US2913327A - Certain thiolcarbamates and use as herbicides - Google Patents
Certain thiolcarbamates and use as herbicides Download PDFInfo
- Publication number
- US2913327A US2913327A US559541A US55954156A US2913327A US 2913327 A US2913327 A US 2913327A US 559541 A US559541 A US 559541A US 55954156 A US55954156 A US 55954156A US 2913327 A US2913327 A US 2913327A
- Authority
- US
- United States
- Prior art keywords
- parts
- mole
- sodium
- added
- chloride
- 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
- 239000004009 herbicide Substances 0.000 title description 9
- 238000000034 method Methods 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000002689 soil Substances 0.000 claims description 9
- 231100000208 phytotoxic Toxicity 0.000 claims description 7
- 230000000885 phytotoxic effect Effects 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 21
- 229910052708 sodium Inorganic materials 0.000 description 21
- 239000011734 sodium Substances 0.000 description 21
- 239000000203 mixture Substances 0.000 description 16
- 241000196324 Embryophyta Species 0.000 description 13
- 239000006185 dispersion Substances 0.000 description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 9
- 239000008096 xylene Substances 0.000 description 9
- 240000008042 Zea mays Species 0.000 description 8
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 8
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 8
- 235000005822 corn Nutrition 0.000 description 8
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 235000007238 Secale cereale Nutrition 0.000 description 4
- -1 alkyl radical Chemical class 0.000 description 4
- OWRABTHGOKNUDV-UHFFFAOYSA-N n,n-dipropylcarbamoyl chloride Chemical compound CCCN(C(Cl)=O)CCC OWRABTHGOKNUDV-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 235000007319 Avena orientalis Nutrition 0.000 description 3
- 244000075850 Avena orientalis Species 0.000 description 3
- GUVLYNGULCJVDO-UHFFFAOYSA-N EPTC Chemical compound CCCN(CCC)C(=O)SCC GUVLYNGULCJVDO-UHFFFAOYSA-N 0.000 description 3
- 230000002363 herbicidal effect Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- GTSSFGPSIKYACK-UHFFFAOYSA-N C(CC)OC(NC=1SC=CC1)=O Chemical compound C(CC)OC(NC=1SC=CC1)=O GTSSFGPSIKYACK-UHFFFAOYSA-N 0.000 description 2
- 240000004713 Pisum sativum Species 0.000 description 2
- 235000010582 Pisum sativum Nutrition 0.000 description 2
- 244000088415 Raphanus sativus Species 0.000 description 2
- 235000006140 Raphanus sativus var sativus Nutrition 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- OSWBZCCZJXCOGL-UHFFFAOYSA-N n,n-dibutylcarbamoyl chloride Chemical compound CCCCN(C(Cl)=O)CCCC OSWBZCCZJXCOGL-UHFFFAOYSA-N 0.000 description 2
- PFWZXDDTAYMUPE-UHFFFAOYSA-N propan-2-ol;1,2-xylene Chemical group CC(C)O.CC1=CC=CC=C1C PFWZXDDTAYMUPE-UHFFFAOYSA-N 0.000 description 2
- KJRCEJOSASVSRA-UHFFFAOYSA-N propane-2-thiol Chemical compound CC(C)S KJRCEJOSASVSRA-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 240000008067 Cucumis sativus Species 0.000 description 1
- 235000010799 Cucumis sativus var sativus Nutrition 0.000 description 1
- 240000004244 Cucurbita moschata Species 0.000 description 1
- 235000009854 Cucurbita moschata Nutrition 0.000 description 1
- 235000009852 Cucurbita pepo Nutrition 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 241000520028 Lamium Species 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 241000209504 Poaceae Species 0.000 description 1
- 241000209056 Secale Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000012364 cultivation method Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 244000013123 dwarf bean Species 0.000 description 1
- 235000005489 dwarf bean Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- RSAFAYLZKCYUQW-UHFFFAOYSA-N n,n-di(propan-2-yl)carbamoyl chloride Chemical compound CC(C)N(C(C)C)C(Cl)=O RSAFAYLZKCYUQW-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001931 phytocidal effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- QJDUDPQVDAASMV-UHFFFAOYSA-M sodium;ethanethiolate Chemical group [Na+].CC[S-] QJDUDPQVDAASMV-UHFFFAOYSA-M 0.000 description 1
- WBQTXTBONIWRGK-UHFFFAOYSA-N sodium;propan-2-olate Chemical compound [Na+].CC(C)[O-] WBQTXTBONIWRGK-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 235000020354 squash Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01Q—ANTENNAS, i.e. RADIO AERIALS
- H01Q1/00—Details of, or arrangements associated with, antennas
- H01Q1/12—Supports; Mounting means
- H01Q1/1235—Collapsible supports; Means for erecting a rigid antenna
-
- 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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/52—Radicals substituted by nitrogen atoms not forming part of a nitro radical
Definitions
- Ethyl N N-di-n-propylthiolcarbamate Methyl ,N-di-n-propylthiolcarbamate. n-Propyl ,N-di-n-propylthiolcarbamate. Ethyl N,N-pentamethylenethiolcarbamate. n-Propyl N,N-pentamethylenethiolcarbamate. Isobutyl N.N-di-n-propylthiolcarbamate. n-Butyl N,N-di-n-propylthiolcarbamate.
- N,N-di-n-butylthiolcarbamate Ethyl N,N-di-n-butylthiolcarbamate. sec-Butyl N,N-di-n-propylthiolcarbamate. n-Amyl N, -di-n-propylthiolcarbamate. n-Propyl N ,N-di-isopropylthiolcarbamate.
- Example II (R-1607).
- 38 parts (0.50 mole) of l-propanethiol, sodium dispersion equivalent to 9.2 parts (.40 mole) of sodium, and 65.5 parts (0.40 mole) of di-n-propylcarbamyl chloride are employed, there is obtained 70.3 parts (86.5% yield) of n-propyl N,N-din- Example Ill (R1880).
- 9.12 parts (0.12 mole) of l-p-ropanethiol, sodium dispersion equivalent to 2.3 parts (0.10 mole) of sodium, and 19.2 parts (0.10 mole) of di-n-butylcarbamyl chloride are employed, there is obtained 20.4 parts (88.3% yield) of n-propyl N,
- Example IV (R-1854).-When the general procedure of Example I is repeated except that 16.9 parts (0.188 mole) of Z-methyl-l-propanethiol, sodium dispersion equivalent to 3.45 parts (0.15 mole) of sodium and 24.5 parts (0.15 mole) of di-n-propylcarbamyl chloride are employed, there is obtained 25.2 parts (77.3% yield) of isobutyl N,N-di-n-propylthiolcarbamate (B.P. (18 mm.) 143145 0, n 1.4744).
- Example V (RJ857).When the general procedure of Example I is repeated except that 16.9 parts (0.188 mole) of l-butanethiol, sodium dispersion equivalent to 3.45 parts (0.15 mole) sodium and 24.5 parts (0.15 mole) of di-n-propylcarbamyl chloride are employed, there is obtained 24.8 parts (76% yield) of n-butyl N,N-di-n-propyl- 3 thiolcarbamate (B.P. (19 mm.) l51.0-151.5' C., 11 1.4766).
- Example VI (R-I866). The general procedure of Example I was followed except that 25 parts (0.52 mole) of methanethiol is added in small portions at 50-60 C. to the sodium dispersion equivalent to 2.3 parts (0.10 mole) of sodium. It is necessary to make sure that unreacted mercaptan does not build up in the reaction mixture since a violent reaction may take place if too much unreacted mercaptan is present with unreacted dispersion. After all of the sodium dispersion has reacted which is evidenced by the reaction mixture changing from a purplish hue to a white color, it is heated to reflux and 19.2 parts (0.10 mole) of di-n-butylcarbamyl chloride is added. After working up in the usual manner, there is obtained 13.9 parts (68.5% yield) of methyl N,N,-din-butylthiolcarbamate (B.P. (20 mm.) 144-146 C., n 1.4760).
- Example X (R-1905).
- Example VIII When the general procedure of Example VIII is repeated except that 13.0 parts (0.125 mole) of l-pentanethiol, 2.3 parts (0.10 mole) of sodium and 16.4 parts of di-isopropylcarbamyl chloride are employed, there is obtained 15.8 parts (68.3%) of n-amyl N,N,-di-isopropylthiolcarbamate (B.P. (22 mm.) 145- 149 C., a 1.4721).
- Example XI (R-1824).Wl1en the general procedure of Example VIII is repeated except that 14.3 parts (0.188 mole) of 2-propanethiol, 3.45 parts (0.15 mole) of sodium and 22.1 parts (0.15 mole) of N,N-pentarnethyl-
- Pre-emergence herbicides are ordinarily used by placing a narrow band of the herbicide over the center of a seeded crop row at time of planting or before crop emerges. If the herbicide is harmless to the desired crop, seeds or seedlings, but phytotoxic to the weed seeds or seedlings most frequently encountered, the crop grows in an almost weedfree environment.
- the pre-emergence herbicide may be used over the entire field, but it is normally used in a narrow band which straddles the crop row and the balance of the weeds are controlled by various cultivation methods.
- the herbicides of the present invention are selective toward small seeded annual grasses and broad-leafed plants, and so are efiective against the most common weeds but have little effect on such valuable row crops as corn and beans.
- the phytocidal composition may be applied to the soil in any convenient form.
- the method-of combatting weeds comprising ap- 2562911 fP July 1951 plying to the soil a phytotoxic amount of n-propyl N,N- 2642451 welllard et a1 June 1953 di n propylthiolcarbamate Kosmin g' 24! 12.
- the method of combatting weeds comprising applying to the soil a phytotoxic amount of n-propy1'N,N- 10 OTHER REFERENCES di-n-butylthiolcarbamate.
- the method of combatting weeds comprising ap- (1953).
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
THIOLCARBAMATES AND USE AS HERBICIDES Harry Tilles, El Cerrito, and Joe Antognini, Mountain View, Calif., assiguors t Staulfer Chemical Company, a corporation of Delaware CERTAIN No Drawing. Application January 17, 1956 Serial No. 559,541
13 Claims. (Cl. 71-2.7)
Code Name Ethyl N N-di-n-propylthiolcarbamate. Methyl ,N-di-n-propylthiolcarbamate. n-Propyl ,N-di-n-propylthiolcarbamate. Ethyl N,N-pentamethylenethiolcarbamate. n-Propyl N,N-pentamethylenethiolcarbamate. Isobutyl N.N-di-n-propylthiolcarbamate. n-Butyl N,N-di-n-propylthiolcarbamate.
M N,N-di-n-butylthiolcarbamate. Ethyl N,N-di-n-butylthiolcarbamate. sec-Butyl N,N-di-n-propylthiolcarbamate. n-Amyl N, -di-n-propylthiolcarbamate. n-Propyl N ,N-di-isopropylthiolcarbamate.
Isopropyl N ,N-di-isobutylthiolcarbamate.
Thus, the compounds of the present invention may be represented by the formula:
wherein R is a lower alkyl radical and, R and R are lower alkyl groups which have at least three carbon atoms. R and R may be a single alkyl group having at least five carbon atoms and having two bonds available nited States Patent for attachment to the nitrogen atom, as in R-1817 wherev in N forms a part of a ring structure.
The following illustrative examples demonstrate the methods which may be employed to make typical compounds of the present invention. In the examples, all parts are by weight.
Example I (R-1608).Sodium is dispersed in xylene using oleic acid as the stabilizing agent until a particle size of 5-200 microns in diameter is obtained. Dispersion, equivalent to an amount of 16.9 parts (0.733 mole) of sodium, is then transferred to a reactor which has been previously flushed out with argon (or other inert gas such as nitrogen). A solution of 50 parts (0.806 mole) of ethanethiol dissolved in 86 parts of xylene is then gradually added to the sodium dispersion over an interval of 30 minutes. The temperature is maintained at 25 to 36 C. by cooling. The sodium ethylmercaptide forms as finely divided crystals which make an easily stirrable slurry. This suspension is heated to reflux, the heat is turned off, and parts (0.733 mole) of di-n-propylcarbarnyl chloride is added over an interval of 17 minutes to the refluxing slurry. The heat of reaction is sufficient to keep the xylene refluxing. After all of the di-mpropylcarbamyl chloride has been added, the mixture is refluxed for an additional 3 hours. It is then cooled, filtered from sodium chloride which has formed during the reaction, and the solvent is removed under reduced pressure. The residual liquid is then distilled under vacuum to give 125.5 parts (90.6% yield) of ethyl N,N-di-npropylthiolcarbamate (B.P. (31.5 mm.) 135.5 C.- 137.0 C., n 1.4770). The following analysis is obtained:
Calculated for Found CoHguN OS Percent C 57.1 67. 41 Percent H. 10.1 10. 26 Percent N- 7. 4 7. 17 16.9 16. 71 189 Example II (R-1607).When the general procedure of Example I is repeated except that 38 parts (0.50 mole) of l-propanethiol, sodium dispersion equivalent to 9.2 parts (.40 mole) of sodium, and 65.5 parts (0.40 mole) of di-n-propylcarbamyl chloride are employed, there is obtained 70.3 parts (86.5% yield) of n-propyl N,N-din- Example Ill (R1880).When the general procedure of Example I is repeated except that 9.12 parts (0.12 mole) of l-p-ropanethiol, sodium dispersion equivalent to 2.3 parts (0.10 mole) of sodium, and 19.2 parts (0.10 mole) of di-n-butylcarbamyl chloride are employed, there is obtained 20.4 parts (88.3% yield) of n-propyl N,N- di-n-butylthiolcarbamate, (B.P. (15 mm.) 156.5-159" C., n 1.4742
Example IV (R-1854).-When the general procedure of Example I is repeated except that 16.9 parts (0.188 mole) of Z-methyl-l-propanethiol, sodium dispersion equivalent to 3.45 parts (0.15 mole) of sodium and 24.5 parts (0.15 mole) of di-n-propylcarbamyl chloride are employed, there is obtained 25.2 parts (77.3% yield) of isobutyl N,N-di-n-propylthiolcarbamate (B.P. (18 mm.) 143145 0, n 1.4744).
Example V (RJ857).When the general procedure of Example I is repeated except that 16.9 parts (0.188 mole) of l-butanethiol, sodium dispersion equivalent to 3.45 parts (0.15 mole) sodium and 24.5 parts (0.15 mole) of di-n-propylcarbamyl chloride are employed, there is obtained 24.8 parts (76% yield) of n-butyl N,N-di-n-propyl- 3 thiolcarbamate (B.P. (19 mm.) l51.0-151.5' C., 11 1.4766).
Example VI (R-I866).The general procedure of Example I was followed except that 25 parts (0.52 mole) of methanethiol is added in small portions at 50-60 C. to the sodium dispersion equivalent to 2.3 parts (0.10 mole) of sodium. It is necessary to make sure that unreacted mercaptan does not build up in the reaction mixture since a violent reaction may take place if too much unreacted mercaptan is present with unreacted dispersion. After all of the sodium dispersion has reacted which is evidenced by the reaction mixture changing from a purplish hue to a white color, it is heated to reflux and 19.2 parts (0.10 mole) of di-n-butylcarbamyl chloride is added. After working up in the usual manner, there is obtained 13.9 parts (68.5% yield) of methyl N,N,-din-butylthiolcarbamate (B.P. (20 mm.) 144-146 C., n 1.4760).
Example VII (R-I870).The general procedure of Example I is followed except that 6.2 parts (0.10 mole) of ethanethiol is added to sodium dispersion equivalent to 2.3 parts (0.10 mole) of sodium at an initial tempera ture of 27 C. and allowing the temperature to rise to 65 C. during the mercaptan addition. The mixture is then heated to reflux and 19.2 parts (0.10 mole) of din-butylcarbamyl chloride is added. There is obtained 16.7 parts (76.8% yield of ethyl N,N-di-n-butylthiolcarbamate (B.P. (22 mm.) 154.0-154.5, r25 1.4740).
Example VIII (R-1606).273 parts of anhydrous isopropanol are added to a glass or steel reactor and 3.5 parts (0.153 mole) of sodium is added. The mixture is heated to reflux and the sodium gradually dissolves. The solution is then rapidly cooled in ice water. At 50 C., a thick solid of sodium isopropoxide comes out of solution. The mixture is cooled to 30 and then 9.17 parts (0.191 mole) of methanethiol is added rapidly. The solid dissolves immediately. The clear solution is heated to boiling and 198 parts of isopropanol is distilled off. 89 parts of anhydrous xylene is then added and 77 parts of isopropanol-xylene mixture is distilled. 89 parts more xylene is added and 89 parts of isopropanol-xylene mixture is distilled. 89 parts more xylene is added and 89 parts of solvent, probably pure xylene by now, is distilled. 49 parts more xylene is added, the mixture is heated to reflux, and 25 parts of di-n-propylcarbamyl chloride is added during 4 minutes. The reaction is not very exothermic. The mixture is then refluxed for 14 hours, cooled, filtered from salt, the cake is washed with a little xylene and the solvent is removed under reduced pressure. The residue is then vacuum. distilled and there is obtained 16.7 parts (62.5% yield) of methyl N,N-din-propylthiolcarbamate (B.P. (30 mm.) 1285-1295, a 1.4808).
Example IX (R-181 7 ).When the general procedure of Example VIII is repeated except that 11.7 parts (0.188 mole) of ethanethiol, 3.45 parts (0.15 mole) of sodium and 22.1 parts of N,N,-pentamethylenecarbamyl chloride are employed, there is obtained 14.4 parts (55.5% yield) of ethyl N,N-pentamethylenethiolcarbamate (B. P. (31.5 mm.) 1505-1510", 11 15168).
Example X (R-1905). When the general procedure of Example VIII is repeated except that 13.0 parts (0.125 mole) of l-pentanethiol, 2.3 parts (0.10 mole) of sodium and 16.4 parts of di-isopropylcarbamyl chloride are employed, there is obtained 15.8 parts (68.3%) of n-amyl N,N,-di-isopropylthiolcarbamate (B.P. (22 mm.) 145- 149 C., a 1.4721).
Example XI (R-1824).Wl1en the general procedure of Example VIII is repeated except that 14.3 parts (0.188 mole) of 2-propanethiol, 3.45 parts (0.15 mole) of sodium and 22.1 parts (0.15 mole) of N,N-pentarnethyl- The compounds of the present invention have been extensively tested as herbicides and have been particularly evaluated as pre-emergence herbicides. Pre-emergence herbicides are ordinarily used by placing a narrow band of the herbicide over the center of a seeded crop row at time of planting or before crop emerges. If the herbicide is harmless to the desired crop, seeds or seedlings, but phytotoxic to the weed seeds or seedlings most frequently encountered, the crop grows in an almost weedfree environment. Of course, the pre-emergence herbicide may be used over the entire field, but it is normally used in a narrow band which straddles the crop row and the balance of the weeds are controlled by various cultivation methods. The herbicides of the present invention are selective toward small seeded annual grasses and broad-leafed plants, and so are efiective against the most common weeds but have little effect on such valuable row crops as corn and beans. The phytocidal composition may be applied to the soil in any convenient form. For instance, it can be dissolved in a solvent, such as acetone, or emulsified and sprayed onto the soil, or it can be combined with a dry inert carrier and applied as a dust or as granules; although the composition may be applied to an entire crop plot, it is generally preferred to apply it in a narrow band, say 6", over the seeded row of a newly planted crop. Generally, rates of application of from one-half to twenty pounds per acre of actual area treated will be found suitable.
The following example shows the effect of R-1608 when used to protect corn from Weeds:
Example XlI.-A field test consisted of applying the compounds at the rate of 1, 2, 4, 8 and 10 pounds/80 gallons/acre as pre-emergence treatments to corn. The compound was dissolved in a small amount of acetone emulsified in water and applied at the desired rate by mounting a spray nozzle behind the planter packer wheel. A 6" band was applied and the rates of application are on the basis of the area of actual application and not on the total area of the plot treated. The weather was sunny, the air temperature 70 F., the soil temperature was 78, and the seed bed was in good tilth and very dry. Immediately after the test, the plots were sprinkler parison with check plots. The following data were obenecarbamyl. chloride are employed, there is obtained tained:
TABLE 1 Results 16 days after application Corn Stand 1 Rye 2 Rate I II III Av. I II III Av. A, lb.
1 10 8 l0 9. 3 100 100 100 100 2 9 15 8 10. 6 100 100 100 100 Rl608 4 11 10 12 11. 0 100 100 100 100 s 12 12 3 9. a 100 100 100 100 10 11 12 s 10. 3 100 100 100 100 Check.--- 0 9 6 11 8. 6 0 0 0 0 Oats 2 Dead Nettle 2 1 100 100 100 100 100 100 100 100 2 100 100 100 100 100 100 100 100 4 100 100 100 100 100 100 100 100 s 100 100 100 100 100 100 100 100 10 100 100 100 100 100 100 100 100 Check... 0 0 0 0 0 0 0 (l 0 1 Corn stand-number of plants/10 it. of row. 2 Percent control of weeds.
Example XIII.A number of the compounds were tested at rates of application of and 20 pounds per acre. The method of testing was to plant the seeds in 3" diameter paper cans and drench the material on at 30 ml can. The seeds tested were peas, corn, radish, cucumm2 81om1510010111 Oats Cucumber 4. As .a composition of matter, v n-propyl N,N-di-r1- propylthiolcarbamat'e.
Rye
Ge. E
5. As a composition of matter, n-propyl N,N-di-nbutylthiolcarbamate.
6. As a composition of matter, n-amyl, N,N-isopropylthiolcarbamate.
7. The method of combatting weeds comprising apply- Radish TABLE 2 The data set TABLE 3 Corn The seeds tested were peas,
sing app Rate/A.,
m N a O 5 a 000 5005000200 50000005000050000005050 79.005400835322002 o m mm m mmm mmm mmmm 11 11 55 T m w3118111 00111100000 1 65215560413033 W. n n u R 5 55 5 00500005000050.0000 M Ww%w%- m %%m% 7m3 2 05760581539298 11 111 1 1 5 5 5 5 8 00 O9 00 W w mm mmmw m mmmmlm N11 1 11 e m D. 000 00000000000 0000 .00 a 00 07 00 n e mmm mmmmwmmmmmwmmmi 1 11 S G 5 55 55 5 n 5 L 0 0 oooomom 08 00 h G mmm mmm mm1m1m 1 1 u S a U q 00000000000000000000 .00 00 e 0 -oO 00 S 6 mmmmmmmmwwmmmmmmmmlm l1 11 G 55 55 L 0 00 00 G mm mmm mmmmmmlm mm 11 11 n m C 00000000000000000000 00 00 I 0 00 90 9 mmmmmwmwmmmmmwmmmmlm l1 1 G 5 555 555 5 5 L 00om00000fi4 507 8 &5&95 86 66 G 11 1111 1 s a e P 5 a 00000000500500005000 07 00 57 00 G mmm mmmm mm mmmm mm m 11 2 2 2 2 2 2 n 2 a 0 oMoWeWoWoMowowowowowowmo mowowowmowo her and either rye or cats. The data set forth in Table 2 were obtained:
a e P 000000 102490 811 G 6 0 00000 M 828282 A W t m d "F" m "n" O p a 1 7 m 0 0 1 o MEN 0 a a a Example XIV.-A number of compounds were tested in flats in the greenhouse, at 2 /2 and pounds/ 80 gallons of solution/ acre. Application made with a fan type corn, squash, snapbeans, rye and oats. forth in Table 3 were obtained:
Compound nozzle at lbs. pressure.
Ge.=Percentage of seeds germinating. Gr.=Growth wherein 10 equals normal growth, and 0 indicates no growth.
We claim: 1. As a composition of matter, a compound of the formula R,s-GN
2. As a composition of matter ethyl N,N-di-n-propylthiolcarbamate.
3. As a composition of matter ethyl N,N-di-n-butylthiolcarbamate.
wherein R is a lower alkyl radical and R and R are identical lower alkyl radicals having at least three carbon 70 atoms. atoms.
ing to the soil :1 phytotoxic amount olf ethyl N,N-di-n- References Cited in the file of this patent propylthiolcarbamate. D T ES PAT NT 10. The method of combatting weeds comprising ap- UNITE S AT E S plying to the soil a phytotoxic amount of ethyl N,N-din- 2*060'733 Hunt et 1936 butynhiolcarbamate 2,160,880 Loane et a1. June 6, 1939 11. The method-of combatting weeds comprising ap- 2562911 fP July 1951 plying to the soil a phytotoxic amount of n-propyl N,N- 2642451 welllard et a1 June 1953 di n propylthiolcarbamate Kosmin g' 24! 12. The method of combatting weeds comprising applying to the soil a phytotoxic amount of n-propy1'N,N- 10 OTHER REFERENCES di-n-butylthiolcarbamate. Riemschneider et a1.: Monatshefte 84, pp. 5 18-21 13. The method of combatting weeds comprising ap- (1953).
plying to the soil a phytotoxic amount of n-amyl N,N-diisopropylthiolcarbamate.
Claims (1)
- 7. THE METHOD OF COMBATTING WEEDS COMPRISING APPLYING TO THE SOIL A PHYTOTOXIC AMOUNT OF A COMPOUND HAVING THE FORMULA
Priority Applications (23)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL213753D NL213753A (en) | 1956-01-17 | ||
| BE559977D BE559977A (en) | 1956-01-17 | ||
| BE571955D BE571955A (en) | 1956-01-17 | ||
| NL232065D NL232065A (en) | 1956-01-17 | ||
| BE582794D BE582794A (en) | 1956-01-17 | ||
| NL108235D NL108235C (en) | 1956-01-17 | ||
| BE554214D BE554214A (en) | 1956-01-17 | ||
| US559541A US2913327A (en) | 1956-01-17 | 1956-01-17 | Certain thiolcarbamates and use as herbicides |
| FR1171404D FR1171404A (en) | 1956-01-17 | 1957-01-15 | Improvements in herbicides and their manufacturing processes |
| GB1845/57A GB808753A (en) | 1956-01-17 | 1957-01-17 | Improvements in or relating to thiolcarbamates |
| DEST1239A DE1031571B (en) | 1956-01-17 | 1957-01-17 | Herbicides |
| GB23841/57A GB862548A (en) | 1956-01-17 | 1957-07-26 | Improvements in or relating to phytocidal compositions of matter |
| CH357238D CH357238A (en) | 1956-01-17 | 1957-07-31 | Herbicides |
| DEST12853A DE1081715B (en) | 1956-01-17 | 1957-08-06 | Herbicides |
| FR72159D FR72159E (en) | 1956-01-17 | 1957-08-07 | Improvements to herbicides and their manufacturing process |
| GB31728/58A GB868111A (en) | 1956-01-17 | 1958-10-03 | Improvements in or relating to thiolcarbamates |
| DEST14328A DE1082452B (en) | 1956-01-17 | 1958-10-10 | Herbicides |
| FR777391A FR74319E (en) | 1956-01-17 | 1958-10-23 | Improvements in herbicides and their manufacturing processes |
| CH6652558A CH371921A (en) | 1956-01-17 | 1958-11-24 | Herbicides |
| GB30509/59A GB862250A (en) | 1956-01-17 | 1959-09-07 | Improvements in or relating to thiolcarbamates |
| FR806064A FR77056E (en) | 1956-01-17 | 1959-09-25 | Improvements in herbicides and their manufacturing processes |
| CH8043159A CH368015A (en) | 1956-01-17 | 1959-11-10 | Herbicides |
| MY19622A MY6200002A (en) | 1956-01-17 | 1962-12-31 | Improvements in or relating to thiolcarbamates |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US559541A US2913327A (en) | 1956-01-17 | 1956-01-17 | Certain thiolcarbamates and use as herbicides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2913327A true US2913327A (en) | 1959-11-17 |
Family
ID=24233981
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US559541A Expired - Lifetime US2913327A (en) | 1956-01-17 | 1956-01-17 | Certain thiolcarbamates and use as herbicides |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US2913327A (en) |
| BE (4) | BE582794A (en) |
| CH (3) | CH357238A (en) |
| DE (3) | DE1031571B (en) |
| FR (4) | FR1171404A (en) |
| GB (4) | GB808753A (en) |
| MY (1) | MY6200002A (en) |
| NL (3) | NL232065A (en) |
Cited By (73)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3037853A (en) * | 1958-04-04 | 1962-06-05 | Du Pont | Herbicidal composition and method employing a mixture of ethyl n, n-dipropylthiolcarbamate and a herbicidal s-triazine |
| US3046189A (en) * | 1957-05-18 | 1962-07-24 | Merck Ag E | Nematocidal agents |
| US3095299A (en) * | 1960-05-11 | 1963-06-25 | Du Pont | Herbicidal composition and method |
| US3101263A (en) * | 1959-04-20 | 1963-08-20 | Stauffer Chemical Co | Herbicidal method |
| US3154402A (en) * | 1962-03-12 | 1964-10-27 | Exxon Research Engineering Co | Wax formulations of thiolcarbamate herbicides |
| US3175897A (en) * | 1962-08-21 | 1965-03-30 | Stauffer Chemical Co | Asymmetric thiolcarbamates as herbicides |
| US3185720A (en) * | 1962-08-21 | 1965-05-25 | Stauffer Chemical Co | Asymmetric thiolcarbamates |
| US3198786A (en) * | 1961-05-01 | 1965-08-03 | Stauffer Chemical Co | Alkyl hexamethylene-thiolcarbamates |
| US3298817A (en) * | 1959-04-16 | 1967-01-17 | Tilles Harry | Method of combating weeds |
| US3305576A (en) * | 1959-07-10 | 1967-02-21 | Monsanto Co | 3-chloropropyl diisopropylthiolcarbamate |
| US3893838A (en) * | 1972-11-16 | 1975-07-08 | Stauffer Chemical Co | Halogenated esters as herbicide antidotes |
| US3923494A (en) * | 1973-05-24 | 1975-12-02 | Stauffer Chemical Co | Gem-bis amide herbicide antidote compositions and methods of use |
| US3976469A (en) * | 1972-11-16 | 1976-08-24 | Stauffer Chemical Company | Halogenated ketones as herbicide antidotes |
| US4021224A (en) * | 1971-12-09 | 1977-05-03 | Stauffer Chemical Company | Herbicide compositions |
| US4036628A (en) * | 1972-11-13 | 1977-07-19 | Stauffer Chemical Company | Phosphorus containing herbicide antidotes |
| US4098599A (en) * | 1975-09-12 | 1978-07-04 | Stauffer Chemical Company | Antidote compositions and method of use with herbicides |
| US4137070A (en) * | 1971-04-16 | 1979-01-30 | Stauffer Chemical Company | Herbicide compositions |
| US4208203A (en) * | 1971-09-17 | 1980-06-17 | Gulf Research & Development Co. | Method of protecting corn from herbicides |
| US4222938A (en) * | 1978-09-29 | 1980-09-16 | Monsanto Company | Preparation of thiolcarbamates |
| US4268456A (en) * | 1979-09-24 | 1981-05-19 | Ppg Industries, Inc. | Process for preparing chlorothiolformates |
| US4273725A (en) * | 1979-07-25 | 1981-06-16 | Ppg Industries, Inc. | Process for preparing chlorothiolformates |
| US4276078A (en) * | 1978-08-04 | 1981-06-30 | Stauffer Chemical Company | Herbicide compositions |
| US4279638A (en) * | 1979-08-13 | 1981-07-21 | Stauffer Chemical Company | 3,5-Disubstituted 1,2,4-oxadiazole herbicidal antidotes |
| US4299616A (en) * | 1980-03-31 | 1981-11-10 | Stauffer Chemical Company | Herbicide compositions of extended soil life |
| US4320070A (en) * | 1979-09-24 | 1982-03-16 | Ppg Industries, Inc. | Process for preparing chlorothiolformates |
| US4321084A (en) * | 1977-09-23 | 1982-03-23 | Stauffer Chemical Company | Certain halogenated phenols as antidotes for thiocarbamate herbicides |
| US4321083A (en) * | 1980-04-21 | 1982-03-23 | Stauffer Chemical Company | N-Acyl-phenyl-thiourea herbicidal antidotes |
| US4338120A (en) * | 1980-04-21 | 1982-07-06 | Stauffer Chemical Company | Halo-substituted thionoacyl ketone herbicidal antidotes |
| FR2509136A1 (en) * | 1981-07-08 | 1983-01-14 | Eszakmagyar Vegyimuevek | HERBICIDE COMPOSITION CONTAINING A MIXTURE OF TWO ESTERS OF THIOCARBAMIC ACIDS |
| US4378239A (en) * | 1981-04-27 | 1983-03-29 | Stauffer Chemical Company | N-Methylcarbamoyloxy benzaldehyde imine herbicide extenders |
| US4380468A (en) * | 1980-10-14 | 1983-04-19 | Stauffer Chemical Company | Isonitriles as herbicide extenders |
| US4380467A (en) * | 1981-03-12 | 1983-04-19 | Stauffer Chemical Company | Amine oxanilic acid salts as herbicide extenders |
| US4381196A (en) * | 1981-04-20 | 1983-04-26 | Stauffer Chemical Company | O-(Substituted phenyl) N-methylcarbamates as herbicide extenders |
| US4381195A (en) * | 1981-04-20 | 1983-04-26 | Stauffer Chemical Company | N-Methylcarbamoyloxy anilides as herbicide extenders |
| US4381936A (en) * | 1980-03-31 | 1983-05-03 | Stauffer Chemical Company | Herbicide compositions of extended soil life |
| US4386955A (en) * | 1981-04-20 | 1983-06-07 | Stauffer Chemical Company | O-(Substituted phenyl) N-methylcarbamates as herbicide extenders |
| US4396419A (en) * | 1981-03-16 | 1983-08-02 | Stauffer Chemical Company | Chloroacetamido alkoxy ethane herbicide antidotes |
| US4400197A (en) * | 1979-12-26 | 1983-08-23 | Ppg Industries, Inc. | N-(Optionally substituted 1,3-dioxolan- or dioxan-2-ylmethyl)-N-alkyl, alkenyl, or alkynyl-2,2-dichloroacetamides |
| US4420322A (en) * | 1979-04-02 | 1983-12-13 | Stauffer Chemical Company | Herbicidal antidotes |
| US4420323A (en) * | 1982-05-10 | 1983-12-13 | Stauffer Chemical Company | Thiophosphoryl carbamate herbicide antidotes |
| US4422869A (en) * | 1981-04-20 | 1983-12-27 | Stauffer Chemical Company | Halogenated allylthioisopropyl N-methylcarbamates as herbicide extenders |
| US4432909A (en) * | 1981-03-12 | 1984-02-21 | Stauffer Chemical Company | Amine oxanilic acid salts as herbicide extenders |
| US4433999A (en) | 1981-07-20 | 1984-02-28 | Stauffer Chemical Company | Herbicide compositions containing soil life extenders and antidotes |
| US4441916A (en) * | 1981-10-19 | 1984-04-10 | Stauffer Chemical Company | Haloalkyloxime herbicidal antidotes |
| US4478636A (en) * | 1982-06-01 | 1984-10-23 | Stauffer Chemical Company | Herbicidal compositions of extended soil life |
| US4490166A (en) * | 1982-06-01 | 1984-12-25 | Stauffer Chemical Company | Iminophenyl N-methylcarbamates as herbicide extenders |
| US4495365A (en) * | 1980-11-21 | 1985-01-22 | Stauffer Chemical Co. | N-Acylsulfonamide herbicidal antidotes |
| US4517012A (en) * | 1979-07-09 | 1985-05-14 | Stauffer Chemical Company | Herbicide compositions |
| US4540429A (en) * | 1981-03-16 | 1985-09-10 | Stauffer Chemical Company | 4-Phenyl-1,2,3-thiadiazoles as herbicide extenders |
| US4546199A (en) * | 1981-04-20 | 1985-10-08 | Stauffer Chemical Company | Halogenated allylthioisopropyl N-methyl carbamates as herbicide extenders |
| US4545805A (en) * | 1982-03-24 | 1985-10-08 | Stauffer Chemical Company | Herbicide compositions of extended soil life |
| US4559082A (en) * | 1983-08-12 | 1985-12-17 | Stauffer Chemical Co. | Herbicide compositions of extended soil life |
| US4613358A (en) * | 1983-05-20 | 1986-09-23 | Stauffer Chemical Co. | Herbicide compositions of extended soil life |
| US4648894A (en) * | 1983-05-20 | 1987-03-10 | Stauffer Chemical Co. | Herbicide compositions of extended soil life |
| US4650516A (en) * | 1979-03-23 | 1987-03-17 | Stauffer Chemical Co. | α-halo-Ω-haloalkylamides herbicidal antidotes |
| US4652298A (en) * | 1983-05-16 | 1987-03-24 | Stauffer Chemical Co. | Herbicide compositions of extended soil life |
| US4652301A (en) * | 1983-05-16 | 1987-03-24 | Stauffer Chemical Co. | Herbicide compositions of extended soil life |
| US4652300A (en) * | 1983-05-16 | 1987-03-24 | Stauffer Chemical Co. | Herbicide compositions of extended soil life |
| US4652296A (en) * | 1983-05-16 | 1987-03-24 | Stauffer Chemical Co. | Herbicide compositions of extended soil life |
| US4652302A (en) * | 1983-05-20 | 1987-03-24 | Stauffer Chemical Co. | Herbicide compositions of extended soil life |
| US4662930A (en) * | 1983-05-20 | 1987-05-05 | Stauffer Chemical Co. | Herbicide compositions of extended soil life |
| WO1989009208A1 (en) * | 1988-03-30 | 1989-10-05 | Bio-Tox Diagnostics Kommanditbolag | Carbamic acid ester and a preparation thereof for treatment of addiction to alcohol |
| US4915725A (en) * | 1978-09-20 | 1990-04-10 | Ici Americas, Inc. | Herbicide compositions of extended soil life |
| US5011526A (en) * | 1978-09-20 | 1991-04-30 | Ici Americas Inc. | Herbicide compositions of extended soil life |
| US5041599A (en) * | 1990-07-30 | 1991-08-20 | Phillips Petroleum Company | Catalytic synthesis of thionocarbamates from xanthates and amines |
| US5171356A (en) * | 1984-09-19 | 1992-12-15 | Ici Americas Inc. | Herbicide compositions of extended soil life |
| US5527762A (en) * | 1990-12-12 | 1996-06-18 | Zeneca Limited | Antidoting herbicidal 3-isoxazolidinone compounds |
| EP2052606A1 (en) | 2007-10-24 | 2009-04-29 | Bayer CropScience AG | Herbicide combination |
| DE102008037620A1 (en) | 2008-08-14 | 2010-02-18 | Bayer Crop Science Ag | Herbicide combination with dimethoxytriazinyl-substituted difluoromethanesulfonylanilides |
| WO2012049266A1 (en) | 2010-10-15 | 2012-04-19 | Bayer Cropscience Ag | Use of als inhibitor herbicides for control of unwanted vegetation in als inhibitor herbicide tolerant beta vulgaris plants |
| WO2012150333A1 (en) | 2011-05-04 | 2012-11-08 | Bayer Intellectual Property Gmbh | Use of als inhibitor herbicides for control of unwanted vegetation in als inhibitor herbicide tolerant brassica, such as b. napus, plants |
| WO2014090760A1 (en) | 2012-12-13 | 2014-06-19 | Bayer Cropscience Ag | Use of als inhibitor herbicides for control of unwanted vegetation in als inhibitor herbicide tolerant beta vulgaris plants |
| WO2023062184A1 (en) | 2021-10-15 | 2023-04-20 | KWS SAAT SE & Co. KGaA | Als inhibitor herbicide tolerant beta vulgaris mutants |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE571955A (en) * | 1956-01-17 | |||
| DE1142464B (en) * | 1959-05-11 | 1963-01-17 | Monsanto Chemicals | Combat unwanted vegetation, weed killing, leaf removal, soil decontamination, fungus and nematode control |
| US3318676A (en) * | 1959-07-10 | 1967-05-09 | Monsanto Co | Controlling vegetation with haloalkyl thiolcarbamates |
| US3839010A (en) * | 1970-05-19 | 1974-10-01 | Exxon Research Engineering Co | Thiocarbamic acid ester pesticides |
| DE2329043A1 (en) * | 1973-06-07 | 1975-01-02 | Basf Ag | CARBOTHIOLATES |
| US4056549A (en) | 1976-06-07 | 1977-11-01 | Ppg Industries, Inc. | S-3-Methoxyphenyl N-alkylthiolcarbamates and S-3-methylthiophenyl N-alkylthiolcarbamates |
| ES8104796A1 (en) * | 1979-07-25 | 1981-05-16 | Hoechst Ag | Fungicidal thioglycolic acid anilides, process for their preparation and pesticides containing them. |
| AU549319B2 (en) * | 1980-10-21 | 1986-01-23 | Hodogaya Chemical Co. Ltd. | Nematocide |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2060733A (en) * | 1934-09-04 | 1936-11-10 | Du Pont | Process of treating cellulose and derivatives thereof |
| US2160880A (en) * | 1936-11-02 | 1939-06-06 | Standard Oil Co | Lubricant |
| US2562011A (en) * | 1948-12-10 | 1951-07-24 | Goodrich Co B F | Herbicidal compositions and application thereof |
| US2642451A (en) * | 1953-06-16 | Thiolurethanes and processes for | ||
| US2687348A (en) * | 1952-09-17 | 1954-08-24 | Monsanto Chemicals | Herbicidal compositions |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE858352C (en) * | 1948-10-02 | 1952-12-04 | Schering Ag | Prevention of germination in root crops and the like like |
| BE571955A (en) * | 1956-01-17 |
-
0
- BE BE571955D patent/BE571955A/xx unknown
- NL NL213753D patent/NL213753A/xx unknown
- BE BE554214D patent/BE554214A/xx unknown
- BE BE559977D patent/BE559977A/xx unknown
- NL NL108235D patent/NL108235C/xx active
- BE BE582794D patent/BE582794A/xx unknown
- NL NL232065D patent/NL232065A/xx unknown
-
1956
- 1956-01-17 US US559541A patent/US2913327A/en not_active Expired - Lifetime
-
1957
- 1957-01-15 FR FR1171404D patent/FR1171404A/en not_active Expired
- 1957-01-17 DE DEST1239A patent/DE1031571B/en active Pending
- 1957-01-17 GB GB1845/57A patent/GB808753A/en not_active Expired
- 1957-07-26 GB GB23841/57A patent/GB862548A/en not_active Expired
- 1957-07-31 CH CH357238D patent/CH357238A/en unknown
- 1957-08-06 DE DEST12853A patent/DE1081715B/en active Pending
- 1957-08-07 FR FR72159D patent/FR72159E/en not_active Expired
-
1958
- 1958-10-03 GB GB31728/58A patent/GB868111A/en not_active Expired
- 1958-10-10 DE DEST14328A patent/DE1082452B/en active Pending
- 1958-10-23 FR FR777391A patent/FR74319E/en not_active Expired
- 1958-11-24 CH CH6652558A patent/CH371921A/en unknown
-
1959
- 1959-09-07 GB GB30509/59A patent/GB862250A/en not_active Expired
- 1959-09-25 FR FR806064A patent/FR77056E/en not_active Expired
- 1959-11-10 CH CH8043159A patent/CH368015A/en unknown
-
1962
- 1962-12-31 MY MY19622A patent/MY6200002A/en unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2642451A (en) * | 1953-06-16 | Thiolurethanes and processes for | ||
| US2060733A (en) * | 1934-09-04 | 1936-11-10 | Du Pont | Process of treating cellulose and derivatives thereof |
| US2160880A (en) * | 1936-11-02 | 1939-06-06 | Standard Oil Co | Lubricant |
| US2562011A (en) * | 1948-12-10 | 1951-07-24 | Goodrich Co B F | Herbicidal compositions and application thereof |
| US2687348A (en) * | 1952-09-17 | 1954-08-24 | Monsanto Chemicals | Herbicidal compositions |
Cited By (81)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3046189A (en) * | 1957-05-18 | 1962-07-24 | Merck Ag E | Nematocidal agents |
| US3037853A (en) * | 1958-04-04 | 1962-06-05 | Du Pont | Herbicidal composition and method employing a mixture of ethyl n, n-dipropylthiolcarbamate and a herbicidal s-triazine |
| US3298817A (en) * | 1959-04-16 | 1967-01-17 | Tilles Harry | Method of combating weeds |
| US3101263A (en) * | 1959-04-20 | 1963-08-20 | Stauffer Chemical Co | Herbicidal method |
| US3305576A (en) * | 1959-07-10 | 1967-02-21 | Monsanto Co | 3-chloropropyl diisopropylthiolcarbamate |
| US3095299A (en) * | 1960-05-11 | 1963-06-25 | Du Pont | Herbicidal composition and method |
| US3198786A (en) * | 1961-05-01 | 1965-08-03 | Stauffer Chemical Co | Alkyl hexamethylene-thiolcarbamates |
| US3154402A (en) * | 1962-03-12 | 1964-10-27 | Exxon Research Engineering Co | Wax formulations of thiolcarbamate herbicides |
| US3175897A (en) * | 1962-08-21 | 1965-03-30 | Stauffer Chemical Co | Asymmetric thiolcarbamates as herbicides |
| US3185720A (en) * | 1962-08-21 | 1965-05-25 | Stauffer Chemical Co | Asymmetric thiolcarbamates |
| US4137070A (en) * | 1971-04-16 | 1979-01-30 | Stauffer Chemical Company | Herbicide compositions |
| US4208203A (en) * | 1971-09-17 | 1980-06-17 | Gulf Research & Development Co. | Method of protecting corn from herbicides |
| US4021224A (en) * | 1971-12-09 | 1977-05-03 | Stauffer Chemical Company | Herbicide compositions |
| US4036628A (en) * | 1972-11-13 | 1977-07-19 | Stauffer Chemical Company | Phosphorus containing herbicide antidotes |
| US3893838A (en) * | 1972-11-16 | 1975-07-08 | Stauffer Chemical Co | Halogenated esters as herbicide antidotes |
| US3976469A (en) * | 1972-11-16 | 1976-08-24 | Stauffer Chemical Company | Halogenated ketones as herbicide antidotes |
| US3923494A (en) * | 1973-05-24 | 1975-12-02 | Stauffer Chemical Co | Gem-bis amide herbicide antidote compositions and methods of use |
| US4098599A (en) * | 1975-09-12 | 1978-07-04 | Stauffer Chemical Company | Antidote compositions and method of use with herbicides |
| US4321084A (en) * | 1977-09-23 | 1982-03-23 | Stauffer Chemical Company | Certain halogenated phenols as antidotes for thiocarbamate herbicides |
| US4276078A (en) * | 1978-08-04 | 1981-06-30 | Stauffer Chemical Company | Herbicide compositions |
| US4915725A (en) * | 1978-09-20 | 1990-04-10 | Ici Americas, Inc. | Herbicide compositions of extended soil life |
| US5011526A (en) * | 1978-09-20 | 1991-04-30 | Ici Americas Inc. | Herbicide compositions of extended soil life |
| US4222938A (en) * | 1978-09-29 | 1980-09-16 | Monsanto Company | Preparation of thiolcarbamates |
| US4650516A (en) * | 1979-03-23 | 1987-03-17 | Stauffer Chemical Co. | α-halo-Ω-haloalkylamides herbicidal antidotes |
| US4420322A (en) * | 1979-04-02 | 1983-12-13 | Stauffer Chemical Company | Herbicidal antidotes |
| US4517012A (en) * | 1979-07-09 | 1985-05-14 | Stauffer Chemical Company | Herbicide compositions |
| US4273725A (en) * | 1979-07-25 | 1981-06-16 | Ppg Industries, Inc. | Process for preparing chlorothiolformates |
| US4279638A (en) * | 1979-08-13 | 1981-07-21 | Stauffer Chemical Company | 3,5-Disubstituted 1,2,4-oxadiazole herbicidal antidotes |
| US4268456A (en) * | 1979-09-24 | 1981-05-19 | Ppg Industries, Inc. | Process for preparing chlorothiolformates |
| US4320070A (en) * | 1979-09-24 | 1982-03-16 | Ppg Industries, Inc. | Process for preparing chlorothiolformates |
| US4400197A (en) * | 1979-12-26 | 1983-08-23 | Ppg Industries, Inc. | N-(Optionally substituted 1,3-dioxolan- or dioxan-2-ylmethyl)-N-alkyl, alkenyl, or alkynyl-2,2-dichloroacetamides |
| US4381936A (en) * | 1980-03-31 | 1983-05-03 | Stauffer Chemical Company | Herbicide compositions of extended soil life |
| EP0038945A3 (en) * | 1980-03-31 | 1981-12-16 | Stauffer Chemical Company | Herbicide compositions of extended soil life |
| US4299616A (en) * | 1980-03-31 | 1981-11-10 | Stauffer Chemical Company | Herbicide compositions of extended soil life |
| US4321083A (en) * | 1980-04-21 | 1982-03-23 | Stauffer Chemical Company | N-Acyl-phenyl-thiourea herbicidal antidotes |
| US4338120A (en) * | 1980-04-21 | 1982-07-06 | Stauffer Chemical Company | Halo-substituted thionoacyl ketone herbicidal antidotes |
| US4380468A (en) * | 1980-10-14 | 1983-04-19 | Stauffer Chemical Company | Isonitriles as herbicide extenders |
| US4495365A (en) * | 1980-11-21 | 1985-01-22 | Stauffer Chemical Co. | N-Acylsulfonamide herbicidal antidotes |
| US4380467A (en) * | 1981-03-12 | 1983-04-19 | Stauffer Chemical Company | Amine oxanilic acid salts as herbicide extenders |
| US4432909A (en) * | 1981-03-12 | 1984-02-21 | Stauffer Chemical Company | Amine oxanilic acid salts as herbicide extenders |
| US4540429A (en) * | 1981-03-16 | 1985-09-10 | Stauffer Chemical Company | 4-Phenyl-1,2,3-thiadiazoles as herbicide extenders |
| US4396419A (en) * | 1981-03-16 | 1983-08-02 | Stauffer Chemical Company | Chloroacetamido alkoxy ethane herbicide antidotes |
| US4422869A (en) * | 1981-04-20 | 1983-12-27 | Stauffer Chemical Company | Halogenated allylthioisopropyl N-methylcarbamates as herbicide extenders |
| US4381196A (en) * | 1981-04-20 | 1983-04-26 | Stauffer Chemical Company | O-(Substituted phenyl) N-methylcarbamates as herbicide extenders |
| US4386955A (en) * | 1981-04-20 | 1983-06-07 | Stauffer Chemical Company | O-(Substituted phenyl) N-methylcarbamates as herbicide extenders |
| US4381195A (en) * | 1981-04-20 | 1983-04-26 | Stauffer Chemical Company | N-Methylcarbamoyloxy anilides as herbicide extenders |
| US4546199A (en) * | 1981-04-20 | 1985-10-08 | Stauffer Chemical Company | Halogenated allylthioisopropyl N-methyl carbamates as herbicide extenders |
| US4378239A (en) * | 1981-04-27 | 1983-03-29 | Stauffer Chemical Company | N-Methylcarbamoyloxy benzaldehyde imine herbicide extenders |
| FR2509136A1 (en) * | 1981-07-08 | 1983-01-14 | Eszakmagyar Vegyimuevek | HERBICIDE COMPOSITION CONTAINING A MIXTURE OF TWO ESTERS OF THIOCARBAMIC ACIDS |
| US4433999A (en) | 1981-07-20 | 1984-02-28 | Stauffer Chemical Company | Herbicide compositions containing soil life extenders and antidotes |
| US4441916A (en) * | 1981-10-19 | 1984-04-10 | Stauffer Chemical Company | Haloalkyloxime herbicidal antidotes |
| US4545805A (en) * | 1982-03-24 | 1985-10-08 | Stauffer Chemical Company | Herbicide compositions of extended soil life |
| US4420323A (en) * | 1982-05-10 | 1983-12-13 | Stauffer Chemical Company | Thiophosphoryl carbamate herbicide antidotes |
| US4478636A (en) * | 1982-06-01 | 1984-10-23 | Stauffer Chemical Company | Herbicidal compositions of extended soil life |
| US4490166A (en) * | 1982-06-01 | 1984-12-25 | Stauffer Chemical Company | Iminophenyl N-methylcarbamates as herbicide extenders |
| US4652300A (en) * | 1983-05-16 | 1987-03-24 | Stauffer Chemical Co. | Herbicide compositions of extended soil life |
| US4652298A (en) * | 1983-05-16 | 1987-03-24 | Stauffer Chemical Co. | Herbicide compositions of extended soil life |
| US4652301A (en) * | 1983-05-16 | 1987-03-24 | Stauffer Chemical Co. | Herbicide compositions of extended soil life |
| US4652296A (en) * | 1983-05-16 | 1987-03-24 | Stauffer Chemical Co. | Herbicide compositions of extended soil life |
| US4648894A (en) * | 1983-05-20 | 1987-03-10 | Stauffer Chemical Co. | Herbicide compositions of extended soil life |
| US4652302A (en) * | 1983-05-20 | 1987-03-24 | Stauffer Chemical Co. | Herbicide compositions of extended soil life |
| US4662930A (en) * | 1983-05-20 | 1987-05-05 | Stauffer Chemical Co. | Herbicide compositions of extended soil life |
| US4613358A (en) * | 1983-05-20 | 1986-09-23 | Stauffer Chemical Co. | Herbicide compositions of extended soil life |
| US4559082A (en) * | 1983-08-12 | 1985-12-17 | Stauffer Chemical Co. | Herbicide compositions of extended soil life |
| US5171356A (en) * | 1984-09-19 | 1992-12-15 | Ici Americas Inc. | Herbicide compositions of extended soil life |
| WO1989009208A1 (en) * | 1988-03-30 | 1989-10-05 | Bio-Tox Diagnostics Kommanditbolag | Carbamic acid ester and a preparation thereof for treatment of addiction to alcohol |
| US5100916A (en) * | 1988-03-30 | 1992-03-31 | Bio-Tox Diagnostics Kommanditbolag | Carbamic acid ester for treatment of addiction to alcohol |
| US5041599A (en) * | 1990-07-30 | 1991-08-20 | Phillips Petroleum Company | Catalytic synthesis of thionocarbamates from xanthates and amines |
| US5527762A (en) * | 1990-12-12 | 1996-06-18 | Zeneca Limited | Antidoting herbicidal 3-isoxazolidinone compounds |
| US5527761A (en) * | 1990-12-12 | 1996-06-18 | Zeneca Limited | Antidoting herbicidal 3-isoxazolidinone compounds |
| EP2052606A1 (en) | 2007-10-24 | 2009-04-29 | Bayer CropScience AG | Herbicide combination |
| US20100099564A1 (en) * | 2008-08-14 | 2010-04-22 | Bayer Cropscience Ag | Herbicide combination comprising dimethoxytriazinyl-substituted difluoromethanesulfonylanilides |
| DE102008037620A1 (en) | 2008-08-14 | 2010-02-18 | Bayer Crop Science Ag | Herbicide combination with dimethoxytriazinyl-substituted difluoromethanesulfonylanilides |
| WO2012049266A1 (en) | 2010-10-15 | 2012-04-19 | Bayer Cropscience Ag | Use of als inhibitor herbicides for control of unwanted vegetation in als inhibitor herbicide tolerant beta vulgaris plants |
| EP3284346A1 (en) | 2010-10-15 | 2018-02-21 | Bayer Intellectual Property GmbH | Use of als inhibitor herbicides for control of unwanted vegetation in als inhibitor herbicide tolerant beta vulgaris plants |
| US10544426B2 (en) | 2010-10-15 | 2020-01-28 | Bayer Intellectual Property Gmbh | Methods of using ALS inhibitor herbicides for control of unwanted vegetation in ALS inhibitor herbicide tolerant beta vulgaris plants |
| US11371057B2 (en) | 2010-10-15 | 2022-06-28 | Bayer Intellectual Property Gmbh | Methods of using ALS inhibitor herbicides for control of unwanted vegetation in ALS inhibitor herbicide tolerant beta vulgaris plants |
| WO2012150333A1 (en) | 2011-05-04 | 2012-11-08 | Bayer Intellectual Property Gmbh | Use of als inhibitor herbicides for control of unwanted vegetation in als inhibitor herbicide tolerant brassica, such as b. napus, plants |
| US9370183B2 (en) | 2011-05-04 | 2016-06-21 | Bayer Intellectual Property Gmbh | Use of ALS inhibitor herbicides for control of unwanted vegetation in ALS inhibitor herbicide tolerant Brassica, such as B. napus, plants |
| WO2014090760A1 (en) | 2012-12-13 | 2014-06-19 | Bayer Cropscience Ag | Use of als inhibitor herbicides for control of unwanted vegetation in als inhibitor herbicide tolerant beta vulgaris plants |
| WO2023062184A1 (en) | 2021-10-15 | 2023-04-20 | KWS SAAT SE & Co. KGaA | Als inhibitor herbicide tolerant beta vulgaris mutants |
Also Published As
| Publication number | Publication date |
|---|---|
| BE554214A (en) | |
| BE571955A (en) | |
| NL108235C (en) | |
| GB862548A (en) | 1961-03-15 |
| FR72159E (en) | 1960-03-30 |
| CH357238A (en) | 1961-09-30 |
| FR77056E (en) | 1962-01-12 |
| FR74319E (en) | 1960-11-07 |
| GB862250A (en) | 1961-03-08 |
| DE1031571B (en) | 1958-06-04 |
| MY6200002A (en) | 1962-12-31 |
| DE1082452B (en) | 1960-05-25 |
| NL232065A (en) | |
| GB808753A (en) | 1959-02-11 |
| FR1171404A (en) | 1959-01-26 |
| GB868111A (en) | 1961-05-17 |
| BE582794A (en) | |
| CH368015A (en) | 1963-03-15 |
| BE559977A (en) | |
| DE1081715B (en) | 1960-05-12 |
| CH371921A (en) | 1963-09-15 |
| NL213753A (en) |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US2913327A (en) | Certain thiolcarbamates and use as herbicides | |
| US2655445A (en) | 3-(halophenyl)-1-methyl-1-(methyl or ethyl) ureas and herbicidal compositions and methods employing same | |
| US3367949A (en) | Sulfanilamides | |
| US3564608A (en) | Selected n-acylsubstituted-n'-hydroxyguanidines | |
| US2913326A (en) | Propyl-n, n-diethylthiolcarbamate and use as herbicide | |
| US2901498A (en) | N-alkyl, n-allyl thiolcarbamate compositions | |
| US2916370A (en) | Chlorinated thiolcarbamates and their use as herbicides | |
| US4331807A (en) | Pyridazine urea plant growth regulators | |
| US4108627A (en) | N-(substituted phenyl) derivatives of saccharin | |
| US2977209A (en) | Method of combatting weeds | |
| US3536473A (en) | Method for regulating plant growth with a halogenated derivative of thiophenecarboxylic acid | |
| US3427146A (en) | Phenoxypyridazines as herbicides | |
| CS214672B2 (en) | Means for regulation of the plant growth and insecticide means and method of making the active substances | |
| US2913328A (en) | Isobutyl-n, n-diethylthiolcarbamate and use as herbicide | |
| US2893855A (en) | N-1-napthylchlorophthalamic herbicides | |
| US3246976A (en) | Method for controlling crab grass and water grass | |
| US3000940A (en) | Perchlorylarylureas | |
| KR830001038B1 (en) | Substituted 1,3 - dithio heterocyclic compounds as herbicidal | |
| US2913325A (en) | Amyl-n, n-diethylthiolcarbamate and use as herbicide | |
| US3246974A (en) | Method of controlling water grass | |
| US3518075A (en) | Method of controlling weeds | |
| US2980578A (en) | Method of combating plant-attacking fungus | |
| US3116995A (en) | Method for destroying undesired plant life | |
| US3383195A (en) | m-(3, 3-dimethylureido) phenyl dimethyl-sulfamate as a herbicide | |
| US3016295A (en) | Method for altering the growth characteristics of plants |