US1755750A - Manufacture of esters of the borneols - Google Patents
Manufacture of esters of the borneols Download PDFInfo
- Publication number
- US1755750A US1755750A US98625A US9862526A US1755750A US 1755750 A US1755750 A US 1755750A US 98625 A US98625 A US 98625A US 9862526 A US9862526 A US 9862526A US 1755750 A US1755750 A US 1755750A
- Authority
- US
- United States
- Prior art keywords
- esters
- borneols
- acid
- manufacture
- acids
- 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
- 150000002148 esters Chemical class 0.000 title description 8
- 150000001637 borneol derivatives Chemical class 0.000 title description 6
- 238000004519 manufacturing process Methods 0.000 title description 5
- 239000002253 acid Substances 0.000 description 7
- CRPUJAZIXJMDBK-UHFFFAOYSA-N camphene Chemical compound C1CC2C(=C)C(C)(C)C1C2 CRPUJAZIXJMDBK-UHFFFAOYSA-N 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 5
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical compound C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- PXRCIOIWVGAZEP-UHFFFAOYSA-N Primaeres Camphenhydrat Natural products C1CC2C(O)(C)C(C)(C)C1C2 PXRCIOIWVGAZEP-UHFFFAOYSA-N 0.000 description 3
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 description 3
- CKDOCTFBFTVPSN-UHFFFAOYSA-N borneol Natural products C1CC2(C)C(C)CC1C2(C)C CKDOCTFBFTVPSN-UHFFFAOYSA-N 0.000 description 3
- 229930006739 camphene Natural products 0.000 description 3
- ZYPYEBYNXWUCEA-UHFFFAOYSA-N camphenilone Natural products C1CC2C(=O)C(C)(C)C1C2 ZYPYEBYNXWUCEA-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- DTGKSKDOIYIVQL-UHFFFAOYSA-N dl-isoborneol Natural products C1CC2(C)C(O)CC1C2(C)C DTGKSKDOIYIVQL-UHFFFAOYSA-N 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DTGKSKDOIYIVQL-MRTMQBJTSA-N Isoborneol Natural products C1C[C@@]2(C)[C@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-MRTMQBJTSA-N 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229940005657 pyrophosphoric acid Drugs 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- REPVLJRCJUVQFA-UHFFFAOYSA-N (-)-isopinocampheol Natural products C1C(O)C(C)C2C(C)(C)C1C2 REPVLJRCJUVQFA-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229940116229 borneol Drugs 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- RDWUNORUTVEHJF-KKZNHRDASA-N isobornyl formate Chemical compound C1C[C@@]2(C)[C@H](OC=O)C[C@@H]1C2(C)C RDWUNORUTVEHJF-KKZNHRDASA-N 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G5/00—Floral handling
- A01G5/06—Devices for preserving flowers
Definitions
- Our invention refers to the manufacture of esters of the borneols (i-soborneol and borneol) from camphene in the presence of catalytic acids.
- camphene can be transfcrmed into isoborneol esters admixed with borneol esters by means of fatty acids, for example acetic acid, when using as catalysis strong mineral acids (for example sulphuric acid, nitric acid or hydrochloric acid) and that the corresponding alcohols can be obtained therefrom by saponification.
- fatty acids for example acetic acid
- catalysis strong mineral acids for example sulphuric acid, nitric acid or hydrochloric acid
- the esters obtained are, however, not pure because strong mineral acids in secondary reaction attack both the camphcne and the esters. This affects both the purity and the yield of isoborneol;
- Esters of substantially greater purity and from them isoborneol of substantially higher melting point can be obtained when according to this invention there is employed, in place of mineral acids, acids of less acidity, such as pyrophosphoric acid.
- the attachment of the fatty acids takes place both more quickly and more completely when they are added in'q'uantities which are in excess of that theoreticallynecessary.
- the same object may also be obtained by the use of highly concentrated fatty acids.
- the fatty acids employed can be recovered easil and quantitatively from the wash waters y evaporation and heating.
- the invention is illustrated in the following example, the parts being by weight 10 parts of camphene are well stirred with 20 parts of 95% formic acid and 2 arts of pyro hosphorio acid and heated to a out 60 C. he temperature rises of itself to. about 70 (1, care being taken that this temperature is not exceeded. The reaction is completed in a few minutes. The excess of formic acid is then distilled off in vacuo and the product of the reaction washed with water until neutral. The pyrosphosphoric acid can easily be recovered from the wash water by evaporation.
- the ester has a saponification value of about 308, corresponding to 100% isoborneol formate and a specific gravity of 1.010 at 20 C.
- the product obtained has the formula t' .,H .().()(H.
- esters of the borneols which consists in heating highly concentrated fatty acid withcamphenein the presence of pyrophosphoric acid at about 60 C. and taking care that a temperature of C. is not exceeded, distilling off the excess of the fatty acid and washing the product of the re- 7 action.
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Environmental Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Fats And Perfumes (AREA)
Description
Patented Apr. 22, 1930 UNITED STATES PATENT OFFICE KARL STEPHAN AND FRITZ ULFFERS, F BERLIN-CHARLOTTENBURG, GERMANY, AS-
SIGNOBS TO SCHERING-KAHLBAUM AK TIENGESELLSCHALFT, OF BERLIN, GERMANY MANUFACTURE OF ESTERS OE THE BORNEOLS No Drawing. Application filed March 30, 1926, Serial No. 98,625, and in Germany April 11, 1925.
Our invention refers to the manufacture of esters of the borneols (i-soborneol and borneol) from camphene in the presence of catalytic acids.
It is known that camphene can be transfcrmed into isoborneol esters admixed with borneol esters by means of fatty acids, for example acetic acid, when using as catalysis strong mineral acids (for example sulphuric acid, nitric acid or hydrochloric acid) and that the corresponding alcohols can be obtained therefrom by saponification. The esters obtained are, however, not pure because strong mineral acids in secondary reaction attack both the camphcne and the esters. This affects both the purity and the yield of isoborneol;
Esters of substantially greater purity and from them isoborneol of substantially higher melting point can be obtained when according to this invention there is employed, in place of mineral acids, acids of less acidity, such as pyrophosphoric acid. y 7
The attachment of the fatty acids takes place both more quickly and more completely when they are added in'q'uantities which are in excess of that theoreticallynecessary. The same object may also be obtained by the use of highly concentrated fatty acids.
The reaction takes place extraordinarily quickly.
The fatty acids employedcan be recovered easil and quantitatively from the wash waters y evaporation and heating.
The invention is illustrated in the following example, the parts being by weight 10 parts of camphene are well stirred with 20 parts of 95% formic acid and 2 arts of pyro hosphorio acid and heated to a out 60 C. he temperature rises of itself to. about 70 (1, care being taken that this temperature is not exceeded. The reaction is completed in a few minutes. The excess of formic acid is then distilled off in vacuo and the product of the reaction washed with water until neutral. The pyrosphosphoric acid can easily be recovered from the wash water by evaporation. The ester has a saponification value of about 308, corresponding to 100% isoborneol formate and a specific gravity of 1.010 at 20 C.
The product obtained has the formula t' .,H .().()(H.
lVe wish it to be understood that the production of the said esters is not limited to the 2. Process of manufacturing esters of the borneols which consists in heating highly concentrated fatty acid withcamphenein the presence of pyrophosphoric acid at about 60 C. and taking care that a temperature of C. is not exceeded, distilling off the excess of the fatty acid and washing the product of the re- 7 action.
In testimony whereof we aflix our signa tures.
KARL STEPHAN. FRITZ ULEFERS.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US412928A US1838465A (en) | 1926-03-30 | 1929-12-09 | Manufacture of esters of the borneols |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1755750X | 1925-04-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US1755750A true US1755750A (en) | 1930-04-22 |
Family
ID=7741981
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US98625A Expired - Lifetime US1755750A (en) | 1925-04-11 | 1926-03-30 | Manufacture of esters of the borneols |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US1755750A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2426725A (en) * | 1944-06-09 | 1947-09-02 | Resinous Prod & Chemical Co | Esters of endoethylene-substituted cyclopentanols |
-
1926
- 1926-03-30 US US98625A patent/US1755750A/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2426725A (en) * | 1944-06-09 | 1947-09-02 | Resinous Prod & Chemical Co | Esters of endoethylene-substituted cyclopentanols |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US2229897A (en) | Method of preparing alpha hydroxy carboxylic acids | |
| US2569440A (en) | Separation of isophthalic acid from terephthalic acid by noncatalytic esterification | |
| US1755750A (en) | Manufacture of esters of the borneols | |
| US2226645A (en) | Manufacture of methacrylic acid and esters thereof | |
| US2476052A (en) | Ester exchange reaction | |
| US1838465A (en) | Manufacture of esters of the borneols | |
| US2453105A (en) | Preparation of hydroxy aromatic carboxylic acids | |
| US2742495A (en) | Esterification of aconitic acid salts | |
| US2079403A (en) | Reduction of acyloins | |
| US3321509A (en) | Preparation of alkyl esters of parahydroxybenzoic acid | |
| US2340294A (en) | Cyclic alcohol and process of preparing | |
| US1961623A (en) | Oxidation of alicyclic alcohols and ketones | |
| US2101821A (en) | Manufacture of unsaturated or ganic compounds | |
| US2305663A (en) | Method for preparing methacrylic acid esters | |
| US2433323A (en) | Production of useful chemicals from crude formic acid distillate | |
| US2373583A (en) | Conversion of methyl formate to formic acid | |
| US2089127A (en) | Manufacture of glycerol monolactate | |
| US2212509A (en) | Method of esterifying phenolic hydroxyls | |
| US2415000A (en) | Production of esters | |
| US2116347A (en) | Alpha-salicylo-aliphatic acid esters | |
| US2349770A (en) | Process for the production of tetrasubstituted ethylenes | |
| US2733266A (en) | mckinnis | |
| US2063162A (en) | Production of cyclic terpene alcohols | |
| US2196580A (en) | Production of useful chemicals from isomeric mono - nitro - ortho - dichlorobenzene mixtures | |
| US1420399A (en) | Process of making acetyl isoborneol |