CN102126925A - Preparation method of hydroxymethyl cyclane - Google Patents
Preparation method of hydroxymethyl cyclane Download PDFInfo
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- CN102126925A CN102126925A CN2011100055496A CN201110005549A CN102126925A CN 102126925 A CN102126925 A CN 102126925A CN 2011100055496 A CN2011100055496 A CN 2011100055496A CN 201110005549 A CN201110005549 A CN 201110005549A CN 102126925 A CN102126925 A CN 102126925A
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- methylol
- naphthenic hydrocarbon
- alcohol
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- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 title abstract 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 73
- 229930195733 hydrocarbon Natural products 0.000 claims description 31
- 239000004215 Carbon black (E152) Substances 0.000 claims description 30
- 150000002430 hydrocarbons Chemical class 0.000 claims description 30
- -1 cycloalkyl carboxylicesters Chemical class 0.000 claims description 14
- 238000004821 distillation Methods 0.000 claims description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000010953 base metal Substances 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- MPNNOLHYOHFJKL-UHFFFAOYSA-N peroxyphosphoric acid Chemical compound OOP(O)(O)=O MPNNOLHYOHFJKL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract 1
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- WPOPOPFNZYPKAV-UHFFFAOYSA-N cyclobutylmethanol Chemical compound OCC1CCC1 WPOPOPFNZYPKAV-UHFFFAOYSA-N 0.000 description 14
- GUDMZGLFZNLYEY-UHFFFAOYSA-N cyclopropylmethanol Chemical compound OCC1CC1 GUDMZGLFZNLYEY-UHFFFAOYSA-N 0.000 description 11
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 238000013019 agitation Methods 0.000 description 8
- 238000009835 boiling Methods 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 239000012044 organic layer Substances 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 208000030507 AIDS Diseases 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- VSSAZBXXNIABDN-UHFFFAOYSA-N cyclohexylmethanol Chemical compound OCC1CCCCC1 VSSAZBXXNIABDN-UHFFFAOYSA-N 0.000 description 2
- ISQVBYGGNVVVHB-UHFFFAOYSA-N cyclopentylmethanol Chemical compound OCC1CCCC1 ISQVBYGGNVVVHB-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical group CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000012280 lithium aluminium hydride Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- PKAHQJNJPDVTDP-UHFFFAOYSA-N methyl cyclopropanecarboxylate Chemical class COC(=O)C1CC1 PKAHQJNJPDVTDP-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- KVVDRQDTODKIJD-UHFFFAOYSA-N 2-cyclopropylacetic acid Chemical compound OC(=O)CC1CC1 KVVDRQDTODKIJD-UHFFFAOYSA-N 0.000 description 1
- XWTWGWCSIXFCEN-UHFFFAOYSA-N 3-methylbutyl cyclopentanecarboxylate Chemical compound CC(C)CCOC(=O)C1CCCC1 XWTWGWCSIXFCEN-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- MFESCIUQSIBMSM-UHFFFAOYSA-N I-BCP Chemical compound ClCCCBr MFESCIUQSIBMSM-UHFFFAOYSA-N 0.000 description 1
- RMOUBSOVHSONPZ-UHFFFAOYSA-N Isopropyl formate Chemical compound CC(C)OC=O RMOUBSOVHSONPZ-UHFFFAOYSA-N 0.000 description 1
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000000730 antalgic agent Substances 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- GAKUKXZINODJOH-UHFFFAOYSA-N cyclobutyl formate Chemical compound O=COC1CCC1 GAKUKXZINODJOH-UHFFFAOYSA-N 0.000 description 1
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- NETZHAKZCGBWSS-CEDHKZHLSA-N nalbuphine Chemical compound C([C@]12[C@H]3OC=4C(O)=CC=C(C2=4)C[C@@H]2[C@]1(O)CC[C@@H]3O)CN2CC1CCC1 NETZHAKZCGBWSS-CEDHKZHLSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000003408 phase transfer catalysis Methods 0.000 description 1
- QEYGAMYURHNUMI-UHFFFAOYSA-N propan-2-yl cyclopropanecarboxylate Chemical compound CC(C)OC(=O)C1CC1 QEYGAMYURHNUMI-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 208000011580 syndromic disease Diseases 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of hydroxymethyl cyclane. The method comprises the following steps of: mixing raw materials of naphthenic base carboxylic ether and alcohol corresponding to the naphthenic base carboxylic ether with an alkaline metal catalyst in a certain ratio; carrying out reaction; neutralizing; distilling and the like to obtain hydroxymethyl cyclane.
Description
Technical field
The invention belongs to the synthetic field of chemical industry, relate to the preparation method of methylol naphthenic hydrocarbon; The preparation method who further relates to C3-6 cycloalkyl methyl alcohol further relates to the preparation method of cyclopropyl-carbinol and cyclobutanemethanol.
Background technology
Methylol naphthenic hydrocarbon (shown in the following formula I) is important organic solvent and organic synthesis intermediate.As the cyclopropyl methylol is the key intermediate of spasmolysis pain medicine and anodyne etc., also is the intermediate that is used for the anti-phorbol of Biochemical Research, as acquired immune deficiency syndrome (AIDS) etc.Cyclobutanemethanol is the intermediate of anodynes such as cloth holder Fino, Nubain.Methylol naphthenic hydrocarbon general all water-soluble, pure, pure chemical property is arranged, hydroxyl can be become ether with halohydrocarbon by halo, becomes ester with carboxylic acid, oxidable one-tenth aldehyde or carboxylic acid, but open loop addition again are a kind of industrial chemicals with very big market potentiality.
Wherein: n is 0,1,2 or 3 integer.
Synthetic for methylol naphthenic hydrocarbon, existing method has multiple, but from not mentioned in the presence of alkali-metal be the technology of feedstock production with the cycloalkyl carboxylicesters.
Proposed to prepare the method for cyclopropyl-carbinol as Chinese patent CN1143065, promptly prepared the method for carboxymethyl cyclopropane by cyclopropanecarboxylcompound.Use the zinc oxide that does not contain chromium to obtain cyclopropyl-carbinol as catalyst hydrogenation cyclopropanecarboxylcompound.
This method is with economical and the mode of environment friendliness obtained cyclopropyl-carbinol, but reaction must be higher by the zinc oxide cost of pressurization and condition that heats up and Chrome-free.
Document [Chinese pharmaceutical chemistry magazine 2003,13 (2) 102-103] has been reported following scheme:
This method is used with diethyl malonate and 1, and the 3-bromo-chloropropane is a starting raw material, close ring, hydrolysis, decarboxylation one pot reaction through phase-transfer catalysis and make cyclobutyl formate, and then reduce cyclobutanemethanol.Though this method reaction conditions gentleness is easy and simple to handle, yield is on the low side to be 41%, causes production cost higher.
[Tetrahedron letters 1981,22 (36) for document; Yiyao Gongye1988,19 (9): 415-417] reported following path of preparing cyclobutanemethanol:
This scheme directly will be encircled fourth formic acid and prepare cyclobutanemethanol with lithium aluminium hydride reduction, and last yield is 72%, and production cost is higher, and the lithium aluminum hydride operation is dangerous.
Document [Tetrahedron Letters 1985,26 (31)] has been reported following operational path:
This route reported ω-iodo-1, and different reagent such as 2-epoxy group(ing) hydride compounds and BuLi make the hydroxy-cyclopentane of different ratios and the mixture of cyclobutanemethanol at Et20 and EtCH2Et reaction.This operational path transformation efficiency is very low, and raw material 6-bromine/iodo-1,2-epoxy group(ing) alkane are difficult to obtain, and final product is difficult to handle and obtains cyclobutanemethanol.
Summary of the invention
The technological deficiency that exists for the preparation method who solves above-mentioned methylol naphthenic hydrocarbon.The preparation method who the purpose of this invention is to provide a kind of methylol naphthenic hydrocarbon further relates to the preparation method of C3-6 cycloalkyl methyl alcohol, further relates to the preparation method of cyclopropyl-carbinol and cyclobutanemethanol.This method raw material is easy to get, and price is low, and synthetic method is simple, and is stable and controllable for quality, and the yield height pollutes few.
To achieve these goals, the present invention has adopted following technical scheme:
A kind of preparation method of methylol naphthenic hydrocarbon, this method is a raw material with cycloalkyl carboxylicesters, alcohol (the corresponding alcohol of cycloalkyl carboxylicesters), mix according to a certain percentage with base metal catalysts such as sodium, potassium,, obtain methylol naphthenic hydrocarbon through steps such as reaction, neutralization, distillations.
This process program cost is all lower than original any scheme; Reduced production cost.
In more detail, the preparation method of methylol naphthenic hydrocarbon of the present invention is characterised in that: with the alcohol shown in the cycloalkyl carboxylicesters shown in the formula II, the formula III is raw material, with base metal catalysts mixing afterreaction, obtains the methylol naphthenic hydrocarbon shown in the formula I;
Reaction equation is as follows:
Among above-mentioned formula I, II or the III, n is 0,1,2 or 3 integer, and R is that carbonatoms is the alkyl of 1-6.N is preferably 1 or 2 integer.
The preparation method that this invents described methylol naphthenic hydrocarbon is characterized in that with basic metal being catalyzer.As preferably, be to be selected from lithium, sodium, potassium, the rubidium one or more.Be more preferably and be selected from sodium, the potassium one or more.
The preparation method that this invents described methylol naphthenic hydrocarbon is characterized in that: after reaction, through the peroxophosphoric acid neutralization, distillation obtains the methylol naphthenic hydrocarbon shown in the formula I.
The preparation method that this invents described methylol naphthenic hydrocarbon is characterized in that: the alcohol shown in the formula III is the corresponding alcohol of cycloalkyl carboxylicesters shown in the formula II.
The preparation method that this invents described methylol naphthenic hydrocarbon is characterized in that, in mole, the usage ratio of cycloalkyl carboxylicesters and catalyzer is 1: 1.0～20.0.As preferably, usage ratio is 1: 1.0-10.0, more preferably 1: 1.0-5.0.
The preparation method that this invents described methylol naphthenic hydrocarbon is characterized in that, in mole, the usage ratio of ester and alcohol is 1: 1.0～30.0.As preferably, usage ratio is 1: 1: 1.0～25.0, more preferably 10.0～15,0.
The preparation method that this invents described methylol naphthenic hydrocarbon is characterized in that the temperature of reacting is 40～150 ℃.As preferably, it is 80～120 ℃.
Alcohol is a kind of in methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, sec-butyl alcohol, amylalcohol, 2-amylalcohol, 3-amylalcohol, the 2-methylpropanol.
The preparation method that this invents described methylol naphthenic hydrocarbon is characterized in that reacting in organic solvent and carries out, and this organic solvent is selected from hydro carbons, aromatic hydrocarbons etc.Preferred aromatic hydrocarbons, preferred especially benzene,toluene,xylene etc.
The present invention has following positively effect owing to adopted above technical scheme:
1, this programme adopts wherein a kind of raw material as the providing of proton hydrogen, and has promoted reaction conversion ratio, improves the yield and the quality product of product.
2, catalysts is selected basic catalysts such as sodium Metal 99.5 for use, has improved the yield of reaction greatly, makes existing yield be up to 90%, all exceeds far away than original any scheme.
3, boil before the gained in the distillation and can be used for secondary response down, realized recycled, make this scheme reach the requirement of Green Chemistry.
Embodiment
Below by preferred embodiment preferred forms of the present invention is described; the embodiment here is to explain the present invention; and should not be construed as limitation of the present invention; under the situation that does not break away from spirit of the present invention and essential scope; can make various changes and modifications, these all should be included within protection scope of the present invention.
Embodiment 1
The preparation of present embodiment explanation cyclopropyl-carbinol
With 150g sodium Metal 99.5,500g toluene, add to be furnished with electric mixing device, in the four-hole boiling flask of thermometer, constant pressure funnel and reflux condensing tube, under agitation mixed solution (Virahol 940g+ cyclopropanecarboxylic acid isopropyl ester 180g) is added drop-wise in the described flask, continue reaction with 6 hours, temperature of reaction is 90-110 ℃.The phosphoric acid of 682g 80% is slowly added in the described flask, tell organic layer, organic layer obtains product through distillation.
The cyclopropyl-carbinol yield is 89.6%, and content is greater than 99.0%.
Embodiment 2
The preparation of present embodiment explanation cyclopropyl-carbinol
With 150g sodium Metal 99.5,500g toluene, add to be furnished with electric mixing device, in the four-hole boiling flask of thermometer, constant pressure funnel and reflux condensing tube, under agitation mixed solution (sec-butyl alcohol 972g+ cyclopropanecarboxylic acid methyl esters 112g) is added drop-wise in the described flask, continue reaction with 6 hours, temperature of reaction is 95-110 ℃, and all the other are all with embodiment 1.
The cyclopropyl-carbinol yield is 89.4%, and content is greater than 99.0%.
Embodiment 3
The preparation of present embodiment explanation cyclopropyl-carbinol
With 150g sodium Metal 99.5,500g toluene, add to be furnished with electric mixing device, in the four-hole boiling flask of thermometer, constant pressure funnel and reflux condensing tube, under agitation mixed solution (ethanol 720g+ cyclopropanecarboxylic acid methyl esters 160g) is added drop-wise in the described flask, continue reaction with 6 hours, temperature of reaction is 90-110 ℃, and all the other are all with embodiment 1.
The cyclopropyl-carbinol yield is 89.3%, and content is greater than 99.0%.
Embodiment 4
The preparation of present embodiment explanation cyclobutanemethanol
With 150g sodium Metal 99.5,500g toluene, add to be furnished with electric mixing device, in the four-hole boiling flask of thermometer, constant pressure funnel and reflux condensing tube, under agitation mixed solution (Virahol 998g+ ring fourth isopropyl formate 196g) is added drop-wise in the described flask, continue reaction with 6 hours, temperature of reaction is 90-110 ℃.The phosphoric acid of 682g 80% is slowly added in the described flask, tell organic layer, organic layer obtains product through distillation.
The cyclobutanemethanol yield is 80.8%, and content is greater than 98.0%.
Embodiment 5
The preparation of present embodiment explanation cyclobutanemethanol
With 150g sodium Metal 99.5,500g toluene, add to be furnished with electric mixing device, in the four-hole boiling flask of thermometer, constant pressure funnel and reflux condensing tube, under agitation mixed solution (methyl alcohol 500g+ ring fourth methyl-formiate 145g) is added drop-wise in the described flask, continue reaction with 6 hours, temperature of reaction is 90-110 ℃, and all the other are all with embodiment 4.
The cyclobutanemethanol yield is 89.4%, and content is greater than 99.0%.
Embodiment 6
The preparation of present embodiment explanation cyclobutanemethanol
With 150g sodium Metal 99.5,500g toluene, add to be furnished with electric mixing device, in the four-hole boiling flask of thermometer, constant pressure funnel and reflux condensing tube, under agitation mixed solution (ethanol 720g+ ring fourth ethyl formate 165g) is added drop-wise in the described flask, continue reaction with 6 hours, temperature of reaction is 90-110 ℃, and all the other are all with embodiment 4.
The cyclobutanemethanol yield is 89.9%, and content is greater than 99.0%.
Embodiment 7
The preparation of present embodiment explanation cyclopentyl carbinol
With 150g sodium Metal 99.5,500g toluene, add to be furnished with electric mixing device, in the four-hole boiling flask of thermometer, constant pressure funnel and reflux condensing tube, under agitation mixed solution (primary isoamyl alcohol 1378g+ cyclopentanecarboxylic acid isopentyl ester 263g) is added drop-wise in the described flask, continue reaction with 6 hours, temperature of reaction is 110-130 ℃.The phosphoric acid of 682g 80% is slowly added in the described flask, tell organic layer, organic layer obtains product through distillation.
The cyclopentyl carbinol yield is 86.0%, and content is greater than 99.0%.
Embodiment 8
The preparation of present embodiment explanation hexahydrobenzyl alcohol
With 150g sodium Metal 99.5,500g toluene, add to be furnished with electric mixing device, in the four-hole boiling flask of thermometer, constant pressure funnel and reflux condensing tube, under agitation mixed solution (the secondary own ester 303g of secondary hexyl alcohol 1598g+ heptanaphthenic acid) is added drop-wise in the described flask, continue reaction with 6 hours, temperature of reaction is 110-140 ℃.The phosphoric acid of 682g 80% is slowly added in the described flask, tell organic layer, organic layer obtains product through distillation.
The hexahydrobenzyl alcohol yield is 80.7%, and content is greater than 99.0%.
Embodiment 9-11
According to the identical step of embodiment 1-3, except potassium as the catalyzer, all the other operating process are equal to.
Table 1 embodiment 9～11 catalyst levelss and processing condition and result
Embodiment 12-14
According to the identical step of embodiment 4-6, except potassium as the catalyzer, all the other operating process are equal to.
Table 2 embodiment 12～14 catalyst levelss and processing condition and result
Claims (10)
1. the preparation method of the methylol naphthenic hydrocarbon shown in the formula I, it is characterized in that: with the alcohol shown in the cycloalkyl carboxylicesters shown in the formula II, the formula III is raw material, with base metal catalysts mixing afterreaction, obtains the methylol naphthenic hydrocarbon shown in the formula I;
Among above-mentioned formula I, II or the III, n is 0,1,2 or 3 integer, and R is that carbonatoms is the alkyl of 1-6.
2. the preparation method of methylol naphthenic hydrocarbon according to claim 1 is characterized in that: among formula I, II or the III, n is 0 or 1 integer.
3. the preparation method of methylol naphthenic hydrocarbon according to claim 1 and 2 is characterized in that: catalyzer is to be selected from lithium, sodium, potassium, the rubidium one or more.
4. the preparation method of methylol naphthenic hydrocarbon according to claim 1 is characterized in that: catalyzer is to be selected from sodium, the potassium one or more.
5. the preparation method of methylol naphthenic hydrocarbon according to claim 1 is characterized in that: after reaction, through the peroxophosphoric acid neutralization, distillation obtains the methylol naphthenic hydrocarbon shown in the formula I.
6. the preparation method of methylol naphthenic hydrocarbon according to claim 1 is characterized in that: the alcohol shown in the formula III is the corresponding alcohol of cycloalkyl carboxylicesters shown in the formula II.
7. the preparation method of methylol naphthenic hydrocarbon according to claim 1 is characterized in that: in mole, the usage ratio of cycloalkyl carboxylicesters and catalyzer is 1: 1.0～20.0.
8. the preparation method of methylol naphthenic hydrocarbon according to claim 1 is characterized in that: in mole, the usage ratio of ester and alcohol is 1: 1.0～30.0.
9. according to the preparation method who requires described methylol naphthenic hydrocarbon of right 1, it is characterized in that: the temperature of reaction is 40～150 ℃.
10. according to any one the preparation method of right 1-6, it is characterized in that: alcohol is a kind of in methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol, sec-butyl alcohol, amylalcohol, 2-amylalcohol, 3-amylalcohol, the 2-methylpropanol.
Priority Applications (1)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107324969A (en) * | 2017-07-14 | 2017-11-07 | 杭州盛弗泰新材料科技有限公司 | A kind of method that utilization cyclopropyl-carbinol synthesizes chloromethyl cyclopropane |
| CN107445797A (en) * | 2017-07-14 | 2017-12-08 | 杭州盛弗泰新材料科技有限公司 | A kind of inexpensive low dangerous synthetic method of cyclopropyl-carbinol |
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| GB351359A (en) * | 1929-11-25 | 1931-06-25 | H Th Boehme Ag | Improvements in or relating to the production of primary alcohols |
| GB589380A (en) * | 1941-07-02 | 1947-06-18 | Innovations Chimiques Sinnova | Improved process for the manufacture of alcohol of high molecular weight |
| US3280199A (en) * | 1962-09-27 | 1966-10-18 | Universal Oil Prod Co | Preparation of primary alcohols |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107324969A (en) * | 2017-07-14 | 2017-11-07 | 杭州盛弗泰新材料科技有限公司 | A kind of method that utilization cyclopropyl-carbinol synthesizes chloromethyl cyclopropane |
| CN107445797A (en) * | 2017-07-14 | 2017-12-08 | 杭州盛弗泰新材料科技有限公司 | A kind of inexpensive low dangerous synthetic method of cyclopropyl-carbinol |
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| CN102126925B (en) | 2015-03-25 |
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