CN1073990C - Process for preparing (inner) N-alkyl imide - Google Patents

Process for preparing (inner) N-alkyl imide Download PDF

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CN1073990C
CN1073990C CN97106999A CN97106999A CN1073990C CN 1073990 C CN1073990 C CN 1073990C CN 97106999 A CN97106999 A CN 97106999A CN 97106999 A CN97106999 A CN 97106999A CN 1073990 C CN1073990 C CN 1073990C
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CN1202485A (en
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宋湛谦
周永红
王延
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Institute of Chemical Industry of Forest Products of CAF
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Abstract

The present invention relates to a method for preparing an (inner) N-alkyl imide (III) compound of which the general formula is disclosed in the following formula (III), wherein R is a C3 to C12 straight chain or branched alkyl, preferably a C6-C12 alkyl group, and particularly-CH2CH(C2H5)C4H9. The method comprises the following steps: an imide compound of which the structural formula is disclosed in (V) and a compound of which the structural formula is equivalent to the structural formula is disclosed in (V) are mixed with a phase transfer catalyst of which the dosage is from 1 to 100 mol% and a cocatalyst; the mixture of solid alkali and organic solvent or the mixture of alkaline water solution and organic solvent are added; thus, the reaction is carried out under the condition of inorganic solid alkali and an organic liquid phase, or inorganic liquid phase and an organic liquid phase; then the mixture is stirred, and is heated to 40 to 150 DEG C; RX organic solution is added drop by drop, wherein R is a C3 to C12 straight chain or branched alkyl, X is chlorine or bromine, and the reaction time is from 2 to 4 hours; the catalyst is removed, and the solvent is distilled.

Description

The preparation method of (interior) N-alkylimide
The present invention relates to a kind of preparation method of N-alkylimide, particularly a kind of preparation method of (interior) N-alkylimide as insecticidal synergist.
General formula is a kind of compound with extensive use for the N-alkylimide of (I).For example, in the prior art, usually with it as one of component of sterilant, play insecticidal synergist:
Figure C9710699900031
For example Japanese Patent JP105602 is with N-(2-ethyl) hexyl-1-sec.-propyl-4-methyl bicyclic [2,2,2]-5-octene-2,3-dicarboximide Synergistic agent as pyrethroid.Japanese Patent JP13141 (1966) has disclosed the preparation method of general formula for the N-alkylimide compound of (I), and this method is by structural formula is made the N-alkylimide for the anhydridization compound of (II) reacts with 2 ethyl hexylamine:
General formula has two kinds of three-dimensional arrangements for the N-alkylimide of (I), i.e. (interior) (endo) N-alkylimide and outer (exo) N-alkylimide, respectively shown in following formula III and (IV):
Figure C9710699900034
Applicant of the present invention finds, as pesticide synergistic agent, the synergism of (interior) N-alkylimide (III) is better than having the N-alkylimide of other three-dimensional arrangement.But because the steric hindrance of (interior) N-alkylimide (III) is bigger, adopt art methods, can not obtain (interior) N-alkylimide (III) compound with the ideal yield.
For example, Japanese Patent JP2235865 (1990) has reported the synthetic method with the imide compound of the similar of (interior) N-alkylimide (III) compound, this method be with corresponding raw material and dihalo hydrocarbon in the presence of phase-transfer catalyst and alkali, in two-phase system, react, but do not indicate the three-dimensional arrangement of imide compound in the document.
The objective of the invention is provides a kind of simple to operate, the method for the preparation that yield is high (interior) N-alkylimide (III) compound for the shortcoming that overcomes prior art.
The present invention relates to a kind of general formula is the preparation method of (interior) N-alkylimide (III) compound of following (III):
Figure C9710699900041
Wherein, R is C 3-C 12The straight or branched alkyl is preferably C 6-C 12Alkyl is preferably-CH especially 2CH (C 2H 5) C 4H 9, this method may further comprise the steps:
With structure is the imide compound of (V)
Figure C9710699900042
Be equivalent to phase-transfer catalyst and the promoter metal organic compound of structural formula for the 1-100% (mole) of the compound amount of (V), after mixing, add solid alkali-ORGANIC SOLVENT MIXTURES or alkaline aqueous solution-ORGANIC SOLVENT MIXTURES, make to be reflected under inoganic solids phase-organic liquid phase or the inorganic liquid phase-organic liquid phase condition and carry out, stir, be heated to 40-150 ℃, drip the organic solution of RX, wherein, R is C 3-C 12The straight or branched alkyl is preferably C 6-C 12Alkyl is preferably-CH especially 2CH (C 2H 5) C 4H 9, X is a halogen, is preferably bromine or chlorine, reacts 2-4 hour, removes catalyzer and boils off solvent, gets product.
According to the inventive method, described phase-transfer catalyst can be a quaternary ammonium salt, and as cetyl trimethylammonium bromide, dodecylbenzyl ammonium chloride or Tetrabutyl amonium bromide, quaternary alkylphosphonium salt is as hexadecyltri-n-butylphosp; Described promotor is a metallocene, as ferrocene, dicyclopentadienyltin; Described solid alkali is the mixture of alkaline carbonate and alkali metal hydroxide, as K 2CO 3And KOH, or Na 2CO 3With the mixture of NaOH, described alkaline aqueous solution is the 30-50%KOH or the NaOH aqueous solution; Described organic solvent is rudimentary property aprotic solvent, and as methylene dichloride, trichloromethane, benzene, toluene or dimethylbenzene, temperature of reaction is 40-150 ℃.
According to the present invention, in described solid alkali-ORGANIC SOLVENT MIXTURES or the alkaline aqueous solution-ORGANIC SOLVENT MIXTURES in employed organic solvent and the described 1-bromo-2-ethyl hexane organic solution employed organic solvent be identical.
Adopt preparation method of the present invention, can synthetic (interior) N-alkylimide (III) compound of high yield as insecticidal synergist.
Describe the present invention in detail with comparative example by the following examples.
Embodiment 1 (interior) N-(2-ethyl) hexyl-1-sec.-propyl-4-methyl bicyclic " 2,2,2 "-5-octene-2,3-dicarboximide (R=-CH 2CH (C 2H 5) C 4H 9) preparation
With 0.7g (interior) 1-sec.-propyl-4-methyl bicyclic " 2,2,2 "-5-octene-2,3-dicarboximide and 0.23gKOH, 0.5gK 2CO 3, 0.20g Tetrabutyl amonium bromide, 0.15g ferrocene, 10ml benzene mix.Be heated with stirring to 80 ℃, be added dropwise to the benzole soln that 10ml contains 0.68gl-bromo-2-ethyl hexane, reacted 3 hours.Filter, remove catalyzer with 2N HCl wash filtrate, redistillation except that desolvate the 0.83g title compound, be weak yellow liquid.
Yield: 80.2%
Boiling point: 190-1935 ℃/0.5mmHg
N 20 d1.4962
R f10.408 (hexane: acetone=9: 1)
Spectral analysis data:
IR(V max,cm -1)：2910(s)2840(m)
1765(s)1395(s)1180(s)700(s)
MS (m/z, relative abundance): 346 (0.4) 345 (1.1)
234 (6.7) 211 (16.0) 135 (base peak, 100.0) 93 (2.6)
1H NMR(H,PPM):5.79-6.01(2H,q,5,6-CH),3.22、3.30(2H,d,R-H),2.47-2.96(2H,q2,3-CH),2.60(1H,m,10-CH),1.48(3H,s,9-CH 3),1.52(1H,s,R-H),1.32-1.41(4H,m,7,8-CH 2),1.28(8H,m,R-H),0.93-1.41(6H,2d,11,12-CH 3)
Embodiment 2 (interior) N-(2-ethyl) hexyl-1-sec.-propyl-4-methyl bicyclic " 2,2,2 "-5-octene-2,3-dicarboximide (R=-CH 2CH (C 2H 5) C 4H 9) preparation
0.70g (interior) 1-sec.-propyl-4-methyl bicyclic " 2.2.2 "-5-octene-2,3-dicarboximide, 0.20g Tetrabutyl amonium bromide, 0.15g ferrocene, 10ml50%NaOH solution and 10ml benzene are mixed.Be heated with stirring to 80 ℃, drip the benzole soln that 10ml contains 0.68gl-bromo-2-ethyl ethane, reacted 3 hours.Remove catalyzer with 2N HCl washing, redistillation remove desolvate the 0.8g title compound, be weak yellow liquid.Yield is 77.3%.Its physical constant and spectral analysis data are with embodiment 1.
Embodiment 3 (interior) N-cyclohexyl-1-sec.-propyl-4-methyl bicyclic " 2,2,2 "-5-octene-2,3-dicarboximide (R=-(CH 2) 6) preparation
Repeat the method identical, just, obtain the 0.85g title compound, be white solid with the 1-bromo-2-ethyl hexane among the chlorocyclohexane replacement embodiment 1 of 0.42g with embodiment 1.
Yield: 89.8%
Fusing point: 82.5-84 ℃
R f0.614 (sherwood oil: ethyl acetate=5: 1)
Spectral analysis data:
IR(V max,cm -1):2940(s),2850(m),1760(s),1695(s),1390(m),1370(s),1190(s),720(m),700(s)
MS (m/z, relative abundance): 316 (0.6), 315 (1.3), 234 (4.8), 181 (14.8), 135 (base peak, 100.0), 119 (11.0), 93 (13.2)
1H NMR(H,PPM):5.80-6.02(2H,q),4.09-4.40(2H,m),2.41-2.90(2H,q),2.60(1H,m),1.47(3H,s),1.32-1.39(4H,m,7,8-CH 2),1.24(10H,s),0.93-1.13(6H,2d)
Embodiment 4 (interior) N-dodecyl-1-sec.-propyl-4-methyl bicyclic " 2,2,2 "-5-octene-2,3-dicarboximide (R=-(CH 2) 11CH 3) preparation
Repeat the method identical, just, obtain the 0.92g title compound, be weak yellow liquid with the 1-bromo-2-ethyl hexane among the 1-bromo-dodecane replacement embodiment 1 of 0.88g with embodiment 1.
Yield: 76.5%
Boiling point: 198-200 ℃/0.5mmHg
N 20 d1.4967
R f0.720 (sherwood oil: ethyl acetate=5: 1)
Spectral analysis data:
IR(V max,cm -1):2910(s),2840(m),1760(s),1695(s),1395(s),1365(m),1170(m),720(m),700(m)
MS (m/z, relative abundance): 402 (0.5), 401 (1.8), 267 (7.4), 135 (base peak, 100.0), 119 (9.3), 110 (3.12), 93 (6.9)
1H NMR(H,PPM):5.79-6.01(2H,q),3.28-3.43(2H,t),2.46-2.95(2H,q),2.61(1H,m),1.48(3H,s),1.31-1.41(4H,m,7,8-CH 2),1.25(10H,s),0.94-1.14(4H,2d)
Embodiment 5 (interior) N-n-octylcyclam-sec.-propyl-4-methyl bicyclic " 2,2,2 "-5-octene-2,3-dicarboximide (R=-(CH 2) 7CH 3) preparation
Repeat the method identical, just, obtain the 0.88g title compound, be weak yellow liquid with the 1-bromo-2-ethyl hexane among the 1-bromooctane replacement embodiment 1 of 0.68g with embodiment 1.
Yield: 85.0%
Boiling point: 180-182 ℃/0.5mmHg
N 20 d1.4975
R f0.420 (hexane: acetone=9: 1)
Spectral analysis data:
IR(V max,cm -1):2910(s),2840(m),1765(s),1695(s),1395(s),1365(m),1170(m),720(m),700(s)
MS (m/z, relative abundance): 346 (0.7), 345 (1.0), 211 (8.9), 136 (35.2), 135 (base peak, 100.0), 119 (8.3), 110 (2.9), 107 (2.7), 105 (2.6), 93 (6.4), 91 (3.3)
1H NMR(H,PPM):5.79-6.01(2H,q),3.28-3.43(2H,t),2.46-2.95(2H,q),2.60(1H,m),1.48(3H,s),1.31-1.41(4H,m,7,8-CH 2),1.25(12H,s),0.94-1.14(6H,2d)
Embodiment 6 (interior) N-sec.-propyl-1-sec.-propyl-4-methyl bicyclic " 2,2,2 "-5-octene-2,3-dicarboximide (R=-CH (CH 3) 2) preparation
Repeat the method identical, just, obtain the 0.76g title compound, be white solid with the 1-bromo-2-ethyl hexane among the bromo propane replacement embodiment 1 of 0.43g with embodiment 1.
Yield: 92.1%
Fusing point: 85-86 ℃
R f0.599 (sherwood oil: ethyl acetate=5: 1)
Spectral analysis data:
IR(V max,cm -1):2950(s),2870(m),1755(m),1695(m),1465(s),1365(s),1230(s),700(s)
MS (m/z, relative abundance): 276 (0.2), 275 (0.7), 149 (15.5), 141 (0.2), 136 (33.0), 135 (base peak, 100.0), 124 (1.3), 119 (11.4), 93 (12.2), 91 (6.2)
1H NMR(H,PPM):5.77-6.00(2H,q),3.66-4.01(1H,m),2.40-2.89(2H,q),2.60(1H,m),1.47(3H,s),1.32-1.39(4H,m,7,8-CH 2),0.93-1.13(12H,2d)
Comparative example 1-5
According to the disclosed method of JP13141 (1966), with 0.70g1-sec.-propyl-4-methyl bicyclic " 2; 2; 2 "-5-octene-2, the 3-dicarboxylic anhydride reacts with 2 ethyl hexylamine, hexahydroaniline, lauryl amine, n-octyl amine, Isopropylamine respectively, prepares N-(2-ethyl) hexyl imide, N-cyclohexyl imide, N-dodecyl imide, N-n-octyl imide and N-sec.-propyl imide respectively.Yield is the result be compared as follows shown in the table.
Compound JP13141 the inventive method N-(2-ethyl) hexyl imide 0.80g 0.83gN-cyclohexyl imide 0.80g 0.85gN-dodecyl imide 0.83g 0.92gN-n-octyl imide 0.84g 0.88gN-sec.-propyl imide 0.77g 0.76g
The effect of comparative example 6 promotors
Repeat the method for embodiment 1,2, just do not add 0.15g promotor ferrocene, relatively the variation of product yield the results are shown in following table.
Press the method for embodiment 1 Press the method for embodiment 2
Add ferrocene 0.83g 0.80g
Do not add ferrocene 0.72g 0.66g
The insecticidal synergistic effect of experimental example (interior) N-alkylimide (III) compound and the insecticidal synergistic effect of (outward) N-alkylimide (IV) compound and the comparison of blended N-alkylimide (III) compound insecticidal synergistic effect
Respectively (interior) N-alkylimide (III) compound, (outward) N-alkylimide (IV) compound and blended N-alkylimide compound are mixed with the sterilant permethrin, by the medicine embrane method test, relatively (interior) N-alkylimide (III) compound, (outward) N-alkylimide (IV) compound and blended N-alkylimide compound are killed the synergistic effect of periplaneta americana to the sterilant permethrin.
Sterilant and synergistic agent Dosage KT 50 KT 95 24 hours mortality ratio
(mg/m 2) (minute) (minute) (％)
Permethrin permethrin+III (interior) permethrin+IV (outward) *Permethrin+III (interior)+IV (outward) 54 54+162 54+162 54+81+81 6.0 3.4 4.9 3.8 11.3 7.9 9.5 8.6 95.0 100.0 98.0 100.0
*The preparation of IV (outward): press J.Org.Chem., Vol.53, No.25,1988, pp5812-5815 preparation (outward) 1-sec.-propyl-4-methyl bicyclic [2,2,2]-and 5-octene-2, the 3-dicarboxylic anhydride prepares IV (outward) according to the disclosed method of JP13141 (1966) then.

Claims (11)

1. the preparation method of general formula N-alkylimide (III) compound that is following (III):
Figure C9710699900021
Wherein, R is C 3-C 12The straight or branched alkyl, this method may further comprise the steps: with structural formula is (V):
Figure C9710699900022
Imide compound and be equivalent to structural formula and mix for the phase-transfer catalyst and the metallocene promotor of the compound amount 1-100% mole of (V), add solid alkali-ORGANIC SOLVENT MIXTURES or alkaline aqueous solution-ORGANIC SOLVENT MIXTURES, make to be reflected under inoganic solids alkali-organic liquid phase or the inorganic liquid phase-organic liquid phase condition and carry out, stir, be heated to 40-150 ℃, drip the organic solution of RX, wherein R is C 3-C 12Straight or branched alkyl, X are chlorine or bromine, react 2-4 hour, remove catalyzer and boil off solvent, get product.
2. method according to claim 1, wherein, described R is C 6-C 12The straight or branched alkyl.
3. method according to claim 1, wherein, described R is-CH 2CH (C 2H 5) C 4H 9
4. method according to claim 1, wherein, described phase-transfer catalyst is quaternary ammonium salt or quaternary alkylphosphonium salt.
5. method according to claim 4.Wherein, described phase-transfer catalyst is a four butyl bromation amine.
6. method according to claim 1, wherein, described promotor is a ferrocene.
7. method according to claim 1, wherein, described solid alkali is the mixture of alkaline carbonate and alkali metal hydroxide.
8. method according to claim 7, wherein, described solid alkali is K 2CO 3With KOH or Na 2CO 3Mixture with NaOH.
9. method according to claim 1, wherein, described alkaline aqueous solution is the 30-50%NaOH or the KOH aqueous solution.
10. method according to claim 1, wherein, described organic solvent is halogenated alkane or aromatic hydrocarbons.
11. method according to claim 10, wherein, described halogenated alkane is methylene dichloride or trichloromethane, and described aromatic hydrocarbons is benzene, toluene or dimethylbenzene.
CN97106999A 1997-06-17 1997-06-17 Process for preparing (inner) N-alkyl imide Expired - Fee Related CN1073990C (en)

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CN102477038B (en) * 2010-11-30 2013-10-23 哈尔滨医科大学 New lactim compound possessing cardiotonic action, its preparation method and its purpose
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Citations (3)

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Publication number Priority date Publication date Assignee Title
US3658957A (en) * 1964-12-17 1972-04-25 Ici Australia Ltd Process for combatting fungi using a bicyclo dicarboxylic anhydride or imide as the fungicide
JPH02235865A (en) * 1989-03-09 1990-09-18 Sumitomo Pharmaceut Co Ltd Production of cyclic imide derivative
CN1117964A (en) * 1994-08-27 1996-03-06 中国林业科学研究院林产化学工业研究所 N-alkylimide and its preparation method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3658957A (en) * 1964-12-17 1972-04-25 Ici Australia Ltd Process for combatting fungi using a bicyclo dicarboxylic anhydride or imide as the fungicide
JPH02235865A (en) * 1989-03-09 1990-09-18 Sumitomo Pharmaceut Co Ltd Production of cyclic imide derivative
CN1117964A (en) * 1994-08-27 1996-03-06 中国林业科学研究院林产化学工业研究所 N-alkylimide and its preparation method

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