Big Chemical Encyclopedia

Chemical substances, components, reactions, process design ...

Articles Figures Tables About

Photochemical conditions

Hydrogen bromide is unique among the hydrogen halides m that it can add to alkenes either by electrophilic or free radical addition Under photochemical conditions or m the presence of peroxides free radical addition is observed and HBr adds to the double bond with a regio selectivity opposite to that of Markovmkov s rule... [Pg.274]

A certain compound A when treated with N bromosuccinimide and benzoyl peroxide under photochemical conditions in refluxing carbon tetrachloride gave 3 4 5 tnbromobenzyl bromide in excellent yield Deduce the structure of compound A... [Pg.469]

Addition Chlorination. Chlorination of olefins such as ethylene, by the addition of chlorine, is a commercially important process and can be carried out either as a catalytic vapor- or Hquid-phase process (16). The reaction is influenced by light, the walls of the reactor vessel, and inhibitors such as oxygen, and proceeds by a radical-chain mechanism. Ionic addition mechanisms can be maximized and accelerated by the use of a Lewis acid such as ferric chloride, aluminum chloride, antimony pentachloride, or cupric chloride. A typical commercial process for the preparation of 1,2-dichloroethane is the chlorination of ethylene at 40—50°C in the presence of ferric chloride (17). The introduction of 5% air to the chlorine feed prevents unwanted substitution chlorination of the 1,2-dichloroethane to generate by-product l,l,2-trichloroethane. The addition of chlorine to tetrachloroethylene using photochemical conditions has been investigated (18). This chlorination, which is strongly inhibited by oxygen, probably proceeds by a radical-chain mechanism as shown in equations 9—13. [Pg.508]

Photoisomerization of perfluoro(4,5-diisopropylpyridazine) is postulated to proceed through Dewar diazabenzenes (25) and (26) to perfluoro(2,5-diisopropylpyrazine) (27), which is in equilibrium with the isomeric perfluoro(2,6-diisopropylpyrazine) (28) after prolonged irradiation in the liquid phase (Scheme 9) (75JCS(P1)1130). Benzo-fused pyridazines do not isomerize readily under photochemical conditions. An exception is perfluorocinnoline which rearranges to perfluoroquinazoline. [Pg.11]

The replacement of hydrogen with halogen takes place under thermal or photochemical conditions [J9, 20, 21] (equations 10-12). [Pg.370]

An explanation for the finding that concerted [4 -I- 2] cycloadditions take place thermally, while concerted [2 + 2] cycloadditions occur under photochemical conditions, is given through the principle of conservation of orbital symmetry. According to the Woodw ard-Hofmann rules derived thereof, a concerted, pericyclic [4 -I- 2] cycloaddition reaction from the ground state is symmetry-allowed. [Pg.90]

A similar result is obtained for the thermal electrocyclic ring-opening of 3,4-dimethylcyclobutene. The trans isomer yields only (2 ,4 )-2,4-hexadiene when heated, and the cis isomer yields only (2 ,4Z)-2,4-hexadiene. On UV irradiation, however, the results are opposite. Cyclization of the 2E,4 isomer under photochemical conditions yields cis product (Figure 30.4). [Pg.1182]

Under photochemical conditions, 12-oxatricyclo[7.2.1.02,8]dodeca-2(8),3,6,10-tetraen-5-one gives 8//-cyclohept[c/]oxepin-8-one in good yield.147 This reaction has been applied to the synthesis of a number of 2- and 2,4-substituted 8//-cyclohept[rf]oxepin-8-ones 17 147,148... [Pg.15]

The 2a,7b-dihydrocyclobuta[7>]benzofuran structure, obtained by addition of activated acetylenes to benzofurans (see Houben-Weyl, Vol.E6b, p 148), isomerizes thermally to a 1-benz-oxepin182 184 185 which reacts further to 1-naphthol derivatives at higher temperature182,185 (see Section 1.2 ). Under photochemical conditions, the 1-benzoxepins undergo ring contraction to the starting material.182 184... [Pg.30]

A direct insertion of sulfur dioxide into a C—C bond has been observed under photochemical conditions 3 (equation 72) a related CH insertion followed by an intramolecular sulfinate to carbonyl addition yields the same system 3 (equation 73). A further sulfolene synthesis utilizes a three-component reaction see equation 74 (cf. Section IV below) 35. [Pg.214]

The regioselectivity observed in these reactions can be correlated with the resonance structure shown in Fig. 2. The reaction with electron-rich or electron-poor alkynes leads to intermediates which are the expected on the basis of polarity matching. In Fig. 2 is represented the reaction with an ynone leading to a metalacycle intermediate (formal [4C+2S] cycloadduct) which produces the final products after a reductive elimination and subsequent isomerisation. Also, these reactions can proceed under photochemical conditions. Thus, Campos, Rodriguez et al. reported the cycloaddition reactions of iminocarbene complexes and alkynes [57,58], alkenes [57] and heteroatom-containing double bonds to give 2Ff-pyrrole, 1-pyrroline and triazoline derivatives, respectively [59]. [Pg.74]

Exo-alkylidene oxacycloalkylidene complexes such as chromium 2-oxacy-clopentylidene 30 are reluctant to react thermally with alkynes. Nevertheless, benzannulation can be achieved under photochemical conditions (for a detailed... [Pg.134]

Cyclic ethers were also obtained by cyclization of alkoxyl radicals, generated in a radical chain reaction by reacting the thione 42 with (TMSfsSiH under photochemical conditions at 20 °C (Reaction 46). Regioselectivities of cyclization have been investigated and a progressive increase of the 6-endo-trig selectivity along the series R2 = H[Pg.140]

A direct method for preparing a carboxylic acid treats an alkyl halide with NaN02 in acetic acid and DMSO. Reaction of an alkyl halide with ClCOCOaMe and (Bu3Sn)2 under photochemical conditions leads to the corresponding methyl... [Pg.564]

Thiols add to alkenes under photochemical conditions to form thioethers, and the reaction can be done intramolecularly to give cyclic thioethers. Thiols also add to alkynes and with a palladium catalyst, vinyl sulfides can be formed. " Selenium compounds (RSeH) add in a similar manner. ... [Pg.999]

The attacking radical need not always be at carbon. Amidyl radical are known and give cyclization reactions. Aminyl radical cyclizations have been reported. Oxygen radical can be generated under photochemical conditions, and they add to alkenes in a normal manner. ... [Pg.1040]

Allylic silanes react with aldehydes, in the presence of Lewis acids, to give an allyl-substituted alcohol. In the case of benzylic silanes, this addition reaction has been induced with Mg(C104)2 under photochemical conditions. The addition of chiral additives leads to the alcohol with good asymmetric induction. In a related reaction, allylic silanes react with acyl halides to produce the corresponding carbonyl derivative. The reaction of phenyl chloroformate, trimethylallylsilane, and AICI3, for example, gave phenyl but-3-enoate. ... [Pg.1239]

The transformation of isoquinoline has been studied both under photochemical conditions with hydrogen peroxide, and in the dark with hydroxyl radicals (Beitz et al. 1998). The former resulted in fission of the pyridine ring with the formation of phthalic dialdehyde and phthalimide, whereas the major product from the latter reaction involved oxidation of the benzene ring with formation of the isoquinoline-5,8-quinone and a hydroxylated quinone. [Pg.7]

This rearrangement ensues principally according to the same scheme as shown in equation 15 yielding o- and/or p-sulfonyl-substituted phenols. Yields under Friedel-Crafts conditions are poor only under photochemical conditions or in exceptional cases are the yields over 10-25%. [Pg.171]

Many such reactions may indeed be carried out preparatively under photochemical conditions, though, for reasons that cannot be gone into here (the detailed mechanism of photochemical changes), they are often not concerted but proceed via biradical intermediates. One photochemical (2n + 2n) cycloaddition that does, however, proceed via a concerted process is the example we have already referred to ... [Pg.349]

Spiroaziridinium compounds have also been synthesized under photochemical conditions. For example, the photolysis of piperidine 83 in acetonitrile resulted in 3-azoniaspirooctane 85 (Equation 19) <1997JOC6903>. Its presence was detected by H NMR spectroscopy and mass spectrometry. This azoniaspiro species was thought to be transient and went on to form N-substituted piperidines which were qualitatively identified by gas liquid chromatography (GLC). [Pg.1050]

Another extremely reactive form of titanocene, namely black tita-nocene, was discovered by Rausch and Alt in 1974 as the product of the photolysis of Cp2TiMe2 (19) in either aliphatic or aromatic solvents (41). Irradiation of a hexane solution of 19 resulted in the deposition of a dark precipitate with concomitant evolution of essentially only methane. Benzene solutions of this photochemically generated titanocene reacted rapidly with CO to give red solutions from which Cp2Ti(CO)2 (1) could be isolated in 60% yield. Similarly, 1 could be prepared directly under photochemical conditions in similar yield if 19 was irradiated in a CO atmosphere (41,42). [Pg.328]

An improved synthesis of 3,4-dihydro-2,l-benzothiazine 2,2-dioxide was reported by Togo and co-workers using photochemical conditions . Treatment of A-alkyl 2-(aryl)ethanesulfonamides 18 with (diacetoxyiodo)arenes under irradiation with a tungsten lamp at 20-30 °C afforded 2,1-benzothiazines 19 and 20. Chemical yields and selectivities were dependent upon the choice of solvents and the reactant s substituents 18 (Table 1). When THF and EtOH were used as solvents, the reactions failed to give the cyclized products, since their a-hydrogen was abstracted by the intermediate sulfonamidyl radical. Compound 20 was obtained as a major product when 1,2-dichloroethane was employed as a solvent. In contrast, in the case of EtOAc as solvent, compound 19 was obtained as the major product. [Pg.4]

Similarly, the addition of a variety H donors under photochemical conditions generally provided mixtures of products 52-54 (Scheme 14) (77CL1127). When xanthene was used as the hydrogen donor, structures 52 usually prevailed. On the other hand, no structures 52 were detected in the case of etheral donors such as tetrahydrofuran or 1,4-dioxane. [Pg.152]

Me3SnPPh2 will add to allenes under photochemical conditions, giving two regioiso-meric products32. The predominant species is that in which the phosphine residue attaches to the central carbon atom (reaction 23). The overall yield, and relative proportions of 16 and 17 produced, depends on the nature of the substituent R. For R = H, yield = 78%, ratio 16 17 = 89 11 for R = Me, yield = 67%, ratio = 73 27 for R = Bu, yield = 58%, ratio = 88 12. [Pg.732]

Haloarenes have been found to undergo nucleopilic substitution when irradiated with the triphenyl stannyl anion46, reacting via a radical S l mechanism. In many cases the reaction will only occur under photochemical conditions. The reaction is found to proceed with chloro- and bromo-substituted arenes, but not iodo-compounds. The anion is produced either by treatment of triphenyltin chloride or hexaphenylditin with sodium metal in liquid ammonia, and will react with a wide variety of arenes (reaction 30). [Pg.736]

In 1987 we reported26 that the three possible C3H2 isomers S-2, T-36, and S-37 can be transformed into each other under photochemical conditions. For several reasons propargylene (36) attracted our attention On the one hand the first C3H2 parent species, identified by direct spectroscopic methods, was triplet propargylene (T-36). Its ESR spectrum was published in 1965,63 and, based on the zero-field-splitting parameters, a linear or nearly linear structure was derived. On the other hand, the structural elucidation of 36 by comparison of the calculated and experimental IR spectra turned out to be rather difficult.64... [Pg.126]

An allylic phosphorus ester rearrangement to form a new C-P bond has been reported under photochemical conditions.179 Under irradiation in the presence of 9,10-dicyanoanthracene, an allylic phosphite ester undergoes rearrangement to form the corresponding allyl-icphosphonite ester (Equation 4.40). Benzophenone serves only poorly as a photosensitizer in this reaction. [Pg.131]

Since the direct carbonylation of C-H bonds with CO leading to aldehydes is endothermic, the reaction is conducted under photochemical conditions.109,109a 109e On the other hand, the direct coupling of a C-H bond, CO, and an olefin leading to a ketone is exothermic and can proceed under thermal reaction conditions. [Pg.235]

A series of experiments on ring expansions under photochemical conditions has been published by Wentrup et al. <1996CC813, 1998J(P1)2247, 20040BC246, 20040BC1227>. Schematic representation of these transformations is shown in Seheme 6. [Pg.649]


See other pages where Photochemical conditions is mentioned: [Pg.253]    [Pg.150]    [Pg.155]    [Pg.22]    [Pg.37]    [Pg.89]    [Pg.877]    [Pg.141]    [Pg.111]    [Pg.274]    [Pg.203]    [Pg.877]    [Pg.21]    [Pg.100]    [Pg.148]    [Pg.266]    [Pg.241]    [Pg.844]   
See also in sourсe #XX -- [ Pg.304 ]

See also in sourсe #XX -- [ Pg.25 ]




SEARCH



Batch conditions, photochemical reaction

Flow conditions, photochemical reaction

Flow conditions, photochemical reaction under

Photochemical conditions for

© 2024 chempedia.info