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 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 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 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.     

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 N-phenylbenzamide oxime and related compounds

Flash vacuum pyrolysis (FVP) of the benzamide oxime 1 at 650 °C leads to the imino-oxadiazole 10 as the major product. It is probably formed by intermolecular cycloaddition of benzonitrile oxide 11 and the diphenylcarbodiimide 12, an unexpected process to take place under FVP conditions. Intermediates 11 and 12 are themselves obtained by competitive dehydration and elimination of aniline from 1. Mixed products were obtained from FVP of the C- and N-p-tolyl analogues of 1 (5 and 6, respectively) probably owing to equilibration of the carbodiimide intermediate.     

Gas‐phase pyrolysis of 2‐heteroaromatic‐1‐dimethylaminoethylenes: Kinetic and mechanistic study

Gas‐phase pyrolysis reactions of 4(2′‐dimethylaminoethenyl)‐2‐oxo‐2H‐benzo[b]pyran‐3‐carbonitrile ( 1 ), 4(2′‐dimethylaminoethenyl)‐2‐oxo‐2H‐naphtho[1,2‐b]pyran‐3‐carbonitrile ( 2 ), 1,6‐dihydro‐4‐(2′‐dimethylaminoethenyl)‐6‐oxo‐1‐phenylpyridazine‐3,5‐dicarbonitrile ( 3 ), 2‐cyano‐5‐dimethylamino‐3‐phenyl‐2,4‐pentadienonitrile ( 4 ), 2‐cyano‐5‐dimethylamino‐3‐(2‐thienyl)‐2,4‐pentadienonitrile( 5 ), 1,2‐dihydro‐4‐(2′‐dimethylaminoethenyl)‐oxo‐quinoline‐4‐carbonitrile ( 6 ), 6‐(ethylthio)‐4‐(2′‐dimethylaminoethenyl)‐2‐phenylpyrimidine‐5‐carbonitrile ( 7 ) (Scheme 1) have been carried out. The rates of gas‐phase pyrolytic reactions of compounds 3, 4, 5, and 7 have been measured and found to correspond to unimolecular first‐order reactions. Product analyses together with kinetic data were used to outline a feasible pathway for the pyrolytic reactions of the compounds under study. © 2001 John Wiley & Sons, Inc. Heteroatom Chem 12:47–51, 2001     

Mechanism and linear free energy relationships in the kinetics of formation of bicyclo[3.3.1]nonane derivatives from 1,3,5‐trinitrobenzene,phenyl‐substituted 1‐benzyl‐1‐(ethoxycarbonyl)‐2‐propanones,and triethylamine

The kinetics and mechanism of cyclization of the anionic sigma complex obtained from the reaction of 1,3,5‐trinitrobenzene (TNB) and 1‐benzyl‐1‐(ethoxycarbonyl)‐2‐propanone (BEP) in the presence of triethylamine (NEt₃) have been studied in CH₃CN–CH₃OH (50% v/v). The order of the reaction has been found to be zero in TNB and BEP, unity in NEt₃, and negative and nonintegral in triethylammonium chloride. The rate has been observed to increase slightly with an increase in the concentration of the added salt (tetraethylammonium chloride). The rate constants for the formation of bicyclic adducts from phenyl‐substituted BEP and TNB in the presence of triethylamine have been correlated with σ values. © 2011 Wiley Periodicals, Inc. Int J Chem Kinet 43: 467–473, 2011     

Studies with 1‐functionally substituted alkyl azoles: Novel synthesis of functionally substituted azolylbenzimidazoles and functionally substituted azolyl‐1,2,4‐triazoles

ω‐Azolylacetophenones 1 and 2 react with dimethylformamide dimethylacetal to yield enaminones 7,8 that were converted into azolylazoles via reaction with hydrazine and with hydroxylamine. Compounds 1,2 also coupled with aromatic diazonium salts to yield arylhydrazones and reacted with nitrous acid to yield corresponding oximes.     

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.     

Unexpected formation of 1,2‐dihydro‐2‐azolyl‐and azinylisoquinolines by the reduction of the corresponding isoquinolinium salts with sodium borohydride in methanol

The reduction of different 2‐azolyl‐and azinylisoquinolinium salts with sodium borohydride in methanol was studied. Surprisingly, contrary to what is found in the literature 1,2‐dihydroisoquinoline derivatives were obtained. Their formation was attributed to the electron withdrawing character of the heterocyclic ring in position 2 of the isoquinolinium moiety. This was corroborated by synthesis and reduction of differently substituted 2‐phenyl‐ and 2‐methylisoquinolinium salts.     

2‐[2‐(Pyrrolidin‐2‐yl)propan‐2‐yl]‐1H‐pyrrole and its amide derivative 1‐{2‐[2‐(1H‐pyrrol‐2‐yl)propan‐2‐yl]pyrrolidin‐1‐yl}ethanone

In the title compounds, C₁₁H₁₈N₂, (II), and C₁₃H₂₀N₂O, (III), the pyrrolidine rings have twist conformations. Compound (II) crystallizes with two independent molecules (A and B) in the asymmetric unit. The mean planes of the pyrrole and pyrrolidine rings are inclined to one another by 89.99 (11) and 89.35 (10)° in molecules A and B, respectively. In (III), the amide derivative of (II), the same dihedral angle is much smaller, at only 13.42 (10)°. In the crystal structure of (II), the individual molecules are linked via N—H...N hydrogen bonds to form inversion dimers, each with an R²₂(12) graph‐set motif. In the crystal structure of (III), the molecules are linked via N—H...O hydrogen bonds to form inversion dimers with an R²₂(16) graph‐set motif.     

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.     

Synthesis of 2‐Arylbenzoxazoles from Flash Vacuum Pyrolysis of 2‐Methoxy‐N‐(arenylidene)anilines

Flash vacuum pyrolysis of 2‐methoxy‐N‐(arenylidene)anilines 2a‐g at 700 °C and 1 × 10^‐2 Torr gave the corresponding 2‐arylbenzoxazoles 1a‐g .     

1‐Azonia‐2‐boratanaphthalenes

The 1‐azonia‐2‐boratanaphthalenes (NH)(BX)C₈H₆ can be synthesized from 2‐aminostyrene and the dihaloboranes XBHal₂ ( 1 ‐ 4 : X = Cl, Br, iPr, tBu). Further derivatives (NH)(BX)C₈H₆ are obtained from 1 by replacing Cl by alkoxy or alkyl groups [ 5 ‐ 8 : X = OMe, OtBu, Me, (CH₂)₃NMe₂]. The hydrolysis of 1 gives a mixture of the bis(azoniaboratanaphthyl) oxide [(NH)BC₈H₆]₂O ( 9 ) and the hydroxy derivative (NH)[B(OH)]C₈H₆ ( 10 ). The diboryl oxide 9 crystallizes in the space group C2/c. The lithiation of 4 at the nitrogen atom gives [NLi(tmen)](BtBu)C₈H₆ ( 11 ), which upon reaction with the diborane(4) B₂Cl₂(NMe₂)₂ yields the 1, 2‐bis(azoniaboratanaphthyl)diborane B₂[N(BtBu)C₈H₆]₂(NMe₂)₂ ( 12 ). The 2‐chloro‐1‐methyl‐4‐phenyl derivative (NMe)(BCl)C₈H₅Ph ( 13 ) of the parent (NH)(BH)C₈H₆ can be synthesized from the aminoborane BCl₂(NMePh) and phenylethyne. Substitution of Cl in 13 gives the derivatives (NMe)(BX)C₈H₅Ph [ 14 ‐ 20 : X = N(SiMe₃)₂, Me, Et, iBu, tBu, CH₂SiMe₃, Ph] and the reaction of 13 with Li₂O affords the bis(azoniaboratanaphthyl) oxide [(NMe)BC₈H₅Ph]₂O ( 21 ). The reaction of 16 or 19 with [(MeCN)₃Cr(CO)₃] yields the complexes [{(NMe)(BX)C₈H₅Ph}Cr(CO)₃] ( 22 , 23 : X = Et, CH₂SiMe₃), in which the chromium atom is hexahapto bound to the homoarene part of 16 or 19 , respectively. The complex 23 crystallizes in the space group P2₁/c. Upon reaction of the phenols para‐C₆H₄R(OH) with the aryldichloroboranes ArBCl₂ and subsequent condensation of the products with phenylethyne, the 1‐oxonia‐2‐boratanaphthalenes O(BAr)C₈H₄RPh with R in position 6 and Ph in position 4 are formed ( 24 ‐ 26 : Ar = Ph, R = H, Me, OMe; 27 ‐ 29 : Ar = C₆F₅, R = H, Me, OMe). The azoniaboratanaphthalenes 1 ‐ 23 were characterized by NMR methods.     

1‐(2‐Pyridyl)ethan‐1‐one 8‐quinolylhydrazone and 1‐(1H‐pyrrol‐2‐yl)ethan‐1‐one 8‐quinolylhydrazone

The structures of the title compounds, C₁₆H₁₄N₄, (I), and C₁₅H₁₄N₄, (II), respectively, have been determined, and their molecular packing arrangements compared. Both are essentially flat mol­ecules, with respective dihedral angles between the quinoline and heterocyclic rings of 19.0 (1) and 8.5 (2)°. The pyridyl derivative, (I), packs in a P2₁/c unit cell, while in the pyrrolyl compound, (II), the mol­ecules pack in Pca2₁ and form a crinkled ribbon arrangement through the association of pyrrole NH groups with the quinoline N atoms.     

1‐(1‐Benzoylpropen‐2‐yl)‐3‐methylisothiosemicarbazide

The structure of the title S‐alkyl­ated iso­thio­semicarbazide, C₁₂H₁₅N₃OS, was determined by single‐crystal diffractometry and compared with the structures of other compounds containing the S‐alkyl­thio­semicarbazide moiety. Such structures cluster into two groups, according to the different orientation of the –SR group with respect to the hydrazine N atom of the thio­semicarbazide. The cis arrangement is preferred by most mol­ecules in the solid state, in spite of the possibility of intramolecular N—H?N interactions in the opposite orientation.     

trans‐1‐Cyano‐2‐(2‐methoxy­phenyl)‐1‐nitro­ethyl­ene

The title compound, C₁₀H₈N₂O₃, has been prepared by condensation of 2‐methoxy­benz­aldehyde and nitro­aceto­nitrile in ethanol at room temperature. Its investigation has been undertaken as a part of search for new nonlinear optical compounds. The π‐conjugated mol­ecule is almost planar. Molecules in the crystal are packed in stacks with antiparallel molecular orientation and slightly alternating distances between mean molecular planes.