SU729183A1

SU729183A1 - Method of preparing citronellol

Info

Publication number: SU729183A1
Application number: SU762397640A
Authority: SU
Inventors: Дмитрий Владимирович Сокольский; Алла Михайловна Пак; Сапаргали Ретаевич Конуспаев; Раиса Фадеевна Шилина
Original assignee: Институт Органического Катализа И Электрохимии Ан Казахской Сср
Priority date: 1976-08-24
Filing date: 1976-08-24
Publication date: 1980-04-25

Description

Изобретение относится к способу получения цитронеллола, который является Ценным душистым веществом, широко используемым в парфюмерной промышленности.The invention relates to a method for producing citronellol, which is a valuable aromatic substance widely used in the perfume industry.

Известен способ получения цитронеллола путем гидрирования цитраля на медно-хромовом катализаторе при давлении 50-200 ат и температуре 95-125°С Г1] .A known method of producing citronellol by hydrogenation of citral on a copper-chromium catalyst at a pressure of 50-200 at and a temperature of 95-125 ° C G1].

. По этому способу получают продукт, содержащий только 83,2% цитронеллола и 10% гераниола. Выход технического целевого продукта в расчете на цитраль составляет 88%.. By this method, a product is obtained containing only 83.2% citronellol and 10% geraniol. The yield of the technical target product based on citral is 88%.

Цель изобретения - повышение селективности процесса и увеличение выхода целевого продукта.The purpose of the invention is to increase the selectivity of the process and increase the yield of the target product.

Поставленная цель достигается тем, что процесс гидрирования цитронеллола . ведут в присутствии добавки соды в дистиллированной воде и никель-хромового катализатора в среде спирта изостроения Сз-С^ при 60-120¾ и давлении 1-8 О ат.The goal is achieved in that the process of hydrogenation of citronellol. lead in the presence of an additive of soda in distilled water and a nickel-chromium catalyst in the environment of alcohol from the isostructure Сз-С ^ at 60-120¾ and a pressure of 1-8 Oat.

. 2. 2

Предложенный способ получения цитронеллона дает возможность подучать продукт, содержащий 92-97% цитронеллола и только 2,0-3,5% побочного продукта -The proposed method for producing citronellone makes it possible to obtain a product containing 92-97% citronellol and only 2.0-3.5% by-product -

2,6-диметилоктанола.2,6-dimethyloctanol.

Выход цитронеллола в расчете на цитраль составляет 96-97%,The yield of citronellol based on citral is 96-97%,

Д,чше процесс вести в присутствии соды, взятой в количестве 9% от веса . катализатора, растворенной в объеме воды, равным 1/10 объема растворителя.D, a better process is carried out in the presence of soda, taken in an amount of 9% by weight. catalyst dissolved in a volume of water equal to 1/10 of the volume of solvent.

Ниже приведены примеры, иллюстрирующие предлагаемый способ.The following are examples illustrating the proposed method.

Пример 1.В реакционный сосуд вносят 0,5 г катализатора Ni θ3 (50 вес.%Ni), восстановленного в токе водорода при 400°С, 0,03 соды в 2,5 мл дистиллированной воды и 22,5 мл абсолютного изопропилового спирта. Катализатор насыщают водородом при перемешивании (700 односторонних качаний в минуту) в течение 1 ч, Затем в реакционный сосуд вносят 1,75 г 100% цитраля. Гидрирование прекращают после поглапе—Example 1. In the reaction vessel contribute 0.5 g of catalyst Ni θ3 (50 wt.% Ni), recovered in a stream of hydrogen at 400 ° C, 0.03 soda in 2.5 ml of distilled water and 22.5 ml of absolute isopropyl alcohol . The catalyst is saturated with hydrogen with stirring (700 one-sided swings per minute) for 1 h. Then 1.75 g of 100% citral are added to the reaction vessel. Hydrogenation is stopped after stroking—

729 пия 2 молей водорода при 6 0^е* С и атмосферном давлении. Выход цитронеллона в расчете па цитраль составляет 96% 2, 6-диметилоктанола - 3,0%, Анализ методом ГЖ.Х, ₅ 729 pd 2 moles of hydrogen at 6 0 ^e * C and atmospheric pressure. The yield of citronellone in the calculation of pa citral is 96% 2, 6-dimethyloctanol - 3.0%, GC analysis. X, ₅

П р и м е р 2. В реакционный сосуд вносят 0,5 катализатора Νί-ΟνρθΒ (50 вес%№), восстановленного в токе водорода при 400°С, 0,03 соды в 2,5 мл дистиллированной воды и 2 2,5 мл абсо- ц киотного изоамилового спирта. Катализатор насыщают водородом при перемешивании (7 00 односторонних качаний в минуту) в течение 1ч. Затем в реакционный сосуд вносят 1,75 г 100% цитраля. Гид- п рирование ведут до поглощения 2 молей водорода. При температуре опыта G0° С и атмосферном давлении выход цитронеллола в расчете на цитраль составляет 97%,PRI me R 2. In the reaction vessel contribute 0.5 catalyst Νί-ΟνρθΒ (50 wt.% No.), recovered in a stream of hydrogen at 400 ° C, 0.03 soda in 2.5 ml of distilled water and 2 2, 5 ml of absolute Kyoto isoamyl alcohol. The catalyst is saturated with hydrogen with stirring (7 00 one-way swings per minute) for 1 h. Then 1.75 g of 100% citral are added to the reaction vessel. Hydrogenation is carried out until 2 moles of hydrogen are absorbed. At a test temperature of G0 ° C and atmospheric pressure, the yield of citronellol based on citral is 97%,

2.6- диметил октанола. 2%. Анализ методом ??2.6-dimethyl octanol. 2% Method analysis ??

DK.X.DK.X.

П р и м е р 3. Гидрирование ведут на каталитической установке высокого давления. В реакционный сосуд вносят 0,5 г катализатора Mi-Cr^Os (50 вес.% Hi). За-2! тем к катализатору добавляют 0,03 г соды в 1 мл дистиллированной воды и 9,0 мл абсолютного изопропилового спирта. В полученную суспензию вносят 18,5 г 100% цитраля. Гидрирование ведут при ?ι .скорости перемешивания 7 00 односторонних качаний в минуту. При давлении водорода 40 атм и 120° получают продукт, содержащий 96,3% цитронеллола, 3,2%PRI me R 3. Hydrogenation is carried out on a catalytic installation of high pressure. 0.5 g of the catalyst Mi-Cr ^ Os (50 wt.% Hi) was added to the reaction vessel. For 2! thus, 0.03 g of soda in 1 ml of distilled water and 9.0 ml of absolute isopropyl alcohol are added to the catalyst. 18.5 g of 100% citral are added to the resulting suspension. Hydrogenation is carried out at? Ι. Mixing speeds of 7 00 one-way swings per minute. At a hydrogen pressure of 40 atm and 120 °, a product is obtained containing 96.3% citronellol, 3.2%

2.6- диметилоктанола. Анализ методом з ГЖХ. Выход цитронеллола в расчете на цитраль составляет 96,3%.2.6-dimethyloctanol. GC analysis. The yield of citronellol based on citral is 96.3%.

П р и м е р 4. Гидрирование ведут на каталитической установке высокого давления. Условия аналогичны с примером 3, но давление 60 атм. Получают продукт, содержащий 96% цитронеллола и 3,5% 2>6-диметилоктанола. Выход цитронеллола 96%. Анализ методом DKX.PRI me R 4. Hydrogenation is carried out on a catalytic installation of high pressure. The conditions are similar to example 3, but the pressure is 60 atm. A product is obtained containing 96% citronellol and 3.5% 2> 6-dimethyloctanol. The yield of citronellol 96%. DKX analysis.

П р и м е р 5» Гидрирование ведут на Каталитической установке высокого давления, Условия аналогичны с примером 3, но вместо изопропилового спирта в качестве растворителя берут изоамиловый спирт. Получают продукт, содержащий 97% цитронеллола и 2,5% 2,6-диметилоктанола,PRI me R 5 "Hydrogenation is carried out on a high-pressure catalytic installation. The conditions are similar to example 3, but instead of isopropyl alcohol, isoamyl alcohol is taken as a solvent. A product is obtained containing 97% citronellol and 2.5% 2,6-dimethyloctanol,

П р и ме р 6_К Гидрирование ведут на каталитической установке высокого давления. Условия аналогичны с примером 3, Но соду берут в количестве 0,045 г. Получают продукт, содержащий 96% цитронеллола и 3,5% 2,6-диметшюктаяола.EXAMPLE 6 _K Hydrogenation is carried out on a high pressure catalytic installation. The conditions are similar to Example 3, but soda is taken in an amount of 0.045 g. A product is obtained containing 96% citronellol and 3.5% 2,6-dimeshuktayola.

3 . 43. 4

Выход цитронеллола в расчете на цитраль 96%.The yield of citronellol based on citral is 96%.

П р и м е р 7. Гидрирование ведут на каталитической установке высокого давления. Условия аналогичны с примером 3, но берут 95% цитраль, полученный из лемогаорассового масла.PRI me R 7. Hydrogenation is carried out on a catalytic installation of high pressure. The conditions are similar to example 3, but they take 95% citral obtained from lemograss oil.

После гидрирования, отделения катализатора (фильтрацией) и отгонки раство) рителя под вакуумом 20 мм рт.ст. получают 18,1 г технического цитронеллола со следующими характеристиками: бромное число 94, альдегидов нет, гаганио* 90 ла нет, содержание спиртов 95% Пр = , 1,454. Выход технического цитронеллола от веса загруженного сырья в граммах - 18,1, в процентах - 98,1 ( в прототипе выход цитронеллола 8 3,2%, кроме того содержится 10% гераниола).After hydrogenation, separation of the catalyst (by filtration) and distillation of the solvent under vacuum, 20 mmHg 18.1 g of technical citronellol are obtained with the following characteristics: bromine number 94, no aldehydes, no gaganio * 90 la, alcohol content 95%, Pr = 1.454. The yield of technical citronellol from the weight of the loaded raw materials in grams is 18.1, in percent - 98.1 (in the prototype the yield of citronellol is 8 3.2%, in addition, 10% of geraniol is contained).

) После последующей вакуумной ректификации получают 16,6 г товарного цитронеллола со следующими характеристиками: бромное числоgl 01,5, содержание спиртов 99,5%, Пр = 1,455 (анализы по техническим условиям на цитронеллол). Выход товарного продукта в граммах 16,6, в процентах от веса цитраля в пересчете на 100% цитраль - 95,0.) After the subsequent vacuum rectification, 16.6 g of commodity citronellol are obtained with the following characteristics: bromine number gl 01.5, alcohol content 99.5%, Pr = 1.455 (analysis according to the technical conditions for citronellol). The output of the commercial product in grams is 16.6, as a percentage of the weight of citral, calculated as 100% citral - 95.0.

Полученный продукт по анализу и за[) паху (оценка парфюмеров) отвечает сорту Экстра.The resulting product for analysis and for [) the groin (evaluation of perfumers) corresponds to Extra.

Π р и мер 8, Гидрирование ведут во вращающемся автоклаве объемом 1л. В автоклав вносят 3,5 ΐ' Μί -Cpg Оз иΠ p and measures 8, Hydrogenation is carried out in a rotating autoclave with a volume of 1 liter. 3.5 ΐ 'Μί -Cpg Oz and

0,21 г ЙЦ£О₃ в 3,4 мл дистиллированной воды, добавляют 30,6 мл абмолютиого изопропилового спирта. К полученной суспензии добавляют 148 г.95% цитраля. Гидрирование ведут при начальном давлении водорода 60 атм, и температуре 115-120°С.0.21 g of JC £ O ₃ in 3.4 ml of distilled water, 30.6 ml of absolute alcohol isopropyl alcohol are added. To the resulting suspension was added 148 g. 95% citral. Hydrogenation is carried out at an initial hydrogen pressure of 60 atm, and a temperature of 115-120 ° C.

После гидрирования (условия'приведены в примере 8), отделения катализатора (фильтрацией) и отгонки растворителя под вакуумом 20 мм рт.ст. получают 146,5 г (1,5г потери при фильтрации и отгонке растворителя) технического цитронеллола со следующими характеристиками: бромное число 94, альдегидов нет, гераниола нет, содержание спиртов 95%,flp = = 1,454. Выход технического цитронеллола от веса загруженного сырья в % 98,9 в граммах - 146,5 (в прототипе выход цитронеллола 83,2%, кроме того в катализаторе содержится 10% гераниола). После вакуумной ректификации технического цитронеллола получают 134,5 г товарного цитронеллола со следующими характеристиками: бромное число 101, содержание спиртов 98%,. альдегидов нет,After hydrogenation (the conditions are given in Example 8), separation of the catalyst (by filtration) and distillation of the solvent under vacuum at 20 mm Hg. 146.5 g (1.5 g of loss during filtration and solvent distillation) are obtained for technical citronellol with the following characteristics: bromine number 94, no aldehydes, no geraniol, 95% alcohol content, flp = 1.454. The yield of technical citronellol from the weight of the loaded raw materials in% 98.9 in grams is 146.5 (in the prototype, the yield of citronellol is 83.2%, in addition, the catalyst contains 10% geraniol). After vacuum rectification of technical citronellol, 134.5 g of marketable citronellol are obtained with the following characteristics: bromine number 101, alcohol content 98%. no aldehydes

П D - 1,455 (анализы по техническим условиям на цитронеллол).P D - 1,455 (analyzes according to the technical conditions for citronellol).

Выход товарного продукта в г - 134,5. в процентах от веса исходного сырья в пересчете на 100% цитраль - 95,8, Полученный продукт по анализу и запаху отвечает сорту 'Экстра*.The output of the product in g - 134.5. as a percentage of the weight of the feedstock in terms of 100% citral - 95.8, The resulting product for analysis and odor corresponds to the grade 'Extra *.

П р и м е р 9 (сравнительный), Ведут без соды. Гидрирование ведут во вращающемся автоклаве объемом 1 л. В автоклав вносят 5,0 г NT - СГ«> Оз, приливают 35 мл (27,6 г) абсолютного изопропилового спирта и 168 мл (148 г) 95% цитраля. Гидрирование ведут при начальном давлении 60 атм и температуре 115-120°С, Получают 146 г продукта, содержащий 7 3,5% цитронеллона, 20,1% 2,6-диметилактанола и 1,3% цитронеллола.PRI me R 9 (comparative), Lead without soda. Hydrogenation is carried out in a 1 liter rotating autoclave. 5.0 g of NT - SG "Oz" are introduced into the autoclave, 35 ml (27.6 g) of absolute isopropyl alcohol and 168 ml (148 g) of 95% citral are added. Hydrogenation is carried out at an initial pressure of 60 atm and a temperature of 115-120 ° C. 146 g of product are obtained containing 7 3.5% citronellone, 20.1% 2,6-dimethylactanol and 1.3% citronellol.

Claims

This invention relates to the field of citrinellol chelate, which is a valuable perfume widely used in perfumery: laziness. A known method for producing citronellol is by hydrogenating citral with a copper-chromium catalyst at a pressure of 5 O-20 O at and a temperature of 95-125 s Sch. By this method, a product containing only 83.2% ditronellol and 10% geraniol is obtained. The yield of the technical target product per citral is 88%. The purpose of the invention is to increase the selectivity of the process and increase the yield of the target product. The goal is achieved by the fact that the process of hydrogenation of citronellol is conducted by the presence of soda in distilled water and nankel-chromium catalyst in an alcohol of C3-C at 60–120 ° C and a pressure of 1–80a. A well-prepared method for producing citronellon gives a product containing 92 -97% citronellol and only 2, O-3.5% by-product of 2, 6-dimethyloctanol. The yield of citroneplol based on citral is 96-97%. Preserve in the presence of soda, in an amount of 9% by weight. catalyst dissolved in a volume of water equal to 1/10 the volume of solvent. The examples are given illustrating the proposed method. Example 1. To the reaction vessel add 0.5 g of catalyst Hi - ((l, -, 0 (50 Bec.% Ni), reduced in a stream of hydrogen at 400 ° C, 0.03 soda in 2.5 ml of distilled water w 22.5 ml of absolute isopropyl alcohol. The catalyst is filled with hydrogen with stirring (7 oC unilateral sweeps per minute) for 1 h. Then 1.75 g of 1OO% citral is introduced into the reaction vessel. Hydrogenation is stopped after a glance (2 mo of hydrogen at bUC and atmospheric pressure, the yield of citroneloma based on citral is 96% 2, 6-dimethyltoctanol - 3.0%. Analysis by GLC method. P r and m 8 p 2, 0.6 Ni Cr203 catalysts (50 wt% N), reduced in a stream of hydrogen at 0.03 soda in 2.5 ml of diluted water and 22.5 ksh of absolute isoamyl alcohol, are introduced into the reaction vessel. The catalyst is saturated with hydrogen. with stirring (700 one-sided 1 hour per minute) for 1 h. Zgethem, 1.75 g of 100% citral is introduced into a reamchion vessel. 2 moles of hydrogen are carried out at an absorbance. At a temperature of 60 ° C and atmospheric pressure, the yield of citronellol is citral is 97%, 2,6-dimethyl octano a. 2%. Analysis method GZH.H. Example 3 Hydrogenation at a high pressure catapult installation. 0.5 g of catalyst (50 wt.% Hi) is introduced into the reaction vessel. At the same time, 0.03 g of soda is added to 1 u of the distilled water and 9.0 ml of aSccOTiOTUoix) ionopsychone spcher to the catalyst. 18.5 100% citral are added to the resulting slurry, Gpdrirovanie carried out with stirring 7 00 unilateral swings per minute. With a hydrogen pressure of 4-0 atm to 12 O °, a product is obtained - containing 96.3% of citroEgellole, Zr2% 2,6-di1-yloyl octanol, Analysis by PCH. The yield of citronellol per citral is 96.3%, P and m ep 4 Hydrogenation is carried out on a high pressure catalytic unit. The conditions are similar with the example 3 yo pressure of 6 O atm. Pachuschot product containing 969o citroneplop and 3.5% 2 | 6.dimetkloktanol. The yield of citronello ™ is 96%. PKH analysis. EXAMPLE 5 Hydrogenation is carried out in a high pressure Catalytic unit. The conditions are similar with ttpsiMepoM 3, Yo, instead of isopropyl alcohol, isoamyl alcohol is taken as the solvent. A product is obtained containing 97% CItronello and 2.5% 2,6-d11 methylinreticme. Example 8 Hydraulic piping is carried out on a high pressure catalytic installation. The conditions are similar with npicMepo 3, tto soda is taken in an amount of O, O45 g. A product is obtained containing 96% nitronellol and 3.5% 2.6 dimeg 1gganol. The yield of citronelap in the calculation of citral 96%, P p and W ep 7, Hydrogenation is carried out on a catalytic installation of high Dashuni. The conditions are similar to example 3, but take 95% citral, obtained from lemoshorassoy oil. After hydrogenation, separation of the catalyst (filtering) and distillation of the solvent under a vacuum of 20 mm Hg, 18.1 g of technical citronellol is obtained with the following characteristics MT: bromine number 94, no aldehydes, 95% discharged alcohol, 1,454 alcohol content, (xx) citronellol, based on the weight of the loaded raw material, in grams - 18.1, in percent - 98.1 (in the prototype, the output of citronelop is 83.2%, in addition, there is 10% geraniol). After the subsequent vacuum distillation, 16.6 g of marketable citronellol are obtained with the following characteristics: bromine number 101.5, alcohol content 99.5%, Po 1.455 (citronellol technical analysis) percent by weight of citral in terms of 100% citral - 95.0. The resulting product analysis and smell (estimated perfumers) corresponds to the class Extra. In the case of f i r 8, the hydrogenation is carried out in a 1l rotating autoclave. 3.5 g of Ni -CTg Oz and 0.21 g in 3.4 ml of distilled water are added to the autoclave, and 30.6 ml of abmolute isopropyl alcohol is added. To the resulting suspension was added 148 g. 95% citral. Hydrogenation is carried out at an initial pressure of hydrogen in atm, and a temperature of 115-120s. After hydrogenation (the conditions are given in Example 8), the separation of the catalyst (filtration) and the distillation of the solvent under vacuum, 2 mm Hg, st. 146.5 g (1 g 5 g loss on filtration and solvent stripping) of technical citronellol are obtained with the following characteristics: bromine number 94, no aldehydes, no geraniol, alcohols 95%, I | e 1.444. The yield of technical citronellol based on the weight of the raw material in% 98, 9 in grams is 146.5 (in the prototype, the output of citronellol is 83.2%, in addition to the galizator contains 1O% geraniol). After vacuum distillation of technical citronellol, 134.5 g of marketable citronellol is obtained with the following characteristics: a bromine number 101, with an alcohol content of 98% ,. there are no aldehydes, G D 1,455 (citronellas technical analysis). The yield of the marketable product in g is 134, in terms of the weight of the raw material in terms of 100% citral, 95.8. The resulting product according to analysis and odor corresponds to the Extra grade. PRI me R 9 (comparative) Lead without soda. Hydrogenation is carried out in a rotating 1 liter autoclave. Into the autoclave, 5.0 g of Ni-CG Oz is introduced, 35 ml (27.6 g) of absolute isopropyl alcohol and 168 ml (148 g) of 95% citral are added. Hydrogenation is carried out at an initial pressure of 60 atm and a temperature of 115-120 ° C. 146 g of product are obtained, containing 73.5% citronellon, 20.1% 2,6-dimethylactanop and 1.3% citronellol. Claim 1. Method for producing citronellol by dripping citral with increased temperature in the presence of a chromium-containing catalyst, characterized in that nickel chromium catalyst is used as a nickel-containing catalyst in order to increase the selectivity and yield of the target product in the environment of absolute alcohol of iso-Cz-Cz at a temperature of 60-120C and a pressure of 1-80 at.

2. A method according to claim 1, characterized in that the process is carried out in the presence of an additive of soda, taken in an amount of 6-9%, of the weight of the catalyst dissolved in a volume of water equal to 1/10 of the volume of solvent. Sources of information taken into account in the examination 1.: USSR author's certificate K9 938881, cl. C 07 C 33 / O2, 1950; (prototype).