TW448137B - An oxidizing catalyst system and the oxidation method thereby - Google Patents

Abstract

An oxidizing catalyst system comprizes an imide compound represented by formula (1) below (such as N-hydroxyphthalimide): (wherein R1 and R2 can be hydrogen or halogen-atom substituents, R1 and R2 also can bind be each other and form a double-bond, or be aromatic or non-aromatic rings of 5-12 members, X is O or OH, n=1-3); and a cocatalyst comprizing an element selected form the group consisting of elements of periodic 2A group, transitional metals (periodic 3A group to 7A group, 8A group, 1B group and 2B group) and periodic 3B group (except phospho-vanadi-molybdic acid). Said system can oxidize the matrix (such as cycloalkanes, polychlic hydrocarbons, and aryl compound with methyl or methylene groups on the ortho position of aryl rings) and obtain oxides (such as ketones, alcohols and carbolic acids).

Description

Printing policy of the Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs ^ 48137 A7 _B7___ V. Description of the Invention (I) Fang Shujuan This invention is about a kind of thorium oxide strip, which can oxidize the substrate and generate corresponding gaseous substances with good efficiency. And the gasification method using this catalyst strip (also known as ketones, alcohols, aldehydes, carboxylic acids > > »Pneumatic gasification reaction is one of the most basic reactions in the organic chemical industry, known There are various gasification methods, especially the method of using nitric acid to vaporize the substrate. For example, adipic acid of nylon 66 raw material can be gasified with nitric acid by cyclohexanol alone or a mixture of cyclohexanol and cyclohexane (KA oil). In addition, the long-chain dicarboxylic acids (such as suberic acid, azelaic acid, sebacic acid, n-sebacic acid) of polyester or polyamide raw materials can also be made of the corresponding macrocyclic naphthenes ( For example, cyclooctane, cyclononane, cyclodecane, cyclododecane > are made by nitric acid gasification. However, in these methods, N20 and NOx produced by nitric acid gasification need to be treated, which must be expensive Exhaust gas treatment facilities. From this point a general review by butyl oxide The sulfonation method, or the production method of adipic acid, such as the C0 insertion method, is not technically yet industrialized. The better gasification method from the perspective of resources and the environment is to directly use gas molecules or air as a gasification agent. The catalytic gasification method. Therefore, in the presence of a cobalt catalyst or a boric acid catalyst, a gasification method in which gas molecules are brought into direct direct contact with the substrate is reviewed. For example, in the presence of a cobalt catalyst or a boric acid catalyst, The gaseous molecules will be reviewed by gasification methods of cycloalkanes or cycloalkenes such as cyclohexane or macrocyclic naphthenes, which are directly catalyzed by gaseous molecules. However, when cobalt is used as the catalyst system, it is expensive to recycle. Cobalt content, precipitation of cobalt lutetium media. This paper size is applicable to China's standard of household standard (CNS) Λ4 standard (210 × 297 cm) (please read the precautions on the back before filling this page) 1 --V. Order economy Printed by the Consumer Standards Cooperative of the Ministry of Standards and Standards: 448137 A7, ^ B7 V. Description of the invention U) In addition, in the catalytic gasification method, in order to activate oxygen, not only must high temperature and pressure be used, but the conversion rate and selection rate are still small. In addition, in the production of adipic acid, in order to maintain the height Selectivity, it is necessary to suppress the conversion rate to about 1 G% to generate adipic acid. Therefore, it is difficult for the catalytic gasification method to produce industrially high conversion and selectivity from mild substrates (cyclohexane) under mild conditions. Cycloalkanes such as alkanes, cycloolefins) generate corresponding oxides (adipic acid, cyclohexanol, cyclohexanone, etc.). Regarding the gasification of macrocyclic oxane, JP 4 3-3 1 ϋ G Gazette No. shows a method in which cyclo + dioxane is oxidized with air in the presence of a boric acid catalyst, and cyclododecanol in the product is provided for dehydrogenation reaction to generate cyclododecanone. It reacts with nitropyrene sulfuric acid and utilizes Beckman translocation to prepare the linamide of the raw material of nylon 12. However, compared with cyclohexane, the large cymbal naphthenes are more stable and less reactive. Therefore, in the aforementioned air oxidation method, the conversion rate of cyclododecane is small, and even if cyclododecanol is contained, the yield of cyclododecane is still small. In particular, it is difficult for the catalytic oxidation method to produce corresponding oxides (such as carbofluorene compounds or carboxylic acids) from large fluorene naphthenes with high yields and good efficiency under mild conditions. In addition, the use of free radical generators such as diisobutyronitrile to oxidize the substrate in the presence of gas has been studied. However, this method is also difficult to obtain a high selectivity and good yield to prepare corresponding oxidized compounds from cycloolefins. On the other hand, polycyclic cigarettes with a master-hydrogen bond (methylene) at the junction or bridgehead of adjacent fluorene can richly obtain polycyclic aromatic compounds (such as Le, Lu, J§, Philip, Phenaelene, or its alkyl substituted _), is made by hydrogenation and heat transfer under high temperature and pressure (to be published, the paper size is subject to the Chinese National Standard (CNS) A4 specification (2l0x2W mm)). (Please read the notes on the back before filling this page) Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 1 3 7 \ · Α7 1 ____ Β7_ V. Description of the invention (3) 5 2-2 9 0 9, 5 2- 1 2 7 0 6, 5 3-3 5 9 4 2, 9 3-3 5 9 4 4, 6 0-2 4 6 3 3 3) β The polyfluorenes produced by these methods have thermal stability It can be used as an advanced lubricating oil that requires heat resistance. Polycyclic hydrocarbons have specific functions because each ring has a stable skeleton with the exception of compounds having a three-dimensional symmetrical structure such as adamantane. Therefore, various polycopolymers can be obtained by introducing an acyl group to a polyfluorinated hydrocarbon, and by deriving an acrylic acid derivative or a ferric acid ester if necessary. For example, a method for producing a polyester by introducing a functional group from adamantane to a bridged cyclic hydrocarbon having a methylene master atom at a bridge head position (Japanese Patent Publication Nos. 42-26792, 43-937, and 4 6-3 4 6 2 8) is proposed. , Japanese Patent Laid-Open No. 5 4-2 1 0 90), method for obtaining polycarbonate: method (US Patent Nos. 3,516,369 and 3,594,427), method for obtaining polyalmine or polyimide (Japanese Patent No. 4 5- Publication No. 2 204, U.S. Patent Nos. 3 8 3 2 3 3 2 and 3814735), a method for obtaining a polyurethane (Japanese Patent Publication Nos. 43-700, 43-6456, 44-6267, and 44-12891) Method for obtaining polyfluorene and polysulfonate (US Pat. Nos. 3738960, 3738965, 3753950) and method for obtaining vinyl polymers (Japanese Patent Publication Nos. 45-36950 and 46-28419 also propose the use of polycyclic hydrocarbons as a unit Homopolymers (U.S. Patent No. 3,649,720). Polymers containing these polycyclic hydrocarbons are generally highly functional, such as heat resistance, humidity resistance, loss of light guide, yield rate, Optical properties such as complex buckling rate, thermal expansion pseudo-numbers, etc., all have the properties of conventional polymers. They are not capable of high standards. Optical elements such as optical elements, optical lenses, holograms, precursors, contact lenses, transparent resin coatings for plexiglass, conductive polymers, photographic materials, fluorescent paper, and remote-use standards. (CNS National Standards (CNS) ) A4 specification (210X297 mm) (please read the notes on the back before filling in this page) Order 448137 A7 ,: __B7_ V. Invention Description u) Materials, etc. On the other hand, cross-linked cyclic hydrocarbon-derived ferments Amine-based derivatives, as represented by sinirietoler, a therapeutic agent for Parkinson's disease, can be used to derive various medicines and pesticides with high pharmacological activity, such as used in adamantane, hemantane, probenbornene, hydrazone, Or its derivatives. Therefore, polycyclic hydrocarbons with functional groups at the bridgehead position are pseudo-widely used compounds, and almost all of these compounds can be derived from the corresponding alcohols. Especially for highly functional materials, Polyols having a hydroxyl substitution at a plurality of bridge heads above 2 are preferred. However, it is difficult to effectively and efficiently introduce hydroxyl groups at the bridge head positions of chemically stable polycyclic hydrocarbons. For example, bridging Hydrocarbons (such as adamantane or its derivatives) are hydrolyzed with excess bromine (for example, more than 10 times moles). When brominated, the resulting bromide is hydrolyzed with an excess of stoichiometric excess silver nitrate or silver sulfate. Hydroxyl (chem Ber >, 92, 1629 (1959), 93 226, 1161 (1960); J. Org. Che., 26 220 7 (1961)). Central Bureau of Standards of the Ministry of Economic Affairs. J n I (Please read the notes on the back before filling this page) However, this method not only requires a large amount of bromine, but also reacts for a long time at about 100¾, once it consumes a lot of expensive silver reagents. Especially for bridgeheads of 2 or more, it is difficult to successively brominate. Therefore, when using adamantane, boron tribromide and aluminum tribromide must be used. However, the loss of the hydrolysis step is large. According to the alcohol produced by the bromination method, about 81% of the adamantane monool and the adamantane diol are recovered at about 57¾. And amantadine triol cannot be directly produced from adamantane, and highly sequentially brominated compounds must be separated and hydrolyzed. Therefore, the yield of amantadine triol is extremely low to about 10 to 30% (Tetrahedron Letters, 19 1849 (1967): Just Liebigs Ann, Chem. 6-This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. V. Description of the invention (Evening) 1 7 1 7 6 C (1 96 8)) 〇 1 1 Method for obtaining King Kong diol > Known There is oxidation method II using chromic acid, such as JP 42-1 66 2 1 m. The bulletin states that 5 times more mols of adamantane are used in order to request the ming acid a on 1 1 in a cycloacetic acid solution at 9 0 ° C. 9 With a yield of 96%, read 1 1 1 I selectivity 96% »to produce adamantanediol 0 This method is suitable for oxidizing polycarbohydrocarbons to the I-type bridgehead 9 to produce alcohol derivatives. > Note 1 must be used in excess | Italian | Paleochromic acid, and not only. Highly toxic > Disposal or recovery of equipment items 1 Preparation and lack of economy '〇 9 In addition to chromic acid, there must be excess sulfuric acid 0 1 written and 9 must control the anti m • ζίΛΛ temperature or the concentration of acetic acid in the solvent > 1 High operability. However, 9 can produce adamantanediol. »Reaction conditions Uk * Sanger 1 I cannot vaporize polyhydric alcohols above alcohol. 1 | About using gas molecules or air as an oxidant directly Catalytic oxidation method> For example, it is described in Japanese Patent Publication No. 4 2 -2 67 9 2 9 in the presence of a catalyst of rffi I in the presence of cobalt acid * in the absence of a solvent 9 air pressure 7 kg / cm • '1 5 1 7 0. . 7 Heat up I I Diamond Academy until the conversion rate of I Diamond Academy reaches 70% * Stop the reaction. 1 i King Kong Yuan where the reaction U compounds generated by these reaction pools are oxidized at the bridge head position • btr early alcohol 1 contains a bb yield of 41%, and the glycol content is not traced. However, when line 1 is heated to a conversion of 99%, 9 adamantanediol will produce a yield of 26%. The th ratio of 1> isomerization and a large number of by-product gasified ketone derivatives * are produced by reaction 1 I Extremely difficult to tld. Refine the target compound 〇i 1 T This is suitable for highly functional polycyclic hydrocarbons such as adamantane »To inhibit the formation of I 1 ketone ym m 9 It is necessary to effectively and form diols with good efficiency, especially 1 I is a diol, tetraol, etc. * It is difficult, especially under mild conditions * It is difficult to produce polyols with high conversion rate 7 and selectivity. 0 1 1 1 1 This paper is suitable for China National Standard (CNS) Λ4 specification (2 丨 0X 297 mm)

A7 B7 V. Description of the invention (b) JP-A-5-3 1 0 6 1 0 shows the results of research on various metals other than iV 丄-samarium cobalt I 1 as air gasification catalysts 9 But this The catalyst 1 described in the literature has a small catalyst capacity. It is difficult to produce high yields and good yields from polycyclic hydrocarbons. ^ N Please make 1% chlorinated compounds at a rate of 0. Read 1 I Read 1 1 In addition > The tertiary m atom at the junction of adjacent fluorenes has a hydroxyl group. © 1 1st generation compound 9 is suitable for use as a physiologically active substance. T In the antiviral agent, antibacterial note 1 I | Agent 9 Food Hall Mongolia and other aspects have a high utilization value. In addition »Matters in the ring {Re-joining part of the carbon atom has a functional group of the compound is widely used as a variety of fragrances * 1 packaging 1 material 9 raw materials of fragrant compounds 〇 Therefore A tertiary alcohol with a hydroxyl group on this page at the junction of osmium * is an important compound. However, a compound having a methylene group at the site of adjacent osmium is a 1 I gaseous crack when the compound of a methylene group is oxidized. »Generate the corresponding two m as the main component. Therefore, it is difficult for j— 'side 1 1 to suppress the formation of the two m body i — while introducing a hydroxyl group at the junction of the ring to obtain 1 secondary alcohol 9 can use a special method > use The substrate is heterogeneous. For example, the method shown in Publication No. 6 2 '5 8 9 4 is a ring-gasified tetrahydroindane filled with tetrahydroindene 1 1 »using an aluminum alcohol catalyst. 1 Ring-opening 9 to obtain a hydroindol with a tertiary hydroxyl group 0 These— [.] Hydroindane line I Alcohol and its derivatives Ren Xianye 9 Green tea 9 Bridges 9 Woody 1 Musk-like r Sue-like »Root-like ϊ Cotton-like 绒» American Hua 阒 -like * Pine root-like! I? Earth-like aroma a. Therefore, it can be used as a cologne food, cigarette and other 11 kinds of materials. You can get the above-X * hydroindolinol. Not only does I 1 need to be hydrogenated to form the indane. Tetrahydrofull step> and the step of epoxidizing the generated 1j into tetrahydrofull * and depending on the reaction. The choice of the reaction step 1 I rate is small> 8 ring-opening steps including ring gas compounds t its The target compound 1 1 1 I 1 1 This paper size is applicable to the Chinese National Standard (CNS) Λ4 specification (2 丨 OX 297 mm) Printed A7 by the Consumer Cooperatives of the Central Standardization Bureau of the Ministry of Economic Affairs, _____ B7_ ^ V. Description of the invention ( 7) The yield is very small overall. Therefore, although the less expensive indane is used as the raw material, it is difficult to obtain the target compound economically and favorably. It will be disclosed in Gazette No. 55-42972 that hydrolysis of 1-halotricyclo [4.3,1.12'5] undecane can be used to obtain 1-hydroxytricyclo [4.3.1.1.2'5] undecane. Hydroxytricyclo [4.3.1.1.% S] Undecane can be used as a compound showing pharmacological activity. For example, raw materials such as amino groups exhibiting strong antiviral activity. To-be-opened BS 5 1-1 3 7 60 indicates that tricyclic [4, 3.1.1.1.2J] undecane is brominated to produce 1-halotricyclo [4.3.1.1. 5 ] Undecane. However, when the yield of Dian compound is about 65%, including the ammoniation step, the yield of amino group is below 60%. When it comes to the corresponding chloride, it cannot be directly derived from tricyclo [4.3.1.1.25] undecane, and can be derived from 1-hydroxytricyclo [4 · 3,1.1.2,5] undecane Reacts with radon gas. Therefore, tricyclic [4.3.1.1. 2, 5] undecane has many vaporizable sites, that is, two joint sites adjacent to each other, two bridgehead sites, and seven methylene sites. Therefore, conventional gasification methods such as chromic acid gasification or air gasification cannot directly introduce hydroxyl groups with high selectivity. To be published in Gazette No. 5 7-1 1 4 5 3 S, it is shown that the tricyclic ring [5.2.1.02, s] decane is treated with an organic pergassing, and the 2-endotriol ring C5.2.1.〇ls can be obtained] Decane. This alcohol is a spice substance with strong aroma like camphor tree. It has antiviral, antibacterial, and plant hormone effects. These properties are also found in the treatment of 2-tricyclic inner tricyclic [5, 2.2 · 02, 6] decane produced by treating inner tricyclic [5.2, 2. 02'e] decane with organic peroxide (Japanese Patent No. 57-114539 Bulletin). Wei Li 9 "! | Γ \ ~ Binding IJ Washing-'V (Please read the precautions on the back before filling this page} This paper size applies to China National Standard (CNS) Λ4 specification (210 × 297 mm) 448 彳 3 7 Printed by A7 __B7___ of the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the Invention (ί) Using the aforementioned gasification of peroxide, the yield of the target compound is as low as about 20-50%. Furthermore, the aforementioned inner tricyclic [5 2.2.〇2 < s] decane as a derivative of dipentadiene is easily available (to be published in Gazette 5 1-3 6 7 48, Synth, Comm, 4, 225 (1974)). It is difficult to introduce hydroxyl groups into the tertiary carbon atoms of the junction portion adjacent to each other in polycyclic hydrocarbons easily and effectively in the cracking of the ring and by-product diketone. Furthermore, nitric acid or heavy chromium is used. A method in which a methyl compound is substituted with a serous compound (for example, methyl) and vaporized by an acid can be made into an aromatic compound having a carboxyl group (for example, benzoic acid). These methods have higher yields and can be used to prepare benzoic acid, etc. An aromatic compound having a carboxyl group. However, the nitric acid gasification method is the same as above. To generate N20 and H0X, expensive exhaust treatment facilities are required. The method using dichromic acid must also treat the chromium component. The method of producing benzoic acid by air gasification method is known, for example, using cobalt hexanoate A method for vaporizing toluene in a liquid phase, and a method for oxidizing toluene in a liquid phase in the presence of a catalyst made of cobalt manganese acetate and bromide, but a method using cobalt cyclohexaneate, its conversion rate and selection The rate is small, and it is difficult to produce benzoic acid with good efficiency. On the other hand, the method using cobalt manganese acetate can produce benzoic acid at a higher yield. However, this method must be anti-blind at a higher temperature (such as 150 ~ 250t: about). Under mild conditions, gasification with oxygen makes it difficult to produce corresponding carboxylic acids from methyl-substituted aromatic hydrocarbons, such as toluene, with high yields and good efficiency. In addition, other aromatic compounds, such as para-xylene air gas When the reaction is carried out in the presence of cobalt acetate and co-oxidant, at a lower temperature (90 ~ 160Ό -10- --------- r " Ϊ 装-(Please read the precautions on the back before filling this page ) Ding- ° paper size Consumption of tSfiJ Home Standard (CNS) Λ4 specification (210X297 gong) 4 48 ί 3.7 Α7 Β7 Printed by the Male Workers Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (1) About 1) 卽 Can produce terephthalic acid However, this method must not only use a large amount of 1 1 catalyst. Circulation > By-product acetic acid equivalent to terephthalic acid 〇1 I In addition »Synthetic resins such as polymamine maleic anhydride 9 Plasticizers, etc. 1 material can be used for butanediol 0 butylene glycol derived from butenediol * available first read 1 1 read I 1 in for example tetrahydrofuran 9 synthesis of butyrolactone, polyester or polyurethane 1 I raw materials 〇The former butylene glycol or butanediol * is produced by the Eeppe reaction. Note 1 1 The acetylene glycol i is produced by hydrogenation of the reduced Abb catalyst 0. Item 1 is another aspect » 1 Large amounts of butadiene are produced in petroleum refining steps Equal to 1 for 1 conjugated diene. Therefore * If it can be directly generated from conjugated diene such as butadiene, this page corresponds to ene diol such as butene diol »It is industrially useful. 0 From conjugated di ί 1 A method for producing alcohol * It is also possible to consider the use of nitric acid to chlorinate the conjugated diene, 1 1 to form a diol. 0, but 1 as described above, N produced by the gasification of nitric acid) 0 1 production 1 and NO X treatment r An expensive exhaust gas treatment facility is required. Therefore > From a resource and environmental point of view > Direct use of gas molecules or air as a gasifier 1 I Catalytic gasification method 9 Can produce oxalic acid with good efficiency Useful 〇1 1 Also uses oxygen or air as a gasifying agent for conjugated 1 compounds other than co-diene »» For example, a > β-unsaturated site line 1 oxidation is also effective 9 as long as it can Corresponding to good efficiency manufacturing Gas 1 This gasification method using oxygen can be extremely useful. I | However, oxidation using gas> Especially under mild conditions, oxygen is used to oxidize I | »Difficult to use from conjugate- * olefinic acrylic acid or its derivatives, etc. Conjugated compound 1 1 generates corresponding diols or their derivatives (1 I, such as ene glycol t acetal m, etc.) C 1 at the local selective rate and yield. 1994 < < Preliminary Lecture Series II > > page 1 1 762 reported that using vanadium molybdenum orthoate and N-hydroxyphthalimide, this benzyl t I 11 1 paper is again suitable for China National Standard (CNS) Α4 Specification (210 × 2 ~ 7 mm) IO / A7, __B7_ V. Description of the Invention (,. ) Alcohols, alcohols such as triphenylmethanol, can be oxidized with air to produce acetophenone, benzophenone, etc. in high yields. Using N-hydroxyphthalimide imine, Ryman, heterochromane adamantane, etc. Gas can be gasified to produce the corresponding monoalcohol or hydrazone. Therefore, an object of the present invention is to provide a gasification catalyst which does not require a special exhaust treatment and is oxidized with gas, so that the substrate can be gasified with good efficiency, and a chlorination method using the catalyst. It is a secondary object of the present invention to provide an oxide catalyst that can utilize gasification of gas molecules with high conversion and selectivity from substrates (璟 · 璟, 类, olefins, polycyclic hydrocarbons, alkyl substitution Aromatic compounds, conjugated compounds, etc.), corresponding vapors (ketones, alcohols, aldehydes, carboxylic acids, etc.) are generated, and the oxidation method of the catalyst and the method of producing the aforementioned vapors. Another object of the present invention is to provide an oxidation catalyst, which can be used directly and with good efficiency from the substrate (naphthenes, cycloolefins, alkyl-substituted aromatic compounds) by contacting with public gas under mild conditions. With high conversion and selectivity, corresponding carboxylic acids (such as adipic acid, long dicarboxylic acids, aromatic carboxylic acids), or ketones (cycloalkanones, cycloketenes, aromatic ketones), As well as the gasification method using this catalyst, there are the aforementioned methods for producing carboxylic acids or ketones. Yet another object of the present invention is to provide an oxidation catalyst capable of gasifying a methylene site at a bridgehead position or a junction position of a polycyclic hydrocarbon with good efficiency, and a gasification method using the catalyst. Another object of the present invention is to provide a gasification catalyst, which can be converted from -12- (please read the precautions on the back before filling in this page) This paper size applies the Chinese National Standard (CNS) Λ4 specification (210 > 2 / V. Explanation of the invention (Polycyclic hydrocarbons, the corresponding diols are cross-linked with cyclic hydrocarbons by A7 B7, with high conversion and selectivity, the production of polyhydric alcohols on the phase, and the oxidation method using this catalyst. The present invention Yet another object is to provide a gasification catalyst that can suppress the ring-opening and by-product diketone production of polyfluorinated hydrocarbons under mild conditions, while introducing tertiary carbon atoms with high efficiency to hydroxyl groups, and The method of bonding site. The present invention can obtain adamantane second exposure in mild strips _ the inventor's N-hydroxyphthalide _ using the substrate with chlorine, can also be vaporized, that is, the present invention and phosphorus vanadium molybdic acid step purpose, The purpose is to provide a method for producing a gold P alkane polyol. Under this condition, the oxidation of gas is used to produce alcohol and triol or higher adamantane polyol at an effective and high yield. For the above purpose, the results of intensive research have been found in Imine compounds and co-touch In the presence of the catalyst 糸, or when the air is gasified, even relatively mild conditions at atmospheric pressure are used for high-efficiency gasification, and the corresponding invention is completed with high selectivity and yield. The gasification catalyst set, Composition of auxiliary catalysts other than fluorene imine compounds represented by formula (1): — ^ 丨 ~ binding 'thread ·'. ... (please read the precautions on the back before filling this page) Central Bureau of Standards, Ministry of Economic Affairs Printed by Employee Consumer Cooperative

, R1NOC \, N-X (1) R2 wherein R1 and I-2 are the same or different, and are hydrogen atom, halogen atom, alkyl, aryl, cycloalkyl, hydroxyl, alkoxy, carboxyl, alkane Air-based succinyl, stilbene, 1? 1 and 1? 2 are combined with each other to form a double bond, and can also form aromatic or 13-paper iML skins applicable to national standards (CNS) Λ4 specifications (2I0X297 mm) 4 48 I 3 7 A7 B7 Member of the Central Standards Bureau of the Ministry of Economic Affairs 4 Consumption and Cooperation Du Zhonggan 5. Description of the Invention (U) Non-aromatic ring 0 X is an oxygen atom or a hydroxyl group, and η is an integer from 1 to 3. The bond between X and t is a tact 単 or double bond. The auxiliary catalyst contains an element selected from Group A of the Periodic Table 2 * Transition Metal t Group 3 of the Periodic Table. The imine compound (1) and the auxiliary catalyst constitute The gasification catalyst strip can be used to oxidize various substrates with good efficiency to generate ketones 9 aldehydes alcohols or carboxylic acids corresponding to the substrate. Therefore, the method of the present invention is based on the aforementioned imine compound (1) and auxiliary catalyst In the presence of an oxidation catalyst consisting of a catalyst, the substrate is brought into contact with the gas. The substrate is pseudo-selected g (a) naphthenes, (b) cycloolefins 9 (C 1) polymethylene containing a methylene ring. When the tati early position 9 is a polyfluorinated hydrocarbon other than adamantane * (dl) aromatic compound, the aromatic compound 7 (e) conjugated compound substituted with at least one alkyl group in the field, the front catalyst is not used. The substrate can be oxidized in the presence of a gasification catalyst composed of the sulfonium imine compound (1). In the coexistence of the aforementioned auxiliary / itsa catalyst (in the presence of an oxidation catalyst strip composed of the fluorene imine compound (1) and the auxiliary catalyst), when the substrate is gasified with oxygen, the f substrate has Aromatic compounds with hydroxyl groups, and the auxiliary catalyst is non-phosphorus molybdic acid *. The auxiliary catalyst is a polyacid (heteropolyacid, isopolyacid) composed of elements of Group 5A or Group 6A of the periodic table. More acid. The matrix is (a) pinanes, (b) cycloolefins > (C 1) polycyclic hydrocarbons other than diamond complexes > (d 1) at least _- alkyl substituted aromatic compounds, (e ) Conjugated compounds > -ϋ Heteropolyacid 4 The phosphorus vanadium molybdenum hafnium may also be used. That is to say, in this case, 9 co-irtnt catalysts can be selected from white oxides, organic acid salts, inorganic acid salts, halogenated hafnium complexes, heteropolyacids or salts thereof, and at least-species of heteropolyacids or salts. Paper size applies Chinese National Standard (CNS) A4 specification (2I0X297 mm) A7 B7 Economy, printed by Deng Central Bureau of Standards Consumer Consumption Cooperative V. Description of invention (t each) 1 i In the preferred oxidation method, t auxiliary catalyst contains White Periodic Group 2A > I 1 I Tojin 靥 j and Periodic Table 3B Group Element Compounds t Use White Oxidation! 1 Item) Organic acid salt 9 Inorganic acid salt halide 1 Complex 9 Heteropoly Acid or please! First 1 of its salt compound 0 Read 1 The present invention is shown in the aforementioned M imine compound (oxidation catalyst consisting of η © 1 I 1 * or ϋ imine compound (1) and auxiliary catalyst Oxidation Presence of mediators 1 things 1 down 1 gasification of the aforementioned substrates »methods for producing ketones, alcohols m or carboxylic acids and then 4 types. Again * the present invention is intended to be used. 1 Description of imidization A Ct (1) Gasification catalyst V formed by filling the container or using the imine compound (1) and auxiliary catalyst! I constitute the gasification m medium strip) oxidizing the substrate 0 1 1 In the present invention In the description, the carboxylic acid J is not limited to having a free carboxyl group α 1 1 物 1 Depending on the reaction conditions, the salt ester or alcohol is substantially contained with carboxylic acid, | Inner 〇 1 In addition, the diamond compound and its derivatives are sometimes called 0ΓΤ. The adamantane component J 〇 1 f was previously called and the methylene group at the bridgehead position of polyalkylenes was C -HC < The covalent methylene group is C > CH-CH <). The metal compound J 1 contains the transition metal compound line I generated in the reaction bar. Furthermore, »plant acrylic acid i methacrylic acid or its derivative J» Sometimes collectively referred to as plant 1 (meth) acrylic acid or its derivative J 〇 Another plant conjugate Compound J Unlimited 1 1 Compounds with double and ao 単 bonds in alternate positions (such as butadiene, etc.) »Not even 1 I Saturated bonds (double and triple bonds) Compound 1 with or without early bonds in alternate positions I (examples) conjugated polyenes, etc. are also included. Therefore, t unsaturated diols are not only early under the limitation of the corresponding gaseous phase of the Γ 1 1 conjugated diene j-double bonds 9 and 1 have multiple double bonds Or double bond unsaturated diols > also m is called olefenediol ". 1 i 1 15 1 1 1 1 This paper size is applicable to Chinese National Standard (CNS) Λ4 specification_: ^ 7 public 漦) 448] 3 7 A 7 ,, ___B7_ V. Description of the invention (14) Implementation _. Issued _ Ming. Alcohol_JT Sub-Compound_ In the compound represented by the above formula (1), the halogen atoms of the substituents R1 and R2 include iodine, bromine, nitrogen, and fluorine atoms. Alkyl includes, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second-butyl, third-butyl, pentyl, hexyl, heptyl, octyl, decyl, and the like Number of straight or branched alkyl groups from 1 to 10. The preferred alkyl group is, for example, about Ci-Ce, and especially a lower-grade group of Ci_C4. Aryl includes phenyl, naphthyl, and the like, and cycloalkyl includes cyclopentyl, cyclohexyl, cyclooctyl, and the like. Alkyl groups include, for example, methylamino, ethoxy, propane, isopropyl, butoxy, isobutyl, tertiary-butoxy, pentyl, and hexyl. The low-grade courtyard gas bases around) are about Cl -Ce, and about Cl -C4 is the best. Examples of the alkanesulfonyl group include methoxysulfonyl, ethoxysulfonyl, propanylsulfonyl, isopropoxysulfonyl, butoxycarbamoyl, isobutylcarbamoyl The radicals such as sulfonyl, tert-butanylsulfonyl, pentanylsulfonyl, and hexylthiol are alcohol radicals around Cl10. The preferred alkane-based sulfonyl group contains about alkoxy groups, which is about Cl ·, especially printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) refers to C; 1 _C4 Low-level hospital gas-based carbon transport base. The fluorenyl group includes, for example, a fluorenyl group of about Cl-c6 such as a methylfluorenyl group, a methylfluorenyl group, an ethylfluorenyl group, a propylfluorenyl group, a butylfluorenyl group, an isobutylfluorenyl group, a pentylfluorenyl group, an isoamyl ester group, or a pentafluorenyl group. The aforementioned substituents R1 and R2 are the same or different. In the aforementioned formula (1), R1 and R2 can also be combined with each other to form a double bond, and aromatic or non-aromatic-1 6-This paper size is applicable to the Chinese National Standard (CNS) Λ4 specification (2 丨 OX "7 mm} 448! 3 A7 B7 V. Description of the invention (β) is more. At this time, the cyclic hydrocarbons and I 5 are as follows, and the ring-ring heteroaromatic compound is aromatic or non-ring-like heteroaromatic is aromatic, which is better. Group 10 cyclist 2 1 refers to the cyclohexene group hexacyclic cycloaliphatic ring, which is fragrant and fragrant, such as the cyclic ring alkyl group which has a fluorene ring and the like. Substitute the ring-based group, substitute incense, take the aromatic ring-based alkenyl group, take the original ring such as ice, etc. 5 Cai You / with ring «! $ 结构 包 彳 δ㈣ RING RING R with 璟 family connection), Xianghuaqiao and other aromatic The amine and sex ring are sub-0 ^ hydrocarbon ring 醯 y scent of good R1 is less bridged before the aromatic connection. R2

CM o b (Please read the notes on the back before filling this page)

R6 R6 ^ Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, Chinese-style base gas alkane to base 3 Junzi original element hydroxy group Binder X Aldehyde 0 Oxyalkyl Gas

Lean with η D means ~ 1 C, especially 3 R means, kiewyl, the same as the alkane, and the examples of the alkane are described above and the same as the alkane-containing alkane. Bakelite-based gas-air alkane grade, -low-base alkane right and left 4 'C left-This paper size applies to China National Standard (CNS) Α4 size (2IO × 297 mm) 4 A7 B7 Zhengong, Central Bureau of Standards, Ministry of Economic Affairs Printed by a consumer cooperative. 5. Description of the invention. (4) The i I group contains the same alkane group as described above. 4 The low-grade compound gas base, especially the oxygen part of the compound, is C ϊ-C 4 1 1. For example, there are the same fluorenyl groups 1 1 9 as described above, and especially fluorenyl groups of about CL to C 3, and the halogen atom includes, for example, fluorine, gas, 谙 J, and 1 bromine atom. Substituents R 3 to R 6 are usually mostly hydrogen atoms. 9 C ϊ-C 4 It reads about 1 1 lower alkyl S carboxyl, nitro) halogen atom. In the formula (1) above, X represents an oxygen atom or a hydroxyl group, and the nitrogen atom N is bound to X. Note that 1 1 is a dct bond or double bond. 0ϋ is usually about 1 ~ 3. 1 or 2 is preferred. Item 1 1 The compound represented by the formula (1) may be used alone or in combination of two or more in the gasification reaction. 1 l · ··················································· ······························································································ Saturated or unsaturated non-aromatic fluorinated polyhydric compounds such as hydrophthalic anhydride (1,2-fluorenehexanedicarboxylic anhydride), 1, 2,3, 4-cyclohexanetetra-1 1 carboxylic acid-1, 2-anhydride Carboxylic anhydride (lipids! Polycyclic carboxylic anhydride), nitro acid (HET ac id anhydride), 1 g of anhydride (H i in Ϊ C aci dian anhydride), etc. bridge 璟 polycarboxylic anhydride (lip I i ring Family of polycarboxylic anhydride), phthalic anhydride, tetrahydrophthalocyanine, tetrachlorophthalic anhydride, ugly! [Anhydride trimellitic anhydride, methylhexenetricarboxylic anhydride, pyromellitic anhydride hexahexa anhydride 1 1 1, 8; 4, 5 ~ Cetricarboxylic dianhydride and other aromatic polycarboxylic anhydrides. I. Preferred fluorene compounds are, for example, N-hydroxysuccinimide 9 N ™ hydroxyl | maleimide Λ N-hydroxyhexahydrophthalimide, N, N '-dihydroxycyclohexane 1! Tetracarboximide Λ N-Hydroxyphthalimide, H-Hydroxytetrabromide Sfe Phenimine 1 i, N-Hydroxytetrachlorophthalimide, N-Hydroxychloropeptamine, N-Hydroxylamine 1 r Mick m PDO. Imine N Η-hydroxytrimethyleneimine, N, Η dihydroxybenzene all [1 tetramethylimine N, Ν '-dihydroxynaphthalene tetramethylimine, etc. Special compound package 1 I alicyclic polycarboxylic anhydride, especially aromatic polycarboxylic carboxylic acid derived N- 1 1 -18 1 1 1 1 This paper adopts Chinese solid standard {CNS) M specifications (2) 0 × 297 male 逄) 4 48 丨 3 A7. B7 V. Description of the invention (Sichuan) Hydroxyl hydrazone imine compound, such as N-hydroxyphthalimide amine and the like. The aforementioned sulfonium imine compound can be reacted with a conventional aldimination, for example, by reacting a relative anhydride with hydroxylamine NH2 0H, ring-opening the anhydride group, and then closing the sulfonium imine. These sulfonium imine compounds have high oxidation activity, so that under mild conditions, they can also catalytically promote the oxidation reaction of the substrate to be determined. Furthermore, when various substrates are gasified in the coexistence of the aforementioned sulfonium imine compound and a cocatalyst, the conversion rate and / or the selectivity can be improved. Therefore, in the present invention, the substrate is determined, and oxidized in the presence of an oxidation catalyst composed of a preammine compound to generate ketones, alcohols, aldehydes or carboxylic acids corresponding to the substrate. In addition, the present invention can oxidize the substrate with good efficiency and high selectivity in the presence of the catalyst 糸 composed of the aforementioned 醯 imine compound 檄 and auxiliary catalyst, and generate _-types, alcohols, aldehydes or Carboxylic acids. Auxiliary base as cocatalyst co-gasifier, containing metal compounds, for example, containing elements of group 2A of the periodic table (magnesium, calcium, strontium, barium, etc.), transition metals, boron compounds and other elements of group 3B of the periodic table (boron B , Aluminum A1, etc.). The auxiliary catalyst may be used singly or in combination of two or more kinds. Printed by the Shell Standard Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the notes on the back before filling out this page). The aforementioned transition metal elements include, for example, Group 3A of the periodic table (for example, ytterbium Sc, yttrium Y, lanthanum La, ytterbium Ce, 钐 381 and other _ 糸 elements, copper Ac and other copper bar elements), group 4A of the periodic table (titanium Ti, W Zr, 铪 Hf, etc.). Group 5A elements (vanadium V, niobium Nb, giant Ta, etc.), group 6A elements (chromium Cr, aluminum Mo, tungsten W, etc.), group 7A elements (manganese Mn, Tc, rhenium, etc.), group 8 elements (iron Fe, Ru, Ru, Qs, Co, Co, 姥 Ph, Ir, Ni, Ni-1, 9- This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) 448] 3 A7 B7 Central Ministry of Economic Affairs Printed by the Bureau of Consumers of the Bureau of Standards, Du printed 5. Invention Description (iS) 1 1 Pd. Platinum Pt, etc.), 1 Group B element < Copper Cu u Silver Ag Gold Au, etc.) 2 Group B element 1 1 (zinc τ, η · Cadmium (Cd, etc.) etc. 〇1 1 The elements that make up the better auxiliary catalyst include >. ϊΐϊΐ Transition metal elements (for example, _ please 1 first f% element, copper bar element and other periodic table 3A group elements 4 price group elements, 5A group Read 1 element * 6 Group A element »7ί Group element 8 Group element * 1 Group B element, 2B Back 1 | Group 1 element), Group 3B element boride A α species etc. 0 Especially with the aforementioned formula (1) Note 1 Filial 1 In the case of a combination of fluorene imine compounds, t contains Group 4A elements such as Ti and Zr, items such as V-S-λ5 Group A elements, β group elements such as Cr, Μ0, and W * Μη »Tc t Re, etc. Fill in this text for Group 7A | Elements »Fe, Ru y Co Ph > Ν i and other Group 8 elements Cu and other Group B elements Page 1 I compounds, showing high oxidation activity 〇1 1 m Catalyst as long as it contains the aforementioned element t and It only needs to have the gasification ability, there is no special 1 1 no limitation, it can be a metal m body »I, such as a hydrogen compound, is usually mostly a metal gas (regasified or oxy acid salt) containing the first order element Λ organic acid Salt 1 An inorganic acid salt or a halide complex compound (1 1 complex) containing the aforementioned gold element, or a heteropolyacid (especially an isopolyacid) or a salt thereof. In addition, the gasification catalyst strip composed of the sulfonium imine compound represented by the formula (1) described in the previous Section I is except for compounds containing Group 5A and Group 6A elements of the periodic table, except for »phosphorus vanadium molybdic acid. Μ | Boron compounds include, for example, boron hydride (eg, borane, diborane, butyl borane 1 院 * * pentyl borane > decane borane, etc.) 'boric acid (orthoboric acid * metaboric acid, tetraboric acid 1 1 etc.) , Borates (such as nickel borate ♦ boric acid m * manganese borate, etc.) r B 2 〇3 1 | etc. boron gasification, boron ammonia institute »boron Mene 9 boroaminoalkyne» boramine, 1 amine, etc. Nitrogen compounds * BF 3 BC 1 3 i, halides such as tetrafluoroborane salts, boron 1 1 acid esters (such as methyl borate, stearic acid borate, etc.) etc. Preferred boron compounds are 1 1 boron gaseous boron, orthoboric acid Isoboric acid or its salt t, especially those containing boric acid. These 1 1 20 1 1 I 1 This paper size is applicable to China National Standards (CNS) Λ4 specifications (2 丨. :: 9, public money) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 48137 A7 '. __B7__ V. Description of the Invention (i?) One or more auxiliary catalysts can be used. The hydroxides include, for example, Mn (OH) 2, MnO (OH), Fe (OH) 2, Fe (OH), and the like. The metal oxide includes, for example, Sm2 03, TiO 2. Zr02, V203 s V 2 0sn CrO, C r 2 0as Η o 0 as Mn 0 s Mn n 3 0 4, Η n 2 0;, Mn 0 2 Η n 2 〇7, FeO, F θ 2 〇3, F ea 0 4, R110 2,

RuO 4. Co0, CoO 2, C 0 2 0 a, EhO 2, E h 2 0 3, Cu 2 0 3, etc. The complex oxide or metal acid salt is MnAl2 04, HnTiD3, La a M η 0 3, K 2 Η η 2 〇5, C a 0 · x Μ η 0 2 (x = 0.5, 1,2,3,5), manganates [for example, Na3Mn04, Ba3 [04π04] 2 and other manganese (V) acid salts , K 2 M n0 4, Na 2 MnO 4, BaMn04 and other manganese (VI) acid salts, KMn04, Ka Η n 0 4, Li Η η 0 4, N Η 4 Η n 0 4, C s Mn n 0 4, A g Η n 0 4, C a {Μ n 0 4) 2, Zn (K n 0 4) 2 5 Ba (HnO 4) 2, H g (Η n 0 4) 2,

Cd (Mn04) 2 and other permanganates]. Organic acid salts include C 2 -C 2 fatty acid salts such as cobalt acetate, manganese acetate, cobalt propionate, manganese propionate, cobalt naphthenate, manganese naphthenate, cobalt stearate, manganese stearate, and sulfur nitrogen Manganese acid, or relative Ce salt, Ti salt, Zr salt, V salt,

Cr salt, Mo salt, Fe salt, Ru salt, Ni salt, Pd salt, Cu salt, Zn salt, etc. The inorganic acid salts include nitrates such as cobalt nitrate, thorium nitrate, manganese nitrate, nickel nickel, copper nitrate, or It corresponds to sulfates, phosphates, and carbonates (such as cobalt sulfate, iron sulfate, manganese sulfate, cobalt phosphate, iron phosphate, manganese phosphate, iron carbonate, manganese carbonate, iron perchlorate, etc.), and the surface compounds have examples of $ 0 S si C 1 a, S m I 2, T i C 1 2, Z r C 1 2, Z r 0 C 1 2, VC 1 3, VO C1 2, MnC1 2, Η n C1 3, F e C1 2 , F e C1 3, Ru C1 3,

Co C1 2, R hC 1 2, RhC1 3, Ni C1 2, P d C1 2, P t C1 2, -2 1-Recognition of this paper, 囡 家家 准 {CNS) 规格 4 specification (210X297 public torch) ( Please read the precautions on the back before filling in this page)-Packing. Order 448 A7 B7 V. Description of the invention (w) C u C 1, C u C 1 2 and other gasification, corresponding fluorides, bromides Or iodide (such as HnF2, HnBr2, MnF3, FeF3, FeBr2, FeBr3, FeI2, CuBr, CuBr2, etc., M1 Η n C1 3, M Table HnCl4, Hi MnCl5, M2 Complex halides such as MnCl6 (M1 represents a monovalent metal), etc. The complexes that form the complex include OH (hydroxyl), methylamino, ethyloxy, propoxy, butoxy, alkoxy, etc. Sulfonyl groups such as methyl, propionyl, alkanesulfonyl groups such as methylsulfonyl alcohol (acetate), ethoxycarbamyl, halogens such as ethynylpyruvate, ethylpentadienyl, chlorine, and bromine Atoms, CO, CN, oxygen atoms, osmium 2 0 (water), phosphorus compounds such as phosphines (such as triarylphosphine such as triphenylphosphonium), N Η 3 (ammonia), Ν 0, Ν 0 2 (nitro), Ν 0 3 (nitrate), ethylenediamine, diethylenetriamine, pyridine, Nitrogen-containing compounds such as azaphenanthrene. In the complex or salt, the same or different ligands can be coordinated by one or two or more. Most of the ligands are, for example, 0Η, alkane, carbyl, and alkane. Base, ethenylpyruvate, halogen atom, phosphorus compounds such as CO, CN, thorium 20 (water), triphenylphosphonium, or nitrogen-containing compounds containing νη3, νο3. Please read the notes on the back before filling in this page.) Anterior transition metal elements can be combined with ligands to form complexes, such as ethylpyruvate complexes (ce, S IB, T i, Z I ·, V, C r, Mo, Mn, Fe, Ru, Co, Ni, Cu, Zn and other ethanoylpyruvate complexes, or titanium titanylacetamidopyruvate complexes TiO (AA) 2 , Oxylated ethylacetamidate propionate complex ZrO (AA > 2, Vanadium acetamidopyruvate complex V0 (AA) 2, etc.), fluorenyl complex (hexafluorenyl manganese) (I) acid salt, hexafluoro iron (II) acid salt, etc.), sulfofluorenyl complex or cyclopentadienyl complex (tricarbofluorenylcyclopentadienylmanganese (I), dicyclopentyl Dienyl-11- This paper is of suitable size Use Chinese National Standard (CNS) Λ4 specification (210X297 Gongao)

44b I A7 B7 Printed by the Central Bureau of Standards of the Ministry of Economic Affairs and Consumer Cooperatives. V. Description of the Invention-1) II Manganese (II) 9 Bispentadienyl iron (II) Fe (C 〇), F e (C0) C ) »IIF e 3 (C 〇) VI, etc.), nitrosino compounds (Fe (N 0) 4 9 F e (C0) 2 I 1 (N 0) 2 etc.), thiocyanate complexes (Tu delta thiophosphonate complex, please! Manganese thio% acid complex, iron thiophosphonate complex, etc.), ethanoyl complexes. Read I 1 read 1 t (acetic acid salt, manganese acetate, iron acetate , Copper acetate, oxygen acetate Zr 0 (〇AC) 2 on the back I 1 titanium titanate 1} T i 0 (0 AC) 2 acetic acid VO (OAc) 2 etc.) etc. Polyacids (isopolyacids or heteropolyacids) Mostly, for example, Group 5 A or Group 6 A of the Periodic Table 1 Re- primes such as V (vanadate), Η 〇 (button acid) or ft (tungstic acid) at least-species Fill 1 atom in Sn heart without any restrictions, for example Cu 9 JB e, B ί A1 Si, Ge 9 Written on this page IT i Ϊ Th Ν, P, As, S b, V, N b, T a, C r, Μ 〇, W 9 S, S e 1 1 Te Η η 9 I, F e, C 〇, Ni, Rh, 0 s, Ir, P t, CU, etc. 1 I specific examples of heteropoly acids include, for example, cobalt molybdate) Cobalt Mirror * Molybdic acid 1 salt »Bimolybdate, Tungstate 4 Manganese molybdate phosphonate vanadium molybdate > 1 but 1 manganese m molybdate 9 manganese molybdate etc. as described above * in This invention constitutes the invention. 1! Among the auxiliary catalysts with an oxidation catalyst% of the preferred »polyacids preferred are isopolyacids» 1 1 heteropolyacids (phosphovanadium macroacids) or salts thereof of molybdenum strips are excluded. The type of the medium of the media can be acr military alone or two or more of them can be used in combination. I 7 The type of the auxiliary catalyst 9 exhibits the following characteristic functions, for example: 0 1 I 1. The atom of the 7 element in the transition metal compound constituting the auxiliary catalyst 1 shell without 1 1 special restrictions 9 2 ~ 6 can be priced around 7 Using a divalent transition metal compound I 1 (such as a divalent cobalt compound, a divalent manganese compound, etc.) as the auxiliary catalyst 9 can improve 1 1 high oxidation activity. 0 For example, the divalent transition metal compound is changed to a divalent transition metal 1 I, which is a compound 9 A catalyst strip composed of the aforementioned m imine compound »can be used to derive oxidation reaction products in a short time and with a high selectivity and yield 〇 In addition 1 1 2 3 I 1 i This paper size applies Chinese national standards ( CNS) Λ4 specification (2) 0 × 297 mm) 448137 A7 B7 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (> >), using divalent transition gold rattan compounds (such as divalent periodic table containing cobalt etc. When the compound of Group 8 element) is used as the auxiliary catalyst, the substrate (such as methyl-substituted aromatic compounds) can also be used at low temperature (for example, 10 ~ 60), especially at room temperature (about 15-30Ϊ). ) Quantitative oxidation to generate corresponding oxides (such as carboxylic acids, etc.). 2. When using a compound containing at least one element of Group 4A (Ti, Zr, etc.), Group 6A (C ", Mo, etc.) and Group 7A (Mη, etc.) of the periodic table as auxiliary catalysts, use reaction conditions to borrow Cool, can also greatly inhibit the inactivation of catalysts (especially amidine compounds). Therefore, industrially advantageous substrates can be hydrogenated with air or hydrogenated with hydrogen. 3. Use of elements containing group 4A of the periodic table (Ti, Zr Etc.), compounds of Group 5A elements (V, etc.), Group 6A elements (Cr, 40, etc.), Group 7A elements (Mη, etc.), and Group 8 elements (Fe, Co, etc.) can be greatly used as auxiliary catalysts. Improve gasification activity and effectively gasify the substrate. For example, compounds containing Periodic Table Group 5A elements (V, etc.), Periodic Table Group 7A elements (MN, etc.) or Periodic Table Group 8 elements (Co, etc.) as auxiliary catalysts Catalyst rhenium, high activity. In addition, the catalyst strips containing compounds of Group 7A elements (Mη, etc.) or Group 8 elements (Fe, etc.) of the periodic table as auxiliary catalysts have high activity on the substrate (such as pinanes). Activity, can generate corresponding gaseous compounds (such as ketones or dicarboxylic acids) with a high selectivity. In particular, it contains Group 5A of the periodic table. When a compound such as vanadium (vanadium) is used as a co-catalyst, it is possible to vaporize a plurality of sites [bridge head positions or junction positions of polycyclic hydrocarbons (adamantane, etc.)] with good efficiency, thereby obtaining a product having multiple hydroxyl groups ( For example, adamantane 7 Π S ?, etc.) 4. M imine compound represented by formula (1) and containing Group B elements of the Periodic Table 1 (C υ -24- Mu Zhi Le scales are applicable to Chinese standards (CNS) Λ 4 Specifications (210X 297 mm) --------- Cloths ------ 1T ------- 0 (Please read the precautions on the back before filling this page) 4 4 8 | 3 7. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of Invention (w) etc.) When the auxiliary catalyst combination constitutes an oxidation catalyst, it can greatly increase the selectivity in the gasification reaction, and at the same time in the industry It is advantageous to suppress the deactivation of the fluorene imine compound. 5. The fluorene imine compound represented by the formula (ii) and the compound containing a group 7A element (manganese compound, etc.) of the periodic table, and the compound containing a group 8 element of the periodic table (iron compound) Etc.), when forming a gasification catalyst strip, the catalyst activity can be improved to improve the conversion rate and selectivity. It is effective and good There is no particular limitation on the proportion of compounds containing Group 8 elements of the Periodic Table (second auxiliary catalyst) in this composite catalyst strip, for example, relative to compounds containing Group 7A elements of the Periodic Table (the first auxiliary Catalyst) 1 mole, most of which are 0.1 to 25 moles (for example, 0.1 to 20 moles), preferably 0.2 to 15 moles, and more preferably about 0.5 to 10 moles. The gasification catalyst or the gasification catalyst composed of the rhenium imine compound and the auxiliary catalyst is homogeneous or non-uniform. The gasification catalyst or the gasification catalyst strip may be in the carrier. A solid catalyst made of catalyst components. The carriers are mostly porous carriers such as activated carbon, zeolite, vaporized silicon, vaporized silicon_gasified aluminum, bentonite and the like. The loading of the catalyst component in the solid catalyst is 0.1 to 50 parts by weight relative to 100 parts by weight of the carrier, preferably 0.5 to 30 parts by weight, and more preferably 0.5 to 25 parts by weight, and 1 to 2 About 0 parts by weight is best. The ratio of the auxiliary catalyst to the fluorene imine compound shown in Table U) can be selected within the range of non-destructive reaction speed and selectivity. For example, the catalyst is 0,001 ~ 10 mol relative to the fluorene imine compound. 0.005 ~ 5 moles is preferred, and about 0,01 ~ 3 moles is best, most of which are 0.01 ~ 5 moles—2 5 _ This paper size is applicable to China National Standard (CNS) Λ4 specification (210 × 297 mm)- ------- 7 " ..ί Install ------ Order ------ 'line (Please read the precautions on the back before filling this page) a 8 13 7 A7., __ B7 V. Description of the invention (> 4) Around ears (especially from 0.00 to 1 mole). Moreover, as the amount of the auxiliary catalyst increases, the activity of the fluorene imine compound decreases. Therefore, for the high activity of the hybrid oxidation catalyst plutonium, the ratio of the auxiliary catalyst is more than the effective amount to less than 0.1 mol relative to 1 mol of the imine compound, for example, 0.001 to 0.1 mol, and 0.005 to 0.08. Mol is better, and about 0.01 to 0.07 mole is even better. In the gasification reaction (in other words, the production method of _, alcohols, aldehydes or alcohols), the amount of the imine compound shown in the foregoing formula (ii) can be selected in a wide range, for example, relative to the substrate 1 Molar, 0.001 ~ 1 Molar (0.1 ~ 100 Molar%), preferably 0.001 ~ 0.5 Molar (0.1 ~ 50 Molar%), and more preferably about 0,0 1 ~ 0.30 Molar, mostly It is about 0.01 to 0.25 mol. The amount of the auxiliary catalyst (co-gasifier) can be appropriately selected within the range that does not reduce the reactivity and selectivity, for example, it is equivalent to 1 mol of the substrate, 0.0001 mol (0.01 mol%) to 0.7 mol. The ear (70 mol%) is preferably 0.0001 to 0.5 mol, and more preferably about 0.001 to 0.3 mol, and in most cases, it is about 0.0005 to 0.1 mol (for example, 0.005 to 0.1 mol). When a polyacid (isopolyacid or heteropolyacid) or a salt thereof is used as a co-catalyst, it is 0.1 to 2 to 5 parts by weight, and 0.5 to 10 parts by weight relative to 100 parts by weight of the substrate. It is better, and about 1 to 5 parts by weight is better. Base. Quality __ Using the aforementioned gasification catalyst composed of the sulfonium imine compound, or the gasification catalyst strip composed of the sulfonium imine compound and the auxiliary catalyst, the various substrates can be effectively -26- 1 n--n I _ 1.- II 1— _ I__1 _ TI. ^ 1 i- __ i — Elephant. -Iw (Please read the notes on the back before filling out this page) Printed on paper This paper is applicable to the standard printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Chinese National Standard (CNS) ί, 210X297 mm 4 48 137 A7. B7 V. Description of the invention (K) (Please read the notes on the back before filling this page), can generate ketones corresponding to the matrix, Alcohols, aldehydes, carboxylic acids, etc. There are no restrictions on the type of substrate, and a wide range of saturated or unsaturated compounds can be used, such as hydrocarbons (aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic smokes), heterocyclic compounds, alcohols, ethers, and esters , Ketones, aldehydes, amines, etc. Depending on the type, these substrates can have various substituents, such as halogen atoms (iodine, bromine, gas, and fluorine atoms), alkyl groups (such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, Ci-CE, such as butyl, tert-butyl, and hexyl, or straight or branched mirror alkyl, especially lower alkyl, left and right, gas, hydroxyl, and alkyl (such as methyl, ethyl, and propyl) Ci-Cs, such as alkyl, isopropoxy, butoxy, isobutoxy, tert-butoxy, and hexyloxy, especially lower alkanoyl groups around Ci-C4), hydroxyalkyl (such as hydroxy Hydroxyl CX-C4 alkyl such as methyl, 2-hydroxyethyl, etc.), carboxyl, alkane carbon (such as methoxycarbaldehyde, ethanesulfamoyl, propanecarbamyl, isopropylsulfonium The number of alkane groups such as sulfonyl, butoxysulfonyl, isobutoxysulfonyl, tert-butoxysulfonyl and hexylcarbamyl is about 1 to 6, especially lower alkane of about 1 to 4. Oxyfluorenyl), fluorenyl (such as methylamyl, ethylamyl, propionyl, butyraldehyde, isobutyryl, pentamyl, isoamyl, tamyl, etc.), town economy Central Bureau of Standards Co-op printing station group, a substituted amino group, a cyano group, a nitro group and the like. Preferred substrates include, for example, compounds which are industrially useful. (a) Examples of pinane-type naphthenes include 3 to 3 G-section naphthenic ring compounds, for example, propane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane , Cyclodecane, cycloundecane, cyclododecane, cyclotridecane, octadecane, -27- 夂 Kan recognized standards are applicable to China® Home Standard (CNS) 8 4 specifications (210X297 cm) 4 4 8 I 3 7 A7 B7 Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs ^ V. Description of the invention () 1 1 Ring 15th House 璟 Decane Ring 18th House, Cyclodecane 18th, Ring 20 House 1 I Ring 2 Dodecanecyclotetracosane > Cyclotrisene etc. 1 1 The pinanes having a substituent include, for example, a cyclic compound having a hydroxyl group (1) Alcohol, cyclooctanol, decyl alcohol, cyclodecyl alcohol, cyclododecyl alcohol, cyclic cycloditol. 1 , Octadecanol, etc.), cycloalkanes with cyclooxyl (cyclopentane m ring back 1 1 hexanone methyl cyclohexanone N dimethyl cyclohexanone, cyclohexadione, m heptone Note 1 I Octanone, cyclooctanedion, cyclononanone, cyclodecanone, cycloundecanone, matters again 1 cyclododecane ketone cyclotetradecanone, cyclooctadecane ketone, cycloicocosone ketone) Gu. 1 Pack ♦ Cycloalkanes with academic bases (methylcyclohexane, 1,2-dimethylpentane · court, page V «· 1 I isopropyl hexamethylene methyloctane, etc.), etc. . 1 I is better. It contains 5 to 30 knots, especially 6 to 25 knots. Among them, 1 1 to 6 to 20 knots (such as 6 λ -1 to 6 knots) are the most. 1 Order another 8-node ring or more according to the method of the present invention (for example, 8 30-node ring) 1 > preferably 8--2 5-node ring, especially 8 to 20-node ring which is industrially useful (for example, 1 1 8 ~ 16 Section 璟) Compounds »Also effective oxidation 〇1 | Gasification catalyst composed of the aforementioned 醯 imine compound (1), or 醯 imine 1 compound (1) and auxiliary catalyst 糸In the presence of these, these naphthenes have risen | Gas can be used for gasification t Even under normal calendar air or gas atmosphere • It is also possible to 1 1 ί The corresponding dicarboxylic acid or alkane is mainly generated with a conversion rate and selectivity of 1 1 Ketones 〇1 I, such as »Gasification of cyclohexane or its derivatives (cyclohexanone or cyclohexanol, etc.) with 1 1 Γ can generate conversion and selectivity of amaranth with good efficiency to produce adipic acid. 1 1 For the matrix of adipic acid (congener ring C 6 compound), cyclohexane 1 I alkanecyclohexanol can be used. The matrix can be used in cyclohexane, cyclohexanol and cyclohexane 1 1 28- 1 1 1 1 This scale is applicable to the Chinese National Standard (CNS) Λ4 specification (210X297 mm) 448137 A7 B7 5. Description of the Invention (Clever) At least one component of _, but it can also be used in combination of two or more. In addition, cyclohexane alone can also generate adipic acid with high conversion or selectivity, but in the presence of cyclohexanol or cyclohexanone in the cyclohexane gasification, cyclohexane is gasified while cyclohexane is being evaporated. When alcohol or panhexanone is vaporized, the conversion and selectivity can be further improved. When the cyclohexane or its derivative is gasified by the aforementioned gasification method, not only the reaction temperature and / or the reaction pressure are increased under mild conditions, but the by-products are hardly formed when the reaction speed is accelerated, and the products are almost uniform. It is adipic acid. Therefore, the separation and purification of adipic acid is extremely simple and easy to perform, and is extremely useful for the production of adipic acid such as nylon 6, 6, polyester, or plasticizer. Printed by the Central Standards Bureau of the Ministry of Economic Affairs and Consumer Cooperatives (please read the precautions on the back before filling out this page). In addition, when using the aforementioned gasification catalyst or gasification catalyst strip, even 8 sections with less reactivity to oxidation Above, especially large cyclic naphthenes with more than 9 knots (for example, naphthenes with 10 to 30 knots), the reactivity to gas will be greatly increased, which can be efficiently gasified and can be obtained in high yield. Fermentation (especially monoketone) or carboxylic acids. That is, in the method of the present invention, under mild conditions, the macrocyclic naphthenes can be oxidized with high conversion and selectivity to obtain ketones or carboxylic acids (especially macrocyclic fluorenone and long-chain dicarboxylic acids). ). For example, when cyclooctane is gasified, cyclooctanoic acid ketone or suberic acid can be generated, and when 9 or more oxanes are gasified in contact with gas, corresponding cycloalkanone or long-chain dicarboxylic acid can be generated. In addition to monoketone bodies as precursors of dicarboxylic acids, they also act as raw materials for lactams. In addition, the monoketone body is converted into a carboxylic acid as the oxidation reaction proceeds. Therefore, polyesters, polyamines, or plasticizers with Cs or more antimony dicarboxylic acid or its precursor monoketone compounds are extremely useful in manufacturing > -29- This paper is applicable in the national standard. (CNS ';. \ 4This pile (210X297 public acid) The central government bureau of the Ministry of Economic Affairs consumes printed bags of cooperatives ^ 48137 A7 B7 V. Description of the invention (β) When the substrate is naphthenes, the special auxiliary catalyst is It is composed of a compound containing at least Group 7A elements (Mη, etc.) of the periodic table. In addition, an effective auxiliary catalyst may be composed of a compound containing Group 7A elements (Mn, etc.) of the periodic table and a compound containing Group 8 elements (Fe, etc.) of the periodic table. In addition, when a divalent transition metal compound (such as a divalent cobalt compound or a manganese compound) is used as the auxiliary catalyst, it is possible to greatly suppress the production of dioxin by-products such as cyclooctane, and significantly increase the naphthene. Selectivity and yield of ketones (such as cyclooctanone), especially dicarboxylic acids (such as suberic acid). (B) _Cyclocyclic cycloolefins have 3 ~; E.g. cycloolefins (e.g. cyclopropene, cyclobutene, pinene, pinohexene, 1-methyl-1-ring Ene, isophorone, cycloheptene, cyclooctene, cyclononene, cyclodecene, cycloundecene, cyclododecene, etc.), cyclodiene (such as pentadiene, 1, Cyclohexadiene, such as 3-cyclohexadiene, 1,4-cyclohexadiene, cycloheptadiene, such as 1,3-cycloheptadiene, fluoroctadiene, such as 1,5-cyclooctadiene S like cyclodecadiene, octadecadiene, etc.), cyclotrienes (such as cyclooctatriene, etc.), and octa tetraenes (such as cyclooctatriene, etc.). Compounds having a ~ 3Q ring (for example, 3 to 20 ring) are preferably 3 to 16 ring, especially 3 to 12 ring (for example, 5 to 1 Q ring). Cyclene with substituent Class, including cycloolefins having examples of WCi-Ca alkyl, hydroxy, hydroxyalkyl, and carboxyl groups (e.g., cyclohexene carboxylic acid, cyclohexene dicarboxylic acid, cyclohexadiene carboxylic acid, cyclohexadiene dicarboxylic acid , Cyclo_geranic acid, cyclogeranol, cyclocitral, cyclogeranol, etc.), cycloalkanones with oxygen groups (such as cyclohexanone, etc.), etc. -30 ™ This paper size applies China National Standard (CNS) Λ4 specification (210 × 297 at public expense) --------- ,,- Packing ------ order ------ 'grade (please read the notes on the back before filling in this tile). Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 4 α 8 1 3 7 Α7. Β7 5 2. Description of the invention (4) The pre-iminoimine compound has high gasification activity, and even under mild conditions, it can catalyze the gasification reaction of cycloolefins, so that the pinenes can be gasified by gas with good efficiency. Gasify cycloolefins with good efficiency, that is, it can generate corresponding cycloolefin oxides (such as ketones, alcohols, aldehydes or carboxylic acids) with high selectivity, especially cycloalkanones or cycloalkanols In addition, in the coexistence of the fluorenimine compound represented by the formula (1) and a co-catalyst, gasification of the pinenes can further improve the conversion rate and / or the selectivity. (c) Polycyclic hydrocarbons containing methylene as a ring constituent unit The aforementioned polycyclic hydrocarbons include crosslinked cyclic hydrocarbons having at least one methylene group (ie, methylene nitrite-hydrogen bonding, -CH <) ( For example, cross-linked cyclic hydrocarbons, terpenes, etc.), and condensed polycyclic hydrocarbons (fluorenes having methylene groups are usually non-aromatic rings, and may be cross-linked rings or condensed rings with unsaturated double bonds. Ortho condensation, or condensed polycyclic hydrocarbons with ortho and perposition (Perri), is not limited to non-aromatic rings with methylene groups, and aromatic fluorene can also be condensed. In polyfluorinated hydrocarbons, more than two methylene groups are mostly present at the bridgehead and / or junction. Even among the cyclic hydrocarbons which are cross-linked, there are condensed polycyclic hydrocarbons which are formed by the combination of dimethyl groups which share adjacent rings with each other. In these compounds, methylene groups can be vaporized in at least one of the bridge head position and the junction position, and a hydroxyl group can be introduced into a tertiary atom. The hydroxyl introduction site can be selected according to the type of matrix. On the other hand, a gas group is mostly introduced at a position (secondary carbon atom) adjacent to the aforementioned bridgehead position and junction position. Cross-linked cyclic hydrocarbons are, for example, bicyclic hydrocarbons (for example, pinane, g-alkane, pyran, pinane, cymene, ortho-berene, ortho-berane, bicyclic [3.2.1.] Octane, Bicyclic [4.3.2.] Undecane, etc.), tricyclic hydrocarbons (that is, tricyclic-3 1-this paper size applies to China National Standard (CNS) A4 specifications (210X297 mm) --------- 1-pack --- ordering ------, line (please read the notes on the back before filling this page) Printed by the shoulder labor consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs Α7. Β7 5. Description of the invention (π ) [4.3_1.12'5] undecane), octahydromethylmethylindene (that is, tricyclo [5.2.1.G3'8] decane), adamantane, hydrazine [5.2 · 1.〇2 'β] decane, bridge tricyclo [5.2.1.02,6] decane, tricyclo [4,3_1.1% S] undecane, bridge tricyclo [5.2.2_〇2, s] undecane Etc.), tetrahydrocarbons (such as tetracyclo [4.4.12 5 17, w] dodecane, etc.), and diene diene such as dicyclohexadiene, dicyclopentadiene, etc. Polymers, hydrogenation products of such dimers (e.g., dioxane, dicyclopentane, dicyclopentene, dicyclohexadiene, dicyclopentadiene, etc.), and derivatives thereof. Crosslinked cyclic hydrocarbons mostly use bicyclic hydrocarbons to tetracyclic hydrocarbons having a large number of rings of about 7 to 16 (especially about 6 to 14). For example, two or more bridge heads or junctions have carbon-hydrogen bonds. Compounds, especially dichens such as pyran, pinane, norbornene, probornyl, and norbornene, tricyclic [4. 3 · 1. 1 2 '5] undecane, octahydromethylene indene , Tricyclic hydrocarbons such as adamantane. Cross-linked cyclic hydrocarbons to which hydroxyl groups can be introduced at the tertiary carbon atom at the bridgehead position include, for example, orbornene, tricyclo [4.3.1.1.2,5] undecane, octahydromethyleneindene, Adamantane, or a derivative thereof. Cross-linked cyclic hydrocarbons that can introduce a hydroxyl group at the tertiary carbon atom at the bonding position, include, for example, tricyclo [5.2_1,02,6] decane, bridge tricyclo [5.2.1. 〇2, s] decane, Tricyclo [4_3.1.1.2,5] undecane, bridge tricyclo [5.2.2.2.0.6] undecane, tetracyclo [4.4.12'5 1m] twelve Alkanes, etc. Terpenes include, for example, monocyclic monoterpenes (pinene, terpineolene, terpinene, phlene, S-ene, etc.), bicyclic monoterpenes (fluorenone, pyrene, pyran, camphor, Limonene, norbornene, fluorenone), monocyclic times -3 2-China National Standard (CNS) 8 4 specifications (210X297 mm) --------- NI equipment -------- Order ----- "line (please read the precautions on the back before filling this page) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs m 448137 A7 ,, B7 V. Description of the invention (even) bisaboiene (disc Dilute), bicyclic sesquiterpene (cadinene, tannene, selinene, mountain year, caryophyllene, etc.), tricyclic sesquiterpene (igutalene, sandalene, longifolene, etc.), Diterpenes (vitamin A, etc.), triterpenes (ambergris, linseum, lupinol, etc.), tetraterpenes (eugenin such as euphorbia, lutein, etc.), polyterpenes and their Derivatives. Conjugated polycyclic hydrocarbons include, for example, various compounds produced by the condensation of condensed polycyclic aromatic hydrocarbons having 5 to 8 ring rings, such as decalin, perhydrofluorene, phenanthrene, phenalene, and Hydrogen festival Condensed polycyclic hydrocarbons are mostly 5- or 6-membered condensed condensates. Condensed polycyclic hydrocarbons are mostly oxidized by methylene in the bonding position. Among the polycyclic hydrocarbons with substituents, crosslinked fluorinated hydrocarbons are derived from For example, derivatives with a halogen atom (such as 2-chlorogen-pyramidane, 1-chloroadamantane, 1,3-dichloroadamantane, etc.), and derivatives with an alkyl group (2,2-dimethyl-orogen) Limonene, 2, 7,7-trimethyl-2-orbornene, i-methyladamantane-1 -ethyladamantane, 1-n-propyladamantane, 1-isopropyladamantane, 1-N-butanyl amantane, 1-butanyl adamantane, 1-ammonium adamantane, 1-pentanyl adamantane, 1-hexyl adamantane, 1-cyclohexyl adamantane, 1, 3-dimethyl Adamantane, 1-methyl-3 -ethyladamantane, 1,3-dicyclohexyl adamantane, 1,3,5-trimethyladamantane, 1-ethyl-3,5-dimethyladamantane Alkane, hemantane, and other compounds having (: 1-(: 6 or so alkyl groups), derivatives having a hydroxyl group (for example, pinoniol, norbornol, isorenol, 1-adamantanol, 1 , 3 -adamantanediol, 1, 3, 5 -adamantanetriol, 1 -Methyl-3 -adamantanol, 1-methyl-3, 5 -adamantanediol, 1--3 3-This paper size applies to China National Standard (CNS) A4 specification (210X297); t)- ---------- 4 I Pack -------- Ί Order ------. Silver (please read the precautions on the back before filling this page). Cooperative printed α 4 β 1 3 7 Α7 ,, __Β7_ V. Description of the invention (3 ×) Ethyl-3 -adamantanol, 1 -ethyl-3,5-adamantanediol, 1,3-dimethyl -5-adamantanol, 1-methyl-3-ethyl-5-adamantanol, propyl-3 -adamantanol, 1-propyl-3, 5-adamantanediol, etc.), alkane group (Bumethoxy adamantane, 1,3-dimethyl adamantane, 1-ethoxy adamantane, 1,3-diethyl adamantane, etc.), derivatives having a gas group < 莰 酲, Menidone, 2-adamantanone, methyladamantanone, dimethyladamantanone, etc.), derivatives having a fluorenyl group (formamyl promenorene, methenyl adamantane, etc.), having Derivatives of carboxyl groups (paneic acid, pinenoic acid, etc.), derivatives with alkoxycarbamyl groups (methoxolinofluorene, ethylsulfonylpinene ), Having a derivative (ice-yl amine, etc.) an amino group, a derivative having a vinyl group (vinyl-norbornene, etc.) and the like. The cyclic terpene derivatives include, for example, cyclic terpene alcohols (algalol, carboxymenthol, terpene alcohol, cedar alcohol), cyclic terpene aldehydes (parsley S_, celeryl, perillaldehyde, etc.) Ketones (ionone, iris_, menthol, carboxymenthone, hydrazone, etc.), terpene terpene oxides (by tree brain, menthol, hydrazone, etc.), cycloterpene carboxylic acids (pinene, Camphoric acid, rosin acid, neo-rosin acid, L-pelicic acid, d-pelicic acid, etc.) etc. Condensed polyfluorene hydroxy derivatives are, for example, derivatized fluorenes having an alkyl group (methylchaetan, ethylnaphthane, n-propylnaphthane, isopropylnaphthane, n-butyllyane, s-butylene, and Butyl decalin, cyclohexyl isane, dimethyl decalin, methyl ethyl isane, trimethyl decalin, ethyl dimethyl pentane, tetramethyl decalin, and so on Hexahydrogens, etc.), derivatives with hydroxyl groups (such as decalinol), derivatives with oxygen groups (such as decalinone), derivatives with carboxyl groups (such as decalincarboxylic acid, etc.), and amino- 34- 1 ^ 1 ^ 1 ^^^^ 1 —ϋ ^^^^ 1 ^^^^ 1 n- ^^^ 1 ^ 1 ^ 11 n ^ — n ^^^^ 1 「M — ^ n 1 Ί 0¾, ^ a bv. (Please read the precautions on the back before filling in this page) This paper size is applicable to China Gujia standard 隼 (C: NS);:〗 0x 2y7 mm) 4 4 8 t 3 7 A7 _ B7 V. Description of the invention (W) derivative alkylamine), etc. The gasification catalyst composed of the aforementioned amidine compound or the gasification catalyst strip composed of the aforementioned _ imine compound and auxiliary catalyst may have good efficiency Polymethylene hydrocarbons containing methylene rings which form a ring, Oxygen is gasified to generate gaseous compounds of polycyclic hydrocarbons (ketones, alcohols, xylates, carboxylic acids), especially ketones and alcohols, with a high selectivity. Therefore, in the method of the present invention, Pyrene hydrocarbons (for example, dipyridene to tetrapyrene hydrocarbons having a methylene group at a plurality of bridgeheads or junctions) are in contact with gas, and hydroxyl groups are introduced at the bridgehead or junctions with high selectivity and yield. Hydroxy-containing polycyclic hydrocarbons, in particular, using a catalyst strip composed of the foregoing fluorene imine compound and a divalent transition metal compound, or the foregoing fluorene imine compound and containing an element selected from Group 4A of the periodic table (Ti, Z, " Etc.) When the catalyst is composed of a compound of a group 5A element (V, etc.), a group 6A element (Cr, Mo, etc.), a group 7A element (Mη, etc.), and a group 8 element (Co, etc.), the polycyclic ring can be improved. Hydrocarbon conversion rate, with high selectivity and yield of hydroxyl-containing polycyclic hydrocarbons. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) and use adamantane as the substrate In the present invention, the present invention can be directly or indirectly introduced into a plural bridge head position. Group to form an adamantane polyol. The adamantane polyol in which a hydroxyl group is introduced at a plurality of bridge head positions can be selected from the group consisting of adamantane in the presence of the above-mentioned M-imine compound and a co-catalyst forming a gasification catalyst 气. The method for contacting the adamantane component of the derivative and gas with (2) in the presence of a gasification catalyst composed of the foregoing amidine compound, or an oxidation catalyst strip composed of the amidine compound and an auxiliary catalyst, Contains at least one of the adamantane monool, adamantanediol, and adamantane triol. The adamantane content and oxygen content of this paper are applicable to the national standard (€ ~ 5), 6 and 4 specifications (210 '/ 297 mm). 8 4 4. 1 3 7 A7., __B7_ V. Description of the invention (correction) It is made by the method of contacting to generate highly hydroxylated adamantane polyol. (Please read the intentions on the back before filling in this page} Former 逑 Π) method, because 傜 choose the type of the aforementioned 醯 imine compound and auxiliary catalyst, the combination constitutes a catalyst strip, which can greatly inhibit the adamantane multivariate Isolation and purification of yeast greatly hinders the formation of ketone bodies and significantly improves the yield of adamantane polyol. For example, when using a divalent transition metal compound as a catalyst (such as a divalent cobalt compound) and the aforementioned sulfonium imine compound as a catalyst, when the adamantane component is oxidized, the selectivity can be high even under mild conditions. Polyols such as adamantanediol are produced in a yield with almost no by-products of ketone bodies. In particular, when the reaction temperature is increased, ketone bodies are hardly produced as a result of the reaction time, and the production amount of polyalcohols such as adamantanediol is larger than that of adamantine. Furthermore, when using compounds containing Group 4A elements, Group 5A elements, Group 7A elements, and Group 8 elements of the periodic table of choice, especially compounds containing Group 5A elements (V, etc.) of the periodic table as auxiliary catalysts, it is advisable to moderate Conditions, high selectivity and yield, polyols such as adamantanediol can be prepared from adamantane components, especially adamantanetriol or adamantanetetraol. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs In addition, the method of (2) above is performed in the presence of alcohols of adamantane (for example, alcohols using adamantane alone, or alcohols containing adamantane and adamantane, As an adamantane component), gas is used to oxidize adamantane, and an adamantane polyol with a higher degree of introduction of hydroxyl groups is effectively and efficiently produced. For example, when the adamantane alcohol alone or the adamantane component composed of adamantane monool and adamantane is argonized, an adamantane polyol (adamantanediol, adamantanetriol, etc.) having a hydroxyl group introduced at a plurality of bridgeheads of two or more fluorene can be obtained Alcohol or adamantane tetraol, etc.), and the adamantanediol alone, or the gold composed of adamantanediol and adamantane ~ 36 ~ This paper size applies to the Chinese National Standard (CNS) Λ4 specification (2 丨 0X297 mm) 448137 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention () 1 When the Gangyuan is composed, it is possible to introduce a hydroxyl 1 1 1 group of Diamond Kong Polyol (adamantanetriol) at three or more bridge heads. Or amantadine methanol, etc.) 〇 Another 1 [Do n’t need to be alone, or amantadine containing amantadine, please] When you first make amantadine, you can get adamantane tetraol. Therefore, when you make an aramid polyol, Interpretation 1 1 Use early alcohol containing taa, adamantandiol and adaman To the back of the triol I | 1 less J * component 1 as the adamantane component > can get more attention to the introduction of hydroxyl 1 thing 1 adamantane polyol 0 item-1 in the method (2) to produce adamantane For alkane polyols, you can fill in the adamantane alcohol-TΓ at least coexistence set 1 to make the adamantane component react t is not particularly limited to the content of the adamantine 1 I alcohol adamantine diol or the content of triol 1 The total amount of adamantane 1 1 may be 5 mol% or more (for example, 10 to 100 mol%), 1 I is preferably 20 10 0 mol%, and 30--1 0 0 mol% It is better to use 0, 1 and 01 in the method of (2) above, using a divalent transition metal compound (eg, a divalent cobalt compound, etc.), or containing an element selected from Group 4A of the periodic table, 5 A group 1 1 element y 6A Group 7A and 8A compounds T as [| aux The medium is still effective. 0 1 1 (d) 茌 aromatic ring aromatic compounds with methyl or methylene in ortho position | _ »tl 刖 逑 aromatic compounds, which may have at least one methyl group or I in the aromatic ring | Methylene substituted aromatic compound * The aromatic ring may be an aromatic hydrocarbon ring or 1 1 aromatic heterocyclic ring. 0 The aromatic compound is a combined biphenyl »triphenyl * binaphthyl, 1]. In the case of ring collection compounds »At least one aromatic 1 I ring may be substituted by a methyl group or a methylene group. In addition, in an aromatic heterocyclic ring> A methyl 1 1 group or a methylene group may be bonded to a heterocyclic group or may be bonded to Condensed heterocyclic Laoxiang 1 | Hydrocarbon 璟 〇 Preferred compounds include compounds with a methyl or methylene group at the benzyl position 1 i 37 1 1 1 1 This paper is applicable to Chinese national standard {('s: i Λ4 specifications (210X297 mm) 448137 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs A7. B7 Described invention (0) thereof. Aromatic hydrocarbon rings include, for example, benzene rings, condensed ring hydrocarbon rings (e.g., fluorene, phenanthrene, phenanthrene, triphenyl, gas, naphthacene, naphtha, etc. 2 to 8 benzene rings are condensed in ortho or ortho and forced positions Condensation ring). Aromatic heterocycles include, for example, heteroatoms containing gas atoms (e.g., 5-membered rings such as furan, oxazole, isoxazole, 6-membered rings such as pyran, benzofuran, isobenzofuran, dibenzofuran). , Condensed rings such as tonone, chroman, heterochroman, chromene, etc.), heterocycles containing sulfur atoms as heteroatoms (such as carbeneazole, isoxazole, iffdiazole, benzofluorene, etc.), containing Heterocyclic ring with nitrogen atom as heteroatom (for example, pyrrolidine, pyrazole, imidazole, triazole, etc. 5 sections of pyrene, pyridine, pyridazine, pyrimidine, pyrazine, etc. 6 sections of pyrene, indene, ind ο 1 ene, isoearthrum Woo, indazole, indolinium, isoindolin, IS-line, iso-line, quinoline, quinoxaline, I-oxazoline, phthalazine, purine, beta-oxazole, acridine, naphthalene®-line , Phenanthrozine, phenanthroline, trimidine, benzo (¾-line, phenoxazole, phthalocyanine, anthcacyanine and other condensed rings), etc. Industrially useful aromatic compounds, mostly aromatic Hydrocarbon rings, 6-membered heterocycles or condensed heterocycles, preferably C s-C 14 aromatic hydrocarbon rings, especially CS -C10 aromatic hydrocarbon rings (including benzene fluorene or naphthalene ring > most The method of the present invention can vaporize the methyl group or methylene group of the aromatic compound with good efficiency, and the number of substitution of the methyl group or methylene group is not particularly limited. It can be widely selected depending on the type or size of the aromatic ring ( For example, 1 ~ 10, preferably about 1 ~ 8) e (dl) Formazan-substituted aromatic compounds Methyl-substituted aromatic compounds, for example, about 1 ~ 6 値 methyl-3 8-(please first (Read the notes on the back and fill out this page).

1. The paper size of the 1T line is applicable to Chinese National Standards (CNS). Λ4 is present (210X297 mm) 137 137 4 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 4 A7, _B7_ V. Aromatic hydrocarbons replaced by the description of the invention (M) Class (toluene, ortho, meta, para-xylene, 1,2,3-trimethylbenzyl, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene, 1,2,3,4-tetramethylbenzene 1,2,3,5-tetratoluene, 1,2,4, 5-tetratoluene, 1,2,3, 4,5,6-hexamethylbenzyl, 1-naphthalene, 2-methanine, 1, 5-dimethylnaphthalene, 2, 5-dimethylnaphthalene, formazan, dimethylamine, trimethylamidine, 4,4'-dimethylbiphenyl, etc.), methyl-substituted heterofluorene compounds of about 1 to 6 amidine ( For example 2-methylfuran, 3-methylfuran, 2-methylpyran, 3-methylpyran, 4-methylpyran, 3, 4-dimethylpyran, 4-methylchromene , 6-methylchromene, 2 ~ methylpyridine, 3-methylpyridine, 4-methylpyridine and other picoline, 2, 3-dimethylpyridine, 2, 4-dimethylpyridine 2,2,5-Dimethylpyridine, 3,5-Dimethylpyridine and other luperidine, 2,3,4-Trimethylpyridine, 2,3,5-trimethylpyridine, 2,3,6 -Trimethylpyridine, 2,4,6-trimethylpyridine, etc. D, 4 - B duo methylindole, 5 - methylindole Jie flowers, 7-- methylindole methotrexate, cha-methyl morpholine, etc.). In a preferred aromatic compound, the number of methyl substitutions is mostly about 1 to 4 (for example, 1 or 2) in the molecule. Especially about 1 to 4 methyl-substituted C s-C ω aromatic hydrocarbons, or heterocyclic compounds containing 5- or 6-membered heterocycles (including methyl-substituted benzene derivatives, most of which are industrially produced) Compounds useful for carboxylic acids. (D 2) compounds having a methyl group in the ortho position of the aromatic ring. Compounds having a methyl group in the ortho position of the aromatic ring. Aromatic compounds having a cyclic methyl group. The aromatic compounds having an alkyl group or a substituted alkyl group include, for example, aromatic hydrocarbons having an alkyl group (ethylbenzene, propylbenzene, pinene, butylbenzene, isobutyl- 39- This paper size applies Chinese National Standard (CNS) Λ4 specification (2IOX 297 mm) (Please read the notes on the back before filling this page) Swim-A 7 B7 V. Description of Invention (β) Benzene, 1, Aromatic hydrocarbons with C2-C6 alkyl groups such as 4-diethylbenzene, 1-ethyl-4-pentylbenzene, bibenzyl, diphenylmethane, triphenylmethane, 1-benzylnaphthalene, etc. Aromatic hydrocarbons, etc.), heterocyclic compounds having a fluorenyl group (ethylpyridine, isopropylpyridine, butylpyridine, etc.) and the like. Aromatic compounds having fluorene methylene, such as condensed polycyclic aromatic hydrocarbons (dihydrofluorene, indene, indan, tetrahydronaphthalene, hydrazine, phenethylhydrazine, etc., with 5 to 8-membered ring condensation) ine), cr-fluorenone, -naphthone, indanone, etc.). Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) Aromatic compounds (d ) May also have methyl and methylene groups adjacent to the aromatic ring. These compounds include, for example, alkyl-substituted hydrocarbons having at least one methyl group and at least ~ C 2 -C 10 alkyl groups (for example, 1-methyl- 2-ethylbenzene, 1-methyl-3-ethylbenzene, 1-methyl-4-ethylbenzene, 1-methyl-3-cumene, 1-methyl-4-cumene, 1-methyl Methyl-4-propenebenzene, 1-methyl-4-butylbenzene, methyl-4-tert-butylbenzene, 1,2-dimethyl-3-ethylbenzene, i, 2-dimethyl-4-ethyl Benzene, 1,3-dimethyl-5-ethylbenzene, 1,3-dimethyl-4-ethylbenzene, 1,3-dimethyl-2-ethylbenzene, 1,4-dimethyl-2 -Ethylbenzene, 1-methyl-2-ethylnaphthalene and other alkyl-substituted hydrocarbons having a methyl group and a C 2 -C e alkyl group), and alkyl-substituted heterocyclic compounds (for example, 2-ethyl-4-methylpyridine) , 3- 4-methylpyridine, 4-ethyl-2-methylpyridine, etc.), hydrocarbons having at least one methyl group and cyclic methylene (3-methyl segment, etc.), etc. Aromatic compounds in methyl In addition to methylene or other substituents, these aromatic compounds have carboxy-substituted hydrocarbons (such as 4-methylbenzoic acid, 1,2-dimethylbenzene-4-carboxylic acid, etc.), halogenated hydrocarbons (E.g. 4-gas-1-methylbenzene, 3, 4,5,6-tetrachloro-1,2-dimethylbenzene, 3,4,5,6-tetrabromo-1, 2-dimethyl Benzene, etc.), hydroxyl-containing hydrocarbons (such as ortho-, meta-, p-cresol, etc. methyl formaldehyde-4 0-ΐΆίΜί degree Applicable to China® National Standard (CNS) Λ4 specification (2j〇X 297 mm) 448 ί 3 Α7 Β7 Ministry of Economic Affairs Production cooperation of employees of the Central Bureau of Standards Du printed 5. Description of invention () 1 1 Class 1 2, 3-xylenol 9 thymol, etc.), hydroxyl-protected aromatic hydrocarbons 1 1 [For example, containing gas-based hydrocarbons (2 -Methoxy-1-methylbenzene 3 ~ methoxy-1-1 I methylbenzene 1 4-methylamino-1 -methylbenzene, 4 -ethoxy-1-methylbenzene > 4 -Please! First · Isopropyl-1- Benzene, etc.) Fluorenyl Substituted Hydrocarbons (2 -Ethylamino-1-1-methyl)! 1 Jirong 3-Ethylamino-1 -methylbenzene, 4 -Ethylamino-1 -methyl Benzene «Back 1 I 1-4-Propanyl-1-methylbenzene, 4-butytoxy-1-methylbenzene, etc.) Note that 1 I may also have an amino-containing hydrocarbon (4 _Gasyl-1-methylbenzene * 4-dimethyl matter-Sh: 1 \ 1yl-1-methylbenzene, etc.) aromatic hydrocarbons 9 halogenated pyridine derivatives (for example, 2-gas -4-methylpyridine, etc.) and other heterocyclic compounds. Page '--- · 1 I In the presence of the above-mentioned fluorene imine compound gasification catalyst > pt / -5AJ aldimine compound 1 1 and gasification ttva catalyst composed of auxiliary catalyst% presence of these aromatic orders When a grouped 1 1 compound is in contact with gas for gasification> A methyl group or an aromatic ring adjacent to methylene can be used to generate 1 radicals with high efficiency. I Choose from methyl-containing aromatic compounds with a high 1 Yields and m yields) (especially aromatic compounds containing carboxyl group 9 1 1 and aromatic compounds from fluorene methylene ') yield 1 I at a rate of selectivity and yield. Ketones particularly 疋 m make in mild When reacting under the conditions »1 '1 can be carried out within a short period of time 1 to facilitate the reaction 1 to produce aromatic i-group compounds or carboxyl groups with carboxyl groups at a selective rate and yield 0 In addition, 1 oxidizes aromatic compound i with multiple methyl groups Reaction conditions such as reaction time Control 9 Depending on the reaction t [Carboxylic acid with methyl residues is generated 1 Continue to perform reverse reaction 1 It is easy to make [[Polyols with carboxyl groups that are more than two dips] So the method of the present invention can be used with l 1 r now having at least one methyl group Or the methylene aromatic compound t is in contact with oxygen 1 1 to form an aromatic compound or ketone having a carboxyl group. Preferred method II of the present invention comprises a methyl-substituted benzene derivative (eg, toluene, xylene, etc.) 1 1 I 41 1 1 1 1 This paper size applies to Chinese National Standard (CNS) Λ4 specification (210X29 * 7mm) 4 4 8 13 Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (ο) In contact with gas, carboxyl-containing benzene derivatives (such as benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, etc.) that are industrially useful compounds, and C 2 -Cs alkyl-substituted aromatic hydrocarbons (such as Ethylbenzene, etc.), contact with gas to produce industrially useful compounds containing sulfofluorenyl-containing benzene Biological (such as acetophenone, etc.) n When using divalent transition metal compounds (such as divalent cobalt compounds, etc.) as auxiliary catalyst Π 5 ~ 30P) can also increase the release rate and yield of polyacids or ketones. For example, when bottle dibenzene is oxidized, terephthalic acid can be produced in a short period of time with a high selectivity and yield, even under mild conditions and a reaction time of about 1/2. In addition, when the catalyst 糸, which is a combination of a divalent transition metal compound and a pre-imine compound, is argonized with o-xylene with air or gas, phthalic anhydride is formed. Therefore, the present invention can be used to oxidize aromatic compounds with high conversion and selectivity under mild conditions to obtain carboxylic acid-containing compounds such as unit carboxylic acids, polycarboxylic acids or ketones, especially aromatic units such as benzoic acid It is extremely useful in the production of aromatic polycarboxylic acids (especially aromatic dicarboxylic acids) such as carboxylic acids, polyesters, and polyamides. (e) Conjugated compounds Conjugated compounds include conjugated diene, α, Θ-unsaturated, or a compound represented by the following formula (2) (cc, unsaturated carboxylic acid or its derivative), etc. ---- -----, —install ------ order ------ step on (please read the precautions on the back before filling this page) 4 48 13 7 Α7 Β7 V. Description of the invention (41) R7 is a hydrogen atom or a methyl group, and Y is -OR8 (R8 is a hydrogen atom, alkyl, aryl, cycloalkyl, hydroxyalkyl, glycidyl, dialkylaminoalkyl), -〇91ϊω (ίθ and RiQ The same or different, is a hydrogen atom, an alkyl group is an alkyl group). Conjugated dienes include compounds having a conjugated double bond such as butadiene (1,3-butadiene), isoprene (2-methyl-1,3-butadiene), and the like. Bonded and triple-bonded compounds (vinylacetylene, divinylacetylene, etc.), and their derivatives. Derivatives of conjugated diene include 2-chlorobutadiene, 2,3-dibutadiene and other compounds having a halogen atom (iodine, bromine, ammonium, and fluorine atom), and 2-ethylbutane Diene, 2,3-dimethylbutadiene, etc. have alkyl groups (such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, butyl, fluorenyl, etc. Ci -C4 Lower alkyl) compounds, compounds having a carboxyl group such as butadiene-1-carboxylic acid. Preferred conjugated dienes are butadiene and isoprene · diene. Co-dienes are gasified with gas to form alkanediols. The substituted alkanediol is not particularly limited as long as it is a diol corresponding to a conjugated diene. For example, the butene diol produced by the gasification of butadiene may be 2-butene-1,4-diol. 1-butene-3,4-diol, etc. Any type can be used. Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the notes on the back before filling this page) oc, stone-unsaturated nitriles include, for example, (meth) acrylonitrile. The conjugated compound represented by the aforementioned formula (2) corresponds to α, / 3-unsaturated carboxylic acid or a derivative thereof. In the substituent R8 in the aforementioned formula (2), the alkyl group includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, butyl, tert-butyl, pentyl, etc. This paper is applicable to China National Standard (CNS) Λ4 specification (210X297 mm) 4 4 8 13 A7 B7 V. Description of the invention (private) Hexyl, heptyl, 2-ethylhexyl, octyl, decyl, tetradecyl and other C!- Straight or branched alkyl groups around 2Π. Preferred alkyl groups include those around Cl-15, especially those around Cl-12 (e.g. around Cl-10). Aryl includes phenyl, naphthyl, and the like. The cycloalkyl group includes a cycloalkyl group having 5 to 10 rings, such as cyclopentyl, cyclohexyl, and octyl. · The hydroxyalkyl group includes a C? -10 hydroxyl group such as 2-hydroxyethyl, 2-hydroxypropyl, 4-hydroxybutyl, and hydroxypentyl. Preferred pornographic bases include those based on C2-4, especially those based on C2 or Ca. The dialkylaminoalkyl group includes dimethylaminoethyl, diethylgylethyl, dibutargylethyl, etc. = Ci-4 alkylamino-C2-3 alkyl, and the like. Substituent group 8 is usually a hydrogen atom, a Ci-10 alkyl group, a C2 or hydroxyalkyl group, a glycidyl group and the like. Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the notes on the back before filling out this page) Compounds with these substituents are, for example, (meth) acrylic acid; (meth) acryl octadecyl methyl ester, (methyl Based) ethyl acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, 2-ethyl (meth) acrylate (Meth) acrylic acid alkyl esters such as methylhexyl ester, lauryl (meth) acrylate; 2-M ethyl (meth) acrylate; (meth) acrylic acid such as 2-hydroxypropyl (meth) acrylate Hydroxyalkyl esters, glycidyl (meth) acrylate; dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and the like. In the substituted amino-NR 9 R 10 represented by Y, the alkyl groups in R 9 and R 1Q are, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, butylene, and butyl. Alkyl groups such as Ct-10, pentyl and the like. Preferred alkyl is

Foundations around Cl t fi, especially those around Cl-4. Jingyuan-44- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 cm) 448137 A7 B7 V. Description of the invention (with) Contains hydroxy-C-10 alkyl, hydroxymethyl, hydroxyethyl Base is better. The substituents R 9 and R w may be the same or different. Usually, most of them are hydrogen atoms, C 1 4 or so, Cl or C 2 via the radical D. Compounds having these substituents, for example, (meth) acrylamide, • y-fluorene-methyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide and other (shenyl) acrylamide derivatives. Let these ct, stone-unsaturated nitrile, α, / 3: unsaturated carboxylic acid or its derivative, be gasified when contacted with gas, α, / 3-non-planing and binding part can choose t anionization, The compound represented by the following formula (3a) or (3b) is produced with high conversion and selectivity. (R11a〇) rr R7 I .CH_C_ (R11a0) m (Please read the precautions on the back before filling out this page) (3a) (3b) In the stamp type of the Consumer Cooperatives of the China Standards Bureau of the Ministry of Economic Affairs, Z is a gas atom or -0 R 11 b, R 11 a and R 11 b are the same or different, and are a hydrogen atom, an alkyl group, a fluorenyl group, and m is 0 or U. The combination of carbon atoms C and Z represents a single bond or a double bond. R7, Y are the same as before. However, when Z is an oxygen atom, m is 0, the combination of the master atom C and Z is double fluorene, and when Z is -0 R 11 b, m is 1, and the combination of the master atom C and Z is a single bond. In the compound fluorene represented by the formula (3 a) or (3 b), the alkyl group in the substituents R 11 3 and R 11 b includes, for example, methyl, ethyl, propyl, isopropyl, butyl, iso C i-e alkyl groups such as butyl, butyl, and tert-butyl groups, and aldehyde groups include C2- 6 fluorenyl groups such as ethyl fluorenyl and propyl fluorenyl. These alkyl, fluorenyl, and fluorenyl groups react with solvents. -45-This paper size is applicable to the Chinese national plutonium heap __ (_NS) Λ4 present grid (210X 297 mm) 448137 A7 B7 V. Description of the invention (from) The degree of vaporization should be based on the generation of glycols U on the substrate as -0 R 11 b, R 11 s and R 11 b —compounds when they are both nitrogen atoms), using dehydration reaction, Xue or its derivatives (compounds when Z is a gas atom) can be formed. In addition, if aprotic solvents (such as organic acids such as acetic acid and propionic acid, methanol, ethanol, n-propanol, isopropanol, n-butanol, and t-butanol, etc.) are used as the reaction solvent, shrinkage or tritium oxide is generated Diol derivatives (such as when Y is -OR 11 b, at least one of R ua and r U b is an alkyl group or a fluorenyl group). These aldehydes or their derivatives, and glycol derivatives such as acetals are pseudo-equivalent compounds. For example, the reaction solvent can be argonized with alcohol (methanol, etc.) to generate 1,1-dialkylchloropropionitrile (1,1-dimethoxypropionitrile, etc.). In addition, when methyl acrylate is vaporized in an alcohol (methanol, etc.) solvent, methyl 1,1-dialkylaminopropionate (such as 1,1 ™ dimethylaminopropionate, etc.) can be formed. N Economic Printed by the Consumer Standards Cooperative of the Ministry of Standards and Standards (please read the precautions on the back before filling out this page). As mentioned earlier, the present invention can use the yoke compound to vaporize it with air or oxygen to make the phase Corresponding oxides, such as olefin diols produced from conjugated diene (e.g., synthetic resins such as polyamine from butadiene, maleic anhydride, plasticizer, butanediol, etc.) Butenediol) from ct, / 3-unsaturated nitrile, a, / 3-unsaturated carboxylic acid or a derivative thereof to produce the compound represented by the above (3a) (3b). (f) Other substrates Other substrates include, for example, a heterocyclic compound (f 1) having a methylene group, a chain hydrocarbon (f 2) having a methylene carbon atom (methylene group), and an ortho position of an unsaturated bond. The methylene compound (f 3) has a methylene compound at the ortho position of the sulfo group. The compound (f 4). -46-This paper size is applicable to China National Standard (/ NS) 8.4 (210X 297 Gongchu) 448137 A7 B7 Printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (from) 1 1 (f 1) Heterocyclic compound having a methylene group 1 Heterocyclic compound having a methylene group ί A 5- or 6-membered ring compound containing a heteroatom such as an optional white nitrogen S oxygen, sulfur 1 | atom, or a heteroatom- V Please condensed heterocyclic compound in which 1 1 5 or 6-membered ring is condensed with an aromatic heterocyclic ring. For example, di m 1 1 hydrofuran tetrahydrofuran dihydrofuran tetrahydropyran, piperidine T & II 1 piperazine N Btt Yakuin, M Purine, etc. Note 1 (f 2) Bonded hydrocarbons with methylene carbon atoms (methylene) 1 Matter of hydrocarbons with methylene τ-tlr in original chain Class 9 contains f with a tertiary sulfon atom. Class 1 »For example Ding Alkane-X isopentane isohexane S. 3-methylpentane 1 1, 2, 3-dimethylbutane S 2-methylhexane, 3- methylhexane N, 2, 3- 1 1 Methylpentane, 2, 4-dimethylpentane S 2, 3, 4-methylpentane, 3-ethyl 1 I pentane S 2, 3-dimethylhexane S 2, 4 " Dimethyl Hexane, 3, 4-dimethyl-1, 1 Diethyl Hexane 2, 5, Dimethyl Hexane 2-propyl Hexane * N 2-Methylheptane 4-Methylheptane 2-Ethyl Gengyuan, 3-ethylheptane 2, 6-dimethylheptan 1 I courtyard N. 2 ™ methyl octane N 3-methyloctane courtyard 2, 7-dimethyloctane courtyard N 2-methyl i 1 C, t-1D aliphatic hydrocarbons such as basenonane. ! (f 3) Compounds with methylene groups adjacent to unsaturated bonds Line 1 Compound (f 3) contains C 5-12 with double and / or triple bonds 1 1 Chained irregularities and hydrocarbons »For example Acrylic, 1-butene 2-butene butadiene 1 i Ν 1-pentene 2-pentene isoprene 1-hexene 2-hexene, 1, i | 5 »hexadiene 2, 3-Dimethyl-2-butene, 3-hexene, 1-heptene, 2-1 1 heptene S 1, 6-heptadiene N 1-octene 2-octene S 3- octene X 1, 7 — oct 1 I — * ene, 2, 6- octadiene x 2-methyl-2-butene, 1-nonene, 2-nonene, 1 I decene decadiene dodecene Ene, undecene 5 heptadiene dodecene diene S 1 1 undecene undecyldiene, undecadiene, etc. 0 1 I-4 7-1 1 This paper is applicable to KWVC-V,, : (AS) Λ · 4 坭 (210X297) 牦 Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 8 1 3 ： / '_ A7', B7 V. Description of Invention (Korean) (f 4) Compounds having a methylene group in the ortho position of the carbofluorenyl group Compounds having a (active) methylene group in the ortho position of the carbofluorenyl group include aldehydes, carboxylic acids, carboxylic acids or derivatives thereof. The hydrazones include aliphatic aldehydes (acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, hexyl, heptaldehyde, capryl, octaaldehyde, ketone, and decaldehyde, etc. Dialdehydes, adipaldehyde, sebacaldehyde and other aliphatic polyaldehydes, etc.), aromatic aldehydes such as benzoaldehyde, anisaldehyde, etc.). Alimentans (such as methanyl cyclohexane, osmanthus, etc.) ), Heterooxal (nicotinaldehyde, furfural, etc.) and so on. Ketones are aliphatic antiketones (acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl tert-butyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 3 -Hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-octanone, 3-octanone, 4-octanone, 2-nonanone, 2-decanone, etc.), aromatic ketones (Acetophenone, stupid acetone, etc.). The heterofluorene or its derivative includes, for example, an aliphatic dicarboxylic acid or its derivative (malonic acid or its ester, succinic acid or its ester, glutaric acid or its ester), and the like. Gas..Reverse..Response The gas used for matrix gasification can be active oxygen, but the use of molecular oxygen is economically advantageous. The molecular gas is not particularly limited, and pure gas may be used, or a gas diluted with an inert gas such as gas, krypton, argon, or carbon dioxide may be used. Not only workability and safety, but also from the economic point of view, m air is better. Qi use scene can be selected according to its quality. Generally, 1 to 100 moles is preferred, and 1 to 100 moles is preferred, and 2 to 50 moles is preferred to 1 mole of the matrix. Excessive molar argon relative to the substrate is mostly used, and the reaction is preferably performed in an atmosphere of molecular gas such as air or gas. -48- This paper size applies to Chinese National Standard (CNS) Λ4 specification (2 丨 〇Χ 297mm) ---------— Selection ------ 1T ----- line production · ( Please read the notes on the back before filling out this page) 3 ί 3 7 Α7 Β7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (decayed) Organic solvents include organic carboxylic acids such as formic acid, acetic acid, propionic acid, or gaseous I 1 carboxylic acids-V acetonitrile > nitriles such as propionitrile, benzonitrile, etc. Amine di ^^ Please! First 1 methylamine (DMF), dimethylacetamide and other amines, tert-butanol, reading 1 alcohol and other alcohols 1 1. .. λ ** > Aliphatic hydrocarbons such as Shuxinyuan, aromatic benzenes such as benzene, etc. 1 I 1 1 gas imitation 9 2 gas methane Λ 2 gas ethane, 4 gas sulfonate, chlorobenzene etc. Note 1 I hydrocarbon nitrobenzene nitromethane Nitro A Compounds »Acetic acid matters 1 Re-Γ acetyl butyl acetic acid and other esters-methyl m, diethyl _, diisoacid, etc. Fill in this paper and other classes * and their mixed solvents 〇 9 bases when using excess substrate Page, _ 1 I can also be used as a reaction solvent. Most of the solvents use organic acids such as acetic acid.) 1 1 Nitrile such as nitrile benzonitrile 0 1 1 When the reaction is performed in the presence of a protonic acid, I can smoothly perform the gasification reaction. The compound with the selectivity and the rate of 1 M. The protonic acid can also be used as a solvent as described above. The protonic acid contains organic acids (formic acid, acetic acid, propionic acid, etc., and organic acids such as oxalic acid, citric acid, tartaric acid, etc. Carboxylic acid 4 methanesulfonic acid, 1 I ethylsulfonic acid and other basic sulfonic acids * benzenesulfonic acid p-toluenesulfonic acid and other arylsulfonic acids, etc.) I * inorganic acid (such as hydrochloric acid, osmic acid, nitric acid, phosphoric acid, etc.) 〇 line I Method of the invention That is, even under mild conditions, the temperature of 9 m can be smoothed for 1 m. The chlorination reaction temperature depends on the type of substrate or catalyst. The appropriate choice is 1 1. For example, 0 to 3 00 t is preferably 30 2 5 0 ° C. 50 ~ 200¾ 1 I It is better to usually react around 70 15 ο υ. As mentioned earlier, depending on the type of gasification catalyst strip, 1 1 1 can be successfully used even in lower temperature 4 such as room vtsi (mL, etc.). 1 degree 40 1 5 0, especially 60--120¾ (for example, 70 ~ ιιου) around 1 49 1 1 1 This paper size is applicable to Chinese National Standard {CNS) 8 4 specifications (210 × 297 total) Central standard of the Ministry of Economic Affairs Printed by the Bureau's Consumer Cooperatives 448137 A7., B7 V. Description of the Invention (3) The reaction can produce adamantane polyol in a short time. The reaction can be carried out at normal pressure or under pressure. When it is carried out under pressure, it is usually mostly at 1 to 10 atmospheres (for example, 1.5 to 80 atmospheres), preferably 2 to 70 atmospheres, and more preferably 5 to 5 f) atmosphere it is good. The reaction time depends on the reaction temperature and pressure, and is appropriately selected, for example, from 0.5 to 48 hours, preferably from 1 to 36 hours, and more preferably from 2 to 24 hours. The reaction is carried out in the presence of molecular gas or under the flow of molecular gas in a batch method, a semi-bifurcation method, a mineral construction method and the like. After the reaction is completed, the reaction product can be easily separated and purified by a conventional method, such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, and other separation methods, or a combination thereof. The method of the present invention does not require special exhaust treatment. Oxygen or air is used for oxidation. Rhenium can oxidize the substrate with good efficiency and obtain an oxide corresponding to the substrate with good efficiency. For example, gasification with molecular oxygen can generate corresponding oxides from the matrix with high conversion and selectivity. In addition, in contact with oxygen under mild conditions, thorium can generate corresponding carboxylic acids directly and with good efficiency from the substrate (pinanes, cycloolefins, alkyl-substituted aromatic compounds), with high conversion and selectivity. (Long-chain dicarboxylic acids such as adipic acid, aromatic carboxylic acids), or amidines (cycloalkanones, cycloolefins, aromatic ketones). Furthermore, the gas can be used to efficiently vaporize the methylene sites at the bridgehead or junction of polycyclic hydrocarbons, and to produce phase with reduced conversion and selectivity from condensed polycyclic hydrocarbons and cross-linked cyclic hydrocarbons. Corresponds to diols or more. 1 50-Family Standard (CNS) Λ4 Specification (210X297 mm) in this body ί t »~--'; Order I: i: A (Please read the precautions on the back before filling this page) 4 43] 3 7 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (< 9) i 1 In addition, under mild conditions 9 while suppressing the ring-opening of polycyclic hydrocarbons and the diketone 1 1 body Production »While introducing hydroxyl 1 1 radicals at the third-order carbon atom in the bonding position with high efficiency and gasification with gas» Effective and local yields of adamantine diols. 1 Ms * mm Libei II 1 1 The present invention will be described in detail with reference to the following examples, but the present invention is not limited to these practical notes 1 matter 1 Example η Item Reimplementation. Implementation. Example A1 Transcript Mounting Ring Hexane 1.68 g (20 mmol Ear), N-hydroxyphthalimide imide 0.2 δ g > «· 1 I (1.6 mmol) acetamidine manganese manganese M n (AA);.» 0.043 g ( 0.12 1 1-^ r pen mole), a mixture of 25 ml of acetic acid, in an oxygen atmosphere, κ loot: 1 1 m. Stir for 6 hours. The product in the reaction solution was checked by gas chromatography to produce 1 Adipic acid conversion rate of 55% and selectivity of 82% were obtained to produce adipic acid (yield 45%) 1 0 In addition, 9 KA oil (cyclohexanone and cyclohexanol) was not formed. 〇1 1 实. JOO 义 1 1 Except that the manganese acetopyruvate was replaced with a gasification clock Mη 0 7, it was learned that the same reaction as in Example A 1 -1 was carried out with a conversion rate of cyclohexane of 5096 and a yield of 42%. 0 oil (cyclohexanone) cyclohexanol has not been seen. 〇1. Shi A.3 1 1 except for the replacement of manganese ethylpyruvate with gasified manganese M η C 1 2 ♦ I | Example A 1 -1 Same reaction for 9 rings Conversion rate of alkane 55% 1 Yield 43% yield 1 1 to adipic acid. Κ A oil (cyclohexanone and hexanol alcohol) was not seen. 〇 1 1 Implementation of ΛΛ 1 to remove manganese ethylpyruvate to Manganese acetate Mη (0 Ac) 5. In addition to replacement, I 1 5 5 1 1 ί 1 This paper size applies to the Chinese national standard (CNS) Λ4 specification (210X 297 mm) A7 B7 V .. Description of the invention (π) Example Al-1 reacted similarly. Adipic acid was prepared with a cyclohexane conversion of 60% and a yield of 50 g. No formation of KA oil (cyclohexanone and cyclohexanol) was observed. Gong_., Shi Xun Adipic acid was prepared by the same reaction as in Example A1-1 except that the acetic acid solvent was changed to benzonitrile, and the conversion of hexane was 45% and the yield was 38%. No formation of KA oil (panhexanone and cyclohexanol) was observed. Example Jfe_ Adipic acid was prepared by the same reaction as in Example A1-1 except that the gas pressure was 10 kg / cra2, with a conversion of cyclohexane of 75% and a yield of 54%. No K A oil (cyclohexyl and cyclohexanol) was seen. Application. JLM—Except that the reaction temperature is 120t: adipic acid was prepared by the same reaction as in Example A1-1, with a conversion rate of 70% in cyclohexane and a yield of 42%. No formation of K A oil (cyclohexane and cyclohexanol) was observed. Practice-Application 1A "-.. Adipic acid was prepared with the same reaction as in Example A1-1 except that cyclohexane was replaced with cyclohexanone, with a conversion rate of 100% in hexane and a yield of 95%. No K A oils were produced (panhexanone and cyclohexanol). Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). Implement J? LA..9. Except for cyclohexane instead of cyclohexanol, stirring time is 10 hours. In the same manner as in Example A1-1, adipic acid was prepared with a conversion of cyclohexane of 95% and a yield of 90%. No formation of KA oil (璟 hexane 璟 and cyclohexanol) was observed. Actually ... apply. In addition to hexane, use cyclohexanone and cyclohexanol at a ratio of 50: 50 (weight tb) -52-This paper applies the Chinese national standard {CNS) Λ4 specification ϊ: ::: () 21 ^ 公 楚) A7 printed by the Consumer Cooperatives of the China Standards Bureau of the Ministry of Economic Affairs,-* B7 'V. The compound of the invention description (θ), the stirring time is 8 hours, according to Example A 1- 1 In the same reaction, adipic acid was prepared with a conversion of 95% and a yield of 90%. No formation of K A oil (panhexanone and tetrahexanol) was observed. Example 1AJ: 1.68 g (20 mmol) of cyclohexane, 0.26 g (1.6 mmol) of N-hydroxyphthalimide, Mn (AA) 2 0, 0 4 3 g (0.12 mmol) Mol), a mixture of 0.06 g (0.24 mmol) of acetamylpyruvic acid and Fe (AA) 2 and 25 mmol of acetic acid. Stir at 100 ° C in a gas atmosphere for S hours. Cyclohexane conversion rate was 72%, adipic acid was obtained with a yield of 65% (the selectivity based on hexane was 9%. Glutaric acid was also obtained with a yield of 5% (the selectivity based on hexane was 7%.) .._ Example. "丄 2. Take 1.68 g (20 mmol) of cyclohexane, 0.26 g (1.6 mmol) of N-hydroxy Ifeimine, MnUA) 2 0.005 g (0.02 mmol) Ear), Fe (AA) 2 0.02 g (0.08 mmol), 25 ml of acetic acid, stirred in a gas atmosphere garden at 100 TC for 6 hours. Hexane conversion of 56% to adipic acid, Yield 52% (selection rate based on cyclohexane 92%). In addition, glutaric acid was obtained, yield 3% (selection rate based on cyclohexane based on 5%). J5U. The compound was reacted in the same manner as in Example A 1-1, and adipic acid was obtained with a cyclohexane conversion rate of 56% and a yield of 10%. In addition, cyclohexanone was produced in a yield of 30%, and hexanol was produced in a yield of 4%.

Implementation: Example il di L Take 1.12 grams of cyclooctane (10 millimolar), 0.13 grams of N-hydroxypeptide pyrimide This paper size applies Chinese National Standard (CNS) Λ4 specification (210X297 mm) I --- ---- ^ r outfit ----- ^ " 丨 -------- Hugh-r (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 448137 A7 B7 V. Description of the invention (P) (0.8 millimolar), a mixture of cobalt (III) acetamylpyruvate Co (AA) s 0.015 g (0.0 beta millimolar 1, 25 ml of benzonitrile, Stirred at 100 C for 20 hours in an oxygen atmosphere. The products in the reaction solution were examined by gas chromatography. The cyclooctane conversion was 94%, and cyclooctanone (yield 43%) was obtained. 13%), suberic acid (yield 22%) and other products (yield 16%). Fen Example B 1-2 Cobalt (III) Acetylpyruvate Co (AA) 3 0.015 g (0.06) Millimoles) ¾ Cobalt (II) Co (AA) 2 with Acetylpropane 1 0.015 g (0.06 millimoles). The same reaction as in Example B 1-1 was performed, and the cyclooctane conversion was 9 9 % To obtain octanone (yield 41%), cyclooctanedione (yield 9%), suberic acid (yield 4 5 %) And other products (yield 4%). Actual pickling example 3.2 .. Except cobalt (III) acetonylpyruvate Co (AA) 3 0.015 g (0.0 6 mmol) changed to ethyl acryl propionate Except for class 1 manganese (II) manganese (II) Mn (AA) 2 0.021 g (0.06 millimolar), the same reaction was carried out as in Example B1-1. The conversion rate of octane was 94%, and cyclooctanone was obtained (yield 6%). , Cyclooctanedione (yield 10%), suberic acid (yield 74%) and other products (yield 4%). Example __Apply_Except for cyclooctane 10 millimolar instead of ring Nonane 10 millimolar, the same reaction as in Example m ~ 1, cyclononane conversion of 93%, cyclononanone (yield 34%), azelaic acid (yield 56%) and other formation (Yield: 3%), no detectable hydrazone. Example 14 -54- This paper size applies the Chinese National Standard (CNS) Ad specifications (2 [0 × 297 mm) I MM clothesline? Line ( #First smell the precautions on the back and then fill out this page)-|, 4 4 8 丨 3 7 A7 ___ _B7_ V. Description of the invention (㈠) In addition to octane 10 millimoles, use cyclononane 10 millimoles , And cobalt acetamylpyruvate UlI) Co (AA) 3 0.015 g (0.06 mmol) was changed to cobalt acetamylpyruvate (II) Co (AA) 2 0.015 g (0.06 mmol), the same reaction as Fen example B1-1 was reported, the cyclononane conversion rate was 99%, the yield of cyclononanone f was 29%), the dipic acid (yield 66%) and other formation (4% yield) and no cyclononadione was detected. In addition to cyclooctane 10 millimoles, the use of pannonane 10 millimoles, while cobalt (III) ethionyl propionate Co (AA) 3 0,015 g (0.06 millimoles) was changed to ethyl acetone Except for 0.021 g (0.06 mmol) of acid (II) Mn (AA) 2, the same reaction was carried out as in Example B 1-1, the cyclononane conversion was 93%, and cyclononanone was obtained (yield 5%) , Azelaic acid (yield 83%), and other products (yield 5%), no cyclononadione was detected. The results of the foregoing Examples B 1 to B 5 are shown in Table 1. (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs -55-This paper size applies to the Chinese National Standard (CNS) Λ4 specification (210 X 297 mm) 4 48] 3 7 A7 B7 Storage porch 1: £, ^ φ 菡 2: U®L storage 0 > 菡 3:11 evasion \ J // / IV Statement issued by the Central Consumers Bureau of the Ministry of Economic Affairs and printed by the Consumer Cooperatives of Example B5 Example of implementation B4 Example B3 Example B2 Example Bl-2 Example Bl-1 筘 ψ m matrix type Mn (II) 1 Co (II) Co (III) | Hn (II). Co (II) Co (III) auxiliary Catalyst type CD CC CO CD to • fo. CO 03 $ 槪 骟 一 CT CO CO Ca5 h · * CO Compound 1 Yield (%) O 〇o to Compound 2 CO CO 05 05 cn Oi " * ^ 3 tJl ΓΟ DO Compound 3 Ol OJ Other 95% 96% 97% 85% 87% 69% Selectivity of mono- and dicarboxylic acids (please read the precautions on the back before filling this page) This paper size is applicable to Chinese national standards ( CNS) Λ4 specification (21 «-publicly available) 1 37 Printed by A7 B7, Central Laboratories of Ministry of Economic Affairs, Consumer Cooperatives V. Description of invention (π) Example W. Take cyclooctane 1.12 g (1 Q Mol), N-Hydroxyphthalimide G. 13 g (0.8 mmol), Cobalt Acetylpyruvate (II) Co (AA) 2 0.015 g (0.06 mmol), acetic acid 25 The milliliter of the warm compound was stirred in a gas atmosphere at 12 ETC for 6 hours. The formation in the reaction solution was examined by gas chromatography. The conversion of octane was 95%, and suberic acid was obtained (yield 70%). Rich example: R 7 take 1.26 g (1G millimolar) of cyclononane, N-hydroxyphthalimide imine hydrazone. 13 g (0.8 mmol), Co (AA) 2 0.015 g (G.G6 mmol) ), 25 ml of acetic acid, stirred in a gas atmosphere at 10 (TC for 6 hours. The products in the reaction solution were checked by gas chromatography, the cyclononanone conversion rate was 92%, and cyclononanone (product Rate 46%), azelaic acid (yield 42%). 1.4.0 g (10 mmol) of cyclodecane and 0.13 g (G. 8 mmol) of N-hydroxyphthalimide , Co (AA) 2 G.015 g (0.06 mmol), a mixture of 25 ml of acetic acid, stirred at 1 G (TC for 6 hours in an oxygen atmosphere. Cyclodecane conversion S 6%, to obtain璟 Decanoic acid (yield 39%), sebacic acid (yield 48%), and cyclosebacic acid (yield 5%). Example R9 Except for the reaction temperature of 9D ° C, use Example B8 In the same reaction, the cyclodecane conversion was 90%, and cyclodecone (yield 64%), sebacic acid (yield 14%), and cyclodecanedone (yield 4%) were obtained. 1 0 Except that the reaction temperature is 12 ° C, the reaction is the same as in Example B8. Cyclodecyl-57-This paper & size applies the China National Standard (CNS) Λ4 specification. (210 > < 297 Gong) --- I--ί-'_— 士 Κ ------ 丁 ----- 泉 0¾ t., I (Please read the notes on the back first (Fill in this page) 448] 37 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (d) The conversion of alkane is 99%, and cyclodecane (yield 24%), sebacic acid (yield 71) %). Actually, except for CoiAA)? 0. 0 15 grams (0.06 millimoles) was replaced with Mη (AA) 2 0.021 grams (0.06 millimoles), according to Example B8. In the same reaction, the conversion rate of cyclodecane was 89¾, and acetodecone (yield 4%) and sebacic acid (yield 82%) were obtained. Example: 1.40 g of decanodecane (10 mmol) Instead of using 1.54 g (10 mmol) of methylcyclodecane, the same reaction was carried out as in Example B8. The methylcyclodecane conversion rate was 85%, and 9 monogasic decanoic acid was obtained (yield 6 7). 2-methylcyclodecanone (yield 15%) 〇 实 'mi Take 璟 + dioxane 1.6δ g (10 millimoles), N-hydroxyphthalimide imine 0.13 g (0.8 millimoles), Co ( AA) 2 0.015 g (0.06 mmol), 2.5 ml of acetic acid, stirred at 100 ° C for 6 hours in an oxygen atmosphere, and the conversion rate of the dodecane was 96 %, To obtain cyclic + dialkanone (yield 36%), dodecanedioic acid (yield 51%), and dodecanedione (yield 7%). __.____________ 1 Remove Co (/ U) 2 0.015 grams (0.06 millimoles) and use Mn (ΑΑ) 2 0.021 grams (0.06 millimoles), and stir for 8 hours at 10〇υ 搀In addition, according to the same reaction as in Example B13, the cyclododecanization rate was 92%, and cyclododecanone (yield 2%), dodecanedioic acid (yield 84%) and cyclododecanedione were obtained. (6% yield). Real __. 陁 .MAli except for mixing at 8 5 I ft for 6 hours, the same reaction as in Example B 1 3, cyclododecane conversion rate of 84%, cyclododecanone (yield 69%), ten Dioxane Please read the precautions before you draw the binding page. The paper size is applicable to the Chinese National Standard (CNS) Λ4 specification (210 X 297 mm) 4 4813 A7 B7 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Description of the invention (^) 1 diacid (yield 12%) and dodecanedione (yield 3%). 1 1 I 〇 * g Έ application 1 1 take 璟 + tetraoxane 1.96 g (10 millimolar), hydrazone-hydroxyphthalimide 0. 13 please! First i grams (0.8 millimolar), Co (ΑΑ) 2 0. 015 g (0,06 millimolar), B reading 1 acid 25 liters of mixture, stirred in a gas atmosphere at 100 t for 6 hours on the back 1 I 1 ring + courtyard conversion The rate was 92%, and cyclotetradecanone (yield 32%) was obtained. Ten attention 1 # 1 second courtyard diacid (yield 52%) and cyclotetradecanedip P (yield 8%). Shi. Μ —C-1 Fill in this pack 1 and take 瑗 hexene ί. 64 grams (20 millimoles), Ν-hydroxyphthalimide_imine 0.26 grams 贲, 〆1 I Π • 6 tip · Moore >, Cobalt ethanoate co (AA): 0.043 g (0.12 1 1 mmol), a mixture of 25 ml of acetonitrile in a gas atmosphere, wedge at 100 1 11 for 6 hours. The formation in the reaction solution and the use of gas chromatography to check the cyclo AI cyclohexene conversion rate of 90%, to obtain 2-cyclohexene-1 range (Cyclohexene benchmark selection 1 rate 72% ♦ yield 65%), and 2 -cyclohexene-1-alcohol (choose 1% of cyclohexene basis 14%, yield 13%). 1 1 tjSs: Έ_ 施 JLC_2. 1 -7 Except that hexene was changed to cyclopentene, the reaction was carried out in the same manner as in Example C1. The cyclopentene 1-ene conversion was 80% to obtain 2-cyclopentene-1 -one ( The cyclopentene-based selectivity is 1 | 66%, and the yield is 53%), and 2-pinepentene-1-ol (the cyclopentene-based selection is 21%, the yield is 17%). 1 | 实. —CJ 1 ί take octene 1. 10 g (10 mmol), Ν-hydroxyphthalimide 0 • 1 3 g 1 ί (0.8 mmol), acetamidine Cobalt pyruvate Co (AA): a mixture of 0.021 g (0.06 I mole) and 25 ml of acetonitrile in a gas atmosphere at 100Ό 1 1 Ι -59 1 1 1 This paper size applies to Chinese national standards (CNS ) Λ4 is present (210X297). A7 B7 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention (may) Stir for 6 hours. The products in the reaction solution were examined by gas chromatography, and the cyclooctene conversion was 35% to obtain 2-cyclooctene-1-one (the selectivity based on cyclooctene was 82%, the yield was 78%), and 2-Cycloctene-1-ol (Cyclooctene-based selectivity 16%, yield 15%). Casement example. 4 Except that acetonitrile was changed to acetic acid and the reaction temperature was 9 ° C, the same reaction as in Example C 1 was carried out, and the cyclohexene conversion was 95% to obtain 2-cyclohexene-butanone (selectivity based on cyclohexene 4 3%, yield 41%), and 1-acetamido-2-cyclohexene (Cyclohexene-based selectivity 45%, yield 43%). Hh Comparative Example C1 Take cyclohexene A mixture of 1.64 g (20 mmol) of azobisisobutyronitrile (5 mol%) and acetonitrile (25 ml) was stirred at 9 (TC for 4 hours in an oxygen atmosphere. Analysis, the conversion of cyclohexene was 34%, and 2-cyclohexene-1 -one was obtained (the selectivity based on cyclohexene was 12%, the yield was 4%), and 2-cyclohexene-1- Alcohol (Cyclohexene-based selectivity 3%, yield 3%) β Miyazaki Example D 1-1 Take adamantane 1.36 g (10 mmol), N-hydroxyphthalimide Q. 13 g (0.8 MM), cobalt (III) acetamidate pyruvate Co (AA) 3 0.D15g (0.G6 millimolar), 25 ml of acetic acid, stirred at 9 Q ° C in an oxygen atmosphere In 8 hours, the adamantane conversion was 65%, and 1-adamantanol was obtained (the adamantyl quasi-selectivity was 71%, the yield was 46%), 1, 3- Adamantanediol (17% selectivity for adamantyl, yield 11%), 2-adamantanone (9% selectivity for adamantane, yield 6%). Selectivity for alcohol is -6 0-This paper size applies to China National Standards (CNS), 8 4 grids: ϋ ... mm) --------- · 1 pack ----- J —Order ----- -Line (please read the precautions on the back before filling this page) 8 4 1 3 7 A7 B7 V. Description of the invention (〇) 89% 0 宁 抡 例 ～ [) 7-1 Except for the conditions shown in Table 1, The reaction was carried out in the same manner as in Example D1-1, and the results in Table 2 were obtained. In Table 2, Compound 1 was 1-adamantane alcohol, Compound 2 was 1,3-adamantanediol, and Compound 3 was 2-adamantanone. In addition, the "other" products in Table 2 are mostly ketoalcohols of adamantane. Window Example 1) 1-2 ~ Except cobalt (III) Co (AA) 3 β (0.5) g of acetamidopyruvate, and 0.015 g of cobalt (II) Co (AA) 2 glyoxal pyruvate, Examples 2-1 to D 7-1 were reacted under the same conditions to obtain the results shown in Table 2 蒈 Example [) 7-2 Except for the conversion of acetic acid to benzonitrile, the same reaction was performed as in Example D 4-2 to obtain Table 2 Results shown. In the examples in Table 2, the "other" products were mostly 1,3,5-triamantanetriol and 1,3,5,7-adamantantetraol, and no alcohol was detected. --------- 1 Pack ----- Custom Order ------ Line (Please read the precautions on the back before filling this page) Printed by the Central Standards Bureau of the Ministry of Economy -61- This paper size is in accordance with the Chinese National Standard (CNS) Λ4 specification (210 × 297 mm) V. Description of the invention (k) A7 B7 Printed by Xu Pingxi, Shellfish Consumer Cooperative of Central Standards Bureau, Ministry of Economic Affairs存 存 遨 2: 1,3- 眇 · 莂 hsl,. {ΓΓα > ^ 3: 眇 · 筘 圏 AcOH ,, ίΝ®. · © .CN: ^ s Μ W wn SH, ΛΓΠ η US n Μ at m Contributory salary m 坌. 宝 漥 窆 S 1 — ο cn οο 〇— cs cn i CO 〇s 1 t— »c = i private 1 CO CJ1 1 h—l C = J CO 1 CO β private 1 1—i α CO 1 ΕΌ ϋ to I α Η " * 1 ΕΌ α CO 1 C3 O ο ο < * ~ s C5 〇o < ra O oo ο ο ra o Ο ο < n ο ο Λ Λ Ο ι · * ™ ·% ca ο / * · »Si S HH 11 V— ·· Ι-Η 1 · —1 ΗΗ ΗΗ Ι · Ή HH Hi 1-HJ—1 -w *-lH h * H ^ _ ^ · Ι-Η ΚΗ 1—-ι 'w * t—1 1 ~ 1 ^ _ »· ►—II—I Ι-Η 1-4 1 ~ l ΗΗ 1-1 μ-1 ΗΗ 11 l—l hH κ- (Woven Ramie * <) CJl C D CJl CO art m cn Reaction temperature (° C) 1— ^ C5 CT > 05 f— * o Oi CO σΐ Reaction time (hr) φ CN AcOH AcOH AcOH AcOH AcOH AcOH AcOH AcOH mm ej% cn ς〇ςο CO UD cr » CD CO CO CD CD IS5 CD 00 05 〇 > σ »CJl cn C71 〇J Conversion rate (%) ii rr OJ CaJ Two Oi σϊ '< 1 CO CO 05 U1 CO Oi ς〇 Office 05 Oi Private OJ to α > m tree ΓΓ μ— * ot 0〇4¾ cn CO CO 05 CJT 00 rc 〇 CJ1 cn CD H ** CO 1— ^ 2 o Π > * · »* · * 漤 CO rr A cn to private 〇ϊCO Ca5 1 —1 CO a > 菡 CO CO CO os CO DO fO CO to K ς〇CO c * 3 • " «3 < LO cn •« 3 CJ1 «5 -J -s3 05 CO 〇ϊ oo CO c〇〇〇 oo C £ 5 C〇00〇to Chengshi® -------------- ΐτ ----- ά.. *, (Please read the notes on the back before filling this page ) This paper size applies to Chinese national standards (CNS > Λ4 size (210 X 297 mm) 8 4 1 3 7 A7 ____B7 V. Description of invention (fri) Central Bureau of Standards, Ministry of Economic Affairs Printed by the Industrial and Commercial Cooperatives .. Shi, .. Example _D__8_ Take 1.64 g of 1,3-dimethyladamantane (10 mmol), 0.13 g of hydroxy-phthalocyanine (0.8 mmol), Co (AA) 2 A mixture of 0.015 g (0,06 mmol) and 10 ml of acetic acid was stirred at 70C for 6 hours in a gas atmosphere. 1, 2-dimethyladamantane conversion of 99%, hydroxy-3,5-dimethyladamantane (yield 39%), 1,3-dihydroxy-5,7-dimethyladamantane (Yield 5 S. The selectivity of alcohol is 9?%. Actual J.—9— except that the reaction temperature was changed to 60o, the same reaction was performed as in Example 8, and 1,3-dimethyladamantane was converted. The yield was 74%, and hydroxy-3,5-dimethyladamantane (yield 49%), 1,3-dihydroxy-5,7-dimethyladamantane (yield 22%). The selectivity rate is 96%. Exempt from the ammonium alcohol. 52 g (10 mmol), H-hydroxypeptide hydrazine 0.13 g (0.8 mmol), CoUA) 2 0.015 g (0.0 6 Millimoles), a mixture of 25 ml of acetic acid, and stirred at 75 C for 3 hours under an oxygen atmosphere. : I-adamantane conversion of 80%, 1,3-adamantanediol (66% selectivity to 1-adamantanol, yield 53%) and 1,3,5-adamantanetriol Alcohol (33% selectivity to 1-adamantanol, 26% yield). The alcohol selectivity was 99%. Real mil. -6 3 ~ (Please read the precautions on the back before filling out this page)-Installed · The size of the paper is suitable for China's Fi CNS. Λ4 specifications (210X 297). Central Bureau of Standards, Ministry of Economic Affairs Beigong Consumer Cooperative Co., Ltd. India policy A7 B7 V. Description of the invention (h) Except that after stirring at 85C for 6 hours, the reaction is the same as that of Cao Shi Example D10. The conversion rate of 1-adamantanol is 99%, and 1,3-adamantane di Alcohol (42% selectivity with respect to almantanol, yield 42%), 1,3,5 -adamantanetriol (46% selectivity with respect to 1-adamantanol, yield 46%), 1,3,5,7-adamantane tetraol (selectivity of 10% to 1-adamantanol, yield of 10%). The alcohol selectivity was 99%. Example. Μ_2.ι. Except after mixing at 9 5¾ for 6 hours, the reaction was the same as in Example D10. The conversion rate of 1-adamantanol was 99%, and 1,3-adamantanediol (relative to 1- The selectivity of amantadine is 22% and the yield is 22%), 1,3,5 -adamantanetriol (the selectivity is 14.1% and the yield is 41% compared to 1-adamantanol), 1, 3, 5, 7-adamantane tetraol (36% selectivity and 36% yield relative to diamantane). Alcohol selectivity was 99%. Real jfeUD 丄 3_. Take 1.68 g (10 mmol) of 1,3-adamantanediol, 0.13 g (0.8 mmol) of N-hydroxyphthalocyanine, and 0,015 g (0.06 mmol) of Co (AA) 2 Ear), 25ml of acetic acid, in a gas atmosphere, mix at 95tti for 6 hours. 1, 3-adamantanediol conversion rate of 99%, to obtain 1, 3, 5-adamantane triol (selection rate of 37% with respect to 1, 3-adamantanediol, yield 37%), 1,3,5,7-adamantane tetraol (62% selectivity to 1,3-adamantanediol, yield 52%). Alcohol selectivity was 99%. Actually ... apply gold_alkane 0, S 8 g (5 mmol), 1-adamantanol 0.26 g (5 mmol), N-hydroxyphthalimide 0.13 g (0.8 Millions), Co (AA) 2 -64- This paper size is applicable to Chinese National Standard (CNS) A4 (2 丨 〇 X 297 mm) (Please read the precautions on the back before filling this page). Order 3 · / 8 A7 '___ B7 printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the Invention (Η) 0. 0 1 5 g ί 0. 6 mmol), a mixture of 2.5 ml of benzonitrile In a gas atmosphere, stir at 8 5 υ for 6 hours. Amantadine conversion rate 1%, amantadine alcohol (yield 33%), 1,3-adamantane dienzyme (yield 41%), 1,3, 5 -adamantanetriol (yield 21%) . Alcohol selectivity was 99%. Actually ... take 0.96 g of original linoleane, (10 mmol), 0.13 g (0.1 mmol) of N-hydroxyphthalimide, 0.015 g (0.06 mmol) of Co (AA) 2, acetic acid 10 ml of the mixture in a gas atmosphere, mixed with 75¾ for 15 hours, the conversion rate of 99% of the original lindenene was obtained, and the 1-hydroxyorborninane was selected (the selectivity relative to the original lindenene was 44%, and the yield was 44%). ), And 1,2-dihydroxyorbornein (55% selectivity and 55% yield). Alcohol selectivity was 99%. Example-Example " Take 1.5 g (10 mmol) of tricyclic [4.3.1.1. 2, 5] undecane, 0.13 g (0.8 mmol) of H-hydroxyphthalocyanine, Co (ΑΑ ) 2 0.015 g (0.06 mmol) of warm compound f in 10 ml of acetic acid, stirred at 751 for 15 hours in a gas atmosphere. Tricyclic [4.3.1.1. 2, s] undecane conversion of 99%, to give 1-hydroxytrisamidine [4.3.1.1. 2, 5] undecane (relative to tricyclic [4, 3.1.1. 2 '5] undecane selectivity of 24%, yield of 24%). And dihydroxytricyclo [4 · 3.1.1. 2, 5] undecane (relative to tricyclo [4.3,1 · 1.2'5 [Undecane selectivity 75%), yield 75% »Alcohol_selectivity 99%. 〇Example. Jm. Take 1.38 g (10 mmol) of pinane, 0.13 g of N-hydroxyphthalimide-6 5-This paper size is applicable to China National Standards (CNS) M specifications (2 丨 0X 297 mm) Pre-ordered · '., (Please read the notes on the back before filling out this page) 448 13 A7 B7 V. Description of the invention (Μ ·) (0.8 millimoles). Co (AA) 2 0.015 A mixture of gram (0.06 mmol) and 25 ml of acetonitrile was stirred in a gas atmosphere at 100 ° F for 6 hours. The conversion rate of pinane was 90%, and 2-hanalkanol was obtained (selectivity of 91% relative to suntan, yield S2%). Implementation. 1-D1 and. Take 1.38 g (10 mmol) of cis decalinane, 0.16 g (1.0 mmol) of N-hydroxyphthalimide, and 0.0003 g (0.05 mmol) ), Acetic acid 10 milli Kelvin, in an argon atmosphere, stirred at 50 TC for 6 hours. The conversion rate of cis-naphthacene is 65%, and 1-hydroxycis-denaphthane is obtained (the selectivity of cis-type pinane is 71%, and the yield is 46%). 17% selectivity relative to cis-methane, yield 11%), hydroxycis denaphthyl hydride that has been argonized in the methylene part (6% selectivity, 4% yield to is-type decalin) , β 1, 6-decalindione (selectivity of 5% with respect to cis decalin, yield of 3%). Alcohol selectivity was 94%. Real ife—example „D.ia Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) Take 1.38 g (10 mmol) of cis-methane, κ-hydroxyphthalide A mixture of rhenium imine 0.16 g (1.0 mmol), 0.003 g (0.05 mmol), and 10 ml of naphthalenenitrile, stirred in a gas atmosphere at 7 5 υ for 6 hours. The conversion of cis-paraffin The rate is S 5%, and the hydroxycis denaphthane is selected (the selectivity of cis-didecane is 72%, and the yield is 61%). (21% yield, 1δ% yield), hydroxycis denaphthenes which are vaporized in the methylene part (selectivity 2%, yield 2%), and 1, 6-pinane Diketones (selection rate 4%, yield 3% relative to cis-pinane). Selectivity rate of alcohols 95%. -6 6- not good. ¾ scale applies Chinese National Standard (CNS) Λ4 specification (2! 0 '〆297 mm) 4 8 13 7 A7 B7 printed by the shellfish consumer cooperation department of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention Ur) Implementation _ 1.38 g (10 millimolar) of cis-type pinane, N- Hydroxyphthalimide 0.16 g (1.0¾ mole), Mo〇3 A mixture of 0.007 g (0.05 mmol) and 10 mmol of acetic acid was stirred in a gas atmosphere at 7 5 t for 6 hours. The conversion rate of cis-type alkane was 91%. Selectivity of 66%, yield 60%), 1,6-dihydroxycis denaphthenes (compared to selectivity of 21%, yield 19%), in the methylene part Gasified hydroxycis denaphthane (selectivity 4% with respect to cis denaphthane, yield 4%), and 1,6-dianedione (selectivity 9% with respect to cis denaphthane, Yield: 8%). Alcohol selectivity: 91%. __ILJ5! UL2 丄. Take 1,38 g (10 mmol) of cis-methane and 0.16 g (1.0 mmol) of N-hydroxyphthalimide '), A mixture of 0.017 g (0.05 millimolar) of manganese acetopropionate Mn (AA), 10 ml of benzonitrile, and agitated at 7 5 1 C jft for 6 hours in a gas atmosphere. The conversion rate of cis-Lerane is 75%, and the hydroxycis-pinenine (with a selectivity of 71% relative to cis-naphthyl, 55% yield), and 1,6-dihydroxynickel-type decalin (relative to cis-type decalin) The selectivity of decalin is 16%, and the yield is 12%.) The selectivity is 4%, the yield is 3%), and 1,6-naphthalkanedione (relative to the selectivity of cis-Ceane is 5%, the yield is 4%). The selectivity of alcohol is 93%. Real milk 1 JX2_2_ Take the bridge tricyclic [5.2.1.02,6] decane 1.36 g (10 mTorr), H-hydroxyphthalimide imine 0.16 g (1.0 mmol), Mo0_3 0.007 g (0.05 mmol), acetic acid 1 〇mL of mixture, in an oxygen atmosphere, -6 7-This paper size applies to Chinese national standards (CNS > A4 size (210X297 mm)) ^ 1 n — ^ 1 Ι1Λ ^^^^ 1 ^^^^ 1 —S fi ^ lf ^^ ii n · I j 凄 ^ i) Shao (Please read the precautions on the back before filling out this page) 8 Printed by the Central Laboratories of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives t 4 A7 B7 Description of Invention (W) Stir at 65 ° C for 6 hours. Bridge tricyclo [5. 2 · 1.. G 2 ^] decane conversion rate of 51%, to obtain 2-hydroxy bridge tricyclo [5. 2. 1. 1.0 2 's] decane 45%, yield 23%), 2,6-dihydroxy bridged tricyclic [5.2.1.02'6] decane (selectivity to substrate 49%, yield 25%), bicyclic [5.2.1] Decane-2,6-two-country (selectivity to substrate 49%, yield 2% h selectivity 94%. Example. J23 Tricyclic [5.2.1.0% 6] decane 1.36 g (10 mmol), N-Hydroxyphthalimide 0.16 g (1.0 mmol), Μ03 (ΚΟ (Πg (0.05 mmol), acetic acid 10 mmol) mixture in an oxygen atmosphere Inside, stir for 6 hours at 65 ° C. Hang tricyclic [5. 2.1 · 0 2 's] decane conversion rate of 43%, to obtain hydroxy hang stilbene [5, 2.1, 02, 6] dec Alkane (selectivity to the substrate 72%, yield 31%), 2,6-dihydroxy hang tricyclo [5.2.1_0 2 J] decane (selectivity to the substrate 23%, yield Rate of 10%), bicyclo [5.2.1] decane-2,6-dione (selectivity of 5% relative to matrix, yield of 2%, selectivity of alcohols S 5%. Cellulose 1 ) 24 Take four 璟 [4.4.0.1. 2,5 I7,1. ] Dodecane 1.62 g (10 mmol), N-Hydroxyarsinimine Q. 16 g (1.0 mmol), MoO 3 0.0 0 7 g (fl.05 mmol), acetic acid 10 ml The mixture was stirred in an oxygen atmosphere at 5 ° C for 6 hours. As a result, the conversion rate of tetracyclo [4.4.0.1.2, sl7'iG] dodecane was 55%, and 1-hydroxytetracyclo [4. 4 · 0. 1 · 2 ， s 1 ～ 10] + dioxane (67% selectivity to substrate, yield 37 ° /.), 1,6-dihydroxytetracyclo ^ 6 8 w Applicable to Chinese National Standard Li (CNS) Λ · 1! Youge: 0 public goods. One pack of Ί 订 order first line (please read the notes on the back before filling this page) 448 1 3 Staff of the Central Standards Bureau Consumer Cooperative Indo A7 B7 Five 'Invention Description (π) [4.4 0. 1. 21 \] Dodecane (selectivity to substrate 18%, yield 10%), tricyclic [6.2, 1.13, 0] Dodecane-2,7-dione (13% selectivity to substrate, 7% yield). Alcohol selectivity · 85%. Fen. Shili_D_2 Five take cis-peroxindene 1.26 g (10 mmol), N-Hydroxyphthalimide 0.16 g (1.0 mmol), M0 30 007 g (0.05 millimolar), 10 ml of warm compound of acetic acid, in a chlorine atmosphere, and stirred at 7 5 υ for 6 hours. The conversion rate of cis-perhydrogen was 87%, and 1-hydroxycis-perhydroindane was obtained (62% selectivity to the substrate, yield 54%). (31% selectivity relative to substrate, 27% yield), hydroxycis-type gold indane with methylene sites vaporized (3% selectivity relative to substrate, yield 2¾), and 1,6- Nonanedione (5% selectivity to matrix, 4% yield). Alcohol selectivity was 95%. Place—Apply JLH2, —6—Except for stirring at a reaction temperature of 140 ° C for 6 hours, the reaction was carried out in the same manner as in Example D 1 8. The full conversion of cis-naphthalene was 95¾. 18% selectivity, 17% yield), 1,6-dihydroxycis-naphthyl naphthalene (3% selectivity to matrix, 3% yield), 1,6-decanedione (relative to matrix The selectivity was 73% and the yield was 69%). Alcohol selectivity was 21%.

Straight example "-2_.L take 10 millimoles of adamantane, 1 millimole of N-hydroxyphthaloimine, acetone acetonone (ΙΠ Cu (AA) 2 0.05 millimoles, 25 ml of acetic acid The mixture is stirred in a gas atmosphere at 7 5 for 6 hours. The adamantane is turned to 6 9. The paper size is applicable to the Chinese National Standard (CNS) Λ4 specification (210X297 mm). I .—------ Η I Packing ------ ordering ------ gland one: (Please read the notes on the back before filling out this page) 448J37 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Description of the invention ( The 60% conversion rate is 53%, and amantadine (yield 50%), and 2-adamantane (yield 4%), the selectivity of alcohol and ketone is 97%. Fenfeng MD? 8 Take adamantane 10 millimoles, N-hydroxyphthalimide 1 millimoles, zirconyl propionate zirconium (IV > Z r (AA) 2 t). 0 5 millimoles, acetic acid 2 5 The mixture was stirred in an oxygen atmosphere at 7 5 ° C for 6 hours. The conversion of adamantane was 43%, and amantadine (yield 28%), 1, 3 -adamantanediol (yield) 6%), 2-adamantanone (yield 3%). Rich example 1) 29 take 10 mM amantadine N-Hydroxyphthalimide 1 millimolar, ZrO (OAc) 2 0.05 millimolar, 25 ml of acetic acid, stirred in an oxygen atmosphere at 7 5 ° C for 6 hours, adamantane conversion The yield was 91%, and 1-adamantanol (yield 42%), 1,3-adamantanediol (yield 31%), and 2-adamantanone (yield 7%) were obtained. Example D 3 0 Take 1D molar of adamantane, 1 mol of N-hydroxyphthalocyanine, VO (AA) 2 acetamidopyruvate 0.05 mol, and stir in an oxygen atmosphere at 7 5 ° C In 6 hours, the adamantane conversion was 98%, and 1-adamantanol (yield 25%), 1,3-adamantanediol (yield 34%), and adamantanetriol (yield 6%) were obtained. Amantadine tetraol (yield 7%). Guan Lili Π.Ή In addition to acetamyl pyruvate gas vanadium V0 (AA) 2 Switch to acetamyl propionate! Vanadium acid V (AA) 3 0.0 5 millimoles In addition, according to Example D3Q, the same reaction was performed, and the adamantane conversion was 99%, and 1-adamantanol (yield 27%), 1, 3 -adamantane-7 0-This paper size applies Chinese national standards ( CNS) Λ4 specification (21 0X 297 mm) ^^ 1----n I -I nn mj a ^ nn ^ i — -I--I-.......-'一 OJ-- --- -.---^ {Please read the notes on the back before filling out this page) 448 1 3 7 Printed by A7 B7, Shellfish Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs 5. Description of Invention () Diol (Yield 34%) , Amantadine triol (yield 6%), Amantadine tetraol (yield 7%). The reaction was carried out in the same manner as in Example D30 except that the acetamylpyruvate oxygen m V 0 (AA) 2 was changed to vanadium oxide V 2 0 05 0.05 mol. Alkanol (yield 24%), 1,3-adamantanediol (yield 35%) S amantadine triol (yield E3%), adamantane tetraol (yield 8%). Example [) 3 3 Except for acetamylpyruvic acid vanadium V 0 (AA) 2 instead of vanadium oxide V 2 〇03 0.05 mmol, according to the same reaction as in Example D3 0, the adamantane conversion was 9 9%. 1 " Amantadine (yield 23%), 1,3-Adamantanediol (yield 3 6%) S Amantadine triol (yield 8 ° / 〇), Amantadine tetraol (yield 8%) = W Example P34 Except for ethyl ii-pyruvate gas vanadium V 0 (AA) 2 instead of nitrogen gas vanadium V 0 C 1 2 9 The same reaction as in Example D 3 〇, the adamantane conversion rate was 98% To obtain 1-adamantanol (yield 28%), 1,3-adamantanediol (yield 32%), amantadine (yield 5%), and amantadine tetraol (yield 4%) 〇xiao 旃Example P3f) Take amantadine 10 millimoles, N ~ hydroxyphthalimide m imine 2 millimoles, acetamidine pyruvate vanadium V (AA) 30.1 millimoles, acetic acid 2 5 ml of a mixture of 9 in gas Stir at 85 ° C for 1 hour in a gas atmosphere. The conversion rate of adamantane is 99%. 1-Amantanol (yield 8%), 1,3-Adamantanediol (yield 22%). Alkanetriol (yield 33%), King Kong Yuan tetraol (yield 20%) 〇 Example D3R -71- (Please read the precautions on the back before filling this page) This paper size is applicable to Chinese interpreters Pillow- < V. CAS: Λ4 specification (2I0X 297 male Zhao) Printed by A7 B7, Shellfish Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs 5. Description of the invention (8) Use V (AA) 3 except vanadylacetonate Manganese acetopyruvate Mn (AA) 3 0.1 millimolar, reacted in the same manner as in Example D3 5 and the conversion of adamantane was 97%, to obtain amantadine (yield 49%), 1, 3-adamantane Alkanediol (yield 24%), adamantanetriol (yield 3%), adamantane tetraol (yield 2%). Except that the acetamylpyruvate V (AA) 2 was changed to arsenic acid 2 MoO 4 0.1 millimolar, the same reaction was carried out as in Example D 35, and the adamantane conversion S 9% was obtained. (Yield 5?%), 1,3-adamantanediol (yield 22%), adamantanetriol (yield 3%), and adamantanetetraol (yield 3%). Window Example D38 The same reaction as in Example D 35 was performed except that Acetylpyruvate V0 (AA) 3 was changed to Acetylpyruvate] (II) C u (AA) 2 ϋ. 1 mmol, Amantadine conversion of 49%, yielding amantadine (yield 42%), 1, 3 -adamantanediol (yield 6%), β Umbell Example Ufl, except vanadylpyruvate V (AA ) 3 Zinc Acetylpyruvate (II)

Zn (AA) 2 0.1 millimolar, according to the same skin application as in Example D35, the adamantane conversion was 4 Q%, and 1-adamantanol (yield 30%), 1, 3 -adamantanediol ( Yield 7%). Example 1) 40 Except that vanadium acetopyruvate VG (AA) 3 was changed to aluminum acetopyruvate (III) A1 (AA) 3 0.1 mol, the reaction was the same as in Example D35. The alkane conversion was 15% to obtain 1-adamantanol (yield 1 Q%), and 1,3-adamantanediol (2% yield). -7 2-This paper size is applicable to Chinese National Standard (CNS) Λ4 specification (2 ίΟ X 297 公 《I -------: I installed -------- Order ----- / line (please (Please read the notes on the back before filling this page) ϋ. Α7 Β7 V. Description of the invention (")

Implementation of MJ AL The same reaction as in Example D 3 5 was carried out except that vanadium acetopyruvate V (AA) 3 was changed to magnesium (II) acetophenone sf AA) 2 0.1 mol. The alkane conversion was 22%, and 1-adamantanol (13% yield) and 1,3-adamantanediol (2% yield) were obtained.

Example: 12L Except for vanadium acetopyruvate (VUA) 3 and 0.1 mol Sr2 iodide, the reaction was carried out in the same manner as in Example D35, and the adamantane conversion was 34% to obtain 1-adamantanol (yield 22%), 1,3-adamantanediol (4% yield). Practice ... Exemplification. "丄 Take 0.921 g (10 mmol) of toluene, 0.16 g (1 mmol) of hydroxy peptide pyrimide, cobalt (II) Co (AA) 2 A mixture of 0.015 g (0.05 mmol) and 25 ml of acetic acid was stirred at 100 t for 6 hours in a chlorine atmosphere. The product in the reaction solution was detected by gas chromatography. The toluene conversion was 95%, and benzoic acid was obtained in a yield of 75% (selection rate 100%). Real — Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling this page), except that it was stirred at 100 ° C for 4 hours, the same reaction as in Example E1, the conversion rate of toluene was 93%, Benzoic acid was obtained with a yield of 92% (selectivity 99%). Actually, Shi M.El took 1.06 g (10 mmol) of p-xylene, 0.32 g (2 mmol) of N-hydroxyphthalocyanine, and cobalt (III) acetamidopyruvate C0 (AA). 3 0.018 g (0,0 5 mmol), 25 ml of acetic acid, stirred in an oxygen atmosphere at 100 t for 12 hours, the conversion of p-xylene was 99%, and p-benzene-73-benzyl was obtained. Paper Size Application Standard (CNS) Λ4 Specification (210X297) 4 4 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 4 A7 B7 V. Description of the Invention 0) Dicarboxylic acid (yield 71%) Methylbenzoic acid (24% yield). Except that R was stirred at 1 G (TC for 6 hours) and reacted in the same manner as in Example E 3, the conversion of p-xylene was 99 ° / °, terephthalic acid (yield 9%) and p-methyl Benzoic acid (yield 76%). Example: 1.06 g (10 mmol) of p-xylene, 0.16 g (1 mmol) of N-hydroxyphthalimide, and cobalt (II) acetamidopyruvate Co (AA) 2 G.018 g (0.05 millimolar), a mixture of 25 ml of acetic acid in an oxygen atmosphere. Stir at 1 fl 0 ° C for 12 hours, the conversion of p-xylene is 99%, and p-benzene is obtained. Di-formic acid (70% yield) and p-methylbenzoic acid (27% yield).

Except for melamine RR, which was stirred at 100 ° C for 6 hours, the reaction was the same as in Example E 5. The conversion of para-xylene was 99% > terephthalic acid (yield 57.7%) and p-methyl Benzoic acid (42% yield).

Example U: Take 1.06 g (10 mmol) of o-xylene, 0.16 g (1 mmol) of N-hydroxyphthalimide, and cobalt (II) Co (AA) 2 0.018 g (0.05 millimolar), a mixture of 25 ml of acetic acid in a gas atmosphere,

Stir at 100 ° C for & hours, conversion of o-xylene is 98%, terephthalic acid (yield 40%), o-methylbenzoic acid C yield 46%) and phthalic anhydride (yield 1 0%). Ninth case ES takes 1.06 g (10 mmol) of o-xylene, 0.16 g (1 mmol) of N-hydroxyphthalocyanine, and cobalt (III) Co (AA) 3 acetamidine propionate (Q.018 g) -7 4-The size of this paper applies to the ten national standards (CNS) Λ4 specification (210X297 mm) ----------..-- installation ------ order -----. (Please read the notes on the back before filling this page) Α7 Β7 V. Description of the invention (ο) (Please read the notes on the back before filling this page) (0.05 millimoles), a mixture of 25 ml of acetic acid, in Stir at 100 ° C for 6 hours in a gas atmosphere. The conversion of o-xylene is 92%, terephthalic acid (yield 18%), and o-methylbenzoic acid (yield 71%).例 例 例 .E9. Take 1.49 g (10 mmol) of 4-to-butyl-1-methylbenzene, 0.16 g (1 mmol) of H-hydroxyphthalocyanine, and cobalt acetamidine pyruvate ( III) Co (AA) 3 0.018 g (0.0 5 mmol), a mixture of 25 ml of acetic acid, stirred in a gas atmosphere garden at 100 t for 6 hours 4-tert-butyl-1 -methylbenzene conversion 95%, to give 4--butyl benzoic acid (. 8% yield). F. Example E .. L0 .. 'Take 1.49 g (10 mmol) of 4-pyridinobutyl-1-methylbenzene, 0.0 3 g (0.2 mmol) of N-hydroxyphthaloimine, Acetyl propionate cobalt (111) (: 0 (to) 3 0.0 1. 8 g (0.0 5 mmol), a mixture of 25 ml of acetic acid, stirred in a gas atmosphere at 1 0 0 1 1 2 Hour, 4-to-butyl M-methylbenzene conversion rate of 70%, 4--butyl benzoic acid (yield 64%) was obtained. Example 11-Ministry of Economic Affairs, Central Bureau of Standards Employee Consumer Cooperative printed 1.49 grams of 4-tert-butyl-1-methylbenzene (10 millimoles), 0.16 grams of N-acetaldehyde-based placentaimine (1 millimoles), acetamidopropanoic acid A mixture of 0.018 g (0.05 mmol) of cobalt (II) Co (AA) 2 and 25 ml of acetic acid was stirred in an oxygen atmosphere at 100 ° for 6 hours. % To obtain 4-tert-butylbenzoic acid (yield 94%). Implementation of JLE.U .. 1. 4-methylamino-1-methylbenzene 1.23 g (10 mmol), N-hydroxyphthalocyanine Amine 0,16 g (1 mmol), cobalt (II) acetopyruvate (Co) (AA) 2 -75- This paper size applies to the Chinese National Standard (CNS) Λ4 specification (210, 匁) d 48 3 A7 B7 Shu V. invention will be described (as) the surrounding atmosphere of 0.018 g% (0.Q5 mmol), a mixture of 25 ml of acetic acid, oxygen

% 2 9 rate production / 1 acid tolyl aerosol ethyl 1 4 yield% 5 9 rate conversion example quality base benzyl% radical 3 ο% 丨 month 7 7 3 _ change rate fet--T liter b car Production base millirotation (Γ oxygen 25 quality aldehyde benzyl 4-ethyl, except for the basic examples and should be applied hydroxy, trans 4- when benzonitrile ear-like) 1 mol% 2 8 mM 1 1 ο E 1 J rate ㈣ fresh Ϊ i Real acid 0 ^ 3 ί For the use of benzene, benzene ¾ ° I Mo I Ε «4-milli 5 31Π ο 2 to get milligrams ο 1X, ran% furan 92 radical methylation 2- conversion to quality modification Ear, Miaoying 10 samples of benzene homobase 12 A E-Example-Shiji Shiqi according to A, I.-.. 4 Xier Ermo% 8 8 Yield / V acid carboxyl 2- Example Nanfurfuran (Please read the precautions on the back before filling in this page) -Installation ·,-& Printed by Cooperative Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs, printed 1 w, 5% of the batch, 85 base rate for conversion 2 to quality Modified basal ears, Mo Yingchao 10 samples of benzene isopropyl 12 A E > Example 1-Shiji Shijiao A,-LT 4 Xi Erduo moran pyridine cellar to take _ material propyl compound formic acid% 3 8 rate Production of ^ fv-acid carboxylic acid mixing ratio of acetic acid conversion, millibenzene-5 ear 2 methanoic acid, At 1 o'clock, the small amine ear and the immo are mixed with the ITS phthalophthaloyl group. The 7 hydroxy group is at 3--, ΑΑ lower ear r (peripheral) c atmosphere mol I gas ο I —-α. 1, — V Oxyphenyl chrome applies the Chinese Standard for Storehouses (CNS) at this paper scale Λ4 is present (210X 297 cm) 8 4 ί 3 / " Ίη & κϋ3 ·; — Α7 Β7 Printed by the Consumers' Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs Preparation 5. Description of the invention (7 ^) i. 42% * Benzoic acid was obtained (yield 37%). 1 1 1 Implementation of Li-E · 1.3- t 1 Take 10 mmol of toluene, N-hydroxyphthalimide 1 mmol > Acetyl please 1 1 1 Nickel pyruvate Π I) nif AA) 2 0 + 0 5 millimoles, 25 ml of acetic acid mixed reading 1 1 The mixture was stirred at 70 1C for 6 hours under a gas atmosphere T Toluene conversion rate Φ 1 I 1 1 37% 4 Benzoic acid (yield 3 296). Ϊ 王 意 1 1 Ψ Cao ShiM E19 item takes toluene 10-^ rm Mor, N-hydroxyphthalimide 1 fir Mortal Acetyl Fill in this pack 1 Vanadium pyruvate (III) VUA) 3 0.0 5 millimoles, 25 ml of acetic acid mixed sheet 1 I compound under the gas Jhts-news »stirred at 70 t! M for 8 hours 9 toluene conversion 1 [1 80% ϊ benzoic acid (yield 68 %). 1 1 Example. 1.2.1.1, j Order 1 Take ethylbenzene 10 millimoles, N-hydroxyphthalimide 1 Mole acetamidopyruvate (III) V (AA) 3 0 .0 5 millimoles, 25 ml of acetic acid, mixed with 1 1 t, mixed with 70 mm for 8 hours under gas atmosphere, ethylbenzene conversion rate 1 | 84¾ t to give acetophenone (yield 76%. Line 1 implementation Example · .E.2J. Take 10 mol of dunes, 1 mol of N-hydroxyphthalocyanine 1 mol of copper acetate | Cu (0 A c)?. 05 mol 1 of acetonitrile 25 ml The mixture i was stirred at 70 v for 3 hours in an atmosphere of gas 1 and 95% of dene was converted to 9 to give 2, 4 1 I, 5-Ξtrimethylbenzoic acid (yield 5996) 〇I | Beneficial J! L— E_2_2— 1 1 Take duene 10 1¾- Mor, Η-hydroxyphthaloyl p ΡΠΕ. Imine 1 -rtr its ethyl ethyl I manganese pyruvate (I I.) Μ η (AA) 0 .5 5 Mo Ear, acetonitrile 25 ml β 1¾ mixed 1 I 77 1 1 1 paper size Use Chinese National Standard (CNS) Λ4 specification (210 X 297 mm) ί 3 7 Α7 Β7 α. Printed by the Bayer Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economics / V. Description of the Invention (rb) 1 1 Compound-* in In a gas atmosphere »Stir at 70 V for 3 hours, and the conversion rate of dune is 1 1 ϊ 94% to obtain 2,4,5--methyl ronganoic acid (yield 57%). 1! Actual. Example. 121 Please I first take dene] 0 millimolar H- hydroxyphthalimide imine 1 millimolar acetamido reading 1 I acetone cool cobalt (II) Co UA) 2 0 .05 Millimolar, 25 ml of acetic acid, 1 ml of 1 I mixed compound «Stirred in a gas atmosphere 9 at 60 for 3 hours, note the conversion of dunes 1 I matter 1 about 10 0¾, get 2,4,5 2 Methyl benzoic acid (yield 87 96) 〇 Item -S- 窨 Example. E.2..4 Manuscript 1 i 1 Take dene 10 0 mM hydroxyimine 1 mM imine 9 acetamyl Page 1 I Cobalt (II) pyruvate Co (AA) 2 0. 0 5 mmol, 2 ml of acetic acid 2 1 mixture »In an air atmosphere * Stir for 12 hours at room temperature (approximately 20 t) > Du 1 1ene conversion rate of about 100%, 2,4,5 Ξ methyl benzoic acid (yield 87%) 〇1 Order. Application-M..3.23-. 1 take duene 10 mmol π 4 hydrazone-hydroxyphthalimide 1 mmol 1 1 Manganese (II) pyruvate Mn η (AA) 2 0.05 millimoles, 2.5 ml of acetic acid · 1 I compound * In a gas-air enclosure »Stir at 70 ° C for 6 hours, The duene conversion was 98% of line 1 *, and 2,4,5 -__ Λ methylbenzoic acid was obtained (yield 36%). Example X2A 1 I Take duene 1 0 mmole Ν-hydroxyphthalimide 1 mmole I acetamyl 1 1 Propionate ferric acid {II I) F e (AA) a 0. 05 mmol Ear 1 acetic acid 25 g liters of mixed 1 | the mixture in a gas atmosphere »stirred at 70 V for 3 hours, the conversion of dune was 1 86% * 2,4, 5-dimethylbenzoic acid (yield 44 %). 1 [act. • fife .. basket 1 I take 10 mM t N-hydroxy. Base peptide amimine 1 mM $ acetamyl propion 1 1 78 1 1 1 1 Standard (CNS) Λ4 is present (210 × 297 mm) 5. Description of the invention (π) Cobalt (II) ketoacetate Co (AA) 2 0.Q5 mmol, mixed solvent (acetonitrile / acetic acid = 4/1) 2 5 ml of the mixture was stirred at 70 ° C. for 3 hours in an oxygen atmosphere, and the conversion ratio was 86.6% to obtain 3,5-dimethylbenzoic acid (yield 63. 3%). Example E28 Take 3 -B A mixture of 10 millimoles of toluene, 1 millimoles of fi-hydroxyphthalimide, 1 millimoles of copper acetate Cu (0Ac) 2, 0.05 millimoles, and 25 milliliters of acetonitrile. Stir at 75 ° C for 6 hours in an oxygen atmosphere. The conversion of 3-ethyltoluene was 9 G%, and m-methylacetophenone was obtained (yield: 57%), 3-ethylbenzoic acid (yield: 7%). Millimolar, N-hydroxyphthalocyanine imine 1 millimolar, cobalt (II) Co (AA) 2 ethyl acetate propionate G.05 millimolar, 25 ml of acetic acid in a gas atmosphere, Stir at 7 5 ° C for 6 hours, 3-ethyltoluene The conversion rate was 93%, and m-methylacetophenone (yield 55%) and 3-ethylbenzoic acid (yield 6%) were obtained. 4-ethyltoluene 1D millimolar, N-hydroxyphthalocyanine Immine 1 millimolar, printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page) Cobalt (II) Co (AA) 2 G.05 millimolar A mixture of 25 ml of acetonitrile was searched in an oxygen atmosphere at 7 5 ° C for 6 hours. The conversion of 4-ethylmethylbenzyl was 99%, and p-methylacetophenone (yield 66%), 4- Ethylbenzoic acid (10% yield).

Example R Take 4 -ethyltoluene 10 millimoles, fi-hydroxyphthaloimine 1 millimoles, acetamidopyruvate cobalt (II) Co (AA) 2 0.05 millimoles, acetic acid 25 millimoles- 7 9-This paper size applies Chinese National Standards (CNS > 8 4 specifications (2IOX29 "? mm) 8 4 A7 B7 V. Description of the invention Stir for 6 hours at 80 ° C in a gas atmosphere. The conversion of 4-ethyltoluene is 96%, and p-methylacetophenone (yield 5 2%), 4-ethylbenzoic acid (yield 6 W) Example K32: 10 millimoles of duene, 1 millimolar of N-hydroxyalcohol imine, cobalt (II) ethyl pyruvate Co (AA) 2 0.5 millimoles > acetic acid 25 milliliters Mixture * Stir at room temperature (approximately 2 trc) for 12 hours in an oxygen atmosphere. The conversion rate of dunes is 100% to obtain 2,4,5 £ methylbenzoic acid (93% yield). Ning, Example E33 Take 10 mol of dunes, 1 mol of N-hydroxyphthalimide, and cobalt (II) acetamidopyruvate C 〇 { AA) 2 0. 5 5 mol, mixed solvent (acetic acid / acetonitrile = 1/2 0) 2 5 ml of the adduct, in an oxygen atmosphere, at room temperature (about 20...) And mix 1 2 Hours »The conversion of dunes was 100%, and 2,4,5-trimethylbenzoic acid was obtained (yield 94%). 0 Rho Example R34 10 mols of dunes, NH 1 millimolar, Cobalt Acetylpyruvate (II) Co (AA) 2 0. 5 millimoles, acetonitrile 2 5 ml of the mixture 1 in an oxygen atmosphere »at room temperature (approximately 20 ...) Stir In 3 hours, the conversion of dune was 98%, and 2,4,5-trimethylbenzoic acid (yield 93%) and 2,4,5-trimethylbenzaldehyde (yield 5%) were obtained. R 3 5 is a mixture of 10 millimolar hydroxyphthalimide m imine 1 millimolar, ethanolic cobalt pyruvate cobalt (II) Co (AA) 2 Q .0 5 millimolar, acetic acid 2 5 ml of the mixture. Stir in an oxygen atmosphere at room temperature (about 15 ° C) for 18 hours, a certain revolution -80- --------- 1 equipment -------- order ------ line (Please read the notes on the back before filling (This page) This paper's standard is applicable to China National Standards (CNS) Λ4 is present (2 丨 0 > < 297 gong) 8 Printed by the Bayer Consumer Cooperative of the Central Standards Bureau of the Ministry of Economy 4 3 i 'A7 B7 V. Invention Explanation (; 7) 60% conversion rate, 3,5-dimethylbenzoic acid (yield 20%), 3,5-dimethylbenzaldehyde (yield 30%). For example, a mixture of ID mol, hydroxyphthalimide 1 mol, acetaldehyde cobalt (II) Co (AA) 2 0.05 mol, and 25 ml of acetonitrile in an oxygen atmosphere Stir at room temperature (approximately 1 δ ° C) for 6 hours. The conversion rate of rutae is 61%. 3, 5-dimethylbenzoic acid (yield 23%), 3, 5-dimethylbenzaldehyde (yield 2) 5%). Example R37 Take a mixture of 10 millimoles of toluene, 1 millimole of N-hydroxyphthalocyanineimide, cobalt (II) co (AA) Co (AA) 2, 0.05 millimoles, and 2 mL of acetic acid. In an oxygen atmosphere, it was stirred at room temperature (about 5 ° C) for 24 hours. The toluene conversion rate was 71%. Benzoic acid (yield 66%) and benzaldehyde (yield 3%) were obtained. gmm K8 8 Take a mixture of toluene 1 [(millimol, .N-hydroxyphthalimide 1imole, acetammonium cobalt (Co (OAc) 2 0.05 millimole, 25 ml of acetic acid, in an oxygen atmosphere, Stir at room temperature (approximately 15 " C) for 24 hours. The toluene conversion rate is 72%. Benzoic acid (yield 60%) and benzaldehyde (yield 3%) are obtained. 窨 旆 仞! R 3 9 Take 10 mmol of p-tert-butyl toluene, 1 mmol of N-hydroxyphthalimidine, cobalt (II) ethylpyroacetate (0) 0.5 mmol, 25 ml of acetic acid The mixture was stirred in an oxygen atmosphere at room temperature (about 15 ° C) for 18 hours. The conversion of butyl toluene was 94%, and p-tert-butylbenzoic acid was obtained (yield: 71%). Aldehyde (yield 2%). * 8 1-This paper size is in accordance with Chinese National Standard (CNS) Λ4 specification I. ::! ...: factory 犮) --------. »1 Pack --- --7 ~ Order ----- line (please read the notes on the back before filling out this page) 44813; printed by the Central Standards Bureau of the Ministry of Economic Affairs and Consumer Cooperatives A7 B7 V. Description of invention (and) Implementation. LFL . Take 10 millimoles, 1 millimole of N-hydroxyphthalocyanine, manganese acetamidopyruvate Mn (AA) 3 0 A mixture of .05 millimoles and 25 ml of benzonitrile was stirred in a gas atmosphere at 100 C for 6 hours. The products in the reaction solution were utilized. Gas analysis was used. The conversion rate was 32%. Ketone (yield 28%). Example 1. Example F 2. 10 millimoles, 1 millimole of N-hydroxyphthalimide, 1 manganese ethylpyruvate (^ /// 1) 7_0.0 5 millimoles, 25 ml of benzyl compound, stirred in a gas atmosphere garden at 100 ° C for 6 hours. The products in the reaction solution were examined by gas chromatography, and the conversion of tritium was 38% Acetophenone (yield: 3 0 9 (^) η Shili. Example [3. 10 millimoles, N-hydroxyphthalimide 1 millimoles, vanadyl pyruvate V (AA ) 3 0.0 5 millimoles, a mixture of 25 ml of acetic acid, stirred at 90 t for 6 hours in a gas atmosphere, the products in the reaction solution were examined by gas chromatography, the conversion rate of rhenium was 54%, 芴 01 (Yield: 4896) ... Example: _Shi_ .. Example: ¥ 10 mmol, N-Hydroxyphthalimide 1 mmol, Cobalt Acetylpyruvate Co (AA)? 0.05 mmol A mixture of 25 ml of acetic acid and acetic acid was stirred at 90 t for 6 hours in an oxygen atmosphere. Gas chromatographic examination showed that the conversion rate was 68%, and acetophenone (yield 44%), ¥ acid (yield 3%). 曹 施 例 _G_1. This paper size applies the Chinese National Standard (CNS.) Λ4 specification ( 2! OX 297 mm) ^ — ^ 1--_--1 ^ 1 ---: ^^^ 1 I (Please read the precautions on the back before filling this page)

'1T .line β' 1ΓΜΜΙΓ printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Description of the invention (Η) Take ammantadane 10 mmol, N-hydroxyphthalimide imine 1 mmol, acetamidine Acid mixture (IV) Zr (AA) 4 0.05 millimoles, 25 ml of acetic acid, mixed with 75TCI1 for 6 hours in a chlorine gas atmosphere, the products in the reaction solution were examined by gas analysis, and the adamantane conversion rate was 74% To produce amantadine (yield 40%), 1,3-adamantanediol (yield 8%), 2-adamantanone (yield 6%), 100% residue of N-hydroxypeptide imine .施. 例. Except for acetamidinepyruvate (IV) Zr (AA) 4, instead of titanium acetamylpyruvate Π Π Τ ′ (AA) 2 〇. 05mmol, according to Example G 1 The same reaction, the conversion of adamantane is 55%, to produce 1-adamantanol (yield 33%), 1, 3-adamantanediol (yield 6%), 2-adamantanone (yield 6 %), 100% of N-hydroxyphthalimide. Actual ... Application Example G., 3 .: Except Acetylpropionate (.IV) Zr (AA) 4 Change to Acetylpyruvate Chromium (III) Cr (AA) 3 0.0 5 mmol Moore, reacted in the same manner as in Example G1, with an adamantane conversion of 57.7%, yielding 1 adamantanol (33% yield), 1, 3-adamantanediol (2% yield), 2-adamantane Ketone (yield 6%), N-hydroxyphthalimide 100% remained. -Actually: Shi_Regulation_0 丄 except for acetamylpyruvate (IV) Zr (AA) 4 instead of acetamylpropane_manganese (III) Mn (AA) 3 0.05 millimoles, according to the examples The same reaction of G1, the conversion of adamantane (58%, to form amantadine (yield 37%), 1, 3-adamantanediol (yield 7%), 2-adamantane (yield 5 % N -Hydroxyphthalimide 85% remains. -------- Ί.Ί 装 -------- Order ----- Thread- '(Please read the precautions on the back before filling in this (Page) This paper size applies Chinese National Standard (CNS) Λ4 specification (210X 297 mm) 8 4 4 ί 3 Ί Α7 Β7 啻 Steal case Fi except for ethyl m-propane _ acid junction (IV) Z r {AA) 4 Modify Acetyl propionate (II) Mη (AA) 2 0. 5 5 mol, the reaction was the same as in Example G1, the diamond turnover was 67% 1 1-adamantanol (yield 39 %) 9 1,3-Adamantanediol (yield 6%), 2 -adamantanone (yield 5%), N-hydroxyphthaloimine 9 ί% Residual Q Acid error (IV) Z r {AA) 4 Switch to molybdenum molybdate 2 Μ 〇 0 4 0 * 0 5 Example G 1 The same reaction, the conversion of adamantane is 79% > 1-adamantanol (yield 49%), 1,3-adamantanediol (yield 15%), 2-adamantanone (Yield 7%), N-Hydroxypeptide 8imine 8 9% Residue 0 窨 m Example Q7 Take King Kong 1 Q mol, N-Hydroxyphthalocyanine 1 mM, Chromium Acetylpyruvate (IV) A mixture of C r (AA) 4 0,5 5 mol and 25 ml of acetic acid i in an air atmosphere, stirred at 85 ° C. for 6 hours, the adamantane conversion rate is 90% ΰ to form I- Amantadine (yield 38%), 1,3-adamantane-alcohol (yield 24%) 3 1, 3,5-adamantanetriol (yield 4%), 2-adamantane noodle ( Yield: 8%), 97% of N-hydroxyphthalimide. A mixture of 10 millimoles of adamantane, 1 millimole of N-hydroxyphthalocyanine imine, acetopyruvate (IV) Zr (AA) 40.05 millimoles, 25 milliliters of acetic acid, Stirred at 85 ° C for 6 hours in an oxygen atmosphere. The adamantane conversion was 80%. Formation of 1-adamantanol (yield 34%), 1,3 -adamantane-8 4 _ Paper Office K ft W sample rate (C: NS) grid (2! 0 X 297) while- ------- Γ Install ------ Order ------- k (Please read the precautions on the back before filling out this page) The Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, printed economy Printed by the Central Standards Bureau of the Ministry of Work and Consumer Cooperatives A 7 B7 V. Description of the invention (Η) Glycol (yield 26%), 1,3,5 -adamantanetriol (yield 3%), 2-adamantane Ketone (yield 6%), 88% N-hydroxyphthalocyanine imine. Example (λ 9. Take 10 mmol of hexane, 1 mmol of N-hydroxyphthaloamine, acetamyl propionate Manganese ring manganese (Mn UA) 3 0.05 millimoles, 25 milliliters of acetic acid in a gas atmosphere at 1 1 0 ΐ: Stir for 6 hours, the product of ° in the reaction solution was checked by liquid chromatography, cyclohexane The conversion of alkane was 85%. Adipic acid (yield 70%) and cyclohexanone (yield 5%) were generated, and 7-7% of fluorene-hydroxyphthalaldehyde imine remained. Example__G_.l., 0 ... Take 10 millimoles, Η-Hydroxyphthaloimide 1 millimolar, Acetyl Propionate ZriAA) 4 0.05 millimoles, 25 ml of acetic acid In the FIG atmosphere, it was stirred at 9 0 ° C 6 hours, the reaction liquid by the liquid product was analyzed to check satiation, fluorenyl conversion of 68%. The fluorenone (42% yield) and the methanol (4% yield) were formed, and 67% of the N-hydroxyphthalimide remained. Actual: Apply a mixture of 10 millimoles of cyclohexane, 1 millimole of ti-hydroxyphthalocyanine, 1 millimoles of cobalt acetamidine pyruvate Co (AA) 2, and 5 milliliters of acetic acid in air. In a gas atmosphere, the mixture was stirred at U 0 ° C for 6 hours. The products in the reaction solution were examined by liquid chromatography. The cyclohexane conversion was 76%. Cyclohexanone (yield 36%) and cyclohexanol (yield 1%), and adipic acid (yield 29%) were generated, and 48% of N-hydroxyphthalimide remained. Real .. Shi Jj._G 丄 2_. 10 Watts Moore \ N-Hydroxyimide 1 mmol, Ethyl Acetyl-85-This paper size applies Chinese National Standard (CNS) Λ4 specification (210X297 Mm) -------- {"install ------ order ------ Yu (please read the notes on the back before filling this page) 8 4 1 〇7 Α7-Β7 5 2. Description of the invention (β) A mixture of cobalt ketoacetate Co (AA) 2 0.0 5 millimolar and 25 ml of acetic acid is stirred in a gas atmosphere at 90¾ for 6 hours. The product in the reaction solution is checked by liquid chromatography. The conversion rate of fluorene is 59%. The formation of watone (yield 40%) and watol (yield 4%), 48% of H-hydroxyphthalimide imide. Example_GU. Take adamantane 10 millimoles, N -A mixture of 1 mol of hydroxyphthalimide, 1 vanadium acetopyruvate V (/ U) 3, 0,05 mol, and 25 ml of acetic acid, stirred at 7 5 ° C for 3 hours in an oxygen atmosphere, The products in the reaction solution were examined by liquid chromatography, and the conversion rate of adamantane was 94%. Amantadine (yield 40%), adamantanediol (yield 25%), and adamantanetriol (quotient) 2%) and adamantanone (yield 7%), N-hydroxyphthalimide imine 49% Example. G 14_ Take adamantane 10 millimoles. N-Hydroxyphthalimide 1 millimoles, ethyl-propionic acid mV (AA) 3 0.03 millimoles, 25 ml of acetic acid, in a gas atmosphere Stir at 75 scoops for 3 hours. The product in the reaction solution is checked by liquid decantation. The conversion rate of adamantane is 89%. Amantadine is produced (4.2%), adamantanediol (yield 2 4 %), Amantadine triol (yield 2%) and amantadone (yield 7%), 54% of N-hydroxyphthalimide imine. For the time being… ..M..G 1..5 .. Take a mixture of adamantane 10 mmol, N-hydroxyphthalimide imine 1 mmol, disc vanadium molybdic acid PVs 〇〇〇 ＊＊ 30H? _ 0 0.03mmol, a mixture of 25 ml of acetic acid in a gas atmosphere Inside, stir it at 7 5 for 3 hours, anti-free liquid -86-This paper size is applicable to China National Standards (CNS) Λ4 specifications (2 丨 "-) --------, Ίί installed --- --- Order ----- line (please read the notes on the back before filling out this page) Printed by the Central Standards Bureau of the Ministry of Economic Affairs, printed by the Shellfish Consumer Cooperative, A7 B7 Invention Description (8JT) 1-| The conversion rate of amantadine is 57%. It produces 1 1 I amantadine alcohol (yield 37%), adamantine diol (yield?%) And adamantine 1 1 ketone (yield 6%), N-hydroxyphthalocyanine 61% of the amine remained. Please 1 first 1 rich example-G 1 6. Reading 1 I take King Kong Yuan 10 mM, N-hydroxyphthalimide 1 mM, hinder vanadium back 1 I 1 I m 酴 PV 4 y R 0 40 * 30H 2 0 0.03 millimoles, 25 ml of acetic acid Note 1 1 Mixture * Stir in an atmosphere of gas > at 7 5 ° C. Stir in the reaction solution for 3 hours 1 Item and then 1 The product is analyzed by liquid calendar Check that the adamantane conversion is 49¾. Generated gold fill in 1 pack of 1 Gangyuan alcohol (yield 3-6%), amantadine diol (yield 7%) and Jingang Yuan country page 1 | (producing E5 96), N-hydroxyphthalimide imine 59% Residual. 1 1 M 313.1 1 1 Take butadiene 1, 08 g (20 mmol), N-hydroxyphthalimide imine 0.26 g, 1 order (1, 6 ττ Mol), cobalt acetocolate C 〇 (AA) 20. 03 g (0.1 21 mmol), 25 ml of acetonitrile, 25 ml of warm compound, and stirred at 60 C 1 ft for 6 hours in an oxygen atmosphere. The product in the anti-vine solution was examined by liquid layer analysis. The conversion rate of butadiene was 35%. 2-butene-1,4-diol (butadiene-based 1-line! M selectivity 63¾, yield 22%), and butylene-3,4-diol (butadiene-based Selectivity 2396, yield 8 96). Alcohol selectivity was 86%. 1 I Example—H2 1 1 Take 1.06 g (2.0 mmol) of acryl, N-hydroxyphthalimide m. 0.26 g 1 1 (1.6 mmol), acetamidopyruvic acid Cobalt Co 〇 (AA) 2 0.03 g (0.1 2 1 I 25 ml of a mixture of methanol in 25 ml, stirred in an oxygen atmosphere at 50 1 1 m for 3 hours. R—r ofe * product in the liquid Using liquid chromatography inspection, the conversion rate of propionate was 99%, and 1, 1-dimethylaminopropionitrile was obtained, with a yield of 99%. I | 87 1 [1 1 The jersey-¾ scale is applicable to Chinese national standard { CNS) Λ4 specification (210X297 mm) A7 .B7 V. Description of invention (Park)

Put JU to take 1.72 g (20 mmol) of methyl acrylate, 0,26 g (1.6 mmol) of N-hydroxyphthalocyanine, and Co (AA) 2 glyoxal pyruvate 0.03 g (0.12 mmol) Mol), 25 ml of methanol, and stirred in an oxygen atmosphere at 5 ο π for 3 hours. The product in the reaction solution was tested for tritium by liquid chromatography, and the conversion rate of methyl acrylate was 99%. Methyl 1,1-dimethylpropionate was obtained in a yield of 99¾. -------- (丨 Install ------ Order ----- line (Please read the precautions on the back before filling out this page) Printed on paper by the Staff Consumer Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs Standards are applicable to Chinese National Standards (CNS) Λ4 specifications {2 丨 〇 X 29? Mm)

Claims (1)

-C yyr J 1L κ In the ABCD formula, the catalyst is used to catalyze oxygen f-species 1 one C: alkane, zygogenic protomine subdentate, the original Chinese formula group v \\ R, π And radical 1 aryl. Is the same or the same phase alkyl alkoxyalkyl hydroxy 香 香 aryl aryl group &quot; g th, carbon or ㉟ 罾 alkoxy aryl aryl aryl, 3 r, to the base bond 1 carboxyl W For the formation of η, form a base, combine with this or other 2 original Ξ. Qi and 4. 1 1 RX Family A 2 The table period contains optional and (please read the ΐ ± · Italian notice on the back before (Complete this page) Printed by the Central Bureau of Standards of the Ministry of Economic Affairs, Consumer Cooperatives 11 Transition metals and auxiliary catalysts of elements such as Group 3B of the periodic table (except Xunxun molybdic acid). 2. The oxidation catalyst strip according to item 1 of the scope of patent application, wherein in the sulfonium imine compound represented by formula Π.), R 1 and R 2 are combined with each other to form an aromatic or non-aromatic 5 to 12-membered ring. 3. The gasification purlin according to item 1 of the scope of patent application, wherein in the ammonium amine compound represented by formula fl), R 1 and R 2 are combined with each other to form a pinane ring which may have a substituent, and may have a substitution. Cycloalkene ring, which may have a substituent, a bridged hydrocarbon ring, and aromatic substituent f 4 which may have a substituent. For example, the gasification catalyst 糸 of the scope of patent application No. 1 is shown in the formula (1). Amine compounds, compounds represented by the following formulae (1 a) to (1 f): * 89- scale applies to Chinese National Standards (CNS) Yaoliengge (2 [0X297 mm) β 4 ABCD otlc R6 Chinese formula radical No. 6 Carboxylan E E, Sufan to ketolide 3, special alkyl group, amino group, such as y hydroxyl, σο group \ 1 / 1f alkane / L. X proton hydrogen can be 1e ) ra fv is not the same phase as the alkyl group. On the basis of the nitrate, the aldehyde is the same as t η, the alkyl group and the acid 2, the sulfonyl β gas, the cyanamide, the dibutyl hydroxyl 1 Ν White selection compound amine imine 0 succinyl hydroxyl, imine imidene phthalophthaline hydroxyl N- group, hydroxyl amine N-imine, alginic acid carboxylic acid sulfonyl tetracyclohexyl hydroxy di 0 β bromide Tetraylhydroxylamine imine _ (N amine amine gas sulfonyl ketone hydroxymi N NH, amine amine nitroimine N-fluorene, phthaloyl e) chloride id Or ffl pi group τ Ε Η ------ -. 丨 Install ------ Order ------ line (please read the notes on the back before filling this page) Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economy hi Sihe y ·-Homogenization OX Benzene dr base species Hy Jingyi κι X ?. I item 4 over 1 family 2 The first ith Wai CO Yuan Fan table family B He Yu 2 Special week and please apply for selection 1B Such as, \ 一 少 Ν 至Ν et al., Amine, imine, tetra-naphthalene, p-phenylene hydroxy dihydroxy ', gas is a gold paper standard applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). Family Media δ 物 ® Family Φ _ ί d f A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A Af A / 1 ABCD A compound containing at least one element selected from Group 4 / \, Group 5A, Group 6A, Group 7A, Group 8 and Group 1B of the periodic table. 8. For example, the gasification catalyst 糸 of the scope of patent application, wherein the auxiliary catalyst is pseudo-selected from at least one of gaseous, organic acid salt, inorganic acid salt, dentate, complex, isopoly acid and its salt. By. 9. The oxidation catalyst strip according to item 1 of the patent application scope, wherein the auxiliary catalyst rhenium contains an element selected from the group consisting of lanthanum strips, Ti, Zr, V, Cr, Mo, W, Mn, Fe, S? U. Co, Rh , Hi and Cu7C. 10. The gasification catalyst rhenium according to item 1 of the scope of the patent application, wherein the sulfonium imine compound represented by the formula Π) and containing at least one of Group 4 A, 6 A, and 7 A elements of the periodic table The auxiliary catalyst of the element combines the builder. 1 1. The oxidation catalyst strip according to item 1 of the scope of patent application, wherein the pseudo-imine compound represented by the formula _ (1) and the auxiliary catalyst bond containing elements of Group B of the periodic table are composed. 1 2. The gasification catalyst strip according to item 1 of the scope of patent application, wherein the pseudoimide compound represented by formula (ii), a compound containing a group element of the periodic table, and a compound containing a group 8 element of the periodic table . 13. If you apply for the gasification catalyst strip of item 12 of the special brake scope, the compound containing a group A element of the periodic table 7 is a manganese compound t and the compound containing a group 8 element of the periodic table is an iron compound. 14. For example, the gasification catalyst bar of item 12 of the patent application, in which the proportion of compounds containing Group 8 elements of the Periodic Table is 0.1 to 20 Molar compared to those containing 1 Molar of Group 7 A of the Periodic Table. ~ 9 1 _ This paper size applies the Chinese National Standard (CNS) Λ4 Washing Box (210X297 mm) I. Binding Line • K ·. (Please read the precautions on the back before filling this page) 48137 Α8 Β8 C8 D8 Economy Printed by the Ministry of Standards and Labor ’s Consumer Cooperatives 6. Scope of patent application 15. For example, the gasification catalyst strip of item 1 of the scope of patent application, where the ratio of the 醯 imine compound to the auxiliary catalyst shown in formula (Π is Imine compound 1 Mole, co-catalyst 0.0 ill to 10 Moore. 16. For example, the gasification catalyst 糸 of the scope of patent application, wherein the 醯 imine compound and co-catalyst shown in formula (1) The ratio of the catalyst is 1 mole to the imine compound, and the catalyst is 0.1 mole or less. 17. A gasification method is the following formula (1) 0 {[X (1) Jn 0 〇〇3-( In the formula, R1 and R2 are the same or different, and are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cycloalkyl group, a hydroxyl group, an alkyl chloride group, a carboxyl group, an alkane carbofluorenyl group, a fluorenyl group, R1 and R2, and are formed by combining each other. Double bond, aromatic or non-aromatic ring, X is a gas atom or a hydroxyl group, and η is an integer of 1 to 3) In the presence of a chelating catalyst, at least one alkyl-substituted aromatic compound selected from polycyclic hydrocarbons other than amarane, cycloolefin, and adamantane containing methylene as a ring constituent unit, and a conjugated compound A substrate, which is in contact with gas. 18. The gasification method as described in item 17 of the patent scope, which is selected from the group consisting of gaseous, organic acid, inorganic acid, halide, complex, and heteropoly. Gases are co-existed with at least one auxiliary catalyst of an acid or a salt thereof. 19. The oxidation method according to item 17 of the patent application scope, wherein the polycyclic hydrocarbon fluorene has at least one methylene crosslinked ring at the bridgehead position. Hydrocarbons or terpenes, condensed polyfluorinated hydrocarbons having at least one methylene group at the junction of each other. ____—- 9? —R · .............——- In this paper Stored in Chinese standard (CNS &gt; M size (210X297mm) I installed—I—HI H. cable (please read the precautions on the back before filling this page) ABCD patent application scope 20. If the patent application scope is 17th The gasification method according to item 1, wherein the polycyclic hydrocarbon 傜 has a plurality of methylene 2-ring to 4-ring hydrocarbons. 21 As described in claim 17 of the scope of patent application Oxidation method, in the presence of an oxidation catalyst, contacting an adamantane component containing at least one of adamantane monool, adamantanediol and adamantanetriol with oxygen to generate a highly hydroxylated adamantane polyol β 2 2. The oxidation method according to item 21 of the scope of patent application, wherein the content of adamantane monool, adamantanediol or adamantanetriol accounts for more than 5 mole% of the whole skeleton of the adamantane component. 23.— This oxidation method is based on the following formula (1) (please read the precautions on the back before filling this page). Install-N ~) Square C〆 (1),-&amp; 'R2 (where R1 and E2 are the same or different Is a gas atom, a halogen atom, an alkyl group, an aryl group, a cycloalkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxysulfonyl group, a fluorenyl group, R 1 and R 2 are combined with each other to form a double bond, aromatic or non- Aromatic ring, _ X is an oxygen atom or a hydroxyl group, η is an integer of 1 to 3, and a co-catalyst containing an element selected from Group A of the Periodic Table 2, a transition metal, and Group 3B of the Periodic Table In the presence of an oxidation catalyst strip, the matrix (but when the matrix is an aromatic compound with a hydroxyl group at the benzyl position) Dummy non-catalytic secondary phosphovanadomolybdic acid) and the gas contacts. 24. The oxidation method according to item 23 of the scope of patent application, wherein the auxiliary catalyst is selected from the group consisting of gaseous, organic acid salts, inorganic acid salts, hafnium halides, and complexes. -93- This paper applies Chinese national standard. (CNS) Α4 Specification (210 X 297 mm) 'Line-Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 448 Printed by A8, B8, C8, D8 of the Consumer Cooperatives of the Central Procurement Bureau of the Ministry of Economic Affairs 6. At least one of the scope of patent application, isopolyacid and its salts. 25. The gasification method according to item 23 of the scope of patent application, wherein the matrix fluorene (a) pinanes, (b) cycloolefins, (c) polyfluorene hydrocarbons containing methylene as a ring constituent unit, (d ) An aromatic compound having a methyl group or a methylene group in the ortho position of the aromatic ring, or a <e) conjugate compound. 26. The gasification method according to item 25 of the scope of application for a patent, wherein the fluorane type hydrazone has a compound having 3 to 30 cycloalkane rings. 27. If the gasification method according to item 23 of the scope of the patent application, in the presence of a gasification catalyst strip, the compound having 3 to 3G rings and rings is oxidized with oxygen to generate a dicarboxylic acid corresponding to dicarboxylic acid. Or those who have ketones. 2 8. The oxidation method according to item 25 of the patent application scope, wherein the polycyclic hydrocarbons are adamantane and its derivatives. 2 S. If you apply the oxidation method of item 23 in the scope of patent application, you will oxidize polycyclic hydrocarbons with molecular gas in the presence of a gasification catalyst strip to generate compounds that introduce hydroxyl groups. 30. If the oxidation method according to item 23 of the scope of patent application, pseudo-in the presence of a gasification catalyst, the adamantane component selected from adamantane and its derivatives is brought into contact with gas to generate a hydroxyl group introduced at a plurality of bridgehead positions. Of adamantane polyols. 31. The gasification method according to claim 25 of the scope of patent application, wherein the compound (d) is an aromatic compound substituted with at least one alkyl group. 32. The gasification method according to item 25 of the scope of patent application, wherein the compound (d) is a pseudo-aromatic heterocyclic ring and has an aromatic hydrocarbon ring of 14. 3 3. The oxidation method according to item 25 of the scope of patent application, in which compound-9 4-This paper size is applicable to Chinese National Standard (CNS) Λ4 (eg I (1 &gt;: 3 7 mm) — ^ —1 II &quot; Binding (please read the notes on the back before filling this page) 84 Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (d) Pseudo-aromatic hydrocarbons with at least one methyl group β 34. If the gasification method in the scope of patent application No. 23, the pseudo- The aromatic compound having at least one methyl group is contacted with gas to generate an aromatic compound having a carboxyl group. 35. The gasification method according to item 25 of the scope of patent application, wherein the conjugated compound (e) is a conjugated diene, &gt; 5-unsaturated nitrile or a compound represented by the following formula, R7 I ^ 0 CH2 = C_C (wherein R7 is a hydrogen atom or a methyl group, Y is -〇Rs (Rs is a hydrogen atom, an alkyl group, an aryl group, a cycloalkyl group, a hydroxyalkyl group, a glycidyl group), and -NR9R 10 (Rs and ϋ1 ( 3 are the same or different, are gas atom, alkyl group, hydroxyalkyl group) 3 6. The gasification method as described in the scope of application for item 2 '5, wherein the conjugated compound (e) is pseudobutadiene, isoprene Diene, (meth) acrylonitrile, (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylamide. 37. For example, the oxidation method according to item 23 of the scope of patent application, wherein the formula ( 1) The amount of fluorene imine compound shown is 0.0C11 to 1 mol relative to 1 mol of the substrate. 3 8. The oxidation method according to item 23 of the patent application range, in which the amount of auxiliary catalyst used, 傜 il GGGl to 0.7 moles relative to 1 mole of the matrix. 39.-A method for producing ketones, alcohols, aldehydes or carboxylic acids in the matrix, which is represented by formula (1) '' 9 5- This paper size applies the Chinese National Standard (CNS) Λ4 now (210X 2 millimeters) (Please read the precautions on the back before filling this page) Order 84 4) -ic ABCD patent application scope (1) 0 ^ R1N〇 C \, N —X 'R2- (wherein R1 and R2 are the same or different, and are ® atom, halogen atom, alkyl group, aryl group, alkyl group, hydroxyl group, alkane group, carboxyl group, alkanesulfonyl group , Fluorenyl, R 1 and R 2 combine with each other to form a double bond, aromatic or non-aromatic fluorene, X is a gas atom or a hydroxyl group, and η is an integer of 1 to 3) The fluorene imine compound shown in FIG. Table 2 Group A, transition metals and timetable Table 3 Group B element of auxiliary catalyst (except phosphorus vanadium molybdic acid) composed of gasification catalyst strips, the substrate and the gas contact, and manufacturing and the corresponding matrix _ .. Alcohols, aldehydes or carboxylic acids. (Please read the notes on the back before filling out this page.) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 96-1 *?隼 （CNS &gt; A4 is present (2 〖0 Father 297mm &gt; -C yyr J 1L κ Please use CD in the following ABCD formula: Catalytic oxygen f-species 1 one C: alkane, zygogenic protomine dentate, and the original Chinese formula Π v \\ R, π and radical 1 aromatic. It is the same or the same phase alkylene oxide The hydroxy group of the fluorene group 'Xanyl aromatic' is carbon or fluorinated, and the alkoxy group of the fluorene group, 3 r, to the base bond 1 and the carboxyl group is formed into a η group, and the hydroxy group is one or the other.子 2 原 Ξ. 气 和 4. 1 RX Family A 2 The period of the week is optional and please (please read the ΐ ± · notes on the back before filling out this page) The Central Consumers Bureau of the Ministry of Economy Staff Consumer Cooperatives Seal 11 Transition Metals and auxiliary catalysts of elements such as Group 3B of the periodic table (except Xunxun molybdic acid). 2. The oxidation catalyst strip according to item 1 of the scope of patent application, wherein in the sulfonium imine compound represented by formula Π.), R 1 and R 2 are combined with each other to form an aromatic or non-aromatic 5 to 12-membered ring. 3. The gasification purlin according to item 1 of the scope of patent application, wherein in the ammonium amine compound represented by formula fl), R 1 and R 2 are combined with each other to form a pinane ring which may have a substituent, and may have a substitution. Cycloalkene ring, which may have a substituent, a bridged hydrocarbon ring, and aromatic substituent f 4 which may have a substituent. For example, the gasification catalyst 糸 of the scope of patent application No. 1 is shown in the formula (1). Amine compounds, compounds represented by the following formulae (1 a) to (1 f): * 89- scale applies to Chinese National Standards (CNS) Yaoliengge (2 [0X297 mm) 84 Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (d) Pseudo-aromatic hydrocarbons with at least one methyl group β 34. If the gasification method in the scope of patent application No. 23, the pseudo- The aromatic compound having at least one methyl group is contacted with gas to generate an aromatic compound having a carboxyl group. 35. The gasification method according to item 25 of the scope of patent application, wherein the conjugated compound (e) is a conjugated diene, &gt; 5-unsaturated nitrile or a compound represented by the following formula, R7 I ^ 0 CH2 = C_C (wherein R7 is a hydrogen atom or a methyl group, Y is -〇Rs (Rs is a hydrogen atom, an alkyl group, an aryl group, a cycloalkyl group, a hydroxyalkyl group, a glycidyl group), and -NR9R 10 (Rs and ϋ1 ( 3 are the same or different, are gas atom, alkyl group, hydroxyalkyl group) 3 6. The gasification method as described in the scope of application for item 2 '5, wherein the conjugated compound (e) is pseudobutadiene, isoprene Diene, (meth) acrylonitrile, (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylamide. 37. For example, the oxidation method according to item 23 of the scope of patent application, wherein the formula ( 1) The amount of fluorene imine compound shown is 0.0C11 to 1 mol relative to 1 mol of the substrate. 3 8. The oxidation method according to item 23 of the patent application range, in which the amount of auxiliary catalyst used, 傜 il GGGl to 0.7 moles relative to 1 mole of the matrix. 39.-A method for producing ketones, alcohols, aldehydes or carboxylic acids in the matrix, which is represented by formula (1) '' 9 5- This paper size applies the Chinese National Standard (CNS) Λ4 is now (210X 2 millimeters) (Please read the precautions on the back before filling this page) Order