CN114890857B - Method for preparing cycloalkane from cyclic alcohol in one step through molecular sieve - Google Patents
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 75
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 75
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 33
- 150000001924 cycloalkanes Chemical class 0.000 title claims abstract description 26
- 125000004122 cyclic group Chemical group 0.000 title claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 69
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 229910052680 mordenite Inorganic materials 0.000 claims abstract description 4
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 39
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 34
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 229910052675 erionite Inorganic materials 0.000 abstract description 2
- -1 propylcyclohexylcyclohexylcyclohexyltoluene Chemical compound 0.000 description 57
- 239000000047 product Substances 0.000 description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 238000002360 preparation method Methods 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 15
- 238000003756 stirring Methods 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 8
- 229910052749 magnesium Inorganic materials 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- ZBTMRBYMKUEVEU-UHFFFAOYSA-N 1-bromo-4-methylbenzene Chemical compound CC1=CC=C(Br)C=C1 ZBTMRBYMKUEVEU-UHFFFAOYSA-N 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- LUMNWCHHXDUKFI-UHFFFAOYSA-N 5-bicyclo[2.2.1]hept-2-enylmethanol Chemical compound C1C2C(CO)CC1C=C2 LUMNWCHHXDUKFI-UHFFFAOYSA-N 0.000 description 4
- YSLROFCMOBCNDL-UHFFFAOYSA-N CCCC(C1CCCCC1)c1ccccc1 Chemical compound CCCC(C1CCCCC1)c1ccccc1 YSLROFCMOBCNDL-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- PSHNPTLDAYUIBE-UHFFFAOYSA-N 2-cyclohexyl-1,3-dimethylbenzene Chemical compound CC1=CC=CC(C)=C1C1CCCCC1 PSHNPTLDAYUIBE-UHFFFAOYSA-N 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- SWDSRPJHMGUNLO-UHFFFAOYSA-N 2-cyclohexyl-2-propylcyclohexan-1-one Chemical compound C(CC)C1(C(CCCC1)=O)C1CCCCC1 SWDSRPJHMGUNLO-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 238000010544 hydroalkylation process reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- QJHIURZXZVAQPR-UHFFFAOYSA-N 1-cyclohexyl-2-propylbenzene Chemical compound CCCC1=CC=CC=C1C1CCCCC1 QJHIURZXZVAQPR-UHFFFAOYSA-N 0.000 description 1
- HNBJZFPJDFJMLP-UHFFFAOYSA-N 1-cyclohexylethylbenzene Chemical class C=1C=CC=CC=1C(C)C1CCCCC1 HNBJZFPJDFJMLP-UHFFFAOYSA-N 0.000 description 1
- AYVWHHOIARKTJG-UHFFFAOYSA-N 2-cyclohexyl-1,3-dipropylbenzene Chemical compound C(CC)C=1C(=C(C=CC1)CCC)C1CCCCC1 AYVWHHOIARKTJG-UHFFFAOYSA-N 0.000 description 1
- XMZQWZJMTBCUFT-UHFFFAOYSA-N 3-bromopropylbenzene Chemical compound BrCCCC1=CC=CC=C1 XMZQWZJMTBCUFT-UHFFFAOYSA-N 0.000 description 1
- VGVHNLRUAMRIEW-UHFFFAOYSA-N 4-methylcyclohexan-1-one Chemical compound CC1CCC(=O)CC1 VGVHNLRUAMRIEW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910010082 LiAlH Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- SNOOUWRIMMFWNE-UHFFFAOYSA-M sodium;6-[(3,4,5-trimethoxybenzoyl)amino]hexanoate Chemical compound [Na+].COC1=CC(C(=O)NCCCCCC([O-])=O)=CC(OC)=C1OC SNOOUWRIMMFWNE-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D309/04—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
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- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
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- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
- C07C2529/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65 containing iron group metals, noble metals or copper
- C07C2529/76—Iron group metals or copper
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- C07C2529/82—Phosphates
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- C07C2601/14—The ring being saturated
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Abstract
The invention relates to a method for preparing cycloalkane from cyclic alcohol in one step by using a molecular sieve, which is characterized in that the method for preparing cycloalkane comprises the following steps: under the protection of inert gas, adding cycloalcohol and a molecular sieve into an organic solvent, and heating for reaction to obtain cycloparaffin, wherein the molecular sieve is a microporous molecular sieve; the molecular sieve is one or a mixture of more of X type, Y type, L type, beta type, mordenite, erionite, CHA, RHO, AEL, TS, SAPO-34, ZSM-5 and ZSM-11. The invention adopts the molecular sieve to prepare the cycloalkane, so that the cycloalkane product mainly has a trans-structure, the stereoselectivity is good, after the reaction is finished, the molecular sieve is filtered out and roasted, the cycloalkane can be recycled, and the production cost can be reduced; the reaction process does not need hydrogen or high pressure, is green and environment-friendly, and is easy to industrialize.
Description
Technical Field
The invention relates to a method for preparing cycloalkane from cycloalkanol by a molecular sieve in one step, belonging to the technical field of organic synthesis.
Background
The preparation of alkanes from alcohols is an important reaction type in organic synthetic chemistry. There are three main approaches:
(1) The alcohol is directly reduced, and the used reducing agents mainly comprise: naBH 4 、R 3 SiH、P 2 I 4 And the like. The reducing agent used in J.O.C53 5143 (1988) is NaBH 4 And CF 3 COOH; the reducing agent used in the document TL2955 (1976) is R 3 SiH and BF 3 (ii) a The reducing agent used in document CL247 (1983) is P 2 I 4 。
(2) From alcohols to sulfonates, which are then reduced to alkanes. The reagent used is C as described in J.O.C34 3667 (1969) 5 H 5 N·SO 3 /LiAlH 4 。
(3) The alkane is prepared by dehydrating the alcohol and then hydrogenating. Propylcyclohexylbenzene is prepared as described in patent CN1807372A, dehydrated in a first step with p-toluenesulphonic acid and then hydrogenated with nickel the product E: Z = 71.7; the patent Jpn.Kokai Tokkyo Koho,2011207782 also prepares the PCH31 by dehydrating and then hydrogenating. PCT int.appl.,2008090780 for preparing PCH3mF is also to dehydrate, hydrogenate, and then transform.
The three methods for preparing alkane from alcohol all have the problems of long reaction steps, low yield and the like. According to the method (1) and the method (2), the product has no stereoselectivity, the used reagent has high toxicity, the reaction process needs anhydrous conditions, and the reaction conditions are very strict; the method (3) is to dehydrate and hydrogenate, if a product with high main selectivity needs to be transformed, the reaction steps are multiple, and pressure equipment and dangerous materials such as hydrogen are also needed.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for preparing cycloalkane from cycloalkanol by a molecular sieve in one step, which has the advantages of mild reaction conditions, no need of high temperature and high pressure conditions, high stereoselectivity of reaction products, high yield and capability of recycling the molecular sieve.
The technical scheme for solving the technical problems is as follows: a method for preparing cycloalkane from cyclic alcohol in one step by using a molecular sieve, wherein the method for preparing cycloalkane comprises the following steps: under the protection of inert gas, adding cycloalcohol and a molecular sieve into an organic solvent, and heating for reaction to obtain cycloparaffin, wherein the structural formula of the cycloalcohol is as follows:
the structural formula of the cycloalkane is as follows:
wherein m =0 or 1,n =0 or 1,p =0, 1, 2 or 3;
R 1 and R 2 Are respectively H and C 1 -C 20 Straight or branched alkyl or alkoxy, C 3 -C 20 Cycloalkane of (C) 4 -C 20 All ofStraight or branched cycloalkanes, F, CN, CF 3 、Cl、Br、CHF 2 、CF 3 O、NCS、SCN；
A is-CH 2 CH 2 -or a single bond;
R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 are each H, F, cl or CF 3 ；
The cyclic alcohol and the cyclane have structural formulas in which the ring is not substituted by heteroatoms or substituted by heteroatoms at different positions.
Furthermore, the molecular sieve is one or a mixture of more of X type, Y type, L type, beta type, mordenite, erionite, CHA, RHO, AEL, TS, SAPO-34, ZSM-5 and ZSM-11.
Further, the molecular sieve type is H type, NH4 type or modified metal ion type.
Further, the BETA-type molecular sieve is HBETA, NH4BETA or MBETA, wherein M represents any one or more metals, such as iron, copper, manganese, nickel, lanthanum, cerium and the like.
Further, the cyclic alcohol is selected from the following structural formulas:
the cycloalkane is selected from the following structural formulae:
further, the heteroatom substitution at different positions is specifically: o replaces CH 2 Or NH in place of CH 2 。
Further, the organic solvent is one or more of n-heptane, petroleum ether, benzene, toluene, xylene, THF, 2-MeTHF, methanol, ethanol, isopropanol, butanol, isobutanol, and tert-butanol.
Further, the temperature of the heating reaction is 40-150 ℃.
Further, the temperature of the heating reaction is 90-120 ℃. The reaction temperature is low, the reaction is not carried out or the conversion rate is low, the boiling point of the solvent is generally selected as the reaction temperature, and the pressure reaction can be carried out on the low-boiling point solvent.
Further, the mass ratio of the molecular sieve to the cyclic alcohol is (1-5): 1.
the invention has the beneficial effects that:
(1) The invention uses molecular sieve to prepare cyclic alcohol into cyclic alkane, and the molecular sieve has acidity and dehydration function, and has stereoselectivity and can provide hydrogen, thus obtaining the product with stereoselectivity. The cycloparaffin is mainly used in the field of liquid crystal materials, the most needed is cycloparaffin with a trans-structure, the invention adopts the molecular sieve to prepare the cycloparaffin, the unique pore diameter in the molecular sieve is favorable for the stereoselectivity of the reaction, the cycloparaffin product mainly has the trans-structure, the stereoselectivity is better, and particularly for products with similar structures, such as propyl cyclohexyl propyl benzene and the like;
(2) After the reaction is finished, the molecular sieve is filtered out and roasted, so that the molecular sieve can be recycled, and the production cost can be reduced;
(3) In the method, hydrogen is not needed in the reaction process, high-pressure conditions are not needed, the two-step reaction of dehydration and hydroalkylation can be completed by a one-step method through the selected molecular sieve, the required cyclane is finally obtained, and the reaction process is green and environment-friendly and is easy to industrialize;
(4) In the traditional conventional method, naphthenic hydrocarbon is prepared from cyclic alcohol, different catalysts are needed in the dehydration process and the hydroalkylation process, the dehydration process and the hydroalkylation process need to be carried out in two steps, hydrogen is needed in the hydrogenation process, the hydrogenation process needs to be carried out in a hydrogenation kettle, the condition requirement of the hydrogenation kettle is higher, the equipment investment is large, the hydrogen is extremely flammable and explosive gas, the danger degree is extremely high, the operation is very strict, and the requirement on the production environment is extremely high. In the invention, the cycloparaffin with the required three-dimensional structure can be prepared by one step only by using the molecular sieve, the preparation process is simpler and more convenient, dangerous raw materials are not required to be used, high-cost equipment is not required to be arranged, the raw materials, equipment and operation cost are reduced, and the method is more suitable for industrialization.
Drawings
FIG. 1 is a GC-MS detection spectrum of propylcyclohexylcyclohexylcyclohexyltoluene product described in example 1;
FIG. 2 is a 1HNMR detection profile of the propylcyclohexylcyclohexylcyclohexyltoluene product described in example 1;
FIG. 3 is a 13CNMR detection profile of the propylcyclohexylcyclohexylcyclohexyltoluene product described in example 1;
Detailed Description
The present invention will be described in detail with reference to the following embodiments in order to make the aforementioned objects, features and advantages of the invention more comprehensible. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Example 1
Preparation of propylcyclohexylcyclohexylcyclohexyltoluene
The reaction equation is as follows:
adding 11.7g magnesium strips into a dry 2L three-necked bottle, and introducing nitrogen for replacement for 30min. 82.1g of p-bromotoluene was dissolved in 246.3g of THF, and an appropriate amount was added dropwise to the system, followed by heating to initiate the reaction. The residual solution is dripped at the temperature of 40-50 ℃ and the temperature of 40-50 ℃ is controlled for 2 hours after about 1.5 hours of dripping. The system is light black and clear, and a small amount of magnesium strips are left. 89g of propylcyclohexyl cyclohexanone is dissolved in 178g of toluene, the internal temperature is controlled to be 50-60 ℃ and is dripped into the system, the reaction releases heat, after about 1.5h of dripping, the system has no obvious color state change, and the internal temperature is kept at 50-60 ℃ for 2h of reaction. The system is slowly poured into a 2L beaker containing 48g of concentrated hydrochloric acid and 240g of ice water, stirred and hydrolyzed at 30-40 ℃ for 30min, and the system is slightly yellow and clear. After stirring uniformly, the mixture is transferred to a liquid separation funnel for standing and layering, a colorless clear water phase at the lower layer is discharged, and 200g of deionized water is washed for 2 to 3 times until the pH value is approximately equal to 7, so that the solution of the cyclol in toluene and THF is obtained.
A2L three-necked flask is added with a solution of cyclic alcohol in toluene and THF, 440g (3.5 g/g of the theoretical amount of cyclic alcohol) of H beta molecular sieve is added under stirring, nitrogen is introduced, and the mixture is stirred and heated to obtain a dark brown turbid system. Setting the bath temperature at 110 ℃, continuously refluxing and dividing water at the internal temperature of 90-100 ℃, gradually discharging the evaporated THF and water, after about 2 hours, no water is evaporated, raising the internal temperature to over 106 ℃, keeping the internal temperature at 108-110 ℃, refluxing and keeping the temperature for 4 hours, after the reaction is finished, filtering to remove a molecular sieve and removing a solvent to obtain the propylcyclohexyl toluene product.
The conversion of propylcyclohexylcyclohexylcyclohexyltoluene in this example was: greater than 99.5%;
this example gives the cis yield in propylcyclohexylcyclohexylcyclohexyltoluene product: 5.5%, trans yield: 92.5 percent.
The GC-MS detection pattern of the propylcyclohexyl toluene product is shown in figure 1, and 1HNMR and 13CNMR are shown in figures 2-3.
Example 2
Preparation of propylcyclohexylcyclohexylcyclohexyltoluene
This example prepared propylcyclohexylcyclohexylcyclohexylcyclohexyltoluene by the same procedure as in example 1, except that: the recovered H β molecular sieve was used in place of the H β molecular sieve in example 1 (the recovered H β molecular sieve was obtained after the H β molecular sieve in example 1 was calcined at 550 ℃ and used in the reaction of this example).
The conversion of propylcyclohexylcyclohexylcyclohexyltoluene in this example was: greater than 99.5%;
this example gives the cis yield in propylcyclohexylcyclohexylcyclohexyltoluene product: 6.1%, trans yield: 90.5 percent.
Example 3
Preparation of propylcyclohexylcyclohexylcyclohexyltoluene
This example prepared propylcyclohexylcyclohexylcyclohexyltoluene by the same method as in example 1 except for the difference: fe beta molecular sieve was used instead of H beta molecular sieve in example 1.
The conversion of propylcyclohexylcyclohexylcyclohexyltoluene in this example was: greater than 99.5%;
this example gives the cis yield in propylcyclohexylcyclohexylcyclohexyltoluene product: 5.1%, trans yield: 92.7 percent.
Example 4
Preparation of propylcyclohexylcyclohexylcyclohexyltoluene
This example prepared propylcyclohexylcyclohexylcyclohexylcyclohexyltoluene by the same procedure as in example 1, except that: ZSM-5 molecular sieve of NH4 type is used instead of the H beta molecular sieve in example 1.
The conversion of propylcyclohexylcyclohexylcyclohexyltoluene in this example was: greater than 99.5%;
this example gives the cis yield in propylcyclohexylcyclohexylcyclohexyltoluene product: 6.8%, trans yield: 91.0 percent.
Example 5
Preparation of propylcyclohexylcyclohexylcyclohexyltoluene
This example prepared propylcyclohexylcyclohexylcyclohexylcyclohexyltoluene by the same procedure as in example 1, except that: the H beta molecular sieve in example 1 was replaced with the Y molecular sieve in H form.
The conversion of propylcyclohexylcyclohexylcyclohexyltoluene in this example was: greater than 99.5%;
this example gives the cis yield in propylcyclohexylcyclohexylcyclohexyltoluene product: 8.0%, trans yield: 89.6 percent.
Example 6
Preparation of propylcyclohexylcyclohexylcyclohexyltoluene
This example prepared propylcyclohexylcyclohexylcyclohexylcyclohexyltoluene by the same procedure as in example 1, except that: mordenite in the H form was used instead of the H beta molecular sieve in example 1.
The conversion of propylcyclohexylcyclohexylcyclohexyltoluene in this example was: greater than 99.5%;
cis yield in propylcyclohexylcyclohexyltoluene product of this example: 7.2%, trans yield: 89.2 percent.
Example 7
Preparation of propylcyclohexylcyclohexylcyclohexyltoluene
This example prepared propylcyclohexylcyclohexylcyclohexylcyclohexyltoluene by the same procedure as in example 1, except that: instead of the H beta molecular sieve in example 1, the SAPO-34 molecular sieve in H form was used.
The conversion of propylcyclohexylcyclohexylcyclohexyltoluene in this example was: greater than 99.5%;
this example gives the cis yield in propylcyclohexylcyclohexylcyclohexyltoluene product: 8.3%, trans yield: 88.2 percent.
Example 8
Preparation of propylcyclohexylcyclohexylcyclohexyltoluene
This example prepared propylcyclohexylcyclohexylcyclohexyltoluene by the same method as in example 1 except for the difference: the amount of molecular sieve H β added was 625g (5 g/g theoretical amount of cyclic alcohol).
The conversion of propylcyclohexylcyclohexylcyclohexyltoluene in this example was: greater than 99.5%;
this example gives the cis yield in propylcyclohexylcyclohexylcyclohexyltoluene product: 5.5%, trans yield: 92.3 percent.
Example 9
Preparation of propylcyclohexylcyclohexylcyclohexyltoluene
This example prepared propylcyclohexylcyclohexylcyclohexylcyclohexyltoluene by the same procedure as in example 1, except that: the amount of H.beta.molecular sieve added was 125g (1 g/g theoretical amount of cyclic alcohol).
The conversion of propylcyclohexylcyclohexylcyclohexyltoluene in this example was: greater than 99.5%;
this example gives the cis yield in propylcyclohexylcyclohexylcyclohexyltoluene product: 5.4%, trans yield: 92.0 percent.
Example 10
Preparation of propylcyclohexylcyclohexylcyclohexyltoluene
The reaction equation is as follows:
the main differences from example 1 are: use of
Instead of the former
The preparation method comprises the following specific steps:
2L three-necked bottle
In a toluene solution of (b), wherein
The amount of (2) was 125g, 440g (3.5 g/g theoretical amount of cycloolefin) of H.beta.molecular sieve was added with stirring, and the mixture was heated with stirring under nitrogen to give a dark brown turbid system. Setting the bath temperature at 110 ℃, continuously refluxing and dividing water at the internal temperature of 90-100 ℃, gradually discharging the distilled water, after about 2 hours, no water is distilled, raising the internal temperature to above 106 ℃, keeping the internal temperature at 108-110 ℃, refluxing and keeping the temperature for 4 hours, after the reaction is finished, filtering to remove a molecular sieve and removing a solvent to obtain the propylcyclohexyl toluene product. />
The conversion of propylcyclohexylcyclohexylcyclohexyltoluene in this example was: greater than 99.5%;
this example gives the cis yield in propylcyclohexylcyclohexylcyclohexyltoluene product: 5.3%, trans yield: 92.8 percent.
Example 11
Preparation of propylcyclohexylcyclohexylcyclohexyltoluene
The reaction equation is as follows:
drying 2L three-necked bottle, adding 11.7g magnesium strip, and introducing nitrogen for replacement for 30min. 82.1g of p-bromotoluene was dissolved in 246.3g of THF, and an appropriate amount was added dropwise to the system, followed by heating to initiate a reaction. And (3) dropwise adding the residual solution at the internal temperature of 40-50 ℃, keeping the internal temperature of 40-50 ℃ for 2 hours after dropwise adding is finished for about 1.5 hours. The system is light black and clear, and a small amount of magnesium strips are left. 89g of propylcyclohexyl cyclohexanone is dissolved in 178g of toluene, the internal temperature is controlled to be 50-60 ℃ and is dripped into the system, the reaction releases heat, after about 1.5h of dripping, the system has no obvious color state change, and the internal temperature is kept at 50-60 ℃ for 2h of reaction. Slowly pouring the system into a 2L beaker containing 48g of concentrated hydrochloric acid and 240g of ice water, stirring and hydrolyzing for 30min at 30-40 ℃, wherein the system is slightly yellow and clear. Stirring uniformly, transferring the mixture into a liquid separation funnel, standing for layering, discharging a colorless clear water phase at the lower layer, washing with 200g of deionized water for 2-3 times until the pH value is approximately equal to 7, removing the solvent under reduced pressure, and adding THF (tetrahydrofuran) for dissolving to obtain a THF solution of cyclol;
adding THF solution of cycloalcohol and 440g of H beta molecular sieve into a pressure kettle, reacting for 4 hours at the internal temperature of 100-110 ℃ and 20atm, filtering the molecular sieve after the reaction is finished, and removing the solvent to obtain the propylcyclohexyl toluene product.
The conversion of propylcyclohexylcyclohexylcyclohexyltoluene in this example was: greater than 99.5%;
this example gives the cis yield in propylcyclohexylcyclohexylcyclohexyltoluene product: 10.1%, trans yield: 87.3 percent.
Example 12
The reaction equation is as follows:
drying 2L three-necked bottle, adding 11.7g magnesium strip, and introducing nitrogen for replacement for 30min. 82.1g of p-bromotoluene was dissolved in 246.3g of THF, and an appropriate amount was added dropwise to the system, followed by heating to initiate the reaction. The residual solution is dripped at the temperature of 40-50 ℃ and the temperature of 40-50 ℃ is controlled for 2 hours after about 1.5 hours of dripping. The system is light black and clear, and a small amount of magnesium strips are left. 89.6g of
Dissolving in 178g of toluene, controlling the internal temperature to be 50-60 ℃ and dripping into the system, releasing heat after reaction, keeping the system color state unchanged obviously after about 1.5h of dripping, and keeping the internal temperature to be 50-60 ℃ for reaction for 2h. The system is slowly poured into a 2L beaker containing 48g of concentrated hydrochloric acid and 240g of ice water, stirred and hydrolyzed at 30-40 ℃ for 30min, and the system is slightly yellow and clear. After stirring uniformly, the mixture is transferred to a liquid separation funnel for standing and layering, a colorless clear water phase at the lower layer is discharged, and 200g of deionized water is washed for 2 to 3 times until the pH value is approximately equal to 7, so that the solution of the cyclol in toluene and THF is obtained.
A2L three-necked flask is added with a solution of cyclic alcohol in toluene and THF, 440g (3.48 g/g of the theoretical amount of cyclic alcohol) of H beta molecular sieve is added under stirring, nitrogen is introduced, and the mixture is stirred and heated to obtain a dark brown turbid system. Setting the bath temperature at 110 ℃, continuously refluxing and dividing water at the internal temperature of 90-100 ℃, gradually discharging the evaporated THF and water, after about 2 hours, no water is evaporated, raising the internal temperature to over 106 ℃, keeping the internal temperature at 108-110 ℃, refluxing and preserving the temperature for 4 hours, and after the reaction is finished, removing the solvent to obtain the product.
This example
The conversion of the product was: greater than 99.5%;
this example
Yield of cis form in product: 5.8%, trans yield: 92.3 percent.
Example 13
Preparation of propylcyclohexylcyclohexylpropylbenzene
The reaction equation is as follows:
this example was carried out to prepare propylcyclohexylpropylpropylbenzene by the same procedures as in example 1, except that 82.1g of p-bromotoluene in example 1 was replaced with 95.5g of p-bromopropylbenzene.
The conversion of propylcyclohexylcyclohexylpropylbenzene product in this example was: greater than 99.5%;
this example gives the cis yield in propylcyclohexylcyclohexylpropylbenzene product: 5.8%, trans yield: 92.1 percent.
Example 14
Preparation of methylcyclohexyltoluenes
The reaction equation is as follows:
adding 11.7g magnesium strips into a dry 2L three-necked bottle, and introducing nitrogen for replacement for 30min. 82.1g of p-bromotoluene was dissolved in 246.3g of THF, and an appropriate amount was added dropwise to the system, followed by heating to initiate the reaction. The residual solution is dripped at the temperature of 40-50 ℃ and the temperature of 40-50 ℃ is controlled for 2 hours after about 1.5 hours of dripping. The system is light black and clear, and a small amount of magnesium strips are left. 44.8g of methylcyclohexanone is dissolved in 178g of toluene, the internal temperature is controlled to be 50-60 ℃ and is dripped into the system, the reaction releases heat, after about 1.5h of dripping, the system has no obvious color state change, and the internal temperature is kept at 50-60 ℃ for 2h of reaction. The system is slowly poured into a 2L beaker containing 48g of concentrated hydrochloric acid and 240g of ice water, stirred and hydrolyzed at 30-40 ℃ for 30min, and the system is slightly yellow and clear. After stirring uniformly, the mixture is transferred to a liquid separation funnel for standing and layering, a colorless clear water phase at the lower layer is discharged, and 200g of deionized water is washed for 2 to 3 times until the pH value is approximately equal to 7, so that the solution of the cyclol in toluene and THF is obtained.
Adding a solution of cyclic alcohol in toluene and THF (tetrahydrofuran), adding 408g (5 g/g of cyclic alcohol theoretical amount) of H beta molecular sieve while stirring, introducing nitrogen, stirring and heating to obtain a dark brown turbid system. Setting the bath temperature at 110 ℃, continuously refluxing and dividing water at the internal temperature of 90-100 ℃, gradually discharging the evaporated THF and water, after about 2 hours, no water is evaporated, raising the internal temperature to over 106 ℃, keeping the internal temperature at 108-110 ℃, refluxing and preserving the temperature for 4 hours, filtering a molecular sieve after the reaction is finished, and removing the solvent to obtain the methyl cyclohexyl toluene product.
The conversion of the methylcyclohexyltoluene product of this example was: greater than 99.5%;
cis-yield in methylcyclohexyltoluene product of this example: 42.5%, trans yield: 56.5 percent.
Comparative example 1
This comparative example prepared propylcyclohexylcyclohexylcyclohexyltoluene product in the same manner as in example 1, except that: the amount of molecular sieve H β added was 112.5g (0.9 g/g theoretical amount of cyclic alcohol).
The conversion of propylcyclohexylcyclohexylcyclohexylcyclohexyltoluene of this comparative example is: 96.0 percent;
this comparative example gives the cis yield in propylcyclohexylcyclohexylcyclohexyltoluene product: 5.0%, trans yield: 86.0 percent.
As can be seen from the comparison of the data of comparative example 1 and example 1, the amount of the molecular sieve used in the invention does not significantly affect the conversion rate of the product.
Comparative example 2
This comparative example prepared propylcyclohexylcyclohexylcyclohexyltoluene product in the same manner as in example 1, except that: the H beta molecular sieve is replaced by an MSU-X mesoporous molecular sieve.
In this comparative example, the reaction did not proceed smoothly, and the conversion of propylcyclohexylcyclohexyltoluene was almost 0.
Comparative example 3
This comparative example prepared a propylcyclohexylcyclohexylcyclohexylcyclohexyltoluene product in the same manner as in example 1, except that: the H beta molecular sieve is replaced by KIT-1 mesoporous molecular sieve.
In this comparative example, the reaction did not proceed smoothly, and the conversion of propylcyclohexylcyclohexylcyclohexyltoluene was almost 0.
Comparative example 4
This comparative example prepared propylcyclohexylcyclohexylcyclohexyltoluene product in the same manner as in example 1, except that: the H beta molecular sieve is replaced by an MSU-S mesoporous molecular sieve.
In this comparative example, the reaction did not proceed smoothly, and the conversion of propylcyclohexylcyclohexylcyclohexyltoluene was almost 0.
It can be seen from the experimental conditions of comparative examples 2 to 4 that the catalytic effect of the microporous molecular sieve cannot be achieved by using the mesoporous molecular sieve.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (6)
1. A method for preparing cycloalkane from cyclic alcohol in one step by using a molecular sieve, wherein the method for preparing cycloalkane comprises: under the protection of inert gas, adding cycloalcohol and a molecular sieve into an organic solvent, and heating for reaction to obtain cycloalkane, wherein the molecular sieve is a microporous molecular sieve, and the structural formula of the cycloalcohol is as follows:
the structural formula of the cycloalkane is as follows:
wherein m =0 or 1,n =0 or 1,p =0 or 1;
R 1 and R 2 Are respectively H and C 1 -C 20 Straight or branched alkyl or alkoxy, F, CN, CF 3 、Cl、Br、CHF 2 、CF 3 O、NCS、SCN；
A is-CH 2 CH 2 -or a single bond;
R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 are each H, F, cl or CF 3 ；
Or, the structural formula of the cyclic alcohol is shown in the specification
(ii) a The structural formula of the cycloalkane is
；
The molecular sieve is one or a mixture of more of H beta molecular sieve, fe beta molecular sieve, NH4 type ZSM-5 molecular sieve, H type Y molecular sieve, H type mordenite and H type SAPO-34 molecular sieve.
2. The method of claim 1, wherein the cyclic alcohol is selected from the group consisting of the following formulas:
the cycloalkane is selected from the following structural formulae:
3. the method for preparing cycloalkane from cyclic alcohol in one step by using molecular sieve according to claim 1, wherein the organic solvent is one or more selected from n-heptane, petroleum ether, benzene, toluene, xylene, THF, 2-MeTHF, methanol, ethanol, isopropanol, butanol, isobutanol, and tert-butanol.
4. The method for preparing cycloalkane from cycloalkanol with molecular sieve in one step according to claim 1, wherein the temperature of the heating reaction is 40 ℃ to 150 ℃.
5. The method for preparing cycloalkane from cycloalkanol with molecular sieve in one step according to claim 1, wherein the temperature of the heating reaction is 90 ℃ to 120 ℃.
6. The method for preparing cycloalkane from cyclic alcohol in one step by using molecular sieve according to claim 1, wherein the mass ratio of the molecular sieve to the cyclic alcohol is (1-5): 1.
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