55756-18-8

Upstream product

• 4238-71-5 1-benzylimidazole 
• 100-39-0 benzyl bromide 
• 77287-34-4 formamide 
• 124-38-9 carbon dioxide 
• 100-46-9 benzylamine 
• 18197-26-7 sodium diformamide 
• 64-18-6 formic acid 

Downstream Products

• 3959-07-7 4-Bromobenzylamine 
• 100-46-9 benzylamine 
• 246257-67-0 benzyl-N,N-dicyclopropylamine 

Relevant academic research and scientific papers

Imidazolium-Based Ionic Liquids Catalyzed Formylation of Amines Using Carbon Dioxide and Phenylsilane at Room Temperature

The CO2-involved synthesis of chemicals is of significance. In this work, we found that 1-alkyl-3-methylimidazolium ionic liquids (ILs) had high efficiency for catalyzing the formylation of amines using CO2 and phenylsilane at room temperature, producing the corresponding formylated products in excellent yields under the metal-free condition. The ILs acted as bifunctional catalysts, which activated the Si-H bond of phenylsilane to react with CO2 to form the formoxysilane intermediate and simultaneously activated the amine substrate through the hydrogen bond. Moreover, the imidazolium cation and the anions of the ILs showed an excellent synergistic effect on catalyzing the formylation of amines.

Additive-free selective methylation of secondary amines with formic acid over a Pd/In2O3 catalyst

Formic acid is used as the sole carbon and hydrogen source in the methylation of aromatic and aliphatic amines to methylamines. The reaction proceeds via a formylation/transfer hydrogenation pathway over a solid Pd/In2O3 catalyst without the need for any additive.

Immobilized Zn(OAc)2on bipyridine-based periodic mesoporous organosilica for N -formylation of amines with CO2and hydrosilanes

Zinc acetate (Zn(OAc)2) was successfully immobilized on a bipyridine-based periodic mesoporous organosilica (BPy-PMO-TMS), as confirmed by solid-state NMR and energy-dispersive X-ray spectroscopies, X-ray diffractometry, and nitrogen adsorption/desorption isotherm analyses. The immobilized Zn complex, Zn(OAc)2(BPy-PMO-TMS), exhibited good catalytic activity during the N-formylations of amines and amides with CO2 and PhSiH3 to produce the corresponding formamides. Zn(OAc)2(BPy-PMO-TMS) with a lower Zn loading was found to exhibit higher catalytic activity.

Selective: N-formylation/N-methylation of amines and N-formylation of amides and carbamates with carbon dioxide and hydrosilanes: Promotion of the basic counter anions of the zinc catalyst

A catalyst composed of commercially available Zn(OAc)2 and 1,10-phenanthroline (phen) was effective in the N-formylation/N-methylation of amines using CO2 as the C1 source in the presence of hydrosilanes. An equimolar reaction of N-methylaniline with PhSiH3 under a CO2 atmosphere yielded the N-formylation product in 92% yield at 25 °C. Scale-up of the reaction using 10 mmol substrate was also successful in affording the desired product in 83% yield (1.1 g). This catalyst exhibits a high thermal stability and a turnover number (TON) of 385000 at 150 °C. In addition, the reaction of N-methylaniline in the presence of excess Ph2SiH2 produced N,N-dimethylaniline. Furthermore, our catalytic protocol was developed for the N-formylation of amides and carbamates, which have smaller pKa values and lower reactivities than the corresponding amines. The present Zn(OAc)2/phen catalyst was found to show versatility in the conversion of CO2 and amines into several functionalized organic chemicals under mild conditions. We propose that the basic counter anion (i.e., the acetate) of the catalyst activates both the Si-H and N-H bonds.

Amide-ligand-controlled highly para-selective arylation of monosubstituted simple arenes with arylboronic acids

Pd-catalyzed highly para-selective arylations of monosubstituted simple arenes with arylboronic acids to widely existed biaryls have been developed. Inspired by requisite amide-directing groups in reported selective oxidative couplings, amide ligands, especially DMF, are designed and found to be critical for the selectivity control in current arylations.

Biomass-derived γ-valerolactone as an efficient solvent and catalyst for the transformation of CO2 to formamides

Efficient conversion of carbon dioxide (CO2) into valuable chemicals is a very attractive topic. Herein, we conducted the first work on the utilization of biomass-derived γ-valerolactone (GVL) as the solvent and catalyst for transformation of CO2 with various primary and secondary amines in the presence of phenylsilane (PhSiH3), and the corresponding desired formamides were produced with high yields without any additional catalyst. Systematic studies indicated that the lactone structure of GVL played a key role in the formation of the active silyl formates and the activation of N-H bonds in amines, thus leading to the excellent performance of GVL for the catalytic reactions.

Iron-catalyzed hydrosilylation of CO2: CO2 conversion to formamides and methylamines

Catalytic hydrosilylation of CO2 is an efficient and selective approach to form chemicals. Herein, we describe the first iron catalysts able to promote the reductive functionalization of CO2 using hydrosilanes as reductants. Iron(ii) salts supported by phosphine donors enable the conversion of CO2 to formamide and methylamine derivatives under mild reaction conditions. This journal is the Partner Organisations 2014.

Cyclopropylamines from N,N-dialkylcarboxamides and grignard reagents in the presence of titanium tetraisopropoxide or methyltitanium triisopropoxide

Thirty-three different N,N-dialkyl- and N-alkyl-N-phosphorylalkyl- substituted carboxamides 9-17 were treated with unsubstituted as well as with 2-alkyl-, 2,2-dialkyl-, and 3-alkenyl-substituted ethylmagnesium bromides 6 in the presence of stoichiometric amounts of titanium tetraisopropoxide or methyltitanium triisopropoxide to furnish substituted cyclopropylamines 20-25 in 20-98 % yield, depending on the substituents with no (1:1) to excellent (>25:1) diastereoselectivities. Generally higher yields (up to 98 %) of the cyclopropylamines 20-28 without loss of the diastereoselectivity were obtained with methyltitanium triisopropoxide as the titanium mediator. Under these conditions, even dioxolane-protected ketones and halogen-substituted and chiral as well as achiral alkyloxyalkyl-substituted carboxamides could be converted to the correspondingly substituted cyclopropylamines with unsubstituted as well as phenyl- and a variety of alkyl-substituted ethylmagnesium bromides in addition to numerous heteroatom-containing (e.g., halogen-, trityloxy-, tetrahydropyranyloxy-substituted) Grignard reagents (62 examples altogether). The transformation of N,N-diformylalkylamines 54 with ethylmagnesium bromide in the presence of methyltitanium triisopropoxide to N,N-dicyclopropyl-N- alkylamines 55 can be brought about in up to 82 % yield (6 examples). An asymmetric variant of the titanium-mediated cyclopropanation of N,N-dialkylcarboxamides has been developed by applying chiral titanium mediators generated from stoichiometric amounts of titanium tetraisopropoxide and chiral diamino or diol ligands, respectively. The most efficient chiral mediators turned out to be titanium bistaddolates that provided the corresponding cyclopropylamines with enantiomeric excesses (ee) of up to 84 %. Evaluation of several silyl-based additives revealed that the reaction can also efficiently be carried out with substoichiometric amounts (down to 25 Mol %) of the titanium reagent, as long as 2-aryl- or 2-ethenyl-substituted ethylmagnesium halides are used and a concomitant slight decrease in yields is accepted. The newly developed methodology was successfully applied for the preparation of analogues with cyclopropylamine moieties of known drugs and natural products such as the nicotine metabolite (S)-Cotinine as well as the insecticides Dinotefuran and Imidacloprid. Ti is it: Cyclopropylamines have been obtained in low to excellent yield through the reaction of different N,N-dialkyl- and N-alkyl-N- phosphorylalkyl-substituted carboxamides with Grignard reagents in the presence of stoichiometric amounts of titanium tetraisopropoxide or methyltitanium triisopropoxide (see scheme). Copyright

OZONOLYSIS OF 1-SUBSTITUTED IMIDAZOLES

1-Substituted imidazoles was ozonolyzed cleanly without any complicated procedures into the corresponding N-acylamides, which were regarded to be much useful derivatives of either amines or acyl compounds.

A Convenient Synthesis of Primary Amines Using Sodium Diformylamide as A Modified Gabriel Reagent

Sodium diformylamide (1) was used as a convenient substitute for phthalimide in the Gabriel synthesis of primary amines.Reagent 1 undergoes smooth N-alkylation with alkyl halides or p-toluenesulfonates 2 in acetonitrile or dimethylformamide to give the corresponding N,N-diformylalkylamines 3 in good yields, except with alkylating agents which are susceptible to base-catalyzed elimination.The formyl group of 3 can be easily removed by hydrochloric acid to give the corresponding alkylamine hydrochlorides 5 or free alkylamines 4.