PL212902B1 - Colourful imidazol salts and production method of colourful imidazol salts - Google Patents

Colourful imidazol salts and production method of colourful imidazol salts

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PL212902B1
PL212902B1 PL382868A PL38286807A PL212902B1 PL 212902 B1 PL212902 B1 PL 212902B1 PL 382868 A PL382868 A PL 382868A PL 38286807 A PL38286807 A PL 38286807A PL 212902 B1 PL212902 B1 PL 212902B1
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iodine
bromine
proton
under reduced
temperature
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PL382868A
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Polish (pl)
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PL382868A1 (en
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Juliusz Pernak
Nina Paczesna
Bartosz Brzycki
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Politechnika Poznanska
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Description

Opis wynalazkuDescription of the invention

Przedmiotem wynalazku s膮: barwne sole imidazoliowe oraz spos贸b wytwarzania barwnych soli imidazoliowych.The present invention relates to colored imidazolium salts and a method for preparing colored imidazolium salts.

Sole imidazoliowe s膮 to zwi膮zki organiczne, sk艂adaj膮ce si臋 z organicznego kationu zawieraj膮cego pier艣cie艅 imidazoliowy, w kt贸rym na azometinowym atomie azotu znajduje si臋 艂adunek dodatni, stabilizuje go jon ujemny, pochodz膮cy od anionu, o charakterze nieorganicznym lub organicznym. Obszar zastosowania soli imidazoliowych powi臋ksza si臋 z roku na rok. Spowodowane jest to unikalnymi w艂a艣ciwo艣ciami tej grupy zwi膮zk贸w. Wykazuj膮 one wysok膮 aktywno艣膰 powierzchniow膮, s膮 skuteczne w niszczeniu bakterii i grzyb贸w, wykazuj膮 w艂a艣ciwo艣ci antyelektrostatyczne oraz antyzbrylaj膮ce. Znalaz艂y r贸wnie偶 zastosowanie w katalizie jako katalizatory przeniesienia mi臋dzy fazowego, w procesach galwanizacji i w produkcji lek贸w.Imidazolium salts are organic compounds consisting of an organic cation containing an imidazole ring with a positive charge on the azomethine nitrogen atom, stabilized by a negative ion, derived from an anion, of an inorganic or organic nature. The area of application of imidazolium salts increases from year to year. This is due to the unique properties of this group of compounds. They show high surface activity, are effective in destroying bacteria and fungi, have antistatic and anti-caking properties. They have also found application in catalysis as phase transfer catalysts, in electroplating processes and in drug production.

Eozyna jest bromopochodn膮 fluoresceiny i wyst臋puje w postaci czerwonych kryszta艂贸w. Jest rozpuszczalna w alkoholu, a jej sole sodowe i potasowe s膮 rozpuszczalne w wodzie, octanie etylu i alkoholu. Eozyna jest stosowana jako barwnik do tekstyli贸w, w produkcji atramentu, w barwieniu kosmetyk贸w i gazoliny oraz jako sk艂adnik toner贸w. Sole eozyny. sodowa albo potasowa, maj膮 posta膰 krystalicznego proszku o zabarwieniu od czerwonego do r贸偶owego. U偶ywane s膮 w biologii do barwienia kom贸rek: wybarwia kwasowe cz膮stki struktur kom贸rkowych takich jak: cytoplazma. w艂贸kna kolagenowe czy wi臋kszo艣膰 ziaren wydzielniczych w kom贸rkach. Eozyna jest r贸wnie偶 silnie wch艂aniana przez czerwone cia艂ka krwi barwi膮c je na kolor jasno czerwony.Eosin is a bromo derivative of fluorescein and is present as red crystals. It is soluble in alcohol, and its sodium and potassium salts are soluble in water, ethyl acetate and alcohol. Eosin is used as a dye for textiles, in the production of ink, in the coloring of cosmetics and gasoline, and as a component of toners. Eosin salts. sodium or potassium, they are a red to pink crystalline powder. They are used in biology for staining cells: they stain acidic particles of cell structures such as cytoplasm. collagen fibers or most of the secretory grains in cells. Eosin is also strongly absorbed by red blood cells, staining them bright red.

Eozyna B lub jej disodowa s贸l posiada wyra藕nie niebieskawy odcie艅, natomiast eozyna Y lub jej disodowa s贸l wyra藕nie 偶贸艂tawy odcie艅. Zwi膮zki te s膮 rozpuszczalne w wodzie.Eosin B or its disodium salt has a distinctly bluish tinge, while Eosin Y or its disodium salt has a distinctly yellowish tinge. These compounds are soluble in water.

Fluoresceina to popularny fluochromatyczny barwnik. Wyst臋puje w postaci 偶贸艂tawego do czerwonego krystalicznego proszku. Jest trudno rozpuszczalna w wodzie, natomiast dobrze rozpuszcza si臋 w rozcie艅czonych kwasach i zasadach. Fluoresceine otrzymuje si臋 w wyniku kondensacji bezwodnika ftalowego z rezorcyny. Jest surowcem do otrzymywania eozyn. Fluoresceina jest stosowana w barwieniu jedwabiu i we艂ny. Jej s贸l sodowa, zwana tak偶e uranin膮. jest stosowana do barwienia tekstyli贸w, w oceanografii jako marker wody morskiej oraz w barwieniu agrochemikali贸w. detergent贸w czy przeciwzamarzaczy. Uranina jest pomara艅czowo-czerwonym krystalicznym proszkiem, rozpuszczalnym w wodzie, bez zapachu.Fluorescein is a popular fluochromatic dye. It comes in the form of a yellowish to red crystalline powder. It is sparingly soluble in water, but dissolves well in dilute acids and bases. Fluoresceine is produced by the condensation of phthalic anhydride with resorcinol. It is the raw material for obtaining eosins. Fluorescein is used in dyeing silk and wool. Its sodium salt, also called uranine. it is used for dyeing textiles, in oceanography as a marker of sea water and in the dyeing of agrochemicals. detergents or antifreeze. Uranine is an orange-red crystalline powder, soluble in water, odorless.

Erytrozyna B jest jodopochodn膮 fluoresceiny o wyra藕nie niebieskawym odcieniu. Stosowana jest do barwienia kosmetyk贸w i 偶ywno艣ci (11127). Erytrozyna jest r贸wnie偶 wykorzystywana jako barwnik kom贸rek nerwowych oraz bakterii w ziemi. Zwi膮zek ten pozwala dostrzec rotacyjn膮 dyfuzj臋 bia艂ek b艂on, dzia艂aj膮c jak fosforyzuj膮ca sonda.Erythrosin B is the iodine derivative of fluorescein with a clearly bluish tinge. It is used to color cosmetics and food (11127). Erythrosine is also used as a dye for nerve cells and bacteria in the soil. This compound allows one to perceive the rotational diffusion of membrane proteins, acting as a phosphorescent probe.

11

Przedmiotem wynalazku s膮 barwne sole imidazoliowe o wzorze og贸lnym I. w kt贸rym R1 ozna23 cza proton lub brom, Iub jod, lub grup臋 nitrow膮, R2 oznacza proton lub brom, Iub jod, R3 oznacza pro45 ton lub brom, Iub jod, R4 proton lub brom, Iub jod, Iub grup臋 nitrow膮, R5 oznacza prosto艂a艅cuchow膮 grup臋 alkilow膮 zawieraj膮c膮 od 2 do 12 atom贸w w臋gla oraz spos贸b wytwarzania barwnych soli imida12 zoliowych o wzorze og贸lnym I, w kt贸rym R1 oznacza proton lub brom, Iub jod, Iub grup臋 nitrow膮, R2 oznacza proton lub brom, lub jod, R3 oznacza proton lub brom, Iub jod, R4 oznacza proton lub brom, 5 The invention relates to colored imidazolium salts of the general formula I. wherein R 1 is a proton or bromine, or iodine or a nitro group, R 2 is a proton or bromine, or iodine, R 3 is a proton or bromine, or iodine, 4 proton or bromine, or iodine, or nitro group, R 5 is a straight chain alkyl group containing from 2 to 12 carbon atoms and a process for the preparation of colored imidolol salts of general formula I in which R 1 is proton or bromine, or iodine, or a nitro group, R2 is a proton or bromine or iodine, R 3 is a proton or bromine, Iub iodine, R 4 is a proton or bromine 5

Iub jod, Iub grup臋 nitrow膮, R5 oznacza prosto艂a艅cuchow膮 grup臋 alkilow膮 zawieraj膮c膮 od 2 do 12 ato5 m贸w w臋gla, kt贸ry polega na tym, 偶e halogenki imidazoliowe o wzorze og贸lnym 2, w kt贸rym R5 oznacza prosto艂a艅cuchow膮 grup臋 alkilow膮 zawieraj膮c膮 od 2 do 12 atom贸w w臋gla reaguj膮 z sol膮 orga12 niczn膮 o wzorze og贸lnym 3, w kt贸rym R1 oznacza proton lub brom, Iub jod, Iub grup臋 nitrow膮, R2 oznacza proton lub brom, Iub jod, R3 oznacza proton lub brom, Iub jod, R4 oznacza proton lub brom, Iub jod, Iub grup臋 nitrow膮, M oznacza kation potasu lub sodu, lub amoniowy, w stosunku molowym 2:1 w temperaturze od 277 K do 373 K w 艣rodowisku wodnym, nast臋pnie odparowuje si臋 rozpuszczalnik w warunkach obni偶onego ci艣nienia w temperaturze od 293 K do 333 K, dodaje bezwodnego rozpuszczalnika organicznego, po czym oddziela si臋 osad przez ods膮czenie, odparowuje aceton i suszy w warunkach obni偶onego ci艣nienia w temperaturze od 303 do 373 K.IUB iodine, Iub nitro, R 5 is a straight chain alkyl group containing from 2 to 12 ATO 5 atoms, which is characterized in that the halides imidazolium general formula 2 wherein R 5 is a straight chain alkyl group containing from 2 to 12 carbon react with an organic salt of general formula 3, wherein R 1 is a proton or bromine, or iodine, or a nitro group, R 2 is a proton or bromine, or iodine, R 3 is a proton or bromine, or iodine, R 4 is proton or bromine, or iodine, or nitro group, M is potassium or sodium or ammonium cation, in a molar ratio of 2: 1 at a temperature of 277 K to 373 K in an aqueous medium, then the solvent is evaporated under reduced pressure at a temperature from 293 K to 333 K, an anhydrous organic solvent is added, then the precipitate is separated by filtration, acetone is evaporated and dried under reduced pressure at a temperature of 303 to 373 K.

11

Drugi spos贸b wytwarzania barwnych soli imidazoliowych o wzorze og贸lnym 1, w kt贸rym R1 23 oznacza proton lub brom, Iub jod, Iub grup臋 nitrow膮, R2 oznacza proton lub brom, Iub jod, R3 oznacza 45 proton lub brom, Iub jod, R4 oznacza proton lub brom, Iub jod, Iub grup臋 nitrow膮, R5 oznacza prosto艂a艅cychow膮 grup臋 alkilow膮 zawieraj膮c膮 od 2 do 12 atom贸w w臋gla, polega na tym, 偶e halogenki imida5 zoliowe o wzorze og贸lnym 2, w kt贸rym R5 oznacza prosto艂a艅cuchow膮 grup臋 alkilow膮 zawieraj膮c膮 od 2 1 do 12 atom贸w w臋gla poddaje si臋 reakcji z sol膮 organiczn膮 o wzorze og贸lnym 3, w kt贸rym R1 oznaczaA second method for producing colored salts of imidazolium general formula 1, wherein R 1 23 is a proton or bromine, Iub iodine, Iub nitro, R 2 is a proton or bromine, Iub iodine, R 3 is 45 proton or bromine, Iub iodine, R 4 is a proton or bromine, Iub iodine, Iub nitro, R 5 is prosto艂a艅cychow膮 alkyl group containing from 2 to 12 carbon atoms, lies in the fact that halides imidazole 5 zoliowe of general formula 2 wherein R 5 is a straight chain alkyl group having 2 from 1 to 12 carbon atoms is reacted with an organic salt of general formula 3 wherein R 1 is

PL 212 902 B1 proton lub brom, Iub jod, Iub grup臋 nitrow膮, R2 oznacza proton lub brom, Iub jod, R3 oznacza proton lub brom, Iub jod, R4 oznacza proton lub brom, Iub jod, Iub grup臋 nitrow膮, M oznacza potas lub s贸d, Iub amon, w stosunku molowym 2:1 w temperaturze od 277 do 373K w 艣rodowisku wodnym, nast臋pnie dodaje si臋 hydrofobowy rozpuszczalnik organiczny, po czym przep艂ukuje si臋 warstw臋 organiczn膮 wod膮 destylowan膮 do momentu zaniku jon贸w halogenowych w odcieku, dalej odparowuje si臋 rozpuszczalnik w warunkach obni偶onego ci艣nienia w temperaturze powy偶ej 293K. i suszy w warunkach obni偶onego ci艣nienia w temperaturze powy偶ej 293K.GB 212 902 B1 proton or bromine, Iub iodine, Iub nitro, R 2 is a proton or bromine, Iub iodine, R 3 is a proton or bromine, Iub iodine, R 4 is a proton or bromine, Iub iodine, Iub nitro, M denotes potassium or sodium, or ammonium, in a 2: 1 molar ratio at a temperature of 277 to 373K in an aqueous medium, then a hydrophobic organic solvent is added, then the organic layer is rinsed with distilled water until the disappearance of halogen ions in the effluent, further evaporation solvent under reduced pressure at a temperature above 293K. and dried in conditions of reduced pressure at a temperature above 293K.

Dzi臋ki zastosowaniu rozwi膮zania wed艂ug wynalazku uzyskano nast臋puj膮ce efekty technicznoekonomiczne: otrzymano nowe zwi膮zki zaliczane do grupy soli imidazoliowych.Due to the solution according to the invention, the following technical and economic effects were obtained: new compounds belonging to the group of imidazolium salts were obtained.

Zastosowanie aplikacyjne tych soli imidazoliowych jest bardzo szerokie, obejmuje ono m.in.:The application use of these imidazolium salts is very wide, including:

- sk艂adniki lakier贸w, farb, tworzyw pow艂okowych typu polimerowego (PHT, PP, PE, PCV),- components of varnishes, paints, polymer-type coating materials (PHT, PP, PE, PVC),

- katalizatory reakcji,- reaction catalysts,

- rozpuszczalniki,- solvents,

- sk艂adniki 艣rodk贸w do ochrony drewna przed grzybami i bakteriami.- ingredients of wood preservatives against fungi and bacteria.

11

Wynalazkiem s膮 barwne sole imidazoliowe o wzorze og贸lnym 1, w kt贸rym R1 oznacza proton 23 lub brom, Iub jod, Iub grup臋 nitrow膮, R2 oznacza proton lub brom, Iub jod, R3 oznacza proton lub 45 brom, Iub jod, R4 oznacza proton lub brom, Iub jod, Iub grup臋 nitrow膮, R5 oznacza prosto艂a艅cuchow膮 grup臋 alkilow膮 zawieraj膮c膮 od 2 do 12 atom贸w w臋gla. Spos贸b ich otrzymywania ilustruj膮 poni偶sze przyk艂ady:Invention are colored imidazolium salts of formula 1 wherein R 1 is a proton 23 or bromine, Iub iodine, Iub nitro, R 2 is a proton or bromine, Iub iodine, R 3 is a proton or 45 bromine, Iub iodine, R 4 R5 represents a proton or bromine, or iodine, or a nitro group, R 5 is a straight chain alkyl group containing from 2 to 12 carbon atoms. The method of their preparation is illustrated by the following examples:

P r z y k 艂 a d IP r z k 艂 a d I

Eozynian B 3-bytuokszymetylo-1-metyloimidazolilowy 3 3-B-estoxymethyl-1-methylimidazolyl eosinate B 3

0,005 mola soli sodowej eozyny B rozpuszczono W 30 cm3 wody destyIowanej i wprowadzono 3 do kolby okr膮g艂odennej o pojemno艣ci 100 cm3 zaopatrzonej W mieszad艂o magnetyczne. Do roztworu 3 dodano 0,01 I mola chlorku 3-butoksymetyIo-1-metyloimidazoliowego rozpuszczonego W 20 cm3 wody destylowanej. Reakcj臋 prowadzono przez 24 godziny W temperaturze 298 K. Na dnie kolby uzyskano 3 hydrofobow膮, g臋st膮, smolist膮 ma藕. Po oddzieleniu wody pozosta艂o艣膰 rozpuszczono W 20 cm3 chloroformu. Powsta艂y roztw贸r przemywano wod膮 w rozdzielaczu do momentu ca艂kowitego usuni臋cia chlork贸w. Zawarto艣膰 soli nieorganicznej monitorowano wodnym roztworem azotanu (V) srebra. Po rozdzieleniu faz z fazy organicznej odparowano chloroform. Pozosta艂o艣膰 suszono W temperaturze 353 K pod obni偶onym ci艣nieniem.0.005 moles of the sodium salt of eosin B were dissolved in 30 cm 3 of distilled water and 3 were introduced into a 100 cm 3 round-bottom flask equipped with a magnetic stirrer. 0.01 l mole of 3-butoxymethyl-1-methylimidazolium chloride dissolved in 20 cm 3 of distilled water was added to solution 3 . The reaction proceeded for 24 hours at 298 K. At the bottom of the flask to obtain 3 hydrophobic thick, tarry gunk. After the water was separated off, the residue was dissolved in 20 cm 3 of chloroform. The resulting solution was washed with water in a separating funnel until all chlorides were removed. The content of inorganic salt was monitored with an aqueous solution of silver nitrate. After phase separation, chloroform was evaporated from the organic phase. The residue was dried at 353 K under reduced pressure.

Struktur臋 zwi膮zku potwierdzono wykonuj膮c analiz臋 elementarn膮 CHN dla C38H41Br2N6O11 (M = 917,57):The compound structure was confirmed by elemental CHN analysis for C38H41Br2N6O11 (M = 917.57):

warto艣ci wyIiczone w %: C = 49,74: 11 = 4,50: N = 9,16: warto艣ci otrzymane w %: C = 49,52: H = 4,33: N = 8,91.values calculated in%: C = 49.74: 11 = 4.50: N = 9.16: values obtained in%: C = 49.52: H = 4.33: N = 8.91.

P r z y k 艂 a d IIP r z x l a d II

Eozynian B 3-decyIoksymetyIo-1-metyIoimidazoliowy 3 Eosinate B 3-decyloxymethyl-1-methylimidazolium 3

Do kolby okr膮g艂odennej o pojemno艣ci 100 cm3 zaopatrzonej w mieszad艂o magnetyczne wprowadzono 0,005 mola eozyny B w postaci soli, rozpuszczonej w 20 cm wody destyIowanej i dodano 3 To a 100 cm 3 round-bottom flask equipped with a magnetic stirrer, 0.005 mol of eosin B in the form of salt, dissolved in 20 cm of distilled water, was introduced and 3

0,009 mola chlorku 3-decyIoksymetyIo-1-metyloimidazoliowego rozpuszczonego w 10 cm3 wody destyIowanej. Mieszanin臋 reakcyjn膮 intensywnie mieszano przez 24 godziny w temperaturze 298K. Na3 st臋pnie oddzielono wod臋 od hydrofobowego produktu, kt贸ry rozpuszczono w 20 cm3 chloroformu. Roztw贸r chloroformowy przemywano wod膮 destylowan膮, a偶 do momentu ca艂kowitego usuni臋cia chlorku sodu z fazy chloroformowej. Obecno艣膰 chlork贸w sprawdzano wodnym roztworem azotanu (V) srebra. Po odparowaniu chloroformu, pozosta艂o艣膰 suszono w temperaturze 353K pod obni偶onym ci艣nieniem. Otrzymano produkt w postaci zielonego wosku. Rozpuszczony w acetonie zyska艂 bardzo jaskrawy pomara艅czowy kolor. Czysto艣膰 otrzymanego zwi膮zku okre艣lono na podstawie miareczkowania dwufazowego (PN-HN-ISO-2871-1) uzyskuj膮c zawarto艣膰 substancji kationowo czynnej 70,5%.0.009 mol of 3-decyloxymethyl-1-methylimidazolium chloride dissolved in 10 cm 3 of distilled water. The reaction mixture was vigorously stirred for 24 hours at the temperature of 298K. 3 was then separated water from hydrophobic product, which is dissolved in 20 cm 3 of chloroform. The chloroform solution was washed with distilled water until the sodium chloride was completely removed from the chloroform phase. The presence of chlorides was checked with an aqueous solution of silver nitrate. After evaporating the chloroform, the residue was dried at 353K under reduced pressure. The product obtained was a green wax. Dissolved in acetone, it has acquired a very bright orange color. The purity of the obtained compound was determined on the basis of a two-phase titration (PN-HN-ISO-2871-1), obtaining a cationic active substance content of 70.5%.

Struktur臋 zwi膮zku potwierdzono wykonuj膮c widma protonowego i w臋glowego magnetycznego rezonansu j膮drowego:The structure of the compound was confirmed by performing proton and carbon nuclear magnetic resonance spectra:

1H NMR (DMSOcfe) Sppm = 0,840 (t, J=4,4 Hz, 6H): 1,207 (m, 28H): 1,467 (m, 4H): 3,459 (t, J=4,3 Hz, 4H): 3,901 (s, 6H): 5,571 (s, 4H): 6,517 (s, 1H): 7,057 (d, J=3,1 Hz, 1H): 7,326 (1, J=3,3 Hz, 1H): 7,510 (1, J=2,5 Hz, 1H): 7,783 (d, J=5,3 Hz, 2H): 7,866 (d, J=4,1 Hz, 2H): 7,994 (d, J=1,9 Hz, 1H): 9,473(s, 2H): 1 H NMR (DMSOcfe) = 0.840 ppm (t, J = 4.4 Hz, 6H): 1.207 (m, 28H): 1.467 (m, 4H) 3.459 (t, J = 4.3 Hz, 4H): 3.901 (s, 6H): 5.571 (s, 4H): 6.517 (s, 1H): 7.057 (d, J = 3.1 Hz, 1H): 7.326 (1, J = 3.3 Hz, 1H): 7.510 (1, J = 2.5 Hz, 1H): 7.783 (d, J = 5.3 Hz, 2H): 7.866 (d, J = 4.1 Hz, 2H): 7.994 (d, J = 1.9 Hz, 1H): 9.473 (s, 2H):

13C NMR (DMSOcfe) Sppm = 13,954: 22,112: 25,321: 28,644: 28,708: 28,964: 28,991: 30,680: 31,301: 35,916: 69,159: 78,089: 101,339: 121,868: 124,023: 124,712: 127,342: 127,730: 129,003: 129,145: 129,012: 130,158: 130,423: 134,285: 135,426: 137,380: 152,541: 163,118: 168,350. 13 C NMR (DMSOcfe) ppm = 13.954: 22.112: 25.321: 28.644: 28.708: 28.964: 28.991: 30.680: 31.301: 35.916: 69.159: 78.089: 101.339: 121.868: 124.023: 124.712: 127.342: 127.730: 129.003: 129.145: 129.012: 130,158: 130,423: 134,285: 135,426: 137,380: 152,541: 163,118: 168,350.

PL 212 902 B1PL 212 902 B1

Analiza elementarna CHN dla C50H65Br2N6O11 (M = 1857,89): warto艣ci wyliczone w %: C = 55,30: H = 6,03: N = 7,74: warto艣ci otrzymane w %: C = 55,12:H = 5,81: N = 7,56.Elemental analysis of CHN for C50H65Br2N6O11 (M = 1857.89): values calculated in%: C = 55.30: H = 6.03: N = 7.74: values obtained in%: C = 55.12: H = 5 , 81: N = 7.56.

P r z y k 艂 a d IIIP r x l a d III

Eozynian B 3-dodecyIoksymetyIo-1-metyIoimidazoliowyEosinate B 3-dodecyloxymethyl-1-methylimidazolium

W kolbie okr膮g艂o dennej, zaopatrzonej w mieszad艂o magnetyczne, rozpuszczono 0,004 mola 3 soli sodowej eozyny B w 30 cm3 wody destylowanej. Do roztworu dodano dwukrotny nadmiar molowy 3 chlorku 3-dodecyIoksymetyIo-1-metyIoimidazoliowy rozpuszczonego w 20 cm3 wody destylowanej.In a round-bottom flask equipped with a magnetic stirrer, 0.004 mol 3 of eosin B sodium salt was dissolved in 30 cm 3 of distilled water. A 2-fold molar excess of 3 -dodecyloxymethyl-1-methylimidazolium chloride dissolved in 20 cm 3 of distilled water was added to the solution.

Reakcj臋 prowadzono przez 24 godziny w temperaturze 295K. Na dnie kolby uzyskano hydrofobow膮, g臋st膮, smolist膮 ma藕. Po oddzieleniu wody. pozosta艂o艣膰 suszono w temp. 353K, pod obni偶onym ci3 艣nieniem. Nast臋pnie produkt rozpuszczono w 50 cm3 bezwodnego acetonu. Ods膮czono osad, a z przes膮czu odparowano rozpuszczalnik. Pozosta艂o艣膰 wysuszono w 353 K pod obni偶onym ci艣nieniem. Otrzymano produkt w postaci g臋stego czarnego wosku.The reaction was carried out for 24 hours at the temperature of 295K. A hydrophobic, thick, tarry goo was obtained at the bottom of the flask. After separating the water. the residue is dried at. 353K under reduced these three pressure. The product was then dissolved in 50 cm 3 of anhydrous acetone. The precipitate was filtered off and the filtrate's solvent was evaporated. The residue was dried at 353 K under reduced pressure. The product was obtained in the form of a thick black wax.

Czysto艣膰 otrzymanego zwi膮zku okre艣lono na podstawie miareczkowania dwufazowego (PN-KN-ISO-2871-1) uzyskuj膮c zawarto艣膰 substancji kationowo czynnej 85%.The purity of the obtained compound was determined on the basis of a two-phase titration (PN-KN-ISO-2871-1), resulting in a cationic active substance content of 85%.

Struktur臋 zwi膮zku potwierdzono wykonuj膮c analiz臋 elementarn膮 CHN dla C54H73Br2N6O11 (M - 1141,99):The compound structure was confirmed by elemental CHN analysis for C54H73Br2N6O11 (M - 1141.99):

warto艣ci wy liczone w %: C = 56,76: 11 = 6,44: N = 7,36:values calculated in%: C = 56.76: 11 = 6.44: N = 7.36:

warto艣ci otrzymane w %: C - 56,55: H = 6,14: N = 7,15.values obtained in%: C - 56.55: H = 6.14: N = 7.15.

P r z y k 艂 a d IVP r x l a d IV

Eozynian Y 3-butoksymetyIo-1-metyIoimidazoliowy 3 3-butoxymetyIo-1-methylimidazolium eosinate 3

Do reaktora wprowadzono 0,005 mola soli sodowej eozyny Y rozpuszczonej w 30 cm3 wody destylowanej i dodano 0,010 mola chlorku 3-butoksymetyIo-1-metyIoimidazoliowego rozpuszczonego 3 w 20 cm3 wody destylowanej. Przy intensywnym mieszaniu, w temperaturze 353K, przez 24 godziny, wypad艂 produkt w postaci zielonego wosku. Po oddzieleniu wody, pozosta艂o艣膰 suszono w temperatu3 rze 353 K, pod obni偶onym ci艣nieniem. Nast臋pnie produkt rozpuszczono w 50 cm3 bezwodnego acetonu. Ods膮czono osad, a z przes膮czu odparowano rozpuszczalnik. Pozosta艂o艣膰 wysuszono w temperaturze 353 K pod obni偶onym ci艣nieniem. Produkt otrzymano w postaci zielonego wosku.The reactor was charged 0.005 mol of the sodium salt of Eosin Y dissolved in 30 cm 3 of distilled water were added 0.010 mol of 3-butoksymetyIo 1 metyIoimidazoliowego 3 dissolved in 20 cm 3 of distilled water. With intensive stirring at the temperature of 353K for 24 hours, the product in the form of a green wax appeared. After separation of water, the residue was dried in a temperatu 3 sculpture 353 K, under reduced pressure. The product was then dissolved in 50 cm 3 of anhydrous acetone. The precipitate was filtered off and the filtrate's solvent was evaporated. The residue was dried at 353 K under reduced pressure. The product was obtained as a green wax.

Struktur臋 zwi膮zku potwierdzono wykonuj膮c widma protonowego i w臋glowego magnetycznego rezonansu j膮drowego:The structure of the compound was confirmed by performing proton and carbon nuclear magnetic resonance spectra:

1H NMR (DMSOd6) 5ppm = 0,828(1, J=4,8 Hz, 6H): 1,242 (m, 411): 1,459 (m, 4H): 3,455 (1, J=4,2 Hz, 4H): 3,867( s, 6H): 5,532 (s, 4H): 6,306 (s, 1H): 6,593 (s, 1H): 6,905 (d, J= 4,0 Hz, 1H): 7,274 ( t, J=2,2 Hz, 1H): 7,630 (t, J=3,0 Hz, 1H): 7,754 (d, 2H): 7,847(d, 2H): 8,073 (d, J=4,5 Hz, 1H): 9,426 (s, 2H): 1 H NMR (DMSOd6) 5ppm = 0.828 (1, J = 4.8 Hz, 6H): 1.242 (m, 411): 1.459 (m, 4H) 3.455 (1, J = 4.2 Hz, 4H) : 3.867 (s, 6H): 5.532 (s, 4H): 6.306 (s, 1H): 6.593 (s, 1H): 6.905 (d, J = 4.0 Hz, 1H): 7.274 (t, J = 2 , 2 Hz, 1H): 7.630 (t, J = 3.0 Hz, 1H): 7.754 (d, 2H): 7.847 (d, 2H): 8.073 (d, J = 4.5 Hz, 1H): 9.426 (s, 2H):

13C NMR (DMSOd6) 5ppm = 13,598: 18,546: 30,680: 35,898: 68,854: 99,125: 109,446: 1 17,997: 121,850: 124,009: 129,095: 129,186: 129,378: 129,451: 129,729: 129,899: 130,345: 132,824: 137,293: 152,911: 167,218: 167,323: 168,167, 13 C NMR (DMSOd6) 5ppm = 13.598: 18.546: 30.680: 35.898: 68.854: 99.125: 109.446 1 17.997: 121.850: 124.009: 129.095: 129.186: 129.378: 129.451: 129.729: 129.899: 130.345: 132.824: 137.293: 152.911: 167.218: 167.323: 168.167,

Analiza elementarna CHN dla C38H41Br4N4O7 (M = 985,37): warto艣ci wyliczone w %: C = 46,32: H = 4,19: N = 5,69: warto艣ci otrzymane w %: C = 46,14: 11 = 3,92: N = 5,35.Elemental analysis of CHN for C38H41Br4N4O7 (M = 985.37): values calculated in%: C = 46.32: H = 4.19: N = 5.69: values obtained in%: C = 46.14: 11 = 3 , 92: N = 5.35.

P r z y k 艂 a d VP r z k 艂 a d V

Eozynian Y 3-decyloksymetylo-1-metyloimidazolilowy 3 3-decyloxymethyl-1-methylimidazolyl eosinate Y 3

W kolbie okr膮g艂o dennej, zaopatrzonej w mieszad艂o magnetyczne, rozpuszczono w 30 cm3 wody destylowanej 0,004 mola soli eozyny Y. Do roztworu dodano dwukrotny nadmiar molowy chlorku 3 In a round-bottom flask, equipped with a magnetic stirrer, 0.004 mol of Eosin Y salt was dissolved in 30 cm 3 of distilled water. A two-fold molar excess of chloride 3 was added to the solution.

3-decyIoksymetyIo-1-metyloimidazoliowego, rozpuszczonego w 20 cm3 wody destylowanej. Reakcj臋 prowadzono przez 24 godziny w temperaturze 315 K. Produkt reakcji wypad艂 w postaci ciek艂ej dolnej warstwy. Po oddzieleniu wody, pozosta艂o艣膰 suszono w temp. w 353 K pod obni偶onym ci艣nieniem. Na3 st臋pnie produkt rozpuszczono w 50 cm3 bezwodnego acetonu. Ods膮czono osad, a z przes膮czu odparowano rozpuszczalnik. Pozosta艂o艣膰 wysuszono w temperaturze 353K pod obni偶onym ci艣nieniem.3-decyloxymethyl-1-methylimidazolium, dissolved in 20 cm 3 of distilled water. The reaction was carried out for 24 hours at a temperature of 315 K. The reaction product came out in the form of a liquid bottom layer. After the water was separated off, the residue was dried at 353 K under reduced pressure. 3 was then dissolved in 50 cm 3 of anhydrous acetone. The precipitate was filtered off and the filtrate's solvent was evaporated. The residue was dried at 353K under reduced pressure.

Czysto艣膰 otrzymanego zwi膮zku okre艣lono na podstawie miareczkowania dwufazowego (PN-KN-ISO-2871-1) uzyskuj膮c zawarto艣膰 substancji kationowo czynnej 97,5%.The purity of the obtained compound was determined on the basis of a two-phase titration (PN-KN-ISO-2871-1), resulting in a cationic active substance content of 97.5%.

Struktur臋 zwi膮zku potwierdzono wykonuj膮c widma protonowego i w臋glowego magnetycznego rezonansu j膮drowego:The structure of the compound was confirmed by performing proton and carbon nuclear magnetic resonance spectra:

1H NMR (DMSOcfe) 5ppm = 0,840(t, J= 4,4 Hz, 6H): 1,198 (m, 28H): 1,447 (m, 4H): 3,429 (t, J= 4,3 Hz, 4H): 3,853 (s, 6H): 5,522 (s, 4H): 6,265 (s, 1H): 6,631 (s, 1H): 7,106 (d, J=2,7 Hz, 1H): 1 H NMR (DMSOcfe) 5ppm = 0.840 (t, J = 4.4 Hz, 6H): 1.198 (m, 28H): 1.447 (m, 4H) 3.429 (t, J = 4.3 Hz, 4H): 3.853 (s, 6H): 5.522 (s, 4H): 6.265 (s, 1H): 6.631 (s, 1H): 7.106 (d, J = 2.7 Hz, 1H):

PL 212 902 B1PL 212 902 B1

7,500 (t, J=2,5 Hz, 1H): 7,765 (d, 2H): 7,848 (d, 2H): 8,018 (t, J=2,9 Hz, 1H): 8,364 (d, 1H): 9,571 (s, 2H):7,500 (t, J = 2.5 Hz, 1H): 7.765 (d, 2H): 7.848 (d, 2H): 8.018 (t, J = 2.9 Hz, 1H): 8.364 (d, 1H): 9.571 (s, 2H):

13C NMR (DMSOcfe) 5ppm = 13,965: 22,109: 25,328: 28,658: 28,704: 28,714: 28,956: 28,988: 31,291:35,802:69,087: 79,175:98,799: 109,409: 117,539: 121,646: 123,790: 127,962: 128,195: 128,530: 129,014: 129,511: 129,646: 129,888: 132,186: 137,279: 152,675: 167,210: 167,814. 13 C NMR (DMSOcfe) 5ppm = 13.965: 22.109: 25.328: 28.658: 28.704: 28.714: 28.956: 28.988: 31.291: 35.802: 69.087: 79.175: 98.799: 109.409: 117.539: 121.646: 123.790: 127.962: 128.195: 128.530: 129.014: 129.511: 129.646: 129.888: 132.186: 137.279: 152.675: 167.210: 167.814.

Analiza elementarna CHN dla C50H65Br4N4O7 (M = 1 153,69): warto艣ci wyliczone w %: C = 52,05: H = 5,68: N =: 4,86: warto艣ci otrzymane w %: C = 51,83: H = 5,38: N = 4,55.Elemental CHN analysis for C50H65Br4N4O7 (M = 1 153.69): values calculated in%: C = 52.05: H = 5.68: N = : 4.86: values obtained in%: C = 51.83: H = 5.38: N = 4.55.

P r z y k 艂 a d VIP r x l a d VI

Eozynian Y 3-dodecyloksymetylo-1-metyloimidazoliowy 3 3-dodecyloxymethyl-1-methylimidazolium-eosinate 3

Do reaktora wprowadzono 0,004 mola soli eozyny Y rozpuszczonej w 30 cm3 wody destylowanej. Do roztworu dodano 0,009 mola chlorku 3-dodecyIoksymetyIo-1-metyIoimidazoliowy rozpuszczo3 nego w 20 cm3 wody destylowanej. Reakcj臋 prowadzono przez 24 godziny w temperaturze 298K. Po oddzieleniu wody, pozosta艂o艣膰 suszono w temperaturze 353 K, pod obni偶onym ci艣nieniem. Nast臋pnie 3 produkt rozpuszczono w 50 cm3 bezwodnego acetonu. Ods膮czono osad, a z przes膮czu odparowano rozpuszczalnik. Pozosta艂o艣膰 wysuszono w temperaturze 353K pod obni偶onym ci艣nieniem. Produkt otrzymano w postaci g臋stej smo艂y. Czysto艣膰 otrzymanego zwi膮zku okre艣lono na podstawie miareczkowania dwufazowego (PN-EN-ISO-2871-1) uzyskuj膮c zawarto艣膰 substancji kationowe czynnej 93%.0.004 mol of Eosin Y salt dissolved in 30 cm 3 of distilled water was introduced into the reactor. To the solution was added 0.009 mol of 3-dodecyIoksymetyIo 1 metyIoimidazoliowy rozpuszczo nego 3 in 20 cm 3 of distilled water. The reaction was carried out for 24 hours at the temperature of 298K. After the water was separated off, the residue was dried at 353 K under reduced pressure. The 3 product was then dissolved in 50 cm 3 of anhydrous acetone. The precipitate was filtered off and the filtrate's solvent was evaporated. The residue was dried at 353K under reduced pressure. The product was obtained in the form of thick tar. The purity of the obtained compound was determined on the basis of a two-phase titration (PN-EN-ISO-2871-1), resulting in a cationic active substance content of 93%.

Struktur臋 zwi膮zku potwierdzono wykonuj膮c widma protonowego i w臋glowego magnetycznego rezonansu j膮drowego:The structure of the compound was confirmed by performing proton and carbon nuclear magnetic resonance spectra:

1H NMR (DMSOcfe) 5ppm = 0,847(t, J=4,4 Hz, 6H): 1,219 (m, 36H): 1,458 (m, 4H): 3,442 (t, J=4,3 Hz, 4H): 3,865 (s, 6H): 5,534 ( s, 4H): 6,277 (s, 1H): 6,614(s, 1H): 7,013 (d, J=8,4 Hz, 1H): 7,137 (1, J=1,3 Hz, 1H): 7,532 (t, J=1,5 Hz, 1H): 7,769 (d, 2H): 7,853 (d, 2H): 8,031 (d, J=1,6 Hz, 1H): 9,509 (s, 2H): 1 H NMR (DMSOcfe) 5ppm = 0.847 (t, J = 4.4 Hz, 6H): 1.219 (m, 36H): 1.458 (m, 4H) 3.442 (t, J = 4.3 Hz, 4H): 3.865 (s, 6H): 5.534 (s, 4H): 6.277 (s, 1H): 6.614 (s, 1H): 7.013 (d, J = 8.4 Hz, 1H): 7.137 (1, J = 1, 3 Hz, 1H): 7.532 (t, J = 1.5 Hz, 1H): 7.769 (d, 2H): 7.853 (d, 2H): 8.031 (d, J = 1.6 Hz, 1H): 9.509 ( s, 2H):

13C NMR (DMSOd6) 5ppm = 13,954: 22,112: 25,330: 28,658: 28,731: 29,009: 29,032: 29,064: 31,310:35,857:69,155:78,016: 98,979: 109,533: 117,778: 121,841: 123,977: 128,583: 128,780: 128,875: 128,953: 129,049: 129,528: 129,889; 129,980: 130,177: 132,514: 137,385: 152,906: 167,451: 168,085. 13 C NMR (DMSO from 6 ) 5ppm = 13.954: 22.112: 25.330: 28.658: 28.731: 29.009: 29.032: 29.064: 31.310: 35.857: 69.155: 78.016: 98.979: 109.533: 117.778: 121.841: 123.977: 128.583: 128.780: 128.875: 128.875: 128.975: : 129,049: 129,528: 129,889; 129.980: 130.177: 132.514: 137.385: 152.906: 167.451: 168.085.

Analiza elementarna CHN dla C54H73Br4N4O7 (螠 = 1209,79): warto艣ci wy liczone w %: C = 53,61: H = 6,08: N = 4,63: warto艣ci otrzymane w %: C = 53,40: 11 = 5,85: N = 4,40.Elemental analysis of CHN for C54H73Br4N4O7 (螠 = 1209.79): values calculated in%: C = 53.61: H = 6.08: N = 4.63: values obtained in%: C = 53.40: 11 = 5.85: N = 4.40.

P r z y k 艂 a d VIIExample VII

Erytrozynian 3-butoksymetylo-1-metyloimidazoliowy 3 3-Butoxymethyl-1-methylimidazolium erythrosinate 3

W kolbie okr膮g艂odennej o pojemno艣ci 100 cm3, zaopatrzonej w mieszad艂o magnetyczne, umiesz3 czono 0,004 mola soli erytrozyny rozpuszczonej w 30 cm3 wody destylowanej. Do roztworu dodano 3 A round bottom flask with a capacity of 100 cm 3, equipped with a magnetic stirrer, Can you 3 czono salt, erythrosine 0.004 mol dissolved in 30 cm 3 of distilled water. 3 was added to the solution

0,009 mola chlorku 3-butoksymetyIo-1-metyIoimidazoliowy rozpuszczonego w 20 cm3 wody destylowanej. Reakcj臋 prowadzono przez 24 godziny w temperaturze 298K. Po odparowaniu wody, pozosta艂o艣膰 3 suszono w temperaturze 353K pod obni偶onym ci艣nieniem. Nast臋pnie produkt rozpuszczono w 50 cm3 bezwodnego acetonu. Ods膮czono osad, a z przes膮czu odparowano rozpuszczalnik. Pozosta艂o艣膰 wysuszono w temperaturze 353K pod obni偶onym ci艣nieniem.0.009 mol of 3-butoxymethyl-1-methylimidazolium chloride dissolved in 20 cm 3 of distilled water. The reaction was carried out for 24 hours at the temperature of 298K. After the water was evaporated, the residue 3 was dried at 353K under reduced pressure. The product was then dissolved in 50 cm 3 of anhydrous acetone. The precipitate was filtered off and the filtrate's solvent was evaporated. The residue was dried at 353K under reduced pressure.

Struktur臋 zwi膮zku potwierdzono wykonuj膮c widma protonowego i w臋glowego magnetycznego rezonansu j膮drowego:The structure of the compound was confirmed by performing proton and carbon nuclear magnetic resonance spectra:

1H NMR (DMSOd6) 5ppm = 0,832 (1, J=4,8 Hz, 6H): 1,245 (m, 4H): 1,460 (m, 4H): 3,477 (1, J=2,6 Hz, 4H): 3,861(s, 611): 5,529(s, 4H): 6,872(s, 2H): 7,105 (d, J=4,1 Hz, 1H): 7,247 (t, J=3,1 Hz, 1H): 7,535 (t, J=2,4 Hz, 1H): 7,754 (d, J=1,6 Hz, 2H): 7,845 (d, J=1,6 Hz, 2H): 8,024 (d, J=4,5 Hz, 1H): 9,456 (s, 2H): 1 H NMR (DMSOd6) 5ppm = 0.832 (1, J = 4.8 Hz, 6H): 1.245 (m, 4H): 1.460 (m, 4H) 3.477 (1, J = 2.6 Hz, 4H) : 3.861 (s, 611): 5.529 (s, 4H): 6.872 (s, 2H): 7.105 (d, J = 4.1 Hz, 1H): 7.247 (t, J = 3.1 Hz, 1H): 7.535 (t, J = 2.4 Hz, 1H): 7.754 (d, J = 1.6 Hz, 2H): 7.845 (d, J = 1.6 Hz, 2H): 8.024 (d, J = 4, 5 Hz, 1H): 9.456 (s, 2H):

13C NMR (DMSOd6) 5ppm = 13,644: 18,569: 30,691: 35,919: 68,817: 75,003: 77,994: 95,194: 111,478: 120,316: 121,674: 123,851: 128,144: 128,544: 128,874: 129,790: 130,009; 132,516: 137,131: 137,670: 156,982: 167,019: 171,001. 13 C NMR (DMSO from 6 ) 5ppm = 13.644: 18.569: 30.691: 35.919: 68.817: 75.003: 77.994: 95.194: 111.478: 120.316: 121.674: 123.851: 128.144: 128.544: 128.874: 129.790: 130.009; 132.516: 137.131: 137.670: 156.982: 167.019: 171.001.

Analiza elementarna CHN dla C38H41I4N4O7 (M = 1173,37): warto艣ci wyliczone w %: C = 38,90; H = 3,52: N = 4,77: warto艣ci otrzymane w %: C = 38,71; H = 3,30: N = 4,56,Elemental CHN analysis for C38H41I4N4O7 (M = 1173.37): values calculated in%: C = 38.90; H = 3.52: N = 4.77: values found in%: C = 38.71; H = 3.30: N = 4.56,

P r z y k 艂 a d VIIIP r x l a d VIII

Erytrozynian 3-decyIoksymetyIo-1-metyIoimidazoliowy3-decyloxymethyl-1-methylimidazolium erythrosinate

Do kolby okr膮g艂odennej, zaopatrzonej w mieszad艂o magnetyczne, wprowadzono 0,004 mola soli 3 erytrozyny rozpuszczonej w 30 cm3 wody destylowanej i dodano 0,008 mola chlorku 3-decyloksymetyIo-16To a round-bottomed flask equipped with a magnetic stirrer, 0.004 mol of erythrosine salt 3 dissolved in 30 cm 3 of distilled water was introduced and 0.008 mol of 3-decyloxymethyl-16 chloride was added.

PL 212 902 B1 3 PL 212 902 B1 3

-metyloimidazoliowy rozpuszczonego w 20 cm3 wody destylowanej. Reakcj臋 prowadzono przez 24 3 godziny w temperaturze 298K. Po odparowaniu wody. pozosta艂o艣膰 rozpuszczono w 20 cm3 chloroformu i przemywano wod膮 destylowan膮 do momentu ca艂kowitego usuni臋cia chlorku sodu z fazy chloroformowej. Zawarto艣膰 jon贸w chlorkowych sprawdzano za pomoc膮 wodnego roztworu azotanu (V) srebra. Po usuni臋ciu rozpuszczalnika z fazy organicznej, pozosta艂o艣膰 suszono w temperaturze 353K pod obni偶onym ci艣nieniem. Czysto艣膰 otrzymanego zwi膮zku okre艣lono na podstawie miareczkowania dwufazowego (PN-EN-ISO-2871-1) uzyskuj膮c zawarto艣膰 substancji kationowo czynnej 87,5掳C.-methylimidazolium dissolved in 20 cm 3 of distilled water. The reaction was carried out for 24 three hours at a temperature of 298K. After the water has evaporated. the residue was dissolved in 20 cm 3 of chloroform and washed with distilled water until the sodium chloride was completely removed from the chloroform phase. The content of chloride ions was checked with an aqueous solution of silver nitrate. After removing the solvent from the organic phase, the residue was dried at 353K under reduced pressure. The purity of the obtained compound was determined on the basis of two-phase titration (PN-EN-ISO-2871-1), obtaining the cationic active substance content of 87.5 掳 C.

Struktur臋 zwi膮zku potwierdzono wykonuj膮c analiz臋 elementarn膮 CHN dla C50H65I4N4O7 (M = 1341,69):The compound structure was confirmed by elemental CHN analysis for C50H65I4N4O7 (M = 1341.69):

warto艣ci wyliczone w %: C = 44,76: H = 4,88: N = 4,18: warto艣ci otrzymane w %: C = 44,5 1:11 = 4,65: N = 3,95.values calculated in%: C = 44.76: H = 4.88: N = 4.18: values obtained in%: C = 44.5 1:11 = 4.65: N = 3.95.

P r z y k 艂 a d IXP r x l a d IX

Erytrozynian 3-dodecyIoksymetyIo-1-metyIoimidazoliowy 3 3-dodecyloxymethyl-1-methylimidazolium erythrosinate 3

Do reaktora wprowadzono 0,004 mola soli sodowej erytrozyny rozpuszczonej w 30 cm3 wody destylowanej. Przy intensywnym mieszaniu roztworu, dodano 0,008 mola chlorku 3-dodecyIoksymetyIo3 0.004 mol of erythrosine sodium dissolved in 30 cm 3 of distilled water was introduced into the reactor. With vigorous stirring the solution was added 0.008 mol of 3-3 dodecyIoksymetyIo

-1-metyIoimidazoliowego rozpuszczonego w 20 cm3 wody destylowanej. Reakcj臋 prowadzono przez godziny w temperaturze 298K. Po odparowaniu wody. pozosta艂o艣膰 suszono w temperaturze 353K 3 pod obni偶onym ci艣nieniem. Nast臋pnie produkt rozpuszczono w 50 cm3 bezwodnego acetonu. Ods膮czono osad, a z przes膮czu odparowano rozpuszczalnik. Pozosta艂o艣膰 wysuszono w temperaturze 353K pod obni偶onym ci艣nieniem. Czysto艣膰 otrzymanego zwi膮zku okre艣lono na podstawie miareczkowania dwufazowego (PN-EN-ISO-2871-1) uzyskuj膮c zawarto艣膰 substancji kationowo czynnej 82%.-1-methylimidazolium dissolved in 20 cm 3 of distilled water. The reaction was carried out for hours at 298K. After the water has evaporated. the residue was dried at 353K 3 under reduced pressure. The product was then dissolved in 50 cm 3 of anhydrous acetone. The precipitate was filtered off and the filtrate's solvent was evaporated. The residue was dried at 353K under reduced pressure. The purity of the obtained compound was determined on the basis of a two-phase titration (PN-EN-ISO-2871-1), resulting in a cationic active substance content of 82%.

Struktur臋 zwi膮zku potwierdzono wykonuj膮c analiz臋 elementarn膮 CHN dla C54H73I4N4O7 (M = 1397,79):The compound structure was confirmed by elemental CHN analysis for C54H73I4N4O7 (M = 1397.79):

warto艣ci wyliczone w %: C = 46,40: H = 5,26: N = 4,01: warto艣ci otrzymane w %: C = 46,10: 11 = 5,05: N = 3,80.values calculated in%: C = 46.40: H = 5.26: N = 4.01: values obtained in%: C = 46.10: 11 = 5.05: N = 3.80.

P r z y k 艂 a d XP r z k 艂 a d X

Fluoresceinian 3-butoksymetylo1-meyloimidazoliowy3-Butoxymethyl-1-methylimidazolium fluoresceinate

Do kolby okr膮g艂odennej, zaopatrzonej w mieszad艂o magnetyczne, wprowadzono 0,007 mola soli 3 fluoresceiny rozpuszczonej w 30 cm3 wody destylowanej. Do roztworu dodano dwukrotny nadmiar 3 molowy chlorku 3-butoksymetylo-1-metyloimidazoliowy, rozpuszczonego w 20 cm3 wody destylowanej. Reakcj臋 prowadzono przez 24 godziny w temperaturze 298K. Po odparowaniu wody, pozosta艂o艣膰 3 suszono w temperaturze 353K pod obni偶onym ci艣nieniem. Nast臋pnie produkt rozpuszczono w 50 cm3 bezwodnego acetonu. Ods膮czono osad, a z przes膮czu odparowano rozpuszczalnik. Pozosta艂o艣膰 wysuszono w temperaturze 353 K pod obni偶onym ci艣nieniem.To a round-bottomed flask equipped with a magnetic stirrer, 0.007 moles of the salt 3 of fluorescein dissolved in 30 cm 3 of distilled water were introduced. A 2-fold excess of 3 molar 3-butoxymethyl-1-methylimidazolium chloride dissolved in 20 cm 3 of distilled water was added to the solution. The reaction was carried out for 24 hours at the temperature of 298K. After the water was evaporated, the residue 3 was dried at 353K under reduced pressure. The product was then dissolved in 50 cm 3 of anhydrous acetone. The precipitate was filtered off and the filtrate's solvent was evaporated. The residue was dried at 353 K under reduced pressure.

Struktur臋 zwi膮zku potwierdzono wykonuj膮c widmo protonowego i w臋glowego magnetycznego rezonansu j膮drowego:The structure of the compound was confirmed by performing proton and carbon nuclear magnetic resonance spectra:

13C NMR (DMSOde) 5ppm = 0,830 (t, J=4,9 Hz, 6H): 1,243 (m, 4H): 1,457 (m, 4H): 3,462 (1, J=4,3 Hz, 4H): 3,869 (s, 6H): 5,555 (s, 4H): 6,327 (t, J=1,8 Hz, 1H): 6,601 (s, 1H): 6,631 (d, J=1,2 Hz, 1H): 7,111 (d, J=1,4 Hz, 1H): 7,139 (d, J=1,6 Hz, 1H): 7,571 (1, J=3,0 Hz, 1H): 7,792 (d, 2H): 7,875 (d, 2H): 7,975 (d, J=1,8 Hz, 1H): 9,562 (s, 2H): 13 C NMR (DMSOd 6) 5ppm = 0.830 (t, J = 4.9 Hz, 6H): 1.243 (m, 4H): 1.457 (m, 4H): 3.462 (1, J = 4.3 Hz, 4H): 3.869 (s, 6H): 5.555 (s, 4H): 6.327 (t, J = 1.8 Hz, 1H): 6.601 (s, 1H): 6.631 (d, J = 1.2 Hz, 1H): 7.111 (d, J = 1.4 Hz, 1H): 7.139 (d, J = 1.6 Hz, 1H): 7.571 (1, J = 3.0 Hz, 1H): 7.792 (d, 2H): 7.875 ( d, 2H): 7.975 (d, J = 1.8 Hz, 1H): 9.562 (s, 2H):

13C NMR (DMSOd6) 5ppm = 13,497: 18,546: 30,681: 35,835: 68,766: 77,919: 102,273: 109,548: 118,641: 120,302: 121,651: 123,809: 127,060: 127,562: 128,144: 128,469: 129,530: 129,846: 130,307: 137,191: 137,679: 155,135: 168,526. 13 C NMR (DMSOd6) 5ppm = 13.497: 18.546: 30.681: 35.835: 68.766: 77.919: 102.273: 109.548: 118.641: 120.302: 121.651: 123.809: 127.060: 127.562: 128.144: 128.469: 129.530: 129.846: 130.307: 137.191: 137.679 : 155,135: 168,526.

Analiza elementarna CHN dla C38H45N4O7 (M = 669,78): warto艣ci wyliczone w %: C = 68,14: H = 6,77: N = 8,36: warto艣ci otrzymane w %: C = 67,90: H = 6,52: N = 8,15.Elemental analysis of CHN for C38H45N4O7 (M = 669.78): values calculated in%: C = 68.14: H = 6.77: N = 8.36: values obtained in%: C = 67.90: H = 6 , 52: N = 8.15.

P r z y k 艂 a d XIP r z x l a d XI

Fluoresceinian 3-decyloksymetyIo-1-metyloimidazoliowy 3 3-decyloxymetyIo-1-methylimidazolium fluoresceinate 3

W kolbie okr膮g艂odennej o pojemno艣ci 100 cm3, zaopatrzonej w mieszad艂o magnetyczne, umiesz3 czono 0,006 mola soli sodowej fluoresceiny rozpuszczonej w 30 cm3 wody destylowanej.A round bottom flask with a capacity of 100 cm 3, equipped with a magnetic stirrer, Can you czono 3 0.006 mol of sodium fluorescein dissolved in 30 cm 3 of distilled water.

Do roztworu dodano 0,012 mola chlorku 3-decyloksymetyIo-1-metyIoimidazoliowy rozpuszczonego 3 w 20 cm3 wody destylowanej. Reakcj臋 prowadzono przez 24 godziny w temperaturze 298K. Po odparowaniu wody. pozosta艂o艣膰 suszono w temperaturze 353K pod obni偶onym ci艣nieniem. Osuszony produkt roz3 puszczono w 20 cm3 bezwodnego acetonu, z uk艂adu wypad艂a s贸l nieorganiczna w postaci osadu. Po ods膮czeniu osadu, z przes膮czu odparowano rozpuszczalnik, a pozosta艂o艣膰 suszono w temperaturze 353KTo the solution was added 0.012 mol of 3-decyloksymetyIo 1 metyIoimidazoliowy 3 dissolved in 20 cm 3 of distilled water. The reaction was carried out for 24 hours at the temperature of 298K. After the water has evaporated. the residue was dried at 353K under reduced pressure. The dried product was dissolved in 3 of a size of 20 cm 3 of anhydrous acetone, dropped from the inorganic salt as a solid. After the precipitate was filtered off, the filtrate's solvent was evaporated, and the residue was dried at the temperature of 353K

PL 212 902 B1 pod obni偶ony m ci艣nieniem. Czysto艣膰 otrzymanego zwi膮zku okre艣lono na podstawie miareczkowania dwufazowego (PN-EN-ISO-2871-1) uzyskuj膮c zawarto艣膰 substancji kationowo czynnej 78%.PL 212 902 B1 under reduced pressure. The purity of the obtained compound was determined on the basis of two-phase titration (PN-EN-ISO-2871-1), obtaining the cationic active substance content of 78%.

Struktur臋 zwi膮zku potwierdzono wykonuj膮c widma protonowego i w臋glowego magnetycznego rezonansu j膮drowego:The structure of the compound was confirmed by performing proton and carbon nuclear magnetic resonance spectra:

1H NMR (DMSOde) 5ppm = 0,845 (1, J=4,5 Hz, 6H): 1,205 (m, 28H): 1,446 (m, 4H): 3,428 (t, J=4,3 Hz, 4H): 3,829 (s, 6H): 5,515 (s, 4H): 6,053 (t, J=4,3 Hz, 1H): 6,119 (s, 1H): 6,623 (d, J=4,5 Hz, 1H): 7,031 (d, J=2,2 Hz, 1H): 7,053 (d, J=1,0 Hz, 1H): 7,431 (t, J=2,4 Hz, 1H): 7,771 (d, 2H): 7,849 (d, 2H): 7,962 (d, J=3,1 Hz, 1H): 9,61 7(s, 2H): 1 H NMR (DMSOd 6) 5ppm = 0.845 (1, J = 4.5 Hz, 6H): 1.205 (m, 28H): 1.446 (m, 4H): 3.428 (t, J = 4.3 Hz, 4H): 3.829 (s, 6H): 5.515 (s, 4H): 6.053 (t, J = 4.3 Hz, 1H): 6.119 (s, 1H): 6.623 (d, J = 4.5 Hz, 1H): 7.031 (d, J = 2.2 Hz, 1H): 7.053 (d, J = 1.0 Hz, 1H): 7.431 (t, J = 2.4 Hz, 1H): 7.771 (d, 2H): 7.849 ( d, 2H): 7.962 (d, J = 3.1 Hz, 1H): 9.61 7 (s, 2H):

13C NMR (DMSOd6) 5ppm = 13,974: 22,128: 25,351: 28,681: 28,718: 28,737: 28,974: 29,002: 31,309: 35,770: 69,068: 77,887: 102,269: 109,082: 120,288: 121,641: 123,786: 127,665: 128,158: 128,455: 128,986: 129,958: 134,404: 137,386: 137,684: 141,316: 156,898: 168,642: 178,224. 13 C NMR (DMSO-d6) 5 ppm = 13.974: 22.128: 25.351: 28.681: 28.718: 28.737: 28.974: 29.002: 31.309: 35.770: 69.068: 77.887: 102.269: 109.082: 120.288: 121.641: 123.786: 127.665: 128.158: 128.455: 128.986: 129.958: 134.404: 137.386: 137.684: 141.316: 156.898: 168.642: 178.224.

Analiza elementarna CHN dla C50H69N4O7 (M = 838,10): warto艣ci wyliczone w %: C = 71,65: H = 8,30: N = 6,68: warto艣ci otrzymane w %: C = 71,47: H = 8,13: N = 6,45.CHN elemental analysis for C50H69N4O7 (M = 838.10): values calculated in%: C = 71.65: H = 8.30: N = 6.68: values obtained in%: C = 71.47: H = 8 , 13: N = 6.45.

P r z y k 艂 a d XIIP r x l a d XII

Fluoresceinian 3-dodecyIoksymetyIo-1-metyloimidazoliowy 3 3-dodecyloxymetyIo-1-methylimidazolium fluoresceinate 3

Do reaktora wprowadzono 0,006 mola soli fluoresceiny rozpuszczonej w 30 cm3 wody destyIowanej. Do roztworu dodano 0,013 mola chlorku 3-dodecyloksymetyIo-1-metyloimidazoliowy rozpusz3 czonego w 20 cm3 wody destylowanej. Reakcj臋 prowadzono przez 24 godziny w temperaturze 298K.0.006 mol of fluorescein salt dissolved in 30 cm 3 of distilled water was introduced into the reactor. To the solution was added 0.013 mol of 3-dodecyloksymetyIo-1-3-methylimidazolium dissolving baggage as 20 cm 3 of distilled water. The reaction was carried out for 24 hours at the temperature of 298K.

Po odparowaniu wody, pozosta艂o艣膰 suszono w temperaturze 353K pod obni偶onym ci艣nieniem. Na3 st臋pnie produkt rozpuszczono w 50 cm3 bezwodnego acetonu, ods膮czono osad, a z przes膮czu odparowano rozpuszczalnik. Pozosta艂o艣膰 wysuszono w temperaturze 353K pod obni偶onym ci艣nieniem.After water was evaporated, the residue was dried at 353K under reduced pressure. 3 was then dissolved in 50 cm 3 of anhydrous acetone, the precipitate was filtered off, and the filtrate solvent was evaporated. The residue was dried at 353K under reduced pressure.

Czysto艣膰 otrzymanego zwi膮zku okre艣lono na podstawie miareczkowania dwufazowego (PN-EN-ISO-2871-1) uzyskuj膮c zawarto艣膰 substancji kationowo czynnej 98,5%.The purity of the obtained compound was determined on the basis of a two-phase titration (PN-EN-ISO-2871-1), resulting in a cationic active substance content of 98.5%.

Struktur臋 zwi膮zku potwierdzono wykonuj膮c analiz臋 elementarn膮 CHN dla C54H77N4O7 (螠 = 894,21):The compound structure was confirmed by elemental CHN analysis for C54H77N4O7 (螠 = 894.21):

warto艣ci wyliczone w %: C = 72,53: H = 8,68: N = 6,27: warto艣ci otrzymane w %: C = 72,30: 11 = 8,45: N = 6,05.values calculated in%: C = 72.53: H = 8.68: N = 6.27: values obtained in%: C = 72.30: 11 = 8.45: N = 6.05.

Claims (3)

1. Barwne sole imidazoliowe o wzorze og贸lnym 1, w kt贸rym R1 oznacza proton lub brom, Iub1. Colored imidazolium salts of the general formula, in which R 1 is a proton or bromine, or 234 jod, Iub grup臋 nitrow膮, R2 oznacza proton lub brom, Iub jod, R3 oznacza proton lub brom, lub jod, R4 5 oznacza proton lub brom, Iub jod, Iub grup臋 nitrow膮, R5 oznacza prosto艂a艅cuchow膮 grup臋 alkilow膮 zawieraj膮c膮 od 2 do 12 atom贸w w臋gla.234 iodine, or nitro group, R 2 is proton or bromine, or iodine, R 3 is proton or bromine or iodine, R 4 5 is proton or bromine, or iodine, or nitro group, R 5 is straight chain alkyl group containing from 2 to 12 carbon atoms. 11 2. Spos贸b wytwarzania barwnych soli imidazoliowych o wzorze og贸lnym 1, w kt贸rym R1 ozna23 cza proton lub brom, Iub jod, Iub grup臋 nitrow膮, R2 oznacza proton lub brom, Iub jod, R3 oznacza pro45 ton lub brom, Iub jod, R4 oznacza proton lub brom, Iub jod, Iub grup臋 nitrow膮, R5 oznacza prosto艂a艅cuchow膮 grup臋 alkilow膮 zawieraj膮c膮 od 2 do 12 atom贸w w臋gla, znamienny tym, 偶e halogenki imida5 zoliowe o wzorze og贸lnym 2, w kt贸rym R5 oznacza prosto艂a艅cuchow膮 grup臋 alkilow膮, zawieraj膮c膮 od 1 Process for the preparation of colored imidazolium salts of general formula I, wherein R 1 is a proton or bromine, or iodine, or a nitro group, R 2 is a proton or bromine, or iodine, R 3 is propton or bromine, or iodine, R 4 is a proton or bromine, Iub iodine, Iub nitro, R 5 is a straight chain alkyl group containing from 2 to 12 carbon atoms, characterized in that the halides imidazole 5 zoliowe of general formula 2 wherein R 5 is a straight chain alkyl group, containing from 1 2 do 12 atom贸w w臋gla, poddaje si臋 reakcji z sol膮 organiczn膮 o wzorze og贸lnym 3, w kt贸rym R1 ozna23 cza proton lub brom, Iub jod, Iub grup臋 nitrow膮, R2 oznacza proton lub brom, lub jod, R3 oznacza proton lub brom, Iub jod, R4 oznacza proton lub brom, lub jod, lub grup臋 nitrow膮, M oznacza kation potasu lub sodu, Iub amoniowy, w stosunku molowym 2:1 w temperaturze od 298K do 353K, korzystnie2 to 12 carbon atoms are reacted with an organic salt of the general formula 3 in which R 1 is proton or bromine, or iodine, or a nitro group, R 2 is a proton or bromine or iodine, R 3 is a proton or bromine , Or iodine, R 4 is a proton or bromine or iodine or a nitro group, M is a potassium or sodium or ammonium cation, in a molar ratio of 2: 1 at a temperature of 298K to 353K, preferably 298K, w 艣rodowisku wodnym, nast臋pnie odparowuje si臋 rozpuszczalnik w warunkach obni偶onego 3 ci艣nienia w temperaturze od 293 K do 353K, korzystnie 318 K, dodaje 50 cm3 bezwodnego acetonu, po czym oddziela si臋 osad, odparowuje aceton i suszy w warunkach obni偶onego ci艣nienia w temperaturze od 303K do 373K.298K in an aqueous medium, and then the solvent is evaporated under reduced 3 pressure at a temperature of 293 K to 353K, preferably 318 K, adding 50 cm 3 of anhydrous acetone, and the precipitate is separated, evaporated acetone and dried under reduced pressure at a temperature of from 303K to 373K. 11 3. Spos贸b wytwarzania barwnych soli imidazoliowych o wzorze og贸lnym 1, w kt贸rym R1 ozna23 cza proton lub brom, lub jod, lub grup臋 nitrow膮, R2 oznacza proton lub brom, Iub jod, R3 oznacza pro45 ton lub brom, Iub jod, R4 oznacza proton lub brom, Iub jod, Iub grup臋 nitrow膮, R5 prosto艂a艅cuchow膮 grup臋 alkilow膮 zawieraj膮c膮 od 2 do 12 atom贸w w臋gla, znamienny tym, 偶e halogenki imidazoliowe 5 o wzorze og贸lnym 2, w kt贸rym R5 oznacza prosto艂a艅cuchow膮 grup臋 alkilow膮 zawieraj膮c膮 od 2 do 12 1 atom贸w w臋gla, poddaje si臋 reakcji z sol膮 organiczn膮 o wzorze og贸lnym 3, w kt贸rym R1 oznacza pro23 ton lub brom, Iub jod, Iub grup臋 nitrow膮, R2 oznacza proton lub brom, Iub jod, R3 oznacza proton lubProcess for the preparation of colored imidazolium salts of the general formula I, wherein R 1 is a proton or bromine or iodine or a nitro group, R 2 is a proton or bromine, or iodine, R 3 is propon or bromine, or iodine, R 4 is a proton or bromine, Iub iodine, Iub nitro, R 5 straight chain alkyl group containing from 2 to 12 carbon atoms, characterized in that halides, imidazolium 5 of formula 2 wherein R 5 is a straight chain alkyl group having from 2 up to 12 1 carbon atoms, is reacted with an organic salt of the general formula 3 in which R 1 is propton or bromine, or iodine, or a nitro group, R 2 is a proton or bromine, or iodine, R 3 is a proton or PL 212 902 B1 brom, lub jod, R4 oznacza proton lub brom, lub jod, Iub grup臋 nitrow膮, M oznacza potas lub s贸d, Iub amon, w stosunku molowym 2:1 w temperaturze od 298K do 353K, korzystnie 298K, w 艣rodowisku 3 wodnym, nast臋pnie dodaje si臋 20 cm3 hydrofobowego rozpuszczalnika organicznego, po czym przep艂ukuje si臋 warstw臋 organiczn膮 wod膮 destylowan膮 do momentu zaniku jon贸w halogenowych w odcieku, dalej odparowuje si臋 rozpuszczalnik w warunkach obni偶onego ci艣nienia w temperaturze powy偶ej 298 K i suszy w warunkach obni偶onego ci艣nienia w temperaturze powy偶ej 298K.PL 212 902 B1 bromine or iodine, R 4 is a proton or bromine or iodine, or a nitro group, M is potassium or sodium, or ammonium, in a molar ratio of 2: 1 at a temperature of 298K to 353K, preferably 298K, in the environment 3 with water, then 20 cm 3 of hydrophobic organic solvent are added, then the organic layer is rinsed with distilled water until the disappearance of halogen ions in the effluent, the solvent is further evaporated under reduced pressure at a temperature above 298 K and dried under reduced pressure at a temperature of above 298K.
PL382868A 2007-07-09 2007-07-09 Colourful imidazol salts and production method of colourful imidazol salts PL212902B1 (en)

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