Flash vacuum pyrolysis of methoxy-substituted lignin model compounds

The flash vacuum pyrolysis (FVP) of methoxy-substituted beta-O-4 lignin model compounds has been studied at 500 degrees C to provide mechanistic insight into the primary reaction pathways that occur under conditions of fast pyrolysis. FVP of PhCH(2)CH(2)OPh (PPE), a model of the dominant beta-O-4 linkage in lignin, proceeds by C-O and C-C cleavage, in a 37:1 ratio, to produce styrene plus phenol as the dominant products and minor amounts of toluene, bibenzyl, and benzaldehyde. From the deuterium isotope effect in the FVP of PhCD(2)CH(2)OPh, it was shown that C-O cleavage occurs by homolysis and by 1,2-elimination in a ratio of 1.4:1, respectively. Methoxy substituents enhance the homolysis of the beta-O-4 linkage, relative to PPE, in o-CH(3)O-C(6)H(4)OCH(2)CH(2)Ph (o-CH(3)O-PPE) and (o-CH(3)O)(2)-C(6)H(3)OCH(2)CH(2)Ph ((o-CH(3)O)(2)-PPE) by a factor of 7.4 and 21, respectively. The methoxy-substituted phenoxy radicals undergo a complex series of reactions, which are dominated by 1,5-, 1,6-, and 1,4-intramolecular hydrogen abstraction, rearrangement, and beta-scission reactions. In the FVP of o-CH(3)O-PPE, the dominant product, salicylaldehyde, forms from the methoxyphenoxy radical by a 1,5-hydrogen shift to form 2-hydroxyphenoxymethyl radical, 1,2-phenyl shift, and beta-scission of a hydrogen atom. The 2-hydroxyphenoxymethyl radical can also cleave to form formaldehyde and phenol in which the ratio of 1, 2-phenyl shift to beta-scission is ca. 4:1. In the FVP of o-CH(3)O-PPE and (o-CH(3)O)(2)-PPE, products (ca. 20 mol %) are also formed by C-O homolysis of the methoxy group. The resulting phenoxy radicals undergo 1,5- and 1,6-hydrogen shifts in a ratio of ca. 2:1 to the aliphatic or benzylic carbon, respectively, of the phenethyl chain. In the FVP of (o-CH(3)O)(2)-PPE, o-cresol was the dominant product. It was formed by decomposition of 2-hydroxy-3-hydroxymethylbenzaldehyde and 2-hydroxybenzyl alcohol, which are formed from a complex series of reactions from the 2, 6-dimethoxyphenoxy radical. The key step in this reaction sequence was the rapid 1,5-hydrogen shift from 2-hydroxy-3-methoxybenzyloxy radical to 2-hydroxymethyl-6-methoxyphenoxy radical before beta-scission of a hydrogen atom to give the substituted benzaldehyde. The 2-hydroxybenzyl alcohols rapidly decompose under the reaction conditions to o-benzoquinone methide and pick up hydrogen from the reactor walls to form o-cresol.     

Flash vacuum pyrolysis of azolylacroleins and azolylbutadienes

2-Aryl-5-acroleinyl-1,2,3,4-tetrazoles (1a–d) and 2-aryl-5-butadienyl-1,2,3,4-tetrazoles (1e–g) were subjected to flash vacuum pyrolysis. Acroleinyl derivatives resulted in nitrogen extrusion to give nitrilimines followed by ring closure to give the corresponding indazoles 3a–d in good yields. On the other hand, butadiene derivatives underwent ring fragmentation to give p-substituted anilines without formation of the expected indazoles. Differences between thermal behaviour of 2-(4-chlorophenyl)-5-acroleinyl-1,2,3,4-tetrazole (1c) and 1-(4-chlorophenyl)-4-acroleinyl-1,2,3-triazole (2) were studied in details. DFT calculations have been used to examine the nitrilimine and carbene nature of the intermediates involved in the thermal reactions of azolyl derivatives.     

Flash pyrolysis of Silopi asphaltite in a free-fall reactor under vacuum

Flash pyrolysis experiments on asphaltite samples were performed in a free-fall reactor under vacuum to determine the effects of pyrolysis temperature, feed rate and particle size. Maximum liquid yield of 13 wt.% was obtained in free-fall reactor under vacuum when the pyrolysis temperature was 700 °C, feed rate was 0.4 g min⁻¹ and particle sizes were between 0.075 and 0.250 mm. The liquid products obtained at various pyrolysis conditions were analyzed by gas chromatography/mass spectrometer (GC/MS) and liquid products were classified as following: C5–C10, C11–C15, C16–C20 and C20+. The amount of saturated hydrocarbons decreased while the amount of unsaturated hydrocarbons increased with increase of temperature. While percent of C5–C10 unsaturated hydrocarbons continuously increased with increase of temperature, the percent of C11–C15 unsaturated hydrocarbons increased up to 750 °C and then started to diminish. Functional group analysis of solid residue was carried out using Fourier transform infrared spectrometry (FT-IR). The proximate analysis of solid residue indicated that percent of fixed carbon and ash increased with temperature.     

Flash pyrolysis of polystyrene wastes in a free-fall reactor under vacuum

Plastic waste minimization and recycling are important for both economical and environmental reasons. In this flash pyrolysis study, polystyrene wastes were degraded in a free-fall reactor under vacuum to regain the monomer. A set of experiments varied the temperature between 700 and 875°C and determined its effects on the phase yields, the benzene, styrene, toluene, and naphthalene distribution of the liquid output and C1–C4 content of the gaseous output. The liquid yield maximized around 750°C and the styrene yield at 825°C. In general, operating at higher temperatures lessened the solid residue and increased the gaseous yield and total conversion. Employing waste particles in four size ranges, a second set of runs indicated that the finer the waste particles fed the higher the gaseous yield and total conversion. This recycling method can be made more promising if the feed particles are allowed more time for degradation and the removal of the primary products speeded up thereby preventing their decomposition. Ways are suggested to obviate these residence time problems.     

闪式真空热解(FVP)在有机合成中的应用

闪式真空热裂解(Flash vacuum pyrolysis,FVP)是一种反应底物在真空条件下蒸发或者升华后迅速通过较高温度的热管道发生热解反应的过程.该热裂解方法经常被运用于合成一些重要的非平面型芳香化合物,比如著名的心环烯C20H10(Corannulene),富勒烯C60等.主要针对FVP方法的发展历史、装置的基本构成、反应的基本历程以及该方法在有机合成中的实际应用等方面进行了系统的综述.相对于传统有机合成化学方法,FVP方法的优势在于可以提供更高的外界能量来帮助产物化学键的形成和更快速的冷却方式来帮助稳定反应所得到的产物,因此该方法不仅能高效、方便地合成得到一些常规有机合成方法不能轻易获得的目标化合物,还可以获得一些热力学极其不稳定的产物.当然,FVP方法也有其限制,比如对于一些在真空条件下难以挥发的化合物FVP方法就不适用了,另外,因为所有FVP反应都是在气相条件下完成,所以该方法主要适用于分子内的消除或环合反应,对于有机合成中普遍存在的双分子反应以及多分子反应也难以通过FVP方法来实现,但作为一类独特、实用的有机合成方法,FVP在有机合成中得到了较广的应用和不断地发展.     

Flash flow pyrolysis: mimicking flash vacuum pyrolysis in a high-temperature/high-pressure liquid-phase microreactor environment

Flash vacuum pyrolysis (FVP) is a gas-phase continuous-flow technique where a substrate is sublimed through a hot quartz tube under high vacuum at temperatures of 400-1100 °C. Thermal activation occurs mainly by molecule-wall collisions with contact times in the region of milliseconds. As a preparative method, FVP is used mainly to induce intramolecular high-temperature transformations leading to products that cannot easily be obtained by other methods. It is demonstrated herein that liquid-phase high-temperature/high-pressure (high-T/p) microreactor conditions (160-350 °C, 90-180 bar) employing near- or supercritical fluids as reaction media can mimic the results obtained using preparative gas-phase FVP protocols. The high-T/p liquid-phase "flash flow pyrolysis" (FFP) technique was applied to the thermolysis of Meldrum's acid derivatives, pyrrole-2,3-diones, and pyrrole-2-carboxylic esters, producing the expected target heterocycles in high yields with residence times between 10 s and 10 min. The exact control over flow rate (and thus residence time) using the liquid-phase FFP method allows a tuning of reaction selectivities not easily achievable using FVP. Since the solution-phase FFP method does not require the substrate to be volatile any more--a major limitation in classical FVP--the transformations become readily scalable, allowing higher productivities and space-time yields compared with gas-phase protocols. Differential scanning calorimetry measurements and extensive DFT calculations provided essential information on pyrolysis energy barriers and the involved reaction mechanisms. A correlation between computed activation energies and experimental gas-phase FVP (molecule-wall collisions) and liquid-phase FFP (molecule-molecule collisions) pyrolysis temperatures was derived.     

Flash vacuum pyrolysis over solid catalysts. 2. pyrazoles over hydrotalcites

Flash vacuum pyrolysis (fvp) reactions of NH-pyrazole (1) and 3,5-diphenylpyrazole (2) were investigated in the presence of anionic clays having hydrotalcite structure (HT). Solid catalysts with Mg:Al ratio equal to 2:1 containing carbonate (HT-1), nitrate (HT-2), and silicate (HT-3) as interlayer anions were employed. Between 400 and 600 degrees C, compound 1 remained almost unchanged and only unidentified volatile products were detected in small amounts. In contrast, 2 afforded benzonitrile (3) and phenylacetonitrile (4) by a ring fragmentation reaction at 450 degrees C. At a higher temperature (660 degrees C), the same products obtained in homogeneous fvp reactions, i.e., 2-phenylindene (5) and 3-phenylindene (6), were obtained showing no catalysis by HT under these conditions. Results showed that the yield is strongly dependent on the nature of the interlayer anion in the hydrotalcite structure. In comparison with reactions of 2 over zeolites, HTs exhibit selectivity for ring fragmentation reaction.     

Thermal fragmentation and rearrangement of some N-phenylbenzamide oxime dervatives II. Synthesis of benzimidazoles

Thermolysis of N-phenylbenzamide oximes I, II and III (R = Cl, NO₂ and OCH₃) under nitrogen gives rise to benzimidazoles as the major products (45-52%), in addition to benzonitrile, arylamines, benzoic acid, phenols, benzanilides, 2-phenyl benzoxazoles and carbazoles. In the presence of naphthalene, I gave α- and β-naphthols beside the previous products. Also heating of I under reflux boiling tetralin lead to the formation of 1-hydroxytetralin, α-tetralone and 1,1′-bitetralyl as the major products. The isolated products have been interpreted in the terms of a free radical mechanism involving the homolysis of N-O and/or C-N bonds.     

Flash vacuum pyrolysis over solid catalysts. 1. Pyrazoles over zeolites

Flash vacuum pyrolysis (fvp) reactions of 1H-pyrazole (1), 3,5-dimethylpyrazole (2), and 3,5-diphenylpyrazole (3) were carried out over zeolites. Reactions were performed using ZCOY-7, NH(4)-Y, and Na-Y zeolites. Reaction temperatures of heterogeneous reactions were lower than the corresponding temperatures in the homogeneous system, showing a catalytic effect of the zeolites. Compounds 1-3 afforded nitrogen extrusion in homogeneous fvp reactions while in the heterogeneous ones different reactions were present. Compounds 1 and 2 also afforded nitrogen extrusion; products arising from ring fragmentation were found in reactions of 2 and 3 while an isomeric imidazole was isolated in reactions of 3. Isomerization of 3 is attributed to a transition-state selectivity by the catalyst due to the relation between the size of the molecule and the cavity of the zeolite. This isomerization reaction was present only when zeolites with active Br?nsted sites were used.     

Flash vacuum pyrolysis of 1-propynoylpyrazoles: a new precursor of tricarbon monoxide

Pyrolysis of 3,5-dimethyl-1-propynoylpyrazole (1) at 640°C/0.1 torr gives 2-methyl-1$\text{H}$-pyrazolo[2,3-a]pyridin-5-one (3) with inversion of the propynoyl chain. 1-Ethynylpyrazole and tricarbon monoxide have been identified in pyrolysates formed at 700–1000°C/0.01–0.1 torr from the parent 1-propynoylpyrazole (4).     

Flash vacuum pyrolysis of azo and nitrosophenols: new routes towards hydroxyarylnitrenes and their reactions

Flash vacuum pyrolysis of phenylazonaphthols and nitrosonaphthols at 700°C and 0.02 Torr yielded quinoline, isoquinoline, indene and naphthols (and aniline only from the phenylazo derivatives). Similar FVP of p-nitroso and p-phenylazophenol gave pyridine. Also, FVP of phenanthraquinonemonophenylhydrazone and monooxime gave phenathridine and fluorenone. The formation of the heterocyclic system was assumed to involve nitrene and azatropone intermediates.     

Flash vacuum pyrolysis (F.V.P.) of 1,2,4-benzotriazine derivatives

Flash vacuum pyrolysis of 3-methylsulfanyl-1,2,4-benzotriazine N-oxide, 3-methylsulfanyl-1,2,4-benzotriazine, and 3-phenyl-1,2,4-benzotriazine are described. The N-oxide derivative underwent deoxygenation between 500 and 600°C, whereas at higher temperatures both methylsulfanyl compounds, besides yielding the same products, also gave benzimidazole formed by an independent mechanism. Transformation of these derivatives between 600 and 750°C led to formation of a complex reaction mixture indicating the radical nature of the processes. The phenyl substituted derivative was studied between 575 and 650°C and afforded benzonitrile and traces of biphenylene.     

Flash vacuum thermolysis of spirocyclohexadienones

In an attempt to prepare short-bridged hydroxymetacyclophanes $\text{1b-d}$, the spirocyclohexadienones $\text{2b-d}$ were pyrolyzed by flash vacuum thermolysis (FVT). Instead of $\text{1b-d}$, variable amounts of 4-(5-hexenyl)phenol ($\text{4b}$), β-hydroxybenzocycloalkenes ($\text{5b-d}$) and 4-(trans-1-alkenyl) phenols ($\text{6c-d}$) were obtained. The formation of these products is explained by invoking cleavage of a spiro bond in $\text{2}$ under formation of the intermediate diradical $\text{3}$ which, depending on the length of the aliphatic chain and on the temperature, has several pathways open for isomerization to spin-paired products.     

Flash vacuum pyrolysis (fvp) of some hexahydroquinazolin-4(1H)-ones

Some cis/trans-2-thioquinazolin-4-ones and their 2,4-dione analogs were subjected to flash vacuum pyrolysis. The cis- and trans-thio compounds reacted at lower temperatures than the cis- and trans-dioxo analogs, showing a lower thermal stability. All of these compounds afforded similar reactions: ring opening to the corresponding iso(thio)cyanate, the loss of H and NCS to form three isomeric cyclohexadienes and then aromatization to form the corresponding benzamide. The cis-dioxo compound also underwent a competitive retro Diels-Alder (RDA) reaction to form 3-phenylpyrimidine-2,4(1H,3H-dione(3-phenyluracil)) and butadiene. Kinetic measurements of the ring opening reaction supported a concerted β-elimination as the most probable mechanism.     

Flash pyrolysis of 4-methylene-1,2,3-benzotriazines

Flash vacuum pyrolysis of 3-alkyl-4-methylene-1,2,3-benzotriazines gives products derived from benzocyclobutane N-alkylimines and to a lesser extent from 2-methylene-benzazetidines. Benzocyclobutane N-phenylimine is formed in high yield by flash pyrolytic elimination of HCI from N-phenyl-2-methyl benzimidoyl chloride.     

The vacuum and oxidative pyrolysis of poly-p-xylylene

Poly-p-xylylene prepared by pyrolysis of di-p-xylylene has been degraded under vacuum and in the presence of oxygen as a function of temperature and oxygen pressure. The vacuum pyrolysis is mainly due to “abnormal” structures. Volatiles are initially produced quite slowly, but the reaction accelerates subsequently. Arrhenius equations were derived for various ranges of volatile formation. A mechanism has been formulated consisting of random chain scission followed by depropagation (dimers to pentamers); simulatanously another zip reaction produces hydrogen. The thermal, oxidative degradation has been studied above and below the softening point of the polymer as a function of oxygen pressure. A first-order reaction of volatile formation due to “abnormal” chain scission is followed by normal chain scission, which is also first order. The postulated mechanism leads initially to hydroperoxide formation. Arrhenius equations for volatile formation are different below and above the softening point. Oxygen consumption also follows a first-order reaction with an energy of activation of 31.5 kcal/mole.     

Catalysis in flash vacuum pyrolysis

The temperature required for flash pyrolytic elimination of water from $\text{o}$-aminobenzyl alcohols and of carbon dioxide from dihydrobenzoxazinones to give azaxylylenes is considerably lowered by the presence of alumina and silica gel in the hot zone.     

Transformations of dubinidine methiodide and related compounds in an alkaline medium and on pyrolysis

The interaction of dubinidine methiodide with dilute aqueous ammonia solution and with pyridine at room temperature has been studied. In the first case the dihydrofuran ring opens, and in the second case dequaternization takes place. The dynamics of the latter process have been investigated with the aid of PMR spectroscopy, the pyrolytic transformation of dubinidine and dubinine methiodides has been studied by electron-impact mass spectrometry. Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbekistan Republic, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 418–424, May–June, 1993.