Dibutyl tartrate

Butanol, which at one time was an unwanted by-product in the preparation of acetone, is now the most important product of the fermentation. The building of a large new factory in Puerto Rico using 10,000 tons of molasses per annum for its production is an indication of this importance. Butanol is probably still the best solvent for cellulose nitrate lacquers. Dibutyl phthalate is certainly the most widely used plasticizer for synthetic resins, and butyl oleate, tributyl citrate and dibutyl tartrate have also been described as plasticizers. Another important use of butanol is as a source of butadiene, which serves as an intermediate in the conversion of sucrose into a synthetic rubber. Although in recent years other methods have been described for the preparation of butanol (for example, from ethyl alcohol and from acetylene), yet the fermentation of carbohydrates is still the cheapest process. 

Tests of the best hydrogen bonding agents in ether-alcohol showed the following compds trimethyl-, trimethallyl-, tributyl phosphates, isophorone, dimethyl acetamide, and dibutyl tartrate were superior to dibutyl phthalate or triacetin in the amts reqd for gelatinization and in the viscosities of the resulting solns... 

Cleavage of open-chain symmetrical diols, which must yield a single alde-hydic product, is clearly of most value. The preparation of butyl glyoxylate from dibutyl (+ )-tartrate (Expt 5.77) using lead tetra-acetate in benzene solution is an interesting example. A second example is the cleavage of the 1,2-diol system... 

In view of the quantities of benzene (CAUTION) required, the entire preparation must be carried out in the fume cupboard. Place a mixture of 125 ml of pure benzene and 32.5 g (0.123 mol) of dibutyl ( + )-tartrate (1) in a 500-ml threenecked flask, equipped with a Hershberg stirrer (Fig. 2.49) and a thermometer. Stir the mixture rapidly and add 58 g (0.13 mol) of lead tetraacetate (Section 4.2.45, p. 441) in small portions over a period of 20 minutes while maintaining the temperature below 30 °C by occasional cooling with cold water. Continue the stirring for a further 60 minutes. Separate the salts by suction filtration and wash with two 25 ml portions of benzene. Remove the benzene and acetic acid from the filtrate by flash distillation and distil the residue under diminished pressure, preferably in a slow stream of nitrogen. Collect the butyl glyoxylate (2) at 66-69 °C/5mmHg. The yield is 26g (81%). 

Notes. (1) The purified commercial dibutyl (+ )-tartrate, m.p. 22 °C, may be used. It may be prepared by using the procedure described under isopropyl lactate (Expt 5.145). Place a mixture of 75g of (-I-)-tartaric acid, lOg of Zerolit 225/H , 110g (135 ml) of redistilled butan-l-ol and 150 ml of sodium-dried benzene in a 1-litre threenecked flask equipped with a sealed stirrer, a double surface condenser and an automatic water separator (cf. Fig. 2.31(a)). Reflux the mixture w th stirring for 10 hours about 21 ml of water collects in the water separator. Filter ol the ion-exchange resin... 

The indium-induced Reformatsky reaction with stoichiometric amounts of chiral amino alcohols such as cinnco-nine and cinchonidine gives optically active /3-hydroxy esters with 40%-70% ee (Table 19). In contrast to the smooth reaction with uncomplexed indium-based Reformatsky reagents, ketones do not react with the complexed indium Reformatsky reagents. Other chiral ligands, including (—)-spartein, (—)-norephedrine, (+)-(l-methylpyrrolidin-2-yl)diphenylmethanol, (+)-Dibutyl tartrate and (+)-l,l -bi-2-naphthol, are not effective for this reaction.324... 

Properties Light-brown paste. Soluble in alcohol, acetone, dibutyl tartrate, ethylene glycol. 

If a chiral liquid is coated on the surface of the column packing particles, a chiral liquid-liquid partition system is obtained. The mobile phase must be saturated with stationary phase. A thermostat must be provided in order to keep the equilibrium of the solution constant. An example of this method is shown in Figure 22.3 with (+ )-dibutyl tartrate as the stationary phase, with which several /3-amino alcohols can be separated. 

Figure 22.3 Separation of norephedrine enantiomers with (+ )-dibutyl tartrate as the liquid stationary phase [reproduced with permission from C. Pettersson and H.W. Stuurman, J. Chromatogr. Sci., 22, 441 (1984)]. Conditions column, 15cm X 4.6mm i.d. stationary phase, ( + )-dibutyl tartrate on 5 j,m Phenyl Hypersil mobile phase, phosphate buffer (pH 6) containing hexafluorophosphate, saturated with dibutyl tatrate UV detector, 254nm.

Butyl myristate Methyl cocoate Oleyl alcohol PEG-300 oleate PEG-300 stearate Propylene glycol myristate plasticizer, delayed tack latex 1,4-Cyclohexanedimethanol dibenzoate plasticizer, dental adhesives n-Butyl phthalyl-n-butyl glycolate plasticizer, dental compounds Carnauba (Copemica cerifera) wax plasticizer, dental impression compounds Japan (Rhus succedanea) wax plasticizer, deodorants Hexyldecyl benzoate plasticizer, depilatories Oxidized beeswax plasticizer, detergents PPG-20 lanolin alcohol ether plasticizer, dip parts Diphenyl octyl phosphate plasticizer, dopes Di butyl tartrate plasticizer, dry cleaning PEG-8 cocoate PEG-20 hydrogenated castor oil PEG-60 hydrogenated tallowate PEG-12 ricinoleate PEG-2 stearate PEG-2 tallowate plasticizer, elastomers Butyl acetyl ricinoleate Butyl cyclohexyl phthalate Dibutyl phthalate Dibutyl tartrate n-Dioctyl phthalate... 

Castor oil, polymerized Dibutyl tartrate PEG-1500 stearate Propylene glycol laurate plasticizer, lubricating oils Methyl cocoate PEG-300 oleate PEG-300 stearate Propylene glycol myristate plasticizer, make up... 

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