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    • 7. 发明公开
    • Verfahren zur Herstellung phosphorhaltiger Dicarbonsäuren
    • Verfahren zur Herstellung phosphorhaltigerDicarbonsäuren
    • EP0708109A1
    • 1996-04-24
    • EP95114369.2
    • 1995-09-13
    • HOECHST AKTIENGESELLSCHAFT
    • Kleiner, Hans-Jerg, Dr.
    • C07F9/6574C07F9/6568C07F9/6571C07F9/38C07F9/53
    • C07F9/657172C07F9/5304
    • Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von phosphorhaltigen Dicarbonsäuren der Formel (I)

      worin R¹ und R² gleich oder verschieden sind und für einen geradkettigen oder verzweigten Alkylrest mit 1 bis 8 Kohlenstoffatomen, einen cycloaliphatischen Rest mit 5 bis 6 Kohlenstoffatomen im Ring, einen unsubstituierten oder substituierten Arylrest mit 6 bis 10 Kohlenstoffatomen stehen oder R¹ und R² unter Einschluß des Phosphoratoms einen Ring mit 5 bis 8 Gliedern bilden, m und n jeweils unabhängig voneinander 0 oder 1 sind, indem man eine Verbindung der Formel (II)

      worin R¹, R² und m die vorstehend genannte Bedeutung haben mit Fumarsäure, Maleinsäure oder Itaconsäure in Gegenwart einer gesättigten aliphatischen Monocarbonsäure mit insgesamt 1 bis 5 Kohlenstoffatomen als Lösungsmittel bei 100 bis 200°C unter Normaldruck oder erhöhtem Druck umsetzt.
    • 制备方法。 的二羧酸 式(I)的P包括在1-5℃饱和的存在下使式(II)的氧化膦与富马酸,马来酸或衣康酸作为二羧酸(III)反应。 脂族单羧酸(IV)作为溶剂,在100-200℃和正常或更高压力下:R 1,R 2 = 1-8C烷基,5-6C脂环族gp。 或选择。 substd。 6-10C芳基; 或PR 1 R 2 = 5-8元环; 和m,n = 0或1。
    • 8. 发明公开
    • Dinucleotide analogues, intermediates therefor and oligonucleotides derived therefrom
    • Dinukleotidanaloga,Zwischenproduktehierfürund daraus abgeleitete寡核苷酸。
    • EP0629633A2
    • 1994-12-21
    • EP94303883.6
    • 1994-05-27
    • CIBA-GEIGY AG
    • Baxter, Anthony DavidBaylis, Eric KeithCollingwood, Stephen PaulTaylor, Roger JohnWeetman, John
    • C07H21/00C07H19/04A61K31/70
    • C07H9/04C07F9/5304C07F9/65586C07H7/02C07H15/18C07H19/06C07H21/00C07H21/02C07H21/04Y02P20/55
    • A compound of formula

      where R 1 is hydrogen, R 1 a or a group of formula


      R 1 a is R l b or a protecting group Q,
      R 1 b is C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 3 -C 10 cycloalkyl, C 6 -C 15 aryl, C 7 -C 16 aralkyl or a 5- or 6- membered heterocyclic group attached by a carbon atom in the heterocyclic group to the indicated phosphorus atom,
      R 2 is an unsubstituted or substituted C 1 -C 20 alkyl or C 2 -C 20 alkenyl group, an unsubstituted or substituted C 3 -C 10 cycloalkyl group, an unsubstituted or substituted C 6 -C 15 aryl group, an unsubstituted or substituted C 7 -C 16 aralkyl group, or a 5- or 6- membered heterocyclic group attached by a carbon atom in the heterocyclic group to the indicated phosphorus atom,
      R 3 is hydrogen, halogen, hydroxy, R 15 , -OR 15 or -OSO 2 R 15
      R 4 is R 4 a or together with R 6 denotes a valence bond,
      R 4 a is hydrogen, halogen or R 16 ,
      R 5 is hydrogen, halogen, hydroxy, R 17 , -OR 17 , -OCOR 17 or -OSO 2 R 17 ,
      R 6 is hydrogen, halogen or R 18 , or together with R 4 denotes a valence bond,
      R 7 is hydrogen, alkyl-N, N-dialkylphosphoramidyl or R 7 a , or R 7 0- together with R 8 a denotes a C 1 -C 15 hydrocarbylidenedioxy group,
      R 7 a is R 19 , -COR 19 , -SO 2 R 19 or tri(C 1 -C 15 hydrocarbyl)silyl,
      R 8 is R 8 a or Z,
      R 8 a is hydrogen, halogen, hydroxy, R 20 , -OR 20 , -OCOR 20 , -OSO 2 R 20 , or tri(C 1 -C 15 hydrocarbyl)silyloxy, or together with R 9 denotes a C 1 -C 15 hydrocarbylidenedioxy group, or together with R 7 0- denotes a C 1 -C 15 hydrocarbylidenedioxy group,
      R 9 is halogen, hydroxy, -OR 21 , -OCOR 21 , -OSO 2 R 21 , or B 2 , or together with R 8 a denotes a C 1 -C 15 hydrocarbylidenedioxy group,
      R 10 is hydrogen or R 10 a ,
      R 10 a is R 22 , -COR 22 , -SO 2 R 22 or tri(C 1 -C 15 hydrocarbyl)silyl,
      R 11 is hydrogen, halogen, hydroxy, R 23 , -OR 23 , -OCOR 23 , -OSO 2 R 23 or Z,
      R 12 is hydrogen, halogen or R 24 ,
      R 13 is R 13 a or Z,
      R 13 a is hydrogen, halogen, hydroxy, R 25 , -OR 25 , -OCOR 25 , -OSO 2 R 25 , or tri(C 1 -C 15 hydrocarbyl)silyloxy, or together with R 14 denotes a C 1 -C 15 hydrocarbylidenedioxy group,
      R 14 is halogen, hydroxy, -OR 26 , -OCOR 26 , -OSO 2 R 26 , or B l , or together with R 13 a denotes a C 1 -C 15 hydrocarbylidenedioxy group,
      R 15 , R16 , R17 , R18 , R19 R 20, R 21, R 22, R 23, R 24 , R 25 and R 26 are independently a C 1 to C 10 aliphatic group, a C 3 to C 10 cycloaliphatic group, a C 6 to C 15 aromatic group or a C 7 -C 30 araliphatic group,
      B 1 and B 2 are independently each a monovalent nucleoside base radical, and
      Z is substituted or unsubstituted C 6 -C 10 aryloxythiocarbonyloxy; provided that compounds where simultaneously R 1 , R 3 , R 4 and R 6 are hydrogen, R 2 is isopropyl, R 5 is methoxy, R 7 is methyl, R 8 and R 9 are each hydroxy or each acetoxy or R 8 and R 9 together denote isopropylidenedioxy, compounds where simultaneously R 1 , R 3 , R 4 and R 6 are hydrogen, R 2 is butyl, R 5 is methoxy, R 7 is benzyl, R 8 and R 9 are each hydroxy or each acetoxy or R 8 and R 9 together denote isopropylidenedioxy, and compounds where simultaneously R 1 , R 3 , R 4 , R 5 , R 6 and R 7 are hydrogen, R 2 is phenyl and R 8 and R 9 together denote isopropylidenedioxy are excluded.
    • 的化合物,其中R 1是氢,R 1a或式 R 1a的基团是R 1b或保护基Q,R 1b 是C 1 -C 20烷基,C 2 -C 20烯基,C 3 -C 10环烷基,C 6 -C 15芳基,C 7 -C 16芳烷基或通过杂环基中的碳原子与所指示的磷原子连接的5-或6-元杂环基, R 2是未取代或取代的C 1 -C 20烷基或C 2 -C 20烯基,未取代或取代的C 3 -C 10环烷基,未取代或取代的C 6 -C 15芳基,未取代或取代的C 7 -C 16芳烷基, 或由杂环基中的碳原子连接到所指示的磷原子上的5或6元杂环基,R 3是氢,卤素,羟基,R 5,-OR 1, R 5或-OSO 2 R 5 R 4是R 4或a与R 6一起代表价键,R 4是氢,卤素或R 1' R 5是氢,卤素,羟基,R 1-7,-OR 1 7,-OCOR 1或7 -OSO 2 R 1,R 6 >是氢,卤素或R 1 <8 >,或与R 4一起表示价键,R 7是氢,烷​​基-N,N-二烷基磷酰胺基或R 7a,或R 7 O-与R 8一起代表a C 1 -C 15亚烷基二氧基,R 7是R 9,-COR 1 9,-SO 2 R 1 9或三(C 1 -C 15烃基)甲硅烷基, R 8是R 8 a或Z,R 8是氢,卤素,羟基,R 2,-OR 2,-OCOR 2, - 或者三(C 1 -C 15烃基)甲硅烷氧基,或与R 9一起表示C 1 -C 15烃亚基二氧基,或与R 7一起代表C 1 -C 15亚烃基二氧基, R 9是卤素,羟基,-OR 2,-OCOR 2,-OSO 2 R 2,或B 2,或与R 8 a一起 表示C1-C15烃基亚二氧基,R 1是氢或R 1,a,R 1a,R 2,R 2,-COR 2, 2,-SO 2 R 2或3(C 1 -C 15烃基)甲硅烷基,R 1是氢,卤素,羟基,R 2,-OR 2, >,-OCOR 2,3,-OSO 2 R 2或Z,R 1,R 2,R 2,R 3,R 4,R 5, R 1 a或Z,R 1'3是氢,卤素,羟基,R 2, OR 2 <5>,-OCOR 2,5-OSO 2 R 2或3(C 1 -C 15烃基)甲硅烷氧基,或与R 1一起表示C1- C 15烃亚基二氧基,R 1 4是卤素,羟基,-OR 2,-OCOR 2,6,-OSO 2 R 2,或B 1,或 与R 1'3一起,a表示C 1 -C 15烃基亚二氧基,R 1,R 5,R 1,R 6,R 17,R 18, R 1,R 2,R 2,R 2,R 2,R 2,R 2, 2 <5>和R 2 <6>独立地为C 1至C 10脂族基团,C 3至C 10脂环族基团,C 6至C 15芳族基团或C 7 -C 30芳脂基基团,B 1和B 2, 2>各自独立地为一价核苷碱基,Z为取代或未取代的C6-C10芳氧基硫代羰基氧基; 条件是其中R 1,R 3,R 4和R 6同时为氢,R 2为异丙基,R 5为甲氧基,R 7为甲基, 8>和R 9各自为羟基或每个乙酰氧基,或R 8和R 9一起表示异丙二烯基,其中R 1,R 3,R 4和R 6同时为 氢,R 2是丁基,R 5是甲氧基,R 7是苄基,R 8和R 9各自是羟基或每个乙酰氧基或R 8和R 9共同表示 异丙烯二氧基和其中R 1,R 3,R 4,R 5,R 6和R 7同时为氢的化合物,R 2为苯基,R 8和 R 9一起表示异亚丙二氧基。
    • 9. 发明公开
    • Phosphosulfonate herbicides
    • 磷酸盐
    • EP0511826A2
    • 1992-11-04
    • EP92303816.0
    • 1992-04-28
    • ROHM AND HAAS COMPANY
    • Rosen, Robert E.Weaver, Damian GerardCornille, Jane WissingerSpangler, Lori Ann
    • C07F9/40C07F9/30C07F9/53A01N57/04C07F9/42C07F9/44C07F9/32C07F9/34C07F9/36C07F9/6574C07F9/6571A01N57/02
    • C07C205/37A01N57/18A01N57/26C07C17/093C07F9/3211C07F9/4006C07F9/425C07F9/4407C07F9/5304C07F9/60C07F9/65033C07F9/65182C07F9/653C07F9/6539C07F9/6541C07F9/655345C07F9/657181C07C25/125
    • This invention concerns phosphosulfonates having the general formula
      wherein

      (1) Y is phenyl ; naphthyl ; benzyl ; (C 5 -C 8 )cycloalkyl ; a 5-membered heteroaromatic ring having from one to four heteroatoms each being independently N, O or S, provided that no more than one is O or S ; a 6-membered heteroaromatic ring having 1, 2 or 3 nitrogen atoms ; or a fused 5,6- or 6,6-membered heteroaromatic ring having from one to four heteroatoms each being independently N, O or S, provided that no more than one is O or S ;
      wherein Y optionally has up to three substituents, each being independently halogen, cyano, nitro, (C 1 -C 6 )alkoxy, halo(C 1 -C 4 )alkoxy, (C 1 -C 6 )alkyl, halo(C 1 -C 4 )alkyl, phenyl, (C 1 -C 4 )alkylcarbonyloxy, di(C 1 -C 4 )alkylcarbamoyl or (C 1 -C 4 )alkoxycarbonyl, provided that

      (a) no more than one of said substituents is present when Y is a thiadiazolyl ring or a tetrazolyl ring, and
      (b) no more than two of said substituents is present when Y is a triazolyl ring, a thiazolyl ring, or an isothiazolyl ring, except that when Y is phenyl, naphthyl or benzyl, it may have up to five substituents each being independently halogen, acetoxy, methyl, methoxy or halomethoxy, but no more than two of which are acetoxy, methyl, methoxy, or halomethoxy;

      (2) X is oxygen or sulfur ; and
      (3) R 1 and R 2 are each independently chloro, or (C 1 -C 6 )alkyl, (C 1 -C 6 )alkoxy, halo(C 2 -C 4 )alkoxy, (C 1 -C 4 )alkylthio, (C 3 -C 4 )alkenyloxy, (C 3 -C 4 )alkynyloxy, (C 1 -C 4 )alkoxy(C 1 -C 4 )alkoxy, (C 4 -C 8 )cycloalkyloxy, (C 3 -C 6 )cycloalkyl(C 1 -C 3 )alkoxy, cyano(C 1 -C 4 )alkoxy, (C 2 -C 4 )alkylideneiminooxy or amino each optionally substituted with one or two of (C 1 -C 4 )alkyl, (C 2 -C 4 )alkenyl or phenyl ; provided that there is not more than one phenyl group on the amino group ; also provided that R 1 may additionally be phenyl or phenoxy; and also provided that R 1 and R 2 may both be alkoxy so as to form together with the phosphorus atom a 6-membered oxygen-containing ring ; except that when R 1 and R 2 are both alkoxy, Y is not phenyl, 4-methylphenyl, 4-chlorophenyl, 4-bromophenyl or 3-nitrophenyl ; compositions containing these compounds and their use as herbicides.
    • 本发明涉及具有通式的磷酸磺酸盐,其中(1)Y是苯基; 萘; 苄基; (C5-C8)环烷基; 具有1至4个杂原子的5元杂芳环各自独立地为N,O或S,条件是不超过一个为O或S; 具有1,2或3个氮原子的6元杂芳环; 或具有1至4个杂原子的稠合的5,6-或6,6-元杂芳环,其各自独立地为N,O或S,条件是不超过一个为O或S; 其中Y任选具有多至三个取代基,各自独立地为卤素,氰基,硝基,(C 1 -C 6)烷氧基,卤代(C 1 -C 4)烷氧基,(C 1 -C 6)烷基,卤代(C 1 -C 4)烷基,苯基, (C1-C4)烷基羰基氧基,二(C1-C4)烷基氨基甲酰基或(C1-C4)烷氧基羰基,条件是(a)当Y是噻二唑基环或四唑基环时,不超过一个所述取代基,(b )当Y是三唑基环,噻唑基环或异噻唑基环时不超过两个所述取代基存在,除了当Y是苯基,萘基或苄基时,它可以具有多至五个取代基,各自独立地为卤素,乙酰氧基 甲基,甲氧基或卤代甲氧基,但其中不超过2个为乙酰氧基,甲基,甲氧基或卤代甲氧基; (2)X是氧或硫; 和(3)R 1和R 2各自独立地为氯,或(C 1 -C 6)烷基,(C 1 -C 6)烷氧基,卤代(C 2 -C 4)烷氧基,(C 1 -C 4)烷硫基,(C 3 (C 1 -C 4)烷氧基,(C 3 -C 4)炔氧基,(C 1 -C 4)烷氧基(C 1 -C 4)烷氧基,(C 4 -C 8)环烷氧基,(C 3 -C 6) (C 1 -C 4)烷基,(C 2 -C 4)亚烷基亚氨基氧基或各自任选被一个或两个(C 1 -C 4)烷基,(C 2 -C 4)烯基或苯基取代的氨基; 条件是氨基上不多于一个苯基; 还提供R 1可以另外是苯基或苯氧基; 并且还提供R 1和R 2都可以是烷氧基,以便与磷原子一起形成6元含氧环; 除了当R 1和R 2都是烷氧基时,Y不是苯基,4-甲基苯基,4-氯苯基,4-溴苯基或3-硝基苯基; 含有这些化合物的组合物及其作为除草剂的用途。 ñ