US2301827A - Process of making higher aliphatic - Google Patents
Process of making higher aliphatic Download PDFInfo
- Publication number
- US2301827A US2301827A US2301827DA US2301827A US 2301827 A US2301827 A US 2301827A US 2301827D A US2301827D A US 2301827DA US 2301827 A US2301827 A US 2301827A
- Authority
- US
- United States
- Prior art keywords
- acid
- acids
- lactones
- higher aliphatic
- making higher
- 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 12
- 125000001931 aliphatic group Chemical group 0.000 title description 6
- 239000002253 acid Substances 0.000 description 22
- 150000002596 lactones Chemical class 0.000 description 16
- BVKZGUZCCUSVTD-UHFFFAOYSA-N Carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 14
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 10
- 150000007513 acids Chemical class 0.000 description 10
- -1 carbocyclic ketones Chemical class 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 125000004432 carbon atoms Chemical group C* 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 230000000875 corresponding Effects 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 235000019253 formic acid Nutrition 0.000 description 4
- 150000004675 formic acid derivatives Chemical class 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- 125000002252 acyl group Chemical group 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000003841 chloride salts Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 150000001261 hydroxy acids Chemical class 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M methanoate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D315/00—Heterocyclic compounds containing rings having one oxygen atom as the only ring hetero atom according to more than one of groups C07D303/00 - C07D313/00
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D313/00—Heterocyclic compounds containing rings of more than six members having one oxygen atom as the only ring hetero atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/16—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D309/28—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D309/30—Oxygen atoms, e.g. delta-lactones
Definitions
- the present method of carrying out the lactonisation is limited to those hydroxycarboxylic acids which possess a chain of eleven or more carbon atoms between their functional groups. It is immaterial whether the chain is branched or normal, whether it is saturated or unsaturated, or whether it still contains other substituted groups.
- the operations may be conducted in the presence of esterifying catalysts. Only those derivatives of the w-hydroxycarboxylic acids can be used which possess a certain stability at about 200 C., such as, for example, the formates or the carbonates of the hydroxycarboxylic acids. In order that the vaporisation' 'takes place at the lowest possible temperature operations are carried out in the best possible vacuum i. e. with a low molecular concentration of the hydroxycarboxylic acid or derivative. It is then preferable to dilute the vapours with other inert gases or vapours.
- the present invention enables higher lactones to be prepared in a manner which is very simple technically and in outstanding yields. As compared with the methods heretofore known, therefore, which either had to commence with costly higher ketones or, in the case of direct lactonisation of the whydroxycarboxylic acids, afforded very small yields, the process according to the present invention represents an important technical advance.
- lactones made according to this invention are intended for use in the perfume industry.
- Example 1 The formic acid ester of l l-hydroxytetradecane-l-carboxylic acid is very slowly led over a titanium dioxide or other acid-splitting catalyst heated to 200 to 300 C. in a vacuum, 1. e. at a reduced partial pressure.
- the distillate collected in the cooled receiver is freed from admixed acid by means of soda solution and is purified by vacuum distillation.
Description
Patented Nov. 10, 1942 PROCESS OF MAKING HIGHER ALIPHATIC LACTONES Max Stoll,
Geneva, Switzerland, assignor to Firmenich & Cie., Successeurs de la Socit Anonyme M. Naef & Cie., Geneva, Switzerland, a corporation of Switzerland No Drawing. Original application May 25, 1934,
Serial No. 727,583. Divided and this application April 29, 1940, Serial No. 332,395. In Switzerland July 17, 1933 2 Claims.
This application is a division of application Serial Number 727,583 filed May 25, 1934.
It is well known that higher lactones can be obtained by suitably oxidising higher carbocyclic ketones. It is also known that higher lactones are obtained if w-halogen fatty acids are heated with metal oxides or the salts of w-halogen fatty acids in indifferent solvents (German patent specification No. 449,217). As is apparent from the examples in the said German patent specification this prior process always involves lactonisation in the heterogeneous phase, that is to say, with undissolved salts, such as for example, copper and silver salts.
In contradistinction thereto it has been found that the higher lactones can be obtained with much better yields if the lactonisation (inner esterification) of the corresponding hydroxy acids or functional derivatives thereof is carried out in the vapor phase under conditions producing a low partial pressure. It is preferable to operate under conditions of reduced pressure so that the reactions taking part can proceed in the mono-molecular form.
Under these new conditions, contrary to what is said in German specification No. 449,217, the lactonisation of free w-hydroxycarboxylic acids can be successfully effected. Of course, corresponding to the esterification reactions chosen for the lactonisation, derivatives of the hydroxycarboxylic acids may be used in place of the free acids, such as, for example, their esters, halides, acid chlorides and so forth.
The present method of carrying out the lactonisation is limited to those hydroxycarboxylic acids which possess a chain of eleven or more carbon atoms between their functional groups. It is immaterial whether the chain is branched or normal, whether it is saturated or unsaturated, or whether it still contains other substituted groups.
The operations may be conducted in the presence of esterifying catalysts. Only those derivatives of the w-hydroxycarboxylic acids can be used which possess a certain stability at about 200 C., such as, for example, the formates or the carbonates of the hydroxycarboxylic acids. In order that the vaporisation' 'takes place at the lowest possible temperature operations are carried out in the best possible vacuum i. e. with a low molecular concentration of the hydroxycarboxylic acid or derivative. It is then preferable to dilute the vapours with other inert gases or vapours.
The present invention enables higher lactones to be prepared in a manner which is very simple technically and in outstanding yields. As compared with the methods heretofore known, therefore, which either had to commence with costly higher ketones or, in the case of direct lactonisation of the whydroxycarboxylic acids, afforded very small yields, the process according to the present invention represents an important technical advance.
The lactones made according to this invention are intended for use in the perfume industry.
Example The formic acid ester of l l-hydroxytetradecane-l-carboxylic acid is very slowly led over a titanium dioxide or other acid-splitting catalyst heated to 200 to 300 C. in a vacuum, 1. e. at a reduced partial pressure. The distillate collected in the cooled receiver is freed from admixed acid by means of soda solution and is purified by vacuum distillation.
What I claim is:
1. A process for making monomeric lactones from the formates of hydroxycarboxylic acids of the form HCOORCOOH, where R is an aliphatic residue containing a chain of at least ten carbon atoms, consisting in removing the elements of formic acid from the acid in the presence of a catalyst consisting of titanium dioxide at elevated temperature, the formate of the acid being in the vapor phase and under a reduced pressure.
2. A process for making monomeric lactones from esters of hydroxy carboxylic acids of the formula XC0.0R.COOI-l. in which XCO is an acyl group, where R is an aliphatic residue containing a chain of at least ten carbon atoms, consisting in removingthe elements of the acid XCOOH from the acids in the presence of a solid phase catalyst at elevated temperature, the ester of the acid being in the vapor phase and under a reduced pressure.
MAX STOLL.
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2301827A true US2301827A (en) | 1942-11-10 |
Family
ID=3432962
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US2301827D Expired - Lifetime US2301827A (en) | Process of making higher aliphatic |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2301827A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2652406A (en) * | 1953-09-15 | Method for the peeparation of | ||
| US4532058A (en) * | 1980-09-25 | 1985-07-30 | Texaco Inc. | Spirolactone condensation product dispersants and lubricants containing same |
-
0
- US US2301827D patent/US2301827A/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2652406A (en) * | 1953-09-15 | Method for the peeparation of | ||
| US4532058A (en) * | 1980-09-25 | 1985-07-30 | Texaco Inc. | Spirolactone condensation product dispersants and lubricants containing same |
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