14865-38-4

Usage

InChI:InChI=1/C8H11N.ClH/c1-7-4-2-3-5-8(7)6-9;/h2-5H,6,9H2,1H3;1H

Upstream product

• 527-85-5 o-Methylbenzamid 
• 126799-83-5 2-methylbenzylazide 
• 89-93-0 ortho-methylbenzylamine 
• 933-88-0 ortho-toluoyl chloride 
• 529-19-1 2-Methylbenzonitrile 

Downstream Products

• 105686-05-3 1-(2-methylbenzyl)-imidazolidine-2,4,5-trione 
• 128043-61-8 ethyl [3-(2-methyl-benzyl)-2,4,5-trioxo-imidazolidin-1-yl]ethanoate 
• 226998-04-5 (R)-N-(2-methylbenzyl)-5,5-dimethyl-1,3-thiazolidine-4-carboxamide 

Relevant academic research and scientific papers

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.

Assembly of two new hybrid chloride materials with potential NLO properties: Structure elucidation, empirical and computational studies

This paper deals with the crystal structure of two new non-centrosymmetric hybrid compounds obtained from an aqueous solution by slow evaporation method and characterized by various techniques mainly single-crystal X-ray diffraction. In the atomic arrangement of 2-methylbenzylammonium chloride (1), the organic cations and the chloride anions are linked to each other via N–H…Cl hydrogen bonds; organic cations in zigzag distribution along b-axis in z = 0 and z = ? are also close enough to enable a C–H…π interaction to occur. In 3-methylbenzylammonium chloride (2), the organic cations are linked together by C–H…π interactions and through N–H…Cl and C–H…Cl hydrogen bonds to form a two-dimensional network. To support experimental results, DFT calculations have been accomplished via the B3LYP method and 6-311++G(d,p) basis set on molecular geometry, vibrational, and electronic properties. The non-covalent interactions were studied quantitatively using the Hirshfeld surfaces (HS) associated with 2D fingerprint plots. The NLO properties have been also investigated by DFT and compared to the urea reference.

Method for preparing amine compound by reducing amide compound

The invention relates to a method for preparing an amine compound by reducing an amide compound, which comprises the following steps: in a protective atmosphere, mixing the amide compound or cyclic amide, a zirconium metal catalyst and pinacol borane, carrying out amide reduction reaction at room temperature, and carrying out aftertreatment by using an ether solution of hydrogen chloride after 12-48 hours to obtain an amine hydrochloride compound. The method is simple to operate, low in cost, good in functional group tolerance and wide in substrate range.

Deoxygenation of primary amides to amines with pinacolborane catalyzed by Ca[N(SiMe3)2]2(THF)2

Deoxygenative reduction of amides is a challenging but favorable synthetic method of accessing amines. In the presence of a catalytic amount of Ca[N(SiMe3)2]2(THF)2, pinacolborane (HBpin) could efficiently reduce a broad scope of amides, primary amides in particular, into corresponding amines. Functional groups and heteroatoms showed good tolerance in this process of transformation, and a plausible reaction mechanism was proposed.

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.

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.

Transition metal-free catalytic reduction of primary amides using an abnormal NHC based potassium complex: Integrating nucleophilicity with Lewis acidic activation

An abnormal N-heterocyclic carbene (aNHC) based potassium complex was used as a transition metal-free catalyst for reduction of primary amides to corresponding primary amines under ambient conditions. Only 2 mol% loading of the catalyst exhibits a broad substrate scope including aromatic, aliphatic and heterocyclic primary amides with excellent functional group tolerance. This method was applicable for reduction of chiral amides and utilized for the synthesis of pharmaceutically valuable precursors on a gram scale. During mechanistic investigation, several intermediates were isolated and characterized through spectroscopic techniques and one of the catalytic intermediates was characterized through single-crystal XRD. A well-defined catalyst and isolable intermediate along with several stoichiometric experiments, in situ NMR experiments and the DFT study helped us to sketch the mechanistic pathway for this reduction process unravelling the dual role of the catalyst involving nucleophilic activation by aNHC along with Lewis acidic activation by K ions.

Synthesis of Molybdenum Pincer Complexes and Their Application in the Catalytic Hydrogenation of Nitriles

A series of molybdenum(0), (I) and (II) complexes ligated by different PNP and NNN pincer ligands were synthesized and structurally characterized. Along with previously described Mo?PNP complexes Mo-1 and Mo-2, all prepared compounds were tested in the catalytic hydrogenation of aromatic nitriles to primary amines. Among the applied catalysts, Mo-1 is particularly well suited for the hydrogenation of electron-rich benzonitriles. Additionally, two aliphatic nitriles were transformed into the desired products in 80 and 86 percent, respectively. Moreover, catalytic intermediate Mo-1a was isolated and its role in the catalytic cycle was subsequently demonstrated.

Primary amides to amines or nitriles: A dual role by a single catalyst

We report a manganese-catalyzed hydrosilylative reduction of various primary amides to amines (25 examples). On simple modification of the reaction conditions such as in the presence of a catalytic amount of secondary amide, the same catalyst can transform the primary amides into intermediate nitrile compounds (16 examples) in excellent yields. This is the first example where such a controlled catalytic transformation of primary amides to amines or nitriles with a single catalyst has been demonstrated.

Hydrosilane Reduction of Nitriles to Primary Amines by Cobalt-Isocyanide Catalysts

Reduction of nitriles to silylated primary amines was achieved by combination of 1,1,3,3-tetramethyldisiloxane (TMDS) as the hydrosilane and a catalytic amount of Co(OPIV)2 (PIV = COtBu) associated with isocyanide ligands. The resulting silylated amines were subjected to acid hydrolysis or treatment with acid chlorides to give the corresponding primary amines or imides in good yields. One-pot synthesis of primary amides to primary amines with hydrosilanes was also achieved by iron-cobalt dual catalyst systems.