Indian Patents. 253466:A DENDRITIC COMPOUND

Title of Invention	A DENDRITIC COMPOUND
Abstract	A dendritic compound, wherein it comprises a core, a branch structure composed of Unit 1 represented by the following structure, and surface functional groups.

Full Text	SPECIFICATION Novel Thioether Derivatives, Their Method for Production and Use BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to novel thioether derivatives, the production method and use thereof, and relates especially to the S containing dendrimers and the synthetic intermediates thereof. The thioether derivatives and their intermediates of the present invention have industrial and pharmaceutical applications. 2. Description of the Prior Art The dendritic molecules, having a unique macromolecular structure, are expected to have a wide field of application. The dendritic molecules which have a unique chemical structure composed of a central core (nucleus), and a branch structure constructed with branches (units) repeated regularly and the surface functional groups, both extending three-dimensionally, have been investigated actively in the field, for example, of nano science, communication science, electro-material science, medical science, pharmaceutical science, biological science, surface science and material science, and so on (References: "Dendritic Molecules", VCH Publication Co. 1996; "Molecular Design of Dendrimers" and "Miscellaneous Functions of Dendrimers" Gendai Kagaku, June, 1998, on pp. 20-40; "Applications of Dendrimers as Non-linear Optical Materials" in Kobunshi, Vol.47, November, 1998.) It may safely be said, however, that the dendrimer science is "one of the latest sciences", because it has been highlighted only since about the middle of the year 1990 and the number of the research on it has increased recently. As for the use of the dendritic molecules, there have been offered a variety of inventions on the subject of industrial use thereof, for example, their use in medicine and agricultural chemicals (JP-A Hei7-330631), use in solar cell and photosensitive material for electrophotography (JP-A Heill-40871), use in electronic material (JP-A Heill-171812), use in liquid crystal (JP-A 2000-264965), use in paint and ink (JP-A Heill-14018O), use in fluorescent resin sheet ( JP-A Heill-323324), use in qualitative and quantitative analyses (JP-A Heill-218494), use in biological response modifier (JP-C Hei8-510761), and so on. SUMMARY OF THE INVENTION The object of the present invention is to provide both novel dendritic molecules with useful functions and novel synthetic intermediates for producing them. More specifically, the main object of the present invention is to provide novel dendrimers which are useful as electronic material (for example, as the switch of memory) due to their ability to emit light from the core by transferring electron which exists in the branch structure into the core which has been made electron deficient by absorbing light or electric energy. Other objects of the present invention will become clear through the explanation hereinafter. The present inventors made an intensive investigation on the aforementioned problems and succeeded in creating the S atom containing dendrimers of the present invention. In addition, the present inventors have obtained a lot of novel knowledge about the dendrimers of the present invention which have many sulfur atom in their branch structures. Namely, in the case of the sulfur atom we can make use of their d-orbital electrons which do not exist in the oxygen atom. As the d-orbital electrons of the sulfur atom are placed farther apart from the nuclei than the p-orbital electrons of the oxygen atom, the electrons of the sulfur atom can move more freely than the electrons of the oxygen atom; the light or electric energy can be transferred to the core, which is in an electron-deficient state, with ease; it becomes possible to make the core emit light by constructing the core from a residue of a luminescent compound; and a larger polarization between the branch structure and the core can be obtained with the sulfur atoms than with the oxygen atoms. Consequently, the present inventors have got the knowledge that the dendrimers of the present invention are useful as an electronic material, for example, as the switch of memory. In addition, the present inventors have found that, although S atom-containing dendrimers can suffer deterioration due to oxidation, it is possible to make them more durable and of a long life by placing substituents with steric bulkiness, preferably t-butyl groups, on the outside of the branch structure, namely, at the opposite end across the branch structure from the core. Furthermore, the present inventors have found that the S atom-containing dendrimers of the present invention can be produced conveniently and industrially advantageously from a series of novel synthetic intermediates of specific structures. Based on a lot of novel knowledge mentionedabove, the present inventors have carried out an intensive investigation on the subject and completed the present invention. That is to say, the present invention relates to the compounds and salts thereof: comprises or preferably [1] A dendritic molecule characterized in that it/has a core, a branch structure composed of Unit 1 represented by the following structure, , wherein ring A stands for a homo- or heterocyclic six-membered ring, and surface functional groups as the essential constituents. comprises or preferably [2] A dendritic molecule characterized in that it/has a core, a branch structure composed of both Unit 1 described in [1] and Unit 2 represented by the following structure, wherein ring A stands for a homo- or heterocyclic six-membered ring, and/or Unit 3 represented by the following structure. wherein ring A stands for a homo- or heterocyclic six-membered ring, and the surface functional groups. [3} A dendritic molecule characterized in that it comprises or preferably has a core, a branch structure composed of two or more of the partial branch structures of Unit 1 described in [1], Unit 2 described in [2], and Unit 3 in [2], and the surface functional groups. [ 4 ] A dendritic molecule of any of [ 1 ] and [ 2 ], wherein the branch structure is of 2-10 generations and is constructed with both a generation or generations of the branch structure composed of Unit 1 described in [1] and a generation or generations of the branch structure Unit 2 described in [2] and/or Unit 3 described in [2]. [5] A dendritic molecule of [1] to [4], wherein the ring A of Unit 1, Unit 2 and Unit 3 is a benzene ring, a pyrimidine ring or a triazine ring. [ 6 ] A dendritic molecule of [ 1 ] to [ 5 ], wherein the surface functional group is an alkyl group which may be substituted, an aralkyl group which may be substituted, an alkoxy group, an alkoxycarbonyl group or a quaternary ammonium group. [ 7 ] A dendritic molecule of [ 6 ], wherein the surface functional group is a t-butyl group. [8] A dendritic molecule of [1] to [7], wherein the core is a color developing functional group. [ 9 ] A dendritic molecule of [ 1 ] to [ 7 ], wherein the core is a rhodamine pigment, a quinazoline, a perylene, an azo-compound, 2,5-dihydroxybenzoic acid methyl ester, a porphyrin, 4,4'-dihydroxybiphenyl or 1-(4.4', 4 " -trihydroxyphenyl)ethane residue. [10] A thio-compound represented by the following structure, / wherein ring A is a ring represented by Formula 5, which has each of the substituent B, substituent C and substituent D at the positions denoted with a bond, and may be substituted at the positions where no bond is attached; substituent B stands for -S(O)nR1, wherein n stands for an integer of 0-2, and R1 stands for a substituent; substituent C stands for -X1R2, , wherein X1 stands for a intervening group, and R2 stands for a substituent; and substituent D stands for a substituent bonded to the ring A through a carbon atom. [11] A thio-compound of [10], wherein R1 and R2 are, each being the same or different, an alkali metal, a hydrogen atom, an alkyl group which may be substituted, an aralkyl group, a carbamoyl group or a thiocarbamoyl group. [12] A thio-compound of [10] or [11], wherein X1 is a methylene group, a dimethylmethylene group, an oxygen atom, a sulfur atom, a sulfinyl group or a sulfonyl group. [13] A thio-compound of any one of [10] to [12], wherein the subtituent D is a cyano group, a formyl group or X2R3, wherein X2 stands for a methylene group which may be substituted, a carbonyl group or a thiocarbonyl group, and R3 stands for a hydroxyl group which may be protected, a mercapto group or an amino group, with the proviso that when X2 is a carbonyl group, then R3 is not a hydroxyl. [14] 3,5-dimercaptobenzyl alcohol. [15] 3,5-dimercaptobenzyl mercaptan. [16] A compound represented by the following structure and a salt thereof, wherein each of R1 and R2 stands for (1) an alkali metal such as sodium and potassium and so on, (2) a hydrogen atom, (3) an alkyl group which may be substituted with a fluorine atom, a chlorine atom, a bromine atom, an alkcoxy group or a thloalkoxy group, and so on, (4) a phenyl group which may be substituted with the aforementioned substituent or substituents,, or (5) an aralkyl group which may be substituted with the aforementioned substituent or substituents, (6) a disubstituted carbamoyl or thlocarbamoyl group represented by the following structure. , wherein R7 stands for (1) an alkyl group which may be substituted with a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, (2) a phenyl group which may be substituted with aforementioned substituent or substituents, or (3) an aralkyl group which may be substituted with aforementioned substituent or substituents, Z stands for an oxygen atom or a sulfur atom, n stands for an integer of 0 to 2, X stands for a methylene group, a dimethylmethylene group, an oxygen atom, a sulfur atom, a sulfinyl group or a sulfonyl group, Each of R3 and R4 stands for (1) a hydrogen atom, (2) an alkyl group which may be substituted with a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, and so on, (3) a phenyl group which may be substituted with aforementioned substituent or substituents, or (4) an aralkyl group which may be substituted with aforementioned substituent or substituents, or R3 and R4 may be combined to form a methylene group, a keto group or a thioketo group, or R3, R4 and R5 taken together with the carbon atom to which they are attached may form a cyano group, R5 stands for (1) a hydroxyl group, (2) a mercapto group, (3) an amino group, (4) a f ormyl group, (5) an alkyl group which may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and so on, (6) an alkoxy group which may be substituted with aforementioned substituent or substituents, (7) a thioalkoxy group which may be substituted with aforementioned substituent or substituents, (8) a phenyl group which may be substituted with aforementioned substituent or substituents, (9) an aralkyl group which may be substituted with aforementioned substituent or substituents, R6 means a hydroxyl group, an alkyl group, an alkoxy group, an alkylthio group, a nitro group, a cyano group, a dimethylamino group, or a diethylammino group. BRIEF DISCRIPTION OF THE DRAWINGS Fig. 1 shows a schematic diagram of the layer structure of a single electron tunneling device of the present invention. Fig. 2 shows the plan of a single electron tunneling device of an embodiment according to the present invention. Fig. 3 is a vertical cross-sectional view taken on line X-Y of Fig. 2. Fig. 4 is a diagram of the junction part of the device. Fig. 5 is a graph showing the I-V (current to voltage) characteristic of a single electron tunneling device according to the present invention, which is measured at 5.2K. Explanation of reference letters or numerals: 1 substrate layer 2 lower electrode 3 lower polylmide LB film layer 4 intermediary electrode layer 5 upper polylmide LB film layer 6 upper electrode 7 reserve upper layer 8 edge-covering layer 9 electron tunneling layer 10 single electron tunneling device 17 step voltage 18 ammeter DETAILED DESCRIPTION OF THE INVENTION In the present invention, as the examples of the homo- or heterocyclic six-membered ring, there can specifically be mentioned a benzen ring, a pyridine ring, a triazine ring, diazine rings (for example, apyridazine ring, a pyrimidine ring, a pyrazine ring), and so on. As the surface functional group, there can specifically be mentioned a t-butyl group, CONH(CH2)2N+(CH3)3, and alkoxy groups including the methoxy group, and so on, the t-butyl group, however, being the most preferred one in the present invention. As the alkyl groups, there can be mentioned those, which may be straight or branched, of, favorably, the carbon number of C1-4, exemplified specifically by methyl, ethyl, n-propyl, isopropyl and t-butyl, and so on. As the aralkyl groups, there can be mentioned benzyl and phenethyl, and so on. As the alkoxy groups, there can be mentioned those, which may be straight or branched, of, favorably, the carbon number of C1-4, exemplified specifically by a methoxy group, an ethoxy group, an i-propoxy group and a t-butoxy group, and so on. As the color developing functional groups, those groups, which may be known per se and can be derived, specifically, from rhodamine pigments, quinazoline, perylene, and azo-compounds, 2,5-dihydroxybenzoic acid methyl ester, porphyrins, 4,4'-dihydroxybiphenyl or 1-(4.4',4"-trihydroxyphenyl)ethane, are favorably used. Although those synthetic intermediates mentioned in [10] to [14] are novel compounds, they can be manufactured with ease according to the methods known per se, as exemplified hereunder. EXAMPLES Next, by using the synthetic intermediates obtained above, the dendrimers of the present invention are produced. In the production, either of the two procedures, known per se: a divergent synthetic method, in which the central core inside, the branch structure outside, and the outermost surface functional groups are constructed successively in this order, or a convergent synthetic method, in which the outermost surface functional groups, the branch structure inside and the core at center are constructed successively in this order. Thus, both the compounds and dendrimers of the present invention shown hereunder can be produced. By repeating the procedure mentioned above, a dendrimer of higher generation shown hereunder can be produced. The invention is illustrated in more detail by reference to the following examples.However the present embodiments are to be considered in all respects as illustrative and not restrictive. Hereunder, the reactions related to the following examples are illustrated in reaction schemes, wherein Ex. means example. By the same method, following compounds are produced. The following is a specific explanation of the use of the compounds of the present invention referring to an illustration. Fig. 1 shows a schematic diagram of the layer structure of a single electron tunneling device of the present invention. In the present invention, a single-electron tunneling device is constructed by depositing on a substrate layers 1 of a lower electrode 2, a lower polylmide LB film layer 3, an intermediary electrode layer 4, an upper polylmide LB film layer 5, and an upper electrode 6 layer by layer. As the material used for the substrate, various materials which are in general use as the substrate of electronic component, such as metals, glasses, chinaware, ceramics and plastics, and so on, can be used without any particular restriction, and as the material for the lower electrode 2 and upper electrode 6, there can be used thin films of metals such as gold, silver and copper, and so on. On the lower electrode 2, the lower polylmide LB film layer 3 is deposited. In the present invention, the term "polylmide LB film" means either a monomolecular film of polylmide or a built-up film thereof, made by the Langmuir-Blodgett technique. In the single electron tunneling device of the present invention, the polylmide LB film layer 3 can be constructed by laminating 13 to 30 monomolecular films. As the polylmide consisting polylmide LB films, polylmide of a variety of structures can be used. Among them, those which has the repeating structural unit represented by Formula 25 are preferably used, because with them, it becomes possible to control the thickness of the monomolecular film to be prepared. Here, in the preparation of the polylmide LB film layer 3, it is preferable to prepare the layer by first depositing the precursor polyamidic acid monomolecular films and then by performing imidation by means of appropriate chemical processes. Next, the intermediary electrode layer 4, a monomolecular polylmide LB film layer in which the dendritic molecules of the present invention are incorporated, is formed on the polylmide LB film layer 3. In this case, it is necessary to get the polylmide LB film containing an adequate concentration (0.01 to 1%) of the dendritic molecule of the present invention, in order to make the dendritic molecule function as an intermediary electrode. On the intermediary electrode layer 4, the upper polylmide LB film layer 5 is formed in a manner similar to the formation of the lower polylmide layer 3. This polylmide LB film layer 5 is constructed by depositing 20 to 30 layers of polylmide unimolecular films. By depositing the upper electrode 6 on this upper polylmide LB film layer 5, a single electron tunneling device of the present invention is prepared. Thus, in this single electron tunneling device obtained, all the three layers which construct the electron tunneling layer, namely, the lower polylmide LB film layer 3, upper polylmide LB film layer 5 and the intermediary electrode layer 4, are composed of organic molecular material made of polylmide LB films, which makes it possible for the device to express a good single electron tunneling conductivity characteristic. EXAMPLE 1 Production of Methyl 3,5-dimethylthiobenzoate. Methyl 3,5-bis(dlmethylcarbamoylthio)benzoate (20g) was dissolved in 500ml of methanol with heating. To this, sodium methoxide (30g) was added in an atmosphere of nitrogen. After completion of the addition, the resulting mixture was then heated for one hour under reflux and cooled a little. To this, an excess amount of methyl iodide was added, and the resulting mixture was heated for three hours under reflux and then concentrated under reduced pressure. The residue thus obtained was purified by means of chromatography with chloroform, giving the objective compound. The yleld was 10.5g (79.3%). The melting point is 46oC. 1H-NMR( δ ppm, CDC13, TMS): 2.5(6H,s), 3.9(3H,s), 7.2(lH,s), 7.6(2H,s). EXAMPLE 2 Production of 3,5-Dimethylthiobenzyl Bromide via 3,5-Dlmethylthiobenzyl Alcohol In an atmosphere of nitrogen, sodium dihydrobis(2-methoxyethoxy)aluminate (70% in toluene, 50g, 0.17mol) was dissolved into dry tetrahydrofuran. To this, a solution of 22.8g of 3,5-dimethylthiobenzoate in 100ml tetrahydrofuran was added dropwise at 5 to 10oC , and the mixture obtained was stirred at the same temperatures for 6 hours. Then, the reaction mixture was added to a mixture of 50ml of concentrated hydrochloric acid and 1L of ice-water, followed by extraction with chloroform. The extract was purified by means of chromatography using chloroform as the developing solvent. The eluate was then evaporated to dryness under reduced pressure and the residue obtained was washed with petroleum ether, giving 3,5 - dimethylthiobenzyl bromide. The yleld was 21.6g (82%). The melting point is 76-77°C. EXAMPLE 3 Production of 3,5-Bis(3,5-dimethylthiobenzyloxy)benzyl Alcohol via Methyl 3,5-Bis-(3,5-dimethylthiobenzyloxy)benzoate 3,5-Dimethylthiobenzyl bromide (20.Og, 0.080mol), methyl 3,5-dihydroxybenzoate (6.7g, 0.040mol), potassium carbonate (28.Og, 0.20mol) and of 18-crown-6 (2.1 g, 0.0080 mol) were added to 500ml of dry acetone, and the resulting mixture was heated for 15 hours under reflux in an atmosphere of nitrogen. The reaction mixture was then filtered to remove insolubles and the filtrate was evaporated to dryness under reduced pressure. The residue was purified by means of chromatography using chloroform as the developing solvent, and the eluate was concentrated under reduced pressure, giving methyl 3,5-bis(3,5-dimethylthiobenzyloxy)benzoate. The yleld was 21.Og (98.9%). The melting point is 121-122'C. 1H-NMR( δ ppm, CDCl3, TMS): 2.4 (12H,s), 3.8 (3H,s), 4.9(4H,s), 6.3-7.2(9H,m) To sodium dihydrobis(2-methoxyethoxy)aluminate (70% in toluene, 22.7g, 0.078mol), was added dropwise a solution of methyl 3,5-bis(3,5-dimethylthiobenzyloxy)benzoate (21.Og) in tetrahydrof uran (180ml) in a stream of nitrogen at 5-10oC during 30 minutes. After completion of the addition, the mixture was stirred for 5 hours and then poured into 2L of diluted hydrochloric acid, followed by extraction with 1L of chloroform. The extract was evaporated to dryness, and the residue was purified by means of chromatography using chloroform as the developing solvent, giving 3,5-bis(3,5-dimethylthiobenzyloxy)benzyl alcohol. The yleld was 17.5g (85.6%). 1H-NMR( δ ppm. CDCl3, TMS): 2.4(12H,s), 4.6(2H,s), 4.9(4H,s), 6.5-7.0(9H,m) EXAMPLE 4 Production of 3,5-Bis(3,5-dimethylthiobenzyloxy)benzyl Bromide 3,5-Bis-(3,5-dimethylthiobenzyloxy)benzyl alcohol (17.0g, 0.033mol) and carbon tetrabromide (14.2g, 0.0043mol) were dissolved in 100ml of tetrahydrofuran. To this, triphenylphosphine (11.3g, 0.043mol) was added portionwise. at the temperature of 1.0 to 10oC . After completion of the addition, the mixture was stirred for 7 hours keeping the mixture at the same temperature. Then, the reaction mixture was poured into 300ml of ice-water and the resulting mixture was extracted with chloroform. The extract was purified by means of chromatography, giving 7.0g of 3,5-bis(3,5-dimethylthiobenzyloxy)benzyl bromide 1H-NMR( δ ppm, CDC13, TMS): 2.4(12H.s), 4.4(2H,s), 4.9(4H,s), 6.5-7.1(9H,m) EXAMPLE 5 Production of Methyl 3,5-Bis(dimethylthiocarbamoyloxy)benzoate In a 5L round bottomed flask equipped with a stirrer, were placed methyl 3,5-dihydroxybenzoate (168.2g, l.OOOmol), dimethylcarbamoyl chloride (280.4g, 2.20mol, 97% pure), potassium carbonate (300g, 2.17mol) and acetone (3000ml), and the mixture was reacted at 40-50oC with stirring. The acetone was removed by concentrating the reaction mixture under reduced pressure. Upon addition of excess amount of water to the residue and upon cooling, methyl 3,5-bis(dimethylthiocarbamoyloxy)benzoate was obtained as colorless crystals, which were recrystallized from ethanol, giving 297.5g (87%) of the pure compound as needles. The melting point is 132-133oC. 1H-NMR(CDCla) : 3.34(6H,s,Me x 2), 3.44(6H,s,Me x 2), 3.90(3H,s,Me), 7.05-7.09(lH,m,ph-H), 7.64-7.67(2H,s,ph-H) [Me stands for CH3, and ph stands for phenyl (the same hereinbefore and hereinafter, throughout this specification).] EXAMPLE 6 Production of Methyl 3,5-Bis(dimethylcarbamoylthio)benzoate Methyl 3,5-bis(dimethylthiocarbamoyloxy)benzoate (297.0g, 0.867mol) was added with stirring to 1,3-imidazolidinone (1000ml) while keeping the temperature at 210-213oC . After heating under reflux for 3 hours, the 1,3-imidazolidinone was distilled off, giving a viscous liquid. To this, ethyl acetate (1000ml) was added, and the mixture was washed with a cold 5% sodium hydroxide solution (300ml) and with a saturated sodium chloride solution (300ml), and then dried over magnesium sulfate. After removing the ethyl acetate by means of distillation, the residue was recrystallized from toluene (500ml), giving 219g (74%) of methyl 3,5-bis(dimethylcarbamoylthio)benzoate as colorless needles. The melting point is 128-130oC. 1H-NMR(CDCl3): 3.05(12H,S,Me X 4), 3.90(3H,s,Me), 7.82(lH,s,ph-H), 8.17(2H,s,ph-H) EXAMPLE 7 Production of Methyl 3,5-Dimercaptobenzoate Methyl 3,5-bis(dimethylcarbamoylthio)benzoate (34.2g, 0. 100mol) was made to react with a mixture of 43g of 28% methanol solution of sodium methoxide (0.223mol) and methanol (150ml) at 22-25cC. After addition of 500ml of ice-water, the reaction mixture was neutralized with concentrated hydrochloric acid to give a colorless crystals. The crystals thus obtained were purified by means of recrystallization from methanol giving 12.5g (62.5%) of methyl 3,5-dimercaptobenzoate as a colorless powder. The melting point is 61-62oC. 1H-NMR(CDCl3): 3.51(2H,s,SH x 4), 3.87(3H,s,Me), 7.30(lH,t,J=0.1Hz,ph-H), 6.67(2H,d,J=0.1Hz,ph-H) EXAMPLE 8 Production of Ethyl 3,5-Dimercaptobenzoate (wherein Et stands for ethyl. The same hereinafter.) The reaction shown above was carried out according to the ordinary method of esterification, ylelding ethyl 3,5-dimercaptobenzoate. The melting point is 49-51oC. 1H-NMRfCDCla) : 1.36(3H,t,J=0.02Hz,Me), 3.51(2H,S,SH x 2), 4.33(2H,q,CH2), 7.31(lH,s, ph-H), 7.68(2H,s,ph-H) In addition, the corresponding free carboxylic acid, 3,5-dimercaptobenzoic acid was prepared according to the method described in Boiko, V.N.; Shchupak, G.M.; Yagupol'skii, L.M., Zh. Org. Khim., (1985), 21(7), 1470-1477. EXAMPLE 9 3,5-Bis(dimethylcarbamoylthio)benzoic acid Methyl 3,5-bis(dimethylcarbamoylthio)benzoate (3.42g, 10mmol) was made to react with 5% aqueous sodium hydroxide solution (10ml. 12.5mmol) for 3 hours at 22-25oC with stirring. After cooling by the addition of 50ml of ice-water, the reaction mixture was extracted with ethyl acetate (300ml X 3) and the extract was dried over magnesium sulfate. The ethyl acetate was evaporated under reduced pressure and the colorless crystals thus obtained was recrystallized from ethanol to give 2.86g (87.2%) of 3,5-bis(dimethylcarbamoylthio)benzoic acid as colorless needles. The melting point is 196-198oC (with decomposition). 1H-NMR(DMSO-d6): 2.96(6H,s,Me x 2), 3.03(6H,s,Me x 2), 7.82(lH,S,ph-H), 7.88(lH.s,ph-H), 8.10(1H,s,ph-H), 10.5(lH,br-s,OH). EXAMPLE 10 3,5-Bis(dimethylcarbamoylthio)benzyl Alcohol A solution of methyl 3,5-bis(dimethylcarbamoylthio)benzoate (3.42g, 10mmol) in 20ml of toluene was added to sodium dihydrobis(2-methoxyethoxy)aluminate (70% in toluene, 8.7g, 30.1mmol) at the temperature of 15-30oC, and the mixture was heated under reflux with stirring. The reaction mixture was cooled by the addition of 50ml of ice-water containing 10ml of concentrated sulfuric acid, followed by extraction with ethyl acetate (30ml X 3). The extract was dried over magnesium sulfate. The ethyl acetate was removed by distillation under reduced pressure, ylelding 2.54g of a colorless oil. This product was then purified by the method of chromatography using chloroform as the developing solvent, giving 3,5-bis(dimethylcarbamoylthio)benzyl alcohol (1.21g, 38.5%) as a colorless oil. 1H-NMR(CDCla): 2.90(6H,s,Me x 2), 2.94(6H,s,Me x 2), 4.50(2H,s,CH2). 7.38(2H,s,ph-H), 7.44(lH,s,ph-H). EXAMPLE 11 Production of 3,5-Dimercaptobenzyl Alcohol 3,5-Bis(dicarbamoylthio)benzyl alcohol was hydrolyzed by the ordinary method of hydrolysis using sodium hydroxide, giving 3,5-dimercaptobenzyl alcohol. EXAMPLE 12 Production of 3,5-Dimercaptobenzyl Mercaptan 3,5-Bis(dimethylcarbamoylthio)benzyl alcohol was treated with sodium hydroxide according to the ordinary method to give 3,5-dimercaptobenzyl alcohol. This alcohol was then brominated in a manner similar to that in EXAMPLE 17, giving 3,5-dimercaptobenzyl bromide, followed by the reaction with urea according to the ordinary method giving 3,5-dimercaptobenzyl mercaptan. EXAMPLE 13 Production of 3,5-Bis(dimethylcarbamoylthlo)aniline 3,5-Bis(dimethylcarbamoylthio)benzamide was made to react with NaN03/HCl according to the ordinary method, giving 3,5-bis(dimethylcarbamoylthio)aniline. EXAMPLE 14 Production of 3,5-Bis(dimethylcarbamoylthio)benzamide 3,5-Bis(dimethylcarbamoylthio)benzoic acid (3.28g, 10mmol) and thionyl chloride (30mmol) were added to 30ml of toluene and the resulting mixture was heated under reflux for 2 hours. After removal of the excess thionyl chloride and the toluene, the residue was poured into an ammonia-ethanol solution (10%, 10ml), giving 3,5-bis(dimethylcarbamoylthio)benzamide as colorless crystals. The melting point is 264-265^. EXAMPLE 15 Production of Methyl 3,5-Bis(3,5-di-tertiary-butylbenzylthio)benzoate Methyl 3,5-dimercaptobenzoate (20.Og, 100.Ommol), 3,5-dl-tertiary-butylbenzyl bromide (57.Og, 201.2mmol). 0.3g of 18-crown-6 (manufactured by Wako Pure Chemicals, Co. Ltd.) and potassium carbonate (28.0g, 202.6mmol) were added to 350ml of acetone and the mixture was heated under reflux for 12 hours. After completion of the reaction and removal of insoluble salts and acetone, the residue was purified by the method of column 'chromatography with n-hexane: dichloromethane=l:l, giving 53.Og of the objective 3,5-bis(3,5-di-tertiary-butylbenzylthio)benzoate as colorless needles. The melting point is 102-103tC. 1H-NMR(CDCla): 1.29(36H,s,tert-Bu-H), 3.70(3H,s,Me), 3.90(4H,s,SCH2), 7.10(4H,s.ph-H), 7.29(3H,br-s,ph-H), 7.77(12H,s,ph-H). EXAMPLE 16 Production of 3,5-Bis(3,5-di-tertiary-butylbenzylthio)benzyl Alcohol Methyl 3,5-bis(3,5-di-tertiary-butylbenzylthio Jbenzoate (52.0g, 86.0mmol) was dissolved In 300ml of toluene. To this, was added dropwise a 70% solution of sodium dihydrobis(2-methoxyethoxy)alumlnate in toluene (52g, 180.0mmol), maintaining the temperature at 35oC or below and the resulting mixture was stirred for 2 hours under the same conditions. After completion of the reaction, the reaction mixture was poured into 500ml of a cold 10% hydrochloric acid solution, followed by stirring for 10 minutes. The toluene layer was separated, dried over anhydrous magnesium sulfate and then concentrated. The resulting residue was then purified by means of chromatography with dichloromethane, giving 4.96g of 3,5-bis(3,5-di-tertiary-bylylbenzylthio)benzyl alcohol as a viscous substance. 1H-NMR(CDCl3) : 1.42(36H,s,tert-Bu-H) , 4.18(4H,s,S-CH2) , 4.67(2H,s,CH2O) , 7.23-7.26(7H,m,ph-H), 7.42(2H,s,ph-H) EXAMPLE 17 Production of 3,5-Bis(3,!i-di-tertiary-butylbenzylthio)benzyl Bromide 3,5-3is(3,5-di-tertiary-butylbenzylthio)benzyl alcohol (49.0g, 84.9mmol) and carbon tetrabromide (28.2g, 85.0mmol) were dissolved in 300 ml of tetrahydrofuran. To this solution was added with stirring triphenylphosphln (23.5g, 89.6mmol), at the temperatures of 10oC or below. The reaction mixture became clear once, and then colorless crystals separated gradually. After stirring overnight at 25-30 crystals vrere removed by filtration and the filtrate was concentrated. The residue obtained was purified by means of chromatography with n-hexane:dichloromethane=l:l, giving 34.8g of 3,5-bis(3.5-di-tertiary-butylbenzylthio)benzyl bromide. 1H-NMIUCDCla) : 1.43(36H,s,tert-Bu-H), 4 .18(4H, s ,SCH2) , 4.44(2H,s,CH2Br), 7.23-7.25(7H,m,ph-H), 7.43(2H,s,ph-H). EXAMPLE 18 Production of Dendrimer I 3,5-Bis(3,5-di-tertiary-butylbenzylthio)benzyl bromide (34.0g, 53.1mmol) was made to react in a manner similar to that in EXAMPLE 15, giving 21. Og of the objective dendrimer I as a colorless viscous substance. 1H-NMR(CDCl3) : 1.28(72H,s,tert-Bu-H), 3.76(3H,s,Me), 3.89(12H,S,SCH2), 7.10(12H,s,ph-H), 7.30(7H,S,ph-H), 7.78(2H,s,ph-H) EXAMPLE 19 Production of Dendrimer II Dendrimer I (20.0g, 15.17mmol) was made to react in a manner similar to that in EXAMPLE 16, giving 13.4g of dendrimer II as a colorless viscous substance. 1H-NMR(CDCl3): 1.40(72H,s,tert-Bu-H), 4.03(12H,s,SCH2) , 4.68(2H,s,CH2O), 7.09-7.16(12H,m,ph-H), 7.30(7H,s,ph-H), 7.76(2H,s,ph-H) EXAMPLE 20 Production of Dendrimer III Dendrimer II (13.0g, lO.Onunol) was made to react in a manner similar to that in EXAMPLE 17, giving 6.7g of dendrimer III as a colorless viscous substance. 1H-NMR(CDC13) : 1.40(72H,s,tert-Bu-H), 4.02(12H,s,SCH2) , 4.41(2H,s,CH2Br), 7.10-7.20(12H,m,ph-H), 7.30(7H,s,ph-H), 7.70(2H,s,ph-H) EXAMPLE 21 Production of Dendrimer IV Dendrimer III was made to react in a manner similar to that in EXAMPLE 18, giving dendrimer IV. Thus, dendrimer III was made to react according to an ordinary method with 6,8-dinitro-2,4-dimercaptoquinazoline and l,8-diazabicyclo(5.4.O)undec-7-en in tetrahydrofuran, giving Dendrimer IV. EXAMPLE 22 Production of 3,5-Dimercaptobenzamide 3,5-Bis(dimethylcarbamoylthio)benzamide was subjected to hydrolysis with aqueous sodium hydroxide according to the ordinary procedure, giving 3,5-dimercaptobenzamide. EXAMPLE 23 Production of 3,5-Dimercaptoaniline 3,5-Bis(dimethylcarbamoylthio)aniline was subjected to hydrolysis with aqueous sodium hydroxide according to the ordinary procedure, giving 3,5-dimercaptoaniline. EXAMPLE 24 Production of 3,5-Dimercaptobenzonitile 3,5-Bis(dlmethylcarbamoylthio)benzonitrile was subjected to hydrolysis with aqueous sodium hydroxide according to the ordinary procedure, giving 3,5-dimercaptobenzonitile. EXAMPLE 25 Production of Methyl 3,5-Bis(3,5-di-tertiary-butylbenzylthio)benzoate Methyl 3,5-dimercaptobenzoate (20.0g, 100.Ommol), 3,5-di-tertiarybutylbenzyl bromide (molecular weight 283.25, 57.Og, 201.2mmol) and potassium carbonate (molecular weight 138.21, 28.Og, 202.6mmol) were dissolved in 350ml of acetone and the mixture was heated under reflux for 12 hours. The acetone and salts were removed, and the residue was purified by means of chromatography with dichloromethane as the developing solvent, giving methyl 3,5-bis(3,5-di-tertiary-butylbenzylthio)benzoate as needles. In addition, throughout in this specification, % means weight %, and ratio of the solvents used are expressed in volume per volume. EXAMPLE 26 Production of Methyl 3-dimethylaminosulfurnyl-5-hydroxybenzoate According to the method of EXAMPLE 5 or 6, but by the use of half amount of dimethylthiocarbamoyl chloride, methyl 3-dimethylaminosulfurnyl-5-hydroxybenzoate was produced from 3,5-dihydroxybenzoate at 26% yleld. Melting point: 135 to 138oC 1H-NMR(CDCl3) ; 3.00 & 3.05(6H, s & s, 2 x Me) , 3.58(1H, br-s, OH), 3.84(3H, s. Me), 7.05, 7.47 & 7.78(3H, s, s & s, Ph-H) EXAMPLE 27 The present invention is illustrated in more detail by reference to the following example. However, the present embodiment is to be considered in all respect as illustrative and not restrictive. Figures 2 to 4 show schematic diagrams of a single electron tunneling device of the present invention. Fig.2 shows the horizontal projection (plan). Fig.3 a vertical cross-sectional view taken on line X-Y of Fig. 2, and Fig. 4 a magnified conceptual diagram of the junction part of the device. In Fig. 3, the numeral 9 indicates the electron tunneling layer consisting of the lower polylmide LB film layer 3, the intermediary electrode 4 and the upper poluimide LB film 5. In this single electron tunneling device, a gold electrode being 100nm thick and free from a surface oxide layer formation was formed on a glass substrate by the method of vacuum evaporation as the lower electrode. Next, on the lower electrode 2, the lower polylmide LB film layer 3, consisting of 25 polylmide LB films of the polylmide which has the degree of polymerization shown by Formula 25, was constructed by first depositing the layers of precursor by the Langmuir-Blodgett technique, followed by a chemical treatment. Then, by the procedure similar to that used for the preparation of the lower polylmide LB layer 3, the intermediary electrode 4 which consists of monomolecular layer of polylmide LB film containing dendritic molecules of the present invention was formed using a mixture of the polylmide of Formula 25 and the dendritic molecule of the present invention shown in Formula 24 in a ratio of 500:1. Molecular occupied area measurement showed that, in the intermediary electrode obtained, there were about 1000 molecules of the compound of Formula 24 in an area of about 1 µ m square. This electrode functioned as an intermediary electrode effectively. On the intermediary electrode layer 4, in a manner similar to that of the lower polylmide LB film layer 3, was deposited 30 layers of the polylmide precursor LB films, followed by lmldation with a chemical treatment, giving the upper polylmide LB film layer 5. Finally, on the upper LB film layer 5, the upper electrode 6 and the upper reserve electrode 7 of gold having a thickness of 50-100nm and being free from a surface oxide layer formation were formed by the method of vacuum evaporation in the direction to cross the lower electrode 2, giving a single electron tunneling device. In the device of this EXAMPLE, the reserve upper electrode 7 was the additional one which was attached together with the upper electrode 6 for use to compare the characteristics of the device based on the present invention. Furthermore, the edge of the lower electrode 2 was covered with an edge-covering layer 8 in order to prevent both the dielectric breakdown from the edge of the lower electrode 2 and the short circuit due to defects among the lower polylmide LB film layer 3, the intermediary electrode layer 4 and the upper polylmide LB film layer 5. Consequently, following these procedures, a single electron tunneling device of the working area of 50x100 square µm was prepared. With the single electron tunneling device prepared using the compound of the present invention, the electric current flow across the junction was measured by means of an ammeter 18 under applied step voltage 17 at a constant temperature in a cryostat. The measurement was carried out by the two-terminal network method, because the resistance between the lower electrode 2 and the upper electrode 6 amounted to 100M to 10GΩ . Fig. 5 shows the I-V (current to voltage) characteristic measured at 5.2K. This Fig. shows clearly, although at a cryogenic temperature of 5.2K, an equally spaced voltage step structure characteristic of a single electron tunneling. It is known that the step width due to the single electron tunneling process uniformly equals to e/C, wherein C is the capacitance between the intermediary electrode 4 and the lower electrode 2 or the upper electrode 6 and e is the electric charge of an electron. As Fig. 5 shows, the voltage step width is uniformly about 100mV, both in the zero and first orders, revealing clearly the characteristic of the single electron tunneling. INDUSTRIAL APPLICABILITY The dendritic molecules of the present invention respond immediately by emission of light when stimulated with light or electric energy, and are useful, for example, as switching material of memory. WE CLAIM: 1. A dendritic compound, wherein it comprises a core a branch structure composed of Unit 1 represented by the following structure, and surface functional groups. and / or Unit 3 represented by the following structure, and the surface functional groups. A dendritic compound, wherein it comprises a core, a branch structure composed of both Unit 1 described in claim 1 and Unit 2 represented by the following structure, 3. A dendritic compound, wherein it comprises a core, a branch structure composed of two or more of the partial branch structures Oof Unit 1 described in claim 1, Unit 2 described in claim 2, and Unit 3 in claim 2, and the surface functional groups. '■*.' 4. A dendritic compound as claimed in any of claims 1 and 2, wherein the branch structure is of 2-10 generations and is constructed with both a generation or generations of the branch structure composed of Unit 1 described in claim 1 and a generation or generations of the branch structure Unit 2 described in claim 2 and/or Unit 3 described in claim 2. 5. A dendritic compound as claimed in claim 1 to 4, wherein the surface functional group is an alkyl group which may be substituted, an aralkyl group which may be substituted, an alkoxy group, an alkoxycarbonyl group or a quaternary ammonium group. 6. A dendritic compound as claimed in claim 5, wherein the surface functional group is a t-butyl group. 7. A dendritic compound as claimed in claim 1 to 6, wherein the core is a color developing functional group. 8. A dendritic compound as claimed in claim 1 to 6, wherein the core is a rhodamine pigment, a quinazoline, a perylene, an azo-compound, 2,5- dihydroxybenzoic add methyl ester, a porphyrin, 4,4' -dihydroxybipheny) or 1-(4.4, 4"-trihydroxyphenyl)ethane residue 9. A thio-compound represented by the following structure, wherein ring A is a ring represented by Formula 5, which has each of the substituent B, substituent C and substitue D at the positions denoted with a bond, and may be substituted at the positions where no bond is attached; substituent B stands for -S(O) nR1, wherein n stands for an integer of 0-2, and R1 stands for a substituent; substituent C stands for -X1R2, wherein X1 stands for a intervening group, and R2 stands for a substituent; and substituent D stands for a substituent bonded to the ring A through a carbon atom. 10. A thio-compound as claimed in claim 9, wherein R1 and R2 are, each being the same or different, an alkali metal, a hydrogen atom, an alkyl group which may be substituted, an aralkyl group, a carbamoyl group or a thiocarbamoyl group. 11. A thio-compound as claimed in claim 9 or 10 wherein X1 is a methylene group, a dimethylmethylene group, an oxygen atom, a sulfur atom, a sulfinyl group or a sulfonyl group. 12. A thio-compound as claimed in any one of claim 9 to 11, wherein the subtituent D is a cyano group, a formly group or X2R3, wherein X2 stands for a methylene group which may be substituted, a carbonyl group or a thiocarbonyl group, and R3 stands for a hydroxyl group which may be protected, a mercapto group or an amino group, with the proviso that when X2 is a carbonyl group, then R3 is not a hydroxyl. 13. 3,5-dimercaptoberrayl alcohol. 14. 3,5-dimercaptobenzy mercaptan. 15. A compound represented by the following structure and a salt thereof, wherein each of R1 and R2 stands for (1) an alkali metal such as sodium and potassium and so on, (2) a hydrogen atom, (3) an alkyl group which may be substituted with a fluorine atom, a chlorine atom, a bromine atom, an alkoxy group or a thioalkoxy group, and so on, (4) a phenyl group which may be substituted with the aforementioned substituent or substituents, or (5) an aralkyl group which may be substituted with the aforementioned substituent or substituents, (6) a disubstituted carbamoyl or thiocarbamoyl group represented by the following structure, wherein R7stands for (1) an alkyl group which may be substituted with a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, (2) a phenyl group which may be substituted with aforementioned substrtuent or substituents, or (3) an aralkyl group which may be substituted with aforementioned substrtuent or substituents, z stands for an oxygen atom or a sulfur atom, n stands for an integer of 0 to 2, x stands for a methylene group, a dimethylmethylene group, an oxygen atom, a sulfur atom, a sulfinyl group or a surfonyl group, Each of R3 and R4 stands for (1) a hydrogen atom, (2) an alkyl group which may be substituted with a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, and so on, (3) a phenyl group which may be substituted with aforementioned substrtuent or substituents, or (4) an aralkyl group which may be substituted with aforementioned substrtuent or substituents, or R3 and R4 may be combined to form a methylene group, a keto group or a thioketo group, or R3, R4 and R5 taken together with the carbon atom to which they are attached may form a cyano group, R5 stands for (1) a hydroxyl group, (2) a mercapto group, (3) an amino group, (4) a formyl group, (5) an alkyl group which may be substituted with a halogen atom such as fluorine atom, a chlorine atom, a bromine atom, and so on, (6) an alkoxy group which may be substituted with aforementioned substrtuent or substituents, (7) a thioalkoxy group which may be substituted with aforementioned substrtuent or substituents, (8) a phenyl group which may be substituted with aforementioned substrtuent or substituents, (9) an aralkyl group which may be substituted with aforementioned substrtuent or substituents, R6 means a hydroxyl group, an alkyl group, an alkoxy group, an alkylthio group, a nrtro group, a cyano group, a dimethylamino group, or a diethylammino group. ABSTRACT Title: A dendritic compound. A dendritic compound, wherein it comprises a core, a branch structure composed of Unit 1 represented by the following structure, and surface functional groups.

Full Text

SPECIFICATION
Novel Thioether Derivatives, Their Method for Production
and Use
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to novel thioether
derivatives, the production method and use thereof, and relates
especially to the S containing dendrimers and the synthetic
intermediates thereof. The thioether derivatives and their
intermediates of the present invention have industrial and
pharmaceutical applications.
2. Description of the Prior Art
The dendritic molecules, having a unique macromolecular
structure, are expected to have a wide field of application.
The dendritic molecules which have a unique chemical structure
composed of a central core (nucleus), and a branch structure
constructed with branches (units) repeated regularly and the
surface functional groups, both extending
three-dimensionally, have been investigated actively in the
field, for example, of nano science, communication science,
electro-material science, medical science, pharmaceutical
science, biological science, surface science and material
science, and so on (References: "Dendritic Molecules", VCH
Publication Co. 1996; "Molecular Design of Dendrimers" and
"Miscellaneous Functions of Dendrimers" Gendai Kagaku, June,
1998, on pp. 20-40; "Applications of Dendrimers as Non-linear
Optical Materials" in Kobunshi, Vol.47, November, 1998.) It

may safely be said, however, that the dendrimer science is "one
of the latest sciences", because it has been highlighted only
since about the middle of the year 1990 and the number of the
research on it has increased recently.
As for the use of the dendritic molecules, there have been offered a variety of inventions on the subject of industrial use thereof, for example, their use in medicine and agricultural
chemicals (JP-A Hei7-330631), use in solar cell and
photosensitive material for electrophotography (JP-A
Heill-40871), use in electronic material (JP-A Heill-171812),
use in liquid crystal (JP-A 2000-264965), use in paint and ink
(JP-A Heill-14018O), use in fluorescent resin sheet ( JP-A
Heill-323324), use in qualitative and quantitative analyses
(JP-A Heill-218494), use in biological response modifier (JP-C
Hei8-510761), and so on.
SUMMARY OF THE INVENTION
The object of the present invention is to provide both
novel dendritic molecules with useful functions and novel
synthetic intermediates for producing them.
More specifically, the main object of the present
invention is to provide novel dendrimers which are useful as
electronic material (for example, as the switch of memory) due
to their ability to emit light from the core by transferring
electron which exists in the branch structure into the core
which has been made electron deficient by absorbing light or
electric energy.
Other objects of the present invention will become clear

through the explanation hereinafter.
The present inventors made an intensive investigation on
the aforementioned problems and succeeded in creating the S atom
containing dendrimers of the present invention.
In addition, the present inventors have obtained a lot
of novel knowledge about the dendrimers of the present invention
which have many sulfur atom in their branch structures. Namely,
in the case of the sulfur atom we can make use of their d-orbital
electrons which do not exist in the oxygen atom. As the
d-orbital electrons of the sulfur atom are placed farther apart
from the nuclei than the p-orbital electrons of the oxygen atom,
the electrons of the sulfur atom can move more freely than the
electrons of the oxygen atom; the light or electric energy can
be transferred to the core, which is in an electron-deficient
state, with ease; it becomes possible to make the core emit light
by constructing the core from a residue of a luminescent
compound; and a larger polarization between the branch
structure and the core can be obtained with the sulfur atoms
than with the oxygen atoms. Consequently, the present
inventors have got the knowledge that the dendrimers of the
present invention are useful as an electronic material, for
example, as the switch of memory.
In addition, the present inventors have found that,
although S atom-containing dendrimers can suffer deterioration
due to oxidation, it is possible to make them more durable and
of a long life by placing substituents with steric bulkiness,
preferably t-butyl groups, on the outside of the branch
structure, namely, at the opposite end across the branch
structure from the core.

Furthermore, the present inventors have found that the
S atom-containing dendrimers of the present invention can be
produced conveniently and industrially advantageously from a
series of novel synthetic intermediates of specific structures. Based on a lot of novel knowledge mentionedabove, the
present inventors have carried out an intensive investigation
on the subject and completed the present invention.
That is to say, the present invention relates to the
compounds and salts thereof:
comprises or preferably
[1] A dendritic molecule characterized in that it/has a
core, a branch structure composed of Unit 1 represented by the
following structure,

, wherein ring A stands for a homo- or heterocyclic six-membered
ring, and surface functional groups as the essential

constituents.
comprises or preferably
[2] A dendritic molecule characterized in that it/has a
core, a branch structure composed of both Unit 1 described in
[1] and Unit 2 represented by the following structure,

wherein ring A stands for a homo- or heterocyclic six-membered
ring, and/or Unit 3 represented by the following structure.

wherein ring A stands for a homo- or heterocyclic six-membered
ring, and the surface functional groups.

[3} A dendritic molecule characterized in that it comprises or preferably has a
core, a branch structure composed of two or more of the partial
branch structures of Unit 1 described in [1], Unit 2 described
in [2], and Unit 3 in [2], and the surface functional groups.
[ 4 ] A dendritic molecule of any of [ 1 ] and [ 2 ], wherein
the branch structure is of 2-10 generations and is constructed
with both a generation or generations of the branch structure
composed of Unit 1 described in [1] and a generation or
generations of the branch structure Unit 2 described in [2]
and/or Unit 3 described in [2].
[5] A dendritic molecule of [1] to [4], wherein the ring
A of Unit 1, Unit 2 and Unit 3 is a benzene ring, a pyrimidine
ring or a triazine ring.
[ 6 ] A dendritic molecule of [ 1 ] to [ 5 ], wherein the surface
functional group is an alkyl group which may be substituted,
an aralkyl group which may be substituted, an alkoxy group, an
alkoxycarbonyl group or a quaternary ammonium group.
[ 7 ] A dendritic molecule of [ 6 ], wherein the surface
functional group is a t-butyl group.
[8] A dendritic molecule of [1] to [7], wherein the core
is a color developing functional group.
[ 9 ] A dendritic molecule of [ 1 ] to [ 7 ], wherein the core
is a rhodamine pigment, a quinazoline, a perylene, an
azo-compound, 2,5-dihydroxybenzoic acid methyl ester, a
porphyrin, 4,4'-dihydroxybiphenyl or
1-(4.4', 4 " -trihydroxyphenyl)ethane residue.
[10] A thio-compound represented by the following

structure,
/
wherein ring A is a ring represented by Formula 5,

which has each of the substituent B, substituent C and
substituent D at the positions denoted with a bond, and may be
substituted at the positions where no bond is attached;
substituent B stands for -S(O)nR1,
wherein n stands for an integer of 0-2, and R1 stands for a
substituent;
substituent C stands for -X1R2,
, wherein X1 stands for a intervening group, and R2 stands for
a substituent; and
substituent D stands for a substituent bonded to the ring A
through a carbon atom.
[11] A thio-compound of [10], wherein R1 and R2 are, each
being the same or different, an alkali metal, a hydrogen atom,
an alkyl group which may be substituted, an aralkyl group, a
carbamoyl group or a thiocarbamoyl group.
[12] A thio-compound of [10] or [11], wherein X1 is a
methylene group, a dimethylmethylene group, an oxygen atom, a
sulfur atom, a sulfinyl group or a sulfonyl group.
[13] A thio-compound of any one of [10] to [12], wherein

the subtituent D is a cyano group, a formyl group or X2R3, wherein
X2 stands for a methylene group which may be substituted, a
carbonyl group or a thiocarbonyl group, and R3 stands for a
hydroxyl group which may be protected, a mercapto group or an
amino group, with the proviso that when X2 is a carbonyl group,
then R3 is not a hydroxyl.
[14] 3,5-dimercaptobenzyl alcohol.
[15] 3,5-dimercaptobenzyl mercaptan.
[16] A compound represented by the following structure
and a salt thereof,

wherein each of R1 and R2 stands for
(1) an alkali metal such as sodium and potassium and so on,
(2) a hydrogen atom,
(3) an alkyl group which may be substituted with a fluorine
atom, a chlorine atom, a bromine atom, an alkcoxy group or
a thloalkoxy group, and so on,

(4) a phenyl group which may be substituted with the
aforementioned substituent or substituents,, or
(5) an aralkyl group which may be substituted with the
aforementioned substituent or substituents,
(6) a disubstituted carbamoyl or thlocarbamoyl group
represented by the following structure.

, wherein R7 stands for
(1) an alkyl group which may be substituted with a halogen
atom such as a fluorine atom, a chlorine atom and a bromine
atom,
(2) a phenyl group which may be substituted with
aforementioned substituent or substituents, or
(3) an aralkyl group which may be substituted with
aforementioned substituent or substituents,
Z stands for an oxygen atom or a sulfur atom,
n stands for an integer of 0 to 2,
X stands for a methylene group, a dimethylmethylene group,
an oxygen atom, a sulfur atom, a sulfinyl group or a sulfonyl
group,
Each of R3 and R4 stands for (1) a hydrogen atom, (2) an
alkyl group which may be substituted with a halogen atom such
as a fluorine atom, a chlorine atom and a bromine atom, and so
on, (3) a phenyl group which may be substituted with
aforementioned substituent or substituents, or (4) an aralkyl
group which may be substituted with aforementioned substituent
or substituents, or R3 and R4 may be combined to form a methylene
group, a keto group or a thioketo group, or R3, R4 and R5 taken
together with the carbon atom to which they are attached may
form a cyano group,
R5 stands for (1) a hydroxyl group, (2) a mercapto group,
(3) an amino group, (4) a f ormyl group, (5) an alkyl group which
may be substituted with a halogen atom such as a fluorine atom,
a chlorine atom, a bromine atom, and so on, (6) an alkoxy group
which may be substituted with aforementioned substituent or
substituents, (7) a thioalkoxy group which may be substituted

with aforementioned substituent or substituents, (8) a phenyl
group which may be substituted with aforementioned substituent
or substituents, (9) an aralkyl group which may be substituted
with aforementioned substituent or substituents,
R6 means a hydroxyl group, an alkyl group, an alkoxy group,
an alkylthio group, a nitro group, a cyano group, a
dimethylamino group, or a diethylammino group.
BRIEF DISCRIPTION OF THE DRAWINGS
Fig. 1 shows a schematic diagram of the layer structure
of a single electron tunneling device of the present invention.
Fig. 2 shows the plan of a single electron tunneling device
of an embodiment according to the present invention.
Fig. 3 is a vertical cross-sectional view taken on line
X-Y of Fig. 2.
Fig. 4 is a diagram of the junction part of the device.
Fig. 5 is a graph showing the I-V (current to voltage)
characteristic of a single electron tunneling device according
to the present invention, which is measured at 5.2K.
Explanation of reference letters or numerals:
1 substrate layer
2 lower electrode
3 lower polylmide LB film layer
4 intermediary electrode layer
5 upper polylmide LB film layer
6 upper electrode
7 reserve upper layer

8 edge-covering layer
9 electron tunneling layer
10 single electron tunneling device

17 step voltage
18 ammeter
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, as the examples of the homo-
or heterocyclic six-membered ring, there can specifically be
mentioned a benzen ring, a pyridine ring, a triazine ring,
diazine rings (for example, apyridazine ring, a pyrimidine ring,
a pyrazine ring), and so on.
As the surface functional group, there can specifically
be mentioned a t-butyl group, CONH(CH2)2N+(CH3)3, and alkoxy
groups including the methoxy group, and so on, the t-butyl group,
however, being the most preferred one in the present invention.
As the alkyl groups, there can be mentioned those, which
may be straight or branched, of, favorably, the carbon number
of C1-4, exemplified specifically by methyl, ethyl, n-propyl,
isopropyl and t-butyl, and so on.
As the aralkyl groups, there can be mentioned benzyl and
phenethyl, and so on. As the alkoxy groups, there can be
mentioned those, which may be straight or branched, of,
favorably, the carbon number of C1-4, exemplified specifically
by a methoxy group, an ethoxy group, an i-propoxy group and a
t-butoxy group, and so on.
As the color developing functional groups, those groups,
which may be known per se and can be derived, specifically, from

rhodamine pigments, quinazoline, perylene, and azo-compounds,
2,5-dihydroxybenzoic acid methyl ester, porphyrins,
4,4'-dihydroxybiphenyl or 1-(4.4',4"-trihydroxyphenyl)ethane,
are favorably used.
Although those synthetic intermediates mentioned in [10]
to [14] are novel compounds, they can be manufactured with ease
according to the methods known per se, as exemplified hereunder.
EXAMPLES

Next, by using the synthetic intermediates obtained above,
the dendrimers of the present invention are produced. In the
production, either of the two procedures, known per se: a
divergent synthetic method, in which the central core inside,
the branch structure outside, and the outermost surface

functional groups are constructed successively in this order,
or a convergent synthetic method, in which the outermost surface
functional groups, the branch structure inside and the core at
center are constructed successively in this order.
Thus, both the compounds and dendrimers of the present
invention shown hereunder can be produced.

By repeating the procedure mentioned above, a dendrimer
of higher generation shown hereunder can be produced.

The invention is illustrated in more detail by reference
to the following examples.However the present embodiments

are to be considered in all respects as illustrative and not
restrictive. Hereunder, the reactions related to the
following examples are illustrated in reaction schemes, wherein
Ex. means example.

By the same method, following compounds are produced.

The following is a specific explanation of the use of the
compounds of the present invention referring to an illustration.
Fig. 1 shows a schematic diagram of the layer structure of a
single electron tunneling device of the present invention. In
the present invention, a single-electron tunneling device is
constructed by depositing on a substrate layers 1 of a lower
electrode 2, a lower polylmide LB film layer 3, an intermediary
electrode layer 4, an upper polylmide LB film layer 5, and an
upper electrode 6 layer by layer.
As the material used for the substrate, various materials
which are in general use as the substrate of electronic
component, such as metals, glasses, chinaware, ceramics and
plastics, and so on, can be used without any particular
restriction, and as the material for the lower electrode 2 and
upper electrode 6, there can be used thin films of metals such

as gold, silver and copper, and so on.
On the lower electrode 2, the lower polylmide LB film layer
3 is deposited. In the present invention, the term "polylmide
LB film" means either a monomolecular film of polylmide or a
built-up film thereof, made by the Langmuir-Blodgett technique.
In the single electron tunneling device of the present invention,
the polylmide LB film layer 3 can be constructed by laminating
13 to 30 monomolecular films.
As the polylmide consisting polylmide LB films, polylmide
of a variety of structures can be used. Among them, those which
has the repeating structural unit represented by Formula 25 are
preferably used, because with them, it becomes possible to
control the thickness of the monomolecular film to be prepared.
Here, in the preparation of the polylmide LB film layer 3, it
is preferable to prepare the layer by first depositing the
precursor polyamidic acid monomolecular films and then by
performing imidation by means of appropriate chemical
processes.

Next, the intermediary electrode layer 4, a monomolecular
polylmide LB film layer in which the dendritic molecules of the
present invention are incorporated, is formed on the polylmide
LB film layer 3. In this case, it is necessary to get the
polylmide LB film containing an adequate concentration (0.01

to 1%) of the dendritic molecule of the present invention, in
order to make the dendritic molecule function as an intermediary
electrode. On the intermediary electrode layer 4, the upper
polylmide LB film layer 5 is formed in a manner similar to the
formation of the lower polylmide layer 3. This polylmide LB
film layer 5 is constructed by depositing 20 to 30 layers of
polylmide unimolecular films. By depositing the upper electrode
6 on this upper polylmide LB film layer 5, a single electron
tunneling device of the present invention is prepared. Thus,
in this single electron tunneling device obtained, all the three
layers which construct the electron tunneling layer, namely,
the lower polylmide LB film layer 3, upper polylmide LB film
layer 5 and the intermediary electrode layer 4, are composed
of organic molecular material made of polylmide LB films, which
makes it possible for the device to express a good single
electron tunneling conductivity characteristic.
EXAMPLE 1
Production of Methyl 3,5-dimethylthiobenzoate.

Methyl 3,5-bis(dlmethylcarbamoylthio)benzoate (20g)
was dissolved in 500ml of methanol with heating. To this,
sodium methoxide (30g) was added in an atmosphere of nitrogen.

After completion of the addition, the resulting mixture was then
heated for one hour under reflux and cooled a little. To this,
an excess amount of methyl iodide was added, and the resulting
mixture was heated for three hours under reflux and then
concentrated under reduced pressure. The residue thus
obtained was purified by means of chromatography with
chloroform, giving the objective compound. The yleld was 10.5g
(79.3%). The melting point is 46oC.
1H-NMR( δ ppm, CDC13, TMS): 2.5(6H,s), 3.9(3H,s), 7.2(lH,s),
7.6(2H,s).
EXAMPLE 2
Production of 3,5-Dimethylthiobenzyl Bromide via
3,5-Dlmethylthiobenzyl Alcohol

In an atmosphere of nitrogen, sodium
dihydrobis(2-methoxyethoxy)aluminate (70% in toluene, 50g,
0.17mol) was dissolved into dry tetrahydrofuran. To this, a
solution of 22.8g of 3,5-dimethylthiobenzoate in 100ml
tetrahydrofuran was added dropwise at 5 to 10oC , and the mixture

obtained was stirred at the same temperatures for 6 hours. Then,
the reaction mixture was added to a mixture of 50ml of
concentrated hydrochloric acid and 1L of ice-water, followed
by extraction with chloroform. The extract was purified by means
of chromatography using chloroform as the developing solvent.
The eluate was then evaporated to dryness under reduced pressure
and the residue obtained was washed with petroleum ether, giving
3,5 - dimethylthiobenzyl bromide. The yleld was 21.6g (82%). The
melting point is 76-77°C.
EXAMPLE 3
Production of 3,5-Bis(3,5-dimethylthiobenzyloxy)benzyl
Alcohol via Methyl
3,5-Bis-(3,5-dimethylthiobenzyloxy)benzoate

3,5-Dimethylthiobenzyl bromide (20.Og, 0.080mol),
methyl 3,5-dihydroxybenzoate (6.7g, 0.040mol), potassium
carbonate (28.Og, 0.20mol) and of 18-crown-6 (2.1 g, 0.0080 mol)
were added to 500ml of dry acetone, and the resulting mixture
was heated for 15 hours under reflux in an atmosphere of nitrogen.
The reaction mixture was then filtered to remove insolubles and
the filtrate was evaporated to dryness under reduced pressure.
The residue was purified by means of chromatography using

chloroform as the developing solvent, and the eluate was
concentrated under reduced pressure, giving methyl
3,5-bis(3,5-dimethylthiobenzyloxy)benzoate. The yleld was
21.Og (98.9%). The melting point is 121-122'C.
1H-NMR( δ ppm, CDCl3, TMS): 2.4 (12H,s), 3.8 (3H,s), 4.9(4H,s),
6.3-7.2(9H,m)
To sodium dihydrobis(2-methoxyethoxy)aluminate (70% in
toluene, 22.7g, 0.078mol), was added dropwise a solution of
methyl 3,5-bis(3,5-dimethylthiobenzyloxy)benzoate (21.Og) in
tetrahydrof uran (180ml) in a stream of nitrogen at 5-10oC during
30 minutes. After completion of the addition, the mixture was
stirred for 5 hours and then poured into 2L of diluted
hydrochloric acid, followed by extraction with 1L of chloroform.
The extract was evaporated to dryness, and the residue was
purified by means of chromatography using chloroform as the
developing solvent, giving
3,5-bis(3,5-dimethylthiobenzyloxy)benzyl alcohol. The yleld
was 17.5g (85.6%).
1H-NMR( δ ppm. CDCl3, TMS): 2.4(12H,s), 4.6(2H,s), 4.9(4H,s),
6.5-7.0(9H,m)
EXAMPLE 4
Production of 3,5-Bis(3,5-dimethylthiobenzyloxy)benzyl
Bromide

3,5-Bis-(3,5-dimethylthiobenzyloxy)benzyl alcohol
(17.0g, 0.033mol) and carbon tetrabromide (14.2g, 0.0043mol)
were dissolved in 100ml of tetrahydrofuran. To this,
triphenylphosphine (11.3g, 0.043mol) was added portionwise. at
the temperature of 1.0 to 10oC . After completion of the addition,
the mixture was stirred for 7 hours keeping the mixture at the
same temperature. Then, the reaction mixture was poured into
300ml of ice-water and the resulting mixture was extracted with
chloroform. The extract was purified by means of chromatography,
giving 7.0g of 3,5-bis(3,5-dimethylthiobenzyloxy)benzyl
bromide
1H-NMR( δ ppm, CDC13, TMS): 2.4(12H.s), 4.4(2H,s), 4.9(4H,s),
6.5-7.1(9H,m)
EXAMPLE 5
Production of Methyl
3,5-Bis(dimethylthiocarbamoyloxy)benzoate

In a 5L round bottomed flask equipped with a stirrer, were
placed methyl 3,5-dihydroxybenzoate (168.2g, l.OOOmol),
dimethylcarbamoyl chloride (280.4g, 2.20mol, 97% pure),
potassium carbonate (300g, 2.17mol) and acetone (3000ml), and
the mixture was reacted at 40-50oC with stirring. The acetone
was removed by concentrating the reaction mixture under reduced
pressure. Upon addition of excess amount of water to the
residue and upon cooling, methyl
3,5-bis(dimethylthiocarbamoyloxy)benzoate was obtained as
colorless crystals, which were recrystallized from ethanol,
giving 297.5g (87%) of the pure compound as needles.
The melting point is 132-133oC.
1H-NMR(CDCla) : 3.34(6H,s,Me x 2), 3.44(6H,s,Me x 2),
3.90(3H,s,Me), 7.05-7.09(lH,m,ph-H), 7.64-7.67(2H,s,ph-H)
[Me stands for CH3, and ph stands for phenyl (the same
hereinbefore and hereinafter, throughout this
specification).]
EXAMPLE 6
Production of Methyl
3,5-Bis(dimethylcarbamoylthio)benzoate

Methyl 3,5-bis(dimethylthiocarbamoyloxy)benzoate
(297.0g, 0.867mol) was added with stirring to
1,3-imidazolidinone (1000ml) while keeping the temperature at
210-213oC . After heating under reflux for 3 hours, the
1,3-imidazolidinone was distilled off, giving a viscous liquid.
To this, ethyl acetate (1000ml) was added, and the mixture was
washed with a cold 5% sodium hydroxide solution (300ml) and with
a saturated sodium chloride solution (300ml), and then dried
over magnesium sulfate.
After removing the ethyl acetate by means of distillation,
the residue was recrystallized from toluene (500ml), giving
219g (74%) of methyl 3,5-bis(dimethylcarbamoylthio)benzoate
as colorless needles. The melting point is 128-130oC.
1H-NMR(CDCl3): 3.05(12H,S,Me X 4), 3.90(3H,s,Me),
7.82(lH,s,ph-H), 8.17(2H,s,ph-H)
EXAMPLE 7
Production of Methyl 3,5-Dimercaptobenzoate

Methyl 3,5-bis(dimethylcarbamoylthio)benzoate (34.2g,
0. 100mol) was made to react with a mixture of 43g of 28% methanol
solution of sodium methoxide (0.223mol) and methanol (150ml)
at 22-25cC. After addition of 500ml of ice-water, the reaction
mixture was neutralized with concentrated hydrochloric acid to
give a colorless crystals. The crystals thus obtained were
purified by means of recrystallization from methanol giving
12.5g (62.5%) of methyl 3,5-dimercaptobenzoate as a colorless
powder. The melting point is 61-62oC.
1H-NMR(CDCl3): 3.51(2H,s,SH x 4), 3.87(3H,s,Me),
7.30(lH,t,J=0.1Hz,ph-H), 6.67(2H,d,J=0.1Hz,ph-H)
EXAMPLE 8
Production of Ethyl 3,5-Dimercaptobenzoate

(wherein Et stands for ethyl. The same hereinafter.)
The reaction shown above was carried out according to the
ordinary method of esterification, ylelding ethyl
3,5-dimercaptobenzoate. The melting point is 49-51oC.

1H-NMRfCDCla) : 1.36(3H,t,J=0.02Hz,Me), 3.51(2H,S,SH x 2),
4.33(2H,q,CH2), 7.31(lH,s, ph-H), 7.68(2H,s,ph-H)
In addition, the corresponding free carboxylic acid,
3,5-dimercaptobenzoic acid was prepared according to the method
described in Boiko, V.N.; Shchupak, G.M.; Yagupol'skii, L.M.,
Zh. Org. Khim., (1985), 21(7), 1470-1477.
EXAMPLE 9
3,5-Bis(dimethylcarbamoylthio)benzoic acid

Methyl 3,5-bis(dimethylcarbamoylthio)benzoate (3.42g,
10mmol) was made to react with 5% aqueous sodium hydroxide
solution (10ml. 12.5mmol) for 3 hours at 22-25oC with stirring.
After cooling by the addition of 50ml of ice-water, the reaction
mixture was extracted with ethyl acetate (300ml X 3) and the
extract was dried over magnesium sulfate. The ethyl acetate
was evaporated under reduced pressure and the colorless
crystals thus obtained was recrystallized from ethanol to give
2.86g (87.2%) of 3,5-bis(dimethylcarbamoylthio)benzoic acid
as colorless needles. The melting point is 196-198oC (with
decomposition).
1H-NMR(DMSO-d6): 2.96(6H,s,Me x 2), 3.03(6H,s,Me x 2),
7.82(lH,S,ph-H), 7.88(lH.s,ph-H), 8.10(1H,s,ph-H),

10.5(lH,br-s,OH).
EXAMPLE 10
3,5-Bis(dimethylcarbamoylthio)benzyl Alcohol

A solution of methyl
3,5-bis(dimethylcarbamoylthio)benzoate (3.42g, 10mmol) in
20ml of toluene was added to sodium
dihydrobis(2-methoxyethoxy)aluminate (70% in toluene, 8.7g,
30.1mmol) at the temperature of 15-30oC, and the mixture was
heated under reflux with stirring. The reaction mixture was
cooled by the addition of 50ml of ice-water containing 10ml of
concentrated sulfuric acid, followed by extraction with ethyl
acetate (30ml X 3). The extract was dried over magnesium
sulfate. The ethyl acetate was removed by distillation under
reduced pressure, ylelding 2.54g of a colorless oil. This
product was then purified by the method of chromatography using
chloroform as the developing solvent, giving
3,5-bis(dimethylcarbamoylthio)benzyl alcohol (1.21g, 38.5%)
as a colorless oil.
1H-NMR(CDCla): 2.90(6H,s,Me x 2), 2.94(6H,s,Me x 2),
4.50(2H,s,CH2). 7.38(2H,s,ph-H), 7.44(lH,s,ph-H).
EXAMPLE 11

Production of 3,5-Dimercaptobenzyl Alcohol

3,5-Bis(dicarbamoylthio)benzyl alcohol was hydrolyzed
by the ordinary method of hydrolysis using sodium hydroxide,
giving 3,5-dimercaptobenzyl alcohol.
EXAMPLE 12
Production of 3,5-Dimercaptobenzyl Mercaptan

3,5-Bis(dimethylcarbamoylthio)benzyl alcohol was
treated with sodium hydroxide according to the ordinary method
to give 3,5-dimercaptobenzyl alcohol. This alcohol was then
brominated in a manner similar to that in EXAMPLE 17, giving
3,5-dimercaptobenzyl bromide, followed by the reaction with
urea according to the ordinary method giving
3,5-dimercaptobenzyl mercaptan.
EXAMPLE 13

Production of 3,5-Bis(dimethylcarbamoylthlo)aniline

3,5-Bis(dimethylcarbamoylthio)benzamide was made to
react with NaN03/HCl according to the ordinary method, giving
3,5-bis(dimethylcarbamoylthio)aniline.
EXAMPLE 14
Production of 3,5-Bis(dimethylcarbamoylthio)benzamide

3,5-Bis(dimethylcarbamoylthio)benzoic acid (3.28g,
10mmol) and thionyl chloride (30mmol) were added to 30ml of
toluene and the resulting mixture was heated under reflux for
2 hours. After removal of the excess thionyl chloride and the
toluene, the residue was poured into an ammonia-ethanol
solution (10%, 10ml), giving
3,5-bis(dimethylcarbamoylthio)benzamide as colorless
crystals. The melting point is 264-265^.
EXAMPLE 15

Production of Methyl
3,5-Bis(3,5-di-tertiary-butylbenzylthio)benzoate

Methyl 3,5-dimercaptobenzoate (20.Og, 100.Ommol),
3,5-dl-tertiary-butylbenzyl bromide (57.Og, 201.2mmol). 0.3g
of 18-crown-6 (manufactured by Wako Pure Chemicals, Co. Ltd.)
and potassium carbonate (28.0g, 202.6mmol) were added to 350ml
of acetone and the mixture was heated under reflux for 12 hours.
After completion of the reaction and removal of insoluble salts
and acetone, the residue was purified by the method of column
'chromatography with n-hexane: dichloromethane=l:l, giving
53.Og of the objective
3,5-bis(3,5-di-tertiary-butylbenzylthio)benzoate as
colorless needles. The melting point is 102-103tC.
1H-NMR(CDCla): 1.29(36H,s,tert-Bu-H), 3.70(3H,s,Me),
3.90(4H,s,SCH2), 7.10(4H,s.ph-H), 7.29(3H,br-s,ph-H),
7.77(12H,s,ph-H).
EXAMPLE 16
Production of
3,5-Bis(3,5-di-tertiary-butylbenzylthio)benzyl Alcohol

Methyl
3,5-bis(3,5-di-tertiary-butylbenzylthio Jbenzoate (52.0g,
86.0mmol) was dissolved In 300ml of toluene. To this, was added
dropwise a 70% solution of sodium
dihydrobis(2-methoxyethoxy)alumlnate in toluene (52g,
180.0mmol), maintaining the temperature at 35oC or below and
the resulting mixture was stirred for 2 hours under the same
conditions. After completion of the reaction, the reaction
mixture was poured into 500ml of a cold 10% hydrochloric acid
solution, followed by stirring for 10 minutes. The toluene
layer was separated, dried over anhydrous magnesium sulfate and
then concentrated. The resulting residue was then purified by
means of chromatography with dichloromethane, giving 4.96g of
3,5-bis(3,5-di-tertiary-bylylbenzylthio)benzyl alcohol as a
viscous substance.
1H-NMR(CDCl3) : 1.42(36H,s,tert-Bu-H) , 4.18(4H,s,S-CH2) ,

4.67(2H,s,CH2O) , 7.23-7.26(7H,m,ph-H), 7.42(2H,s,ph-H)
EXAMPLE 17
Production of
3,5-Bis(3,!i-di-tertiary-butylbenzylthio)benzyl Bromide

3,5-3is(3,5-di-tertiary-butylbenzylthio)benzyl
alcohol (49.0g, 84.9mmol) and carbon tetrabromide (28.2g,
85.0mmol) were dissolved in 300 ml of tetrahydrofuran. To this
solution was added with stirring triphenylphosphln (23.5g,
89.6mmol), at the temperatures of 10oC or below. The reaction
mixture became clear once, and then colorless crystals
separated gradually. After stirring overnight at 25-30 crystals vrere removed by filtration and the filtrate was
concentrated. The residue obtained was purified by means of
chromatography with n-hexane:dichloromethane=l:l, giving
34.8g of 3,5-bis(3.5-di-tertiary-butylbenzylthio)benzyl

bromide.
1H-NMIUCDCla) : 1.43(36H,s,tert-Bu-H), 4 .18(4H, s ,SCH2) ,
4.44(2H,s,CH2Br), 7.23-7.25(7H,m,ph-H), 7.43(2H,s,ph-H).
EXAMPLE 18
Production of Dendrimer I

3,5-Bis(3,5-di-tertiary-butylbenzylthio)benzyl
bromide (34.0g, 53.1mmol) was made to react in a manner similar
to that in EXAMPLE 15, giving 21. Og of the objective dendrimer
I as a colorless viscous substance.

1H-NMR(CDCl3) : 1.28(72H,s,tert-Bu-H), 3.76(3H,s,Me),
3.89(12H,S,SCH2), 7.10(12H,s,ph-H), 7.30(7H,S,ph-H),
7.78(2H,s,ph-H)
EXAMPLE 19
Production of Dendrimer II

Dendrimer I (20.0g, 15.17mmol) was made to react in a
manner similar to that in EXAMPLE 16, giving 13.4g of dendrimer
II as a colorless viscous substance.
1H-NMR(CDCl3): 1.40(72H,s,tert-Bu-H), 4.03(12H,s,SCH2) ,
4.68(2H,s,CH2O), 7.09-7.16(12H,m,ph-H), 7.30(7H,s,ph-H),

7.76(2H,s,ph-H)
EXAMPLE 20
Production of Dendrimer III

Dendrimer II (13.0g, lO.Onunol) was made to react in a
manner similar to that in EXAMPLE 17, giving 6.7g of dendrimer
III as a colorless viscous substance.
1H-NMR(CDC13) : 1.40(72H,s,tert-Bu-H), 4.02(12H,s,SCH2) ,
4.41(2H,s,CH2Br), 7.10-7.20(12H,m,ph-H), 7.30(7H,s,ph-H),
7.70(2H,s,ph-H)
EXAMPLE 21
Production of Dendrimer IV

Dendrimer III was made to react in a manner similar to

that in EXAMPLE 18, giving dendrimer IV. Thus, dendrimer III
was made to react according to an ordinary method with
6,8-dinitro-2,4-dimercaptoquinazoline and
l,8-diazabicyclo(5.4.O)undec-7-en in tetrahydrofuran, giving
Dendrimer IV.
EXAMPLE 22
Production of 3,5-Dimercaptobenzamide

3,5-Bis(dimethylcarbamoylthio)benzamide was subjected
to hydrolysis with aqueous sodium hydroxide according to the
ordinary procedure, giving 3,5-dimercaptobenzamide.
EXAMPLE 23
Production of 3,5-Dimercaptoaniline

3,5-Bis(dimethylcarbamoylthio)aniline was subjected to
hydrolysis with aqueous sodium hydroxide according to the
ordinary procedure, giving 3,5-dimercaptoaniline.

EXAMPLE 24
Production of 3,5-Dimercaptobenzonitile

3,5-Bis(dlmethylcarbamoylthio)benzonitrile was
subjected to hydrolysis with aqueous sodium hydroxide according
to the ordinary procedure, giving 3,5-dimercaptobenzonitile.
EXAMPLE 25
Production of Methyl
3,5-Bis(3,5-di-tertiary-butylbenzylthio)benzoate

Methyl 3,5-dimercaptobenzoate (20.0g, 100.Ommol),
3,5-di-tertiarybutylbenzyl bromide (molecular weight 283.25,
57.Og, 201.2mmol) and potassium carbonate (molecular weight

138.21, 28.Og, 202.6mmol) were dissolved in 350ml of acetone
and the mixture was heated under reflux for 12 hours. The acetone
and salts were removed, and the residue was purified by means
of chromatography with dichloromethane as the developing
solvent, giving methyl
3,5-bis(3,5-di-tertiary-butylbenzylthio)benzoate as needles.
In addition, throughout in this specification, % means
weight %, and ratio of the solvents used are expressed in volume
per volume.
EXAMPLE 26
Production of Methyl
3-dimethylaminosulfurnyl-5-hydroxybenzoate

According to the method of EXAMPLE 5 or 6, but by the use
of half amount of dimethylthiocarbamoyl chloride, methyl
3-dimethylaminosulfurnyl-5-hydroxybenzoate was produced from
3,5-dihydroxybenzoate at 26% yleld.
Melting point: 135 to 138oC

1H-NMR(CDCl3) ; 3.00 & 3.05(6H, s & s, 2 x Me) , 3.58(1H, br-s,
OH), 3.84(3H, s. Me), 7.05, 7.47 & 7.78(3H, s, s & s, Ph-H)
EXAMPLE 27
The present invention is illustrated in more detail by
reference to the following example. However, the present
embodiment is to be considered in all respect as illustrative
and not restrictive.
Figures 2 to 4 show schematic diagrams of a single electron
tunneling device of the present invention. Fig.2 shows the
horizontal projection (plan). Fig.3 a vertical cross-sectional
view taken on line X-Y of Fig. 2, and Fig. 4 a magnified
conceptual diagram of the junction part of the device. In Fig.
3, the numeral 9 indicates the electron tunneling layer
consisting of the lower polylmide LB film layer 3, the
intermediary electrode 4 and the upper poluimide LB film 5.
In this single electron tunneling device, a gold
electrode being 100nm thick and free from a surface oxide layer
formation was formed on a glass substrate by the method of vacuum
evaporation as the lower electrode. Next, on the lower electrode
2, the lower polylmide LB film layer 3, consisting of 25
polylmide LB films of the polylmide which has the degree of
polymerization shown by Formula 25, was constructed by first
depositing the layers of precursor by the Langmuir-Blodgett
technique, followed by a chemical treatment. Then, by the
procedure similar to that used for the preparation of the lower
polylmide LB layer 3, the intermediary electrode 4 which
consists of monomolecular layer of polylmide LB film containing

dendritic molecules of the present invention was formed using
a mixture of the polylmide of Formula 25 and the dendritic
molecule of the present invention shown in Formula 24 in a ratio
of 500:1. Molecular occupied area measurement showed that, in
the intermediary electrode obtained, there were about 1000
molecules of the compound of Formula 24 in an area of about 1
µ m square. This electrode functioned as an intermediary
electrode effectively. On the intermediary electrode layer 4,
in a manner similar to that of the lower polylmide LB film layer
3, was deposited 30 layers of the polylmide precursor LB films,
followed by lmldation with a chemical treatment, giving the
upper polylmide LB film layer 5.
Finally, on the upper LB film layer 5, the upper electrode
6 and the upper reserve electrode 7 of gold having a thickness
of 50-100nm and being free from a surface oxide layer formation
were formed by the method of vacuum evaporation in the direction
to cross the lower electrode 2, giving a single electron
tunneling device. In the device of this EXAMPLE, the reserve
upper electrode 7 was the additional one which was attached
together with the upper electrode 6 for use to compare the
characteristics of the device based on the present invention.
Furthermore, the edge of the lower electrode 2 was covered with
an edge-covering layer 8 in order to prevent both the dielectric
breakdown from the edge of the lower electrode 2 and the short
circuit due to defects among the lower polylmide LB film layer
3, the intermediary electrode layer 4 and the upper polylmide
LB film layer 5. Consequently, following these procedures, a
single electron tunneling device of the working area of 50x100
square µm was prepared.

With the single electron tunneling device prepared using
the compound of the present invention, the electric current flow
across the junction was measured by means of an ammeter 18 under
applied step voltage 17 at a constant temperature in a cryostat.
The measurement was carried out by the two-terminal network
method, because the resistance between the lower electrode 2
and the upper electrode 6 amounted to 100M to 10GΩ .
Fig. 5 shows the I-V (current to voltage) characteristic
measured at 5.2K. This Fig. shows clearly, although at a
cryogenic temperature of 5.2K, an equally spaced voltage step
structure characteristic of a single electron tunneling. It
is known that the step width due to the single electron tunneling
process uniformly equals to e/C, wherein C is the capacitance
between the intermediary electrode 4 and the lower electrode
2 or the upper electrode 6 and e is the electric charge of an
electron. As Fig. 5 shows, the voltage step width is uniformly
about 100mV, both in the zero and first orders, revealing
clearly the characteristic of the single electron tunneling.
INDUSTRIAL APPLICABILITY
The dendritic molecules of the present invention respond
immediately by emission of light when stimulated with light or
electric energy, and are useful, for example, as switching
material of memory.

WE CLAIM:
1. A dendritic compound, wherein it comprises a core a branch structure
composed of Unit 1 represented by the following structure,

and surface functional groups.
and / or Unit 3 represented by the following structure,
and the surface functional groups.
A dendritic compound, wherein it comprises a core, a branch structure
composed of both Unit 1 described in claim 1 and Unit 2 represented
by the following structure,

3. A dendritic compound, wherein it comprises a core, a branch structure
composed of two or more of the partial branch structures Oof Unit 1
described in claim 1, Unit 2 described in claim 2, and Unit 3 in claim 2, and
the surface functional groups.
'■*.'
4. A dendritic compound as claimed in any of claims 1 and 2, wherein the
branch structure is of 2-10 generations and is constructed with both a
generation or generations of the branch structure composed of Unit 1
described in claim 1 and a generation or generations of the branch
structure Unit 2 described in claim 2 and/or Unit 3 described in claim 2.
5. A dendritic compound as claimed in claim 1 to 4, wherein the surface
functional group is an alkyl group which may be substituted, an aralkyl
group which may be substituted, an alkoxy group, an alkoxycarbonyl
group or a quaternary ammonium group.
6. A dendritic compound as claimed in claim 5, wherein the surface
functional group is a t-butyl group.
7. A dendritic compound as claimed in claim 1 to 6, wherein the core is a
color developing functional group.
8. A dendritic compound as claimed in claim 1 to 6, wherein the core is a
rhodamine pigment, a quinazoline, a perylene, an azo-compound, 2,5-
dihydroxybenzoic add methyl ester, a porphyrin, 4,4' -dihydroxybipheny)
or 1-(4.4, 4"-trihydroxyphenyl)ethane residue
9. A thio-compound represented by the following structure,

wherein ring A is a ring represented by Formula 5,

which has each of the substituent B, substituent C and substitue D at the
positions denoted with a bond, and may be substituted at the positions
where no bond is attached; substituent B stands for -S(O) nR1,
wherein n stands for an integer of 0-2, and R1 stands for a substituent;
substituent C stands for -X1R2,
wherein X1 stands for a intervening group, and R2 stands for a substituent;
and
substituent D stands for a substituent bonded to the ring A through a
carbon atom.
10. A thio-compound as claimed in claim 9, wherein R1 and R2 are, each
being the same or different, an alkali metal, a hydrogen atom, an alkyl
group which may be substituted, an aralkyl group, a carbamoyl group or a
thiocarbamoyl group.
11. A thio-compound as claimed in claim 9 or 10 wherein X1 is a methylene
group, a dimethylmethylene group, an oxygen atom, a sulfur atom, a
sulfinyl group or a sulfonyl group.
12. A thio-compound as claimed in any one of claim 9 to 11, wherein the
subtituent D is a cyano group, a formly group or X2R3, wherein X2 stands
for a methylene group which may be substituted, a carbonyl group or a
thiocarbonyl group, and R3 stands for a hydroxyl group which may be
protected, a mercapto group or an amino group, with the proviso that
when X2 is a carbonyl group, then R3 is not a hydroxyl.

13. 3,5-dimercaptoberrayl alcohol.
14. 3,5-dimercaptobenzy mercaptan.
15. A compound represented by the following structure and a salt thereof,

wherein each of R1 and R2 stands for
(1) an alkali metal such as sodium and potassium and so on,
(2) a hydrogen atom,
(3) an alkyl group which may be substituted with a fluorine atom, a
chlorine atom, a bromine atom, an alkoxy group or a thioalkoxy
group, and so on,
(4) a phenyl group which may be substituted with the aforementioned
substituent or substituents, or
(5) an aralkyl group which may be substituted with the aforementioned
substituent or substituents,
(6) a disubstituted carbamoyl or thiocarbamoyl group represented by the
following structure,

wherein R7stands for
(1) an alkyl group which may be substituted with a halogen atom such
as a fluorine atom, a chlorine atom and a bromine atom,

(2) a phenyl group which may be substituted with aforementioned
substrtuent or substituents, or
(3) an aralkyl group which may be substituted with aforementioned
substrtuent or substituents,
z stands for an oxygen atom or a sulfur atom,
n stands for an integer of 0 to 2,
x stands for a methylene group, a dimethylmethylene group, an
oxygen atom, a sulfur atom, a sulfinyl group or a surfonyl group,
Each of R3 and R4 stands for (1) a hydrogen atom, (2) an alkyl
group which may be substituted with a halogen atom such as a
fluorine atom, a chlorine atom and a bromine atom, and so on, (3) a
phenyl group which may be substituted with aforementioned
substrtuent or substituents, or (4) an aralkyl group which may be
substituted with aforementioned substrtuent or substituents, or R3
and R4 may be combined to form a methylene group, a keto group
or a thioketo group, or R3, R4 and R5 taken together with the carbon
atom to which they are attached may form a cyano group,
R5 stands for (1) a hydroxyl group, (2) a mercapto group, (3) an
amino group, (4) a formyl group, (5) an alkyl group which may be
substituted with a halogen atom such as fluorine atom, a chlorine
atom, a bromine atom, and so on, (6) an alkoxy group which may
be substituted with aforementioned substrtuent or substituents, (7)
a thioalkoxy group which may be substituted with aforementioned
substrtuent or substituents, (8) a phenyl group which may be
substituted with aforementioned substrtuent or substituents, (9) an
aralkyl group which may be substituted with aforementioned
substrtuent or substituents,

R6 means a hydroxyl group, an alkyl group, an alkoxy group, an
alkylthio group, a nrtro group, a cyano group, a dimethylamino
group, or a diethylammino group.

ABSTRACT

Title: A dendritic compound.
A dendritic compound, wherein it comprises a core, a branch structure composed
of Unit 1 represented by the following structure,

and surface functional groups.

Documents:

647-cal-2001-abstract.pdf

647-cal-2001-claims.pdf

647-CAL-2001-CORRESPONDENCE-1.1.pdf

647-cal-2001-correspondence.pdf

647-CAL-2001-CORRESPONDENCE1.2.pdf

647-cal-2001-description (complete).pdf

647-cal-2001-drawings.pdf

647-cal-2001-examination report.pdf

647-CAL-2001-EXAMINATION REPORT1.1.pdf

647-cal-2001-form 1.pdf

647-cal-2001-form 18.pdf

647-cal-2001-form 2.pdf

647-CAL-2001-FORM 26.pdf

647-CAL-2001-FORM 3.1.pdf

647-cal-2001-form 3.pdf

647-CAL-2001-FORM 5.1.pdf

647-cal-2001-form 5.pdf

647-CAL-2001-GRANTED-ABSTRACT.pdf

647-CAL-2001-GRANTED-CLAIMS.pdf

647-CAL-2001-GRANTED-DESCRIPTION (COMPLETE).pdf

647-CAL-2001-GRANTED-DRAWINGS.pdf

647-CAL-2001-GRANTED-FORM 1.pdf

647-CAL-2001-GRANTED-FORM 2.pdf

647-CAL-2001-GRANTED-SPECIFICATION.pdf

647-CAL-2001-OTHERS.pdf

647-CAL-2001-OTHERS1.1.pdf

647-cal-2001-priority document.pdf

647-cal-2001-reply to examination report.pdf

647-CAL-2001-REPLY TO EXAMINATION REPORT1.1.pdf

647-cal-2001-specification.pdf

647-cal-2001-translated copy of priority document.pdf

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Patent Number

253466

Indian Patent Application Number

647/CAL/2001

PG Journal Number

30/2012

Publication Date

27-Jul-2012

Grant Date

24-Jul-2012

Date of Filing

21-Nov-2001

Name of Patentee

NATIONAL INSTITUTE OF INFORMATION AND COMMUNICATIONS TECHNOLOGY

Applicant Address

INCORPORATED ADMINISTRATIVE AGENCY, 4-2-1, NUKUI-KITAMACHI, KOGANEI-SHI, TOKYO 184-8795, JAPAN

Inventors:

#	Inventor's Name	Inventor's Address
1	MIKI HIDEKI	C/O COMMUNICATIONS RESEARCH LABORATORY INDEPENDENT ADMINISTRATIVE INSTITUTION 4-2-1, NUKUI-KITAMACHI, KOGANEI-SHI, TOKYO 184-8795, JAPAN
2	YOKOYAMA SHIYOSHI	C/O COMMUNICATIONS RESEARCH LABORATORY INDEPENDENT ADMINISTRATIVE INSTITUTION 4-2-1, NUKUI-KITAMACHI, KOGANEI-SHI, TOKYO 184-8795, JAPAN
3	MASHIKO SHINRO	C/O COMMUNICATIONS RESEARCH LABORATORY INDEPENDENT ADMINISTRATIVE INSTITUTION 4-2-1, NUKUI-KITAMACHI, KOGANEI-SHI, TOKYO 184-8795, JAPAN
4	NAKAHAMA TATSUO	C/O COMMUNICATIONS RESEARCH LABORATORY INDEPENDENT ADMINISTRATIVE INSTITUTION 4-2-1, NUKUI-KITAMACHI, KOGANEI-SHI, TOKYO 184-8795, JAPAN

PCT International Classification Number

C09K 9/02

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	358444/2000	2000-11-24	Japan