659-41-6

Usage

Uses

Used in Pharmaceutical Industry:
4-Fluoro Benzylamine Hydrochloride is used as a key intermediate for the synthesis of various pharmaceuticals and agrochemicals. Its unique structure allows for the formation of carbon-carbon and carbon-nitrogen bonds, which are essential in the development of new drugs and agrochemicals.
Used in Organic Chemistry Reactions:
4-Fluoro Benzylamine Hydrochloride is used as a reagent in organic chemistry reactions, particularly for the formation of carbon-carbon and carbon-nitrogen bonds. Its presence in these reactions facilitates the synthesis of complex organic molecules, contributing to the advancement of organic chemistry.

InChI:InChI=1/C7H8FN.ClH/c8-7-3-1-6(5-9)2-4-7;/h1-4H,5,9H2;1H

Upstream product

• 352-11-4 1-chloromethyl-4-fluorobenzene 
• 159979-96-1 4-fluorobenzyl azide 
• 140-75-0 para-fluorobenzylamine 
• 1194-02-1 4-fluorobenzonitrile 
• 1402844-52-3 1-(4-fluorobenzyl)-3,4-diphenyl-1H-pyrrole-2,5-dione 
• 824-75-9 p-fluorobenzamide 
• 1535-41-7 1-fluoro-4-(nitromethyl)benzene 
• 1849-02-1 2-chloro-1-methyl-benzimidazole 
• 459-57-4 4-fluorobenzaldehyde 
• 403-43-0 4-fluorobenzoyl chloride 

Downstream Products

• 780-22-3 (4-fluoro-benzyl)-carbamic acid-(2-fluoro-ethyl ester) 
• 76523-24-5 1-(4-fluorophenyl)methylurea 
• 144054-88-6 3,7-dimethyl-9-p-fluorobenzylamino-3,7-diazabicyclo<3.3.1>nonane-9-carbonitrile 
• 73733-74-1 N-<(4-fluorophenyl)methyl>-3-nitro-2-pyridinamine 
• 652147-99-4 8-(4-fluoro-benzyl)-8-aza-bicyclo[3.2.1]octan-3-one 
• 1163740-02-0 carboxyeremomycin AA₃,AA₇-bis[N-(p-fluorobenzyl)amide] 
• 1163739-89-6 eremomycin AA₇-N-(p-fluorobenzyl)amide 
• 1333500-45-0 C₁₅H₂₀FN₅*ClH 
• 1333500-33-6 4,6-diamino-1-(4'-fluorobenzyl)-1,2-dihydro-2,2-dimethyl-1,3,5-triazine hydrochloride 
• 2145-65-5 N₁-(4-fluoro)benzyl biguanide hydrochloride 
• 866353-52-8 N-benzoyl-4-fluorobenzamide 
• 187818-92-4 [Pd(OAc)(μ-OAc)(4-FC6H4CH2NH2)]2 
• 187818-85-5 Pd(OOCCH₃)2(H₂NCH₂C₆H₄F)2 
• 3830-97-5 N-(4-fluoro-benzyl)-N',N'-dimethyl-N-thiazol-2-yl-ethylenediamine 

Relevant academic research and scientific papers

Silver-Catalyzed Hydroboration of C-X (X = C, O, N) Multiple Bonds

AgSbF6 was developed as an effective catalyst for the hydroboration of various unsaturated functionalities (nitriles, alkenes, and aldehydes). This atom-economic chemoselective protocol works effectively under low catalyst loading, base- A nd solvent-free moderate conditions. Importantly, this process shows excellent functional group tolerance and compatibility with structurally and electronically diverse substrates (>50 examples). Mechanistic investigations revealed that the reaction proceeds via a radical pathway. Further, the obtained N,N-diborylamines were showcased to be useful precursors for amide synthesis.

Lithium compound catalyzed deoxygenative hydroboration of primary, secondary and tertiary amides

A selective and efficient route for the deoxygenative reduction of primary to tertiary amides to corresponding amines has been achieved with pinacolborane (HBpin) using simple and readily accessible 2,6-di-tert-butyl phenolate lithium·THF (1a) as a catalyst. Both experimental and DFT studies provide mechanistic insight. This journal is

Reduction of Amides to Amines with Pinacolborane Catalyzed by Heterogeneous Lanthanum Catalyst La(CH2C6H4NMe2- o)3@SBA-15

Hydroboration of amides is a useful synthetic strategy to access the corresponding amines. In this contribution, it was found that the supported lanthanum benzyl material La(CH2C6H4NMe2-o)3@SBA-15 was highly active for the hydroboration of primary, secondary, and tertiary amides to amines with pinacolborane. These reactions selectively produced target amines and showed good tolerance for functional groups such as -NO2, -halogen, and -CN, as well as heteroatoms such as S and O. This reduction procedure exhibited the recyclable and reusable property of heterogeneous catalysts and was applicable to gram-scale synthesis. The reaction mechanisms were proposed based on some control experiments and the previous literature. This is the first example of hydroborative reduction of amides to amines mediated by heterogeneous catalysts.

Aluminum Metal-Organic Framework-Ligated Single-Site Nickel(II)-Hydride for Heterogeneous Chemoselective Catalysis

The development of chemoselective and heterogeneous earth-abundant metal catalysts is essential for environmentally friendly chemical synthesis. We report a highly efficient, chemoselective, and reusable single-site nickel(II) hydride catalyst based on robust and porous aluminum metal-organic frameworks (MOFs) (DUT-5) for hydrogenation of nitro and nitrile compounds to the corresponding amines and hydrogenolysis of aryl ethers under mild conditions. The nickel-hydride catalyst was prepared by the metalation of aluminum hydroxide secondary building units (SBUs) of DUT-5 having the formula of Al(μ2-OH)(bpdc) (bpdc = 4,4′-biphenyldicarboxylate) with NiBr2 followed by a reaction with NaEt3BH. DUT-5-NiH has a broad substrate scope with excellent functional group tolerance in the hydrogenation of aromatic and aliphatic nitro and nitrile compounds under 1 bar H2 and could be recycled and reused at least 10 times. By changing the reaction conditions of the hydrogenation of nitriles, symmetric or unsymmetric secondary amines were also afforded selectively. The experimental and computational studies suggested reversible nitrile coordination to nickel followed by 1,2-insertion of coordinated nitrile into the nickel-hydride bond occurring in the turnover-limiting step. In addition, DUT-5-NiH is also an active catalyst for chemoselective hydrogenolysis of carbon-oxygen bonds in aryl ethers to afford hydrocarbons under atmospheric hydrogen in the absence of any base, which is important for the generation of fuels from biomass. This work highlights the potential of MOF-based single-site earth-abundant metal catalysts for practical and eco-friendly production of chemical feedstocks and biofuels.

Phosphine-Free Manganese Catalyst Enables Selective Transfer Hydrogenation of Nitriles to Primary and Secondary Amines Using Ammonia-Borane

Herein we report the synthesis of primary and secondary amines by nitrile hydrogenation, employing a borrowing hydrogenation strategy. A class of phosphine-free manganese(I) complexes bearing sulfur side arms catalyzed the reaction under mild reaction conditions, where ammonia-borane is used as the source of hydrogen. The synthetic protocol is chemodivergent, as the final product is either primary or secondary amine, which can be controlled by changing the catalyst structure and the polarity of the reaction medium. The significant advantage of this method is that the protocol operates without externally added base or other additives as well as obviates the use of high-pressure dihydrogen gas required for other nitrile hydrogenation reactions. Utilizing this method, a wide variety of primary and symmetric and asymmetric secondary amines were synthesized in high yields. A mechanistic study involving kinetic experiments and high-level DFT computations revealed that both outer-sphere dehydrogenation and inner-sphere hydrogenation were predominantly operative in the catalytic cycle.

Deoxygenative hydroboration of primary, secondary, and tertiary amides: Catalyst-free synthesis of various substituted amines

Transformation of relatively less reactive functional groups under catalyst-free conditions is an interesting aspect and requires a typical protocol. Herein, we report the synthesis of various primary, secondary, and tertiary amines through hydroboration of amides using pinacolborane under catalyst-free and solvent-free conditions. The deoxygenative hydroboration of primary and secondary amides proceeded with excellent conversions. The comparatively less reactive tertiary amides were also converted to the corresponding N,N-diamines in moderate yields under catalyst-free conditions, although alcohols were obtained as a minor product.

Fabrication of ω-Transaminase@Metal-Organic Framework Biocomposites for Efficiently Synthesizing Benzylamines and Pyridylmethylamines

In this study, ten ω-transaminases (ω-TAs) have been investigated to efficiently catalyze the synthesis of twenty-four functionalized benzylamines and pyridylmethylamines. We optimized the reactions, screened suitable amino donors and compared ω-transaminases activities for all aromatic aldehyde substrates. Under the optimized conditions, eighteen aromatic amines have been obtained with 60.4%–96.6% conversions and isolated only via simple extraction and recrystallization with 18.5%–81% yields on a preparative scale. Furthermore, we first immobilized the Bm-STA onto the MOFs via the physical adsorption to overcome the limitation of free enzyme and improve their industrial applications. The obtained Bm-STA/UiO-66-NH2 composites exhibited not only high enzymes loading (80.4 mg g?1) and enzyme activity recovery (95.8%), but also the better reusability, storage stability, pH stability and the tolerance to acetone and DMF.

Metal-Free Synthesis of Heteroaryl Amines or Their Hydrochlorides via an External-Base-Free and Solvent-Free C-N Coupling Protocol

Herein, a metal-free and solvent-free protocol was developed for the C-N coupling of heteroaryl halides and amines, which afforded numerous heteroaryl amines or their hydrochlorides without any external base. Further investigations elucidated that the basicity of amines and specific interactions derived from the X-ray crystallography analysis of 3j′·HCl played pivotal roles in the reactions. Moreover, this protocol was scalable to gram scales and applicable to drug molecules, which demonstrated its practical value for further applications.

Cyclic (Alkyl)(amino)carbene Ligand-Promoted Nitro Deoxygenative Hydroboration with Chromium Catalysis: Scope, Mechanism, and Applications

Transition metal catalysis that utilizes N-heterocyclic carbenes as noninnocent ligands in promoting transformations has not been well studied. We report here a cyclic (alkyl)(amino)carbene (CAAC) ligand-promoted nitro deoxygenative hydroboration with cost-effective chromium catalysis. Using 1 mol % of CAAC-Cr precatalyst, the addition of HBpin to nitro scaffolds leads to deoxygenation, allowing for the retention of various reducible functionalities and the compatibility of sensitive groups toward hydroboration, thereby providing a mild, chemoselective, and facile strategy to form anilines, as well as heteroaryl and aliphatic amine derivatives, with broad scope and particularly high turnover numbers (up to 1.8 × 106). Mechanistic studies, based on theoretical calculations, indicate that the CAAC ligand plays an important role in promoting polarity reversal of hydride of HBpin; it serves as an H-shuttle to facilitate deoxygenative hydroboration. The preparation of several commercially available pharmaceuticals by means of this strategy highlights its potential application in medicinal chemistry.

Green method for catalyzing reduction reaction of aliphatic nitro derivative

The invention relates to a green method for catalyzing reduction reaction of aliphatic nitro derivatives. According to the method, non-transition metal compounds, namely triethyl boron and potassium tert-butoxide, are used as a catalytic system for the first time, an aliphatic nitro derivative and pinacolborane which is low in price and easy to obtain are catalyzed to be subjected to a reduction reaction under mild conditions, and an aliphatic amine hydrochloride product is synthesized after acidification with a hydrochloric acid aqueous solution. Compared with a traditional method, the method generally has the advantages that the catalyst is cheap and easy to obtain, operation is convenient, and reaction is safe. The selective reduction reaction of the aliphatic nitro derivative catalyzed by the non-transition metal catalyst and pinacol borane is realized for the first time, and the aliphatic amine hydrochloride product is synthesized through acidification treatment of the hydrochloric acid aqueous solution, so that a practical new reaction strategy is provided for laboratory preparation or industrial production.