CN106964406A - Catalyst for hydroxy citronellol - Google Patents

Catalyst for hydroxy citronellol Download PDF

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CN106964406A
CN106964406A CN 201710241988 CN201710241988A CN106964406A CN 106964406 A CN106964406 A CN 106964406A CN 201710241988 CN201710241988 CN 201710241988 CN 201710241988 A CN201710241988 A CN 201710241988A CN 106964406 A CN106964406 A CN 106964406A
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parts
catalyst
citronellol
hydroxy
nickel
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CN 201710241988
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Chinese (zh)
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王琪宇
曹东立
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王琪宇
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/28Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
    • B01J31/30Halides
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/48Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02Silicon compounds
    • C07F7/08Compounds having one or more C—Si linkages
    • C07F7/12Organo silicon halides
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02Silicon compounds
    • C07F7/08Compounds having one or more C—Si linkages
    • C07F7/12Organo silicon halides
    • C07F7/14Preparation thereof from optionally substituted halogenated silanes and hydrocarbons hydrosilylation reactions

Abstract

The invention provides a catalyst for hydroxy citronellol. 100 parts of boron adsorption resin, 100-500 parts of boron trifluoride diethyl etherate and a certain amount of tetra-n-butyl bis(1,3-dithiole-2-thioketone-4,5-dithiol)nickel, nickel chloride hexahydrate and ceric ammonium nitrate, and even mixing and supporting are performed to obtain the catalyst for hydroxy citronellol.

Description

一种羟基香茅醇用催化剂 One kind of catalyst hydroxy citronellol

技术领域 FIELD

[0001] 本发明涉及一种催化剂的制备方法,尤其是一种羟基香茅醇用催化剂。 [0001] The present invention relates to a method for preparing a catalyst, in particular a hydroxy citronellol catalyst.

背景技术 Background technique

[0002] 经过多年的快速发展,我国香精香料行业逐步完成了从小作坊式生产到工业化生产、从产品仿制到自主研发、从进口设备到专业设备的自主设计制造、从感官评价到使用高精仪器检测、从技术人员的引进到专业人才的自主培养、从野生资源采集到引种栽培和建立基地等多方面的转变,国内香精香料制造行业已发展成一个较完整的工业体系,并涌现出一批能够直接参与国际市场竞争的行业内领先企业。 [0002] After years of rapid development, China's gradual completion of the flavor and fragrance industry, from small workshop production to industrial production, products from imitation to independent research and development, design and manufacture of professional equipment from imported equipment to autonomy, from the sensory evaluation to use high-precision instruments detecting, from the staff to the introduction of technology professionals independent training, resources collected from the wild to establish a base introduction, cultivation and other aspects of the transition, domestic flavor and fragrance manufacturing industry has developed into a relatively complete industrial system, and the emergence of a group leading companies in the industry to participate directly in the international market competition.

[0003] 二氢月桂烯醇主要从二氢月桂烯(自蒎烯的加氢产物蒎烷裂解生成)在酸催化下和水、甲酸加成而得。 [0003] The main dihydromyrcenol (pinane cleaved from the hydrogenation product generated pinene) from dihydromyrcene under acid catalysis and water, formic acid additive derived. 用于白柠檬、柑橘型日用香精。 For lime, orange-type flavor daily. 在香皂、洗涤剂中用量可达5%〜20%。 In the soap, detergent amount of up to 5% ~20%. 是重要的萜类香料;也可以通过加氢反应生成羟基香茅醇,羟基香茅醇是制备香茅醇的中间产品,研制可以催化二氢月桂烯反应生成羟基香茅醇的催化剂有助于提升香茅醇相关产品的质量和生产速度。 It is important terpene perfume; produced by the hydrogenation reaction may be hydroxy citronellol, citronellol hydroxy citronellol intermediate product is prepared, the hydroxyl group can be generated citronellol developed catalytic reaction catalyst dihydromyrcene help citronellol related products to enhance the quality and speed of production.

[0004] CN1184182公开了一种以脂肪烃或芳香烃作溶剂,在惰性气体保护下,以VIII族金属氯化合物作催化剂,用氢硅化试剂与二氢月桂烯按1:1〜1.5的摩尔比反应生成烷基硅化物,再经过氧化氢的水溶液氧化,再分层、萃取、洗涤、干燥收集产物即得香茅醇。 [0004] CN1184182 discloses an aliphatic or aromatic hydrocarbons as a solvent, under inert gas protection, chloro-to Group VIII metal compound as catalyst, hydrosilation agent and dihydromyrcene of 1: 1 molar ratio of ~ 1.5 alkyl silicide reaction product, and then through the oxidation of hydrogen peroxide aqueous solution, and then layers were separated, extracted, washed, and dried to obtain the product was collected citronellol. 该法以易得的二氢月桂烯为原料,实验操作简化,减少许多烦琐的步骤,选择性好、产率高,且成本降低,为工业化创造了条件。 The method with dihydromyrcene readily available raw materials, simplified experimental operation, reduce the number of troublesome steps, selectivity, yield, and cost reduction, create the conditions for industrialization.

[0005] CN100436390公开了一种采用二氢月桂烯为原料制备香茅醇的方法。 [0005] CN100436390 discloses a method of using the preparation of dihydro-myrcene citronellol. 提供一种从二氢月桂烯经硼氢化反应生产香茅醇的方法。 There is provided a method of citronellol from dihydromyrcene produced via hydroboration. 在氮气氛将金属硼氢化物粉末加入溶剂,制成硼氢化物溶液或悬浮液,密封备用;在氮气氛下,在〇°C下将三氯化铝粉末加入溶剂,制成0.5〜2. OmoI/L的溶液或悬浮液,密封备用;制备浓度为0.5〜2. OmoI/L的三氟化硼的醚溶液;再产生硼烷,并进行二氢月桂烯的硼氢化,经减压精馏得香茅醇。 In a nitrogen atmosphere metal borohydride powder was added a solvent to prepare a boron hydride solution or suspension, sealed reserve; under a nitrogen atmosphere, at square ° C the solvent was added aluminum trichloride powder, made of 0.5~2. OmoI / L of a solution or suspension, sealed reserve; prepared at a concentration of 0.5~2 OmoI / L solution of boron trifluoride ether;. regenerate borane, and borohydrides dihydro-myrcene, refined under reduced pressure distillate was citronellol.

[0006] 现有的制备香茅醇工艺,使用金属氯化物作为催化剂,废水废渣较多,催化效果也有待提尚。 [0006] Preparation of citronellol conventional process, using a metal chloride as a catalyst, more waste water sludge, the catalytic effect is yet to be mentioned.

发明内容 SUMMARY

[0007] 本发明的目的是:提供一种羟基香茅醇用催化剂,其特征在于制备步骤包括: 按重量份计,将硼吸附树脂100份,三氟化硼乙醚溶液100-500份,以及一定量的四正丁基合双(1,3-二噻环戊二烯-2-硫酮-4,5-二硫醇)镍,六水氯化镍,硝酸铈铵,混合均匀,在50-1 OOtC反应I -5h,过滤,烘干,得到一种羟基香茅醇用催化剂。 [0007] The object of the present invention are: to provide a catalyst hydroxy citronellol, characterized in that the preparation step comprises: parts by weight 100 parts of boron adsorption resin, 100-500 parts of boron trifluoride ether solution, and an amount of tetra-n-butyl-co-bis (cyclopentadienyl-2-thione 1,3-thiazole-4,5-dithiol) nickel, nickel chloride hexahydrate, ammonium cerium nitrate, mixed in 50-1 OOtC reaction I -5h, filtering and drying, to obtain a catalyst hydroxy citronellol.

[0008] 所述四正丁基合双(1,3-二噻环戊二烯-2-硫酮-4,5-二硫醇)镍(III)为0.01-0.1份。 [0008] The tetra-n-butyl-co-bis (1,3-thiazol-2-thione-4,5 dicyclopentadiene dithiol) nickel (III) 0.01 to 0.1 parts.

[0009] 所述硝酸铈铵为0.5-2份。 [0009] The ammonium cerium nitrate is 0.5-2 parts.

[0010] 所述六水氯化镍0.5-2份, 所述硼吸附树脂为市售产品,四正丁基合双(I,3-二噻环戊二烯-2-硫酮-4,5-二硫醇) 镍,六水氯化镍,硝酸铈铵,三氟化硼乙醚溶液均为市售产品, 本发明的产品具有以下有益效果: 硼吸附树脂具有较大的比表面积,与反应物接触的面积增大,负载四正丁基合双(1,3-二噻环戊二烯-2-硫酮-4,5-二硫醇)镍,六水氯化镍,硝酸铈铵,三氟化硼乙醚溶液后催化效果更强,反应速度快,催化效果明显提高,固体催化剂与水易分离,没有废水废渣的环保问题。 [0010] the nickel chloride hexahydrate 0.5-2 parts, the boron adsorbing resin is a commercially available product, tetra-n-butyl-co-bis (I, 3- dithian-2-thione -4 dicyclopentadiene, 5-thiol) nickel, nickel chloride hexahydrate, ammonium cerium nitrate, boron trifluoride ether solution are commercially available products, the present invention has the following advantages: a boron adsorption resin having a large specific surface area, and increase the area of ​​contact of the reactants, tetra-n-engagement load-bis (1,3-thiazol-cyclopenta-4,5-dithiol-2-thione), nickel chloride hexahydrate, cerium nitrate ammonium, boron trifluoride ether solution after the catalytic effect is stronger, fast response, the catalytic effect is significantly improved, easy separation of the solid catalyst with water, no waste water sludge of environmental issues.

具体实施方式 Detailed ways

[0011]以下实例仅仅是进一步说明本发明,并不是限制本发明保护的范围。 [0011] The following examples further illustrate the invention only and not limit the scope of the invention.

[0012] 实施例1 在反应釜中加入IOOKg硼吸附树脂,300Kg三氟化硼乙醚溶液,0.05Kg四正丁基合双(1, 3-二噻环戊二烯-2-硫酮-4,5-二硫醇)镍,IKg六水氯化镍,硝酸铈铵IKg,混合均匀,在75°C 条件下反应3h,过滤,烘干,得到羟基香茅醇用催化剂。 [0012] Example 1 was added to the kettle IOOKg Adsorption of boron, boron trifluoride ether solution 300Kg, tetra-n-bonded 0.05Kg bis (1, 3-thiazol -4-cyclopenta-2-thione , 5-dithiol) nickel, nickel chloride hexahydrate IKG, IKG cerium ammonium nitrate, mixed at 75 ° C for the reaction conditions for 3h, filtered and dried, to give hydroxy citronellol catalyst. . 产品编号M-1。 Product Code M-1.

[0013] 实施例2 在反应釜中加入IOOKg硼吸附树脂,IOOKg三氟化硼乙醚溶液,0.OlKg四正丁基合双(1, 3-二噻环戊二烯-2-硫酮-4,5-二硫醇)镍,0.5Kg六水氯化镍,硝酸铈铵0.5Kg混合均匀,在50°C条件下反应lh,过滤,烘干,得到一种羟基香茅醇用催化剂。 [0013] Example 2 was added boron IOOKg adsorption resin in an autoclave, IOOKg boron trifluoride ether solution, 0.OlKg tetra-n-bonding bis (1, 3-thiazol-2-thione dicyclopentadiene - 4,5-dithiol) nickel, nickel chloride hexahydrate 0.5Kg, 0.5Kg ceric ammonium nitrate mixed reaction at 50 ° C for lh condition, filtering and drying, to obtain a catalyst hydroxy citronellol. 产品编号M-2。 Product Code M-2.

[00M] 实施例3 在反应釜中加入IOOKg硼吸附树脂,500Kg三氟化硼乙醚溶液,0. IKg四正丁基合双(1, 3-二噻环戊二烯-2-硫酮-4,5-二硫醇)镍,2Kg六水氯化镍,硝酸铈铵2Kg,混合均匀,在100 °C条件下反应5h,过滤,烘干,一种羟基香茅醇用催化剂,产品编号M-3。 [00M] Example 3 Adsorption of boron IOOKg added in an autoclave, boron trifluoride ether solution 500Kg, 0 IKg tetra-n-bonding bis (1, 3-thiazol-2-thione dicyclopentadiene - 4,5-dithiol) nickel, nickel chloride hexahydrate 2Kg, cerium ammonium nitrate 2Kg, mixed uniformly, a reaction at 100 ° C for 5h condition, filtering and drying, the catalyst for one hydroxy citronellol, number M-3.

[0015] 对比例1 不加入四正丁基合双(1,3-二噻环戊二烯-2-硫酮-4,5-二硫醇)镍,其他条件同实施例1。 [0015] Comparative Example 1 was not added tetra-n-butyl-co-bis (1,3-thiazol-cyclopenta-4,5-dithiol-2-thione) nickel, other conditions were the same as in Example 1. 广品编号M-4。 Wide sample No. M-4.

[0016] 对比例2 不加入六水氯化镍,其他条件同实施例1。 [0016] Comparative Example 2 Nickel chloride hexahydrate was not added, the other conditions were the same as in Example 1. 产品编号M-5。 Product Code M-5.

[0017] 对比例3 不加入硝酸铈铵,其他条件同实施例1。 [0017] Comparative Example 3 was not added ammonium cerium nitrate, other conditions were the same as in Example 1. 产品编号M-6。 Product Code M-6.

[0018] 对比例4 不使用本发明所发明催化剂,使用三苯基膦氯化铑作为催化剂。 [0018] Comparative Example 4 of the present invention does not use the inventive catalyst, triphenylphosphine rhodium chloride as a catalyst. 产品编号M-7。 Product No. M-7.

[0019] 实施例4 分别在反应釜中加入二氢月桂烯l〇〇g,并分别加入实施例1-3和对比例1-4所得催化剂产品5g,用二氯甲基硅烷与二氢月桂烯按1:1.5的摩尔比反应生成烷基硅化物,再经过氧化氢的水溶液氧化,再经提纯即得香茅醇。 [0019] Example 4 were added dihydromyrcene l〇〇g in an autoclave, and were 1-3 and Comparative Examples 1-4 were added the resulting catalyst product 5g, with dichloromethylsilane with dihydromyrcenol Example alkenyl of 1: 1.5 molar ratio of alkyl group to generate a silicide, and then through the oxidation of hydrogen peroxide aqueous solution, and then purified to obtain citronellol. 30min后检验香茅醇收率。 After 30min test citronellol yield.

[0020] 表1:不同工艺生产出的催化剂产品催化效果。 [0020] Table 1: a different process for producing a catalytic effect of the catalyst product.

Figure CN106964406AD00041

Figure CN106964406AD00051

Claims (5)

  1. 1. 一种羟基香茅醇用催化剂,其特征在于制备方法为: 按重量份计,将硼吸附树脂100份,三氟化硼乙醚溶液100-500份,以及四正丁基合双(1,3-二噻环戊二烯-2-硫酮-4,5-二硫醇)镍(III),六水氯化镍,硝酸铈铵,混合均匀,在50-100°C反应l-5h,过滤,烘干,得到二氢月桂烯醇生产羟基香茅醇用催化剂产品。 A catalyst hydroxy citronellol, characterized in that the preparation is: in parts by weight, 100 parts of boron adsorption resin, 100-500 parts of boron trifluoride ether solution, and tetra-n-butyl-co-bis (1 , 3-thiazol-cyclopenta-4,5-dithiol-2-thione) nickel (III), nickel chloride hexahydrate, ammonium cerium nitrate, mixing, reaction at 50-100 ° C l- 5h, filtered and dried to give dihydromyrcenol production hydroxy citronellol catalyst product.
  2. 2. 权利要求1所述的一种羟基香茅醇用催化剂,其特征在于:按重量份计,所述四正丁基合双(1,3-二噻环戊二烯-2-硫酮-4,5-二硫醇)镍(III)为0.01-0.1份。 One hydroxy citronellol said catalyst according to claim 1, characterized in that: parts by weight of the tetra-n-bonded-bis (1,3-thiazol-2-thione dicyclopentadiene 4,5-dithiol) nickel (III) 0.01 to 0.1 parts.
  3. 3. 权利要求1所述的一种羟基香茅醇用催化剂,其特征在于:按重量份计,所述硝酸铈铵为0.5-2份。 One hydroxy citronellol catalyst according to claim 1, characterized in that: parts by weight of the cerium ammonium nitrate is 0.5-2 parts.
  4. 4. 权利要求1所述的一种羟基香茅醇用催化剂,其特征在于:按重量份计,所述六水氯化镍0.5-2份。 One hydroxy citronellol said catalyst according to claim 1, characterized in that: in parts by weight, the parts of nickel chloride hexahydrate 0.5-2.
  5. 5. 权利要求1所述的一种羟基香茅醇用催化剂,其特征在于:根据权利要求1-4任一种方法生产的羟基香茅醇用催化剂。 One hydroxy citronellol said catalyst according to claim 1, characterized in that: any of claims 1-4 A method for producing a catalyst hydroxy citronellol.
CN 201710241988 2017-04-14 2017-04-14 Catalyst for hydroxy citronellol CN106964406A (en)

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