Neophyl chloride

Neophyl chloride
Names
	Preferred IUPAC name (1-Chloro-2-methylpropan-2-yl)benzene
	Other names (Chloro-tert-butyl)benzene
Identifiers
CAS Number	515-40-2 ;
3D model (JSmol)	Interactive image;
ChemSpider	61498 ;
ECHA InfoCard	100.007.453
EC Number	208-197-7;
PubChem CID	68191;
UNII	OF6E0410NF ;
CompTox Dashboard (EPA)	DTXSID8027167 ;
	InChI InChI=1S/C10H13Cl/c1-10(2,8-11)9-6-4-3-5-7-9/h3-7H,8H2,1-2H3 Key: DNXXUUPUQXSUFH-UHFFFAOYSA-N ; InChI=1/C10H13Cl/c1-10(2,8-11)9-6-4-3-5-7-9/h3-7H,8H2,1-2H3 Key: DNXXUUPUQXSUFH-UHFFFAOYAJ;
	SMILES ClCC(c1ccccc1)(C)C;
Properties
Chemical formula	C10H13Cl
Molar mass	168.663 g/mol
Appearance	colorless liquid
Density	1.047 g/cm3
Boiling point	223 °C (433 °F; 496 K)
Solubility in water	organic solvents
Hazards
	GHS labelling:
Pictograms
Signal word	Warning
Hazard statements	H315, H319, H335
Precautionary statements	P261, P264, P264+P265, P271, P280, P302+P352, P304+P340, P305+P351+P338, P319, P321, P332+P317, P337+P317, P362+P364, P403+P233, P405, P501
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). verify (what is ?) Infobox references

Neophyl chloride, C₆H₅C(CH₃)₂CH₂Cl, is a halogenated organic compound with unusual nucleophilic substitution properties. Neophyl chloride is used to form a versatile organolithium reagent, neophyl lithium, by reaction with lithium.^[2]^[3]

Preparation

Neophyl chloride was first synthesized by Haller and Ramart from neophyl alcohol by a nucleophilic substitution reaction, using thionyl chloride as the chlorinating agent:^[4]

C₆H₅C(CH₃)₂CH₂OH + SOCl₂ → C₆H₅C(CH₃)₂CH₂Cl + HCl + SO₂

It is easily prepared on a large scale from benzene and methallyl chloride by an electrophilic aromatic substitution reaction, using sulfuric acid as the catalyst:^[4] The reaction is an example of an electrophilic aromatic substitution reaction.

H₂C=C(CH₃)CH₂Cl + C₆H₆ → C₆H₅C(CH₃)₂CH₂Cl

It can also be prepared by free radical halogenation of tert-butylbenzene, using various chlorine donors.^[4]

Reactions and applications

Neophyl chloride can be used to form an organolithium reagent, neophyl lithium, by reaction with lithium. Organolithium reagents are useful due to their nucleophilic properties and their ability to form carbon-to-carbon bonds, like in reactions with carbonyls.

C₆H₅C(CH₃)₂CH₂Cl + 2Li → C₆H₅C(CH₃)₂CH₂Li + LiCl

Neophyl chloride is of interest to organic chemists due to its substitution properties. Neophyl chloride is a neopentyl halide which means it is subject to the neopentyl effect. This effect makes SN₂ nucleophilic substitution highly unlikely because of steric interactions due to the branching of the β-carbon. No rotamer of the molecule would allow a backside attack of the α carbon.

β-Hydride elimination also does not occur with neophyl derivatives as this group lacks hydrogens at the β positions. These factors make neophyl chloride a precursor to intermediates that resist common substitution and elimination reactions.

References

^ "Neophyl chloride". pubchem.ncbi.nlm.nih.gov. Retrieved 27 December 2021.
^ Lide, R. D. (2003). CRC Handbook of Chemistry and Physics. p. 590. ISBN 0-8493-0595-0.
^ Streitwieser, Andrew; Heathcock, Clayton H. (1985). Introduction to Organic Chemistry (3rd ed.). New York: Macmillan Co. ISBN 0-02-946720-9.
^ ^a ^b ^c W. T. Smith, Jr. and J. T. Sellas (1963). "Neophyl chloride". Organic Syntheses.

[1] "Neophyl chloride". pubchem.ncbi.nlm.nih.gov. Retrieved 27 December 2021.

[2] Lide, R. D. (2003). CRC Handbook of Chemistry and Physics. p. 590. ISBN 0-8493-0595-0.

[3] Streitwieser, Andrew; Heathcock, Clayton H. (1985). Introduction to Organic Chemistry (3rd ed.). New York: Macmillan Co. ISBN 0-02-946720-9.

[OS-4] W. T. Smith, Jr. and J. T. Sellas (1963). "Neophyl chloride". Organic Syntheses.

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