Acetal carbon

Selenoaldehydes 104, like thioaldehydes, have also been generated in situ from acetals and then directly trapped with dienes, thus offering a useful one-pot procedure for preparing cyclic seleno-compounds [103,104], The construction of a carbon-selenium double bond was achieved by reacting acetal derivatives with dimethylaluminum selenide (Equation 2.30). Cycloadditions of seleno aldehydes occur even at 0 °C. In these reactions, however, the carbon-selenium bond formed by the nucleophilic attack of the electronegative selenium atom in 105 to the aluminum-coordinated acetal carbon, may require a high reaction temperature [103], The cycloaddition with cyclopentadiene preferentially gave the kinetically favorable endo isomer. 

Pyruvic acid is most often linked to the 4- and 6-positions of a hexopyran-osyl residue. The absolute configuration at the acetal carbon atom may be... 

The commercial process for the production of vinyl acetate monomer (VAM) has evolved over the years. In the 1930s, Wacker developed a process based upon the gas-phase conversion of acetylene and acetic acid over a zinc acetate carbon-supported catalyst. This chemistry and process eventually gave way in the late 1960s to a more economically favorable gas-phase conversion of ethylene and acetic acid over a palladium-based silica-supported catalyst. Today, most of the world s vinyl acetate is derived from the ethylene-based process. The end uses of vinyl acetate are diverse and range from die protective laminate film used in automotive safety glass to polymer-based paints and adhesives. 

The product 6 results from the syn-/i-H-ehmination of the palladium with hydrogen borne by the acetal carbon (Scheme 4) as previously reported for corresponding reactions (9,10). The presence of n-Bu4NOAc noticeably increases... 

Administer just before or with a meal to maximize effects ° Calcium salts (acetate, carbonate, and citrate)... 

The clear solution, obtained by centrifuging a solution of the oxide in aqueous ammonia which had been treated with silver nitrate until precipitation started, exploded on two occasions after 10-14 days storage in closed bottles in the dark. This was ascribed to slow precipitation of amorphous silver imide, which is very explosive even when wet [1], When silver oxide is dissolved in ammonia solution, an extremely explosive precipitate (probably Ag3N4) will separate. The explosive behaviour is completely inhibited by presence of colloids or ammonium salts (acetate, carbonate, citrate or oxalate). Substitution of methylamine for ammonia does not give explosive materials [2],... 

These reactions were carried out using /V-mesyIoxazaborolidine 96 (0.5 eq.) and allylsilane 98 (1.5 eq.) in CH2CI2 at —50°C. Conversion of 97 as high as 63% was observed, and the remaining (2S,4R)-97 was recovered in 92% ee. Modification of the electronic nature of the aryl substituent attached to the acetal carbon at the para position of 97 did not affect the enantioselectivity of ring cleavage. 

The titanium reagent 1 reacts with allyl alcohol derivatives, such as halides, acetates, carbonates, phosphates, or sulfonates to afford allyltitanium complexes of the type (r 1-al-lyl)TiX(OiPr)2, as shown in Eq. 9.21 [42], As a variety of allylic alcohols are easily obtained,... 

The versatile Ti(II) chemistry available using preformed (alkene)Ti(OiPr)2 species was opened up by the discovery of the Kulinkovich cyclopropanation reaction [55]. Since 1995, Sato and collaborators have developed a wide range of elegant and synthetically useful reactions based on the Ti(OiPr)4/iPrMgCl reagent [56]. In particular, it was reported that the Ti(II) complex (q2-propene)Ti(OiPr)2, preformed from Ti(OiPr)4 and 2 equivalents of iPrMgCl, reacts with allylic compounds, such as halide, acetate, carbonate, phosphate, sulfonate, and aryl ether derivatives, to afford allyltitanium compounds as depicted in Scheme 13.27 [57]. 

Three types of photochemical reaction of carbohydrate acetals have been investigated. Early studies centered on the photochemical fragmentation of phenyl glycosides, and the photolysis of o-nitrobenzyli-dene acetals. (The latter reactions will be discussed with the photolysis of other nitro compounds see Sect. VII,1.) Later experiments were concerned with hydrogen-abstraction reactions from acetal carbon atoms by excited carbonyl compounds. 

Scheme 15.—Rationalization for the Importance of Orbital Overlap to Radical Stabilization During Hydrogen Abstraction from an Acetal Carbon Atom.

Reaction of 1 with benzaldehyde and zinc chloride gave a diastereomeric mixture (6) of R- and 5-2,3-O-benzylidene derivatives (4a and 4b). The former (4a) would be identical to the acetal described by Zinner et al. (3) as 2,4-O-benzylidene-D-ribono-1,5-lactone. This structure was further established as 4a, by chemical and physical studies of the product obtained on reaction of 1 with benzaldehyde dimethyl acetal (7). The 2,3-O-benzylidene derivative, obtained by Garegg et al. (8) on reaction of 1 with a,a-dichlorotoluene in pyridine, has the same properties as compound 4a, which would indicate the -configuration for the acetal carbon. 

Some synthetically important allenylmetallics, such as allenylzinc and allenylin-dium reagents, are prepared from allenylpalladium intermediates. These reactions are discussed in appropriate sections of this chapter. This section covers the reactions of allenylpalladium compounds without further transmetallation. Allenylpalladium complexes can be prepared from propargylic halides, acetates, carbonates, mesylates, alcohols and certain alkynes [83-87], The allenylpalladium compound prepared from 3-chloro-3-methyl-l-butyne has been isolated and characterized spectroscopically (Eq. 9.106) [83], It was found to couple with organozinc chlorides to produce homologated allenes quantitatively (Eq. 9.107). 

For acetone, chloroform, ethyl acetate, carbon bisulphide calcium chloride. 

Palladium-catalyzed allylation using nucleophiles with allylic halides, acetates, carbonates, etc. via intermediate allylpalladium complexes, and typically with overall retention of stereochemistry. 

Another anomeric effect is that acetal C-0 bonds, and to a lesser extent, the bonds between acetal carbons and ether oxygens, are shortened or elongated as a function of their associated torsional angles. Jeffrey and Taylor modified MMl to account for these anomeric effects (17) and similar additions were put in the standard 1985 version of MM2 (11). The parameterization of MM3 for anomeric effects is preliminary, with recent (18-20) results being monitored. 

Other uses of blends include controlled rate of fertilizer release(77) based on ethylene/vinyl acetate/carbon monoxide polymers which is U.V. sensitive, polyolefin blends with any biodegradable polymers,(78) and polyolefins blended with metals and autoxidizable substrates. (79) Doane and co-workers(80) at the U.S.D.A. have used grafted starches in many applications, including soil stabilization. 

Synthetic routes to a-nitroalkenes have been discussed in previous sections. General routes include (1) treating /3-nitroacetates with alkali metal acetates, carbonates or bicarbonates, (2) elimination of water from /3-nitroalcohols via heating with phthalic anhydride or in the presence of a base," ° and (3) degradation of the Mannich products derived from a primary nitroalkane, formaldehyde, and a secondary amine. ... 

Lithium ions. Lithium salts (e.g., acetate, carbonate) are effective in controlling the manic phase. The effect becomes evident approx. 10 d after the start of therapy. The small therapeutic index necessitates frequent monitoring of Li+ serum levels. Therapeutic levels should be kept between 0.8-1.0 mM in fasting morning blood samples. At higher values there is a risk of adverse effects. 

Table I. Assienment of ring size bv the observation of the 13°-n.m.r. chemical shift of the orthoester (or acetal) carbon atom...

This FMN-dependent enzyme [EC 1.13.12.4] catalyzes the reaction of (5)-lactate with dioxygen to produce acetate, carbon dioxide, and water. 

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