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Patent US4405816 - 4,4'-Diphenyl ether-dialdehyde-bis-dimethylacetal - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign in<nobr>Advanced Patent Search</nobr>PatentsDisclosed is the novel compound 4,4'-diphenylether-dialdehyde-bis-dimethylacetyl of the formula ##STR1## and a process for its preparation from di-p-tolyl ether ##STR2## by anodic oxidation of the latter in the presence of methanol and of a supporting electrolyte. The anode material used in this reaction...http://www.google.com/patents/US4405816?utm_source=gb-gplus-sharePatent US4405816 - 4,4'-Diphenyl ether-dialdehyde-bis-dimethylacetalAdvanced Patent SearchPublication numberUS4405816 APublication typeGrantApplication numberUS 06/333,013Publication dateSep 20, 1983Filing dateDec 21, 1981Priority dateDec 24, 1980Fee statusPaidAlso published asCA1184207A1, DE3048992A1, EP0054698A1, EP0054698B1, US4457810Publication number06333013, 333013, US 4405816 A, US 4405816A, US-A-4405816, US4405816 A, US4405816AInventorsDetlef H. SkaletzOriginal AssigneeHoechst AktiengesellschaftExport CitationBiBTeX, EndNote, RefManPatent Citations (2), Non-Patent Citations (4), Referenced by (3), Classifications (11), Legal Events (6) External Links: USPTO, USPTO Assignment, Espacenet4,4'-Diphenyl ether-dialdehyde-bis-dimethylacetalUS 4405816 AAbstract Disclosed is the novel compound 4,4'-diphenylether-dialdehyde-bis-dimethylacetyl of the formula ##STR1## and a process for its preparation from di-p-tolyl ether ##STR2## by anodic oxidation of the latter in the presence of methanol and of a supporting electrolyte. The anode material used in this reaction is preferably platinum, lead dioxide, graphite or vitreous carbon, and the cathode material used is preferably steel, nickel, or graphite. The supporting electrolyte used is preferably NaOCH3, KOH, KPF6, CsF, NaBF4, LiBF4, tetraethylammonium p-toluenesulfonate, H2 SO4 or CH3 OSO3 H, individually or as a mixture.
What is claimed is: 1. 4,4'-Diphenyl ether-dialdehyde-bis-dimethylacetal, having the formula ##STR18##
BACKGROUND OF THE INVENTION The present invention relates to 4,4'-diphenyl ether-dialdehyde-bis-dimethylacetal and to a process for its preparation.
It is known that anodic alkoxylation of unsubstituted or substituted methylbenzenes of the general formula (I) can lead to the corresponding benzaldehyde-dialkylacetals of the general formula (II):
______________________________________ ##STR3## ##STR4##REACTANT  R1         R2 PRODUCT______________________________________I a       H               CH3                             II ab         CH3        CH3                             bc         -- --OCH3  CH3                             c                     C2 H5                              c'      ##STR5##       CH3                             de         -- --OCH2CHCH 2                     CH3                             ef      ##STR6##       CH3                             fg         -- --Ot-C4 H9                     CH3                             gh      ##STR7##       CH3                             h______________________________________
According to the article "Anodic Methoxylation of Alkylbenzenes" by K. Sasaki, H. Urata, K. Uneyama and S. Nagaura in Electrochimica Acta, 1967, Vol. 12, pp. 137-146, toluene (Ia) is converted on platinum electrodes in methanol to benzaldehyde-dimethylacetal (IIa) (or, after hydrolysis, to benzaldehyde itself) and to methyl benzyl ether. According to the data in F. Beck, Elektroorganische Chemie, Verlag Chemie-Weinheim, 1974, page 248, the yield of (IIa) is said to be about 10% of the theoretical.
Published French patent application No. 2,351,932 describes the electrochemical oxidation of methylbenzenes, such as toluene (Ia) and xylene (Ib). The following products are obtained in the oxidation of toluene (Ia) in an electrolyte system composed of methanol and a co-solvent, such as methylene chloride, with the use of acidic supporting electrolytes and after subsequent hydrolysis: methyl benzyl ether, benzaldehyde and p-methoxybenzaldehyde, and in addition also, inter alia, o-methoxy-benzaldehyde or p-methoxytoluene. The yields of benzaldehyde are 3.6 to 13.2% of the theoretical. In the corresponding anodic oxidation of p-xylene (Ib), the reaction products (no yield data are given) are methyl-p-xylyl ether, 4-methyl-benzaldehyde, methyl-4-methyl-benzoate and 2-methoxy-4-methyl-benzaldehyde.
According to the article "Anodic Substitution and Addition Reactions" by S. Tsutsumi and K. Koyama in Discussions of the Faraday Society, 1968, No. 45, pp. 247-253, ring-substituted methoxy derivatives of toluene or of tolunitrile are also obtained in the anodic cyanation of toluene on platinum electrodes in a methanol/NaCN system.
More recently, remarkable increases in the selectivity of the electrochemical alkoxylation of toluenes substituted in the 4-position have also been disclosed.
In the article "Nuclear Cyanation of Methylanisoles" by K. Yoshida, M. Shigi and T. Fueno in J. Org. Chem., 1975, Vol. 40, No. 1, pp. 63-66, the reaction of 4-methoxytoluene (Ic) in a methanolic solution of NaCN or Na acetate is described. In this reaction, 4-(methoxymethyl)-anisole and, in a material (current) yield of 15% (24%) of the theoretical, anisaldehyde-dimethylacetal (IIc) are also formed, in addition to the respective ring-substitution products.
A. Nilsson, U. Palmquist, T. Pettersson and A. Ronlan, "Methoxylation of Methyl-substituted Benzene and Anisole Derivatives, and the Synthesis of Aromatic Aldehydes by Anodic Oxidation" in J. Chem. Soc., Perkin Transactions I, 1978, pp. 708-715, have succeeded in methoxylating p-xylene (Ib) and 4-methoxytoluene (Ic) in methanol with the use of NaOCH3 /LiBF4 or NaOCH3 supporting electrolytes on a carbon anode at about 10� C. to give compound (IIb) in a material (current) yield of 57% of the theoretical and compound (IIc) in a material (current) yield of 66% of the theoretical.
In Published European application No. 0,011,712 (see also German Offenlegungsschrift No. 2,848,397), benzaldehyde-dialkylacetals, substituted in the 4-position, of the general formula ##STR8## are described, wherein R1, inter alia, can also represent a phenyl radical or benzyl radical and R2 can represent an alkyl radical having 1 to 4 C atoms. These compounds are prepared by electrochemically oxidizing methylbenzenes (toluenes), substituted in the 4-position, of the general formula ##STR9## in the presence of an alcohol R2 --O--H (R1 and R2 having the meaning indicated above) and of a supporting salt. Examples of suitable supporting salts are: fluorides such as KF, tetrafluoborates such as Et4 NBF4 (where Et=ethyl), perchlorates such as Et4 NClO4, sulfates such as Et4 NSO4 Et, alcoholates such as NaOCH3 and hydroxides such as KOH. The quantitative proportions of the components should be between about 5 and 50% by weight of the substituted methylbenzenes, between about 50 and 95% by weight of the alcohol and between about 0.5 and 15% by weight of the supporting salt. Graphite, graphite-filled plastics and noble metals are mentioned as the anode materials, and graphite, iron, steel, lead and noble metals are mentioned as the cathode materials. The current densities are from 1 to 20 A/dm2, and the electrolysis temperature is between about 0� and 60� C. In detail, the anodic methoxylation or ethoxylation, respectively, of p-xylene (Ib) gives a material yield (current yield) of 32% (18%) of the theoretical of 4-methyl-benzaldehyde-dimethylacetal (IIb), that of 4-methoxytoluene (Ic) gives 42.4% (22%) to 73.1% (56.5%) of anisaldehyde-dimethylacetal (IIc) or 53.4% (-) of anisaldehyde-diethylacetal (IIc'), that of 4-benzyloxytoluene (Id) gives 62.1% (47.9%) of 4-benzyloxy-benzaldehyde-dimethylacetal (IId), that of 4-allyloxytoluene (Ie) gives 36.3% (10.8%) of 4-allyloxy-benzaldehyde-dimethylacetal (IIe), that of 4-phenoxy toluene (If) gives 39.2% (14.3%) of 4-phenoxy-benzaldehyde-dimethylacetal (IIf), that of 4-t-butoxytoluene (Ig) gives 52.5% (19.2%) of 4-t-butoxy-benzaldehyde-dimethylacetal (IIg) and that of 4-N,N-dimethylamino-carboxyl-toluene gives 40.4% (-) of 4-(N,N-dimethylamino-carboxyl)-benzaldehyde-dimethylacetal.
In the process for the preparation of substituted benzaldehyde-dialkylacetals according to Published European application No. 0,012,240, inter alia, methylbenzenes (toluenes), substituted in the 4-position, of the general formula ##STR10## in which R1 can, inter alia, represent an aryloxy or aralkoxy radical, are electrochemically oxidized in solution in an alcohol of the formula R2 --O--H (R2 =alkyl) and in the presence of a supporting salt at a current density of 0.1 to 50 A/dm2. The aryloxy and aralkoxy radicals mentioned are, inter alia, phenoxy, naphthyloxy, anthryloxy, benzyloxy and 2-phenyl-ethoxy, according to which p-phenoxytoluene (=1-methyl-4-phenoxy-benzene) should then, inter alia, also be included with the methylbenzenes substituted in the 4-position. Suitable supporting salts include tetraethylammonium-p-toluene-sulfonate, tetraethylammonium-ethyl-sulfate or tetramethylammonium dimethyl phosphate. Graphite, lead dioxide and noble metals are mentioned as anode materials, and copper, nickel, steel, platinum and graphite are mentioned as cathode materials. In detail, the anodic methoxylation of p-xylene (Ib) gives a material yield (current yield) of 64% (-) of 4-methylbenzaldehyde-dimethylacetal (IIb), that of 4-methoxytoluene (Ic) gives 67% (71%) to 95% (-) of 4-methoxybenzaldehyde-dimethylacetal and that of 4-t-butoxytoluene (Ig) gives 55% (-) to 92% (-) of 4-t-butoxybenzaldehyde-dimethylacetal (IIg).
None of these numerous publications, however, contains even the slightest hint to the effect that it would be possible to alkoxylate aromatic compounds which have 2 methyl groups located on an aromatic system in the molecule, to simultaneously alkoxylate both methyl groups to give the corresponding aromatic dialdehyde-bis-dialkylacetals. Thus, for example, as described by A. Nilsson et al. (cited above), the anodic oxidation of p-xylene (Ib), depending on the experimental conditions (page 709, bottom of right-hand column) either leads via a nuclear methoxylation to 1-methyl-1-methoxy-4-methyl-4-methoxy-cyclohexa-2,5-diene (III) or leads via a side-chain methoxylation to (4-methyl-benzyl)-methyl-ether (IV), to 4-methylbenzaldehyde-dimethylacetal (IIb) or, in the last oxidation stage, to the ortho-ester of p-toluic acid (V): ##STR11##
The even more recent publications (German Offenlegungsschrift No. 2,848,397, European application No. 0,011,712 or European application No. 0,012,240) likewise do not contain any hint to the effect that, in the anodic methoxylation of, e.g., p-xylene (Ib), even traces of terephthaldialdehyde-bis-dimethylacetal (VI) ##STR12## could be formed. Even with the most sensitive analytical methods, such as a combination of gas chromatography and mass spectroscopy according to Published French application No. 2,351,932, it was not possible to detect either the dialdehyde or the corresponding bis-dimethylacetal in this reaction.
These findings coincide with the results in an article "Anodic Oxidation of Arylcyclopropanes" by T. Shono and Y. Matsumura in J. Org. Chem., 1970, Vol. 35, No. 12, pp. 4157-4160, according to which either an α-methoxylation to give 2-(p-tolyl)-2-methoxypropane, or the secondary product p-isopropenyl-toluene obtained therefrom, or an α'-methoxylation to give (p-i-propyl-benzyl)-methyl-ether takes place in the anodic methoxylation of 4-i-propyltoluene. Accordingly, once a methoxy group has entered into the α-position, a possible subsequent α'-substitution in the same molecule is completely inhibited.
SUMMARY OF THE INVENTION It is the therefore an object of the present invention to provide a process for the preparation of bis-dimethylacetals.
It is also an object of the invention to produce a symmetrical bis-dimethylacetal, namely, 4,4'-diphenyl ether-dialdehyde-bis-dimethylacetal, by an anodic methoxylation reaction.
In accomplishing the foregoing objects, there has been provided in accordance with the present invention a new compound, 4,4'-diphenyl ether-dialdehyde-bis-dimethylacetal, having the formula ##STR13##
In accordance with another aspect of the invention, there has been provided a process for the preparation of the foregoing compound which comprises the step of anodically oxidizing di-p-tolyl ether of the formula ##STR14## in the presence of methanol and a supporting electrolyte. Preferably, the supporting electrolyte comprises NaOCH3, KOH, KPF6, CsF, NaBF4, LiBF4, tetraethylammonium p-toluenesulfonate, H2 SO4, CH3 OSO3 H, or a mixture thereof. Most preferably, the supporting electrolyte is a type such that, after the electrolysis has ended, it can be converted into a compound which is insoluble or does not dissociate in methanol.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS The invention relates to the new compound 4,4'-diphenyl ether-dialdehyde-bis-dimethylacetal (VII) ##STR15##
This compound is prepared by anodically oxidizing di-p-tolyl ether (VIII) in the presence of methanol and of a conducting electrolyte. The reaction can be represented as follows: ##STR16##
For the first time in a surprising manner, contrary to the previous findings and expectations, this enables an aromatic compound having 2 methyl groups located on an aromatic system to be anodically methoxylated on both sides, that is partially and at the same time symmetrically, in such a way that the compound (VII) is obtained as the reaction product. The process for the preparation of this compound (VII) represents a modification of the process described by A. Nilsson et al. (cited above).
The process according to the invention can be carried out in the known pressure cells or flow cells of undivided construction, optionally with stirring or with pumped circulation of the electrolyte. The flow velocity of the electrolyte is of rather subordinate importance and can be varied between about 5 cm/second and 10 m/second without significantly impairing the reaction. The anode materials used are the materials customary in organic electrochemistry, such as platinum, lead dioxide, graphite or vitreous carbon. Metal-free anodes are preferred. The cathode materials used are the customary solids, such as steel, nickel or graphite, and materials having a low cathodic hydrogen overvoltage are preferred. The form of the anodes and cathodes is of minor importance and, for example, plates, rods, spheres or even structured shapes can be used.
The anode current densities can be varied within the range from about 5 mA/cm2 (0.5 A/dm2) up to about 500 mA/cm2 (50 A/dm2), and the range between about 50 and 200 mA/cm2, in particular, a range between about 50 and 100 mA/cm2, is preferred.
The supporting electrolytes which can be used for the process according to the invention are those customary in organic electrochemistry. These include, in particular, NaOCH3, KOH, KPF6, CsF, NaBF4, LiBF4, tetraethylammonium p-toluenesulfonate, H2 SO4 or CH3 OSO3 H. Perchlorates, such as, for example, LiClO4, are unsuitable in practice. The supporting electrolytes can be used either individually or as a mixture. Those supporting electrolytes are preferred in the process according to the invention which, after the electrolysis has ended, can be converted into an insoluble or non-dissociating compound by the addition of a suitable auxiliary substance which is as anhydrous as possible. For example, supporting electrolytes, such as H2 SO4 or NaOCH3, can be converted into such an "inactive" compound with stoichiometric quantities of NaOCH3 or H2 SO4, respectively. This possibility of "inactivating" the supporting electrolyte is especially important whenever, after the electrolysis has ended, the reaction mixture containing the bis-dimethylacetal as an intermediate is to be directly processed further to give end products which are to be modified chemically. In this case, additional working-up stages can then be omitted. This process variant is particularly advantageous in the homogeneous hydrogenation, described below, as a possibility for direct further processing of the bis-dimethylacetal. The concentration of the supporting electrolyte or electrolytes is advantageously within the range of from about 0.01 to 20% by weight, preferably from about 0.05 to 5% by weight, relative to the total electrolyte.
The reactant in the process according to the invention, namely di-p-tolyl ether, can be present in the electrolyte in a concentration of from about 1 to 40% by weight, relative to the total electrolyte. The solvent used for the process according to the invention is methanol in the anhydrous form, or alternatively, a technical grade having a small water content of, for example, about 0.2 to 0.3% by weight. The electrolysis temperature can vary within wide limits, and in general it should be between about 10� C. and 65� C., that is to say approximately between room temperature and the boiling point of the electrolyte mixture.
The reaction batch can be worked up by one of the conventional procedures, for example, by distillation or filtration. Preferably, however, it should be carried out with exclusion of moisture, so that the bis-dimethylacetal formed according to the invention is not hydrolyzed to the bis-aldehyde. The supporting electrolytes and solvents, which are obtained by such working-up of the reaction batch and are thus recoverable, can be re-used in subsequent batches not only without problems, but with particular advantage. In one variant of the process according to the invention, as already described above, the supporting electrolytes are converted into "inactive compounds" so that the reaction mixture can be directly processed further to give further products.
In the process according to the invention, in particular at a current conversion of about 8 to 12 Faradays/mole, almost exclusively 4,4'-diphenyl etherdialdehyde-bis-dimethylacetal is obtained from the di-p-tolyl ether. By contrast, at a current conversion of about 4 Faradays/mole, only a very inhomogeneous product mixture of 6 compounds, namely, unconverted di-p-tolyl ether and the side-chain substitution products monomethoxy-, symmetrical dimethoxy-, asymmetrical dimethoxy-, trimethoxy- and tetramethoxy-di-p-tolyl ether, is obtained.
The process according to the invention, by producing a high degree of upgrading, opens up a new route to an industrially important compound, namely 4,4'-bis-methoxy-methyl-diphenyl ether (IX). ##STR17## This compound is of importance, in particular, in the preparation of aromatic polyethers from hydroxymethyl-diaryl ethers or alkoxymethyl-diaryl ethers. (See, for example, German Pat. No. 1,252,903 or U.S. Pat. No. 3,316,186.) These aromatic polyethers are suitable as a binder in the preparation of casting compositions or as an adhesive in the production of laminates. Another known use of the compound (IX) is its reaction, described in German Offenlegungsschrift No. 2,065,732 (=U.S. Pat. No. 3,867,147) with aromatic diazonium compounds to give light-sensitive condensation products from these two components. The preparation of (IX) by homogeneous catalytic hydrogenolysis of 4,4'-diphenyl ether-dialdehyde-dimethylacetal, the compound according to the invention, in methanol in the presence of a soluble cobalt carbonyl catalyst modified with organic nitrogen bases is described in detail in German patent application No. P30 48 993.1, corresponding to U.S. application Ser. No. 333,012, filed concurrently herewith, with the title "Process for the Catalytic Hydrogenolysis of p-Substituted Benzaldehyde-dimethylacetals to Produce the Corresponding Benzyl Methyl Ether Derivatives.
In the examples which follow, unless stated otherwise, % data are by weight. Parts by weight have the same relationship to parts by volume as the kg to the dm3.
EXAMPLE 1 The electrolytic cell used is an undivided flow cell of polyethylene with minimized electrode spacing, wherein the geometrical cathode and anode areas are 0.1 m2, the electrode separation is 1 mm and the flow velocity of the electrolyte is 0.8 m/second. Devices for keeping the temperature constant, for taking samples, or the like, are located in the electrolyte circulation outside the cell. Commercially available apparatus grade graphite impregnated with synthetic resin (Diabon-N from Sigri Elektrographit GmbH, Meitingen) is used as the anode, and a commercially available electrolysis graphite (EH type from the same manufacturer) is used as the cathode. The electrolyte is composed of 4,040 parts by weight (5,100 parts by volume) of technical grade methanol, 29.2 parts by weight of incompletely dissolved NaBF4 and 595 parts by weight of di-p-tolyl ether. The molar ratios are 0.266 mole of conducting salt per 3 moles of reactant. The other reaction conditions are: a temperature of 45� C., a current density of 50 mA/cm2, a cell current of 50 A, a cell voltage of 7.3 to 7.7 V and a current conversion of 9.2 Faradays/mole corresponding to 740 ampere-hours (=115%).
After the reaction has ended, the methanol is distilled off, with exclusion of moisture, over a packed column (main fraction under normal pressure, and the remainder in a vacuum of about 20 to 40 mm Hg), the distillation residue is stirred with 2,000 parts by volume of dry diethyl ether, and the precipitated conducting salt is filtered off with suction. After the residue is washed with dry diethyl ether and is dried, 27.6 g (=94.5% of the theoretical) of the conducting salt are recovered. The diethyl ether is removed from the reaction product by distillation, and 829.3 g of distillable constituents are separated off from 65.2 g of non-volatile, resinous constituents in a thin-layer evaporator (oil circulation temperature 250� C., oil pump vacuum 0.01 to 0.2 mm Hg).
The gas-chromatographic analysis (GC) of the distillate [10% strength in methanol, 1.5 m of Silikon OV 225: 25% of phenyl, 25% of cyanopropyl, methyl on 80 to 100 mesh Chromosorb G AW DMS (manufacturer: John Manville Products), 60 ml of He/minute, 80� C. start, 8�/minute] shows 90.4 area-% of compound (VIII), namely 4,4'-diphenyl ether-dialdehyde-bis-dimethylacetal. In addition to the mass spectrum (molecular mass 318), the elementary analysis
found: C, 67.4%; H, 6.8%; O, 24.4%.
calculated: C, 68.1%; H, 6.7%; O, 25.2%
and the highly symmetrical 1 H-NMR spectrum (60 Mhz in CDCl3) with
C--H (acetal) 12 H, S, 3.3 ppm,
C--H (aldehyde) 2 H, S, 5.32 ppm and
C--H (aromatic, 1,4-disubstituted) 8 H, AA'BB' system, 7.2 ppm
prove the presence of the bis-dimethylacetal according to the invention.
EXAMPLE 2 The electrolytic cell used is an undivided flow cell of polyethylene with a minimized electrode separation. The cell contains 1 VA steel end cathode, 1 end anode of vitreous carbon (Sigradur K) and 4 bipolar center electrodes of vitreous carbon/VA steel (manufacturer of the commercially available electrodes: Sigri Elektrodengraphit GmbH, Meitingen). The electrode separation is defined by 1 mm thick polyethylene grids, the anode and cathode areas are each 5�255 cm2, i.e., a total of 1,275 cm2 each, and the flow velocity is set to 0.8 m/second. Devices for keeping the temperature constant, for taking samples, and the like, are located in the electrolyte circulation outside the cell. The electrolyte is composed of 12,750 parts by volume of technical grade methanol, 30 parts by volume of concentrated H2 SO4 and 595 parts by weight of di-p-tolyl ether. The other reaction conditions are: a temperature of 18� C., a current density of 100 mA/cm2, a cell current of 25.5 A, a cell voltage of 34 to 38 V and a current conversion of 10.6 Faradays/mole corresponding to 852 ampere-hours (=132%).
After the reaction has ended, the conducting electrolyte is neutralized with 61 parts by weight of NaOCH3 (in methanol solution) and the electrolyte is worked up in accordance with the instructions of Example 1 and analyzed by gas chromatography, according to which the high-boiling compounds, which can be separated off, contain 89.7% of compound (VII).
After clarification by filtration, the neutralized electrolyte, without the working-up indicated in Example 1, can be successfully processed further directly, for example, in the homogeneous catalytic hydrogenolysis reaction described in the above-mentioned U.S. patent application Ser. No. 333,012, filed concurrently herewith.
Patent CitationsCited PatentFiling datePublication dateApplicantTitleUS4284825 *Oct 31, 1979Aug 18, 1981Basf AktiengesellschaftIntermediates for perfumes, crop protection agentsUS4318783 *Nov 14, 1979Mar 9, 1982Bayer AktiengesellschaftElectrolytic oxidation of an alcohol-dissolved toluene using an electroconductive ammonium salt* Cited by examinerNon-Patent CitationsReference1 *A. Nilsson, Ulf Palmquist, T. Pettersson, A. Ronlan; "Anodic Functionalisation in Synthesis, Part 1 . . . ," Journal of the Chemical Society, pp. 708-715.2 *K. Sasaki and H. Urata, "Anodic Methoxylation of Alkylbenzenes," Electrochimica Acta, 1967, vol. 12, pp. 137-146.3 *K. Yoshida, Shigi, and T. Fueno, "Anodic Oxidations, VII, Nuclear Cyanation of Methylanisoles," J. Org. Chem. vol. 40, No. 1, 1975, pp. 63-66.4 *S. Tsutsumi and Kikyhiko Koyama, "Anodic Substitution and Addition Reactions," The Electrode Reactions of Organic Compounds, pp. 247-253.* Cited by examinerReferenced byCiting PatentFiling datePublication dateApplicantTitleUS4871430 *Feb 19, 1987Oct 3, 1989The Dow Chemical CompanyUsing nitriles, ketones, acids, or estersUS5168326 *Jul 25, 1991Dec 1, 1992Showa Denko K.K.Method of detecting angle of optical rotation in solution having time-dependent concentration, detection apparatus therefor, and detector cell thereforUS5393876 *Apr 9, 1993Feb 28, 1995Wako Pure Chemical Industries, Ltd.Process for producing maltooligosaccharide derivatives* Cited by examinerClassifications U.S. Classification568/592, 205/456International ClassificationC07C43/315, C07C41/00, C25B3/02, C25B3/10, C07C67/00Cooperative ClassificationC07C43/315, C25B3/02European ClassificationC07C43/315, C25B3/02Legal EventsDateCodeEventDescriptionOct 13, 1999ASAssignmentOwner name: CLARIANT GMBH, GERMANYFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:HOECHST AKTIENGESELLSCHAFE;REEL/FRAME:010299/0415Effective date: 19990602Owner name: CLARIANT GMBH BRUENINGSTRASSE 50 FRANKFURT AM MAINApr 25, 1995REMIMaintenance fee reminder mailedFeb 27, 1995FPAYFee paymentYear of fee payment: 12Feb 19, 1991FPAYFee paymentYear of fee payment: 8Feb 20, 1987FPAYFee paymentYear of fee payment: 4May 26, 1983ASAssignmentOwner name: HOECHST AKTIENGESELLSCHAFT FRANKFURT/MAIN, GERMANYFree format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:SKALETZ, DETLEF H.;REEL/FRAME:004129/0599Effective date: 19811203Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:SKALETZ, DETLEF H.;REEL/FRAME:004129/0599Owner name: HOECHST AKTIENGESELLSCHAFT, GERMANYRotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services©2012 Google