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A mixture of octanols, nonanols and decanols is useful for the preparation of alkoxylates, which alkoxylates may be used as surfactants, which surfactants have surprisingly good biodegradability.

In the direct synthesis of 2-propylheptanol (2-PH) from n-valeraldehyde, a second-metal oxide component Co3O4 was introduced into NiO/Nb2O5-TiO2 catalyst to assist in the reduction of NiO. In order to optimize the catalytic performance of NiO-Co3O4/Nb2O5-TiO2 catalyst, the effects of the Ni/Co mass ratio and NiO-Co3O4 loading were investigated. A series of NiO-Co3O4/Nb2O5-TiO2 catalysts with different Ni/Co mass ratios were prepared by the co-precipitation method and their catalytic performances were evaluated. The result showed that NiO-Co3O4/Nb2O5-TiO2 with a Ni/Co mass ratio of 8/3 demonstrated the best catalytic performance because the number of d-band holes in this catalyst was nearly equal to the number of electrons transferred in hydrogenation reaction. Subsequently, the NiO-Co3O4/Nb2O5-TiO2 catalysts with different Ni/Co mass ratios were characterized by XRD and XPS and the results indicated that both an interaction of Ni with Co and formation of a Ni-Co alloy were the main reasons for the reduction of NiO-Co3O4/Nb2O5-TiO2 catalyst in the reaction process. A higher NiO-Co3O4 loading could increase the catalytic activity but too high a loading resulted in incomplete reduction of NiO-Co3O4 in the reaction process. Thus the NiO-Co3O4/Nb2O5-TiO2 catalyst with a Ni/Co mass ratio of 8/3 and a NiO-Co3O4 loading of 14 wt% showed the best catalytic performance; a 2-PH selectivity of 80.4% was achieved with complete conversion of n-valeraldehyde. Furthermore, the NiO-Co3O4/Nb2O5-TiO2 catalyst showed good stability. This was ascribed to the interaction of Ni with Co, the formation of the Ni-Co alloy and further reservation of both in the process of reuse.

In order to improve the catalytic performance of NiO/Nb2O5-TiO2, several kinds of the second metal oxide component MOx (M = Pd, Co, Ir or Rh) were separately introduced and their effects on the reduction propert

Process intensification is a cornerstone to achieve a significant reduction in energy consumption and CO2emissions in the chemical industry. In this context, a monolithic membrane reactor combining homogeneous catalytic gas-phase hydroformylation of but-1-ene with in situ product removal is here presented. The homogeneous supported ionic liquid-phase (SILP) catalyst consists of a Rh-biphephos complex dissolved in 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [C2C1Im][NTf2] and immobilized on a mesoporous silicon carbide monolith. The resulting monolith is catalytically active and selective towards linear aldehyde formation, but the accumulation of aldehyde products and high boilers in the ionic liquid leads to slow catalyst deactivation. This accumulation is suppressed when bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate is used as alternative solvent, where only marginal aldehyde accumulation and aldol formation occur. A polydimethylsiloxane (PDMS) membrane coating of the monolith increases the aldehyde-alkene ratio by an enrichment factor of 2.2 in the permeate gas compared to the retentate gas from the reactor simplifying further downstream processing. The monolithic membrane reactor loaded with SILP or SLP catalysts presents a scalable, versatile platform to achieve process intensification for diverse hydroformylation reactions as well as related gas-phase reactions.

Abstract: Two silica films -immobilized imidazolium-based ionic liquids (TMICl @silica films) were prepared, characterized and utilized as efficient catalysts for the benzoin reaction. Combined characterization results from FT-IR, elemental analysis, N2 adsorption–desorption isotherms and SEM, suggested that the imidazolium-based ionic liquids were successfully immobilized on the silica films. Moreover, the catalytic performance tests demonstrated that silica films immobilized imidazolium-based ionic liquids (ILs) exhibited excellent activity for the benzoin reactions of aromatic aldehydes. The influence of catalyst concentration, temperature and reaction duration on the catalytic activity were investigated by employing 0.7TMICl @silica film(catalyst C) as the catalyst. The results also showed that the benzoin condensations of aromatic aldehydes could give desired products with satisfactory yields under the optimized conditions. Additionally, the catalyst can be effortlessly separated by filtration and reused more than five times without significant loss of activity. Graphic Abstract: [Figure not available: see fulltext.]

Abstract: Conditions for the condensation of cyclopentanone and n-valeric aldehyde to 2-pentylidenecyclopentanone in the presence of an alcoholic solution of piperidine have been developed. The isomerization of the latter in a continuous-flow system over γ-Al2O3 yields 2-pentylcyclopent-2-en-1-one. The condensation of the obtained unsaturated ketones with ethane-1,2-diol in the presence of a heterogeneous catalyst, a natural aluminosilicate (perlite) modified with zirconyl sulfate, has been studied. The optimum conditions for the preparation of the corresponding unsaturated spiroacetals have been found. The synthesized compounds can be used as synthetic fragrances for different purposes.

The present invention relates to a method for preparing saturated Cn- and C2n-alcohols, wherein the separation of the Cn-alcohols and the C2n-alcohols is effected by means of at least one two-column system or by means of at least one dividing wall column.

The present invention relates to a method for preparing saturated Cn- and C2n-alcohols, wherein the ratio of Cn- to C2n-alcohols is controlled by a distillative separation of the aldehydes used.

The invention relates to an organic compound as well as a preparation method and application thereof. The organic compound has a structural formula I shown in the specification, in the formula, R4 is H; R1, R2 and R3 are alkyl or H of which the carbon number is an integer; the total carbon number of R1, R2, R3 and R4 is 0-3; R5 and R6 are of an identical structure and are both saturated alkyl with 1-3 carbon atoms; A is a polyoxy alkenyl ether group, a sulfation polyoxy alkenyl ether group, an aliphatic, alicyclic or aromatic group which forms an ester group with adjacent oxygen atoms, or an aliphatic, alicyclic or aromatic group which comprises other ester groups. Due to a carbon chain structure similar to Guerbet alcohol and an alcoholic hydroxyl derivative structure at a para-site in the organic compound, the organic compound has excellent low-temperature properties and good degradability in a surfactant, ester type lubricating oil or a plasticizer.

The invention relates to a method for preparing high-carbon branched-chain secondary alcohol. The method comprises the steps: preparing branched-chain olefin aldehyde through self-condensation of linear aliphatic aldehyde or branched-chain aliphatic aldehyde without tertiary carbon, performing a gas-liquid heterogeneous condensation reaction on the branched-chain olefin aldehyde and aliphatic ketone without tertiary carbon under the catalysis action of organic base so as to prepare branched-chain dienone, and performing hydrogenation on the branched-chain dienone so as to prepare unsaturated or saturated branched-chain secondary alcohol. The method has wide sources of raw materials and low cost, and the product has a certain structure, and is particularly suitable for preparation of secondary alcohol polyoxyethylene ether and secondary alcohol polyoxyethylene ether derivatives which have narrow molecular weight distribution; and the alcoholic hydroxyl group of the product is secondary alcohol which has a branched-chain structure but no tertiary carbon, the low temperature performance is excellent, and the biodegradability is good.

Kinetics of the cross aldol condensation of valeraldehyde with cyclopentanone was investigated in a batch reactor under atmospheric pressure at 130?°C using heterogeneous metal modified oxides, such as CeO2–MgO, FeO–MgO, FeO–CaO as well as pristine CaO as catalysts. The catalysts were prepared either by evaporation impregnation or deposition precipitation methods and characterized by XRD, TEM, SEM, nitrogen adsorption, ammonia and CO2 TPD. The results revealed that an optimum amount of strong basic sites gives the highest ratio between cross condensation and self-condensation products of valeraldehyde. The highest yield of the desired product 2-pentylidenecyclopentanone (66%) was obtained with FeO–MgO prepared by the deposition precipitation methods. Graphical Abstract: Cross-condensation of valeraldehyde with cyclopentanone was investigated over heterogeneous Fe–CaO, CeO–MgO, FeO–CaO and CaO catalysts at 130?°C using cyclopentanone as a solvent and reactant. The highest yield of the desired product, 2-pentylidene-cyclopentanone, finding applications as fragrances, flavours and pharmaceuticals, was 66% obtained over FeO–MgO catalyst exhibiting both acid and basic sites.[Figure not available: see fulltext.].

The reactions of 1-aminoalkylphosphonic acids with bromine-water, chlorine-water and iodine-water were investigated. The formation of phosphoric(v) acid, as a result of a halogen-promoted cleavage of the Cα-P bond, accompanied by nitrogen release, was observed. The dephosphonylation of 1-aminoalkylphosphonic acids was found to occur quantitatively. In the reactions of 1-aminoalkylphosphonic acids with other halogen-water reagents investigated by 31P NMR, scission of the Cα-P bond was also observed, the reaction rates being comparable for bromine and chlorine, but much slower for iodine.

The present invention provides a mixed ester of pentaerythritol or a mixed polyhydric alcohol and carboxylic acids; the mixed polyhydric alcohol consisting of pentaerythritol and dipentaerythritol represented by formula (I), and the carboxylic acids comprising 2-ethylhexanoic acid and 2-propylheptanoic acid. The mixed ester exhibits excellent properties (e.g., miscibility with a refrigerant that comprises fluoropropene, low-temperature fluidity, and lubricity) in a well-balanced manner while having the viscosity within the range required for a refrigerant oil, and may be used in an industrial lubricant (e.g., refrigerant oil) and the like.

A one-pot synthesis of polysubstituted benzene derivatives was achieved via a platinum(IV)-catalyzed intramolecular cycloaromatization reaction. The reaction proceeds via a tandem skeletal rearrangment, dehydration and double bond isomerization, which proved to be very useful for the syntheses of a range of interesting polyalkyl-substituted benzenes.

The invention relates to a continuous method for carrying out a multiphase aldol condensation reaction to obtain mixed α, β-unsaturated aldehydes by reacting a mixture of two aliphatic aldehydes having different numbers of carbon atoms, i.e. 2 to 5, in the molecule in a vertical tubular reactor in a concurrent flow in the presence of an aqueous solution of a basically reacting compound. In said method, the aldehyde mixture is dispersed in the aqueous phase in the form of drops, and the aqueous solution of the basically reacting compound flows through the tubular reactor as a continuous phase in laminar conditions.

Ligand-modified Rh complexes were physically adsorbed on the surface of porous silica. The resulting materials were subjected to the continuous gas-phase hydroformylation of C2 and C4 alkenes. The ligands used for catalyst modification were bidentate phosphorus ligands known from the literature, namely, sulfoxantphos (1) and a benzopinacol-based bulky diphosphite 2. The tested catalyst materials were active and, in particular, selective as in comparable homogeneous liquid-phase experiments. Long-term stability experiments over 1000h on stream showed minor deactivation. A significant increase in the catalyst mass after the reaction was detected by weighing and thermogravimetric analysis. By using headspace-GC-MS, the mass increase could be attributed to high-boiling compounds, which are formed insitu during the catalytic reaction itself and accumulate inside the pores of the support. Evidence is given that the initially physisorbed catalyst complexes dissolve in the high-boiling aldol side-products, which are suitable solvents for the active catalyst species and provide a liquid-phase environment held by capillary forces on the support. It's all in the pores! Ligand-modified Rh complexes are physically adsorbed onto the surface of porous silica and the resulting solid materials are subjected to continuous gas-phase hydroformylation of C2 and C4 alkenes. The catalyst materials were surprisingly active and, in particular, exhibited similar selectivity to liquid-phase reactions.

A continuous process and system for preparing branched aldehydes by reacting aldehyde with an acid polymeric catalyst absent any metal from Group VIII to produce a product having about 10 to 99.99% by weight branched unsaturated aldehyde and at least 92% selectivity of reaction to the branched aldehyde and recycling a portion of the product.

The regioselective benzylic metalation of toluenes using BuLi/KO tBu/TMP(H) (LiNK metalation conditions) and subsequent transmetalation to Si by reaction with TMSCl provides a general one-pot procedure for the synthesis of substituted benzyltrimethylsilanes. ArCH 2Si(Me)3 derivatives are bench stable reagents yet can serve as benzyl anion equivalents under mild reaction conditions. Following activation with fluoride they can successfully participate in a wide range of additions to both non-enolizable and enolizable carbonyls. In addition, their use in the synthesis of isochromanones and trifluoromethylated amines is illustrated. The broad synthetic scope and mild practical conditions of use for ArCH2Si(Me)3 reagents demonstrate their general potential as benzyl anion equivalents.

The aldol condensation using cyclopentanone with valeraldehyde was conducted at hydrotalcites catalysis. The catalyst was obtained by calcining the hydrotalcite precursor (Mg/Al = 3:1) at 773 K. Its reaction performance was evaluated on the various molar ratios of cyclopentanone to n-valeraldehyde. A good catalytic selectivity of 90 % and a high conversion of 93 % were achieved under mild conditions.

The invention relates to a method for continuously producing α,β-unsaturated C10-aldehydes from aliphatic C5-aldehydes, comprising the following steps: aldol-condensing aliphatic C5-aldehydes into α,β-unsaturated C10-aldehydes in the presence of an aqueous base in a tube reactor; phase separating the output of the tube reactor into an aqueous catalyst phase and an organic product phase; separating the organic product phase into α,β-unsaturated C10-aldehydes, aliphatic C5-aldehydes, and auxiliary products; discharging a part of the aqueous catalyst phase to remove the reaction water and supplementing said part with liquor solution and subsequently returning said part to the tube reactor. The task of the invention is to improve a method of said kind in a way such that it requires lower energy input. This is achieved in that the aliphatic C5-aldehydes and/or the α,β-unsaturated C10-aldehydes are dispersed in the aqueous base as drops, wherein the average Sauter diameter of the drops is between 0.2 mm and 2 mm.

The invention relates to a process for preparing a mixture of isomeric decane-carboxylic acids, which comprises the following steps: a) hydroformylation of a hydrocarbon mixture containing linear C4-olefins using a rhodium-containing catalyst system; b) aldol condensation of a mixture of aliphatic C5-aldehydes obtained from step a); c) selective hydrogenation of the mixture of unsaturated C10-aldehydes from step b) to aliphatic C10-aldehydes; d) uncatalysed oxidation of the mixture of aliphatic C10-aldehydes from step c) to give a mixture having a proportion of at least 70% by mass of 2-propylheptanoic acid, based on the total content of isomeric decanecarboxylic acids.

An aminopropyltrimethoxysilane functionalized chitosan was found to be an efficient solid base catalyst for the self-aldol condensation of linear aldehydes under solvent-free conditions. The modified catalyst was characterized using physical techniques, elemental analysis, FT-IR, and TGA. The modified chitosan was evaluated for the aldol condensation of C3-C7 linear aldehydes in which the selective formation was obtained for α,β-unsaturated aldehydes. A decreasing trend in the conversion from propanal to heptanal was observed. Propanal and pentanal were subjected for detail investigations to study the effect of parameters like amount of catalyst and aldehyde, and temperature on the conversion and selectivity. Kinetic performance of the modified chitosan investigated for a representative aldehyde, pentanal showed that the rate was increased with the catalyst amount, pentanal and temperature. The catalyst was reused up to six cycles without significant loss in its activity and selectivity.

A self-condensation of aldehydes has been conveniently accomplished by the catalytic action of lysine in water or a solvent-free system under specific emulsion conditions to give α-branched α,β-unsaturated aldehydes in good yields.

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N,N-Dialkylpolyhydroxyalkylamines may be made by the reductive alkylation of an N-alkylpolyhydroxyalkylamine with an aldehyde or ketone, or with an equivalent compound, in the presence of a transition metal catalyst and hydrogen. The reaction is performed in a reaction solvent that contains at least 30 wt% of an organic solvent. The use of a sufficiently high proportion of an appropriate organic solvent in the reaction mixture reduces the amount of water present in the reaction mixture, and provides rapid reaction rates and high yields of the desired product. The N,N-dialkylpolyhydroxyalkylamines may be used in a wide variety of applications.

The liquid-phase isomerization of a variety of epoxides was studied using a complex catalyst system based on magnesium bromide and dimethylformamide. The data obtained elucidate the mechanism of the liquid-phase isomerization and show the range of oxygen-containing compounds which can be prepared through this reaction.

The present invention relates to the field of perfumery. More particularly, it concerns an aldoxane derivative of Formula (I) capable of protecting an active aldehyde R1CHO, for example a perfumery or flavor aldehyde, from a chemically aggressive medium into which they have to be added, and then of releasing said active aldehyde at the desired moment. The present invention concerns also the use of said compound in perfumery or in the flavor industry as well as the compositions or articles associated with said aldoxanes.

The invention relates to a process for the catalytic aldol condensation of aldehydes by means of a multiphase reaction in a tube reactor, wherein the catalyst is present in the continuous phase and at least one aldehyde is present in a dispersed phase and the loading factor B of the tube reactor is equal to or greater than 0.8; the aldol condensation products obtained in this way can be used for preparing alcohols or carboxylic acids.

Reactions of trimethylsilyl-derived iodohydrins of the type R1R2CH-CH(I)OTMS, with electron-rich olefins, and the effects of certain factors on these reactions, were studied. The trimethylsilyl-derived iodohydrins were obtained in situ by reacting R1R2CH-CHO (R1 = R2 = H; R1 = H, R2 = alkyl, phenyl) with TMSI. The corresponding trimethylsilyl enol ether derivatives (R1R2C=CH-OTMS), and 1,1-diarylethylenes were the olefins used. Aldehydes of the type RCH2-CH=O reacted smoothly in the presence of TMSI to yield the condensation product RCH2-CH=C(R)-CH=O. Both RCH(-CH=CAr2)2 and the cyclic acetal 5 were obtained as main products of the RCH=O-TMSI-CH2=CAr2 reaction system, depending on the [RCHO]:[TMSI]:[CH2=CAr2] concentration ratio. The mechanisms of formation for the various main products and by-products are discussed. TMSI substitutes, formed by reacting Me3SiCl with each of several Lewis acids, were also used.

WOCl4 catalyzes dehydrative decarboxylation of 2,3-dihydrocarboxylic acids to enols, likely via β-lactone intermediates.Classical reagents for conversion of 3-hydroxycarboxylic acids to β-lactones fail with these substrates.