US2961457A - New esters of omicron, omicron-dialkylphosphoric or omicron. omicron-dialkylthionophosphoric acids - Google Patents
New esters of omicron, omicron-dialkylphosphoric or omicron. omicron-dialkylthionophosphoric acids Download PDFInfo
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- US2961457A US2961457A US783671A US78367158A US2961457A US 2961457 A US2961457 A US 2961457A US 783671 A US783671 A US 783671A US 78367158 A US78367158 A US 78367158A US 2961457 A US2961457 A US 2961457A
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- omicron
- acid
- butene
- carbon atoms
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- Expired - Lifetime
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- 239000002253 acid Substances 0.000 title description 20
- 150000007513 acids Chemical class 0.000 title description 7
- 150000002148 esters Chemical class 0.000 title description 7
- 150000001875 compounds Chemical class 0.000 claims description 21
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 36
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 32
- 125000004432 carbon atom Chemical group C* 0.000 description 20
- -1 chloro-bis- (beta-chlorethyl)-phosphite Chemical compound 0.000 description 18
- 238000003756 stirring Methods 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 16
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 16
- 239000002904 solvent Substances 0.000 description 16
- 125000000217 alkyl group Chemical group 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- RGKVQEJMMKCODO-UHFFFAOYSA-N CCOOP(O)([ClH]OCC)=S Chemical compound CCOOP(O)([ClH]OCC)=S RGKVQEJMMKCODO-UHFFFAOYSA-N 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- ZEKINDGHYQFYMU-UHFFFAOYSA-N C(C)O[ClH]P(=S)(Cl)[ClH]OCC Chemical compound C(C)O[ClH]P(=S)(Cl)[ClH]OCC ZEKINDGHYQFYMU-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 3
- 125000004414 alkyl thio group Chemical group 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 239000012433 hydrogen halide Substances 0.000 description 3
- 229910000039 hydrogen halide Inorganic materials 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001649 bromium compounds Chemical class 0.000 description 2
- 125000006310 cycloalkyl amino group Chemical group 0.000 description 2
- 125000004663 dialkyl amino group Chemical group 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 150000004694 iodide salts Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000003223 protective agent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 150000005691 triesters Chemical class 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- YBTBLUIZFVXVOK-UHFFFAOYSA-N 1-but-1-enylpiperidine Chemical compound CCC=CN1CCCCC1 YBTBLUIZFVXVOK-UHFFFAOYSA-N 0.000 description 1
- MBDUIEKYVPVZJH-UHFFFAOYSA-N 1-ethylsulfonylethane Chemical compound CCS(=O)(=O)CC MBDUIEKYVPVZJH-UHFFFAOYSA-N 0.000 description 1
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 description 1
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- KAUCBZVOUXXENV-UHFFFAOYSA-N COOP(O)(=O)[BrH]OC Chemical compound COOP(O)(=O)[BrH]OC KAUCBZVOUXXENV-UHFFFAOYSA-N 0.000 description 1
- 101100206391 Caenorhabditis elegans crn-7 gene Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 241000283984 Rodentia Species 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000005336 allyloxy group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- SIIVGPQREKVCOP-UHFFFAOYSA-N but-1-en-1-ol Chemical class CCC=CO SIIVGPQREKVCOP-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008396 flotation agent Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000003151 ovacidal effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
- C07F9/20—Esters of thiophosphoric acids containing P-halide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/113—Esters of phosphoric acids with unsaturated acyclic alcohols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/14—Esters of phosphoric acids containing P(=O)-halide groups
- C07F9/1403—Esters of phosphoric acids containing P(=O)-halide groups containing the structure Hal-P(=O)-O-unsaturated acyclic group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
- C07F9/173—Esters of thiophosphoric acids with unsaturated acyclic alcohols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/572—Five-membered rings
Definitions
- This invention relates to a process for the production of .new esters of O .O-dialky1phosphoric or 0.0-dialkylthionophosphoric acids, and to the new esters themselves. It relates in particular :to-theproduction of esters of 0.0- dialkylphosphoric and 0.0-dialkylthionophosphoric acids with substituted butenols, and to the esters themselves.
- the primary object of the present invention consists in the discovery and production of new halogen-free esters of 0.0-dialkylphosphoric acids and O;O-dialkylthionophosphoric acids which haveboth strong insecticidal and ovicidal properties but which on the contrary are less toxic for warm-blooded animals than the phosphoric acid esters hitherto known.
- a further object consists in the discovery of new insecticides which do not contain any halogen atoms, which can be used against pests of all kinds and which above all have a systematic action.
- Suitable butene-(3)-ol-(2) compounds substituted in l-position and in which Y is an oxygen atom combined with an alkyl radical are1-alkoxybutene-(3)-ols-(2)' with 1 to 4- carbon atoms in the alkoxy groups, such as l-methoxybutene-( 3 .-ol- (2) l-ethoxy-butene- 3 -ol-(2) and also l-propyland l-isopropyl-butene-(3)-o1-(2) and also the isomeric 1-butyl-butene-(3)-ols-(2).
- butene- (3)-ols-(2) substituted in -1-position by an oxygen-containing radical are l allyloxy-butene-(3)-ol-(2) and also 1-phenoxy-butene-(3)rol-(2), and if'desired the phenoxy group .may be substituted by a nitro group.
- butenols of this kind there may also be mentioned l-anilino-butene-(3')-ol-(2) and also l-substituted .butenols in which the N-atom of "the substituents is connected to a'cycloalkane'radical, for example cyclopentyl, cyclohexyl or cyclo-octyl, or is aconstituent of aheterocycliccompound which contains no further unsaturated linkages and further hetero atoms.
- a'cycloalkane'radical for example cyclopentyl, cyclohexyl or cyclo-octyl, or is aconstituent of aheterocycliccompound which contains no further unsaturated linkages and further hetero atoms.
- butenols are for example 1-cyclopentylamino-butene- (3 -ol- 2) 1-cyc1ooctylamino-butene- 3 -ol-(2) l-pyrrolidylbutene- 3 )-ol- (2) and 1-piperidino-butene-.( 3 -ol- (2)
- those are especially suitable initial materialsof which the substitutent is an alkyl mercapto group containing up to 4 carbon atoms or a phenylmercapto group, and the sulfur atom may also be oxidized to a sulfonic acid group.
- 0.0-dialkylphosphoric or 0.0-dialkylthionophosphoric acid monohalides serving as the second reaction component there may be mentioned the chlorides, bromides and iodides of 0.0-dialkylphosphoric and 0.0- dialkylthionophosphoric acids, the chlorides being the preferred compounds.
- the ,alkyl groups may be identical or diiferent alkylradicals with 1 to.4 carbon atoms.
- OD-dialkylphosphoric acid monohalides will hereinafter be referred to briefly as OD-dialkylphosphoric acid monohalides. They are readily accessible known compounds which are obtained for example by reaction of phosphorus oxychloride or thionophosphoric acid trihalides with the calculated amount of analiphatic monohydric alcohol.
- the reaction takes place by introducing the two reaction components in an anhydrous medium and in general it is immaterial which component is introduced first. It is suitable to add the dialkylphosphoric acid monohalide to the substituted butenol.
- the initial materials are used in about equivalent amounts. Sometimes it may be advantageous however to use one or other initial material in slight excess, for example 1.2 to 1.5 times the theoretically calculated amount.
- diluents there may be used for example aromatic, aliphatic and cycloaliphatic hydrocarbons, such as benzene, toluene, xylene, gasolines and cyclohexane or aliphatic chlorohydrocarbons, as for example methylene chloride, chloroform, and also ethylene chloride and carbon tetrachloride.
- aromatic, aliphatic and cycloaliphatic hydrocarbons such as benzene, toluene, xylene, gasolines and cyclohexane or aliphatic chlorohydrocarbons, as for example methylene chloride, chloroform, and also ethylene chloride and carbon tetrachloride.
- solvents is especially recommended when one or both of the reactants is solid.
- reaction already takes place appreciably even in the cold, but it is preferable to work at room temperature or at higher temperatures, for example at about to 130 C., advantageously at about to 75 C., if necessary in closed vessels.
- Example 1 56.4 parts of diethoxythionophosphoric acid monochloride are allowed to react with a mixture of 37.7 parts of l-propyl-amino-butene-(3)-ol-(2) and 23.7 parts of anhydrous pyridine slowly while stirring vigorously. The temperature thereby rises to 50 C. After the completion of the addition, the whole is stirred for another 4 to 5 hours at 45 to 50 C. to complete the reaction. The reaction product is cooled to room temperature, parts of water and 100 parts of benzene are added thereto, stirred well and the aqueous layer separated from the non-aqueous layer in a separator. The latter is dried with sodium sulfate. After distilling off the solvent, 72 parts of a non-distillable oil remain.
- the compound has the formula:
- the compound has the following formula:
- Example 6 CzHoO olrno
- Example 7 68 parts of diethoxythionophosphoric acid monochloride are allowed to drip while stirring well into a mixture of 60 parts of 2-hydroxybutene-(3)-yl ethyl sulfone, 30 parts of anhydrous pyridine and 250 parts of benzene. After the addition had been completed, the whole is stirred for another 5 hours at 45 to 50 C. After the reaction matterial has been cooled it is Washed with Water and then the organic layer is dried over sodium sulfate. After distilling off the solvent there remain behind 91 parts of a pale brown readily mobile oil. The compound has the formula:
- Example 11 37.6 parts of diethoxythionophosphoric acid chloride are allowed to flow into a mixture of 40 parts of l-cyclooctylaminobutene-(3)-ol-(2) and 16 parts of anhydrous pyridine while stirring well. Stirring is then continued for another 5 hours at 50 C. and the whole worked up as in Example 7 after the addition of 100 parts of benzene. After distilling on the solvent, there remain 46 parts of a viscous red-brown oil of the formula:
- Example 14 36.6 parts of diethoxythionophosphoric acid monochloride are added while stirring well to 26.4 parts of l-ethylmercaptobutene-(3)-ol-(2), 50 parts of toluene and 21.2 parts of finely powdered sodium carbonate. The whole is then stirred for another 5 hours at 70 to C. The reaction mixture is cooled to room temperature and worked up as in Example 7. After distilling off the solvent, 30.7 parts of a brownish liquid are obtained having the formula:
- Example 15 28.2 parts of diethoxythionophosphoric acid monochloride are allowed to flow while stirring well into a mixture of 27 parts of 1-phenylmercaptobutene-(3)-ol-(2) and 12 parts of anhydrous pyridine. When the addition is completed, the whole is stirred for another 5 hours at 50 C. Then it is cooled to room temperature. 50 parts of benzene are added and the product worked up as in Example 7. After distilling off the solvent there remain 40 parts of a golden yellow oil. The compound has the formula:
- Example 16 32.4 parts of di-isopropoxythionophosphoric acid chloride are allowed to fiow While stirring into a mixture of 27 parts of l-phenylmercaptobutene-(3)-ol-(2), 50 parts of methylene chloride and 12 parts of anhydrous pyridine. The whole is stirred for another hours at 40 C., then cooled to room temperature and worked up as in Example 7. After distilling off the solvent there remain 43.3 parts of a yellowish oil of the formula:
- Example 20 37.6 parts of diethoxythionophosphoric acid monochloride are allowed to flow while stirring into a mixture of 42 parts of l-(para-nitrophenoxy)-butene-(3)ol-(2) and 16 parts of anhydrous pyridine. The whole is stirred for another 5 hours at 50 C., then cooled to room temperature and 50 parts of benzene added. It is Worked up as in Example 7. After distilling off the solvent, there remains as a residue 25 parts of a red-brown oil of the formula:
- RO O-CH-CH2Y CH CHz in which R and R stand for alkyl groups having 1 to 4 carbon atoms, X stands for a member of the group consisting of oxygen and sulfur and Y stands for a radical from the group consisting of alkoxy with 1 to 4 carbon atoms, allyloxy, phenoxy, nitrophenoxy, monoand dialkylamino with 1 to 4 carbon atoms in the alkyl groups, cycloalkylamino, anilino, pyrrolidyl, alkylmercapto and alkylsulfonyl with 1 to 4 carbon atoms in the alkyl groups, phenylmercapto and phenylsulfonyl.
- R-O s CH CH2 in which R and R are alkyl groups with 1 to 4 carbon atoms and Y stands for an alkylmercapto radical containing 1 to 4 carbon atoms.
- R-O s CH CH2 in which R and R stand for alkyl groups with 1 to 4 carbon atoms and Y for an alkylsulfonyl group which contains 1 to 4 carbon atoms in the alkyl radical.
- RO ⁇ s ⁇ OCH-CH2Y CH OH2 in which R and R' stand for alkyl groups with 1 to 4 carbon atoms and Y for a monoalkylamino group containing 1 to 4 carbon atoms in the alkyl radical.
- R and R stand for alkyl groups with 1 to 4 carbon atoms and Y stands for a dialkylamino group containing from 1 to 4 carbon atoms in the alkyl radicals.
- R and R stand for alkyl groups with 1 to 4 carbon atoms and Y stands for phenylmercapto.
- R--0 O-GH-CHa-Y CH CH in which R and R' stand for alkyl groups with 1 to 4 carbon atoms and Y stands for phenoxy.
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Description
nited States 12 Claims. (CI.-2'60--461) This invention relates to a process for the production of .new esters of O .O-dialky1phosphoric or 0.0-dialkylthionophosphoric acids, and to the new esters themselves. It relates in particular :to-theproduction of esters of 0.0- dialkylphosphoric and 0.0-dialkylthionophosphoric acids with substituted butenols, and to the esters themselves.
it is already known that triesters of phosphoric acids are obtained by reacting dialkoxyphosphoric acid monohalides with alcohols or phenols. According to the process disclosed in US. patentspecificatio-n No. 2,536,647, for example, the alkali salt of para-nitrophenol is allowed to act onthe bis-(beta-ehlorethyl)-thiophosphoryl chloride obtainable by .thereaction of sulfur with chloro-bis- (beta-chlorethyl)-phosphite, whereby there is-formed bis- (chlorethyl)-paranitrophenylthiophosphate. As alcohols for the reaction withphosphoric acid ester halides there have been used both saturated, unsaturated, linear or branched chain alcohols and also thioalcohols. For example by the reaction of methallyl alcohol or its alkali salts with phosphoric acid ester halides, forexample with O-monoor 0.0-di-alkylphosphoric acid halides, the corresponding methallyl phosphates are obtained (cf. US. patent specification No. 2,176,416).
Many of the triesters of phosphoric acids already prepared in large numbers have considerable technical importance and are known as destructive agents for insects or rodents, or may be used, as corrosion protective agents, flame protective agents, flotation agents, softenersor as additives for high pressure lubricants.
The primary object of the present invention consists in the discovery and production of new halogen-free esters of 0.0-dialkylphosphoric acids and O;O-dialkylthionophosphoric acids which haveboth strong insecticidal and ovicidal properties but which on the contrary are less toxic for warm-blooded animals than the phosphoric acid esters hitherto known. A further object consists in the discovery of new insecticides which do not contain any halogen atoms, which can be used against pests of all kinds and which above all have a systematic action.
We have found that the above objects can be achieved and that new halogen-free 0.0- dialkylphosphoric acid esters of substituted butenols of the general formula OHr-CH in which R and R stand for lower aliphatic saturated hydrocarbon radicals, especially alkyl groups with 1 to 4 carbon atoms, 'X stands for an oxygen or sulfur atom, and Y stands for a radical from the group consisting of aikoxy, alloyloxy, phenoxy and nitrophenoxy groups containing 1 to 4 carbon atoms, monoand di-alkylamino groups with 1 to 4 carbon atoms in the alkyl groups, cycloalkylamino, anilino, pyrrolidyl, alkylmercapto and alkylsulfonyl groups with l to 4 carbon atoms in the alkyl radicals and phenylmercapto and phenylsulfonyl groups, are obtained by reacting a 0.0-dialkylphosphoric 2,961,457 Patented Nov.- 22, 1960 2 (or O.O-dialkylthionophosphoric) acid halide of the general formula:
RO/ Hal in which R, R and K have the meaning given above and Hal is a halogen atom, with a butene-(3)-ol-(2) substituted in ,l-positionand of the general formula:
HOCH.CH2Y
in which Y has the'meaning given above.
Suitable butene-(3)-ol-(2) compounds substituted in l-position and in which Y is an oxygen atom combined with an alkyl radical are1-alkoxybutene-(3)-ols-(2)' with 1 to 4- carbon atoms in the alkoxy groups, such as l-methoxybutene-( 3 .-ol- (2) l-ethoxy-butene- 3 -ol-(2) and also l-propyland l-isopropyl-butene-(3)-o1-(2) and also the isomeric 1-butyl-butene-(3)-ols-(2). Further butene- (3)-ols-(2) substituted in -1-position by an oxygen-containing radical are l allyloxy-butene-(3)-ol-(2) and also 1-phenoxy-butene-(3)rol-(2), and if'desired the phenoxy group .may be substituted by a nitro group. As representatives ofbutenols substituted-in l-position in'the substituent contains a nitro-gen atom through which the linkage with the'butenol radical takesplace there may be mentioned for example 1-methylamino-butene(3)-ol-(2) and also the corresponding 1-ethylamino-, .1-propylaminoand l-butylamino-butene-(3)-o1s-(2), as well as l-dimethyl-, l-Jdiethyl-, 1-dipropyl-, 1-dibutyl-, l-methylethy1-, 1-methylpropyl-, l-ethylpropyland l-ethylbutyl-arninobutene-(3)-ols(2). As initial butenols of this kind there may also be mentioned l-anilino-butene-(3')-ol-(2) and also l-substituted .butenols in which the N-atom of "the substituents is connected to a'cycloalkane'radical, for example cyclopentyl, cyclohexyl or cyclo-octyl, or is aconstituent of aheterocycliccompound which contains no further unsaturated linkages and further hetero atoms. Such butenols are for example 1-cyclopentylamino-butene- (3 -ol- 2) 1-cyc1ooctylamino-butene- 3 -ol-(2) l-pyrrolidylbutene- 3 )-ol- (2) and 1-piperidino-butene-.( 3 -ol- (2) Of the derivatives of butene-(3)-ol-(2) compounds substituted in Lposition, those are especially suitable initial materialsof which the substitutent is an alkyl mercapto group containing up to 4 carbon atoms or a phenylmercapto group, and the sulfur atom may also be oxidized to a sulfonic acid group. There may be mentioned for example l-methylmercapto-butene-(3)-ol-( 2), l-ethylmercapto-butene-(3)-0l-(2), l-propylor 'l-butyl-mercapto-butene- (-3)-ol-(2) and also l-methylor l-ethyl-sulfonyl-butene-(3)-ol-(2) l-propylor l-butylsulfonyl-butene-(3)-ol-(2) and l:phenylsulfonyl-butenc-(3)-ol-(2).
Of the 0.0-dialkylphosphoric or 0.0-dialkylthionophosphoric acid monohalides serving as the second reaction component there may be mentioned the chlorides, bromides and iodides of 0.0-dialkylphosphoric and 0.0- dialkylthionophosphoric acids, the chlorides being the preferred compounds. The ,alkyl groups may be identical or diiferent alkylradicals with 1 to.4 carbon atoms. These monohalides of 0.0-dialkylphosphoric or 0.0-dialkylthionophosphor'ic acids will hereinafter be referred to briefly as OD-dialkylphosphoric acid monohalides. They are readily accessible known compounds which are obtained for example by reaction of phosphorus oxychloride or thionophosphoric acid trihalides with the calculated amount of analiphatic monohydric alcohol. As
representative for these reaction components there may be mentioned above all dirnethoxyphosphoric acid mono chloride, dimethoxyphosphoric acid monobromide and monoiodide, and also the corresponding halides of 0.0-
3 diethyl-, 0.0-dipropyland 0.0-dibutyl-phosphoric acid, as well as the chlorides, bromides and iodides of 0.0- dimethylthionophosphoric acid, 0.0-diethylthionophosphoric acid, 0.0-dipropylthionophosphoric acid and 0.0- dibutylthionophosphoric acid.
The reaction takes place by introducing the two reaction components in an anhydrous medium and in general it is immaterial which component is introduced first. It is suitable to add the dialkylphosphoric acid monohalide to the substituted butenol. The initial materials are used in about equivalent amounts. Sometimes it may be advantageous however to use one or other initial material in slight excess, for example 1.2 to 1.5 times the theoretically calculated amount.
Working in the presence of inert organic diluents may be convenient. As diluents there may be used for example aromatic, aliphatic and cycloaliphatic hydrocarbons, such as benzene, toluene, xylene, gasolines and cyclohexane or aliphatic chlorohydrocarbons, as for example methylene chloride, chloroform, and also ethylene chloride and carbon tetrachloride. The use of solvents is especially recommended when one or both of the reactants is solid. It has been found to be advantageous to collect the hydrogen halide set free by means of substances which bind hydrogen halide for example by the addition of pyridine, aniline, methylaniline, triethylamine, tripropylamine or other amines of which the boiling point lies above the reaction temperature. Alkali carbonates or alkali bicarbonates may also be used for the purpose. The said substances effect the removal of the hydrogen halide from the sphere of the reaction as soon as it is formed by the reaction. This removal of the halogen hydracids set free may be described as base neutralization of halogen hydracids.
The reaction already takes place appreciably even in the cold, but it is preferable to work at room temperature or at higher temperatures, for example at about to 130 C., advantageously at about to 75 C., if necessary in closed vessels.
The following examples will further illustrate this invention but the invention is not restricted to these examples.
The parts specified in the examples are parts by weight.
Example 1 56.4 parts of diethoxythionophosphoric acid monochloride are allowed to react with a mixture of 37.7 parts of l-propyl-amino-butene-(3)-ol-(2) and 23.7 parts of anhydrous pyridine slowly while stirring vigorously. The temperature thereby rises to 50 C. After the completion of the addition, the whole is stirred for another 4 to 5 hours at 45 to 50 C. to complete the reaction. The reaction product is cooled to room temperature, parts of water and 100 parts of benzene are added thereto, stirred well and the aqueous layer separated from the non-aqueous layer in a separator. The latter is dried with sodium sulfate. After distilling off the solvent, 72 parts of a non-distillable oil remain.
The compound has the formula:
56.4 parts of diethoxythionophosphoric acid monochloride are allowed to flow while stirring into a mixture of 42.9 parts of diethylaminobutene-(3)-ol-(2) and 23.7 parts of pyridine. After completion of the addition, the Whole is stirred for another 5 hours at about 60 C. and then worked up as in Example 1. After separating into phases and distilling off the solvent from the organic phase, there remain as a residue 68 parts of an oil which cannot be distilled.
The compound has the following formula:
C2H5O S 56.4 parts of diethoxythionophosphoric acid monochloride are added to 39.6 parts of l-ethylmercaptobutene- (3)-ol-(2) and 23.7 parts of anhydrous pyridine while stirring well. It is then stirred for another 5 hours at 40 to 45 C. The reaction mixture is cooled to room temperature, about 20 parts of water and parts of benzene added, stirred well and the layers separated. The benzene solution is then washed with dilute hydrochloric acid and water and dried over sodium sulfate. The solvent is distilled off. The residue may be distilled with partial decomposition. At 0.5 mm. Hg pressure and to C. there are obtained 74 parts of the compound of the following formula:
ozHsO S 37.6 parts of diethoxythionophosphoric acid monochloride are allowed to flow slowly with good stirring into a mixture of 32.6 parts of l-anilino-butene-(S)-ol-(2) and 15.8 parts of anhydrous pyridine. The reaction temperature rises to 45 C. After completion of the addition the whole is stirred for another 5 hours at 55 to 60 C. and then worked up as in Example 1. After distilling off the solvent from the resultant organic phase, there remain 60 parts of the compound of the following formula as a non-distillable oil.
H=CH2 Example 5 42.4 parts of 1-phenylsulfonyl-butene-(3)-ol-(2) and 15.8 parts of pyridine are mixed and, while stirring well, 37.6 parts of diethoxythionophosphoric acid chloride are allowed to flow in. The whole is stirred for another 5 hours at 50 to 60 C., worked up as described in Example 1, and 60 parts of the new phosphoric acid ester are obtained as a non-distillable oil of the formula:
H=CH
Example 6 CzHoO olrno Example 7 68 parts of diethoxythionophosphoric acid monochloride are allowed to drip while stirring well into a mixture of 60 parts of 2-hydroxybutene-(3)-yl ethyl sulfone, 30 parts of anhydrous pyridine and 250 parts of benzene. After the addition had been completed, the whole is stirred for another 5 hours at 45 to 50 C. After the reaction matterial has been cooled it is Washed with Water and then the organic layer is dried over sodium sulfate. After distilling off the solvent there remain behind 91 parts of a pale brown readily mobile oil. The compound has the formula:
IHfiO s P eiulo o-oH-oHismonn H=CH2 Example 8 432 parts of di-isopropoxythionophosphoric acid chloride are allowed to flow slowly into a mixture of 264 parts of l-ethylniercaptobutene-(3)-ol-(2) and 160 parts of anhydrous pyridine heated to 30 C. while stirring powerfully. The whole is then stirred for another 5 hours at 45 to-50 C. ;to complete'the reaction. After the reaction product has been cooled to room temperature, it is worked up in the manner described in Example 7 after the addition of 500 parts of benzene. After distilling off the solvent there are obtained 600 parts of a yellow-brown oil of the formula:
73.2 parts of dibutoxythionophosphoric acid chloride are allowed to flow while stirring into a mixture, heated to 45 C., of 40 parts of l-ethylmercaptobutene-(3)-ol- (2) and 23.7 parts of anhydrous pyridine. After the addition has been completed, the Whole is stirred for another 5 hours at 50 C. and, after the addition of 50 parts of benzene, worked up as in Example 7. After distilling off the solvent, there remain 83.7 parts of a pale brown colored oil of the formula orHro ,s
Example 10 CH=CH2 Example 11 37.6 parts of diethoxythionophosphoric acid chloride are allowed to flow into a mixture of 40 parts of l-cyclooctylaminobutene-(3)-ol-(2) and 16 parts of anhydrous pyridine while stirring well. Stirring is then continued for another 5 hours at 50 C. and the whole worked up as in Example 7 after the addition of 100 parts of benzene. After distilling on the solvent, there remain 46 parts of a viscous red-brown oil of the formula:
canto s CHsO Example 1 3 37.6 paits of diethoxythi'onopho'sphoric acid chloride are allowed to flow slowly while stirring well into a mixture of 28.2 parts of 1-pyrrolidinobutene-(3)-o1-(2), 50 parts of carbon tetrachloride and 16 parts of anhydrous pyridine. The temperature thereby rises to 40 C. After all has been added, the whole is stirred for another 6 hours at 50 C. to complete the reaction. The reaction product is cooled to room temperature and Worked up as in Example 7. After distilling off the solvent, 18 parts of a dark brown liquid remain behind having the formula:
021350 O'-CHCHz-N H when. V
Example 14 36.6 parts of diethoxythionophosphoric acid monochloride are added while stirring well to 26.4 parts of l-ethylmercaptobutene-(3)-ol-(2), 50 parts of toluene and 21.2 parts of finely powdered sodium carbonate. The whole is then stirred for another 5 hours at 70 to C. The reaction mixture is cooled to room temperature and worked up as in Example 7. After distilling off the solvent, 30.7 parts of a brownish liquid are obtained having the formula:
ozHso OCHCH2S C2115 CH oHz Example 15 28.2 parts of diethoxythionophosphoric acid monochloride are allowed to flow while stirring well into a mixture of 27 parts of 1-phenylmercaptobutene-(3)-ol-(2) and 12 parts of anhydrous pyridine. When the addition is completed, the whole is stirred for another 5 hours at 50 C. Then it is cooled to room temperature. 50 parts of benzene are added and the product worked up as in Example 7. After distilling off the solvent there remain 40 parts of a golden yellow oil. The compound has the formula:
7 Example 16 32.4 parts of di-isopropoxythionophosphoric acid chloride are allowed to fiow While stirring into a mixture of 27 parts of l-phenylmercaptobutene-(3)-ol-(2), 50 parts of methylene chloride and 12 parts of anhydrous pyridine. The whole is stirred for another hours at 40 C., then cooled to room temperature and worked up as in Example 7. After distilling off the solvent there remain 43.3 parts of a yellowish oil of the formula:
CHZCHQ Example 17 37.6 parts of diethoxythionophosphoric acid chloride are allowed to flow slowly into a mixture of 32.8 parts of 1-phenoxybutene-(3)-ol-(2) and 16 parts of anhydrous pyridine while stirring well. Then the whole is stirred for another 5 hours at 50 C. After adding 50 parts of benzene, it is worked up as in Example 7. The solvent is distilled off. There remains a residue of 49.8 parts of a yellow oil of the formula:
CzHsO S CH=CH3 t ao Example 18 Example 19 37.6 parts of diethoxythionophosphoric acid monochloride are added while stirring well to 25.6 parts of 1- allyloxybutene-(3)-0l-(2) and 16 parts of anhydrous pyridine. The whole is then stirred for another 5 hours at 50 C. The reaction mixture is cooled to room temperature, 50 parts of benzene are added and the product worked up as in Example 7. After distilling off the solvent, there are obtained 46.8 parts of an ahnost colorless liquid of the formula:
Example 20 37.6 parts of diethoxythionophosphoric acid monochloride are allowed to flow while stirring into a mixture of 42 parts of l-(para-nitrophenoxy)-butene-(3)ol-(2) and 16 parts of anhydrous pyridine. The whole is stirred for another 5 hours at 50 C., then cooled to room temperature and 50 parts of benzene added. It is Worked up as in Example 7. After distilling off the solvent, there remains as a residue 25 parts of a red-brown oil of the formula:
CaHsQ S CH=CH2 Example 21 CzHsO CzHsO We claim: 1. Any compound of the general formula:
RO X
RO O-CH-CH2Y CH=CHz in which R and R stand for alkyl groups having 1 to 4 carbon atoms, X stands for a member of the group consisting of oxygen and sulfur and Y stands for a radical from the group consisting of alkoxy with 1 to 4 carbon atoms, allyloxy, phenoxy, nitrophenoxy, monoand dialkylamino with 1 to 4 carbon atoms in the alkyl groups, cycloalkylamino, anilino, pyrrolidyl, alkylmercapto and alkylsulfonyl with 1 to 4 carbon atoms in the alkyl groups, phenylmercapto and phenylsulfonyl. 2. Any compound of the general formula:
R-O s CH=CH2 in which R and R are alkyl groups with 1 to 4 carbon atoms and Y stands for an alkylmercapto radical containing 1 to 4 carbon atoms.
3. Any compound of the general formula:
R-O s CH=CH2 in which R and R stand for alkyl groups with 1 to 4 carbon atoms and Y for an alkylsulfonyl group which contains 1 to 4 carbon atoms in the alkyl radical.
4. Any compound of the general formula:
RO\ s \OCH-CH2Y CH=OH2 in which R and R' stand for alkyl groups with 1 to 4 carbon atoms and Y for a monoalkylamino group containing 1 to 4 carbon atoms in the alkyl radical.
5. The compound of the formula:
CHa-O s CHr-O OCH,CHZSC2H| 6. The compound of the formula:
CgHsO S \OCHCH:SO1H5 n=crn 7. The compound oi the formula:
CsH1O s CaHzO CHsO 10. A compound having the general formula:
l in which R and R stand for alkyl groups with 1 to 4 carbon atoms and Y stands for a dialkylamino group containing from 1 to 4 carbon atoms in the alkyl radicals.
11. A compound of the general formula:
RO\ s RO O-GHCH:-Y
in which R and R stand for alkyl groups with 1 to 4 carbon atoms and Y stands for phenylmercapto.
12. A compound of the general formula:
R--0 O-GH-CHa-Y CH=CH in which R and R' stand for alkyl groups with 1 to 4 carbon atoms and Y stands for phenoxy.
References Cited in the file of this patent UNITED STATES PATENTS 2,736,726 Gaetzi et a1. Feb. 28, 1956 2,777,792 Lutz et a1. Jan. 15, 1957 2,852,513 Schrader et a1. Sept. 16, 1958 2,865,801 Baker et a1. Dec. 23, 1958 FOREIGN PATENTS 789,122 Great Britain Ian. 15, 1958 795,340 Great Britain Mar. 21, 1958
Claims (1)
1. ANY COMPOUND OF THE GENERAL FORMULA:
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB0047332 | 1958-01-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2961457A true US2961457A (en) | 1960-11-22 |
Family
ID=6968235
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US783671A Expired - Lifetime US2961457A (en) | 1958-01-02 | 1958-12-30 | New esters of omicron, omicron-dialkylphosphoric or omicron. omicron-dialkylthionophosphoric acids |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US2961457A (en) |
| CH (1) | CH377331A (en) |
| DE (1) | DE1072616B (en) |
| FR (1) | FR1220913A (en) |
| GB (1) | GB846229A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3151147A (en) * | 1961-10-12 | 1964-09-29 | Shell Oil Co | Omicron, omicron-dialkyl omicron-1-sulfonylvinyl and omicron, omicron-dialkyl omicron-1-sulfinylvinyl phosphates |
| US3206493A (en) * | 1961-08-21 | 1965-09-14 | Standard Oil Co | Preparation of o, o, s-triesters of monothiophosphoric acid |
| US3359203A (en) * | 1965-09-01 | 1967-12-19 | Exxon Research Engineering Co | Ashless dithiophosphoric acid derivatives |
| US3502677A (en) * | 1963-06-17 | 1970-03-24 | Lubrizol Corp | Nitrogen-containing and phosphorus-containing succinic derivatives |
| US4493817A (en) * | 1983-07-06 | 1985-01-15 | Teck Corporation | Process for recovering pyrochlore mineral containing niobium and tantalum |
| US6187723B1 (en) * | 1993-09-13 | 2001-02-13 | Exxon Research And Engineering Company | Lubricant composition containing antiwear additive combination |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1173723B (en) * | 1960-09-21 | 1964-07-09 | Basf Ag | Preparations for the control of insects |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2736726A (en) * | 1952-03-28 | 1956-02-28 | Geigy Ag J R | Basic phosphoric acid esters |
| US2777792A (en) * | 1954-09-01 | 1957-01-15 | Sandoz Ag | Pest combating agents |
| GB789122A (en) * | 1953-04-24 | 1958-01-15 | Ciba Ltd | New organic compounds containing phosphorus, processes for their manufacture and preparations containing them |
| GB795340A (en) * | 1953-10-07 | 1958-05-21 | Sandoz Ltd | New insecticidal esters of dithiophosphoric acid |
| US2852513A (en) * | 1956-04-27 | 1958-09-16 | Bayer Ag | Thiophosphoric acid esters and their production |
| US2865801A (en) * | 1956-04-06 | 1958-12-23 | Monsanto Chemicals | Propargyl phosphorothioates |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2394829A (en) * | 1944-04-26 | 1946-02-12 | Shell Dev | Allyl-type phosphates and their preparation |
| US2536647A (en) * | 1948-03-06 | 1951-01-02 | Monsanto Chemicals | Process of preparing bis (beta-chlorethyl)-para-nitrophenyl thiophosphate |
-
0
- DE DENDAT1072616D patent/DE1072616B/en active Pending
-
1958
- 1958-12-22 CH CH6759658A patent/CH377331A/en unknown
- 1958-12-30 US US783671A patent/US2961457A/en not_active Expired - Lifetime
-
1959
- 1959-01-01 GB GB26/59A patent/GB846229A/en not_active Expired
- 1959-01-02 FR FR783188A patent/FR1220913A/en not_active Expired
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2736726A (en) * | 1952-03-28 | 1956-02-28 | Geigy Ag J R | Basic phosphoric acid esters |
| GB789122A (en) * | 1953-04-24 | 1958-01-15 | Ciba Ltd | New organic compounds containing phosphorus, processes for their manufacture and preparations containing them |
| GB795340A (en) * | 1953-10-07 | 1958-05-21 | Sandoz Ltd | New insecticidal esters of dithiophosphoric acid |
| US2777792A (en) * | 1954-09-01 | 1957-01-15 | Sandoz Ag | Pest combating agents |
| US2865801A (en) * | 1956-04-06 | 1958-12-23 | Monsanto Chemicals | Propargyl phosphorothioates |
| US2852513A (en) * | 1956-04-27 | 1958-09-16 | Bayer Ag | Thiophosphoric acid esters and their production |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3206493A (en) * | 1961-08-21 | 1965-09-14 | Standard Oil Co | Preparation of o, o, s-triesters of monothiophosphoric acid |
| US3151147A (en) * | 1961-10-12 | 1964-09-29 | Shell Oil Co | Omicron, omicron-dialkyl omicron-1-sulfonylvinyl and omicron, omicron-dialkyl omicron-1-sulfinylvinyl phosphates |
| US3502677A (en) * | 1963-06-17 | 1970-03-24 | Lubrizol Corp | Nitrogen-containing and phosphorus-containing succinic derivatives |
| US3359203A (en) * | 1965-09-01 | 1967-12-19 | Exxon Research Engineering Co | Ashless dithiophosphoric acid derivatives |
| US4493817A (en) * | 1983-07-06 | 1985-01-15 | Teck Corporation | Process for recovering pyrochlore mineral containing niobium and tantalum |
| US6187723B1 (en) * | 1993-09-13 | 2001-02-13 | Exxon Research And Engineering Company | Lubricant composition containing antiwear additive combination |
Also Published As
| Publication number | Publication date |
|---|---|
| FR1220913A (en) | 1960-05-30 |
| GB846229A (en) | 1960-08-31 |
| CH377331A (en) | 1964-05-15 |
| DE1072616B (en) | 1960-01-07 |
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