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

A frustrated Lewis pair, such as tris(tert-butyl) phosphine and tris(pentafluorophenyl)borane, can attach to the NSO chain to yield a R'₃P=N⁺(R)SOB⁻R"₃ compound. ^[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. 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. Bibcode:2015ACIE...54..809L. 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. 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. 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.