CN103254027B - One prepares the method for 1,2-diphenyl propylene compound - Google Patents

One prepares the method for 1,2-diphenyl propylene compound Download PDF

Info

Publication number
CN103254027B
CN103254027B CN201310170872.8A CN201310170872A CN103254027B CN 103254027 B CN103254027 B CN 103254027B CN 201310170872 A CN201310170872 A CN 201310170872A CN 103254027 B CN103254027 B CN 103254027B
Authority
CN
China
Prior art keywords
phenyl
reaction
warming
propylene
hours
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201310170872.8A
Other languages
Chinese (zh)
Other versions
CN103254027A (en
Inventor
姜鹏
孟志
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenyang Sinochem Agrochemicals R&D Co Ltd
Original Assignee
Shenyang Research Institute of Chemical Industry Co Ltd
Sinochem Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shenyang Research Institute of Chemical Industry Co Ltd, Sinochem Corp filed Critical Shenyang Research Institute of Chemical Industry Co Ltd
Priority to CN201310170872.8A priority Critical patent/CN103254027B/en
Publication of CN103254027A publication Critical patent/CN103254027A/en
Application granted granted Critical
Publication of CN103254027B publication Critical patent/CN103254027B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention belongs to organic synthesis field, relate to the method that one prepares 1,2-diphenyl propylene compound particularly.Take substituted phenylacetic acid as starting raw material, react simultaneous isomerization rearrangement obtain target product through halogenation, acylations, wittig.It is simple that the inventive method prepares 1,2-diphenyl propylene compound technique, and operation steps is few, and reaction conditions is gentle, and content and the yield of target product are higher.

Description

One prepares the method for 1,2-diphenyl propylene compound
Technical field
The invention belongs to organic synthesis field, relate to the method that one prepares 1,2-diphenyl propylene compound particularly.
Background technology
1,2-diphenyl propylene compound prepares the important intermediate of azoles methyl oxirane series bactericidal agent.The preparation method of preparation 1,2-diphenyl propylene compound is disclosed in US5268517, US4464381, CN102304014.Conventionally, after 1,2-diphenyl propylene compound adopts wittig to become alkene or Grignard reagent to become alcohol, dehydration or phenyl aldehyde and phenylacetic aldehyde aldol condensation dewater to reduce and prepare and obtain, and reaction formula is as follows:
(l) wittig method
(2) grignard reagent method (3) aldol condensation method
Wherein wittig route yield is lower, and yield is only about 55% (US4464381), and reason is that the Ylide reagent steric hindrance of benzyltriphenyl phosphonium halophosphines is too large; And grignard reagent reaction conditions is comparatively harsh, reaction yield is only 68%(US5268517), and these step needs of dehydration of alcohols add a large amount of diacetyl oxide and the vitriol oil, and environment is unfriendly; Aldol condensation dehydration/reduction method high expensive, step is long, is not suitable for suitability for industrialized production.
Summary of the invention
Technical problem to be solved by this invention overcomes the deficiencies in the prior art, provides one to prepare the method for 1,2-diphenyl propylene compound.
For achieving the above object, the present invention adopts technical scheme to be:
One prepares the method for 1,2-diphenyl propylene compound, take substituted phenylacetic acid as starting raw material, reacts simultaneous isomerization rearrangement obtain target product through halogenation, acylations, wittig.
Concrete reaction formula is as follows:
(1) substituted phenylacetic acid A and halide reagent react and generate carboxylic acid halides B under the katalysis of DMF, and reaction equation is as follows:
(2) substituted benzene C and carboxylic acid halides B reacts and generates substituted-phenyl benzyl ketone D under catalyst, and reaction equation is as follows:
(3) substituted-phenyl benzyl ketone D generates target product 1,2-phenylbenzene propylene E in the basic conditions with methyl triphenyl halogenation phosphine reaction, and reaction equation is as follows:
Wherein X is chlorine or bromine; R 1, R 2it is monosubstituted or the polysubstituted identical or different substituting group on above-mentioned phenyl ring.
Described R 1, R 2for the halogenated alkoxy of the alkyl of identical or different hydrogen, halogen, nitro, amino, cyano group, C1-C4, the alkoxyl group of C1-C4, the haloalkyl of C1-C4 or C1-C4.
Further, R1, R2 are identical or different hydrogen, fluorine, chlorine, bromine, nitro, methoxyl group, oxyethyl group, methyl, ethyl or cyano group.
Described halogen is fluorine, chlorine, bromine or iodine; Described alkyl is methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, cyclopropyl, cyclobutyl; Described alkoxyl group is the group that alkyl end is connected with Sauerstoffatom, as methoxyl group, oxyethyl group, positive propoxy, isopropoxy, tert.-butoxy etc.; Described haloalkyl refers to the group that alkyl is replaced by one or more halogen atom; Halogenated alkoxy refers to that alkyl is replaced by one or more halogen atom, and end is connected with the group of Sauerstoffatom.
Further, the substituted phenylacetic acid shown in general formula A and DMF are dissolved in solvent, then drip after halide reagent in 0 DEG C to solvent boiling point temperature range to react and generate the carboxylic acid halides shown in Formula B in 0.5-24.0 hour;
Carboxylic acid halides shown in Formula B and catalyzer are dissolved in solvent, then add general formula C, at-10 DEG C-50 DEG C, react 1-12 hour to obtain Compound D;
Alkali to be joined in methyl triphenyl halogenation phosphine and in the presence of an organic ,-10 DEG C-30 DEG C reactions added Compound D after 0.5-5.0 hour, in 20 DEG C-100 DEG C reactions after 1-24 hour target product E.
Further, described catalyzer is selected from Aluminum chloride anhydrous, Zinc Chloride Anhydrous, polyphosphoric acid or boron trifluoride; The charged molar ratio of the carboxylic acid halides shown in Formula B and catalyzer is 1:1-3; The charged molar ratio of the carboxylic acid halides shown in Formula B and substituted benzene C is 1:1-10; Described solvent is selected from methylene dichloride, tetracol phenixin, 1,2-ethylene dichloride, dithiocarbonic anhydride, sherwood oil, oil of mirbane or substituted benzene C.
Substituted phenylacetic acid shown in general formula A and DMF are dissolved in solvent, then drip after halide reagent in 20 DEG C to solvent boiling point temperature range to react and generate the carboxylic acid halides shown in Formula B in 0.5-24.0 hour.
The charged molar ratio of described substituted phenylacetic acid and halide reagent is 1:1-10, described halide reagent is selected from oxalyl chloride, sulfur oxychloride, phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride or phosphorus pentabromide, and described solvent is methylene dichloride, the halide reagent of toluene, hexane or above-mentioned liquid state is double makees solvent.
The charged molar ratio of described substituted phenylacetic acid A and halide reagent is 1:1-4; Wherein halide reagent is selected from oxalyl chloride or sulfur oxychloride.
The charged molar ratio of described acyl chlorides B and catalyzer is 1:1.2-2.0; Wherein, catalyzer is Aluminum chloride anhydrous.
The charged molar ratio of described methyl triphenyl halogenation phosphine and alkali is 1:1, and Compound D and alkali mol ratio are 1:1-4; Described alkali is selected from potassium tert.-butoxide, sodium hydride, potassium hydride KH, sodium ethylate, sodium methylate, sodium hydroxide, potassium hydroxide, n-Butyl Lithium, sodium amide, lithium methide or lithium diisopropyl amido; Described organic solvent is selected from acetonitrile, methyl alcohol, ethanol, Virahol, methylene dichloride, DMF, benzene, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO) or dioxane.
Described Compound D and alkali mol ratio are 1:2-3; Wherein, methyl triphenyl halogenation phosphine is methyl triphenyl phosphonium chloride or methyltriphenylphosphonium bromide; Alkali is selected from potassium tert.-butoxide, sodium ethylate or sodium hydride.
The advantage that the present invention has: the present invention synthesizes that 1,2-diphenyl propylene compound route is short, technique is simple, each step reaction all can complete in a mild condition, is beneficial to operation, target product yield and content higher.
Embodiment
Be further described technical scheme of the present invention below in conjunction with specific embodiment, but the present invention is not limited only to these embodiments, if embodiment does not do Special Statement, quality is in g(gram), volume is in mL(milliliter).
Embodiment 12-phenyl-1-(2-chloro-phenyl-) synthesis of propylene
Step 1: the synthesis of o-chlorobenzene acetyl chloride
In reaction flask, add 5.1g(30mmol) o-chlorobenzene acetic acid, 0.1g DMF, then add 50mL methylene dichloride stirring and dissolving, drip 5.3g(45mmol) sulfur oxychloride in above-mentioned solution, 1h dropwises, then be warming up to backflow, after reaction 3h, terminate reaction.Steam solvent and excessive sulfur oxychloride obtains o-chlorobenzene acetyl chloride 5.4g(28.6mmol), yield is 95%.
Step 2: the synthesis of o-chlorobenzyl phenyl ketone
By 4.6g(34.8mmol) Aluminum chloride anhydrous joins 13.5g(174mmol) in benzene, temperature is down to 0 DEG C, then adds o-chlorobenzene acetyl chloride 5.4g(28.6mmol), terminate reaction after being naturally warming up to room temperature reaction 6h.Stir in slow for reaction solution impouring frozen water, be then extracted with ethyl acetate separatory, steam solvent treatment and obtain 5.7g(24.6mmol) o-chlorobenzyl phenyl ketone, yield is 86%.
1H-NMR（300MHz，CDCl 3）：δ（ppm）8.05（d，2H），7.58（m，1H），7.50（m，2H），7.41（m，1H），7.25（m，3H），4.44（s，2H）
Step 3:2-phenyl-1-(2-chloro-phenyl-) synthesis of propylene
By 26.8g(75mmol) methyltriphenylphosphonium bromide is dissolved in 300mL anhydrous tetrahydro furan, adds 8.4g(75mmol altogether in three batches at 0 DEG C) potassium tert.-butoxide, react 0.5 hour to obtain yellow phosphonium ylide solution.Then be naturally warming up to room temperature, drip containing 6.9g(30mmol) the 50mL tetrahydrofuran solution of o-chlorobenzyl phenyl ketone, be warming up to 30 DEG C of insulation reaction after dropwising again and terminate after 1 hour to react.Filter, steam solvent treatment and obtain 6.1g(26.8mol) 2-phenyl-1-(2-chloro-phenyl-) propylene, yield is 89%.
1H-NMR（300MHz，CDCl 3）：δ（ppm）7.11-7.58（m，9H），6.90（s，1H），2.18（d，3H）
Embodiment 22-(4-chloro-phenyl-)-1-(2-chloro-phenyl-) synthesis of propylene
Step 1: the synthesis of o-chlorobenzene acetyl chloride
In reaction flask, add 5.1g(30mmol) o-chlorobenzene acetic acid, 0.1g DMF, then add 50mL methylene dichloride stirring and dissolving, drip 7.6g(60mmol) oxalyl chloride in above-mentioned solution, within one hour, dropwise, then be warming up to backflow, react after 3 hours and terminate reaction.Steam solvent and excessive sulfur oxychloride obtains o-chlorobenzene acetyl chloride 5.5g(29.4mmol), yield is 98%.
Step 2: the synthesis of rubigan o-chlorobenzyl ketone
By 5.8g(44.1mmol) Aluminum chloride anhydrous to join in o-chlorobenzene acetyl chloride (step (1) prepare acyl chlorides 20mL methylene dichloride dissolve), temperature is down to 0 DEG C, then 19.7g(176.4mmol is dripped) chlorobenzene, dropwised in 1 hour, be then naturally warming up to room temperature reaction 6 hours.Stir in slow for reaction solution impouring frozen water, be then extracted with ethyl acetate separatory, steam solvent treatment and obtain 6.8g(25.8mmol) rubigan o-chlorobenzyl ketone, yield is 88%.
1H-NMR（300MHz，CDCl 3）：δ（ppm）7.97（d，2H，J=8.4Hz），7.50（d，2H，J=8.4Hz），7.42（m，1H），7.24（m，3H），4.40（s，2H）
Step 32-(4-chloro-phenyl-)-1-(2-chloro-phenyl-) synthesis of propylene
By 8.9g(25mmol) methyltriphenylphosphonium bromide is dissolved in 100mL anhydrous tetrahydro furan, adds 2.8g(25mmol altogether in three batches at-5 DEG C) potassium tert.-butoxide, react 1 hour to obtain yellow phosphonium ylide solution.Then be naturally warming up to 20 DEG C, within 1 hour, drip containing 2.6g(10mmol) the 20mL tetrahydrofuran solution of rubigan o-chlorobenzyl ketone, be warming up to 30 DEG C of insulation reaction after dropwising again and terminate after 2 hours to react.Filter, steam solvent treatment and obtain 2.3g(8.8mmol) 2-(4-chloro-phenyl-)-1-(2-chloro-phenyl-) propylene, yield is 88%.
1H-NMR（300MHz，CDCl 3）：δ（ppm）7.21-7.50（m，8H），6.87（s，1H），2.15（s，3H）
Embodiment 32-(4-bromophenyl)-1-(2-chloro-phenyl-) propylene
Step 1: the synthesis of o-chlorobenzene acetyl chloride
In reaction flask, add 5.1g(30mmol) o-chlorobenzene acetic acid, 0.1g DMF, then add 35.4g(300mmol) sulfur oxychloride solution, be then warming up to backflow, react after 3 hours terminate reaction.Steam solvent and excessive sulfur oxychloride obtains o-chlorobenzene acetyl chloride 5.6g(29.7mmol), yield is 99%.
Step 2: to the synthesis of bromophenyl o-chlorobenzyl ketone
By 5.5g(41.5mmol) Aluminum chloride anhydrous joins (the acyl chlorides 5.6g of step 1 in the dichloromethane solution of o-chlorobenzene acetyl chloride, 29.7mmol 100mL methylene dichloride dissolves), temperature is down to 0 DEG C, then 9.3g(59.4mmol is dripped) bromobenzene, dropwised in 1 hour, be then naturally warming up to room temperature reaction 1 hour.Stir in slow for reaction solution impouring frozen water, be then extracted with ethyl acetate separatory, steam solvent treatment and obtain 6.6g(21.4mmol) to bromophenyl o-chlorobenzyl ketone, yield is 72%.
1H-NMR（300MHz，CDCl 3）：δ（ppm）7.90（d，2H，J=9Hz），7.62（d，2H，8.7Hz），7.41（m，1H），7.25（m，3H），4.40（s，2H）
Step 32-(4-bromophenyl)-1-(2-chloro-phenyl-) synthesis of propylene
By 8.9g(25mmol) methyltriphenylphosphonium bromide is dissolved in 100mL anhydrous tetrahydro furan, adds 2.8g(25mmol altogether in three batches at-10 DEG C) potassium tert.-butoxide, react 5 hours to obtain yellow phosphonium ylide solution.Then be warming up to 20 DEG C, dripped containing 3.1g(10mmol in 1 hour) 20mL tetrahydrofuran solution to bromophenyl o-chlorobenzyl ketone, be warming up to 30 DEG C of insulation reaction after dropwising again and after 8 hours, terminate reaction.Filter, steam solvent treatment and obtain 2.4g(7.8mmol) 2-(4-bromophenyl)-1-(2-chloro-phenyl-) propylene, yield is 78%.
1H-NMR（300MHz，CDCl 3）：δ（ppm）7.21-7.51（m，8H），6.87（s，1H），2.14（d，3H）
Embodiment 42-(4-p-methoxy-phenyl)-1-(2-chloro-phenyl-) synthesis of propylene
Step 1: the synthesis of o-chlorobenzene acetyl chloride
In reaction flask, add 5.1g(30mmol) o-chlorobenzene acetic acid, 0.1g DMF, then add 35.4g(300mmol) sulfur oxychloride solution, be then warming up to backflow, react after 3 hours terminate reaction.Steam solvent and excessive sulfur oxychloride obtains o-chlorobenzene acetyl chloride 5.6g(29.7mmol), yield is 99%.Step 2: the synthesis of p-methoxyphenyl o-chlorobenzyl ketone
By 7.8g(59.4mmol) Aluminum chloride anhydrous join in o-chlorobenzene acetyl chloride dichloromethane solution in (the product 5.6g of step 1 is dissolved in 50mL methylene dichloride), temperature is down to-10 DEG C, then 6.4g(59.4mmol is dripped) methyl-phenoxide, dropwised in 1 hour, be then naturally warming up to room temperature reaction 10 hours.Stir in slow for reaction solution impouring frozen water, be then extracted with ethyl acetate separatory, steam solvent treatment and obtain 4.3g(16.6mmol) p-methoxyphenyl o-chlorobenzyl ketone, yield is 56%.
1h-NMR(300MHz, CDCl 3): δ (ppm) 8.03(d, 2H, J=8.4Hz), 7.40(m, 1H) and, 7.23(m, 3H), 6.95(d, 2H, J=8.7Hz) and, 4.40(s, 2H), 3.88(s, 3H) and step 32-(4-p-methoxy-phenyl)-1-(2-chloro-phenyl-) synthesis of propylene
By 4.5g(12.5mmol) methyltriphenylphosphonium bromide is dissolved in 50mL anhydrous tetrahydro furan, adds 1.4g(12.5mmol altogether in three batches at 10 DEG C) potassium tert.-butoxide, react 2 hours to obtain yellow phosphonium ylide solution.Then be warming up to 20 DEG C, dripped containing 1.3g(5mmol in 1 hour) the 10mL tetrahydrofuran solution of p-methoxyphenyl o-chlorobenzyl ketone, be warming up to 50 DEG C of insulation reaction after dropwising again and after 24 hours, terminate reaction.Filter, steam solvent treatment and obtain 1.0g(3.9mmol) 2-(4-p-methoxy-phenyl)-1-(2-chloro-phenyl-) propylene, yield is 77%.
1H-NMR（300MHz，CDCl 3）：δ（ppm）6.82-7.41（m，8H），6.85（s，1H），3.85（s，3H），2.16(s,3H)
The fluorine-based phenyl of embodiment 52-(4-)-1-(3-chloro-phenyl-) synthesis of propylene
The synthesis of step 1 chlorophenylacetyl chloride
In reaction flask, add 5.1g(30mmol) between chlorobenzene acetic acid, 0.1g DMF, then add 35.4g(300mmol) sulfur oxychloride solution, be then warming up to backflow, react after 20 hours terminate reaction.Steam solvent and excessive sulfur oxychloride obtains o-chlorobenzene acetyl chloride 5.6g(29.7mmol), yield is 99%.
The synthesis of chlorobenzyl ketone between step 2 pair fluorophenyl
By 5.9g(44.5mmol) Aluminum chloride anhydrous joins between step 1 in chlorophenylacetyl chloride, then adds 28.8g(300mmol) fluorobenzene stirs, temperature is down to 0 DEG C, react naturally to be warming up to room temperature after 2 hours and to react end in 6 hours again and react.Stir in slow for reaction solution impouring frozen water, be then extracted with ethyl acetate separatory, steam solvent treatment and obtain 5.5g(22.0mmol) to chlorobenzyl ketone between fluorophenyl, yield is 74%.
1H-NMR（300MHz，CDCl 3）：δ（ppm）8.02（m，2H），7.26（m，4H），7.13（m，2H），4.24（s，2H）
The fluorine-based phenyl of step 32-(4-)-1-(3-chloro-phenyl-) synthesis of propylene
By 17.8g(50mmol) methyltriphenylphosphonium bromide is dissolved in 100mL anhydrous tetrahydro furan, adds 5.6g(50mmol altogether in three batches at 0 DEG C) potassium tert.-butoxide, react 2 hours to obtain yellow phosphonium ylide solution.Then be warming up to 20 DEG C, within 1 hour, drip containing 5.0g(20mmol) 50mL tetrahydrofuran solution to chlorobenzyl ketone between fluorophenyl, be warming up to 60 DEG C of insulation reaction after dropwising again and terminate after 8 hours to react.Filter, steam solvent treatment and obtain 4.2g(17mmol) the fluorine-based phenyl of 2-(4-)-1-(3-chloro-phenyl-) propylene, yield is 85%.
1H-NMR（300MHz，CDCl 3）：δ（ppm）7.48（m，2H），7.10-7.33（m，4H），7.06（m，2H），6.70（s，1H），2.24（s，3H）
Embodiment 62-(4-fluorophenyl)-1-(2-nitrophenyl) propylene
The synthesis of step 1 ortho-nitrophenyl Acetyl Chloride 98Min.
In reaction flask, add 5.4g(30mmol) o-Nitrophenylacetic acid, add 50mL methylene dichloride stirring and dissolving, then add 0.1g DMF as catalyzer, drip 7.6g(60mmol) oxalyl chloride in above-mentioned solution, within one hour, dropwise, room temperature reaction terminates reaction after 24 hours.Steam solvent and excessive oxalyl chloride obtains ortho-nitrophenyl Acetyl Chloride 98Min. 5.8g(29.4mmol), yield is 98%.
The synthesis of the adjacent nitrobenzyl ketone of step 2 pair fluorophenyl
By 5.0g(37.8mmol) Aluminum chloride anhydrous joins in the ortho-nitrophenyl Acetyl Chloride 98Min. of step 1, add 50mL methylene dichloride stirring and dissolving, temperature is down to 0 DEG C, then drips 9.6g(100mmol) fluorobenzene, dropwised in 1 hour, be then naturally warming up to incubation at room temperature and react 10 hours.Stir in slow for reaction solution impouring frozen water, be then extracted with ethyl acetate separatory, steam solvent treatment and obtain 4.7g(18.2mmol) to the adjacent nitrobenzyl ketone of fluorophenyl, yield is 62%.
1H-NMR（300MHz，CDCl 3）：δ（ppm）8.17（d，1H），8.07（m，2H），7.62（t，1H），7.52（t，1H）,7.35（d，1H），7.17（m，2H），4.71（s，2H）
Step 32-(4-fluorophenyl)-1-(2-nitrophenyl) synthesis of propylene
By 8.9g(25mmol) methyltriphenylphosphonium bromide is dissolved in 50mL anhydrous tetrahydro furan, adds 2.8g(25mmol altogether in three batches at 0 DEG C) potassium tert.-butoxide, react 2 hours to obtain yellow phosphonium ylide solution.Then be warming up to 20 DEG C, within 1 hour, drip containing 2.6g(10mmol) 10mL tetrahydrofuran solution to the adjacent nitrobenzyl ketone of fluorophenyl, be warming up to back flow reaction after dropwising again and terminate after 8 hours to react.Filter, steam solvent treatment and obtain 0.87g(3.4mmol) 2-(4-fluorophenyl)-1-(2-nitrophenyl) propylene, yield is 34%.
1H-NMR（300MHz，CDCl 3）：δ（ppm）8.07（d，1H），7.07-7.63（m，8H），2.08（s，3H）。

Claims (6)

1. a preparation method for 2-phenyl-1-(2-chloro-phenyl-) propylene, is characterized in that:
Step 1: the synthesis of o-chlorobenzene acetyl chloride:
5.1g o-chlorobenzene acetic acid, 0.1g DMF is added in reaction flask, then 50mL methylene dichloride stirring and dissolving is added, drip the sulfur oxychloride of 5.3g in above-mentioned solution, 1h dropwises, then backflow is warming up to, end reaction after reaction 3h, steams solvent and excessive sulfur oxychloride obtains o-chlorobenzene acetyl chloride 5.4g;
Step 2: the synthesis of o-chlorobenzyl phenyl ketone
4.6g Aluminum chloride anhydrous is joined in 13.5g benzene, temperature is down to 0 DEG C, then o-chlorobenzene acetyl chloride 5.4g is added, naturally reaction is terminated after being warming up to room temperature reaction 6h, stir in slow for reaction solution impouring frozen water, then be extracted with ethyl acetate separatory, steam solvent treatment and obtain 5.7g o-chlorobenzyl phenyl ketone;
The synthesis of step 3:2-phenyl-1-(2-chloro-phenyl-) propylene
26.8g methyltriphenylphosphonium bromide is dissolved in 300mL anhydrous tetrahydro furan, the potassium tert.-butoxide of 8.4g is added in three batches altogether at 0 DEG C, react 0.5 hour to obtain yellow phosphonium ylide solution, then naturally room temperature is warming up to, drip the 50mL tetrahydrofuran solution containing 6.9g o-chlorobenzyl phenyl ketone, be warming up to 30 DEG C of insulation reaction after dropwising again and after 1 hour, terminate reaction; Filter, steam solvent treatment and obtain 6.1g 2-phenyl-1-(2-chloro-phenyl-) propylene.
2. a preparation method for 2-(4-chloro-phenyl-)-1-(2-chloro-phenyl-) propylene, is characterized in that:
Step 1: the synthesis of o-chlorobenzene acetyl chloride
5.1g is added: o-chlorobenzene acetic acid, 0.1g DMF in reaction flask, then 50mL methylene dichloride stirring and dissolving is added, drip the oxalyl chloride of 7.6g in above-mentioned solution, within one hour, dropwise, then backflow is warming up to, react after 3 hours and terminate reaction, steam solvent and excessive sulfur oxychloride obtains o-chlorobenzene acetyl chloride 5.5g;
Step 2: the synthesis of rubigan o-chlorobenzyl ketone
Join in o-chlorobenzene acetyl chloride by 5.8g Aluminum chloride anhydrous, temperature is down to 0 DEG C, then drips 19.7g chlorobenzene, dropwises, be then naturally warming up to room temperature reaction 6 hours in 1 hour; Stir in slow for reaction solution impouring frozen water, be then extracted with ethyl acetate separatory, steam solvent treatment and obtain 6.8g rubigan o-chlorobenzyl ketone;
The synthesis of step 3 2-(4-chloro-phenyl-)-1-(2-chloro-phenyl-) propylene
8.9g methyltriphenylphosphonium bromide is dissolved in 100mL anhydrous tetrahydro furan, the potassium tert.-butoxide of 2.8g is added in three batches altogether at-5 DEG C, react 1 hour to obtain yellow phosphonium ylide solution, then 20 DEG C are naturally warming up to, within 1 hour, drip the 20mL tetrahydrofuran solution containing 2.6g rubigan o-chlorobenzyl ketone, be warming up to 30 DEG C of insulation reaction after dropwising again and after 2 hours, terminate reaction, filter, steam solvent treatment and obtain 2.3g 2-(4-chloro-phenyl-)-1-(2-chloro-phenyl-) propylene.
3. a preparation method for 2-(4-bromophenyl)-1-(2-chloro-phenyl-) propylene, is characterized in that:
Step 1: the synthesis of o-chlorobenzene acetyl chloride
In reaction flask, add 5.1g o-chlorobenzene acetic acid, 0.1g DMF, then add the sulfur oxychloride solution of 35.4g, be then warming up to backflow, react after 3 hours and terminate reaction; Steam solvent and excessive sulfur oxychloride obtains o-chlorobenzene acetyl chloride 5.6g; ,
Step 2: to the synthesis of bromophenyl o-chlorobenzyl ketone
5.5g Aluminum chloride anhydrous is joined in the dichloromethane solution of o-chlorobenzene acetyl chloride, temperature is down to 0 DEG C, then 9.3g bromobenzene is dripped, dropwised in 1 hour, then room temperature reaction 1 hour is naturally warming up to, stir in slow for reaction solution impouring frozen water, be then extracted with ethyl acetate separatory, steam solvent treatment and obtain 6.6g to bromophenyl o-chlorobenzyl ketone;
The synthesis of step 3 2-(4-bromophenyl)-1-(2-chloro-phenyl-) propylene
8.9g methyltriphenylphosphonium bromide is dissolved in 100mL anhydrous tetrahydro furan, the potassium tert.-butoxide of 2.8g is added in three batches altogether at-10 DEG C, react 5 hours to obtain yellow phosphonium ylide solution, then 20 DEG C are warming up to, dripped containing the 20mL tetrahydrofuran solution of 3.1g to bromophenyl o-chlorobenzyl ketone in 1 hour, be warming up to 30 DEG C of insulation reaction after dropwising again and after 8 hours, terminate reaction, filter, steam solvent treatment and obtain 2.4g2-(4-bromophenyl)-1-(2-chloro-phenyl-) propylene.
4. a preparation method for 2-(4-p-methoxy-phenyl)-1-(2-chloro-phenyl-) propylene, is characterized in that:
Step 1: the synthesis of o-chlorobenzene acetyl chloride
In reaction flask, add 5.1g o-chlorobenzene acetic acid, 0.1g DMF, then add the sulfur oxychloride solution of 35.4g, be then warming up to backflow, react after 3 hours and terminate reaction, steam solvent and excessive sulfur oxychloride obtains o-chlorobenzene acetyl chloride 5.6g;
Step 2: the synthesis of p-methoxyphenyl o-chlorobenzyl ketone
7.8g Aluminum chloride anhydrous is joined in the dichloromethane solution in o-chlorobenzene acetyl chloride, temperature is down to-10 DEG C, then 6.4g methyl-phenoxide is dripped, dropwised in 1 hour, then room temperature reaction 10 hours are naturally warming up to, stir in slow for reaction solution impouring frozen water, be then extracted with ethyl acetate separatory, steam solvent treatment and obtain 4.3g p-methoxyphenyl o-chlorobenzyl ketone;
The synthesis of step 3 2-(4-p-methoxy-phenyl)-1-(2-chloro-phenyl-) propylene
4.5g methyltriphenylphosphonium bromide is dissolved in 50mL anhydrous tetrahydro furan, the potassium tert.-butoxide of 1.4g is added in three batches altogether at 10 DEG C, react 2 hours to obtain yellow phosphonium ylide solution, then 20 DEG C are warming up to, the 10mL tetrahydrofuran solution containing 1.3g p-methoxyphenyl o-chlorobenzyl ketone is dripped in 1 hour, be warming up to 50 DEG C of insulation reaction after dropwising again and after 24 hours, terminate reaction, filter, steam solvent treatment and obtain 1.0g 2-(4-p-methoxy-phenyl)-1-(2-chloro-phenyl-) propylene.
5. a preparation method for 2-(the fluorine-based phenyl of 4-)-1-(3-chloro-phenyl-) propylene, is characterized in that:
Step 1: the synthesis of a chlorophenylacetyl chloride
In reaction flask, add chlorobenzene acetic acid between 5.1g, 0.1g DMF, then add the sulfur oxychloride solution of 35.4g, be then warming up to backflow, react after 20 hours and terminate reaction, steam solvent and excessive sulfur oxychloride obtains o-chlorobenzene acetyl chloride 5.6g;
The synthesis of chlorobenzyl ketone between step 2 pair fluorophenyl
5.9g Aluminum chloride anhydrous to be joined between step 1 in chlorophenylacetyl chloride, then add 28.8g fluorobenzene to stir, temperature is down to 0 DEG C, react and to be naturally warming up to room temperature after 2 hours and to react again and terminate reaction in 6 hours, stir in slow for reaction solution impouring frozen water, then be extracted with ethyl acetate separatory, steam solvent treatment and obtain 5.5g to chlorobenzyl ketone between fluorophenyl;
The synthesis of step 3 2-(the fluorine-based phenyl of 4-)-1-(3-chloro-phenyl-) propylene
17.8g methyltriphenylphosphonium bromide is dissolved in 100mL anhydrous tetrahydro furan, the potassium tert.-butoxide of 5.6g is added in three batches altogether at 0 DEG C, react 2 hours to obtain yellow phosphonium ylide solution, then 20 DEG C are warming up to, within 1 hour, drip containing 5.0g the 50mL tetrahydrofuran solution of chlorobenzyl ketone between fluorophenyl, be warming up to 60 DEG C of insulation reaction after dropwising again and after 8 hours, terminate reaction, filter, steam solvent treatment and obtain 4.2g2-(the fluorine-based phenyl of 4-)-1-(3-chloro-phenyl-) propylene.
6. a preparation method for 2-(4-fluorophenyl)-1-(2-nitrophenyl) propylene, is characterized in that:
Step 1: the synthesis of ortho-nitrophenyl Acetyl Chloride 98Min.
The o-Nitrophenylacetic acid of 5.4g is added in reaction flask, add 50mL methylene dichloride stirring and dissolving, then 0.1g DMF is added as catalyzer, drip the oxalyl chloride of 7.6g in above-mentioned solution, within one hour, dropwise, room temperature reaction terminates reaction after 24 hours, steam solvent and excessive oxalyl chloride obtains ortho-nitrophenyl Acetyl Chloride 98Min. 5.8g;
The synthesis of the adjacent nitrobenzyl ketone of step 2 pair fluorophenyl
5.0g Aluminum chloride anhydrous is joined in the ortho-nitrophenyl Acetyl Chloride 98Min. of step 1, add 50mL methylene dichloride stirring and dissolving, temperature is down to 0 DEG C, then 9.6g fluorobenzene is dripped, dropwised in 1 hour, be then naturally warming up to incubation at room temperature and react 10 hours, stir in slow for reaction solution impouring frozen water, then be extracted with ethyl acetate separatory, steam solvent treatment and obtain 4.7g to the adjacent nitrobenzyl ketone of fluorophenyl;
The synthesis of step 3 2-(4-fluorophenyl)-1-(2-nitrophenyl) propylene
8.9g methyltriphenylphosphonium bromide is dissolved in 50mL anhydrous tetrahydro furan, the potassium tert.-butoxide of 2.8g is added in three batches altogether at 0 DEG C, react 2 hours to obtain yellow phosphonium ylide solution, then 20 DEG C are warming up to, within 1 hour, drip containing the 10mL tetrahydrofuran solution of 2.6g to the adjacent nitrobenzyl ketone of fluorophenyl, be warming up to back flow reaction after dropwising again and after 8 hours, terminate reaction, filter, steam solvent treatment and obtain 0.87g 2-(4-fluorophenyl)-1-(2-nitrophenyl) propylene.
CN201310170872.8A 2013-05-10 2013-05-10 One prepares the method for 1,2-diphenyl propylene compound Active CN103254027B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310170872.8A CN103254027B (en) 2013-05-10 2013-05-10 One prepares the method for 1,2-diphenyl propylene compound

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310170872.8A CN103254027B (en) 2013-05-10 2013-05-10 One prepares the method for 1,2-diphenyl propylene compound

Publications (2)

Publication Number Publication Date
CN103254027A CN103254027A (en) 2013-08-21
CN103254027B true CN103254027B (en) 2015-09-23

Family

ID=48958305

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310170872.8A Active CN103254027B (en) 2013-05-10 2013-05-10 One prepares the method for 1,2-diphenyl propylene compound

Country Status (1)

Country Link
CN (1) CN103254027B (en)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102304014A (en) * 2011-07-07 2012-01-04 江苏七洲绿色化工股份有限公司 Method for preparing epoxiconazole intermediate

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009173817A (en) * 2008-01-28 2009-08-06 Seiko Epson Corp Nematic liquid crystal mixture and liquid crystal panel

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102304014A (en) * 2011-07-07 2012-01-04 江苏七洲绿色化工股份有限公司 Method for preparing epoxiconazole intermediate

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
(Z)-2-(4-氟苯基)-1-(2-氯苯基)-3-溴丙烯合成新工艺;孟志等;《农药》;20140430;第52卷(第4期);摘要，图1-2，第245-246页第1.2节合成方法 *
ELIMINATION REACTIONS IN THE l,2-DIPHENYL-2-PROPYL SYSTEM;I. Ho and J. G. SMWH;《Tetrahedron》;19700507;第26卷;4277-4286 *

Also Published As

Publication number Publication date
CN103254027A (en) 2013-08-21

Similar Documents

Publication Publication Date Title
EP2556077A1 (en) Monophosphorus ligands and their use in cross-coupling reactions
CN103254027B (en) One prepares the method for 1,2-diphenyl propylene compound
CN109879731B (en) Diaryl methane halogenated olefin derivative and preparation method thereof
CN103030660A (en) Technological method for synthesizing methylboronic acid
CN103787855B (en) The novel method of asymmetry catalysis synthesis (S)-aryl turmerone
CN102675366B (en) 2-alkoxyl group-6-aminophenyl dialkyl phosphine and synthesis thereof and application
KR100411411B1 (en) Preparation of 2- (substituted benzoyl) 1,3 cyclohexanedione
CN102936204A (en) Chiral compound
CN104447604A (en) Synthetic method for chiral quaternary carbon oxazolidinone compound
Zhu et al. Practical and highly stereoselective method for the preparation of several chiral arylsulfinamides and arylsulfinates based on the spontaneous crystallization of diastereomerically pure N-benzyl-N-(1-phenylethyl)-arylsulfinamides
CN102408385A (en) Preparation method of 2-substituent-2H-1,2,3-triazole derivative
CN103936552A (en) Preparation method of epoxiconazole intermediate (Z)-2-(4-fluorophenyl)-1-(2-chlorphenyl)-3-halogen propylene
CN102675125B (en) Simple, convenient and high-efficiency synthesis method of 4-chloro-2-trifluoroacetylaniline and analogs thereof
CN110372544B (en) Iron-catalyzed synthesis method of biaryl and derivatives thereof
JP4464516B2 (en) Method for producing phosphine-borane derivative
JP2019503377A (en) Method for producing substituted 2-aryl-ethanols
JP2019524783A (en) Method for producing difluoroallylborate ester and use thereof
CN105037408A (en) Method for preparing formyl phenylboronic acid
Biswas et al. Expedient synthesis of β, β-disubstituted α-methylenepropionates
JP2004238362A (en) OPTICALLY ACTIVE QUATERNARY AMMONIUM SALT, ITS PRODUCTION METHOD AND METHOD FOR PRODUCING OPTICALLY ACTIVE alpha-AMINO ACID DERIVATIVE USING THE SALT AS PHASE-TRANSFER CATALYST
CN102659706B (en) Preparation and synthetic methodof chiral oxazoline
CN105503551A (en) Method for preparing 2,3-dimethyl benzaldehyde
CN105111229A (en) Synthetic method for silthiopham
CN101883757B (en) Method for producing 6-halogeno-3-arylpyridine derivative
Katritzky et al. Preparation of 2-alkoxy-5-methoxybenzaldehydes and 2-ethoxy-5-alkoxybenzaldehydes

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C41 Transfer of patent application or patent right or utility model
TR01 Transfer of patent right

Effective date of registration: 20160118

Address after: 110021 Liaodong Road, Tiexi District, Liaoning, No. 8-1, No.

Patentee after: SHENYANG SINOCHEM PESTICIDE CHEMICAL RESEARCH AND DEVELOPMENT CO., LTD.

Address before: 100031 Beijing, Xicheng District, the door of the revitalization of the main street, No. 28

Patentee before: Sinochem Corporation

Patentee before: Shenyang Research Institute of Chemical Industry