 | |
| Names | |
|---|---|
| Preferred IUPAC name 1,1,1,3,3,3-Hexafluoropropane-2-thione | |
| Other names Perfluorothioacetone | |
| Identifiers | |
3D model (JSmol) | |
| ChemSpider | |
PubChem CID | |
| |
| Properties | |
| C3F6S | |
| Molar mass | 182.08 g·mol−1 |
| Appearance | blue gas |
| Boiling point | 8 °C (46 °F; 281 K) |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). | |
Hexafluorothioacetone is an organic perfluoro thione compound with formula CF3CSCF3. At standard conditions it is a blue gas. [2]
Hexafluorothioacetone was first produced by Middleton in 1961 by boiling bis-(perfluoroisopropyl)mercury with sulfur.
Hexafluorothioacetone boils at 8 °C. [3] Below this it is a blue liquid. [2]
The blue colour is due to absorption in the visible light range with bands at 800–675 nm and 725–400 nm. These bands are due to T1–S0 and S1–S0 transitions. [2] There is also a strong absorption in ultraviolet around 230-190 nm. [2]
Hexafluorothioacetone acts more like a true thiocarbonyl (C=S) than many other thiocarbonyl compounds, because it is not able to form thioenol compounds (=C-S-H), and the sulfur is not in a negative ionized state (C-S−). [4] Hexafluorothioacetone is not attacked by water or oxygen at standard conditions as are many other thiocarbonyls. [2]
Bases trigger the formation of a dimer 2,2,4,4-tetrakis-(trifluoromethyl)-1,3-dithietane. [2] Bases includes amines. [4]
The dimer can be heated to regenerate the hexafluorothioacetone monomer. [2]
The dimer is also produced in a reaction with hexafluoropropene and sulfur with some potassium fluoride. [2] [5]
Hexafluorothioacetone reacts with bisulfite to form a Bunte salt CH(CF3)2SSO2−. [4]
Thiols reacting with hexafluorothioacetone yield disulfides or a thiohemiketal:
With mercaptoacetic acid, instead of a thiohemiketal, water elimination yields a ring shaped molecule called a dithiolanone -CH2C(O)SC(CF3)2S- (2,2-di(trifluoromethyl)-1,3-dithiolan-4-one). [4] Aqueous hydrogen chloride results in the formation of a dimeric disulfide CH(CF3)2SSC(CF3)2Cl. [4] Hydrogen bromide with water yields the similar CH(CF3)2SSC(CF3)2Br. [4] Dry hydrogen iodide does something different and reduces the sulfur making CH(CF3)2SH. Wet hydrogen iodide only reduces to a disulfide CH(CF3)2SSC(CF3)2H. Strong organic acids add water to yield a disulfide compound CH(CF3)2SSC(CF3)2OH. [4]
Chlorine and bromine add to hexafluorothioacetone to make CCl(CF3)2SCl and CBr(CF3)2SBr. [4]
With diazomethane hexafluorothioacetone produces 2,2,5,5-tetrakis(trifluoromethyl)-l,3-dithiolane, another substituted dithiolane. [4] Diphenyldiazoniethane reacts to form a three membered ring called a thiirane (di-2,2-trifluoromethyl-di-3,3-phenyl-thiirane)
Trialkylphosphites (P(OR)3) react to make a trialkoxybis(trifluoromethyl)methylenephosphorane (RO)3P=C(CF3)2 and a thiophosphite (RO)3PS. [4]
Hexafluorothioacetone can act as a ligand on nickel. [6]
Hexafluorothioacetone is highly reactive to alkenes and dienes combining via addition reactions. With butadiene it reacts even as low as -78 °C to yield 2,2-bis-(trifluoromethyl)-3,6-dihydro-2H-l-thiapyran. [7]
In organic chemistry, an imine is a functional group or organic compound containing a carbon–nitrogen double bond. The nitrogen atom can be attached to a hydrogen or an organic group (R). The carbon atom has two additional single bonds. Imines are common in synthetic and naturally occurring compounds and they participate in many reactions.
Organopalladium chemistry is a branch of organometallic chemistry that deals with organic palladium compounds and their reactions. Palladium is often used as a catalyst in the reduction of alkenes and alkynes with hydrogen. This process involves the formation of a palladium-carbon covalent bond. Palladium is also prominent in carbon-carbon coupling reactions, as demonstrated in tandem reactions.
Organosulfur chemistry is the study of the properties and synthesis of organosulfur compounds, which are organic compounds that contain sulfur. They are often associated with foul odors, but many of the sweetest compounds known are organosulfur derivatives, e.g., saccharin. Nature is abound with organosulfur compounds—sulfur is vital for life. Of the 20 common amino acids, two are organosulfur compounds, and the antibiotics penicillin and sulfa drugs both contain sulfur. While sulfur-containing antibiotics save many lives, sulfur mustard is a deadly chemical warfare agent. Fossil fuels, coal, petroleum, and natural gas, which are derived from ancient organisms, necessarily contain organosulfur compounds, the removal of which is a major focus of oil refineries.
2,2,2-Trifluoroethanol is the organic compound with the formula CF3CH2OH. Also known as TFE or trifluoroethyl alcohol, this colourless, water-miscible liquid has a smell reminiscent of ethanol. Due to the electronegativity of the trifluoromethyl group, this alcohol exhibits a stronger acidic character compared to ethanol.
Hexafluoroacetone (HFA) is a chemical compound with the formula (CF3)2CO. It is structurally similar to acetone; however, its reactivity is markedly different. It a colourless, hygroscopic, nonflammable, highly reactive gas characterized by a musty odour. The most common form of this substance is hexafluoroacetone sesquihydrate (1.5 H2O), which is a hemihydrate of hexafluoropropane-2,2-diol (F
3C)
2C(OH)
2, a geminal diol.
Thiophosgene is a red liquid with the formula CSCl2. It is a molecule with trigonal planar geometry. There are two reactive C–Cl bonds that allow it to be used in diverse organic syntheses.
Iodine compounds are compounds containing the element iodine. Iodine can form compounds using multiple oxidation states. Iodine is quite reactive, but it is much less reactive than the other halogens. For example, while chlorine gas will halogenate carbon monoxide, nitric oxide, and sulfur dioxide, iodine will not do so. Furthermore, iodination of metals tends to result in lower oxidation states than chlorination or bromination; for example, rhenium metal reacts with chlorine to form rhenium hexachloride, but with bromine it forms only rhenium pentabromide and iodine can achieve only rhenium tetraiodide. By the same token, however, since iodine has the lowest ionisation energy among the halogens and is the most easily oxidised of them, it has a more significant cationic chemistry and its higher oxidation states are rather more stable than those of bromine and chlorine, for example in iodine heptafluoride.
The trifluoromethyl group is a functional group that has the formula -CF3. The naming of is group is derived from the methyl group (which has the formula -CH3), by replacing each hydrogen atom by a fluorine atom. Some common examples are trifluoromethane H–CF
3, 1,1,1-trifluoroethane H
3C–CF
3, and hexafluoroacetone F
3C–CO–CF
3. Compounds with this group are a subclass of the organofluorines.
Thiophosphoryl chloride is an inorganic compound with the chemical formula PSCl3. It is a colorless pungent smelling liquid that fumes in air. It is synthesized from phosphorus chloride and used to thiophosphorylate organic compounds, such as to produce insecticides.
Dithietanes are saturated heterocyclic compounds that contain two divalent sulfur atoms and two sp3-hybridized carbon centers. Two isomers are possible for this class of organosulfur compounds:
Trimethylsulfonium is an organic cation with the chemical formula (CH3)3S+.
Fluorination with aminosulfuranes is a chemical reaction that transforms oxidized organic compounds into organofluorine compounds. Aminosulfuranes selectively exchange hydroxyl groups for fluorine, but are also capable of converting carbonyl groups, halides, silyl ethers, and other functionality into organofluorides.
Tetrakis[3,5-bis(trifluoromethyl)phenyl]borate is an anion with chemical formula [{3,5-(CF3)2C6H3}4B]−, which is commonly abbreviated as [BArF4]−, indicating the presence of fluorinated aryl (ArF) groups. It is sometimes referred to as Kobayashi's anion in honour of Hiroshi Kobayashi who led the team that first synthesised it. More commonly it is affectionately nicknamed "BARF." The BARF ion is also abbreviated BArF24−, to distinguish it from the closely related BArF−
20, [(C6F5)4B]−. However, for a small group of chemists, the anion is abbreviated as TFPB otherwise, short for Tetrakis[3,5-bis(triFluoromethyl)Phenyl]Borate.
Sulfanyl (HS•), also known as the mercapto radical, hydrosulfide radical, or hydridosulfur, is a simple radical molecule consisting of one hydrogen and one sulfur atom. The radical appears in metabolism in organisms as H2S is detoxified. Sulfanyl is one of the top three sulfur-containing gasses in gas giants such as Jupiter and is very likely to be found in brown dwarfs and cool stars. It was originally discovered by Margaret N. Lewis and John U. White at the University of California in 1939. They observed molecular absorption bands around 325 nm belonging to the system designated by 2Σ+ ← 2Πi. They generated the radical by means of a radio frequency discharge in hydrogen sulfide. HS• is formed during the degradation of hydrogen sulfide in the atmosphere of the Earth. This may be a deliberate action to destroy odours or a natural phenomenon.
Brookhart's acid is the salt of the diethyl ether oxonium ion and tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (BAr′4). It is a colorless solid, used as a strong acid. The compound was first reported by Volpe, Grant, and Brookhart in 1992.
Tetramethylurea is the organic compound with the formula (Me2N)2CO. It is a substituted urea. This colorless liquid is used as an aprotic-polar solvent, especially for aromatic compounds and is used e. g. for Grignard reagents.
Tris(dimethylamino)methane (TDAM) is the simplest representative of the tris(dialkylamino)methanes of the general formula (R2N)3CH in which three of the four of methane's hydrogen atoms are replaced by dimethylamino groups (−N(CH3)2). Tris(dimethylamino)methane can be regarded as both an amine and an orthoamide.
Dihydroxydisulfane or hypodithionous acid is a reduced sulfur oxyacid with sulfur in a formal oxidation state of +1, but the valence of sulfur is 2. The structural formula is HO−S−S−OH, with all atoms arranged in a chain. It is an isomer of thiosulfurous acid but is lower in energy. Other isomers include HOS(=O)SH, HOS(=S)OH, and HS(=O)2SH. Disulfur monoxide, S2O, can be considered as the anhydride. Unlike many of these other reduced sulfur acids, dihydroxydisulfane can be formed in a pure state by reacting hydrogen sulfide with sulfur dioxide at −70 °C in dichlorodifluoromethane.
Nonafluoro-tert-butyl alcohol is a fluoroalcohol. It is the perfluorinated analog of tert-butyl alcohol. Notably, as a consequence of its electron withdrawing fluorine substituents, it is very acidic for an alcohol, with a pKa value of 5.4, similar to that of a carboxylic acid. As another consequence of being a perfluorinated compound, it is also one of the lowest boiling alcohols, with a boiling point lower than that of methanol.
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