Compounds of formula (I) wherein R1 is C1-C4-alkyl or cyclopropyl; R2 is C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkinyl; or C1-C6-alkyl substituted by 1 to 5 fluorine atoms; R3 is C1-C6-alkyl, C1-C6-alkoxy, C3-C6-cycloalkyl, C3-C6-cycloalkoxy, C2-C6-alkenyl, C2-C6-alkenyloxy, C2-C6-alkinyl, C2-C6-alkinyloxy, C1-C6-alkoxycarbonyl, CN, or aryl, heteroaryl, heterocyclyl, aryloxy, heteroaryloxy or heterocyclyloxy, whereby the above-mentioned groups may be substituted by identical of different substituents, R5 signifies hydrogen or methyl; R6 and R7 are C1-C4-alkyl; have microbicidal, insecticidal and acaricidal activity and may be used for the control of pests and plant-pathogenic fungi in agriculture, horticulture and in the field of hygiene.

The present invention relates to new N-alkoxy-N-phenylcarbamates having microbicidal, insecticidal and acaricidal activity, a process for their preparation, new intermediates for the preparation thereof, agrochemical compositions containing these active ingredients, as well as the use thereof in the control and prevention of plant-pathogenic fungi, acarids and insects in agriculture and in the field of hygiene.
The new N-alkoxy-N-phenylcarbamates fall within formula I,
wherein:
R1 is C1-C4-alkyl or cyclopropyl;
R2 is C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkinyl; or C1-C6-alkyl substituted by 1 to 5 fluorine atoms;
R3 is C1-C6-alkyl, C1-C6-alkoxy, C3-C6-cycloalkyl, C3-C6-cycloalkoxy, C2-C6-alkenyl, C2-C6-alkenyloxy, C2-C6-alkinyl, C2-C6-alkinyloxy, C1-C6-alkoxycarbonyl or CN, whereby, with the exception of CN, the above-mentioned groups may be substituted by one or more identical or different substituents selected from the group comprising halogen, cyano, nitro, C1-C6-alkoxycarbonyl, C1-C6-alkoxy, C1-C6-alkylthio, aminocarbonyl, C1-C6-alkylaminocarbonyl, di-C1-C6-alkylaminocarbonyl, C2-C6-alkenyloxy, C3-C6-cycloalkyl, C3-C6-cycloalkyloxy, heterocyclyl, heterocyclyloxy, aryl, aryloxy, heteroaryl, heteroaryloxy, whereby the cyclic radicals in turn may be substituted by one or more identical or different substituents selected from the group comprising halogen, cyano, nitro, C1-C6-alkyl, C1-C6-halogenalkyl, C1-C6-alkoxy, C1-C6-halogenalkoxy, C1-C6-alkoxycarbonyl, C1-C6-alkylthio, C1-C6-alkylamino, di-C1-C6-alkylamino, C2-C6-alkenyl, optionally substituted benzyl, optionally substituted benzyloxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted heteroaryl and optionally substituted heteroaryloxy; whereby the above-mentioned aromatic groups may be substituted by one or more identical or different substituents selected from the group comprising halogen, cyano, nitro, C1-C6-alkyl, C1-C6-halogenalkyl, C1-C6-alkoxy, C1-C6-halogenalkoxy, C1-C6-alkoxycarbonyl, C1-C6-alkylthio, C1-C6-alkylamino, di-C1-C6-alkylamino and C2-C6-alkenyl; or
R3 signifies aryl, heteroaryl, heterocyclyl, aryloxy, heteroaryloxy or heterocyclyloxy, whereby the above-mentioned groups may be substituted by one or more identical or different substituents selected from the group comprising halogen, C1-C6-alkyl, C1-C6-alkoxy, halogen-C1-C6-alkoxy, halogen-C1-C6-alkyl, C1-C6-alkylthio, halogen-C1-C6-alkylthio, C1-C6-alkylsulfinyl, halogen-C1-C6-alkylsulfinyl, C1-C6-alkylsulfonyl, halogen-C1-C6-alkylsulfonyl, C2-C6-alkenyl, C2-C6-alkenyloxy, C2-C6-alkinyl, C3-C6-alkinyloxy, C1-C6-alkylcarbonyl, halogen-C1-C6-alkylcarbonyl, C1-C6-alkoxycarbonyl, halogen-C1-C6-alkoxycarbonyl, C1-C6-alkylaminocarbonyl, di-(C1-C6-alkyl)-aminocarbonyl, whereby the alkyl groups may be identical or different, C1-C6-alkylaminothiocarbonyl, di-(C1-C6-alkyl)-aminothiocarbonyl, whereby the alkyl groups may be identical or different, C1-C6-alkylamino, di-(C1-C6-alkyl)-amino, NO2, an unsubstituted C1-C4-alkylenedioxy group or one which is mono- to tetra-substituted by C1-C4-alkyl and/or by halogen; or CN, SF5, OH and QR4;
Q signifies a direct bond, O, O(C1-C6-alkylene), (C1-C6-alkylene)O, S(xe2x95x90O)p, S(xe2x95x90O)p(C1-C6-alkylene), (C1-C6-alkylene)S(xe2x95x90O)p, C1-C8-alkylene, C2-C6-alkenylene or C2-C6-alkinylene;
R4 signifies an unsubstituted C2-C6-alkenyl- or C2-C6-alkinyl group or one which is substituted by 1 to 3 halogen atoms, a (C1-C4-alkyl)3Si group, whereby the alkyl groups may be identical or different, CN, an unsubstituted or mono- to penta-substituted C3-C6-cycloalkyl, aryl, heteroaryl or heterocyclyl group, whereby the substituents are selected from the group comprising halogen, C1-C6-alkyl, halogen-C1-C6-alkyl, C1-C6-alkoxy, halogen-C1-C6-alkoxy, phenoxy, CN, SF5, NO2, C1-C6-alkylsulfinyl, halogen-C1-C6-alkylsulfinyl, C1-C6-alkylsulfonyl, halogen-C1-C6-alkylsulfonyl and C1-C4-alkylenedioxy, the latter being unsubstituted or mono- to tetrasubstituted by C1-C4-alkyl and/or by halogen;
p is 0, 1 or 2;
R5 signifies hydrogen or methyl;
R6 and R7 are C1-C4-alkyl;
According to the present application, formula I includes all isomeric forms and mixtures thereof, e.g. racemic mixtures and any [E/Z] mixtures. Alkylxe2x80x94as a group per se and as a structural element of other groups and compounds, such as of halogenalkyl, alkoxy and alkylthioxe2x80x94is either straight-chained, i.e. methyl, ethyl, propyl, butyl, pentyl or hexyl, or branched, e.g. isopropyl, isobutyl, sec.-butyl, tert.-butyl, isopentyl, neopentyl or isohexyl.
Alkenylxe2x80x94as a group per se and as a structural element of other groups and compounds, such as of halogenalkenylxe2x80x94is either straight-chained, e.g. vinyl, 1-methylvinyl, allyl, 1-butenyl or 2-hexenyl, or branched, e.g. isopropenyl.
Alkinylxe2x80x94as a group per se and as a structural element of other groups and compounds, such as of halogenalkinylxe2x80x94is either straight-chained, e.g. propargyl, 2-butinyl or 5-hexinyl, or branched, e.g. 2-ethinylpropyl or 2-propargylisopropyl.
Alkylenedioxy is xe2x80x94O(alkylene)Oxe2x80x94.
Alkylene is either straight-chained, e.g. xe2x80x94CH2CH2xe2x80x94, xe2x80x94CH2CH2CH2xe2x80x94 or xe2x80x94CH2CH2CH2CH2xe2x80x94, or branched, e.g. xe2x80x94CH(CH3)xe2x80x94, xe2x80x94CH(C2H5)xe2x80x94, xe2x80x94C(CH3)2xe2x80x94, xe2x80x94CH(CH3)CH2xe2x80x94 or xe2x80x94CH(CH3)CH(CH3)xe2x80x94.
Alkenylene is either straight-chained, e.g. vin-1,2-ylene, all-1,3-ylene, but-1-en-1,4-ylene or hex-2-en-1,6-ylene, or branched, e.g. 1-methylvin-1,2-ylene.
Alkinylene is either straight-chained, e.g. propargylene, 2-butinylene or 5-hexinylene, or branched, e.g. 2-ethinylpropylene or 2-propargylisopropylene.
Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine. Halogenalkyl may contain identical or different halogen atoms.
Aryl signifies phenyl or naphthyl, preferably phenyl.
Heteroaryl signifies a cyclic aromatic group with 5 to 9 ring members in one or two rings, of which 1 to 3 members are hetero atoms selected from the group oxygen, sulphur and nitrogen. 1 to 2 benzene rings may be condensed on the heterocycle, the binding to the residual molecule taking place either through the hetero or the benzene moiety.
Examples are benzimidazolyl, benzisoxazolyl, benzisothiazolyl, benzocumarinyl, benzofuryl, benzothiadiazolyl, benzothiazolyl, benzothienyl, benzoxazolyl, benzoxdiazolyl, quinazolinyl, quinolyl, quinoxalinyl, carbazolyl, dihydrobenzofuryl, furyl, imidazolyl, indazolyl, indolyl, isoquinolinyl, isothiazolyl, isoxazolyl, methylenedioxyphenyl, ethylenedioxyphenyl, naphthyridinyl, oxazolyl, phenanthridinyl, phthalazinyl, pteridinyl, pudnyl, pyrazinyl, pyrazolyl, pyridazinyl, pyrazolo[3,4-b]pyridyl, pyridyl, pyrimidinyl, pyrrolyl, tetrazolyl, oxadiazolyl, thiadiazolyl, thiazolyl, thienyl, triazinyl and triazolyl.
Preference is given to pyridyl, pyrazinyl, pyrimidinyl, thiazolyl, quinolinyl and thienyl.
Heterocyclyl signifies a 5- to 7-membered, non-aromatic ring with one to three hetero atoms selected from the group comprising N, O and S. Preference is given to non-aromatic 5- and 6-rings that have one nitrogen atom as a hetero atom and optionally one further hetero atom.
Preference is given to pyrazolinyl, thiazolinyl and oxazolinyl.
Of the compounds of formula I, those groups are preferred, wherein:
(1)
a) R1 is methyl, ethyl or cyclopropyl, preferably methyl; or
b) R2 is methyl, ethyl, fluoromethyl or trifluoroethyl, preferably methyl; or
c) R3 is C1-C6-alkyl, C1-C6-alkoxy, C2-C6-alkenyl, C2-C6-alkenyloxy, C2-C6-alkinyl, C3-C6-alkinyloxy, C3-C6-cycloalkyl, C3-C6-cycloalkyloxy or C1-C6-alkoxycarbonyl, whereby the above-mentioned groups may be partially or wholly halogenated; furthermore CN, OCN or halogen; or
d) R3 signifies phenyl which is unsubstituted or mono- to trisubstituted by identical or different substituents from halogen, C1-C6-alkyl, C1-C6-halogenalkyl, C1-C6-alkoxy, C1-C6-halogenalkoxy, C2-C6-alkenyl, C2-C6-alkenyloxy, C2-C6-alkinyl, C3-C6-alkinyloxy, C1-C6-alkoxycarbonyl, CN, OCN, optionally substituted benzyl, optionally substituted phenyl or optionally substituted phenoxy, whereby the above-mentioned aromatic groups may be substituted by one or more identical or different substituents selected from the group comprising halogen, cyano, nitro, C1-C6-alkyl, C1-C6-halogenalkyl, C1-C6-alkoxy, C1-C6halogenalkoxy, C1-C6-alkoxycarbonyl, C1-C6-alkythio, C1-C6-alkylamino, di-C1-C6-alkylamino and C2-C6-alkenyl; or
e) R3 signifies phenyl which is substituted, preferably in 4-position, by QR4, wherein Q is a direct bond, O, OCH2, CH2O, S, CH2xe2x80x94CH2, xe2x80x94CHxe2x95x90CHxe2x80x94 or xe2x80x94Cxe2x89xa1Cxe2x80x94 and R4 signifies phenyl which is unsubstituted or mono- or disubstituted by identical or different substituents from halogen, C1-C4-alkyl, C1-C4-halogenalkyl, C1-C4-alkoxy, C1-C4-halogenalkoxy, C2-C4-alkenyl, C2-C4-alkenyloxy, C2-C4-alkinyl, C3-C4-alkinyloxy, C1-C4-alkoxycarbonyl or CN; or
f) R3 signifies pyridyl, pyrimidinyl, furyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, which are unsubstituted or mono- to trisubstituted by identical or different substituents from halogen, cyano, nitro, aminocarbonyl, C1-C4-alkyl, C1-C4-halogenalkyl, C1-C4-alkylcarbonyl, C1-C4-alkylsulfonyl, C1-C6-alkylsulfoxyl, C3-C6-cycloalkyl, optionally substituted arylcarbonyl, C1-C4-alkoxy, C1-C4-halogenalkoxy, C1-C6-alkoxycarbonyl, C1-C6-alkylthio, C1-C6-alkylamino, di-C1-C6-alkylamino, C1-C6-alkylaminocarbonyl, di-C1-C6-alkylaminocarbonyl, di-C1-C6-alkylaminocarbonyl, or C2-C6-alkenyl; or
g) R5 signifies hydrogen, or
h) R6 and R7 signify methyl or ethyl, preferably methyl.
(2) Compounds of formula I, wherein:
R1 is methyl or ethyl, preferably methyl;
R2 signifies methyl, ethyl, fluoromethyl or trifluoroethyl, preferably methyl;
R3 signifies C1-C6-alkyl, C1-C6-alkoxy, C2-C6-alkenyl, C2-C6-alkenyloxy, C2-C6-alkinyl, C3-C6-alkinyloxy, C3-C6-cycloalkyl, C3-C6-cycloalkyloxy or C1-C6-alkoxycarbonyl, whereby the above-mentioned groups may be partly or wholly halogenated; furthermore CN, OCN or halogen; or
phenyl which is unsubstituted or mono- to trisubstituted by identical or different substituents from halogen, C1-C6-alkyl, C1-C6-halogenalkyl, C1-C6-alkoxy, C1-C6-halogenalkoxy, C2-C6-alkenyl, C2-C6-alkenyloxy, C2-C6-alkinyl, C3-C6-alkinyloxy, C1-C6-alkoxycarbonyl, CN, OCN, optionally substituted benzyl, optionally substituted phenyl or optionally substituted phenoxy, whereby the above-mentioned aromatic groups may be substituted by one or more identical or different substituents selected from the group comprising halogen, cyano, nitro, C1-C6-alkyl, C1-C6-halogenalkyl, C1-C6-alkoxy, C1-C6-halogenalkoxy, C1-C6-alkoxycarbonyl, C1-C6-alkylthio, C1-C6-alkylamino, di-C1-C6-alkylamino and C2-C6-alkenyl; or pyridyl, pyrimidinyl, furyl, thienyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, which are unsubstituted or mono- to trisubstituted by identical or different substituents from halogen, cyano, nitro, aminocarbonyl, C1-C4-alkyl, C1-C4-halogenalkyl, C1-C4-alkylcarbonyl, C1-C4-alkylsulfonyl, C1-C6-alkylsulfoxyl, C3-C6-cycloalkyl, optionally substituted arylcarbonyl, C1-C4-alkoxy, C1-C4-halogenalkoxy, C1-C6-alkoxycarbonyl, C1-C6-alkylthio, C1-C6-alkylamino, di-C1-C6-alkylamino, C1-C6-alkylaminocarbonyl, di-C1-C6-alkylaminocarbonyl, or C2-C6-alkenyl; and
R6 and R7 signify methyl or ethyl, preferably methyl.
(2a) Of those mentioned under (2), especially those in which:
R3 signifies phenyl which is unsubstituted or mono- to trisubstituted by identical or different substituents from halogen, C1-C6-alkyl, C1-C6-halogenalkyl, C1-C6-alkoxy, C1-C6-halogenalkoxy, C2-C6-alkenyl, C2-C6-alkenyloxy, C2-C6-alkinyl, C3-C6-alkinyloxy, C1-C6-alkoxycarbonyl, CN, OCN, optionally substituted benzyl, optionally substituted phenyl or optionally substituted phenoxy, whereby the above-mentioned aromatic groups may be substituted by one or more identical or different substituents selected from the group comprising halogen, cyano, nitro, C1-C6-alkyl, C1-C6-halogenalkyl, C1-C6-alkoxy, C1-C6-halogenalkoxy, C1-C6-alkoxycarbonyl, C1-C6-alkylthio, C1-C6-alkylamino, di-C1-C6-alkylamino and C2-C6-alkenyl.
(3) Compounds of formula I, wherein:
R1 is methyl or ethyl, preferably methyl;
R2 is C1-C6-alkyl or C1-C6-alkyl substituted by 1 to -5 fluorine atoms;
R3 is C1-C6alkyl, C1-C6-alkoxy, C1-C6-alkoxycarbonyl, CN, C3-C6-cycloalkyl, aryl, heteroaryl, heterocyclyl, aryloxy, heteroaryloxy or heterocyclyloxy, whereby, with the exception of CN, the above-mentioned groups may be substituted as mentioned above;
R6 and R7 are methyl or ethyl, preferably methyl.
(3a) Of those mentioned under (3), especially those in which:
R2 is C1-C6-alkyl, fluoromethyl, difluoromethyl or 2,2,2-trifluoroethyl;
R3 is C1-C6-alkyl, C1-C6-alkoxy, C1-C6-alkoxycarbonyl, CN, C3-C6-cycloalkyl, phenyl which is unsubstituted or mono- to tni-substituted by identical or different substituents from halogen, C1-C4-alkyl, C1-C4-halogenalkyl, C1-C4-alkoxy, C1-C4-halogenalkoxy, C2-C4-alkenyl, C2-C4-alkenyloxy, C2-C6-alkinyl, C3-C6-alkinyloxy, CN, OCN, benzyl, phenyl, or phenyloxy, wherein these aromatic groups are unsubstituted or mono- or disubstituted by identical or different substituents from halogen, C1-C2-alkyl, C1-C2-halogenalkyl or C1-C2-alkoxy.
(3b) Of those mentioned under (3a), especially those in which:
R3 is C1-C4-alkyl, C1-C4-alkoxy, C1-C6-alkoxycarbonyl, or phenyl which is unsubstituted or mono- to disubstituted by halogen, C1-C2-alkyl, C1-C2-halogenalkyl or C1-C2-alkoxy.
(4) Compounds of formula I, wherein:
R1 is methyl, ethyl or cyclopropyl, preferably methyl;
R2 is C1-C6-alkyl, preferably methyl or ethyl;
R3 is C1-C6-alkyl, C1-C6-halogenalkyl, C2-C6-alkenyl, C1-C6-alkoxy, C2-C6-alkenyloxy, C1-C6-alkoxycarbonyl, CN, C3-C6-cycloalkyl, aryl, heteroaryl, heterocyclyl, aryloxy, heteroaryloxy or heterocyclyloxy, whereby the hydrocarbon radicals and the cyclic radicals may be substituted as mentioned above;
(4a) Of those mentioned under (4), especially those in which:
R3 is C1-C6-alkyl, C1-C6-halogenalkyl, C2-C6-alkenyl, C1-C6-alkoxy, C2-C6-alkenyloxy, C1-C6-alkoxycarbonyl, C3-C6-cycloalkyl.
(4b) Of those mentioned under (4), especially those in which:
R3 is phenyl which is unsubstituted or mono- or disubstituted by halogen, C1-C4-alkyl, C1-C4-halogenalkyl, C1-C4-alkoxy, C1-C4-halogenalkoxy, C2-C4-alkenyl, C2-C4-alkenyloxy, benzyl, phenyl, or phenyloxy, wherein these aromatic groups are unsubstituted or mono- or disubstituted by halogen, C1-C2-alkyl, C1-C2-halogenalkyl or C1-C2-alkoxy.
(5) Compounds of formula I, wherein:
R1 signifies methyl, ethyl or cyclopropyl;
R2 signifies C1-C6-alkyl, preferably methyl or ethyl, C2-C6-alkenyl, preferably allyl or C2-C6-alkinyl, preferably propargyl.
R3 signifies phenyl which may be substituted by one or more identical or different substituents selected from the group comprising halogen, C1-C6-alkyl, C1-C6-alkoxy, halogen-C1-C6-alkoxy, halogen-C1-C6-alkyl, C1-C6-alkylthio, halogen-C1-C6-alkylthio, C1-C6-alkylsulfinyl, halogen-C1-C6-alkylsulfinyl, C1-C6-alkyl-sulfonyl, halogen-C1-C6-alkylsulfonyl, C2-C6-alkenyl, C2-C6-alkenyloxy, C2-C6-alkinyl, C3-C6-alkinyloxy, C1-C6-alkylcarbonyl, halogen-C1-C6-alkylcarbonyl, C1-C6-alkoxycarbonyl, halogen-C1-C6-alkoxycarbonyl, C1-C6-alkylaminocarbonyl, di-(C1-C6-alkyl)-aminocarbonyl, whereby the alkyl groups may be identical or different, C1-C6-alkylaminothiocarbonyl, di-(C1-C6-alkyl)-aminothiocarbonyl, whereby the alkyl groups may be identical or different, C1-C6-alkylamino, di-(C1-C6-alkyl)-amino, NO2, an unsubstituted C1-C4-alkylenedioxy group or one which is mono- to tetra-substituted by C1-C4-alkyl and/or by halogen; or CN, SF5, OH and QR4;
Q signifies a direct bond, O, O(C1-C6-alkylene), (C1-C6-alkylene)O, C1-C8-alkylene, C2-C6-alkenylene or C2-C6-alkinylene;
R4 signifies an unsubstituted or mono- to penta-substituted C3-C6-cycloalkyl, aryl, heteroaryl or heterocyclyl group, whereby the substituents are selected from the group comprising halogen, C1-C6-alkyl, halogen-C1-C6-alkyl, C1-C6-alkoxy, halogen-C1-C6-alkoxy, phenoxy, CN, SF5, NO2, C1-C6-alkylsulfinyl, halogen-C1-C6-alkylsulfinyl, C1-C6-alkylsulfonyl, halogen-C1-C6-alkylsulfonyl and an unsubstituted C1-C4-alkylenedioxy or one that is mono- to tetra-substituted by C1-C4-alkyl and/or by halogen.
(5a) Of those mentioned under (5), especially those in which:
R3 signifies phenyl which is substituted, preferably in 4-position, by QR4, wherein Q is a direct bond, O, OCH2, CH2O, S, CH2xe2x80x94CH2, xe2x80x94CHxe2x95x90CHxe2x80x94 or xe2x80x94Cxe2x89xa1Cxe2x80x94 and
R4 signifies phenyl which is unsubstituted or mono- or disubstituted by identical or different substituents from halogen, C1-C4-alkyl, C1-C4-halogenalkyl, C1-C4-alkoxy, C1-C4-halogenalkoxy, C2-C4-alkenyl, C2-C4-alkenyloxy, C2-C4-alkinyl, C3-C4-alkinyloxy, C1-C4-alkoxycarbonyl or CN.
Compounds of formula I may be produced as follows:
A) A compound of formula I is produced whereby a hydrazone of the general formula II
wherein R1, R2 and R3 have the significances given for formula I, is reacted with an aldehyde or a ketone of the general formula III or with one of its acetal or imino derivatives of the general formulae IVa and IVb
wherein R8 signifies optionally substituted C1-C6-alkyl or the two R8, together with the two oxygen atoms and the carbon to which they are bonded, signify a cyclic acetal.
The compounds of the general formulae II and III are known from literature (e.g. Ablov et al., Russ.J.Inorg.Chem. (Engl.Transl.), 11, 1966, 39,40; Barton, Derek H. R.; Bashiardes, George; Fourrey, Jan-Louis, Tetrahedron, 44, 1, 1988, 147-162; WO 93/15046) or may be produced by methods known per se. The compounds of the general formulae IVa and IVb may be obtained analogously to the methods described under B) and C) or directly from the carbonyl derivatives of formula III.
B) A compound of formula I is produced whereby a N-hydroxycarbamate of the general formula V,
wherein R1xe2x80x94R3, R5 and R6 are defined as for formula I, is etherified. The compounds of the general formula V are novel and may be produced whereby
a) a N-hydroxyaniline of the general formula VI
wherein R1xe2x80x94R3 and R5 have the significances given for formula I, is reacted with a chloroformic acid ester of the general formula VII
Clxe2x80x94COOR6xe2x80x83xe2x80x83VII
xe2x80x83or
b) a carbonyl compound of the general formula VIII
wherein R5 and R6 have the significances given for formula I, or one of its acetal or imino derivatives VIIIa or VIIIb, is condensed with a hydrazone of the general formula II.
The compounds of formula VI are novel and may be produced by one of the following methods:
aa) a hydrazone of the general formula II is condensed with an aldehyde or ketone of the general formula IX or with one of its acetal or imino derivatives IXa or IXb
wherein R5 is defined as for formula I and R8 is defined as for formula IV. The compounds of formula IX are known (e.g. Bamberger, Elger; Chem. Ber. 36, 3653 (1903); Fijalek, Z.; Zuman, P.; Electroanalysis 5, 53 (1993); Barth, A.; et al.; J.Am. Chem Soc. 119, 4149 (1997); Karakus C.; Zuman, P.; J.Electronanal. Chem. 396, 499 (1995)) and the acetal and imino derivatives thereof may be produced by methods known per se.
ab) a hydrazone of the general formula X
wherein R5 signifies hydrogen or methyl, is condensed with a ketone of formula XI
wherein R1 to R3 are as defined under formula I.
The compounds of formulae X and XI are known (e.g. Buhlmann; Einhorn; Chem. Ber. 34, 3791 (1901)) or may be produced by methods known per se.
ac) A nitro compound of the general formula XII
wherein R1xe2x80x94R3 and R5 are as defined under formula I, is reduced analogously to the methods indicated for the preparation of compounds of formula IX. The compounds of formula XII are novel and may be obtained e.g. by condensation of the corresponding nitrocarbonyl derivatives with hydrazones of formula II.
The compounds of formula VIII are novel and may be prepared by reacting a hydroxyaniline of formula IX with a chloroformic acid ester of formula VII.
C) A compound of formula I is produced whereby an alkoxyaniline of the general formula XIII
wherein R1xe2x80x94R3, R5 and R7 are defined as for formula I, is reacted with a chloroformic acid ester of the general formula VII.
The compounds of formula XIII are novel and may be produced by one of the following methods:
a) A hydrazone of formula II is condensed with an aldehyde or ketone of the general formula XIV or with one of its acetal or imino derivatives
wherein R5 and R7 are defined as for formula I and R8 is defined as for formula IV.
The compounds of formulae XIV, XVa and XVb are novel and may be prepared by etherification of the N-hydroxy derivatives of formula IX.
b) A ketone of formula XI is condensed with a hydrazone of the general formula XVI
wherein R5 and R7 are as defined under formula I. The compounds of formulae XVI are novel and may be prepared by etherificafion of the N-hydroxy derivatives of formula X.
D) A compound of formula I is produced whereby an oxime of the general formula XVII
wherein R1, R3, and R5 to R7 are defined as for formula I, is etherified.
The compounds of formula XVII are novel and may be obtained whereby
a) a ketone of the general formula XVIII
wherein R1, R3 and R5xe2x80x94R7 have the significances given for formula I, is reacted with hydroxylamine or with one of its salts, or
b) a compound of the general formula XIX,
wherein R1, R3 and R5xe2x80x94R7 are defined as for formula I, is reacted with nitrous acid or with an alkyl nitrite in the presence of an acid or base, or
c) a hydrazone of the general formula XX
wherein R1 and R3 are defined as for formula I, is reacted with an aldehyde or ketone of the general formula III or with an acetal or imine of the general formulae IVa or IVb, as a described under A).
The compounds of formulae XVIII and XIX are novel and may be obtained analogously to the preparation of the compounds of formula I.
The compounds of formula XX are known (e.g. Barany et al., J.Chem.Soc., 1951, 1929; Neber; Hartung; Ruopp, Chem.Ber., 58, 1925, 1240; Gnichtel, Horst; Toepper, Bernhard, Liebigs Ann.Chem., GE, 1989, 1071-1074; Rapoport,H.; Nilsson,W., J.Amer.Chem.Soc., 83, 1961, 4262-4267).
E) A compound of formula I may be produced whereby a ketone of the general formula XVIII is reacted with an alkoxyamine of the general formula XXI
R2xe2x80x94ONH2xe2x80x83xe2x80x83XXI
wherein R2 is defined as for formula I, or with one of its salts.
All the above-described reactions are known per se. The novel, above-mentioned intermediates were developed especially for the present invention and similarly form an object of this invention. Those of formulae IV, V, VI, VIII, XII-XIX are of particular significance.
The compounds of formula I are of preventive and/or curative merit as active ingredients for the control of plant pests and may be used in the agricultural sector and related fields The active ingredients of formula I according to the invention are notable for their good activity even at low concentrations, for their good plant tolerance and for their environmental acceptability. They possess very advantageous, especially systemic properties, and may be used for the protection of numerous cultivated plants. Using the active ingredients of formula I, pests appearing on plants or plant parts (fruits, flowers, foliage, stems, tubers, roots) of different crops can be checked or destroyed, whereby parts of the plant which grow later are also protected e.g. from phytopathogenic micro-organisms.
The compounds of formula I may also be be employed as a dressing for seeds (fruits, tubers, grain) and plant cuttings to protect against fungal infections, and to protect against phytopathogenic fungi appearing in the soil.
Compounds I are effective for example against the phytopathogenic fungi belonging to the following classes: Fungi imperfecti (e.g. Botrytis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora and Alternaria); Basidiomycetes (e.g. Rhizoctonia, Hemileia, Puccinia); Ascomycetes (e.g. Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula) and Oomycetes (e.g. Phytophthora, Pythium, Plasmopara).
Target cultivations for the plant-protecting usage in the context of the invention are, for example, the following species of plant: cereals, (wheat, barley, rye, oats, rice, maize, sorghum and related species); beet (sugar beet and fodder beet); pomes, drupes and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); leguminous plants (beans, lentils, peas, soybean); oleaginous fruits (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts); cucumber plants (squashes, cucumbers, melons); fibrous plants (cotton, flax, hemp or jute); citrus fruits (oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); Lauraceae (avocado, cinnamon, camphor); and plants such as tobacco, nuts, coffee, aubergines, sugar cane, tea, pepper, vines, hops, banana plants, natural rubber plants and ornamental.
In addition, the compounds of formula I according to the invention are valuable active ingredients against insects and pests of the order Acarina, such as those appearing on crop plants and ornamentals in agriculture and horticulture and in forestry, whilst being tolerated well by warm-blooded animals, fish and plants. The compounds of formula I are especially suitable for controlling pests in cultivations of cotton, vegetables, fruit and rice, such as spider mites, aphids, caterpillars and plant and leaf hoppers in rice. The pests which are primarily controlled are spider mites such as Panonychus ulmi, aphids such as Aphis craccivora, caterpillars such as those of Heliothis virescens and plant and leaf hoppers in rice, such as Nilaparvata lugens or Nephotettix cincticeps.
The good pesticidal activity of the compounds I according to the invention corresponds to a mortality rate of at least 50-60% of the pests mentioned.
Further fields of application for the active ingredients according to the invention are the protection of stock and material, where the goods stored are protected against rotting and mildew, as well as against animal pests (e.g. grain weevils, mites, maggots, etc). In the hygiene sector, compounds of formula I provide successful control of animal parasites such as ticks, mites, warble flies etc., on domestic animals and productive livestock Compounds I are effective against individual or all stages of development of pests showing normal sensitivity, and also of those showing resistance Their activity may be demonstrated, for example, by the mortality of the pests, which occurs immediately or only after some time, for example during a moult, or by reduced egg laying and/or hatching rate.
Compounds I are used in this instance in unmodified form or preferably together with the excipients that are usual in formulation technology. To this end, they are suitably processed in known manner e.g. into emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, diluted emulsions, wettable powders, soluble powders, dusts or granules, e.g. by encapsulation in e.g. polymeric substances. As with the type of compositions, the methods of application, such as spraying, atomising, dusting, scattering, coating or pouring, are selected in accordance with the intended objectives and the prevailing circumstances.
Suitable carriers and additives may be solid or liquid and are substances that are appropriate in formulation technology, for example natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binding agents or fertilisers.
The compounds of formula I may be mixed with further active ingredients, e.g. fertilisers, trace element intermediates or other plant-protecting compositions, especially with further fungicides. Unexpected synergistic effects may thus occur.
Preferred mixture components are:
azoles, such as azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil, imibenconazole, ipconazole, metconazole, myclobutanil, pefurazoate, penconazole, pyrifenox, prochloraz, propiconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole, tritconazole; pynmidinyl carbinols, such as ancymidol, fenarimol, nuarimol; 2-amino-pyrimidines, such as bupinmate, dimethirimol, ethirimol; morpholines, such as dodemorph, fenpropidine, fenpropimorph, spiroxamine, tridemorph; anilinopyrimidines, such as cyprodinil, mepanipyrim, pyrimethanil; pyrroles, such as fenpiclonil, fludioxonil; phenylamides, such as benalaxyl, furalaxyl, metalaxyl, R-metalaxyl, ofurace, oxadixyl; benzimidazoles, such as benomyl, carbendazim, debacarb, fuberidazole, thiabendazole; dicarboximides, such as chlozolinate, dichlozoline, iprodione, myclozoline, procymidone, vinclozolin; carboxamides, such as carboxin, fenfuram, flutolanil, mepronil, oxycarboxin, thifluzamide; guanidines, such as guazatine, dodine, iminoctadine;
strobilurines, such as azoxystrobin, kresoxim-methyl, metominostrobin, SSF-129, CGA 279202 (trifloxystrobin); dithiocarbamates, such as ferbam, mancozeb, maneb, metiram, propineb, thiram, zineb, ziram; N-halogenmethylthiophthalimides, such as captafol, captan, dichlofluanid, fluoromide, folpet, tolyfluanid; Cu compounds, such as Bordeaux mixture, copper hydroxide, copper oxychloride, copper sulfate, cuprous oxide, mancopper, oxine-copper; nitrophenol derivatives, such as dinocap, nitrothal-isopropyl; organo-P derivatives, such as edifenphos, iprobenphos, isoprothiolane, phosdiphen,. pyrazophos, tolclofos-methyl; various, such as AC 382042, acibenzolar-S-methyl, anilazine, blasticidin-S, quinomethionat, chloroneb, chlorothalonil, cymoxanil, dichlone, diclomezine, dicloran, diethofencarb, dimethomorph, dithianon, etridiazole, famoxadone, fenamidone, fenhexamid, fentin, ferimzone, fluazinam, flusulfamide, fosetyl-aluminium, hymexazol, IKF-916, iprovalicarb, kasugamycin, methasulfocarb, MON65500, pencycuron, phthalide, polyoxins, probenazole, propamocarb, pyroquilon, quinoxyfen, quintozene, RH-7281, RPA 407213, sulfur, triazoxide, tricyclazole, triforine, validamycin.
One preferred method of applying an active ingredient of formula I or an agrochemical composition containing at least one of these active ingredients is application to the foliage (leaf application). The frequency and rate of application depend on the severity of infestation by the invader in question. However, the active ingredients I can also penetrate the plant through the roots via the soil (systemic action) by drenching the locus of the plants with a liquid preparation, or by applying the substances to the soil in solid form, for example in granular form (soil application). With paddy rice cultures, granules may be metered into the flooded paddy field. The compounds I may also be applied to seed grain for seed pre-treatment (coating) by either drenching the grains or tubers in a liquid preparation of the active ingredient or coating them with a solid preparation. The compositions are prepared in known manner, e.g. by intimately mixing and/or grinding the active ingredient with extenders, such as solvents, solid carriers and optionally surface-active compounds (surfactants).
The agrochemical compositions normally contain 0.1 to 99 percent by weight, especially 0.1 to 95 percent by weight, of active ingredient of formula 1, 99.9 to 1 percent by weight, especially 99.8 to 5 percent by weight, of a solid or liquid additive and 0 to 25 percent by weight, especially 0.1 to 25 percent by weight, of a surfactant.
Favourable application rates generally lie between 1 g and 2 kg of active substance (AS) per hectare (ha), preferably between 10 g and 1 kg AS/ha, especially between 20 g and 600 g AS/ha.
For usage as a seed dressing, the dosages advantageously used are 10 mg to 1 g of active substance per kg seeds.
Whereas it is preferred to formulate commercial products as concentrates, the end user will normally use dilute formulations.
The compositions may also contain further additives, such as stabilisers, anti4oaming agents, viscosity regulators, binding agents or tackifiers, as well as fertilisers or other active ingredients, in order to achieve special effects.

A solution of 27.4 g of (2-bromomethyl-phenyl)-N-methoxycarbamic acid methyl ester in 50 ml of acetonitrile is added dropwise at room temperature to 40 g of N-methyl-morpholine-N-oxide in 150 ml of acetonitrile. After stirring for 16 hours, the mixture is concentrated and the residue partitioned between ethyl acetate and water. The aqueous phase is extracted with ethyl acetate and, after drying over sodium sulphate, the solvent is distilled from the combined organic phases. The residue is purified on silica gel using ethyl acetate/hexane (1:5% by volume). The title compound is obtained in the form of a yellow oil.

A solution of 1.05 g of (2-formyl-phenyl)-N-methoxycarbamic acid methyl ester and 1.05 g of 1-(4-fluorophenyl)-2-hydrazono-propan-1-on-O-methyl-oxime in 5 ml of methanol is stirred at room temperature for 4 hours. The resulting by-product (symmetric azine of 1-(4-fluorophenyl)-2-hydrazono-propan-1-on-O-methyl-oxime) is removed by filtration and the filtrate is placed in a refrigerator over night. The product which has crystallised is filtered off (1.0 g). By concentrating the mother liquor and by means of fractional crystallisation of the residue, a further 0.48 g of the title compound are obtained in the form of yellow crystals having a melting point of 88-90xc2x0 C.
The compounds of the following tables may be produced in analogous manner. Abbreviations: i: iso; s: sec; t: tert
Table 1
Compounds of the general formula I.1, in which R2, R6 and R7 signify methyl and R3 corresponds in each case to one line of Table A.
Table 2
Compounds of the general formula I.1, in which R2 signifies ethyl and R6 and R7 signify methyl and R3 corresponds in each case to one line of Table A.
Table 3
Compounds of the general formula I.1, in which R2 signifies difluoromethyl and R6 and R7 signify methyl and R3 corresponds in each case to one line of Table A.
Table 4
Compounds of the general formula I.1, in which R2 signifies 2,2,2-trifluoroethyl and R6 and R7 signify methyl and R3 corresponds in each case to one line of Table A.
Table 5
Compounds of the general formula I.1, in which R2 and R6 signify methyl and R7 signifies ethyl and R3 corresponds in each case to one line of Table A.
Table 6
Compounds of the general formula I.1, in which R2 and R7 signify ethyl and R6 signifies methyl and R3 corresponds in each case to one line of Table A.
Table 7
Compounds of the general formula I.1, in which R2 and R6 signify ethyl and R7 signifies methyl and R3 corresponds in each case to one line of Table A.
Table 8
Compounds of the general formula I.1, in which R2 signifies methyl and R6 and R7 signify ethyl and R3 corresponds in each case to one line of Table A.
Table 9
Compounds of the general formula I.1, in which R2, R6 and R7 signify ethyl and R3 corresponds in each case to one line of Table A.
Table 10
Compounds of the general formula I.1, in which R2 signifies n-propyl and R6 and R7 signify methyl and R3 corresponds in each case to one line of Table A.
Table 11
Compounds of the general formula I.2, in which R2, R6 and R7 signify methyl and R3 corresponds in each case to one line of Table A.
Table 12
Compounds of the general formula I.2, in which R2 signifies ethyl and R6 and R7 signify methyl and R3 corresponds in each case to one line of Table A.
Table 13
Compounds of the general formula I.2, in which R2 signifies difluoromethyl and R6 and R7 signify methyl and R3 corresponds in each case to one line of Table A.
Table 14
Compounds of the general formula I.2, in which R2 signifies 2,2,2-trifluoroethyl and R8 and R7 signify methyl and R3 corresponds in each case to one line of Table A.
Table 15
Compounds of the general formula I.2, in which R2 and R6 signify methyl and R7 signifies ethyl and R3 corresponds in each case to one line of Table A.
Table 16
Compounds of the general formula I.2, in which R2 and R7 signify ethyl and R6 signifies methyl and R3 corresponds in each case to one line of Table A.
Table 17
Compounds of the general formula I.2, in which R2 and R6 signify ethyl and R7 signifies methyl and R3 corresponds in each case to one line of Table A.
Table 18
Compounds of the general formula I.2, in which R2 signifies methyl and R6 and R7 signify ethyl and R3 corresponds in each case to one line of Table A.
Table 19
Compounds of the general formula I.2, in which R2, R6 and R7 signify ethyl and R3 corresponds in each case to one line of Table A.
Table 20
Compounds of the general formula I.2, in which R2 signifies n-propyl and R6 and R7 signify methyl and R3 corresponds in each case to one line of Table A.
Table 21
Compounds of the general formula I.3, in which R2, R6 and R7 signify methyl and R3 corresponds in each case to one line of Table A.
Table 22
Compounds of the general formula I.3, in which R2 signifies ethyl and R6 and R7 signify methyl and R3 corresponds in each case to one line of Table A.
Table 23
Compounds of the general formula I.3, in which R2 signifies difluoromethyl and R6 and R7 signify methyl and R3 corresponds in each case to one line of Table A.
Table 24
Compounds of the general formula I.3, in which R2 signifies 2,2,2-trifluoroethyl and R6 and R7 signify methyl and R3 corresponds in each case to one line of Table A.
Table 25
Compounds of the general formula I.3, in which R2 and R6 signify methyl and R7 signifies ethyl and R3 corresponds in each case to one line of Table A.
Table 26
Compounds of the general formula I.3, in which R2 and R7 signify ethyl and R6 signifies methyl and R3 corresponds in each case to one line of Table A.
Table 27
Compounds of the general formula I.3, in which R2 and R6 signify ethyl and R7 signifies methyl and R3 corresponds in each case to one line of Table A.
Table 28
Compounds of the general formula I.3, in which R2 signifies methyl and R6 and R7 signify ethyl and R3 corresponds in each case to one line of Table A.
Table 29
Compounds of the general formula I.3, in which R2, R6 and R7 signify ethyl and R3 corresponds in each case to one line of Table A.
Table 30
Compounds of the general formula I.3, in which R2 signifies n-propyl and R6 and R7 signify methyl and R3 corresponds in each case to one line of Table A.
Table 31
Compounds of the general formula I.4, in which R2, R6 and R7 signify methyl and R3 corresponds in each case to one line of Table A.
Table 32
Compounds of the general formula I.4, in which R2 signifies ethyl and R6 and R7 signify methyl and R3 corresponds in each case to one line of Table A.
Table 33
Compounds of the general formula I.4, in which R2 signifies difluoromethyl and R6 and R7 signify methyl and R3 corresponds in each case to one line of Table A.
Table 34
Compounds of the general formula I.4, in which R2 signifies 2,2,2-trifluoroethyl and R6 and R7 signify methyl and R3 corresponds in each case to one line of Table A.
Table 35
Compounds of the general formula I.4, in which R2 and R6 signify methyl and R7 signifies ethyl and R3 corresponds in each case to one line of Table A.
Table 36
Compounds of the general formula I.4, in which R2 and R7 signify ethyl and R6 signifies methyl and R3 corresponds in each case to one line of Table A.
Table 37
Compounds of the general formula I.4, in which R2 and R6 signify ethyl and R7 signifies methyl and R3 corresponds in each case to one line of Table A.
Table 38
Compounds of the general formula I.4, in which R2 signifies methyl and R6 and R7 signify ethyl and R3 corresponds in each case to one line of Table A.
Table 39
Compounds of the general formula I.4, in which R2, R6 and R7 signify ethyl and R3 corresponds in each case to one line of Table A.
Table 40
Compounds of the general formula I.4, in which R2 signifies n-propyl and R6 and R7 signify methyl and R3 corresponds in each case to one line of Table A.
Table 41
Compounds of the general formula I.5, in which R2, R6 and R7 signify methyl and R3 corresponds in each case to one line of Table A.
Table 42
Compounds of the general formula I.5, in which R2 signifies ethyl and R6 and R7 signify methyl and R3 corresponds in each case to one line of Table A.
Table 43
Compounds of the general formula I.5, in which R2 signifies difluoromethyl and R6 and R7 signify methyl and R3 corresponds in each case to one line of Table A.
Table 44
Compounds of the general formula I.5, in which R2 signifies 2,2,2-trifluoroethyl and R6 and R7 signify methyl and R3 corresponds in each case to one line of Table A.
Table 45
Compounds of the general formula I.5, in which R2 and R6 signify methyl and R7 signifies ethyl and R3 corresponds in each case to one line of Table A.
Table 46
Compounds of the general formula I.5, in which R2 and R7 signify ethyl and R6 signifies methyl and R3 corresponds in each case to one line of Table A.
Table 47
Compounds of the general formula I.5, in which R2 and R6 signify ethyl and R7 signifies methyl and R3 corresponds in each case to one line of Table A.
Table 48
Compounds of the general formula I.5, in which R2 signifies methyl and R6 and R7 signify ethyl and R3 corresponds in each case to one line of Table A.
Table 49
Compounds of the general formula I.5, in which R2, R6 and R7 signify ethyl and R3 corresponds in each case to one line of Table A.
Table 50
Compounds of the general formula I.5, in which R2 signifies n-propyl and R6 and R7 signify methyl and R3 corresponds in each case to one line of Table A.
Table 51
Compounds of the general formula I.6, in which R2, R6 and R7 signify methyl and R3 corresponds in each case to one line of Table A.
Table 52
Compounds of the general formula I.6, in which R2 signifies ethyl and R6 and R7 signify methyl and R3 corresponds in each case to one line of Table A.
Table 53
Compounds of the general formula I.6, in which R2 signifies difluoromethyl and R6 and R7 signify methyl and R3 corresponds in each case to one line of Table A.
Table 54
Compounds of the general formula I.6, in which R2 signifies 2,2,2-trifluoroethyl and R6 and R7 signify methyl and R3 corresponds in each case to one line of Table A.
Table 55
Compounds of the general formula I.6, in which R2 and R6 signify methyl and R7 signifies ethyl and R3 corresponds in each case to one line of Table A.
Table 56
Compounds of the general formula I.6, in which R2 and R7 signify ethyl and R6 signifies methyl and R3 corresponds in each case to one line of Table A.
Table 57
Compounds of the general formula I.6, in which R2 and R6 signify ethyl and R7 signifies methyl and R3 corresponds in each case to one line of Table A.
Table 58
Compounds of the general formula I.6, in which R2 signifies methyl and R6 and R7 signify ethyl and R3 corresponds in each case to one line of Table A.
Table 59
Compounds of the general formula I.6, in which R2, R6 and R7 signify ethyl and R3 corresponds in each case to one line of Table A.
Table 60
Compounds of the general formula I.6, in which R2 signifies n-propyl and R6 and R7 signify methyl and R3 corresponds in each case to one line of Table A.
Table 62
Compounds of the general formula I.7, wherein R5 signifies H, R1 and R2 signify methyl, Q signifies OCH2 and Z corresponds in each case to one line of Table B.
Table 63
Compounds of the general formula I.7, wherein R5 signifies H, R1 and R2 signify methyl, Q signifies CH2O and Z corresponds in each case to one line of Table B.
Table 64
Compounds of the general formula I.7, wherein R5 signifies H, R1 and R2 signify methyl, Q signifies S and Z corresponds in each case to one line of Table B.
Table 65
Compounds of the general formula I.7, wherein R5 signifies H, R1 and R2 signify methyl, Q signifies xe2x80x94Cxe2x89xa1Cxe2x80x94 and Z corresponds in each case to one line of Table B.
Table 66
Compounds of the general formula I.7, wherein R5 signifies H, R1 and R2 signify methyl, Q signifies xe2x80x94CHxe2x95x90CHxe2x80x94 and Z corresponds in each case to one line of Table B.
Table 67
Compounds of the general formula I.7, wherein R5 signifies H, R1 and R2 signify methyl, Q signifies xe2x80x94CH2xe2x80x94CH2xe2x80x94 and Z corresponds in each case to one line of Table B.
Table 68
Compounds of the general formula I.7, wherein R5 signifies H, R1 and R2 signify methyl, Q signifies a direct bond and Z corresponds in each case to one line of Table B.
Table 69
Compounds of the general formula I.7, wherein R5 signifies H, R1 signifies methyl and R2 signifies ethyl, Q signifies O and Z corresponds in each case to one line of Table B.
Table 70
Compounds of the general formula I.7, wherein R5 signifies H, R1 signifies methyl and R2 signifies ethyl, Q signifies OCH2 and Z corresponds in each case to one line of Table B.
Table 71
Compounds of the general formula I.7, wherein R5 signifies H, R1 signifies methyl and R2 signifies ethyl, Q signifies CH2O and Z corresponds in each case to one line of Table B.
Table 72
Compounds of the general formula I.7, wherein R5 signifies H, R1 signifies methyl and R2 signifies ethyl, Q signifies S and Z corresponds in each case to one line of Table B.
Table 73
Compounds of the general formula I.7, wherein R5 signifies H, R1 signifies methyl and R2 signifies ethyl, Q signifies xe2x80x94Cxe2x89xa1Cxe2x80x94 and Z corresponds in each case to one line of Table B.
Table 74
Compounds of the general formula I.7, wherein R5 signifies H, R1 signifies methyl and R2 signifies ethyl, Q signifies xe2x80x94CHxe2x95x90CHxe2x80x94 and Z corresponds in each case to one line of Table B.
Table 75
Compounds of the general formula I.7, wherein R5 signifies H, R1 signifies methyl and R2 signifies ethyl, Q signifies xe2x80x94CH2xe2x80x94CH2xe2x80x94 and Z corresponds in each case to one line of Table B.
Table 76
Compounds of the general formula I.7, wherein R5 signifies H, R1 signifies methyl and R2 signifies ethyl, Q signifies a direct bond and Z corresponds in each case to one line of Table B.
Table 77
Compounds of the general formula I.7, wherein R5 signifies H, R1 signifies ethyl and R2 signifies methyl, Q signifies O and Z corresponds in each case to one line of Table B.
Table 78
Compounds of the general formula I.7, wherein R5 signifies H, R1 signifies ethyl and R2 signifies methyl, Q signifies OCH2 and Z corresponds in each case to one line of Table B.
Table 79
Compounds of the general formula I.7, wherein R5 signifies H, R1 signifies ethyl and R2 signifies methyl, Q signifies CH2O and Z corresponds in each case to one line of Table B.
Table 80
Compounds of the general formula I.7, wherein R5 signifies H, R1 signifies ethyl and R2 signifies methyl, Q signifies S and Z corresponds in each case to one line of Table B.
Table 81
Compounds of the general formula I.7, wherein R5 signifies H, R1 signifies ethyl and R2 signifies methyl, Q signifies xe2x80x94Cxe2x89xa1Cxe2x80x94 and Z corresponds in each case to one line of Table B.
Table 82
Compounds of the general formula I.7, wherein R5 signifies H, R1 signifies ethyl and R2 signifies methyl, Q signifies xe2x80x94CHxe2x95x90CHxe2x80x94 and Z corresponds in each case to one line of Table B.
Table 83
Compounds of the general formula I.7, wherein R5 signifies H, R1 signifies ethyl and R2 signifies methyl, Q signifies xe2x80x94CH2xe2x80x94CH2xe2x80x94 and Z corresponds in each case to one line of Table B.
Table 84
Compounds of the general formula I.7, wherein R5 signifies H, R1 signifies ethyl and R2 signifies methyl, Q signifies a direct bond and Z corresponds in each case to one line of Table B.
Table 85
Compounds of the general formula I.7, wherein R5 signifies H, R1 signifies ethyl and R2 signifies ethyl, Q signifies O and Z corresponds in each case to one line of Table B.
Table 86
Compounds of the general formula I.7, wherein R5 signifies H, R1 signifies ethyl and R2 signifies ethyl, Q signifies OCH2 and Z corresponds in each case to one line of Table B.
Table 87
Compounds of the general formula I.7, wherein R5 signifies H, R1 signifies ethyl and R2 signifies ethyl, Q signifies CH2O and Z corresponds in each case to one line of Table B.
Table 88
Compounds of the general formula I.7, wherein R5 signifies H, R1 signifies ethyl and R2 signifies ethyl, Q signifies S and Z corresponds in each case to one line of Table B.
Table 89
Compounds of the general formula I.7, wherein R5 signifies H, R1 signifies ethyl and R2 signifies ethyl, Q signifies xe2x80x94Cxe2x89xa1Cxe2x80x94 and Z corresponds in each case to one line of Table B.
Table 90
Compounds of the general formula I.7, wherein R5 signifies H, R1 signifies ethyl and R2 signifies ethyl, Q signifies xe2x80x94CHxe2x95x90CHxe2x80x94 and Z corresponds in each case to one line of Table B.
Table 91
Compounds of the general formula I.7, wherein R5 signifies H, R1 signifies ethyl and R2 signifies ethyl, Q signifies xe2x80x94CH2xe2x80x94CH2xe2x80x94 and Z corresponds in each case to one line of Table B.
Table 92
Compounds of the general formula I.7, wherein R5 signifies H, R1 signifies ethyl and R2 signifies ethyl, Q signifies a direct bond and Z corresponds in each case to one line of Table B.
Table 93
Compounds of the general formula I.7, wherein R5 signifies methyl, R1 and R2 signify methyl, Q signifies O and Z corresponds in each case to one line of Table B.
Table 94
Compounds of the general formula I.7, wherein R5 signifies methyl, R1 signifies ethyl and R2 signifies methyl, Q signifies O and Z corresponds in each case to one line of Table B.
Table 95
Compounds of the general formula I.7, wherein R5 signifies methyl, R1 signifies methyl and R2 signifies ethyl, Q signifies O and Z corresponds in each case to one line of Table B.
Table 96
Compounds of the general formula I.7, wherein R5 signifies methyl, R1 signifies ethyl and R2 signifies ethyl, Q signifies O and Z corresponds in each case to one line of Table B.
Table 97
Compounds of the general formula I.7, wherein R5 signifies H, R1 signifies methyl and R2 signifies propargyl, Q signifies O and Z corresponds in each case to one line of Table B.
Table 98
Compounds of the general formula I.7, wherein R5 signifies H, R1 signifies ethyl and R2 signifies propargyl, Q signifies O and Z corresponds in each case to one line of Table B.
Table 99
Compounds of the general formula I.7, wherein R5 signifies H, R1 signifies methyl and R2 signifies allyl, Q signifies O and Z corresponds in each case to one line of Table B.
Table 100
Compounds of the general formula I.7, wherein R5 signifies H, R1 signifies ethyl and R2 signifies allyl, Q signifies O and Z corresponds in each case to one line of Table B.
Table 101
Compounds of the general formula I.7, wherein R5 signifies H, R1 signifies methyl and R2 signifies n-propyl, Q signifies O and Z corresponds in each case to one line of Table B.
Table 102
Compounds of the general formula I.7, wherein R5 signifies H, R1 signifies ethyl and R2 signifies n-propyl, Q signifies O and Z corresponds in each case to one line of Table B.
Table 103
Compounds of the general formula I.7, wherein R5 signifies H, R1 signifies methyl and R2 signifies isopropyl, Q signifies O and Z corresponds in each case to one line of Table B.
Table 104
Compounds of the general formula I.7, wherein R5 signifies H, R1 signifies ethyl and R2 signifies isopropyl, Q signifies O and Z corresponds in each case to one line of Table B.
Details of the physical data in the following Tables: xc2x0=m.p. in xc2x0Celsius; Number=chemical displacement of R5 in 1H-NMR (.xcex4.in ppm); * isomers
Formulations may be prepared analogously to those described for example in WO 97/33890.
In the following patho-systems, compounds from the tables display good activity.
A. Fungicidal Activity


A registration system for copy sheets uses a pair of drive rolls and a drive system for commonly driving both drive rolls. A differential drive mechanism is provided for changing the relative angular position of one of the rolls with respect to the other roll to deskew the copy sheet. A control system is supplied with inputs representative of the skew of the copy sheet and controls the differential drive mechanism to deskew the copy sheet. The system offers enhanced performance and reduced cost.

1. Field of the Invention
This invention relates to registration of sheets in a feed path. It particularly relates to systems for controlling driving rolls to effect registration and deskewing of copy sheets.
2. Description of Related Art
Conventional sheet registration mechanisms for equipment using paper feed stocks, such as electrophotographic reproduction equipment and printers, use crossed nip rolls in conjunction with fixed guides or gates for positioning the copy sheet. The crossed nip rolls push the sheets against such guides and gates. These conventional systems have many drawbacks. If the sheet is driven against the guide and gate surfaces with excessive force, the edges of the sheets can be bent or crumpled. This condition occurs especially with light weight papers and causes problems in downstream feeding of the paper. Thus, each system must be carefully set for a narrow range of paper weight to provide sufficient driving force for movement of the sheet without damaging it as it is driven against a guide or gate. Further, the guides are subject to wear resulting from the impingement of the edges of a large number of copy sheets. Thus, the guides must be replaced one or more times during the life of a machine, thereby increasing maintenance costs. In addition, undesirable dust is formed as a result of the impact and sliding the paper against the hard guide surfaces. One system of this type, using a passive differential between spaced rolls to allow one of the rolls to rotate at a higher speed than the other of the rolls, has been proposed.
Sheet registration systems without mechanical guides or gates, using drive rolls for sheet registration, have also been proposed. Sheet registration stations of this type are shown in U.S. Pat. Nos. 4,438,917, 4,511,242, 4,971,304 and 5,049,442. In these sheet registration stations, the copy sheet is positioned longitudinally and laterally (registered) and the angular position of the copy sheet (skew) is corrected by driving two coaxial nip rolls at different speeds or by driving one roll at a constant speed and varying the drive speed of the other roll, so that one side of the sheet travels farther than the other, thus changing the angular position of the paper. Each of the two rolls is driven by an independently controlled motor. These designs present control limitations because of the requirements of precisely controlling the velocity difference between the two rolls (to achieve high positional resolution) and operating the drives at high speed (to achieve high throughput rates). This results from the fact that the drive system must accomplish two different functions with conflicting requirements. The rolls must transport the copy paper at relatively high speed, a condition in which the speed of both rolls must be exactly the same. The rolls must also correct the angular position of the copy sheet by precisely changing the relative angular position between the two rolls.

Differential drive for sheet registration drive rolls with skew detection


A method for simultaneously forming multiple line-widths, one of which is less than that achievable employing conventional lithographic techniques. The method includes providing a structure which includes a memory layer and a sidewall image transfer (SIT) layer on top of the memory layer. Then, the SIT layer is patterned resulting in a SIT region. Then, the SIT region is used as a blocking mask during directional etching of the memory layer resulting in a first memory region. Then, a side wall of the SIT region is retreated a retreating distance D in a reference direction resulting in a SIT portion. Said patterning comprises a lithographic process. The retreating distance D is less than a critical dimension CD associated with the lithographic process. The SIT region includes a first dimension W2 and a second dimension W3 in the reference direction, wherein CD<W2<2D<W3.

In the prior art, a conventional lithographic process can be used to form a first line-width greater than or equal to a minimum CD (critical dimension) associated with the lithographic process, or a SIT process can be used to form a second line-width smaller than the CD. Therefore, there is a need for a method for simultaneously forming multiple line-widths greater than and smaller than the CD.

Sidewall image transfer processes for forming multiple line-widths

International Business Machines Corporation


An integrated circuit memory device has multiple subarray partitions which can be independently isolated from the remaining circuitry on the integrated circuit. Subarrays of the integrated circuit can be independently tested. Should a subarray of the integrated circuit be found inoperable it is electrically isolated from the remaining circuitry on the integrated circuit so that it cannot interfere with the normal operation of the remaining circuitry. Defects such as power to ground shorts in a subarray which would have previously been catastrophic can be electrically isolated allowing the remaining functional subarrays to be utilized. Integrated circuit repair by isolation of inoperative elements eliminates the current draw and other performance degradations that have previously been associated with integrated circuits with defects repaired through the incorporation of redundant elements alone.

As the device geometries of integrated circuits continue to decrease with improvements in manufacturing processes, greater numbers of circuits can be arrayed on a single integrated circuit die. There is also an increased probability that at least some of these circuits will be defective in some way. It has become standard practice in the design of Dynamic Random Access Memory (DRAM) devices to provide redundant memory elements that can be used to replace defective memory elements and thereby increase device yields. Redundant elements can only be used to repair certain types of defects by replacing a row, a column or a subarray of an array of devices. Depending on the particular defect repaired, the device may exhibit undesirable characteristics such as increased standby current, speed degradation, reduction in operating temperature range, or reduction in supply voltage range as a result of the defect being present on the die. Certain other types of defects cannot be repaired effectively through redundancy techniques alone. Defects such as power to ground shorts in a portion of the array can prevent the device from operating even to the extent required to locate the defect in a test environment. Memory devices with limited known defects have been sold as "partials", "audio RAMs" or "off spec devices" provided that the defects do not prohibitively degrade the performance of the functional portions of the memory. The value of a partially functional device decreases dramatically as the performance of the device deviates from that of the standard fully functional device. The desire to make use of devices with limited defects, and the problems associated with the performance of these devices due to the defects are well known in the industry.

Efficient method for obtaining usable parts from a partially good memory integrated circuit


A method updating a program in a flash memory includes executing a first image of the program while an address space of the program is imaged onto the memory blocks, which are operated in a single-level mode; copying part of the first image from a range within the address space, which is imaged onto one of the blocks, into a backup block; setting the one of the blocks to a multi-level mode; while the address range is imaged onto the backup block, programming the one of the blocks with part of the second image besides for the part of the first image; switching the address range back to the block while the block remains in the multi-level mode; as long as the second image is incomplete, repeating the copying, programming, and switching with further parts of the second image; and subsequently executing the second image instead of the first image.

A non-volatile electronic memory component whose content is able to be electrically erased is known to one skilled in the art as an electrically erasable programmable read-only memory (EEPROM). Within the scope of the following statements, the term "EEPROM" is used in a broad sense of the word and in addition to conventional EEPROMs, also encompasses the more recent so-called flash memories, which are erasable block by block. To allow for a non-volatile storage at a low energy consumption, these flash EEPROM memories are predominantly used in vehicle electronics according to the related art, where the information stored in individual memory cells is stored in the form of electrical charges on a floating gate or in a charge-trapping memory element of a metal insulator semiconductor field-effect transistor (MISFET). In this case, the memory cells are basically disposed as a matrix in what is known as a cell array, and via a coordinate, the address lines are used for selecting a column or line of memory cells, and in the other coordinate, data lines lead to the memory cells.
In an effort to increase the storage density, multi-level cells (MLC) in which more than one bit per line is stored are sometimes used in this context. To make this possible, the charge quantity stored in a memory cell is dosed more finely and is also evaluated more precisely during the readout in order to be able to distinguish more than two possible states and to store more than one bit. In comparison with a single-level cell (SLC), this has the disadvantage of a reduced read and write speed. An MLC also reacts with considerably greater sensitivity to possible charge losses.
In DE 102014223035 A1, a method is introduced for transmitting data within a computer system between a memory interface of a volatile memory, a memory interface, in particular an MLC-NAND memory, and an interface of a microcontroller, the method including the reading in of data from the memory interface of the MLC-NAND memory at the start of a booting process of the microcontroller and the provision of the read-in data to the memory interface of the volatile memory.

Method and device for updating a program


A method for adjusting the chlorine equilibrium in a sulphate cellulose process, wherein part of the chlorine contained in the cycle is separated and removed. In the method, strong odour gases from the sulphate cellulose process are introduced into a soda recovery boiler for burning so that chlorine contained in the liquor is in the form of hydrogen chloride (HCl) in the upper part of the soda recovery boiler and can subsequently be separated from the flue gases in a flue gas scrubber. The chlorine equilibrium is adjusted by removing part of the chlorine-containing washing solution.

In the process of a sulphate cellulose mill, chlorine (essentially present in the combined form, primarily as sodium chloride) accumlates in the chemical cycle as the amount of chlorine accumlates the process from the raw material, such as wood, from water, together with substituting chemicals, etc., is greater than the amount of chlorine removed from the process in any form. Even though chlorine is removed together with the pulp and at other process stages, it, however, tends to accumlate in the process. Excessive chlorine causes disadvantageous corrosion and pluggings in the soda recovery boiler and is also otherwise disadvantageous in the regeneration of chemicals. Various attempts have been made to remove chlorine, e.g. together with salts in the form of NaCl. U.S. Pat. No. 3,746,612 discloses a method for removing chlorine from white liquor, where white liquor is treated in an extremely complicated way in order that chlorine contained in the solution could be separated as NaCl. In general, the removal of chlorine from the process is difficult in most cases and requires plenty of extra equipment. In addition, chlorine removal processes are difficult to adjust.

Method for controlling chloride concentration in the flue gas of a recovery boiler


An apparatus is disclosed that includes a phase detector circuit for generating a first pulse signal based on first and second input clock signals. A first circuit adjusts the first pulse signal by delaying transmission of a leading edge of the first pulse signal, but not a trailing edge of the first pulse signal. A charge pump circuit charges or discharges a capacitor based on the adjusted first pulse signal, and a voltage controlled oscillator (VCO) circuit generates an output clock signal with a frequency that depends on a voltage on the capacitor.

Digital systems include a variety of circuits, many of which rely on clock signals (hereinafter "clocks") with different frequencies to synchronize the timing of operations, data transfers, etc. Phase-locked loops (PLLs) can supply these needed clocks.
PLLs need a reference clock. A crystal oscillator is often used to generate the reference clock at a base frequency. PLLs use the reference clock to generate clocks with frequencies that are multiples of the base frequency.
In general, a PLL contains a phase frequency detector (PFD), a low-pass loop filter, a voltage controlled oscillator (VCO) and a feedback path that includes a programmable frequency divider (hereinafter divider). The PFD receives two clock inputs; the reference clock, and a feedback clock from the divider. A clock has two edges; a leading edge that rises at the start of the clock period, and a trailing edge that typically marks the end of a half clock period. As will be described below the PFD detects a "phase error" (i.e., a time delay) between leading edges of the reference and feedback clocks. The VCO generates an output clock with a frequency fout that increases or decreases as the phase error increases or decreases.
The divider, also called a clock divider, is positioned in the feedback path between the VCO and the PFD. The divider receives and frequency divides the output clock to produce the feedback clock with a frequency ffb=fout/N, where N is referred to as the divider's integer divide ratio. When no phase error exists between the reference and feedback clocks, the reference and feedback clock frequencies fref and ffb, respectively, are substantially the same, which in turn locks the frequency fout of the output clock. In other words, fout=N·ffb=N·fref when the PLL is in steady state.
Integer-N PLLs generate an output clock with a frequency that is an integer multiple N of the reference clock frequency (i.e., fout=N·fref). In contrast a fractional-N PLL (hereinafter fractional PLL) can generate an output clock with a frequency that is a non-integer multiple of the reference frequency fref. This can be done by switching the integer divide ratio between N and N+1 in such a way that the "average" divide ratio is N+K/F. If for F cycles (e.g. F=10 cycles), the divider divides the output clock by N+1 for the first K (e.g., K=7) cycles, and then by N for the last F-K (e.g., 3) cycles, the average divide ratio is N+K/F (e.g., N+7/10), and the average output clock frequency is fout=(N+K/F)·fref.
The use of the same reference symbols in different drawings indicates similar or identical items.

Fractional N PLL with sigma-delta noise cancellation


Treated electrolytic copper foil wherein the shiny side of the raw foil is modified and smoothed by an electrodeposited copper gilding layer, a copper-clad laminate produced with such foil, and an electrical circuit produced from such a laminate. The preferred foil has the surface of the shiny side of the raw foil modified by an electrodeposited copper gilding layer, a copper dendritic layer electrodeposited on the gilding layer, and a second copper gilding layer electrodeposited on the first dendritic layer, while a copper dendritic layer is electrodeposited on the surface of the matte side of the foil, and a copper gilding is electrodeposited on the latter dendritic layer.

1. Field of the Invention
This invention relates to electrolytic copper foil, more particularly, to such copper foil produced on a rotating drum cathode machine and having its shiny side (drum side) modified by a copper gilding layer electrodeposited thereon, and still more particularly, to such copper foil wherein a copper bonding treatment is formed both on the matte side and the modified shiny side of the foil.
2. Background of the Invention
Electrolytic copper foil produced on rotating drum machines, prior to being treated, is usually referred to as raw foil. The raw foil is pink in color and has two distinctly looking sides--a "shiny side", the side which was plated onto the drum surface and then stripped is smooth, while the other side, the side which was facing the electrolyte and the anodes, is referred to as the "matte" side since it has a velvety finish, due to the difference in the growth rate of differing crystal faces during electrodeposition of the raw foil. The matte side surface, at this stage has a very fine scale micro-roughness and a very specific micro-topography. Viewed under high magnification of a scanning electron microscope, it is composed of peaks and valleys. The peaks are closely packed cones or pyramids. The cone's height, slant, packing and shape depend, as is well known, upon closely controlled independent variables of foil thickness, current density, solution composition and temperature and the type and concentration of the addition agents and the like.
In the fabrication of copper-clad laminates for printed circuit boards (PCBs), copper foil is bonded to polymeric substrates (composite materials: epoxy, polyamide and other similar resins reinforced with glass fiber fabric) by means of mechanical interlocking at the interface between the two materials. To achieve a high degree of interlocking, the bonding side of the foil is provided with a "bonding treatment".
Various patents directed to bonding treatments for copper foil disclose, for example, that one or both sides of the foil which is to be bonded to the substrate is subjected to the bonding treatment (U.S. Pat. No. 5,207,889), or that such treatment for copper foil to be used for lamination to a substrate comprises electrodepositing a dendritic layer of copper followed by a gilding, or encapsulating, layer of copper on the side of the foil that is to be laminated to the board (U.S. Pat. Nos. 3,857,681, Re. 30,180 and 4,572,768).
Such bonding treatment is an extremely dense coating of spherical micro-projections, which is usually electrodeposited to the matte side of base copper foil. This matte side, in itself, is composed of densely packed, micro-conical or micro-pyramidal shapes, which form a micro-topography of peaks and valleys. The peel strength of cooper foil (force necessary at separate, or pull away, the foil from polymer substrate) will depend on the shape of individual micro-projections, their mechanical strength and hardness, density per surface area, and their distribution over micro-peaks and micro-valleys of the matte side of the base foil. In turn, all the factors listed above will depend on the conditions under which the treatment is electrodeposited and the micro-topography of the base foil. Usually, processes for the electrodeposition of bonding treatments employ plating conditions which give rise to high cathodic concentration polarization, namely high current density, low copper concentration and temperature of the electrolyte. Often, the addition of other ionic species, such as chlorides or arsenic, are used to enhance tree-like (on a microscopic scale) structures, which are good for bonding. As such deposits are, by nature, good for increasing surface area, but weak mechanically, the second step of the treatment, locking or encapsulation, usually follows the first step, in order to improve the treatment's mechanical resilience. The treatment operation is conducted in the machines called treaters. Rolls of raw foil are placed at an unwinding station of the treater and fed into the treater by means of driven rollers (similar to the way in which a web of paper is handled in a printing machine), rendered cathodic by means of contact rollers, and passed in a serpentine fashion through a series of plating tanks, facing a rectangular anode in each tank. Each tank has its own supply of appropriate electrolyte and its d.c. power source; between the tanks, the foil is thoroughly rinsed on both sides. The purpose of this operation is to electrodeposit micro-projections of complex shape (visible only under high magnification microscope) on the matte side of the foil, which ensure that the foil may be firmly anchored to the base polymeric materials used in PCB's fabrication. The last tank of the treater provides the foil with a so-called stainproof layer, which prevents staining, tarnishing and oxidation and imparts long shelf life on the foil. Upon leaving the passivation tank, the foil is subjected to the final rinse, dried and coiled into rolls by take-up driven shaft-rollers. At that stage, foil is a finished product. Obviously, to be capable of handling a very thin and fragile copper foil in a manner described above, treater machines are custom built and very carefully engineered. A system of driving the rollers and the foil, web guiding, tension control devices, synchronization at peripheral speed of all guiding rollers, precise machining of "contact rollers" which pass electric current into the foil etc., are the elements of treaters design and engineering which together combine to make treaters very sophisticated and expensive machines.
The basic raw material for manufacture of printed circuits is a laminate clad with copper foil. It is comprised of a thin copper foil firmly bonded to a polymeric, dielectric (insulating) base material. This "bonding" operation is conducted in laminating plants and involves heating and cooling cycles. Sheets of copper foil are laid upon sheets of "prepreg" (e.g. glass fabric impregnated with epoxy resin). Both materials are placed in a hydraulic press having heated pressing plates, while-the two materials are pressed-together under high pressure. At elevated temperatures, the resin liquefies and is forced, by the pressure, to flow into the micro-irregularities of the foil surface. This is followed with a second cycle, when both materials are cooled while the pressure is being maintained. The resin solidifies in the irregularities of the foil surface and both materials are firmly bonded together and are very difficult to pull apart. The "peel strength" between both materials is high, because the bonding side of the copper foil is provided with the bonding treatment. High peel strength is a characteristic of the highest importance since the mechanical support of the circuit elements as well as the current carrying capability of PCB's is provided by the copper foil polymer joint. It is essential that the foil is bonded very tightly and securely to the laminate and also that such an adhesive joint can withstand all the manufacturing steps in PCB's fabrication without a decrease of the initial adhesion, which, moreover should remain constant throughout the service life of the PCB. It is a well-established fact that to achieve satisfactory adhesion in bonding operations, metallic substrates have to be pretreated. A satisfactory pretreatment must not only give the appropriate initial level of adhesion but must also provide "durability". The adhesion must not be seriously affected by environmental conditions, specifically, processing chemicals used in PCB's fabrication, elevated temperatures, high humidity or water. Obviously, copper foil-polymeric substrate bond strength is more and more important as fine-line applications become more common. The adherence between copper foil and the substrate must not only be adequate initially, but ought to be durable and permanent. The usual testing of the peel strength of the sheared 1 cm (or 1 inch) wide specimen of the clad laminate offers only a broad idea of the reliability of the joint to the circuit designer. The permanency of the peel strength under various environmental conditions encountered in PCB's fabrication and their service life is probably no less important. Electrodeposited bonding treatment and its role represent a very special case of industrial application of the electrodeposit. In electrodeposition in general, the adherent, compact deposits are of practical use and the loose, powdery or dendritic deposits are regarded as a nuisance. Powdery electrodeposits, however, have their own technical applications, particularly in the field of powdered metallurgy or catalysis. We have found such deposits to be convenient for providing copper foil with good bonding characteristics.
The parameters of the dendritic (treatment's first step) deposition are purposefully set as to encourage the growth of powdery/dendritic layers. They are:
Low copper concentration PA1 Low temperature PA1 High current density PA1 (a) an electrolytic copper base foil having a matte side and an opposite shiny side; PA1 (b) a first copper bonding treatment on the matte side formed of (i) a first electrodeposited dendritic copper layer on the surface of the matte side, and (ii) a first electrodeposited copper gilding layer on the dendritic layer, forming a treated matte side; and PA1 (c) a micro-roughening copper layer on the shiny side formed of (i) a second electrodeposited copper gilding layer on the surface of the shiny side, (ii) a second electrodeposited dendritic copper layer on the second gilding layer, and (iii) a third electrodeposited gilding layer on the second dendritic layer, forming a treated shiny side.
All these factors lead to high cathodic polarization, or poor mass transport, which enhances the dendritic (tree-like) character of the deposit. What makes the treating process even more complex, is the fact that it is electrodeposited on the matte side of the base foil surface which is not truly flat, but composed of microscopic peaks and valleys. In general, the structure of a deposit depends strongly on the rate of formation of new nuclei and the rate of growth of the already existing crystals. The grain size is especially affected by the ratio of these two rates. If the rate of nucleation is small and the rate of crystal growth large, a deposit with coarse grains results. In the contrary case, the deposit is fine grained. Powder formation can then be regarded as a limiting case in which the rate of nucleation is large and the growth of crystals, particularly their intergrowth, is strongly inhibited. One could add that between the extreme cases of highly dispersed powder and an even, well-adhering deposit, many intermediate cases may occur. Only a narrow range of copper particle size and shape combination is well suited to be the foil bonding. We have mentioned before that powder formation is brought about when the rate of nucleation is large while the growth of crystals is inhibited. These conditions are the consequence of the depletion of copper ions near the cathode (matte side of the foil). It is well established that the depletion of the metallic ions near the cathode is a decisive factor in powder formation. More precisely, powder formation starts when the limiting current is reached or approached, e.g., when the concentration of metallic ions at the cathode-solution interface is zero. The limiting current and, more specifically, the depletion near the cathode, are governed by mass transfer processes.
Bonding treatment may be effected by subjecting the matte side of the "raw" foil to four consecutive electrodeposition steps. The first consists of the deposition of the microdendritic layer which enhances, to a very large degree, the real surface area of the matte side, and thus enhances the foil's bonding ability. This is followed by electrodeposition of an encapsulating (gilding) layer, whose function is to reinforce mechanically the dendritic layer and thus render it immune to the lateral shear forces of liquid resins in the laminating stage of PCB's fabrication. The encapsulating step of the treatment is very important, since it eliminates the foil's tendency toward "treatment transfer" and the resulting "laminate staining" which can cause a decrease of the laminate's dielectric properties. Such a dendrites-encapsulation composite structure should be characterized by high bond strength and the absence of treatment transfer. The treating parameters which assure just that are relatively narrow. If the amount of gilding deposit is too low, the foil will be given to treatment transfer, if on the other hand gilding layer is too thick, a partial loss of peel strength may be expected. These first two steps of the treatment are composed of pure copper, in the form of microscopic, spherical micro-projections. The electrodeposition of this copper bonding treatment is followed by deposition of a very thin layer of zinc or zinc alloy, a so-called barrier layer. Its purpose is to prevent direct copper-epoxy resin contact, and that is why the zinc-alloy layer (which during lamination is converted to alpha brass) is called the barrier layer. If the bonding treatment composed of copper only is subjected to lamination with epoxy resin systems, it tends to react with amino groups of the resin at the high laminating temperatures. It, in turn, creates moisture at the foil-resin interface, causing a harmful effect of "measling" and possibly delamination. A barrier layer which is plated over all-copper treatment prevents these harmful effects entirely. All three stages of the treatment mentioned above, effected by means of electrodeposition, change the geometry and morphology of the matte side of the foil, assuring the mechanical strength of the surface region, as well.
The electrodeposition of the treatment is typically followed by an electrochemical stainproofing which changes the surface chemistry. As a result of this step, the bonding surface is rendered chemically stable. This operation removes weak surface films, which can greatly decrease the adhesion of the solids, and replace them with a stable film of controlled thickness, responsible for imparting "durability" of its properties on the treated surface. The film serves as an undercoat for subsequent bonding. The same stainproofing step protects the shiny side of the foil against atmospheric oxidation.
Contemporary bonding treatments were invented in the early seventies and the major foil manufacturers are using the same techniques today. The changes that have occurred in the intervening years pertain, by and large, to the composition of the barrier layers, and have been made to accommodate technical needs imposed by the emergence of new polymeric dielectric substrates used in the manufacture of PCB's. For example, polyimide substrates introduced to the printed circuit industry fairly recently require a much higher laminating temperature than the epoxy pre-pregs. Consequently, foil manufacturers modified this portion of the overall treating processes in order to achieve the desired composition and performance of barrier layers for the foils that are destined for polyimide applications. Barrier layers on polyimide-grade treatments have to withstand much higher laminating and post-bake temperatures, compared to the treatments destined for epoxy applications. High temperature at the metal-polymer interface can subject the metal surface to oxidation with the attendant partial loss of adhesion. A well designed barrier layer will be self-protected along with the underlaying all-copper treatment from heat oxidation and the loss of bond. Other changes in the technology of the bonding treatment are occurring as well. For example, some major foil manufacturers build their new treaters with a larger number of individual plating tanks, in order to apply twice the sequence of dendritic deposit followed by encapsulating deposit. Thus, quite often, the first four tanks of the treater are devoted to the application of micro-roughening treatment that consists of a dendritic layer followed by an encapsulation layer, and this composite plural layer is repeated twice. This practice is aimed at being able to run the treater at greater speeds, since the initial capital outlay for the construction of the treaters is very high today. Conversely, the larger the number of tanks, with the treater run at more traditional speeds, permits deposition of a greater mass or weight of the treatment to assure acceptable peel-strength on so-called "difficult to bond to" polymeric substrates that aim at higher glass transition temperatures. These substrates, which are often a blend that involves multifunctional epoxies, BT resin, polyimide etc. usually require an increased amount of bonding treatment to assure adequate peel-strength. It should be remembered that aside from its bond-enhancing microstructure, the amount of treatment per surface area of copper foil is also an important factor.
With the advent of miniaturization, very densely packed printed circuit boards are needed. Miniaturization often requires that the copper foil conductor, or track lines, of today's printed circuit board be as narrow as 5 mils, or less. The degree of high definition of fine line circuitry depends on the quality of copper foil manufactured for the electronic industry, particularly on surface quality of both sides of the foil. One side of the foil, whose role is to firmly anchor track lines to the polymeric substrate, is provided with a bonding treatment. After the foil is bonded to the substrate the other side of the foil, which forms the outer surface of copper-clad laminate, is used for image patterning.
It is the practice in manufacturing printed circuit boards from copper-clad laminates to form an image of the desired printed circuit pattern on the exposed copper surface of a laminate by a photographic technique which leaves the desired pattern formed of a photo-resist material on the surface of the copper.
It will be appreciated that for the photographic imaging to be sharp and precise, the photo-resist has to spread well on the foil's surface and adhere well to this surface.
It is a practice in manufacturing PCBs to roughen the exposed surface of the copper to achieve good resist adhesion. This roughening also removes tenacious stainproof films which foil manufacturers apply to the foil to protect it from oxidation and staining before it reaches the user. Photo-resist does not adhere to the stainproof films, which therefore have to be removed. Thus, roughening of the foil surface serves the purpose of removal of stainproof film, as well as changing the copper surface topography from smooth to micro-rough, to facilitate photo-resist adhesion which is a condition of good definition of track lines.
This roughening is performed by either mechanical means, e.g., abrasion by brushes, scrubbing with pumice, or chemical means (so-called micro-etching), which is accomplished by subjecting the copper surface of copper-clad laminates to the etching action of oxidizing mineral acids. Such acids attack the smooth surface of the foil along the copper grain boundaries, thus creating pits and pores and changing the copper surface from smooth to micro-rough.
Multi-layer printed circuit boards, so-called MLBs, now dominate the printed circuit board market, since they permit achieving the highest functional density in electronic packaging. In the fabrication of MLBs, copper foil is laminated (bonded) to polymeric substrates twice. First, thin, double-sided copper clad laminates are produced. These laminates are then subjected to image patterning and etching away of unwanted copper to produce the desired patterns of circuitry. Several layers of double-sided boards prepared in such a manner are stacked together, with sheets of prepreg (glass reinforced polymeric resin composites) inserted in between to dielectrically separate adjacent boards from one another. Such a stack of circuit boards and pre-preg is then laminated together, in the so-called "B-stage lamination", to form a monolithic multi-layer board. Later, holes are punched or drilled through the board in pre-arranged places and so-called thru-hole plating of copper is used to ensure the electrical interconnection between all layers of copper-track conductor lines.
It is a practice in the fabrication of MLBs to subject the inner layer boards, with their patterns of circuitry, to a so-called brown-oxide treatment, which changes the micro-topography of the top surfaces of the track lines to improve their bondability to the polymeric pre-preg. This brown oxide treatment is typically produced by immersing the boards in an alkaline solution of sodium chlorite, which by its oxidizing action causes the conversion of metallic copper on top surfaces of exposed copper tracks into cupric oxide CuO with a possible admixture of cuprous oxide Cu.sub.2 O, depending on the type of the bath and operation conditions.
This oxide coating grows in the form of dendritic crystals, perpendicular to the surface of the copper tracks. Thus, the surface area available for bonding to polymeric substrates is increased and improved "bondability" is achieved.
We have found that adhesion between the copper surface and the photo-resist is a crucially important component in the subsequent processing of boards having fine line circuitry, because the edge of the photo resist defines the area of copper whereon all subsequent processing will be carried out. This processing can be either the removal of copper by etching or the addition of copper required in so-called through hole plating. If adhesion between the resist and the copper is inadequate then the boundary between the original copper and the etched or plated copper will become irregular so that there is the possibility that variations in the cross sectional area of the circuit path could occur. It therefore becomes clear that any adhesion-promoting roughening of the shiny side of the copper must be carried out by techniques that are controllable within close parameters for optimum utility. This is particularly important as line widths of the circuitry decrease.
Accordingly, we have conducted considerable experimentation with ways of improving such adhesion. As a result of this work, we have developed a novel electrolytic copper foil having its shiny side modified by a micro-roughening deposit which comprises an electrodeposited copper gilding layer, which deposit enables superior wetting by and adhesion to photoresist materials and is unusually well-suited for use in producing copper-clad laminates to be used in the manufacture of circuit boards having fine line circuitry. This modified shiny side foil is sometimes hereinafter referred to as "MSS foil".
An object of the present invention is an electrolytic copper MSS foil having a modified shiny side providing superior adhesion to photoresist materials. Another object of the invention is a copper-clad laminate wherein the matte side of such MSS foil is laminated to a polymeric substrate through a copper bonding treatment electrodeposited on the matte side of the foil. A further object of the invention is an electrical circuit formed on the copper-clad laminate by applying a photoresist material on the modified shiny side of the foil, image patterning and etching to form the circuit.

Electrolytic copper foil having a modified shiny side


Combination therapeutics for the treatment of cancer include the use of immune effector cells, IL-15 based superagonists and one or more immunotherapeutic agents such as Bacillus Calmette-Guerin (BCG).

Urothelial carcinoma is the most common bladder cancer (BC) with an incidence of approximately 90%. At diagnosis two-third of urothelial carcinomas are non-muscle invasive and one-third are muscle invasive. Non-muscle invasive bladder cancer (NMIBC) is characterized by a high risk of recurrence (30-85% depending on stage and grade) after transurethral resection of the bladder tumor (TURBT). Moreover, up to 17% of all NMIBC will eventually progress to muscle invasive bladder cancer (MIBC). Non-muscle invasive bladder cancer (NMIBC) begins and stays in the cells lining the bladder without growing into the deeper main muscle layer of the bladder, and accounts for the majority (70-80%) of patients diagnosed with bladder cancer (stages Ta, T1, or CIS). Approximately 30% of patients present with muscle-invasive disease (stages T2-T4). Bladder cancer has the highest recurrence rate of any malignancy.
A significant limitation of current Bacillus Calmette-Guerin (BCG) treatment is the lack of response in a substantial number of patients. For example, depending on the endpoint studied, up to 50% of patients fail to respond and show progression of the cancer to muscle invasive disease. Additionally, approximately one-third of patients that initially respond to therapy will show tumor recurrence (Sylvester, R. J., Int J Urol., February; 18(2):113-20 (2011)). Patients with recurrence after BCG therapy may present with urothelial carcinoma of the upper urinary tract or the prostatic urethra, which is not accessible to BCG. Also, patients with no measurable pre-existing T-cell immunity to BCG (due to previous BCG immunization or natural exposure to mycobacteria) have a lower recurrence-free survival rate (Biot, C., et al., Sci Transl Med., June 6; 4(137):137ra72 (2012)). Patients with BCG-unresponsive non-muscle-invasive bladder cancer (NMIBC) have limited treatment options and the standard of care for these patients is radical cystectomy.

Bacillus Calmette-Guerin (BCG) and antigen presenting cells for treatment of bladder cancer


Asphaltene may be effectively broken into smaller molecules by first elucidating the structure of the asphaltene and then developing a catalyst system based on the elucidated structure. The structure may be determined based on a series of analytical techniques including NMR, FTIR, Raman spectroscopy, XPS, and LDI. The most probable structure is determined using computational methods based on quantum mechanics and classical molecular dynamics and the catalyst system is developed for the most probable structure.

Heavy crude oil from subterranean hydrocarbon reservoirs typically has four fractions: saturates (saturated hydrocarbons), aromatics, resins and asphaltene macromolecules. The high viscosity of heavy crude oil is due, at least partially, to the presence of the asphaltenes. Asphaltenes are further known to adversely impact the viscoelasticity and flow behavior of crude oil.
Asphaltenes also are known to cause operational and safety issues with both hydrocarbon production and processing. For example, they are known to have deleterious effects on the extraction of oil. For instance, asphaltenes are generally stable in bulk oil at relatively high pressures and tend to precipitate at lower pressure or onset pressure. As reservoir pressure decreases and drops below the onset pressure during hydrocarbon production, asphaltenes precipitate and the precipitates block production routes and tubing.
Asphaltene precipitates are further known to flocculate and form deposits in the pores of the formation, coat boreholes and solidify in downhole equipment. Wells with excessive asphaltene deposition may incur high remediation costs but, more importantly, are exposed to levels of formation damage that can greatly shorten the productive life of the well.
In the past, much effort has been undertaken in order to decrease the viscosity of heavy oil and to increase the flow of hydrocarbons from the well by minimizing the precipitation of asphaltenes. Such efforts have been focused on determining an effective catalyst for breaking the bonds of the asphaltenes. However, catalyst selection has not been totally effective. This is attributable, in part, to the fact that catalyst selection has only been based on the activity, selectivity, ease of regeneration and mechanical strength of the catalyst under defined cracking operations.
Improved methods for decreasing the viscosity of heavy oil and to break down asphaltenes are therefore desired.
It should be understood that the above-described discussion is provided for illustrative purposes only and is not intended to limit the scope or subject matter of the appended claims or those of any related patent application or patent. Thus, none of the appended claims or claims of any related application or patent should be limited by the above discussion or construed to address, include or exclude each or any of the above-cited features or disadvantages merely because of the mention thereof herein.

This patent is subject to a terminal disclaimer.

Viscosity reduction of crude oil through structure determination of asphaltene molecule