Condensation Agent Research Articles

ChemInform Abstract: THE CYCLODESULFURIZATION OF THIO‐COMPOUNDS. PART 19: A STUDY OF THE EFFECT OF F MERCURIC CHLORIDE AND ACID CONDENSING AGENTS ON VARIOUS N‐(1,2‐BIS(P‐METHOXYPHENYL)BUTYL)‐N′‐SUBSTITUTED THIOUREA DERIVATIVES

Chemischer InformationsdienstVolume 11, Issue 50 Isocyclic Compounds ChemInform Abstract: THE CYCLODESULFURIZATION OF THIO-COMPOUNDS. PART 19: A STUDY OF THE EFFECT OF F MERCURIC CHLORIDE AND ACID CONDENSING AGENTS ON VARIOUS N-(1,2-BIS(P-METHOXYPHENYL)BUTYL)-N′-SUBSTITUTED THIOUREA DERIVATIVES A.-M. M. E. OMAR, A.-M. M. E. OMARSearch for more papers by this authorA. M. FARGHALY, A. M. FARGHALYSearch for more papers by this authorA. A. B. HAZZA, A. A. B. HAZZASearch for more papers by this authorN. H. ESHBA, N. H. ESHBASearch for more papers by this author A.-M. M. E. OMAR, A.-M. M. E. OMARSearch for more papers by this authorA. M. FARGHALY, A. M. FARGHALYSearch for more papers by this authorA. A. B. HAZZA, A. A. B. HAZZASearch for more papers by this authorN. H. ESHBA, N. H. ESHBASearch for more papers by this author First published: December 16, 1980 https://doi.org/10.1002/chin.198050182Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume11, Issue50December 16, 1980 RelatedInformation

Preparation of polyamides via the phosphorylation reaction. II. Modification of wholly aromatic polyamides with trifunctional monomers

The trifunctional monomers trimesic acid (TMA) and 3,5-diaminobenzoic acid (DAB), each separately and in combination, were used in amounts of 2 to 5 mole-% in order to increase the molecular weight of aromatic polyamides prepared via the Yamazaki phosphorylation reaction. In general, under comparable conditions the use of DAB led to polymer having higher inherent viscosity (IV) values than did TMA. A typical polymer was the polyisophthalamide of 4,4′-methylenedianiline, MDA-I, prepared by the reaction at 100°C of 4,4′-methylenedianiline (MDA) with isophthalic acid (I) in N-methylpyrrolidione (containing 5% dissolved lithium chloride) and employing triphenyl phosphite as condensation agent with pyridine as catalyst. For molar substitutions of 0.0, 2.0, 2.5, and 3.0% of DAB, MDA–I having IV values respectively of 1.1, 1.3, 1.9, and 2.3 was obtained. The latter two samples have IV values in the same range as those obtained for MDA–I prepared from MDA and isophthaloyl chloride in dimethylacetamide (DMAc) via the low-temperature polycondensation method, which prior experience has shown yields polymers that are quite suitable for the spinning of good fibers. At 5 mole-% substitution of DAB, an IV of 3.7 was obtained but a large quantity of gel particles was observed on dissolving the sample in DMAc containing 5% LiCl, indicating that considerable crosslinking had probably occurred. The rod-like polymer poly-p-benzamide (PPB) was prepared in similar fashion to MDA-I from p-aminobenzoic acid and IV values of respectively 1.6, 2.3, 3.8, and 3.9 were obtained when 0.0, 2.0, 2.5, and 3.0 mole-% of mixed trifunctional monomers were present. A solution of the latter sample dissolved in concentrated sulfuric acid contained considerable gel, indicating that crosslinked polymer was probably produced. It would appear that the chain branching approach for producing high molecular weight PPB for spinning to fibers will not prove useful because PPB having an IV value of about 3 to 4 is considered only marginal for the production of commercial-quality fibers (even though PPB of IV value 1.6 can be spun to high-strength/high-modulus fibers) and because the requisite balance of strength and modulus to elongation to break are only obtained for fibers from PPB having an IV value above about 3.5, and preferably about 5 to 6.

DNA condensation with polyamines: I. Spectroscopic studies

The addition of polyamines with three or four positive charges to very dilute solutions of phage T7 DNA leads to a co-operative condensation. The reaction is very rapid and the DNA remains in the B-form as characterized by circular dichroism. The particles which are formed are roughly the size of a phage particle when they are prepared for electron microscopy. This aspect is discussed more completely in the accompanying paper (Chattoraj et al., 1978). Most of the experiments were performed at low ionic strength (roughly 0.002 m) with the triamine, spermidine. The reaction also occurs in 0.15 m-sodium chloride but here the experiments are accompanied by slow irreversible effects which are evidently due to aggregation since they are accompanied by a commensurate increase in turbidity. Consequently, most of the experiments have been done under the reversible low ionic strength conditions. Neither Mg 2+ nor the diamine putrescine produce the reaction at concentrations similar to those found in bacterial cells. The tetramer spermine, on the other hand, which is not found in bacterial cells, is a very strong condensation agent in the μ m region. The spermidine analog, bis-(3-aminopropyl)amine is very similar in behavior to spermidine. The role which polyamines might play in the condensation of DNA in phage heads is discussed.

Re‐Use and Disposal of Waste Acids

AbstractHydrochloric acid and sulfuric acid represent the main waste acid by‐products in chemical manufacture. Neutralisation and conversion to inert solids as methods of disposal are of limited applicability. A number of appropriate methods have been developed for acid recycling. Hydrogen chloride (as a major by‐product of organic chlorination reactions) can be converted to chlorine by oxidation processes or by electrolysis of muriatic acid. Hydrogen chloride itself can be put to use in the synthesis of methyl chloride, vinyl chloride, chloroprene. Sulfuric acid serves as cheap solvent, reaction medium, condensation agent, drying agent, and gives rise to diluted and contaminated waste acids. Regeneration techniques (water evaporation by various methods, separation of precipitated salts, oxidation of organic impurities) lead to acids of sufficient quality to be recycled to the process of their origin. Standard grade sulfuric acid can be made from waste acids by thermal degradation to sulfur dioxide which in turn goes back to the sulfuric acid plant.

The Cross-Linking of Cotton Cellulose by Aliphatic Dicarboxylic Acids

Cross-linked, fibrous, cellulose diesters have been prepared using trifluoroacetic anhydride as a condensation agent for reaction of cotton fabric with eleven different, terminally-substituted, dicarboxylic acids ranging from malonic acid (C 3) to eicosane- 1,20-dicarboxylic acid (C22). In the range C2 to C5, only malonic acid reacts readily, oxalic acid being unreactive, while succinic and glutaric acids have qnly slight reactivity. With diadds from C6 to C 22, reaction occurs readily and a decrease in reactivity with chain length is observed. The reaction products are predominantly cellulose diesters containing a relatively small number of acid-ester residues. For each acid, the effect of varying the degree of cross-linking on the crease recovery, moisture regain, and water imbibition of the fabric has been determined. Crease recovery angles increase with the extent of reaction and, at equivalent degrees of cross-linking, longer chain acids effect more improvement in crease recovery than acids of shorter chain length. In geheral, both the nioisture regain and water imbibition of the fabric are decreased by esterification, the effect being greater the longer the acid chain length. Possible reasons for the observed effects are discussed.

臭素塩素混合置換フルオレスセインの合成

The condensation of the halogeno substitutes of 2-(2′, 4′-dihydroxybenzoyl) benzoic acid (II), derived from the decomposition of either chloro or bromo-fluorescein (I) in concentrated NaOH solution, and either resorcinol or its halogeno derivatives (III), afforded a new chloro-bromo mixed substituted fluorescein (IV), shown in Table I. When polyphosphoric acid was used as a condensation agent in the reaction, a debromination reaction scarecely took place, and a yield of IV was poor. If the condensation was proceeded at 120-150° in the presence of ZnCl2, a yield of IV was pretty rich, even though debromination reaction was accompanied, and the less number of halogeno substitute (IV) was produced subordinately. A little amount of by-products can be removed by treating them in ethanolic HCl, however, a comparatively larger amount of by-products should be separated through the column chromatography of alumina or magnesol, being followed by the elution with 2-3% NH4OH.The production of by-product can be easily identified by the paperchromatography, developed by the solvent mixture of N NaOH-10% C6H5OH-H2O (2:1:7).

Hydrogen Fluoride as a Condensing Agent. VI. Reactions of Fluoroölefins with Formaldehyde in Hydrogen Fluoride1

Hydrogen Fluoride as a Condensing Agent. VI. Reactions of Fluoroölefins with Formaldehyde in Hydrogen Fluoride¹

Studies on the some heterocyclic pyrimidine derivatives of nitrogen. II. Syntheses of pyrimidines

Five kinds of pyrimidine derivatives (VII) substituted in 2-position with phenyl, o-tolyl, p-tolyl, p-nitrophenyl, and p-bromophenyl groups were prepared, following the synthesis of 2-amino-4-methyl-5-ethoxycarbonylpyrimidine (I). 2-Ethoxymethyleneacetoacetate (III) was prepared from ethyl acetoacetate. Five kinds each of nitriles (IV), imidoethers (V), and amidine base hydrochlorides (VI) were prepared from aromatic primary amines such as aniline, o-toluidine, p-toluidine, p-nitroaniline, and p-bromoaniline. Condensation of the amidines (VI) with the ester (III), in the presence of sodium ethoxide as the condensation agent, resulted in smooth reaction to afford the corresponding esters (VII: R=C2H5). Hydrolysis of these esters (VII) by the usual method gave the corresponding free salts (VII: R=H). In the series of this work, condensation of acetamidine hydrochloride and the ester (III) failed to afford the pyrimidine derivative.

Water Insouble Dyes Containing s-Triazine Ring. I

p-Aminoazobenze ne, 4-amino-1, 1'-azonaphthalene, 1-amino-4-cyclohexyl-aminoanthraquinone, and 1-amino-4-hydroxyanthraquinone, respectively, is made to react with cyanuric chloride to give a dichloro-s-triazine type pigment, (F=residual group of the pigment). Reaction of this with monoethanolamine, diethanolamine, N, N-diethylethyl-enediamine, and ethylenimine, respectively yielded dyes with general formula, where R=H or R'; R'=-CH2CHZOH, -CH2CH2N(C2H5)2 or The dyeing properties of these pigments with substituent groups, such as -N(CH2CH2OH)2 and -NHCH2CH2OH were considerably selective, and Nylon. Vinylon and acetate fibers were dyed well, but cotton, rayon. Tetron and acrylonitrile type fibers were not dyed by these pigments. The basic pigments having a substituent group, -NHCH2CH2N(C2H5)2, showed the characteristics of basic pigment and had less selective property, they dye silk well, and the dyeing properties to rayon, wool and acrylonitrile type fibers was increased, while that of to Nylon, Vinylon and acetate fibers decreased. The quarternary salt also showed the same dyeing property. The products containing ethyle-nimino group as substituent had a charcteristic of reactive or polymerizable pigment, they were fixed on cotton by a mere heating at 110-30°c without condensation agent such as alkali, and the dyed materials were fast against the extraction test with pyridine.

Synthesis of penicillins using dicyclohexylcarbodiimide as a condensing agent.

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSynthesis of Penicillins Using Dicyclohexylcarbodiimide as a Condensing AgentDonald C. Hobbs and Arthur R. EnglishCite this: J. Med. Chem. 1961, 4, 1, 207–210Publication Date (Print):July 1, 1961Publication History Published online1 May 2002Published inissue 1 July 1961https://doi.org/10.1021/jm50017a015RIGHTS & PERMISSIONSArticle Views199Altmetric-Citations7LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (197 KB) Get e-Alerts

糖-アミノ酸結合体の研究 (第2報)

In order to synthesize the glycine ester of D-glucose, attempt was made to obtain the starting material, 6-O-(N-benzyloxycarbonylglycyl)-D-glucopyranose, by esterification of N-benzyloxycarbonylglycine with glucose derivative and it was found that dicyclohexylcarbodiimide is a good condensation agent. Compared to the ester condensation of N-benzyloxycabonylglycine and glucose derivative with mixed anhydride of other acids, the use of dicyclohexylcarbodiimide as the condensation agent was found to have the advantage of not forming a large amount of by-products. Further, the latter reagent was found to have entirely no effect on the urethan bond like N-benzyloxycarbonyl group. This process was used to obtain N-benzyloxycarbonylglycine ester of four kinds of glucose derivatives whose hydroxyls other than that at 6-position were protected, and three of them easily afforded 6-O-(N-benzyloxycarbonylglycyl)-α-D-glucopyranose.

Studies on Nitroparaffins. VIII

Reaction of 1-nitropropane and ethyl acrylate in 3:1 molar ratio in the presence of basic condensation agent was proceeded easily with Michael condensation reaction and gave ethyl 4-nitrocaproate. Caustic alakali, carbonate of alkali, sodium bicarbonate, sodium amide, and sodium methylate, etc., were used as the condensation agents, among which sodium hydroxide gave the best result and the objective substance was obtained in 67.6% yield by heating for 5 hrs at 40-45°C.Saponification of the ethyl 4-nitrocaproate with sodium hydroxide solution and application of so-called Nef reaction of using dilute sulfuric acid on an intermediate acid-type salt gave a transition into corresponding 4-ketocaproic acid. The effects of reaction temperature, amount and concentration of sulfuric acid have been investigated. It was indicated that the reaction with dilute sulfuric acid (1: 4.4) at 3-5°C yielded 74.2% 4-ketocaproic acid.

アセトブチロラクトンのPechmann反応

Pechmann reaction was carried out on α-acetyl-γ-butyrolactone with 73% sulfuric acid or phosphoryl chloride as the condensation agent. Corresponding 4-methyl-coumarin derivatives were obtained from resorcinol, pyrogallol, phloroglucinol, and 1-naphthol and ultraviolet absorption spectra of these derivatives were measured. 7-Hydroxy-3-(2-hydroxyethyl) derivative, m. p. 226-228°; 7-hydroxy-3-(2-chloroethyl) derivative, m. p. 186-188°; 7, 8-dihydroxy-3-(2-hydroxyethyl) derivative, m. p. 241-242°; 7, 8-dihydroxy-3-(2-chloroethyl) derivative, m. p. 206°; 5, 7-dihydroxy-3-(2-chloroethyl) derivative, m. p. above 300°; 7, 8-benzo-3-(2-hydroxyethyl) derivative, m. p. 164°.

New Synthesesi of Fatty Derivatives

For mono-alkylation of amino group in aromatic primary amines, it is necessary to use a special alkylating method and alkylating agent. The object is easily attainable by use of W-2 Raney Ni. Namely, heating of aniline in higher alcohol at 120-130°C in the presence of W-2 Raney Ni catalyst givesN-higher alkylaniline with comparatively good yield. This reaction is useful for syntheses of intermediates of surface-active agent and textile auxiliarity. Summaries on Report II.N-Dodecyl urethane was synthesized by the condensation of dodecylamine and ethyl chloroformate, and interesterification between this and ethylenebromohydrin gave bromomethyl N-dodecylcarbamate. Cyclization of this bromomethyl N-dodecylcarbamate in the presence of alkali condensation agent gave an objective N-dodecyloxazolidone. Also, heating of N-dodecyloxazolidone in vacuo caused its decomposition with the liberation of CO2and gave a polymer.Summaries on Report III. 6-Undecy1-2, 4-diamino-1, 3, 5-triazine was synthesized by heating lauronitrile and dicyandiamide in Ethyl Cellosolve.Similarly, 6-lauroylaminoethy1-2, 4-diamino-1, 3, 5-triazine was obtained from lauroylaminopropionitrile and dicyandiamide.The amino group in these diaminotriazines having long alkyl group can easily be hydroxymethylated with formalin and these are useful for permanent softening and water-proofing of textiles as they have the property of combining with the hydroxyl group in cellulose.

Studies on Streptomyces Antibiotic, Cycloheximide. VIII. Hydroxycarbonylation of Optically Active 2, 4-Dimethylcyclohexanone and Chemical Correlation of the Products. (1)

The condensation of cis-d-2, 4-dimethylcyclohexanone with para-substituted benzal-dehyde was carried out using tetramethylammonium hydroxide (aldol condensation) or N-methylanilinomagnesium bromide (Nielsen's condensation) as a basic condensation agent. Aldol and Nielsen's condensation gave the stereoisomeric hydroxycarbonylation products, ketol-As and ketol-Ns, respectively, the former showing positive [α]D values and the latter, negative values.

STUDIES ON THE DYEING OF DIFFICULT DYEING FIBERS

On the dyeing results in the former report, the reaction mechanisms were investigated in point of hue, fastness and some qualitative tests.It is considered that all components do not react on fiber at every stage, but that in one the hue changed one after another. and in another the light fastness remarkably increased. The pigment formed in the condensation process does not dye, but the fiber can be dyed deeply and fast by this dyeing method.These reaction mechsms are not yet known to us in detail, but it is thought that some reactions occure successively. Q1 and N1 are oxidizing and condensation agents, dedced from a comparative test with lead peroxide or the separation of chlorine ion from chloranil which was used instead of Ql.The hue of dyed fiber was dependent upon the active group of the first component-Q1 series being brown, Hl and N1 series blue high croma. These three active components easily react with each other on the fiber, in spite of the low light fastness.

アミノ酸より環状含窒素化合物の合成 (第4報)

Aromatic acyl derivatives of 5-aminopentanoic acid, obtained by the Beckmann rearrangement of cyclopentanone oxime, when dry-distilled with soda lime, barium oxide, sodium amide, or zinc dust, afford a mixture of partially hydrogenated 2-arylpyridines, together with water vapor, ammonia, and inflammable gas. Dehydrogenation of this mixture easily affords 2-arylpyridine. Soda lime is the most effective condensation agent for 5-benzoylaminopentanoic acid (I) and the effect decreases in the order of zinc dust, sodium amide, and barium oxide. The yield also decreases in the respective order of 50%, 30%, 12%, and 3%, calculated as 2-phenyl-3, 4, 5, 6-tetrahydropyridine (II). Dehydrogenation of (II) could best be effected by heating with palladium black, in the presence of safrole, at 170-180° for 4-5 hours, from which 2-phenylpyridine (III) is obtained in 90-95% yield. The picrates of (II) and (III) do not show any depression of the melting point on admixture.Dry-distillation of (I) affords a non-basic substance, in 7-8% of the starting material, and this consists of biphenyl, acetophenone, and benzonitrile.Dry-distillation of 5-o- and -p-toluamidopentanoic acid with soda lime affords 2-tolyl-hydropyridine in 40% yield, whose dehydrogenation easily gives the corresponding 2-tolylpyridine.

アミノ酸より環状含窒素化合物の合成 (第2報)

A condensation agent prepared by heating polyphosphoric acid (30g. of phosphorus pentoxide in 85% phosphoric acid) with 1/3 to 1/4 its amount of phosphoryl chloride on a water bath for 2 hours was used in heating the ethyl ester of N-acetyl-, -benzoyl-, -phenylacetyl-, and -formyl-L-cystelne at 150-160° (bath tem.) for 2 hours and 2-methyl-, -phenyl-, and -benzyl-thiazoles and thiazole were obtained in a respective yield of 4%, 20%, 10%, and 1%. Similar treatment of the diethyl ester of diacetyi-L-cystine the presence of stannous chloride afforded 2-methylthiazole, though in a small amount.As for the reaction mechanism for this formation of thiazole, it was assumed that it is the same as the formation of the isoquinoline ring from phenylalanine, reported in the preceding paper, since the reaction is accompanied with generation of carbon monoxide.

N<sup>1</sup>-Acyl-4-acetaminonaphthalenesulfonamideの合成 (第3報)

N1-Acylation of 4-acetaminonaphthalene-1-sulfonamide using condensation agents other than pyridine, such as trimethylamine, quinoline, or dimethylaniline, with acetone and sodium hydrogen carbonate, was compared with that of the pyridine method and a few new observations were made.

ピリミジン誘導体の合成研究 (第1報)

Condensation-cyclization of 6-guanidinohexanoic acid (I) and chloromalonaldehyde in equimolar amounts in conc. sulfuric acid, by the application of chlorosulfonic acid under ice cooling, yielded 6-(5-chloro-2-pyrimidinyl) aminohexanoic acid (IV). Similar reaction with application of bromomalonaldehyde afforded the corresponding 5-bromo compound. Reaction of the hydrochloride of (I) and sodium nitromalonaldehyde in aqueous solution, with piperidine as a condensation agent, at room temperature yielded 6-(5-nitro-2-pyrimidinyl) aminohexanoic acid (VI), whose reduction with stannous chloride and hydrochloric acid gave the corresponding 5-amino compound (VII). Whereas (I) was resistant to esterification by the ordinary method, (VI) easily submitted to esterification. Fusion of a mixture of 2-methylthio-4, 6-dimethylpyrimidine (XI) and 6-aminohexanoic acid by heating to 200° in an oil bath afforded 6-(4, 6-dimethyl-2-pyrimidinyl) aminohexanoic acid. (XI) was prepared from acetylacetone and S-methylisothiourea according to the method of Hale and others. At the same time, some white needle crystals (X), m. p. 155.5-156°, were obtained as a by-product, whose analytical values corresponded to the formula of C7H10N4 and the substance was determined as 4, 6-dimethylpyrimidine-5-carbamidine by the synthesis of its derivatives.