[*] Dr. S. Narayan, Dr. J. Muldoon, Prof. M. G. Finn, Prof. V. V. Fokin, Prof. H. C. Kolb, Prof. K. B. Sharpless Department of Chemistry and the Skaggs Institute of Chemical Biology The Scripps Research Institute 10550 North Torrey Pines Road La Jolla, CA 92037 (USA) Fax: (+ 1)619-554-6738 E-mail: sharples@scripps.edu [**] We thank Dr. Vladislav Litosh for carrying out preliminary work. Support from the National Institutes of Health, National Institute of General Medical Sciences (GM 28384), the National Science Foundation (CHE9985553), the Skaggs Institute for Chemical Biology, and the W. M. Keck Foundation is gratefully acknowledged. S.N. thanks the Skaggs Institute for a postdoctoral fellowship. We also thank Dr. Suresh Suri, Edwards Air Force Base, California, for a generous gift of quadricyclane. We urge our fellow chemists to float their problematic reactions on water and to send observations of success or failure to us at onwater@scripps.edu for public dissemination with attribution. Supporting information for this article is available on the WWW under http://www.angewandte.org or from the author. Angewandte Chemie

https://onlinelibrary.wiley.com/doi/pdf/10.1002/anie.200462883

“On Water”: Unique Reactivity of Organic Compounds in Aqueous Suspension

Most of biobased polyols for polyurethanes are synthesized from vegetable oils. In the first part, the present review goes into details of these different synthetic routes to obtain polyols. First, olefinic functionalities of triglycerides could easily be epoxidized, leading to reactive epoxide groups. Second, triglycerides double bonds could undergo a wide ranges of reactions to yield polyols. Finally, the carbonyl group could also be used as a reactive group to yield various polyols. In the second part, the present review is dedicated to the commercial biobased polyols, and, based on the patent literature focuses on the industrial synthetic routes.

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From Vegetable Oils to Polyurethanes: Synthetic Routes to Polyols and Main Industrial Products

A comprehensive review of the literature about use of solvents for extraction of oilseeds is presented. Mention has been found of over 70 solvents. Currently, hexane is the major solvent in use, but recent price increases and safety, environmental and health concerns, have generated interest in alternatives. Solvents vary considerably in chemical and physical properties which affect their performance in oil extraction. The choice of solvent depends upon the primary end product desired (oil or meal). Recent research on alternative solvents has focused on ethanol, isopropanol, methylene chloride, aqueous acetone, and hexane/acetone/water mixtures.

Comparison of alternative solvents for oils extraction

Polyurethanes are among the most versatile polymers because of the wide range of monomers, particularly diols or polyols, that can be utilized in their synthesis. This Review focuses on the most recent advances made in the production of polyurethane materials from vegetable oils. Over the past several years, increasing attention has been given to the use of vegetable oils as feedstocks for polymeric materials, because they tend to be very inexpensive and available in large quantities. Using various procedures, a very broad range of polyols or diols and in some cases, poly- or diisocyanates, can be obtained from vegetable oils. The wide range of vegetable oil-based monomers leads to a wide variety of polyurethane materials, from flexible foams to ductile and rigid plastics. The thermal and mechanical properties of these vegetable oil-based polyurethanes are often comparable to or even better than those prepared from petroleum and are suitable for applications in various industries.

Recent advances in vegetable oil-based polyurethanes.

Quenching of labile functionalised lipids by inorganic sulphur species: evidence for the formation of sedimentary organic sulphur compounds at the early stages of diagenesis

The sodium alkoxide-catalyzed reaction of linseed oil or linseed methyl esters with diethanolamine produces almost exclusively linseed diethanolamides. Reaction conditions, e.g., temperature, amount of excess diethanolamine and mode of adding reactants, are reported. The best conditions for producing diethanolamide directly from linseed oil (1 mole) required adding oil to the sodium alkoxide in diethanolamine (6 moles) and heating at 110–115C for 35 min. The linseed diethanolamide isolated in 93–95% yield was an amber oil. Progress of the reaction, followed by thin-layer chromatography, showed only trace amounts of byproducts.

Polyester amides from linseed oil for protective coatings

Reactions of Conjugated Fatty Acids. IV. Diels-Alder Adducts of 9,11-Octadecadienoic Acid1

Synthetic wax esters with properties similar to those of sperm whale oil have been prepared entirely from soybean and linseed oils. the synthesis required: (a) selective hydrogenation of the oils with copper-on-silica gel catalyst, (b) hydrogenolysis of fatty acids to fatty alcohols with copper-cadmiumchromium catalyst, and (c) esterification of hydrogenolysis products to yield predominantly long chain fatty esters which contained unsaturation in both the alcohol and acid moieties. Similarity of physical and chemical properties indicate that these wax esters are possible replacements for sperm oil. After sulfurization, the wax esters also have potential as extreme pressure lubricant additives.

Sperm oil replacements: Synthetic wax esters from selectively hydrogenated soybean and linseed oils

Linseed and soybean diethanolamides, from the sodium alkoxide-catalyzed reaction of the corresponding oil with diethanolamine, were used as diols to prepare a series of polyesteramides. The diols and dibasic acids or anhydrides were heated in refluxing xylene until the theoretical amount of water was collected in a trap. Low acid-value linseed polymers were prepared with 10, 20, and 30 mole percent excess diol over the dibasic acid, and the effect of the excess diol on molecular weight, viscosity, and film properties of the polymers was examined. Polyesteramides which contained 10 mole percent excess fatty diethanolamide were made with 11 dibasic acids or anhydrides. The polymers were brown-orange oils with Gardner viscosities of Z7 to >>Z10.

L. E. Gast

Papers

Polyester amides from linseed oil for protective coatings

Reactions of Conjugated Fatty Acids. IV. Diels-Alder Adducts of 9,11-Octadecadienoic Acid1

Sperm oil replacements: Synthetic wax esters from selectively hydrogenated soybean and linseed oils

Polyesteramides from linseed oil for protective coatings low acid‐value polymers

Synthetic Lubricants from Polyhydroxystearic Acids