CN103980108B - A kind of preparation method of 2-(1-methyl alkyl) succsinic acid - Google Patents
A kind of preparation method of 2-(1-methyl alkyl) succsinic acid Download PDFInfo
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- 239000002253 acid Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 27
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 18
- RGHQKFQZGLKBCF-UHFFFAOYSA-N 2-bromoethyl acetate Chemical compound CC(=O)OCCBr RGHQKFQZGLKBCF-UHFFFAOYSA-N 0.000 claims abstract description 11
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 238000006114 decarboxylation reaction Methods 0.000 claims abstract description 8
- DKMROQRQHGEIOW-UHFFFAOYSA-N Diethyl succinate Chemical compound CCOC(=O)CCC(=O)OCC DKMROQRQHGEIOW-UHFFFAOYSA-N 0.000 claims abstract description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 100
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 23
- -1 acetoacetates ethyl acetate Chemical class 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 19
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 16
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 14
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 7
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 abstract description 16
- 239000002994 raw material Substances 0.000 abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 238000006482 condensation reaction Methods 0.000 abstract 2
- RWLDAJMGAVDXSH-UHFFFAOYSA-N ethane-1,1,2-tricarboxylic acid Chemical compound OC(=O)CC(C(O)=O)C(O)=O RWLDAJMGAVDXSH-UHFFFAOYSA-N 0.000 abstract 2
- 150000002148 esters Chemical class 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000007086 side reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 67
- 235000019439 ethyl acetate Nutrition 0.000 description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 33
- 238000001704 evaporation Methods 0.000 description 29
- 230000008020 evaporation Effects 0.000 description 29
- 239000012074 organic phase Substances 0.000 description 25
- 239000002904 solvent Substances 0.000 description 23
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 22
- 238000000605 extraction Methods 0.000 description 14
- 239000011734 sodium Substances 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 11
- 229960000935 dehydrated alcohol Drugs 0.000 description 11
- 229960004756 ethanol Drugs 0.000 description 11
- 229920006395 saturated elastomer Polymers 0.000 description 11
- 238000010898 silica gel chromatography Methods 0.000 description 11
- 239000011780 sodium chloride Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 238000001819 mass spectrum Methods 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 5
- NGDNVOAEIVQRFH-UHFFFAOYSA-N 2-nonanol Chemical compound CCCCCCCC(C)O NGDNVOAEIVQRFH-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- FVDRFBGMOWJEOR-UHFFFAOYSA-N hexadecan-2-ol Chemical compound CCCCCCCCCCCCCCC(C)O FVDRFBGMOWJEOR-UHFFFAOYSA-N 0.000 description 4
- 239000001384 succinic acid Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000031709 bromination Effects 0.000 description 3
- 238000005893 bromination reaction Methods 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- YZWKKMVJZFACSU-UHFFFAOYSA-N 1-bromopentane Chemical compound CCCCCBr YZWKKMVJZFACSU-UHFFFAOYSA-N 0.000 description 2
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 description 2
- JQEFZTLHNWFZDD-UHFFFAOYSA-N 2-bromononane Chemical compound CCCCCCCC(C)Br JQEFZTLHNWFZDD-UHFFFAOYSA-N 0.000 description 2
- FTJHYGJLHCGQHQ-UHFFFAOYSA-N 2-bromooctane Chemical compound CCCCCCC(C)Br FTJHYGJLHCGQHQ-UHFFFAOYSA-N 0.000 description 2
- ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 2-octanone Chemical compound CCCCCCC(C)=O ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 238000006600 Stobbe condensation reaction Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000002906 microbiologic effect Effects 0.000 description 2
- VKCYHJWLYTUGCC-UHFFFAOYSA-N nonan-2-one Chemical compound CCCCCCCC(C)=O VKCYHJWLYTUGCC-UHFFFAOYSA-N 0.000 description 2
- 239000012925 reference material Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- YEEOQXDOVBYNDC-UHFFFAOYSA-N 2-bromohexadecane Chemical compound CCCCCCCCCCCCCCC(C)Br YEEOQXDOVBYNDC-UHFFFAOYSA-N 0.000 description 1
- OGYSYXDNLPNNPW-UHFFFAOYSA-N 4-butoxy-4-oxobutanoic acid Chemical compound CCCCOC(=O)CCC(O)=O OGYSYXDNLPNNPW-UHFFFAOYSA-N 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- ISRUGXGCCGIOQO-UHFFFAOYSA-N Rhoden Chemical compound CNC(=O)OC1=CC=CC=C1OC(C)C ISRUGXGCCGIOQO-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 150000004729 acetoacetic acid derivatives Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000090 biomarker Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N diethyl maleate Chemical compound CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- FMKOJHQHASLBPH-UHFFFAOYSA-N isopropyl iodide Chemical compound CC(C)I FMKOJHQHASLBPH-UHFFFAOYSA-N 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- OVEHNNQXLPJPPL-UHFFFAOYSA-N lithium;n-propan-2-ylpropan-2-amine Chemical compound [Li].CC(C)NC(C)C OVEHNNQXLPJPPL-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 230000007269 microbial metabolism Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- UAWABSHMGXMCRK-UHFFFAOYSA-L samarium(ii) iodide Chemical compound I[Sm]I UAWABSHMGXMCRK-UHFFFAOYSA-L 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/317—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
- C07C67/32—Decarboxylation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses the preparation method of a kind of 2-(1-methyl alkyl) succsinic acid, comprise the steps: that (1) bromoethyl acetate and diethyl malonate generate 1,1,2-ethane tricarboxylic acid triethyl through condensation reaction; (2) 1,1,2-ethane tricarboxylic acid triethyls and the condensation reaction of 2-brominated alkanes generate 3-methyl alkane-1,2,2-tri-carboxyl triethyl; (3) 3-methyl alkane-1,2,2-tri-carboxyl triethyl and LiCl/H
2the decarboxylation of O Hybrid Heating obtains 2-(1-methyl alkyl) ethyl succinate; (4) ester is hydrolyzed in strong base solution, obtains 2-(1-methyl alkyl) succsinic acid.Reaction raw materials wide material sources of the present invention, cheap; Reaction conditions is gentle, and react completely, side reaction is few, can prepare 2-(1-methyl alkyl) the succsinic acid homologue that alkyl carbon chain lengths is 3 ~ 16 carbon.
Description
Technical field
The present invention relates to organic compound synthesis field, be specifically related to a kind of preparation method of succsinic acid.
Background technology
Alkane, as one of stone main body of oil, is present in subsurface deposit environment widely.Oil reservoir, as a kind of extreme environment, wherein but breeds the microorganism of species diversity.In recent years, the method for room cultivation by experiment, there has been proposed multiple alkane anaerobic degradation approach.Wherein, fumaric acid addition reaction mechanism is the most important and general.This mechanism, by the C-2 position of alkane and fumaric acid addition, obtains 2-(1-methyl alkyl) succsinic acid and activates alkane to carry out follow-up metabolism.Because 2-(1-methyl alkyl) succsinic acid only appears in alkane anaerobic degradation process, and this material is without commercial source, and therefore this material is considered to a kind of biomarker.By detecting this material, the existence of microbiological anaerobic alkane degradation process in sample directly can be shown.
2-(1-methylethyl) succsinic acid and 2-(1-methyl-propyl) succsinic acid is only had to be obtained by synthetic in this kind of material of 2-(1-methyl alkyl) succsinic acid of current bibliographical information.Synthesis as 2-(1-methylethyl) succsinic acid has three kinds of methods, one uses SmI2/ (Me2N) 3P=O or H2/Pd reduction system 2-(1-methylmethylene) succsinic acid, second method mono succinate butyl ester and 2-iodopropane under the existence of lithium diisopropylamine carry out alkylation, and the third method is butene dioic acid diethyl ester and IPMC condensation.First method reaction raw materials cost is high, and hydrogenating reduction operational hazards, second method need be reacted at low temperatures, and condition is harsh, and the third method is poisoned large, unfriendly to environment.2-(1-methyl alkyl) the succsinic acid homologue trace separately having small part to be derived from microbial metabolism is present in hydrocarbon contaminate environment.But this material in the environment general content is low, is difficult to detect, and does not have reference material to understand the character of this type of material for people, and therefore the current recognition capability to 2-(1-methyl alkyl) succsinic acid is limited.By synthetic 2-(1-methyl alkyl) succsinic acid reference material, its mass spectrum property is studied, can instruct and detect this material in actual sample.
At present, 2-(1-methyl alkyl) succsinic acid produces primarily of microbiological anaerobic degradation of hydrocarbon material, less to the artificial synthesis report of 2-(1-methyl alkyl) succsinic acid, be mainly Stobbe reaction product reduction method, the method uses 2-alkane ketone to be raw material, by Stobbe reaction and succinic acid condensation, then by the method for precious metal catalyst hydrogenation, the condensation product reduction of ketone and succinate is obtained 2-(1-methyl alkyl) succsinic acid.The method reaction raw materials can not generally be buied, and severe reaction conditions, need anhydrous and oxygen-free condition, catalytic hydrogenation danger is high, expensive catalyst.And other similar methods can only synthesis of alkyl side chain be the alkyl succinic acid that end position replaces, 2-(1-methyl alkyl) succsinic acid replaced with required target product alkyl time end has certain difference.
Summary of the invention
Therefore, the technical problem to be solved in the present invention is to provide that a kind of reaction raw materials is easily buied, productive rate is high, the preparation method of the 2-of wider homologue scope (1-methyl alkyl) succsinic acid.
Technical scheme of the present invention is, the preparation method of 2-shown in formula I (1-methyl alkyl) succsinic acid, and the method comprises:
(1) in sodium ethylate/ethanolic soln, add diethyl malonate, under normal temperature, react 0.2-1 hour, then under subzero 2-2 DEG C condition, add bromoethyl acetate reaction, obtain 1,1,2-ethane three carboxyl triethyl;
(2) in sodium ethylate/ethanolic soln, add 1,1,2-ethane three carboxyl triethyl, react 0.2-1 hour under subzero 2-2 DEG C condition, then add 2-brominated alkanes, at 70-90 DEG C, be obtained by reacting 3-methyl alkane-1,2,2-tri-carboxyl triethyl;
(3) 3-methyl alkane-1,2,2-tri-carboxyl triethyl is dissolved in dimethyl sulfoxide (DMSO), adds H
2o and LiCl, reacts under 140-160 DEG C of condition, is obtained by reacting 2-(1-methyl alkyl) ethyl succinate;
(4) 2-(1-methyl alkyl) ethyl succinate is hydrolyzed in strong base solution, obtains 2-(1-methyl alkyl) succsinic acid.
2-of the present invention (1-methyl alkyl) succsinic acid preparation process is as follows:
Preparation in accordance with the present invention, preferably, the normal temperature lower reaction times described in step (1) is 0.3-0.8 hour; Described add bromoethyl acetate after reaction times be 3-6 hour.It is further preferred that the reaction times is 4h.
Preparation in accordance with the present invention, preferably, the time of reacting under step (3) described 140-160 DEG C condition is 3-6 hour.It is further preferred that the reaction times is 4h.
Preparation in accordance with the present invention, preferably, step (4) described strong base solution is NaOH solution or KOH solution, and the mass concentration of described strong base solution is 10-30%.More preferably strong base solution concentration is 20%-25%.
Preparation in accordance with the present invention, preferably, the preparation method of described 2-brominated alkanes is:
(1) in sodium ethylate/ethanolic soln, add methyl aceto acetate, stir, then add 1-brominated alkanes, at 70 ~ 80 DEG C, be obtained by reacting 2-alkyl acetoacetates ethyl acetate;
(2) in 2-alkyl acetoacetates ethyl acetate, add excessive strong base solution, at 25 ~ 45 DEG C, be hydrolyzed 4 ~ 6h, then regulator solution pH<1, decarboxylation under 60 ~ 80 DEG C of conditions, obtained 2-alkane ketone;
(3) 2-alkane ketone is dissolved in methyl alcohol, adds NaBH
4, reaction is extremely without H
2produce, after acidifying, 60 ~ 80 DEG C of hydrolysis 1 ~ 2h obtain 2-alkanol;
(4) by 2-alkanol, HBr and H
2sO
4solution reacts at 110-130 DEG C, obtained 2-brominated alkanes.
The strong base solution of step (2) can adopt sodium hydroxide or potassium hydroxide solution.Step (4) reaction times is generally 1-5 hour.Also can be 1 ~ 3h.
The preparation process of the preparation method of 2-brominated alkanes is as follows:
It is further preferred that step (2) the decarboxylation time is 1h, NaOH solution or KOH solution are 10%-15% mass concentration.2-brominated alkanes can be selected to buy, and also can select to be obtained by aforesaid method, and the method is a comparatively preferred scheme.1-brominated alkanes wherein can be bought, and following methods also can be adopted to obtain:
By 1-alkanol, HBr and H
2sO
4solution reacts 1 ~ 3h at 115-125 DEG C, obtained 1-brominated alkanes, or adopt silver carboxylate be dissolved in after tetracol phenixin with Br
2reaction, obtained 1-brominated alkanes.Temperature of reaction preferably 120 DEG C.
Preparation in accordance with the present invention, preferably, in step (1), the mol ratio of described bromoethyl acetate, diethyl malonate and sodium ethylate is 1:1 ~ 1.5:1 ~ 1.5.
Or in a preferred scheme, in step (2), the mol ratio of sodium ethylate, 1,1,2-ethane three carboxyl triethyl, 2-brominated alkanes is 1-1.1:1-1.2:1-1.2.
Or, in a preferred scheme, in step (3), described-methyl alkane 3-1,2,2-tri-carboxyl triethyl, LiCl and H
2the mol ratio of O is 1:2 ~ 3:1 ~ 2.
In the preparation method of 2-brominated alkanes, in step (1), the mol ratio of described 1-brominated alkanes, methyl aceto acetate and sodium ethylate is 1:1 ~ 1.3:1 ~ 1.5.
In the preparation method of 2-brominated alkanes, in step (2), 2-alkyl ketone and NaBH
4molar ratio be 1:1 ~ 1.2.
The invention has the beneficial effects as follows:
Compared with the prior art, the outstanding feature of the preparation method of 2-of the present invention (1-methyl alkyl) succsinic acid can adopt commercially available 1-brominated alkanes or use the 1-alkyl alcohol of easily acquisition or alkyl carboxylic acid to be reaction raw materials, adopt twice alkylated reaction of diethyl malonate, build succsinic acid structure and alkyl group side chain structure, then react decarboxylation and then preparation 2-(1-methyl alkyl) succsinic acid by Krapcho.The method compared with the conventional method, reaction conditions is gentle, and by product is few, and according to the difference of reaction raw materials, the present invention has the advantages that to prepare multiple alkyl succinic acid homologue, can prepare 2-(1-methyl alkyl) the succsinic acid homologue that alkyl carbon chain lengths is 3 ~ 16 carbon.
2-(1-methyl alkyl) succinics is the compound being just found to have special indicative function recently, at present also not for the general synthetic method of this class material.Prior art is just synthesized for some the specific material in this class material of 2-(1-methyl alkyl) succsinic acid; In these specific materials of synthesis, again with the material that specifically will synthesize for target, the reaction raw materials taked, synthetic route etc. are mostly different, and each predetermined substance route of synthesis can not be mutually general; , also exist without corresponding reaction raw materials when these methods being expanded to the synthesis of full homologue, reaction conditions is inapplicable waits series of problems, does not therefore also form synthetic method system applied widely meanwhile.
For low-molecular-weight 2-(1-methyl alkyl) succsinic acid, owing to buying raw material, therefore required reactions steps is few, and productive rate is higher.And for medium and macromolecule (alkyl group side chain more than 5 carbon, i.e. R=C in structural formula
nh
2n+1in n be greater than 3) 2-(1-methyl alkyl) succsinic acid, also do not have synthetic method at present, these materials are that the present invention synthesizes (as example 3 and example 4) first.
Accompanying drawing explanation
Fig. 1 is the ethyl esterified product mass spectra figure of embodiment 1.
Fig. 2 is the ethyl esterified product mass spectra figure of embodiment 2.
Fig. 3 is the ethyl esterified product mass spectra figure of embodiment 3.
Fig. 4 is the ethyl esterified product mass spectra figure of embodiment 4.
Embodiment
The preparation of embodiment 1:2-(1-methylethyl) succsinic acid
(1) in 100mL flask, by 0.4mol 1-Virahol, 0.4mol HBr and 0.4mol H
2sO
4after 0 DEG C of mixing, at 120 DEG C, react 1h, cool rear thin up extracted with diethyl ether 3 times, evaporation of solvent, obtained 1-bromo propane.
(2) in 100mL flask, join after 0.4mol Na is cut into small pieces in 30mL dehydrated alcohol, be stirred to without H under 0 DEG C of condition
2generate, obtained sodium ethylate/ethanolic soln.In solution, add 0.4mol diethyl malonate, move to stirring at normal temperature 0.5h.In this solution, 0.4mol bromoethyl acetate is added again under 0 DEG C of condition.Added latter 0 DEG C and stirred 4h, stirring at normal temperature is spent the night.Steam ethanol after reaction terminates, add NaCl saturated aqueous solution, with rare HCl regulator solution pH<1, product extracted into EtOAc 3 times.After organic phase being merged, evaporation of solvent, obtains 1,1,2-ethane three carboxyl triethyl.
(3) in 100mL flask, join in 30mL dehydrated alcohol after being cut into small pieces by 0.48mol Na, 0 DEG C of condition is down to without H
2generate, obtained sodium ethylate/ethanolic soln.To be added in solution under 0.4mol 1,1,2-ethane three carboxyl triethyl 0 DEG C of condition, reaction 0.5h.Be added in solution by 0.4mol bromo propane again, 80 DEG C of reaction to white solids no longer increase.Steam ethanol after reaction terminates, add NaCl saturated aqueous solution, regulate pH<1 with rare HCl, extraction into ethyl acetate 3 times.After organic phase being merged, evaporation of solvent, obtains 3-methylbutane-1,2,2-tri-carboxyl triethyl.
(4) in 100mL flask, 0.4mol 3-methylbutane-1,2,2-tri-carboxyl triethyl is dissolved in 25mL dimethyl sulfoxide (DMSO), adds 0.4mol H
2o and 0.8mol LiCl, reflux 4h under 150 DEG C of conditions.After reaction terminates, in solution, add H
2o, is extracted with ethyl acetate three times, merges organic phase, evaporation of solvent, is separated, obtains 2-(1-methylethyl) ethyl succinate with silica gel column chromatography.
(5) 2-(1-methylethyl) ethyl succinate is hydrolyzed in the NaOH solution of 80mL 20%, with extraction into ethyl acetate after rare HCl acidify solution 3 times, merge organic phase, evaporation of solvent, with silica gel column chromatography, obtain 2-(1-methylethyl) succsinic acid.Overall yield 50%.
The preparation of embodiment 2:2-(1-methylheptyl) succsinic acid
(1) in 100mL flask, by 0.4mol 1-Pentyl alcohol, 0.42mol HBr and 0.48mol H
2sO
4after 0 DEG C of mixing, at 120 DEG C, react 2h, cool rear thin up petroleum ether extraction 3 times, evaporation of solvent, obtained 1-bromo pentane.
(2) be added to after being cut into small pieces by 0.52mol Na in 30mL dehydrated alcohol, 0 DEG C extremely without H
2generate, obtained sodium ethylate/ethanolic soln.0.48mL methyl aceto acetate is added, 0 DEG C of reaction 0.8h in solution.In this solution, add 0.4mol 1-bromo pentane again, react under 75 DEG C of conditions to white solid and no longer increase.Steam ethanol after reaction terminates, add NaCl saturated aqueous solution, regulate pH<1 with rare HCl solution, extraction into ethyl acetate 3 times.After organic phase being merged, evaporation removing ethyl acetate, obtains 2-amyl group methyl aceto acetate.
(3) 80mL 10%NaOH solution is added, 35 DEG C of Water Under solution 5h in the obtained 2-amyl group methyl aceto acetate of step (2).With rare HCl regulator solution pH<1, decarboxylation 1h under 70 DEG C of conditions, is extracted with ethyl acetate three times, and merge organic phase, evaporation of solvent, obtains methyln-hexyl ketone.
(4) in 100mL flask, 0.4mol methyln-hexyl ketone is dissolved in 30mL methyl alcohol, under stirring at 0 DEG C, adds 0.44mol NaBH in batches
4, be stirred to and no longer produce H
2till, distillation for removing methanol, adds rare HCl solution to pH<1, and 70 DEG C of hydrolysis 1.5h, product extracted into EtOAc three times, merge organic phase, evaporation of solvent obtains sec-n-octyl alcohol.
(5) sec-n-octyl alcohol is carried out bromination according to step (1), with silica gel column chromatography, obtained 2-bromooctane.
(6) in 100mL flask, be added in 30mL dehydrated alcohol after being cut into small pieces by 0.52mol Na, under 0 DEG C of condition, reaction is extremely without H
2generate, obtained sodium ethylate/ethanolic soln.In solution, add 0.52mol diethyl malonate, move to stirring at normal temperature 0.75h.In this solution, 0.4mol bromoethyl acetate is added again under 0 DEG C of condition.Added latter 0 DEG C and stirred 4h, stirring at normal temperature is spent the night.Steam ethanol after reaction terminates, add NaCl saturated aqueous solution, regulate pH<1 with rare HCl solution, extraction into ethyl acetate 3 times.After organic phase being merged, evaporation removing ethyl acetate, obtains 1,1,2-ethane three carboxyl triethyl.
(7) in 100mL flask, be added in 30mL dehydrated alcohol after being cut into small pieces by 0.54mol Na, under 0 DEG C of condition, reaction is extremely without H
2generate, obtained sodium ethylate/ethanolic soln.To be added in solution under 0.4mol 1,1,2-ethane three carboxyl triethyl 0 DEG C of condition, reaction 0.75h.Be added in solution by 0.4mL 2-bromooctane again, 75 DEG C of back flow reaction no longer increase to white solid.Steam ethanol after reaction terminates, add NaCl saturated aqueous solution, regulate pH<1 with rare HCl solution, extraction into ethyl acetate 3 times.After organic phase being merged, evaporation of solvent, obtains 3-methylnonane-1,2,2-tri-carboxyl triethyl.
(8) 0.4mol 3-methylnonane-1,2,2-tri-carboxyl triethyl is dissolved in 25mL DMSO, adds 0.6mol H
2o and 1.0mol LiCl, reflux 4h under 155 DEG C of conditions.After reaction terminates, in solution, add H
2o, is extracted with ethyl acetate three times, and merge organic phase, evaporation of solvent, with silica gel column chromatography, obtains 2-(1-methylheptyl) ethyl succinate.
(9) 2-(1-methylheptyl) ethyl succinate obtained by step (8) is hydrolyzed through 80mL 20%NaOH solution, after rare HCl acidifying, be extracted with ethyl acetate three times, merge organic phase, evaporation of solvent, with silica gel column chromatography, obtain 2-(1-methylheptyl) succsinic acid.Overall yield 42%.
The preparation of embodiment 3:2-(1-Methyl Octyl) succsinic acid
(1) in 100mL flask, by 0.4mol 1-n-hexyl alcohol, 0.48mol HBr and 0.56mol H
2sO
4after 0 DEG C of mixing, at 120 DEG C, react 3h, cool rear thin up petroleum ether extraction 3 times, evaporation of solvent, obtained 1-bromo normal hexane.
(2) be added to after being cut into small pieces by 0.4mol Na in 30mL dehydrated alcohol, 0 DEG C extremely without H
2generate, obtained sodium ethylate/ethanolic soln.In solution, add 0.4mL methyl aceto acetate, 0 DEG C is stirred 0.5h.In this solution, add 0.4mol 1-bromo normal hexane again, react under 70 DEG C of conditions to white solid and no longer increase.Steam ethanol after reaction terminates, add NaCl saturated aqueous solution, regulate pH<1 with rare HCl solution, extraction into ethyl acetate 3 times.After organic phase being merged, evaporation removing ethyl acetate, obtains 2-hexyl methyl aceto acetate.
(3) 80mL 10%NaOH solution is added, 25 DEG C of Water Under solution 4h in the obtained alkyl acetoacetates ethyl acetate of step (2).With rare HCl regulator solution pH<1, decarboxylation 1h under 60 DEG C of conditions, is extracted with ethyl acetate three times, and merge organic phase, evaporation of solvent, obtains methyl n-heptyl ketone.
(4) in 100mL flask, 0.4mol methyl n-heptyl ketone is dissolved in 30mL methyl alcohol, under stirring at 0 DEG C, adds 0.44mol NaBH in batches
4, be stirred to and no longer produce H
2till, distillation for removing methanol, adds rare HCl solution to pH<1, and 60 DEG C of hydrolysis 1h, product extracted into EtOAc three times, merge organic phase, evaporation of solvent obtains 2-nonyl alcohol.
(5) the 2-nonyl alcohol obtained by step (4) is carried out bromination according to step (1), with silica gel column chromatography, obtained 2-bromo nonane.
(6) in 100mL flask, be added in 30mL dehydrated alcohol after being cut into small pieces by 0.4mol Na, 0 DEG C of condition is down to without H
2generate, obtained sodium ethylate/ethanolic soln.In solution, add 0.4mol diethyl malonate, move to stirring at normal temperature 1h.In this solution, 0.4mol bromoethyl acetate is added again in 0 DEG C.Added latter 0 DEG C and stirred 4h, stirring at normal temperature is spent the night.Steam ethanol after reaction terminates, add NaCl saturated aqueous solution, regulate pH<1 with rare HCl, extraction into ethyl acetate 3 times.After organic phase being merged, evaporation removing ethyl acetate, obtains 1,1,2-ethane three carboxyl triethyl.
(7) in 100mL flask, be added in 30mL dehydrated alcohol after being cut into small pieces by 0.48mol Na, 0 DEG C of condition is down to without H
2generate, obtained sodium ethylate/ethanolic soln.To be added in solution under 0.4mol 1,1,2-ethane three carboxyl triethyl 0 DEG C of condition, stir 1h.Be added in solution by 0.4mL 2-bromo nonane again, 70 DEG C of back flow reaction no longer increase to white solid.Steam ethanol after reaction terminates, add NaCl saturated aqueous solution, regulate pH<1 with rare HCl solution, extraction into ethyl acetate 3 times.After organic phase being merged, evaporation of solvent, obtains 3-methyldecane-1,2,2-tri-carboxyl triethyl.
(8) 0.4mol 3-methyldecane-1,2,2-tri-carboxyl triethyl is dissolved in 25mL DMSO, adds 0.4mol H
2o and 0.8mol LiCl, reflux 4h under 150 DEG C of conditions.After reaction terminates, in solution, add H
2o, is extracted with ethyl acetate three times, and merge organic phase, evaporation of solvent, with silica gel column chromatography, obtains 2-(1-Methyl Octyl) ethyl succinate.
(9) 2-(1-Methyl Octyl) ethyl succinate obtained by step (8) is hydrolyzed through 80mL 20%NaOH solution, after rare HCl acidifying, be extracted with ethyl acetate three times, merge organic phase, evaporation of solvent, with silica gel column chromatography, obtain 2-(1-Methyl Octyl) succsinic acid.Overall yield 48%.
The preparation of embodiment 4:2-(1-methyl pentadecyl) succsinic acid
(1) be back to it after adding 0.4mol TETRADECONIC ACID in containing the NaOH solution of 0.4mol all to dissolve, after cooling, add 0.4mol AgNO
3in solution, rapid stirring 0.5h, hold over night, suction filtration, respectively wash 3 times with water and methyl alcohol.Be transferred to 60 DEG C of oven dry in watch-glass.The lipid acid of drying silver grinding powder is placed in 100ml flask, adds dried tetracol phenixin 30mL, under reflux conditions slowly add 0.4mol Br
2, be for redness to solution.Cooled and filtered removing Silver monobromide, distillation, except desolventizing, uses 5%Na
2s
2o
3solution washing product, petroleum ether extraction 3 times, evaporation of solvent, obtained 1-tridecane bromide.
(2) be added to after being cut into small pieces by 0.6mol Na in 30mL dehydrated alcohol, 0 DEG C extremely without H
2generate, obtained sodium ethylate/ethanolic soln.In solution, add 0.52mL methyl aceto acetate, 0 DEG C is stirred 1h.In this solution, add 0.4mol 1-tridecane bromide again, react under 80 DEG C of conditions to white solid and no longer increase.Steam ethanol after reaction terminates, add NaCl saturated aqueous solution, regulate pH<1 with rare HCl solution, extraction into ethyl acetate 3 times.After organic phase being merged, evaporation removing ethyl acetate, obtains 2-tridecyl methyl aceto acetate.
(3) 80mL 10%NaOH solution is added to 2-tridecane methyl aceto acetate, 45 DEG C of Water Under solution 4h.With rare HCl regulator solution pH<1, decarboxylation 1h under 80 DEG C of conditions, is extracted with ethyl acetate three times, and merge organic phase, evaporation of solvent, obtains 2-16 ketone.
(4) in 100mL flask, 0.4mol 2-16 ketone is dissolved in 30mL methyl alcohol, under stirring at 0 DEG C, adds 0.48mol NaBH in batches
4, be stirred to and no longer produce H
2till, distillation for removing methanol, adds HCl solution to pH<1, and 80 DEG C of hydrolysis 2h, product extracted into EtOAc three times, merge organic phase, evaporation of solvent obtains 2-hexadecanol.
(5) the 2-hexadecanol obtained by step (4) is carried out bromination according to step (1), with silica gel column chromatography, obtained 2-bromo hexadecanol alkane.
(6) in 100mL flask, be added in 30mL dehydrated alcohol after being cut into small pieces by 0.6mol Na, 0 DEG C of condition is down to without H
2generate, obtained sodium ethylate/ethanolic soln.In solution, add 0.6mol diethyl malonate, move to stirring at normal temperature 1h.In this solution, 0.4mol bromoethyl acetate is added again in 0 DEG C.Added rear continuation and stirred 4h, stirring at normal temperature is spent the night.Steam ethanol after reaction terminates, add NaCl saturated aqueous solution, regulate pH<1 with rare HCl, extraction into ethyl acetate 3 times.After organic phase being merged, evaporation removing ethyl acetate, obtains 1,1,2-ethane three carboxyl triethyl.
(7) in 100mL flask, be added in 30mL dehydrated alcohol after being cut into small pieces by 0.6mol Na, 0 DEG C of condition is down to without H
2generate, obtained sodium ethylate/ethanolic soln.To be added in solution under 0.4mol 1,1,2-ethane three carboxyl triethyl 0 DEG C of condition, stir 1h.Be added in solution by 0.4mL 2-bromohexadecane again, 80 DEG C of back flow reaction no longer increase to white solid.Steam ethanol after reaction terminates, add NaCl saturated aqueous solution, regulate pH<1 with rare HCl, extraction into ethyl acetate 3 times.After organic phase being merged, evaporation of solvent, obtains 3-methyl heptadecane-1,2,2-tri-carboxyl triethyl.
(8) 0.4mol 3-methyl heptadecane-1,2,2-tri-carboxyl triethyl is dissolved in 25mL DMSO, adds 0.8molH
2o and 1.2mol LiCl, reflux 4h under 160 DEG C of conditions.After reaction terminates, in solution, add H
2o, is extracted with ethyl acetate three times, and merge organic phase, evaporation of solvent, with silica gel column chromatography, obtains 2-(1-methyl pentadecyl) ethyl succinate.
(9) 2-(the 1-methyl pentadecyl) ethyl succinate obtained by step (8) is hydrolyzed through 80mL 20%NaOH solution, after rare HCl acidifying, be extracted with ethyl acetate three times, merge organic phase, evaporation of solvent, with silica gel column chromatography, obtain 2-(1-methyl pentadecyl) succsinic acid.Overall yield 37%.
Preparation method of the present invention, reaction conditions is gentle, and by product is few, and according to the difference of reaction raw materials, the present invention has the advantages that to prepare multiple alkyl succinic acid homologue, can prepare 2-(1-methyl alkyl) the succsinic acid homologue that alkyl carbon chain lengths is 3 ~ 16 carbon.And reaction raw materials wide material sources of the present invention, cheap.
Claims (10)
1. the preparation method of 2-shown in formula I (1-methyl alkyl) succsinic acid, is characterized in that: the method comprises:
(1) in sodium ethylate/ethanolic soln, add diethyl malonate, under normal temperature, react 0.2-1 hour, then under subzero 2-2 DEG C condition, add bromoethyl acetate reaction, obtain 1,1,2-ethane three carboxyl triethyl;
(2) in sodium ethylate/ethanolic soln, add 1,1,2-ethane three carboxyl triethyl, react 0.2-1 hour under subzero 2-2 DEG C condition, then add 2-brominated alkanes, at 70-90 DEG C, be obtained by reacting 3-methyl alkane-1,2,2-tri-carboxyl triethyl;
(3) 3-methyl alkane-1,2,2-tri-carboxyl triethyl is dissolved in dimethyl sulfoxide (DMSO), adds H
2o and LiCl, reacts under 140-160 DEG C of condition, is obtained by reacting 2-(1-methyl alkyl) ethyl succinate;
(4) 2-(1-methyl alkyl) ethyl succinate is hydrolyzed in strong base solution, obtains 2-(1-methyl alkyl) succsinic acid.
2. the preparation method of 2-according to claim 1 (1-methyl alkyl) succsinic acid, is characterized in that, the normal temperature lower reaction times described in step (1) is 0.3-0.8 hour; Described add bromoethyl acetate after reaction times be 3-6 hour.
3. the preparation method of 2-according to claim 1 (1-methyl alkyl) succsinic acid, is characterized in that, the time of reacting under step (3) described 140-160 DEG C condition is 3-6 hour.
4. the preparation method of 2-according to claim 1 (1-methyl alkyl) succsinic acid, is characterized in that, step (4) described strong base solution is NaOH solution or KOH solution, and the mass concentration of described strong base solution is 10-30%.
5. the preparation method of 2-according to claim 1 (1-methyl alkyl) succsinic acid, is characterized in that, the preparation method of described 2-brominated alkanes is,
(1) in sodium ethylate/ethanolic soln, add methyl aceto acetate, stir, then add 1-brominated alkanes, at 70 ~ 80 DEG C, be obtained by reacting 2-alkyl acetoacetates ethyl acetate;
(2) in 2-alkyl acetoacetates ethyl acetate, add excessive strong base solution, at 25 ~ 45 DEG C, be hydrolyzed 4 ~ 6h, then regulator solution pH<1, decarboxylation under 60 ~ 80 DEG C of conditions, obtained 2-alkane ketone;
(3) 2-alkane ketone is dissolved in methyl alcohol, adds NaBH
4, reaction is extremely without H
2produce, after acidifying, 60 ~ 80 DEG C of hydrolysis 1 ~ 2h obtain 2-alkanol;
(4) by 2-alkanol, HBr and H
2sO
4solution reacts at 110-130 DEG C, obtained 2-brominated alkanes.
6. the preparation method of 2-according to claim 1 (1-methyl alkyl) succsinic acid, is characterized in that, in step (1), the mol ratio of described bromoethyl acetate, diethyl malonate and sodium ethylate is 1:1 ~ 1.5:1 ~ 1.5.
7. the preparation method of 2-according to claim 1 (1-methyl alkyl) succsinic acid, it is characterized in that, in step (2), sodium ethylate, 1, the mol ratio of 1,2-ethane three carboxyl triethyl, 2-brominated alkanes is 1-1.1:1-1.2:1-1.2.
8. the preparation method of 2-according to claim 1 (1-methyl alkyl) succsinic acid, is characterized in that, in step (3), and described 3-methyl alkane-1,2,2-tri-carboxyl triethyl, LiCl and H
2the mol ratio of O is 1:2 ~ 3:1 ~ 2.
9. the preparation method of 2-according to claim 5 (1-methyl alkyl) succsinic acid, is characterized in that, in step (1), the mol ratio of described 1-brominated alkanes, methyl aceto acetate and sodium ethylate is 1:1 ~ 1.3:1 ~ 1.5.
10. the preparation method of 2-according to claim 5 (1-methyl alkyl) succsinic acid, is characterized in that, in step (2), and 2-alkyl ketone and NaBH
4molar ratio be 1:1 ~ 1.2.
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