1 3,806,467 United States Patent 0 ICC Patented Apr. 23, 1974

1 2 glycol which is then partially esteri?ed together with a 3,806,467 fatty acid. ORGANIC TIN COMPOUND CONTAINING Also newly proposed is a method (U.S. Pats. 3,360,584, CATALYST SYSTEM USEFUL FOR PRO and 3,351,635) wherein an ole?n and an organic hydro DUCING EPOXY COMPOUNDS peroxide are brought into contact with each other in the Yoshihiro Watanabe, Kobe, Toshio Nishizawa, Takatsuki, 5 and Jiro Kobayashi, Ibaraki, Japan, assignors to Sumi presence of a metallic compound comprising vanadium, tomo Chemical C0,, Ltd., Osaka, Japan molybdenum, tungsten, selenium or mixture. However, No Drawing. Original application Mar. 10, 1970, Ser. No. such method has drawbacks that the organic hydroperox 18,335. Divided and this application Sept. 30, 1971, ide itself is expensive, and that, in principle, a correspond Ser. No. 185,369 ing alcohol in an amount equivalent to the formed epox Int. Cl. C07d 1/08, 1/06 ide compound is by-produced and therefore the economi US. Cl. 252—--429 R 2 Claims cal merit of this method is likely to be in?uenced by the marketability of the by-product. ABSTRACT OF THE DISCLOSURE As described above, the conventional methods of epoxi 15 dizing ole?ns have been not fully satisfactory. Catalyst system useful for producing epoxy compound Recently has come to be economi containing ( 1) at least one organic tin compound as a ?rst cally mass-produced due to the development of improved component having at least one hydroxyl group or a co oxidation of secondary alcohols or quinone compounds ordination group which is capable of being converted and has come to be very cheap particularly in the state to a hydroxyl group in the presence of or hydrogen 20 before puri?cation or concentration. peroxide and (2) a second component selected from com Therefore, some attempts to utilize hydrogen peroxide pounds of molybdenum, tungsten, vanadium, selenium, directly as an epoxidizing agent have been made, e.g. boron and mixtures thereof. Bull. Chem. Soc. Jap. 42, 1604, 69 (I), J. Org. Chem. 22, 1682, ’57 (II). In the former method (I), the epoxy This is a division of application Ser. No. 18,335, ?led 25 compounds of C8, C12 cyclic ole?ns are produced mainly Mar. 10, 1970. by oxidation with hydrogen peroxide in the presence of This invention relates to a novel method of oxidizing a selenium dioxide catalyst. However a very large amount organic compounds and more particularly to a novel proc of the catalyst is required and this publication does not ess for producing epoxy compounds from ole?ns in the mention the epoxidability of aliphatic ole?ns. In the presence of a special catalyst. 30 method (II), grycohol of C5 cyclic ole?n is produced Epoxy compounds play an important role in the in mainly in the presence of such metallic compounds as of dustry as intermediate materials for industrial chemicals, H2WO4 as catalyst. synthetic resins, rubbers, etc. However, a small amount of epoxy compounds have There are already known many methods of epoxidizing been isolated as only intermediates. What can be generally ole?ns. For example, the most typical industrial method 35 said is that, with such simple catalyst systems, the is the gas phase oxidation of ethylene. However, such epoxidizing activity of hydrogen peroxide is so low that, method can proceed in considerably high yields for ethyl as mentioned also in the above literatures, the forma ene which has the simplest chemical structure among tion of a small amount of epoxy compound is recognized ole?ns but is low in the yield for other ole?ns, particularly only on very speci?c compounds, especially cyclic com propylene, so that it has been found to be difficult to 4.0 pounds, and the reaction proceeds to a diol in most cases. industrialize such method in respect to ole?ns other than From such viewpoint, the investigation to use hydrogen ethylene. peroxide directly for an epoxidation has not been estab The most widely used method of epoxidizing ole?ns is lished practically. Therefore, it has been necessary to convert hydrogen peroxide into a peracid as mentioned the so-called chlorohydrin method long known in the art. 45 However, this method has such drawbacks as the high cost hereinbefore or to employ an organic hydroperoxide. required for large electrolytic equipment, corrosion of An object of the present invention is to provide an the apparatus and the waste of expensive chlorine. There advantageous and industrially practical method wherein, fore, a more economical method has been strongly hoped by the adoption of newly discovered catalyst system, hydrogen peroxide may be used effectively and directly as for. 50 From such viewpoint, some improved methods have an epoxidizing agent for the epoxidation of ole?ns. been proposed. Thus, for example, there has been pro It has now been found that, when a catalyst system hav posed a method wherein a strong active substance such ing the below described speci?c composition is used dis as a peracid, particularly peracetic acid is used as an. solved or suspended in the reaction solvent and ole?n, epoxidizing agent for ole?ns. However, this method has hydrogen peroxide can be advantageously used as an various drawbacks that peracetic acid itself is produced 55 epoxy source. from hydrogen peroxide and acetic acid or acetaldehyde According to the present invention, there is used a cat and oxygen; and therefore its production cost is high, alyst system comprising a combination of (1) at least one that peracetic acid is explosive and there is required a tin compound as a ?rst component and (2) a second com special care for its handling. ponent selected from the group consisting of compounds Further, there is also known an “in situ” method (I.E.C. of vanadium, molybdenum, tungsten, selenium, and 47, 147) wherein hydrogen peroxide is utilized as an boron, and mixtures of any two or more of these com epoxidizing agent in the presence of an acid catalyst pounds. together with a fatty acid. However, there is a great dis As for the tin compound which is the ?rst component, advantage that, due to the use of the strong acid catalyst, both organic tin and inorganic tin compounds may be the formed epoxide is hydrolyzed partially to become 65 used. 3,806,467 3 4 As for the organic tin compounds, there can be exem ?rst component to the second component is not inde pli?ed tin compounds having at least one hydroxyl group pendent of reaction products, the ratio may be varied or having a coordination group which can be converted widely. But, the ratio of atom of the ?rst component is to a hydroxyl group in the presence of water or hydrogen preferable more than that of the second component. The peroxide. More particular examples are those having any element of the second component per one tin atom is of the following formulae: 1—0.00l, preferably 0.1-0.01. Generally, a concentration (by weight ratio) of the mixture of the ?rst component and the second component in the reaction system is about 1/l0,000 to 1/ 10, preferably about 1/ 100 to 1/1,000. 10 However, generally, in case a boron compound is used for the second component, the higher the concentration of boron, the better the result. It is desirable therefore to use such boron compound as a saturated solution, if possible. 15 As regards the working mechanism of the catalyst sys tem of the present invention, there have been recognized wherein each of R1, R2, R3, R4, R5 and R6 represents an some phenomena which can explain that the ?rst compo alkyl group, aralkyl group, phenyl group, phenoxy group, nent, the second component and hydrogen peroxide form alkoxy group, hydrogen atom, carbonyl group, nitrile an active complex compound effective or favorable to the group, hydroxyl group, acyl group, halogen group, epoxidizing reaction. --—S—R or —O-R and R represents an alkyl or phenyl The solvent to be used in carrying out the method of group. It is also possible to employ a synthesized solu the present invention may be selected from a consider tion or extract containing such tin compound. ably wide range of ordinary organic compounds, provided Examples of the inorganic tin compounds, are tin chlo that they do not quickly react with the ole?n, hydrogen ride, tin sul?de, sodium stannate, tin oxide and organic acid salts of tin. 25 peroxide and/or catalyst. However, it has been found Generally, an organic tin compound has an activity that, in some solvents, the compatibility with ole?n and much higher than that of an inorganic compound. hydrogen peroxide is low so that the reaction system sepa The second component of the catalyst system of this in rates into a plurality of phases and, in case the reaction vention is selected from organic and inorganic compounds is continued for a long time or in case the reaction tem 30 perature is elevated, the tin compound is deposited on the containing molybdenum, tungsten, vanadium, selenium or wall and bottom of the reaction vessel. boron. Examples of the soluble second component are From the industrial viewpoint, when the solubility and naphthenates, stearates, octoates, carbonyls, acetylace stability of the raw material ole?n and catalyst system tonates polyacid, and the like, of the above-mentioned metals. Examples of the insoluble second component are and the stability of hydrogen peroxide are considered, 35 the proper selection of the solvent is important to the oxides, ammonium salts, phosphates, nitrates, sulfates, method of the present invention. carbonates, and the like. It has been found that, in case the below mentioned In case a boron compound is used as the second com [four operations are carried out in respect of various typi ponent, there can be enumerated 'boric acid, boron tri cal solvents, the stability of organic tin hydroxide and hy oxide, alkylboroxin, alkoxyboroxin, boric acid esters, me 40 tallic borates, halides, carbonyl compounds, alkyl boron drogen peroxide is remarkably in?uenced, as demon compounds and hydrides. strated in Table 2 to be indicated hereinlater: Operation 1: (Me)3SnOH and hydrogen peroxide were Further, composite salts containing any one of molyb dissolved at the room temperature. denum, tungsten, vanadium, selenium and boron, for ex ‘Operation 2: was added to the above men ample, boron tungstic acid, phosphorus molybdic acid, tioned solution. phosphorus tungstic acid, phosphorus vanadic acid, phos 45 Operation 3: The resulting solution was then warmed phorus selenic acid and compounds containing two or up to 60° C. more of these elements may also be used. Operation 4: Then the solution was allowed to stand The ?rst component and second component of the cat at the room temperature for 3 days. alyst to be used in the present invention may be added iIt has been observed from these results of the opera simultaneously as mixed in advance to the reaction sys 50 tions that generally alcohols such as straight chain a1~ tem or may be added separately to the reaction system. cohols, polyhydric alcohols and cyclic alcohols are pref Further, the catalyst can be used in the form of a com erable as solvents for the method of the present inven pound or complex compound containing simultaneously tion, but epoxides, ketones and furfurals can be also used. a tin atom and a molybdenum, tungsten, vanadium, seleni The heat of reaction in the epoxidation is considerably um or boron atom. 55 high so that the maintenance of the reaction tempera However, in the absence of any of these two compo ture is an important requirement in the case of industrial nents, that is, with the ?rst component or second com ly working the invention. However, by properly select ponent alone, no su?icient epoxidizing activity can be ing the solvent from among these solvents, the reaction obtained (refer to “Reference” examples given herein temperature can be maintained constant by utilizing the after). Thus, for example, even if a small amount of the 60 boiling point of the solvent. above described tin compound is added into a mixture of From the above, it will be understood that, in order hydrogen peroxide and cyclohexene and the mixture is to efficiently carry out the method of the present inven heated to 60-80“ C., substantially no chemical change tion, the selection of the solvent is important. occurs. Some tin compounds would senve rather as sta In carrying out the method of this invention, there bilizers for hydrogen peroxide. Further, on the contrary, 65 may be used commercial grade of hydrogen peroxide as it is known that, in case a small amount of only tung such, and generally an aqueous solution of such hydrogen stic acid is added, a large amount of a diol or ether is peroxide of a concentration of 10V to 90% may be used. produced, and substantially no epoxy compound is pro However, as an industrially cheap hydrogen peroxide duced (J. Org. Chem., 22, 1682 (1957)). In sharp con source, it is advantageous to use an unconcentrated un~ trast thereto, if both are made to coexist in the reaction 70 puri?ed intermediate product obtained by a known proc system, a surprisingly large amount of an epoxy com ess for the production of hydrogeniperoxide. pound is produced. For example, it is known that hydrogen peroxide and For the concentration of the catalyst, each of the ?rst ketone are obtained by atmospheric oxidization of a and second components can be selected independently secondary alcohol (US. 'Pat. No. 2,871,101). However, over a considerably wide range. Although the ratio of the 75 the hydrogen peroxide obtained by such process is 3,806,467 5 6 marketed in the form of an aqueous solution generally The present invention will be further explained by prepared through such steps as distillation, concentra referring to the following examples. tion and puri?cation. By such after treatments, the price Example 1 of hydrogen peroxide rises so surprisingly as to obstruct the industrial utilization of hydrogen peroxide. On the There were charged 11 g. of n-propanol (as a solvent), other hand, in the method according to the present in 4.0 g. of cyclohexene and 12 g. of 90% hydrogen vention, alcohols and ketones are very favorable solvents peroxide in a 50 cc. glass ?ask equipped with a re?ux giving results rather more favorable of an aqueous solu condenser and stirrer. Then 0.1 g. of trimethyl tin hy tion. Therefore, the reaction product containing hydro droxide Me3SnOH and 0.01 g. of acetylacetone molyb gen peroxide, alcohol and ketone obtained by the oxida— 10 denum salt MoO2(AcAc)z were added thereto as cata tion of a secondary alcohol can be used directly as such lysts. The mixture was caused to react at 50° C. for or as more or less concentrated as a source of hydrogen 9 hours. peroxide for the method of the present invention. After the reaction, the hydrogen peroxide was colored Further, another known process for producing hydro— with potassium iodide and was titrated with a 0.1 N gen peroxide by the oxidation of an anthraquinone 15 sodium thiosulfate solution to quantitatively determine derivative may also be advantageously combined with the unreacted hydogen peroxide. the epoxidation according to the present invention. The unreacted cyclohexene and produced cyclohexene Thus, it is possible to combine the method of the oxide were analyzed by gas chromatographs. present invention with an already known conventional As a result, the formation of 0.90 g. of cyclohexene process for the production of hydrogen peroxide, so that oxide was observed. This corresponds to 90% based on the method may be worked industrially advantageously. 20 the reacted hydrogen peroxide and 95% on the re— Examples of the compounds which can be epoxidized acted cyclohexene. by the method of the present invention are ole?nic com Examples 2 and 4 to 14 and Reference Examples 1 pounds such as propylene, normal butylene (1 or 2), iso and 2 (the use of various ole?ns and various com butylene, 1,3-butadiene, allyl alcohol, methyl allyl alco 25 binations of catalysts) hol, allyl chloride, isooctane, styrene and a-methyl styrene: unsaturated fatty acids such as soybean oil, Experiments were conducted in substantially the same oleic acid, etc.; cyclic ole?ns such as cyclohexene, 4 manner as in Example 1 except that the combinations of cyanocyclohexene, cyclooctadiene and cyclododecatriene; the kinds of ole?ns and catalysts and some reaction con ditions were changed. The results of the experiments are and the like. 30 'It is preferable, by taking the safety into consideration, collectively indicated in Table 1. to select the initial concentration of hydrogen peroxide Example 3 (the use of an extract) in the reaction mixture to be about 1 to 50% by weight. The procedure of Example 1 was repeated except that The concentration of the ole?n with respect to the hy a catalyst prepared in the following manner was used. drogen peroxide may be varied over a wide range. 35 Thus 1 g. of tributyl tin chloride was dissolved in an aque Though not critical, it is generally economically desirable ous solution containing 0.5 g. of sodium hydroxide, and that the mol ratio of the ole?n to hydrogen peroxide be was made to react at 80° C .for 2 hours. Then the reac 1:30 to 30:1. tion product was extracted with ether. The results ob The temperature to be used in the present reaction tained by the use of $40 the amount of the oil layer to varies over a very wide range depending on the properties 40 gether with 0.01 g. of MoO2(AcAc)2 to the reaction of ole?n to be epoxidized, the concentration of the system are shown in Table 1. catalyst and the ratio of the ole?n to the hydrogen per oxide. However, it is generally ~20° C. to 150° C., pref Example 15 (the use of propylene) erably 0° C. to 120° C. or particularly 20° C. to 100° C. There were charged 9.0 g. of ethanol (as solvent) into The reaction is conducted under a pressure suf?cient 45 a glass autoclave of a capacity of 50 cc. Further, 4.2 g. to maintain a liquid reaction phase. The reaction may of 70% hydrogen peroxide, 0.08 g. of trimethyl tin hy also be conducted below the atmospheric pressure but droxide and 0.014 g. of MoO2(AcAc)2 were added there usually a pressure of about 1 to 100 atmospheres is de to and then the mixture was cooled in a Dry Ice-methanol sirable. bath. After evacuation, there were introduced and dis The reaction time also varies depending on the prop 50 solved 3.8 g. of propylene. The autoclave was dipped in erties of ole?n to be epoxidized, the concentration of a water lbath at 40° C. and the mixture was allowed to the catalyst, the ratio of the ole?n to the hydrogen per react for 20 hours while being stirred. The results of the oxide, the reaction temperature and the desired extent experiment are shown in Table 1. of the reaction. It is possible to carry out the reaction Examples 16, 17 and 18 (the use of various other ole?ns) within such short time as about one minute or for a 55 long time such as 100 hours or longer. Reactions were conducted in the same manner as in Thus, as explained herein above, this invention pro Example 15 except that butene-l, isobutylene and buta~ vides a novel, economical and effective method for the diene (1,3) were respectively used as ole?ns. epoxidation of ole?ns. The present invention is fully The results of the experiments are shown in Table 1. distinguished from conventional methods wherein hy 60 Examples 19 to 34 (effect of reaction solvent) drogen peroxide is once converted to a peracid or organic hydroperoxide and is then used for the epoxidation. This Operation 1: 1 ml. of each of various solvents was invention has thus opened a way to the production of put into a test tube of a capacity of about 10 cc. Then an epoxy compound by the direct use of hydrogen per 0.01 g. of trimethyl tin hydroxide and 0.1 ml. of 90% hydrogen peroxide were added thereto and the solubility oxide, due to the discovery of a novel and very effective 65 catalyst system. The method of the present invention does was observed at the room temperature. not require the use of corrosive materials, is not bound Operation 2: 0.5 ml. of cyclohexene was added to the solution of the Operation 1 and change in solubility was by the by-production of any other industrial chemicals observed. chemicals and is therefore very advantageous to the in Operation 3: The solution of the Operation 2 was dustry. 70 heated on an oil bath and, after 3 hours, the solubility Since there is no acid catalyst which promotes the was again observed. hydrolysis of the formed epoxy compound in the re Operation 4: The solution of the Operation 3 was action system, the undesirable formation of glycols is cooled to the room temperature and was left for 3 days remarkably prevented. This is one of the features of and the solubility was observed. the method of the present invention. 75 The results are shown in Table 2. 3,806,467

TABLE 1 Hy- Reaction Ole?n drogen tempera- Reaction Yield of -—_——————— peroxide ture time epoxide Type G. (g.) Catalyst (° 0.) (hrs.) (g.) Remarks Reference example: 1__; ______Oyclohexene ______._ 4. 0 1. 2 M0Oz(A0A0)2 50 9 0.03 9 do 4. 0 1.2 HzWO; 50 9 0.05 Example: 1 _dn 4.0 1.2 M0Oz(A0A0)2, MeaSnOH 50 9 0.90 Selectivity 90%.1 2 (in 4.0 1. 2 M003, MeaSnOH 50 9 0.88 ‘i .do 4. 0 1. 2 M0O2(AOA0)2, BuzSnOH 50 9 0. 80 4 An 4.0 1.2 HzWOz, MeQSnOH 50 9 1.4 Selectivity 87%.1 5 dn 4. 0 1. 2 V0 (AcAc)z, MegSnOH 50 9 0. 02 6 _r1n 4.0 1.2 MoOz(AcAc)z, MezSnOH 60 12 0.80 Glycol 0.1 g. 7 Isooctane 7. 4: 4. 2 M002(AGAO)2, MeaSnOH 50 5 0. 34 8 ______- Styrene ______.. 8.0 1. 6 M0O2(A0A0)z, MegSnOH 50 24 0. 10 9 ...... __' Hyaneeyclohexene ______9.0 4.2 MOOz(AGAC)-z, MeaSnOH 50 4 0.50 10 Cyolnnnfq?iene 8. 0 1. 6 MOO2(ACAO)2, MezsnOH 50 24 1. 9 (a) 11 ______Cyelododecatriene ____ .- 1.4 1.6 M0O2(A0A0)2, MGQSHOH 50 24 0.85 (1) 12. _ Allyl chlorlde___ 8.0 1.6 M0O2(A0A0)2, MezSnOH 50 24 0.85 Selectivity 83%.1 13. _ Ethyl vinyl ethe 8.7 1.6 MOO2(ACAC)2, MeaSnOH 50 24 0.30 Selectivity 83%.; 14 ______. Allyl alcohol ____ _. 8.6 1. 6 M0Oz(AOA0)z, MegSnOH 50 24 0.32 1'; Propylene 3. 8 4. 2 M00z(AeAc)2, MezSnOH 40 20 0.21 ‘IR Butene-1 2. 6 1. 6 MoO2(AcAc)2, MegSnOH 40 20 0.31 17 ______.. Isobutene ______- 3. 6 4. 2 Mo0z(AcAc)z, MeBSnOH 40 20 0.47 IR 1,3-bufarliena 2. 4: 1. 6 M0O2(AcAc)2, MegSnOH 4O 20 0. 50 (5) 1 Selectivity: Mol percent of formed epoxide based on reacted hydrogen peroxide. 3 Formation of monoepoxide. - TABLE 2 Operation Example number Solvent 1 2 3 4

19 ______-_ (‘3H3 Insoluble ...... Insoluble ...... Insoluble ...... _ Insoluble.

20 ...... ' '.-:.-d0.- ' d"--- ' ' 410- D0.

21... " - C014. ” - -‘ " - do--- - do--. - - Soluble..-..-."..-. White turbid. 22 ______._ C¢H5OH ______.- Highly soluble.. Highly soluble-. Highly soluble.. Highly soluble.

Soluble ...... Soluble ...... Soluble ...... Soluble.

O 24 ______..'.' O '.-...dO...-:;...;..'.--d0--.-;;..-;- White turbid-... White turbid. HaC——C-—(|) H50: 25 ...... ; 0H .---..do_.. Y (10.. Soluble. '~ - Soluble.

H x

26 .... _;.'-.'_ (i-pr)aO._-.;.:.;.-..;;.. Insoluble- - .:.'.'. Insoluble- -...'... White turhid..... White turbid. 27...... /C:H4\ Highly soluble.. Highly soluble.. Highly soluble.. Do.

\ / CQH4 28. ....--... H3O\ ._...do.--..-.>_; ...... _do....-_;-.;.. Soluble_._-.-..... Soluble.

Highly soluble-. Highly soluble.- Highly soluble Highly soluble. . _ _ White turbid. - .- White turbid White turbid. Highly soluble ..... -. 0- ___. o Pyridine do...... Do. Propylene glycol. do .do . - - Highly soluble. Glycerin- ._ " .do. .- Do. Example 35 (catalyst) 01 There were charged 6 g. of (as sol B112 Sn lvent), 2.46 g. (30 mmols) of cyclohexene and 5 g. of an OR isopropyl alcohol Solution of hydrogen peroxide [con- 70 were added thereto as catalysts. The mixture was allowed taining 1.02 g. (30 mmols) of hydrogen peroxide] into to react at 53° C. for 1 hour. The product was analyzed in a 50 cc. glass ?ask equipped with re?ux condenser the same manner as in Example 1. As a result, the forma and stirrer. Then 2.7 mg. of acetylacetone molybdenum tion of 7.3 mmols of cyclohexene oxide was observed. salt MoO2(AcAc)2 and 150 mg. of dibutyl tin mono- This corresponded to selectivity of 81% based on the chlorohydroxide 75 reacted hydrogen peroxide and 94% on the cyclohexene 3,806,467 10

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000000000000000020000000000002900.00 2000000EM000852000m8388mmm00030 0000000008000003020.600008000000203208 mm2088mm008200820003300000308800 2000008.»0000000200m0moi?mxm0080 mm£90050 0000B000000000200300000000m000.0.0000.5.m 8003000009000 300000000020008008000020000000000...0200.»$3 800000080000008 0082000083802000320000000800008000H83 8002008.28000008000.00200590000000000m0 2000.0.000?0000300000000000000000000000083 0000800000208:08000030.008000.m20 “0080002000388800000803000080.w00 002030000“009mm009302080.; 03000.m0308010900800020 8000.00000:000“.0300“3000603355000 3,806,467 11 12 Reference Example 3 Example 62 The procedure of Example 1 was repeated except that The same reactor was used as in Example 57 except on a tin compound (the ?rst component of catalyst) was that methanol cooled with Dry ‘Ice was circulated in the used. As shown in Table 3, the yield of an epoxide was re?ux condenser to prevent the ?ow out of low boiling slight. point component. There were charged 12 g. of isopropyl alcohol (as a Example 57 (the use of boron compound as the solvent), 4.12 g. of allyl chloride as an ole?n and 10 g. second components) of an isopropyl alcohol containing 2.04 g. of hydrogen 10 peroxide into this reactor. Then 0.2 g. of bis(tributyl tin) There were charged 12 g. of isopropyl alcohol (solvent), oxide and 0.14 g. of boron trioxide were added thereto 4.92 g. of cyclohexene and 10 g. of an isopropyl alcohol as catalysts. The mixture was allowed to react at 60° C. solution containing 2.04 g. of hydrogen peroxide into a for 1 hour. There were obtained 1.2 mmols of epichloro 100 cc. glass ?ask equipped with a re?ux condenser and hydrin. The selectivity was 63% on base of the hydrogen stirrer. Then, 0.3 g. of dibutyl tin monochlorohydroxide 15 peroxide and 83% on the allyl chloride employed. and 0.14 g. of boron trioxide were added thereto. The mixture was allowed to react at 60° C. for 1 hour. The Example 63 product was analyzed in the same manner as in Example 1. As a result, the formation of 7.5 mmols of cyclohexene The procedure of Example 61 was repeated except that oxide was observed. The selectivity was 7.0% based on the other catalysts and solvent were employed. Thus 0.15 g. reacted hydrogen peroxide and 9.7% on the cyclohexene of trimethyl tin acetate and 0.14 g. of boron trioxide were employed. used as catalysts, and 12 g. of furfural were used as Example 5 S solvent. There were produced 1.3 mmols of epichloro hydrin. The selectivity was ‘67% based on the hydrogen The procedure of Example 57 was repeated except that 25 peroxide and 85% on the allyl chloride. 0.3 g. of tributyl tin chloride and 0.15 g. of boric acid What we claim is: were used as catalysts. y 1. A catalyst system consisting essentially of a com There were formed 3.1 mmols of cyclohexene oxide. bination of (l) at least one organic tin compound as a The selectivity was 65% based on the reacting hydrogen ?rst component having at least one hydroxyl group or a peroxide and 90% on the cyclohexene employed. 30 coordination group capable of being converted to a hy droxyl group in the presence of water or hydrogen per Example 59 oxide as represented by the formulas: There were charged 50 g. of isopropyl alcohol (as a solvent) and 15 g. of an isopropyl alcohol solution con taining 5.1 g. of hydrogen peroxide into the same reactor 35 as in Example 56. Then 0.9- g. of dibutyl tin monochloro hydroxide and 0.4 g. of tributoxy boroxin as catalysts were added thereto. After a leakage test, the autoclave was cooled in Dry Ice-methanol and evacuated. Then 40 12.6 g. of propylene were added thereto and the reaction was conducted at 60° C. for 4 hours. ‘Propylene oxide was quantitatively determined in the same manner as in Ex ample 55. Hydrogen peroxide was quantitatively deter mined the same as in Example 1. As a result, the formation of 20 mmols of propylene 45 oxide was observed. The yield was 80% based on the reacted hydrogen peroxide. wherein each of R1, R2, R3, R4, R5 and R6 represents an alkyl group, aralkyl group, phenyl group, phenoxy group, Example ‘60 alkoxy group, hydrogen atom, carbonyl group, nitrile 50 group, hydroxyl group, acyl group, halogen group, or There were charged 90 g. of isopropyl alcohol and —S-—R wherein R represents an alkyl or phenyl group, 0.7 g. of AIBN (azobisisobutylonitrile) as an initiator into and (2) a second component selected from the group con the reactor as used in Example 56. The isopropyl alcohol sisting of molybdenic acid, tungstic acid, selenic acid, was oxidized by introducing air. Thus the oxidation was boron tungstic acid, phosphorus molybdic acid, phos conducted for 5 hours by introducing air under pressure 55 phorous tungstic acid, phosphorous vanadic acid, phos during the reaction so that a reaction temperature of phorous selenic acid; and naphthenates, stearates, octo 130° C. and a reaction pressure of 50 kg./'cm.2 might be ates, carbonyls, acetylacetonates, oxides, ammonium kept. After the reaction, a part of the cooled solution was salts, phosphates, nitrates, sulfates or carbonates of taken and analyzed. ‘It contained 1200‘ mmols of isopropyl molybdenum, tungsten, vanadium or selenium; boric acid, alcohol, 150 mmols of a peroxide and 300 mmols of ace 60 boron trioxide, boronhydride, boron halides and boroxin tone. Then, 0.7 g. of tin oxide and 0.5 g. of boric acid were substituted with alkoxy or al-kyl groups, the ratio of the second component to the ?rst component being 1-0.001 added to this solution. ‘Propylene was introduced into to 1. the mixture to cause reaction in the same manner as in 2. The catalyst system according to claim 1, wherein Example 59, to produce 5 mmols of propylene oxide. 65 the ratio of tin atom of the ?rst component to each of The selectivity was 52% based on the reacted hydrogen the elements of molybdenum, tungsten, vanadium, selen peroxide. ium or boron atom of the second component is 10-100 Example 61 to 1. The procedure of Example 57 was repeated except that References Cited 70 0.1 g. of trimethyl tin hydroxide was added instead of UNITED STATES PATENTS dibutyl tin monochlorohydroxide. There were produced 2,833,788 5/ 1958 Skinner et al. __._.. 260—348.5 L 7.2 mmols of cyclohexene oxide. The selectivity was 75% 2,892,826 6/1959‘ Peters et al. ______252-430 X based on hydrogen peroxide and 90% on cyclohexene 2,946,778 7/ 1960 Ke et al. ______.___ 252-430 X employed. 75 (Other references on following page) 3,806,467 13 14 UNITED STATES PATENTS FOREIGN PATENTS 3,119,875 1/1964 Steinmetz et a1. __ 252-431 R X 788,951 1/ 1958 Great Britain ____ .. 252-431 R 3,166,547 1/1965 Loeb ______252-431 R X 3,210,329 10/1965 Jenkins ______.... 252-—431 R X ‘PATRICK P. GARVIN, Primary Examiner 3,455,976 7/1969 Wade ______252-431 R X 5 3,156,709 11/1964 Allan ______.. 260-3485 L U.S. Cl. X.R. 3,326,949 6/1967 Larson ______._ 252-431 R X 252-428, 430, 431 R, 431 C, 431 N; 260-3485 L 3,429,903 2/1969 Larson ______252-431 R X 3,507,809 4/19‘70 Kollar ______252-430 X