5432-30-4

Usage

Synthesis Reference(s)

Synthetic Communications, 25, p. 2457, 1995 DOI: 10.1080/00397919508015450

InChI:InChI=1/C11H22O2/c1-2-3-4-5-6-7-8-11-12-9-10-13-11/h11H,2-10H2,1H3

Upstream product

• 124-19-6 nonan-1-al 
• 107-21-1 ethylene glycol 
• 111-66-0 oct-1-ene 
• 201230-82-2 carbon monoxide 
• 18742-02-4 2-bromo-2-(2-ethyl)dioxolane 
• 83665-55-8 2-(2-iodoethyl)-1,3-dioxolane 
• 4362-36-1 2-(2-chloroethyl)-1,3-dioxolane 
• 75340-08-8 1-phenylthio-1-trimethylsilylnonane 
• 111-25-1 1-bromo-hexane 
• 100057-40-7 2-(5-butyl-[2]thienyl)-[1,3]dioxolane 

Downstream Products

• 16179-40-1 Pelargonsaeure-<2-hydroxy-aethylester> 
• 18913-04-7 ethylene glycol monononyl ether 
• 124-19-6 nonan-1-al 
• 91898-21-4 2-<<1-(phenylthio)nonyl>oxy>ethanol 
• 2348-19-8 nonanal (2,4-dinitrophenyl)hydrazone 

Relevant academic research and scientific papers

Tandem Hydroformylation–Acetalization Using a Water-Soluble Catalytic System: a Promising Procedure for Preparing Valuable Oxygen-Containing Compounds from Olefins and Polyols

Specific features of the tandem hydroformylation–acetalization of a series of unsaturated compounds and polyols in the presence of a water-soluble catalytic system containing a rhodium catalyst precursor, sodium (triphenylphosphino)trisulfonate, and H2SO4 were investigated. The process parameters, including component ratio, temperature, and reaction time, were optimized using model substrates. With the suggested catalytic system, the conversion of unsaturated compounds to target products, acetals, reached 95%, and the catalytic system could be separated from the reaction products and repeatedly used without considerable loss of the activity. The acetal preparation procedure is versatile with respect to the raw materials. Batches of acetal mixtures were prepared by the suggested procedure from 1-octene and polyols, e.g., ethylene glycol, glycerol, and sorbitol.

Co-catalysis of a bi-functional ligand containing phosphine and Lewis acidic phosphonium for hydroformylation-acetalization of olefins

A novel ionic bi-functional ligand of L2 containing a phosphine and a Lewis acidic phosphonium with I- as the counter-anion was prepared and fully characterized. The molecular structure indicated that the bi-functionalities in L2 were well retained without the incompatibility problem for quenching of the acidity of the phosphonium cation by the Lewis basic phosphine fragment or the anionic I- when the incorporated phosphine fragment and the Lewis acidic phosphonium were strictly located in the confined cis-positions. The co-catalysis over L2-Rh(acac)(CO)2 in the ways of synergetic catalysis and sequential catalysis was successfully fulfilled for one-pot hydroformylation-acetalization, which proved not to be the result of the simple mixture of the mono-phosphine (L4) and the phosphonium salt (L4′). In L2, the phosphonium not only acted as a Lewis acid organocatalyst to drive the sequential acetalization of aldehydes, but also contributed to the synergetic catalysis for the preceding hydroformylation through stabilizing the Rh-acyl intermediate with the phosphine cooperatively. The L2-Rh(acac)(CO)2 system is also generally applied to hydroformylation-acetalization of a wide range of olefins in different alcohols. Advantageously, as an ionic phosphonium-based ligand, L2 could be recycled for 7 runs with Rh(acac)(CO)2 together in RTIL of [Bmim]BF4 without obvious activity loss or metal leaching.

Phosphonium-based aminophosphines as bifunctional ligands for sequential catalysis of one-pot hydroformylation-acetalization of olefins

A series of ionic phosphonium-based aminophosphines L1-L3 were prepared and fully characterized, in each of which the involved bifunctional moieties of the phosphine fragment and Lewis acidic phosphonium were linked together by stable chemical bonds and bridged by one N-atom. The molecular structure of the L2-ligated Rh-complex (Rh-L2) indicated that such bifunctionalities were well retained without incompatibility problems. Investigations on co-catalysis over L1-L3 showed that L3 exhibited the best sequential catalysis for both hydroformylation and acetalization. The phosphine fragment in L3 was responsible for hydroformylation together with the Rh-complex and the phosphonium acted as the Lewis acidic catalyst in charge of acetalization. The L3-Rh(acac)(CO)2 system also exhibited good generality to hydroformylation-acetalization of a wide range of olefins in different alcohols.

Cation-exchange resins in the hydroformylation–acetalization tandem reaction

Cation-exchange resins in the acid form (Amberlyst-16, Wofatit KPS 200, Nafion, KU-2) have been tested as the acidic component of a catalyst system for the hydroformylation–acetalization tandem process. It has been shown that the hydroformylation of octene-1 in the presence of ethylene glycol and glycerol using a catalyst system comprising a rhodium complex, a phosphine ligand, and a solid acid leads to the formation of acetals with a yield of up to 99%.

Synthesis of cyclic acetals by hydroformylation of oct-1-ene in the presence of polyols

Rhodium-catalyzed hydroformylation of oct-1-ene in acid medium in the presence of polyols gives acetals of the initially formed aldehydes. The use of water-soluble trisodium salt of tris(sulfonatophenyl)phosphine as a ligand favors easy separation of the reaction products and enables repeated use of the catalytic system. A minor additive (2 wt.%) of the obtained acetal mixture improves the lubricating properties of diesel fuel by 30% and markedly reduces gum formation during combustion.

Tandem hydroformylation-acetalization with a ruthenium catalyst immobilized in ionic liquids

For the first time, a ruthenium catalyzed hydroformylation-acetalization reaction of olefins is presented. The tandem reaction proceeds well with 1,2- or 1,3-diols, trapping the intermediary formed aldehydes as cyclic acetals. In this manner the hydrogenation of the aldehydes to the corresponding alcohols usually observed with Ru catalysts is prevented. The optimized catalytic system consisting of Ru catalyst, ionic liquids, acetic acid and ammonium salt can be recycled and reused for at least two further runs. Interestingly, styrenes as substrate give preferentially terminal acetals.

Acetalization of aldehydes and ketones over H4[SiW 12O40] and H4[SiW12O 40]/SiO2

H4[SiW12O40] (H-SiW12) is demonstrated to be able to efficiently catalyze the acetalization of aldehydes and ketones with ethylene glycol and 1,3-propanediol. Nevertheless, the possible leaching and the recycling of H-SiW12 are two major disadvantages that largely restrict its further application in industry. Moreover, H 4[SiW12O40] tends to deactivate strong proton sites due to the small surface area of 10 m2 g-1. Due to interactions with surface silanol groups, the proton sites of polyoxometalates (POMs) on SiO2 are less susceptible to deactivation. As such, immobilization of H4[SiW12O40] onto SiO 2 leads to the heterogeneous catalyst H4[SiW 12O40]/SiO2 (H-SiW12/SiO 2), which can catalyze the acetalization of aldehydes and ketones with ethylene glycol and 1,3-propanediol selectively and efficiently without the need of a drying agent. The acetalization process can proceed smoothly at a relatively low temperature under solvent-free conditions. The catalyst of H 4[SiW12O40]/SiO2 can be recycled at least ten times without an obvious decrease in its catalytic activity. As far as we know, the TONs of the H-SiW12/SiO2-catalyzed acetalization of cyclohexanone with ethylene glycol, and benzaldehyde with 1,3-propanediol are the highest reported so far.

Tunable catalysts for solvent-free biphasic systems: Pickering interfacial catalysts over amphiphilic silica nanoparticles

Stabilization of oil/oil Pickering emulsions using robust and recyclable catalytic amphiphilic silica nanoparticles bearing alkyl and propylsulfonic acid groups allows fast and efficient solvent-free acetalization of immiscible long-chain fatty aldehydes with ethylene glycol.

Highly effective tandem hydroformylation-acetalization of olefins using a long-life Bronsted acid-Rh bifunctional catalyst in ionic liquid-alcohol systems

A robust and highly effective tandem hydroformylation-acetalization of olefins using a Bronsted acid-Rh bifunctional catalyst (ARBC) in ionic liquid-alcohol systems is reported. The key feature of the ARBC is its use of a zwitterionic phosphine ligand bearing an amino acid tag. This novel ARBC shows an excellent catalytic efficiency and a long service life without a significant drop in both the hydroformylation efficiency and the acetalization efficiency or Rh loss for more than seventeen cycles. We believe that the long-term high activity and acetal selectivity mainly benefit from the synergy between the acidic active site and the Rh active site on the ARBC and the highly effective immobilization and recycling of ARBC in ionic liquid-alcohol systems due to the strong affinity of ARBC for the ionic liquid.