CN103936709B - Synthetic method of piperonal - Google Patents
Synthetic method of piperonal Download PDFInfo
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- CN103936709B CN103936709B CN201410201876.2A CN201410201876A CN103936709B CN 103936709 B CN103936709 B CN 103936709B CN 201410201876 A CN201410201876 A CN 201410201876A CN 103936709 B CN103936709 B CN 103936709B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
- C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
- C07D317/50—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to atoms of the carbocyclic ring
- C07D317/54—Radicals substituted by oxygen atoms
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Abstract
The invention relates to the technical field of the medical intermediate fine chemical industry and in particular relates to a synthetic method of piperonal. The synthetic method comprises the following steps: 1 uniformly mixing benzodioxole, formaldehyde with concentration of 40% and a primary catalyst dodecyl trimethyl ammonium bromide with a solvent, then adding hydrochloric acid with concentration of 35-37% and standing for layering after reaction, thus obtaining a piperonyl chloride solution, wherein the solvent is trichloromethane, tetrachloromethane or methylbenzene; 2 preparing a sodium bicarbonate or sodium carbonate water solution with concentration less than or equal to that of a saturated solution, adding the sodium bicarbonate or sodium carbonate water solution to the piperonyl chloride solution and reacting to obtain a piperonyl alcohol solution; 3 introducing air into the piperonyl alcohol solution to oxidize the piperonyl alcohol solution to generate a piperonal solution by using both ferric nitrate and 4-hydroxy-2,2,4,4-methylpiperidine nitroxyl free radical as final catalysts. The synthetic method provided by the invention has the advantages of accessible raw materials, mild reaction conditions, stable and high yield, few byproducts and low cost.
Description
Technical field
The present invention relates to medicine intermediate technical field of fine, particularly to a kind of synthetic method of heliotropin.
Background technology
Heliotropin (piperonal, cas120-57-0), is piperonal again, and chemical name is 3,4- dioxymethylene benzene
Formaldehyde.Heliotropin is white glossy crystal, and molecular formula is c8h6o3, molecular weight 150.14,35～37 DEG C of fusing point, boiling point 261
～263 DEG C, have with sweet garden heliotrope fragrance, faint pungent perfume (or spice), fragrance is weaker and lasting is lasting.Heliotropin is naturally occurring in Huang
In the plants such as camphor oil, vanilla, gillyflower.
Heliotropin is a kind of extremely wide rare spice of purposes, sells well in decades on international market.Produce foreign jasmine
The primary raw material of jasmine aldehyde contains the Sassafras oil of safrole 75-85%, and the past is always extracts from sassafras root, and root breaks and sets
Extremely, current sassafras has faced exhaustion.
Insider thinks, heliotropin, as a kind of function admirable, broad-spectrum fine chemical material, will have wide
Wealthy development prospect.With heliotropin as raw material, tens kinds of derivative fine chemical products can be developed, such as helional,
Piperonylacetone, heliotrope nitrile, sesamol etc..These derived products are in medicine.Have latent in the industries such as pesticide, food, daily use chemicals
Application market.Piperonyl alcohol and propionic aldehyde carry out in sig water aldol condensation work(, hot decompression dehydration, after catalytic hydrogenating reduction
Can get helional, for preparing floral type and delicate fragrance type essence, in highclass perfumes, cosmetics, articles for washing, spray
In have application, consumption is up to 10%.Heliotropin is reacted with condensation of acetone, can obtain piperonylacetone, in order to prepare after oxidation
Fruity type and flower flavor essence are it is adaptable to the perfuming of soap, detergent.The reduction of heliotropin direct hydrogenation can produce heliotrope
Alcohol, its good stability, can be used as preparing senior essence, there is not allochroic feature, be particularly suited for cream kind daily chemical products.
React generation white crystals with heliotropin and oxammonium sulfate., add acetic anhydride dehydration, heliotrope eyeball can be obtained after conversion, there is bean
The fragrance such as perfume, mattress perfume (or spice) and foundation cream are fragrant, are the essence new products that developed recently gets up.Additionally, medicine also can be developed with heliotropin
And the intermediate sesamol of high-grade antimildew and antibacterial synergist synthesis, pesticide pyrethroid synergist methylenedioxybenzenes alkane
Base ether, antitumor and the preventing and treating downstream such as hypertension disease medicament intermediate and alkaloid deep processed product.
Mostly heliotropin is to be obtained using the method for synthetic at present.The synthetic method of heliotropin can be divided into two big
Class: semisynthesis with plant extract Sassafras oil as raw material and complete synthesis with petrochemicals catechol as raw material
Method.
With Sassafras oil for Material synthesis heliotropin by raw material is limited, can not meet the market demand.Using chemistry
The complete synthesis feasible and competitive method having become heliotropin production of method.
The total synthesis method of existing heliotropin mainly includes following several:
The method disclosing preparing piperonal in one kettle way in list of references 1, using piperonyl cyclonene with glyoxalic acid in dense sulfur
Under acid catalysiss, low-temp reaction generates piperonyl hydroxyacetic acid, adds concentrated nitric acid, heats decarboxylation synthesizing piperonal.Concrete reaction is such as
Under:
The method has the advantages that process is simple, yield be higher, good product quality, but uses a large amount of sulfuric acid catalysis, produces
Raw Waste Sulfuric Acid is more intractable.
Disclose a kind of chemical synthesis and preparation method of heliotropin in reference paper 2, using piperonyl cyclonene and trimerization first
Aldehyde, 30% hydrochloric acid reaction generate Fructus Piperiss chlorine, and Fructus Piperiss chlorine is reacted with hexamethylenamine again, and hydrochloric acid hydrolyzes, and generate heliotropin.The method
The yield of middle purpose product is unstable, and meanwhile, the by-product of generation is more.
Concrete reaction is as follows:
Disclose heliotropin and its derivant synthesis technique in reference paper 3, using piperonyl cyclonene and paraformaldehyde, dense
Hydrochloric acid reaction generates Fructus Piperiss chlorine (3,4- chloromethyl dioxymethylene benzene), and piperonyl chlorine and Sodium Acetate Trihydrate react generation piperonyl alcohol vinegar
Acid esters, piperonyl alcohol acetate and sodium hydroxide react generation piperonyl alcohol, piperonyl alcohol palladium carbon catalysis under with air reaction
Generate heliotropin.
The method each portion reaction yield is all higher, but reactions steps are more, and route is longer；Using hydrogenation technique, safety
Property is poor.
Reference paper:
1st, the method for preparing piperonal in one kettle way, [applicant] Lizhi Biochemical Tech Co., Ltd., Shanghai, [Granted publication
Number] cn101659650b, [authorized announcement date] 2012.09.05；
2nd, the chemical synthesis and preparation method of heliotropin, [applicant] Dongying Yimengsheng Chemical Industry Co., Ltd., [Granted publication
Number] cn101899033b, [authorized announcement date] 2012.05.23；
3rd, heliotropin and its derivant synthesis technique, [applicant] grace draws (common) joint-stock company, [Granted publication
Number] cn100528858, [authorized announcement date] 2009.08.19.
Content of the invention
It is an object of the invention to provide a kind of raw material is easy to get, reaction condition is gentle, stable yield and height, by-product are few,
The synthetic method of heliotropin with low cost.
The object of the present invention is achieved like this, a kind of synthetic method of heliotropin, comprises the steps:
Step 1, piperonyl cyclonene, the formaldehyde of concentration 40% and preliminary catalyst trimethyldodecane base ammonium bromide and solvent are mixed
Close uniformly, add the hydrochloric acid of concentration 35%-37% afterwards, stratification after chloromethylation, obtain piperonyl chlorine molten
Liquid, concrete reaction such as following formula:
Formula (1)；
Wherein, described solvent is any one in chloroform, carbon tetrachloride or toluene.
Step 2, preparation concentration are less than or equal to the sodium bicarbonate of saturated solution concentration or aqueous sodium carbonate, and by itself plus
Enter in prepared described piperonyl chlorine solution, after reaction, obtain piperonyl alcohol solution；Concrete reaction such as following formula:
Formula (2)；
Step 3, with ferric nitrate and 4- hydroxyl -2,2,6,6- methyl piperidine NO free radicals collectively as final catalyst,
To blowing air in described piperonyl alcohol solution, oxidation generates heliotropin solution, vivo reaction type such as following formula:
Formula (3)；
According to statistics, the scheme being provided by the present invention, the yield of the purpose product heliotropin finally giving can reach
To 89.5%-90.7%.
By above-mentioned reaction it can be seen that comparing with list of references 1, in the scheme that the present invention provides, intermediate product is stable,
Pollution-free, and final product is in addition to purpose product, and remaining product only has sodium chloride and carbon dioxide, easily collects, right
Environmental nonpollution, meanwhile, can also secondary utilization after collection.
Contrast with list of references 2, the scheme being provided by the present invention, by-product is few, meanwhile, the by-product of recovery can return
Receive and recycle, and the yield stable of purpose product, the equal energy of yield of the purpose product heliotropin obtaining through many experiments
Enough reach 89.5%-90.7%.
Compared with list of references 3, the scheme that the present invention provides, the not only high income of heliotropin, and, reactions steps are relatively
Few, safe in preparation process, there is not potential safety hazard.
Further, in step 1, the formaldehyde of described piperonyl cyclonene, the hydrochloric acid of concentration 35%-37% and concentration 40%, three
Mol ratio be 1:(1.2-1.5): (1.2-2.0)；
The amount of described preliminary catalyst is the 0.3-0.5% of the integral molar quantity of described piperonyl cyclonene；
Described solvent is (2-4) with the mol ratio of described piperonyl cyclonene: 1.
Further, in step 1, during the hydrochloric acid of described addition concentration 35%-37%, specifically include:
At 20-70 DEG C, it is added dropwise to described hydrochloric acid while stirring, the persistent period of hydrochloric acid described in Deca is 2.5-3 hour.
Further, in step 2, described sodium bicarbonate or sodium carbonate are (1.2-1.6) with the mol ratio of described piperonyl cyclonene:
1 or (0.6-0.8): 1.
Further, in step 2, obtain in piperonyl alcohol solution after described reaction, described reaction specifically includes:
At 20-120 DEG C, hybrid reaction 6-10 hour, stratification, take organic faciess to be piperonyl alcohol solution.
Further, in step 2, obtain in piperonyl alcohol solution after described reaction, during described reaction, using gas
Phase chromatograph detector detects piperonyl chlorine solution, and after reaction completely, reaction terminates.
Further, in step 3, described ferric nitrate is 1:(0.05-0.10 with the mol ratio of described piperonyl cyclonene), described 4-
Hydroxyl -2,2,6,6- methyl piperidine NO free radical is 1:(0.03-0.08 with the mol ratio of described piperonyl cyclonene).
Further, after step 2, before step 3, also include, the described piperonyl alcohol solution generating is carried out with water
Washing；
Specifically include, piperonyl alcohol solution adds water, after being sufficiently stirred for, stratification.
Further, after step 3, also include step 4:
By the described heliotropin solution generating through distilling precipitation, vacuum fractionation, under 1.8kpa vacuum, collect 135-140
DEG C fraction, condensation-crystallization obtains final product heliotropin finished product.
Further, after step 3, before step 4, also include, the heliotropin solution of generation is washed with water；
Specifically include, heliotropin solution adds water, after being sufficiently stirred for, stratification.
Brief description
A kind of synthetic method flow chart of heliotropin that Fig. 1 provides for the present invention.
Specific embodiment
Below by specific embodiment and combine accompanying drawing the present invention is described in further detail.
A kind of synthetic method of heliotropin, as shown in figure 1, comprise the steps:
Step 1, piperonyl cyclonene, the formaldehyde of concentration 40% and preliminary catalyst trimethyldodecane base ammonium bromide and solvent are mixed
Close uniformly, add the hydrochloric acid of concentration 35%-37% afterwards, stratification after chloromethylation, obtain piperonyl chlorine molten
Liquid；Wherein, described solvent is any one in chloroform, carbon tetrachloride or toluene.
Preparation raw material:
Measure the formaldehyde of piperonyl cyclonene, the hydrochloric acid of concentration 35%-37% and concentration 40% respectively, the mol ratio of three is 1:
(1.2-1.5):(1.2-2.0)；
In order to improve the utilization rate of raw material it is preferable that the mol ratio of piperonyl cyclonene, hydrochloric acid and formaldehyde is 1:(1.3-1.4):
(1.4-1.6).
Measure preliminary catalyst trimethyldodecane base ammonium bromide, the amount of described preliminary catalyst is the total of described piperonyl cyclonene
The 0.3-0.5% of mole；
Measure solvent, described solvent is chloroform, any one in carbon tetrachloride or toluene, described solvent with described
The mol ratio of piperonyl cyclonene is (2-4): 1；
In order to enable raw material to be completely dissolved in a solvent, and can fully react, so, the solvent of addition with
The mol ratio of piperonyl cyclonene is (2-4): 1；But, when solvent is excessive, the speed of W-response is slower, when solvent is very few, former
Material not only can not be completely dissolved, and can produce side reaction simultaneously, and preferably, therefore, solvent is 3:1 with the mol ratio of piperonyl cyclonene.
Described piperonyl cyclonene and described formaldehyde are added in described solvent, adds described preliminary catalyst, after stirring,
At 20-70 DEG C, it is added dropwise to described hydrochloric acid while stirring, stratification after chloromethylation, takes off a layer organic facies, as
Piperonyl chlorine solution, concrete reaction such as following formula:
Formula (1)
Wherein piperonyl cyclonene and formaldehyde add the order in solvent regardless of order, but, hydrochloric acid needs being eventually adding, because
Add hydrochloric acid in advance, hydrochloric acid meeting is easily and mixture reaction generates polychloride, and the side reaction of generation is more, and then can bring into relatively
Many by-products.And when adding hydrochloric acid, need lentamente drop by drop to add while stirring.
In order to prevent side reaction, simultaneously so that reaction can gently carry out the hydrochloric acid it is preferable that measuring described in Deca
The time using is 2.5-3 hour, and most preferably, time for adding is 3 hours.
Step 2, preparation concentration are less than or equal to the sodium bicarbonate of saturated solution concentration or aqueous sodium carbonate, and by itself plus
Enter in prepared described piperonyl chlorine solution, after reaction, obtain piperonyl alcohol solution.
Described piperonyl chlorine solution is added thereto to described sodium bicarbonate or aqueous sodium carbonate while stirring, in 20-
At 120 DEG C, hybrid reaction 6-10 hour, stratification, take organic faciess to be piperonyl alcohol solution, concrete reaction such as following formula:
Formula (2)；
Wherein said sodium bicarbonate or sodium carbonate with the mol ratio of described piperonyl cyclonene are:
(1.2-1.6): 1 or (0.6-0.8): 1；
So that the condition of reaction and temperature can more be stablized, and it is easily controlled it is preferable that preparing described ocean jasmine
In jasmine alcoholic solution, described reaction temperature is 50-100 DEG C, and the described response time is 7-8 hour.Most preferably, described reaction temperature
For 75-85 DEG C, the described response time is 8 hours.
Wherein it is preferred to, described sodium carbonate or sodium bicarbonate are (1.3-1.5) with the mol ratio of described piperonyl cyclonene: 1 or
(0.65-0.75): 1.
In order to improve the utilization rate of raw material so that reaction can be carried out completely, observing piperonyl chlorine solution and carbon
It is preferable that detecting using gas chromatograph in the course of reaction of acid sodium aqueous solution, piperonyl chlorine solution reaction is detected complete
Afterwards, reaction terminates.
Preferably, after obtaining piperonyl alcohol solution, in order to reduce the impurity in piperonyl alcohol solution, can be to obtaining
Add water in piperonyl alcohol solution and be followed by stirring and washing, standing is so that organic layer separates with inorganic layer, and then makes to obtain purer
Piperonyl alcohol solution.
Step 3, with ferric nitrate and 4- hydroxyl -2,2,6,6- methyl piperidine NO free radicals collectively as final catalyst,
To blowing air in described piperonyl alcohol solution, oxidation generates heliotropin solution.
With ferric nitrate and 4- hydroxyl -2,2,6,6- methyl piperidine NO free radicals collectively as final catalyst, to described
It is passed through cleaned air, under room temperature, oxidation reaction generates heliotropin solution in piperonyl alcohol solution；
Concrete reaction equation such as following formula:
Formula (3)；
Wherein, described ferric nitrate and the mol ratio of described piperonyl cyclonene are 1:(0.05-0.10) described 4- hydroxyl -2,2,6,6-
Methyl piperidine NO free radical is 1:(0.03-0.08 with the mol ratio of described piperonyl cyclonene).
After tentatively obtaining heliotropin solution, in order to obtain final finished, can will generate heliotropin solution
Carry out distilling precipitation using conventional method, under 1.8kpa vacuum, after vacuum fractionation, collect 135-140 DEG C of fraction, condensation
Crystallization obtains final product heliotropin crystal grain finished product.
Wherein, before carrying out the heliotropin obtaining solution distilling precipitation, miscellaneous in the finished product obtaining in order to reduce
Matter content, can add water in this heliotropin solution of obtaining, be followed by stirring and washing, stratification, obtain purer ocean
Jasminal solution.
According to statistics, the scheme being provided by the present invention, the yield of the purpose product heliotropin finally giving can reach
To 89.5%-90.7%.
By above-mentioned reaction it can be seen that comparing with list of references 1, in the scheme that the present invention provides, intermediate product is stable,
Pollution-free, and final product is in addition to purpose product, and remaining product only has sodium chloride and carbon dioxide, easily collects, right
Environmental nonpollution, meanwhile, can also secondary utilization after collection.
Contrast with list of references 2, the scheme being provided by the present invention, by-product is few, meanwhile, the by-product of recovery can return
Receive and recycle, and the yield stable of purpose product, the equal energy of yield of the purpose product heliotropin obtaining through many experiments
Enough reach 89.5%-90.7%.
Compared with list of references 3, the scheme that the present invention provides, the not only high income of heliotropin, and, reactions steps are relatively
Few, safe in preparation process, be not in potential safety hazard.
Next, the synthesis side of the heliotropin of present invention offer is discussed in detail by following several specific embodiments
Method:
Embodiment 1:
Add solvent chloroform 200ml in 500ml flask, 61 grams of piperonyl cyclonene (0.5mol), concentration are 40% first
46.3 grams of aldehyde solution (0.63mol), 0.5 gram of catalyst trimethyldodecane base ammonium bromide, after stirring, then are added dropwise to concentration
60 grams of hydrochloric acid for 36% (0.7mol), time for adding controls at 150 minutes, reacts 12 hours at 60 DEG C, static, under separating
Layer grease, obtains piperonyl chlorine chloroform soln；
In above-mentioned piperonyl chlorine chloroform soln, it is slowly added to undersaturated sodium carbonate liquor while stirring, wherein
31.8 grams of sodium carbonate (0.3mol), water 200ml, stirring reaction 8 hours under 60 DEG C of insulations, isolating lower floor's organic faciess is heliotrope
Alcoholic solution；
Add 200ml water in the piperonyl alcohol solution obtaining, be sufficiently stirred for, washing；Can be washed twice；Standing
Layering, obtains more pure final piperonyl alcohol solution；
Room temperature is controlled to be 25-30 DEG C, addition catalyst 4- hydroxyl -2 in the final piperonyl alcohol solution obtaining, 2,6,6-
3 grams of methyl piperidine NO free radical (4-oh-tempo), 5 grams of ferric nitrate, are passed through cleaned air, react 12 hours, isolate down
Layer organic facies are preliminary heliotropin solution；
Add 200ml water in the preliminary heliotropin solution obtaining, be sufficiently stirred for, washing, can wash twice；Standing
After layering, obtain final heliotropin solution；
The final heliotropin solution obtaining is used conventional method, vacuum distillation, isolates chloroform solvent,
Collect 135-140 DEG C of fraction, cooling under 1.8kpa vacuum, obtain 67.1 grams of final heliotropin white crystals, yield
89.5%.
Example 2:
Add solvent carbon tetrachloride 200ml in 500ml flask, 61 grams of piperonyl cyclonene (0.5mol), concentration are 40% first
46.3 grams of aldehyde solution (0.63mol), 0.5 gram of catalyst trimethyldodecane base ammonium bromide, after stirring, then are added dropwise to concentration
60 grams of hydrochloric acid for 36% (0.7mol), time for adding controls at 150 minutes, reacts 12 hours at 60 DEG C, static, under separating
Layer grease, obtains piperonyl chlorine carbon tetrachloride solution；
In above-mentioned piperonyl chlorine carbon tetrachloride solution, it is slowly added to undersaturated sodium bicarbonate solution while stirring, its
Middle 52 grams of sodium bicarbonate (0.6mol), water 200ml, stirring reaction 8 hours under 60 DEG C of insulations, isolating lower floor's organic faciess is foreign jasmine
Jasmine alcoholic solution；
Add 200ml water in the piperonyl alcohol solution obtaining, be sufficiently stirred for, washing；Can be washed twice；Standing
Layering, obtains more pure final piperonyl alcohol solution；
Control room temperature to be 25-30 DEG C, add in the final piperonyl alcohol solution obtaining 3 grams of catalyst 4-oh-tempo,
5 grams of ferric nitrate, is passed through cleaned air, reacts 12 hours, isolates lower floor's organic faciess and is preliminary heliotropin solution；
Add 200ml water in the preliminary heliotropin solution obtaining, be sufficiently stirred for, washing, can wash twice；Standing
After layering, obtain final heliotropin solution；
The final heliotropin solution obtaining is used conventional method, vacuum distillation, isolates carbon tetrachloride solvent,
Collect 135-140 DEG C of fraction, cooling under 1.8kpa vacuum, obtain 68.0 grams of final heliotropin white crystals, yield
90.7%.
Example 3:
In 500ml flask add solvent toluene 200ml, 61 grams of piperonyl cyclonene (0.5mol), concentration be 40% formaldehyde molten
46.3 grams of liquid (0.63mol), 0.5 gram of catalyst trimethyldodecane base ammonium bromide, after stirring, then are added dropwise to concentration and are
60 grams of 36% hydrochloric acid (0.7mol), time for adding controls at 150 minutes, reacts 12 hours at 60 DEG C, static, separates lower floor
Grease, obtains piperonyl chlorine toluene solution；
In above-mentioned piperonyl chlorine toluene solution, it is slowly added to undersaturated sodium carbonate liquor, wherein carbonic acid while stirring
35 grams of sodium, water 200ml, stirring reaction 8 hours under 60 DEG C of insulations, isolating lower floor's organic faciess is piperonyl alcohol solution；
Add 200ml water in the piperonyl alcohol solution obtaining, be sufficiently stirred for, washing；Can be washed twice；Standing
Layering, obtains more pure final piperonyl alcohol solution；
Control room temperature to be 25-30 DEG C, add in the final piperonyl alcohol solution obtaining 3 grams of catalyst 4-oh-tempo,
5 grams of ferric nitrate, is passed through cleaned air, reacts 12 hours, isolates lower floor's organic faciess and is preliminary heliotropin solution；
Add 200ml water in the preliminary heliotropin solution obtaining, be sufficiently stirred for, washing, can wash twice；Standing
After layering, obtain final heliotropin solution；
The final heliotropin solution obtaining is used conventional method, vacuum distillation, isolates toluene solvant, 1.8kpa is true
Collect 135-140 DEG C of fraction, cooling under reciprocal of duty cycle, obtain 67.5 grams of final heliotropin white crystals, yield 89.9%.
Example 4:
Add solvent chloroform 200ml in 500ml flask, 61 grams of piperonyl cyclonene (0.5mol), concentration are 40% first
45.8 grams of aldehyde solution (0.6mol), 0.5 gram of catalyst trimethyldodecane base ammonium bromide, after stirring, then are added dropwise to concentration
56 grams of hydrochloric acid for 36% (0.6mol), time for adding controls at 150 minutes, reacts 12 hours at 60 DEG C, static, under separating
Layer grease, obtains piperonyl chlorine chloroform soln；
In above-mentioned piperonyl chlorine chloroform soln, it is slowly added to undersaturated sodium carbonate liquor while stirring, wherein
36 grams of sodium carbonate, water 200ml, stirring reaction 8 hours under 60 DEG C of insulations, isolating lower floor's organic faciess is piperonyl alcohol solution；
Add 200ml water in the piperonyl alcohol solution obtaining, be sufficiently stirred for, washing；Can be washed twice；Standing
Layering, obtains more pure final piperonyl alcohol solution；
Control room temperature to be 25-30 DEG C, add in the final piperonyl alcohol solution obtaining 3 grams of catalyst 4-oh-tempo,
5 grams of ferric nitrate, is passed through cleaned air, reacts 12 hours, isolates lower floor's organic faciess and is preliminary heliotropin solution；
Add 200ml water in the preliminary heliotropin solution obtaining, be sufficiently stirred for, washing, can wash twice；Standing
After layering, obtain final heliotropin solution；
The final heliotropin solution obtaining is used conventional method, vacuum distillation, isolates carbon tetrachloride solvent,
Collect 135-140 DEG C of fraction, cooling under 1.8kpa vacuum, obtain 67.3 grams of final heliotropin white crystals, yield
89.7%.
Example 5:
Add solvent carbon tetrachloride 200ml in 500ml flask, 61 grams of piperonyl cyclonene (0.5mol), concentration are 40% first
80 grams of aldehyde solution (1mol), 0.5 gram of catalyst trimethyldodecane base ammonium bromide, after stirring, then are added dropwise to concentration and are
78 grams of 36% hydrochloric acid (0.75mol), time for adding controls at 150 minutes, reacts 12 hours at 60 DEG C, static, under separating
Layer grease, obtains piperonyl chlorine carbon tetrachloride solution；
In above-mentioned piperonyl chlorine carbon tetrachloride solution, it is slowly added to undersaturated sodium bicarbonate solution while stirring, its
Middle 52 grams of sodium bicarbonate (0.6mol), water 200ml, stirring reaction 8 hours under 60 DEG C of insulations, isolating lower floor's organic faciess is foreign jasmine
Jasmine alcoholic solution；
Add 200ml water in the piperonyl alcohol solution obtaining, be sufficiently stirred for, washing；Can be washed twice；Standing
Layering, obtains more pure final piperonyl alcohol solution；
Control room temperature to be 25-30 DEG C, add in the final piperonyl alcohol solution obtaining 3 grams of catalyst 4-oh-tempo,
5 grams of ferric nitrate, is passed through cleaned air, reacts 12 hours, isolates lower floor's organic faciess and is preliminary heliotropin solution；
Add 200ml water in the preliminary heliotropin solution obtaining, be sufficiently stirred for, washing, can wash twice；Standing
After layering, obtain final heliotropin solution；
The final heliotropin solution obtaining is used conventional method, vacuum distillation, isolates carbon tetrachloride solvent,
Collect 135-140 DEG C of fraction, cooling under 1.8kpa vacuum, obtain 67.8 grams of final heliotropin white crystals, yield
90.5%.
Wherein with embodiment 2 acquired results be optimal.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for the skill of this area
For art personnel, the present invention can have various modifications and variations.All within the spirit and principles in the present invention, made any repair
Change, equivalent, improvement etc., should be included within the scope of the present invention.
Claims (6)
1. a kind of synthetic method of heliotropin is it is characterised in that comprise the steps:
Step 1, piperonyl cyclonene, the formaldehyde of concentration 40% and preliminary catalyst trimethyldodecane base ammonium bromide are mixed all with solvent
Even, add the hydrochloric acid of concentration 35%-37% afterwards, stratification after chloromethylation, obtain piperonyl chlorine solution；Its
In, described solvent is any one in chloroform, carbon tetrachloride or toluene；
Step 2, preparation concentration are less than or equal to sodium bicarbonate or the aqueous sodium carbonate of saturated solution concentration, and are added into making
In the described piperonyl chlorine solution obtaining, after reaction, obtain piperonyl alcohol solution；The described piperonyl alcohol solution water generating is entered
Row washing, specifically includes, and adds water, after being sufficiently stirred for, stratification in piperonyl alcohol solution；
Step 3, with ferric nitrate and 4- hydroxyl-TEMPO collectively as final catalyst, give
Blowing air in described piperonyl alcohol solution, oxidation generates heliotropin solution；The heliotropin solution of generation is washed with water
Wash, specifically include, heliotropin solution adds water, after being sufficiently stirred for, stratification；
Step 4, by generate described heliotropin solution through distill precipitation, vacuum fractionation, under 1.8kpa vacuum collect 135-
140 DEG C of fraction, condensation-crystallization obtains final product heliotropin finished product.
2. a kind of heliotropin according to claim 1 synthetic method it is characterised in that:
In step 1, the formaldehyde of described piperonyl cyclonene, the hydrochloric acid of concentration 35%-37% and concentration 40%, the mol ratio of three is 1:
(1.2-1.5):(1.2-2.0)；
The amount of described preliminary catalyst is the 0.3-0.5% of the integral molar quantity of described piperonyl cyclonene；
Described solvent is (2-4) with the mol ratio of described piperonyl cyclonene: 1.
3. a kind of heliotropin according to claim 2 synthetic method it is characterised in that:
In step 1, during the hydrochloric acid of described addition concentration 35%-37%, specifically include:
At 20-70 DEG C, it is added dropwise to described hydrochloric acid while stirring, the persistent period of hydrochloric acid described in Deca is 2.5-3 hour.
4. a kind of heliotropin according to claim 1 synthetic method it is characterised in that:
In step 2, described sodium bicarbonate or sodium carbonate are (1.2-1.6): 1 or (0.6-0.8) with the mol ratio of described piperonyl cyclonene:
1.
5. a kind of heliotropin according to claim 4 synthetic method it is characterised in that:
In step 2, obtain in piperonyl alcohol solution after described reaction, described reaction specifically includes:
At 20-120 DEG C, hybrid reaction 6-10 hour, stratification, take organic faciess to be piperonyl alcohol solution.
6. a kind of heliotropin according to claim 4 synthetic method it is characterised in that:
In step 2, obtain in piperonyl alcohol solution after described reaction, during described reaction, using gas chromatographic detection instrument
Detection piperonyl chlorine solution, after reaction completely, reaction terminates.
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| CN102177124A (en) * | 2008-10-07 | 2011-09-07 | 宇部兴产株式会社 | Process for producing an aromatic aldehyde compound |
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| CN101899033A (en) * | 2010-04-29 | 2010-12-01 | 东营益盟盛化工有限公司 | Chemical synthesis and preparation method of heliotropin |
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| 从邻苯二酚合成3,4-亚甲二氧基苯甲醇;贺全国等;《应用化学》;20030331;第20卷(第3期);281-283 * |
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