Novel oxiodinium and thiaiodinium compounds

Novel oxiodinium and thiaiodinium compounds having a superior inhibitory effect against micro-organisms coupled with outstanding stability and low toxicity are described.

This invention is further illustrated by the following specific examples: 
EXAMPLE I 
Bis-(dibenz[be][1,4]oxiodinium)sulfate 
A solution of peracetic acid was freshly prepared according to the 
procedure of Collette et al. J. Am. Chem. Soc., 78, 3819 (1956). Two 
hundred fifty milliliters of the solution were placed in a round bottom 
flask equipped with both stirring and cooling means. The solution was 
stirred while a second solution containing 48 g. of 2-iododiphenyl ether 
in 100 ml. of acetic anhydride was added in dropwise fashion. Stirring was 
continued at ambient room temperature for about 14 hours. The reaction 
mixture was then cooled to about 0.degree. C., and 15 ml. of 18 M sulfuric 
acid were added thereto in dropwise fashion. The temperature of the 
reaction was maintained below about 15.degree. C. during the addition. The 
reaction mixture was then allowed to warm up to ambient room temperature 
and was stirred at this temperature for about 5.5 hours. It was then 
poured over about 100 g. of crushed ice. A brownish solid comprising 
dibenz[be][1,4]oxiodinium bisulfate separated. The solid was collected and 
twice recrystallized from a minimal amount of hot water to yield 
bis-(dibenz[be][1,4]oxiodinium)sulfate which melted with decomposition at 
about 250.degree.-252.degree. C. (The recrystallization procedure served 
to convert the bisulfate salt which was the original product of the 
reaction to the sulfate salt.) Analysis-Calc.: C, 42.00; H, 2.35; I, 
36.98; S, 4.67. Found: C, 41.93; H, 2.57; I, 37.13; S, 4.61. 
The aqueous filtrate from the initial filtration of 
dibenz[be][1,4]oxiodinium bisulfate was treated with an excess of a 
saturated sodium chloride solution. An immediate heavy white precipitate 
was formed. This precipitate was collected by filtration and consisted of 
dibenz[be][1,4]oxiodinium chloride. The compound melted with decomposition 
at about 153.degree.-154.degree. C. after recrystallization from a large 
volume of hot water. 
The following compounds were prepared by the method of Example I. 
Bis-(3,7-dichlorodibenz[be][1,4]oxiodinium)sulfate-- 
M.P.=250.degree.-252.degree. C. (with decomposition) Analysis--Calc.: C, 
34.94; H, 1.46; I, 30.80; S, 3.89; Cl, 17.20. Found: C, 34.04; H, 1.92; I, 
29.96; S, 3.60; Cl, 16.62. 
3,7-Dibromodibenz[be][1,4]oxiodinium chloride 
M.P.=255.degree.-256.degree. C. (with decomposition) Analysis--Calc.: C, 
29.51; H, 1.23. Found: C, 29.34; H, 1.36. 
3-Chlorodibenz[be][1,4]oxiodinium chloride 
M.P.=242.degree.-243.degree. C. (with decomposition). 
2,3-Dichlorodibenz[be][1,4]oxiodinium chloride 
M.P.=250.degree.-252.degree. C. (with decomposition). 
1-Chlorodibenz[be][1,4]oxiodinium chloride 
M.P.=226.degree.-228.degree. C. (with decomposition). 
3-Trifluoromethyldibenz[be][1,4]oxiodinium bisulfate 
M.P.=251.degree.-252.degree. C. 
1,3-Dichlorodibenz[be][1,4]oxiodinium chloride 
M.P.=125.degree.-128.degree. C. (with decomposition). 
3,7-Dimethyldibenz[be][1,4]oxiodinium chloride 
M.P.=239.degree.-240.degree. C. Analysis--Calc.: I, 35.39; C, 46.89; H, 
3.37. Found: I, 35.26; C, 47.38; H, 3.56. 
2-Chlorodibenz[be][1,4]oxiodinium chloride 
M.P.=242.degree.-244.degree. C. (with decomposition). 
EXAMPLE II 
Dibenz[be][1,4]oxiodinium phosphate 
A solution of 74 g. of 2-iododiphenyl ether in 75 ml. of chloroform was 
cooled to about 5.degree. C. and was maintained at about that temperature 
with stirring while chlorine gas was introduced just above the surface of 
the solution. A yellow crystalline precipitate of 2-dichloroiododiphenyl 
ether was formed and precipitated. About 300 ml. of hexane were added to 
the solution, and stirring was continued for about 5 minutes. The 
dichloriodo compound was separated by filtration, washed with hexane, and 
dried in air. About 83 g. of 2-dichloriododiphenyl ether were obtained, 
melting at about 70.degree.-72.degree. C. 
Since the compound was somewhat unstable, it was converted immediately into 
the corresponding iodoso compound as follows: 
Two hundred grams of 2-dichloriododiphenyl ether were suspended with 
stirring in 300 ml. of water and the mixture cooled to about 10.degree. C. 
Two hundred forty milliliters of 5 N sodium hydroxide solution were added 
in dropwise fashion. The solution was allowed to warm to room temperature 
and to stand while being stirred for about twelve hours during which time 
the dichloriodo compound was hydrolyzed to the corresponding iodoso 
compound. The iodoso compound was separated by filtration and washed with 
water until the washings were no longer alkaline. 2-Iodosodiphenyl ether 
thus prepared weighed about 157 g. and melted at about 
70.degree.-72.degree. C. 
One hundred fifty grams of 2-iodosodiphenyl ether were added in small 
portions with stirring to 250 ml. of 85 percent phosphoric acid while 
maintaining the mixture at about room temperature. After the addition of 
the iodoso compound had been completed, stirring was continued for about 
eighteen hours. The mixture was then cooled to about 0.degree. C. and 
filtered. The resulting precipitate was washed free from phosphoric acid 
with a small amount of cold acetone. The white crystalline solid 
comprising dibenz[be][1,4]oxiodinium phosphate weighed about 144 g. 
EXAMPLE III 
Bis-(dibenz[be][1,4]oxiodinium)salts 
An aqueous solution containing 5 g. of 
bis-(dibenz[be][1,4]oxiodinium)sulfate in 500 ml. of water was passed over 
an anion exchange resin in the OH.sup.- form. The effluent from the column 
was highly alkaline, indicating that the sulfate anions were being removed 
by the resin and that an aqueous solution of dibenz[be][1,4]oxiodinium 
hydroxide was coming off the column. After 500 ml. of solution had been 
passed through the column, the resin was washed with 250 ml. of deionized 
water. The wash was combined with the effluent, giving a total volume of 
750 ml. Acetic acid was added in dropwise fashion with stirring to an 
aliquot of this solution (which had a pH=13.0) until a pH=5 had been 
attained. The water was removed from the resulting clear solution in 
vacuo. The residue comprising dibenz[be][1,4]oxiodinium acetate was 
dissolved in a minimal amount of anhydrous ethanol. Addition of ether was 
added to the resulting solution caused dibenz[be][1,4]oxiodinium acetate 
to precipitate. The salt was a white crystalline solid melting with 
decomposition at about 160.degree. C. 
Following the above procedure, dibenz[be][1,4]oxiodinium phenate, a cream 
colored solid melting at about 113.degree.-115.degree. C., was prepared. 
Other salts prepared in the same fashion include: 
dibenz[be][1,4]oxiodinium lactate melting at about 122.degree. C. with 
decomposition; dibenz[be][1,4]oxiodinium benzoate melting at about 
108.degree.-110.degree. C.; 3-chlorodibenz[be][1,4]oxiodinium 
methanesulfonate melting at about 207.degree.-209.degree. C.; 
3,7-dichlorodibenz[be][1,4]oxiodinium lactate melting at about 
227.degree.-228.degree. C.; 3,7-dimethyldibenz[be][1,4]oxiodinium 
methanesulfonate melting at about 195.degree.-196.degree. C. and the 
following salts of the dibenz[be][1,4]oxiodinium cation: salicylate 
M.P.=180.degree.-182.degree. C.; 1-naphthalenacetate 
M.P.=180.degree.-181.degree. C.; 2-benzoylbenzoate 
M.P.=175.degree.-176.degree. C.; 2-naphthalenesulfonate 
M.P.=222.degree.-224.degree. C.; 3,4-dichlorobenzenesulfonate 
M.P.=210.degree.-212.degree. C.; dihydrogenphosphate 
M.P.=245.degree.-246.degree. C.; methanesulfonate 
M.P.=220.degree.-223.degree. C.; and 3-chlorodibenz[be][1,4]oxiodinium 
methanesulfonate M.P.=207.degree.-209.degree. C. 
Salts of the oxiodinium cations coming within the scope of formula I can be 
prepared by substituting the corresponding acid for acetic acid in the 
above example while using the appropriate oxiodinium sulfate or bisulfate 
as a source of the cation.