1-Acet­amido-1-(1-naphthyl)­ethyl­ene

The crystal structure and synthesis of 1-acet­amido-1-(1-naphthyl)­ethyl­ene, C₁₄H₁₃NO, are reported.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.047
• wR factor = 0.154
• Data-to-parameter ratio = 18.7

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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S1. Comment

Enamides were extensively studied for practical use as the prochiral materials for the asymmetric synthesis of chiral amines, which can be used as resolving reagents, chiral auxiliaries and intermediates for the synthesis of many biological active substances (Burk et al., 1996; Noyori et al., 1986; Kitamura et al., 1994; Tschaen et al., 1995; Meth-Cohn et al., 1984; Mpango et al., 1980; Baldwin et al., 1980). Herein, we report the crystal structure of an enamide, 1-acetamido-1-(1-naphthyl)ethylene, (I). We have been using it as the substrate for the synthesis of corresponding optical active amide through catalytic hydrogenation in our laboratory.

S2. Experimental

The title compound was prepared according to the literature method of Burk et al. (1998). Acetic anhydride (8.39 g, 82.3 mmol), followed by acetic acid (4.94 g, 82.3 mmol) was added to a solution of 1-acetonaphthone oxime (5.07 g, 27.4 mmol) in toluene (40 ml) under a nitrogen atmosphere. Fe powder (3.08 g, 55 mmol) was then added and the mixture was heated to 343 K for 8 h. The reaction mixture was then cooled to room temperature and filtered through celite to remove solid residues, which were then washed with toluene (2 × 5 ml). The combined filtrates were diluted with dichloromethane (50 ml) and the mixture cooled in an ice-bath and washed with 2M NaOH (2 × 30 ml). The organic phase was separated, dried over Na₂SO₄, and evaporated to a volume of 30 ml, the solution was cooled to room temperature and then the desired enamide was precipitated, After filtration, followed by recrystalization from hexane and ethyl acetate, crystals were obtained.

S3. Refinement

The C-bound H atoms were placed in their geometrically calculated positions and included in the final refinement in the riding-model approximation.

Computing details

Data collection: SMART (Siemens, 1995); cell refinement: SMART; data reduction: SHELXTL-NT (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-NT; software used to prepare material for publication: SHELXTL-NT.

Figures

Fig. 1. The molecular structure of (I) with ellipsoids at the 30% probability level (Siemens, 1995).

1-Acetamido-1-(1-naphthyl)ethylene

Crystal data

C14H13NO	Dx = 1.185 Mg m^−3
Mr = 211.25	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 3813 reflections
a = 11.2035 (15) Å	θ = 1–27.5°
b = 9.2977 (13) Å	µ = 0.08 mm^−1
c = 22.738 (3) Å	T = 294 K
V = 2368.6 (6) Å^3	Block, colorless
Z = 8	0.30 × 0.16 × 0.14 mm
F(000) = 896

Data collection

Bruker CCD area-detector diffractometer	2715 independent reflections
Radiation source: fine-focus sealed tube	1200 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.047
ϕ and ω scans	θmax = 27.6°, θmin = 3.0°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −14→11
Tmin = 0.978, Tmax = 0.990	k = −12→12
15120 measured reflections	l = −27→29

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.154	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.07P)^2] where P = (Fo^2 + 2Fc^2)/3
2715 reflections	(Δ/σ)max < 0.001
145 parameters	Δρmax = 0.19 e Å^−3
0 restraints	Δρmin = −0.22 e Å^−3

Special details

Experimental. ? #Insert any special details here.

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.27806 (13)	0.26222 (14)	0.55689 (7)	0.0811 (5)
N1	0.32706 (13)	0.03131 (15)	0.57421 (7)	0.0582 (5)
H1A	0.2945	−0.0590	0.5680	0.070*
C1	0.43930 (18)	0.0490 (2)	0.60172 (9)	0.0635 (5)
C2	0.4909 (2)	0.1736 (3)	0.61349 (12)	0.0947 (8)
H2A	0.4569	0.2668	0.6045	0.114*
H2B	0.5648	0.1731	0.6365	0.114*
C3	0.49925 (17)	−0.0898 (2)	0.61534 (9)	0.0607 (5)
C4	0.60170 (19)	−0.1258 (3)	0.58605 (10)	0.0824 (7)
H4A	0.6328	−0.0623	0.5584	0.099*
C5	0.6604 (2)	−0.2551 (3)	0.59665 (13)	0.0992 (8)
H5A	0.7299	−0.2766	0.5761	0.119*
C6	0.6178 (2)	−0.3489 (3)	0.63617 (13)	0.0960 (8)
H6A	0.6582	−0.4348	0.6427	0.115*
C7	0.5116 (2)	−0.3189 (2)	0.66842 (10)	0.0742 (6)
C8	0.4647 (3)	−0.4147 (3)	0.70999 (13)	0.0980 (8)
H8A	0.5029	−0.5019	0.7168	0.118*
C9	0.3641 (3)	−0.3818 (3)	0.74041 (12)	0.1020 (9)
H9A	0.3341	−0.4462	0.7680	0.122*
C10	0.3061 (2)	−0.2529 (3)	0.73052 (11)	0.0886 (7)
H10A	0.2372	−0.2315	0.7516	0.106*
C11	0.34805 (18)	−0.1570 (2)	0.69048 (9)	0.0702 (6)
H11A	0.3077	−0.0708	0.6845	0.084*
C12	0.45229 (17)	−0.1869 (2)	0.65783 (8)	0.0594 (5)
C13	0.25292 (17)	0.1346 (2)	0.55456 (8)	0.0581 (5)
C14	0.13884 (19)	0.0832 (2)	0.52842 (10)	0.0754 (6)
H14A	0.1286	−0.0107	0.5112	0.090*
H14B	0.1165	0.1514	0.4985	0.090*
H14C	0.0770	0.0908	0.5584	0.090*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0879 (11)	0.0403 (8)	0.1152 (13)	0.0022 (7)	0.0118 (9)	−0.0009 (8)
N1	0.0595 (10)	0.0413 (9)	0.0737 (11)	−0.0045 (8)	−0.0026 (8)	0.0017 (7)
C1	0.0630 (13)	0.0619 (13)	0.0657 (14)	−0.0113 (11)	0.0018 (10)	0.0022 (10)
C2	0.0946 (17)	0.0713 (16)	0.118 (2)	−0.0251 (14)	−0.0249 (15)	0.0081 (14)
C3	0.0570 (12)	0.0660 (13)	0.0591 (13)	−0.0008 (10)	−0.0051 (10)	−0.0018 (10)
C4	0.0609 (14)	0.1083 (19)	0.0781 (16)	0.0075 (14)	0.0042 (12)	0.0051 (14)
C5	0.0689 (16)	0.130 (2)	0.098 (2)	0.0311 (16)	−0.0064 (15)	−0.0059 (19)
C6	0.092 (2)	0.102 (2)	0.093 (2)	0.0375 (16)	−0.0328 (15)	−0.0085 (16)
C7	0.0831 (16)	0.0738 (15)	0.0658 (15)	0.0082 (13)	−0.0263 (12)	−0.0010 (12)
C8	0.139 (3)	0.0742 (17)	0.0809 (19)	−0.0020 (17)	−0.0411 (18)	0.0157 (15)
C9	0.137 (3)	0.095 (2)	0.0734 (18)	−0.0284 (19)	−0.0158 (17)	0.0233 (15)
C10	0.0997 (18)	0.0951 (18)	0.0710 (17)	−0.0172 (15)	0.0103 (13)	0.0121 (14)
C11	0.0774 (15)	0.0698 (13)	0.0636 (14)	−0.0060 (11)	0.0038 (11)	0.0003 (11)
C12	0.0625 (13)	0.0615 (13)	0.0541 (12)	−0.0025 (10)	−0.0091 (10)	−0.0021 (10)
C13	0.0654 (13)	0.0421 (11)	0.0668 (13)	0.0039 (10)	0.0110 (10)	−0.0014 (9)
C14	0.0699 (13)	0.0595 (12)	0.0967 (17)	0.0092 (10)	−0.0040 (12)	0.0003 (12)

Geometric parameters (Å, º)

O1—C13	1.221 (2)	C6—H6A	0.9300
N1—C13	1.346 (2)	C7—C8	1.401 (3)
N1—C1	1.414 (2)	C7—C12	1.416 (3)
N1—H1A	0.9263	C8—C9	1.358 (4)
C1—C2	1.322 (3)	C8—H8A	0.9300
C1—C3	1.488 (3)	C9—C10	1.381 (4)
C2—H2A	0.9681	C9—H9A	0.9300
C2—H2B	0.9794	C10—C11	1.359 (3)
C3—C4	1.368 (3)	C10—H10A	0.9300
C3—C12	1.423 (3)	C11—C12	1.412 (3)
C4—C5	1.392 (3)	C11—H11A	0.9300
C4—H4A	0.9300	C13—C14	1.488 (3)
C5—C6	1.340 (3)	C14—H14A	0.9631
C5—H5A	0.9300	C14—H14B	0.9635
C6—C7	1.426 (3)	C14—H14C	0.9745
C13—N1—C1	127.77 (16)	C9—C8—C7	120.8 (3)
C13—N1—H1A	110.7	C9—C8—H8A	119.6
C1—N1—H1A	121.5	C7—C8—H8A	119.6
C2—C1—N1	125.47 (19)	C8—C9—C10	120.2 (3)
C2—C1—C3	121.40 (19)	C8—C9—H9A	119.9
N1—C1—C3	113.10 (16)	C10—C9—H9A	119.9
C1—C2—H2A	124.7	C11—C10—C9	121.0 (2)
C1—C2—H2B	118.2	C11—C10—H10A	119.5
H2A—C2—H2B	116.8	C9—C10—H10A	119.5
C4—C3—C12	119.06 (19)	C10—C11—C12	120.6 (2)
C4—C3—C1	119.29 (19)	C10—C11—H11A	119.7
C12—C3—C1	121.65 (17)	C12—C11—H11A	119.7
C3—C4—C5	121.5 (2)	C11—C12—C7	118.0 (2)
C3—C4—H4A	119.2	C11—C12—C3	122.55 (18)
C5—C4—H4A	119.2	C7—C12—C3	119.46 (19)
C6—C5—C4	120.7 (2)	O1—C13—N1	122.47 (19)
C6—C5—H5A	119.7	O1—C13—C14	121.83 (18)
C4—C5—H5A	119.7	N1—C13—C14	115.69 (16)
C5—C6—C7	121.0 (2)	C13—C14—H14A	123.7
C5—C6—H6A	119.5	C13—C14—H14B	107.1
C7—C6—H6A	119.5	H14A—C14—H14B	106.2
C8—C7—C12	119.3 (2)	C13—C14—H14C	107.9
C8—C7—C6	122.4 (3)	H14A—C14—H14C	105.3
C12—C7—C6	118.3 (2)	H14B—C14—H14C	105.2
C13—N1—C1—C2	0.7 (3)	C8—C9—C10—C11	0.0 (4)
C13—N1—C1—C3	−177.47 (18)	C9—C10—C11—C12	0.1 (3)
C2—C1—C3—C4	−65.5 (3)	C10—C11—C12—C7	−0.4 (3)
N1—C1—C3—C4	112.8 (2)	C10—C11—C12—C3	179.79 (19)
C2—C1—C3—C12	115.0 (2)	C8—C7—C12—C11	0.6 (3)
N1—C1—C3—C12	−66.8 (2)	C6—C7—C12—C11	−179.14 (18)
C12—C3—C4—C5	0.4 (3)	C8—C7—C12—C3	−179.57 (19)
C1—C3—C4—C5	−179.2 (2)	C6—C7—C12—C3	0.7 (3)
C3—C4—C5—C6	0.0 (4)	C4—C3—C12—C11	179.10 (18)
C4—C5—C6—C7	0.0 (4)	C1—C3—C12—C11	−1.3 (3)
C5—C6—C7—C8	180.0 (2)	C4—C3—C12—C7	−0.7 (3)
C5—C6—C7—C12	−0.3 (3)	C1—C3—C12—C7	178.85 (17)
C12—C7—C8—C9	−0.5 (4)	C1—N1—C13—O1	2.5 (3)
C6—C7—C8—C9	179.2 (2)	C1—N1—C13—C14	−178.79 (18)
C7—C8—C9—C10	0.3 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1^i	0.93	1.87	2.7931 (19)	177.2

Symmetry code: (i) −x+1/2, y−1/2, z.