Method for producing epoxy compound and catalyst composition for epoxidation reaction

Abstract

A method of producing an epoxy compound, which comprises reacting hydrogen peroxide with a compound having a carbon-carbon double bond, in the presence of at least one of a tungsten compound and a molybdenum compound; and an onium salt comprising 20 or more carbon atoms and one or more of substituents convertible to a functional group containing an active hydrogen or a salt thereof.

Claims

1. A method for producing an epoxy compound, the method comprising: reacting hydrogen peroxide with a compound having a carbon-carbon double bond in a two-phase reaction system having an organic phase and an aqueous phase, the two-phase reaction system comprising: at least one compound selected from the group consisting of a tungsten compound and a molybdenum compound; and an onium salt having 20 or more carbon atoms and containing one or more substituents convertible to an active hydrogen-containing functional group or a salt thereof, to obtain an epoxy compound; after the reacting, converting the one or more substituents contained in the onium salt to an active hydrogen-containing functional group or a salt thereof; and separating the onium salt from the epoxy compound.

2. The method of claim 1, wherein said active hydrogen-containing functional group is a hydroxyl group, a carboxyl group, an amino group, a mercapto group, a sulfonic acid group or a phosphoric acid group.

3. The method of claim 1, wherein the two-phase reaction system further comprises at least one acid selected from the group consisting of a phosphoric acid and a phosphonic acid, excluding an onium salt.

4. The method of claim 1, wherein the aqueous phase of the two-phase reaction system has a pH of from 2 to 6.

5. The method of claim 1, wherein said onium salt is an ammonium salt, a pyridinium salt, an imidazolinium salt or a phosphonium salt.

6. The method of claim 1, wherein the converting is achieved by hydrolyzing said one or more substituents with a basic compound.

7. The method of claim 1, further comprising: washing said compound having a carbon-carbon double bond with an acidic aqueous solution prior to the reacting.

8. The method of claim 1, further comprising: washing said compound having a carbon-carbon double bond with an aqueous chelating agent solution prior to the reacting.

9. The method of claim 1, wherein the two-phase reaction system further comprises a chelating agent.

10. A method for producing an epoxy resin, the method comprising: producing an epoxy compound by the method claimed in claim 1; and polymerizing the epoxy compound.

11. The method of claim 1, wherein the onium salt is represented by formula (8) to (10), (12) or (31): ##STR00038## wherein R.sup.20 represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group having a carbon number of 1 to 25, in which a part of carbon atoms is optionally substituted with a heteroatom, a phenyl group, a phenoxy group, a benzyl group, an alkoxycarbonyl group, an N-alkylcarbamoyl group or an N-alkylsulfamoyl group; each of R.sup.21 to R.sup.23 independently represents an alkyl group having a carbon number of 1 to 25, in which a part of carbon atoms is optionally substituted with a heteroatom, or a benzyl group; R.sup.20 to R.sup.23 optionally combine in the same compound to form a ring; k represents an integer of 1 to 4; each of R.sup.31 and R.sup.32 independently represents a divalent aliphatic hydrocarbon group having a carbon number of 1 to 25, in which a part of carbon atoms is optionally substituted with a heteroatom; R.sup.33 represents a monovalent aliphatic hydrocarbon group having a carbon number of 1 to 25, in which a part of carbon atoms is optionally substituted with a heteroatom, or a monovalent aromatic hydrocarbon group having a carbon number of 4 to 25, which optionally has a substituent; provided that a plurality of k, R.sup.20 or R.sup.31 present in the same compound is optionally the same or different and the total number of carbon atoms contained in the cation moiety in the formulae is 20 or more; and X.sup. represents a monovalent anion.

12. The method of claim 1, wherein, during the reacting, the onium salt does not contain an active hydrogen-containing functional group or a salt thereof.

13. The method of claim 1, wherein the active hydrogen-containing functional group is a hydroxyl group.

14. The method of claim 1, wherein the active hydrogen-containing functional group is a carboxyl group.

15. The method of claim 1, wherein the onium salt is an ammonium salt.

16. The method of claim 1, wherein the onium salt is a pyridinium salt.

17. The method of claim 1, wherein the onium salt is an imidazolinium salt.

18. The method of claim 1, wherein the onium salt is a phosphonium salt.

19. A method for producing an epoxy compound, the method comprising: reacting hydrogen peroxide with a compound having a carbon-carbon double bond in the presence of at least one compound selected from the group consisting of a tungsten compound and a molybdenum compound; and an onium salt having 20 or more carbon atoms and containing one or more substituents convertible to an active hydrogen-containing functional group or a salt thereof, wherein said one or more sub substituents contained in the onium salt is an alkoxycarbonyl group or an acyloxy group.

20. The method of claim 19, further comprising, after the reacting, converting the one or more substituents contained in the onium salt to an active hydrogen-containing functional group or a salt thereof, wherein the converting is achieved by hydrolyzing said one or more substituents with a basic compound.

21. A method for producing an epoxy compound, the method comprising: reacting hydrogen peroxide with a compound having a carbon-carbon double bond in the presence of at least one compound selected from the group consisting of a tungsten compound and a molybdenum compound; and an onium salt having 20 or more carbon atoms and containing one or more substituents convertible to an active hydrogen-containing functional group or a salt thereof, wherein said onium salt is a compound represented by any one of formulae (1) to (3): ##STR00039## wherein each of any one or more of R.sup.1 to R.sup.4, any one or more of R.sup.5 to R.sup.10 and any one or more of R.sup.11 to R.sup.15 independently represents YCOOZ or YOCOZ, Y represents a direct bond or a divalent aliphatic hydrocarbon group having a carbon number of 1 to 25, in which a part of carbon atoms is optionally substituted with a heteroatom and which optionally has a substituent, and Z represents a monovalent aliphatic hydrocarbon group having a carbon number of 1 to 25, in which a part of carbon atoms is optionally substituted with a heteroatom, or a monovalent aromatic hydrocarbon group having a carbon number of 4 to 25, which optionally has a substituent, each of R.sup.1 to R.sup.5, R.sup.11 and R.sup.13, when these are not YCOOZ or YOCOZ, independently represents an alkyl group having a carbon number of 1 to 25, in which a part of carbon atoms is optionally substituted with a heteroatom and which optionally has a substituent, or a benzyl group, each of R.sup.6 to R.sup.10, R.sup.12,R.sup.14 and R.sup.15, when these are not YCOOZ or YOCOZ, independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group having a carbon number of 1 to 25, in which a part of carbon atoms is optionally substituted with a heteroatom and which optionally has a substituent, a phenyl group, a phenoxy group, a benzyl group, an N-alkylcarbamoyl group or an N-alkylsulfamoyl group, R.sup.1 to R.sup.15 optionally combine in the same compound to form a ring, provided that the total number of carbon atoms contained in R.sup.1 to R.sup.4 is 20 or more, the total number of carbon atoms contained in R.sup.5 to R.sup.10 is 15 or more, and the total number of carbon atoms contained in R.sup.11 to R.sup.15 is 17 or more, and X.sup. represents a monovalent anion.

Description

EXAMPLES

(1) The present invention is described in greater detail below by referring to Examples, but the present invention should not be construed as being limited to these Examples.

(2) <.sup.1H-NMR Analysis Conditions>

(3) Apparatus: AVANCE400, manufactured by BRUKER, 400 MHz

(4) Solvent: deuterium chloroform containing 0.03 vol % tetramethylsilane

(5) Cumulated number: 128 times

(6) The date in Examples show the 8 value in .sup.1H-NMR (400 MHz, CDCl.sub.3).

(7) Also, the underline in the NMR date described in Examples indicates the proton position identified.

(8) <LC Analysis Conditions>

(9) LC Apparatus: SPD-10Avp, manufactured by Shimadzu Corporation

(10) Temperature: 35 C.

(11) Column: Mightysil RP-18GP aqua 150-4.6 (5 m) (produced by Kanto Chemical Co., Inc.)

(12) (The following conditions are designated as Analysis Condition 1 and unless otherwise indicated, LC analysis was performed under this condition.)

(13) Detector: UV 280 nm

(14) Eluent: acetonitrile/aqueous 0.1% trifluoroacetic acid solution=90/10 (vol %)

(15) Flow rate: 0.5 ml/min

(16) (The following conditions are designated as Analysis Condition 2.)

(17) Detector: UV 254 nm

(18) Eluent: acetonitrile/aqueous 0.1% trifluoroacetic acid solution 60/40.fwdarw.100/0 (vol %), 20 minutes, and thereafter, kept at 100/0 (vol %) for 10 minutes

(19) Flow rate: 0.5 ml/min

(20) <LC-Mass Analysis Conditions>

(21) LC Apparatus: Waters Acquity

(22) Temperature: 40 C.

(23) Column: UPLC BEH C.sub.18 2.1100 mm (1.7 m)

(24) Eluent: acetonitrile/aqueous 20 mM ammonium acetate solution=50/50 (vol %).fwdarw.100/0 in 10 min, kept at 100/0 for 10 min

(25) Flow rate: 0.25 m1/min

(26) MS Apparatus: Waters LCT Premier XE

(27) Ionization method: ESI(+) method

(28) <GC Analysis Conditions>

(29) Apparatus: GC-1700, manufactured by Shimadzu Corporation

(30) Column: ZB-5 (30 m0.25 mm, 0.25 m), manufactured by phenomenex

(31) Detector: hydrogen flame ion detector (FID)

(32) Carrier gas (nitrogen flow rate): 28 ml/min

(33) Column temperature: raised from 100 C. to 300 C. at 10 C./min

(34) INJ Temperature: 250 C.

(35) DET Temperature: 300 C.

(36) <GC/Mass Analysis Conditions>

(37) GC Apparatus: GC-2010, manufactured by Shimadzu Corporation

(38) MS Apparatus: GCMS-QP2010Plus, manufactured by Shimadzu Corporation

(39) Column: DB-5 25 M0.25 (0.25)

(40) Ionization method: EI method and CI method

(41) <RI Analysis Conditions>

(42) RI Apparatus: JASCO RI-930, manufactured by JASCO Corporation

(43) Temperature: 35 C.

(44) Column: ODS-3 150-4.6 (5 m) (manufactured by GL Sciences Inc.

(45) Eluent: acetonitrile

(46) Flow rate: 0.5 ml/min

(47) As for the chlorine content (ppm by weight), the combined total chlorine amount of inorganic and organic components was measured by the following method. The sample was burned, absorbed by an absorbing liquid and then measured by ion chromatography. The burning apparatus used was AQF-100 manufactured by Mitsubishi Chemical Corporation, and the ion chromatograph used was DX-500 manufactured by DIONEX. In the ion chromatograph, Ion Pac AS12A manufactured by DIONEX was used for the column, and the detection was performed by measuring the electrical conductivity.

(48) The tungsten content (ppm by weight) was measured by the following method. From 0.1 to 0.5 g of the sample was weighted, 2 ml of sulfuric acid was added, and after heating and carbonization, nitric acid and hydrogen peroxide were further added, followed by heating to effect wet digestion. Thereto, 2 ml of aqueous hydrogen peroxide was added and after heating, the mixture was diluted to about 40 ml total with pure water. Furthermore, 2 ml of aqueous hydrogen peroxide was added, and the mixture was diluted to 50 ml with pure water. The resulting solution was analyzed by ICP-AES (ULTIMA 2C, manufactured by HORIBA Jobin Yvon).

(49) The nitrogen content (ppm by weight) was measured by the following method. 8 mg of the sample was burned in an oxygen and argon atmosphere, and the decomposition gas generated was measured by a trace nitrogen analyzer (Model TN-10, manufactured by Mitsubishi Chemical Analytech Co., Ltd.) using a combustion and reduced pressure chemiluminescence method. Also, as the standard sample, aniline dissolved in toluene was used.

(50) The pH of the aqueous phase was measured using pH test papers, Comparator (produced by Johnson Test Papers), for the pH of 1.0 to 3.5 and the pH of 3.6 to 5.1.

(51) (Epoxidation Reaction Raw Material)

(52) As 3,3,5,5-tetramethyl-4,4-bis(2-propen-1-yloxy)-1,1-biphenyl (another name: 3,3,5,5-tetramethylbiphenyl-4,4-diallyl ether), a compound synthesized by a method in conformity with Example 2 of JP-A-2011-213716 was used. The compound contained 23 ppm of chlorine, and the purity was 99.9% (LC area %, Analysis Condition 1).

(53) As 1,5-cyclooctadiene, a reagent produced by Tokyo Chemical Industry Co., Ltd. was used.

(54) As for the diol compound (Compound 23) contained in the epoxy compound (Compound 21), a specimen was synthesized by the method described in Reference Example 1 and using this specimen, the assignment of NMR peaks and the retention time and UV absorption intensity by LC analysis were confirmed and used for the determination of the content of Compound 23 in Compound 21.

(55) As for the ester compound (Compound 22) in Examples 12, 14, 16, 18, 20, 22, 25 and 26, a specimen was synthesized according to the method described in Reference Example 2, and the NMR analysis of this specimen was performed to confirm the assignment of each peak of NMR. The NMR analysis of Compound 21 was performed based thereon, and the results were used for the determination of the content of Compound 22 in Compound 21. In other Examples, the content of Compound 22 in Compound 21 was determined by analogy with NMR of the compound obtained in Reference Example 2.

(56) Incidentally, the molecular weight of the ester compound (Compound 22) in Examples 2, 8 and 9 was confirmed by LC-Mass. m/z: 470.3.

(57) For determining the abundance ratio of the compound or the compound to the compound , the composition obtained by the epoxidation reaction was subjected to LC analysis (in Example 28, GC analysis) to measure the LC area % of each component.

(58) As for the abundance ratio of the compound to the compound , the peak area ratio of the compound to the compound determined by LC analysis (in Example 28, GC analysis) was corrected for the detection sensitivity of each compound and converted to a molar ratio. The detection sensitivity of each compound was determined by previously preparing a specimen of each compound with a purity of 95% or more and calculating the sensitivity from the approximation (purity/100 estimated by molar numberLC area %) of the net molar number of the compound and the LC peak area thereof.

(59) Subsequently, the composition obtained by the epoxidation reaction was subjected to NMR analysis. The abundance ratio of the compound was determined by comparing the integrated value of proton peaks of the terminal methyl group of a hexanoic acid ester, the tert-butyl group of a tert-butylbenzoic acid ester, etc., which are easy to specify and integrate, with the integrated value of peaks of the epoxy compound .

(60) The contents of the compounds and are expressed by the abundance ratio to the epoxy compound , that is, the molar ratio (mol %) based on the epoxy compound that is taken as 100.

(61) In Examples, in the process of synthesizing (21) by an epoxidation reaction, a slight amount of a compound (a compound of m/z 370.2 in LC-Mass) considered to result from aldehyde isomerization and subsequent oxidation of an epoxy ring by heat or an acid during the reaction is produced in addition to the compounds and . Both of the compound above and the compound have higher polarity than the epoxy compound (21) and give a faster retention time than the compound (21) in LC analysis. In Examples, these compounds giving a faster retention time than the epoxy compound (21) are sometimes collectively referred to as polar compound.

Example 1

Synthesis of Onium Salt [1]

(62) ##STR00027##

(63) To a mixed solution containing 5.0 g (27 mmol) of triethanolamine hydrochloride, 200 ml of toluene and 10.9 g (4 times mol/substrate) of triethylamine, 10.8 g (3.0 times mol/substrate) of hexanoic acid chloride was added dropwise under ice-water cooling. After the reaction with stirring at room temperature for 1 day, the reaction solution was washed twice with water, i.e., with 150 ml and then with 100 ml, and then concentrated to obtain 9.8 g of crude triethanolamine trihexanoate.

(64) A 7.8 g portion of the crude triethanolamine trihexanoate obtained by the method above was subjected to column purification (200 g of silica gel 60N, developing system: hexane/ethyl acetate=4/1) to obtain 1.63 g of triethanolamine trihexanoat with a purity of 91.2% (GC area %). M+H.sup.+: 444.3 (GC-Mass).

(65) The NMR data of the triethanolamine trihexanoate were as follows.

(66) 0.90 (9H, t, CH3), 1.30 (12H, m, CH3-CH2-CH2-), 1.61 (6H, m,CH2-CH2-CO), 2.30 (6H, t, J=7.56,CH2-CH2-CO), 2.83 (6H, t, J=6.08, NCH2-), 4.12 (6H, t, J=6.08, CH2-OCO).

(67) 4 ml of toluene, 0.46 g (1.0 times mol/substrate) of dimethyl sulfate and 0.51 g (1.0 times mol/substrate) of potassium carbonate were added to 1.63 g of triethanolamine trihexanoate above and reacted at 80 C. for 5.5 hours. After confirming the conversion of the raw material by the disappearance of the peak attributable to the ethylene moiety of the triethanolamine trihexanoate in NMR analysis, the reaction solution was washed with 5 ml of water, washed three times with 5 ml of 20% sulfuric acid solution, further washed with 5 ml of water and then concentrated to obtain 2.1 g of crude N-methyl-N,N,N-tri[2-(pentylcarbonyloxy)ethyl]ammonium hydrogen sulfate. m/z: 458.3 (LC-Mass) and purity: 75% (RI). This product was used without purification in the epoxidation reaction.

(68) Incidentally, in the following, N-methyl-N,N,N-tri[2-(pentylcarbonyloxy)ethyl]ammonium hydrogen sulfate is sometimes referred to as Onium Salt [1].

(69) The NMR measurement data of Onium Salt [1] are as follows. N-Methyl-N,N,N-tri[2-(pentylcarbonyloxy)ethyl]ammonium hydrogen sulfate

(70) 0.90 (9H, t, CH3), 1.31 (12H, m, CH3-CH2-CH21), 1.61 (6H, m-CH2-CH2-CO), 2.33 (6H, t, CH2-CO), 3.38 (3H, s, NCH3), 3.92 (6H, br, NCH2-), 4.60 (6H, br, CH2-OCO), 5, 78 (1H, br, HOSO2).

Example 2

(71) Epoxidation Reaction Using Onium Salt [1]

(72) ##STR00028##

(73) A mixed solution containing 5.0 g (15.5 mmol) of 3,3,5,5-tetramethyl-4,4-bis(2-propen-1-yloxy)-1,1-biphenyl, 512 mg (10% mol/substrate) of sodium tungstate dihydrate, 1.97 ml (11% mol/substrate) of an aqueous 8.5% (weight/volume) phosphoric acid solution, 432 mg (5% mol/substrate) of crude N-methyl-N,N,N-tri[2-(pentylcarbonyloxy)ethyl]ammonium hydrogen sulfate, and 3 ml of toluene was heated at 65 C. Under a nitrogen stream, the solution above was added with 0.5 ml (0.5 times mol/substrate) of 45% hydrogen peroxide 6 times every hour and further held at 65 to 68 C. for 7 hours, thereby performing the reaction for a total of 12 hours. It was confirmed by the LC analysis above that 3,3,5,5-tetramethylbiphenyl-4,4-diglycidyl ether was produced in a reaction yield of 81% (LC area %).

(74) In addition, 7.0% of 3,3,5,5-tetramethylbiphenyl-4,4-monoallyl ether monoglycidyl ether (hereinafter, this compound is sometimes referred to as a monoepoxy compound) as a reaction intermediate, and 9.5% of a polar compound containing the above-described diol compound (both are LC area %) were produced.

(75) Here, the LC area indicates the peak area of the target compound of analysis, which is obtained by liquid chromatograph (LC) analysis, and LC area % indicates the ratio of the peak area of the target compound to the peak area of the total amount of the composition.

(76) After the completion of reaction, 7.5 ml of toluene was additionally added and then, the aqueous phase was separated, washed twice with 5 ml of water and washed in sequence with 5 ml of an aqueous 5% sodium thiosulfate solution and with 5 ml of water. Furthermore, 10 ml of an aqueous 1N sodium hydroxide solution was added and after stirring for 1 hour, the aqueous phase was discharged. The toluene phase was analyzed by NMR, and it was confirmed by the disappearance of the peak attributable to the ethylene moiety of N-methyl-N,N,N-tri[2-(pentylcarbonyloxy)ethyl]ammonium hydrogen sulfate that Onium Salt [1] was hydrolyzed. Washing with the same aqueous sodium hydroxide solution and NMR analysis were repeated three times, and the resulting solution was washed with 10 ml of water. The obtained toluene phase was concentrated to obtain 3.8 g of 3,3,5,5-tetramethylbiphenyl-4,4-diglycidyl ether (Compound 21) as a crude crystal. The purity was 86.4%, and the yield was 60%. This crud crystal contained 2.7 mol % of the ester compound (Compound 22) and 5.2 mol % of the diol compound (Compound 23).

(77) The NMR data of the compound before and after the reaction were as follows. 3,3,5,5-Tetramethyl-4,4-bis(2-propen-1-yloxy)-1,1-biphenyl

(78) 2.32 (12H, s, CH3), 4.34 (4H, dt, OCH2-), 5.27 (2H, ddd, CHCH2), 5.44 (2H, ddd, CHCH2), 6.13 (2H, m,CHCH2), 7.18 (4H, s, C6H2 (Me)2-). 3,3,5,5-Tetramethylbiphenyl-4,4-diglycidyl ether (Compound 21)

(79) 2.34 (12H, s, CH3), 2.75 (2H, dd, CH2-), 2.90 (2H, dd, CH2-), 3.38 (2H, m, CH), 3.73 (2H, dd, CH2-), 4.07 (2H, dd, CH2-), 7.18 (4H, s, C6H2 (Me)2-).

(80) The contents of chlorine, tungsten and nitrogen in the compound were analyzed by the methods described above. The results are shown in Table 1.

Example 3

Synthesis of Onium Salt [2]

(81) ##STR00029##

(82) A mixed solution containing 0.92 g (4.1 mmol) of ethyl bromohexanoate, 1.0 g (1 times mol/substrate) of dioctylamine, 5 ml of ethanol and 0.57 g (1 times mol/substrate) of potassium carbonate was relaxed for 10 hours. After additionally adding 0.46 g of ethyl bromohexanoate and 0.29 g of potassium carbonate and relaxing the mixed solution for another 5 hours, 0.25 g of dioctylamine was additionally added, and the mixed solution was relaxed for 12 hours. Disappearance of ethyl bromohexanoate and dioctylamine was confirmed by NMR analysis and thereafter, 0.52 g (1 times mol/substrate) of dimethyl sulfate and 0.57 g (1 times mol/substrate) of potassium carbonate were added and reacted at 60 C. for 2 hours. Subsequently, 0.52 g of dimethyl sulfate and 0.57 g of potassium carbonate were additionally added and reacted at 60 C. for another 2 hours, and furthermore, 0.18 g of dimethyl sulfate and 0.15 g of potassium carbonate were additionally added and reacted at 60 C. for 2 hours. Disappearance of N-(6-ethoxy-6-oxohexyl)-N,N-dioctylamine as a reaction intermediate was confirmed by NMR analysis and thereafter, the insoluble matter was separated by filtration and concentrated to obtain 2.39 g of N-(6-ethoxy-6-oxohexyl)-N-methyl-N,N-dioctylammonium monomethyl sulfate. Yield: 91%.

(83) 1.0 g of N-(6-ethoxy-6-oxohexyl)-N-methyl-N,N-dioctylammonium monomethyl sulfate obtained by the method above was dissolved in 2 ml of toluene, and 1 ml of 20% sulfuric acid solution was added, followed by stirring at room temperature for 20 minutes. After discharging the aqueous phase, 1 ml of 20% sulfuric acid solution was again added, followed by stirring at room temperature for 20 minutes. After discharging the aqueous phase, 1 ml of water was added, followed by stirring at room temperature for 20 minutes, and the aqueous phase was discharged. The residue was concentrated to obtain 1.0 g of N-(6-ethoxy-6-oxohexyl)-N-methyl-N,N-dioctylammonium hydrogen sulfate (hereinafter, Onium Salt [2]). This product was used without purification in the epoxidation reaction.

(84) The NMR data of Onium Salt [2] obtained are as follows. N-(6-Ethoxy-6-oxohexyl)-N-methyl-N,N-dioctylammonium hydrogen sulfate

(85) 0.90 (6H, m, CH3), 1.15-1.5 (25H, m, CH2-+CH3), 1.5-1.8 (8H, m, CH2-), 2.3-2.4 (2H, m, CH2-CO), 3.23 (3H, s, NCH3), 3.2-3.4 (6H, m, NCH2-), 4.12 (2H, dd, CH2-OCO), 5.66 (1H, br, HOSO2).

Example 4

Epoxidation Reaction Using Onium Salt [2]

(86) The reaction was performed in the same manner by the same method as in Example 2 by using, as the ammonium salt, N-(6-ethoxy-6-oxohexyl)-N-methyl-N,N-dioctylammonium hydrogen sulfate (5% mol/substrate) in place of N-methyl-N,N,N-tri[2-(pentylcarbonyloxy)ethyl]ammonium hydrogen sulfate. The reaction yield: 80% (LC area %). The obtained crude crystal of Compound 21 contained 1.1 mol % of the ester compound (Compound 22). The content of tungsten in the compound was measured by the method described above. The measurement results are shown in Table 1.

Example 5

Synthesis of Onium Salt [3]

(87) ##STR00030##

(88) A mixed solution containing 5.0 g (14.1 mol) of trioctylamine, 25 ml of toluene and 1.92 g (1.0 times mol/substrate) of methyl bromoacetate was heated at 40 C. for 4 hours. After confirming disappearance of methyl bromoacetate by NMR analysis, the reaction solution was washed twice with 25 ml of an aqueous 8.5% phosphoric acid solution to obtain a toluene solution of 0.57 mol/L N,N,N-trioctyl-N-(2-methoxy-2-oxoethyl)ammonium phosphate (hereinafter, Onium Salt [3]). This product was used without purification in the epoxidation reaction.

(89) The NMR data of Onium Salt [3] obtained are as follows. N,N,N-Trioctyl-N-(2-methoxy-2-oxoethyl)ammonium phosphate

(90) 0.88 (9H, t, CH3), 1.20-1.40 (30H, m, CH2-), 1.76 (6H, m, CH2-), 3.60-3.67 (6H, m, CH2-), 3.81 (3H, s, CH3), 4.85 (2H, s-NCH2-).

Example 6

Epoxidation Reaction Using Onium Salt [3]

(91) The reaction was performed in the same manner by the same method as in Example 2 by using, as the ammonium salt, N,N,N-trioctyl-N-(2-methoxy-2-oxoethypammonium phosphate (5% mol/substrate). The reaction stopped proceeding 4 hours after the initiation of the reaction, and the reaction yield was 23% (LC area %). The NMR analysis of the reaction mixture was performed by the same method as in Example 2, as a result, disappearance of the 2-methoxy-2-oxoethyl moiety of the N,N,N-trioctyl-N-(2-methoxy-2-oxoethyl)ammonium salt was confirmed, suggesting that decomposition of Onium Salt [3] occurred.

Comparative Example 1

Epoxidation Reaction Using Methyltrioctylammonium Hydrogen sulfate

(92) 150.0 g (0.47 mol) of 3,3,5,5-tetramethyl-4,4-bis(2-propen-1-yloxy)-1,1-biphenyl was reacted by the same method as in Example 2 by using methyltrioctylammonium hydrogen sulfate (5% mol/substrate) as the ammonium salt. The reaction yield of 3,3,5,5-tetramethylbiphenyl-4,4-diglycidyl ether was 84% (LC area %). After the completion of reaction, the reaction solution was treated by the same method to obtain 147 g of 3,3,5,5-tetramethylbiphenyl-4,4-diglycidyl ether as a crude crystal. Yield: 76% and purity: 91.2% (LC area %, LC Analysis Condition 2). This crude crystal contained methyltrioctylammonium salt, and the content thereof was estimated by NMR analysis to be 6 mol % (expressed by the ratio based on 3,3,5,5-tetramethylbiphenyl-4,4-diglycidyl ether that is taken as 100). The residual amount of each of nitrogen and tungsten was measured by inorganic analysis. The analysis results are shown in Table 1.

Comparative Example 2

(93) After adding 10.5 ml of methanol to 1.5 g of 3,3,5,5-tetramethylbiphenyl-4,4-diglycidyl ether obtained by the method of Comparative Example 1, the mixture was stirred and crystalized at 50 C. for 2 hours and cooled to 6 C., and 0.89 g of a crystal was collected by filtration. Yield: 62%. Purity: 95.2% (LC area %, LC Analysis Condition 2). This crystal contained methyltrioctylammonium salt, and the content thereof was 1.75 mol % (the same NMR analysis as above; corresponding to a residual nitrogen amount of 690 ppm).

Example 7

Synthesis Method of Onium Salt [1] (with the Counter Cation being Monomethylsulfuric Acid

(94) A mixed solution containing 20.0 g (207 mmol) of triethanolamine hydrochloride, 60 ml of octane, 43.3 g (3.0 times mol/substrate) of hexanoic acid and 5.28 g of sulfuric acid was heated in an oil bath at 135 C. and reacted for 61 hours while distilling off the occurring water. After allowing the reaction system to cool, 200 ml of ethyl acetate and 400 ml of a saturated sodium bicarbonate solution were added, and the mixture was stirred. Thereafter, the aqueous phase was discharged, and the organic phase was washed with 100 ml of water. The obtained compound was a mixture of hexanoic acid monoester, diester and triester, and the esterification ratio (the proportion of the esterified hydroxyl group determined from the H integration ratio in NMR analysis) was 79%.

(95) The crude triethanolamine trihexanoate obtained by the method above was subjected to column purification (silica gel 60N, 300 g, developing system: hexane/ethyl acetate=10/1.fwdarw.>5/1) to obtain 15.6 g of triethanolamine trihexanoate with a purity of 98.3% (GC). The yield was 33%.

(96) To 0.34 g (0.78 mmol) of triethanolamine trihexanoate obtained above, 1.1 ml of toluene and 0.12 g (1.2 times mol/triethanolamine trihexanoate) of dimethyl sulfate were added and reacted at 90 C. for 2 hours. As a result, N-methyl-N,N,N-tri[2-(pentylcarbonyloxy)ethyl]ammonium monomethyl sulfate (hereinafter, referred to as Onium Salt [1]) in an yield of 84% (molar ratio determined from the H integration degree of ethylene chain in NMR analysis). This reaction solution was used directly without purification in the epoxidation reaction.

Example 8

Epoxidation Reaction Using Onium Salt [1]

(97) A solution prepared by dissolving 5.0 g (15.5 mmol) of 3,3,5,5-tetramethyl-4,4-bis(2-propen-1-yloxy)-1,1-biphenyl in 6.3 ml of toluene was washed with 15 ml of an aqueous solution containing 1 wt % of anhydrous sodium sulfate and 1 vol % of acetic acid, then washed with a mixed solution containing 0.23 ml of an aqueous 3 wt % sodium pyrophosphate solution, 0.06 ml of a 10 wt % ethylenediaminetetraacetic acid solution and 15 ml of water, and further washed with 10 ml of water, and to the obtained toluene layer, 511 mg (10% mol/substrate) of sodium tungstate dihydrate, 0.9 ml (5% mol/substrate) of an aqueous 8.5% (weight/volume) phosphoric acid solution, 2 ml of water and a toluene solution of N-methyl-N,N,N-tri[2-(pentylcarbonyloxy)ethyl]ammonium monomethyl sulfate obtained above were added, followed by stirring. Furthermore, an aqueous phosphoric acid solution was added to the resulting mixed solution, whereby the pH of the aqueous phase of the mixed solution was adjusted to 4.8. The amount of the aqueous phosphoric acid solution added here was 0.5 ml (3% mol/substrate). The mixed solution was heated at 65 C. and thereafter, under a nitrogen stream, added with 0.5 ml (0.5 times mol/substrate) of 45% hydrogen peroxide a total of 5 times, that is, at the initiation of reaction and after 1 hour, 2 hours, 3 hours and 6 hours therefrom, at an inner temperature of 65 to 68 C. When the reaction was started, an aqueous 1N sodium hydroxide solution was added in an amount of 0.4 ml after 1.5 hours, 0.1 ml after 4.5 hours, and 0.1 ml after 6.5 hours, to adjust the pH of the aqueous solution to a range of 3.0 to 3.5. The reaction was performed for a total of 8 hours at an inner temperature of 65 to 68 C., and it was confirmed by the LC analysis above that 3,3,5,5-tetramethylbiphenyl-4,4-diglycidyl ether was produced in a reaction yield of 82% (LC area %). In addition, production of 11% (LC area %) of a monoepoxy compound as a reaction intermediate and 6% (LC area %) of a polar compound was confirmed.

(98) After the completion of reaction, 7.5 ml of toluene was additionally added and then, the aqueous phase was separated, washed three times with 5 ml of water. Furthermore, 10 ml of an aqueous 1N sodium hydroxide solution was added and after stirring for 1 hour, the aqueous phase was discharged. Washing with the same aqueous sodium hydroxide solution was repeated three times, and the resulting solution was washed with 10 ml of water. The obtained organic phase was concentrated to obtain 4.5 g of 3,3,5,5-tetramethylbiphenyl-4,4-diglycidyl ether (Compound 21) with a purity of 83% (LC area %) as a crystal. The yield was 69%. This crystal contained 2.4 mol % of the ester compound (Compound 22) and 3.5 mol % of the diol compound (Compound 23). The contents of chlorine, tungsten and nitrogen in the compound were analyzed by the methods described above. The measurement results are shown in Table 1.

Example 9

(99) After adding 15 ml of methanol to 2.0 g of 3,3,5,5-tetramethylbiphenyl-4,4-diglycidyl ether obtained by the method above, the mixture was stirred and crystalized at 50 C. for 1 hour to obtain 1.8 g of a crystal of 3,3,5,5-tetramethylbiphenyl-4,4-diglycidyl ether (Compound 21) with a purity of 91% (LC area %). Recovery percentage: 98%. This crystal contained 0.3 mol % of the ester compound (Compound 22).

Example 10

Synthesis of Onium Salt [4]

(100) The reaction was performed by the same method as in Example 8 without performing the addition of an aqueous sodium hydroxide solution during the reaction. It was confirmed that 3,3,5,5-tetramethylbiphenyl-4,4-diglycidyl ether was produced in a reaction yield of 77% (LC area %). In addition, production of 9% (LC area %) of a monoepoxy compound as a reaction intermediate and 12% (LC area %) of the compound resulting from ring opening of an epoxy ring due to an acid was confirmed.

Example 11

(101) ##STR00031##

(102) (In the structural formula above, R.sup.25 represents a C8-C18 alkyl group.)

(103) While heating a mixed solution containing 12.0 g of Ethoquad C/12 produced by Lion Akzo Corporation (N-alkyl(C8-C-18)-N,N-bis(2-hydroxyethyl)-N-methylammonium chloride; containing about 20% of isopropanol) and 200 ml of toluene, 50 ml of a mixed solution of toluene and isopropanol was distilled off. Thereafter, 5.0 g of triethylamine was added and after adding 6.7 g of benzoyl chloride at an inner temperature of 60 to 80 C., the reaction was performed at an inner temperature of 65 C. for 30 minutes and at 80 C. for 2 hours. As for the change over time of the reaction system, about 0.1 ml of the reaction mixture was dissolved in 1 ml of methanol, the unreacted benzoyl chloride was converted to benzoic acid methyl eater, and LC analysis was performed under Analysis Condition 2. Triethylamine and benzoyl chloride were gradually added at 80 C., and the point where consumption of benzoyl chloride was stopped was designated as the end point. The amounts of the additionally added triethylamine and benzoyl chloride were 4.8 g and 3.6 g, respectively.

(104) After the completion of reaction, 100 ml of toluene and 100 ml of water were added to the reaction system and after stirring, the aqueous phase turned white turbid was discharged. When the aqueous phase was left standing still, an organic phase was liberated and therefore, this organic phase was combined with the separated organic phase and washed with 100 ml of water to obtain 13 g of a benzoic acid ester form of Ethoquad C/12, which is N-alkyl-N,N-bis[2-(phenylcarbonyloxy)ethyl]-N-methylammonium chloride. The purity was 82% (LC area %, LC Analysis Condition 2), and the product contained 11% (LC area %) of benzoic acid. The carbon number of the alkyl chain was estimated to be about 14 on average from the H integration value in NMR (hereinafter, referred to as Onium Salt [4]).

(105) The NMR data of Onium Salt [4] obtained are as follows. N-Alkyl-N,N-bis[2-(phenylcarbonyloxy)ethyl]-N-methylammonium chloride

(106) 0.88 (3H, CH3), 1.0-1.4 (about 20H, br, CH2-), 1.76 (2H, m, CH2-), 2.00 (2H, m, CH2-), 3.63 (3H, s, NCH3), 3.63 (2H, m-CH2-), 4.38 (4H, m, NCH2-), 4.91 (4H, m, CH2-CO), 7.42 (4H, dd, -Ph), 7.56 (2H, dd, -Ph), 8.00 (4H, d, -Ph).

Example 12

Epoxidation Reaction Using Onium Salt [4]

(107) A solution prepared by dissolving 10.0 g (31.0 mmol) of 3,3,5,5-tetramethyl-4,4-bis(2-propen-1-yloxy)-1,1-biphenyl in 10 ml of toluene was washed with 30 ml of an aqueous solution containing 1 wt % of anhydrous sodium sulfate and 1 vol % of acetic acid, then washed with a mixed solution containing 0.26 ml of an aqueous 3 wt % sodium pyrophosphate solution, 0.12 ml of a 10% ethylenediaminetetraacetic acid solution and 30 ml of water, and further washed with 30 ml of water, and to the obtained organic phase, 1.02 g (10% mol/substrate) of sodium tungstate dihydrate, 1.79 ml (5% mol/substrate) of an aqueous 8.5% (weight/volume) phosphoric acid solution, 2 ml of water and 1.0 g of the benzoic acid ester form of Ethoquad C/12 obtained above were added, followed by stirring. Under a nitrogen stream, 0.5 ml (0.5 times mol/substrate) of 45% hydrogen peroxide was added at an inner temperature of 65 to 68 C., and thereafter, 1.79 ml (5% mol/substrate) of an aqueous phosphoric acid solution was further added to the resulting mixed solution, whereby the pH of the aqueous solution of the mixed solution was adjusted to 3.5. While heating the mixed solution at 65 C., 0.5 ml (0.5 times mol/substrate) of 45% hydrogen peroxide was added a total of 5 times, that is, after 1 hour, 2 hours, 3 hours and 6 hours therefrom, and 0.1 g of the benzoic acid ester form of Ethoquad C/12 was additionally added after 8 hours. The reaction was performed for a total of 12 hours at an inner temperature of 65 to 68 C., and it was confirmed by the LC analysis above that 3,3,5,5-tetramethylbiphenyl-4,4-diglycidyl ether was produced in a reaction yield of 82% (LC area %). In addition, production of 8% (LC area %) of a monoepoxy compound as a reaction intermediate and 5% (LC area %) of a polar compound was confirmed.

(108) After the completion of reaction, the aqueous phase was discharged, and the residue was washed twice, that is, with 20 ml of water and with 2 ml of saturated brine, further washed twice with 20 ml of water, and then cooled to precipitate the reaction content as a solid. The supernatant water and the toluene mixed solution were discharged by decantation, and the remaining solvent was distilled off by blowing nitrogen, as a result, a solid of the reaction content was obtained.

(109) The obtained solid was added with 20 ml of an aqueous 1N sodium hydroxide solution and after stirring for 1 hour, the aqueous phase was discharged. After repeating the same operation three times, the resulting solution was washed with 2 ml of an aqueous 5% sodium thiosulfate solution and 20 ml of water and further washed with 20 ml of water, and the obtained solid was dried to obtain 8.2 g of 3,3,5,5-tetramethylbiphenyl-4,4-diglycidyl ether (Compound 21) with a purity of 94% (LC area %) as a crude crystal (yield: 70%). This crud crystal contained 0.6 mol % of the ester compound (Compound 22) and 6.8 mol % of the diol compound (Compound 23).

(110) The content of tungsten in the compound was analyzed by the method described above. The measurement results are shown in Table 1.

Example 13

Synthesis of Onium Salt [5]

(111) ##STR00032##

(112) A mixed solution containing 80 g (0.44 mmol) of 4-tert-butylbenzoic acid, 240 ml of toluene and 0.68 g (0.015 times mol/substrate) of triethylamine was heated at 75 C. and thereafter, 64.1 g (1.2 times mol/substrate) of thionyl chloride was added over 1.5 hours. The reaction was performed at 75 C. for another 1.5 hours. After the completion of reaction, 100 ml of toluene was added under atmospheric pressure, 50 ml of toluene was further added under reduced-pressure conditions, and excess thionyl chloride was distilled off to obtain 90.8 g of 4-tert-butylbenzoyl chloride.

(113) To a mixed solution containing 2.0 g (10.8 mmol) of triethanolamine hydrochloride, 20 ml of toluene and 4.36 g (4 times mol/substrate) of triethylamine, 7.0 g (3.0 times mol/substrate) of 4-tert-butylbenzoyl chloride obtained by the method above was added dropwise under ice-water cooling. After the reaction with stirring at 60 C. for 5 hours, 1.42 (1.3 times mol/substrate) of triethylamine and 0.4 g of triethanolamine hydrochloride were additionally added and reacted with stirring at 80 C. for 10 hours. After the completion of reaction, the reaction solution was washed three times with 20 ml of water and then concentrated. The obtained crude triethanolamine trihexanoate was added with 40 ml of hexane for crystallization, and the crystal was collected by filtration to obtain 5.12 g of triethanolamine tri-4-tert-butylbenzoate. Purity: 98.2% (LC Analysis Condition 2) and yield: 63%.

(114) A 0.54 g (0.85 mmol) portion of the triethanolamine tri-4-tert-butylbenzoate obtained by the method above was added with 1.6 ml of toluene and heated at 80 C., and the reaction was performed for 3.5 hours while adding in parts 135 mg (1.2 times mol/substrate) of dimethyl sulfate. Production of N-methyl-N,N,N-tri[2-(4-tert-butylphenylcarbonyloxy)ethyl]ammonium monomethyl sulfate (hereinafter, referred to as Onium Salt [5]) at a conversion ratio of 91% (LC area %, LC Analysis Condition 2) was confirmed. This reaction solution was used directly without purification in the epoxidation reaction.

(115) The NMR data of Onium Salt [5] obtained are as follows. N-Methyl-N,N,N-tri[2-(4-tert-butylphenylcarbonyloxy)ethyl]ammonium monomethyl sulfate

(116) 1.28 (27H, s, t-Bu), 3.58 (3H, s, CH3), 3.67 (3H, s, CH3OSO2-), 4.26 (6H, br, NCH2-), 4.92 (6H, br, CH2-CO), 7.38 (6H, dd, Ar), 7.88 (6H, dd, Ar).

Example 14

Epoxidation Reaction Using Onium Salt [5]

(117) 5.0 g (15.5 mmol) of 3,3,5,5-tetramethyl-4,4-bis(2-propen-1-yloxy)-1,1-biphenyl pretreated by the same method as above, 3.8 ml of toluene, 512 mg (10% mol substrate) of sodium tungstate dihydrate, 1.61 ml (9% mol/substrate) of an aqueous 8.5% (weight/volume) phosphoric acid solution, 3.4 ml of water and a toluene solution of N-methyl-N,N,N-tri[2-(4-tert-butylphenylcarbonyloxy)ethyl]ammonium monomethyl sulfate obtained above were previously added and stirred. This mixed solution was heated at 65 C. and thereafter, under a nitrogen stream, added with 0.5 ml (0.5 times mol/substrate) of 45% hydrogen peroxide a total of 5 times, that is, at the initiation of reaction and after 1 hour, 2 hours, 3 hours and 4 hours therefrom, and the reaction was performed for 7 hours. The pH of the aqueous layer was adjusted to 2.5 by adding 0.5 ml of an aqueous 1N sodium hydroxide solution halfway therethrough. It was confirmed that 3,3,5,5-tetramethylbiphenyl-4,4-diglycidyl ether was produced in a reaction yield of 78% (LC area %, Analysis Condition 1). In addition, 8.2% (LC area %) of a monoepoxy compound as a reaction intermediate and 10.7% (LC area %) of a polar compound were produced.

(118) After the completion of reaction, 25 ml of toluene was additionally added, the aqueous layer was discharged, and the residue was washed twice with 10 ml of water and then washed with 12.5 ml of an aqueous 5% sodium thiosulfate solution. Furthermore, 25 ml of an aqueous 1N sodium hydroxide solution was added and after stirring at 25 C. for 15 minutes, the aqueous layer was discharged. Washing with the aqueous sodium hydroxide solution was repeated three times at an inner temperature of 35 C. for 30 minutes, and the resulting solution was washed with 25 ml of water. It was confirmed by LC and NMR that N-methyl-N,N,N-tri[2-(4-tert-butylphenylcarbonyloxy)ethyl]ammonium monomethyl was hydrolyzed and disappeared. The obtained organic phase was concentrated to obtain 4.7 g of 3,3,5,5-tetramethylbiphenyl-4,4-diglycidyl ether (Compound 21) as a crude crystal. Purity: 89.5% (LC area %, LC Analysis Condition 2) and yield: 77%. This crude crystal contained 4.6 mol % of the ester compound (Compound 22) and 1.4 mol % of the diol compound (Compound 23).

(119) The contents of tungsten and nitrogen in the compound were analyzed by the methods described above. The measurement results are shown in Table 1.

Example 15

Synthesis of Onium Salt [6]

(120) ##STR00033##

(121) To a mixed solution containing 2.40 g (13.6 mmol) of 3-diethylamino-1,2-propanediol, 20 ml of toluene and 4.13 g (3 times mol/substrate) of triethylamine, 5.8 g (2.2 times mol/substrate) of 4-tert-butylbenzoyl chloride obtained by the method above was added dropwise under ice-water cooling. The reaction was performed with stirring at 60 C. for 3 hours. The reaction yield was 98% (LC area %, LC Analysis Condition 2). After the completion of reaction, the reaction solution was washed three times with 20 ml of water and then concentrated. The obtained crude 3-diethylamino-1,2-propanediol-di-4-tert-butylbenzoate was purified by silica gel column chromatography (silica gel 60N, 200 g, developing system; hexane/ethyl acetate=4/1.fwdarw.2/1) to obtain 5.5 g of 3-diethylamino-1,2-propanediol-di-4-tert-butylbenzoate with a purity of 98% (LC area %). Purity: 98% (LC area %, LC Analysis Condition 2) and yield: 71%.

(122) A 0.16 g (0.30 mmol) portion of the diester obtained by the method above was added with 1 ml of toluene and 51 mg (1.2 times mol/substrate) of dimethyl sulfate and reacted at 80 C. for 2 hours. Production of 2,3-bis(4-tert-butyl-phenyloxy)-N,N-diethyl-N-methyl-1-propane ammonium monomethyl sulfate (hereinafter, referred to as Onium Salt [6]) at a conversion ratio of 99% or more was confirmed by NMR analysis. This reaction solution was used directly without purification in the epoxidation reaction.

(123) The NMR data of Onium Salt [6] obtained were as follows. 2,3-Bis(4-tert-butyl-phenyloxy)-N,N-diethyl-N-methyl-1-propane ammonium monomethyl sulfate

(124) 1.37 (18H, s, t-Bu), 1.43 (6H, s, CH3), 3.26 (3H, s, CH3-N), 3.56 (4H, m, N-CH2-CH3), 3.73 (3H, s, CH3OSO2-), 4.36 (2H, m, CH2-OCO), 4.58 (1H, dd, CH2-N), 4.78 (1H, dd, CH2-N), 6.03 (1H, m, CH), 7.41 (2H, dd, Ar), 7.46 (2H, dd, Ar), 7.87 (2H, dd, Ar), 7.96 (2H, dd, Ar).

Example 16

Epoxidation Reaction Using Onium Salt [6]

(125) 2.0 g (6.2 mmol) of 3,3,5,5-tetramethyl-4,4-bis(2-propen-1-yloxy)-1,1-biphenyl pretreated by the same method as above, 1.4 ml of toluene, 204 mg (10% mol/substrate) of sodium tungstate dihydrate, 0.36 ml (5% mol/substrate) of an aqueous 8.5% (weight/volume) phosphoric acid solution, 3.6 ml of water and a toluene solution of 2,3-bis(4-tert-butyl-phenyloxy)-N,N-diethyl-N-methyl-1-propane ammonium monomethyl sulfate obtained above were previously added and stirred. This mixed solution was heated at 65 C. and thereafter, under a nitrogen stream, added with 0.1 ml (0.5 times mol/substrate) of 45% hydrogen peroxide a total of 5 times, that is, at the initiation of reaction and after 1 hour, 2 hours, 3 hours and 6 hours therefrom, at an inner temperature of 65 to 68 C. The reaction was performed for a total of 7 hours at an inner temperature of 65 to 68 C., and it was confirmed by the LC analysis above that 3,3,5,5-tetramethylbiphenyl-4,4-diglycidyl ether was produced in a reaction yield of 77% (LC area %, Analysis Condition 1). In addition, 11% (LC area %) of a monoepoxy compound as a reaction intermediate and 8% (LC area %) of a polar compound were produced.

(126) After the completion of reaction, 6 ml of toluene was additionally added, the aqueous layer was discharged, and the organic phase was washed with 4 ml of an aqueous 5 wt % sodium thiosulfate solution. Furthermore, 4 ml of an aqueous 1N sodium hydroxide solution was added and after stirring for 1 hour, the aqueous layer was discharged. After repeating washing with the same aqueous sodium hydroxide solution four times, it was confirmed by LC that 2,3-bis(4-tert-butyl-phenyloxy)-N,N-diethyl-N-methyl-1-propane ammonium monomethyl was hydrolyzed and disappeared. The obtained organic phase was washed with 4 ml of water and then concentrated to obtain 1.9 g of 3,3,5,5-tetramethylbiphenyl-4,4-diglycidyl ether (Compound 21) with a purity of 83% (LC area %) as a crude crystal. Yield: 72%. This crude crystal contained 5.0 mol % of the ester compound (Compound 22) and 5.1 mol % of the diol compound (Compound 23).

(127) The contents of tungsten and nitrogen in the compound were analyzed by the methods described above. The measurement results are shown in Table 1.

Example 17

Synthesis of Onium Salt [7]

(128) ##STR00034##

(129) 10.3 g (93.2 mol) of 1-chloro-2,3-propanediol and 14.1 g (1.5 times mol/substrate) of triethylamine were heated with stirring at 80 C. for 12 hours, and 10 ml of ethanol was added. After homogenizing the reaction system, hexane was added to obtain 2,3-dihydroxypropyltriethylammonium chloride as a precipitate. The remaining ethanol was azeotropically distilled off by using toluene, and the residue was dried under reduced pressure to obtain 19.4 g of 2,3-dihydroxypropyltriethylammonium chloride. Crude yield: 98%.

(130) A mixed solution containing 3.0 g of crude 2,3-dihydroxypropyltriethylammonium chloride obtained by the method above, 30 ml of toluene and 5.17 g (2.2 times mol/substrate) of triethylamine was heated at 70 C., and 7.4 g (2.2 times mol/substrate) of 4-tert-butylbenzoyl chloride synthesized by the method above was added. The reaction was performed for 16 hours while adding 10 ml of tetrahydrofuran halfway therethrough and additionally adding 2.2 g (1.3 mol/substrate) of triethylamine. After allowing to cool, the precipitated solid in the reaction system was collected by filtration. This solid was dissolved in 50 ml of chloroform and washed twice with 10 ml of water and then, the solvent was distilled off to obtain 4.8 g of 2,3-bis(4-tert-butyl-phenyloxy)-N,N,N-triethyl-1-propane ammonium chloride. Purity: 96% (LC). Yield: 92%.

(131) A 2 g portion of the ammonium chloride obtained by the method above was purified (developing solvent: ethanol) with 100 ml of Diaion HP120 (produced by Mitsubishi Chemical Corporation) and concentrated. The obtained residue was dissolved in 30 ml of ethyl acetate, washed twice with 5 ml of a 10% (v/v) sulfuric acid solution and then concentrated to obtain 1.42 g of 2,3-bis(4-tert-butyl-phenyloxy)-N,N,N-triethyl-1-propane ammonium hydrogen sulfate (hereinafter, referred to as Onium Salt [7]). Purity: 98% (LC area %, LC Analysis Condition 2).

(132) The NMR data of Onium Salt [7] obtained are as follows. 2,3-Bis(4-tert-butyl-phenyloxy)-N,N,N-triethyl-1-propane ammonium hydrogen sulfate

(133) 1.32 (18H, s, t-Bu), 1.47 (9H, s, CH3), 3.59 (6H, m, NCH2-CH3), 4.29 (1H, m, HSO4), 4.37 (2H, m, CH2-OCO), 4.64 (1H, dd, CH2-N), 4.82 (1H, dd, CH2-N), 6.00 (1H, m, CH), 7.42 (4H, dd, Ar), 7.90 (4H, dd, Ar).

Example 18

Epoxidation Reaction Using Onium Salt [7]

(134) 5.0 g (15.5 mmol) of 3,3,5,5-tetramethyl-4,4-bis(2-propen-1-yloxy)-1,1-biphenyl pretreated by the same method as above, 3.8 ml of toluene, 51.2 mg (10% mol/substrate) of sodium tungstate dihydrate, 1.25 ml (7% mol/substrate) of an aqueous 8.5% (weight/volume) phosphoric acid solution, 3.4 ml of water and 0.46 g (5% mol/substrate) of 2,3-bis(4-tert-butyl-phenyloxy)-N,N,N-triethyl-1-propane ammonium sulfate obtained above were previously added and stirred. This mixed solution was heated at 65 C. and thereafter, under a nitrogen stream, added with 0.5 ml (0.5 times mol/substrate) of 45% hydrogen peroxide a total of 6 times, that is, at the initiation of reaction and after 1 hour, 2 hours, 3 hours, 4 hours and 6 hours therefrom. The reaction was performed for a total of 10 hours, that is, for 4 hours at an inner temperature of 65 to 66 C. and for 6 hours at an inner temperature of 68 to 69 C., and it was confirmed by the LC analysis above that 3,3,5,5-tetramethylbiphenyl-4,4-diglycidyl ether was produced in a reaction yield of 82% (LC area %, Analysis Condition 1). In addition, 5.4% (LC area %) of a monoepoxy compound as a reaction intermediate and 10.7% (LC area %) of a polar compound were produced.

(135) After the completion of reaction, 20 ml of toluene was additionally added, the aqueous layer was discharged, and the residue was washed twice with 10 ml of water and then washed with 12.5 ml of an aqueous 5% sodium thiosulfate solution. Furthermore, 25 ml of an aqueous 1N sodium hydroxide solution was added and after stirring at 25 C. for 1 hour, the aqueous layer was discharged. Washing with the aqueous sodium hydroxide solution was repeated three times at an inner temperature of 35 C. for 30 minutes, and it was confirmed by LC and NMR that Onium Salt [7] was hydrolyzed and disappeared and tert-butylberizoic acid as a hydrolysate of Onium Salt [7] did not remain. The obtained organic phase was washed with 25 ml of water and then concentrated to obtain 4.88 g of 3,3,5,5-tetramethylbiphenyl-4,4-diglycidyl ether (Compound 21) as a crude crystal. Purity: 87.5% (LC area %, LC Analysis Condition 2). Yield: 78%. This crude crystal contained 4.5 mol % of the ester compound (Compound 22) and 3.7 mol % of the diol compound (Compound 23).

(136) The contents of nitrogen and tungsten in the compound were analyzed by the methods described above. The measurement results are shown in Table 1.

Example 19

Synthesis of Onium Salt [8]

(137) ##STR00035##

(138) A mixed solution containing 2.00 g (18.1 mmol) of 3-chloro-1,2-propanediol and 4.58 g (2.5 times mol/substrate) of triethylamine was added dropwise to 4-tert-butylbenzoyl chloride synthesized in the same manner as above from 6.45 g (2.0 times mol/substrate) of 4-tert-butylbenzoic acid, 4.3 g (2 times mol/substrate) of thionyl chloride and 20 ml of toluene. The reaction was performed at 50 C. for 7 hours. After the completion of reaction, the reaction solution was washed twice with 10 ml of water and concentrated. The obtained crude 3-chloro-1,2-propanediol-di-4-tert-butylbenzoate was crystallized by adding hexane to obtain 5.0 g of 3-chloro-1,2-propanediol-di-4-tert-butylbenzoate. LC Purity: 98.5% (LC area %, LC Analysis Condition 2) and yield: 64%.

(139) A 1.00 g portion of the 3-chloro-1,2-propanediol-di-4-tert-butyl benzoate. obtained by the method above was added with 5.24 g (30 times mol/substrate) of pyridine and 37 mg (0.1 times mol/substrate) of potassium iodide and reacted with stirring under reflux conditions for 32 hours, whereby 1-[2,3-bis[(4-tert-butylphenylcarbonyloxy)propyl]pyridinium chloride was obtained at a conversion ratio of 98% with a selectivity of 62% (LC area %, LC Condition 2). After distilling off pyridine, 20 ml of hexane was added to the resulting residue to obtain 0.32 g of 1-[2,3-bis[(4-tert-butylphenylcarbonyloxy)propyl]pyridinium chloride (hereinafter, Onium Salt [8]). Purity: 92.9% (LC area %, LC Analysis Condition 2). Yield: 28%.

(140) The NMR data of Onium Salt [8] obtained are as follows.

1-[2,3-Bis[(4-tert-butylphenylcarbonyloxy)propyl]pyridinium chloride

(141) 1.32 (18H, d, t-Bu), 4.91 (2H, m, CH2-OCO), 5.38 (2H, m, CH2-N), 5.93 (1H, m, CH1-), 6.22 (1H, m, CH2-N), 6.03 (111, m, CH), 7.42 (2H, dd, Ar), 7.45 (2H, dd, Ar), 7.82 (2H, dd, Ar), 7.97 (2H, dd, Ar), 8.40 (1H, m, Py), 9.61 (2H, m, Py).

Example 20

Epoxidation Reaction Using Onium Salt [8]

(142) An aqueous solution containing 1 wt % of anhydrous sodium sulfate and 1 vol % of acetic acid, which was obtained by the same method as above, then a mixed solution of an aqueous 3 wt % sodium pyrophosphate solution and a 10 wt % ethylenediaminetetraacetic acid solution, furthermore, 1.0 g (3.1 mmol) of 3,3,5,5-tetramethyl-4,4-bis(2-propen-1-yloxy)-1,1-biphenyl washed with water, 1.0 ml of toluene, 102 mg (10% mol/substrate) of sodium tungstate dihydrate, 0.36 ml (5% mol/substrate) of an aqueous 8.5% (weight/volume) phosphoric acid solution, 1 ml of water and 81 mg (5% mol/substrate) of 1-[2,3-bis[(4-tert-butylphenylcarbonyloxy)propyl]pyridinium chloride obtained above were previously added and stirred. This mixed solution was heated at 65 C. and thereafter, under a nitrogen stream, added with 0.1 ml (0.5 times mol/substrate) of 45% hydrogen peroxide a total of 5 times, that is, at the initiation of reaction and after 1 hour, 2 hours, 3 hours and 4 hours therefrom, at an inner temperature of 65 to 68 C. The reaction was performed for 1 hour after each addition. Thereafter, 0.10 ml of an aqueous phosphoric acid solution was added to adjust the pH of the aqueous layer to 2.5, and the reaction was performed at an inner temperature of 68 C. while further adding 0.1 ml (0.5 times mol/substrate) of 45% hydrogen peroxide twice every hour, thereby performing the reaction for a total of 9 hours. It was confirmed that 3,3,5,5-tetramethylbiphenyl-4,4-diglycidyl ether was produced in a reaction yield of 68%. In addition, 13.7% of a monoepoxy compound as a reaction intermediate and 10.2% (LC area %) of a polar compound were produced.

(143) After the completion of reaction, 10 ml of toluene was additionally added, the aqueous layer was discharged, and the organic phase was washed with 5 ml of an aqueous 5% sodium thiosulfate solution. Furthermore, 5 ml of an aqueous 1N sodium hydroxide solution was added and after stirring for 1 hour, the aqueous layer was discharged. Washing with the same aqueous sodium hydroxide solution was repeated four times, and it was confirmed by LC and NMR that Onium Salt [8] was hydrolyzed and disappeared and tert-butylbenzoic acid as a hydrolysate did not remain. The obtained organic phase was washed with 5 ml of water and then concentrated to obtain 0.9 g of 3,3,5,5-tetramethylbiphenyl-4,4-diglycidyl ether with a purity of 68% (LC area %, LC Analysis Condition 2) as a crude crystal. Yield: 56%. This crude crystal contained 6.2 mol % of the ester compound 1 (Compound 22).

(144) The content of tungsten in the compound was analyzed by the method described above. The measurement results are shown in Table 1.

Example 21

Synthesis of Onium Salt [9]

(145) ##STR00036##

(146) A mixed solution containing 5 g (18.8 mmol) of 12-bromododecanoic acid, 2.35 ml (1 times mol/substrate) of hexanol, 100 ml of toluene and 0.2 ml of sulfuric acid was reacted for 4 hours while azeotropically distilling off the occurring water together with toluene, and after additionally adding 0.47 ml (0.2 times mol/substrate) of hexanol, the reaction was performed for another 2.5 hours. The reaction solution was washed with 100 ml of water, then with 50 ml of a saturated sodium bicarbonate solution and further with 50 ml of water, and the solvent was distilled off to obtain 6.3 g of 2-bromododecanoic acid hexyl ester with a purity of 99% or more. Yield: 92% (GC area %).

(147) A 2.20 g (6.1 mmol) portion of the 12-bromododecanoic acid hexyl ester obtained by the method above and 0.78 g (1.0 times mol/substrate) of dibutylamine were added, and the reaction was performed at 110 C. for 19 hours while additionally adding 0.31 g (0.4 times mol/substrate) of dibutylamine twice halfway therethrough. After the completion of reaction, 20 ml of ethyl acetate was added, and the resulting solution was washed twice with 10 ml of water. The obtained organic layer was concentrated and then subjected to column purification (Silica 60N, 100 g, developing solvent: hexane/ethyl acetate=4/1.fwdarw.2/1) to obtain 1.68 g of 12-N,N-dibutyldodecanoic acid hexyl ester. Yield: 67%.

(148) A 0.165 g (0.4 mmol) portion of the 12-N,N-dibutyldodecanoic acid hexyl ester obtained by the method above was added with 1.2 ml of toluene and 57.5 mg (1.5 times mol/substrate) of dimethyl sulfate and reacted at 70 C. for 3 hours. Production of N,N-diethyl-N-methyl-1-dodecanoic acid hexyl ester ammonium methylsulfate (hereinafter, referred to as Onium Salt [9]) at a conversion ratio of 99% or more was confirmed by NMR analysis. This reaction solution was used directly without purification in the oxidation reaction.

(149) The NMR data of Onium Salt [9] obtained are as follows.

N,N-diethyl-N-methyl-1-dodecanoic acid hexyl ester ammonium methylsulfate

(150) 0.85-1.10 (9H, m, CH3), 1.25-1.80 (34H, m, CH2-CH2-CH2-), 2.38 (2H, m, COCH2-), 3.07 (3H, s, NCH3), 3.21 (6H, m, NCH2-), 3.83 (3H, s, CH3SO2-), 4.12 (2H, m, COOCH2).

Example 22

Epoxidation Reaction Using Onium Salt [9]

(151) 2.0 g (6.2 mmol) of 3,3,5,5-tetramethyl-4,4-bis(2-propen-1-yloxy)-1,1-biphenyl pretreated by the same method as above, 1.2 ml of toluene, 0.205 g (10% mol/substrate) of sodium tungstate dihydrate, 0.64 ml (9% mol/substrate) of an aqueous 8.5% (weight/volume) phosphoric acid solution, 1.4 ml of water and a toluene solution of 12-N,N-dibutyldodecanoic acid hexyl ester ammonium monomethyl sulfate obtained above were previously added and stirred. This mixed solution was heated at 65 C. and thereafter, under a nitrogen stream, added with 0.1 ml (0.5 times mol/substrate) of 45% hydrogen peroxide a total of 6 times, that is, at the initiation of reaction and after 1 hour, 2 hours, 3 hours, 4 hours and 6 hours therefrom, at an inner temperature of 65 to 68 C. The pH of the aqueous phase during reaction was 2.0. The reaction was performed at an inner temperature of 65 to 68 C. for a total of 6 hours, and it was confirmed by the LC analysis above that 3,3,5,5-tetramethylbiphenyl-4,4-diglycidyl ether was produced in a reaction yield of 81.3% (LC area %). In addition, 10.7% of a monoepoxy compound and 7.4% (LC area %) of a polar compound were produced.

(152) After the completion of reaction, 20 ml of toluene was additionally added, the aqueous layer was discharged, and the organic phase was washed with 10 ml of an aqueous 5% sodium thiosulfate solution. Furthermore, 10 ml of an aqueous 1N sodium hydroxide solution was added and after stirring for 1 hour, the aqueous layer was discharged. Washing with the same aqueous sodium hydroxide solution was repeated three times, and the resulting solution was washed with 8 ml of water. The obtained organic phase was concentrated to obtain 2.08 g of 3,3,5,5-tetramethylbiphenyl-4,4-diglycidyl ether as a crude crystal. Purity: 86.4% (LC area %, LC Analysis Condition 2) and yield: 82%.

(153) A 1 g (2.4 mmol) portion of the crude crystal obtained above was added with 3 ml of toluene and dissolved by heating at 50 C., and 7 ml of methanol was added thereto. The resulting solution was cooled to 6 C., and the precipitated crystal was collected by filtration to obtain 0.52 g of a crystal of 3,3,5,5-tetramethylbiphenyl-4,4-diglycidyl ether. It was confirmed by NMR that the crystal was free from Onium Salt (10) and a decomposition product of the onium salt. Purity: 95.6% (LC area %, LC Analysis Condition 2). Recovery percentage: 58%. This crystal contained 0.7 mol % of the ester compound (Compound 22) and 6.9 mol % of the diol compound (Compound 23).

Example 23

Synthesis of Onium Salt [10]

(154) ##STR00037##

(155) 2.81 g (1.0 times mol/chlorobutanol) of hexadecyl chloroformate was added to 1 g (9.2 mmol) of 4-chlorobutanol, 7.4 ml of pyridine and 10 ml of toluene and reacted at room temperature for 3 hours. The precipitated pyridine hydrochloride was separated by filtration using a small amount of toluene, whereby 37 g of a mixed solution of 4-chlorobutyl hexadecyl carbonate, pyridine and toluene. A 1 g portion of the obtained solution was reacted for 10 hours while additionally adding 2 ml of pyridine halfway therethrough. After confirming by NMR analysis of the reaction solution that hexadecyl chloroformate disappeared, pyridine was distilled off, and hexane was added to the resulting residue to obtain a crystal. This crystal was dissolved in ethanol and after filtering insoluble matters, the resulting solution was concentrated to obtain 0.11 g of 1-[(hexadecyloxycarbonyl)oxy]butyl]pyridinium chloride (hereinafter, referred to as Onium Salt [10]). Yield: 95% or more. Purity: 90% or more (NMR).

(156) The NMR data of Onium Salt [10] obtained are as follows.

1-[(Hexadecyloxycarbonyl)oxy]butyl]pyridinium chloride

(157) 0.88 (3H, dd, CH3), 1.2-1.4 (26H, m, CH2-), 1.66 (2H, m, CH2-), 1.85 (2H, m, CH2-), 2.20 (2H, m, CH2-), 4.11 (2H, dd, CH2-), 4.20 (2H, dd, CH2-), 5.20 (2H, dd, NCH2-), 8.09 (2H, dd, Py), 8.46 (1H, dd, Py), 9.53 (2H, dd, Py).

Example 24

Epoxidation Reaction Using Onium Salt [10]

(158) 1.5 g (4.7 mmol) of 3,3,5,5-tetramethyl-4,4-bis(2-propen-1-yloxy)-1,1-biphenyl pretreated by the same method as above, 1 ml of toluene, 1 ml of octane, 0.154 g (10% mol/substrate) of sodium tungstate dihydrate, 0.48 ml (9% mol/substrate) of an aqueous 8.5% (weight/volume) phosphoric acid solution, 1.0 ml of water and 0.106 g (5% mol/substrate) of 1-[(hexadecyloxycarbonyl)oxy]butyl]pyridinium chloride obtained above were previously added and stirred. This mixed solution was heated at 65 C. and thereafter, under a nitrogen stream, added with 0.5 ml (0.5 times mol/substrate) of 45% hydrogen peroxide a total of 6 times, that is, at the initiation of reaction and after 1 hour, 2 hours, 3 hours, 4 hours and 6 hours therefrom. The pH of the aqueous phase during reaction was about 3.0. The reaction was performed for a total of 17 hours, that is, for 7 hours at an inner temperature of 65 to 66 C. and for 10 hours at an inner temperature of 68 to 69 C., and it was confirmed by the LC analysis above that 3,3,5,5-tetramethylbiphenyl-4,4-diglycidyl ether was produced in a reaction yield of 53.7% (LC area %, Analysis Condition 1). In addition, 10.3% (LC area %) of a monoepoxy compound as a reaction intermediate and 22.0% (LC area %) of a polar compound were produced.

(159) After the completion of reaction, 7.5 ml of toluene was additionally added, the aqueous layer was discharged, and the residue was washed twice with 7.5 ml of water and then washed with 7.5 ml of an aqueous 5% sodium thiosulfate solution. Furthermore, 7.5 ml of an aqueous 1N sodium hydroxide solution was added and after stirring at 25 C. for 1 hour, the aqueous layer was discharged. Washing with the aqueous sodium hydroxide solution was repeated three times at an inner temperature of 30 C. for 30 minutes, and it was confirmed by LC and NMR that Onium Salt [11] was hydrolyzed and disappeared. The obtained organic phase was washed with 25 ml of water and then concentrated to obtain 0.94 g of 3,3,5,5-tetramethylbiphenyl-4,4-diglycidyl ether as a crude crystal. Purity: 63.0% (LC area %, LC Analysis Condition 2). Yield: 36%.

Example 25

(160) After adding 14 ml of methanol to 2.0 g of the 3,3,5,5-tetramethylbiphenyl-4,4-diglycidyl ether crude crystal obtained in Example 14, the mixture was stirred and crystalized at 50 C. for 3 hours and cooled to 6 C. and thereafter, the crystal was collected by filtration to obtain 1.55 g of 3,3,5,5-tetramethylbiphenyl-4,4-diglycidyl ether with a purity of 90.9% (LC area %, LC Analysis Condition 2). Recovery percentage: 79%. This crystal contained 2.6 mol % of the ester compound (Compound 22) and 0.6 mol % of the diol compound (Compound 23). The contents of nitrogen and chlorine in the compound were analyzed by the methods described above. The measurement results are shown in Table 1.

Example 26

(161) After adding 3 ml of methanol to 0.69 g of the 3,3,5,5-tetramethylbiphenyl-4,4-diglycidyl ether crude crystal obtained in Example 16, the mixture was stirred and crystalized at 50 C. for 1 hour and cooled to 6 C. and thereafter, the crystal was collected by filtration to obtain 0.52 g of 3,3,5,5-tetramethylbiphenyl-4,4-diglycidyl ether with a purity of 90.4% (LC area %, LC Analysis Condition 2). Recovery percentage: 80%. This crystal contained 2.0 mol % of the ester compound (Compound 22) and 1.2 mol % of the diol compound (Compound 23). The content of nitrogen in the compound was analyzed by the method described above. The measurement results are shown in Table 1.

Example 27

(162) After adding 3 ml of toluene to 2.0 g of the 3,3,5,5-tetramethylbiphenyl-4,4-diglycidyl ether crude crystal obtained in Example 18, the mixture was heated/dissolved at 50 C., then added with 14 ml of methanol and cooled to 6 C. and thereafter, the crystal was collected by filtration to obtain 1.38 g of 3,3,5,5-tetramethylbiphenyl-4,4-diglycidyl ether with a purity of 96.1% (LC area %, LC Analysis Condition 2). Recovery percentage: 71%. This crystal contained 0.2 mol % of the ester compound (3 and 0.5 mol % of the diol compound .

(163) The content of nitrogen in the compound was analyzed by the method described above. The measurement results are shown in Table 1.

Example 28

Epoxidation Reaction of 1,5-Cyclooctadiene Using Onium Salt [7]

(164) 3.0 g (27.7 mmol) of 1,5-cyclooctadiene (produced by Tokyo Chemical Industry Co., Ltd.), 9 ml of toluene, 0.183 g (2% mol/substrate) of sodium tungstate dihydrate, 0.32 ml (1% mol/substrate) of an aqueous 8.5% (weight/volume) phosphoric acid solution, 3.4 ml of water and 0.16 g (1% mol/substrate) of the 2,3-bis(4-tert-butyl-phenyloxy)-N,N,N-triethyl-1-propane ammonium hydrogen sulfate (Onium Salt [7]) obtained above were added and stirred. This mixed solution was heated at 50 C. and thereafter, under a nitrogen stream, added with 0.9 ml (0.5 times mol/substrate) of 45% hydrogen peroxide a total of 6 times, that is, at the initiation of reaction and after 1 hour, 2 hours, 3 hours, 5 hours and 7 hours therefrom. The pH of the aqueous phase 2 hours after the initiation of reaction was 4.8. The reaction was performed for a total of 9 hours at an inner temperature of 50 to 51 C. It was confirmed by the GC analysis above that 1,2,5,6-diepoxycyclooctane was produced in a reaction yield of 90.2% (GC area %). In addition, 6.6% (LC area %) of a monoepoxy compound as a reaction intermediate and 3.2% (GC area %) of a compound resulting from ring opening of epoxy were produced.

(165) After the completion of reaction, 10 ml of toluene was additionally added, the aqueous layer was discharged, and the residue was washed with 3 ml of water and then washed with 10 ml of an aqueous 5% sodium thiosulfate solution. Furthermore, 10 ml of an aqueous 1N sodium hydroxide solution was added and after stirring at 25 C. for 15 minutes, the aqueous layer was discharged. Washing with the aqueous sodium hydroxide solution was repeated three times at an inner temperature of 30 C. for 30 minutes, and it was confirmed by LC and NMR that Onium Salt [7] was hydrolyzed and disappeared and tert-butylbenzoic acid as a hydrolysate of Onium Salt [7] did not remain. The organic phase was further washed twice with 4 ml of water, and the obtained organic phase was concentrated to obtain 1.0 g of 1,2,5,6-diepoxycyclooctane in a liquid form. Purity: 97% (GC area %) and yield: 26%. This crude crystal contained 1.8 mol % of the ester compound .

(166) The contents of tungsten and nitrogen in the compound were analyzed by the methods described above. The measurement results are shown in Table 1.

(167) The NMR data of 1,2,5,6-diepoxycyclooctane are as follows, 1,2,5,6-Diepoxycyclooctane:

(168) 1.82-2.05 (8H, m, CH2-), 3.00 (4H, m, CHO).

Reference Example 1

Synthesis of Impurity Specimen

(169) Synthesis of 3-[[3,3,5,5-tetramethyl-4-(2-oxylanylmethoxy)[1,1-biphenyl]-4-yl]oxy]-1,2-propanediol (compound ):

(170) 50 ml of acetic acid was added to 10 g (0.028 mol) of 3,3,5,5-tetramethylbiphenyl-4,4-diglycidyl ether, and the mixture was reacted at an inner temperature of about 85 C. for 9 hours. The acetic acid was distilled off under reduced pressure azeotropically together with toluene to obtain 16.1 g of a residue. This was added with 60 ml of an aqueous 1N sodium hydroxide solution and reacted at room temperature for 2 hours. The precipitated solid containing, as the main component, [[3,3,5,5-tetramethyl-[1,1-biphenyl]-4,4-yl]oxy]bis-(1,2-propanediol) was separated by filtration, and the filter product was washed with 100 ml of ethyl acetate. The ethyl acetate of the wash liquid was combined with the aqueous phase and separated, and the obtained organic phase was concentrated. The residue obtained was purified by column chromatography (Silica 60N, 300 g, developing solvent: hexane/ethyl acetate=from 1/1 to 1/2) to obtain 3.8 g of 3-[[3,3,5,5-tetramethyl-4-(2-oxylanylmethoxy)[1,1-biphenyl]-4-yl]oxy]-1,2-propanediol as a crystal. Yield: 36%. Purity: 95.5% (LC area %, LC Analysis Condition 2).

(171) The NMR data of the diol compound obtained are as follows.

3-[[3,3,5,5-Tetramethyl-4-(2-oxylanylmethoxy)[1,1-biphenyl]-4-yl]oxy]-1,2-propanediol

(172) 2.34 (12H, s, CH3), 2.72 (1H, dd, CH2-), 2.91 (1H, dd, CH2-), 3.44 (1H, m, CH), 3.76 (1H, dd, CH2-), 3.79 (2H, m, CH2-OH), 3.90 (2H, d, O-CH2-CH(OH)), 4.08 (1H, dd, CH2-), 4.09 (1H, m, CHOH), 7.18 (4H, s, C6H2 (Me)2-).

Reference Example 2

Synthesis of 4-tert-butylbenzoic acid-2-hydroxy-3-[[3,3,5,5-tetramethyl-4-(2-oxylanylmethoxy)[1,1-biphenyl]-4-yl]oxy]propyl ester (compound )

(173) 0.08 g (1.5 times mol/substrate) of tert-butylbenzoyl chloride obtained by the method above was added to a mixed solution containing 0.1 g (0.3 mmol) of the diol compound obtained by the method above, 2 ml of toluene and 0.11 ml (3 times mol/substrate) of triethylamine, and the mixture was reacted at room temperature for 5 hours. After the reaction, 6 ml of ethyl acetate and 2 ml of water were added, followed by stirring, and the obtained organic phase was purified by column chromatography (silica 60N, 30 g, developing solvent: hexane/ethyl acetate=4/1) to obtain about 50 mg of 4-tert-butylbenzoic acid-2-hydroxy-3-[[3,3,5,5-tetramethyl-4-(2-oxylanylmethoxy)[1,1-biphenyl]-4-yl]oxy]propyl ester (compound 13) in about 50 mg. Purity: 96.3% (LC area %, LC Analysis Condition 2).

(174) The NMR data of the compound obtained are as follows.

4-Tert-butylbenzoic acid-2-hydroxy-3-[[3,3,5,5-tetramethyl-4-(2-oxylanylmethoxy) [1,1-biphenyl]-4-yl]oxy]propyl ester

(175) 1.32 (9H, s, t-Bu), 2.34 (12H, s, CH3), 2.73 (1H, dd, CH2-), 2.90 (1H, dd, CH2-), 3.40 (1H, m, CH), 3.78 (1H, dd, CH2-), 3.95 (2H, m, O-CH2-CH(OH)), 4.10 (1H, m, CH2-), 4.39 (1H, m, CHOH), 4.60 (2H, m, CH2-OCO), 7.18 (4H, s, C6H2 (Me)2-), 7.49 (2H, d, t-Bu-C6H4-), 7.99 (2H, d, t-Bu-C6H4-).

(176) TABLE-US-00001 TABLE 1 Tungsten Nitrogen Chlorine Compound / (ppm by (ppm by (ppm by Compound weight) weight) weight) (mol %) Example 2 0.06 100 31 2.7 Example 4 38 1.1 Example 8 0.07 84 <10 2.4 Example 9 10 <10 0.3 Example 12 3.46 0.6 Example 14 0.58 20 4.6 Example 16 0.45 56 5.0 Example 18 5.2 7 4.5 Example 20 1.82 6.2 Example 22 1.6 0.7 Example 25 7 <10 2.6 Example 26 15 2.0 Example 27 2 0.2 Example 28 0.04 7 1.8 Comparative 142 1600 30 Example 1

(177) While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the invention. This application is based on Japanese Patent Application (Patent Application No. 2012-082319) filed on Mar. 30, 2012, Japanese Patent Application (Patent Application No. 2012-226995) filed on Oct. 12, 2012, and Japanese Patent Application (Patent Application No. 2013-012207) filed on Jan. 25, 2013, the contents of which are incorporated herein by way of reference.