Butyryl

CH3CH2CH3COOH + SOClj —> CH3CH3CH3COCI + SOj + HCl n.But3rric acid n-Butyryl chloride (b.p. 101")... 

Prepare n-heptoyl chloride from the acid by treatment with thionyl chloride as detailed for n-butyryl chloride (Section 111,87) b.p. 173-175°. 

Exceptions formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, oxalyl, malonyl, succinyl, glutaryl, furoyl, and thenoyl. 

Butylidyne Butyryl or butanoyl) Camphoroyl Carbamoyl Carbazolyl Carbazoyl Carbonimidoyl Carbonohydrazido preferred to carbohydazido or carbazido)... 

Gyclodextrins. As indicated previously, the native cyclodextrins, which are thermally stable, have been used extensively in Hquid chromatographic chiral separations, but their utihty in gc appHcations was hampered because their highly crystallinity and insolubiUty in most organic solvents made them difficult to formulate into a gc stationary phase. However, some functionali2ed cyclodextrins form viscous oils suitable for gc stationary-phase coatings and have been used either neat or diluted in a polysiloxane polymer as chiral stationary phases for gc (119). Some of the derivati2ed cyclodextrins which have been adapted to gc phases are 3-0-acetyl-2,6-di-0-pentyl, 3-0-butyryl-2,6-di-0-pentyl,... 

The commercially important normal to branched aldehyde isomer ratio is critically dependent on CO partial pressure which, in propylene hydroformylation, determines the rate of interconversion of the -butyryl and isobutyryl cobalt tetracarbonyl intermediates (11). 

In contrast to triphenylphosphine-modified rhodium catalysis, a high aldehyde product isomer ratio via cobalt-catalyzed hydroformylation requires high CO partial pressures, eg, 9 MPa (1305 psi) and 110°C. Under such conditions alkyl isomerization is almost completely suppressed, and the 4.4 1 isomer ratio reflects the precursor mixture which contains principally the kinetically favored -butyryl to isobutyryl cobalt tetracarbonyl. At lower CO partial pressures, eg, 0.25 MPa (36.25 psi) and 110°C, the rate of isomerization of the -butyryl cobalt intermediate is competitive with butyryl reductive elimination to aldehyde. The product n/iso ratio of 1.6 1 obtained under these conditions reflects the equihbrium isomer ratio of the precursor butyryl cobalt tetracarbonyls (11). 

Several methods are available to supplement the phenol alkylations described above. Primary alkylphenols can be produced using the more traditional Friedel-Crafts reaction. Thus an -butylphenol can be synthesized direcdy from a butyl haUde, phenol, and mild Lewis acid catalyst. Alternatively, butyryl chloride can be used to acylate phenol producing a butyrophenone. Reduction with hydrazine (a Wolff-Kishner reduction) generates butylphenol. 

Tests with laboratory-reared P. papatasi show that the duration of complete protection (no bites) provided by DEET, (9-ethoxy-W,A/-diethylbenzamide, (9-chloro-W,W-diethylbenzamide, or A/-butyryl-l,2,3,4-tetrahydroquinoline, averages at least 4 h, but perspiration contributes to a high rate of repellent loss... 

Many related complexes, such as the platenomycin complex (initially YL-704) from S. platensis suhsp. malvinus have been obtained (201—206). A series designated by abbreviations (DHP, DOA) was obtained from another strain of S. platensis (207) the midecamycin complex (initially SF-837) was produced by S. mjcarojaciens (208—212) the espinomycin factors were produced by S. Jungicidicus var. espinomjceticus (213,214) the turimycin series of fifteen components, isolated from culture broths of S. hjgroscopicus are identical to other members of the leucomycin group (215). Niddamycin (42, R = H, R = butyryl) was isolated from cultures of S. djakartensis (216). 

Fig. 2. Semisynthetic derivatives of I6-membered macroHdes rokitamycin (62, R = R " = H, R = butyryl, R" = propionyl) miokamycin (62,...

Fig. 3. Effects of composition on physical properties. A, acetyl B, butyryl C, cellulose. 1, increased tensile strength, stiffness 2, decreased moisture sorption 3, increased melting point 4, increased plasticizer compatibiUty 5, increased solubiUties in polar solvents 6, increased solubiUties in nonpolar...

Propionyl or butyryl of total acyl in esterification bath, %... 

Fig. 5. Composition of cellulose acetate butyrate (propionate) as a function of butyryl (propionyl) content of esterification bath.

Fig. 6. Conversion of weight percent to degree of substitution per anhydroglucose unit (max = 3.0), where is butyryl, is propionyl, and 0 is acetyl.

The price of cellulose ester flake has generally increased with inflation and as of mid-1987 was estimated at ca 3.64— 4.71/kg for cellulose diacetate molding resin and from ca 4.16— 4.71/kg for the mixed esters molding resins depending on purity and the number of propionyl or butyryl esters (4). 

Determining the degree of substitution using standard proton nmr refles on the integral ratio between the ceUulosic ring protons ( i 5.0-2.96) and the ester alkyl protons ( i 1.26 for butyryl and propionyl and i 2.06 for acetyl methyl groups). This simple procedure is used extensively to determine the extent of esterification and is currently the fastest, easiest way for determining the DS of mixed cellulose esters. 

Acetyl, % Butyryl, % Hydioxyl, % Acetate Butyrate Hydroxyl AppHcation... 

Cellulose acetate butyrates with high butyryl content and low viscosity are soluble in inexpensive lacquer solvents. They are widely used in lacquers for protective and decorative coatings appHed to automobiles and wood furniture. 

Higher butyryl esters, formulated with acryUc polymers, provide coatings with excellent weather resistance, good colorfastness and dispersibiUty, and good flow properties (154). Formulations for a typical automotive refinishing lacquer and a wood furniture lacquer are given in Tables 12 and 13, respectively. Low viscosity, high butyryl cellulose esters tolerate substantial amounts of alcohol solvent without appreciable increase in solution viscosity. 

An alcohol-soluble cellulose acetate butyrate containing ca 50% butyryl and ca 4.5% hydroxyls available commercially. 

Low viscosity cellulose propionate butyrate esters containing 3—5% butyryl, 40—50% propionyl, and 2—3% hydroxyl groups have excellent compatibihty with oil-modified alkyd resins (qv) and are used in wood furniture coatings (155). Acetate butyrate esters have been used in such varied apphcations as hot-melt adhesive formulations (156), electrostatically spray-coated powders for fusible, non-cratering coatings on metal surfaces (157—159), contact lenses (qv) with improved oxygen permeabiUty and excellent wear characteristics (160—162), and as reverse-osmosis membranes for desalination of water (163). 

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