CN103391916B - The manufacture method of dehydroabietic acid derivative and manufacture method and 12-carboxyl dehydroabietic acid derivative - Google Patents

The manufacture method of dehydroabietic acid derivative and manufacture method and 12-carboxyl dehydroabietic acid derivative Download PDF

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CN103391916B
CN103391916B CN201280009971.1A CN201280009971A CN103391916B CN 103391916 B CN103391916 B CN 103391916B CN 201280009971 A CN201280009971 A CN 201280009971A CN 103391916 B CN103391916 B CN 103391916B
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acid derivative
dehydroabietic acid
carbonatoms
hydrogen atom
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CN103391916A (en
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上平茂生
佐藤幸藏
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Fujifilm Corp
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    • C—CHEMISTRY; METALLURGY
    • 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
    • C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/377—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
    • C07C51/38—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups by decarboxylation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • C07C69/757—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
    • C07C2603/26—Phenanthrenes; Hydrogenated phenanthrenes

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Abstract

The invention provides the dehydroabietic acid derivative that the manufacture method with 12-carboxyl dehydroabietic acid derivative that derive from the main framing of the compound being derived from plant, that can form polymkeric substance and this manufacture method use.By to be oxidized the dehydroabietic acid derivative represented by following general formula (I) and decarboxylation manufactures 12-carboxyl dehydroabietic acid derivative. (in general formula (I), R 1represent hydrogen atom, the alkyl that substituent aryl maybe can have substituent carbonatoms 1 ~ 10 can be had, R 2represent that hydrogen atom maybe can have the alkyl of substituent carbonatoms 1 ~ 10.X represents carbonyl, hydroxy methylene or acyloxy methylene radical).

Description

The manufacture method of dehydroabietic acid derivative and manufacture method and 12-carboxyl dehydroabietic acid derivative
Technical field
The present invention relates to the manufacture method of dehydroabietic acid derivative and manufacture method and 12-carboxyl dehydroabietic acid derivative.
Background technology
In recent years, from the view point of global environment protection, the de-petrochemical of resources for research, is conceived to various natural resource.Even if also seeking de-petrochemical at plastic applications, the poly(lactic acid) that the lactic acid obtained with the fermentation by glucose is raw material is just being widely used in wrapping material etc.The transparency of poly(lactic acid) is excellent, but thermotolerance is low, and therefore it is towards the application of the products formed obtained by injection molding etc., rests on the limited use not being exposed to high temperature always.
In addition, as the composition being derived from natural goods (being preferably plant), the rosin that can gather from rosin etc. is had.Known this rosin is made up of various carboxylic acid, is used by the abietic acid in these carboxylic acids as macromolecular material.Such as, disclose by using the terminal part of abietic acid to resol or epoxy resin to modify, thus the tackiness agent (for example, referring to Japanese Unexamined Patent Publication 2008-274150 publication and Japanese Unexamined Patent Publication 6-87946 publication) of coating etc. is made as rosin modified phenolic resin and Abietyl modified epoxyeicosatrienoic acid resin.
Summary of the invention
Invent problem to be solved
But; Japanese Unexamined Patent Publication 2008-274150 publication or the resin described in Japanese Unexamined Patent Publication 6-87946 publication with resol or epoxy resin for main skeleton; therefore be still the raw material depending on oil, with regard to realize global environment protection viewpoint with regard to and miss one's purpose.
The present invention in view of the above problems, its problem is, the dehydroabietic acid derivative providing the manufacture method with 12-carboxyl dehydroabietic acid derivative that derive from the main framing of the compound being derived from plant, that can form polymkeric substance and this manufacture method to use and manufacture method thereof.
For solving the method for problem
Concrete grammar for solving described problem is as follows.
Dehydroabietic acid derivative represented by <1> following general formula (I).
(in general formula (I), R 1represent hydrogen atom, the alkyl that substituent aryl maybe can have substituent carbonatoms 1 ~ 10 can be had, R 2represent that hydrogen atom maybe can have the alkyl of substituent carbonatoms 1 ~ 10.X represents carbonyl, hydroxy methylene or acyloxy methylene radical)
The dehydroabietic acid derivative of <2> according to described <1>, wherein, in described general formula (I), R 1represent hydrogen atom, the alkyl that the aryl of substituent carbonatoms 6 ~ 15 maybe can have substituent carbonatoms 1 ~ 8 can be had, R 2represent hydrogen atom, can have the alkyl or phenyl of substituent carbonatoms 1 ~ 4, X represents the acyloxy methylene radical of carbonyl, hydroxy methylene or carbonatoms 2 ~ 5.
The dehydroabietic acid derivative of <3> according to described <1>, wherein, in described general formula (I), R 1represent hydrogen atom, the alkyl that the aryl of substituent carbonatoms 6 ~ 12 maybe can have substituent carbonatoms 1 ~ 3 can be had, R 2represent hydrogen atom, can have substituent methyl or ethyl respectively, X represents the acyloxy methylene radical of carbonyl, hydroxy methylene or carbonatoms 2 ~ 4.
The dehydroabietic acid derivative of <4> according to described <1> or <2>, wherein, described R 1for being selected from hydrogen atom, the one that can have respectively in substituent phenyl, naphthyl, xenyl, methyl, ethyl, propyl group, sec.-propyl, cyclopropyl, butyl, isobutyl-, sec-butyl, the tertiary butyl, hexyl, cyclohexyl, octyl group, ethylhexyl, decyl and 2-ethylhexyl.
The dehydroabietic acid derivative of <5> according to described <1>, wherein, described R 2for being selected from hydrogen atom, the one that can have respectively in substituent methyl, ethyl, propyl group, sec.-propyl, cyclopropyl, butyl, isobutyl-, sec-butyl, the tertiary butyl, hexyl, cyclohexyl, octyl group, ethylhexyl, decyl and 2-ethylhexyl.
The dehydroabietic acid derivative of <6> according to described <1>, wherein, described dehydroabietic acid derivative is represented by general formula (A) or general formula (B).
In general formula (A) and general formula (B), R 1represent hydrogen atom, the alkyl that substituent aryl maybe can have substituent carbonatoms 1 ~ 10 can be had, R 2represent that hydrogen atom maybe can have the alkyl of substituent carbonatoms 1 ~ 10.R 3represent hydrogen atom or acyl group.
The dehydroabietic acid derivative of <7> according to described <6>, wherein, described R 1for being selected from hydrogen atom, the one that can have respectively in substituent phenyl, naphthyl, xenyl, methyl, ethyl, propyl group, sec.-propyl, cyclopropyl, butyl, isobutyl-, sec-butyl, the tertiary butyl, hexyl, cyclohexyl, octyl group, ethylhexyl, decyl and 2-ethylhexyl.
The dehydroabietic acid derivative of <8> according to described <6> or <7>, wherein, described R 2for being selected from hydrogen atom, the one that can have respectively in substituent methyl, ethyl, propyl group, sec.-propyl, cyclopropyl, butyl, isobutyl-, sec-butyl, the tertiary butyl, hexyl, cyclohexyl, octyl group, ethylhexyl, decyl and 2-ethylhexyl.
<9> according to the dehydroabietic acid derivative in described <6> ~ <8> described in any one, wherein, described R 3for being selected from the one in hydrogen atom, formyl radical, ethanoyl, propionyl, butyryl radicals, (methyl) acryl, crotonoyl, benzoyl and cinnamoyl.
The manufacture method of the 12-carboxyl dehydroabietic acid derivative represented by <10> following general formula (II), it comprises: be oxidized the dehydroabietic acid derivative represented by following general formula (I) and the operation of decarboxylation.
[chemical formula 3]
(in general formula (I) and general formula (II), R 1represent hydrogen atom, the alkyl that substituent aryl maybe can have substituent carbonatoms 1 ~ 10 can be had, R 2represent that hydrogen atom maybe can have the alkyl of substituent carbonatoms 1 ~ 10.X represents carbonyl, hydroxy methylene or acyloxy methylene radical)
The manufacture method of the dehydroabietic acid derivative represented by <11> following general formula (I), it comprises: make the compound represented by following general formula (III) and the compound represented by following general formula (IV) carry out the operation of reacting.
[chemical formula 4]
(in general formula (I), general formula (III) and general formula (IV), R 1represent hydrogen atom, the alkyl that substituent aryl maybe can have substituent carbonatoms 1 ~ 10 can be had, R 2represent that hydrogen atom maybe can have the alkyl of substituent carbonatoms 1 ~ 10.X represents carbonyl, hydroxy methylene or acyloxy methylene radical.Y represents hydrogen atom or leavings group)
The manufacture method of the dehydroabietic acid derivative of <12> according to described <11>, wherein, described Y is selected from the one in hydrogen atom, halogen atom, alkyl and aryl-sulfonyl oxygen and alkyl and arylamino sulfonyloxy.
Invention effect
According to the present invention, the dehydroabietic acid derivative that the manufacture method with that derive from the main framing of the compound being derived from plant, that polymkeric substance can be formed 12-carboxyl dehydroabietic acid derivative and this manufacture method can be provided to use and manufacture method thereof.
Accompanying drawing explanation
The exemplary compounds (A-1) of Fig. 1 involved by expression embodiments of the invention 1the figure of one example of H-NMR spectrum.
The exemplary compounds (A-8) of Fig. 2 involved by expression embodiments of the invention 1the figure of one example of H-NMR spectrum.
The exemplary compounds (A-6) of Fig. 3 involved by expression embodiments of the invention 1the figure of one example of H-NMR spectrum.
The exemplary compounds (B-1) of Fig. 4 involved by expression embodiments of the invention 1the figure of one example of H-NMR spectrum.
The 12-carboxyl dehydroabietic acid of Fig. 5 involved by expression embodiments of the invention 1the figure of one example of H-NMR spectrum.
The 12-carboxyl methyl dehydroabietate of Fig. 6 involved by expression embodiments of the invention 1the figure of one example of H-NMR spectrum.
Embodiment
In this manual, " engineering " this word not merely represents independently operation, even if when not distinguishing clearly with other operations, as long as can realize the effect desired by this operation, is just included in this term.
In addition, in this manual, use the numerical range represented by " ~ ", represent the scope comprised as minimum value and maximum value by the numerical value described in the front and back of " ~ ".
The feature of dehydroabietic acid derivative of the present invention is, is represented by following general formula (I).
By having the substituting group of described ad hoc structure, utilize oxidation and the such easy operation of decarboxylation, thus can high purity ground and there is 12-carboxyl dehydroabietic acid derivative that derive from the main framing of the compound being derived from plant, that can form polymkeric substance with the yield manufacture of excellence.
In addition, in the compound represented by general formula (I), X is that the compound of hydroxy methylene has the part-structure being similar to lactic acid.Therefore, such as, described in Japanese Patent No. 423704 publications etc., by polymerization separately or form with the copolymerization of lactic acid etc. the polymkeric substance being similar to poly(lactic acid).
In addition, in the compound represented by general formula (I), X is that the compound of carbonyl has α, beta-diketon structure.Therefore, can utilize α, beta-diketon features simple structure ground forms heterocycle.Such as, according to the record of International Publication No. 2008/33999 brochure etc., heterocycle can be imported to dehydroabietic acid skeleton.
In general formula (I), R 1represent hydrogen atom, the alkyl that substituent aryl maybe can have substituent carbonatoms 1 ~ 10 can be had, R 2represent that hydrogen atom maybe can have the alkyl of substituent carbonatoms 1 ~ 10.X represents carbonyl, hydroxy methylene or acyloxy methylene radical.
As R 1represented aryl, is preferably the aryl of carbonatoms 6 ~ 15, is more preferably the aryl of carbonatoms 6 ~ 12.As the concrete example of aryl, can list: phenyl, naphthyl and xenyl etc.Wherein, be preferably phenyl or xenyl, be more preferably phenyl.
R 1the alkyl of represented carbonatoms 1 ~ 10 can be any one in straight-chain, branched and ring-type.Specifically, such as, can list: methyl, ethyl, propyl group, sec.-propyl, cyclopropyl, butyl, isobutyl-, sec-butyl, the tertiary butyl, hexyl, cyclohexyl, octyl group, ethylhexyl, decyl and 2-ethylhexyl etc.Wherein, be preferably the alkyl of the straight-chain of carbonatoms 1 ~ 8, branched or ring-type, be more preferably the alkyl of the straight-chain of carbonatoms 1 ~ 6, branched or ring-type, more preferably the alkyl of the straight-chain of carbonatoms 1 ~ 3, branched or ring-type.
R 1represented aryl and alkyl can have substituting group, also can not be substituted.Alternatively base, such as, can list: aryl, halogen atom, hydroxyl, the alkoxyl group of carbonatoms 1 ~ 10, the acyloxy of carbonatoms 1 ~ 10, the amide group etc. of carbonatoms 1 ~ 10 such as alkyl, phenyl of carbonatoms 1 ~ 10.
In addition, R 1in substituting group can be the substituting group be made up of at least one in the alkyl of the group being selected from the compound derived from represented by general formula (I), carbonatoms 1 ~ 10, phenyl and Sauerstoffatom.At this, the group deriving from the compound represented by general formula (I) refers to and removes a hydrogen atom from the compound represented by general formula (I) and the group formed, and the position removing hydrogen atom is not particularly limited.
It should be noted that, R 1substituent carbonatoms is not comprised in the carbonatoms of represented alkyl.
R 2the alkyl of represented carbonatoms 1 ~ 10 and R 1the alkyl of represented carbonatoms 1 ~ 10 has identical implication, and the details of preferred exemplary etc. is also identical.Wherein, the alkyl of preferred carbonatoms 1 ~ 4, is more preferably methyl or ethyl.
X represents carbonyl, hydroxy methylene or acyloxy methylene radical.The group of these divalence and together with the carboxyl of X bonding or ester group, constitutes the functional group's (hereinafter also referred to as " particular functional base ") being transformed to carboxyl by oxidation and decarboxylic reaction.Westvaco rosin derivative represented by general formula (I) has particular functional base at 12, thus can be easy and westvaco rosin derivative efficiently represented by general formula (I) manufactures 12-carboxyl dehydroabietic acid derivative.
Specifically, the dehydroabietic acid derivative represented by general formula (I) with particular functional base is represented by following general formula (A) or general formula (B).
In formula, R 1and R 2with the R in general formula (I) 1and R 2have identical implication respectively, the details of preferred exemplary etc. is also identical.R 3represent hydrogen atom or acyl group.
R 3the carbonatoms of represented acyl group is not particularly limited.Such as, carbonatoms can be made to be 1 ~ 30, and carbonatoms is preferably 1 ~ 10, and carbonatoms is more preferably 1 ~ 4, carbonatoms more preferably 1 ~ 3.
In addition, acyl group can be any one in representative examples of saturated aliphatic acyl group, unsaturated aliphatic acyl group and aromatic acyl.Wherein, be preferably the representative examples of saturated aliphatic acyl group of carbonatoms 1 ~ 6 or the unsaturated aliphatic acyl group of carbonatoms 3 ~ 8; be more preferably the representative examples of saturated aliphatic acyl group of carbonatoms 1 ~ 4 or the unsaturated aliphatic acyl group of carbonatoms 3 ~ 4, more preferably the representative examples of saturated aliphatic acyl group of carbonatoms 1 ~ 3 or the unsaturated aliphatic acyl group of carbonatoms 3.
As R 3the concrete example of represented acyl group, such as, can list: formyl radical, ethanoyl, propionyl, butyryl radicals, (methyl) acryl, crotonoyl, benzoyl and cinnamoyl etc.
Wherein, the acyl group in formyl radical, ethanoyl, propionyl and (methyl) acryl is preferably selected from.
Particularly, when acyl group is the unsaturated aliphatic acyl groups such as (methyl) acryl, the formation of the acrylic polymers with dehydroabietic acid skeleton can be preferably applied to.
Below, show the concrete example of the dehydroabietic acid derivative represented by general formula (I), but the present invention is not limited to following concrete example.
[chemical formula 7]
The manufacture method > of < dehydroabietic acid derivative
Dehydroabietic acid derivative represented by general formula (I) can be manufactured by dehydroabietic acid or its ester derivative.In addition, dehydroabietic acid can be prepared by rosin.
Rosin is the resinous principle gathered from rosin, is representative according to acquisition method with " gum resin ", " starex " and " wood rosin " three kinds.The place of production etc. of the method that the constituent contained by rosin gathers according to them, pine and different, is generally the mixture of the diterpenes resinous acids such as structure abietic acid as follows (1), neoabietic acid (2), palustric acid (3), levopimaric acid (4), dehydroabietic acid (5), pimaric acid (6), isopimaric acid (7).
[chemical formula 9]
In above-mentioned diterpenes resinous acid, (1) to each compound represented by (4) can under the existence of the catalyzer 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, modification can be carried out with reference to Japanese Unexamined Patent Publication 2002-284732 publication etc.
Dehydroabietic acid derivative represented by general formula (I) manufactures by following manufacture method, described manufacture method comprises makes the compound represented by following general formula (III) (dehydroabietic acid and ester derivative thereof) and the compound represented by following general formula (IV) carry out the operation of reacting, and comprises other operation as required.
Utilize above-mentioned manufacture method, can with the yield of excellence and regioselectivity import particular functional base to the compound represented by general formula (III).
[chemical formula 11]
In general formula (I), general formula (III) and general formula (IV), R 1represent hydrogen atom, alkyl, R that substituent aryl maybe can have substituent carbonatoms 1 ~ 10 can be had 2represent that hydrogen atom maybe can have the alkyl of substituent carbonatoms 1 ~ 10.X represents carbonyl, hydroxy methylene or acyloxy methylene radical.In addition, Y represents hydrogen atom or leavings group.
R 1, R 2and the details of X is described above, preferred mode is also identical.
As the leavings group represented by Y, halogen atom, alkyl and aryl-sulfonyl oxygen and alkyl and the arylamino sulfonyloxies etc. such as fluorine atom, chlorine atom, bromine atoms, atomic iodine can be listed.In these groups, as the leavings group represented by Y, from the view point of reactive and productivity, be preferably halogen atom.
The operation making the compound represented by general formula (III) and the compound represented by general formula (IV) carry out reacting is so-called aromatic series electrophilic substitution.The reaction conditions of aromatic series electrophilic substitution is not particularly limited, can the structure etc. of compound represented by general formula (IV), suitably selects from the reaction conditions usually adopted.Such as, in acid condition, the method etc. by the compound represented by general formula (III) and the compound represented by general formula (IV) can be listed.
More specifically, in the compound represented by general formula (I), the compound represented by general formula (A) such as synthesizes by following such synthetic route.
In following general formula, R 1and R 2with the R in general formula (I) 1and R 2have identical implication respectively, the details of preferred exemplary etc. is also identical.In addition, by R 4and with R 4the acyl group of carbonyl formation of bonding and the R of general formula (A) 3represented acyl group has identical implication, and the details of preferred example etc. is also identical.
[chemical formula 12]
In the compound represented by general formula (III), R 1compound for hydrogen atom is dehydroabietic acid itself.In addition, R 1for the compound beyond hydrogen atom by normally used esterification process by dehydroabietic acid and correspond to R 1alcohol manufacture.
Under the existence of the carboxylic acid represented by logical formula V, glyoxalic acid derivative represented by general formula (IVa) and the compound represented by general formula (III) are reacted, the dehydroabietic acid derivative represented by general formula (A1) can be manufactured thus.The reaction conditions that reaction conditions can be applied from common aromatic series electrophilic substitution is suitably selected.Such as, using the carboxylic acid represented by logical formula V as solvent, can react under the existence of the strong acid such as the vitriol oil.
In addition, the dehydroabietic acid derivative represented by general formula (A1) and the middle R of general formula (A) 3for the dehydroabietic acid derivative of acyl group is suitable.
Compound represented by the glyoxalic acid derivative made represented by general formula (IVa) and general formula (III) carries out in the operation of reacting, relative to the compound represented by general formula (III), the usage quantity of glyoxalic acid derivative represented by general formula (IVa) is not particularly limited.Such as can be set to more than 1 equivalent, to be preferably more than 1 equivalent and below 5 equivalents.
Glyoxalic acid derivative represented by the compound made represented by general formula (III) and general formula (IVa) carries out, in the operation of reacting, can using catalyzer.As catalyzer, such as, iron(ic) chloride and zinc chloride etc. can be listed.
In addition, the usage quantity of catalyzer is not particularly limited.Such as, more than 0.01 equivalent can be set to relative to the compound represented by general formula (III), be preferably more than 0.01 equivalent and below 3 equivalents.
Glyoxalic acid derivative represented by the compound made represented by general formula (III) and general formula (IVa) carries out, in the operation of reacting, can using solvent.As solvent, except the carboxylic acid represented by logical formula V, can also list: the halons etc. such as the carboxylicesterss such as vinyl acetic monomer, methylene dichloride and chlorobenzene.
When reaction employs solvent, the usage quantity of solvent is not particularly limited.Such as can be set to more than 50 quality % relative to the compound represented by general formula (III), be preferably more than 50 quality % and below 2000 quality %.
In addition, temperature of reaction is not particularly limited, and such as, can be set to-20 ~ 100 DEG C, is preferably 0 ~ 80 DEG C.
Dehydroabietic acid derivative represented by general formula (A2) is by supplying to manufacture with ester hydrolysis reaction by the dehydroabietic acid derivative represented by general formula (A1).As long as the reaction conditions that can obtain desired compound then ester hydrolysis reaction is not particularly limited, suitably can select from the reaction conditions of normally used ester hydrolysis reaction.Such as, the common hydrolysis reaction condition etc. employing alkaline aqueous solution can be listed.
In addition, the dehydroabietic acid derivative represented by general formula (A2) and the middle R of general formula (A) 3for the dehydroabietic acid derivative of hydrogen atom is suitable.
In the operation making the compound hydrolysis represented by general formula (A1), solvent can be used.As solvent, it is not particularly limited, and can the solvability etc. of compound represented by general formula (A1) suitably select.Specifically, tetrahydrofuran (THF) etc. can be listed.
In addition, temperature of reaction is not particularly limited, and such as, can be set to 10 ~ 200 DEG C, is preferably 20 ~ 150 DEG C.
In addition, in the compound represented by general formula (I), the compound represented by general formula (B) such as synthesizes by following such synthesis path.
In following general formula, R 1and R 2with the R in general formula (I) 1and R 2have identical implication respectively, the details of preferred example etc. is also identical.In addition, LG represents leavings group, and have identical implication with the leavings group represented by the Y of general formula (IV), the details of preferred example etc. is also identical.
By making the compound represented by the oxalic acid derivatives represented by general formula (IVb) and general formula (III) react, manufacture the dehydroabietic acid derivative represented by general formula (B).The reaction conditions that reaction conditions can be applied from common aromatic series electrophilic substitution is suitably selected.Such as, the reaction conditions of common Fu Kexing (Friedel Crafts) can be selected.
Compound represented by the oxalic acid derivatives made represented by general formula (IVb) and general formula (III) carries out in the operation of reacting, relative to the compound represented by general formula (III), the usage quantity of oxalic acid derivatives represented by general formula (IVb) is not particularly limited.Such as, more than 1 equivalent can be set to, be preferably more than 1 equivalent and below 3 equivalents.
Oxalic acid derivatives represented by the compound made represented by general formula (III) and general formula (IVb) carries out, in the operation of reacting, can using catalyzer.As catalyzer, such as, iron(ic) chloride and zinc chloride etc. can be listed.
In addition, the usage quantity of catalyzer is not particularly limited.Such as, more than 0.01 equivalent can be set to relative to the compound represented by general formula (III), be preferably more than 0.01 equivalent and below 3 equivalents.
Oxalic acid derivatives represented by the compound made represented by general formula (III) and general formula (IVb) carries out, in the operation of reacting, can using solvent.As solvent, be then not particularly limited as long as desired compound can be obtained.Such as, the halon such as methylene dichloride and chlorobenzene etc. can be listed.
When reaction employs solvent, the usage quantity of solvent is not particularly limited.Such as can be set to more than 50 quality % relative to the compound represented by general formula (III), be preferably more than 50 quality % and below 2000 quality %.
In addition, temperature of reaction is not particularly limited, and such as, can be set to-20 ~ 100 DEG C, is preferably-10 ~ 50 DEG C.
The manufacture method of the dehydroabietic acid derivative represented by general formula of the present invention (I) also preferably includes the separation circuit of resultant.
As separation circuit, be then not particularly limited as long as desired resultant can be obtained, can suitably select from normally used separation method and be used.Such as, can list: merely by method that the crystallization of resultant of separating out in reaction leaches; After reaction, the method that the resultant of separating out injecting frozen water in reaction solution leaches; Inject frozen water in reaction solution after, water layer is separated, is then washed to after till washing lotion roughly reaches neutrality, the solvent of underpressure distillation removing organic layer and obtain the method etc. of resultant.
The resultant of gained can also carry out refining step.As the process for purification of resultant, it is not particularly limited.Such as, suitably can select from the process for purification that recrystallize, redeposition, column chromatography etc. are conventional.
The manufacture method > of <12-carboxyl dehydroabietic acid derivative
The manufacture method of the 12-carboxyl dehydroabietic acid derivative represented by following general formula (II) of the present invention comprises makes dehydroabietic acid derivative oxidation represented by following general formula (I) and the operation of decarboxylation, and comprises other operation as required and form.By using the dehydroabietic acid derivative represented by general formula (I) as starting material, thus can easily and with the yield of excellence, manufacture the 12-carboxyl dehydroabietic acid derivative represented by general formula (II).
In general formula (I) and general formula (II), R 1represent hydrogen atom, the alkyl that substituent aryl maybe can have substituent carbonatoms 1 ~ 10 can be had, R 2represent that hydrogen atom maybe can have the alkyl of substituent carbonatoms 1 ~ 10.X represents carbonyl, hydroxy methylene or acyloxy methylene radical.
R 1, R 2and the details of X is described above, preferred mode is also identical.
Dehydroabietic acid derivative represented by general formula (I) via oxidation operation and decarboxylation operation, thus is transformed to the 12-carboxyl dehydroabietic acid derivative represented by general formula (II).
Oxidation operation and decarboxylation operation can be applied as an operation, in addition, also can apply successively respectively as independently operation.
When oxidation operation and decarboxylation operation are applied as an operation, as its reaction conditions, such as, can list: utilize hydrogen peroxide to carry out the method processed in the basic conditions; Under mildly acidic conditions, under the existence of sodium tungstate catalyst, hydrogen peroxide is utilized to carry out the method processed; Hypochlorous acid/chlorous acid is utilized to carry out the method processed under mildly acidic conditions; Under the existence of noble metal catalyst, utilize Periodic acid to carry out the method etc. processed.
In addition, carrying out under applicable cases using oxidation operation and decarboxylation operation as operation independently, its application order suitably can be selected according to the kind etc. of the X in general formula (I).
As the reaction conditions of oxidation operation, it is not particularly limited, and suitably can select from normally used oxidation reaction condition.Such as, can list: employ the method for the superoxide such as hydrogen peroxide, employ the method etc. of hypochlorous acid etc.
As the reaction conditions of decarboxylation operation, it is not particularly limited, and suitably can select from normally used decarboxylation reaction conditions.Such as, can list: carry out the method that processes in acid condition and carry out light-struck method etc.
When the compound represented by general formula (I) represents with general formula (B), the R in the compound represented by the general formula (B) that oxidation operation and decarboxylation operation supply 1and R 2be not particularly limited.Wherein, from the view point of reaction efficiency, preferred R 2for hydrogen atom.
R 2compound represented by the general formula (B) of hydrogen atom can be prepared as follows: before oxidation operation and the supply of decarboxylation operation, in advance by R 2compound represented by the general formula (B) beyond hydrogen atom is prepared by ester hydrolysis reaction etc.In addition, following operation can be carried out continuously: by R 2r in compound represented by the general formula (B) beyond hydrogen atom 2change the operation of hydrogen atom, oxidation operation and decarboxylation operation into.
In addition, when the compound represented by general formula (I) represents with general formula (A), the R in the compound represented by the general formula (A) that oxidation operation and decarboxylation operation supply 1, R 2and R 3be not particularly limited.
Such as, R 3compound represented by the general formula (A) of hydrogen atom can be prepared as follows: before oxidation operation and the supply of decarboxylation operation, in advance by R 3compound represented by the general formula (A) of acyl group is prepared by ester hydrolysis reaction etc.In addition, following operation can be carried out continuously: by R 3r in compound represented by the general formula (A) of acyl group 3change the operation of hydrogen atom, oxidation operation and decarboxylation operation into.
12-carboxyl dehydroabietic acid derivative represented by general formula (II) is the dicarboxylic acid compound with the skeleton being derived from plant.Usually, dicarboxylic acid compound can be used as a part for the textural element of polyester polymers, polyamide polymer and polyether polyols with reduced unsaturation.Therefore, the 12-carboxyl dehydroabietic acid derivative represented by general formula (II) can be used for being manufactured on main chain and has the polyester polymers of the skeleton being derived from plant, polyamide polymer and polyether polyols with reduced unsaturation.
Specifically, polyester polymers described in International Publication No. 2010/150847 specification sheets etc. can be preferred for manufacturing.
Embodiment
Below, utilize embodiment to be specifically described the present invention, but the present invention is not limited to following examples.In addition, as long as no specified otherwise, " portion " and " % " is quality criteria.
< embodiment 1>
The synthesis of exemplary compounds (A-1)
By following synthesis path synthesis exemplary compounds (A-1).
At room temperature, to 92% dehydroabietic acid (hereinafter also referred to as " DHA ": Huang Chuan chemical industrial company manufacture) 1.00Kg and methylene dichloride 2L mixture in drip oxalyl chloride 0.45Kg.Stir after 5 hours, underpressure distillation, except desolventizing, drips methyl alcohol 0.55Kg wherein.At room temperature stir after 5 hours, the methyl alcohol that underpressure distillation removing is superfluous, obtain the white crystals 1.10Kg of methyl dehydroabietate (DHA-Me).
To in the Glacial acetic acid 1.5L being cooled to 15 DEG C, while remaining on below 25 DEG C by the temperature in system, drip vitriol oil 500ml lentamente.Add the DHA-Me 314g and glyoxylic acid hydrate 136g that obtain in the above described manner, stir after 4 hours 30 minutes at 40 DEG C, 10 DEG C will be cooled in system.Solution while water after stirring is ice-cold in interpolation system, leaches the crystallization of precipitation, obtains exemplary compounds (A-1) 500g as white crystals.
By the exemplary compounds (A-1) of gained 1h-NMR spectrum (solvent: CDCl 3) one be illustrated in Fig. 1.
< embodiment 2>
The synthesis of exemplary compounds (A-8)
By following synthesis path synthesis exemplary compounds (A-8).
[chemical formula 16]
The aqueous sodium hydroxide solution 60mL of 50wt/v% is dripped in the tetrahydrofuran (THF) 500mL solution of the exemplary compounds of being synthesized by embodiment 1 (A-1) 117.7g.Be warming up to room temperature with this state, place an evening.Add vinyl acetic monomer 500mL, frozen water 200mL, utilize concentrated hydrochloric acid to neutralize, carry out separatory, washing, underpressure distillation removing organic layer, separates out white crystals thus.After utilizing hexane to carry out dispensing laundry, carry out drying, obtain the white crystals 95.2g of exemplary compounds (A-8) thus.
By exemplary compounds (A-8) 1h-NMR spectrum (solvent: CDCl 3) one be illustrated in Fig. 2.
< embodiment 3>
The synthesis of exemplary compounds (A-6)
By following synthesis path synthesis exemplary compounds (A-6).
To in the vinylformic acid 150mL being cooled to 5 DEG C, while remaining on below 15 DEG C by the temperature in system, drip vitriol oil 50mL lentamente.Add DHA-Me 31.4g and glyoxylic acid hydrate 13.6g, stir after 5 hours at 40 DEG C, 10 DEG C will be cooled in system.Solution while water after stirring is ice-cold in interpolation system, utilizes vinyl acetic monomer 500mL to extract.After washing extracting solution according to the order of sodium bicarbonate water, water, distillation is except desolventizing.Utilize hexane/ethyl acetate mixed solvent to adopt the oily matter of column chromatography to gained to refine, obtain the oily matter 32.2g of exemplary compounds (A-6) thus.
By exemplary compounds (A-6) 1h-NMR spectrum (solvent: CDCl 3) one be illustrated in Fig. 3.
< embodiment 4>
The synthesis of exemplary compounds (B-1)
By following synthesis path synthesis exemplary compounds (B-1).
Oxalyl chloride ethyl ester 163.8g is added in the chlorobenzene solution 1L of DHA-Me 314g.Temperature in system being cooled to 5 DEG C, making the temperature in system remain on while about 10 DEG C, dividing three portion-wise addition aluminum chloride (III) 333.4g.After stirring 2 hours with this state, while remaining on below 15 DEG C by the temperature in system, add vinyl acetic monomer 1.5L.Afterwards, while remaining on below 30 DEG C by the temperature in system, add the mixing solutions of water 1.5L/ methyl alcohol 0.2L.By separatory except after the aqueous phase of sub-cloud, 5mol/L aqueous hydrochloric acid 1L is utilized to wash.Then, the salt solution of 15% is utilized to repeat washing for several times until the PH of aqueous phase reaches the scope of 4 ~ 7.Concentration of organic layers, utilizes hexane to carry out crystallization, obtains the white crystals 320g of exemplary compounds (B-1) thus.
By exemplary compounds (B-1) 1h-NMR spectrum (solvent: CDCl 3) one be illustrated in Fig. 4.
< embodiment 5>
The synthesis of exemplary compounds (A-18)
By following synthesis path synthesis exemplary compounds (A-18).
In embodiment 1, use n-propyl alcohol to replace methyl alcohol, in addition, carry out the operation identical with embodiment 1, obtain dehydroabietic acid n-propyl (DHA-PR).
Use the DHA-PR of gained, in addition, carry out the operation identical with embodiment 1, obtain exemplary compounds (A-18).
< embodiment 6>
The synthesis of exemplary compounds (A-4)
By following synthesis path synthesis exemplary compounds (A-4).
In embodiment 1, use propionic acid to replace Glacial acetic acid, in addition, carry out the operation identical with embodiment 1, obtain exemplary compounds (A-4).
< embodiment 7>
The synthesis of exemplary compounds (A-13)
By following synthesis path synthesis exemplary compounds (A-13).
By Songzhi Jiagong Gongyi, China Forestry Publication, Beijing, Chinese, the method that 1998, pp.49-51. records is refined the dehydroabietic acid (manufacture of Huang Chuan chemical industrial company) of 92%, obtains 99% dehydroabietic acid.
Make 99% dehydroabietic acid 300g of gained, acetoxyl group biphenyl 135g, sodium-acetate 4g under a nitrogen, melting at 160 DEG C, stir 1 hour.Afterwards, while the acetic acid that distillation removing generates, 280 degree are periodically warming up to.After utilizing TLC to confirm that raw material disappears, be cooled to room temperature.After adding vinyl acetic monomer dissolving, carry out washing separatory with water, distillation is except desolventizing.Utilize the mixed solvent of vinyl acetic monomer/hexane to carry out crystallization, obtain DHA-Bp 340g thus.
To in the Glacial acetic acid 300ml being cooled to 15 DEG C, while remaining on below 25 DEG C by temperature in system, drip vitriol oil 100ml lentamente.Add the DHA-Bp 75g and glyoxylic acid hydrate 27g that obtain in the above described manner, stir after 5 hours at 40 DEG C, 10 DEG C will be cooled in system.Solution while water after stirring is ice-cold in interpolation system, leaches the crystallization of precipitation, obtains exemplary compounds (A-13) 81g as white crystals thus.
< embodiment 8>
Use the synthesis of the 12-carboxyl dehydroabietic acid of exemplary compounds (B-1)
[chemical formula 22]
The aqueous sodium hydroxide solution 536ml of the exemplary compounds obtained in the above described manner (B-1) 254.5g, 4mol/L and the slurry soln of ethylene glycol 216ml are heated to internal temperature and reach 100 DEG C, stir 5 hours.Reaction system is changed to transparent solution by paste-like.The temperature of system is cooled to 10 DEG C, after adding water 710ml, while remaining on below 25 DEG C by temperature in system, drips the aqueous hydrogen peroxide solution 88.3g of 30%.See in system and slightly foaming, after foaming disappears, continue stirring 1 hour.After the aqueous solution 200ml of slow dropping S-WAT 19.4g, starch potassium iodide paper is utilized to confirm not remaining hydrogen peroxide.After adding methyl alcohol 710ml, utilize the aqueous hydrochloric acid of 10mol/L to neutralize in system, separate out white crystals thus.Leach crystallization by suction funnel, after washing with water, carry out drying, obtain the white crystals 210g (yield is 99%, and purity is 99.5%) of 12-carboxyl dehydroabietic acid thus.
By the 12-carboxyl dehydroabietic acid of gained 1h-NMR spectrum (solvent: DMSO-d 6) one be illustrated in Fig. 5.
< embodiment 9>
Use the synthesis of the 12-carboxyl dehydroabietic acid derivative of exemplary compounds (B-1)
[chemical formula 23]
Under the internal temperature of 15 DEG C, by the solution stirring containing the aqueous sodium hydroxide solution 125ml of exemplary compounds (B-1) 207g, 4mol/L obtained in the above described manner and tetrahydrofuran (THF) 500ml 5 hours.After confirming that raw material disappears, the temperature of system is cooled to 10 DEG C.After vinyl acetic monomer dilution, add hydrochloric acid and neutralize, and carry out washing, separatory.Distillation, except after desolventizing, makes it be dissolved in the aqueous sodium hydroxide solution 1L of 4mol/L.In gained solution, the aqueous hydrogen peroxide solution 70g of 30% is dripped while remaining on below 25 DEG C by the temperature in system.See in system and slightly foaming, after foaming disappears, continue stirring 1 hour.After the aqueous solution 150ml of slow dropping S-WAT 15g, starch potassium iodide paper is utilized to confirm non-residual hydrogen dioxide.Utilize the aqueous hydrochloric acid of 10mol/L to neutralize in system, separate out white crystals.Leached by the crystallization of suction funnel by precipitation, after washing with water, carry out drying, obtain the white crystals 170g (yield is 95%, and purity is 99.0%) of 12-carboxyl methyl dehydroabietate thus.
By the 12-carboxyl methyl dehydroabietate's of gained 1h-NMR spectrum (solvent: CDCl 3) one be illustrated in Fig. 6.
< embodiment 10>
Use the synthesis of the 12-carboxyl dehydroabietic acid of exemplary compounds (A-1)
[chemical formula 24]
The slurry soln of the aqueous sodium hydroxide solution 320ml of the exemplary compounds obtained in the above described manner (A-1) 80.3g, 3.2mol/L is heated to internal temperature and reaches 100 DEG C, stir 5 hours.Reaction system is changed to transparent solution by paste-like.The temperature of system is cooled to 10 DEG C and after adding water 700ml, utilizes aqueous hydrochloric acid to neutralize, leach the powder of precipitation, obtain compound (A-1-2) 64.0g.
Process according to (A-1-2) of the method recorded in J.Am.Chem.Soc.1997, Vol.119, p12386-12387 to gained, 12-carboxyl dehydroabietic acid (yield is 92%, and purity is 99.1%) can be obtained.
From above content, undertaken being oxidized and decarboxylation by the dehydroabietic acid derivative represented by mutual-through type (I), thus can easily and with the yield of excellence, high purity ground manufactures the 12-carboxyl dehydroabietic acid derivative represented by general formula (II).
The disclosure of Japanese patent application 2010-071229 is introduced in this specification sheets with the form of reference.The whole document recorded in this specification sheets, patent application and technological standard with as with reference to and introduces each document, patent application and technological standard specifically and the identical degree of situation about recording respectively, introduce in this specification sheets as reference.The above record relevant to illustrated embodiment of the present invention illustrates and be illustrated as object, and do not intend to carry out describing in detail or being defined in the form of open invention itself.Certainly, the present invention can carry out numerous changes or change is apparent to those skilled in the art.Above-mentioned embodiment is selected for following object and is recorded, namely, in order to the most successfully be described the principle of invention and practical application, and other those skilled in the art are made to understand invention with being suitable for the so various embodiment of contemplated specific end use or various change.Scope of the present invention wishes to specify according to following claim and suitable thing thereof.

Claims (9)

1. the dehydroabietic acid derivative represented by following general formula (I),
In general formula (I), R 1represent the alkyl of hydrogen atom, aryl or carbonatoms 1 ~ 10, R 2represent the alkyl of hydrogen atom or carbonatoms 1 ~ 10, X represents the acyloxy methylene radical of carbonyl, hydroxy methylene or carbonatoms 1 ~ 30.
2. dehydroabietic acid derivative according to claim 1, wherein, in described general formula (I), R 1represent hydrogen atom, the aryl of carbonatoms 6 ~ 12 or the alkyl of carbonatoms 1 ~ 3, R 2represent hydrogen atom, methyl or ethyl, X represents the acyloxy methylene radical of carbonyl, hydroxy methylene or carbonatoms 2 ~ 4.
3. dehydroabietic acid derivative according to claim 1, wherein, described R 2for being selected from the one in hydrogen atom, methyl, ethyl, propyl group, cyclopropyl, butyl, hexyl, cyclohexyl, octyl group and decyl.
4. dehydroabietic acid derivative according to claim 1, wherein, described R 2for being selected from the one in sec.-propyl, isobutyl-, sec-butyl, the tertiary butyl or ethylhexyl.
5. dehydroabietic acid derivative according to claim 1, wherein, described R 2be 2 ethylhexyls.
6. dehydroabietic acid derivative according to claim 1, wherein, described dehydroabietic acid derivative is represented by general formula (A) or general formula (B),
In general formula (A) and general formula (B), R 1represent the alkyl of hydrogen atom, aryl or carbonatoms 1 ~ 10, R 2represent the alkyl of hydrogen atom or carbonatoms 1 ~ 10, R 3represent hydrogen atom or acyl group.
7. a manufacture method for 12 1 carboxyl dehydroabietic acid derivatives represented by following general formula (II), it comprises: be oxidized the dehydroabietic acid derivative represented by following general formula (I) and the operation of decarboxylation,
In general formula (I) and general formula (II), R 1represent the alkyl of hydrogen atom, aryl or carbonatoms 1 ~ 10, R 2represent the alkyl of hydrogen atom or carbonatoms 1 ~ 10, X represents the acyloxy methylene radical of carbonyl, hydroxy methylene or carbonatoms 1 ~ 30.
8. a manufacture method for the dehydroabietic acid derivative represented by following general formula (I), it comprises: make the compound represented by following general formula (III) and the compound represented by following general formula (IV) carry out the operation of reacting,
In general formula (I), general formula (III) and general formula (IV), R 1represent the alkyl of hydrogen atom, aryl or carbonatoms 1 ~ 10, R 2represent the alkyl of hydrogen atom or carbonatoms 1 ~ 10, X represents the acyloxy methylene radical of carbonyl, hydroxy methylene or carbonatoms 1 ~ 30, and Y represents hydrogen atom or leavings group.
9. the manufacture method of dehydroabietic acid derivative according to claim 8, wherein, described Y is selected from the one in hydrogen atom, halogen atom, alkyl and aryl-sulfonyl oxygen and alkyl and arylamino sulfonyloxy.
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