2-Tetrahydrofurfuryl alcohol

Unlike furfuryl alcohol, tetrahydrofurfuryl alcohol cannot be made successfully with a copper chromite catalyst as the latter has essentially no effect on the fiiran ring, its action being limited to the reduction of the carbonyl group. 

Tetrahydrofurfuryl alcohol is made commercially from furfural by a high-pressme hydrogenation at 1000 to 1500 psi (67.889 to 101.833 ATM) and 170 to 180 °C, using a mixture of copper chromite and RANEY nickel as the catalyst [103]  

Under the given conditions, the yield ranges from 70 to 80 percent, the by-product being 1,5-pentanediol. Higher yields up to 90 percent can be obtained at lower temperatures, between 100 and 125 °C, but this requires unreasonably longer reaction times. The RANEY nickel is made by leaching a nickel-aluminum alloy with caustic. 

Tetrahydrofurfuryl alcohol does not seem to have any direct application, but it is needed as a stepping stone for the production of dihydropyran [104] as shown in the next chapter. 

Dihydropyran (DHP), having an atmospheric boiling point of 86 °C and a very limited solubility in water (3 g in 100 g of water at 20 °C), can be produced from tetra-hydrofurfuryl alcohol by dehydration and ring expansion over an aluminum oxide catalyst at 

Vapor presaira seepg.8 Flash point (Tag closad up),  

Surface tension al 29C, dynas/cm 37 Dielectric constant al23 C 13.6 

I Dinitronaphthaiene Diphenyl I Naphthaiene j p.NHrophenol O NKrotoluene P NHrotoluene Xylol 

8 s s s s s Ethylene glycol monoethyf Halldest Benzyl chloride Bromobenzene Bromoform Chloroform Dlchlorobenzene p Dlehlorobenzene S S 3 3 3 3 38 3 

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Tetrahydrofurfuryl chloride. Place 204 g. (194 ml.) of freshly distilled tetrahydrofurfuryl alcohol (b.p. 177°) and 174 g. (178 ml.) of dry pyridine in a 1-litre three-necked flask, fitted with a dropping funnel, mechanical stirrer and thermometer. Cool in an ice bath, stir vigorously and add 250 g. (153 ml.) of freshly distilled thionyl chloride at the rate of 3-5 drops per second. A pasty crystalline mass begins to separate and the temperar ture commences to rise rapidly when one-third to one-half of the thionyl chloride has been added subsequently the mass largely redissolves and a dark brown liquid forms. Remove the ice bath when the addition is complete and stir the mixture for 3-4 hours. Pour the reaction product into a large separatory funnel and extract with seven 250 ml. portions of ether break up any lumps that may form with a glass rod. Remove the ether from the combined extracts by distillation, wash the residue with three 50 ml. portions of water, dry with anhydrous magnesium sulphate and distil under reduced pressure. The yield of tetrahydrofurfuryl chloride, b.p. 47-48°/15 mm., is 180 g. 

The most important physical properties of furfural, as well as similar properties for furfuryl alcohol, tetrahydrofurfuryl alcohol and furan are given in Table 1. The tabulated properties of furfural are supplemented by a plot (Fig. 1) of the vapor—Hquid compositions for the system, furfural—water (15,16). 

Furfural Furfuryl alcohol Furan Tetrahydrofurfuryl alcohol... 

Uses. Furfural is primarily a chemical feedstock for a number of monomeric compounds and resins. One route produces furan by decarbonylation. Tetrahydrofuran is derived from furan by hydrogenation. Polytetramethylene ether glycol [25190-06-1] is manufactured from tetrahydrofuran by a ring opening polymeri2ation reaction. Another route (hydrogenation) produces furfuryl alcohol, tetrahydrofurfuryl alcohol, 2-methylfuran, and 2-methyltetrahydrofuran. A variety of proprietary synthetic resins are manufactured from furfural and/or furfuryl alcohol. Other... 

As can be seen, most of the furfural produced in this country is consumed as an intermediate for other chemicals. Hydrogenation to furfuryl alcohol is the largest use. Some of the furfuryl alcohol is further hydrogenated to produce tetrahydrofurfuryl alcohol. The next major product is furan, produced by decarbonylation. Furan is a chemical intermediate, most of it is hydrogenated to tetrahydrofuran, which in turn is polymerized to produce polytetramethylene ether glycol (PTMEG). 

Hydrogenation of furfuryl alcohol can yield 2-tetrahydrofurfuryl alcohol, 2-methylfuran, 2-methyltetrahydrofuran, or straight-chain compounds by hydrogenolysis of the ring. Ethoxylation and propoxylation of furfuryl alcohol provide usefiil ether alcohols. 

Physical Properties. Tetrahydrofurfuryl alcohol (2-tetrahydrofuranmethanol) [97-99-4] (20) is a colorless, high-boiling liquid with a mild, pleasant odor. It is completely miscible with water and common organic solvents. Tetrahydrofurfuryl alcohol is an excellent solvent, moderately hydrogen-bonded, essentially nontoxic, biodegradable, and has a low photochemical oxidation potential. Most appHcations make use of its high solvency. The more important physical properties of tetrahydrofurfuryl alcohol are Hsted in Table 1. 

Chemical Properties. Without inhibitors, tetrahydrofurfuryl alcohol is susceptible to autoxidation, developing color and carbonyl functionality. In the absence of air, however, no observable changes occur even after several years storage. In the presence of air, if a stabilizer such as Naugard is added, tetrahydrofurfuryl alcohol remains colorless after protracted periods of storage. Peroxide accumulation is low, not dangerous, and readily dischargeable on redistillation. 

AH the common monobasic (107) and dibasic esters (108) of tetrahydrofurfuryl alcohol have been prepared by conventional techniques the dibasic esters and some of the mono esters are effective as primary or secondary plasticizers for vinyl polymers. Tetrahydrofurfuryl acrylate [2399-48-6] and methacrjiate [2455-24-5] specialty monomers, have been produced by carbonylation (nickel carbonyl and acetylene) of the alcohol (109) as weU as by direct esterification (110—112) and ester interchange (111). 

Tetrahydrofurfuryl alcohol reacts with ammonia to give a variety of nitrogen containing compounds depending on the conditions employed. Over a barium hydroxide-promoted skeletal nickel—aluminum catalyst, 2-tetrahydrofurfur5iarnine [4795-29-3] is produced (113—115). With paHadium on alumina catalyst in the vapor phase (250—300°C), pyridine [110-86-1] is the principal product (116—117) pyridine also is formed using Zn and Cr based catalysts (118,119). At low pressure and 200°C over a reduced nickel catalyst, piperidine is obtained in good yield (120,121). 

Tetrahydrofurfuryl alcohol is oxidized to 2-tetrahydrofurfural [7681-84-7] in good yield by passage, with oxygen, over silver gauze at 500°C (123—124). With chromate oxidizing agents, lactones are also formed (124,125). 

Tetrahydrofurfuryl alcohol is surprisingly resistant to hydrogenolysis under vigorous conditions, however, cleavage of the ring or side chain occurs (126,127). 

Manufacture. Tetrahydrofurfuryl alcohol is produced commercially by the vapor-phase catalytic hydrogenation of furfuryl alcohol. Liquid phase reduction is also possible. 

Normal precautions for chemicals of mild toxicity are appHcable to the safe handling and storage of commercial tetrahydrofurfuryl alcohol. Discoloration in storage rarely occurs if the proper precautions are observed prevention of exposure to air wiH prevent autoxidation. The Hst price of tetrahydrofurfuryl alcohol (1997) is 1.15/lb. 

Uses. Tetrahydrofurfuryl alcohol is of interest in chemical and related industries where low toxicity and minimal environmental impact are important (134). For many years tetrahydrofurfuryl alcohol has been used as a specialty organic solvent. The fastest growing appHcations are in formulations for cleaners (135) and paint strippers (136), often as a replacement for chlorinated solvents (137). Other major appHcations include formulations for crop sprays, water-based paints, and the dyeing and finishing of textiles and leathers. Tetrahydrofurfuryl alcohol also finds appHcation as an intermediate in pharmaceutical appHcations. 

Because tetrahydrofurfuryl alcohol is virtuaHy colorless, it is used in lacquer formulations for aH colors as weU as water-white clear products. More speciftcaHy, tetrahydrofurfuryl alcohol is a wetting dispersant for most pigments. It has a high boiling point, high toluene dilution ratio, and good miscibility with oils, eg, linseed and soya, and is an exceUent solvent for a wide range of resins. 

Tetrahydrofurfuryl alcohol also has been cleared for use in California under Rule 66. It meets the rigid specifications for uv degradation in environmentally sensitive areas. In addition to domestic use, a substantial amount of tetrahydrofurfuryl alcohol is used as a solvent for agricultural chemicals in Europe. 

Tetrahydrofurfuryl alcohol is a solvent and coupling agent for a phosphate-type insecticide used to control the gypsy moth. Esters of tetrahydrofurfuryl alcohol are used in preparations employed as insect repeUents. Tetrahydrofurfuryl alcohol is also used as a solvent—carrier for an EPA-approved paper sHmicide formulation. In this appHcation, the exceptional solvent action of tetrahydrofurfuryl alcohol prevents separation of the... 

Tetrahydrofurfuryl alcohol is used in elastomer production. As a solvent for the polymerization initiator, it finds appHcation in the manufacture of chlorohydrin mbber. Additionally, tetrahydrofurfuryl alcohol is used as a catalyst solvent-activator and reactive diluent in epoxy formulations for a variety of apphcations. Where exceptional moisture resistance is needed, as for outdoor appHcations, furfuryl alcohol is used jointly with tetrahydrofurfuryl alcohol in epoxy adhesive formulations. 

Other furan compounds, best derived from furfural, are of interest although commercial volumes are considerably less than those of furfural, furfuryl alcohol, furan, or tetrahydrofurfuryl alcohol. Some of these compounds are stiU in developmental stages. Apphcations include solvents, resin intermediates, synthetic mbber modifiers, therapeutic uses, as well as general chemical intermediates. 

Since double bonds are no longer present, these compounds are more stable than the corresponding furan derivatives. Tetrahydrofurfuryl alcohol—ethylene oxide adducts [31692-85-0] are also usehil solvents for paint stripping formulations (136,141,143). 2-Methylfuran is a good solvent, but... 

Rubber Modifiers. Derivatives of furan and tetrahydrofurfuryl alcohol are used in the polymerization of synthetic mbber to control stereoregularity and otherproperti.es (149,150). 

Intermediates. 3,4-Dihydro-2H-pyran [110-87-2] is prepared by a ring-expanding dehydration of tetrahydrofurfuryl alcohol. It is used as a protecting agent for hydroxyl compounds and as an intermediate. 2-Methylfuran is a chemical intermediate for 5-methylfurfural [620-02-0] (151) and... 

Ring expansion of ftve-membered ring heterocycHc compounds has been accompHshed to form pyridine derivatives. Reaction of tetrahydrofurfuryl alcohol with ammonia gives pyridine (1) under dehydrogenating conditions, and gives piperidine (18) under reductive conditions. 

The tetrahydrofurfuryl alcohol available from the Quaker Oats Company, or the Practical grade from the Eastman Kodak Company, has been used. If the material a ailable does not hydrogenate satisfactorily, it may be purified by hydrogenation over Raney nickel at 150 /100-200 atmospheres pressure. A sample of good quality boils at 177-178°/740 mm. and does not become dark-colored when a few milliliters are shaken with 1 drop of concentrated sulfuric acid at room temperature. 

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