The spectra of 3-OXO-2, 3-dihydrothianaphthene and its derivatives

Condensation of isatin--anil with acetylacetone and with derivatives of malonic and acetoacetic acids in acetic anhydride has given 5 indogenides. It is observed that isatin--anil is readily acetylated by acetic anhydride. The acetyl derivative is very reactive, and is an intermediate in the condensation of isatin--anil with acetylacetone in acetic anhydride. The indogenides which have been synthesized are nonphototropic as a result of the presence of intramolecular hydrogen bonds.For part IX, see [1].     

1,3-diphenyl-2-azaanthracene and 8-aza-7-phenylbenzo[a]fluoranthene in the diene synthesis

The diene condensation of 1,3-diphenyl-2-azaanthracene with maleic anhydride proceeds under more severe conditions than the analogous condensation with anthracene. On the basis of an analysis of the PMR data for the adduct obtained it was assumed that isomers of ,-[9,10-dihydro-2-aza-1,3-diphenylanthrylene(9,10)]succinic anhydride with respect to the position of the anhydride bridge relative to the pyridine ring are formed in this condensation. 9,10-Dihydro-2-aza-1,3-diphenyl-9, 10-(1-cyanoethylene)anthracene was obtained in the condensation of the same azaanthracene with acrylonitrile. ,-[5H-8-Aza-7-phenylbenzo[a]fluoranthrylene (5,12b) ]succinic anhydride is formed as a result of the similar condensation of 8-aza-7-phenylbenzo[a]fluoranthene with maleic anhydride, while isomeric (with respect to the position of the nitrile group in the ethylene bridge) 5H-8-aza-7-phenyl-5,12b-(cyanoethylene)benzo[a]fluoranthenes were isolated in its condensation with the acrylonitrile. Data from the PMR and IR spectra were used to prove the structures of the adducts of the diene synthesis obtained.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1645–1647, December, 1980.     

Silica Matrix with anhydride groups for immobilization of enzymes

We have studied the process of preparing a silica support with anhydride groups. The process includes introducing vinyl groups onto the surface with subsequent radiative copolymerization of maleic anhydride with them. The maximum degree of grafting of the functional groups of the matrix occurs for -irradiation doses of 20–30 Mrad. The carboxyl groups grafted to the aerosil surface, formed upon hydrolysis of the support, can be converted to anhydride by calcination at 403 K for 3 h.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 6, pp. 750–753, November–December, 1989.     

Polyetherimides. I. Preparation of dianhydrides containing aromatic ether groups

A general synthetic method and characterization of bis(ether anhydride)s, the ether containing aromatic dianhydrides of the following structure, are presented. The method involves aromatic nitro-displacement of N-substituted 3- or 4-nitrophthalimide with bisphenoxides to form N-substituted arylene-bis(phthalimido)ethers or bis(ether imide)s. Sixteen structurally different bis(ether imide)s have been prepared and subsequently converted to the corresponding bis(ether anhydride)s. Bis(ether anhydride)s are stable crystalline compounds of a moderate reactivity. Unlike highly reactive dianydrides such as pyromellitic and benzophenonetetracarboxylic dianhydrides bis(ether anhydride)s are semipermanently stable against hydrolysis in the presence of atmospheric moisture.     

Covalent Immobilization of Subtilisin A onto Thin Films of Maleic Anhydride Copolymers

Enzymes cleaving the biopolymer adhesives of fouling organisms are attracting attention for the prevention of biofouling. We report a versatile and robust method to confine the serine protease Subtilisin A (or Subtilisin Carlsberg) to surfaces to be protected against biofouling. The approach consists of the covalent immobilization of the protease onto maleic anhydride copolymer thin film coatings. High‐swelling poly(ethylene‐alt‐maleic anhydride) (PEMA) copolymer layers permitted significantly higher enzyme loadings and activities than compact poly(octadecene‐alt‐maleic anhydride) (POMA) films. Substantial fractions of the immobilized, active enzyme layers were found to be conserved upon storage in deionized water for several hours. Ongoing studies explore the potentialities of the developed bioactive coatings to reduce the adhesion of various fouling organisms.

     

Tandem A N—A N reactions in the synthesis of 1H-pyrrolo[3,2-e]-1,2,4-triazines and products of their oxidative transformations

The reactions of 3-aryl-1,2,4-triazines with -aminovinyl ketones or ethyl -aminocrotonates in acetic anhydride at room temperature afforded cyclic products of the tandem nucleophilic addition, viz., 3a,4,7,7a-tetrahydro-1H-pyrrolo[3,2-e]-1,2,4-triazines, in good yields. Under oxidative conditions, the latter compounds underwent the pyrrole-ring opening under the action of potassium permanganate to form the corresponding triazinones and were transformed into thriazolyl-substituted pyridines under the action of selenious acid.     

Morphology Evolution during the Phase Separation of Polyetherimide/Epoxy Blends

The results of time‐resolved light scattering for the phase separation of epoxy/polyetherimide/anhydride blends show that the evolution of scattering vector q_m follows a Maxwell‐type relaxation equation. The relaxation time may be suggested as the time taken for the diffusion of the epoxy‐anhydride n‐mers from the PEI‐rich phase by their relaxation movement, and the apparent activation energy of the relaxation movement is obtained.

Values of q_m versus time at different temperatures.     

Reaction of triphenylantimony and triphenylbismuth withtert-butyl peracetate

Triphenylantimony and triphenylbismuth diacetates, Ph₃M(OAc)₂ (M = Sb, Bi), were obtained in 50–94 % yields by the reaction of triphenylantimony and triphenylbismuth withtert-butyl peracetate in the presence of acetic acid or acetic anhydride (molar ratio 1 1 1) in toluene.tert-Butyl peracetate oxidizes Ph₃M into alkoxides, Ph₃M(OAc)OBu^t, which at the instant of formation are acylated with acetic acid or acetic anhydride to give the corresponding derivatives, Ph₃M(OAc)₂.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 964–967, May, 1995.This study was financially supported by the Russian Foundation for Basic Research (Grant 94-03-08846).     

Synthesis,structure, and spectral and photochemical properties of fulgides of the indole series with an adamantylidene fragment

New fulgides of the indole series with adamantylidene fragments were synthesized: 3-(adamant-2-ylidene)-2-[1-(3-indolylethylidene)]succinic anhydride (I) and 3-(adamant-2-ylidene)-2-(3-indolylmethylene)]succinic anhydride (2). By means of electronic absorption and¹H NMR spectroscopy and X-ray diffraction analysis, fulgides1 and2 were shown to haveZ- andE-configurations, respectively. The photochemical properties of1 and2 were studied. It was shown that along withZ-E photoisomerization of these compounds, in solution they undergo a cyclization reaction to yield a colored photoproduct. Specific structural features of fulgide1 affecting its photochemical properties were discussed. The introduction of a bulky adamantylidene group decreases the extent of the conversion of compound1 into cyclic isomerC.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2301–2305, September, 1996.     

Stereochemistry of cyclic compounds Communication 64. Stereochemistry of the oxidation and bromination of 4,5-dimethyl-4-cyclohexene-cis-1,2-dicarboxylic acid and its anhydride

Conclusions A study was made of the oxidation and bromination of 4,5-dimethyl-4-cyclohexene-cis-1,2-dicarboxylic acid (I) and its anhydride (II), and proof is given for the configurations of the then formed-epoxy anhydride (III), 5-hydroxy and 5-bromo-lactone acids (IV) and (V), and cis-glycol (IX). On the basis of the results of the acid hydrolysis of the trans-dibromo anhydride (VI) it is suggested that the bromine atoms in this compound have a diaxial arrangement.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 689–695, April, 1966     

Heats of solution and neutralization ofLewis acids and bases in acetic anhydride

Heats solution of someLewis acids and bases in acetic anhydride have been determined and the following order of their relative strengths is proposed: SbCl₅>SO₃>SnCl₄>TiCl₄>AsCl₃ and piperidine> n-butylamine>potassium acetate>sodium acetate -picoline>quinoline. Heats neutralization of theseLewis acids and bases in acetic anhydride suggest that the major enthalpy change in these neutralization reactions is due to the combination of a proton and the (CH₂COOCOCH₃)-ion, resulting in the formation of acetic anhydride.

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Lösungs- und Neutralisationswärmen von Lewis-Säuren und-Basen in Essigsäureanhydrid

Zusammenfassung Es wurden die Lösungswärmen einigerLewis-Säuren in Essigsäureanhydrid bestimmt und folgende Reihung nach ihrer relativen Stärke vorgeschlagen: SbCl₅>SO₃>SnCl₄>TiCl₄>AsCl₃ und Piperidin> n-Butylamin>KAc>NaAc-Picolin>Chinolin. Die Neutralisationswärmen dieserLewis-Säuren und-Basen legen nahe, daß der Hauptanteil daran auf die Reaktion eines Protons mit (CH₂–COOCOCH₃)-zurückzuführen ist.

     

Synthesis of benzo[g]quinoline derivatives

It has been established that the cyclization of -(2-carboxy-3-naphthylamino)propionic acid into N-acetyl-4-oxo-1, 2, 3, 4-tetrahydrobenzo[g]quinoline takes place with the participation of acetic anhydride and an alkali metal acetate. In the absence of the alkali metal acetate cyclization takes place in a different direction. A mechanism for this reaction has been proposed as taking place through the formation of an internal mixed anhydride, which decomposes under the reaction conditions into N-acetyl-4-oxo-1, 2, 3, 4-tetrahydrobenzo[g]-quinoline and carbon dioxide.For part V, see [1].     

Fluorosulfonyl-containing heterocyclic compounds

When hexafluoroisobutenylidene sulfate is heated above 80°C, hexafluorodimethylketene is liberated and the inner anhydride of hexafluoro--pyrosulfoisobutyric acid (I) is formed. On storage, anhydride I is spontaneously isomerized to hexafluoroisobutenylidene pyrosulfate, which is converted to the mixed anhydride of pentafluoromethacrylic and fluoropyrosulfonic acids on heating above 130° for many hours. On heating above 160°, I is decarboxylated to give hexafluoropropane-2,2-disulfonic acid anhydride, which is inclined to isomerize to pentafluoropropene-2-pyrosulfonyl fluoride.See [1] for Communication IV.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No, 10, pp. 1321–1324, October, 1973.     

Synthesis of 3-phenyl- and 3-phenyl-1-methylimidazo [5, 1-b] benzoxazoles

Reduction of 2-benzoylbenzoxazole oxime gives 2-(-aminobenzyl) benzoxazole, converted to the formyl or acetyl derivative by treatment with, respectively, ethyl formate or acetic anhydride. Thiourea derivatives are obtained by treating 2-(-aminobenzyl) benzoxazole with arylisothiocyanates. Heating the above formyl or acetyl derivative with phosphorus oxychloride converts them to 3-phenyl- and 3-phenyl-1-methylimidazo [5, 1-b]-benzoxazole, which are representative members of a new tricyclic system. It did not prove possible to cyclize 1-[-(benzoxazolyl-2) benzyl]-3-phenylthiourea.     

Controlled Release of IgG by Novel UV Induced Polysaccharide/Poly(amino acid) Hydrogels

The development of new protein and peptide drugs needs new delivery systems able to entrap such drugs in safe conditions without affecting their structure and biological activity. In this context, the present work reports a new approach to load IgG, used as a model of therapeutic proteins such as anti‐TNF‐α monoclonal antibodies, into a polymeric system able to release the entrapped IgG in a controlled manner. In particular, new polysaccharide/poly(amino acid) UV induced hydrogels are proposed as colon delivery systems for human IgG. The poly(amino acid), α,β‐poly[N‐(2‐hydroxyethyl)‐D ,L ‐aspartamide], has been functionalized with methacrylic anhydride, while the polysaccharide, inulin, has been functionalized with methacrylic anhydride and succinic anhydride. The hydrogels were obtained by a short‐time UV irradiation, in physiological‐like conditions, without the use of radical initiators, at low temperature and in the presence or in the absence of PEGDM₅₅₀ used as a co‐crosslinker in order to evaluate potential differences in terms of physicochemical properties and release profile. The obtained hydrogels were degradable by inulinase, showed a high cell compatibility and the released antibodies, analyzed by SEC and ELISA, retained their biological activity.

     

Peculiar Features of Intermolecular Interactions in Organic Compounds with Anomalously Low Boiling Points

Comparison of the boiling points (Tb) of the members of the organic triglyceride and anhydride homologous series (with unbranched hydrocarbon chains) with the Tb of n-alkanes at equal Van der Waals molecular volumes showed that the boiling points of compounds with functional groups, centers of strong intermolecular interactions, are lower than those of hydrocarbons, compounds containing no functional groups. In the triglyceride and anhydride homologous series, the Tb sharply (by more than 100°C) decreases from homolog to homolog (rather than increasing, as usually observed). To explain these anomalies, computer modeling of conformations of individual and associated molecules was performed. Standard enthalpies of vaporization (H _v ⁰), energies of intermolecular interactions (EIMI), and the ratios EIMI/H _v ⁰ = IMI (coefficients of intermolecular interactions, which may serve as a criterion of the fraction of such interactions, converted into intramolecular interactions) were calculated for all the compounds. The Tb of triglycerides and anhydrides calculated in terms of the model of pair reversible interactions of like atomic groups with allowance for IMI nicely fit with experimental values. The resulting data show that part of intermolecular interactions in triglycerides and anhydrides converts into intramolecular, which results in anomalously low Tb and sharp fall of Tb along the triglyceride and anhydride homologous series.     

Synthesis of the tetranitrates of conduritol-E andα-epoxyconduritol-E

Conclusions The general method for O-nitration of unsaturated and-epoxidized alcohols of the aliphatic series with an equimolar mixture of concentrated HNO₃ and acetic anhydride has been extended to the corresponding alcohols of the alicyclic series. The tetranitrates of conduritol-E (cyclohexene-3,4/5,6-tetraol) and of-epoxyconduritol-E (1,2-anhydroalloinositol) have been synthesized.Translated from Izvestiya Akademii Nauk SSSR, No. 4, pp. 920–922, April, 1970.     

Triflic Anhydride: A Mild Reagent for Highly Efficient Synthesis of 1,2-Benzisoxazoles,Isoxazolo, and Isothiazolo Quinolines Without Additive or Base

The synthetic utility of trifluoromethanesulphonic anhydride (triflic anhydride, TA) without additive or base for the high-yielding synthesis of a wide variety of 1,2-benzisoxazoles from 2-hydroxyaryl aldoximes and ketoximes under mild conditions has been carried out for the first time. As a continuation of our study, syntheses of isoxazolo and isothiazolo quinolones have also been demonstrated using triflic anhydride under similar conditions. This method is simple and has benefits from the easy way to isolate the products in excellent yields.

[Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for the following free supplemental resource(s): Full experimental and spectral details.]     

The mechanism of the cyclization of β-(2-carboxyaryl)aminopropionic acids to 1,2,3,4-tetrahydro-4-oxoquinolines

It is shown that cyclization of -(2-carboxyaryl) aminopropionic acids to 1,2,3,4-tetrahydro-4-oxoquinolines in the presence of acetic anhydride and alkali metal acetates proceeds via the intermediate formation of the N-acetyl derivative of the monopotassium salt of the starting acid, which undergoes further conversion into the cyclic mixed anhydride. The latter decomposes with loss of CO₂ to give the corresponding 1,2, 3,4-tetrahydro-4-oxoquinoline.     

Novel Four-Step Synthesis of Thioxo-quinazolino[3,4-a]quinazolinone Derivatives

A novel synthesis of thioxo-quinazolino[3,4-a]quinazolinone framework was developed through a four-step reaction starting from isatoic anhydride. The resulting 2-aminobenzamides from the reaction of isatoic anhydride and different amines underwent coupling–cyclization reaction with 2-nitrobenzaldehydes, reduction of nitro group, and then cyclization reaction with carbon disulfide (CS₂). All steps were carried out under easy and user-friendly conditions in a short time without using expensive catalysts or reagents.

[Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for the following free supplemental resource(s): Full experimental and spectral details.]