Acetates, secondary

One of the exciting results to come out of heterogeneous catalysis research since the early 1980s is the discovery and development of catalysts that employ hydrogen peroxide to selectively oxidize organic compounds at low temperatures in the liquid phase. These catalysts are based on titanium, and the important discovery was a way to isolate titanium in framework locations of the inner cavities of zeolites (molecular sieves). Thus, mild oxidations may be run in water or water-soluble solvents. Practicing organic chemists now have a way to catalytically oxidize benzene to phenols alkanes to alcohols and ketones primary alcohols to aldehydes, acids, esters, and acetals secondary alcohols to ketones primary amines to oximes secondary amines to hydroxyl-amines and tertiary amines to amine oxides. 

Anomeric selectivity is diminished in the case of 0,/V-acetals. This means that the starting hemiacetal may give a mixture of a- or /J-anomers with amines. Therefore, a measurement of diastereomeric ratios is less useful than in the case of pure 0,0-acetals. Secondary amino compounds may react cleanly with the e.w-MBF-OH, whereas primary amines give, with both starting materials, mixtures of a- and /J-anomers. 

TNTC Trifluoroacetic anhydride, Nitromethane, Ammonium nitrate, NIHT HCL, Ethyl acetate Secondary high explosive ... 

Butyl Acetate, Secondary (For Use in Org Coatings) sec-BuAc TT-B-840B Jan I960... 

Amine Primary alcohol % Secondary or tertiary Alcohol % Primauy acetate % Secondary or tertiary acetate %... 

Oxidative acetalization. Secondary alcohols are converted to 1,3-dioxolanes directly in a Re-catalyzed oxidation in the presence of DMSO and 1,2-ethanediol. 

Regenerated cellulose (cellophane) Cellulose acetate (secondary) Cellulose triacetate Cellulose acetate- butyrate Ethyl cellulose... 

In Table 5.4 are listed correlations for the CH group. The hydrocarbon CH stretch occurs near 2900 cm" and is usually lost among other aliphatic absorptions. The CH deformation absorbs weakly in hydrocarbons at 1350-1315 cm" in the infrared. This vibration is more distinctive in the Raman effect. In nonhydrocarbons, such as ortAo-formates, acetals, secondary peroxides, or a-subsdtuted amines, the CH deformation at 1350-1315 cm" is intensified in the infrared. In secondary alcohols, the CH and OH deformation interact to give two bands sensitive to hydrogen bonding at 1440-1350 and 1350-1200 cm" (see alcohols). A chlorine next to the CH will raise the stretching (ca. 3000 cm" ) and lower and intensify the bending frequency (1250-1200 cm" ). 

Hie cellulose esters triacetate and acetate (secondary acetate) are the two major fibers of this type. The production of acetate fibers resulted from an attempt to find a new outlet for cellulose acetate used as aircraft "dope" in World War 1. By 1921, the first acetate fibers were being produced. Although small quantities of cellulose triacetate fibers were produced before World War I, it was not until after 1954 that cellulose triacetate fibers were produced commercially in large quantities. 

Cigarette filter tows are made from cellulose acetate (secondary), which is plasticized by - glyceryl triacetate... 

If a primary or secondary amine is heated with glacial acetic acid, the... 

One disadvantage of using acetic anhydride is that with primary amines, traces of the diacctyl compound, RN(COCH3)2, niay be formed the chances of this secondary acetylation are, however, usually remote, and recrystallisation from an aqueous solvent will generally hydrolyse the diacetyl derivative rapidly back to the mono-acetyl compound. 

Acetyl derivatives. Primary and secondary amines are best acetylated with acetic anhydride ... 

The quinaldine is separated from any unreacted aniline and from the alkyl-anilines by treatment with acetic anhydride, basified with sodium carbonate and steam distilled. Only the primary and secondary amines are acetylated the acetylated amines are now much less volatile so that separation from the steam-volatile quinaldine (a tertiary amine) is facile. 

Acetyl chloride reacts vigorously with primary and secondary alcohols to yield esters it also reacts readily with any water present to form acetic acid ... 

For this reason, acetic anhydride is generally preferred for the preparation of acetyl derivatives, but acetyl chloride, in view of its greater reactivity, is a better diagnostic reagent for primary and secondary amines. 

Based on the above-mentioned stereochemistry of the allylation reactions, nucleophiles have been classified into Nu (overall retention group) and Nu (overall inversion group) by the following experiments with the cyclic exo- and ent/n-acetales 12 and 13[25], No Pd-catalyzed reaction takes place with the exo-allylic acetate 12, because attack of Pd(0) from the rear side to form Tr-allyl-palladium is sterically difficult. On the other hand, smooth 7r-allylpalladium complex formation should take place with the endo-sWyWc acetate 13. The Nu -type nucleophiles must attack the 7r-allylic ligand from the endo side 14, namely tram to the exo-oriented Pd, but this is difficult. On the other hand, the attack of the Nu -type nucleophiles is directed to the Pd. and subsequent reductive elimination affords the exo products 15. Thus the allylation reaction of 13 takes place with the Nu nucleophiles (PhZnCl, formate, indenide anion) and no reaction with Nu nucleophiles (malonate. secondary amines, LiP(S)Ph2, cyclopentadienide anion). 

Hydroxylysine (328) was synthesized by chemoselective reaction of (Z)-4-acet-oxy-2-butenyl methyl carbonate (325) with two different nucleophiles first with At,(9-Boc-protected hydroxylamine (326) under neutral conditions and then with methyl (diphenylmethyleneamino)acetate (327) in the presence of BSA[202]. The primary allylic amine 331 is prepared by the highly selective monoallylation of 4,4 -dimethoxybenzhydrylamine (329). Deprotection of the allylated secondary amine 330 with 80% formic acid affords the primary ally-lamine 331. The reaction was applied to the total synthesis of gabaculine 332(203]. 

Four other groups of synthetic adhesives find uses in secondary processing, ie, overlaying, assembly gluing, etc, and in furniture and cabinet manufacture. Poly(vinyl acetate) (PVA) adhesives are widely used in appHcation of veneers and other overlays to panel substrates and in some unit-assembly operations. PVA adhesives are an emulsion of polyvinyl acetate in water and cure by loss of water. The PVA adhesives are somewhat... 

Olefins add anhydrous acetic acid to give esters, usually of secondary or tertiary alcohols propjiene [115-07-1] yields isopropyl acetate [108-21-4], isobutjiene [115-11-7] gives tert-huty acetate [540-88-5]. Minute amounts of water inhibit the reaction. Unsaturated esters can be prepared by a combined oxidative esterification over a platinum group metal catalyst. Eor example, ethylene-air-acetic acid passed over a palladium—Hthium acetate catalyst yields vinyl acetate. 

With aldehydes, primary alcohols readily form acetals, RCH(OR )2. Acetone also forms acetals (often called ketals), (CH2)2C(OR)2, in an exothermic reaction, but the equiUbrium concentration is small at ambient temperature. However, the methyl acetal of acetone, 2,2-dimethoxypropane [77-76-9] was once made commercially by reaction with methanol at low temperature for use as a gasoline additive (5). Isopropenyl methyl ether [116-11-OJ, useful as a hydroxyl blocking agent in urethane and epoxy polymer chemistry (6), is obtained in good yield by thermal pyrolysis of 2,2-dimethoxypropane. With other primary, secondary, and tertiary alcohols, the equiUbrium is progressively less favorable to the formation of ketals, in that order. However, acetals of acetone with other primary and secondary alcohols, and of other ketones, can be made from 2,2-dimethoxypropane by transacetalation procedures (7,8). Because they hydroly2e extensively, ketals of primary and especially secondary alcohols are effective water scavengers. 

The predominant cellulose ester fiber is cellulose acetate, a partially acetylated cellulose, also called acetate or secondary acetate. It is widely used in textiles because of its attractive economics, bright color, styling versatiUty, and other favorable aesthetic properties. However, its largest commercial appHcation is as the fibrous material in cigarette filters, where its smoke removal properties and contribution to taste make it the standard for the cigarette industry. Cellulose triacetate fiber, also known as primary cellulose acetate, is an almost completely acetylated cellulose. Although it has fiber properties that are different, and in many ways better than cellulose acetate, it is of lower commercial significance primarily because of environmental considerations in fiber preparation. 

Cellulose triacetate is obtained by the esterification of cellulose (qv) with acetic anhydride (see Cellulose esters). Commercial triacetate is not quite the precise chemical entity depicted as (1) because acetylation does not quite reach the maximum 3.0 acetyl groups per glucose unit. Secondary cellulose acetate is obtained by hydrolysis of the triacetate to an average degree of substitution (DS) of 2.4 acetyl groups per glucose unit. There is no satisfactory commercial means to acetylate direcdy to the 2.4 acetyl level and obtain a secondary acetate that has the desired solubiUty needed for fiber preparation. 

The elongation of a stretched fiber is best described as a combination of instantaneous extension and a time-dependent extension or creep. This viscoelastic behavior is common to many textile fibers, including acetate. Conversely, recovery of viscoelastic fibers is typically described as a combination of immediate elastic recovery, delayed recovery, and permanent set or secondary creep. The permanent set is the residual extension that is not recoverable. These three components of recovery for acetate are given in Table 1 (4). The elastic recovery of acetate fibers alone and in blends has also been reported (5). In textile processing strains of more than 10% are avoided in order to produce a fabric of acceptable dimensional or shape stabiUty. 

Secondary Acetate Processes. There is no commercial process to directiy produce secondary cellulose acetate sufficientiy soluble in acetone to produce fiber. Hence, the cellulose is completely acetylated to the triacetate during the dissolution step and then hydrolyzed to the required acetyl value. 

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