JPH0142929B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to the liquid phase rearrangement reaction of allylic tertiary alcohols to allylic primary or secondary alcohols in the presence of vanadium-containing catalysts at moderate temperatures (usually 50-250°C, advantageously 100-200°C). This invention relates to a method for increasing allylic rearrangement beyond the equilibrium between allylic primary or secondary alcohols and allylic tertiary alcohols obtained in . These are the liquid phase catalytic allylic tertiary alcohol isomerization conditions referred to herein, and these are U.S. Pat.
et al.). US Pat. No. 3,925,485 exemplifies the use of temperatures such as 150°, 160°, and 161° C. to rearrange linalool into geraniol and nerol in this manner. The equilibrium obtained by such an operation is approximately 30% of these primary alcohols.
and 70% tertiary alcohol. Nerol is a geometric isomer of geraniol. In the present invention, a precursor of an allylic tertiary alcohol (an alcohol precursor is a compound that does not contain a catalytic metal but can be cleaved to form the corresponding alcohol)
An isomerization reaction mixture containing . (Alcohol precursors are sometimes referred to herein as alcohologens.) The allylic tertiary alcohologens are prepared under liquid-phase catalytic allylic tertiary alcohol isomerization conditions (generally related to temperature and catalyst).
(as shown by Chabardes et al.), the allylic groups or residues remaining in the mixture (including those in free allyl alcohol) are in the allylic primary or tertiary configuration rather than in the allylic primary or tertiary configuration. In other words, isomerization of such residues can be obtained using either the methods of Chabardes et al. or Ninagawa et al. until the normal equilibrium between the corresponding allylic alcohols becomes more abundant in the two-configuration. It will be isomerized until it surpasses. Producing alcohologens can also be carried out at temperatures slightly higher than those exemplified by Chabares et al. (e.g. in the case of geraniol-nerol production from linalool).
160-180℃) and can be advantageously operated under atmospheric pressure. An associated advantage is the completeness of the reaction as well as its speed. Although the present invention is not to be construed solely as a liquid phase contact process for producing allylic primary or secondary alcohols from allylic tertiary alcohols, it is likely that such products are most readily commercially available. Will. The present invention is characterized in that the allylic alcohologen is formed before or during the liquid phase catalytic isomerization of the allylic third moiety of the various allylic compounds present into the first or second allylic moiety. . In one major aspect of the invention, an allylic tertiary alcohologen (eg, linalyl isobutyl borate) is preformed and this material is then subjected to catalytic liquid phase isomerization. In such isomerization, free tertiary alcohol does not appear to have any significant effect, and if it is present, this appears to be independent of the amount of free alcohol present. That is, the reaction is zero order with respect to the free tertiary alcohol. In another main aspect of the invention, an allylic tertiary alcohol (e.g., linalyl isobutyl borate) is produced by a parallel reaction (e.g., transesterification of isobutyl borate), while an allylic tertiary alcohol (e.g., linalool) also isomerizes to free allylic primary or secondary alcohols (eg geraniol and nerol), with concomitant formation of allylic primary or secondary alcohologens (eg geranyl borate and neryl borate). Apparently, by starting the isomerization with some amount of preformed allylic tertiary alcohol and the corresponding free allylic tertiary alcohol,
The above two aspects can be combined in various ways. In an extreme example of the second main aspect above, it is possible to produce a slightly smaller proportion of allylic tertiary alcohols compared to free allylic primary or secondary alcohols, and such production Things convert into their specific alcohologens during manipulation. Since one of the most important applications of the present invention is the conversion of linalool to geraniol and nerol (the molar ratio of geraniol to nerol is approximately 1.63:1), it is sometimes referred to herein as "linaloologen". ), "geraniologen" and "nerologen." These terms refer to the alcohologens that produce linalool, geraniol, and nerol, respectively. Similarly,
"Butanologen" produces butanol upon cleavage. Isobutanol-linalyl mixed esters of polyacid acids such as boric acid, which can also be both "isobutanologenic" and "linaloologenic", are not included in this specification. Purpose includes "linaloologen" or "allylictertiary alcohologen"
(because the alkanol cleavage product is normally considered a by-product that would be recovered for reuse in isomerization). The accompanying drawings are process flow diagrams outlining two main applications of the invention for possible industrial production. In the figure, pumps, compressors, ejectors, measuring instruments, valves and joints, agitators, and heaters are not shown. These can be provided in a conventional manner wherever necessary or desired. Although all figures are intended to be described in connection with the production of geraniol or nerol from linalool, similar operations can be performed with other volatile tertiary allyl alcohol starting materials. The present invention will be explained in detail below. In the application example shown in Figure 1, tonalologen is produced in parallel isomerizations, i.e. (a) geraniol and nerol from linalool and (b) geraniologen and nerologen from such linalologen.
These alcohologens are various orthoborates of linalool and geraniol. In addition to producing linalogen, which is isomerized to geraniologen and nerologen, geraniol and nerol produced from the isomerization of linalool now produce geraniologen and nerologen. This serves to move the isomerization of linalool to the right, i.e., to isomeric products. In the application example shown in Figure 2, linalologen is pre-produced as linalyl flutoborate;
These allylic alcohologens are then isomerized to their geranyl and neryl counterparts. Now, if we look at Figure 1, it shows the basic design diagram of a pilot plant that uses industrial linalool (at least about 30% purity and as high as 95-98% purity) at a daily production weight of about 681 kg (1500 lbs) or less. There is.
The linalool ingredient in this example is only 48% linalool. The balance of such raw materials is almost exclusively cyclic non-allylic terpene alcohols such as phenols, purinols, 2-pinanols, and small amounts of alphaterpineol. The present invention can advantageously utilize such raw materials. This is because isomerization appears to be limited to tertiary allylic substances, and the usual impurities that are difficult to separate from linalool are inactive here. Those substances in the linalool feed that are difficult to separate from nerol and geraniol but are easily separated from linalool (eg, most of the alphaterpineol) are of course advantageously removed from the linalool feed. The process of the present invention can be operated to obtain significantly higher amounts of geraniol and nerol from linalool than the cited processes, so that the use of highly dilute raw materials is also economical. At least some of the common impurities, such as 2-pinanols, can be economically recovered for reuse. Typically, the linalool source can be conveniently derived from alpha-pinene (preferably) or beta-pinene. Furthermore, side reactions in the cited process may result in the degradation of allylic primary and secondary alcohol products (this probably occurs via the unsaturated aldehyde formation pathway, which is present at temperatures between 140 and 160 °C).
(and is unstable at low temperatures, leading to the formation of dimeric aldol condensation products). The processing alcohologen of the process of the invention is not subject to such degradation at such temperatures, which results in much improved yields. Referring to FIG. 1, reaction vessel 12 has a heating and cooling jacket and is equipped with a stirrer. It can also have internal heating and cooling coils if desired or necessary. A 20% aqueous solution of boric acid, 1087 parts of isobutanol, 1000 parts of 48% linalool (a "very lean" industrial grade) and 2 parts of ammonium metavanadate catalyst are added to reactor kettle 12, 700 parts of toluene. Prepare with. Some or all of the boric acid solution used can be recovered from a previous similar operation. Stir and heat the reactor contents. The steam generated therefrom ascends the fractional distillation column 13. The column is refluxed at the top with a separated organic phase reflux stream from line 21. Distillate vapor is in line 14
It is then condensed in a condenser 16. Condenser 16 is indirectly water-cooled and communicates with the atmosphere. The condensate flows in line 17 and enters decanter 18. Here, gravity separates the upper organic-rich phase from the lower aqueous phase (the "water layer").
separate into This aqueous layer, containing approximately 2% isobutanol, is drawn off from the bottom of decanter 18 through line 19. Such layers are 2022
part, which is saved to wash the crude product in the third stage of the operation. Following water removal, 485 parts of the toluene-isobutanol mixture is added to the reflux column 13.
Instead of being returned to the system, it is withdrawn from line 21 as condensate (via a discharge pipe, not shown). In this first step, not only water is removed, but also isobutyl borates, along with some linalylbutyl borate, some geranyl and nenyl borates, and some free geraniol and nerol. The temperature of the distillation operation ranges from 90℃ to remove water at the end of the total heating time of 14 hours.
It becomes 160℃. The operating pressure is atmospheric pressure. It is isolated from the atmosphere by the suction of nitrogen gas which is removed from the outlet on the operating condenser. The second stage of operation is initiated by charging reactor kettle 26 with 2080 parts of additional linalool coming in from line 24 and inlet tube 23 and the liquid product of the first stage exiting reactor kettle 12. The latter is transferred via line 22 and inlet pipe 23.
The reaction vessel 26 is provided with an internal heating coil. The vapor from the reaction vessel ascends the fractional distillation column 27, line 28, is condensed in the condenser 29, the condensate passes through line 32, then is refluxed to the column via line 34, and is distilled via line 33 as a distillate. be captured. The various distillate fractions are sent to storage tanks, not shown. First, the concentrator is vented to atmosphere. When a lower absolute pressure is used, line 31 is connected to a vacuum line. As this distillation progresses, the total pressure on the distillation column is usually reduced to maintain a temperature of 160°C in the reaction vessel. This removes most of the isobutanol and sends it to the storage tank via line 33 while a relatively small amount of reflux is used in line 34.
This isobutanol contains a small amount of toluene
It consists of 1170 copies. This is stored for reuse. When the reaction vessel 26 is boiled for an additional 12 hours at 200 mmHg abs, the temperature therein reaches 170°C. Furthermore
When boiling at 200mm for 8 hours, the reaction pot temperature is 174℃.
become. Analysis of the allylic alcohol in the reaction kettle at this point is approximately 10.9% linalool and 80.1% nerol and geraniol after hydrolyzing the sample. The third stage begins by transferring the stripped contents from reaction vessel 26 to reaction vessel 37, which is open to the atmosphere and equipped with a stirrer and heating means (not shown). Here, the crude product is successively washed three times at 85° C. by stirring with an aqueous substance, allowing it to stand each time, and withdrawing the aqueous layer (“aqueous layer”) that has been allowed to stand each time. The first wash is 1652
of water, preferably the aqueous material saved from the first stage and drawn off from the decanter 18 via line 19. A second wash is carried out with 400 parts of water and/or such aqueous substances, and a third wash is carried out in the same manner. The third wash may be performed with 400 parts of 7% ammonium hydroxide instead of water. The washing liquid left standing is extracted from the reaction vessel 37 through a line 39 and passed through a filter 41. A small amount of precipitate, less than 1%, is removed from the operating system via a discharge pipe 42. This deposit is a vanadium-containing material. The overwash solution containing about 14.7% dissolved boric acid is stored in wash solution storage tank 44 (2798 parts) and reused in a new first stage. The crude product is the top or oily layer. This is extracted from the reactor via line 39, and is
1, and any precipitate removed at this time is removed to the outside of the operating system via the discharge pipe 42. The filtered crude product passes through a line 46 to a crude product storage tank 47.
Enter. This is 3217 copies. The stored 3217 parts of crude product and 3 parts of potassium stearate are transferred from line 48 to static pot 49 and the fourth stage, purification distillation, begins.
The product contents are heated indirectly by means not shown. The vapor ascends through a fractional distillation column 51 and a line 52, and is condensed in a water-cooled water condenser 54. The condensate flows down line 56 and into line 58
is refluxed to the column via line 57 and withdrawn as a distillate fraction. First, the condenser is vented to atmosphere and a small amount of isobutanol and an initial volume of water are collected. The pot temperature is 140 to improve the smell of the product alcohol and improve the yield.
C., although the temperature may be as high as 170.degree. C. in the final residue stripping operation. Therefore, during the distillation operation, the total pressure is lowered step by step to maintain a pot temperature of 140°C. These steps typically start at atmospheric pressure, then are brought to 100 mmHg abs when the pot reaches 140°C, then to 10 mmHg abs when the pot reaches 140°C again, and finally to less than 1 mmHg abs to strip anything of value from the residue. be made into The fractions are as follows. First distillate - 449 parts of isobutyl alcohol and 103 parts of water; "waste" fraction - 252 parts, mainly hydrocarbons;
334 parts of mainly various alcohols containing 10.3% linalool; for the purpose of this operation other alcohols are mainly considered as impurities; middle distillates -
642 parts, containing 23% linalool; intermediate nerol and geraniol fraction, 152 parts, containing about 80% of these alcohols and saved for recirculation to the subsequent purification distillation; main product fraction - 1062 copies, 99
% of nerol and geraniol; and an additional 25 parts of high purity nerol and geraniol, but this is usually slightly off in odor and color and is recycled for redistillation. After the “waste” fraction, the overhead pressure is
10 mmHg abs except for the last recycle fraction, which is derived from the stripping step described above. The standing residue is 191 parts. With respect to both Figures 1 and 2, the fractional distillation column is conveniently a packed column, but may be of various other types, such as sieve plates and the like. Packed columns are preferred here because of their low pressure drop. Although the preferred material for manufacturing the devices described herein is austenitic stainless steel, glass-lined steel, Monel metal, and other rust-resistant materials can also be used, eliminating the need for unwanted release of flavoring materials during handling. A very good effect is obtained in removing impurities. “One-pot” except for the final purification
The operation can be carried out in which the "pot" or reaction vessel is equipped with heating and cooling means with a stirrer under atmospheric pressure or under reduced pressure, and can also be used as a washing vessel, from which the fractionation is carried out. It should be clear that distillation was possible, and the ability to decant and handle the distillate fraction was made available. Now, referring to Figure 2, the raw material for linalool is 95
% purity and is described in more detail in connection with the Examples below. In many cases, the equipment for this operation is substantially the same as for the operation described in FIG. 1 with regulating devices in the inlet and outlet pipes. The reaction vessel 62 and its accessories in FIG. 2 are similar to the reaction vessel 26 and its accessories in FIG. 1. The flush container 102 may be the same as the similar container 37 of FIG. The purification distillation pot 112 and its appurtenances in FIG. 2 are essentially the same as the purification distillation pot 49 and its appurtenances in FIG. 975 parts of isobutanol, 252 parts of boric anhydride, and 500 parts of toluene are charged into the reaction vessel 62 from the line 61. The contents of the reaction vessel are stirred and heated.
The steam emerging therefrom ascends the fractional distillation column 63. Reaction water and toluene are sent to column 63 and line 64
Distilled through the process. The steam is condensed in a condenser 65. Condensate flows from the condenser into a decanter 66. The toluene is separated here and returned to the top of the column via line 67 as reflux. A water layer of 228 parts is withdrawn from the decanter via line 68. This layer contains approximately 2% isobutanol. The operation takes about 10 hours, and the temperature of the reaction vessel increases from about 94℃ during this time.
The temperature gradually rises to 134℃. Operation is at atmospheric pressure.
The product, 1513 parts of crude triisobutyl borate, is transferred from reaction vessel 62 to reaction vessel 71 via line 69. In this purification operation, the contents of reaction vessel 71 are boiled and the vapor ascends through fractional distillation column 72, line 73, and is condensed in condenser 76. The condenser is first vented to atmosphere and connected to a vacuum line by connecting tube 74. The condensate enters reflux column 72 via lines 77 and 78. A portion of the condensate is withdrawn as another distillation fraction via line 79 and transferred to a storage tank, not shown. Triisobutyl borate is distilled at 10 mmHg Abs in tank 82.
stored within. This is 105°~106 under this pressure
It boils at 805 degrees Celsius, of which there are 805 parts. The other initially removed distillate fractions are 567 parts of a mixture of toluene and isobutanol (collected at atmospheric pressure and 100 mm Hg abs) and a recycled middle distillate rich in triisobutyl borate. The reactor temperature is not allowed to rise above about 140-150°C, but the product is very stable to thermal degradation so higher temperatures may be used. Nine parts of the residue are extracted from the reaction vessel 71 through a discharge pipe (not shown). 250 parts of triisobutyl borate from storage tank 82 is transferred via line 83 to reaction vessel 84. 150 parts of linalool is charged into the reaction kettle 84 via line 85. The mixed contents of reaction vessel 84 are brought to a boil. The vapor rises via fractional distillation column 86 and line 87. These are condensed in a condenser 89.
A reduced pressure is maintained by connecting this device to a vacuum line via a connecting tube 88. Condensate from the condenser is returned via lines 91 and 92 and refluxed to the distillation column. A distillate fraction is removed via line 94. The pot temperature is 150°C and 50 parts of the first distillate fraction are removed at a pressure of 100 mmHg abs. At the same pot temperature, a second fraction of 112 parts is removed at a pressure of 10 mmHg abs. 238 parts of linalyl diisobutyl borate are transferred via line 96 to storage tank 97. Fifty parts of linalyl diisobutyl borate are charged to reactor 100 via line 98 from a storage tank. Line 99 also charges a portion of the catalyst, in particular the orthovanadate ester of triethanolamine. This operation is carried out through the atmosphere,
It may be surrounded by a nitrogen atmosphere to eliminate the possibility of contamination from the atmosphere. The substances in the reactor 100 are
Heat to 160-165°C for 2 hours under stirring. At this point, the reactor contents are transferred to the water wash vessel 102 via line 1.
Transferred using 01. The water washing in the container 102 is performed in the container 3 in FIG. 1 except that a larger amount of water is required because boric anhydride is used in the operation in FIG.
The operation in step 7 is similar to that described above.
(Boric acid can be used as a liquid or as dry crystals.
Alternatively, it can be used as an aqueous slurry, which may be salvaged or new, or a mixture thereof. ) The overflow by the overpass device 106 is similar to the overflow through the overpass device 41 in FIG. The filtered wash liquor enters storage tank 109 via line 108, and the crude allylic alcohol product passes through line 10.
7 and enters the storage tank 110. Analysis of the crude product shows 16.95% linalool, 32.80% nerol and 50.25% geraniol, with neol and geraniol totaling 83.05%. Pot 112 is charged with crude product via line 111. Purifying distillation is carried out using pot 112 and its appurtenances in exactly the same manner as described in connection with pot 49 and its appurtenances in FIG. The present invention will be explained in more detail below. Catalysts that can be used in the process of the invention are catalysts containing vanadium. The proportion of catalyst used in the present invention per unit weight of allylic tertiary alcohol charged to the reactor is usually greater than 0.001%, preferably from 0.5 to about 2.0% of such alcohol. When determining the proportion of catalyzed preformed alcohologen, the proportion of catalyst is based on the equivalent weight of allylic tertiary alcohol of such alcohologen. No catalyst should be present when fractionally distilling the crude allylic alcohol product. This is to eliminate some of the product from reverting to allylic tertiary alcohol. Anything that produces strong acids during operation is usually harmful to allyl alcohols. Therefore, it is desirable to avoid such substances. For this reason, it is preferable to avoid the presence of unstable halogenated substances and sulfate or sulfate ester substances. Some useful catalysts require an induction period to allow at least a portion of these materials to be incorporated into the reaction mixture before operating at maximum activity. The isomerization of the present invention is preferably carried out at a wide temperature range of about 50 to 250°C (e.g., less harmful when using a mild catalyst of 1% hexyl orthovanadate or less and a stable alcohologen such as linalyl orthoborate). (Temperatures as high as 275°C are possible without becoming too hot). Preferably, the temperature is in the range of 140 to 180°C from the viewpoint of efficiency, economy, speed, and suppression of side reactions. The pressure of isomerization (for example, when removing alkanol from alcohologen as borate ester)
Preferably it is about 1 mmHg abs from atmospheric pressure. Higher pressures can be used to maintain the desired temperature. Liquid phase conditions will of course depend on the reactants. Although it is believed that the most effective catalytic reactions are carried out by homogeneous metal compounds, the catalyst can be introduced as a solid or as a solution of dissolved solids or a supported solid material. Reactants such as boric acid can be added as solids if desired. These esters are usually liquid, dissolved in the reaction mixture, or can be effectively brought into the liquid phase by dissolving in an additional organic solvent inert to the reaction. Such organic solvents are preferably used for example at useful operating pressures (1 mmHg
liquid aromatic or It is an aliphatic hydrocarbon. Other alcohologen esters can likewise be mixed into the reaction mixture or dissolved by the use of external inert solvents for this purpose. Alcohologens particularly useful for the isomerization of the present invention are esters, especially orthoborates (and metaborates, which are converted to orthoborates in the presence of more than 1 mole of alcohol per mole of equivalent boric acid in the metaborate). ),and,
Other metal or metal compounds such as orthotitanates, zirconates, orthosilicates, aluminum alcoholates, carbonates, stannates (e.g. copper tetraisopropoxide) and carboxylic acid esters, lanthanum alcoholates (e.g. lanthanum) isopropoxide), etc. The most unstable of these are the carbonate esters, which makes them more disadvantageous than the others. For the purposes of this invention, aluminum alkoxides are considered esters insofar as aluminum is amphoteric and its hydroxide dissolves in aqueous caustic soda to form sodium aluminate. Part b, a
and elements of group b are preferred. Lanthanum converts geraniol directly to citronellol in this method. Esters of such alkanols, advantageously
The C ₂₀ or less, preferably C ₄ -C ₈ alkanol is about
Wide range of temperatures from 150 to 250℃, preferably from 140 to
It is used to transesterify with allylic tertiary alcohols at 180°C, producing allylic alcohologens at the same time or before isomerization occurs.
N-butanol or isobutanol is the preferred such alkanol from a cost perspective, with the slightly more expensive sec-butanol also technically superior for operation at atmospheric pressure in multiple stages of processing. Esters of thiol carboxylic acids are also possible alcohologens, but these are much less practical than the oxyesters listed above due to cost and the potential for producing malodorous compounds. The alcohologen in the crude reaction product is cleaved to the alcohol in a variety of ways, but the best such method is hydrolysis using moderately high temperatures (80-90°C) and, if necessary, a base such as caustic soda. It depends. Cleavage can also be carried out by alcoholysis (using alcohols such as methanol), and carboxylic esters can also be cleaved by reaction with ammonia or secondary amines, releasing the alcohol. Generates amides. Another valuable alternative to aqueous hydrolysis of primary allylic borate esters (produced in this invention) to recover boric acid crystals or aqueous boric acid solutions is to produce other borate esters. This is alcoholysis. Alcoholysis with higher or lower boiling alcohols than the allylic alcohols present (eg, lineol, nerol, and geraniol) can be used. If a higher boiling alcohol is used, the allylic alcohol can be removed by distillation from the higher boiling alcohol's newly formed borate ester. Borate esters of such high boiling alcohols (eg, lauryl alcohol and myristyl alcohol) are expected to be valuable as heat transfer fluids and fuel additives. Alternatively, the alcoholysis of the allyl borate ester produced in the present invention can be carried out using a low boiling alcohol such as methanol. This methanolysis is carried out by adding about 10 to 50 moles of methanol per mole of allyl boric acid ester, followed by refluxing for 30 minutes at atmospheric pressure, as described in US Pat.
This can be done by distillation under atmospheric pressure as described in No. 3117153. under atmospheric pressure
Distillates within the boiling range of 55-78°C will contain trimethyl borate and methanol. This distillate can be split into a trimethyl borate-methanol azeotrope fraction and a methanol fraction by fractional distillation as described in U.S. Pat. No. 3,117,153. The trimethyl borate-methanol azeotrope fraction may be further salted out with lithium chloride or calcium chloride to produce a pure trimethyl borate fraction if desired. Both trimethyl borate and its methanol azeotrope are valuable commercial products and have uses, for example, as boric acid esterification agents and fuel additives.
For example, the recovered trimethyl borate, which is used in moderate excess for boric acid esterification of linalool, becomes a useful boric acid esterifying agent in the method of the present invention for producing such a raw material tertiary allylic alcohologen. It is expected that there will be more deafness. Just above, two types were outlined _specifically for boric acid and orthoboric acid esters;
It is expected that zirconates, orthosilicates and titanates of higher boiling alcohols, such as aluminum alcoholates and lauryl alcohol (above), as well as orthosilicates and titanates, may be used as well. Although hydrolysis is a very useful reaction for converting allylic alcohologen reaction products to the corresponding alcohols, many other reactions of such alcohologens are possible. Otzpenauer oxidation of carbonyl compounds with these is possible. Thus, aluminum geraniolate and nerolat (preferably substantially free of alkanol groups and mixtures with free alkanols) are 55
It can be reacted with excess and acetone at temperatures of ~60 °C (or higher under pressure) to produce pseudoionones (via the intermediate citral), and can also be reacted with furfural at temperatures of about 40 °C to yield citral. [U.S. Patent No.
See No. 4055601 (WJEhmamn)]. Other possible reactions using allylic alcohol products would be amination and hydrolysis with ammonia or amines followed by oxidation using, for example, aqueous chromic acid. Another unique and valuable isomerization related to the present invention relates to the production of high purity linalool from nerol and/or geraniol. Linalool produced from α-pinene contains several by-products such as purinols and phenols that are difficult to remove by fractional distillation. The distillation equipment used to produce very high purity perfume linalool therefore requires substantial capital investment and operating costs. However, linalool provides high conversion of nerol and geraniol as shown herein. All of these alcohols can be easily separated from each other by fractional distillation. Traditionally, geraniol has been used because it has a more pleasant odor and is easier to process into valuable products such as citronellol, citronellal, and citral.
Of these two primary allylic alcohols, it was always the more valuable. Nellore, on the other hand, has less value. Thus, this conversion to linalool could be commercially attractive. Linalool has the lowest boiling point among the three types of allyl alcohols produced by the metal catalytic isomerization method of the present invention. Its removal from the reaction equilibrium was equipped with a distillation column capable of efficiently separating linalool from nerol and/or geraniol. This can be achieved by isomerizing nerol (and/or geraniol) in a reactor. This technology can be easily adopted with commercially available processing equipment;
The fact is that long reaction times of ~12 hours promote the formation of dimeric products due to the reaction of the primary alcohol present with the vanadium or other catalytic metal present. The use of neryl and/or geranyl borates as raw materials to produce linalool is due to the chemical stability of these esters in the presence of active metal-supported isomerization catalysts such as orthovanadate esters. Like very attractive. These catalytic esters will be in equilibrium with the linalyl borate ester (or other linalyl ester alcohologen), but such equilibrium is influenced by the active metal catalyst. Linalool is then conveniently driven from its borate ester by adding a stable alcohol that does not isomerize in the presence of an active metal catalyst. Such alcohol should preferably have a higher boiling point than linalool. Examples of such alcohols are decanol, lauryl alcohol, myristyl alcohol, and the like. Other embodiments of producing relatively pure linalool by isomerization of nerol and/or geraniol include reacting higher boiling secondary or tertiary alcohols with boric acid to produce boric acid esters. A vanadium catalyst, such as trihexyl orthovanadate, is introduced in a catalytic amount to the reaction mass. Nerol (or geraniol), a primary alcohol, is added, which displaces the higher boiling secondary or tertiary alcohol from the borate ester,
Produces neryl (or geranyl) borate. Neryl (or geranyl) borate is isomerized in the presence of a vanadium catalyst, resulting in an equilibrium containing a small amount of linalyl borate. The higher boiling point secondary or tertiary alcohol then displaces the linalool and tertiary alcohol from the linalool borate to liberate linalool. Linalool, which has the lowest boiling point, is removed by fractional distillation. Continuously introducing nerol (and/or geraniol) at a rate corresponding to linalool production enables continuous production of relatively high purity linalool. Other methods of this process for producing linalool from nerol and/or geraniol via borates or similar very stable esters (silicates, aluminates, titanates, stannates or zirconates) The point of view is that the isomerization is carried out in the presence of such stable esters of primary (or secondary) alcohols such as decanol, lauryl alcohol or myristyl alcohol. For convenience, the procedures are described below with respect to borate esters. The first boric acid ester charge is trilauryl borate. In such reaction examples, the active metal catalyst would be dissolved in the reaction mixture at 160-180°C. Nerol and/or geraniol is then charged at a controlled rate to the reaction medium in which it can react with lauryl borate to form neryl borate bonds. Such metal catalytic isomerization of neryl borate produces the corresponding linalyl derivative. Linalool is displaced from the borate ester by the primary alcohols present, nerol and lauryl alcohol. The free linalool thus produced is removed via a fractional distillation column provided on the reactor. The pressure during the treatment was reduced (10 to 100 mmHg) to sufficiently evaporate linalool from the reaction medium at a temperature of 140 to 180 °C.
abs). The overall value of this mode of operation for producing linalool from nerol and/or geraniol is that
This consists in the fact that free nerol and/or geraniol in the long processing times typical of the cited processes or in the presence of metal isomerization catalysts is avoided. Rather, this "reverse" isomerization occurs primarily through stable alcohologens, which are chemically more stable under the reaction conditions. Only the allylic tertiary alcohol, such as linalool, needs to be consumed (excluding very small losses) of the solvent of the reaction used in the process of the invention; ) Of particular note is the production of allylic primary alcohols and allylic secondary alcohols (such as trans-piperitol from trans-2-menthen-1-ol). Even the catalyst remaining in the boric acid solution remains for reuse. It is possible to recover other catalysts or catalyst-forming substances (from the percake and/or distillation residue), but it is usually not economical to do so here. The following examples show various methods of implementing the present invention in glass, but these are not intended to limit the present invention. In most cases,
These outline the research and development that has been undertaken to arrive at the best mode for operating the two major aspects of the invention. Such formats are described in connection with the above-mentioned figures. As used herein, all parts are by weight, all percentages are mole percentages, and all temperatures are in degrees Celsius, unless indicated otherwise. The experimental reactor used for isomerization was a three-necked glass flask equipped with a thermowell for temperature sensing, a stirrer heating mantle, and a Barret collector, which collected vapors from the flask. The condensate is then raised through a short column with an indirectly water-cooled condenser installed at the top of the column, allowing the condensate to flow down the column and finally to a vertical leg, where the condensate is liquid, especially a distinct aqueous phase, could be discharged. Unless otherwise noted, condensers were open to atmosphere. In those isomerization experiments indicated as being conducted under reduced pressure, the condenser vapor outlet was connected to a vacuum line. Vacuum distillation was used in some of the experiments to separate and/or regenerate alkanols. In such instances, a short 20.3
An 8 inch (cm) Vigreaux fractional distillation column was used. Steam from the distillation column enters the condenser;
The condensate from the condenser could be refluxed to the top of the column and/or the distillate product could be discharged.
The steam exhaust pipe of the condenser was connected to a vacuum line to obtain reduced pressure if necessary. Analysis of the crude and intermediate products was carried out by measuring the alcohol obtained by gas chromatography of aqueous samples hydrolyzed with NaOH. The molar ratio of geraniol to nemol in a hydrolyzed sample is typically
It showed 62 parts of geraniol to 38 parts of nerol. Unless otherwise specified, the linalool charged for isomerization was approximately 95% pure technical grade, with the remainder being primarily purinol.
IR analysis was also used throughout. Example 1 154 g of linalool in a flask (reaction pot), 100 g
cc of toluene, 163 g n-butanol, 62 g boric acid, and 0.3 g ammonium metavanadate were charged. The mixture was stirred and heated to maintain it at 160° C. for 8 hours, after which the organic material and water were distilled off under atmospheric pressure using a collector. A sample of the product showed that 82.9% of the allylic alcohols present were geraniol and nerol. Then 308 g of fresh linalool and 25 c.c. of fresh toluene were added to the flask and 160 c.c.
The operation was continued for an additional 8 hours at 0.degree. C., and then the temperature of the reactor was gradually increased to 180.degree. C. over a further 8 hours. The sample showed that 72.4% of the allylic alcohols present were geraniol and nerol. The crude isomerization batch was stirred with 55 g of tap water at 60°C for 4 hours, an additional 200 g of tap water was added, stirred for another 15 minutes at 80-90°C, and finally an additional 10 c.c. of tap water was added to the batch. and mix, then let the mixture stand still in a separatory funnel heated with a heat lamp,
Finished by draining the water (bottom) layer. The remaining oil layer was washed twice with 50 c.c. of tap water each time. The lower layer and the resulting wash were combined and filtered to remove the vanadium-loaded sludge, and its boric acid and other valuables in subsequent operations were retained for reuse. The washed oil layer was subjected to fractional distillation under reduced pressure using the Viclot column described above. 1 g of potassium stearate was mixed with the distilling agent. First distillation is 100mmHg
Most of the operations were done with abs. Stripping the residue first with 1mmHg abs and finally with 0.2mmHg
I did it with abs. The aqueous layer and solution were combined and saved for reuse. The combined aqueous layer and water washes were used in a similar procedure to that of Example 1, except that most of the water from such recycle was removed by azeotroping the linalool with toluene before charging it to the flask. . The allylic alcohol of the product is 65% geraniol and nerol (24.5% nerol and 40.5%
geraniol) and 35% linalool. Approximately 90% of the allylic alcohol in the product in the connecting operation removes alkanol in larger quantities
% of geraniol and nerol. Example 2 154 g of linalool and 50 c.c. of toluene were added to a flask equipped with a bullet water collector. The solution was refluxed under atmospheric pressure to 160° C. with removal of water and finally toluene. The solution was then cooled to 90°C, at which point 1.5g of orthovanadate of triethanolamine and 77g (1/3
Tri-sec-butyl borate (mol/mol linalool) was added. The reaction was then heated to 160° C. under atmospheric pressure and maintained at reflux with removal of toluene and sec-butyl alcohol as necessary. Samples were removed after 4 hours at 160°C. This was a molar ratio of linalool to citral to nerol + geraniol of 30.7:0.3:69.0. After 8 hours, the corresponding ratio was 22.3:1.7:75.9. Only trace amounts of the dimeric product were observed by gas chromatography. other vanadate esters,
For example, the use of trihexyl vanadate produces less citral. The reaction was repeated under the same conditions except that tri-sec-butyl borate was not used. The ratio of linalool to citrol to nerol + geraniol was as follows.

Table: It was observed (using chromatography) that a substantial amount of dimeric product was formed. The 8 hour product was steam distilled to separate the alcohol from the non-volatile dimer residue. The amount of such residue is
It was found to be 24.4%. These data not only demonstrate the utility of the borate esterification technique to greatly improve the conversion of linalool to nerol + geraniol, but also demonstrate its valuable protective effects. Little or no citral is produced and dimer losses are greatly reduced. Typically at high conversions to nerol + geraniol the loss to dimer is about 5
~7%. Example 3 A flask was charged with 50.0 g of substantially pure linalyl dibutyryl borate and heated to 160°C. 1.0 g of triethanolamine orthovanadate (OVTEA) was added to the hot liquid and the mixture was stirred at 160-162° C. for 2 hours. The product was then cooled and hydrolyzed with 100 ml of 5% aqueous sodium hydroxide solution. Allyl alcohol analysis showed the product to contain 16.95% linalool, 32.80% nerol and 50.26% geraniol. 1 mol of linalyl dibutyl borate
It is produced by reacting linalool with a purity of 95% or more and 1.1 mol of tributyl borate under reduced pressure (100 mmHg abs), and the butyl alcohol is removed at 140°C, and then further at 140°C and under a pressure of 10 mmHg abs. Excess tributyl borate and substantially all volatiles were removed by heating. Example 4 77 g of approximately 95% pure linalool and 50 c.c. of toluene were added to a flask equipped with a collector. Traces of water were then removed by heating the solution to reflux under atmospheric pressure. Toluene was then removed until the flask contents temperature reached 160°C under reflux.
The solution was cooled to 100° C. and then 0.75 g trihexyl orthovanadate and 68 g methyl benzoate were added. The benzoate ester present was then hydrolyzed by heating the reaction in a 25% sodium hydroxide solution in the usual manner under atmospheric pressure. Analysis of the hydrolysis product by gas chromatography revealed that 45.3% of the allylic alcohol present was linalool, and 54.7% was nerol and geraniol. Example 5 77 g of approximately 95% pure linalool and 50 c.c. of toluene were added to a flask equipped with a stirrer and a distillation head. Heat the solution to reflux and add some toluene (to remove traces of water) until the pot temperature is 160°C.
It was removed until it was. The reaction was cooled to 90°C and then 0.8g trihexyl orthovanadate and 68g diethyl carbonate were added. The reaction was then heated to reflux to bring the pot temperature to 120°C. The distillate temperature was maintained above 110° C. by periodically withdrawing small amounts of distillate. After heating at 120°C for a total of 31 hours, a sample of the flask contents was analyzed for the presence of nerol + geraniol vs. nerylethyl carbonate + geranylethyl carbonate vs. linalool.
It turned out to be 29.4:25.2:49.9. These ratios indicate that substantial amounts of nerol and geraniol were removed from the equilibrium system by transesterification with diethyl carbonate. The carbonate ester present was hydrolyzed by heating the reaction mixture to reflux under atmospheric pressure with a sufficient amount of 25% aqueous sodium hydroxide in a conventional manner. Approximately 50% of all allylic alcohols present
of nerol and geraniol and 50% linalool. Example 6 18.5 g of approximately 95% pure linalool, 40 g of n-octyl acetate, and 50 c.c. of toluene were added to a flask equipped with a collector. The solution was refluxed at 140° C. under atmospheric pressure to remove traces of water and toluene.
A sample was taken from the solution and analyzed by gas chromatography and found to be 27.4% toluene, 49.6% n-octyl acetate, and 21.7% linalool. 0.6% trihexyl orthovanadate was added to the cooled solution. The reaction was then heated to 140°C.
Heated for 28 hours. Gas chromatography analysis of the reaction showed 26.2% toluene, 39.9% n-octyl acetate, 6.5% linalool, 10.1% n-octanol, 3.2% nerol and geraniol, and 11.6% nenyl acetate and geranyl acetate. Ta. (No correction factors were introduced in this analysis to take into account the differences in the responses of octyl acetate and octanol and the responses of linalool, nerol + geraniol and neryl acetate + geranyl acetate.) Linalool vs. nerol + geraniol and their The ratio of the total amount of acetate ester is 30.9:69.5. Hydrolysis of the esters in conventional manner will produce the corresponding allylic alcohols, linalool, nerol and geraniol. Example 7 15.4 g of linalool and 25 c.c. of toluene were added to a 100 ml 3-necked flask equipped with a water collector.
Traces of water were removed by heating the solution under atmospheric pressure, and the reactor temperature was finally brought to reflux temperature of 140°C. After the solution was cooled to 100° C., 20.8 g of tetraethyl silicate and 0.2 g of trihexyl orthovanadate were added thereto. The reaction was then brought to a kettle temperature of 160° C. at atmospheric reflux by removing toluene and driven off ethanol. After 4 hours at 160°C, analysis of the batch showed substantial conversion of linalool to neryltriethyl silicate and geranyltriethyl silicate. The resulting ratio of linalool to nerol + geraniol to neryltriethyl silicate + geranyltriethyl silicate was 3.3:2.3:94.4. The crude alcoholic product to be purified was obtained by hydrolysis of the silicate ester therein by refluxing the reaction product with 50% aqueous sodium hydroxide solution. Example 8 41 g of linalool was placed in a 500 ml one-neck flask with a polytetrafluoroethylene coated magnetic stirrer connected to a condenser and a distillation head. Then linalool was added at a pressure of 100 mmHg abs.
It was dried by heating to 140°C. After 1 hour, the flask was cooled to approximately 90°C and to it was added 110 g of aluminum isopropylate as a 50% toluene solution.
A Vigreux column was attached to the flask as described above. The flask was then heated at a temperature of 120 °C under atmospheric pressure to obtain 15 g of distillate with a boiling point range of 82-83 °C. This was thought to be primarily toluene.The flask was then cooled, placed under a pressure of 100 mmHg abs, and heated to 120°C to release 51 g.
A distillate with a boiling range of 45-52°C was obtained. Cooling of the flask and analysis of a sample of the solution by infrared spectroscopy revealed that there was virtually no free linalool, but that the linalool had instead displaced a substantial amount of isopropanol from its bond with the aluminum. Indicated. Then 0.4 g of trihexyl orthovanadate was added to the reaction mixture. The reactants are then 140
It was kept at ℃ for 36 hours. IR analysis of the clear solution showed that any OH absorption typically located at 3500 cm ^-1 was virtually absent. Hydrolysis of the sample with 50% aqueous sodium hydroxide gave an alcohol-oil layer, which showed the presence of 29.4% linalool, 22.1% nerol and 38.9% geraniol by gas chromatography analysis. The ratio of linalool to nerol + geraniol is 32.5.
It was 67.5. Example 9 154 g of linalool and 50 c.c. of toluene were added to a flask equipped with a collector. The solution was then refluxed under atmospheric pressure to remove traces of water. solution
Cooled to 90°C at which point 1.5g of trihexyl orthovanadate was added. Then the reactants
Heating to 160°C and removing toluene under atmospheric pressure,
It was held at 160°C for 1 hour. At this point, we analyzed the ratio of linalool to nerol + geraniol.
78:22. Then 136 g of 50% aluminum isopropoxide in toluene was added after the reaction had cooled to about 120°C. The reaction was heated to reflux at 140°C. After heating at 140°C for 5 hours, the sample was removed, washed with 25% sodium hydroxide solution, and then analyzed by gas chromatography to determine the ratio of linalool to nerol + geraniol of 61:39.
It turned out to be. 100 c.c. of toluene was then added and the toluene and isopropanol were distilled off from the reaction mass under atmospheric pressure and brought back to 140°C. The reaction was held at 140° C. for 10 hours, at which point it was analyzed and the ratio of linalool to nerol + geraniol was found to be 25:75. Again 100 c.c. of toluene was mixed into the reaction and then
Substantially all isopropanol present was removed by heating to reflux at 140°C. The reaction was kept under reflux at 140°C for an additional 4 hours. When the reactants were analyzed as described above, it was found that the ratio of linalool to nerol + geraniol was 13:87. 600 c.c. of dry acetone was added to the reaction mixture to establish a favorable perspective for the formation of aluminum alkoxides of nerol and geraniol to alter the equilibrium. The reaction was then heated to reflux under atmospheric pressure for 3 hours. Analysis of the crude reaction product by gas chromatography revealed that linalool vs. nerol + geraniol vs. cis- and trans-
It was found that the ratio of pseudoionone was 15.0:4.36:41.6. The reaction was then treated with 350 c.c. of H ₂ SO ₄ solution at room temperature and washed twice with 300 c.c. of water. The recovered oil layer was then heated under reduced pressure (1 mm from 10 mmHg abs during distillation).
A distillate was obtained by refluxing through a Vigreux column with Hg (reduced to abs) and contained 13.5 g of linalool, 44.3 g of nerol + geraniol and 41.4 g of cis- and trans-pseudoionones as determined by gas chromatographic analysis. Ta. Example 10 25 g of nerolidol containing cis- and trans-isomers with approximately 95% purity and 50 c.c. of toluene were added to a flask equipped with a water collector. Traces of water were removed by refluxing the solution at 120° C. under atmospheric pressure. Cool the solution to 90 °C, at this point
0.25g trihexyl orthovanadate and
26.0g of triisobutyl borate was added. The reaction was then refluxed at 160° C. by distilling off the toluene and isobutanol that was driven into the reaction. After 8 hours at 160°C, the borate ester was hydrolyzed by treating the reaction sample with dilute sodium hydroxide solution. Gas chromatography analysis of the hydrolyzed sample showed that the ratio of nerolidol to faarnesol was 19.4:80.6. Corresponding reactions were carried out under identical conditions except that no triisobutyl borate or other similar agents were added. After 8 hours at 160°C, the ratio of nerolidol to faarnesol was 68.6:31.4. Example 11 20 g of trans-2-menthen-1-ol, approximately 93% pure, and 25 c.c. of toluene were added to a flask equipped with a water collector. The solution is heated to 155-160 mL at atmospheric pressure by removing toluene and traces of water.
It was refluxed at ℃. The solution was then cooled to 100°C, at which point 0.2g of trihexyl vanadate and
16.5g of tri-n-butyl borate was added. The reaction was heated to reflux with a pot temperature adjusted to 160° C. by removing butanol and toluene during the subsequent distillation. After 2 hours under reflux, a sample was removed, hydrolyzed and analyzed by gas chromatography (uncorrected for response factors): 1.8% toluene, 50% n-butanol, 4.8% p-menthadienes, 27.9 % trans-2-menthen-1-ol and 47.2% trans-pepilitol. The procedure was repeated in exactly the same manner except that tri-n-butyl borate or similar agents were not used. After 1 hour at 160°C, there was a substantial amount of dehydration and formation of p-menthadienes. The batch was analyzed by gas chromatography to contain 21% toluene, 12.9% p-mentadienes, 36.9% trans-2-menthen-1-ol, and 10.5% trans-piperitol. These data indicate that the boric acid esterification agent not only enabled the production of higher amounts of trans-piperitol, but also had a protective effect because stabilization against dehydration occurred as a result of the boric acid esterification. Example 12 154g linalool, 100c.c. toluene, 163g
of isobutanol, 62 g of boric acid, and 1.5 g of trihexyl orthovanadate were added to the flask and refluxed under atmospheric pressure. The reflux temperature is gradually increased to 94°C until 54.2g of water is separated from the toluene azeotrope.
The temperature rose from 145℃ to 145℃. The reaction mass was then heated to reflux at 160° C. under atmospheric pressure with removal of toluene and kept at this temperature for 8 hours. Gas chromatography analysis of the hydrolyzed reactant sample showed the allylic alcohol composition to be 11.3% linalool and 88.7% nerol+geraniol. This reaction shows the advantageous effect obtained by using a 1:1 molar ratio of boric acid to linalool. If a larger amount of linalool was used at this time, so as to change the corresponding ratio to 1:3, the reaction mass would take an additional 8 hours at 160° C. and atmospheric pressure to isomerize to give the product, but Gas chromatographic analysis of a hydrolyzed sample of this will yield approximately 25-30% linalool and 70-75% nerol+geraniol. Higher conversion of linalool to nerol+geraniol could be achieved by removing butanol from the reaction mixture by distillation under reduced pressure. The metal-containing isomerization catalyst useful for the isomerization of allylic tertiary alcohols to allylic primary or secondary alcohols is or carboxylic esters and other esters, carboxylic esters and alcohols or carboxylic esters and other carboxylic esters. It appears to be effective in catalyzing transesterification with acids. Polyacids, polyols and polyesters as well as monobasic or monofunctional substances can be used here. Vanadium and tungsten compounds are most useful for such operations. This is of moderate assistance if these are readily soluble in the reaction mixture. If the reaction products can be removed, this of course serves to shift the equilibrium to the residual products remaining in the reaction mixture. The following examples illustrate typical such operations. Example 13 Two identical flasks were prepared separately, and each
57 g of n-octyl acetate, 39 g of 98% geraniol and 50 c.c. of toluene were added. Both were refluxed at 140°C by removing excess toluene from the bullet collector. 0.5 g of ammonium metavanadate was added to one side of the briefly cooled flask. These two reactors are placed under atmospheric pressure.
The mixture was refluxed at 140°C for 16 hours. At the end of this time a sample was removed from each. Gas chromatographic analysis of the reaction conducted in the absence of ammonium metavanadate showed that virtually no reaction occurred. On the other hand, a similar analysis of the reactants containing the vanadium catalyst showed 47.9% n-octyl acetate, 14.2% n-octanol, 6.9% linalool, 2.9% neryl acetate, 21.6 g geranyl acetate, and 4.2% geraniol. showed its existence. These data demonstrate that vanadium catalysts are not only effective for isomerizing allylic alcohols, in this case between geraniol and n-octyl acetate, but may also be highly effective catalysts for promoting transesterification. It is shown that. Example 14 This example illustrates the use of tin alkoxide as a protecting group for the isomerization of linalool to geraniol. Thirty-one grams of linalool, approximately 95% pure, was refluxed with 100 c.c. of toluene in a 3-necked flask equipped with a stirrer and an 8-inch Vigreux column. Above the column, the reflux was cooled with a glass water condenser and returned to the reaction flask. Any water present or formed during the reaction was removed from the distillate by the use of a bullet collector between the column and the condenser. 140 by removing toluene from the distillate
A pot reflux temperature of °C was obtained. Infrared analysis of the hot contents showed the presence of linalool. then 60
g (Bu ₃ Sn) ₂ O was added and about 1 c.c. of free water was taken up in the distillate. After refluxing for 2 hours, the contents of the pot were analyzed by infrared spectroscopy. Substantially all of the linalool had reacted to form linalyltributyl stannate. At this point, 1.0 g of trihexyl vanadate was added and the reaction was heated at 140<0>C for 6 hours, then heated longer at 165-175<0>C for 12.5 hours. The sample was removed and the stannate was hydrolyzed by steam distillation, and the terpene alcohol was removed from the tin residue. Gas chromatographic analysis of the oil showed a composition of 49.6% nerol/geraniol of the terpene allylic alcohols present. Example 15 This example illustrates the use of zirconium acid as the alcohologen. Zirconate, like titanic acid in Example 10 above, appears to isomerize nerol and geraniol to isogeraniol, with a small amount of citronellol formation. A 250 ml three-necked flask was equipped with a 10 c.c. bullet collector attached to a water-cooled glass condenser. Stirring was performed using a Teflon-coated magnetic stirrer rod. Approximately 95% purity in flask
38.5g linalool and 50ml heptane were added. The contents were refluxed for 30 minutes and water was removed by azeotropic distillation. Cool the solution quickly and add 28.5 g
of tetra-n-butyl zirconate was added. The solution was brought to reflux at 160° C. by removing distillate from a bullet collector. The solution was kept at 160° C. for 2 hours, at the end of which time a sample was removed and subjected to hydrolysis followed by gas chromatographic analysis. Isomerization of linalool to geraniol did not occur. After adding 1.0 g of tri-n-hexyl orthovanadate catalyst, the solution was then held at reflux for 4 hours at 160°C. When the sample was taken out, hydrolyzed, and analyzed by gas chromatography, the result was 53.6:
It had a ratio of linalool to nerol, geraniol and other isomeric primary alcohols of 46.4. cis- and trans-3,7-dimethyl-3,6-
Octadien-1-ol and 7-methyl-3-
All of these isomers, such as methylene-6-octen-1-ol, are useful in the production of perfume alcohols, citronelle and dimethyloctanol, by catalytic hydrogenation processes.

[Brief explanation of drawings]

FIGS. 1 and 2 are process flow diagrams outlining the main application examples of the present invention, respectively. 12,26,49...Reaction pot, 13,27,5
1... Distillation column, 16, 24, 54... Condenser, 4
1... Passer, 37... Water washer, 44, 47...
Storage tank, 62, 71, 84, 100, 112... Reaction vessel, 63, 72, 86, 113... Distillation column, 6
5, 76, 89, 116... Condenser, 106...
Filter vessel, 102... Water washer, 82, 97, 10
9,110...Storage tank.

Claims (1)

[Claims] 1. A method for producing an isomer allylic primary, secondary, or tertiary alcohol of a different series from the starting allylic primary, secondary, or tertiary alcohol from a starting allylic primary, secondary, or tertiary alcohol, including: ( i) forming a reaction mixture for isomerization comprising a precursor of said raw alcohol which is an ester or alcoholate of an acid or hydroxide of an element of Group 1 or Group of the Periodic Table of the Elements; (ii) containing vanadium; isomerize the precursor of the raw alcohol by subjecting it to liquid phase catalytic isomerization conditions in the presence of a catalyst; and (iii) cleave the resulting isomerized allylic precursor to obtain the desired isomer. A method for producing an allyl alcohol, characterized in that: obtaining an allyl alcohol product. 2. The method of claim 1, wherein the reaction mixture further comprises a non-allylic alcohol having a different vapor pressure than either the raw allylic alcohol or the isomeric allylic alcohol product. . 3. The method of claim 2, further characterized in that the temperature at which the isomerization reaction is carried out is sufficiently high to distill off the non-allylic alcohol and the isomeric allylic alcohol product. . 4. A non-allylic alcohol in which the isomer allylic alcohol product has lower volatility than the raw allylic alcohol, and the isomerization mixture has a vapor pressure greater than the vapor pressure of the isomer allylic alcohol product. The method of claim 1 further comprising: 5. said isomeric allylic alcohol product is more volatile than the raw allylic alcohol, and said isomerization mixture has a non-allylic alcohol having a vapor pressure lower than the vapor pressure of said isomeric allylic alcohol product. The method according to claim 1, which also includes: 6. The method of claim 1, wherein the isomeric allylic alcohol product is a primary allylic alcohol. 7. The method of claim 1, wherein the precursor of the arylic tertiary alcohol is preformed before isomerization, and at least one of the allylic residues of the precursor has a tertiary conformation. 8. The method according to claim 7, wherein all the allylic residues of the precursor of the allylic tertiary alcohol have a tertiary conformation. 9. Claim 8 further comprising decomposing any allylic alcohol precursors remaining after isomerization to obtain an allylic alcohol product.
The method described in section. 10. The method of claim 6, wherein the alcohol precursor of the allylic primary alcohol product is formed simultaneously in the reaction mixture with isomerization of the alcohol precursor. 11. The method of claim 6, wherein the alcohol precursor is a hydrolyzable ester. 12. The method according to claim 11, wherein the ester is an allyl borate ester. 13. The boric acid ester is further characterized in that the boric acid ester is produced by transesterification of a boric acid ester, and when the alkanol moiety of the boric acid ester is liberated, its boiling point is equal to that of the allylic alcohol product. 13. The method according to claim 12, wherein the boiling point is lower than the boiling point of . 14. The method of claim 13, further comprising cleaving the alkyl borate into primary and/or secondary alkanols. 15 The precursor is a precursor of linalool,
7. The method of claim 6, wherein the desired isomeric allylic alcohol products are geraniol and nerol. 16. The method of claim 15, wherein the linalool precursor is formed from butyl borate. 17. The method of claim 16, wherein the butyl borate is isobutyl borate. 18 Claim 5, wherein the isomeric allylic alcohol product is an allylic tertiary alcohol.
The method described in section. 19. The method according to claim 18, wherein the allylic tertiary alcohol is linalool. 20. The method according to claim 5, wherein the precursor of the raw allylic alcohol is a precursor of an alcohol selected from nerol, geraniol, and mixtures thereof. 21. The method of claim 20, wherein the alcohol precursor is a hydrolyzable ester. 22. The method of claim 21, wherein the hydrolyzable ester comprises a boric acid ester. 23 Perform the isomerization reaction under reduced pressure and at about 140°C to about 180°C.
5. The method according to claim 4, which is carried out at <0>C. 24. The method of claim 5, wherein the non-allylic alcohol is lauryl alcohol. 25. The method according to claim 1, wherein the precursor is an allyl borate ester. 26 (i) forming a reaction mixture for isomerization comprising a precursor of an allylic tertiary alcohol selected from esters or alcoholates of acids or hydroxides of elements of groups or groups of the periodic table; (ii) isomerizing the mixture into precursors of allylic primary and/or secondary alcohols by subjecting said mixture to liquid-phase catalytic isomerization conditions in the presence of a vanadium-containing catalyst; and (iii) the resulting isomerization. The method according to claim 1, which is a method for allylic rearrangement of allylic alcohols, characterized in that the converted allylic precursor is cleaved to obtain the desired isomeric allylic alcohol product. 27 (i) forming an isomerization reaction mixture comprising a non-allylic alcohol having a different vapor pressure than either the isomeric alcohol product or the feed alcohol and a precursor of the feed alcohol; and (ii) a vanadium-containing catalyst. isomerizing the allylic alcohol precursor by a liquid phase rearrangement reaction in the presence of a liquid phase rearrangement reaction at a temperature high enough to distill off the non-allylic alcohol and one of the isomeric alcohol products. The method according to claim 1, characterized in that; 28 (i) forming a reaction mixture for the isomerization of the allylic alcohol precursor of the feed allylic alcohol having lower volatility with the non-allylic alcohol; and (ii) in the presence of a vanadium-containing catalyst; isomerizing said precursor by a liquid phase rearrangement reaction at a temperature high enough to distill off the higher volatility allylic alcohol product; characterized by the production of allylic alcohol products with higher volatility from allylic alcohols,
A method according to claim 1. 29. The method of claim 6, wherein the allylic primary alcohol is nerol. 30. The method of claim 6, wherein the allylic primary alcohol is geraniol. 31. The method according to claim 6, wherein the raw material allylic tertiary alcohol is linalool.