Process Development of 1,2-Benzisothiazolin-3(2H)-one by Replacing of the Toxic Materials

Abstract

1,2-Benzisothiazolin-3(2H)-one (2) was synthesized by 2,2′-dithiodibenzoic acid (1) with acetamide or urea in high yield via one-pot amidation-cyclization process.

1,2-benzisothiazolin-3(2H)-one - amidation-cyclization - one-pot-procedure

References

<A NAME="RU13803ST-1">1</A>

Dozen Tech Company, Ltd., 955-1 Dohwa, 402-060 Incheon, Republic of Korea.

<A NAME="RU13803ST-2">2</A> Mckibben M. McClelland EW. J. Chem. Soc.  1923,  123:  170 

<A NAME="RU13803ST-3A">3a</A> Morley JS. inventors; British Patents,  848,130.  ; Chem Abstr. 1961, 55, 9430

<A NAME="RU13803ST-3B">3b</A> Morley JS. inventors; British Patents,  861,379.  ; Chem Abstr. 1961, 55, 22723

<A NAME="RU13803ST-3C">3c</A> Gialdi F. Ponci R. Caccialonza P. Mycopathol. Mycol. Appl.  1964,  24:  163 

<A NAME="RU13803ST-3D">3d</A> Fisher R. Hurni H. Arzneim.-Forsch.  1964,  14:  1301 

<A NAME="RU13803ST-3E">3e</A> Fisher R. Hurni H. Arzneim.-Forsch.  1964,  14:  1306 

<A NAME="RU13803ST-4">4</A> Neustadt PT, and Ludwigshafen HJ. inventors; U. S. Patent,  4,736,040. 

<A NAME="RU13803ST-5A">5a</A> McClelland EW. Gait AJ. J. Chem. Soc.  1926,  921 

<A NAME="RU13803ST-5B">5b</A> Grivas JC. J. Org. Chem.  1975,  40:  2029 

<A NAME="RU13803ST-5C">5c</A> Yevich JP. New JS. Smith DW. Lobeck WG. Catt JD. Minielli JL. Eison MS. Taylor DP. Riblet LA. Temple DL. J. Med. Chem.  1986,  29:  359 

<A NAME="RU13803ST-5D">5d</A> Miura Y. J. Org. Chem.  1988,  53:  2850 

<A NAME="RU13803ST-5E">5e</A> inventors; J.P. Patent Appl. No.  176752. 

<A NAME="RU13803ST-5F">5f</A> Shimizu M. Kikumoto H. Konakahara T. Gama Y. Shibuya I. Heterocycles  1999,  51:  3005 

<A NAME="RU13803ST-5G">5g</A> Chiyoda T. Iida K. Takatori K. Kajiwara M. Synlett Lett.  2000,  1427 

<A NAME="RU13803ST-5H">5h</A> inventors; J.P. Patent Appl. No.  266310. 

<A NAME="RU13803ST-6A">6a</A> Vitali T. Amoretti L. Plazzi V. Farmaco Ed. Sci.  1968,  23:  1075 

<A NAME="RU13803ST-6B">6b</A> Grivas JC. Chem. Abstr.  1972,  76:  46193n 

<A NAME="RU13803ST-6C">6c</A> Davis M. Adv. Heterocycl. Chem.  1972,  14:  58 

<A NAME="RU13803ST-6D">6d</A> Butti A. Gazzani G. Chem Abstr.  1977,  86:  145938x 

<A NAME="RU13803ST-6E">6e</A> Kamigata N. Hashimoto S. Kobatashi M. Nakanishi H. Bull. Chem. Soc. Jpn.  1985,  58:  3131 

<A NAME="RU13803ST-6F">6f</A> Bryce MR. Dransfield TA. Kandeel KA. Vernon JM. J. Chem. Soc., Perkin Trans. 1  1988,  2141 

<A NAME="RU13803ST-6G">6g</A> Scurlock R. Rougee M. Bensasson RV. Evers M. Dereu N. Phytochem. Photobiol.  1991,  54:  733 

<A NAME="RU13803ST-6H">6h</A> Daich A. Decroix B. J. Heterocycl. Chem.  1991,  28:  1881 

<A NAME="RU13803ST-6I">6i</A> Wright SW. Petraitis JJ. Abelman MM. Bostrom LL. Corbett RL. Green AM. Kindt RM. Magolda RL. Bioorg. Med. Chem. Lett.  1993,  3:  2875 

<A NAME="RU13803ST-6J">6j</A> Kim W. Dannaldson J. Gates KS. Tetrahedron Lett.  1996,  37:  5337 

<A NAME="RU13803ST-6K">6k</A> Kagano H, Goda H, Yoshida K, Yamamoto M, and Sakaue S. inventors; U. S. Patent  5,633,384.  ; and references cited therein

<A NAME="RU13803ST-7">7</A>

Procedure of 1,2-Benzisothiazolin-3(2H)-one (2).¹¹ To a 1000 L reactor was equipped with a mechanical stirrer, a thermometer, and a condenser, 28% NaOMe (52.1 kg) in MeOH solution was added for 10 min and distilled under reduced pressure (60 °C/750 mmHg, 2.5 h) to get the MeOH (15 L). In order to get rid of the extra MeOH, toluene (100 kg) was added and distilled to get the MeOH (15 L) for 1.5 h. Acetamide (16 kg) was added and refluxed for 1 h, then, the reactor was cooled to 25 °C. Dimethyl 2,2′-dithiodibenzoate (3) (23.5 kg) was slowly added at 25 °C, the reaction mixture was refluxed at 80 °C for 2 h, cooled to <20 °C, added H₂O (150 L), stirred for 30 min, filtered, and separated to give aqueous layer and toluene layer (70 kg). The aqueous layer was added 28% H₂O₂ (12 kg) dropwisely for 30 min (increasing temperature to 50-55 °C). The basic active carbon (3 kg) and Al₂O₃ (DN-3) (300 g) were added, stirred for 1 h at 25 °C, and filtered. Addition of conc. HCl (20 kg, 35% solution, and pH = 3-4) was added dropwisely to precipitate the wet 1,2-benzisothiazolin-3(2H)-one (2), which was filtered, washed with cold water (30 L), and dried on air to afford 2 (18 kg, 85%) as off-white solid (MeOH), mp 157-158 °C (lit. [12] mp 158-159 °C).
IR (KBr): 3420, 3056, 2911, 1630 cm^-1.
¹H NMR (300 MHz, CDCl₃): δ = 1.37 (s, 9 H), 5.70 (br s,
1 H), 6.53 (d, 1 H, J = 1.7 Hz), 7.37-7.62 (m, 5 H), 11.64
(br s, 1 H).
Anal. Calcd for C₇H₅NOS: C, 55.61; H, 3.33; N, 9.26; S, 21.21. Found: C, 55.45; H, 3.50; N, 9.52; S, 21.08.

<A NAME="RU13803ST-8">8</A>

The purity of 2 was verified by HPLC analysis employing the Shimadzu LC-6A instrument equipped with an SPD-6A UV detector as follows: Compound 2: Detector, Youngjin M 720; pump, waters 510; integrator, waters 746, Youngjin D 520B; wave length, UV-225 nm, column, ODS-2 (250 nm × 4.6Ψ); end time, 30 min; eluent MeOH-H₂O (35:65, v/v); flow rate, 1.0 mL/min; attenuation, 1.28; chart speed, 0.5.
Procedure is as follows: 10 mg standard 1,2-benzisothiazolin-3(2H)-one (BIT) (2) is weighed to 0.1 mg accuracy in 100 mL flask and added 10 mL of 0.5 (w/v)% methylbenzoate/MeOH. The flask is filled up with HPLC eluent to 100 mL. Compound 2 is prepared as same as standard BIT. At least three HPLC tests are conducted until constant areas are obtained. Compound 2 assay is calculated from the HPLC area in proportion to standard BIT. Calculation was conducted as follows: Compound 2 assay = (the area of compound 2 ÷ the area of methylbenzoate)/(the area of standard BIT ÷ the area of methylbenzoate) × 100.

<A NAME="RU13803ST-9">9</A> Oae M. Doi JT. Organic Sulfur Chemistry: Structure and Mechanism   CRC Press; Boca Raton, Ann Arbor, Boston, London: 1991.  p.230 

<A NAME="RU13803ST-10">10</A> Neustadt PT, and Ludwigshafen HJ. inventors; U. S. Patent  4,736,040. 

<A NAME="RU13803ST-11">11</A> Nam KS, and Lee WS. inventors; KR Appl. No.  2001-43498. 

<A NAME="RU13803ST-12">12</A> Miura Y. J. Org. Chem.  1988,  53:  2850