Thiobenzophenone

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Thiobenzophenone
Thiobenzophenone-2D-skeletal.png
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Identifiers
CAS number 1450-31-3
Jmol-3D images Image 1
Properties
Molecular formula C13H10S
Molar mass 198.28 g mol−1
Appearance Deep blue solid
Melting point 53-54 °C
Boiling point 174 °C
Hazards
Flash point no
Except where noted otherwise, data are given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
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Infobox references

Thiobenzophenone is an organosulfur compound with the formula (C6H5)2CS. It is the prototypical thioketone. Unlike other thioketones that tend to dimerize to form rings and polymers, thiobenzophenone is quite stable, although it photoxidizes in air to form benzophenone and sulfur.[1] Thiobenzophenone is deep blue and dissolves readily in many organic solvents.

Structure[edit]

According to the double bond rule, the C=S double bond of most thioketones is unstable with respect to dimerization making the stability of thiobenzophenone valuable for studying C=S chemistry.[1] The energy difference between the p orbitals of sulfur and carbon is greater than that between oxygen and carbon in ketones.[2] The relative difference in energy and diffusity of the atomic orbitals of sulfur compared to carbon results in poor overlap of the orbitals and the energy gap between the HOMO and LUMO is thus reduced for C=S relative to C=O.[3] The striking blue appearance of thiobenzophenone is due to π→ π* transitions upon the absorption of light with a wavelength of 314.5 nm.[2] The C=S bond length of thiobenzophenone is 1.63 Å, which is comparable to 1.64 Å, the C=S bond length of thioformaldehyde, measured in the gas phase. Due to steric interactions, the phenyl groups are not coplanar and the dihydral angle SC-CC is 36°.[3] A variety of thiones with structures and stability related to thiobenzophenone have also been prepared.[1]

Synthesis[edit]

One of the first reported syntheses of thiobenzophenone involves the reaction of sodium hydrosulfide and benzophenone dichloride:[4]

Ph2CCl2 + 2 NaSH → Ph2C=S + 2 NaCl + H2S

A method adapted from the sequence above that has been found to be more convenient and gives more reproducible results involves the use of benzophenone as the starting material:[5]

Ph2C=O + H2S → Ph2C=S + H2O

In the above reaction scheme, a mixture of gaseous hydrogen chloride and hydrogen sulfide are passed into a cooled solution of benzophenone in ethanol. Thiobenzophenone can also be produced by a Friedel-Crafts reaction of thiobenzoyl chloride and benzene.[6]

Reactivity[edit]

Due to the weakness of the C=S bond, thiobenzophenone is more reactive than its C=O benzophenone counterpart. Thiobenzophenone as well as other thioketones are considered to be superdipolarophiles and dienophiles that rapidly combine with 1,3-dienes in Diels-Alder cycloadditions.[2] The rate of thioketones in cycloadditions is related but not limited to the size of the small HOMO/LUMO energy gap of the π-MOs of the C=S double bond.[3] Reactions between thiobenzophenone and most dienes yield Diels-Alder adducts whereas reactions with monoolefins yield bicyclic compounds.[7]

References[edit]

  1. ^ a b c Organosulfur Chemistry I: Topics in Current Chemistry, 1999, Volume 204/1999, 127-181, doi:10.1007/3-540-48956-8_2
  2. ^ a b c Fisera, L.; Huisgen, R.; Kalwinsch, I.; Langhals,E.; Li, X.; Mloston, G.; Polborn, K.; Rapp, J.; Sicking, W.; Sustmann, R. "New Thione Chemistry". Pure & Appl. Chem., 1996, 68, 789-798. doi:10.1351/pac199668040789
  3. ^ a b c Sustmann, R.; Sicking, W.; Huisgen, R. "A Computational Study of the Cycloaddition of Thiobenzophenone S-Methylide to Thiobenzophenone". J. Am. Chem. Soc. 2003, 125, 14425-14434. doi:10.1021/ja0377551
  4. ^ Organic Syntheses, Coll. Vol. 4, p.927 (1963); Vol. 35, p.97 (1955).
  5. ^ Org. Syntheses Coll. Vol. 2, 573 (1943).
  6. ^ Horst Viola, Steffen Scheithauer and Roland Mayer "Organische Schwefelverbindungen,97. Friedel-Crafts-Reaktionen mit Thiosäurechloriden" Chem. Ber. 1968, volume 101, pages 3517–3529. doi:10.1002/cber.19681011024
  7. ^ Okuma, K.; Yamamoto, T.; Shirokawa, T.; Kitamura, T.; Fujiwara, Y. "The First Isolation of Benzyne-Thiobenzophenone Adducts". Tetrahedron Letters, 1996, 49, 8883-8886. doi:10.1016/S0040-4039(96)02074-6