US1836287A - Process for obtaining bornyl and isobornyl esters - Google Patents
Process for obtaining bornyl and isobornyl esters Download PDFInfo
- Publication number
- US1836287A US1836287A US300949A US30094928A US1836287A US 1836287 A US1836287 A US 1836287A US 300949 A US300949 A US 300949A US 30094928 A US30094928 A US 30094928A US 1836287 A US1836287 A US 1836287A
- Authority
- US
- United States
- Prior art keywords
- acid
- bornyl
- obtaining
- anhydride
- aliphatic monocarboxylic
- 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
- 238000000034 method Methods 0.000 title description 14
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 title description 12
- -1 aliphatic monocarboxylic acid Chemical class 0.000 description 10
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 9
- 239000004327 boric acid Substances 0.000 description 9
- 150000008065 acid anhydrides Chemical class 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 150000008064 anhydrides Chemical class 0.000 description 5
- 230000032050 esterification Effects 0.000 description 5
- 238000005886 esterification reaction Methods 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- WWJLCYHYLZZXBE-UHFFFAOYSA-N 5-chloro-1,3-dihydroindol-2-one Chemical compound ClC1=CC=C2NC(=O)CC2=C1 WWJLCYHYLZZXBE-UHFFFAOYSA-N 0.000 description 2
- KGEKLUUHTZCSIP-HOSYDEDBSA-N Bornyl acetate Natural products C1C[C@]2(C)[C@H](OC(=O)C)C[C@H]1C2(C)C KGEKLUUHTZCSIP-HOSYDEDBSA-N 0.000 description 2
- KGEKLUUHTZCSIP-UHFFFAOYSA-N Isobornyl acetate Natural products C1CC2(C)C(OC(=O)C)CC1C2(C)C KGEKLUUHTZCSIP-UHFFFAOYSA-N 0.000 description 2
- 239000001940 [(1R,4S,6R)-1,7,7-trimethyl-6-bicyclo[2.2.1]heptanyl] acetate Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000005382 boronyl group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- pinene or oils containing pinene are treated with mixed acid anhydride of boric acid and another acid, for instance acetoboric anhydride, the latter either in the finished state or so to be formed in situ, alone, i. e. without addition of the organic acid to be esterified, for instance acetic acid.
- the quantity of the mixed acid anhydride of boric and other acid can vary within relatively wide. limits and this preesterification serves chiefly for the purpose of obtaining as high a temperature as possible, for the purpose of converting the condensation agent i. e. the mixed anhydride of boric and other acid, into the condition which is most effective for the subsequent esterification.
- the process is interrupted and it is found that the yield of ester, owing to the separate method of procedure is on an average 1 520% higher than if the free organic acid were introduced into the process from the outset.
- the technical effect of the present process as compared with the known process consists broadly in obtaining higher yields of ester. For instance the final outputs from 136 kgs. pinene plus 30 kgs. acetoboric anhydride and 100 kgs. glacial acetic, acid according to the known process, that is to say in one single operation amount on an average to 60% P T OFFICE.
- reaction product is treated with water, in which case the acetoboric anhydride decomposes into boric acid and acetic acid, while the bornyl and isobornyl acetate formed separates at the top as an oily layer.
- Purification is then carried out in a known manner either by steam distillation or vacuum distillation, and then saponification with alcoholic alkali, a mixture of pure bornyl and isobornyl acetate of melting point 196199 0. being formed.
- esterification is effected in two stages the first stage being effected With the mixed acid anhydride of boric acid and an aliphatic monocarboxylic acid, the esteri- .fication being thereupon completed by the addition of free aliphatic monocarboxylic acid.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
, In this way the subsequent esterification is 1 Patented Dec. 15, 1931 UNITED STATES LUDWIG SCHMIDT, or HAMBURG-BERGEDORF, GERMANY, ASSIGNOR TO SOGIETE ALSAOIENNE DE rnonorrs GHIMIQUES, or PARIS, FRANCE, A rnnncn COMPANY PROCESS FOR OBTAINING BORNYL AND ISOBORNYL ESTERS No Drawing. Application filed August 20, 1928, Serial No. 300,949, and in France February 18, 1928.
It is known that bornyl and isobornyl esters are obtained with satisfactory technical outputs by heating at an ordinary pressure pinene or oils containing pinene with organic acids with the addition of mixed acig anhydride of boric acid and another aci According to the present application it has been found that in this operation the ester content can be substantially increased by carrying out the condensation in two separate processes side by side, as follows:
(1) First of all, pinene or oils containing pinene are treated with mixed acid anhydride of boric acid and another acid, for instance acetoboric anhydride, the latter either in the finished state or so to be formed in situ, alone, i. e. without addition of the organic acid to be esterified, for instance acetic acid. The quantity of the mixed acid anhydride of boric and other acid can vary within relatively wide. limits and this preesterification serves chiefly for the purpose of obtaining as high a temperature as possible, for the purpose of converting the condensation agent i. e. the mixed anhydride of boric and other acid, into the condition which is most effective for the subsequent esterification.
(2) When the desired maximum temperature is obtained, there then takes place in the second operation the addition of the free organic acid, preferably in a measured excess, to the reaction mixture, which addition takes place slowly while continuously heating.
cifected with the continuous action of the condensing agent, until a maximum ester content is reached. When this is reached,
the process is interrupted and it is found that the yield of ester, owing to the separate method of procedure is on an average 1 520% higher than if the free organic acid were introduced into the process from the outset.
This fact was not to be foreseen. In this case too boronyl and isoboronyl esters are obtained exclusively, without any formation of resin.
The technical effect of the present process as compared with the known process consists broadly in obtaining higher yields of ester. For instance the final outputs from 136 kgs. pinene plus 30 kgs. acetoboric anhydride and 100 kgs. glacial acetic, acid according to the known process, that is to say in one single operation amount on an average to 60% P T OFFICE.
at the end to 60-65%. The reactionproduct is treated with water, in which case the acetoboric anhydride decomposes into boric acid and acetic acid, while the bornyl and isobornyl acetate formed separates at the top as an oily layer. Purification is then carried out in a known manner either by steam distillation or vacuum distillation, and then saponification with alcoholic alkali, a mixture of pure bornyl and isobornyl acetate of melting point 196199 0. being formed.
Having now described my invention, what I claim as new and desire to secure by Letters Patent is 1. In the process of obtaining bornyl and isobornyl esters by heating at an ordinary pressure pinene with an aliphatic monocarboxylic acid with the addition of mixed acid anhydride .of boric acid and an aliphatic monocarboxylic acid, the feature that the esterification is effected in two stages the first stage being efi'ected with the mixed acid anhydride of boric acid and an aliphatic monocarboxylic acid, the esterifi-cation being thereupon completed by the addition of free aliphatic monocarboxylic acid.
2. In the process of obtaining bornyl and isobornyl' esters by heating at an ordinary pressure oils containing pinene with an aliphatic monocarboxylic acid with the addition of mixed acid anhydride of boric acid and an aliphatic monocarboxylic acid, the
feature that the esterification is effected in two stages the first stage being effected With the mixed acid anhydride of boric acid and an aliphatic monocarboxylic acid, the esteri- .fication being thereupon completed by the addition of free aliphatic monocarboxylic acid.
3. The process as claimed in claim 1 in which the mixed acid anhydride of boric acid and an aliphatic monocarboxylic acid is formed in situ.
4. The process as claimed in claim 2 in which the mixed acid anhydride of boric acid and an aliphatic monocarboxylic acid is formed in situ.
In testimony whereof I aflix my signature.
DR. LUDWIG SCHMIDT.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1836287X | 1928-02-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US1836287A true US1836287A (en) | 1931-12-15 |
Family
ID=9681540
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US300949A Expired - Lifetime US1836287A (en) | 1928-02-18 | 1928-08-20 | Process for obtaining bornyl and isobornyl esters |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US1836287A (en) |
-
1928
- 1928-08-20 US US300949A patent/US1836287A/en not_active Expired - Lifetime
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