CN105017010B - The preparation method of p-phthalic acid and the preparation method of 4-methyl-3-cyclohexene-1-methyl formate - Google Patents
The preparation method of p-phthalic acid and the preparation method of 4-methyl-3-cyclohexene-1-methyl formate Download PDFInfo
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Abstract
The preparation method of a kind of p-phthalic acid, is included under the catalysis of aluminum chloride, makes isoprene and acrylic acid methyl ester. carry out the reaction of Di Ershia Dare and generates a crude product, and the reaction of this Di Ershia Dare is to carry out under solvent-free and at a temperature of 20 to 50 DEG C；This crude product is carried out decompression and is distilled to yield a predecessor；And this predecessor is sequentially carried out dehydrogenation, hydrolysis and oxidation reaction, with prepared p-phthalic acid.This preparation method can effectively save the use of organic solvent and heat energy, to reduce the harm to environment and the consuming of the energy, and can quickly prepare high yield and the crude product containing high selective para-position product.
Description
Technical field
The present invention relates to the preparation method of a kind of p-phthalic acid, particularly relate to a kind of under solvent-free
And under low temperature, carry out the catalysis processing procedure that Di Ershi-A Deer (Diels-Alder) reacts.
Background technology
PETP (polyethylene terephthalate, PET) is by extensively
It is applied in the article of everyday use industry such as fiber, container, packing timber, p-phthalic acid (purified
Terephthalic acid, PTA) it is one of them principal monomer raw material.
Nazarov et al. discloses one in Russ.Chem.Bull.1959,8,1362-1369
Plant the preparation method of p-phthalic acid, be to utilize hydroquinone (hydroquinone) to urge under solvent-free
Change isoprene (isoprene) and acrylic acid methyl ester. (methyl acrylate) carry out Di Ershi-
A Deer reacts, then prepares p-phthalic acid via dehydrogenation reaction, hydrolysis and oxidation reaction.
But, the Di Ershi-A Deer reaction in above-mentioned processing procedure is the most slowly (at 20 DEG C
Take 7 months), therefore common practices is often required for being additionally provided energy sources for heating, to accelerate
Reaction carries out (taking at 120 DEG C 6 hours, taking 2 hours at 200 DEG C, at 400 DEG C
Under can be running system), and the selectivity of its para-position product can along with reaction temperature improve and drop
Low.Additionally, the oxidation reaction in above-mentioned processing procedure is with chromic acid [chromium (VI)
Trioxide] as oxidant, rear extended meeting causes heavy metal chromium pollution；And above-mentioned processing procedure is final
The p-phthalic acid obtained and M-phthalic acid (isophthalic acid) mixture, need into
One step is separated by other reagent.
TAKASHI et al. discloses one in J.Org.Chem.1966,31,1121-1123
The preparation method of 4-methyl-3-cyclohexene-1-methyl formate, is to utilize aluminum chloride to be catalyzed isoamyl in benzene
Diene and acrylic acid methyl ester. carry out Di Ershi-A Deer reaction.But, above-mentioned processing procedure not only needs
The cost of organic solvent to be expended (benzene), and follow-up needs process asking of solvent contamination and recovery
Topic.The more important thing is, generally use solvent and carry out reacting the yield contributing to promoting product, but
In the result disclosed in above-mentioned document, it only carries out the yield of 3 hours at 10 to 20 DEG C
It is 50%.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of p-phthalic acid, can overcome above-mentioned previously
Technology expends organic solvent or the shortcoming of heat energy.
The preparation method of p-phthalic acid of the present invention, comprises: under the catalysis of aluminum chloride, makes isoamyl two
Alkene and acrylic acid methyl ester. carry out Di Ershi-A Deer reaction and generate a crude product, this Di Ershi-Ah
Dare reaction is to carry out under solvent-free and at a temperature of-20 to 50 DEG C；This crude product is carried out
Decompression is distilled to yield a predecessor；And this predecessor is sequentially carried out dehydrogenation, hydrolyzes and aoxidize
Reaction, with prepared p-phthalic acid.
Another object of the present invention, is i.e. providing a kind of 4-methyl-3-cyclohexene-1-methyl formate
Preparation method, comprise: under the catalysis of aluminum chloride, make isoprene and acrylic acid methyl ester. carry out Di
Er Shi-A Deer reaction generates a crude product, and this Di Ershi-A Deer reaction is under solvent-free
And carry out at a temperature of-20 to 50 DEG C；And this crude product is carried out decompression distillation.
The heat energy that relatively low reaction temperature contributes to being additionally provided needed for reducing on processing procedure expends.Relatively
Goodly, this Di Ershi-A Deer reaction is to carry out at a temperature of-10 to 30 DEG C.More preferably,
This Di Ershi-A Deer reaction is to carry out at a temperature of 0 to 5 DEG C.
It is preferred that the reaction time range of this Di Ershi-A Deer reaction is 1 to 24 hour.
More preferably, the reaction time range of this Di Ershi-A Deer reaction is 2 to 10 hours.Most preferably
Ground, the reaction time range of this Di Ershi-A Deer reaction is 2 to 3 hours.
It is preferred that the consumption molar ratio of aluminum chloride and isoprene is 0.1:1 to 0.5:
1。
It is preferred that this dehydrogenation reaction is included in palladium and aluminium oxide (Pd and Al2O3) catalysis under add
Heat.
It is preferred that this Di Ershi-A Deer reaction includes first acrylic acid methyl ester. and aluminum chloride being mixed
Close, under the ice bath of 0 to 5 DEG C, isoprene is added thereto.
Above-mentioned isoprene can be by the natural goods (such as Oleum Terebinthinae) containing terpenes (terpene) or sky
So rubber is obtained by raw material.Aforesaid propylene acid methyl ester can be made through esterification reaction of organic acid by acrylic acid
, acrylic acid can be obtained through fermentable and dehydration by raw matter sources such as glucoses.
The beneficial effects of the present invention is: this preparation method can effectively save organic solvent and heat energy
Use, to reduce the harm to environment and the consuming of the energy, and can quickly prepare high yield and contain
There is the crude product of high selective para-position product.
Detailed description of the invention
Embodiment
＜ embodiment 1 ＞ E1
A. Di Ershi-A Deer reacts (Diels-Alder reaction)
75.8g acrylic acid methyl ester. and 9.78g aluminum chloride are inserted in 250mL round-bottomed bottle and uniformly mixes
Close, under ice bath and stirring, 50g isoprene is slowly added to (acrylic acid methyl ester.,
Aluminum chloride is 1.2:0.1:1.0 with the mol ratio of isoprene), and it is little to react 2 at 0 DEG C
Time (solvent-free), after adding 200mL water and 200mL ethyl acetate and stirring 10 minutes,
Extract organic layer (ethyl acetate layer) and clean organic layer with saturated sodium bicarbonate aqueous solution,
After organic layer is carried out concentrating under reduced pressure, obtain a crude product.With1H NMR analyze learn above-mentioned slightly
In product, the selectivity of para-position product is 93.5%.Above-mentioned crude product is carried out decompression distillation to enter
Row separate, under 10mmHg pressure collect 80 to 84 DEG C time product of distillation, obtain 95.2g
Predecessor.
Identifying above-mentioned predecessor with NMR (Nuclear Magnetic Resonance) spectrum, its qualification result is as follows:1H NMR
(400MHz,CDCl3)δ:5.37(brs,1H),3.68(s,3H),2.44-2.53(m,
1H),2.20-2.23(m,2H),1.97-2.02(m,3H),1.66-1.76(m,1H),
1.64(s,3H).Analysis result learns that above-mentioned predecessor is 4-methyl-3-cyclohexene-1-formic acid
Methyl ester (methyl 4-methyl-3-cyclohexene-1-carboxylate).
B. dehydrogenation reaction
At room temperature, the 4-methyl-3-cyclohexene-1-formic acid of 7.68g above-mentioned step A gained is taken
Methyl ester is dissolved in 200mL triethylene glycol dimethyl ether. (triethyleneglycoldimethyl
Ether), in, 1.7g (0.5g%) Pd and Al is added2O3, at 210 DEG C, backflow 10 is little
Shi Hou, water-bath is cooled to room temperature.Extract after mixing with 200mL water and 400mL ether afterwards
Organic layer (ether layer), and clean 3 times with 300mL water, to remove remaining 2,2'-ethylenedioxybis(ethanol). diformazan
Ether, then with magnesium sulfate except water, remove solvent with spin concentration subsequently, obtain 7.51g dehydrogenation and produce
Thing.
With1HNMR analyzes above-mentioned dehydrogenation product, learn its contain methyl 4 methylbenzoate and
4-methylcyclohexyl methyl formate (mol ratio is 85:15).
C. hydrolysis
The dehydrogenation product taking 3g above-mentioned step B gained is dissolved in 50mL ether, then in room temperature
The methanol solution of lower addition 20mL 2M sodium hydroxide, after stirring 20 hours, adds 100mL
Extract water layer after water, be acidified to pH value for 2 to 3 with 6M hydrochloric acid afterwards, add 100mL
Extract organic layer (ether layer) after ether, and with magnesium sulfate except removing solvent after water, obtain water
Hydrolysis products.
D. oxidation reaction
The hydrolyzate of above-mentioned step C gained is dissolved in 50mL 0.8M sodium hydrate aqueous solution
In and be cooled to 0 DEG C, then divide 3 by every minor tick in the way of 2 minutes by 6.32g potassium permanganate
Secondary addition, and stir 1 hour after being heated to 80 DEG C, it is again heated to 120 DEG C of backflows 12 afterwards
Hour.Kieselguhr is added after being cooled to room temperature, continuously stirred to adsorb remaining potassium permanganate
(and other reduzates containing manganese), after 0.5 hour, filter and remove kieselguhr and adsorbate thereof,
Under ice bath and stirring, slowly 30mL 18M aqueous sulfuric acid is added above-mentioned filtration gained
In solution, continuously stirred 3 hours, after confirming that pH value is 1 to 2, filter.Incited somebody to action
The solid of filter gained is placed under 100 DEG C of vacuum drying 10 hours, and with dimethyl acetylamide
(dimethylacetamide, DMAC) carries out recrystallization, obtains 1.66g oxidation product (the most right
Phthalic acid) crystal.
＜ embodiment 2 to 6 ＞ E2 to E6
The preparation method of embodiment 2 to 6 is same as in Example 1, and different places is step A
Reaction temperature change into-20 DEG C ,-10 DEG C, 5 DEG C, 30 DEG C and 50 DEG C respectively.
＜ embodiment 7 ＞ E7
The preparation method of embodiment 7 is same as in Example 1, and it is anti-that different places is step A
10 hours are changed between Ying Shi.
＜ embodiment 8 to 10 ＞ E8 to E10
The preparation method of embodiment 8 to 10 is same as in Example 1, and different places is to walk A
The mol ratio of rapid aluminum chloride and isoprene changes into 0.5:1.0,1:1.0 and 2 respectively:
1.0。
＜ comparative example 1 ＞ CE1
Comparative example 1 is J.Org.Chem.1966,31, the 1121-1123 preparation methods disclosed,
It is in the benzene of 280mL and at 10 to 20 DEG C, makes acrylic acid methyl ester., aluminum chloride and isoamyl
Diene (mol ratio is 0.303:0.032:0.307) carries out reacting 3 hours.
＜ comparative example 2 ＞ CE2
The system that comparative example 2 discloses for Russ.Chem.Bull.1959,8,1362-1369
Method, it is at 120 DEG C, and (mol ratio is to make acrylic acid methyl ester., hydroquinone and isoprene
0.3485:0.0009:0.2936) carry out reacting 6 hours (solvent-free).
＜ comparative example 3 to 7 ＞ CE3 to CE7
The preparation method of comparative example 3 to 7 is same as in Example 1, and different places is step A
Aluminum chloride change into respectively trifluoromethanesulfonic acid scandium (III) [scandium (III) triflate,
Sc(OTf)3], iron chloride (III) [FeCl3], copper trifluoromethanesulfcomposite (II) [Cu (OTf)2]、
Stannic chloride (II) [SnCl2] and trifluoromethanesulfonic acid zinc [Zn (OTf)2], the response time will change into 24
Hour, and the reaction temperature of comparative example 4 is changed into 25 DEG C.
The reaction condition of Di Ershi-A Deer reaction in embodiment 1 to 9 and comparative example 1 to 7
And the yield of crude product is as shown in table 1 below with the selectivity of para-position product.
Table 1
" N/A " expression does not obtains.
It is appreciated that by table 1: embodiment 1 to 9 is under the catalysis of aluminum chloride and solvent-free
Carry out under reaction condition Di Ershi-A Deer reaction, the yield of its crude product all more than 66%,
And the selectivity of its para-position product is all more than 69%.Wherein, the crude product of E1 to E5 and E8
Yield all more than 74%；The selectivity of the para-position product of E1 to E5 and E7 all 89% with
On.And comparative example 1 is to react in organic solvent-benzene, the yield of its crude product is only
50%；Comparative example 2 to 7 is respectively under the catalysis of different catalysts and solvent-free reaction bar
Carrying out under part, the yield of its crude product is all below 74%.Wherein, CE2 needs higher
React the longer time (6 hours) under reaction temperature (120 DEG C), can be only achieved the yield of crude product
It is 74% and the selectivity of para-position product is 79%；The yield of the crude product of CE5 to CE7 is only 0
To 5%.
In sum, the preparation method of p-phthalic acid of the present invention is under the catalysis of aluminum chloride, and
Carry out Di Ershi-A Deer reaction under solvent-free and at a temperature of-20 to 50 DEG C, be not required to use
Solvent can the most quickly prepare high yield and contain the thick of high selective para-position product
Product, can effectively save the use of organic solvent and heat energy, and reduce the impact to environment, really
The purpose of the present invention can be reached in fact.
The above, only presently preferred embodiments of the present invention and concrete example, when can not be with this
Limit the scope that the present invention implements, the most generally made according to the claims in the present invention and description
Simple equivalence change with modify, the most still belong in the range of the present invention contains.
Claims (10)
1. the preparation method of a p-phthalic acid, it is characterised in that it comprises:
Under the catalysis of aluminum chloride, isoprene and acrylic acid methyl ester. is made to carry out Di Ershi-A De
Your reaction generates a crude product, this Di Ershi-A Deer reaction be solvent-free lower and-20 to
Carry out at a temperature of 50 DEG C；
This crude product is carried out decompression and is distilled to yield a predecessor；And
This predecessor is sequentially carried out dehydrogenation, hydrolysis and oxidation reaction, with prepared terephthaldehyde
Acid.
The preparation method of p-phthalic acid the most according to claim 1, it is characterised in that: should
Di Ershi-A Deer reaction is to carry out at a temperature of-10 to 30 DEG C.
The preparation method of p-phthalic acid the most according to claim 2, it is characterised in that: should
Di Ershi-A Deer reaction is to carry out at a temperature of 0 to 5 DEG C.
The preparation method of p-phthalic acid the most according to claim 1, it is characterised in that: should
The reaction time range of Di Ershi-A Deer reaction is 1 to 24 hour.
The preparation method of p-phthalic acid the most according to claim 4, it is characterised in that: should
The reaction time range of Di Ershi-A Deer reaction is 2 to 10 hours.
The preparation method of p-phthalic acid the most according to claim 5, it is characterised in that: should
The reaction time range of Di Ershi-A Deer reaction is 2 to 3 hours.
The preparation method of p-phthalic acid the most according to claim 1, it is characterised in that: chlorine
The consumption molar ratio changing aluminum and isoprene is 0.1:1 to 0.5:1.
The preparation method of p-phthalic acid the most according to claim 1, it is characterised in that: should
Dehydrogenation reaction is included under the catalysis of palladium and aluminium oxide and heats.
The preparation method of p-phthalic acid the most according to claim 1, it is characterised in that: should
Di Ershi-A Deer reaction includes first acrylic acid methyl ester. and aluminum chloride being mixed, under ice bath
Isoprene is added thereto.
10. the preparation method of a 4-methyl-3-cyclohexene-1-methyl formate, it is characterised in that its
Comprise:
Under the catalysis of aluminum chloride, isoprene and acrylic acid methyl ester. is made to carry out Di Ershi-A De
Your reaction generates a crude product, this Di Ershi-A Deer reaction be solvent-free lower and-20 to
Carry out at a temperature of 50 DEG C；And
This crude product is carried out decompression distillation.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410153407.8A CN105017010B (en) | 2014-04-16 | 2014-04-16 | The preparation method of p-phthalic acid and the preparation method of 4-methyl-3-cyclohexene-1-methyl formate |
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| CN201410153407.8A CN105017010B (en) | 2014-04-16 | 2014-04-16 | The preparation method of p-phthalic acid and the preparation method of 4-methyl-3-cyclohexene-1-methyl formate |
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| CN105017010B true CN105017010B (en) | 2016-08-17 |
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| CN201410153407.8A Expired - Fee Related CN105017010B (en) | 2014-04-16 | 2014-04-16 | The preparation method of p-phthalic acid and the preparation method of 4-methyl-3-cyclohexene-1-methyl formate |
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Non-Patent Citations (3)
| Title |
|---|
| Catalytic Actions of Aluminum Chloride on the Isoprene-Methy 1 Acrylate Diels-Alder Reaction;TAKASHI Inukai et al.,;《J.Org.Chem.》;19660430;第31卷;1121-1123 * |
| Isoprene/Methyl Acrylate Diels-Alder Reaction in Supercritical Carbon Dioxide;Bin Lin et al.,;《Ind. Eng. Chem. Res.》;19990925;第38卷(第12期);4525-4530 * |
| 含水LaCl3催化异戊二烯与丙烯酸甲酯的Diels-Alder反应;陈斌等;《化学与生物工程》;20061231;第23卷(第4期);第47-49页 * |
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