Shaanxi BLOOM Tech Co., Ltd. is one of the most experienced manufacturers and suppliers of ditertiary butyl dicarbonate cas 24424-99-5 in China. Welcome to wholesale bulk high quality ditertiary butyl dicarbonate cas 24424-99-5 for sale here from our factory. Good service and reasonable price are available.
Ditertiary butyl dicarbonate , CAS 24424-99-5, Molecular formula C10H18O5, the finished product is colorless crystal or colorless liquid, slightly soluble in water, insoluble in cold water. Soluble in most organic solvents, such as carbon tetrachloride, tetrahydrofuran, n-hexane, benzene, trichloromethane, dioxane, alcohols, acetone, acetonitrile, N, N-dimethylformamide, etc. It is a new type of amino protectant.
Used to introduce tert butoxycarbonyl (BOC) protectants in organic synthesis, particularly suitable for amino protection of amino acids. Widely used in the synthesis of pharmaceuticals, proteins and peptides, biochemistry, food, cosmetics and other products. In organic chemical reactions, tert butoxycarbonylation reagents are commonly used as substrates for amines, phenols, thiols, amides, lactams, amino esters, etc.
The reaction rate is fast and the yield is relatively high. Tert butoxycarbonylation reaction (protection of functional groups); Due to the poor stability of acyl halide reagents, they are widely used as protective groups for amino groups, which can be removed under acidic conditions (such as hydrochloric acid, trifluoroacetic acid, etc.). Fatty amines, cyclic amines, aromatic amines, and heterocyclic amines can all react with (Boc).
|
Chemical Formula |
C10H22O6 |
|
Exact Mass |
238 |
|
Molecular Weight |
238 |
|
m/z |
238 (100.0%), 239 (10.8%), 240 (1.2%) |
|
Elemental Analysis |
C, 50.41; H, 9.31; O, 40.29 |
|
|
|
Ditertiary butyl dicarbonate (chemical formula C10H18O5, CAS number 24424-99-5) is an organic compound with unique chemical properties, appearing as a colorless transparent liquid or low melting point solid at room temperature. Its core function originates from the tert butoxycarbonyl (BOC) group in the molecular structure, which can be combined with active functional groups such as amino groups through condensation reactions to form a stable protective structure and can be controllably removed under acidic conditions.
Biochemistry: Tools and reagents from enzyme catalysis to genetic engineering
1. Construction of genetic engineering vectors
In gene cloning and expression, it can be used to modify the ends of vector DNA to prevent self ligation or degradation. For example, when constructing plasmid vectors, the BOC group can protect the sticky end after restriction endonuclease cleavage, avoiding the filling effect of DNA polymerase and thus improving the efficiency of ligation. In addition, BOC modified primers can also be used for PCR amplification to prevent the formation of primer dimers.
2. Biomolecular labeling and separation
Can be used to synthesize biotin or fluorescein labeled probes for protein or nucleic acid detection and separation. For example, protecting the carboxyl groups in biotin through BOC groups can prevent them from reacting with amino groups during synthesis, and ultimately remove the BOC groups under acidic conditions to obtain active markers.
Food industry: auxiliary reagents from natural pigment extraction to food additives
1. Enhanced stability of natural pigments
In food pigment extraction, it can be used to protect the active groups of pigment molecules and improve their stability.
For example, when extracting anthocyanins, BOC groups can modify the phenolic hydroxyl groups in anthocyanin molecules to prevent oxidation or degradation during processing, thereby extending the shelf life of the pigments.In addition, BOC modified pigments can achieve precise control of pigment release by adjusting deprotection conditions.
2. Synthesis of food additives
Di tert butyl dicarbonate can be used as an intermediate for the synthesis of certain food additives.
For example, in the synthesis of antioxidant TBHQ (tert butylhydroquinone), the BOC group can protect the phenolic hydroxyl group in the intermediate, prevent it from being oxidized during the synthesis process, and improve the purity of the product. In addition, BOC groups can also be used as key intermediates for the synthesis of additives such as sweeteners and thickeners.
3. Modification of food packaging materials
In the field of food packaging materials, ditertiary butyl dicarbonate can be used to modify the surface properties of polymers. For example, by modifying the surface of polyethylene (PE) or polypropylene (PP) with BOC groups, active groups such as amino or carboxyl groups can be introduced to improve the adhesion between the material and printing inks or coatings. In addition, BOC modified polymers can also be used to prepare biodegradable food packaging films, achieving controllable degradation of materials by controlling deprotection conditions.
Materials Science: From Polymer Synthesis to Surface Modification of Nanomaterials
1. Synthesis of polymer materials
Can be used for synthesizing high-performance polymer materials such as polycarbonate (PC) and polyester (PET). For example, in the synthesis of PC, the BOC group can protect the phenolic hydroxyl group in bisphenol A, avoiding side reactions during the condensation reaction, thereby improving the uniformity of molecular weight distribution.
In addition, BOC modified monomers can also be used to synthesize temperature responsive polymers, achieving phase transition behavior of materials by controlling deprotection conditions.
2. Surface modification of nanomaterials
In the field of nanomaterials, it can be used to modify the surface of quantum dots, metal nanoparticles, or carbon nanotubes.
For example, by modifying the surface of quantum dots with BOC groups, active groups such as amino or carboxyl groups can be introduced to enhance their binding ability with biomolecules, which can be used for biological imaging or drug delivery. In addition, BOC modified nanoparticles can achieve dynamic control of surface properties by controlling the deprotection conditions.
3. Coating and Adhesive Modification
In the coatings and adhesives industry, it can be used to modify the cross-linking properties of resins. For example, by modifying the hydroxyl groups in epoxy resin with BOC groups, the rate of crosslinking reaction can be controlled, and the hardness and scratch resistance of the coating can be improved. In addition, BOC modified polyurethane (PU) can also be used to prepare high elasticity adhesives, achieving dynamic adjustment of adhesive strength by controlling the deprotection conditions.
Other fields: Extended applications from cosmetics to agricultural chemistry
1. Synthesis of cosmetic ingredients
In the cosmetics industry, it can be used as a key intermediate for synthesizing sunscreens, moisturizers, or antioxidants. For example, in the synthesis of benzophenone sunscreens, the BOC group can protect the phenolic hydroxyl group in the intermediate, prevent it from being oxidized during the synthesis process, and improve the purity of the product. In addition, BOC modified hyaluronic acid can also be used to prepare long-lasting moisturizers, achieving sustained release of moisturizing effects by controlling deprotection conditions.
2. Agricultural chemical intermediates
In the field of agricultural chemistry, ditertiary butyl dicarbonate can be used as a key intermediate for synthesizing herbicides, insecticides, or plant growth regulators. For example, in the synthesis of sulfonylurea herbicides, the BOC group can protect the amino group in the intermediate, prevent it from being oxidized or hydrolyzed during the synthesis process, and improve the yield of the product. In addition, BOC modified gibberellin analogues can also be used to regulate plant growth cycles and achieve precise drug release by controlling deprotection conditions.
Di tert butyl dicarbonate has become an indispensable reagent in modern chemical industry due to its unique chemical properties and wide application potential. From pharmaceutical synthesis to materials science, from the food industry to agricultural chemistry, its applications continue to expand, providing important support for human health, quality of life, and technological progress.
Synthesis of di tert butyl dicarbonate:
1. Potassium tert butyl alcohol is dissolved in anhydrous tetrahydrofuran, dry carbon dioxide is introduced at - 5~- 20 ℃ to form a slurry, and the low temperature is maintained continuously. Then, phosgene benzene solution is added dropwise to obtain di tert butyl tricarbonate. Dissolve it in carbon tetrachloride, add an appropriate amount of 1,4-diazabicyclo [2,2,2] octane, stir at 25 ℃ to completely release carbon dioxide, and convert it into di tert butyl dicarbonate.
2. Attention! The use of highly toxic phosgene should be handled carefully in a ventilated kitchen. All glassware stuck with phosgene should be cleaned before taking out the fume hood.
(1) Preparation of di tert butyl tricarbonate: dry a 1L three necked flask with a mechanical agitator, a 200ml constant pressure dropping funnel, a calcium chloride drying tube, and an inner diameter of no less than 6mm extending close to the bottom of the flask. Calibrate and mark the level of the funnel containing 85 ml and 105 ml of liquid in advance. Fill in dry nitrogen, add 44.8 g (0.40 mol) of potassium tert butyl alcohol without alcohol and 550 ml of anhydrous tetrahydrofuran into the flask, and stir for 5-10 minutes to form a solution. Immerse the reaction flask in an ice salt bath to maintain - 5-20 ℃. Under vigorous stirring, inject dry carbon dioxide for about 30 minutes to form a dense slurry.
At the same time, add 86 ml of anhydrous benzene into the dropping funnel and blow in light bubbles until the solution volume of phosgene in benzene reaches 105 ml, which is equivalent to 24 g (0.24 mol) of phosgene. When the addition reaction of carbon dioxide is completed, the phosgene solution is dropped into the cooled reactant under vigorous stirring, which takes about 1 hour. The temperature of the cold bath is maintained at - 5~- 10 ℃, and the viscosity of the reaction mixture becomes smaller, and it is still a white emulsion. When the addition reaction of phosgene is completed, continue to stir for 45 minutes. At the same time, inject anhydrous nitroethylene wool to blow out most of the excess phosgene.
Remove the instrument from the flask, plug two necks, and concentrate about 650 ml of solvent to 100 ml with a rotary evaporator under reduced pressure. The flask is still cooled with an ice salt bath to maintain a temperature of - 5-10 ℃. As there is a small amount of phosgene left in the reaction mixture, the exhaust gas from the air extraction pump or vacuum pump should be discharged into the fume hood. The materials collected in the cold trap should also be evacuated in the fume hood. The residues containing finely dispersed potassium chloride should be filtered with a large diameter sand core funnel. The funnel should be precooled by 50 ml ice cooled pentane before use.
When filtering, use a large diameter funnel to cover the filter funnel upside down, and pass nitrogen to isolate the moist air from the material. Wash the residue in the flask into the filter funnel with J}} ml cold pentane, and then wash the filter residue with 2 * 100ml cold pentane. The filtrate is combined with pentane washing solution, and concentrated with a rotary evaporator under 0 ℃ decompression to obtain a white solid weighing 33.7g. Dissolve the crude product in 1250ml pentane, cool it to - 15 ℃, and remove the white crystal. Two batches of crystals can also be obtained after mother liquor is concentrated in the rotary evaporator. In total, 31.2-32.8 (59~62%) pure di tert butyl tricarbonate is obtained, which is white crystals.
(2) Preparation of di tert butyl dicarbonate: add 20.0 g (0.076 mol) of ditertiary butyl dicarbonate solution dissolved in i} ml of carbon tetrachloride and 0.10 g (0.0009 mol) of newly sublimed 1.4-diazabicyclo [2.2 · 2] octane into a beaker with an electromagnetic stirring rod to immediately and rapidly release carbon dioxide. Stir at 25 ℃ for 45 minutes to fully release carbon dioxide, and then add 35 ml of water solution containing proper amount of citric acid, which is enough to make the water layer weakly acidic.
The organic layer is separated, dried with anhydrous magnesium sulfate, concentrated with a rotary evaporator at 25 ℃, and the residual liquid is distilled under reduced pressure to obtain a colorless liquid of di tert butylphenol dicarbonate, producing 13.3 -- 15.1 g (80~91%). Similar results are obtained with triethylamine as catalyst. However, triethylamine is not as effective as 1,4-diazabicyclooctane because triethylamine may react with solvent and it is difficult to separate triethylamine from product.
3. Under the catalysis of 1,4-diazabicyclo [2.2.2] octane, carbonyl chloride is directly reacted with tert butyl carbonate to prepare.
Frequently Asked Questions
What are the obscure features of Boc ₂ O's slow self degradation at room temperature and its non hydrolytic endogenous decomposition pathway?
+
-
Conventional cognition only focuses on the hydrolysis of water to produce tert butanol and CO ₂; Under anhydrous and acid-base conditions, Boc ₂ O can undergo intramolecular rearrangement and cleavage, generating tert butoxycarbonyl radicals and tert butoxycarbonyl radicals, which further isomerize into isobutene and trace by-products of carbon dioxide. The thermal induced free radical degradation does not require proton involvement and is the core implicit reason for the slow color change and purity decrease during the storage period of anhydrous organic solvents, which is rarely indicated in the synthesis manual.
Why is the site selectivity of weakly basic heterocyclic amines finely regulated by the steric hindrance of Boc ₂ O itself in Boc acylation reaction?
+
-
ABoc ₂ O has a super large volume of tert butyl spatial skeleton, which exhibits a strong stereo screening effect compared to acetylation and Cbz reagents. For multi nitrogen substrates containing primary, secondary, and heterocyclic nitrogen simultaneously, under mild neutral conditions, priority is given to modifying fatty primary amines with smaller steric hindrance, while aromatic heterocyclic amines such as pyridine nitrogen, pyrazine nitrogen, and indole nitrogen hardly react; The chemical selectivity mediated by this steric hindrance is a niche key strategy for complex polyamine molecules that does not require protective groups.
What kind of obscure solid-phase catalytic enhancement mechanism exists when Boc ₂ O is combined with inorganic weak bases such as carbonates and bicarbonates?
+
-
Organic bases (triethylamine, DIPEA) are commonly used catalytic systems, but they are prone to racemization and side reactions; Inorganic weak bases are insoluble in organic solvents, but can activate the anhydride carbonyl of Boc ₂ O through solid-liquid interface adsorption, reducing the nucleophilic attack energy barrier. Moreover, inorganic bases do not ionize nucleophilic anions, avoiding side reactions such as ester hydrolysis and ring opening, making them a niche preferred condition for chiral amino acids and sensitive heterocyclic amines without racemic Boc protection.
What is the obscure rule of selective deprotection of weakly acidic systems in addition to trifluoroacetic acid in the Boc reaction?
+
-
The classic solution is high concentration TFA strong acid complete cutting; Under low concentration organic acid and Lewis acid buffer systems, differential removal can be achieved: mild removal of single Boc groups, while Boc deactivated by strong electron withdrawing neighboring groups and hindered double substituted Boc can be retained. This gradient acidolysis property can be used for the stepwise disassembly of multi Boc labeled molecules and belongs to a niche fine operation logic in the synthesis of multi fragment drug intermediates.
Hot Tags: ditertiary butyl dicarbonate cas 24424-99-5, suppliers, manufacturers, factory, wholesale, buy, price, bulk, for sale, 3 Phenyltoluene, Additive, N N N Trimethylethylenediamine, 2 Chloro 4 pyridinecarboxylic acid, Synthetic Chemical, BENZENE D6