O,O′-Diisopropyl S-[2-(benzene­sulfon­amido)­eth­yl]phospho­rodithio­ate

Hai-Feng Wu; Xin-Yi Liu; Fan-Hua Zhang; Yun-Xiao He

doi:10.1107/S160053681105536X

. 2012 Jan 7;68(Pt 2):o282. doi: 10.1107/S160053681105536X

O,O′-Diisopropyl S-[2-(benzenesulfonamido)ethyl]phosphorodithioate

Hai-Feng Wu ^a,^*, Xin-Yi Liu ^a, Fan-Hua Zhang ^a, Yun-Xiao He ^a

PMCID: PMC3274979 PMID: 22346924

Abstract

The molecular conformation of the title compound, C₁₄H₂₄NO₄PS₃, the selective herbicide bensulide, is stabilized by a weak intramolecular C—H⋯S interaction. In the crystal, chains are formed through intermolecular N—H⋯S hydrogen bonds.

Related literature

For applications of N-(β-diorganodithiophosphorylethyl) aryl and alkyl sulfonamides in the field of agrochemicals, see: Llewellyn & Chester (1963 ▶). Bensulide is a selective organophosphate herbicide which is mainly used on vegetable crops such as carrots, cucumbers, peppers and melons, see: Meister (1992 ▶). For the synthesis, see: Llewellyn & Jeffrey (1978 ▶).

Experimental

Crystal data

C₁₄H₂₄NO₄PS₃
M _r = 397.49
Monoclinic,
a = 8.6431 (17) Å
b = 24.465 (5) Å
c = 9.875 (2) Å
β = 104.99 (3)°
V = 2017.1 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.46 mm⁻¹
T = 293 K
0.37 × 0.35 × 0.27 mm

Data collection

Rigaku R-AXIS RAPID CCD diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.843, T _max = 0.883
19632 measured reflections
4605 independent reflections
3083 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.127
S = 1.11
4605 reflections
208 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Data collection: RAPID-AUTO (Rigaku, 1998 ▶); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPII (Johnson, 1976 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681105536X/zs2173sup1.cif

e-68-0o282-sup1.cif^{(18.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681105536X/zs2173Isup2.hkl

e-68-0o282-Isup2.hkl^{(225.6KB, hkl)}

Supplementary material file. DOI: 10.1107/S160053681105536X/zs2173Isup3.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
N—H0A⋯S1ⁱ	0.86	2.86	3.496 (2)	132
C7—H7B⋯S1	0.97	2.83	3.447 (3)	122

Open in a new tab

Symmetry code: (i) Inline graphic .

Acknowledgments

We thank Professor Yueqing Zheng (Ningbo University, Ningbo, China) for helpful discussions and Wenxiang Huang for the X-ray data collection.

supplementary crystallographic information

Comment

N-(β-Diorganodithiophosphorylethyl) aryl and alkyl sulfonamides are known for their applications in the field of agrochemicals because of their significant biological properties (Llewellyn et al., 1963). The title compound C₁₄H₂₄NO₄PS₃ (I), with the common name bensulide, is a selective organophosphate herbicide which is mainly used on vegetable crops such as carrots, cucumbers, peppers and melons (Meister, 1992). This typical organic phosphorus compound is one of our plant products that can be synthesized by combining the sodium salt of 2-(phenylsulfonamido)ethyl sulfate (II) and O,O'-diisopropyl phosphorodithioate (III) (Llewellyn et al., 1978) (Fig. 3).

In the title compound (Fig. 1), bond distances and angles are as expected. The P atom is coordinated by two S atoms and two O atoms. The O1—P—S1, S1—P—S2 and O2—P—S1 bond angles [117.91 (7), 114.48 (5), 111.46 (7)°, respectively] are larger than those for angles O2—P—S2, O1—P—O2 and O1—P—S2 [108.85 (8), 102.35 (9), 100.58 (7)°, respectively], indicating a distorted tetrahedral configuration. The molecular conformation is stabilized by weak intramolecular C—H···S and C—H···O interactions and one-dimensional chains are formed through intermolecular N—H···S hydrogen bonds (Table 1, Fig. 2).

Experimental

A 30% aqueous solution of sodium 2-(phenylsulfonamido)ethyl sulfate [(II), 0.5mol] was added to a 30% aqueous solution of sodium O,O'-diisopropyl phosphorodithioate [(III), 0.5 mol]. Addition of 50% aqueous sodium hydroxide brought the pH to 10.5. The mixture was then heated to 85 °C for 4 h with vigorous stirring after which the reaction flask was cooled to 25 °C. The pH was lowered from 12 to approximately 8 by the addition of concentrated sulfuric acid. The product was extracted with toluene (400 ml), washed with 2% sodium bicarbonate solution followed by a saturated sodium chloride solution, then dried and evaporated. Recrystallization from toluene gave colourless blocks of (I).