Di-tert-butyl cyclo­hex-2-ene-1,4-diyl dicarbonate

Ali, S.N.; Winnik, M.A.; Begum, S.; Lough, A.J.

doi:10.1107/S1600536809040343

organic compounds

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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page o2690

https://doi.org/10.1107/S1600536809040343

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Di-tert-butyl cyclohex-2-ene-1,4-diyl dicarbonate

Syed Nawazish Ali,^a ^* Mitchell A. Winnik,^b Sabira Begum ^a and Alan J. Lough ^b

^aH.E.J. Research Institute of Chemistry, International Center for Chemical and Biological Sciences, University of Karachi, Karachi 75270, Pakistan, and ^bDepartment of Chemistry, University of Toronto, Toronto, Ontario, Canada M5S 3H6
^*Correspondence e-mail: syed.nawazish@gmail.com

(Received 5 September 2009; accepted 3 October 2009; online 10 October 2009)

In the title molecule, C₁₆H₂₆O₆, the central cyclohexene ring is in a half-chair conformation. The carbonyl groups are in a trans arrangement with respect to each other and the dihedral angle between the mean planes of the carbonate groups is 10.8 (2)°.

Related literature

For synthetic applications of the title compound, see: Ali, Ghafouri et al. (2008 ). For a related structures, see: Ali, Begum et al. (2008 ); Rademeyer et al. (2003 ).

Experimental

Crystal data

C₁₆H₂₆O₆
M_r = 314.37
Monoclinic, P 2₁ /c
a = 12.6548 (11) Å
b = 5.8862 (6) Å
c = 23.126 (2) Å
β = 103.147 (5)°
V = 1677.5 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 150 K
0.10 × 0.09 × 0.02 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SORTAV; Blessing 1995 ) T_min = 0.865, T_max = 1.00
9313 measured reflections
2893 independent reflections
1407 reflections with I > 2σ(I)
R_int = 0.101

Refinement

R[F² > 2σ(F²)] = 0.068
wR(F²) = 0.191
S = 1.00
2893 reflections
205 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Data collection: COLLECT (Nonius, 2002 ); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997 ); data reduction: DENZO-SMN; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ); program(s) used to refine structure: SHELXTL (Sheldrick, 2008 ); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536809040343/ez2186sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809040343/ez2186Isup2.hkl

checkCIF report

Comment top

The title compound (I), is a new synthetic precursor of trans-cyclohex-2-ene-1,4-diol which has been synthesized for plasticizing purposes in order to break the crystallinity of a number of polyformals, and polycarbonates (Ali, Ghafouri et al., 2008). The molecular structure of (I) is shown in Fig. 1. Unlike the crystal structure of trans-Cyclohex-2-ene-1,4-diyl bis(4-nitrophenyl) dicarbonate (Ali, Begum et al., 2008) the central cyclohexene ring is completely ordered.

Related literature top

For synthetic applications of the title compound, see: Ali, Ghafouri et al. (2008). For a related crystal structure, see: Ali, Begum et al. (2008). For a related structure, see: Rademeyer et al. (2003).

Experimental top

A reaction mixture containing trans-cyclohex-2-ene-1,4-diol (0.59 g, 5.18 mmol), di-tert-butyldicarbonate (2.26 g, 10.36 mmol) and N,N-dimethylaminopyridine (DMAP) (0.80 g, 6.57 mmol) was stirred in dry dichloromethane (80 ml) at room temperature in a 250 ml round-bottom flask (see Fig. 2). After 4 h, it was transferred to a separatory funnel (250 ml) and washed with CH₃COOH (30 ml x 3, 0.1 M) to remove the excess of DMAP. The lower organic phase was removed and the aqueous phase was washed with dichloromethane (30 ml x 2). All the dichloromethane solutions were combined, washed with deionized water (30 ml x 3), and dried over anhydrous MgSO₄. After filtration, the solvent was removed by rotary evaporator. The resulting oily product was dried in vacuum oven at room temperature to obtain di-tert-butyl-cyclohex-2-ene-1,4-diyl dicarbonate (I, 1.14 g, 69.5%). The product was then recrystallized from a mixture of CHCl₃: MeOH (1:1) to afford needle-shaped crystals by slow evaporation of the solvent at room temperature. In addition to the X-ray structure determination, the structure was also confirmed by comparing the ¹H and ¹³C NMR data with a related t-Boc protected compound (Rademeyer et al., 2003). ¹H NMR (CDCl₃, p.p.m., relative to TMS, 400 MHz): 5.98 (2H, br.s, CH=CH), 5.16 (2H, m, CH—O), 2.08 (2H, m, CH₂—CH₂), 1.80 (2H, m, CH₂—CH₂), 1.48 (18H, s, CH₃); ¹³C NMR (CDCl₃, p.p.m., relative to TMS, 100 MHz): 168.4 (C=O), 129.1 (CH=CH), 71.4 (2H, CH—O), 66.3 (C(CH₃)₃O), 25.2 (CH₂), 28.0 (CH₃)

Structure description top

Computing details top

Data collection: COLLECT (Nonius, 2002); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound showing 30% probability ellipsoids.
	Fig. 2. Preparation of the title compound.

Di-tert-butyl cyclohex-2-ene-1,4-diyl dicarbonate top

Crystal data top

C₁₆H₂₆O₆	F(000) = 680
M_r = 314.37	D_x = 1.245 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9313 reflections
a = 12.6548 (11) Å	θ = 2.7–25.0°
b = 5.8862 (6) Å	µ = 0.09 mm⁻¹
c = 23.126 (2) Å	T = 150 K
β = 103.147 (5)°	Plate, colourless
V = 1677.5 (3) Å³	0.10 × 0.09 × 0.02 mm
Z = 4

Data collection top

Nonius KappaCCD diffractometer	2893 independent reflections
Radiation source: fine-focus sealed tube	1407 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.101
Detector resolution: 9 pixels mm^-1	θ_max = 25.0°, θ_min = 2.7°
φ scans and ω scans with κ offsets	h = −15→15
Absorption correction: multi-scan (SORTAV; Blessing 1995)	k = −6→6
T_min = 0.865, T_max = 1.00	l = −27→27
9313 measured reflections

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)] = 0.068	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.191	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0826P)²] where P = (F_o² + 2F_c²)/3
2893 reflections	(Δ/σ)_max < 0.001
205 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₁₆H₂₆O₆	V = 1677.5 (3) Å³
M_r = 314.37	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.6548 (11) Å	µ = 0.09 mm⁻¹
b = 5.8862 (6) Å	T = 150 K
c = 23.126 (2) Å	0.10 × 0.09 × 0.02 mm
β = 103.147 (5)°

Data collection top

Nonius KappaCCD diffractometer	2893 independent reflections
Absorption correction: multi-scan (SORTAV; Blessing 1995)	1407 reflections with I > 2σ(I)
T_min = 0.865, T_max = 1.00	R_int = 0.101
9313 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.068	0 restraints
wR(F²) = 0.191	H-atom parameters constrained
S = 1.00	Δρ_max = 0.24 e Å⁻³
2893 reflections	Δρ_min = −0.26 e Å⁻³
205 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	0.3871 (2)	−0.2647 (5)	0.54229 (13)	0.0663 (10)
O2	0.28611 (18)	−0.5049 (4)	0.48553 (11)	0.0489 (7)
O3	0.2107 (2)	−0.2869 (4)	0.54593 (11)	0.0503 (7)
O4	0.62164 (19)	0.3112 (4)	0.70717 (12)	0.0558 (8)
O5	0.72570 (17)	0.5487 (4)	0.76245 (10)	0.0448 (7)
O6	0.80169 (19)	0.2813 (4)	0.71320 (11)	0.0460 (7)
C1	0.4089 (3)	−0.0972 (7)	0.59017 (18)	0.0585 (12)
H1A	0.3386	−0.0373	0.5968	0.070*
C2	0.4714 (4)	0.0915 (7)	0.57122 (18)	0.0634 (13)
H2A	0.4502	0.1443	0.5314	0.076*
C3	0.5543 (4)	0.1881 (6)	0.60687 (19)	0.0620 (12)
H3A	0.5873	0.3142	0.5924	0.074*
C4	0.5991 (3)	0.1123 (6)	0.66812 (17)	0.0494 (11)
H4A	0.6678	0.0259	0.6699	0.059*
C5	0.5203 (3)	−0.0339 (7)	0.69112 (17)	0.0589 (12)
H5A	0.5584	−0.1110	0.7280	0.071*
H5B	0.4624	0.0625	0.7007	0.071*
C6	0.4707 (4)	−0.2079 (7)	0.64578 (17)	0.0627 (12)
H6A	0.5287	−0.3047	0.6365	0.075*
H6B	0.4213	−0.3065	0.6622	0.075*
C7	0.2865 (3)	−0.3486 (6)	0.52697 (16)	0.0449 (10)
C8	0.1825 (3)	−0.6087 (6)	0.45306 (15)	0.0405 (9)
C9	0.1263 (3)	−0.7330 (6)	0.49534 (16)	0.0555 (12)
H9A	0.1044	−0.6234	0.5223	0.083*
H9B	0.1764	−0.8441	0.5185	0.083*
H9C	0.0620	−0.8117	0.4725	0.083*
C10	0.1114 (3)	−0.4266 (6)	0.41818 (16)	0.0475 (10)
H10A	0.0908	−0.3174	0.4457	0.071*
H10B	0.0459	−0.4964	0.3938	0.071*
H10C	0.1513	−0.3480	0.3924	0.071*
C11	0.2218 (3)	−0.7736 (6)	0.41206 (17)	0.0551 (12)
H11A	0.2735	−0.8804	0.4357	0.083*
H11B	0.2575	−0.6891	0.3853	0.083*
H11C	0.1598	−0.8577	0.3886	0.083*
C12	0.7258 (3)	0.3718 (6)	0.72638 (15)	0.0387 (9)
C13	0.8304 (3)	0.6424 (6)	0.79714 (15)	0.0389 (9)
C14	0.8905 (3)	0.4608 (6)	0.83795 (16)	0.0506 (11)
H14A	0.9138	0.3407	0.8142	0.076*
H14B	0.8425	0.3961	0.8614	0.076*
H14C	0.9543	0.5278	0.8646	0.076*
C15	0.8964 (3)	0.7397 (6)	0.75658 (16)	0.0441 (10)
H15A	0.8539	0.8562	0.7312	0.066*
H15B	0.9155	0.6184	0.7318	0.066*
H15C	0.9628	0.8081	0.7804	0.066*
C16	0.7894 (3)	0.8280 (6)	0.83263 (16)	0.0498 (10)
H16A	0.7443	0.9354	0.8053	0.075*
H16B	0.8513	0.9086	0.8572	0.075*
H16C	0.7461	0.7591	0.8582	0.075*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0400 (15)	0.080 (2)	0.074 (2)	−0.0034 (15)	0.0022 (14)	−0.0451 (17)
O2	0.0407 (14)	0.0519 (16)	0.0495 (16)	−0.0001 (12)	0.0006 (12)	−0.0191 (13)
O3	0.0462 (15)	0.0593 (18)	0.0468 (18)	−0.0065 (13)	0.0135 (14)	−0.0159 (13)
O4	0.0369 (14)	0.0573 (17)	0.071 (2)	−0.0031 (13)	0.0078 (13)	−0.0341 (15)
O5	0.0377 (14)	0.0478 (15)	0.0467 (16)	−0.0061 (12)	0.0049 (12)	−0.0142 (13)
O6	0.0397 (14)	0.0440 (15)	0.0536 (18)	0.0009 (12)	0.0090 (13)	−0.0072 (13)
C1	0.043 (2)	0.067 (3)	0.060 (3)	−0.002 (2)	0.000 (2)	−0.034 (2)
C2	0.090 (3)	0.047 (3)	0.043 (3)	0.003 (2)	−0.005 (2)	−0.002 (2)
C3	0.098 (3)	0.039 (2)	0.054 (3)	−0.014 (2)	0.027 (3)	−0.012 (2)
C4	0.043 (2)	0.052 (2)	0.053 (3)	−0.0016 (19)	0.0120 (19)	−0.022 (2)
C5	0.073 (3)	0.052 (2)	0.048 (3)	−0.011 (2)	0.006 (2)	0.003 (2)
C6	0.086 (3)	0.057 (3)	0.048 (3)	−0.028 (2)	0.022 (2)	−0.009 (2)
C7	0.050 (2)	0.045 (2)	0.035 (2)	0.001 (2)	0.000 (2)	−0.0070 (19)
C8	0.041 (2)	0.041 (2)	0.035 (2)	−0.0049 (17)	−0.0024 (17)	−0.0031 (17)
C9	0.065 (3)	0.052 (3)	0.045 (3)	−0.007 (2)	0.003 (2)	0.001 (2)
C10	0.048 (2)	0.051 (2)	0.040 (2)	−0.0012 (19)	0.0032 (18)	0.0025 (19)
C11	0.055 (2)	0.057 (3)	0.048 (3)	0.003 (2)	0.001 (2)	−0.015 (2)
C12	0.039 (2)	0.042 (2)	0.034 (2)	−0.0034 (19)	0.0052 (18)	0.0001 (18)
C13	0.038 (2)	0.039 (2)	0.035 (2)	−0.0065 (17)	0.0003 (17)	−0.0009 (17)
C14	0.060 (2)	0.044 (2)	0.043 (2)	−0.006 (2)	0.0008 (19)	0.0045 (19)
C15	0.045 (2)	0.042 (2)	0.043 (2)	−0.0025 (18)	0.0069 (18)	−0.0016 (18)
C16	0.052 (2)	0.051 (2)	0.043 (2)	−0.010 (2)	0.0044 (19)	−0.0085 (19)

Geometric parameters (Å, º) top

O1—C7	1.337 (4)	C8—C10	1.510 (4)
O1—C1	1.461 (4)	C8—C11	1.518 (5)
O2—C7	1.328 (4)	C8—C9	1.521 (5)
O2—C8	1.486 (4)	C9—H9A	0.9800
O3—C7	1.197 (4)	C9—H9B	0.9800
O4—C12	1.340 (4)	C9—H9C	0.9800
O4—C4	1.466 (4)	C10—H10A	0.9800
O5—C12	1.334 (4)	C10—H10B	0.9800
O5—C13	1.490 (4)	C10—H10C	0.9800
O6—C12	1.197 (4)	C11—H11A	0.9800
C1—C2	1.486 (6)	C11—H11B	0.9800
C1—C6	1.494 (5)	C11—H11C	0.9800
C1—H1A	1.0000	C13—C15	1.504 (5)
C2—C3	1.307 (5)	C13—C14	1.512 (4)
C2—H2A	0.9500	C13—C16	1.527 (5)
C3—C4	1.470 (5)	C14—H14A	0.9800
C3—H3A	0.9500	C14—H14B	0.9800
C4—C5	1.503 (5)	C14—H14C	0.9800
C4—H4A	1.0000	C15—H15A	0.9800
C5—C6	1.497 (5)	C15—H15B	0.9800
C5—H5A	0.9900	C15—H15C	0.9800
C5—H5B	0.9900	C16—H16A	0.9800
C6—H6A	0.9900	C16—H16B	0.9800
C6—H6B	0.9900	C16—H16C	0.9800

C7—O1—C1	117.0 (3)	C8—C9—H9B	109.5
C7—O2—C8	120.5 (3)	H9A—C9—H9B	109.5
C12—O4—C4	117.1 (3)	C8—C9—H9C	109.5
C12—O5—C13	119.9 (3)	H9A—C9—H9C	109.5
O1—C1—C2	107.6 (3)	H9B—C9—H9C	109.5
O1—C1—C6	109.2 (3)	C8—C10—H10A	109.5
C2—C1—C6	111.7 (3)	C8—C10—H10B	109.5
O1—C1—H1A	109.4	H10A—C10—H10B	109.5
C2—C1—H1A	109.4	C8—C10—H10C	109.5
C6—C1—H1A	109.4	H10A—C10—H10C	109.5
C3—C2—C1	122.9 (4)	H10B—C10—H10C	109.5
C3—C2—H2A	118.5	C8—C11—H11A	109.5
C1—C2—H2A	118.5	C8—C11—H11B	109.5
C2—C3—C4	123.6 (4)	H11A—C11—H11B	109.5
C2—C3—H3A	118.2	C8—C11—H11C	109.5
C4—C3—H3A	118.2	H11A—C11—H11C	109.5
O4—C4—C3	109.2 (3)	H11B—C11—H11C	109.5
O4—C4—C5	106.9 (3)	O6—C12—O5	128.4 (3)
C3—C4—C5	111.9 (3)	O6—C12—O4	125.7 (3)
O4—C4—H4A	109.6	O5—C12—O4	106.0 (3)
C3—C4—H4A	109.6	O5—C13—C15	110.9 (3)
C5—C4—H4A	109.6	O5—C13—C14	109.5 (3)
C6—C5—C4	110.5 (3)	C15—C13—C14	112.8 (3)
C6—C5—H5A	109.6	O5—C13—C16	100.6 (3)
C4—C5—H5A	109.6	C15—C13—C16	111.6 (3)
C6—C5—H5B	109.6	C14—C13—C16	110.8 (3)
C4—C5—H5B	109.6	C13—C14—H14A	109.5
H5A—C5—H5B	108.1	C13—C14—H14B	109.5
C1—C6—C5	111.0 (3)	H14A—C14—H14B	109.5
C1—C6—H6A	109.4	C13—C14—H14C	109.5
C5—C6—H6A	109.4	H14A—C14—H14C	109.5
C1—C6—H6B	109.4	H14B—C14—H14C	109.5
C5—C6—H6B	109.4	C13—C15—H15A	109.5
H6A—C6—H6B	108.0	C13—C15—H15B	109.5
O3—C7—O2	127.1 (3)	H15A—C15—H15B	109.5
O3—C7—O1	125.8 (3)	C13—C15—H15C	109.5
O2—C7—O1	107.1 (3)	H15A—C15—H15C	109.5
O2—C8—C10	109.2 (3)	H15B—C15—H15C	109.5
O2—C8—C11	101.6 (3)	C13—C16—H16A	109.5
C10—C8—C11	111.1 (3)	C13—C16—H16B	109.5
O2—C8—C9	111.1 (3)	H16A—C16—H16B	109.5
C10—C8—C9	112.1 (3)	C13—C16—H16C	109.5
C11—C8—C9	111.2 (3)	H16A—C16—H16C	109.5
C8—C9—H9A	109.5	H16B—C16—H16C	109.5

Experimental details

Crystal data
Chemical formula	C₁₆H₂₆O₆
M_r	314.37
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	150
a, b, c (Å)	12.6548 (11), 5.8862 (6), 23.126 (2)
β (°)	103.147 (5)
V (Å³)	1677.5 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.10 × 0.09 × 0.02

Data collection
Diffractometer	Nonius KappaCCD
Absorption correction	Multi-scan (SORTAV; Blessing 1995)
T_min, T_max	0.865, 1.00
No. of measured, independent and observed [I > 2σ(I)] reflections	9313, 2893, 1407
R_int	0.101
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.068, 0.191, 1.00
No. of reflections	2893
No. of parameters	205
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.26

Computer programs: COLLECT (Nonius, 2002), DENZO-SMN (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1994), SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009).

Acknowledgements

The authors acknowledge funding from the Higher Education Commission (HEC), Pakistan, Materials and Manufacturing Ontario (MMO), Canada, NSERC Canada and the University of Toronto.

References

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