C/.s-Isomerization

The photoirradiation of (9) covalently bound to porphyrin induces irreversible cis,trans-isomerization The influence of picric acid on the photochemical tmns,c/s-isomerization of 4-(4 -dimethylaminostyryl)pyridine has been evaluated. Details about the photophysical and photochemical behaviour of trans-di-(2-naphthyl)ethene have been published. The styryl dye (10) has been synthesized and its photochemistry and photochemical properties studied. The photochromic properties depend upon the cis,trans-isomerization and also on (2 + 2)-cycloaddition processes. ... 

Abrash S, Repinec S and Hochstrasser R M 1990 The viscosity dependence and reaction coordinate for isomerization of c/s-stilbene J. Chem. Phys. 93 1041-53... 

JOC1537). The mechanisms of these transformations may involve homolytic or heterolytic C —S bond fission. A sulfur-walk mechanism has been proposed to account for isomerization or automerization of Dewar thiophenes and their 5-oxides e.g. 31 in Scheme 17) (76JA4325). Calculations show that a symmetrical pyramidal intermediate with the sulfur atom centered over the plane of the four carbon atoms is unlikely <79JOU140l). Reactions which may be mechanistically similar to that shown in Scheme 18 are the thermal isomerization of thiirane (32 Scheme 19) (70CB949) and the rearrangement of (6) to a benzothio-phene (80JOC4366). 

Fi re 12.6 Schematic diagram Illustrating the proton movements in the photocycle of bacteriorhodopsin. The protein adopts two main conformational states, tense (T) and relaxed (R). The T state binds trans-tetinal tightly and the R state binds c/s-retinal. (a) Stmcture of bacteriorhodopsin in the T state with hflus-retinal bound to Lys 216 via a Schiff base, (b) A proton is transferred from the Schiff base to Asp 85 following isomerization of retinal and a conformational change of the protein. 

Related to stereoregularity is the possibility of cis, trans isomerism. The molecule of natural rubber is a c/s-1,4-polyisoprene whilst that of gutta percha is the trans isomer. 

Experimental studies have indicated that all of the isomers prepared to date are quite reactive, but whether the most stable isomer has been observed is uncertain. Two of the isomeric [lOJarmulenes, as well as other products, are formed by photolysis of c/s-9,10-dihydronaphthalene ... 

In a similar manner diethyl maleate (actually diethyl fumarate since the basic enamine catalyzes the maleate s isomerization upon contact) forms unstable 1,2 cycloadducts with enamines with hydrogens at temperatures below 30°C (37). At higher temperatures simple alkylated products are formed (41). Enamines with no )3 hydrogens form very stable 1,2 cycloadducts with diethyl maleate (36,37,41). The two adjacent carboethoxy groups of the cyclobutane adduct have been shown to be Irons to one another (36,37). 

The parent thionine system 1 up to now has not been prepared probably because the C-S bond in valence isomeric forms is too weak giving rise to facile rearrangement or decomposition. The obvious synthetic route, photochemical transformation of cyclooctatetraenccpisulfide 2 (9-thiabicyclo[6.1.0]nona-2,4,6-triene), does not lead to 1, but intriguingly to another valence isomer, the sulfur-bridged homotropylidene system 3.20... 

Reversible formation of ionic intermediates in halogenated solvents has been suggested to be due to the weakly nucleophilic character of the counteranion, the tribromide ion, which should dissociate into nucleophilic bromide and free bromine before reacting with the bromonium ion (refs. 11,25,26). In order to check this hypothesis the product distribution of the c/s-stilbene bromination in chloroform was investigated (ref. 27). In the latter solvent the formation constant of Br3 is considerably lower than in DCE, Kf = 2.77 (0.13) x 10 against > 2 x 107 M 1. (ref. 28). As a consequence, at 10 3 M [Br2] relevant amounts of bromide ions are present as counteranion of the bromonium intermediate. Nevertheless, the same trend for the isomerization of cis- to rran -stilbene, as well as an increase of... 

This type of isomerism is also possible with other double bonds, such as C=N, N=N, or even C=S, though in these cases only two or three groups are connected to the double-bond atoms. In the case of imines, oximes, and other C=N compounds, if W = Y 60 may be called syn and 61 anti, though ( ) and (Z) are often used here too. In azo compounds there is no ambiguity. Compound 62 is always syn or (Z) regardless of the nature of W and Y, and 63 is E. 

The isomerization takes place because the excited states, both 5i and T, of many alkenes have a perpendicular instead of a planar geometry (p. 311), so cis-trans isomerism disappears upon excitation. When the excited molecule drops back to the So state, either isomer can be formed. A useful example is the photochemical conversion of c/s-cyclooctene to the much less stable trans isomer." Another interesting example of this isomerization involves azo crown ethers. The crown ether (5), in which the N=N bond is anti, preferentially binds NH4, Li, and Na, but the syn isomer preferentially binds and Rb (see p. 105). Thus, ions can be selectively put in or taken out of solution merely by turning a light source on or off." ... 

The isomerization observed in the methylenation of c/s-a-decalones has been turned to good advantage. Mixtures of cis- and tra/is-isomers of the a-decalones (44) and (46) gave only the /ra/i -decalins (45) and (47). 

One of the most important problems that has to be solved in the thiepin chemistry is the mechanism of the sulfur extrusion reaction. Ready loss of sulfur of the simplest thiepins presumably occurs by valence isomerization to the corresponding thianorcaradiene, which requires a [4n -I- 2] disrotatory electrocyclic process leading to a c/s-fused three-membered ring, followed by cheletropic loss of sulfur. A lot of evidence supporting the above mechanism, though inconclusive, is available to date. 

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