Acetic trichloro

Successful results have been obtained (Renfrew and Chaney, 1946) with ethyl formate methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec.-butyl and iso-amyl acetat ethyleneglycol diacetate ethyl monochloro- and trichloro-acetates methyl, n-propyl, n-octyl and n-dodecyl propionates ethyl butyrate n-butyl and n-amyl valerates ethyl laurate ethyl lactate ethyl acetoacetate diethyl carbonate dimethyl and diethyl oxalates diethyl malonate diethyl adipate di-n-butyl tartrate ethyl phenylacetate methyl and ethyl benzoates methyl and ethyl salicylates diethyl and di-n-butyl phthalates. The method fails for vinyl acetate, ieri.-butyl acetate, n-octadecyl propionate, ethyl and >i-butyl stearate, phenyl, benzyl- and guaicol-acetate, methyl and ethyl cinnamate, diethyl sulphate and ethyl p-aminobenzoate. 

In acetic acid the rates of nitration of chlorobenzene and bromo-benzene were fairly close to being first order in the concentration of aromatic, and nitration fully according to a first-order law was observed with O, m-, and/i-dichlorobenzene, ethyl benzoate and 1,2,4-trichloro-benzene. 

Trichloro- and 2,2,2-tribromoethoxycarbonyl (Tceoc and Tbeoc) protecting groups are introduced with the commercially available 2,2,2-trihaloethyl chloroformates. These derivatives are stable towards CrOj and acids, but can smoothly be cleaved by reduction with zinc in acetic acid at 20 °C to yield 1,1-dihaloethene and CO. Several examples in lipid (F.R. Pfeiffer, 1968, 1970) and nucleotide syntheses (A.F. Cook, 1968) have been described. 

Trityl Ethers. Treatment of sucrose with four molar equivalents of chlorotriphenylmethyl chloride (trityl chloride) in pyridine gives, after acetylation and chromatography, 6,1, 6 -tri-O-tritylsucrose [35674-14-7] and 6,6 -di-O-tritylsucrose [35674-15-8] in 50 and 30% yield, respectively (16). Conventional acetylation of 6,1, 6 -tri-O-tritylsucrose, followed by detritylation and concomitant C-4 to C-6 acetyl migration using aqueous acetic acid, yields a pentaacetate, which on chlorination using thionyl chloride in pyridine and deacetylation produces 4,l, 6 -trichloro-4,l, 6 -trideoxygalactosucrose [56038-13-2] (sucralose), alow calorie sweetener (17). 

Acetic acid, (3,5,6-trichloro-2-pyridinyloxy)-as herbicide, 2, 513 Acetic formic anhydride... 

Trichloroacetaldehyde (chloral) reacts with glucose in the presence of sulfuric acid to form two monoacetals and four diacetals. The trichloro acetal is cleaved by reduction (H2, Raney Ni, 50% NaOH, EtOH, 15 min). The trichloro acetal can probably be cleaved with Zn/AcOH [cf. ROCH(R )OCH2CCl3 cleaved by Zn/ AcOH, AcONa, 20°, 3 h, 90% yield ]. 

Trichloroacetic acid behaves somewhat similarly in that protonation of the enamine occurs l7J7d). Subsequent decarboxylation of the trichloro-acetate gives trichloromethyl anion, which adds to the iminium cation to give the trichloromethyl amine derivative. Thus the enamine (113) undergoes reaction with trichloroacetic acid to give N-[l-(trichloromethyl)cyclo-hexyl]-morpholine (8). The latter compound undergoes rearrangement on... 

Direct bromination readily yields the 6-bromo derivative (111), just as with uracil. Analogous chlorination and iodination requires the presence of alkalies and even then proceeds in low yield. The 6-chloro derivative (113) was also obtained by partial hydrolysis of the postulated 3,5,6-trichloro-l,2,4-triazine (e.g.. Section II,B,6). The 6-bromo derivative (5-bromo-6-azauracil) served as the starting substance for several other derivatives. It was converted to the amino derivative (114) by ammonium acetate which, by means of sodium nitrite in hydrochloric acid, yielded a mixture of 6-chloro and 6-hydroxy derivatives. A modified Schiemann reaction was not suitable for preparing the 6-fluoro derivative. The 6-hydroxy derivative (115) (an isomer of cyanuric acid and the most acidic substance of this group, pKa — 2.95) was more conveniently prepared by alkaline hydrolysis of the 6-amino derivative. Further the bromo derivative was reacted with ethanolamine to prepare the 6-(2-hydroxyethyl) derivative however, this could not be converted to the corresponding 2-chloroethyl derivative. Similarly, the dimethylamino, morpholino, and hydrazino derivatives were prepared from the 6-bromo com-pound. ... 

Substituents in the 6-position (cf. 267) show appreciable reactivity. 6-Bromo-as-triazine-3,5(2j, 4j )-dione (316) undergoes 6-substitution with secondary amines or hydrazine, with mercaptide anions or thiourea (78°, 16 hr), with molten ammonium acetate (170°, 24 hr, 53% yield), and with chloride ion during phosphorous oxychloride treatment to form 3,5,6-trichloro-as-triazine. The latter was characterized as the chloro analog of 316 by treatment with methanol (20°, heat evolution) and hydrolysis (neutral or acid) to the dioxo compound. The mercapto substituent in 6-mercapto-as-triazine-3,5(2iI,4if)-dione is displaced by secondary... 

Trichloro- and dichloromethane, ether, dioxane, benzene, toluene, chlorobenzene, acetonitrile, or even pyridine itself has been employed to carry out the one-pot syntheses. Tliese solvents allow straightforward preparation of the salts. The temperature range between 0° and 20°C is usually employed and the salts formed are sufficiently soluble. In the case of slow reactions, selection of a solvent with a higher boiling point is prohtable since thermal instability of the A -(l-haloalkyl)heteroarylium halides has not been reported. Addition of water or an aqueous solution of sodium acetate does not cause a rapid decomposition of the salts so that this constitutes a useful step in the optimization of some procedures. 

N-Nitroso N phenylglycine, 46, 96 reaction with acetic anhydride to yield 3 phenylsydnone, 46, 96 Nitrosyl chloride, addition to bicyclo-[2 2 ljhepta 2,5 diene, 46, 75 2,4-Nonanedione, 47, 92 Nonane, 1,1,3 trichloro-, 46,104 Nortricyclanol, 46, 74 oxidation by chromic acid, 46, 78 Nortricyclanone, 46, 77 Nortncj clyl acetate 46, 74 frombicyclo[2 2 ljhepta 2,5 dieneand acetic acid, 46, 74 saponification of, 46, 75... 

Because of its high chemical reactivity, acetylene has found wide use in synthesis of vinyl chloride, vinyl acetate, acrylonitrile, vinyl ethers, vinyl acetylene, trichloro- and tetrachloro-ethylene etc., in oxyacetylene cutting and welding, and as a fuel for atomic absorption instruments. 

M. St. C. Flett and P. H. Plesch, J, Chem. Soc., 1952 3355, found evidence for the presence of the trisubstituted ethylene end group and also for trichloro-acetate end groups in low molecular weight polyisobutylenes prepared at 0°C using TiCh and CI3COOH as catalyst and co-catalyst, respectively. For results on the similar polymerization of styrene with TiCh, see P. H. Plesch, J. Chem. Soc., 1963, 1653, 1659, 1662. 

Oxidation of benzene to phenol. This was attempted in the former U.S.S.R. and Japan on a pilot-plant scale. High yields were reported, but full-scale operation apparently was discontinued because of destruction of product by irradiation and the possibility of explosion in the reaction vessel. The latter danger can be controlled in the oxidation of halo-genated hydrocarbons such as trichloro- or tetrachloroethylenes, where a chain reaction leads to the formation of dichloro- or trichloro-acetic acid chlorides through the respective oxides. 

In a more complex type of reaction, propene reacts with methyl trichloro-acetate under the catalytic influence of cyclopentadienylmolybdenum tricarbonyl or cyclopentadienyliron dicarbonyl dimers to give 4-methyl-2,2 -... 

It is important to keep in mind that any extraction of organic matter from soil will include both naturally occurring organic matter and organic contaminants. Separating the two at some later stage of analysis is thus an essential analytical step. For example, extraction of soil with hexane or dichloromethane will extract both l,l,l-trichloro-2,2-di(4-dicholorphenyl)ethane (DDT), a contaminant, and octadecanoic acid, a natural fatty acid. Also, the herbicide 2,4-dichlorophenoxy acetic acid, a contaminant, and indole-3-acetic acid, a natural plant hormone, are both extracted by water (see Figure 12.3). These... 

Co-catalysts other than water. Trichloro- and monochloro-acetic acids, when used as cocatalysts, induced instantaneous polymerisation at -140°. With the following co-catalysts the rate of polymerisation at -78° decreased in the order acetic acid > nitroethane > nitromethane > phenol > water [75a]. Since this is also the sequence of the acid dissociation constants of these substances in water, it appears that the catalytic activity , as shown by the rate of polymerisation, is correlated with the acidity of the cocatalyst in aqueous solution. Flowever, there are two reasons for questioning the validity of this correlation. 

Acetic anhydride Acetyl chloride Alkylaluminums Allyl trichloro silane Aluminum chloride, anhydrous... 

These considerations lead, for example, to the assignment of a predominantly outer sphere character to Cl, Br, F, CIO3, NO3, sulfonate, and trichloro-acetate complexes and an inner sphere character to F", IO3, SO, and acetate complexes of trivalent actinides and lanthanides. The variation in AH° and AS° of complexation of related ligands indicates that those whose pA), values are <2 form predominantly outer sphere complexes, while those for whom > 2 form predominantly inner sphere complexes with the trivalent lanthanides and actinides. As the pK increases above 2, increasing predominance of inner sphere complexation is expected for these metals. 

---