21545-31-3

Usage

Uses

Used in Pharmaceutical Industry:
2,3-Dihydro-1,4-naphthoquinone is used as a precursor in the synthesis of pharmaceuticals for its structural similarity to vitamin K, which is essential in various biological processes.
Used in Vitamin K Supplements:
2,3-Dihydro-1,4-naphthoquinone is used as a key ingredient in the production of vitamin K supplements, contributing to the maintenance of bone health and blood clotting processes.
Used in Laboratory Experiments:
2,3-Dihydro-1,4-naphthoquinone is used as a chemical reagent in laboratory experiments, taking advantage of its chemical properties for research purposes.
However, due to its potential toxic effects on the liver and the risk of hemolytic anemia in high doses, the use of 2,3-Dihydro-1,4-naphthoquinone in food and pharmaceutical applications is limited, necessitating careful consideration and regulation in its application across industries.

Upstream product

• 119-64-2 tetralin 
• 75-91-2 tert.-butylhydroperoxide 
• 529-33-9 1,2,3,4-Tetrahydro-1-naphthol 
• 3090-45-7 5,8-dihydro-1,4-naphthalenediol 
• 130-15-4 [1,4]naphthoquinone 
• 87051-06-7 1,8-Dimethoxy-9,10-dioxa-tricyclo[6.2.2.0^2,7]dodeca-2⁽⁷⁾,3,5,11-tetraene 
• 75-07-0 acetaldehyde 
• 6295-28-9 5,8-dihydronaphthalene-1,4-dione 

Downstream Products

• 136229-46-4 2-(2-hydroxyphenyl)anthraquinone 
• 796-30-5 1,4-diphenylnaphthalene 
• 571-58-4 1,4-dimethylnaphthalene 
• 5697-00-7 1,4-diacetoxynaphthalene 

Relevant academic research and scientific papers

Chromium-promoted benzylic oxidations by tert-butyl hydroperoxide: A new catalyst and a comparison of the different procedures

Homogeneous data from literature reports concerning chromium-induced benzylic oxidations by tert-butyl hydroperoxide and from an efficient system using bistriphenylsilyl chromate as catalyst are presented.

Selective Oxidation of Benzylic sp3C-H Bonds using Molecular Oxygen in a Continuous-Flow Microreactor

Selective aerobic oxidation of benzylic sp3 C-H bonds to generate the corresponding ketones was achieved under continuous-flow conditions. The catalysts N-hydroxyphthalimide (NHPI) and tert-butyl nitrite (TBN) as the precursor of the radical under aerobic conditions motivated this process. Flow microreactors operating under optimized conditions enabled this oxidation with higher efficiency and a shortened reaction time of 54 s (total time was 10 min), which was improved 466 times compared with the batch parallel reaction (7.0 h). Notably, the catalyst and solvent recycling (92.6 and 94.5%) and scale-up experiments (0.87 g h-1 in 28 h) demonstrated the practicability of the protocol. The high product selectivity and functional group tolerance of the process allowed the production of ketones in yields of 41.2 to 90.3%. To reveal the versatility and applicability of this protocol, the late-stage modification of an antiepileptic drug to obtain oxcarbazepine was further conducted.

A Copper-Containing Polyoxometalate-Based Metal-Organic Framework as an Efficient Catalyst for Selective Catalytic Oxidation of Alkylbenzenes

A copper-containing polyoxometalate-based metal-organic framework (POMOF), CuI12Cl2(trz)8[HPW12O40] (HENU-7, HENU = Henan University; trz = 1,2,4-triazole), has been successfully synthesized and well-characterized. In addition, the excellent catalytic ability of HENU-7 has been proved by the selective oxidation of diphenylmethane. Under the optimal conditions, the diphenylmethane conversion obtained over HENU-7 is 96%, while the selectivity to benzophenone is 99%, which outperforms most noble-metal-free POM-based catalysts. Moreover, HENU-7 is stable to reuse for five runs without an obvious loss in activity and also can catalyze the oxidation of different benzylic C-H with satisfactory conversions and selectivities, which implied the significant catalytic activity and recyclability.

Oxyfunctionalization of Alkanes Based on a Tricobalt(II)-Substituted Dawson-Type Rhenium Carbonyl Derivative as Catalyst

POM-supported metal carbonyl derivatives (PMCDs) represent a family of tremendous potential catalysts owing to their peculiar physical and chemical properties. Yet low-valence transition metal-substituted Dawson-type PMCD catalysts are uncommon. Hence, we synthesized a tricobalt-substituted PMCDs by conventional aqueous solution method, [Na(H2O)5](NH4)7[P2W15O56Co3(H2O)3(OH)3Re(CO)3]·13H2O (1), and characterized by single crystal X-ray diffraction crystallography, IR, and thermogravimetric analyses (TGA), etc. The obtained compound 1 was employed as a catalyst for the oxidation of diphenylmethane (DPM) to benzophenone, giving 96.8percent yield in the presence of tert-butyl hydroperoxide (TBHP) and pyridine. The control experiments indicate that Co metal ion plays an important role in the catalytic reactions. As a side note, the electrospray ionization mass spectrometry (ESI-MS) and UV spectroscopy showed that 1 can retain its integrity in solution, and magnetic measurements indicated that 1 exhibited a weaker ferromagnetic interaction at low temperature.

Green Organic Solvent-Free Oxidation of Alkylarenes with tert-Butyl Hydroperoxide Catalyzed by Water-Soluble Copper Complex

Different benzylic compounds were efficiently oxidized to the corresponding ketones with aqueous 70% tert-butyl hydroperoxide (TBHP) and the catalytic system composed of CuCl2.2H2O and 2,2'-biquinoline-4,4'-dicarboxylic acid dipotassium salt (BQC). The catalytic system CuCl2/BQC/TBHP allows obtaining high yields at room temperature under organic solvent-free conditions. The interest of this system lies in its cost effectiveness and its benign nature towards the environment. Benzylic tertbutylperoxy ethers and benzylic alcohols were observed and suggested as the reaction intermediates. Analysis of organic products by atomic absorption did not show any contamination with copper metal. In terms of efficiency, CuCl2/BQC system is comparable or superior to the most of the catalytic systems described in the literature and which are based on toxic organic solvent.

Photocatalytic Oxidation of Α-C?H Bonds in Unsaturated Hydrocarbons through a Radical Pathway Induced by a Molecular Cocatalyst

To improve the photocatalytic oxidation of α-C?H bonds in unsaturated hydrocarbons, N-hydroxyphthalimide (NHPI) was used as a molecular cocatalyst with CdS as the photoabsorber. Compared with previously reported photocatalysts involving solid cocatalysts, metal-free NHPI offers better sustainability in addition to the significantly enhanced performance as cocatalyst. The photogenerated holes were transferred into the more active phthalimide-N-oxyl radical (PINO) by reacting with NHPI. In this way, α-C?H bond oxidation was significantly improved through the activation by PINO; even for the sluggish toluene oxidation, the apparent quantum efficiency was as high as 36.5 %. The effects of substrates/NHPI concentration ratio, reaction temperature, and time as well as the reaction intermediates were comprehensively studied. It was possible to identify ketones/aldehydes as the primary products, and overoxidation was controlled by adjusting the substrates/NHPI concentration ratio and reaction time. Thus, the radical path induced by the NHPI–PINO redox pair is an efficient alternative to boost the sluggish photocatalytic oxidation of α-C?H bonds.

Aerobic Co-/ N-Hydroxysuccinimide-Catalyzed Oxidation of p-Tolylsiloxanes to p-Carboxyphenylsiloxanes: Synthesis of Functionalized Siloxanes as Promising Building Blocks for Siloxane-Based Materials

Synthesis of organosilicon products with a "polar" functional group within organic substituents is one of the most fundamentally and practically important challenges in today's chemistry of silicones. In our study, we suggest a solution to this problem, viz., a high-efficiency preparative method based on aerobic Co-/N-hydroxysuccinimide (NHSI) catalyzed oxidation of p-tolylsiloxanes to p-carboxyphenylsiloxanes. This approach is based on "green", commercially available, simple, and inexpensive reagents and employs mild reaction conditions: Co(OAc)2/NHSI catalytic system, O2 as the oxidant, process temperature from 40 to 60 °C, atmospheric pressure. This reaction is general and allows for synthesizing both mono- and di-, tri-, and poly(p-carboxyphenyl)siloxanes with p-carboxyphenyl groups at 1,1-, 1,3-, 1,5-, and 1,1,1-positions. All the products were obtained and isolated in gram amounts (up to 5 g) and in high yields (80-96%) and characterized by NMR, ESI-HRMS, GPC, IR, and X-ray data: p-carboxyphenylsiloxanes in crystalline state form HOF-like structures. Furthermore, it was shown that the suggested method is applicable for the oxidation of organic alkylarene derivatives (Ar-CH3, Ar-CH2-R) to the corresponding acids and ketones (Ar-C(O)OH and Ar-C(O)-R), as well as hydride silanes ([Si]-H) to silanols ([Si]-OH). The possibility of synthesizing monomeric (methyl) and polymeric (siloxane-containing PET analogue, Sila-PET) esters based on 1,3-bis(p-carboxyphenyl)disiloxane was studied. These processes occur with retention of the organosiloxane frame and allow to obtain the corresponding products in 90 and 99% yields.

A Cu-Doped ZIF-8 metal organic framework as a heterogeneous solid catalyst for aerobic oxidation of benzylic hydrocarbons

Mixed-metal metal organic frameworks have received considerable attention in recent years and it has been shown that the activity of the parent metal organic framework (MOF) is often enhanced upon doping with external metal ions within the framework. In this context, Cu2+ ions with different loadings were incorporated within the ZIF-8 framework to obtain a series of Cu-doped ZIF-8 materials and their activity was examined in the aerobic oxidation of hydrocarbons. The as-synthesized Cu-doped solids were characterized by powder X-ray diffraction (XRD), ultraviolet diffuse reflectance spectroscopy (UV-DRS), scanning electron microscopy (SEM), Fourier Transform infrared (FT-IR), electron paramagnetic resonance (EPR) and inductively coupled plasma (ICP) analysis. The experimental results revealed that the activity of Cu-doped ZIF-8 is much higher than that of the parent ZIF-8 in all the tested substrates at 120 °C. Furthermore, the activity of the Cu-doped ZIF-8 with the highest Cu loading was eight fold higher than that of the parent ZIF-8 in the aerobic oxidation of cyclooctane (1) at 120 °C with more than 80% selectivity to the corresponding cyclooctanol/cyclooctanone (ol/one) mixture. Cu-doped ZIF-8 was reused two times with no significant drop in its activity under identical conditions. Furthermore, comparison of the two times reused solid with that of the fresh solid by powder XRD and SEM analysis revealed identical structural integrity and morphology, respectively during the oxidation reactions.

Arylruthenium(III) Porphyrin-Catalyzed C-H Oxidation and Epoxidation at Room Temperature and [RuV(Por)(O)(Ph)] Intermediate by Spectroscopic Analysis and Density Functional Theory Calculations

The development of highly active and selective metal catalysts for efficient oxidation of hydrocarbons and identification of the reactive intermediates in the oxidation catalysis are long-standing challenges. In the rapid hydrocarbon oxidation catalyzed by ruthenium(IV) and -(III) porphyrins, the putative Ru(V)-oxo intermediates remain elusive. Herein we report that arylruthenium(III) porphyrins are highly active catalysts for hydrocarbon oxidation. Using catalyst [RuIII(TDCPP)(Ph)(OEt2)] (H2TDCPP = 5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrin), the oxidation of C-H bonds of various hydrocarbons with oxidant m-CPBA at room temperature gave alcohols/ketones in up to 99% yield within 1 h; use of [nBu4N]IO4 as a mild alternative oxidant avoided formation of lactone from cyclic ketone in C-H oxidation, and the catalytic epoxidation with up to 99% yield and high selectivity (no aldehydes as side product) was accomplished within 5 min. UV-vis, electrospray ionization-mass spectrometry, resonance Raman, electron paramagnetic resonance, and kinetic measurements and density functional theory calculations lend evidence for the formation of Ru(V)-oxo intermediate [RuV(TDCPP)(O)(Ph)].

Earth-Abundant Mixed-Metal Catalysts for Hydrocarbon Oxygenation

The oxygenation of aliphatic and aromatic hydrocarbons using earth-abundant Fe and Cu catalysts and "green" oxidants such as hydrogen peroxide is becoming increasingly important to atom-economical chemical processing. In light of this, we describe that dinuclear CuII complexes of pyrrolic Schiff-base macrocycles, in combination with ferric chloride (FeCl3), catalyze the oxygenation of π-activated benzylic substrates with hydroperoxide oxidants at room temperature and low loadings, representing a novel design in oxidation catalysis. Mass spectrometry and extended X-ray absorption fine structure analysis indicate that a cooperative action between CuII and FeIII occurs, most likely because of the interaction of FeCl3 or FeCl4- with the dinuclear CuII macrocycle. Voltammetric measurements highlight a modulation of both CuII and FeIII redox potentials in this adduct, but electron paramagnetic resonance spectroscopy indicates that any Cu-Fe intermetallic interaction is weak. High ketone/alcohol product ratios, a small reaction constant (Hammett analysis), and small kinetic isotope effect for H-atom abstraction point toward a free-radical reaction. However, the lack of reactivity with cyclohexane, oxidation of 9,10-dihydroanthracene, oxygenation by the hydroperoxide MPPH (radical mechanistic probe), and oxygenation in dinitrogen-purge experiments indicate a metal-based reaction. Through detailed reaction monitoring and associated kinetic modeling, a network of oxidation pathways is proposed that includes "well-disguised" radical chemistry via the formation of metal-associated radical intermediates.