US1838465A - Manufacture of esters of the borneols - Google Patents

Manufacture of esters of the borneols Download PDF

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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
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United States
Prior art keywords
esters
acid
borneols
camphene
manufacture
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Expired - Lifetime
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US412928A
Inventor
Stephan Karl
Ulffers Fritz
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Schering Kahlbaum AG
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Schering Kahlbaum AG
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Filing date
Publication date
Priority claimed from US98625A external-priority patent/US1755750A/en
Application filed by Schering Kahlbaum AG filed Critical Schering Kahlbaum AG
Priority to US412928A priority Critical patent/US1838465A/en
Application granted granted Critical
Publication of US1838465A publication Critical patent/US1838465A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • 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.

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.
US412928A 1926-03-30 1929-12-09 Manufacture of esters of the borneols Expired - Lifetime US1838465A (en)

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

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US1838465A true US1838465A (en) 1931-12-29

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Cited By (3)

* Cited by examiner, † Cited by third party
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

Cited By (3)

* Cited by examiner, † Cited by third party
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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