阅读说明：本技术 用于由二氧化碳和1,3-丁二烯制造δ-内酯的制造方法的催化剂组合物 (Carbon monoxide-olefin polymeric for the manufacturing method by carbon dioxide and 1,3- butadiene manufacture delta-lactone ) 是由 苏奇温·乔奇卡塔万科 彭皮莫·旺格玛哈斯里坤 梭蓬·凯奥提普 哈姆佩·福姆帕莱 于 2017-11-08 设计创作，主要内容包括：本发明涉及一种用于由二氧化碳和1,3-丁二烯制造δ-内酯的制造方法的催化剂组合物,该催化剂组合物具有良好的δ-内酯选择性,能够有效地催化δ-内酯的合成反应,其中所述催化剂组合物包含：a)结构(I)所示的钯金属络合物<Image he="605" wi="432" file="DDA0002111614310000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>其中,R<Sup>1</Sup>、R<Sup>2</Sup>、R<Sup>3</Sup>和R<Sup>4</Sup>独立地表示选自氢原子、卤素原子、烷基、烷氧基、胺基、或任选的链烯基、炔基、苯基、苄基或含有杂原子的环烃基；以及b)磷化合物,其选自具有通式<Image he="69" wi="92" file="DDA0002111614310000012.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>的膦基团,其中R<Sup>5</Sup>选自烷基、环烷基或芳基。(The present invention relates to one kind for by carbon dioxide and 1,3- butadiene manufactures the carbon monoxide-olefin polymeric of the manufacturing method of delta-lactone, the carbon monoxide-olefin polymeric has good delta-lactone selectivity, it can be effectively catalyzed the synthetic reaction of delta-lactone, wherein the carbon monoxide-olefin polymeric includes: a) palladium metal complex shown in structure (I) Wherein, R 1 、R 2 、R 3 And R 4 It independently indicates selected from hydrogen atom, halogen atom, alkyl, alkoxy, amido or optional alkenyl, alkynyl, phenyl, benzyl or contains heteroatomic cyclic hydrocarbon radical；And b) phosphorus compound, selected from having general formula Phosphine groups, wherein R 5 Selected from alkyl, naphthenic base or aryl.)

1. a kind of carbon monoxide-olefin polymeric for the manufacturing method by carbon dioxide and 1,3-butadiene manufacture delta-lactone, wherein institute Stating carbon monoxide-olefin polymeric includes:

A) palladium metal complex shown in structure (I)

Wherein,

R¹、R²、R³And R⁴Independently indicate selected from hydrogen atom, halogen atom, alkyl, alkoxy, amido or optional alkenyl, Alkynyl, phenyl, benzyl contain heteroatomic cyclic hydrocarbon radical；And

B) phosphorus compound is selected from general formulaPhosphine groups, wherein R⁵Selected from alkyl, naphthenic base or aryl.

2. the catalysis according to claim 1 for the manufacturing method by carbon dioxide and 1,3- butadiene manufacture delta-lactone Agent composition, wherein a) in the palladium metal complex R¹、R²、R³And R⁴Independently indicate group selected from the following: hydrogen is former Son, halogen atom, the alkyl with 1 to 4 carbon atom, the alkoxy with 1 to 4 carbon atom or general formula are's Secondary amine, wherein R⁶For the alkyl with 1 to 4 carbon atom.

3. the manufacturing method according to claim 1 or 2 for by carbon dioxide and 1,3- butadiene manufacture delta-lactone Carbon monoxide-olefin polymeric, wherein a) in the palladium metal complex be selected from palladium (II) salicylide, palladium (II) methoxysalicyl aldehyde, palladium (II) 4-methoxysalicylaldehyde, palladium (II) 5- methoxysalicyl aldehyde, palladium (II) 4,6- dimethoxy salicylide, palladium (II) 4- diethyl Aminosalicyclic aldehyde, palladium (II) 4- dibutylamino salicylide, palladium (II) 5- bromosalicylaldehyde, palladium (II) 5- chloro-salicylic aldehyde, palladium (II) 3, 5- dichloro-salicylaldehyde, palladium (II) 3- cresotinic acid aldehyde, palladium (II) 4-Methyl Salicylaldehyde and palladium (II) 5- cresotinic acid aldehyde.

4. the catalysis according to claim 3 for the manufacturing method by carbon dioxide and 1,3- butadiene manufacture delta-lactone Agent composition, wherein a) in the palladium metal complex be selected from palladium (II) salicylide, palladium (II) 4,6- dimethoxy salicylide, Palladium (II) 4- lignocaine salicylide, palladium (II) 4- dibutylamino salicylide, palladium (II) 5- chloro-salicylic aldehyde and palladium (II) 3,5- bis- Chloro-salicylic aldehyde.

5. the catalysis according to claim 1 for the manufacturing method by carbon dioxide and 1,3- butadiene manufacture delta-lactone Agent composition, wherein b) in the phosphorus compound be selected from triphenylphosphine, tricyclohexyl phosphine, three (2- methoxyphenyl) phosphines, three (4- methoxyphenyl) phosphine or their mixture.

6. the catalysis according to claim 5 for the manufacturing method by carbon dioxide and 1,3- butadiene manufacture delta-lactone Agent composition, wherein b) in the phosphorus compound be triphenylphosphine.

7. the system according to any one of claim 1 to 6 for by carbon dioxide and 1,3- butadiene manufacture delta-lactone The carbon monoxide-olefin polymeric of method is made, wherein the ratio in the composition a) and b) is in the range of 1:1 to 1:5.

8. the catalysis according to claim 7 for the manufacturing method by carbon dioxide and 1,3- butadiene manufacture delta-lactone Agent composition, wherein the proportional region in the composition a) and b) is in the range of 1:3 to 1:4.

9. a kind of manufacture for manufacturing delta-lactone by carbon dioxide and 1,3- butadiene in organic solvent using carbon monoxide-olefin polymeric Method, the carbon monoxide-olefin polymeric includes:

A) palladium metal complex shown in structure (I)

Wherein,

R¹、R²、R³And R⁴Independently indicate selected from hydrogen atom, halogen atom, alkyl, alkoxy, amido or optional alkenyl, Alkynyl, phenyl, benzyl contain heteroatomic cyclic hydrocarbon radical；And

B) phosphorus compound is selected from general formulaPhosphine groups, wherein R⁵Selected from alkyl, naphthenic base or aryl.

10. the manufacturing method of delta-lactone according to claim 9, wherein a) in the palladium metal complex R¹、R²、 R³And R⁴Independently indicate group selected from the following: hydrogen atom, the alkyl containing 1 to 4 carbon atom, contains 1 at halogen atom The alkoxy or general formula of a to 4 carbon atoms beSecondary amine, wherein R⁶For the alkyl containing 1 to 4 carbon atom.

11. the manufacturing method of delta-lactone according to claim 9 or 10, wherein a) in the palladium metal complex be selected from Palladium (II) salicylide, palladium (II) methoxysalicyl aldehyde, palladium (II) 4-methoxysalicylaldehyde, palladium (II) 5- methoxysalicyl aldehyde, palladium (II) 4,6- dimethoxy salicylide, palladium (II) 4- lignocaine salicylide, palladium (II) 4- dibutylamino salicylide, palladium (II) 5- Bromosalicylaldehyde, palladium (II) 5- chloro-salicylic aldehyde, palladium (II) 3,5- dichloro-salicylaldehyde, palladium (II) 3- cresotinic acid aldehyde, palladium (II) 4- first Base salicylide and palladium (II) 5- cresotinic acid aldehyde.

12. the manufacturing method of delta-lactone according to claim 11, wherein a) in the palladium metal complex be selected from palladium (II) salicylide, palladium (II) 4,6- dimethoxy salicylide, palladium (II) 4- lignocaine salicylide, palladium (II) 4- dibutylamino water Poplar aldehyde, palladium (II) 5- chloro-salicylic aldehyde and palladium (II) 3,5- dichloro-salicylaldehyde.

13. the manufacturing method of delta-lactone according to claim 9, wherein b) in the phosphorus compound be selected from triphenyl Phosphine, tricyclohexyl phosphine, three (2- methoxyphenyl) phosphines, three (4- methoxyphenyl) phosphines or their mixture.

14. the manufacturing method of delta-lactone according to claim 13, wherein b) in the phosphorus compound be triphenylphosphine.

15. the manufacturing method of the delta-lactone according to any one of claim 9 to 14, the wherein ratio in composition a) and b) Example is in the range of 1:1 to 1:5.

16. the manufacturing method of delta-lactone according to claim 15, wherein the ratio in composition a) and b) is in 1:3 to 1: In the range of 4.

Technical field

The present invention relates to a kind of carbon monoxide-olefin polymerics for the manufacturing method by carbon dioxide and alkene manufacture delta-lactone.

Background technique

Carbon dioxide gas is many industries (including petroleum and the petrochemical industry by such as coal, cement and power industry etc Industry) burn one of the greenhouse gases generated.Although carbon dioxide gas has hypotoxicity, the carbon dioxide gas largely discharged Know from experience the greenhouse effects for causing to improve surface temperature.

However, carbon dioxide gas is renewable resource.In addition, carbon dioxide gas is used as manufacturing such as urea, water The C of the expensive chemicals such as poplar acid, cyclic carbonate and lactone₁Structural unit.However, mainly asking using carbon dioxide gas Topic is the inert chemi-cal character of carbon dioxide gas.Therefore, it in order to convert carbon dioxide gas to required chemical substance, needs Catalyst is reacted or used with highly reactive species.

Since lactone is used as the precursor of polyester synthesis, thus lactone is required cyclic annular ester group.Lactone is also For manufacturing the precursor of many other expensive derivatives.Preparing synthesizing for lactone by carbon dioxide can be made by using catalyst Carbon dioxide carries out telomerisation with small alkene to complete.

Journal of the Chemical Society, Chemical Communications (1976) and Bulletin of the Chemical Society of Japan (1978), which is disclosed, uses Pd- diphosphonic complex as urging Agent synthesizes gamma lactone by the reaction of carbon dioxide and 1,3- butadiene in solvent dimethylformamide.It was found that with starting 1, 3- butadiene is compared, and interior Lipase absobed can reach 12.3%, selection rate 15%.

Inorganica Chimica Acta(1978)、Journal of the Chemical Society、Perkin Transactions 1 (1980) and US 4167513 discloses the mono- phosphine complex compound of Pd- as catalyst and such as benzene etc Purposes of the nonpolar solvent in synthesis delta-lactone.

US 4393224, which is disclosed, uses palladium phosphine complex compound tertiary amine and quinone or hydroquinone compound as catalyst system, by dioxy The reaction of change carbon gas and 1,3- butadiene prepares the synthetic method of delta-lactone.The selection rate of the delta-lactone of the reaction is 89%.

Synthesis (1983) and EP 0124725A1 disclose using oxidation number be 2 palladium complex (Pd (II)) and The beta-dicarbonyl ligand and dicarboxylate of such as acetylacetonate, allyl or diene etc are together with Phosphine ligands as catalysis Agent synthesizes delta-lactone by carbon dioxide and 1,3-butadiene.

Journal of the American Chemical Society (1988) and FR 2617163 disclose sun from Sub- palladium complex manufactures the purposes of delta-lactone as catalyst, and wherein ligand is selected from the group of phosphine compound or nitrile or halide In.

In addition, Journal of Molecular Catalysis A:Chemical (1997) is disclosed with itrile group The purposes of synthetic reaction of the Phosphine ligands as catalyst for carrying out the delta-lactone with palladium complex in organic solvent.δ-is interior The selection rate of ester is 74%.

In the same way, Journal of Organometallic Chemistry (2012) is disclosed molten in acetonitrile Delta-lactone is synthesized using the palladium complex with tertiary amine phosphine bidentate ligand in agent.The complex compound can provide up to 60% production Rate, selection rate 79%.Tetrahedron Letters (2016) and CN 105622560 are disclosed under the conditions of no ligand Palladium nano-particles and quaternary ammonium salt.It has been found that the catalyst can provide 51% delta-lactone product, selection rate 94%.

However, the disclosed catalyst for synthesizing delta-lactone by the reaction of carbon dioxide and 1,3-butadiene only limits In palladium complex and phosphine, beta-dicarbonyl, allyl or diene, carboxylic acid, amine, nitrile or dibenzalacetone ligand.It is not found to be Exploitation catalytic activity and the disclosure for carrying out the structure optimization of the compound.In addition, the foundation structure of ligand is in electronics It is restricted in terms of performance and space performance two.

For these reasons, interior for the reaction synthesis δ-by carbon dioxide and 1,3-butadiene the present invention is directed to develop The effect of catalyst system of ester.The carbon monoxide-olefin polymeric include as catalyst palladium complex and salicylide ligand (including Its derivative) and phosphorus phosphine groups, the carbon monoxide-olefin polymeric be readily synthesized, air and moisture are stablized, and can be with good Good delta-lactone selectivity is effectively catalyzed the synthetic reaction of delta-lactone.

Summary of the invention

The present invention relates to the catalyst combinations for the manufacturing method by carbon dioxide and 1,3- butadiene manufacture delta-lactone Object, which can effectively be catalyzed the synthetic reaction of delta-lactone with good delta-lactone selectivity, wherein described Carbon monoxide-olefin polymeric includes:

A) palladium metal complex shown in structure (I)

Wherein,

R¹、R²、R³And R⁴It independently indicates to be selected from hydrogen atom, halogen atom, alkyl, alkoxy, amido or optional chain Alkenyl, alkynyl, phenyl, benzyl contain heteroatomic ring alkyl；And

B) phosphorus compound is selected from general formulaPhosphine groups, wherein R⁵Selected from alkyl, naphthenic base or aryl.

Specific embodiment

The present invention relates to the catalyst combinations for the manufacturing method by carbon dioxide and 1,3- butadiene manufacture delta-lactone Object, wherein catalyst according to the invention can effectively be catalyzed the synthetic reaction of delta-lactone with good delta-lactone selectivity. Moreover, catalyst according to the invention is readily synthesized and air and moisture is stablized.It can be according to described further below right Catalyst according to the invention is described.

Unless otherwise stated, any aspect shown in this article all refer to include other aspects of the present invention application.

Unless otherwise stated, terminology used herein or scientific term have such as those of ordinary skill in the art The definition understood.

Any tool, equipment, method or the chemicals being mentioned herein refer to that those skilled in the art usually operate or use Tool, equipment, method or chemicals, unless it is stated that they are only specific tool, equipment, method or chemistry in the present invention Product.

The use of singular noun or singular pronoun with "comprising" or " comprising " in claim or specification refers to "one" and " one or more ", "at least one" and " one or more than one ".

Disclosed herein and claimed all compositions and/or method are intended to cover such embodiment: though It is not illustrated especially in right claim, but without carrying out any experiment dramatically different with the present invention, it can be general by this field Any function that logical technical staff obtains, identical with the effectiveness purpose and result of the present embodiment, performance, modification or adjustment institute Obtained embodiment.Therefore, the replaceable or similar purpose of the present embodiment (is clearly seen including those skilled in the art Any minor modifications or adjustment) spirit of the invention occurred in appended claims, range and general should be interpreted as belonging to It reads.

In entire the application, term " about " refers to be occurred or any number for showing may change or partially herein From arbitrary deviation caused by the equipment as described in equipment, method or personal use or method, including being caused by the variation of physical property Variation or deviation.

Hereinafter, the invention of the present embodiment is shown, any purpose without limiting any range of the invention.

The present invention relates to the catalyst combinations for the manufacturing method by carbon dioxide and 1,3- butadiene manufacture delta-lactone Object, which can effectively be catalyzed the synthetic reaction of delta-lactone with good delta-lactone selectivity, wherein described Carbon monoxide-olefin polymeric includes:

A) palladium metal complex shown in structure (I)

Wherein,

R¹、R²、R³And R⁴It independently indicates to be selected from hydrogen atom, halogen atom, alkyl, alkoxy, amido or optional chain Alkenyl, alkynyl, phenyl, benzyl contain heteroatomic cyclic hydrocarbon radical；And

B) phosphorus compound is selected from general formulaPhosphine groups, wherein R⁵Selected from alkyl, naphthenic base or aryl.

In one embodiment, a) in palladium metal complex R¹、R²、R³And R⁴It independently indicates selected from the following Group: hydrogen atom, halogen atom, the alkyl with 1 to 4 carbon atom, the alkoxy with 1 to 4 carbon atom or logical Formula isSecondary amine, wherein R⁶For the alkyl with 1 to 4 carbon atom.

In one embodiment, a) in palladium metal complex R¹、R²、R³And R⁴It independently indicates selected from (but unlimited In) following group: hydrogen atom, chlorine atom, bromine atom, methyl atom, ethyl atom, isopropyl atom, normal-butyl atom, tertiary fourth Base, methoxyl group atom, ethyoxyl atom, isopropoxy atom, n-butoxy atom, tert-butoxy atom, dimethylamine are former Son, diethylamine atom, di-n-butylamine atom.

In one embodiment, a) in palladium metal complex can be selected from (but being not limited to) palladium (II) salicylide, palladium (II) methoxysalicyl aldehyde, palladium (II) 4-methoxysalicylaldehyde, palladium (II) 5- methoxysalicyl aldehyde, palladium (II) 4,6- dimethoxy Salicylide, palladium (II) 4- lignocaine salicylide, palladium (II) 4- dibutylamino salicylide, palladium (II) 5- bromosalicylaldehyde, palladium (II) 5- chloro-salicylic aldehyde, palladium (II) 3,5- dichloro-salicylaldehyde, palladium (II) 3- cresotinic acid aldehyde, palladium (II) 4-Methyl Salicylaldehyde and palladium (II) 5- cresotinic acid aldehyde.

Preferably, a) in palladium metal complex be selected from palladium (II) salicylide, palladium (II) 4,6- dimethoxy salicylide, palladium (II) 4- lignocaine salicylide, palladium (II) 4- dibutylamino salicylide, palladium (II) 5- chloro-salicylic aldehyde and palladium (II) 3,5- dichloro Salicylide.

In one embodiment, a) in palladium metal complex can be under conditions of pH be about 5 to 8, by palladium metal The reaction of the group of salt and salicylide ligand and its derivative synthesizes, wherein the molar ratio in the reacting of palladium and ligand 3:1 extremely In the range of 1:3.

In one embodiment, palladium metal salt precursor can be selected from (but being not limited to) palladium chloride (PdCl₂), palladium bromide (PdBr₂), palladium trifluoroacetate (Pd (TFA)₂) or acid chloride (Pd (OAc)₂).Preferably, palladium metal salt precursor is palladium chloride.

In another embodiment of the present invention, salicylide ligand and its derivative can be selected from (but being not limited to) bigcatkin willow Aldehyde, 3- methoxysalicyl aldehyde, 4-methoxysalicylaldehyde, 5- methoxysalicyl aldehyde, 4,6- dimethoxy salicylide, 4- lignocaine Salicylide, 4- dibutylamino salicylide, 5- bromosalicylaldehyde, 5- chloro-salicylic aldehyde, 3,5- dichloro-salicylaldehyde, 3- cresotinic acid aldehyde, 4- Cresotinic acid aldehyde and 5- cresotinic acid aldehyde.

In one embodiment, b) in phosphorus compound be selected from (but being not limited to) triphenylphosphine, tricyclohexyl phosphine, three (2- methoxyphenyl) phosphine, three (4- methoxyphenyl) phosphines or their mixture.Preferably, b) in phosphorus compound be selected from three Phenylphosphine.

In one embodiment, the ratio in composition a) and b) is in the range of 1:1 to 1:5, it is preferable that composition Middle ratio a) and b) is in the range of 1:3 to 1:4.

In another aspect of the invention, the present invention relates to resulting in organic solvent by dioxy according to the present invention Change the purposes of the catalyst of the manufacturing method of carbon and 1,3- butadiene manufacture delta-lactone.

In one embodiment, in organic solvent by the manufacturer of carbon dioxide and 1,3-butadiene manufacture delta-lactone Method includes: that catalyst according to the invention, carbon dioxide and 1,3- butadiene are added to filled with organic solvent by step i) In reactor, wherein the molar ratio of carbon dioxide and 1,3-butadiene is in the range of 1:1 to 1:3, and palladium catalyst and 1, The molar ratio of 3- butadiene precursor is in the range of 1:1000 to 1:3000；And ii) within the temperature range of 60 DEG C to 120 DEG C Heating response device 1 hour to 10 hours.

Preferably, in organic solvent by carbon dioxide and 1,3-butadiene manufacture delta-lactone manufacturing method include: step It is rapid that i) catalyst according to the invention, carbon dioxide and 1,3-butadiene are added in the reactor filled with organic solvent, Wherein the molar ratio of carbon dioxide and 1,3-butadiene is in the range of 1.2:1 to 1.5:1, and palladium catalyst and 1,3- fourth two The molar ratio of alkene precursor is in the range of 1:1,500 to 1:1,700；And ii) heated within the temperature range of 70 DEG C to 80 DEG C Reactor 3 hours to 4 hours.

In each step of the manufacturing method of delta-lactone according to the present invention, unless otherwise indicated, what be can choose has Solvent is acetonitrile, ethylene carbonate, propylene carbonate, pyridine, benzene, dimethylformamide, dimethyl sulfoxide or theirs is mixed Object is closed, but not limited to this.Preferably, solvent is selected from acetonitrile, ethylene carbonate or their mixture.

If desired, the manufacturing method of delta-lactone according to the present invention can further comprise drying steps, wherein the step Suddenly (but being not limited to) stirring evaporation, vacuum drying etc. be can be selected from.

In one aspect, the manufacturing method of delta-lactone according to the present invention can operate in the reactor, but be not limited to fix Bed reactor.Operation can be completed in batches or continuously.

It is embodiment below, is only used as one embodiment of the invention, and is not intended to be limiting in any manner this Invention.