- An efficient and convenient method for the synthesis of dialkoxymethanes using kaolinite as a catalyst
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A one pot synthesis of dialkoxymethanes (2a-h) is described from the reaction of alcohols (1a-h) with paraformaldehyde under reflux in the presence of catalytic amount of kaolinite.
- Pathak, Devendra D.,Gerald, J. Joe
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- Utilization of Formic Acid as C1 Building Block for the Ruthenium-Catalyzed Synthesis of Formaldehyde Surrogates
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Dialkoxymethanes are becoming increasingly important as fuel additives, formaldehyde surrogates, and chemical intermediates, but the effective synthesis remains challenging. Herein, the catalytic synthesis of dialkoxymethane products using a molecular catalyst is reported. The catalytic system, comprising the [Ru(triphos)(tmm)] in combination with the Lewis acid Al(OTf)3, enables the direct synthesis of dialkoxymethane products with formic acid as C1 building block in high to excellent turnover numbers.
- Beydoun, Kassem,Thenert, Katharina,Wiesenthal, Jan,Hoppe, Corinna,Klankermayer, Jürgen
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p. 1944 - 1947
(2020/04/08)
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- Novel synthesis method of alkoxymethylamine compound
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The invention relates to a novel synthesis method of an alkoxymethylamine compound. The novel synthesis method comprises the steps: (1) dehydrating formaldehyde HCHO and alcohol R1OH by carrying out an aldolization under the action of an acid catalyst to obtain dialkoxymethane; and (2) carrying out a hydrocarbylation reaction on dialkoxymethane obtained in step (1) and substituted amine R2-NH2 toremove alcohol to obtain an alkoxymethyl substituent amine compound N-R1 oxymethyl-N-R2 amine. The synthesis method disclosed by the invention is simple in operation and high in yield reaching 92% orabove; and compared with the prior art, the novel synthesis method has the advantages that no acid wastewater, waste salts and chloromethyl alkyl ether serving as a cancerogen are greatly generated, the environment protection cost is favorably reduced, and the industrial prospect is higher.
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Paragraph 0047; 0048
(2019/10/01)
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- Br?nsted-acidic ionic liquids as efficient catalysts for the synthesis of polyoxymethylene dialkyl ethers
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Acetalation of formaldehyde (HCHO) with dialkyl formal or aliphatic alcohol to prepare polyoxymethylene dialkyl ethers (RO(CH2O)nR, n ≥ 1) catalyzed by Br?nsted-acidic ionic liquids has been developed. The correlation between the structure and acidity activity of various ionic liquids was studied. Among the ionic liquids investigated, 1-(4-sulfonic acid)butyl-3-methylimidazolium hydrogen sulfate ([MIMBs]HSO4) exhibited the best catalytic performance in the reaction of diethoxymethane (DEM1) with trioxane. The influences of ionic liquid loading, molar ratio of DEM1 to HCHO, reaction temperature, pressure, time, and reactant source on the catalytic reaction were explored using [MIMBs]HSO4 as the catalyst. Under the optimal conditions of n([MIMBs]HSO4):n(DEM1):n(HCHO) = 1:80:80, 140 °C, and 4 h, the conversion of HCHO and selectivity for DEM2–8 were 92.6% and 95.1%, respectively. The [MIMBs]HSO4 catalyst could be easily separated and reused. A feasible mechanism for the catalytic performance of [MIMBs]HSO4 was proposed.
- Song, Heyuan,Kang, Meirong,Jin, Fuxiang,Wang, Guoqin,Li, Zhen,Chen, Jing
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p. 853 - 861
(2017/05/24)
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- Tailor-made Molecular Cobalt Catalyst System for the Selective Transformation of Carbon Dioxide to Dialkoxymethane Ethers
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Herein a non-precious transition-metal catalyst system for the selective synthesis of dialkoxymethane ethers from carbon dioxide and molecular hydrogen is presented. The development of a tailored catalyst system based on cobalt salts in combination with selected Triphos ligands and acidic co-catalysts enabled a synthetic pathway, avoiding the oxidation of methanol to attain the formaldehyde level of the central CH2 unit. This unprecedented productivity based on the molecular cobalt catalyst is the first example of a non-precious transition-metal system for this transformation utilizing renewable carbon dioxide sources.
- Schieweck, Benjamin G.,Klankermayer, Jürgen
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supporting information
p. 10854 - 10857
(2017/08/30)
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- Preparation method of dibutoxymethane
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The invention discloses a preparation method of dibutoxymethane and relates to a preparation method of methane. The method comprises the process as follows: dimethoxymethane and n-butanol in a certain proportion are taken as raw materials, various liquid acids and supported liquid acids are taken as catalysts, the mixture is subjected to a reaction at the temperature of 0-160 DEG C and under the pressure of 0.1-10.0 MPa, and dibutoxymethane is generated in a high-selectivity manner; a heteropolyacid catalyst is prepared with an equivalent-volume impregnation method, and at least one of activated carbon, TiO2, Al2O3, SiO2, SBA-15 and MCM-41 is taken as a supporter; the supported heteropolyacid catalyst comprises heteropolyacid and a supporter for supporting the heteropolyacid, and heteropolyacid is one or more of phosphotungstic acid, silicotungstic acid, phosphomolybdic acid and silicomolybdic acid. A product prepared with the method is relatively single, the selectivity is high, required raw materials are cheap and easy to obtain, the whole process is simple to operate, no chemical substances polluting the environment are produced, and the preparation method belongs to an environment-friendly technological route.
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Paragraph 0035; 0036
(2016/10/10)
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- Method for synthesizing butoxy methoxymethane
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The invention provides a method for synthesizing methane, in particular to a method for synthesizing butoxy methoxymethane. A brand-new synthesis path for butyl cellosolve and the preparation method for butoxy methoxymethane are developed. The path is characterized in that butoxy methoxymethane is synthesized by methylal and butanol at high selectivity; butoxy methoxymethane is subjected to directional carbonylation, and butoxy methyl acetate is generated; butoxy methyl acetate is hydrogenated to generate butyl cellosolve and methyl alcohol. The preparation method includes the steps that dimethoxymethane and n-butyl alcohol at a certain ratio serve as raw materials, at certain temperature and pressure, molecular sieves of different topological structures serve as catalysts, and butoxy methoxymethane is prepared at high selectivity. The raw materials needed for the method are cheap and easy to get, the whole process is simple in operation, and the product is single, high in selectivity and suitable for industrial production, and has good application prospects.
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Paragraph 0031; 0032
(2017/04/03)
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- Method for preparing dibutoxymethane from dimethoxymethane and n-butyl alcohol
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The invention provides a method for preparing dibutoxymethane from dimethoxymethane and n-butyl alcohol and relates to a method for preparing dibutoxymethane. The method comprises steps as follows: dimethoxymethane and n-butyl alcohol which serve as raw materials are subjected to a reaction in the presence of catalysts, namely, liquid acid and supported liquid acid, at the reaction temperature of 0-160 DEG C under the reaction pressure of 0.1-10.0 MPa, and dibutoxymethane is produced in a high-selective manner; a resin catalyst is one or more of KAD302, KC107, NKC-9, DA-330, D009B, Amberlyst-15, D072H and the like which contain sulfonic acid functional groups; the reaction temperature is 0-160 DEG C and the reaction pressure is 0.1-10.0 MPa. According to the method, a single product is produced, the selectivity is high, required raw materials are low in price and easy to obtain, the operation is simple in the whole procedure, no chemical substances polluting the environment are produced, and the method is an environment-friendly technological process.
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Paragraph 0026
(2017/04/03)
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- Method for preparing dibutoxymethane
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The invention discloses a method for preparing dibutoxymethane, and relates to a method for preparing methane. The method comprises the following processes: dimethoxymethane and n-butanol are adopted as raw materials, and molecular sieves adopting different topological structures are adopted as catalysts for preparing dibutoxymethane at a temperature under the pressure; the atomic ratio of silicon to aluminum in the catalysts, namely, the molecular sieves adopting the different topological structures is as follows: Si/Al=3-100; the molecular sieves adopting the different topological structures are one or more of an H-type MCM-22 molecular sieve, an H-type ZSM-35 molecular sieve, an H-type ZSM-5 molecular sieve, H-mordenite, H-zeolite Y and an H-type Beta molecular sieve; structure types of the catalysts, namely, the molecular sieves adopting the different topological structures are selected from at least one of MWW, FER, MFI, MOR, FAU and BEA. According to the method, relatively single products are produced, the selectivity is high, required raw materials are cheap and easy to obtain, and the whole process is easy to operate; meanwhile, no chemical substances polluting the environment are produced, and the method belongs to an environment-friendly technological path.
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Paragraph 0034-0035
(2017/07/05)
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- Ruthenium-Catalyzed Synthesis of Dialkoxymethane Ethers Utilizing Carbon Dioxide and Molecular Hydrogen
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The synthesis of dimethoxymethane (DMM) by a multistep reaction of methanol with carbon dioxide and molecular hydrogen is reported. Using the molecular catalyst [Ru(triphos)(tmm)] in combination with the Lewis acid Al(OTf)3resulted in a versatile catalytic system for the synthesis of various dialkoxymethane ethers. This new catalytic reaction provides the first synthetic example for the selective conversion of carbon dioxide and hydrogen into a formaldehyde oxidation level, thus opening access to new molecular structures using this important C1source.
- Thenert, Katharina,Beydoun, Kassem,Wiesenthal, Jan,Leitner, Walter,Klankermayer, Jürgen
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supporting information
p. 12266 - 12269
(2016/10/13)
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- The bromodiazirinyl anion: A weakly bound complex of diazirinylidene and a bromide ion
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Experimental and computational evidence suggests that the cleavage of n-butyl and tert-butyl 3-bromodiazirine-3-carboxylates by sodium n-butoxide in DMF, affording high yields of dibutyl carbonates, may proceed by nucleophilic acyl displacement of the bromodiazirinyl anion, a weakly bound complex of a cyclic carbene c-CN2 (diazirinylidene) and a bromide ion. We explain the formation of substantial amounts of di-n-butoxymethane in the presence of n-butanol by a sequence of O-H insertion and denitrogenation reactions of the putative c-CN2 carbene. This ground-state singlet species is the last undescribed member of the CN2 family of reactive intermediates. It differs from classical N-heterocyclic carbenes by its high ionization potential and electron affinity.
- Martinu, Tomas,Boehm, Stanislav,Hanzlova, Eva
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experimental part
p. 6254 - 6260
(2011/12/15)
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- PREPARATION OF DIBUTOXYMETHANE
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A process for the preparation of dibutoxymethane, in one embodiment from 50% formaldehyde, in a condensation reaction without the use of co-solvent.
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Page/Page column 14; 15; 16
(2010/04/03)
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- Montmorillonite, an efficient catalyst for the preparation of dialkoxymethanes
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The reaction of various alcohols with paraformaldehyde in presence of montmorillonite to give dialkoxymethanes (2a-g) in very good yield is described.
- Deshmukh,Gumaste,Bhawal
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p. 3939 - 3944
(2007/10/03)
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- Synthesis of Formaldehyde Acetals by Phase Transfer Catalysis
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By employing phase transfer catalysis, formaldehyde acetals were synthesized from the reaction of alcohols and dibromomethane at moderate temperatures.Using a high alkaline concentration, the reaction could be improved to obtain a 100percent yield by reacting dibromomethane and 1-alcohol employing tetrabutylammonium bromide (TBAB) as a phase transfer catalyst.Six kinds of alcohols with various structures, four sorts of solvents with various dielectric constants and seven types of catalysts were examined to test their reactivities to the reactions.Only one unique product with two alkoxides substituents was observed which indicated the presence of a rather fast reaction rate during the second reaction of the organic phase.The reaction was dramatically enhanced by adding a small amount of quaternary ammonium salt (QX) to obtain a 100percent yield utilizing the alcohols with nonbonding electron pairs within a short period of reaction time.The conversion was also observed to be strongly dependent upon the structure of the quaternary ammonium salts.The reaction rate and the product yield were satisfactorily accounted for the chemical reaction equilibrium of alcohols and KOH in the aqueous phase, the hydration of the active catalyst (QOR) in the organic phase and the distribution of QOR between two phases.
- Wang, Maw-Ling,Chang, Shahng-Wern
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p. 2149 - 2155
(2007/10/02)
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- AROMATIC TERTIARY AMINES AND n-BUTYL NITRITE
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The reaction between alkyl nitrites, particularly n-butyl nitrite, and tertiary aromatic amines under a variety of experimental conditions promptly yielded products of N-dealkylation-N-nitrosation, ring nitration, ipso-substitution and, occasionally, combinations of these processes.Aminoethers were detected as final products and intermediates on the way to N-nitrosations.Reaction pathways are suggested for some of the observed behaviours on the basis of experimental evidences whereas other alternatives are discarded.
- Varardo, Giancarlo,Giumanini, Angelo G.,Strazzolini, Paolo
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p. 4303 - 4332
(2007/10/02)
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- Stereoelectronic Effects in the Gas Phase. 2. Negative Ion Reactions of 1,3-Dithianes and 1,3-Dithiane 1-Oxides
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Reactions of gaseous anions (methoxide, hydroxide, and thermal electrons) with cis-4,6-dimethyl-1,3-dithiane and the corresponding axial and equatorial 1-oxides have been investigated using the techniques of ion cyclotron resonance (ICR) spectroscopy and pulsed positive-negative ion chemical ionization (PPNICI) spectroscopy.Deprotonation to (M-H)(1-) ions and extensive fragmentation to ions m/z 99 and 101 were observed for all three compounds with all three reactant anions.When compounds labeled with deuterium specifically at the C2 position were used, it was foundthat deprotonation occurred at C2 and elsewhere in the molecule.The axial hydrogen at C2 was removed as readily or more so than the equatorial hydrogen, depending on the reactants and conditions of ion generation. (These results differ from the corresponding condensed-phase reactions, which show strong selectivity for C2 equatorial deprotonation).Deuterium isotope effects were estimated to be 1.2 and 1.3 for ions generated by MeO(1-) and e, respectively.Exchange (H/D) between hydroxide and cis-4,6-dimethyl-1,3-dithiane-2-d2 was insignificant, although exchange was observed in comparable reactions of hydroxide with 1,3-dithiane-d2 and bis(methylthio)methane-d2.Stereoelectronic effects that may contribute to selectivity in solution do not account for the gas-phase results.Ab initio calculations at the 3-21G(*) level applied to methanedithiol and the anion (HS)2CH(1-) (as models for the 1,3-dithiane system) provide insight into the nature of the gas-phase reactions.Possible reaction pathways are discussed.
- Fisher, Cindy L.,Kahn, Scott D.,Hehre, Warren J.,Caserio, Marjorie C.
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p. 7379 - 7387
(2007/10/02)
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- QUATERNARY AMMONIUM SALTS IN ALKYLATION REACTIONS (SYNTHESIS OF FORMALDEHYDE ACETALS).
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The influence of the nature of the catalyst on the reaction yields was studied in the synthesis of formaldehyde bis( beta -methoxyethyl) and dibenzyl acetals. The acetal yields were not greatly influenced by the nature of the catalyst. The synthesis was also effected in presence of polymeric ammonium salts. In comparison with earlier results, the polymeric salts in this case were more effective than their monomeric analogs.
- Nazaretyan,Torosyan,Babayan
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p. 2396 - 2400
(2007/10/02)
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- SYNTHESIS OF UNSYMMETRICAL 1,1-DIALKOXYALKANES AND THEIR SULFUR-CONTAINING ANALOGS
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Acyclic acetals and 1,1-di(alkylthio)alkanes enter into exchange reactions in the presence of aprotic acids and of the KU-2 cation-exchange resin with the formation of the unsymmetric acetals and 1-alkoxy-1-alkylthioalkanes.In reaction with ethylal di(ethylthio)methane forms 3,5,7-trioxanonane in addition to ethylthioethoxymethane. 2-Methyl-4-thia-2-hexene was found in the products from the reaction of 1,1-di(ethylthio)-2-methylpropane with methylal.
- Gazizova, L. B.,Imashev, U. B.,Musavirov, R. S.,Kantor, E. A.,Zlotskii, S. S.,et al.
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p. 226 - 231
(2007/10/02)
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- ACTION D'ORGANOMETALLIQUES SUR L'ORTHOFORMIATE DE DIPHENYLE ET D'ETHYLE. PREPARATION D'ACETALS MIXTES DE TYPE RCH(OC2H5)OC6H5
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The reaction between an organometallic compound RM and the mixed orthoester (C6H5O)2CHOC2H5 gives either a mixed acetal RCH(OC2H5)OC6H5 or an ether R2CHOC2H5, depending on the structure of the organometallic compound used.
- Barbot, F.,Miginiac, Ph.
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