Diols from anhydrides

Powerful complex hydrides like lithium aluminum hydride in refluxing ether [5i] or refluxing tetrahydrofuran [1017] reduce cyclic anhydrides to diols. Phthalic anhydride was thus transformed to phthalyl alcohol (o-hydroxy-methylbenzyl alcohol) in 87% yield [5i]. Similar yields of phthalyl alcohol were obtained from phthalic anhydride and sodium bis 2-methoxyethoxy) aluminum hydride [544, 969]. 

Condensation of pyrazine-2,3-dicarboxylic anhydride with hydrazine furnishes pyrazino[2,3-diols from pyrazine-2,3-dicarboxylic esters (see Section 7.4.9.1,1.1.). 

Just as simple esters and amides can be made by condensation reactions, polyesters such as Dacron and Mylar are made by reacting diols with dicarboxylic acids (Figure 13.15 A). Similarly, polyamides such as nylon form from amines and carboxylic acids. Starting from anhydrides and amines, polyimides can be formed. These structures tend to be extremely stable, and so are valuable in high temperature applications. 

Lacfols via lactones, and diols from dicarboxylic acid anhydrides Labeled terpenoids... 

Diester/Ether Diol of Tetrabromophthalic Anhydride. This material [77098-07-8] is prepared from TBPA in a two-step reaction. First TBPA reacts with diethylene glycol to produce an acid ester. The acid ester and propylene oxide then react to give a diester. The final product, a triol having two primary and one secondary hydroxyl group, is used exclusively as a flame retardant for rigid polyurethane foam (53,54). 

MixedPhosphona.te Esters. Unsaturated, mixed phosphonate esters have been prepared from monoesters of 1,4-cyclohexanedimethanol and unsaturated dicarboxyhc acids. Eor example, maleic anhydride reacts with this diol to form the maleate, which is treated with benzenephosphonic acid to yield an unsaturated product. These esters have been used as flame-retardant additives for thermoplastic and thermosetting resias (97). 

Powder coatings are formulated from the reaction product of trimethylolpropane and IPDI, blocked with caprolactam, and polyester polyols. The saturated polyester polyols are based on aromatic acid diols, neopentyl glycol, and trimellitic anhydride for further branching. To avoid the release of caprolactam in the curing reaction, systems based on IPDI dimer diols are used. 

The following data are for the hydrolysis of cinnamic anhydride in (2-amino-2-hydroxymethyl-1,3-propane diol buffers. Extrapolate them to zero buffer concentration, and, together with data from Problem 9, plot the pH-rate profile. Determine the order with respect to hydroxide, and calculate the rate constant for hydrolysis. 

Bis(3-nitrofurazanoxymethyl)oxetane 221 was synthesized in 52% yield by base-promoted ring closure of the corresponding 3-hydroxy-l-propyl triflate, 219, which is readily available from the diol and triflic anhydride. Oxetane 221 can also be prepared in 74% yield by treatment of the trifurazanyl ether 220 with DBU. Polymerization and copolymerization reactions of oxetane 220 have also been investigated (97MI7) (Scheme 148). 

Five hundred milligrams of (dl)-reg.-Tphenvl-2-dichloroacetamidopropane-1,3-diol is added to a solution consisting of 1 cc of pyridine and 1 cc of acetic anhydride and the resulting reaction mixture heated at 100°C for % hour. The reaction mixture is evaporated to dryness under reduced pressure and the residue taken up in and crystallized from methanol. Recrystallization from methanol produces the pure diacetate of (dl)-reg.-1-phenyl-2-dichloro-acetamidopropane-1,3-diol (MP 94°C). 

A solution of the piperidino-diol (9 grams) in acetic anhydride (18 ml) was heated at 90°C for 1 hour, the solution cooled, excess acetic anhydride destroyed by the careful addition of water, and the resulting solution carefully made alkaline with 2N caustic soda solution to precipitate a solid product. The soiid was dried, extracted with n-hexane and the solution filtered free of insoluble material before percolation down a column (4x1" diameter) of alumina. Eiution with n-hexane gave a fraction (4.2 grams) which was crystallized twice from ether to give the diacetate, MP 176°-180°C. 

The production of 1,4-butanediol (1,4-BDO) from propylene via the carbonylation of allyl acetate is noted in Chapter 8. 1,4-Butanediol from maleic anhydride is discussed later in this chapter. An alternative route for the diol is through the acetoxylation of butadiene with acetic acid followed by hydrogenation and hydrolysis. 

In 1970, it was disclosed that it is possible to achieve the conversion of dimethylformamide cyclic acetals, prepared in one step from vicinal diols, into alkenes through thermolysis in the presence of acetic anhydride." In the context of 31, this two-step process performs admirably and furnishes the desired trans alkene 33 in an overall yield of 40 % from 29. In the event, when diol 31 is heated in the presence of V, V-dimethylforrnamide dimethyl acetal, cyclic dimethylformamide acetal 32 forms. When this substance is heated further in the presence of acetic anhydride, an elimination reaction takes place to give trans olefin 33. Although the mechanism for the elimination step was not established, it was demonstrated in the original report that acetic acid, yV, V-dimethylacetamide, and carbon dioxide are produced in addition to the alkene product."... 

N 42.74% OB to C02 —30.51% cryst (meso), liq (racemic) mp 70—71° (cryst) bp 150° (decompn). Sol in acet and ethanol. Prepn is by nitration of 2,3-diazido-l, 4-butanediol with mixed acid. The procedure involves dropwise addn of 2.58g of the diol to a cooled (0—5°) mixt (1/1) of acetic anhydride/100% nitric acid. The reaction is held to 5—15° and stirred for 30 mins. Several recrysts from ethanol give a (approx) 40% yield. The compd is friction sensitive Qc 682.8 and 671.8kcal/mole Qf 98.8 kcal/mole impact sensy at 50% pt is 6.3cm using a 2kg wt in an Aberdeen Impact App and No 12 tools (PETN=26.7cm) impact sensy of proplnt films (85.15% NC/14.85% diazido compd) is 29—36cm (M2 film=34—36cm) at the 50% pt... 

Acid anhydride-diol reaction, 65 Acid anhydride-epoxy reaction, 85 Acid binders, 155, 157 Acid catalysis, of PET, 548-549 Acid-catalyzed hydrolysis of nylon-6, 567-568 of nylon-6,6, 568 Acid chloride, poly(p-benzamide) synthesis from, 188-189 Acid chloride-alcohol reaction, 75-77 Acid chloride-alkali metal diphenol salt interfacial reactions, 77 Acid chloride polymerization, of polyamides, 155-157 Acid chloride-terminated polyesters, reaction with hydroxy-terminated polyethers, 89 Acid-etch tests, 245 Acid number, 94 Acidolysis, 74 of nylon-6,6, 568... 

A dispersant that can be used in drilling fluids, spacer fluids, cement slurries, completion fluids, and mixtures of drilling fluids and cement slurries controls the rheologic properties of and enhances the filtrate control in these fluids. The dispersant consists of polymers derived from monomeric residues, including low-molecular-weight olefins that may be sulfonated or phosphonated, unsaturated dicarboxylic acids, ethylenically unsaturated anhydrides, unsaturated aliphatic monocarboxylic acids, vinyl alcohols and diols, and sulfonated or phosphonated styrene. The sulfonic acid, phosphonic acid, and carboxylic acid groups on the polymers may be present in neutralized form as alkali metal or ammonium salts [192,193]. 

The addition of Grignard reagents to aldehydes, ketones, and esters is the basis for the synthesis of a wide variety of alcohols, and several examples are given in Scheme 7.3. Primary alcohols can be made from formaldehyde (Entry 1) or, with addition of two carbons, from ethylene oxide (Entry 2). Secondary alcohols are obtained from aldehydes (Entries 3 to 6) or formate esters (Entry 7). Tertiary alcohols can be made from esters (Entries 8 and 9) or ketones (Entry 10). Lactones give diols (Entry 11). Aldehydes can be prepared from trialkyl orthoformate esters (Entries 12 and 13). Ketones can be made from nitriles (Entries 14 and 15), pyridine-2-thiol esters (Entry 16), N-methoxy-A-methyl carboxamides (Entries 17 and 18), or anhydrides (Entry 19). Carboxylic acids are available by reaction with C02 (Entries 20 to 22). Amines can be prepared from imines (Entry 23). Two-step procedures that involve formation and dehydration of alcohols provide routes to certain alkenes (Entries 24 and 25). 

Various additives show considerable extraction resistance, such as impact modifiers (polyacrylates and polyblends PVC/EVA, PVC/ABS, etc.), highpolymeric processing aids (PMMA-based), elastomers as high-MW plasticisers, reactive flame retardants (e.g. tetrabromobisphenol-A, tetrabromophthalic anhydride, tetrabromophthalate diol, dibromostyrene). Direct measurement of additives by UV and IR spectroscopy of moulded films is particularly useful in analysing for additives that are difficult to extract, although in such cases the calibration of standards may present a problem and interferences from other additives are possible. 

Reaction of estrone (2) with an excess of the lithium reagent from 3-iodofuran gives intermediate diol 3. The stereochemical assignment follows from the well-known propensity of steroids for attack from the less-hindered backside (a) of the molecule. Acylation of 3 with acetic anhydride then affords the estrogen estrvfurate (4).1... 

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