CN105237337A - Novel synthesis method for 5-[10-(9-carbosyl anthryl)]-isophthalic acid - Google Patents
Novel synthesis method for 5-[10-(9-carbosyl anthryl)]-isophthalic acid Download PDFInfo
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
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- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
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- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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Abstract
The invention provides a novel synthesis method for 5-[10-(9-carbosyl anthryl)]-isophthalic acid. A diazotization bromination reaction is conducted on 5-amino-1,3-benzenedicarboxylic acid dimethyl ester to synthesize a compound A, namely, 5-bromine-1,3-benzenedicarboxylic acid dimethyl ester, and catalysts are added to 5-bromine-1,3-benzenedicarboxylic acid dimethyl ester under the condition of nitrogen protection to make 5-bromine-1,3-benzenedicarboxylic acid dimethyl ester react with bis(pinacolato)diboron so as to generate a compound B, namely, 3,5-bis(methoxycarbonylethyl)phenylboronic acid pinacol ester. In addition, anthracene-9-carboxylic acid is bromized to obtain a compound C, namely, 10-bromine-9-carboxylic acid, the compound C is subjected to methyl esterification to generate a compound D, namely, 10-bromine-9-anthracene methyl formate, and the compound D and the compound B are subjected to a nitrogen protection reaction under the effect of catalysts to generate a compound E, namely, 5-[10-(9-methoxycarbonyl group anthryl)]-benzenedicarboxylic acid dimethyl ester, and a target compound F, namely, 5-[10-(9-carboxyl anthryl)]-isophthalic acid through a hydrolysis reaction. The target compound F is shown in the figure.
Description
Technical field
The present invention relates to a kind of synthetic method of synthetic method, particularly a kind of novel 5-[10-(9-carboxyl anthryl)]-m-phthalic acid of rigidity dibenzyl tricarboxylic acid ligand compound.
Background technology
The rigidity tricarboxylic acids part extended is widely used in the synthesis of MOFs material, this kind of material has good pore passage structure, large internal surface area usually, makes this kind of material have potential application in different field such as gaseous storage, chemical sensitisation, catalysis and medicament slow releases.Such as with the three-dimensional porous compound (HKUST-1) being secondary structure unit with colyliform double-core copper that trimesic acid and cupric nitrate synthesize under hydrothermal conditions; The MOF-177 with qom topological network synthesized with zinc nitrate solvent thermal process, [Zn
4o (BTB)
2(DMF)
15(H
2o)
3].The specific surface area of this compound reaches 4500m
2g
-1, have stronger absorption property for organic macromolecule, multiple gases molecule and dye molecule.And the rigidity triangle Carboxylic acid ligand extended can obtain novel structure, many micropores MOFs material that specific surface area is large usually, and can microvoid structure be changed, electronic environment in its pore is made to be optimized thus to improve above-mentioned application performance, therefore, design and synthesis novel structure prolongation poly carboxylic acid part and the synthesis being applied to MOFs material has become one of focus of current research.But large-sized rigidity multi-carboxylic acid compounds synthesis ratio is more difficult.5-[10-(9-carboxyl anthryl)]-m-phthalic acid of therefore involved in the present invention novel structure is a kind of part with huge potential using value.There is no this compound of bibliographical information at present.
Summary of the invention
The object of this invention is to provide a kind of synthetic method of synthesizing novel 5-[10-(9-carboxyl anthryl)]-m-phthalic acid that cost is low, productive rate is high, product purity is high.
The synthetic method of 5-of the present invention [10-(9-carboxyl anthryl)]-m-phthalic acid, synthesis step is:
(I) is with 5-amino-1, 3-rutgers is raw material, 15% hydrobromic acid solution is added under low temperature, slowly sodium nitrite solution is dripped under adding rear rapid stirring, slowly drip the hydrobromic acid solution of cuprous bromide subsequently, mol ratio 5-amino-1, 3-rutgers: Sodium Nitrite: cuprous bromide is 1:1.1 ~ 1.3:1.4 ~ 1.6, add stirring at room temperature 2 hours, vacuum filtration obtains reacting coarse product, by sherwood oil after dry: the mixed solvent of ethyl acetate volume ratio 2 ~ 3:1 is that eluent pillar layer separation is purified to obtain white powder A:5-bromo-1, 3-rutgers,
(II) is under the condition of argon gas or nitrogen protection, with 5-bromo-1, 3-rutgers, connection boric acid pinacol ester and potassium acetate in molar ratio 1:1 ~ 1.5:2.5 ~ 3.5 are dissolved in anhydrous dioxane after mixing, 5-bromo-1, the amount ratio of 3-rutgers and dioxane is that 1 milli rubs: 2.5 ~ 3.5 milliliters, add appropriate catalyzer, back flow reaction 10 ~ 20 hours under 110 ~ 130 DEG C of oil baths, after cooling, first dilute with water extracts system by ethyl acetate again, then with saturated aqueous common salt, organic layer is washed, collect organic phase and carry out except water treatment by anhydrous sodium sulphate to it, filter, vacuum concentration, finally with sherwood oil and ethyl acetate by volume for the mixed solvent of 16:0.8 ~ 1.2 is that eluent column chromatography separating-purifying obtains compd B: 3, 5-dimethoxycarbonyl phenylo boric acid pinacol ester,
(III) 9-anthroic acid is dissolved in glacial acetic acid, drips the acetum of bromine under ice bath, and the mol ratio of 9-anthroic acid and bromine is 1:1.5 ~ 1.8, and drip off and be warming up to 65 DEG C of reactions 2 ~ 4 hours, reaction solution adds in the frozen water of 500 ~ 800mL, separates out precipitation, filters.Solid is dissolved in 500 ~ 600mL5 ~ 10%K
2cO
3in solution, filter removal of contamination, filtrate uses rare HNO
3precipitation is separated out in acidifying, and dehydrated alcohol recrystallization obtains the bromo-9-anthroic acid of pale yellow powder C:10-;
Excessive SOCl is added in (IV) 10-bromo-9-anthroic acid
2, catalyzer made by a little pyridine, and 80 ° of C react 10 ~ 12 hours, and excessive SOCl is removed in underpressure distillation
2be cooled to normal temperature, 40 ~ 60mL methyl alcohol is added in round-bottomed flask, add 50 ~ 80mL methylene dichloride and make solvent, 85 ° of C reacting by heating 2 ~ 3 hours, steam excessive methyl alcohol, finally with sherwood oil and methylene dichloride by volume for the mixed solvent of 4:0.8 ~ 1 is that eluent column chromatography separating-purifying obtains Compound D: 10-bromo-9-anthroic acid methyl esters;
(V) under argon gas or nitrogen protection, by B, D and K
3pO
480 ~ 100mL1 is dissolved in 1.2:1:3 mixing in molar ratio, in 4-dioxane solvent, passes into N
2after 10 minutes, add proper catalyst, react 10 ~ 20 hours under 90 ~ 110 DEG C of oil baths, steam excessive dioxane, first dilute with water after cooling, with methylene dichloride, system is extracted again, collect organic phase and carry out except water treatment with sodium sulphite anhydrous 99.3 to it, filter, vacuum concentration, then with sherwood oil and ethyl acetate by volume for 100:0.8 ~ 1 is for eluent, obtain white product E:5-[10-(9-methoxycarbonyl anthryl)]-dimethyl isophthalate with column chromatography separating-purifying;
5-[10-(9-methoxycarbonyl anthryl)]-dimethyl isophthalate and NaOH add in the mixed solvent of Isosorbide-5-Nitrae-dioxane and water in 1:10 ~ 15 by (VI) in molar ratio, and volume ratio is 2 ~ 3:1.95 DEG C are refluxed 4 ~ 6 hours, steam Isosorbide-5-Nitrae-dioxane that removing is excessive, add excessive rare HNO
3carry out being acidified to pH ≈ 2, separate out yellow solid, vacuum-drying obtains finalization compound F:5-[10-(9-carboxyl anthryl)]-m-phthalic acid.
The synthetic method of the novel 5-of described one [10-(9-carboxyl anthryl)]-m-phthalic acid, when there is diazotization reaction in preparation A, temperature of reaction should control below 5 DEG C, and eluent during purifying A is sherwood oil: ethyl acetate volume ratio 2 ~ 3:1.
The synthetic method of the novel 5-of described one [10-(9-carboxyl anthryl)]-m-phthalic acid, with bromo-1, the 3-rutgers of 5-, connection boric acid pinacol ester and potassium acetate 1:1.2:2.5 synthetic compound B in molar ratio.Purifying B sherwood oil and ethyl acetate volume ratio are 16:1.
The synthetic method of the novel 5-of described one [10-(9-carboxyl anthryl)]-m-phthalic acid, during preparation Compound C, the mol ratio of 9-anthroic acid and bromine is 1:1.8.
The synthetic method of the novel 5-of described one [10-(9-carboxyl anthryl)]-m-phthalic acid, during preparation Compound D, SOCl
2all need excessive with methyl alcohol, need add 50 ~ 80mL methylene dichloride and make solvent, sherwood oil and methylene dichloride are by volume for the mixed solvent of 4:1 is eluent.
The synthetic method of the novel 5-of described one [10-(9-carboxyl anthryl)]-m-phthalic acid, the catalyzer preparing compd B use is [1,1 '-bis-(diphenylphosphino) ferrocene] palladium chloride, consumption is participate in reactant total mass 0.5 ~ 1%.
The synthetic method of the novel 5-of described one [10-(9-carboxyl anthryl)]-m-phthalic acid, the catalyzer preparing compd E use is tetrakis triphenylphosphine palladium, and consumption is participate in reactant total mass 1 ~ 2%.
The synthetic method of the novel 5-of described one [10-(9-carboxyl anthryl)]-m-phthalic acid, prepares compd E and uses B, D and K
3pO
41.2:1:3 in molar ratio, sherwood oil and ethyl acetate are by volume for 100:1 is eluent.
The synthetic method of the novel 5-of described one [10-(9-carboxyl anthryl)]-m-phthalic acid, 5-[10-(9-methoxycarbonyl anthryl)]-dimethyl isophthalate and NaOH 1:12 in molar ratio, solvent 1, in the mixed solvent of 4-dioxane and water, volume ratio is 2 ~ 3:1, is acidified to pH=2.
With the beneficial effect of 5-[10-(9-carboxyl anthryl)]-m-phthalic acid of present method composite structure novelty be: the rigidity tricarboxylic acids part of prolongation is widely used in the synthesis of MOFs material, this kind of material has good pore passage structure, large internal surface area usually, makes this kind of material have potential application in different field such as gaseous storage, chemical sensitisation, catalysis and medicament slow releases.The rigidity triangle Carboxylic acid ligand extended can obtain novel structure, many micropores MOFs material that specific surface area is large usually, and can microvoid structure be changed, electronic environment in its pore is made to be optimized thus to improve above-mentioned application performance, therefore, design and synthesis novel structure prolongation poly carboxylic acid part and the synthesis being applied to MOFs material has become one of focus of current research.But large-sized rigidity multi-carboxylic acid compounds synthesis ratio is more difficult.Therefore, be a kind of part with huge potential using value with 5-[10-(9-carboxyl anthryl)]-m-phthalic acid of present method composite structure novelty.
Accompanying drawing explanation
The chemical structural formula schematic diagram of target compound F in Fig. 1 the present invention.
The synthesis schematic diagram of compd A and B in Fig. 2 the present invention.
The synthesis schematic diagram of Compound C and D in Fig. 3 the present invention.
The synthesis schematic diagram of compd E and F in Fig. 4 the present invention.
Embodiment
The synthetic method of 5-of the present invention [10-(9-carboxyl anthryl)]-m-phthalic acid, synthesis step is:
With amino-1, the 3-rutgers of 5-for raw material, diazotization bromine replaces generation 5-bromo-1,3-rutgers (A), A generates 3,5-dimethoxycarbonyl phenylo boric acid pinacol ester (B) with connection boric acid pinacol ester through linked reaction, and synthetic route as shown in Figure 2.In addition, with 9-anthroic acid for raw material, bromination reaction generates the bromo-9-anthroic acid (C) of 10-, and C and thionyl chloride react and generate 10-bromo-9-anthracene formyl chloride, then react with methyl alcohol and generate 10-bromo-9-anthroic acid methyl esters (D), synthetic route as shown in Figure 3.Finally, compd B and D generate 5-[10-(9-methoxycarbonyl anthryl)]-dimethyl isophthalate (E) through Suzuki linked reaction, E obtains target product 5-[10-(9-carboxyl anthryl)]-m-phthalic acid (F) through hydrolysis again, and synthetic route as shown in Figure 4.
Specific embodiment is as follows:
(I) as shown in Figure 2: take 5-amino-1, 3-rutgers (10.0g, 47.6mmol) in 500mL there-necked flask, slow dropping hydrobromic acid solution (15%, 225mL), drip and finish, ice bath cooling solution to 5 DEG C, sodium nitrite solution (2.5M is slowly dripped under rapid stirring, 23mL), the Hydrogen bromide (45% of CuBr (9.8g) is slowly dripped in there-necked flask, 90mL) solution, keep temperature of reaction lower than 5 DEG C, add stirring at room temperature 2h, filter to obtain crude product, white powder A (8.28g) is obtained through silica gel column chromatography (eluent: petrol ether/ethyl acetate=8/3) purifying after drying, productive rate 63.4%.Fusing point: 88 ~ 89 DEG C.
Compd A nuclear-magnetism
1hNMR,
13cNMR and high resolution mass spectrum data:
1hNMR (400MHz, CDCl
3) δ 8.59 (s, 1H), 8.34 (s, 2H), 3.95 (s, 7H).
13cNMR (101MHz, CDCl
3) δ 164.78,136.53,132.12,129.22,122.49,52.62.HRMS (EI), C
10h
9brO
4, measured value (calculated value),
m/z: 273.0812 [M
+] (273.0801).
(II) as shown in Figure 2: take 5-bromo-1,3-rutgers (5.4g, 19.8mmol), boric acid pinacol ester (6.0g, 23.6mmol) is joined, potassium acetate (5.6g, 57.2mmol), be placed in 250mL there-necked flask, add anhydrous 1,4-dioxane (50mL) makes solvent, logical N
2protection, adds Pd (dppf) after 0.5h
2cl
2(0.2g, 0.27mmol), is warming up to 100 DEG C of reaction 12h, is down to after room temperature and steams excessive Isosorbide-5-Nitrae-dioxane, add H until temperature
2o (20mL) dilutes, and ethyl acetate (30mL) extracts, continuous extraction 3 times, collects organic phase, anhydrous Na
2sO
3drying, filtrate obtains crude product after revolving steaming, and crude on silica gel column chromatography (eluent: petrol ether/ethyl acetate=94/6) purifying obtains white powder B (4.59g), productive rate 72.5%.Fusing point: 126 ~ 127 DEG C.
Compd B nuclear-magnetism
1hNMR,
13cNMR and high resolution mass spectrum data:
1hNMR (400MHz, CDCl
3) δ 8.75 (t,
j=1.7Hz, 1H), 8.64 – 8.61 (m, 2H), 3.94 (s, 6H), 1.35 (s, 12H).
13cNMR (101MHz, CDCl
3) δ 166.30,139.88,133.35,132.19,130.02,84.11,52.37,24.86.HRMS (EI), C
16h
21bO
6, measured value (calculated value),
m/z: 320.1455 [M
+] (320.1453).
(III) as shown in Figure 3: get 9-anthroic acid (5.0g, 22.5mmol) in 500mL there-necked flask, ice acetic acid (300mL) dissolves 9-anthroic acid in there-necked flask, and ice bath is cooled to 5 DEG C, slowly drips Br
2(2mL39mmol) 20mL acetic acid solution, drips and finishes, and be warming up to 65 DEG C of reaction 2h, added by reaction solution in the frozen water of 800mL, separate out precipitation, filter, solid is dissolved in K
2cO
3(5%500mL) in solution, filtering and impurity removing matter, rare HNO
3acidified filtrate, separate out precipitation, dehydrated alcohol recrystallization obtains pale yellow powder C (5.76g), productive rate 85%.Fusing point: 265 ~ 267 DEG C.
Compound C nuclear-magnetism
1hNMR,
13cNMR and high resolution mass spectrum data:
1hNMR (400MHz,
d 6 -DMSO) δ 8.34 (d, J=8.2Hz, 2H), 8.21 (d, J=7.6Hz, 2H), 7.65 – 7.58 (m, 2H), 7.51 – 7.44 (m, 2H).
13cNMR (101MHz,
d 6 -DMSO) δ 171.80,144.31,135.11,130.06,128.95,127.95,127.21,126.97,126.88,124.99,117.51.HRMS (EI), C
15h
9brO
2, measured value (calculated value),
m/z: 301.1340 [M
+] (301.1348).
(IV) as shown in Figure 3: take the bromo-9-anthroic acid (5.2g, 17.3mmol) of 10-in 250mL there-necked flask, add 40mLSOCl
2, 5 pyridines, 80 ° of C react 12h, and decompression steams excessive SOCl
2be cooled to normal temperature, add 40mL methyl alcohol, add methylene chloride (40mL) make solvent, 85 ° of C react 2h, steam excessive methanol and solvent, reacting coarse product obtains pale yellow powder D (4.89g), productive rate 89.9% through silica gel column chromatography (eluent: sherwood oil/methylene dichloride=4/1) purifying.Fusing point: 114 ~ 115 DEG C.
Compound D nuclear-magnetism
1hNMR,
13cNMR and high resolution mass spectrum data:
1hNMR (400MHz, CDCl
3) δ 8.58 (t,
j=9.4Hz, 1H), 7.98 (t,
j=9.8Hz, 1H), 7.72 – 7.49 (m, 2H), 4.19 (s, 2H).
13cNMR (101MHz, CDCl
3) δ 169.80,129.99,128.68,128.24,127.30,127.17,126.91,125.37,125.22,52.86.HRMS (EI), C
16h
11brO
2, measured value (calculated value),
m/z: 315.1608 [M
+] (315.1613).
(V) as shown in Figure 4: in the there-necked flask of 250mL, add B (4.8g, 1.5eq) respectively, 10-bromo-9-anthroic acid methyl esters (3.15g, 10mmol), K
3pO
4(6.4g, 30mmol), 100mL1,4-dioxane heat, passes into N
2after 10min, add tetrakis triphenylphosphine palladium (0.2g, 2%), 90 DEG C of reaction 12h, reaction end steams Isosorbide-5-Nitrae-dioxane, thin up (30mL), methylene dichloride (60mL) extracts 3 times, collects lower organic layer, anhydrous Na
2sO
3drying, steams solvent and obtains reacting coarse product, through silica gel column chromatography (eluent: petrol ether/ethyl acetate=10/1) purifying after drying, obtains white powder E (3.74g, 8mmol), productive rate 87.4%.Fusing point: 273 ~ 274 DEG C.
Compd E nuclear-magnetism
1hNMR,
13cNMR and high resolution mass spectrum data:
1hNMR (400MHz, CDCl
3) δ 8.90 (s, 1H), 8.28 (s, 2H), 8.05 (d,
j=8.8Hz, 2H), 7.52 (dd,
j=14.6,8.6Hz, 4H), 7.40 (d,
j=7.6Hz, 2H), 4.23 (s, 3H), 3.96 (s, 6H).
13cNMR (101MHz, CDCl
3) δ 170.09,166.10,139.24,137.09,136.14,131.08,130.26,129.51,129.05,127.85,126.79,126.56,126.04,125.25,52.82,52.55.HRMS (EI), C
26h
20o
6, measured value (calculated value),
m/z: 428.4329 [M
+] (428.4334).
(VI) as shown in Figure 4: in the round-bottomed flask of 250mL, add E (3.5g, 8mmol) successively, NaOH (5g, 125mmol), H
2o (20mL), Isosorbide-5-Nitrae-dioxane 50mL, 95 DEG C are reacted 12 hours, steam Isosorbide-5-Nitrae-dioxane, add suitable quantity of water and dissolve carboxylic acid sodium salt, filter, add rare HNO in filtrate
3being acidified to pH is about 2, and separate out precipitation, hold over night, topples over supernatant liquor, and suction filtration is dry obtains target compound yellow mercury oxide F (3.1g), productive rate 98.5%.Fusing point: 348 ~ 350 DEG C
Compound F 17-hydroxy-corticosterone nuclear-magnetism
1hNMR,
13cNMR and high resolution mass spectrum data:
1hNMR (400MHz,
d 6 -DMSO) δ 8.68 (s, 1H), 8.10 (d, J=10.0Hz, 4H), 7.60 (d, J=4.1Hz, 2H), 7.47 (s, 4H).
13cNMR (101MHz,
d 6 -DMSO) δ 171.06,167.00,138.83,135.67,132.77,130.03,129.36,126.88,126.63,126.41,126.19.HRMS (EI), C
23h
14o
6, measured value (calculated value),
m/z: 386.3530 [M
+] (386.3537).
The above, it is only preferred embodiment of the present invention, not any pro forma restriction is done to the present invention, anyly do not depart from technical solution of the present invention content, the any simple modification done above embodiment according to technical spirit of the present invention, equivalent variations and modification, all still belong in the scope of technical solution of the present invention.
Claims (9)
1. a synthetic method for novel 5-[10-(9-carboxyl anthryl)]-m-phthalic acid, is characterized in that: synthesis step is:
(I) is with 5-amino-1, 3-rutgers is raw material, 15% hydrobromic acid solution is added under low temperature, slowly sodium nitrite solution is dripped under adding rear rapid stirring, slowly drip the hydrobromic acid solution of cuprous bromide subsequently, mol ratio 5-amino-1, 3-rutgers: Sodium Nitrite: cuprous bromide is 1:1.1 ~ 1.3:1.4 ~ 1.6, add stirring at room temperature 2 hours, vacuum filtration obtains reacting coarse product, by sherwood oil after dry: the mixed solvent of ethyl acetate volume ratio 2 ~ 3:1 is that eluent pillar layer separation is purified to obtain white powder A:5-bromo-1, 3-rutgers,
(II) is under the condition of argon gas or nitrogen protection, with 5-bromo-1, 3-rutgers, connection boric acid pinacol ester and potassium acetate in molar ratio 1:1 ~ 1.5:2.5 ~ 3.5 are dissolved in anhydrous dioxane after mixing, 5-bromo-1, the amount ratio of 3-rutgers and dioxane is that 1 milli rubs: 2.5 ~ 3.5 milliliters, add appropriate catalyzer, back flow reaction 10 ~ 20 hours under 110 ~ 130 DEG C of oil baths, after cooling, first dilute with water extracts system by ethyl acetate again, then with saturated aqueous common salt, organic layer is washed, collect organic phase and carry out except water treatment by anhydrous sodium sulphate to it, filter, vacuum concentration, finally with sherwood oil and ethyl acetate by volume for the mixed solvent of 16:0.8 ~ 1.2 is that eluent column chromatography separating-purifying obtains compd B: 3, 5-dimethoxycarbonyl phenylo boric acid pinacol ester,
(III) 9-anthroic acid is dissolved in glacial acetic acid, drips the acetum of bromine under ice bath, and the mol ratio of 9-anthroic acid and bromine is 1:1.5 ~ 1.8, and drip off and be warming up to 65 DEG C of reactions 2 ~ 4 hours, reaction solution adds in the frozen water of 500 ~ 800mL, separates out precipitation, filters;
Solid is dissolved in 500 ~ 600mL5 ~ 10%K
2cO
3in solution, filter removal of contamination, filtrate uses rare HNO
3precipitation is separated out in acidifying, and dehydrated alcohol recrystallization obtains the bromo-9-anthroic acid of pale yellow powder C:10-;
Excessive SOCl is added in (IV) 10-bromo-9-anthroic acid
2, catalyzer made by a little pyridine, and 80 ° of C react 10 ~ 12 hours, and excessive SOCl is removed in underpressure distillation
2be cooled to normal temperature, 40 ~ 60mL methyl alcohol is added in round-bottomed flask, add 50 ~ 80mL methylene dichloride and make solvent, 85 ° of C reacting by heating 2 ~ 3 hours, steam excessive methyl alcohol, finally with sherwood oil and methylene dichloride by volume for the mixed solvent of 4:0.8 ~ 1 is that eluent column chromatography separating-purifying obtains Compound D: 10-bromo-9-anthroic acid methyl esters;
(V) under argon gas or nitrogen protection, by B, D and K
3pO
480 ~ 100mL1 is dissolved in 1.2:1:3 mixing in molar ratio, in 4-dioxane solvent, passes into N
2after 10 minutes, add proper catalyst, react 10 ~ 20 hours under 90 ~ 110 DEG C of oil baths, steam excessive dioxane, first dilute with water after cooling, with methylene dichloride, system is extracted again, collect organic phase and carry out except water treatment with sodium sulphite anhydrous 99.3 to it, filter, vacuum concentration, then with sherwood oil and ethyl acetate by volume for 100:0.8 ~ 1 is for eluent, obtain white product E:5-[10-(9-methoxycarbonyl anthryl)]-dimethyl isophthalate with column chromatography separating-purifying;
5-[10-(9-methoxycarbonyl anthryl)]-dimethyl isophthalate and NaOH are added 1 in 1:10 ~ 15 by (VI) in molar ratio, in the mixed solvent of 4-dioxane and water, volume ratio is 2 ~ 3:1,95 DEG C are refluxed 4 ~ 6 hours, steam removing excessive 1,4-dioxane, adds excessive rare HNO
3carry out being acidified to pH ≈ 2, separate out yellow solid, vacuum-drying obtains finalization compound F:5-[10-(9-carboxyl anthryl)]-m-phthalic acid, and its chemical structural formula is:
。
2. the synthetic method of novel 5-according to claim 1 [10-(9-carboxyl anthryl)]-m-phthalic acid, it is characterized in that: when diazotization reaction occurs preparation A, temperature of reaction should control below 5 DEG C, and eluent during purifying A is sherwood oil: ethyl acetate volume ratio 2 ~ 3:1.
3. the synthetic method of novel 5-according to claim 1 [10-(9-carboxyl anthryl)]-m-phthalic acid, it is characterized in that: with 5-bromo-1,3-rutgers, connection boric acid pinacol ester and potassium acetate 1:1.2:2.5 synthetic compound B in molar ratio, purifying B sherwood oil and ethyl acetate volume ratio are 16:1.
4. the synthetic method of novel 5-according to claim 1 [10-(9-carboxyl anthryl)]-m-phthalic acid, is characterized in that: during preparation Compound C, the mol ratio of 9-anthroic acid and bromine is 1:1.8.
5. the synthetic method of novel 5-according to claim 1 [10-(9-carboxyl anthryl)]-m-phthalic acid, is characterized in that: during preparation Compound D, SOCl
2all need excessive with methyl alcohol, need add 50 ~ 80mL methylene dichloride and make solvent, sherwood oil and methylene dichloride are by volume for the mixed solvent of 4:1 is eluent.
6. the synthetic method of novel 5-according to claim 1 [10-(9-carboxyl anthryl)]-m-phthalic acid, it is characterized in that: the catalyzer preparing compd B use is [1,1 '-bis-(diphenylphosphino) ferrocene] palladium chloride, consumption is participate in reactant total mass 0.5 ~ 1%.
7. the synthetic method of novel 5-according to claim 1 [10-(9-carboxyl anthryl)]-m-phthalic acid, it is characterized in that: the catalyzer preparing compd E use is tetrakis triphenylphosphine palladium, consumption is participate in reactant total mass 1 ~ 2%.
8. the synthetic method of novel 5-according to claim 1 [10-(9-carboxyl anthryl)]-m-phthalic acid, is characterized in that: prepare compd E and use B, D and K
3pO
41.2:1:3 in molar ratio, sherwood oil and ethyl acetate are by volume for 100:1 is eluent.
9. the synthetic method of novel 5-according to claim 1 [10-(9-carboxyl anthryl)]-m-phthalic acid, it is characterized in that: 5-[10-(9-methoxycarbonyl anthryl)]-dimethyl isophthalate and NaOH 1:12 in molar ratio, solvent 1, in the mixed solvent of 4-dioxane and water, volume ratio is 2 ~ 3:1, is acidified to pH ≈ 2.
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