tert-Butyl N-(4-hy­droxy­benz­yl)-N-[4-(prop-2-yn­yloxy)benz­yl]carbamate

Lei Ao; Jie-Hong Tu; Xuan Huang; Bao-Yue Ding

doi:10.1107/S160053681103683X

. 2011 Sep 14;67(Pt 10):o2642. doi: 10.1107/S160053681103683X

tert-Butyl N-(4-hydroxybenzyl)-N-[4-(prop-2-ynyloxy)benzyl]carbamate

Lei Ao ^a,^*, Jie-Hong Tu ^a, Xuan Huang ^a, Bao-Yue Ding ^a

PMCID: PMC3201299 PMID: 22058772

Abstract

In the crystal structure of the title compound, C₂₂H₂₅NO₄, intermolecular O—H⋯O hydrogen bonds involving the hydroxy group of the 4-(amimomethyl)phenol fragment and the C=O group connect the molecules into infinite chains along the c axis. Two C atoms of the propyne group are disordered over two sites with occupancy factors of 0.53 (2) and 0.47 (2).

Related literature

For applications of the title compound, see: Späth & König (2010 ▶); Juríček et al. (2011 ▶). For the synthesis of the title compound, see: Kim et al. (2004 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₂₂H₂₅NO₄
M _r = 367.43
Monoclinic,
a = 18.6904 (8) Å
b = 6.2611 (4) Å
c = 17.3567 (7) Å
β = 96.791 (1)°
V = 2016.87 (18) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 296 K
0.41 × 0.37 × 0.29 mm

Data collection

Rigaku R-AXIS RAPID/ZJUG diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.957, T _max = 0.976
15741 measured reflections
3750 independent reflections
2099 reflections with I > 2σ(I)
R _int = 0.038

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.149
S = 1.00
3750 reflections
268 parameters
4 restraints
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Data collection: RAPID-AUTO (Rigaku, 1998 ▶); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ▶); 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, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681103683X/kj2185sup1.cif

e-67-o2642-sup1.cif^{(21.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681103683X/kj2185Isup2.hkl

e-67-o2642-Isup2.hkl^{(180.1KB, hkl)}

Supplementary material file. DOI: 10.1107/S160053681103683X/kj2185Isup3.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
O1—H1⋯O4ⁱ	0.82	1.94	2.745 (2)	167

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank Mr Jian Ming Gu of the X-ray crystallographic facility of Zhejiang University for assistance with the crystal structure analysis.

supplementary crystallographic information

Comment

The amino group is one of the most important functional groups in molecules of biological relevance, of which histamine and dopamine are two representative examples. In the synthesis of amino-contaning compounds, the boc group is commonly used to protect the amino group when performing parallel chemical transformations (Späth et al. , 2010). The acetylene group, due to the presence of the carbon-carbon triple bond, is an ideal functional group for further postmodification by numerous synthetic transformations (Juríček et al. , 2011). In our exploration of structure-activity relationships of amino-contaning compounds, we recently obtained a crystal of an intermediate, which contains both a boc-protecting amino group and an acetylene group. We report its crystal structure here.

The molecular structure of the title compound is shown in Fig. 1. The dihedral angle of the rings C1—C6 and C9—C14 is 11.7 (3)°. The bond lengths and angles are within normal ranges (Allen et al., 1987). The C18—N1 distance is 1.348 (3) Å, which is in the range of a typical double C=N bond. Atom O4 has a partial anionic character, as is shown by the lengthening of the C=O bond [1.226 (3) Å] compared to what is normally found for carbonyl groups. This atom acts as a hydrogen-bond acceptor for an intermolecular O—H···O hydrogen bond (Table 1). The hydrogen bonds are forming one-dimensional infinite chains along the c axis (Fig. 2).

Experimental

The title compound was synthesized according to the method proposed by Kim et al. (2004). 4-(Amimomethyl)phenol (0.01 mol,1.23 g) and 4-(prop-2-gnyloxy)benzoldehyde were heated in anhydrous methanol for 2 h, then NaBH₄ (0.1 mol,0.38 g) was added to the solution. The resulting solution was stirred for 30 minutes, then Boc₂O (0.01 mol,2.18 g) was dropped into the solution. Colourless block-shaped single crystals suitable for X-ray structure determination were obtained by slow evaporation of the solution in a mixture of PE:EA(1:1,v:v). Yield: 51.7%.