CN115010634A - Dithiooxamide compound and preparation method thereof - Google Patents
Dithiooxamide compound and preparation method thereof Download PDFInfo
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- CN115010634A CN115010634A CN202210813896.XA CN202210813896A CN115010634A CN 115010634 A CN115010634 A CN 115010634A CN 202210813896 A CN202210813896 A CN 202210813896A CN 115010634 A CN115010634 A CN 115010634A
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- -1 Dithiooxamide compound Chemical class 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims abstract description 34
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 16
- 239000011593 sulfur Substances 0.000 claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 8
- OAEGRYMCJYIXQT-UHFFFAOYSA-N dithiooxamide Chemical class NC(=S)C(N)=S OAEGRYMCJYIXQT-UHFFFAOYSA-N 0.000 claims description 30
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 24
- 150000004820 halides Chemical group 0.000 claims description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 11
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 7
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- 125000004185 ester group Chemical group 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 6
- 150000007514 bases Chemical class 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229950005499 carbon tetrachloride Drugs 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 239000011698 potassium fluoride Substances 0.000 claims description 3
- 235000003270 potassium fluoride Nutrition 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 abstract description 13
- 239000000203 mixture Substances 0.000 abstract description 7
- 238000003756 stirring Methods 0.000 abstract description 4
- 239000000178 monomer Substances 0.000 abstract description 3
- 150000001412 amines Chemical class 0.000 abstract description 2
- 150000002894 organic compounds Chemical class 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 60
- 239000000243 solution Substances 0.000 description 27
- 239000012074 organic phase Substances 0.000 description 18
- 239000007787 solid Substances 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 14
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical group [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 238000006452 multicomponent reaction Methods 0.000 description 10
- 238000001914 filtration Methods 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 7
- 239000012264 purified product Substances 0.000 description 7
- 235000019270 ammonium chloride Nutrition 0.000 description 6
- 239000008346 aqueous phase Substances 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 239000003480 eluent Substances 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000010791 quenching Methods 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 238000010898 silica gel chromatography Methods 0.000 description 6
- 238000010189 synthetic method Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- BHHGXPLMPWCGHP-UHFFFAOYSA-N Phenethylamine Chemical compound NCCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-N 0.000 description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IDPURXSQCKYKIJ-UHFFFAOYSA-N 1-(4-methoxyphenyl)methanamine Chemical compound COC1=CC=C(CN)C=C1 IDPURXSQCKYKIJ-UHFFFAOYSA-N 0.000 description 2
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 150000001924 cycloalkanes Chemical class 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 150000003556 thioamides Chemical class 0.000 description 2
- FNQJDLTXOVEEFB-UHFFFAOYSA-N 1,2,3-benzothiadiazole Chemical class C1=CC=C2SN=NC2=C1 FNQJDLTXOVEEFB-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 101710172072 Kexin Proteins 0.000 description 1
- 238000005659 Kindler reaction Methods 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- SPWVRYZQLGQKGK-UHFFFAOYSA-N dichloromethane;hexane Chemical compound ClCCl.CCCCCC SPWVRYZQLGQKGK-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 125000005936 piperidyl group Chemical group 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003558 thiocarbamic acid derivatives Chemical class 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C327/00—Thiocarboxylic acids
- C07C327/38—Amides of thiocarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
- C07D295/20—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carbonic acid, or sulfur or nitrogen analogues thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a dithiooxamide compound and a preparation method thereof, belonging to the technical field of organic compound preparation. The method comprises the steps of mixing the monomer sulfur, tetrachloroethane and amine monomers, heating and stirring the mixture in a solvent or under the solvent-free condition for reaction, and purifying the mixture after the reaction is finished to obtain the N, N-disubstituted dithiooxamide compound. The invention realizes the high-efficiency and low-cost preparation of the N, N-di-aliphatic group substituted dithiooxamide compound and the N, N-di-aromatic group substituted dithiooxamide compound which are rarely reported, and the preparation method has the characteristics of mild reaction conditions, simple operation, various product structures and the like.
Description
Technical Field
The invention relates to the technical field of organic compound preparation, in particular to a dithiooxamide compound and a preparation method thereof.
Background
At present, compounds containing nitrogen atoms and sulfur atoms, such as thiourea compounds, thioamide compounds, thiocarbamate compounds, benzothiadiazole compounds, and the like, have wide application in the fields of biomedicine, organic synthetic chemistry, coordination chemistry, solar cells, pesticides and other fields, and have important significance in the research on the synthesis and application of the compounds. Dithiooxamide compounds having similar structures have also found important applications in the fields of organic synthetic chemistry, coordination chemistry, and the like, but studies on the applications of dithiooxamide compounds in the fields have been limited because the methods for synthesizing dithiooxamide compounds are relatively few compared to the above-mentioned compounds.
The methods of preparation of dithiooxamide compounds that have been reported so far can be classified into two categories: 1. treating the oxamide compound with lawson's reagent or phosphorus pentasulfide having an unpleasant taste and obtaining the corresponding dithiooxamide compound; 2. the amino-unsubstituted dithiooxamide is used to react with an amine compound and to give the corresponding dithiooxamide compound. Lawson's reagent or phosphorus pentasulfide is offensive, costly and may substitute only one oxygen atom in an oxamide compound and produce a monothiooxamide compound, while the amine unsubstituted dithiooxamide is also costly and the reaction evolves ammonia gas, which makes the dithiooxamide compound costly to produce. Therefore, it is of great interest to develop a low cost method of making dithiooxamides using inexpensive and readily available monomers. Multicomponent reactions (MCRs) with mild Reaction conditions, simple operation, and versatile product structures have been demonstrated to allow inexpensive, readily available or abundant compounds, such as water, carbon dioxide, etc., to participate efficiently in reactions and to build functional molecules with complex structures. The development of the petroleum industry increases the yield and storage capacity of elemental sulfur, but the property of elemental sulfur that is easily oxidized into sulfur oxides causes certain safety problems and potential environmental problems for sulfur storage. Some multi-component reactions, such as Willgenodt-Kindler reaction in which an amine compound, an aldehyde compound and elemental sulfur participate, can efficiently convert the elemental sulfur with low cost into the thioamide compound, so that the synthesis cost of the compound containing the nitrogen element and the sulfur element is reduced, and the compound is more environment-friendly. Multicomponent reactions that have been demonstrated to efficiently convert low-cost elemental sulfur into various sulfur-containing compounds such as thioamide compounds are also expected to be useful for the synthesis of dithiooxamide compounds.
Disclosure of Invention
The invention aims to provide a dithiooxamide compound and a preparation method of the dithiooxamide compound, which has the advantages of low cost, mild conditions and high reaction efficiency.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a dithiooxamide compound, which comprises one of the following structural general formulas:
wherein R is 1 And R 2 Independently is aliphatic alkyl, oxo-aliphatic alkyl, aliphatic alkyl with aromatic substituent, oxo-aliphatic alkyl with aromatic substituent, aliphatic alkyl with halide substituent or oxo-aliphatic alkyl with halide substituent;
R 3 and R 4 Independently is a hydrogen atom, a hydrocarbyl group, an alkoxy group, a halogen, a hydroxyl group, an ester group, a carbonyl group, an aryl group or a cyano group;
R 5 and R 6 Independently is a hydrocarbyl, a hydrocarbyl with aromatic substituent or a hydrocarbyl with halide substituent, both sides of which are simultaneously connected with nitrogen atoms;
R 7 and R 8 Independently is aliphatic alkyl, aliphatic alkyl with aromatic substituent or aliphatic beltA halogenated aliphatic hydrocarbon group.
Further, the dithiooxamide compound specifically comprises one of the following structural formulas:
the invention provides a preparation method of dithiooxamide compound, which comprises the following steps:
the product obtained by reacting sulfur, tetrachloroethane and an amine compound is the dithiooxamide compound.
Further, the molar ratio of the sulfur to the tetrachloromethane to the amine compound is 0.25-10.0: 0.17-4.0: 1.0 to 10.0.
Further, the amine compound comprises one of the following structural formulas:
wherein R is 1 And R 2 Independently is aliphatic alkyl, oxo-aliphatic alkyl, aliphatic alkyl with aromatic substituent, oxo-aliphatic alkyl with aromatic substituent, aliphatic alkyl with halide substituent or oxo-aliphatic alkyl with halide substituent;
R 3 and R 4 Independently is a hydrogen atom, a hydrocarbyl group, an alkoxy group, a halogen, a hydroxyl group, an ester group, a carbonyl group, an aryl group or a cyano group;
R 5 and R 6 Independently is a hydrocarbyl, a hydrocarbyl with aromatic substituent or a hydrocarbyl with halide substituent, both sides of which are simultaneously connected with nitrogen atoms;
R 7 and R 8 Independently an aliphatic hydrocarbon group, an aliphatic hydrocarbon group with an aromatic substituent or a substituent with a halideAn aliphatic hydrocarbon group.
Further, the amine compound specifically comprises one of the following structural formulas:
wherein n and k are independently integers of 1-30.
Further, the reaction is carried out in a solvent, and the molar volume ratio of the amine compound to the solvent is 0.01-5 mol: 1L;
the solvent comprises one or more of N, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide.
Further, the reaction is carried out under a protective atmosphere comprising nitrogen and/or argon.
Further, the reaction temperature is 20-120 ℃, and the reaction time is 2-48 h.
Further, the reaction is carried out under the action of a catalyst, the catalyst is a basic compound, and the basic compound contains one or more of N, N-diisopropylethylamine, triethylamine, potassium fluoride and potassium carbonate; the dosage of the catalyst is 10-40: 1 to 10.
The invention has the beneficial effects that:
(1) the present invention can provide aryl-substituted dithiooxamide compounds without being limited to aliphatic-substituted dithiooxamide compounds prepared by other methods.
(2) The preparation method has the advantages of cheap reaction raw materials, no need of additional synthesis steps, mild organic reaction conditions, simple process and high reaction efficiency, and can be purchased from commercial sources. At the same time, the present invention can achieve a previously reduced one-step conversion of elemental sulfur to dithiooxamide compounds.
(3) The preparation method has good reactant universality, is compatible with aliphatic primary amine, aliphatic secondary amine and aromatic primary amine, and can synthesize dithiooxamide compounds with wider structural range.
(4) The preparation method of the present invention can prepare the dithiooxamide compound on a gram scale in a single time.
(5) The dithiooxamide compounds prepared according to the present invention were found to have the ability to coordinate with metal ions, indicating that the dithiooxamide compounds can be applied in the field of coordination chemistry.
Drawings
FIG. 1 is a single crystal X-ray diffraction analysis chart of a single crystal of dithiooxamide compound prepared in example 2 of the present invention cultured in a dichloromethane-n-hexane solvent system;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of dithiooxamide compound prepared in example 1 of the present invention in deuterated dimethyl sulfoxide;
FIG. 3 is a nuclear magnetic resonance carbon spectrum of dithiooxamide compound prepared in example 1 of the present invention in deuterated dimethyl sulfoxide.
Detailed Description
The invention provides a dithiooxamide compound, which comprises one of the following structural general formulas:
wherein R is 1 And R 2 Independently is aliphatic alkyl, oxo-aliphatic alkyl, aliphatic alkyl with aromatic substituent, oxo-aliphatic alkyl with aromatic substituent, aliphatic alkyl with halide substituent or oxo-aliphatic alkyl with halide substituent;
R 3 and R 4 Independently is a hydrogen atom, a hydrocarbyl group, an alkoxy group, a halogen, a hydroxyl group, an ester group, a carbonyl group, an aryl group or a cyano group;
R 5 and R 6 Independently is a hydrocarbyl, a hydrocarbyl with aromatic substituent or a hydrocarbyl with halide substituent, both sides of which are simultaneously connected with nitrogen atoms;
R 7 and R 8 Independently is aliphatic alkyl, aliphatic alkyl with aromatic substituent or substituent with halideThe aliphatic hydrocarbon group of (2).
In the present invention, R 1 And R 2 Independently, cyclohexyl, cyclopentyl, benzyl or phenethyl are preferred.
In the present invention, R 3 And R 4 Independently, a hydrogen atom, methyl group or bromine is preferred.
In the present invention, R 5 And R 6 Independently preferably a cyclic alkane of 4 to 8 carbon atoms.
In the present invention, R 7 And R 8 Independently, the preferred alkane is a chain alkane with 4-8 carbon atoms.
In the present invention, the dithiooxamide compound is preferably one of the following structural formulae:
the invention provides a preparation method of dithiooxamide compound, which comprises the following steps:
the product obtained by reacting sulfur, tetrachloroethane and an amine compound is the dithiooxamide compound.
In the present invention, the reaction equation of the dithiooxamide compound is as follows (i):
wherein R is 9 And R 10 Independently is R 1 ～R 8 Any one of the above.
In the invention, the molar ratio of the sulfur to the tetrachloromethane to the amine compound is 0.25-10.0: 0.17-4.0: 1.0 to 10.0, preferably 0.5 to 8.0: 0.3-3.0: 2.0 to 8.0, and more preferably 1.0 to 6.0: 1.0-2.0: 8.0.
in the present invention, the amine compound comprises one of the following structural formulas:
wherein R is 1 And R 2 Independently is aliphatic alkyl, oxo aliphatic alkyl, aliphatic alkyl with aromatic substituent, oxo aliphatic alkyl with aromatic substituent, aliphatic alkyl with halide substituent or oxo aliphatic alkyl with halide substituent;
R 3 and R 4 Independently is a hydrogen atom, a hydrocarbyl group, an alkoxy group, a halogen, a hydroxyl group, an ester group, a carbonyl group, an aryl group or a cyano group;
R 5 and R 6 Independently is a hydrocarbyl, a hydrocarbyl with aromatic substituent or a hydrocarbyl with halide substituent, both sides of which are simultaneously connected with nitrogen atoms;
R 7 and R 8 Independently, the alkyl group is aliphatic alkyl, aliphatic alkyl with aromatic substituent or aliphatic alkyl with halide substituent.
In the present invention, said R 1 Cyclohexyl, cyclopentyl, benzyl or phenethyl are preferred.
In the present invention, R 3 Preferably a hydrogen atom, methyl or bromine.
In the present invention, R 5 Preferably a cyclic alkane having 4 to 8 carbon atoms.
In the present invention, R 7 And R 8 Independently, the preferred alkane is a chain alkane with 4-8 carbon atoms.
In the present invention, the amine compound is further preferably one of the following structural formulae:
wherein n and k are independently integers of 1-30.
In the present invention, n and k are independently preferably an integer of 5 to 20, and more preferably an integer of 10 to 15.
In the invention, the reaction is carried out in a solvent, and the molar volume ratio of the amine compound to the solvent is 0.01-5 mol: 1L, preferably 0.5-4 mol: 1L, more preferably 1 to 3 mol: 1L of the compound.
In the present invention, the solvent comprises one or more of N, N-dimethylformamide, N-dimethylacetamide and dimethylsulfoxide, preferably dimethylsulfoxide.
In the present invention, the reaction is carried out under a protective atmosphere comprising nitrogen and/or argon, preferably nitrogen.
In the invention, the reaction temperature is 20-120 ℃, and the reaction time is 2-48 h; preferably, the reaction temperature is 50-100 ℃, and the reaction time is 5-40 h; more preferably, the reaction temperature is 60-80 ℃, and the reaction time is 10-30 h.
In the invention, the reaction is accelerated by stirring, and the rotation speed of the stirring is 300-800 rpm, preferably 500 rpm.
In the invention, the reaction is carried out under the action of a catalyst, the catalyst is a basic compound, and the basic compound contains one or more of N, N-diisopropylethylamine, triethylamine, potassium fluoride and potassium carbonate, and preferably N, N-diisopropylethylamine.
In the invention, the molar ratio of the catalyst to the amine compound is 10-40: 1-10, preferably 40: 10.
in the invention, after the reaction is finished, the reaction product needs to be purified, and the purification treatment is as follows: diluting the reaction solution with ethyl acetate, filtering to remove solid substances, and sequentially performing extraction treatment, elution treatment and drying on the residual liquid to obtain a purified product.
In the invention, the water phase of the extraction treatment is saturated ammonium chloride aqueous solution, and the oil phase is ethyl acetate; the volume ratio of the solvent used for elution is 3-5: 1, preferably 4: 1.
in the invention, the drying temperature is 50-70 ℃, and the drying time is 10-30 min; preferably, the drying temperature is 60 ℃ and the drying time is 20 min.
In the present invention, the chemicals used are all available from chemical agents, wherein cyclohexylamine, tetrachloroethane, N-dimethylacetamide, N-diisopropylethylamine and 2-phenylethylamine are available from Annaige, p-methoxybenzylamine is available from TCI, piperidine is available from Kexin, sulphur (sublimed sulphur) is available from Afaexate, and dodecylamine is available from Aladdin.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
The cyclohexyl substituted dithiooxamide is prepared by utilizing multicomponent reaction of simple substance sulfur, tetrachloroethane and amine compound to prepare dithiooxamide compound, and the reaction equation is shown as a formula (II):
the synthetic method comprises the following steps:
in a nitrogen-purged reactor, 8mmol of cyclohexylamine, 2mmol of tetrachloroethane and 10mmol of sulfur were added to 8mmol of dimethylacetamide, dissolved, and heated to 100 ℃ and stirred at 500rpm for 8 hours.
After the reaction was completed, heating was stopped, 100mL of ethyl acetate was added thereto to quench and dilute the reaction solution, and then the precipitated solid was removed from the reaction solution by filtration. The reaction solution from which the solids were removed was extracted using a saturated aqueous ammonium chloride solution as an aqueous phase and ethyl acetate as an organic phase, and then the resulting organic phases were combined. The solvent of the combined organic phases was removed by evaporation under reduced pressure with heating and the crude product was obtained. Then, silica gel column chromatography was performed using a petroleum ether to ethyl acetate volume ratio of 4: 1 as eluent, the purified product was separated from the system and dried at 60 c for 20min to finally obtain an orange-red solid product, i.e., cyclohexyl-substituted dithiooxamide compound, in 59% yield.
The dithiooxamide compounds obtained in this example are shown in Compound 1.
Characterization data for dithiooxamide compounds prepared in this example are shown below:
dithiooxamide compound, orange red solid, yield 59%. The nuclear magnetic data are as follows: 1 H NMR(400MHz,CDCl 3 -d),δ(TMS,ppm):10.35(d,1H,-NH-),4.25(m,1H),2.05(m,2H),1.79(m,2H),1.66(m,1H),1.44(m,4H),1.33(m,1H). 13 C NMR(100MHz,CDCl 3 -d),δ(TMS,ppm):183.09(C＝S),55.82,30.64,25.45,24.35。
example 2
Preparing p-methoxybenzyl substituted dithiooxamide by utilizing multicomponent reaction of elemental sulfur, tetrachloroethane and amine compound to prepare dithiooxamide compound, wherein the reaction equation is as shown in formula (III):
the synthetic method comprises the following steps:
8mmol of p-methoxybenzylamine, 2mmol of tetrachloroethane and 10mmol of sulfur are added into a reactor, nitrogen is poured into the reactor, and the reactor is heated to 100 ℃ and stirred at 500rpm for 8 hours.
After the reaction was completed, heating was stopped and 60mL of ethyl acetate and 50mL of purified water were added to quench and dilute the reaction solution, and then the solid precipitated in the reaction solution was removed by filtration. The reaction solution from which the solids were removed was extracted using a saturated aqueous ammonium chloride solution as an aqueous phase and ethyl acetate as an organic phase, and then the resulting organic phases were combined. The solvent of the combined organic phases was removed by evaporation under reduced pressure with heating and the crude product was obtained. Then, silica gel column chromatography was performed using a petroleum ether to ethyl acetate volume ratio of 4: 1 as eluent, the purified product was separated from the system and dried at 60 c for 20min to finally obtain a yellow solid product, i.e., a p-methoxybenzyl-substituted dithiooxamide compound, in a yield of 47%.
The dithiooxamide compounds obtained in this example are shown as Compound 2.
As a structure proof means for the dithiooxamide compound obtained in example 2, the compound was prepared in a volume ratio of 1: 1, dichloromethane and n-hexane are used as mixed solvents, strip-shaped single crystals of the compound are cultured, single crystal X-ray diffraction tests are carried out on the single crystals, the test results prove the structure of the dithiooxamide compound, and the compound structure shown by single crystal X-ray diffraction analysis is shown in figure 1.
Example 3
Multicomponent reaction for preparing dithiooxamide compound by using elemental sulfur, tetrachloroethane and amine compound prepares p-methylphenyl substituted dithiooxamide under the condition of adding alkali reagent, and the reaction equation is shown as formula (IV):
the synthetic method comprises the following steps:
in an argon-purged reactor, 8mL of N, N-dimethylacetamide and 5573.7. mu.L of N, N-diisopropylethylamine (32.0mmol) were added to 8mmol of p-methylaniline, 6mmol of tetrachloroethane and 10mmol of sublimed sulfur, dissolved, and heated to 100 ℃ at 400rpm for stirring for 8 hours.
After the reaction was completed, heating was stopped, 100mL of ethyl acetate was added thereto to quench and dilute the reaction solution, and then the precipitated solid was removed from the reaction solution by filtration. The reaction solution from which the solids were removed was extracted using a saturated aqueous ammonium chloride solution as an aqueous phase and ethyl acetate as an organic phase, and then the resulting organic phases were combined. The solvent of the combined organic phases was removed by evaporation under reduced pressure with heating and the crude product was obtained. Then, the mixture is purified by silica gel column chromatography using a petroleum ether to ethyl acetate volume ratio of 4: 1 as eluent, and the purified product was separated from the system and dried at 50 c for 10min to finally obtain an orange-red solid product, i.e., p-methylphenyl substituted dithiooxamide compound, in a yield of 26%.
The dithiooxamide Compound obtained in this example is shown as Compound 3.
Example 4
The multi-component reaction for preparing dithiooxamide compound by using elemental sulfur, tetrachloroethane and amine compound is used for preparing the piperidyl substituted fully-substituted dithiooxamide, and the reaction equation is shown as the formula (V):
the synthetic method comprises the following steps:
in an argon-filled reactor, 8mL of N, N-dimethylacetamide was dissolved by adding 8mmol of piperidine, 2mmol of tetrachloroethane, and 10mmol of sulfur, and the mixture was heated to 100 ℃ and stirred at 800rpm for 8 hours.
After the reaction was completed, heating was stopped, 100mL of ethyl acetate was added thereto to quench and dilute the reaction solution, and then the precipitated solid was removed from the reaction solution by filtration. The reaction solution from which the solids were removed was extracted using a saturated aqueous ammonium chloride solution as an aqueous phase and ethyl acetate as an organic phase, and then the resulting organic phases were combined. The solvent of the combined organic phases was removed by evaporation under reduced pressure with heating and the crude product was obtained. Then, the mixture is purified by silica gel column chromatography using a petroleum ether to ethyl acetate volume ratio of 4: 1 as eluent, the purified product was separated from the system and dried at 60 c for 10min to finally obtain the piperidinyl-substituted fully substituted dithiooxamide compound as a yellow solid product in 38% yield.
The dithiooxamide Compound obtained in this example is shown as Compound 4.
Example 5
The (2-phenethyl) substituted dithiooxamide is prepared by a multi-component reaction of elemental sulfur, tetrachloroethane and an amine compound to prepare the dithiooxamide compound, and the reaction equation is shown as the formula (VI):
the synthetic method comprises the following steps:
in an argon-filled reactor, 8mL of N, N-dimethylacetamide was dissolved by adding 8mmol of 2-phenylethylamine, 2mmol of tetrachloroethane, and 10mmol of sulfur, and the mixture was heated to 100 ℃ and stirred at 800rpm for 8 hours.
After the reaction was completed, heating was stopped, 100mL of ethyl acetate was added thereto to quench and dilute the reaction solution, and then the precipitated solid was removed from the reaction solution by filtration. The reaction solution from which the solids were removed was extracted using a saturated aqueous ammonium chloride solution as an aqueous phase and ethyl acetate as an organic phase, and then the resulting organic phases were combined. The solvent of the combined organic phases was removed by evaporation under reduced pressure with heating and the crude product was obtained. Then, silica gel column chromatography was performed using a petroleum ether to ethyl acetate volume ratio of 4: 1 as eluent, the purified product was separated from the system and dried at 60 c for 10min to finally obtain the product (2-phenylethyl) substituted fully substituted dithiooxamide compound as a yellow solid in a yield of 25%.
The dithiooxamide Compound obtained in this example is shown as Compound 5.
Example 6
The dodecyl-substituted dithiooxamide is prepared by utilizing the multicomponent reaction of elemental sulfur, tetrachloroethane and amine compound to prepare dithiooxamide compound, wherein the reaction equation is shown as a formula (VII):
the synthetic method comprises the following steps:
in a reactor filled with argon, 8mL of N, N-dimethylacetamide was dissolved by adding 8mmol of dodecylamine, 2mmol of tetrachloroethane, and 10mmol of sulfur, and the mixture was heated to 100 ℃ and stirred at 800rpm for 8 hours.
After the reaction was completed, heating was stopped, 100mL of ethyl acetate was added thereto to quench and dilute the reaction solution, and then the precipitated solid was removed from the reaction solution by filtration. The reaction solution from which the solids were removed was extracted using a saturated aqueous ammonium chloride solution as an aqueous phase and ethyl acetate as an organic phase, and then the resulting organic phases were combined. The solvent of the combined organic phases was removed by evaporation under reduced pressure with heating and the crude product was obtained. Then, silica gel column chromatography was performed using a petroleum ether to ethyl acetate volume ratio of 4: 1 as eluent, the purified product was separated from the system and dried at 60 c for 10min to finally obtain the product dodecyl-substituted dithiooxamide compound as a black viscous solid in a yield of 20%.
The dithiooxamide Compound obtained in this example is shown as Compound 6.
The above embodiments show that the invention provides a dithiooxamide compound and a preparation method thereof, and the invention realizes the efficient and low-cost preparation of the rarely reported N, N-di-aliphatic group substituted dithiooxamide compound and N, N-di-aromatic group substituted dithiooxamide compound, and the preparation method of the invention has the characteristics of mild reaction conditions, simple operation, various product structures and the like.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A dithiooxamide compound comprising one of the following structural formulas:
wherein R is 1 And R 2 Independently is aliphatic alkyl, oxo aliphatic alkyl, aliphatic alkyl with aromatic substituent, oxo aliphatic alkyl with aromatic substituent, aliphatic alkyl with halide substituent or oxo aliphatic alkyl with halide substituent;
R 3 and R 4 Independently hydrogen atom, alkyl, alkoxy, halogen, hydroxyl, ester group, carbonyl, aryl or cyano;
R 5 and R 6 Independently is a hydrocarbyl, a hydrocarbyl with aromatic substituent or a hydrocarbyl with halide substituent, both sides of which are simultaneously connected with nitrogen atoms;
R 7 and R 8 Independently, the alkyl group is aliphatic alkyl, aliphatic alkyl with aromatic substituent or aliphatic alkyl with halide substituent.
2. Dithiooxamide compound according to claim 1, characterized in that it comprises in particular one of the following structural formulae:
3. a method for producing dithiooxamide compounds as claimed in claim 1 or claim 2, comprising the steps of:
the product obtained by reacting sulfur, tetrachloroethane and an amine compound is the dithiooxamide compound.
4. The method for producing dithiooxamide compounds according to claim 3, wherein the molar ratio of the sulfur, tetrachloromethane and amine compound is from 0.25 to 10.0: 0.17-4.0: 1.0 to 10.0.
5. The method for producing dithiooxamide compounds according to claim 3 or 4, wherein the amine compound comprises one of the following structural formulae:
wherein R is 1 And R 2 Independently is aliphatic alkyl, oxo-aliphatic alkyl, aliphatic alkyl with aromatic substituent, oxo-aliphatic alkyl with aromatic substituent, aliphatic alkyl with halide substituent or oxo-aliphatic alkyl with halide substituent;
R 3 and R 4 Independently is a hydrogen atom, a hydrocarbyl group, an alkoxy group, a halogen, a hydroxyl group, an ester group, a carbonyl group, an aryl group or a cyano group;
R 5 and R 6 Independently is a hydrocarbyl, a hydrocarbyl with aromatic substituent or a hydrocarbyl with halide substituent, both sides of which are simultaneously connected with nitrogen atoms;
R 7 and R 8 Independently is an aliphatic hydrocarbon radical, a beltAliphatic hydrocarbon groups having aromatic substituents or aliphatic hydrocarbon groups having halide substituents.
6. The method for preparing dithiooxamide compounds according to claim 5, wherein the amine compound specifically comprises one of the following structural formulas:
wherein n and k are independently integers of 1-30.
7. The method for producing dithiooxamide compounds according to claim 6, wherein the reaction is carried out in a solvent, and the molar volume ratio of the amine compound to the solvent is from 0.01 to 5 mol: 1L;
the solvent comprises one or more of N, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide.
8. Process for the preparation of dithiooxamide compounds according to claim 4 or 6 or 7, characterised in that the reaction is carried out under a protective atmosphere comprising nitrogen and/or argon.
9. The method for producing dithiooxamide compounds according to claim 8, wherein the reaction temperature is 20 to 120 ℃ and the reaction time is 2 to 48 hours.
10. The method for preparing dithiooxamide compounds according to claim 3 or 9, wherein the reaction is carried out under the action of a catalyst which is a basic compound comprising one or more of N, N-diisopropylethylamine, triethylamine, potassium fluoride and potassium carbonate; the molar ratio of the catalyst to the amine compound is 10-40: 1 to 10.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1219853A (en) * | 1967-04-28 | 1971-01-20 | Basf Ag | Production or dithio-oxamides |
| DE2246025A1 (en) * | 1972-09-20 | 1974-03-28 | Akzo Gmbh | Dithiooxamides derivs prepn - from amines and alkali cyanodithioformate |
| CN104151220A (en) * | 2014-08-12 | 2014-11-19 | 湖南凯米尔生物科技有限公司 | N,N'-dialkyl dithiooxamide as well as preparation method and application thereof |
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- 2022-07-12 CN CN202210813896.XA patent/CN115010634A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1219853A (en) * | 1967-04-28 | 1971-01-20 | Basf Ag | Production or dithio-oxamides |
| DE2246025A1 (en) * | 1972-09-20 | 1974-03-28 | Akzo Gmbh | Dithiooxamides derivs prepn - from amines and alkali cyanodithioformate |
| CN104151220A (en) * | 2014-08-12 | 2014-11-19 | 湖南凯米尔生物科技有限公司 | N,N'-dialkyl dithiooxamide as well as preparation method and application thereof |
Non-Patent Citations (1)
| Title |
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| LIHUI ZHANG 等: "Room temperature synthesis of polythioamides from multicomponent polymerization of sulfur, pyridine-activated alkyne, and amines" * |
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