Acid chlorides derivatives

Ben zotricbl oride is hydrolyzed to benzoic acid by hot water, concentrated sulfuric acid, or dilute aqueous alkaH. Benzoyl chloride [98-88-4] is produced by the reaction of benzotrichloride with an equimolar amount of water or an equivalent of benzoic acid. The reaction is catalyzed by Lewis acids such as ferric chloride and zinc chloride (25). Reaction of benzotrichloride with other organic acids or with anhydrides yields mixtures of benzoyl chloride and the acid chloride derived from the acid or anhydride (26). Benzo triflu oride [98-08-8] is formed by the reaction of benzotrichloride with anhydrous hydrogen fluoride under both Hquid- and vapor-phase reaction conditions. 

A substituted benzoic acid serves as precursor for the nontricyclic antidepressant bipena-mol (175). Selective. saponification of ester 171 afford.s the half-acid 172. Reaction of the acid chloride derived from this intermediate (173) with ammonia gives the amide 174. Reduction of the last by means of lithium aluminum hydride gives bipenamol (175) [44]. 

The antibiotic cephalosporin derivative 48 has been reported it was prepared by the coupling reaction of the 1,2,4-thiadiazole acid chloride derivative 46 with the amino cephalosporin derivative 47. Similar cephalosporin derivatives were mentioned in CHEC-II(1996) (Equation 13) <2001JAN364>. 

The heterocyclic acylphosphines (52) and (53) have been prepared by the reaction of phenylbis(trimethylsilyl)phosphine with the acid chlorides derived from phthalic and diphenic acids. The reaction of 2,3-dichloromaleic anhydride or thioanhydride with phenylbis(trimethylsilyl)phosphine gives derivatives of the 1,4-dihydro-p-diphosphorin system (54).45... 

Ester derivatives of cellulose, chitin, dextran, amylose, and amylopectin were prepared utilizing the acid chloride derivatives described in Part B of the Experimental Section. 

A classical method for the preparation of a-amino aldehydes is the conversion of N -pro-tected a-amino acid chloride derivatives to aldehydes by hydrogenation in the presence of palladium on charcoal 15 or barium sulfate. 16 This method is especially used for the conversion of phthalyl-a-amino acid chlorides into the corresponding aldehydes. N -Protected amino acid chlorides or fluorides are also readily reduced by lithium tri-ferf-butoxyaluminum hydride1 7 at low temperature without epimerization, but this method is of limited application because overreduction into the respective alcohols also occurs. 

A similar approach has been used in the synthesis of khellin analogues. The acid chloride derived from khellin (457) yields the chromone (458) through reaction with piperidinocyc-loalkenes and subsequent hydrolysis with acid. Some demethylation is observed and the amide (459) is formed in small amounts (Scheme 164) <78JCS(Pi)726). 

Optically pure 1,2-diols.1 The acyllactones 1, obtained by reaction of a Grig-nard reagent with the acid chloride derived from (R)-( -)- or S-( + )-glutamic acid, are reduced by lithium tri-sec-butylborohydride almost exclusively to syn-alcohols (2), regardless of the nature of the R group. In contrast, reduction of 1 with sodium... 

Intramolecular Friedel-Crafts cyclisation of the acid 1 to the 4-position takes place perfectly normally to give the tricyclic ketone. Under almost identical conditions (AlCl3/nitrobenzene/0°C), the acid chloride derived from 2 cyclised smoothly to give a 50% yield of a tricyclic ketone. This however, was shown to be 3, and not the expected product. 

Pyrrole and its N-derivatives 363 react smoothly with acid chlorides in the presence of metallic zinc powder as promoter in toluene under very mild and neutral conditions (at room temperature for 1-3 h) to afford the corresponding 2-acetyl pyrrole derivatives 362 and 364 in high yields (75-90%) with high regioselectivity (Equations 80 and 81) <2002TL8133>. No N-acylated products were obtained under these reaction conditions. Thus, treatment of pyrrole with the acid chloride derivative of cyhalothrin 361 and zinc metal in toluene resulted in the formation of the corresponding 2-acyl pyrrole 362 in 87% yield (Equations 80). 

Variants of the ethyl ketone function of methadone, an aspect already broached with mention of dextromoramide, include ester, sulphone, and secondary alcohol functions in addition to (-amides. The ethyl ester analog 14a obtained by treating the acid chloride derived from methadone cyanide with ethanol is markedly inferior in potency to methadone, while the sulfone 14b (obtained by aminoalkylation of benzhydryl ethyl sulfone) is equipotent... 

Acid chloride derivatives of phosphinous acids [R2POH] and phosphonous acids [RP(OH)2] have been mentioned previously (see Section 3.2) as precursors in the preparation of phosphines. In addition to the coimnon routes of preparation for these trivalent phosphoms acids, particularly through the use of organometallic reagents and Friedel Crafts reactions as noted, several other routes have been developed for their syntheses that are worthy of note. 

For example, two reports of preparation of such species from elemental (red) phosphorus have been noted. The direct preparation of 1-hydroxyphosphonous acids, albeit in moderate yield, is accomphshed by the treatment of elemental phosphorus with aldehydes in aqueous basic medium (equation 12). Using polar aprotic solvents, the double direct addition of elemental phosphoms to arylalkenes proceeds to form phosphinous acids in better yields. Further, acid chloride derivatives are available also by the controlled reaction of elemental phosphoms with chloroalkanes. ... 

The diacetylene ester 771 containing the TTF substituent was obtained in 80% yield by reaction of the acid chloride derived from the acid 769 with the hydroxymethyl-TTF 770. Solid-state polymerization of 771, proceeding via 1,4-addition, gave the polydiacetylene 772 containing TTF side groups (Scheme 113) <1997CC1421>. 

The earlier-mentioned chiral acid (S)-naproxen [15] has also been used, as the acid chloride derived from the S acid, to form diastereomeric esters... 

Phosgene and tertiary carboxylic acid amides form very labile adducts (17 equation 6 not yet isolated or used for preparative purposes as such), which decompose with loss of CO2 very rapidly to give amide chlorides (see Section 2.7.2.2.1.i). Decomposition with evolution of CO2 is a common fate of primary adducts of carbonic acid chloride derivatives. Primary adducts from DMF and chloroformic acid esters (18), for example, decompose immediately to give alkoxymethyleneiminium chlorides, which react to give alkyl chlorides and DMF (equation 7). Adducts (19) from secondary and tertiary carboxamides... 

The synthesis of the protein conjugates is shown in Figure 3. Commercially available carboxylic acids were converted to activated esters by direct DCC (N,N-dicyclohexylcarbodiimide) coupling with N-hydroxysuccinimide or by conversion to the corresponding acid chloride derivative followed by reaction with N-hydroxysuccinimide. Reactiion of the resulting N-hydroxysuccinimide esters with either BSA or OVA led to the desired lysine bonded nitroaromatic hapten-protein conjugates. 

The largest commercial production of a chiral cyanohydrin is that of (S)-3-phenoxy-benzaldehyde cyanohydrin, which is used for the production of synthetic pyrethroids, i.e., coupling of a chiral pyrethrum acid chloride derivative with the (S)-configured cyanohydrin yields insecticides, which represent a valuable market. 

Other examples of heterocycle-annelation using a carboxylic acid or an acid chloride derivative of benzo[b] thiophene dioxides are given below (Scheme 76) [205-207]. ... 

The reactions of acids and acid chlorides derived from a number of different heterocyclic systems have been studied. Cyclizations either onto a benzene ring or onto a ir-excessive heterocycle have been reported. Reactions of 2-phenylquinoline-3-carbonyl chlorides give good yields of the expected products. The product shown in equation (19) was obtained in 90% yield. It was found that the cyclization of pyrrole I-aspartates proceeds more efficiently using phosphoric anhydride (equation 20) than was the... 

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