Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
  • C08G77/28—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen sulfur-containing groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
  • C07F7/1804—Compounds having Si-O-C linkages
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
  • C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages

Definitions

• the invention relates to new organopolysiloxanes and their use for example as cation and anion exchangers, organic and inorganic compound scavengers, solid phase purification or extraction materials, immobilisation materials for bio-molecules, anti-microbial agents, hydrophilicity modifiers, flameproofing agents, antistatic agents, coatings for biomedical devices, water repellent films and coatings, solid phase synthesis materials and chromatography materials.
• the invention also relates to precursors of these new products and processes for their production.
• API active pharmaceutical ingredients
• solvents potable water and aqueous based wastes and from contaminated waters.
• metal catalysts are increasing being used in the manufacture of APIs or their intermediates. Given the toxicity of these metals very low residual levels have to be achieved in the API.
• simple and quick processes are required to purify reaction mixtures in order to screen thousands of compounds to identify leads for optimisation and development programmes.
• the electronics industry has a particular need for ultra pure water with very low levels of both cations and anions.
• Substituted polystyrene derivatives are an important class of materials being used for scavenging metal ions and organic compounds.
• the chemical and physical properties of a variety of such polystyrene based systems are described in the Bio-Rad Life Science Research Products catalogue 1998/99, pages 56-64.
• one limitation of these polystyrene resins is that a range of chemical functionality cannot be readily attached to these organic polymers due to the physical limitations of these polymers and the range of chemistry that can be used to attache functional groups onto the aromatic rings.
• these polystyrene resins may possess disadvantages, for example poor chemical stability and thermal stability, believed to be due to the organic polymeric backbone. Additional problems for example swelling and shrinking in organic solvents as well as the production of highly coloured unwanted side products may also be encountered. Generally, due to their poor thermal stability, these polystyrene resins cannot be used for any length of time above 8O 0 C, thus limiting their general applicability.
• Inorganic polymer systems such as silica, aluminium oxide and titanium oxide have also been disclosed as functionalised materials.
• Active functional groups or metals can be attached by a variety of means to these systems.
• the functional groups are only physically adsorbed for example low functional group loading along with limitations in the range of solvents that can be used and removal of the functional groups on use or on standing. This is believed to be due to the rather weak attachment between the functional group and the surface atoms on the support.
• Building the functional group into the framework may provide a more robust material and may also permit higher functional group loadings.
• there are limited synthetic methodologies for the preparation of suitable starting materials from available precursors A need exists to provide new synthetic methods as well as starting compounds in order to make such functionalised materials.
• Functionalised solid materials are used in solution phase organic synthesis to aid rapid purification and workup. These materials, also known as scavengers, may remove excess reagents and side products. Typically, a scavenger is added to a solution to quench and selectively react with excess or unreacted reagents and reaction side products. The unwanted chemicals now attached to the functionalised materials are removed by simple filtration. This simple process circumvents the standard purification methodologies of liquid-liquid extraction, chromatography and crystallisation.
• Substituted polystyrene derivatives are known for use as scavengers but have a number of limitations such as lack of thermal stability, swelling and shrinking in organic solvents and a limited range of functional groups. In solid phase synthesis substituted polystyrene derivatives are the main class of materials being used and likewise these materials suffer the same limitations as described above. The use of functionalised silica materials for this application is limited by the availability of suitable functionalised materials.
• arsenates, chromates and permanganates are highly toxic and so their concentrations in water or other medium has to be very carefully controlled. New materials with very high affinity for such anions are needed in order to achieve very low acceptable limits.
• Precious metal mediated reactions enable the organic chemist to conduct a wide range of reactions used in the manufacture of products for a number of industries. Typical reactions include Suzuki, Heck, oxidations and reductions and metals and their complexes such as platinum, palladium and rhodium are extensively used. A major problem encountered with the use of these systems is the significant loss of these expensive and highly toxic metals. Furthermore in the production of active pharmaceutical agents (APIs) using such metal mediated reactions, it is found that the metal invariably complexes to the desired API and residual metal contents in the range of 600-1000 ppm are not uncommon. The current target for palladium, platinum, rhodium and nickel is less than 5 ppm.
• the inventors have discovered a class of compounds which have a desirable combination of characteristics and make them suitable for use in a range of applications including acting as scavengers for inorganic and organic compounds, solid phase purification or extraction materials, ion exchange materials, catalysts, catalyst immobilisation supports, immobilisation materials for bio-molecules, anti-microbial agents, hydrophilicity modifiers, flameproofing agents, antistatic agents, solid phase synthesis materials and chromatography materials, or which are precursors for these.
• a compound of formula 1 [(O 3/2 )Si CH 2 CH 2 SX] a [Si (CXw 2 )] b [Si (O ⁇ V)] c wherein X is selected from CH 2 A; [CH 2 CH 2 NR 1 I p R 2 ; CHCOX 1 CH 2 COX 2 (CH 2 ) e CO Y [CO (CH 2 ) e SCH 2 CH 2 Si (O 312 )] m [CO (CH 2 ) e SH] n and wherein A is the residue of an amino acid or a derivative or a salt of an amino acid of formula
• R 1 and R 2 are independently selected from hydrogen, C 1-22 alkyl group, C 1-22 acyl group and a C 1-22 alkaryl group;
• X 3 is selected from OR, NR 1 R 2 , an amino acid and a protein; R is selected from hydrogen, a metal ion, a Ci -22 alkyl group e is 1 or 2; p is 1 to 100;
• X 1 and X 2 are independently selected from OR and N R 1 R 2
• Y is a polyol moiety having z hydroxyl groups wherein z or fewer hydroxyl groups are deprotonated, m and n are, independently, less than z such that m+n+1 is less than or equal to z and m+n+1 hydroxyl groups of the polyol are deprotonated;
• V is a group which is optionally substituted and selected from a C 1-22 -alkyl group, C 2-22 -alkenyl group, a C 2 . 22 -alkynyl group, an aryl group a C 1-22 alkylaryl sulphide group, a sulfoxide, a sulfone, an amine, a polyalkyl amine, a phosphine and other phosphorous containing group; the free valences of the silicate oxygen atoms are saturated by one or more of: a silicon atom of other groups of Formula 1 , hydrogen, a linear or branched C 1-22 -alkyl group, an end group R 3 3 M 1 O 1/2 , a cross-linking bridge member or by a chain R 3 q M 1 (OR 4 ) g O k/2 or
• the ratio of end group, cross linker or polymer chains to a+b+c is from 0 to 999:1 preferably 0.001 to 999:1 and especially 0.01 to 99:1.
• Advantages of the new scavengers for inorganic and organic compounds, solid phase extraction or purification materials, catalysts, catalyst immobilisation supports, bio-molecule immobilisation supports, anti-microbial agents, hydrophilicity modifiers, flameproofing agents, antistatic agents, solid phase synthesis materials and chromatography materials, and ion exchanger materials based on compounds of Formula 1 include high intrinsic activity of particular functional groups for specific applications and that the functional group or groups can be tuned to have either a high or low level of loading according to the requirements of the user.
• Other advantages include high thermal stability, fixed and rigid structures, good stability to a wide range of chemical conditions, insolubility in organic solvents, high resistance to ageing, easily purified and high reusability.
• compounds of Formula 1 are very flexible, allowing a wide range of functionalised materials to be made from a small number of common intermediates and also the porosity of the materials can be varied from micro to macro porous and the loading of the functional groups as well as the other substituents in the fragment V to be varied as needed.
• Compounds of Formula 1 have the added advantage of their respective functional groups being firmly attached to a very stable and inert medium.
• compounds of Formula 1 have the added advantages of a very high affinity for both cations and anions coupled with fast kinetics thus enabling very rapid removal of toxic compounds or impurities to very low levels.
• compounds of Formula 1 can be used as heterogeneous catalysts to conduct a number of chemical transformations and posses the key advantages of being easily separated from the reaction mixture by filtration and also of being recycled and reused.
• the optionally substituted linear or branched group selected from d. 22 -alkyl, C 2 - 22 -alkenyl, C 2 . 22 -alkynyl group, an aryl and C 1-22 -alkylaryl group, R 1"4 groups may independently be linear or branched and/or may be substituted with one or more substituents but preferably contain only hydrogen and carbon atoms. If a substituent is present, it may be selected from nitro, chloro, fluoro, bromo, nitrile, hydroxyl, carboxylic acid carboxylic esters, sulfides, sulfoxides, sulfones, C-
• the optionally substituted linear or branched group selected from C 1-22 -alkyl, C 2 . 22 - alkenyl, C 2 - 22 -alkynyl group, an aryl and Ci. 22 -alkylaryl group, R 1"4 are independently selected from linear or branched C 1 ⁇ and desirably Ci -12 -alkyl, C 2-22 - and desirably C 2 .i 2 -alkenyl, aryl and a C ⁇ -alkylaryl group and it is especially preferred that these groups are independently selected from a linear or branched Cv ⁇ -alkyI, C 2 - 8 -alkenyl, aryl and a C ⁇ e-alkylaryl group.
• R 1'4 are independently a C ⁇ -alkyl group for example methyl or ethyl, or a phenyl group.
• q is from 0 to 2
• k is from 1 to 3
• alkyl groups examples include methyl, ethyl, isopropyl, ⁇ -propyl, butyl, tert-butyl, n- hexyl, n-decyl, n-dodecyl, cyclohexyl, octyl, /so-octyl, hexadecyl, octadecyl, /so-octadecyl and docosyl.
• alkenyl groups include ethenyl, 2-propenyl, cyclohexenyl, octenyl, /so-octenyl, hexadecenyl, octadecenyl, /so-octadecenyl and docosenyl.
• C 1-6 -alkoxy refers to a straight or branched hydrocarbon chain having from one to six carbon atoms and attached to an oxygen atom. Examples include methoxy, ethoxy, propoxy, tert- butoxy and n-butoxy.
• polyol refers to an organic compound particularly with an alkyl chain having two or more hydroxyl groups and specific examples include glycerol, pentaerythritol and dipentaerythritol as well as polyethylene oxide and polypropylene oxide.
• aryl refers to a five or six membered cyclic, 8-10 membered bicyclic or 10-13 membered tricyclic group with aromatic character and includes systems which contain one or more heteroatoms, for example, N, O or S.
• suitable aryl groups include phenyl, pyridinyl and furanyl.
• alkylaryl is employed herein, the immediately preceding carbon atom range refers to the alky! substituent only and does not include any aryl carbon atoms.
• suitable alkaryl groups include benzyl, phenylethyl and pyridylmethyl.
• Preferred polyols include glycerol, pentaerythritol and dipentaerythritol.
• the ratio of end groups or cross linker or polymer chains to a+b+c varies from 0 to 99:1 , preferably 0.01 to 99:1.
• Particularly suitable cross linkers or polymer chains are derived from titanium alkoxides, aluminium trialkoxides and alkyl alkoxy silanes.
• Examples of cross linkers include aluminium triethoxide, aluminium tributoxide and titanium isopropoxide and for polymer chains alkyl alkoxy silanes.
• the end group, cross linking bridge or polymer chain member is preferably R 3 3 M 1 O 1/2l R 3 2 SiOR 4 O 1/2 , (R 3 J 2 SiO 2Z2 , TiO 4/2 , R 3 Ti0 3/2 , (R 3 ) 2 Ti0 2/2 , AIO 3/2 or R 3 AIO 272 .
• R 3 and R 4 are preferably C 1-4 -alkyl, especially methyl or ethyl.
• the invention also provides novel precursor compounds for formula 1, the precursor being of formula (R 4 O) 3 SiCH 2 CH 2 SX .
• the general procedure used for the production of the compounds of Formula 1 comprises first forming the compounds (R 4 O) 3 SiCH 2 CH 2 SX and depending on the reagents and then combining with tetraalkyl orthosilicate and with other compounds such as (R 4 O) 3 SiV, titanium alkoxides, aluminium trialkoxides and alkyl alkoxy silanes, in the desired ratios, in solvent with either dilute acid or base.
• the surfaces of materials such as silica, aluminium oxide or carbon can be treated with (R 4 O) 3 SiCH 2 CH 2 SX and if necessary with other compounds such as (R 4 O) 3 SiV, titanium alkoxides, aluminium trialkoxides and alkyl alkoxy silanes to give compounds of Formula 1.
• materials can then be subsequently transformed using known chemistry.
• R 4 is a linear or branched d. ⁇ -alkyl, C 2 . 22 -alkenyl or C 2 . 22 -alkynyl group, aryl or C 1-22 -alkylaryl group.
• a wide range of free radical initiators can be used for this reaction and preferred are the peroxides and in particular the alkyl peroxides. Addition of a very small amount of the initiator every few hours improves the overall yield.
• Reaction temperatures between 20-170 0 C can be used, though a reaction temperature of between 20- 12O 0 C is preferred.
• Di-fert-buty! peroxide is the preferred free radical initiator. Reaction times of between 5 minutes to 48 hours have been used with 1/2 to 2 hours preferred.
• sol-gel technology was used to produce the organopolysiloxanes of Formula 1.
• the state of the arts of sol-gel technology and the hydrolysis of silicon esters are described by M.A. Brook in Silicon in Organic, Organometallic and Polymer Chemistry Chapter 10, page 318, John Wiley & Sons, Inc., 2000, G.A. Scherer in Sol-gel science: the physics and chemistry of sol-gel processing, Boston: Academic Press, 1990, and J. D. Wright in Sol-gel materials: chemistry and applications, Amsterdam: Gordon & Breach Science Publishers, 2001 and the references contained within.
• Acids and bases were used to catalyse the hydrolysis of the silicon esters of (R 4 O) 3 SiCH 2 CH 2 SX and if necessary with other compounds such as (R 4 O) 3 SiV, and tetraalkyl orthosilicate to produce the organopolysiloxanes of Formula 1.
• a range of solvents well known to those skilled in the art of organic chemistry, can be used to conduct this reaction. Alcohols are the preferred solvents particularly methanol and ethanol. After standing for a period of time the solution can be warmed to speed up the formation of the glass. Ratios, by weight, of the alcohol solvent to the combined weight of the reagents from 100 to 0.01 can be used, with ranges from 2-10 being preferred.
• a range of acids can be used to aid hydrolysis with hydrochloric acid in concentrations ranging from 0.1 to 4 M being preferred.
• Hydrochloric acid, 1 molar was routinely used. Ratios, from 0.000001 to10, of hydrochloric acid, 1 molar, to the combined weight of the reagents can be used, with ranges from 0.0001 to 1 being preferred.
• the reaction mixture was left to stand at temperatures ranging from 0°C-12O 0 C to aid hydrolysis and the formation of the Si-O-Si bonds. Temperatures between 20°C-90°C are preferred and warming is continued until all the solvent has evaporated and a clear glass is obtained.
• end groups, cross-linking bridge members or polymer chains such as (R 3 ) 3 Si0 1/2 or R 3 Si0 3/2 or (R 3 ) 2 Si0 2 / 2 or TiO 4 / 2 or R 3 TiO 3/2 or (R ⁇ 2 TiO 2Z2 or AIO 3/2 or R 3 AIO 2/2l where R 3 is as defined above, but is preferably methyl or ethyl, or other oxo metals can be added in varying ratios to produce the desired compound of Formula 1.
• end groups, cross linking bridge or polymer chain precursors are added at the same time as compounds (R 4 O) 3 SiCH 2 CH 2 SX and tetraalkyl orthosilicate and (R 4 O) 3 SiV.
• Compounds of Formula 1 can also be prepared by treating a preformed material such as silica, or aluminium oxide or other oxides or carbon with (R 4 O) 3 SiCH 2 CH 2 SX and with (R 4 O) 3 SiV if required, and with other end groups, cross linkers or polymers chains if required, in varying ratios in a solvent. At the end of the reaction the solid is filtered off and washed extensively with solvents such as water or alcohols to remove any remaining starting materials.
• a preformed material such as silica, or aluminium oxide or other oxides or carbon
• (R 4 O) 3 SiCH 2 CH 2 SX and with (R 4 O) 3 SiV if required, and with other end groups, cross linkers or polymers chains if required, in varying ratios in a solvent.
• solvents such as water or alcohols to remove any remaining starting materials.
• Compounds of Formula 1 where A is CHNR 1 R 2 CO 2 R are similarly prepared by a two step process.
• the first step is a free radical reaction between a thiol and trimethoxy vinyl silane followed either by a sol gel or coating process described above.
• a free radical reaction involving the correspondingly substituted cysteine and trimethoxyvinyl silane gives (CH 3 O) 3 SiCH 2 CH 2 SCH 2 CH(NR 1 R 2 JCO 2 R which on sol gel with tetraethyl orthosilicate or coating preformed silica gave compounds of Formula 1 where A is CHNR 1 R 2 CO 2 R.
• Another example is the free radical reaction between pentaerythritol tetrakis (2-mercaptoacetate) and trimethoxyvinyl silane to give (CH 3 O) 3 SiCH 2 CH 2 SCH 2 CO Y [COCH 2 SCH 2 CH 2 Si(OCH 3 ) 3 ] m [COCH 2 SH] n which on sol gel with tetraethyl orthosilicate or coating preformed silica gave compounds of Formula 1 where X is CH 2 COY[COCH 2 SCH 2 CH 2 Si(O 3/2 )] JCOCH 2 SH] n -The integers m and n are dependent on the relative amounts of the vinyl trimethoxy silane to the polyol used in the preparation.
• Templates to aid the preparation of pores with particular sizes and distributions in compounds of Formula 1 can be added at the sol gel stage. On preparation of the solid organopolysiloxane of Formula 1 these templates can be washed out using known methods.
• Compounds of Formula 1 may be linked to a metal complex, for example as a ligand.
• a further aspect of the invention provides a Compound of Formula 1 further comprising a metal complex M(L) j where M is derived from a lanthanide, actinide, main group or transition metal with oxidation states ranging from zero to four and L is one or more optionally substituted ligands selected from halide, nitrate, acetate, carboxylate, cyanide, sulfate, carbonyl, imine, alkoxy, triaryl or trialkylphosphine and phenoxy and j is an integer from 0 to 8 and where the compound of Formula 1 is linked to the said metal complex .
• M is derived from cobalt, manganese, iron, nickel, palladium, platinum, rhodium, with oxidation states ranging from zero to four and L is one or more optionally substituted ligands selected from halide, nitrate, acetate, carboxylate, cyanide, sulfate, carbonyl, imine, alkoxy, triaryl or trialkylphosphine and phenoxy and j is an integer from 0 to 4.
• the present invention provides a process for treating a feed material comprising contacting a compound of Formula 1 with a feed material: i) to effect a chemical reaction by catalytic transformation of a component of the feed material to produce a desired product; ii) to remove a component of the feed material so as to produce a material depleted in the removed component; or iii) to remove an ionic species in the feed material in an ion exchange process.
• the feed material may be a continuous stream for example a continuous process reaction feedstock, or may be in the form of a batch of material for discrete treatment.
• the feed material for example a waste water or waste process stream, may be treated to selectively remove a components of the feed.
• the removed component may be an undesirable material in the feed and the process acts to provide a desired composition for the feed material that has been depleted in the selectively removed component after contact with compounds of Formula 1.
• This process may be used for example in removing unwanted species from a feed material in a pharmaceutical manufacturing or formulation process to improve the purity level of the pharmaceutical product as regards the removed material, for example metal species.
• the process may be employed to remove desired species from a feed material for subsequent processing or analysis, for example a biological molecule such as an enzyme, peptide, protein and nucleic acid may be removed from a feed material to enable further processing or analysis of the removed components.
• a biological molecule such as an enzyme, peptide, protein and nucleic acid may be removed from a feed material to enable further processing or analysis of the removed components.
• Compounds of Formula 1 are very effective at abstracting a wide range of cations and anions from various environments. For cations these include the lanthanides, actinides, main group and transition metals. Anions include arsenates, borates, chromates, permanganates and perchlorates.
• Compounds of Formula 1 were designed to have very high affinity for ions and thus be able to remove them from various environments. Such high affinity is required when metal ions are tightly bound to particular functional groups for example in highly polar active pharmaceutical ingredients.
• the design of compounds of Formula 1 for these applications involves the presence of two or more different ligands to bind strongly to the ion. Depending on the ion to be removed the ligands are designed to be either soft or hard or a combination of both in order to optimise the affinity of the functionalised material for the ion.
• the compounds of Formula 1 have been designed with easily modified functional groups in order to simply find the optimum combination of ligands for specific ion impurities.
• the products from Examples 9, 10, 12-16, and 24-29 are very effective for the removal of cupric (II) ions from various solutions.
• Ferrous and ferric ions present in hydro- processing streams are readily removed using the products from Examples 9, 10 and 24-29.
• the scavenging of metal ions from strong metal chelates is a major challenge facing the water and associated industries. Examples of such chelates include EDTA 1 citrates and oxalates. These metals chelates pose a significant health problem due to the their high toxicity. To effectively scavenge the metal ions from these chelates requires functional groups with a higher affinity for the metal ions. This requires a functionalised material with particularly designed range of functionality.
• Compounds of Formula 1 have been designed to possess a range of functionality to enable the metal ion to be removed from a strong chelating group. As illustrated in Examples 32 and 33 the products from Examples 12-15 are very effective for the removal of cupric (II) ions bound to chelating groups such as EDTA and citrate.
• Compounds of Formula 1 can also remove precious metals such as palladium, platinum and rhodium ion as well as nickel (0) and nickel (II) from various different solutions and also bound to functional groups commonly found in active pharmaceutical ingredients such as amides, amines and carboxylic acids.
• precious metals such as palladium, platinum and rhodium ion as well as nickel (0) and nickel (II)
• II nickel
• treatment of a palladium acetate solution in tetrahydrofuran or dichloromethane with any of the products from Examples 4, 9, 10, 12-16 and 24-29 results in the complete removal of the palladium ions from solution.
• solutions containing bis(triphenylphosphine) palladium chloride or acetate the products from Examples 12-14, and 24-29 are equally effective for its removal.
• the products from Examples 4, 12-14 and 24-29 are effective for the removal of chlorotris(triphenylphosphine) rhodium(l) from various solutions.
• the products from Examples 4, 12-142, and 24-29 are effective for the removal of platinum chloride from various solutions.
• Rhodium (III) is readily removed from various solutions using any of the products from Examples 4, 12-4, and 24-29.
• Compounds of Formula 1 can be used to remove anions such as arsenates, chromates, permanganates, borates and perchlorates. These anions pose many significant problems to the environment and health. For example toxic chromate anions can be removed using the materials prepared in Example 45 through exchange of the halide anion for chromate.
• Compounds of Formula 1 can be used, as scavengers, to remove excess inorganic or organic reagents and side products from reactions mixtures or from impure chemical products.
• impurities are removed by matching functionality contained in these impurities with specific functionalised materials.
• the amines and polyamine materials prepared in Example 12-16 respectively can readily remove carboxylic acids and mineral acids as well as other acidic reagents from reaction mixtures.
• the amines and polyamines prepared in Examples 12-16 respectively can remove isocyanates, acid chlorides, aldehydes, sulfonyl halides and chloroformates.
• the following examples illustrate the scavenging of unwanted organic and inorganic compounds by compounds of Formula 1 but are not intended to limit the scope of their capability.
• organopolysiloxane compounds of Formula 1 can work in all solvents and are not limited in their application to reaction temperatures below 8O 0 C. In addition compounds of Formula 1 do not suffer from swelling and possess the significant advantage of very fast kinetics compared to organic polymers.
• Metal salt/complexes of Formula 1 can catalyse a wide range of reactions well known to practitioners of organic and inorganic chemistry. Examples include but not limited to oxidations, reductions, alkylations, carbon-carbon bond formation, polymerisations, hydroformylations, arylations, acylations, isomerisations, alkylations, carboxylations, carbonylations, esterifications, trans-esterifications and rearrangements.
• These organopolysiloxane compounds of Formula 1 have many advantages for example they possess good thermal and chemical stability and broad solvent compatibility. One of the advantages of these catalysts is that on completion of the reaction they can be simply filtered off and reused. No apparent loss of activity was observed. Thus an important application of the metal derivatives of Formula 1 is their use as heterogeneous catalysts.
• Compounds of Formula 1 can also be used for solid phase synthesis through first attachment of the starting material. A number of chemical reactions can then be conducted and in each step purification is facile through simple filtration. At the end of the sequence the desired material is released from the solid phase.
• compounds of Formula 1 can be used as materials for solid phase extraction where a desired product is purified through selective retention on the functionalised materials whilst the impurities are removed. The desired material is then subsequently released using a different solvent system.
• Compounds of Formula 1 can also be used for the separation or removal of gases, including the removal of malodorous volatile organic compounds.
• the removal of malodorous amines can be achieved with acids prepared in Examples 4 and 9.
• compounds of Formula 1 include the use as materials for chromatographic separations.
• the materials of Formula 1 can be used in the separation of amines, including optically active amines.
• Primary amines can be selectively separated from secondary amines using compounds of Formula 1.
• Compounds of Formula 1 can be used as materials for gel filtration and high speed size- exclusion chromatography as well as for high pressure liquid chromatography and solid phase extraction.
• Compounds of Formula 1 can be used both to immobilise biological molecules such as enzymes, polypeptides, proteins and nucleic acids as well as for their separation and purification.
• nucleic acids immobilised on compounds of Formula 1 can be used for conducting high volume nucleic acid hybridization assays.
• Compounds of Formula 1 can be used as anti-microbial agents.
• the invention also provides an antimicrobial composition comprising a compound of Formula 1 and a carrier.
• Compounds of Formula 1 can be applied as thin films onto a variety of surfaces.
• Example 1 A mixture containing trimethoxyvinylsilane (78 ml, 0.51 mol), N acetyl cysteine (81.6 g, 0.5 mol) and di-tert butyl peroxide (10 drops) was stirred at room temperature and then warmed to 115 0 C under an atmosphere of nitrogen. The mixture was maintained at this temperature for 4 h during which butyl peroxide (10 drops) was added every 20 min. The solution was then cooled to room temperature to give (2-trimethoxysilylethyl) N acetyl cysteine.
• Example 11 A mixture of the product from Example 9 (8.5 g) in distilled water (80 ml) was brought to pH 7 using 1 M sodium hydroxide solution. The solid was filtered and washed with water and then methanol and then dried to give a disodium carboxylate of Formula 1 as a white powder.
• Example 11 A mixture of the product from Example 9 (8.5 g) in distilled water (80 ml) was brought to pH 7 using 1 M sodium hydroxide solution. The solid was filtered and washed with water and then methanol and then dried to give a disodium carboxylate of Formula 1 as a white powder.
• Example 11 A mixture of the product from Example 9 (8.5 g) in distilled water (80 ml) was brought to pH 7 using 1 M sodium hydroxide solution. The solid was filtered and washed with water and then methanol and then dried to give a disodium carboxylate of Formula 1 as a white powder.
• Example 11 A mixture of the product from Example 9 (8.5 g) in
• R 1 and R 2 are hydrogen,
• Example 15 A mixture of the product from Example 11 (41.0 g,) and polyethylene amine (average M n 423,
• Example 12 (10.0 g,) in water (80 ml) and the resultant mixture was stirred for a further 15 min. The solid was filtered and washed well with distilled water.
• Example 21 Concentrated hydrochloric acid (8 ml) was added to a stirred mixture of the product from Example 13(10.0 g,) in water (80 ml) and the resultant mixture was stirred for a further 15 min. The solid was filtered and washed well with distilled water.
• Example 22 Concentrated hydrochloric acid (8 ml) was added to a stirred mixture of the product from Example 14(10.0 g,) in water (80 ml) and the resultant mixture was stirred for a further 15 min. The solid was filtered and washed well with distilled water.
• Example 23 A mixture of the product from Example 10 (0.7 g) in water (30 ml) was treated with an aqueous solution of copper nitrate.
• Example 24 A mixture of pentaerythritol tetrakis(2-mercaptoacetate) (10.4 g, 0.024 mol) and vinyl trimethoxysilane (5.5 ml, 0.0361 mol) was warmed with stirring at 100 0 C for 1 hour and then cooled to room temperature.
• Example 31 A mixture of the product from Example 1 (4.9 g) and tetraethyl orthosilicate (41.3 g) and trimethoxy methyl silane (3.1 g) was dissolved in methanol (160 ml) and 1 M HCI (21 ml
• Example 32 The product from Example 14 (0.2g) was added to a sample (40ml) of a 20 ppm blue coloured solution of copper ethylenediaminetetraacetate in water. The mixture was agitated gently at room temperature for 2 hours. It was then filtered. Analysis of the filtrate showed that the copper complex had been removed. Examples 12, 13, 15, 16, (0.2g) were also effective in the above test.
• Example 33
• Example 34 The product from Example 3 (0.2g) was added to a sample (40ml) of a 20 ppm green coloured solution of nickel citrate in water. The mixture was agitated gently at room temperature for 2 hours. It was then filtered. Analysis of the filtrate showed that the nickel complex had been removed. Examples 12, 13, 15, 16 (0.2g) were also effective in the above test.
• Example 34
• Example 4 The product from Example 4 (0.06 g) was added to a sample (1 ml) of a 500 ppm dark orange/brown coloured solution of ruthenium trichloride in a mixture of chloroform and dichloromethane. The solution went completely colourless. The mixture was filtered. Analysis of the filtrate showed that the ruthenium had been removed. Examples 12 and 24-29 were equally effective in the above test.
• Example 35 The product from Example 4 (0.06 g) was added to a sample (1 ml) of a 150 ppm orange coloured solution of chlorotris(triphenylphosphine)rhodium (Wilkinson's catalyst) in chloroform. The solution went completely colourless. The mixture was then filtered. Analysis of the filtrate showed that the rhodium had been removed. Examples 12-16 and 24-29 were equally effective in the above test.
• Example 36 The product from Example 4 (0.06 g) was added to a sample (1 ml) of a 500 ppm
• Example 4 The product from Example 4 (0.06 g) was added to a sample (1 ml) of a 160 ppm orange coloured solution of palladium acetate in dichloromethane. The solution went completely colourless. The mixture was then filtered. Analysis of the filtrate showed that the palladium had been removed. Examples 12 and 24-29 were equally effective in the above test.
• Example 37 The product from Example 4 (0.06 g) was added to a sample (1 ml) of a 160 ppm orange coloured solution of palladium acetate in dichloromethane. The solution went completely colourless. The mixture was then filtered. Analysis of the filtrate showed that the palladium had been removed. Examples 12 and 24-29 were equally effective in the above test. Example 37
• Example 4 The product from Example 4 (0.06 g) was added to a sample (1 ml) of a 160 ppm orange coloured solution of tetrakistriphenylphosphine palladium in dichloromethane. The solution went completely colourless. The mixture was then filtered. Analysis of the filtrate showed that the palladium had been removed. Examples 24-29 were equally effective in the above test.
• Example 38 The product from Example 4 (0.06 g) was added to a sample (1 ml) of a 160 ppm orange coloured solution of tetrakistriphenylphosphine palladium in dichloromethane. The solution went completely colourless. The mixture was then filtered. Analysis of the filtrate showed that the palladium had been removed. Examples 24-29 were equally effective in the above test. Example 38
• Example 39 The product from Example 4 (0.06 g) was added to a sample (1 ml) of a 1300 ppm light yellow coloured solution of potassium tetrachloro platinate in water. The solution went completely colourless. The mixture was then filtered. Analysis of the filtrate showed that the platinum had been removed. Examples 12 and 24-29 were equally effective in the above test.
• Example 39 The product from Example 4 (0.06 g) was added to a sample (1 ml) of a 1300 ppm light yellow coloured solution of potassium tetrachloro platinate in water. The solution went completely colourless. The mixture was then filtered. Analysis of the filtrate showed that the platinum had been removed. Examples 12 and 24-29 were equally effective in the above test. Example 39
• Example 40 The product from Example 24 (0.06 g) was added to a sample (1 ml) of a 2000 ppm green coloured solution of nickel acetate in water. The solution went completely colourless. The mixture was then filtered. Analysis of the filtrate showed that the nickel had been removed. Example 25-29 and 10 were equally effective in the above test.
• Example 40 The product from Example 24 (0.06 g) was added to a sample (1 ml) of a 2000 ppm green coloured solution of nickel acetate in water. The solution went completely colourless. The mixture was then filtered. Analysis of the filtrate showed that the nickel had been removed.
• Example 25-29 and 10 were equally effective in the above test.
• Example 40 The product from Example 24 (0.06 g) was added to a sample (1 ml) of a 2000 ppm green coloured solution of nickel acetate in water. The solution went completely colourless. The mixture was then filtered. Analysis of the filtrate showed that the nickel had been removed.
• Example 25-29 and 10 were equally
• Example 4 The product from Example 4 (0.06 g) was added to a sample (1 ml) of a 1000 ppm yellow coloured solution of ammonium cerium nitrate in water. The solution went completely colourless. The mixture was then filtered. Analysis of the filtrate showed that the cerium had been removed.
• Example 12 The product from Example 12 (0.2 g) was added to a sample (40 ml) of a 20 ppm light blue coloured solution of copper sulfate in water. The solution was left to agitate gently for 2 hours.
• Example 42 The product from Example 4 (0.06 g) was added to a sample (1 ml) of a 1700 ppm yellow coloured solution of iron nitrate hexahydrate in water. The solution went completely colourless.
• the mixture was then filtered. Analysis of the filtrate showed that the iron had been removed.
• Example 9 was equally effective in the above test.
• Example 43 The product from Example 14 (0.06 g) was added to a sample (1 ml) of a 500 ppm dark blue/grey solution of chromium nitrate nonahydrate in water. The solution went completely colourless. The mixture was then filtered. Analysis of the filtrate showed that the chromium had been removed.
• Example 44 The product from Example 10 (0.9 g) was added to a sample (5 ml) of a 1000 ppm solution of zinc chloride in water. The mixture was then filtered. Analysis of the filtrate showed that the zinc had been removed.
• Example 20 The product from Example 20 (0.06 g) was added to a sample (1 ml) of a 250 ppm solution of potassium dichromate in water. The solution went colourless. The mixture was then filtered.
• Example 47 A mixture of anisole (0.035 g, 0.33 mmol) as a marker, benzylamine (0.041 g, .0.38 mmol) and the product from Example 9 (0.65 g, 1.2 mmol) was stirred in CDCI 3 (2.5 cm 3 ) at room temperature for 1 h. The mixture was then centrifuged and a 1 H NMR spectrum of the chloroform solution showed that the benzylamine was completely removed.
• Example 50 A mixture of dimethoxyethane (0.022 g, 0.25 mmol), phenyl isocyanate (0.029 g, 0. 24 mmol) and the product from Example 12 (0.45 g, 0.97 mmol) was stirred in CDCI 3 (2.5 cm 3 ) at room temperature for 1.5 h. The mixture was then centrifuged and a 1 H NMR spectrum of the chloroform solution showed that the phenyl isocyanate was completely removed. Examples

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