Pivaloyl

Pivalates. The selective pivaloylation of sucrose with pivaloyl (2,2-dimethylpropionyl) chloride has been thoroughly investigated (56). The reactivity of sucrose toward pivaloylation was shown to be significantly different from other sulfonic or carboxyflc acid chlorides. For example, reaction of sucrose with four molar equivalent of toluene-/)-sulfonyl chloride in pyridine revealed, based on product isolation, the reactivity order ofO-6 0-6 > 0-1 > 0-2 (57). In contrast, a reactivity order for the pivaloylation reaction, under similar reaction conditions, was observed to be 0-6 0-6 > 0-1 > 0-4. 

Other Rea.ctlons, The anhydride of neopentanoic acid, neopentanoyl anhydride [1538-75-6] can be made by the reaction of neopentanoic acid with acetic anhydride (25). The reaction of neopentanoic acid with acetone using various catalysts, such as titanium dioxide (26) or 2irconium oxide (27), gives 3,3-dimethyl-2-butanone [75-97-8] commonly referred to as pinacolone. Other routes to pinacolone include the reaction of pivaloyl chloride [3282-30-2] with Grignard reagents (28) and the condensation of neopentanoic acid with acetic acid using a rare-earth oxide catalyst (29). Amides of neopentanoic acid can be prepared direcdy from the acid, from the acid chloride, or from esters, using primary or secondary amines. 

Acetanilides, benzoyl-colour couplers in colour photography, 1, 372 Acetanilides, pivaloyl-colour couplers in colour photography, 1, 372 Acetazolamide — see l,3,4-Thiadiazole-2-sulfonamide, 5-acetamido-Acetic acid, acetamidocyano-ethyl ester, 1, 307 Acetic acid, 2-acylphenyl-isochroman-3-one synthesis from, 3, 858 Acetic acid, 3-benzo[6]thiophenyl-biological activity, 4, 912 Acetic acid, l,2-benzoxazol-3-yl-electrophilic substitution, 6, 48... 

Thiophene, 3-pentadeuterophenyl-chemical shifts, 4, 730 Thiophene, 2-phenyl-oxidation, 4, 800 phototranspositions, 4, 743 rearrangement, 4, 42 reduction, 4, 775 synthesis, 4, 865, 914 UV spectrum, 4, 735 Thiophene, 3-phenyl-photochemical rearrangements, 4, 735 phototranspositions, 4, 743 lsmeier formylation, 4, 759 Thiophene, 2-pivaloyl-Birch reduction, 4, 775 Thiophene, polybromo-reactivity, 4, 829 Thiophene, polylithio-synthesis, 4, 831 Thiophene, (propargylthio)-rearrangement, 4, 746 Thiophene, 2-(3-pyridinyl)-synthesis, 4, 781 Thiophene, 2-(5-pyrimidinyl)-synthesis, 4, 781 Thiophene, 3-pyrrolidinyl-cycloaddition reactions, 4, 68 with dimethyl acetylenedicarboxylate, 4, 788-789... 

Pivaloyl chloride reacts selectively with the less hindered phenol group. 

Pivaloyl chloride (trimethylacetyl chloride) [3282-30-2] M 120.6, b 57.6"/150mm, 70.5-71/250mm, 104"/754mm, 104-105"/atm, 105-108"/atm, d 1.003, n p 1.4142. First check the IR to see if OH hands are present. If absent, or present in small amounts, then redistil under moderate vac. If present in large amounts then treat with oxalyl chloride or thionyl chloride and reflux for 2-3h, evap and distil residue. Strongly LACHRYMATORY - work in a fumecupboard. Store in sealed ampoules under N2. [Traynham and Battiste J Org Chem 22 1551 1957, Grignard reactns Whitmore et al. J Am Chem Soc 63 647 1941.]... 

Acylation of ami noketone 8 with the acid chloride from p-toluic acid affords the corresponding ester (10) catalytic hydrogenation leads to the bronchodilator bitolerol (11). An analogous scheme starting from the N-methyl ketone (12) and pivaloyl chloride gives ami noalcohol (14). This compound is then resolved to isolate the levorotatory isomer. There is thus obtained the drug dipivefrin. 

Seebach and coworkers have developed the rtmldple coupling reagent, 2-tiitro-2-propenyl 2,2-dimethylpropanoate fNPPi. The reaction of nitromethane v/ith formaldehyde gives 1,3-dihydroxy-2-nitropropane in 95% yield. Subsequent acyladon v/ith two eqidviilents of pivaloyl chloride and elimination of pivalic acid affords NPP. The reacdon may be run on a 40- to 200-g... 

Next, 25.3 g, 0.125 mol, of the above product are dissolved in 250 ml ethyl acetate and 0.125 mol perchloric acid as a 70% aqueous solution is slowly added thereto with continuous stirring. Then, an excess of pivaloyl chloride, 280 ml. Is added and the mixture slowly warmed to reflux temperature. The reaction mixture is refluxed for about 5 hours and allowed to cool to room temperature with continuous stirring. The product is precipitated as the perchlorate salt by the addition of perchloric acid, HCIO4, in 500 ml ether. The product is isolated and purified by dissolving in 75 ml acetone and precipitating it with 150 to 200 ml of water. 

V-(2,3,4,6-Tctra-0-pivaloyl-/l-D-galactopyranosyl)aldiinines General Procedures51 ... 

With Aromatic Aldehydes. To a solution of 10.3 g (20 mmol) of 2,3,4,6-tetra O-pivaloyl-/ -i>galactopyra-nosylaminc in 50 rnL of /-PrOI 1 or heptane are added 30 mmol of the corresponding aromatic aldehyde and 30 drops of acetic acid. After 30 min to 2 h, the Schiff base precipitates from the /-PrOH solution. When the reaction is carried out in heptane, 2 g of Na2S04 or 3 g of 3 A molecular sieves are added after 15 min, and the mixture is filtered. On cooling to 0 °C the Schiff base crystallizes from the heptane solution. The aldimines are collected by filtration and rapidly washed with ice-cold /-PrOH or pentane, respectively. Generally, they are pure enough for further transformations. 

Alternatively, penta-O-acetyl-galactose can be converted to the known 2,3,4,6-tetra-O-acetylgalactopyranosyl azide59 which after treatment with sodium methoxide in methanol and subsequent pivaloylation with pivaloyl chloride in pyridine, also furnishes the O-pivaloylated galactosyl azide60. 

Stereoselective Strecker reactions with galactosylamine 1 can also be achieved with sodium cyanide and acetic acid in 2-propanol. The reactions, however, proceed slowly and with a lower stereoselectivity, giving diastereomeric ratios of the products between 3 1 and 7 1. The scope of the method can be extended to other glycosylamines, e.g., 2,3,4-tri-O-pivaloyl-a-D-arabinosyl-amine which allows the stereoselective synthesis of (A )-amino nitriles61,62. 

A solution of 2 g (4 mmol) of l-deoxy-2.3,4,6-tetra-(9-pivaloyl-/i-n-galactopyranosylamine. 4.1 mmol of the respective aldehyde, 0.2 g (4.4 mmol) of formic acid and 0.35 g (4.2 mmol) of rm-butyl isocyanide in... 

S)-A -Formyl-.Y-(2,.3,4-tri-D-pivaloyl-z-n-arabinopyranosylWert-leucine ferf-Butylamide Typical Procedure76 7S ... 

Although the 3 - and 5 -polyphosphate derivatives mentioned above exhibit exquisite inhibitory potency these compounds are not cell permeable. To take advantage ofthepotency of such derivatives for studies with intact cells and tissues, there are two possibilities. One is chemically to protect the phosphate groups from exonucleotidases that also allows the compound to transit the membrane intact. The other is to provide a precursor molecule that is cell permeable and is then metabolized into an inhibitor by intracellular enzymes. The general term for such a compound is prodrug nucleotide precursors are also referred to as pronucleotides. Families of protected monophosphate derivatives were synthesized, based on (3-L- and 3-D-2, 5 -dd-3 -AMP, 3-L-2, 3 -dd-5 -AMP, and the acyclic 9-substituted adenines, PMEA and PMPA. Protective substituents were (i) -( -pivaloyl-2-thioethyl) ... 

In exceptional circumstances the acylium ion (or the polarised complex) can decompose to give an alkyl cation so that alkylation accompanies acylation. This occurs in the aluminium chloride-catalysed reaction of pivaloyl chloride which gives acylation with reactive aromatics such as anisole, but with less reactive aromatics such as benzene, the acylium ion has time to decompose, viz. 

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