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The first direct fabrication of A2B- and A3-type B(III)subchlorins from meso-ethoxycarbonyl-substituted tripyrrane has been realized by condensation with appropriate acid chlorides (benzoyl chloride, butyryl chloride, and ethyl chlorooxoacetate). The aliphatic acid chloride-based annulation reaction is new to subporphyrinoid chemistry. The phenyl (6a)- or n-propyl (6b)-substituted derivatives could be oxidized to the corresponding B(III)subporphyrins upon refluxing with DDQ, whereas the triethoxycarbonyl moiety (6c) was found to be resistant to oxidation and exhibits the most red-shifted absorption (587 nm) and emission (604 nm). The study indicates that absorption and emission behaviors of the B(III)subchlorin can be tuned by the introduction of electron-rich or electron-deficient substituents at the meso-position. B(III)subchlorins 6a and 6c generate singlet oxygen efficiently (44 and 40%, respectively) and, thus, may find application as potential photosensitizers in photodynamic therapy (PDT).

Cellulose nanocrystals (CNCs) and cellulose nanofibrils (CNFs) extracted from renewable resources possess many attractive characteristics, making them ideal Pickering emulsion stabilizers. However, unmodified pristine CNCs with high surface charge density are not effective in stabilizing oil–water emulsions, thereby limiting their application as interfacial stabilizers. Grafting hydrophobic polymers onto CNCs enhanced their wettability by the oil phase, which reduced the interfacial tension. Thus, hydrophobic modification was performed by grafting cinnamoyl chloride or butyryl chloride to the surface of CNFs. The modified CNFs were further hydrolyzed for 1 or 2 h to produce nanocellulose of varying sizes and hydrophobicity, and they were effective Pickering emulsifiers. The effect of nanocellulose concentration, polarity of solvents, hydrophobicity, size and electrolyte on the characteristics of the Pickering emulsions were examined and elucidated.

Tetraamido-oxacalix[4]arene derivatives have been synthesized via the reactions of tetraamino-oxacalix[4]arene with excess butyryl chloride, octanoyl chloride, benzoyl chloride and p-toluenesulfonyl chloride, respectively. 1H NMR results suggest that these oxacalix[4]arene derivatives preferentially adopt the 1,3-alternate (saddle-like) conformation in solution, which were also the case in the solid state as demonstrated by single crystal X-ray analysis. A dimerized slipped capsule could be formed by tetra-butyramido-oxacalix[4]arene in the solid state via intermolecular hydrogen bond interactions under the assistance of two encapsulated methanol molecules. On the other hand, a molecular cavity was formed by tetra-p-toluenesulfonamido-oxacalix[4]arene which can encapsulate a solvent molecule of ethyl acetate.

To enhance the hydrophobicity and thermal stability of hemicelluloses for the production of functional biopolymer, hemicelluloses was homogeneously butyrylated with butyryl chloride in 1-butyl-3-methylimidazolium chloride ([BMIM]Cl) ionic liquid using triethylamine as a neutralizer. This efficient method to prepare butyrylated hemicelluloses was confirmed by FT-IR, 1H, and 13C NMR spectroscopies. The results showed that the biopolymers with degrees of substitution (DS) between 0.91 and 1.89 were accessible in this completely homogeneous system by changing reaction conditions. The preferred reaction parameters that resulted in the highest DS (1.89) were as follows: 2:1 molar ratio of butyryl chloride to hydroxyl groups, 90 °C, and 120 min. The hydrophobicity and thermal stability of the prepared hemicellulosic derivatives were investigated by thermogravimetric analysis (TGA). The results indicated that the hydrophobicity of the butyrylated hemicelluloses was increased by increasing the value of DS. The thermal stability of the butyrylated hemicelluloses was increased while the derivative with a high DS value and decreased with a low DS value. The enhanced hydrophobicity and thermal stability of the butyrylated hemicelluloses with a high DS value make it beneficial for the production of functional biopolymer.

A mild and efficient method for the synthesis of organic peroxyesters from acid chlorides and tertiary alkyl hydroperoxides in the presence of aqueous solution of inorganic base is described. The process was conducted in a tri-liquid system using quaternary onium salts and polyethylene glycols as phase-transfer catalysts. A model reaction of cumyl hydroperoxide (CHP) with butyryl chloride was investigated under a wide range of conditions. Selected peroxyesters were obtained in moderate to high yields (62–93%).

Wood meal was dissolved under identical conditions in the ionic liquid 1-butyl-3-methylimidazolium chloride ([C 4 mim]Cl) and homogeneously esterified with butyryl chloride and lauroyl chloride in the presence of triethylamine as a neutralizer. The effect of the molar ratio of reagent to the hydroxyl groups in wood on the properties of the esterified wood and the possible mechanism of the homogeneous esterification of wood in this reaction medium were studied. Furthermore, the physicochemical properties of the esterified wood were characterized by FTIR, solid-state CP/MAS 13 C NMR, TGA/DTG and SEM. The results confirmed that the homogeneous modifications were successfully processed and highly substituted wood esters could be obtained by reacting the dissolved wood in this homogeneous system.

In this study, we discovered and isolated an attractant for a mealybug-parasitic wasp Anagyrussawadai from an esterification product prepared with commercialized lavandulol (2-isopropenyl-5-methyl-4-hexen-1-ol) and butyryl chloride. Using gas chromatography-mass spectrometry (GC-MS) and nuclear magnetic resonance spectroscopy, we determined the structure of the compound to be (2,4,4-trimethyl-2-cyclohexenyl)methyl butyrate (cyclolavandulyl butyrate). This is a novel compound as far as we know, although the alcohol moiety has been known as a cyclization product from lavandulol. Cyclolavandulyl butyrate has two enantiomers, and the (−)-isomer, which is suggested to have S configuration, showed higher attractiveness. A potential use for the A. sawadai attractant for mealybug management in agricultural fields is discussed.

The photochlorination at room temperature of butyryl, valeryl and caproyl chloride in the liquid phase has been investigated. The acid chlorides were allowed to interact with a third of the equimolecular amount of chlorine under irradiation with a mercury lamp. The reaction mixtures obtained were separated by fractional distillation and counter current distribution according to Craig. The monochloro-derivatives of the acid chlorides were characterized by preparing the ρ-toluidides. The identity of α-, β-, δ- and ϵ-chlorocaproic acids was established by synthesis. It is found that butyryl chloride yields

The pure rotational spectrum of perfluorobutyryl fluoride, C3F7COF, was measured using a pulsed nozzle, chirped pulse Fourier transform microwave spectrometer. A total of 280 transitions for the only observed conformer were recorded and analyzed. The rotational constants are A = 1397.4330(1) MHz, B = 619.17456(8) MHz, and C = 592.06831(8) MHz. Quantum chemical calculations and the spectral analysis indicate that the observed conformer is the skew–anti form with calculated dihedral angles ∠ CCCO = 120°, and ∠ CCCC ≈ 170°. Conformational differences between perfluorobutyryl fluoride, perfluorobutyryl chloride, butyryl fluoride and butyryl chloride are discussed.

The pure rotational spectrum of butyryl chloride has been recorded between 8 and 16 GHz using a chirped pulse, Fourier transform microwave spectrometer. The transitions recorded were assigned to two different conformers which have previously been designated syn-gauche and syn-anti. Quantum chemical calculations have produced rotational constants in good agreement with those obtained from the observed spectra. For the syn-gauche conformer the τ 1 (CCCO) dihedral angle is calculated to be 10° and the τ 2 (CCCC) dihedral angle is calculated to be 70°. For the syn-anti conformer τ 1 (CCCO) is calculated to be 0° and τ 2 (CCCC) is calculated to be 180°. For both MP2 and M06-2X methods with 6-311G∗∗ basis sets the syn-gauche conformer is calculated to be marginally lower in energy than the syn-anti conformer. The resolution of the experiments was sufficient to resolve hyperfine structure from the 35 Cl and 37 Cl nuclei in both conformers, and in all cases the full Cl nuclear quadrupole coupling tensors have been determined for the first time.

A discotic 2,6,10-trihydroxy-3,7,11-tripentyloxytriphenylene material and a triphenylene-based hyperbranched macromolecule were synthesized, in which the latter was prepared from AB m molecules in a one-pot reaction. Adipic chloride and butyryl chloride were chosen as terminal groups to the 2,6,10-trihydroxy-3,7,11-tripentyloxytriphenylene. Mesophase and their structural orders were determined using a polarized optical microscope and a differential scanning calorimeter. Carrier mobilities of the pure and composite materials were measured via a time-of-flight method. A change in carrier mobility on the morphology of the materials was further discussed. It was found that degree of crystallization was the key for a discotic triphenylene material to possess charge-transporting properties, no matter it is ordered or disordered.

Electrochemical perfluorination (ECPF) of the title compounds containing primary, secondary and tertiary carbon atoms was carried out in anhydrous hydrofluoric acid (AHF). Detailed analysis of major and minor products suggest that carbon chain isomerisation involving cyclo-propane intermediate is more prevalent during ECPF of i-butyryl chloride when compared to n-butyryl chloride. Simple statistical probability involving free radical intermediates also support this observation. ECPF involving cyclo-propane intermediate is even more prevalent in pivaloyl chloride containing three methyl substituents. In this case, perfluorinated cyclo-propane intermediates were also observed in the product sample. Distribution of minor perfluorinated and partially fluorinated products also suggest the predominant role of normal free radical pathway involving single-electron transfer.

Acid chloride (ROCl) hydrolysis in a 1,2-dichloroethane (DCE)/water system has been investigated over a wide range of conditions using microelectrochemical measurements at expanding droplets (MEMED). Hydrolysis occurred spontaneously when DCE droplets containing either butyryl chloride, valeryl chloride, hexanoyl chloride, or decanoyl chloride were expanded into an aqueous buffer solution (pH 4−11). The reaction was monitored using a potentiometric Ag/AgCl ultramicroelectrode to measure local changes in Cl- concentration in the aqueous phase near the surface of the droplets during the reaction. For butyryl chloride and decanoyl chloride, the hydrolysis rate increased gradually with increasing pH. For valeryl chloride and hexanoyl chloride, the hydrolysis rate increased with pH in the range of 4−9 but decreased at higher pH values, due to the blocking of the liquid/liquid interface by products. A mechanism for the ROCl hydrolysis reaction, involving rapid (Langmuirian) adsorption of ROCl at the interface f...

A highly selective and sensitive fluorometric method for the determination of bisphenols has been developed. This method is based on an intramolecular excimer-forming fluorescence derivatization with a pyrene reagent, 4-(1-pyrene)butyryl chloride (PBC), followed by reversed-phase liquid chromatography (LC). The bisphenols, containing two phenolic hydroxyl groups in a molecule, were converted to the corresponding dipyrene-labeled derivatives by reaction with PBC. The derivatives afforded intramolecular excimer fluorescence (440–520 nm) which can clearly be discriminated from normal fluorescence (360–420 nm) emitted from PBC and monopyrene-labeled derivatives of monophenols. The PBC derivatives of bisphenols could be separated by reversed-phase LC on an octyl column with isocratic elution. The detection limits (signal-to-noise ratio = 3) for bisphenols were 3.0–5.0 fmol, for a 20 μl injection. The method was successfully applied to the determination of bisphenol A in hot water in contact with commercially available baby bottle samples after solid-phase extraction.

In the research described below, we have developed a convenient and effective method of synthesis of organic peroxyesters to achieve 60–98% yields under extreme mild conditions. The study has been conducted on a model system using a reaction of acylation of 1-methyl-1-phenylethyl hydroperoxide (CHP) by means of butyryl chloride in the presence of solid Na2CO3 and being performed under conditions of phase transfer catalysis (PTC). The effect of the following parameters on the reaction was tested: temperature, Na2CO3 amount, catalyst structure and solvent polarity.

Liquid phase acylation of benzene by acyl chloride (e.g., benzoyl chloride, butyryl chloride or phenyl acetyl chloride) over InCl3, GaCl3 and ZnCl2 supported on commercial clays (viz. montmorillonite-K10, montmorillonite-KSF and kaolin) or high silica mesoporous MCM-41 at 80°C has been investigated. The Mont.-K10 and Si-MCM-41 supported InCl3 and GaCl3 catalysts showed high activity in the acyation of benzene by benzoyl chloride even in the presence of moisture in the reaction mixture. The redox function of the supported InCl3, GaCl3 or ZnCl2 catalysts seems to play a very important role in the acylation process.

Butyric esters (BuPC) of hydroxypropylcellulose (HPC) with different degrees of substitution (DS) were obtained by the reaction of (2-hydroxypropyl)cellulose with butyryl chloride. Blends of these BuPCs were obtained from ternary solutions by removal of the com mon solvent. The blends displayed thermotropic choles teric mesophases and showed iridescent colors at ambient temperatures depending on the blend composition. The spectroscopic analysis of the blends showed systematic variations of the reflection colors with variations of the ratio of the blend components between the reflection colors of the pure blend components covering the range from 453-938 nm corresponding to pitch heights from 308 640 nm.

The alcoholysis of acetyl chloride, propionyl chloride and butyryl chloride with some alcohols in acetone and toluene has been investigated by means of calorimetric measurements. Furthermore a comparison with benzoyl chloride has been made. In the case of i-propanol in acetone, a smaller rate constant has been found for the alcoholysis of propionyl chloride than for butyryl chloride. In contrast to this, almost equal rate constants have been determined for the reactions of these acyl chlorides with n-propanol and ethanol. In toluene, the rate constants for the reaction of acetyl chloride with all considered alcohols has the highest values under similar conditions but then decrease from acetyl chloride to butyryl chloride. The observed differences and the changes of rate constants are discussed and compared with literature data.

Butyric esters of (2-hydroxypropyl) cellulose (BuPC) with different degree of substitution (DS) were synthesized via control of the esterification time of butyryl chloride and (2-hydroxypropyl) cellulose. These BuPCs are thermotropic and displayed different colors at ambient temperature due to the formation of a cholesteric structure and the occurrence of a corresponding cholesteric reflection. The pitch height was found to increase significantly with a decrease of the degree of substitution. Both the glass transition temperature and the melting temperature are not affected by variation of the DS. The BuPC samples displayed a banded texture of focal-conic texture, respectively. The X-ray diffraction studies revealed the presence of a layer structure. The d-spacing between two adjacent layers in the cholesteric structure displayed no significant dependence on the DS in the range from 2 to 3.

The acylation of thiophene by butyryl chloride has been studied in the liquid phase in the presence of 12 catalysts: HZSM-5, H-mordenite, and HY (ultrastable Y) with various framework Si/Al ratios, various numbers of Bronsted and Lewis sites, and various amounts of nonframework aluminum. The numbers of Bronsted and Lewis acid sites were obtained by FT-IR using chemisorbed ammonia, as described elsewhere. There is a correlation between the initial rates of reaction and the number of Lewis acid sites, whereas there is no correlation between the initial rates and the number of Bronsted sites. The correlation with the number of Lewis sites may be considered significant, since it expands on more than one order of magnitude. Poisoning of the catalyst probably results from the oligomerization on butyryl chloride. No carboxylic acid has been detected in the course of the reaction. No attempt has been made to determine the nature of the poisoning reaction.

2 When3-dihydro-1H-cyclohepta[b]pyrazine (3) was treated with acetyl chloride under the Friedel-Crafts conditions, its pyrazine ring opened to afford 2-[N'-acetyl-(2-aminoethyl)amino]tropone. Reactions with propionyl and butyryl chloride also gave similarly ring-opened products. On the other hand, aromatic benzoyl chlorides reacted with compound 3 to afford N-benzoyl-substituted 2,3-dihydro-1H-cyclohepta[b]pyrazines, in addition to ring-opened compounds.

Acylation of aromatic compounds (benzene, toluene, p -xylene, mesitylene, anisole, naphthalene, methylnaphthalene and methoxynaphthalene) by an acyl chloride (benzoyl chloride, phenylacetyl chloride, propionyl chloride or butyryl chloride) in high yield, in a short reaction period (3 h), even in the presence of moisture in the aromatic substrate or solvent (dichloroethane), can be accomplished at low temperature (80±1°C) using an InCl 3 impregnated Si-MCM-41 catalyst in low catalyst concentration.

As asymmetric route to [14C]β-hydroxycompactin 1 bearing the (S)-2-methyl-[1-14C]butanoate side chain has been developed. Methylation of [N-[1-14C]butyryl-4-(S)-phenylmethyl-2-oxazolidinone 4 afforded a 95:5 mixture of diastereomeric [N-(S,R)-2-methyl-[1-14C]butyryl]-4-(S)-phenylmethyl-2-oxazolidinones 5,6 which were separated by preparative HPLC. Oxidative cleavage of 5 afforded optically pure (S)-2-methyl-[1-14C]butanoic acid. Acylation of alcohol 9 with optically pure (S)-2-methyl-[1]14C]butyryl chloride afforded ester 10. Removal of the silyl either produced diastereomerically pure compactin 11. Hydroxylation was carried out by biotransformation with Mucor hiemelus to afford diastereomerically pure [[1-14C]butanoate]β-hydroxycompactin, [14C]Pravastatin 1.

The enantiogenic syntheses of (−)-indolizidine 167B (1) and (+)-monomorine (2) are described. D-Norvaline and L-alanine are converted into their 1-pyrrole derivatives by reaction with 2,5-dimethoxytetrahydrofuran. Thereafter, Arndt-Eistert homologation of the N-alkanoic acid substituent, followed by rhodium (II) acetate catalyzed decomposition of its α-diazo ketone derivative, provides the relevant bicyclic precursors, the vested chirality of which directs catalytic hydrogenation affording 1 and 2. Provision for the 5-butyl side chain in 2 is made by prior Lewis acid catalyzed rearrangement of the mixed anhydride obtained from butyryl chloride and the pyrrole analogue of L-alanine

Diethyl L-glutamate hydrochloride ( 3 ) was converted to its N-pyrrole derivative 5 . Submission of 5 to butyryl chloride in boiling toluene gave the 2-butyryl derivative, and by treatment with NaBH 3 CN and ZnI 2 , the 2-butyl analogue 9 . Cyclization of 9 with BBr 3 afforded (5S)-3-butyl-5-ethoxycarbonyl-5,6-dihydro-8(7H)-indolizinone ( 10 ). Hydrogenation of 10 over Pd/C in acidified EtOH gave (3S,5S,9R)-3-butyl-5-ethoxycarbonylindolizidine. By successive reduction of the latter to the primary alcohol, formation of the chloride and reductive dechlorination with tributyltin hydride, (3S,5R,9R)-3-butyl-5-methylindolizidine, or (-)-monomorine, was obtained in 8 steps from 3 in a yield of 25%.

2 When3-dihydro-1H-cyclohepta[b]pyrazine (3) was treated with acetyl chloride under the Friedel-Crafts conditions, its pyrazine ring opened to afford 2-[N'-acetyl-(2-aminoethyl)amino]tropone. Reactions with propionyl and butyryl chloride also gave similarly ring-opened products. On the other hand, aromatic benzoyl chlorides reacted with compound 3 to afford N-benzoyl-substituted 2,3-dihydro-1H-cyclohepta[b]pyrazines, in addition to ring-opened compounds.

Acylation of aromatic compounds (benzene, toluene, p -xylene, mesitylene, anisole, naphthalene, methylnaphthalene and methoxynaphthalene) by an acyl chloride (benzoyl chloride, phenylacetyl chloride, propionyl chloride or butyryl chloride) in high yield, in a short reaction period (3 h), even in the presence of moisture in the aromatic substrate or solvent (dichloroethane), can be accomplished at low temperature (80±1°C) using an InCl 3 impregnated Si-MCM-41 catalyst in low catalyst concentration.

The synthesis of highly uniform (1,08 ≤ Mw/Mn ≤ 1,13) telechelic poly(e-caprolactone) terminated at both ends with OH groups and its derivatization leading to poly(e-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(e-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(e-caprolactone), HO-poly(eCL)-OH, with 4-(1-pyrenyl)butyryl chloride yields α,ω-di-1-pyrenylpoly(e-caprolactone), Py-poly(eCL)-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.

The aldimines derived from (1S,2S)-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.

Water sorption kinetics and water contact angles have been characterized for a range of pharmaceutical powders: ambroxol hydrochloride, griseofulvin, N,n-octyl-D-gluconamide, paracetamol, sulfathiazole, and theophylline. The uptake of water by powder samples at saturated vapor pressure was modeled using a pseudo first-order kinetic relationship. Parameters from this model have been correlated with the concentration and reactivity of the active surface sites of the pharmaceutical powders and their contact angles. The study has shown that analysis of water adsorption kinetics can be a powerful technique for characterizing the surface chemistry and wettability of pharmaceutical powders, and is particularly sensitive to their surface modification through excipient adsorption: ethyl(hydroxyethyl)cellulose treatment of griseofulvin and butyryl chloride treatment of sulfathiazole are reported as case studies.

n-Butyryl chloride product: n-Butyryl chloride Keywords: replacement reactions, hydroxy by halogen; butyryl chloride, preparation of

A 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.

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.

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.

The 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).

The polymerization of N-alkyl-8-oct anelactams (N-alkylcapryllactams) at 150—200°C is a first order reaction with respect to monomer and hydrogen chloride; both the activation energy and the frequency factor decrease with increasing size of the substituent. The polymerization initiated with butyryl chloride proceeds ten times slower than with hydrogen chloride or an equimolar mixture of butyryl chloride and dibutylamine hydrochloride. The main monomer fraction is incorporated into the polymer by a sequence of two reactions, namely, cleavage of N-alkyllactam with hydrogen chloride to N-alkyl-8-ami nooctanoyl chloride followed by its bimolecular condensation. However, the participation of sec-amine hydrochloride catalyzed polyaddition of lactams to the carbonyl chloride group cannot be excluded so far. Of the initiators of the polymerization of N-methyl-8-oc tanelactam (/), hydrogen chloride or lactam hydrochloride1 is the most effective. The effect of hydrogen chloride in the cationic polymerization of the above lactam consists in the deacylating cleavage of the amide bond with formation of N-methyl-8-am inooctanoyl chloride hydrochloride2

Partial esters of cellulose varying in degree of substitution from 0.02 to 0.58 were prepared by reacting cellulose immersed in dimethylformamide with either perfluoro butyryl chloride or perfluorooctanoyl chloride in the presence of a tertiary aromatic amine. The use of essentially homogeneous solutions of acid chlorides resulted in prod ucts which retained properties of the original cotton and showed in addition oil and water repellency which was durable to dry cleanings and aqueous launderings in the presence of neutral detergents. Rates of uncatalyzed hydrolysis of the perfluorooctanoyl cellulose esters were determined at 25°, 35°, and 45° C., and the rate of the alkaline catalyzed hydrolysis was estimated at 25° C. The energy and entropy of activation for the uncatalyzed hydrolysis were determined.

Cotton fabric was esterified with C4-18 aliphatic monobasic acid chlorides in dimethyl formamide, with pyridine as acid scavenger, at temperatures of 30-85°C. Reaction for 15-60 min at 85°C produced 0.02-0.36 ester groups per monomer unit, which provided water-repellency ratings of 50-80 in the AATCC spray test; water-repellency generally improved with increasing chain length and reaction temperature. Dry-cleaning resistance was good in perchloroethylene alone, but addition of alkaline soap required longer chain lengths and preferably an aqueous post-rinse to retain water repellency. Air permeability decreased during the reaction, but this was due primarily to shrinkage rather than inherent in the pro duction of water repellency. Tensile strength decreased gradually with increasing chain length, temperature, and time, but it was possible to produce a maximum spray rating of 80 with a tensile loss of only 33% and spray ratings of 70 with tensile losses as low as 12%.

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.

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.

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.

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.

3beta-Hydroxy-13alpha-amino-13,17-seco-5alpha-androstan-17-oic-13,17-lactam 4-[p[bis(2chloroethyl)amino]phenyl]butyrate was prepared by reacting 4-[p-[bis(2-chloroethyl)amino]phenyl]butyryl chloride hydrochloride with 3beta-hydroxy-13alpha-amino-13,17-seco-5alpha-androstan-17-oic-13,17-lactam. They cytostatic action of the ester was investigated on two tumor systems (B16 melanoma on C57 b1 mice and T8-Guerin on rats).