CN101508669B - Green synthesis of indole compounds - Google Patents
Green synthesis of indole compounds Download PDFInfo
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- CN101508669B CN101508669B CN2009100971921A CN200910097192A CN101508669B CN 101508669 B CN101508669 B CN 101508669B CN 2009100971921 A CN2009100971921 A CN 2009100971921A CN 200910097192 A CN200910097192 A CN 200910097192A CN 101508669 B CN101508669 B CN 101508669B
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- hso
- disulfonic acid
- acid type
- 5mmol
- acidic ion
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- 150000002475 indoles Chemical class 0.000 title abstract description 12
- 230000015572 biosynthetic process Effects 0.000 title abstract description 6
- 238000003786 synthesis reaction Methods 0.000 title abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 85
- 239000002253 acid Substances 0.000 claims abstract description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 10
- 150000002576 ketones Chemical class 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 239000011541 reaction mixture Substances 0.000 claims abstract description 5
- 239000000758 substrate Substances 0.000 claims abstract description 3
- 230000002378 acidificating effect Effects 0.000 claims description 60
- 239000007788 liquid Substances 0.000 claims description 55
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical class C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 23
- 238000001914 filtration Methods 0.000 claims description 13
- 238000001308 synthesis method Methods 0.000 claims description 11
- -1 aryl hydrazine Chemical compound 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 4
- 239000011831 acidic ionic liquid Substances 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000012065 filter cake Substances 0.000 claims 1
- 239000000706 filtrate Substances 0.000 claims 1
- 239000002608 ionic liquid Substances 0.000 abstract description 45
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 238000010189 synthetic method Methods 0.000 abstract 3
- 125000003118 aryl group Chemical group 0.000 abstract 2
- 238000000926 separation method Methods 0.000 abstract 1
- 238000010907 mechanical stirring Methods 0.000 description 73
- 150000002500 ions Chemical class 0.000 description 50
- 239000007864 aqueous solution Substances 0.000 description 38
- 238000001035 drying Methods 0.000 description 36
- 238000010438 heat treatment Methods 0.000 description 35
- 238000001816 cooling Methods 0.000 description 30
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 20
- 229940067157 phenylhydrazine Drugs 0.000 description 20
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- VGVHNLRUAMRIEW-UHFFFAOYSA-N 4-methylcyclohexan-1-one Chemical compound CC1CCC(=O)CC1 VGVHNLRUAMRIEW-UHFFFAOYSA-N 0.000 description 12
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 11
- 239000011259 mixed solution Substances 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- MQWCXKGKQLNYQG-UHFFFAOYSA-N methyl cyclohexan-4-ol Natural products CC1CCC(O)CC1 MQWCXKGKQLNYQG-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OLPGNDQLPDCSGF-UHFFFAOYSA-N NN.ClC1=CC=CC(=C1)Cl Chemical compound NN.ClC1=CC=CC(=C1)Cl OLPGNDQLPDCSGF-UHFFFAOYSA-N 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- AGKPWKVADJCEDP-UHFFFAOYSA-N (1-methylnaphthalen-2-yl)hydrazine Chemical compound C1=CC=C2C(C)=C(NN)C=CC2=C1 AGKPWKVADJCEDP-UHFFFAOYSA-N 0.000 description 2
- KYAXCYQVBBQQHB-UHFFFAOYSA-N 3-methyl-2-phenyl-1h-indole Chemical class N1C2=CC=CC=C2C(C)=C1C1=CC=CC=C1 KYAXCYQVBBQQHB-UHFFFAOYSA-N 0.000 description 2
- KMVPXBDOWDXXEN-UHFFFAOYSA-N 4-nitrophenylhydrazine Chemical compound NNC1=CC=C([N+]([O-])=O)C=C1 KMVPXBDOWDXXEN-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- AYDQIZKZTQHYIY-UHFFFAOYSA-N OC(=O)C1(C)CC(C(O)=O)=CC=C1 Chemical compound OC(=O)C1(C)CC(C(O)=O)=CC=C1 AYDQIZKZTQHYIY-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- CGZZMOTZOONQIA-UHFFFAOYSA-N cycloheptanone Chemical compound O=C1CCCCCC1 CGZZMOTZOONQIA-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical group O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 2
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- DTUQWGWMVIHBKE-UHFFFAOYSA-N phenylacetaldehyde Chemical compound O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 description 2
- 229960000624 procarbazine Drugs 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- NGPPYFDQGFGQHM-UHFFFAOYSA-N (1-chloronaphthalen-2-yl)hydrazine Chemical compound C1=CC=CC2=C(Cl)C(NN)=CC=C21 NGPPYFDQGFGQHM-UHFFFAOYSA-N 0.000 description 1
- GHGPIPTUDQZJJS-UHFFFAOYSA-N (2-chlorophenyl)hydrazine Chemical compound NNC1=CC=CC=C1Cl GHGPIPTUDQZJJS-UHFFFAOYSA-N 0.000 description 1
- WRMQLRIKRPMUEY-UHFFFAOYSA-N (5-methylnaphthalen-2-yl)hydrazine Chemical compound NNC1=CC=C2C(C)=CC=CC2=C1 WRMQLRIKRPMUEY-UHFFFAOYSA-N 0.000 description 1
- UMKLWBFJFMDZAH-UHFFFAOYSA-N 1-chloro-1-phenylhydrazine Chemical group NN(Cl)C1=CC=CC=C1 UMKLWBFJFMDZAH-UHFFFAOYSA-N 0.000 description 1
- ZYEJTCXNJSMXDS-UHFFFAOYSA-N 11,13-dimethyltricosan-12-one Chemical compound CCCCCCCCCCC(C)C(=O)C(C)CCCCCCCCCC ZYEJTCXNJSMXDS-UHFFFAOYSA-N 0.000 description 1
- XKLNOVWDVMWTOB-UHFFFAOYSA-N 2,3,4,9-tetrahydro-1h-carbazole Chemical compound N1C2=CC=CC=C2C2=C1CCCC2 XKLNOVWDVMWTOB-UHFFFAOYSA-N 0.000 description 1
- WEDBVPQYBDSVSX-UHFFFAOYSA-N 2-methyl-3-propan-2-yl-1h-indole Chemical compound C1=CC=C2C(C(C)C)=C(C)NC2=C1 WEDBVPQYBDSVSX-UHFFFAOYSA-N 0.000 description 1
- HNUYRDWMYRCVNO-UHFFFAOYSA-N 3-benzyl-1h-indole Chemical class C=1NC2=CC=CC=C2C=1CC1=CC=CC=C1 HNUYRDWMYRCVNO-UHFFFAOYSA-N 0.000 description 1
- XZNGTBLWFCRXKR-UHFFFAOYSA-N 3-phenyl-1h-indole Chemical compound C=1NC2=CC=CC=C2C=1C1=CC=CC=C1 XZNGTBLWFCRXKR-UHFFFAOYSA-N 0.000 description 1
- YGCZTXZTJXYWCO-UHFFFAOYSA-N 3-phenylpropanal Chemical compound O=CCCC1=CC=CC=C1 YGCZTXZTJXYWCO-UHFFFAOYSA-N 0.000 description 1
- XYZJEGBDTNCSPW-UHFFFAOYSA-N 4-chloro-2,3-dimethyl-1H-indole Chemical compound Cc1[nH]c2cccc(Cl)c2c1C XYZJEGBDTNCSPW-UHFFFAOYSA-N 0.000 description 1
- XXNOGQJZAOXWAQ-UHFFFAOYSA-N 4-chlorophenylhydrazine Chemical compound NNC1=CC=C(Cl)C=C1 XXNOGQJZAOXWAQ-UHFFFAOYSA-N 0.000 description 1
- OVZTWOBMVBFCSZ-UHFFFAOYSA-N C1(=CC=CC=C1)NN.ClN(N)C1=CC=CC=C1 Chemical compound C1(=CC=CC=C1)NN.ClN(N)C1=CC=CC=C1 OVZTWOBMVBFCSZ-UHFFFAOYSA-N 0.000 description 1
- IGNBOJICOKZFPU-UHFFFAOYSA-N ClC=1C=CC=C2C=CC(=CC12)NN Chemical compound ClC=1C=CC=C2C=CC(=CC12)NN IGNBOJICOKZFPU-UHFFFAOYSA-N 0.000 description 1
- 238000006783 Fischer indole synthesis reaction Methods 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000002246 antineoplastic agent Substances 0.000 description 1
- 229940041181 antineoplastic drug Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- OILAIQUEIWYQPH-UHFFFAOYSA-N cyclohexane-1,2-dione Chemical class O=C1CCCCC1=O OILAIQUEIWYQPH-UHFFFAOYSA-N 0.000 description 1
- HJSLFCCWAKVHIW-UHFFFAOYSA-N cyclohexane-1,3-dione Chemical compound O=C1CCCC(=O)C1 HJSLFCCWAKVHIW-UHFFFAOYSA-N 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 150000007857 hydrazones Chemical class 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 206010025482 malaise Diseases 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- XBCIOBSQHJYVBQ-UHFFFAOYSA-N naphthalen-1-ylhydrazine Chemical compound C1=CC=C2C(NN)=CC=CC2=C1 XBCIOBSQHJYVBQ-UHFFFAOYSA-N 0.000 description 1
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N perisophthalic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical compound CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 1
- 235000019633 pungent taste Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229940074386 skatole Drugs 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
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- Indole Compounds (AREA)
Abstract
The invention discloses a green synthetic method for indole compounds. The synthetic method uses aldehyde or ketone and aromatic polyhydrazide as substrates, the aldehyde or the ketone and the aromatic polyhydrazide are fully reacted at a temperature between 20 and 100 DEG C in a water solvent under the catalysis of disulfonic acid type ionic liquid, and the obtained reaction mixture is filtered and dried to obtain the indole compounds. The preparation method has mild reaction conditions, simple and convenient operation, easy separation for products and environment protection during synthesis; the obtained indole compounds have high purity; the catalyst can be repeatedly used; and the method is the green synthetic method, and is suitable for industrialized production.
Description
(1) technical field
The present invention relates to a kind of compound method of Benzazole compounds
(2) background technology
Benzazole compounds has important purposes in fields such as medicine, agricultural chemicals, and especially in recent years, the indoles alkaloid frequent application was in antitumor drug.The method of synthesis of indole compounds is more, and the Fischer indole synthesis is considered to one of convenient and the most economic method of a kind of application, in indoles is synthetic, has a wide range of applications.In the traditional F ischer indole synthesis; Lewis acid such as sulfuric acid, hydrochloric acid, trifluoroacetic acid, polyphosphoric acid etc.
acid, zinc chloride and solid acid all have as catalyzer and are used, and when these traditional catalyst of practical application, often have problems such as consumption is big, strong to equipment corrosion, yield is generally not high; Secondly, using mostly in the traditional method has pungency and volatile organic solvent, and like acetate, benzene, toluene etc., there is certain toxicity in this kind solvent, and environment is also had certain harm; Moreover the most first synthetic aroma hydrazone of traditional method is reset under acidic conditions again, operates loaded down with trivial details relatively.Therefore, invention indoles compound method simple and green high-efficient seems particularly important.Ionic liquid because have that solubility property is good, low-steam pressure, higher advantages such as thermostability; Be considered to a kind of green solvent; Simultaneously; In many reactions, also shown higher reaction preference and reactive behavior, wherein, the functionalization acidic ionic liquid body has shown good catalytic performance in catalyzed reaction.Khadikar and Jenkins etc. have reported that respectively the Lewis acidic ion liquid is not only as catalyzer but also as method (Synthesis-Stuttgart, 2001, the 370-372 of solvent catalysis synthesis of indole compounds; Chem.commun., 2004,158-159).But the Lewis acidic ion liquid is unstable in air, is prone to suction, and storage requires harsh, and the method for foundation such as Khadikar and Jenkins is unwell to practical application.
(3) summary of the invention
Be big, a series of problems such as equipment corrosion strong, solvent is unfriendly to environment, complex operation of catalyst levels that exist in the prior art that solves the preparation Benzazole compounds; Follow a kind of green more and synthetic theory efficiently simultaneously, the objective of the invention is to disclose and a kind ofly be catalyzer, substitute the method for conventional organic solvents synthesis of indole compounds with water with the disulfonic acid type acidic ion liquid.This method reaction conditions is gentle, and easy and simple to handle, building-up process is environmentally friendly, and product is easily separated, and gained Benzazole compounds purity is high.
For reaching goal of the invention, the technical scheme that the present invention adopts is following:
A kind of green synthesis method of Benzazole compounds; The structure of said Benzazole compounds is suc as formula shown in (I)～formula (VII); Described compound method be with structure suc as formula the aldehydes or ketones of (i)～formula shown in (iv) and structure suc as formula (v) or formula (aryl hydrazine vi) is a substrate; Under the disulfonic acid type presence of acidic ionic liquid catalyst, in water solvent, fully react in 20～100 ℃, the gained reaction mixture filters, is drying to obtain described Benzazole compounds.
Reaction formula is following:
In above-mentioned each structural formula, R
1Alkyl for the substituted alkyl of the phenyl of H, phenyl, C7～C20 or C1～C20;
R
2The substituted alkyl of phenyl for alkyl, phenyl or the C7～C20 of C1～C20;
R
3, R
4, R
5, R
6, R
12, R
13, R
14, R
15, R
16, R
17Independent separately is the alkyl of H, C1～C4, alkoxyl group, nitro or the halogen of C1～C4;
R
7, R
8, R
9, R
10, R
11Independent separately is the alkyl of H or C1～C5;
R is S or C;
n＝1～4。
Disulfonic acid type acidic ion liquid of the present invention, its structure suc as formula (vii):
(vii), m is 1 or 2 to formula, and when m was 1, said disulfonic acid type acidic ion liquid was designated as: [(HSO
3-p)
2Im] [Y]; When m was 2, said disulfonic acid type acidic ion liquid was designated as: [(HSO
3-b)
2Im] [Y]; It is one of following that Y is selected from: HSO
4, H
2PO
4, p-CH
3C
6H
4SO
3
The preferred [(HSO of disulfonic acid type acidic ion liquid of the present invention
3-p)
2Im] [HSO
4].
Aldehydes or ketones according to the invention is generally 1: 0.5～2 with the ratio of the amount of substance of said aryl hydrazine, and preferred 1: 1～1.5, most preferably be 1: 1; Said disulfonic acid type acidic ion liquid is 1: 1～5 with the ratio of the amount of substance of said aldehydes or ketones, preferred 1: 1～3, and most preferably 1: 2.
The concentration of disulfonic acid type acidic ion liquid according to the invention in water solvent is generally 0.01～1mol/L, preferred 0.1～0.3mol/L, most preferably 0.17mol/L.
The present invention reacts at 20～100 ℃, and the reaction times is preferably being reacted 1～8h at 60～100 ℃ generally at 0.5～40h.
The disulfonic acid type acidic ion liquid that the present invention uses can recovery set usefulness after reaction finishes, and recovery method is: said reaction mixture is filtered gained filtrating remove the NH that dereaction generates through the acid exchange
4 +After, can continue at following secondary response relaying and apply mechanically.The acid that described acid exchange is used is hydrochloric acid or strong-acid ion exchange resin, preferred strong-acid ion exchange resin.Used strongly acidic cationic exchange resin then can continue to use after pickling regeneration.
Of the present invention is that catalyzer, water are that the beneficial effect that reaction medium prepares the method for Benzazole compounds is mainly reflected in following five aspects with the disulfonic acid type acidic ion liquid:
1) replaces traditional inorganic acids and solid acid as catalyzer with the disulfonic acid type acidic ion liquid, can effectively reduce to the influence of environment with to corrosion on Equipment;
2) replace organic solvents such as traditional acetate, toluene with green solvent water, environmentally friendly, cost is low;
3) one kettle way is synthetic, and is easy and simple to handle;
4) reaction conditions is gentle, and product is easy to separate, and aftertreatment is simple, good product purity, yield height;
5) the employed catalyzer disulfonic acid type of this method acidic ion liquid is reusable, and product yield is unaffected.
To sum up, the compound method of Benzazole compounds according to the invention is a kind of green synthesis method, is suitable for suitability for industrialized production.
(4) embodiment
Below in conjunction with specific embodiment the present invention is described further, but protection scope of the present invention is not limited in this.
Embodiment 1:
Disulfonic acid type acidic ion liquid [(HSO
3-p)
2Im] [HSO
4] (2.5mmol) add and to fill in the 25ml twoport round-bottomed flask of water (15ml), mechanical stirring evenly is the ionic liquid homogeneous phase aqueous solution, pimelinketone (0.490g, 5mmol) and phenylhydrazine (0.540g 5mmol) joins in this reaction vessel successively; Under mechanical stirring, 70 ℃ of oil bath heating, insulation reaction 0.5h, cool to room temperature; The mixed solution direct filtration, drying obtains 1,2; 3,4-tetrahydro carbazole 0.83g, yield 93%, the product structure formula is:
Embodiment 2:
Disulfonic acid type acidic ion liquid [(HSO
3-p)
2Im] [HSO
4] (2.5mmol) add and to fill in the 25ml twoport round-bottomed flask of water (30ml), mechanical stirring evenly is the ionic liquid homogeneous phase aqueous solution, pimelinketone (0.490g, 5mmol) and phenylhydrazine (0.540g 5mmol) joins in this reaction vessel successively; Under mechanical stirring, 70 ℃ of oil bath heating, insulation reaction 1h, cool to room temperature; The mixed solution direct filtration, drying obtains 1,2; 3,4-tetrahydro carbazole 0.76g, yield 87%, the product structure formula is:
Embodiment 3:
Disulfonic acid type acidic ion liquid [(HSO
3-p)
2Im] [HSO
4] (2.5mmol) add and to fill in the 25ml twoport round-bottomed flask of water (15ml), mechanical stirring evenly is the ionic liquid homogeneous phase aqueous solution, and pimelinketone (0.490g, 5mmol) and phenylhydrazine (0.540g; 5mmol) join successively in this reaction vessel, under mechanical stirring, room temperature reaction 12h, mixed solution direct filtration; Drying obtains 1,2,3; 4-tetrahydro carbazole 0.83g, yield 90%, the product structure formula is:
Embodiment 4
The method of reference example 1, respectively with above-mentioned each ionic liquid as catalyzer, catalysis of pimelinketone (0.490g, 5mmol) and phenylhydrazine (0.540g, 5mmol) reaction obtains 1,2,3, the 4-tetrahydro carbazole, reaction back yield is shown in table one
The catalysis of table 1 different ionic liquid synthesizes 1,2,3,4-tetrahydro carbazole result
Embodiment 5:
Disulfonic acid type acidic ion liquid [(HSO
3-p)
2Im] [HSO
4] (2.5mmol) add and to fill in the 25ml twoport round-bottomed flask of water (15ml), mechanical stirring evenly is the ionic liquid homogeneous phase aqueous solution, and butanone (0.360g, 5mmol) and phenylhydrazine (0.540g; In 5mmol) joining in this reaction vessel successively, under mechanical stirring, 90 ℃ of oil bath heating, insulation reaction 1h; Cooling, filtration, drying obtain 2; 3-dimethyl indole 0.65g, yield 90%, the product structure formula is:
Embodiment 6:
Disulfonic acid type acidic ion liquid [(HSO
3-p)
2Im] [HSO
4] (2.5mmol) add and to fill in the 25ml twoport round-bottomed flask of water (15ml), mechanical stirring evenly be the ionic liquid homogeneous phase aqueous solution, and butanone (0.360g, 5mmol) and 2-procarbazine (0.610g; 5mmol) add successively in this reaction vessel, under mechanical stirring, 85 ℃ of oil bath heating, reaction 2h; Cooling is filtered, and drying obtains 2; 3,7-tri-methyl indole 0.72g, yield 88%, the product structure formula is:
Embodiment 7:
Disulfonic acid type acidic ion liquid [(HSO
3-p)
2Im] [HSO
4] (5mmol) add and to fill in the 25ml twoport round-bottomed flask of water (15ml), mechanical stirring evenly be the ionic liquid homogeneous phase aqueous solution, and butanone (0.52g, 6mmol) and 2,4 dichloro benzene hydrazine (0.531g; 3mmol) join successively in this reaction vessel, under mechanical stirring, 100 ℃ of oil bath heating, reaction 4h; Cooling is filtered, and drying obtains 5; 7-two chloro-2,3-dimethyl indole 0.884g, yield 83%, the product structure formula is:
Embodiment 8:
Disulfonic acid type acidic ion liquid [(HSO
3-p)
2Im] [HSO
4] (2.5mmol) add and to fill in the 25ml twoport round-bottomed flask of water (15ml), mechanical stirring evenly is the ionic liquid homogeneous phase aqueous solution, and propione (0.430g, 5mmol) and phenylhydrazine (0.540g; 5mmol) join successively in this reaction vessel, under mechanical stirring, 80 ℃ of oil bath heating, reaction 1h; Drying is filtered in cooling; Obtain 2-ethyl-3-skatole 0.67g, yield 83%, the product structure formula is:
Embodiment 9:
Disulfonic acid type acidic ion liquid [(HSO
3-p)
2Im] [HSO
4] (2.5mmol) add and to fill in the 25ml twoport round-bottomed flask of water (15ml), mechanical stirring evenly is the ionic liquid homogeneous phase aqueous solution, and 2-dodecyl ketone (1.104g, 6mmol) and phenylhydrazine (0.540g; 5mmol) join successively in this reaction vessel, under mechanical stirring, 90 ℃ of oil bath heating, reaction 3h; Drying is filtered in cooling; Obtain product 1.12g, yield 87%, the product structure formula is:
Embodiment 10:
Disulfonic acid type acidic ion liquid [(HSO
3-p)
2Im] [HSO
4] (2.5mmol) add and to fill in the 25ml twoport round-bottomed flask of water (15ml), mechanical stirring evenly is the ionic liquid homogeneous phase aqueous solution, and Propiophenone (0.804g, 6mmol) and phenylhydrazine (0.540g; 5mmol) add successively in this reaction vessel, under mechanical stirring, 95 ℃ of oil bath heating; Reaction 2h, cooling is filtered; Obtain 2-phenyl-3-methyl-indoles 0.86g, yield 83%, the product structure formula is:
Embodiment 11:
Disulfonic acid type acidic ion liquid [(HSO
3-p)
2Im] [HSO
4] (2.5mmol) add and to fill in the 25ml twoport round-bottomed flask of water (15ml), mechanical stirring evenly is the ionic liquid homogeneous phase aqueous solution, and 4-methyl-2 pentanone (0.500g, 5mmol) and phenylhydrazine (0.540g; 5mmol) join successively in this reaction vessel, under mechanical stirring, 85 ℃ of oil bath heating, reaction 2h; Cooling separates, distillation; Obtain 2-methyl-3-isopropyl indole 0.735g, yield 85%, the product structure formula is:
Embodiment 12:
Disulfonic acid type acidic ion liquid [(HSO
3-p)
2Im] [HSO
4] (5mmol) add and to fill in the 25ml twoport round-bottomed flask of water (15ml), mechanical stirring evenly is the ionic liquid homogeneous phase aqueous solution, and phenylacetic aldehyde (1.008g, 8mmol) and phenylhydrazine (0.540g; 5mmol) join successively in this reaction vessel, under mechanical stirring, 90 ℃ of oil bath heating, reaction 3.5h; Drying is filtered in cooling; Obtain 3-Phenylindole 0.79g, yield 82%, the product structure formula is:
Embodiment 13:
Disulfonic acid type acidic ion liquid [(HSO
3-p)
2Im] [HSO
4] (5mmol) add and to fill in the 25ml twoport round-bottomed flask of water (15ml), mechanical stirring evenly is the ionic liquid homogeneous phase aqueous solution, and the 3-phenylpropyl aldehyde (0.67g, 5mmol) and phenylhydrazine (0.44g; 4mmol) add successively in this reaction vessel, under mechanical stirring, 90 ℃ of oil bath heating, reaction 2.5h; Drying is filtered in cooling; Obtain 3-phenmethyl indoles 0.89g, yield 86%, the product structure formula is:
Embodiment 14:
Disulfonic acid type acidic ion liquid [(HSO
3-p)
2Im] [HSO
4] (2.5mmol) add and to fill in the 25ml twoport round-bottomed flask of water (15ml), mechanical stirring evenly is the ionic liquid homogeneous phase aqueous solution, and ketopentamethylene (0.420g, 5mmol) and phenylhydrazine (0.540g; 5mmol) add successively in this reaction vessel, under mechanical stirring, 78 ℃ of oil bath heating, reaction 2h; Drying is filtered in cooling; Obtain cyclopentyl [b] indoles 0.683g, yield 87%, the product structure formula is:
Embodiment 15:
Disulfonic acid type acidic ion liquid [(HSO
3-p)
2Im] [HSO
4] (2.5mmol) add and to fill in the 25ml twoport round-bottomed flask of water (15ml), mechanical stirring evenly is the ionic liquid homogeneous phase aqueous solution, and suberone (0.560g, 5mmol) and phenylhydrazine (0.540g; 5mmol) add successively in this reaction vessel, under mechanical stirring, 80 ℃ of oil bath heating, reaction 0.6h; Cooling is filtered, washing, drying; Obtain suberyl [b] indoles 0.814g, yield 88%, the product structure formula is:
Embodiment 16:
Disulfonic acid type acidic ion liquid [(HSO
3-p)
2Im] [HSO
4] (2.5mmol) add and to fill in the 25ml twoport round-bottomed flask of water (15ml), mechanical stirring evenly is the ionic liquid homogeneous phase aqueous solution, the 4-methylcyclohexanone (0.560g, 5mmol) and phenylhydrazine (0.540g 5mmol) adds in this reaction vessel successively; Under mechanical stirring, 85 ℃ of oil bath heating, reaction 1h, cooling; Filter, drying obtains the 3-methyl isophthalic acid, 2; 3,4-tetrahydro carbazole 0.8325g, yield 90%, the product structure formula is:
Embodiment 17:
Disulfonic acid type acidic ion liquid [(HSO
3-p)
2Im] [HSO
4] (5mmol) add and to fill in the 25ml twoport round-bottomed flask of water (15ml), mechanical stirring evenly is the ionic liquid homogeneous phase aqueous solution, and the 4-methylcyclohexanone (0.560g, 5mmol) and phenylhydrazine (0.540g; 5mmol) add successively in this reaction vessel, room temperature condition is reaction 36h down, filters drying; Obtain the 3-methyl isophthalic acid, 2,3; 4-tetrahydro carbazole 0.814g, yield 88%, the product structure formula is:
Embodiment 18:
Disulfonic acid type acidic ion liquid [(HSO
3-p)
2Im] [HSO
4] (2.5mmol) add and to fill in the 25ml twoport round-bottomed flask of water (15ml), mechanical stirring evenly is the ionic liquid homogeneous phase aqueous solution, 4-tertiary butyl pimelinketone (0.463,3mmol) and phenylhydrazine (0.350g 3mmol) adds in this reaction vessel successively; Under mechanical stirring, 88 ℃ of oil bath heating, reaction 1h, cooling; Filter, drying obtains the 3-tertiary butyl-1,2; 3,4-tetrahydro carbazole 1.09g, yield 96%, the product structure formula is:
Embodiment 19:
Disulfonic acid type acidic ion liquid [(HSO
3-p)
2Im] [HSO
4] (2.5mmol) add and to fill in the 25ml twoport round-bottomed flask of water (15ml), mechanical stirring evenly is the ionic liquid homogeneous phase aqueous solution, and pimelinketone (0.490g, 5mmol) (0.610g 5mmol) adds in this reaction vessel successively with the 2-procarbazine; Under mechanical stirring, 85 ℃ of oil bath heating, reaction 1h, cooling; The mixed solution direct filtration, drying obtains the 8-methyl isophthalic acid, 2; 3,4-tetrahydro carbazole 0.8325g, yield 90%, the product structure formula is:
Embodiment 20:
Disulfonic acid type acidic ion liquid [(HSO
3-p)
2Im] [HSO
4] (2.5mmol) add and to fill in the 25ml twoport round-bottomed flask of water (15ml), mechanical stirring evenly is the ionic liquid homogeneous phase aqueous solution, and pimelinketone (0.490g, 5mmol) (0.690g 5mmol) adds in this reaction vessel successively with 4-methoxyl group phenylhydrazine; Under mechanical stirring, 90 ℃ of oil bath heating, reaction 2.5h, cooling; Filter, drying obtains 6-methoxyl group-1,2; 3,4-tetrahydro carbazole 0.874g, yield 87%, the product structure formula is:
Embodiment 21:
Disulfonic acid type acidic ion liquid [(HSO
3-p)
2Im] [HSO
4] (2.5mmol) add and to fill in the 25ml twoport round-bottomed flask of water (15ml), mechanical stirring evenly is the ionic liquid homogeneous phase aqueous solution, and pimelinketone (0.490g, 5mmol) (0.713g 5mmol) adds in this reaction vessel successively with the 4-chlorophenyl hydrazine; Under mechanical stirring, 90 ℃ of oil bath heating, reaction 1.5h, cooling; Filter, drying obtains product and obtains 6-chloro-1,2; 3,4-tetrahydro carbazole 0.943g, yield 92%, the product structure formula is:
Embodiment 22:
Disulfonic acid type acidic ion liquid [(HSO
3-p)
2Im] [HSO
4] (2.5mmol) add and to fill in the 25ml twoport round-bottomed flask of water (15ml), mechanical stirring evenly is the ionic liquid homogeneous phase aqueous solution, and pimelinketone (0.490g, 5mmol) (0.713g 5mmol) adds in this reaction vessel successively with the 2-chlorophenyl hydrazine;, under mechanical stirring, 90 ℃ of oil bath heating, reaction 1h, cooling; Filter, drying obtains product 8-chloro-1,2; 3,4-tetrahydro carbazole 0.93g, yield 91%, the product structure formula is:
Embodiment 23:
Disulfonic acid type acidic ion liquid [(HSO
3-p)
2Im] [HSO
4] (5mmol) add and to fill in the 25ml twoport round-bottomed flask of water (15ml), mechanical stirring evenly is the ionic liquid homogeneous phase aqueous solution, and pimelinketone (0.588g, 6mmol) (0.620g 5mmol) adds in this reaction vessel successively with the 4-nitrophenyl hydrazine; Under mechanical stirring, 100 ℃ of oil bath heating, reaction 5h, cool to room temperature filters; Washing, drying, 6-nitro-1,2; 3,4-tetrahydro carbazole 0.91g, yield 84%, the product structure formula is:
Embodiment 24:
Disulfonic acid type acidic ion liquid [(HSO
3-p)
2Im] [HSO
4] (5mmol) add and to fill in the 25ml twoport round-bottomed flask of water (15ml), mechanical stirring evenly is the ionic liquid homogeneous phase aqueous solution, and the 4-methylcyclohexanone (0.84g, 7.5mmol) (0.765g 5mmol) adds in this reaction vessel successively with the 4-nitrophenyl hydrazine; Under mechanical stirring, 100 ℃ of oil bath heating, reaction 5.5h, cooling; The mixed solution direct filtration, drying obtains product 3-methyl-6-nitro-1,2; 3,4-tetrahydro carbazole 0.977g, yield 85%, the product structure formula is:
Embodiment 25:
Disulfonic acid type acidic ion liquid [(HSO
3-p)
2Im] [HSO
4] (3mmol) add and to fill in the 25ml twoport round-bottomed flask of water (15ml), mechanical stirring evenly is the ionic liquid homogeneous phase aqueous solution, and the 4-methylcyclohexanone (0.56g, 5mmol) (0.71g 5mmol) adds in this reaction vessel successively with adjacent chlorophenyl hydrazine; Under mechanical stirring, 90 ℃ of oil bath heating, reaction 2h, cooling; The mixed solution direct filtration, drying obtains product 3-methyl-8-chloro-1,2; 3,4-tetrahydro carbazole 0.953g, yield 87%, the product structure formula is:
Embodiment 26:
Disulfonic acid type acidic ion liquid [(HSO
3-p)
2Im] [HSO
4] (3mmol) add and to fill in the 25ml twoport round-bottomed flask of water (15ml), mechanical stirring evenly is the ionic liquid homogeneous phase aqueous solution, the 4-methylcyclohexanone (0.56g, 5mmol) and a chlorophenyl hydrazine phenylhydrazine (0.71g 5mmol) adds in this reaction vessel successively; Under mechanical stirring, 90 ℃ of oil bath heating, 1h, cooling; The mixed solution direct filtration, drying obtains product 3-methyl-8-chloro-1,2; 3,4-tetrahydro carbazole 0.953g, yield 87%, the product structure formula is:
Embodiment 27:
Disulfonic acid type acidic ion liquid [(HSO
3-p)
2Im] [HSO
4] (5mmol) add and to fill in the 25ml twoport round-bottomed flask of water (15ml), mechanical stirring evenly be the ionic liquid homogeneous phase aqueous solution, and pimelinketone (0.294g, 3mmol) and 2,4 dichloro benzene hydrazine (0.531; 3mmol) add successively in this reaction vessel, under mechanical stirring, 95 ℃ of oil bath heating, reaction 7h, cooling; The mixed solution direct filtration, drying obtains 5,8-two chloro-1,2; 3,4-tetrahydro carbazole 1.04g, yield 87%, the product structure formula is:
Embodiment 28:
Disulfonic acid type acidic ion liquid [(HSO
3-p)
2Im] [HSO
4] (5mmol) add and to fill in the 25ml twoport round-bottomed flask of water (15ml), mechanical stirring evenly be the ionic liquid homogeneous phase aqueous solution, and the 4-methylcyclohexanone (0.490g, 5mmol) and 2,4 dichloro benzene hydrazine (0.89g; 5mmol) add successively in this reaction vessel, under mechanical stirring, 100 ℃ of oil bath heating, reaction 6.5h, cooling; The mixed solution direct filtration, drying obtains 3-methyl-5,8-two chloro-1,2; 3,4-tetrahydro carbazole 1.07g, yield 85%, the product structure formula is:
Embodiment 29:
Disulfonic acid type acidic ion liquid [(HSO
3-p)
2Im] [HSO
4] (2.5mmol) add and to fill in the 25ml twoport round-bottomed flask of water (15ml), mechanical stirring evenly is the ionic liquid homogeneous phase aqueous solution, and tetrahydric thiapyran-4-ketone (0.348g, 3mmol) and phenylhydrazine (0.324g; 3mmol) add successively in this reaction vessel, under mechanical stirring, 90 ℃ of oil bath heating, reaction 1h; Cooling is filtered, and drying obtains thiapyran [4; 3-b] indoles 0.538g, yield 95%, the product structure formula is:
Embodiment 30:
Disulfonic acid type acidic ion liquid [(HSO
3-p)
2Im] [HSO
4] (4mmol) add and to fill in the 25ml twoport round-bottomed flask of water (15ml), mechanical stirring evenly is the ionic liquid homogeneous phase aqueous solution, and ketopentamethylene (0.420g, 5mmol) and naphthylhydrazine (0.790g; 5mmol) add successively in this reaction vessel, under mechanical stirring, 90 ℃ of oil bath heating, reaction 2h; Drying is filtered in cooling; Obtain product 0.869g, yield 84%, the product structure formula is:
Embodiment 31:
Disulfonic acid type acidic ion liquid [(HSO
3-p)
2Im] [HSO
4] (4mmol) add and to fill in the 25ml twoport round-bottomed flask of water (15ml), mechanical stirring evenly be the ionic liquid homogeneous phase aqueous solution, and pimelinketone (0.49g, 5mmol) and 5-methyl-2-naphthylhydrazine (0.790g; 5mmol) add successively in this reaction vessel, under mechanical stirring, 85 ℃ of oil bath heating, reaction 1.5h; Drying is filtered in cooling; Obtain product 1.022g, yield 87%, the product structure formula is:
Embodiment 32:
Disulfonic acid type acidic ion liquid [(HSO
3-p)
2Im] [HSO
4] (3.5mmol) add and to fill in the 25ml twoport round-bottomed flask of water (15ml), mechanical stirring evenly be the ionic liquid homogeneous phase aqueous solution, and suberone (0.560g, 5mmol) and 8-chloro-2-naphthylhydrazine (0.790g; 5mmol) add successively in this reaction vessel, under mechanical stirring, 90 ℃ of oil bath heating, reaction 2h; Drying is filtered in cooling; Obtain product 1.135g, yield 85%, the product structure formula is:
Embodiment 33:
Disulfonic acid type acidic ion liquid [(HSO
3-p)
2Im] [HSO
4] (4mmol) add and to fill in the 25ml twoport round-bottomed flask of water (15ml), mechanical stirring evenly be the ionic liquid homogeneous phase aqueous solution, and butanone (0.360g, 5mmol) and 1-methyl-2-naphthylhydrazine (0.860g; 5mmol) add successively in this reaction vessel, under mechanical stirring, 84 ℃ of oil bath heating, reaction 3h; Drying is filtered in cooling; Obtain product 0.89g, yield 84%, the product structure formula is:
Embodiment 34:
Disulfonic acid type acidic ion liquid [(HSO
3-p)
2Im] [HSO
4] (4mmol) add and to fill in the 25ml twoport round-bottomed flask of water (15ml), mechanical stirring evenly be the ionic liquid homogeneous phase aqueous solution, and butanone (0.360g, 5mmol) and 1-chloro-2-naphthylhydrazine (0.963g; 5mmol) add successively in this reaction vessel, under mechanical stirring, 87 ℃ of oil bath heating, reaction 3h; Cooling is filtered, washing, drying; Obtain product 0.912g, yield 80%, the product structure formula is:
Embodiment 35:
Disulfonic acid type acidic ion liquid [(HSO
3-p)
2Im] [HSO
4] (4.5mmol) add and to fill in the 25ml twoport round-bottomed flask of water (15ml), mechanical stirring evenly be the ionic liquid homogeneous phase aqueous solution, and butanone (0.360g, 5mmol) and 1-methoxyl group-2-naphthylhydrazine (0.940; 5mmol) add successively in this reaction vessel, under mechanical stirring, 90 ℃ of oil bath heating, reaction 3h; Cooling is filtered, washing, drying; Obtain product 0.923g, yield 82%, the product structure formula is:
Embodiment 36:
Disulfonic acid type acidic ion liquid [(HSO
3-p)
2Im] [HSO
4] (3.5mmol) add and to fill in the 25ml twoport round-bottomed flask of water (15ml), mechanical stirring evenly be the ionic liquid homogeneous phase aqueous solution, and tetrahydric thiapyran-4-ketone (0.348g, 3mmol) and 1-methyl-2-naphthylhydrazine (0.516g; 3mmol) add successively in this reaction vessel, under mechanical stirring, 90 ℃ of oil bath heating, reaction 1.5h; Drying is filtered in cooling; Obtain product 0.73g, yield 96%, the product structure formula is:
Embodiment 37:
Disulfonic acid type acidic ion liquid [(HSO
3-p)
2Im] [HSO
4] (5mmol) add and to fill in the 25ml twoport round-bottomed flask of water (15ml), mechanical stirring evenly is the ionic liquid homogeneous phase aqueous solution, 1,3 cyclohexanedione (0.560g; 5mmol) and phenylhydrazine (0.540g 5mmol) joins in this reaction vessel successively, under mechanical stirring, 100 ℃ of reactions of oil bath heating 12h; The mixed solution direct filtration, drying obtains 1,2; 3,9-tetrahydrochysene-4H-carbazole-4-ketone 0.63g, yield 68%, the product structure formula is:
Embodiment 38:
Disulfonic acid type acidic ion liquid [(HSO
3-p)
2Im] [HSO
4] (5mmol) add and to fill in the 25ml twoport round-bottomed flask of water (15ml), mechanical stirring evenly is the ionic liquid homogeneous phase aqueous solution, 5, and 5-dimethyl-1; 3 cyclohexanediones (0.70g, 5mmol) and phenylhydrazine (0.540g 5mmol) joins in this reaction vessel, successively under mechanical stirring; 100 ℃ of reactions of oil bath heating 10h, mixed solution direct filtration, drying; Obtain title product 0.70g, yield 66%, the product structure formula is:
Embodiment 39: ionic liquid recycles experiment
The remaining solution in back is filtered in reaction among the embodiment 1 directly need not continue to add ionic liquid as catalyzer, in this solution, directly add raw material and can be used for reacting next time through can be used as reaction medium behind the strongly acidic styrene type cation exchange resin.React according to embodiment 1 step, ionic liquid aqueous solution can recycle more than 12 times at least, and the gained result sees table 1.
Table 2: [(HSO
3-p)
2Im] [HSO
4] experiment of ionic liquid recycled
| Cycle index | Yield (%) |
| 1 | 93 |
| 2 | 90 |
| 3 | 89 |
| 4 | 90 |
| 5 | 88 |
| 6 | 87 |
| 7 | 88 |
| 8 | 87 |
| 9 | 89 |
| 10 | 88 |
| 11 | 89 |
| 12 | 87 |
Claims (8)
1. the green synthesis method of a Benzazole compounds; The structure of said Benzazole compounds is suc as formula shown in (I)～formula (VII); It is characterized in that described compound method be with structure suc as formula the aldehydes or ketones of (i)～formula shown in (iv) and structure suc as formula (v) or formula (aryl hydrazine vi) is a substrate; Structure suc as formula (under the disulfonic acid type presence of acidic ionic liquid catalyst vii) in water solvent in 20～100 ℃ of fully reactions; The gained reaction mixture filters, and must filtrate and filter cake, and filtration cakes torrefaction promptly obtains described Benzazole compounds; Said aldehydes or ketones is 1: 0.5～2 with the ratio of the amount of substance of said aryl hydrazine; Said disulfonic acid type acidic ion liquid is 1: 1～5 with the ratio of the amount of substance of said aldehydes or ketones; The concentration of said disulfonic acid type acidic ion liquid in water solvent is 0.01～1mol/L;
Wherein, R
1Alkyl for the substituted alkyl of the phenyl of H, phenyl, C7～C20 or C1～C20;
R
2Be the alkyl of C1～C20, the substituted alkyl of phenyl of come together base or C7～C20;
R
3, R
4, R
5, R
6, R
12, R
13, R
14, R
15, R
16, R
17Independent separately is the alkyl of H, C1～C4, alkoxyl group, nitro or the halogen of C1～C4;
R
7, R
8, R
9, R
10, R
11Independent separately is the alkyl of H or C1～C5;
n＝1～4；
R is S or C;
(vii), m is 1 or 2 to formula, and it is one of following that Y is selected from: HSO
4, H
2PO
4, p-CH
3C
6H
4SO
3
2. the green synthesis method of Benzazole compounds as claimed in claim 1 is characterized in that described disulfonic acid type acidic ion liquid is [(HSO
3-p)
2Im] [HSO
4].
3. the green synthesis method of Benzazole compounds as claimed in claim 1 is characterized in that the said aldehydes or ketones and the ratio of the amount of substance of said aryl hydrazine are 1: 1～1.5; Said disulfonic acid type acidic ion liquid is 1: 1～3 with the ratio of the amount of substance of said aldehydes or ketones.
4. the green synthesis method of Benzazole compounds as claimed in claim 3 is characterized in that the concentration of said disulfonic acid type acidic ion liquid in water solvent is 0.1～0.3mol/L.
5. like the green synthesis method of the described Benzazole compounds of one of claim 1～4, it is characterized in that the described reaction times is 0.5～40h.
6. the green synthesis method of Benzazole compounds as claimed in claim 5 is characterized in that describedly being reflected at 60～100 ℃ and carrying out 1～8h.
7. like the green synthesis method of the described Benzazole compounds of one of claim 1～4, it is characterized in that said reaction mixture filters gained filtrating and removes the NH that dereaction generates through the acid exchange
4 +After, in reaction, continue to apply mechanically; The acid that described acid exchange is used is hydrochloric acid or strongly acidic cationic exchange resin.
8. the green synthesis method of Benzazole compounds as claimed in claim 7 is characterized in that the acid that described acid exchange is used is strongly acidic cationic exchange resin.
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