CN104961616B - The method of purification of longifolene - Google Patents
The method of purification of longifolene Download PDFInfo
- Publication number
- CN104961616B CN104961616B CN201510277374.2A CN201510277374A CN104961616B CN 104961616 B CN104961616 B CN 104961616B CN 201510277374 A CN201510277374 A CN 201510277374A CN 104961616 B CN104961616 B CN 104961616B
- Authority
- CN
- China
- Prior art keywords
- longifolene
- crude product
- present
- hours
- reactor
- 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.)
- Expired - Fee Related
Links
- ZPUKHRHPJKNORC-UHFFFAOYSA-N Longifolene Natural products CC1(C)CCCC2(C)C3CCC1(C3)C2=C ZPUKHRHPJKNORC-UHFFFAOYSA-N 0.000 title claims abstract description 55
- PDSNLYSELAIEBU-UHFFFAOYSA-N Longifolene Chemical compound C1CCC(C)(C)C2C3CCC2C1(C)C3=C PDSNLYSELAIEBU-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000000746 purification Methods 0.000 title claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 18
- 239000012043 crude product Substances 0.000 claims abstract description 15
- 239000000047 product Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000013019 agitation Methods 0.000 claims description 7
- 235000011007 phosphoric acid Nutrition 0.000 claims description 7
- 150000003016 phosphoric acids Chemical class 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001293 FEMA 3089 Substances 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 description 3
- WRLRISOTNFYPMU-UHFFFAOYSA-N [S].CC1=CC=CC=C1 Chemical compound [S].CC1=CC=CC=C1 WRLRISOTNFYPMU-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- LGSKOQUJWNADCQ-BONVTDFDSA-N (-)-isolongifolen-9-one Chemical compound C([C@@H](C1)C2(C)C)C[C@]31C2=CC(=O)CC3(C)C LGSKOQUJWNADCQ-BONVTDFDSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- 240000003421 Dianthus chinensis Species 0.000 description 1
- 241000779819 Syncarpia glomulifera Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- 239000008396 flotation agent Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- -1 longifolene Alkene Chemical class 0.000 description 1
- 239000001739 pinus spp. Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 229940036248 turpentine Drugs 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a kind of method of purification of longifolene, belongs to turpentine oil deep process technology field.The present invention includes first being reacted pending longifolene with solid phosphoric acid catalyst, and the material for obtaining reaction is evaporated under reduced pressure to obtain longifolene crude product, then it is transferred in another reactor, add acetum, hydroquinones and p-methyl benzenesulfonic acid, are stirred, after stopping stirring, standing separation goes out material bed, and obtained material is then carried out into rectifying after washing.The present invention has gentle reaction condition, technique and simple flow, using the advantages of equipment is few, cost is low, and using the present invention, the purity of longifolene product can be made to reach more than 90%.
Description
Technical field
The invention belongs to turpentine oil deep process technology field, more particularly to a kind of method of purification of longifolene.
Background technology
Longifolene is a kind of natural perfume material extracted from heavy duty turpentine oil, has special chemism, is synthesis
Resin, synthetic perfume, flotation agent and the raw material of organic synthesis, isolonglifolene, Isolongifolenone can be manufactured using longifolene
Deng product, the allotment for essence can replace some expensive spices.
In the preparation process of longifolene, because longifolene and carypohyllene boiling point in heavy turpentine approach, obtained length
10%~12% carypohyllene is usually contained in leaf alkene product so that the purity of longifolene is only 65%~68% or so, largely
Reduction longifolene use value.Now, try generally by the method for physics and chemistry by the China pink in thick longifolene
Alkene eliminates, so as to reach the purpose for improving longifolene purity.For example, some is taken carypohyllene catalytic isomerization into other sequiterpenes
Alkene reduces carypohyllene content in heavy oil, and the refining effect of this method is not preferable；Some uses acid-exchange resin
Carry out hydration reaction and eliminate carypohyllene, also eliminate carypohyllene using elution tower elution processes, but these methods are mostly in the presence of anti-
Answer the problem of condition harshness, complex process, equipment requirement are high, cost is high.
The content of the invention
Present invention solves the technical problem that being to provide a kind of method of purification of longifolene, the method for purification can solve existing
The refining effect of longifolene is undesirable, and purifying technique is complicated, the problem of severe reaction conditions.
In order to solve the above-mentioned technical problem, the technical solution adopted in the present invention is：
It comprises the following steps：
A. by weight, under agitation, 100 parts of pending longifolene is put into reactor, with 1 part~5
Part solid phosphoric acid is used as catalyst, react at 120 DEG C~135 DEG C 1 hour~3 hours, then stops reacting, vacuum distillation,
Obtain longifolene crude product；
B. the longifolene crude product obtained after step A is handled is put into another reactor, is first heated to 40 DEG C~60 DEG C, so
Sequentially add afterwards in advance be preheated to 40 DEG C~60 DEG C 12 parts~15 parts concentration be 1mol/L acetum, 4 parts~6 parts it is right
Benzenediol and 8 parts~10 parts p-methyl benzenesulfonic acid, are stirred, and stop stirring after 6 hours~10 hours, and standing separation goes out material
Layer, then carries out rectifying by obtained material, obtains longifolene finished product after washing.
Due to using above-mentioned technical proposal, the beneficial effect that the present invention obtains is：
1. the present invention has gentle reaction condition, technique and simple flow, utilizes the advantages of equipment is few, cost is low.
2. using the present invention, the purity of longifolene product can be made to reach more than 90%.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described, and protection scope of the present invention is not only limited to
In following examples.
Embodiment 1
The present embodiment comprises the following steps：
A. under agitation, 1000g pending longifolene is put into reactor, using 10g solid phosphoric acids as urging
Agent, reacted at 120 DEG C 3 hours, then stop reaction, be evaporated under reduced pressure, obtain longifolene crude product；
B. the longifolene crude product obtained after step A is handled is put into another reactor, is first heated to 40 DEG C, then again according to
The 120g concentration that secondary addition is preheated to 40 DEG C in advance is 1mol/L acetum, 60g hydroquinones and 80g to toluene sulphur
Acid, it is stirred, stops stirring after 6 hours, standing separation goes out material bed, and obtained material is then carried out into essence after washing
Evaporate, obtain longifolene finished product.
Longifolene product after the present embodiment is handled, the content of its longifolene bring up to 90%.
Embodiment 2
The present embodiment comprises the following steps：
A. under agitation, 1000g pending longifolene is put into reactor, using 50g solid phosphoric acids as urging
Agent, reacted at 125 DEG C 2 hours, then stop reaction, be evaporated under reduced pressure, obtain longifolene crude product；
B. the longifolene crude product obtained after step A is handled is put into another reactor, is first heated to 60 DEG C, then again according to
The 150g concentration that secondary addition is preheated to 60 DEG C in advance is 1mol/L acetum, 40g hydroquinones and 90g to toluene sulphur
Acid, it is stirred, stops stirring after 10 hours, standing separation goes out material bed, and obtained material is then carried out into essence after washing
Evaporate, obtain longifolene finished product.
Longifolene product after the present embodiment is handled, the content of its longifolene bring up to 91%.
Embodiment 3
The present embodiment comprises the following steps：
A. under agitation, 1000g pending longifolene is put into reactor, using 30g solid phosphoric acids as urging
Agent, reacted at 135 DEG C 1 hour, then stop reaction, be evaporated under reduced pressure, obtain longifolene crude product；
B. the longifolene crude product obtained after step A is handled is put into another reactor, is first heated to 50 DEG C, then again according to
The 130g concentration that secondary addition is preheated to 50 DEG C in advance is 1mol/L acetum, 50g hydroquinones and 100g to toluene
Sulfonic acid, it is stirred, stops stirring after 8 hours, standing separation goes out material bed, and obtained material is then carried out into essence after washing
Evaporate, obtain longifolene finished product.
Longifolene product after the present embodiment is handled, the content of its longifolene bring up to 90.5%.
Claims (3)
1. a kind of method of purification of longifolene, it is characterised in that comprise the following steps：
A. under agitation, 1000g pending longifolene is put into reactor, using 10g solid phosphoric acids as catalyst,
Reacted at 120 DEG C 3 hours, then stop reaction, be evaporated under reduced pressure, obtain longifolene crude product；
B. the longifolene crude product obtained after step A is handled is put into another reactor, is first heated to 40 DEG C, is then added successively again
Acetum, 60g hydroquinones and the 80g p-methyl benzenesulfonic acid that the 120g concentration for entering to be preheated to 40 DEG C in advance is 1mol/L,
It is stirred, stops stirring after 6 hours, standing separation goes out material bed, and obtained material is then carried out into rectifying after washing, obtained
To longifolene finished product.
2. a kind of method of purification of longifolene, it is characterised in that comprise the following steps：
A. under agitation, 1000g pending longifolene is put into reactor, using 50g solid phosphoric acids as catalyst,
Reacted at 125 DEG C 2 hours, then stop reaction, be evaporated under reduced pressure, obtain longifolene crude product；
B. the longifolene crude product obtained after step A is handled is put into another reactor, is first heated to 60 DEG C, is then added successively again
Acetum, 40g hydroquinones and the 90g p-methyl benzenesulfonic acid that the 150g concentration for entering to be preheated to 60 DEG C in advance is 1mol/L,
It is stirred, stops stirring after 10 hours, standing separation goes out material bed, and obtained material is then carried out into rectifying after washing,
Obtain longifolene finished product.
3. a kind of method of purification of longifolene, it is characterised in that comprise the following steps：
A. under agitation, 1000g pending longifolene is put into reactor, using 30g solid phosphoric acids as catalyst,
Reacted at 135 DEG C 1 hour, then stop reaction, be evaporated under reduced pressure, obtain longifolene crude product；
B. the longifolene crude product obtained after step A is handled is put into another reactor, is first heated to 50 DEG C, is then added successively again
Acetum, 50g hydroquinones and the 100g p-methyl benzenesulfonic acid that the 130g concentration for entering to be preheated to 50 DEG C in advance is 1mol/L,
It is stirred, stops stirring after 8 hours, standing separation goes out material bed, and obtained material is then carried out into rectifying after washing, obtained
To longifolene finished product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510277374.2A CN104961616B (en) | 2015-05-27 | 2015-05-27 | The method of purification of longifolene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510277374.2A CN104961616B (en) | 2015-05-27 | 2015-05-27 | The method of purification of longifolene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104961616A CN104961616A (en) | 2015-10-07 |
| CN104961616B true CN104961616B (en) | 2018-03-13 |
Family
ID=54215744
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510277374.2A Expired - Fee Related CN104961616B (en) | 2015-05-27 | 2015-05-27 | The method of purification of longifolene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104961616B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106083517A (en) * | 2016-06-28 | 2016-11-09 | 广西梧松林化集团有限公司 | The preparation method of high-purity longifolene |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104193579A (en) * | 2014-07-25 | 2014-12-10 | 广西梧州松脂股份有限公司 | Purification method for longifolene |
-
2015
- 2015-05-27 CN CN201510277374.2A patent/CN104961616B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN104961616A (en) | 2015-10-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104496778B (en) | A kind of solid acid alkali catalytic synthesizes the method for raspberry ketone | |
| CN103467475B (en) | The purification process of 1, 8-Cineole | |
| CN104151128A (en) | Preparation method of isolongifolene | |
| CN108586207A (en) | A kind of separating technology extracting 2,4- xylenols and 2,5- xylenols from crude phenols | |
| CN101823998B (en) | Pollution-free production process for ethoxy quinoline by coupling reactor and simulation moving bed | |
| CN109761851A (en) | A kind of preparation method of isophthalodinitrile | |
| CN104193579A (en) | Purification method for longifolene | |
| CN104961616B (en) | The method of purification of longifolene | |
| CN106542970A (en) | The method that a kind of synthesis of dicyclopentadiene phenol resin and feedstock circulation are utilized | |
| CN102731333B (en) | Method for preparing tetracaine | |
| CN104909976A (en) | Longifolene purification method | |
| CN108164395A (en) | A kind of synthetic method of terpinol and its application | |
| CN104892410B (en) | A kind of methyl acrylate waste oil recovery process | |
| CN112159300A (en) | Method for extracting squalene from plant deodorized distillate | |
| CN101125827A (en) | Method for preparing 3-mercaptopropionic acid | |
| CN104529746A (en) | Method for synthesizing dimer acid by compounding catalyst | |
| CN104447199A (en) | Method for preparing isopropanol by salt-adopted extraction rectification-based separation of acetone hydrogenation reaction products | |
| CN103288641B (en) | A kind of synthetic method of Rocryl 410 | |
| CN102351633A (en) | Preparation method of p-cymene | |
| CN105693658A (en) | Stearolactone synthesis process | |
| CN104710308A (en) | Synthesis method of ethyl trifluoroacetate | |
| CN112023979A (en) | Catalyst for synthesizing 2-tert-butyl aniline and preparation method and application thereof | |
| CN105038602B (en) | The method of the miscellaneous many rosin catalyzed polymerizations of Inorganic-organic Hybrid Material of bisgallic acid type | |
| CN104355976B (en) | A kind of method of acetone through one-step method synthesis mesityl oxide | |
| CN104177234B (en) | The refined purifying plant of a kind of by-product diisopropyl ether in isopropanol produces and method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180313 Termination date: 20190527 |