Nitrogen-containing oxacalixarene and calixarene derivatives, polymers including groups related to such derivatives, polymers including groups related to such derivatives, and use of such compounds

Abstract: The application described a nitrogen-containing oxacalixarene or calixarene derivative of formula I: wherein m′ + m″ = 0-8 n = 0-8 m¹ ≧ 1/₂ (m′ + m″) 3 ≦ m′ + m″ + n ≦ 8 if n = 0, m′ + m″ ≧ 4 R³ is H, halogen, or hydrocarbyl, aryl, hydrocarbylaryl or a substituted derivative thereof and R³ may be the same or different on each aryl group; R¹ and R¹⁵ which may be the same or different are H or hydrocarbyl, aryl, hydrocarbylaryl or a substituted derivative thereof; R² is selected from: R⁴ which is H, or hydrocarbyl, aryl, hydrocarbylaryl or a substituted derivative thereof, wherein R⁵ and R⁶ which may be the same or different are H, or hydrocarbyl, aryl, hydrocarbylaryl, or a substituted derivative thereof, -OR¹, wherein R¹ is as defined above and R¹⁷ which is a residue of a hydrocarbyl, aryl, or hydrocarbylaryl group or of a substituted derivative thereof providing a bond to another oxacalixarene or calixarene derivative of formula I wherein R² is R¹⁷. The derivatives may be polymer-bound. Use of the derivatives for sequestration of metals is also described.

Description: This invention relates to the use of nitrogen-containing oxacalixarene and calixarene derivatives and polymers including groups related to such derivatives for the sequestration of metals. U.S. Patents 4556700 and 4642362 Harris et al ., describe certain calixarene derivatives. McKervey et al ., J. Chem. Soc. Commun. 1985 p388 describes the cation transfer properties of alkyl calixaryl acetates. Olmstead et al ., J. Am. Chem. Soc., 1985, 107 , 8087-8091, describe complexes of p-tert.-Butylcalix[4]arene with the transition metals Titanium (IV), Iron (III) and Cobalt (II). Izatt et al ., J. Am. Chem. Soc., 1985 107 , 63-66 describe cation transport from multiple alkali metal cation mixtures using a liquid membrane system containing a series of calixarene carriers, specifically p- tert .-butylcalix[4]arene, - calix[6]arene, and -calix[8]arene and p.- tert .-pentylcalix[4]arene, -calix[6]arene and -calix[8]arene. Calestani et al ., J. Chem. Soc., Chem. Commun., 1987 P344 describe the diethylacetamide of p.- tert .-butylcalix(4)arene and the use of this compound in sequestering alkali metals. EP-A-0237265 (Loctite (Ireland) Limited) describes certain nitrogen-containing calixarene derivatives and their use in sequestering transition metals selectively. The present invention provides use of oxacalixarene and calixarene derivatives of formula (I): wherein m' + m'' = 0-8 n = 0-8 m' ≧ 1/2 (m' + m'') 3 ≦ m' + m'' + n ≦ 8 if n = 0, m' + m'' ≧ 4 R³ is H, halogen, or C₁-C₁₀ aliphatic hydrocarbyl, C₆-C₂₀ aryl, C₆-C₂₀ aliphatic hydrocarbylaryl or a derivative thereof substituted by one or more halo groups or substituted or interrupted by one or more oxo groups and R³ may be the same or different on each aryl group; R¹ and R¹⁵ which may be the same or different are H or C₁-C₁₀ aliphatic hydrocarbyl, C₆-C₂₀ aryl, C₆-C₂₀ aliphatic hydrocarbylaryl or a derivative thereof substituted by one or more halo groups or substituted or interrupted by one or more oxo groups; R² is selected from: R⁴ which is H, or C₁-C₁₀ aliphatic hydrocarbyl, C₆-C₂₀ aryl, C₆-C₂₀ aliphatic hydrocarbylaryl or a derivative thereof substituted by one or more halo groups or substituted or interrupted by one or more oxo groups, wherein R⁵ and R⁶ which may be the same or different are H, or C₁-C₁₀ aliphatic hydrocarbyl, C₆-C₂₀ aryl, C₆-C₂₀ aliphatic hydrocarbylaryl, or a derivative thereof substituted by one or more halo groups or substituted or interrupted by one or more oxo groups, -OR¹, wherein R¹ is as defined above and R¹⁷ which is a residue of a C₁-C₁₀ aliphatic hydrocarbyl, C₆-C₂₀ aryl, or C₆-C₂₀ aliphatic hydrocarbylaryl group or of a derivative thereof substituted by one or more halo groups or substituted or interrupted by one or more oxo groups providing bond to another oxacalixarene or calixarene derivative of formula 1 wherein R² is R¹⁷; or a polyamide polymer having a plurality of calixarene groups bound thereon, of the formula (XIII) wherein x > 1, m' ≧ 2, m' + m'' ≧ 4 and R³, R¹⁵, and R¹⁷, are as defined above; for the sequestration of metals other than alkali metals. The use according to the invention generally involves a method of sequestering metals other than alkali metals which comprises contacting a metal-containing medium with an oxacalixarene or calixarene derivative of formula I, or a polymer bound calixarene of formula (XIII) as defined above. In one aspect, the use according to the present invention involves amide-functional oxacalixarene derivatives of formula I above wherein n is at least 1 and R² is R⁴. Preferred oxacalixarene derivatives for the use according to the invention are (i) an oxacalix-4-arene of formula (ii) a dioxacalix-4-arene of formula (iii) a trioxacalix-3-arene of formula wherein R¹⁶ is -CH₂C(O)N(R¹)(R⁴), and R¹, R³ and R⁴ are as defined above. These amide-functional oxacalixarene derivatives, as well as the amide functional calixarene derivatives of formula I wherein m'' = n = 0 and R² is R⁴, have the surprising capability of sequestering transition metals such as copper and silver, transition series elements such as manganese, alkaline earth elements such as calcium and magnesium, and Group III elements such as aluminium in addition to alkali metals. In another aspect the present invention involves the use of oxacalixarene and calixarene hydrazide ester derivatives of formula I wherein R² is and oxacalixarene and calixarene hydroxamic acid derivatives of formula I wherein A² is -OR¹. These compounds are selective sequestration agents in that they sequester transition metals such as copper but not alkali metals such as sodium. In a further aspect, the invention involves the use of a polyamide polymer having a plurality of calixarene groups bound thereon, of the formula (XIII) wherein x > 1, m' ≧ 2, m' + m'' ≧ 4 and R³, R¹⁵, and R¹⁷, are as defined above. Such a polyamide may be prepared by reacting a calixarene derivative having at least two acid chloride groups with a polyaminoalkane by methods known per se . In the above compounds of formula I - IV and XIII, the aliphatic hydrocarbyl groups preferably contain from 1 to 5 carbon atoms and the aryl and aliphatic hydrocarbylaryl groups preferably contain from 6 to 10 carbon atoms. Aliphatic hydrocarbyl groups are preferred, especially alkyl or alkenyl groups. Halo substituents may be chlorine, bromine, fluorine or iodine. The preferred calixarene or oxacalixarene derivatives of formula I are those in which m'' = 0. The preparation of calixarene derivatives is known and is described, for example, in C. Gutsche et al ., Acc. Chem. Res., 16 , 161-170 (1983); in U.S. Patent 4556700 Harris et al ., and in J. Inclusion Phenomena 2 , 199-206 (1984) D. Reidel Publishing Company. The preparation of aryl calixarene derivatives is described in European Patent Application No. 0259016 and equivalent applications in other countries. Mixed functionality calixarene derivatives are described in European Patent Application No. 0196895 A2 and U.S. Patent 4642362 Harris et al . When m'' is greater than or equal to 2 in the compounds of formula I, the aryl groups having the -O-R¹⁵ side chain may be interspersed around the ring between the aryl groups having the OCH₂C (O) N(R¹)(R²)side chain. In the oxacalixarene derivatives of formula I when (m' + m'') and n are greater than 2, the methylene and ether bridges may or may not alternate within the oxacalixarene molecule. Oxacalixarene compounds may be readily synthesised by methods described in C. Gutsche et al ., J. Am. Chem. Soc. 103 , 3782 (1981); B. Dhawan et al ., J. Org. Chem. 48 , 1536 (1983) and U.S. Patent 4098717 Buriks et al . Etherified oxacalixarenes of formula I may be produced by reacting a phenolic oxacalixarene with a halomethyl acetone or a haloalkyl acetate. Potassium iodide may be added to accelerate etherification. This method of production and the etherified oxacalixarenes are the subject of Irish Patent Application No. 153/87 filed 21 January 1987 (European Patent Application No. 0,279,521). Amide - functional calixarenes and oxacalixarenes of formula I may be prepared by methods described in G. Calestani et al., J. Chem. Soc., Chem. Commun., 1987, 344. Description of the Preferred Embodiments The invention is illustrated in the following Examples:- EXAMPLE 1 Preparation: Acid Hydrazide of p-t-Butylcalix-4-arene 2.48g of the tetraethyl acetate of p-t-butyl calix-4-arene prepared as in U.S. Patent 4556700 by S. Harris et al Loctite (0.0025 mole) was treated with hydrazine mono-hydrate 10g (0.2 mole) following procedure given in Vogels Textbook of Practical Organic Chemistry 4th Edition revised by B.S. Furniss, A.J. Hannaford, V. Rogers, P.W.G. Smith and A.R. Tatchell, Longman Publishers, London and New York, 1978 page 1125. After gentle reflux for 15 minutes just enough absolute ethanol was added through the condenser to produce a clear solution which was then refluxed for a further 3 hours. After cooling colourless shiny platelets of hydrazide ester were formed which were filtered off-yield 2.5g (95%) - which were recrystallised from absolute ethanol to give high purity product m.p.> 280°C characterised by i.r. spectroscopy and elemental analysis as i.r. spectroscopy results =ν 3300 (m)NH, 1668 (S) C=O Elemental Analysis results: (Calc'd for C₅₂H₇₂O₈N₈ C : 66.63, H : 7.76, N : 11.96, O : 13.66; Found C : 65.80, H : 7.61, N : 11.68, O : 13.06). EXAMPLE 2 Preparation: Diacid Hydrazide of the Diallyl ether of p-t-Butylcalix-4-arene 0.73g of the diallylether of the diethylacetate of p-t-butylcalix-4-arene prepared as in U.S. Patent 4,642,362 by S. Harris et al Loctite (0.0008 mole) was treated with hydrazine monohydrate 1.5g (0.03 mole) and the same procedure followed as in Example 1 to give 0.7g (94%) as a colourless solid recrystallised from absolute ethanol to give colourless crystalline product m.p. 242-5°C characterised by i.r. spectroscopy and elemental analysis as i.r. spectroscopy results =ν 3325 (m)NH, 1672 (S) C = O Elemental Analysis results: (Calc'd for C₅₄H₇₂O₆N₄ C : 74.28, H : 8.31, N : 6.42, O: 10.99; Found C : 74.71, H:8.47, N : 6.44, O : 10.87). EXAMPLE 3 Preparation and isolation of Cupric picrate-Dihydrazide Calixarene Complex A 5% methanolic solution of dihydrazide from Example 2 was added to 5% methanolic solution of cupric picrate prepared following a procedure of R.C. Aggarwal and N.K. Singh, Def. Sci. J. 25(4) 1975 p153 to give a pale green precipitate which was washed several times with hot methanol and dried under vacuum to give a pale green solid which was confirmed to be the hydrazide cupric picrate complex by i.r. spectroscopy and elemental analysis. The solid did not melt up to 265°C. The complex is probably of the following structure: ref. Vol. 2 p1051 in Comprehensive Organic Chemistry, "The synthesis and Reactions of Organic Compounds" by D. Barton and W.D. Ollis. Edited by I.O. Sutherland Pergamon Press. i.r. spectroscopy results = ν 1650 sh(m) 1630 sh(s) 1610(s) C = O, C ····· C Elemental Analysis results : (Calc'd for C₆₆H₈₀O₂₂N₁₀Cu C : 55.47, H : 5.64, N : 9.80, O : 24.63, Cu : 4.44; Found C : 55.11, H : 5.55, N : 9.60, O : 23.86, Cu 4.56). EXAMPLE 4 Preparation Hydroxamic Acid Calixarene To a cooled solution of 1.8g of the tetraethylacetate of p-t-butylcalix-4-arene prepared by U.S. Patent 4556700 S. Harris et al Loctite (0.0073 mole) and 2.02 g (0.029 mole) hydroxylamine hydrochloride in a mixture of 80 mls methanol and 40 mls THF was added a solution of 2.04g (0.036 mole) KOH in a mixture of 24 ml methanol and 12 ml THF dropwise at -5°C following a method of A. Liguori in Gaz. Chim. Ital 116 1986 p379. The reaction mixture was then stirred for 5 hrs at -5°C and then 5 days at room temperature. All volatiles were then removed under vacuum and dilute acetic acid was added to the residue to give 1.5g product which was recrystallised with dichloromethane to give colourless crystalline shiny platelets product, m.p. 198-200°C characterised by i.r. spectroscopy and elemental analysis as i.r. spectroscopy results = ν 3230 (m)NH, 1655 (S) C = O Elemental Analysis results : (Calc'd for C₅₂H₆₈O₁₂N₄ C : 66.36, H : 7.28, O : 20.40; Found : C : 64.59, H : 7.57, O : 20.35). EXAMPLE 5 0.29g of the ethyl acetate of p-t-butylpseudocalix-4-arene (prepared as in Irish Application 153/87 Loctite (Ireland) Limited, EP-A-0 279 521). (0.00028 mole) was added to 1.1g of hydrazine hydrate (0.022 mole) and the entire was refluxed for twenty minutes following method of Vogel Practical Organic Chemistry 4th Edition revised by B. S. Furniss, A. J. Hannaford, V. Rogers, P. W. G. Smith and A. R. Tatchell, Longman Publishers, London and New York, 1978 p1125. Then sufficient absolute ethanol was added to give a clear solution after which it was further refluxed overnight, then cooled and the volatiles removed to give 0.23g colourless solid product (85%). m.p.>280°C confirmed to be by i.r. spectroscopy and elemental analysis results: i.r. spectroscopy results : ν 3320 (m)NH, 1673 (S) C = O Elemental Analysis results : (Calc'd for C₅₃H₇₄N₈O₉ C : 65.81, H : 7.71, N : 11.59, O : 14.89; Found C : 64.90, H : 7.09, N : 11.22, O : 14.63). EXAMPLE 6 Preparation Diethylacetamide of p-t-Butylpseudocalix-4-arene To 3.84g p-t-butylpseudocalix-4-arene also called 7, 13, 19, 25-tetra- tert.butyl-27, 28, 29, 30 - tetrahydroxy-2,3-dihomo-3-oxacalix-4-arene prepared following the method of C. D. Gutsche, B. Dhawan, K. H. No and R. Muthikrishnan J. Am. Chem. Soc. 103 p3782 1981 from p-t-butylphenol, paraformaldehyde and aqueous potassium hydroxide in refluxing xylene (0.0056 mole) in 25 mls dry DMSO was added 4.50g (0.030 mole) 2-chloro-N,N-diethylacetamide, 2.6g (0.022 mole) potassium bromide and 5.60g (0.041 mole) anhydrous potassium carbonate was stirred under nitrogen at room temperature for 72 hours after which the reaction mixture was poured into 3% sulphuric acid to give an off white precipitate which was washed well with water and dried to give 5.8g (90%) yield of off white product. Chromatography through neutral alumina using dichloromethane as eluent gave off-white product m.p. 111-114°C characterised by infra red spectroscopy and elemental analysis as i.r. spectroscopy results: ν 1652 (S) C = O Elemental Analysis results : (Calc'd for C₆₉H₁₀₂N₄O₉) C : 73.24, H : 9.09; Found C : 73.15, H : 8.77) EXAMPLE 7 Preparation This compound was prepared following the method of G. Calestani et. al. J. Chem. Soc. Chem. Commun. 1987 p344. In the same reference it is reported that this compound sequesters alkali metal ions e.g. sodium. We have made the rather unexpected discovery that this compound also sequesters transition metals such as copper. Ion extraction by Nitrogen-containing Calixarenes . The ion binding abilities of nitrogen-containing calixarenes were measured by extraction of metal picrates from aqueous into organic media. In each experiment a solution of the nitrogen-containing calixarene in dichloromethane was prepared at 2.5 X 10⁻⁴M. Silver and cupric picrates were prepared as aqueous 2.5 X 10⁻⁴M solutions (see Aggarwal et al Def. Sci.J., Vol. 25, October 1975, 153). A neutral aqueous sodium picrate solution was prepared such that the concentration of sodium picrate was 2.5 x 10⁻⁴M. Equal volumes of each solution (5 millimetres) were shaken together for 3 minutes and the percentage extraction of metal picrate into organic phase was determined by measuring the increase in absorbance of dichloromethane layer atλm ca 355 nm (cupric and silver picrate) and λm 387 nm (sodium picrate) in a u.v. spectrophotometer. The results are presented in the following table. Compound m.p. % ε Silver Picrate Cupric Picrate Sodium Picrate (Comparative) Ex 1> 280°C 5.9 30.0 <1 Ex 2 242-5°C <1 3.8 <1 Ex 4 198-200°C <1 3.9 <1 Ex 5> 280°C 6.6 31.6 <1 Ex 6 111-4°C 48.2 10.4 57.0 Ex 7 230-3°C 81.3 9.6 95.4 EXAMPLE 8 Preliminary Preparation A. 1.4g of the diallyl ether of the diethyl acetate of p-t-butylcalix-4-arene prepared as in U.S. Patent 4,642,362 S. Harris et al (0.00155 mole) was hydrolysed with excess KOH in water/ethanol by refluxing for 48 hours following the method described in EP-A-0 237 265 Loctite (Ireland) Limited. Acidification with sulphuric acid and water washing of the colourless precipitated solid gave upon drying 0.95g product as a colourless solid (73%) confirmed by infra red analysis to be the desired diacid product A: i.r. spectroscopy results: ν 3370 (S) broad-COH, 1735 (S)-(HO) C=O Preliminary Preparation B. 0.95g (0.0011 mole) of diacid product A was treated with 2.5g (0.0197 mole) oxalyl chloride in 10 mls dichloromethane under nitrogen with stirring at room temperature following the procedure described in EP-A-0 237 265 Loctite (Ireland) Limited. Removal of volatiles gave 0.99g (100%) of buff coloured acid chloride product which was not further purified in view of its moisture sensitivity. Infra red analysis confirmed its structure to be the diacid chloride B: i.r. spectroscopy results ν 1810 (S) (Cl) C = O Preparation of Polymer Calixarene Compound Following the method of W.R. Sorenson and T.W. Campbell in Preparative Methods of Polymer Chemistry Second Edition Interscience Publishers 1968 p96 the 0.99g of calixarene diacid chloride B (0.00112 mole) in 30 mls of dry 1,2,4-trichlorobenzene (in place of chloroform) was added at room temperature to 0.162g (0.00112 mole) 1,8-diaminooctane and 0.227g (0.00224 mole) triethylamine (as acid acceptor) in 40 mls dry 1,2,4-trichlorobenzene under nitrogen with stirring. After 24 hours reaction time the reaction mixture was poured into 1 litre of heptane to give a white precipitate which quickly fell to the bottom. The precipitate was filtered off and washed well with further heptane and dried to give 0.8g (75%) polyamide calixarene as an off-white solid. The material was further taken up in dichloromethane which was washed well with water to remove amine salts and dried. Following solvent removal, pure off-white solid product was collected which was confirmed by HPLC, infra red and elemental analysis to be polyamide calixarene product n′= ca 6. The product softened at 168°C and completely melted by 173°C. H.P.L.C. analysis: Waters Millipore Sugar Analyzer/Liquid Chromatograph; PL gel 10µ; 100 Å, 500 Å, and 1000 Å columns in series; dichloromethane as eluent, 1.2 mls/min; U.V Detector λ m 250 nm; retention volume: 15.2 minutes. H.P.L.C. Comparison Polystyrene of 9500 molecular weight as standard; retention volume: 14.3 minutes. The calixarene derivative of formula C having a molecular weight of 901; retention volume: 18.5 minutes. If in Formula XIV, n′ = 1, the molecular weight of the product would be 953. Based on retention volume time, the molecular weight of the actual product XIV obtained was estimated as approximately 5750. Therefore n′ = 6 approximately (6 x 953 = 5718). i.r. results: ν 3350 (m) NH, 1653 (S) (NH) C= O Elemental Analysis results: (Calculated for C₆₂H₈₄O₆N₂ C: 78.11, H: 8.88, N: 2.94, found C: 78.88 H: 8.81 N: 2.95) Ion extraction by Nitrogen-Containing Calixarene . The ion binding ability of the nitrogen-containing calixarene was measured as described above. The results are presented in the following table. Compound m.p. % ε Silver Picrate Cupric Picrate Sodium Picrate Example 8 168-173°C 9.8 10.8 6.9 As can be clearly seen the polyamide bound calixarene compound sequesters transition and precious metals such as copper and silver as well as alkali metals such as sodium. This particular example is important because the polyamide calixarene is linear and so is soluble in organic solvents and may therefore be used to provide easy application of a coating to a substrate. Crosslinked polyamides would have to be prepared on a substrate when in formula XIII m′ is greater than 2. The compounds of Examples 6 and 7 were submitted to further ion extraction tests, using the procedure described above but with picrates of other metals as well as silver, copper and sodium. The results are presented in the following tables: Compound % ε Picrates Ca Mg K (Comparative) Al Mn Example 6 62.4 3.3 17.9 6.6 39.0 Example 7 80.9 10.0 54.0 13.1 48.6 These results illustrate the surprising capability of the nitrogen-containing calixarene and oxacalixarene derivatives to sequester elements in Groups IIa, III and VIIa of the periodic table. The results for calcium and manganese are particularly good.

Claims: Use of oxacalixarene and calixarene derivatives of formula (I): wherein m' + m'' = 0-8 n = 0-8 m' ≧ 1/2 (m' + m'') 3 ≦ m' + m'' + n ≦ 8 if n = 0, m' + m'' ≧ 4 R³ is H, halogen, or C₁-C₁₀ aliphatic hydrocarbyl, C₆-C₂₀ aryl, C₆-C₂₀ aliphatic hydrocarbylaryl or a derivative thereof substituted by one or more halo groups or substituted or interrupted by one or more oxo groups and R³ may be the same or different on each aryl group; R¹ and R¹⁵ which may be the same or different are H or C₁-C₁₀ aliphatic hydrocarbyl, C₆-C₂₀ aryl, C₆-C₂₀ aliphatic hydrocarbylaryl or a derivative thereof substituted by one or more halo groups or substituted or interrupted by one or more oxo groups; R² is selected from: R⁴ which is H, or C₁-C₁₀ aliphatic hydrocarbyl, C₆-C₂₀ aryl, C₆-C₂₀ aliphatic hydrocarbylaryl or a derivative thereof substituted by one or more halo groups or substituted or interrupted by one or more oxo groups, wherein R⁵ and R⁶ which may be the same or different are H, or C₁-C₁₀ aliphatic hydrocarbyl, C₆-C₂₀ aryl, C₆-C₂₀ aliphatic hydrocarbylaryl, or a derivative thereof substituted by one or more halo groups or substituted or interrupted by one or more oxo groups, -OR¹, wherein R¹ is as defined above and R¹⁷ which is a residue of a C₁-C₁₀ aliphatic hydrocarbyl, C₆-C₂₀ aryl, or C₆-C₂₀ aliphatic hydrocarbylaryl group or of a derivative thereof substituted by one or more halo groups or substituted or interrupted by one or more oxo groups providing bond to another oxacalixarene or calixarene derivative of formula 1 wherein R² is R¹⁷; or a polyamide polymer having a plurality of calixarene groups bound thereon, of the formula (XIII) wherein x > 1, m' ≧ 2, m' + m'' ≧ 4 and R³, R¹⁵, and R¹⁷, are as defined above; for the sequestration of metals other than alkali metals. Use according to Claim 1 wherein n in formula (I) is at least 1 and R² is R⁴. Use according to Claim 2 wherein the oxacalixarene derivative is selected from: (i) an oxacalix-4-arene of formula (ii) a dioxacalix-4-arene of formula (iii) a trioxacalix-3-arene of formula wherein R¹⁶ is -CH₂C(O)N(R¹)(R⁴), and R¹, R³ and R⁴ are as defined in Claim 1. Use according to Claim 1 wherein in formula I m'' = n = 0 and R² is R⁴. Use according to Claim 1 wherein in formula I R² is Use according to Claim 1 wherein in formula I R² is -OR¹. Use according to Claim 1 wherein in formula I aliphatic hydrocarbyl as a group or part of a group is alkyl or alkenyl. Use according to Claim 1 wherein in formula I m'' = 0. Use according to Claim 1 wherein in formula I R² is selected from: R⁴ which is H, or C₁-C₁₀ aliphatic hydrocarbyl, C₆-C₂₀ aryl, C₆-C₂₀ aliphatic hydrocarbylaryl or a substituted derivative thereof, wherein R⁵ and R⁶ which may be the same or different are H, or C₁-C₁₀ aliphatic hydrocarbyl, C₆-C₂₀ aryl, C₆-C₂₀ aliphatic hydrocarbylaryl, or a derivative thereof substituted by one or more halo groups or substituted or interrupted by one or more oxo groups, and -OR¹, wherein R¹ is as defined in Claim 1.

Inventors: GUTHRIE JOHN, HARRIS STEPHEN J, MACMANUS MAUREEN G, GUTHRIE, JOHN, HARRIS, STEPHEN J., MACMANUS, MAUREEN G.
Applicants: LOCTITE IRELAND LTD, LOCTITE (IRELAND) LTD.
Application year: 1988
Main classification: C07D313
IPC codes: C07D313, C07D323, C07D321