trans-4-(Tosyl­oxymeth­yl)cyclo­hexane­carboxylic acid

Qing-Rong Qi; Wen-Cai Huang; Hu Zheng

doi:10.1107/S1600536807068572

. 2008 Jan 9;64(Pt 2):o405. doi: 10.1107/S1600536807068572

trans-4-(Tosyloxymethyl)cyclohexanecarboxylic acid

Qing-Rong Qi ^a, Wen-Cai Huang ^b, Hu Zheng ^a,^*

PMCID: PMC2960345 PMID: 21201433

Abstract

The title compound, C₁₅H₂₀O₅S, is an intermediate in the synthesis of a new type of poly(amidoamine) (PAMAM) dendrimer. The cyclohexane ring exhibits a chair conformation, with C—C bond lengths in the range 1.518 (3)–1.531 (3) Å and C—C—C angles in the range 110.45 (19)–112.09 (19)°; these agree well with the values in other cyclohexane derivatives described in the literature. In the crystal structure, adjacent molecules are linked by O—H⋯·O hydrogen bonds. The H atoms of the methyl group are disordered equally over two positions.

Related literature

For related literature, see: Ahmed et al. (2001 ▶); Bucourt & Hainaut (1965 ▶); Dunitz & Strickler (1966 ▶); Grabchev et al. (2003 ▶); Luger et al. (1972 ▶); Wang et al. (2004 ▶); van Koningsveld & Jansen (1984 ▶).

Experimental

Crystal data

C₁₅H₂₀O₅S
M _r = 312.37
Triclinic,
a = 5.9006 (5) Å
b = 7.0880 (9) Å
c = 20.2754 (18) Å
α = 90.371 (3)°
β = 97.479 (2)°
γ = 111.222 (2)°
V = 782.44 (14) Å³
Z = 2
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 293 (2) K
0.53 × 0.48 × 0.12 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.890, T _max = 0.974
7685 measured reflections
3562 independent reflections
2442 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.179
S = 1.01
3562 reflections
195 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.48 e Å⁻³

Data collection: RAPID-AUTO (Rigaku, 2004 ▶); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 1997 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807068572/wn2233sup1.cif

e-64-0o405-sup1.cif^{(19.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807068572/wn2233Isup2.hkl

e-64-0o405-Isup2.hkl^{(174.6KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4O⋯O5ⁱ	0.89 (4)	1.76 (4)	2.654 (3)	178 (3)

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank Mr Kai-Bei Yu of the Chengdu Branch of the Chinese Academy of Science for the X-ray measurements.

supplementary crystallographic information

Comment

PAMAM (poly(amidoamine)) dendrimers have attracted much interest for their symmetry, high degree of branching and high density of terminal functional groups, which can participate in different reactions. The modification of the periphery of PAMAM dendrimers, aimed to change their physical or chemical properties, have been reported recently (Grabchev et al.,2003; Ahmed et al.,2001; Wang et al.,2004). To improve the lipophilicity of PAMAM dendrimers and provide a new type of linker with special stereostructure, a series of cyclohexane derivatives were synthesized. In our synthetic work on PAMAM dendrimers, we obtained the title compound, and report here its crystal structure.

The crystal structure shows that molecules are linked by O—H···.O hydrogen bonds and the cyclohexane ring exists in the chair conformation. The mean C—C bond length of the cyclohexane ring is 1.524 (3) Å, which is close to the value in trans-1,4-cyclohexane dicarboxylic acid (1.523 (3) Å; Luger et al., 1972). The mean endocyclic angle is 111.3 (2)°, which is close to the value for an ideal cyclohexane ring, (C—C—C 111.1°; Bucourt & Hainaut, 1965) and the mean value in trans-1,4-cyclohexanedicarboxylic acid (111.4 (4)°; Dunitz & Strickler, 1966; Luger et al., 1972).

Experimental

trans-4-(Methoxycarbonyl)cyclohexanemethanol (10 mmol), triethylamine (10 mmol) and a small amount of trimethylamine hydrochloride were suspended in dichloromethane (20 ml), and p-toluenesulfonyl chloride (11 mmol) was added dropwise with vigorous stirring at room temperature; after 1 h the reaction was quenched by addition of water. The organic layer which separated was evaporated to give an oil and the oil was hydrolyzed in a methanol and aqueous NaOH (11 mmol) solution for 5 h at 323 K. The title compound was then obtained by acidification with hydrochloric acid and recrystallized from acetone. Colorless crystals suitable for X-ray analysis were obtained by slow evaporation of a cyclohexane and acetone solution at room temperature.