Higher Aliphatic

Colorless liquid with a mild sweet odor hygroscopic bp 205.5°C mp —15°C density 

044 at 25°C soluble in water (4 g/100 mL), readily mixes with alcohol, ether, and chloroform. 

Benzyl alcohol is a low acute toxicant with a mild irritation effect on the skin. The irritation in 24 hours from the pure compound was mild on rabbit skin and moderate on pig skin. A dose of 750 pg produced severe eye irritation in rabbits. The toxicity of benzyl alcohol is of low order, the effects varying with the species. Oral intake of high concentrations of this compound produced behavioral effects in rats. The symptoms progressed from somnolence and excitement to coma. Intravenous administration in dogs produced ataxia, dyspnea, diarrhea, and hypermotility in the animals. 

Adult and neonatal mice treated with benzyl alcohol exhibited behavioral change, including sedation, dyspnea, and loss of motor function. Pretreatment with pyrazole increased the toxicity of benzyl alcohol. With disulfiram the toxicity remained unchanged. The study indicated that the acute toxicity was due to the alcohol itself and not to bezaldehyde, its primary metabolite (McCloskey et al. 1986). 

No exposure limit is set. Because of its low vapor pressure and low toxicity, the health hazard to humans from occupational exposure should be very low. 

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With higher aliphatic acids, RCOOH, keten yields first a mixed anhydride CH3COOCOR, which can be distilled under reduced pressure by slow distillation at atmospheric pressure the mixed anhydride undergoes rearrangement into the anhydride of the higher fatty acid and acetic acid, for example ... 

Direct, acid catalyzed esterification of acryhc acid is the main route for the manufacture of higher alkyl esters. The most important higher alkyl acrylate is 2-ethyIhexyi acrylate prepared from the available 0x0 alcohol 2-ethyl-1-hexanol (see Alcohols, higher aliphatic). The most common catalysts are sulfuric or toluenesulfonic acid and sulfonic acid functional cation-exchange resins. Solvents are used as entraining agents for the removal of water of reaction. The product is washed with base to remove unreacted acryhc acid and catalyst and then purified by distillation. The esters are obtained in 80—90% yield and in exceUent purity. 

Higher aliphatic alcohols (C —C g) are produced ia a number of important industrial processes using petroleum-based raw materials. These processes are summarized in Table 1, as are the principal synthetic products and most important feedstocks (qv). Worldwide capacity for all higher alcohols was approximately 5.3 million metric tons per annum in early 1990, 90% of which was petroleum-derived. Table 2 Hsts the major higher aliphatic alcohol producers in the world in early 1990. 

Table 1. Synthetic Industrial Processes for Higher Aliphatic Alcohols...

Table 2. Major Cg and Higher Aliphatic Alcohol Producers ...

Vista has offered for ficense a stoichiometric process, which has not yet been commercialized, although the related primary alcohol process has been described (see Alcohols, higher aliphatic-synthetic processes). Other processes, including developments by Dow and Exxon, have been reported in the hterature. 

A number of physical and chemical properties of 1-propanol are Hsted ia Table 1 (2,3). The chemistry of 1-propanol is typical of low molecular weight primary alcohols (see Alcohols, higher aliphatic). Biologically, 1-propanol is easily degraded by activated sludge and is the easiest alcohol to degrade (4). 

Xanthates have been synthesized from C -Cg oxo alcohols ia a reactor with iatensive stirring at 25°C. The water and unreacted alcohol are removed from the product at 40—50°C under vacuum to give a friable powder of 80% purity ia 77% yield (79) (see Oxo process Alcohols, higher aliphatic). 

Cobalt in Catalysis. Over 40% of the cobalt in nonmetaUic appHcations is used in catalysis. About 80% of those catalysts are employed in three areas (/) hydrotreating/desulfurization in combination with molybdenum for the oil and gas industry (see Sulfurremoval and recovery) (2) homogeneous catalysts used in the production of terphthaUc acid or dimethylterphthalate (see Phthalic acid and otherbenzene polycarboxylic acids) and (i) the high pressure oxo process for the production of aldehydes (qv) and alcohols (see Alcohols, higher aliphatic Alcohols, polyhydric). There are also several smaller scale uses of cobalt as oxidation and polymerization catalysts (44—46). 

Propionates and higher aliphatic esters generally become less toxic as the si2e of the alkyl carboxylate increases. As an example, the LD q (rat, oral) for ethyl nonanoate [123-29-5] is greater than 43 g/kg, and the LD q (rat, oral) for ethyl heptanoate [106-30-9] is 34.6 g/kg. 

In 1950, Dahlquist et al. [82] reported the use of polyvinyl A -alkyl carbamates as PSA release materials. Since then, many other types of alkyl side chain polymers have been patented for use as release coatings, including copolymers based on higher alkyl acrylates or methaci ylates [83-86], polyvinyl esters of higher aliphatic fatty acids [87], higher alkyl vinyl esters or ethers and a maleic... 

The calcium salt is used in the preparation of aldehydes by beating it with the calcium salt of a higher aliphatic acid,... 

Benzyl alcohol may be also obtained by the action of caustic potash on benzaldehyde (see Reaction 4, p. 197). This leaction is specially characteristic of cyclic-compounds containing an aldehyde-group in the nucleus, although some of the higher aliphatic aldehydes behave in a similar fashion (Canmzzaio), 2C0H5COII -I KOII = CuII,CH,OII 4- Q,I/r,COOK. 

The higher aliphatic alcohols, from octyl alcohol upwards, have-recently been introduced as perfume materials with considerable success. Only one or two of them, such as nonyl and undeeylenic alcohols, have so far been detected as natural constituents of essential oils, but other members of the series are prepared artificially, and are employed in minute quantities in the preparation of perfumes with characteristic, fruity bouquets. These alcohols are greatly diminished in perfume value by traces of impurities. According to H. J. Prins, the first interesting member of the series is octyl alcohol it has a very sweet, rose-like odour, and is especially suitable for giving a rose perfume that pecnliar sweet smell which distinguishes a rose from a rose perfume. This feature of the aliphatic alcohols diminishes in the series from Cg to Cjg. 

It is strange that only the normal alcohols amongst the higher aliphatic alcohols are of any value as perfumes, the iso-alcohols being useless. 

G. Ethyl or Higher Aliphatic Esters of Aromatic Acids... 

A similar process allows reacting triethyl phosphate and phosphorous pentoxide to form a polyphosphate in an organic solvent [871]. An excess of 1.3 moles of triethyl phosphate with respect to phosphorous pentoxide is the most preferred ratio. In the second stage, a mixture of higher aliphatic alcohols from hexanol to decanol is added in an amount of 3 moles per 1 mole phosphorous pentoxide. Aluminum sulfate is used as a crosslinker. Hexanol results in a high-temperature viscosity of the gel, while maintaining at a pumpable viscosity at ambient temperatures [870]. 

Alcohols. Higher aliphatic alcohols with polyethyleneoxide and poly-propyleneoxide are particularly effective at reducing the gas content of drilling solutions [1442]. 

The removal of fatty acids from neutral higher aliphatic compounds requires vigorous stirring of the hot aqueous and organic phases. 

This is a general method for the preparation of higher aliphatic ketones, it has been found suitable for the preparation of ketones from fatty acids containing 12 to 20 carbon atoms. 

Edeleanu (2) A process for extracting higher aliphatic hydrocarbons from hydrocarbon mixtures by extraction with aqueous urea. 

Alcohol(s), 10 488. See also C12 alcohol Detergent range alcohols Ethanol Fuel alcohol Higher aliphatic alcohols Plasticizer range alcohols Polyhydric alcohols... 

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