CN100358857C - 2-cyclohexenones and process for preparing same - Google Patents
2-cyclohexenones and process for preparing same Download PDFInfo
- Publication number
- CN100358857C CN100358857C CNB2006100503167A CN200610050316A CN100358857C CN 100358857 C CN100358857 C CN 100358857C CN B2006100503167 A CNB2006100503167 A CN B2006100503167A CN 200610050316 A CN200610050316 A CN 200610050316A CN 100358857 C CN100358857 C CN 100358857C
- Authority
- CN
- China
- Prior art keywords
- preparation
- acid
- compounds
- methyl
- cyclonene
- 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.)
- Expired - Fee Related
Links
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohex-2-enone Chemical class O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 title claims description 20
- 238000004519 manufacturing process Methods 0.000 title description 2
- 238000002360 preparation method Methods 0.000 claims abstract description 47
- -1 2-cyclohexene ketone compound Chemical class 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 5
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 5
- 230000036571 hydration Effects 0.000 claims abstract description 5
- 238000006703 hydration reaction Methods 0.000 claims abstract description 5
- 125000000524 functional group Chemical group 0.000 claims abstract description 4
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical group [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 3
- RSPZSDWVQWRAEF-UHFFFAOYSA-N hepta-1,6-diyne Chemical class C#CCCCC#C RSPZSDWVQWRAEF-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims abstract description 3
- 239000002184 metal Substances 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 15
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 13
- 150000002500 ions Chemical class 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000010931 gold Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000003377 acid catalyst Substances 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 3
- 150000001555 benzenes Chemical class 0.000 claims description 3
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- 239000003446 ligand Substances 0.000 claims description 2
- 150000001457 metallic cations Chemical class 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- AVFBYUADVDVJQL-UHFFFAOYSA-N phosphoric acid;trioxotungsten;hydrate Chemical compound O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O AVFBYUADVDVJQL-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 10
- 238000004440 column chromatography Methods 0.000 abstract description 3
- 238000004821 distillation Methods 0.000 abstract description 3
- 238000007670 refining Methods 0.000 abstract description 3
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 abstract description 2
- 238000001953 recrystallisation Methods 0.000 abstract description 2
- 238000000638 solvent extraction Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 229910052723 transition metal Inorganic materials 0.000 abstract description 2
- 150000003624 transition metals Chemical class 0.000 abstract description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 34
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 24
- 150000002148 esters Chemical group 0.000 description 21
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 11
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- ANYMQYWBWSHVDG-UHFFFAOYSA-N carbanide;gold(1+) Chemical compound [CH3-].[Au+] ANYMQYWBWSHVDG-UHFFFAOYSA-N 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- YORCIIVHUBAYBQ-UHFFFAOYSA-N propargyl bromide Chemical compound BrCC#C YORCIIVHUBAYBQ-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JXPHYRUGMBAGFY-UHFFFAOYSA-N 2,2-bis(prop-2-ynyl)propanedioic acid Chemical compound C#CCC(C(=O)O)(CC#C)C(O)=O JXPHYRUGMBAGFY-UHFFFAOYSA-N 0.000 description 1
- OZLFQDAFPVAJSY-UHFFFAOYSA-N C(=O)OCC.C(C#C)C(C)CC#C Chemical compound C(=O)OCC.C(C#C)C(C)CC#C OZLFQDAFPVAJSY-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910003803 Gold(III) chloride Inorganic materials 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 238000007239 Wittig reaction Methods 0.000 description 1
- VDFHYFWUXJGDSX-UHFFFAOYSA-N [N+](=O)([O-])[Au] Chemical compound [N+](=O)([O-])[Au] VDFHYFWUXJGDSX-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000005575 aldol reaction Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000002508 compound effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- HJSLFCCWAKVHIW-UHFFFAOYSA-N cyclohexane-1,3-dione Chemical class O=C1CCCC(=O)C1 HJSLFCCWAKVHIW-UHFFFAOYSA-N 0.000 description 1
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- RGILGBAQZZXTFS-UHFFFAOYSA-N ethyl 2-prop-2-ynylpent-4-ynoate Chemical compound CCOC(=O)C(CC#C)CC#C RGILGBAQZZXTFS-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002343 gold Chemical class 0.000 description 1
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical compound Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 description 1
- 229940076131 gold trichloride Drugs 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000010422 internal standard material Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- SUSQOBVLVYHIEX-UHFFFAOYSA-N phenylacetonitrile Chemical compound N#CCC1=CC=CC=C1 SUSQOBVLVYHIEX-UHFFFAOYSA-N 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a 2-cyclohexene ketone compound which has a structure general formula in the right, wherein R<1>, R<2>, R<3>, R<4>, R<5>, R<6>, R<7> and R<8> can be identical and can also be different, and the types of the R<1>, the R<2>, the R<3>, the R<4>, the R<5>, the R<6>, the R<7> and the R<8> are functional groups of hydrocarbyl, carbonyl, phosphoryl, cyano, etc. In the preparation method of the present invention, 1, 6-heptadiyne compounds and water are used for carrying out hydration cyclization reactions under the catalyst of transition metal of gold complexes for preparing the 2-cyclohexene ketone compound. The refining process of the synthesis reaction of the present invention can be completed in usual separating refining methods such as solvent extraction, recrystallization, distillation, column chromatography, etc. The method of the present invention can be carried out in the hydration and intramolecular cyclization reactions of various 1, 6-bis-alkyne compounds under the catalysis of used specific metal complexes and various kinds of protonic acid for obtaining various 2-cyclohexene ketone compounds; the method of the present invention for preparing 2-cyclohexene ketone compounds has the advantages of simple, convenient and reliable operation and industrialized implementation.
Description
Technical field
The invention belongs to new compound and manufacture method thereof, relate generally to 2-cyclohexenone compounds and preparation method thereof.
Background technology
Cyclohexenone compounds is a class important chemical material, is widely used in synthesizing of medicine, agricultural chemicals, light reaching the film material and other important chemicals or medicine.There is the synthesis method of multiple 2-cyclohexenone compounds to be in the news at present, mainly concentrate on from tetrahydrobenzene through oxidizing reaction (referring to reference 1,2), 1, the hydroresorcinol compounds sets out through oxidative dehydrogenation (referring to reference 3), the intramolecularly aldol reaction of diketone is (referring to reference 4,6,7), ketone compounds and 3,5, pass through Micheal addition cyclization (referring to reference 5 between the 5-three replacement 2-cyclohexenone compounds, 7), generate unsaturated aldehydes or ketones from aldehyde compound through Wittig reaction, again with the cyclization under alkaline condition of the matrix with α-active hydrogen atom (referring to reference 8) etc.Yet because its functional derivatives specificity structurally makes its synthetic being very limited, for example the synthetic of the 4-substitutive derivative of 2-cyclohexenone analog need import substituting group in advance before cyclization, at least to just can finish through 4～5 step chemical reactions, and as synthetic will be restricted of this compounds under alkaline condition when having carbonyl, cyano group or other functional groups in the raw molecule of setting out.
Summary of the invention
An object of the present invention is to provide the 2-cyclohexenone compounds, have following general structure:
Wherein: R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8Can be identical, also can be different, its kind can be functional groups such as alkyl, carbonyl, phosphoryl, cyano group.
Another object of the present invention provides the preparation method of 2-cyclohexenone compounds, realize by following steps: with 1,6-heptadiyne compounds and water carries out the hydration cyclization and prepare the 2-cyclohexenone compounds under the catalysis of transition metal gold complex, for the treating process of this building-up reactions, can utilize common separation and purification methods such as solvent extraction, recrystallization, distillation and column chromatography to finish.
Concrete preparation method is:
In reactor, drop into accurate load weighted Au catalyst, 1,6-two acetylene compounds, water, solvent, add acid catalyst at last, mixture heating up is flung to solvent after refluxing, residue is dissolved in ethyl acetate, with saturated sodium bicarbonate liquid washing secondary, organic layer is flung to solvent after with dried over mgso, promptly gets pure product after the crude product upper prop is refining.
Reaction formula is:
(1) employed two acetylene compound (R wherein
1Or R
2For not participating in the substituting group of this reaction) can utilize commercially available product or make with utilizing conventional organic synthesis cheap and simple, can import two substituent R on its 4
3, R
4, they can be identical, also can be different; R
3, R
4Be respectively alkyl, alkoxyl group, amide group, carbonyl, ester group, phosphoryl, cyano group etc.;
(2) the molar ratio scope of employed 1 in the method, 6-heptadiyne compounds and water was good with 1: 10 o'clock in 1: 1～1: 100;
(3) amount ranges of reacting middle catalyst is 0.1～20mol%, with 0.1～5mol% is best, M is Jinyang ion among the MXnL, X is the negatively charged ion of selecting in the middle of halide anion, nitro negatively charged ion, alkyl negatively charged ion, trifyl negatively charged ion, n is the valence mumber of metal M, and L is and metallic cation coordinate ligand;
(4) about temperature of reaction, cross that low temperature makes that this reaction can not be carried out with favourable speed of response, too high temperature can cause the problem that side reaction also can bring economy simultaneously, temperature of reaction of the present invention generally speaking is chosen between 0～100 ℃, preferred 50～100 ℃;
(5) acid catalyst (HY) can be selecting in the middle of assorted tungstophosphoric acid, assorted tungstosilicic acid, assorted molybdophosphate, sulfuric acid, Phenylsulfonic acid, methylsulfonic acid, trifluoromethanesulfonic acid etc. in the reaction, and is wherein best with the trifluoromethanesulfonic acid effect;
(6) chemical reaction of the present invention carries out in organic solvent, but also can be not with an organic solvent.Organic solvent selects for use substituted benzene (as toluene, chlorobenzene etc.), alcohol compound to be enumerated, and wherein pure based compound effect is best, specifically by illustrative methyl alcohol, ethanol, Virahol, propyl carbinol etc. is arranged.
Method of the present invention is reasonable in design, can use under the specific metal complex and all kinds of protonic acid katalysis, hydration and intramolecular cyclization various 1, the two alkine compounds of 6-can be easy to carry out, and obtain all kinds of 2-cyclohexenone compounds with good yield.Prepare the 2-cyclohexenone compounds with the inventive method, easy and simple to handle, reliable, but industrializing implementation.
Embodiment
The present invention is further described by embodiment.
Embodiment 1:3-methyl-5, the preparation of 5-dimethyl ester group-2-cyclonene
With 2, and 2-dipropargyl dimethyl malonate (104.1mg, 0.5mmol), methyl gold complex (MeAuPPh
35mg, 0.01mmol), trifluoromethanesulfonic acid (100 μ L, 0.5mmol), water (100 μ L, 5.0mmol) and octane (50 μ L, the internal standard material that GC analyzes) mixing in methyl alcohol (2.0mL), this mixed solution was reacted in heating below 50 ℃ in 1 hour, reaction finishes the back according to gas chromatographic analysis, and target compound is identified with 94% yield.Then, reaction mixture is through column chromatography (silicagel column; Developping agent: sherwood oil: ethyl acetate=5: 1; R
f=0.3) separation and purification obtains target compound 95mg (yield 84%), and carries out boiling point, NMR, IR, and mass analysis and ultimate analysis, its result is as follows: Bp:120 ℃ (5mm Hg);
1H NMR (499.10MHz, CDCl
3): δ 2.01 (s, 3H), 2.87 (s, 2H), 2.90 (s, 2H), 3.75 (s, 6H), 5.88 (br, 1H);
13C NMR (125.4MHz, CDCl
3): δ 24.32,36.27, and 41.70,53.26,55.45,126.17,158.69,170.19,194.55; IR (neat) 2957.3,1735.6,1675.8,1436.7,1380.8,1300.8,1249.7,1075.1,1054.9; GC-MS:M
+226. ultimate analysis calculated value C
13H
18O
5: C, 58.40; H, 6.24. measured value: C, 58.43; H, 6.25.
Embodiment 2:3-methyl-5, the preparation of 5-diformazan ester group-2-cyclonene
Operation just replaces trifluoromethanesulfonic acid with assorted phospho-wolframic acid with reference to embodiment 1, obtains target compound 55mg (yield 48%).
Embodiment 3:3-methyl-5, the preparation of 5-diformazan ester group-2-cyclonene
Operation just replaces trifluoromethanesulfonic acid with assorted phospho-molybdic acid referring to embodiment 1, obtains target compound 42mg (yield 37%).
Embodiment 4:3-methyl-5, the preparation of 5-two-methoxycarbonyl-2-cyclonene
Operation just replaces trifluoromethanesulfonic acid with assorted silicotungstic acid referring to embodiment 1, obtains target compound 33mg (yield 29%).
Embodiment 5:3-methyl-5, the preparation of 5-diformazan ester group-2-cyclonene
Operation just replaces trifluoromethanesulfonic acid with sulfuric acid referring to embodiment 1, obtains target compound 44mg (yield 39%).
Embodiment 6:3-methyl-5, the preparation of 5-diformazan ester group-2-cyclonene
Operation just replaces trifluoromethanesulfonic acid with methylsulfonic acid referring to embodiment 1, obtains target compound 98mg (yield 86%).
Embodiment 7:3-methyl-5, the preparation of 5-diformazan ester group-2-cyclonene
Operation just replaces trifluoromethanesulfonic acid with Phenylsulfonic acid referring to embodiment 1, obtains target compound 100mg (yield 88%).
Embodiment 8:3-methyl-5, the preparation of 5-diformazan ester group-2-cyclonene
Operation is referring to embodiment 1, and just the trifluoromethanesulfonic acid input amount is 200 μ L (1.0mmol), obtains target compound 35mg (yield 31%).
Embodiment 9:3-methyl-5, the preparation of 5-two-methoxycarbonyl-2-cyclonene
Operation is referring to embodiment 1, and just the trifluoromethanesulfonic acid input amount is 50 μ L (0.25mmol), obtains target compound 66mg (yield 58%).
Embodiment 10:3-methyl-5, the preparation of 5-diformazan ester group-2-cyclonene
Operation is referring to embodiment 1, and just replacing methyl alcohol with toluene is solvent, obtains target compound 70mg (yield 61%).
Embodiment 11:3-methyl-5, the preparation of 5-diformazan ester group-2-cyclonene
Operation is referring to embodiment 1, and just replacing methyl alcohol with chlorobenzene is solvent, obtains target compound 22mg (yield 19%).
Embodiment 12:3-methyl-5, the preparation of 5-diformazan ester group-2-cyclonene
Operation is referring to embodiment 1, and just replacing methyl alcohol with ethanol is solvent, obtains target compound 89mg (yield 78%).
Embodiment 13:3-methyl-5, the preparation of 5-di-isopropyl ester group-2-cyclonene
Operation is referring to embodiment 1, and just replacing methyl alcohol with Virahol is solvent, obtains target compound 118mg (yield 84%).
Embodiment 14:3-methyl-5, the preparation of 5-diformazan ester group-2-cyclonene
Operation is referring to embodiment 1, and just replacing methyl alcohol with propyl carbinol is solvent, obtains target compound 46mg (yield 40%)
Embodiment 15:3-methyl-5, the preparation of 5-diformazan ester group-2-cyclonene
Operation just adds entry 300 μ L referring to embodiment 1, obtains target compound 28mg (yield 25%).
Embodiment 16:3-methyl-5, the preparation of 5-diformazan ester group-2-cyclonene
Operation just adds entry 50 μ L referring to embodiment 1, obtains target compound 25mg (yield 22%).
Embodiment 17:3-methyl-5, the preparation of 5-diformazan ester group-2-cyclonene
Operation is referring to embodiment 1, just with nitro gold complex (O
2NAuPPh
3, 5.0mg) replace the methyl gold complex, obtain target compound 99mg (yield 87%).
Embodiment 18:3-methyl-5, the preparation of 5-diformazan ester group-2-cyclonene
Operation is referring to embodiment 1, just with gold trichloride complex compound (ClAuPPh
3, 4.5mg) replace the methyl gold complex, obtain target compound 59mg (yield 52%).
Embodiment 19:3-methyl-5, the preparation of 5-diformazan ester group-2-cyclonene
Operation is referring to embodiment 1, just with gold perchloride (Cl
3Au 10.0mg) replaces the methyl gold complex, obtains target compound 37mg (yield 32%).
Embodiment 20:3-methyl-5, the preparation of 5-diformazan ester group-2-cyclonene
Operation is referring to embodiment 1, just with the sulfonated gold complex (CF of trifluoro
3SO
3AuPPh
3, 5.0mg) replace the methyl gold complex, obtain target compound 105mg (yield 92%).
Embodiment 21:3-methyl-5, the preparation of 5-diethyl-ester group-2-cyclonene
Operation is referring to embodiment 1, and with 2,2-dipropargyl diethyl malonate replaces 2, and 2-dipropargyl dimethyl malonate gets target compound 115mg (yield 91%); Boiling point, NMR, IR, mass analysis and results of elemental analyses are as follows: Bp:130 ℃/4mmHg;
1H NMR (500MHz, CDCl
3): δ 1.24 (t, J=7.0Hz, 6H), 2.01 (d, J=1.2Hz, 3H), 2.86 (s, 2H), 2.89 (s, 2H), 4.20 (q, J=7.0Hz, 4H), 5.88 (q, J=1.2Hz, 1H);
13C NMR (125.4MHz, CDCl
3): δ 13.95,24.34, and 36.19,41.74,55.50,62.15,126.17,158.70,169.76,194.79; IR (neat) 2983.8,1733.2,1678.3,1300.8,1244.3,1188.4,1073.2,1053.4,855.8; GCMS:M
+254.C
13H
18O
5: C, 61.40; H, 7.14. measured value: C, 61.32; H, 7.30.
Embodiment 22:3-methyl-5, the preparation of 5-diisopropanol ester group-2-cyclonene
Operation is referring to embodiment 1, and with 2,2-dipropargyl propanedioic acid diisopropyl alcohol ester replaces 2, and 2-dipropargyl dimethyl malonate gets target compound 123mg (yield 87.4%).Fusing point, NMR, IR, mass analysis and results of elemental analyses are as follows: mp:50.4-52.4 ℃;
1H NMR (400 MHz, CDCl
3): δ 5.87 (s, 1H), 5.03 (m, 2H), 2.85 (m, 4H), 1.99 (s, 3H), 1.22 (m, 12H);
13CNMR (100Hz, CDCl
3): δ 194.7,169.0,158.5,125.9,77.2,76.9,76.6,69.5,55.3,41.5,35.9,24.1,21.3,21.2.IR (CHCl
3, cm
-1): 2982,2937,1730,1678,1636,1377,1297,1245,1193,1147,1105,1072,1047; GCMS:M
+263; Ultimate analysis calculated value C
15H
20O
4: C 68.16, and H 7.63. measured value: C 68.20, and H 7.43.
Embodiment 23:3-methyl-5, the preparation of 5-dimethoxy-methyl-2-cyclonene
Operation is with 4 referring to embodiment 1,4-dimethoxy-methyl-1, and the 6-heptadiyne replaces 2, and 2-dipropargyl dimethyl malonate obtains target compound 73mg (yield 74%). boiling point, NMR, IR, mass analysis and results of elemental analyses are as follows:
1H NMR (400Hz, CDCl
3): δ 1.94 (s, 3H), 2.32 (s, 2H), 2.34 (s, 2H), 3.23 (s, 4H), 3.30 (s, 6H), 5.86 (s, 1H);
13C NMR (100Hz, CDCl
3): δ 198.9,159.8, and 125.4,77.2,76.9,76.6,75.4,59.2,53.3,41.6,41.3,34.8,24.3; IR (CHCl
3, cm
-1): 2925,1669,1438,1379,1248,1105; GC-MS:M
+179; Ultimate analysis calculated value C
11H
16O
2: C 73.3, and H 8.95; Measured value: C 73.41, H 8.85.
Embodiment 24:3-methyl-5, the preparation of 5-benzyloxy methyl-2-cyclonene
Operation is with 4 referring to embodiment 1,4-benzyloxy methyl isophthalic acid, and the 6-heptadiyne replaces 2, and 2-dipropargyl dimethyl malonate obtains target compound (yield 91%).Boiling point, NMR, IR, mass analysis and results of elemental analyses are as follows:
1H NMR (400 MHz, CDCl
3): δ 1.87 (s, 3H), 2.35 (s, 2H), 2.41 (s, 2H), 3.35 (s, 4H), 4.44 (m, 4H), 5.82 (s, 1H), 7.21-7.32 (m, 10H);
13C NMR (100Hz, CDCl
3): δ 198.6,159.7,138.0,128.1,127.3,127.1,125.3,77.3,76.9,76.6,73.0,72.6,41.7,41.4,34.8,24.2.IR (CHCl
3, cm
-1): 3030,2858,1666,1496,1453,1363,1249,1206,1093,1027,905; GCMS:M
+179. ultimate analysis calculated value C
11H
16O
2: C 73.3, and H 8.95. measured value: C 73.41, and H 8.85.
Embodiment 25:4-diphenylphosphine acyl group-4-ethoxycarbonyl-1, the preparation of 6-heptadiyne
(288mg, in tetrahydrofuran (THF) 12mmol) (20mL) suspension liquid, (1.153g, tetrahydrofuran (THF) 4mmol) (40mL) solution dropwises, and stirs 1h slowly to add 2-diphenylphosphine acyl acetic acid ethyl ester to sodium hydride under 0 ℃.Propargyl bromide (0.78mL, tetrahydrofuran (THF) 8.8mmol) (5mL) solution being added drop-wise in the said mixture slowly, spend the night by stirring at normal temperature.Add saturated ammonium chloride solution and handle, ether (50mL * 3) extraction, the extraction liquid anhydrous sodium sulfate drying gets target compound, mp:135 ℃ after concentrating.
Implement the preparation of 26:3-methyl 4-diphenylphosphine acyl group-4-ethoxycarbonyl-2-cyclonene
Operation is with 4 referring to embodiment 1,4-benzyloxy methyl isophthalic acid, and the 6-heptadiyne replaces 2, and 2-dipropargyl dimethyl malonate obtains target compound 174mg (yield 91%).Fusing point, NMR, IR, mass analysis and results of elemental analyses are as follows: mp:124-125.5 ℃;
1H NMR (400Hz, CDCl
3): δ 0.90 (m, 3H), 1.94 (s, 3H), 2.99 (m, 4H), 3.88 (m, 2H), 5.85 (s, 1H), 7.52 (m, 6H), 7.88 (dd, 2H, J=1.2Hz), 8.05 (dd, 2H, J=1.2Hz);
13C NMR (100Hz, CDCl
3): δ 194.3,170.8, and 159.2,132.2,132.1,131.9,131.8,131.6,131.5,129.0,128.9,128.3,128.2,128.0,127.9,125.6,61.7,59.9,53.3,52.7,39.1,33.9,24.1,20.6,13.8,13.0; IR (CHCl
3, cm
-1): 2982,1717,1672,1632,1438,1377,1290,1252,1191,1113,1065,1013.
Embodiment 27:4, the preparation of 4-dipropargyl propanedioic acid
(1g adds entry (6mL), 4 in methyl alcohol 18mmol) (20mL) solution, and 4-dipropargyl diethyl malonate (1g, 4.8mmol), spend the night by backflow to potassium hydroxide.The gained suspension liquid transfers to pH 2-3 with 6N hydrochloric acid, tells organic layer, and anhydrous sodium sulfate drying gets target compound 85mg (yield 94%) after concentrating.mp：91℃。
Embodiment 28:3-methyl-5, the preparation of 5-diformazan ester group-2-cyclonene
Operation is referring to embodiment 1, and just with 2,2-dipropargyl propanedioic acid replaces 2, and 2-dipropargyl dimethyl malonate obtains 3-methyl-5,5-diformazan ester group-2-cyclonene 46mg (yield 40%).
Embodiment 29:4-itrile group-4-phenyl-1, the preparation of 6-heptadiyne
At 0 ℃, to sodium hydride (1.23g, 25.6mmol) tetrahydrofuran (THF) (20mL) suspension liquid in, slowly add benzyl cyanide (1g, 8.5mmol) tetrahydrofuran (THF) (20mL) solution, dropwise, stir 1h. propargyl bromide (1.9mL, 21.4mmol) tetrahydrofuran (THF) (5mL) solution being added drop-wise in the said mixture slowly, stirring at normal temperature is spent the night.Saturated ammonium chloride solution is handled, ether (50mL * 3) extraction, and the extraction liquid anhydrous sodium sulfate drying gets target compound after concentrating.mp：94-95℃；
1H?NMR(400Hz，CDCl
3)：δ7.53-7.51(m，2H)，7.45-7.36(m，3H)，3.06(dd，J＝2.4Hz，2H)，2.98(dd，J＝2.4Hz，2H)，2.17(t，J＝2.4Hz，2H)。
The preparation of embodiment 30:3-methyl-5-itrile group-5-phenyl-2-cyclonene
Operation is referring to embodiment 1, and just with 4-itrile group-4-phenyl-1, the 6-heptadiyne replaces 2, and 2-dipropargyl dimethyl malonate obtains 5-itrile group-5-phenyl-3-methyl-2-cyclonene 13mg (yield 12%):
1H NMR (400Hz, CDCl
3): δ 7.49-7.39 (m, 5H), 6.12 (s, 1H), 3.01-2.90 (m, 4H), 2.07 (s, 3H) .IR (CHCl3, cm
-1): 3022.1,2402.4,1678.0,1525.9,1429.4,1382.9.
The preparation of embodiment 31:3-methyl-2-cyclonene
Operation is referring to embodiment 1, and just with 1, the 6-heptadiyne replaces 2, and 2-dipropargyl dimethyl malonate obtains 3-methyl-2-cyclonene 47mg, yield 85%.
Embodiment 32 4-ethoxycarbonyies-1, the preparation of 6-heptadiyne
2, and 2-dipropargyl diethyl malonate (20.0g, 84.7mmol), H
2O (1.41mL; 84.7mmol) and lithium chloride (7.04g; the reflux under nitrogen protection of DMSO solution 169mmol); clear soln is overstrike gradually, after 5 hours, and the solution cooling; add 400mL water; water 200mL * 2 n-hexane extractions, the normal hexane layer anhydrous magnesium sulfate drying of merging, distillation obtains target compound 67mg (yield 82%).
1H?NMR(400Hz，CDCl
3)δ4.23-4.17(q，J7.2Hz，3H)，2.78-2.73(m，1H)，2.69-2.57(m，4H)，2.02-2.01(t，J?2.8Hz，2H)。
The preparation of embodiment 33:3-methyl-5-ethoxycarbonyl-2-cyclonene
Operation just replaces 2 with 2-propargyl-4-pentyne-1-ethyl formate referring to embodiment 1, and 2-dipropargyl dimethyl malonate obtains 5-ethoxycarbonyl-3-methyl-2-cyclonene 82mg (yield 90%).
1HNMR(400Hz，CDCl
3)：δ5.91(s，1H)，3.72(s，3H)，3.10-3.04(m，1H)，2.67-2.51(m，4H)，2.00(s，3H)。
The preparation of embodiment 34:3-methyl-5-phenyl-5-methoxycarbonyl-2-cyclonene
Operation is referring to embodiment 1, and just with 4-methoxycarbonyl-4-phenyl-1, the 6-heptadiyne replaces 2, and 2-dipropargyl dimethyl malonate obtains 5-phenyl-5-methoxycarbonyl-3-methyl-2-cyclonene 93mg (yield 76%).mp：83-84℃；
1H?NMR(400Hz，CDCl
3)：δ7.37-7.29(m，5H)，5.93(d，1H)，3.63(s，3H)，3.25(dq，2H)，2.76(dq，2H)，2.05(s，3H)；
13CNMR(100Hz，CDCl
3)：δ196.6，174.0，160.4，140.0，128.8，127.7，126.5，125.5，52.8，51.8，45.1，40.1，24.5；IR(KBr，cm
-1)：2977，1725.4，1665.9，1286.8，1072.3，920.7。
The preparation of embodiment 35:3-methyl-5-phenyl-5-ethoxycarbonyl-2-cyclonene
Operation just replaces 2 with 2-propargyl-4-pentynoic acid ethyl ester referring to embodiment 1, and 2-dipropargyl dimethyl malonate obtains 5-ethoxycarbonyl-3-methyl-2-cyclonene 82mg (yield 90%).mp：83-84℃。
Embodiment 36:3,4,6-trimethylammonium-5, the preparation of 5-diformazan ester group-2-cyclonene
Operation is with 3 referring to embodiment 1,5-dimethyl-4, and 4-diformazan ester group-1, the 6-heptadiyne replaces 2, and 2-dipropargyl dimethyl malonate obtains target compound 3,4,6-trimethylammonium-5,5-diformazan ester group-2-cyclonene 92mg (yield 65%).mp：128-129℃。
Need not further to elaborate, believe and adopt the disclosed content in front, those skilled in the art can use the present invention to greatest extent.Therefore, the preferred specific embodiments of front is interpreted as only illustrating, but not limits the scope of the invention by any way.
The reference that the present invention relates to:
1：J.Heterocycl.Chem.9，741(1972)
2：J.Org.Chem.42，p1349(1977)
3：J.Am.Chem.Soc.98，p4887(1976)
4：Bull.Chem.Soc.Jap.79，p1879(1997)
5：J.Org.Chem.62，p9323(1997)
6：US?5,554,582；1996
7：US?5,523,462；1996
8：US?5,201,935；1993
Claims (6)
1. the preparation method of a 2-cyclohexenone compounds, the 2-cyclohexenone compounds has following general structure:
Wherein: R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8Identical or different; its kind is any functional group in alkyl, carbonyl, phosphoryl, the cyano group; it is characterized in that realizing by following steps: with 1,6-heptadiyne compounds, water and acid catalyst carry out the hydration cyclization and prepare the 2-cyclohexenone compounds under the catalysis of MXnL gold complex:
Wherein MXnL gold complex catalyst consumption scope is 0.1～20mol%; M is Jinyang ion among the MXnL; X is the negatively charged ion of selecting in the middle of halide anion, nitro negatively charged ion, alkyl negatively charged ion, trifyl negatively charged ion; n is the valence mumber of metal M, and L is and metallic cation coordinate ligand.
2. the preparation method of 2-cyclohexenone compounds according to claim 1 is characterized in that: drop into load weighted Au catalyst, 1 in reactor, 6-heptadiyne compounds, water, solvent add acid catalyst at last, wherein:
(1) the molar ratio scope of employed two acetylene compounds and water is 1: 1-1: 100;
(2) temperature of reaction is selected 50～100 ℃;
(3) acid catalyst is selected in assorted tungstophosphoric acid, assorted tungstosilicic acid, assorted molybdophosphate, sulfuric acid, Phenylsulfonic acid, methylsulfonic acid, the trifluoromethanesulfonic acid any for use in the reaction;
(4) solvent is an organic solvent.
3. the preparation method of 2-cyclohexenone compounds according to claim 2, it is characterized in that: organic solvent is substituted benzene or alcohol compound, described substituted benzene is selected toluene or chlorobenzene for use, and described alcohol compound is selected in methyl alcohol, ethanol, Virahol, the propyl carbinol any for use.
4. the preparation method of 2-cyclohexenone compounds according to claim 2 is characterized in that: employed 1, the molar ratio of 6-heptadiyne compounds and water is 1: 10.
5. the preparation method of 2-cyclohexenone compounds according to claim 2 is characterized in that: the gold complex catalyst consumption is 0.1～5mol% in the reaction.
6. the preparation method of 2-cyclohexenone compounds according to claim 2 is characterized in that: acid catalyst is selected trifluoromethanesulfonic acid for use in the reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100503167A CN100358857C (en) | 2006-04-12 | 2006-04-12 | 2-cyclohexenones and process for preparing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100503167A CN100358857C (en) | 2006-04-12 | 2006-04-12 | 2-cyclohexenones and process for preparing same |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200710127790XA Division CN101104587B (en) | 2006-04-12 | 2006-04-12 | 2-cyclohexenone compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1827577A CN1827577A (en) | 2006-09-06 |
| CN100358857C true CN100358857C (en) | 2008-01-02 |
Family
ID=36946159
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100503167A Expired - Fee Related CN100358857C (en) | 2006-04-12 | 2006-04-12 | 2-cyclohexenones and process for preparing same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100358857C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101412667B (en) * | 2008-11-06 | 2012-06-27 | 浙江工业大学 | Preparation of 2-pimelie kelone compound |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1075954A (en) * | 1992-03-05 | 1993-09-08 | 北美埃尔夫爱托化学股份有限公司 | 3-cyano group-3,5,5-trialkyl cyclohexanone catalyst and preparation method thereof |
| US5523462A (en) * | 1991-10-25 | 1996-06-04 | Basf Aktiengesellschaft | Cyclohexenone derivatives |
| CN1235954A (en) * | 1998-05-13 | 1999-11-24 | 德古萨－于尔斯股份公司 | Improved process for preparation of 3,5,5-trimethylcyclohexa-3-en-1-one |
| CN1342135A (en) * | 1999-03-30 | 2002-03-27 | 快思特国际公司 | Preparation of carvone |
| CN1639099A (en) * | 2002-03-06 | 2005-07-13 | 独立行政法人产业技术综合研究所 | Process for producing carbonyl compound |
| CN1683297A (en) * | 2005-03-07 | 2005-10-19 | 中国科学院广州化学研究所 | Synthetic method for 4-(1,5-dimethyl-1-vinyl-4-hexenyl) phenol |
-
2006
- 2006-04-12 CN CNB2006100503167A patent/CN100358857C/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5523462A (en) * | 1991-10-25 | 1996-06-04 | Basf Aktiengesellschaft | Cyclohexenone derivatives |
| CN1075954A (en) * | 1992-03-05 | 1993-09-08 | 北美埃尔夫爱托化学股份有限公司 | 3-cyano group-3,5,5-trialkyl cyclohexanone catalyst and preparation method thereof |
| CN1235954A (en) * | 1998-05-13 | 1999-11-24 | 德古萨－于尔斯股份公司 | Improved process for preparation of 3,5,5-trimethylcyclohexa-3-en-1-one |
| CN1342135A (en) * | 1999-03-30 | 2002-03-27 | 快思特国际公司 | Preparation of carvone |
| CN1639099A (en) * | 2002-03-06 | 2005-07-13 | 独立行政法人产业技术综合研究所 | Process for producing carbonyl compound |
| CN1683297A (en) * | 2005-03-07 | 2005-10-19 | 中国科学院广州化学研究所 | Synthetic method for 4-(1,5-dimethyl-1-vinyl-4-hexenyl) phenol |
Non-Patent Citations (3)
| Title |
|---|
| 2,5,6-三苯基-2-环己烯酮催化脱氢制2,3,6--三苯基苯酚. 高燕等.石油化工，第27卷. 1998 * |
| 3-甲基-4-乙氧甲酰-2-环己烯酮合成方法的改进. 胡炳成等.应用化学，第20卷第10期. 2003 * |
| 液晶中间体4-烷基环己酮的新合成方法研究. 张智勇等.化学试剂，第19卷第3期. 1997 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1827577A (en) | 2006-09-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Bergbreiter et al. | Michael additions of nitroalkanes to. alpha.,. beta.-unsaturated carbonyl compounds using potassium fluoride/basic alumina | |
| Colvin et al. | Improved nitroaldol reactions and reductive routes to vicinal aminoalcohols | |
| Panev et al. | Chiral aminoalcohols with a menthane skeleton as catalysts for the enantioselective addition of diethylzinc to benzaldehyde | |
| Padwa et al. | An Unusual example of a 6-endo-dig addition to an unactivated carbon-carbon triple bond | |
| US6946556B1 (en) | Preparation of opioid analgesics by a one-pot process | |
| CN113735701A (en) | Preparation method of 8-hydroxy-2,2,14, 14-tetramethylpentadecanedioic acid | |
| CN100358857C (en) | 2-cyclohexenones and process for preparing same | |
| Senda et al. | Asymmetric Synthesis of (R, Z)-(—)-5-(l-Decenyl) oxacyclo-pentan-2-one, the Pheromone of the Japanese Beetle | |
| Kawabata et al. | Preparation of organocalcium halides in hydrocarbon solvents | |
| US4018838A (en) | Process of preparing alkenes | |
| CN106083724A (en) | A kind of preparation method of dexmedetomidine | |
| CN101104587B (en) | 2-cyclohexenone compounds | |
| Morizawa et al. | Pd (O) Promoted Transformation of 1, 1‐Dialkoxycarbonyl‐2‐(1, 3‐butadienyl) cyclopropanes into 2‐Ethenyl‐3‐cyclopentenes | |
| CN100448841C (en) | Process for preparing 2-cyclohexenone compounds | |
| JPH0673042A (en) | Production 0f gamma-butyrolactone | |
| JP2620437B2 (en) | Process for producing ω-hydroxy- (ω-3) -ketonitrile and ω-hydroxy fatty acid | |
| US3173939A (en) | Process for the preparation of cyanomethyleneglutaric and cyanomethylglutaric compounds | |
| MILLER et al. | STUDIES IN THE THIOPHENE SERIES. VII. 1 THE APPLICATION OF THE REFORMATSKY REACTION TO THIOPHENE ALDEHYDES AND KETONES | |
| CN100430346C (en) | Selective alkylation reaction of acid anhydride or ester | |
| SU1759825A1 (en) | Method of producing a mixture of 2-methyl- and 4-methylpenta-1,3-dienes | |
| US2772295A (en) | Process of manufacturing esters of 3-substituted 2-furoic acids | |
| Caccia et al. | Synthesis of (+)-(S)-4-s. Butyl and (+)-(S)-2-Methyl-4-s. Butylpyridine | |
| Blair et al. | A new positive halogen reagent. Oxidation of secondary alcohols to ketones by bis (quinuclidine) bromine (I) bromide in the presence of pyridinium catalyst | |
| JPH06503328A (en) | Preparation method of α-alkyl lactone | |
| CN109422604A (en) | A method of synthesis phenanthrene and its derivative |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080102 Termination date: 20140412 |