Thioacid chloride

Formation of Carbon-Transition and Inner Transition Metal Bond 5.8.2.13. from Carbon Disulfide, Thioacid Chlorides, or Carbon Diselenide... 

As an extension of this chemistry, the [3+2] cycloaddition reaction of new atropisomeric 4-dialkylamino-5-chloro-l,2-dithiole-3-thiones 130 and DMAD or its diethyl analogue has been utilized to give thioacid chlorides 131 (Scheme 13) <20030L929>. These have been converted into thioamides 132 with 2 equiv of pyrrolidine (or morpholine) by substitution of the 5-chloro substituent and phthalimide ring opening. Similar reactivity toward 1 or 2 equiv of pyrrolidine was noted for 130, which was obtained according to the general method described. 

In 1981 Martin et al. reported that thiophosgene reacts with dimethy-lketene to yield a bis(thioacid chloride) that combines rapidly in Diels-Alder fashion with cyclopentadiene, leading to a [4 + 2] cycloadduct [Eq. (14)].31... 

Friedel-Crafts synthesis with thioacid chlorides... 

Reaction of etio acid 67 with N,N-dimethylthioformamidoyl chloride probably gives initially the mixed anhydride 71 this is not isolated but undergoes O to S carbonyl migration to the anhydride 72. Saponification then leads to the thioacid 73. Reaction of the sodium salt of the acid witli bromochloromethane affords cloticasone propionate (74). The corresponding reaction with hioniofluoromethane leads to fluticasone propionate (75) [16]. 

Thiadiazole, formation, 312, 313, 445 Thiazole formation bromoester, 298-304 bromoketone, 565 Thiazolidinone formation beta lactam, disulfide cleavage, 552 nitrile addition, 301 Thiehopyridine formation, 586 Thienothiazinol formation, 593 Thioacetal formation, 130, 185, 248 glyoxylate, 355 ethyl mercaptopropionate, 447 Thioacid formation, thioformamidoyl chloride, 184... 

The crude peptide thioacid (100 mg) and bromoacetic acid (10 equiv) were added to 6M guanidinium chloride and 100 mM NaOAc, pH 4.6 (10 mL). The peptide soln was mixed briefly and reacted at 25 °C for 1 h. The peptide thioester was immediately purified by HPLC and lyophilized. 

Replacement of side chain carbon C21 by thioester sulfur retains corticoid activity and at the same time provides a function that is destroyed by serum enzymes. The synthesis starts with the potent antiallergic agent flumethasone (32-1). Reaction of that steroid with periodic acid cleaves the terminal bond in the hydroxyacetone side chain to give the hydroxyl acid 32-2 (Scheme 7.32). Steric hindrance around the acid invoke the need for extra activation of that function. Reaction of 32-2 with diphenyl chlorophosphate thus provides the mixed anhydride 32-3. This intermediate is not isolated but reacted in situ with AA -thioformamido chloride. The transient new mixed anhydride, 32.4, then undergoes an internal O to S rearrangement to give the acyl thioacid 32-5. Saponification with sodium hydroxide affords the corresponding thioacid. Alkylation of that intermediate with fluoromethyl bromide then yields the fluoromethyl thioester fluticasone (32-6). 

Thioacids can be prepared by the action of potassium hydrosulphide on acid chlorides —... 

The alternate use of sulfinic acids for penem synthesis entails as the key step a reductive acylation to acyldithioazetidinones 147 [93]. When treated with 3 mol equiv. of a thioacid RCOSH, the sulfinyl chlorides derived from 159... 

A rapid and high-yielding two-step synthesis of fatty thioacids has been devised it involves the reaction of an acid chloride with thioacetic acid followed by deacetylation with propylamine or butylamine (99). The synthesis of positional isomers of unsaturated and hydroxy alkylseleno fatty acids [27] (100), 2,5-disubstituted... 

As has been indicated in a number of studies, sulfur-containing compounds give a synergic effect with amines and phenols in the stabilization of high-molecular compounds [89, 279]. The following have been proposed and are used as stabilizers of polyvinyl chloride mercaptides of antimony [280, 281], condensation products of aldehydes or ketones with mercaptans [63], thioesters [282], salts of thioacids [283], aromatic esters of aliphatic sulfonic acids [284], esters of xanthic acids [285] the use of the polysulfide of the composition... 

Silver nitrate-ammonium hydroxide-chloride (sodium) for thioacids. 

TBD) as base gave superior results. The exception was thioacids, as the products were too unstable to be isolated in this case. Importantly, functional groups such as chloride, alcohol, or azide incorporated on the EBX reagent were also tolerated. 

Compelling spectroscopic evidence in support of the mixed valence formulation (all other known diphosphine disulphides contain P— P bonds) has been presented, together with supporting chemical evidence. Thus, both compounds react with hydrogen chloride to form the quinquevalent thioacid and tervalent... 

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