Orthoboric acid, esters

Organic coordination groups, nomenclature of, 2 267 Organogermanium compounds, 5 64 nomenclature of, 5 64 Organosilazane compounds, 5 55, 62 Organosilicon compounds, 3 50 nomenclature of, 2 266 3 55 Orthite, extraction of, 2 44 Orthoboric acid, esters of, 6 29 Orthoperiodic acid (HsICh), 1 172, 173... 

Although all four tocopherols have been synthesized as their all-rac forms, the commercially significant form of tocopherol is i7//-n7i a-tocopheryl acetate. The commercial processes ia use are based on the work reported by several groups ia 1938 (15—17). These processes utilize a Friedel-Crafts-type condensation of 2,3,5-trimethylhydroquinone with either phytol (16), a phytyl haUde (7,16,17), or phytadiene (7). The principal synthesis (Fig. 3) ia current commercial use iavolves condensation of 2,3,5-trimethylhydroquiQone (13) with synthetic isophytol (14) ia an iaert solvent, such as benzene or hexane, with an acid catalyst, such as ziac chloride, boron trifluoride, or orthoboric acid/oxaUc acid (7,8,18) to give the all-rac-acetate ester (15b) by reaction with acetic anhydride. Purification of tocopheryl acetate is readily accompHshed by high vacuum molecular distillation and rectification (<1 mm Hg) to achieve the required USP standard. 

The general formula for boric acid esters is B(OR)2. The lower molecular weight esters such as methyl, ethyl, and phenyl are most commonly referred to as methyl borate [121 -43-7] ethyl borate [130-46-9J, and phenyl borate [1095-03-0] respectively. Some of the most common boric acid esters used in industrial appHcations are Hsted in Table 1. The nomenclature in the boric acid ester series can be confusing. The lUPAC committee on boron chemistry has suggested using trialkoxy- and triaryloxyboranes (5) for compounds usually referred to as boric acid esters, trialkyl (or aryl) borates, trialkyl (or aryl) orthoborates, alkyl (or aryl) borates, alkyl (or aryl) orthoborates, and in the older Hterature as boron alkoxides and aryloxides. CycHc boric acid esters, which are trimeric derivatives of metaboric acid (HBO2), are known as boroxines (1). 

Ebelman and Bouquet prepared the first examples of boric acid esters in 1846 from boron trichloride and alcohols. Literature reviews of this subject are available. B The general class of boric acid esters includes the more common orthoboric acid based trialkoxy- and triaryloxyboranes, B(0R)3 (1), and also the cyclic boroxins, (ROBO)3, which are based on metaboric acid (2). The boranes can be simple trialkoxyboranes, cyclic diol derivatives, or more complex trigonal and tetrahedral derivatives of polyhydric alcohols. Nomenclature is confusing in boric acid ester chemistry. Many trialkoxy- and triaryloxyboranes such as methyl, ethyl, and phenyl are commonly referred to simply as methyl, ethyl, and phenyl borates. The lUPAC boron nomenclature committee has recommended the use of trialkoxy- and triaryloxyboranes for these compounds, but they are referred to in the literature as boric acid esters, trialkoxy and triaryloxy borates, trialkyl and triaryl borates or orthoborates, and boron alkoxides and aryloxides. The lUPAC nomenclature will be used in this review except for relatively common compounds such as methyl borate. Boroxins are also referred to as metaborates and more commonly as boroxines. Boroxin is preferred by the lUPAC nomenclature committee and will be used in this review. 

Ethyl orthoborate has a boiling point of 120°, a density of 0.86426, and a refractive index (n ) of 1.3721. It is readily hydrolyzed to ethanol and orthoboric acid. The ester may be analyzed for boron by dissolving a weighed sample in water, adding mannitol (about ten times the weight of sample taken), and titrating the boric acid to the phenolphthalein end point. This determination works best if the solution is protected from atmospheric carbon dioxide in the region of the end point. 

In addition to diolefins, there are other bifunctional compounds that will form boron heterocyclics under analogous reaction conditions. For example, the triallyl ester of orthoboric acid reacts with trialkylamine-borane in the presence of trialkylboranes to give B-alkyl-l,2-oxaborolane (XXXVIII) (5). 

Trialkylboranes can also be replaced by esters of orthoboric acid (tri-alkoxyboranes). An equimolar mixture of R3B, R3NBH3, and B(OR3 ) yields B-alkoxy-l-boraindanes in this manner, B-butoxy-3-methylbora-indane (LXI) was obtained in 85 % yield at 190° C (7f). 

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