CN100558691C - The method of a kind of synthetic 6-hydroxyl-2-naphthoic acid - Google Patents
The method of a kind of synthetic 6-hydroxyl-2-naphthoic acid Download PDFInfo
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- CN100558691C CN100558691C CNB2006100209510A CN200610020951A CN100558691C CN 100558691 C CN100558691 C CN 100558691C CN B2006100209510 A CNB2006100209510 A CN B2006100209510A CN 200610020951 A CN200610020951 A CN 200610020951A CN 100558691 C CN100558691 C CN 100558691C
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- 238000000034 method Methods 0.000 title claims abstract description 13
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 title abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 8
- 150000002367 halogens Chemical class 0.000 claims abstract description 8
- 238000010992 reflux Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 56
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 10
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- SJJCQDRGABAVBB-UHFFFAOYSA-N 1-hydroxy-2-naphthoic acid Chemical compound C1=CC=CC2=C(O)C(C(=O)O)=CC=C21 SJJCQDRGABAVBB-UHFFFAOYSA-N 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 24
- 238000003756 stirring Methods 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 23
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- 229960004756 ethanol Drugs 0.000 description 11
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 10
- 238000002425 crystallisation Methods 0.000 description 9
- 230000008025 crystallization Effects 0.000 description 9
- 238000010792 warming Methods 0.000 description 9
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 8
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000012065 filter cake Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 5
- 229950011260 betanaphthol Drugs 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- CRWJEUDFKNYSBX-UHFFFAOYSA-N sodium;hypobromite Chemical compound [Na+].Br[O-] CRWJEUDFKNYSBX-UHFFFAOYSA-N 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- UOBYKYZJUGYBDK-UHFFFAOYSA-N 2-naphthoic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC=C21 UOBYKYZJUGYBDK-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000006473 carboxylation reaction Methods 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- -1 2-hydroxyl-6-naphthoic acid-3-naphthoic acid Chemical compound 0.000 description 1
- DLLDUYJRQNTEOR-UHFFFAOYSA-N 6-bromonaphthalene-2-carbaldehyde Chemical compound C1=C(C=O)C=CC2=CC(Br)=CC=C21 DLLDUYJRQNTEOR-UHFFFAOYSA-N 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005911 haloform reaction Methods 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides the novel method of a kind of 6-of preparation hydroxyl-2-naphthoic acid.Comprise the steps: that formula (I) compound gets formula (II) compound with halogen in 0～100 ℃ of reaction 7～12hr under alkaline condition; Formula (II) compound with HX in acetum, under 70 ℃～reflux temperature, react formula (III) compound.Present method has the yield height, the characteristics such as purity height of the target product 6-hydroxyl-2-naphthoic acid of gained.
Description
Technical field
To the present invention relates to 6-methoxyl group-2-acetonaphthone be raw material prepares the innovation synthetic method of 6-hydroxyl-2-naphthoic acid through haloform reaction, belongs to meticulous organic chemical industry field.
Background technology
Suc as formula the hydroxyl of 6-shown in (III)-2-naphthoic acid is the important source material of producing various aromatic polyester classes, especially produce liquid crystalline polymers with excellent processing characteristics and flowing property and have favorable elasticity and heat-resistant resin or fiber institute requisite.
As the method for producing 6-hydroxyl-2-naphthoic acid, known have following four kinds:
1.Koble-Schimmit reaction prepares 6-hydroxyl-2-naphthoic acid.This reaction is that the sylvite with 2-Naphthol is that 6 carboxylation reaction takes place with carbonic acid gas under High Temperature High Pressure raw material, makes 6-hydroxyl-2-naphthoic acid.(U.S?Patents?Nos.1,593,816，4,287,357 4,345,095 4,329,494?and?4,345,094)
2. the Koble-Schimmit in the high-temperature medium reacts and prepares 6-hydroxyl-2-naphthoic acid.This reaction is to be that 6 carboxylation reaction takes place with carbonic acid gas under High Temperature High Pressure raw material with the sylvite of 2-Naphthol in high-temperature medium, makes 6-hydroxyl-2-naphthoic acid.(Japanese Patent Applications Laid-Open{ is open } NO.57-95939 andNO.58-99436)
3. use the carbonylation reaction Synthetic 2 of aryl halide, 6-acid.This reaction is to be that raw material makes 6-hydroxyl-2-naphthoic acid with reaction of carbon monoxide in the presence of catalyzer with 6-bromo-beta naphthal.(Japanese?Patent?ApplicationLaid-Open?NO.57-91955)
4. be equipped with 2 with 2-(2-hydroxyl-2-propyl group) naphthalene-6-carboxylic acid oxidative legal system, 6-acid.This reaction is to be that raw material makes 6-hydroxyl-2-naphthoic acid through hydrogen peroxide oxidation under the catalysis at mineral acid in second cyanogen solution with 2-(2-hydroxyl-2-propyl group) naphthalene-6-carboxylic acid.(GB2174706)
But above-described synthetic method has following shortcoming respectively:
For method 1 and 2, in reaction, have the isomer 2-hydroxyl of 2-hydroxyl-6-naphthoic acid-3-naphthoic acid and generate, so in method 1 and 22, the productive rate of 6-acid has only 26.5% and 45% respectively.And the 2-Naphthol that every generation a part 2 in method 1 and 2,6-acid just have a part generates, and has also brought isolating difficulty to aftertreatment when having caused the 2-Naphthol transformation efficiency low.And for method 3, in reaction, use CO (carbon monoxide converter) gas relatively more dangerous, reaction is at 70kg/cm
2Carry out under the high pressure, this requirement to conversion unit is very high, and facility investment is very big, and also more complicated of Preparation of catalysts, and the yield of reaction has only 37%.And for method 4, the yield of reaction be quantitative and the condition of reaction also comparatively gentle, but the raw material of reaction is rare, the preparation trouble.
Summary of the invention
The invention provides the method for a kind of novelty, simple to operate, yield is high synthetic 6-hydroxyl-2-naphthoic acid compound suc as formula (III).
Described synthetic method comprises the steps: that formula (I) compound gets formula (II) compound with halogen in 0～100 ℃ of reaction 7～12hr under alkaline condition.Formula (II) compound with HX acetum under 70 ℃～reflux temperature, react formula (III) compound.
Described is Cl by formula (I) compound used halogen in the reaction that formula (II) compound changes
2, Br
2, I
2Formula (I) compound is 1: 2.0～1: 8.0 with the equivalence ratio of halogen, be preferably 1: 3.0～and 6.0.
Used alkali is NaOH in the reaction, the mixture of KOH or its arbitrary proportion.Reaction Chinese style (I) compound is 1: 3.0～8.0 with the equivalence ratio of alkali, be preferably 1: 4.0～and 6.0.Temperature of reaction is 0～100 ℃, is preferably 40～80 ℃.Reaction times is 7～12hr, is preferably 8～9hr.The system of used halogen/alkali can replace with the saturated aqueous solution of clorox in the reaction.Reaction substrate formula (I) is 1: 4.0～9.0 with the equivalence ratio of clorox, and being preferably is 1: 5.0～8.0.Reaction finish postcooling, filter the sodium salt of formula (II) compound.The sodium salt drying of formula (II) compound is after acidifying, filtration promptly get formula (II) compound crude product.Formula (II) compound crude product gets the pure product of formula (II) compound through DMF/MeOH mixed solvent recrystallization.
Wherein the mass ratio of DMF/MeOH is 1: 5.0～10.0, be preferably 1: 6.0～and 8.0.
Describedly can be HCl, haloid acid such as HBr by the used HX acid in the reaction that formula (III) compound changes of formula (II) compound.Reaction substrate formula (II) compound is 1: 4.0～10.0 with the equivalence ratio of HX acid, be preferably 1: 5.0～and 8.0.The consumption that reacts described acetic acid is that every 1g formula (II) compound is calculated as 1～5ml.Described temperature of reaction is 70 ℃～backflow, is preferably 95 ℃～100 ℃.
Only need cooling after described reaction response finishes, filtration can obtain formula (III) compound.Get final product to such an extent that purity reaches formula (III) compound more than 99.5% through crystallization, yield can reach more than 85%.
The invention provides the method for preparing compound (III) 6-hydroxyl-2-naphthoic acid, present method have the route novelty, simple to operate, raw material is easy to get and characteristics such as yield height.
Embodiment
The invention will be further described below in conjunction with embodiment, but protection scope of the present invention is not limited to this.
Embodiment 1
In the 500mL there-necked flask, add 48.1g sodium hydroxide (1.2mol) and 250mL water, stir under the ice bath cooling, slowly drip 15mL bromine (0.6mol) control reaction temperature and be lower than 5 ℃, dropwise back control low temperature and continue to stir 20min.In the sodium hypobromite solution for preparing, add 80mL dioxane, 27.0g sodium hydroxide (0.67mol), 20.1g I.Be warming up to 75 ℃, back flow reaction 2hr.Stopped reaction is cooled to below 10 ℃, continues to stir 30min.Filter, the gained solid adds 100 water, adds concentrated hydrochloric acid under the whipped state and transfers pH to 3～4.Be heated to backflow, stir more than 1 hour, be cooled to below 10 ℃, keep about 0.5 hour.Filter, filter cake 100 water washings, drying gets the 20g colorless solid.The gained solid is with ethanol 70g/DMF10g crystallization.Get 2-methoxyl group-6-naphthoic acid, 15g (yield: 74%).
1H?NMR(300MHz，DMSO)：δ3.90(s，3H，OCH3)，7.22(m，1H，ArH)，7.40(d，1H，J＝2.46)，7.90(m，2H，ArH)，8.00(d，1H，ArH).8.52(s，1H，ArH)12.92(s，1H，COOH)；
13CNMR(300MHz，DMSO)：δ55.3，105.9，125.7，125.8，126.9，127.5，130.4，130.9，136.7，159.1，167.7。
Embodiment 2
In the 500mL there-necked flask, add 20.0g sodium hydroxide (1.2mol) and 200mL water, stir under the ice bath cooling, slowly drip 12mL bromine (0.48mol) control reaction temperature and be lower than 5 ℃, dropwise back control low temperature and continue to stir 20min.In the sodium hypobromite solution for preparing, add 80mL dioxane, 27.0g sodium hydroxide (0.67mol), 20.1g I.Be warming up to 75 ℃, back flow reaction 2hr.Stopped reaction is cooled to below 10 ℃, continues to stir 30min.Filter, the gained solid adds 100mL water, adds concentrated hydrochloric acid under the whipped state and transfers pH to 3～4.Be heated to backflow, stir more than 1 hour, be cooled to below 10 ℃, keep about 0.5 hour.Filter, filter cake 100mL water washing, drying gets the 20g colorless solid.The gained solid is with ethanol 70g/DMF 10g crystallization.Get 2-methoxyl group-6-naphthoic acid, 13g (yield: 64%).
Embodiment 3
In the 500mL there-necked flask, add 48.1g sodium hydroxide (1.2mol) and 250mL water, stir under the ice bath cooling, slowly drip 15mL bromine (0.6mol) control reaction temperature and be lower than 5 ℃, dropwise back control low temperature and continue to stir 20min.In the sodium hypobromite solution for preparing, add 80mL dioxane, 27.0g sodium hydroxide (0.67mol), 20.1g I.Be warming up to 50 ℃, insulation reaction 10hr.Stopped reaction is cooled to below 10 ℃, continues to stir 30min.Filter, the gained solid adds 100mL water, adds concentrated hydrochloric acid under the whipped state and transfers pH to 3～4.Be heated to backflow, stir more than 1 hour, be cooled to below 10 ℃, keep about 0.5 hour.Filter, filter cake 100mL water washing, drying gets the 19g colorless solid.The gained solid is with ethanol 70g/DMF 10g recrystallization.Get 2-methoxyl group-6-naphthoic acid, 11g (yield: 54%).
Embodiment 4
580g adds in the 500mL there-necked flask with NaClO liquid (content 10%), adds 6-methoxyl group-2-acetonaphthone 25g, and sodium hydroxide 17g was 45 ℃ of reactions about 4 hours.Be warming up to 75 ℃ then, insulation reaction 5-6 hour.Stopped reaction is cooled to below 10 ℃, keeps more than 0.5 hour.Filter, the gained solid adds 100mL water, adds concentrated hydrochloric acid under the whipped state and transfers pH to 3～4.Be heated to backflow, stir more than 1 hour, be cooled to below 10 ℃, keep about 0.5 hour.Filter, filter cake 100mL water washing, drying gets the 26g colorless solid.The gained solid is with ethanol (industrial goods, dehydrated alcohol) 105g, DMF 14g crystallization.Get 2-methoxyl group-6-naphthoic acid, 22g (yield: 87%).
Embodiment 5
380g adds in the 500mL there-necked flask with NaClO liquid (content 10%), adds 6-methoxyl group-2-acetonaphthone 25g, and sodium hydroxide 17g was 45 ℃ of reactions about 4 hours.Be warming up to 75 ℃, reacted 5-6 hour.Stopped reaction is cooled to below 10 ℃, keeps more than 0.5 hour.Filter, gained solids 100mL water adds concentrated hydrochloric acid and transfers pH to 3～4 under the whipped state.Be heated to backflow, stir more than 1 hour, be cooled to below 10 ℃, keep about 0.5 hour.Filter, filter cake 100 water washings, drying gets the 25g colorless solid.Thick product is with ethanol 105g/DMF 14g recrystallization.Get 2-methoxyl group-6-naphthoic acid, 18.6g (yield: 74%).
Embodiment 6
380g adds in the 500mL there-necked flask with NaClO liquid (content 10%), adds 6-methoxyl group-2-acetonaphthone 25g, and sodium hydroxide 17g was 45 ℃ of reactions 12 hours.Stopped reaction is cooled to below 10 ℃, keeps more than 0.5 hour.Filter, be added to 100mL in the gained solids, add concentrated hydrochloric acid under the whipped state and transfer pH to 3～4.Be heated to backflow, stir more than 1 hour, be cooled to below 10 ℃, keep about 0.5 hour.Filter, filter cake 100mL water washing, drying gets the 24g colorless solid.The gained solid is with ethanol 105g/DMF 14g recrystallization.Get 2-methoxyl group-6-naphthoic acid, 17g (yield: 70%).
Embodiment 7
580g adds in the 500mL there-necked flask with NaClO liquid (content 10%), adds 6-methoxyl group-2-acetonaphthone 25g, and sodium hydroxide 17g was 45 ℃ of reactions about 4 hours.Be warming up to 75 ℃ then, the chloroform that will produce in will reacting simultaneously steams insulation reaction 3～4 hours continuously.Stopped reaction is cooled to below 10 ℃, keeps more than 0.5 hour.Filter, the gained solid adds 100mL water, adds concentrated hydrochloric acid under the whipped state and transfers pH to 3～4.Be heated to backflow, stir more than 1 hour, be cooled to below 10 ℃, keep about 0.5 hour.Filter, filter cake 100mL water washing, drying gets the 27g colorless solid.The gained solid is with ethanol (industrial goods, dehydrated alcohol) 105g, DMF 14g crystallization.Get 2-methoxyl group-6-naphthoic acid, 23g (yield: 91%).
Embodiment 8
With 20.5g 2-methoxyl group-6-naphthoic acid, 100g Hydrogen bromide (content 48%), 39g acetic acid adds in the 250mL there-necked flask.Be warming up to the reaction of backflow shape after 2 hours more than 10 hours in reaction about 95 ℃.Be cooled to below 10 ℃, stir more than 0.5 hour and filter, get crude product 17.5g (content is about 99%).The gained crude product is dissolved in the NaOH solution of 100mL 10%, and gained alkali lye is with 3 * 40mL n-butyl acetate extraction.Gained water liquid, controlled temperature are lower than under 10 ℃ of conditions transfers PH to 2～3 with concentrated hydrochloric acid, and low temperature stirs the 30min after-filtration.After the solid oven dry, get 6-hydroxyl-2-naphthoic acid 16.0g (yield: 85%) with ethanol 100g/ water 50g crystallization.
1HNMR(300MHz，DMSO)：δ7.13(m，2H，ArH)，7.72(d，1H，J＝8.64)，7.83(m，1H，ArH)，7.93(d，1H，J＝8.64)，8.46(s，1H，ArH)，10.15(s，1H，OH)，12.82(s，1H，COOH)
13CNMR(300MHz，DMSO)：δ108.7，1.19.5，124.8，125.5，126.2?130.6，131.2，137.0，157.6，167.7。
Embodiment 9
With 20.5g 2-methoxyl group-6-naphthoic acid, 100g Hydrogen bromide (content 48%), 20g acetic acid adds in the 250mL there-necked flask.Be warming up to the reaction of backflow shape after 2 hours more than 10 hours in reaction about 95 ℃.Be cooled to below 10 ℃, stir more than 0.5 hour and filter, get colourless 17.0g.The gained solid is dissolved in the NaOH solution of 100mL 10%, and gained alkali lye is with 3 * 40mL n-butyl acetate extraction.Gained water liquid, controlled temperature are lower than under 10 ℃ of conditions transfers PH to 2～3 with concentrated hydrochloric acid, and low temperature stirs the 30min after-filtration.After the solid oven dry, get 6-hydroxyl-2-naphthoic acid 15.0g (yield: 80%) with ethanol 100g/ water 50g crystallization.
Embodiment 10
With 20.5g 2-methoxyl group-6-naphthoic acid, 60g Hydrogen bromide (content 48%), 23g acetic acid adds in the 250mL there-necked flask.Be warming up to the reaction of backflow shape after 2 hours more than 10 hours in reaction about 95 ℃.Be cooled to below 10 ℃, stir more than 0.5 hour and filter, get colorless solid 16.5g.The gained crude product is dissolved in the NaOH solution of 100mL 10%, and gained alkali lye is with 3 * 40mL n-butyl acetate extraction.Gained water liquid, controlled temperature are lower than under 10 ℃ of conditions transfers PH to 2～3 with concentrated hydrochloric acid, and low temperature stirs the 30min after-filtration.After the solid oven dry, get 6-hydroxyl-2-naphthoic acid 14.0g (yield: 74%) with ethanol 100g/ water 50g crystallization.
Embodiment 11
With 20.5g 2-methoxyl group-6-naphthoic acid, 100g Hydrogen bromide (content 48%), 39g acetic acid adds in the 250mL there-necked flask.Reacting more than 15 hours about 75 ℃.Be cooled to below 10 ℃, stir more than 0.5 hour and filter, get colorless solid 16.2g.The gained crude product is dissolved in the NaOH solution of 100mL 10%, and gained alkali lye is with 3 * 40mL n-butyl acetate extraction.Gained water liquid, controlled temperature are lower than under 10 ℃ of conditions transfers PH to 2～3 with concentrated hydrochloric acid, and low temperature stirs the 30min after-filtration.After the solid oven dry, get 6-hydroxyl-2-naphthoic acid 12.0g (yield: 64%) with ethanol 100g/ water 50g crystallization.
Claims (9)
1. the preparation method of the 6-hydroxyl suc as formula (III)-2-naphthoic acid compound,
It is characterized in that: present method comprises the steps: that formula (I) compound gets formula (II) compound with halogen in 0～100 ℃ of reaction 7～12hr under alkaline condition; Formula (II) compound with haloid acid in acetum, under 70 ℃～reflux temperature, react formula (III) compound.
2. preparation method as claimed in claim 1 is characterized in that: formula (I) compound is 1: 2.0～8.0 with the equivalence ratio of halogen.
3. preparation method as claimed in claim 1 is characterized in that: used alkali is the mixture of NaOH, KOH or its arbitrary proportion.
4. preparation method as claimed in claim 1 is characterized in that: reaction Chinese style (I) compound is 1: 3.0～8.0 with the equivalence ratio of alkali.
5. preparation method as claimed in claim 1 is characterized in that: the system of used halogen/alkali replaces with the saturated aqueous solution of clorox in the reaction.
6. preparation method as claimed in claim 5 is characterized in that: reaction substrate formula (I) is 1: 4.0～9.0 with the equivalence ratio of clorox.
7. preparation method as claimed in claim 1 is characterized in that: described haloid acid is HCl or HBr.
8. preparation method as claimed in claim 1 is characterized in that: reaction substrate formula (II) compound is 1: 4.0～10.0 with the equivalence ratio of haloid acid.
9. preparation method as claimed in claim 1 is characterized in that: the consumption of acetic acid is that every 1g formula (II) compound is calculated as 1～5ml.
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| CN100558691C true CN100558691C (en) | 2009-11-11 |
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| CN101508643B (en) * | 2009-03-23 | 2012-02-01 | 浙江工业大学 | Method of preparing rhein |
| CN103360242A (en) * | 2012-04-09 | 2013-10-23 | 盐城拜克化学工业有限公司 | Preparation method of 6-hydroxy-2-naphthoic acid |
| CN102659576A (en) * | 2012-05-02 | 2012-09-12 | 苏州思睿屹新材料股份有限公司 | Refining method for 2-hydroxyl-6-naphthoic acid |
| CN113698292A (en) * | 2021-09-16 | 2021-11-26 | 宿迁思睿屹新材料有限公司 | Preparation method of 6-hydroxy-2-naphthoic acid |
| CN114057566A (en) * | 2021-12-09 | 2022-02-18 | 宁夏清研高分子新材料有限公司 | Preparation method of 2-hydroxy-6-naphthoic acid |
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