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Thiosulfinate

October 20, 2023

In organosulfur chemistry, thiosulfinate is a functional group consisting of the linkage R-S(O)-S-R (R are organic substituents). Thiolsulfinates are also named as alkanethiosulfinic (or arenethiosulfinic) acid esters.

General structure of a thiosulfinate, drawn in expanded octet style[1]

They are the first of the series of functional groups containing an oxidized disulfide bond. Other members of this family include thiosulfonates (R-SO2-S-R), α-disulfoxides (R-S(O)-S(O)-R), sulfinyl sulfones (R-S(O)-SO2-R), and α-disulfones (R-SO2-SO2-R), all of which are known. The thiosulfinate group can occur in cyclic as well as acyclic structures.[2][3][4]

Occurrence Edit

 
Allicin

A variety of acyclic and cyclic thiosulfinates are found in plants, or formed when the plants are cut or crushed.

A well-known thiosulfinate is allicin, one of the active ingredients formed when garlic is crushed. Allicin was discovered in 1944 by Chester J. Cavallito and coworkers. Thiosulfinates containing various combinations of the methyl, n-propyl, 1-propenyl, 2-propenyl, n-butyl, 1-butenyl and 2-butenyl groups are formed upon crushing different Allium as well as Brassica species.[5][6]

Zeylanoxides are cyclic thiosulfinates containing the 1,2-dithiolane-1-oxide ring, isolated from the tropical weed Sphenoclea zeylanica. These heterocyclic thiosulfinates are chiral at carbon as well as at sulfur.[7]

Crushing the roots of Petiveria alliacea affords the thiosulfinates S-(2-hydroxyethyl) 2-hydroxyethane)thiosulfinate, S-(2-hydroxylethyl) phenylmethanethiosulfinate, S-benzyl 2-hydroxyethane)thiosulfinate and S-benzyl phenylmethanethiosulfinate (petivericin; PhCH2S(O)SCH2Ph).[8] Asparagusic acid S-oxide[9] and brugierol[10] are other natural 1,2-dithiolane-1-oxides occurring in Asparagus officinalis and Bruguiera conjugata, respectively.

Properties Edit

Allicin, S-benzyl phenylmethanethiosulfinate, and related thiosulfinates show radical-trapping antioxidant activity associated with easy formation of sulfenic acids[11] The acyclic thiosulfinates from Allium and Brassica species possess antimicrobial, antiparasitic, antitumor and cysteine protease inhibitory activity while the natural 1,2-dithiolane-1-oxides are growth inhibitors. The thiosulfinates from Petiveria also exhibit antimicrobial activity.[12]

Thiosulfinates feature a S(IV) center linked to a S(II) center, the former being stereogenic. Conversion of simple disulfides to thiosulfinates results in a considerable weakening of the S–S bond from about 70 to 34.5 kcal mol−1 (16.7 to 8.25 kJ mol−1) for the S-S bond in PhS(O)SPh,[13] with the consequence that most thiosulfinates are both unstable and quite reactive. For this reason the mixtures of thiosulfinates from Allium plants can best be separated by HPLC at room temperature rather than by gas chromatography (GC), although GC has been used with some low molecular weight thiosulfinates. Thiosulfinates can be distinguished from sulfoxides by infrared spectroscopy since they have a characteristic S=O band at about 1078 cm−1 compared to 1030–1060 cm−1 in sulfoxides.[14]

Formation and reactions Edit

Synthetic thiosulfinates were first reported in 1947 by Cavallito and coworkers by oxidation of the corresponding disulfides.[15]

One example of a moderately stable thiosulfinate is the tert-butyl derivative, (CH3)3CS(O)SC(CH3)3. This thiosulfinate can be obtained in optical purity by catalytic asymmetric oxidation of di-tert-butyl disulfide with hydrogen peroxide.[16] Upon heating, (CH3)3CS(O)SC(CH3)3 decomposes into tert-butanethiosulfoxylic acid (CH3)3CSSOH) as shown by trapping studies.[17]

In a similar manner racemic methyl methanethiosulfinate (CH3S(O)SCH3) can be obtained by peracetic acid oxidation of dimethyl disulfide.[18] Methyl methanethiosulfinate decomposes thermally giving methanesulfenic acid (CH3SOH), the simplest sulfenic acid, as well as thioformaldehyde (CH2=S). Methyl methanethiosulfinate can also disproportionate to a 1:1 mixture of dimethyl disulfide and methyl methanethiosulfonate (CH3SO2SCH3) and rearrange via a Pummerer rearrangement to CH3S(O)CH2SSCH3.[19][20]

An unusual three-membered ring thiosulfinate (a dithiirane 1-oxide) has been prepared through rearrangement of a 1,3-dithietane.[21] A related compound, 3-(9-triptycyl)dithiirane-1-oxide, was prepared by the reaction of (9-triptycyl)diazomethane and S8O. The X-ray structure of the dithiirane-1-oxide reveals a significantly lengthened sulfur-sulfur bond (211.9(3)pm).[22]

Thiosulfinates have also been invoked as intermediates in the oxidation of thiols to sulfonic acids.

References Edit

  1. ^ See sulfoxide for discussion and references regarding the bonding in divalent monooxosulfur structures.
  2. ^ Kice JL (1980). "Mechanisms and reactivity in reactions of organic oxyacids of sulfur and their anhydrides". Advances in Physical Organic Chemistry. 17: 65–181. doi:10.1016/S0065-3160(08)60128-8. ISBN 9780120335176.
  3. ^ Takata, T; Endo, T (1990). "Thiosulphinic acids and esters". The Chemistry of Sulphinic Acids, Esters and Their Derivatives, S. Patai, Ed. (John Wiley, NY): 527–575. doi:10.1002/9780470772270.ch18. ISBN 9780470772270.
  4. ^ Braverman, S; Cherkinsky, M.; Levinger, S. (2007). "Alkanethiosulfinic Acid Esters". Sci. Synth. 39: 229–235.
  5. ^ Kubec, R; Cody, RB; Dane, AJ; Musah, RA; Schraml, J; Vattekkatte, A; Block, E (2010). "Applications of DART Mass Spectrometry in Allium Chemistry. (Z)-Butanethial S-Oxide and 1-Butenyl Thiosulfinates and their S-(E)-1-Butenylcysteine S-Oxide Precursor from Allium siculum". J. Agric. Food Chem. 58 (2): 1121–1128. doi:10.1021/jf903733e. PMID 20047275.
  6. ^ Block, E; Dane, AJ; Thomas, S; Cody, RB (2010). "Applications of Direct Analysis in Real Time–Mass Spectrometry (DART-MS) in Allium Chemistry. 2-Propenesulfenic and 2-Propenesulfinic Acids, Diallyl Trisulfane S-Oxide and Other Reactive Sulfur Compounds from Crushed Garlic and Other Alliums". J. Agric. Food Chem. 58 (8): 4617–4625. doi:10.1021/jf1000106. PMID 20225897.
  7. ^ Hirai, N; Sakashita, S; Sano, T; Inoue, T; Ohigashi, H; Premasthira, C; Asakawa, Y; Harada, J; Fujii, Y (2000). "Allelochemicals of the tropical weed Sphenoclea zeylanica". Phytochemistry. 55 (2): 131–140. doi:10.1016/S0031-9422(00)00264-8. PMID 11065289.
  8. ^ Kubec, R; Kim, S; Musah, RA (2002). "S-Substituted cysteine derivatives and thiosulfinate formation in Petiveria alliacea--Part II" (PDF). Phytochemistry. 61 (6): 675–680. doi:10.1016/S0031-9422(02)00328-X. PMID 12423888.
  9. ^ Yanagawa, H; Kato, T; Kitahara, Y (1973). "Asparagusic acid-S-oxides, new plant growth regulators in etiolated young asparagus shoots". Tetrahedron Letters. 14 (13): 1073–1075. doi:10.1016/S0040-4039(01)95907-6.
  10. ^ Kato, A; Numata M (1972). "Brugierol and isobrugierol, trans- and cis-1,2-dithiolane-1-oxide, from Brugiera conjugata". Tetrahedron Letters. 13 (3): 203–206. doi:10.1016/S0040-4039(01)84280-5.
  11. ^ Lynett, PT; Butts, K; Vaidya, V; Garretta, GE; Pratt, DA (2011). "The mechanism of radical-trapping antioxidant activity of plant-derived thiosulfinates". Org. Biomol. Chem. 9 (9): 3320–3330. doi:10.1039/c1ob05192j. PMID 21445384.
  12. ^ Kim, S; Kubec, R; Musah, RA (2006). "Antibacterial and antifungal activity of sulfur-containing compounds from Petiveria alliacea" (PDF). Journal of Ethnopharmacology. 104 (1–2): 188–192. doi:10.1016/j.jep.2005.08.072. PMID 16229980.
  13. ^ Koch, P; Ciuffarin, E; Fava, A (1970). "Thermal disproportionation of aryl arenethiolsulfinates. Kinetics and mechanism". J. Am. Chem. Soc. 92 (20): 5971–5977. doi:10.1021/ja00723a026.
  14. ^ Block E (2010). Garlic and Other Alliums: The Lore and the Science. Royal Society of Chemistry. ISBN 978-0-85404-190-9.
  15. ^ Small, LD; Bailey, JH; Cavallito, CJ (1947). "Alkyl thiolsulfinates". J. Am. Chem. Soc. 69 (7): 1710–1713. doi:10.1021/ja01199a040. PMID 20251406.
  16. ^ Weix, DJ; Ellman, JA (2005). "(RS)-(+)-2-Methyl-2-Propanesulfinamide [tert-Butanesulfinamide]". Organic Syntheses. 82: 157. doi:10.1002/0471264229.os082.24.
  17. ^ Block, E (1972). "The Chemistry of Alkyl Thiosulfinate Esters. III. tert-Butanethiosulfoxylic Acid". J. Am. Chem. Soc. 94 (2): 644–645. doi:10.1021/ja00757a060.
  18. ^ Moore, TL; O'Connor, DE (1966). "The Reaction of Methanesulfenyl Chloride with Alkoxides and Alcohols. Preparation of Aliphatic Sulfenate and Sulfinate Esters". J. Org. Chem. 31 (11): 3587–3592. doi:10.1021/jo01349a027.
  19. ^ Block, E; O'Connor, J (1974). "The Chemistry of Alkyl Thiosulfinate Esters. VI. Preparation and Spectral Studies". J. Am. Chem. Soc. 96 (12): 3921–3929. doi:10.1021/ja00819a033.
  20. ^ Block, E; O'Connor, J (1974). "The Chemistry of Alkyl Thiosulfinate Esters. VII. Mechanistic Studies and Synthetic Applications". J. Am. Chem. Soc. 96 (12): 3929–3944. doi:10.1021/ja00819a034.
  21. ^ Ishii, A; Akazawa, T; Ding, MX; Honjo, T; Nakayama, J; Hoshino, M; Shiro, M (1993). "First isolable dithiiranes: 3-(1,1,3,3-tetramethyl-4-oxo-4-phenylbutyl)-3-phenyldithiirane 1-oxides". J. Am. Chem. Soc. 115 (11): 4914–4915. doi:10.1021/ja00064a072.
  22. ^ Ishii, A; Kawai, T; Noji, M; Nakayama, J (2005). "Synthesis and reactions of a monosubstituted dithiirane 1-oxide, 3-(9-triptycyl)dithiirane 1-oxide". Tetrahedron. 61 (28): 6693–6699. doi:10.1016/j.tet.2005.05.017.

October 20, 2023
thiosulfinate, organosulfur, chemistry, thiosulfinate, functional, group, consisting, linkage, organic, substituents, thiolsulfinates, also, named, alkanethiosulfinic, arenethiosulfinic, acid, esters, general, structure, thiosulfinate, drawn, expanded, octet, . In organosulfur chemistry thiosulfinate is a functional group consisting of the linkage R S O S R R are organic substituents Thiolsulfinates are also named as alkanethiosulfinic or arenethiosulfinic acid esters General structure of a thiosulfinate drawn in expanded octet style 1 They are the first of the series of functional groups containing an oxidized disulfide bond Other members of this family include thiosulfonates R SO2 S R a disulfoxides R S O S O R sulfinyl sulfones R S O SO2 R and a disulfones R SO2 SO2 R all of which are known The thiosulfinate group can occur in cyclic as well as acyclic structures 2 3 4 Contents 1 Occurrence 2 Properties 3 Formation and reactions 4 ReferencesOccurrence Edit nbsp AllicinA variety of acyclic and cyclic thiosulfinates are found in plants or formed when the plants are cut or crushed A well known thiosulfinate is allicin one of the active ingredients formed when garlic is crushed Allicin was discovered in 1944 by Chester J Cavallito and coworkers Thiosulfinates containing various combinations of the methyl n propyl 1 propenyl 2 propenyl n butyl 1 butenyl and 2 butenyl groups are formed upon crushing different Allium as well as Brassica species 5 6 Zeylanoxides are cyclic thiosulfinates containing the 1 2 dithiolane 1 oxide ring isolated from the tropical weed Sphenoclea zeylanica These heterocyclic thiosulfinates are chiral at carbon as well as at sulfur 7 Crushing the roots of Petiveria alliacea affords the thiosulfinates S 2 hydroxyethyl 2 hydroxyethane thiosulfinate S 2 hydroxylethyl phenylmethanethiosulfinate S benzyl 2 hydroxyethane thiosulfinate and S benzyl phenylmethanethiosulfinate petivericin PhCH2S O SCH2Ph 8 Asparagusic acid S oxide 9 and brugierol 10 are other natural 1 2 dithiolane 1 oxides occurring in Asparagus officinalis and Bruguiera conjugata respectively Properties EditAllicin S benzyl phenylmethanethiosulfinate and related thiosulfinates show radical trapping antioxidant activity associated with easy formation of sulfenic acids 11 The acyclic thiosulfinates from Allium and Brassica species possess antimicrobial antiparasitic antitumor and cysteine protease inhibitory activity while the natural 1 2 dithiolane 1 oxides are growth inhibitors The thiosulfinates from Petiveria also exhibit antimicrobial activity 12 Thiosulfinates feature a S IV center linked to a S II center the former being stereogenic Conversion of simple disulfides to thiosulfinates results in a considerable weakening of the S S bond from about 70 to 34 5 kcal mol 1 16 7 to 8 25 kJ mol 1 for the S S bond in PhS O SPh 13 with the consequence that most thiosulfinates are both unstable and quite reactive For this reason the mixtures of thiosulfinates from Allium plants can best be separated by HPLC at room temperature rather than by gas chromatography GC although GC has been used with some low molecular weight thiosulfinates Thiosulfinates can be distinguished from sulfoxides by infrared spectroscopy since they have a characteristic S O band at about 1078 cm 1 compared to 1030 1060 cm 1 in sulfoxides 14 Formation and reactions EditSynthetic thiosulfinates were first reported in 1947 by Cavallito and coworkers by oxidation of the corresponding disulfides 15 One example of a moderately stable thiosulfinate is the tert butyl derivative CH3 3CS O SC CH3 3 This thiosulfinate can be obtained in optical purity by catalytic asymmetric oxidation of di tert butyl disulfide with hydrogen peroxide 16 Upon heating CH3 3CS O SC CH3 3 decomposes into tert butanethiosulfoxylic acid CH3 3CSSOH as shown by trapping studies 17 In a similar manner racemic methyl methanethiosulfinate CH3S O SCH3 can be obtained by peracetic acid oxidation of dimethyl disulfide 18 Methyl methanethiosulfinate decomposes thermally giving methanesulfenic acid CH3SOH the simplest sulfenic acid as well as thioformaldehyde CH2 S Methyl methanethiosulfinate can also disproportionate to a 1 1 mixture of dimethyl disulfide and methyl methanethiosulfonate CH3SO2SCH3 and rearrange via a Pummerer rearrangement to CH3S O CH2SSCH3 19 20 An unusual three membered ring thiosulfinate a dithiirane 1 oxide has been prepared through rearrangement of a 1 3 dithietane 21 A related compound 3 9 triptycyl dithiirane 1 oxide was prepared by the reaction of 9 triptycyl diazomethane and S8O The X ray structure of the dithiirane 1 oxide reveals a significantly lengthened sulfur sulfur bond 211 9 3 pm 22 Thiosulfinates have also been invoked as intermediates in the oxidation of thiols to sulfonic acids References Edit See sulfoxide for discussion and references regarding the bonding in divalent monooxosulfur structures Kice JL 1980 Mechanisms and reactivity in reactions of organic oxyacids of sulfur and their anhydrides Advances in Physical Organic Chemistry 17 65 181 doi 10 1016 S0065 3160 08 60128 8 ISBN 9780120335176 Takata T Endo T 1990 Thiosulphinic acids and esters The Chemistry of Sulphinic Acids Esters and Their Derivatives S Patai Ed John Wiley NY 527 575 doi 10 1002 9780470772270 ch18 ISBN 9780470772270 Braverman S Cherkinsky M Levinger S 2007 Alkanethiosulfinic Acid Esters Sci Synth 39 229 235 Kubec R Cody RB Dane AJ Musah RA Schraml J Vattekkatte A Block E 2010 Applications of DART Mass Spectrometry in Allium Chemistry Z Butanethial S Oxide and 1 Butenyl Thiosulfinates and their S E 1 Butenylcysteine S Oxide Precursor from Allium siculum J Agric Food Chem 58 2 1121 1128 doi 10 1021 jf903733e PMID 20047275 Block E Dane AJ Thomas S Cody RB 2010 Applications of Direct Analysis in Real Time Mass Spectrometry DART MS in Allium Chemistry 2 Propenesulfenic and 2 Propenesulfinic Acids Diallyl Trisulfane S Oxide and Other Reactive Sulfur Compounds from Crushed Garlic and Other Alliums J Agric Food Chem 58 8 4617 4625 doi 10 1021 jf1000106 PMID 20225897 Hirai N Sakashita S Sano T Inoue T Ohigashi H Premasthira C Asakawa Y Harada J Fujii Y 2000 Allelochemicals of the tropical weed Sphenoclea zeylanica Phytochemistry 55 2 131 140 doi 10 1016 S0031 9422 00 00264 8 PMID 11065289 Kubec R Kim S Musah RA 2002 S Substituted cysteine derivatives and thiosulfinate formation in Petiveria alliacea Part II PDF Phytochemistry 61 6 675 680 doi 10 1016 S0031 9422 02 00328 X PMID 12423888 Yanagawa H Kato T Kitahara Y 1973 Asparagusic acid S oxides new plant growth regulators in etiolated young asparagus shoots Tetrahedron Letters 14 13 1073 1075 doi 10 1016 S0040 4039 01 95907 6 Kato A Numata M 1972 Brugierol and isobrugierol trans and cis 1 2 dithiolane 1 oxide from Brugiera conjugata Tetrahedron Letters 13 3 203 206 doi 10 1016 S0040 4039 01 84280 5 Lynett PT Butts K Vaidya V Garretta GE Pratt DA 2011 The mechanism of radical trapping antioxidant activity of plant derived thiosulfinates Org Biomol Chem 9 9 3320 3330 doi 10 1039 c1ob05192j PMID 21445384 Kim S Kubec R Musah RA 2006 Antibacterial and antifungal activity of sulfur containing compounds from Petiveria alliacea PDF Journal of Ethnopharmacology 104 1 2 188 192 doi 10 1016 j jep 2005 08 072 PMID 16229980 Koch P Ciuffarin E Fava A 1970 Thermal disproportionation of aryl arenethiolsulfinates Kinetics and mechanism J Am Chem Soc 92 20 5971 5977 doi 10 1021 ja00723a026 Block E 2010 Garlic and Other Alliums The Lore and the Science Royal Society of Chemistry ISBN 978 0 85404 190 9 Small LD Bailey JH Cavallito CJ 1947 Alkyl thiolsulfinates J Am Chem Soc 69 7 1710 1713 doi 10 1021 ja01199a040 PMID 20251406 Weix DJ Ellman JA 2005 RS 2 Methyl 2 Propanesulfinamide tert Butanesulfinamide Organic Syntheses 82 157 doi 10 1002 0471264229 os082 24 Block E 1972 The Chemistry of Alkyl Thiosulfinate Esters III tert Butanethiosulfoxylic Acid J Am Chem Soc 94 2 644 645 doi 10 1021 ja00757a060 Moore TL O Connor DE 1966 The Reaction of Methanesulfenyl Chloride with Alkoxides and Alcohols Preparation of Aliphatic Sulfenate and Sulfinate Esters J Org Chem 31 11 3587 3592 doi 10 1021 jo01349a027 Block E O Connor J 1974 The Chemistry of Alkyl Thiosulfinate Esters VI Preparation and Spectral Studies J Am Chem Soc 96 12 3921 3929 doi 10 1021 ja00819a033 Block E O Connor J 1974 The Chemistry of Alkyl Thiosulfinate Esters VII Mechanistic Studies and Synthetic Applications J Am Chem Soc 96 12 3929 3944 doi 10 1021 ja00819a034 Ishii A Akazawa T Ding MX Honjo T Nakayama J Hoshino M Shiro M 1993 First isolable dithiiranes 3 1 1 3 3 tetramethyl 4 oxo 4 phenylbutyl 3 phenyldithiirane 1 oxides J Am Chem Soc 115 11 4914 4915 doi 10 1021 ja00064a072 Ishii A Kawai T Noji M Nakayama J 2005 Synthesis and reactions of a monosubstituted dithiirane 1 oxide 3 9 triptycyl dithiirane 1 oxide Tetrahedron 61 28 6693 6699 doi 10 1016 j tet 2005 05 017 Retrieved from https en wikipedia org w index php title Thiosulfinate amp oldid 1156013894, wikipedia, wiki, book, books, library,

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