2,2-Bis(3-chloro­methyl-4-ethoxy­phen­yl)propane

Jaballah, N.; Guerfel, T.; Majdoub, M.

doi:10.1107/S1600536808018783

organic compounds

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ISSN: 2056-9890

Volume 64| Part 7| July 2008| Page o1360

doi:10.1107/S1600536808018783

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2,2-Bis(3-chloromethyl-4-ethoxyphenyl)propane

Nejmeddine Jaballah,^a ^* Taha Guerfel ^a and Mustapha Majdoub ^a

^aDépartement de Chimie, Faculté des Sciences, 5019 Monastir, Tunisia
^*Correspondence e-mail: nejm_1@yahoo.fr

(Received 11 June 2008; accepted 20 June 2008; online 28 June 2008)

The title compound, C₂₁H₂₆Cl₂O₂, a bis-chloromethyl derivative of O-ethylated bisphenol A, exhibits C₂ molecular symmetry. It shows a bent conformation with the two benzene rings nearly perpendicular [dihedral angle = 87.17 (6)°].

Related literature

For more information on the synthesis, see: Miyazawa et al. (1999 ). For background to the investigation of new conjugated polymers derived from bisphenols as potential organic semi-conducting materials, see: Jaballah et al. (2006 ). For the use of bis-chloromethyl bisphenol A ethers for the control of fungal and bacterial organisms, see: Priddy & Hennis (1970 ).

Experimental

Crystal data

C₂₁H₂₆Cl₂O₂
M_r = 381.32
Monoclinic, C 2/c
a = 13.856 (5) Å
b = 15.185 (6) Å
c = 10.999 (4) Å
β = 118.82 (3)°
V = 2027.7 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 293 (2) K
0.42 × 0.33 × 0.21 mm

Data collection

Enraf–Nonius TurboCAD-4 diffractometer
Absorption correction: none
2374 measured reflections
1960 independent reflections
1173 reflections with I > 2σ(I)
R_int = 0.022
2 standard reflections frequency: 120 min intensity decay: 2%

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.118
S = 1.02
1960 reflections
166 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.21 e Å⁻³

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: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808018783/kp2175sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808018783/kp2175Isup2.hkl

checkCIF report

Comment top

BPAEtCl was synthesized as part of an ongoing program on the investigation of new conjugated polymers derived from bisphenols as potential organic semi-conducting materials (Jaballah et al., 2006). This intermediate is of value in synthetic work inasmuch as the CH₂C1 group can be converted to other groups such as CH₂CN, CH₂OH and CHO. Particularly, the bend-like structure of bisphenol A (BPA) nucleus offers a special interest in metacyclophanes synthesis (Miyazawa et al., 1999). Bis-chloromethyl bisphenol A ethers are also useful as microbicides for control of fungal and bacterial organisms (Priddy & Hennis, 1970). The molecular structure of BPAEtCl is shown in Fig. 1. The two benzene rings are nearly perpendicular, forming a dihedral angle of 87.17 (6)°. The ethoxy group plan [O1—C8—C9] is almost parallel with the benzene ring with the dihedral angle of 6.82 (37)° whereas chloromethyl group plan [C1—C7—Cl] is close to be perpendicular [82.62 (13)°].

Related literature top

For more information on the synthesis, see: Miyazawa et al. (1999). For background to the investigation of new conjugated polymers derived from bisphenols as potential organicsemi-conducting materials, see: Jaballah et al. (2006). For the use of bis-chloromethyl bisphenol A ethers for the control of fungal and bacterial organisms, see: Priddy & Hennis (1970).

Experimental top

BPAEtCl was synthesized in two steps from 4,4'-isopropylidenediphenol [Bisphenol A, BPA]. To a stirred mixture of BPA (10 mmoles) and K₂CO₃ (40 mmoles) in 20 mL of dimethylformamide, was added dropwise bromoethane (30 mmoles). After stirring for 5 h at room temperature, the reaction mixture was poured into distilled water and extracted with diethyl ether. The extract was washed with distilled water, dried over anhydrous MgSO₄, and then evaporated. The resultant crude product was purified by recrystallization from ethanol/water (3/1) to afford the 2,2-bis-(4-ethoxyphenyl)propane [BPAEt] as needle-like white crystals. A mixture of BPAEt (10 mmoles), paraformaldehyde (2.5 g), and 37% aqueous HCl (8.5 mL) in acetic acid (30 mL) was heated at 328 K for 5 h. The resulting mixture was then poured into distilled water and extracted with diethyl ether. The organic layer was washed several times with distilled water and dried over anhydrous MgSO₄. After solvent removal and two recrystallizations from hexane, we obtained BPAEtCl as colourless crystals. Yield: 75%; mp: 352–354 K.

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: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. The molecular structure of BPAEtCl, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted. Symmetry code: (i) -x + 1, y, -z + 5/2.

2,2-Bis(3-chloromethyl-4-ethoxyphenyl)propane top

Crystal data top

C₂₁H₂₆Cl₂O₂	F(000) = 808
M_r = 381.32	D_x = 1.249 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 25 reflections
a = 13.856 (5) Å	θ = 11.6–15.7°
b = 15.185 (6) Å	µ = 0.33 mm⁻¹
c = 10.999 (4) Å	T = 293 K
β = 118.82 (3)°	Prism, colourless
V = 2027.7 (13) Å³	0.42 × 0.33 × 0.21 mm
Z = 4

Data collection top

Enraf–Nonius TurboCAD-4 diffractometer	R_int = 0.022
Radiation source: fine-focus sealed tube	θ_max = 26.0°, θ_min = 2.2°
Graphite monochromator	h = −17→17
non–profiled ω scans	k = −6→18
2374 measured reflections	l = −1→13
1960 independent reflections	2 standard reflections every 120 min
1173 reflections with I > 2σ(I)	intensity decay: 2%

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.036	w = 1/[σ²(F_o²) + (0.052P)² + 0.7485P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.118	(Δ/σ)_max < 0.001
S = 1.03	Δρ_max = 0.25 e Å⁻³
1960 reflections	Δρ_min = −0.21 e Å⁻³
166 parameters

Crystal data top

C₂₁H₂₆Cl₂O₂	V = 2027.7 (13) Å³
M_r = 381.32	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 13.856 (5) Å	µ = 0.33 mm⁻¹
b = 15.185 (6) Å	T = 293 K
c = 10.999 (4) Å	0.42 × 0.33 × 0.21 mm
β = 118.82 (3)°

Data collection top

Enraf–Nonius TurboCAD-4 diffractometer	R_int = 0.022
2374 measured reflections	2 standard reflections every 120 min
1960 independent reflections	intensity decay: 2%
1173 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.118	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.25 e Å⁻³
1960 reflections	Δρ_min = −0.21 e Å⁻³
166 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
HC2	0.2827 (17)	0.0620 (14)	1.052 (2)	0.046 (6)*
HC4	0.5740 (19)	0.1686 (14)	1.147 (2)	0.050 (6)*
H111	0.641 (2)	0.0223 (19)	1.220 (3)	0.085 (9)*
H211	0.6149 (19)	−0.0548 (15)	1.306 (3)	0.052 (6)*
H1C7	0.124 (2)	0.1193 (16)	0.880 (3)	0.064 (8)*
HC5	0.4965 (18)	0.2588 (15)	0.961 (2)	0.051 (6)*
H311	0.5386 (19)	−0.0493 (15)	1.142 (3)	0.056 (6)*
H2C7	0.126 (2)	0.2044 (18)	0.786 (3)	0.077 (8)*
H2C8	0.403 (3)	0.278 (2)	0.719 (3)	0.102 (11)*
H1C9	0.318 (3)	0.390 (2)	0.568 (4)	0.109 (13)*
H2C9	0.217 (3)	0.403 (3)	0.598 (4)	0.128 (14)*
H3C9	0.224 (4)	0.315 (3)	0.524 (5)	0.152 (17)*
H1C8	0.392 (3)	0.362 (2)	0.807 (4)	0.107 (12)*
Cl	0.11729 (5)	0.08024 (5)	0.67435 (7)	0.0780 (3)
C10	0.5	0.04410 (18)	1.25	0.0424 (7)
O1	0.28391 (12)	0.26525 (10)	0.77132 (17)	0.0557 (5)
C3	0.43999 (15)	0.10349 (12)	1.1219 (2)	0.0360 (5)
C1	0.27565 (15)	0.15480 (13)	0.9159 (2)	0.0395 (5)
C5	0.45100 (18)	0.21933 (13)	0.9770 (2)	0.0436 (5)
C2	0.32750 (16)	0.10062 (13)	1.0324 (2)	0.0386 (5)
C4	0.49939 (17)	0.16456 (13)	1.0907 (2)	0.0420 (5)
C6	0.33857 (16)	0.21428 (12)	0.8875 (2)	0.0408 (5)
C7	0.15422 (18)	0.14840 (18)	0.8252 (3)	0.0522 (6)
C11	0.5796 (2)	−0.01497 (17)	1.2272 (3)	0.0600 (8)
C8	0.3483 (3)	0.3195 (2)	0.7315 (4)	0.0752 (9)
C9	0.2741 (4)	0.3638 (3)	0.5969 (4)	0.0863 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl	0.0520 (4)	0.0956 (5)	0.0591 (5)	0.0027 (3)	0.0050 (3)	−0.0129 (4)
C10	0.0475 (15)	0.0365 (14)	0.0313 (17)	0	0.0095 (13)	0
O1	0.0532 (9)	0.0566 (9)	0.0505 (11)	0.0097 (7)	0.0195 (8)	0.0228 (8)
C3	0.0406 (10)	0.0330 (9)	0.0282 (12)	−0.0002 (7)	0.0116 (8)	−0.0029 (8)
C1	0.0371 (10)	0.0412 (10)	0.0358 (12)	0.0050 (8)	0.0141 (9)	0.0017 (9)
C5	0.0467 (11)	0.0390 (10)	0.0434 (14)	−0.0058 (9)	0.0204 (10)	0.0022 (10)
C2	0.0382 (10)	0.0382 (10)	0.0367 (13)	−0.0020 (8)	0.0159 (9)	−0.0001 (9)
C4	0.0358 (10)	0.0433 (11)	0.0363 (13)	−0.0055 (8)	0.0090 (9)	−0.0046 (9)
C6	0.0450 (11)	0.0383 (10)	0.0344 (13)	0.0055 (8)	0.0154 (9)	0.0030 (9)
C7	0.0400 (11)	0.0592 (14)	0.0478 (16)	0.0077 (10)	0.0135 (10)	0.0061 (12)
C11	0.0727 (17)	0.0472 (13)	0.0393 (16)	0.0191 (12)	0.0104 (13)	−0.0055 (12)
C8	0.0762 (19)	0.078 (2)	0.071 (2)	0.0090 (16)	0.0357 (17)	0.0314 (17)
C9	0.102 (3)	0.087 (2)	0.080 (3)	0.027 (2)	0.052 (2)	0.042 (2)

Geometric parameters (Å, º) top

Cl—C7	1.808 (3)	C5—HC5	0.95 (2)
C10—C11ⁱ	1.533 (3)	C2—HC2	0.95 (2)
C10—C11	1.533 (3)	C4—HC4	0.92 (2)
C10—C3ⁱ	1.537 (3)	C7—H1C7	0.99 (3)
C10—C3	1.537 (2)	C7—H2C7	0.95 (3)
O1—C6	1.368 (2)	C11—H111	1.06 (3)
O1—C8	1.430 (3)	C11—H211	0.97 (2)
C3—C2	1.386 (3)	C11—H311	0.98 (3)
C3—C4	1.388 (3)	C8—C9	1.494 (4)
C1—C6	1.392 (3)	C8—H2C8	1.04 (3)
C1—C2	1.395 (3)	C8—H1C8	1.00 (4)
C1—C7	1.489 (3)	C9—H1C9	0.91 (4)
C5—C4	1.377 (3)	C9—H2C9	0.99 (4)
C5—C6	1.387 (3)	C9—H3C9	1.07 (5)
C8—C9	1.494 (4)

C11ⁱ—C10—C11	108.4 (3)	C1—C7—Cl	112.38 (17)
C11ⁱ—C10—C3ⁱ	107.90 (14)	C1—C7—H1C7	107.3 (15)
C11—C10—C3ⁱ	112.29 (13)	Cl—C7—H1C7	106.6 (15)
C11ⁱ—C10—C3	112.29 (13)	C1—C7—H2C7	109.6 (16)
C11—C10—C3	107.90 (14)	Cl—C7—H2C7	102.7 (17)
C3ⁱ—C10—C3	108.1 (2)	H1C7—C7—H2C7	118 (2)
C6—O1—C8	117.78 (18)	C10—C11—H111	111.7 (16)
C2—C3—C4	116.32 (18)	C10—C11—H211	108.1 (14)
C2—C3—C10	123.99 (17)	H111—C11—H211	109 (2)
C4—C3—C10	119.69 (16)	C10—C11—H311	109.7 (14)
C6—C1—C2	119.21 (18)	H111—C11—H311	109 (2)
C6—C1—C7	121.3 (2)	H211—C11—H311	109.5 (18)
C2—C1—C7	119.5 (2)	O1—C8—C9	109.2 (3)
C4—C5—C6	120.0 (2)	O1—C8—H2C8	107.3 (17)
C4—C5—HC5	118.4 (14)	C9—C8—H2C8	109.7 (19)
C6—C5—HC5	121.6 (14)	O1—C8—H1C8	110 (2)
C3—C2—C1	122.58 (19)	C9—C8—H1C8	113 (2)
C3—C2—HC2	119.3 (13)	H2C8—C8—H1C8	108 (3)
C1—C2—HC2	118.1 (13)	C8—C9—H1C9	107 (2)
C5—C4—C3	122.72 (19)	C8—C9—H2C9	115 (2)
C5—C4—HC4	118.3 (14)	H1C9—C9—H2C9	115 (3)
C3—C4—HC4	119.0 (14)	C8—C9—H3C9	109 (2)
O1—C6—C5	123.96 (19)	H1C9—C9—H3C9	110 (3)
O1—C6—C1	116.89 (18)	H2C9—C9—H3C9	101 (3)
C5—C6—C1	119.15 (19)

Symmetry code: (i) −x+1, y, −z+5/2.

Experimental details

Crystal data
Chemical formula	C₂₁H₂₆Cl₂O₂
M_r	381.32
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	13.856 (5), 15.185 (6), 10.999 (4)
β (°)	118.82 (3)
V (Å³)	2027.7 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.33
Crystal size (mm)	0.42 × 0.33 × 0.21

Data collection
Diffractometer	Enraf–Nonius TurboCAD-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	2374, 1960, 1173
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.616

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.118, 1.03
No. of reflections	1960
No. of parameters	166
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.21

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Acknowledgements

The authors gratefully acknowledge financial support from the Ministry of Higher Education, Scientific Research and Technology of Tunisia.

References

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