And octanoyl chloride

Poly(hydroxymaleimide-co-hydroxystyrene) (5.60 mmol) was dissolved in 20 ml of /V-mcthylpyrralidonc and then cooled to 0°C. The solution was then treated with tri-ethylamine (20.16 mmol) and stirred for 60 minutes and then further treated with the step 4 product (0.656 g) and octanoyl chloride (4.03 mmol). The mixture was heated to ambient temperature and stirred for 24 hours and then precipitated by pouring in methanol and water. It was filtered, extracted with methanol, and 5.3 g product isolated. 

Other studies by Drakesmith and Hughes [124] have used the fluorination of propene and octanoyl chloride as model compounds to investigate the effects of anode potential, current density, reactant concentration, temperature, etc. on reproducibility, product structure, distribution and yield in novel cell designs ranging in scale from 100 ml to 1001 cell capacities. 

Conventional synthesis of such materials employs fiitty-acid chlorides or anhydrides in organic solvents. Recently, a fiee-solvent method to esterify starch was developed in our laboratory using formic acid and octanoyl chloride as the gelatinizing and acylating agents respectively. After optimization of reaction conditions, starch octanoate with DS of 1.7 was obtained with a recuperation yield of 89 %. ... 

During electrochemical fluorination retention of important functional groups or atoms in molecules is essential. Acyl fluorides and chlorides, but not carboxylic acids and anhydrides (which decarboxylate), survive perfluorination to the perfluorinated acid fluorides, albeit with some cyclization in longer chain (>C4) species [73]. Electrochemical fluorination of acetyl fluoride produces perfluoro-acetyl fluoride in 36-45% yields [85]. Electrochemical fluorination of octanoyl chloride results in perfluorinated cyclic ethers as well as perfluorinated octanoyl fluonde. Cyclization decreases as initial substrate concentration increases and has been linked to hydrogen-bonded onium polycations [73]. Cyclization is a common phenomenon involving longer (>C4) and branched chains. a-Alkyl-substituted carboxylic acid chlorides, fluorides, and methyl esters produce both the perfluorinated cyclic five- and six-membered ring ethers as well as the perfluorinated acid... 

In a later publication [ 129], using the same equipment, Liu et al. describe process improvements in the electrochemical fluorination of octanoyl chloride in which formation of polymeric tar at the anode surface was limited by addition of a mercaptan (1-methyl-1-propanethiol), and by constant current density operation (7 mA cm-2). Continuous operation was achieved by frequent additions of a solution of reactant in hydrogen fluoride. Conversion of reactant to perfluori-nated products was increased to 80%, with good selectivity. 

Scheme 36. Composition of reaction mixtures in the ECF of 4-(perfluoro-n-butyl)-n-butanoyl chloride (Expts.l -4) and n-octanoyl chloride (Expts.5-6)...

Phenyl heptyl ketone has been prepared by the Friedel-Crafts acylation of benzene with octanoyl chloride.6 It is also a product of the thermal decomposition of the mixed ferrous salts of benzoic and octanoic acids.7... 

Add octanoyl chloride and then the b/ s(4-pivaloxybutyl)zinc solution (4 mL of the above prepared solution). 

A recent article reported the use of strongly acidic mesoporous aluminosilicates prepared from zeolite seeds in the acylation of anisole with octanoyl chloride.[30] The mesoporosity improving the transport of the reactants and the presence of strong acid sites lead to high conversion (>90 %) and high selectivity (100 %). 

Octanoyl chloride (1.67 mol) was heated to 55 °C, Br2 (2.34 mol) added over 8 hours, and the reaction stirred overnight. Thereafter, the mixture was distilled at 111 °C at 8mmHg, and 100% yield of a mixture of 2-bromooctanoyl chloride and 2-bromooctanoyl bromide, 35 65, isolated. 

Ioxynil and bromoxynil can be easily esterified with add chlorides ydth longer carbon atom chains. Thus, esterified with octanoyl chloride, ioxynil octanoate and bromoxynil octanoate are formed. These derivatives are readily soluble in xylene (SOO and 400 g/1 resp.), and are thus, suitable for the preparation of emulsifiable concentration formulations (Totril, 250 g ioxynil/1) and Brominal , 240 g active ingredient/1. In the plants the esters are degraded to the parent herbidde and exert their action in this form. 

Acylation of isobutylbenzene with acetic anhydride leads with high yield and selectivity to para-acetylisobutylbenzene (Eq. 9) which is an intermediate in the synthesis of ibuprofen, an important antiinflammatory drug [18]. With H/1 zeolite at 140 °C after 1 h the yield is 80 % with 96 % para selectivity. Acylation of tetra-lin with acid chlorides and different zeolites has also been studied [19], For this reaction again acetyl chloride is much less reactive than higher acid chlorides such as butanoyl or octanoyl chloride. The selectivity is in favor of the 2-substituted isomer (85-90%) and limited quantities of the 1 isomer (10-15%) are formed (Eq. 10). 

Tridimensional Y and BEA zeolites are also utilized as efficient catalysts in the acylation of tetralin with acyl chlorides. By using octanoyl chloride and butyroyl chloride in the presence of zeolite Y(40), good yields in the acylation products are achieved (83% and 77% yield, respectively, after 8 h), whereas acetyl chloride (AC) leads only to less than 20% yield of the two isomeric ketones 1 and 2 (1/2 = 7.5) (Scheme 4.2). This trend is correlated to the influence of the chain length of the acylating agent on the efficiency of Friedel-Crafts acylation over zeolite catalysts previously discovered and rationalized. The lower activity of zeolite Y(40) with AC is related to the strong adsorption of organic species, either acetic acid (AAC) or acetyl tetralin. 

The mesoporous aluminosilicate AlMCM-41-type material, prepared from BEA zeolite seeds, can be utilized as catalyst in the acylation of anisole with acyl chloride with the aim of improving the transport of the reactants, especially for the relatively hindered molecules such as octanoyl chloride. The catalyst shows good activity, being para-octanoyl anisole obtained in 90% yield after 1 h. As commonly observed, the use of carboxylic acid as acylating agent results in a slower process (-20% yield after 26 h) due to its lower electrophilicity and the production of water that inhibits the active sites of the zeolite, as previously observed by Beers et al. ... 

Shih, R-C., Wang, J.-H., and Moub, C.-Y. 2004. Strongly acidic mesoporous aluminosilicates prepared from zeolite seeds acylation of anisole with octanoyl chloride. Catal. Today 93-95 365-370. 

Stage 2 A 50 mL three-necked flask was charged with CoBr2 (218 mg, I mmol) in NMP (4mL) and ether (2mL). The reaction mixture was cooled to — 10°C and n-octanoyl chloride (1.62g, lOmmol) was added, followed by /> (4-pivaloxybutyl)zinc (4mL of the prepared solution in Stage 1, 10 mmol). The resulting deep-blue solution was stirred for 0.5 h at — 10°C and worked up as usual. After evaporation of the solvents, the crude residue was purified by flash chromatography (hexane/ether, 95 5) providing the ketone 65 (2.2 g, 78% yield) as a colorless oil. 

An excellent method for converting an acid chloride to a ketone employs transition metal catalysts such as ferric chloride in conjunction with low reaction temperatures. Reaction of butylmagnesium bromide with octanoyl chloride at -60°C gave a mixture of 13% of 80, 4% of 81 (from the secondary reaction of butyl-magnesium bromide and 80), and 60% of 82. when a catalytic amount (2 mol %) of ferric chloride (FeCls) was added, however, a 76% yield of ketone 80 was obtained, along with 3% of the over alkylation product, 81.94 If the intermediate ketone is unreactive to nucleophilic substitution due steric hindrance or peculiar electronic factors (diisopropyl ketone and phenyl-rerr-butyl ketone are both sterically hindered) the ketone can usually be isolated (sec. 8.4.G for problems with hindered ketones). In many instances, however, even dry ice temperatures and reverse addition techniques give poor yields of the ketone.95... 

Octanoyl chloride to perfluoro-octanoic acid c 3M, Dai Nippon, Asahi Glass, Bayer Drakesmith and Hu es (1986) (see also Simons, 1950)... 

Figure 20.1 FTIR spectra of Oakwood sawdust before (a) and after (b) esterification with octanoyl chloride. (Reproduced by permission of Elsevier. Copyright 1995. Reprinted from Reference [10].)...

A process patent and subsequent publication by Fujita and cowoikers, disclosed an improved, large-scale synthesis of fingohmod. In particular, the problem of competing styrene formation that plagued the original synthesis was addressed. In this approach, a Friedel-Crafts acylation of phenylethyl bromide (8) with octanoyl chloride yielded ketone 9 (Scheme 2). Treatment of ketone 9 with sodium ethoxide affords the expected styrene product (10) however, in this case, styrene 10 can function as a Michael-type acceptor to generate the desired amino malonate product 11 in 55% yield (2 steps). Next, hydrogenolysis of the ketone with palladium on carbon in ethanol provided... 

Similar to perfluoroalkanesulfonic acids, the yield of the fluorination reaction decreases with the increasing chain length of the starting material. For example, the electrochemical fluorination of acetyl fluoride yields 76% of perfluoroacetyl fluoride, whereas the fluorination of octanoyl fluoride yields only 10% of perfluorooctanoyl fluoride. The yield is also lower when the readily available acid chlorides, and not the fluorides, are employed as starting materials. A major side reaction of the fluorination of acid chlorides such as octanoyl chloride is the formation of cyclic products. Other by-products and impurities present in PFCA fluorides obtained by electrochemical fluorination include short-chain PFCA fluorides, perfluoroalkanes, COFj, and HF. Perfluorooctanoyl fluoride, the most important PFCA, was industrially synthesized from the corresponding chloride despite the lower yield and formation of cyclic by-products. ... 

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