CA1156247A - 4-halogeno-oxetan-2-ones and process for their production - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

Novel compounds having the formula I

(I) are described wherein x is a chlorine bromine or iodine atom and Y
is a residue having the formula RIR2R3C- where n R and R are the same or different and each is a fluorine chlorine or bromine atom and R3 is a hydrogen,fluorine chlorine or bromine atom a group -CR R5P6 a cyano group, a group-COR7 or -Po(R8)2 wherein R R5 R6 independently, are F, Cl or Br R7 and R8 are the same or differ-ent and each is a chlorine atom or a group -oR9 wherein R9 is a Cl-C4 straight chain or branched alkyl group with the proviso that when X is chlorine- atom none of R1 R2 R3, R4 R5 and R6 can be a bromin atom They can be obtained by reacting dikecane with a compound XY in the presence of an agent capabl of forming free radical, Compounds have biocital aceivity against various organism, e,g, bacteria fungi and algae. They are paticularly suitable for antifoulant composi-tions.

Description

1 15~247 6-12780/MA 1766/~

4-Halo~eno-oxetan-2-ones and process for their production .

The present invention relates eo ~e~ 4-halogeno-oxetan-2-ones, a pro-cess for their production, as well as antifoulant composieions~contain-ing said 4-halogeno-oxatan-2-ones as active ingredients.

~ccorting co the pr2sent invention, ehere are provided compounds having the formula I

Y C~2 i f (I) wherein X is a chlorine, bromine or iodine atom and Y is a residue having the formula RlR2R3C-, wherein Rl and R2 are the same or differ-ent and each is a fluorine, chlorine or bromine atom and R3 i9 a hydrogen, fluorine, chlorine or bromine atom, a group -CR4R5R6, a cyano group,a group -COR or -PO~R )2 ~hereLn R , R , R ,independently, are F, Cl or ~r, R7 and R ar~ the jame or different and each is a chlorine atom or a group -oR9 wherein R9 is a Cl-C4 straight chain or branched alkyl group ~ith the proviso that when X is a chlorine atom, none of Rl, R2, R , R4, R5 ant R6 can be a bromine atom.

When R is a Cl-C4 alkyl group, it may be a methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.butyl or t-butyl group. X preferably repre-sents a chlorine or bromine atom. Rl, R and R3 preferably are each a fluorine, chlorine or bromine atom. Specific Examples of compounds of formula I include:
~k 4-Chloro-4-(2,2,2-trichloroethyl)oxetan-2-one, 4-bromo-4-(2-chloro-

2,2-difluoroechyl)oxetan-2-one, 4-bromo-4-(2-bromo-2,2-difluoroethyl)-oxetane-2-one, 4-bromo-4-(2,2~2-trichloroethyl)oxetan-2-one, 4-bromo-4-(2-bromo-2,2-dichloroethyl)oxetan-2-one, 4-bromo-4-(2,2,2-~ribromo-echyl)oxeean-2-one, 4-chloro-4-(2-chlorocarbony1-2,2-dichloroethyl)-oxetan-2-one, 4-chloro-4-(2,2-dichloro-2-methoxycarbonylethyl)oxetan-2-one, 4-chloro-4-(2,2-dichloro-2-ethoxycarbonylethyl)oxetan-2-one, 4-chloro-4-(2,2-dichloro-2-n-butoxycarbonylethyl~oxetan-2-one, 4-chloro-4-(2,2-tichloro-2-dichlorophosphonylethyl)oxetan-2-one, 4-chlorQ-4-(2,2-dichloro-2-tiethylphosphonoethyl)oxetan-2-one, 4-chlor.o-4-(2,2~dichloro-2-cyanoethyl)oxetan-2-one, 4-bromo-4-(2,2-dihromo-2-methoxycarbonylethyl)oxetan-2-one, 4-bromo-4-(2,2-dibromo-2-cyanoethyl)oxetan-2-one, 4-chloro-4-(2,2,3,3,3-pentachloropropyl)-oxetan-2-one, 4-bro -4-(2-bromo-2 r 3,3,3-tetrachloropropyl)oxetan-2-one, 4-bromo-4-(2-bromo-2-chloro-3,3,3-trifluoropropyl)oxetan-2-one, and 4-iodo-4-(2,2,2-trifluoroethyl)oxetan-2-one.

Preferred compo.unds of formula I incIude: 4-Chloro-4-(2,2,2-trichloro-ethyl)oxetan-2-one, 4-bromo-4-(2,2,2-trichloroethyl)oxetan-2-one, 4-bromo-4-(2,2,2-tribromoethyl)oxetan-2-one, 4-chloro-4-(2,2-dichloro-2-ethoxycarbonyl-ethyl)oxetan-2-one, and 4-bromo-4-(2-chloro-2-bromo-

3,3,3-trifluoropropyl)oxetan-2-one.

The present invention al90 provides a process for the production of compounds of formula I comprising reacting diketene with a compound XY in.the presence of an agent capable of forming free radicals.

Examples of compounds XY are tetrahalomethanes such as carbontetra-chloride, carbontetrabromide or bromotricbloromethane; trihalomethyl compounds such as ethyltrichloroacetate, trichloromethylphosphonyldi-chloride, trichloroacetonitrile, l-chloro-l,l-dibromotrifluoroethane or hexachloroethane.

Agents forming free radicals i~clude for cxample:
i~ Ionising radiation;
ii) Ultraviolet radiation;
iii) Organic peroxides e.g. t-butylperacetate, t-butylperbenzoate, acetylperoxide, benzoylperoxide, di-isopropylperdicarbonate, bis-(t-butylcyclohexyl)-perdicarbonate, di-t-butylperoxide, and t-butyl-hydroperoxide;
iv) Inorganic peroxy compounds e.g. hydrogen peroxide and~a = nium persulphate;
v~ Orgsnic azo compounds e.g. azobisisobutyronitrile, and azobis-isopropane;
vi) Combination of iii) or v) with ultraviolet radiation;
vii) Combination of iii) or iv), with a metal ion catalyst, e.g. Cu, Ti, V, Fe to give a radical producing redox-system e.g.

H22 + Fe NH + O S-O-O-SO NH4 ~ Cu t-Butylhydroperoxide + Ti Preferred agents forming ree raticals are organic peroxides, organic azo compounds, and combinations of organic peroxides or organic azo compounds with ultraviolet ratiation.

The radical forming substances [iii), iv), v)] may be used advantage-ously in catalytic amounts-of 0.1-10 mol~, preferably 1-5 mol%, based on diketene. The preferred molar ratio of compound XY to diketene i9 from 1:1 to 20:1. In the above process, the reactant XX may act as the solvent but, if desired, the reaction may optionally be carriet out in the presence of a solvent inert under the reaction conditions e.g. petroleum ether in low temperature reactions; benzene, toluene or carbon tetrachloride in moderate temperature reactions; or chloro-benzene in high temperature reactions. The reaction may be effected under conditions well-known per se e.g. in the temperature range -20C

to 1;0C, according to ehe radical producing ~ethod employed, pre-fsrably be~ween 0C to 100C; and, if the compound XY is a gas, optionally in an inert gas atmosphere and optionally under pressure.
The reactions can be carried out batchwise, or, preferably, in a con-tinuous manner, for example in a cascade reactor.

Compounds of formula I show broad spectrum biocidal activity in the range of 1000 ~g/ml and lower against a range of organisms. In parti-cular the compounts of formula I control the growth of bacteria, fungi and aIgae, at low concentration. The compounds of formula I are also useful as intermediate~ for a wide variety of chemirals.

Accordingly, the present invention also provides antifoulant composi-tions comprising, as active ingredient, a compound of formula I, optionallg in admixture with suitable carriers.

They are particularly effective in~controlling the growth of bacteria, fungi and algae in still or circulating water systems, for example in industrial cooling towers, swimming pools etc., in other aqueous-based or oil-based systems e.g. cutting fluids and secondary oil re-covery processes; in industrial processing waters e.g. processing waters in woot, pulp, paper~ te~tiles and leather processing; and in surface disinfection e.g. in hospitals, dairies etc.

The compounds of formula I can be applied as biocides in pure form or as concentrated or dilute solutions or emulsions, which may be option-ally stabilised with alkali- or alkaline earth metal carbonates. It is also possible to apply them in admixture with solit carriers. The compounds can also be applied as suspensions in liquid compositions, in which case wetting agents or emulsifiers may be used to assist the distribution of the active ingredient to form homogeneous disper-sions. If desired, the compounds may be used together with other biocides.

1 lSfi2A7 One field of appLication is the treatment of cooling wa~er. For pro-tection against the growth of microorganisms, the active compounds can advantageously be added direct to the cooling water.

When using the compounds for treating water, it is possible to add simultaneously other additives, for example, corrosion inhibitors, antiincrustants, water softeners, complexing agents and low foaming surfactants or penetrants, for example, polymeric phosphites, phos-phates 9 amides of phsophoric acids, polymeric carboxylic acids or anhydrides, for example polyacrylic acids or polymaleic acids, or salts thereof and other additives.

Organisms whose growth is controlled include for example:

Class/type Examples Problems caused Algae Green Chlorella vulgaris . General matting Chlorella pyrenoitosa Scenedesmus spec. and fouling Vlothrix subtilissima usually by Blue-green Oscillatoria geminata Nostoc spec. blocking of pipes Phormidium foveolarum Anacystis nidulans pumps, filters, etc.
Brown Tribonema aequale Bacteria Gram positive Bacillus cereus var. mycoides Bacillus subtilis Bacterlal slimes Streptomyces griseus Streptomyces aureofasciculu5 produced which Staphylococcus aureus cause reduced Gram negative Pseudomonas aeruginosa Aerobacter aerogenes plant efflciency Serratia marcescens Alcaligenes denitrificans and mcreased Escherichia coli Proteus vulgaris corroslon.

_lass/type Examples Problems caused ~aerobic Desulphovibrio desulphuricans H2S produced Sulphate w~th resultant retucing severe corrosion.
Fung Aspergillus niger Surface rot, Aspergillus phoenicus Penicillium funiculosum d~scolouratlon, Alternaria alternata slime production Cladosporium cladosporioides Candita albicans and internal Endomyces geotrichum wood decay.
Aureobasidium pullulans The foLlowing Examples, in which parts and percentages are by weight, further illustrate the present invention.

Example l: A mixture of 25.2 parts of diketene, 62.7 parts of bromo-trichloromethane and 1.5 parts of azobisisobutyronitrile dissolved in 978 parts of carbon tetrachloride was irradiated by W light at room ~emperature (20-25C) for 5 hours. The mixture was evaporated at the water pump and the product, 4-bromo-4-(2,2,2-trichloroethyl)-oxetan-2-one, was obtained as a yellow oil which crystallised on cooling. Recrystallis~ation of this material three times from light petroleu~ ether (b.p. 40-60C) gave white needles m.p. 55-56C.
CalcuLated for C5H4BrC1302: C 21.27; H 1.43 Found C 21.09; H 1.53.

: 2.0 parts of benzoyl peroxide (containing 252 of water) were dissolved in 163 parts of carbon tetrachloride and dried over magnesium sulphate. To the filtered dry solution were added 42 parts of diketene ant the resulting solution was added dropwise over 5 hours to 815 parts of refluxing carbon tetrachloride. After completion of the addition the mixture was heated for a further 1 hour, then evapo-rated to dryness on the water pump. Extraction of the product into hot petroleum ether gave 4-chloro-4-(2,2,2-trichloroethyl)oxetan-2-one, shown to be 95% pure by GLC (ground level concentration).

, Distillation of a portion of the extracted material gave an analytical-ly pure sample, b.p. 70-75C at 0.0133 mb(millibar).
Calculated for C5H4C1402 C 25.25; H 1-69; Cl 59-61 Found C 25.47; H 1.87; Cl 59.62.

Example 3: 210 psrts of freshly distilled diketene and 30 part~ of bis-(t-butylcyclohexyl~perdicarbonate were dissolved in 795 parts of car-bon tetrachloride. This solution was added dropwise over l~hour, with stirring, to 3180 parts of carbon tetrachloride held at reflux tempe-rature in an atmosphere of dry nitro~en. When the addition was comp-lete, stirring at reflux temperature was continued for 1 hour and the solution was then allowed to cool. The excess carbon ~etrachloride was distilled off on a rotary evaporator under water pump vacuum at a bath temperature of 30-40C. The crude product was purified by distil-lation on a wiped-wall still giving 398 parts of pure 4-chloro-4-(2,2,2-trichloroethyl)oxetan-2-one.

Example 4: A carbon tetrachloride solution containing 26.35 parts di-ketene and 3.76 parts of bi~-(t-butylcyclohexyl)-perdicarbonate per 1592 parts of carbon tetrachloride was pumped through a two vèssel csscade at such a rate as to give residence time of 60 ~inutes (resi-dence time - vessel volume~vo-lume pumped per minute). The vessels were stirred vigorously ant heated at carbon tetrachloride reflux tem-perature. The product stream contained 2.5 parts unreacted diketene and 67 parts of 4-chloro-4-(2,2,2-trichloroethyl)oxetan-2-one per 1592 parts carbon tetrachloride.

Bxample 5: A mixture of 8.4 parts of diketene, 33.1 parts of carbon tetrabromide, 0.5 part3 of bis-(t-butylcyclohexyl)perdicarbonate and 326 parts of carbon tetrachloride was heated at 60~C for 2 hours, then evaporated at the water pump. The residue was recrystalliset twice from light petroleum ether (b.p. 40-60C) and the product,

4-bromo-4-(2,2,2-tribromoethyl)oxetan-2-one, obtained as white need-lesrm.p. 71-73~C.

Calculated for C5H4Br402 C 14-4S; H 0.97; Br 76-89 Found C 14.75; H 0.97; Br 76.20.

Example 6: A mixture of 8.4 parts of diketene, 19.2 parts of ethyl trichloroacetate and 1.3 parts of bis-(t-butylcyclohexyl)perdicarbonate was added dropwise over 3 hours to 96 parts of ethyl trichloroacetate stirred at 85C in a nitrogen at sphere. After the addition, the mix-~ure was stirred at 85C for a further L~2 hour, then the ùnreacted starting materials were removed-on a wiped wall still at 90C/0.27 mb.
The residue was distilled twice in a Kugelrohr at 100C~0.33 mb. IR
and NMR on the distillate showed the major component to be 4-chloro-4-(2,2-dichloro-2-ethoxycarbonyl-ethyl)oxetan-2-one.

Example 7: 1.68 parts of diketene and 0.4 parts of bis-(t-butylcyclo-hexyl)perdicarbonate were dissolved in 25 parts n-hexane and added over 1 hour to a stirred ~olution of 5.53 parts of l-chloro-l,l-di-bromotrifLuoroethane in 25 parts n-hexane at 60C. The mixture was stirred a further l.S hours at 60C,then cooled to room temperature.
The solution was decanted from an insoluble oil,then evaporated cold in vacuo~to give 3.8 parts of 4-bromo-4-(2-chloro-2-bromo-3,3,3-tri-fluoropropyl~oxetan-2-one as a mobile yellow oil, with a characteristic I.R. carbonyl frequency of 1860 cm 1.

Example 8: A mixet culture of slime-forming bacteria including Pseu-domonas aeruginosa, Enterobacter aerogenes, Escherichia coli, Proteus w lgaris, Bacillus mycoides and Staphylococcus aureus in saline containing 107 organisms~ml was treated with 30 ppm of the product of Example 2. After one hour, the number of organisms had been re-duced to 102 organisms~ml and within 24 hours all the bacteria had been killed, thereby temonstrating the high bacteriocidal activity of the product of Example 2.

1 1562~7 Example 9: Test demonstrating algistat~
The organisms against which the compounds are to be tested are grown in an Erlenmeyer flask in a nutrient medium under sterile conditions oll a shaking ~ater bath at 18C with exposure (14 hours in light alter-nating with 10 hours in the dark).

Tests are carried out against three algae, namely the blue algae a~ Phormidium foveolarum (A) which lives in polluted water or moist earth and forms trichomes;

the green algae b) the simple filament-forming Ulothrix subtilissima (B) generally found at colder times of the year in rapidly flowing water;

and the algae with brown chromatophors c) the widespread, unbranched filament-forming Tribonema aequale (C) occurring in bodies of water especially in the spring at low tempera-ture or in the autumn, even in mild winters.

The composition of the medium is as follows (according to Algae broth, Difco Laboratories):
1.0 g o NaN03, 0 05 g of CaC12, 0.058 g of CaC12, 0.5 g of MgSa4 7 H20, 0.25 g of K2HP04, 0.003 g of FeC13, dissolved in 1 litre o distilled water. The nutrient medium treated with the biocide is innoculated with the respective algae suspension such that a final dilution of V100 (algae divided with a stirrer) is attained. Evaluation is made after a 3 week incubation in the Erlen-meyer flask on a shaking water bath. The activity is reported as the minimum inhibitory concentration (MIC in mg/l) which indicates that algicide concentration at which the growth of the algae is ~till inhibited. The results are summarised in Table 1.

Table 1 _ Compound of formula Minimum inhibitory Concentration, MIC mg/l Pbor~idium Ulothrix Tribonema foveolarum subtilissima aequale _ Product of Example 2 2 2 ¦ f .~ 30 30

Claims (9)

WHAT WE CLAIM IS: IS:

1. A compound having the formula I

( I ) wherein X is a chlorine, bromine or iodine atom and Y is a residue having the formula RlR2R3C-, wherein 21 and R2 are the same or differ-ent and each is a fluorine, chlorine or bromine atom ant R3 is a hydrogen, fluorine chlorine or bromine atom, a group -CR4R5R6, a cyano group, a group -CoR7 or -po(R382 wherein R , R , R6, indepen-dently, are F, Cl or Br, R and R are the same or different and each is a chlorine atom or a group -OR wherein R is a Cl-C4 straight chain or branched alkyl group with the proviso that when X is a chlorine atom, none of Rl, R2, R3, R4, R5 and R6 can be a bromine atom.

2. A compound as claimed in Claim 1 wherein X is a chlorine or bromine atom.

3. A compound as claimed in Claim 1 wherein Rl, R2 and R3 are each a fluorine, chlorine or bromine atom.

4. A compound as claimed in Claim 1 which is selected from the group consisting of 4-chloro-4-(2,2,2-trichloroeehyl)oxetan-2-one, 4-bromo- -4-(2,2,2-trichloroethyl)oxetan-2-one, 4-bromo-4-(2,2,2-tribromoethyl)-oxetan-2-one,4-chloro-4-(2,2-dichloro-2-ethoxycarbonylethyloxettan-2-one, and4-bromo-4-(2-chloro-2-bromo-3,3,3-erifluoropropyl))oxetan-2-one.

5. A process of producing a compound of formula I as claimed in Claim 1, comprising reacting dikecene with a compound XY wherein X ant Y
are as defined in Claim 1, in the presence of an agent capable of forming free radicals.

6. A process as claimed in Claim 5 wherein the compound XY is a tetra-halomethane or a trihalomethyl compound.

7. A process as claimed in Claim 5 wherein the compound XY is carbon-tetrachloride, carbontetrabromide, bromotrichloromethane, ethyleri-chloroacetate, trichloromethylphosphonyl dichloride, trichloro-acetonitrile, l-chloro-l,l-dibromotrifluoroethane or hexachloroethane.

8. A process as claimed in Claim 5 wherein the agent capable of form-ing free radicals is an organic peroxide; an organic azo compound;
or a combination of an organic peroxide or an organic azo compound with ultraviolet radiation.

9. A process as claimed in Claim ; which is carried out in a conti-nuous manner.