106-73-0Relevant articles and documents
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Cobern,D. et al.
, p. 1897 - 1902 (1966)
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Bertelo,Schwartz
, p. 228 (1975)
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Urry,Huyser
, p. 4876 (1953)
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Deslongchamps,Moreau
, p. 2465 (1971)
Platinum Complex Catalyzed Carbonylation of Organic Iodides: Effective Carbonylation of Organic Iodides Having β-Hydrogens on Saturated sp3 Carbons
Takeuchi, Ryo,Tsuji, Yasushi,Fujita, Masayuki,Kondo, Teruyuki,Watanabe, Yoshihisa
, p. 1831 - 1836 (1989)
Dichlorobis(triphenylphosphine)platinum(II) is an effective catalyst precursor for the carbonylation of organic iodides having β-hydrogens on saturated sp3 carbons.The carbonylation under carbon monoxide pressure in the presence of alcohol gives esters, and aldehydes are obtained by the reaction under carbon monoxide and hydrogen pressure.Thus, 1-iodohexane is carbonylated to methyl heptanoate in 79percent yield in the presence of methanol at 120 deg C under 70 kg cm-2 of initial carbon monoxide pressure.Heptanal is formed in 86percent yield from 1-iodohexane at 120 deg Cunder carbon monoxide (50 kg cm-2) and hydrogen (50 kg cm-2).Alkenyl und alkynyl iodides are also smoothly carbonylated in the presence of alcohol into the corresponding esters without reduction of unsaturated bonds.
Methoxycarbonylation of olefins catalysed by homogeneous palladium(II) complexes of (phenoxy)imine ligands bearing alkoxy silane groups
Akiri, Saphan O.,Ojwach, Stephen O.
, p. 236 - 243 (2019)
The Schiff base compounds 2-phenyl-2-((3(triethoxysilyl)propyl)imino)ethanol (HL1) and 4-methyl-2-((3(triethoxysilyl)propyl)imino)methyl)phenol (HL2) were synthesized via condensation reactions of a suitable ketone or aldehyde and (3-aminopropyl) triethoxy silane (APTES). Whereas the reactions of HL1 and HL2 with [Pd(OAc)2] afforded the bis(chelated) palladium compounds [Pd(L1)2] (1) and [Pd(L2)2] (2), treatments of HL1 and HL2 with [Pd(NCMe)2Cl2] gave the mono(chelated) complexes [Pd(HL1)2Cl2] (3) and [Pd(HL2)2Cl2] (4) respectively. Structural characterization of the compounds was achieved using NMR and FT-IR spectroscopies, mass spectrometry and micro-analyses. Complexes 1–4 gave active catalysts in the methoxycarbonylation of higher olefins producing linear esters as the major products. The coordination environment around the palladium center of the complexes dictated the relative catalytic activity, where the bis(chelated) analogues 1 and 2 were more active than the mono(chelated) analogues 3 and 4. The nature of the acid promoter, phosphine groups, solvent system, olefin substrate and reactions conditions influenced the catalytic behaviour of the complexes.
Pd-catalysed formation of ester products from cascade reaction of 5-hydroxymethylfurfural with 1-hexene
Garcia-Suarez, Eduardo J.,Paolicchi, Dario,Li, Hu,He, Jian,Yang, Song,Riisager, Anders,Saravanamurugan, Shunmugavel
, p. 170 - 174 (2019)
A cascade reaction involving decarbonylation of 5-hydroxymethylfurfural (HMF) followed by methoxycarbonylation of 1-hexene produces methyl heptanoate (MH) using a catalytic system composed of a Pd-phosphine complex and methanesulfonic acid (MSA) co-catalyst at moderate reaction temperature. Concomitant hydration of HMF followed by hydrogenation of methyl levulinate (ML) to γ-valerolactone (GVL) occurs with the catalytic system under the same reaction conditions using HMF and methanol as the source of CO and H2, respectively. Under optimized reaction conditions, about 50% of MH along with 12% ML and 35% GVL is obtained from HMF using Pd-(1,2-bis(di-tert-butylphosphinomethyl)benzene) (DTBPMB), MSA and 1-hexene in methanol at 120 °C. Interestingly, sugars, such as glucose, fructose and xylose, are able to be converted to MH, ML and GVL as well. Isotopic labeling studies with 13C1-fructose in methanol-d4 and 13C-methanol-d4 confirm that H2 originates from methanol, while CO generates predominantly from the formyl group of the HMF formed by fructose dehydration.
Palladium(II) complexes of (pyridyl)imine ligands as catalysts for the methoxycarbonylation of olefins
Zulu, Zethu,Nyamato, George S.,Tshabalala, Thandeka A.,Ojwach, Stephen O.
, (2020)
Reactions of 2-methoxy-N-((pyridin-2-yl)methylene)ethanamine (L1), 2-((pyridin-2-yl)methyleneamino)ethanol (L2) and 3-methoxy-N-((pyridin-2-yl)methylene)propan-1-amine (L3) ligands with either [PdCl2(COD)] or [PdCl(Me)(COD)] produced the corresponding monometallic complexes [PdCl2(L1)] (1), [PdClMe(L1)] (2), [PdCl2(L2)] (3) and [PdCl2(L3)] (4). The solid state structure of complex 1 confirmed the bidentate coordination mode of L1, giving a distorted square planar geometry. All the complexes (1–4) formed active catalysts for the methoxycarbonylation of higher olefins to give linear and branched esters. The catalytic behavior of complexes 1–4 were influenced by both the complex structure and olefin chain length.
PHOTOCHEMICAL CARBONYLATION OF ALKYL IODIDES IN THE PRESENCE OF VARIOUS METAL CARBONYLS
Kondo, Teruyuki,Tsuji, Yasushi,Watanabe, Yoshihisa
, p. 3833 - 3836 (1988)
Various transition metal complexes including group VII and VIII metal carbonyls are highly active catalyst precursors for the photochemical carbonylation of organic iodides at room temperature under an atmospheric pressure of carbon monoxide.Primary, secondary and tertiary alkyl iodides which have β-hydrogens on sp3-carbons were smoothly carbonylated by this catalyst system without β-hydride elimination to give the corresponding esters in yields of 63 - 88 percent.
Electron-transfer Reductions by Active Aldehydes catalysed by Thiazolium Salt in the Presence of Triethylamine
Inoue, Hiroo,Higashiura, Kunihiko
, p. 549 - 550 (1980)
3-Benzylthiazolium salts, in methanol containing triethylamine, catalyse the redox reaction in which aldehydes are oxidized to methyl esters concurrently with the reduction of several organic compounds.
Flexible polyurethanes, renewable fuels, and flavorings from a microalgae oil waste stream
Burkart, Michael D.,Griffin, Graham,Mayfield, Stephen P.,Neelakantan, Nitin,Phung Hai, Thien An,Pomeroy, Robert,Sherman, Suryendra D.,Tessman, Marissa
, p. 3088 - 3094 (2020)
Renewable polymers have become an important focus in next-generation materials, and algae biomass offers an environmentally low-impact feedstock that can serve multiple uses. This study aims to develop a scalable methodology for production of microalgae-based polyols for polyurethane synthesis from waste oils derived from algae biomass. Following separation of omega-3 fatty acids from algae oil, residual oils can offer valuable building blocks for petrochemical replacements. However, unlike vegetable oils, algae oils contain organic contaminants, including photosynthetic pigments and hydrophobic cofactors that can complicate preparative methodologies. Here we convert and purify waste streams from omega-3 depleted Nannochloropsis salina algae oil, with major components consisting of palmitic and palmitoleic acid, into azelaic acid (AA) as a building block for flexible polyurethanes, with a simultaneous production of heptanoic acid (HA) as a flavor and fragrance precursor. Conversion of free fatty acid mixtures into a soft soap allows extraction of organic contaminants, and urea complexation provides isolated palmitoleic acid, which is subsequently ozonolyzed to produce AA and HA. Bio-based polyester diols are prepared from AA via esterification to provide a polyol monomer for flexible polyurethane foam preparation. The HA co-product is modified to produce the flavoring agent methyl heptanoate and also decarboxylated to produce hexane as a renewable solvent. This scalable process can be performed on oils from multiple algal species, offering valuable monomers from a highly sustainable source.
Photo-, electro-, and thermal carbonylation of alkyl iodides in the presence of Group 7 and 8-10 metal carbonyl catalysts
Kondo, Teruyuki,Sone, Yoshitsugu,Tsuji, Yasushi,Watanabe, Yoshihisa
, p. 163 - 174 (1994)
Various transition-metal complexes including Group 7 and 8-10 metal carbonyls are highly active catalyst precursors for the photochemical carbonylation of alkyl iodides having β-hydrogens on saturated sp3-carbons at room temperature under 1 atm of carbon monoxide.Primary, secondary and tertiary alkyl iodides are smoothly carbonylated by this catalyst system without β-hydride elimination (dehydrohalogenation) to give the corresponding esters or amides in high yields.In employment of Mn2(CO)10 as a catalyst, electrochemical carbonylation of alkyl iodides also occurred via generation of an anionic manganese carbonyl intermediate.Actually, anionic manganese carbonyl complexes (pentacarbonylmanganates) showed high catalytic activity for thermal carbonylation of alkyl iodides at room temperature under 1 atm of carbon monoxide without photo-irradiation and electrolysis.Mechanistic studies were performed with kinetics and ESR and it was suggested that the present photo-, electro- and thermal carbonylation would involve a non-chain radical mechanism. Key words: Group 7; Group 8; Group 9; Group 10; Carbonylation; Catalysis; Alkyl iodide
FLOW CHEMISTRY SYNTHESIS OF ISOCYANATES
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Paragraph 0175; 0186-0187; 0206-0208, (2021/06/22)
The disclosure provides, inter alia, safe and environmentally-friendly methods, such as flow chemistry, to synthesize isocyanates, such as methylene diphenyl diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and tetramethylxylene diisocyanate.
Sterically hindered (pyridyl)benzamidine palladium(II) complexes: Syntheses, structural studies, and applications as catalysts in the methoxycarbonylation of olefins
Akiri, Saphan O.,Ojwach, Stephen O.
, (2021/09/09)
Reactions of ligands (E)-N′-(2,6-diisopropylphenyl)-N-(4-methylpyridin-2-yl)benzimidamide (L1), (E)-N′-(2,6-diisopropylphenyl)-N-(6-methylpyridin-2-yl)benzimidamide (L2), (E)-N′-(2,6-dimethylphenyl)-N-(6-methylpyridin-2-yl)benzimidamide (L3), (E)-N′-(2,6-dimethylphenyl)-N-(4-methylpyridin-2-yl)benzimidamide (L4), and (E)-N-(6-methylpyridin-2-yl)-N′-phenylbenzimidamide (L5) with [Pd(NCMe)2Cl2] furnished the corresponding palladium(II) precatalysts (Pd1–Pd5), in good yields. Molecular structures of Pd2 and Pd3 revealed that the ligands coordinate in a N^N bidentate mode to afford square planar compounds. Activation of the palladium(II) complexes with para-tolyl sulfonic acid (PTSA) afforded active catalysts in the methoxycarbonylation of a number of alkene. The resultant catalytic activities were controlled by the both the complex structure and alkene substrate. While aliphatic substrates favored the formation of linear esters (>70%), styrene substrate resulted in the formation of predominantly branched esters of up to 91%.