Claims
- 1. A process for the preparation of a compound of formula I ##STR32## wherein R.sup.1 is --OH, --SH, --CHO, --CN, --COOH, --B(OH).sub.2, --COX, with X being Cl or Br, or is --COOR.sup.2, --SiR.sub.3.sup.2 or --B(OR.sup.2).sub.2, with R.sup.2 being a C.sub.1 -C.sub.12 alcohol moiety without the hydroxy group, wherein R.sup.1 is further --C.sub.n H.sub.2n COOR.sup.2, with n being an integer from 1 to 4, or linear or branched C.sub.1 -C.sub.12 hydroxyalkyl which is unsubstituted or is substituted by --F, --CN, C.sub.1 -C.sub.6 alkoxy, phenyl, fluorophenyl, C.sub.1 -C.sub.4 alkoxy-phenyl, C.sub.1 -C.sub.4 alkylthio-phenyl, C.sub.1 -C.sub.4 alkyl-phenyl, C.sub.1 -C.sub.4 fluoroalkyl-phenyl, nitrophenyl or by cyanophenyl, or wherein R.sup.1 is a benzyl alcohol or a C.sub.1 -C.sub.12 acyl moiety, each unsubstituted or substituted by F, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 alkylthio, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 fluoroalkyl, nitro or by cyano, or wherein R.sup.1 is a radical of formula II ##STR33## wherein R.sup.5 is --CN, --CF.sub.3, --COOR.sup.2, --CONH.sub.2, --CO--NHR.sup.2 or --CONR.sub.2.sup.2, R.sup.3 and R.sup.4 are a direct bond or each is H, or R.sup.3 is H and R.sup.4 independently has the meanings of R.sup.5,
- which process comprises
- a) in an inert solvent, reacting 2,2-difluorobenzo-1,3-dioxole with an alkali metal compound with a strong anion base to give a compound of formula IV ##STR34## wherein Y is an alkali metal, and optionally then reacting with an anhydrous metal halide from the group MgZ.sub.2, ZnZ.sub.2, CdZ.sub.2, CuZ, CuZ.sub.2, PdZ.sub.2, NiZ.sub.2, AlZ.sub.3, SiZ.sub.4, SnZ.sub.2, SnZ.sub.4, TiZ.sub.4, BZ.sub.3 or ZrZ.sub.4 to give a compound of formula IV wherein Y is --Cu, --MgZ, --ZnZ, --CdZ, --CuZ, --PdZ, --NiZ, --AlZ.sub.2, --SiZ.sub.3, SnZ, --SnZ.sub.3, TiZ.sub.3, --BZ.sub.2 or --ZrZ.sub.3 and Z is --Cl, --Br or --I and, in the case of boron, is also --OC.sub.1 -C.sub.4 alkyl or --O--aryl,
- b) reacting the compound of formula IV with an electrophilic compound from the group X--CN, CO.sub.2, S.sub.8, COX.sub.2, B(OR.sup.2).sub.3, X--SIR.sub.3.sup.2, R.sup.2 O--SiR.sub.3.sup.2 or XCOOR.sup.2, with X being --Cl or --Br, or with a formylating reagent, CH.sub.2 O, an epoxide, a benzaldehyde which is unsubstituted or is substituted by F, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 alkylthio, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 fluoroalkyl, nitro or by cyano, a C.sub.1 -C.sub.11 alkyl-CHO which is unsubstituted or is substituted by --F, --Cl, --CN, C.sub.1 -C.sub.6 alkoxy, phenyl, fluorophenyl, C.sub.1 -C.sub.4 alkoxyphenyl, C.sub.1 -C.sub.4 -alkylthiophenyl, C.sub.1 -C.sub.4 alkylphenyl, C.sub.1 -C.sub.4 fluoroalkylphenyl, nitrophenyl or by cyanophenyl, or with C.sub.1 -C.sub.12 acyl-X.sup.1 or C.sub.1 -C.sub.12 fluoroacyl-X.sup.1, wherein X.sup.1 is --Cl, --Br, C.sub.1 -C.sub.6 alkoxy or the radical of a secondary amine, or with X.sup.2 C.sub.n H.sub.2n COOR.sup.2, X.sup.2 --CR.sup.3 .dbd.CR.sup.4 R.sup.5
- wherein X.sup.2 is a leaving group, and
- c) isolating the compound of formula I or first hydrolysing the reaction mixture and then isolating the compound of formula I.
- 2. A process for the preparation of a compound of formula I according to claim 1, wherein R.sup.1 is --CHO, --CN, --COOH, --B(OH).sub.2, --COX, with X being Cl or Br, or is --COOR.sup.2 or --B(OR.sup.2).sub.2, with R.sup.2 being a C.sub.1 -C.sub.12 alcohol moiety without the hydroxy group, wherein R.sup.1 is further --C.sub.n H.sub.2n COOR.sup.2, with n being an integer from 1 to 4, or linear or branced C .sub.1 -C.sub.12 hydroxyalkyl or C.sub.1 -C.sub.12 acyl each unsubstituted or substituted by --F, --CN, C.sub.1 -C.sub.6 alkoxy, phenyl, fluorophenyl, C.sub.1 -C.sub.4 alkoxyphenyl, C.sub.1 -C.sub.4 alkylthiophenyl, C.sub.1 -C.sub.4 alkylphenyl, C.sub.1 -C.sub.4 fluoroalkylphenyl, nitrophenyl or by cyanophenyl, or wherein R.sup.1 is a radical of formula II ##STR35## wherein R.sup.5 is --CN, --CF.sub.3, --COOR.sup.2, --CONH.sub.2, --CO--NHR.sup.2 or --CONR.sub.2.sup.2, R.sup.3 and R.sup.4 are a direct bond or each is H, or R.sup.3 is H and R.sup.4 independently has the meanings of R.sup.5,
- which process comprises
- a) in an inert solvent, reacting 2,2-difluorobenzo-1,3-dioxole with an alkali metal compound with a strong anion base to give a compound of formula IV ##STR36## wherein Y is an alkali metal, and optionally then reacting with an anhydrous metal halide from the group MgZ.sub.2, ZnZ.sub.2, CdZ.sub.2, CuZ, CuZ.sub.2, PdZ.sub.2, NiZ.sub.2, AlZ.sub.3, SiZ.sub.4, SnZ.sub.2, SnZ.sub.4, TiZ.sub.4, BZ.sub.3 or ZrZ.sub.4 to give a compound of formula IV wherein Y is --Cu, --MgZ, --ZnZ, --CdZ, --CuZ, --PdZ, --NiZ, --AlZ.sub.2, --SiZ.sub.3, --SnZ, --SnZ.sub.3, --TiZ.sub.3, --BZ.sub.2 or --ZrZ.sub.3 and Z is --Cl, --Br or --I and, in the case of boron, is also --OC.sub.1-C.sub.4 alkyl,
- b) reacting the compound of formula IV with an electrophilic compound from the group X--CN, CO.sub.2, B(OR.sup.2).sub.3, COX.sub.2 or XCOOR.sup.2, with X being --Cl or --Br, or with a formylating reagent, CH.sub.2 O, an epoxide, a C.sub.1 -C.sub.11 alkyl-CHO which is unsubstituted or is substituted by --F, --Cl, --CN, C.sub.1 -C.sub.6 -alkoxy, phenyl, fluorophenyl, C.sub.1 -C.sub.4 alkoxyphenyl, C.sub.1 -C.sub.4 -alkylthiophenyl, C.sub.1 -C.sub.4 -alkylphenyl, C.sub.1 -C.sub.4 fluoroalkylphenyl, nitrophenyl or by cyanophenyl, or with C.sub.1 -C.sub.12 acyl-X.sup.1 wherein X.sup.1 is --Cl, --Br, C.sub.1 -C.sub.6 alkoxy or the radical of a secondary amine, or with X.sup.2 C.sub.n H.sub.2n COOR.sup.2, X.sup.2 --CR.sup.3 .dbd.CR.sup.4 R.sup.5
- wherein X.sup.2 is a leaving group, and
- c) isolating the compound of formula I or first hydrolysing the reaction mixture and then isolating the compound of formula I.
- 3. A process for the preparation of a compound of formula I according to claim 2, ##STR37## wherein R.sup.1 is --CHO, --CN, --COOH, --COX, with X being Cl or Br, --COOR.sup.2, with R.sup.2 being a C.sub.1 -C.sub.12 alcohol moiety without the hydroxy group, --C.sub.n H.sub.2n COOR.sup.2, with n being an integer from 1 to 4, linear or branched C.sub.1 -C.sub.12 hydroxyalkyl or C.sub.1 -C.sub.12 acyl each unsubstituted or substituted by --F, --CN, C.sub.1 -C.sub.6 alkoxy, phenyl, fluorophenyl, C.sub.1 -C.sub.4 alkoxyphenyl, C.sub.1 -C.sub.4 alkylthiophenyl, C.sub.1 -C.sub.4 alkylphenyl, C.sub.1 -C.sub.4 fluoroalkylphenyl, nitrophenyl or by cyanophenyl, or is a radical or formula ##STR38## wherein R.sup.5 is --CN, --CF.sub.3, --COOR.sup.2 or --CONR.sub.2.sup.2, R.sup.3 and R.sup.4 are a direct bond or each is H, or R.sup.3 is H and R.sup.4 independently has the meanings of R.sup.5,
- which process comprises
- a) in an inert solvent, reacting 2,2-difluorobenzo-1,3-dioxole with an alkali metal compound with a strong anion base to give a compound of formula IV ##STR39## wherein Y is an alkali metal, and optionally then reacting with an anhydrous metal halide from the group MgZ.sub.2, ZnZ.sub.2, CdZ.sub.2, CuZ, CuZ.sub.2, PdZ.sub.2, NiZ.sub.2, AlZ.sub.3, SiZ.sub.4, SnZ.sub.2, SnZ.sub.4, TiZ.sub.4 or ZrZ.sub.4 to give a compound of formula IV wherein Y is --Cu, --MgZ, --ZnZ, --CdZ, --CuZ, --PdZ, --NiZ, --AlZ.sub.2, --SiZ.sub.3, --SnZ, --SnZ.sub.3, --TiZ.sub.3 or --ZrZ.sub.3 and Z is --Cl, --Br or --I,
- b) reacting the compound of formula IV with an electrophilic compound from the group X--CN, CO.sub.2, COX.sub.2 or XCOOR.sup.2, with X being --Cl or --Br, or with a formylating reagent, CH.sub.2 O, a C.sub.1 -C.sub.11 alkyl-CHO which is unsubstituted or is substituted by --F, --CN, C.sub.1 -C.sub.6 alkoxy, phenyl, fluorophenyl, C.sub.1 -C.sub.4 alkoxyphenyl, C.sub.1 -C.sub.4 alkylthiophenyl, C.sub.1 -C.sub.4 alkylphenyl, C.sub.1 -C.sub.4 fluoroalkylphenyl, nitrophenyl or by cyanophenyl, an epoxide, a benzaldehyde which is unsubstituted or is substituted by --F, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 alkylthio, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 fluoroalkyl, nitro or by cyano, or with C.sub.1 -C.sub.12 acyl-X.sup.1 wherein X.sup.1 is --Cl, --Br, C.sub.1 -C.sub.6 alkoxy or the radical of a secondary amine, or with X.sup.2 C.sub.n H.sub.2n COOR.sup.2, X.sup.2 --CR.sup.3 .dbd.CR.sup.4 R.sup.5
- wherein X.sup.2 is a leaving group, and
- c) isolating the compound of formula I or first hydrolysing the reaction mixture and then isolating the compound of formula I.
- 4. A process for the preparation of a compound of formula I according to claim 3, ##STR40## wherein R.sup.1 is --CHO or a radical of formula II ##STR41## wherein R.sup.5 is --CN, --COOR.sup.2 or --CONH.sub.2, each of R.sup.3 and R.sup.4 is H, or R.sup.3 is H and R.sup.4 independently has the meanings of R.sup.5.
- 5. A process for the preparation of 2,2-difluoro-1,3-benzodioxol-4-yl-carbaldehyde of the formula ##STR42## according to claim 4.
- 6. A process according to claim 3, wherein the reaction is carried out at from -150.degree. C. to 150.degree. C.
- 7. A process according to claim 6, wherein the reaction is carried out at from -30.degree. C. to +10.degree. C.
- 8. A process according to claim 5, wherein the reaction is carried out with butyllithium as metallating reagent, in the presence of a complex-forming compound at from -15.degree. C. to +10.degree. C.
- 9. A process according to claim 3, wherein the solvent is a non-polar or polar aprotic solvent.
- 10. A process according to claim 3, wherein the reaction mixture contains, in addition, a complexing agent.
- 11. A process according to claim 3, wherein the alkali metal compound is a Li-, Na-, K-, -alkyl, -amide or -alcoholate.
- 12. A process according to claim 11, wherein the alkali metal is Li.
- 13. A process according to claim 5, wherein the formylating reagent is a formic acid ester, an orthoformic acid ester, an alkoxymethyleneaniline or an N-disubstituted formamide.
- 14. A process according to claim 13, wherein the formylating reagent is dimethyl formamide.
- 15. A process according to claim 3, wherein, as the radical of a secondary amine, X.sup.1 is ##STR43## or the radical of a 5- or 6-membered heterocyclic amine which may contain a further hetero atom from the group --O-- and .dbd.N--C.sub.1 -C.sub.4 alkyl.
- 16. A process according to claim 3, wherein X.sup.2 is a leaving group is a halide, C.sub.1 -C.sub.6 alkoxy, C.sub.6 -C.sub.10 aryloxy, C.sub.1 -C.sub.12 -secondary amino, C.sub.1 -C.sub.8 acyloxy or the radical of a sulfonic acid.
- 17. A process according to claim 8, wherein the complex-forming compound is selected from a group consisting of ethers, tert.-amines, cyclic ureas and N-substituted acid amides.
- 18. A process according to claim 17, wherein the complex-forming compound is selected from a group consisting of ethylene glycol dimethyl ether, hexamethylphosphoric acid triamide, 1,3-dimethyl-2-imidazolone, dimethylethyleneurea, dimethylpropyleneurea and N,N,N',N'-tetramethylethylenediamine, and an organolithium compound is used as the metal compound.
- 19. A process according to claim 18, wherein a suspension of n-butyllithium is reacted with the equivalent amount of tetramethylethylenediamine at -15.degree. to -10.degree. C., and the resulting reaction mixture is added to 2,2-difluoro-1,3-benzodioxole at a maximum molar ratio of n-butyllithium to 2,2-difluoro-1,3-benzodioxole of 0.99 to 1.02 in an inert solvent and the reaction mixture is reacted in succession by adding an equivalent amount of dimethyl formamide to the reaction mixture, by hydrolysing the reaction mixture, and the reaction product is isolated.
- 20. A process according to claim 18, wherein a suspension of n-butyllithium is added at -15.degree. C. to -10.degree. C. to a solution of 2,2-difluoro-1,3-benzodioxole and of the approximately equimolar amount of tetramethylethylenediamine at a maximum molar ratio of n-butyllithium to 2,2-difluoro-1,3-benzodioxole of 0.99 to 1.02, in an inert solvent and the reaction mixture is reacted in succession by adding an equivalent amount of dimethyl formamide to the reaction mixture, by hydrolysing the reaction mixture, and the reaction product is isolated.
- 21. A process according to claim 18, wherein s suspension of n-butyllithium is continuously fed into a prepared solution of difluoro-1,3-benzodioxole and of tetramethylethylenediamine at a maximum molar ratio of n-butyllithium to 2,2-difluoro-1,3-benzodioxole of 0.99 to 1.02, at -5.degree. to +10.degree. C., in an inert solvent and the reaction mixture is immediately and continuously reacted with dimethyl formamide and hydrolised, and the reaction product is isolated.
Priority Claims (2)
Number |
Date |
Country |
Kind |
1044/88 |
Mar 1988 |
CHX |
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1052/88 |
Mar 1988 |
CHX |
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Parent Case Info
This is a divisional of Ser. No. 987,902, filed Dec. 4, 1992, now U.S. Pat. No. 5,281,718, issued Jan. 25, 1994, which in turn is a divisional of Ser. No. 583,787, filed Sep. 14, 1990, now U.S. Pat. No. 5,194,628, issued Mar. 16, 1993, which in turn is a continuation-in-part of Ser. No. 321,939, filed Mar. 10, 1989, now abandoned.
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EPX |
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Divisions (2)
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Number |
Date |
Country |
Parent |
987902 |
Dec 1992 |
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Parent |
583787 |
Sep 1990 |
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