Fatty acid chlorides

Fatty Held—Peptide Condensates. These proteia detergents are reaction products of fatty acid chlorides and hydrolyzed proteias. They are used ia shampoos because of their mildness on skin, hair, and to eyes when used alone or ia combination with alkyl surfactants (8). 

A.gllsethionates. These are among the oldest of the synthetic detergents and were developed ia Germany to overcome problems of hard water. They are prepared by reaction of fatty acid chlorides with a salt of isethionic acid, ie, 2-hydroxyethanesulfonic acid [107-36-8]. These detergents have moderate foaming properties and have seen only limited use ia shampoos. 

A Acylsarcosinates. Sodium A/-lautoylsarcosinate [7631-98-3] is a good soap-like surfactant. Table 4 gives trade names and properties. The amido group in the hydrophobe chain lessens the interaction with hardness ions. A/-Acylosarcosinates have been used in dentifrices (qv) where they ate claimed to inactivate enzymes that convert glucose to lactic acid in the mouth (57). They ate prepared from a fatty acid chloride and satcosine ... 

The viscous fatty acid chloride is mixed with soHd sodium isothionate and is heated under vacuum and agitation without water or solvent HCl is evolved, leaving the product as a finely divided powder. The direct esterification of fatty acid and sodium isethionate has been patented (69). 

Fatty acid chlorides are very reactive and can be used instead of conventional methods to faciUtate production of amides and esters. lmida2oles are effective recyclable catalysts for the reaction with phosgene (qv) (24). 

Dzulkefly, K Koon, S. Y. Kassim, A. Sharif, A. and Abdullah, A. H. (2007). Chemical modification of SAGO starch by solventless esterification with fatty acid chlorides. The Malaysian. Analy. Set, 11,395-399. 

In the development of the protein-fatty acid condensates it was possible to combine the renewable resources fatty acids (from vegetable oil) and protein, which can be obtained from both animal waste (leather) as well as from many plants, to construct a surfactant structure with a hydrophobic (fatty acid) and a hydrophilic (protein) part (Fig. 4.12). This was carried out by reacting protein hydrolysate with fatty acid chloride under Schotten-Baumann conditions using water as solvent. Products are obtained that have an excellent skin compatibility and, additionally, a good cleaning effect (particularly on the skin) and, in combination with other surfactants, lead to an increase in performance. For instance, even small additions of the acylated protein hydrolysate improve the skin compatibility. An... 

It has been reported that thermoplastic properties can be imparted to wood by modification of wood particles with fatty acid chlorides in a dinitrogen tetroxide -dimethylformamide - pyridine mixture (Funakoshi etal., 1979 Shiraishi etal, 1979, 1983). A method has also been developed for the modification of wood sawdust without the addition of organic solvents (Thiebaud and Borredon, 1995), and the thermal properties of such modified wood determined (Thiebaud etal, 1997). 

Thiebaud, S. and Borredon, M.E. (1995). Solvent-free wood esterification with fatty acid chlorides. Bioresource Technology, 52(2), 169-173. 

One synthesis pathway for preparation of nonionic surfactants containing an amide bond from a fatty acid chloride and tetra(ethylene glycol) is illustrated in Fig. 12 [39]. 

Parrish (1977) reviewed the research and development of lactose ester-type surfactants carried out by Scholnick and his colleagues (Scholnick et al. 1974, 1975 Scholnick and Linfield 1977). Their initial attempts to form lactose esters followed the same transesterification procedures that had been used with sucrose (a fatty acid methyl ester in N,N-dimethylformamide with potassium carbonate as the catalyst). Their successful approach was the reaction of lactose in N-methyl-2-pyrrolidone as the solvent with fatty acid chlorides, resulting in yields of 88 to 95% for esters of lauric, myristic, palmitic, stearic, oleic, and tallow fatty acids. The principal product was the monoester, which is important for detergent use, since diesters and higher esters of lactose are not water soluble. 

Fatty Acid—Sarcosine Condensates. These surfactants are prepared by the reaction of fatty acid chlorides with methyl glycine sodium lauroyl sarcosinate [137-16-6] is an example of this group. They are most effective at pH 5.5—6.0 for foaming activity in soft to moderately hard water. The action of these deteigents is gready reduced under severe hard water conditions. The sarcosinates exhibit compatibility with cationic surfactants and have been suggested for use in formulation of conditioning shampoos (7). 

N-Acylsarcosinates. Sodium AMauroylsarcosinatc is a good soaplike surfactant. The amido group in the hydrophobe chain lessens the interaction with hardness ions. A-Acylosarcosinates are prepared from a fatty acid chloride and sarcosine. 

Figure 5.15 Synthesis of cellulose organic esters by reaction with fatty acid chlorides...

Fatty acid chlorides have been discussed in Section 4.4.3. As with isethionates and sar-cosinates, the cocoyl derivative is predominant. 

The first chlorine atom substituted for hydrogen causes a much larger rise in b.p. than the second or third. Henryk noticed the alternation in b.p. differences, in the fatty acid chlorides, beginning with acetyl chloride ... 

In principle the acyloin coupling of acyl chlorides, in which the enediolate dianion is trapped by unreacted acyl chloride, might be an effective alternative to trapping with TMS-Cl, but the method has rarely been used. Good yields of the enediol diesters (6) were obtained with several fatty acid chlorides using sodium in ether, and the enediol diesters could easily be hydrolyzed to give the acyloins. ... 

Another interesting aspect is the elegant one-step synthesis of manifold substituted isocyanates achieved simultaneously by Washburne et al. and Kricheldorf who both used acyl chlorides acid anhydrides and esters to prepare isocyanates (457) via a Curtius rearrangement. This synthesis is especially useful since it enables for instance long chain isocyanates to be obtained (from fatty acid chlorides) and perfluorated compounds If a perfluoro-... 

It is reported that the covalent attachment of PEG or other polymers to enzymes allows them to be soluble in polar organic solvents (e.g., dioxane, carbon tetrachloride, and benzene), which in turn enhances their catalytic rates. ° The methodology involves tedious bioconjugation chemistry steps to attach activated forms of polymers (e.g., PEG monomethyl ether) to the free amino (lysine) groups of enzymes. In addition, isolation of the modified protein from the bioconjugate chemical reaction mixtnre is required. Proteins can also be modified using fatty acid chlorides, to create hydrophobic derivatives for cell membrane insertion. Modification is not recommended by the author for most situations due to the modest... 

N-Acyl L-Glutamates (AG), RCONHCH(COO M+)CH2CHyCOO M+, M=H+ or Cation Produced by /V-acylation of L-glutamic acid with fatty acid chloride in a mixed solvent of water and water-miscible organic solvent. RCO is usually from coconut and tallow acids. AG is a dibasic acid, so both mono- and di-neutralized materials are possible. The carboxyl group at the a-position is neutralized prior to that at the y-position. The water solubility of monosodium AG is low, so organic amines, i.e., triethanolamine or diethanolamine, or K+ are used as counter-ions. 

Esters from unsaturated fatty acid chlorides are usually viscous or limpid oils soluble in hydrocarbons and turpentine, and whose primary applications are as varnishes, films, artificial threads, aqueous emulsions, and rubber-like plastics.2067,2068 Heating them in an inert gas produced insoluble products formed by polymerization involving double bonds in the acyl moieites.2069 As mentioned in the section on nitrates, acetates of amylose are less compact than amylopectin acetate.1468 Esters of unsaturated acids have also been proposed as re-moistenable adhesives.1971 1972... 

Thiebaud S, Borredon ME (1995) Solvent-free esterification of wood with fatty acid chloride. Bioresource Technology 52... 

Carboxylic esters cannot be brominated by elemental bromine. However, mixtures of esters and acid chlorides in molar proportions 1 1 to 5 1 can be brominated, yields being the same as from 2-6 moles of acid chloride 562 here the 2-bromo fatty acid chloride, formed as intermediate, reacts with the fatty acid ester in a transesterification that leads to the oc-bromo ester and the un-brominated chloride. 

Such reactions were also reported for commercial cosmetic products [66], in which hydrolized proteins were reacted with various fatty acid chlorides to yield protein-fatty acid condensates that have detergent properties. 

Reactions of fatty acids and hydroxyalkylamines yield low purity products which are water soluble (40). They are prepared at 160—180°C while venting the water produced with 85—95% yields. Higher purity can be obtained by the reaction of fatty acid esters with hydroxyalkjiamines in the presence of alkali (41) or alkali metal oxides (42,43). These "superamides" are water insoluble and have better foam stability and rheological characteristics in aqueous dispersions. Disubstituted alkanolamides can be synthesized from many mono or dialkjdene oxide amine condensation products. More complex but commercially usefljl Lamepon, RCON(CH2)CH2COONa (44), and Igepon, RCON(CH2) 2 2 3 i es can be prepared from acylation with fatty acid chlorides. 

The lack of an easily removable amino-protecting group led Fischer to the idea of introducing a-halogen fatty acid chlorides. These were coupled to the free amino group of the partner, the a-halogen fatty-acyl compound formed was reacted with ammonia to yield a new aminoacyl terminus [10]. 

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