N-(4-Amino­pyrimidin-5-yl)-4-methyl-N-(4-methyl­phenyl­sulfon­yl)benzene­sulfonamide

Abu Taher; Vincent J Smith

doi:10.1107/S1600536812046442

. 2012 Nov 17;68(Pt 12):o3362. doi: 10.1107/S1600536812046442

N-(4-Aminopyrimidin-5-yl)-4-methyl-N-(4-methylphenylsulfonyl)benzenesulfonamide

Abu Taher ^a,^*, Vincent J Smith ^a

PMCID: PMC3588960 PMID: 23476196

Abstract

In the title compound, C₁₈H₁₈N₄O₄S₂, the mean planes passing through the tosyl benzene rings form dihedral angles of 48.42 (9) and 15.1 (1)° with the aminopyrimidine ring. In the crystal, molecules associate via N—H⋯N and N—H⋯O hydrogen bonds, forming extended hydrogen-bonded sheets that lie parallel to the bc plane. The N—H⋯N hydrogen bonds propagate along the b-axis direction, while the N—H⋯O hydrogen bonds propagate along the c-axis direction.

Related literature

For the synthesis of related sulfonamides, see: Schetty (1969 ▶); Taher & Smith (2012 ▶). For applications of ring-closing metathesis (RCM) on sulfonamide-protected allyl-containing substrates, see: Yadav et al. (2011 ▶); Panayides et al. (2007a ▶,b ▶).

Experimental

Crystal data

C₁₈H₁₈N₄O₄S₂
M _r = 418.48
Monoclinic,
a = 36.559 (9) Å
b = 6.9044 (18) Å
c = 15.524 (4) Å
β = 103.852 (3)°
V = 3804.6 (17) Å³
Z = 8
Mo Kα radiation
μ = 0.31 mm⁻¹
T = 103 K
0.13 × 0.13 × 0.10 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.962, T _max = 0.969
11288 measured reflections
4459 independent reflections
3156 reflections with I > 2σ(I)
R _int = 0.041

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.116
S = 1.04
4459 reflections
254 parameters
H-atom parameters constrained
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.58 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶; Atwood & Barbour, 2003 ▶); software used to prepare material for publication: X-SEED.

Supplementary Material

Click here for additional data file.^{(21.3KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812046442/hg5262sup1.cif

e-68-o3362-sup1.cif^{(21.3KB, cif)}

Click here for additional data file.^{(218.6KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812046442/hg5262Isup2.hkl

e-68-o3362-Isup2.hkl^{(218.6KB, hkl)}

Click here for additional data file.^{(7.2KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536812046442/hg5262Isup3.cml

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
N3—H3A⋯O1ⁱ	0.88	2.16	3.036 (3)	178
N3—H3B⋯N1ⁱⁱ	0.88	2.30	2.986 (3)	135

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

AT thanks the National Research Foundation (NRF), Pretoria, for providing an Innovation Fellowship and Professor W. A. L. van Otterlo for his research oversight. Stellenbosch University’s Science Faculty is also acknowledged for providing the laboratory space and addition financial research support.

supplementary crystallographic information

Comment

The para-toluene sulfonyl group (Ts) is frequently used as a protecting group for amines, particularly when monoalkylation of the amine is desired as the sulfonamide can then be cleaved in a subsequent step. The van Otterlo research group have successfully utilized the Ts group during their syntheses of annulated heterocycles using ring-closing metathesis (RCM) and isomerization strategies (see for example: Panayides et al., 2007a, 2007b; Yadav et al., 2011). In this present research the main aim was to synthesize pyrimidine-annulated heterocycles in which a 4,5-disulfonamide-protected 4,5-diaminopyrimidine was required. Surprisingly, instead of the desired 4,5-diTs compound the isomeric 5,5-disulfonamide-protected 4,5-diaminopyrimidine was obtained. It should be pointed out that according to literature it is uncommon for this type of ditosylation to occur on one amine in the presence of another amine group [see for instance Schetty (1969) and Taher et al. (2012)].

Experimental

To an ice-cooled solution of 4,5-diaminopyrimidine (0.100 g, 0.908 mmol) in pyridine (10 ml), was slowly added 4-methylbenzene-1-sulfonyl chloride (0.380 g, 2.00 mmol). The mixture was then stirred at 273.15 K for 2 h. After completion of the reaction, as monitored by TLC, ice-cooled water (10 ml) was added to the reaction mixture. A white solid precipitate was formed which was collected by filteration and washed with dilute HCl (15 ml, 1 M) and plenty of water, after which it was dried in an oven (373.15 K). The residue was recrystallized from MeOH/CH₂Cl₂ to afford the product N-(4-aminopyrimidin-5-yl)-4-methyl-N-tosylbenzenesulfonamide as a colourless crystalline material (0.357 g, 94%).