- HETEROGENEOUS SYNTHESIS OF METHYLENE DIANILINE
-
The present invention relates to a catalytic material for the preparation of one or more of 4,4'- methylenedianiline, 2,2'-methylenedianiline, 2,4'-methylenedianiline, and oligomers of two or more thereof, the catalytic material comprising an oxidic support, wherein the oxidic support comprises an element EOS1 selected from the group consisting of Ti, Zr, Al, Si, and mixtures of two or more thereof, and further comprising a supported material supported on the oxidic support, wherein the supported material comprises an element ESM1 selected from the group consisting of Ti, Zr, V, Nb, Ta, Mo, W, Ge, Sn, Sc, Y, La, Ce, Nd, Pr, Hf, Cr, Fe, Co, Ni, Cu, Zn, Pb, and mixtures of two or more thereof. Further, the present invention relates in particular to a process for the preparation of a catalytic material and to a process for the preparation of one or more of 4,4'-methylenedianiline, 2,2'-methylenedianiline, 2,4'-methylenedianiline and oligomers of two or more thereof.
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Page/Page column 33-35
(2021/06/22)
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- Lewis acid solid catalysts for the synthesis of methylenedianiline from aniline and formaldehyde
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A catalyst containing Hf4+ and Zn2+ supported on silica has been found to be highly effective for the synthesis of methylenedianiline (MDA), an indispensable precursor in the polyurethane industry. Its performance was further improved when the silica support was replaced by silica-alumina, which resulted in a catalyst that was both active and selective, as indicated by the high MDA yield and high 4,4′–MDA/(2,2′–MDA + 2,4′–MDA) isomer ratio obtained. Furthermore, the catalyst also gave an appreciable oligomeric MDA (OMDA) yield and was noticeably more stable than the zeolites that were used in comparative tests: it could be used in at least five consecutive runs without any significant loss in activity. The combination of Br?nsted and Lewis acidity strongly increases the overall activity and yields a catalyst that represents a remarkably stable and reusable alternative to the commonly studied systems for this reaction.
- Cheung, Ka Yan,De Baerdemaeker, Trees,De Vos, Dirk,Gordillo, Alvaro,Marquez, Carlos,Parvulescu, Andrei-Nicolae,Tomkins, Patrick
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p. 114 - 123
(2021/06/16)
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- METHOD OF PRODUCING DIAMINES AND POLYAMINES OF THE DIPHENYLMETHANE SERIES
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The invention relates to a method for producing diamines and polyamines of the diphenylmethane series, by condensing aniline and formaldehyde followed by an acid-catalysed rearrangement at different production capacities with alteration of the isomer composition in the resulting diamines of the diphenylmethane series (altering the 2,4′-MDA content). Adapting the molar ratios of the total used aniline to the total used formaldehyde and of the total used acid catalyst to the total used aniline, and adapting the reaction temperature, allows the rearrangement reaction to be fully completed despite the change in dwell time inevitably associated with a change in production capacity, and allows the formation of undesired by-products to be avoided as far as possible; the intended modification to binuclear content is likewise achieved.
- -
-
Paragraph 0134-0140; 0152-0159
(2020/03/28)
-
- Synthetic method of 2-(4-aminobenzyl) aniline
-
The invention discloses a synthetic method of 2-(4-aminobenzyl) aniline. The method comprises the following steps: carrying out Suzuki coupling reaction on 2-aminophenylboronic acid (1) and nitrobenzyl bromide (2) in a mixed solvent of water and an organic solvent to generate 2-(4-nitrobenzyl) aniline (3); dissolving the 2-(4-nitrobenzyl) aniline (3) obtained in the previous step into methanol, and carrying out catalytic hydrogenation in the hydrogen atmosphere to obtain 2-(4-aminobenzyl) aniline (4). According to the synthetic method disclosed by the invention, the problems of generation of aplurality of isomers and complex separation in the prior art are solved; the synthetic method has the advantages of mild reaction conditions of a path, simple purification conditions and suitabilityfor enlarged production; a final product is prepared at higher yield and high purity.
- -
-
Paragraph 0043-0045
(2018/05/16)
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- For the preparation of diamino diphenyl alkane method
-
The invention relates to a method for producing diaminodiphenyl alkanes, wherein an aromatic amine, which can be substituted or unsubstituted, is reacted with a C1-C3 aldehyde in the presence of a heterogeneous catalyst, said catalyst being a mesoporous acidic ion exchanger based on a divinylbenzene/styrene copolymer and the catalyst having acid centers in a concentration of 2 to 6 eq/kg measured according to DIN 54403 and the average pore diameter of the catalyst particles being 10 to 32 nm measured according to ASTM D 4222, and the content of polynuclear compounds in the reaction mixture being >10 and ?15% by weight.
- -
-
Paragraph 0056-0060
(2017/03/17)
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- Efficient Sc triflate mesoporous-based catalysts for the synthesis of 4,4′-methylenedianiline from aniline and 4-aminobenzylalcohol
-
Sc triflate mesoporous-based catalysts have been prepared using a two-step strategy (i.e., Atrane method) based on the formation of the hierarchic bimodal porosity in the first step and the formation of Sc triflate complexes at the materials surface in the second step. All solids were analyzed by EPMA, surface area, and pore size values, XRD, TEM, FTIR, and 45Sc NMR static spectra. The catalysts have been investigated in the synthesis of 4,4′-methylenedianiline (4,4′-MDA) from aniline and 4-aminobenzylalcohol. 4,4′-MDA was obtained with selectivities over 85.0% for a conversion of aniline of 31%, at 80 °C and after 24 h. Using microwaves, selectivities of 90% in 4,4′-MDA were reached in only 3 h. Important key parameters influencing the catalytic performances seem to be the scandium content and the nature of the formed Sc species. By replacing formaldehyde with 4-aminobenzylalcohol, the necessity of additional steps for neutralization and separation of the wastes can be eliminated.
- Candu, Natalia,Ciobanu, Madalina,Filip, Petru,Haskouri, Jamal El,Guillem, Carmen,Amoros, Pedro,Beltran, Daniel,Coman, Simona M.,Parvulescu, Vasile I.
-
scheme or table
p. 76 - 85
(2012/03/27)
-
- Reaction network and mechanism of the synthesis of methylenedianiline over dealuminated Y-type zeolites
-
The reaction network and mechanism of the synthesis of methylenedianiline (MDA) from the condensation product of aniline and formaldehyde (aminal) on microporous acidic materials has been elucidated. The first step of the reaction, the decomposition of the aminal to N-benzylanilines, is limited by film diffusion, and the second and significantly slower step, the acid catalyzed rearrangement of these intermediates to MDA, is controlled by microkinetics on mesoporous dealuminated Y-type zeolites. This second step of the reaction network is limited by pore diffusion on zeolite BEA as an example for non-mesoporous materials. Based on time-concentration profiles, we were able to determine the reaction orders of the initial decomposition of the aminal to one and two for the following rearrangement of para-aminobenylaniline to 4,4′-MDA. From the kinetic data we deduced an SN2-type reaction mechanism and a complex reaction network, which is able to simulate the observed concentration profiles. The aniline to formaldehyde ratio in the starting mixture had a negligible influence on the final product distribution.
- Salzinger, Michael,Lercher, Johannes A.
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experimental part
p. 149 - 155
(2011/03/22)
-
- Towards an industrial synthesis of diamino diphenyl methane (DADPM) using novel delaminated materials: A breakthrough step in the production of isocyanates for polyurethanes
-
Delaminated materials ITQ-2, ITQ-6 and ITQ-18 are very efficient catalysts of zeolitic nature for the synthesis of diamino diphenyl methane (DADPM), the polyamine precursor in the production of MDI for polyurethanes. The exfoliation process results in excellent accessibility of their active sites to reactant molecules as well as fast desorption of products. These catalysts present higher activity and slower rates of deactivation than their corresponding zeolites. Moreover, the topology of the delaminated structure imposes a precise control of the isomer distribution, offering an additional flexibility in the synthesis of DADPM. By optimizing the process conditions it is possible to achieve final DADPM crude under industrial production specifications with ITQ-18. This catalyst represents a real chance for replacing HCl in the industrial production of DADPM.
- Botella,Corma,Carr, Robert H.,Mitchell, Christopher J.
-
experimental part
p. 143 - 149
(2012/02/13)
-
- LOW CHLORINE, MULTI-STAGED METHOD FOR PRODUCING CYCLOALIPHATIC DISOCYANATES
-
Low chlorine, multi-staged method for producing cycloaliphatic diisocyanates. The invention relates to a multi-staged method for the continuous low-chlorine production of cycloaliphatic diisocyanates, comprising the synthesis of diaminodipheynl alkanes, the hydration thereof into the corresponding cycloaliphatic diamines and the subsequent conversion of cycloaliphatic diamines to the corresponding cycloalkylene biscarbamates and the thermal cleaving of the latter into the cycloaliphatic diisocyanates and alcohol.
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Page/Page column 14
(2011/02/25)
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- Method of preparing polymethylene-polyphenyl-polyamine
-
The present invention provides a method of preparing polymethylene-polyphenyl-polyamine (briefly referred to as polyamine, DAM), in which a high gravity rotating bed is used as the mixing reactor of formaldehyde and aniline hydrochloride, the mixing solution of aniline hydrochloride and circulation solution and the formaldehyde are fed into the high gravity rotating bed reactor proportionally to carry out mixing and condensation reaction under a condition of a very high gravity; the materials leaving the high gravity rotating bed reactor is introduced into a stirred vessel to proceed with the pre-condensation reaction and obtain a condensation solution; and the process steps of heating, molecular rearrangement, neutralization, water washing and purification, etc. are completed to obtain the refined DAM. With the method according to the present invention, the main by-products is obviously reduced in the condensation process, the phenomenon of deposit attaching to the inner walls of circulation pipes and heat exchanger and blockage are prevented in the condensation process, the impurity content is low in the refined DAM, and the subsequent product MDI has a lighter color, the product quality is stable and may be improved to a certain extent.
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Page/Page column 8-9; 11
(2011/04/13)
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- PROCESS FOR PREPARING POLYAROMATIC POLYISOCYANATE COMPOSITIONS
-
Process for the preparation of polyaromatic polyamines comprising the step of reacting formaldehyde with at least one monoaromatic monoamine and at least one monoaromatic compound containing at least two amino functions in the presence of an acidic catalyst where a) the total amount of di-aromatic compounds in the polyaromatic polyamine mixture is in the range from about 25 wt % to about 50 wt % and b) the amount of monoaromatic compound containing at least two amine functions is in the range 5 to 30 mole % relative to 100 mole % of the total amount of monoaromatic monoamines and c) the amount of acidic catalyst used in the preparation of the polyaromatic polyamine mixture is less than about 0.4 moles per mole of formaldehyde or formaldehyde equivalents.
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Page/Page column 7-8
(2011/08/08)
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- PRODUCTION OF MIXTURES OF METHYLENEDIANILINE AND ITS HIGHER HOMOLOGUES USING CALCINED METAL OXIDE-SILICA CATALYSTS
-
The present disclosure relates to compositions, systems, and methods of forming an amine (e.g., methylenedianiline (MDA)) using an acid catalyst including, for example, a metal oxide-silica catalyst calcined at temperature(s) of about ≥ 500°C to form a solid acid silica-metal oxide catalyst. A metal oxide of a solid acid silica-metal oxide catalyst may comprise alumina. A process for making a solid acid silica-metal oxide catalyst may comprise calcining an amorphous alumina-silica material at temperature(s) of about ≥ 500°C and/or under an anhydrous and/or inert atmosphere. A rearrangement reaction of the condensation product of aniline and formaldehyde in the presence of a solid acid silica-metal oxide catalyst may yield more MDA and/or more desirable isomer(s) of MDA than reactions performed with a corresponding catalyst calcined at temperature(s) of less than 500°C.
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Page/Page column 18; 19
(2010/04/03)
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- A PROCESS FOR PREPARATION OF POLYMETHYLENE POLYPHENYL POLYAMINE
-
The present invention provides a method of preparing polymethylene-polyphenyl-polyamine (briefly referred to as polyamine, DAM), in which a high gravity rotating bed is used as the mixing reactor of formaldehyde and aniline hydrochloride, the mixing solution of aniline hydrochloride and circulation solution and the formaldehyde are fed into the high gravity rotating bed reactor proportionally to carry out mixing and condensation reaction under a condition of a very high gravity; the materials leaving the high gravity rotating bed reactor is introduced into a stirred vessel to proceed with the pre-condensation reaction and obtain a condensation solution; and the process steps of heating, molecular rearrangement, neutralization, water washing and purification, etc. are completed to obtain the refined DAM. With the method according to the present invention, the main by-products is obviously reduced in the condensation process, the phenomenon of deposit attaching to the inner walls of circulation pipes and heat exchange and blockage are prevented in the condensation process, the impurity content is low in the refined DAM, and the subsequent product MDI has a lighter color, the product quality is stable and may be improved to a certain extent.
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-
Page/Page column 6
(2010/02/17)
-
- METHOD FOR PRODUCING DIAMINODIPHENYL ALKANES
-
The invention relates to a method for producing diaminodiphenyl alkanes, wherein an aromatic amine, which can be substituted or unsubstituted, is reacted with a C1-C3 aldehyde in the presence of a heterogeneous catalyst, said catalyst being a mesoporous acidic ion exchanger based on a divinylbenzene/styrene copolymer and the catalyst having acid centers in a concentration of 4 to 6 eq/kg as measured according to DIN 54 403 and the average pore diameter of the catalyst particles being 10 to 32 nm as measured according to ASTM D 4222 10, and the content of polynuclear compounds in the reaction mixture being ≦10% by weight.
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Page/Page column 3; 4
(2010/12/29)
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- PROCESS FOR PREPARING DIAMINODIPHENYLMETHANES
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Process for preparing diamino diphenyl methane and poly-(diamino diphenyl methane) comprising reacting aniline with formaldehyde in the presence of hydrogen chloride added in the gaseous form wherein the aniline contains 0.1 to 7 wt%, preferably 2 to 5 wt% of a protic chemical, preferably water.
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-
Page/Page column 11-12
(2008/06/13)
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- Process for the production of 4,4'-diphenylmethane diisocyanate
-
The present invention relates to a process for the production of 4,4′-diphenylmethane diisocyanate (4,4′-MDI) by acid-catalyzed condensation of aniline with formaldehyde, reaction of the mixtures of di- and polyamines obtained with phosgene to form the corresponding mixture of MDI isomers and homologues (di- and polyisocyanates of the diphenylmethane series) and subsequent separation of the mixture by distillation to form 4,4′-MDI and polymeric MDI.
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Page/Page column 3; 4
(2008/06/13)
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- Process for the production of isocyanates
-
Isocyanates, preferably diisocyanates and polyisocyanates of the diphenylmethane series (MDI), are produced by reaction of amines dissolved in a solvent with phosgene in the same solvent to form the corresponding isocyanates. Hydrogen chloride and excess phosgene are subsequently removed from the reaction mixture to obtain a crude isocyanate-containing solution. Subsequently, the crude isocyanate-containing solution is separated by distillation into isocyanates and solvent. The solvent is recycled and used for the production of solutions of the amines and of phosgene. The solvent being recycled is treated to reduce the phosgene and diisocyanate contents before being used for the production of the solution of the amine.
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Page/Page column 4
(2008/06/13)
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- Process for the preparation of 4,4'-diphenylmethane diisocyanate
-
4,4'-diphenylmethane diisocyanate is produced at two different sites by a) reacting aniline and formaldehyde in the presence of an acid catalyst to produce a mixture of diamines and polyamines of the diphenylmethane series at a first production site, b) these diamines and polyamines are then reacted with phosgene to give the corresponding diisocyanates and polyisocyanates of the diphenylmethane series, which may optionally be separated by distillation to give a mixture of diisocyanates and polyisocyanates containing from 50 to 80 wt.% of 4,4'-diphenylmethane diisocyanate, from 1 to 12 wt.% of 2,4'- and/or 2,2'-diphenylmethane diisocyanate taken together, and from 10 to 45 wt.% of trifunctional and higher-functional polyisocyanates, based on the weight of the mixture of diisocyanates and polyisocyanates, c) transferring the mixture of diisocyanates and polyisocyanates to transport containers and transporting these isocyanate-containing containers to a second production site remote from the first, and d) separating the mixture of diisocyanates and polyisocyanates by distillation and/or crystallization to give a pure 4,4'-diphenylmethane diisocyanate containing at least 97 wt.% of 4,4'-diphenylmethane diisocyanate and a maximum of 3 wt.% of 2,4'-diphenylmethane diisocyanate.
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Page/Page column 5-6
(2008/06/13)
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- Process for the production of di-and polyamines of the diphenylmethane series
-
Di- and polyamines of the diphenylmethane series are produced by a) converting nitrobenzene and methanol in the presence of a catalyst to aniline, formaldehyde and carbon monoxide, and then b) converting the aniline and formaldehyde produced in step a) in the presence of an acid catalyst to di- and polyamines of the diphenylmethane series, and c) converting the carbon monoxide produced in step a) with chlorine to phosgene.
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Page/Page column 4
(2008/06/13)
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- Process for the preparation of (poly)-methylenedi(phenylamine)
-
Preparation of di- and polyamine of diphenylmethane comprises: (A) mixing a first portion of aniline with an acid catalyst; (B) mixing a second portion of aniline with formaldehyde; and (C) mixing and subsequently reacting the obtained mixtures.
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Page/Page column 5-9
(2008/06/13)
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- PROCESS FOR THE PRODUCTION OF DIAMINODIPHENYLMETHANE AND ITS HIGHER HOMOLOGUES
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A method of preparing diaminodiphenylmethane and higher homologues thereof from aniline and formaldehyde in the presence of heterogeneous solid acid catalysts selected from (a) delaminated zeolites and/or (b) metal silicate catalysts having an ordered mesoporous pore structure.
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Page/Page column 8
(2008/06/13)
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- Chemical behaviour of seven aromatic diisocyanates (toluenediisocyanates and diphenylmethanediisocyanates) under in vitro conditions in relationship to their results in the Salmonella/microsome test
-
There are conflicting results on the mutagenicity of toluenediisocyanate (TDI) and diphenylmethanediisocyanate (MDI). It was found that the organic solvent chosen to dissolve the compounds dictates the outcome of the bacterial tests. The Salmonella/microsome tests showed uniformly mutagenic effects for all the compounds that were predissolved in DMSO. Due to the instability of aromatic diisocyanates in DMSO this solvent was replaced by ethyleneglycoldimethylether (EGDE). TDI and MDI endured the dissolving and were therefore still available for the subsequent bacterial tests. Furthermore, no aromatic diamines (TDA or MDA) could be detected in EGDE prior to the start of the assays. The Salmonella/microsome tests, however, revealed unexpected differences between TDI and MDI. As previously published the four types of MDI showed negative results, whereas the data presented in this paper demonstrated mutagenic effects of all three types of TDI if EGDE is the solvent. To gain deeper insight into the chemical changes that occurred during the Salmonella/microsome test, the possible reactions were modelled in the laboratory by mixing predissolved diisocyanates with a defined surplus of water and monitoring the progress of the chemical reactions by analytical methods. Additionally, the quality of the model was checked by exposing solutions of 2,6-TDI and 4,4'-MDI to the real biological test environment. In both cases, the reaction patterns of TDI were different to those of MDI. Within 1 min, which is the maximum time needed to mix the predissolved compounds with water before they are poured onto the agar plate, the TDI content was reduced in favour of different ureas and TDA. In addition water was replaced by the complete set of test ingredients. While the TDA content remained more or less constant, the amount of residual TDI was reduced considerably. Reactions of MDI were markedly slower than those of TDI. More than 90% of the predissolved MDI remained intact when it was mixed with water. The biological test ingredients accelerated the reduction of the MDI content. Within 45 s, more than two thirds of the MDI disappeared. Evidently, the chemical reactions continue during incubation. It is assumed that the contrasting results of TDI and MDI in the Salmonella/microsome test are due to the different reaction patterns-and reaction products-of the predissolved diisocyanates created under the specific conditions of the test. These findings indicate that the chemical interactions between reactive test compounds and solvents or test media need to be considered in the interpretation of the relevance of test results. Copyright (C) 1999 Elsevier Science B.V.
- Seel,Walber,Herbold,Kopp
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p. 109 - 123
(2007/10/03)
-
- 2-Propanol derivatives as corrosion inhibitors
-
New composition comprises a functional fluid in contact with ferrous metal and a corrosion inhibiting amount of at least one compound of formula (I) STR1 or a derivative thereof in which R1, R2 and R3 are, independently, hydrogen, a C1 -C15 straight or branched chain alkyl residue, a C5 -C12 cycloalkyl residue, a C6 -C15 aryl residue or C7 -C12 alkaryl residue, and R4 and R5 are, independently, hydrogen, 2-hydroxyethyl or 2-hydroxypropyl with the provisos that (a) R4 and R5 are not simultaneously hydrogen, (b) when R4 and R5 are each --CH2 --CH2 --OH, R1 and R2 are not simultaneously hydrogen and R3 is not a pentyl residue and (c) that polyalkylene and phenol or polycarboxylic ester co-additives are absent; as well as salts thereof. Some of the compounds of formula I are new.
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-
-
- Corrosion inhibiting composition
-
A composition, in contact with a corrodable metal surface, which composition comprises: (a) an aqueous-based or oil-based system; and (b) as inhibitor for protecting the metal surface against corrosion, at least one compound having the formula I: STR1 as well as salts or partial esters thereof wherein: n is 0 or an integer ranging from 1 to 20, R is a straight or branched chain C4 -C30 alkyl group, optionally interrupted by one, two or three oxygen atoms or substituted by one, two or three hydroxy groups, a C5 -C12 cycloalkyl group, a C6 -C10 aryl group optionally substituted by one, two or three C1 -C12 alkyl groups, or a C7 -C13 aralkyl group which is optionally substituted by a hydroxyl group; R1 is H or a straight- or branched chain C1 -C4 alkyl group; R2 is H, a straight or branched chain C1 -C4 alkyl group or CO2 H; R3 is H, a straight or branched chain C1 -C4 alkyl group, --CH2 CO2 H or --CH2 CH2 CO2 H; R4 is H, a straight or branched chain C1 -C4 alkyl group or CO2 H; R5 is H, a straight or branched chain C1 -C4 alkyl group, CH2 CO2 H or CH2 CH2 CO2 H; provided that at least one group R4 must be CO2 H, with the provisio, that compositions comprising an oil-based system and a compound having the formula STR2 wherein R, R1 and R2 are hydrogen or alkyl radicals, having a total from 10 to 38 C-atoms, are excluded.
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-
-
- SYNTHESIS OF PIPERIDINE DERIVATIVES AS POTENTIAL ANALGETIC AGENTS
-
Reaction of N-(1-(2-phenylethyl)-4-piperidinyl)propionanilide (I) with phosphorus pentasulfide gave the thioamide VI.Acylation of N-(1-(2-phenylethyl)-4-piperidinyl)aniline with 2-(methoxy)acetic and 2-(methylthio)acetic anhydrides afforded the amides II and III.Treatment of 4-anilino-1-benzylpiperidine-4-methanol with thionyl chloride gave the spirocyclic sulfurous acid ester amide XIV.Reduction of the hydrochloride of ethyl 3-(1-ethoxycarbonyl-4-phenylimino-3-piperidinyl)propionate (XXII) with sodium cyanoborohydride gave the perhydro-1,6-naphthyridine derivative XIX, a model compound in the synthesis of the cyclic analogue of fentanyl (I).Ethyl 4-anilino-1-(2-phenylethyl)-1,2,3,6-tetrahydropyridine-3-carboxylate (XXIX) hydrochloride, obtained by reaction of ethyl 4-oxo-1-(2-phenylethyl)piperidine-3-carboxylate hydrochloride with aniline, was reduced with lithium aluminium hydride to 4-anilino-1-(2-phenylethyl)piperidine-3-methanol (XXXI). 1-Methyl- and 1-benzyl-4-piperidone were reacted with 4-cyclopropylphenylmagnesium bromide and the tertiary alcohols XXXVII and XXXVIII obtained were acylated with propionyl chloride to give the esters XXXIX and XL.The piperidine derivatives XLI, XLVI and XLVIII were prepared as potential neurotropic agents.Alkylation of 8-hydroxy-6,11-dimethyl-1,2,3,4,5,6-hexahydro-2,6-methano-3-benzazocine (XLIX) with 2-(2-chloroethyl)-1,3-dioxane and -1,3-dioxolane resulted in the 6,7-benzomorphan derivatives L and LI.Out of the compounds prepared, only the closest fentanyl analogues II, III, and VI showed very strong analgetic activity.
- Jilek, Jiri,Rajsner, Miroslav,Valenta, Vladimir,Borovicka, Milos,Holubek, Jiri,et al.
-
p. 1828 - 1853
(2007/10/02)
-
- REDUCTION WITH METAL BOROHYDRIDE-TRANSITION METAL SALT SYSTEM. I. REDUCTION OF AROMATIC NITRO COMPOUNDS WITH POTASSIUM BOROHYDRIDE-COPPER(I) CHLORIDE
-
Upon treatment with potassium borohydride-copper(I) chloride, aromatic nitro compounds afforded cleanly primary amines in high yields.Similarly, nitroso-, azoxy-, and azobenzene were reduced by the same reagent system to give aniline.
- He, Yun,Zhao, He,Pan, Xinfu,Wang, Shaofei
-
p. 3047 - 3050
(2007/10/02)
-
- Triazole-organodithiophosphate reaction product additives for functional fluids
-
New reaction products, useful as additives for functional fluids, are obtained by reacting, at elevated temperature, (A) a triazole having the formula IA or IB: STR1 wherein R7 is hydrogen or a C1 -C20 alkyl residue; R8 and R9 are the same or different and each is C1 -C20 alkyl, C3 -C20 alkenyl, C5 -C12 cycloalkyl, C7 -C13 aralkyl, C6 -C10 aryl or R8 and R9, together with the nitrogen atom to which they are attached, form a 5-, 6- or 7-membered heterocyclic residue or R8 and R9 is each a residue of formula: wherein X is O, S or N(R12), R12 is hydrogen or C1 -C20 alkyl, "alkylene" is a C1 -C12 alkylene residue and n is 0 or an integer from 1 to 6; R10 is hydrogen, C1 -C20 alkyl or C6 -C10 aryl or C7 -C18 alkyl phenyl; and R11 is hydrogen, C1 -C20 alkyl or a residue --CH2 NR8 R9 wherein R8 and R9 have their previous significance; with (B) an organodithiophosphate having the formula: STR2 in which R13 is a C1 -C20 alkyl or C7 -C18 alkyl phenyl or C7 -C13 aralkyl group, M is a metal ion of Group IA, IB, IIA, IIB, VB, VIB, VIIB or VIII of the Periodic System of Elements, and y is the valency of M.
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-
-
- PROTODEALKYLATION OF BIS(AMINOPHENYL)METHANES
-
Contrary to earlier reports, the formation of bis(aminophenyl)methanes in the acid-catalyzed condensation of aniline and formaldehyde can result in carbon-carbon bond cleavage proceeding via an ipso protodealkylation mechanism.
- Whitman, Peter J.,Frulla, Floro F.,Temme, George H.,Stuber, Fred A.
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p. 1887 - 1890
(2007/10/02)
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- TRINUCLEAR INTERMEDIATES IN ANILINE-FORMALDEHYDE CONDENSATION
-
The trinuclear intermediate products 4-(4-anilinomethylanilinomethyl)aniline and 4-aniline were isolated and identified by TLC during investigation of the aniline-formaldehyde condensation in the presence of acidic catalysts.The transformation of these compounds and of 4-anilinomethylaniline in methanol and under the conditions of acid aniline-formaldehyde condensation and rearrangement are described.It was established that the fromation of polyamines is possible not only as a result of the initial reaction of the final diamines with formaldehyde but also of the reaction of protonated anilinomethylanilines with aromatic amines present in the reaction mixture.
- Ringel', Kh.,Popov, L.K.,Ushakova, M.B.
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p. 882 - 885
(2007/10/02)
-