CN103709025B - Preparation method for 2,2-dimethylol alkanoic acid - Google Patents

Preparation method for 2,2-dimethylol alkanoic acid Download PDF

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CN103709025B
CN103709025B CN201310744244.6A CN201310744244A CN103709025B CN 103709025 B CN103709025 B CN 103709025B CN 201310744244 A CN201310744244 A CN 201310744244A CN 103709025 B CN103709025 B CN 103709025B
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alkyl nitrile
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reaction
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CN103709025A (en
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牟通
王漭
谢增勇
信勇
刘运海
叶天
丛鑫
董岩峰
朱发明
王爱发
程英
曹善健
黎源
华卫琦
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Wanhua Chemical Group Co Ltd
Wanhua Chemical Ningbo Co Ltd
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Wanhua Chemical Group Co Ltd
Wanhua Chemical Ningbo Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/08—Preparation of carboxylic acids or their salts, halides or anhydrides from nitriles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

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Abstract

The invention relates to a preparation method for 2,2-dimethylol alkanoic acid. The preparation method comprises the following steps: reacting alkylnitrile and chloromethyl methyl ether under the effect of an alkali to generate 2,2-dimethoxy alkylnitrile; carrying out acidic hydrolysis on 2,2-dimethoxy alkylnitrile, so as to obtain the product 2,2-dimethylol alkanoic acid. The process is simple and convenient to react; 2,2-dimethylol alkanoic acid has the advantages of high total yield and high purity; the technical problem that the product is difficult to prepare and purify is overcome.

Description

A kind of preparation method of 2,2-dimethylolalkanoic acids
Technical field
The invention belongs to organic synthesis field, relate to a kind of preparation method of 2,2-dimethylolalkanoic acids more specifically.
Background technology
With 2, the dimethylolalkanoic acids compounds that 2-dimethylol propionic acid (DMPA) and 2,2-dimethylolpropionic acid (DMBA) are representative has special molecular structure: in a quaternary carbon atom, be connected with the functional group that three kinds, methylol, carboxyl and alkyl is different in the heart.This special molecular structure determines the special chemical property of this compounds.
Concrete, the supercentral polysubstituted structure of quaternary carbon atom, covalent linkage form is similar to the tetrahedral configuration in diamond, makes this quasi-molecule have good photo and thermal stability; And lipophilic alkyl group and hydrophilic hydroxy group, the coexisting of carboxyl, make it in oil-based solvent and aqueous solvent, have unique solubility property; Meanwhile, the change of the reactive behavior that hydroxyl and carboxylic group cause because space is adjacent, makes it have certain reaction preference to reactive groups such as NCO.
Above-mentioned all features, make 2,2-dimethylolalkanoic acids compounds (especially DMPA and DMBA) as linking agent and emulsifying agent, are widely used in the aspects such as water-soluble poly propylhomoserin, water-soluble polyester, epoxy resin, sizing agent.
From 2,2-dimethylol propionic acid is synthesized so far in 20 beginnings of the century, the study on the synthesis of dimethylolalkanoic acids compounds there is no important breakthrough, existing synthesis technique mainly adopts alkyl aldehydes (propionic aldehyde or butyraldehyde) and formaldehyde condensation to prepare 2,2-dihydroxymethyl alkanal, different oxygenants (hydrogen peroxide or the oxygen) oxidation of this alkanal, is separated and obtains required product 2,2-dimethylolalkanoic acids.
Adopt trimethylamine-triethylamine (TEA) to be catalyzer in patent US4594461 first, after reaction solution distillation, obtain 2,2-dihydroxymethyl butyraldehyde.Further expanded the scope of tertiary amine in patent EP0860419A1, comprised alkyl tertiary amine, other aliphatic amides, the cyclic amine that N replaces, the amine containing aromatic group and quaternary ammonium salt have good katalysis to this reaction.
From 1998, Mitsubishi KCC Hengshan Mountain person of outstanding talent the patent EP0860419A1 that delivers and US5994592 such as to control and discloses about 2, the preparation method of 2-dihydroxymethyl alkanal, discuss with butyraldehyde-n and formaldehyde as raw material production 2, the selection of catalyzer alkali and consumption in 2-dihydroxymethyl butyraldehyde process, the reuse of by product 2-alkyl aldehyde (EA).After 1999, Nippon Kasei Chemical Company's neat rattan show history etc. is delivered patent US6072082 and EP0937701A1 to aforesaid method and has been carried out Improvement and perfection, illustrate complete process prepared by DMBA, the total recovery (in butyraldehyde) of this technique DMBA reaches 45%, the little and epigranular of products obtained therefrom particle diameter.This is also the operational path having been reported middle best results.
In Japanese Patent Laid-Open 6-192169, clay fertilizer constitution the people such as to control with 2,2-dihydroxymethyl alkanal (DMB) and formaldehyde pass through disproportionation reaction, first generate TriMethylolPropane(TMP) (TMP), again under the katalysis of palladium or platinum, use oxygen-containing gas to be oxidized, yield can reach more than 90%, preparation DMBA and salt thereof.This technological advantage is that oxidizing reaction selectivity is high, but significantly shortcoming is again oxidized after intermediate product alkanal is reduced, and add the change procedure of redox state, Atom economy is low.
In addition, in English Patent GB1167274, by TMP and formaldehyde or acetone are formed 1,3-dioxane compound NaClO is oxidized to corresponding carboxylic acid, slough methylene radical under acidic conditions and obtain dimethylolalkanoic acids product, two step yields are respectively 75% and 34%, overall yield about 25%.US Patent No. 3466309 reports with substituted oxazole quinoline for raw material, and under the effect of mineral acid (as concentrated hydrochloric acid), hydrolysis obtains corresponding dimethylolalkanoic acids.Above-mentioned two kinds of handicraft product purification difficult, total recovery is very low, and therefore the method is only for preparing special dimethylolalkanoic acids under laboratory condition, and is not suitable for suitability for industrialized production.
In sum, the subject matter that the synthesis technique of existing 2,2-dimethylolalkanoic acids exists has: feed stock conversion is low, and product yield is difficult to reach 50%, product purification difficulty, and operation generation wastewater flow rate is large, organic solvent usage quantity is large.
Summary of the invention
The object of the invention is to provide one to prepare the method for 2,2-dimethylolalkanoic acids, to simplifying reactions steps, improving feed stock conversion, significantly improving product yield.
For realizing above-mentioned target, technical solution of the present invention comprises following steps: (1) with structural formula is alkyl nitrile and chloromethyl methyl ether for raw material, under alkali effect, generating structure formula is
2,2-dimethoxy alkyl nitrile;
(2) under the action of an acid, hydrolysis reaction generating structure formula occurs is 2,2-dimethoxy alkyl nitrile in step (1) 2,2-dimethylolalkanoic acids, wherein R is the alkyl or cycloalkyl of C1-C6, one in preferable methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, n-pentyl, isopentyl, neo-pentyl, cyclopentyl, n-hexyl and cyclohexyl, more preferably the one in methyl, ethyl, n-propyl, n-pentyl and cyclohexyl, further preferable methyl or ethyl.
In step of the present invention (1), there is nucleophilic substitution reaction in alkyl nitrile and chloromethyl methyl ether under the effect of alkali, and the mol ratio of alkyl nitrile and chloromethyl methyl ether is 1:2-10, preferred 1:2-5, be more preferably 1:2.05-2.5, ensure that alkyl nitrile reacts completely, improve reaction yield.
Because the acidic hydrogen activity of alkyl nitrile cyano group α position is more weak, for making effectively nucleophilic substitution reaction to occur, the alkali selected is mineral alkali or organic bases, comprise the one or two or more in the alkoxide of the hydride of the oxyhydroxide of basic metal or alkaline-earth metal, basic metal or alkaline-earth metal and the C1-C4 of basic metal or alkaline-earth metal, the one or two or more in preferred sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium methylate, sodium ethylate, aluminum isopropylate, sodium tert-butoxide, potassium tert.-butoxide, sodium hydride, potassium hydride KH and hydrolith; Be more preferably the one or two or more in sodium hydroxide, sodium hydride and potassium tert.-butoxide, one or both more preferably in sodium hydride and potassium tert.-butoxide.
Consider the consumption of chloromethyl methyl ether in step of the present invention (1), the molar weight of the one or two or more of hydroxide ion, hydride ion and alcoxyl negative ion contained in alkali used at least should be suitable with the molar weight of chloromethyl methyl ether, the mol ratio of the one or two or more of the hydroxide ion, hydride ion and the alcoxyl negative ion that contain in alkyl nitrile and alkali used is 1:2-10, preferred 1:2-5, is more preferably 1:2.05-2.5.The reaction of 1mol alkyl nitrile consumes 2mol chloromethyl methyl ether, and when the alkali selected is the one or two or more in the alkoxide of the oxyhydroxide of basic metal or alkaline-earth metal and the C1-C4 of basic metal or alkaline-earth metal, alkali and chloromethyl methyl ether can once add; When the alkali selected is the one or two or more in the hydride of basic metal or alkaline-earth metal, alkali and chloromethyl methyl ether can add in batches.
Step of the present invention (1) is preferably carried out in the presence of the solvent, described solvent is trichloromethane, tetracol phenixin, 1, 2-ethylene dichloride, tetrahydrofuran (THF), tetrahydropyrans, dioxane, glycol dimethyl ether, the tertiary butyl ether of ethylene glycol bisthioglycolate, toluene, dimethylbenzene and N, one or two or more in dinethylformamide, be preferably tetracol phenixin, glycol dimethyl ether, tetrahydrofuran (THF), toluene and N, one or two or more in dinethylformamide, be more preferably tetrahydrofuran (THF) and N, one or both in dinethylformamide, the mass ratio of described solvent and alkyl nitrile is 1-10:1, preferred 1.5-5:1.
The temperature of reaction of step of the present invention (1) is 0-100 DEG C, and the reaction times is 0.2-24h, preferred 0.5-12h.Particularly, step (1) temperature of reaction is according to selecting the difference of alkali and different, when selecting the oxyhydroxide of basic metal or alkaline-earth metal, desired reaction temperature is higher, temperature of reaction is 50-100 DEG C, preferred 70-100 DEG C, the boiling point that generally need reach reaction solvent refluxes, and now this temperature condition lower reaction times is 2-8h; When the alkoxide of the C1-C4 selecting basic metal or alkaline-earth metal is alkali, required reaction conditions is comparatively gentle, and now temperature of reaction is 0-50 DEG C, preferred 30-50 DEG C, and this temperature condition lower reaction times is 1-4h; When the hydride selecting basic metal or alkaline-earth metal is alkali, for controlling speed of reaction and exothermic heat of reaction, reaction is carried out at a lower temperature, therefore temperature of reaction is 0-30 DEG C, preferred 0-10 DEG C, and the reaction times under this temperature condition is 0.5-2h.
After step of the present invention (1) reaction terminates, carry out aftertreatment to reaction solution, the treatment process of the reaction solution of step (1) is different because selecting the difference of alkali.When being the one or two or more of the oxyhydroxide of basic metal or alkaline-earth metal when selecting alkali, after reaction terminates, excessive alkali and the salt of generation are crossed and are filtered, and gained filtrate carries out concentrated obtaining the thick product of 2,2-dimethoxy alkyl nitrile, proceeds in step (2), when being the one or two or more in the alkoxide of the hydride of basic metal or alkaline-earth metal and the C1-C4 of basic metal or alkaline-earth metal when selecting alkali, excessive alkali needs use water to carry out cancellation, through extraction, concentrate and obtain 2, the thick product of 2-dimethoxy alkyl nitrile, proceed in step (2), extraction solvent is the one or two or more in the C1-C4 alkyl ester of acetic acid and the C1-C4 alkyl ester of propionic acid, preferred methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, tert.-butyl acetate, methyl propionate, ethyl propionate, n propyl propionate, isopropyl propionate, n-butyl propionate, one or two or more in isobutyl propionate and propanoic acid tert-butyl ester etc.
The transformation efficiency of step (1) is 95-99%, and thick product directly proceeds to step (2), and overall yield calculates with alkyl nitrile mole number.
Due to 2, poorly soluble in water of 2-dimethoxy alkyl nitrile, therefore the organic solvent dissolution 2 dissolved each other with water is preferably used, the thick product of 2-dimethoxy alkyl nitrile, then be hydrolyzed reaction in strong aqueous acid, consider that hydrolysis reaction can produce methyl alcohol, dissolve 2, the organic solvent particular methanol of the thick product of 2-dimethoxy alkyl nitrile, dissolve 2, the consumption of the organic solvent of the thick product of 2-dimethoxy alkyl nitrile and the mass ratio 0.2-1.0:1 of the thick product of 2,2-dimethoxy alkyl nitrile, preferred 0.4-0.6:1.
There is the hydrolysis of high yield in the cyano group in step of the present invention (2) in 2,2-dimethoxy alkyl nitrile, by product is only the ammonium salt class being insoluble to organic solvent, is conducive to subsequent purification process under strongly acidic conditions.
In step of the present invention (2), the hydrolysis reaction of 1mol cyano group produces 1mol NH 3, neutralize with acid and need consume 1mol hydrogen ion, thus in step (2) in 2,2-dimethoxy alkyl nitrile and acid contained hydrionic mol ratio be 1:1-12, preferred 1:1-3, is more preferably 1:1-1.5.
In step of the present invention (2), acid is the one or two or more in mineral acid and organic acid, one or two or more in preferred hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, perchloric acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid and tosic acid etc., be more preferably the one or two or more in hydrochloric acid, sulfuric acid, trifluoroacetic acid and tosic acid, one or both more preferably in sulfuric acid and tosic acid.
In step of the present invention (2), because the hydrolysis reaction of 2,2-dimethoxy alkyl nitrile decomposes or the side reaction such as polymerization too high can the generation of temperature, therefore hydrolysising reacting temperature is 20-110 DEG C, preferred 40-100 DEG C, more preferably 70-90 DEG C; The consumption of 2,2-dimethoxy alkyl nitrile can think that reaction is complete completely, and the reaction times is 0.2-12h, preferred 0.5-5h, more preferably 1-3h.
In the hydrolysis reaction liquid of step of the present invention (2) gained, containing the thick product of 2,2-dimethylolalkanoic acids and inorganic salt, any known post-processing step can be adopted, 2,2-dimethylolalkanoic acids of purifying from hydrolysis reaction liquid.Preferred post-processing step is crystallization processes, comprises the following steps: the hydrolysis reaction liquid of step (2) is regulated pH to 2-4, while existing, ensures the quality of crystallization to make 2,2-dimethylolalkanoic acids with the form of acid.If pH is higher, then 2,2-dimethylolalkanoic acids parts exist in a salt form, effectively cannot obtain product; If pH is on the low side, then 2,2-dimethylolalkanoic acids may generate ester when concentrated process operation, cause product loss.Underpressure distillation obtains thickness enriched material, gained thickness enriched material is dissolved in recrystallisation solvent, the consumption of recrystallisation solvent and the mass ratio of thickness enriched material are 1-20:1, are preferably 1-10:1, are more preferably 2-4:1, be heated to boiling, and filtered while hot, removing inorganic salt, gained hot mother liquor is cooled to room temperature, crystallize out, can obtain qualified product after filtration.
Recrystallisation solvent of the present invention comprises the ketone of C3-C9, one or two or more in the ester of C3-C9, preferred acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl isopropyl Ketone, methyl n-butyl ketone, methyl iso-butyl ketone (MIBK), metacetone, ethyl n-propyl ketone, ethyl isopropyl ketone, ethyl normal-butyl ketone, ethyl isobutylo ketone, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, tert.-butyl acetate, hexalin acetate, methyl propionate, ethyl propionate, the one or two or more of n propyl propionate and propanoic acid tert-butyl ester etc., more preferably methyl ethyl ketone, methyl iso-butyl ketone (MIBK), one or two or more in ethyl acetate and methyl propionate.
Major advantage of the present invention is:
1) a kind of operational path of preparation 2,2-dimethylolalkanoic acids is newly provided;
2) overall yield of product 2, the 2-dimethylolalkanoic acids obtained is high, purity is high, and wherein the overall yield of 2,2-dimethylol propionic acids can reach 92.9%, and the overall yield that purity can reach 99.2%, 2,2-dimethylolpropionic acid can reach 89.3%, and purity can reach 99.5%;
3) industrialization can realize solvent and applies mechanically, and by-product is only a small amount of inorganic salt.
Accompanying drawing illustrates:
Fig. 1 is the 1HNMR spectrogram of 2,2-dimethylolpropionic acids prepared by embodiment 1;
Fig. 2 is the infrared spectrum of 2,2-dimethylolpropionic acids prepared by embodiment 1;
Fig. 3 is the 1HNMR spectrogram of 2,2-dimethylol propionic acids prepared by embodiment 2;
Fig. 4 is the infrared spectrum of 2,2-dimethylol propionic acids prepared by embodiment 2;
Fig. 5 is 2,2-dihydroxymethyl-2-cyclohexyl acetic acid 1HNMR spectrograms prepared by embodiment 5;
Fig. 6 is 2,2-dihydroxymethyl-2-cyclohexyl acetic acid infrared spectrums prepared by embodiment 5.
Embodiment
Below in conjunction with embodiment, the present invention is further described, it is pointed out that embodiment does not form the restriction to application claims protection domain.
Main raw material source involved in the present invention is as follows:
Methyl alcohol, methyl iso-butyl ketone (MIBK), tetracol phenixin, tetrahydrofuran (THF), DMF (DMF), ethyl acetate, n-propyl acetate: Tianjin Kermel Chemical Reagent Co., Ltd.;
Propionitrile, n-Butyronitrile, sodium hydride: Chemical Reagent Co., Ltd., Sinopharm Group;
Chloromethyl methyl ether, cyclohexyl acetonitrile, sodium methylate, potassium tert.-butoxide: Sigma-Aldrich;
Sodium hydroxide, sulfuric acid, hydrochloric acid, phosphoric acid, tosic acid: Xilong Chemical Co., Ltd;
1HNMR uses Bruker AV300 test, and 50mg sample is dissolved in 0.5mL D2O.
Infrared use Nicolet Nexus470 tests, and adopts KBr coating method.
Embodiment 1
By 207g(3.0mol in the 2L there-necked flask that agitator, return line, thermometer are housed) n-Butyronitrile is dissolved in 650mL(1040g) tetracol phenixin, add NaOH solid 246g(6.15mol), start and to stir and heating is preheated to 50 DEG C; This temperature is kept to drip chloromethyl methyl ether 492g(6.15mol), after dropwising, temperature of reaction system is increased to 80 DEG C, keeps system backflow 12h.
After reaction terminates, suction filtration removes the NaCl of excessive NaOH and reaction generation, and the distillation of gained solution decompression removes desolventizing and obtains concentrated solution 480g, and this concentrated solution 250g dissolve with methanol, drips the H of 40wt% under agitation condition 2sO 4aqueous solution 551.3g(2.25mol), after be heated to 70 DEG C hydrolysis 5h, hydrolyzed solution cooling after, add the NaOH aqueous solution 120g of 50wt%, survey system pH be 3.0.
Hydrolysis reaction liquid (1400g) underpressure distillation is removed most of solvent (620g), add methyl iso-butyl ketone (MIBK) 2350g, be heated to 70 DEG C under stirring, heat filtering removing vitriol, mother liquor slowly cools to 5 DEG C, separate out white solid, filter final vacuum loft drier 45 DEG C of dry 1.5h, obtain white crystal 313.5g, 2,2-dimethylolpropionic acid content 97.5%, total recovery (with n-Butyronitrile molar basis) is 68.8%.
Product 1h NMR data (D 2o is solvent, and TMS is interior mark): 0.74(t, 3H ,-CH 3), 1.43(q, 2H, CH 3cH 2-), 3.63(dd, 4H ,-CH 2oH).
Infrared results: 3345(ν -COOH, ν -CH2OH), 2832 ~ 2957(ν -C-CH3), 1697(ν -C=O) 1338(ν cH2), 1026(ν- cH2CH3).
Embodiment 2
Being equipped with agitator, return line, temperature take into account 100g(1.8mol in the 1L there-necked flask of protection of inert gas) propionitrile is dissolved in 200mL(180g) tetrahydrofuran (THF) (THF); potassium tert.-butoxide 423.4g(3.8mol is added) under room temperature; after; increase ice-water bath; chloromethyl methyl ether 302g(3.8mol is dripped under abundant stirring), after dropwising, keep 0-5 DEG C of 0.5h; start heating after removing ice bath, system is heated to 60 DEG C of reaction 6h.
Reaction terminates system temperature and is down to room temperature, drips H 2o6.5g cancellation Excess t-butanol potassium, adds rear stirring 0.2h, adds H 2o400g diluting reaction system, extracts with n-propyl acetate 2 × 350mL, and except desolventizing after organic phase merges, obtain thickness concentrated solution 280g, this concentrated solution 140g dissolve with methanol, drips the H of 40wt% under agitation condition 3pO 4aqueous solution 464g, after be heated to 80 DEG C reaction 2h, hydrolyzed solution cooling after, add the NaOH aqueous solution 7.5g of 50wt%, survey system pH be 3.0.
Hydrolysis reaction liquid (885g) underpressure distillation is removed most of solvent (about 420g), gained enriched material adds ethyl acetate 950g, be heated to 60 DEG C under stirring, heat filtering removing phosphoric acid salt, mother liquor slowly cools to 10 DEG C, separate out white solid, filter final vacuum loft drier 45 DEG C of dry 1.5h, obtain white crystal 228g, 2,2-dimethylol propionic acid content 99.2%, total recovery (with propionitrile molar basis) is 92.9%.
Product 1hNMR result: 0.94(s, 3H ,-CH 3), 3.50(dd, 4H ,-CH 2oH).
Infrared results (σ/cm -1): 3373(ν -CH2OH), 3232(ν -COOH), 2820 ~ 2960(ν -C-CH3), 1693(ν -C=O), 1308(ν cH2).
Embodiment 3
Being equipped with agitator, return line, temperature take into account 100g(1.8mol in the 1L there-necked flask of protection of inert gas) propionitrile is dissolved in 300mL(280g) DMF; sodium methylate 205.2g(3.8mol is added) under room temperature; after adding completely; increase ice-water bath; chloromethyl methyl ether 304g(3.8mol is dripped) under abundant stirring; after dropwising, keep 0-5 DEG C of 0.5h, start after removing ice bath to be heated to 80 DEG C of reaction 3h.
Reaction terminates system temperature and is down to room temperature, drips H 2o6.5g cancellation excess sodium methoxide, adds rear stirring 0.2h, adds H 2o600g diluting reaction system, extract with n-propyl acetate 2 × 300mL, except desolventizing after organic phase merges, obtain thickness concentrated solution 265g, this concentrated solution 120g dissolve with methanol, under agitation condition, drip the HCl aqueous solution 361g of 20wt%, after be heated to 80 DEG C hydrolysis 3h, after hydrolyzed solution cooling, add the NaOH aqueous solution 14.3g of 50wt%, surveying system pH is 3.0.
Hydrolysis reaction liquid (760g) underpressure distillation removes most of solvent (about 410g), gained enriched material adds methyl ethyl ketone 1050g, is heated to 70 DEG C under stirring, filtered while hot removing ammonium chloride and sodium-chlor, mother liquor slowly cools to 5 DEG C, separate out white solid, filter final vacuum loft drier 45 DEG C of dry 1.5h, obtain 2,2-dimethylol propionic acid white crystal 219.3g, 2,2-dimethylol propionic acid content 96.0%, total recovery (with propionitrile molar basis) is 86.5%.
Embodiment 4
Being equipped with agitator, in 500mL there-necked flask that temperature takes into account protection of inert gas by 27.6g(0.4mol) n-Butyronitrile is dissolved in 100mL(94g) in solvent DMF; solution is cooled to lower than 5 DEG C by ice-water bath; slowly add sodium hydride 10.56g(0.44mol) in batches; adition process keeps system temperature not higher than 5 DEG C, and uses N 2purge, observed H 2bubble produces.Bubble drips the chloromethyl methyl ether-DMF solution 70.4g(0.44mol of 50wt% after producing and stopping), be warming up to 25 DEG C after dropwising, stirring reaction 1h.
Again cool, repeat said process, add sodium hydride 10.56g, and the chloromethyl methyl ether-DMF solution 70.4g of 50wt%.After be warming up to 30 DEG C, keep thermotonus 2h.
After reaction terminates, drip H 2o3.0g cancellation is reacted, and adds H 2o100g diluting reaction system, extracts with ethyl acetate 2 × 150mL, except desolventizing after organic phase merges, obtains colorless viscous concentrated solution 60.0g.
This concentrated solution 30g dissolve with methanol, drips the tosic acid aqueous solution 238.7g(0.42mol of 30wt% under agitation condition), after be heated to 90 DEG C hydrolysis 2h, hydrolyzed solution cooling after, add the NaOH aqueous solution 1.6g of 50wt%, survey system pH be 3.2.
Hydrolysis reaction liquid (330g) underpressure distillation removes most of solvent (about 200g), gained enriched material adds methyl iso-butyl ketone (MIBK) 260g, be heated to 70 DEG C under stirring, heat filtering removing tosilate, mother liquor slowly cools to 5 DEG C, separate out white solid, filter final vacuum loft drier 45 DEG C of dry 1.5h, obtain white crystal 53.1g, 2,2-dimethylolpropionic acid content 99.5%, total recovery (with n-Butyronitrile molar basis) is 89.3%.
Embodiment 5
Being equipped with agitator, return line, temperature take into account 123g(1.0mol in the 1L there-necked flask of protection of inert gas) cyclohexyl acetonitrile is dissolved in 300mL(270g) tetrahydrofuran (THF); potassium tert.-butoxide 280g(2.5mol is added) under room temperature; after adding completely; increase ice-water bath, fully stir lower dropping chloromethyl methyl ether 200g(2.5mol), after dropwising; keep 0-5 DEG C of 0.5h; start after removing ice bath to be heated to 70 DEG C, keep solvent refluxing, reaction 3h.
Reaction terminates system temperature and is down to room temperature, drips H 2o20g cancellation Excess t-butanol potassium, adds H 2o450g diluting reaction system, extracts with ethyl acetate 2 × 300mL, except desolventizing after organic phase merges, obtains concentrated solution 208g.
This concentrated solution 100g dissolve with methanol, drips the H of 40wt% under agitation condition 2sO 4aqueous solution 184g(0.75mol), after be heated to 70 DEG C hydrolysis 5h, hydrolyzed solution cooling after, add the NaOH aqueous solution 40g of 50wt%, survey system pH be 3.0.
Hydrolysis reaction liquid (530g) underpressure distillation removing methyl alcohol and water (about 230g), gained enriched material adds n-propyl acetate 600g, be heated to 90 DEG C under stirring, heat filtering removing vitriol, mother liquor slowly cools to 5 DEG C, separate out white solid, filter final vacuum loft drier 45 DEG C of dry 1.5h, obtain white crystal 176.2g, 2,2-dihydroxymethyl-2-cyclohexyl acetic acid content 94.0%, total recovery (with cyclohexyl acetonitrile molar basis) is for 82.0%.
Product 1hNMR result: 0.18-0.75(m, 10H ,-C 5h 10), 0.95(m, 1H ,-CHC 5h 10), 3.67(dd, 4H ,-CH 2oH).
Infrared results (σ/cm -1): 3365(br, ν -COOH, ν -CH2OH), 2800 ~ 3020(ν -C5H10), 1293(ν -OCH2), 742(ν -CH2CH2CH2-).

Claims (23)

1. prepare the method for 2,2-dimethylolalkanoic acids for one kind, comprise following reactions steps:
(1) with structural formula be alkyl nitrile and chloromethyl methyl ether be raw material, under alkali effect, generating structure formula is 2,2-dimethoxy alkyl nitrile;
(2) under the action of an acid, hydrolysis reaction generating structure formula occurs is 2,2-dimethoxy alkyl nitrile in step (1) 2,2-dimethylolalkanoic acids, wherein R is the alkyl or cycloalkyl of C1-C6.
2. method according to claim 1, is characterized in that, described R is selected from the one in methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, n-pentyl, isopentyl, neo-pentyl, cyclopentyl, n-hexyl and cyclohexyl.
3. method according to claim 1, is characterized in that, the mol ratio of described alkyl nitrile and chloromethyl methyl ether is 1:2-10.
4. method according to claim 3, is characterized in that, the mol ratio of described alkyl nitrile and chloromethyl methyl ether is 1:2-5.
5. method according to claim 4, is characterized in that, the mol ratio of described alkyl nitrile and chloromethyl methyl ether is 1:2.05-2.5.
6. method according to claim 1, is characterized in that, described alkali comprise in the alkoxide of the oxyhydroxide of basic metal or alkaline-earth metal, basic metal or the hydride of alkaline-earth metal and the C1-C4 of basic metal or alkaline-earth metal one or more; The mol ratio of negative ion contained in described alkyl nitrile and alkali is 1:2-10.
7. method according to claim 6, it is characterized in that, described alkali be selected from sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium methylate, sodium ethylate, aluminum isopropylate, sodium tert-butoxide, potassium tert.-butoxide, sodium hydride, potassium hydride KH and hydrolith one or more; The mol ratio of negative ion contained in described alkyl nitrile and alkali is 1:2-5.
8. method according to claim 7, is characterized in that, the mol ratio of negative ion contained in described alkyl nitrile and alkali is 1:2.05-2.5.
9. method according to claim 1, it is characterized in that, the reaction of step (1) is carried out in the presence of the solvent, described solvent is trichloromethane, tetracol phenixin, 1, the tertiary butyl ether of 2-ethylene dichloride, tetrahydrofuran (THF), tetrahydropyrans, dioxane, glycol dimethyl ether, ethylene glycol bisthioglycolate, toluene, dimethylbenzene and N, one or more in dinethylformamide, the mass ratio of solvent and alkyl nitrile is 1-10:1.
10. method according to claim 9, is characterized in that, the mass ratio of described solvent and alkyl nitrile is 1.5-5:1.
11. methods according to claim 1, is characterized in that, step (1) temperature of reaction is 0-100 DEG C; Reaction times is 0.2-24h.
12. methods according to claim 11, is characterized in that, step (1) reaction times is 0.5-12h.
13. methods according to claim 1, is characterized in that, acid described in step (2) is one or more in hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, perchloric acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid and tosic acid; In 2,2-dimethoxy alkyl nitrile and acid, contained hydrionic mol ratio is 1:1-12.
14. methods according to claim 13, is characterized in that, in 2,2-dimethoxy alkyl nitrile described in step (2) and acid, contained hydrionic mol ratio is 1:1-3.
15. methods according to claim 14, is characterized in that, in 2,2-dimethoxy alkyl nitrile described in step (2) and acid, contained hydrionic mol ratio is 1:1-1.5.
16. methods according to claim 1, is characterized in that, step (2) hydrolysising reacting temperature is 20-110 DEG C; Step (2) hydrolysis time is 0.2-12h.
17. methods according to claim 16, is characterized in that, step (2) hydrolysising reacting temperature is 40-100 DEG C; Step (2) hydrolysis time is 0.5-5h.
18. methods according to claim 17, is characterized in that, step (2) hydrolysising reacting temperature is 70-90 DEG C; Step (2) hydrolysis time is 1-3h.
19. according to the method in claim 1-18 described in any one, it is characterized in that, after step (2) hydrolysis reaction, crystallization processes is adopted to obtain 2, 2-dimethylolalkanoic acids sterling, the hydrolysis reaction liquid of step (2) is comprised the steps: to regulate pH to 2-4, underpressure distillation obtains thickness enriched material, thickness enriched material is dissolved in recrystallisation solvent, the consumption of recrystallisation solvent and the mass ratio of thickness enriched material are 1-20:1, be heated to boiling, and filtered while hot, removing inorganic salt, gained hot mother liquor is cooled to room temperature, crystallize out, 2 are obtained after filtration, 2-dimethylolalkanoic acids sterling.
20. methods according to claim 19, is characterized in that, the consumption of described recrystallisation solvent and the mass ratio of thickness enriched material are 1-10:1.
21. methods according to claim 20, is characterized in that, the consumption of described recrystallisation solvent and the mass ratio of thickness enriched material are 2-4:1.
22. methods according to claim 19, is characterized in that, described recrystallisation solvent comprise in the ester of the ketone of C3-C9, C3-C9 one or more.
23. methods according to claim 22, it is characterized in that, described recrystallisation solvent be selected from acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl isopropyl Ketone, methyl n-butyl ketone, methyl iso-butyl ketone (MIBK), metacetone, ethyl n-propyl ketone, ethyl isopropyl ketone, ethyl normal-butyl ketone, ethyl isobutylo ketone, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, tert.-butyl acetate, hexalin acetate, methyl propionate, ethyl propionate, n propyl propionate and propanoic acid tert-butyl ester one or more.
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