CN114105744A - Method for catalyzing Claisen rearrangement at lower temperature - Google Patents
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- 238000005821 Claisen rearrangement reaction Methods 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 6
- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical compound CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 claims description 15
- WTEVQBCEXWBHNA-UHFFFAOYSA-N Citral Natural products CC(C)=CCCC(C)=CC=O WTEVQBCEXWBHNA-UHFFFAOYSA-N 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 230000008707 rearrangement Effects 0.000 claims description 8
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- PJDVDOYSDZKWPD-UHFFFAOYSA-N 3,3-dimethyl-2-prop-1-en-2-ylpent-4-enal Chemical compound CC(=C)C(C=O)C(C)(C)C=C PJDVDOYSDZKWPD-UHFFFAOYSA-N 0.000 claims description 4
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 claims description 4
- 239000007810 chemical reaction solvent Substances 0.000 claims description 4
- 150000002085 enols Chemical class 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- -1 trimethyl-3-formyl-1, 5-hexadiene Chemical compound 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 21
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000006837 decompression Effects 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 229940043350 citral Drugs 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 125000005336 allyloxy group Chemical group 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- LPIOLZJIOZTRMR-UHFFFAOYSA-N spiro[4.5]dec-8-ene Chemical compound C1CCCC21CC=CCC2 LPIOLZJIOZTRMR-UHFFFAOYSA-N 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000005662 Paraffin oil Substances 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000006462 rearrangement reaction Methods 0.000 description 2
- 125000005017 substituted alkenyl group Chemical group 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- WPFFGMCNILGTEA-UHFFFAOYSA-N 1-spiro[4.5]dec-8-en-9-ylpent-4-en-1-one Chemical compound C1C(C(=O)CCC=C)=CCCC11CCCC1 WPFFGMCNILGTEA-UHFFFAOYSA-N 0.000 description 1
- BAXOFTOLAUCFNW-UHFFFAOYSA-N 1H-indazole Chemical compound C1=CC=C2C=NNC2=C1 BAXOFTOLAUCFNW-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- QQBGXQSMYXJUFF-UHFFFAOYSA-N 4-methyl-1h-pyrrolo[3,2-c]pyridine Chemical compound CC1=NC=CC2=C1C=CN2 QQBGXQSMYXJUFF-UHFFFAOYSA-N 0.000 description 1
- JKDDRTJZRHDYKE-UHFFFAOYSA-N C1=CNP=N1 Chemical compound C1=CNP=N1 JKDDRTJZRHDYKE-UHFFFAOYSA-N 0.000 description 1
- OJLMARCQPSGYNE-UXBLZVDNSA-N Isocitral Chemical compound CC(C)=CC\C=C(/C)CC=O OJLMARCQPSGYNE-UXBLZVDNSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005837 enolization reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002683 reaction inhibitor Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
- C07C45/513—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being an etherified hydroxyl group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/50—Spiro compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a method for catalyzing Claisen rearrangement at a lower temperature, which relates to the field of catalysis. The reaction can reduce production energy consumption, simplify operation and lower equipment requirement.
Description
Technical Field
The invention relates to the field of catalysis, in particular to a method for catalyzing Claisen rearrangement at a lower temperature.
Background
Heating the allyl ether of an enol to 200 ℃ causes an intramolecular rearrangement in which the allyl group migrates from the oxygen atom to the carbon atom, also known as a claisen rearrangement. The claisen rearrangement was initially found in aromatic compounds and later it was found that the reaction could be extended to nonaromatic compounds, the rearrangement of nonaromatic allyl vinyl ethers, which, because of the lack of enolization driving force, stayed in the carbonyl stage, known as aliphatic claisen rearrangement. Therefore, it is an important synthetic method for industrial products, pharmaceuticals, agricultural chemicals, and the like to provide a synthetically useful intermediate. Therefore, most of the Cleisen rearrangement reactions at present need the existence of solvents with high boiling points such as carbitol, paraffin oil, N-dimethylaniline and the like or no solvents, and are carried out at the high temperature of about 150-.
For example, cis/trans-isopentenyl-3-methyl butadiene ether is an important intermediate for synthesizing 3, 7-dimethyl-2, 6-octadienal (natural citral), and the Claisen rearrangement of the substance is a key step of synthesis and can directly influence the yield and quality of citral. The relevant reaction is shown as the following formula:
at present, the rearrangement step is carried out in a high-temperature mode, which directly causes the generation of a large amount of polymers and directly influences the yield; but also can cause the generation of rearrangement isomer and influence the product quality. For example, patent CN108117484 discloses a Claisen rearrangement of cis/trans-isopentenyl-3-methylbutadiene ether by high temperature high pressure flash method by adding one of aluminum hydride, trialkylaluminum and SnCl4 as a catalyst. The method has strict requirements on equipment, overlarge pressure and overhigh temperature. Patent CN106977383 discloses a method for reducing the production of rearrangement isomers by adding esters as rearrangement side reaction inhibitors. However, the method requires a temperature of 150 ℃ or higher, and is large in energy consumption and incapable of inhibiting the generation of high-temperature polymers. Patent CN112225655 discloses the catalysis of Claisen rearrangement of cis/trans-isopentenyl-3-methylbutadiene ether by the addition of azaindole as catalyst. The method reports that the content of the isocitral can be controlled to be about 0.3 percent, but the temperature still needs to reach more than 150 ℃, and polymerization and leftover increase are still inevitable.
For another example, 8- (1- (allyloxy) vinyl) spiro [4.5] dec-7-ene is an intermediate of spirocyclic galbanone (a perfume component), and the compound is subjected to Claisen rearrangement to obtain spirocyclic galbanone, and the synthesis is performed by a high-temperature high-pressure method in the prior art. The relevant reaction is shown as the following formula:
CN108602745 discloses an operation to obtain spiro galbanone by Claisen rearrangement. The method comprises the steps of reacting 8- (1- (allyloxy) vinyl) spiro [4.5] dec-7-ene in paraffin oil at the high temperature of 150 ℃ and the high pressure of 1MPa, and distilling to obtain the spirocyclic galbanone. The reaction equipment has high requirement and large energy consumption, the patent reported yield is about 90 percent, which indicates that about 10 percent of high polymer leftover material is generated; the patent does not wait for the content of the isomer.
Aiming at various problems of high temperature, high pressure, low product quality and the like of the Claisen rearrangement method in the prior art, a method for catalyzing Claisen rearrangement with low temperature and high product quality needs to be found urgently.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for catalyzing Claisen rearrangement at a lower temperature, and the reaction can reduce production energy consumption, simplify operation and simultaneously have lower requirements on equipment.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a method for catalyzing Claisen rearrangement, which uses DAPs as a catalyst to catalyze allyl ether of enol to obtain a Claisen rearrangement product through rearrangement.
The chemical reaction formula is shown as follows:
when either R1 or R2 is alkenyl or substituted alkenyl, the product continues to undergo a Claisen rearrangement, which has the general chemical reaction:
wherein R1 and R2 are selected from hydrogen or a straight or branched alkyl, alkenyl, substituted alkenyl or aryl group containing 1 to 6 carbon atoms; r3 is selected from hydrogen or a straight chain alkyl group containing 1 to 6 carbon atoms, a carbocyclic or spiro ring of 3 to 10 carbon atoms; r4 and R5 are selected from hydrogen or straight chain alkyl groups containing 1 to 6 carbon atoms, and R6 and R7 are selected from hydrogen or straight chain alkyl groups containing 1 to 6 carbon atoms.
Further, the temperature of the catalytic reaction is 50-150 ℃; preferably 80-130 deg.C.
Further, the chemical structural formula of the catalyst DAPs is shown as formula I, formula II or formula III:
Further, the catalyst DAPs is used in an amount of 0.05 to 0.5 mol% (based on the raw material).
Further, the reaction solvent in the catalytic process comprises one or more of paraxylene, mesitylene, n-heptane and toluene.
Further, the adding amount of the reaction solvent is 0.1W-5W; wherein W is the weight of the substrate material.
Further, the reaction can be carried out in the absence of a solvent.
The technical effects obtained by the invention are as follows:
the invention adopts the novel catalyst DAPs to catalyze allyl ether of enol to carry out Claisen rearrangement, directly inhibits the generation of a polymerization product from the reaction process stage, can avoid a complex tower plate rectification method when the product is finally distilled, and can directly adopt conventional high vacuum distillation to obtain a Claisen rearrangement product with the GC purity of more than 98 percent.
Compared with the prior art, the invention reduces the rearrangement reaction temperature, so that the high-temperature polymer caused by the generated polymer is successfully reduced to below 1 percent; the reaction can reduce production energy consumption, simplify operation and lower equipment requirement.
Detailed Description
It should be noted that the raw materials used in the present invention are all common commercial products, and thus the sources thereof are not particularly limited.
Example 1
152.24g (1.0mol) of cis/trans-isopentenyl-3-methylbutadiene ether and a catalyst of the formula:
namely, 105.1mg (0.5mmol) of 2-ethoxy-1,3-dimethyl-2, 3-dihydro-1H-benzol [ d ] [1,3,2] diazaphosphole (0.05 mol percent relative to the raw material cis/trans-isopentenyl-3-methylbutadiene ether) is added into a kettle type reactor, then the reaction kettle is replaced by nitrogen for three times, stirring is started after the replacement is finished, the temperature is raised to about 80 ℃ of the system, and after the reaction is carried out for 40min, the residual of the raw material is detected to be less than 3 percent by GC; starting three groups of decompression pumps, slowly raising the temperature to 110 ℃, keeping the pressure in the kettle at about 400Pa, and carrying out decompression distillation at the temperature of 110 ℃ and 120 ℃ until no liquid drops flow out. The distillate was collected to give 139.9g of a mixture of 3, 3-dimethyl-2-isopropenyl-4-pentene-1-aldehyde (isomer) and 3, 7-dimethyl-2, 6-octadienal (citral), with a yield of 90% and a GC purity of 47.3% (isomer); 51.4% (citral).
The relevant chemical reaction formula is shown as the following formula:
example 2
1522.4g of toluene, 152.24g (1.0mol) of cis/trans-isopentenyl-3-methylbutadiene ether, and a catalyst of the formula:
namely 2,5,6-trimethoxy-1,3-dimethyl-2, 3-dihydrazide-1H-benzol [ d ] [1,3,2] diazaphosphole1281.25mg (5mmol) (0.5 mol% relative to the raw material cis/trans-isopentenyl-3-methyl butadiene ether) is added into a kettle type reactor, then the reaction kettle is replaced by nitrogen for three times, after the replacement is finished, stirring is started, the temperature is raised to about 120 ℃ of the system, and after the reaction is carried out for 60min, no residue is left in the raw material through GC detection; starting a group of decompression pumps, decompressing and distilling 1500pa of pressure in the kettle to obtain a low-boiling point solvent p-xylene, and keeping the temperature at 50-80 ℃; reducing the pressure until no liquid drops flow out; starting three groups of decompression pumps, slowly raising the temperature to 110 ℃, keeping the pressure in the kettle at about 500Pa, and keeping the temperature in the kettle at 110-140 ℃ for decompression distillation until no liquid drops flow out. The distillate was collected to obtain 147.7g of a mixture of 3, 3-dimethyl-2-isopropenyl-4-pentene-1-aldehyde (isomer) and 3, 7-dimethyl-2, 6-octadienal (citral), with a yield of 97% and a GC purity of 40.1% (isomer); 59.4% (citral).
The relevant chemical reaction formula is shown as the following formula:
example 3
1091g of xylene, 8- (1- (allyloxy) vinyl) spiro [4.5] dec-7-ene 218.34g (1mol), a catalyst represented by the following formula:
namely 2,5,6-triethoxy-1,3-dimethyl-2, 3-dihydrazide-1H-benzod ] [1,3,2] diazaphosphahole 298.32mg (1mmol), adding the mixture into a kettle type reactor, then carrying out nitrogen replacement on the reaction kettle for three times, starting stirring after the replacement is finished, heating to the system temperature of about 70 ℃, and detecting that no residue exists in the raw materials by GC after the reaction is carried out for 5 hours. Starting a group of decompression pumps, decompressing and distilling 1500pa of pressure in the kettle to obtain a low-boiling-point solvent xylene, decompressing until no liquid drops flow out; starting three groups of decompression pumps, slowly raising the temperature to 130 ℃, keeping the pressure in the kettle at about 300Pa, and carrying out decompression distillation at the temperature of 130 ℃ in the kettle until no liquid drops flow out. Collecting distillate to obtain 209.7g of spirocyclic galbanone, wherein the yield is 96%, and the GC purity is 98.88%; isomer 0.56%.
The relevant chemical reaction formula is shown as the following formula:
comparative example 1
Adding 680g of trimethylbenzene and 152.24g (1.0mol) of cis/trans-isopentenyl-3-methyl butadiene ether into a kettle type reactor, then carrying out nitrogen replacement on the reaction kettle for three times, starting stirring after the replacement is finished, heating to the system temperature of about 150 ℃, reacting for 30min, cooling to 50 ℃, and distilling the solvent under reduced pressure; the temperature was then raised to 90 ℃ and the product was pressed off while maintaining a pressure of 300 Pa. The distillate was collected to obtain 107.38g of a mixture of 3, 3-dimethyl-2-isopropenyl-4-pentene-1-aldehyde (isomer) and 3, 7-dimethyl-2, 6-octadienal (citral), the yield was 70.3%, and the GC purity was 33.0% (isomer); 37.7% (citral).
Comparative example 2
The only difference from example 1 is that the catalyst was replaced by 4-methyl-5-azaindole, the other conditions were not changed, and the resulting 3, 7-dimethyl-2, 6-octadienal mixture was obtained. The yield was 33%, a large amount of the raw material was not reacted, the GC purity was 50.3%, and the isomer content was 40.4%.
Finally, it should be noted that the above-mentioned contents are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, and that the simple modifications or equivalent substitutions of the technical solutions of the present invention by those of ordinary skill in the art can be made without departing from the spirit and scope of the technical solutions of the present invention.
Claims (8)
1. A method of catalyzing a Claisen rearrangement, comprising: the catalysts DAPs are used to catalyze the allyl ether of an enol to obtain a Claisen rearrangement product by rearrangement.
2. The process of catalyzing a Claisen rearrangement according to claim 1, wherein: the temperature of the catalytic reaction is 50-150 ℃.
3. The process of catalyzing a Claisen rearrangement according to claim 1, wherein: the chemical structural formula of the catalyst DAPs is shown as formula I, formula II or formula III:
4. The process of catalyzing a Claisen rearrangement according to claim 1, wherein: the dosage of the catalyst DAPs is 0.05-0.5 mol%.
5. The process of catalyzing a Claisen rearrangement according to claim 1, wherein: the reaction solvent in the catalysis process comprises one or more of paraxylene, mesitylene, n-heptane and toluene.
6. The process of catalyzing a Claisen rearrangement according to claim 5, wherein: the addition amount of the reaction solvent is 0.1W-5W; wherein W is the weight of the substrate material.
7. The process of catalyzing a Claisen rearrangement according to claim 1, wherein: the catalytic process may be carried out in the absence of a solvent.
8. A method for synthesizing 3, 7-dimethyl-2, 6-octadienal, which is characterized by comprising the following steps: the method comprises the following steps:
(1) obtaining 2,4, 4-trimethyl-3-formyl-1, 5-hexadiene by the process of catalyzing a Claisen rearrangement of claim 1;
(2) and (2) carrying out Claisen rearrangement on the 2,4,4_ trimethyl-3-formyl-1, 5-hexadiene obtained in the step (1) to obtain 3, 7-dimethyl-2, 6-octadienal.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114478413A (en) * | 2022-01-14 | 2022-05-13 | 北京富盛嘉华医药科技有限公司 | Preparation method and application of 2- (2' -hydroxy-3 ' -methallyl-5 ' -methylphenyl) benzotriazole |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108117484A (en) * | 2017-12-15 | 2018-06-05 | 万华化学集团股份有限公司 | A kind of preparation method of citral |
| CN112225655A (en) * | 2020-09-10 | 2021-01-15 | 万华化学集团股份有限公司 | Preparation method of citral |
| CN113563173A (en) * | 2021-08-03 | 2021-10-29 | 万华化学集团股份有限公司 | Preparation method of citral |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108117484A (en) * | 2017-12-15 | 2018-06-05 | 万华化学集团股份有限公司 | A kind of preparation method of citral |
| CN112225655A (en) * | 2020-09-10 | 2021-01-15 | 万华化学集团股份有限公司 | Preparation method of citral |
| CN113563173A (en) * | 2021-08-03 | 2021-10-29 | 万华化学集团股份有限公司 | Preparation method of citral |
Non-Patent Citations (2)
| Title |
|---|
| F. YUSHRA THANZEEL等: "Quantitative Chirality and Concentration Sensing of Alcohols, Diols, Hydroxy Acids, Amines and Amino Alcohols using Chlorophosphite Sensors in a Relay Assay", ANGEW. CHEM. INT. ED., vol. 59, pages 21382 - 21386, XP072094397, DOI: 10.1002/anie.202005324 * |
| JOHN H. REED等: "A 1, 3, 2-Diazaphospholene-Catalyzed Reductive Claisen Rearrangement", ANGEW. CHEM. INT. ED., vol. 58, pages 8893 - 8897 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114478413A (en) * | 2022-01-14 | 2022-05-13 | 北京富盛嘉华医药科技有限公司 | Preparation method and application of 2- (2' -hydroxy-3 ' -methallyl-5 ' -methylphenyl) benzotriazole |
| CN114478413B (en) * | 2022-01-14 | 2023-06-23 | 北京富盛嘉华医药科技有限公司 | Preparation method and application of 2- (2 ' -hydroxy-3 ' -methallyl-5 ' -methylphenyl) benzotriazole |
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