Butyryl Chloride Research Articles

Telechelic poly(ε‐caprolactone) terminated at both ends with OH groups and its derivatization

AbstractThe synthesis of highly uniform (1,08 ≤ Mw/Mn ≤ 1,13) telechelic poly(ε‐caprolactone) terminated at both ends with OH groups and its derivatization leading to poly(ε‐caprolactone) with pyrene end‐groups are described. The synthesis, carried out in THF at room temperature, involves initiation with (CH3CH2)2AlO(CH2CH2O)3Al(CH2CH3)2, leading to poly(ε‐caprolactone) macromolecules growing at both ends. The active centers were deactivated with acetic acid, giving macromolecules with OH end‐groups. Reaction of α,ω‐dihydroxypoly(ε‐caprolactone), HO‐poly(εCL)‐OH, with 4‐(1‐pyrenyl)butyryl chloride yields α,ω‐di‐1‐pyrenylpoly(ε‐caprolactone), Py‐poly(εCL)‐Py. Polymers are characterized by GPC, 1H NMR, and UV spectroscopies. The UV spectra of polymers with pyrene end‐groups are compared with the UV spectra of the model compound.

ChemInform Abstract: Synthesis and NMR‐Spectral Characterization of N,N‐Dialkyl‐3‐nitroanilines, N,N‐Dialkyl‐1,3‐benzenediamines and Their Acyl Derivatives.

AbstractThe alkylation of the nitroaniline (I) yields a mixture of mono‐ (III) and dialkylated product (IV).

ChemInform Abstract: Synthesis of 2‐Butanoyl‐3‐alkylamino‐2‐cyclohexene‐1‐ones.

AbstractIn the presence of pyridine the enaminoketones (I) undergo C‐acylation on treatment with butanoyl chloride (II) to give the title compounds (III).

Enantiospecific synthesis and absolute configuration of β-lactam, intermediates from 2-amino-1-phenyl-1,3-propanediols

The aldimines derived from (1 S,2 S)-2-amino-1-phenyl-1,3-propanediols as chiral starting materials were used to prepare cis-β-lactams ( 3, 4) via the Staudinger-reaction. High diastereoselectivity was reached only with large silyl protecting groups. The 6 oxazine derivative was obtained when using butyryl chloride as ketene precursor.

Synthesis and NMR‐spectral characterization of N,N‐dialkyl‐3‐nitroanilines, N,N‐dialkyl‐1,3‐benzenediamines and their acyl derivatives

AbstractA recently discovered method for the synthesis of N,N‐dialkyl‐1,3‐benzenediamines with two different alkyl groups is shown to be general. This is demonstrated by the synthesis of N‐butyl‐N‐phenethyl‐1,3‐benzenediamine by the condensation of 3‐nitroaniline with phenyl‐acetaldehyde and benzotriazole, reduction of the adduct with sodium borohydride, acylation of the resulting N‐phenethyl‐3‐nitroaniline with butyryl chloride, catalytic reduction of the nitro group by formic acid in the presence of triethylamine and palladium and finally reduction of the butyramide carbonyl group to the butyl substituent by lithium aluminum hydride. Several other routes were less efficient or failed completely.Classical methods for the synthesis of N,N‐diethyl‐1,3‐benzenediamine were reexamined and improved. The recommended procedure involves alkylation of 3‐nitroaniline with diethyl sulfate, trapping of N‐ethyl‐3‐nitroaniline (by‐product) by benzoylation, distillation of N,N‐diethyl‐3‐nitro‐aniline under reduced pressure and reduction of the nitro group by formic acid catalyzed by palladium.

ChemInform Abstract: Reactivities of Stable Rotamers. Part 24. Formation of Isomeric Ketones by Cyclization of Rotameric 3‐Methyl‐3‐(1,2,3,4‐tetrahalo‐9‐triptycyl)butanoyl Chloride and Barriers to Isomerization of the Ketones.

AbstractThe rotameric alkenyltriptycenes (III) and (IV) isomerize in boiling 1‐chloronaphthalene and serve to prepare the ketones (VII) and (VIII) via carboxylic acids (V) (and their rotamers, from (III)).

Reactivities of Stable Rotamers. XXIV. Formation of Isomeric Ketones by Cydization of Rotameric 3-Methyl-3-(1,2,3,4-tetrahalo-9-triptycyl)butanoyl Chloride and Barriers to Isomerization of the Ketones

Abstract Rotational isomers of 3-methyl-3-(1,2,3,4-tetrahalo-9-triptycyl)butanoic acid, where the halo is either fluoro or chloro have been prepared. Cyclization of their acid chlorides afforded ap- and sc-ketones from ap- and sc-isomers, respectively. The barriers to isomerization were 29.9 and 26.8 kcal mol−1 at 363 K, for the fluoro and the chloro ketones, respectively, for the ap→±sc process. The equilibrium constants (sc/ap) at 363 K were 2.34 and 18.5 for the fluoro and the chloro compounds respectively. The barriers to isomerization and the relative stabilities of the isomeric ketones were discussed based on the MMP2(NONPLANAR) calculation results and the steric congestion in the ground state.

ChemInform Abstract: On the Structure of Cyclic Self‐Condensation Products of Propionyl and Butyryl Chloride in the Presence of Aluminum Chloride.

ChemInform Abstract: On the Structure of Cyclic Self‐Condensation Products of Propionyl and Butyryl Chloride in the Presence of Aluminum Chloride.

ChemInform Abstract: Reaction of Aliphatic Dicarboxylic Acids with Acyl Chlorides in the Presence of Aluminum Chloride.

AbstractBernsteinsäure (I) reagiert mit den Säurechloriden (II) unter Friedel‐ Crafts‐Bedingungen zu den Iß‐Cyclopentandionen (III).

Reaction of aliphatic dicarboxylic acids with acyl chlorides in the presence of aluminum chloride.

The treatment of succinic acid with lauroyl or stearoyl chloride gave the five-membered β-diketone (II) substituted with a long chain at the α-position, together with a trimer (III) of the acyl chloride. Bicyclo[3.3.1]nonane-2, 4-dione (VI) substituted with a methyl or ethyl group at the C3-position was prepared from cyclohexane-1, 3-dicarboxylic acid (V) and propionyl or butyryl chloride, respectively. D-Camphoric acid afforded an unexpected product, 4-acyl-2, 2, 3-trimethyl-3-cyclopentenecarboxylic acid (IX), on reaction with acyl chloride. Although acetyl chloride gave no product on treatment with succinic acid, it afforded 3-acetylbicyclo[3.2.1]octane-2, 4-dione (XI), 3-acetylbicyclo[3.3.1]nonane-2, 4-dione (VId), and 2-acetylcyclohexane-1, 3-dione (XII) on reaction with the corresponding dicarboxylic acids.

A conformational study of butyronitrile and butyryl chloride by low resolution microwave spectroscopy

The ( B + C) values of both anti and gauche conformers of butyronitrile and both syn—anti and syn—gauche conformers of butyryl chlorides (either Cl 35 and Cl 37 isotopic species) have been measured from low resolution microwave (LRMW) spectroscopy data. One structure has been assumed for each molecule in order to estimate the respective torsion angles of the methyl group around the next CC bond to originate the gauche conformers by torsion from their respective anti conformers. These angles are 114±2° and 102±2° for butyronitrile and butyryl chloride, respectively.

Reductive coupling of butyryl chloride in the presence of CoCl(PPh3)3

1. Reductive coupling of butyryl chloride with CoCl(PPh3)3 affords 4-heptanone, 4,5-octanedione, 4-hydroxy-5-octanone, 4-butyryloxy-5-octanone, and 4,5-dibutyryloxy-4-octene. 2. A mechanism for the reductive coupling of butyryl chloride is proposed, involving the intermediate formation of an acylcobalt(III) dichloride complex.

O‐deuterio‐butanoic acid

AbstractA literature procedure for the preparation of O‐deuterioacetic acid from the anhydride gives substantial deuterium incorporation at C‐2 when used to prepare deuteriobutanoic acid. The enol form of butanoic anhydride is implicated as the intermediate which causes the isotopic scrambling. The required title compound was obtained by the reaction of butanoyl chloride and deuterium oxide.

Some Properties of Fluorine-adsorbed Active Carbon

Abstract Properties of fluorine-adsorbed active carbon (FAAC), expected to be a new fluorinating agent, were investigated by means of TG, X-ray diffraction, and ESCA. The fluorine in FAAC was desorbed by heat treatment in a vacuum at temperatures higher than 200 °C. The X-ray diffraction and ESCA measurements suggest that fluorine is inserted between the carbon layer planes of the active carbon, and combines with carbon atoms weakly in comparison with the C–F covalent bond. The reactivity of FAAC against several organic compounds was studied. 1-Butanol, 1-butanethiol, and cyclohexylamine were oxidized. Butyryl chloride was fluorinated to give butyryl fluoride.

Chlorination of Butyryl Chloride in the Liquid Phase.

Chlorination of Butyryl Chloride in the Liquid Phase.

Electronic and photoelectron spectral studies of electroactive species attached to silanized carbon and platinum electrodes

Abstract : Depending on silanization reaction conditions, aminophenylferrocene and tetrakis (p-aminophenyl) porphyrin can be covalently attached in monolayer or multi-molecular layer quantities to glassy carbon and superficially oxidized Pt electrodes using 4-(methyldichlorosily)butyryl chloride. This study applies various spectroscopies to surface structure of the attached porphyrin: XPS (number of surface amide bonds), fluorescence (quantity of porphyrin attached to a siloxane polymer film compared to quantity of electroactive porphyrin), and reflectance spectroscopies (spectroelectrochemical observation of oxidation state changes with electrode under potential control, including an electrochemically silent Co(III/II) porphyrin reaction). Electroactive films 500 monolayers thick can be prepared from the ferrocene by spin coating reactive silane; in aqueous sulfuric acid voltammetry of these films indicates a phase-like property. (Author)

Synthesen von polyhalogenierten Butyrylchloriden, Vorläufern der pyrethroiden Haloketene

Synthesis of Polyhalogenated Butyryl Chlorides, Precursors of Pyrethroid HaloketenesThe copper (I)‐catalyzed free radical addition of halomethanes to acrylates and the addition of halogenated acetic acid derivatives to fluoro‐ or chloro‐substituted ethylenes affords polyhalogenated butyric acid derivatives. Chlorides of these acids serve as precursors for haloketenes used in efficient syntheses of pyrethroids.

Protected polyvinylamine fragments capable of liberation under mild conditions

AbstractThe synthesis and polymerization of 2‐cyanoethyl N‐vinylcarbamate (3b) and of the corresponding 2‐trimethylsilylethyl isomer 3c are reported. The homopolymers 4b and 4c, derived from 3b and 3c, could be deblocked under mild conditions (ethanolamine for 4b and trifluoroacetic acid or tetraethylammonium fluoride for 4c) with essentially 100% unmasking of the amino function. Treatment of such unmasked amino groups in a copolymer derived from N‐vinyl‐2‐pyrrolidone and 3b with 4‐{4‐[bis(2‐chloroethyl)amino]phenyl}butyryl chloride (13) (chlorambucil chloride) gave the corresponding amide, a potential antitumor agent. Kinetic studies showed that fluoride ion cleavage of poly(2‐trimethylsilylethyl N‐vinylcarbamate) occurred at rates comparable to those observed for the low molecular weight analog 2‐trimethylsilylethyl N‐isopropylcarbamate (10).

New Compounds: Antitumor Activity of 3β - Hydroxy-13 α - amino -13,17 - seco - 5α- androstan -17 - oic -13,17 - lactam 4-[p-[Bis(2-chloroethyl)amino]phenyl]butyrate

3/β-Hydroxy-l 3α-amino-13,17-seco-5α-androstan-17-oic- 13,17-lactam 4-[p-[bis(2-chloroethyl)amino]phenyl]butyrate was prepared by reacting 4-[p-[bis(2-chloroethyl)amino]phenyl]butyryl chloride hydrochloride with 3β-hydroxy-13α-amino-13,17-seco-5α-androstan- 17-oic-13,17-lactam. The cytostatic action of the ester was investigated on two tumor systems (B16 melanoma on C57 bl mice and T8-Guerin on rats).

Improved staining characteristics of serum lipids after halogenation and esterification of thin-layer chromatograms.

We describe a procedure for treatment of thin-layer chromatographic serum lipid patterns so that they may be stained by dyes for evaluation by densitometry. After development of the chromatogram [Clin. Chem. 18, 384 (1972)] the plates are dried and sprayed with butyryl chloride. This esterifies the free cholesterol. After drying, the plate is treated with iodine monobromide, to add iodline to the double bonds. The triacylglycerols (triglycerides), cholesterol esters, free cholesterol, and phospholipids are now all in the form of esters with no unsaturated double bonds. The free fatty acids are also now saturated. The chromatogram is now stained with basic fuchsine in acetate buffer (0.1 mol/liter, pH 5.0). Excess stain is removed with a buffered solution of guanidine hydrochloride. Erythrosine B may also be used. With basic fuchsine the background will be a uniform pink. With erythrosine B the background is white, but the stain tends to be washed out of the free fatty acids. The chromatograms are evaluated by densitometry, with use of a 540-nm filter for basic fuchsine and a 520-nm filter for erythrosine B. The stained chromatograms and densitometric scans accurately represent the relative concentration of the various lipid fractions as compared to that of an internal standard, and correlate with the nature of the disease being explored.