PREPARATION OF MONOMERS

Abstract: A method for the preparation of monomers, especially aromatic ester monomers, which comprises reacting a stannylated compound generally of formula (I) or formula (II), where A<1> is usually an aromatic group and A<3> is usually an aromatic group or a hydrogen atom, with a second compound, usually an acid chloride or di(acid chloride). The stannylated compound and second compound react to eliminate the compound Bu3SnCl and form an aromatic ester monomer. Some novel monomers can be prepared using this method.

Description: PREPARATION OF MONOMERS This invention relates to the preparation of orga¬ nic compounds and especially to the preparation of monomers for subsequent use in polymerisation reactions. Known.industrial methods for producing monomers, especially aromatic monomers wherein an aromatic group is bonded directly to a functional group such as an ester, thioester or carbonate, often have a number of disadvantages. For example high temperatures are usually required and/or unpleasant solvents such as pyridine are necessary. Aromatic ester monomers, for example can be prepared using a phase-transfer cataly¬ sis method, but this method has the disadvantage that two or more recrystallisations of the product are usually necessary in order to obtain a satisfactorily pure monomer. In a paper by J Valade and M Pereyrf entitled • Etude de la scission de la liaison Sn-O-C dans les monoalcoxytrialcoyέtains' , Chimie Organique, Seance du 21 Mai 1962, pp. 3693 there is described a method for making simple aliphatic esters by reacting methoxytri- butyltin with acetyl chloride or benzoyl chloride, the reaction producing methyl acetate or phenyl acetate. The use of tin in intermediates for making polymers is described in European Patent Publication No.0,154,506. In a first aspect the present invention provides a method for the preparation of an organic compound comprising reacting a first compound of the formula x (R)-.-M-Y-A-T—Y-M-(R) r where each R is independently a substituted or unsubstituted alkyl or aryl group; each r is independently an integer from 1 to 4 inclusive depending upon the element M used; each M is independently an element selected from Group IIIB, IVB or VB of the Periodic Table (IUPAC 1965 revi¬ sion) or a transition metal, excluding carbon, silicon, nitro¬ gen, phosphorus, boron, aluminium and titanium; each Y is independently an oxygen atom, a sulphur atom, a substituted nitro- H gen atom other than -N-, or a substituted phosphorus atom other H <H>3 OH I I t than -P-, -P-, or -P-; and A * ** is an aromatic, aliphatic, aromatic/ aliphatic, heterocyclic, ali- cyclic, siloxyl or silane group, with a second compound of the formula: X-B-A 2 I (E) where X is a halogen atom or a group capable of reacting with the first compound to eliminate a compound containing M and X; B is an atom selected from carbon, phosphorus, sulphur or silicon; D is an oxygen or sulphur atom or an amine group; d is 1 if B is carbon, zero or 1 if B is phosphorus, zero, 1 or 2 if B is __ sulphur or zero if B is silicon; E is selected from an aromatic group, aliphatic group, OR' or NR'2 if B is phosphorus, or from an aromatic group, aliphatic group or -OR 1 if B is sili¬ con, where R 1 is a substituted or unsubstituted alkyl or aryl group; e is zero if B is carbon or sulphur, 1 if B is phosphorus or 2 if B is silicon; and A 2 is an aromatic, aliphatic, aromatic/ aliphatic, heterocyclic, alicyclic, siloxyl or silane group, iminate the compound (R) r MX and produce a compound e formula: where G is either the group -M-(R) r , or the group Preferably the stoichiometric ratio of the first compound to the second compound is 1:2 to produce a compound, usually a monomer, of the formula: An example of this reaction is as follows: O O O Bu 3 SnO-A 1 -O-SnBU3 + 2 Cl-C-A 2 ■ > A 2 -C-O-A 1 -O-C-A 2 In a " second aspect the present invention provides a method for the preparation of an organic compound comprising reacting a first compound of the formula: (R) r -M- -A-i-Y-M-(R) r where each R is independently a substituted or unsubstituted alkyl or aryl group; each r is independently an integer from 1 to 4 inclusive depending upon the ele¬ ment M used; each M is independently an element selected from Group IIIB, IVB or VB of the Periodic Table (IUPAC 1965 revi¬ sion) or a transition metal, excluding carbon, silicon, nitro¬ gen, phosphorus, boron, aluminium and titanium; each Y is independently an oxygen atom, a sulphur atom, a substituted nitro- H I gen atom other than -N-, or a substituted phosphorus atom other H ( H ) 3 OH I I I than -P- , -P- , or -P- ; and A- is an aromatic, aliphatic, aromatic/ aliphatic, heterocyclic, alicyclic, siloxyl or silane group, with a second compound of the formula: where X is a halogen atom or a grq,up capable of reacting with the first compound to eli¬ minate a compound containing M and X; B is an atom selected from carbon, phosphorus, sulphur or silicon; D is an oxygen or sulphur atom or an amine group; d is 1 if B is carbon, zero or 1 if B is phosphorus, zero, 1 or 2 if B is sulphur or zero if B is silicon; E is selected from an aromatic group, aliphatic group, OR 1 or NR'2 if B is phosphorus, or from an aromatic group, aliphatic group or -OR' if B is silicon, where R 1 is a substituted or unsubsti- tuted alkyl or aryl group; e is zero if B is carbon or sulphur, 1 if B is phosphorus or 2 if B is silicon; and p is zero or 1, to eliminate the compound (R) r MX and produce a compound of the formula: where Q is the either the group (R) r M-, or the group ;and T is°either the atom or group X, or the group -Y-A 1 -Y-M-(R) r . The method according to this second aspect is especially useful when it is desired to produce a monomer having reactive end groups of the type (R) r M- (D) d II α or -B-X which can then be used directly in polymerisa- <E ) e tion reactions. An especially preferred monomer is one O I having acid chloride, -C-Cl, end groups. When carrying out the method according to the second aspect of the invention, the reaction conditions should be selected so as to prevent a polymerisation reaction between the first and second compounds. Therefore it is preferred to add a solution of the first compound gradually, for example dropwise, to a solution of the second compound. Also it is preferred that the reaction is carried out in a solvent in which the product is substantially insoluble so that the pro¬ duct precipitates out of solution once it is formed. When p is zero, the second compound being phosgene for example, the reaction produces a compound wherein (D) d the group -B H- is bonded at both sides to a Y atom, such <E>e as in a carbonate. However, it is generally preferred that p is 1 and examples of reactions according to the second aspect of the invention are as follows: (a) + Cl-C-A 4 -C-Cl — ■ > Bu 3 SnO-A 1 -0-C-A 4 -C-Cl (b) Bu 3 0 0 0 0 (c) Bu 3 SnO-A 1 -OSnBU3 + C1-C-A -C-C1 -— ■ Bu 3 SnO-A 1 -O-C-A 4 -C-OSnBU3 The first compound may also be 'polymeric' and thus a third aspect of the present invention provides a method for the preparation of an organic compound comprising reacting a first compound of the formula: where R is or unsub- situted alkyl or aryl group; r' is independently zero or an integer from 1 to 3 depending upon the element M used; each Y is independently an oxygen atom, a sulphur atom, a substituted nitrogen atom other H I than -N-, or a substituted phosphorus - 8 - H (H ) 3 OH I I I atom other than -P-, -P-, or -P-; A 1 is an aromatic, aliphatic, aromatic/ aliphatic, heterocyclic, alicyclic, siloxyl or silane group, and x is an integer greater than 1, with a second compound of the formula: where X is a halogen atom or a group capable of reacting with the first compound to eliminate a compound containing M and X; B is an atom selected from carbon, phosphorus, sulphur or silicon; D is an oxygen or sulphur atom or an amine group; d is 1 if B is carbon, zero or 1 if B is phosphorus, zero, 1 or 2 if B is sulphur or zero if B is silicon; E is selected from an aromatic group, aliphatic group, OR' or NR » 2 if B is phosphorus, or from an aromatic group, aliphatic group or -OR* if B is sili¬ con, where R' is a substituted or unsubstituted alkyl or aryl group; e is zero if B is carbon or sulphur, 1 if B is phosphorus or 2 if B is silicon; and A 2 is an aromatic, aliphatic, aromatic/ aliphatic, heterocyclic, alicyclic, siloxyl or silane group, (R) r - I to eliminate the compound -M-X and produce a compound of the formula: Many different types of compounds can be prepared by the method according to any of the above aspects of the invention. These include, for example, esters, thioesters, amides, thioamides, imides, thioimides, carbonates, thiocarbonates and urethanes, but pre¬ ferably esters, thioesters, carbonates or thiocar¬ bonates are prepared. Therefore it is preferred that (D) d O II II the group -B- is a carbonyl -C- group or a thiocarbonyl S (E) e II e -C- group, more preferably a carbonyl group, and that the atom Y is an oxygen or sulphur atom, more pre¬ ferably an oxygen atom. The methods of the invention are especially advantageous for the preparation of aro¬ matic esters, aromatic thioesters, aromatic carbonates or aromatic thiocarbonates, these being difficult to produce by known commercial methods. By 'aromatic ester', 'aromatic thioester', etc, is meant a compound containing an ester group, thioester group, carbonate group or thiocarbonate group bonded to an aromatic group, for example Thus it is preferred that the group A- in the first compound is partly aromatic and each atom Y is bonded to an aromatic group of A-^. It is especially preferred that the compound produced by the reaction contains an ester, thioester, carbonate or thiocar- bonate group that is bonded on both sides to an aroma¬ tic group; that is to say the resulting compound contains, for example, an aromatic ester group Aromatic esters, thioesters, carbonates or thiocarbonates may be prepared by reacting a difunc- tional compound containing two (R) r M- groups or a poly- meric compound containing the repeat uniitt — t_-Mv-Y ~ -'A- .l—Y- IJ— as defined in the above aspects of the invention, or they may be prepared by reacting a monofunctional com¬ pound containing only one (R) r -M- group with a second compound which may be either mono- or difunctional. Accordingly, in a fourth aspect the present inven¬ tion provides a method for the preparation of an aroma¬ tic ester, aromatic thioester, aromatic carbonate or aromatic thiocarbonate compound comprising reacting a first compound of the formula: where each R is independently a substituted or unsubstituted alkyl or aryl group; r is an integer from 1 to 4 inclusive depending upon the element M used; M is an element selected from Group IIIB, IVB or VB of the Periodic Table or a transition metal. excluding carbon, silicon, nitro¬ gen, phosphorus, boron, aluminium and titanium; Z*-*- is an oxygen or a sulphur atom, and; A 3 is an aromatic, aliphatic, aromatic/ aliphatic, heterocyclic, ali- cyclic, siloxyl or silane group, or a hydrogen atom with a second compound of the formula: Z 2 • - II X-C-J where X is a halogen atom or a group capable of reacting with the first compound to eliminate M and X; Z 2 is either an oxygen or a sulphur atom; and J is either the atom or group X, or the group A 2 where A 2 is an aromatic, aliphatic, aromatic/aliphatic, hetero¬ cyclic, alicyclic, siloxyl or silane group, or Z 2 the group A 4 -C-X, where A 4 is an aroma¬ tic, aliphatic, aromatic/aliphatic, heterocyclic, alicyclic, siloxyl or silane group, to eliminate the compound (R) r MX and produce an aroma¬ tic ester, aromatic thioester, aromatic carbonate or aromatic thiocarbonate compound of the formula: - 12 - where L is either the atom or group X, the group Z 2 A-*, the group -A A 4 -CI'-X, or the group . The preferred stoichiometric ratio of the first compound to the second compound according to the fourth aspect of the invention is either 1:1 or 2:1. If a stoichiometric ratio of 1:1 is chosen the second com¬ pound may be of the formula: z 2 X-C-A 2 and reaction of the two ' compounds produces a compound of the formula: An example of this reaction is: Bu 3 SnO- Λ >-A 3 + Cl- Alternatively the second compound may be of the formula: Z 2 Z 2 II . II X-C-A 4 -C-X to produce; again using a stoichiometric ratio of first to second, compounds of 1:1, a compound of the formula: Z 2 A 3 -<( ^-Z * - * —C-A 4 -C-X An example of this reaction is: Bu 3 SnO-< ~ Λ-A 3 + C1- To prevent the product from reacting with a further molecule of the first compound it is preferred that the first and second compounds are reacted together by gradually adding, for example in drops, a solution of the first compound to a solution of the second compound, and also that the reaction is carried out in a solvent in which the compound produced by the reaction is substantially insoluble so that it precipi¬ tates out of solution once it is formed. In another alternative the second compound may be Z 2 II of the formula X-C-X to produce a monomer of the for¬ mula: An example of this reaction is: Bu 3 SnO-<(~~Λ-A 3 + Cl- If a stoichiometric ratio of 2:1 is used in the method according to the fourth aspect of the invention, the second compound is preferably of the formula: Z 2 Z 2 I , II X-C-A 4 -C-X the reaction of first and second compounds then pro¬ ducing a monomer of the formula: An example of this reaction is: Z 2 Preferably in the resulting compound the -C-Z^- group is bonded on both sides to an aromatic group. Therefore it is preferred that the A 2 and A 4 groups in the second compounds are each at least partly aromatic, z 2 ; ' and the -C- group is bonded to an aromatic group of the A 2 or A 4 group. Thus the compound produced by the reaction preferably contains a group of the formula and Z 2 are oxygen atoms, the react on between the f rst and second com¬ pounds therefore producing an aromatic ester. Hereinafter the description of the invention rela¬ tes to all aspects of the invention unless otherwise specified. The method according to the invention is espe¬ cially advantageous for the preparation of compounds wherein at least one end group, and preferably both end groups, are aromatic, for example a phenyl group. Such compounds are useful as monomers which can be poly¬ merised with one or more other types of monomers, or with themselves, to form, for example, polyesters or polyetheresters. However, the method according to the invention may also be used for the preparation of com¬ pounds which are not for subsequent use in polymerisa¬ tion reactions. One advantage of the invention is that compounds can often be prepared using relatively low reaction temperatures, usually between -30 degrees and 150 degrees C (although it is to be understood that higher and lower temperatures can also be used) . The use of low temperatures enables thermally sensitive groups to be included in the compound, for example carbon-carbon double and triple bonds. Another advantage is that the reagents and solvents used in the reaction can be chosen to be rela¬ tively non-hazardous. Also the eliminated compounds or by-product, (R) r MX, of the reaction is generally soluble in many solvents, making purification of the resulting compound an unusually easy task.- Furthermore this by-product may form a starting reagent for the preparation of the first compound. Preferably the element M in the first compound is selected from Group IVB of the Periodic Table and is in oxidation state (+4). More preferably M is either tin or germanium, and tin (+4) is especially preferred. Suitable groups for R include unsubstituted alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, octyl etc., substituted alkyl groups such as benzyl or phenylethyl, or a substituted or unsubstituted aryl group such as phenyl, naphthyl or biphenyl. Preferably, however, R is an alkyl group containing 3 or 4 carbon atoms, an n-butyl group being especially preferred. The number, r, of R groups attached to the element M depends upon the valency of the element M; for example when M is tin (+4) then r is 3. Thus in the first and second aspects of the invention the first compound preferably has the formula B^Sn-Y-A**—Y-SnBU3, and in the third aspect the first compound preferably has There are many groups suitable for use as the A*^-, A 2 , A 3 and A 4 groups of the first and second compounds. As stated above these are selected from an aromatic, aliphatic, aromatic/aliphatic, heterocyclic, alicyclic, siloxyl or silane group, or for A 3 a hydrogen atom. This includes substituted or unsubstituted groups, heteroaromatic, heteroaliphatic and multiple aromatic groups which may be joined by an oxygen or sulphur atom or sulphone, i ide or ketone group for example. The A^ and A 4 groups are difunctional, the A-^ group being bonded at each end to a Y atom or group, and the A 4 (D) d Z 2 II α II group belncp'bonded at each end to a -B- group or -C- " . (E) e group. The A 2 and A 3 groups are monofunctional and, as mentioned above, it is preferred that the end of the A 2 or A 3 group remote from the B or Z*-*- atom respectively is aromatic. The following list gives examples of suitable groups for the monofunctional A 2 and A 3 groups. Similar groups are also suitable for A-^ and A 4 by removal of a hydrogen atom, thus providing a difunc¬ tional group. o H* f CF2 } " ■ H -__ °{ CF2 \;° - These examples listed for the A groups are bonded to the B or Y atom with an aromatic carbon atom. However groups may also be chosen for any one of the A groups wherein an aliphatic carbon atom or a silicon atom is bonded to the Y atom of the first compound or the B or C atom of the second compound as appropriate. Also the A 2 and A 4 groups may contain an oxygen, nitro- gen, or sulphur for example which bonds to the B or C atom respectively in the second compound in the first, second or third aspects of the invention. Typical solvents used in the process of the present invention include, for example, chloroform, xylene, toluene, tetrahydrofuran, chlorobenzene, 1,2-dichloro- ethane, benzophenone, diphenylsulphone, or mixtures thereof, although it should be remembered that when the compound produced has end groups of the formula (R) r M- or -X then the solvent chosen should be one in which the compound produced is substantially insoluble. Once ' the compound has been isolated it is possible for the by-product to be easily removed, for example by extraction with acetone, hexane, methanol or other simple solvents which do not affect the resulting com¬ pound adversely. The by-product can then be recovered by distillation or crystallisation for example. There are a number of possible routes for preparing the first compound for the method according to the invention. In the first aspect of the invention the first compound, for example B^SnO-A^-OSnBu3, may be prepared by reaction of B^SnOMe with HO-A-^-OH. Similarly in the second aspect of the invention the • De Pre¬ The invention will now be illustrated by the following examples. Example 1 To 400 mis of xylene was added 50g of thiophenol and 135.3g of bis(tributyltin)oxide. The reaction mix¬ ture was heated to boiling and water of reaction removed using a Dean-Stark head. After all the water had been removed heating was discontinued and when refluxing had- subsided 46.06g of isophthaloyl dichloride added. This produced a slight yellowing of the solution. The mix¬ ture was then heated to reflux for 3 hours and then allowed to cool. The colourless crystalline product was collected by filtration, washed with cold toluene and dried. A further crop of crystals was obtained by con¬ centrating the mother liquors. Yield was 76.5 g, 96%. The product *was identified as . The analogous terephthaloyl product was prepared by repeating the above reaction, replacing the isopthaloyl dichloride with terephthaloyl dichloride. Example 2 To 225 mis of xylene was added 5.50g of hydro- quinone and 29.81g of bis(tributyltin)oxide. The reac¬ tion mixture was heated to boiling and water of reaction removed using a Dean-Stark head. After all the water had been removed heating was discontinued and when refluxing has subsided 24.43g of 4-phenoxybenzoyl- chloride added. The mixture was then heated to reflux for 3 hours and then allowed to cool. The colourless crystalline product was collected by filtration, washed with cold toluene and dried. A further crop of crystals was obtained by concentrating the mother liquor. Yield was 24.Og, 90%. The product was identified as This monomer may be reacted with a mixture of terephthaloyl and isophthaloyl chlorides in 1,2-dichloroethane together with N,N-dimethylformamide and aluminium chloride to produce a polymer of the repeat unit: Example 3 To 125 mis of xylene was added 6.0g of phenoxyphe- nol .ahd 9.60 ' g-of bis(tributyltin)oxide. The reaction mixture wa.s heated to boiling and water of reaction removed using a Dean-Stark head. After all the water had been removed heating was discontinued and when refluxing had subsided 3.27g of terephthaloyl chloride added. The mixture was heated to reflux for 3 hours and then allowed to cool. The colourless crystalline pro¬ duct was collected by filtration, washed with cold toluene and dried. A further crop of crystals was obtained by concentrating the mother liquor. Yield 7.5g, 91%. The product was identified as The analogous isophthaloyl product was prepared by repeating the above reaction, replacing the terephtha¬ loyl dichloride with isophthaloyl dichloride. This monomer may be reacted with a mixture of terephthaloyl and isophthaloyl chloride in 1,2-dichloroethane together with N,N-dimethylformamide and aluiminium chloride to produce a polymer of the repeat unit: Example 4 To 500 mis of toluene was added 15.32g of bisphenol A and 43.lg of tributyltinmethoxide. The reaction was heated to boiling and using a fractionating column ethanol was removed. When all the methanol had been removed heating was discontinued and when refluxing had subsided 18.86g of benzoylchloride added. The mixture was then heated to reflux for 3 hours and then allowed to cool. * The colourless crystalline product was collected by filtration, washed with cold toluene and dried. A further crop of crystals was obtained by con¬ centrating the mother liquors. Yield 27.2g, 93%. The product was identified as The above reaction was repeated a number of times, the bisphenol A being replaced in each repeated reaction with a different compound as indicated below: a) replacing bisphenol A with hydroquinone to produce the monomer O O ©- • ϊ- β -ø-- 0" * " © b) replacing biphenol A with methylhydroquinone to produce the monomer c) replacing bisphenol A with 4,4'-dihydroxydiphenyl ether to produce the monomer to produce the monomer Example 5 To 100 is of xylene was added 3.1g of methylhydro¬ quinone and 14.70g of bis(tributyltin)oxide. The reac¬ tion mixture was heated to boiling and water of reaction removed using a Dean-Stark head. After all the water had been removed heating was discontinued and when refluxing had subsided 9g of 4-n-propylbenzoyl chloride added. The mixture was then heated to reflux for 3 hours. The pale yellow solution was concentrated on a rotary evaporator leaving a yellow oil. This was dissolved in methylcyclohexane and cooled to -15C 0 to give a colourless, crystalline product. Yield 9g, 86% - 23 - The product was identified as Me Example 6 To 200 mis of toluene was added 13.84g of 4-bromophenol and 23.84g of bis(tributyltin)oxide. The reaction mixture was heated to boiling and water of reaction reπrσved using a Dean-Stark head. After all the water had * been removed heating was discontinued and when refluxing had subsided 8.12g of terephthaloyl chloride added. The mixture was then refluxed for two hours and then allowed to cool. The white crystalline product was collected by filtration, washed with cold toluene and dried. A further crop of crystals was obtained by con¬ centrating the mother liquor. Yield 17.68g, 93% The product was identified as. Example 7 To 150m mis of toluene was added 6.61g of hydro- quinone and 35.76g of bis(tributyltin)oxide. The reac¬ tion mixture was heated to boiling and water of reaction removed using a Dean-Stark head. After all the water had been removed heating was discontinued and when refluxing had subsided 19.03g of p-fluorobenzoyl chloride added. The mixture was refluxed for one hour and then allowed to cool. The white crystalline product was collected by filtration, washed with cold toluene and dried. A further crop of crystals was obtained by concentrating the mother liquor. Yield 19.89g 93.5% The product was identified as, Example 8 To 150m mis of toluene was added 9.97g of ethyl-4-hydrόxybenzoate and 17.88g of bis(tributyltin)oxide. The reaction mixture was heated to boiling and water of reaction removed using a Dean-Stark head. After all the water had been removed heating was discontinued and when refluxing had subsided 27.92g of 4-phenoxybenzoyl chloride added. The mixture was refluxed for one hour and then allowed to cool. No precipitate formed on cooling. The toluene was removed under reduced pressure and replaced by hexane. After cooling to -18°C a white crystalline product was obtained. A further crop of crystals was obtained by concentrating the mother liquor. This material was very soluble at room temperature in a number of solvents. Yield 37.40g 86% The product was identified as Example 9 To 150 mis of toluene was added 5.51g of hydro- quinone and 29.80g of bis(tributyltin)oxide. The reac¬ tion mixture was heated to boiling and water of reaction removed using a Dean-Stark head. After allowing to cool - 25 - the solution was transferred to a dropping funnel equipped with a pressure equalising side arm. This solution was then slowly added to an almost refluxing solution of 30.45g of terephthaloyl chloride in 150 mis of toluene. After the addition was complete the mixture was refluxed for 2 hours and then allowed to cool. The white crystalline product * was collected by filtration washed with cold toluene and dried. Yield 20g 88% The product was identified as Example 10 To 200 ml of toluene was added 20.43g of 4-phenylphenol and 35.76g of bis(tributyltin)oxide. The reaction mixture was heated to boiling and water of reaction removed using a Dean-Stark head. After all the water had been removed the reaction mixture was allowed to cool. When cool the solution was transferred to a dropping funnel fitted with a pressure equalising side arm. This solution was then slowly added to a warm solution of 48.72g of terephthaloyl chloride in 150 mis of toluene. After the addition was complete the mixture ws heated to reflux for one hour and then allowed to cool. The pale yellow crystalline product was collected by filtration washed with cold toluene and dried. Two products were identified: 1 ) .29g, 85% yield. 2) ιo% yieid* - 26 - was prepared in a similar manner. Example 11 To 200 mis of toluene was added 16.52g of hydro- quinone and 89.41g of bis(tributyltin)oxide. The reac¬ tion mixture was heated to boiling and water of reaction removed using a Dean-Stark head. After all the water had been removed heating was discontinued. One the tem¬ perature of the solution had droped to 80°C a solution of 12.18g of . " terephthaloyl chloride in 50 mis of toluene was slowly added over 45 minutes. After the addition was complete the whole mixture was refluxed for 2 hours. Once cool the toluene was removed and replaced with 200 mis of methanol plus 20 mis of a 50% solution of a hydrochloric acid. The white solid was collected by filtration and washed with 300 mis of methanol at 50°C. Yield 16.40g 80% The product was identified as Example 12 To 150 mis of toluene was added lOg of 4-phenoxyphenol and 16.00g of bis(tributyltin)oxide. The reaction mixture was heating to boiling and water of reaction removed using a Dean-Stark head. After all the water had been removed heating was discontinued and the mixture allowed to cool to room temperature. Once cool a solution of 2.66g of phosgene in 18 mis of toluene was slowly added. Upon completion of the addition the mix¬ ture was stirred at room temperature for 1 hour and then - 27 - at reflux for 1 hour. After cooling to -18°C the white crystalline solid was collected by filtration washed with cold toluene and dried. Yield 9.6g 89% The product was identified as o < 0 * -° * "0 ^"O " °^G > Example 13 To 20,0 mis of toluene was added 20g of bisphenol A and 21.80g of dibutyltin oxide. The reaction mixture was heated to boiling and water of reaction removed using a Dean-Stark head. After all the water had been removed heating was discontinued and the viscous solu¬ tion allowed to cool to 90°C. To this solution was added 40.73g of 4-phenoxybenzoyl chloride and the mix¬ ture heated to reflux for 1 hour. After cooling the white crystalline product was collected by filtration, washed with cold toluene and dried. Yield 49.71g 91.5% The product was identified as

Claims: CLAIMS 1. A method for the preparation of an organic com¬ pound comprising reacting a first compound of the for¬ mula : where each R is independently a substituted or unsubstituted alkyl or aryl group; each r is independently an integer from 1 to 4 inclusive depending upon -the element M used; each M is independently an element selected from Group IIIB, IVB or VB of the Periodic .Table or a transition metal, excluding carbon, silicon, nitrogen, phosphorus, boron, alu¬ minium and titanium; each Y is independently an oxygen atom, a sulphur atom, a substituted nitro- H I gen atom other than -N-, or a substituted phosphorus atom other H <H>3 OH I I I than -P-, -P-, or -P-; and Al is an aromatic, aliphatic, aromatic/ aliphatic, heterocyclic, ali¬ cyclic, siloxyl or silane group, with a second compound of the formula: (D) d II d „ X-B-A 2 I - 29 - where X is a halogen atom or a group capable of reacting with the first compound to eliminate a compound containing M and X; B is an atom selected from carbon, phosphorus, sulphur or silicon; D is an oxygen or sulphur atom or an amine group; d is 1 if B is carbon, zero or 1 if B is phosphorus, zero, 1 or 2 if B is . ' sulphur or zero if B is silicon; E is selected from an aromatic group, aliphatic group, OR' or NR' 2 if B is phosphorus, or from an aromatic group, aliphatic group or -OR 1 if B is sili¬ con, where R' is a substituted or unsubstituted alkyl or aryl group; e is zero if B is carbon or sulphur, 1 if B is phosphorus or 2 if B is silicon; and A 2 is an aromatic, aliphatic, aromatic/ aliphatic, heterocyclic, alicyclic, siloxyl or silane group, to eliminate the compound (R) r MX and produce a compound of the formula: where G is either the group -M-(R) r , or the group - 30 - 2. A method according to claim 1, wherein the stoichiometric ratio of the first compound to the second compound is 1:2 and reaction of the first and second compounds produces a compound of the formula: 3. A method for the preparation of an organic compound comprising reacting a first compound of the formula: • • (R) r -M-Y-A 1 -Y-M-(R) r where each R is independently a substituted or unsubstituted alkyl or aryl group; each r is independently an integer from 1 to 4 inclusive depending upon the ele¬ ment M used; each M is independently an element selected from Group IIIB, IVB or VB of the Periodic Table (IUPAC 1965 revi¬ sion) or a transition metal, excluding carbon, silicon, nitro¬ gen, phosphorus, boron, aluminium and titanium; each Y is independently an oxygen atom, a sulphur atom, a substituted nitro- H gen atom other than -N-, or a substituted phosphorus atom other f <?>3 OH I I i than -P-, -p-, or -P-; and Al is an aromatic, aliphatic, aromatic/ aliphatic, heterocyclic, alicyclic. - 31 - siloxyl or silane group, with a second compound of the formula: where X is a halogen atom or a group capable of reacting with the first compound to eli¬ minate a compound containing M and X; B is an atom selected from carbon, k - phosphorus, sulphur or silicon; D is an oxygen or sulphur atom or an amine group; d is 1 if B is carbon, zero or 1 if B is phosphorus, zero, 1 or 2 if B is sulphur or zero if B is silicon; E is selected from an aromatic group, aliphatic group, OR 1 or NR' 2 if B is phosphorus, or from an aromatic group, aliphatic group or -OR* if B is silicon, where R * is a substituted or unsubsti¬ tuted alkyl or aryl group; e is zero if B is carbon or sulphur, 1 if B is phosphorus or 2 if B is silicon; and p is zero or 1, to eliminate the compound (R) r MX and produce a compound of the formula: (D) d (D) d Q-Y-A-ιL-Y-B'I ■ A A 4 -BI' (E). (E), Up where Q is the either the group (R) r M-, or the group ;and T is either the atom or group X, or the group 4. A method according to claim 3 wherein the first and second compounds are reacted together by gradually adding a solution of the first compound to a solution of the second, compound. 5. A method according to claim 3 or 4 wherein the first and second compounds are reacted together in a solvent in which the compound produced by the reaction is substantially insoluble so that the compound is pre¬ cipitated substantially as soon as it is produced. 6. A method according to any one of claims 3 to 5 wherein p is 1. 7. A method according to claim 6 wherein the first and second compounds are reacted to produce a compound of the formula: (D) d (D) d (D) d (D) d X-B II-A 4 A-B»-Y-A 1 i-Y-B«-A 4 A-B'I-X I I I I (E) e (E) e (E) e (E) e 8. A method for the preparation of an organic compound comprising reacting a first compound of the formula: where R is independently a substituted or unsub- situted alkyl or aryl group; - 33 - r' is independently zero or an integer from 1 to 3 depending upon the element M used; each Y is independently an oxygen atom, a sulphur atom, a substituted nitrogen atom other H I than -N-,- or a substituted phosphorus H <H>3 OH I I i atom other than -P-, -P-, or -P-; A1 is an aromatic, aliphatic, aromatic/ aliphatic, heterocyclic, alicyclic, - ' siloxyl or silane group, and x is an integer greater than 1, with a second compound of the formula: where X is a halogen atom or a group capable of reacting with the first compound to eli¬ minate a compound containing M and X; B is an atom selected from carbon, phosphorus, sulphur or silicon; D is an oxygen or sulphur atom or an amine group; d is 1 if B is carbon, zero or 1 if B is phosphorus, zero, 1 or 2 if B is sulphur or zero if B is silicon; E is selected from an aromatic group, aliphatic group, OR' or NR' 2 if B is - 34 - phosphorus, or from an aromatic group, aliphatic group or -OR' if B is silicon, where R' is a substituted or unsubsti¬ tuted alkyl or aryl group; e is zero if B is carbon or sulphur, 1 if B is phosphorus or 2 if B is silicon; and A 2 is an aromatic, aliphatic, aromatic/ aliphatic, heterocyclic, alicyclic, siloxyl or silane group, ( R ) r « . - • I to eliminate-the compound -M-X and produce a compound of the formula: (D) d (D) d A -B-Y-A 1 -Y-B-A 2 I I (E) e (E) e 9. A method according to any one of the preceding (D) d 0 II α II claims wherein the group -B- is a carbonyl group -C-, or S (E) e II e a thiocarbonyl group -C-. (D) d II 10. A method according to claim 9 wherein the group -B- 0 (E) e II e is a carbonyl group -C-. 11. A method according to any one of the preceding claims wherein Y is oxygen or sulphur. 12. A method according to claim 11 wherein Y is oxygen 13. A method according to any one of the preceding claims wherein the group A^ is at least partly aromatic and each atom Y is bonded to an aromatic group of A- . - 35 - 14. A method according to any one of the preceding claims wherein the first and second compounds are selected so that reaction of the compounds produces an aromatic ester, aromatic thioester, aromatic carbonate or aromatic thiocarbonate compound. 15. A method for the preparation of an aromatic ester, aromatic thioester, aromatic carbonate or aromatic thiocarbonate compound comprising reacting a first com¬ pound of the formula: where 'each R is independently a substituted or unsubstituted alkyl or aryl group; r is an integer from 1 to 4 inclusive depending upon the element M used; M is an element selected from Group IIIB, IVB or VB of the Periodic Table or a transition metal, excluding carbon, silicon, nitro¬ gen, phosphorus, boron, aluminium and titanium; Z^ is an oxygen or a sulphur atom; and A 3 is an aromatic, aliphatic, aromatic/ aliphatic, heterocyclic, ali¬ cyclic, siloxyl or silane group, or a hydrogen atom with a second compound of the formula: Z 2 * II X-C-J where X is a halogen atom or a group capable of reacting with the first compound to - 36 - eliminate M and X; Z 2 is either an oxygen or a sulphur atom; and J is either the atom or group X, or the group A 2 where A 2 is an aromatic, aliphatic, aromatic/aliphatic, hetero¬ cyclic, alicyclic, siloxyl or silane group, or Z 2 the group A 4 -C-X, where A 4 is an aroma¬ tic aliphatic, aromatic/aliphatic, . ' heterocyclic, alicyclic, siloxyl or silane group, to eliminate the compound (R) r MX and produce an aromatic ester, aromatic thioester, aromatic carbonate or aroma¬ tic thiocarbonate compound of the formula: where L is either the atom or group X, the group Z 2 Δ n , the group -A A * *-C'I-X, or the group 16. A method according to claim 15 wherein Z^- is an oxygen atom. 17. A method according to claim 15 or 16 wherein Z 2 is an oxygen atom. 18. A method according to any one of claims 15 to 17 wherein the stoichiometric ratio of the first compound to the second compound is 1:1. 19. A method according to claim 18 wherein the second compound is of the formula: - 37 - Z 2 X-C-A 2 and the first and second compounds react to produce an aromatic ester, aromatic thioester, aromatic carbonate or aromatic thiocarbonate compound of the formula: 20. A method according to claim 19 wherein the group A 2 Z 2 is at least partly aromatic and the group -C- is bonded to an aromatic group of A 2 . 21. A method according to claim 18 wherein the second compound is of the formula: Z 2 Z 2 II . II X-C-A -C-X and the first and second compounds react to produce an aromatic ester, aromatic thioester, aromatic carbonate or aromatic thiocarbonate of the formula: 22. A method according to claim 21 wherein the first and second compounds are reacted together by gradually adding a solution of the first compound to a solution of the second compound. 23. A method according to claim 21 or 22 wherein the first and second compounds are reacted together in a sovlent in which the compound produced by the reaction is substantially insoluble so that the compound is pre¬ cipitated substantially as soon as it is produced. - 38 - 24. A method according to any one of claims 15 to 17 wherein the second compound is of the formula: and the first and second compounds are reacted together in a stoichiometric ratio of 2:1 to produce an aromatic ester, aromatic thioester, aromatic carbonate or aroma¬ tic thiocarbonate of the formula: 25. A method according to any one of claims 21 to 24 wherein the group A 4 is at least partly aromatic and the Z 2 groups -C II- are each bonded to an aromatic group of A* A. 26. A method according to any one of the preceding claims wherein M is selected from Group IVB of the Periodic Table. 27. A method according to claim 25 wherein M is tin. 28. A method according to claim 25 or 26 wherein r is 3. 29. A method according to any one of the preceding claims wherein R is a butyl group. 30. A method according to any one of the preceding claims wherein X is a halogen atom. 31. A method according to claim 29 wherein X is a chlorine atom. 32. An organic compound of the formula: _ 33. An organic compound of the formula: 34. An organic compound of the formula: 35. An organic compound of the formula: 36. An organic compound of the formula: l J o-Q * * * * * *

Inventors: TOWLE IAN DAVID HENDERSON, TOWLE, IAN, DAVID, HENDERSON
Applicants: RAYCHEM LTD, RAYCHEM LIMITED
Application year: 1985
Main classification: C07C67
IPC codes: C07C69, C07C327, C08G61, C08G73, C08G75