CN101921202A - 3 of 1 replacement, the manufacture method of 5-diaminobenzene - Google Patents
3 of 1 replacement, the manufacture method of 5-diaminobenzene Download PDFInfo
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- CN101921202A CN101921202A CN2010101989338A CN201010198933A CN101921202A CN 101921202 A CN101921202 A CN 101921202A CN 2010101989338 A CN2010101989338 A CN 2010101989338A CN 201010198933 A CN201010198933 A CN 201010198933A CN 101921202 A CN101921202 A CN 101921202A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
- C07C215/74—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
- C07C215/76—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton of the same non-condensed six-membered aromatic ring
- C07C215/80—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton of the same non-condensed six-membered aromatic ring containing at least two amino groups bound to the carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
- C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
- C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
- C07C217/82—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring
- C07C217/90—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the oxygen atom of at least one of the etherified hydroxy groups being further bound to a carbon atom of a six-membered aromatic ring, e.g. amino-diphenylethers
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/52—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
- C07C229/54—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring
- C07C229/60—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring with amino and carboxyl groups bound in meta- or para- positions
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Abstract
The present invention relates to 3 of a kind of 1 replacement, the manufacture method of 5-diaminobenzene.Problem of the present invention provides simply and makes safely 3 of 1 replacement, the method for 5-diaminobenzene.Above-mentioned problem is made 3 of 1 replacement by using the compound shown in the following formula (1), and the 5-diaminobenzene realizes,
In the formula (1), R is that hydrogen atom, carbonatoms are that 1～20 alkyl, carbonatoms are that 6～20 aryl or carbonatoms are 7～20 aralkyl, wherein, and group-N (CH
2CH=CHR)
2The hydrogen atom that is had can be 1～20 alkyl replacement by carbonatoms.
Description
Technical field
The present invention relates to 3 of 1 replacement, the manufacture method of 5-diaminobenzene.In more detail, particularly relate to simply and make safely as 3 of 1 useful replacement of the raw material of polyamic acid that contains in the liquid crystal aligning agent or polyimide, the novel method of 5-diaminobenzene.
Background technology
In liquid crystal display device, use liquid crystal orientation film with liquid crystal molecular orientation.As the material of this liquid crystal orientation film, can use various organic resins such as polyimide, polyamic acid, polymeric amide and polyester.Particularly polyamic acid and polyimide since demonstrate thermotolerance, with excellent rerum natura such as the affinity of liquid crystal, physical strength, so in many liquid crystal display device, use (patent documentation 1～3).
Above-mentioned polyamic acid obtains by the reaction of tetracarboxylic dianhydride and diamines, and above-mentioned polyimide is by obtaining this polyamic acid dehydration closed-loop.The part of the diamines in the raw material of polyamic acid and polyimide preferably use 1 have liquid crystal aligning can the diaminobenzene of 1 replacement of group, thereby improve the liquid crystal aligning of the liquid crystal orientation film of gained.As the diaminobenzene of this 1 replacement, use 2 of 1 replacement mostly, 3 of 4-diaminobenzene and 1 replacement, 5-diaminobenzene.Wherein, 2,4-diamino product is because molecule is a unsymmetric structure, so 2 amino is reactive widely different, polyreaction is difficult to carry out equably, obtains block polymer easily.If use the material of the uneven block polymer of molecular structure as liquid crystal orientation film, when then it being applied as liquid crystal aligning agent, except may producing the coating inequality, also may damage the homogeneity of performance of the liquid crystal orientation film of gained, so improper.Therefore, as the polyamic acid of liquid crystal aligning mould material and the raw material of polyimide, have the symmetrical molecule structure 1 replacement 3, the 5-diaminobenzene is useful.
3 of 1 replacement, 5-diaminobenzene are at present by having passed through the operation manufacturing (patent documentation 4) as the compound with dinitrobenzene structure of synthetic intermediate.Therefore, manufacturing process's quantity is many, and has volatile nitro-compound owing to having passed through, and needs to carry out security measures on engineering, thereby has the high difficult point of manufacturing cost.
[prior art document]
[patent documentation]
[patent documentation 1] Japanese kokai publication hei 9-197411 communique
[patent documentation 2] TOHKEMY 2003-149648 communique
[patent documentation 3] TOHKEMY 2003-107486 communique
[patent documentation 4] TOHKEMY 2008-266421 communique
Summary of the invention
The present invention proposes according to the problems referred to above, and its purpose is to provide simply and safely on the process industry 3 of useful 1 replacement, the method for 5-diaminobenzene.
According to the present invention, above-mentioned purpose of the present invention and advantage are made 3 of 1 replacement by using the compound shown in the following formula (1), and the 5-diaminobenzene is realized.
(in the formula (1), R is that hydrogen atom, carbonatoms are that 1～20 alkyl, carbonatoms are that 6～20 aryl or carbonatoms are 7～20 aralkyl, wherein, and group-N (CH
2CH=CHR)
2The hydrogen atom that is had can be 1～20 alkyl replacement by carbonatoms).
According to the present invention, can provide simply and make safely to have 3 of substituent industrial useful 1 replacement of wide region, the method for 5-diaminobenzene.In the method for the invention, easy as the compound shown in the following formula (1) of raw material use owing to synthesizing, so the present invention helps to reduce 3 of 1 replacement, the cost of 5-diaminobenzene, and then the cost of the various products, particularly liquid crystal display device of this compound manufacturing is used in minimizing.
Embodiment
The main contents of method of the present invention are to use the compound shown in the following formula (1) to make 3 of 1 replacement, 5-diaminobenzene.
" compound shown in the following formula (1) "
As the carbonatoms of the R in the following formula (1) is 1～20 alkyl, and preferred carbonatoms is 1～12 alkyl, can list for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl etc.As the carbonatoms of R is 6～20 aryl, and preferred carbonatoms is 6～12 aryl, can list for example phenyl, aminomethyl phenyl, ethylphenyl, 3,5-dimethylphenyl etc.As the carbonatoms of R is 7～20 aralkyl, and preferred carbonatoms is 7～13 aralkyl, can list for example benzyl, 2-phenylethyl, 3-phenyl propyl etc.Be preferably hydrogen atom as the radicals R in the following formula (1).
In the following formula (1), group-N (CH
2CH=CHR)
2The hydrogen atom that is had can be 1～20 alkyl replacement by carbonatoms.In this case, all group-N (CH that below occur in the explanation
2CH=CHR)
2Should be read as is this substituent.
Compound shown in this following formula (1) for example can pass through 1,3, and the compound reaction shown in 5-trihydroxybenzene and the following formula (4) obtains.
HN(CH
2CH＝CHR)
2 (4)
(in the formula (4), R is identical with the definition in the following formula (1).)
This reaction is confirmed to be this two steps reaction shown in the following synthetic route.
(in the said synthesis route, R is identical with the definition in the following formula (1).)
Therefore, by selecting appropriate reaction conditions, can obtain the compound shown in the needed following formula (1) more with high yield.
As 1,3, the usage ratio of the compound shown in 5-trihydroxybenzene and the following formula (4), with respect to 1,3 of 1mol, the scale of 5-trihydroxybenzene shows, is preferably 2～3mol, more preferably 2～2.5mol with the compound shown in the following formula (4).
Above-mentioned reaction can preferably be carried out in the presence of catalyzer in solvent-free or appropriate solvent.
As the solvent that can use, can list for example aromatics, ether compound, halogenated hydrocarbon compound, hydrocarbon etc. here; As their object lesson, can list respectively: as aromatics is for example benzene,toluene,xylene, ethylbenzene etc.;
As ether compound is for example tetrahydrofuran (THF), dipropyl ether, dibutyl ether, diphenyl ether etc.;
As halohydrocarbon is methylene dichloride, 1 for example, 2-ethylene dichloride, chloroform, tetracol phenixin, 1,4-dichlorobutane, trichloroethane, chlorobenzene, orthodichlorobenzene etc.;
As hydrocarbon is for example hexane, heptane, octane etc.In these solvents, the preferred fragrance compounds of group.
Above-mentioned reaction is preferably solvent-free or carry out in toluene, dimethylbenzene or ethylbenzene.
Above-mentioned being reflected at when carrying out in the solvent, the solid component concentration that is preferably reaction soln as the usage ratio of solvent (is meant that the gross weight of the solvent composition in addition in the reaction soln occupies the ratio of reaction soln gross weight, below identical) be the above ratios of 10 weight %, be more preferably the above ratio of 50 weight %.
Operable catalyzer during as above-mentioned reaction can list for example hydrosulphite (for example, sodium bisulfite, Potassium hydrogen sulfite, ammonium bisulfite etc.), the sulfurous acid aqueous solution, zinc chloride, iodine, calcium chloride, sulfanilic acid, sulfuric acid etc.With respect to 1,3 of 1mol, the 5-trihydroxybenzene, the usage ratio of catalyzer is preferably 0.01～10mol, and more preferably 0.1～3mol is preferably 1～2mol especially.
Temperature of reaction is preferably 30～300 ℃, more preferably 70～200 ℃.Reaction times is preferably 1～100 hour, more preferably 4～24 hours.
Above-mentioned reaction can or add to depress under normal pressure to be carried out, and preference preferably carries out under 1～5 normal atmosphere as carrying out under 1 normal atmosphere (open under the inert atmosphere)～10 normal atmosphere.In addition, when carrying out above-mentioned reaction, not necessarily will pressurize, even react, also can obtain the compound shown in the following formula (1) with high yield under normal pressure, this is an advantage of the present invention.
" 3 of 1 replacement, 5-diaminobenzene "
3 of 1 replacement of making by the present invention, the 5-diaminobenzene is the compound shown in the following formula (2) preferably.
(in the formula (2), Z is the divalent linking group of ether-containing key or ester bond, R
1Be that carbonatoms is 2～51 1 valency group.)。
Linking group Z in the following formula (2) be preferably Sauerstoffatom ,-COO-
*,-O-(CH
2)
n-O-
*,-COO-(CH
2)
n-O-
*,-OCO-(CH
2)
n-O-
*Or-OCO-(CH
2)
n-COO-
*(wherein, above-mentioned in, n is respectively 1～20 integer, the band " * " connecting key be connected with diamino-phenyl).Be preferably 1～6 integer as the n in them, more preferably 1,2 or 6.
R in the following formula (2)
1Preferably,, more preferably do not possess the group of reactive group from the easiness and the reaction efficiency aspect of reaction by the atomic building of the group that is selected from carbon atom, hydrogen atom, Sauerstoffatom, nitrogen-atoms, sulphur atom, phosphorus atom and halogen atom.For example at R
1When serving as reasons the group of atomic building of the group that is selected from carbon atom, hydrogen atom, Sauerstoffatom, nitrogen-atoms and halogen atom, be preferably do not possess belong to by-COOH base ,-the OH base ,-COX base (wherein, X is a halogen atom) ,-NH
2Base ,-the CHO base ,-the OCN base ,-the NCO base ,-N
3Base ,-the NO base ,-NO
2Base ,-the NH-base ,-the O-O-base ,=N
2Base and=group of any group of the group that NH base constitutes.In addition, at R
1Further contain the atomic time more than a kind by the group that is selected from sulphur atom and phosphorus atom, the preferred form that only contains the sulphur atom that contains in the heterocycle of the group that contains heterocycle structure of sulphur with the constituting atom of the sulphur atom that contains in the thioether bond or ring of sulphur atom exists.The heterocycle structure that contains sulphur in the constituting atom as above-mentioned ring can list for example various structures such as tetramethylene sulphur, oxathiane, thiazole, isothiazole, thiophene, thionaphthene, dibenzothiophene, tetramethylene sulfide.On the other hand, preferred form with the phosphorus atom in the group that contains phosphorus naphthalene (ホ ス Off ア ネ Off タ レ Application) structure of the phosphorus atom of above-mentioned situation exists.
As this R
1Be preferably that to have by being selected from carbonatoms be that 1～30 alkyl, carbonatoms are that 1～30 fluoro-alkyl, carbonatoms are that 2～30 thiazolinyl, carbonatoms are 2～30 alkynyl, tetramethyleneimine-2,5-diketone-1-base, carbonatoms are that 3～51 alicyclic radical, carbonatoms are that the carbonatoms of 1 above group of the group of 6～30 aryl and epoxy group(ing) is 2～51 1 valency group (wherein, this 1 valency group is by the atomic building of the group that is selected from carbon atom, hydrogen atom, Sauerstoffatom, nitrogen-atoms and fluorine atom).In above-mentioned, carbonatoms is that 3～51 alicyclic radical and carbonatoms are that 6～30 aryl can be respectively 1 valency group or divalent group.
As above-mentioned R
1The carbonatoms that is had is 1～30 alkyl, be preferably carbonatoms and be 1～20 alkyl, can list for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, n-pentyl, the 3-methyl butyl, the 2-methyl butyl, the 1-methyl butyl, 2, the 2-dimethyl propyl, n-hexyl, the 4-methyl amyl, the 3-methyl amyl, the 2-methyl amyl, the 1-methyl amyl, 3, the 3-dimethylbutyl, 2, the 3-dimethylbutyl, 1, the 3-dimethylbutyl, 2, the 2-dimethylbutyl, 1, the 2-dimethylbutyl, 1, the 1-dimethylbutyl, n-heptyl, 5-methyl hexyl, 4-methyl hexyl, 3-methyl hexyl, 2-methyl hexyl, 1-methyl hexyl, 4,4-dimethyl amyl group, 3,4-dimethyl amyl group, 2,4-dimethyl amyl group, 1,4-dimethyl amyl group, 3,3-dimethyl amyl group, 2,3-dimethyl amyl group, 1,3-dimethyl amyl group, 2,2-dimethyl amyl group, 1,2-dimethyl amyl group, 1,1-dimethyl amyl group, 2,3,3-trimethylammonium butyl, 1,3,3-trimethylammonium butyl, 1,2,3-trimethylammonium butyl, n-octyl, the 6-methylheptyl, the 5-methylheptyl, the 4-methylheptyl, the 3-methylheptyl, the 2-methylheptyl, the 1-methylheptyl, the 2-ethylhexyl, n-nonyl, the ring nonyl, positive decyl, the n-undecane base, dodecyl, n-heptadecane base etc.
As above-mentioned R
1The carbonatoms that is had is 1～30 fluoro-alkyl, and preferred carbonatoms is 3～30 fluoro-alkyl, for example can list 3,3,3-trifluoro propyl, 4,4,4-trifluoro butyl, 5,5,5-trifluoro amyl group, pentafluoroethyl group, 2,2,3,3,3-five fluoropropyls, 3,3,4,4,4-five fluorine butyl, 4,4,5,5,5-five fluorine amyl groups, seven fluoropropyls, 2,2,3,3,4,4,4-seven fluorine butyl, 3,3,4,4,5,5,5-seven fluorine amyl groups, nine fluorine butyl, 2,2,3,3,4,4,5,5,5-nine fluorine amyl groups etc.
As above-mentioned R
1The carbonatoms that is had is 2～30 thiazolinyl, can list for example vinyl, propenyl, butenyl, pentenyl etc.
As above-mentioned R
1The carbonatoms that is had is 2～30 alkynyl, can list for example propargyl, proyl, butynyl, pentynyl etc.
Above-mentioned R
1The carbonatoms that has is that 3～51 alicyclic radical can be 1 valency group or divalent group, and the carbonatoms that as this 1 valency group, can list carbonatoms for example and be 5～10 cycloalkyl, has a steroid skeleton is alkyl of 17～51 etc.;
As the divalent group, can list two cyclohexylene etc.As above-mentioned carbonatoms is 5～10 cycloalkyl, can list for example cyclopentyl, cyclohexyl, suberyl, ring octyl group, ring nonyl, ring decyl, cyclo-dodecyl etc.;
As the carbonatoms with above-mentioned steroid skeleton is 17～51 alkyl, can list for example 3-cholestane base, 3-cholesteryl, 3-lanostane base, 3-lanostene base etc.
Above-mentioned R
1The carbonatoms that is had is that 6～30 aryl can be 1 valency group or divalent group, as this 1 valency group, can list for example phenyl, 4-aminomethyl phenyl, 4-ethylphenyl, 3, the group shown in 5-3,5-dimethylphenyl, naphthyl, the following formula etc.;
As the group of divalent, can list for example naphthylidene etc.
Has the R of special groups as this
1Be preferably for example following formula (R
1-1)～(R
1-10) group of representing respectively, but be not limited to these groups,
(formula (R
1-1) and (R
1-6) a in is respectively 1～20 integer, and b is respectively 0 or 1;
Formula (R
1-7) c in is 1～20 integer,
Formula (R
1-7)～(R
1-9) d in is respectively 0～20 integer,
Wherein, at formula (R
1-7) in, c+d is 1～30 integer,
Formula (R
1-10) e in is 1～20 integer).
" using the compound shown in the following formula (1) to make 3 of 1 replacement, the method for 5-diaminobenzene "
During from the compound shown in the manufacturing following formula of the compound shown in the following formula (1) (2),, for example can followingly carry out according to the kind of the group Z in the following formula (2).
At first, the group Z in following formula (2) is-O-(CH
2)
n-O-
*,-COO-(CH
2)
n-O-
*,-OCO-(CH
2)
n-O-
*When (wherein, n is respectively 1～20 integer, and the connecting key that has " * " is connected with diamino-phenyl), change the compound shown in the following formula (1) into shown in the following formula (3) compound earlier,
(in the formula (3), Y be can with-OH base or-group of COOH radical reaction, n is 1～20 integer, the definition of the R in R and the following formula (1) is identical).
At group Y is can be with the group of-OH radical reaction the time, with compound and the compound R shown in this following formula (3)
1-OH reaction; At group Y is can be with the group of-COOH radical reaction the time, with compound and the compound R shown in this following formula (3)
1-COOH (wherein, in above-mentioned, R
1Respectively and the R in the following formula (2)
1Definition identical) reaction, then, with group-N (CH
2-CH=CHR)
2(wherein, the definition of the R in R and the following formula (1) is identical) changes amino into, thereby obtains the compound shown in the following formula (2).Numerical value n in the following formula (3) selects according to the desirable value of the n in the following formula (2).
The secondth,, the group Z in following formula (2) is-COO-
*Or-OCO-(CH
2)
n-COO-
*When (wherein, in above-mentioned, n is 1～20 integer, and the connecting key that has " * " is connected with diamino-phenyl), make compound and the compound R shown in the following formula (1)
1-Y-COOH (wherein, R
1And the R in the following formula (2)
1Definition identical, Y be singly-bound or
*-COO-(CH
2)
n-(wherein, n is 1～20 integer, has the connecting key and the radicals R of " * "
1Connect)) reaction, then, with group-N (CH
2-CH=CHR)
2(wherein, the definition of the R in R and the following formula (1) is identical) changes amino into, thereby obtains the compound shown in the following formula (2).At compound R
1Y among the-Y-COOH is-COO-(CH
2)
nIn-time, numerical value n selects according to the desirable value of the n in the following formula (2).
The 3rd is, when the group Z in following formula (2) is Sauerstoffatom, with compound and the compound R shown in the following formula (1)
1-Q (wherein, R
1And the R in the following formula (2)
1Definition identical, Q is the group shown in the following formula (Q-1)) reaction,
R’SO
2O-(Q-1)
(in the formula (Q-1), R ' is hydrogen atom, methyl, phenyl, to chlorophenyl or p-methylphenyl))
Then, with group-N (CH
2-CH=CHR)
2(wherein, the definition of the R in R and the following formula (1) is identical) changes amino into, can obtain the compound shown in the following formula (2).
Below, above-mentioned each reaction is described successively.
＜group Z is-O-(CH
2)
n-O-
*Or-COO-(CH
2)
n-O-
*Situation
Among the group Y in the following formula (3), as can and-group of OH radical reaction, for example can list the group shown in halogen atom, carboxyl, the following formula (Y-1) etc.;
R”SO
2O-(Y-1)
(in the formula (Y-1), R " be hydrogen atom, methyl, phenyl, to chlorophenyl or p-methylphenyl)
As can and-group of COOH radical reaction, for example can list the group shown in halogen atom, the following formula (Y-1) etc.Wherein, as halogen atom, can list for example chlorine atom, bromine atoms etc.
When the group Y in following formula (3) is a group shown in halogen atom or the following formula (Y-1), the compound shown in the following formula (3) can and compound R
1-OH or compound R
1(final product of this moment is using compound R in-COOH reaction
1During-OH, be that the Z in the following formula (2) is-O-(CH
2)
n-O-
*Compound; Using compound R
1During-COOH, be that the Z in the following formula (2) is-COO-(CH
2)
n-O-
*Compound).
On the other hand, when the group Y in following formula (3) is carboxyl, the compound shown in the following formula (3) can and compound R
1(final product of this moment is that the Z in the following formula (2) is-OCO-(CH in-OH reaction
2)
n-O-
*Compound).
Below, to above-mentioned each reaction, every kind of group Y is described successively.
[group Y is the situation of halogen atom]
Compound shown in the following formula (1) is being changed in the following formula (3), when group Y is the compound of halogen atom, can pass through compound shown in the following formula (1) and for example compound TsO-(CH
2)
n-X (wherein, Ts is the group shown in the following formula (Y-1), and X is a halogen atom, and the definition of the n in n and the following formula (3) is identical) reaction (reaction (I-1)).Halogen atom as above-mentioned X is preferably chlorine atom or bromine atoms.
Follow and compound R by the reaction product that reaction (I-1) obtains
1-OH or R
1-COOH reaction (respectively by reaction (I-2-1) and (I-2-2)) can obtain the compound shown in the following formula (2).
(in the above-mentioned reaction formula, R is identical with the definition in the following formula (1), and Ts is the group shown in the following formula (Y-1), and X is a halogen atom, and n is identical with the definition in the following formula (3), R
1Identical with the definition in the following formula (2).)
Below, respectively reacting of above-mentioned reaction formula described.
Reaction (I-1)
Compound TsO-(the CH that uses in the reaction (I-1)
2)
n-X (wherein, Ts is the group shown in the following formula (Y-1), and X is a halogen atom, and the definition of the n in n and the following formula (3) is identical) can be connected the compound H O-(CH of chain length (n value) by having desirable methylene radical
2)
n-X and compound TsX (wherein, in above-mentioned, X is a halogen atom) with desirable group Ts solvent-free down or in the appropriate solvent, preferably in the presence of suitable alkali, reaction obtains.As compound H O-(CH
2)
nHalogen atom among-X and the compound TsX can list for example chlorine atom, bromine atoms or iodine atom respectively.
As compound H O-(CH
2)
nThe usage ratio of-X and compound TsX, with compound TsX with respect to 1mol compound H O-(CH
2)
nThe consumption meter of-X is preferably 1～2mol, more preferably 1～1.2mol.
As compound H O-(CH
2)
nOperable solvent when-X and compound TsX reaction, can list for example N, dinethylformamide, N, the N-N,N-DIMETHYLACETAMIDE, gamma-butyrolactone, N-Methyl pyrrolidone, 1,3-dimethyl-2-imidazolidone, dimethyl sulfoxide (DMSO), diglyme, diethoxyethane, glycol dimethyl ether, benzene, toluene, dimethylbenzene, ethylbenzene, tetrahydrofuran (THF) diox, Anaesthetie Ether, dipropyl ether, dibutyl ether, diphenyl ether, methylene dichloride, 1, the 2-ethylene dichloride, chloroform, tetracol phenixin, 1, the 4-dichlorobutane, trichloroethane, chlorobenzene, orthodichlorobenzene, hexane, heptane, octane etc., among them, preferred methylene dichloride, chloroform, toluene, tetrahydrofuran (THF), tetracol phenixin Huo diox.The solid component concentration that is preferably reaction soln as the usage ratio of solvent is the ratio of 3～30 weight %, more preferably the ratio of 5～20 weight %.
As above-mentioned alkali, can list for example triethylamine, Trimethylamine 99, diisopropyl ethyl amine, triisopropylamine, three n-propyl amine, tri-n-butyl amine, N, the N-dimethylcyclohexylam,ne, pyridine, picoline, lutidine, trimethylpyridine, quinoline, isoquinoline 99.9, acridine, phenanthridines, the N-methyl piperidine, the N-crassitude, 1,8-diazabicylo [5.4.0] 11-7-alkene, 1,5-diazabicylo [4.3.0] ninth of the ten Heavenly Stems-5-alkene, N, the N-dimethyl aminopyridine, N, N-dimethyl-9-acridine amine, sodium bicarbonate, saleratus, yellow soda ash, salt of wormwood, sodium methoxide, Sodium Ethoxide, tert.-butoxy potassium etc., among them, preferred triethylamine, diisopropyl ethyl amine or pyridine.With respect to 1mol compound H O-(CH
2)
n-X is preferably 1～10mol as the usage ratio of alkali, more preferably 1～2mol.
The temperature of reaction of this reaction is preferably-50～200 ℃, more preferably 0～100 ℃.Reaction times is preferably 1～100 hour, more preferably 2～24 hours.
This reaction is preferably carried out under inert atmospheres such as nitrogen or argon gas.
Compound and compound TsO-(CH shown in the following formula (1) in the reaction (I-1)
2)
nThe usage ratio of-X is with compound TsO-(CH
2)
n-X represents with respect to the consumption of the compound shown in the 1mol following formula (1), is preferably 0.8～5mol, more preferably 1～2mol.
Reaction (I-1) is preferably carried out in the presence of appropriate solvent and catalyzer.
As above-mentioned solvent, can list for example N, dinethylformamide, N, the N-N,N-DIMETHYLACETAMIDE, gamma-butyrolactone, diethylene glycol dimethyl ether, diethoxyethane, glycol dimethyl ether, acetone, methylethylketone, methyl iso-butyl ketone (MIBK), 2-heptanone, benzene, toluene, dimethylbenzene, ethylbenzene, tetrahydrofuran (THF) diox, Anaesthetie Ether, dipropyl ether, dibutyl ether, methylene dichloride, 1, the 2-ethylene dichloride, chloroform, tetracol phenixin, 1, the 4-dichlorobutane, trichloroethane, chlorobenzene, orthodichlorobenzene, hexane, heptane, octane, ethanol, methyl alcohol, Virahol, the trimethyl carbinol etc., among them, preferred N, dinethylformamide, N,N-dimethylacetamide, diethylene glycol dimethyl ether, diethoxyethane, tetrahydrofuran (THF) Huo diox.The solid component concentration that is preferably reaction soln as the usage ratio of solvent is the ratio of 5～50 weight %.
As above-mentioned catalyzer, can list alkaline catalysts, as preferred object lesson, can list for example sodium bicarbonate, saleratus, lithium bicarbonate, yellow soda ash, salt of wormwood, Quilonum Retard, lime carbonate, barium carbonate, lithium hydride, sodium hydride, potassium hydride KH, hydrolith, metallic lithium, sodium Metal 99.5, potassium metal, sodium methoxide, Sodium Ethoxide, tert.-butoxy potassium, triethylamine, Trimethylamine 99, diisopropyl ethyl amine, triisopropylamine, three n-propyl amine, tri-n-butyl amine, N, the N-dimethylcyclohexylam,ne, pyridine, picoline, lutidine, trimethylpyridine, quinoline, isoquinoline 99.9, acridine, phenanthridines, the N-methyl piperidine, the N-crassitude, 1,8-diazabicylo [5.4.0] 11-7-alkene, 1,5-diazabicylo [4.3.0] ninth of the ten Heavenly Stems-5-alkene, N, the N-dimethyl aminopyridine, N, N-dimethyl-9-acridine amine etc., preferred especially lithium hydride, sodium hydride, potassium hydride KH, hydrolith, metallic lithium, sodium Metal 99.5, potassium metal, sodium methoxide, Sodium Ethoxide, tert.-butoxy potassium or N, the N-dimethyl aminopyridine.As the usage ratio of these catalyzer, with respect to 1mol compound TsO-(CH
2)
n-X is preferably 0.01～10mol, more preferably 1～3mol.
The temperature of reaction (I-1) is preferably 0～300 ℃, more preferably 20～200 ℃.Reaction times is preferably 1～200 hour, more preferably 2～72 hours.
Reaction (I-1) is preferably carried out under inert atmospheres such as nitrogen or argon gas.
Reaction (I-2-1)
Reaction (I-2-1) can be by as above reacting reaction product and the compound R that (I-1) obtains
1-OH (wherein, R
1Identical with the definition in the following formula (2)) react and carry out.
The reaction product and the compound R that obtain as the reaction (I-1) in this reaction (I-2-1)
1The usage ratio of-OH is with compound R
1The consumption meter of the reaction product that-OH obtains with respect to 1mol reaction (I-1) is preferably 0.8～5mol, more preferably 1～2mol.
Reaction (I-2-1) preferably in appropriate solvent, is carried out in the presence of alkali and catalyzer.
As the solvent that can in reaction (I-2-1), use, can list for example N, dinethylformamide, N, the N-N,N-DIMETHYLACETAMIDE, gamma-butyrolactone, diethylene glycol dimethyl ether, diethoxyethane, glycol dimethyl ether, acetone, methylethylketone, methyl iso-butyl ketone (MIBK), 2-heptanone, benzene, toluene, dimethylbenzene, ethylbenzene, tetrahydrofuran (THF) diox, Anaesthetie Ether, dipropyl ether, dibutyl ether, methylene dichloride, 1, the 2-ethylene dichloride, chloroform, tetracol phenixin, 1, the 4-dichlorobutane, trichloroethane, chlorobenzene, orthodichlorobenzene, hexane, heptane, octane, ethanol, methyl alcohol, Virahol, the trimethyl carbinol etc., among them, preferred N, dinethylformamide, N,N-dimethylacetamide, diethylene glycol dimethyl ether, diethoxyethane, tetrahydrofuran (THF) diox, acetone, methylethylketone, methyl iso-butyl ketone (MIBK), 2-heptanone, ethanol, methyl alcohol, the Virahol or the trimethyl carbinol.The solid component concentration that is preferably reaction soln as the usage ratio of solvent is the ratio of 5～50 weight %.
As the preferred alkali of above-mentioned alkali according to the compound R that uses
1The kind of-OH and difference.
As compound R
1Preferred alkali when-OH is alcohol can list for example lithium hydride, sodium hydride, potassium hydride KH, hydrolith, metallic lithium, sodium Metal 99.5, potassium metal, sodium methoxide, Sodium Ethoxide, tert.-butoxy potassium, N, N-dimethyl aminopyridine etc.On the other hand, as compound R
1Preferred alkali in the time that-OH being amphyl, can list for example yellow soda ash, salt of wormwood, Quilonum Retard, lime carbonate, barium carbonate, lithium hydride, sodium hydride, potassium hydride KH, hydrolith, triethylamine, Trimethylamine 99, diisopropyl ethyl amine, triisopropylamine, three n-propyl amine, tri-n-butyl amine, N, N-dimethylcyclohexylam,ne etc.As the usage ratio of these alkali, the reaction product with respect to 1mol reaction (I-1) obtains is preferably 0.01～10mol, more preferably 1～3mol.
As above-mentioned catalyzer, for example can list chlorination tetra-n-butyl ammonium, iodate tetra-n-butyl ammonium, fluoridize tetra-n-butyl ammonium, tetraethylammonium bromide, etamon chloride, iodate tetraethyl ammonium, fluoridize tetraethyl ammonium etc.As the usage ratio of these catalyzer, the reaction product with respect to 1mol reaction (I-1) obtains is preferably 0.01～10mol, more preferably 0.05～2mol.
The temperature of reaction of reaction (I-2-1) is preferably 0～300 ℃, more preferably 20～200 ℃.Reaction times is preferably 1～100 hour, more preferably 2～24 hours.
Reaction (I-2-1) is preferably carried out under inert atmospheres such as nitrogen or argon gas.
[reaction (I-2-2)]
Reaction (I-2-2) can be by as above reacting reaction product and the compound R that (I-1) obtains
1-COOH (wherein, R
1Identical with the definition in the following formula (2)) react and carry out.
The reaction product and the compound R that obtain as the reaction (I-1) in this reaction (I-2-2)
1The usage ratio of-COOH is with compound R
1The consumption meter of the reaction product that-COOH obtains with respect to 1mol reaction (I-1) is preferably 0.8～5mol, more preferably 1～2mol.
Reaction (I-2-2) preferably in appropriate solvent, is carried out in the presence of alkali and catalyzer.
Solvent that can in reaction (I-2-2), use and catalyzer respectively and solvent that can use in reaction (I-2-1) and catalyzer and above-mentioned expression equally.
As preferred alkali in the reaction (I-2-2), can list for example sodium bicarbonate, saleratus, lithium bicarbonate, yellow soda ash, salt of wormwood, Quilonum Retard, triethylamine, Trimethylamine 99, diisopropyl ethyl amine, triisopropylamine, three n-propyl amine, tri-n-butyl amine, N, N-dimethylcyclohexylam,ne, N, N-dimethyl aminopyridine etc.As the usage ratio of alkali, the reaction product with respect to 1mol reaction (I-1) obtains is preferably 0.01～10mol, more preferably 1～3mol.
The temperature of reaction of reaction (I-2-2) is preferably 0～300 ℃, more preferably 20～200 ℃.Reaction times is preferably 1～100 hour, more preferably 2～24 hours.
Reaction (I-2-2) is preferably carried out under inert atmospheres such as nitrogen or argon gas.
[group Y is the situation of carboxyl]
When the compound shown in the following formula (1) being changed into group Y is the compound of carboxyl in the following formula (3), can be by making compound shown in the following formula (1) and for example compound R
2OCO-(CH
2)
n-X (wherein, R
2Be that carbonatoms is 1～10 alkyl, X is a halogen atom, and n is identical with the definition in the following formula (3)) reaction, obtain intermediate (ester products) (reaction (II-1)) after, the ester linkage hydrolyzing (reaction II-2) of this intermediate is carried out.
Then, will react reaction product that (II-2) obtain again and compound R
1-OH reaction can obtain (the reaction (II-3) of the compound shown in the following formula (2).
(in the above-mentioned reaction formula, R is identical with the definition in the following formula (1), and n is identical with the definition in the following formula (3), R
1Identical with the definition in the following formula (2), R
2Be that carbonatoms is 1～10 alkyl, X is a halogen atom).
As the halogen atom of above-mentioned X, be preferably chlorine atom or bromine atoms.
Reaction (II-1)
As compound and the compound R shown in the following formula (1) in the above-mentioned reaction (II-1)
2OCO-(CH
2)
nThe usage ratio of-X is with compound R
2OCO-(CH
2)
n-X is preferably 0.8～5mol, more preferably 1～2mol with respect to the consumption meter of the compound shown in the 1mol following formula (1).
Above-mentioned reaction (II-1) is preferably carried out in the presence of appropriate solvent, alkali and catalyzer.
As above-mentioned solvent, can list for example N, dinethylformamide, N, the N-N,N-DIMETHYLACETAMIDE, gamma-butyrolactone, diethylene glycol dimethyl ether, diethoxyethane, glycol dimethyl ether, acetone, methylethylketone, methyl iso-butyl ketone (MIBK), 2-heptanone, benzene, toluene, dimethylbenzene, ethylbenzene, tetrahydrofuran (THF) diox, Anaesthetie Ether, dipropyl ether, dibutyl ether, methylene dichloride, 1, the 2-ethylene dichloride, chloroform, tetracol phenixin, 1, the 4-dichlorobutane, trichloroethane, chlorobenzene, orthodichlorobenzene, hexane, heptane, octane, ethanol, methyl alcohol, Virahol, the trimethyl carbinol etc., among them, preferred N, dinethylformamide, N,N-dimethylacetamide, diethylene glycol dimethyl ether, diethoxyethane, tetrahydrofuran (THF) Huo diox.The solid component concentration that is preferably reaction soln as the usage ratio of solvent is the ratio of 5～50 weight %.
As above-mentioned alkali, can list for example sodium bicarbonate, saleratus, lithium bicarbonate, yellow soda ash, salt of wormwood, Quilonum Retard, lime carbonate, barium carbonate, lithium hydride, sodium hydride, potassium hydride KH, hydrolith, metallic lithium, sodium Metal 99.5, potassium metal, sodium methoxide, Sodium Ethoxide, tert.-butoxy potassium, triethylamine, Trimethylamine 99, diisopropyl ethyl amine, triisopropylamine, three n-propyl amine, tri-n-butyl amine, N, the N-dimethylcyclohexylam,ne, pyridine, picoline, lutidine, trimethylpyridine, quinoline, isoquinoline 99.9, acridine, phenanthridines, the N-methyl piperidine, the N-crassitude, 1,8-diazabicylo [5.4.0] 11-7-alkene, 1,5-diazabicylo [4.3.0] ninth of the ten Heavenly Stems-5-alkene, N, the N-dimethyl aminopyridine, N, N-dimethyl-9-acridine amine etc., preferred especially lithium hydride, sodium hydride, potassium hydride KH, metallic lithium, sodium Metal 99.5, potassium metal, sodium methoxide, Sodium Ethoxide, tert.-butoxy potassium or N, the N-dimethyl aminopyridine.As the usage ratio of these alkali, the compound with respect to shown in the 1mol following formula (1) is preferably 0.01～10mol, more preferably 1～3mol.
As above-mentioned catalyzer, for example can list chlorination tetra-n-butyl ammonium, iodate tetra-n-butyl ammonium, fluoridize tetra-n-butyl ammonium, tetraethylammonium bromide, etamon chloride, iodate tetraethyl ammonium, fluoridize tetraethyl ammonium etc.The usage ratio of these catalyzer, the compound with respect to shown in the 1mol following formula (1) is preferably 0.01～10mol, more preferably 0.05～2mol.
The temperature of reaction of reaction (II-1) is preferably 0～300 ℃, more preferably 20～200 ℃.Reaction times is preferably 1～200 hour, more preferably 2～72 hours.
Reaction (II-2)
The hydrolysis reaction of reaction (II-2) preferably carries out in the presence of appropriate solvent and suitable alkali.
As the solvent that can in reaction (II-2), use, can list for example ethanol, methyl alcohol, Virahol, the trimethyl carbinol, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, diethylene glycol dimethyl ether, diethoxyethane, glycol dimethyl ether, acetone, methylethylketone, methyl iso-butyl ketone (MIBK), 2-heptanone, tetrahydrofuran (THF), diox, water etc., among them, preferred alcohol, methyl alcohol, Virahol, the trimethyl carbinol, N, dinethylformamide, N,N-dimethylacetamide, diethoxyethane, tetrahydrofuran (THF), diox or water.The solid component concentration that is preferably reaction soln as the usage ratio of solvent is the ratio of 1～50 weight %.
As above-mentioned alkali, can list for example lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, hydrated barta, sodium bicarbonate, saleratus, lithium bicarbonate, yellow soda ash, salt of wormwood, Quilonum Retard, lime carbonate, barium carbonate, sodium methoxide, Sodium Ethoxide, tert.-butoxy potassium, triethylamine, Trimethylamine 99, diisopropyl ethyl amine, triisopropylamine, three n-propyl amine, tri-n-butyl amine, N, N-dimethylcyclohexylam,ne etc., among them, preferred lithium hydroxide, sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, Quilonum Retard, sodium methoxide, Sodium Ethoxide, tert.-butoxy potassium or triethylamine.As the usage ratio of these alkali,, be preferably 0.1～5mol, more preferably 0.5～2mol with respect to 1mol intermediate (ester products).
The temperature of reaction of reaction (II-2) is preferably-50～200 ℃, more preferably 0～100 ℃.Reaction times is preferably 1～200 hour, more preferably 2～72 hours.
Reaction II-3
Reaction (II-3) can be by reaction product and the compound R that as above reaction (II-2) is obtained
1-OH (wherein, R
1Identical with the definition in the following formula (2)) react and carry out.
The reaction product and the compound R that obtain as the reaction (II-2) in this reaction (II-3)
1The usage ratio of-OH is with compound R
1The consumption meter of the reaction product that-OH obtains with respect to 1mol reaction (II-2) is preferably 0.8～5mol, more preferably 1～2mol.
Reaction (II-3) is at N, and N-dimethyl aminopyridine and N under the existence of N '-dicyclohexyl carbon imide, preferably carry out in appropriate solvent.
As N, the usage ratio of N-dimethyl aminopyridine, the reaction product with respect to 1mol reaction (II-2) obtains is preferably 0.01～0.5mol, more preferably 0.05～0.2mol.As N, the usage ratio of N '-dicyclohexyl carbon imide, the reaction product with respect to 1mol reaction (II-2) obtains is preferably 1～5mol, more preferably 1～1.5mol.
As the solvent that can in reaction (II-3), use, can list for example N, dinethylformamide, N, the N-N,N-DIMETHYLACETAMIDE, gamma-butyrolactone, diethylene glycol dimethyl ether, diethoxyethane, glycol dimethyl ether, benzene, toluene, dimethylbenzene, ethylbenzene, tetrahydrofuran (THF) diox, Anaesthetie Ether, dipropyl ether, dibutyl ether, methylene dichloride, 1, the 2-ethylene dichloride, chloroform, tetracol phenixin, 1, the 4-dichlorobutane, trichloroethane, chlorobenzene, neighbour-dichlorobenzene, hexane, heptane, octane etc., among them, preferred methylene dichloride, 1, the 2-ethylene dichloride, chloroform, tetracol phenixin, N, dinethylformamide, N,N-dimethylacetamide, diethylene glycol dimethyl ether, diethoxyethane, glycol dimethyl ether, tetrahydrofuran (THF) Huo diox.The solid component concentration that is preferably reaction soln as the usage ratio of solvent is the ratio of 5～50 weight %.
The temperature of reaction of reaction (II-3) is preferably-50～100 ℃, more preferably 0～50 ℃.Reaction times is preferably 1～100 hour, more preferably 2～24 hours.
Reaction (II-3) is preferably carried out under inert atmospheres such as nitrogen or argon gas.
＜basic Y is the situation of the group shown in the following formula (Y-1) 〉
Compound shown in the following formula (1) is changed in the following formula (3), when group Y is the compound of the group shown in the following formula (Y-1), can be by making compound shown in the following formula (1) and for example compound shown in the following formula (alkylene carbonates) reaction, after obtaining intermediate (reaction (III-1)), make this intermediate again with compound Y-X (wherein, Y is the group shown in the following formula (Y-1), and X is a halogen atom) reaction (reaction (III-2)) carries out.
(wherein, the definition of the n in n and the following formula (3) is identical)
Pass through again and compound R by the reaction product that reaction (III-2) obtains
1-OH or compound R
1-COOH reaction (be respectively reaction (III-3-1) and (III-3-2)) can obtain the compound shown in the following formula (2).
(in the above-mentioned reaction formula, R is identical with the definition in the following formula (1), and n is identical with the definition in the following formula (3), and Y is the group shown in the following formula (Y-1), and X is a halogen atom, R
1Identical with the definition in the following formula (2).)
In this case, in the alkylene carbonates of following formula-(CH
2)
n-numerical value n select according to the desirable value of the n in the following formula (2), from reactive viewpoint, be preferably 2 or 3, preferred especially 2.As the halogen atom among the compound Y-X, preferred chlorine atom.
Reaction (III-1)
As the compound shown in the following formula (1) in the reaction (III-1) and the usage ratio of alkylene carbonates,, be preferably 1～10mol, more preferably 1～2mol in the consumption of alkylene carbonates with respect to the compound shown in the 1mol following formula (1).
Compound shown in the following formula (1) of reaction in (III-1) and the alkylene carbonates shown in the following formula be reflected at solvent-free or appropriate solvent in, preferably in the presence of suitable reaction promotor, carry out.
As the solvent that can in reaction (III-1), use, can list for example ethyl acetate, methyl acetate, propyl acetate, butylacetate, N, dinethylformamide, N, the N-N,N-DIMETHYLACETAMIDE, gamma-butyrolactone, N-Methyl pyrrolidone, 1,3-dimethyl-2-imidazolidone, dimethyl sulfoxide (DMSO), diethylene glycol dimethyl ether, diethoxyethane, glycol dimethyl ether, benzene, toluene, dimethylbenzene, ethylbenzene, tetrahydrofuran (THF) diox, dipropyl ether, dibutyl ether, diphenyl ether, methylene dichloride, 1, the 2-ethylene dichloride, chloroform, tetracol phenixin, 1, the 4-dichlorobutane, trichloroethane, chlorobenzene, neighbour-dichlorobenzene, hexane, heptane, octane etc., among them, preferred N, dinethylformamide, N, the N-N,N-DIMETHYLACETAMIDE, gamma-butyrolactone, N-Methyl pyrrolidone, 1,3-dimethyl-2-imidazolidone or dimethyl sulfoxide (DMSO).The solid component concentration that is preferably reaction soln as the usage ratio of solvent is the ratio of 5～50 weight %.
As the preferred reaction promotor that uses in the reaction (III-1), can list for example bromination tetra-n-butyl ammonium, chlorination tetra-n-butyl ammonium, iodate tetra-n-butyl ammonium, fluoridize the tetra-n-butyl ammonium, tetraethylammonium bromide, etamon chloride, the iodate tetraethyl ammonium, fluoridize tetraethyl ammonium, lithium fluoride, lithium chloride, lithiumbromide, lithium iodide, Sodium Fluoride, sodium-chlor, Sodium Bromide, sodium iodide, Potassium monofluoride, Repone K, Potassium Bromide, potassiumiodide, rubidium chloride, cesium chloride, calcium chloride, magnesium chloride, aluminum chloride, zinc chloride, tin chloride, cobalt chloride, salt of wormwood, lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide etc.As the usage ratio of this reaction promotor, the compound with respect to shown in the 1mol following formula (1) is preferably 0.01～10mol, more preferably 0.05～2mol.
The temperature of reaction of reaction (III-1) is preferably 30～300 ℃, more preferably 70～200 ℃.Reaction times is preferably 1～100 hour, more preferably 2～24 hours.
Above-mentioned reaction (III-1) can carried out under the normal pressure or under the decompression under inert atmospheres such as nitrogen or argon gas, for example can carry out under 1 normal atmosphere (open under the inert atmosphere)～10 normal atmosphere, preferably carries out under 1～5 normal atmosphere.
Reaction (III-2)
As intermediate in the reaction (III-2) of next stage and the usage ratio of compound Y-X,, be preferably 1～2mol, more preferably 1～1.2mol in the consumption of compound Y-X with respect to the 1mol intermediate.
Reaction (III-2) is preferably carried out in the presence of suitable alkali in solvent-free or appropriate solvent.
As the solvent that can in reaction (III-2), use, can list for example N, dinethylformamide, N, the N-N,N-DIMETHYLACETAMIDE, gamma-butyrolactone, N-Methyl pyrrolidone, 1,3-dimethyl-2-imidazolidone, dimethyl sulfoxide (DMSO), diethylene glycol dimethyl ether, diethoxyethane, glycol dimethyl ether, benzene, toluene, dimethylbenzene, ethylbenzene, tetrahydrofuran (THF) diox, Anaesthetie Ether, dipropyl ether, dibutyl ether, diphenyl ether, methylene dichloride, 1, the 2-ethylene dichloride, chloroform, tetracol phenixin, 1, the 4-dichlorobutane, trichloroethane, chlorobenzene, neighbour-dichlorobenzene, hexane, heptane, octane etc., among them, preferred methylene dichloride, chloroform, toluene, tetrahydrofuran (THF), tetracol phenixin Huo diox.Use is during solvent in reaction (III-2), and the solid component concentration that is preferably reaction soln as the usage ratio of solvent is the ratio of 3～30 weight %, more preferably the ratio of 5～20 weight %.
As the preferred alkali that uses in the reaction (III-2), can list for example triethylamine, Trimethylamine 99, diisopropyl ethyl amine, triisopropylamine, three n-propyl amine, tri-n-butyl amine, N, the N-dimethylcyclohexylam,ne, pyridine, picoline, lutidine, trimethylpyridine, quinoline, isoquinoline 99.9, acridine, phenanthridines, the N-methyl piperidine, the N-crassitude, 1,8-diazabicylo [5.4.0] 11-7-alkene, 1,5-diazabicylo [4.3.0] ninth of the ten Heavenly Stems-5-alkene, N, the N-dimethyl aminopyridine, N, N-dimethyl-9-acridine amine, sodium bicarbonate, saleratus, yellow soda ash, salt of wormwood, sodium methoxide, Sodium Ethoxide, tert.-butoxy potassium etc., among them, more preferably use triethylamine, diisopropyl ethyl amine or pyridine.With respect to the 1mol intermediate, be preferably 1～10mol as the usage ratio of these alkali, more preferably 1～2mol.
The temperature of reaction of reaction (III-2) is preferably-50～200 ℃, more preferably 0～100 ℃.Reaction times is preferably 1～100 hour, more preferably 2～24 hours.
Reaction (III-2) is preferably carried out under inert atmospheres such as nitrogen or argon gas.
Reaction (III-3-1)
Reaction (III-3-1) can be by as above reacting reaction product and the compound R that (III-2) obtains
1-OH (wherein, R
1Identical with the definition in the following formula (2)) react and carry out.
The reaction product and the compound R that obtain as the reaction (III-2) in this reaction (III-3-1)
1The usage ratio of-OH is with compound R
1-OH is preferably 0.8～5mol, more preferably 1～2mol with respect to the reaction product consumption meter that 1mol reaction (III-2) obtains.
Reaction (III-3-1) preferably in appropriate solvent, is carried out in the presence of alkali.
As the solvent that can in reaction (III-3-1), use, can list for example N, dinethylformamide, N, the N-N,N-DIMETHYLACETAMIDE, gamma-butyrolactone, diethylene glycol dimethyl ether, diethoxyethane, glycol dimethyl ether, acetone, methylethylketone, methyl iso-butyl ketone (MIBK), 2-heptanone, benzene, toluene, dimethylbenzene, ethylbenzene, tetrahydrofuran (THF) diox, Anaesthetie Ether, dipropyl ether, dibutyl ether, methylene dichloride, 1, the 2-ethylene dichloride, chloroform, tetracol phenixin, 1, the 4-dichlorobutane, trichloroethane, chlorobenzene, neighbour-dichlorobenzene, hexane, heptane, octane, ethanol, methyl alcohol, Virahol, the trimethyl carbinol etc., among them, preferred N, dinethylformamide, N,N-dimethylacetamide, diethylene glycol dimethyl ether, diethoxyethane, tetrahydrofuran (THF) diox, acetone, methylethylketone, methyl iso-butyl ketone (MIBK), 2-heptanone, ethanol, methyl alcohol, the Virahol or the trimethyl carbinol.The solid component concentration that is preferably reaction soln as the usage ratio of solvent is the ratio of 5～50 weight %.
The preferred alkali of above-mentioned alkali is according to the compound R that uses
1The kind of-OH and different.
As compound R
1Preferred alkali when-OH is alcohol can list for example lithium hydride, sodium hydride, potassium hydride KH, hydrolith, metallic lithium, sodium Metal 99.5, potassium metal, sodium methoxide, Sodium Ethoxide, tert.-butoxy potassium, N, N-dimethyl aminopyridine etc.On the other hand, as compound R
1Preferred alkali in the time that-OH being amphyl, can list for example yellow soda ash, salt of wormwood, Quilonum Retard, lime carbonate, barium carbonate, lithium hydride, sodium hydride, potassium hydride KH, hydrolith, triethylamine, Trimethylamine 99, diisopropyl ethyl amine, triisopropylamine, three n-propyl amine, tri-n-butyl amine, N, N-dimethylcyclohexylam,ne etc.As the usage ratio of alkali, the reaction product with respect to 1mol reaction (III-2) obtains is preferably 0.01～10mol, more preferably 1～3mol.
The temperature of reaction of reaction (III-3-1) is preferably 0～300 ℃, more preferably 20～200 ℃.Reaction times is preferably 1～100 hour, more preferably 2～24 hours.
Reaction (III-3-1) is preferably carried out under inert atmospheres such as nitrogen or argon gas.
Reaction (III-3-2)
Reaction (III-3-2) can be by reaction product and the compound R that as above reaction (III-2) is obtained
1-COOH (wherein, R
1Identical with the definition in the following formula (2)) react and carry out.
The reaction product and the compound R that obtain as the reaction (III-2) in this reaction (III-3-2)
1The usage ratio of-COOH is with compound R
1-COOH is preferably 0.8～5mol, more preferably 1～2mol with respect to the reaction product consumption meter that 1mol reaction (III-2) obtains.
Reaction (III-3-2) preferably in appropriate solvent, is carried out in the presence of alkali and catalyzer.
The solvent that can in reaction (III-3-2), use with as solvent that can use in reaction (III-3-2) and above-mentioned list identical.
As preferred alkali in the reaction (III-3-2), can list for example sodium bicarbonate, saleratus, lithium bicarbonate, yellow soda ash, salt of wormwood, Quilonum Retard, triethylamine, Trimethylamine 99, diisopropyl ethyl amine, triisopropylamine, three n-propyl amine, tri-n-butyl amine, N, N-dimethylcyclohexylam,ne, N, N-dimethyl aminopyridine etc.As the usage ratio of alkali, the reaction product with respect to 1mol reaction (III-2) obtains is preferably 0.01～10mol, more preferably 1～3mol.
The temperature of reaction of reaction (III-3-2) is preferably 0～300 ℃, more preferably 20～200 ℃.Reaction times is preferably 1～100 hour, more preferably 2～24 hours.
Reaction (III-3-2) is preferably carried out under inert atmospheres such as nitrogen or argon gas.
[the radicals R in above-mentioned each reaction
1Selection]
Group Z in the following formula (2) is-O-(CH
2)
n-O-
*Or-COO-(CH
2)
n-O-
*When (wherein, n is respectively 1～20 integer, and the connecting key of band " * " is connected with diamino-phenyl), radicals R
1Selection can carry out arbitrarily in above-mentioned scope.Radicals R in the following formula (2)
1Though can be following formula (R for example
1-1) or (R
1-2) base shown in, but be not limited to these groups.
In addition, with group-N (CH of each reaction product of obtaining like this
2-CH=CHR)
2(wherein, the definition of the R in R and the following formula (1) is identical) changes amino method into as described later.
＜group Z is-COO-
*Or-OCO-(CH
2)
n-COO-
*Situation
The secondth,, the group Z in following formula (2) is-COO-
*Or-OCO-(CH
2)
n-COO-
*When (wherein, in above-mentioned, n is 1～20 integer, and the connecting key of band " * " is connected with diamino-phenyl), with compound and the compound R shown in the following formula (1)
1-Y-COOH (wherein, R
1And the R in the following formula (2)
1Definition identical, Y be singly-bound or
*-COO-(CH
2)
n-(wherein, n is 1～20 integer, the connecting key and the radicals R of band " * "
1Connect)) reaction (reaction (IV-1), the following reaction formula of reference),
(in the above-mentioned reaction formula, R is identical with the definition in the following formula (1), R
1Identical with the definition in the following formula (2), Y be singly-bound or
*-COO-(CH
2)
n-(wherein, n is 1～20 integer, the connecting key and the radicals R of band " * "
1Connect)).
Then, by with group-N (CH
2-CH=CHR)
2(wherein, the definition of the R in R and the following formula (1) is identical) changes amino into, can obtain the compound shown in the following formula (2).Compound R
1Y among the-Y-COOH is-COO-(CH
2)
nThe numerical value n in-time selects according to the desirable value of the n in the following formula (2).
Reaction (IV-1)
The compound R that uses in the reaction (IV-1)
1-Y-COOH (wherein, R
1And the R in the following formula (2)
1Definition identical, Y be singly-bound or
*-COO-(CH
2)
n-(wherein, n is 1～20 integer, the connecting key and the radicals R of band " * "
1Connect)), when Y is singly-bound, can will have desirable R
1Carboxylic acid directly as compound R
1-Y-COOH uses; On the other hand, Y is
*-COO-(CH
2)
n-(wherein, n is 1～20 integer, has the connecting key and the radicals R of " * "
1Connect) time, can be by having desirable radicals R
1Compound R
1Compound shown in-OH and the following formula (α, ω-alkylidene group dicarboxylic anhydride), in solvent-free or appropriate solvent, preferably reaction is synthetic in the presence of Tetrabutylammonium bromide and suitable alkali.
(in the following formula, n and group Y are
*-COO-(CH
2)
nThe n in-time is identical.)
In this case, the α of following formula, in ω-alkylidene group dicarboxylic anhydride-(CH
2)
n-numerical value n select according to the desirable value of the n in the following formula (2), but from reactive viewpoint, be preferably 2.
Wherein, as compound R
1-OH and α, the usage ratio of ω-alkylidene group dicarboxylic anhydride, with α, ω-alkylidene group dicarboxylic anhydride is with respect to the 1mol compound R
1The consumption of-OH and counting is preferably 1～10mol, more preferably 1～3mol.
As the solvent that can in this reaction, use, can list for example ethyl acetate, methyl acetate, propyl acetate, butylacetate, N, dinethylformamide, N, the N-N,N-DIMETHYLACETAMIDE, gamma-butyrolactone, N-Methyl pyrrolidone, 1,3-dimethyl-2-imidazolidone, dimethyl sulfoxide (DMSO), diethylene glycol dimethyl ether, diethoxyethane, glycol dimethyl ether, benzene, toluene, dimethylbenzene, ethylbenzene, tetrahydrofuran (THF) diox, dipropyl ether, dibutyl ether, diphenyl ether, methylene dichloride, 1, the 2-ethylene dichloride, chloroform, tetracol phenixin, 1, the 4-dichlorobutane, trichloroethane, chlorobenzene, orthodichlorobenzene, hexane, heptane, octane etc., among them, ethyl acetate, methyl acetate, propyl acetate, butylacetate, N, the N-dimethyl formamide, N,N-dimethylacetamide, gamma-butyrolactone or N-Methyl pyrrolidone.The solid component concentration that is preferably reaction soln as the usage ratio of solvent is the ratio of 5～50 weight %.
The temperature of reaction of this reaction is preferably 0～300 ℃, more preferably 30～200 ℃.Reaction times is preferably 1～100 hour, more preferably 2～24 hours.
This reaction is preferably carried out in inert atmospheres such as nitrogen or argon gas.
As compound and the compound R shown in the following formula (1) in the reaction (IV-1)
1The usage ratio of-Y-COOH is with compound R
1-Y-COOH is preferably 0.8～5mol, more preferably 1～2mol with respect to the consumption meter of the compound shown in the 1mol following formula (1).
Reaction (IV-1) is at N, and N-dimethyl aminopyridine and N under the existence of N '-dicyclohexyl carbon imide, preferably carry out in appropriate solvent.
As N, the usage ratio of N-dimethyl aminopyridine, the compound with respect to shown in the 1mol following formula (1) is preferably 0.01～0.5mol.As N, the usage ratio of N '-dicyclohexyl carbon imide, the compound with respect to shown in the 1mol following formula (1) is preferably 1～2mol.
As the solvent that can in reaction (IV-1), use, can list for example N, dinethylformamide, N, the N-N,N-DIMETHYLACETAMIDE, gamma-butyrolactone, diethylene glycol dimethyl ether, diethoxyethane, glycol dimethyl ether, benzene, toluene, dimethylbenzene, ethylbenzene, tetrahydrofuran (THF) diox, Anaesthetie Ether, dipropyl ether, dibutyl ether, methylene dichloride, 1, the 2-ethylene dichloride, chloroform, tetracol phenixin, 1, the 4-dichlorobutane, trichloroethane, chlorobenzene, orthodichlorobenzene, hexane, heptane, octane etc., among them, preferred methylene dichloride, 1, the 2-ethylene dichloride, chloroform, tetracol phenixin, N, dinethylformamide, N,N-dimethylacetamide, diethylene glycol dimethyl ether, diethoxyethane, glycol dimethyl ether, toluene, tetrahydrofuran (THF) Huo diox.The solid component concentration that is preferably reaction soln as the usage ratio of solvent is the ratio of 5～50 weight %.
The temperature of reaction of reaction (IV-1) is preferably-50～100 ℃, more preferably 0～50 ℃.Reaction times is preferably 1～100 hour, more preferably 2～24 hours.
Reaction (IV-1) is preferably carried out under inert atmospheres such as nitrogen or argon gas.
[the radicals R in the reaction (IV-1)
1Selection]
Group Z in the following formula (2) is-COO-
*Or-OCO-(CH
2)
n-COO-
*When (wherein, in above-mentioned, n is 1～20 integer, and the connecting key of band " * " is connected with diamino-phenyl), radicals R
1Selection can in above-mentioned scope, carry out arbitrarily.Radicals R in the following formula (2)
1Can be following formula (R for example
1-1) or (R
1-3)～(R
1-5) group of representing respectively, but be not limited to these groups.
In addition, with group-N (CH
2-CH=CHR)
2(wherein, the definition of the R in R and the following formula (1) is identical) changes amino method into as described later.
" group Z is the situation of Sauerstoffatom "
The 3rd is, when the group Z in following formula (2) is Sauerstoffatom, makes compound and the compound R shown in the following formula (1)
1-Q (wherein, R
1And the R in the following formula (2)
1Definition identical, Q is the group shown in the following formula (Q-1)) reaction (reaction (V-1), with reference to following reaction formula),
(in the above-mentioned reaction formula, R is identical with the definition in the following formula (1), R
1And the R in the following formula (2)
1Definition identical, Q is the group shown in the following formula (Q-1))
Then, by with group-N (CH
2-CH=CHR)
2(wherein, the definition of the R in R and the following formula (1) is identical) changes amino into, can obtain the compound shown in the following formula (2).
The compound R that uses in the reaction (V-1)
1-Q can have desirable radicals R by making
1Compound R
1-OH obtains with compound Q-X (wherein, X the is a halogen atom) reaction with desirable group Q.As this compound R
1Compound R in the reaction of-OH and compound Q-X
1The usage ratio of-OH and compound Q-X, with compound Q-X with respect to the 1mol compound R
1The consumption meter of-OH is preferably 1～2mol, more preferably 1～1.2mol.This be reflected at solvent-free or appropriate solvent in, preferably in the presence of suitable alkali, carry out.
As the solvent that can here use, can list for example N, dinethylformamide, N, the N-N,N-DIMETHYLACETAMIDE, gamma-butyrolactone, N-Methyl pyrrolidone, 1,3-dimethyl-2-imidazolidone, dimethyl sulfoxide (DMSO), diethylene glycol dimethyl ether, diethoxyethane, glycol dimethyl ether, benzene, toluene, dimethylbenzene, ethylbenzene, tetrahydrofuran (THF) diox, Anaesthetie Ether, dipropyl ether, dibutyl ether, diphenyl ether, methylene dichloride, 1, the 2-ethylene dichloride, chloroform, tetracol phenixin, 1, the 4-dichlorobutane, trichloroethane, chlorobenzene, orthodichlorobenzene, hexane, heptane, octane etc., among them, preferred methylene dichloride, chloroform, toluene, tetrahydrofuran (THF), tetracol phenixin Huo diox.When using solvent in this reaction, the solid component concentration that is preferably reaction soln as the usage ratio of solvent is the ratio of 3～30 weight %, more preferably the ratio of 5～20 weight %.
As compound R
1The preferred alkali that uses in the reaction of-OH and compound Q-X, can list for example triethylamine, Trimethylamine 99, diisopropyl ethyl amine, triisopropylamine, three n-propyl amine, tri-n-butyl amine, N, the N-dimethylcyclohexylam,ne, pyridine, picoline, lutidine, trimethylpyridine, quinoline, isoquinoline 99.9, acridine, phenanthridines, the N-methyl piperidine, the N-crassitude, 1,8-diazabicylo [5.4.0] 11-7-alkene, 1,5-diazabicylo [4.3.0] ninth of the ten Heavenly Stems-5-alkene, N, the N-dimethyl aminopyridine, N, N-dimethyl-9-acridine amine, sodium bicarbonate, saleratus, yellow soda ash, salt of wormwood, sodium methoxide, Sodium Ethoxide, tert.-butoxy potassium etc., among them, more preferably triethylamine, diisopropyl ethyl amine or pyridine.With respect to the 1mol compound R
1-OH, the usage ratio of these alkali is preferably 1～10mol, more preferably 1～2mol.
The temperature of reaction of this reaction is preferably-50～200 ℃, more preferably 0～100 ℃.Reaction times is preferably 1～100 hour, more preferably 2～24 hours.This reaction is preferably carried out under inert atmospheres such as nitrogen or argon gas.
As making the compound R that obtains like this
1Compound R in the reaction (V-1) of the compound reaction shown in-Q and the following formula (1)
1The usage ratio of the compound shown in-Q and the following formula (1) is with compound R
1-Q is preferably 1～2mol, more preferably 1～1.2mol with respect to the consumption meter of the compound shown in the 1mol following formula (1).
Reaction (V-1) is preferably carried out in the presence of suitable alkali in solvent-free or appropriate solvent.
As the solvent that can in reaction (V-1), use, can list for example N, dinethylformamide, N, the N-N,N-DIMETHYLACETAMIDE, gamma-butyrolactone, N-Methyl pyrrolidone, 1,3-dimethyl-2-imidazolidone, dimethyl sulfoxide (DMSO), diethylene glycol dimethyl ether, diethoxyethane, glycol dimethyl ether, benzene, toluene, dimethylbenzene, ethylbenzene, tetrahydrofuran (THF) diox, Anaesthetie Ether, dipropyl ether, dibutyl ether, diphenyl ether, methylene dichloride, 1, the 2-ethylene dichloride, chloroform, tetracol phenixin, 1, the 4-dichlorobutane, trichloroethane, chlorobenzene, orthodichlorobenzene, hexane, heptane, octane etc., among them, preferred methylene dichloride, chloroform, toluene, tetrahydrofuran (THF), tetracol phenixin Huo diox.Use is during solvent in reaction (V-1), and the solid component concentration that is preferably reaction soln as the usage ratio of solvent is the ratio of 3～30 weight %, more preferably the ratio of 5～20 weight %.
As the preferred alkali that uses in the reaction (V-1), can list for example triethylamine, Trimethylamine 99, diisopropyl ethyl amine, triisopropylamine, three n-propyl amine, tri-n-butyl amine, N, the N-dimethylcyclohexylam,ne, pyridine, picoline, lutidine, trimethylpyridine, quinoline, isoquinoline 99.9, acridine, phenanthridines, the N-methyl piperidine, the N-crassitude, 1,8-diazabicylo [5.4.0] 11-7-alkene, 1,5-diazabicylo [4.3.0] ninth of the ten Heavenly Stems-5-alkene, N, the N-dimethyl aminopyridine, N, N-dimethyl-9-acridine amine, sodium bicarbonate, saleratus, yellow soda ash, salt of wormwood, sodium methoxide, Sodium Ethoxide, tert.-butoxy potassium etc., among them, more preferably triethylamine, diisopropyl ethyl amine or pyridine.With respect to the compound shown in the 1mol following formula (1), the usage ratio of these alkali is preferably 1～10mol, more preferably 1～2mol.
The temperature of reaction of reaction (V-1) is preferably-50～200 ℃, more preferably 0～100 ℃.Reaction times is preferably 1～100 hour, more preferably 2～24 hours.Reaction (V-1) is preferably carried out under inert atmospheres such as nitrogen or argon gas.
[the radicals R in the reaction (V-1)
1Selection]
Radicals R when the group Z in the following formula (2) is Sauerstoffatom
1Selection can in above-mentioned scope, carry out arbitrarily.Radicals R in the following formula (2)
1For example can be following formula (R
1-3)～(R
1-10) group of representing respectively, but be not limited to these groups.
In addition, with group-N (CH
2-CH=CHR)
2(wherein, the definition of the R in R and the following formula (1) is identical) changes amino method into as described later.
" with group-N (CH
2-CH=CHR)
2Change amino method into "
Group-N (CH at each midbody compound that will obtain by aforesaid method
2-CH=CHR)
2(wherein, the definition of the R in R and the following formula (1) is identical) when changing amino into, for example can be preferably in appropriate solvent with above-mentioned each midbody compound, and preferably at N, under the existence of N-dimethyl barbituric acid and suitable catalyzer, with group-CH
2-CH=CHR breaks away from, and forms amino and carries out.
As the solvent that can use, can list for example methylene dichloride, chloroform, tetrahydrofuran (THF), diox, ethyl acetate, Anaesthetie Ether, toluene, benzene, N, dinethylformamide, N,N-dimethylacetamide, acetonitrile etc. here.The solid component concentration that is preferably reaction soln as the usage ratio of solvent is the ratio of 3～50 weight %, more preferably 5～20 weight %.
As N, the usage ratio of N-dimethyl barbituric acid is with respect to 1mol group-N (CH
2-CH=CHR)
2, be preferably 0.5～3mol, more preferably 0.5～1mol.
As above-mentioned catalyzer, can list for example palladium compound or palladium complex, rhodium compound or rhodium complex, nickel compound or nickel complex etc.As their object lesson, can list respectively:
As palladium compound or palladium complex is tetrakis triphenylphosphine palladium for example, two (1,2-two (diphenylphosphine acyl group) ethane) palladium, two (dibenzalacetone) palladium, two (tri-butyl phosphine) palladium, two (tricyclohexyl phosphine) palladium, three (dibenzalacetones), two palladiums, palladium-carbon, palladium, Palladous chloride, palladium bromide, palladium iodide, acid chloride, the tetrachloro-palladium acid ammonium, diacetyl two (triphenylphosphine) palladium, dichloro-two (acetonitrile) palladium, dichloro-two (cyanobenzene) palladium, dichloro-(1,2-two (diphenylphosphine acyl group) ethane) palladium, instead-dichloro-two (tricyclohexyl phosphine) palladium, instead-dichloro-two (triphenylphosphine) palladium, instead-dichloro-two (three-o-tolyl phosphine) palladium, dichloro-(1, the 5-cyclooctadiene) palladium, palladium 2,4-pentadiene hydrochlorate, pyruvic acid palladium etc.;
As rhodium compound or rhodium complex is for example Acetyl Acetone acid two (ethylidene) rhodium, two (1, the 5-cyclooctadiene) rhodium, chloro dicarbapentaborane rhodium, chloro norbornadiene rhodium, chloro norbornadiene trialkenyl phosphine rhodium, chloro five amine rhodium muriates, chloro three (triphenylphosphine) rhodium, dicarbapentaborane Acetyl Acetone acid rhodium, dicarbapentaborane (pentamethyl-cyclopentadienyl) rhodium, dichloro-(pentamethyl-cyclopentadienyl) rhodium, 16 carbonyls close six rhodiums, hydrogenized carbonyl three (triphenylphosphine) rhodium, rhodium chloride, the bromination rhodium, the iodate rhodium, rhodium acetate, sad rhodium, the trifluoroacetic acid rhodium, ten dicarbapentaborane close four rhodiums, three (ethylene diamine) rhodium muriate etc.;
As nickel compound or nickel complex is to exemplify as nickle carbonoxide etc.As the usage ratio of these catalyzer, with respect to 1mol group-N (CH
2-CH=CHR)
2, be preferably 0.001～0.05mol.
This temperature of reaction is preferably-20～100 ℃, more preferably 0～50 ℃.Reaction times is preferably 1～120 hour, more preferably 3～24 hours.
3 of＜1 replacement, the 5-diaminobenzene 〉
3 of 1 replacement of above-mentioned manufacturing, the 5-diaminobenzene is suitable as the raw material of various organic synthesis, and is particularly useful as the raw material of polyamic acid that contains in the liquid crystal aligning agent or polyimide.
[embodiment]
In following examples, each compound
1H-NMR measures by following condition respectively.
Determinator: AVANCE E500 (manufacturing of BRUKER company)
Magneticstrength: 500MHz
Solvent: CDCl
3
Reference material: tetramethylsilane
Measure temperature: 30 ℃
In addition, during each compound synthetic, repeat the flow process of following record as required among the following embodiment, thus synthetic necessary amount after guaranteeing.
The synthesis example of the compound the shown in＜following formula (1) 〉
Embodiment 1
In the eggplant type flask of 1L, take by weighing 63g (0.5mol) 1,3,5-trihydroxybenzene and 291g (3mol) diallyl amine adds 52g (0.5mol) sodium bisulfite (NaHSO again
3).Under shading, solvent-free, nitrogen atmosphere, warming while stirring refluxes (140～150 ℃) to diallyl amine with this mixture, carries out reaction in 12 hours again under heating.After reaction finishes, be cooled to 40 ℃ after, in reaction mixture, add 250ml toluene, stir, separate soluble part (solution part) and insoluble part (stores) by decant(-ation), taking-up solution.Add the extraction of 50mL toluene in above-mentioned stores, extraction liquid and the solution that takes out earlier merge.Then, this solution is heated on the limit, and the limit under reduced pressure distillates toluene and unreacted diallyl amine, the residue distilled water wash of gained.
Add the dissolving of 200mL toluene again in the stores after above-mentioned toluene extraction, distilled water wash 3 times of the solution of gained.Toluene layer after this washing and the aforementioned residue that distillates after toluene and the diallyl amine are merged, under reduced pressure distillate toluene, obtain product.This product by NMR (Nuclear Magnetic Resonance) spectrum (
1H-NMR), infrared absorption spectrum (IR) and mass spectroscopy, analyzing this product is 3,5-two (diallyl amino) phenol (below, be called " compound (1-1) ").The output of product is 133g, and yield is 94%.
Each spectrum is as follows.
1H-NMR, chemical shift σ: 5.9～5.8ppm (hydrogen of alkene, 4H), 5.7ppm (4 hydrogen, 1H on the aromatic ring), 5.6ppm (2,6 hydrogen, 2H on the aromatic ring), 5.2～5.1ppm (hydrogen of terminal olefin, 8H), 3.9～3.8ppm (N-C
H 2-, 8H).
IR:3,300cm
-1(hydroxyl), 3,081cm
-1(aryl), 1,839cm
-1, 1,614cm
-1, 1,592cm
-1, 1,585cm
-1, 1,509cm
-1(aromatic series, olefinic double bonds), 798cm
-1, 680cm
-1(aryl).
Mass spectrum: m/z=285 (M
++ 1)
3 of＜1 replacement, the synthesis example of 5-diaminobenzene 〉
Embodiment 2
[synthesizing of the compound shown in the following formula (3)]
According to following synthetic route 1-1, synthetic compound (3-1).
Synthetic route 1-1
(among the synthetic route 1-1, Rs is to the chlorinated benzene alkylsulfonyl).
In the there-necked flask of 300mL, the N of compound (1-1), 22.02g (250mmol) ethylene carbonate, 1.61g Tetrabutylammonium bromide and 100g that adding 14.2g (50.0mmol) the foregoing description 1 obtains, dinethylformamide stirs under 150 ℃ and reacted in 2.5 hours.After reaction finishes, in reaction mixture, after adding 200mL ethyl acetate and the 50mL methanol mixed, all move on in the separating funnel, wash organic layer successively by 10 weight % aqueous sodium hydroxide solutions and distilled water.Afterwards, removal of solvent under reduced pressure obtains 14.8g compound (3-1).
Measure this compound (3-1)
1During H-NMR, chemical shift is as follows.
1H-NMR, chemical shift σ: 7.8ppm (hydrogen of aromatic ring, 2H), 7.5ppm (hydrogen of aromatic ring, 2H), 5.85～5.75ppm (hydrogen of alkene, 4H), 5.7ppm (4 hydrogen, 1H on the aromatic ring), 5.55ppm (2,6 hydrogen, 2H on the aromatic ring), 5.2～5.1ppm (hydrogen of terminal olefin, 8H), 4.4ppm (O-C
H 2-, 2H), 4.1ppm (O-C
H 2-, 2H), 3.9～3.8ppm (N-C
H 2-, 8H).
[compound R
1-OH's is synthetic]
According to following synthetic route 1-2, synthetic compound (R
1-OH-1).
Synthetic route 1-2
(among the synthetic route 1-2, Rs is to the chlorinated benzene alkylsulfonyl.)
In the flask of 200mL, the trans P-coumaric acid of 4.84g (29.5mmol) is dissolved into the N of 55mL, in the dinethylformamide, add 3.88g (45.4mmol) sodium bicarbonate and 10.0g (22.7mmol) compound (R therein
1-OH-1a), under 105 ℃, stir and reacted in 6.5 hours.After reaction finishes, behind the reaction mixture cool to room temperature, add distilled water, suction strainer reclaims the coarse crystallization of separating out, with distilled water wash.Then, (ethyl acetate: recrystallization normal hexane=1: 10 (volume ratio)) obtains 9.3g compound (R to the mixed solvent that the coarse crystallization of gained is formed with ethyl acetate and normal hexane
1-OH-1).
Measure this compound (R
1-OH-1)
1During H-NMR, chemical shift is as follows.
1H-NMR, chemical shift σ: 7.65ppm (hydrogen of alkene, 1H), 7.45ppm (hydrogen of aromatic ring, 2H), 6.85ppm (hydrogen of aromatic ring, 2H), 6.3ppm (hydrogen of alkene, 1H), 4.0ppm (O-C
H 2-, 2H), 1.9～0.85ppm (hydrogen of amyl group dicyclohexyl, 31H).
[3 of 1 replacement, 5-diaminobenzene synthetic]
According to following synthetic route 1-3, synthetic compound (2-1).
(among the synthetic route 1-3, Rs is to the chlorinated benzene alkylsulfonyl.)
In the flask of 500mL, with the above-mentioned 19.0g that obtains (37.7mmol) compound (3-1) and 15.6g (37.7mmol) compound (R
1-OH-1), be dissolved into the N of 150mL, in the N-dimethyl formamide, add 15.6g (113mmol) salt of wormwood therein, stir down at 120 ℃ and reacted in 1 hour.After reaction finishes, behind the reaction mixture cool to room temperature, add distilled water, use chloroform extraction, obtain organic layer.This organic layer with distilled water wash after, removal of solvent under reduced pressure obtains crude product.Then, (weighting agent: silica gel), (ethyl acetate: flow point normal hexane=1: 10 (volume ratio)), removal of solvent under reduced pressure obtains 21.0g compound (2-1a) to the mixed solvent that forms from ethyl acetate and normal hexane with chromatographic column on the crude product that obtains.
Measure this compound (2-1a)
1During H-NMR, chemical shift is as follows.
1H-NMR, chemical shift σ: 7.65ppm (hydrogen of alkene, 1H), 7.45ppm (hydrogen of aromatic ring, 2H), 6.85ppm (hydrogen of aromatic ring, 2H), 6.3ppm (hydrogen of alkene, 1H), 5.9～5.7ppm (hydrogen of alkene, 4H), 5.7ppm (2,4 and 6 hydrogen, 1H on the aromatic ring), 5.2～5.1ppm (hydrogen of terminal olefin, 8H), 4.4ppm (O-C
H 2-, 2H), 4.0ppm (O-C
H 2-, 2H), 3.9～3.8ppm (N-C
H 2-, 8H), 1.9～0.85ppm (hydrogen of amyl group dicyclohexyl, 31H).
Then, the above-mentioned compound that obtains of 21.0g (29.1mmol) (2-1a) is dissolved in the 150mL methylene dichloride, add 13.6g (87.2mmol) 1 therein, 3-dimethyl barbituric acid and 0.67g (0.58mmol) tetrakis triphenylphosphine palladium (O) stirs under 35 ℃ and reacted in 3 hours.Reaction is cooled to 25 ℃ with reaction mixture after finishing, and suction strainer reclaims the crystallization of separating out, and obtains coarse crystallization.This coarse crystallization ethyl alcohol recrystallization obtains 12.3g compound (2-1).
Measure this compound (2-1)
1During H-NMR, chemical shift is as follows.
1H-NMR, chemical shift σ: 7.65ppm (hydrogen of alkene, 1H), 7.45ppm (hydrogen of aromatic ring, 2H), 6.85ppm (hydrogen of aromatic ring, 2H), 6.3ppm (hydrogen of alkene, 1H), 5.9～5.7ppm (hydrogen of alkene, 4H), 5.7ppm (2 and 6 hydrogen, 2H on the aromatic ring), 5.65ppm (4 hydrogen, 1H on the aromatic ring), 4.3ppm (O-C
H 2-, 4H), 4.2ppm (O-C
H 2-, 4H), 4.0ppm (O-C
H 2-, 2H), 1.9～0.85ppm (hydrogen of amyl group dicyclohexyl, 31H).
Synthetic route 2-1
In the 40mL ethyl acetate, mix 7.77g (20mmol) beta-cholestanol, 4.0g (40mmol) succinyl oxide and 0.29g (2.4mmol) dimethyl aminopyridine.After adding 3.3mL (24mmol) triethylamine therein, under 95 ℃, stir and reacted in 5 hours.After reaction finished, solvent washed successively with 10 weight % hydrochloric acid and distilled water after replacing with chloroform.Afterwards, removal of solvent under reduced pressure, the solid that obtains ethyl acetate thorough washing, ethyl acetate is removed in decompression, obtains 4.67g (9.56mmol) compound (R
1-COOH-1) (yield 47.8%).
Measure this compound (R
1-COOH-1)
1During H-NMR, chemical shift is as follows.
1H-NMR, chemical shift σ: 4.71ppm (O-C
H, 1H), 2.65ppm (C
H 2-COO-, 2H), 2.60ppm (C
H 2-COO-, 2H), 2.0～0.65ppm (hydrogen of cholestane base, 46H).
[3 of 1 replacement, 5-diaminobenzene synthetic]
According to following synthetic route 2-2, synthetic compound (2-2).
Synthetic route 2-2
(among the synthetic route 2-2, Rs be) to the chlorinated benzene alkylsulfonyl
In the 40mL methylene dichloride, add 2.84g (10mmol) and the foregoing description 2 similarly synthetic compound (3-1) and the above-mentioned compound (R that obtains of 4.67g (9.56mmol)
1-COOH-1), stir down at 0 ℃.Add 2.48g (12mmol) N therein, behind N '-dicyclohexyl carbon imide and 0.24g (2mmol) 4-dimethylaminopyridine, under 25 ℃, stir and reacted in 4 hours.After reaction finishes, in reaction mixture, add chloroform, the organic layer that washing obtains, removal of solvent under reduced pressure, (the weighting agent: silica gel) of chromatographic column on the crude product of gained, (ethyl acetate: flow point removal of solvent under reduced pressure normal hexane=1: 10 (volume ratio)) obtains 4.0g compound (2-2a) (yield 70%) to the mixed solvent that forms from ethyl acetate and normal hexane.
Measure this compound (2-2a)
1During H-NMR, chemical shift is as follows.
1H-NMR, chemical shift σ: 5.88ppm (hydrogen of aromatic ring, 1H), 5.85～5.80ppm (hydrogen of alkene, 4H), 5.79ppm (hydrogen of aromatic ring, 2H), 5.18～5.12ppm (hydrogen of terminal olefin, 8H), 4.71ppm (O-C
H, 1H), 3.84ppm (N-C
H 2-, 8H), 2.81ppm (C
H 2-COO-, 2H), 2.67ppm (C
H 2-COO-, 2H), 2.0～0.65ppm (hydrogen of cholestane base, 46H).
Mix the above-mentioned compound that obtains of 3.78g (5mmol) (2-2a), 2.34g (15mmol) 1 in the methylene dichloride of 20mL, 3-dimethyl barbituric acid and 0.11g (0.1mmol) tetrakis triphenylphosphine palladium (O) stirs under 35 ℃ and reacted in 7 hours.After reaction finishes, reaction mixture is cooled to 25 ℃ after, wash successively with saturated aqueous sodium carbonate and distilled water.Then, decompression removes from organic layer down and desolvates, and chromatographic column on the crude product that obtains (weighting agent: silica gel), from the mixed solvent (chloroform: flow point ethanol=95: 5 (volume ratio)) of chloroform and ethanol formation, decompression removes down and desolvates, and obtains 1.28g compound (2-2) (yield 43%).
Measure this compound (2-2)
1During H-NMR, chemical shift is as follows.
1H-NMR, chemical shift σ: 5.86ppm (hydrogen of aromatic ring, 3H), 4.71ppm (O-C
H, 1H), 3.60ppm (N
H 2, 4H), 2.80ppm (C
H 2-COO-, 2H), 2.66ppm (C
H 2-COO-, 2H), 2.0～0.65ppm (hydrogen of cholestane base, 46H).
Embodiment 4
[compound (R
1-Q-1) synthetic]
According to following synthetic route 3-1, synthetic compound (R
1-Q-1).
Synthetic route 3-1
(among the synthetic route 3-1, Rs is a p-toluenesulfonyl).
In the 1L there-necked flask of thermometer and dropping funnel has been installed, with the trans amyl group dicyclohexyl of 50g (188mmol) dissolve with methanol in 250mL toluene, therein, under nitrogen atmosphere, the hydrogen chlorate who adds 65.4g (470mmol) triethylamine and 19.8g (207mmol) Trimethylamine 99, the frozen water cooling.Then, spend 1 hour from dropping funnel, toward wherein dripping after 43.0g (225mmol) Tosyl chloride is dissolved into the solution that forms in the 250mL toluene, making reaction mixture is room temperature (25 ℃), and then stirs 6 hours.After the trans amyl group dicyclohexyl methyl alcohol completely dissolve in the tlc affirmation reaction mixture, the suction strainer reaction mixture obtains filtrate.Add the N of 15g in the filtrate of gained, the N-dimethyl-ethylenediamine stirred 1 hour.Reaction mixture after the stirring moves on in the separating funnel, washs successively with 150mL distilled water, 150mL saturated sodium bicarbonate aqueous solution and 150mL distilled water, from the organic layer removal of solvent under reduced pressure, obtains 78g compound (R
1-Q-1) (solid state, yield 97%).
Measure this compound (R
1-Q-1)
1During H-NMR, chemical shift is as follows.
1H-NMR, chemical shift σ: 7.8ppm (hydrogen of aromatic ring, 2H), 7.3ppm (hydrogen of aromatic ring, 2H), 3.8ppm (O-C
H 2-, 2H), 1.8～0.8ppm (amyl group dicyclohexyl, 31H).
[synthesizing of compound (2-3)]
According to following synthetic route 3-2, synthetic compound (2-3),
Synthetic route 3-2
(among the synthetic route 3-2, Rs is a p-toluenesulfonyl).
In the there-necked flask of 1L, take by weighing 28.6g potassium hydride KH (30 weight % mineral oil suspension liquid) (be scaled pure potassium hydride KH and be equivalent to 219mmol), it is used 100mL petroleum ether 2 times (using the sherwood oil that amounts to 200mL).Then, thermometer and dropping funnel are installed in there-necked flask, container is interior with nitrogen replacement.
Add the 500mL tetrahydrofuran (THF) in above-mentioned there-necked flask, the frozen water cooling is dissolved into the solution that the 100mL tetrahydrofuran (THF) forms with 52.6g (186mmol) compound (1-1), divides dropping in 30 minutes from dropping funnel.This operation is after 10 minutes, with the above-mentioned synthetic compound of 78g (186mmol) (R
1-Q-1) the directly each 5g ground of solid state added in the solution whole the branch in 30 minutes.After adding end, mixture frozen water cooling ground stirred after 30 minutes, at room temperature stirred and reacted in 6 hours.
Afterwards, reaction mixture is infused in the 200g ice covered in the mixture of 40g ammonium chloride, stir, the organic layer of gained adds separating funnel, and this organic layer is with 500mL toluene extraction 2 times.Merge this organic layer, behind the distilled water wash, decompression removes down and desolvates, and obtains crude product.Silica gel chromatographic column on this crude product, (ethyl acetate: flow point normal hexane=1: 50 (volume ratio)), removal of solvent under reduced pressure obtains 48g mixture (2-3a) (yield 47%) to the mixed solvent that forms from ethyl acetate and normal hexane.
Measure this compound (2-3a)
1During H-NMR, chemical shift is as follows.
1H-NMR, chemical shift σ: 5.88ppm (hydrogen of aromatic ring, 1H), 5.85～5.80ppm (hydrogen of alkene, 4H), 5.79ppm (hydrogen of aromatic ring, 2H), 5.18～5.12ppm (hydrogen of terminal olefin, 8H), 4.71ppm (O-C
H, 1H), 3.84ppm (N-C
H 2-, 8H), 3.66ppm (O-C
H 2-, 2H), 1.8～0.8ppm (amyl group dicyclohexyl, 31H).
Then, the above-mentioned compound that obtains of 47.7g (89.7mmol) (2-3a) is dissolved in the 400mL methylene dichloride, add 84.0g (538mmol) N, N-dimethyl barbituric acid and 1.04g (0.9mmol) tetrakis triphenylphosphine palladium (0) stirs under 35 ℃ and reacted in 7 hours.After reaction finished, reaction mixture moved in the separating funnel, uses saturated sodium bicarbonate aqueous solution and distilled water wash successively.Desolvate from following the removing of organic layer decompression of gained, obtain crude product.Silica gel chromatographic column on this crude product, from the chloroform flow point, decompression removes down and desolvates, obtain solids after, this solids is washed with normal hexane, obtain 17.0g compound (2-3) (yield 45%).
Measure this compound
1During H-NMR, chemical shift is as follows.
1H-NMR, chemical shift σ: 5.86ppm (hydrogen of aromatic ring, 3H), 3.66ppm (O-C
H 2-, 2H), 1.8～0.8ppm (amyl group dicyclohexyl, 31H).
With similarly above-mentioned, or according to aforesaid method, can obtain 3 of 1 replacement that following formula (2-4)～(2-14) represents respectively with high yield, the 5-diaminobenzene.
According to these embodiment, shown in the following formula (1) compound had-the OH base is the group that can react under the usual terms in organic chemical reactions, reality has proved utilizes this reaction to import group arbitrarily on 1 carbon of phenyl ring, and group-N (CH of the compound shown in the following formula (1)
2-CH=CHR)
2Can easily change amino into, thereby show the compound shown in the following formula (1) as making 3 of 1 replacement, the raw material of 5-diaminobenzene is useful.
Claims (12)
1. the compound shown in the following formula (1) is made 3 of 1 replacement, the purposes of 5-diaminobenzene,
In the formula (1), R is that hydrogen atom, carbonatoms are that 1～20 alkyl, carbonatoms are that 6～20 aryl or carbonatoms are 7～20 aralkyl, wherein, and group-N (CH
2CH=CHR)
2The hydrogen atom that is had can be 1～20 alkyl replacement by carbonatoms.
2. the purposes of putting down in writing according to claim 1,3 of wherein above-mentioned 1 replacement, the 5-diaminobenzene is the compound shown in the following formula (2),
In the formula (2), Z is the divalent linking group of ether-containing key or ester bond, R
1Be that carbonatoms is 2～51 1 valency group.
3. the purposes of putting down in writing according to claim 2, wherein the Z in the following formula (2) be Sauerstoffatom ,-COO-
*,-O-(CH
2)
n-O-
*,-COO-(CH
2)
n-O-
*,-OCO-(CH
2)
n-O-
*Or-OCO-(CH
2)
n-COO-
*(wherein, above-mentioned in, n is respectively 1～20 integer, the band " * " connecting key be connected with diamino-phenyl);
R
1Be to have that to be selected from carbonatoms be that 1～30 alkyl, carbonatoms are that 1～30 fluoro-alkyl, carbonatoms are that 2～30 thiazolinyl, carbonatoms are 2～30 alkynyl, tetramethyleneimine-2,5-diketone-1-base, carbonatoms are that 3～51 alicyclic radical, carbonatoms are that the carbonatoms of 1 above group of the group of 6～30 aryl and epoxy group(ing) is 2～51 1 valency group (wherein, this 1 valency group is by the atomic building of the group that is selected from carbon atom, hydrogen atom, Sauerstoffatom, nitrogen-atoms and fluorine atom).
4. (wherein, the group Z in the following formula (2) is-O-(CH the compound shown in the manufacturing following formula (2)
2)
n-O-
*Or-COO-(CH
2)
n-O-
*(wherein, n is respectively 1～20 integer, and the connecting key that has " * " is connected with diamino-phenyl)) method, it is characterized in that: change the compound shown in the following formula (1) into shown in the following formula (3) compound,
(in the formula (3), Y be can with-OH base or-group of COOH radical reaction, n is 1～20 integer, group-N (CH
2-CH=CHR)
2Identical with the definition in the following formula (1))
At group Y is can be with the group of-OH radical reaction the time, with compound and the compound R shown in this following formula (3)
1-OH reaction; At group Y is can be with the group of-COOH radical reaction the time, with compound and the compound R shown in this following formula (3)
1-COOH (wherein, in above-mentioned, R
1Respectively and the R in the following formula (2)
1Definition identical) reaction, then, with group-N (CH
2-CH=CHR)
2(wherein, the definition of the R in R and the following formula (1) is identical) changes amino into.
5. the method for putting down in writing according to claim 4, wherein above-mentioned Y is the group shown in halogen atom, carboxyl or the following formula (Y-1),
R”SO
2O-(Y-1)
In the formula (Y-1), R " be hydrogen atom, methyl, phenyl, to chlorophenyl or p-methylphenyl.
6. according to claim 4 or 5 methods of putting down in writing, wherein above-mentioned R
1Be following formula (R
1-1) or (R
1-2) group shown in,
Formula (R
1-1) a in is 1～20 integer, and b is 0 or 1.
7. (wherein, the group Z in the following formula (2) is-COO-the compound shown in the manufacturing following formula (2)
*Or-OCO-(CH
2)
n-COO-
*(wherein, in above-mentioned, n is respectively 1～20 integer, and the connecting key that has " * " is connected with diamino-phenyl)) method, it is characterized in that: with compound and the compound R shown in the following formula (1)
1-Y-COOH (wherein, R
1And the R in the following formula (2)
1Definition identical, Y be singly-bound or
*-COO-(CH
2)
n-(wherein, n is 1～20 integer, has the connecting key and the radicals R of " * "
1Connect)) reaction, then, with group-N (CH
2-CH=CHR)
2(wherein, the definition of the R in R and the following formula (1) is identical) changes amino into.
8. the method for putting down in writing according to claim 7, wherein above-mentioned R
1Be following formula (R
1-1) or following formula (R
1-3)～(R
1-5) group of each expression,
Formula (R
1-3)～(R
1-5) in, " * " represents connecting key respectively.
9. the manufacture method of the compound shown in the following formula (2) (wherein, the group Z in the following formula (2) is a Sauerstoffatom) is characterized in that: with compound and the compound R shown in the following formula (1)
1-Q (wherein, R
1And the R in the following formula (2)
1Definition identical, Q is the group shown in the following formula (Q-1)) reaction,
R’SO
2O-(Q-1)
(in the formula (Q-1), R ' is hydrogen atom, methyl, phenyl, to chlorophenyl or p-methylphenyl))
Then, with group-N (CH
2-CH=CHR)
2(wherein, the definition of the R in R and the following formula (1) is identical) changes amino into.
10. the method for putting down in writing according to claim 9, wherein above-mentioned R
1Be following formula (R
1-3)～(R
1-5) or following formula (R
1-6)～(R
1-10) group of each expression,
C
cF
2c+1—(CH
2)
d——* (R
1-7)
CH≡C—(CH
2)
d——* (R
1-8)
(formula (R
1-6) a in is 1～20 integer, and b is respectively 0 or 1;
Formula (R
1-7) c in is 1～20 integer,
Formula (R
1-7)～(R
1-9) d in is respectively 0～20 integer,
Wherein, at formula (R
1-7) in, c+d is 1～30 integer,
Formula (R
1-10) e in is 1～20 integer).
11. the compound shown in the following formula (1).
12. the manufacture method of the compound shown in the following formula (1) is characterized in that: with 1,3, the compound reaction shown in 5-trihydroxybenzene and the following formula (4),
HN(CH
2CH＝CHR)
2?(4)
In the formula (4), group-N (CH
2CH=CHR)
2Identical with the definition in the following formula (1).
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| JP2009-139214 | 2009-06-10 |
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|---|---|---|---|---|
| CN108640846A (en) * | 2018-04-25 | 2018-10-12 | 哈尔滨工业大学 | A kind of flexible aromatic diamine monomers of the side group containing aromatic ring and preparation method thereof |
| CN111647412A (en) * | 2020-06-12 | 2020-09-11 | 江苏三月科技股份有限公司 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
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| JP5590304B2 (en) * | 2009-06-11 | 2014-09-17 | Ｊｓｒ株式会社 | Liquid crystal aligning agent and liquid crystal display element |
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| KR101685400B1 (en) | 2016-12-12 |
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