Tubes sealing

Boron trichloride, BCI3. Colourless mobile liquid, m.p. — 107°C, b.p. 12-5°C. Obtained directly from the elements or by heating B2O3 with pels in a sealed tube. The product may be purified by distillation in vacuo. It is extremely readily hydrolysed by water to boric acid. TetrachJoroborates containing the BCJ4 " ion are prepared by addition of BCI3 to metal chlorides. 

Figure A2.5.31. Calculated TIT, 0 2 phase diagram in the vicmity of the tricritical point for binary mixtures of ethane n = 2) witii a higher hydrocarbon of contmuous n. The system is in a sealed tube at fixed tricritical density and composition. The tricritical point is at the confluence of the four lines. Because of the fixing of the density and the composition, the system does not pass tiirough critical end points if the critical end-point lines were shown, the three-phase region would be larger. An experiment increasing the temperature in a closed tube would be represented by a vertical line on this diagram. Reproduced from [40], figure 8, by pennission of the American Institute of Physics.

Both the primary amine (D) and the tertiary amine (E) are reasonably strong bases, and will absorb carbon dioxide if exposed to the air. They should therefore be stored in ground-glass stoppered bottles or in sealed tubes. 

Principle. A known weight of the substance is heated with fuming nitric acid and silver nitrate in a sealed tube. The organic material is thus oxidised to carbon dioxide and water, whilst the halogen is converted quantitatively into the corresponding silver halide. The latter js subsequently washed out of the tube, filtered and weighed. 

Now roll up the Carius tube (while still in a vertical position) in a strip of ordinary thick drying paper, and then place it in the heavy iron protector tube if the Carius tube is too short and tends to disappear within the iron tube, a short section of old glass tubing should first be placed in the iron tube so that the capillary of the Carius tube just projects. The function of the paper is to protect the Carius tubing from being scratched, and also (more important) to prevent the local overheating which would otherwise occur at places where the Carius tube is in direct contact with the iron tube. The sealed tube, throughout its manipulation, should be left as nearly vertical as possible, so that the contents do not leave the rounded end. 

Principle. This is essentially a small-scale modification of the macro piethod described on p. 416, the substance being completely oxidised in a sealed tube with fuming nitric acid in the presence of silver nitrate, the halogen being thus converted into silver halide. The collection and weighing of the silver halide require special techniques on the semi-micro scale. 

Place the sealed tube F (Fig. 90) in a strong iron tube, so that only the tip projects cf. Fig. 74, p. 420), and heat it preferably in an electric... 

The m.ps. of the-ir acids v,iry with the rate of heating, and the values given are those obtained on rapid heating in sealed tubes, t Anhydrous. 

Wolff - Kishner reduction of aldehydes and ketones. Upon heating the hydrazoiie or semicarbazone of an aldehyde or ketone with potassium hydroxide or with sodium ethoxide solution (sealed tube), the corresponding hydrocarbon is obtained ... 

It is believed that the red phosphorus is the true reducing agent and the iodine (or iodide) functions as a hydrogen carrier. This proc ure replaces the obsolete method of heating with red phosphorus and concentrated hydriodic acid in a sealed tube. 

Dinitrobenzoyl chloride reacts readily with water and it should be kept in sealed tubes or under light petroleum. When required for qualitative organic analysis it is usually best prepared from 3 5 dinitrobenzoic acid immediately before use (see Section 111,27,2). 

A mixture of 4-bromo-l-(4-methylphenylsulfonyl)indole (88 mg, 0.25 mmol), methyl a-acetamidoacrylate (91 mg, 0.64 mmol), PdCl2(PPh3)2 (16 mg, 0.023 mmol) and NaOAc (82 mg, 0.98 mmol) in EtjN (0.8 ml) and DMF (0.4 ml) was heated to 120°C in a sealed tube for 2 h. The tube was opened and the contents diluted with EtOAc and filtered through Celite. The EtOAc was washed successively with 10% HCl, sat. NaHC03 and brine and then dried (MgS04). The residue was purified by elution through silica gel with 10 1 benzene-EtOAc to give the product as a yellow solid (93 mg, 90%). 

A solution of l-methylpyrano[4,3-b]indol-3-one (1 mmol) and methyl vinyl ketone (5 ml) in toluene (5 ml) containing 5% Pd/C (40 mg) was heated for 48 h in a sealed tube at 110°C. The reaction mixture was evaporated in vacuo and the residue purified by silica gel chromatography to give the product in 80% yield. 

Hydroxy-4-methylthiazole failed to react when submitted to Friedel-Crafts benzoylation conditions (349) on the other hand, it reacted normally in Gattermann and in Reimer-Tiemann formylation reactions, affording the 5-formyl derivative (348). 4-Methylthiazole is insufficiently activated and fails to react under the same conditions. 2,4-Dimethylthiazole undergoes perfluoroalkylation when heated at 200° for 8 hr in a sealed tube with perfluoropropyl iodide and sodium acetate (116) (358). 

Dissolve 1.000 g Rh by the sealed-tube method described under iridium. 

This compound is sometimes called a nylon salt. The salt polymer equilibrium is more favorable to the production of polymer than in the case of polyesters, so this reaction is often carried out in a sealed tube or autoclave at about 200°C until a fairly high extent of reaction is reached then the temperature is raised and the water driven off to attain the high molecular weight polymer. 

Reimschuessel and Deget polymerized caprolactam in sealed tubes containing about 0.0205 mol HjO per mole caprolactam. In addition, acetic acid (V), sebacic acid (S), hexamethylene diamine (H), and trimesic acid (T) were introduced as additives into separate runs. The following table lists (all data per mole caprolactam) the amounts of additive present and the analysis for end groups in various runs ... 

In the study described in the last problem, caprolactam was polymerized for 24 hr at 225°C in sealed tubes containing various amounts of water. M and were measured for the resulting mixture by osmometry and light scattering, respectively, and the following results were obtained ... 

Urea [57-13-6] was discovered ia urine by Rouelle ia 1773 and first synthesized from ammonia (qv) and cyanic acid by Woehler ia 1828. This was the first synthesis of an organic compound from an inorganic compound, and it dealt a deathblow to the vital-force theory. In 1870, urea was produced by heating ammonium carbamate ia a sealed tube. 

Metaldehyde [9002-91-9] a cycHc tetramer of acetaldehyde, is formed at temperatures below 0°C in the presence of dry hydrogen chloride or pyridine—hydrogen bromide. The metaldehyde crystallizes from solution and is separated from the paraldehyde by filtration (48). Metaldehyde melts in a sealed tube at 246.2°C and sublimes at 115°C with partial depolymerization. 

Halogenation. Liquid-phase monochlorination of ben2otrifluoride gives pronounced meta orientation (295) in contrast, vapor-phase halogenation favors para substitution (296). Sealed tube, photochemical, or dark chlorination (radical initiator) forms... 

Various inorganic, organic, and organometaUic compounds are known to cataly2e this polymerization (4,8,9). Among these, BCl is a very effective catalyst, although proprietary catalysts that signiftcandy lower polymerization temperature from the usual, sealed-tube reaction at 250°C are involved in the industrial manufacture of the polymer. A polycondensation process has also been developed for the synthesis of (4) (10—12). This involves elimination of phosphoryl chloride from a monomer prepared from (NH 2 04 and PCl. ... 

Hydrogen embritdement at higher temperatures. In sealed tubes. 

When the dihydrate is carefully heated to 100°C it loses its water to give anhydrous oxaUc acid. On the other hand, when the dihydrate is heated rapidly or ia a sealed tube, it melts at 101.5°C. 

Qualitative Analysis. Several quaUtative analyses can be employed. For example, in the oxamide method (59), oxaUc acid is first heated at approximately 200°C with concentrated aqueous ammonia in a sealed tube. When thiobarbituric acid is added and heated to 140°C, a condensed compound of red color forms. The analysis limit is 1.6 pg. In the diphenylamine blue method (59,60), oxaUc acid is heated with diphenylamine to form a blue color, aniline blue. The analysis limit is 5 pg. 

In both the Hquid and vapor states, phosphoms(III) oxide exists as the P40 molecule. The vapor of phosphoms(III) oxide ionizes air. Phosphoms tetroxide is made by heating P40 in a sealed tube to 440°C. P40 sublimes under vacuum at I80°C and forms colorless, glossy crystals. 

In most cases, the activator impurity must be incorporated during crystal growth. An appropriate amount of impurity element is dissolved in the molten Ge and, as crystal growth proceeds, enters the crystal at a concentration that depends on the magnitude of the distribution coefficient. For volatile impurities, eg, Zn, Cd, and Hg, special precautions must be taken to maintain a constant impurity concentration in the melt. Growth occurs either in a sealed tube to prevent escape of the impurity vapor or in a flow system in which loss caused by vaporization from the melt is replenished from an upstream reservoir. 

Protein Hydrolysis. Acid hydrolysis of protein by 6 MHQ in a sealed tube is generally used (110°C, 24-h). During hydrolysis, slight decomposition takes place in serine (ca 10%) and threonine (ca 5%). Cystine and tryptophan in protein cannot be deterruined by this method because of complete decomposition. 

The most recent, and probably most elegant, process for the asymmetric synthesis of (+)-estrone appHes a tandem Claisen rearrangement and intramolecular ene-reaction (Eig. 23). StereochemicaHy pure (185) is synthesized from (2R)-l,2-0-isopropyhdene-3-butanone in an overall yield of 86% in four chemical steps. Heating a toluene solution of (185), enol ether (187), and 2,6-dimethylphenol to 180°C in a sealed tube for 60 h produces (190) in 76% yield after purification. Ozonolysis of (190) followed by base-catalyzed epimerization of the C8a-hydrogen to a C8P-hydrogen (again similar to conversion of (175) to (176)) produces (184) in 46% yield from (190). Aldehyde (184) was converted to 9,11-dehydroestrone methyl ether (177) as discussed above. The overall yield of 9,11-dehydroestrone methyl ether (177) was 17% in five steps from 6-methoxy-l-tetralone (186) and (185) (201). 

Tellurium Tetraiodide. Tellurium tertaiodide [7790-48-9] Tel, forms gray-black volatile crystals which above 100°C decompose into the elements. They melt at 280°C in a sealed tube. 

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