• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:

    公开号:SU952108A3
    申请号:SU792842001
    申请日:1979-11-11
    公开日:1982-08-15
    发明作者:Финке Манфред；Мюндних Райнер
    申请人:Хехст Аг (Фирма)；
    IPC主号:
    专利说明:

    is reacted with nitril substituted vinyl acetic acid of the general formula CHo C — C — C, 1 where RjH R is independently of each other H, CH3 or Cji.H5 ;; Ry - cocHaj coCa.H5, 0005% or, at a temperature of 100–170 ° C in the presence of 1.5–7.5 mol.% Tert, butyl peroxide, tert, butyl perinoate or terbutyl perbenzoate. The process can be carried out as in. conventional conditions, and in an inert atmosphere. The proposed method characterizes the simplicity of the technology and the ability to carry out the process both periodically and continuously and obtain the product with a yield of 50-98%. Example 1. (3-Acetoxy-3-cyano-propyl) -dimethyl-phosphine oxide P-CHCH-Ch-C1t osn, 62.5 g of dimethylphosphine oxide is heated under nitrogen atmosphere until added to it with vigorous stirring drops for about 1 hour 50 g of acrolein cyanohydrin acetate containing 4 g (4.6 mol;%) of tert. butyl peroctoate. After completion of the dropping, the mixture is stirred for another 15 minutes at 115 s, and then subjected to fractional distillation under high vacuum. At 178-180 (pressure 0.66 mbar), 57 g (3-acetox-3-diano-propyl) -dimethylphosphine oxide is distilled off, which corresponds to 70% of the theoretical yield. The results of the analysis based on (M 203.2): Calculated,%: C47.3; H 6.9; N 6.9; P 15.2. Found,%: C 45.9; H 7.0; N 6.0 P 15.2. Example 2.- {3-Acetoxy-3-cyano-propyl) -methylphosphinic acid methyl ester. 80 g of methylphosphonic acid monomethyl ester is heated under a nitrogen atmosphere and then added to it under vigorous stirring. For about 1 hour, 36 g of acrolein cyanohydrinacetate containing 2 g (3.2 mol.%) Of tert butyl peroctoate are added dropwise. After completion of the addition, the solution is stirred for another 15 minutes at 120 ° C, and then subjected to fractional distillation under reduced pressure. 58 g of methyl (3-acetoxy-3-cyano-propyl) -methylphosphinic acid methyl ester are obtained as a result of a bale (pressure of 0.27 mbar), which corresponds to 92% of the theoretical yield. The results of the analysis based on C8H 404NP (M 219.2); Calculated,%: C, 43.8; H 6.4; N 6.4; R 14.1} Found,%: C 42.5; -H 6.4; N 6.6 / P 14.7. Example 3. (3-Acetoxy-3-cyano-propyl) -methylphosphinic acid mi O 3 II P-CHjCHj-CH-CN 50 jcoCH ethyl ester 110 g of methylphosphonic acid monoethyl ester is heated in a nitrogen atmosphere to 140 ° C, after which with vigorous stirring, 50 g of acrolein dianhydride acetate containing a mixture of 2 g (2.3 mol.%) of tert.butyl peroctoate and 1 g (1.3 mol.%) of t, butyl perbenzoate are added to it over about 1 hour. After the completion of the dropping, the reaction mixture was stirred for another 15 minutes at, the excess of methylphosphonic acid monoethyl ester was distilled off under reduced pressure, and the residue was subjected to fractional distillation under high vacuum. The result is 77 g of ethyl ester (3-acetoxy-Z-cyano-propyl) -methylphosphinic acid with temp. kip 150 ° C (pressure 0.27 mbar), which corresponds to 83% of the third temperature output. The results of the analysis based on (M 233.2): Calculated,%; C, 46.4; H 6/9; N 6.0; R 13.3. Found,%: C 45.4; H 6.9; N 6.0; P 13.5. Example 4. (3-Acetoxy-Z-cyano-propyl) -methylphosphinic acid isobutyl ester. p-CHoCHn-CH-CN 030-C ,, HjO A. To 110 g of methylphosphonate monoisbutyl ester is added dropwise over 1 hour at 120125 ° C under nitrogen atmosphere 50 g of acrolein cyanohydrin acetate containing
    4 g (4.6 mol.%) Tert, butyl peroctoate. After the completion of the dropping, the mixture is stirred for 15 minutes at, and then subjected to fractional distillation under high vacuum. 93 g of isobutyl ester (3-acetoxy-3-cyano-propyl) -methylphosphinic acid with a boiling point are obtained. 168-172s (pressure 0.66 mbar) which corresponds to 89.5% of the theoretical yield.
    The results of the analysis based on (M 0261,3) 1
    Calculated,%: C 50.5; H 7.7; N 5.4; R 11.9.
    Found,%: C 49.5; H 7.7; N 5.5; R 12.1.
    B.110 g of methylphosphonic acid monoisobutyl ester is heated under nitrogen to 140 ° C, after which, with vigorous stirring, 50 g of acroleincyan idrinacetate containing a mixture of
    2 g (2.3 mol.%) Tert, butyl peroctoate and 1 g (1.3 mol.%) Tert, butyl perbenzoate. After completion of the dropping, the reaction mixture is stirred for another 15 minutes at 140 ° C. The excess methanophosphonic acid monoisobutyl ester is separated under reduced pressure, and the residue is distilled under a high vacuum. The result is 90 g of isobutyl ether (3-acetoxy-3-cyano-propyl) -methylphosphonic acid with temp. kip 16.8-172 ° C (pressure 0.66 mbar), which corresponds to 87% of theoretical yield.
    C. To 110 g of methylphosphonic acid monoisobutyl ester is added dropwise over about
    1 h at 130-135 ° С 50 g of acrolein cyanhydrin acetate containing 4 g (4.6 mol.%) Of t, butyl peroctoate. The mixture was stirred for another 15 minutes at, and then subjected to fractional distillation under high vacuum. The result is 9.2 g of isobutyl ester of (3-acetoxy-3-cyino-propyl) -methylphosphonic acid with a temp. kip 168-172 ° C (pressure 0.66 mbar), which is 89% of the theoretical yield.
    E. 89 g of methylphosphonic acid monoisobutyl ester is heated under nitrogen to 115 ° C, after which, with vigorous stirring, 50 g of acrolein cyanohydrin acetate A containing 4 g (4.6 mol.%) Of tert. Are added dropwise to it over about 1 hour. butylperoctate. After the completion of the dropping, the mixture is stirred for 15 minutes at 120 ° C, the excess methylphosphonic acid iso-butyl ester is distilled off from it under reduced pressure, and the residue is distilled under high vacuum. 92 g of (3-acetoxy-3-cyano-propyl) -methylphosphinic acid isobutyl ester are obtained with a temp. kip 166 172 ° C (pressure 0.66 mbar), which corresponds to 67% of the theoretical yield.
    E. 110 g of methylphosphonic acid monoisobutyl ester is heated under nitrogen to 145 ° C, after which, with vigorous stirring, 50 g of acrolein cyanohydrin acetate containing 4 g (4.4 mol.%) Of tert is added dropwise to it over about 1 hour. , butyl perinoate. After graduation-. The mixture is stirred additionally for another 15 minutes at 140 ° C, an excess of methylphosphonate monoisobutyl ester is distilled off from it under reduced pressure, and the residue is subjected to fractional distillation under high vacuum. At 166-172 ° C (pressure 0.66 mbar), 88 g of isobutyl ester (3-acetoxy-3-diano-propyl) -methylphosphinic acid are distilled off, which corresponds to 84.5% of the theoretical yield.
    G. 914 g of monoisobutyl methyl ether is heated under nitrogen to 115 ° C, then added vigorously under stirring to it dropwise over about 2 hours and 250 g. Of acrolein cyanohydrin acetate containing 8 g (1.83 mole%) tert, butylperoctate. After the completion of the dropping, the reaction mixture is stirred for another 15 minutes, the excess monoisobutyl methyl ester of the acid is distilled off under reduced pressure until the temperature rises to 175 ° C and the residue is distilled in a thin film evaporator.
    machine. As a result, 513 g of (3-acetoxy-3-diano-propyl) -methylphosphinic acid isobutyl ester is obtained, which corresponds to 98% of the theoretical yield.
    Example B. (3-Acetoxy-Z-cyano-Z-methyl-propyl) -methylphosphinic acid isobutyl ester
    % J
    SI,
    p-sagSn- -s-SB ososn.
    122 g of methylphosphonic acid monoisobutyl ester is heated under nitrogen to 115 ° C, after which it is added dropwise to it with vigorous stirring
    about 1 h 40 g of methyl vinyl ketone cyanohydrin acetate containing 3 g (4.8 mol%) of tert-butyl peroctoate. After completion of the dropping, the reaction mixture is stirred for another 15 minutes at 120 ° C. The result is 39 g of isobutyl ether (3-acetoxy-3. Cyano-3-methylpropyl) methyl-phosphinic acid as a brown oily liquid. The yield is 50% of the theoretical. For analysis, part of the product is subjected to distillation under high vacuum (temperature 1b4-172 ° C, pressure 0.54 mbar). Analysis results calculated as ll04NP (M 275.3): Calculated,%: C 52.4; H 8.1; N- 5.1; R 11.3, Found,%: C 52.3} H, 8.0; N 5, P 12,5. Example 6. Isobutyl ether (3-acetoxy-3-cyano-2 - ethyl propyl) -methylphosphinic acid; pcc% ccn-cc / 1 I WD-dqHgOCjHg OCOdHj 110 g of monoisobutyl methyl phosphonic acid ester is heated in a nitrogen atmosphere to 120 ° C, then, with vigorous stirring, is added dropwise to it for about 1 hour 60 g of 2-ethylacrolein-hydrin acetate containing 4 g (4.9 mol.%) Tert, butyl peroctoate. - After the completion of the dropping, the reaction mixture is stirred for another 15.min at 130 ° C, excess of methylphosphonic acid monoisobutyl ester is distilled off under reduced pressure, and the residue is distilled under high vacuum. At 155158 ° С (pressure 0.27 mbar), 73 g of isobutyl ester (3-acetoxy-3 cyano-2-ethylpropyl) -methylphosphonic acid are distilled off, which corresponds to 64% of the theoretical yield. The results of the analysis based on (M 288.3): Calculated,%: C 54.2; H 8.0, N4, 9-, Found: C 55.4) H 8.7; N 5.4. PR and MER. 7. Isobutyl eff (3-propionyloxy-Z-cyano-propyl) -methylphosphinic acid
    about ;
    SNS
    P-CHjCHj-CH-CN OSOS2N5
    110 g of methylphosphonic acid monoisobutyl ester is heated under nitrogen to 125 ° C, after which O with vigorous stirring is added dropwise to it over about 1 hour (-6.6 mol%) tert-butyl peroctoate. After the completion of the dropping, the editorial mixture stirred for 65
    Sbnb
    ; p-CH CHjX
    Cjhao
    权利要求:
    Claims (1)
    [1]
    65 g of benzenephosphonic acid monoethyl ester are heated under nitrogen to 130 ° C, after which, with vigorous stirring, 24 g of acrolein cyanohydrin acetate containing a mixture of 1 g (2.4 mol.%) Tert, butyl peroctoate and 1 g (2.7 mol%) for an additional 15 minutes at 120 ° C, and then an excess of methanophosphonic acid monoisobutyl ester is distilled off from it under reduced pressure. The residue is distilled under high vacuum. At 178184 ° С (pressure 0.66 mbar), 94 g of isobutyl ester (3-propionyloxy-3-cyano-propyl) -methylphosphinic acid is distilled off, which corresponds to 84.5% of the theoretical yield. The results of the analysis based on C-fiH-i O NP (M 275.3): Calculated%: C 51.4; H 8D; N5.1, P 11.3. Found,%: C 52.4; H 8.1; N 5.5; R 11.8. PR and M e R 8. (3-Benzoyloxy-Z-cyano-propyl) methylphosphinic acid 3 II P-CH CH-CH-CN OCoCgHj isobutyl ester 100 g of methylphosphonic acid monoisobutyl ester is heated under nitrogen to 115 ° C, then, with vigorous stirring, 47 g of acrolein cyanohydrinbenzoate containing 4 g (7.4 mol.%) of tert. butyl peroctoate are added dropwise to it under about 1 h. After the completion of the dropping, the reaction mixture is stirred for another 15 min at. The starting materials are then distilled off under reduced pressure. As a result, 49 g of isobutyl ester of (3-benzyl-hydroxy-3-diano-propyl) -methylphosphinic acid are obtained in the form of a brown oily liquid, which corresponds to 60% of the theoretical yield. The resulting product contains practically no impurities according to thin-layer chromatography; it has the following IR-spectroscopic characteristics: 1748, 2300, 1613, 1190, 719 cm Example 9 (3-acetoxy-3-cyano-propyl) ethyl ester butyl benzoate. After the completion of the dropping, the reaction mixture is stirred for another 15 minutes at, and then the starting materials are distilled off under reduced pressure. 53 g of (3-acetoxy-3-cyano-propyl) phenylphosphinic acid ethyl ester are obtained as a brown oily liquid. The yield is 53% of theoretical, 1H-NMR data: chemical shift) at the EELS (multiplicity of signals in brackets): -CHj: 1.35 (t), -CHjC -: 2.05 (S), - CH, O -:: 4.15 (m), - C (, E 5: 7.0 - 8.9 (m) Example 10. Izbutyl ester (-3-acetoxy-3-cyano-propyl) -methylthiophosphinic acid P -CH CHj-CH-C WO-Ct gO OOSOH, 40 g of monoisobutyl ester, methylthiophosphonic acid are heated under nitrogen to 115 ° C, then 15 g of acroleincyanthine acetate are added dropwise to it under vigorous stirring containing 3.9 mol.% tert, butylperoctate..After ending none additionally, the reaction mixture is stirred for an additional 15 minutes at 120 ° C, then an excess of methylthiophosphonate methyl monoisobyl ester is distilled off under reduced pressure, and the residue is subjected to fractional distillation under high vacuum. At 180-185 ° C (pressure 0.66 mbar ) 24 g of isobutyl ester (3-acetoxy-3-cyano-propyl) is distilled off: 1. methylthiophosphinic acid, which corresponds to 72% of the theoretical yield. The results of the analysis based on C HaoOsSNP (M 277.3). Calculated,%: N 5.0; S 11.6; R 11.2; . Found:% N 4,4, S 12,5, P 12,2 Example 11. Isobutyl ester, 3-ethoxycarbonyloxy-3-cyapopropyl) -methylphosphinic acid T-CH CH-i-CH.-CN OCOOCjHs ieo-C H 3 O 20 g of methylphosphonic acid monoisobutyl ester is heated under nitrogen to 125 ° C, then 30 g of acrolein cyanhydride of ethyl carbonate containing 2 g (4.8 mol%) of tertl are added dropwise over about 1 hour to it with vigorous stirring After the completion of the dropping, the reaction mixture is stirred for another 15 minutes at 125 ° C, then the excess is distilled from it under reduced pressure. methylphosphonic acid monoisobutyl ester, and the residue is subjected to fractional distillation under high vacuum. At 160-164 ° C (pressure 0.66 mbar), 39 g of isobutyl ester (3-ethoxycarbonyloxy-zcyano-propyl) -methylphosphinic acid is distilled off, which corresponds to 67.5% of the theoretical yield. The results of the analysis based on .N05P (M 291.3): Calculated,%: C 49.5; H 7.6; N 4.8; P 10.6; Found,%: C 48, 9; H 7.4; N 5.2; R 10.1. Example 12. (3-Acetoxy-3-cyano-propyl) methylphosphinic acid isoamyl ester. 185 g of methylphosphonate monoisoamyl ester are heated under nitrogen to. When energy After stirring for about 1 hour, 50 g of acrolein cyanohydrin acetate, which contains 22 (2.3 mol.%) tert, butyl peroctoate, are added dropwise, stirred for 15 minutes at 130 ° C and then the unreacted starting materials are distilled off to a temperature under reduced pressure. bath 150 ° C. The residue is distilled at a pressure of 1.3 mbar and a bath temperature of 220 ° C through a thin layer evaporator. 104 g of isoamyl ester (3-acetoxy-3-cyano-propyl) -methylphosphinic acid (temperature 160 ° C, pressure 13 mbar) are obtained. The yield is 95% of theoretical. The results of the analysis based on (M 275.3). Calculated,%: C 52.4, - H 8.1; N 5.1; R 11.3-, Found,%: C 51.5; H 8.1; N 4.9, P 10.7. PR and M e R 13. 110 g of monoisobutyl ether methanephosphonic acid is heated in a nitrogen atmosphere to 170 ° C. With vigorous stirring, 50 g of acrodidine cyanohydrin acetate, which contains a mixture of 2 g (2.3 mol.%) Tert, butyl peroctoate and 1 g (1.3 mol.%) Tert, butyl perbenzoate, are added dropwise for about 1 hour. After completion of the dropping, the reaction mass is stirred at 140 ° C for 15 minutes. Then, under reduced pressure, the excess monoisobutyl ester of methylphosphonic acid is separated and the residue is distilled under high vacuum. 90 g of (3-acetoxy-3-cyano-propyl) -methylphosphinic acid isobutyl ester are obtained with a bp. 169-172 ° C (pressure 0.66 mbar). Ji.95210 Analysis results calculated for C - (.- 1 Hjo N04 (261.3): Calculated,%: C50.6, H7.7; N 5.4, R. 11.9. Found:%: C 49.5; H 7.7 / N 5.5;. P 12.1. .5 Claims of the Invention A method of preparing alkyl esters of phosphinic acids or phosphinoxy-f. Of the general formula K, XD, -N -li-tC ", H L15.. Where R is C (, R is C-Cg alkyl; RjH is K-independent of each other H, CH3 or 20 RS-COCHj, COCfiHy, or COOCij H; X is oxygen or sulfur;, p-O or 1, concludes with that 25 8 phosphonic or phosphonic acid of the General formula .В. Н р / ... Xi Щ Щ, / - Rj.RiX and п have the indicated values, are reacted with nitri-substituted vinyl lusus acid of the general formula Rg | I SLgs4-ga, ..., where I, Rj have the indicated values, at a temperature of 100-170 ° C in the presence of 1.5--7.5 mol.% tert-butylperoctoate, tert, butylperinoate or tert, butyl perbenzoate. Sources of information accepted in the examination 1. Kirby A., Warren S. Organic phosphorus chemistry. M., Mir, 1971, p.62.
    类似技术:
    公开号 | 公开日 | 专利标题
    SU952108A3|1982-08-15|Process for producing alkyl esters of phosphinic acids or phosphoneoxides
    US4267125A|1981-05-12|Process for the manufacture of phosphinic and phosphonic acid anhydrides
    US4377537A|1983-03-22|Preparation of alkane phosphonic and phosphinic acid aryl esters
    CA1066715A|1979-11-20|Production of organic phosphorus compounds containing carboxylic groups
    CA2154627A1|1996-01-28|Preparation of phosphonic esters
    US2875231A|1959-02-24|Catalytic process of reacting a phosphite and lactone
    US4529559A|1985-07-16|Process for making derivatives of vinylphosphonic acid or vinylpyrophosphonic acid
    US4855087A|1989-08-08|Process for the preparation of 2-chloroethanephosphonyl dichloride
    SU1754720A1|1992-08-15|Method of 3-|-propanoic acid esters synthesis
    US3989772A|1976-11-02|N,N-bis-|-acrylamides
    SU584008A1|1977-12-15|Method of preparing phenyl esters of phosphinic acids
    US4761252A|1988-08-02|Process for the preparation of vinylphosphonic dichloride
    IE41812B1|1980-03-26|Unsaturated phophorus-containing carboxylic acid derivatives
    SU584009A1|1977-12-15|Method of preparing a-methacryloyloxyethyldialylphosphonates
    IL99202A|1995-10-31|Acylaminomethyl phosphinic acids a process for their preparation and some novel acylaminomethyl phosphinic acid
    SU1512972A1|1989-10-07|Method of producing o-| phosphonites
    US3998915A|1976-12-21|Process for the production of 1-acyloxy alkylene phosphonic acid dialkyl esters
    US4173578A|1979-11-06|Production of alkenyl phosphinic acids
    SU826713A1|1986-05-23|Method of producing tris-| antimonite
    US3770853A|1973-11-06|Marshall dann
    SU502901A1|1976-02-15|The method of obtaining alkylxanthioalkyl esters of typhoid acids
    SU1081167A1|1984-03-23|Process for preparing vinyl esters of trivalent phosphorus acids
    SU1268589A1|1986-11-07|Method of producing dialkyl esters of methylcyclopentylphosphonic acid
    SU707922A1|1980-01-05|Method of preparing gamma-dialkylphosphonopropanols
    SU1490123A1|1989-06-30|Method of producing asterofluoroanhydrides of alkylphosphonic acids
    同族专利:
    公开号 | 公开日
    ZA796044B|1980-10-29|
    JPS6345395B2|1988-09-09|
    AT4644T|1983-09-15|
    IL58671A|1985-06-30|
    DE2966163D1|1983-10-20|
    DE2849003A1|1980-08-21|
    JPS5566598A|1980-05-20|
    EP0011245B1|1983-09-14|
    IL58671D0|1980-02-29|
    EP0011245A1|1980-05-28|
    US4521348A|1985-06-04|
    DD146955A5|1981-03-11|
    CA1161861A|1984-02-07|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2957931A|1949-07-28|1960-10-25|Socony Mobil Oil Co Inc|Synthesis of compounds having a carbonphosphorus linkage|
    FR2321484B1|1975-08-18|1977-12-16|Poudres & Explosifs Ste Nale|
    DE2613546A1|1976-03-30|1977-10-06|Hoechst Ag|PROCESS FOR THE PREPARATION OF TERTIAER PHOSPHINOXIDE|
    US4122148A|1976-04-20|1978-10-24|Davy Powergas Inc.|Sulfur dioxide removal process|
    DE2717440C2|1976-05-17|1984-04-05|Hoechst Ag, 6230 Frankfurt|Weed control with [ propyl-1] methylphosphinic acid derivatives|
    DE2849003A1|1978-11-11|1980-08-21|Hoechst Ag|CYANHYDRINE DERIVATIVES CONTAINING PHOSPHORUS AND METHOD FOR THE PRODUCTION THEREOF|DE3047024A1|1978-11-11|1982-07-22|Hoechst Ag, 6000 Frankfurt|Phosphorus-contg. cyanohydrin deriv. prepn. - by reacting phosphinate ester with cyanohydrin deriv. e.g. acrolein cyanohydrin|
    DE2849003A1|1978-11-11|1980-08-21|Hoechst Ag|CYANHYDRINE DERIVATIVES CONTAINING PHOSPHORUS AND METHOD FOR THE PRODUCTION THEREOF|
    DE3070229D1|1979-12-08|1985-03-28|Fbc Ltd|Derivatives of 4--2-oxobutanoic acid, herbicidal compositions containing them, and intermediates and methods for their production|
    DE3312165A1|1983-04-02|1984-10-04|Hoechst Ag, 6230 Frankfurt|METHOD FOR PRODUCING PHOSPHINOTHRICIN|
    DE3319850C2|1983-06-01|1985-05-09|Hoechst Ag, 6230 Frankfurt|Process for the preparation of phosphorus-containing cyanohydrin derivatives|
    DE3508573A1|1985-03-11|1986-09-11|Hoechst Ag, 6230 Frankfurt|PHOSPHORUSAMINONITRILE AND METHOD FOR THE PRODUCTION THEREOF|
    AT144519T|1989-02-06|1996-11-15|Hoechst Schering Agrevo Gmbh|N-ACYL-2-AMINO ACID AMIDES CONTAINING PHOSPHINESE, METHOD FOR THE PRODUCTION THEREOF AND N-ACYL-2-AMINO ACID NITRILES AS PRE-PRODUCTS|
    IL104056A|1991-12-13|1997-02-18|Hoechst Ag|Process for the preparation of L-phosphinothricin and its derivatives|
    DE19736125A1|1997-08-20|1999-02-25|Hoechst Schering Agrevo Gmbh|Preparation of phosphinyl-butyric acid derivatives|
    DE19828863C1|1998-06-29|1999-09-02|Clariant Gmbh|Production of phosphinate esters, useful as reactive fire retardants for thermoplastics and thermosetting resins and also as synthetic intermediates|
    DE19923619C2|1999-05-25|2001-08-23|Clariant Gmbh|Process for the preparation of dialkylphosphinic acids and their salts|
    DE19923615C1|1999-05-25|2000-12-14|Clariant Gmbh|Process for the preparation of alkylphosphonous esters|
    DE19923617C2|1999-05-25|2001-10-31|Clariant Gmbh|Process for the preparation of phosphinic acid esters|
    EP1260514A1|2001-05-18|2002-11-27|Aventis Animal Nutrition S.A.|Process for the production of a phosphorus-containing organic compound|
    CN102399240A|2011-12-27|2012-04-04|江苏优士化学有限公司|Improved synthesis method for glufosinate and analogue thereof|
    CA2948713A1|2014-05-13|2015-11-19|Bayer Cropscience Aktiengesellschaft|Process for preparing phosphorus-containing cyanohydrins|
    AU2016254233B2|2015-04-27|2020-10-08|Basf Se|Herbicide combinations comprising glufosinate and indaziflam|
    CN105131034B|2015-07-08|2017-11-21|河北威远生物化工有限公司|The method for synthesizing and purifying of methyl phosphiinic acid ester compound|
    EP3344637B1|2015-09-02|2019-08-07|Basf Se|Method for producing cyanohydrin esters containing phosphorous|
    WO2017037009A1|2015-09-02|2017-03-09|Bayer Cropscience Aktiengesellschaft|Method for producing cyanohydrin esters containing phosphorous|
    WO2017037033A1|2015-09-02|2017-03-09|Bayer Cropscience Aktiengesellschaft|Method for producing cyanohydrin esters containing phosphorous|
    KR20180048662A|2015-09-02|2018-05-10|바이엘 크롭사이언스 악티엔게젤샤프트|Process for producing phosphorus-containing cyanohydrin esters|
    ES2754603T3|2015-09-29|2020-04-20|Basf Se|Procedure for the preparation of phosphinates|
    WO2018108794A1|2016-12-15|2018-06-21|Bayer Cropscience Aktiengesellschaft|Method for producing d-glufosinate or salts thereof using ephedrine|
    WO2018108797A1|2016-12-15|2018-06-21|Bayer Cropscience Aktiengesellschaft|Method for producing l-glufosinate or the salts thereof using ephedrine|
    TW201840578A|2017-02-22|2018-11-16|以色列商亞當阿甘公司|Process for preparing methyl phosphinic acid butyl ester|
    EP3392237B1|2017-04-21|2019-10-02|Evonik Degussa GmbH|Method for manufacturing acrolein cyanohydrins|
    WO2019015909A1|2017-07-21|2019-01-24|Basf Se|Production of glufosinate by reaction of 3-[n-butoxyphosphoryl]-1-cyanopropyl acetate to afford a mixture of n-butyl methylphosphinate and methylphosphinic acid ammonium salt|
    EP3728278A1|2017-12-19|2020-10-28|Basf Se|Method for producing phosphorus-containing-aminonitriles|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE19782849003|DE2849003A1|1978-11-11|1978-11-11|CYANHYDRINE DERIVATIVES CONTAINING PHOSPHORUS AND METHOD FOR THE PRODUCTION THEREOF|
    [返回顶部]