takes place like test A' except that
 EMI40.1
 uses 30% aqueous ü202.



   Part M 'is carried out like run 1 except that 0.4 ml of concentrated HCl is used in place of methane sulfonic acid and 30% H 2 O 2 in place of 98% H 2 O 2.

 <Desc / Clms Page number 41>

 



   EXAMPLE 45.



   The superior light-producing ability exhibited by bis (1,2-dihydro-2-oxo-1-pyridyl) glyoxal is demonstrated in Table XI.



   All the measurements relating to the chemiluminescence shown in Table XIII are made using a radiometer-spectrophotometer in a solution of 0.01 moles per liter of the chemiluminescent compound and 6 x 10-4 moles per liter of 9.10- diphenylanthracene at 25 ° C. Other reagents and solvents used vary as shown below: 1. The experiments are carried out in solution in dimethyl phthalate in the presence of various amounts of hydrogen peroxide, as follows: a. the hydrogen peroxide present is in a concentration of 0.024 moles per liter; b. the concentration of hydrogen peroxide present is
0.090 mole per liter.



  2. The experiment is carried out in solution in dimethyl phthalate in the presence of 0.024 mol per liter of hydrogen peroxide.



  3. The experiment is carried out in solution in dimethyl phthalate in the presence of various amounts of hydrogen peroxide, as follows: a. the concentration of hydrogen peroxide is 0.024 mol per liter; b. the concentration of hydrogen peroxide is 0.09 moles per liter; vs. the concentration of hydrogen peroxide is 0.09 mole per liter but there is also 8.3 x 10-6 mole per liter of triethylamine.



  4. The experiment is carried out in solution in triethyl phosphate in the presence of 0.018 mol of hydrogen peroxide per liter.

 <Desc / Clms Page number 42>

      at. the experiment is carried out in solution in dimethyl phthalate in the presence of 0.09 moles of hydrogen peroxide per liter; @ b, the experiment is carried out in solution in 1,2-dimethoxyethane in the presence of 0.042 mole of hydrogen peroxide per liter; c, the experiment is carried out in dimethyl adipate in solution in the presence of 0.099 moles of hydrogen peroxide per liter.



    5. The experiment is carried out in solution in dimethyl phthalate in the presence of 0.064 mol of hydrogen peroxide per liter and 0.0037 mol of methane sulfonic acid per liter,

 <Desc / Clms Page number 43>

 
 EMI43.1
 7PJI, lJ XI 1.



  CXn; <': LG' ue bi5 (2-nvin71} - 4vai # ;. iiçn
 EMI43.2
 Ex. V Cor.dil.io'sde r4 * ctirn ### '## n #### I' ###### T "Part ..0: '. T.ia tE.rL.: C 'r "i: 30: t'; iCE'S. This ieroxy rpse cîde Zi: W S.2L Lifespan 1 9,10-diphnyl- anhydrous doyenne Long * - * '& r.t.hrùCr H202 B1 H202 KCH Low Long 1 st aqueous Medium Loin z0? 0? F202 ¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯ pi HzG - H 3 weak :: oyer .ne gl Rubrbne H? 02 H, O aible;: ap4-de gl D:;:. ii2t '(i: lj DPn # éÔ'ɵ0, KCH 3; u31e G uht à'. h àe J "A;> nh.; .. l; .e - - î7 Lorii e.) h 3!, A 4 il y.1 weak 53.'Ì; 'li; o çgibye gl ÎIPA H202 KCH Weak I ,.

   DPA H202 14.0 + Strong J Acid ac- DF 3G 11202 Strong Lonruc ¯¯¯¯¯ ¯¯¯¯¯¯¯¯t-içuē¯¯¯¯¯¯¯ # ¯¯¯¯ ####### ############## '"#################### fluorescéir.e 3 0, H202 - - 2: ulle'" L1SGC1CttlA "############ 'Ll water ¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯ 3C 4 2 0 2 YCH? Alley -scthyl- chloride Ir 20 2 HC1: , ul3e acridirium

 <Desc / Clms Page number 44>

 
 EMI44.1
 Lrrd atlcau XII.



       The qualitative intensities are low on those of oxalyl chloride which is considered to be strong.
 EMI44.2
 



  Aciue acid was used instead of c;, c: L;.; .. :: c SII.ihll.tü8,

 <Desc / Clms Page number 45>

 
 EMI45.1
 T :. v r r, "1 XII T.



  Cr, r, c; -t4e, ie raj1atinn = 2e ,, r.e.
 EMI45.2
 



  ! '' Cc;.; Osr chhi-uircscort Solvent- * Peroxide é r.lallsatîon 1, 3 w SVcÉ re (e.steir. L 'x 102 friax - ¯¯¯¯¯¯¯¯¯¯¯¯¯¯ ¯¯ ¯¯¯¯¯ ç-- "'-' 1--. I (eraieir. 1 x i0 ¯¯¯¯¯¯ r1 .. <'<=" = <.> .- "'.> > j #., 0, 0-- 4 8, b) D: -: P 0, CC 8,1 12 t.:-.âr ;,: ¯: xs,. ', - ,: r :: r: -.....-.'-. t:.; 3ï ::. '. ryse) D ::' C, Ù2 # 1 ?, 2 '' .xt s} p: - 's (2- f & nr.yl-2-rtit, rcT, hr.yie) '0, CP4 8.7 80 bj D;: PC, G 0 tri, 0 z'S c) D:.: PG, .g0 7.0 20 4 Cx ..: 2ete dp DiS "lLifiU rCII.ôh.J'II.hn3'le) TLP 0.018 7.2 26 5; x, = iz3te, jt: - bis (rer. & Riuorh-.yieÏ 'D:.: P 0.090 7.6 58 b) D: 3. ! c1, a.z Àél z. #. c) DI.' 0.059 8.1 20 aser ss 6 bls (., 2-d! i.hydro-2-oxo-l.-Fyricyl) clycxal J?. 1P 0.064 1-619 <. 1, ". 1
 EMI45.3
 !.,.



  ...



  ..



  ..
 EMI45.4
 



  5 "? == F :: t.alae je àîn4: .hyLe, J13 = 1,2-d- éthcxy4-thzine, Dl.li - aàiçàte àe Éi;: / thjù, 1 ± P = phosrrta-e,; e tri, xx Reprscr.te 1 * Ccp & cites to> pystèr.e chii, iolun.inescent to produce a chictiolui.-inescence. xxx î '<mps re iis for-. leir.te .-. sity of 1 .; niére ulirît.-ue of the quarter, of its value: =. to; inal.

 <Desc / Clms Page number 46>

 



     EXAMPLE 46.



  The preparation of bis (5-oxo-1,5-
 EMI46.1
 dihydro-1-quinolyelyoxal as described in Example 40 for bis (.., 2..dihydro 2.oxoWl.-pridyl) lyoxal except that 5-hydroxy quinoline is used instead of 2- hydroxy pyriaine.



   It is within the scope of the present invention to include such modifications of compositions and products.
 EMI46.2
 c :: o.:;, described in this specification which would be obvious to one skilled in the art and it is obvious that the examples illustrating the present invention are not intended to be
 EMI46.3
 tin H 1; limit the prser.t invention.'It between equal.ent within the scope of the present invention to include an apparatus
 EMI46.4
 or article such as a racipicnt which can be for example either a substantially insoluble capsule or a soluble capsule in which the reagent or the composition according to the present invention is enclosed to subsequently react with the other ingredients which are necessary for produce the
 EMI46.5
 light by chin.iolwuinescence.



  , r; t;,.; PL: '1 Le bis :, 2-dihyûra.-2..oxo- * pYri.:yhjlyoxa. is early to dethinate its chemiluminosconce during rô # ciian with hydroporoxyLe.-D other than peroxyae 1'i> y.irotùne. The tests are carried out con, c, e night:,:. Approxin. ,,, i vc; cnt 3 nir, ùe tlyoxal is added to 5 µl of a solution of alia, ue 3? and 25 ml of p. acid: roxy "'4-n1t.robcnzo! rlue in ,, 2-diii ,, thoxyolhane (I19, lE) maintained at about 25%. No chiiniolumins are observed. - this, -, this substantial.



   N. The test is similar to the M test except that
 EMI46.6
 he adds, 2 g of voli more. Cn does not observe any chin.io- r, cil ce.



  0. The essay is similar to i'i l 'i; nzai:'. except that 0.1 ml of water is also added. No chilliio- lun.ÍnlJ $ ccr: ce is observed.

 <Desc / Clms Page number 47>

 
 EMI47.1
 



  P. L'eùo / .i is. similar if l'c5üi 1: auuf that r., rrrutc 1téÙ ('t. (Hlt 0.1 ml of ocido rs.! thrtne ruli'oric; ue. We 1 1 observe 11: C: lin, i , nlutrnTlE 'ûCé.'nC8 1..oym, lJelh! 1nt low,: "XH. PiJ: 4.



  Cn ... 'r:' 0Jc char.c iex i; It is combined with example 47 except that we use el! ' 1h, urv ,. , xyae \ le t-Lutyle .1 lu places u 1 <.tciuc} croxy-l, -nitroben2oTçue. L05 result .... t.s of the tests are as follows: 1.i. No chiI..iolumincsconce is observed. he, ljr. does not observe any chi.;. iolun.inc5conce.



  0. No ch.r..io.uuir.escence is observed.



  P. We observe an average cüir..ialn: f, ine> car: cc. i, 1 KXK: 'PLK t.



  Pr'srutior (the oxolate of dF :: a = iimïno (i.e.! "'O a <; n ci'l h, J <t rcxy 1;> 1 ;. i ne) ¯ ¯ ¯¯ ¯, Cn diS50ut l., 6) J: (O, Oi n.riej de; ... hyuroxypht, Ùlr: 1ide in lC0 Ir.l -le 1,2-diniôthoxy.àthiine i'raicin; r. To the i11'it.ée ri> pidol1.er.t solution, 0.43 l (0.005 n.ol) of citoxalyl chloride and 1.4 ml (0.01 n.ol) are added. of Eriolylamine at 25 ° C. for 3 hour in a vacuum, the T.lar.e is evaporated to dryness in vacuo and the solid residue of three ssi is removed with a portion of 3G. 'ni of chlorofrme for nbte: .¯,' J: reads forr..e cri5tiAUX white sounds, 1'.Y. 23) - 234 C with a rel; ue: r.ent Je J + 2 ;.



  Anal, c ;, lc.Jl, 1 for C CH808: c: 56.65 jµ:?,. 2ja; 11: 7,) 7J Tn'uvu here IT '. '0' "li; 2, ùJ; 1;.", 7.45.



  KXi- ,:! F. 5 (
 EMI47.2
 ; '1I uLili5an1' oxlZ je aia} ttalit ;; iuc do example 4 (. Nt.,.: A, 1 (> 5 (HiSl ... lS .9 4 *. '. N',! ' t'llIr dM, f'rr; dr \ f! T "11 ± ùl.re \ 10 life,.,, ': nt fjuantique and. rcfiutinn capacity, eri ut il. L, lit. t,'. .IU phtlLe Je dii;, <Sihyli; crr, rn: solvent and in fhi- sc, rit, vary 1i.'5 q'JantiL6s of oxidized and 110 hydrogen peroxide.

 <Desc / Clms Page number 48>

 
 EMI48.1
 As fluorescent aront, 9,10dinhenylanthracene is used. All measurements are made at approximately 25 C.



  The lifetime is expressed in terms of (t 4 Imax), which is the time necessary for the intensity of the light to decrease to a quarter of its maximum value. For the part P, we add 0.015 mole per liter of water to the reaction. For part @, 8.3 x 10-6 moles per liter of triethylamine were added to the reaction.



   For the R and S parts, the procedure is the same as that described in the above-mentioned examples M to 0 except that propylene carbonate is used as solvent and that the relative amounts of reactants are varied.



   The concentrations of oxalate and hydrogen peroxide are shown in Table XIV below.
 EMI48.2
 



  Quantitative P9uros on the chiii.iolumines ce, ce these measurements are carried out in two different solvents and are shown in Table XIV.

 <Desc / Clms Page number 49>

 



    TABLE XIV.
 EMI49.1
 



  'J .-' ;. c "- r, ai icl '.:' Ir '' 'pcc: c caacit. Rc.it,': r '-i'? Lcxal & t.e Cj1; 7: 1in2iF: .lC .1: eJ.;, E "'" ";' ..,: vr .: j:.;. T; C c> <>; 1: îcl1 '"iI: Ç'CC: e and c1f' [: ci t ..: 'rie d. I :: t (r Ijt l' cxRl; t.e diDht, al; -: -. Ide
 EMI49.2
 Exer..ple III O-ox, lyl- N 2 O 2 t4 imax d <.er.t. G: .1 & .r, tiGuè Radiation capacity 9É'ôÀà hY0:

  --oxylar .-. ir..e f- <1 -1 X 2 (einstein 1 ..1 .. x 104 T '. irie (\ i.0 B 1 r -1 mole 2 2 1-1 4 lr ..sp.'lr. r.sIe x ï0 (ei-nsl.ein
 EMI49.3
 
<tb> A <SEP> 0.001 <SEP> 0, C24 <SEP> 94.0 <SEP> 8.7 <SEP> 0.9
<tb> B <SEP> 0.010 <SEP> 0.0024 <SEP> 3 (, 7.1 <SEP> 2.3 <SEP> 2.3
<tb>
 
 EMI49.4
 C 0, C10 0, ce90 26E ', 0 .i, g 1.9 D e, r ,, 10 C, C090 169, c 2.7 2.7
 EMI49.5
 
<tb> E <SEP> 0.010 <SEP> 0.0090 <SEP> 184.0 <SEP> 4.3 <SEP> 4.3
<tb> F <SEP> '<SEP> 0.0010 <SEP> 0.034 <SEP> 6.7 <SEP> 2.64 <SEP> 0.26
<tb> G <SEP> 0.0100 <SEP> 0.034 <SEP> 10.1 <SEP> 1.41 <SEP> 1, it
<tb>
 

 <Desc / Clms Page number 50>

 
EXAMPLE 51.



   Diphthalimido oxalate is tested for chemiluminescence during a reaction with hydroperoxides other than hydrogen peroxide.



   The tests carried out are as follows:
T. Approximately 3 mg of diphthalimido oxalate is added to 5 ml of a solution of 1 mg of 9,10-diphenylanthracene (DPA) and 25 mg of 4-nitroperoxy-benzoic acid in 1,2-dimethoxyethane ( DME) maintained at about 25 ° C. Weak chemiluminescence is observed.



     U. The test is similar to the T test except that 0.2 g of KOH is also added. Moderately weak chemiluminescence is observed.



     V. The test is similar to the T test except that 0.1 ml of water is also added. No chemonuninescence is observed.



     W. The test is similar to test T except that 0.1 ml of methanesulfonic acid is also added. No substantial chemiluminescence is observed.



   EXAMPLE 52.



   The tests are carried out as in Example 51 but ue t-butyl hydroperoxide is used instead of 4-nitroperoxybenzolque acid. The results of the tests are as follows: T. Very weak chemiluminescence is observed.



     U. Medium chemiluminescence is observed.



   V. Very weak chemiluminescence is observed.



   W. No chemiluminescence is observed.



   EXAMPLE 53,
The preparation of dimaleimidoxalate is carried out by proceeding as in Example 49 except that N-hydroxy-maleimide is used in place of N-hydroxy phthalin.iue.

 <Desc / Clms Page number 51>

 
 EMI51.1
 



  : XI ':,'. "FLE 5l, .. Preparation of dipipridino oxalate
 EMI51.2
 
 EMI51.3
 gold: proceed coi; J..e example jar9 except that dcz is used N-hydroxy pipérloino instead of K-hydroxy plitalitii (the.



  Vol <, JIJ <ī, 'lez 1 <# ¯, ¯ ;;'. Vj ',: 1J rC "\ T! (J:;,.



  1.- iiôucLi1 chi.iolundrp.::!cEHlt, comprising, a compound of formula nt- C-GU-r1, Ùn5 lJqueiàe 100 two symbols A can be water or dii'f brerLa and Ltr.z; e (a) Ulte where R is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a terocyclic group such as the pyridyl, furyl, acddinylc group, a substituted h <bL4rocyciiquP yraupe or a group i) j 1 <yl ir.8 ± (, ur6:

   (b) -0 i <lt where I1 is. a 1-.roup ..lkyl (t: \ ubst.it, u (or not or a cyclolkyle group subsiiLu4 or not, an aryl group, a froupc c xtCrocyc.frue or an unsbtur6 alkyl group; or (c) N / ! l2 -,, where at least one of the 3 symbols R.) and, fi) represents a 6elect.ronéDu ',;., U' with ur.f, "ue sior.a equal to about 0.7, the other substance is hydrogen, an alkyl, aryl, alkyl or alternatively H;

  2 and HJ taken ensex-ble force, with nitrogen an i7, roui) tc heterocycl irue which can cor. Obtain oxygen, sulfur or a keto group, X is (CO) n where n is an integer ne 0 to 9 or the rump
 EMI51.4
 

 <Desc / Clms Page number 52>

 where m is an integer from 0 to 4, the symbols
Y are the same or are different and may be hydrogen, chlorine, bromine, fluorine, phenyl, alkyl or alkoxy radicals and Z is an alkyl or substituted phenyl radical, and at least one ingredient. additional required for the production of light by chemiluminescence.



   2. Chemiluminescent reagent according to claim 1, characterized in that the additional essential incredent is a fluorescent compound or fluorescent agent and / or a hydroxyperoxide compound or a hydroperoxide producing compound.



   3. - Chemiluminescent reagent according to claim 1, characterized in that the compound A-CO-X-CO-A in which A and X are as defined above, is the fluorescent compound.
 EMI52.1
 



  1 -. "6 active cheml01uIIIlnc5cent according to 100 claims 1 and 3, characterized in that the compound A-CO-X-CO-A has the formula ROOCOCOOCOR 'in which R is hydrogen, a substituted or unsubstituted alkyl radical. and R 'is hydrogen, a substituted or unsubstituted alkyl radical, a substituted or unsubstituted aryl radical.



     5.- Chemiluminescent reagent according to claims 1 and 3, characterized in that the compound A-CO-X-CO-A corresponds to the formula RCOOCOCOOCOR 'in which R and R' are
 EMI52.2
 unsubstituted aryl, arylmethyl, diarylmt <, th5ler tri ± lryln.Ótflylo, alkylaryl, alkoxyaryl, sulfoaryl, cartoxyaryl, arylaryl or aryloxyaryl radicals.



   6.- chemiluminescent reagent according to claims 1 to 3, characterized in that the compound of formula A-CO-X-CO-A is 2,4-dinitrophenyl oxalate, oxalate
 EMI52.3
 2,4,6-trinitraphcnyl, 4-cyanophenyl oxalate,

 <Desc / Clms Page number 53>

 
 EMI53.1
 4-acetylphenyl oxalate, 4-phenylphenyl oxalate, diisopropenyl oxalate.



   7. Chemiluminescent reagent according to the claims. to 3, characterized in that the compound of formula @ le
 EMI53.2
 A-CC-X-C0-A estis (1, 2-dihydro-2-oxa-1pyridyl jl yoxal.



     8.- Chemiluminescent reagent according to claims 1 to 3, characterized in that the compound of formula
 EMI53.3
 A-CO-X-CO-A is 9,10- (alkylpuroxycrrbonylj-9,10-diaryl-9,10-dihydroanthracene or 9-alkylperoxycurbonyl-10-cui-boxy-9, LG-dizryl.-9, 10-d ihydroanthracene.



   9. A chemilurninescent reagent according to claim 1, characterized in that the compound of formula A-CO-X-CO-A is an ester of an acid of oxalic type and of an aromatic alcohol, alcohol being substituted with a substituent characterized by a positive Hammett sigma value.
 EMI53.4
 



  10.- A chemiluminescent reagent according to either of the preceding claims :), characterized in that all the ingredients are in solid form.
 EMI53.5
 



  11.- Chintiluminescent composition comprising (a) a compound of 'formula e-C0.-X-CG-Pr in which 1', and X are as defined above, (b) a hydroxyperoxide compound or a compound: .1 'hydropt'roxide producer (c) is a fluorescent compound when the compound A-CO-X-CO-A is not itself a fluorescent agent or when the reaction product is not a ( 1)
 EMI53.6
 Fluorescence / and Caesire is used in diluent, water and an acidic or basic cc% olj-1s-> ir.



  . '& 2.- Chemoiumincsct'nK' coriiposition according to claim 11, characterized and, that the diluent is water
 EMI53.7
 while the hydroproxy compound is hyuro-gene peroxide. 3.i Chemiluminexcet composition, according to claim 11, characterized in that the compound -CO-X-C-h, in which A and X are as defined above, is. the

 <Desc / Clms Page number 54>

 fluorescent compound.



   14.- Composition, chemiluminescent according to claim 11, characterized in that the compound of formula A-CO-X-CO-A corresponds to the formula ROOCOCOOCOR 'in which R is hydrogen, a substituted or unsubstituted alkyl radical. while R 'is hydrogen, a substituted or unsubstituted alkyl radical, a substituted or unsubstituted aryl radical.



     15.- A chemiluminescent composition according to claim 11, characterized in that the compound of formula
 EMI54.1
 A-Ci) -X-C0-à corresponds to the formula RCOOCOCUOCOR 'in which R and R' are unsubstituted aryl, arylmethyl, diarylmethyl, triarylmethyl, alkylaryl, alkoxyaryl, sulfoaryl, carboxyaryl, arylaryl or aryloxy radicals.



   16.- A chemiluminescent composition followed claim 11, characterized in that the compound of formula A-CO-X-CO-A is 2,4-dinitrophenyl oxalate, oxalate
 EMI54.2
 ue 2,4, -tri.nitrophenyl, 4-cyanophnyl oxalate, oxa-, 1¯'ox; 41, atc (the ,, iisnj; rn: ,, ':. j, iie. late of ië-ac3tyll) h (, nyl, 1oxaite u, F: 4-ph () nylphlyl ('or Le bis (1,2-dihydro-2-oxo-1-pyridyl) lyoxal.



  17. A chin, iolur, inescent composition according to claim 11. characterized in that the compound of formula is g, .0- (alkylFaroxycrrrLony.). r3, .10 .diaryl- 9,10-'dihydroanthracenc or 9-alkylpcroxycarbonyl'-i0-carbaxy, 1C? wci i aryl-9,1Û-di htr ra art hr cs: rse.



  16, - Composition chitiioluii, int-, scente according to claim 11, characterized in that the compound of formula A-CO-X-CO-A is an ester of an acid of type oxalic and an aromatic alcohol, the alcohol being pure substituted with a substituent characterized by a positive Hammett sigma value.
 EMI54.3
 i ,, .. Chemilu: .inescent.e composition according to claims 11 to 18, characterized in that all the ingredients are in solid form.

 <Desc / Clms Page number 55>

 
 EMI55.1
 



  2 '.- Proc' '' of the rie production a csinsinlus, .izsr: nct: nCe,.,; R, i4:;, l'tl cc that '01} Mn / Uee un c ('mpotl6 of formula, ± z; .. j> .5, .t LJ, Jr: ^ li: tü (, ti A and. X J3t> r7i. '.cl !: than defined more,; ,,' 1t .., 11. hC :.,: 1 ^ 7: it: ilj't: r'C) 7f "l't) X'fCiG 'or Ull cm.'. Pos producer à'iiy-; at: f;.,;, 7t = .i a diluent ,, the x "(; i3. (:: fi comprci, iiil .AU inviriti., it, 1; ph4 (> f> 1; l'Lù <" t'Ùscelit *, 'j. .- w1 "'jcr'vJ, i Juivai; i 1wt, t'I: vf':! id le; J t '1. on .0, CivrtaCS.!".



  "; ';' '' '<; 1;'; ' l, i ï,; # c ;; inj> vu4 .ic x (7rItrUJ.G 'Si-Èi, -X- <lV-, 1, tir7fµ ..i (Llf: a ..F: A c', ; (". ('!)'. t> <, lr> (lJC1 <l011nis plue hut., (:: 3t. le compo:., '. l, .L 4.'. A 4'WJ L ri Sa 2,:, - Process according to claim 20, currtct, t- rin, F ers ce (jUC the diluent is water and. In co quc the compound: if ';:,> j: r.r'tiX 'tit: G3 In jo: t'OXI (, C' ltiry.lIo ', tr7E.' ".'i" Í'ro <:! ': dt iUlVr..7: 1; <rn'lCI (1iciltioli 2 ("Cü7" aCLc; - r! .Nf * un eu: z17 (', the C (-J: ,, IfO: ie,; - cù-01-1; c- ;, r'îi (JS. ( ! (1 lu fot'.uic A> 1. <'<. I: 1.C <. <: <' <1 [\ 1 :; ia <7, iscllty it is, (the 1.'hy (xroryrre , un l'lldi CI, ',; ,,;, 1 ± \:, rc; U.it ,, r,'., <: not eL: e ;; t <the hydrogen, a r <; ; <ii <:;, 1 "tk: 1Y: 1! d ';, t, j Lli'; r3 :: hP1l, uryie usxh; st, .t.lf or not.



  2 / v, - i'i <> <: àii <0. :; WiVilht. 1.;> Claim 20, curact ,, .- ::. ¯ #; r 1.:1; ,; <..:; / ('le t.'Cïta, r> 3S:, - [; (1 ...: \ ... CO "' / 1 rt} por, J 1, IJ 1'01 '11, \. 11 (:, Ls-j..r: ït'aïç ..: 4 '' '.tt' iT,.; ... = tilL.tiC it and ii 'nont. Des 1' < HiiCil \ J;>: uryle â,: 'tx alli'; ii (.ila ', ..i'! F.ii :: ei.ilY.1 ('(1ÜH'ylr: .., tnyle, tT. irt ", yÂilyLt.l'1! 'j; .jiçjrL; ii, j ,, ¯;, ,, 1;>: <à'i <;, y> there <7, vllAit): ij", (' ; ti, 'l ,, r'ltJXy'vS'li.E' and,;> i? 1;,;. yl <;.



  *; m.-; '(' 1: <: \ 1..1 (\ t1ui v :, nt. lu 1'ovcndlcútlon 20, Gi> iil '; r: ri; #, j (' there '.¯ ., =. 1 ("(i1: .pOU .: '1 <; i'or..ul0 t1 * é.Îwr,' ..;: Ç .. 'i" 5t 1 tt1l;:., 7, t: .v; cH '.: ritiaâti.i.vr'tifril'rlyiL .LtOiaIz's. (,',. (i.!, l., h¯t.ris: it! '() jh,'! 1ytû , .1,. ',,. Ii, .. sifyt' of 1y-c yui; <> j> h4nyir, 1 '.; X; <i; i:. <, (U} iw' "; tC, 'tJ; l; ita: aj'a' .l..t''JX.JLti vIé? i, -1, ;; #iyl;> nyie or. tt? 'fl, ild.C' de dii "oprc 'p,', yg1.



  .. '6, -' 'OC'C, l': S171V: i1'rti la reVfJl (11Ct1t.1 (11, i7; 1 cr-'L ':, - ri:; t vri ce: 7. .iC '. le G: ti' .: 'de Ù.2'r; ul (l j1' "" iilrT, (iwlt esL 1 <: ', ", 1) - é11iiy1.i", retlj'ç, Wt'r '") tlJl, 10-ri4, j'; f" ji.w "!; LJry (ir't7Ft;, t.tlf'il4'J:, t ', lï: 9- .. <; ; .j; t: t'rl: y, yrrr: fl, t.-ttrboxy., IGf-dïtaryß - (,?,. i? .- ci hyar: -, lz ..; k <; .tit. : r, or ta \ ,; 1 (.1., 2 ... j UlYllro-2-oxo- ... py dJ yl) -r, l yc, xa:.

 <Desc / Clms Page number 56>

 
 EMI56.1
 



  27.- Proceed according to the rovandtcHt1on 20, carcr,., The ir'IÍ in co that the composa if; '' onhule 1 - (, I, -, GO is ur. r :: tQr of an oxalic acid and. of an alcohol & "A .. the substituted alcohol plI ?: 'a ui .; t.ttr, rrt which is c: l'uc, rLsu for a value of 5ir: rn.'1 of positive rarretC.