CN1560029A - Substituting Cis-1,2-dicyano vinyl and synthesis process thereof - Google Patents
Substituting Cis-1,2-dicyano vinyl and synthesis process thereof Download PDFInfo
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- CN1560029A CN1560029A CNA2004100135698A CN200410013569A CN1560029A CN 1560029 A CN1560029 A CN 1560029A CN A2004100135698 A CNA2004100135698 A CN A2004100135698A CN 200410013569 A CN200410013569 A CN 200410013569A CN 1560029 A CN1560029 A CN 1560029A
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- acrylonitriles
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- 238000000034 method Methods 0.000 title claims description 15
- 230000015572 biosynthetic process Effects 0.000 title claims description 3
- 238000003786 synthesis reaction Methods 0.000 title claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 title 1
- 229920002554 vinyl polymer Polymers 0.000 title 1
- 238000010189 synthetic method Methods 0.000 claims abstract description 10
- 150000008360 acrylonitriles Chemical class 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 35
- -1 sec.-propyl Chemical group 0.000 claims description 25
- 239000003960 organic solvent Substances 0.000 claims description 19
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 13
- 238000004440 column chromatography Methods 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 150000001345 alkine derivatives Chemical class 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 238000001953 recrystallisation Methods 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 238000005194 fractionation Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical group [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052753 mercury Inorganic materials 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 230000005855 radiation Effects 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Natural products CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000012074 organic phase Substances 0.000 claims description 2
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 claims description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 2
- 229960000583 acetic acid Drugs 0.000 claims 1
- 239000012362 glacial acetic acid Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 9
- 230000003287 optical effect Effects 0.000 abstract description 8
- 239000005977 Ethylene Substances 0.000 abstract description 6
- 231100000053 low toxicity Toxicity 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract 2
- 150000004696 coordination complex Chemical class 0.000 abstract 1
- YKENVNAJIQUGKU-UHFFFAOYSA-N tetraazaporphin Chemical compound C=1C(C=N2)=NC2=NC(NN2)=NC2=CC(C=C2)=NC2=CC2=NC=1C=C2 YKENVNAJIQUGKU-UHFFFAOYSA-N 0.000 abstract 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 48
- 150000004032 porphyrins Chemical class 0.000 description 11
- 238000002329 infrared spectrum Methods 0.000 description 10
- 239000000543 intermediate Substances 0.000 description 8
- 150000002825 nitriles Chemical class 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- URFPRAHGGBYNPW-UHFFFAOYSA-N 1-bromo-4-ethylbenzene Chemical compound CCC1=CC=C(Br)C=C1 URFPRAHGGBYNPW-UHFFFAOYSA-N 0.000 description 2
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000004414 alkyl thio group Chemical group 0.000 description 2
- 125000003963 dichloro group Chemical group Cl* 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 2
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 1
- BRGVKVZXDWGJBX-UHFFFAOYSA-N 1-bromo-4-butylbenzene Chemical compound CCCCC1=CC=C(Br)C=C1 BRGVKVZXDWGJBX-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical group CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- XGMLKGHOPUBSND-UHFFFAOYSA-N 2-bromo-3,3-dimethylbut-1-ene Chemical compound CC(C)(C)C(Br)=C XGMLKGHOPUBSND-UHFFFAOYSA-N 0.000 description 1
- GQYAWVVNZAWBEI-UHFFFAOYSA-N C#C.C(CCC)C1=CC=CC=C1 Chemical group C#C.C(CCC)C1=CC=CC=C1 GQYAWVVNZAWBEI-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- JKFPHRRMFFHRDM-UHFFFAOYSA-N acetylene ethylbenzene Chemical group C#C.C(C)C1=CC=CC=C1 JKFPHRRMFFHRDM-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000001093 anti-cancer Effects 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000186 gas chromatography-infrared spectroscopy Methods 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 238000007699 photoisomerization reaction Methods 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
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Abstract
The invention is a substituted cis-1, 2-ethylene dicyanide and its synthetic method: (1) synthesizing substituted trans-1, 2-ethylene dihalide and substituted cis-1, 2-ethylene dihalide; (2) synthesizing substituted trans-1, 2-ethylene dicyanide and substituted cis-1, 2-ethylene dicyanide; (3) converting substituted trans-1, 2-ethylene dicyanide to the optical isomer of substituted cis-1, 2-ethylene dicyanide; it broadens the modifiability of tetraazaporphyrin complex, and increases the solubility of its metal complex; the synthetic method and conditions are moderate, have no special requirements for the reacting system, the raw materials have low toxicity and the total productivity is high.
Description
Technical field
The present invention relates to a kind of replacement cis 1,2-two acrylonitriles and synthetic method thereof, the particularly cis 1 that replaces about alkyl, aryl, 2-dicyan ethylene product and synthetic method.Method of the present invention can be widely used in the cis 1 that alkyl, aryl replace, 2-two acrylonitriles synthetic, and its compound and derivative thereof are one of synthetic important intermediate that replaces tetraazatetradecane porphyrin class title complex.
Background technology
Tetraazatetradecane porphyrin and title complex thereof make it all have very wide application prospect in fields such as biology, bionics, materialogy, pharmacology, electrochemistry, optical physics chemistry as anticancer photosensitizer, optical storage media, nonlinear optical material, the quick material of air humidity or the like because it has special macrocyclic structure and excellent physics, chemical property.Do not replace the poorly soluble of tetraazatetradecane porphyrin and title complex thereof owing to have, the research and the application of a lot of character are restricted, thereby improve the solvability of tetraazatetradecane porphyrin title complex, and the high-efficiency synthesis method of seeking solubility tetraazatetradecane porphyrin title complex becomes the major issue that needs to be resolved hurrily at present.Cis-1,2-two acrylonitriles (also being Maleic nitrile) and trans-1,2-two acrylonitriles (also being flumaronitrile) and derivative thereof are one of intermediates of synthetic this compounds necessity, but trans-isomer(ide) trans-1,2-two acrylonitriles and derivative thereof are owing to structural reason, synthetic yield is far away from cis-isomeride, thereby is domestic and international scientist's research focus to the synthetic and performance study of Maleic nitrile (cis-1,2-two acrylonitriles) and their various derivatives always.Once reported the synthetic cis 1 that replaces of several differences in the document, the method of 2-two acrylonitriles: (1) document Zh.Org.Khim.1992,28 (10): 2149-2155 and Zh.Org.Khim.1979,15 (5): the method for 1076-1082 be with one or the dichloro Maleic nitrile in active chlorine atom carry out the synthetic target Maleic nitrile intermediate of nucleophilic substitution with other substituting group (as alkoxyl group, alkylthio etc.), the raw material one of this method or dichloro Maleic nitrile normally with succinonitrile or with phosphorus pentachloride or with chlorine reaction synthetic.The main drawback of this method is that raw material is expensive, phosphorus pentachloride or chlorine are the materials of strong moisture absorption and severe toxicity, and in the nucleophilic substitution process, there are some unsettled intermediates to produce, so the control to conversion unit and experiment condition requires also very high (such as waterless operation, temperature control), it is mainly used in the tetraazatetradecane porphyrin title complex of synthetic alkoxyl group, aryloxy replacement simultaneously.(2) document Inorg.Synth.1967,10:8-26 and Inorg.Chem.1980,19:383-385 is with a halohydrocarbon or dihalo hydrocarbon and the effect of Maleic nitrile disodium salt, obtain the Maleic nitrile intermediate that the dialkyl group of cis replaces, can react with dithiocarbonic anhydride by sodium cyanide as the Maleic nitrile disodium salt of raw material and obtain.The starting raw material sodium cyanide of this method and dithiocarbonic anhydride all are highly toxic substances, easily operator and environment are damaged, and in addition, this method can only be synthesized the tetraazatetradecane porphyrin title complex that is connected with eight alkylthios.Document Zh.Obshch.Khim.1977,47 (9): 2143-2148 once reported with cis-1,2-two bromo-tertiary butyl ethene are raw material, prepare cis-1 through cyaniding, the process of 2-dicyan-tertiary butyl ethene, and document Synthesis.1991,686-688 reported once that to replace alkynes be raw material, through bromination, reaction such as cyaniding and photoisomerization, preparation alkyl or aryl Maleic nitrile intermediate, the main drawback of these two kinds of methods are that per step reaction all needs pure substance, especially replace trans-1,2-sym-dibromoethane and replacement cis-1,2-sym-dibromoethane similar performance, separation difficulty, the trans-1 that separates, the 2-sym-dibromoethane is not used to next step reaction, thereby the synthetic overall yield is very low, and cost increases.
Summary of the invention
Purpose of the present invention is exactly the problem and shortage that exists in the above-mentioned prior art, research and design provides a kind of replacement cis 1,2-two acrylonitriles and synthetic method thereof, reach improve the sintetics overall yield, reduce production costs, raw material low toxicity and utilization ratio height, reaction conditions gentleness, purpose that reaction system is had no special requirements, alleviates and avoids operation producers and environment are damaged.
Basic design of the present invention is, replaces cis 1, and the general formula of molecular structure of 2-two acrylonitriles is as follows:
C in the structural formula and N represent carbon and nitrogen respectively; R and R ' represent hydrogen atom, methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl and other straight chain, side chain and cyclic alkyl (C
1-20Individual carbon atom), aromatic base, heterocyclic radical; Above-mentioned replacement cis 1, two itrile groups of 2-two acrylonitriles are active groups that cyclization forms metal complexes.Above-mentioned replacement cis 1, the R of 2-two acrylonitriles and R ' substituting group have regulating effect to the metal complexes that forms in the solubleness of general organic solvent, are the important intermediate of preparation solubility tetraazatetradecane porphyrin title complex.
Replace cis 1,2-two acrylonitrile synthetic methods are as follows:
(1) replaces trans-1,2-acetylenedihalide and replace cis-1,2-acetylenedihalide synthetic
In reaction flask, add organic solvent 1 and replace alkynes, slowly splash in the above-mentioned solution with the mixed solution of dropping funnel with halogen and organic solvent 1, the mol ratio that replaces alkynes and halogen is 1: (1-1.4), and after dripping off, normal temperature continued stirring reaction 1-20 hour, reaction solution obtains product and replaces trans-1 after washing, boiling off solvent, 2-acetylenedihalide and replacement cis-1,2-acetylenedihalide mixture, the two mixture is directly used in the next step without separation, and also available column chromatography is further purified.
(2) replace trans-1,2-two acrylonitriles and replace cis-1,2-two acrylonitriles synthetic
Add cyanating reagent in reaction flask, organic solvent 2 stirs, be heated to room temperature-200 ℃, be cooled to room temperature, add and replace trans-1,2-acetylenedihalide and replacement cis-1,2-acetylenedihalide mixture, described replacement trans/cis-1, the mol ratio of 2-acetylenedihalide mixture and cyanating reagent is 1: (2-10), reheat is to 50-200 ℃, reacted 1-20 hour, and after reacting completely, be cooled to room temperature.Reaction solution is poured in ammoniacal liquor or the water, stirred 1-10 hour,, merge organic phase with organic solvent 3 extractions, washing after the drying, separates with the method for vacuum fractionation, recrystallization or column chromatography, obtain replacing trans-1 respectively, 2-two acrylonitriles and replacement cis-1,2-two acrylonitriles.
Described cyanating reagent can be cuprous cyanide, potassium cyanide, sodium cyanide and other cyanating reagent; Described organic solvent 2 is N, the mixed solvent of one or more of intensive polar solvents such as dinethylformamide (DMF), N,N-dimethylacetamide, N-Methyl pyrrolidone, methyl-sulphoxide.Described organic solvent 3 can be ether, methyl ethyl ether, chloroform, the mixed solvent of one or more of the non-polar solvent that tetracol phenixin, benzene, toluene, tetrahydrofuran (THF), sherwood oil, hexane etc. can not dissolve each other with water.
(3) replace trans-1,2-two acrylonitriles are to replacing cis-1, and the light isomery of 2-two acrylonitriles transforms
Add isolated replacement trans-1 in (2) in reaction flask, 2-two acrylonitriles join in the organic solvent 4, stir and use 100-1000 watt of high voltage mercury lamp radiation down, react 1-20 hour.Reaction boils off solvent after finishing, and carries out vacuum fractionation, recrystallization or column chromatography for separation, obtains replacing trans-1 respectively, 2-two acrylonitriles and replacement cis-1,2-two acrylonitriles.Isolated replacement trans-1,2-two acrylonitriles repeat the operation of this step, replace cis-1,2-two acrylonitriles until all being converted into.
Described organic solvent 4 can be one or more a mixed solvent of the low solvent of uv-absorbing such as acetonitrile, propionitrile, methyl alcohol, hexane.
Its reaction formula is as follows:
Wherein X represents halogen or class halogen atoms such as fluorine, chlorine, bromine, iodine.
The invention provides a kind of replacement cis 1 of above-mentioned molecular structure, 2-two acrylonitriles simply, synthetic method efficiently.The present invention has the reaction conditions gentleness, reaction system is had no special requirements, raw material low toxicity and utilization ratio height, synthetic overall yield advantages of higher.Preparation method of the present invention is that a kind of preparation of highly effective replaces cis 1, and the method for 2-two acrylonitriles both had been fit to prepared in laboratory, also was fit to suitability for industrialized production.Replacement cis 1 of the present invention, 2-two acrylonitriles are preparation solubility and the important intermediate that replaces the tetraazatetradecane porphyrin title complex, have widened the modifiability of tetraazatetradecane porphyrin title complex greatly.In general organic solvent (as methyl alcohol, chloroform, methylene dichloride, DMF, toluene, hexane etc.), good solubleness is arranged behind the tetraazatetradecane porphyrin title complex metal complexes that compound cyclization of the present invention forms, such title complex has physics, the chemical property of many excellences simultaneously, and it all has very wide application prospect in fields such as materialogy, electrochemistry, optical physics chemistry as photoelectric switching device, optical conductor, optical information storage medium, nonlinear optical material or the like.
Description of drawings
Fig. 1 is 1, the infrared spectra of 2-two bromo-(4-ethylbenzene) ethene (trans 1a and cis 1a ');
Fig. 2 is 1, the infrared spectra of 2-two bromo-(4-butylbenzene) ethene (trans 1b and cis 1b ');
Fig. 3 is trans-1,2-dicyan-(4-ethylbenzene) ethene (2a) infrared spectra;
Fig. 4 is cis-1, and 2-dicyan-(4-ethylbenzene) ethene (2a ') infrared spectra;
Fig. 5 is trans-1,2-dicyan-(4-butylbenzene) ethene (2b) infrared spectra;
Fig. 6 is cis-1, and 2-dicyan-(4-butylbenzene) ethene (2b ') infrared spectra;
Fig. 7 is trans-1, the NMR (Nuclear Magnetic Resonance) spectrum of 2-dicyan-(4-butylbenzene) ethene (2b);
Fig. 8 is cis-1, the NMR (Nuclear Magnetic Resonance) spectrum of 2-dicyan-(4-butylbenzene) ethene (2b ').
Embodiment
Embodiment 1:
(1) trans-1,2-two bromo-(4-ethylbenzene) ethene (1a) and cis-1,2-two bromo-(4-ethylbenzene) ethene (1a ') synthetic
In reaction flask, add 200ml exsiccant CCl
4, 25.0ml4-ethylbenzene acetylene, with dropping funnel with the dry CCl of 10ml bromine and 100ml
4Mixed solution slowly splash in the above-mentioned solution, after dripping off, normal temperature continued stirring reaction 4 hours, and reaction solution obtains product trans-1 after washing, boiling off solvent, 2-two bromo-(4-ethylbenzene) ethene (1a) and cis-1,2-two bromo-(4-ethylbenzene) ethene (1a ') mixture, the two mixture is directly used in the next step, and also available column chromatography is further purified, weigh, calculate productive rate, measure the makings connection spectrum and the infrared spectra (as table 1) of product.
Table 11,2-two bromo-(4-ethylbenzene) ethene (trans 1a and cis 1a ') and 1, the analytical results of 2-two bromo-(4-ethylbenzene) ethene (trans 1b and cis 1b ')
GC IR
Compound?Yield(％) MS(m/e)
％oftotal?R.T.(min) V(cm
-1)
1a 42.89 10.04
97.0 290[M]
+See Fig. 1
1a’ 49.03 8.98
1b 60.02 12.83
96.0 318[M]
+See Fig. 2
1b’ 30.09 11.27
(2) trans-1,2-dicyan-(4-ethylbenzene) ethene (2a) and cis-1,2-dicyan-(4-ethylbenzene) ethene (2a ') synthetic
In reaction flask, add the 35.67g cuprous cyanide; 200ml exsiccant DMF feeds nitrogen protection, stirs; be heated to 90-140 ℃; the reaction postcooling adds 42.53gtrans-1,2-two bromo-(4-ethylbenzene) ethene and cis-1 to room temperature; 2-two bromo-(4-ethylbenzene) mixture of ethylene; reheat after reacting completely, is cooled to room temperature to 90-140 ℃.Reaction solution is poured in the ammoniacal liquor, stirred 2 hours.With the extraction that agent solvent (3) are arranged, washing, after the drying, boil off solvent, method with recrystallization or column chromatography is separated, and obtains trans-1 respectively, 2-dicyan-(4-ethylbenzene) ethene (2a) and cis-1,2-dicyan-(4-ethylbenzene) ethene (2a '), weigh respectively, calculate productive rate, the fusing point of measuring product, infrared spectra, makings connection spectrum,
1H NMR and CHN content (as table 2).
Table 21,2-dicyan-(4-ethylbenzene) ethene (trans 2a and cis 2a ') and 1, the analytical results of 2-dicyan-(4-butylbenzene) ethene (trans 2b and cis 2b ')
Com- Elemental?analysis(％) IR
Yield(％) mp(℃) Found(Calcd)
pound V(cm
-1)
C H N
2a 90.0 70.3-70.8 78.51 5.45 15.39 see Fig. 3
(79.10) (5.53) (15.37)
2a ' 93.0 46.5-47.0 78.96 5.55 15.70 see Fig. 4
(79.10) (5.53) (15.37)
2b 88.5 58.6-59.5 79.88 7.32 13.86 see Fig. 5
(79.97) (6.71) (13.32)
2b ' 73.6 normal temperature liquid 79.86 6.36 13.12 are seen Fig. 6
(79.97) (6.71) (13.32)
Continuous table 21,2-dicyan-(4-ethylbenzene) ethene (trans 2a and cis 2a ') and 1, the analytical results of 2-dicyan-(4-butylbenzene) ethene (trans 2b and cis 2b ')
Com- GC H-NMR(CDCl
3/TMS)
MS(m/e)
pound?％oftotal?R.T.(min) δ(ppm)
2a 97.4 11.26 1.26(t，J＝7.6，3H)，2.72(m，2H)，6.32(s，1H)，7.33(d，J＝8.4，2H)
182(M
+)?7.58(d，J＝8.4，2H)
2a’98.2 9.04 1.27(t，J＝7.6，3H)，2.73(m，2H)，6.06(s，1H)，7.36(d，J＝8.4，2H)
7.86(d，J＝8.4，2H)
2b 90.5 14.56 0.93(t，J＝7.2Hz，3H)，1.35(m，2H)，1.61(m，2H)，2.68(m，2H)
210 (M
+) 6.32 (s, 1H), 7.31 (d, J=8.4,2H), 7.57 (dJ=8.4,2H) (see figure 7)s
2b’96.6 11.06
0.94(t，J＝7.2Hz，3H)，1.36(m，2H)，1.62(m，2H)，2.69(m，2H)
6.06 (s, 1H), 7.33 (d, J=8.4,2H), 7.86 (dJ=8.4,2H) (see figure 8)s
(3) trans-1,2-dicyan-(4-ethylbenzene) ethene (2a) is to cis-1, and the light isomery of 2-dicyan-(4-ethylbenzene) ethene (2a ') transforms
In reaction flask, add isolated trans-1 in (3), 2-dicyan-(4-ethylbenzene) ethene 4.0g, the 150ml acetonitrile feeds nitrogen protection, stirs down with 500 watts of high voltage mercury lamp radiations.After reaction finishes, boil off solvent, column chromatography for separation obtains trans-1,2-dicyan-(4-ethylbenzene) ethene (2a) and cis-1,2-dicyan-(4-ethylbenzene) ethene (2a '), weigh respectively, transformation efficiency is 50%, isolated trans-1,2-dicyan-(4-ethylbenzene) ethene repeats the operation of this step, until all being converted into cis-1,2-dicyan-(4-ethylbenzene) ethene (2a ').
Embodiment 2
(1) trans-1,2-two bromo-(4-butylbenzene) ethene (1b) and cis-1,2-two bromo-(4-butylbenzene) ethene (1b ') synthetic
Change the 4-ethylbenzene acetylene in embodiment 1 the first step into equimolar 4-butylbenzene acetylene, reaction makes trans-1 under similarity condition, 2-two bromo-(4-butylbenzene) ethene (1b) and cis-1, and 2-two bromo-(4-butylbenzene) ethene (1b '), the two mixture is directly used in the next step.Also available column chromatography is further purified, and weighs, calculates productive rate, measures the makings connection spectrum and the infrared spectra (as table 1) of product.
(2) trans-1,2-dicyan-(4-butylbenzene) ethene (2b) and cis-1,2-dicyan-(4-butylbenzene) ethene (2b ') synthetic
With the trans-1 of embodiment in 1 second step, 2-two bromo-(4-ethylbenzene) ethene and cis-1,2-two bromo-(4-ethylbenzene) mixture of ethylene changes trans-1 into, 2-two bromo-(4-butylbenzene) ethene and cis-1,2-two bromo-(4-butylbenzene) mixture of ethylene, reaction makes trans-1,2-dicyan-(4-butylbenzene) ethene and cis-1,2-dicyan-(4-butylbenzene) ethene under similarity condition.Weigh, calculate productive rate respectively, measure product fusing point, infrared spectra, makings connection spectrum,
1H NMR and CHN content (as table 2).
(3) trans-1,2-dicyan-(4-butylbenzene) ethene (2b) is to cis-1, and the light isomery of 2-dicyan-(4-butylbenzene) ethene (2b ') transforms
With the trans-1 of embodiment 1 in the 3rd step, 2-dicyan-(4-ethylbenzene) ethene changes trans-1 into, 2-dicyan-(4-butylbenzene) ethene, under similarity condition, react, make trans-1,2-dicyan-(4-butylbenzene) ethene (2b) and cis-1,2-dicyan-(4-butylbenzene) ethene (2b '), weigh respectively, transformation efficiency is 48%, isolated trans-1, and 2-dicyan-(4-butylbenzene) ethene repeats the operation of this step, until all being converted into cis-1,2-dicyan-(4-butylbenzene) ethene (2b ').
Claims (3)
1, a kind of replacement cis 1,2-two acrylonitriles is characterized in that this replacement cis 1, the general formula of molecular structure of 2-two acrylonitriles is as follows:
C in the structural formula and N represent carbon and nitrogen respectively; R and R ' represent hydrogen atom, methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl and other straight chain, side chain and cyclic alkyl (C
1-20Individual carbon atom), aromatic base, heterocyclic radical.
2, a kind of replacement cis 1,2-two acrylonitrile synthetic methods is characterized in that synthesis step is as follows:
(1) replaces trans-1,2-acetylenedihalide and replace cis-1,2-acetylenedihalide synthetic
In reaction flask, add organic solvent 1 and replace alkynes, slowly splash in the above-mentioned solution with the mixed solution of dropping funnel with halogen and organic solvent 1, the mol ratio that replaces alkynes and halogen is 1: (1-1.4), and after dripping off, normal temperature continued stirring reaction 1-20 hour, reaction solution obtains product and replaces trans-1 after washing, boiling off solvent, 2-acetylenedihalide and replacement cis-1,2-acetylenedihalide mixture, the two mixture is directly used in the next step without separation, and also available column chromatography is further purified.
(2) replace trans-1,2-two acrylonitriles and replace cis-1,2-two acrylonitriles synthetic
Add cyanating reagent in reaction flask, organic solvent 2 stirs, be heated to room temperature-200 ℃, be cooled to room temperature, add and replace trans-1,2-acetylenedihalide and replacement cis1,2-acetylenedihalide mixture, described replacement trans/cis-1, the mol ratio of 2-acetylenedihalide mixture and cyanating reagent is 1: (2-10), reheat is to 50-200 ℃, reacted 1-20 hour, and after reacting completely, be cooled to room temperature.Reaction solution is poured in ammoniacal liquor or the water, stirred 1-10 hour,, merge organic phase with organic solvent 3 extractions, washing after the drying, separates with the method for vacuum fractionation, recrystallization or column chromatography, obtain replacing trans-1 respectively, 2-two acrylonitriles and replacement cis-1,2-two acrylonitriles.
(3) replace trans-1,2-two acrylonitriles are to replacing cis-1, and the light isomery of 2-two acrylonitriles transforms
Add isolated replacement trans-1 in (2) in reaction flask, 2-two acrylonitriles join in the organic solvent 4, stir and use 100-1000 watt of high voltage mercury lamp radiation down, react 1-20 hour.Reaction boils off solvent after finishing, and carries out vacuum fractionation, recrystallization or column chromatography for separation, obtains replacing trans-1 respectively, 2-two acrylonitriles and replacement cis-1,2-two acrylonitriles.Isolated replacement trans-1,2-two acrylonitriles repeat the operation of this step, replace cis-1,2-two acrylonitriles until all being converted into.
Its reaction formula is as follows:
Wherein X represents halogen or class halogen atoms such as fluorine, chlorine, bromine, iodine.
3, replacement cis 1 according to claim 2,2-two acrylonitrile synthetic methods is characterized in that described organic solvent 1 is one or more a mixed solvent of tetracol phenixin, Glacial acetic acid equal solvent.Described cyanating reagent is cuprous cyanide, potassium cyanide, sodium cyanide and other cyanating reagent; Described organic solvent 2 is N, the mixed solvent of one or more of dinethylformamide (DMF), N,N-dimethylacetamide, N-Methyl pyrrolidone, methyl-sulphoxide equal solvent.Described organic solvent 3 is ether, methyl ethyl ether, chloroform, the mixed solvent of one or more of tetracol phenixin, benzene, toluene, tetrahydrofuran (THF), sherwood oil, hexane equal solvent.Described organic solvent 4 is one or more mixed solvents of acetonitrile, propionitrile, methyl alcohol, hexane equal solvent.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109232222A (en) * | 2018-10-19 | 2019-01-18 | 武汉嘉诺康医药技术有限公司 | A kind of preparation method of (E)-octyl- 4- alkene -1,8- diacid |
| CN109400431A (en) * | 2018-08-28 | 2019-03-01 | 浙江工业大学 | A kind of synthetic method of the double bromine compounds of phenylacetylene class compound |
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2004
- 2004-02-20 CN CNA2004100135698A patent/CN1560029A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109400431A (en) * | 2018-08-28 | 2019-03-01 | 浙江工业大学 | A kind of synthetic method of the double bromine compounds of phenylacetylene class compound |
| CN109232222A (en) * | 2018-10-19 | 2019-01-18 | 武汉嘉诺康医药技术有限公司 | A kind of preparation method of (E)-octyl- 4- alkene -1,8- diacid |
| CN109232222B (en) * | 2018-10-19 | 2021-03-23 | 武汉嘉诺康医药技术有限公司 | Preparation method of (E) -octyl-4-ene-1, 8-diacid |
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