US1838465A - Manufacture of esters of the borneols - Google Patents
Manufacture of esters of the borneols Download PDFInfo
- Publication number
- US1838465A US1838465A US412928A US41292829A US1838465A US 1838465 A US1838465 A US 1838465A US 412928 A US412928 A US 412928A US 41292829 A US41292829 A US 41292829A US 1838465 A US1838465 A US 1838465A
- Authority
- US
- United States
- Prior art keywords
- esters
- acid
- borneols
- camphene
- manufacture
- 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 15
- 150000001637 borneol derivatives Chemical class 0.000 title description 10
- 238000004519 manufacturing process Methods 0.000 title description 9
- CRPUJAZIXJMDBK-UHFFFAOYSA-N camphene Chemical compound C1CC2C(=C)C(C)(C)C1C2 CRPUJAZIXJMDBK-UHFFFAOYSA-N 0.000 description 20
- PXRCIOIWVGAZEP-UHFFFAOYSA-N Primaeres Camphenhydrat Natural products C1CC2C(O)(C)C(C)(C)C1C2 PXRCIOIWVGAZEP-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 10
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 description 10
- 229930006739 camphene Natural products 0.000 description 10
- ZYPYEBYNXWUCEA-UHFFFAOYSA-N camphenilone Natural products C1CC2C(=O)C(C)(C)C1C2 ZYPYEBYNXWUCEA-UHFFFAOYSA-N 0.000 description 10
- 229910052500 inorganic mineral Inorganic materials 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 239000011707 mineral Substances 0.000 description 6
- 150000004671 saturated fatty acids Chemical class 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000001117 sulphuric acid Substances 0.000 description 5
- 235000011149 sulphuric acid Nutrition 0.000 description 5
- 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 4
- 150000007513 acids Chemical class 0.000 description 4
- CKDOCTFBFTVPSN-UHFFFAOYSA-N borneol Natural products C1CC2(C)C(C)CC1C2(C)C CKDOCTFBFTVPSN-UHFFFAOYSA-N 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- DTGKSKDOIYIVQL-UHFFFAOYSA-N dl-isoborneol Natural products C1CC2(C)C(O)CC1C2(C)C DTGKSKDOIYIVQL-UHFFFAOYSA-N 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 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 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 235000019253 formic acid Nutrition 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229940116229 borneol Drugs 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002101 lytic effect Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C35/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C35/22—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system
- C07C35/23—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system with hydroxy on a condensed ring system having two rings
- C07C35/28—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system with hydroxy on a condensed ring system having two rings the condensed ring system containing seven carbon atoms
- C07C35/29—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system with hydroxy on a condensed ring system having two rings the condensed ring system containing seven carbon atoms being a (2.2.1) system
- C07C35/30—Borneol; Isoborneol
Definitions
- camphene can be transformed into isoborneol esters admixed with borneol esters by means of fatty acids, for example aceticacid, when using as catalysts 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 aceticacid
- 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 camphene and the esters. This aflects 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 mineral acids are caused to react at considerably lower temperatures than is usual.
- the attachment of the fatty acids takes place both more quickly and more completely when they are added in quantities which are in excess of that theoretically necessary.
- the same object may also be obtained by the use of highly concentrated fatty acids.
- the fatty acids employed can be recovered easily and quantitatively from the wash waters by evaporation and heating
- This invention is illustrated in the following example, the parts being by weight 136 parts of camphene are stirred for some time with 5 1 parts of 91% formic acid and the mixture cooled to below 0 C. 13 parts of 95% sulphuric acid are slowly added to the cold mixture while stirring briskly, care being taken to prevent a rise of temperature until the ester content no longer increases; the sulphuric acid is then allowed to settle and is separated from the ester mixture. An ester mixture of about 95% ester content is obtained. V
- esters of the borneols which consists in causing a saturated fatty acid to react upon camphene in the presence of sulphuric acid at a temperature of about 0 C.
- esters of the borneols which consists in causing a saturated fatty acid to reactupon camphene in the presence of a strong mineral acid at a the borneols which consists in causing a highly concentrated saturated fatty acid to react upon camphene in the presence of sulphigic acid at a temperature of about 4:.
- a process of manufacturing esters of the borneols which consists in causing a highly concentrated saturated fatty acid to react upon camphene in the presence of a strong mineral acid at a temperature of about 0 C.
- esters of the borneols which consists in causing an excess of a saturatedfatty acid to react upon camphene in the presence of sulphuric acid at a temperature of about 0 C.
- esters of the borneols which consistsin causing an excess of a saturated fatty acid to react upon camphene in the presence of a strong mineral acid at a temperature of about 0 C.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
' Patented Dec. 29, 1931 No Drawing. Original application .lytic acids.
UNITED STATES PATENT OFFICE KARL STEPI-IAN AND FRITZ ULFLEERS, OF BERLIN-OHARLOTTENBURG, GERMANY, AS-
SIGNORS TO SCKERI'NG-KAHLBAULI AKTIENG-ESELLSCHAFT,
OF BERLIN, GERMANY MANUFACTURE OF ESTERS OF THE BOR'NEOLS 1925. Divided and this application Our invention refers to the manufacture of esters of the borneols (isoborneol and borneol) from camphene in the presence of cata- This application is a division of our co-pending application Serial No. 98,625 filed March 30, 1.926, which matured into Patent No. 1,755,750, dated April 22, 1930.
It is known that camphene can be transformed into isoborneol esters admixed with borneol esters by means of fatty acids, for example aceticacid, when using as catalysts 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 camphene and the esters. This aflects 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 mineral acids are caused to react at considerably lower temperatures than is usual.
The attachment of the fatty acids takes place both more quickly and more completely when they are added in quantities which are in excess of that theoretically necessary. The same object may also be obtained by the use of highly concentrated fatty acids.
The reaction takes place extraordinarily quickly. I
The fatty acids employed can be recovered easily and quantitatively from the wash waters by evaporation and heating This invention is illustrated in the following example, the parts being by weight 136 parts of camphene are stirred for some time with 5 1 parts of 91% formic acid and the mixture cooled to below 0 C. 13 parts of 95% sulphuric acid are slowly added to the cold mixture while stirring briskly, care being taken to prevent a rise of temperature until the ester content no longer increases; the sulphuric acid is then allowed to settle and is separated from the ester mixture. An ester mixture of about 95% ester content is obtained. V
filed March 30, 1926, Serial No. 98,625, and in Germany April 11,
filed December 9, 1929. Serial No. 412,928. I
If the 91% formic acid is replaced by 99% formic acid 2 parts of sulphuric'acid will suffice toobtain the highest content in formate, and danger of sidereactions being caused by this acid is still further diminished.
We wish it to be understood that the production of said esters is not limited to the exact proportions and operations described, for obvious modifications will occur to a person skilled in the art. 7
We claim as our. invention:
1. A process of manufacturing esters of the borneols which consists in causing a saturated fatty acid to react upon camphene in the presence of sulphuric acid at a temperature of about 0 C.
2. A process of manufacturing esters of the borneols which consists in causing a saturated fatty acid to reactupon camphene in the presence of a strong mineral acid at a the borneols which consists in causing a highly concentrated saturated fatty acid to react upon camphene in the presence of sulphigic acid at a temperature of about 4:. A process of manufacturing esters of the borneols which consists in causing a highly concentrated saturated fatty acid to react upon camphene in the presence of a strong mineral acid at a temperature of about 0 C.
5. A process of manufacturing esters of the borneols which consists in causing an excess of a saturatedfatty acid to react upon camphene in the presence of sulphuric acid at a temperature of about 0 C.
6. A process of manufacturing esters of the borneols which consistsin causing an excess of a saturated fatty acid to react upon camphene in the presence of a strong mineral acid at a temperature of about 0 C.
' KARL STEPHAN. FRITZ ULFFERS.
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 (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US98625A US1755750A (en) | 1925-04-11 | 1926-03-30 | Manufacture of esters of the borneols |
| US412928A US1838465A (en) | 1926-03-30 | 1929-12-09 | Manufacture of esters of the borneols |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US1838465A true US1838465A (en) | 1931-12-29 |
Family
ID=26794939
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US412928A Expired - Lifetime US1838465A (en) | 1926-03-30 | 1929-12-09 | Manufacture of esters of the borneols |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US1838465A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2425173A (en) * | 1944-06-22 | 1947-08-05 | Resinous Prod & Chemical Co | Beta-norbornyl esters |
| US2426725A (en) * | 1944-06-09 | 1947-09-02 | Resinous Prod & Chemical Co | Esters of endoethylene-substituted cyclopentanols |
| US3860635A (en) * | 1969-10-06 | 1975-01-14 | Givaudan Corp | Substituted norbornyl and nortricyclyl derivatives and their use in perfumery |
-
1929
- 1929-12-09 US US412928A patent/US1838465A/en not_active Expired - Lifetime
Cited By (3)
| 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 |
| US2425173A (en) * | 1944-06-22 | 1947-08-05 | Resinous Prod & Chemical Co | Beta-norbornyl esters |
| US3860635A (en) * | 1969-10-06 | 1975-01-14 | Givaudan Corp | Substituted norbornyl and nortricyclyl derivatives and their use in perfumery |
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