CA2023392A1 - Method for making octyloxy substituted diphenyl iodonium hexafluoro metalloid salts - Google Patents
Method for making octyloxy substituted diphenyl iodonium hexafluoro metalloid saltsInfo
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- CA2023392A1 CA2023392A1 CA002023392A CA2023392A CA2023392A1 CA 2023392 A1 CA2023392 A1 CA 2023392A1 CA 002023392 A CA002023392 A CA 002023392A CA 2023392 A CA2023392 A CA 2023392A CA 2023392 A1 CA2023392 A1 CA 2023392A1
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- Prior art keywords
- octyloxyphenyl
- phenyliodonium
- salt
- tosylate
- mixture
- Prior art date
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- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/90—Antimony compounds
- C07F9/902—Compounds without antimony-carbon linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/225—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing halogen
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Pyrrole Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Saccharide Compounds (AREA)
Abstract
RD-19,343 METHOD FOR MAKING OCTYLOXY SUBSTITUTED DIPHENYL IODONIUM
HEXAFLUORO METALLOID SALTS
Abstract of the Disclosure A one pot method is provided for preparing an (octyloxyphenyl) phenyliodonium tosylate and the corresponding hexafluorometalloid salt. n-Octylphenyl ether is initially prepared using a halooctane and phenol in the presence of a phase transfer catalyst followed by the addition of iodobenzene, a peracid, and p-toluene sulfonic acid. The resulting (octyloxyphenyl)phenyl iodonium tosylate can be directly methathesized after an optional treatment step with an alkali metal hexafluoroantimonate salt. The (octyloxyphenyl)phenyl iodonium hexafluorometalloid salt can be used as a photoinitiator for UV curable organic materials such as epoxy resins.
HEXAFLUORO METALLOID SALTS
Abstract of the Disclosure A one pot method is provided for preparing an (octyloxyphenyl) phenyliodonium tosylate and the corresponding hexafluorometalloid salt. n-Octylphenyl ether is initially prepared using a halooctane and phenol in the presence of a phase transfer catalyst followed by the addition of iodobenzene, a peracid, and p-toluene sulfonic acid. The resulting (octyloxyphenyl)phenyl iodonium tosylate can be directly methathesized after an optional treatment step with an alkali metal hexafluoroantimonate salt. The (octyloxyphenyl)phenyl iodonium hexafluorometalloid salt can be used as a photoinitiator for UV curable organic materials such as epoxy resins.
Description
rJ~,~
RD-19,343 DlP~N~L I~ L~ 5~L~o~5 ~I~
~LQ~a-~9f~nce tV B~ d ~Qli~a~iQn~
Reference is made to copending application Crivello et al, Serial No. 171063, filed 3/21/1988 for NON-TOXIC ARYL O~IUM SALTS, UV CUR~BLE COATING COMPOSITIONS AND
FOOD PACKAGING USE which is assigned to the same assignee as the pres~nt invention and incorporated herein by reference Prior to the present invention, as shown by Cri~ello, U.S. Patent 3,981,897, Method for Making Certain Halonium Salt Photoinitiators, diaryliodonium salts, such as diphenyliodonium hexafluoroantimonate were prepared by effecting reaction betwee~ an intermedia~e diarylhalonium bisulfate and an alkylhexafluoro salt, such as diphenyliodonium hexafluoroantimonate.
In copending application Serial No. 171063, filed 3/21/1988, a step-~ise procedure is shown for making an (octyloxyphenyl) phenyliodonium hexafluorometalloid salt which is used as a photoinitiator in non-toxic W curable coating compoqitions. The procedure of Serial No. 171063 is directed to the initial synthesis of n-octylphenylether and the separate synthesis of a phenyliodosotosylate. The (octyloxyphenyl) phenyliodonium tosylate is synthesized in a separate reaction. Finally, th* (octyloxyphenyl) phenyliodonium to~ylate is metathasized with sodium hexafluoroantimonate to provide the desired (octyloxyphenyl) phenyliodonium hexafluoroantimonate salt. Although the method of Serial No. 171063 can provide the preferred (4--2 ~
RD-19,343 octyloxyphenyl) phenyliodonium hexafluoroantimonate salt at satisfactory yields, severaL steps are required which renders the procedure unsuitable for commercial production.
S Summ~Y of t~e InventiQn The present invention is based on the discovery that (octyloxyphenyl) phenyliodonium hexafluoroantimonate can be made by a one pot procedure involving the employment of a phase transfer catalyst in the initial synthesis of the n-oc~ylphenyl ether, followed by the removal of the aqueous basic solution from tha initial synthe is mixture. Phenyl iodide and a peracid can be added directly to the n-octylphenyl ether followed by the addition of p-toluene ; 15 sulfonlc acid in the same reaction vessel. The resulting hydroxy(tosyloxy)iodobenzene which forms, reacts in situ with ~he n-octylphenyl ether while the tempera~ure is maintained at about 30C or below. Recovery of the resulting (octyloxyphenyl)phenyliodonium tosylate can be achieved by extracting the reaction mixture with an organic solvent and water and triturating the reaction mixture with aliphatic hydrocarbon solvent. The metathesis of the (octyloxyphenyl)phenyliodonium ~osylate and an alkali metal hexafluoroantimonate salt can be effected in the same vessel.
As used hereinaf~er the term "(octyloxyphenyl)phenyliodonium hexafluorometalloid salt~ means the corresponding hexafluoroantimonate, hexafluorophosphate, or hexafluoroarsenate salt.
:
There is provided by the present invention, a one pot method for making an (oc~yloxyphenyl) phenyliodonium hexafluorome~alloid salt which comprises, ~ Jr RD-19,343 (1) effecting reaction between phenol and a-bromo octane in the presence of an aqueous basic solution and a phase transfer catalyst to form n-octylphenyL ether, (2) effecting the removal of the aqueous basic solution from the mixture of (1), (3) adding with agitation to the mixture of (2), iodobenzene, a peracid and a toluenesulfonic acid, while maintaining the resulting mixture at a temperature of from -20C to 100C to form an (octyloxyphenyl) phenyliodonium tosylate complex, (4) effecting ~he separation of the (octyloxyphenyl) phenyliodonium tosylate from the complex of (3) and, (5) effecting a metathesis reaction between the (octyloxyphenyl) phenyliodonium tosylate of (4) and an al~ali metal hexafluorome~alloid salt to form the (octyloxyphenyl) phenyliodonium hexafluorometalloid salt.
In the practice of the method of the present invention, n-octylphenyl e~her is initially synthesized by effecting reaction between 1 to 3 mols of phenol, per mol of a halooctane such as l-bromooctane in the presence of a phase transfer catalyst, for example tetrabutylammoniumbromide,cetylammonium chloride, and trime~hylben~ylammonium chloride, an inert organic solvent, for example, toluene, benzene, xylene, chlorobenzene, n-hexane, n-heptane, n-octane, dichloromethane, and an aqueous alkali metal hydroxide olution, such as sodium or potassium hydroxide. The reaction mixture can be agitated and refluxed for a period of from 3 to 36 hours and then allowed to cool to room temperature. The aqueous layer can be removed by decantation and the organic layer can be extracted with an alkali metal hydroxide solution with water thereafter the organic solvent can be removed under reduced pressure. Iodobenzene can be added to the same pot ,, '- ' RD-19,343 containing the n-octylphenyl ether in substantially equal molar amounts at temperatures in a range of from 0C to 60C.
A suitable peracid, such as peracetic acid, perbenzoic acid, m-chloroperbenzoic, or perphthalic acid can be added gradually to the resulting mixture of iodobenzene and n-octylphenyl ether while it is being stirred and ma~n~ained at a temperature of 20C to 40C over a period of from 15 to 120 minutes. After the peracid has been added, the reaction mixture can be agitated for an additional 1 to 30 hours. A
toluenesulfonic acid, such as p-toluenesulfonic acid can then be added to the mixture which can be agita~ed for an additional 1 to 8 hours. The heterogeneous reaction mixture then can become homogeneou~ t and the mixture can turn orange after a short period of time~
Various workup procedures can be used to recover the (octyloxyphenyl) phenyliodonium to~ylate from the reaction mixture prior to the additi.on of the alkali metal hexafluorometalloid salt. One procedure involves the addition of an inert organic solvent, such as toluene and water to the reaction mixture while it is agitated, followed by the separation of the aqueous layer and extraction thereof with an inert organic solvent. The organic solvent extract can be combined with ~he original organic phase. The organic solvent layer can then be extracted once with water followed ; 25 by treatment with n aliphatic hydrocarbon solvent, such as n-heptanP or n-octane to efec~ the precipitation of the desired tosylate product which can be an off-white solid.
Another procedure which can be used to recover the (octyloxyphenyl) phenyliodonium tosylate i~ triturating the reaction mixture with an aliphatic hydrocarbon, such as heptane followed by decanting the alipha~ic hydrocarbon from the resulting orange oil. A second trituration with the aliphatic hydrocarbon can be used followed by triturating with water at least twice. ~he resulting solven~ can then bP
RD-19,343 triturated once more with the aliphatic hydrocarbon and thereafter filtered and washed.
An additional work-up procedure which can be employed to recover the (octyloxyphenyl)phenyliodonium tosylate product is to initlally add with stirring an inert aromatic orqanic solvent, such as toluene, t.o the re~ction mixture with an equal volume of water foll~w~d by separating the aqueous layer and extracting it once with the aromatic organic solvent. The tosylate product can then be extracted once with water; thereafter the solvent can be removed under reduced pressure resulting in an orange solid. The orange solid can be broken up and triturated with the aliphatic organic ~olvent, such a~ heptane, filtered and washed again with the aliphatic organic solvent.
The metathesis reaction can be effected with a mixture of an inert org~nic solvent, such as acetone and an alkali metal hexafluorometalloid salt, such as the corresponding hexafluoroantimonate, hexafluorophosphate or hexafluoroarensate, referred to hereinafter as the hexafluoroantimonate salt. The hexa~luoroantimonate salt can be added to the (octyloxyphenyl~ phenyliodonium tosylate followed by agitating the resulting mixture for a period of from 15 to 180 minutes. The mixture can then be filtered and then added to an excess amount of distilled water. The resulting oil can then be triturated with water and the water decan~ed followed by the addition of further amounts of water. The mixture can then be stirred for another 15 to 180 minu~es and the water ~ecan~ed and an inert aliphatic sol~ent such as n-heptane or n-octane can be added. This procedure result~ in the cryqtallization of the solid (octyloxyphenyl) phenyliodonium hexafluoroantimonate which can be broken up, waQhed with additional aliphatic organic solvent and then filtered.
RD-19,343 DlP~N~L I~ L~ 5~L~o~5 ~I~
~LQ~a-~9f~nce tV B~ d ~Qli~a~iQn~
Reference is made to copending application Crivello et al, Serial No. 171063, filed 3/21/1988 for NON-TOXIC ARYL O~IUM SALTS, UV CUR~BLE COATING COMPOSITIONS AND
FOOD PACKAGING USE which is assigned to the same assignee as the pres~nt invention and incorporated herein by reference Prior to the present invention, as shown by Cri~ello, U.S. Patent 3,981,897, Method for Making Certain Halonium Salt Photoinitiators, diaryliodonium salts, such as diphenyliodonium hexafluoroantimonate were prepared by effecting reaction betwee~ an intermedia~e diarylhalonium bisulfate and an alkylhexafluoro salt, such as diphenyliodonium hexafluoroantimonate.
In copending application Serial No. 171063, filed 3/21/1988, a step-~ise procedure is shown for making an (octyloxyphenyl) phenyliodonium hexafluorometalloid salt which is used as a photoinitiator in non-toxic W curable coating compoqitions. The procedure of Serial No. 171063 is directed to the initial synthesis of n-octylphenylether and the separate synthesis of a phenyliodosotosylate. The (octyloxyphenyl) phenyliodonium tosylate is synthesized in a separate reaction. Finally, th* (octyloxyphenyl) phenyliodonium to~ylate is metathasized with sodium hexafluoroantimonate to provide the desired (octyloxyphenyl) phenyliodonium hexafluoroantimonate salt. Although the method of Serial No. 171063 can provide the preferred (4--2 ~
RD-19,343 octyloxyphenyl) phenyliodonium hexafluoroantimonate salt at satisfactory yields, severaL steps are required which renders the procedure unsuitable for commercial production.
S Summ~Y of t~e InventiQn The present invention is based on the discovery that (octyloxyphenyl) phenyliodonium hexafluoroantimonate can be made by a one pot procedure involving the employment of a phase transfer catalyst in the initial synthesis of the n-oc~ylphenyl ether, followed by the removal of the aqueous basic solution from tha initial synthe is mixture. Phenyl iodide and a peracid can be added directly to the n-octylphenyl ether followed by the addition of p-toluene ; 15 sulfonlc acid in the same reaction vessel. The resulting hydroxy(tosyloxy)iodobenzene which forms, reacts in situ with ~he n-octylphenyl ether while the tempera~ure is maintained at about 30C or below. Recovery of the resulting (octyloxyphenyl)phenyliodonium tosylate can be achieved by extracting the reaction mixture with an organic solvent and water and triturating the reaction mixture with aliphatic hydrocarbon solvent. The metathesis of the (octyloxyphenyl)phenyliodonium ~osylate and an alkali metal hexafluoroantimonate salt can be effected in the same vessel.
As used hereinaf~er the term "(octyloxyphenyl)phenyliodonium hexafluorometalloid salt~ means the corresponding hexafluoroantimonate, hexafluorophosphate, or hexafluoroarsenate salt.
:
There is provided by the present invention, a one pot method for making an (oc~yloxyphenyl) phenyliodonium hexafluorome~alloid salt which comprises, ~ Jr RD-19,343 (1) effecting reaction between phenol and a-bromo octane in the presence of an aqueous basic solution and a phase transfer catalyst to form n-octylphenyL ether, (2) effecting the removal of the aqueous basic solution from the mixture of (1), (3) adding with agitation to the mixture of (2), iodobenzene, a peracid and a toluenesulfonic acid, while maintaining the resulting mixture at a temperature of from -20C to 100C to form an (octyloxyphenyl) phenyliodonium tosylate complex, (4) effecting ~he separation of the (octyloxyphenyl) phenyliodonium tosylate from the complex of (3) and, (5) effecting a metathesis reaction between the (octyloxyphenyl) phenyliodonium tosylate of (4) and an al~ali metal hexafluorome~alloid salt to form the (octyloxyphenyl) phenyliodonium hexafluorometalloid salt.
In the practice of the method of the present invention, n-octylphenyl e~her is initially synthesized by effecting reaction between 1 to 3 mols of phenol, per mol of a halooctane such as l-bromooctane in the presence of a phase transfer catalyst, for example tetrabutylammoniumbromide,cetylammonium chloride, and trime~hylben~ylammonium chloride, an inert organic solvent, for example, toluene, benzene, xylene, chlorobenzene, n-hexane, n-heptane, n-octane, dichloromethane, and an aqueous alkali metal hydroxide olution, such as sodium or potassium hydroxide. The reaction mixture can be agitated and refluxed for a period of from 3 to 36 hours and then allowed to cool to room temperature. The aqueous layer can be removed by decantation and the organic layer can be extracted with an alkali metal hydroxide solution with water thereafter the organic solvent can be removed under reduced pressure. Iodobenzene can be added to the same pot ,, '- ' RD-19,343 containing the n-octylphenyl ether in substantially equal molar amounts at temperatures in a range of from 0C to 60C.
A suitable peracid, such as peracetic acid, perbenzoic acid, m-chloroperbenzoic, or perphthalic acid can be added gradually to the resulting mixture of iodobenzene and n-octylphenyl ether while it is being stirred and ma~n~ained at a temperature of 20C to 40C over a period of from 15 to 120 minutes. After the peracid has been added, the reaction mixture can be agitated for an additional 1 to 30 hours. A
toluenesulfonic acid, such as p-toluenesulfonic acid can then be added to the mixture which can be agita~ed for an additional 1 to 8 hours. The heterogeneous reaction mixture then can become homogeneou~ t and the mixture can turn orange after a short period of time~
Various workup procedures can be used to recover the (octyloxyphenyl) phenyliodonium to~ylate from the reaction mixture prior to the additi.on of the alkali metal hexafluorometalloid salt. One procedure involves the addition of an inert organic solvent, such as toluene and water to the reaction mixture while it is agitated, followed by the separation of the aqueous layer and extraction thereof with an inert organic solvent. The organic solvent extract can be combined with ~he original organic phase. The organic solvent layer can then be extracted once with water followed ; 25 by treatment with n aliphatic hydrocarbon solvent, such as n-heptanP or n-octane to efec~ the precipitation of the desired tosylate product which can be an off-white solid.
Another procedure which can be used to recover the (octyloxyphenyl) phenyliodonium tosylate i~ triturating the reaction mixture with an aliphatic hydrocarbon, such as heptane followed by decanting the alipha~ic hydrocarbon from the resulting orange oil. A second trituration with the aliphatic hydrocarbon can be used followed by triturating with water at least twice. ~he resulting solven~ can then bP
RD-19,343 triturated once more with the aliphatic hydrocarbon and thereafter filtered and washed.
An additional work-up procedure which can be employed to recover the (octyloxyphenyl)phenyliodonium tosylate product is to initlally add with stirring an inert aromatic orqanic solvent, such as toluene, t.o the re~ction mixture with an equal volume of water foll~w~d by separating the aqueous layer and extracting it once with the aromatic organic solvent. The tosylate product can then be extracted once with water; thereafter the solvent can be removed under reduced pressure resulting in an orange solid. The orange solid can be broken up and triturated with the aliphatic organic ~olvent, such a~ heptane, filtered and washed again with the aliphatic organic solvent.
The metathesis reaction can be effected with a mixture of an inert org~nic solvent, such as acetone and an alkali metal hexafluorometalloid salt, such as the corresponding hexafluoroantimonate, hexafluorophosphate or hexafluoroarensate, referred to hereinafter as the hexafluoroantimonate salt. The hexa~luoroantimonate salt can be added to the (octyloxyphenyl~ phenyliodonium tosylate followed by agitating the resulting mixture for a period of from 15 to 180 minutes. The mixture can then be filtered and then added to an excess amount of distilled water. The resulting oil can then be triturated with water and the water decan~ed followed by the addition of further amounts of water. The mixture can then be stirred for another 15 to 180 minu~es and the water ~ecan~ed and an inert aliphatic sol~ent such as n-heptane or n-octane can be added. This procedure result~ in the cryqtallization of the solid (octyloxyphenyl) phenyliodonium hexafluoroantimonate which can be broken up, waQhed with additional aliphatic organic solvent and then filtered.
-6 - 2~ Ji~
RD-19,343 In order that those skilled in the art will be better able to practice the present invention the following example is given by way of illustration and not by way of limitation. All parts are by weight unless otherwise indicated.
A mixture of 10.70 grams (liquified, 88%) phenol, (0.10 mol), .44 grams (33.0 mmol) of l-bromooctane, 5 ml of toluene, 1.66 grams (S.0 mmol) of tetrabutylammonium bromide, 10 ml of water and 12.5 grams of a 40~ solution (0.10 mol) of potas~ium hydroxide, was heated to reflux for a period of 18 hours with stirring. The reaction was then cooLed to room temperature and the aqueous layer was remo~ed. The organic ; 15 layer was extracted once with 0.5 N KOH (20 ml) once with water (20 ml). The toluene was remo~ed under reduced pressure and the n-octylphenyl ether carried on without additional purification.
There was added 6.8 grams (33.0 mmol) of iodobenzene to the n-octylphenylether which was being stirred while the mixture was maintained at room temperature. There were then added dropwise, 19.5 grams (0.08 mol) of 32%
peracetic acid to the mixture, while it was being stirred and maintained at a ~emperature of about 30C. Following the addition of the peracetic acid, the reaction mixture was allowed ~o stir for 15 hours regul~ing in the formation of a precipita~e. ~here were then added 10.0 gram~, ~.053 mol) of p-tolu~nesulfonic acid and the resulting reaction mixture was tirred f or an additional 4 hours. The resulting mixture became homogeneous after a short period of time.
The re~ction mixture was triturated twice with 70 ml of water and once with 70 ml o~ n-heptane. After each wash the solvent was filtered from the solid produc~. It was then added to the resulting mix~ure 60 ml of acetone and 9.4 ' 7" ~
RD-19,343 grams of sodium hexafluoroantimonate while the mixture was stirred for an additional 30 minute period. The acetone solution was then filtered and the acetone mixture was added to S00 ml of distilled water. There was obtained an oil S which was triturated for S minuteq and the water was decanted and 200 ml of fresh water was added. After stirring for another S minutes, the water was decanted and 200 ml of heptane was added. The material crystallized and the solid mass was broken up, triturated with neptane and than filtered. There was obtained a 82% yield of (4-octyloxyphenyl) phenyliodonium hexafluoroantimonate.
The (4-octyloxyphenyl) phenyliodonium hexafluoroantimonate salt is found to be useful as a photo initiator for 4-vinylcyclohexene dioxide when employed at about 3% by weight using a GE~3T7 lamp at a distance of 6 incheq at an exposure of about l ~econd.
Although the above example is directed to only a few of the very many variables which can be used in the practice of the method of the present invention, it should be understood tnat the preqent inven~ion i9 directed to the employment of a much broader variety of the agents in conditions as set forth in the description preceding this example.
RD-19,343 In order that those skilled in the art will be better able to practice the present invention the following example is given by way of illustration and not by way of limitation. All parts are by weight unless otherwise indicated.
A mixture of 10.70 grams (liquified, 88%) phenol, (0.10 mol), .44 grams (33.0 mmol) of l-bromooctane, 5 ml of toluene, 1.66 grams (S.0 mmol) of tetrabutylammonium bromide, 10 ml of water and 12.5 grams of a 40~ solution (0.10 mol) of potas~ium hydroxide, was heated to reflux for a period of 18 hours with stirring. The reaction was then cooLed to room temperature and the aqueous layer was remo~ed. The organic ; 15 layer was extracted once with 0.5 N KOH (20 ml) once with water (20 ml). The toluene was remo~ed under reduced pressure and the n-octylphenyl ether carried on without additional purification.
There was added 6.8 grams (33.0 mmol) of iodobenzene to the n-octylphenylether which was being stirred while the mixture was maintained at room temperature. There were then added dropwise, 19.5 grams (0.08 mol) of 32%
peracetic acid to the mixture, while it was being stirred and maintained at a ~emperature of about 30C. Following the addition of the peracetic acid, the reaction mixture was allowed ~o stir for 15 hours regul~ing in the formation of a precipita~e. ~here were then added 10.0 gram~, ~.053 mol) of p-tolu~nesulfonic acid and the resulting reaction mixture was tirred f or an additional 4 hours. The resulting mixture became homogeneous after a short period of time.
The re~ction mixture was triturated twice with 70 ml of water and once with 70 ml o~ n-heptane. After each wash the solvent was filtered from the solid produc~. It was then added to the resulting mix~ure 60 ml of acetone and 9.4 ' 7" ~
RD-19,343 grams of sodium hexafluoroantimonate while the mixture was stirred for an additional 30 minute period. The acetone solution was then filtered and the acetone mixture was added to S00 ml of distilled water. There was obtained an oil S which was triturated for S minuteq and the water was decanted and 200 ml of fresh water was added. After stirring for another S minutes, the water was decanted and 200 ml of heptane was added. The material crystallized and the solid mass was broken up, triturated with neptane and than filtered. There was obtained a 82% yield of (4-octyloxyphenyl) phenyliodonium hexafluoroantimonate.
The (4-octyloxyphenyl) phenyliodonium hexafluoroantimonate salt is found to be useful as a photo initiator for 4-vinylcyclohexene dioxide when employed at about 3% by weight using a GE~3T7 lamp at a distance of 6 incheq at an exposure of about l ~econd.
Although the above example is directed to only a few of the very many variables which can be used in the practice of the method of the present invention, it should be understood tnat the preqent inven~ion i9 directed to the employment of a much broader variety of the agents in conditions as set forth in the description preceding this example.
Claims (7)
1. A one pot method for making an (octyloxyphenyl) phenyliodonium hexafluorometalloid salt which comprises:
(1) effecting reaction between phenol and 1-bromo octane in the presence of an aqueous basic solution and a phase transfer catalyst to form n-octylphenyl ether, (2) effecting the removal of the aqueous basic solution from the mixture of (1), (3) adding with agitation to the mixture of (2), iodobenzene, peracid and a toluenesulfonic acid while maintaining the resulting mixture at a temperature of from 20°C to 100°C to form an (octyloxyphenyl) phenyliodonium tosylate complex, (4) effecting the separation of the (octyloxyphenyl) phenyliodonium tosylate from the complex of (3) and, (5) effecting a metathesis reaction between the (octyloxyphenyl) phenyliodonium tosylate of (4) and an alkali metal hexafluorometalloid salt to form the (octyloxyphenyl) phenyliodonium hexafluorometalloid salt.
(1) effecting reaction between phenol and 1-bromo octane in the presence of an aqueous basic solution and a phase transfer catalyst to form n-octylphenyl ether, (2) effecting the removal of the aqueous basic solution from the mixture of (1), (3) adding with agitation to the mixture of (2), iodobenzene, peracid and a toluenesulfonic acid while maintaining the resulting mixture at a temperature of from 20°C to 100°C to form an (octyloxyphenyl) phenyliodonium tosylate complex, (4) effecting the separation of the (octyloxyphenyl) phenyliodonium tosylate from the complex of (3) and, (5) effecting a metathesis reaction between the (octyloxyphenyl) phenyliodonium tosylate of (4) and an alkali metal hexafluorometalloid salt to form the (octyloxyphenyl) phenyliodonium hexafluorometalloid salt.
2. A method in accordance with claim 1, where the (octyloxyphenyl) phenyliodonium salt hexafluorometalloid salt is (4-octyloxyphenyl) phenyliodonium hexafluoroantimonate.
3. A method in accordance with claim 1 where the phase transfer catalyst in step 1 is tetrabutylammonium bromide.
4. A method in accordance with claim 1 where the peracid in step 3 is peracetic acid.
RD-19,343
RD-19,343
5. A method in accordance with claim 1, where the octyloxyphenyl phenyliodonium tosylate is separated from the complex by initially adding an aromatic organic solvent in water to the complex followed by separation of the aqueous layer and extraction with the aromatic organic solvent and the trituration of the solid residue with n-octane.
6. A method in accordance with claim 1, where the metathesis is effected with sodium hexafluoroantimonate.
7. The invention as defined in any of the preceding claims including any further features of novelty disclosed.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/429,744 US4992571A (en) | 1989-10-31 | 1989-10-31 | Method for making octyloxy substituted diphenyl iodonium hexafluoro metalloid salts |
| US429,744 | 1989-10-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2023392A1 true CA2023392A1 (en) | 1991-05-01 |
Family
ID=23704556
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002023392A Abandoned CA2023392A1 (en) | 1989-10-31 | 1990-08-16 | Method for making octyloxy substituted diphenyl iodonium hexafluoro metalloid salts |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US4992571A (en) |
| EP (1) | EP0425920B1 (en) |
| JP (1) | JPH0751524B2 (en) |
| AT (1) | ATE110706T1 (en) |
| CA (1) | CA2023392A1 (en) |
| DE (1) | DE69012047T2 (en) |
| FI (1) | FI905354A0 (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5401607A (en) * | 1991-04-17 | 1995-03-28 | Polaroid Corporation | Processes and compositions for photogeneration of acid |
| US6147184A (en) * | 1992-03-23 | 2000-11-14 | Rhone-Poulenc Chimie | Onium borates/borates of organometallic complexes and cationic initiation of polymerization therewith |
| FR2688783A1 (en) * | 1992-03-23 | 1993-09-24 | Rhone Poulenc Chimie | NOVEL BORONES OF ONIUM OR ORGANOMETALLIC COMPLEX CATIONIC PRIMERS FOR POLYMERIZATION. |
| US5334489A (en) * | 1992-10-23 | 1994-08-02 | Polaroid Corporation | Process for generation of squaric acid and for imaging, and imaging medium for use therein |
| US5286612A (en) * | 1992-10-23 | 1994-02-15 | Polaroid Corporation | Process for generation of free superacid and for imaging, and imaging medium for use therein |
| US5441850A (en) * | 1994-04-25 | 1995-08-15 | Polaroid Corporation | Imaging medium and process for producing an image |
| US5741630A (en) * | 1994-04-25 | 1998-04-21 | Polaroid Corporation | Process for fixing an image, and medium for use therein |
| US5488147A (en) * | 1994-07-21 | 1996-01-30 | Minnesota Mining And Manufacturing Company | Diaryliodonium fluoroalkyl sulfonate salts and a method of making |
| US5914213A (en) | 1996-11-27 | 1999-06-22 | Polaroid Corporation | Process and composition for generation of acid |
| US6015907A (en) * | 1996-11-27 | 2000-01-18 | Polaroid Corporation | Trisubstituted pyridine dyes |
| US6110638A (en) * | 1996-11-27 | 2000-08-29 | Polaroid Corporation | Process and composition for generation of acid |
| EP1390664A4 (en) | 2001-03-30 | 2008-01-02 | Univ Arizona | Materials, methods, and uses for photochemical generation of acids and/or radical species |
| US8048981B2 (en) * | 2005-09-20 | 2011-11-01 | General Electric Company | Thermally curable compositions and method |
| US8343608B2 (en) | 2010-08-31 | 2013-01-01 | General Electric Company | Use of appended dyes in optical data storage media |
| CN104628540A (en) * | 2013-11-08 | 2015-05-20 | 上海予利化学科技有限公司 | Cation photoinitiator (4-octyloxyphenyl)phenyl iodonium hexafluoroantimonate preparation method |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4058400A (en) * | 1974-05-02 | 1977-11-15 | General Electric Company | Cationically polymerizable compositions containing group VIa onium salts |
| US3981897A (en) * | 1975-05-02 | 1976-09-21 | General Electric Company | Method for making certain halonium salt photoinitiators |
| US4310469A (en) * | 1978-12-29 | 1982-01-12 | General Electric Company | Diaryliodonium salts |
| US4399071A (en) * | 1982-03-12 | 1983-08-16 | General Electric Company | Method for making diaryliodonium salts |
| US4537725A (en) * | 1982-09-18 | 1985-08-27 | Ciba-Geigy Corporation | Diaryliodosyl salts |
| US4933377A (en) * | 1988-02-29 | 1990-06-12 | Saeva Franklin D | Novel sulfonium salts and the use thereof as photoinitiators |
| US4882201A (en) * | 1988-03-21 | 1989-11-21 | General Electric Company | Non-toxic aryl onium salts, UV curable coating compositions and food packaging use |
-
1989
- 1989-10-31 US US07/429,744 patent/US4992571A/en not_active Expired - Lifetime
-
1990
- 1990-08-16 CA CA002023392A patent/CA2023392A1/en not_active Abandoned
- 1990-10-19 EP EP90120047A patent/EP0425920B1/en not_active Expired - Lifetime
- 1990-10-19 AT AT90120047T patent/ATE110706T1/en not_active IP Right Cessation
- 1990-10-19 DE DE69012047T patent/DE69012047T2/en not_active Expired - Fee Related
- 1990-10-30 FI FI905354A patent/FI905354A0/en not_active Application Discontinuation
- 1990-10-31 JP JP2292219A patent/JPH0751524B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0751524B2 (en) | 1995-06-05 |
| EP0425920A2 (en) | 1991-05-08 |
| FI905354A0 (en) | 1990-10-30 |
| ATE110706T1 (en) | 1994-09-15 |
| US4992571A (en) | 1991-02-12 |
| EP0425920B1 (en) | 1994-08-31 |
| DE69012047D1 (en) | 1994-10-06 |
| JPH03209341A (en) | 1991-09-12 |
| EP0425920A3 (en) | 1991-10-09 |
| DE69012047T2 (en) | 1995-04-06 |
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Legal Events
| Date | Code | Title | Description |
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| FZDE | Discontinued |