CN100999474A - Improved production process of p-iso propyl aniline - Google Patents
Improved production process of p-iso propyl aniline Download PDFInfo
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- CN100999474A CN100999474A CN 200610000799 CN200610000799A CN100999474A CN 100999474 A CN100999474 A CN 100999474A CN 200610000799 CN200610000799 CN 200610000799 CN 200610000799 A CN200610000799 A CN 200610000799A CN 100999474 A CN100999474 A CN 100999474A
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- LRTFPLFDLJYEKT-UHFFFAOYSA-N para-isopropylaniline Chemical compound CC(C)C1=CC=C(N)C=C1 LRTFPLFDLJYEKT-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 8
- 238000006193 diazotization reaction Methods 0.000 claims abstract description 6
- FRCFWPVMFJMNDP-UHFFFAOYSA-N n-propan-2-ylaniline Chemical compound CC(C)NC1=CC=CC=C1 FRCFWPVMFJMNDP-UHFFFAOYSA-N 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 30
- 239000012954 diazonium Substances 0.000 claims description 28
- 150000001989 diazonium salts Chemical class 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- VLJSLTNSFSOYQR-UHFFFAOYSA-N 3-propan-2-ylphenol Chemical compound CC(C)C1=CC=CC(O)=C1 VLJSLTNSFSOYQR-UHFFFAOYSA-N 0.000 claims description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- MFURVJLMZSKTJQ-UHFFFAOYSA-N C1(=CC=CC=C1)S.C(C)(C)C=1C=CC=CC1 Chemical compound C1(=CC=CC=C1)S.C(C)(C)C=1C=CC=CC1 MFURVJLMZSKTJQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- -1 isopropyl phenyl Chemical group 0.000 claims description 6
- 229940067157 phenylhydrazine Drugs 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- MYUDUSLZWQIEFZ-UHFFFAOYSA-N N#C.CC(C)C1=CC=CC=C1 Chemical compound N#C.CC(C)C1=CC=CC=C1 MYUDUSLZWQIEFZ-UHFFFAOYSA-N 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 4
- 229960002050 hydrofluoric acid Drugs 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 3
- 150000001350 alkyl halides Chemical class 0.000 claims description 3
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 claims description 3
- 230000004044 response Effects 0.000 claims description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- HGOYEVBBUJBBCY-UHFFFAOYSA-N CC(C)N(C1=CC=CC=C1)[N+]#N Chemical class CC(C)N(C1=CC=CC=C1)[N+]#N HGOYEVBBUJBBCY-UHFFFAOYSA-N 0.000 claims 7
- 238000007039 two-step reaction Methods 0.000 claims 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims 1
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 claims 1
- 150000004820 halides Chemical class 0.000 claims 1
- 239000006227 byproduct Substances 0.000 abstract description 7
- 239000002699 waste material Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 32
- 238000002360 preparation method Methods 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 13
- 238000003756 stirring Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 238000000605 extraction Methods 0.000 description 6
- MCGSDKVOKTWDRB-UHFFFAOYSA-N 1-chloro-3-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC(Cl)=C1 MCGSDKVOKTWDRB-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 235000010288 sodium nitrite Nutrition 0.000 description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 239000003905 agrochemical Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 3
- 229940045803 cuprous chloride Drugs 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- YKOLZVXSPGIIBJ-UHFFFAOYSA-N 2-Isopropylaniline Chemical compound CC(C)C1=CC=CC=C1N YKOLZVXSPGIIBJ-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000006396 nitration reaction Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- LECYCYNAEJDSIL-UHFFFAOYSA-N 1-bromo-2-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC=C1Br LECYCYNAEJDSIL-UHFFFAOYSA-N 0.000 description 1
- BSMKYQUHXQAVKG-UHFFFAOYSA-N 1-nitro-2-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC=C1[N+]([O-])=O BSMKYQUHXQAVKG-UHFFFAOYSA-N 0.000 description 1
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 description 1
- PEXGTUZWTLMFID-UHFFFAOYSA-N 2-phenyldiazenylphenol Chemical compound OC1=CC=CC=C1N=NC1=CC=CC=C1 PEXGTUZWTLMFID-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- QPQKUYVSJWQSDY-UHFFFAOYSA-N 4-phenyldiazenylaniline Chemical compound C1=CC(N)=CC=C1N=NC1=CC=CC=C1 QPQKUYVSJWQSDY-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- 229940122440 HIV protease inhibitor Drugs 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000001857 anti-mycotic effect Effects 0.000 description 1
- 239000002543 antimycotic Substances 0.000 description 1
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- YDVNLQGCLLPHAH-UHFFFAOYSA-N dichloromethane;hydrate Chemical compound O.ClCCl YDVNLQGCLLPHAH-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000004030 hiv protease inhibitor Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- PUIYMUZLKQOUOZ-UHFFFAOYSA-N isoproturon Chemical compound CC(C)C1=CC=C(NC(=O)N(C)C)C=C1 PUIYMUZLKQOUOZ-UHFFFAOYSA-N 0.000 description 1
- ALIFPGGMJDWMJH-UHFFFAOYSA-N n-phenyldiazenylaniline Chemical class C=1C=CC=CC=1NN=NC1=CC=CC=C1 ALIFPGGMJDWMJH-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
This invention is using amino direct reaction and the diazotization to convert inter-isopropylaniline into other interposition substitutive cumene derivate. The inter-isopropylaniline is the by-products in the cumidine production process. It greatly expands the use of inter-isopropylaniline, which used to be waste material, and realizes the importance of environmental protection and conservation of resources.
Description
Technical field
Utilization of the present invention with nitrated, reduction method produce produce in the cumidine process a kind of byproduct---an isopropyl aniline has prepared multiple isopropyl benzene derivative.
Background of invention
Cumidine is the important source material of producing the agricultural chemicals isoproturon, the normally isopropyl benzene nitrated back reduction of its production technique.In the nitration reaction of isopropyl benzene, can produce three kinds of isomer, promptly adjacent, and to nitrocumene, corresponding content is respectively 21%, 2% and 76%.In three kinds of isomer of the isopropyl aniline that obtains after the reduction, contraposition and ortho position product all have been widely used at pesticide field, though a but position product---an isopropyl aniline can be used for medicines such as synthetic dyestuff, photographic developer, microbiotic and hiv protease inhibitor, and the antimycotic agricultural chemicals of treatment rice blast and wheat leaf rust, but its consumption and range of application be far smaller than to o-isopropyl aniline.Though the shared ratio of isopropyl aniline is very little between producing in the nitrated and reduction process of isopropyl benzene, but because the output of cumidine is bigger, the also corresponding increase of the total amount of isopropyl aniline between by product, if this part product is given it up, can cause the pollution of environment and the waste of resource.Therefore, the present invention will be converted into the isopropyl benzene derivative that other positions replace with an isopropyl aniline by a step or a multistep simple chemical reaction, and these derivatives can have purposes more widely owing to have different character.
The preparation of isopropyl benzene derivative is a raw material with the isopropyl benzene normally, introduces corresponding functional group on phenyl ring, tend to like this obtain the neighbour,, to three kinds of isomer, and because the orientation effect of sec.-propyl, adjacent and para-isomeride accounts for major part usually, and the content of meta-isomer is then seldom.Because the physicochemical property of these three kinds of isomer, for example boiling point, solvability etc. are very nearly the same usually, bring very big difficulty therefore for the separation Purification, and chemical compound lot all can not be realized separation and purification completely.For example in the preparation process of m-Chlorocumene, adopt the isopropyl benzene direct chlorination, the isomer mixture that obtains need adopt the method for molecular sieving just can obtain a small amount of pure meta-isomer.Such preparation method not only productive rate is low, and the sepn process complexity, is unfavorable for realizing scale operation.
The another kind of method for preparing the isopropyl benzene derivative is to utilize the Fu Ke alkylated reaction, introduces sec.-propyl in substituted benzene.This method also can form usually the neighbour,, to three kinds of isomer, the ratio between three kinds of isomer changes because of the difference of substituent characteristic, but it is essential, equally also very difficult to separate the process of three kinds of isomer.For example in the preparation method of NSC 2209, carry out alkylated reaction with propylene or Virahol and phenol, three kinds of isomer interpositions that obtain only account for 6%, and most of product is an ortho isomer, and temperature of reaction is more than 200 ℃.
If with an isopropyl aniline is raw material, utilize amino reactive behavior, then can obtain a series of isopropyl benzene derivatives easily, the reaction conditions gentleness, there is not the problem of isomer in product, and the separation and purification process is simple.Can getable isopropyl benzene derivative as follows by an isopropyl aniline by simple reaction:
Wherein R refers to the straight or branched alkyl, cycloalkyl or aryl, aralkyl etc.
Amino direct and haloalkane, oxyethane or carboxylic acid and anhydride reaction form N-substitution compound or amide compound.And diazotization reaction can change amino into more functional group, for example hydroxyl, halogen atom, sulfydryl, alkoxyl group, itrile group etc.
Can see, promptly can obtain multiple isopropyl benzene derivative by simple chemical reaction by an isopropyl aniline, the Application Areas of these derivatives is very extensive, for example m-Chlorocumene and NSC 2209 all are important chemical reaction raw materials, not only can be used to prepare medicine and agricultural chemicals, very big application potential is also arranged aspect Polymer Synthesizing.
Isopropyl aniline between utilization, not only simplified the preparation method of many isopropyl benzene derivatives, reduced preparation cost, the downstream use of isopropyl aniline between also having widened simultaneously, so just can turn waste into wealth, intended use waste material is seldom become have extensive use, important chemical material.
Summary of the invention
The present invention is to be prepared the byproduct that produces in the cumidine process by isopropyl benzene---and an isopropyl aniline is a raw material, utilizes amino reactive behavior, obtains various isopropyl benzene derivatives, and main reaction is as follows:
Wherein R refers to the straight or branched alkyl, cycloalkyl or aryl, aralkyl etc.
Utilize the Sodium Nitrite and the vitriol oil or concentrated hydrochloric acid,-10-10 ℃ down will between isopropyl aniline be converted into diazonium salt, in this diazotization reaction, the consumption of Sodium Nitrite is a 1.0-1.5 of isopropyl aniline mole number times, the consumption of concentrated acid is a 3-5 of isopropyl aniline weight times, 0.5-5 hour diazotization reaction time.
Adopt limit coronite distillatory mode, this diazonium salt is added drop-wise in the ebullient dilute acid soln, reaction obtains NSC 2209 (ii) to no longer including overhead product under the boiling temperature of diluted acid.
In this diazonium salt solution, add, the crystal of separating out in the adition process is heated to fusion and decomposition, behind no gas evolution, obtain a sec.-propyl fluorobenzene (iii) by boric acid and the formulated boron fluoric acid of fluoric acid.
This diazonium salt solution is slowly joined the hydrochloric acid soln of cuprous chloride or the hydrobromic acid solution of cuprous bromide between-10-10 ℃, or in the aqueous solution of cuprous iodide, between 0-50 ℃, reacted 5-20 hour subsequently, wet distillation after reaction is finished obtains m-Chlorocumene, a bromo-cumene or a sec.-propyl iodobenzene respectively (iv).
This diazonium salt solution is slowly joined in the aqueous solution of potassium ethyl xanthonate,, handled 5-15 hour at reflux temperature with highly basic after reaction is finished, obtain an isopropylbenzene thiophenol (v) 20-60 ℃ of reaction 5-40 minute.
Most of water in this diazonium salt is boiled off, and the reaction of adding alcohol reflux obtained a sec.-propyl alkoxy benzene after 2-10 hour, and (vi), described alcohol is methyl alcohol, ethanol, Virahol, the trimethyl carbinol etc.
Aqueous solution with the aqueous solution and the sodium cyanide of sodium-chlor obtains complex salt solution, then to wherein adding above-mentioned diazonium salt solution, 20-80 ℃ down reaction obtained an isopropyl benzene formonitrile HCN (vii) in 30-100 minute.
This diazonium salt solution is joined in the mixing solutions of sodium bisulfite and sodium hydroxide, the control reacting solution pH value is 5-7, obtains a sec.-propyl phenylhydrazine (viii) in reaction under 40-90 ℃ after 2-10 hour.
Coupled reaction can also take place at-5-50 ℃ with phenol, aniline etc. in the diazonium salt of this outer room isopropyl aniline, reacts to obtain azo-compound or diazoamino benzene compounds such as hydroxyazobenzene, aminoazobenzene after 1-10 hour.
Except that utilizing diazotization reaction, amino also can be participated in reaction directly, obtains the isopropyl benzene derivative.Between the 50-100 ℃ of reaction under pressurized conditions of isopropyl aniline and oxyethane obtained isopropyl aniline between the N-hydroxy ethoxy (ix) in 5-20 hour; And acid or acid anhydrides react under reflux temperature and obtained isopropyl aniline between the N-acyl group (x) in 5-10 hour; Direct and haloalkane obtains isopropyl aniline between the N-alkyl (xi) in 10-50 ℃ of reaction reaction in 10-30 hour.
Except that the above-mentioned reaction of mentioning, also can be reflected on the phenyl ring of an isopropyl aniline and introduce another substituting group again by nitrated, sulfonation or alkylation etc.
Embodiment 1
The preparation of m-Chlorocumene
With phosphoric acid, nitration mixture that isopropyl benzene is nitrated at 0-20 ℃, to obtain a sec.-propyl oil of mirbane 80-110 ℃ of reduction with iron powder and hydrochloric acid soln, thereby obtain the mixture of cumidine, o-isopropyl aniline and an isopropyl aniline, rectifying separation obtains an isopropyl aniline.
Add the 80ml hydrochloric acid soln in the 250ml flask, be cooled to below 5 ℃ ℃ to drip isopropyl aniline between 21.6g (0.16mol), dropwise after 30 minutes, 3 ℃ of solution temperatures continue to stir 15 minutes under this temperature.Be cooled to below 0 ℃, drip the solution of 11.54g (0.167mol) Sodium Nitrite and 27ml water.Dropwise after 80 minutes, solution temperature-3 ℃ obtains diazonium salt solution.
Above-mentioned diazonium salt solution is added drop-wise in the 500ml flask that is equipped with cuprous chloride hydrochloric acid soln (do not have hydration copper sulfate (0.4mol) prepared fresh by 100g, then be dissolved in the 120ml hydrochloric acid), and temperature remains at about 0 ℃.Dropwised in 20 minutes, and rose to room temperature (27 ℃) in 1 hour, stir then and spend the night.
With 100ml toluene extractive reaction liquid, the washing extraction liquid is to neutral.Boil off wet distillation behind the toluene wherein, obtain m-Chlorocumene.
Embodiment 2
The preparation of NSC 2209
In the 100ml flask, add 27ml 98% vitriol oil and 45ml water, be cooled to begin below 5 ℃ to drip the byproduct that 13.5g (0.1mol) obtains by the method among the embodiment 1 a---isopropyl aniline.Dropwise after 20 minutes, with ice bath temperature is remained on about 3 ℃ and stirred 20 minutes.Be cooled to below 0 ℃ with the temperature of ice bath again, drip the solution of 7.2g (0.104mol) Sodium Nitrite and 15ml water reaction soln.Dropwise after 95 minutes, temperature keeps again-1 ℃, stirs 15 minutes at 0 ℃ then, obtains diazonium salt solution.
In the 500ml flask, add 200ml water and 30ml sulfuric acid, join water distilling apparatus, and be heated to boiling.Above-mentioned diazonium salt solution slowly is added drop-wise in this ebullient acid, and constantly wet distillation goes out product simultaneously.Dropwise after 35 minutes, continued wet distillation 45 minutes, collect thick product.Continue distillation reaction solution, and the water in the extraction overhead product.
9.48g add 75ml 10% sodium hydroxide solution in the above-mentioned thick product, in ice bath, stir after 30 minutes with toluene extraction three times.Water adds the 18ml hcl acidifying to pH=2-3, separates out oily matter.Extract this mixing solutions once more with toluene, obtain NSC 2209 after boiling off toluene.
Embodiment 3
Between the preparation of sec.-propyl fluorobenzene
The preparation of diazonium salt is with embodiment 1.
(40%, 0.4mol) the formulated fluoroboric acid of fluoric acid under agitation joins in the diazonium salt solution rapidly then with 6.2g (0.1mol) boric acid and 20g.Separate out a large amount of crystal immediately, fully stirring, cooled and filtered, oven dry.The dry NITRODIAZONIUM FLUOROBORATE that obtains is placed the 100ml flask, and distribution bulk absorption device slowly is heated to the solid fusion, has bubble to overflow, and treats that bubble effusion stopping back rectifying goes out sec.-propyl fluorobenzene between product.
Embodiment 4
Between the preparation of isopropylbenzene thiophenol
The preparation of diazonium salt is with embodiment 1
In the 100ml flask, add 19.2 (0.12mol) potassium ethyl xanthonates and 30ml water, stirring and dissolving, and temperature risen to about 45 ℃.Diazonium salt solution is slowly added wherein, have a large amount of gases to emit, add the back and continued stirring reaction 10 minutes.Oil-yielding stratum is divided in the cooling back, and water merges with dichloromethane extraction twice, extraction liquid and oil reservoir, boils off solvent.The transesterify that obtains in the 250ml flask, is added the 70ml dissolve with ethanol.Heating in water bath adds 21g (0.375mol) potassium hydroxide to refluxing in batches, adds fashionable meeting at every turn vigorous reaction takes place, and adds next batch again after question response is steady.Add post-heating to reflux temperature stirring reaction 8 hours.Rotation steamed most of ethanol after reaction was finished, and resistates is joined in the 100ml frozen water dichloromethane extraction.Water to pH=2, adds the zinc powder steam distillation with sulfuric acid acidation.The overhead product crystallisation by cooling obtains an isopropylbenzene thiophenol.
Embodiment 5
Between the preparation of isopropyl benzene methyl ether
The preparation of diazonium salt is with embodiment 1.
Diazonium salt solution rotation under comparatively gentle condition boils off most of hydrochloric acid, obtains the diazonium salt strong solution.With this diazonium salt strong solution and 50ml methyl alcohol, be heated to reflux temperature reaction 5 hours.Rotation boils off methyl alcohol behind the stopped reaction, adds the methylene dichloride dissolving, wash successively with saturated sodium carbonate solution and water again, organic phase with anhydrous sodium sulfate drying after rectification under vacuum, obtain an isopropyl benzene methyl ether.
Embodiment 6
Between the preparation of isopropyl benzene formonitrile HCN
The preparation of diazonium salt is with embodiment 1.
In the 500ml flask, add 10g (0.21mol) cuprous chloride and 50ml water, form suspension.The 50ml aqueous solution with 17g (0.34mol) sodium cyanide under agitation adds wherein then, and exothermic heat of reaction forms double salt.This solution is heated to about 55 ℃, slowly adds diazonium salt solution then, immediate response sends gas.Add the back restir and react half an hour.Add methylene dichloride after reaction is finished, tell organic layer behind the standing demix, rectification under vacuum obtains an isopropyl benzene formonitrile HCN.
Embodiment 7
Between the preparation of sec.-propyl phenylhydrazine
The preparation of diazonium salt is with embodiment 1
In the 250ml flask, 27.5g (0.25mol) sodium bisulfite is dissolved in 15ml water.Stir and add 25g (0.25mol) 40% sodium hydroxide solution down, control pH=6.Added diazonium salt solution then in about 10 minutes, be heated to about 70 ℃, separate out the phenylhydrazine crystal, insulation is 3-4 hour under this temperature, and cool to room temperature is placed and spent the night.The crystal that obtains after the filtration joins in 15ml 40% sodium hydroxide solution about 40 ℃, tells organic phase after fully stirring, and adds the solid sodium hydroxide drying, and rectification under vacuum afterwards obtains a sec.-propyl phenylhydrazine.
Embodiment 8
The preparation of isopropyl aniline between the N-hydroxy ethoxy
In voltage-resistant reactor, add the byproduct that 125g (1mol) obtains by the method among the embodiment 1---an isopropyl aniline and 20ml water, temperature is risen to about 70 ℃, in 5 hours, be pressed into 44g oxyethane continuously, insulation reaction is 5 hours afterwards, and rectification under vacuum obtains isopropyl aniline between the N-hydroxy ethoxy.
Embodiment 9
The preparation of isopropyl aniline between the N-ethanoyl
The byproduct that in the 50ml flask 12.5g (0.1mol) is obtained by the method among the embodiment 1 a---isopropyl aniline mixes with the 10ml glacial acetic acid, is heated to reflux temperature reaction 8 hours.Reclaim under reduced pressure acetate after reaction finishes, residuum adds a large amount of hot water while hot, is neutralized to neutrality with yellow soda ash then.Separate out crystal after the cooling, obtain isopropyl aniline between the N-ethanoyl after filtering, drying.
Embodiment 10
The preparation of isopropyl aniline between the N-ethyl
The byproduct that in the 50ml flask 12.5g (0.1mol) is obtained by the method among the embodiment 1 a---isopropyl aniline mixes with 12g (0.11mol) monobromethane, maintain the temperature at about 25 ℃ and reacted 5 hours, about 30 ℃, be incubated 5 hours then, insulation is 5 hours about 35 ℃, solution transferred in the 100ml beaker to stir spend the night, to wherein adding sodium hydroxide solution, tell organic phase after fully stirring then, obtain isopropyl aniline between the N-ethyl after the rectification under vacuum.
Claims (15)
1. one kind prepares the cumidine improved technological process by isopropyl benzene, comprise isopropyl benzene through nitrated, reduction two-step reaction, thereby obtain cumidine, it is characterized in that: separate obtain between byproduct---the isopropyl aniline that replaces of position, by and the direct reaction of amino obtain the isopropyl benzene derivative that various positions replace.
2. as claimed in claim 1 improving one's methods is characterized in that: described isopropyl benzene derivative is isopropyl aniline etc. between isopropyl aniline, N-alkyl between isopropyl aniline between the N-hydroxy ethoxy, N-acyl group.
3. as claimed in claim 2 improving one's methods is characterized in that: isopropyl aniline prepares by an isopropyl aniline and reacting ethylene oxide between described N-hydroxy ethoxy.
4. as claimed in claim 2 improving one's methods is characterized in that: isopropyl aniline prepares by an isopropyl aniline and carboxylic acid or anhydride reaction between described N-acyl group.
5. as claimed in claim 2 improving one's methods is characterized in that: between described N-alkyl isopropyl aniline by an isopropyl aniline with the haloalkane prepared in reaction.
6. one kind prepares the cumidine improved technological process by isopropyl benzene, comprise isopropyl benzene through nitrated, reduction two-step reaction, thereby obtain cumidine, it is characterized in that: separate obtain between byproduct---the isopropyl aniline that replaces of position, diazotization reaction by amino obtains diazonium salt, then by and the reaction of diazonium salt obtain the isopropyl benzene derivative that various positions replace.
7. as claimed in claim 6 improving one's methods is characterized in that: described isopropyl benzene derivative is the azo-compound of NSC 2209, a sec.-propyl fluorobenzene, a sec.-propyl halogeno-benzene, an isopropylbenzene thiophenol, an isopropyl phenyl alkyl oxide, an isopropyl benzene formonitrile HCN, a sec.-propyl phenylhydrazine, an isopropyl benzene or diazoamino compound etc.
8. as claimed in claim 7 improving one's methods is characterized in that: described NSC 2209 prepares by an isopropyl aniline diazonium salt and diluted acid reaction.
9. as claimed in claim 7 improving one's methods is characterized in that: described sec.-propyl fluorobenzene prepares by an isopropyl aniline diazonium salt and the reaction of boron fluoric acid.
10. as claimed in claim 7 improving one's methods is characterized in that: described sec.-propyl halogeno-benzene prepares by an isopropyl aniline diazonium salt and halide reaction.
11. as claimed in claim 7 improving one's methods is characterized in that: described isopropylbenzene thiophenol prepares by an isopropyl aniline diazonium salt and xanthogenic acid nak response.
12. as claimed in claim 7 improving one's methods is characterized in that: described isopropyl phenyl alkyl oxide prepares by an isopropyl aniline diazonium salt and alcohol reaction.
13. as claimed in claim 7 improving one's methods is characterized in that: described isopropyl benzene formonitrile HCN prepares by an isopropyl aniline diazonium salt and sodium cyanide reaction.
14. as claimed in claim 7 improving one's methods is characterized in that: described sec.-propyl phenylhydrazine prepares by an isopropyl aniline diazonium salt and sodium bisulfite reaction.
15. as claimed in claim 7 improving one's methods is characterized in that: the azo-compound of described isopropyl benzene is to prepare by the coupled reaction between described diazonium salt and phenol, aniline etc.
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