GB2037284A - Benzothiazole compositions - Google Patents

Benzothiazole compositions Download PDF

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GB2037284A
GB2037284A GB7940882A GB7940882A GB2037284A GB 2037284 A GB2037284 A GB 2037284A GB 7940882 A GB7940882 A GB 7940882A GB 7940882 A GB7940882 A GB 7940882A GB 2037284 A GB2037284 A GB 2037284A
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F3/00—Compounds of beryllium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/005—Preparation involving liquid-liquid extraction, absorption or ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/10—Preparation or treatment, e.g. separation or purification
    • C01F17/17—Preparation or treatment, e.g. separation or purification involving a liquid-liquid extraction
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F5/00—Compounds of magnesium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G11/00—Compounds of cadmium
    • C01G11/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G15/00—Compounds of gallium, indium or thallium
    • C01G15/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G21/00—Compounds of lead
    • C01G21/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G29/00—Compounds of bismuth
    • C01G29/003—Preparations involving a liquid-liquid extraction, an adsorption or an ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G30/00—Compounds of antimony
    • C01G30/001—Preparation involving a solvent-solvent extraction, an adsorption or an ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G37/00—Compounds of chromium
    • C01G37/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G39/00—Compounds of molybdenum
    • C01G39/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/0009—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G55/00—Compounds of ruthenium, rhodium, palladium, osmium, iridium, or platinum
    • C01G55/001—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/15—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/64—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2
    • C07D277/66—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2 with aromatic rings or ring systems directly attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/34—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing sulfur, e.g. sulfonium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

A compound, having chelating and fluorescent properties, has the formula <IMAGE> wherein R<1>, R<2> and R<3> are the same or different and are hydrogen or linear or branched alkyl groups having from 1 to 4 carbon atoms, and R<4> is either hydrogen or tertiary butyl, provided that when R<4> is hydrogen, at least two of R<1>, R<2> and R<3> are alkyl, or when R<4> is tertiary butyl at least one of R<1>, R<2> and R<3> is alkyl. A method of preparing the compound is described.

Description

SPECIFICATION Benzothiazole compositions The invention relates to a benzothiazole compound having the following structure:
Wherein R', R2 and R3 are the same or different and are hydrogen or a linear or branched alkyl group having 1-4 carbon atoms and R4 is either hydrogen or tertiary butyl provided that when R4 is hydrogen, at least two of said groups B1 through R3 are alkyl groups or when B4 is tertiary butyl at least one of said groups R' through R3 is an alkyl group.
The aforesaid composition possesses a tendency for chelation and a strong capacity for fluorescence.
Of the many hydroxyphenylbenzothiazoles known in the literature, two are known to have two alkyl substituents on the phenyl ring. One is an isomer of 2-(2-benzothiazolyl)-4,6-bis(1 1 -dimethylethyl)phenol, one of the preferred species of the invention, and is 4-(2-benzothiazolyl)-2,6-bis(1 , 1 -dimethylethyl (phenol.
The latter compound is disclosed in Germay Patent Publication No. 2,008,414. We have found that the compounds of the present invention are superior in chelating ability to an isomer such as the compound of the cited German Patent. Other benzothiazolylbis (1,1-dimethylethyl)phenols are not known in the literature at the present time.
Another benzothiazolyl dialkyiphenol, 2-(2-benzOthiazolyl)-6-(1,1-dimethylethyl)-3-methylphenol, has been reported in the Journal of Physical Chemistry 74, #26,4473(1970). The compounds of the present invention are far superior to this compound as a fluorescing agent. Fluorescent compounds are used as optical brightners.
This invention is concerned with new compositions of matter which have been found to possess chelating properties. These compositions have also been found to possess very strong fluorescent capabilities.
Generally the composition of the present invention possesses the following structure.
wherein R1, R2 and R3 are the same or different and are hydrogen or a linear or branched alkyl group having 1-4 carbon atoms and R4 is either hydrogen or tertiary butyl, provided that when R4 is hydrogen, at least two of said groups R' through R3 are alkyl groups or when R4 is tertiary butyl at least one of said groups R through R3 is an alkyl group.
The preferred compound of this invention is 2-(2-benzothiazolyl)-4,6-bis(1,1 -dimethylethyl)phenol having the following structure.
This compound has not been reported in the literature.
Other than the above two compounds disclosed in the above-noted German reference and the Journal of Physical Chemistry no benzothiazolyl dialkyl phenols have been found in the literature.
There are numerous references in the literature to the preparation of benzothiazoles of this type. Two of the most pertinent are H.B. Freyermuth, U.S. 3,669,979 and R.F. Smith, U.S. 3,647,812. Both of these patents involve preparation of benzothiazoles by reacting an o-aminothiophenol with an aromatic acid in the presence of phosphorus trichloride. These methods have been adapted for preparation of the novel compounds of the present invention.
The following example shows the detailed preparation of the preferred composition
Example I Preparation of 2-(2-benzothiazolyl)-4,6-bis(1 ,1 -dimethylethyl)phenol 3,5-bis(1,1 -dimethylethyl)sa licylic acid (4519, 1.8 mole) and 255 g, 1.8 mole) 2-aminothiophenol were dissolved in 1800 ml of toluene. Phosphorus trichloride (246 g, 1.8 mole) was then added dropwise maintaining a reaction temperature of 55 C. When the evolution of HC1 subsided, the solution was refluxed (115 C) for four hours, cooled, and decanted from a viscous oil which remained in the flask. The toluene solution was concentrated to a viscous oil. The oil was warmed and dissolved in isopropyl alcohol. Upon cooling, the product crystallized out.Recrystallization from isopropyl alcohol followed by a cold isopropyl alcohol wash gave 425 g (70% yield) of pure pale yellow crystals, m.p. 112-1 140C. IR and NMR data confirm the structure.
Anal. Calc'd. for C27 H25NOS: C, 74.31; H, 7.42; N, 4.13.
Found: C, 74.30; H, 7.31; N, 4.16.
The starting acid, 3,5-bis(1,1 -dimethylethyl) salicylic acid, is not readily available, but can be prepared by the method of W.H. Meek and C.H. Fuchsman, J. Chem. and Eng. Data, (3), 388-91(1969). A detailed preparation is described in Example II hereinafter.
Example II Sodium metal (69.0g, 3.0 mole) was dissolved in 1500 ml of ethanol, and a solution of 206g (1.0 mole) 2,4-bis (1,1-dimethylethyl)phenol in 500 ml of ethanol was added in one portion. Carbon dioxide (150g, 3.3 mole) was bubbled through the solution at 55"C. The reaction mixture became quite thick with precipitate during the addition which required 1 hour and 45 min.
N,N-Dimethylacetamide (500ml) was added, and solvent was distilled off until a reaction temperature of 180"C was reached. For best results the temperature should be monitored carefully and very thorough agitation is required. The 1 80"C temperature was held for 1 hour and 15 minutes during which periodic removal of solvent was necessary. The mixture was then cooled to 90"C. Water (2500 ml) was added and the mixture extracted with three 500 ml portions oftoluene. The aqueous layer was made acidic with concentrated hydrochloric acid, and the resulting oil was taken up in ether. The solution was dried over anhydrous magnesium sulfate.Evaporation of the ether gave a crude solid which, after recrystallization from acetonitrile, melted at 162 - 1 64"C, wt. 1 44g (58%).
Example Ill Using essentially the methods described in Examples I and II above, the following compounds are prepared: wherein R1 R2 R3 R4 C1 C1 C1 tert-C4 iso-C3 C1 iso-C3 tert-C4 tert-C4 C2 iso-C3 tert-C4 tert-C4 tert-C4 tert-C4 H iso-C3 C2 tert-C4 tert-C4 iso-C3 C1 iso-C3 H tert-C4 iso-C3 tert-C4 H iso-C3 iso-C3 iso-C3 H It has been determined that the compositions of the present invention have the ability to form a complex with metal ions and remove them from aqueous solution. These compositions are much more effective at doing this than the closest prior art compounds.
The chelating ability has been with copper ions (preferred) but the procedure may also be adaptable to other ions such as Bi3+, Be2+, Mg2+, Ca2+, Sr2+, Ba2+, Zn2+, Cd2+, Al3+, Ga3+, ln3+, Tl3+, Yet3+, Lea3', Pb2+, Sub3"+ Cr3+, B3+,MoO22+, Mn2+, Fe3+, Co2+, Ni2+, Pd2+, Ce3+, Pr3+.
The metal ions can be removed from aqueous solutions of very dilute concentration. Concentrations of approximately 800 ppm were used although concentrations as low as 1 ppm or less could be employed. Also higher concentrations (up to 5%) could be used.
A solution of the compositions of the present invention in an organic solvent is employed for extraction purposes. Almost any solvent which will dissolve said compositions and is insoluble in water may be used.
Examples of solvents include chloroform, carbon tertrachloride, 1,2-dichloroethane, toluene, ether and ethyl acetate.
The concentration of the compositions in the solvent is not critical, but the more concentrated solutions seem to be more effective then dilute solutions. Concentration between 0.001M and saturated solutions may be used.
The pH of the solution is somewhat critical and varies with the particular ion being extracted. In the case of copper, very little is extracted below a pH of 4.5. On the other hand, if a pH above 5.3 is maintained for any length of time the copper can precipitate as the hydroxide and make extractions difficult. The pH can be adjusted by using a sodium acetate solution and small amounts of sulfuric acid.
The complex of the preferred composition of the present invention with the metal ions in the organic solvent produces a dark amber color. The complex can be readily broken with aqueous acid. Any strong material acid could be used. It was found that the complex could be more effectively broken with IN rather than with 6N hydrochloric acid.
The following example shows that the preferred composition is more efficient at removing copper from aqueous solution than the composition described in the German reference cited above.
Example IV Comparative extraction of copper The following standard solutions are prepared: 100 ml 0.1 M 2-(2-benzothiazolyl)-4,6-bis(1 ,1 - dimethylethyl)phenol (hereinafter "A") in chloroform, 100 ml 0.1 M 4-(2-benzothiazolyl)-2,6-bis(1,1- dimethylethyl)phenol (hereinafter "B") in chloroform and 0.2789 Cu Br2 in 100 ml demineralized water.
A solution of 1.0 ml 10% sodium acetate and 20.0 ml of the above copper bromide solution was prepared and extracted four times with 20 ml portions of the A solution. One drop of concentrated sulfuric acid was added to the aqueous solution and it was submitted for Atomic Absorption Analysis to determine the amount of copper which has not been extracted. The combined chloroform extracts were extracted four times with 10 ml portions of 1 N HC1 and the combined aqueous extracts were diluted to 40 ml. This solution was submitted for analysis of copper which had been extracted with A.
A similar experiment was run, extracting with the B solution in place of the A. In this case, emulsions were formed which separated slowly. Also, the chloroform extracts had to be filtered with Celite (trademark) in order to clarify the solution, thus accounting for somewhat incomplete recovery of the copper. The analogous aqueous solutions of copper were submitted for analysis.
The following table summarizes results of copper found: PPM Cu Theoretical Found & ftotal Initial CuBr2 solution 793 827 Residual Cu after A extraction 755 267 35 Residual Cu after B extraction 755 421 56 Cu extracted with A 396 286 72 Cu extracted with B 396 120 30 A repeat of the above experiment was made in order to confirm reproducibility of results. The data are shown below: PPM Cu Theoretical Found % of total Initial CuBr2 solution 791 750 Residual Cu afterAextraction 753 310 41 Residual Cu after B extraction 753 436 58 Cu extracted with A 396 279 70 Cu extracted with B 396 72 18 Fluorescent properties 2-(2-benzothiazolyl)phenols are known to be fluorescent compounds, whereas the m- and p-hydroxy derivatives show little or no fluorescence. (J. Phys. Chem. 74,4473(1970), U.S. 3,647,812 and U.S. 3,669,979).
The degree of fluorescence of 0-hydroxy derivative varies considerably depending on the additional substituents on the phenyl ring. More often that not, the presence of additional substituents decreases the amount of fluorescence of the compounds, but in the case of the prior art compound 2-(2-benzothiazolyl)-6 (1,1 dimethylethyl)-3-methylphenol (hereinafter "C"), slightly more fluorescence is observed. The fluoresc- ence of A and C were compared and it was found that A fluoresces much stronger than C. Example V shows the details of this comparison: Example V Methanol solutions of A and C were prepared at a concentration of 10.0 mg/liter (2.94 x 10-5M for A and 3.37 x 10-5M for C).These solutions were examined for fluorescent intensities with a Perkin-Elmer Model 203 Fluorescence Spectrometer, using a Xenon lamp source, two grating monochromators (one for excitation, the second for analysis), a photomultiplier, and a microammeter readout. Complete spectra were at exciting radiations of 295 nm and 330 nm, with fluorescent intensities recorded between 220 and 550 nm.
Data are given in Tables 1 and 2. These data show that A fluoresces much more intensely at all wavelengths than C.
TABLE 1 Exciting Wavelength 330 nm. Sensitivity 5, Selector X 1, % 100.
A/C Analyzers, Intensity Units Ratio nm A C Intensity/Wt./Vol. Intensity/molesil 220 < 1 -0- 250 < 1 -0- 300 1 1 350 59 44 1.3 1.5 360 70 50 1.4 1.6 370 76 47 1.6 1.8 380 82 44 1.9 2.2 390 92 46 2.0 2.3 400 110 47 2.3 2.6 410 109 47 2.3 2.6 420 109 44 2.5 2.9 430 102 39 2.6 3.0 440 91 33 2.8 3.2 450 76 27 2.8 3.2 460 63 21 3.0 3.4 470 50 16 3.1 3.6 480 40 12 3.3 3.8 490 31 9 3.4 3.9 500 25 7 3.6 4.1 510 20 5 4.0 4.6 520 17 4 4.2 4.8 530 14 2.5 5.6 6.4 540 11 2 5.5 6.3 550 9 1 9 10 560 6.5 < 1 TABLE 2 Exciting Wavelength 295 nm. Sensitivity 7, Selector X10, % 100.
A/C Analyzers, Intensity Units Ratio nm A C lntensity/Wt/Vol. * Intensity/moles/l 220 -0- -0- 250 -0- -0- 300 80 53 1.5 1.7 310 44 35 1.3 1.5 320 70 59 1.2 1.4 330 97 84 1.2 1.4 340 99 82 350 90 70 1.3 1.5 360 78 56 1.4 1.6 370 65 42 1.6 1.8 380 54 32 1.7 2.0 390 45 25 1.9 2.2 400 40 20 2.0 2.3 410 36 16 2.2 2.5 420 32 13 2.5 2.9 430 28 11 2.5 2.9 440 24 9 2.7 3.1 450 20 7 2.9 3.3 460 16 5 3.2 3.7 470 13 4 3.2 3.7 480 10 3 3.3 3.8 490 8 2 4.0 4.6 500 7 2 3.5 4.0 510 6 1 6.0 6.9 520 5 1 5.0 5.8 530 5 < 1 - 540 4 < 1 - 550 3 < 1 -

Claims (18)

1. Acompound having the formula:
wherein R1, R2 and R3 are the same or different and are hydrogen or linear or branched alkyl group having from 1 to 4 carbon atoms, and R4 is either hydrogen or tertiary butyl, provided that when R4 is hydrogen, at least two of R1, R2 and R3 are alkyl, or when R4 is tertiary butyl at least one of R1, R2 and R3 is alkyl.
2. A compound according to claim 1 wherein at least one of R1, R2 and R3 is secondary or tertiary alkyl.
3. A compound according to claim 2 wherein at least one of R1, R2 and R3 is tertiary alkyl.
4. A compound according to any of the preceding claims wherein R4 is hydrogen.
5. A compound according to claim 4 wherein at least two of R1, R2 and R3 are secondary or tertiary alkyl.
6. A compound according to claim 5 wherein R1 and R3 are tertiary butyl and R2 is hydrogen.
7. 2-(2-benzothiazolyl )-4,6-bis(1 ,1 -dimethylethyl)phenol.
8. A method for chelating metal ions from aqueous solution, the method comprising contacting the aqueous solution with a compound as claimed in any of the preceding claims.
9. A fluorescent composition comprising a compound as claimed in any of claims 1 to 7 and a carrier or dilutent therefor.
10. A method of preparation of a compound as claimed in claim 1 comprising reacting a compound of the formula
with a compound of the formula
in the presence of phosphorus trichloride, where R1, R2, R3 and R4 are as defined in claim 1.
11. A compound according to claim 1 and substantially as herein described.
12. A compound according to claim 1 and substantially as described in any of Examples I to Ill.
13. A method according to claim 8 and substantially as herein described.
14. A method for chelating metal ions from aqueous solution substantially as described in Example III or Example IV.
15. A fluorescent composition according to claim 9 and substantially as herein described.
16. A fluorescent composition according to claim 9 and substantially as described in Example V.
17. A method according to claim 10 and substantially as herein described.
18. A method of preparation of a compound as claimed in claim 1 substantially as described in any of Examples I to Ill.
GB7940882A 1978-11-27 1979-11-27 Benzothiazole compositions Expired GB2037284B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5858560A (en) * 1993-11-09 1999-01-12 Shinko Electric Industries Co., Ltd. Organic material for el device and el device
US6083634A (en) * 1994-09-12 2000-07-04 Motorola, Inc. Organometallic complexes for use in light emitting devices

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH516339A (en) * 1969-03-03 1971-12-15 Ciba Geigy Ag Use of azole compounds as antioxidants
US3928617A (en) * 1973-11-30 1975-12-23 Uniroyal Inc Control of acarids using certain benzothiazoles or benzothiazolines

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5858560A (en) * 1993-11-09 1999-01-12 Shinko Electric Industries Co., Ltd. Organic material for el device and el device
US6083634A (en) * 1994-09-12 2000-07-04 Motorola, Inc. Organometallic complexes for use in light emitting devices

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DE2947525A1 (en) 1980-06-04
JPS5573673A (en) 1980-06-03
FR2442233A1 (en) 1980-06-20
IT7969281A0 (en) 1979-11-26
AU5316679A (en) 1980-05-29
BR7907646A (en) 1980-08-05
GB2037284B (en) 1983-05-05
AR224881A1 (en) 1982-01-29

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