68285-26-7

Basic information

• Product Name: Benzenemethanamine, 2-chloro-a-methyl-,(S)-
• Synonyms: (S)-1-(2-CHLOROPHENYL)ETHANAMINE-HCl;(alphaS)-2-Chloro-alpha-methylbenzenemethanamine;(S)-2-Chloro-alpha-methylbenzenemethanamine;(1S)-1-(2-CHLOROPHENYL)ETHAN-1-AMINE-HCL;(1S)-1-(2-CHLOROPHENYL)ETHAN-1-AMINE;Benzenemethamine, 2-chloro-a-methyl-,(S)-;Benzenemethanamine, 2-chloro-a-methyl-,(S)-;Benzenemethanamine, 2-chloro-α-methyl-, (αS)-
• CAS NO: 68285-26-7
• Molecular Formula: C₈H₁₀ClN
• Molecular Weight: 155.6247
• Product Categories: API intermediates
• Mol File: 68285-26-7.mol

Chemical Properties

• Boiling Point: 217.4 °C at 760 mmHg
• Flash Point: 93.3 °C
• Appearance: /
• Density: 1.122
• Storage Temp.: under inert gas (nitrogen or Argon) at 2–8 °C
• PKA: 8.50±0.10(Predicted)
• CAS DataBase Reference: Benzenemethanamine, 2-chloro-a-methyl-,(S)-(CAS DataBase Reference)
• NIST Chemistry Reference: Benzenemethanamine, 2-chloro-a-methyl-,(S)-(68285-26-7)
• EPA Substance Registry System: Benzenemethanamine, 2-chloro-a-methyl-,(S)-(68285-26-7)

Safety Data

• Hazardous Substances Data: 68285-26-7(Hazardous Substances Data)

Usage

Uses

Used in Pharmaceutical Industry:
Benzenemethanamine, 2-chloro-a-methyl-,(S)is used as a key intermediate in the synthesis of various pharmaceutical compounds. Its unique structure and chiral center make it a valuable building block for the development of new drugs and medications.
Used in Organic Synthesis:
In the field of organic synthesis, Benzenemethanamine, 2-chloro-a-methyl-,(S)serves as a versatile reagent and catalyst. Its presence in various chemical reactions allows for the formation of a wide range of organic compounds, contributing to the advancement of chemical research and development.

Upstream product

• 121443-77-4 N-<(S)-1-phenylethyl>(trimethylsilyl)amine 
• 2627-86-3 (S)-1-phenyl-ethylamine 
• 13524-04-4 2'-chloro-sec-phenethyl alcohol 
• 124-20-9 N-(3-aminopropyl)-1,4-diaminobutane 
• 2142-68-9 1-(2-chlorophenyl)ethanone 
• 109-73-9 N-butylamine 
• 39959-67-6 1-(2-Chloro-phenyl)-ethylamine 
• 1149756-73-9 2-methylpropane-2-sulfinic acid [1-(2-chlorophenyl)ethylidene]amide 
• 87227-77-8 bishydrochloride salt of cis-1,4-diamino-but-2-ene 
• 83834-86-0 N-[1-(2-chloro-phenyl)-ethyl]-formamide 
• 2856-63-5 2-Chlorophenylacetonitrile 
• 1239016-36-4 (R)-2-(2-chlorophenyl)propanoic acid 

Downstream Products

• 39959-67-6 (R)-α-(o-chlorophenyl)ethylamine 
• 126017-87-6 5-Allyl-1-[(S)-1-(2-chloro-phenyl)-ethyl]-pyrrolidin-2-one 
• 126017-77-4 1-[(S)-1-(2-Chloro-phenyl)-ethyl]-piperidine-2,6-dione 
• 121443-80-9 (S)-N-<1-(2-Chlorophenyl)ethyl>-2-(3,4-dimethoxyphenyl)acetamide 
• 1198107-13-9 (R)-N-(1-(2-chlorophenyl)ethyl)benzamide 
• 1637437-40-1 C₂₁H₁₉ClN₄O 
• 127733-51-1 2-{[(E)-(R)-1-(2-Chloro-phenyl)-ethylimino]-methyl}-phenol 
• 1567834-46-1 (2E,2'E)-3,3'-(1,4-phenylene)bis(N-(2-chlorobenzyl)-2-cyanoacrylamide) 

Relevant articles and documents

Direct reductive amination of ketones with ammonium salt catalysed by Cp*Ir(iii) complexes bearing an amidato ligand

A series of half-sandwich Ir(iii) complexes1-6bearing an amidato bidentate ligand were conveniently synthesized and applied to the catalytic Leuckart-Wallach reaction to produce racemic α-chiral primary amines. With 0.1 mol% of complex1, a broad range of ketones, including aryl ketones, dialkyl ketones, cyclic ketones, α-keto acids, α-keto esters and diketones, could be transformed to their corresponding primary amines with moderate to excellent yields (40%-95%). Asymmetric transformation was also attempted with chiral Ir complexes3-6, and 16% ee of the desired primary amine was obtained. Despite the unsatisfactory enantio-control achieved so far, the current exploration might stimulate more efforts towards the discovery of better chiral catalysts for this challenging but important transformation.

One-Pot C-H Arylation/Lactamization Cascade Reaction of Free Benzylamines

An efficient method has been developed for the synthesis of seven-membered biaryl lactams involving Pd-catalyzed, native amine-directed, ortho-arylation of benzylamines followed by in situ lactamization. This cascade sequence is enabled by the use of 2-iodobenzoates, which facilitates C-H arylation from the free amine under conditions that typically require an improved directing group approach. This reaction is characterized by a broad substrate scope with good functional group tolerance. The need for an ester versus carboxylic acid-functionalized coupling partner is also explored, as is the potential for synthesizing eight-membered biaryl lactams. Various applications are also investigated, including access to the aza-brassinolide core.

Reductive amination of ketonic compounds catalyzed by Cp*Ir(III) complexes bearing a picolinamidato ligand

Cp*Ir complexes bearing a 2-picolinamide moiety serve as effective catalysts for the direct reductive amination of ketonic compounds to give primary amines under transfer hydrogenation conditions using ammonium formate as both the nitrogen and hydrogen source. The clean and operationally simple transformation proceeds with a substrate to catalyst molar ratio (S/C) of up to 20,000 at relatively low temperature and exhibits excellent chemoselectivity toward primary amines.

Carbon Dioxide-Mediated C(sp2)-H Arylation of Primary and Secondary Benzylamines

C-C bond formation by transition metal-catalyzed C-H activation has become an important strategy to fabricate new bonds in a rapid fashion. Despite the pharmacological importance of ortho-arylbenzylamines, however, effective ortho-C-C bond formation of free primary and secondary benzylamines using PdII remains an outstanding challenge. Presented herein is a new strategy for constructing ortho-arylated primary and secondary benzylamines mediated by carbon dioxide (CO2). The use of CO2 with Pd is critical to allowing this transformation to proceed under relatively mild conditions, and mechanistic studies indicate that it (CO2) is directly involved in the rate-determining step. Furthermore, the milder temperatures furnish free amine products that can be directly used or elaborated without the need for deprotection. In cases where diarylation is possible, an interesting chelate effect is shown to facilitate selective monoarylation.

N-Alkylation of Aqueous Ammonia with Alcohols Leading to Primary Amines Catalyzed by Water-Soluble N-Heterocyclic Carbene Complexes of Iridium

A new catalytic system for the N-monoalkylation of aqueous ammonia with a variety of alcohols was developed. Water-soluble dicationic complexes of iridium bearing N-heterocyclic carbene and diammine ligands exhibited high catalytic activity for this type of reaction on the basis of hydrogen-transfer processes without generating harmful or wasteful byproducts. Various primary amines were efficiently synthesized by using safe, inexpensive, and easily handled aqueous ammonia as a nitrogen source. For example, the reaction of 1-(4-methylphenyl)ethanol with aqueous ammonia in the presence of a water-soluble N-heterocyclic carbene complex of iridium at 150 °C for 40 h gave 1-(4-methylphenyl)ethylamine in 83 % yield.

Substituent effects on chiral resolutions of derivatized 1-phenylalkylamines by heptakis(2,3-di-O-methyl-6-O-tert-butyldimethylsilyl)-β-cyclodextrin GC stationary phase

Chiral resolutions of trifluoroacetyl-derivatized 1-phenylalkylamines with different type and position of substituent were investigated by capillary gas chromatography by using heptakis(2,3-di-O-methyl-6-O-tert-butyldimethylsilyl)-β-cyclodextrin diluted in OV-1701 as a chiral stationary phase. The influence of column temperature on retention and enantioselectivity was examined. All enantiomers of meta-substituted analytes as well as fluoro-substituted analytes could be resolved. Temperature had a favorable influence on enantioselectivity for small amines with substituents at the ortho-position. The type of substituent at the stereogenic center of amines also had a crucial effect as the ethyl group led to poor enantioseparation. Among all analytes studied, trifluoroacetyl-derivatized 1-(2′-fluorophenyl)ethylamine exhibited baseline resolution with the shortest analysis time.

n-Butylamine as an alternative amine donor for the stereoselective biocatalytic transamination of ketones

Formal reductive amination has been a main focus of biocatalysis research in recent times. Among the enzymes able to perform this transformation, pyridoxal-5′-phosphate-dependent transaminases have shown the greatest promise in terms of extensive substrate scope and industrial application. Despite concerted research efforts in this area, there exist relatively few options regarding efficient amino donor co-substrates capable of allowing high conversion and atom efficiency with stable enzyme systems. Herein we describe the implementation of the recently described spuC gene, coding for a putrescine transaminase, exploiting its unusual amine donor tolerance to allow use of inexpensive and readily-available n-butylamine as an alternative to traditional methods. Via the integration of SpuC homologues with tandem co-product removal and cofactor regeneration enzymes, high conversion could be achieved with just 1.5 equivalents of the amine with products displaying excellent enantiopurity.

Stereoselective amination of racemic sec-alcohols through sequential application of laccases and transaminases

A one-pot/two-step bienzymatic asymmetric amination of secondary alcohols is disclosed. The approach is based on a sequential strategy involving the use of a laccase/TEMPO catalytic system for the oxidation of alcohols into ketone intermediates, and their following transformation into optically enriched amines by using transaminases. Individual optimizations of the oxidation and biotransamination reactions have been carried out, studying later their applicability in a concurrent process. Therefore, 17 racemic (hetero) aromatic sec-alcohols with different substitutions in the aromatic ring have been converted into enantioenriched amines with good to excellent selectivities (90-99% ee) and conversion values (67-99%). The scalability of the process was also demonstrated when two different amine donors were used in the transamination step, such as isopropylamine and cis-2-buten-1,4-diamine. Satisfyingly, both sacrificial amine donors can shift the equilibrium toward the amine formation, leading to the corresponding isolated enantioenriched amines with good to excellent results.

Biocatalytic transamination with near-stoichiometric inexpensive amine donors mediated by bifunctional mono- and di-amine transaminases

The discovery and characterisation of enzymes with both monoamine and diamine transaminase activity is reported, allowing conversion of a wide range of target ketone substrates with just a small excess of amine donor. The diamine co-substrates (putrescine, cadaverine or spermidine) are bio-derived and the enzyme system results in very little waste, making it a greener strategy for the production of valuable amine fine chemicals and pharmaceuticals.

But-2-ene-1,4-diamine and But-2-ene-1,4-diol as Donors for Thermodynamically Favored Transaminase- and Alcohol Dehydrogenase-Catalyzed Processes

Both cis- and trans-but-2-ene-1,4-diamines have been prepared and efficiently applied as sacrificial cosubstrates in enzymatic transamination reactions. The best results were obtained with the cis-diamine. The thermodynamic equilibrium of the stereoselective transamination process is shifted to the amine formation due to tautomerization of 5H-pyrrole into 1H-pyrrole, achieving high conversions (78–99%) and enantiomeric excess (up to >99%) by using a small excess of the amine donor. Furthermore, when the reaction proceeded, a strong coloration was observed due to polymerization of 1H-pyrrole. A structurally related compound, cis-but-2-ene-1,4-diol, has been utilized as cosubstrate in different alcohol dehydrogenase (ADH)-mediated bioreductions. In this case, high conversions (91–99%) were observed due to a lactonization process. Both strategies are convenient from both synthetic and atom economy points of view in the production of valuable optically active products. (Figure presented.).