CN103980095B - A kind of preparation method of template intermediate 4,5-dimethyl dicyclo [2.2.2] octane-2-alcohol - Google Patents

A kind of preparation method of template intermediate 4,5-dimethyl dicyclo [2.2.2] octane-2-alcohol Download PDF

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CN103980095B
CN103980095B CN201410238652.9A CN201410238652A CN103980095B CN 103980095 B CN103980095 B CN 103980095B CN 201410238652 A CN201410238652 A CN 201410238652A CN 103980095 B CN103980095 B CN 103980095B
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octane
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dicyclo
ketone
alcohol
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刘一
房立平
周银波
孙宽
吴同川
于琳
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Valiant Co Ltd
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    • 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 Table
    • 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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Abstract

The present invention relates to a kind of 4, the preparation method of 5-dimethyl dicyclo [2.2.2] octane-2-alcohol, comprise the following steps: 1) 3-methyl-2-tetrahydrobenzene-1-ketone and lithium reagent are reacted, and then react with trimethylchlorosilane and generate trimethylammonium (5-tetrahydrotoluene-1-5-dialkylene oxygen base) silane; 2) trimethylammonium (5-tetrahydrotoluene-1-5-dialkylene oxygen base) silane and vinyl cyanide are carried out diels-alder reaction, then hydrolysis generates 1-methyl-5-ketone dicyclo [2.2.2] octane-2-cyanogen; 3) 1-methyl-5-ketone dicyclo [2.2.2] octane-2-cyanogen is obtained 4,5-dimethyl dicyclo [2.2.2] octane-2-alcohol under the catalysis of palladium carbon with hydrogen reaction.The present invention adopts three-step reaction process and the total recovery of each reactions steps is greater than 85%, purity all reaches more than 88%, the purity of intermediate steps product can 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 the need to being purified by column chromatography, time saving and energy saving, purity is high, cost-saving.

Description

A kind of preparation method of template intermediate 4,5-dimethyl dicyclo [2.2.2] octane-2-alcohol
Technical field
The present invention relates to a kind of preparation method of template intermediate 4,5-dimethyl dicyclo [2.2.2] octane-2-alcohol, belong to molecular sieve art.
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 are applied to petrochemical industry heterogeneous catalyst material the most widely at present.In modern zeolite molecular sieve synthesis, the use of organic formwork agent plays very important effect, the exploitation of new topology zeolite molecular sieve and the exploration of new synthetic route all closely related with new type formwork molecule, usual template molecule play a part in the synthesis of zeolite molecular sieve structure directing, duct fill and balance skeleton electric charge.
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, thus extensively concerned, high silica alumina ratio imparts the higher thermostability of product 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 that Cu exchanges is in the reaction of elimination nitrogen oxides pollution taking NH3 as reductive agent, demonstrates the catalytic activity more more excellent than other molecular sieve and selectivity.But the pore size less due to SSZ-13 zeolite molecular sieve and the restriction of exchange capacity, limit the raising of its catalytic activity, the novel molecular sieve SSZ-52 of Gregory seminar research and development well compensate for this shortcoming, SSZ-52 and SSZ-13 compares, its aperture is larger, adsorptive power is stronger, higher to oxynitrides conversion capability.The template that the synthesis needs of SSZ-52 molecular sieve use is: 2-azonia dicyclo [3.2.2] nonane, 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 domestic and international relevant report of synthesis of this template is less, one section of patent WO0109037A1 is only had to report its building-up process, this patent with 3-methyl-2-tetrahydrobenzene-1-ketone for starting raw material, ring is closed through Michael, 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.Dangerous inflammable substance tetrahydrochysene lithium aluminium (LiAlH is employed in this route 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 be purified by column chromatography, both waste man-hour, again reduce yield, make product cost higher.
Summary of the invention
Technical problem to be solved by this invention puies forward a kind of preparation method for template intermediate 4,5-dimethyl dicyclo [2.2.2] octane-2-alcohol, and its step reduces, and yield is high and be beneficial to suitability for industrialized production, overcomes above-mentioned defect of the prior art.
8. the technical scheme that solves the problems of the technologies described above of the present invention is as follows: a kind of preparation method of template intermediate 4,5-dimethyl dicyclo [2.2.2] octane-2-alcohol, the structural formula of described 4,5-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 and lithium reagent are reacted, and then react with trimethylchlorosilane and generate trimethylammonium (5-tetrahydrotoluene-1-5-dialkylene oxygen base) silane; 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 generate trimethylammonium (5-tetrahydrotoluene-1-5-dialkylene oxygen base) silane and vinyl cyanide join in organic solvent, carry out heating through diels-alder reaction, then the reaction that is hydrolyzed generates described 1-methyl-5-ketone dicyclo [2.2.2] octane-2-cyanogen; Diels-Alder reaction, Diene-addition reaction are named again in described diels-alder reaction (English: Diels – Alderreaction);
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 that generates 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 three-step reaction process and the total recovery of each reactions steps is greater than 85%, purity all reaches more than 88%, the purity of intermediate steps product can 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 the need to being purified 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 and the lithium reagent processing condition of reacting be: at the temperature of 50 DEG C ~-100 DEG C, drip lithium reagent.
Further, in step 2) described in heating processing condition be: at the temperature of 50 DEG C ~ 150 DEG C heat 5 ~ 15 hours.Be more preferably and heat 10 ~ 12 hours at the temperature of 100 ~ 110 DEG C.
Further, in step 2) described in organic solvent comprise any one or 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 DEG C ~ 100 DEG C, 0.1MPa ~ 5MPa heating under pressure 2 ~ 20 hours.Be more preferably at the temperature of 60 DEG C, 1MPa ~ 1.5MPa heating under pressure 12 hours.
Further, in step 3) in, described catalyzer comprises nickel, palladium carbon, platinum carbon, ruthenium carbon, rhodium carbon wherein any one.
Embodiment
Be described principle of the present invention and feature below in conjunction with embodiment, example, only for explaining the present invention, is not intended to limit scope of the present invention.
Embodiment 1
The preparation method of a kind of template intermediate 4,5-of the present invention 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-70 ~-80 DEG C, drip 2.2mol/L n-Butyl Lithium hexane solution (545.50mL, 1.20mol), continuation insulation 2 hours are dropwised.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, aqueous phase toluene (300mL × 2) extraction, merge organic phase, use the saturated NaCl solution washing of 400mL water, 400mL successively, washing is finished, and adds 150g anhydrous Na 2sO 4drying, decompression desolventizing, obtains weak yellow liquid 163.8g.Yield is 90.3%, purity 97.3% (GC).
Step 2, the preparation of Compound II per 1-methyl-5-ketone dicyclo [2.2.2] octane-2-cyanogen:
The Compound I (91.00g, 0.50mol) step 1 prepared is dissolved in 360mL toluene, adds vinyl cyanide (53.00g, 1.00mol), is warming up to system temperature at 100 ~ 110 DEG C, 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:
Compound II per (81.60g prepared by step 2,0.50mol), 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 DEG C, heated and stirred 12h, be cooled to 20 DEG C, 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
The preparation method of a kind of template intermediate 4,5-of the present invention 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 DEG C, drip 2.0mol/L lithium diisopropylamine tetrahydrofuran solution (600.00mL, 1.20mol), continuation insulation 2 hours are dropwised.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, aqueous phase toluene (300mL × 2) extraction, merge organic phase, use the saturated NaCl solution washing of 400mL water, 400mL successively, washing is finished, and adds 150g anhydrous Na 2sO 4drying, decompression desolventizing, obtains weak yellow liquid 163.8g.Yield is 89.2%, purity 96.0% (GC).
Step 2, the preparation of Compound II per 1-methyl-5-ketone dicyclo [2.2.2] octane-2-cyanogen:
The Compound I (91.00g, 0.50mol) step 1 prepared is dissolved in 360mL dimethylbenzene, adds vinyl cyanide (53.00g, 1.00mol), is warming up to system temperature at 120 ~ 130 DEG C, 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:
Compound II per (81.60g prepared by step 2,0.50mol), 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 DEG C, heated and stirred 12h, is cooled to 20 DEG C, 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, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (6)

1. the preparation method of template intermediate 4,5-dimethyl dicyclo [2.2.2] octane-2-alcohol, the structural formula of described 4,5-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 and lithium reagent are reacted, and then react with trimethylchlorosilane and generate trimethylammonium (5-tetrahydrotoluene-1-5-dialkylene oxygen base) silane; 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 generate trimethylammonium (5-tetrahydrotoluene-1-5-dialkylene oxygen base) silane and vinyl cyanide join in organic solvent, heat, then the reaction that is hydrolyzed generates described 1-methyl-5-ketone dicyclo [2.2.2] octane-2-cyanogen; The processing condition of described heating are: heat 5 ~ 15 hours at the temperature of 50 DEG C ~ 150 DEG C, 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 that generates 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 and lithium reagent react is 50 DEG C ~-100 DEG C.
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 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 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 DEG C ~ 100 DEG C, 0.1MPa ~ 5MPa heating under pressure 2 ~ 20 hours.
6. the preparation method of a kind of template intermediate 4,5-dimethyl dicyclo [2.2.2] octane-2-alcohol according to any one of claim 1 to 5, is characterized in that, in step 3) in, described catalyzer is nickel, palladium carbon, platinum carbon, ruthenium carbon, a kind of or several arbitrarily mixing in rhodium carbon.
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