US20020103388A1 - Process for the preparation of substitued pyranes - Google Patents
Process for the preparation of substitued pyranes Download PDFInfo
- Publication number
- US20020103388A1 US20020103388A1 US09/943,669 US94366901A US2002103388A1 US 20020103388 A1 US20020103388 A1 US 20020103388A1 US 94366901 A US94366901 A US 94366901A US 2002103388 A1 US2002103388 A1 US 2002103388A1
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- United States
- Prior art keywords
- compound
- formula
- solid acid
- wessalith
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 0 [1*]C1([2*])CCCC([3*])(C#C)O1 Chemical compound [1*]C1([2*])CCCC([3*])(C#C)O1 0.000 description 5
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D309/04—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
Definitions
- the present invention relates to a novel process for the preparation of substituted pyranes of the general formula I
- R 1 , R 2 and R 3 are lower alkyl.
- the compounds of formula I belong to a known class of compounds.
- the compound of formula I wherein each of R 1 , R 2 and R 3 is methyl, 2-ethinyl-tetrahydro-2,6,6-trimethylpyran is a known intermediate, e.g., in the manufacture of flavours and has been prepared so far from dehydrolinalool by ring closure catalyzed by tungsten, molybdenum or polyphosphoric acid (Strickler et al., Helv. Chem. Acta 1966, 49, 2055; Erman et al., Tetrahedron 1976, 34, 2981 and Belgian Patent No. 852 918).
- the process of the present invention proceeds in high yields and in short reaction time. Further, the process of the present invention has the advantage that the use of a solvent and unwanted pressure increase in closed reaction vessels is avoided.
- microwave refers to the region of the electromagnetic spectrum having frequencies of 30 GHz to 300 MHz thus corresponding to wavelengths of 1 cm to 1 m.
- household or industrial microwave heaters are required to operate at either 12.2 cm (2.45 GHz) or 33.3 cm (918 MHz).
- the term microwaves refers particularly to such wavelenghts.
- conventional microwave equipment can be used.
- Microwave equipment suitable in the process of this invention is supplied, e.g., by the firms MLS, Leutkirch, Germany (Lavis Multiquant 1000); or MILESTONE Inc., Monroe, Conn. 06468, USA (Ethos reactors).
- the irradiation in the process of this invention is carried out applying a power of irradiation of from about 600 W to 1200 W, more preferably from about 800 W to about 1000 W.
- solid acid means an ordered solid having defined acidic centers selected from Lewis and Bronstedt centers. Such centers may be engineered to control which reaction product is favored in a particular reaction.
- solid acids which may be used as catalysts in the present invention not only accelerate the rate of the reaction, but in reaction systems where multiple products may be formed, they may strongly influence which of the products is produced in the greatest amount.
- the solid acid used as a catalyst in the present invention is suitably a strong organic acid, such as a polymeric sulfonic acid, e.g., a polyperfluoroalkylene sulfonic acid, particularly Deloxan® ASP (Degussa, Frankfurt/M., Germany) or Nafion® NR 50 (DuPont, Wilmington, Del.,USA), or an anionic ion exchange resin such as Amberlyst® 15 (Rohm & Haas, Philadelphia, Pa.,USA); or an inorganic acid, such as sulfuric acid/silizium dioxide, or silicates such as zeolithes, e.g., Zeocat®, and Wessalith® types (Degussa), montmorillonites, e.g. Montmorillonit K 10 and KSF (Fluka, Buchs, Switzerland) and mesoporous (pore size 2-50 nm) metal-doped silica gels (Degussa).
- microporous (pore size ⁇ 2 nm) zeolithes such as Wessalith®Day P and and Zeocat® types such as Zeocat Z6-05-02.
- R 1 , R 2 and R 3 are each methyl.
- any compound of the general formula I wherein R 1 , R 2 and R 3 are, independently, lower alkyl can be prepared by the process of this invention.
- the term lower alkyl as used herein denotes straight or branched chain alkyl groups having up to 7 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, sek.butyl, tert.butyl, n-pentyl and isomers thereof.
- the process of the presence invention is carried out by exposing the compound of formula II to elevated temperature, the compound of formula II is heated, in the presence of a solid acid, to a temperature of about 40° C. to about 100° C., preferably of about 60° C. to about 100° C.
- the present invention relates to the preparation of a compound of formula I wherein a compound of the general formula I is excposed to microwave irradiation.
- the process according to the present invention is carried out in dry state, i.e., in the absence of solvents.
- the starting compound of formula II Prior to exposure to elevated temperature or irradiation, the starting compound of formula II is suitably thoroughly mixed with the catalyst, e.g., by suspending the catalyst in a solution of the compound of formula II, e.g., in dichloromethane or an ether such as methyl-tert.butyl ether, with stirring and subsequent removal of the solvent or, if the catalyst is a porous material, simply adding the compound of formula II to the catalyst.
- the catalyst is suitably used in an amount of about 0.5 to about 10, preferably about 1 to about 2 parts of weight per part of weight of compound of formula II.
- reaction time yield ETTP amount DLL conversion catalyst [sec] [%] [%] [%] [%] a) Deloxan ® ASP 10 84.0 14.9 85.1 b) Amberlys ® 15 10 80.0 19.5 80.5 c) Fulmont ® XMP3 36 63.1 36.1 63.9 d) Montmorillonit K10 15 76.4 20.9 79.1 e) Montmorillonit KSF 20 62.3 37.1 62.9 f) Nafion ® NR 50 63 32.6 67.4 32.6 g) H2SO4/SiO2 4 96.6 3.4 96.6 h) Wessalith ® Day P 4 99.1 0.0 100 i) mesoporeous silica gel 60 8.0 85.0 15.0 j) mesoporeous silica gelH+ ⁇ form 0 43.0 55.0 45.0
- DDL D,L-3,7-dimethyl-6-octen-1-in-3-ol
- MTBE methyl tert.butyl ether
- experiments using Wessalith® Day P were carried out without solvent
- the solid was stirred for 60 min at room temperature, 40° C., 60° C., 80° C., and 100° C.
- the organic material was desorbed with 250 ml MTBE, and the organic layer was concentrated in vacuum (40° C., 50 mbar).
Abstract
Substituted pyranes such as 2-ethinyl-tetrahydro-2,6,6-trimethylpyran are prepared from dehydrolinalool or higher homologues thereof by heating or treatment with microwaves in the presence of a solid acid.
Description
- The present invention relates to a novel process for the preparation of substituted pyranes of the general formula I
- wherein R 1, R2 and R3 are lower alkyl.
- The compounds of formula I belong to a known class of compounds. For instance, the compound of formula I wherein each of R 1, R2 and R3 is methyl, 2-ethinyl-tetrahydro-2,6,6-trimethylpyran, is a known intermediate, e.g., in the manufacture of flavours and has been prepared so far from dehydrolinalool by ring closure catalyzed by tungsten, molybdenum or polyphosphoric acid (Strickler et al., Helv. Chem. Acta 1966, 49, 2055; Erman et al., Tetrahedron 1976, 34, 2981 and Belgian Patent No. 852 918).
- In accordance with the present invention it has been found that the compounds of formula I can be conveniently prepared by exposing a compound of the general formula II
- wherein R 1, R2 and R3 are as above,
- in the presence of a solid acid to elevated temperature or irradiation with microwaves.
- The process of the present invention proceeds in high yields and in short reaction time. Further, the process of the present invention has the advantage that the use of a solvent and unwanted pressure increase in closed reaction vessels is avoided.
- The term “microwave” as used herein refers to the region of the electromagnetic spectrum having frequencies of 30 GHz to 300 MHz thus corresponding to wavelengths of 1 cm to 1 m. In order not to interfere with wavelengths for Radar (1 cm-25 cm), household or industrial microwave heaters are required to operate at either 12.2 cm (2.45 GHz) or 33.3 cm (918 MHz). Thus, in a preferred embodiment of the invention, the term microwaves refers particularly to such wavelenghts. In the process of this invention, conventional microwave equipment can be used. Microwave equipment suitable in the process of this invention is supplied, e.g., by the firms MLS, Leutkirch, Germany (Lavis Multiquant 1000); or MILESTONE Inc., Monroe, Conn. 06468, USA (Ethos reactors). Conveniently, the irradiation in the process of this invention is carried out applying a power of irradiation of from about 600 W to 1200 W, more preferably from about 800 W to about 1000 W.
- As used herein, “solid acid” means an ordered solid having defined acidic centers selected from Lewis and Bronstedt centers. Such centers may be engineered to control which reaction product is favored in a particular reaction. Thus, solid acids, which may be used as catalysts in the present invention not only accelerate the rate of the reaction, but in reaction systems where multiple products may be formed, they may strongly influence which of the products is produced in the greatest amount. The solid acid used as a catalyst in the present invention is suitably a strong organic acid, such as a polymeric sulfonic acid, e.g., a polyperfluoroalkylene sulfonic acid, particularly Deloxan® ASP (Degussa, Frankfurt/M., Germany) or Nafion® NR 50 (DuPont, Wilmington, Del.,USA), or an anionic ion exchange resin such as Amberlyst® 15 (Rohm & Haas, Philadelphia, Pa.,USA); or an inorganic acid, such as sulfuric acid/silizium dioxide, or silicates such as zeolithes, e.g., Zeocat®, and Wessalith® types (Degussa), montmorillonites, e.g. Montmorillonit K 10 and KSF (Fluka, Buchs, Switzerland) and mesoporous (pore size 2-50 nm) metal-doped silica gels (Degussa).
- Particularly preferred are microporous (pore size<2 nm) zeolithes such as Wessalith®Day P and and Zeocat® types such as Zeocat Z6-05-02.
- In a preferred aspect, R 1, R2 and R3 are each methyl. However, any compound of the general formula I wherein R1, R2 and R3 are, independently, lower alkyl, can be prepared by the process of this invention. The term lower alkyl as used herein denotes straight or branched chain alkyl groups having up to 7 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, sek.butyl, tert.butyl, n-pentyl and isomers thereof.
- If the process of the presence invention is carried out by exposing the compound of formula II to elevated temperature, the compound of formula II is heated, in the presence of a solid acid, to a temperature of about 40° C. to about 100° C., preferably of about 60° C. to about 100° C. However, in a preferred aspect, the present invention relates to the preparation of a compound of formula I wherein a compound of the general formula I is excposed to microwave irradiation.
- The process according to the present invention is carried out in dry state, i.e., in the absence of solvents. Prior to exposure to elevated temperature or irradiation, the starting compound of formula II is suitably thoroughly mixed with the catalyst, e.g., by suspending the catalyst in a solution of the compound of formula II, e.g., in dichloromethane or an ether such as methyl-tert.butyl ether, with stirring and subsequent removal of the solvent or, if the catalyst is a porous material, simply adding the compound of formula II to the catalyst. The catalyst is suitably used in an amount of about 0.5 to about 10, preferably about 1 to about 2 parts of weight per part of weight of compound of formula II.
- The following Examples illustrate the invention further. The reactions were carried out under Ar atmosphere. The microwave equipment used was Lavis Multiquant 1000 (MLS). ETTP means 2-ethynyl-tetrahydro-2,6,6-trimethylpyran; DLL means D,L-3,7-dimethyl-6-octen-1-in-3-ol (dehydrolinalool).
- A solution of 13.82 g (0.09 mol) of dehydrolinalool (II, R 1, R2 and R3=methyl) in 200 ml of methyl tert.butyl ether was added to 28.35 g of Zeocat® Z6-05-02 and stirred for 30 min. The reaction mixture was evaporated (40° C., 300 mbar) and the resulting solid was subjected to microwave irradiation (600 W power for 4 s). The product was separated from the solid by dissolving in 300 ml acetone and evaporating the solvent in vacuo. The crude 2-ethinyl-tetrahydro-2,6,6-trimethylpyran was obtained in 13.30 g (96.2%) yield as yellowish liquid.
- In analogy to the procedure of Example 1 but substituting other solid acid catalysts for Zeocat® Z6-05-02 the following results were obtained:
reaction time yield ETTP amount DLL conversion catalyst [sec] [%] [%] [%] a) Deloxan ® ASP 10 84.0 14.9 85.1 b) Amberlys ® 15 10 80.0 19.5 80.5 c) Fulmont ® XMP3 36 63.1 36.1 63.9 d) Montmorillonit K10 15 76.4 20.9 79.1 e) Montmorillonit KSF 20 62.3 37.1 62.9 f) Nafion ® NR 50 63 32.6 67.4 32.6 g) H2SO4/SiO2 4 96.6 3.4 96.6 h) Wessalith ® Day P 4 99.1 0.0 100 i) mesoporeous silica gel 60 8.0 85.0 15.0 j) mesoporeous silica gelH+−form 0 43.0 55.0 45.0 - The procedure of Examples 1 and 2 was repeated re-using the catalysts recovered from the first run in two further runs. The results were as shown below:
Catalyst run 1 run 2 run 3 run 1 run 2 run 2 Deloxan ® ASP 84.1 83.9 82.9 85.1 84.2 94.3 Wessalith ® DayP 99.1 97.8 97.5 99.1 97.9 96.3 Zeocat ® Z6-05-02 96.2 98.3 96.9 96.4 98.5 99.0 - D,L-3,7-dimethyl-6-octen-1-in-3-ol (DDL) (0.92 g, 6 mmol) was adsorbed on the solid acid (2 g). After evaporation of the solvent (experiments using mesoporeous silica gel were carried out with a solution of DDL in methyl tert.butyl ether (MTBE); experiments using Wessalith® Day P were carried out without solvent), the solid was stirred for 60 min at room temperature, 40° C., 60° C., 80° C., and 100° C. After cooling to room temperature, the organic material was desorbed with 250 ml MTBE, and the organic layer was concentrated in vacuum (40° C., 50 mbar). The crude product was analyzed by GC. The results are summarized below:
reaction temperature Catalyst [° C.] yield ETTP [%] Wessalith room temperature 8 Wessalith 40 29 Wessalith 60 77 Wessalith 80 71 Wessalith 100 69 mesoporeous silica gel−H+ room temperature 10 mesoporeous silica gel−H+ 40 26 mesoporeous silica gel−H+ 60 89 mesoporeous silica gel−H+ 80 96 mesoporeous silica gel−H+ 100 92 - 500 ml (456.6 g, 2.87 mol) of DLL and 16 g of Amberlyst 15 were heated to 70° C. After 7 h reaction time the conversion was 92% (control by gaschromatography). The mixture was destillated at 99.4° C./147 mbar. There were thus obtained 370 g of ETTP (purity 97.32%), corresponding to a yield of 82.4%.
- The invention being thus described, it will be obvious that the same may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention and all such modifications are intended to be included within the scope of the following claims.
Claims (8)
1. Process for the preparation of compounds of the general formula I
wherein R1, R2 and R3 are lower alkyl,
which comprises exposing a compound of the general formula II
wherein R1, R2 and R3 are as above,
in the presence of a solid acid to elevated temperature or irradiation with microwaves.
2. A process as in claim 1 , wherein a compound of formula II is irradiated with microwaves in the presence of a solid acid.
3. A process as in claim 1 or 2, wherein the solid acid is a zeolithe.
4. A process as in claim 3 , wherein the zeolithe is Wessalith® Day P or Zeocat® Z6-05-02.
5. A process as in any one of claims 1 to 4 , wherein the amount of solid acid used is about 0.5 to about 10, preferably about 1 to about 2 parts of weight per part of weight of compound of formula II.
6. A process as in any one of claims 1 to 5 wherein a microwave source of about 800 to about 1000 W is used.
7. A process as in any one of claims 1 to 6 , wherein in the compound of formula II R1, R2 and R3 are methyl.
8. The invention as particularly described hereinbefore, especially with reference to the Examples.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP00119257 | 2000-09-06 | ||
| EP00119257.4 | 2000-09-06 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| US20020103388A1 true US20020103388A1 (en) | 2002-08-01 |
| US6455707B1 US6455707B1 (en) | 2002-09-24 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US09/943,669 Expired - Fee Related US6455707B1 (en) | 2000-09-06 | 2001-08-31 | Process for the preparation of substitued pyranes |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US6455707B1 (en) |
| JP (1) | JP2002145874A (en) |
| KR (1) | KR100802869B1 (en) |
| CN (1) | CN100418961C (en) |
| AT (1) | ATE261436T1 (en) |
| BR (1) | BR0103900A (en) |
| CA (1) | CA2356582A1 (en) |
| DE (1) | DE60102272T2 (en) |
| TW (1) | TW555756B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090248205A1 (en) * | 2008-03-26 | 2009-10-01 | Ok Sun Yu | Controlling method for driving a drawer of a refrigerator |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100599382B1 (en) | 2004-10-11 | 2006-07-12 | 한국에너지기술연구원 | Micro channel heater for even heating |
| WO2014083121A1 (en) * | 2012-11-28 | 2014-06-05 | Dsm Ip Assets B. V. | Synthesis of tetrahydromyrcenol |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1058547B (en) | 1976-03-26 | 1982-05-10 | Snam Progetti | Dehydro-linalol cyclisation using polyphosphoric acid - prods. being useful as perfume (intermediates) |
| DE3732950A1 (en) | 1987-09-30 | 1989-04-20 | Basf Ag | METHOD FOR PRODUCING TETRAHYDROFURANES FROM 1,4-BUTANDIOLES |
| EP0949254B1 (en) | 1998-03-31 | 2003-09-03 | Dairen Chemical Corporation | Process for producing cyclic ethers by liquid phase reaction |
-
2001
- 2001-08-30 DE DE60102272T patent/DE60102272T2/en not_active Expired - Fee Related
- 2001-08-30 AT AT01120831T patent/ATE261436T1/en not_active IP Right Cessation
- 2001-08-31 US US09/943,669 patent/US6455707B1/en not_active Expired - Fee Related
- 2001-08-31 TW TW090121604A patent/TW555756B/en not_active IP Right Cessation
- 2001-09-04 CA CA002356582A patent/CA2356582A1/en not_active Abandoned
- 2001-09-04 KR KR1020010054140A patent/KR100802869B1/en not_active IP Right Cessation
- 2001-09-05 BR BR0103900-8A patent/BR0103900A/en not_active Application Discontinuation
- 2001-09-06 JP JP2001269760A patent/JP2002145874A/en not_active Withdrawn
- 2001-09-06 CN CNB011252944A patent/CN100418961C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090248205A1 (en) * | 2008-03-26 | 2009-10-01 | Ok Sun Yu | Controlling method for driving a drawer of a refrigerator |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1347879A (en) | 2002-05-08 |
| ATE261436T1 (en) | 2004-03-15 |
| KR20020020193A (en) | 2002-03-14 |
| CA2356582A1 (en) | 2002-03-06 |
| CN100418961C (en) | 2008-09-17 |
| DE60102272D1 (en) | 2004-04-15 |
| DE60102272T2 (en) | 2005-02-24 |
| TW555756B (en) | 2003-10-01 |
| KR100802869B1 (en) | 2008-02-13 |
| US6455707B1 (en) | 2002-09-24 |
| BR0103900A (en) | 2002-05-21 |
| JP2002145874A (en) | 2002-05-22 |
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