CN103980095A - Preparation method of template agent intermediate 4,5-dimethyl bicyclo[2.2.2] octane-2-alcohol - Google Patents
Preparation method of template agent intermediate 4,5-dimethyl bicyclo[2.2.2] octane-2-alcohol Download PDFInfo
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- CN103980095A CN103980095A CN201410238652.9A CN201410238652A CN103980095A CN 103980095 A CN103980095 A CN 103980095A CN 201410238652 A CN201410238652 A CN 201410238652A CN 103980095 A CN103980095 A CN 103980095A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims abstract description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 12
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 12
- 229910000077 silane Inorganic materials 0.000 claims abstract description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000005051 trimethylchlorosilane Substances 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 2
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 claims description 2
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 claims description 2
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical group [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 claims description 2
- OVEHNNQXLPJPPL-UHFFFAOYSA-N lithium;n-propan-2-ylpropan-2-amine Chemical compound [Li].CC(C)NC(C)C OVEHNNQXLPJPPL-UHFFFAOYSA-N 0.000 claims description 2
- RPNNPZHFJPXFQS-UHFFFAOYSA-N methane;rhodium Chemical compound C.[Rh] RPNNPZHFJPXFQS-UHFFFAOYSA-N 0.000 claims description 2
- NCPHGZWGGANCAY-UHFFFAOYSA-N methane;ruthenium Chemical compound C.[Ru] NCPHGZWGGANCAY-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000004440 column chromatography Methods 0.000 abstract description 3
- -1 oxyl Chemical group 0.000 abstract description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract 2
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000012280 lithium aluminium hydride Substances 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 239000002808 molecular sieve Substances 0.000 description 10
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 10
- 229910021536 Zeolite Inorganic materials 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000010457 zeolite Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 4
- 238000005698 Diels-Alder reaction Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000006837 decompression Effects 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000009415 formwork Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 229910010082 LiAlH Inorganic materials 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910002796 Si–Al Inorganic materials 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- ANUZKYYBDVLEEI-UHFFFAOYSA-N butane;hexane;lithium Chemical compound [Li]CCCC.CCCCCC ANUZKYYBDVLEEI-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000006200 ethylation reaction Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- MACWUZNMKDMGGJ-UHFFFAOYSA-N lithium;oxolane;n-propan-2-ylpropan-2-amine Chemical compound [Li].C1CCOC1.CC(C)NC(C)C MACWUZNMKDMGGJ-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006462 rearrangement reaction Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
- C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
- C07C2602/44—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing eight carbon atoms
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of 4,5-dimethyl bicyclo[2.2.2] octane-2-alcohol. The preparation method of the 4,5-dimethyl bicyclo[2.2.2] octane-2-alcohol comprises the following steps: 1) carrying out reaction on 3-methyl-2-cyclohexene-1-ketone and a lithium reagent, then carrying out reaction with trimethylchlorosilane, so that trimethyl (5-methyl cyclohexene-1-5-dialkylene oxyl) silane is generated; 2) carrying out Diers-Alder reaction on trimethyl (5-methyl cyclohexene-1-5-dialkylene oxyl) silane and acrylonitrile, and hydrolyzing for generating 1-methyl-5-ketone bicycle[2.2.2]octane-2-cyanogen; 3) carrying out reaction on 1-methyl-5-ketone bicycle[2.2.2]octane-2-cyanogen and hydrogen under the catalytic action of palladium on carbon, so that the 4,5-dimethyl bicyclo[2.2.2] octane-2-alcohol is obtained. The preparation method of the 4,5-dimethyl bicyclo[2.2.2] octane-2-alcohol has the advantages that a three-step reaction process is adopted, the total yield of each reaction step is more than 85%, purity is respectively more than 88%, purity of a product of a middle step can be 97.3, and steps are simple; meanwhile, lithium aluminium hydride is not used in the reaction process, and aftertreatment is simple, so that the preparation method of the 4,5-dimethyl bicyclo[2.2.2] octane-2-alcohol is more applicable to industrial production; purification through column chromatography does not need to be carried out, time and labour are saved, purity is high, and cost is saved.
Description
Technical field
The present invention relates to a kind of template intermediate 4, the preparation method of 5-dimethyl dicyclo [2.2.2] octane-2-alcohol, belongs to molecular sieve field.
Background technology
Zeolite molecular sieve material, especially Si-Al zeolite molecular screen material, the well-regulated micropore canals of tool, large specific surface area, higher thermostability and hydrothermal stability, be to be applied at present petrochemical industry heterogeneous catalyst material the most widely.In modern zeolite molecular sieve is synthetic, the use of organic formwork agent plays very important effect, the exploration of the exploitation of new topological framework zeolite molecular sieve and new synthetic route is all closely related with new type formwork molecule, and template molecule plays a part structure directing in zeolite molecular sieve synthetic conventionally, fill and balance skeleton electric charge in duct.
In recent years, the SSZ-13 zeolite molecular sieve with high silica alumina ratio and octatomic ring pore passage structure has higher catalytic activity and selectivity in MTO reaction, thereby extensively concerned, high silica alumina ratio has given product higher thermostability and hydrothermal stability, and the pore passage structure of octatomic ring makes it have good shape selectivity in MTO reaction, and the SSZ-13 zeolite of Cu exchange, take in the reaction of the elimination nitrogen oxides pollution that NH3 is reductive agent, demonstrates than the more excellent catalytic activity of other molecular sieve and selectivity.But the restriction due to the less pore size of SSZ-13 zeolite molecular sieve and exchange capacity, limited the raising of its catalytic activity, the novel molecular sieve SSZ-52 of Gregory seminar research and development has well made up this shortcoming, SSZ-52 compares with SSZ-13, its aperture is larger, adsorptive power is stronger, higher to oxynitrides conversion capability.The synthetic template of using that needs of SSZ-52 molecular sieve is: 2-azonia dicyclo [3.2.2] nonane, and 2,2-diethyl-5,6-dimethyl-, hydroxide radical, molecular formula is C14H29NO, has following structural formula:
4, 5-dimethyl dicyclo [2.2.2] octane-2-alcohol is preparation template 2-azonia dicyclo [3.2.2] nonane, 2, 2-diethyl-5, 6-dimethyl-, important intermediate hydroxy, this intermediate is through peroxidation, become oxime and rearrangement reaction, the To Template agent that ethylation reaction and ion-exchange can be made, at present, the synthetic domestic and international relevant report of this template is less, only have one piece of patent WO0109037A1 to report its building-up process, it is starting raw material that this patent be take 3-methyl-2-tetrahydrobenzene-1-ketone, through Michael, close ring, tetrahydrochysene lithium aluminium reducing, Tosyl chloride esterification, a step tetrahydrochysene lithium aluminium reducing prepares 4 again, 5-dimethyl dicyclo [2.2.2] octane-2-alcohol.In this route, used dangerous inflammable substance tetrahydrochysene lithium aluminium (LiAlH
4) as reductive agent, greatly reduce the security of whole piece synthetic route, be unsuitable for Workshop Production and amplify; And when Tosyl chloride esterification, need purify by column chromatography, both waste man-hour, reduce again yield, make product cost higher.
Summary of the invention
Technical problem to be solved by this invention is to carry a kind of template intermediate 4 that supplies, the preparation method of 5-dimethyl dicyclo [2.2.2] octane-2-alcohol, and its step reduces, and yield is high and be beneficial to suitability for industrialized production, has overcome above-mentioned defect of the prior art.
8. the technical scheme that the present invention solves the problems of the technologies described above is as follows: a kind of template intermediate 4, and the preparation method of 5-dimethyl dicyclo [2.2.2] octane-2-alcohol, described 4, the structural formula of 5-dimethyl dicyclo [2.2.2] octane-2-alcohol is
It is characterized in that, comprise the following steps:
1) 3-methyl-2-tetrahydrobenzene-1-ketone is reacted with lithium reagent, and then react generation trimethylammonium (5-tetrahydrotoluene-1-5-dialkylene oxygen base) silane with trimethylchlorosilane; Wherein,
The structural formula of described 3-methyl-2-tetrahydrobenzene-1-ketone is as follows:
The structural formula of described trimethylammonium (5-tetrahydrotoluene-1-5-dialkylene oxygen base) silane is as follows:
The mol ratio of described lithium reagent and described 3-methyl-2-tetrahydrobenzene-1-ketone is 1～2:1, and the mol ratio of described trimethylchlorosilane and described 3-methyl-2-tetrahydrobenzene-1-ketone is 2～4:1;
2) by step 1) in trimethylammonium (5-tetrahydrotoluene-1-5-dialkylene oxygen base) silane and the vinyl cyanide that generate join in organic solvent, heat through diels-alder reaction, then the reaction that is hydrolyzed generates described 1-methyl-5-ketone dicyclo [2.2.2] octane-2-cyanogen; Described diels-alder reaction (English: Diels – Alder reaction) cry again Diels-Alder reaction, Diene-addition reaction;
Wherein,
The structural formula of described 1-methyl-5-ketone dicyclo [2.2.2] octane-2-cyanogen is as follows:
The mol ratio of described vinyl cyanide and described trimethylammonium (5-tetrahydrotoluene-1-5-dialkylene oxygen base) silane is 1～5:1;
3) by step 2) in 1-methyl-5-ketone dicyclo [2.2.2] octane-2-cyanogen of generating under catalyst with hydrogen reaction, generate 4,5-dimethyl dicyclo [2.2.2] octane-2-alcohol.
The invention has the beneficial effects as follows: the present invention adopts the total recovery of three-step reaction process and each reactions steps to be greater than 85%, purity all reaches more than 88%, the purity of intermediate steps product can be up to 97.3, and step is simple, does not use tetrahydrochysene lithium aluminium in reaction process, aftertreatment is simple, more be applicable to suitability for industrialized production, without purifying by column chromatography, time saving and energy saving, purity is high, cost-saving.
On the basis of technique scheme, the present invention can also do following improvement.
Further, in step 1) described lithium reagent is lithium methide, n-Butyl Lithium, s-butyl lithium, tert-butyl lithium, lithium diisopropylamine, any one in Tetramethyl Ethylene Diamine base lithium.
Further, in step 1) described in 3-methyl-2-tetrahydrobenzene-1-ketone processing condition of reacting with lithium reagent be: at the temperature of 50 ℃～-100 ℃, drip lithium reagent.
Further, in step 2) described in heating processing condition be: at the temperature of 50 ℃～150 ℃, heat 5～15 hours.More preferably at the temperature of 100～110 ℃, heat 10～12 hours.
Further, in step 2) described in organic solvent comprise any one or the two or more mixing in methyl alcohol, ethanol, Virahol, acetonitrile, acetone, tetrahydrofuran (THF), dioxane, toluene, dimethylbenzene.
Further, in step 3) in, described in carry out hydrogenation processing condition be: at the temperature of 20 ℃～100 ℃, under 0.1MPa～5MPa pressure, heat 2～20 hours.More preferably, at the temperature of 60 ℃, under 1MPa～1.5MPa pressure, heat 12 hours.
Further, in step 3) in, described catalyzer comprises nickel, palladium carbon, platinum carbon, ruthenium carbon, rhodium carbon wherein any one.
Embodiment
Below in conjunction with embodiment, principle of the present invention and feature are described, example, only for explaining the present invention, is not intended to limit scope of the present invention.
Embodiment 1
A kind of template intermediate 4 of the present invention, the preparation method of 5-dimethyl dicyclo [2.2.2] octane-2-alcohol, comprises the following steps:
Step 1, the preparation of Compound I trimethylammonium (5-tetrahydrotoluene-1-5-dialkylene oxygen base) silane:
3-methyl-2-tetrahydrobenzene-1-ketone (110.00g, 1.00mol) is dissolved in to 550mL tetrahydrofuran (THF), is cooled to-70～-80 ℃, drip 2.2mol/L n-Butyl Lithium hexane solution (545.50mL, 1.20mol), dropwise and continue insulation 2 hours.Drip trimethylchlorosilane (141.20g, 1.30mol), dropwise and continue insulation 2 hours.In reaction solution, add water and each 300mL of toluene, stir 20 minutes, separatory, toluene for water (300mL * 2) extraction, merges organic phase, uses successively 400mL water, the saturated NaCl solution washing of 400mL, and washing is finished, and adds 150g anhydrous Na
2sO
4dry, decompression desolventizing, obtains weak yellow liquid 163.8g.Yield is 90.3%, purity 97.3% (GC).
Step 2, the preparation of Compound I I1-methyl-5-ketone dicyclo [2.2.2] octane-2-cyanogen:
The Compound I (91.00g, 0.50mol) of step 1 preparation is dissolved in 360mL toluene, adds vinyl cyanide (53.00g, 1.00mol), be warming up to system temperature at 100～110 ℃, stirring reaction 12h at this temperature.Add 200mL10% dilute hydrochloric acid, stir 0.5h, separatory, by toluene (200mL * 1) aqueous phase extracted.Merge organic phase, successively with 300mL tap water and the washing of 300mL saturated sodium-chloride water solution.Washing is finished, and adds 50g anhydrous sodium sulfate drying 1h, and decompression desolventizing, obtains weak yellow liquid 73.40g, yield 90.0%, purity 90.2% (GC).
Compound III (preparation of 4,5-dimethyl dicyclo [2.2.2] octane-2-alcohol:
By the Compound I I (81.60g of step 2 preparation, 0.50mol), 4.08g5% palladium carbon and 408.00g methyl alcohol drop in autoclave, and hydrogen exchange leads to hydrogen for three times afterwards to 1MPa, is warming up to 60 ℃, heated and stirred 12h, be cooled to 20 ℃, take out filtration catalizer, remove solvent under reduced pressure and obtain weak yellow liquid 69.40g, yield 90.0%, purity 91.20% (GC).
1H-NMR(CDCl
3)：δ3.60(1H,m),2.00(1H,m)，1.59(1H,t)，1.57(1H,m)，1.49(1H,m)，1.46(1H,m)，1.35(1H,d)，1.32(1H,d)，1.25(1H,t)，1.24(1H,t)，1.16(3H,s)，1.07(1H,t)，1.06(3H,d)，1.04(1H,m)。
Embodiment 2
A kind of template intermediate 4 of the present invention, the preparation method of 5-dimethyl dicyclo [2.2.2] octane-2-alcohol, comprises the following steps:
Step 1, the preparation of Compound I trimethylammonium (5-tetrahydrotoluene-1-5-dialkylene oxygen base) silane:
By 3-methyl-2-tetrahydrobenzene-1-ketone (110.00g, 1.00mol) be dissolved in 550mL tetrahydrofuran (THF), be cooled to-60～-70 ℃, drip 2.0mol/L lithium diisopropylamine tetrahydrofuran solution (600.00mL, 1.20mol), dropwise and continue insulation 2 hours.Drip trimethylchlorosilane (141.20g, 1.30mol), dropwise and continue insulation 2 hours.In reaction solution, add water and each 300mL of toluene, stir 20 minutes, separatory, toluene for water (300mL * 2) extraction, merges organic phase, uses successively 400mL water, the saturated NaCl solution washing of 400mL, and washing is finished, and adds 150g anhydrous Na
2sO
4dry, decompression desolventizing, obtains weak yellow liquid 163.8g.Yield is 89.2%, purity 96.0% (GC).
Step 2, the preparation of Compound I I1-methyl-5-ketone dicyclo [2.2.2] octane-2-cyanogen:
The Compound I (91.00g, 0.50mol) of step 1 preparation is dissolved in 360mL dimethylbenzene, adds vinyl cyanide (53.00g, 1.00mol), be warming up to system temperature at 120～130 ℃, stirring reaction 10h at this temperature.Add 200mL10% dilute hydrochloric acid, stir 0.5h, separatory, by toluene (200mL * 1) aqueous phase extracted.Merge organic phase, successively with 300mL tap water and the washing of 300mL saturated sodium-chloride water solution.Washing is finished, and adds 50g anhydrous sodium sulfate drying 1h, and decompression desolventizing, obtains weak yellow liquid 73.40g, yield 86.2%, purity 89.2% (GC).
Step 3, compound III (preparation of 4,5-dimethyl dicyclo [2.2.2] octane-2-alcohol:
By the Compound I I (81.60g of step 2 preparation, 0.50mol), 8.16g nickel and 408.00g methyl alcohol drop in autoclave, and hydrogen exchange leads to hydrogen for three times afterwards to 1.5MPa, be warming up to 60 ℃, heated and stirred 12h, is cooled to 20 ℃, takes out filtration catalizer, remove solvent under reduced pressure and obtain weak yellow liquid 69.40g, yield 85.5%, purity 88.10% (GC)
1h-NMR (CDCl
3): δ 3.60 (1H, m), 2.00 (1H, m), 1.59 (1H, t), 1.57 (1H, m), 1.49 (1H, m), 1.46 (1H, m), 1.35 (1H, d), 1.32 (1H, d), 1.25 (1H, t), 1.24 (1H, t), 1.16 (3H, s), 1.07 (1H, t), 1.06 (3H, d), 1.04 (1H, m).
The foregoing is only preferred embodiment of the present invention, in order to limit the present invention, within the spirit and principles in the present invention not all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (7)
1. a template intermediate 4, the preparation method of 5-dimethyl dicyclo [2.2.2] octane-2-alcohol, described 4, the structural formula of 5-dimethyl dicyclo [2.2.2] octane-2-alcohol is
It is characterized in that, comprise the following steps:
1) 3-methyl-2-tetrahydrobenzene-1-ketone is reacted with lithium reagent, and then react generation trimethylammonium (5-tetrahydrotoluene-1-5-dialkylene oxygen base) silane with trimethylchlorosilane; Wherein,
The structural formula of described 3-methyl-2-tetrahydrobenzene-1-ketone is as follows:
The structural formula of described trimethylammonium (5-tetrahydrotoluene-1-5-dialkylene oxygen base) silane is as follows:
The mol ratio of described lithium reagent and described 3-methyl-2-tetrahydrobenzene-1-ketone is 1～2:1, and the mol ratio of described trimethylchlorosilane and described 3-methyl-2-tetrahydrobenzene-1-ketone is 2～4:1;
2) by step 1) in trimethylammonium (5-tetrahydrotoluene-1-5-dialkylene oxygen base) silane and the vinyl cyanide that generate join in organic solvent, heat, then the reaction that is hydrolyzed generates described 1-methyl-5-ketone dicyclo [2.2.2] octane-2-cyanogen; Wherein,
The structural formula of described 1-methyl-5-ketone dicyclo [2.2.2] octane-2-cyanogen is as follows:
The mol ratio of described vinyl cyanide and described trimethylammonium (5-tetrahydrotoluene-1-5-dialkylene oxygen base) silane is 1～5:1;
3) by step 2) in 1-methyl-5-ketone dicyclo [2.2.2] octane-2-cyanogen of generating under catalyst with hydrogen reaction, generate 4,5-dimethyl dicyclo [2.2.2] octane-2-alcohol.
2. a kind of template intermediate 4 according to claim 1, the preparation method of 5-dimethyl dicyclo [2.2.2] octane-2-alcohol, it is characterized in that, in step 1) in, described lithium reagent is lithium methide, n-Butyl Lithium, s-butyl lithium, tert-butyl lithium, lithium diisopropylamine, any one in Tetramethyl Ethylene Diamine base lithium.
3. a kind of template intermediate 4 according to claim 1, the preparation method of 5-dimethyl dicyclo [2.2.2] octane-2-alcohol, it is characterized in that, in step 1) in, the temperature range that described 3-methyl-2-tetrahydrobenzene-1-ketone reacts with lithium reagent is 50 ℃～-100 ℃.
4. a kind of template intermediate 4 according to claim 1, the preparation method of 5-dimethyl dicyclo [2.2.2] octane-2-alcohol, it is characterized in that, in step 2) in, described organic solvent comprises any one or the two or more mixing in methyl alcohol, ethanol, Virahol, acetonitrile, acetone, tetrahydrofuran (THF), dioxane, toluene, dimethylbenzene.
5. a kind of template intermediate 4 according to claim 1, the preparation method of 5-dimethyl dicyclo [2.2.2] octane-2-alcohol, it is characterized in that, in step 2) in, the processing condition of described heating are: at the temperature of 50 ℃～150 ℃, heat 5～15 hours.
6. a kind of template intermediate 4 according to claim 1, the preparation method of 5-dimethyl dicyclo [2.2.2] octane-2-alcohol, it is characterized in that, in step 3) in, described 1-methyl-5-ketone dicyclo [2.2.2] octane-2-cyanogen with the condition of hydrogen reaction is under catalyst: at the temperature of 20 ℃～100 ℃, under 0.1MPa～5MPa pressure, heat 2～20 hours.
7. according to a kind of template intermediate 4 described in claim 1 to 6 any one, the preparation method of 5-dimethyl dicyclo [2.2.2] octane-2-alcohol, is characterized in that, in step 3) in, described catalyzer is nickel, palladium carbon, platinum carbon, ruthenium carbon, a kind of or several mixing arbitrarily in rhodium carbon.
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| S. LAHIRI ET AL.: "Face-Selective Diels-Alder Reactions between Unsymmetrical Cyclohexadienes and Symmetric trans-Dienophile: An Experimental and Computational Investigation", 《J. ORG. CHEM.》, vol. 73, 19 December 2007 (2007-12-19), pages 435 - 444 * |
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