Adrenochrome Powder is the core component of adrenaline powder. It is the oxidation product of adrenaline. It is a red powder. It is an effective coronary vasoconstrictor for rat heart. The adrenal pigment can be used in the study of neurological diseases. A large amount of evidence shows that it can be oxidized by body fluid and tissue fluid in many mammals. According to research, there are hallucinogenic works. It is one of the causes of schizophrenia. It can reduce capillary permeability. It is used 1 ~ 2 per kilogram of human body μ G has a strong hemostatic effect In addition, melanin exists widely in animals, and I is an intermediate for melanin production 34) Predecessors pointed out that when contaminated by trace metals or coexisting with II, the pharmacological experiments were invalid. According to the quotation of sigma reagent company in 1997, the I per gram is as high as 304 90 dollars, and about 10 dollars per gram. Therefore, it is of theoretical and economic value to study the method of preparing I There are two problems in the existing preparation methods of adrenaline red Generally speaking, the higher the yield (50%), the lower the purity (6 ~ 10); When the purity is high, the yield is often only 17% 1, and these operating conditions must be controlled at - 80 ° C. It is also reported that organic oxidants can also be used for preparation, but the preparation process of such oxidants is complex and involves more pollution.
Melting point |
115-120 ° C |
Boiling point |
311.69 ° C (rough estimate) |
Density |
1.2822 (rough estimate) |
Storage conditions |
− 20 ° C |
Dangerous goods sign |
Xi |
Acidity coefficient ( pKa ) |
3.31 ± 0.20 (predicted) |
Refractive index |
1.5600 (estimated) |
Dangerous goods sign |
Xi |
Hazard category code |
36 / 37 / 38 |
Safety instructions |
36-26 |
|
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Melting point 115-120 ° C, Boiling point 311.69 ° C (rough estimate), Density 1.2822 (rough estimate), Refractive index 1.5600 (estimated), Storage conditions − 20 ° C, Acidity coefficient (PKA) 13.31 ± 0.20 (predicted), security information, Dangerous goods sign Xi, Hazard category code 36 / 37 / 38, Safety instructions 26-36, WGK Germany 3.
In previous experiments, most of the synthetic adrenochrome powder was prepared by organic oxidants, but the preparation process of this kind of oxidant is complex and involves more pollution. Therefore, after repeated inquiries and experiments, our laboratory has provided a synthetic method. This method is the simplest method to prepare high-purity adrenaline red by chemical method at present, and the yield is more than 30%. The practice has proved that the purity of adrenaline red obtained by this method can be maintained for a long time at - 10 ~ 20 ° C and in dark conditions. With the continuous progress of science and technology and the in-depth implementation of environmental protection law, The preparation of adrenaline red will gradually develop towards electrochemical preparation and automatic control. At the same time, the reaction medium is gradually changing from organic solvent to aqueous solvent (16 ~ 18) This research will be beneficial to the realization of artificial intelligence technology.
The specific precautions are as follows: put adrenaline in methanol solvent and add formic acid dropwise until it is clear Add the newly prepared Ag2O into the above solution in batches under strong stirring and strictly control the reaction time, then filter the solution through anhydrous sodium sulfate bed, wash the residue with an appropriate amount of methanol and incorporate it into the filtrate, place the filtrate in a low-temperature bath and cool it at - 30 ° C to obtain purplish red crystal, wash the crystal with cold methanol ether, and dry it at low temperature to obtain the product, place it in a sealed container and store it in a dark place at - 10 ~ 20 ° C According to the results of the obtained crystal in UV test, the purity of the material obtained by this method is high.
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A preparation method for dl adrenaline, using sinephrine hydrochloride as the raw material, which is protected by boc groups under the action of an acid binding agent to obtain compound a, which is then oxidized by 2-iodobenzoic acid and reduced by sodium bisulfite to obtain compound b. Compound b is then deprotected by hydrochloric acid to obtain dl adrenaline like white powder. The reaction steps of the preparation method for dl adrenaline are as follows:
Add Xinfulin hydrochloride to a reaction flask, first add solvent and acid binding agent, then add boc anhydride and stir at room temperature for 1 hour. Then, raise the temperature to 60 ℃~70 ℃, extract the solution and collect the organic phase. Wash the organic phase with 0.1n hydrochloric acid and saturated salt water respectively. After washing, add n-hexane, drop the temperature to precipitate, filter, and dry to obtain compound a;
Add compound a and solvent 1 to the reaction flask, then add 2-iodoylbenzoic acid, and react for 1-3 hours. Then, add water and sodium hydrosulfite, and react for 1 hour before filtering. The filtrate is distilled under reduced pressure until an oily substance appears in the solution. Extract twice with solvent 2, wash once with saturated sodium bicarbonate solution and once with saturated salt water. Dry with anhydrous sodium sulfate and recover the solvent through reduced pressure distillation. Dissolve with solvent 3, then add n-hexane and stir at room temperature for crystallization, Filter and dry the filter cake to obtain compound b;
Add a hydrochloric acid solution with a concentration of 3mol/l to the reaction flask, raise the temperature to 45 ° C-60 ° C, and then add compound b for 1-3 hours. After the reaction is completed, reduce to room temperature, adjust the pH value with concentrated ammonia water, crystallize, filter, wash with water, wash with methanol, and vacuum dry to obtain dl adrenaline.
The total molar yield of dl adrenaline prepared by this method is greater than 50%, the chromatographic purity is greater than 96%, and the ee value is close to zero, significantly saving the preparation cost of dl adrenaline. The operation is simple, environmentally friendly, and is conducive to industrial production, with broad application prospects.
Adrenochrome powder, as an important fluorescent dye, its unique molecular structure endows it with excellent fluorescence performance and biocompatibility. In molecular structure analysis, we not only need to focus on its basic chemical composition, but also deeply understand its spatial configuration and electron distribution to reveal its properties and mechanisms of action in applications.
1. The chemical composition of D, L-adrenergic red
D. The basic structure of L-adrenergic red includes multiple functional groups and a benzene ring. Among them, the most crucial ones are sulfonyl (-SO3H) and Rhodamine B skeleton. Sulfonyl groups endow molecules with good water solubility and stability, while the Rhodamine B framework provides strong fluorescence emission. In addition, the molecule also contains functional groups such as amino (-NH2) and carboxyl (-COOH), which not only affect the solubility and stability of the molecule, but also provide possibilities for its application in biomarkers and detection.
2. The spatial configuration of D, L-adrenergic red
D. The spatial configuration of L-adrenergic red exhibits a typical planar conjugated structure. The benzene ring and dimethylaminophenyl in the Rhodamine B skeleton are connected by double bonds to form a planar π - conjugated system. This conjugated system is a key region for fluorescence emission, where electron transitions and energy transfer occur. In addition, functional groups such as sulfonyl and amino groups are located on both sides of the conjugated system and are covalently linked to the Rhodamine B skeleton.
3. The electronic distribution of D, L-adrenergic red
The electron distribution is an important factor affecting the fluorescence properties of D, L-adrenergic red molecules. The π - conjugated system in the Rhodamine B framework allows electrons to freely flow and transfer energy within it. When exposed to external light, electrons will transition from the ground state to the excited state, and then return to the ground state and emit fluorescence in an extremely short time. In addition, functional groups such as sulfonyl and amino groups can also affect the distribution and transition process of electrons. For example, sulfonyl groups can attract surrounding water molecules through electrostatic interactions, forming a stable hydration layer to protect fluorescent groups from external environmental influences.
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