Title:
PROCESS FOR THE PREPARATION OF $g(a)-METHYLENE LACTONES
Document Type and Number:
WIPO Patent Application WO/2000/058297
Kind Code:
A2
Abstract:
This invention concerns a process for the addition of formaldehyde to the $g(a) carbon atom of lactones for the production of $g(a)-methylenelactones, and specifically $g(a)-methylene-$g(g)-butyrolactone.
Inventors:
MANZER LEO E (US)
COULSON DALE ROBERT (US)
COULSON DALE ROBERT (US)
Application Number:
PCT/US2000/006958
Publication Date:
October 05, 2000
Filing Date:
March 16, 2000
Export Citation:
Assignee:
DU PONT (US)
MANZER LEO E (US)
COULSON DALE ROBERT (US)
MANZER LEO E (US)
COULSON DALE ROBERT (US)
International Classes:
C07D307/33; C07B61/00; C07D307/58; (IPC1-7): C07D307/00
Foreign References:
| EP0295553A1 | 1988-12-21 | |||
| EP0366304A2 | 1990-05-02 |
Other References:
PATENT ABSTRACTS OF JAPAN vol. 1999, no. 02, 26 February 1999 (1999-02-26) -& JP 10 298172 A (MITSUBISHI RAYON CO LTD), 10 November 1998 (1998-11-10) cited in the application
A.W. MURRAY ET AL.: "Convenient Synthesis of alpha-Epoxylactones (4-Oxo-1,5-dioxaspiro[2.4Üheptanes and -[2.5Üoctanes)" SYNTHESIS, 1985, pages 35-38, XP002152086 STUTTGART DE cited in the application
J. MARTIN ET AL.: "A New Method for the Synthesis of alpha-Methylenebutyrolactones" JOURNAL OF THE CHEMICAL SOCIETY, CHEMICAL COMMUNICATIONS, 1970, page 27 XP002152087 LETCHWORTH GB cited in the application
A.W. MURRAY ET AL.: "Convenient Synthesis of alpha-Epoxylactones (4-Oxo-1,5-dioxaspiro[2.4Üheptanes and -[2.5Üoctanes)" SYNTHESIS, 1985, pages 35-38, XP002152086 STUTTGART DE cited in the application
J. MARTIN ET AL.: "A New Method for the Synthesis of alpha-Methylenebutyrolactones" JOURNAL OF THE CHEMICAL SOCIETY, CHEMICAL COMMUNICATIONS, 1970, page 27 XP002152087 LETCHWORTH GB cited in the application
Attorney, Agent or Firm:
Feltham, Neil S. (DE, US)
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Claims:
CLAIMS What is claimed is:
| 1. | A process for preparing amethylenelactones of Formula II comprising heating lactones of Formula I and formaldehyde in the vapor phase at a temperature of above 200°C in the presence of a basic catalyst: 0 0 \0 + base \/"\/ Rc)/, c/ R2 RI (Cl), 4 basc Formula I Formula II wherein, n=111; RI, R2, R3 and R4 taken independently are hydrogen, hydrocarbyl or substituted hydrocarbyl, ClCl8 unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted cycloalkyl, unsubstituted or substituted cycloalkyl containing at least one heteroatom unsubstituted or substituted aromatic ring, and unsubstituted or substituted aromatic ring containing at least one heteroatom. |
| 2. | A process according to Claim 1 wherein R1, R2, R3 and, R4 are joined to form members of a ring structure selected from the group consisting of unsubstituted or substituted cycloalkyl, unsubstituted or substituted cycloalkyl containing at least one heteroatom in the ring unsubstituted or substituted aromatic ring, and unsubstituted or substituted aromatic ring containing at least one heteroatom in the ring. |
| 3. | The process of Claims 1 or 2 wherein the lactone of Formula I is ybutyrolactone and the amethylenelactone of Formula II is amethyleney butyrolactone. |
| 4. | The process of Claim 1 or 2 wherein R3 is CH3. |
| 5. | A process according to Claim 1 wherein the temperature is from about 250°C to about 400°C. |
| 6. | A process according to Claim 5 wherein the temperature is from about 300°C to about 340°C. |
| 7. | A process according to Claim 1 wherein the base catalyst is selected from the group consisting of metal oxides, metal hydroxides, and metal carbonates. |
| 8. | A process according to Claim 7 wherein the base catalyst is selected from the group consisting of magnesium oxide, barium hydroxide, barium oxide, lanthanum oxide potassium hydroxide, cadmium oxide, rubidium oxide, lithium hydroxide, strontium hydroxide, sodium hydroxide, calcium hydroxide, barium carbonate and mixtures thereof. |
| 9. | A process according to Claim 7wherein the base catalyst is optionally supported on a suitable support. |
| 10. | A process according to Claim 7wherein the base catalyst optionally comprises a catalyst promoter. |
| 11. | A process according to Claim 10 wherein said catalyst promoter is gold. |
| 12. | A process according to Claim 9 wherein the suitable support is selected from the group consisting of silica, titania, zirconia, alumina, carbon, zeolites and mixtures thereof. |
| 13. | A process according to Claim 9 wherein the base catalyst is selected from the group consisting of magnesium oxide, barium hydroxide, barium oxide, lanthanum oxide, potassium hydroxide, cadmium oxide, rubidium oxide, lithium hydroxide, strontium hydroxide, sodium hydroxide, barium carbonate, calcium hydroxide, and wherein the suitable support is SiO2. |
| 14. | A process according to Claim 8 wherein the amethylenelactone is produced at a selectivity of at least 50%. |
| 15. | A process according to Claim 14 wherein the amethylenelactone is produced at a selectivity of at least 95%. |
| 16. | A process according to Claim 13 wherein the supported catalyst is Ba (OH) 2/Si02. |
| 17. | A process according to Claim 13 wherein the supported catalyst is La (OH) 2/Si02. |
| 18. | A process according to Claim 12 wherein the supported catalyst is Ba (OH) 2/Carbon. |
| 19. | A process according to Claim 11 wherein the supported catalyst is Ba (OH) 2/Au/Si02. |
| 20. | A process according to Claim 1 wherein the formaldehyde is in the form of formalin. |
| 21. | A process according to Claim 1 wherein the formaldehyde is in the form of formaldehyde polymer. |
| 22. | A process for preparing amethylenelactones of Formula II comprising: (a) heating lactones of Formula I and formaldehyde in the vapor phase at a temperature of above 200°C in the presence of a basic catalyst for a time sufficient for the amethylenelactones of Formula II to be formed; O O \0 + base o \/ \/ Rz R3 R4 Ri Rz R3 R4 Formula I Formula II wherein, <BR> <BR> <BR> roi=111;<BR> <BR> <BR> <BR> <BR> RI, R2, R3 and R4 taken independently are hydrogen, hydrocarbyl or substituted hydrocarbyl, C1Cl8 unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted cycloalkyl, unsubstituted or substituted cycloalkyl containing at least one heteroatom, unsubstituted or substituted aromatic ring, and unsubstituted or substituted aromatic ring containing at least one heteroatom, (b) separating the lactones of Formula I from the basic catalyst; (c) contacting the basic catalyst with oxygen for a time sufficient to permit catalyst regeneration; and (d) repeating steps (a) through (c). |
| 23. | A process according to Claim 22 wherein the contacting of the basic catalyst with oxygen of step (c) is for a time of about 5 min to about 60 min. |
| 24. | A process according to Claim 22 wherein the contacting of the basic catalyst with oxygen of step (c) is at a temperature of about 300°C to about 500°C. |
| 25. | A process according to Claim 24 wherein the contacting of the basic catalyst with oxygen of step (c) is at a temperature of about 400°C to about 425°C. |
| 26. | A process for preparing amethylenelactones of Formula II comprising: (a) heating lactones of Formula I and formaldehyde in the vapor phase at a temperature of above 200°C in the presence of a basic catalyst for a time sufficient for the amethylenelactones of Formula II to be formed in a reactor effluent; 0 0 \O + base (CH20r (c>/, c R2 R3 R4 R2 R3 R4 Formula I Formula II wherein, <BR> <BR> <BR> ri=111;<BR> <BR> <BR> <BR> <BR> R1, R2, R3 and R4 taken independently are hydrogen, hydrocarbyl or substituted hydrocarbyl, ClCl8 unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted cycloalkyl, unsubstituted or substituted cycloalkyl containing at least one heteroatom, unsubstituted or substituted aromatic ring, and unsubstituted or substituted aromatic ring containing at least one heteroatom, (b) collecting the reactor effluent of step (a); and (c) contacting the collected effluent with the base catalyst at a temperature of above 200°C. |
| 27. | The process of Claim 26 wherein steps (b) and (c) are repeated from about 1 to about 10 times. |
Description:
INTERNATIONALSEARCHREPORT ma mm PCT/US00/06958 C. (Continuatlon) DOCUMENTS CONSIDEREDTOBERELEVANT Category* Citationofdocument,withincicatlon, where appropriate.oftherelevantpassages RelevanttodaimNo. AA.W.MURRAYET AL. :"ConvenientSynthesis1,22,27 ofalpha-Epoxylactones (4-Oxo-1,5-dioxaspiro'2.4!heptanesand -'2.5!octanes)" SYNTHESIS, 1985,pages35-38,XP002152086 STUTTGARTDE citedintheapplication page35;figureA AJ.MARTINETAL.:"ANewMethodforthe1,22,27 Synthesisof alpha-Methylenebutyrolactones" JOURNALOFTHECHEMICALSOCIETY,CHEMICAL COMMUNICATIONS, 1970,page27XP002152087 LETCHWORTHGB citedintheapplication thewholedocument AEP0366304A(BEECHAMGROUPPLC)1,22,27 2May1990(1990-05-02) citedintheapplication page16,line20-line42 1 INTERNATIONALSEARCHREPORT Inte onel AppilcatlonNo IMamatlon on peteM tamily msmbsrs PCT/US 00/06958 PatentdocumentPublicationPatentfamily Publication citedinsearch report date membeqs) date JP10298172A10-11-1998NONE EP0295553A21-12-1988DE3719873A29-12-1988 CA1337819A26-12-1995 DE3864322A26-09-1991 JP1019026A23-01-1989 US4997955A05-03-1991 EP0366304A02-05-1990AT165095T15-05-1998 AU4278289A26-04-1990 CA2000041A13-04-1990 DE68928644D20-05-1998 DE68928644T27-08-1998 DK504889A14-04-1990 JP2134380A23-05-1990 JP2934743B16-08-1999 PT91956A,B30-04-1990 US5166357A24-11-1992 ZA 8907698 A 26-09-1990ZA8907698A 26-09-1990