CN105916833A - Method for producing cyclobutanetetracarboxylic acid and anhydride thereof - Google Patents
Method for producing cyclobutanetetracarboxylic acid and anhydride thereof Download PDFInfo
- Publication number
- CN105916833A CN105916833A CN201580004814.5A CN201580004814A CN105916833A CN 105916833 A CN105916833 A CN 105916833A CN 201580004814 A CN201580004814 A CN 201580004814A CN 105916833 A CN105916833 A CN 105916833A
- Authority
- CN
- China
- Prior art keywords
- formula
- acid
- carbon number
- alkyl
- carboxylic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 0 CC(C(C(C1C(O2)=O)C(O3)=O)C3=*)(C1C2=O)*=C Chemical compound CC(C(C(C1C(O2)=O)C(O3)=O)C3=*)(C1C2=O)*=C 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C61/00—Compounds having carboxyl groups bound to carbon atoms of rings other than six-membered aromatic rings
- C07C61/04—Saturated compounds having a carboxyl group bound to a three or four-membered ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/04—Systems containing only non-condensed rings with a four-membered ring
Abstract
Provided is a method for obtaining cyclobutanetetracarboxylic acid and/or a dianhydride thereof by using, as the raw material, the residue remaining after a target substance generated in a process for producing a cyclobutanetetracarboxylic acid derivative or the like has been separated. A method for: producing a tetracarboxylic acid represented by formula [7] by hydrolysis, in a solvent, of a mixture of a tetracarboxylic acid dialkyl ester represented by formula [1] and a tetracarboxylic acid dialkyl ester represented by formula [2]; and, as necessary, dehydrating the tetracarboxylic acid and producing a tetracarboxylic dianhydride represented by formula [5]. In the formula, R1 is a C1-5 alkyl group, R2 is a C1-5 alkyl group, n is 2 or 4, and R1 and R2 may be the same or different.
Description
Technical field
The present invention relates to novel Tetramethylene. tetrabasic carboxylic acid and the manufacture method of anhydride thereof.
Background technology
The tetracarboxylic acid derivatives such as tetrabasic carboxylic acid dialkyl are become polyamide, polyester or polyimides etc. former
The important substance of material.
Such as, there is as main chain the synthesis example of the polyimides of Tetramethylene. skeleton, report there is following example:
After making double (chloroformyl) cyclobutane dicarboxylic acid dimethyl ester and diamine reactant obtain polyamic acid methyl ester, will
It heats and makes polyimides (with reference to non-patent literature 1).
It addition, as having the Tetramethylene. tetrabasic carboxylic acid of substituent group on Tetramethylene. ring, in patent documentation 1
Report Tetramethylene. tetrabasic carboxylic acid dialkyl and it is carried out chlorination and double (chloroformyl) that obtain change
Compound.
In patent documentation 1, although obtained the Tetramethylene. tetrabasic carboxylic acid dialkyl as target using high yield
Derivant, but obtaining, for using, produce during object Tetramethylene. tetrabasic carboxylic acid dialkyl residual
Slag, is silent on as the useful thing such as Tetramethylene. tetracarboxylic dianhydride of initial substance by described Slag recovering.
Prior art literature
Patent documentation
Patent documentation 1: the open WO2010/092989 pamphlet of international patent application
Non-patent literature
Non-patent literature 1:High Performance Polymers, (1998), 10 (1), p11-21
Summary of the invention
The problem that invention is to be solved
It is an object of the invention to, it is provided that for by the manufacture process of Tetramethylene. tetracarboxylic acid derivatives etc.
Residue after the object separation produced, as raw material, is conveniently and efficiently obtained utility ring fourth by it
Alkane tetrabasic carboxylic acid and/or the novel method of Tetramethylene. tetracarboxylic dianhydride.
For solving the scheme of problem
The present invention is used for solving above-mentioned problem, has following purport.
1. the manufacture method of the tetrabasic carboxylic acid shown in formula [7], wherein, by the tetrabasic carboxylic acid dialkyl group shown in formula [1]
Ester is hydrolyzed in a solvent with the mixture of the tetrabasic carboxylic acid dialkyl shown in formula [2],
(in formula, R1For the alkyl of carbon number 1～5, R2For the alkyl of carbon number 1～5, n is 2 or 4, R1With R2
The most identical or different)
(in formula, R2Aforesaid meaning is represented) with n.
2. the manufacture method of the acid dianhydride shown in formula [5], wherein, takes off the tetrabasic carboxylic acid shown in formula [7]
Water.
(in formula, R2Aforesaid meaning is represented) with n
(in formula, R2Aforesaid meaning is represented) with n.
3. according to the manufacture method described in 1., wherein, formula [1] and formula [2] are respectively formula [1-a] and formula [2-a],
Formula [7] is following formula [7-a].
(in formula, R1For the alkyl of carbon number 1～5, R2For the alkyl of carbon number 1～5, R1With R2The most identical or
Different)
(in formula, R2Represent the alkyl of carbon number 1～5)
4. according to the manufacture method described in 2., wherein, formula [7] is following formula [7-a], and formula [5] is formula [5-a].
(in formula, R2Represent the alkyl of carbon number 1～5)
(in formula, R2Represent the alkyl of carbon number 1～5)
5. a tetracarboxylic compound, it represents by following formula [7-a].
(in formula, R2Alkyl for carbon number 1～5)
The effect of invention
The method according to the invention, it is possible to will produce in the manufacture process of Tetramethylene. tetracarboxylic acid derivatives etc.
Object separate after residue as raw material, be conveniently and efficiently produced from the ring as utility
BTCA and/or its dianhydride etc..
Detailed description of the invention
[Tetramethylene. tetrabasic carboxylic acid dialkyl]
Raw material in the manufacture method of the present invention is the manufacture process at Tetramethylene. tetrabasic carboxylic acid dialkyl etc.
Following formula [1] contained by the residue of middle generation or the compound shown in formula [2].
(in formula, R1For the alkyl of carbon number 1～5, R2For the alkyl of carbon number 1～5, n is 2 or 4.When n is 2,
R2It is preferably identical substituent group, when n is 4, whole R2The most identical, it is also possible to different.R1With R2
The most identical or different)
R1For carbon number 1～5, preferably 1～the alkyl of 3, as the concrete example of alkyl, methyl, second can be listed
Base, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl etc..Need
Illustrate, by carrying out imidizate after synthesizing polyamides acid esters, thus when being used as polyimides,
R1It is preferably the group that carbon number is few and is easily separated from, more preferably methyl.
R2For carbon number 1～5, preferably 1～the alkyl of 3, as the concrete example of alkyl, methyl, second can be listed
Base, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl etc..
N represents the integer of 1～4, preferably 2.
In above-mentioned formula [1] or formula [2], R2For the concrete example row that methyl, n are tetrabasic carboxylic acid dialkyl when 2
Lifting in table 1 below and table 2, applicable tetrabasic carboxylic acid dialkyl is not limited to them.
It should be noted that in table 1 below and table 2, a1～a4 and b1～b4 represents shown in following formula [6]
Respective position, the symbol in Tables 1 and 2 represents following meaning respectively.
Me: methyl, Et: ethyl, Pr-n: n-pro-pyl, Pr-iso: isopropyl, Bu-n: normal-butyl,
Bu-sec: sec-butyl, Bu-iso: isobutyl group, Bu-t: the tert-butyl group, Pen-n: n-pentyl, OMe:
Methoxyl group, OEt: ethyoxyl, OPr-n: positive propyl ether base, OPr-iso: isopropyl ether, OBu-n: just
Butoxy, OBu-sec: sec-butoxy, OBu-iso: isobutoxy, OBu-t: tert-butoxy, Open-n:
N-amylether base
[table 1]
[table 2]
It addition, in above-mentioned formula [1] or formula [2], be 2 and R at n2For ethyl, n-pro-pyl, isopropyl, just
In the case of the compound of butyl, sec-butyl, isobutyl group, the tert-butyl group or n-pentyl, can exemplify upper
State the Me in b1～b4 of Tables 1 and 2 be replaced as respectively Et, Pr-n, Pr-iso, Bu-n, Bu-sec, Bu-iso,
Bu-t or Pen-n and the compound that obtains.
Then, as example produced by the raw material in the present invention, for Tetramethylene. tetrabasic carboxylic acid dialkyl
Manufacture process describe.As shown in following reaction equation, Tetramethylene. tetrabasic carboxylic acid dialkyl passes through
Make Tetramethylene. tetracarboxylic dianhydride [5] and R1Carbon number shown in OH be 1～5 alcohol react and manufacture.
(in formula, R1For the alkyl of carbon number 1～5, R2For the alkyl of carbon number 1～5, n is 2 or 4.When n is 2,
R2It is preferably identical substituent group, when n is 4, whole R2The most identical, it is also possible to different.R1With R2
The most identical or different)
Above-mentioned reaction can still belong to the alcohol (R of reaction raw materials1OH) carry out as solvent, it addition,
Other solvent can be used as required.As long as described solvent does not limits the most especially to reaction is active
Fixed, the such as hydrocarbon such as hexane, heptane or toluene can be listed；The halogen such as chloroform, 1,2-dichloroethanes or chlorobenzene
For hydrocarbon；The ethers such as diethyl ether or 1,4-dioxane；The esters such as ethyl acetate；The ketone such as acetone or butanone；Acetonitrile
Or the nitrile such as propionitrile；Or their mixture.Preferably list ethyl acetate or acetonitrile, more preferably
Acetonitrile.
Alcohol (R1OH) generally use relative to tetracarboxylic dianhydride [5] 2～100 times moles, be preferably used 2～40
Times mole, more preferably use 2～20 times moles.
Above-mentioned reaction is carried out in neutral conditions, it is also possible to add alkali or acid.
As alkali, the inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate or sodium bicarbonate can be listed；
Triethylamine, pyridine, quinoline, 8-quinolinol, 1,10-phenanthroline, bath phenanthroline, bathocuproine, 2,2 '-connection
Pyridine, 2-phenylpyridine, 2,6-diphenyl amino pyridine, 2-dimethylamino naphthyridine, DMAP,
2-(2-hydroxyethyl) pyridine, N, accelerine, 1,8-diazabicyclo [5,4,0]-7-endecatylene
(DBU) organic base such as；The metal alkoxides such as Feldalat NM, Feldalat KM or potassium tert-butoxide.Be preferably Feldalat NM,
Feldalat KM or pyridine, more preferably pyridine.
As above-mentioned acid, the heteropoly acid such as phosphomolybdic acid, phosphotungstic acid, methyl borate., triphenyl can be listed
The organic acid such as phosphine；The mineral acids such as hydrochloric acid, sulphuric acid or phosphoric acid；The hydrocarbon acid such as formic acid, acetic acid or p-methyl benzenesulfonic acid；
The halogenated hydrocarbons acid such as trifluoracetic acid.It is preferably p-methyl benzenesulfonic acid, phosphoric acid or acetic acid, more preferably to toluene sulphur
Acid.
Above-mentioned alkali or acid generally use relative to tetracarboxylic dianhydride [5] 0～100 times moles, be preferably used
0.01～10 times moles.
Reaction temperature is not particularly limited, for example,-90～200 DEG C, preferably-30～100 DEG C.During reaction
Between usually 0.05～200 hour, be preferably 0.5～100 hour.
In above-mentioned formula [1] or [2], n is among the Tetramethylene. tetrabasic carboxylic acid dialkyl of 2, the most effectively makes
Make the method for compound shown in specific position isomer, i.e. previously described formula [1-a], formula [2-a] or formula [2-b] such as
Lower described.
Compound shown in formula [1-a] or formula [2-a] can be by using the tetrabasic carboxylic acid two shown in following formula [5-a]
Acid anhydride manufactures as the tetracarboxylic dianhydride [5] of previous reaction formula.
(in formula, R2Represent the alkyl of carbon number 1～5)
Now, reaction temperature is the lowest, then the selection rate of formula [1-a] more can improve.Therefore, it is desirable to raising formula
During the reaction yield of [1-a], preferred reaction temperature is 10～30 DEG C.On the other hand, it is desirable to improve formula
During the reaction yield of [2-a], preferred reaction temperature is 50～100 DEG C.
During it addition, there occurs reaction in the presence of alkali or acid, it is also possible to improve formula [1-a] selection rate and
Response speed, is more preferably the presence of alkali compounds.The alkali now used or acid can list aforementioned illustration
Alkali or acid, preferred alkali or acid and preferably addition are also as described above.
It addition, this reaction can be easily separated the object generated in reaction.Such as, using formula [5-a] as
In the case of raw material, by distilling the alcohol that removal is used after the completion of reaction, the crystal of precipitation is being had
After machine solvent is heated to reflux, cool down, when leaching is cleaned the crystal separated out and is dried, it is possible to
Obtain a crystal of the high-purity goods of formula [1-a].As organic solvent, it is possible to use such as toluene,
Acetonitrile, ethyl acetate, ethyl acetate normal heptane mixed liquor, ethyl acetate alcohol mixed liquor, acetonitrile alcohol
Mixed liquor etc..It is preferably acetonitrile, ethyl acetate, ethyl acetate alcohol mixed liquor or the mixing of acetonitrile alcohol
Liquid.As alcohol, the rudimentary of the carbon numbers 1～5 such as methanol, ethanol, propanol, butanol, isopropanol can be listed
Alcohol.
One time crystal can also improve purity further by cleaning, recrystallization.As recrystallization method,
Can list after adding organic solvent in a crystal and heating, the method carrying out ice-cold filtration drying.
As organic solvent, it is possible to use such as toluene, acetonitrile, ethyl acetate, ethyl acetate normal heptane mix
Close liquid, ethyl acetate various alcohol mixed liquor, acetonitrile various alcohol mixed liquor etc..It is preferably acetonitrile, acetic acid
Ethyl ester, ethyl acetate various alcohol mixed liquor or acetonitrile various alcohol mixed liquor.As various alcohol, can
List methanol, ethanol, propanol, butanol, isopropanol etc..
About obtain these crystal time use organic solvent amount, generally by with 100% yield from
Weight during raw material acquisition target product, as benchmark, is preferably used 2 times amount～20 times amount of its weight.Separately
Outward, it is desirable to when improving yield, preferably reduce the consumption of organic solvent, it is desirable to when obtaining high-purity goods,
Preferably increase the consumption of organic solvent.During in view of their yield, purity, more preferably 2.5 times～5
Times.
On the other hand, by obtain a crystal time filtrate be carried out, recrystallization, it is possible to obtain
The high-purity goods of formula [2-a].That is, by gained filtrate being carried out solvent distillation removal, the crystalline substance that will separate out
Body is heated to reflux in organic solvent, then cools down, after the crystal thus separated out is carried out leaching,
When being carried out being dried, it is possible to obtain the secondary crystal of the high-purity goods of formula [2-a] as target.
As organic solvent, it is possible to use such as toluene, acetonitrile, ethyl acetate, ethyl acetate positive heptan
Alkane mixed liquor, ethyl acetate various alcohol mixed liquor, acetonitrile various alcohol mixed liquor etc..Be preferably acetonitrile,
Ethyl acetate, ethyl acetate various alcohol mixed liquor or acetonitrile various alcohol mixed liquor.As various alcohol,
Methanol, ethanol, propanol, butanol, isopropanol etc. can be listed.
Secondary crystal can also improve purity further by cleaning, recrystallization.As recrystallization method,
Can list after adding organic solvent in secondary crystal and heating, the method carrying out ice-cold filtration drying.
As organic solvent, it is possible to use such as toluene, acetonitrile, ethyl acetate, ethyl acetate normal heptane mix
Close liquid, ethyl acetate various alcohol mixed liquor, acetonitrile various alcohol mixed liquor etc..It is preferably acetonitrile, acetic acid
Ethyl ester, ethyl acetate various alcohol mixed liquor or acetonitrile various alcohol mixed liquor.As various alcohol, can
List methanol, ethanol, propanol, butanol, isopropanol etc..
About the consumption of organic solvent when obtaining these secondary crystals, generally by with 100% yield from
Weight when raw material obtains target product deduct above-mentioned taking-up after the wt part of a crystal and obtain
Weight as benchmark, its 2 times amount～20 times amount are preferably used.During it addition, want to improve yield, preferably
Reduce the consumption of organic solvent, it is desirable to when obtaining high-purity goods, preferably increase the consumption of organic solvent.
During in view of yield, purity, more preferably 2.5 times amount～5 times amount.
As above-mentioned formula [5], use the Tetramethylene. tetracarboxylic dianhydride shown in following formula [5-b], make this compound
Alcohol (aforesaid R with carbon number 1～51OH) react such that it is able to manufacture the chemical combination shown in formula [2-b]
Thing.
(in formula, R2Represent the alkyl of carbon number 1～5)
Now, by reacting in the presence of alkali or acid, it is possible to increase the selection rate of formula [2-b] is with anti-
Answer speed, be more preferably the presence of alkali compounds.The alkali now used or acid can list the alkali of aforementioned illustration
Or acid, preferred alkali or sour and preferred addition are the most as implied above.
(in formula, R1For the alkyl of carbon number 1～5, R2For the alkyl of carbon number 1～5, n is 2 or 4.When n is 2,
R2It is preferably identical substituent group, when n is 4, whole R2The most identical, it is also possible to different.R1With R2
The most identical or different)
[being manufactured Tetramethylene. tetrabasic carboxylic acid and/or Tetramethylene. tetracarboxylic dianhydride by the compound of formula [1] and formula [2]]
In the present invention, as shown in described as follows [reaction equation 1] and [reaction equation 2], by will be at Tetramethylene.
Contained by the residue produced in the manufacture process of tetrabasic carboxylic acid dialkyl etc., above-mentioned formula [1] and formula [2]
Compound is hydrolyzed and manufactures Tetramethylene. tetrabasic carboxylic acid [7], is made by this Tetramethylene. tetrabasic carboxylic acid [7] further
Anhydride such that it is able to manufacture Tetramethylene. tetrabasic carboxylic acid and/or Tetramethylene. tetracarboxylic dianhydride.
(in formula, R1For the alkyl of carbon number 1～5, R2For the alkyl of carbon number 1～5, n is 2 or 4, R1With R2
The most identical or different)
In the reaction of above-mentioned [reaction equation 1], such as by by-product when isolating the object generated in esterification
Filtrate in solvent carry out distillation remove after, add general formula R CO2Carboxylic acid shown in H, acidic aqueous solution
Or alkaline aqueous solution, preferably cool down after being heated to reflux, the crystal leaching thus separated out is cleaned
And time dry, it is possible to obtain the crystal of the high-purity goods of Tetramethylene. tetrabasic carboxylic acid [7].
Above-mentioned carboxylic acid (RCO2H) as long as present the carboxylic acid of liquid condition at the reaction temperatures, just do not have
It is particularly limited to, the such as carbon number such as formic acid, acetic acid, propanoic acid can be listed and be preferably the aliphatic carboxylic acid of 1～5,
More preferably formic acid.As long as it addition, the acid used in acidic aqueous solution is dissolved in water at the reaction temperatures
Acid, be just not particularly limited, the such as heteropoly acid such as phosphomolybdic acid, phosphotungstic acid can be listed；Hydrochloric acid, sulfur
The mineral acids such as acid or phosphoric acid；The hydrocarbon acid such as formic acid, acetic acid, p-methyl benzenesulfonic acid；The halogenated hydrocarbons acid such as trifluoracetic acid.
It is preferably hydrochloric acid, sulphuric acid, phosphoric acid, p-methyl benzenesulfonic acid, formic acid or acetic acid, more preferably hydrochloric acid, sulphuric acid
Or p-methyl benzenesulfonic acid.
Sour consumption for acidic aqueous solution generally uses 0.01～100 relative to tetrabasic carboxylic acid diester [1] and [2]
Times mole, be preferably used 0.01～10 times moles.
If the amount that the acid being used to for the water consumption of acidic aqueous solution is dissolved at the reaction temperatures, just
It is not particularly limited, relative to acid to be used, generally uses 1～100 mass times, be preferably used 1～10
Quality times.
Alkali for alkaline aqueous solution is not particularly limited, and can list sodium hydroxide, potassium hydroxide, hydrogen
The alkali metal such as lithium oxide, sodium carbonate, potassium carbonate, lithium carbonate；The alkaline earth such as magnesium hydroxide, calcium hydroxide gold
Belong to.Wherein, sodium hydroxide, potassium hydroxide or Lithium hydrate are preferably listed.
Alkali consumption for alkaline aqueous solution generally uses 0.01～100 relative to tetrabasic carboxylic acid diester [1] and [2]
Times mole, be preferably used 0.01～10 times moles.
As long as the amount that the alkali used for the water consumption of alkaline aqueous solution dissolves at the reaction temperatures, just
It is not particularly limited, relative to acid to be used, usually 1～100 mass times, preferably 1～10 times of matter
Amount times.
Carboxylic acid (RCO2H), acidic aqueous solution or alkaline aqueous solution are relative to the tetrabasic carboxylic acid diester in filtrate
[1] generally use 2～100 times of weight with [2], 2～40 times of weight, more preferably use 2～6 weight are preferably used
Times.
It addition, use above-mentioned carboxylic acid (RCO2When H) reacting, it is also possible in the acid as catalyst
In the presence of carry out.As long as acid has the acid of comparatively strong acidity, it is not particularly limited.As this acid,
The heteropoly acid such as phosphomolybdic acid, phosphotungstic acid can be listed；The organic acid such as methyl borate., triphenylphosphine；Hydrochloric acid,
The mineral acid such as sulphuric acid or phosphoric acid；The hydrocarbon acid such as formic acid, acetic acid, p-methyl benzenesulfonic acid；The halogenated hydrocarbons such as trifluoracetic acid
Acid.It is preferably sulphuric acid, p-methyl benzenesulfonic acid, phosphoric acid or acetic acid, more preferably sulphuric acid or p-methyl benzenesulfonic acid.
Acid relative to tetrabasic carboxylic acid diester [1] and [2] generally use 0～100 times moles, be preferably used 0.01～10
Times mole.
Reaction temperature is not particularly limited, for example,-90～200 DEG C, preferably 80～130 DEG C.It addition,
Use carboxylic acid (RCO2When H) reacting, during especially with formic acid, by what reaction system generated
Reaction when alkyl formate is removed from reaction system is fast, it is therefore preferable that to be higher than generated formic acid
The boiling point of Arrcostab is implemented.
Response time is usually 0.05～200 hour, is preferably 0.5～100 hour.
On the other hand, in the reaction of above-mentioned [reaction equation 2], by making the Tetramethylene. obtained in [reaction equation 1]
Tetrabasic carboxylic acid [7] carries out dehydrant dehydration, it is possible to obtain Tetramethylene. tetracarboxylic dianhydride [5].
As dehydrant, as long as making dehydrant contact ring BTCA [7], just it is not particularly limited, example
As tetrabasic carboxylic acid [7] and dehydrant mixed in a solvent.As dehydrant, preferably acetic anhydride, third
The carboxylic acid anhydrides such as anhydride, trifluoro-acetic anhydride, it is preferred that carbon number preferably 1～3, carbon number more preferably 1～2 low
Level carboxylic acid anhydrides, wherein, easily removes, from the viewpoint of economical advantages after anhydride, particularly preferably
For acetic anhydride.
The consumption of dehydrant is not particularly limited, relative to Tetramethylene. tetrabasic carboxylic acid [7], and preferably 2～50 equivalents,
Particularly preferably 4～20 equivalents.It is 2～during 50 equivalent, is sufficiently carried out anhydride, and gained tetrabasic carboxylic acid two
The meltage of acid anhydride [5] will not too increase, it is possible to separates out tetracarboxylic dianhydride [5] with high yield.
It should be noted that need not make tetrabasic carboxylic acid [7] be completely dissolved and anhydride occur in homogeneous system
Reaction, it is also possible to implement anhydrideization reaction in heterogeneous system.
Carry out in the range of heating-up temperature in the reaction preferably 30～200 DEG C, more preferably 40～180 DEG C
, reaction temperature is the highest, then response speed more can improve.It is therefore preferable that with the backflow of solvent for use
Temperature is implemented.
It addition, the response time suitably sets according to conditions such as dehydrant kind used, temperature, excellent
Elect 0.5～20 hour as.Anhydride reaction can occur within this time fully.
Reacted by above-mentioned anhydrideization, it is possible to obtain suspended having tetracarboxylic dianhydride [5] in the dehydrant used
Suspension.After anhydrideization is reacted, gained suspension is filtered such that it is able to reclaim tetrabasic carboxylic acid
The powder of dianhydride [5].It addition, above-mentioned suspension can also be concentrated as required.And then, dry by decompression
Dry etc. remove dehydrant such that it is able to obtain highly purified raw material tetracarboxylic dianhydride [5].
It should be noted that the Tetramethylene. tetrabasic carboxylic acid shown in above-mentioned formula [7] obtained in the present invention is in document
The new compound not yet recorded, as it has been described above, can be used for be easily manufactured Tetramethylene. tetracarboxylic acid by it
The various uses such as acid dianhydride [5].
Embodiment
It is exemplified below out embodiment, illustrates in greater detail the present invention, but the present invention not limited by them
Explain.It addition, the analysis method used in embodiment is as follows.
<1H NMR analysis condition >
Device: Fourier transform type superconduction nuclear magnetic resonance device (FT-NMR) INOVA-400
(Varian company) 400MHz
Solvent: DMSO-d6
Internal standard material: tetramethylsilane (TMS)
The manufacture of<reference example 1>Tetramethylene. tetrabasic carboxylic acid dialkyl
Under stream of nitrogen gas, in the four-neck flask of 3L, put into 1,3-DM-CBDA 240g (1.07mol)
With ethyl acetate 720g, add pyridine 8.47g (0.107mol), with 25 DEG C under the stirring of magnetic stirring apparatus
Make it suspended.In the way of internal temperature reaches below 25 DEG C, expend 1 hour in this suspension and drip first
Alcohol 600g (18.73mol, relative to 1,3-DM-CBDA is 2.5wt times), also stirs 20 after completion of dropwise addition
Minute time, it is possible to obtain uniform reaction solution.When analyzing this reactant liquor with HPLC, compound (1-1)
HPLC relative area be 77%, the HPLC relative area of compound (2-1) is 22%.
With vaporizer, this reactant liquor is carried out solvent distillation under conditions of water-bath 40 DEG C, 170～140Torr
Remove, till inner capacities reaches 561.65g.Then, after adding ethyl acetate 1450g and stirring, use
Vaporizer carries out solvent distillation under conditions of water-bath 40 DEG C, 170～140Torr and removes, until inner capacities reaches
To 597.51g.Thereafter, after again adding ethyl acetate 1450g and stirring, with vaporizer in water-bath
Carry out solvent distillation under conditions of 40 DEG C, 170～140Torr to remove, till inner capacities reaches 1852g.
During it addition, be now analyzed, by gas chromatogram, the solvent that distillation is removed, the area % of methanol is 0.3%.
Then, the pulp solution of residual is heated to 80 DEG C so that it is after refluxing 30 minutes, in 10 minutes with
The speed of 2～3 DEG C is cooled to till internal temperature reaches 25 DEG C.After directly with 25 DEG C of stirrings 30 minutes, logical
Filter and obtain the white crystal separated out, this crystal ethyl acetate 192.88g is cleaned 2 times.Logical
Cross and it is carried out drying under reduced pressure, thus obtain white crystal 223.77g.Pass through1H NMR analysis result and
Confirm: this crystal is compound (1-1) (HPLC relative area is 99.0%) (yield is 72.5%).
<embodiment 1-1>manufactures (7-1) by the hydrolysis of dicarboxylic diester
In the four-neck flask of 1 liter, by filtering when will take out the crystal of (1-1) in reference example 1
The solution that the filtrate obtained merges with the cleanout fluid of crystal and obtains is removed with 40 DEG C of distillations carrying out solvent
Till gross weight reaches 170g, in gained solution, add the formic acid 424g of 88% purity, further
Carry out the distillation removal of solvent till gross weight reaches 340g.Sulphuric acid 29.5g is added in this solution,
Heated and stirred is carried out with 102 DEG C.Now, after removing the initial stage solvent that gradually distillates of 75g, further with
110 DEG C carry out 20 hours be heated to reflux.It addition, now confirm retention time according to following HPLC condition
Being that the peak area % of 6.3 minutes becomes less than 0.5%, cooling reactant liquor is until internal temperature reaches 23 DEG C is
Only.
Thereafter, after 20～25 DEG C of stirrings 1 hour, the crystal separated out is filtered, with the formic acid of 88% purity
42.4g carries out 2 times and cleans gained crystal, obtains coarse crystal (wet product) 97.3g of (7-1).And then,
In this coarse crystal 97.3g, add ethyl acetate 425g, under the internal temperature of 25 DEG C, carry out the slurry of 1 hour
After material stirring, filtering crystals, after cleaning 2 times with ethyl acetate 42.5g, gained white crystal is subtracted
When pressing dry dry, obtain (7-1) 72.01g (yield is 94.0%).
Pass through1H NMR analysis result and confirm: this crystal be (7-1).
1H NMR (DMSO-d6, δ ppm): 12.49 (s, 2H), 3.29 (s, 2H), 1.42 (s, 6H).
The HPLC (high performance liquid chromatography) used in this mensuration analyzes and implements according to following condition.
HPLC analysis condition:
Post: Atlantis cd18 (Waters company), 5um, 4.6 × 250mm, baking oven: 40 DEG C
Eluent: acetonitrile/0.5% phosphate aqueous solution=16/84 detection wavelength: 211nm
Flow velocity: 1.0mL/ minute sample injection rate: 10 μ L sample concentration: 1wt%
The manufacture of the anhydride (5-1) of<embodiment 1-2>tetrabasic carboxylic acid
Under stream of nitrogen gas, in the four-neck flask of 500mL, put into the tetrabasic carboxylic acid utilizing embodiment 1-1 to obtain
(7-1) 70g, acetic anhydride 350g, after making it suspended with 25 DEG C under the stirring of magnetic stirring apparatus, heating
Backflow (130 DEG C) 4 hours.Thereafter, it is cooled to internal temperature and reaches less than 25 DEG C, stir below 25 DEG C
Mix 1 hour.Thereafter, filter the white crystal separated out, this crystal dehydration acetonitrile 32g is cleaned 2 times
After, when gained white crystal is carried out drying under reduced pressure, obtain (5-1) 57.5g (yield 95%).
Pass through1H NMR analysis result and confirm: this crystal be (5-1).
1H NMR(DMSO-d6,δppm):3.89(s,2H),1.38(s,6H).
Industrial applicability
The manufacture method of the present invention is with the mesh that will produce in the manufacture process of Tetramethylene. tetracarboxylic acid derivatives etc.
Residue after mark thing separation is as raw material, it is possible to obtain Tetramethylene. tetrabasic carboxylic acid and/or Tetramethylene. tetrabasic carboxylic acid two
Acid anhydride, can be consequently used for field widely.
It should be noted that the saying of Japanese patent application filed in 17 days January in 2014 2014-007188
The full content of bright book, claims, accompanying drawing and summary is quoted so far, as the description of the present invention
Disclosure.
Claims (10)
1. the manufacture method of the tetrabasic carboxylic acid shown in formula [7], wherein, by the tetrabasic carboxylic acid dialkyl group shown in formula [1]
Ester is hydrolyzed in a solvent with the mixture of the tetrabasic carboxylic acid dialkyl shown in formula [2],
R1For the alkyl of carbon number 1～5, R2For the alkyl of carbon number 1～5, n is 2 or 4, R1With R2The most identical
Or different,
R2With the meaning of n as hereinbefore.
Manufacture method the most according to claim 1, wherein, with organic carboxylic with general formula R COOH
Acid reaction and be hydrolyzed, R is hydrogen or the alkyl of carbon number 1～10.
Manufacture method the most according to claim 1 and 2, wherein, is carried out in the presence of acid catalyst
Hydrolysis.
4. according to the manufacture method according to any one of claims 1 to 3, wherein, described solvent is for being selected from
Organic solvent in the group being made up of hydrocarbon, halogenated hydrocarbons, ester, ketone and nitrile.
5. the manufacture method of the acid dianhydride shown in formula [5], wherein, takes off the tetrabasic carboxylic acid shown in formula [7]
Water,
R2For the alkyl of carbon number 1～5, n is 2 or 4,
R2With the meaning of n as hereinbefore.
Manufacture method the most according to claim 5, wherein, in the presence of dehydrant, is heated to
40～160 DEG C and be dehydrated.
Manufacture method the most according to claim 5, wherein, dehydrant is the low-grade carboxylic acid of carbon number 1～3
Acid anhydride.
Manufacture method the most according to claim 1, wherein, formula [1] and formula [2] are respectively formula [1-a]
With formula [2-a], formula [7] is following formula [7-a],
R1For the alkyl of carbon number 1～5, R2For the alkyl of carbon number 1～5, R1With R2It is the most identical or different,
R2Alkyl for carbon number 1～5.
Manufacture method the most according to claim 5, wherein, formula [7] is following formula [7-a], formula [5]
For formula [5-a],
R2For the alkyl of carbon number 1～5,
R2Alkyl for carbon number 1～5.
10. a tetracarboxylic compound, its use following formula [7-a] represents,
R2Alkyl for carbon number 1～5.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014-007188 | 2014-01-17 | ||
| JP2014007188 | 2014-01-17 | ||
| PCT/JP2015/051149 WO2015108170A1 (en) | 2014-01-17 | 2015-01-16 | Method for producing cyclobutanetetracarboxylic acid and anhydride thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105916833A true CN105916833A (en) | 2016-08-31 |
Family
ID=53543053
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580004814.5A Pending CN105916833A (en) | 2014-01-17 | 2015-01-16 | Method for producing cyclobutanetetracarboxylic acid and anhydride thereof |
Country Status (5)
| Country | Link |
|---|---|
| JP (2) | JP6697178B2 (en) |
| KR (2) | KR102272227B1 (en) |
| CN (1) | CN105916833A (en) |
| TW (1) | TWI653225B (en) |
| WO (1) | WO2015108170A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6697178B2 (en) * | 2014-01-17 | 2020-05-20 | 日産化学株式会社 | Process for producing cyclobutane tetracarboxylic acid and its anhydride |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101044108A (en) * | 2004-10-20 | 2007-09-26 | 日产化学工业株式会社 | Cage-shaped cyclobutanoic dianhydrides and process for production thereof |
| US20080033199A1 (en) * | 2004-10-20 | 2008-02-07 | Eternal Chemical Co., Ltd. | Cyclobutanetetracarboxylate compound and preparation method thereof |
| JP2013163710A (en) * | 2012-02-09 | 2013-08-22 | Nissan Chem Ind Ltd | Polyimide precursor, polyimide, charge transport composition, and method for producing polyimide precursor |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60112736A (en) * | 1983-11-22 | 1985-06-19 | Mitsubishi Chem Ind Ltd | Production of cinnamic acid |
| CN104744257A (en) * | 2009-02-12 | 2015-07-01 | 日产化学工业株式会社 | Tetracarboxylic acid derivatives, processes for producing same, and liquid-crystal alignment material |
| JP6697178B2 (en) * | 2014-01-17 | 2020-05-20 | 日産化学株式会社 | Process for producing cyclobutane tetracarboxylic acid and its anhydride |
| KR102342657B1 (en) * | 2014-05-09 | 2021-12-22 | 닛산 가가쿠 가부시키가이샤 | Novel method for producing 1,3-di-substituted-cyclobutane-1,2,3,4-tetracarboxylic acid and dianhydride of said acid |
-
2015
- 2015-01-16 JP JP2015557904A patent/JP6697178B2/en active Active
- 2015-01-16 WO PCT/JP2015/051149 patent/WO2015108170A1/en active Application Filing
- 2015-01-16 KR KR1020217002662A patent/KR102272227B1/en active IP Right Grant
- 2015-01-16 KR KR1020167018418A patent/KR102247402B1/en active IP Right Grant
- 2015-01-16 CN CN201580004814.5A patent/CN105916833A/en active Pending
- 2015-01-19 TW TW104101673A patent/TWI653225B/en active
-
2020
- 2020-01-23 JP JP2020009324A patent/JP2020079247A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101044108A (en) * | 2004-10-20 | 2007-09-26 | 日产化学工业株式会社 | Cage-shaped cyclobutanoic dianhydrides and process for production thereof |
| US20080033199A1 (en) * | 2004-10-20 | 2008-02-07 | Eternal Chemical Co., Ltd. | Cyclobutanetetracarboxylate compound and preparation method thereof |
| JP2013163710A (en) * | 2012-02-09 | 2013-08-22 | Nissan Chem Ind Ltd | Polyimide precursor, polyimide, charge transport composition, and method for producing polyimide precursor |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6697178B2 (en) | 2020-05-20 |
| JP2020079247A (en) | 2020-05-28 |
| TW201542514A (en) | 2015-11-16 |
| KR102247402B1 (en) | 2021-04-30 |
| KR20210013332A (en) | 2021-02-03 |
| KR102272227B1 (en) | 2021-07-01 |
| KR20160108334A (en) | 2016-09-19 |
| WO2015108170A1 (en) | 2015-07-23 |
| TWI653225B (en) | 2019-03-11 |
| JPWO2015108170A1 (en) | 2017-03-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5247436B2 (en) | Method for producing methylene disulfonate compound | |
| US8329905B2 (en) | Synthesis of diethyl{[5-(3-fluorophenyl)-pyridine-2yl]methyl}phosphonate | |
| CN101538228B (en) | Method for synthesizing medical compound peramivir for resisting influenza viruses and avian influenza viruses | |
| JP2014040376A (en) | Method of producing bisphenol compound | |
| CN102146079B (en) | Preparation method of scopolamine butylbromide | |
| CN105916833A (en) | Method for producing cyclobutanetetracarboxylic acid and anhydride thereof | |
| CN105111238A (en) | Method for producing minodronic acid monohydrate by using water as solvent | |
| CN108191858A (en) | A kind of intermediate and preparation method for preparing pyrroloquinoline quinone | |
| CN108997229B (en) | 1,2,3, 4-tetrahydroquinoxaline-6-carboxylic acid methyl ester and preparation method thereof | |
| CN101519407B (en) | Synthesis method of cyclic acid anhydride capable of having substituent group | |
| CN109553595A (en) | A kind of Preparation Method And Their Intermediate of chiral gamma-butyrolactone | |
| CN108948077A (en) | A kind of the a-amino acid esters compound and its synthetic method of α-phosphorylated | |
| CN101605773B (en) | Process for production of dibenzoxepin compound | |
| CN101248060B (en) | Process for preparing benzimidazole compounds | |
| JP4734974B2 (en) | 2- (4-Cyanotetrahydropyran-4-yl) -2-oxoacetic acid ester and process for producing the same | |
| TWI791708B (en) | The production method of diol | |
| EP2419394A1 (en) | Process for the preparation of 2,4,6-octatriene-1-oic acid and 2,4,6-octatriene-1-ol | |
| CN102659713A (en) | Preparation method for cefdinir side-chain acid active ester | |
| CN104203887A (en) | Trisphenol production method | |
| RU2785963C1 (en) | Method for producing a condensed tricyclic compound and a corresponding intermediate | |
| JP4788049B2 (en) | Dicarboxylic acid diester derivative and method for producing the same | |
| WO2014206903A1 (en) | METHODS FOR THE PREPARATION OF SUBSTITUTED [1,2,4]TRIAZOLO[1,5-a]PYRIDINES | |
| JP4752121B2 (en) | Method for producing nitrile derivative, intermediate thereof and method for producing intermediate | |
| CN103242189A (en) | Method for catalytic preparation of aromatic amide compound by solid alkali | |
| CN116515089A (en) | Preparation method for synthesizing phenanthrenedione unit-containing conjugated polymer through direct functionalization of C-H bond |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160831 |
|
| RJ01 | Rejection of invention patent application after publication |