CN104039763A - Process for preparing n-substituted cyclic imides - Google Patents
Process for preparing n-substituted cyclic imides Download PDFInfo
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- CN104039763A CN104039763A CN201080071274.XA CN201080071274A CN104039763A CN 104039763 A CN104039763 A CN 104039763A CN 201080071274 A CN201080071274 A CN 201080071274A CN 104039763 A CN104039763 A CN 104039763A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
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Abstract
In a process for making an N-substituted phthalimide compound, an amine is contacted with a carboxylic acid anhydride and allowed to react in an aqueous solution at a pH of about 2 to about 6. Optionally, the reactants are combined with an acid to lower the pH of the reaction solution wherein the lowering of the pH optimizes the yield of the desired N-substituted phthalimide product. The N-substituted phthalimide may be, for example, N- hydroxyphthalimide, and the reactants may be phthalic anhydride and hydroxylamine or a salt thereof. The N-substituted phthalimide compound is useful for, among other things, the oxidation of various hydrocarbons.
Description
The cross reference of related application
The application requires in the right of priority of the formerly U.S. provisional application sequence number 61/165,714 of submission on April 1st, 2009, and the full content of this application is hereby incorporated by.
Technical field
The present invention relates to the technique of the cyclic imide of synthetic N-replacement, and the technique of particularly synthesizing HP.
Background technology
The oxidation of hydrocarbon is the important reaction in industrial organic chemistry.Therefore, for example the oxidation of hexanaphthene is commercially for the preparation of hexalin and pimelinketone-they are the important as precursors during nylon is produced, and the precursor of the oxidation of alkylaromatic hydrocarbons in producing for the preparation of phenol-polycarbonate and epoxy resin.
The cyclic imide that N-replaces can be used as free radical medium in many oxidizing reactions based on free radical.Especially, the phthalic imidine that uses N-to replace allows the speed of reaction, selectivity and/or the productive rate that improve conventionally.The phthalic imidine, particularly HP that some N-replaces is for sec-butylbenzene (SBB) and phenylcyclohexane (CHB), to be oxidized to the good catalyst material standed for of their corresponding superoxide.SBB superoxide is the intermediate during phenol and MEK produce, and CHB superoxide is the intermediate in phenol and Cyclohexanone Production.
The oxidation of hydrocarbon can be used known oxygenant, for example KMnO
4, CrO
3and HNO
3carry out.Yet the use that these oxygenants have them is accompanied by the shortcoming that makes unwanted by product, described by product may cause to be processed and pollution problem.Therefore preferably use based on superoxide or N
2the oxygenant of O.Yet the most cheap oxygenant is pure form or as the molecular oxygen of atmosphericoxygen or dilute form.Yet oxygen itself is not suitable for oxygenated hydrocarbon conventionally, because the O occurring with the favourable triplet state form of energy
2the reactive behavior of molecule is not enough.
Can be used for the shortcoming that cyclic imide that the N-of the oxidation of hydrocarbon replaces can not be obtained with large-scale commercial quantity by they at present.The extensive technique of the cyclic imide so, not replacing for the preparation of N-.
According to the present invention, a kind of optimization method of preparing the cyclic imide of some N-replacement has been proposed, the cyclic imide that wherein N-replaces can obtain by acceptable productive rate.
Summary of the invention
Summary of the invention
In one aspect, the present invention relates to a kind of technique of cyclic imide of the N-of preparation replacement, described technique comprises:
A. make cyclic carboxylic acids acid anhydrides in the aqueous solution, contact to form the first mixture with oxyamine or its salt, the pH of wherein said the first mixture is about 2-approximately 6, and wherein before reaction in described the first mixture the mol ratio of oxyamine and carboxylic acid anhydride be about 0.8-approximately 2.0; With
B. make described mixture react, make to form the cyclic imide compound that N-replaces.
Expediently, described technique may further include:
A. acid is added described the first mixture to reduce the pH of described the first mixture, form the second mixture; With
B. from described the second mixture, take out the cyclic imide compound of the described N-replacement of at least a portion.
Expediently, described technique can even further comprise:
A. other acid is added described the second mixture further to reduce the pH of described the second mixture; With
B. take out the cyclic imide compound of the described N-replacement of at least a portion.
The detailed description of embodiment
" deprotonation choline " refers to oxyamine reactant salt and makes enough oxyamines with the alkali with cyclic carboxylic acids anhydride reaction.By the indefiniteness example of the deprotonation choline of the cyclic imide replacing for the synthesis of N-, be NaOH, Na
2cO
3and NH
3." aqueous solution " refers to any moisture liquid or slurries.
The invention provides a kind of technique of cyclic imide of the N-of preparation replacement.Described technique comprises makes cyclic carboxylic acids acid anhydrides contact with oxyamine.The cyclic imide synthesis condition that N-replaces is confirmed as allowing for example, by the aqueous solution of oxyamine or its salt (, hydroxylamine sulfate and hydroxy amine hydrochloric acid salt) and the cyclic carboxylic acids acid anhydrides cyclic imide with the reproducible formation high purity N-replacement of high yield.
Preferably use hydroxyl amine salt for example hydroxylamine sulfate and hydroxy amine hydrochloric acid salt.Can use free oxyamine, but free oxyamine may be more difficult and dangerous than the processing of hydroxyl amine salt.Yet BASF has made the freing hydroxy amine that can be used for technique of the present invention at present, be called as Hydroxylamine Free Base
tM(50% aqueous solution).
That the cyclic acid anhydride that can be used for technique of the present invention comprises is alicyclic, the acid anhydrides of aromatics or heterocycle di-carboxylic acid.Suitable acid anhydrides includes, but not limited to 1,2,4,5-benzene tetracarboxylic acid acid anhydrides, 1,2,4-benzene tricarboxylic acid acid anhydrides, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, Tetra hydro Phthalic anhydride, 4-methyl nadic anhydride, tetrabromophthalic anhydride and tetrachlorophthalic tetrachlorophthalic anhydrid, tetraphenyl Tetra hydro Phthalic anhydride, 3-nitrophthalic acid acid anhydride, cis-1,2,3,6-Tetra Hydro Phthalic Anhydride etc.Preferably, the cyclic acid anhydride that can be used for technique of the present invention comprises the Tetra hydro Phthalic anhydride of Tetra hydro Phthalic anhydride and replacement.
In one embodiment, Tetra hydro Phthalic anhydride reacts with oxyamine and forms HP (hereinafter " NHPI ").Reproduced NHPI below synthetic.In the time of in the aqueous solution when Tetra hydro Phthalic anhydride being joined to oxyamine as follows, the speed of reaction during NHPI is synthetic is conducive to prepare NHPI.Do not wish that by phthalic acid path (be k
2) order about reaction, because reaction rate constant k
2and k
3be not conducive to this path and form NHPI.
The cyclic imide compound that N-replaces can be prepared by making cyclic carboxylic acids acid anhydrides and oxyamine or its salt contact to form the first mixture in the aqueous solution.For example, the cyclic imide compound that N-replaces can be NHPI, and cyclic carboxylic acids acid anhydrides can be Tetra hydro Phthalic anhydride, and oxyamine can be hydroxyl amine salt.
When using hydroxyl amine salt, preferably spend protonated base by the deprotonation of hydroxyl amine salt to form oxyamine mixture.Oxyamine mixture preferably has about 3-approximately 10, about 4-approximately 9, about 5-approximately 8, about 6-approximately 8, or the pH of about 6-approximately 7.
For the situation of synthetic NHPI, when initial by the oxyamine of complete deprotonation in the aqueous solution, reactor speed and productive rate are the highest.Increase oxyamine concentration and provide excessive oxyamine can cause the productive rate increasing.For example, 1.5 times of excessive oxyamines (referring to embodiment 2) can cause higher product purity.
Before reaction, the mol ratio of oxyamine and cyclic carboxylic acids acid anhydrides is about 0.8-approximately 2.0, about 1-approximately 1.8, about 1-approximately 1.6, about 1-approximately 1.5, about 1.1-approximately 1.4, about 1.2-approximately 1.3.Preferably the ratio of oxyamine and cyclic carboxylic acids acid anhydrides is greater than 1.0.
Preferably, the pH of described the first mixture is about 2-approximately 10, about 2-approximately 8, about 3-approximately 7, about 2-approximately 6, about 3-approximately 6, about 4-approximately 6, or about 5-approximately 6.Can make described the first mixture react, make to form for example NHPI of cyclic imide compound that N-replaces, wherein respond, substantially respond, the described reaction of most of reaction or at least a portion is being less than approximately 100 ℃, or be less than approximately 90 ℃, or be less than approximately 80 ℃, or be less than at the temperature of approximately 70 ℃ and carry out." substantially respond " and refer to that the reaction more than approximately 90% is for example less than approximately 100 ℃ in given temperature, or be less than approximately 90 ℃, or be less than approximately 80 ℃, or be less than at the temperature of approximately 70 ℃ and carry out.
Final pH is depended in the recovery of the phthalic imidine that N-replaces.For example, the pH of about 1-approximately 2 allows maximum NHPI to reclaim the decomposition with minimum NHPI.If pH is brought down below approximately 1, NHPI may resolve into phthalic acid, and this is undesirable.
Therefore, supplementary acid can be added the first mixture to reduce the pH of described the first mixture, form the second mixture.Optionally, before adding acid, can from the first mixture, take out the cyclic imide compound of the described N-replacement of at least a portion.The preferred conventional acid that uses sulfuric acid or hydrochloric acid or other can add to reduce the pH of solution and do not participate in described reaction directly.The pH of described the second mixture can be less than approximately 7, is less than approximately 6, is less than approximately 5, is less than approximately 4, is less than approximately 3, is less than approximately 2, or is less than approximately 1.In another embodiment, the pH of described the second mixture can be about 1-approximately 7, about 1-approximately 4, about 1-approximately 3,1-approximately 2, about 2-approximately 6, or about 3-approximately 6.
Described acid being added described the first mixture to form after described the second mixture, desirable product is precipitated in described the second mixture.In one embodiment, described the first mixture can be heated to be less than the temperature of approximately 100 ℃.In another embodiment, the temperature of described the first mixture can be less than approximately 90 ℃, be less than approximately 80 ℃, or is less than approximately 70 ℃.In another embodiment still, the temperature of described reaction can be approximately 100 ℃-Yue 90 ℃, approximately 90 ℃-Yue 80 ℃, approximately 80 ℃-Yue 70 ℃.The pH of described the second mixture can be reduced to and be less than approximately 7, is less than approximately 6, is less than approximately 5, is less than approximately 4, is less than approximately 3, or is less than approximately 2.
Optionally, the pH that described the first mixture can occur in series of steps reduces, wherein (i) adds described the first mixture to form the second mixture acid, (ii) take out the cyclic imide of the N-replacement of at least a portion, (iii) add described the second mixture to reduce the pH of described the second mixture acid after taking out the cyclic imide that described N-replaces, (iv) from described the second mixture, take out the cyclic imide of the described N-replacement of at least a portion, (v) other acid is added to described the second mixture; (vi) from described the second mixture, take out the cyclic imide of the described N-replacement of at least a portion; Etc..The end that adds step in each acid, the pH of described the second mixture can be reduced to and be less than approximately 7, is less than approximately 6, is less than approximately 5, is less than approximately 4, is less than approximately 3, is less than approximately 2, or is less than approximately 1.In this embodiment, the temperature of described reaction can be less than approximately 90 ℃, be less than approximately 80 ℃, or is less than approximately 70 ℃.In addition, the temperature of described reaction can be approximately 100 ℃-Yue 90 ℃, approximately 90 ℃-Yue 80 ℃, approximately 80 ℃-Yue 70 ℃.
In addition, for example, for example, in alcohol (2-butanols and methyl alcohol) or the two-phase medium (, 2-butanol/water) that comprises alcohol and water, proved by hydroxyl amine salt (hydroxylamine sulfate and hydroxy amine hydrochloric acid salt) and the synthetic NHPI of Tetra hydro Phthalic anhydride.Use the order of methyl alcohol and hydroxy amine hydrochloric acid salt to allow homogeneous reaction condition, and promote to remove the inorganic salt that form between the reaction period.Use two-phase conditions permit simply to take out organic product.
The catalyzer of preparing by the present invention can be used for making hydrocarbon to be oxidized to corresponding hydroperoxide, alcohol, ketone, carboxylic acid or dicarboxylic acid.Oxidizing process comprises makes the reaction medium that wraps hydrocarbonaceous feed contact in reaction zone and under the catalyzer that comprises the cyclic imide of preparing by the inventive method exists with oxygen-containing gas.Hydrocarbon charging and conventional method for oxidation are described below.
Hydrocarbon charging
The cyclic imide that N-that use is prepared by method disclosed by the invention replaces, replacement or unsubstituted saturated or unsaturated hydrocarbons, for example paraffinic hydrocarbons, naphthenic hydrocarbon, alkene, cycloolefin and aromatic substances that can selective oxidation wide range of types.Yet especially, present method is oxidized to tert-butyl hydroperoxide and the trimethyl carbinol for selective isobutene, and hexanaphthene selective oxidation becomes hexalin and pimelinketone, becomes corresponding hydroperoxide with the Alkylaromatics selective oxidation of general formula (II):
R wherein
4and R
5represent independently of one another hydrogen or have the alkyl of 1-4 carbon atom, condition is R
4and R
5can be connected to form the cyclic group with 4-10 carbon atom, described cyclic group is optionally substituted, and R
6represent hydrogen, one or more alkyl or cyclohexyl with 1-4 carbon atom.In one embodiment, R
4and R
5being connected to form by the alkyl of one or more 1-4 of having carbon atom or the cyclic group with 4-10 carbon atom that replaced by one or more phenyl, is cyclohexyl expediently.The example of suitable Alkylaromatics is ethylbenzene, isopropyl benzene, sec-butylbenzene, secondary penta benzene, p-methyl sec-butylbenzene, Isosorbide-5-Nitrae-phenylbenzene hexanaphthene, secondary own benzene and phenylcyclohexane, preferably sec-butylbenzene and phenylcyclohexane.It will also be understood that R therein
4and R
5be connected to form under the situation of cyclic group, the carbon number that forms cyclic rings is 4-10.Yet described ring itself can be with one or more substituting groups, one or more alkyl or one or more phenyl with 1-4 carbon atom for example, as the situation of Isosorbide-5-Nitrae-phenylbenzene hexanaphthene.
In an actual embodiment, the Alkylaromatics of general formula (II) is sec-butylbenzene and by under alkylation conditions and at heterogeneous catalyst, for example zeolite beta or more preferably under the existence of at least one MCM-22 family molecular sieve (as giving a definition) with C at least
4alkylating reagent is prepared benzene alkylation.
In another actual embodiment, the Alkylaromatics of general formula (II) is phenylcyclohexane, and by make benzene and hydrogen contact preparation under the existence of heterogeneous dual-function catalyst, this dual-function catalyst comprises at least one metal that is conventionally selected from palladium, ruthenium, nickel and cobalt with hydrogenation activity, with the crystalline inorganic oxide material with alkylation activity, at least one MCM-22 family molecular sieve (as giving a definition) normally.
The oxidation of hydrocarbon
Term " group ", " base " and " substituting group " are used interchangeably in the literature.For the object of present disclosure, " alkyl " is defined as comprising hydrogen atom and 20 carbon atoms and can be the group of line style, branching or ring-type at the most, and when ring-type, is aromatics or non-aromatic." alkyl of replacement " is the group that wherein at least one hydrogen atom in alkyl is replaced by least one functional group or wherein at least one non--hydrocarbon atom or group have inserted alkyl.
Oxidation step in this technique is by making hydrocarbon substrate contact and carry out in reaction zone and under the cyclic imide catalyzer replacing at N-existence with oxygen-containing gas.
Generally speaking, the cyclic imide that can be used as oxide catalyst is deferred to following general formula
R wherein
7, R
8, R
9and R
10in each independently selected from thering is the alkyl of 1-20 carbon atom and the alkyl of replacement, or group SO
3h, NH
2, OH and NO
2, or atom H, F, Cl, Br and I; Each in X and Z is independently selected from C, S, CH
2, N, P and periodictable the 4th family's element; Y is O or OH; K is 0,1 or 2; With 1 be 0,1 or 2.Expediently, R
7, R
8, R
9and R
10in each independently selected from aliphatic alkoxyl group or aromatics alkoxyl group, carboxyl, alkoxyl group-carbonyl and alkyl, each of described group has 1-20 carbon atom.
The desirable product that derives from technique of the present invention will drop within the scope of the cyclic imide of general formula above.Therefore, various cyclic carboxylic acids, include but not limited to that Tetra hydro Phthalic anhydride can be used as intermediate with the cyclic imide of general formula above obtaining together with oxyamine or its salt.
In an actual embodiment, cyclic imide catalyzer comprises HP (NHPI), and preferably with the about 5wt% of approximately 0.0001wt%-of hydrocarbon substrate, for example the amount of the about 1wt% of about 0.1wt%-is present in reaction zone.
The oxidation of hydrocarbon substrate is conventionally at approximately 20 ℃-Yue 300 ℃, be more particularly temperature and/or the about 7000kPa of about 100kPa-of approximately 50 ℃-Yue 130 ℃, more particularly be greater than 500kPa to 0.1-100 volume % in the pressure of about 5000kPa and/or oxygen-containing gas, under the oxygen concn of common about 2-approximately 10 volume % oxygen, carry out.
Oxidation products
The product of this oxidizing process depends on the character of oxidized hydrocarbon substrate, but normally hydroperoxide, alcohol, ketone, carboxylic acid or dicarboxylic acid, especially hydroperoxide.
In the situation that hydrocarbon substrate is the Alkylaromatics of general formula (II), the product of oxidizing reaction comprises the hydroperoxide of general formula (IV):
R wherein
4, R
5and R
6have and implication identical in formula (II).Preferably, hydroperoxide are sec-butylbenzene hydroperoxide or phenylcyclohexane hydroperoxide.Then these hydroperoxide can change into by acid cleavage phenol and the general formula R of phenol or replacement
4cOCH
2r
5(V) aldehydes or ketones, wherein R
4and R
5have and implication identical in formula (II).
In one embodiment, the Alkylaromatics of oxidation is phenylcyclohexane, and oxidation products is phenylcyclohexane hydroperoxide, and split product comprises phenol and pimelinketone.Derive from the rough pimelinketone of cleavage step and pimelinketone and the phenol that rough phenol can be further purified to make purifying.Suitable purifying process includes, but not limited to a series of distillation towers so that pimelinketone and phenol and other separating substances.Pimelinketone itself rough or purifying can carry out hydrogenation so that it changes into phenol.This hydrogenation can for example for example be carried out on platinum, nickel or palladium at catalyzer.
Now with reference to following non-limiting examples, the present invention is more particularly described.
Hydroxylamine sulfate, Tetra hydro Phthalic anhydride and HP for following non-limiting examples are provided by Sigma-Aldrich company.
Embodiment 1 (the present invention)
By 6.7 grams of (40.9mmol; 1.25 equivalents) hydroxylamine sulfate [(NH
2oH)
2sO
4] be dissolved in 13.4mL deionized water and be slowly incorporated in 4.3mL50wt% (81.8mmol) NaOH in 7.3mL water so that hydroxylamine sulfate deprotonation.Add 10.9 grams of (73.6mmol) Tetra hydro Phthalic anhydride thin slices to form mixture to react with oxyamine.Therefore, the mol ratio of oxyamine and Tetra hydro Phthalic anhydride is about 1.25.Add after Tetra hydro Phthalic anhydride, start mixture to be heated to 90 ℃.After 9 minutes, (67 ℃) mixture becomes muddy; At this moment Tetra hydro Phthalic anhydride does not dissolve completely.Once it is muddy that mixture becomes, and adds 25mL DI water.Continue heating and mixture is remained at 90 ℃ to 15 minutes.After amounting to 30 minute reaction times, stop heating and stir.Make it be cooled to room temperature.Elimination white solid and make its at 75 ℃ dry 3 hours after 16 hours.Mother liquor pH is at about 4-5.
Filter for the first time the 8.9 grams of HPs (NHPI) that obtain 98% purity.It transforms into about 72% productive rate.
By 1mL30vol% (6.2mmol) H
2sO
4add mother liquor, until pH is down to 2.Do not precipitate.Mild heat to 75 ℃ continues 5 minutes, then makes it be cooled to room temperature.After 24 hours, form spicule.Elimination solid and 75 ℃ of drying solids 3 hours.
Filter for the second time the NHPI that obtains other 1.1 gram of 98% purity, it transforms into about other 9% productive rate.
After filtration, at room temperature further from mother liquor, precipitate.Elimination spicule and " dripping shape " crystal.
Filter and obtain other 0.3 gram of NHPI for the third time; Yet the purity of this NHPI is only approximately 62%.
Embodiment 2 (the present invention)
By 9.84 grams of (60mmol; 1.5 equivalents) hydroxylamine sulfate (HAS) is dissolved in 54mL deionized water solution.Slowly add 6.3mL50wt%NaOH solution.Not observing gas emits.Add 11.84 grams of (80mmol) Tetra hydro Phthalic anhydrides (PA) thin slice.Therefore, the mol ratio of oxyamine and Tetra hydro Phthalic anhydride is 1.5.After adding, start to be heated to 90 ℃.PA dissolves (pH=3-4) completely and rapidly.At 80 ℃, after 10 minutes, orange mixture becomes muddy.After 15 minutes, at 90 ℃, close heating.Mother liquor is under the pH of about 6-7.Make it be cooled to room temperature.Elimination faint yellow solid and dry 3 hours at 75 ℃ after 1 hour.Mother liquor is under approximately 6 pH.
Filter for the first time the NHPI that obtains 6.64 gram of 100% purity, productive rate approximately 50.9%.
By rare (30vol%) H
2sO
4slowly add mother liquor:
(i) add 1mLH
2sO
4make pH be reduced to approximately 4 and solution become less orange and more muddy.
(ii) further add 1mL H
2sO
4make pH be reduced to approximately 3, and the temperature of mother liquor is increased to approximately 90 ℃.It is thicker that suspension becomes.
(iii) further add 1mL H
2sO
4make pH be reduced to about 2-3.Suspension becomes very limpid (white) and makes it be cooled to room temperature.Elimination white solid and dry 3 hours at 75 ℃.
Add in addition 3mL H
2sO
4obtain the NHPI of other 5.04 gram of 100% purity.
Reclaim 11.68 grams of total solidss, overall yield approximately 89.7%.
Embodiment 3 (NHPI in 2-butanols is synthetic)
20mL2-butanols is added to 3.07 grams of (18.3mmol) hydroxyl ammonium vitriol (HAS) in the three-necked flask that reflux exchanger and stirring rod are housed, and be heated to 100 ℃.Not observing HAS dissolves.Add 5.42 grams of (36.6mmol) Tetra hydro Phthalic anhydrides (PA) and make temperature increase to 120 ℃ (boiling points).PA dissolves completely, and HAS is only partly dissolved.The thin out Huang of dispersion liquid.At 120 ℃, continue vigorous stirring.HAS does not still dissolve completely.Add about 0.5mL deionized water to promote material to carry, and under refluxing, continue to stir to amount to 3.5 hours.Remove yellow organic phase and leach white spicule, forming first organic fraction.From mother liquor, evaporating solvent obtains second organic fraction.2-butanols is added to white crystal and be heated to and reflux, but crystal does not dissolve.Add 2-butanols/white crystal suspension to form solvent fraction about 4mL deionized water, white crystal is approximately 120 ℃ of dissolvings thus.When suspension is cooling, in water, form transparent crystals.All fractions are at N
2dry in draft furnace.
In first organic fraction, reclaim 1.14 grams of solids, described solid comprises 78%NHPI, 18% ester and 3% phthalic acid.
In second organic fraction, reclaim 5.17 grams of solids, described solid comprises 5%NHPI, 77% ester and 18% phthalic acid.
In solvent fraction, reclaim 1.00 grams of solids, it is not containing NHPI, ester or phthalic acid.
Embodiment 4 (NHPI in methyl alcohol is synthetic)
5.42 grams of (36.6mmol) Tetra hydro Phthalic anhydrides (PA) are added to 15mL methyl alcohol and temperature is increased to approximately 80 ℃ until dissolution of solid.Add 2.55 grams of (36.7mmol) NH
2oH (HCl) and continuation are stirred until hydroxy amine hydrochloric acid salt [NH
2oH (HCl)] dissolve.At this moment do not see and reacting.Add 1.9 grams of (18.3mmol) Na
2cO
3and see CO
2emit.Continue to stir and amount to 3 hours.Close heating and make it be cooled to room temperature.Evaporating solvent, but only obtain the yellow oil of the white solid with dispersion.Add 20mL deionized water, oil dissolves completely thus.Under the pH of about 6-7, spend the night and there is no solid precipitation.Drip the vitriol oil (H
2sO
4).In adding of acid, a little occur that solid forms, it is slowly dissolved in water.Add acid until pH reaches about 3-4, and precipitation is no longer dissolved.Temperature is increased to 80 ℃ and continues 10 minutes, thus dissolution of solid.Make it be cooled to room temperature.Leach solid (thin spicule) and be dried 3 hours at 75 ℃.
Filter and obtain 0.93 gram of precipitation (96%NHPI and 4% phthalic acid) for the first time.
From mother liquor except desolventizing and by adding 30mL deionized water to make its recrystallization.Solid does not dissolve completely.Make it be cooled to room temperature.Leach solid (thin spicule) and be dried 3 hours at 75 ℃.
Filter and obtain 2.72 grams of precipitations (86%NHPI, 14% ester) for the second time.
Embodiment 5 (NHPI is synthetic under two-phase condition)
10mL2-butanols is added to 5.42 grams of (36.6mmol) Tetra hydro Phthalic anhydrides (PA) in the three-necked flask that reflux exchanger and stirring rod are housed, and be heated to 75 ℃.Add 2mL deionized water and temperature is increased to 105 ℃.PA does not dissolve completely.Add 5mL2-butanols and increase temperature until reach boiling point.Add after 1mL deionized water, form clear solution (not seeing water).Slowly add 3.07 grams of hydroxyl ammonium vitriol (HAS).Add after end, have second-phase.After approximately 1 hour, solution becomes slight yellow.Under refluxing, stir and amount to 4 hours, then make temperature be down to room temperature and close and stir several hours.In water layer, form transparent crystals; Organic layer contains faint yellow spicule and " dripping shape " cauliflower form crystal.Temperature be increased to 120 ℃ and at 60 ℃ all spicules be dissolved in organic layer.But " drip shape ", crystal still exists, and shows that the neighbour phthalate anhydride of NHPI is dissolved in 2-butanols more.All crystals in water layer also dissolves.At 120 ℃ of separated organic phases and water, and make it be cooled to room temperature.In water, form transparent crystals and in organic phase, form yellow mercury oxide.Leach crystal and at N
2in draft furnace, at 50 ℃, be dried 4 hours.
Filter organic layer and obtain 840mg precipitation (24%NHPI, 65% phthalic acid, 11% ester).
Filter water layer and obtain 2.58 grams of precipitations (there is no organic compound).
NHPI product fraction in all embodiment is passed through
13c NMR characterizes.
Although describe and illustrated the present invention with reference to particular, those of ordinary skill in the art are applicable to not necessarily in the modification illustrating herein understanding the present invention.For this reason, in order to determine the object of true scope of the present invention, should be only with reference to appended claims.
Claims (20)
1. a technique of preparing the cyclic imide compound of N-replacement, comprises the following steps:
A. make cyclic carboxylic acids acid anhydrides in the aqueous solution, contact to form the first mixture with oxyamine or its salt, the pH of wherein said the first mixture is about 2-approximately 6, and wherein before reaction in described the first mixture the mol ratio of oxyamine and carboxylic acid anhydride be about 0.8-approximately 2.0; With
B. make described mixture react, make to form the cyclic imide compound that N-replaces.
2. the technique of claim 1, further comprising the steps:
A. acid is added described the first mixture to reduce the pH of described the first mixture, form the second mixture; With
B. from described the second mixture, take out the cyclic imide compound of the described N-replacement of at least a portion.
3. the technique of claim 2, further comprising the steps:
A. acid is added described the second mixture to reduce the pH of described the second mixture; With
B. take out the cyclic imide compound of the described N-replacement of at least a portion.
4. claim 2 or 3 technique, wherein add and from described the first mixture, take out the cyclic imide compound that the described N-of at least a portion replaces before described acid.
5. the technique of claim 1, the cyclic imide compound that wherein said N-replaces is deferred to following general formula:
R wherein
7, R
8, R
9and R
10in each independently selected from thering is the alkyl of 1-20 carbon atom and the alkyl of replacement, or group SO
3h, NH
2, OH and NO
2, or atom H, F, Cl, Br and I; Each in X and Z is independently selected from C, S, CH
2, N, P and periodictable the 4th family's element; Y is O or OH; K is 0,1 or 2; With 1 be 0,1 or 2.
6. the technique of the aforementioned claim of any one, the cyclic imide compound that wherein said N-replaces is HP.
7. the technique of the aforementioned claim of any one, wherein said carboxylic acid anhydride is Tetra hydro Phthalic anhydride.
8. the technique of the aforementioned claim of any one, wherein said carboxylic acid anhydride is the Tetra hydro Phthalic anhydride replacing.
9. the technique of the aforementioned claim of any one, wherein said oxyamine is derived from hydroxylamine sulfate and hydroxy amine hydrochloric acid salt.
10. the technique of the aforementioned claim of any one, wherein in described contact (a) before, makes described hydroxyl amine salt contact with deprotonation choline, makes oxyamine that the described hydroxyl amine salt of at least a portion changes into deprotonation to form oxyamine mixture.
The technique of 11. claims 10, wherein said oxyamine mixture has the pH of about 6-approximately 8.
The technique of the aforementioned claim of 12. any one, the pH of wherein said the first mixture is about 4-approximately 6.
The technique of the aforementioned claim of 13. any one, the pH of wherein said the second mixture is about 1-approximately 3.
The technique of the aforementioned claim of 14. any one, the pH of wherein said the second mixture is about 1-approximately 2.
The technique of the aforementioned claim of 15. any one, wherein the described reaction of at least a portion is carried out being less than at the temperature of approximately 100 ℃.
The technique of the aforementioned claim of 16. any one, wherein the described reaction of at least a portion is carried out being less than at the temperature of approximately 90 ℃.
The technique of the aforementioned claim of 17. any one, wherein before reaction, the mol ratio of oxyamine and carboxylic acid anhydride is about 1-approximately 1.8 in described the first mixture.
The technique of the aforementioned claim of 18. any one, wherein before reaction, the mol ratio of oxyamine and carboxylic acid anhydride is about 1-approximately 1.5 in described the first mixture.
The technique of the aforementioned claim of 19. any one, wherein before reaction, the mol ratio of oxyamine and carboxylic acid anhydride is about 1.1-approximately 1.4 in described the first mixture.
The technique of the aforementioned claim of 20. any one, wherein before reaction, the mol ratio of oxyamine and carboxylic acid anhydride is about 1.2-approximately 1.3 in described the first mixture.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US16571409P | 2009-04-01 | 2009-04-01 | |
| US61/165,714 | 2009-04-01 | ||
| PCT/US2010/022727 WO2010120398A2 (en) | 2009-04-01 | 2010-02-01 | Process for preparing n-substituted cyclic imides |
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| CN104039763A true CN104039763A (en) | 2014-09-10 |
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| CN201080071274.XA Pending CN104039763A (en) | 2009-04-01 | 2010-02-01 | Process for preparing n-substituted cyclic imides |
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| TW (1) | TWI510468B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106831535A (en) * | 2016-12-19 | 2017-06-13 | 南京红宝丽醇胺化学有限公司 | A kind of method that low corrosion produces N hydroxyphthalimides |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1239715A (en) * | 1999-06-15 | 1999-12-29 | 中国科学院广州化学研究所 | Synthesis process of N-hydroxyl phthalimide |
| JP2003081941A (en) * | 2001-09-12 | 2003-03-19 | Sumitomo Chem Co Ltd | Method for producing n-hydroxyl cyclic imide |
| CN1476352A (en) * | 2001-09-28 | 2004-02-18 | ����贻�ѧ��ҵ��ʽ���� | Catalysts comprised of N-substituted cyclic imides and processes for preparing organic compounds with catalysts |
| CN1953963A (en) * | 2004-05-17 | 2007-04-25 | 大赛璐化学工业株式会社 | Process for producing cyclic N-hydroxyimide compound |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4080026B2 (en) * | 1997-05-13 | 2008-04-23 | ダイセル化学工業株式会社 | Oxidation method of ethers |
| JP4451939B2 (en) * | 1999-02-19 | 2010-04-14 | ダイセル化学工業株式会社 | Method for producing cycloalkanone |
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- 2010-02-01 CN CN201080071274.XA patent/CN104039763A/en active Pending
- 2010-02-09 TW TW099103961A patent/TWI510468B/en not_active IP Right Cessation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1239715A (en) * | 1999-06-15 | 1999-12-29 | 中国科学院广州化学研究所 | Synthesis process of N-hydroxyl phthalimide |
| JP2003081941A (en) * | 2001-09-12 | 2003-03-19 | Sumitomo Chem Co Ltd | Method for producing n-hydroxyl cyclic imide |
| CN1476352A (en) * | 2001-09-28 | 2004-02-18 | ����贻�ѧ��ҵ��ʽ���� | Catalysts comprised of N-substituted cyclic imides and processes for preparing organic compounds with catalysts |
| CN1953963A (en) * | 2004-05-17 | 2007-04-25 | 大赛璐化学工业株式会社 | Process for producing cyclic N-hydroxyimide compound |
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| 王明霞等: "N-羟基琥珀酰亚胺合成工艺的改进", 《工业药学》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106831535A (en) * | 2016-12-19 | 2017-06-13 | 南京红宝丽醇胺化学有限公司 | A kind of method that low corrosion produces N hydroxyphthalimides |
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| TWI510468B (en) | 2015-12-01 |
| TW201040140A (en) | 2010-11-16 |
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