CN102267857A - Preparation method for nopadiene - Google Patents
Preparation method for nopadiene Download PDFInfo
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- CN102267857A CN102267857A CN2010101933309A CN201010193330A CN102267857A CN 102267857 A CN102267857 A CN 102267857A CN 2010101933309 A CN2010101933309 A CN 2010101933309A CN 201010193330 A CN201010193330 A CN 201010193330A CN 102267857 A CN102267857 A CN 102267857A
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Abstract
The invention discloses a preparation method for nopadiene. The method comprises the following steps: dissolving nopol in an inert solvent; adding a new prepared dehydrolyzing agent; carrying out stirring, refluxing and water dividing for 1-12 hours in the presence of a polymerization inhibitor under the protection of nitrogen gas; carrying out cooling to a room temperature after completing the reaction; carrying out sucking filtration to remove the dehydrolyzing agent; washing the filtrate to remove the residual dehydrolyzing agent; carrying out drying through anhydrous sodium sulfate; carrying out vacuum distillation under the protection of the nitrogen gas to remove the solvent to obtain the crude nopadiene; finally carrying out purification to obtain the nopadiene. The dehydrolyzing agent is a copper salt, or a copper salt-silica gel compound, or a silica gel-loaded copper salt. The use amount of the dehydrolyzing agent is according to a ratio of the amount of the copper in the copper salt to the nopol of 1:0.5-4. With the method provided by the present invention, reaction conditions are mild, operation is simple, the solvent and the product are easy to be separated, product yield is high, the product purity is good, the dehydrolyzing agent and the solvent can be recycled.
Description
Technical field
The present invention relates to a kind of promise and foretell the preparation method of diene, relating generally to a kind of is that raw material prepares the method that diene is foretold in promise with the nopol in the presence of dewatering agent, solvent are held concurrently the band aqua.
Background technology
Turps is the extremely abundant natural reproducible resource of China, and we occupy first place in the world at turps output.α-Pai Xi content is in the majority in the turps, and slash pine had entered the resin tapping phase in recent years, and beta-pinene content is abundant in the slash pine, raw material is provided for single production from beta-pinene, for condition has been created in the fine chemistry utilization of beta-pinene.China's beta-pinene output has occupied former positions, the world now.Beta-pinene and Paraformaldehyde 96 obtain nopol through the Prins reaction, and nopol is mainly used to blending at present, or the synthetic perfume nopyl acetate, and purposes is more single and consumption is limited.Seek the new approaches and methods that utilizes of nopol and will enlarge its market space effectively, help improving the added value of turps firpene and even nopol.Kitchen report [US, 2537638] is the nopol De Nuobu diene that dewaters, i.e. 2-vinyl-6,6-dimethyl two ring [3.1.1]-heptene.
Promise is foretold diene as a kind of natural source organic compound, not only has special aroma, also has nontoxic, normal temperature simultaneously down for liquid, easily and a series of good characteristics such as other material is miscible, so can be directly use, and normal and other terpene compound one are used from during various fine chemicals fill a prescription as the fine chemicals system component.Kemp etc. [GB, 881534] find, are that the polymer thermostable of principal monomer composition is all poor with vinylchlorid, if with promise foretell diene be the terpenoid of representative as stablizer, can strengthen the stability of polyvinyl chloride-base polymkeric substance and reduce its melting viscosity.More can utilize the special construction of its dicyclo and conjugated double bond, be used for organic synthesis, synthetic multiple chiral ligand, spices, optically active substance, biologically active substance, macromolecular material etc.Because the structural instability of diene is foretold in promise, and reactions such as isomery, polymerization very easily take place, present preparation cost is higher, and productive rate is lower.Prepare promise cheaply and foretell diene, and expand it and utilize approach, can enlarge the utility value of beta-pinene.
The direct dehydration of nopol that is obtained through the Prins reaction by beta-pinene and Paraformaldehyde 96 is that diene method is the earliest foretold in synthetic promise.Because the diene acid labile is foretold in promise, the acid catalysis isomerization reaction takes place easily, so generally should not directly use the acid-catalyzed dehydration method.[US such as Kitchen, 2537638] nopol is carried out the E1cb unimolecular elimination reaction with an alkali metal salt, redistillation is purified and is synthesized promise fore-telling diene, productive rate only about 10%, undesired polymerization has taken place in most of product, but add diethylene glycol diethyl ether make solvent after productive rate can bring up to 70%.Cupas etc. [J Org Chem, 1969,34 (3): 742-744] find, because reaction conditions is violent (highly basic, high temperature) relatively, except that diene is foretold in promise, also have 2-ethylidene-6,6-dimethyl two ring [3.1.1]-3-heptene etc. are multiple to be difficult to isolating isomer in a large number and to produce.
Nopinone Yu Geshi reagent react can make promise and foretell diene [Tetrahedron Lett, 1976,17 (45): 4033-4036].Generate 6 behind the nopinone Yu Geshi reagent react, 6-dimethyl-2-vinyl-two ring [3.1.1] hexane-2-alcohol, this compound is a kind of tertiary alcohol, can dewater to generate promise fore-telling diene under very gentle condition.But nopinone and Grignard reagent all compare expensive, and the strictness of grignard reaction operational requirement, study mainly as basic reaction.
Margot etc. [Tetrahedron, 1990,46 (7): 2411-2424] find that high allyl or high benzyl class ether can be converted into diene or cinnamic structure smoothly under reagent effects such as lithium diisopropylamine (LDA), potassium tert.-butoxide.2-(2-methoxy ethyl)-6,6-dimethyl two ring [3.1.1]-heptene (being that ether is foretold in the methyl promise) in tetrahydrofuran (THF), obtain promise and foretell diene, productive rate 72% under highly basic effects such as potassium tert.-butoxide, lithium diisopropylamine.But this method cost is higher, and operation is difficulty relatively.
[Journal of the Chemical Society (Section D): Chemical Communications such as Achmatowicz, 1971:1014-10156] find that nopol generates the thiobenzoic acid ester with the thiobenzoic acid reaction earlier, and then be dissolved in hexanaphthene and be loaded in the narrow-mouth flask, utilize the mercury lamp of medium tenacity to shine elimination reaction, conjugated double bond forms rapidly, and productive rate is very high.This reaction is applicable to that equally also other have the compound of latent conjugated structure.Though the relatively environmental protection of this method, because thiobenzoic acid cost height, practicality is relatively poor.
The tosic acid root is good leavings group, is commonly used in the organic synthesis.[J Org Chem such as Paquette, 1987,52 (21): 4732-4730] nopol and Tosyl chloride reaction are generated tosic acid promise fore-telling ester, elimination reaction generation promise takes place under the effect of potassium tert.-butoxide in dimethyl sulfoxide solution then foretell diene, productive rate about 80%.This method productive rate height, by product is less, and the chemist that mostly is afterwards adopts, but the use of reagent such as pyridine, potassium tert.-butoxide, methyl-sulphoxide has increased the operation easier and the cost of this method.
Maercker[Org.React, 1965,14:271-434] with myrthenal and triphenyl phosphorus methylene radical reaction De Nuobu diene, productive rate is near 60%.This reaction is the Witting reaction, and Tong Geshi reagent is the same, and the preparation of phosphorus ylide is same cumbersome and cost is very high, and this method only sees in the fundamental research.
Summary of the invention
The present invention is directed to promise in the past and foretell the reaction conditions that exists in the diene synthetic method and require shortcomings such as height, complicated operation, cost height, productive rate are low, proposed a kind of preparation method with reacting phase to the promises fore-telling diene of gentle, easy and simple to handle, characteristics such as cost is low, productive rate height.
Technical scheme of the present invention is: the preparation method of diene is foretold in a kind of promise, comprise the steps nopol is dissolved in the inert solvent, add freshly prepd dewatering agent, stirring and refluxing divides the water reaction 1～12h under stopper existence and nitrogen protection, the reaction postcooling is to room temperature, suction filtration is removed dewatering agent, and residual dewatering agent is removed in the filtrate water eccysis, again with anhydrous sodium sulfate drying, then, underpressure distillation removes and desolvates under nitrogen protection, obtains thick promise and foretells diene, purifies at last to obtain promise fore-telling diene;
Described dewatering agent is mantoquita or mantoquita-silica gel compound or silica gel load mantoquita, and the consumption of dewatering agent is 1: 0.5～4 with the ratio of the amount of substance of copper in the mantoquita wherein and the amount of substance of nopol.
Thick promise fore-telling diene is purified by underpressure distillation, and the cut of collecting 78 ℃/3.332kPa is promise and foretells the diene product.
Thick promise is foretold diene by the gradient column chromatographic purification, is that eluent carries out the gradient column chromatographic separation with V (sherwood oil): V (ethyl acetate)=100: 1,60: 1,20: 1 during purification, and the light yellow transparent liquid that obtains is refining promise and foretells diene.
When described dewatering agent is mantoquita-silica gel compound or mantoquita, preparation by the following method: is that 0～5: 1 ratio is evenly mixed with chromatographic grade silica gel and mantoquita according to mass ratio, be placed in the baking oven and toast 3h or, promptly get mantoquita-silica gel compound or mantoquita dewatering agent in 240 ℃ of baking 1h in 200 ℃.
When described dewatering agent is the silica gel load mantoquita, preparation by the following method: according to the mass ratio of mantoquita and chromatographic grade silica gel be 1: 0～5 and the amount of chromatographic grade silica gel be not 0 ratio, it is evenly mixed to adopt equi-volume impregnating that chromatographic grade silica gel is put into copper salt solution, mantoquita is loaded on the silica gel, underpressure distillation boils off water, the silica gel of load mantoquita is transferred in the crucible, in 240 ℃ of baking 1h or in 200 ℃ of baking 3h, get the silica gel of load mantoquita, be silica gel load mantoquita dewatering agent, cooling is placed in the moisture eliminator standby.
Described mantoquita is any one in copper sulfate, cupric chloride, the cupric nitrate.
Described inert solvent is any one in benzene, toluene, zellon, pentyl acetate, dimethylbenzene, the oil of mirbane.
Described stopper is Resorcinol, para benzoquinone or Phenyl beta naphthylamine, its usage quantity by throwing raw material nopol quality 0.2%.
The promise that the present invention relates to is foretold diene synthetic chemistry reaction formula and is expressed as follows:
Beneficial effect:
1) adopts mantoquita or mantoquita-silica gel compound or silica gel load mantoquita, especially be dewatering agent with copper sulfate or copper sulfate-silica gel compound or silica gel load copper sulfate, be that the raw material preparation promise of dewatering is foretold the reacting phase of diene to gentleness with the nopol, doing the double band of solvent aqua reflux water-dividing with inert solvents such as benzene,toluene,xylene, pentyl acetates can fully dewater, but dewatering agent is relatively inexpensive and reuse, has the meaning of green, economy, environmental protection.
2) reaction is simple, practical, is easy to realize suitability for industrialized production.
3) operation and aftertreatment are fairly simple, and the available after a little while column chromatography of sample is separated purification, and the available for a long time underpressure distillation of sample is purified and obtained the purity high product.
Description of drawings
Fig. 1 foretells the GC figure of diene product for promise.
Fig. 2 foretells the infrared spectrogram of diene for the synthetic product promise.
Fig. 3 is the infrared spectrogram of raw material nopol (content 94.6%).
Fig. 4 foretells the mass spectrum of diene for the synthetic product promise.
Embodiment
Analytical study method and condition
The product promise is foretold diene and is identified through GC-MS.
Main analysis condition is: adopt Agilent Agilent GC-MS gaseous mass spectrum combined instrument.Chromatographic column is DB-5 (30m * ID0.25mm, thickness 0.25 μ m), fid detector, 80 ℃ of heating schedules (7 ℃/min) → 190 ℃, and 190 ℃ of detected temperatures, 190 ℃ of sampler temperature, nitrogen is carrier gas, sample size 0.4 μ L.The mass spectrum condition: the ionization mode is EI, and electron energy is 70eV.
The preparation method:
The preparation method of diene is foretold in a kind of promise, comprise the steps nopol is dissolved in the inert solvent, add freshly prepd dewatering agent, stirring and refluxing divides the water reaction 1～12h under stopper existence and nitrogen protection, the reaction postcooling is to room temperature, remove dewatering agent with No. 4 sand core funnel suction filtrations, residual dewatering agent is removed in the filtrate water eccysis, again with anhydrous sodium sulfate drying, then, underpressure distillation removes and desolvates under nitrogen protection, obtains thick promise and foretells diene, purifies at last to obtain promise fore-telling diene;
Described dewatering agent is mantoquita or mantoquita-silica gel compound or silica gel load mantoquita, and the consumption of dewatering agent is 1: 0.5～4 with the ratio of the amount of substance of copper in the mantoquita wherein and the amount of substance of nopol.
The purification that diene is foretold in thick promise has dual mode to select, and a kind of is that equivalence ratio can be purified by underpressure distillation bigger the time, and the cut of collecting 78 ℃/3.332kPa is promise and foretells the diene product.Equivalence ratio hour, just can purify by the gradient column chromatographic separation, be that eluent carries out the gradient column chromatographic separation with V (sherwood oil): V (ethyl acetate)=100: 1,60: 1,20: 1 during purification, the light yellow transparent liquid that obtains is refining promise and foretells diene.
When described dewatering agent is mantoquita-silica gel compound or mantoquita, preparation by the following method: is that 0～5: 1 ratio is evenly mixed with chromatographic grade silica gel and mantoquita according to mass ratio, be placed in the baking oven and toast 3h or, promptly get mantoquita-silica gel compound or mantoquita dewatering agent in 240 ℃ of baking 1h in 200 ℃.
When described dewatering agent is the silica gel load mantoquita, preparation by the following method: according to the mass ratio of mantoquita and chromatographic grade silica gel be 1: 0～5 and the amount of chromatographic grade silica gel be not 0 ratio, it is evenly mixed to adopt equi-volume impregnating that chromatographic grade silica gel is put into copper salt solution, mantoquita is loaded on the silica gel, underpressure distillation boils off water, the silica gel of load mantoquita is transferred in the crucible, in 240 ℃ of baking 1h or in 200 ℃ of baking 3h, get the silica gel of load mantoquita, be silica gel load mantoquita dewatering agent, cooling is placed in the moisture eliminator standby.
Preparation dewatering agent used mantoquita is in the mantoquita that can make Lewis acid and use such as copper sulfate, cupric chloride, the cupric nitrate any one.
Described inert solvent is any one in benzene, toluene, zellon, pentyl acetate, dimethylbenzene, the oil of mirbane, and its usage quantity is approximately 5～12 times of nopol quality, here inert solvent be solvent also be the band aqua.
Described stopper is Resorcinol (HQ), para benzoquinone (PBQ) or Phenyl beta naphthylamine (PBN), its usage quantity by throwing raw material nopol quality 0.2%.
Fig. 1 foretells the GC figure of diene product for the product promise.
Wherein: 1#, 8.25min, the isomer of diene is foretold in promise, 2#, 8.475min, diene, 3#, 9.425min, unknown impuritie peak, 4#, 13.00min, nopol (raw material) are foretold in promise.The content 90.6% of diene is foretold in promise.
Fig. 2 foretells the infrared spectrogram of diene for the synthetic product promise.
Wherein: main absorption peak (cm
-1): 3056,2922,2867,1643,1630,1380,1366.1643cm wherein
-1And 1630cm
-1Be the stretching vibration of the C=C-C=C of conjugated double bond, symmetric 1642cm
-1(weak), asymmetric 1630cm
-1(by force), 3056 is (=C-H) stretching vibration, the 1380cm of hydrogen on the alkene unsaturated carbon
-1And 1360cm
-1Flexural vibration for gem-dimethyl.Accompanying drawing 3 is compared with accompanying drawing 4, does not interact because there is the stretching vibration of the ethylene linkage in the conjugated dienes of symmetry centre to exist, and has produced the flexible bands of a spectrum (1643cm of two C=C
-1And 1630cm
-1).Lacked 3500～3000cm
-1The strong wide absorption peak of O-H stretching vibration, illustrate that the hydroxyl in the nopol is sloughed.
Fig. 3 is the infrared spectrogram of raw material nopol (content 94.6%).
Wherein: 3500～3000cm
-1Strong wide absorption peak be the O-H stretching vibration, 1330cm
-1Be O-H in-plane bending vibration, 1048cm
-1Locating strong absorption band is the C-O stretching vibration, 1654cm
-1The place is the stretching vibration absorption peak of two keys.
Fig. 4 foretells the mass spectrum of diene for the synthetic product promise.
Wherein: m/z 148 is a molecular ion peak, and m/z 133 is the fragment ion peak behind the molion demethylating, and m/z 105 sloughs fragment ion peak behind the sec.-propyl for molion, and m/z 79 sloughs fragment ion peak behind vinyl and the sec.-propyl for molion.
Place baking oven in 200 ℃ of baking 3h or in 240 ℃ of baking 1h commercially available anhydrous cupric sulfate, take out postcooling and promptly get the mantoquita dewatering agent.Place moisture eliminator standby.
Embodiment 2 preparation mantoquita-silica gel compound dewatering agents
Is not that 0 mass ratio is mixed and stir with commercially available anhydrous cupric sulfate and chromatographic grade silica gel by m (copper sulfate): m (silica gel)=1: 0～5 and copper sulfate quality, be placed in the baking oven in 200 ℃ of baking 3h or in 240 ℃ of baking 1h, take out postcooling and promptly get mantoquita-silica gel composite dewatering agent.Place moisture eliminator standby.
Embodiment 3 preparation silica gel load mantoquita dewatering agents
The silica gel for preparing load copper sulfate according to equi-volume impregnating, the mass ratio of silica gel and copper sulfate is respectively 5,4,3,2,1 ratio, place retort furnace in 200 ℃ of baking 3h in the silica gel of the good copper sulfate of load, or 240 ℃ of baking 1h, obtain silica gel load copper sulfate dewatering agent after taking out cooling, place moisture eliminator standby.
Embodiment 4
In the there-necked flask of 150mL; add 5g (30mmol) nopol (94%wt content), 0.01g Resorcinol, solvent are held concurrently and be with aqua is dimethylbenzene 70mL; freshly prepd dewatering agent 4.8g among the embodiment 1; stir logical nitrogen protection, fully reflux water-dividing; the back flow reaction temperature is greatly about 138～140 ℃; reaction 12h postcooling is to room temperature, removes dewatering agent with No. 4 sand core funnel suction filtrations under-0.06MPa pressure, must tawny filtrate.Filtrate washing 3 times, filtrate merges after anhydrous sodium sulfate drying, and underpressure distillation removes removal xylene to get yellow liquid is that diene is foretold in thick promise under nitrogen protection.Slightly the glycol purification is foretold in promise: a kind of is the cut that 78 ℃/3.332kPa is collected in distillation, gets the yellow liquid promise and foretells diene; Or with V (sherwood oil): V (ethyl acetate)=100: 1,60: 1,20: 1 eluent is done the gradient column chromatographic separation, thin-layer chromatography follow the tracks of to detect (developping agent be V (sherwood oil): V (ethyl acetate)=20: 1), get light yellow liquid 0.7g, be promise and foretell diene product, productive rate 16.7%.
Embodiment 5
Change the dimethylbenzene among the embodiment 4 into toluene, change the dewatering agent among the embodiment 4 into embodiment 2 freshly prepd silica gel-copper sulfate composite dewatering agent 24.0g, wherein silica gel and copper sulfate mass ratio are 4: 1, other working method are with embodiment 4, get light yellow liquid product 0.5g, diene productive rate 11.9% is foretold in promise.
Embodiment 6
Change the toluene among the embodiment 5 into zellon, all the other are with embodiment 5.Get light yellow liquid product 0.4g, the productive rate that diene is foretold in promise is 9.5%.
Embodiment 7
Change the toluene among the embodiment 5 into pentyl acetate, all the other are with embodiment 5.Get light yellow liquid product 2.3g, the productive rate that diene is foretold in promise is 54.6%.
Embodiment 8
Change dewatering agent the silica gel load copper sulfate dewatering agent of embodiment 3 gained into, wherein silica gel and copper sulfate mass ratio are 4: 1, and all the other are with embodiment 5.De Nuobu diene product 3.4g, productive rate 81.3%.
Embodiment 9
Change the double band of the solvent among the embodiment 8 aqua into dimethylbenzene, all the other are with embodiment 8.De Nuobu diene product 2.34g, productive rate 55.8%.
Embodiment 10:
Change the double band of the solvent among the embodiment 8 aqua into zellon, all the other are with embodiment 8.De Nuobu diene product 2.9g, productive rate 70.2%.
Embodiment 11
With nopol 20g; toluene 240mL; Resorcinol 0.04g; (wherein anhydrous cupric sulfate is 1: 4 with the ratio of silica gel quality to the silica gel load copper sulfate 95g of gained among the embodiment 3; and through 200 ℃ of baking 3h) place the 500mL there-necked flask; under the nitrogen protection, stirring and refluxing is divided water reaction 2h, 110～112 ℃ of reflux temperatures.Reaction finishes the back sand core funnel and removes by filter dewatering agent, and filtrate is through washing after drying 3 times, and vacuum distillation recovered solvent toluene under the nitrogen protection is collected the cut 8.7g of 78 ℃/3.332kPa then, and diene productive rate 51.9% is foretold in promise.Distillation residue are chocolate, the sticky material of special odor is arranged.
Embodiment 12
Among the embodiment 4～11, reaction finishes the back and reclaims the dewatering agent that obtains with sand core funnel from reaction system, can handle obtaining the regeneration dewatering agent respectively by the method for implementing 1～3.
Embodiment 13
Change the dewatering agent among the embodiment 8 the regeneration dewatering agent 22.7g of embodiment 12 gained into, all the other are with embodiment 8.De Nuobu diene product 3.3g, productive rate is 76.0%.Illustrate that thus dewatering agent can reclaim and regeneration.
Embodiment 14
Change the dewatering agent among the embodiment 4 into freshly prepd silica gel load cupric chloride, the mass ratio of cupric chloride and silica gel be 5: 1, stopper change into para benzoquinone all the other with embodiment 4, equally can obtain promise and foretell the diene product.
Embodiment 15
Change the dewatering agent among the embodiment 4 into freshly prepd silica gel load cupric nitrate, the mass ratio of cupric nitrate and silica gel be 1: 1, stopper change into Phenyl beta naphthylamine all the other with embodiment 4, equally can obtain promise and foretell the diene product.
Claims (8)
1. the preparation method of a promise fore-telling diene is characterized in that, comprises the steps nopol is dissolved in the inert solvent, add freshly prepd dewatering agent, stirring and refluxing divides the water reaction 1～12h under stopper existence and nitrogen protection, and the reaction postcooling is to room temperature, and suction filtration is removed dewatering agent, residual dewatering agent is removed in the filtrate water eccysis, with anhydrous sodium sulfate drying, then, underpressure distillation removes and desolvates under nitrogen protection again, obtain thick promise and foretell diene, purifying at last obtains promise fore-telling diene;
Described dewatering agent is mantoquita or mantoquita-silica gel compound or silica gel load mantoquita, and the consumption of dewatering agent is 1: 0.5～4 with the ratio of the amount of substance of copper in the mantoquita wherein and the amount of substance of nopol.
2. the preparation method of diene is foretold in promise as claimed in claim 1, it is characterized in that, thick promise fore-telling diene is purified by underpressure distillation, and the cut of collecting 78 ℃/3.332kPa is promise and foretells the diene product.
3. the preparation method of diene is foretold in promise as claimed in claim 1, it is characterized in that, thick promise is foretold diene by the gradient column chromatographic purification, be that eluent carries out the gradient column chromatographic separation with V (sherwood oil): V (ethyl acetate)=100: 1,60: 1,20: 1 during purification, the light yellow transparent liquid that obtains is refining promise and foretells diene.
4. the preparation method of diene is foretold in promise as claimed in claim 1, it is characterized in that, when described dewatering agent is mantoquita-silica gel compound or mantoquita, preparation by the following method: is that 0～5: 1 ratio is evenly mixed with chromatographic grade silica gel and mantoquita according to mass ratio, be placed in the baking oven and toast 3h or, promptly get mantoquita-silica gel compound or mantoquita dewatering agent in 240 ℃ of baking 1h in 200 ℃.
5. the preparation method of diene is foretold in promise as claimed in claim 1, it is characterized in that, when described dewatering agent is the silica gel load mantoquita, preparation by the following method: the mass ratio according to mantoquita and chromatographic grade silica gel is 1: 0～5, and the amount of chromatographic grade silica gel is not 0 ratio, it is evenly mixed to adopt equi-volume impregnating that chromatographic grade silica gel is put into copper salt solution, mantoquita is loaded on the silica gel, underpressure distillation boils off water, the silica gel of load mantoquita is transferred in the crucible, in 240 ℃ of baking 1h or in 200 ℃ of baking 3h, the silica gel of load mantoquita, i.e. silica gel load mantoquita dewatering agent, cooling is placed in the moisture eliminator standby.
6. foretell the preparation method of diene as claim 1,4,5 arbitrary described promises, it is characterized in that described mantoquita is any one in copper sulfate, cupric chloride, the cupric nitrate.
7. the preparation method of diene is foretold in promise as claimed in claim 1, it is characterized in that described inert solvent is any one in benzene, toluene, zellon, pentyl acetate, dimethylbenzene, the oil of mirbane.
8. the preparation method of diene is foretold in promise as claimed in claim 1, it is characterized in that described stopper is Resorcinol, para benzoquinone or Phenyl beta naphthylamine, its usage quantity by throwing raw material nopol quality 0.2%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113880099A (en) * | 2021-10-29 | 2022-01-04 | 山东东岳有机硅材料股份有限公司 | Method for preparing sodium silicate by utilizing organic silicon three wastes in green recycling manner |
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| GB881534A (en) * | 1958-01-24 | 1961-11-08 | Du Pont | Improvements in or relating to the stabilisation of films of vinyl halide polymers |
| CN1171980A (en) * | 1996-07-25 | 1998-02-04 | 中国科学院大连化学物理研究所 | One step method for synthesis of catalyst for 2, 5 -dimethyl-2, 4 -hexadiene reaction and its application |
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2010
- 2010-06-03 CN CN2010101933309A patent/CN102267857A/en active Pending
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| US2537638A (en) * | 1949-03-17 | 1951-01-09 | Firestone Tire & Rubber Co | 6, 6-dimethyl-2-vinyl-bicyclo-(3.1.1)-2-heptene and its production |
| GB881534A (en) * | 1958-01-24 | 1961-11-08 | Du Pont | Improvements in or relating to the stabilisation of films of vinyl halide polymers |
| CN1171980A (en) * | 1996-07-25 | 1998-02-04 | 中国科学院大连化学物理研究所 | One step method for synthesis of catalyst for 2, 5 -dimethyl-2, 4 -hexadiene reaction and its application |
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| TAKESHI NISHIGUCHI 等: "DEHYDRATION OF ALCOHOLS CATALYZED BY COPPER(I1) SULFATE ADSORBED ON SILICA GEL", 《TETRAHEDRON LETTERS》 * |
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| CN113880099A (en) * | 2021-10-29 | 2022-01-04 | 山东东岳有机硅材料股份有限公司 | Method for preparing sodium silicate by utilizing organic silicon three wastes in green recycling manner |
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Application publication date: 20111207 |