US937928A - Preparation of camphene. - Google Patents
Preparation of camphene. Download PDFInfo
- Publication number
- US937928A US937928A US31017506A US1906310175A US937928A US 937928 A US937928 A US 937928A US 31017506 A US31017506 A US 31017506A US 1906310175 A US1906310175 A US 1906310175A US 937928 A US937928 A US 937928A
- Authority
- US
- United States
- Prior art keywords
- camphene
- hydrochlorid
- peroxid
- preparation
- pinene
- 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
- CRPUJAZIXJMDBK-UHFFFAOYSA-N camphene Chemical compound C1CC2C(=C)C(C)(C)C1C2 CRPUJAZIXJMDBK-UHFFFAOYSA-N 0.000 title description 20
- PXRCIOIWVGAZEP-UHFFFAOYSA-N Primaeres Camphenhydrat Natural products C1CC2C(O)(C)C(C)(C)C1C2 PXRCIOIWVGAZEP-UHFFFAOYSA-N 0.000 title description 10
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 title description 10
- 229930006739 camphene Natural products 0.000 title description 10
- ZYPYEBYNXWUCEA-UHFFFAOYSA-N camphenilone Natural products C1CC2C(=O)C(C)(C)C1C2 ZYPYEBYNXWUCEA-UHFFFAOYSA-N 0.000 title description 10
- 238000002360 preparation method Methods 0.000 title description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 3
- 241000723346 Cinnamomum camphora Species 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- 229930008380 camphor Natural products 0.000 description 3
- 229960000846 camphor Drugs 0.000 description 3
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 229910001018 Cast iron Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- LUTSRLYCMSCGCS-BWOMAWGNSA-N [(3s,8r,9s,10r,13s)-10,13-dimethyl-17-oxo-1,2,3,4,7,8,9,11,12,16-decahydrocyclopenta[a]phenanthren-3-yl] acetate Chemical compound C([C@@H]12)C[C@]3(C)C(=O)CC=C3[C@@H]1CC=C1[C@]2(C)CC[C@H](OC(=O)C)C1 LUTSRLYCMSCGCS-BWOMAWGNSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- GRWFGVWFFZKLTI-YGPZHTELSA-N (5r)-4,6,6-trimethylbicyclo[3.1.1]hept-3-ene Chemical compound C1C2CC=C(C)[C@]1([H])C2(C)C GRWFGVWFFZKLTI-YGPZHTELSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000007514 turning Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/26—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms
- C07C1/30—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms by splitting-off the elements of hydrogen halide from a single molecule
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
- C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
- C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
- C07C13/39—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with a bicyclo ring system containing seven carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
- C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms
Definitions
- OLIVIER LOUIS ANDRE DUBOSC OF ROUEN, FRANCE, ASSIGNOR T0 STE. J. BASLER & CIR, OF BASEL, SWITZERLAND.
- This invention provides a'method of preparing camphene from hydrochlorid of pinene with the aid of metals and peroxids, the camphene thus obtained being oxidized to form camphor.
- the method which is the object of this application consists in the action at the same time upon the melted hydrochlorid of a metal susceptible of forming with the hydroehlorid, a chlorid, and a peroxid susceptible of forming water with the hydrogen.
- the reaction in iigures is as follows
- For two molecular proportions of hydrochlorid of pinene it is necessary to use one proportion of .metal and one of peroxid.
- the metals which have given "the best results are powdered zinc,- the finely pulverized turn-' ings of cast iron, copper and fine lead dust.
- the best operating'peroxids are the peroxid of barium and the dioxid of manganese.
- the camphene obtained is oxidized and transformed into camphor preferably by means of the chromic sulfuric liquor of Berthelot Spublished in La Uhz'mie Organz'gue of Be ml, Vol. II, page 5&0), to which l/1000 of vanadium chlorid is added.
- the liquor in question is a saturated solution of an alkaline sodic or potassic bichromate, to which is a ded a quantity 0 sulfuric acid such that the base of the bichromate is first combined to the state of sulfate, and so that the remaining sulfuric acid is in such pro- Specification of Letters Patent.
- the conditions of heat and pressure are the following:
- the reactions can occur as described only when the hydrochlorid of inene is in a state of fusion, or between 125 and 130 degrees centigrade. No pressure is necessary, the reaction taking place at nor mal atmospheric pressure.
- a reflux or circulating apparatus of any type may be used.
- the hydrochlorid of pinene is first mixed with the indicated quantities of pure metal in the form of a powder, and of the peroxid. If we use zinc powder and dioxid of manganese, the mixture is easily effected. If
- the oxidation of the camphene takes place at a temperature of 105 degrees Centigrade in a circulating apparatus, at ordinary pressures, but in a great quantity of water. Unless a great quantity of water is used, there is risk of explosion.
- the water should be at least twenty times the weight of the camphene.
- the end of the operation may be recognized by the fact that all the bichromate is transformed into sulfate. The coloration of the liquor changes from red to dark green, and this permits an empiric determlnation of the operation.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
} metallic zinc,
UNITED STATES PATENT OFFICE.
OLIVIER LOUIS ANDRE DUBOSC, OF ROUEN, FRANCE, ASSIGNOR T0 STE. J. BASLER & CIR, OF BASEL, SWITZERLAND.
PREPARATION OF CAMPI-IENE.
No Drawing.
T 0 all whom it may concern:
Be it known that I, OLIVIER Louis ANDRE DUBosc, a citizen of the Republic of France, residing at Rouen, Seine Infrieure, France, have invented certain new and useful Improvements in the Preparation of Camphene, of which the following is a specification.
This invention provides a'method of preparing camphene from hydrochlorid of pinene with the aid of metals and peroxids, the camphene thus obtained being oxidized to form camphor.
The transformation of hydrochlorid of pmene into camphene has been realized by me more simply than by previous methods proposed.
The method which is the object of this application consists in the action at the same time upon the melted hydrochlorid of a metal susceptible of forming with the hydroehlorid, a chlorid, and a peroxid susceptible of forming water with the hydrogen. The reaction in iigures is as follows For two molecular proportions of hydrochlorid of pinene, it is necessary to use one proportion of .metal and one of peroxid. Thus for two molecular proportions or 34.4 parts by weight of solid hydrochlorid of pinen'e, there are used 65 parts by weight of 169 parts by weight of the peroxid of barium; or 56 parts by weight of iron and 87 parts of peroxid of manganese. The metals which have given "the best results are powdered zinc,- the finely pulverized turn-' ings of cast iron, copper and fine lead dust. The best operating'peroxids are the peroxid of barium and the dioxid of manganese.
The camphene obtained is oxidized and transformed into camphor preferably by means of the chromic sulfuric liquor of Berthelot Spublished in La Uhz'mie Organz'gue of Be ml, Vol. II, page 5&0), to which l/1000 of vanadium chlorid is added. The liquor in question is a saturated solution of an alkaline sodic or potassic bichromate, to which is a ded a quantity 0 sulfuric acid such that the base of the bichromate is first combined to the state of sulfate, and so that the remaining sulfuric acid is in such pro- Specification of Letters Patent.
Patented Oct. 26, 1909.
Application filed. April 5, 1906. Serial No. 310,175.
portion as chromic acid set free in the formation of the sulfate, protoxid of chromium, thus generating oxygen, thus,-
The conditions of heat and pressure are the following: The reactions can occur as described only when the hydrochlorid of inene is in a state of fusion, or between 125 and 130 degrees centigrade. No pressure is necessary, the reaction taking place at nor mal atmospheric pressure. A reflux or circulating apparatus of any type may be used. The hydrochlorid of pinene is first mixed with the indicated quantities of pure metal in the form of a powder, and of the peroxid. If we use zinc powder and dioxid of manganese, the mixture is easily effected. If
.turnings of cast iron are used, they must be finely pulverized. l/Vith iron one can heat the mass without special care up to the point of fusion of the hydrochlorid. W ith zinc or aluminum the heating must be very cautious, the reaction being very strong and quick; so much so that practically iron is preferable. The operation continues for 24 to 36 hours. The end of the operation is indicated by applying to nitrate of silver the liquid part of the mass. If there remains any hydrochlorid of pinene not transformed, there is formation of a cloudy precipitate of silver. The camphene is separated from the chlorid of zinc or iron and from the sediment of barium or of manganese by distillation in a current of vapor.
The oxidation of the camphene takes place at a temperature of 105 degrees Centigrade in a circulating apparatus, at ordinary pressures, but in a great quantity of water. Unless a great quantity of water is used, there is risk of explosion. The water should be at least twenty times the weight of the camphene. In order to avoid superoxidations it is well to add the chromic liquor in successive small parts. The end of the operation may be recognized by the fact that all the bichromate is transformed into sulfate. The coloration of the liquor changes from red to dark green, and this permits an empiric determlnation of the operation. The
to be able to form with the camphor formed is carried ofi by a current In witness whereof Ihave hereunto signed of vapor in order. to separate it from the sulmy name this 27th day of March 1906, in the 19 fate of chrome. presence of two subscribing witnesses. What I claim is The process which consistsin transform- OLIVER LOUIS ANDRE DUBOSG' ing hydrochlorid of pinene into camphene Witnesses:
through the cooperatlng action of a metal HANSON C. (30x12,
and a peroxid on the melted hydrochlorid. GABRIEL Bmmno.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US31017506A US937928A (en) | 1906-04-05 | 1906-04-05 | Preparation of camphene. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US31017506A US937928A (en) | 1906-04-05 | 1906-04-05 | Preparation of camphene. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US937928A true US937928A (en) | 1909-10-26 |
Family
ID=3006348
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US31017506A Expired - Lifetime US937928A (en) | 1906-04-05 | 1906-04-05 | Preparation of camphene. |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US937928A (en) |
-
1906
- 1906-04-05 US US31017506A patent/US937928A/en not_active Expired - Lifetime
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