CN106986848B - The method that base catalysis prepares 2- hydroxyl cyclohexadienylidene acetic acid enol lactone - Google Patents
The method that base catalysis prepares 2- hydroxyl cyclohexadienylidene acetic acid enol lactone Download PDFInfo
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- cyclohexadienylidene
- acetic acid
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- -1 2- hydroxyl cyclohexadienylidene acetic acid enol lactone Chemical class 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000005815 base catalysis Methods 0.000 title claims abstract description 16
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims abstract description 68
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 238000010792 warming Methods 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 238000009413 insulation Methods 0.000 claims abstract description 10
- 238000005292 vacuum distillation Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 230000009467 reduction Effects 0.000 claims abstract description 7
- 238000009834 vaporization Methods 0.000 claims abstract description 7
- 230000008016 vaporization Effects 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 125000002243 cyclohexanonyl group Chemical group *C1(*)C(=O)C(*)(*)C(*)(*)C(*)(*)C1(*)* 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 17
- 239000007864 aqueous solution Substances 0.000 description 7
- 230000006837 decompression Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- 238000007171 acid catalysis Methods 0.000 description 3
- IANQTJSKSUMEQM-UHFFFAOYSA-N benzofuran Natural products C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000006280 Rosenmund reaction Methods 0.000 description 1
- WJEIYVAPNMUNIU-UHFFFAOYSA-N [Na].OC(O)=O Chemical compound [Na].OC(O)=O WJEIYVAPNMUNIU-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000006273 synthetic pesticide Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
- C07D307/82—Benzo [b] furans; Hydrogenated benzo [b] furans with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
- C07D307/83—Oxygen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of methods that base catalysis prepares 2- hydroxyl cyclohexadienylidene acetic acid enol lactone, it is 45~55% glyoxalic acid solutions as raw material using cyclohexanone and mass concentration, the following steps are included: basic catalyst is added in glyoxalic acid solution, it is warming up to 90 DEG C of dropwise addition cyclohexanone, 1~2h of insulation reaction after 90~130 DEG C are warming up to after being added dropwise；The mass ratio of the basic catalyst and glyoxalic acid solution is 1~20%；The molar ratio 1.2:1 of cyclohexanone and glyoxalic acid；After reaction, resulting reaction solution is evaporated under reduced pressure, collects and evaporates resulting mixed liquor；Reaction solution after reduction vaporization is cooled to 60 ± 5 DEG C, and vacuum distillation obtains 2- hydroxyl cyclohexadienylidene acetic acid enol lactone.
Description
Technical field
The present invention relates to a kind of methods for preparing 2- hydroxyl cyclohexadienylidene acetic acid enol lactone, belong to organic synthesis neck
Domain.
Background technique
2- coumarone, also known as 3H-2- benzofuran-2-ones are being agriculturally the important foundation raw material of synthetic pesticide, 2-
Hydroxyl cyclohexadienylidene acetic acid enol lactone is the important intermediate for synthesizing 2- coumarone, Stanek Michael et al. (EP
Describe one kind with Jean-Claude Vallejos et al. (US005773632) 1449838A1) with 2- hydroxyl Asia cyclohexene
Guanidine-acetic acid enol lactone is the method that catalytic material synthesizes 2- coumarone, and catalytic efficiency is higher, can satisfy industrialized production
It is required that.
So far, the synthetic method of 2- hydroxyl cyclohexadienylidene acetic acid enol lactone reported in the literature has following several
Kind:
1), acetic acid catalysis method:
Jean-Claude Vallejos et al. (US005616733) once reported made of the pure acetic acid of 3520g (54.2mol) it is molten
Heating reflux reaction for 24 hours, is concentrated under reduced pressure under agent, 736g cyclohexanone (7.5mol) and 80% (weight) glyoxalic acid (7.5mol) normal pressure
3520g mixed liquor is obtained afterwards, wherein containing 64.35g 2- hydroxyl cyclohexadienylidene acetic acid enol lactone, conversion ratio (6.3%) is low,
Waste liquid is more.
2), 37% (quality) HCL aqueous solution two-step catalysis method
Jean-Claude Vallejos et al. (US005773632) later again once with 147g cyclohexanone (1.5mol) and
148g 50% (quality) glyoxalic acid (1mol) aqueous solution is raw material, adds it to 10g 37% (quality) hydrochloric acid (0.1mol)
In 10g water, 2h is heated to reflux under normal pressure and obtains reaction mixture.
Reaction mixture is added in 250ml paraxylene, adds 10g p-methyl benzenesulfonic acid and carries out azeotropic distillation, after neutralization
Vacuum distillation obtains 118g 2- hydroxyl cyclohexadienylidene acetic acid enol lactone, and yield is 87% (with glyoxalic acid molar amount).Instead
Answer process longer, in addition to this, reaction will also remove extra cyclohexanone after completing, and subsequent also introduce organic solvent
Paraxylene azeotropic water removing generates a large amount of waste water.
The method of many document reports synthesis enol lactone class compound and path, such as K.W.Ros enmund,
Arch.Pharm,287,441(1954)；Yu Wang,Hua Hsueh Hsueh Pao,26(2),84-99(1960)；
Nakano,J..C.s.,Chem.Commun.,1981,815-816；Yu.A.Arbuzov,Zh.Obshch.Khim.32,3676-
81(1962)；A.Mondon et al,Chem.Ber,96,826,(1963)；A.W.Noltes et al,
Rec.Trav.Chim.,80,1334(1961)；M.N.Kolosov et al,Zhur.Obschei Khim.,32,2987,
(1962)。
But these documents all do not provide a kind of side of high yield production 2- hydroxyl cyclohexadienylidene acetic acid enol lactone
Method.
Summary of the invention
The technical problem to be solved in the present invention is to provide in a kind of base catalysis preparation 2- hydroxyl cyclohexadienylidene acetic acid enol
The method of ester；There is simple process, high income, high-quality using this method production 2- hydroxyl cyclohexadienylidene acetic acid enol lactone
With feature easy to industrialized production.
In order to solve the above technical problem, the present invention provides a kind of base catalysis to prepare 2- hydroxyl cyclohexadienylidene acetic acid enol
The method of lactone is 45~55% (preferably 50%) glyoxalic acid solutions as raw material using cyclohexanone and mass concentration, including with
Lower step:
Basic catalyst is added in glyoxalic acid solution, 90 DEG C of dropwise addition cyclohexanone are warming up to, (is added dropwise after being added dropwise
Time control at 10 ± 2 minutes) be warming up to 90~130 DEG C after 1~2h of insulation reaction；The basic catalyst and glyoxalic acid are water-soluble
The mass ratio of liquid is 1~20%；The molar ratio 1.2:1 of cyclohexanone and glyoxalic acid；
After reaction, (water pump decompression, 0.01Mpa, it is therefore an objective to steam in reaction solution is evaporated under reduced pressure in resulting reaction solution
Extra cyclohexanone and water), it collects and evaporates resulting mixed liquor；
Reaction solution after reduction vaporization is cooled to 60 ± 5 DEG C, and vacuum distillation (is evaporated under reduced pressure, 20mmHg, 130 for oil pump
DEG C), obtain 2- hydroxyl cyclohexadienylidene acetic acid enol lactone.
The improvement of the method for 2- hydroxyl cyclohexadienylidene acetic acid enol lactone is prepared as base catalysis of the invention: evaporation institute
The mixed liquor obtained is layered after standing, and upper layer is cyclohexanone, be can be recycled；Lower layer is water.
The further improvements in methods of 2- hydroxyl cyclohexadienylidene acetic acid enol lactone are prepared as base catalysis of the invention:
Basic catalyst is sodium carbonate, potassium carbonate, sodium bicarbonate, saleratus, sodium hydroxide, potassium hydroxide.
The further improvements in methods of 2- hydroxyl cyclohexadienylidene acetic acid enol lactone are prepared as base catalysis of the invention:
The mass ratio of the basic catalyst and glyoxalic acid solution is 2.5~10%.
The further improvements in methods of 2- hydroxyl cyclohexadienylidene acetic acid enol lactone are prepared as base catalysis of the invention:
The temperature of insulation reaction is 100~130 DEG C.
Cyclohexanone and glyoxalic acid solution are prepared reacting coarse product by the present invention in the presence of base catalyst, in reaction process
Supplement water and other organic solvents are not needed.
In the present invention, base catalyst is preferably sodium carbonate, sodium bicarbonate, potassium carbonate, saleratus, more preferably carbonic acid
Sodium.
Cyclohexanone and glyoxalic acid of the invention generates 2- hydroxyl cyclohexadienylidene acetic acid enol lactone under the action of catalyst
Reaction equation it is as follows:
Preferred version of the invention are as follows:
Using cyclohexanone and 50% (quality) glyoxalic acid solution as raw material.By 5% (opposite glyoxalic acid solution quality) carbon
Sour sodium is added to 50% (quality) glyoxalic acid solution, is warming up to 90 DEG C, and the cyclohexanone (molar ratio of cyclohexanone and glyoxalic acid is added dropwise
1:1.2), it is added dropwise after being added dropwise after being warming up to 110 DEG C, insulation reaction 1h, water pump decompression steams the extra ring of reaction solution
Hexanone and water, collection obtains mixed liquor, and after standing overnight, layering obtains extra cyclohexanone (upper layer), gives over to recycling.It is surplus
Remaining reaction solution is cooled to 60 DEG C, uses oil pump vacuum distillation (20mmHg, 130 DEG C) instead and obtains product 2- hydroxyl cyclohexadienylidene second
Sour enol lactone.
The present invention has following technical advantage:
1, high income, the present invention can be obtained by 2- hydroxyl cyclohexadienylidene acetic acid enol lactone by single step reaction, produce
Product are stablized, purity is high.
2, simple process.The present invention only needs a step to complete, and the reaction time is short, does not need to introduce water and organic molten in reaction
Agent, is easy to control and technique is relatively easy, can satisfy the requirement of industrialization large-scale production completely.
3, preparation cost is low.The raw materials used in the present invention is inexpensive, and preparation flow is short, high production efficiency.
4, the reaction time is short；Relative to the prior art informed in above-mentioned background technique, the reaction time is substantially reduced.
Specific embodiment
The present invention is described further combined with specific embodiments below, but protection scope of the present invention is not limited in
This.
A kind of method that embodiment 1, base catalysis prepare 2- hydroxyl cyclohexadienylidene acetic acid enol lactone:
It is 50% (quality %) glyoxalic acid (1moL) aqueous solution 148g that concentration is added in the round-bottomed flask of volume 500mL,
7.4g (0.07mol) sodium carbonate, pH value is about 12.6 at this time；90 DEG C are warming up to, is added dropwise 117.6g cyclohexanone (1.2moL), is added dropwise
It finishes after (time for adding is about 10 minutes) be warming up to 110 DEG C, insulation reaction 1h, water pump decompression (pressure of 0.01MPa) steams
Reaction solution extra cyclohexanone and water, collection obtain mixed liquor 90mL, after standing overnight, layering obtain extra cyclohexanone (on
Layer) 20mL, recycling is given over to, lower layer is water.Reaction solution after reduction vaporization is cooled to 60 DEG C, uses oil pump vacuum distillation instead
(20mmHg, 130 DEG C) obtains 127.5g 2- hydroxyl cyclohexadienylidene acetic acid enol lactone, yield 93.4%.
A kind of method that embodiment 2, base catalysis prepare 2- hydroxyl cyclohexadienylidene acetic acid enol lactone:
50% (quality) glyoxalic acid (1moL) solution 148g, 4.4g (0.05mol) is added in the round-bottomed flask of volume 500mL
Sodium bicarbonate, pH value is about 11.3 at this time；90 DEG C are warming up to, 117.6g (1.2moL) cyclohexanone is added dropwise, is added dropwise and is warming up to
After 130 DEG C, insulation reaction 1.5h, water pump decompression steams reaction solution extra cyclohexanone and water, and collection obtains mixed liquor 91mL, quiet
After setting overnight, layering obtains extra cyclohexanone (upper layer) 20mL, gives over to recycling.Reaction solution after reduction vaporization is cooled to
It 60 DEG C or so, uses oil pump vacuum distillation (20mmHg, 130 DEG C) instead, obtains in 115.6g 2- hydroxyl cyclohexadienylidene acetic acid enol
Ester, yield 90.0%.
A kind of method that embodiment 3, base catalysis prepare 2- hydroxyl cyclohexadienylidene acetic acid enol lactone:
50% (quality) glyoxalic acid (1moL) solution 148g, 8g (0.06mol) carbon is added in the round-bottomed flask of volume 500mL
Sour potassium, pH value is about 13.2 at this time；90 DEG C are warming up to, 117.6g (1.2moL) cyclohexanone is added dropwise, is added dropwise and is warming up to 100 DEG C
Afterwards, insulation reaction 2h, water pump decompression steam reaction solution extra cyclohexanone and water, and collection obtains mixed liquor 91mL, stands overnight
Afterwards, layering obtains extra cyclohexanone (upper layer) 20mL, gives over to recycling.Reaction solution after reduction vaporization is cooled to 60 DEG C,
It uses oil pump vacuum distillation (20mmHg, 130 DEG C) instead, obtains 111.5g 2- hydroxyl cyclohexadienylidene acetic acid enol lactone, yield is
92.0%.
A kind of method that embodiment 4, base catalysis prepare 2- hydroxyl cyclohexadienylidene acetic acid enol lactone:
50% (quality) glyoxalic acid (1moL) solution 148g, 14.8g is added in the round-bottomed flask of volume 500mL
(0.15mol) saleratus, pH value is about 13.5 at this time；90 DEG C are warming up to, 117.6g (1.2moL) cyclohexanone is added dropwise, drips
Finish after being warming up to 120 DEG C, insulation reaction 1h, water pump decompression steams extra cyclohexanone and water, and collection obtains mixed liquor 91mL, quiet
After setting overnight, layering obtains extra cyclohexanone (upper layer) 20mL, gives over to recycling.Reaction solution after reduction vaporization is cooled to
It 60 DEG C, uses oil pump vacuum distillation (20mmHg, 130 DEG C) instead and obtains 120.2g 2- hydroxyl cyclohexadienylidene acetic acid enol lactone, receive
Rate is 94.4%.
7.4g sodium carbonate in embodiment 1 is changed to 5.6g sodium hydroxide by embodiment 5, to make pH value with embodiment 1；
Remaining is equal to embodiment 1.
Acquired results are as follows: 2- hydroxyl cyclohexadienylidene acetic acid enol lactone 102.4g, yield 75.3%.
7.4g sodium carbonate in embodiment 1 is changed to 7.4g potassium hydroxide by embodiment 6, to make pH value with embodiment 1；
Remaining is equal to embodiment 1.
Acquired results are as follows: 2- hydroxyl cyclohexadienylidene acetic acid enol lactone 80.2g, yield 59.0%.
Comparative example 1-1:7% (quality) HCL aqueous solution catalysis preparation 2- hydroxyl cyclohexadienylidene acetic acid enol lactone:
By " sodium carbonate " in embodiment 1 be changed to as " background technique 2) --- 37% (quality) HCL aqueous solution two-step catalysis
Described in method " " 37% (quality) HCL aqueous solution ", mole is constant；Remaining is equal to embodiment 1.
Acquired results are as follows: 2- hydroxyl cyclohexadienylidene acetic acid enol lactone 63.2g, yield 46.5%.
Comparative example 1-2: Catalyzed by p-Toluenesulfonic Acid prepares 2- hydroxyl cyclohexadienylidene acetic acid enol lactone:
By " sodium carbonate " in embodiment 1 be changed to as " background technique 2) --- 37% (quality) HCL aqueous solution two-step catalysis
Described in method " " p-methyl benzenesulfonic acid ", mole is constant；Remaining is equal to embodiment 1.
Acquired results are as follows: 2- hydroxyl cyclohexadienylidene acetic acid enol lactone 78.2g, yield 57.5%.
Comparative example 1-3: acetic acid catalysis prepares 2- hydroxyl cyclohexadienylidene acetic acid enol lactone:
" sodium carbonate " in embodiment 1 is changed to " acetic acid " as described in " background technique 1) --- acetic acid catalysis method ", is rubbed
Your amount is constant, i.e., acetic acid is 0.07mol；Remaining is equal to embodiment 1.
Acquired results are as follows: 2- hydroxyl cyclohexadienylidene acetic acid enol lactone 25.5g, yield 18.8%.
Comparative example 2-1, the dosage of cyclohexanone in embodiment 1 is changed to 1moL by 1.2moL；Remaining is equal to embodiment 1.
Acquired results are as follows: 2- hydroxyl cyclohexadienylidene acetic acid enol lactone 106.5g, yield 78.3%.
Comparative example 2-2, the dosage of cyclohexanone in embodiment 1 is changed to 1.5moL by 1.2moL；Remaining is equal to embodiment
1。
Acquired results are as follows: 2- hydroxyl cyclohexadienylidene acetic acid enol lactone 113.4g, yield 83.4%.
Finally, it should also be noted that it is listed above be only several specific examples of the invention.Obviously, of the invention
It is not limited to above example, acceptable there are many deformations.Those skilled in the art can be direct from present disclosure
All deformations for exporting or associating, are considered as protection scope of the present invention.
Claims (3)
1. the method that base catalysis prepares 2- hydroxyl cyclohexadienylidene acetic acid enol lactone, it is characterised in that: with cyclohexanone and quality
Concentration is that 45~55% glyoxalic acid solutions are raw material, comprising the following steps:
Basic catalyst is added in glyoxalic acid solution, 90 DEG C of dropwise addition cyclohexanone is warming up to, is warming up to 90 after being added dropwise
1~2h of insulation reaction after~130 DEG C；The mass ratio of the basic catalyst and glyoxalic acid solution is 2.5~10%；Cyclohexanone
With the molar ratio 1.2:1 of glyoxalic acid；
Basic catalyst is sodium carbonate, potassium carbonate, sodium bicarbonate, saleratus, sodium hydroxide, potassium hydroxide；
After reaction, resulting reaction solution is evaporated under reduced pressure, collects and evaporates resulting mixed liquor；
Reaction solution after reduction vaporization is cooled to 60 ± 5 DEG C, and vacuum distillation obtains in 2- hydroxyl cyclohexadienylidene acetic acid enol
Ester.
2. the method that base catalysis according to claim 1 prepares 2- hydroxyl cyclohexadienylidene acetic acid enol lactone, it is characterised in that:
It evaporates after resulting mixed liquor is stood and is layered, upper layer is cyclohexanone, be can be recycled；Lower layer is water.
3. the method that base catalysis according to claim 1 or 2 prepares 2- hydroxyl cyclohexadienylidene acetic acid enol lactone, feature exist
In: the temperature of insulation reaction is 100~130 DEG C.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5773632A (en) * | 1996-07-09 | 1998-06-30 | Clariant Chimie S.A. | Process for the preparation of the enol lactone of 2-oxocyclohexlidene acetic acid and application to the preparation of 2-cuomaranone |
| CN1434815A (en) * | 2000-06-06 | 2003-08-06 | Dsm精细化学奥地利Nfg两合公司 | Method for the production of 2-coumarone and substituted 2-coumarones |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5773632A (en) * | 1996-07-09 | 1998-06-30 | Clariant Chimie S.A. | Process for the preparation of the enol lactone of 2-oxocyclohexlidene acetic acid and application to the preparation of 2-cuomaranone |
| CN1434815A (en) * | 2000-06-06 | 2003-08-06 | Dsm精细化学奥地利Nfg两合公司 | Method for the production of 2-coumarone and substituted 2-coumarones |
Non-Patent Citations (2)
| Title |
|---|
| 1,6-Additionen an 3-Methyl-5-methyliden-2(5H)-furanon-Derivate;von Heinz Wyss et al.;《Helvetica Chimica Acta》;19811231;第64卷(第7期);第2272-2278页 |
| Synthesis of novel 7-substituted 5,6-dihydroindol-2-ones via a Suzuki–Miyaura cross-coupling strategy;Wai Kean Goh et al.;《Tetrahedron Letters》;20071012;第48卷;第9008-9011页 |
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