CN101445447A - Synthesis method for 4-chlorobutyryl chloride - Google Patents
Synthesis method for 4-chlorobutyryl chloride Download PDFInfo
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- CN101445447A CN101445447A CNA2008101636926A CN200810163692A CN101445447A CN 101445447 A CN101445447 A CN 101445447A CN A2008101636926 A CNA2008101636926 A CN A2008101636926A CN 200810163692 A CN200810163692 A CN 200810163692A CN 101445447 A CN101445447 A CN 101445447A
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- Prior art keywords
- butyrolactone
- gamma
- reaction
- chlorobutanoylchloride
- trichloromethyl
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- CDIIZULDSLKBKV-UHFFFAOYSA-N 4-chlorobutanoyl chloride Chemical compound ClCCCC(Cl)=O CDIIZULDSLKBKV-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000001308 synthesis method Methods 0.000 title abstract 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims abstract description 72
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 19
- 239000003960 organic solvent Substances 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 150000001412 amines Chemical class 0.000 claims abstract description 8
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 20
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 claims description 20
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 238000010189 synthetic method Methods 0.000 claims description 15
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 14
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 238000004821 distillation Methods 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- -1 zellon Chemical compound 0.000 claims description 11
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 10
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 150000002170 ethers Chemical class 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- ZZUYIRISBMWFMV-UHFFFAOYSA-N methyl 4-chlorobutanoate Chemical class COC(=O)CCCCl ZZUYIRISBMWFMV-UHFFFAOYSA-N 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- OKDGRDCXVWSXDC-UHFFFAOYSA-N 2-chloropyridine Chemical compound ClC1=CC=CC=N1 OKDGRDCXVWSXDC-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000003049 inorganic solvent Substances 0.000 abstract 1
- 229910001867 inorganic solvent Inorganic materials 0.000 abstract 1
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 10
- 238000009835 boiling Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- LISFMEBWQUVKPJ-UHFFFAOYSA-N quinolin-2-ol Chemical compound C1=CC=C2NC(=O)C=CC2=C1 LISFMEBWQUVKPJ-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- RGZYGIJEMXUPRT-UHFFFAOYSA-N C1CC1.[Br] Chemical compound C1CC1.[Br] RGZYGIJEMXUPRT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000005571 Isoxaflutole Substances 0.000 description 1
- 229940124350 antibacterial drug Drugs 0.000 description 1
- 239000000164 antipsychotic agent Substances 0.000 description 1
- 229940005529 antipsychotics Drugs 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229960003405 ciprofloxacin Drugs 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- OYIKARCXOQLFHF-UHFFFAOYSA-N isoxaflutole Chemical compound CS(=O)(=O)C1=CC(C(F)(F)F)=CC=C1C(=O)C1=C(C2CC2)ON=C1 OYIKARCXOQLFHF-UHFFFAOYSA-N 0.000 description 1
- 229940088649 isoxaflutole Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- DZZWHBIBMUVIIW-DTORHVGOSA-N sparfloxacin Chemical compound C1[C@@H](C)N[C@@H](C)CN1C1=C(F)C(N)=C2C(=O)C(C(O)=O)=CN(C3CC3)C2=C1F DZZWHBIBMUVIIW-DTORHVGOSA-N 0.000 description 1
- 229960004954 sparfloxacin Drugs 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- GPMXUUPHFNMNDH-UHFFFAOYSA-N trifluperidol Chemical compound C1CC(O)(C=2C=C(C=CC=2)C(F)(F)F)CCN1CCCC(=O)C1=CC=C(F)C=C1 GPMXUUPHFNMNDH-UHFFFAOYSA-N 0.000 description 1
- 229960002341 trifluperidol Drugs 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a chemical synthesis method for 4-chlorobutyryl chloride as is shown in formula (I). The method is characterized in that in the presence of inorganic solvent or organic solvent, chlorination happens between gamma-butyrolactone and bis(trichloromethyl) carbonate as are shown in forma (II) under the function of an organic amine catalyst and at the temperature of 50-180 DEG C. After the reaction, reaction liquid is treated to obtain the 4-chlorobutyryl chloride as is shown in the formula (I). Adding amount of the catalyst is 0.1-10mol percent of gamma-butyrolactone. The synthesis method for the 4-chlorobutyryl chloride provided by the invention has the advantages of easy obtained raw materials and simple and safe operation and can be applied to industrialized production.
Description
(1) technical field:
The present invention relates to a kind of synthetic method of 4-chlorobutanoylchloride.
(2) background technology:
The 4-chlorobutanoylchloride is a kind of important organic synthesis intermediate.At medicine industry, the 4-chlorobutanoylchloride is used to produce antipsychotics Triperidol, trichlorine Serenase, carbostyril family antibacterial drugs Ciprofloxacin, Profloxacin, sparfloxacin etc.Can be used for preparing isoxachlorotole, isoxaflutole etc. at pesticide industry.
At present, existing 4-chlorobutanoylchloride industrialized preparing process mainly is under zinc chloride catalysis, is got through the sulfur oxychloride chlorination by gamma-butyrolactone, about yield 87%, as Chen Ziming etc. bromine cyclopropane synthetic. Chinese Journal of Pharmaceuticals, 1993,24 (1): 21～22; WO2005040109; Russianjournal of Bioorganic Chemistry, 2005,31 (6), 549-555; CN1654461, though this technology is simple to operate, raw material is easy to get, and material cost is higher, and the three wastes are more.
Also have in addition with the phosgene for the raw material substitution sulfur oxychloride is a chlorination reagent, by the synthetic 4-chlorobutanoylchloride of gamma-butyrolactone, yield reaches 95%.As patent US2778852, GB743557, EP0413264 etc.This method yield height, the raw material phosgene is cheap than sulfur oxychloride, and technology is simple, no SO
2Waste gas, the three wastes are less, but the chlorination reagent phosgene itself is exactly hypertoxic chemical, and transport, store inconvenience, operational requirement height.
(3) summary of the invention:
The objective of the invention is to overcome the shortcoming of existing synthetic method, a kind of synthetic method of 4-chlorobutanoylchloride is provided.
The technical solution used in the present invention is as follows:
In the presence of solvent-free or organic solvent, suc as formula gamma-butyrolactone and two (trichloromethyl) carbonic ether shown in (II) under the organic amine catalyst action, 50～180 ℃ of temperature condition carry out chlorination reaction, and reaction finishes, and the reaction solution aftertreatment obtains the 4-chlorobutanoylchloride shown in the formula (I); The add-on of described catalyzer is 0.1～10mol% of gamma-butyrolactone;
The reaction equation of synthetic method of the present invention is as follows:
The amount of substance of two (trichloromethyl) carbonic ethers of the present invention and gamma-butyrolactone is preferably 1:1～5 than for 1:0.5～10.
Catalyzer of the present invention is an organic amine, and as pyridine, 2-chloropyridine, DMF, N, accelerine, triethylamine or Tri-n-Propylamine are preferably pyridine, DMF or N, accelerine.Described catalyzer add-on is the 0.1-10mol% of gamma-butyrolactone.
Chlorination reaction of the present invention is carried out under 50-180 ℃ of temperature condition, is preferably 120-140 ℃.The described chlorination reaction time is 0.5～8h.
Chlorination reaction of the present invention can in the presence of solvent-free or be carried out in the presence of the organic solvent
When described chlorination reaction is carried out in the presence of organic solvent, described organic solvent is following one or more arbitrary proportion mixture: zellon, orthodichlorobenzene, chlorine benzene,toluene,xylene, 1,2-ethylene dichloride, ortho-chlorotolu'ene, Meta Dichlorobenzene, 4-chloro-butyric acid methyl esters are preferably ortho-chlorotolu'ene, Meta Dichlorobenzene or orthodichlorobenzene.The consumption of described organic solvent is for to count 2～10ml/g with the gamma-butyrolactone quality.Carry out when being reflected under the organic solvent, described aftertreatment is: reaction solution is through the distillation desolventizing, and drying gets the 4-chlorobutanoylchloride.More preferably, reaction solution is behind the distillation desolventizing, and 105 ℃ of-112 ℃ of fractions are got in rectifying, and drying gets the 4-chlorobutanoylchloride.
Comparatively concrete, when chlorination reaction of the present invention is carried out in the presence of organic solvent, recommendation is carried out according to following steps: the gamma-butyrolactone shown in the adding formula (II), organic amine catalyzer in reaction vessel, be dissolved with the organic solvent of two (trichloromethyl) carbonic ether, 120～140 ℃ of temperature condition carry out chlorination reaction 0.5～8h, and reaction finishes, reaction solution is through the distillation desolventizing, 105 ℃ of-112 ℃ of fractions are got in rectifying then, and drying obtains the 4-chlorobutanoylchloride shown in the formula (I); Described catalyzer is: pyridine, DMF or N, and accelerine, the add-on of catalyzer is 0.1～10mol% of gamma-butyrolactone; The amount of substance of described two (trichloromethyl) carbonic ethers and gamma-butyrolactone is than being 1:0.5～10, and described organic solvent is ortho-chlorotolu'ene, Meta Dichlorobenzene or orthodichlorobenzene, and the consumption of organic solvent is for to count 2～10ml/g with the gamma-butyrolactone quality.
When chlorination reaction of the present invention was carried out in the presence of solvent-free, described aftertreatment was: the reaction solution distillation, drying gets the 4-chlorobutanoylchloride.More preferably, after the reaction solution distillation, 105 ℃ of-112 ℃ of fractions are got in rectifying, and drying gets the 4-chlorobutanoylchloride.
Comparatively concrete, when chlorination reaction of the present invention is carried out in the presence of solvent-free, recommendation is carried out according to following steps: in the presence of solvent-free, under the organic amine catalyst action, carry out chlorination reaction 0.5～8h under 120～140 ℃ of temperature condition suc as formula gamma-butyrolactone and two (trichloromethyl) carbonic ether shown in (II), reaction finishes, the reaction solution distillation, 105 ℃ of-112 ℃ of fractions of rectifying, drying obtains the 4-chlorobutanoylchloride shown in the formula (I); Described catalyzer is: pyridine, DMF or N, and accelerine, the add-on of catalyzer is 0.1～10mol% of gamma-butyrolactone; The amount of substance of described two (trichloromethyl) carbonic ethers and gamma-butyrolactone is than being 1:0.5～10.
4-chlorobutanoylchloride synthetic method provided by the invention, raw material is easy to get, operational safety, suitability for industrialized production.
(4) embodiment:
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:
Implement 1
The preparation of 4-chlorobutanoylchloride: in four-hole boiling flask, add 8.60g (0.10mol) gamma-butyrolactone, 0.22g (0.003mol) DMF, stir, oil bath is warming up to 140 ℃, drips the 50ml xylene solution of 29.6g (0.10mol) two (trichloromethyl) carbonic ether, drip and finish, reaction 4h is after reaction finishes, feed nitrogen, the remaining phosgene of extracting gets crude reaction liquid, GC analyzes, and 4-chlorobutanoylchloride content is 80.4%.Reaction solution is through the Rotary Evaporators precipitation, and underpressure distillation is collected 105 ℃ of-112 ℃ of fractions (50mmHg), anhydrous MgSO
4Drying gets 4-chlorobutanoylchloride 10.3g, yield 73.6%.
Embodiment 2
The preparation of 4-chlorobutanoylchloride: in four-hole boiling flask, add 8.58g (0.10mol) gamma-butyrolactone, 0.08g (0.001mol) pyridine, stir, oil bath is warming up to 120 ℃, drips the 45ml zellon solution of 17.6g (0.06mol) two (trichloromethyl) carbonic ether, drip and finish, reaction 6h after reaction finishes, feeds nitrogen, the remaining phosgene of extracting, get crude reaction liquid, GC analyzes, and 4-chlorobutanoylchloride content is 45.1%.
Embodiment 3
The preparation of 4-chlorobutanoylchloride: in four-hole boiling flask, add 8.58g (0.10mol) gamma-butyrolactone, 0.20g (0.002mol) triethylamine, stir, oil bath is warming up to 130 ℃, the 20ml zellon solution of Dropwise 5 .92g (0.02mol) two (trichloromethyl) carbonic ether, drip and finish, reaction 8h after reaction finishes, feeds nitrogen, the remaining phosgene of extracting, get crude reaction liquid, GC analyzes, and 4-chlorobutanoylchloride content is 31.2%.
Embodiment 4
The preparation of 4-chlorobutanoylchloride: in four-hole boiling flask, add 8.58g (0.1mol) gamma-butyrolactone, 0.61g (0.005mol) N, accelerine stirs, and oil bath is warming up to 120 ℃, drip the 35ml ortho-chlorotolu'ene solution of 11.8g (0.04mol) two (trichloromethyl) carbonic ether, reaction 0.5h after reaction finishes, feeds nitrogen, the remaining phosgene of extracting, get crude reaction liquid, GC analyzes, and 4-chlorobutanoylchloride content is 93.6%.Reaction solution is through the Rotary Evaporators precipitation, and rectification under vacuum is collected 105 ℃ of-112 ℃ of fractions (50mmHg), anhydrous MgSO
4Drying gets 4-chlorobutanoylchloride 12.8g, yield 91.4%.
Embodiment 5-7
The method of reference example 4 changes temperature of reaction, and other reaction conditionss are identical with embodiment 4, obtain the 4-chlorobutanoylchloride, result such as table 1.
Table 1: temperature of reaction is to the influence of reaction
| Embodiment | Temperature of reaction (℃) | 4-chlorobutanoylchloride content (%) |
| 5 | 50 | 5.2 |
| 6 | 130 | 80.7 |
| 7 | 180 | 65.2 |
Embodiment 8-10
The method of reference example 4 changes catalyst type, and other reaction conditionss are identical with embodiment 4, and the add-on of catalyzer is the 5.0mol% of gamma-butyrolactone still, obtains the 4-chlorobutanoylchloride, result such as table 2.
Table 2: different catalysts is to the influence of reaction
| Embodiment | Catalyzer | 4-chlorobutanoylchloride content (%) |
| 8 | Triethylamine | 89.9 |
| 9 | Pyridine | 93.2 |
| 10 | DMF | 95.4 |
Embodiment 11-13
The method of reference example 4 changes the consumption that reacts catalyst system therefor, and other reaction conditionss are identical with embodiment 4, obtain the 4-chlorobutanoylchloride, result such as table 3.
Table 3: catalyst levels is to the influence of reaction
| Embodiment | Catalyst levels (mol%) | 4-chlorobutanoylchloride content % |
| 11 | 0.1 | 78.3 |
| 12 | 3.0 | 91.5 |
| 13 | 10.0 | 85.0 |
Embodiment 14
The preparation of 4-chlorobutanoylchloride: in four-hole boiling flask, add 8.58g (0.1mol) gamma-butyrolactone, 0.20g (0.003mol) triethylamine, stir, oil bath is warming up to 130 ℃, drips the 50ml4-chloro-butyric acid methyl ester solution of 10.0g (0.034mol) two (trichloromethyl) carbonic ether, drip and finish, reaction 4.5h after reaction finishes, feeds nitrogen, the remaining phosgene of extracting, get crude reaction liquid, GC analyzes, and 4-chloro-butyric acid methyl esters content is 95.9% (esterification of 4-chlorobutanoylchloride elder generation is handled).
Embodiment 15
The preparation of 4-chlorobutanoylchloride: in four-hole boiling flask, add 8.58g (0.12mol) gamma-butyrolactone, 0.22g (0.003mol) DMF, stir, oil bath is warming up to 120 ℃, drips the 40ml zellon and the 20ml o-dichlorobenzene solution of 24.5g (0.085mol) two (trichloromethyl) carbonic ether, reaction 1h, after reaction finishes, feed nitrogen, the remaining phosgene of extracting gets crude reaction liquid, GC analyzes, and 4-chlorobutanoylchloride content is 72%.
Embodiment 16
The preparation of 4-chlorobutanoylchloride: except 40ml zellon and 20ml orthodichlorobenzene changed 30ml ortho-chlorotolu'ene and 30ml chlorobenzene into, other operations were all identical with embodiment 15, and GC analyzes, and 4-chlorobutanoylchloride content is 80.4%.
Embodiment 17
In four-hole boiling flask, add 10.0g (0.034mol) two (trichloromethyl) carbonic ether, 8.58g (0.12mol) gamma-butyrolactone, 0.08g (0.001mol) pyridine, oil bath is warming up to 120 ℃, stirring reaction 6h.After reaction finishes, feed nitrogen, the remaining phosgene of extracting gets crude reaction liquid, GC content 25.0%.The reaction solution underpressure distillation is collected 105 ℃ of-112 ℃ of fractions (50mmHg), anhydrous MgSO
4Drying gets 4-chlorobutanoylchloride 2.8g, yield 20.0%
Claims (10)
1. the chemical synthesis process of the 4-chlorobutanoylchloride shown in the formula (I), it is characterized in that described method is: in the presence of solvent-free or organic solvent, suc as formula gamma-butyrolactone and two (trichloromethyl) carbonic ether shown in (II) under the organic amine catalyst action, carry out chlorination reaction under 50～180 ℃ of temperature condition, reaction finishes, and the reaction solution aftertreatment obtains the 4-chlorobutanoylchloride shown in the formula (I); The add-on of described catalyzer is 0.1～10mol% of gamma-butyrolactone;
2. synthetic method as claimed in claim 1, the amount of substance that it is characterized in that described two (trichloromethyl) carbonic ethers and gamma-butyrolactone is than being 1:0.5～10.
3. the synthetic method of stating as claim 2 is characterized in that the amount of substance ratio of described two (trichloromethyl) carbonic ethers and gamma-butyrolactone is 1:1～5.
4. synthetic method as claimed in claim 1 is characterized in that described catalyzer is pyridine, DMF, N, accelerine, 2-chloropyridine, triethylamine or Tri-n-Propylamine.
5. synthetic method as claimed in claim 1 is characterized in that the described chlorination reaction time is 0.5～8h.
6. synthetic method as claimed in claim 1, the consumption that it is characterized in that described organic solvent is for to count 2～10ml/g with the gamma-butyrolactone quality.
7. synthetic method as claimed in claim 6, it is characterized in that described organic solvent is following one or more arbitrary proportion mixture: toluene, zellon, 1,2-ethylene dichloride, 4-chloro-butyric acid methyl esters, dimethylbenzene, chlorobenzene, ortho-chlorotolu'ene, orthodichlorobenzene, Meta Dichlorobenzene; Described aftertreatment is: reaction solution distillation desolventizing, drying gets the 4-chlorobutanoylchloride.
8. synthetic method as claimed in claim 1 is characterized in that described chlorination reaction carries out in the presence of solvent-free, described aftertreatment is: the reaction solution distillation, drying, the 4-chlorobutanoylchloride.
9. synthetic method as claimed in claim 1, it is characterized in that described method is: in the presence of solvent-free, suc as formula gamma-butyrolactone and two (trichloromethyl) carbonic ether shown in (II) under the organic amine catalyst action, carry out chlorination reaction 0.5～8h under 120～140 ℃ of temperature condition, reaction finishes, the reaction solution distillation, 105 ℃ of-112 ℃ of fractions are got in rectifying then, and drying obtains the 4-chlorobutanoylchloride shown in the formula (I); Described catalyzer is: pyridine, DMF or N, and accelerine, the add-on of catalyzer is 0.1～10mol% of gamma-butyrolactone; The amount of substance of described two (trichloromethyl) carbonic ethers and gamma-butyrolactone is than being 1:0.5～10.
10. synthetic method as claimed in claim 1, it is characterized in that described method is: the gamma-butyrolactone shown in the adding formula (II), organic amine catalyzer in reaction vessel, be dissolved with the organic solvent of two (trichloromethyl) carbonic ether, 120～140 ℃ of temperature condition carry out chlorination reaction 0.5～8h, reaction finishes, reaction solution is through the distillation precipitation, and 105 ℃ of-112 ℃ of fractions are got in rectifying then, and drying obtains the 4-chlorobutanoylchloride shown in the formula (I); Described catalyzer is: pyridine, DMF or N, accelerine; The add-on of described catalyzer is 0.1～10mol% of gamma-butyrolactone; The amount of substance of described two (trichloromethyl) carbonic ethers and gamma-butyrolactone is than being 1:0.5～10, and described organic solvent is ortho-chlorotolu'ene, Meta Dichlorobenzene or orthodichlorobenzene, and the consumption of organic solvent is for to count 2～10ml/g with the gamma-butyrolactone quality.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101624340B (en) * | 2009-08-13 | 2011-11-30 | 浙江国邦药业有限公司 | Preparation method of 4-chlorobutyroyl chloride |
| CN102557938A (en) * | 2011-12-23 | 2012-07-11 | 成都玉岭生物科技有限公司 | Production method of methyl 4-chlorobutyrate |
| CN104086402A (en) * | 2014-07-16 | 2014-10-08 | 胡妍 | Method for synthesizing 4-chlorobutyryl chloride |
| CN108722494A (en) * | 2018-08-08 | 2018-11-02 | 杨秀莲 | A kind of purposes of organic amine-intercalated compound |
| CN108863767A (en) * | 2018-08-08 | 2018-11-23 | 杨秀莲 | A kind of synthetic method of 4- chlorobutanoylchloride |
| CN115260026A (en) * | 2022-04-29 | 2022-11-01 | 浙江沙星科技有限公司 | Green synthesis method of 4-chlorobutyryl chloride |
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2008
- 2008-12-24 CN CNA2008101636926A patent/CN101445447A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101624340B (en) * | 2009-08-13 | 2011-11-30 | 浙江国邦药业有限公司 | Preparation method of 4-chlorobutyroyl chloride |
| CN102557938A (en) * | 2011-12-23 | 2012-07-11 | 成都玉岭生物科技有限公司 | Production method of methyl 4-chlorobutyrate |
| CN104086402A (en) * | 2014-07-16 | 2014-10-08 | 胡妍 | Method for synthesizing 4-chlorobutyryl chloride |
| CN108722494A (en) * | 2018-08-08 | 2018-11-02 | 杨秀莲 | A kind of purposes of organic amine-intercalated compound |
| CN108863767A (en) * | 2018-08-08 | 2018-11-23 | 杨秀莲 | A kind of synthetic method of 4- chlorobutanoylchloride |
| CN115260026A (en) * | 2022-04-29 | 2022-11-01 | 浙江沙星科技有限公司 | Green synthesis method of 4-chlorobutyryl chloride |
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