CN106397387A - Method for preparing pepper ring - Google Patents
Method for preparing pepper ring Download PDFInfo
- Publication number
- CN106397387A CN106397387A CN201610833315.3A CN201610833315A CN106397387A CN 106397387 A CN106397387 A CN 106397387A CN 201610833315 A CN201610833315 A CN 201610833315A CN 106397387 A CN106397387 A CN 106397387A
- Authority
- CN
- China
- Prior art keywords
- dichloromethane
- dmso
- deca
- piperonyl cyclonene
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
Abstract
The invention discloses a price relatively inexpensive, reaction condition mild synthetic pepper ring process method that adopts DMSO, methylene chloride and sodium hydroxide as the base material, drips with DMSO solution of catechol, regulates reaction temperature at 120 DEG C or below, cuts down solvent decomposition phenomenon caused by high temperature, takes separation means of oil-water separator instead of hydraulic steam distillation to extract products during post processing, reduces greatly the amount of resulted waste water, gives better process safety. The method recycles and reuses the disengaged water, and reduces the amount of waste water to the minimum. The method recycles and reapplies dichloromethane and DMSO recovered by distillation, which is shown by study result produces no effect on reaction, achieving the green recycled use of organic solvent, the method cuts down production cost.
Description
Technical field
The present invention relates to the field of chemical synthesis is and in particular to a kind of method of synthesis piperonyl cyclonene.
Background technology
Piperonyl cyclonene, chemical name 1,2- methylenedioxybenzenes, be widely used in low toxic pesticide, berberine, heliotropin and
The preparation of sesamol and antioxidant etc., piperonyl cyclonene and its derivant are subject to the extensive pass of people because of its special biochemical activity
Note, the research and development of its technology of preparing become one of emphasis in synthetic drug and synthetic perfume research.Due to social development
Needs, the technology of preparing with plants essential oil as initiation material more and more limited by ecological resource protection, research and development with
Petrochemicals are that the full chemistry synthesis route of initiation material has become an urgent demand of social development.
The synthetic method of current document introduction has several as follows：
1., with catechol, dichloromethane as raw material, synthesize piperonyl cyclonene using reaction under high pressure technique, this method is to equipment requirements relatively
High.
2. with catechol, dichloromethane as raw material, piperonyl cyclonene is synthesized with Catalyzed By Phase-transfer Catalyst, but reclaims difficult,
Relatively costly, serious environmental pollution can be caused.
3., with catechol, dichloromethane as raw material, piperonyl cyclonene is synthesized with special organic base, but price is prohibitively expensive,
It is difficult to industrialization.
4., with catechol, dichloromethane as raw material, piperonyl cyclonene is synthesized for medium with non-polar solven DMF, DMSO, exists
Solvent reaction temperature is higher（130 DEG C about）, easily decompose situation.
5., with catechol as raw material, using the reaction of gas phase dichloromethane, there is dichloromethane loss serious phenomenon.
6. other document introductions adopt solvent-free reaction or molecular sieve catalytic, are all difficult to because of special expensive catalyst
Industrialization.
The present invention introduces that a kind of relative price is cheap, the gentle synthesis piperonyl cyclonene process of reaction condition.
Content of the invention
It is bed material, at a reflux temperature, Deca catechol that this patent adopts DMSO, dichloromethane, sodium hydroxide
DMSO solution, reaction isolates product and dichloromethane using oil water separator after terminating, and yield reaches more than 85%.
Synthetic route：
The present invention is achieved through the following technical solutions：A kind of piperonyl cyclonene preparation method, using DMSO, dichloromethane, sodium hydroxide
For bed material, the DMSO solution of Deca catechol, reaction isolates piperonyl cyclonene and dichloromethane using oil water separator after terminating.
Specifically, DMSO, dichloromethane, sodium hydroxide are put in flask, heat up.
Specifically, system temperature is controlled to be less than 120 DEG C during the DMSO solution of Deca catechol, Deca 3 to 4 hours.
Specifically, after dripping off the DMSO solution of catechol, then Deca dichloromethane, drip off and flow back in 110 DEG C ~ 115 DEG C
Insulation half an hour, then it is cooled to room temperature, filtration from sodium chloride, adds water.
Specifically, isolate dichloromethane and piperonyl cyclonene using oil water separator, be separated to no substantially oil phase distillation substantially
Out, then start Distillation recovery water, the aqueous phase steaming is extracted with appropriate dichloromethane, the set capable of circulation of the aqueous phase after extraction
With.Distill 100 DEG C of top temperature, start to switch Distillation recovery DMSO, the DMSO of recovery is capable of circulation to be applied mechanically.
Specifically, above-mentioned preparation method is specially：By 440mlDMSO, dichloromethane 120ml, sodium hydroxide 230g put into
To in 2 liters of there-necked flasks, it is warmed up to 95 DEG C, start the solution that the catechol of Deca 110g is dissolved in 440ml DMSO,
Control system temperature is less than 120 DEG C, and Deca 3 to 4 hours drips off Deca 90ml dichloromethane again, drips off in 110 DEG C ~ 115 DEG C
Backflow insulation half an hour, it is cooled to room temperature, filtration from sodium chloride, adds water 400ml, isolate remnants using oil water separator
Dichloromethane and piperonyl cyclonene, be separated to substantially no substantially oil phase distill, start Distillation recovery water, the aqueous phase steaming is with suitable
The dichloromethane extraction of amount, the aqueous phase after extraction is capable of circulation to be applied mechanically.Distill 100 DEG C of top temperature, start to switch Distillation recovery DMSO
, the DMSO of recovery is capable of circulation to be applied mechanically, remnants about 90g.Oil-water separation obtains organic faciess piperonyl cyclonene 129g, gas phase purity 97%, yield
85.4%.
The beneficial effects of the present invention is：It is solvent that the present invention adopts DMSO, with low-cost sodium hydroxide for tiing up acid
Agent, controls the temperature of reaction system simultaneously below 120 DEG C, decreases the solvolysiss phenomenon that high temperature leads to, post processing is taken
Oil water separator separate mode replaces vapor distillation mode to extract product, greatly reduces waste water yield, process safety is more
Good.The wastewater flow rate amount of being minimized that the water separating recovery once again, order are produced.By the dichloromethane of Distillation recovery and DMSO
Recovery once again, research finds reaction is not affected, and the green circulatory realizing organic solvent uses, and reduces and produces into
This.
Specific embodiment
Embodiment 1：Prepared by piperonyl cyclonene
By 440mlDMSO, dichloromethane 120ml, sodium hydroxide 230g puts in 2 liters of there-necked flask, is warmed up to 95 DEG C, opens
The catechol of beginning Deca 110g is dissolved in the solution in 440ml DMSO, and control system temperature is less than 120 DEG C, Deca 3 to 4
Hour, drip off Deca 90ml dichloromethane again, dripped off in 110 DEG C ~ 115 DEG C backflow insulation half an hour, be cooled to room temperature, cross and filter
Remove sodium chloride, add water 400ml, isolate dichloromethane and the piperonyl cyclonene of remnants using oil water separator, be separated to substantially no
Substantially oil phase distills, and starts Distillation recovery water, and the aqueous phase steaming is extracted with appropriate dichloromethane, and the aqueous phase after extraction can
Recycled.Distill 100 DEG C of top temperature, start to switch Distillation recovery DMSO, the DMSO of recovery is capable of circulation to be applied mechanically, and remnants are about
90g.Oil-water separation obtains organic faciess piperonyl cyclonene 129g, gas phase purity 97%, yield 85.4%.
Embodiment 2：Prepared by piperonyl cyclonene
The DMSO that 440ml is reclaimed（More than GC98%）, dichloromethane 120ml, sodium hydroxide 230g put into 2 liters of three mouthfuls of burnings
In bottle, it is warmed up to 95 DEG C, the catechol starting Deca 110g is dissolved in the solution in 440ml DMSO（100ml reclaims DMSO
Plus the fresh DMSO of 300ml）, control system temperature be less than 120 DEG C, Deca 3 to 4 hours, drip off Deca 90ml dichloromethane again
Alkane, is dripped off in 110 DEG C ~ 115 DEG C backflow insulation half an hour, is cooled to room temperature, filtration from sodium chloride, adds recycle-water 400ml,
Isolate dichloromethane and the piperonyl cyclonene of remnants using oil water separator, be separated to substantially no obvious oil phase and distill, start
Distillation recovery water, the aqueous phase steaming is extracted with appropriate dichloromethane, and the aqueous phase after extraction is capable of circulation to be applied mechanically.Distill top temperature
100 DEG C, start to switch Distillation recovery DMSO.Oil-water separation obtains organic faciess piperonyl cyclonene 125g, gas phase purity 96.5%, yield
82.3%.
Embodiment 3：Prepared by piperonyl cyclonene
By the DMSO of 55ml, the dichloromethane of 13ml and 18g sodium hydroxide are put in three mouthfuls of reaction flasks, are heated under stirring
95 DEG C, at 95 ~ 110 DEG C, Deca 16.5g catechol is dissolved in the aqueous solution of 55ml water, Deca 1.5 hours, drips off intensification
To 110 ~ 115 DEG C, it is incubated 4 hours, adds 5ml dichloromethane, raw material converts completely substantially halfway, add 80ml water and carry out azeotropic
Distillation, obtains piperonyl cyclonene about 12g, content GC98%, yield 64%.
Comparison example 1：（Taking potassium carbonate as a example）
By 65mlDMSO, dichloromethane 13ml, potassium carbonate 30g puts in there-necked flask, is warmed up to 112 DEG C, starts Deca
The catechol of 16.5g is dissolved in the solution in 55ml DMSO, and control system temperature is less than 130 DEG C, Deca 1.5 hours, drips
Complete Deca 12ml dichloromethane again, dripping off in 130 DEG C about backflow insulation 5 hours, be cooled to room temperature, be filtered to remove potassium chloride and
Potassium carbonate salt, adds water 140ml, and air-distillation goes out dichloromethane and the piperonyl cyclonene of remnants, basic to the aqueous phase distilling out
No obvious oil phase, carries out a standing point liquid, and the aqueous phase separating adds sodium chloride to be extracted with appropriate dichloromethane, merging organic faciess,
Concentrate dichloromethane, finally give piperonyl cyclonene 16.9g, gas phase purity 91.7%, yield 84.6%.
Comparison example 2：（Taking potassium hydroxide as a example, documents and materials）
The catechol of 20g, the dichloromethane of 100ml, the diformazan of 75ml is sequentially added in the flask with three necks,round bottom of 500ml
Sulfoxide, slowly Deca 20g under heated and stirred（Mass fraction 50%）Potassium hydroxide solution, oil bath temperature controls at 85 ~ 90 DEG C
Lower backflow.Reaction 4 ~ 5 hours（TLC follows the tracks of reaction）, then carry out Distillation recovery dichloromethane, steam distillation obtains crude product,
Wash with water to neutrality, with anhydrous sodium sulfate drying, obtain anhydrous oily goods and materials 10.4g, yield 57.2%.（《Chemical Engineering Technology with open
Send out》Vol35No1 in January, 2006, author Dong Xinrong, Li Hui）
Comparison example 3：（With triethylamine as acid binding agent）
With triethylamine as acid binding agent, the same terms, backflow insulation 2h, product only converts 1.7%, failure.
Comparison example 4：（With pyridine as acid binding agent）
With triethylamine as acid binding agent, the same terms, backflow insulation 1h, product only converts 0.98%, failure.
Comparison example 5：（With sodium carbonate as acid binding agent）
With sodium carbonate as acid binding agent, the same terms, backflow insulation 11.5h, product conversion 18%, failure.
Claims (7)
1. a kind of piperonyl cyclonene preparation method it is characterised in that using DMSO, dichloromethane, sodium hydroxide be bed material, Deca neighbour benzene
The DMSO solution of diphenol, reaction isolates piperonyl cyclonene and dichloromethane using oil water separator after terminating.
2. piperonyl cyclonene preparation method according to claim 1 is it is characterised in that throw DMSO, dichloromethane, sodium hydroxide
Enter in flask, heat up.
3. piperonyl cyclonene preparation method according to claim 1 is it is characterised in that the DMSO solution time control of Deca catechol
System temperature processed is less than 120 DEG C.
4. piperonyl cyclonene preparation method according to claim 3 is it is characterised in that Deca 3 to 4 hours.
5. after piperonyl cyclonene preparation method according to claim 1 is it is characterised in that drip off the DMSO solution of catechol,
Deca dichloromethane again, being dripped off in 110 DEG C ~ 115 DEG C backflow insulation half an hour, being then cooled to room temperature, filtration from sodium chloride,
Add water.
6. piperonyl cyclonene preparation method according to claim 1 is it is characterised in that use oil water separator separation dichloromethane
And piperonyl cyclonene, it is separated to no obvious oil phase and distills, then start Distillation recovery water, the aqueous phase dichloromethane steaming extracts
Take, the aqueous phase recycled after extraction, distill 100 DEG C of top temperature, switch Distillation recovery DMSO, the DMSO recycled of recovery.
7. piperonyl cyclonene preparation method according to claim 1 is it is characterised in that concretely comprise the following steps：By 440mlDMSO, two
Chloromethanes 120ml, sodium hydroxide 230g puts in 2 liters of there-necked flask, is warmed up to 95 DEG C, starts the adjacent benzene two of Deca 110g
Phenol is dissolved in the solution in 440ml DMSO, and control system temperature is less than 120 DEG C, and Deca 3 to 4 hours drips off Deca again
90ml dichloromethane, is dripped off in 110 DEG C ~ 115 DEG C backflow insulation half an hour, is cooled to room temperature, filtration from sodium chloride, adds water
400ml, isolates dichloromethane and the piperonyl cyclonene of remnants using oil water separator, is separated to no obvious oil phase and distills, opens
Beginning Distillation recovery water, the aqueous phase dichloromethane steaming extracts.Distill 100 DEG C of top temperature, start to switch Distillation recovery DMSO.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610833315.3A CN106397387A (en) | 2016-09-20 | 2016-09-20 | Method for preparing pepper ring |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610833315.3A CN106397387A (en) | 2016-09-20 | 2016-09-20 | Method for preparing pepper ring |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106397387A true CN106397387A (en) | 2017-02-15 |
Family
ID=57997791
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610833315.3A Pending CN106397387A (en) | 2016-09-20 | 2016-09-20 | Method for preparing pepper ring |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106397387A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108727330A (en) * | 2018-06-18 | 2018-11-02 | 苏州盖德精细材料有限公司 | The novel synthesis of sesamol |
| CN110563693A (en) * | 2019-09-30 | 2019-12-13 | 苏州弘森药业股份有限公司 | Preparation method of pepper ring |
| CN110590732A (en) * | 2019-09-26 | 2019-12-20 | 河北海力香料股份有限公司 | Preparation method of piper nigrum rings |
| CN111004205A (en) * | 2019-12-30 | 2020-04-14 | 江西兄弟医药有限公司 | Synthetic method for preparing piperonyl butoxide under catalysis of composite alkali |
| CN115057841A (en) * | 2022-03-24 | 2022-09-16 | 万华化学集团股份有限公司 | Method for preparing 1, 2-methylenedioxybenzene |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03275683A (en) * | 1990-03-27 | 1991-12-06 | Hokko Chem Ind Co Ltd | Production of benzo-1,3-dioxole |
| CN102617543A (en) * | 2012-03-13 | 2012-08-01 | 天津科技大学 | Synthesis methods for piperonyl ethanol and derivatives thereof |
| CN103664536A (en) * | 2012-09-17 | 2014-03-26 | 天津科技大学 | Synthetic method of hydroxytyrosol |
-
2016
- 2016-09-20 CN CN201610833315.3A patent/CN106397387A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03275683A (en) * | 1990-03-27 | 1991-12-06 | Hokko Chem Ind Co Ltd | Production of benzo-1,3-dioxole |
| CN102617543A (en) * | 2012-03-13 | 2012-08-01 | 天津科技大学 | Synthesis methods for piperonyl ethanol and derivatives thereof |
| CN103664536A (en) * | 2012-09-17 | 2014-03-26 | 天津科技大学 | Synthetic method of hydroxytyrosol |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108727330A (en) * | 2018-06-18 | 2018-11-02 | 苏州盖德精细材料有限公司 | The novel synthesis of sesamol |
| CN110590732A (en) * | 2019-09-26 | 2019-12-20 | 河北海力香料股份有限公司 | Preparation method of piper nigrum rings |
| CN110563693A (en) * | 2019-09-30 | 2019-12-13 | 苏州弘森药业股份有限公司 | Preparation method of pepper ring |
| CN110563693B (en) * | 2019-09-30 | 2022-10-21 | 苏州弘森药业股份有限公司 | Preparation method of pepper ring |
| CN111004205A (en) * | 2019-12-30 | 2020-04-14 | 江西兄弟医药有限公司 | Synthetic method for preparing piperonyl butoxide under catalysis of composite alkali |
| CN115057841A (en) * | 2022-03-24 | 2022-09-16 | 万华化学集团股份有限公司 | Method for preparing 1, 2-methylenedioxybenzene |
| CN115057841B (en) * | 2022-03-24 | 2023-09-19 | 万华化学集团股份有限公司 | Method for preparing 1, 2-methylenedioxybenzene |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106397387A (en) | Method for preparing pepper ring | |
| CN106588758B (en) | Synthesis process of 2-hydrazinopyridine derivative | |
| CN101774879B (en) | Method for simultaneously extracting high-purity beta-methylnaphthalene and indole from coal tar | |
| CN105367370A (en) | Method of extracting squalene from bottom sediment with natural vitamin E extracted | |
| CN105330540A (en) | Preparation method for montelukast sodium intermediate | |
| CN112300071B (en) | Synthetic method of high-purity chloroquine phosphate | |
| CN106397241A (en) | Eco-friendly aftertreatment method of 4-methyl-3-oxo-N-phenylvaleramide | |
| CN106117186B (en) | A kind of preparation method of voriconazole and its intermediate | |
| CN102702122B (en) | Method for preparing tetrazine by oxidizing dihydro tetrazine | |
| CN103819320B (en) | Method for preparing anisaldehyde by using natural anethole as raw material | |
| EP1824811B1 (en) | Process for the purification of benzphetamine hydrochloride | |
| CN102382044A (en) | Purification method for 2,3-dimethylpyridine | |
| CN106966980B (en) | The preparation method of high-purity Eptazocine intermediate | |
| CN105461525B (en) | The preparation of 1,3,5 3 aldehyde radical 1,3,5-trihydroxybenzene and the reuse method of preparation process trifluoroacetic acid | |
| CN104356103A (en) | Synthetic method of 6, 7-dimethoxyl coumarin | |
| CN102382045A (en) | Purification of 2,3-dimethyl pyridine | |
| CN110563693B (en) | Preparation method of pepper ring | |
| CN102408371A (en) | Method for purifying 2,3-dimethyl pyridine | |
| CN114436883A (en) | Method for recovering N, N-dimethylacetamide from multi-component solution system | |
| CN100360506C (en) | 1,2,3,9-tetrahydro-9-methyl-4H-carbazole-4-one preparation method | |
| CN110255656B (en) | Treatment method of industrial wastewater of triazone | |
| CN107585821A (en) | A kind of method of phenolic compound in extraction wastewater | |
| CN113666814B (en) | Synthesis method of high-purity raspberry ketone | |
| CN113603641B (en) | Preparation method of flometoquin | |
| CN114933541B (en) | Method for preparing 2-methylamino-5-chlorobenzophenone |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170215 |
|
| RJ01 | Rejection of invention patent application after publication |