CN103237783B - The position different structure mixture of dehydroabietic acid derivant and manufacture method thereof - Google Patents
The position different structure mixture of dehydroabietic acid derivant and manufacture method thereof Download PDFInfo
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- CN103237783B CN103237783B CN201180057560.5A CN201180057560A CN103237783B CN 103237783 B CN103237783 B CN 103237783B CN 201180057560 A CN201180057560 A CN 201180057560A CN 103237783 B CN103237783 B CN 103237783B
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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- C07—ORGANIC CHEMISTRY
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- C07C61/00—Compounds having carboxyl groups bound to carbon atoms of rings other than six-membered aromatic rings
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- C07C61/39—Unsaturated compounds containing six-membered aromatic rings
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C69/753—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring of polycyclic acids
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Abstract
The invention discloses the position different structure mixture of a kind of dehydroabietic acid derivant, it contains the two or more dehydroabietic acid derivant represented by following formula (I) in di-2-ethylhexylphosphine oxide dehydroabietic acid and derivant thereof.It addition, the invention discloses the manufacture method of the position different structure mixture of dehydroabietic acid derivant represented by following formula (I).In formula (I), X separately represents hydroxyl or the alkoxyl of carbon number 1～4.
Description
Technical field
The present invention relates to the position different structure mixture of dehydroabietic acid derivant and manufacture method thereof.
Background technology
In recent years, from the view point of earth environment protection, the de-petrochemical of resources for research, it is conceived to various natural resources.Even if also seeking de-petrochemical at plastic applications, the polylactic acid that the lactic acid obtained with the fermentation by glucose is raw material is increasingly used in packaging material etc..
The transparency of polylactic acid is excellent, but thermostability is low, and therefore it rests on, towards the application of the products formed obtained by injection moulding etc., the limited use that cannot be exposed to high temperature always.It addition, polylactic acid is easily hydrolyzed under hot and humid condition or acid or alkaline environment, it is therefore desirable for it is improved.
It addition, as the composition being derived from natural goods, have the Colophonium that can gather from Colophonium etc..This Colophonium contains various carboxylic acid.Known abietic acid class in these carboxylic acids is used in macromolecular material (for example, referring to Japanese Unexamined Patent Publication 2008-274150 publication and Japanese Unexamined Patent Publication 6-87946 publication).
Such as, Japanese Unexamined Patent Publication 2008-274150 publication and Japanese Unexamined Patent Publication 6-87946 publication disclose the use of the abietic acid terminal part to phenolic resin or epoxy resin and modify, thus make the binding agent of coating etc. as rosin modified phenolic resin and Abietyl modified epoxyeicosatrienoic acid resin.But, these resins, with phenolic resin or epoxy resin for main skeleton, are therefore still to rely on the raw material of oil, for the viewpoint realizing earth environment protection and miss one's purpose.
Additionally, it is known that make the polyhydric alcohol such as disproportionated rosin and glycerol react, then with omega-dicarboxylic acids polycondensation and the polymer (for example, referring to Japanese Unexamined Patent Publication 2010-20170 publication) that obtains.
Summary of the invention
Invent problem to be solved
But, the impurity of polymer described in Japanese Unexamined Patent Publication 2010-20170 publication is more, does not form the linear polymer of high molecular.Therefore, such polymer cannot be used in the purposes such as the molded body that requires mechanical strength.
The present invention completes in view of described situation, and it is to realize following purpose for problem.
Namely, it is an object of the invention to, there is provided and be derived from natural goods and the di-2-ethylhexylphosphine oxide dehydroabietic acid of raw material of polyester or polyamide and the position different structure mixture of derivant thereof can be become, and, it is an object of the invention to, it is provided that can carrying capacity of environment little and the manufacture method of said mixture can be efficiently synthesized.
For the method solving problem
The synthetic method of di-2-ethylhexylphosphine oxide dehydroabietic acid and derivant thereof is conducted in-depth research by the present inventor, and its result is successfully develop can manufacture di-2-ethylhexylphosphine oxide dehydroabietic acid and derivant thereof efficiently and the little synthetic method of carrying capacity of environment.Simultaneously, it has been found that dehydroabietic acid derivant in presence of an acid catalyst and the condensation of formaldehyde are simultaneously generated two kinds of position isomers, thus completing the present invention.
That is, the method for solving described problem is as described below.
<1>position different structure mixture of a kind of dehydroabietic acid derivant, it contains the dehydroabietic acid derivant represented by two or more, the following formula (I) in di-2-ethylhexylphosphine oxide dehydroabietic acid and derivant thereof.
[chemical formula 1]
In formula (I), X separately represents hydroxyl or the alkoxyl of carbon number 1～4.
<2>position different structure mixture of the dehydroabietic acid derivant according to described<1>, wherein, the dehydroabietic acid derivant represented by described formula (I) contains the compound represented by following formula (II) and the compound represented by following formula (III).
[chemical formula 2]
In formula (II) and (III), X separately represents hydroxyl or the alkoxyl of carbon number 1～4.
<3>position different structure mixture of the dehydroabietic acid derivant according to described<2>, wherein, the Compound Phase represented by described formula (III) is 0.05～0.60 for the content ratio of the compound represented by described formula (II).
<4>position different structure mixture of the dehydroabietic acid derivant according to any one in described<1>～<3>, wherein, described X separately represents the alkoxyl of carbon number 1～4.
<5>manufacture method of the position different structure mixture of the dehydroabietic acid derivant represented by a kind of following formula (I), comprising: using at least one in acetic acid and acetate as reaction dissolvent, under the existence of at least one acid catalyst in sulphuric acid, aliphatic sulfonic and aromatic sulphonic acid, make the operation that at least one compound being selected from dehydroabietic acid and derivant thereof reacts with formaldehyde.
[chemical formula 3]
In formula (I), X separately represents hydroxyl or the alkoxyl of carbon number 1～4.
<6>manufacture method of the position different structure mixture according to described<5>, wherein, reaction by described dehydroabietic acid or derivatives thereof Yu described formaldehyde, with the generation ratio of 1: 0.05～1: 0.60, generate the compound represented by following formula (II) and the compound represented by following formula (III).
[chemical formula 4]
In formula (II) and (III), X separately represents hydroxyl or the alkoxyl of carbon number 1～4.
<7>manufacture method of the position different structure mixture according to described<5>or<6>, wherein, described formaldehyde is derived from paraformaldehyde.
<8>manufacture method of the position different structure mixture according to any one in described<5>～<7>, wherein, in the reaction of described dehydroabietic acid or derivatives thereof and described formaldehyde, mol ratio between described dehydroabietic acid or derivatives thereof and described formaldehyde be 1.0: 0.55～1.0: 2.0.
<9>manufacture method of the position different structure mixture according to any one in described<5>～<8>, wherein, described acid catalyst is at least one acid catalyst in sulphuric acid and aliphatic sulfonic.
<10>manufacture method of the position different structure mixture according to any one in described<5>～<9>, wherein, described reaction dissolvent is at least one acetate in methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate and isobutyl acetate.
<11>manufacture method of the position different structure mixture according to any one in described<5>～<10>, wherein, described reaction dissolvent is ethyl acetate.
The effect of invention
It is derived from natural goods and can as the position different structure mixture of the di-2-ethylhexylphosphine oxide dehydroabietic acid of polyester or the raw material of polyamide and derivant thereof in accordance with the invention it is possible to provide.And, in accordance with the invention it is possible to provide carrying capacity of environment little and the manufacture method of position different structure mixture of di-2-ethylhexylphosphine oxide dehydroabietic acid and derivant thereof can be efficiently synthesized.
Accompanying drawing explanation
Fig. 1 is the position different structure mixture representing the di-2-ethylhexylphosphine oxide dehydroabietic acid dimethyl ester involved by the present embodiment1The figure of one example of H-NMR spectrum.
Fig. 2 represents 12 involved by the present embodiment, 12 '-di-2-ethylhexylphosphine oxide dehydroabietic acid dimethyl ester1The figure of one example of H-NMR spectrum.
Detailed description of the invention
Hereinafter, the position different structure mixture of the dehydroabietic acid derivant (hereinafter also referred to as " di-2-ethylhexylphosphine oxide dehydroabietic acid and derivant thereof ") of the present invention is described in detail.
It should be noted that in this manual, "～" used as the implication of higher limit and lower limit according to including numerical value described before and after it.
<position different structure mixture>
The position different structure mixture of dehydroabietic acid derivant contains the dehydroabietic acid derivant represented by two or more, the following formula (I) in di-2-ethylhexylphosphine oxide dehydroabietic acid and derivant thereof.
[chemical formula 5]
In formula (I), X separately represents hydroxyl or the alkoxyl of carbon number 1～4.Two X in formula (I) can be identical or different.In the present invention, from the view point of manufacture efficiency, it is preferable that the alkoxyl of carbon number 1～4.
Dehydroabietic acid such as can be prepared by Colophonium.
Colophonium is the resinous principle gathered from Colophonium, according to acquisition method with " gum rosin ", " Starex " and " wood rosin " three kinds for representative.Method that constituent contained by Colophonium gathers according to them, the place of production etc. of pine and different, be generally the mixture of the Diterpenes resinic acid such as structure abietic acid as follows (1), neoabietic acid (2), palustric acid (3), levopimaric acid (4), dehydroabietic acid (5), dextropimaric acid (6), isodextropimaric acid (7).
[chemical formula 6]
In above-mentioned Diterpenes resinic acid, (1) to each compound represented by (4) can under the existence of the catalyst such as such as phosphorus ash stone, cause disproportionation by heat treated, be modified as the dihydroabietic acid (8) of dehydroabietic acid (5) and following structure.Such as, it is referred to Japanese Unexamined Patent Publication 2002-284732 publication etc. be modified.
[chemical formula 7]
Di-2-ethylhexylphosphine oxide dehydroabietic acid represented by formula (I) and derivant thereof as described later, are synthesized by the reaction of at least one compound in dehydroabietic acid and derivant thereof Yu formaldehyde.
At the di-2-ethylhexylphosphine oxide dehydroabietic acid represented by formula (I) and in derivant, with the isopropyl of dehydroabietic acid for 13, then the dehydroabietic acid of two can be any one in 11,12 and 14 with the bonding position of methylene, it is preferred to 12 or 14.It addition, the position of substitution of two dehydroabietic acids can be identical or different.
Namely, the position different structure mixture of the dehydroabietic acid derivant of the present invention contains selected from the compound represented by following formula (II) (following, also referred to as " 12/12 ' isomer "), compound represented by following formula (III) (following, also referred to as " 12/14 ' isomer ") and following formula (IV) represented by compound (hereinafter also referred to as " 14/14 ' isomer ") and at least two in 12/13 ' isomer, 14/13 ' isomer and 13/13 ' isomer.
[chemical formula 8]
X in formula (II), formula (III) and formula (IV) is identical with the X implication in formula (I), it is preferable that mode is also identical.
Wherein from the view point of manufacture efficiency, the position different structure mixture of described dehydroabietic acid derivant preferably comprises at least two in the compound represented by the compound represented by formula (II), formula (III) and the compound represented by formula (IV), more preferably at containing the compound represented by formula (II) and the compound represented by formula (III).
The position different structure mixture of dehydroabietic acid derivant is when containing 12/12 ' isomer and 12/14 ' isomer, 12/12 ' isomer and the gross mass of 12/14 ' isomer in the gross mass of isomer mixture are preferably more than 50 mass %, more preferably more than 70 mass %.
Additionally, 12/14 ' isomer is not particularly limited relative to the content ratio (" 12/14 ' isomer "/" 12/12 ' isomer ") of 12/12 ' isomer, but from the view point of manufacture efficiency, it is preferred to 0.05～0.60, more preferably 0.05～0.50.
The position different structure mixture of described dehydroabietic acid derivant is dicarboxylic acids or the ester derivant in molecule with two carboxyls or ester group, therefore, can become the compound constituting polyester and polyamide.It addition, have the structure division of rigidity and large volume in molecule, this structure division may make up a part for the main chain of polyester and polyamide, therefore may make up the polyester of excellent heat resistance and polyamide.
<manufacture method of position different structure mixture>
The position different structure mixture of the dehydroabietic acid derivant of the present invention, is manufactured by the reaction of at least one compound in dehydroabietic acid and derivant thereof Yu formaldehyde.
The manufacture method of the position different structure mixture of the dehydroabietic acid derivant represented by described formula (I) of the present invention includes: using at least one solvent in acetic acid and acetate as reaction dissolvent, under the existence of at least one acid catalyst in sulphuric acid, aliphatic sulfonic and aromatic sulphonic acid, make the operation that dehydroabietic acid or derivatives thereof and formaldehyde react, and contain other operation as desired and constitute.
Dehydroabietic acid can operate as follows and obtain.Such as, gum rosin or Starex are implemented dismutation reaction, in the presence of a catalyst, be heated processing, it is possible to obtain the thick dehydroabietic acid that content is more than 60 mass %.Then, by thick dehydroabietic acid is carried out suitable refinement treatment, thus the dehydroabietic acid that purity is more than 80 mass % can be obtained.Generally, the dehydroabietic acid of this purity can be used as raw material, but as required, it is possible to use highly purified dehydroabietic acid is as raw material.
Dehydroabietic acid easily can be derived as derivant by various methods.As derivant, it is possible to list esters or amide-type.Useful especially derivant is esters, and as the raw material of polyester or the synthesis of polyamide, the lower alkyl esters of carbon number 1～4 is useful.
If making dehydroabietic acid ester and formaldehyde react, then can obtain the dialkyl of di-2-ethylhexylphosphine oxide dehydroabietic acid.
Lower alkyl esters as the carbon number 1～4 of dehydroabietic acid, it is possible to list: methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, hydroxy methacrylate, hydroxy propyl ester etc., as preferred example, can list methyl ester as preferred example.
The formaldehyde reacted with at least one compound in dehydroabietic acid and derivant thereof can the form of various compounds use.Can be preferably used: as the formalin of 35 mass %～37 mass % aqueous solutions of formaldehyde, the paraformaldehyde or metaformaldehyde etc. that exist as solid using its polymeric form.Furthermore it is also possible to be preferably used: trimerical three alkane as ring-type, the dimethylacetal as formaldehyde dimethoxymethane etc..Wherein it is more preferably paraformaldehyde.
At least one compound in the dehydroabietic acid used selected from reaction and derivant thereof and the mol ratio of formaldehyde, i.e. at least one compound in dehydroabietic acid and derivant thereof: the mol ratio of formaldehyde is preferably in the scope of 1.0: 0.55～1.0: 2.0, more preferably in the scope of 1.0: 0.60～1.0: 1.5.It addition, the situation employing the derivant of formaldehyde is the ratio after having carried out formaldehyde conversion.
The reaction of at least one compound in dehydroabietic acid and derivant thereof and formaldehyde can carry out in the presence of acid catalyst.As acid catalyst, it is possible to use at least one acid catalyst in sulphuric acid, aliphatic sulfonic and aromatic sulphonic acid.
As aliphatic sulfonic, for instance, it is possible to list: the aliphatic sulfonic of the carbon number such as pyrovinic acid, ethylsulfonic acid 1～6.It addition, as aromatic sulphonic acid, for instance, it is possible to list: p-methyl benzenesulfonic acid, o-toluene sulfonic acid, chlorobenzenesulfonic acid, DBSA etc..
Acid catalyst can use above-mentioned such strong acid, but, in these acid, from catalyst activity and Eco-power viewpoint, it is preferably selected from least one acid catalyst in sulphuric acid and aliphatic sulfonic, it is more preferably at least one acid catalyst in the aliphatic sulfonic of sulphuric acid and carbon number 1～6, it is more preferably at least one acid catalyst in the aliphatic sulfonic of sulphuric acid and carbon number 1～3, more preferably at least one acid catalyst in sulphuric acid and pyrovinic acid.
Acid catalyst in the present invention can be used alone one, it is also possible to combines two or more use.
And, on the basis of sulphuric acid, aliphatic sulfonic and aromatic sulphonic acid, it is also possible to use the alkylcarboxylic acid etc. such as trifluoracetic acid simultaneously.
The amount of acid catalyst is suitably selected according to the acid catalyst used.The amount of preferred acid catalyst is different according to the kind of acid, but is preferably 10 mass %～80 mass % relative to the reaction dissolvent used, more preferably 10 mass %～60 mass %.If it makes consumption be more than 10 mass %, reaction is sufficiently carried out, if being additionally below 80 mass %, side reaction is inhibited, and the separation yield of target product improves.
For the reaction between at least one compound and the formaldehyde in dehydroabietic acid and derivant thereof of the present invention, generally, generate the di-2-ethylhexylphosphine oxide dehydroabietic acid or derivatives thereof reacted and obtain at each other 12 places of dehydroabietic acid, namely 12/12 ' isomer represented by described formula (II) is generated, but also can generate 14 position isomers reacted and obtain of a dehydroabietic acid 12 and another dehydroabietic acid simultaneously, namely generate 12/14 ' isomer represented by described formula (III).
On the other hand, generally do not observe each other 14 position isomers reacted and obtain of dehydroabietic acid in a large number, namely do not observe 14/14 ' isomer represented by described formula (IV) in a large number.
It addition, the ratio that generates of position isomer can by reaction product1The parsing of H-NMR spectrum and readily calculate.
Hereinafter, the computational methods generating ratio of position isomer are illustrated.
In Fig. 21Shown in H-NMR spectrum, the chemical shift of the aromatic rings proton of 12/12 ' isomer represented by formula (II) is belonged to as follows.
[chemical formula 9]
On the other hand, the chemical shift of the aromatic rings proton of 12/14 ' isomer represented by formula (III) is belonged to as follows.Particularly the chemical shift of the proton of 11 is subject to the circular current effect (screen effect) of aromatic rings because of the special spatial configuration (conformation) caused by steric hindrance, and upfield shift occurs.
[chemical formula 10]
Therefore, mixture in Fig. 11Shown in one example of H-NMR spectrum, the generation ratio of 12/12 ' isomer and 12/14 ' isomer by the ratio of the integrated value of the two of 6.68ppm and the 6.25ppm being mutually sufficiently separated signals, can be calculated.
The generation of 12/12 ' isomer in the reaction of the dehydroabietic acid of the present invention and derivant and formaldehyde and 12/14 ' isomer than (12/12 ' isomer: 12/14 ' isomer) generally in the scope of 1: 0.05～1: 0.60, it is preferable that in the scope of 1: 0.05～1: 0.50.
12/12 ' isomer generates than the slightly impact being subject to reaction condition with 12/14 ' isomer.Such as, there is the strong acid tendency that then 12/14 ' isomer increases.Specifically, if using sulphuric acid or the such aliphatic sulfonic of pyrovinic acid, then generally generating the 12/14 ' isomer of more than 20 mass % in total product, on the other hand, in trifluoroacetic situation, the generation of then 12/14 ' isomer becomes below 20 mass %.
For the manufacture method of the position different structure mixture of the present invention, in the reaction with formaldehyde of at least one compound in dehydroabietic acid and derivant thereof, as reaction dissolvent, at least one in acetic acid and acetate can be used, but at least one acetate is preferably used.
By using such specific solvent, it is possible to increase the dissolubility of raw material, further, since solvent effect promotes that reaction carries out, the separation of product becomes easy, and can reduce carrying capacity of environment.
By using acetic acid, it is suppressed that side reaction also promotes that reaction carries out, and the separation of product becomes easy.
It addition, by using acetate, promoted that reaction carries out and the separation of product becomes easy, and carrying capacity of environment can have been reduced.
As acetate, for instance, it is possible to list: methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate etc..In these acetates, more preferably use ethyl acetate.
Can pass through to use acetate (preferably except methyl acetate) as reaction dissolvent, thus after the completion of reaction, add water and be separated into two-layer, from organic layer, solvent under reduced pressure is distilled off, and solvent recovery is recycled, even if being also therefore preferred in reducing carrying capacity of environment.
As the esters beyond acetate, formic acid esters, propionic acid ester, butyric acid esters, succinate compound, maleic acid esters, fumaric acid esters, adipic acid esters etc. reaction carry out in there is the effect suitable with acetates, but from becoming the easness aspect of present aspect and recycling, it is preferable that acetates.
Additionally, for reacting the aspect carried out, the halogen based solvents such as preferred dichloromethane or dichloroethanes, but due to the impact on environment such as atmospheric pollution and underground water pollution, therefore preferably it is not used, it addition, target product is soluble in halogen based solvents, therefore the separation of target product is likely to become numerous and diverse.
Even if also can carry out it addition, react in the aromatic hydrocarbons such as toluene, dimethylbenzene, chlorobenzene, dichloro-benzenes, if but use these solvents, then partial solvent is likely to react with formaldehyde, therefore not preferred.
The consumption that makes of the reaction dissolvent that the reaction of at least one compound in dehydroabietic acid and derivant thereof and formaldehyde uses is not particularly limited, and suitably can select according to the solvent used.Such as, relative to reacting the dehydroabietic acid and derivant thereof that use, the consumption that makes of reaction dissolvent can be 150 mass %～1000 mass %, it is preferred to 200 mass %～500 mass %.
At least one compound in dehydroabietic acid and derivant thereof of the present invention carries out in large-scale temperature province with the reaction of formaldehyde.Preferred reaction temperature is 0 DEG C～50 DEG C, more preferably 10 DEG C～40 DEG C.If reaction temperature is more than 0 DEG C, promote that reaction carries out.If it addition, reaction temperature is less than 50 DEG C, the generation of by-product can be suppressed, or suppress the painted of reactant liquor.
The manufacture method of the position different structure mixture of the present invention is it is also preferred that include the separation circuit of product.
In separation circuit, after the completion of reaction, by various methods, the position different structure mixture of di-2-ethylhexylphosphine oxide dehydroabietic acid and derivant thereof can be easily separated.Such as, can use: the method merely crystallization of the target product precipitated out in reaction leached；After reaction, frozen water, the method leached by the target product of precipitation will be injected in reactant liquor；Inject after frozen water in reactant liquor, make water layer separate, be then washed to washing liquid and approximately reach after till neutrality, the method etc. reducing pressure the solvent that organic layer is distilled off and obtaining target product.For the separation method of target product, as long as coordinating the physical characteristic of di-2-ethylhexylphosphine oxide dehydroabietic acid or derivatives thereof and position isomer to generate ratio and reaction condition and adopt best separation method.
Generally, compared with 12/12 ' isomer, the crystallinity of 12/14 ' isomer is poor, if the generation of 12/14 ' isomer can be suppressed, the separation of target product becomes easy.If using acetates in reaction dissolvent, as a rule, di-2-ethylhexylphosphine oxide dehydroabietic acid or derivatives thereof as target precipitates out from reaction system with the form of crystallization as the mixture of position isomer, therefore separate and become extremely easy, productivity ratio can be improved.
As mentioned above, in the present invention, usual di-2-ethylhexylphosphine oxide dehydroabietic acid and derivant thereof are obtained as the mixture of position isomer, in most cases, many-sided purposes can be used in the state of mixture, but obtain highly purified 12/12 ' isomer also dependent on needs.Generally, can by making mixture recrystallization from suitable organic solvent remove 12/14 ' isomer, thus highly purified 12/12 ' isomer can be obtained.
In order to obtain the 12/14 ' isomer of the opposing party with high-purity, the method utilizing liquid chromatography to be easily separated etc. can be adopted.
Hereinafter, the present invention is described in detail to enumerate embodiment, but the present invention is not limited to below example.
<embodiment 1>
The position different structure mixture of dehydroabietic acid derivant is manufactured according to reaction scheme shown below.
[chemical formula 11]
In the there-necked flask of 500ml, add ethyl acetate 100ml, cool down at 15 DEG C～20 DEG C, in there-necked flask, drip sulphuric acid 30ml.Then, add methyl dehydroabietate (31.4g, 0.100mol) and paraformaldehyde (2.40g, 0.0800mol), stir 4 hours at 30 DEG C.In reactant liquor, add frozen water 200ml and ethyl acetate 50ml, separate aqueous layer, repeat washing organic layer.After the dry organic layer of anhydrous magnesium sulfate, decompression is distilled off ethyl acetate, adds methanol 100ml, at room temperature stirring 1 hour in residue.Leach the crystallization after solidification, wash with methanol, obtain the white crystals (24.0g, separation yield is 75%, and 12/12 ' isomer containing ratio is 88%) of di-2-ethylhexylphosphine oxide dehydroabietic acid dimethyl ester.It addition, it is 1: 0.30 that the position isomer of reaction generates than (12/12 ' isomer: 12/14 ' isomer).
The 1H-NMR spectrogram of the sterling of 12/12 ' isomer is shown in Fig. 2, the sterling of described 12/12 ' isomer by make above-mentioned di-2-ethylhexylphosphine oxide dehydroabietic acid dimethyl ester (position different structure mixture) from ethyl acetate/methanol twice of recrystallization and obtain.It addition, the NMR spectra figure of the position different structure mixture obtained concentrating its filtrate (product after concentration 12/14 ' isomer) is shown in Fig. 1.Additionally, after reaction terminates, take a small amount of reactant liquor, add water separation organic layer, the NMR spectra of the residue obtained ethyl acetate is distilled off is measured, the ratio of the integrated value of the signal (14 protons of 12/12 ' isomer) of 6.68ppm and integrated value × 2 of the signal (11 protons of 12/14 ' isomer) of 6.25ppm the position isomer calculating reaction generates ratio.
<embodiment 2>
In the there-necked flask of 500ml, add ethyl acetate 150ml, cool down at 15 DEG C～20 DEG C, in there-necked flask, drip sulphuric acid 40ml.Then, add dehydroabietic acid (30.0g, 0.100mol) and paraformaldehyde (2.40g, 0.0800mol), stir 4 hours at 40 DEG C.After reaction terminates, add dichloromethane 40ml, be cooled to 15 DEG C, leach the crystallization of precipitation, wash with acetonitrile, obtain the white crystals (15.6g, separation yield is 51%, and 12/12 ' isomer containing ratio is 92%) of di-2-ethylhexylphosphine oxide dehydroabietic acid.It addition, it is 1: 0.25 that the position isomer of reaction generates ratio.
<embodiment 3>
In the there-necked flask of 500ml, add methyl dehydroabietate (31.4g, 0.100mol), paraformaldehyde (2.10g, 0.07mol) and methyl acetate 100ml, be at room temperature stirred.Cool down while drip the sulphuric acid of 23.0ml internal temperature less than 25 DEG C.At room temperature stirring 4 hours, have precipitated out the crystallization of the di-2-ethylhexylphosphine oxide dehydroabietic acid dimethyl ester as target.After stirring 1 hour at 15 DEG C～20 DEG C, the crystallization precipitated out is carried out filtration under diminished pressure, washs with methanol, then wash with water again.Add the methanol of 90ml to the crystallization of gained, carry out 20 minutes be heated to reflux.It is cooled to till internal temperature reaches 25 DEG C, the water of dropping 45ml.The crystallization precipitated out is carried out filtration under diminished pressure, obtains di-2-ethylhexylphosphine oxide dehydroabietic acid dimethyl ester (20.0g, separation yield is 62.4%, and 12/12 ' isomer containing ratio is 91%).It addition, it is 1: 0.28 that the position isomer of reaction generates ratio.
<embodiment 4～13, comparative example 1～5>
In embodiment 1, as described in Table 1, the dehydroabietic acid that uses of reaction and derivant thereof, the kind of acid catalyst, the kind of formaldehyde, reaction dissolvent are modified, in addition, carry out the operation identical with above-described embodiment 1, manufacture the position different structure mixture of dehydroabietic acid derivant.Position isomer is generated when separation yield and is shown in table 1.
It should be noted that the X in table 1 represents the X in described formula (I).
[table 1]
As can be known from the above results, the method according to the invention, the position different structure mixture of di-2-ethylhexylphosphine oxide dehydroabietic acid derivant can be easily synthesized by easy method.
Full content disclosed in Japanese publication 2010-285030 and Japanese publication 2011-262310 is introduced in this specification with the form of reference.
The degree that whole documents, patent application and the technical standard recorded in this specification are identical with the situation that each document, patent application and the technical standard that introduce as reference specifically and are respectively recorded, introduces in this specification as reference.
Claims (8)
1. a position different structure mixture for dehydroabietic acid derivant, its dehydroabietic acid derivant represented by two or more, the following formula (I) in di-2-ethylhexylphosphine oxide dehydroabietic acid and derivant thereof forms,
The dehydroabietic acid derivant represented by formula (I) more than the two contains the compound represented by following formula (II) and the compound represented by following formula (III),
Compound Phase represented by described formula (III) is 0.05～0.60 for the content ratio of the compound represented by described formula (II),
In formula (I), (II) and (III), X separately represents hydroxyl or the alkoxyl of carbon number 1～4.
2. the position different structure mixture of dehydroabietic acid derivant according to claim 1, wherein, described X is separately the alkoxyl of carbon number 1～4.
3. the manufacture method of the position different structure mixture of the dehydroabietic acid derivant represented by a following formula (I), comprising: using at least one in acetic acid and acetate as reaction dissolvent, under the existence of at least one acid catalyst in sulphuric acid, the aliphatic sulfonic of carbon number 1～6, p-methyl benzenesulfonic acid, o-toluene sulfonic acid, chlorobenzenesulfonic acid and DBSA, make the operation that at least one compound being selected from the lower alkyl esters of dehydroabietic acid or its carbon number 1～4 reacts with formaldehyde
Dehydroabietic acid derivant represented by described formula (I) contains the compound represented by following formula (II) and the compound represented by following formula (III),
Compound Phase represented by described formula (III) is 0.05～0.60 for the content ratio of the compound represented by described formula (II),
In formula (I), (II) and (III), X separately represents hydroxyl or the alkoxyl of carbon number 1～4.
4. the manufacture method of position different structure mixture according to claim 3, wherein, described formaldehyde is derived from paraformaldehyde.
5. the manufacture method of the position different structure mixture according to claim 3 or 4, wherein, in the lower alkyl esters of described dehydroabietic acid or its carbon number 1～4 and the reaction of described formaldehyde, mol ratio between described dehydroabietic acid or lower alkyl esters and the described formaldehyde of its carbon number 1～4 be 1.0: 0.55～1.0: 2.0.
6. the manufacture method of the position different structure mixture according to claim 3 or 4, wherein, described acid catalyst is at least one acid catalyst in the aliphatic sulfonic of sulphuric acid and carbon number 1～6.
7. the manufacture method of the position different structure mixture according to claim 3 or 4, wherein, described reaction dissolvent is at least one acetate in methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate and isobutyl acetate.
8. the manufacture method of the position different structure mixture according to claim 3 or 4, wherein, described reaction dissolvent is ethyl acetate.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| JP2010285030 | 2010-12-21 | ||
| JP2010-285030 | 2010-12-21 | ||
| PCT/JP2011/078195 WO2012086409A1 (en) | 2010-12-21 | 2011-12-06 | Mixture of regioisomers of dehydroabietic acid derivatives, and process for production thereof |
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| CN103237783A CN103237783A (en) | 2013-08-07 |
| CN103237783B true CN103237783B (en) | 2016-07-13 |
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| JP (1) | JP5797537B2 (en) |
| CN (1) | CN103237783B (en) |
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| JP5767619B2 (en) * | 2011-11-25 | 2015-08-19 | 富士フイルム株式会社 | Liquid crystal composition and chiral agent used therefor |
| WO2014030652A1 (en) * | 2012-08-22 | 2014-02-27 | 荒川化学工業株式会社 | Polymerised rosin compound and production method therefor |
| CN102921349B (en) * | 2012-11-30 | 2014-08-06 | 中国林业科学研究院林产化学工业研究所 | Disproportionated rosinyl anion/non-ion composite surfactant and preparation method thereof |
| CN104016882B (en) * | 2014-05-09 | 2017-01-04 | 上海大学 | 12-oxime ether dehydroabietic acid compound and synthetic method thereof |
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| JPH02104565A (en) * | 1988-10-14 | 1990-04-17 | Harima Chem Inc | Novel phenanthlene derivative and its production |
| JP2004231584A (en) * | 2003-01-31 | 2004-08-19 | Arakawa Chem Ind Co Ltd | Method for producing resin acid composition, crystal-nucleating agent for crystalline thermoplastic resin, and crystalline thermoplastic resin composition |
| JP5398650B2 (en) * | 2009-06-25 | 2014-01-29 | 富士フイルム株式会社 | Novel dehydroabietic acid polymer |
| JP5300680B2 (en) * | 2009-09-30 | 2013-09-25 | 富士フイルム株式会社 | Novel abietane polymer |
| JP5796274B2 (en) * | 2010-03-11 | 2015-10-21 | 荒川化学工業株式会社 | Rosin-modified phenolic resin, its production method and printing ink |
| JP5714442B2 (en) * | 2010-12-24 | 2015-05-07 | 富士フイルム株式会社 | POLYAMIDE POLYMER AND PROCESS FOR PRODUCING THE SAME, RESIN COMPOSITION, MOLDED BODY, FIBER, FILM AND POROUS FILM |
| JP5734779B2 (en) * | 2010-12-24 | 2015-06-17 | 富士フイルム株式会社 | Polyester polymer, resin composition, molded article, and film |
| JP5689444B2 (en) * | 2011-06-23 | 2015-03-25 | 富士フイルム株式会社 | Transparent insulating laminate and printed circuit board using the same |
| JP2013018874A (en) * | 2011-07-11 | 2013-01-31 | Fujifilm Corp | Porous film, and reflection plate using the same |
| CN103827166B (en) * | 2011-07-26 | 2016-08-17 | 富士胶片株式会社 | Resin, resin combination and preparation method thereof and use the toner of this resin combination |
| JP2013064067A (en) * | 2011-09-16 | 2013-04-11 | Fujifilm Corp | Resin composition and method for producing the same, and toner using the same |
| JP5718783B2 (en) * | 2011-10-07 | 2015-05-13 | 富士フイルム株式会社 | Electrophotographic photoreceptor, copier using the same, and dope for forming photosensitive layer thereof |
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| Publication number | Publication date |
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| JP2012144514A (en) | 2012-08-02 |
| CN103237783A (en) | 2013-08-07 |
| JP5797537B2 (en) | 2015-10-21 |
| WO2012086409A1 (en) | 2012-06-28 |
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