US876137A - Process of making camphene. - Google Patents
Process of making camphene. Download PDFInfo
- Publication number
- US876137A US876137A US33437006A US1906334370A US876137A US 876137 A US876137 A US 876137A US 33437006 A US33437006 A US 33437006A US 1906334370 A US1906334370 A US 1906334370A US 876137 A US876137 A US 876137A
- Authority
- US
- United States
- Prior art keywords
- camphene
- hydrochlorid
- salts
- steam
- higher fatty
- 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 36
- PXRCIOIWVGAZEP-UHFFFAOYSA-N Primaeres Camphenhydrat Natural products C1CC2C(O)(C)C(C)(C)C1C2 PXRCIOIWVGAZEP-UHFFFAOYSA-N 0.000 title description 18
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 title description 18
- 229930006739 camphene Natural products 0.000 title description 18
- ZYPYEBYNXWUCEA-UHFFFAOYSA-N camphenilone Natural products C1CC2C(=O)C(C)(C)C1C2 ZYPYEBYNXWUCEA-UHFFFAOYSA-N 0.000 title description 18
- 238000000034 method Methods 0.000 title description 13
- 150000003839 salts Chemical class 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- 239000000194 fatty acid Substances 0.000 description 10
- 235000014113 dietary fatty acids Nutrition 0.000 description 9
- 229930195729 fatty acid Natural products 0.000 description 9
- 150000004665 fatty acids Chemical class 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 235000021355 Stearic acid Nutrition 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- IPCSVZSSVZVIGE-UHFFFAOYSA-N palmitic acid group Chemical group C(CCCCCCCCCCCCCCC)(=O)O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- SURLGNKAQXKNSP-DBLYXWCISA-N chlorin Chemical compound C\1=C/2\N/C(=C\C3=N/C(=C\C=4NC(/C=C\5/C=CC/1=N/5)=CC=4)/C=C3)/CC\2 SURLGNKAQXKNSP-DBLYXWCISA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229940049964 oleate Drugs 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 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 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229930008380 camphor Natural products 0.000 description 1
- 229960000846 camphor Drugs 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical class [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 description 1
- 230000037213 diet Effects 0.000 description 1
- 235000005911 diet Nutrition 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- -1 fatty acid salt Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- QZWHQSRWOYUNFT-UHFFFAOYSA-L hexadecanoate;lead(2+) Chemical compound [Pb+2].CCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCC([O-])=O QZWHQSRWOYUNFT-UHFFFAOYSA-L 0.000 description 1
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- XYXLRVFDLJOZJC-CVBJKYQLSA-L manganese(2+);(z)-octadec-9-enoate Chemical compound [Mn+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O XYXLRVFDLJOZJC-CVBJKYQLSA-L 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 150000002730 mercury Chemical class 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 150000002889 oleic acids Chemical class 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 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
- GIE OF BASE'L, SWITZERLAND, A FIRM.
- the present invention relates to the manufacture of camphene used for the manufacture of camphor.
- One of the oldest methods for obtaining camphene free from chlorin consists in heating pinene hydrochlorid with a large excess of powdered sodium stearate or benzoate for 40 hours at 200.C.
- the chief objections to this process are the large excess of soap and the prolonged heating.
- inene hydrochlorid is heated with an easily usible anhydrous metal salt of a higher fatty acid for some hours at about 200 C. It is thus converted into camphene without using an autoclave and in a considerably shorter time than is possible according to either of the aforesaid processes.
- suitable easily fusible salts of higher fatty acids may be named the co per salts, manganese salts, lead salts an. mercury salts.
- the vessel In order that theoperation may be conducted in a vessel without pressure, the vessel is provided with a column which serves as a reflux condenser and is so-large that the temperature within the mass in which the Specification of Letters Patent. Application filed September 13 1906. Serial No; 334.870.
- reaction is proceeding can riseto 200 C.
- a part of the camphene may distil during the process, but the bulk of it is distilled in steam when the reaction is at an end.
- Example I 75 parts (I litharge are dissolved with aid of heat in 200 parts of stearic acid and the heating is continued until the salt is anhydrous.
- 100 parts ofpinene hydrochlorid are introduced and the solution is heated to 195 200 C. for 4 hours in a vessel having a column as a reflux condenser.
- Lead stearochlorid separates at first and gradually reacts with the pinene hydrochlorid with formation of lead chlorid. The mass is allowed to cool to about 140 C. and the camphene is distilled in steam. The stearic acid is regenerated and is used again in the process.
- reaction is analogous when lead oleate is used, but in this case lead oleochlorid does not separate, but only lead chlorid. Lead palmitate behaves similarly. It is not necessary, however, to use the said acids in the pure state; a mixture of acids such as is obtained by saponifying oils or fats may be used.
- Example 11 A mlxture ofoleic and stearic acids, which may also contain palmitic acid, is converted into 00 per salts in the known manner by means of the calculated proportion of freshly precipitated copper carbonate or cupric oxids. 300 parts of the dried copper salts are heated for some 5 hours at 195- 200 C. with 100 parts of pinene hydrochlorid. From time to time a sample of the oil condensed in the reflux condenser is removed and tested to see if it is free from chlorin. The cam hene is distilled in steam and the fatty aci s recovered. When the fatty acid salt is not so easily melted as those mentioned in the previous examples, a substance which will aid the liquefaction, such as diethylanilin, may be added.
- a substance which will aid the liquefaction such as diethylanilin
- Example III Manganese oleate is made by adding manganese sulfate to anoleic acid soa 240 parts of this oleate are heated with 100 parts of inene hydrochlorid and 100 arts of diet iylanilin at 195200 C. for 8 hours. When the reaction is complete the mixture is distilled in steam and the diethylanilin separated from the camphene in the distillate by addition of acid.
- camphene consisting of heating piene hydrochlorid with an easily fusible, anhydrous metal salt of a higher fatty acid, and distilling the mixture of the reaction in steam in order to separate the camphene.
- camphene consisting of heating pinene hydrochlorid with an easily fusible anhydrous metal salt of a higher fatty acid for some hours at about 200 C. and distilling the mixture of the reaction in steam in order to separate the camphene.
- camphene consisting of heating pinene hydrochlorid with an easily fusible anhydrous metal salt of a higher-fatty acid for some hours at about 200 C. in a vessel provided 'With a column serving as a reflux condenser and distilling the mixture of the reaction in steam in order to separate the camphene.
- camphene consisting of heating pinene hydrochlorid with an easily fusible, anhydrous metal salt of a higher fatty acid in presence of diethylanilin at about 200 C. distilling the mixture of the reaction in steam, in order to separate from it the camphene and the diethylanilin and finally adding an acid to the distillate in order to separate the camphene from the diethylanilin.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
' acids as solvents,
UNITED STATES PATENT OFFICE.
AUGUSTUS BISOHLER. AND ANTON BASELLI, OF BASEL, SWITZERLAND, ASSIGNORS, BY MESNE ASSIGNMENTS, TO I. BASLER &
GIE., OF BASE'L, SWITZERLAND, A FIRM.
PROCESS MAKING CAMPHENE.
T 0 all whom it may concern:
Be it known that we, AUGUSTUS BISCH- LER, doctor of philosophy and chemist, a subjectof the Emperor of Russia, and resident of Basel, Switzerland, and ANTON BASELLI, doctor of philosophy and chemist, a subject of the Emperor of Austria-Hungary, and resident of Basel, Switzerland, have invented a new and useful Process for the Manufacture of Camphene, of which the following is a full, clear, and exact specification.
The present invention relates to the manufacture of camphene used for the manufacture of camphor. One of the oldest methods for obtaining camphene free from chlorin consists in heating pinene hydrochlorid with a large excess of powdered sodium stearate or benzoate for 40 hours at 200.C. The chief objections to this process are the large excess of soap and the prolonged heating.
The process described in the British specification No. 26618 of 1901, namely heating pinene hydrochlorid with bases in aqueous solution as for instance soda 1 e or potash lye, in presence of alkali salts 0 higher fatty for 20 hours at 210220 Q. iln an autoclave, is said to be more economica The alkali salts of higher fatty acids do not melt easily when they are anhydrous. On the other hand numerous salts of higher fatty acids are known, which melt easily even when anhydrous. By higher fatty acids we mean palmitic, 'stearic and oleic acids, and as an example of the easily melted salts just referred to, we would refer to salts of either of these acids with heavy metals.
According to the present invention inene hydrochlorid is heated with an easily usible anhydrous metal salt of a higher fatty acid for some hours at about 200 C. It is thus converted into camphene without using an autoclave and in a considerably shorter time than is possible according to either of the aforesaid processes.
As suitable easily fusible salts of higher fatty acids, may be named the co per salts, manganese salts, lead salts an. mercury salts.
In order that theoperation may be conducted in a vessel without pressure, the vessel is provided with a column which serves as a reflux condenser and is so-large that the temperature within the mass in which the Specification of Letters Patent. Application filed September 13 1906. Serial No; 334.870.
Patented Jan. 7, 1908.
reaction is proceeding can riseto 200 C. A part of the camphene may distil during the process, but the bulk of it is distilled in steam when the reaction is at an end.
Example I: 75 parts (I litharge are dissolved with aid of heat in 200 parts of stearic acid and the heating is continued until the salt is anhydrous. Into this lead stearate 100 parts ofpinene hydrochlorid are introduced and the solution is heated to 195 200 C. for 4 hours in a vessel having a column as a reflux condenser. Lead stearochlorid separates at first and gradually reacts with the pinene hydrochlorid with formation of lead chlorid. The mass is allowed to cool to about 140 C. and the camphene is distilled in steam. The stearic acid is regenerated and is used again in the process. The reaction is analogous when lead oleate is used, but in this case lead oleochlorid does not separate, but only lead chlorid. Lead palmitate behaves similarly. It is not necessary, however, to use the said acids in the pure state; a mixture of acids such as is obtained by saponifying oils or fats may be used.
Example 11 A mlxture ofoleic and stearic acids, which may also contain palmitic acid, is converted into 00 per salts in the known manner by means of the calculated proportion of freshly precipitated copper carbonate or cupric oxids. 300 parts of the dried copper salts are heated for some 5 hours at 195- 200 C. with 100 parts of pinene hydrochlorid. From time to time a sample of the oil condensed in the reflux condenser is removed and tested to see if it is free from chlorin. The cam hene is distilled in steam and the fatty aci s recovered. When the fatty acid salt is not so easily melted as those mentioned in the previous examples, a substance which will aid the liquefaction, such as diethylanilin, may be added.
Example III: Manganese oleate is made by adding manganese sulfate to anoleic acid soa 240 parts of this oleate are heated with 100 parts of inene hydrochlorid and 100 arts of diet iylanilin at 195200 C. for 8 hours. When the reaction is complete the mixture is distilled in steam and the diethylanilin separated from the camphene in the distillate by addition of acid.
What we'claim is:
1. The described process for the manufacture of camphene consisting of heating piene hydrochlorid with an easily fusible, anhydrous metal salt of a higher fatty acid, and distilling the mixture of the reaction in steam in order to separate the camphene.
2. The described process for the manufacture of camphene consisting of heating pinene hydrochlorid with an easily fusible anhydrous metal salt of a higher fatty acid for some hours at about 200 C. and distilling the mixture of the reaction in steam in order to separate the camphene.
3. The described process for the manufacture of camphene consisting of heating pinene hydrochlorid with an easily fusible anhydrous metal salt of a higher-fatty acid for some hours at about 200 C. in a vessel provided 'With a column serving as a reflux condenser and distilling the mixture of the reaction in steam in order to separate the camphene. A
4 The described process for the manufacture of camphene consisting of heating pinene hydrochlorid with an easily fusible, anhydrous metal salt of a higher fatty acid in presence of diethylanilin at about 200 C. distilling the mixture of the reaction in steam, in order to separate from it the camphene and the diethylanilin and finally adding an acid to the distillate in order to separate the camphene from the diethylanilin.
In witness whereof We have hereunto signed our names this 1st day of September,
AUGUSTUS BISCHLER. ANTON BASELLI.
Witnesses GEO. GIFFORD. AMAND BITTER.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US33437006A US876137A (en) | 1906-09-13 | 1906-09-13 | Process of making camphene. |
| US368612A US876310A (en) | 1906-09-13 | 1907-04-17 | Process for the manufacture of isobornyl oxalates from camphene. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US33437006A US876137A (en) | 1906-09-13 | 1906-09-13 | Process of making camphene. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US876137A true US876137A (en) | 1908-01-07 |
Family
ID=2944581
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US33437006A Expired - Lifetime US876137A (en) | 1906-09-13 | 1906-09-13 | Process of making camphene. |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US876137A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2490973A (en) * | 1946-10-10 | 1949-12-13 | Standard Oil Co | Dehydrohalogenation |
-
1906
- 1906-09-13 US US33437006A patent/US876137A/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2490973A (en) * | 1946-10-10 | 1949-12-13 | Standard Oil Co | Dehydrohalogenation |
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