US2237356A - Insecticide - Google Patents
Insecticide Download PDFInfo
- Publication number
- US2237356A US2237356A US271283A US27128339A US2237356A US 2237356 A US2237356 A US 2237356A US 271283 A US271283 A US 271283A US 27128339 A US27128339 A US 27128339A US 2237356 A US2237356 A US 2237356A
- Authority
- US
- United States
- Prior art keywords
- ester
- esters
- insecticide
- employed
- carrier
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000002917 insecticide Substances 0.000 title description 13
- 150000002148 esters Chemical class 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 239000007921 spray Substances 0.000 description 12
- 239000003921 oil Substances 0.000 description 10
- 125000005907 alkyl ester group Chemical group 0.000 description 9
- 235000007586 terpenes Nutrition 0.000 description 7
- 239000003350 kerosene Substances 0.000 description 6
- 150000003505 terpenes Chemical class 0.000 description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- 150000008064 anhydrides Chemical class 0.000 description 4
- 150000005690 diesters Chemical class 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 230000000749 insecticidal effect Effects 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000005871 repellent Substances 0.000 description 4
- 230000002940 repellent Effects 0.000 description 4
- 231100000331 toxic Toxicity 0.000 description 4
- 230000002588 toxic effect Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- 150000007519 polyprotic acids Polymers 0.000 description 3
- JUVIOZPCNVVQFO-UHFFFAOYSA-N rotenone Natural products O1C2=C3CC(C(C)=C)OC3=CC=C2C(=O)C2C1COC1=C2C=C(OC)C(OC)=C1 JUVIOZPCNVVQFO-UHFFFAOYSA-N 0.000 description 3
- -1 terpene esters Chemical class 0.000 description 3
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 2
- 241000283690 Bos taurus Species 0.000 description 2
- 241000522187 Derris Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- 240000004460 Tanacetum coccineum Species 0.000 description 2
- ROVGZAWFACYCSP-MQBLHHJJSA-N [2-methyl-4-oxo-3-[(2z)-penta-2,4-dienyl]cyclopent-2-en-1-yl] (1r,3r)-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropane-1-carboxylate Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OC1C(C)=C(C\C=C/C=C)C(=O)C1 ROVGZAWFACYCSP-MQBLHHJJSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical group CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 229940015367 pyrethrum Drugs 0.000 description 2
- JUVIOZPCNVVQFO-HBGVWJBISA-N rotenone Chemical compound O([C@H](CC1=C2O3)C(C)=C)C1=CC=C2C(=O)[C@@H]1[C@H]3COC2=C1C=C(OC)C(OC)=C2 JUVIOZPCNVVQFO-HBGVWJBISA-N 0.000 description 2
- 235000015096 spirit Nutrition 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000004166 Lanolin Substances 0.000 description 1
- VQXSOUPNOZTNAI-UHFFFAOYSA-N Pyrethrin I Natural products CC(=CC1CC1C(=O)OC2CC(=O)C(=C2C)CC=C/C=C)C VQXSOUPNOZTNAI-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229940039717 lanolin Drugs 0.000 description 1
- 235000019388 lanolin Nutrition 0.000 description 1
- 229940059904 light mineral oil Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- HYJYGLGUBUDSLJ-UHFFFAOYSA-N pyrethrin Natural products CCC(=O)OC1CC(=C)C2CC3OC3(C)C2C2OC(=O)C(=C)C12 HYJYGLGUBUDSLJ-UHFFFAOYSA-N 0.000 description 1
- VJFUPGQZSXIULQ-XIGJTORUSA-N pyrethrin II Chemical compound CC1(C)[C@H](/C=C(\C)C(=O)OC)[C@H]1C(=O)O[C@@H]1C(C)=C(C\C=C/C=C)C(=O)C1 VJFUPGQZSXIULQ-XIGJTORUSA-N 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing carboxylic groups or thio analogues thereof, directly attached by the carbon atom to a cycloaliphatic ring; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C69/75—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring of acids with a six-membered ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
Definitions
- This invention relates to insecticides, particularly to insecticidal sprays such as fly sprays, cattle sprays and the like wherein the active agent is contained in a carrier or solvent, and it also relates to insecticides in which the active agent is carried on an inert or active dry carrier or dust, or also in unctious form.
- the object or the present invention is to provide insecticides oi the type indicated containing as an important active constituent a material of greater repellent value than heretofore employed in commercial uses of the indicated type, and wherein the repellent material employed in the various carriers is non-volatile, non-subliming and stable.
- the active constituent is an alkyl ester of a terpene dicarboxylic acid
- the invention involves an alkyl ester (e. e. diethyl ester) of a polybasic acid of terpene origin produced from an anhydride known as 3-isopropyl-d-rnethyl-3,6-endoethylene- A tetrahydro phthalic anhydride.
- anhydride actually employed as the startingmaterial is a commercial synthetic product containing; polymeric materials
- the ester product also contains lymeric materials in minor quantities. This material also has the characteristic 01-increasing toxic action of other materials which have in themselves toxic action, such as pyrethrin, derris extracts and kindred organic toxic materials usable in sprays of this type.
- the invention resides in the use of such alkyl ester from said substituted polybasic acid anhydride as an insecticide.
- the invention also resides in a mineral oil fraction as a carrier for said alkyl ester.
- a mineral oil fraction may be kerosene or the like where the material is to be used for fly sprays for example, or it may be a less volatile heavier material commonly known as mineral spray oil, or other appropriate fraction.
- the invention also resides in the use of said modified terpene esters in any other appropriate carrier such as a dust or unctious body.
- the invention resides in compositions containing the mentioned esters which also additionally contain toxic agents such as pyrethrurn and the like whose toxic action is increased through'the presence of said esters.
- the allnrl tetrahydro phthalic anhydride employed for production of the esters of this invention may be obtained on the market under the trade name Petrex manufactured by Hercules Powder Company, this material also containing a small quantity of polymeric materials.
- the essential constituent is the phthalic anhydride substitution product mentioned which is a synthetic, resinous, polybasic acid anhydride of terpene origin. This anhydride is substantially non-volatile, does not sublime on heating andretains its pale yellow color at elevated temperatures.
- Said substituted phthalic anhydride appears to be 3-isopropyl-6-rnethyl 3,6 endoethylene-M- tetrahydro phthalic anl iydride, having the following indicated structure, and an ester of the invention has the corresponding indicated structure where R is an alkyl group:
- Anhydride Di-cster CH: CH3 t t H O H O H e tear Haj is new I l I 0 i i I H-l CH2 OC HC CH2 C-C-O-R /ii ii HaC-JJ-CH3 H3C( 3CH3 1'; 1'1
- CIIHs c HzC equal parts of alcohol and water'containing 6%.
- the separated solution contains the mono-ester which may be in turn separated by acidifying the extract and washing.
- the di-ester which did not enter into the extracting solution, was recovered simply by washing with water in the cold.
- the di-ester product is a yellowish to orange liquid of high viscosity approximating that of heavy lubricating oil. It has an acid number of 0.72 and a saponification number of 306.
- the mono-ester is normally con-' siderably more viscous than the di-ester and is nearly solid.
- the boiling point of both esters is above 400 F.
- the acid number of the monoester is considerably higher than that of the diester being about 154.
- oils for horticultural uses commonly possess highly unsulfonatable residues in the neighborhood of Ong.
- oils in these viscosity ranges may possess lower unsulfonatable residues, for example in the range of to deOng or even lower or higher as uses may permit.
- 5% of ethyl Petrex, as above described, employed in a kerosene type out in the range commonly used for fly sprays has been employed and found to be highly preferable as a repellent to all other types of synthetic material used in the same concentration.
- Petrex ester in petroleum fractions as described, it may be desirable to add other insecticidal constituents-such as pyrethrum, or derris or cube extracts, or alkyl thiocyanates, and the like.
- insecticidal constituents such as pyrethrum, or derris or cube extracts, or alkyl thiocyanates, and the like.
- insecticide it may be preferable to prepare the insecticide as a dust in which case it may be carried in an inert carrier such as diatomaceous earth or it may be carried on an active carrier such as powdered pyrethrum flowers or ground derris root or the like.
- the Petrex alkyl esters may be carried in an unctious type carrier such as lanolin or other greasy or pasty material.
- An insecticide comprising a lower alkyl ester of 3-isopropyl 6-methyl 3,6-endoethylene A -tetrahydro-phthalic acid.
- ester is one of the class consisting of methyl, ethyl, propyl and butyl esters.
- An insecticide according to claim 1 including a mineral oil fraction as a carrier.
- An insecticide according to claim 1- including a carrier and wherein the ester is one of the class consisting of methyl, ethyl, propyl and butyl esters.
- An insecticide comprising a slowly volatilizing petroleum fraction, and a low alkyl ester of 3-isopropyl B-methyl 3,6-endoethylene A -tetrahydro-phthalic acid.
- ester is the ester of an alcohol of the group consisting of methyl, ethyl, propyl and butyl alcohols.
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Dentistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
INSECTIMDE David R. Merrill, Long Beach, Caliii, assignor to Union Oil Company of California, Los Angeles, Calif., a corporation of California No Drawing. Application May 2, 1939,
' Serial No. 271,283
7 Claim.
This invention relates to insecticides, particularly to insecticidal sprays such as fly sprays, cattle sprays and the like wherein the active agent is contained in a carrier or solvent, and it also relates to insecticides in which the active agent is carried on an inert or active dry carrier or dust, or also in unctious form.
The object or the present invention is to provide insecticides oi the type indicated containing as an important active constituent a material of greater repellent value than heretofore employed in commercial uses of the indicated type, and wherein the repellent material employed in the various carriers is non-volatile, non-subliming and stable.
according to this invention, the active constituent is an alkyl ester of a terpene dicarboxylic acid, and specifically the invention involves an alkyl ester (e. e. diethyl ester) of a polybasic acid of terpene origin produced from an anhydride known as 3-isopropyl-d-rnethyl-3,6-endoethylene- A tetrahydro phthalic anhydride. Since the anhydride actually employed as the startingmaterial is a commercial synthetic product containing; polymeric materials, the ester product also contains lymeric materials in minor quantities. This material also has the characteristic 01-increasing toxic action of other materials which have in themselves toxic action, such as pyrethrin, derris extracts and kindred organic toxic materials usable in sprays of this type.
The invention resides in the use of such alkyl ester from said substituted polybasic acid anhydride as an insecticide. The invention also resides in a mineral oil fraction as a carrier for said alkyl ester. Such a fraction may be kerosene or the like where the material is to be used for fly sprays for example, or it may be a less volatile heavier material commonly known as mineral spray oil, or other appropriate fraction. The invention also resides in the use of said modified terpene esters in any other appropriate carrier such as a dust or unctious body. Also the invention resides in compositions containing the mentioned esters which also additionally contain toxic agents such as pyrethrurn and the like whose toxic action is increased through'the presence of said esters.
The allnrl tetrahydro phthalic anhydride employed for production of the esters of this invention may be obtained on the market under the trade name Petrex manufactured by Hercules Powder Company, this material also containing a small quantity of polymeric materials. The essential constituent is the phthalic anhydride substitution product mentioned which is a synthetic, resinous, polybasic acid anhydride of terpene origin. This anhydride is substantially non-volatile, does not sublime on heating andretains its pale yellow color at elevated temperatures. It possesses an acid number of about 530, has a softening point of ill i to lit, a specific grayity of l.l5, and is soluble in alcohols, various drying oils, acetates, coal tar hydrocarbons, mineral spirits and other petroleum fractions such as kerosene, mineral spray oils and similar light mineral oil fractions adapted to insecticidal uses.
Said substituted phthalic anhydride appears to be 3-isopropyl-6-rnethyl 3,6 endoethylene-M- tetrahydro phthalic anl iydride, having the following indicated structure, and an ester of the invention has the corresponding indicated structure where R is an alkyl group:
Anhydride Di-cster CH: CH3 t t H O H O H e tear Haj is new I l I 0 i i I H-l CH2 OC HC CH2 C-C-O-R /ii ii HaC-JJ-CH3 H3C( 3CH3 1'; 1'1
The above materials are of terpene origin as is apparent from a well known terpene (C10H1c) having the structure:
CIIHs c HzC equal parts of alcohol and water'containing 6%.
sodium hydroxide. The separated solution contains the mono-ester which may be in turn separated by acidifying the extract and washing. The di-ester, which did not enter into the extracting solution, was recovered simply by washing with water in the cold. The di-ester product is a yellowish to orange liquid of high viscosity approximating that of heavy lubricating oil. It has an acid number of 0.72 and a saponification number of 306. The mono-ester is normally con-' siderably more viscous than the di-ester and is nearly solid. The boiling point of both esters is above 400 F. The acid number of the monoester is considerably higher than that of the diester being about 154. Both are soluble in alcohols, mineral spirits, mineral oil fractions and the like and, being highly stable, are well adapted to the present uses, especially in view of the fact that they have high repellent values for insecticidal purposes. By somewhat similar procedures, obvious to the skilled chemist, other alkyl esters of the lower alcohols also may be produced and employed, such as the lower alkyl esters methyl, propyl and butyl esters.
The above described alkyl ester products of the indicated terpene dicarboxylic acid which are herein sometimes referred to as Petrex" esters for convenience, are added to various petroleum oils suitable for individual purposes, in concentrations varying from about 1% to about 10%. Perhaps a good general average is in the vicinity of 3% to 5% based on the oil fraction employed. For the purpose of fly sprays an appropriate cut in the kerosene range, which may be if desired either in the nature of a light kerosene cut or a heavy kerosene cut, may be employed. For other uses it may be desirable to employ heavier maf terials such as spray oils, for example where making up cattle sprays. Mineral spray oils are well known in the agricultural industry. They are lighter than ordinary light lubricating oils, although they have lubricating characteristics, and
possess viscosities in the order of about 50 to 125 seconds Saybolt Universal at 100 F. Such. oils for horticultural uses commonly possess highly unsulfonatable residues in the neighborhood of Ong. However, oils in these viscosity ranges may possess lower unsulfonatable residues, for example in the range of to deOng or even lower or higher as uses may permit.
As a specific example, 5% of ethyl Petrex, as above described, employed in a kerosene type out in the range commonly used for fly sprays has been employed and found to be highly preferable as a repellent to all other types of synthetic material used in the same concentration. I
In addition to using the Petrex ester in petroleum fractions as described, it may be desirable to add other insecticidal constituents-such as pyrethrum, or derris or cube extracts, or alkyl thiocyanates, and the like. In some instances it may be preferable to prepare the insecticide as a dust in which case it may be carried in an inert carrier such as diatomaceous earth or it may be carried on an active carrier such as powdered pyrethrum flowers or ground derris root or the like. Again the Petrex alkyl esters may be carried in an unctious type carrier such as lanolin or other greasy or pasty material.
It is to be understood that; these disclosures are given as illustrative of the generic invention within the scope of the appended claims, rather than as limiting thereof.
I claim:
1. An insecticide comprising a lower alkyl ester of 3-isopropyl 6-methyl 3,6-endoethylene A -tetrahydro-phthalic acid.
2. An insecticide according to claim 1 wherein the ester is one of the class consisting of methyl, ethyl, propyl and butyl esters.
3. An insecticide according to claim 1 wherein the ester is the di-ethyl ester.
4. An insecticide according to claim 1 including a mineral oil fraction as a carrier.
5. An insecticide according to claim 1- including a carrier and wherein the ester is one of the class consisting of methyl, ethyl, propyl and butyl esters.
6. An insecticide comprising a slowly volatilizing petroleum fraction, and a low alkyl ester of 3-isopropyl B-methyl 3,6-endoethylene A -tetrahydro-phthalic acid.
7. An insecticide according to claim 6 wherein the ester is the ester of an alcohol of the group consisting of methyl, ethyl, propyl and butyl alcohols.
DAVID R. MERRILL.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US271283A US2237356A (en) | 1939-05-02 | 1939-05-02 | Insecticide |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US271283A US2237356A (en) | 1939-05-02 | 1939-05-02 | Insecticide |
Publications (1)
Publication Number | Publication Date |
---|---|
US2237356A true US2237356A (en) | 1941-04-08 |
Family
ID=23034925
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US271283A Expired - Lifetime US2237356A (en) | 1939-05-02 | 1939-05-02 | Insecticide |
Country Status (1)
Country | Link |
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US (1) | US2237356A (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2471790A (en) * | 1945-04-26 | 1949-05-31 | Sowa | Insect-affecting compositions |
US2492266A (en) * | 1947-10-15 | 1949-12-27 | Hercules Powder Co Ltd | Tetrahydrodicyclopentadiene ether compounds and insecticides thereof |
US2527322A (en) * | 1945-07-21 | 1950-10-24 | Commercial Solvents Corp | Insect repellent compositions |
DE1025879B (en) * | 1952-03-26 | 1958-03-13 | Velsicol Chemical Corp | Process for the preparation of N-Mercuri-1, 2, 3, 6-tetrahydro-3, 6-endomethylene-3, 4, 5, 6, 7, 7-hexachlorophthalimides |
US2867648A (en) * | 1955-07-21 | 1959-01-06 | Monsanto Chemicals | Process of producing turpentine-unsaturated dicarboxylic ester adducts |
US3476546A (en) * | 1964-12-17 | 1969-11-04 | Ici Australia Ltd | Bicyclo(2,2,2)oct-5-ene-2,3-dicarboxylic anhydrides as herbicides |
-
1939
- 1939-05-02 US US271283A patent/US2237356A/en not_active Expired - Lifetime
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2471790A (en) * | 1945-04-26 | 1949-05-31 | Sowa | Insect-affecting compositions |
US2527322A (en) * | 1945-07-21 | 1950-10-24 | Commercial Solvents Corp | Insect repellent compositions |
US2492266A (en) * | 1947-10-15 | 1949-12-27 | Hercules Powder Co Ltd | Tetrahydrodicyclopentadiene ether compounds and insecticides thereof |
DE1025879B (en) * | 1952-03-26 | 1958-03-13 | Velsicol Chemical Corp | Process for the preparation of N-Mercuri-1, 2, 3, 6-tetrahydro-3, 6-endomethylene-3, 4, 5, 6, 7, 7-hexachlorophthalimides |
US2867648A (en) * | 1955-07-21 | 1959-01-06 | Monsanto Chemicals | Process of producing turpentine-unsaturated dicarboxylic ester adducts |
US3476546A (en) * | 1964-12-17 | 1969-11-04 | Ici Australia Ltd | Bicyclo(2,2,2)oct-5-ene-2,3-dicarboxylic anhydrides as herbicides |
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