Vacuum sublimator

Sublimation under reduced pressure. The so-called vacuum sublimation may be carried out in the apparatus of Fig. II, 45, 4. The cold finger is fitted into the larger tube by means of a rubber stopper... 

A solution of 1.05 M diborane in THF (25 ml, 26 mraol) was added slowly to a stirred suspension of 3-acetyl-5-hydroxy-2-methylindole (1.0 g, 5.3 mmol) in THF (10 ml). After hydrogen evolution ceased, the mixture was heated at reflux for I h, cooled and poured into acetone (75 ml). The mixture was heated briefly to boiling and then evaporated in vacuo. The residue was heated with methanol (50ml) for 20min. The solution was concentrated and 3NHC1 (40ml) was added. The mixture was extracted with ether and the extracts dried (MgSO ) and evaporated to yield a yellow oil. Vacuum sublimation or recrystallization yielded pure product (0.76 g, 82%). 

Niobium Penta.fIuoride, Niobium pentafluoride is prepared best by direct fluorination of the metal with either fluorine or anhydrous hydrofluoric acid at 250—300°C. The volatile NbF is condensed in a pyrex or quartz cold trap, from which it can be vacuum-sublimed at 120°C to yield colorless monoclinic crystals. It is very hygroscopic and reacts vigorously with water to give a clear solution of hydrofluoric acid and H2NbOF ... 

It melts at 39°C and may be purified by vacuum sublimation. The Hquid boils at 233°C to give a monomeric vapor in which the Ti—Br distance is 231 pm. Titanium tetrabromide is soluble in dry chloroform, carbon tetrachloride, ether, and alcohol. Like titanium tetrachloride, TiBr forms a range of adducts with molecules such as ammonia, amines, nitrogen heterocycles, esters, and ethers. 

Titanium tetraiodide can be prepared by direct combination of the elements at 150—200°C it can be made by reaction of gaseous hydrogen iodide with a solution of titanium tetrachloride in a suitable solvent and it can be purified by vacuum sublimation at 200°C. In the van Arkel method for the preparation of pure titanium metal, the sublimed tetraiodide is decomposed on a tungsten or titanium filament held at ca 1300°C (152). There are frequent hterature references to its use as a catalyst, eg, for the production of ethylene glycol from acetylene (153). 

The same color variety is not typical with inorganic insertion/extraction materials blue is a common transmitted color. However, rare-earth diphthalocyanine complexes have been discussed, and these exhibit a wide variety of colors as a function of potential (73—75). Lutetium diphthalocyanine [12369-74-3] has been studied the most. It is an ion-insertion/extraction material that does not fit into any one of the groups herein but has been classed with the organics in reviews. Films of this complex, and also erbium diphthalocyanine [11060-87-0] have been prepared successfiiUy by vacuum sublimation and even embodied in soHd-state cells (76,77). 

Alkannin occurs in the roots of the plant as the alkah-sensitive ester of angelic acid (62). It may be extracted from the roots by using boiling light petroleum ether. Treatment of this extract with dilute sodium hydroxide gives a blue solution from which the dye is precipitated by the addition of acid. The cmde product is purified by vacuum sublimation (63). Its stmcture (11) is a hydroxylated naphthoquinone with a long, unsaturated side chain (64,65) it has the (3)-configuration. 

If the pump is a filter pump off a high-pressure water supply, its performance will be limited by the temperature of the water because the vapour pressure of water at 10°, 15°, 20° and 25° is 9.2, 12.8, 17.5 and 23.8 mm Hg respectively. The pressure can be measured with an ordinary manometer. For vacuums in the range lO" mm Hg to 10 mm Hg, rotary mechanical pumps (oil pumps) are used and the pressure can be measured with a Vacustat McLeod type gauge. If still higher vacuums are required, for example for high vacuum sublimations, a mercury diffusion pump is suitable. Such a pump can provide a vacuum up to 10" mm Hg. For better efficiencies, the pump can be backed up by a mechanical pump. In all cases, the mercury pump is connected to the distillation apparatus through several traps to remove mercury vapours. These traps may operate by chemical action, for example the use of sodium hydroxide pellets to react with acids, or by condensation, in which case empty tubes cooled in solid carbon dioxide-ethanol or liquid nitrogen (contained in wide-mouthed Dewar flasks) are used. 

Crystd from water (charcoal). Has also been crystd from 50% aqueous acetic acid. Can be vacuum sublimed. 

Benz[a]anthracene [56-55-3] M 228.3, m 159-160". Crystd from MeOH, EtOH or benzene (charcoal), then chromatographed on alumina from sodium-dried benzene (twice), using vacuum distn to remove benzene. Final purification was by vacuum sublimation. 

Biphenyl [92-52-4] M 154.2, m 70-71 , b 255 , d 0.992. Crystd from EtOH, MeOH, aq MeOH, pet ether (b 40-60 ) or glacial acetic acid. Freed from polar impurities by passage through an alumina column in benzene, followed by evapn. A in CCI4 has been purified by vac distn and by zone refining. Treatment with maleic anhydride removed anthracene-like impurities. Recrystd from EtOH followed by repeated vacuum sublimation and passage through a zone refiner. [Taliani and Breed Phys Chem 88 2351 1984.]... 

Cyanoanthracene (anthracene-9-carbonitrile) [1210-12-4] M 203.2, m 134-137°. Purified by crystn from EtOH or toluene, and vacuum sublimed in the dark and in an inert atmosphere [Ebied et al. 7 Chem Soc, Faraday Trans 7 76 2170 1980 Kikuchi et al. J Phys Chem 91 574 1987. ... 

Dimethylphenol [95-65-8] M 122.2, m 65°, b 225°/757mm, pK 10.36. Heated with an equal weight of cone H2SO4 at 103-105° for 2-3h, then diluted with four volumes of water, refluxed for Ih, and either steam distd or extracted repeatedly with diethyl ether after cooling to room temperature. The steam distillate was also extracted and evaporated to dryness. (The purification process depends on the much slower sulfonation of 3,5-dimethylphenol than most of its likely contaminants.). It can also be crystd from water, hexane or pet ether, and vacuum sublimed. [Kester Ind Eng Chem (Anal Ed) 24 770 1932 Bernasconi and Paschalis J Am Chem Soc 108 29691986.]... 

W-Metbylpbenotbiazine [1207-72-3] M 213.2, a-form m 99.3" and b 360-365", 0-form m 78-79". Recrystn (three times) from EtOH gave a-form (prisms). Recrystn from EtOH/ benzene gave the B-form (needles). Also purified by vacuum sublimation and carefully dried in a vacuum line. Also crystd from toluene and stored in the dark [Guarr et al. J Am Chem Soc 107 5104 1985 Olmsted et al. J Am Chem Soc 109 3297 1987.]... 

Naphthazarin (5,8-dihydroxy-1,4-naphthoquinone) [475-38-7] M 190.2, m 220-230°(dec), m 225-230°, pKEst(i) 9.5, pKEst(2) ll-l Red-brown needles with a green shine from EtOH. Also recrystd from hexane and purified by vacuum sublimation. [Huppert et al. J Phys Chem 89 5811 1985.] It is sparingly soluble in H2O but soluble in alkalis. It sublimes at 2-10mm. The diacetate forms golden yellow prisms from CHCI3, m 192-193° and the 5,8-dimethoxy derivative has m 157° (155°) (from pet ether) [Bruce and Thompson J Chem Soc 1089 7955 IR Schmand and Boldt J Am Chem Soc 97 447 1975 NMR Brockmann and Zeeck Chem Ber 101 4221 1968]. The monothiosemicarbazone has m 168°(dec) from EtOH [Gardner et al. J Am Chem Soc 74 2106 7952]. 

Succinonitrile [110-61-2] M 80.1, m 57.9 , b 108 /lmm, 267 /760mm. Purified by vacuum sublimation, also crystd from acetone. 

VinyIanthracene [2444-68-0] M 204.3, m 65-67 , b 61-66 /10mm. Purified by vacuum sublimation. Also by chromatography on silica gel with cyclohexane as eluent, and recrystd from EtOH [Werst et al. J Am Chem Soc 109 32 1987],... 

V-Vinylcarbazole [1484-13-5] M 193.3, m 66 . Crystd repeatedly from MeOH in amber glassware. Vacuum sublimed. 

Lead (bis-cyclopentadienyl) [1294-74-2] M 337.4. Purified by vacuum sublimation. Handled and stored under N2. 

Nickelocene [bis-(cyclopentadienyl)nickel II] [1271-28-9] M 188.9, m 173-174 (under N2). Dissolve in Et20, filter and evaporate in a vacuum. Purify rapidly by recrystn from pet ether using a solid C02-Me2C0 bath, m 171-173°(in an evacuated tube). Also purified by vacuum sublimation. [J Am Chem Soc 76 1970 954 J Inorg Nud Chem 2 95, 110 7956.]... 

Stannous bis-cyclopentadienyl [26078-96-6] M 248.9. Purified by vacuum sublimation, and stored under dry N2. The related thallium and indium compounds are similarly prepared. 

Fig. 8. Summary of real and imaginary e2(tu) parts of the dielectric function for Cgo vacuum-sublimed solid films at room temperature over a wide frequency range, using a variety of experimental techniques. The arrow at the left axis points to i = 4.4, the observed low frequency value of ei obtained from optical data [81].

Freeze-drying, like all drying processes, is a method to separate liquid water from a wet solid product or from a solution or dispersion of given concentration. However, the main difference is that the liquid water is separated by solidification (i.e., the formation of ice crystals) and subsequent vacuum sublimation instead of evaporation. This allows a drying at subzero temperatures which can be advantageous in case of heat-sensitive products. There are two general applications... 

High vacuum sublimation of the 3-monobenzoate of (32) or tosylchloride dehydration gives 3/ -benzoyloxy-7-methylenecholest-5-ene (33). The configuration of (32) is probably as shown since 7a-hydroxy steroids dehydrate readily to yield homoannular dienes. In an analogous reaction ethyl and iso-butyl Grignard reagents give alkylidene compounds as the only isolated products. 

The corresponding tellurium diimide BuNTe( -N Bu)2TeN Bu (10.7) may be obtained in good yields from the reaction of lithium tert-butylamide with TeCU in THE (Eq. 10.3). °" In toluene solution this reaction also produces the cyclic tellurium(II) imide (TcN Bu)3. The dimer 10.7 is obtained as an orange solid, which can be purified by vacuum sublimation at ca. 90°C. 

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