CN107118187A - A kind of preparation method of 3 hydroxyl phthalic anhydride - Google Patents
A kind of preparation method of 3 hydroxyl phthalic anhydride Download PDFInfo
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- CN107118187A CN107118187A CN201710499901.3A CN201710499901A CN107118187A CN 107118187 A CN107118187 A CN 107118187A CN 201710499901 A CN201710499901 A CN 201710499901A CN 107118187 A CN107118187 A CN 107118187A
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- 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
- C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
- C07D307/89—Benzo [c] furans; Hydrogenated benzo [c] furans with two oxygen atoms directly attached in positions 1 and 3
Abstract
The invention belongs to technical field of organic synthesis, and in particular to a kind of preparation method of the hydroxyl phthalic anhydride of critical medication intermediate 3.This method makees raw material with compound I, and the oxidized methoxyl group phthalic acid of generation 3,3 methoxyl group phthalic acids generate 3 hydroxyl phthalic anhydrides by reaction 3 hydroxyl phthalics of generation, 3 hydroxyl phthalics through dehydrating condensation.Using 3 hydroxyl phthalic anhydride produced by the present invention, high income, purity is good, and this method is in course of industrialization, no especial equipment requirements, mild condition, safety and environmental protection, and technology of the invention can carry out industrial production.
Description
Technical field
The invention belongs to technical field of organic synthesis, and in particular to a kind of critical medication intermediate 3- hydroxyl phthalics
The preparation method of acid anhydride.
Background technology
3- hydroxyl phthalic anhydrides can be used for the external active material to anti-herpes simplex virus of modification ovalbumin
Prepare, the lateral reactivity material medicine is expected to the newtype drug for killing microorganism as preventative disease.In addition, 3- hydroxyls are adjacent
Phthalate anhydride can be used as the modification of the heat stable resin raw material such as epoxy resin, polyester, polyimides, the crucial medicine intermediate,
It is with a wide range of applications.
At present, generally there is following synthetic method：
Method one：2- hydroxybutyric acids ketone and acetic anhydride in concentrated sulfuric acid, generation 2- oxos-DHF, 2- oxos-
DHF generates 2- trimethyl acetoxyl furans in triethylamine with trimethyl-aceyl chloride reaction, then 2- trimethyls
The addition product dense sulfuric acid treatment of acetoxyl group furans and maleic anhydride, obtains 3- hydroxyl phthalic anhydrides.The reactions steps
Long, raw material is not easy to obtain, and is not suitable for industrialized production.
Method two：3- halophthalic acids acid anhydride in the presence of a phase transfer catalyst, reacts with alkali metal hydrogencarbonate, raw
Into 3- hydroxyl phthalic anhydrides.Although this method step is simple, raw material is not easy to obtain and phase transfer catalyst is expensive,
It is not suitable for industrialized production.
Method three：3- nitrophthalic acid acid anhydrides hydro-reduction is 3- aminophthalic acid acid anhydrides, then by the adjacent benzene of 3- amino
Dicarboxylic acid anhydride diazotising obtains 3- hydroxyl phthalic anhydrides.Still there is initiation material and be not easy to obtain in this method, while this two step is anti-
Yield is answered all than relatively low, to industrialize cost higher.
The content of the invention
The method processing step for synthesizing 3- hydroxyl phthalic anhydrides for prior art is complicated, and initiation material is difficult to obtain
, expensive, the problems such as yield is relatively low, the present invention propose a kind of preparation method of 3- hydroxyl phthalic anhydrides.
The present invention is to make raw material with compound I, by strong oxidizer oxidation generation 3- methoxyl group phthalic acids, 3- methoxies
Base phthalic acid generates 3- hydroxyls by reaction generation 3- hydroxyl phthalics, 3- hydroxyl phthalics through dehydrating condensation
Phthalic anhydride.Its specific reaction scheme is：
Compound I
Wherein, n is 0 or 1 or 2；
R1And R2Methyl or methylene or ethyl or propyl group or isopropyl or butyl are independently selected from respectively.
It is preferred that, when n is 0, R1And R2Methyl or ethyl or propyl group or isopropyl or fourth are independently selected from respectively
Base；When n is 1 or 2, R1And R2It is each independent respectively to select methylene.
A kind of preparation method of 3- hydroxyl phthalic anhydrides of the present invention, its specific step is：
(1) reaction dissolvent I is added into reactor, compound I and cetyl trimethylammonium bromide is added, is warming up to
70-80 DEG C, potassium permanganate is added, then 80-90 DEG C of insulation reaction 2-8h, cooled, filtered, washed, dried, obtain 3- methoxyl groups adjacent
Phthalic acid；
(2) into reactor add 3- methoxyl group phthalic acids, control temperature 10-30 DEG C add lewis' acid or
Acid, is finished, and stirring reaction 5-8h, reaction is finished, and reaction solution is poured slowly into frozen water, is stirred, filters, washes, is dried, obtains 3-
Hydroxyl phthalic；
(3) reaction dissolvent III is added into reactor, 60-150 DEG C is warming up to, 3- hydroxyl phthalics are then added,
Dehydrating agent is added, 60-150 DEG C of insulation reaction 1-3h, reaction is finished, filtered, be concentrated under reduced pressure to obtain 3- hydroxyl phthalic anhydrides.
In the present invention, potassium permanganate is oxidant, and in order to avoid reaction is excessively fierce, potassium permanganate is using batch charging
Mode.In order to ensure yield and excessive accessory substance is avoided, in step (1) of the present invention, with the molar ratio computing of pure material, chemical combination
Thing I：Potassium permanganate：Cetyl trimethylammonium bromide=1:2.0~3.5:0.1~0.5.Described reaction dissolvent I be DMF or
DMSO or water or its mixture, described solvent are not involved in reaction；By quality ratio, solvent I：Compound I=3-8:1.
In step (2), because the excessive phenolic hydroxyl group of temperature is oxidized easily, temperature is too low, and methoxyl group is de- incomplete, therefore 3-
Methoxyl group phthalic acid is with lewis' acid or acid in 10-30 DEG C of reaction.Described lewis' acid is Boron tribromide or trichlorine
Change aluminium or its mixture；Described acid is hydrobromic acid.Lewis' acid or acid are by the way of batch charging.With rubbing for pure material
You are than meter, 3- methoxyl group phthalic acids：Lewis' acid or acid=1：1.0-2.5.In the step, reaction dissolvent can use two
Chloromethanes can also directly use described acid.The mass ratio of solvent and 3- methoxyl group phthalic acids is 3-10:1.
Reaction dissolvent III described in step (3) is DMF or dioxane or benzene or DMSO or toluene or its mixture,
For aprotic solvent, reaction is not involved in.Described dehydrating agent is phosphorus pentoxide or DCC or CDI or polyphosphoric acids.With mass ratio
Meter, 3- hydroxyl phthalics：Dehydrating agent：Reaction dissolvent III=1:2~8:10~20.
The present invention does raw material using compound I, can prepare 3- hydroxyl phthalic anhydrides, the technology of this method is in work
In industry, no especial equipment requirements, yield is higher, purity is preferable, mild condition, safety and environmental protection.
Embodiment
Embodiment 1：
DMF100.00g, 1- methoxyl group -2,3- dimethyl benzene 27.24g (0.20mol) are added into 500mL there-necked flask
With cetyl trimethylammonium bromide 14.58g (0.04mol), 70 DEG C are warming up to, starts that potassium permanganate 79.01g is added portionwise
(0.50mol), temperature control is no more than 90 DEG C, and about 30min is added, and 80~90 DEG C of reaction 4h are incubated after adding, room temperature is cooled to, is added dropwise
300g water, filtering, water 100.00g*3 washings obtain off-white powder, and 55~60 DEG C of dryings, theoretical 39.23g is real to obtain 30.11g,
Yield 76.75%, purity 98.70%.
Dichloromethane 160.01g and 3- methoxyl group phthalic acid 30.00g is added into 500mL there-necked flask
(0.15mol), 10~15 DEG C of water-bath temperature control is added dropwise after Boron tribromide 76.67g (0.31mol), completion of dropping, continues insulation reaction
6h.400.00g mixture of ice and water is added in another 1000mL there-necked flask, above-mentioned reaction solution is poured slowly into frozen water, is controlled
Temperature is no more than 30 DEG C, continues to stir 1h afterwards, filtering is washed to pH=6,55~60 DEG C of dryings obtain off-white powder, theoretical
27.79g, it is real to obtain 25.43g, yield 91.50%, purity 99.11%.
Toluene 300.00g is added into 500mL there-necked flask, 80 DEG C are warming up to, 3- hydroxyl phthalics are added
25.01g (0.14mol), phosphorus pentoxide 50.00g, are incubated 80 DEG C of reaction 2h afterwards, and filtering has been concentrated under reduced pressure into solid analysis
Go out, be cooled to room temperature, filter to obtain light yellow solid, 55~60 DEG C of dryings obtain 18.12g, theoretical 22.53g, yield 80.42%,
Purity 98.21%.
Embodiment 2：
Water 240.00g, 1- methoxyl group -2- ethyl -3- toluene 30.04g (0.20mol) are added into 500mL there-necked flask
With cetyl trimethylammonium bromide 7.29g (0.02mol), 80 DEG C are warming up to, starts that potassium permanganate 63.21g is added portionwise
(0.40mol), temperature control is no more than 90 DEG C, and about 30min is added, and 80~90 DEG C of reaction 6h are incubated after adding, room temperature, mistake is cooled to
Filter, water 100.00g*3 washings obtain off-white powder, and 55~60 DEG C of dryings, theoretical 39.23g is real to obtain 32.17g, yield
82.00%, purity 98.32%.
Dichloromethane 290.00g and 3- methoxyl group phthalic acid 30.00g is added into 500mL there-necked flask
Aluminum trichloride (anhydrous) 51.00g (0.38mol) is added portionwise in (0.15mol), 25~30 DEG C of water-bath temperature control, adds after finishing, and continues to protect
Temperature reaction 7.5h.600.00g mixture of ice and water is added in another 1000mL there-necked flask, above-mentioned reaction solution is poured slowly into ice
In water, temperature control is no more than 30 DEG C, continues to stir 1h afterwards, filtering is washed to pH=6, and 55~60 DEG C of dryings obtain off-white color and consolidated
Body, theoretical 27.79g is real to obtain 25.12g, yield 90.39%, purity 98.63%.
DMF300.00g is added into 500mL there-necked flask, 150 DEG C are warming up to, 3- hydroxyl phthalics are added
25.01g (0.14mol), CDI155.50g (0.96mol), are incubated 150 DEG C of reaction 1h, are concentrated under reduced pressure, are cooled to room temperature afterwards,
Dichloromethane 100g mashing 1h are added, light yellow solid are filtered to obtain, 55~60 DEG C of dryings obtain 18.54g, theoretical 22.53g, yield
82.29%, purity 98.73%.
Embodiment 3：
DMSO120.00g, 5- methoxyl groups -1,2,3,4- naphthane 32.45g are added into 1000mL there-necked flask
(0.20mol) and cetyl trimethylammonium bromide 36.44g (0.10mol), is warming up to 75 DEG C, starts that permanganic acid is added portionwise
Potassium 110.62g (0.70mol), temperature control is no more than 90 DEG C, and about 40min is added, and 80~90 DEG C of reaction 2.5h, cooling are incubated after adding
To room temperature, 600g water is added dropwise, filtering, water 100.00g*3 washings obtain off-white powder, 55~60 DEG C of dryings, theoretical 39.23g,
It is real to obtain 28.07g, yield 71.55%, purity 98.41%.
48% hydrobromic acid 150.00g and 3- methoxyl group phthalic acid 25.00g is added into 500mL there-necked flask
(0.13mol), 25~30 DEG C of stirring reaction 5h.500.00g mixture of ice and water is added in another 1000mL there-necked flask, upper
State reaction solution to be poured slowly into frozen water, temperature control is no more than 30 DEG C, continue to stir 1h afterwards, filtering is washed to pH=6,55~60
DEG C drying, obtains off-white powder, theoretical 23.21g, real 20.18g, yield 86.95%, purity 98.33%.
Toluene 300.00g is added into 500mL there-necked flask, 60 DEG C are warming up to, 3- hydroxyl phthalics are added
20.00g (0.11mol), polyphosphoric acids 100.01g, are incubated 60 DEG C of reaction 3h, pour out supernatant, filter light yellow afterwards
Solid, 55~60 DEG C of dryings obtain 14.25g, theoretical 18.02g, yield 79.08%, purity 98.63%.
48% described hydrobromic acid refers to the hydrobromic acid aqueous solution that mass fraction is 48%.
Embodiment 4：
Water 250.00g, 1- methoxyl group -2- propyl group -3- ethylbenzene 35.65g (0.20mol) are added into 500mL there-necked flask
With cetyl trimethylammonium bromide 7.29g (0.02mol), 70 DEG C are warming up to, starts that potassium permanganate 63.21g is added portionwise
(0.41mol), temperature control is no more than 90 DEG C, and about 30min is added, and 80~90 DEG C of reaction 8h are incubated after adding, room temperature, mistake is cooled to
Filter, water 100.00g*3 washings obtain off-white powder, and 55~60 DEG C of dryings, theoretical 39.23g is real to obtain 31.70g, yield
80.80%, purity 98.03%.
Dichloromethane 290.00g and 3- methoxyl group phthalic acid 30.00g is added into 500mL there-necked flask
Aluminum trichloride (anhydrous) 20.40g (0.15mol) is added portionwise in (0.15mol), 15~20 DEG C of water-bath temperature control, adds after finishing, and is added dropwise three
Boron bromide 38.34g (0.15mol), continues insulation reaction 5h.600.00g frozen water is added in another 1000mL there-necked flask to mix
Compound, above-mentioned reaction solution is poured slowly into frozen water, and temperature control is no more than 30 DEG C, continues to stir 1h afterwards, filtering is washed to pH=
6,55~60 DEG C of dryings, obtain off-white powder, and theoretical 27.79g is real to obtain 25.60g, yield 92.12%, purity 98., 3%.
Toluene 500.00g is added into 500mL there-necked flask, 80 DEG C are warming up to, 3- hydroxyl phthalics are added
25.00g (0.14mol), polyphosphoric acids 40.01g and phosphorus pentoxide 30.00g, are incubated 80 DEG C of reaction 1h, pour out afterwards
Clear liquid, filters to obtain light yellow solid, and 55~60 DEG C of dryings obtain 19.61g, theoretical 22.53g, yield 87.04%, purity
98.14%.
Embodiment 5：
Water 210.00g, 4- methoxyindan 29.64g (0.20mol) and cetyl are added into 500mL there-necked flask
Trimethylammonium bromide 7.29g (0.02mol), is warming up to 70 DEG C, starts that potassium permanganate 79.02g (0.50mol) is added portionwise, control
Temperature is no more than 90 DEG C, and about 30min is added, and 80~90 DEG C of reaction 7h are incubated after adding, room temperature is cooled to, filters, water 100.00g*3
Washing, obtains off-white powder, and 55~60 DEG C of dryings, theoretical 39.23g is real to obtain 32.16g, yield 81.98%, purity 98.53%.
Dichloromethane 240.00g and 3- methoxyl group phthalic acid 30.00g is added into 500mL there-necked flask
Aluminum trichloride (anhydrous) 51.00g (0.38mol) is added portionwise in (0.15mol), 25~30 DEG C of water-bath temperature control, adds after finishing, and continues to protect
Temperature reaction 6.5h.600.00g mixture of ice and water is added in another 1000mL there-necked flask, above-mentioned reaction solution is poured slowly into ice
In water, temperature control is no more than 30 DEG C, continues to stir 1h afterwards, filtering is washed to pH=6, and 55~60 DEG C of dryings obtain off-white color and consolidated
Body, theoretical 27.79g is real to obtain 25.01g, yield 90.00%, purity 98.42%.
DMSO300.00g is added into 500mL there-necked flask, 150 DEG C are warming up to, 3- hydroxyl phthalics are added
25.00g (0.14mol), DCC195.00g, are incubated 150 DEG C of reaction 1h, are concentrated under reduced pressure, are cooled to room temperature, add dichloromethane afterwards
Alkane 100.00g is beaten 1h, filters to obtain light yellow solid, 55~60 DEG C of dryings obtain 17.96g, theoretical 22.53g, yield
79.72%, purity 98.83%.
Embodiment 6：
Add DMF100.00g into 500mL there-necked flask, 1- methoxyl group -2,3- dipropyl benzene 38.46g (0.2mol) and
Cetyl trimethylammonium bromide 14.58g (0.04mol), is warming up to 70 DEG C, starts that potassium permanganate 79.01g is added portionwise
(0.50mol), temperature control is no more than 90 DEG C, and about 30min is added, and 80~90 DEG C of reaction 4h are incubated after adding, room temperature is cooled to, is added dropwise
300.00g water, filtering, water 100.00g*3 washings obtain off-white powder, and 55~60 DEG C of dryings, theoretical 39.23g is real to obtain
30.43g, yield 77.57%, purity 98.91%.
Dichloromethane 150.00g and 3- methoxyl group phthalic acid 30.00g is added into 500mL there-necked flask
(0.15mol), 10~15 DEG C of water-bath temperature control is added dropwise after Boron tribromide 95.22g (0.38mol), completion of dropping, continues insulation reaction
5h.450.00g mixture of ice and water is added in another 1000mL there-necked flask, above-mentioned reaction solution is poured slowly into frozen water, is controlled
Temperature is no more than 30 DEG C, continues to stir 1h afterwards, filtering is washed to pH=6,55~60 DEG C of dryings obtain off-white powder, theoretical
27.79g, it is real to obtain 25.56g, yield 91.98%, purity 99.23%.
Dioxane 200.00g and benzene 150.00g is added into 500mL there-necked flask, 80 DEG C are warming up to, 3- hydroxyls are added
Phthalic acid 25.00g (0.14mol), phosphorus pentoxide 75.02g, are incubated 80 DEG C of reaction 2h afterwards, and filtering is concentrated under reduced pressure into
There is solid precipitation, be cooled to room temperature, filter to obtain light yellow solid, 55~60 DEG C of dryings obtain 17.60g, theoretical 22.53g, yield
78.12%, purity 98.33%.
Claims (9)
1. a kind of preparation method of 3- hydroxyl phthalic anhydrides, it is characterised in that：This method makees raw material with compound I, through oxygen
Metaplasia generates 3- hydroxyl O-phthalics into 3- methoxyl group phthalic acids, 3- methoxyl groups phthalic acid by demethylation reaction
Acid, 3- hydroxyl phthalics generate 3- hydroxyl phthalic anhydrides through dehydrating condensation；
Compound I is：
Wherein, n is 0 or 1 or 2；
R1And R2Methyl or methylene or ethyl or propyl group or isopropyl or butyl are independently selected from respectively.
2. a kind of preparation method of 3- hydroxyl phthalic anhydrides according to claim 1, it is characterised in that：It is specifically walked
Suddenly it is：
(1) reaction dissolvent I is added into reactor, compound I and cetyl trimethylammonium bromide is added, is warming up to 70-80
DEG C, potassium permanganate is added, then 80-90 DEG C of insulation reaction 2-8h, cooled, filtered, washed, dried, obtain the adjacent benzene two of 3- methoxyl groups
Formic acid；
(2) 3- methoxyl group phthalic acids are added into reactor, control temperature adds lewis' acid or acid at 10-30 DEG C, plus
Finish, stirring reaction 5-8h, reaction is finished, and reaction solution is poured slowly into frozen water, stir, filter, wash, dry, obtain 3- hydroxyls
Phthalic acid；
(3) reaction dissolvent III is added into reactor, 60-150 DEG C is warming up to, 3- hydroxyl phthalics are then added, then add
Enter dehydrating agent, 60-150 DEG C of insulation reaction 1-3h, reaction is finished, filter, be concentrated under reduced pressure to obtain 3- hydroxyl phthalic anhydrides.
3. a kind of preparation method of 3- hydroxyl phthalic anhydrides according to claim 2, it is characterised in that：Step (1)
In, with the molar ratio computing of pure material, compound I：Potassium permanganate：Cetyl trimethylammonium bromide=1:2.0~3.5:0.1~
0.5。
4. a kind of preparation method of 3- hydroxyl phthalic anhydrides according to claim 2, it is characterised in that：Step (1)
Described in reaction dissolvent I be DMF or DMSO or water or its mixture；By quality ratio, solvent I：Compound I=3-8:1.
5. a kind of preparation method of 3- hydroxyl phthalic anhydrides according to claim 2, it is characterised in that：Step (2)
Described in lewis' acid be Boron tribromide or alchlor or its mixture；Described acid is hydrobromic acid.
6. a kind of preparation method of 3- hydroxyl phthalic anhydrides according to claim 2, it is characterised in that：Step (2)
In with the molar ratio computing of pure material, 3- methoxyl group phthalic acids：Lewis' acid or acid=1：1.0-2.5.
7. a kind of preparation method of 3- hydroxyl phthalic anhydrides according to claim 2, it is characterised in that：Step (3)
Described in reaction dissolvent III be DMF or dioxane or benzene or DMSO or toluene or its mixture.
8. a kind of preparation method of 3- hydroxyl phthalic anhydrides according to claim 2, it is characterised in that：Step (3)
Described in dehydrating agent be phosphorus pentoxide or DCC or CDI or polyphosphoric acids.
9. a kind of preparation method of 3- hydroxyl phthalic anhydrides according to claim 2, it is characterised in that：Step (3)
In, by quality ratio, 3- hydroxyl phthalics：Dehydrating agent：Reaction dissolvent III=1:2~8:10~20.
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Cited By (4)
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| CN114479552A (en) * | 2022-01-28 | 2022-05-13 | 达高工业技术研究院(广州)有限公司 | Solder resist ink and preparation method and application thereof |
| CN114573535A (en) * | 2022-03-18 | 2022-06-03 | 常州大学 | Preparation method of chemical intermediate 3-hydroxyphthalic anhydride |
| CN115490657A (en) * | 2022-09-29 | 2022-12-20 | 天津众泰材料科技有限公司 | Preparation method of 3,3', 4' -benzophenone tetracarboxylic dianhydride |
| CN115677636A (en) * | 2022-10-27 | 2023-02-03 | 天津众泰材料科技有限公司 | Preparation method of 2, 3',4' -biphenyl tetracarboxylic dianhydride |
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Cited By (8)
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| CN114479552A (en) * | 2022-01-28 | 2022-05-13 | 达高工业技术研究院(广州)有限公司 | Solder resist ink and preparation method and application thereof |
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| CN114573535A (en) * | 2022-03-18 | 2022-06-03 | 常州大学 | Preparation method of chemical intermediate 3-hydroxyphthalic anhydride |
| CN114573535B (en) * | 2022-03-18 | 2024-01-23 | 常州大学 | Preparation method of chemical intermediate 3-hydroxyphthalic anhydride |
| CN115490657A (en) * | 2022-09-29 | 2022-12-20 | 天津众泰材料科技有限公司 | Preparation method of 3,3', 4' -benzophenone tetracarboxylic dianhydride |
| CN115490657B (en) * | 2022-09-29 | 2024-01-26 | 天津众泰材料科技有限公司 | Preparation method of 3,3', 4' -benzophenone tetracarboxylic dianhydride |
| CN115677636A (en) * | 2022-10-27 | 2023-02-03 | 天津众泰材料科技有限公司 | Preparation method of 2, 3',4' -biphenyl tetracarboxylic dianhydride |
| CN115677636B (en) * | 2022-10-27 | 2024-01-26 | 天津众泰材料科技有限公司 | Preparation method of 2, 3',4' -biphenyl tetracarboxylic dianhydride |
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