Diols anhydrides

The carbonylation of 2-methyl-3-butyn-2-oI (50) in benzene gives teraconic anhydride (51). Fulgide (53) (a dimethylenesuccinic anhydride derivative), which is a photochromic compound, can be prepared by the carbonylation of 2,5-dimethyl-3-hexyne-2,5-diol (52)[21], The reaction proceeds under milder conditions when PdlOAc) is used as a catalyst in the presence of iodine [23],... 

Acetals are readily formed with alcohols and cycHc acetals with 1,2 and 1,3-diols (19). Furfural reacts with poly(vinyl alcohol) under acid catalysis to effect acetalization of the hydroxyl groups (20,21). Reaction with acetic anhydride under appropriate conditions gives the acylal, furfuryUdene diacetate... 

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). 

Other minor raw materials are used for specific needs. Eumaric acid [110-17-8] the geometric isomer of maleic acid, is selected to maximize thermal or corrosion performance and is the sole acid esterified with bisphenol A diol derivatives to obtain optimum polymer performance. CycloaUphatics such as hydrogenated bisphenol A (HBPA) and cyclohexanedimethanol (CHDM) are used in selective formulations for electrical apphcations. TetrahydrophthaUc anhydride [85-43-8] (THPA) can be used to improve resiUence and impart useful air-drying properties to polyester resins intended for coating or lining apphcations. 

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. 

Lipase-catalyzed enantioselective transesterification of 0-substituted-l,2-diols is another practical route for the synthesis of P-blockers. Lipase PS suspended in toluene catalyzes the transesterification of (63) with vinyl acetate to give the (5)-ester in 43% yield and >98% ee (78). The desired product, optically pure (R)-ttitylglycidol, is then easily obtained by treating the ester with alcohoHc alkaU. Moreover, Pseudomonas Hpase catalyzes the acylation of oxazohdinone (64) with acetic anhydride in very good yield and selectivity (74). PPL-catalyzed transesterification of a number of /n j -norbomene derivatives proceeds in about 30% yield and 92% ee (79,80). 

Acetoxy-21-nor-5a-cholestan-20-one (73a) as well as the free alcohol (73b) react with methylmagnesium iodide to give a mixture of epimeric diols (74). After treatment with acetic anhydride and subsequent hydrogenation over reduced platinum oxide this mixture alfords 3j5-acetoxy-5oc-cholestane (75) which is identical with the natural product. This synthesis has been used to prepare the 21- C compound (75) in a total yield of 18... 

Preparation of /m -3) -Acetoxypregna-5,17(20)-dien-21-aI A solution of 12.2 g of 17a-ethynylandrost-5-ene-3/ ,17jS-diol diacetate and 0.5 g of silver acetate in 250 ml acetic acid and 100 ml of acetic anhydride is refluxed under... 

Epoxides are easily attacked by trifluoroacetic anhydride. The reactions lead to diesters of vicinal diols and monoesters of unsaturated allylic alcohols in ratios depending on the reaction conditions [24] (equation 13). 

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). 

In further modifications of these norprogestins, reaction of norethindrone with acetic anhydride in the presence of p-toluene-sulfonic acid, followed by hydrolysis of the first-formed enol acetate, affords norethindrone acetate (41). This in turn affords, on reaction with excess cyclopentanol in the presence of phosphorus pentoxide, the 3-cyclopentyl enol ether (42) the progestational component of Riglovic . Reduction of norethindrone affords the 3,17-diol. The 33-hydroxy compound is the desired product since reactions at 3 do not show nearly the stereoselectivity of those at 17 by virtue of the relative lack of stereo-directing proximate substituents, the formation of the desired isomer is engendered by use of a bulky reducing agent, lithium aluminum-tri-t-butoxide. Acetylation of the 33,173-diol iffords ethynodiol diacetate, one of the most potent oral proves tins (44). ... 

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 mixture of 30 parts of 17o -ethvnvl-19-norandrost-4-ene-30,17(3-diol, 360 parts of dry pyridine, and 111 parts of acetic anhydride, under nitrogen, is stirred and heated at the reflux temperature for about 5 hours. This reaction mixture is cooled, then poured into approximately 3,500 parts of cold water and the resulting aqueous mixture is stirred at room temperature for about 0.5 hour. The precipitate which forms is collected by filtration, then is washed on the filter with water and dried in air. This solid material is extracted into ether, and the ether solution is washed successively with 10% aqueous hydrochloric acid and 5% aqueous sodium bicarbonate. 

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. 

Cyclohexadiene has been prepared by dehydration of cyclohexen-3-ol,3 by pyrolysis at 540° of the diacetate of cyclohexane-1,2-diol,4 by dehydrobromination with quinoline of 3-hromocyclohexene,6 by treating the ethyl ether of cyclohexen-3-ol with potassium bisulfatc,6 7 by heating cyclohexene oxide with phthalic anhydride,8 by treating cyclohexane-1,2-diol with concentrated sulfuric acid,9 by treatment of 1,2-dibromocyclo-hexane with tributylamine,10 with sodium hydroxide in ethylene glycol,10 and with quinoline,6 and by treatment of 3,6-dibromo-cyclohexene with sodium.6... 

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... 

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