CN104918901A - Methods of producing para-xylene and terephthalic acid - Google Patents

Methods of producing para-xylene and terephthalic acid Download PDF

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Publication number
CN104918901A
CN104918901A CN201380059080.1A CN201380059080A CN104918901A CN 104918901 A CN104918901 A CN 104918901A CN 201380059080 A CN201380059080 A CN 201380059080A CN 104918901 A CN104918901 A CN 104918901A
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otf
catalyzer
solvent
acid
alkyl
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增野真家
R·L·史密斯
J·比斯尔
M·福斯特
P·B·史密斯
D·A·赫克尔
E·J·斯塔克
D·R·亨顿
A·杜米特拉斯库
K·布龙
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Origin Materials Operating Inc
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Micromidas Inc
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Priority claimed from US13/838,761 external-priority patent/US8889938B2/en
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Abstract

The present disclosure provides methods to produce para-xylene, toluene, and other compounds from renewable sources (e.g., cellulose, hemicellulose, starch, sugar) and ethylene in the presence of a catalyst. For example, cellulose and/or hemicellulose may be converted into 2,5-dimethylfuran (DMF), which may be converted into para-xylene by cycloaddition of ethylene to DMF. Para-xylene can then be oxidized to form terephthalic acid.

Description

The manufacture method of p-Xylol and terephthalic acid
the cross reference of related application
This application claims the U.S. Provisional Patent Application the 61/701st submitted on September 14th, 2012, the U.S. Patent application the 13/838th that No. 276 and on March 15th, 2013 submit to, the right of priority of No. 761, at this, its full text is incorporated herein by reference.
Technical field
Present disclosure relates generally to the manufacture of p-Xylol and terephthalic acid, more specifically, relates to and manufactures p-Xylol and terephthalic acid by reproducible biomass resource (such as, Mierocrystalline cellulose, hemicellulose, starch, sugar) and ethene.
Background technology
Very high demand is had for the manufacture of clothes and plastics to by reproducible biomass resource manufacture p-Xylol and terephthalic acid.Terephthalic acid is the precursor that can be used for the polyethylene terephthalate (PET) manufacturing polyester textile.Terephthalic acid can by the oxidation manufacture of p-Xylol.
P-Xylol is naturally occurring aromatic hydrocarbons in oil and coal tar.The business manufacture of p-Xylol is realized by the catalytic reforming of petroleum derivative usually.See, such as, No. 2012/0029257th, U.S. Patent application.But, use the raw material based on oil to carry out business manufacture p-Xylol (and manufacturing terephthalic acid thus) and produce greenhouse gas emission, and keep the dependence to petroleum resources.
Optionally in addition manufacture the method for p-Xylol under study for action by reproducible biomass resource.Biomass containing Mierocrystalline cellulose and/or hemicellulose can change into DMF, and then DMF can change into p-Xylol by the Di Ersi of ethene-Alder cycloaddition.See, such as, United States Patent (USP) the 8th, 314, No. 267; WO 2009/110402.This area at present known Di Ersi-Alder condition manufacturing p-Xylol by ethene and the cycloaddition of DMF causes DMF at least partially to change into 2, the 5-hexanediones (HD) be usually polymerized usually.The side reaction relating to HD like this causes reducing for the selectivity of p-Xylol.See, such as, the people such as Williams, ACS Catal.2012,2,935-939; The people such as Do, ACS Catal.2013,3,41-46.
Therefore, this area needs the optional method manufacturing p-Xylol and terephthalic acid in addition.
Summary of the invention
Present disclosure solves this demand by providing the method using special catalyst, solvent and reaction conditions to manufacture p-Xylol by 2,5-dimethyl furan, 2,5-hexanediones or its combination.The p-Xylol produced then can be oxidized manufacture terephthalic acid.
On the one hand, the method for the compound by following one or more formula I of manufacture is provided:
Wherein each R 1and R 2be hydrogen, alkyl, cycloalkyl, Heterocyclylalkyl, aryl or heteroaryl independently:
A) by the compound of one or more formula A, the compound of one or more formula B:
Or its arbitrary combination and ethene, catalyzer and optional solvent merge, forming reactions mixture; With
B) by the compound of one or more the formula A in reaction mixture, the compound of one or more formula B or its arbitrary combination at least partially with the compound producing one or more formula I at least partially of ethene.
Provide by following manufacture p-Xylol (that is, wherein R in formula I 1and R 2is separately methyl) method:
A) by 2,5-dimethyl furan (DMF), 2,5-hexanediones (HD) or its combination merge with ethene, catalyzer and optional solvent, forming reactions mixture; With
B) by DMF, the HD in reaction mixture or its combination at least partially with the p-Xylol of generation at least partially of ethene.
Provide in addition by following manufacture p-Xylol (that is, wherein R in formula I 1and R 2is separately methyl), toluene (that is, wherein R in formula I 1methyl, and R 2hydrogen) or its method combined:
A) by 2,5-dimethyl furan, 2-methyl furan, 2,5-hexanediones, 4-oxo valeral or its arbitrary combination and ethene, catalyzer and optional solvent merge, forming reactions mixture; With
B) by 2,5-dimethyl furans in reaction mixture, 2-methyl furan, 2,5-hexanediones, 4-oxo valeral or its combination at least partially with the p-Xylol of generation at least partially of ethene.
In a variation pattern, provide by following manufacture p-Xylol (that is, wherein R in formula I 1and R 2is separately methyl) method:
A) provide starting raw material, wherein starting raw material is 2,5-dimethyl furan (DMF), 2,5-hexanediones (HD) or its combination;
B) ethene is provided;
C) catalyzer is provided;
D) optionally solvent is provided;
E) starting raw material and ethene, catalyzer and optional solvent are merged, forming reactions mixture; With
F) by DMF, the HD in reaction mixture or its p-Xylol of generation at least partially combined.
In another variation pattern, provide by following manufacture p-Xylol (that is, wherein R in formula I 1and R 2is separately methyl) method:
2,5-dimethyl furan (DMF) a) is provided;
B) ethene is provided;
C) catalyzer is provided;
D) solvent is provided;
E) DMF and ethene, catalysts and solvents are merged, forming reactions mixture; With
F) by the p-Xylol of generation at least partially of the DMF in reaction mixture.
In another variation pattern again, provide by following manufacture p-Xylol (that is, wherein R in formula I 1and R 2is separately methyl) method:
2,5-hexanedione (HD) a) is provided;
B) ethene is provided;
C) catalyzer is provided;
D) optionally solvent is provided;
E) HD and ethene, catalyzer and optional solvent are merged, forming reactions mixture; With
F) by the p-Xylol of generation at least partially of the HD in reaction mixture.
In some embodiments of any aforesaid method, the method also comprises separating paraxylene from reaction mixture.
In some embodiments of any aforesaid method, catalyzer is the catalyzer containing metal.Catalyzer can comprise metallic cation and counter ion.Metallic cation can be selected from, such as, and 3 races, 9 races, 10 races, 11 races or lanthanon.In some embodiments, catalyzer comprises monovalent metal cation, divalent metal or trivalent metal cation.Monovalent metal cation can be, such as, and Cu +.Divalent metal can be, such as, and Cu 2+, Co 2+, Cr 3+, Ni 2+, Mg 2+or Zn 2+.Trivalent metal cation can be, such as, and Al 3+, Bi 3+, Fe 3+, Gd 3+, In 3+, Nd 3+, La 3+, Sc 3+or Y 3+.Counter ion suitable in catalyzer can comprise, such as, and halogenide (such as, muriate, bromide), fluoroform sulphonate (-OTf) and carboxylate salt (such as, formate, acetate, acetyl pyruvate).
In some embodiments, catalyzer is aluminum chloride, aluminum bromide, trifluoromethanesulfonic acid aluminium, bismuth chloride, bismuth bromide, Bismuth triflate, cupric chloride, cupric bromide, copper trifluoromethanesulfcomposite, copper (II) two (trifyl) imide, cobalt chloride, cobaltous bromide, trifluoromethanesulfonic acid cobalt, chromium chloride, chromic bromide, trifluoromethanesulfonic acid chromium, iron(ic) chloride, iron bromide, trifluoromethanesulfonic acid iron, Gadolinium trichloride, gadolinium bromide, trifluoromethanesulfonic acid gadolinium, indium chloride, indium bromide, trifluoromethanesulfonic acid indium, nickelous chloride, nickelous bromide, trifluoromethanesulfonic acid nickel, Neodymium trichloride, neodymium bromide, trifluoromethanesulfonic acid neodymium, magnesium chloride, magnesium bromide, trifluoromethanesulfonic acid magnesium, Lanthanum trichloride, lanthanum bromide, trifluoromethanesulfonic acid lanthanum, Scium trichloride, scandium bromide, trifluoromethanesulfonic acid scandium, tin chloride, Tin tetrabromide, trifluoromethanesulfonic acid tin, titanium chloride, titanium bromide, trifluoromethanesulfonic acid titanium, vanadium chloride, bromination vanadium, trifluoromethanesulfonic acid vanadium, Yttrium trichloride, yttrium bromide, trifluoromethanesulfonic acid yttrium, zinc chloride, zinc bromide, trifluoromethanesulfonic acid zinc, or its arbitrary combination.In one embodiment, catalyzer is cupric chloride, copper trifluoromethanesulfcomposite or trifluoromethanesulfonic acid yttrium.
In some embodiments, catalyzer is Al (OTf) 3, Bi (OTf) 3, Cu (OTf) 2, Cu (OTf), Cr (OTf) 3, Fe (OTf) 3, Gd (OTf) 3, In (OTf) 3, Ni (OTf) 2, Nd (OTf) 3, Rb (OTf), Cs (OTf), Mg (OTf) 2, La (OTf) 3, Sc (OTf) 3, Ti (OTf) 4, V (OTf) 5, Y (OTf) 3, Zn (OTf) 2, Pt (OTf) 2, Pd (OTf) 2, AgOTf, Au (OTf) 3, Tl (OTf) 3, Tl (OTf), Re (OTf) 3, Hg 2(OTf) 2, Hg (OTf) 2, NH 4(OTf), Sn (OTf) 4, Sn (OTf) 3, Sn (OTf) 2, B (OTf) 3, Ga (OTf) 3, Pb (OTf) 4, Pb (OTf) 2, Co (OTf) 3, Co (OTf) 2, Ge (OTf) 4, Ge (OTf) 3, Ge (OTf) 2, Ge (OTf), Ce (OTf) 4, Ce (OTf) 3or its arbitrary combination.
Catalyzer can be metal-salt, comprises anyly to change into the salt of the different catalytic species for reaction described herein by in-situ transesterification.Such as, the catalyzer of use can be copper trifluoromethanesulfcomposite.Be not intended to stick to any theory, under some reaction conditions, copper trifluoromethanesulfcomposite can produce trifluoromethanesulfonic acid, and it can contribute to the speed increasing chemical reaction at least in part.
In some embodiments, catalyzer is non-load.In other embodiments, catalyzer is solid supported.Such as, can by one or more above-mentioned metallic cations deposition on a solid support.Suitable carrier comprises, such as, and silicon-dioxide, aluminum oxide, mordenite, carbon (comprise, such as, gac) and zeolite.In one embodiment, catalyzer can be the copper (II) on mordenite, the cupric chloride on aluminum oxide or the cupric chloride on HY zeolite.The catalyzer of such solid supported can more easily reclaim in a continuous process, recirculation and use.
In other embodiment again, catalyzer can be acid, comprises Lewis acid or weak acid.In other embodiment again, catalyzer can be heteropolyacid.Such as, in one embodiment, catalyzer is silicomolybdic acid (molybdosilicic acid) or phospho-molybdic acid.
In other embodiment again, catalyzer can be (a) sulfonic acid or its salt, ester, acid anhydrides or resin, (b) sulphonamide or its salt or (c) sulfimide or its salt.The suitable example of such catalyzer can comprise trifluoromethanesulfonic acid (trifluoromethanesulfonic acid or triflic acid), 4-toluene sulfonic acide (also referred to as tosic acid) and trifluoromethanesulfonic acid imide (triflimide).
In some embodiments of any aforesaid method, solvent system comprises aprotic solvent.Solvent also can be water-fast.Solvent can have one or more functional group, and it comprises, such as, and ether, ester, ketone, alcohol and halogen.
In some embodiments, solvent system comprises ether, and it can comprise cyclic ethers, polyethers, glycol ether and other copolyethers.Suitable ether solvents can comprise diox, dioxin, glyme, diglyme, triglyme, tetrahydrofuran (THF) and arbitrary combination thereof or mixture.In one embodiment, solvent system comprises Isosorbide-5-Nitrae-diox.In another embodiment, solvent system comprises triglyme.
In other embodiments, solvent system comprises N,N-DIMETHYLACETAMIDE (such as, N,N-dimethylacetamide), dimethyl formamide (such as, DMF), acetonitrile, tetramethylene sulfone, diox, diox, dme, ether, ethylene glycol dimethyl ether (monoglyme), diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme), TEG dimethyl ether (tetraethylene glycol dimethyl ether), tetrahydrofuran (THF), ethylene glycol, Diethylene Glycol, triethylene glycol, polyoxyethylene glycol, cyclobutanone, cyclopentanone, pimelinketone, suberone, cyclooctanone, methyl acetate, ethyl acetate, propyl acetate, butylacetate, methyl lactate, ethyl lactate, propyl lactate, n-Butyl lactate, triactin, Dibutyl phthalate, butane, pentane, pentamethylene, hexane, hexanaphthene, heptane, suberane, octane, cyclooctane, nonane, decane, hendecane, 12 carbon alkane, hexadecane, tetrachloride, chloroform, methylene dichloride, Nitromethane 99Min., toluene, methyl-phenoxide, oil of mirbane, bromobenzene, methylpyrrole (such as, N-methylpyrrole), methyl-2-pyrrolidone (such as, N-Methyl pyrrolidone), dimethyl furan (such as, 2,5-dimethyl furan), dichlorobenzene (such as, orthodichlorobenzene), water, p-Xylol, sym-trimethylbenzene, 12 carbon alkylbenzenes, amylbenzene, hexyl benzene, Wibaryl A, Wibaryl B, Wibaryl AB, Wibaryl F, Wibaryl R, Cepsa Petrepar 550-Q, Santovac, phenyl ether, methyl diphenyl ether, ethyl phenyl ether, water or its arbitrary combination or mixture.In some embodiments, solvent system comprises diox, 12 carbon alkane, hexadecane, sym-trimethylbenzene, 2,5-dimethyl furans, p-Xylol or its arbitrary combination or mixture.In one embodiment, solvent system comprises diox, 12 carbon alkane, p-Xylol or its arbitrary combination or mixture.
In some embodiments, solvent system comprises water, aliphatic solvent (it can be side chain or straight chain), aromatic solvent or alkyl benzene solvent.In one embodiment, solvent system comprises phenyl ether or alkyl diphenyl ether.
In other embodiment again, solvent system comprises ionic liquid.Suitable ionic liquid can comprise, such as, and 1-allyl group-3-tri-methylimidazolium bromide, 1-benzyl-3-methyl imidazolium tetrafluoroborate or its arbitrary combination or mixture.
Be to be understood that, any explanation for used catalyst in methods described herein all can be combined with any explanation for solvent, as each, respectively combination is listed all separately.
Such as, in some embodiments:
I () catalyzer is metal chloride, metal trifluoroacetate mesylate, metal acetate or metal acetyl acetonate; And
(ii) solvent system comprises ether, C 8+alkyl solvents (such as, decane, 12 carbon alkane) or p-Xylol.
In some embodiments:
I () catalyzer is metal chloride, metal trifluoroacetate mesylate, metal acetate or metal acetyl acetonate; And
(ii) solvent system comprises ether, C 4+alkyl solvents (such as, decane, 12 carbon alkane), p-Xylol or its any mixture or combination.
In some embodiments, catalyzer is metal trifluoroacetate mesylate; And solvent system comprises diox or 12 carbon alkane or its any mixture or combination.In other implementations, solvent system also comprises the p-Xylol as solvent.In other embodiment again, catalyzer is metal trifluoroacetate mesylate; And solvent system comprises p-Xylol.
In some embodiments:
I () catalyzer is cupric chloride, copper trifluoromethanesulfcomposite or trifluoromethanesulfonic acid yttrium; And
(ii) solvent system comprises ether, C 4+alkyl solvents, p-Xylol or its any mixture or combination.
In one embodiment, catalyzer is copper trifluoromethanesulfcomposite (I).In another embodiment, catalyzer is copper trifluoromethanesulfcomposite (II).
In some embodiments:
I () catalyzer is cupric chloride, copper trifluoromethanesulfcomposite or trifluoromethanesulfonic acid yttrium; And
(ii) solvent system comprises diox, 12 carbon alkane, p-Xylol or its any mixture or combination.
In one embodiment, catalyzer is copper trifluoromethanesulfcomposite (I).In another embodiment, catalyzer is copper trifluoromethanesulfcomposite (II).
In some embodiments:
I () catalyzer is copper trifluoromethanesulfcomposite; And
(ii) solvent system comprises p-Xylol and C 8+the mixture of alkyl solvents.
In one embodiment, catalyzer is copper trifluoromethanesulfcomposite (I).In another embodiment, catalyzer is copper trifluoromethanesulfcomposite (II).In one embodiment, C 8+alkyl solvents is 12 carbon alkane.
In some embodiments:
I () catalyzer is sulfonic acid; And
(ii) solvent system comprises ether, C 8+alkyl solvents, p-Xylol or its any mixture or combination.
In some embodiments:
I () catalyzer is sulfonic acid; And
(ii) solvent system comprises diox, 12 carbon alkane, p-Xylol or its any mixture or combination.
In some embodiments:
I () catalyzer is trifluoromethanesulfonic acid; And
(ii) solvent system comprises ether, C 4+alkyl solvents, p-Xylol or its any mixture or combination.
In some embodiments:
I () catalyzer is trifluoromethanesulfonic acid; And
(ii) solvent system comprises diox, 12 carbon alkane, hexadecane, p-Xylol or its any mixture or combination.
In some embodiments:
I () catalyzer is trifluoromethanesulfonic acid; And
(ii) solvent system comprises C 4+alkyl solvents.
In one embodiment:
I () catalyzer is trifluoromethanesulfonic acid; And
(ii) solvent system comprises 12 carbon alkane or hexadecane.
In some embodiments:
I () catalyzer is metal trifluoroacetate mesylate, trifluoromethanesulfonic acid or heteropolyacid; And
(ii) solvent system comprises ether or normal alkane.
In one embodiment, catalyzer is selected from La (OTf) 3, Nd (OTf) 3, Sc (OTf) 3, Cu [N (Tf) 2] 2, Y (OTf) 3, [Cu (I) OSO 2cF 3] 2c 6h 6and the metal trifluoroacetate mesylate of arbitrary combination.In another embodiment, catalyzer is trifluoromethanesulfonic acid.In another embodiment again, heteropolyacid is H 4[SiMo 12o 40] x H 2o, H 3[PMo 12o 40] x H 2o or its arbitrary combination.In one embodiment, solvent system comprises ether, such as ， diox or triglyme.In another embodiment, solvent system comprises alkane, such as 12 carbon alkane.
In some embodiments:
I () catalyzer is heteropolyacid; And
(ii) solvent system comprises ether, C 8+alkyl solvents (such as, decane, 12 carbon alkane), p-Xylol or its any mixture or combination.
In some embodiments:
I () catalyzer is heteropolyacid; And
(ii) solvent system comprises diox, 12 carbon alkane, p-Xylol or its any mixture or combination.
In some embodiments:
I () catalyzer is aluminum chloride; And
(ii) solvent system comprises ether, C 8+alkyl solvents (such as, decane, 12 carbon alkane), p-Xylol or its any mixture or combination.
In some embodiments:
I () catalyzer is aluminum chloride; And
(ii) solvent system comprises diox, 12 carbon alkane, p-Xylol or its any mixture or combination.
In one embodiment:
I () catalyzer is cupric chloride, copper trifluoromethanesulfcomposite, trifluoromethanesulfonic acid yttrium, crystal aerugo or cupric acetylacetonate; And
(ii) solvent system comprises diox, triglyme or its any mixture or combination.
In one embodiment:
I () catalyzer is copper trifluoromethanesulfcomposite or trifluoromethanesulfonic acid yttrium; And
(ii) solvent system comprises diox or triglyme.
In another embodiment:
I () catalyzer is copper trifluoromethanesulfcomposite or trifluoromethanesulfonic acid yttrium; And
(ii) solvent system comprises C 8+alkyl solvents (such as, decane, 12 carbon alkane).
In another embodiment again:
I () catalyzer is copper trifluoromethanesulfcomposite or trifluoromethanesulfonic acid yttrium; And
(ii) solvent system comprises p-Xylol.
In another embodiment again, catalyzer is copper trifluoromethanesulfcomposite, and solvent system comprises ether, such as diox or triglyme.In another embodiment again, catalyzer is crystal aerugo or cupric acetylacetonate, and solvent system comprises ether, such as diox or triglyme.
Should understand further, above-mentioned catalyst/solvent combination may be used for using HD as starting raw material, using DMF as starting raw material or use both HD and DMF as the reaction of starting raw material.
Such as, provide the method by following manufacture p-Xylol: starting raw material, ethene, solvent system and catalyzer are merged, forming reactions mixture, wherein starting raw material is 2,5-dimethyl furan, 2,5-hexanediones or its combination; With the p-Xylol of generation at least partially by the starting raw material in reaction mixture.
Provide the method by following manufacture p-Xylol:
A) provide starting raw material, wherein starting raw material is 2,5-dimethyl furan;
B) ethene is provided;
C) provide catalyzer, wherein catalyzer is metal chloride, metal trifluoroacetate mesylate, metal acetate, metal acetyl acetonate or heteropolyacid;
D) provide solvent system, wherein solvent system comprises ether, C 8+alkyl solvents, aromatic solvent, ionic liquid or its any mixture or combination;
E) starting raw material, ethene, solvent system and catalyzer are merged, forming reactions mixture; With
F) by the p-Xylol of generation at least partially of the starting raw material in reaction mixture.
Manufactured in the embodiment of p-Xylol by 2,5-dimethyl furan at some, catalyzer is cupric chloride, copper trifluoromethanesulfcomposite, trifluoromethanesulfonic acid yttrium, venus crystals or cupric acetylacetonate.Manufactured in the embodiment of p-Xylol by 2,5-dimethyl furan at some, solvent system comprises diox, 12 carbon alkane, decane, p-Xylol, phenyl ether, alkyl diphenyl ether or its any mixture or combination.
Provide the method by following manufacture p-Xylol in addition:
A) provide starting raw material, wherein starting raw material is 2,5-dimethyl furan, 2,5-hexanediones or its combination;
B) ethene is provided;
C) provide catalyzer, wherein catalyzer is heteropolyacid or sulfonic acid;
D) solvent system is provided;
E) starting raw material, ethene, solvent system and catalyzer are merged, forming reactions mixture; With
F) by the p-Xylol of generation at least partially of the starting raw material in reaction mixture.
At some by 2,5-dimethyl furan, 2,5-hexanedione or its combination manufacture in the embodiment of p-Xylol, and solvent system comprises diox, 12 carbon alkane, decane, hexadecane, 2,5-dimethyl furans, p-Xylol, phenyl ether, alkyl diphenyl ether or its any mixture or combination.
In other embodiment again, at the temperature of at least 150 DEG C or 150 ~ 300 DEG C, DMF (if present) at least partially, HD (if present) or its combination are changed into p-Xylol.
The p-Xylol manufactured by above-mentioned any means may be used for manufacturing plastics or fuel.
Provide by the following method being manufactured terephthalic acid by p-Xylol in addition:
A) p-Xylol is manufactured according to any means as herein described; With
B) make p xylene oxidation, produce terephthalic acid.
Embodiment
Below describe and illustrate many example arrangement, method, parameter etc.But will be appreciated that, these descriptions have no intention to be limited the scope of present disclosure, but provide as the description to illustrative embodiments.
Following description relates to the compound of compound by formula A or formula B:
and/or
The method of the compound of manufacture formula I:
Wherein each R 1and R 2be hydrogen, alkyl, cycloalkyl, Heterocyclylalkyl, aryl or heteroaryl independently.R 1and R 2it can be identical or different substituting groups.In some embodiments, each R 1and R 2be hydrogen or alkyl independently.
In some embodiments, the compound of formula I is the compound of p-Xylol (PX), formula A is 2,5-dimethyl furan (DMF), and the compound of formula B is 2,5-hexanedione (HD).Therefore, the method being manufactured p-Xylol (PX) by 2,5-dimethyl furan (DMF), 2,5-hexanediones (HD) or its combination is provided.
On the one hand, provide by the compound of following manufacture formula I (such as, p-Xylol) method: by the compound of formula A (such as, DMF), the compound of formula B (such as, HD) or its combination merge with ethene, catalyzer and optional solvent, forming reactions mixture; With by the compound (such as, DMF) of reaction mixture Chinese style A, the compound (such as, HD) of formula B or its combination the p-Xylol of manufacture at least partially.
The application of special catalyst provided herein, solvent (depending on the circumstances) and reaction conditions makes the compound of formula A (such as, DMF), the compound of formula B (such as, HD) or its combination can be used as the starting raw material of the compound (such as, p-Xylol) of manufacture formula I.
starting raw material
The compound of formula A and the compound of formula B
According to method as herein described, the compound of one or more formula A and/or the compound of one or more formula B can be used:
Starting raw material as the compound for the manufacture of one or more formula I:
In some embodiments, each R 1and R 2be hydrogen, alkyl, cycloalkyl, Heterocyclylalkyl, aryl or heteroaryl independently.In some embodiments, each R 1and R 2be hydrogen or alkyl independently.In some embodiments, each R 1and R 2be C independently 1-10or C 1-6or C 1-4alkyl.In one embodiment, R 1and R 2be methyl separately.In another embodiment, R 1methyl, and R 2hydrogen.
In some embodiments, aforesaid method relates to the compound of use formula A.Such as, in one embodiment, in method provided herein, 2,5-dimethyl furan is used to manufacture p-Xylol.In another embodiment, in method provided herein, use 2-methyl furan to manufacture p-Xylol.In some embodiments, aforesaid method relates to the compound of use formula B.Such as, in one embodiment, in method provided herein, 2,5-hexanedione is used to manufacture toluene.In another embodiment, in method provided herein, use 4-oxo valeral to manufacture toluene.
In some embodiments, aforesaid method relates to the mixture of the compound of use formula A to manufacture the mixture of the compound of formula I.Such as, in one embodiment, can in method provided herein, 2,5-dimethyl furan and 2-methyl furan be used to manufacture the mixture of p-Xylol and toluene.In other embodiments, aforesaid method relates to the mixture of the compound of use formula B to manufacture the mixture of the compound of formula I.Such as, in one embodiment, 2,5-hexanedione and 4-oxo valeral can be used in method provided herein to manufacture the mixture of p-Xylol and toluene.In other embodiment again, aforesaid method relates to the mixture of the compound of use formula A and the compound of formula B to manufacture the mixture of the compound of formula I.Such as, in one embodiment, 2,5-dimethyl furan, 2-methyl furan, 2,5-hexanediones and 4-oxo valeral can be used in method provided herein to manufacture the mixture of p-Xylol and toluene.
" alkyl " refers to the straight or branched saturated hydrocarbon chain of unit price.In some embodiments, as used herein, such as, in formula I, (A) or (B), alkyl has 1-20 carbon atom (that is, C 1-20alkyl), a 1-8 carbon atom (that is, C 1-8alkyl), a 1-6 carbon atom (that is, C 1-6alkyl) or 1-4 carbon atom (that is, C 1-4alkyl).The example of alkyl comprises methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, amyl group, 2-amyl group, isopentyl, pungent amyl group, hexyl, 2-hexyl, 3-hexyl and 3-methyl amyl.When appointment has the alkyl of given number carbon, all geometrical isomers with this number carbon can be comprised; Therefore, such as, " butyl " can comprise normal-butyl, sec-butyl, isobutyl-and the tertiary butyl; " propyl group " can comprise n-propyl and sec.-propyl.
" cycloalkyl " refers to cyclic alkyl.In some embodiments, as used herein, such as, in formula I, (A) or (B), cycloalkyl has 3-20 ring carbon atom (that is, C 3-20cycloalkyl), or 3-12 ring carbon atom (that is, C 3-12cycloalkyl), or 3-8 ring carbon atom (that is, C 3-8cycloalkyl).The example of cycloalkyl comprises cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
" Heterocyclylalkyl " refers to have one or more heteroatomic cyclic alkyl independently selected from nitrogen, oxygen and sulphur.In some embodiments, as used herein, such as, in the compound of formula I, (A) or (B), Heterocyclylalkyl has 2-20 ring carbon atom (that is, C 2-20heterocyclylalkyl), a 2-12 ring carbon atom (that is, C 2-12heterocyclylalkyl) or 2-8 ring carbon atom (that is, C 2-8heterocyclylalkyl); With 1-5 ring hetero atom, a 1-4 ring hetero atom, a 1-3 ring hetero atom, 1 or 2 ring hetero atom or 1 ring hetero atom, it is independently selected from nitrogen, sulphur or oxygen.In an example, Heterocyclylalkyl has 2-8 ring carbon atom, and 1-3 the ring hetero atom independently selected from nitrogen, oxygen and sulphur.The example of Heterocyclylalkyl can comprise pyrrolidyl, piperidyl, piperazinyl, oxetanylmethoxy, dioxolanyl, azelidinyl and morpholinyl.
" aryl " refers to the aromatic carbocyclic group with single ring (such as, phenyl), multiple ring (such as, xenyl) or multiple condensed ring (such as, naphthyl, fluorenyl and anthryl).In some embodiments, as used herein, such as, in the compound of formula I, (A) or (B), aryl has 6-20 ring carbon atom (that is, C 6-20aryl) or 6-12 ring carbon atom (that is, C 6-12aryl).But aryl does not comprise or overlaps with the heteroaryl of following independent definition by any way.In some embodiments, if one or more aryl and hetero-aromatic ring condense, the member ring systems of generation is heteroaryl.
" heteroaryl " refers to the aromatic group with one or more ring hetero atom independently selected from nitrogen, oxygen and sulphur with single ring, multiple ring or multiple condensed ring.In some embodiments, heteroaryl is containing one or more heteroatoms independently selected from nitrogen, oxygen and sulphur and all the other annular atomses are aromatic monocyclic or two rings of carbon.In some embodiments, as used herein, such as, in the compound of formula I, (A) or (B), heteroaryl has 3-20 ring carbon atom (i.e. C 3-20heteroaryl), a 3-12 ring carbon atom (i.e. C 3-12heteroaryl) or 3-8 ring carbon atom (i.e. C 3-8heteroaryl); With 1-5 heteroatoms, a 1-4 heteroatoms, a 1-3 ring hetero atom, 1 or 2 ring hetero atom or 1 ring hetero atom, it is independently selected from nitrogen, oxygen and sulphur.In an example, heteroaryl has 3-8 ring carbon atom, and 1-3 the ring hetero atom independently selected from nitrogen, oxygen and sulphur.The example of heteroaryl comprises pyridyl, pyridazinyl, pyrimidyl, benzothiazolyl and pyrazolyl.Heteroaryl does not comprise or overlaps with aryl defined above.
As used herein, term " replacement " refers to that any one or more hydrogen atoms on specified atom or group are replaced by the part beyond hydrogen, and condition is no more than the normal valency of specified atom.
And, being to be understood that, when listing numerical range, being intended to comprise each numerical value within the scope of this and subrange.Such as, " C 1 – 6alkyl " (also can be called 1-6C alkyl, C1-C6 alkyl or C1-6 alkyl) be intended to comprise C 1, C 2, C 3, C 4, C 5, C 6, C 1 – 6, C 1 – 5, C 1 – 4, C 1 – 3, C 1 – 2, C 2 – 6, C 2 – 5, C 2 – 4, C 2 – 3, C 3 – 6, C 3 – 5, C 3 – 4, C 4 – 6, C 4 – 5and C 5 – 6alkyl.
The compound of the formula A used in method as herein described and the compound of formula B available from any source (comprising any commercial source), or can be manufactured by any methods known in the art.And be to be understood that, the compound of formula B can be produced by reaction mixture original position.
Such as, the DMF used in method as herein described can be commercially available, or can be derived from carbonaceous material.The example that can produce the suitable carbonaceous material of DMF by it comprises Agricultural Materials (such as, maize straw, rice husk, Pericarppium arachidis hypogaeae, cereal slag, pine sawdust), processing waste material (such as, paper mill sludge), reclaim cellulose materials (such as, fiber board, old corrugated container (old corrugated containers, OCC), mixed paper, old newspaper (ONP)) and fructose (such as, high-fructose corn syrup), sucrose, glucose or starch.The many kinds of methods being obtained DMF by biomass are known in the art.Such as, Mierocrystalline cellulose and hemicellulose (if present) or other hexose (such as, glucose, fructose) can be changed into 5-chloromethyl furfural, it directly or via 5 hydroxymethyl furfural can change into DMF.See, such as, Chidambaram & Bell, Green Chem., 2010,12,1253-1262.
In another example, the HD (also referred to as acetonyl-acetone) used in method as herein described can be commercially available, or can prepare according to methods known in the art.Such as, known HD can be prepared by the oxidation of allylacetone.See, United States Patent (USP) the 3rd, 947, No. 521.HD can also pass through the interior ester hydrolysis preparation of α-ethanoyl-γ-cyano group-γ-hydroxypentanoic acid.See, United States Patent (USP) the 3rd, 819, No. 714.And will be appreciated that, HD can be produced by reaction mixture original position.
Ethene
Ethene is also the starting raw material for this reaction.The ethene being provided for methods described herein can available from any source (comprising any commercial source).Such as, ethene available from fossil oil source or renewable source, such as, can be dewatered by ethanol (such as, based on the ethanol of fermentation).
catalyzer
Multiple catalysts perhaps can be used in the method, the compound (such as DMF) of formula A and/or the compound (such as HD) of formula B are transformed the compound (such as p-Xylol) of accepted way of doing sth I.Such as, catalyzer can be selected from a class or multiclass catalyzer, it comprises (i) catalyzer containing metal, comprise catalytic or the salt containing metal of catalytic species can be changed into by in-situ transesterification, (ii) acid (such as, Lewis acid, weak acid, sulfonic acid, heteropolyacid).
But be to be understood that, catalyzer can fall within this class listed or multiclass.Such as, catalyzer can be copper trifluoromethanesulfcomposite, and it is the catalyzer containing metal, is also Lewis acid.Catalyzer also can be load or non-load.Catalyzer can be homogeneous phase or out-phase based on the solvent system used in reaction.Catalyzer also can be the form of solvate, and it comprises, such as, and hydrate.Catalyzer also can be polymkeric substance.
Should also be appreciated that, catalyzer adds the speed of chemical reaction, and this increase can be that directly or indirectly (such as, changing into different catalyst species by in-situ transesterification) causes.Such as, the catalyzer of use can be copper trifluoromethanesulfcomposite.Be not intended to stick to any theory, under some reaction conditions, copper trifluoromethanesulfcomposite can produce the trifluoromethanesulfonic acid that can contribute to increasing chemical reaction rate.In another example, the catalyzer of use can be trifluoromethanesulfonic acid imide (triflimide).In another example, have no intention to stick to any theory, trifluoromethanesulfonic acid imide can produce the trifluoromethanesulfonic acid that can contribute to increasing chemical reaction rate in the reactive mixture.
Be provided for method as herein described available from any source (comprising any commercial source), or can be prepared by any means known in the art or technology with the catalyzer manufacturing the compound (such as p-Xylol) of formula I.Should also be appreciated that, providing catalyzer to comprise provides catalyzer itself, or provides formation (such as, original position is formed) can contribute to the precursor of the catalytic species increasing chemical reaction rate.
Metal catalyst
In some embodiments, catalyzer is metal catalyst.Metal catalyst can be any metal catalyst or the catalyzer containing metal ligand.Metal can comprise, such as, and basic metal, alkaline-earth metal, transition metal or lanthanon.In one embodiment, metal can comprise transition metal or lanthanon.In some embodiments, metal is selected from 3 races, 9 races, 10 races, 11 races and lanthanon.In some embodiments, metal is selected from 3 races, 9 races, 11 races and lanthanon.
In some embodiments, metal is aluminium, bismuth, copper, chromium, iron, gadolinium, indium, nickel, neodymium, lithium, sodium, potassium, rubidium, caesium, beryllium, magnesium, calcium, strontium, barium, lanthanum, scandium, titanium, vanadium, yttrium, zinc, platinum, palladium, silver, gold, thallium, rhenium, mercury, tin, boron, gallium, lead, cobalt, germanium and cerium.
Be not intended to stick to any theory, under certain conditions, the catalytic species in reaction as herein described also can be formed by providing suitable precursor original position.Such as, copper metal and chlorine can be provided to reaction, produce cupric chloride with original position.Should also be appreciated that, catalytic species can be formed by the reaction original position between metal precursor and the ethene provided in reacting.Such as, under certain conditions, copper trifluoromethanesulfcomposite is provided to reaction, and catalytic species can be formed with ethene.
In one embodiment, metal catalyst is the catalyzer containing metal.Catalyzer containing metal has one or more metallic cation and one or more counter ion or part.Such as, catalyzer can be the catalyzer of metal center.In some embodiments, can be transition-metal cation or lanthanide cation containing the metallic cation in the catalyzer of metal.In some embodiments, 3 races, 9 races, 10 races, 11 races and lanthanon is selected from containing the metallic cation in the catalyzer of metal.In some embodiments, metallic cation is selected from 3 races, 9 races, 11 races and/or lanthanon.In one embodiment, metallic cation is 11 race's positively charged ions.Be to be understood that, for metal use race's number in accordance with IUPAC well known in the art or long formula nomenclature.
In some embodiments, catalyzer can have monovalent metal cation.Such as, in some embodiments, monovalent metal cation is Cu +, Li +, Na +, K +, Rb +, Cs +, Ag +, Tl +or Hg 2 2+.In one embodiment, monovalent metal cation is Cu 1+.
In other embodiments, catalyzer can have divalent metal or trivalent metal cation.Such as, in some embodiments, divalent metal is Cu 2+, Ni 2+, Be 2+, Mg 2+, Ca 2+, Sr 2+, Ba 2+, Zn 2+, Pt 2+, Pd 2+, Hg 2+, Sn 2+, Pb 2+, Co 2+or Ge 2+.In some embodiments, divalent metal is Cu 2+, Co 2+, Cr 3+, Ni 2+, Mg 2+or Zn 2+.In some embodiments, divalent metal is Cu 2+, Co 2+, Ni 2+or Zn 2+.In one embodiment, divalent metal is Cu 2+, Co 2+or Zn 2+.In one embodiment, divalent metal is Cu 2+.
In some embodiments, trivalent metal cation is Al 3+, Bi 3+, Cr 3+, Fe 3+, Gd 3+, In 3+, Nd 3+, La 3+, Sc 3+, Y 3+, Au 3+, Tl 3+, Re 3+, Sn 3+, B 3+, Ga 3+, Co 3+or Ce 3+.In some embodiments, trivalent metal cation is Al 3+, Bi 3+, Fe 3+, Gd 3+, In 3+, Nd 3+, La 3+, Sc 3+or Y 3+.In some embodiments, trivalent metal cation is Al 3+, Fe 3+, Gd 3+, In 3+, La 3+or Y 3+.In one embodiment, trivalent metal cation is Al 3+, Gd 3+, In 3+, La 3+or Y 3+.In another embodiment, trivalent metal cation is Gd 3+, In 3+, La 3+or Y 3+.
In other embodiment again, catalyzer can have quadrivalent metallic ion.
Metallic cation can with one or more cation coordination.Such as, the divalence of catalyzer or trivalent metal cation can respectively with two or three counter ion coordinations.Each counter ion can be independently selected from, such as, and halogenide (such as, muriate, bromide), fluoroform sulphonate (-OTf) and carboxylate salt (such as, formate, acetate, acetyl pyruvate).But be to be understood that, any suitable counter ion can be used.In one embodiment, counter ion can be muriate or fluoroform sulphonate.Be to be understood that, counter ion can be all identical, and counter ion can be all different, or two counter ion can be identical, and the 3rd counter ion can be different.
In some embodiments, counter ion can be the parts with metal-complexing.Part can be cationic, negatively charged ion or neutrality.Such as, catalyzer can be η 2-ethylidene-copper (II) fluoroform sulphonate.
In some embodiments, catalyzer is aluminum chloride, aluminum bromide, trifluoromethanesulfonic acid aluminium, bismuth chloride, bismuth bromide, Bismuth triflate, cupric chloride, cupric bromide, copper trifluoromethanesulfcomposite, cobalt chloride, cobaltous bromide, trifluoromethanesulfonic acid cobalt, chromium chloride, chromic bromide, trifluoromethanesulfonic acid chromium, iron(ic) chloride, iron bromide, trifluoromethanesulfonic acid iron, Gadolinium trichloride, gadolinium bromide, trifluoromethanesulfonic acid gadolinium, indium chloride, indium bromide, trifluoromethanesulfonic acid indium, nickelous chloride, nickelous bromide, trifluoromethanesulfonic acid nickel, Neodymium trichloride, neodymium bromide, trifluoromethanesulfonic acid neodymium, magnesium chloride, magnesium bromide, trifluoromethanesulfonic acid magnesium, Lanthanum trichloride, lanthanum bromide, trifluoromethanesulfonic acid lanthanum, Scium trichloride, scandium bromide, trifluoromethanesulfonic acid scandium, tin chloride, Tin tetrabromide, trifluoromethanesulfonic acid tin, titanium chloride, titanium bromide, trifluoromethanesulfonic acid titanium, vanadium chloride, bromination vanadium, trifluoromethanesulfonic acid vanadium, Yttrium trichloride, yttrium bromide, trifluoromethanesulfonic acid yttrium, zinc chloride, zinc bromide, trifluoromethanesulfonic acid zinc, or its arbitrary combination.
In some embodiments, catalyzer is cupric chloride, copper trifluoromethanesulfcomposite, trifluoromethanesulfonic acid yttrium, trifluoromethanesulfonic acid scandium, trifluoromethanesulfonic acid lanthanum, trifluoromethanesulfonic acid neodymium, trifluoromethanesulfonic acid imide copper or its arbitrary combination.In other embodiments, catalyzer is aluminum chloride, cupric chloride, copper trifluoromethanesulfcomposite, trifluoromethanesulfonic acid yttrium or its arbitrary combination.In one embodiment, catalyzer is cupric chloride or copper trifluoromethanesulfcomposite or its combination.In another embodiment, catalyzer is that (that is, trifluoromethanesulfonic acid imide copper, also referred to as Cu [N (Tf) for copper (II) two (trifyl) imide 2] 2).
In other embodiments, catalyzer is the salt catalyst containing metal, and it comprises anyly converted in-situ can be paired in the salt that reaction as herein described is the species of catalyzer.Such as, metal salt catalyst can comprise 11 race's metals and one or more counter ion.The metal of metal salt catalyst can be copper positively charged ion.In one embodiment, catalyzer is venus crystals or cupric acetylacetonate.As discussed above, any suitable counter ion all may reside in the salt catalyst containing metal.
In some embodiments, catalyzer comprises copper or cupric ion.In one embodiment, catalyzer comprises copper (I) ion.In another embodiment, catalyzer comprises copper (II) ion.In one embodiment, catalyzer is Cu [N (Tf) 2] 2, CuCl 2, Cu (OCOCH 3) 2, Cu (CH 3cOCH 2cOCH 3) 2, Cu (II) (BF 4) 2, Cu (I) (BF 4) (CH 3cN) 4, [Cu (I) OSO 2cF 3] 2c 6h 6, (Cu (I) OSO 2cF 3) (CH 3cN) 4or its arbitrary combination.These catalyzer available from any commercial source, or can be prepared by any proper method known in the art.Some catalyzer can also original position be formed.Such as, in one embodiment, copper metal can provide as precursor, produces CuCl with original position 2.In another embodiment, can with HBF 4and CH 3cN combines and provides cupric oxide (Cu 2o), Cu (I) (BF is produced with original position 4) (CH 3cN) 4.In another embodiment again, can with CF 3sO 3h and CH 3cN combines and provides cupric oxide (Cu 2o), (Cu (I) OSO is produced with original position 2cF 3) (CH 3cN) 4.
Lewis acid
In some embodiments, catalyzer is Lewis acid.As used herein, " Lewis acid " refers to that the lone-pair electron can applied from another molecule complete the acid substance of the stable group of one of himself atom.
Be to be understood that, above-mentioned one or more catalyzer (comprising the catalyzer that one or more contain metal) can be Lewis acids.Such as, catalyzer can be Lewis acid, such as, and aluminum chloride, zinc chloride, indium chloride, the divalent transition metal ion of copper, nickel or cobalt or its mixture such as CuCl 2or CoCl 2, the fluoroform sulphonate of fluoroform sulphonate such as indium, copper, gadolinium or yttrium, from trivalent metal ion or its mixture of lanthanon.
Catalyzer can be solvate, and it can comprise hydrate, or anhydrous.Such as, in one embodiment, catalyzer is CuCl 2x 2H 2o.In another embodiment, catalyzer is CuCl 2, be wherein less than 5%, be less than 4%, be less than 3%, be less than 2% or the catalyzer that is less than 1% be water.
In other embodiments, catalyzer can also comprise acetic acid, halogenated acetic acids (such as, Mono Chloro Acetic Acid, dichloro acetic acid, trichoroacetic acid(TCA), gifblaar poison, difluoroacetic acid, trifluoroacetic acid).These acid can be Lewis acid in the reaction.Acid can also available from the acid anhydrides being hydrolyzed into its corresponding sour form in presence of water.Such as, diacetyl oxide can be used as the acetic acid of catalysts containing less percentage composition.In addition, the diacetyl oxide in reaction mixture can change into acetic acid in the reaction further.
Heteropolyacid
In other embodiments, Lewis acid is heteropolyacid.Heteropolyacid is that a class comprises hydrogen and Sauerstoffatom and some metal and/or nonmetallic acid.Heteropolyacid generally includes at least one supplement atom (addenda atom), oxygen, heteroatoms and acid hydrogen atom.In some embodiments, supplement atom can be selected from one or more metals, and it comprises, such as, and tungsten, molybdenum or vanadium.In some embodiments, heteroatoms can be selected from p-block element, such as silicon or phosphorus.Be to be understood that, the explanation of any supplement atom for heteropolyacid used in methods described herein all can be combined for heteroatomic explanation with any, as each each combination is specifically listed all separately.Suitable heteropolyacid can comprise, such as, and silicotungstic acid (tungstosilicic acid), phospho-wolframic acid (tungostophosphoric acid), silicomolybdic acid (molybdosilicic acid), phospho-molybdic acid.Also heteropolyacid mixture can be used.
Heteropolyacid can have structures more known in the art.In one embodiment, heteropolyacid has formula H nxM 12o 40structure with Keggin, wherein X is heteroatoms, M be supplement atom, and n be greater than 0 integer.In another embodiment, heteropolyacid has formula H nx 2m 18o 62dawson structure, wherein X is heteroatoms, M be supplement atom, and n be greater than 0 integer.
In one embodiment, catalyzer is the heteropolyacid being selected from 12-phospho-wolframic acid, 12-phospho-molybdic acid, 12-silicotungstic acid, 12-silicomolybdic acid and arbitrary combination thereof.
In some embodiments, catalyzer can be the solvate of heteropolyacid.Suitable solvate can comprise hydrate or solvate.
In other embodiments that can combine with any aforementioned embodiments, heteropolyacid catalyst can be non-load or load.In one embodiment, catalyzer is the heteropolyacid of load.Suitable heteropolyacid solid carrier can comprise, such as, carbon, aluminum oxide, silicon-dioxide, cerium dioxide, titanium dioxide, zirconium white, niobium oxides (niobia), zeolite, magnesium oxide, clay, ferric oxide, silicon carbide, aluminosilicate and modifier, mixture or combination arbitrarily thereof.
Sulfonic acid, sulphonamide and sulfimide
In some embodiments, catalyzer is sulfonic acid or its salt, ester, acid anhydrides or resin.Sulfonic acid used herein can have formula R xsO 3the structure of H.In some embodiments, R xalkyl, haloalkyl, cycloalkyl, Heterocyclylalkyl, aryl or heteroaryl, wherein each alkyl, haloalkyl, cycloalkyl, Heterocyclylalkyl, aryl or heteroaryl optionally by 1-8 or 1-5 or 1-3 independently selected from alkyl, haloalkyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl, nitro ,-OR ' ,-C (O) OR ' ,-C (O) NR ' R "-CHO ,-COR ' and the substituting group replacement of cyano group, and wherein each R ' and R " be hydrogen, alkyl or haloalkyl independently.In some embodiments, R xalkyl or haloalkyl.In another embodiment, R xit is alkyl.In some embodiments, R xc1-C10 alkyl or C1-C10 haloalkyl.In some embodiments, R xmethyl, ethyl, propyl group, CHF 2, CH 2f or CF 3.In some embodiments, alkyl or haloalkyl can be replaced by ether moiety further.Such as, alkyl or haloalkyl can further by-OR ' replace, wherein R ' is alkyl or haloalkyl.In other embodiments, R xoptionally by the alkyl of alkyl, haloalkyl or nitro replacement, haloalkyl or aryl.
As used herein, " haloalkyl " refers to the alkyl of straight or branched, and wherein one or more hydrogen atoms are optionally substituted by halogen.Such as, when residue is by more than one halogen substiuted, it can be mentioned by using the prefix corresponding with the number of the halogen moiety connected.Such as, dihalo alkyl or tri haloalkyl refer to the alkyl replaced by two (" two ") or three (" three ") halogen groups, and it is passable, but also optionally, are identical halogens; Therefore, such as, 2-chloro-2-fluorine butyl is in the scope of dihalo alkyl.Wherein each H is all referred to as " whole haloalkyl " by the alkyl that halogen group replaces.An example of whole haloalkyl is trifluoromethyl (-CF 3).
The sulfonic acid used in method as herein described can comprise, such as, and CF 3sO 3h (that is, trifluoromethanesulfonic acid), HCF 2cF 2sO 3h, C 6f 5sO 3h, 4-toluene sulfonic acide (that is, tosic acid) or 2,4-dinitrobenzene sulfonic acid.In one embodiment, sulfonic acid is trifluoromethanesulfonic acid.In another embodiment again, sulfonic acid is tosic acid.
Sulfonate used herein can have formula Q r+[R xsO 3 -] rstructure, wherein: Q is positively charged ion; R xas above for as described in sulfonic acid; And r is cationic electric charge.In some embodiments, Q r+al 3+, Bi 3+, Cu 2+, Cu +, Cr 3+, Fe 3+, Gd 3+, In 3+, Ni 2+, Nd 3+, Li +, Na +, K +, Rb +, Cs +, Mg 2+, Ba 2+, Ca 2+, La 3+, Sc 3+, Ti 4+, V 5+, Y 3+, Zn 2+, Pt 2+, Pd 2+, Ag +, Au 3+, Tl 3+, Tl +, Re 3+, Hg 2 2+, Hg 2+, NH 4 +, Sn 4+, Sn 3+, Sn 2+, B 3+, Ga 3+, Pb 4+, Pb 2+, Co 3+, Co 2+, Ge 4+, Ge 2+, Ce 4+or Ce 3+.
The sulfonate used in method as herein described can comprise, such as, and Al (OTf) 3, Bi (OTf) 3, Cu (OTf) 2, Cu (OTf), Cr (OTf) 3, Fe (OTf) 3, Gd (OTf) 3, In (OTf) 3, Ni (OTf) 2, Nd (OTf) 3, Rb (OTf), Cs (OTf), Mg (OTf) 2, La (OTf) 3, Sc (OTf) 3, Ti (OTf) 4, V (OTf) 5, Y (OTf) 3, Zn (OTf) 2, Pt (OTf) 2, Pd (OTf) 2, AgOTf, Au (OTf) 3, Tl (OTf) 3, Tl (OTf), Re (OTf) 3, Hg 2(OTf) 2, Hg (OTf) 2, NH 4(OTf), Sn (OTf) 4, Sn (OTf) 3, Sn (OTf) 2, B (OTf) 3, Ga (OTf) 3, Pb (OTf) 4, Pb (OTf) 2, Co (OTf) 3, Co (OTf) 2, Ge (OTf) 4, Ge (OTf) 3, Ge (OTf) 2, Ge (OTf), Ce (OTf) 4, Ce (OTf) 3or its arbitrary combination.
In some embodiments, sulfonate can be the form of ionic liquid.In other embodiment again, sulfonic acid can be hydrate.In other implementations, sulfonic acid can be anhydrous.Such as, catalyzer can be trifluoromethanesulfanhydride anhydride.In other implementations, catalyzer is quaternary amine fluoroform sulphonate.
In other embodiment again, sulfonic acid catalyst can be sulfonic acid polymer, and it comprises, such as, and sulfonate resin.In some embodiments, sulfonate resin is halogenosulfonic acid resin.In some embodiments, sulfonate resin is flurosulphonic acid resin.In one embodiment, sulfonate resin is R x1cF 2sO 3h, wherein R x1alkyl or haloalkyl.Such as, sulfonate resin is sulfonated tertafluorethylene polymkeric substance, such as Nafion.
In some embodiments, catalyzer can be have formula R xsO 3si (R m) 3sulfonate, wherein R xas above for sulfonic acid define; And R mbe alkyl or haloalkyl independently when occurring at every turn.Such as, sulfonate is trimethyl silyl fluoroform sulphonate.
In some embodiments, catalyzer is sulphonamide or its salt.Sulphonamide used herein can have formula (R y1sO 2) NH 2or (R y1sO 2) NH (R z) structure.In some embodiments, R y1and R zbe alkyl, haloalkyl, cycloalkyl, Heterocyclylalkyl, aryl or heteroaryl independently of one another, wherein each alkyl, haloalkyl, cycloalkyl, Heterocyclylalkyl, aryl or heteroaryl optionally by 1-8 or 1-5 or 1-3 independently selected from alkyl, haloalkyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl, nitro ,-OR ' ,-C (O) OR ' ,-C (O) NR ' R "-CHO ,-COR ' and the substituting group replacement of cyano group, wherein each R ' and R " be hydrogen, alkyl or haloalkyl independently.In some embodiments, R y1and R zbe alkyl or haloalkyl independently of one another.In another embodiment, R y1and R zbe alkyl independently of one another.In some embodiments, R y1and R zbe C1-C10 alkyl or C1-C10 haloalkyl independently of one another.In some embodiments, R y1and R zbe methyl, ethyl, propyl group, CHF independently of one another 2, CH 2f or CF 3.In some embodiments, alkyl or haloalkyl can be replaced by ether moiety further.Such as, alkyl or haloalkyl can further by-OR ' replace, wherein R ' is alkyl or haloalkyl.In other embodiments, R y1and R zbe optionally by the alkyl of alkyl, haloalkyl or nitro replacement, haloalkyl or aryl independently of one another.
Sulfonamide used herein can have formula Q r+[(R y1sO 2) N (R z)] ror Q r+[(R y1sO 2) NH] rstructure, wherein: Q is positively charged ion; R y1and R z(if present) as above for as described in sulphonamide; And r is cationic electric charge.In some embodiments, Q r+al 3+, Bi 3+, Cu 2+, Cu +, Cr 3+, Fe 3+, Gd 3+, In 3+, Ni 2+, Nd 3+, Li +, Na +, K +, Rb +, Cs +, Mg 2+, Ba 2+, Ca 2+, La 3+, Sc 3+, Ti 4+, V 5+, Y 3+, Zn 2+, Pt 2+, Pd 2+, Ag +, Au 3+, Tl 3+, Tl +, Re 3+, Hg 2 2+, Hg 2+, NH 4 +, Sn 4+, Sn 3+, Sn 2+, B 3+, Ga 3+, Pb 4+, Pb 2+, Co 3+, Co 2+, Ge 4+, Ge 2+, Ce 4+or Ce 3+.
In some embodiments, catalyzer is sulfimide or its salt.Sulfimide used herein can have formula (R y1sO 2) NH (SO 2r y2) structure.In some embodiments, R y1and R y2be alkyl, haloalkyl, cycloalkyl, Heterocyclylalkyl, aryl or heteroaryl independently of one another, wherein each alkyl, haloalkyl, cycloalkyl, Heterocyclylalkyl, aryl or heteroaryl optionally by 1-8 or 1-5 or 1-3 independently selected from alkyl, haloalkyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl, nitro ,-OR ' ,-C (O) OR ' ,-C (O) NR ' R "-CHO ,-COR ' and the substituting group replacement of cyano group, and wherein each R ' and R " be hydrogen, alkyl or haloalkyl independently.In some embodiments, R y1and R zbe alkyl or haloalkyl independently of one another.In another embodiment, R y1and R y2be alkyl independently of one another.In some embodiments, R y1and R y2be C1-C10 alkyl or C1-C10 haloalkyl independently of one another.In some embodiments, R y1and R y2be methyl, ethyl, propyl group, CHF independently of one another 2, CH 2f or CF 3.In some embodiments, alkyl or haloalkyl can be replaced by ether moiety further.Such as, alkyl or haloalkyl can further by-OR ' replace, wherein R ' is alkyl or haloalkyl.In other embodiments, R xoptionally by the alkyl of alkyl, haloalkyl or nitro replacement, haloalkyl or aryl.
The sulfimide used in method as herein described can comprise, such as, and NH (Tf) 2(that is, trifluoromethanesulfonic acid imide).Be to be understood that, as used herein, "-Tf " refers to trifyl.
Trifluoromethanesulfonic acid imide salts used herein can have formula Q r+[(R y1sO 2) N (R y2sO 2)] rstructure, wherein: Q is positively charged ion; R y1and R y2as above for as described in sulfimide; And r is cationic electric charge.In some embodiments, Q r+al 3+, Bi 3+, Cu 2+, Cu +, Cr 3+, Fe 3+, Gd 3+, In 3+, Ni 2+, Nd 3+, Li +, Na +, K +, Rb +, Cs +, Mg 2+, Ba 2+, Ca 2+, La 3+, Sc 3+, Ti 4+, V 5+, Y 3+, Zn 2+, Pt 2+, Pd 2+, Ag +, Au 3+, Tl 3+, Tl +, Re 3+, Hg 2 2+, Hg 2+, NH 4 +, Sn 4+, Sn 3+, Sn 2+, B 3+, Ga 3+, Pb 4+, Pb 2+, Co 3+, Co 2+, Ge 4+, Ge 2+, Ce 4+or Ce 3+.
Sulfimide salt used herein can comprise, such as, and Al [N (Tf) 2] 3, Bi [N (Tf) 2] 3, Cu [N (Tf) 2] 2, Cu [N (Tf) 2], Cr [N (Tf) 2] 3, Fe [N (Tf) 2] 3, Gd [N (Tf) 2] 3, In [N (Tf) 2] 3, Ni [N (Tf) 2] 2, Nd [N (Tf) 2] 3, Li [N (Tf) 2], Na [N (Tf) 2], K [N (Tf) 2], Rb [N (Tf) 2], Cs [N (Tf) 2], Mg [N (Tf) 2] 2, Ba [N (Tf) 2] 2, Ca [N (Tf) 2] 2, La [N (Tf) 2] 3, Sc [N (Tf) 2] 3, Ti [N (Tf) 2] 4, V [N (Tf) 2] 5, Y [N (Tf) 2] 3, Zn [N (Tf) 2] 2, Pt [N (Tf) 2] 2, Pd [N (Tf) 2] 2, Ag [N (Tf) 2], Ag [N (Tf) 2] 2, Au [N (Tf) 2] 3, Tl [N (Tf) 2] 3, Tl [N (Tf) 2], Re [N (Tf) 2] 3, Hg 2[N (Tf) 2] 2, Hg [N (Tf) 2] 2, NH 4[N (Tf) 2], Sn [N (Tf) 2] 4, Sn [N (Tf) 2] 3, Sn [N (Tf) 2] 2, B [N (Tf) 2] 3, Ga [N (Tf) 2] 3, Pb [N (Tf) 2] 4, Pb [N (Tf) 2] 2, Co [N (Tf) 2] 3, Co [N (Tf) 2] 2, Ge [N (Tf) 2] 4, Ge [N (Tf) 2] 3, Ge [N (Tf) 2] 2, Ge [N (Tf) 2], Ce [N (Tf) 2] 4, Ce [N (Tf) 2] 3or its arbitrary combination.In other implementations, sulfimide salt is two (trifyl) imide of ethyl dimethyl propyl ammonium, two (trifyl) imide of 1-butyl-1-crassitude, two (trifyl) imide of 1-ethyl-3-methylimidazole, two (trifyl) imide of 1-butyl-3-Methylimidazole, two (trifyl) imide of 1-allyl group-3-Methylimidazole, two (trifyl) imide of triethyl sulfonium, two (trifyl) acid amides of three hexyl n-tetradecane Ji Phosphonium, 1, two (trifyl) imide of 2-dimethyl-3-propyl imidazole, [(C 6h 13) 3(C 14h 29) P] +[(CF 3sO 2) 2n] -, [C 11h 16n] +[N (SO 2cF 3) 2] -, [C 8h 15n 2] +[N (SO 2cF 3) 2] -, [C 6h 11n 2] +[N (SO 2cF 2cF 3) 2] -, [C 6h 11n 2] +[N (SO 2cF 3) 2] -, [C 6h 14n] +[N (SO 2cF 3) 2] -, 1-butyl-1-crassitude fluoroform sulphonate, 1-ethyl-3-methylimidazole fluoroform sulphonate, 1-butyl-3-Methylimidazole fluoroform sulphonate, 1-butyl-3-Methylimidazole fluoroform sulphonate or its arbitrary combination.In one embodiment, sulfimide salt is two (pentafluoroethyl group alkylsulfonyl) imide salts.
In other embodiment again, the salt of sulfonic acid, sulphonamide or sulfimide has positively charged ion, wherein positively charged ion is reduced into its element state (that is, zero oxidation state) and is greater than-0.2eV relative to the standard electrode potential of standard hydrogen current potential.Any appropriate means known in the art or commercial measurement standard electrode potential can be used.
Other acid
Other suitable acid can also be used in method as herein described as catalyzer.In some embodiments, sour pKa is lower than the pKa of sulfuric acid.In other implementations, acid is HClO 4or H 2sO 4.
Water-fast catalyzer
In some embodiments, catalyzer can also be water-fast (water-tolerant) catalyzer.As used herein, " water-fast catalyzer " to refer in given reaction can not because of the existence of water the catalyzer of inactivation.It will be recognized by those skilled in the art, given catalyzer can show water stability for the object of a reaction, then can not for another reaction.Water-fast catalyzer can improve the recyclability of used catalyst in plant-scale reaction, produces because of the by product in water Chang Zuowei reaction.In some embodiments, the pK of water-fast catalyzer hcan be 4.3 to 10.08.K hit is hydrolytic constant.PK hbe defined as follows:
PK h=-log K xy, wherein
It is based on following reaction: wherein M is metallic cation.In other implementations, the water coke slurry rate constant of water-fast catalyzer can be at least 3.2x 10 6m -1s -1.Usually see people such as Kobayashi, J.Am.Chem.Soc.1998,120,8287-8288.
The example of water-fast catalyzer can comprise having and is selected from Sc (III), Y (III), Ln (III), Fe (II), Cu (II), Zn (II), Cd (II), Pb (II), La (III), Ce (III), Pr (III), Nd (III), Sm (III), Eu (III), Gd (III), Tb (III), Dy (III), Ho (III), Er (III), Tm (III), the catalyzer of the metallic cation of Yb (III) and Lu (III).In some embodiments, catalyzer can comprise Fe (II), Cu (II), Zn (II), Cd (II), Pb (II) Sc (III), Y (III), Ln (III), Mn (II) or Ag (I).Water-fast catalyzer can comprise, such as, and ScCl 3, Sc (ClO 4) 3, Mn (ClO 4) 2, FeCl 2, Fe (ClO 4) 2, FeCl 3, Fe (ClO 4) 3, Co (ClO 4) 2, Ni (ClO 4) 2, CuCl 2, Cu (ClO 4) 2, ZnCl 2, Zn (ClO 4) 2, YCl 3, Y (ClO 4) 3, AgClO 4, CdCl 2, Cd (ClO 4) 2, InCl 3, In (ClO 4) 3, SnCl 2, La (OTf) 3, Ce (OTf) 3, Pr (OTf) 3, Nd (OTf) 3, Sm (OTf) 3, Eu (OTf) 3, Gd (OTf) 3, Tb (OTf) 3, Dy (OTf) 3, Ho (OTf) 3, Er (OTf) 3, Tm (OTf) 3, YbCl 3, Yb (ClO 4) 3, Yb (OTf) 3, Lu (OTf) 3, PbCl 2with Pb (ClO 4) 2.
The catalyzer of load or non-load
Above-mentioned any catalyzer can be non-load or load.In one embodiment, catalyzer is non-load.In another embodiment, catalyzer is by solid carrier load.Suitable carrier can comprise, such as, and carbon, aluminum oxide, silicon-dioxide, cerium dioxide, titanium dioxide, zirconium white, niobium oxides, zeolite, magnesium oxide, clay, ferric oxide, silicon carbide, silico-aluminate and modifier, mixture or combination arbitrarily thereof.In some embodiments, carrier is silicon-dioxide, aluminum oxide, mordenite, carbon (comprise, such as, gac) or zeolite (such as, HY zeolite).The example of supported catalyst can comprise the copper on mordenite, aluminum oxide or zeolite.In one embodiment, catalyzer is the copper (II) on mordenite, the cupric chloride on silicon-dioxide, the cupric chloride on aluminum oxide or the cupric chloride on HY zeolite.In another embodiment, carrier is gac.Gac can also be processed further, such as, with acid treatment (such as, H 3pO 4process).
The catalyzer of solid supported can more easily reclaim in a continuous process, recirculation and utilization.When using support of the catalyst, any method known in the art can be used to carry out metal refining.See, such as, the people such as Schwarz, Chem.Rev.95,477-510, (1995).
Homogeneous or heterogenous catalyst
In some embodiments, catalyzer is homogeneous in the reactive mixture.As used herein, " homogeneous catalysis " refers to that catalyzer is dissolved in reaction mixture at reaction conditions substantially.Such as, the acetic acid as catalyzer is dissolved in diox substantially.In another example, copper trifluoromethanesulfcomposite is dissolved in 12 carbon alkane at reaction conditions substantially, but is not under all conditions all so (such as, at standard temperature and pressure).When the amount of the catalyzer dissolved at reaction conditions exceedes the amount of undissolved catalyzer, catalyzer " dissolves " substantially.In some embodiments, when the ratio of the amount of the amount of undissolved catalyzer and the catalyzer of dissolving is at reaction conditions 0:1 to 1:1, catalyzer dissolves substantially.In one embodiment, the ratio of the amount of the amount of undissolved catalyzer and the catalyzer of dissolving is approximately 0 at reaction conditions.Any appropriate means can be used measure or the solvability of weighed catalyst.
In one embodiment, homogeneous catalysis is sulfonic acid or its salt, ester, acid anhydrides or resin, sulphonamide or its salt, or sulfimide or its salt.
In other embodiments, catalyzer is heterogeneous in the reaction.As used herein, " heterogenous catalyst " refers to that any is not the catalyzer of homogeneous catalysis as above.
Be to be understood that, the uniformity of catalyzer or heterogeneity can depend on solvent used or solvent mixture and reaction conditions.
The amount of catalyzer
The amount of used catalyst can depend on catalyzer, starting raw material, solvent and reaction conditions and change.As used herein, " catalyst loadings " refers to the amount of the used catalyst of the amount relative to DMF used, and it is expressed as the weight ratio of DMF (as starting raw material) and used catalyst.Such as, in some embodiments, catalyst loadings is 10 to 500, or 10 to 300, or 50 to 500, or 100 to 500, or 100 to 300, or 200 to 500.Under certain conditions, unexpectedly observe, add the selectivity of produced PX relative to the amount of the amount reduction used catalyst of DMF used.
And, be to be understood that, in some embodiments, one or more catalyzer as herein described can be used.
solvent system
Optionally the combination of solvent or solvent or mixture can also be added in reaction mixture.The dissolution with solvents used in method as herein described is the compound of ethene, formula A and/or the compound (if present) of formula B at least partially.The solvent used in method as herein described available from any source, can comprise any commercial source.In some embodiments, method as herein described uses some solvents, with by DMF, HD or its combination based on mole at least 50%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95% or at least 99% yield change into p-Xylol.
The specific solvent used in method as herein described can dissolve or dissolve at least partly starting raw material (such as, DMF, HD or its combination, ethene) and/or catalyzer, and it can contribute to increasing solvation effect and improving speed of reaction.Such as, in some embodiments, when measuring ethylene dissolution and spend at the temperature of about 23 DEG C, the ethylene dissolution degree of solvent system is about 0mol/L to about 0.82mol/L, approximately 0.82mol/L to about 1.2mol/L or about 1.2mol/L to about 4.0mol/L.
The solvent used also can be selected based on its boiling point.Solvent can be selected based on its boiling point under standard pressure or working pressure.In some embodiments, the boiling point of solvent can be 80 DEG C to 400 DEG C or 150 DEG C to 350 DEG C or 350 DEG C to 450 DEG C.And the boiling point of selected solvent or the combination of solvent or mixture can higher than p-Xylol.This makes p-Xylol can distill from reaction mixture, leaves catalysts and solvents to be recycled and/or to reclaim.
In addition, solvent is stable for processing condition usually, and preferably can recirculation so that again in reaction.The recyclability of solvent is useful especially for carrying out under commercial size method as herein described.
Solvent used herein can be aliphatic or aromatic.Solvent also can have one or more functional group, such as halogen, ester, ether, ketone and alcohol or its arbitrary combination or mixture.Solvent can also be acyclic (comprising straight chain or side chain) or ring-type.Although described below is different classes of solvent (such as, aprotic solvent, aliphatic solvent, aromatic solvent, alkyl phenyl solvent, ether solvents, alcoholic solvent, ketone solvent, halogenated solvent or ionic liquid), but be to be understood that, solvent can fall into described one or more classifications.Such as ， diox is sprotic ether.
In one embodiment, solvent system comprises N,N-DIMETHYLACETAMIDE (such as, N,N-dimethylacetamide), dimethyl formamide (such as, DMF), acetonitrile, tetramethylene sulfone, diox, diox, dme, ether, ethylene glycol dimethyl ether (monoglyme), ethylene glycol bisthioglycolate ethyl ether (glycol diethyl ether), diethylene glycol dimethyl ether (diglyme), diethylene glycol diethyl ether (diethyl carbitol), triethylene glycol dimethyl ether (triglyme), diethylene glycol dibutyl ether (diethylene glycol dibutyl ether), TEG dimethyl ether (tetraethylene glycol dimethyl ether), multiethylene-glycol dme (polygyme), dimethyl ether (proglyme), higlyme, tetrahydrofuran (THF), ethylene glycol, Diethylene Glycol, triethylene glycol, polyoxyethylene glycol, cyclobutanone, cyclopentanone, pimelinketone, suberone, cyclooctanone, methyl acetate, ethyl acetate, propyl acetate, butylacetate, methyl lactate, ethyl lactate, propyl lactate, n-Butyl lactate, triactin, Dibutyl phthalate, butane, pentane, pentamethylene, hexane, hexanaphthene, heptane, suberane, octane, cyclooctane, nonane, decane, hendecane, 12 carbon alkane, hexadecane, tetrachloride, chloroform, methylene dichloride, Nitromethane 99Min., toluene, methyl-phenoxide, oil of mirbane, bromobenzene, methylpyrrole (such as, N-methylpyrrole), methyl-2-pyrrolidone (such as, N-Methyl pyrrolidone), dimethyl furan (such as, 2,5-dimethyl furan), dichlorobenzene (such as, orthodichlorobenzene), p-Xylol, sym-trimethylbenzene, 12 carbon alkylbenzenes, amylbenzene, hexyl benzene, Wibaryl A, Wibaryl B, Wibaryl AB, Wibaryl F, Wibaryl R, Cepsa Petrepar 550-Q, Santovac, phenyl ether, methyl diphenyl ether, ethyl phenyl ether, water or its arbitrary combination or mixture.
In some embodiments, solvent system comprises diox, tetrahydrofuran (THF), tetramethylene sulfone, triglyme or its arbitrary combination or mixture.One preferred embodiment in, solvent system comprises Isosorbide-5-Nitrae-diox.In other implementations, solvent system comprises glymes (glymes).Such as, in one embodiment, solvent comprises triglyme.Yu diox or triglyme can be used to have any above-mentioned solvent of identical characteristics as the solvent in methods described herein.
Aprotic solvent
In some embodiments, solvent system comprises aprotic solvent.Such as, the moment of dipole of aprotic solvent can be greater than 0.1.It will be understood to those of skill in the art that moment of dipole is the tolerance of solvent polarity.The moment of dipole of liquid can be measured with dipole meter (dipole meter).Suitable aprotic solvent can comprise, such as, N,N-DIMETHYLACETAMIDE, dimethyl formamide (comprises, such as, N, dinethylformamide), methyl-2-pyrrolidone (such as, N-Methyl pyrrolidone), diox, polyethers (comprises, such as, glyme, diglyme, triglyme, tetraethylene glycol dimethyl ether), acetonitrile, tetramethylene sulfone, ether (comprises, such as, tetrahydrofuran (THF), dialkyl ether (such as dme, ether)), Nitromethane 99Min., methyl-phenoxide, oil of mirbane, bromobenzene, chlorobenzene or its arbitrary combination or mixture.
Aliphatic solvent
In one embodiment, solvent system comprises aliphatic solvent.Aliphatic solvent can be straight chain, side chain or ring-type.Aliphatic solvent can also be saturated (such as, alkane) or undersaturated (such as, alkene or alkynes).In some embodiments, solvent system comprises C1-C20 aliphatic solvent, C1-C10 aliphatic solvent or C1-C6 aliphatic solvent.In some embodiments, solvent systems comprises C4-C30 aliphatic solvent, C6-C30 aliphatic solvent, C6-C24 aliphatic solvent or C6-C20 aliphatic solvent.In some embodiments, solvent system comprises C8+ alkyl solvents, or C8-C50 alkyl solvents, C8-C40 alkyl solvents, C8-C30 alkyl solvents, C8-C20 alkyl solvents or C8-C16 alkyl solvents.Suitable aliphatic solvent can comprise, such as, and butane, pentane, pentamethylene, hexane, hexanaphthene, heptane, suberane, octane, cyclooctane, nonane, decane, hendecane, 12 carbon alkane, hexadecane or its arbitrary combination or mixture.In some embodiments, aliphatic solvent is straight chain.
Aliphatic solvent available from oil refining aliphatics cut, can comprise any isomer and any mixture thereof of aliphatic solvent.Such as, alkane solvent available from oil refining aliphatic fraction, can comprise any isomer and any mixture thereof of alkane solvent.In some embodiments, solvent system comprises oil refining aliphatic fraction.
Aromatic solvent
In another embodiment, solvent system comprises aromatic solvent.In some embodiments, solvent system comprises C6-C20 aromatic solvent, C6-C12 aromatic solvent or C13-C20 aromatic solvent.Aromatic solvent can be optional replacement.Suitable aromatic solvent can comprise, and such as, toluene, methyl-phenoxide, oil of mirbane, bromobenzene, chlorobenzene (comprise, such as, dichlorobenzene), dimethyl furan (comprise, such as, 2,5-dimethyl furan) and methylpyrrole (comprise, such as, N-methylpyrrole).In one embodiment, solvent system comprises p-Xylol (it can produce in the reaction or be provided to reaction system).
Alkyl phenyl solvent
As used herein, " alkyl phenyl solvent " refers to a kind solvent can with one or more alkyl chain and one or more phenyl or the member ring systems containing phenyl.Alkyl phenyl solvent can be called alkylbenzene or phenyl alkanes.It will be recognized by those skilled in the art, some phenyl alkanes also can be called alkylbenzene interchangeably.Such as, (1-phenyl) pentane and amylbenzene refer to same solvent.
In some embodiments, solvent system comprises alkylbenzene.Example can comprise (monoalkyl) benzene, (dialkyl group) benzene and (many alkyl) benzene.In some embodiments, alkylbenzene has an alkyl chain be connected with a phenyl ring.Alkyl chain can have one or two site be connected with phenyl ring.There is an alkyl chain and the example that alkyl chain has the alkylbenzene in the site that is connected with phenyl ring comprises amylbenzene, hexyl benzene and 12 carbon alkylbenzenes.Alkyl chain has in the embodiment in the site that two are connected with phenyl ring wherein, and alkyl chain can form the cycloalkyl ring condensed on benzene.There is an alkyl and the example that alkyl has the alkylbenzene in the site that two are connected with phenyl ring comprises tetraline.Be to be understood that, the cycloalkyl ring condensed can be replaced by one or more alkyl ring further.
In other implementations, alkylbenzene has two or more alkyl chains be connected with a phenyl ring (such as, 2,3,4,5 or 6 alkyl chains).
In other embodiment again, alkylbenzene is the fused benzene rings system that alkyl replaces.Fused benzene rings system can comprise and one or more heterocyclic fused benzene.In one embodiment, fused benzene rings system can be two or more fused benzene rings, such as naphthalene.Fused benzene rings system can optionally be replaced by one or more alkyl chain.
In some embodiments, solvent system comprises phenyl alkanes.Example can comprise (single phenyl) alkane, (phenylbenzene) alkane and (many phenyl) alkane.In some embodiments, phenyl alkanes can have a phenyl ring be connected with an alkyl chain.Phenyl ring can be connected with any carbon on alkyl chain.Such as, the phenylalkyl with an alkyl chain can be (1-phenyl) pentane, (2-phenyl) pentane, (1-phenyl) hexane, (2-phenyl) hexane, (3-phenyl) hexane, (1-phenyl) 12 carbon alkane and (2-phenyl) 12 carbon alkane.
In other implementations, phenyl alkanes has two or more phenyl ring be connected with an alkyl chain.
In one embodiment, solvent system comprises Wibaryl A, Wibaryl B, Wibaryl AB, Wibaryl F, Wibaryl R, Cepsa Petrepar 550-Q or its arbitrary combination or mixture.
In some embodiments, the alkyl chain of solvent can be 1-20 carbon atom (such as, C 1-20alkyl).In one embodiment, alkyl chain can be 4-15 carbon (such as, C 4-15alkyl) or 10-13 carbon (such as, C 10-13alkyl).Alkyl chain can be straight chain or side chain.Straight chained alkyl can comprise, such as, and n-propyl, normal-butyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecyl and positive 12 carbon alkyl.Branched alkyl chain can comprise, such as, and sec.-propyl, sec-butyl, isobutyl-, the tertiary butyl and neo-pentyl.Solvent comprises in some embodiments of two or more alkyl chains wherein, and some alkyl chains can be straight chains, and other alkyl chains can be side chains.Solvent comprises in other embodiments of two or more alkyl chains wherein, and all alkyl chains can be all straight chains, or all alkyl chains can be all side chains.
Such as, solvent system comprises linear alkylbenzene (" LAB ").Linear alkylbenzene is that a class has formula C 6h 5c nh 2n+1solvent.Such as, in one embodiment, linear alkylbenzene is 12 carbon alkylbenzenes.12 carbon alkylbenzenes are commercially available, and can be " gravity dies " or " soft-type ".Gravity die 12 carbon alkylbenzene is the mixture of branched chain isomer.Soft-type 12 carbon alkylbenzene is the mixture of linear isomers.In one embodiment, solvent system comprises gravity die 12 carbon alkylbenzene.
In some embodiments, solvent system comprises any abovementioned alkyl benzene-based solvents, and wherein phenyl ring is optionally substituted with one or more halogen atoms.In some embodiments, solvent system comprises alkyl (halogeno-benzene).Such as, alkyl (halogeno-benzene) can comprise alkyl (chlorobenzene).In one embodiment, the halogenic substituent of phenyl ring can be, such as, and chlorine, bromine or its arbitrary combination.
In other implementations, solvent system comprises naphthalene, naphthenic oil, alkylated naphthalene, biphenyl, polychlorinated biphenyls, Ppolynuclear aromatic hydrocarbon or halon.
Ether solvents
In other embodiments, solvent system comprises ether solvents, and it refers to the solvent with at least one ether group.Such as, solvent system comprises C2-C20 ether or C2-C10 ether.Ether solvents can be acyclic or ring-type.Such as, ether solvents can be alkyl oxide (such as, ether, ethylene glycol dimethyl ether (glyme), diethylene glycol dimethyl ether (diglyme) or triethylene glycol dimethyl ether (triglyme)).In another example, ether solvents can be ring-type, such as diox (such as, Isosorbide-5-Nitrae-diox), dioxin, tetrahydrofuran (THF) or cycloakyl alkyl ethers (such as, cyclopentyl-methyl ether).
Solvent system can comprise acetal, such as dioxolane (such as, DOX).
Solvent system can also comprise the polyethers with two or more Sauerstoffatoms.In some embodiments, ether solvents has following structural formula:
Wherein each R aand R bbe aliphatic portion independently, and n and m be more than or equal to 1 integer.In some embodiments, each R aand R bbe alkyl independently.In some embodiments, each R aand R bbe C1-C10 alkyl or C1-C6 alkyl independently.R aand R bcan be identical or different.In other embodiments, each n and m is 1-10 independently, or 1-6, and wherein n and m can be identical or different.
Above formula comprises dimethyl ether (such as dipropylene glycol dimethyl ether) or glymes (such as based on the ethylene glycol diether of oxyethane).In one embodiment, solvent system comprises glyme, diglyme, triglyme or tetraethylene glycol dimethyl ether.
Should also be appreciated that, the solvent with ether group can also have other functional group one or more.But be to be understood that, solvent can have the ether functional group combined with one or more extra functional group such as alcohol.Such as, solvent system comprises aklylene glycol class (such as, ethylene glycol, Diethylene Glycol, triethylene glycol, polyoxyethylene glycol), phenyl ether (such as, phenyl ether, polyphenylene oxide) or alkyl phenyl ether (such as, alkyl diphenyl ether).
In some embodiments, solvent system comprises polyphenylene oxide, and it connects at ether and comprises at least one phenoxy group or at least one sulfo-phenoxy moieties as recurring group.Such as, in one embodiment, solvent system turnkey draws together Santovac.
Ester solvent
In other embodiment again, solvent system comprises ester solvent, and it refers to the solvent with at least one ester group.Such as, solvent system comprises C2-C20 ester or C2-C10 ester.Ester solvent can be acyclic (straight or branched) or ring-type.Such as, non-annularity ester solvent can comprise alkyl acetates (such as, methyl acetate, ethyl acetate, propyl acetate, butylacetate), triactin and Dibutyl phthalate.The example of cyclic ester is, such as, and propylene carbonate.But will be appreciated that, the solvent with ester group can also have other functional group one or more.Ester solvent can also comprise alkyl lactate ester (such as, methyl lactate, ethyl lactate, propyl lactate, n-Butyl lactate), and it has ester group and hydroxyl.
Alcoholic solvent
In other embodiment again, solvent system comprises alcohol, and it refers to the solvent with at least hydroxyl.Such as, solvent can be C1-C20 alcohol, C1-C10 alcohol or C1-C6 alcohol.Alcoholic solvent can comprise, such as, and methyl alcohol, ethanol and propyl alcohol.Solvent can also be alkane glycol, such as 1,3-PD or propylene glycol.
Ketone solvent
In other embodiment again, solvent system comprises ketone.Such as, solvent can be C2-C20 ketone, C2-C10 ketone or C2-C6 ketone.Ketone solvent can be acyclic (straight or branched) or ring-type.Such as, solvent system comprises cyclobutanone, cyclopentanone, pimelinketone, suberone or cyclooctanone.
Halogenated solvent
In other embodiment again, solvent system comprises halogenated solvent.Such as, solvent can be chlorinated solvent.Suitable chlorinated solvent can comprise, such as, and tetracol phenixin, chloroform, methylene dichloride, bromobenzene and dichlorobenzene.
Ionic liquid
Solvent can also be ionic liquid.Suitable ionic liquid can comprise, such as, and 1-allyl group-3-methyl imidazolium bromide and 1-benzyl-3-methyl imidazolium tetrafluoroborate.
Solvent combination or mixture
Combination or the mixture of solvent can also be used in method as herein described.In some embodiments, ether solvents can comprise such as aliphatic solvent with the solvent of one or more other types listed above and combines.In one embodiment, solvent combination or mixture are diox and aliphatic solvent.Such as, solvent combination is diox and 12 carbon alkane or p-Xylol and 12 carbon alkane.
When using the combination of solvent or mixture, can by two or more solvents with any combinationally using, so that DMF and/or HD is changed into PX suitably.Such as, when using dual-solvent system, two kinds of solvents can with about 1 than about 1 or about 1 than about 2 about 1 than about 3 or about 1 than about 4 or about 1 weight ratio than about 5 exist.In one embodiment, when solvent system comprises diox and 12 carbon alkane or p-Xylol and 12 carbon alkane, two kinds of solvents use with about 1 weight ratio than about 1.
The amount of solvent
The amount of solvent for use can depend on starting raw material, catalyzer used and reaction conditions and change.Such as, in some embodiments, in reaction mixture, the concentration of DMF and/or HD is the about 1wt% to about 75wt% in solvent, or the about 3wt% to about 50wt% in solvent.Should also be appreciated that, the amount of solvent for use can depend on that reaction is batch system or continuous system and changes.Such as, in batch operation, in reaction mixture, the concentration of DMF and/or HD can start from 50wt%, and 0.01wt% finally.
ethene
The ethene used in method as herein described can use any appropriate means or technology to be added in reactor.Such as, in some embodiments, ethene can be added in reactor as gas.
Original ethylenic pressure refers to pressure when being added in reactor by ethene (as gas).Ethene can add with original pressure, makes the concentration of this reactant in solvent for enough high peak optimization reaction speed.In some embodiments, original ethylenic pressure is at least 10psi, at least 50psi, at least 75psi, at least 100psi, at least 200psi, at least 250psi, at least 300psi or at least 400psi.In some embodiments, original ethylenic pressure is 50psi to 20,000psi, or 100psi to 20,000psi, or 300psi to 20,000psi, or 400psi to 1,000psi, or 400psi to 800psi, or 600psi to 1000psi, or 600 to 6000psi, or 760psi to 6000psi, or 1000psi to 6000psi.
In other embodiments, ethene can dissolve or be dissolved at least partly in one or more solvents as herein described, and is added in reactor.In some embodiments, when measuring ethylene dissolution and spend at the temperature of about 23 DEG C, the solubleness of ethene in solvent system is about 0mol/L extremely about 0.82mol/L, about 0.82mol/L extremely about 1.2mol/L, or about 1.2mol/L to about 4.0mol/L.
Ethene also can provide under supercritical pressure and/or supercritical temperature.
reaction conditions
Service temperature refers to the medial temperature of reaction mixture in container.In some embodiments, service temperature can be at least 150 DEG C or at least 200 DEG C.In other implementations, service temperature can be 100 DEG C to 300 DEG C, 150 DEG C to 400 DEG C, 150 DEG C to 300 DEG C, 125 DEG C to 175 DEG C, 200 DEG C to 350 DEG C, 200 DEG C to 250 DEG C, 200 DEG C to 400 DEG C, 270 DEG C to 400 DEG C, 220 DEG C to 230 DEG C, 250 DEG C to 300 DEG C or 150 DEG C to 220 DEG C.In one embodiment, service temperature is that room temperature (such as, 18 DEG C-22 DEG C) is to 300 DEG C.Can use higher service temperature, the solvent that condition is selected is comparatively stable.
Working pressure refers to the interior pressure of the average absolute of container.In some embodiments, reaction can be clung at 1 bar to 1000,10 bar to 1000 cling to, 20 bar to 1000 cling to, 50 bar to 1000 cling to, 100 bar to 1000 cling to, 150 bar to 500 cling to, 35 to 38 bar, 1 bar to 50 cling to, 1 bar to 40 clings to, 1 bar to 30 clings to, 1 bar to 20 clings to, 1 bar to 10 clings to, 1 bar to 5 clings to, 5 bar to 30 cling to, 5 bar to 20 cling to or carry out under the working pressure of 5 bar to 10 bar.Under such working pressure, the concentration of ethylene reaction thing is sufficiently high for peak optimization reaction speed.
In other implementations, working pressure is 50psi to 1,000psi, or 50psi to 800psi, or 50psi to 700psi, 50psi to 600psi, or 600psi to 1000psi.
Be to be understood that, depend on available device, higher working pressure can be used.In other embodiments, ethene is close to stagnation point, and wherein temperature is about 270K to about 290K, and the operation dividing potential drop of ethene is that about 45 bar are to about 65 bar.In other implementations, ethene is postcritical, and wherein temperature is more than or equal to about 282K, and the operation dividing potential drop of ethene is greater than about 734psi.In other embodiment again, ethene is postcritical, and wherein temperature is more than or equal to about 282K, and the operation dividing potential drop of ethene is more than or equal to about 734psi.
Be to be understood that, and express clearly at this, service temperature and working pressure can be identical, list all separately as each each combination.Such as, in a variation pattern, the method is carried out under the working pressure of the service temperature of about 225 DEG C and about 34 bar (equaling about 500psi).
Method as herein described also can (such as, supercritical pressure and/or supercritical temperature) be carried out at supercritical conditions.Such as, in one embodiment, if do not use solvent in the reaction, super critical condition can be used.In one embodiment, the method is carried out under being more than or equal to 50 bar and/or being more than or equal to 9 DEG C (i.e. 282K).
Be to be understood that, temperature can be expressed as degree Celsius (DEG C) or degree Kelvin (K).Temperature as herein described can be become another unit from a unit conversion by those of ordinary skill in the art.Pressure also can be expressed as gauge pressure (barg), and it refers to the pressure that the Israel and Palestine of more than environmental stress or normal atmosphere represent.Pressure also can be expressed as bar, normal atmosphere (atm), pascal (Pa) or ft lbf/square inch (psi).Pressure as herein described can be become another unit from a unit conversion by those of ordinary skill in the art.
The method can be carried out under the condition stirred or do not stir.Some preferred embodiment in, the method is carried out under agitation, to increase transformation efficiency and/or selectivity.
In addition, the method can be carried out in batches or continuously.Reaction times (in batch process) or the residence time (in a continuous process) also will change along with the productive rate of reaction conditions and hope, but normally about 1-72 hour.In some aforementioned embodiments, reaction times or the residence time are determined by the conversion rate of starting raw material.In some aforementioned embodiments, reaction mixture reaction 1-24 hour.In some aforementioned embodiments, reaction mixture reaction 1-10 hour.In some aforementioned embodiments, reaction mixture reaction 1-5 hour.In some aforementioned embodiments, reaction mixture reaction 1-3 hour.In some aforementioned embodiments, reaction mixture reaction is less than 2 hours.
abstraction and purification
Reaction as herein described can also comprise the compound of separate type I from reaction mixture.In some embodiments, method as herein described also comprises separating paraxylene from reaction mixture.Any method separated product known in the art can be used.Such as, the compound (such as, p-Xylol) of formula I can pass through fractionation by distillation.
In an illustrative embodiments, in order to the compound (such as, p-Xylol) of separate type I from reaction mixture, first reaction mixture can be filtered, to remove any solid catalyst and siccative (if present).Then the mixture of filtration can be transferred to distillation tower.Those skilled in the art will know how by the compound (such as, p-Xylol) of Distillation recovery formula I, because the boiling point of the various component of reaction mixture is known, comprise the boiling point of solvent for use.Such as, in the embodiment using Isosorbide-5-Nitrae-diox, the boiling point of solvent is 101 DEG C.The boiling point being known in the art p-Xylol is 138 DEG C; The boiling point of HD is 191 DEG C; The boiling point of DMF is 94 DEG C.Recovered solvent, HD and/or DMF all can recirculation.
Method as herein described can also comprise the compound (such as, p-Xylol) of the formula I of purifies and separates.Any methods known in the art can be used to carry out the compound (such as, p-Xylol) of the formula I of purifies and separates, comprise such as column chromatography or recrystallize.
yield, transformation efficiency and selectivity
The yield of product take into account the transformation efficiency that starting raw material changes into product, and the selectivity of by product that product may be formed relative to other.
Yield, difference between transformation efficiency and selectivity are explained in the following embodiment provided.Such as, for transformation efficiency HD being changed into p-Xylol, reaction can be summarized as follows, and wherein " A " represents the mole number of HD; " B " represents the mole number of ethene; " C " represents the mole number of p-Xylol; " D " represents the mole number of the water produced; And " a ", " b ", " c " and " d " are stoichiometric coefficients.For transformation efficiency DMF being changed into p-Xylol, reaction can be summarized as follows, and wherein " A " represents the mole number of DMF; " B " represents the mole number of ethene; " C " represents the mole number of p-Xylol; " D " represents the mole number of the water produced; And " a ", " b ", " c " and " d " are stoichiometric coefficients.Such as, for the transformation efficiency HD and DMF being changed into p-Xylol, reaction can be summarized as follows, and wherein " A " represents the total mole number of HD and DMF; " B " represents the mole number of ethene; " C " represents the mole number of p-Xylol; " D " represents the mole number of the water produced; And " a ", " b ", " c " and " d " represent stoichiometric coefficient.
aA+bB→cC+dD，
The transformation efficiency of A is the per-cent of the reactant A consumed in above-mentioned reaction process, represented by following equation:
Wherein A oit is the starting molar number of reactant A; A fit is the final mole number of reactant A.
Selectivity is the stoichiometry relative quantity of the product C produced by the reactant A of inversion quantity, as being expressed as per-cent by following equation:
Wherein A oit is the starting molar number of reactant A; A fit is the final mole number of reactant A; C fit is the mole number of product C.In some embodiments of " a/c "=1 wherein, this equation can be reduced to:
The yield of product C is the per-cent of the reactant A changing into product C, as passed through represented by following equation:
Yield (%)=transformation efficiency (%) * selectivity (%).
Be to be understood that, when there is both DMF and HD, such as, selectivity is based on mole total of DMF and HD.
In some embodiments, the yield of methods described herein is at least 10wt%, at least 20wt%, at least 30wt%, at least 40wt%, at least 50wt%, at least 60wt%, at least 70wt%, at least 75wt%, at least 80wt%, at least 85wt%, at least 90wt%, at least 95wt% or at least 99wt%.In other embodiments, yield is 10wt% to 100wt%, 10wt% to 90wt%, 20wt% to 80wt%, 30wt% to 80wt%, 40wt% to 80wt%, 50wt% to 80wt% or 60wt% to 80wt%.
In some embodiments, the selectivity of methods described herein is at least 10wt%, at least 20wt%, at least 30wt%, at least 40wt%, at least 50wt%, at least 60wt%, at least 70wt%, at least 80wt%, at least 90wt% or at least 99wt%.In other embodiments, selectivity is 40% to 99%, 40% to 95%, 40% to 90%, 40% to 80%, 50% to 99%, 50% to 95%, 50% to 90%, 50% to 80%, 60% to 99%, 60% to 95%, 60% to 90%, 60% to 80%, 70% to 99%, 70% to 95%, 70% to 90% or 70% to 80%.
downstream product
The compound of the formula I manufactured according to method as herein described comprises such as p-Xylol (PX or p-dimethylbenzene) and goes for manufacturing one or more plastics, solvent or fuel.As discussed above, p-Xylol can be oxidized further, manufacture terephthalic acid.Terephthalic acid can process further, to manufacture one or more plastics.
Be to be understood that, mention " approximately " numerical value in this article or parameter comprises the embodiment that (and describing) relate to this numerical value or parameter itself.Such as, the explanation relating to " about x " comprises the explanation to x itself.In other situations, term " approximately " with other measure be combined or for modifying numerical value, unit, constant or numerical range time, refer to the change of +/-10%.
Should also be appreciated that, " extremely " mentioned in this article between two numerical value or parameter comprises the embodiment that (and describing) comprises these two numerical value or parameter itself.Such as, the explanation relating to " x to y " comprises the explanation own to " x " and " y ".
The embodiment enumerated
The embodiment below enumerated represents aspects more of the present invention.
1. manufacture a method for p-Xylol, it comprises:
A) 2,5-hexanedione is provided;
B) ethene is provided;
C) catalyzer is provided;
D) by 2,5-hexanedione, ethene and catalyzer merge, forming reactions mixture; With
E) by the p-Xylol of generation at least partially of 2,5-hexanediones in reaction mixture.
2. the method according to embodiment 1, it also comprises separating paraxylene from reaction mixture.
3. the method according to embodiment 1, it also comprises provides solvent system, and 2,5-hexanedione, ethene, catalysts and solvents system is merged, forming reactions mixture.
4. the method according to embodiment 3, wherein solvent system comprises aprotic solvent.
5. the method according to embodiment 3, wherein solvent system comprises ether solvents.
6. the method according to embodiment 3, wherein solvent system comprises C1-C20 aliphatic solvent, C6-C20 aromatic solvent, alkyl phenyl solvent, C2-C20 ether, C2-C20 ester, C1-C20 alcohol, C2-C20 ketone or its arbitrary combination or mixture.
7. the method according to embodiment 3, wherein solvent system comprises N,N-DIMETHYLACETAMIDE, acetonitrile, tetramethylene sulfone, diox, diox, dme, ether, ethylene glycol dimethyl ether (monoglyme), ethylene glycol bisthioglycolate ethyl ether (glycol diethyl ether), diethylene glycol dimethyl ether (diglyme), diethylene glycol diethyl ether (diethyl carbitol), triethylene glycol dimethyl ether (triglyme), diethylene glycol dibutyl ether (diethylene glycol dibutyl ether), TEG dimethyl ether (tetraethylene glycol dimethyl ether), multiethylene-glycol dme, dimethyl ether, higlyme, tetrahydrofuran (THF), ethylene glycol, Diethylene Glycol, triethylene glycol, polyoxyethylene glycol, cyclobutanone, cyclopentanone, pimelinketone, suberone, cyclooctanone, methyl acetate, ethyl acetate, propyl acetate, butylacetate, methyl lactate, ethyl lactate, propyl lactate, n-Butyl lactate, triactin, Dibutyl phthalate, butane, pentane, pentamethylene, hexane, hexanaphthene, heptane, suberane, octane, cyclooctane, nonane, decane, hendecane, 12 carbon alkane, hexadecane, tetrachloride, chloroform, methylene dichloride, Nitromethane 99Min., toluene, methyl-phenoxide, oil of mirbane, bromobenzene, N-methylpyrrole, p-Xylol, sym-trimethylbenzene, 12 carbon alkylbenzenes, amylbenzene, hexyl benzene, Wibaryl A, Wibaryl B, Wibaryl AB, Wibaryl F, Wibaryl R, Cepsa Petrepar 550-Q, phenyl ether, methyl diphenyl ether, ethyl phenyl ether, water or its arbitrary combination or mixture.
8. the method according to embodiment 7, wherein solvent system comprises diox, glyme, diglyme, triglyme, decane, 12 carbon alkane, p-Xylol or its arbitrary combination or mixture.
9. the method according to embodiment 8, wherein solvent system comprises p-Xylol.
10. the method according to embodiment 1, wherein catalyzer comprises 3 race's metallic cations, 9 race's metallic cations, 10 race's metallic cations, 11 race's metallic cation or lanthanide metal cations.
11. methods according to embodiment 1, wherein catalyzer comprises divalent metal or trivalent metal cation.
12. methods according to embodiment 1, wherein catalyzer comprises and is selected from Zn 2+, Cu 2+, Ni 2+, Co 2+, Al 3+, In 3+, Fe 3+, La 3+, Gd 3+and Y 3+metallic cation.
13. methods according to embodiment 1, wherein catalyzer is aluminum chloride, aluminum bromide, trifluoromethanesulfonic acid aluminium, bismuth chloride, bismuth bromide, Bismuth triflate, cupric chloride, cupric bromide, copper trifluoromethanesulfcomposite, cobalt chloride, cobaltous bromide, trifluoromethanesulfonic acid cobalt, chromium chloride, chromic bromide, trifluoromethanesulfonic acid chromium, iron(ic) chloride, iron bromide, trifluoromethanesulfonic acid iron, Gadolinium trichloride, gadolinium bromide, trifluoromethanesulfonic acid gadolinium, indium chloride, indium bromide, trifluoromethanesulfonic acid indium, nickelous chloride, nickelous bromide, trifluoromethanesulfonic acid nickel, Neodymium trichloride, neodymium bromide, trifluoromethanesulfonic acid neodymium, magnesium chloride, magnesium bromide, trifluoromethanesulfonic acid magnesium, Lanthanum trichloride, lanthanum bromide, trifluoromethanesulfonic acid lanthanum, Scium trichloride, scandium bromide, trifluoromethanesulfonic acid scandium, tin chloride, Tin tetrabromide, trifluoromethanesulfonic acid tin, titanium chloride, titanium bromide, trifluoromethanesulfonic acid titanium, vanadium chloride, bromination vanadium, trifluoromethanesulfonic acid vanadium, Yttrium trichloride, yttrium bromide, trifluoromethanesulfonic acid yttrium, zinc chloride, zinc bromide, trifluoromethanesulfonic acid zinc, venus crystals, cupric acetylacetonate or its arbitrary combination.
14. methods according to embodiment 13, wherein catalyzer is cupric chloride, copper trifluoromethanesulfcomposite or trifluoromethanesulfonic acid yttrium.
15. methods according to embodiment 1, wherein catalyzer is heteropolyacid.
16. methods according to embodiment 1, wherein catalyzer is η 2-ethylidene-copper (II) fluoroform sulphonate.
17. methods according to embodiment 1, wherein catalyzer is metal chloride, metal trifluoroacetate mesylate, metal acetate or metal acetyl acetonate; And solvent system comprises ether, C 8+alkyl solvents or p-Xylol.
18. methods according to embodiment 1, wherein catalyzer is cupric chloride, copper trifluoromethanesulfcomposite or trifluoromethanesulfonic acid yttrium; And solvent system comprises diox, 12 carbon alkane, p-Xylol or its any mixture or combination.
2,5-hexanediones at least partially are wherein changed into p-Xylol by 19. methods according to embodiment 1 at the temperature of at least 150 DEG C.
2,5-hexanediones at least partially are wherein changed into p-Xylol by 20. methods according to embodiment 19 at the temperature of 150 DEG C to 300 DEG C.
21. 1 kinds of methods manufacturing terephthalic acid, it comprises:
A) 2,5-hexanedione is provided;
B) ethene is provided;
C) catalyzer is provided;
D) by 2,5-hexanedione, ethene and catalyzer merge, forming reactions mixture; With
E) by the p-Xylol of generation at least partially of 2,5-hexanediones in reaction mixture; With
F) by p xylene oxidation, terephthalic acid is produced.
22. methods according to embodiment 21, it is also included in 2, the 5-hexanediones produced in separating step (e) before oxidation produces terephthalic acid.
The method of the compound of 23. 1 kinds of one or more formula I of manufacture:
Wherein each R 1and R 2be hydrogen, alkyl, cycloalkyl, Heterocyclylalkyl, aryl or heteroaryl independently, the method comprises:
A) by the compound of one or more formula A, the compound of one or more formula B:
Or its arbitrary combination and (i) ethene and (ii) sulfonic acid or its salt, ester, acid anhydrides or resin, or sulphonamide or its salt, or sulfimide or its salt merge, forming reactions mixture; With
B) by the compound of one or more the formula A in reaction mixture, the compound of one or more formula B or its arbitrary combination at least partially with the compound producing one or more formula I at least partially of ethene.
24. methods according to embodiment 23, wherein sulfonic acid or its salt, ester, acid anhydrides or resin, sulphonamide or its salt, or sulfimide or its salt are that original position is formed.
25. methods according to embodiment 23 or 24, wherein merge the compound of formula A, the compound of formula B or its arbitrary combination and (i) ethene and (ii) sulfonic acid or its salt, ester, acid anhydrides or polymkeric substance.
26. methods according to embodiment 25, wherein sulfonic acid has formula R xsO 3the structure of H, wherein R xalkyl, haloalkyl, cycloalkyl, Heterocyclylalkyl, aryl or heteroaryl,
Wherein each alkyl, haloalkyl, cycloalkyl, Heterocyclylalkyl, aryl or heteroaryl optionally by 1-8 independently selected from alkyl, haloalkyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl, nitro ,-OR ' ,-C (O) OR ' ,-C (O) NR ' R "-CHO ,-COR ' and the substituting group replacement of cyano group
Wherein each R ' and R " be hydrogen, alkyl or haloalkyl independently.
27. methods according to embodiment 26, wherein R xoptionally by the alkyl of alkyl, haloalkyl or nitro replacement, haloalkyl or aryl.
28. methods according to embodiment 25, wherein sulfonic acid is CF 3sO 3h (that is, trifluoromethanesulfonic acid), HCF 2cF 2sO 3h, C 6f 5sO 3h, 4-toluene sulfonic acide (that is, tosic acid) or 2,4-dinitrobenzene sulfonic acid.
29. methods according to embodiment 25, wherein sulfonate has formula Q r+[R xsO 3 -] rstructure, wherein:
Q is positively charged ion;
R xalkyl, haloalkyl, cycloalkyl, Heterocyclylalkyl, aryl or heteroaryl,
Wherein each alkyl, haloalkyl, cycloalkyl, Heterocyclylalkyl, aryl or heteroaryl optionally by 1-5 independently selected from alkyl, haloalkyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl, nitro ,-C (O) OR ' ,-C (O) NR ' R "-CHO ,-COR ' or the substituting group of cyano group replace
Wherein each R ' and R " be hydrogen or alkyl independently; And
R is cationic electric charge.
30. according to the method for embodiment [0108], wherein Q r+al 3+, Bi 3+, Cu 2+, Cu +, Cr 3+, Fe 3+, Gd 3+, In 3+, Ni 2+, Nd 3+, Li +, Na +, K +, Rb +, Cs +, Mg 2+, Ba 2+, Ca 2+, La 3+, Sc 3+, Ti 4+, V 5+, Y 3+, Zn 2+, Pt 2+, Pd 2+, Ag +, Au 3+, Tl 3+, Tl +, Re 3+, Hg 2 2+, Hg 2+, NH 4 +, Sn 4+, Sn 3+, Sn 2+, B 3+, Ga 3+, Pb 4+, Pb 2+, Co 3+, Co 2+, Ge 4+, Ge 2+, Ce 4+or Ce 3+.
31. methods according to embodiment [0108], wherein Q r+al 3+, Bi 3+, Cu 2+, Cu +, Cr 3+, Fe 3+, Gd 3+, In 3+, Ni 2+, Nd 3+, Mg 2+, Ba 2+, Ca 2+, La 3+, Sc 3+, Ti 4+, V 5+, Y 3+, Zn 2+, Pt 2+, Pd 2+, Ag +, Au 3+, NH 4 +, Sn 4+, Sn 3+, Sn 2+or B 3+.
32. methods according to embodiment [0108], wherein Q r+al 3+, Cu 2+, Cu +, Gd 3+, In 3+, Ni 2+, Nd 3+, La 3+, Sc 3+, Y 3+, Zn 2+or Co 2+.
33. methods according to embodiment [0108], wherein Q r+cu 2+, Cu +, Gd 3+, In 3+, Nd 3+, La 3+, Sc 3+or Y 3+.
34. methods according to embodiment [0108], wherein sulfonate is Al (OTf) 3, Bi (OTf) 3, Cu (OTf) 2, Cu (OTf), Cr (OTf) 3, Fe (OTf) 3, Gd (OTf) 3, In (OTf) 3, Ni (OTf) 2, Nd (OTf) 3, Rb (OTf), Cs (OTf), Mg (OTf) 2, La (OTf) 3, Sc (OTf) 3, Ti (OTf) 4, V (OTf) 5, Y (OTf) 3, Zn (OTf) 2, Pt (OTf) 2, Pd (OTf) 2, AgOTf, Au (OTf) 3, Tl (OTf) 3, Tl (OTf), Re (OTf) 3, Hg 2(OTf) 2, Hg (OTf) 2, NH 4(OTf), Sn (OTf) 4, Sn (OTf) 3, Sn (OTf) 2, B (OTf) 3, Ga (OTf) 3, Pb (OTf) 4, Pb (OTf) 2, Co (OTf) 3, Co (OTf) 2, Ge (OTf) 4, Ge (OTf) 3, Ge (OTf) 2, Ge (OTf), Ce (OTf) 4, Ce (OTf) 3or its arbitrary combination.
35. methods according to embodiment [0109], wherein sulfonate is Al (OTf) 3, Bi (OTf) 3, Cu (OTf) 2, Cu (OTf), Cr (OTf) 3, Fe (OTf) 3, Gd (OTf) 3, In (OTf) 3, Ni (OTf) 2, Nd (OTf) 3, Mg (OTf) 2, La (OTf) 3, Sc (OTf) 3, Ti (OTf) 4, V (OTf) 5, Y (OTf) 3, Zn (OTf) 2, Pt (OTf) 2, Pd (OTf) 2, Ag (OTf), Au (OTf) 3, NH 4(OTf), Sn (OTf) 4, Sn (OTf) 3, Sn (OTf) 2, B (OTf) 3or its arbitrary combination.
36. methods according to embodiment [0109], wherein sulfonate is Al (OTf) 3, Cu (OTf) 2, Cu (OTf), Gd (OTf) 3, In (OTf) 3, Ni (OTf) 2, Nd (OTf) 3, La (OTf) 3, Sc (OTf) 3, Y (OTf) 3, Zn (OTf) 2or Co (OTf) 2or its arbitrary combination.
37. methods according to embodiment [0109], wherein sulfonate is Cu (OTf) 2, Cu (OTf), Gd (OTf) 3, In (OTf) 3, Nd (OTf) 3, La (OTf) 3, Sc (OTf) 3, Y (OTf) 3or its arbitrary combination.
38. methods according to embodiment 25, wherein merge the compound of formula A, the compound of formula B or its arbitrary combination and (i) ethene and (ii) sulfonate resin.
39. methods according to embodiment 38, wherein sulfonate resin is halogenosulfonic acid resin.
40. methods according to embodiment [0111], wherein sulfonate resin is flurosulphonic acid resin.
41. methods according to embodiment [0111], wherein sulfonate resin is R x1cF 2sO 3h, wherein R x1alkyl or haloalkyl.
42. methods according to embodiment 25, wherein merge the compound of formula A, the compound of formula B or its arbitrary combination and (i) ethene and (ii) sulfimide or its salt.
43. methods according to embodiment 42, wherein sulfimide has formula (R y1sO 2) NH (SO 2r y2) structure, wherein R y1and R y2be alkyl, haloalkyl, cycloalkyl, Heterocyclylalkyl, aryl or heteroaryl independently of one another,
Wherein each alkyl, haloalkyl, cycloalkyl, Heterocyclylalkyl, aryl or heteroaryl are optionally replaced by the individual substituting group independently selected from alkyl, haloalkyl, cycloalkyl, Heterocyclylalkyl, aryl and heteroaryl of 1-5.
44. methods according to embodiment 43, wherein sulfimide is NH (Tf) 2(that is, trifluoromethanesulfonic acid imide).
45. methods according to embodiment 42, wherein sulfimide salt has formula Q r+[(R y1sO 2) N (R y2sO 2)] rstructure, wherein:
Q is positively charged ion;
Each R y1and R y2be alkyl, haloalkyl, cycloalkyl, Heterocyclylalkyl, aryl or heteroaryl independently,
Wherein each alkyl, haloalkyl, cycloalkyl, Heterocyclylalkyl, aryl or heteroaryl optionally by 1-5 independently selected from alkyl, haloalkyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl, nitro ,-C (O) OR ' ,-C (O) NR ' R "-CHO ,-COR ' or the substituting group of cyano group replace
Wherein each R ' and R " be hydrogen or alkyl independently; And
R is cationic electric charge.
46. methods according to embodiment 45, wherein Q r+al 3+, Bi 3+, Cu 2+, Cu +, Cr 3+, Fe 3+, Gd 3+, In 3+, Ni 2+, Nd 3+, Li +, Na +, K +, Rb +, Cs +, Mg 2+, Ba 2+, Ca 2+, La 3+, Sc 3+, Ti 4+, V 5+, Y 3+, Zn 2+, Pt 2+, Pd 2+, Ag +, Au 3+, Tl 3+, Tl +, Re 3+, Hg 2 2+, Hg 2+, NH 4 +, Sn 4+, Sn 3+, Sn 2+, B 3+, Ga 3+, Pb 4+, Pb 2+, Co 3+, Co 2+, Ge 4+, Ge 2+, Ce 4+or Ce 3+.
47. methods according to embodiment 46, wherein Q r+al 3+, Bi 3+, Cu 2+, Cu +, Cr 3+, Fe 3+, Gd 3+, In 3+, Ni 2+, Nd 3+, Mg 2+, Ba 2+, Ca 2+, La 3+, Sc 3+, Ti 4+, V 5+, Y 3+, Zn 2+, Pt 2+, Pd 2+, Ag +, Au 3+, NH 4 +, Sn 4+, Sn 3+, Sn 2+or B 3+.
48. methods according to embodiment 46, wherein Q r+al 3+, Cu 2+, Cu +, Gd 3+, In 3+, Ni 2+, Nd 3+, La 3+, Sc 3+, Y 3+, Zn 2+or Co 2+.
49. methods according to embodiment 46, wherein Q r+cu 2+, Cu +, Gd 3+, In 3+, Nd 3+, La 3+, Sc 3+or Y 3+.
50. methods according to embodiment 45, wherein sulfimide salt is Al [N (Tf) 2] 3, Bi [N (Tf) 2] 3, Cu [N (Tf) 2] 2, Cu [N (Tf) 2], Cr [N (Tf) 2] 3, Fe [N (Tf) 2] 3, Gd [N (Tf) 2] 3, In [N (Tf) 2] 3, Ni [N (Tf) 2] 2, Nd [N (Tf) 2] 3, Li [N (Tf) 2], Na [N (Tf) 2], K [N (Tf) 2], Rb [N (Tf) 2], Cs [N (Tf) 2], Mg [N (Tf) 2] 2, Ba [N (Tf) 2] 2, Ca [N (Tf) 2] 2, La [N (Tf) 2] 3, Sc [N (Tf) 2] 3, Ti [N (Tf) 2] 4, V [N (Tf) 2] 5, Y [N (Tf) 2] 3, Zn [N (Tf) 2] 2, Pt [N (Tf) 2] 2, Pd [N (Tf) 2] 2, Ag [N (Tf) 2], Ag [N (Tf) 2] 2, Au [N (Tf) 2] 3, Tl [N (Tf) 2] 3, Tl [N (Tf) 2], Re [N (Tf) 2] 3, Hg 2[N (Tf) 2] 2, Hg [N (Tf) 2] 2, NH 4[N (Tf) 2], Sn [N (Tf) 2] 4, Sn [N (Tf) 2] 3, Sn [N (Tf) 2] 2, B [N (Tf) 2] 3, Ga [N (Tf) 2] 3, Pb [N (Tf) 2] 4, Pb [N (Tf) 2] 2, Co [N (Tf) 2] 3, Co [N (Tf) 2] 2, Ge [N (Tf) 2] 4, Ge [N (Tf) 2] 3, Ge [N (Tf) 2] 2, Ge [N (Tf) 2], Ce [N (Tf) 2] 4, Ce [N (Tf) 2] 3or its arbitrary combination.
51. methods according to embodiment 45, wherein sulfimide salt is Al [N (Tf) 2] 3, Bi [N (Tf) 2] 3, Cu [N (Tf) 2] 2, Cu [N (Tf) 2], Cr [N (Tf) 2] 3, Fe [N (Tf) 2] 3, Gd [N (Tf) 2] 3, In [N (Tf) 2] 3, Ni [N (Tf) 2] 2, Nd [N (Tf) 2] 3, Mg [N (Tf) 2] 2, Ba [N (Tf) 2] 2, Ca [N (Tf) 2] 2, La [N (Tf) 2] 3, Sc [N (Tf) 2] 3, Ti [N (Tf) 2] 4, V [N (Tf) 2] 5, Y [N (Tf) 2] 3, Zn [N (Tf) 2] 2, Pt [N (Tf) 2] 2, Pd [N (Tf) 2] 2, Ag [N (Tf) 2], Ag [N (Tf) 2] 2, Au [N (Tf) 2] 3, NH 4[N (Tf) 2], Sn [N (Tf) 2] 4, Sn [N (Tf) 2] 3, Sn [N (Tf) 2] 2, B [N (Tf) 2] 3or its arbitrary combination.
52. methods according to embodiment 45, wherein sulfimide salt is Al [N (Tf) 2] 3, Cu [N (Tf) 2] 2, Cu [N (Tf) 2], Gd [N (Tf) 2] 3, In [N (Tf) 2] 3, Ni [N (Tf) 2] 2, Nd [N (Tf) 2] 3, La [N (Tf) 2] 3, Sc [N (Tf) 2] 3, Y [N (Tf) 2] 3, Zn [N (Tf) 2] 2or Co [N (Tf) 2] 2or its arbitrary combination.
53. methods according to embodiment 45, wherein sulfimide salt is Cu [N (Tf) 2] 2, Cu [N (Tf) 2], Gd [N (Tf) 2] 3, In [N (Tf) 2] 3, Nd [N (Tf) 2] 3, La [N (Tf) 2] 3, Sc [N (Tf) 2] 3, Y [N (Tf) 2] 3or its arbitrary combination.
54. methods according to embodiment 42, wherein sulfimide salt is two (trifyl) imide of ethyl dimethyl propyl ammonium, two (trifyl) imide of 1-butyl-1-crassitude, two (trifyl) imide of 1-ethyl-3-methylimidazole, two (trifyl) imide of 1-butyl-3-Methylimidazole, two (trifyl) imide of 1-allyl group-3-Methylimidazole, two (trifyl) imides of triethyl sulfonium or its arbitrary combination.
55. methods according to embodiment 23; wherein sulfonic acid or its salt, ester, acid anhydrides or resin; sulphonamide or its salt; or sulfimide or its salt are two (trifyl) acid amides of three hexyl n-tetradecane Ji Phosphonium, 1,2-dimethyl-3-propyl imidazole two (trifyl) imide, [(C 6h 13) 3(C 14h 29) P] +[(CF 3sO 2) 2n] -, [C 11h 16n] +[N (SO 2cF 3) 2] -, [C 8h 15n 2] +[N (SO 2cF 3) 2] -, [C 6h 11n 2] +[N (SO 2cF 2cF 3) 2] -, [C 6h 11n 2] +[N (SO 2cF 3) 2] -, [C 6h 14n] +[N (SO 2cF 3) 2] -, 1-butyl-1-crassitude fluoroform sulphonate, 1-ethyl-3-methylimidazole fluoroform sulphonate, 1-butyl-3-Methylimidazole fluoroform sulphonate, 1-butyl-3-Methylimidazole fluoroform sulphonate or its arbitrary combination.
56. according to embodiment 23 method, wherein the salt of sulfonic acid, sulphonamide or sulfimide has positively charged ion, and its cationic is greater than-0.2eV relative to the standard electrode potential of standard hydrogen current potential.
The method of the compound of 57. 1 kinds of one or more formula I of manufacture:
Wherein each R 1and R 2be hydrogen, alkyl, cycloalkyl, Heterocyclylalkyl, aryl or heteroaryl independently, the method comprises:
A) by the compound of one or more formula A, the compound of one or more formula B:
Or its arbitrary combination and ethene and the catalyzer that comprises monovalent metal cation merge, forming reactions mixture; With
B) by the compound of one or more the formula A in reaction mixture, the compound of one or more formula B or its arbitrary combination at least partially with the compound producing one or more formula I at least partially of ethene.
58. methods according to embodiment 57, wherein monovalent metal cation is Cu +.
59. methods according to embodiment 57, wherein catalyzer is Cu [(BF 4) (CH 3cN) 4], [Cu (OTf)] 2c 6h 6or [Cu (OTf)] (CH 3cN) 4.
The method of the compound of 60. 1 kinds of one or more formula I of manufacture:
Wherein each R 1and R 2be hydrogen, alkyl, cycloalkyl, Heterocyclylalkyl, aryl or heteroaryl independently, the method comprises:
A) by the compound of one or more formula A, the compound of one or more formula B:
Or its arbitrary combination and ethene and pKa merge lower than the acid of the pKa of sulfuric acid, forming reactions mixture; With
B) by the compound of one or more the formula A in reaction mixture, the compound of one or more formula B or its arbitrary combination at least partially with the compound producing one or more formula I at least partially of ethene.
The method of the compound of 61. 1 kinds of one or more formula I of manufacture:
Wherein each R 1and R 2be hydrogen, alkyl, cycloalkyl, Heterocyclylalkyl, aryl or heteroaryl independently, the method comprises:
A) by the compound of one or more formula A, the compound of one or more formula B:
Or its arbitrary combination merges with ethene and heteropolyacid, forming reactions mixture; With
B) by the compound producing one or more formula I at least partially in the compound of one or more the formula A in reaction mixture, the compound of one or more formula B or its arbitrary combination.
62. according to the method in embodiment 23-61 described in any one, wherein R 1and R 2be alkyl separately.
63. methods according to embodiment 62, wherein R 1and R 2be methyl separately.
64. according to the method in embodiment 23-63 described in any one, and it also comprises and the compound of one or more formula A, the compound of one or more formula B or its arbitrary combination and solvent system being merged.
65. methods according to embodiment 64, wherein solvent system comprises aliphatic solvent, aromatic solvent, alkyl phenyl solvent, ether solvents, ester solvent, alcoholic solvent, ketone solvent, ionic liquid or its arbitrary combination or mixture.
66. methods according to embodiment 65, wherein solvent system comprises alkyl solvents or polyphenylene oxide.
67. methods according to embodiment 65, wherein solvent system comprises N,N-DIMETHYLACETAMIDE, acetonitrile, tetramethylene sulfone, diox, diox, dme, ether, ethylene glycol dimethyl ether (monoglyme), ethylene glycol bisthioglycolate ethyl ether (glycol diethyl ether), diethylene glycol dimethyl ether (diglyme), diethylene glycol diethyl ether (diethyl carbitol), triethylene glycol dimethyl ether (triglyme), diethylene glycol dibutyl ether (diethylene glycol dibutyl ether), TEG dimethyl ether (tetraethylene glycol dimethyl ether), multiethylene-glycol dme, dimethyl ether, higlyme, tetrahydrofuran (THF), ethylene glycol, Diethylene Glycol, triethylene glycol, polyoxyethylene glycol, cyclobutanone, cyclopentanone, pimelinketone, suberone, cyclooctanone, methyl acetate, ethyl acetate, propyl acetate, butylacetate, methyl lactate, ethyl lactate, propyl lactate, n-Butyl lactate, triactin, Dibutyl phthalate, butane, pentane, pentamethylene, hexane, hexanaphthene, heptane, suberane, octane, cyclooctane, nonane, decane, hendecane, 12 carbon alkane, hexadecane, tetrachloride, chloroform, methylene dichloride, Nitromethane 99Min., toluene, methyl-phenoxide, oil of mirbane, bromobenzene, methylpyrrole, methyl-2-pyrrolidone, dimethyl furan, dichlorobenzene, water, p-Xylol, sym-trimethylbenzene, 12 carbon alkylbenzenes, amylbenzene, hexyl benzene, Wibaryl A, Wibaryl B, Wibaryl AB, Wibaryl F, Wibaryl R, Cepsa Petrepar 550-Q, Santovac, phenyl ether, methyl diphenyl ether, ethyl phenyl ether, water or its arbitrary combination or mixture.
68. methods according to embodiment 23, wherein:
R 1and R 2be methyl separately; Or R 1methyl, and R 2hydrogen; With
Sulfonic acid or its salt, ester, acid anhydrides or polymkeric substance.
69. methods according to embodiment 23, wherein:
R 1and R 2be methyl separately; With
Sulfonic acid or its salt, ester, acid anhydrides or polymkeric substance.
70. methods according to embodiment 69 or 69, wherein:
Sulfonic acid or its salt are trifluoromethanesulfonic acid or its salt.
71. methods according to embodiment 64, wherein solvent system comprises p-Xylol.
72. methods according to embodiment 64, wherein solvent system comprises C4-C30 alkyl solvents.
73. methods according to embodiment 72, wherein C4-C30 alkyl solvents is side chain.
74. methods according to embodiment 64, wherein:
R 1and R 2be methyl separately; Or R 1methyl, and R 2hydrogen; And
Solvent system comprises p-Xylol, C4-C30 alkyl solvents or its any mixture.
75. methods according to embodiment 64, wherein:
R 1and R 2be methyl separately; And
Solvent system comprises p-Xylol, C4-C30 alkyl solvents or its any mixture.
Embodiment
Following examples are only Illustrative, are limited by any way unintentionally to any aspect of present disclosure.
Embodiment 1
PX is prepared by DMF
The mixture of 5.0g DMF, 0.025g copper trifluoromethanesulfcomposite and 100mL diox is encased in and is equipped with in the angle of rake autoclave of gas entrainment.By autoclave nitrogen purging 3 times, purge 1 time with ethene, be then forced into 500psig (3,447kpas) with ethene.Autoclave is heated to 250 DEG C, pressure is increased to 2250psig (15,513kpas) at such a temperature.Reactor is kept pressurization 7 hours at 250 DEG C, wherein closes well heater, reactor is cooled under RT.Pressure release, and reaction soln is poured in storage bottle.Reaction mixture is the pale yellow solution with a small amount of black precipitate.Pass through 1h and 13c NMR spectrum is analyzed mutually to solution, identifies as remaining DMF, the PX of main ingredient, ethene and HD and as solvent diox.These components are passed through 1h NMR composes in addition quantitative, and numerical value provides in table 1 below.In this sample, the ethene of about 0.3mol% is observed by NMR.
For various catalyzer, solvent and temperature shown in following table 1, repeat the scheme in this embodiment.
Table 1
Mol% refers to the mol% in diox, and HD is calculated as except the mol% of initial DMF.
Embodiment 2
PX is prepared by DMF and HD
The mixture of 8.0g DMF, 2.0g HD, 0.5g trifluoromethanesulfonic acid yttrium and 200g diox is encased in and is equipped with in the angle of rake autoclave of gas entrainment.By autoclave nitrogen purging 3 times, purge 1 time with ethene, be then forced into 500psig (3,447kpas) with ethene.Autoclave is heated to 250 DEG C, pressure is increased to 2,000psig (13,790kpas) at such a temperature.Reactor is kept pressurization 7 hours at 250 DEG C.With hour for interval sampling, and by NMR spectrum analysis transformation efficiency and selectivity.After 7 hours, close well heater, and make reactor cooling to RT.Pressure release, and reaction soln is poured in storage bottle.Obtain the transformation efficiency of 100% after 7 hours, PX is 90% based on the molar selectivity of HD and DMF, and yield equals 90%.
Embodiment 3
PX is prepared by HD
The mixture of 5.0g HD, 0.05g copper trifluoromethanesulfcomposite and 100g diox is encased in and is equipped with in the angle of rake autoclave of gas entrainment.By autoclave nitrogen purging 3 times, purge 1 time with ethene, be then forced into 500psig (3,447kpas) with ethene.Autoclave is heated to 250 DEG C, pressure is increased to 1900psig (13,100kpas) at such a temperature.Reactor is kept pressurization 7 hours at 250 DEG C.With hour for interval sampling, and by NMR spectrum analysis transformation efficiency and selectivity.After 7 hours, close well heater, and make reactor cooling to RT.Pressure release, and reaction soln is poured in storage bottle.Obtain the transformation efficiency of 94% after 7 hours, PX is 99% based on the molar selectivity of HD, and yield equals 93%.
Embodiment 4 (comparative example)
Gac is used to manufacture comparing of PX with other catalyzer by DMF
By 10.0g DMF, 1.0g Norit Darco G60 gac, 2.1g the mixture of molecular sieve (predrying mistake) and 200g diox is encased in and is equipped with in the angle of rake autoclave of gas entrainment.By autoclave nitrogen purging 3 times, purge 1 time with ethene, be then forced into 460psig (3,1712kpas).Autoclave is heated to 190 DEG C, pressure is increased to 1270psig (8,756kpas) at such a temperature.When closing well heater, reactor being kept pressurization 24 hours at 190 DEG C, making reactor cooling to RT.Before cooling, pressure has been down to 1240psig (8.549kpas).Pressure release, and reaction soln is poured in storage bottle.Reaction mixture is black, muddiness, but once leaving standstill, when Norit sedimentation, it is clarified to a certain extent.Pass through 1h and 13c NMR spectrum is analyzed solution, identifies as remaining DMF, the PX of main ingredient, ethene and HD and as solvent diox.These components are passed through 1h NMR composes in addition quantitative, and numerical value provides in lower Table A.The DMF transformation efficiency observed is very low, and only 4.6%, this amount only has 19% to change into PX.
For various catalyzer, solvent and temperature shown in following table 2, repeat the scheme in this comparative example.
Table 2
Mol% refers to the mol% in diox, and HD is calculated as except the mol% of initial DMF.
ND refers to " countless certificate ".
Embodiment 5
Load with the comparing of the catalyzer of non-load
This embodiment is to working load catalyzer (such as, CuCl 2/ aluminum oxide, CuCl 2/ HY zeolite) with catalyzer (such as, the CuCl of non-load 2, Cu (OTf) 2, Y (OTf) 3) speed of reaction that DMF changed into PX compares.
The mixture of 10g DMF, catalyzer (type and consumption are as shown in Table 3 below) and 200g diox is encased in and is equipped with in the angle of rake autoclave of gas entrainment.By autoclave nitrogen purging 3 times, purge 1 time with ethene, be then forced into 500psig (3,447kpas) with ethene.Autoclave is heated to 250 DEG C.Reactor is kept pressurization 7 hours at 250 DEG C.With hour for interval sampling, and by NMR spectrum analysis transformation efficiency and selectivity.After 7 hours, close well heater, and make reactor cooling to RT.Pressure release, and reaction soln is poured in storage bottle.The transformation efficiency of each catalyzer, molar selectivity and yield are summarized in following table 3.
Table 3. Data Summary (10g DMF, 200g diox, 250 DEG C, 500psig C 2h 4)
Based on the result of upper table 3, DMF is changed into PX than supported catalyst by catalyzer quickly that observe non-load.
Embodiment 6
The comparison of different catalysts type and amount
This embodiment compares the speed of reaction using different amount catalyzer DMF to be changed into PX.
Respectively according to the condition shown in following table 4,5,6, for three kinds of different catalyzer (that is, CuCl 2, Cu (OTf) 2with Y (OTf) 3), use the scheme for DNM being changed into PX described in above embodiment 5.The transformation efficiency of each catalyzer, molar selectivity and yield are also summarized in following table.
Table 4.CuCl 2sum up (10g DMF, 200g diox, 250 DEG C, 500psig C 2h 4)
Table 5.Cu (OTf) 2data Summary (250 DEG C, 500psig C 2h 4)
Table 6.Y (OTf) 3data Summary (10g DMF, 200g diox, 250 DEG C, 500psig C 2h 4)
Embodiment 7
The comparison of solvent strength
This embodiment compares the speed of reaction using different concns diox DMF to be changed into PX as solvent.
According to the condition shown in following table 7, use the scheme for DMF being changed into PX described in above embodiment 5.Isolate the sample taking from reacting phase separately.What observe is the opaque rich PX phase on top and the water/diox phase of bottom mutually.The transformation efficiency of each catalyzer, molar selectivity and yield are also summarized in following table 7.
Table 7. solvent strength Data Summary (0.5g Y (OTf) 3, 200g diox, 250 DEG C, 500psigC 2h 4).
Embodiment 8
The comparison of type of solvent
To using different solvents to comprise, speed of reaction that DMF to change into PX by diox, triglycol dimethyl ester, triethylene glycol (TEG), N-methylpyrrole (NMP), tetramethylene sulfone, propylene carbonate and methyl-sulphoxide (DMSO) compares this embodiment.
According to the condition shown in following table 8, use the scheme for DMF being changed into PX described in above embodiment 5.The transformation efficiency of each catalyzer of diox, TEG, tetramethylene sulfone, triglyme and NMP, molar selectivity and yield are also summarized in following table 8.It is unstable for observing propylene carbonate at 250 DEG C, seems to resolve into CO 2.Similarly, DMSO is also unstable at 250 DEG C, seems to decompose.Like this, the reaction of propylene carbonate and DMSO is used not sample.
Table 8. solvent Data Summary (0.5g Y (OTf) 3, 10g DMF, 250 DEG C, 500psig C 2h 4)
ND refers to " countless certificate ".
Based on the data in table 8, observe diox and triglyme has similar reaction kinetics in process DMF being changed into PX.Also observing NMP is in addition suitable solvent for DMF being changed into PX.
Embodiment 9
For improving the comparison of PX optionally solvent
This embodiment compares the speed of reaction using different solvents and catalyzer DMF to be changed into PX.The solvent used comprises triglyme and triethylene glycol (TEG).Catalyzer comprises Cu (OTf) 2with Y (OTf) 3.
The scheme for DMF being changed into PX described in above embodiment 5 is used according to the condition shown in following table 9 and 10.The transformation efficiency of each catalyzer, molar selectivity and yield are combined for each solvent/catalyst be summarized in following table.
Table 9. triglyme Data Summary (10g DMF, 250 DEG C, 500psig C 2h 4)
Table 10.TEG Data Summary (500psig C 2h 4)
Based on the data in upper table 9, triglyme is as solvent and Cu (OTf) 2in process DMF being changed into PX, Yu diox is shown as solvent and Cu (OTf) as catalyzer 2as catalyzer (data based in above embodiment 6 table 5) comparable reaction kinetics.
Embodiment 10
The comparison of temperature
This embodiment compares the speed of reaction at different temperature DMF being changed into PX.The scheme for DMF being changed into PX described in above embodiment 5 is used according to the temperature shown in following table 11.Reaction in this embodiment uses 10g DMF, 1.0g CuCl 2, 200g diox and 500psig C 2h 4.Transformation efficiency, molar selectivity and yield are summarized in following table 11.
Table 11. temperature data sums up (1.0g CuCl 2, 10g DMF, 200g diox, 500psigC 2h 4)
Observe the kinetics of temperature on reaction and have impact.In order to make reaction that about 90% transformation efficiency occur in rational time quantum, the temperature close to 250 DEG C should be used.Reduce temperature of reaction and unexpectedly do not increase selectivity, increase along with the transformation efficiency in 180 DEG C of reactions at the end of time and 7 hours because observe selectivity.
Embodiment 11
The comparison of pressure
This embodiment compares the speed of reaction at various pressures DMF being changed into PX.The scheme for DMF being changed into PX described in above embodiment 5 is used according to the condition shown in following table 12 and 13.The solvent Shi diox used in this embodiment, and the catalyzer used is CuCl 2with Y (OTf) 3.The transformation efficiency of each catalyzer of combination of each catalyzer/pressure, molar selectivity and yield are summarized in following table.
Table 12.Y (OTf) 3/ pressure data sums up (0.5g Y (OTf) 3, 10g DMF, 200g diox, 250 DEG C)
Table 13CuCl 2/ pressure data sums up (1.0g CuCl 2, 10g DMF, 200g diox, 180 DEG C)
Embodiment 12
PX is manufactured by HD
This embodiment illustrates the conversion of HD to PX.Scheme described in embodiment 5 is used for the HD (2g) as starting raw material.Use Y (OTf) 3as catalyzer (0.5g), use diox (200g) as solvent.Ethene provides under 500psig, and temperature of reaction is 250 DEG C.Transformation efficiency, molar selectivity and yield are summarized in following table 14.
Table 14.HD Data Summary
Based on the data in upper table 14, for Y (OTf) 3catalyzer, observe HD with about 99% selective conversion become PX.
In contrast, carry out use HD and do not use the reaction of ethene or catalyzer (5g HD, 100g diox, 250 DEG C).Do not observe HD in the absence of a catalyst and change into DMF.In addition, also carried out there is catalyzer but there is no HD (5g HD, the 0.25g Y (OTf) of ethene 3, 100g diox, 250 DEG C).After the reaction times of 1 hour, the HD of 86% with 62% be selectively converted to DMF.
Embodiment 13
Use the comparison of heteropolyacid
This embodiment compares the speed of reaction using heteropolyacid catalyst DMF to be changed into PX.For each catalysts and solvents together with reaction conditions, use the scheme described in embodiment 5, as in following table 15 sum up.The PX yield of each reaction is also provided in the following table in 15.
Table 15.HPA Data Summary (10g DMF, 0.5g catalyzer, 200g solvent, 250 DEG C, 500psig C 2h 4)
ND=NMR composes off-duty
Embodiment 14
Use the comparison of all kinds of SOLVENTS
This embodiment compares the speed of reaction using aliphatic solvent and solvent mixture DMF to be changed into PX.For each catalysts and solvents together with reaction conditions, use the scheme described in embodiment 5, as in following table 16 and 17 sum up.The PX yield of each reaction is also provided in the following table in 16 and 17.
Table 16. solvent Data Summary (10g DMF, 0.5g catalyzer, 200g solvent, 250 DEG C, 500psig C 2h 4)
Table 17. aliphatic solvent Data Summary
ND=is quantitative non-availability optionally, but observes the PX as product
Embodiment 15
Use the comparison of the salt catalyst containing copper
This embodiment compares using speed of reaction DMF being changed into PX containing the salt catalyst such as venus crystals and levulinic acid copper of metal.For each catalysts and solvents together with reaction conditions, use the scheme described in embodiment 5, as in following table 18 sum up.The PX yield of each reaction is also provided in the following table in 18.
Salt catalyst Data Summary (2.5g DMF, 50g diox, 0.125g catalyzer, 250 DEG C, the 1500-1600psig C of table 18. containing copper 2h 4)
Salt catalyst containing copper Transformation efficiency (mole) Selectivity (mole)
Venus crystals 85.9 ND
Levulinic acid copper 80.1 94.5
ND=is quantitative non-availability optionally, but observes the PX as product
Embodiment 16
The comparison of solvent
This embodiment is using Cu (OTf) to all kinds of SOLVENTS 2as catalyzer, by DMF, the impact changed in PX compares.
Catalyzer shown in DMF and following table 16 is encased in Parr container, reactor is sealed, is placed in heating mantles, and is connected with nitrogen pipeline, ethene gas cylinder, temperature regulator and waste material container (passing through purging valve).Reaction mixture nitrogen (the about 80psig of nitrogen pressure) is rinsed 3 times, rinses 3 times with ethene (the about 100psig of ethylene pressure), then 500psig ethene is incorporated in reaction mixture, stirs the mixture.Ethylene pressure is a certain numerical value (depending on solvent used) along with mixing is reduced to, and is able to stabilization herein.By adding more ethene, pressure is adjusted to 500psig again.Reaction mixture is heated to 250 DEG C, and keeps 7 hours at such a temperature.At the end of the reaction times, remove heating mantles, and make Parr reactor experience nitrogen gas stream, to realize cooling.When reactor gets back to room temperature, by the ethene that purging valve slow releasing is excessive, reaction mixture is transferred in sampling receptacle, and is analyzed by NMR and GC-MS.The PX transformation efficiency of each reaction and selectivity are also provided in table 19.
Table 19. solvent screening Data Summary
1)pressure was sharply increased to 2000psig (250 DEG C) from 1600psig in about 15 minutes, stopped heating
2)temperature of reaction=200 DEG C
3)use 0.1g diox as mark in GC-MS analysis
4)c 2h 4original pressure=400psig, instead of 500psig
5)observe solvent hydrolysis, and increase as the amount of the n-propyl toluene of by product.
6)do not pass through 1h-NMR identifies product.
7)use diox (6.1g) as solvent.
8selectivity cannot be determined.
Embodiment 17
The optimization of DMF and catalyst concn
This embodiment illustrates DMF and Cu (OTf) of various concentration 2dMF is being changed into the impact in PX by (as catalyzer).Use 12 independent carbon alkane or 12 carbon alkane with the mixture of diox is as solvent.For each reagent together with reaction conditions, use the scheme described in embodiment 16, as in following table 20 sum up.The PX transformation efficiency of each reaction and selectivity are also provided in the following table in 20.
Table 20. Data Summary
Embodiment 18
The comparison of solvent mixture
This embodiment illustrates solvent mixture and DMF is being changed into the impact in PX.The solvent used in this embodiment comprises p-Xylol, 12 carbon alkane with diox.For each reagent together with reaction conditions, use the scheme described in embodiment 16, as in following table 21 sum up.The PX transformation efficiency of each reaction and selectivity are also provided in the following table in 21.
Table 21. solvent mixture Data Summary
* venus crystals (II), instead of copper trifluoromethanesulfcomposite (II)
Embodiment 19
The comparison of catalyzer
This embodiment on various catalyzer by DMF, the impact changed in PX compares.For each catalysts and solvents together with reaction conditions, use the scheme described in embodiment 16, as in following table 22 sum up.The PX transformation efficiency of each reaction and selectivity are also provided in the following table in 22.
Table 22. catalyst data is summed up
15.01g diox is used with the mixture of 12 carbon alkane;
2use 0.1g diox as interior mark;
3use 0.22g diox as interior mark;
4400psig C 2h 4, instead of 500psig;
5hBF 4excessive use (3.69/1);
6cF 3sO 3the excessive use of H (1.7/1)
Based on the result of upper table 22, observe DMF and under the existence of trifluoromethanesulfonic acid salt catalyst, change into PX in diox or 12 carbon alkane, transformation efficiency is at least 98%, and selectivity is at least 84%.When using diox as solvent, observe heteropolyacid such as 12-silicomolybdic acid monohydrate and 12-phospho-molybdic acid monohydrate and transform PX, transformation efficiency is about 98%, and selectivity is about 80%.In addition, unexpectedly observe independent triflic acid catalyzes DMF and change into PX.
Embodiment 20
The comparison of ethylene pressure
This embodiment on change ethylene pressure by DMF, the impact changed in PX compares.Scheme described in embodiment 16 is used for ethylene pressure, as table 23 (ethylene pressure is near super critical point) and table 24 (ethylene pressure is lower than 500psig) middle sum up.Ethene super critical point is about 50 bar (725psi) at 10 DEG C.At 250 DEG C, supercritical pressure is about 725psi (739.7psig).For each ethylene pressure shown in following table 23, carry out twice experiment (stir and do not stir), to evaluate the impact of mixing on reaction in addition.The PX transformation efficiency of each reaction and selectivity are also provided in the following table in 23 and 24.
Data Summary (initial composition of reaction mixture: 30.0g 12 carbon alkane+20.0g DMF, the 0.15g Cu (OTf) of ethylene pressure near table 23. super critical point 2+ 0.10g diox)
Data Summary (initial composition of reaction mixture: 30.0g 12 carbon alkane+20.0g DMF, the 0.15g Cu (OTf) of table below 24.500psig ethylene pressure 2+ 0.10g diox)
*p after C2H4 refillsthe total ethene loaded in=Parr reactor, consider in the original pressure of loading and reaction mixture along with mixed ethylene dissolve to make pressure get back to after the pressure caused reduces original pressure needs refilling.Such as, when initial load 100psig ethene time, pressure is reduced to 90psig along with mixing.By adding 10psig (refilling), pressure is adjusted to original pressure again, the total pressure therefore loaded is 110psig.
Embodiment 21
There is the comparison of the reacting middle catalyst of SolTrol
Catalyzer shown in Soltrol 170 (30g), 2,5-dimethyl furans (20g, 0.208mol) and following table 25 is encased in Parr container.Reactor is sealed, is placed in heating mantles, and is connected with nitrogen pipeline, ethene gas cylinder, temperature regulator and waste material container (passing through purging valve).By reaction mixture nitrogen rinse 3 times, use ethene rinse 3 times, then 500psig ethene is incorporated in reaction mixture, and stirs the mixture with 1020-1025Hz.Ethylene pressure is reduced to 357psi along with stirring.By adding more ethene, pressure being adjusted to 500psig again, making the ethene of total introducing be 655psi.Reaction mixture is heated to 250 DEG C, and keeps 7 hours at such a temperature.At the end of the reaction times, remove heating mantles, and make the outside experience nitrogen gas stream of Parr reactor, to realize cooling.When reactor gets back to room temperature, by the ethene that purging valve slow releasing is excessive, and reaction mixture is transferred in sampling receptacle, and is analyzed by NMR and GC-MS.
Table 25. Data Summary
Embodiment 22
There is the comparison of solvent in the reaction of trifluoromethanesulfonic acid
By the solvent, 2 shown in following table 26,5-dimethyl furan and trifluoromethanesulfonic acid are encased in Parr container, and reactor is sealed, be placed in heating mantles, and be connected with nitrogen pipeline, ethene gas cylinder, temperature regulator and waste material container (passing through purging valve).By reaction mixture nitrogen rinse 3 times, use ethene rinse 3 times, then 500psig ethene is incorporated in reaction mixture, and stirs the mixture with 1020-1025Hz.Ethylene pressure is a certain numerical value (depending on solvent used) along with stirring is reduced to, and is able to stabilization herein.By adding more ethene, pressure being adjusted to 500psig again, making the ethene of total introducing be 655psi.Reaction mixture is heated to 250 DEG C, and keeps 7 hours at such a temperature.At the end of the reaction times, remove heating mantles, and make the outside experience nitrogen gas stream of Parr reactor, to realize cooling.When reactor gets back to room temperature, by the ethene that purging valve slow releasing is excessive, reaction mixture is transferred in sampling receptacle, and is analyzed by NMR and GC-MS.
Table 26. Data Summary
Embodiment 23
As the normal heptane of solvent and the impact of 12 carbon alkane and the zeolite as catalyzer
By normal heptane (52.3g), 12 carbon alkane (7.82g), 2,5-dimethyl furan (11.54g, 0.120mol) (2, the 1.2M solution of 5-dimethyl furan in the mixture of normal heptane and 12 carbon alkane) and the beta-zeolite (Zeolyst CP 814E) of 0.45g calcining be encased in Parr container, and reactor is sealed, be placed in heating mantles, be connected with nitrogen pipeline, ethene gas cylinder, temperature regulator and waste material container (passing through purging valve).By reaction mixture nitrogen rinse 3 times, use ethene rinse 3 times, then 200psig ethene is incorporated in reaction mixture under the stirring of 1020Hz.Reaction mixture is heated to 250 DEG C, and keeps 24 hours at such a temperature.At the end of the reaction times, remove heating mantles, and make the outside experience nitrogen gas stream of Parr reactor, to realize cooling.When reactor gets back to room temperature, by the ethene that purging valve slow releasing is excessive.
Table 27. Data Summary
* the catalyzer used in twice experiment is available from two different batches.

Claims (26)

1. manufacture a method for p-Xylol, it comprises:
A) 2,5-hexanedione is provided;
B) ethene is provided;
C) catalyzer is provided;
D) by 2,5-hexanedione, ethene and described catalyzer merge, forming reactions mixture; With
E) by the p-Xylol of generation at least partially of 2,5-hexanediones in described reaction mixture.
2. method according to claim 1, it also comprises separating paraxylene from described reaction mixture.
3. method according to claim 1, it also comprises provides solvent system, and 2,5-hexanedione, ethene, described catalyzer and described solvent system is merged, forming reactions mixture.
4. method according to claim 3, wherein said solvent system comprises C1-C20 aliphatic solvent, C6-C20 aromatic solvent, alkyl phenyl solvent, C2-C20 ether, C2-C20 ester, C1-C20 alcohol, C2-C20 ketone or its arbitrary combination or mixture.
5. method according to claim 3, wherein said solvent system comprises N,N-DIMETHYLACETAMIDE, acetonitrile, tetramethylene sulfone, diox, diox, dme, ether, ethylene glycol dimethyl ether (monoglyme), ethylene glycol bisthioglycolate ethyl ether (glycol diethyl ether), diethylene glycol dimethyl ether (diglyme), diethylene glycol diethyl ether (diethyl carbitol), triethylene glycol dimethyl ether (triglyme), diethylene glycol dibutyl ether (diethylene glycol dibutyl ether), TEG dimethyl ether (tetraethylene glycol dimethyl ether), multiethylene-glycol dme, dimethyl ether, higlyme, tetrahydrofuran (THF), ethylene glycol, Diethylene Glycol, triethylene glycol, polyoxyethylene glycol, cyclobutanone, cyclopentanone, pimelinketone, suberone, cyclooctanone, methyl acetate, ethyl acetate, propyl acetate, butylacetate, methyl lactate, ethyl lactate, propyl lactate, n-Butyl lactate, triactin, Dibutyl phthalate, butane, pentane, pentamethylene, hexane, hexanaphthene, heptane, suberane, octane, cyclooctane, nonane, decane, hendecane, 12 carbon alkane, hexadecane, tetrachloride, chloroform, methylene dichloride, Nitromethane 99Min., toluene, methyl-phenoxide, oil of mirbane, bromobenzene, N-methylpyrrole, p-Xylol, sym-trimethylbenzene, 12 carbon alkylbenzenes, amylbenzene, hexyl benzene, Wibaryl A, Wibaryl B, Wibaryl AB, Wibaryl F, Wibaryl R, Cepsa Petrepar 550-Q, phenyl ether, methyl diphenyl ether, ethyl phenyl ether, water, or its arbitrary combination or mixture.
6. method according to claim 5, wherein said solvent system comprises diox, glyme, diglyme, triglyme, decane, 12 carbon alkane, p-Xylol or its arbitrary combination or mixture.
7. method according to claim 1, wherein said catalyzer comprises and is selected from Zn 2+, Cu 2+, Ni 2+, Co 2+, Al 3+, In 3+, Fe 3+, La 3+, Gd 3+and Y 3+metallic cation.
8. method according to claim 1, wherein said catalyzer is aluminum chloride, aluminum bromide, trifluoromethanesulfonic acid aluminium, bismuth chloride, bismuth bromide, Bismuth triflate, cupric chloride, cupric bromide, copper trifluoromethanesulfcomposite, cobalt chloride, cobaltous bromide, trifluoromethanesulfonic acid cobalt, chromium chloride, chromic bromide, trifluoromethanesulfonic acid chromium, iron(ic) chloride, iron bromide, trifluoromethanesulfonic acid iron, Gadolinium trichloride, gadolinium bromide, trifluoromethanesulfonic acid gadolinium, indium chloride, indium bromide, trifluoromethanesulfonic acid indium, nickelous chloride, nickelous bromide, trifluoromethanesulfonic acid nickel, Neodymium trichloride, neodymium bromide, trifluoromethanesulfonic acid neodymium, magnesium chloride, magnesium bromide, trifluoromethanesulfonic acid magnesium, Lanthanum trichloride, lanthanum bromide, trifluoromethanesulfonic acid lanthanum, Scium trichloride, scandium bromide, trifluoromethanesulfonic acid scandium, tin chloride, Tin tetrabromide, trifluoromethanesulfonic acid tin, titanium chloride, titanium bromide, trifluoromethanesulfonic acid titanium, vanadium chloride, bromination vanadium, trifluoromethanesulfonic acid vanadium, Yttrium trichloride, yttrium bromide, trifluoromethanesulfonic acid yttrium, zinc chloride, zinc bromide, trifluoromethanesulfonic acid zinc, venus crystals, levulinic acid copper, or its arbitrary combination.
9. method according to claim 8, wherein said catalyzer is cupric chloride, copper trifluoromethanesulfcomposite or trifluoromethanesulfonic acid yttrium.
10. method according to claim 1, wherein said catalyzer is heteropolyacid.
11. 1 kinds of methods manufacturing terephthalic acid, it comprises:
A) 2,5-hexanedione is provided;
B) ethene is provided;
C) catalyzer is provided;
D) by 2,5-hexanedione, ethene and described catalyzer merge, forming reactions mixture; With
E) by the p-Xylol of generation at least partially of 2,5-hexanediones in described reaction mixture; With
F) make p xylene oxidation, produce terephthalic acid.
The method of the compound of 12. 1 kinds of one or more formula I of manufacture:
Wherein each R 1and R 2be hydrogen, alkyl, cycloalkyl, Heterocyclylalkyl, aryl or heteroaryl independently, described method comprises:
A) by the compound of one or more formula A, the compound of one or more formula B:
Or its arbitrary combination and (i) ethene and (ii) sulfonic acid or its salt, ester, acid anhydrides or resin, sulphonamide or its salt, or sulfimide or its salt merge, forming reactions mixture; With
B) by the compound of one or more the formula A in described reaction mixture, the compound of one or more formula B or its arbitrary combination at least partially with the compound producing one or more formula I at least partially of ethene.
13. methods according to claim 12, wherein each R 1and R 2be hydrogen or alkyl independently.
14. methods according to claim 13, wherein each R 1and R 2be alkyl independently; Or R 1alkyl, R 2hydrogen.
15. methods according to any one of claim 12-14, wherein:
Described sulfonic acid has formula R xsO 3the structure of H; And
The salt of described sulfonic acid has formula Q r+[R xsO 3 -] rstructure,
Wherein R xalkyl, haloalkyl, cycloalkyl, Heterocyclylalkyl, aryl or heteroaryl,
Wherein each alkyl, haloalkyl, cycloalkyl, Heterocyclylalkyl, aryl or heteroaryl optionally by 1-8 independently selected from alkyl, haloalkyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl, nitro ,-OR ' ,-C (O) OR ' ,-C (O) NR ' R "-CHO ,-COR ' and the substituting group replacement of cyano group
Wherein each R ' and R " be hydrogen, alkyl or haloalkyl independently,
Q (if present) is positively charged ion; And
R (if present) is described cationic electric charge.
16. methods according to any one of claim 12-14, wherein:
Described sulfimide has formula (R y1sO 2) NH (SO 2r y2) structure; And
The salt of described sulfimide has formula Q r+[(R y1sO 2) N (R y2sO 2)] rstructure,
Wherein each R y1and R y2be alkyl, haloalkyl, cycloalkyl, Heterocyclylalkyl, aryl or heteroaryl independently,
Wherein each alkyl, haloalkyl, cycloalkyl, Heterocyclylalkyl, aryl or heteroaryl optionally by 1-8 independently selected from alkyl, haloalkyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl, nitro ,-OR ' ,-C (O) OR ' ,-C (O) NR ' R "-CHO ,-COR ' and the substituting group replacement of cyano group
Wherein each R ' and R " be hydrogen, alkyl or haloalkyl independently,
Q (if present) is positively charged ion; And
R (if present) is described cationic electric charge.
17. methods according to claim 15 or 16, wherein Q r+al 3+, Bi 3+, Cu 2+, Cu +, Cr 3+, Fe 3+, Gd 3+, In 3+, Ni 2+, Nd 3+, Li +, Na +, K +, Rb +, Cs +, Mg 2+, Ba 2+, Ca 2+, La 3+, Sc 3+, Ti 4+, V 5+, Y 3+, Zn 2+, Pt 2+, Pd 2+, Ag +, Au 3+, Tl 3+, Tl +, Re 3+, Hg 2 2+, Hg 2+, NH 4 +, Sn 4+, Sn 3+, Sn 2+, B 3+, Ga 3+, Pb 4+, Pb 2+, Co 3+, Co 2+, Ge 4+, Ge 2+, Ce 4+or Ce 3+.
18. according to the method according to any one of claim 12-14, wherein said sulfonic acid or its salt, ester, acid anhydrides or resin, described sulfonamide or its salt, or described sulfimide or its salt are CF 3SO 3H (i.e. TFMS), HCF 2CF 2SO 3H, C 6F 5SO 3H, 4-toluene sulfonic acide (i.e. p-methyl benzenesulfonic acid), 2,4-dinitrobenzene sulfonic acid, Al (OTf) 3, Bi (OTf) 3, Cu (OTf) 2, Cu (OTf), Cr (OTf) 3, Fe (OTf) 3, Gd (OTf) 3, In (OTf) 3, Ni (OTf) 2, Nd (OTf) 3, LiRb (OTf), Cs (OTf), Mg (OTf) 2, La (OTf) 3, Sc (OTf) 3, Ti (OTf) 4, V (OTf) 5, Y (OTf) 3, Zn (OTf) 2, Pt (OTf) 2, Pd (OTf) 2, AgOTf,Au (OTf) 3, Tl (OTf) 3, Tl (OTf), Re (OTf) 3, Hg 2(OTf) 2, Hg (OTf) 2, NH 4(OTf), Sn (OTf) 4, Sn (OTf) 3, Sn (OTf) 2, B (OTf) 3, Ga (OTf) 3, Pb (OTf) 4, Pb (OTf) 2, Co (OTf) 3, Co (OTf) 2, Ge (OTf) 4, Ge (OTf) 3, Ge (OTf) 2, Ge (OTf), Ce (OTf) 4, Ce (OTf) 3, Nafion, NH (Tf) 2(i.e. TFMS acid imide), Al [N (Tf) 2] 3, Bi [N (Tf) 2] 3, Cu [N (Tf) 2] 2,Cu [N (Tf) 2], Cr [N (Tf) 2] 3, Fe [N (Tf) 2] 3, Gd [N (Tf) 2] 3, In [N (Tf) 2] 3, Ni [N (Tf) 2] 2, Nd [N (Tf) 2] 3, Li [N (Tf) 2], Na [N (Tf) 2], K [N (Tf) 2], Rb [N (Tf) 2], Cs [N (Tf) 2], Mg [N (Tf) 2] 2, Ba [N (Tf) 2] 2, Ca [N (Tf) 2] 2, La [N (Tf) 2] 3, Sc [N (Tf) 2] 3, Ti [N (Tf) 2] 4,V [N (Tf) 2] 5, Y [N (Tf) 2] 3, Zn [N (Tf) 2] 2, Pt [N (Tf) 2] 2, Pd [N (Tf) 2] 2, Ag [N (Tf) 2], Ag [N (Tf) 2] 2, Au [N (Tf) 2] 3, Tl [N (Tf) 2] 3, Tl [N (Tf) 2], Re [N (Tf) 2] 3, Hg 2[N (Tf) 2] 2, Hg [N (Tf) 2] 2, NH 4[N (Tf) 2], Sn [N (Tf) 2] 4, Sn [N (Tf) 2] 3,Sn [N (Tf) 2] 2, B [N (Tf) 2] 3, Ga [N (Tf) 2] 3, Pb [N (Tf) 2] 4, Pb [N (Tf) 2] 2, Co [N (Tf) 2] 3, Co [N (Tf) 2] 2, Ge [N (Tf) 2] 4, Ge [N (Tf) 2] 3, Ge [N (Tf) 2] 2, Ge [N (Tf) 2], Ce [N (Tf) 2] 4, Ce [N (Tf) 2] 3, two (trifyl) acid imides of ethyl dimethyl propyl ammonium, two (trifyl) acid imides of 1-butyl-1-crassitude, two (trifyl) acid imides of 1-ethyl-3-methylimidazole, two (trifyl) acid imides of 1-butyl-3-methylimidazole, two (trifyl) acid imides of 1-pi-allyl-3-methylimidazole, two (trifyl) acid imides of triethyl group sulfonium, two (trifyl) acid imides of three hexyl tetradecane Ji Phosphonium, 1, two (trifyl) acid imides of 2-dimethyl-3-propyl imidazole,[(C 6H 13) 3(C 14H 29) P] +[(CF 3SO 2) 2N] -, [C 11H 16N] +[N (SO 2CF 3) 2] -, [C 8H 15N 2] +[N (SO 2CF 3) 2] -, [C 6H 11N 2] +[N (SO 2CF 2CF 3) 2] -,[C 6H 11N 2] +[N (SO 2CF 3) 2] -, [C 6H 14N] +[N (SO 2CF 3) 2] -, 1-butyl-1-crassitude fluoroform sulphonate, 1-ethyl-3-methylimidazole fluoroform sulphonate, 1-butyl-3-methylimidazole fluoroform sulphonate, 1-butyl-3-methylimidazole fluoroform sulphonate or its any combination.
19. methods according to any one of claim 12-18, wherein R 1and R 2be alkyl separately.
20. method according to claim 19, wherein R 1and R 2be methyl separately.
21. methods according to any one of claim 12-20, it also comprises solvent system and the compound of formula A, the compound of formula B or its arbitrary combination, ethene, and described sulfonic acid or its salt, ester, acid anhydrides or resin, described sulphonamide or its salt, or described sulfimide or its salt merge, forming reactions mixture.
22. methods according to claim 21, wherein said solvent system comprises aliphatic solvent, aromatic solvent, alkyl phenyl solvent, ether solvents, ester solvent, alcoholic solvent, ketone solvent, ionic liquid or its arbitrary combination or mixture.
23. methods according to claim 21, wherein said solvent system comprises N,N-DIMETHYLACETAMIDE, acetonitrile, tetramethylene sulfone, diox, diox, dme, ether, ethylene glycol dimethyl ether (monoglyme), ethylene glycol bisthioglycolate ethyl ether (glycol diethyl ether), diethylene glycol dimethyl ether (diglyme), diethylene glycol diethyl ether (diethyl carbitol), triethylene glycol dimethyl ether (triglyme), diethylene glycol dibutyl ether (diethylene glycol dibutyl ether), TEG dimethyl ether (tetraethylene glycol dimethyl ether), multiethylene-glycol dme, dimethyl ether, higlyme, tetrahydrofuran (THF), ethylene glycol, Diethylene Glycol, triethylene glycol, polyoxyethylene glycol, cyclobutanone, cyclopentanone, pimelinketone, suberone, cyclooctanone, methyl acetate, ethyl acetate, propyl acetate, butylacetate, methyl lactate, ethyl lactate, propyl lactate, n-Butyl lactate, triactin, Dibutyl phthalate, butane, pentane, pentamethylene, hexane, hexanaphthene, heptane, suberane, octane, cyclooctane, nonane, decane, hendecane, 12 carbon alkane, hexadecane, tetrachloride, chloroform, methylene dichloride, Nitromethane 99Min., toluene, methyl-phenoxide, oil of mirbane, bromobenzene, methylpyrrole, methyl-2-pyrrolidone, dimethyl furan, dichlorobenzene, water, p-Xylol, sym-trimethylbenzene, 12 carbon alkylbenzenes, amylbenzene, hexyl benzene, Wibaryl A, Wibaryl B, Wibaryl AB, Wibaryl F, Wibaryl R, Cepsa Petrepar 550-Q, Santovac, phenyl ether, methyl diphenyl ether, ethyl phenyl ether, water, or its arbitrary combination or mixture.
24. methods according to claim 12, wherein:
R 1and R 2be methyl separately; And
Reagent is sulfonic acid or its salt, ester, acid anhydrides or polymkeric substance.
25. methods according to claim 24, wherein:
Described reagent is trifluoromethanesulfonic acid or its salt.
26. methods according to claim 25, wherein said solvent system comprises p-Xylol, C4-C30 alkyl solvents or its arbitrary combination or mixture.
CN201380059080.1A 2012-09-14 2013-09-13 Methods of producing para-xylene and terephthalic acid Pending CN104918901A (en)

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