Benzophenone imine

Benzophenone imine
Names
	Preferred IUPAC name Diphenylmethanimine
Identifiers
CAS Number	1013-88-3;
3D model (JSmol)	Interactive image;
ChemSpider	120561;
ECHA InfoCard	100.103.715
EC Number	600-205-0; 440-870-2;
PubChem CID	136809;
UNII	EJJ21NA7VI;
CompTox Dashboard (EPA)	DTXSID10870832 ;
	InChI InChI=1S/C13H11N/c14-13(11-7-3-1-4-8-11)12-9-5-2-6-10-12/h1-10,14H Key: SXZIXHOMFPUIRK-UHFFFAOYSA-N;
	SMILES C1=CC=C(C=C1)C(=N)C2=CC=CC=C2;
Properties
Chemical formula	C13H11N
Molar mass	181.238 g·mol−1
Hazards
	GHS labelling:
Pictograms
Signal word	Warning
Hazard statements	H315, H319, H335
Precautionary statements	P261, P264, P271, P280, P302 P352, P304 P340, P305 P351 P338, P312, P321, P332 P313, P337 P313, P362, P403 P233, P405, P501
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). Infobox references

Benzophenone imine is an organic compound with the formula of (C₆H₅)₂C=NH. A pale yellow liquid, benzophenone imine is used as a reagent in organic synthesis.^[1]

Synthesis

Benzophenone imine can be prepared by the thermal decomposition of benzophenone oxime:^[2]

2 (C₆H₅)₂C=NOH → (C₆H₅)₂C=NH (C₆H₅)₂C=O

Benzophenone imine can also be synthesized by addition of phenylmagnesium bromide to benzonitrile followed by careful hydrolysis (lest the imine be hydrolyzed):^[3]

C₆H₅CN C₆H₅MgBr → (C₆H₅)₂C=NMgBr

(C₆H₅)₂C=NMgBr H₂O → (C₆H₅)₂C=NH MgBr(OH)

This method is known as Moureu-Mignonac ketimine synthesis.^[4] Yet another route to benzophenone imine involves reaction of benzophenone and ammonia.^[5]

Reactions

Benzophenone imine undergoes deprotonation with alkyl lithium reagents.^[6]

(C₆H₅)₂C=NH CH₃Li → (C₆H₅)₂C=NLi CH₄

(C₆H₅)₂C=NLi CH₃I → (C₆H₅)₂C=NCH₃ LiI

Primary amines can be protected as benzophenone imines, and the protected amines are stable in flash chromatography.^[7]

Buchwald-Hartwig amination involves coupling aromatic halide and amine to form carbon-nitrogen bonds with the help of palladium-based catalysts. Benzophenone imine can be used as an ammonia-equivalent in such reactions.^[1]

References

^ ^a ^b Wolfe, John P.; Åhman, Jens; Sadighi, Joseph P.; Singer, Robert A.; Buchwald, Stephen L. (1997-09-08). "An Ammonia Equivalent for the Palladium-Catalyzed Amination of Aryl Halides and Triflates". Tetrahedron Letters. 38 (36): 6367–6370. doi:10.1016/S0040-4039(97)01465-2. ISSN 0040-4039.
^ Arthur Lachman (1930). "Diphenylmethane Imine Hydrochloride". Organic Syntheses. 10: 28. doi:10.15227/orgsyn.010.0028.
^ Pickard, P. L.; Tolbert, T. L. (December 1961). "An Improved Method of Ketimine Synthesis". The Journal of Organic Chemistry. 26 (12): 4886–4888. doi:10.1021/jo01070a025. ISSN 0022-3263.
^ "Moureau-Mignonac Ketimine Synthesis". Hoboken, NJ, USA: John Wiley & Sons, Inc. 2010-09-15. pp. 1988–1990. doi:10.1002/9780470638859.conrr446. ISBN 9780470638859. {{cite book}}: |journal= ignored (help); Missing or empty |title= (help)
^ Verardo, G.; Giumanini, A. G.; Strazzolini, P.; Poiana, M. (1988). "Ketimines From Ketones and Ammonia". Synthetic Communications. 18 (13): 1501–1511. doi:10.1080/00397918808081307.
^ Nottingham, Chris; Lloyd-Jones, Guy C. (2018). "Trimethylsilyldiazo[13C]methane: A Versatile ¹³C-Labelling Reagent". Organic Syntheses. 95: 374–402. doi:10.15227/orgsyn.095.0374. hdl:20.500.11820/c801073c-6b4b-4a85-be68-2c4313b6e53d.
^ O'Donnell, Martin J. (2001-04-15). "Benzophenone Imine". Chichester, UK: John Wiley & Sons, Ltd. doi:10.1002/047084289x.rb031. ISBN 978-0471936237. {{cite book}}: |journal= ignored (help); Missing or empty |title= (help)

[:2-1] Wolfe, John P.; Åhman, Jens; Sadighi, Joseph P.; Singer, Robert A.; Buchwald, Stephen L. (1997-09-08). "An Ammonia Equivalent for the Palladium-Catalyzed Amination of Aryl Halides and Triflates". Tetrahedron Letters. 38 (36): 6367–6370. doi:10.1016/S0040-4039(97)01465-2. ISSN 0040-4039.

[2] Arthur Lachman (1930). "Diphenylmethane Imine Hydrochloride". Organic Syntheses. 10: 28. doi:10.15227/orgsyn.010.0028.

[:0-3] Pickard, P. L.; Tolbert, T. L. (December 1961). "An Improved Method of Ketimine Synthesis". The Journal of Organic Chemistry. 26 (12): 4886–4888. doi:10.1021/jo01070a025. ISSN 0022-3263.

[4] "Moureau-Mignonac Ketimine Synthesis". Hoboken, NJ, USA: John Wiley & Sons, Inc. 2010-09-15. pp. 1988–1990. doi:10.1002/9780470638859.conrr446. ISBN 9780470638859. {{cite book}}: |journal= ignored (help); Missing or empty |title= (help)

[5] Verardo, G.; Giumanini, A. G.; Strazzolini, P.; Poiana, M. (1988). "Ketimines From Ketones and Ammonia". Synthetic Communications. 18 (13): 1501–1511. doi:10.1080/00397918808081307.

[6] Nottingham, Chris; Lloyd-Jones, Guy C. (2018). "Trimethylsilyldiazo[13C]methane: A Versatile ¹³C-Labelling Reagent". Organic Syntheses. 95: 374–402. doi:10.15227/orgsyn.095.0374. hdl:20.500.11820/c801073c-6b4b-4a85-be68-2c4313b6e53d.

[7] O'Donnell, Martin J. (2001-04-15). "Benzophenone Imine". Chichester, UK: John Wiley & Sons, Ltd. doi:10.1002/047084289x.rb031. ISBN 978-0471936237. {{cite book}}: |journal= ignored (help); Missing or empty |title= (help)

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