140874-33-5

Upstream product

• 939-97-9 4-tert-Butylbenzaldehyde 
• 877-65-6 p-tert-butylbenzyl alcohol 
• 98-88-4 benzoyl chloride 
• 19692-45-6 4-tert-butylbenzyl chloride 
• 98-51-1 4-tert-butyltoluene 
• 26537-19-9 methyl 4-tert-butylbenzoate 
• 1058648-68-2 4-tert-butyl-1-(methoxymethoxy)methyl benzene 
• 1058648-72-8 4-tert-butyl-1-[(ethoxymethoxy)methyl]benzene 
• 18880-00-7 1-(bromomethyl)-4-(1,1-dimethylethyl)benzene 

Downstream Products

• 3288-99-1 4-tert-butylbenzyl cyanide 
• 32857-63-9 4-t-butylphenylacetic acid 
• 1373356-95-6 2,2-di(4-tert-butylphenylmethyl)malononitrile 
• 1373357-05-1 (S)-2-(1,3-bis(4-tert-butylphenyl)-2-((S)-4,5-dihydro-4-isopropyloxazol-2-yl)propan-2-yl)-4,5-dihydro-4-isopropyloxazole 
• 22927-07-7 1,2-bis(4-tert-butylphenyl)ethane 

Relevant academic research and scientific papers

Phase-transfer agents as catalysts for a nucleophilic substitution reaction in microemulsions

The reaction between 4-tert-butylbenzyl bromide and potassium iodide was carried out in microemulsions based on different nonionic surfactants, and the reaction rates were compared with those obtained in two-phase systems with added phase-transfer agent, either a quaternary ammonium salt or a crown ether. The reactions were relatively fast in the microemulsions and extremely sluggish in the two-phase systems without additional phase-transfer agent. Addition of a phase-transfer agent did not accelerate the reaction when a hydrocarbon was used as organic solvent, neither in the two-phase system nor in the microemulsion. When a chlorinated hydrocarbon was used as solvent, phase-transfer catalysis became effective and the rate obtained in the two-phase system with an equimolar amount of phase-transfer agent added was higher than that obtained in the microemulsion. When a catalytic amount of phase-transfer agent was used, the rate in the two-phase system was about the same as the rate obtained in the micro-emulsion without the phase-transfer agent. The combined approach, that is, use of a microemulsion as the reaction medium and addition of a phase-transfer agent, gave the highest reaction rate. The quaternary ammonium salt (tetrabutylammonium hydrogen sulfate) was a more efficient catalyst in the microemulsion system than the crown ether ([18]crown-6).

Conversion of Aryl Aldehydes to Benzyl Iodides and Diarylmethanes by H3PO3/I2

For the first time, H3PO3 was used as both the reducing reagent and the promotor in the reductive benzylation reactions with aryl aldehydes. By using a H3PO3/I2 combination, various aromatic aldehydes underwent iodination reactions and Friedel-Crafts type reactions with arenes via benzyl iodide intermediates, readily producing benzyl iodides and diarylmethanes in good yields. Intramolecular cyclization reactions also took place, giving the corresponding cyclic compounds. This new strategy features easy-handling, low-cost, and metal-free conditions.

Preparation method of benzyl iodide and derivatives thereof

The invention discloses a preparation method of benzyl iodide and derivatives thereof, which comprises the following steps: in a protective atmosphere, carrying out heating reaction on aryl aldehyde and iodine elementary substance in the presence of a solvent and phosphorous acid to obtain benzyl iodide and derivatives thereof. According to the method, cheap and green solid phosphorous acid is selected as a reduction reagent for reaction, elemental iodine is selected as an iodine source, the benzyl iodide and the derivatives thereof are efficiently prepared from the aryl aldehyde compounds which are simple and easy to obtain by a one-pot one-step method under mild conditions, and the method has the advantages of simplicity in operation, cheap and easily available reagents, environmental friendliness and the like; and the use of expensive silicon-hydrogen compounds and transition metal catalysts is avoided, and the yield can reach 94% at most, so that the method is beneficial to industrial production.

Continuous Flow Preparation of (Hetero)benzylic Lithiums via Iodine-Lithium Exchange Reaction under Barbier Conditions

Herein we report the generation of benzylic lithiums via an iodine-lithium exchange reaction on benzylic iodides performed in continuous flow using tBuLi as the exchange reagent. The resulting benzylic lithium species are trapped in situ by carbonyl electrophiles under Barbier conditions, resulting in benzylic secondary and tertiary alcohols. This flow procedure further allows the generation of highly reactive heterobenzylic lithium compounds, which are difficult to generate under batch conditions. A general scale-up was possible without further optimization.

Systematic Evaluation of Sulfoxides as Catalysts in Nucleophilic Substitutions of Alcohols

Herein, a method for the nucleophilic substitution (SN) of benzyl alcohols yielding chloro alkanes is introduced that relies on aromatic sulfoxides as Lewis base catalysts (down to 1.5 mol-%) and benzoyl chloride (BzCl) as reagent. A systematic screening of various sulfoxides and other sulfinyl containing Lewis bases afforded (2-methoxyphenyl)methyl sulfoxide as optimal catalyst. In contrast to reported formamide catalysts, sulfoxides also enable the application of plain acetyl chloride (AcCl) as reagent. In addition, it was demonstrated that weakly electrophilic carboxylic acid chlorides like BzCl promote Pummerer rearrangement of sulfoxides already at room temperature. This side-reaction also provided the explanation, why sulfoxide catalyzed SN-reactions of alcohols do not allow the effective production of aliphatic and electron deficient chloro alkanes. Comparison experiments provided further insight into the reaction mechanism.

A General Catalytic Method for Highly Cost- and Atom-Efficient Nucleophilic Substitutions

A general formamide-catalyzed protocol for the efficient transformation of alcohols into alkyl chlorides, which is promoted by substoichiometric amounts (down to 34 mol %) of inexpensive trichlorotriazine (TCT), is introduced. This is the first example of a TCT-mediated dihydroxychlorination of an OH-containing substrate (e.g., alcohols and carboxylic acids) in which all three chlorine atoms of TCT are transferred to the starting material. The consequently enhanced atom economy facilitates a significantly improved waste balance (E-factors down to 4), cost efficiency, and scalability (>50 g). Furthermore, the current procedure is distinguished by high levels of functional-group compatibility and stereoselectivity, as only weakly acidic cyanuric acid is released as exclusive byproduct. Finally, a one-pot protocol for the preparation of amines, azides, ethers, and sulfides enabled the synthesis of the drug rivastigmine with twofold SN2 inversion, which demonstrates the high practical value of the presented method.

N-Hydroxyphthalimide-Mediated Electrochemical Iodination of Methylarenes and Comparison to Electron-Transfer-Initiated C-H Functionalization

An electrochemical method has been developed for selective benzylic iodination of methylarenes. The reactions feature the first use of N-hydroxyphthalimide as an electrochemical mediator for C-H oxidation to nonoxygenated products. The method provides the basis for direct (in situ) or sequential benzylation of diverse nucleophiles using methylarenes as the alkylating agent. The hydrogen-atom transfer mechanism for C-H iodination allows C-H oxidation to proceed with minimal dependence on the substrate electronic properties and at electrode potentials 0.5-1.2 V lower than that of direct electrochemical C-H oxidation.

Nucleophilic Substitutions of Alcohols in High Levels of Catalytic Efficiency

A practical method for the nucleophilic substitution (SN) of alcohols furnishing alkyl chlorides, bromides, and iodides under stereochemical inversion in high catalytic efficacy is introduced. The fusion of diethylcyclopropenone as a simple Lewis base organocatalyst and benzoyl chloride as a reagent allows notable turnover numbers up to 100. Moreover, the use of plain acetyl chloride as a stoichiometric promotor in an invertive SN-type transformation is demonstrated for the first time. The operationally straightforward protocol exhibits high levels of stereoselectivity and scalability and tolerates a variety of functional groups.

METHOD OF CONVERTING ALCOHOL TO HALIDE

The present invention relates to a method of converting an alcohol into a corresponding halide. This method comprises reacting the alcohol with an optionally substituted aromatic carboxylic acid halide in presence of an N-substituted formamide to replace a hydroxyl group of the alcohol by a halogen atom. The present invention also relates to a method of converting an alcohol into a corresponding substitution product. The second method comprises: (a) performing the method of the invention of converting an alcohol into the corresponding halide; and (b) reacting the corresponding halide with a nucleophile to convert the halide into the nucleophilic substitution product.

One-pot preparation of alkyl iodides from esters by indium-catalyzed reductive cleavage of a carbon-oxygen bond

We describe the indium-catalyzed reductive iodination of aliphatic and aromatic esters with iodine and 1,1,3,3- tetramethyldisiloxane (TMDS). This reducing procedure accommodates a variety of esters, including esters containing alkyl groups, halogens, a hydroxy group, a thioether, and an alkene moiety. Also, this procedure was applied to the cleavage of carbon-oxygen bonds in acrylate polymers.