sign in sign up
<<
Home , Ruthenium tetroxide

Patented Mar. 9, 1948 2,437,648

UNITED STATES PATENT of FICE 2,437,648 f CATALYTIC OX DATION OF UNSATURATED ORGANIC COMPOUNDS Nicholas A. Milas, Belmont, Mass., assignor to Research Corporation, New York, N. Y., a cor poration of New York No Drawing. Application September 15, 1943, Seria No. 502,525 11. Claims. (CL 260-617) 2 This invention relates to the catalytic oxida and/or hydroxy acids. In the case of tion of unsaturated organic compounds, and its benzenoid hydrocarbons the glycols produced de principal object is to provide a simple, economi hydrate to yield phenols which may be further cal and efficient process of producing useful oxidized to produce quinones. oxygenated organic compounds such as glycols, I have successfully produced substantially phenols, aldehydes, , quinones and Or-. good yields of ethylene glycol from ethylene, ganic acids. propylene glycol from propylene, isobutylene gly Further objects will be apparent from a con col from isobutylene, glycollic acid from acet sideration of the following description wherein ylene, trimethyl ethylene glycol from tri-methyl I have illustrated the application of my new 10 ethylene, pinacol from tetramethyethylene, 2 process in the preparation of various substances methylbutane diol-1,2 from 2-methyl buttene-1, constituting the class of oxygenated organic pentane diol-2,3 from pentene-2, cetene glycol Compounds. from cetene, hexane tetrol-1,2,5,6, from di-ally, The term "unsaturated organic compound' and phenyl glycol from styrene, cis-cyclohexane derivatives thereof, as herein used, is confined 15 diol-12, adipic and adipic acid from to compounds embodying an unsaturation be cyclohexene, p-menthane tetrol-1,2,8.9 from d tween atoms, such for example as the limonene, cyclopentenediol-1,4' and cyclopen olefins, aromatic hydrocarbons, acetylene, com tanetetrol-1,2,3,4, from cyclopentadiene, ethyl pounds of the general formula, R-C=CH, where- . dihydroxybutyrate from ethyl crotonate, diethyl in R represents a monovalent hydrocarbon 20 mesotartrate from diethyl maleate, diethyl race radical, and compounds of the general formula mate from diethyl fumarate, 2-methyl-pentene R-CsC-R1 wherein R, and R1 represent diol-2,3-one-4 from mesityl , glycol-alde monovalent hydrocarbon radicals, and the term hyde from vinyl acetate, glycolaldehyde from "oxygenated organic compound,' or the like ex divinyl ether, glycolaldehyde from vinyl bromide, pression, as herein used, embraces only those 25 9,10-dihydroxy-stearic acid from oleic acid, Substances which are classified as glycols, phenols, beta-phenylglycerol and di- (beta-phenylglycerol) aldehydes, quinones, ketones and organic acids. ether from cinnamyl , phenol from ben I have found that when an unsaturated organic Zene, Cresols from toluene, naphthaquinone from compound is treated with , in naphthalene, anthraquinone from anthracene, the presence of an essentially anhydrous inert 30 phenanthrenequinone from phenanthrene, glyc Organic and of a Small amount of a erol from allyl alcohol, phenyl glyceric acid Catalytically active oxide of a metal known to from cinnamic acid, di-hydroxybutyric acid from form very unstable paracids including Os, Ti, Zr, crotonic acid, mesotartaric acid from maleic Th, W, Nb, Ta, Cr, Mo, W, U and Ru-(see J. A. acid, racemic acid from fumaric acid, anisalde C. S., 59, pages 2342 and 2343; and Berichte, 41. 35 hyde and anisic acid from anethol, vanillin from (1908), page 3536), preferably, tetroxide, isoeugenol, piperonal from isosafrole, homopiper tetroxide, pentoxide, molyb onal from safrole, di-hydroxy-stearic acid from denum oxide or trioxide, in an essen oleic acid, etc. tially non-alkaline environment (that is, in the . The reaction of the various types of olef absence of an inorganic ), there is produced 40 with hydrogen peroxide, in accordance with the an Oxygenated organic compound, the nature of present invention, may therefore be generalized which depends upon the particular type of un by the following equations: Saturated compound subjected to such treat ment, the temperature, the pressure (if the com I. (Monosubstituted olefins) 45 pound treated be in gaseous phase), the solvent catalyst medium, the extent of oxidation and other such (a) R-(-CH, -- OOI um) factors. For example, olefins and their deriva tives invariably yield glycols which may be fur bH bH ther oxidized to produce aldehydes, ketones : wherein R represents a monovalent organic radi and/or organic acids, and acetylene and its 50 cal of the group consisting of alkyl and aryl radi mono- or di-substitution products yield hydroxy cals. 2,437,648 3 4. Further oxidation of the glycol thus formed and the aldehyde may be further oxidized to pro produces aldehydes, as follows: duce an organic acid as in I (c). (b) IV. (Tetrasubstituted olefins) catalyst R--CH, -- HOOBI su R R. Catalystalyst R. R. be bh (a) R-(--R, -- IOO - R-b-b-R, and still further Oxidation results in the forma on be tion of Organic acids, as follows: wherein R1, R2, R3 and R4 represent monovalent organic radicals of the group consisting of alkyl H E. catalyst 10 and aryl radicals. (c) R-(-0 -- H--0 -- 200 - 0 This type of glycol may be oxidized to produce O O ketOnes, as follows: R-(-og -- E-5-on -- 2EO (b) R. R. catalyst R R II. (Disubstituted olefins) s R---R+Ho O - C=O-- C=O-2HO R R de bH R R (c) R-(-)-H - HOOH catalyst R-(-)-H The reaction of hydrogen peroxide and ethyl ene, a typical olefin, to produce ethylene glycol bH Öh proceeds as follows: wherein R1 and R2 represent monovalent organic 20 catalyst radicals of the group consisting of alkyl and aryl W. BC=CH -- HOOBI - C-CBI radicals. Further oxidation of the glycol thus formed on be produces a and an aldehyde, as follows: 25 Although further oxidation of ethylene glycol (b) R. H. yields formaldehyde which may be oxidized to catalyst formic acid as illustrated in Equations (a) and R-C-C-H -- OO e-H) I (b), this does not take place to a great degree, bH bh since yields Of glycol as high as 97% have been produced. R R 30 Similarly, the reaction of the aforesaid acety C=O -- C=O -- 2BO lenic compounds and hydrogen peroxide may be / H^ illustrated by the following equations:

VI. (Monosubstituted acetylene) catalyst OB OB - HOOH (a) RCsCH -- HOOH N- RC-CH - RC-CH -- HO - - R-GH au R(-CH bH OBI. bH & and the aldehyde may be further oxidized to pro wherein R represents a monovalent organic radi duce formic acid, cal of the group consisting Of alkyl and aryl radi III. (Trisubstituted olefins) Cals. R. Rs catalyst R. R. The hydroxy and keto aldehydes thus formed (c) R-(-)-H -- HOOH murd R---H 50 may be oxidized further to produce organic acids Ös bH as follows: wherein R1,R2 and R3 represent monovalent or ganic radicals Of the group Consisting of alkyl and aryl radicals. SS E. Oxidation of the glycol thus formed produces / catalyst a ketone and an aldehyde, as follows: (8) r-i-Hba - HOOH - RC-COOHba -- HO (b) R---ER. R. + Hoog catalyst 60o H be R 8 catalyst C=O -- R-6-0 -- 20, (e) RC-C -- HOOH - RC-COOH -- HO R

VII (Disubstituted acetylene) catalyst O OB (a) RCSCR - HOOH -- HOOH - RC-C-R - R-C-C-R -- 2BO N be bit RCameC-R mm) R-C-O-m-R

37,069 5 5 wherein R and Ra represent monovalent organic radicals of the group consisting of alkyl and aryl / radicals. catalyst H CeO +2Ho VII. The reaction of hydrogen peroxide and - acetylene (CH3) to produce ca) glyoxal and is C-O glycollic aldehyde, - (b) glycollic acid, and (c) Oxalic acid may proceed as follows: Adiplo aldehyde

(o) HCsCE + EIOOE -ofa" EI-CH - Big-g-H + 3EO bH be

Y Cuu-CE are all--0 a de de catalyst (8) CaCE - 2HOOH al-A BIC-C-C-OE - 20 B. B. a (e) all--o -- IOOE cataly al-c OOH -- HO E. bH

CK. For cyclohexene the addition of hydrogen c) - peroxide proceeds as follows: / 8 so catalyst H COO -- 2BOOBI - 0 - 20 (s) B E. so B COOB + goon ata / BS Y4 YE i 3. B O Adipic acid X. For benzene, toluene, naphthalene, an thracene, phenanthrene and the like, the addi Cyclohetes - Oyelohexanediol-2 tionfollows: of hydrogen peroxide may be illustrated as

O) H on O O s +Hoogeatalyst r um) B -- BO Bl E. Phenol

(b) CE. O. C - OE O aua) - HO CE, H. Jh Catalyst B - BOO YL o-Cresol CB Catalyst B B N ummd - HO B. B B B OB " - O B 2,437,648 7 8 (e) O O

2IOOF Catalystarmamrud Y. -- 20 B

- HOOHov/ O. p-Naphthaquinoneuin Catalyst OB . Catalysilatoon sum) -- HO OB I OB a-Naphthol a-28 O

-OB O B OE O Catalyst 8HOOBI -- 2HO

COO o-Naphthaquinone 8EO COOBI Phthalo acid (d) B OB Catalyst - HOOH - 0

B OB Catalystatioon O

- 2HO

Anthraquinone (e)

Catalyst OH2HooH O - HOOH - ead --2HO S-OB Catalyst O

Phenanthraquinone In carrying out my process successfully, it is . Illustrative examples of operable advisable to employ substantially anhydrous Sol ethers include: ethyl, propyl, butyl and amyl di vents, preferably selected from such organic sub 65 Oxane, ethers of ethylene glycol and diethylene stances that do not undergo oxidation during glycol, etc. Among operable inert (that is, un the reaction, Tertiary , in general, and reactive) organic solvent media is nitromethane. particularly tertiary butyl and tertiary any al The organic Solvent employed is, in all cases, cohols, have been found to be suitable Strictly a medium or vehicle, and is not a re for this purpose, although it is to be understood 70 actant. that the invention is not confined to these Sol The reaction mixture (material to be oxidized, vents since various other reagents, such as ni the hydrogen peroxide treating agent, the or triles and certain types of ethers, acetic acid ganic solvent medium-where used-and the tertiary alcohol mixtures, etc., may be used to catalyst) preferably is initially substantially an advantage. Illustrative of operable nitriles is 75 hydrous.

9 2,437,648 A preferred procedure for the preparation of O the hydrogen peroxide reagent in tertiary butyl of isobutylene glycol from isobutylene using alcohol is as follows: chronic acid, vanadium pentoxide or molybde 400 cc. of pure tertiary butyl alcohol is added nun. Oxide as catalyst; and, using osmium tetrox to 100 cc. of 30% hydrogen peroxide (Albone C), as catalyst, over 30% glycollic acid from acet and the solution treated with small portions of ylene. anhydrous sulphate, thereby forming two layers. The alcohol layer, containing most of 2-LIQUID AND SOLID UNSATURATED SUBSTANCEs the hydroger peroxide, is removed. The so sepa (a) Hydrocarbons rated hydrogen peroxide-rich layer may be used The unsaturated hydrocarbons are dissolved without further treatment; however, I may fur O or mixed with the peroxide reagent containing a ther dehydrate the same by treating it with more suitable catalyst of the type previously suggested anhydrous sodium sulphate, and finally with an and the reaction is allowed to proceed either at hydrous sulphate or sulphate. or below room temperature if glycols are desired, A solution containing approximately 6% hydro or above room temperature if aldehydes, ketonés gen peroxide in tertiary butyl alcohol is thus ob 5 and organic acids are desired. The hydrocar tained, and this solution may be concentrated bons may be present preferably in the ratio of by vacuum distillation of the alcohol at room One mole to one or two moles of the peroxide, temperature to any desired concentration with although greater excess of peroxide is necessary out loss of the peroxide, provided an all-glass or when aldehydes, ketones and acids are desired. other suitable apparatus is employed. 20 The Speed of the reaction up to certain limits An catalyst may be prepared depends upon the concentration of the catalyst by dissolving substantially anhydrous osmium which may be present preferably in concentra tetroxide in substantially pure tertiary butyl al tions from .05 g. to .5 g. per mole of the sub cohol, free from isobutylene. stance to be oxidized, although it is to be under A catalyst similarly may 25 stood that these limits may at times be exceeded be prepared by dissolving Substantially anhydrous without affecting appreciably the yields of the chromic acid (CrO3) in a substantially pure Sat Oxygenated products. The end of the reaction urated tertiary alphatic alcohol (CnH2n--1)3 is usually indicated by a color change or by the COH, e. g., substantially pure tertiary butyl or absence of peroxide. The glycols or other oxy amyl alcohol, or in a substantially anhydrous 30 genated products may then be separated either mixture of acetic acid and a tertiary alcohol; Or, by fractionation. Or in any other well known man the substantially anhydrous CrO3 may be added ner. Using this general procedure I have suc directly in the solid form to the substantially ceeded in producing over 30% of pentane diol-2,3 anhydrous medium containing hydrogen peroxide from pentene-2; 38% of trimethyl ethylene gly and the substance to be hydroxylated. Prepara 35 col from trimethyl ethylene; 51% of 2-methyl tion of the other catalytic metal may sin butane diol-1,2 from 2-methyl butene-1; 82% of ilarly be formed by dissolving the metal oxide in cetene glycol from cetene; over 50% of phenyl one or another of the organic Solvents above glycol from styrene; 58% cyclohexane diol-12 stated. Or, the selected catalytic metal oxide and about 35% adipic acid from cyclohexene; may be added, in powdered or finely divided State, . 40 45% of hexane tetrol-1,2,5,6 from di-allyl; 35% to the hydrogen peroxide reagent wherein the of p-menthane tetrol-1,2,8.9 from limonene; same eventually dissolves forming a completely 22-30% phenol from benzene; about 30% of homogeneous solution. The catalyst may be used Cresols from toluene; and almost quantitative alone or in combination. yield of anthraquinone from anthracene. The I have found that the temperature playS an 45 yields in all cases were based on the amount of important role in directing the type of oxygenated hydrocarbon used up in the reaction. product to be formed. For example, formation of glycols in high yields is usually favored be (b) Miscellaneous tween room temperature (e. g., 21 C.) and Using the same procedure as in the foregoing several degrees below 0° C., whereas aldehydes, 50 examples, I have produced 60% glycerol from ketones and organic acids are produced more ad ally alcohol; 54% of a.,8-dihydroxy butyric acid vantageously at temperatures higher than room from crotonic acid; 56% of phenyl glyceric acid temperature (e. g., between 21 C. and the boil from cinnamic acid; 48% of racemic acid from ing point of the non-aqueous solvent employed). fumaric acid; over 30% mesotartaric acid from The following examples are illustrative of the 55 maleic acid; 60% 9,10-dihydroxy stearic acid application of the invention: from oleic acid; 57% of diethyl racemate from diethyl fumarate; 55% of anisaldehyde from. 1-GASEOUS UNSATURATED SUBSTANCE anethol; 66% of vanillin from isoeugenol; 68% For the production of ethylene glycol or of any yield of piperonal from isosafrole; and 44% of glycol from any unsaturated gaseous Substance, 60 homopiperonal from safrole. In the case of some the latter may be bubbled through the peroxide essential oils in which the double bonds are very reagent containing any one of the catalysts above active, the oxidation is apt to go beyond the glycol suggested, or any combination of them, or it may state, although it may be controlled to produce be introduuced under pressure of various mag the glycol. nitudes from one to several atmospheres or even 65 The invention is more particularly described several hundred atmospheres. The end of the and further illustrated in the following: reaction is usually indicated by a color change Mesotartaric acid from maleic acid.--To 2.9 g. or by the complete utilization of the peroxide as (0.025 mole) of maleic acid were added 27.2 cc. determined by titration. The glycol or other (0.05 mole) of 6.3% solution of hydrogen per products may be separated by fractionation or 70 oxide in anhydrous tertiary butyl alcohol and in any other suitable manner. Using the pro 2 cc. osmium tetroxide solution in tertiary butyl cedure herein disclosed I have succeeded in pro alcohol, and the mixture was allowed to stand ducing 97% of ethylene glycol from ethylene; overnight at room temperature. The reaction. 68% of propylene glycol from propylene; 38-40% was complete on the following day when the 75 solvent was removed under reduced pressure and

2,487,648 12 11 removed from the reaction mixture by distilla the residue dissolved in . The Solution was tion under reduced pressure and in an atmosphere then made ammoniacal, heated to boiling and of , and the dark brown, viscous residue treated with excess 10% calcium chloride Solu was repeatedly extracted first with petroleum tion, whereby the calcium oxalate and mesotar ether and then with ethyl ether. Finally, the trate precipitated out. This precipitate was re residue was fractionated under reduced pressure moved, dried and weighed: yield 1.9 g. To remove and 23.7 g. of a fraction boiling at 80-83 (1 mm.) the calcium nesotartrate, the precipitate was was collected and found to consist essentially of extracted with 20% sodium hydroxide solution. cyclopentene-2-diol-1,4, This separation yielded 1.2 g. of calcium meso This glycol is a pale yellow, highly viscous liq tartrate and 0.7 g. of calcium oxalate. The cal O luid, Soluble in Water, alcohol and ethyl acetate; cium mesotartrate was further purified by repre insoluble in ether, benzene and other hydrocarbon cipitation and analyzed. Solvents. It rapidly reduces ammoniacal The yield of mesotartaric acid was 30.3%, and nitrate in the cold, and instantly decolorizes bro that of oxalic acid 14.6%, of the 1.9 g, of maleic mine Water. It is not a ketonic Substance. It acid consumed in the reaction. 15 Vanillin from isoeugenol-Five grams of is believed that the product is the cis isomer isoeugenol was mixed with 45 cc. of 6.3% solution of hydrogen peroxide in anhydrous tertiary amyl alcohol and 0.02 g. of vanadium pentoxide. The catalyst went into solution, which heated up Spon 20 re o taneously. The reaction was complete in about since a benzylidene derivative was obtained by twelve hours when the mixture had become more Condensation of the unsaturated glycol with benz intensely red. An analysis for the presence of aldehyde in accordance with the method of Platt vanillin by precipitating the p-nitrophenylhy and Hibbert (Can. J. Res., vol. 7, 1932, p. 629). drazone gave a yield of 66% of vanillin. 25 The aforesaid residue contained also a minor Anisaldehyde from anethole (p-methoacy amount (about 5-10%) of cyclopentanetetrol propenyl ben2ene).--To 5 g. of anethole Were 1,2,3,4. This latter compound is an amorphous, added 45 cc. of 6.3% solution of hydrogen per slightly colored, very hygroscopic solid (having no oxide in anhydrous tertiary amyl alcohol and definite , turning brown at 190° C. 0.02 g. of vanadium pentoxide. The catalyst 30 and black at 200 C.); soluble in water and alco went slowly into solution, which heated up almost hol but insoluble in ether, ethyl acetate and vari to the of the solvent. The reaction Ous hydrocarbon Solvents. was over in about two hours when the mixture Glycolaldehyde from vinyl acetate.--To. 17.7 g. became deep red and the peroxide had com of vinyl acetate (B.P. 72.5-73) was added 110 cc. pletely disappeared. Considerable amounts of 35 of 6.23% solution of hydrogen peroxide intertiary acetaldehyde vapor came off during the reaction. butyl alcohol; the mixture was cooled to 0, and The solvent was then removed under reduced to it was added 1 cc. of a solution of osmium tet pressure and the residue dissolved in glacial roxide in tertiary butyl alcohol. After five days acetic acid. Aliquot parts of this were analyzed at 0' the reaction was complete (reaction mixture for anisaldehyde. The yield of anisaldehyde 40 turned brown, and peroxide had completely dis amounted to 55%. In addition to anisaldehyde appeared), whereupon the reaction mixture was some anisic acid was isolated from the reaction, distilled to remove unconverted vinyl acetate and and a small amount of a deep red Solid which is the Solvent. There was obtained a yield of 60% of presumably an addition product of vanadium glycolaldehyde pentoxide with anisaldehyde. CH-C- Phenol from benzene-Fifteen and six-tenths grams of benzene (thiophene-free) was mixed (bit 6 With an equimolecular quantity of the hydrogen based on the amount of vinyl acetate consumed. perOxide Solution and 0.04 g. of Vanadium pent 9.10 dihydroacgstearic acid from oleic acid-7 g. oxide. The catalyst went slowly into solution 50 of oleic acid, B. P. 230-235 (21 mm.), was mixed which, after a few hours, acquired a blood red with 14.3 cc. of a 5.95% solution of hydrogen color. At the end of twenty-four hours, the reac peroxide intertiary butyl alcohol; the mixture was tion was complete, the red color had disappeared, cooled to 0, and to it was added 0.5 cc. of a solu and the catalyst separated out as a dark green tion of osmium tetroxide in tertiary butyl alcohol. precipitate. The mixture was then filtered, the The solution became orange in color, but after filtrate fractionated to remove the solvent and Standing Over night at 0 it turned colorless and the unused benzene (13 g.), the residue dissolved the reaction was complete. A considerable in water, and the amount of phenol estimated by amount of 9,10-dihydroxystearic acid had precipi precipitating the insoluble tribromophenol. Two tated. The Solvent was removed under reduced and nine-tenths grams of tribromophenol was 60 pressure and the residue was washed thoroughly obtained corresponding to 30% yield of phenol with ether to remove any unconverted oleic acid. calculated on the basis of the amount of benzene The washed, Solid, product was recrystallized from used. A sample of tribromophenol was recrys absolute alcohol: M. P. 129-131 corr.). Its neu tallized from dilute alcohol, M. P. 93, and showed tralization equivalent was found to be 319. The nO depression upon mixing With an authentic 65 yield amounted to 60%. sample of tribromophenol. This application contains subject-matter in Cyclopentene-2-diol-1.4 from cyclo- penta common with my application Serial No. 382.273, denie-A Solution of 0.85 mole of hydrogen per now abandoned, filed March 7, 1941, and is a oxide in 560 cc. of tertiary butyl alcohol (anhy continuation-in-part thereof. drous) was cooled to about 2° C. and then mixed 70 I claim: with 51 g (0.773 mole) of freshly distilled cyclo 1. Process for the direct production of poly pentadiene (B. P. 40-43 under total reflux) and hydroxy derivatives of unsaturated hydrocarbons 5 cc. of a 0.5% solution of osmium tetroxide in containing at least one olefinic linkage, which tertiary butyl alcohol. The reaction was com comprises treating the hydrocarbon with hydro plete at 0 in three days. The solvent was then 75 gen peroxide in a neutral and initially substan 2,487,848 3 tially anhydrous environment and in the presence 14 of a catalytically active oxide of a metal which drous solution of hydrogen peroxide in the pres forms unstable per-acids, and recovering the re ence of a catalytically active oxide of a metal sulting polyhydroxy derivative from the reaction which forms unstable per-acids, and recovering mixture. the resulting polyhydroxy derivative.from the rea 2. Process for the direct production of poly 5 action mixture. hydroxy derivatives of unsaturated hydrocarbons 8. Process for the direct production of a prod containing at least one olefinic linkage, which uct consisting mostly of cyclopentene-2-diol comprises treating the hydrocarbon with a neutral 1,4(cis) from cyclopentadiene, which comprises and initially substantially anhydrous solution of treating cyclopentadiene with a neutral and ini hydrogen peroxide in the presence of a catalyti 10 tially substantially anhydrous solution of hydro cally active oxide of a metal which forms unstable gen peroxide in an inert organic solvent medium per-acids, and recovering the resulting polyhy in the presence of a catalytically active oxide of droxy derivative from the reaction mixture. a metal which forms unstable per-acids, at a ten 3. Process for the direct production of poly perature below normal room temperature, and hydroxy derivatives of unsaturated hydrocarbons 5 recovering the resulting diol from the reaction containing at least one olefinic linkage, which mixture. comprises treating the hydrocarbon with a neu 9. Process for the direct production of isobu tral and initially substantially anhydrous Solution tylene glycol from isobutylene, which comprises of hydrogen peroxide in an inert organic solvent treating isobutylene with a neutral and initially medium in the presence of a catalytically active 20 substantially anhydrous solution of hydrogen oxide of a metal which forms unstable per-acids, peroxide in an inert organic solvent medium in and recovering the resulting polyhydroxy deriva the presence of a catalytically active oxide of a tive from the reaction mixture. metal which forms unstable per-acids, and recoV 4. Process for the direct production of polyhy ering the resulting isobutylene glycol from the re droxy derivatives of unsaturated hydrocarbons 25 action mixture. containing at least one olefinic linkage, which 10. Process for the direct production of hex comprises treating the hydrocarbon with a neu anetetrol-1,2,5,6 from di-allyl, which comprises tral and initially substantially anhydrous solu treating di-ally with a neutral and initially sub tion of hydrogen peroxide in a solvent medium stantially anhydrous solution. Of hydrogen per essentially consisting of a tertiary monohydric 30 oxide in an inert organic solvent medium in the saturated aliphatic alcohol in the presence of a presence of a catalytically active oxide of a metal catalytically active oxide of a metal which forms which forms unstable per-acids, and recovering unstable per-acids, and recovering the resulting the resulting hexanetetrol-1,2,5,6 from the reac polyhydroxy derivative from the reaction mix tion mixture. ture. 35 11. As a new product, cyclopentene-2-diol 5. Process for the direct production of polyhy 1,4(cis). droxy derivatives of olefins, which comprises NICHOLAS A. MILAS. treating the olefin with a neutral and initially substantially anhydrous Solution of hydrogen per REFERENCES C TED oxide in an inert organic solvent medium in the 40 The following references are of record in the presence of a catalytically active oxide of a metal file of this patent: which forms unstable per-acids, at a temperature FOREIGN PATENTS below the boiling point of a solvent medium, and recovering the resulting polyhydroxy derivative Number Country Date of the olefin from the reaction mixture. 508,526 Great Britain ------July 3, 1939 6. Process for the direct production of poly y OTEER REFERENCES hydroxy derivatives of diolefins, which comprises treating the diolefin with a neutral and initially Milas et al.: "Jour. Am. Ch. Soc.," vol. 58, pages substantially anhydrous solution of hydrogen 1302-1304 (1936); vol. 59, pages 543-544 (1937); peroxide ln an inert organic solvent medium in 50 vol. 59, pages 23424-2347 (1937) ; vol. 61, pages the presence of a catalytically active oxide of a 1844-1847 (1939) ; vol. 62, pages 1841-1843 (1940). metal which forms unstable per-acids, at a tem "Chemical Abstracts'; vol. 15, p. 237 (1921), perature below the boiling point of the solvent abstract of article by Boeseken et al. in "Proc. medium, and recovering the resulting polyhy Acad. Sci. Amsterdam'; vol. 23, pp. 69-73 (1920); droxy derivative of the diolefin from the reaction 55 vol. 24, pp. 52867 (1930), abstract of article by mixture. Criegee in 'Ann" vol. 481, pp. 263-302 (1920); 7. Process for the direct production of a poly vol. 32, col. 122 (1938), abstract of article by hydroxy derivative of an unsaturated aliphatic Dane et al. in "Ann" vol. 532, pp. 29-38 (1937). hydrocarbon containing a conjugated system of Criegee: 'Annalen der Chemie," vol. 522, pages double bonds, which comprises treating the hy 60 94-96 (1936). drocarbon with an initially substantially anhy Daneet i: Ibid, vol.532, pages 29–35 (1937).