Alcohols monounsaturated

Silver nitrate -f triglycerides, saturated and heat to 230 to 250 °C phosphotungstic monounsaturated alcohols acid + cobalt nitrate [205, 206]... 

Fig.i General biosynthetic pathways for the production of alcohol, aldehyde, and acetate ester pheromone components in female moths. Top production of saturated fatty acids. Middle production of monounsaturated fatty acids and limited chain shortening produces intermediate compounds that can be reduced to an alcohol. Aldehyde and acetate ester pheromones are produced by an oxidase and acetyl-transferase, respectively. Bottom biosynthetic pathway for the production of the acetate ester pheromone components in the cabbage looper moth, Trichoplusia ni. The CoA derivatives are reduced and acetylated to form the acetate esters. Additional pheromone components include 12 OAc and ll-12 OAc... 

Fig. 2 Action of desaturases and limited chain shortening can produce a variety of mono-unsaturated acyl-CoA precursors that can be modified to form unsaturated pheromone compounds. The arrow pointing down indicates limited chain shortening by two carbons. Modification of all 16-, 14-, 12-, and 10-carbon acyl-CoA derivatives on the carbonyl carbon can account for the majority of monounsaturated acetate esters, aldehydes, and alcohols identified as sex pheromones...

Escolar and oilfish contain a mixture of wax esters with different carbon-chain length, mainly C32, C34, C36, and C38, formed by combining different fatty acids and fatty alcohols. The dominant fatty acids in escolar and oilfish wax esters are the monounsaturated fatty acids (Table 1.3), namely oleic acid (18 1 oo9) and eicosenoic acid (20 loo9), while the dominant fatty alcohols are saturated and monoenoic fatty alcohols (Table 1.4), known as cetyl alcohol (16 0) and oleyl alcohol (18 1 9). PUFA, which are trace components in muscle wax esters, are commonly found in wax esters from roe, they include 20 4o)6, 20 5(b3, 22 5cd3 and 22 6 3. These differences could be due to the functional role in muscle for providing buoyancy, while that of roe is to store energy and key essential PUFA for fry development (Lee and Patton, 1989). 

General recommendations include limiting total calories from fat to 20-25% of daily intake, saturated fats to less than 8%, and cholesterol to less than 200 mg/d. Reductions in serum cholesterol range from 10% to 20% on this regimen. Use of complex carbohydrates and fiber is recommended, and c/s-monounsaturated fats should predominate. Weight reduction, caloric restriction, and avoidance of alcohol are especially important for patients with elevated VLDL and IDL. 

Interesting research assessing the influence of select nutrients on apo A-I expression has been published (reviewed in Mooradian et al.36). Among some of the nutrients associated with decreased expression of the apo A-I gene in cell culture or animal models are polyunsaturated fatty acids, trans-fatty acids, omega-3 fatty acids, glucose, antioxidant vitamins, and zinc deficiency. In contrast, monounsaturated fatty acids, soy proteins, alcohol, and copper deficiency are associated with increased expression of the human apo A-I gene. 

More extensive studies have been done on the spruce budworm, Choristoneura fumiferana, (2JL) which uses (E) - and (Z) -11-tetradecenal as pheromone components. Once again, the first step appears to be reduction of the acid to an alcohol. Then an acetyl Co A fatty alcohol acetyltransferase converts the alcohol to the acetate ester (12.). The enzyme is specific for alcohols with chain lengths of 12-15 carbons, and prefers monounsaturated alcohols to saturated ones. It is located specifically in the pheromone gland, and appears to be microsomal. 

The redbanded leafroller moth uses a mixture of (E) and (Z) -11-tetradecenyl acetates as pheromone components. The pheromone gland of this insect also contains an acetyl Co A fatty alcohol acyl transferase (22.). This enzyme will acetylate 12, 14 and 16 carbon alcohols, and prefers the saturated alcohol to the Z monounsaturated derivative, and the Z to the E, in the approximate ratios of 5 3 1 for saturated, Z and E, respectively. 

Several aspects of the MEP pathway reaction sequence are unexpected, including the conversion of two highly oxidized carbohydrate derivatives, pyruvate 9 and glyceraidehyde phosphate 10 (GAP), into two monounsaturated alcohol diphosphates, IPP 7 and DMAPP 8 (Fig. 2). 

High aliphatic alcohols and wax esters in which aliphatic alcohols or sterols are esterified to fatty or phenolic acids are also present in cmde vegetable oils at low levels and are partially removed in the winterization process during oil refining. Waxes, mainly esters of long-chain saturated fatty acids and a monounsaturated alcohol, especially eicosenoic alcohol, are found in crude vegetable oils such as olive, sunflower, soybean or peanut but are absent from com or rice bran oils... 

Another oil of interest for lubricants is jojoba oil as a replacement of sperm whale oil, the use of which is now banned. Jojoba oil is not a triglyceride but is a wax ester composed mainly of straight chain esters of C20-C22 monounsaturated acids and alcohols. The major constituents, shown in Fig. 6.11, are eicosenyl and docosenyl eicosenoates, where m = 9 and n = 10, 12 ... 

---