CN114276221A - Preparation method of alkyl-substituted diether electron donor - Google Patents
Preparation method of alkyl-substituted diether electron donor Download PDFInfo
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- CN114276221A CN114276221A CN202111638302.8A CN202111638302A CN114276221A CN 114276221 A CN114276221 A CN 114276221A CN 202111638302 A CN202111638302 A CN 202111638302A CN 114276221 A CN114276221 A CN 114276221A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 120
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000006266 etherification reaction Methods 0.000 claims abstract description 17
- 150000002148 esters Chemical class 0.000 claims abstract description 13
- 238000006722 reduction reaction Methods 0.000 claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 150000007530 organic bases Chemical class 0.000 claims abstract description 12
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 11
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 11
- 150000007529 inorganic bases Chemical class 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 8
- 230000009471 action Effects 0.000 claims abstract description 4
- 230000003197 catalytic effect Effects 0.000 claims abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 22
- 239000000725 suspension Substances 0.000 claims description 22
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 20
- -1 lithium aluminum hydride Chemical compound 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 9
- 239000012312 sodium hydride Substances 0.000 claims description 9
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 6
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 claims description 4
- 229910000105 potassium hydride Inorganic materials 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-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
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 5
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract description 3
- 229910000510 noble metal Inorganic materials 0.000 abstract description 3
- 150000002894 organic compounds Chemical class 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 description 24
- 239000000243 solution Substances 0.000 description 23
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 18
- 239000011259 mixed solution Substances 0.000 description 18
- 238000005406 washing Methods 0.000 description 18
- 239000007788 liquid Substances 0.000 description 11
- 230000009286 beneficial effect Effects 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 9
- 238000004817 gas chromatography Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 150000002009 diols Chemical class 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000010791 quenching Methods 0.000 description 6
- 230000000171 quenching effect Effects 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- HYWXVLUNERUJHH-UHFFFAOYSA-N 3-methoxy-4-(methoxymethyl)-2,7-dimethyloctane Chemical compound COCC(C(OC)C(C)C)CCC(C)C HYWXVLUNERUJHH-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 238000007865 diluting Methods 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- HLVFKOKELQSXIQ-UHFFFAOYSA-N 1-bromo-2-methylpropane Chemical compound CC(C)CBr HLVFKOKELQSXIQ-UHFFFAOYSA-N 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- FBWBRAFPAIZRLY-UHFFFAOYSA-N 3-methoxy-4-(methoxymethyl)-2,6-dimethylheptane Chemical compound COCC(CC(C)C)C(OC)C(C)C FBWBRAFPAIZRLY-UHFFFAOYSA-N 0.000 description 3
- PVWCLOAAEFMTLH-UHFFFAOYSA-N 4,4-bis(methoxymethyl)-2,6-dimethylheptane Chemical compound COCC(COC)(CC(C)C)CC(C)C PVWCLOAAEFMTLH-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- YXZFFTJAHVMMLF-UHFFFAOYSA-N 1-bromo-3-methylbutane Chemical compound CC(C)CCBr YXZFFTJAHVMMLF-UHFFFAOYSA-N 0.000 description 2
- YGHRJJRRZDOVPD-UHFFFAOYSA-N 3-methylbutanal Chemical compound CC(C)CC=O YGHRJJRRZDOVPD-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- OFRFGNSZCYDFOH-UHFFFAOYSA-N diethyl 2-(2-methylpropyl)propanedioate Chemical compound CCOC(=O)C(CC(C)C)C(=O)OCC OFRFGNSZCYDFOH-UHFFFAOYSA-N 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- JIWDQJYCCQFDAF-UHFFFAOYSA-N potassium;2-methylpropan-2-olate;oxolane Chemical compound [K+].CC(C)(C)[O-].C1CCOC1 JIWDQJYCCQFDAF-UHFFFAOYSA-N 0.000 description 2
- BKLMTHMYQTUCKU-UHFFFAOYSA-M potassium;n,n-dimethylformamide;hydroxide Chemical compound [OH-].[K+].CN(C)C=O BKLMTHMYQTUCKU-UHFFFAOYSA-M 0.000 description 2
- IOLQAHFPDADCHJ-POHAHGRESA-N (e)-5-methyl-2-propan-2-ylhex-2-enal Chemical compound CC(C)C\C=C(\C=O)C(C)C IOLQAHFPDADCHJ-POHAHGRESA-N 0.000 description 1
- DFMQCGIZWRYGLW-UHFFFAOYSA-N 1-methoxy-2-(methoxymethyl)-5-methylhexane Chemical compound COCC(COC)CCC(C)C DFMQCGIZWRYGLW-UHFFFAOYSA-N 0.000 description 1
- ZGHOZASFRNLRAS-UHFFFAOYSA-N 2-(3-methylbutyl)-2-propan-2-ylpropane-1,3-diol Chemical compound CC(C)CCC(CO)(CO)C(C)C ZGHOZASFRNLRAS-UHFFFAOYSA-N 0.000 description 1
- BHPDSAAGSUWVMP-UHFFFAOYSA-N 3,3-bis(methoxymethyl)-2,6-dimethylheptane Chemical compound COCC(C(C)C)(COC)CCC(C)C BHPDSAAGSUWVMP-UHFFFAOYSA-N 0.000 description 1
- STZPMOIAPWTLNJ-UHFFFAOYSA-N 5-methyl-2-propan-2-ylhexanal Chemical compound CC(C)CCC(C=O)C(C)C STZPMOIAPWTLNJ-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- BYQFBFWERHXONI-UHFFFAOYSA-N diethyl 2-propan-2-ylpropanedioate Chemical compound CCOC(=O)C(C(C)C)C(=O)OCC BYQFBFWERHXONI-UHFFFAOYSA-N 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- GYBMSOFSBPZKCX-UHFFFAOYSA-N sodium;ethanol;ethanolate Chemical compound [Na+].CCO.CC[O-] GYBMSOFSBPZKCX-UHFFFAOYSA-N 0.000 description 1
- ADURZWBRKMHZSG-UHFFFAOYSA-M sodium;n,n-dimethylformamide;hydroxide Chemical compound [OH-].[Na+].CN(C)C=O ADURZWBRKMHZSG-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of diether type organic compounds, in particular to a preparation method of an alkyl-substituted diether type electron donor. The specific reaction steps are as follows: under the catalytic action of organic base, adding a compound b into the compound a to carry out alkylation reaction of carbonyl alpha-carbon to obtain a compound c; carrying out ester reduction reaction on the compound c to obtain a compound d; and (3) carrying out etherification reaction on the compound d and the compound e under the action of inorganic base to obtain a diether compound f. The method adopts the diethyl alkylmalonate as the raw material, can be used for various alkyl-substituted diether electron donors, has simple intermediate treatment process, does not use other noble metal catalysts, and has high product yield, short reaction route and low preparation cost.
Description
Technical Field
The invention relates to the technical field of diether type organic compounds, in particular to a preparation method of an alkyl-substituted diether type electron donor.
Background
In the development of Ziegler-Natta catalysts for olefin polymerization, the use of electron donors plays a very important role.
In 1990, Himont company firstly reported that diether electron donor compounds are introduced into a catalyst system, and the prepared catalyst has obvious advantages compared with fourth generation diester catalysts, is called as fifth generation high-efficiency Ziegler-Natta catalysts, and has few synthetic documents about electron donors of diethers.
At present, patent document CN201010296432.3 discloses a preparation method of a diether type electron donor, which comprises the steps of using 1, 3-methylbutyraldehyde as a raw material to obtain 2-isopropyl-5-methyl-2-hexenal through a condensation reaction, then reducing double bonds through hydrogenation to obtain 2-isopropyl-5-methylhexanal, then reacting with a formaldehyde solution to generate 2-isopropyl-2-isoamyl-1, 3-propanediol, and finally performing an etherification reaction to obtain 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane. The process has the following limitations: 1. because of the structural limitation of the raw materials, the method can only be used for synthesizing 2-isoamyl-1, 3-dimethoxypropane diether compounds; 2. a noble metal catalyst is needed for hydrogenation reaction, so that the synthesis cost is high; 3. long reaction step
In view of the above, there is a need to provide a method for preparing an alkyl-substituted diether type electron donor to overcome the deficiencies of the prior art.
Disclosure of Invention
The invention aims to provide a preparation method of an alkyl-substituted diether electron donor. The method adopts the diethyl alkylmalonate as the raw material, can be used for various alkyl-substituted diether electron donors, has simple intermediate treatment process, does not use other noble metal catalysts, and has high product purity, short reaction route and low preparation cost.
The technical scheme for solving the technical problems is as follows:
the invention provides a preparation method of an alkyl-substituted diether electron donor, which has the following reaction equation:
the specific reaction steps of the above reaction equation are as follows:
step A, as shown in equation 1, under the catalytic action of organic base, adding a compound a into a compound b to carry out alkylation reaction of carbonyl alpha carbon to obtain a compound c;
B. as shown in equation 2, the compound c is subjected to ester reduction reaction to obtain a compound d;
C. as shown in equation 3, carrying out etherification reaction on the compound d and the compound e under the action of inorganic base to obtain a diether compound f;
wherein R is1And R2Are all one of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, n-pentyl, isopentyl and n-hexyl;
R3is a straight or branched chain saturated aliphatic group having 1 to 20 carbon atoms, and X is chlorine, bromine or iodine.
The preparation method of the alkyl-substituted diether electron donor has the beneficial effects that: the preparation method of the diether electron donor provided by the invention uses diethyl alkylmalonate as a raw material, and can prepare the alkyl substituted diether electron donor through alkylation reaction of carbonyl alpha carbon, reduction reaction of the ester and etherification reaction, wherein the yield of the alkyl substituted diether electron donor is high, the preparation process route is short, and the cost is low.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, in the step A, the molar ratio of the compound a to the compound b is 1: 1-1: 6, and the molar ratio of the compound a to the organic base is 1: 1-1: 3.
The beneficial effect of adopting the further scheme is that: the compound a, the compound b and the organic base in the molar ratio can ensure that the compound a fully reacts to generate a compound c, and the organic base plays a role in generating carbocation in the alkylation reaction of the carbon at the alpha position of the carbonyl group.
Further, in step a, the compound c is prepared by the following method: preparing organic base and a first solvent into a first suspension, dropwise adding a compound a, and then dropwise adding a compound b to perform alkylation reaction of carbonyl alpha carbon until the mass concentration of the compound a is less than 5% to obtain a compound c; the organic base is any one of sodium ethoxide, potassium ethoxide, sodium methoxide, potassium tert-butoxide, butyl lithium, phenyl lithium and lithium diisopropylamide, and the first solvent is any one or a mixture of more than two of methanol, ethanol, n-hexane, diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 4-dioxane and methyl tert-butyl ether.
The beneficial effect of adopting the further scheme is that: the organic base and the solvent 1 are prepared into a suspension 1 with the concentration of 15-20%, the suspension can ensure that the compound a is fully dissolved, and the alkylation reaction of the compound a and the compound b at the carbon alpha position of carbonyl group is facilitated to generate the compound c.
Further, in the step A, the temperature of the alkylation reaction of the carbon at the alpha position of the carbonyl group is 10-70 ℃.
The beneficial effect of adopting the further scheme is that: and the alkylation reaction efficiency of the carbonyl alpha-carbon is high at the temperature, and the yield of the compound c is high.
Further, in step B, the compound d is prepared by the following method: preparing a negative hydrogen reducing agent and a second solvent into a second suspension, and adding a compound c into the second suspension to perform ester reduction reaction to obtain a compound d; the negative hydrogen reducing agent is any one of sodium hydride, potassium hydride, sodium borohydride, lithium aluminum hydride, lithium triethylboronate, sodium triethylborohydride, lithium tri-sec-butylborohydride, lithium tri-tert-butylhydride and sodium tri-sec-butylborohydride, and the second solvent is any one or a mixture of more than two of diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 4-dioxane and methyl tert-butyl ether.
The beneficial effect of adopting the further scheme is that: the ester can be reduced by adopting a negative hydrogen reducing agent to prepare the diol of the compound d, the reduction reaction is thorough, and the yield of the compound d is high.
Further, the molar ratio of the compound c to the hydrogen-negative reducing agent is 1: 1-1: 3.
The beneficial effect of adopting the further scheme is that: by adopting the compound c and the negative hydrogen reducing agent in the molar ratio, the ester structure of the compound c can be ensured to be reduced into hydroxyl, and the yield of the compound d is high.
Further, the temperature of the reduction reaction of the ester is 20-100 ℃.
The beneficial effect of adopting the further scheme is that: at this temperature, the reduction reaction efficiency is high, and the yield of the compound d is high.
Further, in step C, the compound f is prepared by the following method: preparing inorganic base and a third solvent into a third suspension, dropwise adding a compound d, and then dropwise adding a compound e for etherification reaction to obtain a compound f; the inorganic base is any one of sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate, and the third solvent is any one or a mixture of more than two of tetrahydrofuran, 2-methyltetrahydrofuran, 1, 4-dioxane, methyl tert-butyl ether, dimethyl sulfoxide and N, N-dimethylformamide.
The beneficial effect of adopting the further scheme is that: under the action of inorganic base, the compound d can react with the compound e to generate the compound f, the etherification reaction is stable, and the yield of the compound f is high.
Further, the molar ratio of the compound d to the compound e is 1: 1-1: 2, and the molar ratio of the compound d to the inorganic base is 1: 1-1: 4.
The beneficial effect of adopting the further scheme is that: the compound d with the molar ratio can fully react to generate the compound f, the compound f can form a diether structure, and the yield of the compound f is high.
Further, the temperature of the etherification reaction is 20-100 ℃.
The beneficial effect of adopting the further scheme is that: at this temperature, the etherification reaction efficiency is high and the yield of the compound f is high.
Detailed Description
The principles and features of this invention are described below in conjunction with specific embodiments, which are set forth merely to illustrate the invention and are not intended to limit the scope of the invention.
Example 1
The preparation process of isopropyl-2-isoamyl-1, 3-dimethoxypropane has the following reaction equation:
wherein R1 is isopropyl, R2 is isoamyl, and R3 is methyl.
The specific reaction steps of the above reaction equation are as follows:
step A, as shown in equation 1, under the protection of inert gas at room temperature, weighing 260g of sodium ethoxide-ethanol solution with the mass concentration of 17%, adding the solution into a 3L reaction bottle, dropwise adding 101g of compound diethyl isopropylmalonate into the reaction bottle, keeping the temperature at 10-35 ℃, and stirring for 2-4 hours after the dropwise addition is finished; gradually dripping 90.5g of compound b bromo-isopentane into a reaction bottle, monitoring the reaction progress through gas chromatography analysis, and stopping dripping the compound b bromo-isopentane when the mass concentration of the compound a diethyl isopropylmalonate is less than 5% to prepare a reaction mixed solution 1; filtering and separating the reaction mixed solution 1, and distilling the filtrate obtained by filtering and separating under vacuum and reduced pressure to obtain 125g of a compound c;
step B, as shown in equation 2, diluting 21g of lithium aluminum hydride with tetrahydrofuran to prepare 15-20% mass concentration lithium aluminum hydride-tetrahydrofuran suspension, dropwise adding 105g of the compound c prepared in the step A into the lithium aluminum hydride-tetrahydrofuran suspension to perform ester reduction reaction, controlling the reaction temperature to be less than 60 ℃ in the process of dropwise adding the compound c, and after the dropwise adding of the compound c is finished, keeping the temperature at 60 ℃ to react for 1-2h to prepare a reaction mixed solution 2; adding the reaction mixed solution 2 into a sodium hydroxide aqueous solution for quenching, filtering and separating after the quenching reaction is finished, washing a solid obtained by filtering and separating for 2-3 times by using tetrahydrofuran, collecting tetrahydrofuran washing liquid, mixing the tetrahydrofuran washing liquid with a liquid phase obtained by filtering and separating, concentrating under reduced pressure to obtain 66g of a diol crude product containing a compound d, and diluting the diol crude product to a diol solution containing the compound c with the molar concentration of 20-25% by using tetrahydrofuran for later use.
Step C, as shown in equation 3, under the protection of argon, weighing 30g of sodium hydride containing 60% by mass of mineral oil, placing the sodium hydride in a 1.0L dry reaction bottle, adding tetrahydrofuran to dilute the sodium hydride to prepare a sodium hydride-tetrahydrofuran suspension with the mass concentration of the sodium hydride of 20-30%, then dropwise adding the glycol solution prepared in the step B into the sodium hydride suspension to carry out etherification reaction, introducing chloromethane gas as a compound e in the dropwise adding process of the glycol solution, and controlling the temperature of the etherification reaction at 20-40 ℃ until the dropwise adding of the glycol solution is finished to prepare a reaction mixed solution 3 containing a product compound f; and (3) filtering and separating the reaction mixed solution 3, washing the solid obtained by filtering and separating with n-hexane for 2-3 times, collecting a n-hexane washing solution, mixing the n-hexane washing solution with the liquid phase obtained by filtering and separating, and concentrating and distilling to obtain 68g of solution containing the compound f isopropyl-2-isoamyl-1, 3-dimethoxypropane.
In this example, the properties, mass spectrum and gas chromatography of the isopropyl-2-isoamyl-1, 3-dimethoxypropane product are shown below:
1HNMR(400MHz，CDCl3)δ0.83ppm(t,J＝8.5Hz,12H),1.14ppm(m，2H)，1.32ppm(m,2H),1.45ppm(m,2H),3.24ppm(s,4H)，3.28ppm(s,6H)；
colorless liquid, 68g, SE54 column gas chromatography test purity 98.5%.
Example 2
The reaction equation of this example is the same as that of example 1:
in contrast to example 1, R1 is isopropyl, R2 is isobutyl, and R3 is methyl.
The specific preparation procedure for isopropyl-2-isobutyl-1, 3-dimethoxypropane of this example is as follows:
step A, weighing 1532g of potassium tert-butoxide-tetrahydrofuran solution with the mass concentration of 13.05% under the protection of inert gas at room temperature, adding the solution into a 3L reaction bottle, dropwise adding 296g of compound a diethyl isobutylmalonate into the reaction bottle, keeping the temperature at 10-35 ℃, and stirring for 2-4 hours after the dropwise addition is finished; dropwise adding 201g of compound b bromoisopropane into a reaction bottle, monitoring the reaction progress through gas chromatography analysis, and stopping dropwise adding compound b bromoisobutane when the mass concentration of compound a isobutyl diethyl malonate is less than 2%, so as to prepare a reaction mixed solution 1; filtering and separating the reaction mixed solution 1, and distilling the filtrate obtained by filtering and separating under vacuum and reduced pressure to obtain 282g of a compound c;
step B, diluting 52g of sodium borohydride with tetrahydrofuran to prepare 20% sodium borohydride-tetrahydrofuran suspension, dropwise adding 200g of the compound c prepared in the step A into the sodium borohydride-tetrahydrofuran suspension, and performing ester reduction reaction to prepare a reaction mixed solution 2; adding the reaction mixed solution 2 into a sodium hydroxide aqueous solution for quenching, filtering and separating after the quenching reaction is finished, washing the solid obtained by filtering and separating for 2-3 times by using tetrahydrofuran, collecting tetrahydrofuran washing liquid, mixing the tetrahydrofuran washing liquid with the liquid phase obtained by filtering and separating, and concentrating under reduced pressure to obtain 124g of crude diol containing the compound d.
Step C, under the protection of argon, weighing 23g of sodium hydroxide solid, placing the sodium hydroxide solid in a 1.0L dry reaction bottle, adding N, N-dimethylformamide to dilute the sodium hydroxide to prepare a sodium hydroxide-N, N-dimethylformamide suspension with the mass concentration of 20-30% of the sodium hydroxide, then dropwise adding the glycol solution prepared in the step B into the sodium oxide-N, N-dimethylformamide suspension to perform etherification reaction, introducing a compound e bromomethane gas in the dropwise adding process of the glycol solution, and controlling the temperature of the etherification reaction at 40-60 ℃ until the dropwise adding of the glycol solution is completed to prepare a reaction mixed solution 3 containing a product compound f; and (3) filtering and separating the reaction mixed solution 3, washing the solid obtained by filtering and separating with n-hexane for 2-3 times, collecting n-hexane washing liquid, mixing the n-hexane washing liquid with the liquid phase obtained by filtering and separating, and concentrating and distilling to obtain 123g of solution containing the compound f isopropyl-2-isobutyl-1, 3-dimethoxypropane.
In this example, the properties, mass spectrum and gas chromatography of the isopropyl-2-isobutyl-1, 3-dimethoxypropane product are shown below:
1HNMR(400MHz，CDCl3)δ0.83ppm(t,J＝8.5Hz,12H),1.14ppm(m，2H)，1.32ppm(m,2H),1.45ppm(m,2H),3.24ppm(s,4H)，3.28ppm(s,6H)；
colorless liquid, 123g, SE54 column test purity 98.4%.
Example 3
The reaction equation of the preparation process of 4, 4-bis (methoxymethyl) -2, 6-dimethylheptane in this example is the same as that in example 1:
in contrast to example 1, R1 is isobutyl, R2 is isobutyl and R3 is methyl.
The specific preparation procedure for 4, 4-bis (methoxymethyl) -2, 6-dimethylheptane of this example was as follows:
A. weighing 1532g of potassium tert-butoxide-tetrahydrofuran solution with the mass concentration of 13.05 percent under the protection of inert gas at room temperature, adding the solution into a 3L reaction bottle, dropwise adding 296g of compound a diethyl isobutylmalonate into the reaction bottle, keeping the temperature at 10-35 ℃, and stirring for 2-4h after the dropwise addition is finished; dropping 225g of compound b bromo-isobutane into the reaction bottle, monitoring the reaction progress through gas chromatography analysis, and stopping dropping compound b bromo-isobutane when the mass concentration of compound a isobutyl diethyl malonate is less than 5%, so as to prepare a reaction mixed solution 1; filtering and separating the reaction mixed solution 1, and distilling the filtrate obtained by filtering and separating under vacuum and reduced pressure to obtain 412g of a compound c;
B. diluting 42g of sodium borohydride with tetrahydrofuran to prepare 20% sodium borohydride-tetrahydrofuran suspension, dropwise adding 200g of the compound c prepared in the step A into the sodium borohydride-tetrahydrofuran suspension, and performing ester reduction reaction to prepare a reaction mixed solution 2; adding the reaction mixed solution 2 into a sodium hydroxide aqueous solution for quenching, filtering and separating after the quenching reaction is finished, washing the solid obtained by filtering and separating for 2-3 times by using tetrahydrofuran, collecting tetrahydrofuran washing liquid, mixing the tetrahydrofuran washing liquid with the liquid phase obtained by filtering and separating, and concentrating under reduced pressure to obtain 124g of crude diol containing the compound d.
C. Under the protection of argon, weighing 30g of potassium hydroxide solid, placing the solid in a 1.0L dry reaction bottle, adding N, N-dimethylformamide to dilute the potassium hydroxide to prepare a potassium hydroxide-N, N-dimethylformamide suspension with the mass concentration of the potassium hydroxide being 20-30%, then dropwise adding the glycol solution prepared in the step B into the potassium hydroxide-N, N-dimethylformamide suspension to perform etherification reaction, introducing bromomethane gas of a compound e in the dropwise adding process of the glycol solution, controlling the temperature of the etherification reaction at 40-60 ℃ until the dropwise adding of the glycol solution is completed, and preparing a reaction mixed solution 3 containing a product compound f; and (3) filtering and separating the reaction mixed solution 3, washing the solid obtained by filtering and separating with n-hexane for 2-3 times, collecting a n-hexane washing solution, mixing the n-hexane washing solution with the liquid phase obtained by filtering and separating, and concentrating and distilling to obtain 114g of solution containing the compound f isopropyl-2-isoamyl-1, 3-dimethoxypropane.
In this example, the properties, mass spectrum and gas chromatography of the 4, 4-bis (methoxymethyl) -2, 6-dimethylheptane product were all tested as follows:
1HNMR(400MHz，CDCl3)δ0.92ppm(d,J＝8.2Hz,12H),1.17ppm(d,J＝12.5Hz,4H),1.75ppm(m,2H),3.02ppm(s,6H),3.72ppm(s,4H)；
colorless liquid, 114g, SE54 gas chromatography column test purity 98.7%.
The experimental results show that: in embodiments 1 to 3, the diether electron donor can be prepared by the preparation method of the alkyl-substituted diether electron donor, and the product has high purity, short reaction route and low preparation cost.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of an alkyl-substituted diether electron donor is characterized in that the reaction equation is as follows:
the specific reaction steps of the above reaction equation are as follows:
step A: as shown in equation 1, under the catalytic action of an organic base, adding the compound a into the compound b to perform an alkylation reaction of carbonyl alpha carbon, so as to obtain a compound c;
and B: as shown in equation 2, the compound c is subjected to ester reduction reaction to obtain a compound d;
and C: as shown in equation 3, carrying out etherification reaction on the compound d and the compound e under the action of inorganic base to obtain a diether compound f;
wherein R is1And R2Are any one of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, n-pentyl, isopentyl and n-hexyl;
R3is a straight-chain or branched saturated aliphatic group having 1 to 20 carbon atoms, and X is any one of chlorine, bromine and iodine.
2. The method for preparing an alkyl-substituted diether electron donor according to claim 1, wherein in the step A, the molar ratio of the compound a to the compound b is 1: 1-1: 6, and the molar ratio of the compound a to the organic base is 1: 1-1: 3.
3. The process for the preparation of alkyl-substituted diether type electron donors according to claim 1 or 2, characterized in that in step a, said compound c is prepared by: preparing organic base and a first solvent into a first suspension, dropwise adding a compound a, and then dropwise adding a compound b to perform alkylation reaction of carbonyl alpha carbon until the mass concentration of the compound a is less than 5% to obtain a compound c; the organic base is any one of sodium ethoxide, potassium ethoxide, sodium methoxide, potassium tert-butoxide, butyl lithium, phenyl lithium and lithium diisopropylamide, and the first solvent is any one or a mixture of more than two of methanol, ethanol, n-hexane, diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 4-dioxane and methyl tert-butyl ether.
4. The method for preparing an alkyl-substituted diether electron donor according to claim 3, wherein the temperature of the alkylation reaction of the carbon at the α -position of the carbonyl group is 10-70 ℃.
5. The method for preparing an alkyl-substituted diether type electron donor according to claim 1, wherein in step B, the compound d is prepared by the following method: preparing a negative hydrogen reducing agent and a second solvent into a second suspension, and adding a compound c into the second suspension to perform ester reduction reaction to obtain a compound d; the negative hydrogen reducing agent is any one of sodium hydride, potassium hydride, sodium borohydride, lithium aluminum hydride, lithium triethylboronate, sodium triethylborohydride, lithium tri-sec-butylborohydride, lithium tri-tert-butylhydride and sodium tri-sec-butylborohydride, and the second solvent is any one or a mixture of more than two of diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 4-dioxane and methyl tert-butyl ether.
6. The method for preparing an alkyl-substituted diether electron donor according to claim 5, wherein the molar ratio of the compound c to the hydrogen-negative reducing agent is 1:1 to 1: 3.
7. The method for preparing an alkyl-substituted diether electron donor according to claim 5, wherein the temperature of the reduction reaction of the ester is 20-100 ℃.
8. The method for preparing an alkyl-substituted diether type electron donor according to claim 1, wherein in step C, the compound f is prepared by: preparing inorganic base and a third solvent into a third suspension, dropwise adding a compound d, and then dropwise adding a compound e for etherification reaction to obtain a compound f; the inorganic base is any one of sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate, and the third solvent is any one or a mixture of more than two of tetrahydrofuran, 2-methyltetrahydrofuran, 1, 4-dioxane, methyl tert-butyl ether, dimethyl sulfoxide and N, N-dimethylformamide.
9. The method for preparing an alkyl-substituted diether electron donor according to claim 8, wherein the molar ratio of the compound d to the compound e is 1: 1-1: 2, and the molar ratio of the compound d to the inorganic base is 1: 1-1: 4.
10. The method for preparing an alkyl-substituted diether electron donor according to claim 8, wherein the temperature of the etherification reaction is 20 to 100 ℃.
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