CN1204318A - Aromatic thioether acylation method - Google Patents
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- CN1204318A CN1204318A CN96198952A CN96198952A CN1204318A CN 1204318 A CN1204318 A CN 1204318A CN 96198952 A CN96198952 A CN 96198952A CN 96198952 A CN96198952 A CN 96198952A CN 1204318 A CN1204318 A CN 1204318A
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Abstract
The present invention relates to a process for the acylation of an aromatic thioether. In its preferred variant, the invention resides in a process for the condensation of acetic anhydride or acetyl chloride with thioanisole. The process for the acylation of an aromatic thioether according to the invention is characterised in that it consists in reacting said thioether with an acylating agent chosen from the group formed by the halides of carboxylic acids and the anhydrides of carboxylic acids, in the presence of an effective quantity of an acid zeolite.
Description
The present invention relates to the process for acylating of aromatic thioether.
In its preferred version, the present invention relates to the method for condensing of acetic anhydride or Acetyl Chloride 98Min. and thioanisole.
In following explanation of the present invention, the aromatic substance that the hydrogen atom that term " aromatic thioether " is meant directly and fragrant nuclear phase connects is replaced by a sulfide group, term " aromatic substance " is meant as document, Jerry MARCH particularly, Advanced Organic Chemistry, the 4th edition, John Willy and Sons, 1992, the conventional conception of defined aromatics such as pp.40.
Have now found that the aromatic thioether process for acylating that constitutes theme of the present invention is characterised in that in the presence of the significant quantity acid zeolite, make described thioether and the acylation reaction that is selected from carboxylic acid halides and acid anhydrides.
More particularly, the present invention relates to the process for acylating of formula I aromatic thioether:
Wherein: the A representative constitutes the cyclic group of all or part of aromatics monobasic or polynary carbocyclic ring system, the system that contains at least one SR ' group, described group can have one or more substituting groups, one or more substituting groups that the R representative is identical or different, R ' representative contains the alkyl that particular case replaces of looking of 1-24 carbon atom, and these alkyl can be non-cycloaliphatic groups saturated or unsaturated, straight or branched; The monobasic or the polynary ring alicyclic group of saturated, unsaturated or aromatics; Saturated or the unsaturated straight or branched aliphatic group that has ring substituents, R ' and R can form to be looked particular case and contains other heteroatomic ring, and n represents the number of substitution in ring base.
In the present invention, briefly, term " sulfide group " is meant-S-R ' type group that wherein R ' definition is the same.So R ' represents aliphatic or alicyclic, saturated, the unsaturated or aromatic group of acyclic simultaneously and has the saturated of ring substituents or the unsaturated aliphatic group.
The aromatic thioether of Shi Yonging is corresponding with formula I in the methods of the invention, the non-cycloaliphatic groups of the wherein saturated or unsaturation of R ' representative, straight or branched.
Comparatively preferably R ' representative contains 1-12 carbon atom, preferably contains the straight or branched alkyl of 1-6 carbon atom; This hydrocarbon chain can be determined on a case-by-case basis by a heteroatoms (for example oxygen), and a functional group (for example-CO-) is interrupted and/or has a substituting group (for example halogen atom).
Above-mentioned non-cycloaliphatic groups saturated or unsaturated, straight or branched also can be determined on a case-by-case basis and have a ring substituents.Term " ring " preferably refers to the carbocyclic ring of saturated, unsaturated or aromatics, and preferred alicyclic or aromatic ring especially contains the alicyclic of 6 carbon atoms in ring or in the phenyl ring.
Non-cycloaliphatic groups can link to each other with ring by the chemical combination key, and heteroatoms or functional group and embodiment all provide hereinafter.
Described ring can be determined on a case-by-case basis and be substituted, and the example of ring substituents especially comprises the substituting group such as R, and (I specifies in a) its implication in formula.
R ' also can represent saturated or on ring 1 or 2 place's degrees of unsaturation be arranged, and contains 3-8 carbon atom in the ring usually, the carbon ring group of preferred 6 carbon atoms; Described ring can be replaced by the substituting group such as R.
R ' also can represent the aromatic carbocyclic group, and preferred monobasic ring contains at least 4, preferred 6 carbon atoms in the ring usually; Described ring can be replaced by the substituting group such as R.
More particularly, method of the present invention is applicable to the aromatic thioether of formula I, and wherein R ' representative contains the straight or branched alkyl of 1-4 carbon atom, or phenyl.
Radicals R of the present invention ' preferred embodiment comprise methyl and ethyl.
In the aromatic thioether of logical formula I, group A can represent one to contain at least 4, the aromatics monobasic isocyclic compound group of preferred 6 carbon atoms, or form by at least two aromatic carbocyclic, and form the ortho position each other-or ortho position-and the polynary isocyclic compound group of peri-position condensation system; Or by wherein at least one is aromatics and forms ortho position-or ortho position-and polynary isocyclic compound group of forming of at least two carbocyclic rings of peri-position condensation system each other.Particularly what deserves to be mentioned is naphthalene nucleus.
Group A can have one or more substituting groups on its virtue nuclear.
Substituent number according to whether having degree of unsaturation on carbon condensation situation of encircling and the ring is decided.
This area professional can easily determine a portable substituent maximum number of ring.
In the present invention, term " a plurality of " typically refers to have on virtue nuclear and is less than 4 substituting groups.Substituent example will provide with non-limiting way hereinafter.As long as desired product is not hindered, can on ring, have any substituting group.
Specifically, method of the present invention be applicable to following formula (I aromatic thioether a):
Wherein: n is less than or equal to 4, preferably equals 0,1 or 2; Radicals R ' to represent and contain 1-6 carbon atom, preferred 1-4 carbon atom is determined on a case-by-case basis and is interrupted and/or has one or more halogen atoms by a Sauerstoffatom or carbonyl, the straight or branched alkyl of preferred chlorine atom, or phenyl; Radicals R is represented in following atom or the group:
-hydrogen atom
-containing 1-6 carbon atom, the straight or branched alkyl of preferred 1-4 carbon atom is methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl for example
-contain 2-6 carbon atom, the straight or branched thiazolinyl of preferred 2-4 carbon atom such as vinyl, allyl group
-cyclohexyl or benzyl
-contain 1-6 carbon atom, the straight or branched alkoxyl group of preferred 1-4 carbon atom, for example: methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert.-butoxy
-contain the acyl group of 2-6 carbon atom
-hydroxyl
-halogen atom, preferred fluorine, chlorine or bromine atom
-trifluoromethyl
Two R groups that-amino is positioned on two vicinal carbon atoms can form a phenyl ring with the carbon atom that links to each other with them, two adjacent atoms on group SR ' and R and the phenyl ring can form 5-7 unit ring, can be determined on a case-by-case basis in addition and contain another heteroatoms.
If n is more than or equal to 1, radicals R ' and R and phenyl ring on two adjacent atoms alkylidene group, alkenylene or alkynylene that can be contained 2-4 carbon atom link together, form a heterocycle that contains saturated, the unsaturated or aromatics of 5-7 carbon atom, one or more carbon atoms can be by another heteroatoms, and preferred sulphur atom replaces.So group SR ' and R can represent a methylene disulfide group or inferior ethylene dithiol base.
More particularly, method of the present invention be applicable to corresponding to formula (I aromatic thioether a), wherein n equals 1, radicals R ' representative contains the alkyl of 1-4 carbon atom, R represents hydrogen atom, contains alkyl or the alkoxyl group or the hydroxyl of 1-4 carbon atom.
More specifically provide below and the example of formula I corresponding compounds: between thioanisole neighbour-thiocresol-thiocresol is right-thiocresol 2-sulphur ethyl naphthalene S-phenyl thioacetate 3-(first sulfydryl) aniline S-phenyl thiopropionate
The inventive method is applicable to thioanisole in the most interesting mode.
Wish to use aromatic thioether with good chemical purity.Gratifying purity should be 97% at least.Can prove that when starting substrate contained the impurity that can poison zeolite catalyst, it was necessary coming the purifying starting substrate by for example distillation.
Acylating agent is selected from carboxylic acid halides and acid anhydrides.
Described derivative preferred source self-saturation or unsaturated, the aliphatic carboxylic acid of straight or branched, or be derived from the saturated or unsaturated cycloaliphatic carboxylic acid that is determined on a case-by-case basis and replaces.
Specifically, they are corresponding with following formula II:
Wherein: R
1Representative:
-contain the aliphatic group of saturated or unsaturated, the straight or branched of 1-24 carbon atom; Saturated or the unsaturated monobasic or the polynary ring alicyclic group that contain 3-12 carbon atom; X ' representative:
-halogen atom, preferred chlorine or bromine atom,
--O-CO-R
2Group, wherein can with R
1Identical or different R
2As R
1Define; R
2With R
1Can form an aliphatic divalent group that contains saturated or unsaturated, the straight or branched of at least 2 carbon atoms together.
The definition of term " ring substituents " is the same.
More particularly, R
1Representative contains 1-12 carbon atom, the straight or branched alkyl of preferred 1-6 carbon atom, this hydrocarbon chain can be determined on a case-by-case basis by a heteroatoms (for example oxygen), functional group (interruption and/or can have a substituting group (for example a halogen atom or a CF for example-CO-)
3Group).
R
1Preferred representative contains the alkyl of 1-4 carbon atom, for example: methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl.
R
1Also representative contains the alkenyl of 2-10 carbon atom, for example: vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, decene base.
R
1Also can represent a non-aromatic group, preferred alicyclic group, cyclohexyl for example, this group can be determined on a case-by-case basis and be substituted.Only otherwise influence desired product, on encircling, can there be any substituting group.
Substituent specific examples comprises: contain the straight or branched alkyl of individual, preferred 1-4 the carbon atom of 1-6, for example: methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl; The straight or branched alkoxyl group that contains individual, preferred 1-4 the carbon atom of 1-6, for example: methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert.-butoxy, halogen atom, preferred fluorine, chlorine or bromine atom.
Preferred acylating agent is an acid anhydrides.Particularly, they are corresponding with formula II, wherein R
1And R
2Identical and representative contains the alkyl of 1-4 carbon atom, and these groups also can be determined on a case-by-case basis and have halogen atom, preferred chlorine.
If acylating agent is an acyl halide, then it is preferably corresponding with formula II, and wherein X ' represents chlorine atom, R
1Representative contains 1-4 carbon atom, and the alkyl of preferable methyl or ethyl, this alkyl can be determined on a case-by-case basis and have halogen atom, preferred chlorine.
Specific examples corresponding to the acylating agent of formula II comprises:
Diacetyl oxide
Propionic anhydride
Isobutyric anhydride
Trifluoroacetic anhydride
Trichloroacetic anhydride
The Monochloro Acetic Acid acid anhydride
The dichloro acetic acid acid anhydride
Acetyl Chloride 98Min.
Monochloro-acetyl chloride
Dichloroacetyl chloride
Propionyl chloride
Isobutyryl chloride
Pivalyl chloride
Crotonyl chloride
According to the inventive method, acylation reaction is carried out in the presence of the catalyzer of being made up of acid zeolite.
Term " zeolite " is meant the tectosilicate class that is derived from natural or synthetic crystal form, and its crystallization is SiO
2And TO
4The result of tetrahedron element three-dimensional array; T represents trivalent element, for example: aluminium, gallium, boron, iron, preferred aluminium.
The zeolite of silico-aluminate type is the most common.
In lattice, zeolite has one and is referred to as " hole ", the hole system that is coupled together by the passage with definite diameter.
Zeolite can have one dimension, two dimension or three-dimensional channel network.
Can use natural or synthetic zeolite in the methods of the invention.
The example of spendable natural zeolite comprises: for example, and chabazite, clinoptilolite, erionite, phillipsite, offretite.
Synthetic zeolite is particularly suitable for the present invention.
Example with synthetic zeolite of one dimensional network comprises: zeolite ZSM-4, zeolite L, zeolite ZSM-12, zeolite ZSM-22, zeolite ZSM-23, zeolite ZSM-48.
The preferred zeolite examples of using with two-dimensional network comprises: mordenite, ferrierite.
Specific examples with three-dimensional network zeolite comprises: zeolite-β, zeolite Y, X zeolite, zeolite ZSM-5, zeolite ZSM-11, offretite.
The preferred synthetic zeolite that uses particularly is meant the zeolite with following structure:
The Si/Al mol ratio is 3.4 magnesium saspachite
The Si/Al mol ratio is the zeolite L of 1.5-3.5
The Si/Al mol ratio is 5-150, preferred 10-100, the more preferably mordenite of 10-25
The Si/Al mol ratio is the ferrierite of 3-10
The Si/Al mol ratio is the offretite of 4-8.5
The Si/Al mol ratio is greater than 8, preferably at 10-35, and the more preferably zeolite-β between 12-35
Zeolite Y is particularly passed through dealumination treatment (as hydrotreatment, with the salt acid elution or use SiCl
4Handle) zeolite that obtains, particularly, be the Si/Al mol ratio greater than 3, be preferable over the zeolite US-Y between the 6-60
The Si/Al mol ratio is the faujasite zeolitic X of 0.7-1.5
The Si/Al mol ratio is zeolite ZSM-5 or the silico-aluminate of 10-500
The Si/Al mol ratio is the zeolite ZSM-11 of 5-30
In all these zeolites, zeolite-β is the most suitable in the method for the invention.
The zeolite that uses in the inventive method is a known product (referring to " zeolite structure type atlas " (Atlas of zeolies structure types) of W.M.Meier and D.H.Olson, Structure Commission of the International ZeoliteAssocistion publishes (1992)) on the books in the literature.
Can use commercially available zeolite or synthesize according to the method for putting down in writing in the document.
Can be with reference to above-mentioned atlas, more specifically say so at following zeolite preparation: zeolite L, according to Barrer R.M. etc., Z.Kristallogr. publish, 128, pp352 (1969), zeolite ZSM-12, according to people's such as U.S. Pat 3 832 449 and LaPierre article, Zeolites5, pp346
(1985), zeolite ZSM-22 delivers according to people such as Kokotallo G.T., and Zeolites 5, pp.349 (1985), and zeolite ZSM-23 is according to people's such as United States Patent (USP) 4 076 842 and Rohrman A.C. article, Zeolites5, pp.352
(1985), zeolite ZSM-48, according to people's such as SchlenkerJ.L. works, Zeolites5, pp.355 (1985), zeolite-β is according to people's such as United States Patent (USP) 3 308 069 and CaulletP. article, Zeolites12, pp.240
(1992), mordenite is according to people's such as Itabashi works, Zeolites6, pp30 (1986), X zeolite and Y, respectively according to United States Patent (USP) 2 882 244 and 3 130 007, zeolite ZSM-5 is according to people's such as United States Patent (USP) 3 702 886 and Shiralkar V.P. article, pp.363 (1989), zeolite ZSM-11, according to people's such as Harrison I.D. works, Zeolites 7, pp.21 (1987).
Described zeolite has constituted the catalysis phase.Can mix use with its independent use or with mineral substrate.In the present invention, term " catalyzer " is meant according to well known to a person skilled in the art method, all by zeolite or the catalyzer to make with matrix blended form.
For this reason can be from metal oxide, as: aluminium, silicon and/or Zirconium oxide, or, specifically from kaolin, talcum or polynite, select matrix from clay.
In this catalyzer, the activation phase content is the 5-100% of catalyst weight.
Can use multi-form catalyzer in the methods of the invention: powder, as molding particles product (for example extrudate or pearl), by the bead of extruding, molding, compacting or other any currently known methods make.In actual applications, under technical scale, particle or pearl all are advantageous forms the most with regard to the facility of efficient and use.
No matter select which kind of catalyzer, if desired it is handled so that make it be acid.
Use conventional treatment method for this purpose.
Therefore, can be by zeolite being handled with ammonia, with the ammonium ion exchange alkaline kation, calcining so that make the ammonium ion pyrolysis, and is used H through the zeolite of this exchange then
+Ion replaces.
The consumption of amine equals whole alkaline kations are changed into NH at least
4+Needed amount.
For every gram zeolite, use 10 at least
-5-5 * 10
-3The amine of mole.
Can be by NH
4+The cation exchange reaction of exchange can carry out between the reaction medium reflux temperature in envrionment temperature.Reaction can continue a few hours and can repeat.
Also can make the zeolite acidifying by the acidification of routine.Can be by adding acid, for example particularly hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, phosphoric acid and trifluoromethanesulfonic acid carry out this processing.
Preferred working method is to be that the acid of 0.1-2N is passed through with the amount of 10ml/g-100ml/g zeolite by making equivalent concentration, carries out the acidifying of zeolite.Can be at an one step or preferably in several consecutive steps, finish this process.
According to the present invention, acylation reaction is preferably in catalyzer and exists down, carries out in the liquid phase that contains aromatic thioether and acylating agent.
One of initial reagent can be used as reaction solvent, but also can use a kind of organic solvent.
The specific examples that is applicable to solvent of the present invention comprises: aliphatic series or aromatics, halo or non-halogenated aliphatic hydrocarbon.Aliphatic, alicyclic or aromatic oxide.
More particularly, the example of aliphatic hydrocrbon comprises: paraffinic hydrocarbons such as hexane, heptane, octane, nonane, decane, undecane, dodecane, the tetradecane or hexanaphthene, naphthalene and aromatic hydrocarbon, the petroleum fractions of more specifically saying so and forming, the specifically aromatic hydrocarbons of solvesso cut as benzene,toluene,xylene, cumene, by alkylbenzene mixture.
The object lesson of aliphatic series or aromatic halohydrocarbons comprises: high hydrochloric ether such as zellon, hexachloroethane, part hydrochloric ether such as methylene dichloride, chloroform, 1, the 2-ethylene dichloride, 1,1,1,2, the 2-tetrachloroethane, pentaline, trieline, 1-chlorobutane, 1, the 2-dichlorobutane, monochloro-benzene, 1, the 2-dichlorobenzene, 1, the 3-dichlorobenzene, 1, the 4-dichlorobenzene, 1,2, the mixture of 4-trichlorobenzene or different chlorinated benzene, bromofom, monobromethane or glycol dibromide, the mixture of phenyl-monobromide or phenyl-monobromide and one or more dibromo-benzenes, the 1-naphthalene bromide.
Spendable organic solvent also comprises: aliphatic, alicyclic or aromatic oxide, concrete example has: ether, propyl ether, isopropyl ether, butyl ether, methyl tertiary butyl ether, amyl ether, isoamyl oxide, 1, the dimethyl ether of 2-ethylene glycol (or 1, the 2-glycol dimethyl ether), the dme of glycol ether (or 1,5-dimethoxy-3-oxa-pentane), benzyl oxide, dioxan and tetrahydrofuran (THF) (THF).
The specific examples sprotic, organic solvent that polarity is stronger that can be used for the inventive method equally comprises: nitrated compound, as Nitromethane 99Min., nitroethane, 1-nitropropane, 2-nitropropane or its mixture, oil of mirbane; Aliphatic series or aromatics nitrile are as acetonitrile, propionitrile, butyronitrile, isopropyl cyanide, benzonitrile, benzyl cyanide; Chain or cyclic carboxamide, as N,N-dimethylacetamide (DMAC), N, N-diethyl acetamide, dimethyl formamide (DMF), diethyl acetamide or 1-Methyl-2-Pyrrolidone (NMP); Methyl-sulphoxide (DMSO); Tetramethylene sulfone (tetramethylene sulfone); Hexamethylphosphorictriamide (HMPT).
Preferred solvent is methylene dichloride, tetrachloromethane, THF and ether.
Mixture with an organic solvent.
The initial substrate of preferred use is as reaction solvent.
As previously mentioned, be determined on a case-by-case basis and make aromatic thioether and acylation reaction at the previous reaction solvent with in the presence of zeolite catalyst.
Because matrix can be used as reaction solvent, so the mol ratio of aromatic thioether and acylating agent can change.This ratio can be 0.1-10, preferred 0.5-4.0.
Catalyst consumption can change within a large range in the inventive method.
If implement method of the present invention with intermittent mode, with regard to the aromatic thioether that uses, catalyst consumption is 0.01-50wt%, preferred 5-25wt%.If but implement the inventive method with continuous processing; the mixture of aromatic thioether and acylating agent is reacted on catalyst fixed bed; then the ratio of catalyzer/aromatic thioether is nonsensical, and in some given moment, catalyst weight is excessive with respect to initial aromatic thioether.
It is 0-100 that the selection of consumption of organic solvent causes the mol ratio of organic solvent and aromatic thioether usually, preferred 0-50.
The temperature of acylation reaction is decided according to the reactive behavior of starting substrate and acylating agent.
This temperature between 20 ℃-300 ℃, preferred 40 ℃-200 ℃.
Reaction is under atmospheric pressure carried out usually, but lower or higher pressure also is suitable for.If temperature of reaction is higher than the boiling point of reagent and/or product, then is reflected under the autogenous pressure and carries out.
Proceed from the reality, present method can intermittently or be carried out continuously.
According to first kind of scheme, without limits for the use of reagent.Can add with any order.
After reaction reagent begins contact, make reaction mixture rise to required temperature.
Other scheme of the present invention comprises making to be reflected in the tubular reactor carries out continuously, and this reactor has the solid catalyst that is arranged on the fixed bed.
Aromatic thioether and acylating agent can be imported reactor respectively or with the form of mixture.
Also it can be imported in the above-mentioned solvent.
The residence time of logistics is for example 15 minutes-10 hours, preferred 30 minutes-5 hours on the catalyst bed.
At reaction terminating constantly, can use ordinary method, by distillation or after removing excess reagent in advance, recrystallization in a kind of suitable solvent such as water or alcohols (methyl alcohol, ethanol) reclaims and contains by the liquid phase of the aromatic thioether of acylations.
The inventive method is specially adapted to prepare 4-methylthio phenyl ethyl ketone by the acidylate thioanisole.
The advantage of the inventive method is need not that initial aromatic thioether is carried out the processing of S-dealkylation can carry out acylation reaction.
Following embodiment of the present invention is only for specifically illustrating the meaning of the unlimited range of determining.
In these embodiments, productive rate is represented following implication: productive rate: the acylating agent mole number % embodiment 1 of acidylate aromatic thioether mole number/adding that RRAA=generates:
The zeolite of Shi Yonging is zeolite-β that PQ Zeolites company sells in this embodiment, and the Si/Al mol ratio is 12.5, is numbered CVB 8llBL25.
Following material is added in the airtight 30ml reactor: 5g (40mmol) thioanisole, Aldrich sells (purity=97%), 2.05g (20mmol) diacetyl oxide, the described zeolite-β of 0.5g calcines in 550 ℃ drying air stream in advance.
Reactor was heated 8 hours in 90 ℃.
After 8 hours, filter reaction mixture is analyzed with gas-chromatography then.
Reaction yield 60%.Embodiment 2:
Following material is added in the airtight 30ml reactor: the described thioanisole of 35g (282mmol), 28.7g (282mmol) diacetyl oxide, zeolite-β described in the 3.5g embodiment 1 calcines in 550 ℃ drying air stream in advance.
Reactor was heated 8 hours in 90 ℃.
After 12 hours, filter reaction mixture is analyzed with gas-chromatography then.
Reaction yield 45%.Embodiment 3:
Following embodiment is a comparing embodiment.
Following material is added in the airtight 30ml reactor: 2.5g acetate, the 1ml thioanisole in the 50ml chlorobenzene.
Add the zeolite-β described in the embodiment 1 then.
After lasting 10 hours under 200 ℃, do not detect the formation of acetyl thioanisole.
Claims (23)
1. the process for acylating of aromatic thioether is characterized in that in the presence of the acid zeolite of significant quantity, makes described thioether and the acylation reaction that is selected from carboxylic acid halides and carboxylic acid anhydride.
2. according to the method for claim 1, it is characterized in that described aromatic thioether has following logical formula I:
Wherein:
The A representative constitutes the cyclic group of all or part of aromatics monobasic or polynary carbocyclic ring system, contains the system of at least one SR ' group, and described group can have one or more substituting groups;
R representative can be identical or different one or more substituting groups;
What R ' representative contained 1-24 carbon atom looks the substituted alkyl of particular case, and these alkyl can be non-cycloaliphatic groups saturated or unsaturated, straight or branched; The monobasic or the polynary cycloaliphatic groups of saturated, undersaturated or aromatics; The saturated or unsaturated straight or branched aliphatic group that has ring substituents;
R ' and R can form to be determined on a case-by-case basis and contain other heteroatomic ring;
N represents the number of substitution in ring base.
3. according to the method for claim 1 and 2, it is characterized in that R ' representative in the aromatic thioether of logical formula I:
The non-cycloaliphatic groups of saturated or unsaturated, straight or branched preferably contains 1-12, the straight or branched alkyl of preferred 1-6 carbon atom; This hydrocarbon chain can be determined on a case-by-case basis by a heteroatoms, and a functional group is interrupted and/or has a substituting group;
Have the non-cycloaliphatic groups of saturated or unsaturated, the straight or branched of the substituted ring substituents that is determined on a case-by-case basis, described non-cycloaliphatic groups can pass through chemical combination key, heteroatoms or functional group and link to each other with ring;
Usually contain 3-8 on ring, the carbon ring group of preferred 6 carbon atoms, this group are saturated or on ring 1 or 2 degree of unsaturation are arranged that described ring can be substituted;
The aromatic carbocyclic group usually preferably contains at least 4, the monobasic ring of preferred 6 carbon atoms on ring, described ring can be substituted.
4. according to the method for claim 1, it is characterized in that R ' representative in the aromatic thioether of logical formula I contains straight or branched alkyl, preferable methyl or the phenyl of 1-4 carbon atom.
5. according to each method among the claim 1-3, it is characterized in that the A representative contains at least 4 carbon atoms, the monobasic aromatic carbocyclic compound group of preferred 6 carbon atoms, or polynary isocyclic compound group in the aromatic thioether of logical formula I; This group A can have one or more substituting groups on virtue nuclear.
6. according to each method among the claim 1-3, it is characterized in that the aromatic thioether of general formula (Ia):
N is less than or equal to 4 in the formula, preferably equals 0,1 or 2;
Radicals R ' to represent and contain 1-6 carbon atom, preferred 1-4 carbon atom is determined on a case-by-case basis and is interrupted and/or has one or more halogen atoms by a Sauerstoffatom or carbonyl, the straight or branched alkyl of preferred chlorine atom, or phenyl;
Radicals R is represented in following atom or the group:
-hydrogen atom
-contain 1-6 carbon atom, the straight or branched alkyl of preferred 1-4 carbon atom, for example: methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl
-contain 2-6 carbon atom, the straight or branched thiazolinyl of preferred 2-4 carbon atom, as: vinyl, allyl group
-cyclohexyl or benzyl
-containing 1-6, the straight or branched alkoxyl group of preferred 1-4 carbon atom is methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert.-butoxy for example
-contain the acyl group of 2-6 carbon atom
-hydroxyl
-halogen atom, preferred fluorine, chlorine or bromine atom
-trifluoromethyl
-amino
Being positioned at two two R groups on company's carbon atom can form a phenyl ring with the carbon atom that they link to each other,
Two adjacent atoms on group SR ' and R and the phenyl ring can form 5-7 unit ring, can be determined on a case-by-case basis in addition and contain another heteroatoms.
7. according to the method for claim 6, (n is more than or equal to 1 in I aromatic thioether a) to it is characterized in that general formula, radicals R ' and R and phenyl ring on two adjacent atoms alkylidene group, alkenylene or alkynylene that can be contained 2-4 carbon atom link together, form a heterocycle that contains saturated, the unsaturated or aromatics of 5-7 carbon atom, wherein one or more carbon atoms can be by a heteroatoms, and preferred sulphur atom replaces; Group SR ' and R are preferably formed a methylene disulfide group or inferior ethylene dithiol base group.
8. according to each method in claim 6 and 7, it is characterized in that formula (n equals 1, radicals R in I aromatic thioether a) ' representative contains the alkyl of 1-4 carbon atom, R represents hydrogen atom, contains alkyl or the alkoxyl group or the hydroxyl of 1-4 carbon atom.
9. according to the method for claim 1 and 2, it is characterized in that aromatic thioether is a thioanisole.
10. according to each method in the claim 1～9, it is characterized in that in the acylating agent of formula II:
R in the formula
1Representative:
-contain the aliphatic group of saturated or unsaturated, the straight or branched of 1-24 carbon atom; Saturated or the unsaturated monobasic or the polynary cycloaliphatic groups that contain 3-12 carbon atom; X ' representative:
-halogen atom, preferred chlorine or bromine atom;
--O-CO-R
2Group, wherein can with R
1Identical or different R
2As R
1Define; R
2With R
1Can form an aliphatic divalent group that contains saturated or unsaturated, the straight or branched of at least 2 carbon atoms.
11., it is characterized in that X ' represents chlorine atom, R in the acylating agent of formula II according to the method for claim 10
1Representative contains 1-12 carbon atom, and the straight or branched alkyl of preferred 1-4 carbon atom, this hydrocarbon chain can be determined on a case-by-case basis and be interrupted or have a substituting group by a heteroatoms, functional group, preferred halogen atom; X ' representative-O-CO-R
2Group, wherein R
1And R
2Identical, representative can be determined on a case-by-case basis and have the alkyl that contains 1-4 carbon atom of halogen atom.
12., it is characterized in that acylating agent is selected from according to the method for claim 10 and 11:
Diacetyl oxide
Propionic anhydride
Isobutyric anhydride
Trifluoroacetic anhydride
Trichloroacetic anhydride
The Monochloro Acetic Acid acid anhydride
The dichloro acetic acid acid anhydride
Acetyl Chloride 98Min.
Monochloro-acetyl chloride
Dichloroacetyl chloride
Propionyl chloride
Isobutyryl chloride
Pivalyl chloride
Crotonyl chloride.
13., it is characterized in that zeolite is natural or synthetic zeolite according to each method among the claim 1-12.
14., it is characterized in that this zeolite is to be selected from: the natural zeolite of chabazite, clinoptilolite, erionite, mordenite, phillipsite, offretite according to the method for claim 13.
15., it is characterized in that this zeolite is selected from according to the method for claim 13:
Synthetic zeolite with one dimensional network is zeolite ZSM-4, zeolite L, zeolite ZSM-12, zeolite ZSM-22, zeolite ZSM-23, zeolite ZSM-48 for example;
Zeolite with two-dimensional network, for example: mordenite, ferrierite;
Zeolite with three-dimensional network is zeolite-β, zeolite Y, X zeolite, zeolite ZSM-5, zeolite ZSM-11, offretite for example.
16. according to the method for claim 15, it is characterized in that described zeolite be the Si/Al mol ratio greater than 8, preferably between 10-35, the more preferably zeolite-β between 12-35, or Si/Al mol ratio is greater than 3, preferably the zeolite US-Y between 6-60.
17. according to each method among the claim 1-16, it is characterized in that reaction is to be determined on a case-by-case basis by halo at aqueous medium or being selected from, the aliphatic series and/or the aromatic hydrocarbon of preferred chloro, aliphatic series, alicyclic or aromatic oxide, sprotic polar solvent, preferred nitro-compound, aliphatic series or aromatics nitrile, chain or cyclic carboxylic acid amides; Methyl-sulphoxide; The tetramethylene sulfone; Hexamethylphosphorictriamide.
18. according to each method among the claim 1-17, the mol ratio that it is characterized in that aromatic thioether and acylating agent is 0.1-10, preferred 0.5-4.
19. according to each method among the claim 1-18, it is characterized in that catalyst consumption is 0.01-50wt% with regard to the aromatic thioether that uses, preferred 5-25wt%.
20. according to each method among the claim 1-19, the temperature that it is characterized in that carrying out acylation reaction is 20 ℃-300 ℃, preferred 40 ℃-200 ℃.
21. according to each method among the claim 1-20, it is characterized in that with intermittently or the successive mode implement this method.
22. contain acid zeolite, be used for the catalyzer of aromatic thioether acidylate.
23. contain zeolite-β, be used for the catalyzer of aromatic thioether acidylate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96198952A CN1204318A (en) | 1995-11-10 | 1996-11-08 | Aromatic thioether acylation method |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR95/13310 | 1995-11-10 | ||
| CN96198952A CN1204318A (en) | 1995-11-10 | 1996-11-08 | Aromatic thioether acylation method |
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| Publication Number | Publication Date |
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| CN1204318A true CN1204318A (en) | 1999-01-06 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111116478A (en) * | 2019-12-18 | 2020-05-08 | 浙江金伯士药业有限公司 | Preparation method of antibiotic virginiamycin intermediate for livestock |
-
1996
- 1996-11-08 CN CN96198952A patent/CN1204318A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111116478A (en) * | 2019-12-18 | 2020-05-08 | 浙江金伯士药业有限公司 | Preparation method of antibiotic virginiamycin intermediate for livestock |
| CN111116478B (en) * | 2019-12-18 | 2021-10-26 | 浙江金伯士药业有限公司 | Preparation method of antibiotic virginiamycin intermediate for livestock |
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