CN1546449A - Process for producing geranyl acetone - Google Patents
Process for producing geranyl acetone Download PDFInfo
- Publication number
- CN1546449A CN1546449A CNA2003101064483A CN200310106448A CN1546449A CN 1546449 A CN1546449 A CN 1546449A CN A2003101064483 A CNA2003101064483 A CN A2003101064483A CN 200310106448 A CN200310106448 A CN 200310106448A CN 1546449 A CN1546449 A CN 1546449A
- Authority
- CN
- China
- Prior art keywords
- reaction
- geranyl acetone
- methyl aceto
- reaction solution
- aceto acetate
- 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.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a process for preparing geranyl acetone which comprises, mixing acetoacetic acid ethylester with organic aluminium catalyst 0.1%-10% wt% of the acetoacetic acid ethylester, heating to elevate the temperature to 70-250 deg. C, charging linalool 1.0-2.0 times by mole number of acetoacetic acid ethylester, obtaining reaction solution and distillate, finally purifying the reaction solution. The advantages of the invention are easy reaction control, low raw material deterioration, and increased product yield.
Description
One, technical field
The present invention relates to a kind of processing method of making geranyl acetone.
Two, background technology
Geranyl acetone is one of ketones derivant of acyclic isoprenoid.Say that in general sense the geranyl acetone that industrial production obtains is meant by cis-isomeride (being also referred to as neryl C10H17-acetone) and these two mixtures that isomers is formed of trans-isomer(ide) (also can be described as geranyl acetone).Its odour characteristics is a scent type.In cigarette, can increase cigarette perfume (or spice), play coordinative role.Be prevalent in flue-cured tobacco, burley tobaccos and the Turkish tobaccos, external perfumers are widely used for it among cigarette essence.Also can be used as other foodstuff essence and detergents and cosmetic category raw material for essence uses.Simultaneously, the prior intermediate that also is to can be used as synthesising complex E etc. uses, and is an important fragrance material and intermediate materials.
In the synthetic method of knowing altogether, having the allyl group tertiary alcohols compound of a fixed structure such as phantol and acetoacetic ester such as methyl aceto acetate and carry out the synthetic ketone compounds that increases by 3 carbon atoms of Carroll reaction under the katalysis of known catalyzer aluminum isopropylate, is a relatively more classical building-up reactions.The synthetic geranyl acetone that obtains having increased than phantol 3 carbon atoms, this is one of important representative of this class reaction.Known geranyl acetone synthetic method is that phantol and methyl aceto acetate carry out Carroll reaction and finish under aluminum compound katalysis such as aluminum isopropylate.Though this building-up reactions once mentioned in many patents, in China continuously in several the patents of application, special patent application at this building-up reactions does not but have such as, German BASF AG.
What C. oersted etc. related in CN1251832 is a kind of continuous method for preparing beta-unsaturated ketone that comprises the special reaction device, various unsaturated alcohols and various Acetacetic acid alkyl ester (mol ratio 0.8～1.2) react in separation column, generate the acetylacetic ester of unsaturated alcohol, the alcohol of Chan Shenging steams (cat head separation) through cat head in addition; At tower bottom, the acetylacetic ester of unsaturated alcohol forms beta-unsaturated ketone (separating 120～300 ℃ of column bottom temperatures at the bottom of the tower) through the organoaluminum catalytically rearranging, discharges CO simultaneously
2(returning use), residence time of material 0.25～6h.
That C. oersted etc. relates generally in CN1271716 is the preparation method of higher unsaturated ketone, be the α of various replacements, beta unsaturated alcohol (high-carbon) carries out the Carroll reaction with the Acetacetic acid alkyl ester of various replacements in the presence of 0.1～0.5% organo aluminum catalyst.Its process modification is mainly reflected in, and adds Acetacetic acid alkyl ester or logical inert gas flow by mixing nozzle, with mixing and the promotion distilling alcohols by product that improves mixture, the CO of rare gas element or recovery
2Returning reactor recycles.
S. Kai Shamumo etc. relates to uncle's vinyl carbinol and alkenyl alkyl ethers prepared in reaction γ in CN1228757, the method for delta unsaturated ketone, and the main phosphorated acid catalyst that is to use is as phenyl-phosphonic acid, phenylbenzene phosphonic acids, phosphoric acid phenylester, di(2-ethylhexyl)phosphate phenylester etc.
H. CN1348434 such as Jie Dike, what relate generally to is with Karol prepared in reaction γ, delta unsaturated ketone, the Acetacetic acid alkyl ester of various replacement vinyl carbinols or propargyl alcohol and various replacements (mainly referring to ester) with high-boiling point alcohol formation, 150～220 ℃ of reactions (organoaluminum is a catalyzer), and distilling out the alkanol (boiling point is greater than 140 ℃) of generation simultaneously, method is simple, technology is continuous, can shorten the reaction times and further improve productive rate.
H. the Ai Ciluode top grade in CN1348434, relate generally to a kind of by Karol prepared in reaction γ, the method for delta unsaturated ketone and be used for new catalyzer of this method and preparation.Its emphasis is the mixture of the organo aluminum catalyst of various replacement modes (various acetoacetyls, alkoxyl group etc.), is liquid under the room temperature.Use tubular type or ring-type flow reactor.
H. EZE rood etc. relates generally in CN1184096 with cyclic carbonate ester or gamma lactone and makes solvent by Karol prepared in reaction γ, delta unsaturated ketone, representational solvent has: ethylene carbonate, carbonic acid-1, the inferior propyl ester of 2-, carbonic acid-1, the inferior isobutyl ester of 2-Aden ester or carbonic acid, gamma-butyrolactone, 3-methyl-gamma-butyrolactone, 3,4-dimethyl-δ-butyrolactone, 4,5-dimethyl-gamma-butyrolactone or 5-ethyl-gamma-butyrolactone etc.
J. Kui etc. relates generally to the preparation of beta-unsaturated ketone in the henry in CN1217316, and substituting group can be H or be replaced by oxy radical or unsubstituted alkyl, alkylene, cycloalkyl, cycloalkenyl group, aryl or aralkyl etc. in the beta-unsaturated ketone product.Reaction relates to armorphous silicic acid zinc catalyst.
Though the technical scheme of mentioning in existing patent has the processing method that sporadicly relates to geranyl acetone, does not relate to the complete technical scheme that geranyl acetone produces processing method.Though people such as Xu Qixin have reported relevant synthetic method in the 3rd the 2nd phase of volume of Chinese tobacco journal, what adopt is to add the method for phantol earlier, and does not realize suitability for industrialized production.
Three, technology contents
The invention provides and a kind ofly be easy to control and can reduce material loss and help to improve the processing method of the manufacturing geranyl acetone of product recovery rate.
The present invention takes following technical scheme to solve its technical problem: the present invention is a kind of processing method of making geranyl acetone, this method is: earlier methyl aceto acetate and 0.1%～10% the organo aluminum catalyst that accounts for the methyl aceto acetate quality are mixed, and be heated and be warming up to 70～250 ℃, press the adding speed of 0.1～10kg/min then, within 0.1～10h, adding molal quantity is the phantol of 1.0～2.0 times of methyl aceto acetates, and make and be reflected at 70～250 ℃, reaction times finishes more than 1h, get reaction solution and distillate, at last, purification promptly gets geranyl acetone to reaction solution.In reaction process, the present invention carries out capillary gas chromatography by sampling in the differential responses time, checks the content of its purpose product geranyl acetone, thereby judges whether reaction is carried out and proceeded to which kind of degree.The underlying condition of gas chromatographic analysis is: internal diameter is that 0.25mm and length are SE-54 or the OV-17 quartz capillary chromatographic column of 30m, is carrier gas with nitrogen.Analysis temperature adopts the mode of temperature programming, and initial temperature is 120 ℃, behind constant temperature 5 min, be raised to 160 ℃ with the speed of 4 ℃/min after constant temperature 10min again.Use fid detector, detected temperatures is 200 ℃.250 ℃ of sampler temperature temperature, sample size are 0.2 μ L.
Compared with prior art, the present invention has following beneficial effect: employing charging technology 1. of the present invention is: add methyl aceto acetate and catalyzer earlier, limit coronite adding phantol reacts then, shortened the phantol heated time, thereby avoided phantol dehydration decomposition, methyl aceto acetate bumping and at high temperature carried secretly easily and caused loss, the influence reaction makes the present invention have the reaction low advantage of control material loss easily, and helps to improve the rate of recovery of product.2. processing method of the present invention is carried out at synthetic various process segmentation control reaction and operational condition in same rectifying reactor, making and make the comprising of geranyl acetone whole chemical reaction processes such as " methyl aceto acetate and phantols carry out transesterification reaction generate etheric acid phantol ester → etheric acid phantol ester carry out the isomery rearrangement reaction and generate beta-keto acid → beta-keto acid and carry out decarboxylic reaction and generate a small amount of unreacted raw material of geranyl acetone → rectifying separation and other impurity components → rectifying acquisition high quality finished product " and physical purification process can include same production unit in is to finish in the batch fractionating formula reactor, carry out the what is called simple production mode of " treating different things alike ", have reduced investment, simple to operate, control easily, the product recovery rate height, high and the stable advantage of quality product.3. processing method of the present invention is at containing a small amount of unreacted raw material methyl aceto acetate in the reaction distillate, the reaction distillate that collection is obtained turns back to that heat temperature raising carries out rectifying in the rectifying formula reactor, isolate wherein low-boiling point material ethanol and other impurity components after recycle this part methyl aceto acetate and phantol, and then react.Therefore, processing method of the present invention has can make full use of raw material, makes raw materials consumption reach bottom line, from the advantage of the actual recovery that can improve purpose product geranyl acetone.4. processing method of the present invention, at still there being organo aluminum catalyst in the reaction residue behind the refined product geranyl acetone, and catalyst activity does not have the fact of loss substantially, as long as replenish a spot of organo aluminum catalyst, just can be used further to new geranyl acetone building-up reactions.Like this, Technology of the present invention has can obviously reduce catalyst consumption, improves the advantage of catalyst utilization and minimizing production cost.
Four, specific embodiments
Embodiment 1
A kind of processing method of making geranyl acetone, earlier methyl aceto acetate and 0.1%～10% the organo aluminum catalyst that accounts for the methyl aceto acetate quality are mixed, and be heated and be warming up to 70～250 ℃, press the adding speed of 0.1～10kg/min then, within 0.1～10h, adding molal quantity is the phantol of 1.0～2.0 times of methyl aceto acetates, and make and be reflected at 70～250 ℃, reaction times finishes more than 1h, get reaction solution and distillate, at last, purification promptly gets geranyl acetone to reaction solution, above-mentioned organo aluminum catalyst can be the alkyl aluminium alcoholates, alkylphenol aluminium or ALUMINUM CARBOXYLIC etc., in the present embodiment, with methyl aceto acetate, after organo aluminum catalyst and phantol place rectifying formula reactor to finish reaction, and the reaction solution of Geranyl acetone is cooled to below the rectification temperature, after this, it is 50～250 ℃ at rectification temperature, rectifying pressure is under the condition of 0.1～100kPa, in the rectifying tower of above-mentioned rectifying formula reactor Geranyl acetone reaction solution is carried out rectifying.
Embodiment 2
A kind of processing method of making geranyl acetone, earlier methyl aceto acetate and 0.1%～10% the organo aluminum catalyst that accounts for the methyl aceto acetate quality are mixed, and be heated and be warming up to 70～250 ℃, press the adding speed of 0.1～10kg/min then, within 0.1～10h, adding molal quantity is the phantol of 1.0～2.0 times of methyl aceto acetates, and make and be reflected at 70～250 ℃, reaction times finishes more than 1h, get reaction solution and distillate, at last, purification promptly gets geranyl acetone to reaction solution, in the present embodiment, purify and adopt the rectifying mode, and with reacting distillate from the collection of rectifying tower top after the condenser condenses, the by product ethanol that mainly containing in the reaction distillate responds generates and methyl aceto acetate and the phantol that reacts and carried secretly out that do not have enough time on a small quantity to participate in, the above-mentioned reaction distillate heat temperature raising that collection is obtained carries out rectifying, still temperature during rectifying is between 70～250 ℃, tower top temperature is 50～150 ℃, isolate wherein low-boiling point material ethanol and other impurity components, just obtain containing the residual mixed solution of methyl aceto acetate and phantol, record methyl aceto acetate and phantol content by gas chromatographic analysis, 0.1%～10% the organo aluminum catalyst that replenish to add methyl aceto acetate and account for the methyl aceto acetate quality in residual mixed solution mixes, and be heated be warming up to 70～250 ℃ after, again with the adding speed of 0.1～10kg/min, within 0.1～10h, in heated residual still liquid, replenish and add phantol, the ratio of phantol and methyl aceto acetate is met (1.0～2.0): 1 molar mass ratio, and make and be reflected at 70～250 ℃, reaction times finishes more than 1h, get reaction solution and distillate thus again, at last, to obtaining geranyl acetone again after the reaction solution purification that gets again.
Embodiment 3
A kind of producing and manufacturing technique of making geranyl acetone, earlier methyl aceto acetate and 0.1%～10% the organo aluminum catalyst that accounts for the methyl aceto acetate quality are mixed, and be heated and be warming up to 70～250 ℃, press the adding speed of 0.1～10kg/min then, within 0.1～10h, adding molal quantity is the phantol of 1.0～2.0 times of methyl aceto acetates, and make and be reflected at 70～250 ℃, reaction times finishes more than 1h, get reaction solution and distillate, at last, purification promptly gets geranyl acetone to reaction solution, in the present embodiment, with methyl aceto acetate, after organo aluminum catalyst and phantol place rectifying formula reactor to finish reaction, Geranyl acetone reaction solution is cooled to below the rectification temperature, at rectification temperature is 50～250 ℃, rectifying pressure is under the condition of 0.1～100kPa, in the rectifying tower of above-mentioned rectifying formula reactor, Geranyl acetone reaction solution is carried out rectifying, after this, replenish in the reaction residue after purification and add organo aluminum catalyst, make methyl aceto acetate and organo aluminum catalyst meet 1: (0.1%～10%) mass ratio relation, then to its heat temperature raising to 70～250 ℃, reaction times is more than 1h, after getting reaction solution, reaction solution is purified promptly get geranyl acetone again.
Embodiment integrated synchronous reaction of 4 geranyl acetone synthetic and rectification and purification
In the cold or warm rectifying formula of 200L reactor, drop into methyl aceto acetate (content is more than 96%) 50～100kg, drop into simultaneously and account for 0.1～10% of methyl aceto acetate quality, be preferably 0.5～5.0% alkyl alcohol (phenol, carboxylic acid) Al catalysts, with material heat temperature raising to 70～250 ℃, then from flow velocity by 0.1～10kg/min, adding phantol (content is more than 96%) 60kg within 0.1～10h, be reflected between 100～250 ℃ and finish, be preferably between 100～200 ℃ and finish, reaction times is preferably in 8～20h and finishes more than 1h.The reaction distillate flows out by the rectifying tower top, and collects through after the condenser condenses, in order to recycling.The by product ethanol that mainly containing in the reaction distillate responds generates and methyl aceto acetate and the phantol that reacts and carried secretly out that do not have enough time on a small quantity to participate in.
Carry out gas chromatographic analysis from the thief hole sampling in the reaction process, see Table 1.
Inspection by sampling for example in table 1 reaction process
| Sample time/h | Gas-chromatography content/% |
| ????6 | ????35.50 |
| ????8 | ????39.41 |
| ????10 | ????68.04 |
| ????12 | ????88.61 |
| ????14 | ????90.85 |
Stop heating when being reacted to reaction solution after the assay was approved with gas-chromatography.Generally being controlled at the reaction solution that obtains Geranyl acetone about 65～95% is advisable.
The reaction solution that obtains does not need to shift, and directly carries out rectification under vacuum in same rectifying formula reactor, removes dehydration by product, isomery by product and the polymeric by-products of a small amount of unreacted raw material, reaction generation.The vacuum tightness of rectifying is at 0.13～20kPa, and 50～250 ℃ of rectification temperatures are preferably in 50～200 ℃.The gas-chromatography composition of the cut of the different steps in the rectifying sees Table 2.
Each the cut check of table 2 rectification process process for example
| Sample time/h | Gas-chromatography content/% |
| ????2.5 | ????16.97 |
| ????3.5 | ????42.91 |
| ????4.5 | ????77.97 |
| ????6.5 | ????95.48 |
| ????7.5 | ????97.79 |
| ????9.0 | ????99.29 |
| ????10.0 | ????99.12 |
| Finished product | ????99.52 |
Collection obtains geranyl acetone (total content of two isomer geranyl acetones and neryl C10H17-acetone is more than 99%) finished product 65.3kg, and product yield is 90.0% (is that 100% phantol is a basic calculation with content) of theoretical molar yield.
Embodiment 5 utilizes and reclaims methyl aceto acetate and the synthetic geranyl acetone of phantol
In the 200L reactor, drop into and collect the reaction distillate that obtains, being heated then heats up carries out rectifying, still temperature during rectifying is between 70～250 ℃, tower top temperature is 50～150 ℃ the boiling point of 180.4 ℃ of the boiling points of methyl aceto acetate and phantol (should be lower than respectively 197～199 ℃), tell wherein low-boiling point material ethanol and other impurity components, contain methyl aceto acetate and phantol in the residual still liquid, its content records by gas chromatographic analysis.Replenish the methyl aceto acetate that adds insufficient section and make it reach 66kg, the phantol that replenishes the adding insufficient section then is to 60kg.Other operating process and processing condition control are with embodiment 1.Obtain qualified finished product geranyl acetone 62.5kg, product yield is 86.1% (is that 100% phantol is a basic calculation with content) of theoretical molar yield.
Embodiment 6 utilizes the catalyzer in the rectifying still raffinate to make geranyl acetone
Finish after the technological process of embodiment 1, stay the raffinate in the still, the catalyzer that replenishes a small amount of insufficient section is to accounting for 0.1%～10% of methyl aceto acetate quality, and other operating procedure processes and processing condition are identical with embodiment 1.Obtain qualified finished product geranyl acetone 59.6kg, product yield is 82.1% (is that 100% phantol is a basic calculation with content) of theoretical molar yield.
Claims (4)
1, a kind of processing method of making geranyl acetone, it is characterized in that earlier methyl aceto acetate and 0.1%～10% the organo aluminum catalyst that accounts for the methyl aceto acetate quality are mixed, and be heated and be warming up to 70～250 ℃, press the adding speed of 0.1～10kg/min then, within 0.1～10h, adding molal quantity is the phantol of 1.0～2.0 times of methyl aceto acetates, and make and be reflected at 70～250 ℃, reaction times finishes more than 1h, get reaction solution and distillate, at last, purification promptly gets geranyl acetone to reaction solution.
2, the processing method of manufacturing geranyl acetone according to claim 1, after it is characterized in that placing rectifying formula reactor to finish reaction methyl aceto acetate, organo aluminum catalyst and the phantol, Geranyl acetone reaction solution is cooled to below the rectification temperature, after this, at rectification temperature is that 50～250 ℃, rectifying pressure are under the condition of 0.1～100kPa, in the rectifying tower of above-mentioned same rectifying formula reactor Geranyl acetone reaction solution is carried out rectifying.
3, the processing method of manufacturing geranyl acetone according to claim 1, it is characterized in that the reaction distillate heat temperature raising that collection is obtained carries out rectifying, still temperature during rectifying is between 70～250 ℃, tower top temperature is 50～150 ℃, isolate wherein low-boiling point material ethanol and other impurity components, just obtain containing the residual mixed solution of methyl aceto acetate and phantol, 0.1%～10% the organo aluminum catalyst that replenish to add methyl aceto acetate and account for whole methyl aceto acetate quality in residual mixed solution mixes, and be heated be warming up to 70～250 ℃ after, again with the adding speed of 0.1～10kg/min, within 0.1～10h, in heated residual still liquid, replenish and add phantol, the ratio of phantol and methyl aceto acetate is met (1.0～2.0): 1 mol ratio, and make and be reflected at 70～250 ℃, the reaction times finishes more than 1h, thus again reaction solution and distillate, at last, to obtaining geranyl acetone again after the reaction solution purification that gets again.
4, the processing method of manufacturing geranyl acetone according to claim 1, it is characterized in that replenishing in the reaction residue after purification and add organo aluminum catalyst, make methyl aceto acetate and organo aluminum catalyst meet 1: (0.1%～10%) mass ratio relation, then to its heat temperature raising to 70～250 ℃, reaction times is more than 1h, after getting reaction solution, purification promptly gets geranyl acetone to reaction solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2003101064483A CN1546449A (en) | 2003-11-28 | 2003-11-28 | Process for producing geranyl acetone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2003101064483A CN1546449A (en) | 2003-11-28 | 2003-11-28 | Process for producing geranyl acetone |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1546449A true CN1546449A (en) | 2004-11-17 |
Family
ID=34334173
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2003101064483A Pending CN1546449A (en) | 2003-11-28 | 2003-11-28 | Process for producing geranyl acetone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1546449A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102115437A (en) * | 2010-04-12 | 2011-07-06 | 上海迪赛诺医药发展有限公司 | Method for preparing gamma and delta unsaturated ketone |
| CN103755538A (en) * | 2014-01-09 | 2014-04-30 | 吉林北沙制药有限公司 | Synthetic method of dihydrogen geranyl acetone and dihydrogen nicky acetone |
| CN112250554A (en) * | 2020-10-13 | 2021-01-22 | 万香科技股份有限公司 | Method for synthesizing geranylacetone by carroll reaction |
-
2003
- 2003-11-28 CN CNA2003101064483A patent/CN1546449A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102115437A (en) * | 2010-04-12 | 2011-07-06 | 上海迪赛诺医药发展有限公司 | Method for preparing gamma and delta unsaturated ketone |
| CN102115437B (en) * | 2010-04-12 | 2014-05-07 | 上海海嘉诺医药发展股份有限公司 | Method for preparing gamma and delta unsaturated ketone |
| CN103755538A (en) * | 2014-01-09 | 2014-04-30 | 吉林北沙制药有限公司 | Synthetic method of dihydrogen geranyl acetone and dihydrogen nicky acetone |
| CN103755538B (en) * | 2014-01-09 | 2015-04-22 | 吉林北沙制药有限公司 | Synthetic method of dihydrogen geranyl acetone and dihydrogen nicky acetone |
| CN112250554A (en) * | 2020-10-13 | 2021-01-22 | 万香科技股份有限公司 | Method for synthesizing geranylacetone by carroll reaction |
| CN112250554B (en) * | 2020-10-13 | 2022-04-19 | 江苏宏邦化工科技有限公司 | Method for synthesizing geranylacetone by carroll reaction |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7838707B2 (en) | Process for the preparation of a tetraalkylcyclobutane-1,3-diol using an ruthenium-promoted cobalt-based catalyst | |
| TWI422581B (en) | 2-methyl-3-(3,4-methylenedioxyphenyl) propionaldehyde and a process for producing the same | |
| US4484009A (en) | Process for the manufacture of glycol monoethers | |
| US7560600B2 (en) | Process for the preparation of a tetraalkylcyclobutane-1,3-diol using a promoted nickel-based catalyst | |
| US20050154239A1 (en) | Methods for preparing 1,3 butylene glycol | |
| US6329554B1 (en) | Continuous preparation of unsaturated ketones | |
| CN1546449A (en) | Process for producing geranyl acetone | |
| Barlow et al. | New building blocks for efficient and highly diastereoselective polyol production—synthesis and utility of (R′, R′, S, S) and (S′, S′, R, R)-2, 3-butane diacetal protected butane tetrol derivatives | |
| US7524994B2 (en) | Process for the preparation of a tetraalkylcyclobutane-1,3-diol using an iridium-promoted cobalt-based catalyst | |
| IT9022119A1 (en) | PROCEDURE FOR THE PREPARATION OF DIETERS | |
| JPS5826331B2 (en) | Method for producing stereo-regulated farnesyl acetate | |
| US7521583B2 (en) | Process for the preparation of tetraalkylcyclobutane-1,3-diol in the presence of a cobalt-based catalyst | |
| US3963754A (en) | 2-Vinyl-5-methyl-1,3-dioxane | |
| KR20190023466A (en) | High purity 1,3-butanediol and its preparation method | |
| CN111423317A (en) | Production device and method for synthesizing dihydro jasmone spice through solid acid catalysis | |
| JP2003525220A (en) | Method for improving the color value of polyhydric alcohols by hydrogenation | |
| US3963755A (en) | Mixture of 2(2'-propanal)-5-methyl-1,3-dioxane and 2(3'-propanal)-5-methyl-1,3-dioxane | |
| US4990697A (en) | Process for producing homoallyl alcohols | |
| US4677230A (en) | Preparation of 2-methyl-2-alkenals | |
| JPS5826330B2 (en) | Method for producing stereo-regulated farnesyl acetate | |
| US4024197A (en) | Production of butanediol | |
| US9199900B2 (en) | Method for converting farnesol to nerolidol in the presence of alpha-bisabolol | |
| US6072089A (en) | Process for producing 1,5-pentanediol derivatives | |
| CN116462578A (en) | Method for synthesizing delta-methyl ketone by one-pot method | |
| Chickos et al. | A study of the catalytic deuteration of 1, 4-butynediol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |