[go: up one dir, main page]

WO2015123984A1 - Procédé de préparation de 2,6-diméthyl-6-alkyloxy(ou hydroxyl)heptaldéhyde - Google Patents

Procédé de préparation de 2,6-diméthyl-6-alkyloxy(ou hydroxyl)heptaldéhyde Download PDF

Info

Publication number
WO2015123984A1
WO2015123984A1 PCT/CN2014/085701 CN2014085701W WO2015123984A1 WO 2015123984 A1 WO2015123984 A1 WO 2015123984A1 CN 2014085701 W CN2014085701 W CN 2014085701W WO 2015123984 A1 WO2015123984 A1 WO 2015123984A1
Authority
WO
WIPO (PCT)
Prior art keywords
dimethyl
hydroxy
alkoxy
octene
reaction
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.)
Ceased
Application number
PCT/CN2014/085701
Other languages
English (en)
Chinese (zh)
Inventor
杨高东
林力克
王宝荣
周政
张志炳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NANJING ENETEKS CO LTD
Original Assignee
NANJING ENETEKS CO LTD
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by NANJING ENETEKS CO LTD filed Critical NANJING ENETEKS CO LTD
Publication of WO2015123984A1 publication Critical patent/WO2015123984A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/293—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/40—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with ozone; by ozonolysis
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/297—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D323/00—Heterocyclic compounds containing more than two oxygen atoms as the only ring hetero atoms
    • C07D323/02—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated

Definitions

  • the invention belongs to the field of perfumes, in particular to an important derivative of melon aldehyde, and more particularly to a preparation method of 2,6-dimethyl-6-alkoxy (or hydroxy)heptanal.
  • 2,6-Dimethyl-6-alkoxy (or hydroxy)heptanal (hereinafter referred to as heptaldehyde) has a structural formula of the formula (3) and is an important derivative of melon aldehyde.
  • R is H, methyl, ethyl, acetyl, propyl, isopropyl, butyl, isobutyl, pentyl, 1-hydroxy-2-methyl-1-methyl, isopentyl, cyclopentyl One of a base, an n-hexyl group or an allyl group.
  • 2,6-dimethyl-6-hydroxyheptanal with the aroma of melon, tropical fruit, raspberry, lily of the valley, can be used in tobacco, food, detergent, soap, fabric softener, perfume, etc.
  • 2,6-dimethyl-6-methoxyheptanal a colorless to pale yellow viscous liquid with a light floral aroma, a slight fruity aroma, and a characteristic aroma of citrus.
  • a fresh herbaceous taste and a light melon-like fruity aroma that can be used in functional and cosmetic fragrances with floral and herbal notes.
  • U.S. Patent 4,287,133 discloses a process for the preparation of heptaldehyde. It is prepared by using a 2,6-dimethyl-5-hepten-2-one as a raw material, and is synthesized by a Darzens condensation reaction with ethyl chloroacetate under the action of sodium alkoxide, and then saponified to form melon aldehyde under strong alkali conditions, and then Under the protection of sulfite or enamine salt, the aldehyde group is hydrated under the catalysis of concentrated sulfuric acid at the 6-position double bond, and finally deprotected under strong alkali conditions to form 2,6-dimethyl-6. -Hydroxyheptanal, the reaction mechanism is as follows:
  • Chinese patent CN103396296A also discloses a method for preparing heptaldehyde, which is based on 2,6-dimethyl-5-hepten-2-one and firstly produces 6-methyl group with methanol under concentrated sulfuric acid catalysis. -6-methoxy-2-heptanone, then Darzens condensation reaction with ethyl chloroacetate under the action of sodium alkoxide, followed by saponification reaction under strong alkali conditions to obtain 2,6-dimethyl-6 -Methoxyheptanal, the reaction mechanism is as follows:
  • the object of the present invention is to provide a process for preparing 2,6-dimethyl-6-alkoxy (or hydroxy)heptanal which is simple in process, high in yield and environmentally friendly.
  • the reaction mechanism of the present invention is as follows:
  • Step 1 Ozonation of 2,6-dimethyl-2-alkoxy (or hydroxy)-7-octene
  • the 2,6-dimethyl-2-alkoxy (or hydroxy)-7-octene of the formula (1) is placed in a reactor with a solvent and water, and O 3 /O is introduced into the reactor.
  • the 2,6-dimethyl-2-alkoxy (or hydroxy)-7-octene ozonation product is introduced into a protective gas to 2,6-dimethyl-2-alkoxy (or hydroxy)-7-octene ozonation product for protection;
  • R is selected from the group consisting of H, methyl, ethyl, acetyl, propyl, isopropyl, butyl, isobutyl, pentyl, 1-hydroxy-2-methyl-1-propyl
  • R is selected from the group consisting of H, methyl, ethyl, acetyl, propyl, isopropyl, butyl, isobutyl, pentyl, 1-hydroxy-2-methyl-1-propyl
  • R is selected from the group consisting of H, methyl, ethyl, acetyl, propyl, isopropyl, butyl, isobutyl, pentyl, 1-hydroxy-2-methyl-1-propyl
  • Step 2 Reduction of 2,6-dimethyl-2-alkoxy (or hydroxy)-7-octene ozonation product
  • the above preparation method further comprises the third step, the crude 2,6-dimethyl-6-alkoxy (or hydroxy)heptanal obtained in the second step is subjected to vacuum distillation to obtain a 2,6-dimethyl group having a purity of more than 90%. -6-alkoxy (or hydroxy) heptanal.
  • the reaction temperature of the ozonation reaction in the step (1) is -30 ° C to 30 ° C, preferably -10 ° C to 15 °C; reaction time is from 0.5 h to 8 h, preferably from 1 to 3 h.
  • the reaction temperature in the reduction reaction in the step (2) is from 20 ° C to 100 ° C, preferably from 40 ° C to 90 ° C; the reaction time is from 0.5 h to 10 h, preferably from 1 h to 6 h; the reaction temperature and reaction time of the reduction reaction are selected in this The range allows the reduction reaction to proceed very thoroughly.
  • the mass ratio of 2,6-dimethyl-2-alkoxy (or hydroxy)-7-octene to the solvent and water in the step (1) is 1: (0.5 to 4): (0.5 to 4), preferably It is 1: (1 ⁇ 3): (1 ⁇ 3); it not only ensures that the raw materials in the liquid material can fully contact ozone, and the ozonation reaction occurs, and the difficulty of subsequent separation is reduced.
  • the molar percentage of O 3 in the O 3 /O 2 mixture is from 1% to 20%, preferably from 5% to 10%; and the aeration rate of the O 3 /O 2 mixture is from 0.5 to 5 m 3 /h. / (kg raw material), preferably 1 to 4.5 m 3 /h / (kg raw material).
  • the molar percentage of O 3 in the mixture and the aeration rate are selected within the above range, which reduces the severity of the ozonation reaction while ensuring that sufficient ozone is involved in the reaction.
  • the solvent in the step (1) is selected from the group consisting of anhydrous ethanol, isopropanol, butanol, tert-butanol, acetone, methyl ethyl ketone, acetonitrile, propionitrile, isobutyronitrile, ethyl acetate, butyl acetate, chloroform, and One of methyl chloride, 1,2-dichloroethane, dipropyl ether, diisopropyl ether, cyclohexanone, methyl ethyl ketone, xylene, anisole, dimethylacetamide.
  • the molar ratio of the solute in the bisulfite or pyrosulfite solution to the ozonation product of 2,6-dimethyl-2-alkoxy (or hydroxy)-7-octene is ( 0.5 to 5): 1, preferably (1 to 3): 1; the molar ratio ensures sufficient reducing agent to reduce ozonation products.
  • the bisulfite or pyrosulfite is selected from the group consisting of sodium hydrogen sulfite, potassium hydrogen sulfite, sodium metabisulfite, potassium metabisulfite; mass concentration of the bisulfite or pyrosulfite solution It is 5% to 40%, preferably 10% to 20%.
  • the mass concentration of bisulfite or pyrosulfite solution selects this The range not only ensures that its acidity is not enough to cause great damage to the equipment, but also meets the requirements of reduction.
  • the alkaline solution has a mass concentration of 5% to 30%, and the base is selected from the group consisting of sodium carbonate, potassium carbonate, sodium hydroxide, and potassium hydroxide; and the alkali in the concentration range is selected.
  • the solution satisfies the requirements of neutralizing acidic products and has low harm to equipment.
  • the invention has simple process, high conversion rate of raw materials and high yield of products, no protection group is needed to protect aldehyde groups during preparation, and is environmentally friendly; no catalyst is used in ozonation reaction and reduction step, and subsequent separation Low difficulty, good industrial reliability, suitable for industrial production.
  • the aeration rate is 0.5 to 5 m 3 /h / (kg of raw material) refers to 1 kg of the raw material [the raw material is 2,6-dimethyl-2-alkoxy (or hydroxy)-7-octene] It is required to pass gas 0.5 to 5 m 3 per hour.
  • a preparation method of 2,6-dimethyl-6-hydroxy-heptanal comprising the following steps:
  • the temperature was lowered to below 50 ° C, and 90 kg of a sodium carbonate solution having a mass concentration of 17% was prepared, and the mixture was injected into a stirred tank reactor by a plunger pump for neutralization, and stirred while being added, and the addition time was 40 minutes.
  • the material in the reactor was passed to a phase separator to take out the oil layer, and then the oil phase was washed with water. After the pH of the wash water was measured to be neutral, the upper oil phase pH was 8.3, and the obtained oil phase 45 kg was crude 2,6-dimethyl-6-hydroxy-heptanal, which was 2,6-dimethyl.
  • the crude -6-hydroxy-heptanal was distilled under reduced pressure to obtain 8.6 kg of 2,6-dimethyl-6-hydroxy-heptanal product.
  • the product was analyzed by GC to obtain a mass percentage of 91.4%, using GC. - MS determined that the product structure was 2,6-dimethyl-6-hydroxy-heptanal.
  • a preparation method of 2,6-dimethyl-6-methoxy-heptanal comprising the following steps:
  • a preparation method of 2,6-dimethyl-6-acetoxy-heptanal comprising the following steps:
  • the reaction temperature was 11 °C, 4 hours after the occurrence of ozone, using KI paper test reactor outlet gas, KI paper blue, continued After reacting the O 3 /O 2 mixture for 1 h, the material was transferred from the reactor to a separatory funnel, and the oil phase of the dihydrogen lauryl acetate ozonation product 740 g was taken out and stored in a bottle and protected with nitrogen.
  • a 2,6-dimethyl-6-n-propoxy-heptanal comprising the following steps:
  • reaction temperature was 8 °C, after 1 hour of reaction occurs ozonized using KI paper test reactor outlet gas, KI paper blue, After continuing to react with the O 3 /O 2 mixture for 2 h, the material was transferred from the bottom of the reactor to the separatory funnel, and the oil phase 2,6-dimethyl-2-n-propoxy-7-octene ozonation product was taken out. 730g was stored in the bottle and protected with nitrogen.
  • a preparation method of 2,6-dimethyl-6-isopentyloxy-heptanal comprising the following steps:
  • the temperature is reduced to below 50 ° C, and 10 kg of sodium carbonate solution having a mass concentration of 19% is prepared, and the plunger pump is used to drive into the stirred tank reactor.
  • the addition time is 45 minutes, and after stirring for 10 minutes, the upper oil phase PH is measured to be 9.1, and then the material in the reactor is moved to the phase separator to take out the oil layer, and then the oil is removed.
  • the obtained oil phase was 8.1 kg of crude 2,6-dimethyl-6-isopentyloxy-heptanal, and 2,6-dimethyl-
  • the crude 6-isopentyloxy-heptanal was distilled under reduced pressure to obtain 2.3 kg of 2,6-dimethyl-6-isopentyloxy-heptanal product, which was analyzed by GC.
  • the mass percentage was 96.7%, and the molecular weight was 228.4 as determined by MS.
  • the structure of the product was determined to be 2,6-dimethyl-6-isopentyloxy-heptanal by 1 H NMR and 13 C NMR.
  • a preparation method of 2,6-dimethyl-6-isobutoxy-heptanal comprising the following steps:
  • a preparation method of 2,6-dimethyl-6-cyclopentyloxy-heptanal comprising the following steps:
  • the temperature was lowered to below 50 °C, and 136 kg of potassium hydroxide solution with a mass concentration of 17% was prepared, and the mixture was stirred by a plunger pump.
  • the reactor was neutralized, stirred while stirring, and the addition time was 60 minutes. After the addition, the mixture was stirred for another 20 minutes, and the pH of the upper oil phase was measured to be 7.9. Then, the material in the reactor was moved to the phase separator to remove the oil layer.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé de préparation de 2,6-diméthyl-6-alkyloxy(ou hydroxyl)heptaldéhyde, comprenant les étapes suivantes consistant : I, à placer du 2,6-diméthyl-2-alkyloxy(ou hydroxyl)-7-octène, un solvant et de l'eau dans un réacteur, à charger un mélange de O3/O2 dans le réacteur, après l'achèvement de la réaction, à séparer les couches de produits obtenus et à charger un gaz de protection dans la phase huileuse obtenue pour la protection ; II, à ajouter une solution de bisulfite ou de pyrosulfite dans la phase huileuse obtenue à l'étape I, puis à augmenter la température, après l'achèvement de la réaction, à neutraliser les produits obtenus à l'aide d'une solution alcaline, puis à séparer les phases huileuse et aqueuse, à laver la phase huileuse jusqu'à un pH neutre et à séparer les phases huileuse et aqueuse, la phase huileuse obtenue étant un produit brut de 2,6-diméthyl-6-alkyloxy(ou hydroxyl)heptaldéhyde. La présente invention présente un procédé simple, un taux élevé de conversion des matières premières, un rendement élevé en produits, est respectueuse de l'environnement, présente une faible difficulté de séparation ultérieure, une bonne fiabilité industrielle et convient à la production industrielle.
PCT/CN2014/085701 2014-02-24 2014-09-02 Procédé de préparation de 2,6-diméthyl-6-alkyloxy(ou hydroxyl)heptaldéhyde Ceased WO2015123984A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201410062238.7A CN103819335B (zh) 2014-02-24 2014-02-24 一种2,6-二甲基-6-烷氧基（或羟基）庚醛的制备方法
CN2014100622387 2014-02-24

Publications (1)

Publication Number Publication Date
WO2015123984A1 true WO2015123984A1 (fr) 2015-08-27

Family

ID=50754672

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2014/085701 Ceased WO2015123984A1 (fr) 2014-02-24 2014-09-02 Procédé de préparation de 2,6-diméthyl-6-alkyloxy(ou hydroxyl)heptaldéhyde

Country Status (2)

Country Link
CN (1) CN103819335B (fr)
WO (1) WO2015123984A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023044460A1 (fr) * 2021-09-17 2023-03-23 P2 Science, Inc. Compositions de parfum et d'arôme comprenant un ester de formiate d'hydroxymélonal

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103819335B (zh) * 2014-02-24 2016-01-20 南京运华立太能源科技有限公司 一种2,6-二甲基-6-烷氧基（或羟基）庚醛的制备方法
CN110713442A (zh) * 2018-07-11 2020-01-21 程先波 一种邻硝基苯甲醛的制备方法
CN111763221A (zh) * 2020-07-31 2020-10-13 重庆医药高等专科学校 一种头孢维星中间体及其制备方法
CN117003627B (zh) * 2023-08-07 2025-07-11 武穴坤悦生物科技有限公司 一种2,6-二甲基-2-羟基-庚醛的合成方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4287133A (en) * 1978-11-17 1981-09-01 International Flavors & Fragrances Inc. 6-Hydroxy-2,6-dimethylheptanal, organoleptic uses thereof and processes for preparing the same
WO2013053102A1 (fr) * 2011-10-11 2013-04-18 Givaudan Sa Améliorations à ou relatives à des composés organiques
CN103396296A (zh) * 2013-08-07 2013-11-20 上海应用技术学院 一种2,6-二甲基-6-甲氧基庚醇系列衍生物及其制备方法
CN103819335A (zh) * 2014-02-24 2014-05-28 南京运华立太能源科技有限公司 一种2,6-二甲基-6-烷氧基（或羟基）庚醛的制备方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101508634B (zh) * 2009-03-23 2011-09-28 中国科学院新疆理化技术研究所 一种臭氧化制备2-壬烯醛的方法
CN103102256A (zh) * 2013-01-24 2013-05-15 复旦大学 一种光学活性7-取代氧基-6-羟基庚-3-乙烯-2-酮的制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4287133A (en) * 1978-11-17 1981-09-01 International Flavors & Fragrances Inc. 6-Hydroxy-2,6-dimethylheptanal, organoleptic uses thereof and processes for preparing the same
WO2013053102A1 (fr) * 2011-10-11 2013-04-18 Givaudan Sa Améliorations à ou relatives à des composés organiques
CN103396296A (zh) * 2013-08-07 2013-11-20 上海应用技术学院 一种2,6-二甲基-6-甲氧基庚醇系列衍生物及其制备方法
CN103819335A (zh) * 2014-02-24 2014-05-28 南京运华立太能源科技有限公司 一种2,6-二甲基-6-烷氧基（或羟基）庚醛的制备方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023044460A1 (fr) * 2021-09-17 2023-03-23 P2 Science, Inc. Compositions de parfum et d'arôme comprenant un ester de formiate d'hydroxymélonal

Also Published As

Publication number Publication date
CN103819335A (zh) 2014-05-28
CN103819335B (zh) 2016-01-20

Similar Documents

Publication Publication Date Title
WO2015123984A1 (fr) Procédé de préparation de 2,6-diméthyl-6-alkyloxy(ou hydroxyl)heptaldéhyde
US20220306570A1 (en) New quaternary ammonium compounds
US9040592B2 (en) Process for preparing 4-cyclohexyl-2-methyl-2-butanol
CN105399603A (zh) 同时合成2,2,4-三甲基-1,3-戊二醇双异丁酸酯和2,2,4-三甲基-1,3-戊二醇的方法
CN104817436A (zh) 一种制备高纯度乙基己基甘油的方法
CN109942407B (zh) 一种合成9，10-二羟基十八碳硬脂酸的方法
JP7330907B2 (ja) 組み換え宿主細胞により産生された脂肪族アルコール組成物の下流処理
CN104520270A (zh) 视黄醇酯的酯交换方法
US8993812B2 (en) Method for preparing 2-methyl-4-phenylbutan-2-OL
CN103508898A (zh) 一种新的枸橼酸阿尔维林的制备方法
CN104262320A (zh) 一种黄樟油素转化为异黄樟油素的方法
CN103435795A (zh) 一种四氢糠醇聚氧乙烯醚的合成方法
CN101270048B (zh) 1-氯-2-甲基-4-乙酰氧基-2-丁烯的合成方法
SU618374A1 (ru) 4-Метил-2-(2,6-диметилгептадиен1,5-ил-1-)тетрагидропиранол-4 в качестве душистого вещества дл парфюмерных композиций
EP1652845B1 (fr) Procédé pour la préparation des lactones et leur utilisation comme substances odorantes
US9255050B2 (en) Process for the production of 2-alkyl-3-butyn-2-ols
CN105492415B (zh) 用于生产二氯代醇的方法
EP3271369B1 (fr) Procédé d'obtention de dérivés et de compositions à base d'acide d-galacturonique directement à partir de pectines
CN102746145B (zh) 一种甲酸乙酯的制备方法
RU2513111C1 (ru) Способ очистки пара-диоксанона
RU2420508C1 (ru) Способ получения циклооктанола
JP5089899B2 (ja) ポリオキシエチレンソルビタン脂肪酸エステル組成物
JP2005187419A (ja) グリセリンポリアルキレングリコールエーテル誘導体の製造方法
CN106660911B (zh) 用于从甘油和酰氯生产氯醇的方法
RU2510629C1 (ru) Способ получения трихлоргидрина пентаэритрита

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14883074

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14883074

Country of ref document: EP

Kind code of ref document: A1