Sulfinylamine

General structure of an N-sulfinyl amine
N-Sulfinylaniline is a common sulfinylamine

Sulfinylamines (formerly N-sulfinyl amines) are organosulfur compounds with the formula RNSO where R = an organic substituent. These compounds are, formally speaking, derivatives of HN=S=O, i.e. analogues of sulfur dioxide and of sulfur diimide. A common example is N-sulfinylaniline. Sulfinyl amines are dienophile.[1] They undergo [2+2] cycloaddition to ketenes.[2]

According to X-ray crystallography, sulfinylamines have planar C-N=S=O cores with syn geometry.[3]

Preparation

Sulfinylamines can be made when thionyl chloride SOCl2 reacts with a primary amine.[4] Indeed, the parent thionylamide, HNSO, can be made that way at low temperature.[5]

Reactions

Mixtures of phosphine and borane derivatives can attach to the NSO chain to yield a R'3P=N+(R)SOB−R"3 compound. This can happen with tris(tert-butyl) phosphine and tris(pentafluorophenyl)borane.[4]

Compounds

Formula Name CAS No PubChem CID Chemspider ID MW (g/mol) Reference
HNSO Thionylimide
Sulfinylamine
Sulfoximine 		13817-04-4 139610 123125 63.074 [6]
C6H5NSO N-Sulfinylaniline
N-Thionylaniline 		1122-83-4 70739 63904 139.172 [7]
N-Sulfinyl-2,6-diethyl benzenamine [7]
N-Sulfinyl-2-aminopyrimidine 110526-12-0 14790782 141.148
N-Sulfinyl-n-butylamine [8]
N-Sulfinyl-n-pentylamine [8]

References

  1. ^ Kresze, G.; Wucherpfennig, W. (1967). "New Methods of Preparative Organic Chemistry V: Organic Syntheses with Imides of Sulfur Dioxide". Angewandte Chemie International Edition in English. 6 (2): 149–167. doi:10.1002/anie.196701491. PMID 4962859.
  2. ^ Heravi, Majid M.; Talaei, Bahareh (2014). Ketenes as Privileged Synthons in the Syntheses of Heterocyclic Compounds. Part 1. Advances in Heterocyclic Chemistry. Vol. 113. pp. 143–244. doi:10.1016/B978-0-12-800170-7.00004-3. ISBN 9780128001707.
  3. ^ Romano, R.M.; Della Védova, C.O. (2000). "N-Sulfinylimine compounds, R–N=S=O: A chemistry family with strong temperament". Journal of Molecular Structure. 522 (1–3): 1–26. Bibcode:2000JMoSt.522....1R. doi:10.1016/S0022-2860(99)00453-6..
  4. ^ a b Longobardi, Lauren E.; Wolter, Vanessa; Stephan, Douglas W. (12 January 2015). "Frustrated Lewis Pair Activation of an N-Sulfinylamine: A Source of Sulfur Monoxide". Angewandte Chemie International Edition. 54 (3): 809–812. doi:10.1002/anie.201409969. PMID 25376102.
  5. ^ Roesky, H. W. (1971). "The Sulfur–Nitrogen Bond". In Senning, Alexander (ed.). Sulfur in Organic and Inorganic Chemistry. Vol. 1. New York: Marcel Dekker. p. 24. ISBN 0-8247-1615-9. LCCN 70-154612.
  6. ^ Kresze, G.; Maschke, A.; Albrecht, R.; Bederke, K.; Patzschke, H. P.; Smalla, H.; Trede, A. (February 1962). "Organic N-Sulfinyl Compounds". Angewandte Chemie International Edition in English. 1 (2): 89–98. doi:10.1002/anie.196200891.
  7. ^ a b Romano, R.M; Della Védova, C.O; Boese, R (January 1999). "A solid state study of the configuration and conformation of OSN–R (R=C6H5 and C6H3(CH3–CH2)2-2,6)". Journal of Molecular Structure. 475 (1): 1–4. Bibcode:1999JMoSt.475....1R. doi:10.1016/S0022-2860(98)00439-6.
  8. ^ a b Ammoscato, Vince (1990). "Part I. A study of the alkylation chemistry of N-sulfinyl amines. Part II. Attempted preparation of the camphor imine of stereospecifically deuterated glycine". Electronic Theses and Dissertations. University of Windsor. Retrieved 28 January 2018.