CN106964406A - A kind of hydroxycitronellol catalyst - Google Patents
A kind of hydroxycitronellol catalyst Download PDFInfo
- Publication number
- CN106964406A CN106964406A CN201710241988.4A CN201710241988A CN106964406A CN 106964406 A CN106964406 A CN 106964406A CN 201710241988 A CN201710241988 A CN 201710241988A CN 106964406 A CN106964406 A CN 106964406A
- Authority
- CN
- China
- Prior art keywords
- hydroxycitronellol
- catalyst
- nickel
- parts
- dithiole
- Prior art date
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts 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
- B01J31/30—Halides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/48—Preparation 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/12—Organo silicon halides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/12—Organo silicon halides
- C07F7/14—Preparation thereof from optionally substituted halogenated silanes and hydrocarbons hydrosilylation reactions
Abstract
The invention provides a kind of hydroxycitronellol catalyst：By 100 parts of boron polymeric adsorbent, 100 500 parts of boron trifluoride ether solution, and a certain amount of tetra-n-butyl close double (1, the mercaptan of 3 dithiole, 2 thioketones 4,5 two) nickel, six water nickel chlorides, ammonium ceric nitrate, is well mixed, and load obtains a kind of hydroxycitronellol catalyst.
Description
Technical field
The present invention relates to a kind of preparation method of catalyst, especially a kind of hydroxycitronellol catalyst.
Background technology
By fast development for many years, China's essence and flavoring agent industry has been gradually completing from small workshop mode production to industrial metaplasia
Production, the autonomous Design from product image to independent research, from import equipment to professional equipment are manufactured, from sensory evaluation to using high
The detection of smart instrument, from the autonomous culture for being introduced into professional of technical staff, collect introducing and planting from wild resource and build
Many transformations such as vertical base, domestic essence and flavoring agent manufacturing has evolved into a more complete industrial system, and emerges in large numbers
Going out a collection of can directly participate in leading companies in the industry of competition in the international market.
Dihydromyrcenol is mainly from dihydromyrcene (being cracked to form from the hydrogenation products pinane of firpene) under acid catalysis
With water, formic acid addition and obtain.For limette, citrus type daily essence.Consumption is up to 5%~20% in perfumed soap, detergent.It is
Important terpene spices；Hydroxycitronellol can also be generated by hydrogenation reaction, hydroxycitronellol is the centre for preparing citronellol
Product, the catalyst that development can be catalyzed dihydromyrcene reaction generation hydroxycitronellol helps to lift citronellol Related product
Quality and speed of production.
CN1184182 discloses one kind and makees solvent with aliphatic hydrocarbon or aromatic hydrocarbon, under inert gas shielding, with VIII
Metal chlorination compound makees catalyst, and alkyl silicon is generated by 1: 1~1.5 molar ratio reaction with hydrogen silication reagent and dihydromyrcene
Compound, then the aqueous solution chlorination through hydrogen peroxide, then be layered, extract, washing, dry collect product produce citronellol.The method with
The dihydromyrcene being easy to get is raw material, and experimental implementation simplifies, and reduces many loaded down with trivial details steps, the good, yield of selectivity is high, and cost
Reduction, condition is created for industrialization.
CN100436390 discloses a kind of method for using dihydromyrcene to prepare citronellol for raw material.There is provided it is a kind of from
The method that dihydromyrcene produces citronellol through hydroboration.Metallic boron hydrides powder is added into solvent, system in blanket of nitrogen
Into borohydride solution or suspension, seal standby；Under nitrogen atmosphere, alchlor powder is added into solvent at 0 DEG C, be made
0.5~2.0mol/L solution or suspension, is sealed standby；The ether that concentration is prepared for 0.5~2.0mol/L boron trifluoride is molten
Liquid；Borine is produced again, and carries out the hydroboration of dihydromyrcene, and citronellol is obtained through rectification under vacuum.
Existing to prepare citronellol technique, using metal chloride as catalyst, waste water and dregs are more, catalytic effect
Have much room for improvement.
The content of the invention
The purpose of the present invention is：There is provided a kind of hydroxycitronellol catalyst, it is characterised in that preparation process includes：
By weight, by 100 parts of boron polymeric adsorbent, 100-500 parts of boron trifluoride ether solution, and a certain amount of four positive fourth
Base closes double (mercaptan of 1,3- dithiole -2- thioketones -4,5- bis-) nickel, and six water nickel chlorides, ammonium ceric nitrate is well mixed,
50-100 DEG C of reaction 1-5h, is filtered, and drying obtains a kind of hydroxycitronellol catalyst.
It is 0.01- that the tetra-n-butyl, which closes double (mercaptan of 1,3- dithiole -2- thioketones -4,5- two) nickel (III),
0.1 part.
The ammonium ceric nitrate is 0.5-2 parts.
0.5-2 parts of the six water nickel chloride,
The boron polymeric adsorbent is commercially available prod, and tetra-n-butyl is closed double (mercaptan of 1,3- dithiole -2- thioketones -4,5- bis-)
Nickel, six water nickel chlorides, ammonium ceric nitrate, boron trifluoride ether solution is commercially available prod,
The product of the present invention has the advantages that：
Boron polymeric adsorbent has larger specific surface area, and the area increase contacted with reactant, load tetra-n-butyl closes double (1,3-
The mercaptan of dithiole -2- thioketones -4,5- two) nickel, six water nickel chlorides, ammonium ceric nitrate is catalyzed after boron trifluoride ether solution
Effect is stronger, and reaction speed is fast, and catalytic effect is significantly improved, and solid catalyst is easily separated with water, the environmental protection without waste water and dregs
Problem.
Embodiment
Following instance is only to further illustrate the present invention, is not limitation the scope of protection of the invention.
Embodiment 1
Add 100Kg boron polymeric adsorbents, 300Kg boron trifluoride ether solutions in a kettle., 0.05Kg tetra-n-butyls close it is double (1,
The mercaptan of 3- dithiole -2- thioketones -4,5- bis-) nickel, the water nickel chlorides of 1Kg six, ammonium ceric nitrate 1Kg, be well mixed, at 75 DEG C
Under the conditions of react 3h, filter, drying, obtain hydroxycitronellol catalyst..Production code member M-1.
Embodiment 2
Add 100Kg boron polymeric adsorbents, 100Kg boron trifluoride ether solutions in a kettle., 0.01Kg tetra-n-butyls close it is double (1,
The mercaptan of 3- dithiole -2- thioketones -4,5- bis-) nickel, the water nickel chlorides of 0.5Kg six, ammonium ceric nitrate 0.5Kg be well mixed,
1h is reacted under the conditions of 50 DEG C, is filtered, drying obtains a kind of hydroxycitronellol catalyst.Production code member M-2.
Embodiment 3
Add 100Kg boron polymeric adsorbents, 500Kg boron trifluoride ether solutions in a kettle., 0.1Kg tetra-n-butyls close it is double (1,
The mercaptan of 3- dithiole -2- thioketones -4,5- bis-) nickel, the water nickel chlorides of 2Kg six, ammonium ceric nitrate 2Kg, be well mixed, 100
5h is reacted under the conditions of DEG C, is filtered, drying, a kind of hydroxycitronellol catalyst, production code member M-3.
Comparative example 1
It is added without tetra-n-butyl and closes double (mercaptan of 1,3- dithiole -2- thioketones -4,5- bis-) nickel, other conditions be the same as Example
1.Production code member M-4.
Comparative example 2
It is added without six water nickel chlorides, other conditions be the same as Example 1.Production code member M-5.
Comparative example 3
It is added without ammonium ceric nitrate, other conditions be the same as Example 1.Production code member M-6.
Comparative example 4
Without using institute's invention catalyst of the present invention, catalyst is used as using triphenylphosphine radium chloride.Production code member M-7.
Embodiment 4
Add dihydromyrcene 100g in a kettle. respectively, and be separately added into catalyst obtained by embodiment 1-3 and comparative example 1-4
Product 5g, alkyl silicide is generated with dichloro methyl silane and dihydromyrcene by 1: 1.5 molar ratio reaction, then through peroxidating
The aqueous solution chlorination of hydrogen, then purified produce citronellol.Citronellol yield is examined after 30min.
Table 1：The catalyst prod catalytic effect that different process is produced.
| Production code member | Citronellol yield % |
| M-1 | 95 |
| M-2 | 95 |
| M-3 | 97 |
| M-4 | 91 |
| M-5 | 92 |
| M-6 | 91 |
| M-7 | 86 |
Claims (5)
1. a kind of hydroxycitronellol catalyst, it is characterised in that preparation method is：
By weight, by 100 parts of boron polymeric adsorbent, 100-500 parts of boron trifluoride ether solution, and tetra-n-butyl close double
(mercaptan of 1,3- dithiole -2- thioketones -4,5- bis-) nickel (III), six water nickel chlorides, ammonium ceric nitrate is well mixed,
50-100 DEG C of reaction 1-5h, is filtered, and drying obtains dihydromyrcene alcohol production hydroxycitronellol catalyst prod.
2. a kind of hydroxycitronellol catalyst described in claim 1, it is characterised in that：By weight, described four positive fourth
It is 0.01-0.1 parts that base, which closes double (mercaptan of 1,3- dithiole -2- thioketones -4,5- two) nickel (III),.
3. a kind of hydroxycitronellol catalyst described in claim 1, it is characterised in that：By weight, the cerous nitrate
Ammonium is 0.5-2 parts.
4. a kind of hydroxycitronellol catalyst described in claim 1, it is characterised in that：By weight, the six water chlorine
Change 0.5-2 parts of nickel.
5. a kind of hydroxycitronellol catalyst described in claim 1, it is characterised in that：It is any according to claim 1-4
The hydroxycitronellol catalyst of method production.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710241988.4A CN106964406A (en) | 2017-04-14 | 2017-04-14 | A kind of hydroxycitronellol catalyst |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710241988.4A CN106964406A (en) | 2017-04-14 | 2017-04-14 | A kind of hydroxycitronellol catalyst |
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| CN201710241988.4A Pending CN106964406A (en) | 2017-04-14 | 2017-04-14 | A kind of hydroxycitronellol catalyst |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1440961A (en) * | 2003-02-21 | 2003-09-10 | 中国科学院广州化学研究所 | New method of synthesizing dihydromyrcene into citronellol |
| CN101012154A (en) * | 2007-02-01 | 2007-08-08 | 厦门中坤化学有限公司 | Method of preparing citronellol |
| CN104072531A (en) * | 2014-06-13 | 2014-10-01 | 王金明 | Catalytic hydrolysis method of dimethyl dichlorosilane |
-
2017
- 2017-04-14 CN CN201710241988.4A patent/CN106964406A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1440961A (en) * | 2003-02-21 | 2003-09-10 | 中国科学院广州化学研究所 | New method of synthesizing dihydromyrcene into citronellol |
| CN101012154A (en) * | 2007-02-01 | 2007-08-08 | 厦门中坤化学有限公司 | Method of preparing citronellol |
| CN104072531A (en) * | 2014-06-13 | 2014-10-01 | 王金明 | Catalytic hydrolysis method of dimethyl dichlorosilane |
Non-Patent Citations (3)
| Title |
|---|
| JOSÉ LUIZ F. MONTEIRO: "Catalytic Conversion of Terpenes into Fine Chemicals", 《TOPICS IN CATALYSIS》 * |
| 李敬芬: "《药物合成反应》", 31 August 2010 * |
| 熊竹君: "硅氢加成反应催化机理的研究进展", 《有机硅材料》 * |
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Application publication date: 20170721 |