CN115677653B - Method for preparing thiophene derivative - Google Patents
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- CN115677653B CN115677653B CN202110863057.4A CN202110863057A CN115677653B CN 115677653 B CN115677653 B CN 115677653B CN 202110863057 A CN202110863057 A CN 202110863057A CN 115677653 B CN115677653 B CN 115677653B
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- 238000000034 method Methods 0.000 title claims abstract description 33
- 150000003577 thiophenes Chemical class 0.000 title claims abstract description 14
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims abstract description 51
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims abstract description 42
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 15
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229930192474 thiophene Natural products 0.000 claims abstract description 12
- -1 thiophene compound Chemical class 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000654 additive Substances 0.000 claims description 11
- 230000000996 additive effect Effects 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-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
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 6
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 6
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 3
- BBFCIBZLAVOLCF-UHFFFAOYSA-N pyridin-1-ium;bromide Chemical compound Br.C1=CC=NC=C1 BBFCIBZLAVOLCF-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- NRTLTGGGUQIRRT-UHFFFAOYSA-N triethylazanium;bromide Chemical compound [Br-].CC[NH+](CC)CC NRTLTGGGUQIRRT-UHFFFAOYSA-N 0.000 claims description 3
- MNZMECMQTYGSOI-UHFFFAOYSA-N acetic acid;hydron;bromide Chemical compound Br.CC(O)=O MNZMECMQTYGSOI-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical group FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 1
- 229910052794 bromium Inorganic materials 0.000 claims 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 239000000460 chlorine Chemical group 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Chemical group 0.000 claims 1
- 229910052740 iodine Inorganic materials 0.000 claims 1
- 239000011630 iodine Chemical group 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims 1
- 238000010189 synthetic method Methods 0.000 abstract description 2
- 238000005580 one pot reaction Methods 0.000 abstract 1
- 238000001228 spectrum Methods 0.000 description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 20
- 229910052799 carbon Inorganic materials 0.000 description 20
- 229910052739 hydrogen Inorganic materials 0.000 description 20
- 239000001257 hydrogen Substances 0.000 description 20
- 238000004896 high resolution mass spectrometry Methods 0.000 description 19
- 230000005311 nuclear magnetism Effects 0.000 description 17
- 239000007858 starting material Substances 0.000 description 8
- 230000002194 synthesizing effect Effects 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- OOCCDEMITAIZTP-DAXSKMNVSA-N (Z)-cinnamyl alcohol Chemical class OC\C=C/C1=CC=CC=C1 OOCCDEMITAIZTP-DAXSKMNVSA-N 0.000 description 1
- 150000004808 allyl alcohols Chemical class 0.000 description 1
- 239000002259 anti human immunodeficiency virus agent Substances 0.000 description 1
- 230000003178 anti-diabetic effect Effects 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 229940125715 antihistaminic agent Drugs 0.000 description 1
- 239000000739 antihistaminic agent Substances 0.000 description 1
- 239000002246 antineoplastic agent Substances 0.000 description 1
- 229940041181 antineoplastic drug Drugs 0.000 description 1
- 239000003435 antirheumatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000000041 non-steroidal anti-inflammatory agent Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention relates to a synthetic method of a substituted thiophene compound. Specifically, allyl alcohol is prepared by a one-pot method under the action of dimethyl sulfoxide and a raw material containing hydrogen bromide. The invention starts from simple and easily available raw materials to obtain a series of substituted thiophene compounds.
Description
Technical Field
The invention relates to a method for synthesizing thiophene derivative compounds.
Background
Thiophene is one of the most common aromatic five-membered heterocycles. Thiophene is widely used in various functional organic materials due to its unique properties, and has unique physiological activity in medicines, and important roles in the development of anti-inflammatory analgesics, anti-AIDS drugs, antirheumatic drugs, antihistamines, antidiabetics, anticancer drugs and the like. In addition, thiophene can also be used in the fields of synthesizing novel dyes, fragrances, high polymer materials, chemical reagents and the like. In conventional methods for synthesizing thiophenes, highly functionalized starting materials are often required, which greatly limits the efficiency of synthesizing substituted thiophenes.
Compared with the prior synthetic method of the substituted thiophene, the method has the advantages that the raw materials are simple and easy to obtain, and the substituted thiophene compound is directly constructed by using allyl alcohol by taking dimethyl sulfoxide as an oxidant and a sulfur source.
In summary, a method for directly synthesizing high added value substituted thiophene compounds by taking dimethyl sulfoxide as a sulfur source and an oxidant from simple and easily available raw materials is described.
Disclosure of Invention
The invention aims to provide a method for synthesizing a substituted thiophene derivative.
Reaction equation 1: synthesis of substituted thiophene derivatives
The specific operation steps are as follows (reaction equation 1):
carrying out reaction in a reactor, sequentially adding allyl alcohol 1, DMSO, a raw material containing HBr, an additive and a solvent, and reacting at 80-120 ℃ for 6-18 hours; after the reaction, the substituted thiophene derivative 2 is separated.
Allyl alcohol 1 and DMSO, and HBr-containing raw material in a molar ratio of 1:1-3:1-3, preferably 1:1.5-2:2-3.
The HBr-containing raw material is one or two of 39-41% of aqueous hydrogen bromide solution by mass fraction, 32-34% of aqueous hydrogen bromide acetic acid solution by mass fraction, triethylamine hydrobromide and pyridine hydrobromide, and preferably 39-41% of aqueous hydrogen bromide solution by mass fraction.
The additive is one or more than two of potassium bromide, sodium bromide and lithium bromide; the amount of the additive is 0.20 to 5.0 molar equivalents or molar multiples of the amount of allyl alcohol 1, preferably 0.5 to 2.0 molar equivalents or molar multiples.
The solvent is one or more of nitromethane, 1, 2-dichloroethane, ethyl acetate, acetonitrile, toluene, tetrahydrofuran, 1, 4-dioxane and ethylene glycol dimethyl ether, preferably ethyl acetate; the solvent is used in an amount of 0.1 to 5.0 ml, preferably 1.0 to 2.0 ml, per millimole of allyl alcohol 1.
The invention has the following advantages:
firstly, the reaction raw materials of allyl alcohol, dimethyl sulfoxide and hydrogen bromide are all simple, easy to obtain and cheap, and the reaction system is simple. And secondly, dimethyl sulfoxide is used as a sulfur source and is used as an oxidant in the reaction, so that the addition of an additional oxidant is avoided, and the reaction is more green. Finally, the obtained raw material has high added value of substituted thiophene, and can be used for synthesizing various natural products, medicines, organic functional materials and the like.
Detailed Description
For a better understanding of the present invention, it is illustrated by the following examples. The starting materials and results for examples 1-19 are shown in Table 1.
TABLE 1 reaction results of various substituted allylic alcohols
As can be seen from the results in table 1: phenyl allyl alcohol compounds containing different substituent groups on phenyl can be well converted into thiophene compounds under the action of dimethyl sulfoxide and raw materials containing hydrogen bromide.
Example 1
The reaction is carried out in a reactor, allyl alcohol 1 (0.2 mmol), DMSO (0.3 mmol), 40% mass fraction hydrogen bromide aqueous solution (HBr molar amount 0.4 mmol), additive KBr (0.1 mmol) and ethyl acetate (1.0 mL) are added in sequence to react at 100 ℃ for 12 hours; after the reaction is finished, the yield of the high allyl silicon compound 2b is 54% through column chromatography separation, and the compound is subjected to infrared, nuclear magnetism (hydrogen spectrum and carbon spectrum) and high-resolution mass spectrum identification structure.
The detection data are as follows:
2b:White solid,18.6mg,54％yield,R f ＝0.6(petroleum ether). 1 H NMR(400MHz,Chloroform-d)δ7.53–7.50(m,2H),7.43–7.41(m,1H),7.41–7.37(m,2H),7.23(d,J＝7.8Hz,2H),2.39(s,3H)； 13 C NMR(100MHz,Chloroform-d)δ142.45,136.99,133.19,129.61,126.45,126.18,119.77,21.29。
example 2:
the procedure and conditions were the same as in example 1, except that the additive was lithium bromide in an amount of 3.0 molar equivalents (3.0 molar equivalents to 1 allyl alcohol) and the product 2c yield was 52% except that the compound was subjected to infrared, nuclear magnetism (hydrogen spectrum and carbon spectrum), high resolution mass spectrometry to identify the structure, as in example 1.
Example 3:
the procedure and conditions were the same as in example 1, except that the reaction temperature was 80℃and the yield of product 2d was 63% as compared with example 1, and the structure was identified by infrared, nuclear magnetism (hydrogen spectrum and carbon spectrum) and high-resolution mass spectrometry, except for the differences expressed in Table 1.
Example 4:
the procedure and conditions were the same as in example 1, except that the solvent was 1, 4-dioxane, the yield of product 2e was 61% and the structure was identified by infrared, nuclear magnetism (hydrogen spectrum and carbon spectrum), high resolution mass spectrometry, except for the differences expressed in table 1.
Example 5:
the procedure and conditions were the same as in example 1, except that the difference in Table 1 was that DMSO was used in an amount of 2.0 molar equivalents (2.0 molar equivalents based on 1 amount of allyl alcohol) and the yield of product 2f was 74%, and the structure was identified by infrared, nuclear magnetism (hydrogen spectrum and carbon spectrum), high resolution mass spectrometry.
Product 2f can be synthesized as an electrochromic copolymer film (ref.: 1]G.R.d.B.S.Lacerda,C.R.Calado,H.D.R.Calado,J.Solid State Electrochem.2019,23,823-835.).
Example 6:
the procedure and conditions were the same as in example 1, except that the difference expressed in Table 1 was that the 40% by mass aqueous hydrogen bromide was used in an amount of 3.0 molar equivalents (HBr was used in an amount of 3.0 equivalents based on 1 mole of allyl alcohol) and the yield of 2g was 65%, and the compound was subjected to infrared, nuclear magnetic (hydrogen spectrum and carbon spectrum), high-resolution mass spectrometry to identify the structure.
Example 7:
the procedure and conditions were the same as in example 1, except that the solvent was ethylene glycol dimethyl ether, the yield of the product 2h was 72%, and the structure was identified by infrared, nuclear magnetism (hydrogen spectrum and carbon spectrum), high resolution mass spectrometry, except for the differences expressed in table 1.
Example 8:
the procedure and conditions were the same as in example 1, except for the differences expressed in Table 1, the reaction time was 18h, the yield of product 2i was 70%, and the compounds were subjected to infrared, nuclear magnetism (hydrogen spectrum and carbon spectrum), high resolution mass spectrometry.
The product 2i has a certain antifungal activity (ref: [2] M.S. C. Pedras, M.Suchy, biorg. Med. Chem.2006,14, 714-723.).
Example 9:
the procedure and conditions were the same as in example 1, except that the reaction temperature was 90℃and the yield of product 2j was 56% except for the differences expressed in Table 1, and the structure was identified by infrared, nuclear magnetism (hydrogen spectrum and carbon spectrum), high resolution mass spectrometry.
Example 10:
the procedure and conditions were the same as in example 1, except that, except for the differences expressed in Table 1, DMSO was used in an amount of 2.0 molar equivalents (amount of 2.0 molar equivalents to allyl alcohol 1), 40% by mass aqueous hydrogen bromide was used in an amount of 2.0 molar equivalents (HBr molar amount of 2.0 equivalents to allyl alcohol 1), the yield of 2k was 55%, and the structure was identified by nuclear magnetism (hydrogen spectrum and carbon spectrum), high resolution mass spectrometry.
Example 11:
the procedure and conditions were the same as in example 1, except that the solvent was nitromethane and the yield of product 2i was 40% and the structure was identified by infrared, nuclear magnetism (hydrogen and carbon) and high resolution mass spectrometry, except for the differences expressed in table 1.
Example 12:
the procedure and conditions were the same as in example 1, except that the solvent was acetonitrile and the yield of product 2i was 43% and the structure was identified by infrared, nuclear magnetism (hydrogen spectrum and carbon spectrum), high resolution mass spectrometry, except for the differences expressed in table 1.
Example 13:
the procedure and conditions were the same as in example 1, except that the solvent was 1, 2-dichloroethane, the yield of product 2i was 44% and the structure was identified by infrared, nuclear magnetism (hydrogen spectrum and carbon spectrum), high resolution mass spectrometry, except for the differences expressed in table 1.
Example 14:
the procedure and conditions were the same as in example 1, except that the solvent was tetrahydrofuran, the yield of product 2i was 46% and the structure was identified by infrared, nuclear magnetism (hydrogen spectrum and carbon spectrum), high resolution mass spectrometry, except for the differences expressed in table 1.
Example 15:
the procedure and conditions were the same as in example 1, except that the solvent was toluene and the yield of product 2i was 47% and the structure was identified by infrared, nuclear magnetism (hydrogen spectrum and carbon spectrum), high resolution mass spectrometry, except for the differences expressed in table 1.
Example 16:
the procedure and conditions were the same as in example 1, except that the additive was NaBr, the yield of product 2i was 50% and the structure was identified by infrared, nuclear magnetism (hydrogen spectrum and carbon spectrum), high resolution mass spectrometry, except for the differences expressed in table 1.
Example 17:
the procedure and conditions were the same as in example 1, except that the HBr-containing starting material was a 33% by mass solution of hydrogen bromide in acetic acid, the yield of product 2i was 52% and the structure was identified by infrared, nuclear magnetic (hydrogen and carbon) and high resolution mass spectrometry, except for the differences expressed in table 1.
Example 18:
the procedure and conditions were the same as in example 1, except that the HBr-containing starting material was triethylamine hydrobromide and the product 2i yield was 44% and the structure was identified by infrared, nuclear magnetic (hydrogen and carbon) and high resolution mass spectrometry, except for the differences set forth in table 1.
Example 19:
the procedure and conditions were as in example 1, except for the differences described in Table 1, the HBr-containing starting material was pyridine hydrobromide, the product 2i yield was 42%, and the structure was identified by infrared, nuclear magnetism (hydrogen and carbon) and high resolution mass spectrometry.
Comparative example 1:
the starting materials, procedure and conditions used were the same as in example 1, except that, except for the differences expressed in Table 1, no HBr-containing starting materials were added, and no product 2b was obtained.
Comparative example 2:
the starting materials, procedure and conditions used were the same as in example 1, except that no additives were added, the yield of product 2b was 30% and the structure was identified by infrared, nuclear magnetism (hydrogen and carbon) and high resolution mass spectrometry, except for the differences expressed in table 1.
Claims (8)
1. A process for preparing a substituted thiophene compound characterized by:
allyl alcohol 1 and dimethyl sulfoxide (DMSO) shown in the following formula are used as raw materials to generate thiophene derivative 2, and the reaction formula is as follows:
；
wherein R is phenyl or phenyl containing substituent groups, the substituent groups on the phenyl are one or two of methyl, ethyl, tertiary butyl, fluorine, chlorine, bromine, iodine and trifluoromethyl, and the number of the substituent groups on the phenyl is 1-2;
wherein the raw material containing HBr is one or more than two of 39-41% of hydrogen bromide aqueous solution, 32-34% of hydrogen bromide acetic acid solution, triethylamine hydrobromide and pyridine hydrobromide;
the additive is one or more than two of potassium bromide, sodium bromide and lithium bromide.
2. The process for preparing a substituted thiophene compound according to claim 1, wherein:
the specific operation steps are as follows:
carrying out reaction in a reactor, sequentially adding allyl alcohol 1, DMSO, a raw material containing HBr, an additive and a solvent, and reacting at 80-120 ℃ for 6-18 hours; after the reaction, thiophene derivative 2 was isolated.
3. A method according to claim 1 or 2, characterized in that:
the molar usage ratio of the allyl alcohol 1 to the DMSO and the HBr in the raw material containing the HBr is 1:1-3:1-3.
4. A method according to claim 1 or 2, characterized in that:
the amount of the additive is 0.2-5.0 molar equivalents of the amount of the allyl alcohol 1.
5. A method according to claim 1 or 2, characterized in that:
the solvent is one or more than two of nitromethane, 1, 2-dichloroethane, ethyl acetate, acetonitrile, toluene, tetrahydrofuran, 1, 4-dioxane and ethylene glycol dimethyl ether; the solvent is used in an amount of 0.1 to 5.0 ml per millimole of allyl alcohol 1.
6. A method according to claim 3, characterized in that: the molar usage ratio of the allyl alcohol 1 to the DMSO and the HBr in the raw material containing the HBr is 1:1.5-2:2-3.
7. The method according to claim 5, wherein: the amount of the additive is 0.5-2.0 molar equivalents of the amount of the allyl alcohol 1.
8. The method of claim 6, wherein: the solvent is used in an amount of 1.0 to 2.0 ml per millimole of allyl alcohol 1.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2017139940A1 (en) * | 2016-02-18 | 2017-08-24 | 肖丽芳 | Preparation method for graphene/polythiophene/sulfur composite positive electrode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2017139940A1 (en) * | 2016-02-18 | 2017-08-24 | 肖丽芳 | Preparation method for graphene/polythiophene/sulfur composite positive electrode material |
Non-Patent Citations (2)
| Title |
|---|
| Design, synthesis, and antifungal activity of inhibitors of brassilexin detoxification in the plant pathogenic fungus Leptosphaeria maculans;M. Soledade. C. Pedras 等;Bioorganic & Medicinal Chemistry;第14卷;第714-723页 * |
| Highly Efficient Monophosphine-Based Catalyst for the Palladium-Catalyzed Suzuki-Miyaura Reaction of Heteroaryl Halides and Heteroaryl Boronic Acids and Esters;Kelvin Billingsley 等;Journal of American Chemistry Society;第11卷;第3358-3366页 * |
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