CN117736087B - Preparation method of triammonium rhodotricarboxylic acid - Google Patents
Preparation method of triammonium rhodotricarboxylic acid Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000002253 acid Substances 0.000 title abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims abstract description 30
- 150000003627 tricarboxylic acid derivatives Chemical class 0.000 claims abstract description 19
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 18
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229960004889 salicylic acid Drugs 0.000 claims abstract description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 14
- 239000000376 reactant Substances 0.000 claims abstract description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000007787 solid Substances 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 239000000706 filtrate Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 239000002808 molecular sieve Substances 0.000 claims description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- -1 aluminum ions Chemical class 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- 230000000536 complexating effect Effects 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 abstract description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 15
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 15
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 13
- 235000010288 sodium nitrite Nutrition 0.000 abstract description 9
- 239000003054 catalyst Substances 0.000 abstract description 7
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 abstract description 5
- 239000002841 Lewis acid Substances 0.000 abstract description 5
- 230000002152 alkylating effect Effects 0.000 abstract description 5
- 238000002425 crystallisation Methods 0.000 abstract description 5
- 230000008025 crystallization Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 150000007517 lewis acids Chemical class 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 5
- 238000005804 alkylation reaction Methods 0.000 abstract description 3
- 238000003889 chemical engineering Methods 0.000 abstract description 3
- 239000012295 chemical reaction liquid Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 24
- 238000000034 method Methods 0.000 description 12
- 239000013078 crystal Substances 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 239000002168 alkylating agent Substances 0.000 description 3
- 229940100198 alkylating agent Drugs 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- RXQNKKRGJJRMKD-UHFFFAOYSA-N 5-bromo-2-methylaniline Chemical compound CC1=CC=C(Br)C=C1N RXQNKKRGJJRMKD-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 241000220317 Rosa Species 0.000 description 2
- AIPNSHNRCQOTRI-UHFFFAOYSA-N aluminon Chemical compound [NH4+].[NH4+].[NH4+].C1=C(C([O-])=O)C(O)=CC=C1C(C=1C=C(C(O)=CC=1)C([O-])=O)=C1C=C(C([O-])=O)C(=O)C=C1 AIPNSHNRCQOTRI-UHFFFAOYSA-N 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000008098 formaldehyde solution Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 241001165494 Rhodiola Species 0.000 description 1
- 244000042430 Rhodiola rosea Species 0.000 description 1
- 235000003713 Rhodiola rosea Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007922 dissolution test Methods 0.000 description 1
- 238000007336 electrophilic substitution reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229930187593 rose bengal Natural products 0.000 description 1
- 229940081623 rose bengal Drugs 0.000 description 1
- STRXNPAVPKGJQR-UHFFFAOYSA-N rose bengal A Natural products O1C(=O)C(C(=CC=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 STRXNPAVPKGJQR-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of triammonium rhodotricarboxylic acid, which belongs to the technical field of aluminum reagent preparation and comprises the following steps: friedel-Crafts Alkylation is adopted for alkylation reaction, lewis acid is used as a catalyst, salicylic acid reacts with an alkylating reagent to synthesize the rose-red tricarboxylic acid, and the rose-red tricarboxylic acid is neutralized by ammonia water to obtain a product. The invention has the advantages that: 1. the invention can avoid using high-risk concentrated sulfuric acid, solves the problem of easy crystallization of reaction liquid, simplifies operation, has relatively simple post-treatment, and is relatively environment-friendly in the whole production process; 2. the sodium nitrite and formaldehyde are not used any more, the solvent is a reactant, the environment-friendly chemical engineering concept is met, the reaction conditions are relatively mild, the operation is simpler under the same effect, and the cost is effectively reduced.
Description
Technical Field
The invention relates to the technical field of aluminum reagent preparation, in particular to a preparation method of triammonium rhodotricarboxylic acid.
Background
The trisammonium rhodotricarboxylic acid, also known as aluminum reagent, is mainly used in the field of organic analysis. 3- [ bis (3-carboxy-4-hydroxyphenyl) methylene ] -6-oxo-1, 4-cyclohexadiene-1-carboxylic acid triammonium salt, lysofon, C.I.43810 (rose bengal tricarboxylic acid). Orange to brown glassy powder. Relative molecular mass 473.43. Melting point 223-225 deg.c (decomposition). The absorption wavelength λmax522nm. Is insoluble in diethyl ether, acetone, chloroform, slightly soluble in ethanol, and easily soluble in water. Can form color lake with aluminum, chromium, iron and beryllium. The product has triarylmethane structure, and has hydroxy and-NH 4 group on aromatic ring, so that it has color development effect. The application is as follows: used for measuring aluminum in water, food, tissue, etc.
The existing preparation method of the triammonium rhodotricarboxylic acid comprises the following steps: method 1: 10g (0.145 mol) of solid sodium nitrite is added into 20ml of concentrated sulfuric acid in batches, meanwhile, the adding speed is controlled so as to release a small amount of nitric oxide, and after the nitric oxide is completely dissolved, 20g (0.145 mol) of salicylic acid is added into the concentrated sulfuric acid in batches under stirring, wherein the whole process is about 15min; then, at 20 ℃, the mixture is stirred until all solids are dissolved, and the viscous liquid is bright red to brown; placing the brown liquid on an ice bath, reducing the temperature to 0 ℃, slowly dropwise adding 5ml (0.065 mol) of 35% -40% formaldehyde solution while stirring, keeping the reaction temperature below 5 ℃, adding 100g of crushed ice and 500ml of ice water after the reaction is completed, and stirring until solid small blocks are formed; filtering, washing with ice water for several times, pumping, and dissolving in 1:2 (volume ratio) in ammonia water, filtering with filter paper; the filtrate was evaporated to dryness on a steam bath to give 19.22g of a brown-yellow glassy solid in 83% -86% yield. Method 2: uniformly mixing salicylic acid and hydrochloric acid, heating to 70 ℃ under continuous stirring, slowly adding formaldehyde, controlling the temperature to be no more than 80 ℃, heating to 95 ℃ after adding, preserving heat for 8 hours, cooling after the reaction is finished, pouring into distilled water, standing for crystallization, washing the filtered crystallization with a large amount of distilled water, drying at 100 ℃, uniformly mixing the obtained methine salicylic acid with the salicylic acid, adding the mixture into nitrosylsulfuric acid (obtained by rapidly mixing sodium nitrite solid with concentrated sulfuric acid at 0 ℃), controlling the temperature to be below 15 ℃ for 20-24 hours, washing the obtained crystallization with a large amount of distilled water, boiling and washing the crystals with hot water until the crystals are loose, washing the crystals with distilled water until the washing solution is neutral, dissolving the crystals with dilute ammonia water, decoloring the crystals with active carbon, adding analytically pure hydrochloric acid into filtrate, washing the separated crystals with water until the crystals are qualified, and drying the crystals to obtain the aluminum reagent. Method 3: adding solid sodium nitrite into concentrated sulfuric acid in a divided manner under the condition of rapid stirring, controlling the adding speed to avoid red smoke, adding salicylic acid into the concentrated sulfuric acid in a small amount in a divided manner after complete dissolution, controlling the temperature to be not more than 20 ℃, stirring until the mixture is completely dissolved, enabling the mixture to be light red to brown and sticky, cooling the temperature to 0 ℃, slowly adding 37% formaldehyde solution under the condition of rapid stirring, enabling the temperature to be lower than 5 ℃, adding a large amount of ice-water mixture while stirring until the solid is dispersed after the reaction is finished, washing the obtained solid for a plurality of times by cold water, filtering to dissolve the solid by using 1:2 dilute ammonia water, filtering to remove insoluble matters, and evaporating the solid by steam to obtain yellow ammonium salt.
The prior art has the following problems: in the sodium nitrite method adopted in the prior art, the generated nitrosylsulfuric acid solution has small solubility of sodium bisulfate generated by the reaction in sulfuric acid, solid crystals can be separated out from a reaction system, the viscosity of a reaction solution is increased, the operation steps are complex, the reaction between concentrated sulfuric acid and sodium nitrite is not easy to control, the release of nitrogen dioxide is easy to cause, and a large amount of salt and waste acid which are difficult to treat are generated at the same time, so that the environmental impact is large; concentrated sulfuric acid is highly dangerous, causing serious occupational health risks.
Disclosure of Invention
The invention aims to provide a preparation method of triammonium rhodotricarboxylic acid, which avoids using high-risk concentrated sulfuric acid, solves the problem that reaction liquid is easy to crystallize, simplifies operation, has relatively simple post-treatment, and is relatively environment-friendly in the whole production process; the sodium nitrite and formaldehyde are not used any more, the solvent is a reactant, the environment-friendly chemical engineering concept is met, the reaction conditions are relatively mild, the operation is simpler under the same effect, and the cost is effectively reduced.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of triammonium rhodotricarboxylic acid comprises the following steps:
Friedel-Crafts Alkylation is adopted, lewis acid is used as a catalyst, salicylic acid is used as a raw material, carbon tetrachloride is used as an alkylating reagent and a solvent, the reaction is carried out to generate the rose-red tricarboxylic acid, and the rose-red tricarboxylic acid is neutralized by ammonia water to obtain the product.
Preferably, the lewis acid is anhydrous aluminum trichloride.
Preferably, the alkylating agent is carbon tetrachloride.
Preferably, the specific steps are as follows:
s1, rapidly dissolving salicylic acid in a cold water bath flask with a reflux device and containing carbon tetrachloride dehydrated by a molecular sieve to form a first stable solution;
s2, rapidly dissolving anhydrous aluminum trichloride in anhydrous carbon tetrachloride dehydrated by a molecular sieve to form a second stable solution;
S3, slowly adding a second stable solution into the first stable solution under stirring, controlling the reaction temperature to be less than or equal to 40 ℃, and stopping the reaction after 30 minutes, wherein the mixture is red to brownish red sticky and insoluble substances are generated;
S4, cooling the reactant in ice bath, slowly dropwise adding cold dilute hydrochloric acid under stirring, controlling the reaction temperature to be less than or equal to 15 ℃, complexing aluminum ions with the product, dissolving in a water phase, separating out lower carbon tetrachloride after the reaction is finished, washing with pure water for 1-2 times until no obvious red color exists, and merging into a water layer to obtain a rose-red tricarboxylic acid solution;
S5, neutralizing the rosy tricarboxylic acid solution in the step S4 by using 10% -25% of diluted ammonia water until the pH=8-9, dissolving, filtering out insoluble substances, and collecting filtrate;
s6, heating the filtrate obtained in the step S5, concentrating to be sticky, pouring the sticky filtrate into carbon tetrachloride, separating out solid, carrying out suction filtration, and then placing the obtained solid into a vacuum drying oven for drying to obtain the rose-red tri-carboxylic acid tri-ammonium.
Preferably, after step S6, step S7 is added: and (5) recovering and reutilizing the carbon tetrachloride.
Preferably, in step S6, carbon tetrachloride may be replaced by chloroform, absolute ethanol or acetone.
The reaction mechanism of the invention is as follows: salicylic acid as aromatic hydrocarbon and carbon tetrachloride as alkylating reagent are subjected to electrophilic substitution reaction on the aromatic ring of salicylic acid in the presence of anhydrous aluminum trichloride and other Lewis acid, hydrogen atoms on the aromatic ring of salicylic acid are substituted by alkyl groups in the alkylating reagent to generate rose tricarboxylic acid, and then ammonia water is used for neutralization to obtain the rose tricarboxylic acid triammonium.
Compared with the prior art, the invention has the advantages that:
1. the invention can avoid using high-risk concentrated sulfuric acid, solves the problem of easy crystallization of reaction liquid, simplifies operation, has relatively simple post-treatment and is relatively environment-friendly in the whole production process.
2. Sodium nitrite and formaldehyde are not used any more, carbon tetrachloride is used as an alkylating reagent and a solvent, the solvent is a reactant, the environment-friendly chemical engineering concept is met, the reaction condition is relatively mild, the operation is simpler under the same effect, and the cost is effectively reduced.
The invention is described in detail below with reference to the drawings and the detailed description. It is to be understood that the examples described relate only to the preferred embodiments of the present invention and that various changes and modifications of the components and contents are possible without departing from the spirit and scope of the present invention.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
In order to more clearly illustrate the invention or the technical solutions of the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the invention, and other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an infrared spectrum (IR) diagram of an intermediate rhodiola-trihydroxy acid prepared in example 1 of the present invention.
FIG. 2 is an Infrared (IR) spectrum of the product aluminum reagent prepared in example 1 of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is apparent that the described embodiments are some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The following examples are illustrative of the invention but are not intended to limit the scope of the invention.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the embodiments of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
Unless otherwise specified, the starting materials required in the following examples are all conventional starting materials commercially available in the art, and the reaction vessel and the controlled reaction conditions used are all conventional reaction vessels and reaction conditions; the instruments required for product confirmation are all conventional instruments in the field, and the test conditions are all conventional conditions; the units are all weight units.
Example 1
A preparation method of the triammonium rhodiola tricarboxylic acid comprises the steps of adopting Friedel-Crafts Alkylation alkylation reaction, using salicylic acid as a raw material, using aluminum trichloride as a catalyst, using carbon tetrachloride as an alkylating agent and a reaction solvent, adopting a one-step method to synthesize the trisrhodiola tricarboxylic acid, and neutralizing by ammonia water to obtain a product; the chemical reaction formula is as follows:
；
the method comprises the following specific steps:
(1) Rapidly dissolving 30g of salicylic acid in a cold water bath flask with a reflux device and containing 1000ml of carbon tetrachloride dehydrated by a molecular sieve to form a first stable solution;
(2) Rapidly dissolving 5g of anhydrous aluminum trichloride in 50ml of anhydrous carbon tetrachloride dehydrated by a molecular sieve to form a second stable solution;
(3) Slowly adding the second stable solution into the first stable solution under stirring, controlling the reaction temperature at 30 ℃, and stopping the reaction after 30 minutes, wherein the mixture is red to brownish red viscous and insoluble substances are generated;
(4) Cooling the reactant to 0 ℃ in ice bath, slowly dropwise adding cold dilute hydrochloric acid under stirring, controlling the reaction temperature at 15 ℃, complexing aluminum ions with the product, dissolving in a water phase, separating out carbon tetrachloride at the lower layer after the reaction is finished, washing with pure water for 2 times until no obvious red color exists, and merging into a water layer to obtain a rosy tricarboxylic acid solution;
(5) Neutralizing the rosy tricarboxylic acid solution in the step (4) with 20% diluted ammonia water until the pH=8, dissolving, filtering out insoluble matters, and collecting filtrate;
(6) Heating the filtrate obtained in the step (5), concentrating to be sticky, pouring the sticky filtrate into carbon tetrachloride, precipitating solid, carrying out suction filtration, putting the obtained solid into a vacuum drying oven, and drying for 3 hours to obtain the pure aluminum reagent, namely the triammonium rhodiola rosea tricarboxylic acid, wherein the yield is 82.45%;
(7) And (5) recovering and reutilizing the carbon tetrachloride.
After the test, the product is tested for aluminum, the sensitivity is qualified, the ammonia water dissolution test is qualified, and the analytical pure aluminum reagent test standard is met.
Dilute ammonia dissolution experiment
1G of the sample was weighed, dissolved in 100mL of water and 0.5mL of aqueous ammonia (10%) and the solution was clear.
Sensitivity test to aluminium
0.025G of the sample was weighed to 0.0001g, and 20mL of water and 0.1mL of aqueous ammonia (10%) were added and dissolved to prepare solution I.
10ML of water was measured, 0.01mL of aluminum standard solution (0.1 mg/mL) was added, 0.1mL of solution I and 0.1mL of glacial acetic acid were added, and the solution was shaken well, and a clear pink color was developed in 15 min.
Product confirmation:
1. The intermediate and final products of example 1 of the present invention were identified, including infrared spectroscopy and nuclear magnetic resonance analysis, as shown in FIG. 1, which is an infrared spectrum (IR) plot of the intermediate, rosy tricarboxylic acid, prepared in example 1 of the present invention; the intermediate obtained by nuclear magnetic resonance analysis is rosy trihydroxy acid, and the specific data are as follows:
1HNMR:δ4.73(1H,d,J=1.6Hz),5.52(1H,dd,J=10.4,1.6Hz),6.26(1H,d, J=10.4Hz),7.02-7.15(2H,7.08(dd,J=8.4,0.5Hz),7.08(dd,J=8.4,0.5Hz)), 7.59-7.74(3H,7.66(dd,J=8.4,1.9Hz), 7.66(dd,J=8.4,1.9Hz),7.69(S)),8.42-8.53(2H,8.47(dd,J=1.9,0.5Hz),8.47(dd, J=1.9, 0.5Hz) );
its distribution, chemical shift, multiplexing and coupling constants are shown in table 1 below;
TABLE 1
FIG. 2 is an Infrared (IR) spectrum of the aluminum reagent product prepared in example 1 of the present invention; confirming that the aluminum reagent is obtained in the step (6);
The final product obtained was confirmed to be an aluminum reagent by nuclear magnetic resonance analysis, and the specific data are as follows:
1HNMR:δ4.57(1H,d,J=1.6Hz),5.47(1H,dd,J=10.2,1.6Hz),6.18(1H,d, J=10.2Hz),6.68(1H,S),6.91-7.15(4H,6.97(dd,J=8.4,0.4Hz),6.97(dd, J=8.4,0.4Hz),7.09(dd,J=8.4,1.9Hz),7.09(dd, J=8.4,1.9Hz)),7.63-7.73(2H,7.68(dd, J=1.9, 0.4Hz), 7.68(dd, J=1.9, 0.4Hz) );
Their distribution, chemical shift, multiplexing and coupling constants are shown in Table 2 below;
TABLE 2
Example 2-example 7
Otherwise, the reaction temperature was controlled in the same manner as in example 1, and the following Table 3 was obtained.
TABLE 3 Table 3
Example 8-example 13
Otherwise, the reaction times were controlled in the same manner as in example 1, see Table 4 below.
TABLE 4 Table 4
Example 14-example 18
Otherwise the same as in example 1, different catalysts were controlled, see table 5 below.
TABLE 5
The reaction temperature is less than or equal to 40 ℃ and the reaction time is 30min when the product is synthesized, and the catalyst is aluminum trichloride with the best effect.
The invention has the beneficial effects that:
1. Adopts Friedel-Crafts Alkylation alkylation reaction, takes Lewis acid as catalyst and carbon tetrachloride as alkylating agent, adopts one-step method to produce the rhodotricarboxylic acid by salicylic acid, and then carries out neutralization by ammonia water to obtain the product, thus the complex synthesis scheme is not needed to be carried out by adopting raw materials such as concentrated sulfuric acid, sodium nitrite, formaldehyde and the like, and the production process has less harm to the environment.
2. The Friedel-crafts alkylation reaction mechanism needs manual fine control in a laboratory, is influenced by technology, equipment and process in actual industrial production, cannot control process parameters finely, has high production technology difficulty and unsatisfactory reaction efficiency, and has low cost performance in both the laboratory and industrial production, so that enterprises or research personnel do not participate in the field.
3. The inventor has found a technical route for finely controlling process parameters, including reaction temperature, reaction time and catalyst, by multiple experiments, which overcomes the technical bias in the field.
Although the claimed subject matter has been described in language specific to structural features and/or methodological acts, it is to be understood that the claimed subject matter is not limited to the specific features or acts described in the claims. Rather, the specific structural features and methods described in the claims are merely examples of the invention.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (1)
1. The preparation method of the triammonium rhodo tricarboxylic acid is characterized by comprising the following steps:
s1, rapidly dissolving salicylic acid in a cold water bath flask with a reflux device and containing carbon tetrachloride dehydrated by a molecular sieve to form a first stable solution;
s2, rapidly dissolving anhydrous aluminum trichloride in anhydrous carbon tetrachloride dehydrated by a molecular sieve to form a second stable solution;
S3, adding a second stable solution into the first stable solution under stirring, controlling the reaction temperature to be less than or equal to 40 ℃, and stopping the reaction after 30 minutes, wherein the mixture is red to brownish red viscous and insoluble substances are generated;
S4, cooling the reactant in ice bath, slowly dropwise adding cold dilute hydrochloric acid under stirring, controlling the reaction temperature to be less than or equal to 15 ℃, complexing aluminum ions with the product, dissolving in a water phase, separating out lower carbon tetrachloride after the reaction is finished, washing with pure water for 1-2 times until no obvious red color exists, and merging into a water layer to obtain a rose-red tricarboxylic acid solution;
S5, neutralizing the rosy tricarboxylic acid solution in the step S4 by using 10% -25% of diluted ammonia water until the pH=8-9, dissolving, filtering out insoluble substances, and collecting filtrate;
s6, heating the filtrate obtained in the step S5, concentrating to be sticky, pouring the sticky filtrate into carbon tetrachloride, separating out solid, carrying out suction filtration, and then placing the obtained solid into a vacuum drying oven for drying to obtain the rose-red tri-carboxylic acid tri-ammonium.
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| CN107793301A (en) * | 2016-08-30 | 2018-03-13 | 天津市科密欧化学试剂有限公司 | A kind of preparation method of rosolic acid |
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| CN107793301A (en) * | 2016-08-30 | 2018-03-13 | 天津市科密欧化学试剂有限公司 | A kind of preparation method of rosolic acid |
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