US3014928A - Wilke - Google Patents

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US3014928A
US3014928A US73033958A US3014928A US 3014928 A US3014928 A US 3014928A US 73033958 A US73033958 A US 73033958A US 3014928 A US3014928 A US 3014928A
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acid
cyclododecatriene
cyclododecadiene
acetaldehyde
trans
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/14—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic peracids, or salts, anhydrides or esters thereof

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  • Belgian patent specification No. 555,180 describes a process which is concerned with the production of cyclododecatri-(l,S,9)-enes concurrently with other cyclic hydrocarbons from butadiene and other diolefines.
  • organometallic mixed catalysts such as have been developed by K. Ziegler and collaborators for the polymerisation of ethylene
  • -It has been pointed out in said Belgian patent that these cyclododecatrienes are valuable starting materials for organic syntheses, especially for the production of a,w-difunctional derivatives of n-dodecane.
  • cyclic hydrocarbons can be converted by oxidation into difunctional open-chain compounds with the same number of carbon atoms.
  • Such a process has for example been achieved in the oxidation of cyclooctane to suberic acid.
  • These ring-splitting reactions can however only be carried out with good yields if it is possible for the cyclic hydrocarbon to be converted, prior to the splitting reaction proper, into a monofunctional or 1,2-difunctional oxidation product, for example into an alcohol or a glycol, since in this case the splitting reaction takes place preferentially on the carbon atoms already combined with oxygen.
  • suberic acid is obtained in a high yield from cyclooctanol by means of nitric acid.
  • cyclododecatriene can be converted simply with high yields into the desired monofunctional derivative by converting the cyclododccatriene into cyclododecadiene monoepoxide.
  • cyclododecatrienes of any desired configuration but specially the trans-trans-cis-configuration and the trans-trans-trans-configuration, are oxidised with or- 3,014,928 Patented Dec. 26, 1961 ice when no excess of per compounds is used, the formation velocity of this monoepoxide clearly being very much greater than the formation velocity of the diepoxides or triepoxides.
  • per acids such as performic acid, peracetic acid, trilluoroperacetic acid, perbenzoic acid or acetaldehyde peracetate.
  • acetaldehyde peracetate which is formed under certain conditions when acetaldehyde is oxidised and can be utilised in accordance with British Patent No. 735,974 for epoxidation purposes.
  • this per-compound the cyclododecadiene monoepoxide is obtained with a yield higher than and in addition acetaldehyde and acetic acid are recovered. This process can be carried out continuously particularly smoothly.
  • the oxidation is advantageously carried out at temperatures from 0 to 0, preferably from 20 to 50 C., in a solvent which is inert with respect to per-compounds.
  • Aliphatic or aromatic hydrocarbons, or their halogen or oxygen derivatives can for example be used as such inert solvents.
  • the cyclododecadiene monoepoxide obtained by the process of the invention can be hydrogenated selectively to cyclododecane epoxide or completely to cyclododecanol.
  • the cyclododecanol can be oxidised to cyclododecanone.
  • the cyclododecanone can'in its turn be converted in known manner into its oxime and the latter by Beckmann transformation into the lactarn of w-aminododecane carboxylic acid. It is known that the'lactam is an important initial material for the production of polyamide plastics.
  • the cyclododecanol can also be split, for example with nitric acid, to form dodecane-1,12-carboxylic acid, which also is an important material for the production of polyamides and polyesters.
  • Example 1 44 g. of 68% peracetic acid are added dropwise over a period of 1 /2 hours to a solution of 134 g. of cyclododecatriene in 462 g. of chloroform, the temperature being kept between 25 and30 C. by cooling. After the dropwise addition is complete, almost the whole of the peracetic acid has reacted. After the reaction mixture has been washed with a bicarbonate solution and the solvent removed, distillation of the residue yields 45.6 g. of cyclododecadiene epoxide, RP. 05 mm, 68-71 C., n 1.5060, as well as unmodified cyclododecatriene. The yield is 97% of the theoretical, based on reacted cyclododecatriene, and 64% of the theoretical, based on peracetic acid.
  • Example 2 The procedure is as set out in Example 1, but a mixture of glacial acetic acid and acetic acid anhydride (5:1) is used as solvent. The yield is 93% of the theoretical, based on reacted cyclododecatriene, and 72% of the theoretical, based on peracetic acid.
  • the solution is slowly heated to room temperature and left to stand for 2 hours, after which it is no longer possible to detect any peracid.
  • the chlorobenzene is distilled oil in vacuo and the residue is fractionated. 3.9 g. of cyclododecadiene epoxide are obtained, this corresponding to a yield of 65% of the theoretical.
  • Example 4 45.2 g. of acetaldehyde mono-peracetate, dissolved in 140 g. of glacial acetic acid, are added dropwise over a period of 50 minutes to 120 g. of trans-trans-cis-cyclododecatri-(1,5,9)-ene. The temperature is kept below 10 C. The reaction mixture is stirred for another 3 hours and thereafter the solvent is distilled off in vacuo. Fractionation of the residue through a highly effective column at 13 mm. Hg yields 44.4 g. of cyclododecadiene epoxide, RP 13 mm 133.8-1342" C.; i7 :1.5060. The yield is 83% of the reacted cyclododecatriene, or 66.5% based on the acetaldehyde mono-peracetate.
  • Example 5 The procedure is as set out in Example 4, except that trans-trans-trans-cyclododecatri-(1,5,9,)-ene, dissolved in glacial acetic acid, is used for the epoxidation. A similar yield of cyclododecadiene epoxide is obtained; the infrared spectrum of the product, as shown on the right hand side of the accompanying drawing, still gives an indication of the absorption due to a cis-double bond only in the middle position. B.P. mm 71-73" C.; 11 1.4995; M.P. 26-27 C.
  • Example 6 The procedure set out in Example 4 is used, but ethyl acetate is used as solvent, and the reaction temperature is kept between 25 and 30 C. The reaction is complete after only 1 hour. The yield is 92%, based on reacted cyclododecatriene, and 78% of the theoretical, based on acetaldehyde monoperacetate.
  • Example 7 The continuous epoxidation of cyclododecatri-(1,5,9)- ene with acetaldehyde peracetate is carried out as follows: A solution of acetaldehyde monoperacetate in ethyl acetate is continuously mixed at 5 to C. with a solution of cyclododecatriene in acetic ester (molar ratio between cyclododecatriene and peracetate 2:1). The cold mixture is introduced by suction into a separating column which is kept at 40-50" C. and which is under a vacuum of 30 to 50 mm. Hg. The separating column serves as reactor.
  • Acetaldehyde, ethyl acetate and the glacial acetic acid which is formed are drawn off through the head of the column.
  • the reaction product and unreacted cyclododecatriene are withdrawn from the lower part of the column and are separated from one another by being re-distilled in vacuo.
  • Example 8 The procedure followed is that set out in Example 3, but hexane is used instead of chlorobenzene as solvent.
  • the yield of cyclododecadiene epoxide is 85% of the theoretical, based on reacted cyclododecatriene, and 70% of the theoretical based on perbenzoic acid.
  • Example 9 215 g. of formic acid are run into vigorously stirred mixture of 1,300 g. of cyclododecatriene and 1,350 g. of 25% hydrogen peroxide. After a time, the internal temperature rises and the temperature is kept below 35 C. by cooling with ice and later with water. The mixture is stirred for 48 hours, whereupon the resulting two layers are separated and the organic layer is washed with water, dilute sodium hydroxide solution and bisulphite solution and dried over CaCl Distillation by means of an efiicient column yields 520 g. of unreacted cyclododecatriene, 846 g. of 1,Z-epoxycyclododecadi-S,9-ene and 12 g. of residue, i.e. a yield of 98% of the theoretical is obtained, with a conversion of 60%.
  • 1,2 monoepoxycyclododeca-di-(5,9)-ene which comprises oxidizing cyclododecatri-(l,5,9)-ene at a temperature between about 0 and 100 degrees C. with an oxidizing agent selected from the group consisting of acetaldehyde, monoperacetate, performic acid, perbenzoic acid and peracetic acid.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US73033958 1957-04-26 1958-04-23 Wilke Expired - Lifetime US3014928A (en)

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DEST12498A DE1058987B (de) 1957-04-26 1957-04-26 Darstellung von Cyclododecadienmonoepoxyd aus Cyclododecatrienen

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3138569A (en) * 1960-05-17 1964-06-23 Rhone Poulenc Sa Epoxide plasticizers and stabilizers for vinyl resins
US3374187A (en) * 1963-12-06 1968-03-19 Monsanto Chemicals Flame retardant compositions prepared from halogenated 1, 2-monoepoxycyclododeca-5, 9 -diene and adducts thereof
EP1035119B2 (en) † 1999-03-12 2005-01-12 Ube Industries, Ltd. Process for producing epoxycyclododecadiene

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1203765B (de) * 1960-02-20 1965-10-28 Rhone Poulenc Sa Verfahren zur Herstellung von trans, trans-Cyclo-dodecadien-(5, 9)-ol-(1) und einem Gemisch der cis, trans- und trans, cis-Cyclododecadien-(5, 9)-ol-(1)-Stereoisomeren
DE1196646B (de) * 1962-05-18 1965-07-15 Basf Ag Verfahren zur Herstellung von Cyclododecanol
DE3002838B1 (de) * 1980-01-26 1981-05-27 Degussa Ag, 6000 Frankfurt Verfahren zur Herstellung von 1,2-Epoxy-5,9-cyclododecadien
DE3002826C2 (de) * 1980-01-26 1982-02-04 Degussa Ag, 6000 Frankfurt Verfahren zur Herstellung von α-Epoxiden mit 11 bis 24 Kohlenstoffatomen
DE3002793B1 (de) * 1980-01-26 1981-06-25 Degussa Ag, 6000 Frankfurt Verfahren zur Herstellung von 1,2-Epoxycyclooctan
DE3002811C2 (de) * 1980-01-26 1981-11-19 Degussa Ag, 6000 Frankfurt Verfahren zur Epoxydierung von Cyclododecen oder Tricyclodecen-3

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2201200A (en) * 1938-04-04 1940-05-21 Du Pont Process of preparing thiolactams
US2221369A (en) * 1940-11-12 Process foe producing lactams
US2250445A (en) * 1938-10-01 1941-07-29 Rohm & Haas Process for producing acetylenic alcohols
US2281253A (en) * 1941-03-05 1942-04-28 Purdue Research Foundation Nitro alcohol
US2351352A (en) * 1941-07-29 1944-06-13 Shell Dev Separation of by-products from isophorone
US2359935A (en) * 1944-04-18 1944-10-10 Usa Composition of matter
US2426224A (en) * 1943-09-20 1947-08-26 Lilly Co Eli Processes for producing dibasic acids and derivatives of dibasic acids
US2438485A (en) * 1946-10-04 1948-03-23 Univ Ohio State Res Found Fluorinated dibasic acids and method of preparing same
US2500599A (en) * 1944-12-19 1950-03-14 Shell Dev Catalytic hydroxylation of olefinic compounds
US2524432A (en) * 1945-08-17 1950-10-03 Du Pont Esters of epoxy alcohols with propenoic compounds
US2541670A (en) * 1948-02-20 1951-02-13 Canadian Ind Reaction products of 4-vinylcyclohexene dioxide
US2752376A (en) * 1952-04-19 1956-06-26 Glidden Co Hydroxylation of vegetable oils and products thereof
AT192907B (de) * 1955-08-09 1957-11-11 Union Carbide & Carbon Corp Verfahren zur Herstellung von neuem 1, 2, 5, 6-Diepoxycyclooctan

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB735974A (en) * 1952-08-07 1955-08-31 Union Carbide & Carbon Corp Improvements in the epoxidation of ethylenically unsaturated organic compounds
AT187900B (de) * 1953-11-12 1956-12-10 Heilmittelwerke Wien Ges Mit B Verfahren zur Herstellung von Oxidoverbindungen des α-Dicyclopentadiens und des Dihydro-α-dicyclopentadiens
US2736730A (en) * 1954-12-02 1956-02-28 Velsicol Chemical Corp Epoxy-polychloro-bicyclo(2.2.1) heptene
DE962073C (de) * 1955-01-09 1957-04-18 Basf Ag Verfahren zur Herstellung von 1, 2-Epoxycyclooktan

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2221369A (en) * 1940-11-12 Process foe producing lactams
US2201200A (en) * 1938-04-04 1940-05-21 Du Pont Process of preparing thiolactams
US2250445A (en) * 1938-10-01 1941-07-29 Rohm & Haas Process for producing acetylenic alcohols
US2281253A (en) * 1941-03-05 1942-04-28 Purdue Research Foundation Nitro alcohol
US2351352A (en) * 1941-07-29 1944-06-13 Shell Dev Separation of by-products from isophorone
US2426224A (en) * 1943-09-20 1947-08-26 Lilly Co Eli Processes for producing dibasic acids and derivatives of dibasic acids
US2359935A (en) * 1944-04-18 1944-10-10 Usa Composition of matter
US2500599A (en) * 1944-12-19 1950-03-14 Shell Dev Catalytic hydroxylation of olefinic compounds
US2524432A (en) * 1945-08-17 1950-10-03 Du Pont Esters of epoxy alcohols with propenoic compounds
US2438485A (en) * 1946-10-04 1948-03-23 Univ Ohio State Res Found Fluorinated dibasic acids and method of preparing same
US2541670A (en) * 1948-02-20 1951-02-13 Canadian Ind Reaction products of 4-vinylcyclohexene dioxide
US2752376A (en) * 1952-04-19 1956-06-26 Glidden Co Hydroxylation of vegetable oils and products thereof
AT192907B (de) * 1955-08-09 1957-11-11 Union Carbide & Carbon Corp Verfahren zur Herstellung von neuem 1, 2, 5, 6-Diepoxycyclooctan

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3138569A (en) * 1960-05-17 1964-06-23 Rhone Poulenc Sa Epoxide plasticizers and stabilizers for vinyl resins
US3374187A (en) * 1963-12-06 1968-03-19 Monsanto Chemicals Flame retardant compositions prepared from halogenated 1, 2-monoepoxycyclododeca-5, 9 -diene and adducts thereof
EP1035119B2 (en) † 1999-03-12 2005-01-12 Ube Industries, Ltd. Process for producing epoxycyclododecadiene

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DE1058987B (de) 1959-06-11
DE1058987C2 (cg-RX-API-DMAC7.html) 1959-11-26

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