Acid sensitivity

Carbanions stabilized by phosphorus and acyl substituents have also been frequently used in sophisticated cyclization reactions under mild reaction conditions. Perhaps the most spectacular case is the formation of an ylide from the >S-lactam given below using polymeric Hflnig base (diisopropylaminomethylated polystyrene) for removal of protons. The phosphorus ylide in hot toluene then underwent an intramolecular Wlttig reaction with an acetyl-thio group to yield the extremely acid-sensitive penicillin analogue (a penem I. Ernest, 1979). 

Diallylsulfonium salts undergo intramolecular allylic rearrangement with strong bases to yield 1,5-dienes after reductive desulfurization. The straight-chain 1,5-dienes may be obtained by double sulfur extrusion with concomitant allylic rearrangements from diallyl disulfides. The first step is achieved with phosphines or phosphites, the second with benzyne. This procedure is especially suitable for the synthesis of acid sensitive olefins and has been used in oligoisoprene synthesis (G.M. Blackburn, 1969). 

Selective oxidation of secondary alcohols to ketones is usually performed with CrOj/HjSO, I I in acetone (Jones reagent) or with CrOjPyj (Collin s reagent) in the presence of acid-sensitive groups (H.G. Bosche, 1975 C. Djerassi, 1956 W.S. Allen, 1954). As mentioned above, a,)S-unsaturated secondary alcohols are selectively oxidized by MnOj (D.G. Lee, 1969 D. Arndt, 1975) or by DDQ (D. Walker, 1967 H.H. Stechl, 1975). 

The reaction conditions applied are usually heating the amine with a slight excess of aldehyde and a considerable.excess of 2d-30hydrochloric acid at 100 °C for a few hours, but much milder ( physiological ) conditions can be used with good success. Diols, olefinic double bonds, enol ethers, and glycosidic bonds survive a Pictet-Spengler reaction very well, since phenol and indole systems are much more reactive than any of these acid sensitive functional groups (W.M. Whaley, 1951 J.E.D. Barton, 1965 A.R. Battersby, 1969). 

The solubHity properties of the PAG itself can play an important role in the overaH resist performance as weU (50). SolubHity differences between the neutral onium salt and the acidic photoproducts can be quite high and wHl affect the resist contrast. In fact onium salts can serve as dissolution inhibitors in novolac polymers, analogous to diazonaphthoquinones, even in the absence of any acid-sensitive chemical function (51). 

Multiple ether oxygen atoms can be present in the molecule. Cleavage and coupling reactions occur with direct fluorination although to a lesser extent than with ECF. This allows the direct fluorination of acid-sensitive materials, such as the formal shown below, which would not survive ECF (8). 

In general, hydroboration—protonolysis is a stereoselective noncatalytic method of cis-hydrogenation providing access to alkanes, alkenes, dienes, and enynes from olefinic and acetylenic precursors (108,212). Procedures for the protonolysis of alkenylboranes containing acid-sensitive functional groups under neutral or basic conditions have been developed (213,214). 

Diperoxyketals, and many other organic peroxides, are acid-sensitive, therefore removal of all traces of the acid catalysts must be accompHshed before attempting distillations or kinetic decomposition studies. The low molecular weight diperoxyketals can decompose with explosive force and commercial formulations are available only as mineral spirits or phthalate ester solutions. 

Carbonless Copy Paper. In carbonless copy paper, also referred to as pressure-sensitive record sheet, an acid-sensitive dye precursor, such as crystal violet lactone or /V-hen2oy11eucomethy1ene blue, is microencapsulated with a high boiling solvent or oil within a cross-linked gelatin (76,83,84) or in synthetic mononuclear microcapsules. Microcapsules that have a starch binder are coated onto the back of the top sheet. This is referred to as a coated-back (CB) sheet. The sheet intended to receive the image is treated on the front (coated-front (CF)) with an acid. When the top sheet is mechanically impacted, the dye capsules mpture and the dye solution is transferred to the receiving sheet where the acid developer activates the dye. 

Pyrotechnic mixtures may also contain additional components that are added to modify the bum rate, enhance the pyrotechnic effect, or serve as a binder to maintain the homogeneity of the blended mixture and provide mechanical strength when the composition is pressed or consoHdated into a tube or other container. These additional components may also function as oxidizers or fuels in the composition, and it can be anticipated that the heat output, bum rate, and ignition sensitivity may all be affected by the addition of another component to a pyrotechnic composition. An example of an additional component is the use of a catalyst, such as iron oxide, to enhance the decomposition rate of ammonium perchlorate. Diatomaceous earth or coarse sawdust may be used to slow up the bum rate of a composition, or magnesium carbonate (an acid neutralizer) may be added to help stabilize mixtures that contain an acid-sensitive component such as potassium chlorate. Binders include such materials as dextrin (partially hydrolyzed starch), various gums, and assorted polymers such as poly(vinyl alcohol), epoxies, and polyesters. Polybutadiene mbber binders are widely used as fuels and binders in the soHd propellant industry. The production of colored flames is enhanced by the presence of chlorine atoms in the pyrotechnic flame, so chlorine donors such as poly(vinyl chloride) or chlorinated mbber are often added to color-producing compositions, where they also serve as fuels. 

AH latex compounds should contain at least 5 phr of zinc oxide. This is needed to absorb evolved hydrochloric acid either in the compound or finished part. A larger amount should be considered if the part contains or is in contact with acid-sensitive materials such as cotton cloth. Magnesium oxide may destabilize anionic soap systems, and is avoided for that reason. The compound should also contain two parts of an antioxidant, and consideration should be given to the need for a uv screen in light-colored products. 

The range of preparatively useful electrophilic substitution reactions is often limited by the acid sensitivity of the substrates. Whereas thiophene can be successfully sulfonated in 95% sulfuric acid at room temperature, such strongly acidic conditions cannot be used for the sulfonation of furan or pyrrole. Attempts to nitrate thiophene, furan or pyrrole under conditions used to nitrate benzene and its derivatives invariably result in failure. In the... 

CH3CH(Cl)OEt, PhNMc2, CH2CI2, 0°, 10-60 min. These conditions are effective for extremely acid-sensitive substrates or where conditions 1 and 2 fail. 

The introduction of the BDT group proceeds under these rather neutral conditions, and this may prove advantageous for acid-sensitive substrates. The BDT group can also be reduced with Raney nickel to a methyl group or with Bu3SnH to a 2-[(methylthio)phenylthio]methyl ether (MTPM ether)... 

TsOH, DMF, Mc2C(OMe)2, 24 h. This method has become one of the most popular methods for the preparation of acetonides. It generally gives high yields and is compatible with acid-sensitive protective groups such as the TBDMS group. 

LiBF4, wet CH3CN, 96% yield.Unsubstituted 1,3-dioxolanes are hydrolyzed only slowly, but substituted dioxolanes are completely stable.This reagent proved excellent for hydrolysis of the dimethyl ketal in the presence of the acid-sensitive oxazolidine. ... 

The TBDMS ester can be converted directly to an acid chloride [DMF, (COCl)2, It, CH2CI2] and then converted to another ester, with different properties, by standard means. This procedure avoids the generation of HCl during the acid chloride formation and is thus suitable for acid-sensitive substrates. ... 

The 1,3-dioxolane group is probably the most widely used carbonyl protective group. For the protection of carbonyls containing other acid-sensitive functionality, one should use acids of low acidity or pyridinium salts. In general, a molecule containing two similar ketones can be selectively protected at the less hindered carbonyl, assuming that neither or both of the carbonyls are conjugated to an al-kene. ... 

Oxygen ortho esters are readily cleaved by mild aqueous acid (TsOH Pyr, H20 NaHS04, 5 1 DME, H2O, 0°, 20 min ) to form esters that are then hydrolyzed with aqueous base to give the acid. Note that a trimethyl ortho ester is readily hydrolyzed in the presence of an acid-sensitive ethoxyethyl acetal. The order of acid stability is... 

Rapid procedure Dry over anhydrous K2CO3 for 24h, followed by further drying for 24h over 3A molecular sieves or boric anhydride, followed by distn. Alternatively, stir over P2O5 (5% w/v) for 24h then distil. However this last method is not suitable for use in reactions with very acid sensitive compounds. 

The first total synthesis of erythronolide A was accomplished from iodide A and lactone B, the same intermediate which had been used for the synthesis of erythronolide B. The pronounced acid sensitivity of erythronolide A necessitated a digression of the final steps of the synthesis from those used for the earlier synthesis of erythronolide B. 

Snatzke has found that a solution prepared from chromium trioxide and dimethylformamide with a small amount of sulfuric acid has similar chemical properties as the Sarett reagent. It is useful with acid sensitive compounds and oxidation occurs at such a moderate rate that selective oxidations are often possible. Although the position allylic to a A -double bond is not attacked, the 3-hydroxy-A -system cannot be oxidized satisfactorily to the cor-... 

The 21-hydroxyl group in the corticosteroid series can be protected as the base stable triphenylmethyl ether and tetrahydropyranyl ether. " " Mixed acetals from 21-alcohols are extremely acid sensitive compounds. ... 

In Sarett s total synthesis of cortisone, mild acid conditions were developed for the hydration of an ethoxyacetylenic carbinol to the ester without complete dehydration of the tertiary hydroxyl group. An acid-sensitive ketal group in another part of the molecule was also maintained. 

The conversion of 3 to 8 is summarized in Scheme 2. The trityl group (too large and too acid sensitive for the ensuing steps) was removed from N, and both N s were protected by Cbz (benzyloxycarbonyl) groups. Protection of the tertiary OH specifically as the robust TBS (f-butyldimethylsilyl) group was found to be necessary for the sequence involving the electrophilic aromatic substitution step, 5 to 6, and the Stille coupling steps (6 + 7 —> 8). 

HgCl2, CaCO, MeCN, H2O. The calcium carbonate is used as an acid scavenger for acid-sensitive substrates. 

Me3Si)20, PyH TsO, PhH, mol. sieves, reflux, 4 days, 80-90% yield. These mildly acidic conditions are suitable for acid-sensitive alcohols. 

BZOSO2CF3, —78°, CH2CI2, few min. With acid-sensitive substrates, pyridine is used as a cosolvent. This reagent also reacts with ketals, epoxides, and aldehydes. ... 

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