US3109863A - Psocess for the preparation of - Google Patents
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- US3109863A US3109863A US3109863DA US3109863A US 3109863 A US3109863 A US 3109863A US 3109863D A US3109863D A US 3109863DA US 3109863 A US3109863 A US 3109863A
- Authority
- US
- United States
- Prior art keywords
- epoxyphenylethane
- hydrogenation
- alcohol
- atmospheres
- suspension
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000002360 preparation method Methods 0.000 title description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims description 30
- QJQZRLXDLORINA-UHFFFAOYSA-N 2-cyclohexylethanol Chemical compound OCCC1CCCCC1 QJQZRLXDLORINA-UHFFFAOYSA-N 0.000 claims description 28
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 28
- SJWKDXPDDXULJS-UHFFFAOYSA-N 6-ethyl-7-oxabicyclo[4.1.0]hepta-2,4-diene Chemical compound C1=CC=CC2(CC)C1O2 SJWKDXPDDXULJS-UHFFFAOYSA-N 0.000 claims description 18
- 239000007868 Raney catalyst Substances 0.000 claims description 16
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 12
- 239000005092 Ruthenium Substances 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- KJTLSVCANCCWHF-UHFFFAOYSA-N ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 10
- 229910052707 ruthenium Inorganic materials 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052803 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 description 8
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- WRMNZCZEMHIOCP-UHFFFAOYSA-N Phenethyl alcohol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N AI2O3 Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229960003563 Calcium Carbonate Drugs 0.000 description 2
- 229940067107 Phenylethyl Alcohol Drugs 0.000 description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 2
- 235000011613 Pinus brutia Nutrition 0.000 description 2
- 241000018646 Pinus brutia Species 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000875 corresponding Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
- C07C29/172—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with the obtention of a fully saturated alcohol
Definitions
- a process for the production of cyclohexylethyl alcohol in excellent yields which comprises introducing gradually 1,2-epoxyphenylethane into a suspension of a hydrogenation catalyst in an inert liquid medium at a temperature from 100 to 200 C. and under 50 to 300 atmospheres of hydrogen.
- the speed of introduction of the epoxyphenylethane should be controlled so that its proportion in the reaction vessel remains as low as possi- -le throughout the hydrogenation, thus avoiding as far as possible the formation of by-products.
- Suitable catalysts are those capable of facilitating the hydrogenation of the aromatic nucleus, for example, Raney nickel, Raney cobalt and supported ruthenium.
- the inert liquid medium should be a liquid inert to the conditions of the reaction, for example, methanol, ethanol or the hydrogenation product itself, i.e. cyclohexylethyl alcohol.
- the quantity of catalyst which should be employed depends upon its activity.
- supported ruthenium e.g. on calcium carbonate or alumina
- Raney nickel a quantity corresponding to 1% by weight may be employed, but it is preferable to use 540%.
- the nickel can be recovered and used again for a subsequent hydrogenation, if desired after the addition of a small quantity of fresh catalyst.
- the nickel may be alloyed with small quantities of activator metals, such as iron or chromium.
- the preferred hydrogenation temperatures range from 13 0 to 150 C. and the preferred pressures range from to 120 atmospheres.
- the catalyst After cooling and filtering oil the catalyst, the following are separated by distillation: 125 g. of ethylcyclohexane; 806 g. of cyclohexylethyl alcohol, boiling at 106 C. at 19 mm. Hg; and 20 g. of residues (consisting mainly of polymers of epoxyphenylethane).
- the yield of cyclohexylethyl alcohol is 75.5% based on the weight of the epoxyphenylethane.
- a process for the production of cyclohexylethyl alcohol which comprises gradually introducing 1,2-epoxyphenylethane into a suspension of a hydrogenation catalyst selected from the class consisting of Raney nickel, Raney cobalt and supported ruthenium in an inert liquid medium selected from the class consisting of methanol, ethanol and cyclohexylethyl alcohol, at a temperature from to 200 C. and under 50 to 300 atmospheres of hydrogen, the rate of addition of the 1,2-epoxyphenylethane being such that the proportion thereof in the suspension is maintained as low as possible throughout he hydrogenation.
- a hydrogenation catalyst selected from the class consisting of Raney nickel, Raney cobalt and supported ruthenium
- an inert liquid medium selected from the class consisting of methanol, ethanol and cyclohexylethyl alcohol
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
United States Patent 3,109,863 PRGCESE? FOR THE PREPARATION OF CYCLQHEXYLETHYL ALCOHGL Gilbert Bo and Philippe Perras, Lyon, France, assignors to Societe des Usines Chimi ues Rhone-Paulette, laris, rance, a French body corporate No Drawing. Filed lllay 23, 1960, Ser. No. 31,220 Claims priority, application France May 29, 1959 2 Claims. (Cl. 260-617) This invention relates to a new process for the preparation of cyclohexylethyl alcohol, which product and its esters are employed in perfumes.
It is known to prepare cyclohexylethyl alcohol by catalytic hydrogenation of phenylethyl alcohol which, in turn, can be obtained by catalytic hydrogenation of l,2epox phenylethane.
It follows that it would be advantageous to devise a method whereby cyclohexyiethyl alcohol could be obtained in one operation, that is by a single hydrogenation of 1,2-epoxyphenylethane. In the first phase, i.e. the reduction of an epoxy group to an hydroxy group, good yields are obtained by operating, for example, with Raney nickel at low temperatures. The second phase, i.e. hydrogenation of the aromatic nucleus, requires more vigorous operating conditions. Hydrogenation with 6% by weight of Raney nickel at 200 C. under 210 atmospheres pressure has previously been described and under these conditions the yield of cyclohexylethyl alcohol is only 53%. A quantitive yield has been obtained, however, by operating at low temperatures, i.e. -30 C., but in order to obtain this result it has been necessary to employ 150% by weight of Ran y nickel and a reaction period of 96 hours, which cond ions render the industrial application of this process impracticable. In view of the present state of knowledge in the art, therefore, there would seem a priori to be very little chance of exceeding a yield of 50% in an industrial process for the production of cyclohexylethyl alcohol by combining the aforesaid two hydrogenation phases. Moreover, it has been observed that if 1,2- epoxyphenylethane is hydrogenated at 130140 C. and under pressure in the presence of Raney nickel, two side reactions take place: polymerisation of the 1,2-epoxyphenylethane, and formation of ethylcyclohexane, both of which lower the yield of cyclohexylethyl alcohol.
According to the present invention there is provided a process for the production of cyclohexylethyl alcohol in excellent yields, which comprises introducing gradually 1,2-epoxyphenylethane into a suspension of a hydrogenation catalyst in an inert liquid medium at a temperature from 100 to 200 C. and under 50 to 300 atmospheres of hydrogen.
In order to obtain the higher yields in the foregoing process, it is desirable that the speed of introduction of the epoxyphenylethane should be controlled so that its proportion in the reaction vessel remains as low as possi- -le throughout the hydrogenation, thus avoiding as far as possible the formation of by-products.
Suitable catalysts are those capable of facilitating the hydrogenation of the aromatic nucleus, for example, Raney nickel, Raney cobalt and supported ruthenium. The inert liquid medium should be a liquid inert to the conditions of the reaction, for example, methanol, ethanol or the hydrogenation product itself, i.e. cyclohexylethyl alcohol. The quantity of catalyst which should be employed depends upon its activity. Thus, supported ruthenium (e.g. on calcium carbonate or alumina) can efl'ecddddfifiB Patented Nov. 5, i903 tively be employed in a proportion as small as 0.1% by weight of ruthenium calculated on the total quantity of 1,2-epoxyphenylethane introduced. In the case of Raney nickel, a quantity corresponding to 1% by weight may be employed, but it is preferable to use 540%. After the reaction, the nickel can be recovered and used again for a subsequent hydrogenation, if desired after the addition of a small quantity of fresh catalyst. The nickel may be alloyed with small quantities of activator metals, such as iron or chromium.
The preferred hydrogenation temperatures range from 13 0 to 150 C. and the preferred pressures range from to 120 atmospheres.
The following example will serve to illustrate the invention.
Example Into a 3.6 litre autoclave provided with a rotating-frame agitator are introduced 100 g. of Raney nickel in suspension in 200 ml. of ethanol. The air in the autoclave is replaced by nitrogen, and then by hydrogen, after which at 140 C. by slight heating.
1000 g. of the epoxyphenylethane is injected during 3 hours and the pressure drops from 100 to 80 atmospheres and is restored to 100 atmospheres 15 times. The hydrogenation is continued for a further 3 hours 40 minutes at 140 C. until the absorption of hydrogen ceases, but during this latter period the pressure drops from 100 to 80 atmospheres and is restored only 3 times and on the fourth drop settles at atmospheres.
After cooling and filtering oil the catalyst, the following are separated by distillation: 125 g. of ethylcyclohexane; 806 g. of cyclohexylethyl alcohol, boiling at 106 C. at 19 mm. Hg; and 20 g. of residues (consisting mainly of polymers of epoxyphenylethane). The yield of cyclohexylethyl alcohol is 75.5% based on the weight of the epoxyphenylethane.
If, instead of the epoxyphenylethane being progressively introduced over a period of 3 hours, the same quantity is introduced all at once, then, after hydrogenating for 8 hours 30 minutes (all other conditions being the same) the following are separated by distillation: 372 g. of ethylcyclohexane; 484 g. of cyclohexylethyl alcohol; and 67 g. of residues. The yield of cyclohexylethyl alcohol in this instance is therefore only 45% based on the weight of the epoxyphenylethane.
We claim:
1. A process for the production of cyclohexylethyl alcohol which comprises gradually introducing 1,2-epoxyphenylethane into a suspension of a hydrogenation catalyst selected from the class consisting of Raney nickel, Raney cobalt and supported ruthenium in an inert liquid medium selected from the class consisting of methanol, ethanol and cyclohexylethyl alcohol, at a temperature from to 200 C. and under 50 to 300 atmospheres of hydrogen, the rate of addition of the 1,2-epoxyphenylethane being such that the proportion thereof in the suspension is maintained as low as possible throughout he hydrogenation.
2. A process according to claim 1 wherein the hydro- 3 genation is effected at a temgerature from 130 to 150 C. OTHER REFERENCES and under 80 to 120 atmosPneres of hydrogen- Newman et 211.: Jour. Amer. Chem. 800., 71:3362- References Cited in the file of this patent 63 2 P g 222 Offi'fifi yn Pines et a1.: Jour. Chem. 800., vol. 77 (1955), pp.
UNITED STATE? PATENTS 5 5099 to 5102 4 pages). (Copy in Scientific Library.)
2,555,912 Arnold June 5, 1951
Claims (1)
1. A PROCESS FOR THE PRODUCTION OF CYCLOHEXLETHYL ALCOHOL WHICH COMPRISES GRADUALLY INTRODUCING 1,2-EPOXYPHENYLETHANE INTO A SUSPENSION OF A HYDROGENATION CATALYST SELECTED FROM THE CLASS CONSISTING OF RANEY NICKEL, RANEY COBALT AND SUPPORTED RUTHENIUM IN AN INERT LIQUID MEDIUM SELECTED FROM THE CLASS CONSISTING OF METHANOL, ETHANOL AND CYCLOHEXYLETHYL ALCOHOL, AT A TEMPERATURE FROM 100* TO 200*C. AND UNDER 50 TO 300 ATMOSPHERES OF HYDROGEN, THE RATE OF ADDITION OF THE 1,2-EPOXYPHENYLETHANE BEING SUCH THAT THE PROPORTION THEREOF IN THE SUSPENSION IS MAINTAINED AS LOW AS POSSIBLE THROUGHOUT THE HYDROGENATION.
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3109863A true US3109863A (en) | 1963-11-05 |
Family
ID=3452191
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US3109863D Expired - Lifetime US3109863A (en) | Psocess for the preparation of |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3109863A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0328116A1 (en) * | 1988-02-10 | 1989-08-16 | Kao Corporation | 2-(alkyl-cyclohexyl)-1-propanol, a process for preparing the same, and perfumery composition containing the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2555912A (en) * | 1948-08-18 | 1951-06-05 | Du Pont | Cyclohexyl-substituted alpha, omega glycols and process for preparing them |
-
0
- US US3109863D patent/US3109863A/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2555912A (en) * | 1948-08-18 | 1951-06-05 | Du Pont | Cyclohexyl-substituted alpha, omega glycols and process for preparing them |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0328116A1 (en) * | 1988-02-10 | 1989-08-16 | Kao Corporation | 2-(alkyl-cyclohexyl)-1-propanol, a process for preparing the same, and perfumery composition containing the same |
| US5104851A (en) * | 1988-02-10 | 1992-04-14 | Kao Corporation | 2-(alkyl-cyclo)-1-propanol, a process for preparing the same and perfumery composition containing the same |
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