Ethyl N-(2-acetyl-3-oxo-1-phenyl­but­yl)carbamate

Volov, A.N.; Zamilatskov, I.A.

doi:10.1107/S1600536813024884

organic compounds

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Volume 69| Part 10| October 2013| Page o1529

doi:10.1107/S1600536813024884

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Ethyl N-(2-acetyl-3-oxo-1-phenylbutyl)carbamate

Alexander N. Volov ^a ^* and Ilia A. Zamilatskov ^a

^aA. N. Frumkin Institute of Physical Chemistry and Electrochemistry RAS, Leninsky prospect 31, Moscow 119071, Russian Federation
^*Correspondence e-mail: alex123.87@mail.ru

(Received 4 September 2013; accepted 6 September 2013; online 12 September 2013)

In the title compound, C₁₅H₁₉NO₄, all three carbonyl groups are syn-oriented with respect to the methine group attached to the phenyl ring. The mean planes of the phenyl ring and ethyl carbamate moiety form a dihedral angle of 65.2 (1)°. In the crystal, molecules related by translation in [100] are linked into chains via N—H⋯O hydrogen bonds.

Related literature

For details of the synthesis, see: Kuzmina et al. (2013 ). For the crystal structures of related compounds, see: Hatano et al. (2008 ).

Experimental

Crystal data

C₁₅H₁₉NO₄
M_r = 277.31
Triclinic, $[P \overline 1]$
a = 5.392 (2) Å
b = 9.204 (2) Å
c = 15.841 (6) Å
α = 81.58 (2)°
β = 81.98 (2)°
γ = 89.13 (3)°
V = 770.1 (4) Å³
Z = 2
Cu Kα radiation
μ = 0.71 mm⁻¹
T = 295 K
0.50 × 0.21 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.76, T_max = 0.92
4976 measured reflections
3176 independent reflections
2057 reflections with I > 2σ(I)
R_int = 0.022
2 standard reflections every 150 reflections intensity decay: 3%

Refinement

R[F² > 2σ(F²)] = 0.068
wR(F²) = 0.231
S = 1.04
3176 reflections
189 parameters
15 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2ⁱ	0.97 (3)	2.26 (3)	3.180 (4)	158 (2)
Symmetry code: (i) x+1, y, z.

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, 1R. DOI: 10.1107/S1600536813024884/rk2414sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813024884/rk2414Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813024884/rk2414Isup3.cml

checkCIF report

Comment top

Recently, we have developed a simple general five-step approach for the synthesis of macrocycles containing semicarbazide moieties via heterocyclization of semicarbazides with oxo group in 3 position (Kuzmina et al., 2013). The title compound, I, has been obtained as an intermediate product. Herewith we present its molecular and crystal structure.

In I (Fig. 1), all bond lengths and angles are normal and correspond well to those observed in the related (1R,2R)-benzyl (3-oxo-2-((2-oxo-1,3-oxazolidin-3-yl)carbonyl)-1-phenylbutyl)carbamate and (S)-benzyl (2-acetyl-1-(4-bromophenyl)-2-hydroxy-3-oxobutyl)carbamate (Hatano et al., 2008). In the molecule, all three carbonyl groups are syn oriented with respect to the methine group attached to the phenyl ring.

In the crystal, the molecules related by translation in [1 0 0] are linked into chains via intermolecular classical N–H···O hydrogen bonds (Table 1, Fig. 2).

Related literature top

For details of the synthesis, see: Kuzmina et al. (2013). For the crystal structures of related compounds, see: Hatano et al. (2008).

Experimental top

To a solution of KOH (0.277 g, 0.0049 mol) in 30 ml ethanol was added acetylacetone (0.495 g, 0.0049 mol) and stirred vigorously for 10 minutes. Ethyl N-[(tosyl)(phenyl)methyl]carbamate (1.5 g, 0.0045 mol) was added and reaction mixture stirred for 6.5 h. After completion of reaction, solution was evaporated to dryness and residue washed with saturated solution of NaHCO₃, hexane and dried to give 1.1 g (88%) of ethyl N-[(2-acetyl-3-oxo-1-phenyl)butyl]carbamate as white powder. An analytically pure sample was obtained by recrystallization from MeOH-H₂O (2:3). M.p. 421-422 K (MeOH-H₂O (2:3)).

¹H NMR (600 MHz; DMSO-d6): δ_H, p.p.m. 7.76(1H, d, J = 9.16 Hz, NH), 7.21-7.30 (5H, m, H in Ph), 5.15 (1H, t, J = 9.78 Hz, CH), 4.47(1H, d, J = 11.12 Hz, CH), 3.87-3.93 (2H, m, CH₂ in COOEt), 2.22 (3H, s, CH₃ in acetyl), 1.87 (3H, s, CH₃ in acetyl), 1.08 (3H, t, J = 7.04 Hz, CH₃ in COOEt). ¹³C NMR (150 MHz; DMSO-d6): δ_H, p.p.m. 14.4, 30.1, 30.7, 54.1, 59.9, 71.7, 127.3, 127.5, 128.4, 140.6, 155.3, 201.3, 201.5 Anal. Calcd for C₁₅H₁₉NO₄: C, 64.97; H, 6.91; N 5.05. Found: C, 65.09; H, 6.98; N, 5.12.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of I whith the atom numbering scheme. Displacement ellipsoids are drawn at 50% probability level. H atoms are presented as a small spheres of arbitrary radius.
	Fig. 2. Portion of the crystal packing in I. Dotted blue lines denote hydrogen bonds.

Ethyl N-(2-acetyl-3-oxo-1-phenylbutyl)carbamate top

Crystal data top

C₁₅H₁₉NO₄	F(000) = 296
M_r = 277.31	D_x = 1.196 Mg m⁻³
Triclinic, P1	Melting point = 421–422 K
a = 5.392 (2) Å	Cu Kα radiation, λ = 1.54184 Å
b = 9.204 (2) Å	Cell parameters from 25 reflections
c = 15.841 (6) Å	θ = 31.6–34.9°
α = 81.58 (2)°	µ = 0.71 mm⁻¹
β = 81.98 (2)°	T = 295 K
γ = 89.13 (3)°	Prism, colourless
V = 770.1 (4) Å³	0.50 × 0.21 × 0.10 mm
Z = 2

Data collection top

Enraf–Nonius CAD-4 diffractometer	2057 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.022
Graphite monochromator	θ_max = 74.9°, θ_min = 2.9°
non–profiled ω–scans	h = −3→6
Absorption correction: ψ scan (North et al., 1968)	k = −11→11
T_min = 0.76, T_max = 0.92	l = −19→19
4976 measured reflections	2 standard reflections every 150 reflections
3176 independent reflections	intensity decay: 3%

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)] = 0.068	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.231	w = 1/[σ²(F_o²) + (0.11P)² + 0.24P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
3176 reflections	Δρ_max = 0.30 e Å⁻³
189 parameters	Δρ_min = −0.19 e Å⁻³
15 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: 0.009 (2)

Crystal data top

C₁₅H₁₉NO₄	γ = 89.13 (3)°
M_r = 277.31	V = 770.1 (4) Å³
Triclinic, P1	Z = 2
a = 5.392 (2) Å	Cu Kα radiation
b = 9.204 (2) Å	µ = 0.71 mm⁻¹
c = 15.841 (6) Å	T = 295 K
α = 81.58 (2)°	0.50 × 0.21 × 0.10 mm
β = 81.98 (2)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	2057 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.022
T_min = 0.76, T_max = 0.92	2 standard reflections every 150 reflections
4976 measured reflections	intensity decay: 3%
3176 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.068	15 restraints
wR(F²) = 0.231	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.30 e Å⁻³
3176 reflections	Δρ_min = −0.19 e Å⁻³
189 parameters

Special details top

Geometry. All s.u.'s (except the s.u. 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 s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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	0.1419 (4)	0.4031 (2)	0.90111 (13)	0.0701 (6)
O2	−0.1063 (4)	0.5365 (2)	0.81579 (14)	0.0702 (6)
O3	0.3293 (5)	0.8086 (4)	0.55078 (16)	0.1061 (10)
O4	0.3031 (5)	0.4665 (3)	0.6140 (3)	0.1242 (12)
N1	0.3154 (5)	0.5683 (3)	0.79670 (16)	0.0609 (6)
H1	0.473 (6)	0.541 (3)	0.8167 (19)	0.064 (8)*
C1	0.3263 (5)	0.6871 (3)	0.72419 (17)	0.0553 (6)
H1A	0.1667	0.6874	0.7012	0.066*
C2	0.5335 (5)	0.6570 (3)	0.65270 (18)	0.0581 (7)
H2	0.6965	0.6633	0.6726	0.070*
C3	0.5268 (6)	0.7669 (4)	0.57095 (19)	0.0649 (7)
C4	0.7610 (7)	0.8120 (5)	0.5160 (3)	0.1017 (13)
H4A	0.7268	0.8494	0.4589	0.153*
H4B	0.8706	0.7291	0.5137	0.153*
H4C	0.8396	0.8873	0.5391	0.153*
C5	0.5017 (6)	0.5036 (4)	0.6283 (2)	0.0691 (8)
C6	0.7211 (7)	0.4071 (4)	0.6219 (3)	0.0900 (11)
H6A	0.6725	0.3140	0.6088	0.135*
H6B	0.7871	0.3930	0.6758	0.135*
H6C	0.8470	0.4515	0.5770	0.135*
C7	0.1002 (5)	0.5061 (3)	0.83558 (17)	0.0548 (6)
C8	−0.0754 (8)	0.3217 (4)	0.9476 (2)	0.0914 (12)
H8A	−0.1578	0.2732	0.9086	0.110*
H8B	−0.1940	0.3873	0.9743	0.110*
C9	0.0159 (12)	0.2109 (5)	1.0147 (3)	0.1292 (19)
H9A	0.1200	0.1409	0.9873	0.194*
H9B	−0.1247	0.1611	1.0506	0.194*
H9C	0.1111	0.2595	1.0493	0.194*
C10	0.3566 (5)	0.8362 (3)	0.75167 (17)	0.0588 (7)
C11	0.5396 (6)	0.8614 (3)	0.8002 (2)	0.0796 (9)
H11	0.6451	0.7851	0.8171	0.096*
C12	0.5704 (8)	0.9968 (3)	0.8243 (3)	0.0980 (12)
H12	0.6966	1.0120	0.8566	0.118*
C13	0.4143 (8)	1.1085 (4)	0.8004 (3)	0.1067 (15)
H13	0.4308	1.1995	0.8181	0.128*
C14	0.2344 (9)	1.0878 (4)	0.7509 (3)	0.1055 (14)
H14	0.1319	1.1652	0.7331	0.127*
C15	0.2056 (7)	0.9521 (3)	0.7275 (2)	0.0822 (10)
H15	0.0808	0.9382	0.6944	0.099*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0820 (15)	0.0563 (11)	0.0669 (12)	−0.0039 (10)	−0.0069 (10)	0.0051 (9)
O2	0.0492 (11)	0.0760 (13)	0.0806 (13)	−0.0023 (9)	−0.0063 (10)	0.0021 (10)
O3	0.0653 (15)	0.159 (3)	0.0856 (17)	0.0111 (16)	−0.0218 (13)	0.0192 (17)
O4	0.0603 (15)	0.115 (2)	0.220 (4)	−0.0017 (14)	−0.0398 (19)	−0.079 (2)
N1	0.0470 (13)	0.0575 (13)	0.0750 (15)	−0.0004 (10)	−0.0148 (11)	0.0071 (11)
C1	0.0428 (13)	0.0567 (14)	0.0633 (15)	0.0001 (11)	−0.0069 (11)	0.0010 (12)
C2	0.0391 (13)	0.0660 (16)	0.0710 (16)	0.0013 (11)	−0.0118 (12)	−0.0116 (13)
C3	0.0503 (16)	0.0802 (19)	0.0655 (16)	0.0004 (14)	−0.0103 (13)	−0.0128 (14)
C4	0.071 (2)	0.113 (3)	0.108 (3)	−0.014 (2)	0.003 (2)	0.016 (2)
C5	0.0503 (16)	0.0778 (19)	0.083 (2)	−0.0032 (14)	−0.0095 (14)	−0.0224 (16)
C6	0.067 (2)	0.086 (2)	0.125 (3)	0.0126 (18)	−0.016 (2)	−0.039 (2)
C7	0.0602 (17)	0.0465 (13)	0.0571 (14)	−0.0002 (11)	−0.0058 (12)	−0.0076 (11)
C8	0.108 (3)	0.076 (2)	0.080 (2)	−0.017 (2)	0.008 (2)	0.0016 (18)
C9	0.195 (6)	0.083 (3)	0.092 (3)	−0.001 (3)	0.011 (3)	0.017 (2)
C10	0.0480 (14)	0.0566 (15)	0.0660 (16)	0.0041 (11)	0.0049 (12)	−0.0026 (12)
C11	0.070 (2)	0.0651 (18)	0.109 (3)	0.0108 (15)	−0.0193 (18)	−0.0244 (18)
C12	0.091 (3)	0.074 (2)	0.136 (3)	0.002 (2)	−0.016 (2)	−0.039 (2)
C13	0.106 (3)	0.064 (2)	0.142 (4)	0.003 (2)	0.020 (3)	−0.028 (2)
C14	0.107 (3)	0.068 (2)	0.134 (4)	0.028 (2)	−0.002 (3)	−0.006 (2)
C15	0.073 (2)	0.071 (2)	0.097 (2)	0.0179 (17)	−0.0054 (18)	−0.0011 (17)

Geometric parameters (Å, º) top

O1—C7	1.341 (3)	C6—H6B	0.9600
O1—C8	1.450 (4)	C6—H6C	0.9600
O2—C7	1.216 (3)	C8—C9	1.491 (6)
O3—C3	1.196 (4)	C8—H8A	0.9700
O4—C5	1.190 (4)	C8—H8B	0.9700
N1—C7	1.331 (4)	C9—H9A	0.9600
N1—C1	1.461 (3)	C9—H9B	0.9600
N1—H1	0.97 (3)	C9—H9C	0.9600
C1—C10	1.516 (4)	C10—C11	1.374 (3)
C1—C2	1.529 (4)	C10—C15	1.375 (3)
C1—H1A	0.9800	C11—C12	1.375 (3)
C2—C3	1.526 (4)	C11—H11	0.9300
C2—C5	1.536 (4)	C12—C13	1.363 (3)
C2—H2	0.9800	C12—H12	0.9300
C3—C4	1.459 (5)	C13—C14	1.362 (3)
C4—H4A	0.9600	C13—H13	0.9300
C4—H4B	0.9600	C14—C15	1.371 (3)
C4—H4C	0.9600	C14—H14	0.9300
C5—C6	1.469 (5)	C15—H15	0.9300
C6—H6A	0.9600

C7—O1—C8	116.4 (3)	O2—C7—N1	126.0 (3)
C7—N1—C1	122.2 (2)	O2—C7—O1	123.9 (3)
C7—N1—H1	121.8 (18)	N1—C7—O1	110.1 (2)
C1—N1—H1	116.0 (18)	O1—C8—C9	107.0 (4)
N1—C1—C10	112.0 (2)	O1—C8—H8A	110.3
N1—C1—C2	109.9 (2)	C9—C8—H8A	110.3
C10—C1—C2	112.1 (2)	O1—C8—H8B	110.3
N1—C1—H1A	107.6	C9—C8—H8B	110.3
C10—C1—H1A	107.6	H8A—C8—H8B	108.6
C2—C1—H1A	107.6	C8—C9—H9A	109.5
C3—C2—C1	111.4 (2)	C8—C9—H9B	109.5
C3—C2—C5	106.9 (2)	H9A—C9—H9B	109.5
C1—C2—C5	110.7 (2)	C8—C9—H9C	109.5
C3—C2—H2	109.3	H9A—C9—H9C	109.5
C1—C2—H2	109.3	H9B—C9—H9C	109.5
C5—C2—H2	109.3	C11—C10—C15	117.4 (3)
O3—C3—C4	121.1 (3)	C11—C10—C1	121.3 (2)
O3—C3—C2	119.5 (3)	C15—C10—C1	121.3 (3)
C4—C3—C2	119.3 (3)	C10—C11—C12	121.6 (3)
C3—C4—H4A	109.5	C10—C11—H11	119.2
C3—C4—H4B	109.5	C12—C11—H11	119.2
H4A—C4—H4B	109.5	C13—C12—C11	119.4 (4)
C3—C4—H4C	109.5	C13—C12—H12	120.3
H4A—C4—H4C	109.5	C11—C12—H12	120.3
H4B—C4—H4C	109.5	C14—C13—C12	120.4 (4)
O4—C5—C6	121.7 (3)	C14—C13—H13	119.8
O4—C5—C2	119.8 (3)	C12—C13—H13	119.8
C6—C5—C2	118.5 (3)	C13—C14—C15	119.5 (4)
C5—C6—H6A	109.5	C13—C14—H14	120.2
C5—C6—H6B	109.5	C15—C14—H14	120.2
H6A—C6—H6B	109.5	C14—C15—C10	121.6 (3)
C5—C6—H6C	109.5	C14—C15—H15	119.2
H6A—C6—H6C	109.5	C10—C15—H15	119.2
H6B—C6—H6C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ⁱ	0.97 (3)	2.26 (3)	3.180 (4)	158 (2)

Symmetry code: (i) x+1, y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ⁱ	0.97 (3)	2.26 (3)	3.180 (4)	158 (2)

Symmetry code: (i) x+1, y, z.

References

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doi:10.1107/S1600536813024884

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