Methyl N-{(1R)-2-[(meth­oxy­carbon­yl)­oxy]-1-phenyleth­yl}carbamate

Mendoza Herrera, M. del C.; Sampedro Cruz, M.; Pérez Díaz, L.M.; Rivera Márquez, J.A.; Orea Flores, L.; Bernès, S.

doi:10.1107/S2414314624002220

organic compounds

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ISSN: 2414-3146

Volume 9| Part 3| March 2024| x240222

https://doi.org/10.1107/S2414314624002220

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Methyl N-{(1R)-2-[(methoxycarbonyl)oxy]-1-phenylethyl}carbamate

María del Consuelo Mendoza Herrera,^a Mario Sampedro Cruz,^a Lydia María Pérez Díaz,^a José Antonio Rivera Márquez,^a Laura Orea Flores ^b and Sylvain Bernès ^c ^*

^aFacultad de Ingeniería Química, Benemérita Universidad Autónoma de Puebla, 72570 Puebla, Pue., Mexico, ^bInstituto de Ciencias, Benemérita Universidad Autónoma de Puebla, 72570 Puebla, Pue., Mexico, and ^cInstituto de Física Luis Rivera Terrazas, Benemérita Universidad Autónoma de Puebla, 72570 Puebla, Pue., Mexico
^*Correspondence e-mail: sylvain_bernes@hotmail.com

Edited by W. T. A. Harrison, University of Aberdeen, United Kingdom (Received 6 March 2024; accepted 7 March 2024; online 21 March 2024)

The title molecule, C₁₂H₁₅NO₅, is a methyl carbamate derivative obtained by reacting (R)-2-phenylglycinol and methyl chloroformate, with calcium hydroxide as heterogeneous catalyst. Supramolecular chains are formed in the [100] direction, based on N—H⋯O hydrogen bonds between the amide and carboxylate groups. These chains weakly interact in the crystal, and the phenyl rings do not display significant π–π interactions.

Keywords: crystal structure; carbamate; phenylglycinol; supramolecular chain; Sohncke group.

CCDC reference: 2338571

Structure description

Methyl carbamate, Me(O)CONH₂, the methyl ester of carbamic acid, is an important intermediate in the manufacture of carbamate-based resins used in the textile and polymer industries. On a smaller scale, it is also a pharmaceutical intermediate. The primary amine group can be functionalized, in the same way as for primary amides. From another point of view, the formation of a carbamate via a N-methyloxycarbonylation reaction can also be considered as a useful protection of a primary amine (Sartori et al., 2004 ). Finally, alternative routes allow both the formation of the carbamate and the N-functionalization. The title compound, C₁₂H₁₅NO₅, resulted from such a reaction, between methyl chloroformate and a chiral amino alcohol, namely (R)-2-phenylglycinol, under basic conditions, and using Ca(OH)₂ as a heterogeneous catalyst.

We assumed that the R absolute configuration of the starting material was retained during the reaction, affording an enantiomerically pure compound, which crystallized in the Sohncke space group P2₁2₁2₁. Molecular dimensions are as expected, and the amide group displays a geometry quite different from that of the carboxylate group, with bond lengths C2—N1 = 1.333 (3) and C10—O3 = 1.445 (3) Å (Fig. 1). The geometry of the carbamate group is virtually identical to that observed in the closely related chiral compound methyl(1S-phenylethyl)carbamate, which crystallizes with four independent molecules in the asymmetric unit (Thakar et al., 2018 ).

Figure 1
The molecular structure of the title compound (50% probability ellipsoids).

In the extended structure, the amide NH group serves as a donor, forming an intermolecular hydrogen bond with the carboxylate group C11=O4 of a neighbouring molecule (Table 1). Infinite chains are then formed in the crystal, running along the short a axis (Fig. 2). Molecules are further connected through weak C—H⋯O contacts involving the methyl group of the carbamate moiety as donor. Chains are arranged in the crystal with two neighbouring chains having the phenyl rings facing upwards (Fig. 3). However, no significant π–π contacts are observed: the distance separating two rings is large [4.6763 (17) Å] and the dihedral angle between corresponding mean planes is 21.84 (13)°. Aside from the weak C—H⋯O bonds mentioned above and van der Waals contacts, no other significant interactions between the supramolecular chains are present in the crystal structure. As a consequence, the Kitaigorodskii packing index of 67.8% is rather low for this small organic molecule (Spek, 2020 ).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O4ⁱ	0.82 (3)	2.10 (3)	2.917 (2)	175 (2)
C1—H1B⋯O4ⁱⁱ	0.96	2.59	3.494 (3)	158
C1—H1C⋯O5ⁱⁱⁱ	0.96	2.62	3.332 (4)	131
Symmetry codes: (i) ; (ii) $[-x+{\script{1\over 2}}, -y+1, z+{\script{1\over 2}}]$ ; (iii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Figure 2
Supramolecular chains formed in the [100] direction, based on amide–carboxylate N—H⋯O hydrogen bonds (dashed bonds).

Figure 3
Part of the crystal structure of the title compound, viewed down the crystallographic a axis. The asymmetric unit is shown as a ball and stick model, and the dashed line represents the weak π–π interaction between phenyl rings.

Synthesis and crystallization

(R)-2-Phenylglycinol (100 mg, 0.73 mmol) was dissolved in dry THF. The catalyst, Ca(OH)₂ (10%), and methyl chloroformate (0.56 ml, 7.2 mmol) were added, and the mixture was refluxed (333 K) under a nitrogen atmosphere. After completion (TLC), the catalyst was separated by filtration, and the crude product recovered by elimination of the solvent under reduced pressure. The crude product was recrystallized from a mixture of solvents (hexane:CH₂Cl₂, 4:1 v:v), affording single crystals suitable for X-ray diffraction. ¹H-NMR (500 MHz, CDCl₃): δ 3.66 (s, 3H), 3.76 (s, 3H), 4.35 (s, 2H), 5.05 (broad, 1H), 5.64 (broad, 1H), 7.29–7.37 (m, 5H) p.p.m. ¹³C-NMR (126 MHz, CDCl₃): δ 52.33, 54.2, 55.06, 69.66, 126.59, 128.06, 128.80, 138.20, 155.68, 156.41 p.p.m.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The amide H atom (H1) was refined with free coordinates and isotropic displacement parameter. Other H atoms are in calculated positions. The absolute configuration was inferred from the synthesis.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₂H₁₅NO₅
M_r	253.25
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	295
a, b, c (Å)	6.2497 (2), 13.8633 (6), 14.6254 (5)
V (Å³)	1267.17 (8)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.10
Crystal size (mm)	0.67 × 0.29 × 0.16

Data collection
Diffractometer	Xcalibur, Atlas, Gemini
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2022 $[Rigaku OD (2022). CrysAlis PRO. Rigaku Oxford Diffraction Ltd, Yarnton, England.]$ )
T_min, T_max	0.967, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	24119, 3859, 2841
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.714

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.118, 1.03
No. of reflections	3859
No. of parameters	169
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.16
Computer programs: CrysAlis PRO (Rigaku OD, 2022 $[Rigaku OD (2022). CrysAlis PRO. Rigaku Oxford Diffraction Ltd, Yarnton, England.]$ ), SHELXT2018/2 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ), XP in SHELXTL-Plus (Sheldrick, 2008 ), Mercury (Macrae et al., 2020 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 2338571

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314624002220/hb4464sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314624002220/hb4464Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314624002220/hb4464Isup3.cml

checkCIF report

Computing details top

Methyl N-{(1R)-2-[(methoxycarbonyl)oxy]-1-phenylethyl}carbamate top

Crystal data top

C₁₂H₁₅NO₅	D_x = 1.327 Mg m⁻³
M_r = 253.25	Melting point: 345 K
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
a = 6.2497 (2) Å	Cell parameters from 4907 reflections
b = 13.8633 (6) Å	θ = 3.3–26.1°
c = 14.6254 (5) Å	µ = 0.10 mm⁻¹
V = 1267.17 (8) Å³	T = 295 K
Z = 4	Block, colourless
F(000) = 536	0.67 × 0.29 × 0.16 mm

Data collection top

Xcalibur, Atlas, Gemini diffractometer	3859 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	2841 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
Detector resolution: 10.5564 pixels mm^-1	θ_max = 30.5°, θ_min = 2.9°
ω scans	h = −8→8
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2022)	k = −19→19
T_min = 0.967, T_max = 1.000	l = −20→20
24119 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.046	Hydrogen site location: mixed
wR(F²) = 0.118	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0587P)² + 0.052P] where P = (F_o² + 2F_c²)/3
3859 reflections	(Δ/σ)_max < 0.001
169 parameters	Δρ_max = 0.14 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³
0 constraints

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

	x	y	z	U_iso*/U_eq
O1	−0.2085 (3)	0.43365 (12)	0.59140 (10)	0.0598 (4)
O2	0.1160 (3)	0.49818 (13)	0.62348 (10)	0.0670 (5)
O3	0.2905 (2)	0.37368 (12)	0.36207 (12)	0.0607 (4)
O4	0.6279 (2)	0.42897 (11)	0.36564 (11)	0.0597 (4)
O5	0.5449 (3)	0.27357 (12)	0.38930 (13)	0.0668 (5)
N1	−0.0043 (3)	0.48073 (14)	0.47814 (11)	0.0527 (4)
H1	−0.105 (4)	0.4625 (18)	0.4474 (16)	0.053 (6)*
C1	−0.2419 (5)	0.4127 (2)	0.68630 (17)	0.0769 (8)
H1A	−0.387398	0.392701	0.695569	0.115*
H1B	−0.213777	0.469417	0.721969	0.115*
H1C	−0.147035	0.361905	0.704931	0.115*
C2	−0.0183 (3)	0.47379 (15)	0.56885 (13)	0.0475 (4)
C3	0.1699 (3)	0.52669 (16)	0.43010 (13)	0.0473 (5)
H3	0.297760	0.524175	0.468833	0.057*
C4	0.1259 (4)	0.63165 (16)	0.40547 (13)	0.0492 (5)
C5	−0.0757 (4)	0.6723 (2)	0.41155 (19)	0.0678 (7)
H5	−0.190104	0.634538	0.430815	0.081*
C6	−0.1102 (5)	0.7682 (2)	0.3895 (2)	0.0834 (8)
H6	−0.246934	0.794183	0.394150	0.100*
C7	0.0544 (6)	0.8242 (2)	0.36108 (19)	0.0790 (8)
H7	0.030618	0.888693	0.346652	0.095*
C8	0.2556 (6)	0.7862 (2)	0.3536 (2)	0.0868 (9)
H8	0.368411	0.824713	0.333876	0.104*
C9	0.2916 (5)	0.6898 (2)	0.37548 (19)	0.0725 (7)
H9	0.428547	0.664215	0.369869	0.087*
C10	0.2142 (4)	0.46992 (18)	0.34271 (14)	0.0541 (5)
H10A	0.083947	0.465903	0.306877	0.065*
H10B	0.320390	0.503898	0.306596	0.065*
C11	0.5013 (4)	0.36477 (15)	0.37178 (13)	0.0492 (4)
C12	0.7676 (4)	0.2503 (2)	0.4027 (2)	0.0787 (8)
H12A	0.850042	0.275381	0.352705	0.118*
H12B	0.784356	0.181520	0.405485	0.118*
H12C	0.816598	0.278478	0.458896	0.118*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0627 (9)	0.0623 (9)	0.0543 (8)	−0.0127 (8)	0.0094 (7)	−0.0026 (7)
O2	0.0727 (10)	0.0791 (12)	0.0492 (8)	−0.0157 (9)	−0.0091 (8)	−0.0040 (8)
O3	0.0484 (8)	0.0545 (9)	0.0791 (10)	−0.0078 (7)	0.0020 (8)	−0.0061 (8)
O4	0.0521 (8)	0.0539 (9)	0.0732 (10)	−0.0146 (7)	−0.0156 (8)	0.0141 (8)
O5	0.0597 (9)	0.0467 (9)	0.0940 (12)	−0.0059 (7)	0.0045 (8)	0.0026 (8)
N1	0.0464 (9)	0.0661 (11)	0.0457 (9)	−0.0137 (9)	−0.0059 (8)	0.0020 (8)
C1	0.098 (2)	0.0742 (19)	0.0583 (13)	−0.0119 (15)	0.0262 (14)	−0.0041 (12)
C2	0.0533 (11)	0.0412 (10)	0.0479 (10)	0.0005 (9)	−0.0004 (9)	−0.0013 (8)
C3	0.0395 (9)	0.0585 (12)	0.0439 (9)	−0.0055 (9)	−0.0062 (7)	0.0019 (8)
C4	0.0512 (11)	0.0560 (12)	0.0403 (9)	−0.0038 (10)	−0.0048 (9)	−0.0002 (9)
C5	0.0576 (14)	0.0716 (17)	0.0742 (15)	0.0022 (12)	−0.0028 (11)	0.0071 (14)
C6	0.0823 (19)	0.0727 (19)	0.095 (2)	0.0178 (16)	−0.0093 (17)	0.0056 (15)
C7	0.107 (3)	0.0602 (15)	0.0697 (16)	0.0062 (16)	−0.0161 (15)	0.0083 (13)
C8	0.102 (2)	0.069 (2)	0.0893 (19)	−0.0242 (17)	−0.0026 (18)	0.0189 (15)
C9	0.0614 (14)	0.0686 (16)	0.0873 (17)	−0.0081 (12)	0.0014 (14)	0.0136 (14)
C10	0.0488 (10)	0.0626 (14)	0.0508 (10)	0.0009 (10)	−0.0021 (9)	0.0004 (10)
C11	0.0524 (11)	0.0489 (11)	0.0464 (10)	−0.0090 (10)	−0.0008 (10)	−0.0009 (9)
C12	0.0703 (16)	0.0606 (16)	0.105 (2)	0.0071 (12)	−0.0097 (17)	0.0120 (15)

Geometric parameters (Å, º) top

O1—C2	1.353 (3)	C4—C5	1.383 (3)
O1—C1	1.433 (3)	C4—C9	1.384 (3)
O2—C2	1.207 (2)	C5—C6	1.385 (4)
O3—C11	1.331 (3)	C5—H5	0.9300
O3—C10	1.445 (3)	C6—C7	1.355 (4)
O4—C11	1.194 (2)	C6—H6	0.9300
O5—C11	1.318 (3)	C7—C8	1.368 (5)
O5—C12	1.442 (3)	C7—H7	0.9300
N1—C2	1.333 (3)	C8—C9	1.392 (4)
N1—C3	1.444 (3)	C8—H8	0.9300
N1—H1	0.82 (3)	C9—H9	0.9300
C1—H1A	0.9600	C10—H10A	0.9700
C1—H1B	0.9600	C10—H10B	0.9700
C1—H1C	0.9600	C12—H12A	0.9600
C3—C4	1.524 (3)	C12—H12B	0.9600
C3—C10	1.526 (3)	C12—H12C	0.9600
C3—H3	0.9800

C2—O1—C1	116.6 (2)	C7—C6—C5	120.3 (3)
C11—O3—C10	115.66 (17)	C7—C6—H6	119.9
C11—O5—C12	116.11 (19)	C5—C6—H6	119.9
C2—N1—C3	124.45 (18)	C6—C7—C8	120.1 (3)
C2—N1—H1	118.4 (17)	C6—C7—H7	120.0
C3—N1—H1	116.9 (17)	C8—C7—H7	120.0
O1—C1—H1A	109.5	C7—C8—C9	120.0 (3)
O1—C1—H1B	109.5	C7—C8—H8	120.0
H1A—C1—H1B	109.5	C9—C8—H8	120.0
O1—C1—H1C	109.5	C4—C9—C8	120.7 (3)
H1A—C1—H1C	109.5	C4—C9—H9	119.6
H1B—C1—H1C	109.5	C8—C9—H9	119.6
O2—C2—N1	126.4 (2)	O3—C10—C3	111.83 (17)
O2—C2—O1	124.37 (19)	O3—C10—H10A	109.2
N1—C2—O1	109.27 (18)	C3—C10—H10A	109.2
N1—C3—C4	113.60 (18)	O3—C10—H10B	109.2
N1—C3—C10	108.46 (18)	C3—C10—H10B	109.2
C4—C3—C10	109.09 (17)	H10A—C10—H10B	107.9
N1—C3—H3	108.5	O4—C11—O5	126.4 (2)
C4—C3—H3	108.5	O4—C11—O3	125.3 (2)
C10—C3—H3	108.5	O5—C11—O3	108.30 (18)
C5—C4—C9	117.7 (2)	O5—C12—H12A	109.5
C5—C4—C3	122.6 (2)	O5—C12—H12B	109.5
C9—C4—C3	119.8 (2)	H12A—C12—H12B	109.5
C4—C5—C6	121.2 (3)	O5—C12—H12C	109.5
C4—C5—H5	119.4	H12A—C12—H12C	109.5
C6—C5—H5	119.4	H12B—C12—H12C	109.5

C3—N1—C2—O2	−5.4 (4)	C5—C6—C7—C8	0.4 (5)
C3—N1—C2—O1	175.16 (19)	C6—C7—C8—C9	−0.2 (5)
C1—O1—C2—O2	−5.0 (3)	C5—C4—C9—C8	0.9 (4)
C1—O1—C2—N1	174.4 (2)	C3—C4—C9—C8	−179.3 (2)
C2—N1—C3—C4	−95.0 (2)	C7—C8—C9—C4	−0.4 (5)
C2—N1—C3—C10	143.5 (2)	C11—O3—C10—C3	−88.4 (2)
N1—C3—C4—C5	−12.6 (3)	N1—C3—C10—O3	−65.0 (2)
C10—C3—C4—C5	108.5 (2)	C4—C3—C10—O3	170.79 (16)
N1—C3—C4—C9	167.6 (2)	C12—O5—C11—O4	0.4 (4)
C10—C3—C4—C9	−71.3 (3)	C12—O5—C11—O3	−179.5 (2)
C9—C4—C5—C6	−0.8 (4)	C10—O3—C11—O4	−0.1 (3)
C3—C4—C5—C6	179.4 (2)	C10—O3—C11—O5	179.81 (17)
C4—C5—C6—C7	0.2 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O4ⁱ	0.82 (3)	2.10 (3)	2.917 (2)	175 (2)
C1—H1B···O4ⁱⁱ	0.96	2.59	3.494 (3)	158
C1—H1C···O5ⁱⁱⁱ	0.96	2.62	3.332 (4)	131

Symmetry codes: (i) x−1, y, z; (ii) −x+1/2, −y+1, z+1/2; (iii) x−1/2, −y+1/2, −z+1.

Acknowledgements

We thank Dr Angel Mendoza (ICUAP, Puebla) for diffractometer time.

References

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