(S)-N-(1-Hydroxy­methyl-2-methyl­prop­yl)-2-methoxy­benzamide

Li, J.; Wang, W.; Lan, J.; You, J.

doi:10.1107/S160053680801009X

organic compounds

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Volume 64| Part 6| June 2008| Page o1052

doi:10.1107/S160053680801009X

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(S)-N-(1-Hydroxymethyl-2-methylpropyl)-2-methoxybenzamide

Jihong Li,^a Wenhai Wang,^a Jingbo Lan ^a ^* and Jingsong You ^a

^aKey Laboratory of Green Chemistry and Technology of the Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, People's Republic of China
^*Correspondence e-mail: jingbolan@scu.edu.cn

(Received 8 March 2008; accepted 13 April 2008; online 10 May 2008)

The title compound, C₁₃H₁₉NO₃, is an important synthetic intermediate. Weak O—H⋯O and N—H⋯O hydrogen bonds enhance the stability of the crystal structure.

Related literature

For related literature, see: Ma & You (2007 ); Rechavi & Lemaire (2002 ).

Experimental

Crystal data

C₁₃H₁₉NO₃
M_r = 237.29
Orthorhombic, P 2₁ 2₁ 2₁
a = 9.015 (4) Å
b = 10.386 (4) Å
c = 14.005 (4) Å
V = 1311.3 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 291 (2) K
0.50 × 0.44 × 0.40 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: none
1457 measured reflections
1397 independent reflections
848 reflections with I > 2σ(I)
R_int = 0.010
3 standard reflections every 120 reflections intensity decay: 0.4%

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.136
S = 1.02
1397 reflections
164 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O2ⁱ	0.82	2.00	2.806 (4)	170
N1—H1N1⋯O1	0.86	1.96	2.656 (4)	137
Symmetry code: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ .

Data collection: DIFRAC (Gabe & White, 1993 ); cell refinement: DIFRAC; data reduction: NRCVAX (Gabe et al., 1989 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680801009X/er2052sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680801009X/er2052Isup2.hkl

checkCIF report

Comment top

Oxazoline ligands have been proved to be a class of chiral ligands, being capable of forming a broad variety of metal complexes that are capable of catalyzing a great number of reactions with excellent enantioselectivity (Rechavi & Lemaire, 2002). It is believed that the oxazoline ring can be modified structurally by replacing the O atom with a substituted N atom, leading to new types of imidazoline ligands (Ma & You, 2007). However, all those ligands can prepared by this compound as an intermediate. Herein, we report the synthesis and structure of the title compound (I).

As shown in Fig. 1, there is a chiral center at C9 derived from L-valinol. The C—N bond lengths are 1.318 (4) Å and 1.463 (4) Å, and the C8—N1—C9 angle is 125.3 (3) °. A combination of O—H···O and N—H···O hydrogen bonds interactions provide packing forces in the crystal structure of the title compound.

Related literature top

For related literature, see: Ma & You (2007); Rechavi & Lemaire (2002).

Experimental top

NaH (8.7 g, 60%, 0.216 mol) was added portionwise to a stirred solution of L-valinol (22.1 g, 0.215 mol) in dry THF (120 ml). The mixture was stirred at ambient temperature for 1 h. To this solution was added 2-Methoxy-benzoic acid methyl ester (17.8 g, 0.107 mol) dissolved in THF (50 ml). The mixture was refluxed for 12 h under nitrogen, quenched with H₂O (10 ml) and concentrated by evaporation of the solvent. The residue was dissolved in CH₂Cl₂ (100 ml), washed with H₂O, brine, and dried over MgSO₄. And then removal of the solvent in vacuo gave a white solid, which was recrystallized from ethyl acetate and petroleum ether to afford the title compound as white crystals (22.8 g, 90%).

Computing details top

Data collection: DIFRAC (Gabe & White, 1993); cell refinement: DIFRAC (Gabe & White, 1993); data reduction: NRCVAX (Gabe et al., 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I), showing 30% probability displacement ellipsoids and the atomic numbering.

(S)-N-(1-Hydroxymethyl-2-methylpropyl)-2-methoxybenzamide top

Crystal data top

C₁₃H₁₉NO₃	F(000) = 512
M_r = 237.29	D_x = 1.202 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 25 reflections
a = 9.015 (4) Å	θ = 4.5–6.7°
b = 10.386 (4) Å	µ = 0.09 mm⁻¹
c = 14.005 (4) Å	T = 291 K
V = 1311.3 (9) Å³	Block, colourless
Z = 4	0.50 × 0.44 × 0.40 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.010
Radiation source: fine-focus sealed tube	θ_max = 25.5°, θ_min = 2.4°
Graphite monochromator	h = −3→10
ω/2θ scans	k = −3→12
1457 measured reflections	l = −5→16
1397 independent reflections	3 standard reflections every 120 reflections
848 reflections with I > 2σ(I)	intensity decay: 0.4%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.045	H-atom parameters constrained
wR(F²) = 0.136	w = 1/[σ²(F_o²) + (0.0778P)² + 0.0096P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
1397 reflections	Δρ_max = 0.21 e Å⁻³
164 parameters	Δρ_min = −0.14 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.069 (8)

Crystal data top

C₁₃H₁₉NO₃	V = 1311.3 (9) Å³
M_r = 237.29	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 9.015 (4) Å	µ = 0.09 mm⁻¹
b = 10.386 (4) Å	T = 291 K
c = 14.005 (4) Å	0.50 × 0.44 × 0.40 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.010
1457 measured reflections	3 standard reflections every 120 reflections
1397 independent reflections	intensity decay: 0.4%
848 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.136	H-atom parameters constrained
S = 1.02	Δρ_max = 0.21 e Å⁻³
1397 reflections	Δρ_min = −0.14 e Å⁻³
164 parameters

Special details top

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
O1	0.1432 (3)	0.3872 (3)	0.16126 (19)	0.0666 (8)
O2	0.5192 (3)	0.3286 (3)	−0.00264 (18)	0.0703 (8)
O3	0.2632 (4)	0.0046 (3)	−0.0111 (2)	0.0810 (10)
H3	0.1945	0.0562	−0.0140	0.097*
N1	0.3536 (3)	0.2340 (2)	0.0926 (2)	0.0487 (8)
H1N1	0.2711	0.2433	0.1227	0.058*
C1	0.1842 (4)	0.4786 (3)	0.0963 (3)	0.0514 (9)
C2	0.1074 (5)	0.5935 (4)	0.0851 (3)	0.0709 (12)
H2	0.0240	0.6099	0.1223	0.085*
C3	0.1535 (6)	0.6826 (4)	0.0201 (4)	0.0878 (16)
H3A	0.1009	0.7591	0.0133	0.105*
C4	0.2760 (6)	0.6610 (4)	−0.0355 (4)	0.0929 (18)
H4	0.3078	0.7226	−0.0791	0.112*
C5	0.3519 (5)	0.5457 (4)	−0.0255 (3)	0.0745 (13)
H5	0.4337	0.5300	−0.0642	0.089*
C6	0.3096 (4)	0.4533 (3)	0.0402 (3)	0.0489 (9)
C7	0.0018 (6)	0.3961 (7)	0.2048 (3)	0.109 (2)
H7A	−0.0038	0.4739	0.2416	0.163*
H7B	−0.0130	0.3233	0.2460	0.163*
H7C	−0.0735	0.3970	0.1564	0.163*
C8	0.4020 (4)	0.3328 (3)	0.0425 (2)	0.0459 (9)
C9	0.4288 (4)	0.1097 (3)	0.1012 (2)	0.0456 (8)
H9	0.5050	0.1060	0.0514	0.055*
C10	0.3202 (5)	0.0025 (3)	0.0824 (3)	0.0609 (10)
H10A	0.3691	−0.0794	0.0932	0.073*
H10B	0.2387	0.0091	0.1273	0.073*
C11	0.5075 (5)	0.0978 (4)	0.1981 (3)	0.0632 (11)
H11	0.5515	0.0115	0.2002	0.076*
C12	0.6339 (6)	0.1925 (5)	0.2074 (4)	0.0939 (16)
H12A	0.5957	0.2787	0.2045	0.141*
H12B	0.7031	0.1794	0.1562	0.141*
H12C	0.6832	0.1796	0.2674	0.141*
C13	0.4068 (6)	0.1084 (6)	0.2833 (3)	0.107 (2)
H13A	0.4630	0.0946	0.3406	0.160*
H13B	0.3299	0.0447	0.2788	0.160*
H13C	0.3631	0.1926	0.2849	0.160*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0560 (16)	0.0735 (18)	0.0704 (16)	0.0177 (16)	0.0102 (13)	0.0020 (15)
O2	0.0553 (16)	0.0652 (18)	0.0903 (18)	−0.0022 (15)	0.0249 (16)	0.0137 (16)
O3	0.072 (2)	0.071 (2)	0.099 (2)	0.0007 (16)	−0.0180 (18)	−0.0113 (17)
N1	0.0369 (15)	0.0481 (16)	0.0610 (17)	0.0057 (15)	0.0078 (14)	0.0039 (14)
C1	0.050 (2)	0.046 (2)	0.058 (2)	−0.0001 (18)	−0.0117 (19)	−0.0054 (18)
C2	0.064 (3)	0.060 (3)	0.089 (3)	0.015 (2)	−0.016 (2)	−0.019 (2)
C3	0.070 (3)	0.048 (2)	0.146 (4)	0.002 (2)	−0.043 (3)	0.008 (3)
C4	0.067 (3)	0.059 (3)	0.152 (5)	−0.011 (3)	−0.030 (3)	0.047 (3)
C5	0.053 (2)	0.066 (2)	0.104 (3)	−0.010 (2)	−0.011 (2)	0.031 (3)
C6	0.044 (2)	0.0442 (18)	0.059 (2)	−0.0051 (17)	−0.0149 (17)	0.0013 (17)
C7	0.077 (3)	0.156 (6)	0.094 (3)	0.036 (4)	0.030 (3)	0.020 (4)
C8	0.037 (2)	0.046 (2)	0.054 (2)	−0.0041 (17)	−0.0023 (16)	0.0044 (18)
C9	0.0387 (18)	0.0447 (19)	0.0534 (19)	0.0069 (17)	0.0040 (15)	−0.0004 (17)
C10	0.053 (2)	0.050 (2)	0.080 (3)	0.0044 (19)	0.000 (2)	0.004 (2)
C11	0.062 (3)	0.061 (3)	0.067 (2)	0.016 (2)	−0.009 (2)	0.011 (2)
C12	0.096 (3)	0.093 (3)	0.093 (3)	0.000 (3)	−0.037 (3)	−0.011 (3)
C13	0.120 (4)	0.146 (5)	0.054 (2)	0.031 (5)	0.004 (3)	0.016 (3)

Geometric parameters (Å, º) top

O1—C1	1.365 (4)	C6—C8	1.504 (5)
O1—C7	1.416 (5)	C7—H7A	0.9600
O2—C8	1.232 (4)	C7—H7B	0.9600
O3—C10	1.406 (5)	C7—H7C	0.9600
O3—H3	0.8200	C9—C10	1.506 (5)
N1—C8	1.318 (4)	C9—C11	1.537 (5)
N1—C9	1.463 (4)	C9—H9	0.9800
N1—H1N1	0.8600	C10—H10A	0.9700
C1—C2	1.389 (5)	C10—H10B	0.9700
C1—C6	1.402 (5)	C11—C13	1.503 (6)
C2—C3	1.363 (6)	C11—C12	1.511 (6)
C2—H2	0.9300	C11—H11	0.9800
C3—C4	1.369 (7)	C12—H12A	0.9600
C3—H3A	0.9300	C12—H12B	0.9600
C4—C5	1.386 (6)	C12—H12C	0.9600
C4—H4	0.9300	C13—H13A	0.9600
C5—C6	1.383 (5)	C13—H13B	0.9600
C5—H5	0.9300	C13—H13C	0.9600

C1—O1—C7	119.1 (4)	N1—C8—C6	118.4 (3)
C10—O3—H3	109.5	N1—C9—C10	109.7 (3)
C8—N1—C9	125.3 (3)	N1—C9—C11	111.0 (3)
C8—N1—H1N1	117.4	C10—C9—C11	113.3 (3)
C9—N1—H1N1	117.4	N1—C9—H9	107.5
O1—C1—C2	122.5 (4)	C10—C9—H9	107.5
O1—C1—C6	117.5 (3)	C11—C9—H9	107.5
C2—C1—C6	120.0 (4)	O3—C10—C9	112.9 (3)
C3—C2—C1	120.4 (4)	O3—C10—H10A	109.0
C3—C2—H2	119.8	C9—C10—H10A	109.0
C1—C2—H2	119.8	O3—C10—H10B	109.0
C2—C3—C4	121.0 (4)	C9—C10—H10B	109.0
C2—C3—H3A	119.5	H10A—C10—H10B	107.8
C4—C3—H3A	119.5	C13—C11—C12	109.8 (4)
C3—C4—C5	118.8 (4)	C13—C11—C9	114.6 (3)
C3—C4—H4	120.6	C12—C11—C9	111.8 (3)
C5—C4—H4	120.6	C13—C11—H11	106.7
C6—C5—C4	122.0 (5)	C12—C11—H11	106.7
C6—C5—H5	119.0	C9—C11—H11	106.7
C4—C5—H5	119.0	C11—C12—H12A	109.5
C5—C6—C1	117.7 (4)	C11—C12—H12B	109.5
C5—C6—C8	116.0 (3)	H12A—C12—H12B	109.5
C1—C6—C8	126.2 (3)	C11—C12—H12C	109.5
O1—C7—H7A	109.5	H12A—C12—H12C	109.5
O1—C7—H7B	109.5	H12B—C12—H12C	109.5
H7A—C7—H7B	109.5	C11—C13—H13A	109.5
O1—C7—H7C	109.5	C11—C13—H13B	109.5
H7A—C7—H7C	109.5	H13A—C13—H13B	109.5
H7B—C7—H7C	109.5	C11—C13—H13C	109.5
O2—C8—N1	122.0 (3)	H13A—C13—H13C	109.5
O2—C8—C6	119.6 (3)	H13B—C13—H13C	109.5

C7—O1—C1—C2	13.4 (5)	C9—N1—C8—C6	179.2 (3)
C7—O1—C1—C6	−167.0 (4)	C5—C6—C8—O2	9.9 (5)
O1—C1—C2—C3	179.3 (3)	C1—C6—C8—O2	−171.7 (3)
C6—C1—C2—C3	−0.3 (6)	C5—C6—C8—N1	−169.6 (3)
C1—C2—C3—C4	−0.0 (6)	C1—C6—C8—N1	8.8 (5)
C2—C3—C4—C5	0.9 (7)	C8—N1—C9—C10	−130.9 (4)
C3—C4—C5—C6	−1.5 (7)	C8—N1—C9—C11	103.2 (4)
C4—C5—C6—C1	1.2 (6)	N1—C9—C10—O3	63.2 (4)
C4—C5—C6—C8	179.7 (4)	C11—C9—C10—O3	−172.2 (3)
O1—C1—C6—C5	−179.8 (3)	N1—C9—C11—C13	59.7 (4)
C2—C1—C6—C5	−0.2 (5)	C10—C9—C11—C13	−64.2 (5)
O1—C1—C6—C8	1.8 (5)	N1—C9—C11—C12	−66.1 (4)
C2—C1—C6—C8	−178.6 (3)	C10—C9—C11—C12	170.0 (3)
C9—N1—C8—O2	−0.3 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2ⁱ	0.82	2.00	2.806 (4)	170
N1—H1N1···O1	0.86	1.96	2.656 (4)	137

Symmetry code: (i) x−1/2, −y+1/2, −z.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₉NO₃
M_r	237.29
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	291
a, b, c (Å)	9.015 (4), 10.386 (4), 14.005 (4)
V (Å³)	1311.3 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.50 × 0.44 × 0.40

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	1457, 1397, 848
R_int	0.010
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.136, 1.02
No. of reflections	1397
No. of parameters	164
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.14

Computer programs: DIFRAC (Gabe & White, 1993), NRCVAX (Gabe et al., 1989), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2ⁱ	0.82	2.00	2.806 (4)	169.7
N1—H1N1···O1	0.86	1.96	2.656 (4)	136.7

Symmetry code: (i) x−1/2, −y+1/2, −z.

References

Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
Gabe, E. J., Le Page, Y., Charland, J.-P., Lee, F. L. & White, P. S. (1989). J. Appl. Cryst. 22, 384–387. CrossRef CAS Web of Science IUCr Journals Google Scholar
Gabe, E. J. & White, P. S. (1993). DIFRAC. American Crystallographic Association, Pittsburgh Meeting. Abstract PA104. Google Scholar
Ma, K. & You, J. (2007). Chem. Eur. J. 13, 1863–1871. Web of Science CrossRef PubMed CAS Google Scholar
Rechavi, D. & Lemaire, M. (2002). Chem. Rev. 102, 3467–3494. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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doi:10.1107/S160053680801009X

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