Dichloromaleic Anhydride Research Articles

Bindungsdelokalisierte Betaine; 1. Mitteilung. Neuartige Stickstoff-, Phosphor- und Arsen-Betaine des Maleinsäure-anhydrids durch Dreikomponenten-Reaktion

Bond-Delocalized Betaines; Part 1. Novel Nitrogen, Phosphorus and Arsenic Betaines of Maleic Anhydride by a Three-Component Reaction Novel betaines derived from maleic anhydride were prepared by reaction of dichloromaleic anhydride with a cationogenic species such as pyridines, isoquinoline, quinoline, pyrazine, 1-methylimidazole, 4-methylmorpholine, triphenylphosphine, or triphenylarsine and water (Method A) or acetic anhydride (Method B).

ChemInform Abstract: High Pressure (4 + 2) Cycloaddition Reactions of 3,4‐Dimethoxyfuran with Dichloromaleic Anhydride and with Cyclopropane Derivatives.

Abstract3,4‐Dimethoxyfuran undergoes a cycloaddition reaction with dichloromaleic anhydride (II) under high pressure to give the adduct (III) which rearranges to yield (IV).

High pressure [4 + 2] cycloaddition reactions of 3,4-dimethoxyfuran with dichloromaleic anhydride and with cyclopropane derivatives

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTHigh pressure [4 + 2] cycloaddition reactions of 3,4-dimethoxyfuran with dichloromaleic anhydride and with cyclopropane derivativesKiyoshi Matsumoto, Yukio Ikemi, Shiro Hashimoto, H. S. Lee, and Yoshiyuki OkamotoCite this: J. Org. Chem. 1986, 51, 19, 3729–3730Publication Date (Print):September 1, 1986Publication History Published online1 May 2002Published inissue 1 September 1986https://doi.org/10.1021/jo00369a040RIGHTS & PERMISSIONSArticle Views153Altmetric-Citations11LEARN 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 (267 KB) Get e-Alerts Get e-Alerts

Copolymerization of styrene with α‐chloromaleic anhydride, 2. Spontaneous copolymerization in 1,4‐dioxane

Abstractα‐Chloromaleic anhydride (CMA) copolymerizes spontaneously with styrene (ST) at a higher rate than maleic anhydride (MA), and α,α′ ‐dichloromaleic anhydride (DCMA) does not copolymerize, even in the presence of a radical initiator. The results obtained from the copolymerization of ST with CMA in 1,4‐dioxane in the absence of a radical initiator are as follows: the copolymerization is strongly accelerated by UV‐irradiation; the monomer reactivity ratios of ST and CMA at 60°C are 0,06 and 0,00, respectively; the over‐all activation energy of the copolymerization is 77,4 kJ · mol−1 (18,5 kcal · mol−1); the maximum rate of copolymerization at a constant total monomer concentration is observed at a mole fraction of ST of 0,4 to 0,5. The rate of copolymerization at equimolar feed composition is of second order with respect to the total monomer concentration. From the results obtained here and shown in the preceding paper, it was inferred that initiating radicals for the spontaneous copolymerization are formed through a charge transfer (CT) complex between the comonomers.

The use of esters of dichloromaleic acid in intramolecular diels alder reactions

Intramolecular cyclisation of acyclic triene esters derived from dichloromaleic anhydride affords bicyclic lactones, which by dechlorodecarboxylation, dechlorination or dehydrochlorination are readily elaborated to give novel unsaturated lactones.

Essai de stabilisation du polychlorure de vinyle par un système totalement organique

Owing to its Lewis acid character, dichloromaleic anhydride (DCAM) has been tried as a thermal stabilizer of polyvinylchloride (PVC), in association with nucleophilic oxiranes; comparative experiments have been carried out using maleic anhydride and maleic acid. Chlorohexene was used as model compound for labile allylic chloride in dichlorobutane solution at 80°. Experiments with plasticized PVC were carried out at 180°. DCAM in an efficient catalyst for the production of the intermediate carbocation, although it is less efficient than organostannic chlorides; it causes oxirane polymerization and other secondary reactions more than nucleophilic substiution on the carbocation. Moreover it is not an efficient dienophilic agent for conjugated polyene, although it gives with them a strongly coloured complex. For these reasons, it cannot be used as a major component of a stabilizer recipe for PVC.

Synthesis of mono and difunctional oligoisobutylenes—III. Modification of α-chlorooligoisobutylene by reaction with maleic anhydride

Reaction of monofunctional oligoisobutylene with maleic anhydride is described. In a preliminary study, thermal dehydrochlorination of α-chlorooligoisobutylene is examined; the double bond of the resulting olefin can be endo or exo. Ene reaction of maleic anhdride with this oligomer is first studied on a model, 2,4,4-trimethyl-1-pentene; resulting mixture is completely analysed by 13C- and 1H-NMR spectroscopy: two isomeric oligomer anhydrides are formed. Ene synthesis is also carried out on α-(2-methyl-2-propenyl)oligoisobutylene; only exo bonds are able to react; the functionality of the resulting oligomeric anhydride mixture is 0.92. In the presence of a catalyst (dichloromaleic anhydride) disubstitution can take place, because the double bond formed in the first reaction is able to react a second time with maleic anhydride.

Synthesis of mono and difunctional oligoisobutylenes—IV. Modification of α,ω-dichlorooligoisobutylene by reaction with maleic anhydride. Preliminary study on block polycondensation

Thermal dehydrochlorination of α,ω-dichlorooligoisobutylene leads to the formation of both endo and exo double bonds; endo bonds are mainly those of 4-phenyl-2,4-dimethyl-2-pentene; exo double bonds belong either to “short” end-groups. Reaction of dichlorinated oligomers with maleic anhydride gives a mixture of oligomers with anhydride or substituted propenyl or indanic terminations. Pure α,ω-di(2-methyl-2-propenyl)oligoisobutylene was prepared by basic dehydrochlorination of α,ω-dichlorinated oligomer; only exo double bonds are formed. This α,ω-unsaturated oligomer reacts with maleic anhydride, giving an oligomeric mixture with functionality, with respect to anhydride, of 1.25 but containing endo double bonds and indane rings. When a catalyst is added (dichloromaleic anhydride), two molecules of anhydride can react with the same end of chain. Various polyamides were prepared from the α,ω-dianhydride oligomers.

2 + 2] Photocycloadditions of dichloromaleimide and dichloromaleic anhydride to cyclic olefins

The photocycloaddition of dichloromaleimide to cyclohexadiene, cyclopentadiene, and cyclopentene on direct photolysis gave [2 + 2] addition products with the cis,endo- and cis,exo-configurations as the major products. However, a similar photocycloaddition to cyclohexene yielded the trans-fused cycloaddition product (between the four- and six-membered rings) as the major product in addition to the cis,endo- and cis,exo-isomers. The photocycloadditions of dichloromaleic anhydride to cyclopentadiene and cyclohexadiene were reinvestigated; two major products were obtained which were identified as the cis,endo- and cis,exo-addition products, while the reported trans-fused isomers were not isolated. The structures of these photoaddition products were investigated by 400 MHz n.m.r. spectroscopy to ascertain the configuration of the ring fusion. An X-ray crystallographic analysis established the stereochemistry of one product.

High pressure [4 + 2] cycloaddition of dichloromaleic anhydride and furan

High pressure [4 + 2] cycloaddition of dichloromaleic anhydride and furan

The Low Lying Electronic States of Dichloromaleic Anhydride

Abstract The polarized Raman and infrared spectra of dichloromaleic anhydride were studied and the assignments of the normal vibrations were reinvestigated based on the polarization behaviors of the spectral bands and on the normal coordinate calculation. Using the assignments the vibrational structure of the phosphorescence spectrum was analyzed and the phosphorescence lifetime was also measured. These results indicate that the lowest triplet state of this molecule is a 3(π, π*) state perturbed by closely located 3(n, π*) states. The near ultraviolet absorption and phosphorescence excitation spectra were measured and four absorption bands due to 3(n, π*)←1A1, 1A2(n, π*)←1A1, 1B1(n, π*)←1A1, and 1A1(π, π*)←1A1 transitions were found. The polarization experiment made on the 1A2(n, π*)←1A1 absorption suggests that this transition borrows the intensity from the 1A1(π, π*)←1A1 transition.

Phosphorus-Containing Imide Resins. I

Abstract Recently we reported the general features of bisimide resins based on bis(m-aminophenyl)methylphosphine oxide. Graphite fabric composites fabricated from one of these resins did not burn in pure oxygen even at 300°C. However, curing of these resins was done above 270°C. It is desirable to have organic matrix resins with lower curing temperatures. We now report the synthesis of several bislmides and triimide resins based on tris(m-aminophenyl)phosphine oxide. These monomers were prepared according to the procedure of Searle or Martin et al. by reacting triamine with appropriate amounts of maleic anhydride, citraconic anhydride, dichloromaleic anhydride, and benzophenone tetracarboxylic dianhydride. Cross-linked imide resins insoluble in DMF were obtained by thermal polymerizations at 180°C with some of these monomers. Anaerobic char yields at 800°C in the range of 60–70% were obtained. A four-ply graphite cloth laminate prepared from one of these resins at 180°C, and after postcuring at 220°C for 4 h, had a limiting oxygen index above 100. The glass transition temperature of this laminate (as evaluated by DMA) was 385°C.

Surface interaction in the [formula omitted] system

A rapid (1.5 h) one-step ball milling (BM) method was developed to synthesize VOx/TiO2 (VTi-BM) and WOx or MoOx doped VOx/TiO2 (VWTi-BM or VMoTi-BM). Catalytic activity on gaseous POPs removal was tested using hexachlorobenzene (HCB) as surrogate. Catalytic performance decreased in the order of VWTi-BM (T50% = 230 °C) > VMoTi-BM (260 °C) > VTi-BM (270 °C) > VTi-WI (300 °C; VOx/TiO2 synthesized by wetness impregnation method). The intermediates from oxidation of HCB were analyzed by off gas analysis, from which 2,2,4,5-tetrachloro-4-cyclopentene-1,3-dione (TCCD), dichloromaleic anhydride (DCMA) and tetrachloro-1,4-bezoquinone (TCBQ) were identified. Furthermore, a possible mechanism for the oxidation of HCB over VOx/TiO2 catalysts was proposed. Mechanism studies showed that BM samples possess better dispersion of the VOx species and more surface chemisorbed oxygen. Doping WOx or MoOx into VOx/TiO2 by ball milling can further enhance catalytic performance by increasing surface acid sites.

Preparation of maleic anhydride derivatives by catalytic oxidation of halogenobutadienes

1. 1. A study was made using a laboratory continuous device of oxidation of chloroprene to chloromaleic anhydride (chloromaleic acid) in a fluidized layer of a vanadium-phosphorus catalyst. At the optimum temperature of 470°C, a contact time of 0·80 sec maximum chloromaleic acid yield (32·0 wt.%) is ensured; catalyst output is 203 g of chloromaleic acid/l.·cat·hr. 2. 2. A study was made of oxidation of hexachlorobutadiene to dichloromaleic anhydride on a VP catalyst. The optimum temperature was found to be 480°C, contact time 0·70 sec. Under the conditions observed process selectivity was 80 mole % with 90% conversion of hexachlorobutadiene.

Seven-membered acetals based on cis-2,3-Dichloro-2-butene-1,4-diol

cis-2,3-Dichloro-2-butene-1,4-diol was obtained by reduction of dichloromaleic anhydride with lithium aluminum hydride. Condensation of the diol with carbonyl compounds leads to seven-membered unsaturated acetals, viz., 5,6-dichloro-1,3-dioxa-5-cycloheptenes.

ChemInform Abstract: AN ELECTRON DIFFRACTION INVESTIGATION OF THE MOLECULAR STRUCTURE OF DICHLOROMALEIC ANHYDRIDE

Abstract The molecular structure of gaseous dichloromaleic anhydride has been investigated by electron diffraction at a nozzle-tip temperature of 164–170°C. The molecule is planar to within experimental error, but small deviations from planarity corresponding to torsion up to about 10° around the carbon-carbon single bonds cannot be ruled out. Values of the more important r α distances and angles with estimated 2σ uncertainties are r (CO) = 1.188(2) A, r (CC) = 1.332(5) A, r (C-O) = 1.389(3) A, r (C—C) = 1.495(3) A, r (C—Cl) = 1.685(2) A, ∠CC-Cl = 129.4(2)°, ∠C-CO = 128.5(4)° and ∠CC—C = 107.9(2)°. The shortening of the carbonyl bond relative to that in maleic anhydride itself is discussed in terms of a possible general effect of vicinal substitution.

An electron diffraction investigation of the molecular structure of dichloromaleic anhydride

The molecular structure of gaseous dichloromaleic anhydride has been investigated by electron diffraction at a nozzle-tip temperature of 164–170°C. The molecule is planar to within experimental error, but small deviations from planarity corresponding to torsion up to about 10° around the carbon-carbon single bonds cannot be ruled out. Values of the more important r α distances and angles with estimated 2σ uncertainties are r(CO) = 1.188(2) Å, r(CC) = 1.332(5) Å, r(C-O) = 1.389(3) Å, r(C—C) = 1.495(3) Å, r(C—Cl) = 1.685(2) Å, ∠CC-Cl = 129.4(2)°, ∠C-CO = 128.5(4)° and ∠CC—C = 107.9(2)°. The shortening of the carbonyl bond relative to that in maleic anhydride itself is discussed in terms of a possible general effect of vicinal substitution.

Polymer Formation by ylrradiation of Dichloromaleic Anhydride (DC I MA) in Benzene Solution

Abstract In the γ-irradiation of dichloromaleic anhydride (DC1MA) in benzene solution, the first step of the reaction, analogous to photochemistry, is the formation of α-chloro-α-phenyl-maleic anhydride (CIPhMA). In contrast to photochemistry, where this intermediate is transformed into a cycloaddition product, a polymer is formed in radiolysis. The polymer consists of CIPhMA units as well as components resulting from benzene radiolysis.

ChemInform Abstract: PHOTOCYCLOADDITION OF DICHLOROMALEIC ANHYDRIDE TO BENZENE

AbstractBei UV‐Bestrahlung einer Lösung von Dichlor‐maleinsäureanhydrid (II) in Benzol (I) erhält man das Dianhydrid (V), vermutlich durch Kondensation der beiden Zwischenverbindungen (III) und (IV).

Photocycloaddition of dichloromaleic anhydride to benzene

In the photocycloaddition of dichloromaleic anhydride to benzene the processes of addition and substitution in the benzene ring proceed in parallel, and also the subsequent photoreaction of the obtained products to give compounds of the tricyclo[6.2.05,6.04,7]decene series.