1- Butanol Table

The prediction of yAB from this rule is approximate but found to be useful in a large number of systems (such as alkanes water), with some exceptions (such as water butanol) (Table 2.3). For example,... 

The HO2 product of the initiation step is a polar species. Therefore, it is quite natural to expect the transition state of the initiation step to show some ionic character. That this is so can be seen from the enhancement in in 20 going from 2,2,4-isooctane to ethanol or n-butanol (Table 26). 

Isopropyl methyl groups in 3-methyl-2-butanol (Table 4.23) are diastereotopk (Sc =18.1 and 18.3 ppm) due to the adjacent asymmetric carbon atom. It was shown that... 

Note that control and maintenance of low water contents during esterification progress was a difficult task only for reactions carried out with ferf-butanol (Table 2). Besides affecting reaction yields, high water contents favors the reverse reaction (ester hydrolysis) by decreasing even more the amount of ester formed (1,4). 

The hydroxylation of n-hexane on TS-1, in contrast to the epoxidation of propene, reached its maximum rate in the least polar solvent, t-butanol (Table 18.13). Acetonitrile behaved quite similarly to methanol and water [24, 25, 169]. On the assumption that t-butanol was comparable to i-propanol for the effects on adsorption, a clear relationship between rates and partition coefficients was lacking. Considering that hydroxylation and epoxidation involve different active species and mechanisms, a diverse role of the solvent in the two active species could contribute to the differences, whereas the partition coefficients alone could not... 

Table 9.9 lists the commercial specifications of butanols. Tables 9.10 and 9.11 give the uses and production of n-butanoi and isobutanol for Western Europe, the United States and Japan in 1984. 

Axial-chiral enantiomerically highly enriched binaphthols 4, which are highly useful chiral auxiliaries, are accessible either through acylation of the racemic diol with vinyl acetate or deacylation of the racemic diacetate with butanol (Table 11.1-22), both catalyzed by Pseudomonas cepacia lipase. 

S5, 25, 3S )-2-(Phenylsulflnyl)-3-butanol (Table 5, Entry 8) Typical Procedure27 ... 

As outlined m Table 7 1 (+) 2 butanol has the S configuration Its mirror image IS (—) 2 butanol which has the R configuration... 

Asymmetric Hydroboration. Hydroboration—oxidation of (Z)-2-butene with diisopinocampheylborane was the first highly enantioselective asymmetric synthesis (496) the product was R(—)2-butanol in 87% ee. Since then several asymmetric hydroborating agents have been developed. Enantioselectivity in the hydroboration of significant classes of prochiral alkenes with representative asymmetric hydroborating agents is shown in Table 3. 

Acute oral LD q data for nitro alcohols in mice are given in Table 1. Because of their low volatiHty, the nitro alcohols present no vapor inhalation ha2ard. They are nonirritating to the skin and, except for 2-nitro-1-butanol, are nonirritating when introduced as a 1 wt % aqueous solution in the eye of a rabbit. When 0.1 mL of 1 wt % commercial-grade 2-nitro-1-butanol in water is introduced into the eyes of rabbits, severe and permanent corneal scarring results. This anomalous behavior may be caused by the presence of a nitro-olefin impurity in the unpurifted commercial product. 

Commercial primary amyl alcohol is a mixture of 1-pentanol and 2-methyl-1-butanol, iu a ratio of ca 65 to 35 (available from Union Carbide Chemicals and Plastics Company Inc. iu other ratios upon request). Typical physical properties of this amyl alcohol mixture are Hsted iu Table 2 (17). 

Like the lower alcohols, amyl alcohols are completely miscible with numerous organic solvents and are excellent solvents for nitrocellulose, resia lacquers, higher esters, and various natural and synthetic gums and resius. However, iu contrast to the lower alcohols, they are only slightly soluble iu water. Only 2-methyl-2-butanol exhibits significant water solubiUty. As associated Hquids, amyl alcohols form a2eotropes with water and//or a variety of organic compounds (Table 3). 

Table 8 summarizes domestic consumption by use for amyl alcohols. About 55% of the total 1-pentanol and 2-methyl-1-butanol production is used for zinc diamyldithiophosphate lubrication oil additives (150) as important corrosion inhibitors and antiwear additives. Amyl xanthate salts are useful as frothers in the flotation of metal ores because of their low water solubiUty and miscibility with phenoHcs and natural oils. Potassium amyl xanthate, a collector in flotation of copper, lead, and zinc ores, is no longer produced in the United States, but imports from Germany and Yugoslavia were 910 —1100 t in 1989 (150). 

Recovery and Purification. The dalbaheptides are present in both the fermentation broth and the mycelial mass, from which they can be extracted with acetone or methanol, or by raising the pH of the harvested material, eg, to a pH of 10.5—11 for A47934 (16) (44) and A41030 (41) and actaplanin (Table 2) (28). A detailed review on the isolation of dalbaheptides has been written (14). Recovery from aqueous solution is made by ion pair (avoparcin) or butanol (teicoplanin) extraction. The described isolation schemes use ion-exchange matrices such as Dowex and Amberlite IR, acidic alumina, cross-linked polymeric adsorbents such as Diaion HP and Amberlite XAD, cation-exchange dextran gel (Sephadex), and polyamides in various sequences. Reverse-phase hplc, ion-exchange, or affinity resins may be used for further purification (14,89). 

Propylene oxide is a colorless, low hoiling (34.2°C) liquid. Table 1 lists general physical properties Table 2 provides equations for temperature variation on some thermodynamic functions. Vapor—liquid equilibrium data for binary mixtures of propylene oxide and other chemicals of commercial importance ate available. References for binary mixtures include 1,2-propanediol (14), water (7,8,15), 1,2-dichloropropane [78-87-5] (16), 2-propanol [67-63-0] (17), 2-methyl-2-pentene [625-27-4] (18), methyl formate [107-31-3] (19), acetaldehyde [75-07-0] (17), methanol [67-56-1] (20), ptopanal [123-38-6] (16), 1-phenylethanol [60-12-8] (21), and / /f-butanol [75-65-0] (22,23). 

Nicotinamide is a colorless, crystalline solid. It is very soluble in water (1 g is soluble in 1 mL of water) and in 95% ethanol (1 g is soluble in 1.5 mL of solvent). The compound is soluble in butanol, amyl alcohol, ethylene glycol, acetone, and chloroform, but is only slightly soluble in ether or benzene. Physical properties are Hsted in Table 1. 

The butanols are all colorless, clear Hquids at room temperature and atmospheric pressure with the exception of /-butyl alcohol which is a low melting soHd (mp 25.82°C) it also has a substantially higher water miscibility than the other three alcohols. Physical constants (1) of the four butyl alcohols are given in Table 1. 

Table 1. Physical Properties of the Butyl Alcohols (Butanols)...

The most common a2eotropes (3,4) formed by the butanols are given in Table 2. Butyl alcohol Hquid vapor pressure/temperature responses (5,6), which are important parameters in direct solvent appHcations, are presented in Figure 1. Similarly, viscosity/temperature plots (1) for the four butanols are presented in Figure 2. 

With the exception of gasoHne grade /-butyl alcohol (GTBA), the butanols are generally marketed in bulk in the pure isomeric form. ASTM specifications (29) for n-, iso- and j -butyl alcohol are given in Table 3. Butanol specification purity is routinely obtained by gas chromatography (30). 

AH four butanols are thought to have a generaHy low order of human toxicity (32). However, large dosages of the butanols generaHy serve as central nervous system depressants and mucous membrane irritants. Animal toxicity and irritancy data (32) are given in Table 4. 

Table 4.. Animal Toxicity and Irritancy Data for Butanols...

Flammability characteristics (1) of the four butanols are given ia Table 5. ... 

Chemicals. Although the amount of butylenes produced ia the United States is roughly equal to the amounts of ethylene and propylene produced, the amount consumed for chemical use is considerably less. Thus, as shown ia Table 10, the utilisation of either ethylene or propylene for each of at least five principal chemical derivatives is about the same or greater than the utilisa tion of butenes for butadiene, their main use. This production is only about one-third of the total the two-thirds is derived directiy from butane. The undedyiag reasons are poorer price—performance compared to derivatives of ethylene and propylene and the lack of appHcations of butylene derivatives. Some of the products are more easily derived from 1-, 2-, and 3-carbon atom species, eg, butanol, 1,4-butanediol, and isobutyl alcohol (see Acetylene-DERIVED chemicals Butyl alcohols). 

Ethanol s use as a chemical iatemiediate (Table 8) suffered considerably from its replacement ia the production of acetaldehyde, butyraldehyde, acetic acid, and ethyUiexanol. The switch from the ethanol route to those products has depressed demand for ethanol by more than 300 x 10 L (80 x 10 gal) siace 1970. This decrease reflects newer technologies for the manufacture of acetaldehyde and acetic acid, which is the largest use for acetaldehyde, by direct routes usiag ethylene, butane (173), and methanol. Oxo processes (qv) such as Union Carbide s Low Pressure Oxo process for the production of butanol and ethyUiexanol have totaUy replaced the processes based on acetaldehyde. For example, U.S. consumption of ethanol for acetaldehyde manufacture declined steadily from 50% ia 1962 to 37% ia 1964 and none ia 1990. Butadiene was made from ethanol on a large scale duriag World War II, but this route is no longer competitive with butadiene derived from petroleum operations. 

The structure of 2-butanol is CH3CHOHCH2CH3. Determine group contributions from Table 2-385. 

Not all organic compounds that contain —OH groups are soluble in water (Table 10.1). As molar mass increases, the polar —OH group represents an increasingly smaller portion of the molecule. At the same time, the nonpolar hydrocarbon portion becomes larger. As a result, solubility decreases with increasing molar mass. Butanol, CH3CH2CH2CH2 OH, is... 

TABLE 33 Epoxidation of Cyclohexene with Hydrogen Peroxide at Oxodiperoxohexa-methylphosphortriamidomolybdenum(VI) in the Presence of Alkanesulfonates (50°C, 40 mmol cyclohexene in 30 g ter/-butanol, 0.4 mmol Mo05 HMPT, 50 mmol H,02 as 30 wt % aqueous solution)... 

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