I Benzenethiol

Figure 6 Gold(I) benzenethiolate complexes exhibiting room temperature luminescence. (Adapted from Watase, Nakamota, Kitamura, Kanehisa, Kai and Yanagida. Reproduced by permission of The Royal Society of Chemistry)...

Fig. 28.4. Conducting molecules (I) 2,7-dithiolpyrene (II) 4,4Cdithiol-diphenylacetylene (III) l-thiol-4-ethynylphenyl-4 -ethynylphenyl- F-benzenethiolate and (IV) 2 -amino-4-ethynylphenyl-4Cethynylphenyl-5 -nitro- I -benzenethiolate.

Reaction of pentafluorobenzene with copper(i) benzenethiolate gives 2,4-difluoro-l,3,5-tris(phenylthio)benzene. This orientation is not inconsistent with the F n.m.r. . The fluorine para to the hydrogen in pentafluorobenzene has been replaced by a variety of nucleophiles, such as p-HCeF4S- forming p-HCeF4SC6F4H-p . 

Considerable use has been made of the copper(i) benzenethiolate and butanethiolate in the preparation of thioethers. A large series of compounds of general formula (RS)nX, n>l, R = Ph or Bu, and X is an aryl group, have been prepared from the copper(i) thiolates and aryl halides (aryl bromides only reacted with the butanethiolate) . ... 

Analogous chemistry was independently described by de Meijere (Scheme 8.113) [310,311]. The best results were achieved with Cu(I) benzenethiolate or preactivated nanosized copper powder (Cu -NP) catalysts. These conditions allowed better functional group compatibility and generally led to the formation of pyrroles 324 with a higher efficiency. 

Solid-state luminescence and crystal structures of novel gold(I) benzenethiolate complexes, S. Watase, M. Makamoto, T. Kitamura, N. Kanehisa, Y. Kai, S. Yanagida, J. Chem. Soc., Dalton Trans. 2000, 3585. 

Carboxylic acids, a-bromination of 55, 31 CARBOXYLIC ACID CHLORIDES, ketones from, 55, 122 CARBYLAMINE REACTION, 55, 96 Ceric ammonium nitrate [Ammonium hexa mtrocerate(IV)[, 55, 43 Chlorine, 55, 33, 35, 63 CHROMIUM TRIOXIDE-PYRIDINE COMPLEX, preparation in situ, 55, 84 Cinnamomtnle, a-phenyl- [2-Propeneni-tnle 2,3-diphenyl-], 55, 92 Copper(l) iodide, 55, 105, 123, 124 Copper thiophenoxide [Benzenethiol, copper(I) salt], 55, 123 CYCLIZATION, free radical, 55, 57 CYCLOBUTADIENE, 55, 43 Cyclobutadieneiron tricarbonyl [Iron, tn-carbonyl(r)4-l,3-cyclo-butadiene)-], 55,43... 

Benzenesulfonyl chloride, 4-methyl- [p-Tol-uenesulfonyl chloride], 55, 57, 59 Benzenethiol [Phenol, thio-], 55, 122 Benzenethiol, copper(I) salt [Thiophenol, copper(I) salt], 55, 123 Benzenethiol, lithium salt [Thiophenol, lithium salt], 55, 1 22 Benzoic acid, 2-amino- [Anthramlic acid], p bromination of, 55, 23... 

Bratt, J. and Suschitzky, H., Reactions of polyhalogenopyridines and their N-oxides with benzenethiols, with nitrite, and with trialkyl phosphites, and of pentachloropyridine N-oxide with magnesium, /. Chem. Soc., Perkin I, 1689, 1973. 

Benzenethiol adsorbs on Au(lll) from the aqueous solution to form a well-ordered monolayer of a commensurate (.yi3 X. yi3)i 13.9° symmetry [159]. It has been found that the ordered phase... 

A synthetic study has revealed that the combination of anhydrous hydrogen chloride and zinc(II) chloride in the presence of a nucleophile, e.g. benzenethiol, promotes the ring cleavage of cyclobutanones such as bicyclo[3.2.0]heptan-6-one (28) to provide / -sulfanyl ketones such as 3-phenylsulfanylcycloheptanone (27).63 Alternatively, iodotrimethylsilane in the presence of either mercury/water or zinc(II) iodide also converts cyclobutanones to /i-iodo ketones 29.64 The synthetic applications of these transformations are summarized in Table 5. 

A considerable difference in reactivity toward gold-carbon bond cleavage is found for methylgold(I) and -gold(III) compounds. Thus, for the reactions with benzenethiol, which proceed by elimination of methane, the following order of reactivity is obtained 207, 208) ... 

The 4,7-diaryl-4,5-dihydro-l,3-oxazepinones 27 can be accessed from a two-step sequence involving the reaction of l-aryl-2-aroylcyclopropanes 25 with chlorosulfonyl isocyanate, followed by removal of the chlorosulfonyl group from 26 with benzenethiol in pyridine (Scheme 2) <1995SC1939>. Yields in each step were low to moderate, for example, for 27 (Ar1 = />-Mc(XV,I Is, Ar2 = Ph), the yield was 50% while for the corresponding intermediate 26, the yield was 53%. 

FIGURE 3.6. (a) Cross-sectional schematics of a silicon wafer with a nanopore etched through a suspended silicon nitride membrance. SAM is formed between sandwiched Au eletrodes in the pore area (circled), (b) I(V) characteristics of a Au-2 -amino-4-ethynylphenyl-4-ethynylphenyl-5 -nitro-1 -benzenethiolate-Au (chemical structure shown below) molecular junction device at 60 K. The peak current density is 50 A/cm2, the NDR is 2400 pQ. cm2, the peak-to-valley ratio is 1030 1. [Adapted from Ref.30 Chen el al., Science 286, 1550-1552 (1999).]... 

Sulfur compounds I, II and IV, methyl sulfonic acid, ethylsulfonic acid and benzenesulfonic acid could have been derived from a number of precursors in the parent coal samples. Firstly, mercaptans and thiols will form sulfonic acids when oxidized with peroxides. However, the presence of methylmercaptan, ethylmercaptan and benzenethiol in an exhaustively extracted coal sample is highly unlikely and we believe that the sulfonic acids did not arise from these compounds. In addition, there is a possibility that these sulfonic acids may have come from pendant or terminal thioether groups. 

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