Reaction Of Acid Chlorides Research Articles

Modification of poly(vinyl alcohol) with acid chlorides and crosslinking with difunctional hardeners

The reaction of acid chlorides with poly(vinyl alcohol) (PVA) leads to vinyl alcohol-vinyl ester copolymers. The esterification by Schotten-Baumann enables degrees of modification to be reached which depend on the chemical structure of the pendant unit introduced. High degrees of modification were obtained in the reaction with water-stable acid chlorides such as benzoyl or cinnamoyl chloride. The copolymers obtained were characterized by spectroscopic techniques, elemental analysis, thermal methods, and viscosity determinations. Since in all cases they were only partially modified, the remaining hydroxyl groups were reacted with difunctional hardeners, Epiclon B-4400, hexamethylene diisocyanate, and tolylene 2,4-diisocyanate, to obtain tridimensional networks. Vinyl alcohol-vinyl benzoate copolymers with different degrees of modification were crosslinked to study how the percentage of remaining hydroxylic groups affects the crosslinking process. The exotherm maximum of the curing process was lower when diisocyanates were used as hardeners and the degree of crosslinking was higher when hexamethylene diisocyanate was used according to the observed increase in T g values. Whereas the TGA curves of linear polymers only showed one degradation, in crosslinked polymers two degradation steps were detected, suggesting several degradation mechanisms.

Modification of poly(vinyl alcohol) with acid chlorides and crosslinking with difunctional hardeners

The reaction of acid chlorides with poly(vinyl alcohol) (PVA) leads to vinyl alcohol-vinyl ester copolymers. The esterification by Schotten-Baumann enables degrees of modification to be reached which depend on the chemical structure of the pendant unit introduced. High degrees of modification were obtained in the reaction with water-stable acid chlorides such as benzoyl or cinnamoyl chloride. The copolymers obtained were characterized by spectroscopic techniques, elemental analysis, thermal methods, and viscosity determinations. Since in all cases they were only partially modified, the remaining hydroxyl groups were reacted with difunctional hardeners, Epiclon B-4400, hexamethylene diisocyanate, and tolylene 2,4-diisocyanate, to obtain tridimensional networks. Vinyl alcohol-vinyl benzoate copolymers with different degrees of modification were crosslinked to study how the percentage of remaining hydroxylic groups affects the crosslinking process. The exotherm maximum of the curing process was lower when diisocyanates were used as hardeners and the degree of crosslinking was higher when hexamethylene diisocyanate was used according to the observed increase in Tg values. Whereas the TGA curves of linear polymers only showed one degradation, in crosslinked polymers two degradation steps were detected, suggesting several degradation mechanisms. © 1996 John Wiley & Sons, Inc.

A New Directed Synthesis of Enol Borates from gem-Borazirconocene Alkanes, and their Regioselective Conversion to α-Bromo Ketones

Reaction of acid chlorides and gem-borazirconocene alkanes produces enol borates by rearrangement of α-bora ketones. Reaction of the enol borates with NBS occurs with complete regioselectivity to give unsymmetrical α-bromo ketones.

A new directed synthesis of enol borates from gem-borazirconocene alkanes, and their regioselective conversion to α-bromo ketones

Reaction of acid chlorides and gem-borazirconocene alkanes produces enol borates by rearrangement of α-bora ketones. Reaction of the enol borates with NBS occurs with complete regioselectivity to give unsymmetrical α-bromo ketones. Graphic

Characteristic properties of cutting fluid additives derived from the derivatives of ricinoleic acid polymers

AbstractA number of esters were prepared from the reaction of acid chlorides with ricinoleic acid polymers and screened for anti‐rust properties and antimicrobial activity in spent coolants of water‐based cutting fluids. Aqueous solutions of triethanolamine salts with decanoic acid, undecanoic acid and oleic acid esters of ricinoleic acid dimer, trimer, tetramer and hexamer showed good anti‐rust properties for water‐based cutting fluids. Dehydrates of ricinoleic acid polymers also showed good anti‐rust properties for water‐based cutting fluids.

Characteristic properties of cutting fluid additives derived from the adducts of diamines and acid chlorides

AbstractA number of N,N′‐diacylalkyldiamines were prepared from the reaction of acid chlorides with 1,8‐diaminooctane and 1,12‐diaminododecane and screened for anti‐rust properties and antimicrobial activity in spent coolants of water‐based cutting fluids. Aqueous solutions of N,N′‐dihexanoyl‐1,8‐diaminooctane and N,N′‐isobutyroyl‐1,12‐diaminododecane showed good anti‐rust properties for water‐based cutting fluids. Aqueous emulsions of N,N′‐dibutyroyl‐, dipentanoyl‐, dihexanoyl‐ and dioctanoyl‐1,12‐diaminododecane showed good lubricities and antimicrobial activity for water‐based cutting fluids.

Alkane diazonium ion pairs and deamination. 48. Inert-molecule-separated ion pairs. Stereochemical, oxygen-18, and product studies

Nitrogen- and nitrous oxide-separated carbocation-carboxylate ion pairs have been prepared by five different reactions: the rearrangement of N-nitroso amides, the reaction of acid chlorides with anti-diazoates, the reaction of acid chlorides with syn-diazoates, the reaction of acid chlorides with anions of N-nitroamines, and the decomposition of N-nitroso-O-acylhydroxylamines. Comparative stereochemical, 18 O scrambling, and product analyses have been made where common alkyl groups (1-phenylethyl), acyl groups (2-naphthoyl), solvent, and temperature areemployed

Hexafluoraceton als Schutzgruppen‐ und Aktivierungsreagenz in der Aminosäure‐ und Peptidchemie, 7. Synthese von γ‐Oxo‐α‐aminosäure‐Derivaten aus Asparaginsäure

Hexafluoroacetone as Protecting Group and Activation Reagent in Amino Acid and Peptide Chemistry, 7. – Synthesis of γ‐Oxo α‐Amino Acid Derivatives from Aspartic AcidOptically pure γ‐oxo α‐amino acids are obtained on reaction of acid chloride 2 with aromatic and heteroaromatic compounds under Friedel‐Crafts conditions.

ChemInform Abstract: Novel Ketene Formation by Reactions of Acid Chlorides with Low‐Valent Platinum Complexes.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Novel ketene formation by reactions of acid chlorides with low-valent platinum complexes

Pt(CO)in n(PPh 3) 4- n ( n = 012-2) reacts with Ph 2CHCOCl under CO to afford diphenylketene and trans-PtHCl(PPh 3) 2. For this reaction, the rate law is zero order in the platinum complex, first order in Ph 2CHCOCl, and first order in free PPh 3. A primary isotope effect ( k H/ k D = 4.5) was observed in the reaction of Ph 2CDCOCl. A mechanism is proposed which involves the rate-determining enolization of Ph 2CHCOCl by PPh 3 followed by fast abstraction of HCl by a plantinum(0) complex.

A novel, general, totally stereoselective one-pot synthesis of cis-3-substituted 4-formylazetidin-2-ones

A general, totally stereoselective one-pot synthesis of cis-3-substituted-4-formylazetidin-2-ones based upon the reaction of acid chlorides and 1,4- bis-(4-methoxyphenyl)-1,4-diazabuta-1,3-diene, as synthetic equivalent of the corresponding unknown α—formylimine, has been developed.

ChemInform Abstract: Syntheses in the Isocamphane Series. Part 34. Synthesis of Isocamphane Derivatives with Fungicidal Activity.

AbstractThe title compounds, e.g. (I) and (II), are synthesized via reaction of acid chlorides with the corresponding alcohols.

Comparison of Phosphonic and Pyrophosphonic Acids as Collectors for the Cassiterite Flotation

Abstract Styryl phosphonic acid (SPA) is a collector used in the industrial flotation of cassiterite, During its production from styrene and PCl5 by-products are formed in different amounts. One of these is condensed SPA caused by uncomplete hydrolysis of the intermediary phosphonic acid chloride. Attempts were made to synthesize definite forms of condensed SPA in order to study their influence on the results of flotation. Conventional methods-partial hydrolysis of phosphonic acid chlorides or reaction of acid chlorides with the free acid-did not lead to the desired result. Diammonium salt of the pyro-SPA was obtained by the method of (1) using dehydration of phosphonic acid by heating with urea. A series of analogous aromatic pyro-phosphonic acids was synthesized. The hydrophobization effect on Sn02 surfaces was studied by microflotation tests in a modified Hallimond tube. Pyrophosphonic acids are more hydrophobic than the corresponding phosphonic acids. The results of the microflotation experiments were...

N-vinyl and N-unsubstituted β-lactams from 1-substituted 2-aza-1, 3-butadienes

The reaction of acid chlorides and N-vinyl imines results in the stereoselective formation of cis N-vinyl β-lactams. The N-vinyl protecting group can be removed either oxidatively or hydrolytically to yield N-unsubstituted β-lactams.

Selectivity in carbon-oxygen bond formation: reaction of acid chlorides and methyl iodide with trans-(MeO)Ir(CO)(PPh3)2

Dans chacune de ces reactions, un compose d'addition est forme RIr(OMe)(CO)(PPh 3 ) 2 X stable pour R=Me. Les liaisons C−O conduisant aux esters est formee plus rapidement que la liaison C−O conduisant a l'ether dimethylique

Silylamines in organic synthesis: A new access to functional pyrroles via organocuprates addition on methyl-bis(trimethylsilyl)aminomethylpropiolate

Organocuprate addition reactions on methyl-bis(trimethylsilyl)aminomethyl-propiolate lead to the formation of a Z-vinyl cuprate with a high stereoselectivity. Upon reaction of acid chloride, pyrroles are formed by a spontaneous intramolecular cyclisation of the intermediate Z-silylamino enone. Various functional substituted pyrroles can be obtained in one step by this route.

Convenient preparation of acyltrimethylsilanes from carboxylic acid derivatives

Acylsilanes are prepared in good yields by the reaction of acid chlorides (or anhydrides) with LiAl(SiMe 3) 4 or LiMeAl(SiMe 3) 3 in the presence of a catalytic amount of CuCN.

Aspects of tautomerism. Part 15. Investigations on oxo-participation in δ-oxocarboxylic acid chlorides during their formation and alcoholysis

Oxalyl chloride converts ring-substituted 4-benzoylbutyric acids into a mixture of normal and pseudo-acid chlorides by two independent and competing pathways. Pseudoacid chlorides are formed by a concerted 2σ+ 2π+ 2σ pathway. It is suggested that the reaction of acid chlorides with a poor nucleophile involves a transition state wherein the attacking nucleophile and the departing group make an angle of ca. 45 ° to the plane of the carbonyl group. There is evidence against involvement of any common transition state or an equilibration process during the formation of normal and pseudoacid chlorides. Alcoholysis of normal acid chlorides derived from the above mentioned acids does not involve oxo-participation.

Bis(alkylaminoalkoxy-2-benzofuranyl)ketone 誘導体及び Bis(acyloxy-2-benzofuranyl)ketone 誘導体の合成と抗 Virus 活性について

Bis(alkylaminoalkoxy-2-benzofuranyl)ketone (IIa-o) were synthesized by the reaction of alkylaminoalkyl halide with bis(hydroxy-2-benzofuranyl)ketones (I). Bis(alkylaminoalkoxy-2-benzofuranyl)keton N, N-dioxides (IIIa, b) were prepared from II by treatment with hydrogen peroxide. Bis(acyloxy-2-benzofuranyl)ketones (IVa-q) were synthesized by the reaction of acid chloride and acid anhydride with I. Bis(6-acetoxy-2-benzofuranyl)ketone (IVb) showed the most potent inhibitory activity on the multiplication of influenza virus in vitro. Bis(7-diethylaminoethoxy-2-benzofuranyl)ketone N, N-dioxide (IIIa) showed a potent interferon inducing activity in mice. IVb and IIIa given orally were effective against the infection of an influenza virus in mice.

ChemInform Abstract: N‐METHYL‐N‐(PHENYLSULFONYL)BENZOHYDRAZONOYL CHLORIDE AS A POTENTIAL INTERMEDIATE FOR NITROGEN HETEROCYCLES. PREPARATION OF 1‐METHYL‐3‐PHENYL‐1H‐1,2,4‐TRIAZOLES AND ‐PYRAZOLES

AbstractDie aus dem Chlorid (I) bzw. dem Keton (III) zugängliche Titelverbindung (II) (Ausb.‐Angaben in g) reagiert mit den Nitrilen (IV) in guter bis sehr guter Ausb. zu den Triazolen (Va) und mit den Acetylenen (VI) in geringer Ausb. zu den Pyrazolen (VII).