CN105541684B - A kind of oxide-reduction method of four acetylene compounds and Diphenylthiocarbazone - Google Patents
A kind of oxide-reduction method of four acetylene compounds and Diphenylthiocarbazone Download PDFInfo
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- CN105541684B CN105541684B CN201610109262.0A CN201610109262A CN105541684B CN 105541684 B CN105541684 B CN 105541684B CN 201610109262 A CN201610109262 A CN 201610109262A CN 105541684 B CN105541684 B CN 105541684B
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- diphenylthiocarbazone
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- acetylene compounds
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- UOFGSWVZMUXXIY-UHFFFAOYSA-N 1,5-Diphenyl-3-thiocarbazone Chemical compound C=1C=CC=CC=1N=NC(=S)NNC1=CC=CC=C1 UOFGSWVZMUXXIY-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 33
- 239000000047 product Substances 0.000 claims description 20
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 11
- 238000004440 column chromatography Methods 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- 229940125904 compound 1 Drugs 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- -1 acetylene compound Chemical class 0.000 claims description 7
- 239000003208 petroleum Substances 0.000 claims description 7
- 230000006837 decompression Effects 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 239000012265 solid product Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- AZQCFLDDJHERFZ-UHFFFAOYSA-N Br.C#Cc1ccccc1 Chemical compound Br.C#Cc1ccccc1 AZQCFLDDJHERFZ-UHFFFAOYSA-N 0.000 claims description 5
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- YORCIIVHUBAYBQ-UHFFFAOYSA-N propargyl bromide Chemical compound BrCC#C YORCIIVHUBAYBQ-UHFFFAOYSA-N 0.000 claims description 5
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 4
- 239000005457 ice water Substances 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 4
- 239000012312 sodium hydride Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 229940125782 compound 2 Drugs 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 0 *OC(C(Cc1ccc2-c3ccccc3)(Cc1c2C#Cc1ccccc1)C(O*)=[U])=O Chemical compound *OC(C(Cc1ccc2-c3ccccc3)(Cc1c2C#Cc1ccccc1)C(O*)=[U])=O 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000003810 ethyl acetate extraction Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- OEWAXXLOSKFJKT-UHFFFAOYSA-N 1-imino-3-(n-phenylanilino)thiourea Chemical class C=1C=CC=CC=1N(NC(=S)N=N)C1=CC=CC=C1 OEWAXXLOSKFJKT-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 150000007857 hydrazones Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- JGOAZQAXRONCCI-SDNWHVSQSA-N n-[(e)-benzylideneamino]aniline Chemical compound C=1C=CC=CC=1N\N=C\C1=CC=CC=C1 JGOAZQAXRONCCI-SDNWHVSQSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000005323 thioketone group Chemical group 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C337/00—Derivatives of thiocarbonic acids containing functional groups covered by groups C07C333/00 or C07C335/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group
- C07C337/10—Derivatives of thiocarbonic acids containing functional groups covered by groups C07C333/00 or C07C335/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group the two nitrogen atoms of the functional groups being doubly-bound to each other
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of oxide-reduction methods of four acetylene compounds and Diphenylthiocarbazone.Compared with prior art, the oxide-reduction method of a kind of completely new four acetylene compounds and Diphenylthiocarbazone provided by the invention, generates new redox products, has broad application prospects；Moreover, oxide-reduction method provided by the invention, easy to operate, reaction efficiency is high, and reaction condition is mild.
Description
Technical field
The invention belongs to organic synthesis fields, and in particular to a kind of oxygen of four acetylene compounds and Diphenylthiocarbazone
Change restoring method.
Background technology
Diphenylthiocarbazone is also known as dithizone or beats Sa hydrazone, belongs to sulphur hydrazone analog derivative.Diphenylthiocarbazone
Structural formula：
Diphenylthiocarbazone derivative is the vulcanization azo carbonyl hydrazides for having thioketones base and nitrence base, and the compound is easy
It aoxidized, restored, the reactions such as halogenation, being the raw material for synthesizing various compounds.Research shows that Diphenylthiocarbazone conduct
Chelating agent is allowed to react generation band color substance with metal ion, the concentration of the metal ion is then measured with spectrophotometry.Separately
Outside, Diphenylthiocarbazone is experimental determination water, food, the lead content common agents in cosmetics biomaterial.Hexichol
Base thiocarbohydrazone can not only measure the content of lead, can also measure the heavy metals such as cobalt, mercury, cadmium and silver, be to be complexed well
Indicator.
Currently, just worldwide actively being carried out by the research of raw material, exploitation of Diphenylthiocarbazone.
Invention content
The object of the present invention is to provide a kind of redox sides of four acetylene compound and Diphenylthiocarbazone
Method, method is simple, reaction condition is mild.
The oxide-reduction method of a kind of four acetylene compounds and Diphenylthiocarbazone provided by the invention, including with
Lower step：
Under conditions of 90-110 DEG C, four acetylene compounds react 6- using toluene as solvent, with Diphenylthiocarbazone
10 hours, product obtained redox products through isolating and purifying.
The structural formula of the four acetylene compounds compound is：The thio kappa of diphenyl
Hydrazone structural formula is：Obtained oxidation product is
Obtained reduzate isR is straight chained alkyl, branched alkyl, satisfies in above compound
With hydro carbons, unsaturated hydro carbons or arene group, R1For halogen, straight chained alkyl, branched alkyl, ester group, alkoxy and its
Corresponding derivative；
The purifies and separates are specially：Product is washed with water, and ethyl acetate extraction, decompression is spin-dried for, with volume ratio 1:50
Ethyl acetate：Petroleum ether column chromatography for separation, obtains atropurpureus solid, as oxidation product, and column chromatography yield is about 66.3%.
The molar ratio of four acetylene compounds, Diphenylthiocarbazone and toluene is 1.1-1.5：1.0-2.0：28-66.
The preparation method of four acetylene compound, includes the following steps：
(1) using sodium hydride as catalyst, dimethyl malenate and propargyl bromide are added to ice-water bath in anhydrous acetonitrile,
It is stirred to react 8 hours, product purification separation obtains white solid product, i.e. compound 1；Structural formula is：
(2) compound 1 and phenylacetylene bromide are blended in Pd (PPh3)2Cl2In the anhydrous and oxygen-free catalyst system and catalyzing of/CuI, with
Triethylamine makees alkali, using anhydrous acetonitrile as solvent, is stirred to react at room temperature 12 hours, and product purification separation obtains faint yellow solid
Product, i.e. precursor compound 2, i.e. four acetylene compounds；Structural formula is
Further, the wherein molar ratio of sodium hydride, dimethyl malenate, propargyl bromide and anhydrous acetonitrile in step (1)
It is 4.15：1：2.2-3.2：20-23；The purifies and separates are specially：Product adds water washing, is extracted with ethyl acetate, decompression rotation
It is dry, with volume ratio 1:40 ethyl acetate：Petroleum ether column chromatography for separation obtains white solid product, i.e. compound 1；
The molar ratio of compound 1 described in step (2) and phenylacetylene bromide is 1:2.2-3.2；Pd (the PPh3)2Cl2/
In the anhydrous and oxygen-free catalyst system and catalyzing of CuI, molar ratio Pd (PPh3)2Cl2:CuI=3:1；The purifies and separates are specially：It is washed with water
It washs, is extracted with ethyl acetate, decompression is spin-dried for, with volume ratio 1:40 ethyl acetate：Petroleum ether column chromatography for separation.
Compared with prior art, a kind of completely new four acetylene compounds and Diphenylthiocarbazone provided by the invention
Oxide-reduction method generates new redox products, has broad application prospects；Moreover, redox provided by the invention
Method, easy to operate, reaction efficiency is high, and reaction condition is mild.
Description of the drawings
Fig. 1 is the structural formula of 1 Diphenylthiocarbazone of embodiment；
Fig. 2 is the structural formula of oxidation product prepared by embodiment 1；
Fig. 3 is the structural formula of oxidation product prepared by embodiment 11H NMR figures.
Specific implementation mode
Embodiment 1
A kind of oxide-reduction method of four acetylene compounds and Diphenylthiocarbazone, includes the following steps：
(1) using 830mmol sodium hydrides as catalyst, 200mmol dimethyl malenates and 440mmol propargyl bromides are added
To ice-water bath in 210mL anhydrous acetonitriles, (temperature of ice-water bath is 0-5 DEG C) is stirred to react 8 hours, and product adds water washing, uses second
Acetoacetic ester extracts, and decompression is spin-dried for, with volume ratio 1:40 ethyl acetate：Petroleum ether column chromatography for separation obtains yellow-brown solid production
Object, i.e. compound 1；Structural formula is：
(2) 80mmol compounds 1 and 200mmol phenylacetylene bromides are blended in Pd (PPh3)2Cl2The anhydrous and oxygen-free of/CuI
In catalyst system and catalyzing (2.56mmol/0.85mmol), molar ratio Pd (PPh3)2Cl2:CuI=3:1, made with 336mmol triethylamines
Alkali is stirred to react 12 hours, product is washed with water, and is extracted with ethyl acetate, and subtracts at room temperature using 150mL anhydrous acetonitriles as solvent
Pressure is spin-dried for, with volume ratio 1:40 ethyl acetate：Petroleum ether column chromatography for separation obtains faint yellow solid product, i.e. precursor chemical combination
Object 2, structural formula are
Reaction equation：
(3) under conditions of 100 DEG C, the precursor compound 2 prepared by step (2), i.e. four acetylene compounds (1.2mmol)
Solvent reaction is made 8 hours with toluene (5ml) with Diphenylthiocarbazone (2mmol), obtains crude product；Crude product with water is washed
It washs, ethyl acetate extraction, decompression is spin-dried for, with volume ratio 1:50 ethyl acetate：It is solid to obtain atropurpureus for petroleum ether column chromatography for separation
Body product, i.e. oxidation product, column chromatography yield are about 66.3%.
Atropurpureus solid passes through1H NMR are measured
1H NMR(300MHz,CDCl3) δ 8.16 (d, J=8.0Hz, 1H), 7.95 (dd, J=6.4,3.0Hz, 1H), 7.52
(dd, J=9.9,6.1Hz, 4H), 7.45-7.20 (m, 2H), 7.00 (s, 2H).
Claims (3)
1. a kind of oxide-reduction method of four acetylene compounds and Diphenylthiocarbazone, which is characterized in that the oxidation
Restoring method includes the following steps：
Under conditions of 90-110 DEG C, it is small that four acetylene compounds using toluene as solvent, with Diphenylthiocarbazone react 6-10
When, product obtains redox products through isolating and purifying；
The structural formula of four acetylene compound is：Wherein R is-CH3；
The Diphenylthiocarbazone structural formula isR1For H；
The redox products are
The molar ratio of four acetylene compounds, Diphenylthiocarbazone and toluene is 1.1-1.5：1.0-2.0：28-66；
The preparation method of four acetylene compound, includes the following steps：
(1) using sodium hydride as catalyst, dimethyl malenate and propargyl bromide are added to ice-water bath in anhydrous acetonitrile, stirring is anti-
It answers 8 hours, product purification separation obtains white solid product, i.e. compound 1；Structural formula is：
(2) compound 1 and phenylacetylene bromide are blended in Pd (PPh3)2Cl2In the anhydrous and oxygen-free catalyst system and catalyzing of/CuI, with three second
Amine makees alkali, using anhydrous acetonitrile as solvent, is stirred to react at room temperature 12 hours, and product purification separation obtains faint yellow solid product,
That is precursor compound 2, i.e. four acetylene compounds；Structural formula is
Wherein the molar ratio of sodium hydride, dimethyl malenate, propargyl bromide and anhydrous acetonitrile is 4.15 in step (1)：1：2.2-
3.2：20-23；
The molar ratio of compound 1 described in step (2) and phenylacetylene bromide is 1:2.2-3.2.
2. oxide-reduction method according to claim 1, which is characterized in that Pd (PPh described in step (2)3)2Cl2/CuI
Anhydrous and oxygen-free catalyst system and catalyzing in, molar ratio Pd (PPh3)2Cl2:CuI=3:1.
3. oxide-reduction method according to claim 1, which is characterized in that purifies and separates are specially described in step (2)：
It is washed with water, is extracted with ethyl acetate, decompression is spin-dried for, with volume ratio 1:40 ethyl acetate：Petroleum ether column chromatography for separation.
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| CN104402696B (en) * | 2014-12-04 | 2016-02-03 | 安徽师范大学 | A kind of oxide-reduction method of bitter almond oil camphor type organic |
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