Methyl N-hy­droxy-N-(2-methyl­phen­yl)carbamate

Binbin Zhang; Yifeng Wang; Kun Dong; Danqian Xu

doi:10.1107/S1600536813000421

. 2013 Jan 12;69(Pt 2):o230. doi: 10.1107/S1600536813000421

Methyl N-hydroxy-N-(2-methylphenyl)carbamate

Binbin Zhang ^a, Yifeng Wang ^a, Kun Dong ^a, Danqian Xu ^a,^*

PMCID: PMC3569764 PMID: 23424510

Abstract

There are three independent molecules in the asymmetric unit of the title compound, C₉H₁₁NO₃, which are connected by O—H⋯O hydrogen bonds, forming an R ₃ ³(15) ring. The dihedral angles between the planes of the benzene and amide groups are 75.16 (3), 71.47 (3) and 70.56 (3)°. The hydroxy O atom lies 0.912 (3), 1.172 (2) and 1.339 (2) Å from the mean plane of the corresponding benzene ring in the three molecules.

Related literature

The title compound is an intermediate in the synthesis of the strobilurin fungicide pyraclostrobin. For general background, see: Hou et al. (2002 ▶); Yang et al. (2012 ▶); Tao et al. (2009 ▶). For related structures, see: Mercader et al. (2011 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₉H₁₁NO₃
M _r = 181.19
Monoclinic,
a = 7.6418 (3) Å
b = 20.8825 (9) Å
c = 18.0412 (9) Å
β = 94.485 (1)°
V = 2870.2 (2) Å³
Z = 12
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 296 K
0.54 × 0.37 × 0.18 mm

Data collection

Rigaku R-AXIS RAPID/ZJUG diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.946, T _max = 0.983
24402 measured reflections
5643 independent reflections
3163 reflections with I > 2σ(I)
R _int = 0.051

Refinement

R[F ² > 2σ(F ²)] = 0.063
wR(F ²) = 0.161
S = 1.01
5643 reflections
362 parameters
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Data collection: PROCESS-AUTO (Rigaku, 2006 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku, 2007 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Supplementary Material

Click here for additional data file.^{(33.8KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813000421/pk2462sup1.cif

e-69-0o230-sup1.cif^{(33.8KB, cif)}

Click here for additional data file.^{(270.7KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813000421/pk2462Isup2.hkl

e-69-0o230-Isup2.hkl^{(270.7KB, hkl)}

Click here for additional data file.^{(3.7KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813000421/pk2462Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1A—H1A⋯O2B	0.82	1.94	2.719 (3)	157
O1B—H1B⋯O2C	0.82	1.94	2.716 (3)	157
O1C—H1C⋯O2A	0.82	1.99	2.757 (3)	156

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Acknowledgments

This work was supported by the Zhejiang Provincial Natural Science Foundation of China (No. Y4110373). We are also grateful for the help of Professor Jian-Ming Gu of Zhejiang University.

supplementary crystallographic information

Comment

N-aryl hydroxylamines are a significant class of compounds that are key building blocks in the synthesis of natural products and biologically active compounds. The title compound, which was readily synthesized from (N)-(2-methylphenyl)hydroxylamine, act as an intermediate for the synthesis of Strobilurin fungicide Pyraclostrobin. In this article, the crystal structure of the title compound methyl(N)-hydroxy-2- methylphenylcarbamate is described (Fig. 1). There are three independent molecules in the asymmetric unit, which are connected by intermolecular O—H···O hydrogen bonds to construct a large ring involving 15 atoms with graph set notation R³₃(15) (Fig. 2). In each molecule, the dihedral angles of the plane of the phenyl ring and the plane of the amide moiety are 75.16 (3)°, 71.47 (3)°, 70.56 (3)° respectively, while the phenyl rings of the three molecules make dihedral angles of 79.87 (3)°, 71.01 (3)°, 55.86 (3)° with each other. Each hydroxyl O atom lies 0.912 (3) Å, 1.172 (2) Å and 1.339 (2) Å from the mean plane of the corresponding phenyl ring.

Experimental

To a solution of (N)-(2-methylphenyl)hydroxylamine (0.022 mol) in CH₂Cl₂ (20 ml), sodium bicarbonate (0.033 mol) was added and methyl chloroformate(0.024 mol) was added dropwise, and the mixture was stirred at 0° C for 2 h (monitored by HPLC). Then the reaction mixture was filtered and distilled under vacuum, and the residue was recrystallized from petroleum ether to give the title compound. Single crystals were obtained by slow evaporation of a CH₂Cl₂ and cyclohexane solution.