US3775458A - Substituted phenylethyl sulfites - Google Patents

Abstract

THIS INVENTION RELATES TO NEW COMPOSITIONS OF MATTER HAVING THE FORMULAS:

R-O-CH(-R'')-CH2-O-SO-O-R", OR R-O-CH2-CH(-R'')-O-SO-O-R"

WHERE R'' IS AROMATIC AND R AND R" ARE AROMATIC OR ALIPHATIC. THESE COMPOSITIONS ARE USEFUL FOR CONTROLLING MITES.

Description

United I States Patent 3,775,458 SUBSTITUTED PHENYLETHYL SULFITES Rupert A. ,Covey, Wolcott, Allen E. Smith, Bethany, and Winchester L. Hubbard, Woodbridge, Conn., assignors to Uniroyal, Inc., New York, N.Y. No Drawing. Filed Nov. 1, 1967, Ser. No. 685,226 Int. Cl. C07c 137/00 US. Cl. 260-456 R 6 Claims ABSTRACT OF THE DISCLOSURE This invention relates to new compositions of matter having the formulas:

I ROCHCHQOQOR" or ROCH GHOdOR" r t' R where R is aromatic and R and R" are aromatic or aliphatic. These compositions are useful for controlling mites.

This invention relates to new compositions of matter, specifically, mixed sulfite diesters of aliphatic or aromatic alcohols and an aryl-substituted ethylene glycol ether.

The compounds of the invention are useful for controlling mites.

The compounds of this invention may be represented by either of the two general formulas:

O O I ROCHCHaO 03." and ROCHzCHO LOB" where R' has up to 15 carbon atoms and is aryl, alkaryl,

. alkoxyaryl or haloaryl, R is alkyl having up to 18 carbon atoms or, aryl, alkaryl, haloaryl having up to 15 carbon atoms, R" is aliphatic, e.g., alkyl having up to 18 carbon atoms, alkenyl having from 3 to carbon atoms, alkynyl having 3 to 10 carbon atoms or, cycloalkyl, haloalkyl, cyanoalkyl and alkoxyalkyl having up to 18 carbon atoms or aromatic, e.g., aryl, haloaryl, alkoxyaryl, alkaryl and cycloalkaryl having up to carbon atoms.

Examples of R' are phenyl, 1-naphthyl, 2-naphthyl, p-tolyl, o-tolyl, 2-methyl-4-t-butylphenyl, isopropylphenyl, tert.-butylphenyl, tert.-amylphenyl, nonylphenyl, cyclohexylphenyl, methoxyphenyl, bromophenyl, 2-chlorophenyl, 2,4-dichlorophenyl, trichlorophenyl, pentachlorophenyl.

Examples of R are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec.-butyl, tert.-butyl, amyl, hexyl, 2-ethylhexyl, octyl, decyl, isodecyl, dodecyl, hexadecyl, octadecyl, phenyl, l-naphthyl, 2-naphthy1, p-tolyl, o-tolyl, Z-methyl- 4-t-butylphenyl, isopropylphenyl, tert.-butylphenyl, tert.- amylphenyl, nonylphenyl, bromophenyl, 2-chlorophenyl, 2,4-dichlorophenyl, trichlorophenyl, pentachlorophenyl.

Examples of R" are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec.-buty1, tert.-butyl, amyl, hexyl, 2-ethylhexyl, octyl, decyl, isodecyl, dodecyl, hexadecyl, octadecyl, allyl, methallyl, alkynyl radicals having 3 to 10 carbon atoms, e.g., propargyl and l-(3-nonynyl), cyclohexyl, 4- methoxycyclohexyl, 2-chloroethyl, 2,2,2-trichloroethyl, 'ychloropropyl, 2,4-dichlorobutyl, w-trichloroamyl, 2-cyanoethyl, methoxyethyl, sec.-butoxyisopropyl, phenyl, 1- naphthyl, Z-naphthyl, p-tolyl, o-tolyl, 2-methyl-4-t-butylphenyl, isopropylphenyl, tert.-butylphenyl, tert.-amylphenyl, nonylphenyl, cyclohexylphenyl, chloromethylphenyl, methoxyphenyl, bromophenyl, 2-chloropheny1, 2,4-dichlorophenyl, trichlorophenyl, pentachlorophenyl.

3,775,458 Patented Nov. 27, 1973 Examples of sulfite diesters of the present invention are:

methyl 1-phenyl-2-methoxyethyl sulfite ethyl 2-phenyl-2-methoxyethyl sulfite butyl 2-phenyl-2-ethoxyethyl sulfite methyl l-phenyl-Z-butoxyethyl sulfite methyl l-phenyl-Z-docoxyethyl sulfite octyl 2-phenyl-2-phenoxyethyl sulfite allyl l-phenyl-Z-o-toloxyethyl sulfite propargyl 2-phenyl-2-p-toloxyethyl sulfite 1-(2-butyny1) 1-phenyl-2-p-isopropylphenoxyethyl sulfite cyclohexyl 1-phenyl-2-p-t-butylphenoxyethyl sulfite 2-ch1oroethyl 2-phenyl-2-p-t-butylphenoxyethyl sulfite 2-cyanoethyl l-phenyl-Z-m-toloxyethyl sulfite methoxyethyl 1-p-tolyl-2-o-chlorophenoxyethyl sulfite phenyl 2-m-methoxyphenyl-2-p-chlorophenoxyethyl sulfite o-tolyl 1-phenyl-2-o-t-butylphenoxyethyl sulfite pt-butylphenyl 2-0-chlorophenyl-2-p-t-butylphenoxyethyl sulfite o-chlorophenyl 1-phenyl-2-p-toloxyethyl sulfite m-tolyl 1-m-tolyl-2-p-t-butylphenoxyethyl sulfite methoxyphenyl 2-phenyl-2-o-chlorophenoxyethyl sulfite.

The compounds of this invention may be prepared by reacting an alcohol or phenol with the separately prepared chlorosulfinate of a selected glycol monoether, which may be made by reacting the glycol ether with thionyl chloride. The glycol ether may be made by reacting an alcohol or phenol with styrene oxide or a substituted styrene oxide. A mixture of two isomeric glycol ethers generally is formed, one of which is a primary and the other a secondary alcohol, and the amount of each depends on the direction of opening of the oxide ring. The ratio of the isomers can be varied depending on the catalyst used. Such preparations are illustrated by the following reactions with the same symbols R, R and R" as in the above general formulas.

Alternatively some of the compounds of this invention may be prepared by reacting the glycol ether with the chlorosulfinate of an alcohol as illustrated in the following reaction 0 ROCH OHOH CldOCH CH Cl i ROCH $HO S OCH CHZCI The chemicals of the present invention may be applied in various manners for the control of insects. They may be applied to loci to be protected against insects as dusts when admixed with or absorbed on powdered solid carriers, such as the various mineral silicates, e.g. mica, talc, pyrophyllite and clays, or as liquids or sprays when in a liquid carrier, as in solution in a suitable solvent, such as acetone, benzene or kerosene, or dispersed in a suitable non-solvent medium, for example, water. In protecting plants (the term including plant parts) which are subject to attack by insects, the chemicals of the present invention are preferably applied as aqueous emulsions containing a surface-active dispersing agent, which may be an anionic, non-ionic or cationic surface-active agent. Such surface-active agents are well known and reference is made to U.S. Pat. No. 2,547,724, columns 3 and 4 for detailed examples of the same. The chemicals of the invention may be mixed with such surface-active dispersing agents, with or without an organic solvent as insecticidal concentrates for subsequent addition of water to make aqueous suspensions of the chemicals of the desired concentration. The chemicals of the invention may be admixed with powdered solid carriers, such as mineral silicates together with a surface-active dispersing agent so that a wettable powder may be obtained, which may be applied directly to loci to be protected against insects, or which may be shaken up wih water to form a suspension of the chemical (and powdered solid carrier) in water for application in that form. The chemicals of the present invention may be applied to loci to be protected against insects by the aerosol method. Solutions for the aerosol treatment may be prepared by dissolving the chemical directly in the aerosol carrier which is liquid under pressure but which is a gas at ordinary temperature (e.g., 20 C.) and atmospheric pressure, or the aerosol solution may be prepared by first dissolving the chemical in a less volatile solvent and then admixing such solution with the higly volatile liquid aerosol carrier. The chemicals may be used admixed with carriers that are active of themselves, for example, other insecticides, fungicides or bactericides.

The amount of chemical which is used for control of mites varies widely depending largely on the amount of foliage to be covered. From as little as 1 oz. per acre on a young field crop to six pounds or more per acre on an orchard may be used. This could be applied in, as little as 5 gallons of liquid by airplane spray application, or in as much as 600 gallons with a more conventional ground sprayer which drenches the foliage.

Dust applications, similarly, would vary in the amounts of material required to control mites as do the liquid spray preparation with the range of active ingredient needed per acre comparable to that used in the spray applications.

Aerosol treatments of confined areas such as a greenhouse would range from /2 oz. to 8 oz. of active material for 10,000 cu. ft. of space to be treated.

The preparation of the glycol ether can be illustrated by the following example.

EXAMPLE I l-(or 2-) phenyl-2-p-t-butylphenoxyethanol p-Tert.-butylphenol (112 g., 0.75 mole) and 2.2 g. sodium hydroxide were combined and the mixture heated to 150. Styrene oxide (85.5 ml., 90.0 g., 0.75 mole) was added during three hours maintaining the reaction temperature at ISO-160. The mixture was cooled, the catalyst was neutralized with concentrated hydrochloric acid, and the product taken up in xylene. The xylene was distilled off leaving the crude product which is a mixture of 1- and 2-phenyl p-t-butylphenoxyethanol. The mixture can be used directly in making the sulfite esters or can be distilled, 'B.P. 140-147 (0.1 mm.). Upon standing, crystals formed in the distillate which, after recrystallization from hexane, melted 96-98.

The chlorosulfinates can be prepared by well-known reactions (see U.S. 3,179,682 to 687 and 2,529,494 for examples of their preparations).

The preparation of the sulfite esters is carried out in the presence of an HCl acceptor, such as pyridine, dimethylaniline or trimeth'ylamine, and in a solvent such as benzene, xylene or solvent naphths. The reaction temperature is generally between -l0 and 50, preferably near 0.

The following example illustrates the preparation of the sulfite esters.

EXAMPLE II S-chloroethyl l-(or 2-) phenyl-2-p-t-butylphenoxyethyl sulfite l-(or 2-) phenyl-Z-p-t-butylphenoxyethanol (7.0 g., 0.026 mole), 2.3 ml. (2.2 g., 0.029 mole) pyridine and 50 ml. xylene were combined and the solution was cooled to 0-5. A solution of 4.7 g. (0.029 mole) fl-chloroethyl chlorosulfinate in 20 ml. xylene was added during 15 min., keeping the temperature below 15. The mixture was stirred for 30 min. and then washed successively with two 25 ml. portions water, 25 ml. 2 N NaOH and several portions of saturated salt solution until the last portion was neutral to pH paper. The xylene was removed under reduced pressure and the residue heated to (0.7 mm.) to remove volatile impurities. The residue was slurried with Dicalite (filter-aid) aid filtered, giving 8.6 g. (83.5%) of viscous liquid.

Analysis.Calcd. for C H ClO S: S, 8.08. Found: 7.94, 7.98.

Sulfur analyses of other chemicals of the present invention were:

Propargyl l-(or 2-)phenyl-2-p-t-butylphenoxyethyl sulfite. Calculated S: 8.67. Found: 7.79, 7.64.

o-Tolyl l-(or 2-)phenyl-2-p-t-butylphenoxyethyl sulfite. Calculated S: 7.55. Found: 6.79, 7.09.

Infrared spectra obtained on all of the prepared sulfites of this invention showed sulfite absorption at 8.3 and were consistent with the structures.

To show that the compounds of the present invention are effective for controlling mites the following example is set forth:

EXAMPLE III Pinto beans in the two-leaf stage and grown in 4" baskets under greenhouse conditions at 70 F.75 F. were used. Three plants for a total of six leaves were in each basket for each test. The tests on the chemicals and checks were replicated once. Aqueous suspensions of the chemicals were prepared by adding to 0.2 gram of the chemical one drop (0.03 gram) of a commercial surface-active dispersing agent (isooctylphenyl polyethoxy ethanol) and 1 ml. of acetone, diluting to 200 ml. with water for 1000 p.p.m. Additional water was used for diluting to 200 p.p.m.

The plants were sprayed with the dispersions of the chemicals at the various concentrations so that the upper surface of the leaves was thoroughly wet. The plants were returned to the greenhouse. The following day (20-24 hours later), rings of an adhesive preparation non-toxic to the organisms under test, such as is used on fly papers and for ringing trees, were placed around the borders of the upper surfaces of the leaves to restrict the mites to the upper leaf surface. Mites were transferred to the thus treated leaves by placing bean leaflets heavily infested with adult two-spotted spider mites, Tetranychus urticae koch, within the border of the adhesive preparation on the leaves of the plants under test. A count of the number of mites transferred was made the same day. The counts ranged from 30 to 300 mites on the six leaves. The plants were kept in the greenhouse for another four days. A final count f the number of living mites remaining on the leaves was then made. The percent control is found by the formula:

Percent contro1=100 F1nal count 11v1ng mites) Original count The control of mites by the chemicals of the present invention at the various concentrations is shown in the following table (the check treatments without the chemicals had negligible mortality).

Having thus described our invention, what we claim and desire to protect by Letters Patent is:

1. A compound represented the formula wherein the substituent is an alkyl group having up to 9 carbon atoms; and R" is alkyl or haloalkyl having up to 18 carbon atoms, alkenyl, alkynyl having .from 3 to 10 carbon atoms, cyclohexyl, phenyl, phenyl having substituents consisting of up to 5 halo radicals selected from chloro and bromo, or mono-substituted phenyl wherein the substituent is an alkyl group having up to 9 carbon atoms.

2. The compound of claim 1: propargyl l-(or 2-)- phenyl-2-p-t-butylphenoxyethyl sulfite.

3. The compound of claim 1: o-tolyl l-(or 2-)-phenyl- Z-p-t-butylphenoxyethyl sulfite.

4. The compound of claim 1: fi-chloroethyl 1-(or 2-) phenyl-2-p-t-butylphenoxyethyl sulfite.

5. The compound of claim 1: propargyl l-(or 2-) phenyl-Z-o-toloxyethyl sulfite.

6. The compound of claim 1: propargyl l-(or 2-)-ptolyl-Z-o-toloxyethyl sulfite.

References Cited UNITED STATES PATENTS 3,179,682 4/1965 Covey et al 260-456 2,529,494 10/1948 Harris 260-456 2,208,581 7/1940 Hoeifelman 260-456 2,620,359 12/1952 Britton et a1 260-611 A 3,401,120 9/ 1968 Chiddix et a1 260-611 A 3,463,859 8/1969 Covey et al 260-456 LEON ZITVER, Primary Examiner L. DECRE'SCENTE, Assistant Examiner US. Cl. X.R. 424-303