2-tert-Butyl-4-methyl-6-(1,3-oxazinan-1-ylmeth­yl)phenol

Lei, W.-J.; Zhan, S.-Z.; Ng, S.W.

doi:10.1107/S1600536810012109

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 5| May 2010| Page o1030

https://doi.org/10.1107/S1600536810012109

Open

access

2-tert-Butyl-4-methyl-6-(1,3-oxazinan-1-ylmethyl)phenol

Wen-Jun Lei,^a Shu-Zhong Zhan ^a and Seik Weng Ng ^b ^*

^aCollege of Chemistry & Chemical Engineering, South China University of Technology, Guangzhou, 510640, People's Republic of China, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 30 March 2010; accepted 30 March 2010; online 10 April 2010)

The title compound, C₁₆H₂₅NO₂, which was synthesized by a Mannich reaction route, is a rare example of an organic compound containing the six-membered oxazine ring. The ring adopts a chair conformation and the N atom is pyramidal. The N atom serves as a hydrogen-bond acceptor to the phenolic OH group.

Related literature

The synthesis from 2-tert-butyl-4-methylphenol, 3-amino-1-propanol and formaldehyde is an example of carbon–carbon bond formation by the Mannich reaction. For another variation of the Mannich reaction involving 3-amino-1-propanol, see: Korepin et al. (2001 ).

Experimental

Crystal data

C₁₆H₂₅NO₂
M_r = 263.37
Orthorhombic, P 2₁ 2₁ 2₁
a = 6.4740 (7) Å
b = 14.1928 (13) Å
c = 16.7914 (16) Å
V = 1542.9 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 293 K
0.28 × 0.20 × 0.12 mm

Data collection

Rigaku R-AXIS Spider IP diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.980, T_max = 0.991
15222 measured reflections
2044 independent reflections
1664 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.117
S = 1.11
2044 reflections
180 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.12 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.85 (1)	1.90 (2)	2.665 (2)	149 (3)

Data collection: RAPID-AUTO (Rigaku, 2002 ); cell refinement: RAPID-AUTO; data reduction: CrystalClear (Rigaku/MSC, 2002 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810012109/bt5237sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810012109/bt5237Isup2.hkl

checkCIF report

Comment top

Organic synthesis centers largely on stereoselective carbon–carbon and carbon–heteroatom bond-forming reactions; among such reactions is the class of Mannich reactions, which can be regarded as being the most important carbon–carbon bond-forming reaction. The reactions lead to β-aminocarbonyl compounds, which are important intermediates for pharmaceuticals.

One variation of the Mannich reaction involves the catalytic addition of an amine, R₂NH, to an alkene or alkyne, i. e., hydroamination. In the 2-tert-butyl-4-methylphenol reacts with 3-amino-1-propanol to yield a compound having a 1,3-oxazinyl ring (Scheme I, Fig. 1). Such a ring is difficult to synthesis by conventional routes.

Related literature top

Experimental top

2-tert-Butyl-4-methylphenol (2.24 g, 12.3 mmol), 3-amino-1-propanol (0.93 g, 12.3 mmol), 37% aqueous formaldehyde (1.83 ml, 24.6 mmol) and triethylamine (2.49 g, 24.6 mmol) in ethanol (50 ml) were heated for 6 hours. Slow evaporation of the filtrate gave light-yellow crystals in 70% yield.

Structure description top

Computing details top

Data collection: RAPID-AUTO (Rigaku, 2002); cell refinement: RAPID-AUTO (Rigaku, 2002); data reduction: CrystalClear (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Anisotropic displacement ellipsoid plot (Barbour, 2001) of the title compound at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

2-tert-Butyl-4-methyl-6-(1,3-oxazinan-1-ylmethyl)phenol top

Crystal data top

C₁₆H₂₅NO₂	F(000) = 576
M_r = 263.37	D_x = 1.134 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 12093 reflections
a = 6.4740 (7) Å	θ = 3.1–27.5°
b = 14.1928 (13) Å	µ = 0.07 mm⁻¹
c = 16.7914 (16) Å	T = 293 K
V = 1542.9 (3) Å³	Block, yellow
Z = 4	0.28 × 0.20 × 0.12 mm

Data collection top

Rigaku R-AXIS Spider IP diffractometer	2044 independent reflections
Radiation source: fine-focus sealed tube	1664 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ω scan	θ_max = 27.5°, θ_min = 3.1°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −8→8
T_min = 0.980, T_max = 0.991	k = −18→18
15222 measured reflections	l = −21→21

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.117	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ²(F_o²) + (0.0739P)² + 0.0371P] where P = (F_o² + 2F_c²)/3
2044 reflections	(Δ/σ)_max = 0.001
180 parameters	Δρ_max = 0.14 e Å⁻³
1 restraint	Δρ_min = −0.12 e Å⁻³

Crystal data top

C₁₆H₂₅NO₂	V = 1542.9 (3) Å³
M_r = 263.37	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 6.4740 (7) Å	µ = 0.07 mm⁻¹
b = 14.1928 (13) Å	T = 293 K
c = 16.7914 (16) Å	0.28 × 0.20 × 0.12 mm

Data collection top

Rigaku R-AXIS Spider IP diffractometer	2044 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1664 reflections with I > 2σ(I)
T_min = 0.980, T_max = 0.991	R_int = 0.022
15222 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	1 restraint
wR(F²) = 0.117	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	Δρ_max = 0.14 e Å⁻³
2044 reflections	Δρ_min = −0.12 e Å⁻³
180 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.8894 (2)	0.48173 (11)	0.62162 (8)	0.0654 (4)
H1	0.972 (4)	0.5284 (14)	0.6242 (18)	0.095 (9)*
O2	0.9444 (3)	0.75355 (12)	0.59189 (10)	0.0816 (5)
N1	1.0668 (3)	0.63695 (11)	0.67909 (9)	0.0550 (4)
C1	0.7719 (3)	0.47819 (12)	0.68939 (10)	0.0494 (4)
C2	0.8294 (3)	0.53321 (12)	0.75571 (10)	0.0506 (4)
C3	0.7081 (3)	0.53034 (12)	0.82338 (10)	0.0536 (4)
H3	0.7451	0.5670	0.8670	0.064*
C4	0.5332 (3)	0.47461 (12)	0.82833 (10)	0.0524 (4)
C5	0.4816 (3)	0.42039 (12)	0.76175 (10)	0.0501 (4)
H5	0.3656	0.3819	0.7646	0.060*
C6	0.5953 (3)	0.42121 (12)	0.69126 (10)	0.0468 (4)
C7	1.0274 (3)	0.58874 (15)	0.75529 (11)	0.0594 (5)
H7A	1.0222	0.6353	0.7975	0.071*
H7B	1.1415	0.5465	0.7666	0.071*
C8	0.4047 (4)	0.47229 (16)	0.90293 (11)	0.0731 (6)
H8A	0.2749	0.4423	0.8919	0.110*
H8B	0.3806	0.5355	0.9211	0.110*
H8C	0.4765	0.4376	0.9434	0.110*
C9	0.5275 (3)	0.36320 (13)	0.61807 (10)	0.0539 (4)
C10	0.4755 (5)	0.43096 (16)	0.54936 (12)	0.0754 (6)
H10A	0.3555	0.4673	0.5630	0.113*
H10B	0.4484	0.3953	0.5019	0.113*
H10C	0.5901	0.4725	0.5403	0.113*
C11	0.3358 (4)	0.30415 (17)	0.63527 (14)	0.0745 (6)
H11A	0.2244	0.3448	0.6510	0.112*
H11B	0.3651	0.2605	0.6774	0.112*
H11C	0.2971	0.2701	0.5882	0.112*
C12	0.7001 (4)	0.29608 (16)	0.59218 (13)	0.0731 (6)
H12A	0.6504	0.2558	0.5504	0.110*
H12B	0.7423	0.2584	0.6368	0.110*
H12C	0.8157	0.3320	0.5731	0.110*
C13	0.9229 (3)	0.71409 (15)	0.66757 (13)	0.0668 (5)
H13A	0.7828	0.6912	0.6742	0.080*
H13B	0.9476	0.7621	0.7076	0.080*
C14	1.1466 (4)	0.79381 (18)	0.58285 (17)	0.0839 (7)
H14A	1.1654	0.8439	0.6215	0.101*
H14B	1.1600	0.8208	0.5300	0.101*
C15	1.3100 (4)	0.71942 (18)	0.59488 (14)	0.0743 (6)
H15A	1.3017	0.6732	0.5524	0.089*
H15B	1.4457	0.7482	0.5930	0.089*
C16	1.2798 (3)	0.67164 (15)	0.67383 (13)	0.0633 (5)
H16A	1.3757	0.6195	0.6790	0.076*
H16B	1.3065	0.7158	0.7167	0.076*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0583 (9)	0.0845 (9)	0.0533 (7)	−0.0116 (8)	0.0156 (7)	−0.0123 (7)
O2	0.0656 (10)	0.0945 (10)	0.0847 (10)	−0.0108 (9)	−0.0202 (8)	0.0295 (9)
N1	0.0417 (8)	0.0652 (8)	0.0579 (8)	−0.0029 (7)	−0.0030 (7)	0.0015 (7)
C1	0.0461 (9)	0.0594 (8)	0.0427 (8)	0.0024 (8)	0.0025 (7)	−0.0022 (7)
C2	0.0480 (10)	0.0563 (9)	0.0474 (8)	0.0045 (8)	−0.0048 (7)	0.0002 (8)
C3	0.0618 (11)	0.0578 (9)	0.0412 (8)	0.0048 (9)	−0.0042 (8)	−0.0049 (7)
C4	0.0547 (10)	0.0583 (8)	0.0443 (8)	0.0077 (8)	0.0048 (8)	−0.0005 (8)
C5	0.0474 (10)	0.0540 (8)	0.0491 (8)	0.0026 (8)	0.0026 (7)	0.0007 (7)
C6	0.0456 (9)	0.0517 (8)	0.0431 (7)	0.0058 (7)	−0.0011 (7)	−0.0018 (7)
C7	0.0526 (11)	0.0719 (10)	0.0537 (9)	−0.0032 (10)	−0.0084 (9)	0.0020 (9)
C8	0.0795 (16)	0.0877 (13)	0.0519 (11)	0.0033 (13)	0.0197 (10)	−0.0034 (10)
C9	0.0553 (11)	0.0637 (10)	0.0428 (8)	0.0006 (9)	−0.0051 (8)	−0.0044 (8)
C10	0.0868 (17)	0.0854 (13)	0.0541 (10)	−0.0005 (13)	−0.0201 (11)	0.0065 (10)
C11	0.0764 (16)	0.0823 (13)	0.0649 (12)	−0.0191 (12)	−0.0065 (11)	−0.0106 (11)
C12	0.0834 (17)	0.0754 (12)	0.0606 (11)	0.0122 (13)	0.0005 (11)	−0.0172 (10)
C13	0.0492 (11)	0.0760 (11)	0.0752 (13)	0.0046 (10)	−0.0018 (11)	0.0095 (11)
C14	0.0771 (17)	0.0884 (14)	0.0861 (16)	−0.0235 (14)	−0.0163 (14)	0.0215 (13)
C15	0.0625 (14)	0.0911 (14)	0.0694 (13)	−0.0203 (12)	0.0040 (11)	−0.0028 (11)
C16	0.0458 (10)	0.0732 (11)	0.0708 (12)	−0.0052 (9)	−0.0033 (10)	−0.0011 (10)

Geometric parameters (Å, º) top

O1—C1	1.370 (2)	C9—C11	1.526 (3)
O1—H1	0.852 (10)	C9—C12	1.531 (3)
O2—C13	1.396 (3)	C9—C10	1.539 (3)
O2—C14	1.436 (3)	C10—H10A	0.9600
N1—C13	1.450 (3)	C10—H10B	0.9600
N1—C16	1.467 (3)	C10—H10C	0.9600
N1—C7	1.473 (2)	C11—H11A	0.9600
C1—C6	1.401 (3)	C11—H11B	0.9600
C1—C2	1.410 (2)	C11—H11C	0.9600
C2—C3	1.382 (3)	C12—H12A	0.9600
C2—C7	1.505 (3)	C12—H12B	0.9600
C3—C4	1.384 (3)	C12—H12C	0.9600
C3—H3	0.9300	C13—H13A	0.9700
C4—C5	1.398 (2)	C13—H13B	0.9700
C4—C8	1.504 (2)	C14—C15	1.508 (4)
C5—C6	1.394 (2)	C14—H14A	0.9700
C5—H5	0.9300	C14—H14B	0.9700
C6—C9	1.543 (2)	C15—C16	1.502 (3)
C7—H7A	0.9700	C15—H15A	0.9700
C7—H7B	0.9700	C15—H15B	0.9700
C8—H8A	0.9600	C16—H16A	0.9700
C8—H8B	0.9600	C16—H16B	0.9700
C8—H8C	0.9600

C1—O1—H1	110 (2)	C9—C10—H10B	109.5
C13—O2—C14	110.29 (18)	H10A—C10—H10B	109.5
C13—N1—C16	110.01 (15)	C9—C10—H10C	109.5
C13—N1—C7	110.80 (16)	H10A—C10—H10C	109.5
C16—N1—C7	111.79 (16)	H10B—C10—H10C	109.5
O1—C1—C6	119.54 (15)	C9—C11—H11A	109.5
O1—C1—C2	119.30 (17)	C9—C11—H11B	109.5
C6—C1—C2	121.15 (16)	H11A—C11—H11B	109.5
C3—C2—C1	118.89 (18)	C9—C11—H11C	109.5
C3—C2—C7	120.23 (16)	H11A—C11—H11C	109.5
C1—C2—C7	120.73 (17)	H11B—C11—H11C	109.5
C2—C3—C4	122.09 (16)	C9—C12—H12A	109.5
C2—C3—H3	119.0	C9—C12—H12B	109.5
C4—C3—H3	119.0	H12A—C12—H12B	109.5
C3—C4—C5	117.54 (16)	C9—C12—H12C	109.5
C3—C4—C8	121.00 (16)	H12A—C12—H12C	109.5
C5—C4—C8	121.45 (18)	H12B—C12—H12C	109.5
C6—C5—C4	123.24 (18)	O2—C13—N1	111.13 (18)
C6—C5—H5	118.4	O2—C13—H13A	109.4
C4—C5—H5	118.4	N1—C13—H13A	109.4
C5—C6—C1	117.06 (15)	O2—C13—H13B	109.4
C5—C6—C9	121.45 (17)	N1—C13—H13B	109.4
C1—C6—C9	121.49 (15)	H13A—C13—H13B	108.0
N1—C7—C2	113.26 (15)	O2—C14—C15	110.27 (18)
N1—C7—H7A	108.9	O2—C14—H14A	109.6
C2—C7—H7A	108.9	C15—C14—H14A	109.6
N1—C7—H7B	108.9	O2—C14—H14B	109.6
C2—C7—H7B	108.9	C15—C14—H14B	109.6
H7A—C7—H7B	107.7	H14A—C14—H14B	108.1
C4—C8—H8A	109.5	C16—C15—C14	110.1 (2)
C4—C8—H8B	109.5	C16—C15—H15A	109.6
H8A—C8—H8B	109.5	C14—C15—H15A	109.6
C4—C8—H8C	109.5	C16—C15—H15B	109.6
H8A—C8—H8C	109.5	C14—C15—H15B	109.6
H8B—C8—H8C	109.5	H15A—C15—H15B	108.2
C11—C9—C12	107.79 (16)	N1—C16—C15	109.08 (18)
C11—C9—C10	107.87 (19)	N1—C16—H16A	109.9
C12—C9—C10	109.61 (18)	C15—C16—H16A	109.9
C11—C9—C6	111.95 (16)	N1—C16—H16B	109.9
C12—C9—C6	110.53 (17)	C15—C16—H16B	109.9
C10—C9—C6	109.03 (15)	H16A—C16—H16B	108.3
C9—C10—H10A	109.5

O1—C1—C2—C3	178.97 (16)	C16—N1—C7—C2	−166.73 (16)
C6—C1—C2—C3	0.0 (3)	C3—C2—C7—N1	−142.23 (18)
O1—C1—C2—C7	−5.4 (3)	C1—C2—C7—N1	42.2 (2)
C6—C1—C2—C7	175.57 (16)	C5—C6—C9—C11	−3.1 (2)
C1—C2—C3—C4	0.6 (3)	C1—C6—C9—C11	177.96 (17)
C7—C2—C3—C4	−175.06 (16)	C5—C6—C9—C12	−123.27 (19)
C2—C3—C4—C5	−0.1 (2)	C1—C6—C9—C12	57.8 (2)
C2—C3—C4—C8	179.57 (19)	C5—C6—C9—C10	116.2 (2)
C3—C4—C5—C6	−1.0 (3)	C1—C6—C9—C10	−62.8 (2)
C8—C4—C5—C6	179.35 (17)	C14—O2—C13—N1	−63.1 (2)
C4—C5—C6—C1	1.5 (3)	C16—N1—C13—O2	62.4 (2)
C4—C5—C6—C9	−177.50 (16)	C7—N1—C13—O2	−173.52 (16)
O1—C1—C6—C5	−179.96 (17)	C13—O2—C14—C15	59.0 (3)
C2—C1—C6—C5	−0.9 (2)	O2—C14—C15—C16	−54.6 (3)
O1—C1—C6—C9	−1.0 (2)	C13—N1—C16—C15	−56.7 (2)
C2—C1—C6—C9	178.05 (16)	C7—N1—C16—C15	179.72 (18)
C13—N1—C7—C2	70.2 (2)	C14—C15—C16—N1	53.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.85 (1)	1.90 (2)	2.665 (2)	149 (3)

Experimental details

Crystal data
Chemical formula	C₁₆H₂₅NO₂
M_r	263.37
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	293
a, b, c (Å)	6.4740 (7), 14.1928 (13), 16.7914 (16)
V (Å³)	1542.9 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.28 × 0.20 × 0.12

Data collection
Diffractometer	Rigaku R-AXIS Spider IP diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.980, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	15222, 2044, 1664
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.117, 1.11
No. of reflections	2044
No. of parameters	180
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.12

Computer programs: RAPID-AUTO (Rigaku, 2002), CrystalClear (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.85 (1)	1.90 (2)	2.665 (2)	149 (3)

Acknowledgements

We thank South China University of Technology and the University of Malaya for supporting this study.

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Korepin, A. G., Galkin, P. V., Glushakova, N. M., Lagodzinskaya, G. V., Loginova, M. V., Lodygina, V. P. & Eremenko, L. T. (2001). Russ. Chem. Bull. 50, 104–109. Web of Science CrossRef CAS Google Scholar
Rigaku (2002). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2002). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). publCIF. In preparation. Google Scholar