Propargyl amine, reaction with carbon

Recently, it has been reported that l,3-dithiole-2-thione (12) reacts with primary amine to give the corresponding thiourea and A-4-thia2oline-2-thione (Scheme 5) (14). 5-Methylenethiazolidine-2-thione (13) obtained from the reaction of propargyl amine and carbon disulfide... 

REPPE PROCESS. Any of several processes involving reaction of acetylene (1) with formaldehyde to produce 2-butync-l,4-diol which can be converted to butadiene (2) with formaldehyde under different conditions to produce propargyl alcohol and, form this, allyl alcohol (3) with hydrogen cyanide to yield acrylonitrile (4) with alcohols to give vinyl ethers (5) with amines or phenols to give vinyl derivatives (6) with carbon monoxide and alcohols to give esters of acrylic acid (7) by polymerization to produce cyclooctatetraene and (8) with phenols to make resins. The use of catalysis, pressures up to 30 atm, and special techniques to avoid or contain explosions are important factors in these processes. 

A-allylic amines are conveniently prepared in high yields by the reaction of azides with allylindium reagents in the presence of sodium iodide at ambient temperature (Equation (74)).307 Stannylation with tributylchloro-stannane occurs exclusively at the a-carbon, yielding allyltributylstannanes (E, Z)-isomerization of the allylic double bond depends largely upon the substitution pattern on the allylic moiety (Equation (75)).26 Allyl and propargyl bromides react with diphenyl diselenides in aqueous media to give allyl and propargyl selenides (Equation (76)).308 309... 

Propargylic carbonates are converted to substituted allenyllithium species but I -alkynylsilanols undergo dilithiation (with r-BuLi-HMPA) and the subsequent reaction with electrophiles at the propargylic position. The doubly lithiated A-methyl aminals can be used in the preparation of Si-N- and P-N-containing heterocycles. ... 

The catalytic [2 + 2 + 1]-cycloaddition reaction of two carbon—carbon multiple bonds with carbon monoxide has become a general synthetic method for five-membered cyclic carbonyl compounds. In particular, the Pauson-Khand reaction has been widely investigated and established as a powerful tool to synthesize cyclopentenone derivatives.110 Various kinds of transition metals, such as cobalt, titanium, ruthenium, rhodium, and iridium, are used as a catalyst for the Pauson-Khand reaction. The intramolecular Pauson-Khand reaction of the allyl propargyl ether and amine 91 produces the bicyclic ketones 93, which bear a heterocyclic ring as shown in Scheme 31. The reaction proceeds through formation of the bicyclic metallacyclopentene intermediate 92, which subsequently undergoes insertion of CO to give 93. 

Fujita reported the carboxylative cyclisation of propargylic amines with carbon dioxide in water (Scheme 16.32). The success of this reaction in aqueous media lies in the nature of the catalyst. Fujita and coworkers synthesised a family of gold(i) complexes bearing dendritic NHC ligands. Amongst them, complex XXI appeared to be the most efficient catalyst, enabling the synthesis of 2-oxazolidinones at room temperature in water. 

Ionic liquids have also been found to be efficient reaction media for the activation of CO2 [82-84]. Diurea derivatives are easily obtained from amines and carbon dioxide with a CsOH/ionic liquid catalyst system [83]. N-Substituted 4-methylene-2-oxazolidinones are also efficiently synthesized in IL media by reaction of carbon dioxide with propargylic alcohol and different amines [82]. Other examples include the cycloaddition of CO2 to epoxides to produce cyclic carbonates [85] and synthesis of cyclic urethanes [86,87]. 

Aside from alkoxycarbonylations, hydroxycarbonylations in the presence of water to yield allenic carboxylic acids [15] (93, Y = OH) and aminocarbonylations in the presence of amines to give the analogous amides [139] (93, Y = NRR ) have also been carried out, respectively (Scheme 7.13). These products of structure 102 can also be obtained if using the propargylamines 101 with R1 = Ph or R3 Z H as starting materials (Scheme 7.15) [140]. Additionally, hydroxycarbonylations, also termed carboxyla-tions, are successful without palladium catalysis by reaction of propargyl halides and carbon monoxide in the presence of nickel(II) cyanide under phase-transfer conditions [141, 142]. 

---