SE187378C1

SE187378C1 -

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Publication number: SE187378C1
Authority: SE
Publication date: 1963-01-01

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KLASS INTERNATIONELLSVENSK C 09 b22b:8 PATENT- OCH REGISTRERINGSVERKET Ans. 7588/1958 den 16/8 1958 V SVOBODA, D TERZIJSKA, BRUNN oar J KORBL, LYSA. N. LABEM, TJECKOSLOVAKIEN Satt aft framstalla som indikatorer eller reagens Yid kemisk analys anyandbara, substituerade sulfonftaleinfargamnen Prioritet begiird frail den 17 augasti 1957 (Tjeekoslovakien) Det har pa senare lid klarlagts, att kondensationsprodukter av sulfonftaleinfargamnen med iminodiattiksyra uppvisar overraskande gala metallokroma egenskaper, dvs., att de ge liisliga, odissocierade, fargade foreningar med metalljoner. Dessa produkter ha clarfOr anvants som komplexometriska indikatorer och analysreagens. Aven om deras reaktion som indikatorer är ovanligt kanslig, dr deras anvandning i manga fall i nagon man inskrankt, beroende pa deras ringa specifika egenskaper, emedan forandringar i de fiesta fall framkallas av ett flertal joner. Selektiviteten har vasentligt forbattrats genom att ersatta iminodiattiksyra med glykoler (aminoattiksyra). Erhallna produkter (t. ex. glycintymolblatt, glycinkresolrott och liknande) aro specifika reagenser pa kuprij oner. CLASS INTERNATIONAL SWEDISH C 09 b22b: 8 PATENT AND REGISTRATION AGENCY Ans. 7588/1958 den 16/8 1958 V SVOBODA, D TERZIJSKA, BRUNN oar J KORBL, LYSA. N. LABEM, CZECHOSLOVAKIA Set out to present as indicators or reagents Yid chemical analysis anyandable, substituted sulfonphthalein dyes Priority requested from 17 August 1957 (Czechoslovakia) , that they give liisliga, undissociated, colored compounds with metal ions. These products have been used as complexometric indicators and analytical reagents. Although their reaction as indicators is unusually probable, their use is in many cases restricted in some man, depending on their low specific properties, since changes in most cases are induced by a number of ions. The selectivity has been substantially improved by replacing iminodiacetic acid with glycols (aminoacetic acid). Products obtained (eg glycine thymol leaf, glycine crescent root and the like) are specific reagents on cups.

Uppfinningen avser an ett satt att framstalla andra substituerade sulfonftaleinfargamnen med en sidokedj a vid fenolkarnorna av foljande formel: RIR, H0—/\ R3\ NCH,— \/\ R2 \/ C0 —SO, van i R, och R, beteckna samma eller olika alkylgrupper med 1-4 kolatomer (huvudsakligen metyl- eller isopropylgrupper) eller vate, R3 och -ate, alkyl (eventuellt bildande en heterocyklisk ring med lcvave), aryl, arylkyl, cykloalkyl eller liknande grupper, varvid de hada sist angivna substituenterna karma vara av samma slag eller aka. I hada fallen har clock minst en av dessa substituenter en lamplig saltbildande grupp t. ex. — COOH, —SO,H, —SH, —OH eller dylikt (med undantag av substitutionen R,R, = —CH,COOH och R3 = H, R4 = —CH2COOH, cla harvid dessa fall utgora foremalet for tidigare patent). The invention relates to a process for the preparation of other substituted sulfonphthalein dyes with a side chain at the phenolic nuclei of the following formula: RIR, H0 - / \ R3 \ NCH, - \ / \ R2 \ / CO - SO, denoted in R, and R, denote the same or various alkyl groups having 1-4 carbon atoms (mainly methyl or isopropyl groups) or vate, R 3 and -ate, alkyl (optionally forming a heterocyclic ring with lcvave), aryl, arylkyl, cycloalkyl or similar groups, the latter substituents being karma be of the same kind or aka. In these cases, at least one of these substituents has a suitable salt-forming group, e.g. COOH, -SO, H, -SH, -OH or the like (with the exception of the substitution R, R, = -CH, COOH and R3 = H, R4 = -CH2COOH, cla in these cases form the subject of previous patents).

Framstallningen av dessa substituerade salfonftaleinlargämneii sker enligt uppfinningen genom kondensation av ett enkelt sulfonftaleinfargamne med Raj ande allmanna formel HO—)\ R2 \/ B2(II) C 0 —SO, med en substituerad aminoforening med allmanna formeln HNR,R, (t. ex. en lamplig alifatisk, aromatisk eller heterocyklisk aminosyra eller dylikt) i narvaro av formaldehyd. Kondensationen genomfores vid forhojd temperatur (50-100° C) i narvaro av isattika eller en annan la.gre karbonsyra under tillsats av ett alkaliskt reagerande salt, t. ex. natrium- eller kaliumacetat. Formaldehyd tillsattes antingen som losning i ett lampligt lOsningsmedel (vatten, alkohol eller dylikt) —OH 2— i737 eller i form av sin polymer, varvid densammas avdunstning under reaktionen forhindras genom kondensation i1 ett tryckkarl. The substitution of these substituted sulphon-phthalein compounds takes place according to the invention by condensation of a simple sulphon-phthalein dye of the general formula HO -) \ R2 \ / B2 (II) C 0 -SO, with a substituted amino compound of the general formula HNR, R, (e.g. a suitable aliphatic, aromatic or heterocyclic amino acid or the like) in the presence of formaldehyde. The condensation is carried out at elevated temperature (50-100 ° C) in the presence of glacial acetic acid or another lower carbonic acid with the addition of an alkaline reacting salt, e.g. sodium or potassium acetate. Formaldehyde was added either as a solution in a suitable solvent (water, alcohol or the like) —OH 2 - i737 or in the form of its polymer, the evaporation of which during the reaction being prevented by condensation in a pressure vessel.

Isoleringen av slutprodukten (det substituerade sulfonftaleinfdrgamnet) frail reaktionsblandningen genomfores bast ph sa satt, att man utspader blandningen med en ldgre alkohol efter delvis eller fullstandig avdestillering av reaktionsmediet, varpa fargamnets alkaliska salt utskilj es genom tillsats av ett med vatten blandbart,- svagt poldrt losningsmedel, t. ex. aceton, dioxan, tetrahydrofuran och liknande. The isolation of the final product (the substituted sulphonaphthalene solvent) from the reaction mixture is carried out in such a way that the mixture is diluted with a lower alcohol after partial or complete distillation of the reaction medium, the alkaline salt of the dye is separated by , e.g. acetone, dioxane, tetrahydrofuran and the like.

Kondensationsprodukterna, som icke bilda ndgot alkaliskt salt i reaktionsblandningen, isoleras bast genoit att reaktionsloshingen, sedan kondensationen slutforts, infores under onirornirig 1 en stor vattenmdngd, varigenom det substituerade sullonftaleinfargarrinet utskiljes i. oloslig form. Om produkter med olikartade egenskaper bildas vid kondensationen, kan man Astadkomma en fullstandig separering genom att kombinera de hada angivna isoleringssdtten. The condensation products, which do not form any alkaline salt in the reaction mixture, are isolated sufficiently that the reaction solution, after the condensation is completed, is introduced under a large amount of water, whereby the substituted sulphonaphthalene dye is separated into an insoluble form. If products with different properties are formed during the condensation, a complete separation can be achieved by combining the specified insulation methods.

Det erhallna substituerade fargamnet bildar ehelat under phfallande fargfordndring med olika katjoner, varvid den speciella selektiviteten kan installas mot olika joner i bestamda granser genom att andra substituenterna R, och 114. Pd grund av denna egenskap kan man anvanda angivna substituerade sulfonftaleinfdrgdnanen som indikatorer sarskilt vid kvalitativ titrimetrisk och kolorimetrisk analys. The resulting substituted dye forms ehelate during falling color change with different cations, whereby the special selectivity can be installed against different ions within certain limits by the other substituents R titrimetric and colorimetric analysis.

Utforingsexemp el 1. 3,56 delar sarkosin (CH, NHCH„COOH) loses tillsammans med 9,30 delar tymolblatt CH\ /,CH, CT-I,\ /CH, C HC H HO och 5,50 delar kristalliserat natriumacetat 150 delar isattilra. Losningen forsattes med 4,4 delar av en vattenhaltig 37 %-ig formaldehydlosning och reaktionsblandningen upphettas i ett slutet karl till en temperatur av 50-75° C, till dess en produkt frail reaktionsblandningen icke mer rOdfargas efter utspadning med vatten och surgoring: - Man avdestillerar attiksyran i vakuum, sam-: manriir aterstoden fried nAgot alkohol och utfaller natriumsaltet av det substituerade sulfon ftaleinfargamnet genom tillsats av aceton eller ett annat ldmpligt poldrt losningsmedel (dioxan, tetrahydrofuran och dylikt). Example 1 3.56 parts of sarcosine (CH, NHCH 2 COOH) are dissolved together with 9.30 parts of thymol blue CH 2+, CH, CT-I, 1 / CH, C HC H HO and 5.50 parts of crystallized sodium acetate 150 parts isattilra. The solution was continued with 4.4 parts of an aqueous 37% formaldehyde solution and the reaction mixture was heated in a closed vessel to a temperature of 50-75 ° C, until a product from the reaction mixture was no longer red-colored after dilution with water and acidification: distills off the attic acid in vacuo, converts the residue to some alcohol and precipitates the sodium salt of the substituted sulfone phthalein dye by the addition of acetone or another suitable powdered solvent (dioxane, tetrahydrofuran and the like).

Det isolerade och torkade indikatorfargamnet, s. k. sarkosintymolblatt, utgor ett ockerbrunt till gratt pulver, som dr ldttlosligt i vatten. Vattenlosningen fdrgas gni vid ett pH av c:a 5 och ger med Cu2+-joner intensivt blafdrgade komplexer, som ha en lagre stabilitet an Ga2+-komplexen av etylendiamintetradttiksyra. Derma. egenskap kan med fordel utnyttjas for indikation av ekvivalentpunkten vid den direkta chelatometriska kopparbestdmningen. 4,60 delar prolin H2CCH—COOH I H2C CH2 \ / 5,5 delar kristalliserat natriumacetat och 9,3 delar tymolblatt upphettas med 4,4 delar koncentrerad, yattenhaltig formaldehydlosning och 50 delar isdttika i ett slutet karl till 50-80° C, till dess ett prov av reaktionsblandningen efter utspadning med vatten och surgoring icke rodfargas. Lasningen av reaktionsprodukten indunstas ddrefter i vakuum och det sub stituerade sulfonftaleinfdrgainnet isoleras pa samma sat som angivits exempel 1. The isolated and dried indicator dye, so-called sarcosine thymol leaf, forms an ocher brown to gray powder, which dissolves in water. The aqueous solution is first rubbed at a pH of about 5 and gives Cu2 + ions intensively blistered complexes, which have a lower stability than the Ga2 + complexes of ethylenediaminetetraacetic acid. Derma. property can be advantageously used to indicate the equivalent point in the direct chelatometric copper determination. 4.60 parts of proline H2CCH-COOH In H2C CH2 / 5.5 parts of crystallized sodium acetate and 9.3 parts of thymol leaf are heated with 4.4 parts of concentrated formaldehyde-containing formaldehyde solution and 50 parts of glacial acetic acid in a closed vessel to 50-80 ° C. until a sample of the reaction mixture after dilution with water and acidification is not reddened. The charge of the reaction product is then evaporated in vacuo and the substituted sulphonaphthalene solvent is isolated in the same manner as in Example 1.

Fdrgdmnet, s. k. prolintymolblatt, utgor ett graft till gronsvart pulver, som i vatten dr lattlosligt. Vid ett pH av c:a 5 Or denna lOsning gulfdrgad (rmax = 440 nap) och andrar sig av spar av Cu2+-salter till en intensiv bid farg (rniax — 595 ma). Denna egenskap kan med fordel utnyttjas vid kolorimetrisk bestamning av spar av koppar. The substance, so-called prolintymol leaf, forms a graft to greenish-black powder, which in water dries easily. At a pH of about 5 Or this solution is yellow-dried (rmax = 440 nap) and changes from traces of Cu2 + salts to an intense bite color (rniax - 595 ma). This property can be used to advantage in colorimetric determination of copper traces.

COOH 4,62 delar DL-serin NH,—CH, CH,OH 5,99 delar kristalliserat natriumacetat och 9,3 delar tymolblatt losas i 50 delar attiksyra och 6 delar av en koneentrerad vattenlosning av formaldehyd tillsattes. Den fortsatta kondensationen on isoleringen genomfores enligt exempel 1. 6,94 delar cysteinhydroklorid COOH NH2--CH, 'CH ,SH 11,98 delar kristalliserat natriumacetat och 9,3 delar tymolblatt sdttes till 50 delar isattika under tillsats av 6 delar av en 35 %-ig vattenlbsning av formaldehyd. Kondensationen genomfores enligt exempel 1. 4,13 delar alfa-aminoisosmorsyra NH2— C(CH,), COOH, 5,5 delar kristalliserat natriumacetat och 9,3 delar tymolbliitt upphettas med 50 delar isattika och 5 delar av en vattenlosning av formaldehyd ph oyan. angivet sdtt. Reaktionsblandningen koncentreras och (let' substituerade sulfonftaleinfargamnet isoleras enligt exempel 1. COOH 4.62 parts DL-serine NH, -CH, CH, OH 5.99 parts crystallized sodium acetate and 9.3 parts thymol leaf are dissolved in 50 parts acetic acid and 6 parts of a concentrated aqueous solution of formaldehyde were added. The further condensation on the isolation is carried out according to Example 1. 6.94 parts of cysteine hydrochloride COOH NH2 - CH, CH, SH 11.98 parts of crystallized sodium acetate and 9.3 parts of thymol leaf were added to 50 parts of glacial acetic acid with the addition of 6 parts of a % water drop of formaldehyde. The condensation is carried out according to Example 1. 4.13 parts of alpha-aminoisosmorphic acid NH 2 - C (CH 2), COOH, 5.5 parts of crystallized sodium acetate and 9.3 parts of thymol blit are heated with 50 parts of glacial acetic acid and 5 parts of an aqueous solution of formaldehyde . specified sdtt. The reaction mixture is concentrated and the (slightly 'substituted sulfonphthalein dye is isolated according to Example 1).

I N CH, CH, C" 0 —SO2 — 1873.78 — 4,13 delar alfa-aminoisosmorsyra NH2* C(CH,),COOH, 5,5 delar kristalliserat natriumacetat och 7,6 delar kresolrott CH, CH, HO—/K /\ —OH / G- 0 losas i 50 delar isattika och losningen forsattes med 6 delar av en vattenhaltig, koncentrerad losfling av formaldehyd. Kondensationen och isoleringen av slutprodukten utfores enligt ovanstaende exempel. 4,63 delar dietanolamin NH(CH,CH,OH),, 5,99 delar kristalliserat natriumacetat och 9,3 delar tymolblatt kondenseras under tillsats av 6 delar vattenhaltig, koncentrerad formaldehydlosning och 50 delar isattika pa ovan angivet satt. Isoleringen av kondensationsprodukten genomlikes genom att infora reaktionsblandningen i 700 delar isvatten, varigenom det substituerade sulfonftaleinfarglinnet utskiljes i svarloslig form. 3,98 delar beta-alanin NH, CH,—CH,— C001-1, 5,5 delar kristalliserat natriumacetat och 9,3 delar tymolblatt losas i 50 delar isattika, och forsattes med 6 delar av en vattenlosning av form. aldehyd och den erhallna losningen kondenseras pa ovan angivet satt. Mar avslutad kondensation utspades reaktionsblandningen med en liten mangd etanol och infores i isvatten under omrorning. Den utskilda olOsliga biprodukten avfiltreras och filtratet indunstas till torrhet i vakuum. Indunstningsaterstoden upptages i en liten mangd etanol och sulfonftaleinfargamnet utskiljes i form av silt natriumsalt med aeeton eller ett annat lampligt, svagt polart losningsmedel. IN CH, CH, C 2 O -SO 2 - 1873.78 - 4.13 parts of alpha-aminoisobutyric acid NH 2 * C (CH 2), COOH, 5.5 parts of crystallized sodium acetate and 7.6 parts of cresol root CH, CH, HO- / K / / —OH / G- 0 is dissolved in 50 parts of glacial acetic acid and the solution is continued with 6 parts of an aqueous, concentrated solution of formaldehyde.The condensation and isolation of the final product are carried out according to the above example 4.63 parts of diethanolamine NH (CH, CH, OH 5.99 parts of crystallized sodium acetate and 9.3 parts of thymol leaf are condensed with the addition of 6 parts of aqueous, concentrated formaldehyde solution and 50 parts of glacial acetic acid in the manner indicated above. The isolation of the condensation product is effected by introducing the reaction mixture into 700 parts of ice water. 3.98 parts of beta-alanine NH, CH, -CH 2 -C001-1, 5.5 parts of crystallized sodium acetate and 9.3 parts of thymol leaf are dissolved in 50 parts of glacial acetic acid, and continued with 6 parts of a aqueous solution of aldehyde form and the resulting solution is condensed in the manner indicated above. At the end of the condensation, the reaction mixture is diluted with a small amount of ethanol and introduced into ice water with stirring. The separated insoluble by-product is filtered off and the filtrate is evaporated to dryness in vacuo. The evaporation residue is taken up in a small amount of ethanol and the sulphonaphthalein dye is separated off in the form of silt sodium salt with acetone or another suitable, slightly polar solvent.

For de enligt exemplen 3-8 framstallda fargamnena galla samma egenskaper, som angivits for exemplen 1 och 2. De kunna med fordel anvandas vid kvalitativ och kvantitativ analys samt aven vid kolometrisk analys. For the dyes prepared according to Examples 3-8, the same properties apply as given for Examples 1 and 2. They can be used to advantage in qualitative and quantitative analysis as well as in colometric analysis.

Claims

Patent claim:

Set to produce substituted sulphonaphthalene dyes which can be used as indicators or reagents in chemical analysis, characterized in that a sulphon dye of the formula is condensed with formaldehyde and; an amino prefilter of the general formula HNR, R „, wherein the radicals R„ R „R ,, R, have the meaning given below, at a temperature of at most, 100 ° G, that the dye is then isolated, with the formula / \ - OH / R, —CH2 • N \ R7 \ / \ / \ / `11.4 IR, \ / C * R, O / \ SO2 van in R, and R, represent hydrogen, halogen or an alkyl of 1-4 carbon atoms, R, hydrogen or a carboxyalkyl having 2-3 carbon atoms and R, a carboxyalkyl having 3-4 carbon atoms optionally further substituted by an -OH- or -SH- group or an alkyl having 1-3 carbon atoms, which optionally forms a 5- to 6-membered ring with the nitrogen atom and the radical R

2. According to patent claim 1, it is noted ("dray") that sarcosine was used as the amino compound in the condensation.

3. According to claim 1, it can be claimed that the amino compound proline H, CCH COOH II H, C CH, N / N was used.

4. According to claim 1, COOH is characterized in that DL-serine NH3 • CH, • CHan-CH, OH is obtained as an amino compound. -

5. San according to claim 1, COOH can be characterized in that cysteine NH, -CH, CH, SH is used as the amino compound.

6. Set according to claim 1, it can be claimed that α-aminoisobutyric acid NH C (CFI3) 2 COOH was used as the amino compound.

7. A kit according to claim 1, characterized in that p-alanine NH, CH, CH, COOH was used as amino compound.

Set according to claim 1, characterized in that the base dye thymol blue CH, CH, CH, CH, CH 3 CH 3 HO - "I OH / 1 \ / CH3 \ CH3 C9 CO2 \ /

9. Set according to patent claim 1, characterized in that the base dye cresolite is used.

10. According to claim 1, characterized in that the condensation reaction is carried out in the presence of glacial acetic acid.

11. According to patent claim 1, it is claimed ("dray") that the necessary cations are added in the form of salts of weak acids and bases of such acids, which are present in the reaction mixture. Introduced publications: Patents from Germany 946 251. Gmbud: CH, CH, \ / \ / \ / C0 anvandes.Ing. M Kierkegaard, Stockholm Stockholm 1964. Kungl. Eoktr. PA Norstedt & Soner. 640089