High-pressure irradiation

High Pressure. Irradiation under high pressure increases the crosslinking yield of some polymers (64-66). This has mechanistic implications which need to be further explored. 

With short periods of irradiation (with high-pressure mercury lamps) under oxygen in chloroform containing methylene blue as a sensitizer, variously substituted 2-arylthiazoles are converted in the corresponding 2-aryloxazoles (823). 

On the other hand, 2-arylthiazoles are easily isomerized to 3-aryliso-thiazoles in 407o yield upon irradiation with a high-pressure mercury lamp, in benzene solution in the presence of iodine (738). A valence bond isomerization was proposed among several alternatives to account for these results. 

The photolysis of 4-substituted 2,3-dimethyl-3-isoxazolin-5-ones has been studied. Irradiation in methanol or ethanol with a 100 W high-pressure mercury lamp through a Pyrex filter of a 4-phenylthio compound produced a semithioacetal (Scheme 5). In contrast, an H, Cl or OPh moiety gave no reaction. The use of alkylthio substitution gave similar products. Cyclic compounds yielded cyclic products (Scheme 5), and the photolysis of (29) in benzene... 

Engle, G.B. and Eatherly, W.P., Irradiation behavior of graphite at high temperature, High Temperatures—High Pressures, 1972, 4, 119-158. 

Detection and result The chromatogram was dried in a stream of warm air for 10 min, immersed in the reagent solution for 3 s and then subjected to intense UV radiation (high pressure lamp, A = 365 nm) for up to 10 min. Terephthalic (hRf 0 - 5), pimelic (hRf 55), suberic (hRf 60), sebacic (hRf 65 — 70) and benzoic acids (hRf 70 — 75) together with sorbic, malic, adipic, citric, tartaric, lactic and fumaric acids only exhibited a reaction on silica gel layers at higher concentrations. 4-Hydroxybenzoic, salicylic and acetylsalicylic acids fluoresced light blue after irradiation. The detection limit per chromatogram zone was 0.5 pg for salicylic acid and more than 5 pg for benzoic acid. 

A solution of 500 mg 3 -acetoxypregn-5-en-20-one-[17a,16a-c]-A -pyrazoline in 100 ml of anhydrous dioxane is stirred with a magnetic stirrer and irradiated in a water-cooled quartz reactor with a high pressure Biosol Philips 250 W quartz lamp for 1 hr. The solvent is removed at reduced pressure and the residue is chromatographed on alumina (activity III). Elution with petroleum ether-benzene (3 1) gives 0.2 g (42%) of 3 -acetoxy-16a,17a-methylene-pregn-5-en-20-one mp 193-193.5° after two recrystallizations from methylene dichloride-ethyl acetate. 

Preparation of 18,20-Cyclo-5a-pregnane-3, 20-diol 3-Acetate ° A solution of 5 g of 3j9-hydroxy-5oc-pregnan-20-one 3-acetate in 1000 ml of spectroscopically pure ethanol is irradiated with a 250 Watt Philips Biosol A mercury high pressure lamp No. 10/27 through a cental water cooled pyrex jacket under nitrogen for 4 hr. The solvent is then evaporated under reduced pressure and the residues from 2 such reactions are combined and chromatographed on 300 g of neutral alumina (activity II). 

Irradiations of Testosterone Acetate (114), —In t-Butanol. 1.25 g of (114) in 250 ml t-butanol is irradiated for 32 hr at 30° under nitrogen with a Hanau Q81 high-pressure mercury lamp placed in a central water-cooled Pyrex immersion well with acetone filter. The solvent is evaporated in vacuo and the residue chromatographed on 125 g silica gel with benzene-ethyl acetate (4 1) to yield 0.29 g 17 -hydroxy-la,5 -cyclo-10a-androstan-2-one acetate [(118) 23%] mp 164-165°, after crystallization from acetone-hexane [a]i3 37 (CHCI3) 0.14 g cyclopentanone (120) (11%) mp 106-107° [aJo 38° (CHCI3) and 0.58 g starting material [(114) 46%]. Ratio (118) (120) - 2 1. 

Sensitized by Acetophenone. A -butanol solution of (114) (2.10 M) and acetophenone (0.8 M) is irradiated for 6 hr at 30° under nitrogen with a Hanau Q 81 high-pressure mercury lamp through a Pyrex-acetone filter (path length 1 cm, cut-off of wavelengths below 3270 A). Better than 98 % of the incident light is absorbed by the acetophenone. A 70% conversion of (114) to the same products as listed above is observed. The ratio (118) (120) is again -2 1. 

A solution of 5 g of (267) in 140 ml of benzene is irradiated for 24 hr at 15-20° with a 70-W Hanau Q81 high pressure mercury lamp in a central pyrex immersion well. A stream of ethylene is bubbled through the solution during the irradiation. After evaporation of the solvent the residue is... 

Reaction times can be shonened and yields improved through the use of high pressure [40] (equation 28) Reactions may also be conducted in aqueous medium under ultraviolet irradiation [41] (equation 29)... 

Irradiation of piperidine 62 in CH2CI2 at concentration of 3mg/ml in the presence of 1-methylimidazole using a high-pressure mercury lamp (150 w) yielded 2-phenyl-4,6,7,8,9,9n-hexahydropyrido[2,l-h][l, 3]oxazin-4-one (01 SI258). 

The heat of fusion of the rotator phase in n-paraffms is 38-40 cal/g, while AHo- m for PE irradiated with 1000 Mrad is about 29 cal/g. The corresponding value of AHo->m for hexagonal PE at high pressure (500 MPa) is only around 15 cal/g. Thermograms of constrained PE fibers showed similarly low heats of fusion of the hexagonal phase. 

The proposed mechanism is based on the basis of the fact that ylides (Scheme 23 and Scheme 24) undergo bond fission between the phosphorus atom and the phenyl group in TPPY as reported by Nagao et al. [51] and between the sulfur atom and the phenyl group in POSY as observed in triphenylsulfonium salts [52-55] when they are irradiated by a high-pressure mercury lamp. The phenyl radicals thus produced participate in the initiation of polymerization. 

Irradiation of 1-benzothiepins 1 in tetrahydrofuran with a high-pressure 450-W mercury lamp and a Pyrex filter at 0"C for four hours results in a reversal of the thiepin-synthesis method startingfrom 3,4-benzo-2-thiabicyclo[3.2.0]hept-3,6-dienes (see Section 2.1.3.3.), giving the photoproducts 2 along with some of the corresponding naphthalenes.1019... 

Acridine-9-carbonitrile 10-oxide (la 3.00g, 13.6 mmol) in benzene (1.8 L) in a quartz immersion well was irradiated for 3 h with a Hanovia high-pressure 450-W Hg lamp equipped with a Pyrex filter. The resulting solution was evaporated under reduced pressure and the residue was extracted with pentane (3 x 50 mL). The combined extracts were evaporated under reduced pressure at 20 C to give orange crystals yield 1.8 g (60%) mp 105-109 C (Et20/pentane). 

Pyridine-2,6-dicarbonitrile 1-oxide (500 mg, 3.45 mmol) in CH2C12 (500 mL) was irradiated for 10 h with a high-pressure 450-W Hanovia Hg lamp. The solution was evaporated under reduced pressure and the residue was extracted several times with pentane. The combined extracts were concentrated and the residue was repeatedly recrystallized (pentane) to give yellow needles yield 150mg (30%) mp 61-63 C (dec.). 

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