Hydrolysis with water

Hoesch synthesis A variation of the Gattermann synthesis of hydroxy-aldehydes, this reaction has been widely applied to the synthesis of anthocyanidins. It consists of the condensation of polyhydric phenols with nitriles by the action of hydrochloric acid (with or without ZnCl2 as a catalyst). This gives an iminehydrochloride which on hydrolysis with water gives the hydroxy-ketone. 

The acetylations may alternatively be performed in 100 ml. conical flasks, and the contents after dilution and hydrolysis with water can then be carefully washed into 250 ml. beakers for the titration with alkali. The calculation is precisely similar to that of the first method. Excellent results are r>btalned. 

Phosphoms oxychloride is stable to above 300°C. Hydrolysis with water yields phosphoric acid. 

As indicated in Section 29.3, the conversion of the chlorosilane intermediates into polymers is accomplished by hydrolysis with water followed by spontaneous condensation. In practice there are three important stages ... 

The formation of 65 must have taken place via the normal alkylation product (66) which undergoes hydrolysis with water followed by reaction of pyrrolidine with the more reactive aldehyde group to give an intermediate (67), which can then cyclize to give the observed product (65). 

Hydrolysis with water occurs slowly, but is violent with aqueous acids. 

The coordination of the alkyne to the rhodium catalyst allows the carborhodation of the triple bond to afford the vinylrhodium intermediate 47 (Scheme 14). The rearrangement of this organometallic compound into the 2-(alkenyl)phenylrhodium intermediate 48 is evidenced by one deuterium incorporation resulting from the deuter-iolysis of the Rh-C bond. The addition of the phenylrhodium intermediate 45 must occur before its hydrolysis with water. The 2-(alkenyl)phenylrhodium intermediate 45, generated by the phenylrhodation of an alkyne followed by... 

The formation of the linear cyclic polymers is dependent upon the reaction conditions. Hydrolysis with water alone gives rise to 50-80 per cent linear polydimethyl siloxane a, w-diols and 50-20 per cent polydimethyl-cyclosiloxanes. 

PA Loss of molecular weight by hydrolysis with water contamination... 

A naphthalene-catalyzed (<10%) lithiation of a,a-dibromo esters 152 in THF at —78°C was used to generate ester dianions 153, which by warming at 0°C gave lithium ynolates 154. These intermediates were trapped by carbonyl compounds, for instance benzophenone, to give, after final hydrolysis with water, a,/3-unsaturated acids 155 (Scheme 55)" ... 

Chlorinated ketals 221 were lithiated using a catalytic amount (8%) of naphthalene in THE at —78°C to generate the corresponding masked lithium 5-enolates 222, which upon treatment with different electrophiles in THE at temperatures ranging between —78 and 20 °C, and final hydrolysis with water, afforded protected functionalized ketals 223 (Scheme 76). The application of this methodology to the chlorinated dithiane 224, under the same reaction conditions, gave the intermediate 225 and finally products 226 (Scheme 76) -... 

The hthiation of the to-chloro acetal 230 using a catalytic amount of naphthalene (4%) in THF at —78°C gave the corresponding masked tu-lithio enolate 231, which reacted with different electrophiles at —78 °C to room temperature yielding, after hydrolysis with water, the expected functionalized acetals 232 (Scheme 78) . 

A special case of functionalized aryllithium reagents appears when the corresponding aryl group bears a ketal moiety at the benzylic position due to the lability of the benzyUc carbon-oxygen bonds. However, working under Barbier-type conditions and using naphthalene (10%) as the electron carrier catalyst, the reaction of chlorinated materials 242 afforded, after hydrolysis with water, the corresponding polyfunctionalized products 243 (Scheme 81). ... 

A chiral version of the above-mentioned ring opening of oxetanes has been applied to chiral oxetanes. An example is shown in Scheme 90 starting from oxetane 303, which after DTBB-catalyzed (5%) lithiation in TFIF at 0°C gave the (/-functionalized organohthium intermediate 304, which by treatment with different electrophiles and final hydrolysis with water yielded the corresponding products 305 (Scheme 90) °. 

Phenylthietane (321) was opened with lithium and a catalytic amount of DTBB (5%) in THF at —78°C to generate the most stable benzylic intermediate 322 which, by reacting with an electrophile at the same temperature followed by hydrolysis with water, gave functionalized thiols 323 (Scheme 94) . When carbon dioxide was used as electrophilic reagent, 2-phenyl y-thiolactone was directly obtained. 

Another type of heterocycle containing two heteroatoms susceptible of being cleaved reductively are 1,3-dioxanes or 1,3-oxathianes 422. They were treated with lithium and a catalytic amount of DTBB (4.5%) in THF at room temperature (Y = O) or at —78 °C (Y = S) to yield, after hydrolysis with water, functionalized homobenzylic alcohols 425 (Scheme 119) . The participation of intermediates 423 and 424 has been postulated in order to explain the obtained results. 

Y = O) or —90°C (Y = NMe, S) gave the corresponding intermediates 427 resulting from a carbon-sulfur cleavage. Further reaction of these functionalized organolithium compounds with different electrophiles at the same temperature, followed by hydrolysis with water, yielded products 428 (Scheme 120) . 

The reaction of dichloromethane (or its dideuterio derivative) (430) with lithium and a catalytic amount of DTBB (5%) in the presence of a carbonyl compound as electrophile in THF at —40 °C led, after final hydrolysis with water, to the corresponding 1,3-diols... 

In the case of chlorobenzyl chlorides 504, the same process had to be performed under Barbier-type reaction conditions. These dichlorinated materials 504 were lithiated with DTBB in a catalytic amount (4%) in the presence of different electrophiles to give, after final hydrolysis with water, the corresponding difunctionalized products 505 (Scheme 141) ". ... 

Phenone imines 587 were lithiated with lithium and a catalytic amount of naphthalene (8%) in the presence of different carbonyl compounds as electrophiles in THF at temperatures ranging between —78 and room temperature, giving, after hydrolysis with water, the corresponding 1,2-aminoalcohols 588 (Scheme 154). ... 

The reaction mechanism proposed for the addition of organostannanes [29] is similar to that for organoboronic acids. An example of the reaction of methyl vinyl ketone 42 is outlined in Scheme 3.15. The catalytic cycle involves a cationic rhodium complex G, phenylrhodium H, and oxa-n -allylrhodium I. Stannyl enol ether 44 is formed by the reaction of oxa-n -allylrhodium I with Me3SnBF4, which upon hydrolysis gives the ketone 43. The lower yields in the absence of water were explained by the further reaction of 44 with methyl vinyl ketone 42. The rapid hydrolysis with water may prevent such oligomerization. 

The resulting product is then hydrolyzed by the enzyme Citrusi acetylesterase to the potassium salt of 3-hydroxymethyl-7-methoxy-7-[2-(2-thienyl)acetamido]-3-cefem-4-carboxylic acid (32.1.2.38). Using the method described above, i.e. the initial reaction with chlorosulfonyl isocyanate followed by hydrolysis with water, the resulting compound,... 

Lee S, Jeon C, Park Y (2004) Eabrication of Xi02 tubules by template synthesis and hydrolysis with water vapor. Chem Mater 16 4292-4295... 

This compound on reduction with sodium amalgam and hydrolysis with water gives tryptophane —... 

Hydrolysis with water gives arsenous acid and HCl ... 

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