US2837569A - Method of fixing lower alkyl radicals on ethylenic double bonds of terpenes - Google Patents
Method of fixing lower alkyl radicals on ethylenic double bonds of terpenes Download PDFInfo
- Publication number
- US2837569A US2837569A US424779A US42477954A US2837569A US 2837569 A US2837569 A US 2837569A US 424779 A US424779 A US 424779A US 42477954 A US42477954 A US 42477954A US 2837569 A US2837569 A US 2837569A
- Authority
- US
- United States
- Prior art keywords
- lower alkyl
- ethylenic double
- double bonds
- alkyl radicals
- terpenes
- 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 claims description 12
- 150000003505 terpenes Chemical class 0.000 title description 3
- 235000007586 terpenes Nutrition 0.000 title description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 14
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- QMVPMAAFGQKVCJ-UHFFFAOYSA-N citronellol Chemical compound OCCC(C)CCC=C(C)C QMVPMAAFGQKVCJ-UHFFFAOYSA-N 0.000 claims description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 7
- 239000005792 Geraniol Substances 0.000 claims description 6
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 claims description 6
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical class N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 6
- 229940113087 geraniol Drugs 0.000 claims description 6
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 claims description 6
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 6
- 150000003512 tertiary amines Chemical class 0.000 claims description 6
- WTEVQBCEXWBHNA-UHFFFAOYSA-N Citral Natural products CC(C)=CCCC(C)=CC=O WTEVQBCEXWBHNA-UHFFFAOYSA-N 0.000 claims description 4
- 229940043350 citral Drugs 0.000 claims description 4
- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical compound CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 claims description 4
- 239000001490 (3R)-3,7-dimethylocta-1,6-dien-3-ol Substances 0.000 claims description 3
- QMVPMAAFGQKVCJ-SNVBAGLBSA-N (R)-(+)-citronellol Natural products OCC[C@H](C)CCC=C(C)C QMVPMAAFGQKVCJ-SNVBAGLBSA-N 0.000 claims description 3
- CDOSHBSSFJOMGT-JTQLQIEISA-N (R)-linalool Natural products CC(C)=CCC[C@@](C)(O)C=C CDOSHBSSFJOMGT-JTQLQIEISA-N 0.000 claims description 3
- JGQFVRIQXUFPAH-UHFFFAOYSA-N beta-citronellol Natural products OCCC(C)CCCC(C)=C JGQFVRIQXUFPAH-UHFFFAOYSA-N 0.000 claims description 3
- 235000000484 citronellol Nutrition 0.000 claims description 3
- 229930007744 linalool Natural products 0.000 claims description 3
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UZFLPKAIBPNNCA-BQYQJAHWSA-N alpha-ionone Chemical compound CC(=O)\C=C\C1C(C)=CCCC1(C)C UZFLPKAIBPNNCA-BQYQJAHWSA-N 0.000 description 4
- JZQOJFLIJNRDHK-CMDGGOBGSA-N alpha-irone Chemical compound CC1CC=C(C)C(\C=C\C(C)=O)C1(C)C JZQOJFLIJNRDHK-CMDGGOBGSA-N 0.000 description 4
- -1 phosphoric Chemical class 0.000 description 4
- ZEUWCZMRCKECEG-UHFFFAOYSA-N (2E)-3,7-dimethylnona-2,6-dien-1-ol Chemical compound CCC(C)=CCCC(C)=CCO ZEUWCZMRCKECEG-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- NEHNMFOYXAPHSD-UHFFFAOYSA-N citronellal Chemical compound O=CCC(C)CCC=C(C)C NEHNMFOYXAPHSD-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000003248 quinolines Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- BCEQJZNLIKMDEU-UHFFFAOYSA-N 3,7-dimethylnona-2,6-dienal Chemical compound CCC(C)=CCCC(C)=CC=O BCEQJZNLIKMDEU-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- 239000004135 Bone phosphate Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical class CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- UZFLPKAIBPNNCA-UHFFFAOYSA-N alpha-ionone Natural products CC(=O)C=CC1C(C)=CCCC1(C)C UZFLPKAIBPNNCA-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229930003633 citronellal Natural products 0.000 description 1
- 235000000983 citronellal Nutrition 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 150000003864 primary ammonium salts Chemical class 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 150000003865 secondary ammonium salts Chemical class 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 125000002298 terpene group Chemical group 0.000 description 1
- 150000003866 tertiary ammonium salts Chemical class 0.000 description 1
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
- C07C403/14—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by doubly-bound oxygen atoms
- C07C403/16—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by doubly-bound oxygen atoms not being part of —CHO groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
Definitions
- This invention relates generally to a method of fixing simple or composite alkyl radicals to ethylenic double bonds of organic molecules. It applies more especially to substances in the terpene group and, in particular, to the synthetic production of irone and its homologues, which are of high olfactory value.
- a tertiary amine is employed as an agent for the substitution of an alkyl radical for hydrogen on an ethylenic double bond.
- This method utilises the properties of nitrogen which may be trivalent or pentavalent.
- the primary, secondary and tertiary amines in which nitrogen is trivalent are capable of fixing an acid radical linked with either one hydrogen atom or with an alkyl radical.
- tetramethylammonium bromide is split up by simple distillation into trimethylamine and methyl bromide just as ammonium chloride reduced to the vapour state is a mixture of hydrochloric acid and free amrnonia.
- ammonium salts which are exothermic, regenerate their constituents by an endothermic reaction fed by an external source of heat.
- the invention is a new application of the following phenomenon: if heat is employed to promote the dissociation of a quaternary ammonium salt in the presence of an organic molecule containing certain double bonds, the acid and alkyl radicals, which break away separately from the quaternary ammonium molecule, are capable of fixing on certain double bonds, whilst at the same time the tertiary amine is regenerated.
- Any tertiary amine may be employed; but pyridine and quinoline compounds are preferred.
- esters with the alkyl radical to be substituted may be either esters of strong acid such as hydrochloric, hydrobromic, hydriodic or sulphuric acid but it is equally possible, and more advantageous in certain cases, to employ esters of less energetic acids such as phosphoric, boric, oxalic, malonic and acetylacetic acids.
- the quaternary ammonium salts are formed transitorily when the mixture is brought to boiling, and lead finally to the appearance of the prodnot sought.
- the most suitable ester must be chosen and, at the same time, the most suitable solvent to complete the operation. It is suflicient that this latter should not react with the pyridine .or quinoline compound.
- irone constituted by a mixture of irone-alpha and irone-beta.
- the irone-alpha predominates in the mixture.
- R1 Rs is the most suitable for fixation of the alkyl groupings:
- the methyl grouping can be fixed by the mechanism as described for geraniol whereby iso-irone is obtained, the odour of which differs only slightly from that of oc-lOl'lOIlE itself and does not recall the odour of iris as does irone.
- the method of operation is similar to that for methyl geraniol as described above.
- iromethylgeraniol will have the formula:
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Fats And Perfumes (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
ilni'ted States Patent METHOD OF FIXING LOWER ALKYL RADICALS ON ETHYLENIC DOUBLE BONDS OF TERPENES Albert Verley, Neuilly-sur-Seine, France No Drawing. Application April 21, 1954 Serial No. 424,779
Claims priority, application France April 27, 1953 2 Claims. (Cl. 260-587) This invention relates generally to a method of fixing simple or composite alkyl radicals to ethylenic double bonds of organic molecules. It applies more especially to substances in the terpene group and, in particular, to the synthetic production of irone and its homologues, which are of high olfactory value.
According to the invention, a tertiary amine is employed as an agent for the substitution of an alkyl radical for hydrogen on an ethylenic double bond.
This method utilises the properties of nitrogen which may be trivalent or pentavalent.
It is known that the primary, secondary and tertiary amines in which nitrogen is trivalent are capable of fixing an acid radical linked with either one hydrogen atom or with an alkyl radical.
In this way, primary, secondary, tertiary and quaternary ammonium salts are obtained: but, whilst the trivalent amines are perfectly stable within the temperature limits at which the organic products are operated upon, quaternary ammonium salts on the other hand decompose easily at temperatures between 150 and 300 whilst regenerating the tertiary amines.
Thus, tetramethylammonium bromide is split up by simple distillation into trimethylamine and methyl bromide just as ammonium chloride reduced to the vapour state is a mixture of hydrochloric acid and free amrnonia.
The ammonium salts, which are exothermic, regenerate their constituents by an endothermic reaction fed by an external source of heat.
The invention is a new application of the following phenomenon: if heat is employed to promote the dissociation of a quaternary ammonium salt in the presence of an organic molecule containing certain double bonds, the acid and alkyl radicals, which break away separately from the quaternary ammonium molecule, are capable of fixing on certain double bonds, whilst at the same time the tertiary amine is regenerated.
Any tertiary amine may be employed; but pyridine and quinoline compounds are preferred.
In this case it is always one of these two bases which is regenerated, and the reagent may be employed indefinitely.
The esters with the alkyl radical to be substituted may be either esters of strong acid such as hydrochloric, hydrobromic, hydriodic or sulphuric acid but it is equally possible, and more advantageous in certain cases, to employ esters of less energetic acids such as phosphoric, boric, oxalic, malonic and acetylacetic acids.
With certain of these esters, the quaternary ammonium salts are formed transitorily when the mixture is brought to boiling, and lead finally to the appearance of the prodnot sought. Naturally, in each particular case, the most suitable ester must be chosen and, at the same time, the most suitable solvent to complete the operation. It is suflicient that this latter should not react with the pyridine .or quinoline compound.
The general method employed in accordance with the invention may be as follows:
One mixes a molecule of the product to be substituted, a molecule of the ester of the alcohol whose radical has to be substituted, and a molecule of pyridine or quinoline base.
Even if the acid is tribasic or dibasic, it will not be necessary to employ more than one molecule of pyridine or of quinoline in each case.
Next, a quantity of solvent is added to obtain a homogeneous mixture, and this mixture is boiled, with reflux cooling, for the necessary period to ensure completion of the reaction.
The uses of this method have been studied principally in relation to the derivatives of the terpene series such as citral, geraniol, rhodinol, linalool, citronellol and a-ionone.
These substances, geraniol for example, contain ethylenic double bonds of the type concerned in the present invention. In this case, it is solely the double bond at the end of the chain which reacts.
Two examples of the method of the invention are given below:
A.Preparati0n 0 methylgeraniol The following are mixed:
Grs. 1 molecule geraniol 154 1 molecule methyl sulphate 126 1 molecule pyridine 79 For methyl geraniol, the constants are as follows:
B. P. =110.5 C.
If the same reaction is repeated on citral, one obtains methyl citral which, on condensation with acetone in the presence of dilute soda, gives pure pseudoirone of which the constants are:
E12: a d =0.8967 n =1.5279
Pseudoirone cyclised by phosphoric acid in accordance with the method employed for preparing the alpha-ionone,
gives irone, constituted by a mixture of irone-alpha and irone-beta. The irone-alpha predominates in the mixture.
I have found the following constants for pure ironealpha:
R1 Rs is the most suitable for fixation of the alkyl groupings:
CH3 CH3 H2? GHOH=CHCO.CHs H;C\ 20.0113 oi (a-ionone) Cg: /C s Hi CHGH=CHCO.CH;
H1O 0.0m
Consequently, on the u-ionone containing this grouping the methyl grouping can be fixed by the mechanism as described for geraniol whereby iso-irone is obtained, the odour of which differs only slightly from that of oc-lOl'lOIlE itself and does not recall the odour of iris as does irone.
The method of operation is similar to that for methyl geraniol as described above.
In order to distinguish the substances thus obtained from those obtained by fixation of the alkyl groupings with formation of oxide esters on the alcohols and of acetals on the aldehydes, the term iro is placed before all derivatives of the class indicated above in order to 4 make it clear that these derivatives contain the groupings which are at the basis of the formation of the irone and of its homologues.
For example, iromethylgeraniol will have the formula:
CH(CH3)2 iromethylcitronellal, the formula:
OH; /H C=CCH2CHa-GH-CH2C C a CH; CH: 0
and by hydration, this last substance will give iromethylhydroxy: citronellal.
All the substances have an olfactive value superior to that of the derivatives from which they were taken, and the method according to the present invention appears to be capable of producing these on a commercial basis.
I claim:
1. A method of inserting a lower alkyl group on an ethylenic double bond in a substance selected from the group consisting of citral, geraniol, rhodinol, linalool, citronellol and a-ionone, wherein said substance is reacted with a quaternary ammonium salt formed from a lower alkyl ester and a tertiary amine, selected from the group consisting of pyridine and quinoline compounds, to cause replacement of a hydrogen atom attached to the ethylenic double bond by the alkyl radical of said ester.
2. A method as claimed in claim 1, wherein the alkyl ester is dimcthyl sulphate.
References Cited in the file of this patent Favre et al., Helv. Chim. Acta 35, 1627-36 (1952).
Claims (1)
1. A METHOD OF INSERTING A LOWER ALKYL GROUP ON AN ETHYLENEIC DOUBLE BOND IN A SUBSTANCE SELECTED FROM THE GROUP CONSISTING OF CITRAL, GERANIOL, RHODINOL, LINALOOL, CITRONELLOL AND A-IONONE, WHEREIN SAILD SUBSTANCE IS REACTED WITH A QUATERNARY AMMONIUM SALT FORMED FROM A LOWER ALKYL ESTER AND A TERTIARY AMINE, SELECTED FROM THE GROUP CONSISTING OF PYRIDINE AND QUINOLINE COMPOUNDS, TO CAUSE REPLACEMENT OF A HYDROGEN ATOM ATTACHED TO THE ETHYLENIC DOUBLE BOND BY THE ALKYL RADICAL OF SAID ESTER.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1076478T | 1953-04-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2837569A true US2837569A (en) | 1958-06-03 |
Family
ID=9607657
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US424779A Expired - Lifetime US2837569A (en) | 1953-04-27 | 1954-04-21 | Method of fixing lower alkyl radicals on ethylenic double bonds of terpenes |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US2837569A (en) |
| FR (1) | FR1076478A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3021359A (en) * | 1959-03-20 | 1962-02-13 | Hoffmann La Roche | Unsaturated acyclic esters, and method of producing same |
| US3859366A (en) * | 1971-12-23 | 1975-01-07 | Monsanto Co | 2-alkyl-oct-5-en-2-ols and their esters |
| US3959396A (en) * | 1966-08-03 | 1976-05-25 | Givaudan Corporation | Unsaturated alcohols and perfume compositions containing same |
| US3966648A (en) * | 1971-12-23 | 1976-06-29 | Monsanto Company | 2-Alkyl-oct-5-en-2-ols in fragrance compositions |
-
1953
- 1953-04-27 FR FR1076478D patent/FR1076478A/en not_active Expired
-
1954
- 1954-04-21 US US424779A patent/US2837569A/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| None * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3021359A (en) * | 1959-03-20 | 1962-02-13 | Hoffmann La Roche | Unsaturated acyclic esters, and method of producing same |
| US3959396A (en) * | 1966-08-03 | 1976-05-25 | Givaudan Corporation | Unsaturated alcohols and perfume compositions containing same |
| US3859366A (en) * | 1971-12-23 | 1975-01-07 | Monsanto Co | 2-alkyl-oct-5-en-2-ols and their esters |
| US3966648A (en) * | 1971-12-23 | 1976-06-29 | Monsanto Company | 2-Alkyl-oct-5-en-2-ols in fragrance compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| FR1076478A (en) | 1954-10-27 |
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