Claims
- 1. A process for the selective epoxidation of a non-acrylic ethylenic double bond in an unsaturated (meth) acrylic compound of formula: ##STR5## wherein: R.sub.1 is hydrogen or alkyl having 1-5 carbon atoms;
- R.sub.2 is hydrogen, alkyl, or aryl;
- R.sub.3 is a straight-chain, branched, or cyclic alkylene or oxyalkylene radical having 1-12 carbon atoms and, optionally, when R.sub.2 is alkyl, one of the carbon atoms thereof may be linked to one of the carbon atoms of R.sub.3 to form a ring; and
- A is oxygen, sulfur, NH, or NR.sub.4, R.sub.4 being alkyl having 1-12 carbon atoms,
- comprising reacting hydrogen peroxide with said unsaturated (meth)acrylic compound at a temperature of between 10.degree.-50.degree. C. and a pH of 1.3 to 3.5, in contact with at least one catalyst, said catalyst being an alkali metal molybdate or an alkali metal tungstate, and in the presence of at least one phase transfer agent,
- wherein the concentration of hydrogen peroxide is 5 to 50%, and the molar ratio between hydrogen peroxide and the unsaturated (meth)acrylic compound is at least 1 mole of peroxide per mole of said compound, and
- wherein the compound of formula (I) is converted in a selective manner, with a degree of conversion of more than 70% to an epoxide of formula ##STR6##
- 2. A process according to claim 1, wherein the reaction is carried out in the presence of an organic solvent.
- 3. A process according to claim 1, wherein the phase transfer agent is a quaternary ammonium or phosphonium salt.
- 4. A process according to claim 1, wherein the catalyst is used in an amount of at least 0.1 mol % relative to the compound to be epoxidized.
- 5. A process according to claim 1, where the phase transfer agent is used in an amount of at least 0.5 mol % relative to the compound to be epoxidized.
- 6. A process according to claim 1, wherein prior to the epoxidation reaction, the compound of formula I is stabilized by the addition of a stabilizing agent selected from the group consisting of hydroquinone, hydroquinone monomethyl ether, phenothiazine, N,N-diethylhydroxylamine, nitrobenzene, di-tert-butylcatechol, p-anilinophenol, di-(2-ethylhexyl)octylphenyl phosphite and mixtures thereof.
- 7. A process according to claim 1, wherein the phase transfer agent is a quaternary ammonium or phosphonium salt and is present in a molar proportion to the compound to be epoxidized of between 1% and 3%; hydrogen peroxide is employed in a ratio 1.5-3 moles per mole of formula I and at a concentration in aqueous solution of 10-35%; and the pH of the reaction mixture is 1.5-3.
- 8. A process according to claim 7, wherein prior to the epoxidation reaction, the compound of formula I is stabilized by the addition of a stabilizing agent selected from the group consisting of hydroquinone, hydroquinone monomethyl ether, phenothiazine, N,N-diethylhydroxylamine, nitrobenzene, di-tert-butylcatechol, p-anilinophenol, di-(2-ethylhexyl)octylphenyl phosphite and mixtures thereof.
- 9. A process according to claim 1, wherein the compound of formula (I) is allyl (meth)acrylate or allyl acrylate.
- 10. A process according to claim 1, wherein the pH of the reaction mixture has a value between 2.6 and 3.5, inclusive.
- 11. A process according to claim 1, wherein the pH of the reaction mixture has a value between 1.5 and 3.5, inclusive.
- 12. A process according to claim 1, wherein
- R.sup.1 =H or CH.sub.3 ;
- A=O or S;
- R.sub.2 =H, C.sub.1 -C.sub.12 alkyl or C.sub.6 -C.sub.14 aryl;
- R.sub.3 =straight chain, branched or cyclic alkylene radical having 1-12 carbon atoms and, optionally, when R.sub.2 is alkyl, one of the carbon atoms thereof may be linked to one of the carbon atoms of R.sub.3 to form a ring.
Priority Claims (1)
Number |
Date |
Country |
Kind |
89/17134 |
Dec 1989 |
FRX |
|
Parent Case Info
This application is a continuation of application Ser. No. 08/026,235, filed Mar. 1, 1993, now abandoned, which in turn is a continuation of application Ser. No. 07/630,972, filed Dec. 21. 1990, now abandoned.
US Referenced Citations (9)
Foreign Referenced Citations (10)
Number |
Date |
Country |
151941 |
Aug 1985 |
EPX |
190609 |
Aug 1986 |
EPX |
0190609 |
Aug 1986 |
EPX |
1205350 |
Feb 1960 |
FRX |
1206666 |
Feb 1960 |
FRX |
3602254 |
Jul 1987 |
DEX |
156475 |
Sep 1982 |
JPX |
56975 |
Apr 1985 |
JPX |
991452 |
May 1965 |
GBX |
2055821 |
Mar 1981 |
GBX |
Non-Patent Literature Citations (3)
Entry |
Chemical Abstracts, vol. 108, No. 16, Apr. 18, 1988, p. 8, 132450e (JP-A-62-81378). (Okamoto). |
Chow et al. "Homo-and Copolymers of Vinyl Esters, Acrylates and Methacrylates of Some Derivatives of Fatty Acids," Journal of Applied Polymer Science, vol. 13, pp. 1545-1553 (1969). |
Prandi et al, Tetrahydron Letters, vol. 27, No. 23, pp. 2617-2620, 1986. |
Continuations (2)
|
Number |
Date |
Country |
Parent |
26235 |
Mar 1993 |
|
Parent |
630972 |
Dec 1990 |
|