CN107952459A - The synthetic method of big annulenones and a kind of catalyst and its application - Google Patents
The synthetic method of big annulenones and a kind of catalyst and its application Download PDFInfo
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- CN107952459A CN107952459A CN201711288992.2A CN201711288992A CN107952459A CN 107952459 A CN107952459 A CN 107952459A CN 201711288992 A CN201711288992 A CN 201711288992A CN 107952459 A CN107952459 A CN 107952459A
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B01J37/18—Reducing with gases containing free hydrogen
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- 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
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Abstract
The present invention provides synthetic method and a kind of catalyst and its application of a kind of big annulenones, the catalyst provided by the present invention for synthesizing big annulenones, including carrier, and the transition metal being supported on carrier and bronsted acid；The carrier is metal oxide；Preferably, the quality based on catalyst, bronsted sour load capacity is 1 10% on carrier, and the load capacity of transition metal is 0.1 10%, and the load capacity of transition metal is more preferably 1 5%.Big annulenones is synthesized to be catalyzed macrocyclic ketone using the catalyst of the present invention, it is simple with preparation process, it is easy to operate, it is easy to the advantages such as large-scale production.
Description
Technical field
The present invention relates to the preparing technical field of big annulenones, more particularly to a kind of catalyst and utilize the catalyst
The method that macrocyclic ketone dehydrogenation prepares big annulenones.
Background technology
Many big annulenones have very graceful Moschus fragrance, such as natural cibetone (9- cycloheptadecenones), and
Artificial synthesized sounds of nature Moschus (3- methyl -5- ring tetradecenes ketone), Moschus ketenes (3- methyl -5- cyclopentadecylenes ketone), 5- rings ten
Six ketenes, 8- ring hexadecylene ketone etc..Compared with the macrocyclic ketone of saturation, these big annulenones have the Moschus fragrance of close threshold value,
And due to the presence of double bond, big annulenones is easier to degrade, and has more preferable biocompatibility.In addition, some big annulenones
Or important intermediate, such as 2- cyclopentadecylene ketone, can react, convenient synthesis of natural muskone with methyl Grignard
(3- muscones).
,, can be very high by oxidation or dehydrogenation reaction using saturated cyclic ketone as starting material when preparing ring-type ketenes
Effect, efficiently synthesis of cyclic ketenes.At present, there are document (Regio-and Enantio-selective Enolisations of
Cyclic Ketones UsingChiral Lithium Amide Bases,J.Chem.Soc.Perkin Trans.1,
1995,2535-2541) report is aoxidized two-step reaction by silyl enol ether, palladium, is realized using the amido lithium reagent of equivalent
The dehydrogenation of cyclohexanone derivative, obtains cyclonene product.In another document (Iodine (V) Reagents in Organic
Synthesis.Part 4.o-Iodoxybenzoic Acid as a Chemospecific Tool for Single
Electron Transfer-Based Oxidation Processes,J.Am.Chem.Soc.,2002,124,2245-
2258) in report uses the 2- iodosobenzoic acids of equivalent as oxidant, realizes cyclodecanone, cycloundecanone, cyclopentadecanone
Oxidation, when good yield obtains corresponding ring-type ketenes product in.These reports are real using the organic reagent of equivalent
Existing dehydrogenation, organic reagent used is expensive, can not recycling, financial cost is high.
Also there are some document reports to realize the dehydrogenation of cyclic ketone using the method for catalysis oxidation at present, such as have document
(Aerobic Dehydrogenation of Cyclic Ketones into Corresponding Phenols
Catalyzed by Heterogeneous Pd Nanocatalysts,Catalysis.Communications,2017,89,
60-63) report realizes the dehydrogenation reaction of cyclohexanone, cyclonene and benzene is obtained with moderate yield using Technique of Nano Pd as catalyst
The mixture of phenol.Also document (Aerobic Dehydrogenation of Cyclohexanone to Phenol
Catalyzed by Pd(TFA)2/2-Dimethylaminopyridine:Evidence for the Role of Pd
Nanoparticles, J.Am.Chem.Soc., 2013,135,8213-8221) report is using homogeneous palladium as catalyst, by
The regulation and control of body and reaction dissolvent, it is possible to achieve the selective dehydrogenation of cyclohexanone, respectively obtains cyclonene and phenol product, still
Substrate is limited to cyclohexanone, and catalyst amount is also bigger (3-5mol%).
In general, at present this area on the synthetically prepared ring-type ketenes of dehydrogenation of cyclic ketone document report also very
It is few, or and these reports using expensive high price iodine oxidation agent, or needing the noble metal of high catalytic amount, substrate spectrum is big
It is confined to cyclohexanone and its derivative more.
In view of big annulenones was not only widely used in essence and flavoring agent field, but also synthetic intermediate is very important, therefore
Easy to operate, the economic and environment-friendly big annulenones technique of macrocyclic ketone dehydrogenation synthesis is developed to have great importance.
The content of the invention
The present invention is makes up the deficiencies in the prior art, there is provided a kind of catalyst for being used to synthesize big annulenones and utilization this urge
The method that agent catalysis macrocyclic ketone dehydrogenation prepares big annulenones.Using the catalyst of the present invention big cyclenes is synthesized to be catalyzed macrocyclic ketone
Ketone, it is simple with preparation process, it is easy to operate, it is easy to the advantages such as large-scale production.
For the present invention to reach its purpose, the technical solution of use is as follows：
First aspect present invention provides a kind of catalyst for being used to synthesize big annulenones, and the catalyst includes carrier, and
The transition metal and bronsted acid being supported on carrier；The carrier is metal oxide.
Big annulenones is synthesized using the catalyst macrocyclic ketone dehydrogenation of the present invention, accessory substance simple with reaction process
Less, the features such as and being easy to large-scale production.
In the catalyst of the present invention, it is preferred that the quality based on catalyst, bronsted sour load capacity is 1- on carrier
10%, the load capacity of transition metal is 0.1-10%.In further preferred scheme, the load capacity of transition metal is more preferably 1-
5%.
In the catalyst of the present invention, the carrier is preferably in magnesia, calcium oxide, silica, titanium oxide and aluminium oxide
One kind or at least two, more preferably aluminium oxide, it is preferred to use aluminium oxide, has stronger acidity, can promote substrate alkene
Alcohol isomery, is conducive to dehydrogenation reaction progress.
In the catalyst of the present invention, the transition metal is preferably in iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper
One kind or at least two, more preferably nickel, to reach more preferably dehydrogenation activity and stability, promote the quick complete of dehydrogenation reaction
Into.
The present invention catalyst in, it is described it is bronsted acid be preferably phosphoric acid, sulfuric acid, perchloric acid, one kind in nitric acid or
At least two, more preferably phosphoric acid, to reach the isomery for accelerating substrate, promote substrate and metal coordination, improve conversion ratio
And selectivity；In the scheme being more highly preferred to, the Bu Lansite acid in catalyst is phosphoric acid, while transition metal is nickel, the two group
Close, more preferable catalytic activity can be obtained, conversion ratio, selectivity, dehydrogenation reaction speed are higher.
The catalyst of the present invention, can use the technique sides known in the art such as coprecipitation, infusion process, ion-exchange
Prepared by method, be more preferably made, prepare simple and easy to get using infusion process.
Second aspect of the present invention provides a kind of synthetic method of big annulenones, includes the following steps, is urged in described above
In the presence of agent, corresponding big annulenones is made in the macrocyclic ketone dehydrogenation of catalysis such as following formula (I)：
Wherein, the R in formula (I) is hydrogen, the alkyl of C1-C20, naphthyl, phenyl or the phenyl ring containing substituent.As preferred
, R can be located at the positions such as the α of carbonyl, beta, gamma, ω.Formula (I) carries the macrocyclic ketone of R substituent, its ring specifically on ring
It is upper to contain 10-18 carbon atom.
In the synthetic method of the present invention, it is preferred that when the R in formula (I) is the phenyl ring containing substituent, which can be single
Substitution or polysubstituted phenyl ring, herein the implication of " more " in " polysubstituted " refer to more than two (containing this number two), polysubstituted benzene
Ring is, for example, two substitutions, three substitutions or quaternary phenyl ring etc..For mono-substituted phenyl ring when, the substituent on phenyl ring is methyl,
Methoxyl group, benzyloxy, fluorine, chlorine, trifluoromethyl or methoxycarbonyl group；For polysubstituted phenyl ring when, multiple substituents on phenyl ring are mutual
Identical or different between phase, each substituent is independently selected from methyl, methoxyl group, benzyloxy, fluorine, chlorine, trifluoromethyl or first
Oxygen carbonyl.
In the synthetic method of the present invention, preferably using hypochlorite as oxidant in reaction system, the hypochlorite is preferred
One or more in lithium hypochlorite, sodium hypochlorite, postassium hypochlorite, calcium hypochlorite, more preferably calcium hypochlorite, price are low
It is honest and clean, and reaction speed is fast；Preferably, the dosage of hypochlorite is the 40-150% of the amount of macrocyclic ketone material, more preferably 50-
110%.
The synthetic method of the present invention, in a preferred approach, prepared big annulenones include α, alpha, beta-unsaturated ketone or α, and β-
One or more in double beta-unsaturated ketones.The class of product can be controlled by the addition of oxidant (such as calcium hypochlorite)
Type, for example, can obtain α when adding the calcium hypochlorite relative to 0.5 equivalent of macrocyclic ketone substrate, alpha, beta-unsaturated ketone, and add 1 equivalent
Or more the calcium hypochlorite of equivalent when, can obtain α, β-bis- beta-unsaturated ketones.
Further, in preferred embodiments, the α, alpha, beta-unsaturated ketone have a following structure formula (II), and the α, β-
Double beta-unsaturated ketones have following structure formula (III)：
R in formula (II) or formula (III) is hydrogen, the alkyl of C1-C20, naphthyl, phenyl or the phenyl ring containing substituent；It is excellent
Choosing, the phenyl ring containing substituent is monosubstituted or polysubstituted phenyl ring, when being mono-substituted phenyl ring, the substitution on phenyl ring
Base is methyl, methoxyl group, benzyloxy, fluorine, chlorine, trifluoromethyl or methoxycarbonyl group；For polysubstituted phenyl ring when, it is multiple on phenyl ring
Substituent is independently selected from methyl, methoxyl group, benzyloxy, fluorine, chlorine, trifluoromethyl or methoxycarbonyl group.
The synthetic method of the present invention, preferably carries out the dehydrogenation reaction, the solvent is further preferred in the presence of solvent
One or more in toluene, dimethylbenzene, n,N-Dimethylformamide, acetic acid, dimethyl sulfoxide (DMSO), more preferably acetic acid,
It is preferred that acetic acid, obtained target product yield is higher.
In the synthetic method of the present invention, with transition metal contained in catalyst, the dosage of catalyst is preferably big ring
The 0.1-10% of the amount of ketone material, more preferably 1-5%.
In the synthetic method of the present invention, the temperature of macrocyclic ketone dehydrogenation reaction is preferably 80-160 DEG C, more preferably 90-110
DEG C, to reach higher reaction yield.
In the synthetic method of the present invention, the dehydrogenation reaction of macrocyclic ketone carries out preferably in the atmosphere containing oxygen, example
As carried out in other mixed gas in atmosphere, in oxygen or containing oxygen, more preferably carried out in oxygen atmosphere.
Technical solution provided by the invention has the advantages that：
1st, big annulenones is synthesized using the catalyst of the present invention, there is catalyst amount is small, high selectivity, and accessory substance is few etc.
Feature, and economic and environment-friendly, easily operated, the amplification synthesis of suitable big annulenones.
2nd, catalyst preparation process of the invention is simple, is easy to amplification synthesis, simple filtration can be achieved with after reaction
The separation of catalyst and product.In addition, the addition by adjusting oxidant hypochlorous acid's salt, the present invention can also be realized to oxidation
The regulation and control of product, selective obtains α, alpha, beta-unsaturated ketone or α, β-bis- beta-unsaturated ketones..
3. the ketenes product purity that the synthetic method of the present invention obtains is high, fragrance is good, can be used as synthetic intermediate, also can be straight
Connect for fields such as essence, spices, cosmetics.
Embodiment
For a better understanding of the technical solution of the present invention, with reference to the embodiment content that the present invention is further explained,
But present disclosure is not limited only to following embodiments.
Below in embodiment using to reagent illustrate：
Ni(acac)2(98wt%), RuCl3(98wt%), CoCl2(98wt%), aldrich corp；Phosphoric acid
(85wt%), sulfuric acid (98wt%), perchloric acid (70%), ethanol (AR), traditional Chinese medicines reagent；Calcium hypochlorite (98wt%), hypochlorous acid
Sodium (98wt%)；Aluminium oxide (300~400 mesh, 99wt%), silica (300~400 mesh, 98wt%), titanium oxide (300~
400 mesh, 97wt%), acetic acid (AR), decahydronaphthalene (99wt%), Aladdin reagent；Ring decanone (97wt%), cyclododecanone
(99wt%), ring tridecane ketone (98wt%), cyclopentadecanone (98wt%), Cyclohexadecanone (98wt%), pacifies resistance to Jilin Chemical；
It is prepared by 3- methylcyclopentadecanones (96wt%), laboratory.
Used gas-chromatography test condition is as follows in embodiment：
Instrument model：SHIMADZU GC-2010-plus；
Chromatographic column：DB-5(30m×0.25mm×0.25μm)；
Column temperature：50 DEG C of initial temperature, is warming up to 150 DEG C with 15 DEG C/min, keeps 5min, then heated up with 20 DEG C/min
280 DEG C, keep 10min；
Injector temperature：220℃；
Fid detector temperature：300℃；
Split sampling, split ratio 50:1；
Sample size：2.0μL；
N2Flow：40mL/min；
H2Flow：400mL/min.
Used nuclear-magnetism instrument is in embodiment：Bruker Avance Neo,400MHz.
Embodiment 1：Catalyst preparation
The nickel-phosphor acid catalyst of alumina load is prepared using infusion process：Weigh Ni (acac)2(17.52g) phosphoric acid
(85wt%) (11.76g), is dissolved in ethanol (400mL) under quick (600-800 revs/min) stirring, obtains uniform solution；So
(186.00g) alumina powder (300-400 mesh) is added afterwards, when dipping 6 is small, slowly stirs lower water bath method for (200 revs/min)
Ethanol, obtained solid powder are dried at 80 DEG C, when vacuum decomposition 2 is small at 300 DEG C, be subsequently passed hydrogen reducing 2 it is small when, warp
Tabletting, broken and screening, obtain nickel-phosphoric acid catalyst.Quality based on catalyst, loads in the catalyst
Nickel mass fraction is 2%, and phosphoric acid quality fraction is 5%, which is named as 2%Ni-5%H3PO4/Al2O3。
Embodiment 2-11：Catalyst preparation
Using the method for preparing catalyst identical with embodiment 1, change transition metal, bronsted acid, carrier etc., can
Different catalyst is prepared, specifically see following table.The name of catalyst is with 1%Ni-5%H3PO4/Al2O3Exemplified by, 1%
The mass fraction of nickel in catalyst is represented, 5% represents phosphoric acid quality fraction, Al2O3Represent catalyst carrier.
1. dehydrogenation of table
Embodiment 12
In air, by the nickel-phosphor acid catalyst of alumina load made from embodiment 1 (dosage using reach Ni contents as
0.01mol), cyclododecanone (1.0mmol), acetic acid (3.0mL) and calcium hypochlorite (0.55mol) sequentially add 50mL reaction bulbs
In, reaction bulb is put into 100 DEG C of oil baths, when reaction 12 is small under quick (800 revs/min) stirrings.After reaction, will react
Liquid is down to room temperature, filtering, adds internal standard compound (decahydronaphthalene), subsequent gas chromatographic analysis reaction solution, detects and determine cyclododecene ketone
Yield is 91%, and product is the suitable back mixing compound of cyclododecene ketone.Product nuclear-magnetism information is as follows：1H-NMR(400MHz,CDCl3):
6.78 (dt, J=15.8,7.6Hz, 1H), 6.30 (dt, J=15.8Hz, 1H), 2.48 (t, J=6.6Hz, 2H), 2.25 (qd, J
=4.8Hz, 2H), 1.73 (q, J=6.6Hz, 2H)；1.69-1.54(m,2H),1.46-1.22(m,10H).
The fundamental reaction equation of the present embodiment is as follows：
Embodiment 13-23
The preparation method and embodiment 12 of embodiment 13-23 is essentially identical, is different only in that catalyst used is different, urges
Agent is specifically shown in Table 2.Each catalyst comes from obtained corresponding catalyst in embodiment 1-11.
The cyclododecene ketone yield of embodiment 13-23 is shown in Table 2.
2. cyclododecanone dehydrogenation reaction conditions of table optimize
aCyclododecanone (1.0mmol), 2%Ni-5%H3PO4/Al2O3(0.01mmol Ni), calcium hypochlorite (0.55mol),
Acetic acid (3.0mL).bInternal standard yield, decahydronaphthalene are internal standard compound.cSodium hypochlorite (1.1mol).
Embodiment 24-30 substrates are expanded
In air, 2%Ni-5%H3PO4/Al2O3(dosage is to reach Ni contents as 0.01mmol), macrocyclic ketone
(1.0mmol), calcium hypochlorite (0.55mmol), acetic acid (3.0mL) are sequentially added in 50mL reaction bulbs, and reaction bulb is put into 100
When DEG C oil bath, the quick lower reaction 12 of (800 revs/min) stirrings are small.After reaction, reaction solution is down to room temperature, filtered, directly
Column chromatography for separation product.
The target product yield of macrocyclic ketone used and each embodiment is specifically shown in Table 3 in embodiment 24-30；It is each to implement
Example product is confirmed to obtain target product, this is no longer repeated one by one by nmr analysis.
The fundamental reaction equation of embodiment 24-30 is as follows：
3. macrocyclic ketone dehydrogenation of table synthesizes big annulenones substrate and expands
Embodiment 31-36 substrates are expanded
In air, 2%Ni-5%H3PO4/Al2O3(dosage is to reach Ni contents as 0.01mmol), macrocyclic ketone
(1.0mmol), calcium hypochlorite (1.1mmol), acetic acid (3.0mL) are sequentially added in 50mL reaction bulbs, and reaction bulb is put into 100 DEG C
In oil bath, when reaction 24 is small under quick (800 revs/min) stirrings.After reaction, reaction solution is down to room temperature, filtered, directly
Column chromatography for separation product.
The target product yield of macrocyclic ketone used and each embodiment is specifically shown in Table 4 in embodiment 31-36, each to implement
Example product is confirmed to obtain target product, this is no longer repeated one by one by nmr analysis.
The fundamental reaction equation of embodiment 31-36 is as follows：
4. macrocyclic ketone dehydrogenation of table synthesizes big annulenones substrate and expands
It will be understood by those skilled in the art that under the teaching of this specification, the present invention can be made some modifications or
Adjustment.These modifications or adjustment should also be as within the scope of the claims in the present invention.
Claims (11)
1. a kind of catalyst for being used to synthesize big annulenones, it is characterised in that the catalyst includes carrier, and is supported on carrier
On transition metal and bronsted acid；The carrier is metal oxide；Preferably, the quality based on catalyst, on carrier
Bronsted sour load capacity is 1-10%, and the load capacity of transition metal is 0.1-10%, and the load capacity of transition metal is more preferably
For 1-5%.
2. catalyst according to claim 1, it is characterised in that the carrier is magnesia, calcium oxide, silica, oxygen
Change titanium and one kind in aluminium oxide or at least two.
3. according to claim 1-2 any one of them catalyst, it is characterised in that the transition metal for iron, ruthenium, osmium, cobalt,
One kind in rhodium, iridium, nickel, palladium, platinum, copper or at least two, more preferably nickel.
4. according to claim 1-3 any one of them catalyst, it is characterised in that it is described it is bronsted acid for phosphoric acid, sulfuric acid,
One kind in perchloric acid, nitric acid or at least two, more preferably phosphoric acid.
5. a kind of synthetic method of big annulenones, it is characterised in that include the following steps, described in claim any one of 1-4
Catalyst in the presence of, the macrocyclic ketone of catalysis such as following formula (I) carries out dehydrogenation reaction and corresponding big annulenones is made：
Wherein, the R in formula (I) is hydrogen, the alkyl of C1-C20, naphthyl, phenyl or the phenyl ring containing substituent；
Preferably, the phenyl ring containing substituent is monosubstituted or polysubstituted phenyl ring, when being mono-substituted phenyl ring, on phenyl ring
Substituent be methyl, methoxyl group, benzyloxy, fluorine, chlorine, trifluoromethyl or methoxycarbonyl group；For polysubstituted phenyl ring when, on phenyl ring
Multiple substituents be independently selected from methyl, methoxyl group, benzyloxy, fluorine, chlorine, trifluoromethyl or methoxycarbonyl group.
6. synthetic method according to claim 5, it is characterised in that using hypochlorite as oxidant in reaction system, institute
State the one or more that hypochlorite is preferably selected from lithium hypochlorite, sodium hypochlorite, postassium hypochlorite, calcium hypochlorite, preferably secondary chlorine
Sour calcium；Preferably, the dosage of hypochlorite is the 40-150% of the amount of macrocyclic ketone material.
7. synthetic method according to claim 5, it is characterised in that the big annulenones includes α, alpha, beta-unsaturated ketone or α,
One or more in β-bis- beta-unsaturated ketones；
Preferably, the α, alpha, beta-unsaturated ketone have following structure formula (II), and the α, β-bis- beta-unsaturated ketones have such as lower structure
Formula (III)：
R in formula (II) or formula (III) is hydrogen, the alkyl of C1-C20, naphthyl, phenyl or the phenyl ring containing substituent；Preferably,
The phenyl ring containing substituent is monosubstituted or polysubstituted phenyl ring, and when being mono-substituted phenyl ring, the substituent on phenyl ring is
Methyl, methoxyl group, benzyloxy, fluorine, chlorine, trifluoromethyl or methoxycarbonyl group；For polysubstituted phenyl ring when, multiple substitutions on phenyl ring
Base is independently selected from methyl, methoxyl group, benzyloxy, fluorine, chlorine, trifluoromethyl or methoxycarbonyl group.
8. according to claim 5-7 any one of them synthetic methods, it is characterised in that carry out the dehydrogenation in the presence of solvent
Reaction, one or more of the solvent in toluene, dimethylbenzene, n,N-Dimethylformamide, acetic acid, dimethyl sulfoxide (DMSO),
Preferably acetic acid.
9. according to claim 5-8 any one of them synthetic methods, it is characterised in that with transition metal contained in catalyst
Meter, catalyst amount are the 0.1-10% of the amount of macrocyclic ketone material.
10. according to claim 5-9 any one of them synthetic methods, it is characterised in that the temperature of macrocyclic ketone dehydrogenation reaction is
80-160℃。
11. according to claim 5-10 any one of them synthetic methods, it is characterised in that the dehydrogenation reaction of macrocyclic ketone containing
Carried out in the atmosphere of oxygen.
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| CN110227512A (en) * | 2019-06-17 | 2019-09-13 | 万华化学集团股份有限公司 | A kind of preparation method and its application of the catalyst preparing beta-unsaturated ketone for Saucy-Marbet reaction |
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| CN110227512B (en) * | 2019-06-17 | 2022-01-07 | 万华化学集团股份有限公司 | Preparation method and application of catalyst for preparing unsaturated ketone by Saucy-Marbet reaction |
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