CN1803758A - Method for synthesizing 4-nitrobenzyl chloroformate - Google Patents
Method for synthesizing 4-nitrobenzyl chloroformate Download PDFInfo
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- CN1803758A CN1803758A CN 200610049249 CN200610049249A CN1803758A CN 1803758 A CN1803758 A CN 1803758A CN 200610049249 CN200610049249 CN 200610049249 CN 200610049249 A CN200610049249 A CN 200610049249A CN 1803758 A CN1803758 A CN 1803758A
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- Prior art keywords
- benzyl formate
- nitrophenyl
- chloride benzyl
- ether
- binding agent
- Prior art date
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- MHSGOABISYIYKP-UHFFFAOYSA-N (4-nitrophenyl)methyl carbonochloridate Chemical compound [O-][N+](=O)C1=CC=C(COC(Cl)=O)C=C1 MHSGOABISYIYKP-UHFFFAOYSA-N 0.000 title abstract 2
- 238000000034 method Methods 0.000 title abstract 2
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- 239000002253 acid Substances 0.000 claims abstract description 53
- 239000011230 binding agent Substances 0.000 claims abstract description 53
- JKTYGPATCNUWKN-UHFFFAOYSA-N 4-nitrobenzyl alcohol Chemical compound OCC1=CC=C([N+]([O-])=O)C=C1 JKTYGPATCNUWKN-UHFFFAOYSA-N 0.000 claims abstract description 48
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 90
- LDQZXZSMXKRZOV-UHFFFAOYSA-N N=O.O=COCC1=CC=CC=C1.Cl Chemical compound N=O.O=COCC1=CC=CC=C1.Cl LDQZXZSMXKRZOV-UHFFFAOYSA-N 0.000 claims description 61
- -1 p-nitrophenyl methyl Chemical group 0.000 claims description 57
- 239000003960 organic solvent Substances 0.000 claims description 49
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 48
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 41
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 claims description 36
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 35
- 125000004432 carbon atom Chemical group C* 0.000 claims description 22
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 14
- 238000010189 synthetic method Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 238000001953 recrystallisation Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- PVFOMCVHYWHZJE-UHFFFAOYSA-N trichloroacetyl chloride Chemical compound ClC(=O)C(Cl)(Cl)Cl PVFOMCVHYWHZJE-UHFFFAOYSA-N 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 8
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 claims description 8
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 8
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 claims description 8
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 claims description 8
- 229960001701 chloroform Drugs 0.000 claims description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 5
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 4
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 claims description 4
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims description 4
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 4
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 claims description 4
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 claims description 4
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 claims description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 4
- YEJCDKJIEMIWRQ-UHFFFAOYSA-N Linopirdine Chemical compound O=C1N(C=2C=CC=CC=2)C2=CC=CC=C2C1(CC=1C=CN=CC=1)CC1=CC=NC=C1 YEJCDKJIEMIWRQ-UHFFFAOYSA-N 0.000 claims description 4
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 4
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 4
- 229940043232 butyl acetate Drugs 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 claims description 4
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims description 4
- 229940093499 ethyl acetate Drugs 0.000 claims description 4
- 150000005826 halohydrocarbons Chemical class 0.000 claims description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 claims description 4
- 229940117955 isoamyl acetate Drugs 0.000 claims description 4
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 claims description 4
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 claims description 4
- 229940011051 isopropyl acetate Drugs 0.000 claims description 4
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims description 4
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 claims description 4
- 229940017219 methyl propionate Drugs 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 4
- 239000003921 oil Substances 0.000 claims description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 4
- TWSRVQVEYJNFKQ-UHFFFAOYSA-N pentyl propanoate Chemical compound CCCCCOC(=O)CC TWSRVQVEYJNFKQ-UHFFFAOYSA-N 0.000 claims description 4
- 229940090181 propyl acetate Drugs 0.000 claims description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 4
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000012043 crude product Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- MMFBQHXDINNBMW-UHFFFAOYSA-N n,n-dipropylaniline Chemical compound CCCN(CCC)C1=CC=CC=C1 MMFBQHXDINNBMW-UHFFFAOYSA-N 0.000 claims description 2
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 2
- HCUYBXPSSCRKRF-UHFFFAOYSA-N diphosgene Chemical compound ClC(=O)OC(Cl)(Cl)Cl HCUYBXPSSCRKRF-UHFFFAOYSA-N 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
- 238000004128 high performance liquid chromatography Methods 0.000 description 40
- 239000007787 solid Substances 0.000 description 40
- 238000002360 preparation method Methods 0.000 description 39
- 125000003944 tolyl group Chemical group 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a process for synthesizing 4-Nitrobenzyl chloroformate, which comprises reacting trichloromethyl chloroformate or bis(trichloromethyl)carbonate with p-nitrobenzyl alcohol at -40-20 deg C under the action of acid-binding agent, finally carrying out post-treatment to obtain the outcome yield.
Description
(1) technical field
The present invention relates to a kind of synthetic method to the nitroxyl chloride benzyl formate.
(2) background technology
The nitroxyl chloride benzyl formate mainly as the hydroxyl and the amido protecting agent of ucleosides, is widely used in medicine and synthesizes.
Before the present invention makes, be to be that raw material reaction makes with p-nitrophenyl methyl alcohol and phosgene to the chemical synthesis process of nitroxyl chloride benzyl formate.For example: JP 2004300052 and J.Am.Chem.Soc., 1952,74,3818-3820 etc.Phosgene is a kind of extremely dangerous hypertoxicity gas, is difficult to accurate metering, has potential safety hazard in the suitability for industrialized production.To nitroxyl chloride benzyl formate poor heat stability, very easily decompose, be not easy to store and transportation.
(3) summary of the invention
It is a kind of easy and simple to handle that the object of the invention is to provide, and production safety is reliable, the synthetic method to the nitroxyl chloride benzyl formate that production cost is low.
Synthetic method to the nitroxyl chloride benzyl formate of the present invention, comprise the steps: superpalite or two (trichloromethyl) carbonic ether and p-nitrophenyl methyl alcohol under the acid binding agent effect in organic solvent in-40～20 ℃ of reactions, aftertreatment gets described product; Described acid binding agent is for replacing or unsubstituted C
6H
5NR
1 2Or NR
2 3Or HCONR
3 2Or pyridine or pyridine derivate, wherein said R
1, R
2, R
3Independent separately is the alkyl of carbonatoms 1～3.
Described acid binding agent is preferably one of following formula or more than one arbitrary combination: Trimethylamine 99, triethylamine, tripropyl amine, pyridine, 2-picoline, 3-picoline, 4-picoline, N, dinethylformamide, N, N-diethylformamide, N, accelerine, N, N-Diethyl Aniline, N, N-dipropyl aniline.
Described organic solvent can be one of following formula or more than one arbitrary combination: the 1. hydrocarbon compound of carbonatoms 5～10,2. the halohydrocarbon of carbonatoms 1～8,3. the ester compound of carbonatoms 2～8,4. the ketone compounds of carbonatoms 3～8,5. the ether compound of carbonatoms 4～8, one of row specific as follows or more than one arbitrary combination: Skellysolve A, pentamethylene, normal hexane, hexanaphthene, sherwood oil, benzene, toluene, chlorobenzene, dimethylbenzene, methylene dichloride, trichloromethane, tetracol phenixin, 1, the 1-ethylene dichloride, 1, the 2-ethylene dichloride, 1,1, the 1-trichloroethane, 1,1, the 2-trichloroethane, methyl acetate, ethyl acetate, propyl acetate, butylacetate, isopropyl acetate, isobutyl acetate, pentyl acetate, Isoamyl Acetate FCC, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, amyl propionate, acetone, butanone, cyclopentanone, pimelinketone, ether, propyl ether, isopropyl ether, butyl ether, tetrahydrofuran (THF), 1, the 4-dioxane.Described consumption of organic solvent is generally 2～20 times of p-nitrophenyl methanol quality, is preferably 3～5 times.
Described p-nitrophenyl methyl alcohol: two (trichloromethyl) carbonic ether: the molar ratio of acid binding agent is generally 1: 0.33～1: 0.01～1, be preferably 1: 0.34～0.4: 0.85～and 0.9.
Described p-nitrophenyl methyl alcohol: superpalite: acid binding agent is generally 1: 0.5～1.5: 0.01～1, be preferably 1: 0.55～0.6: 0.85～and 0.9.
Described aftertreatment can be for joining reaction solution in the recrystallisation solvent, and cooling, filtration promptly get the pure product of nitroxyl chloride benzyl formate; Described recrystallisation solvent can be selected from one of following or more than one arbitrary combination: the 1. hydrocarbon compound of carbonatoms 5～10,2. the halohydrocarbon of carbonatoms 1～8,3. the ester compound of carbonatoms 2～8,4. the ketone compounds of carbonatoms 3～8,5. the ether compound of carbonatoms 4～8, recrystallisation solvent is preferably one of following or more than one arbitrary combination: Skellysolve A, pentamethylene, normal hexane, hexanaphthene, sherwood oil, benzene, toluene, chlorobenzene, dimethylbenzene, methylene dichloride, trichloromethane, tetracol phenixin, 1, the 1-ethylene dichloride, 1, the 2-ethylene dichloride, 1,1, the 1-trichloroethane, 1,1, the 2-trichloroethane, methyl acetate, ethyl acetate, propyl acetate, butylacetate, isopropyl acetate, isobutyl acetate, pentyl acetate, Isoamyl Acetate FCC, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, amyl propionate, acetone, butanone, cyclopentanone, pimelinketone, ether, propyl ether, isopropyl ether, butyl ether, tetrahydrofuran (THF), 1, the 4-dioxane; Described recrystallisation solvent consumption is 10～60 times to nitroxyl chloride benzyl formate crude product quality, is preferably 5～20 times.
The present invention has compared with prior art eliminated production safety hidden danger from the technology source, has reduced three wastes generation significantly, and the reaction yield height, quality product is excellent, production cost is low, do not have the three wastes substantially, has tangible implementary value and society, economic benefit.
(4) embodiment
The invention will be further described below in conjunction with embodiment, but protection scope of the present invention is not limited to this.
Embodiment 1
Molar ratio is a p-nitrophenyl methyl alcohol: two (trichloromethyl) carbonic ether: acid binding agent is 1: 0.4: 0.9, and organic solvent is a methylene dichloride, and its consumption is 5 times of p-nitrophenyl methanol quality.
In the four-hole boiling flask that thermometer, reflux condensing tube, constant pressure funnel and churned mechanically 500mL are housed, add two (trichloromethyl) carbonic ethers of 48g, organic solvent and 1g N, dinethylformamide, ice bath to 0 ℃～5 ℃, open and stir, after the dissolving, add 61.2g p-nitrophenyl methyl alcohol, begin to drip 43.5g N then, accelerine stirred 4 hours down at 0 ℃～5 ℃.After reaction finishes reaction solution slowly is added drop-wise in the 1200g sherwood oil, put into refrigerator-freezer 24 hours.Filter, vacuum-drying must be light yellow to nitroxyl chloride benzyl formate solid 82g, yield 95%, and purity is 99.5% (HPLC) after testing, fusing point is 31.0 ℃～32.0 ℃.
Embodiment 2
Molar ratio changes p-nitrophenyl methyl alcohol into: two (trichloromethyl) carbonic ether: acid binding agent is 1: 0.5: 0.9, and organic solvent is a methylene dichloride, and its consumption is 5 times of p-nitrophenyl methanol quality.
Other condition preparation process must be to nitroxyl chloride benzyl formate solid 82.5g, yield 95.7% all with embodiment 1.Purity is 99.5% (HPLC) after testing, and fusing point is 31.0 ℃～32.0 ℃.
Embodiment 3
Molar ratio changes p-nitrophenyl methyl alcohol into: two (trichloromethyl) carbonic ether: acid binding agent is 1: 0.8: 0.9, and organic solvent is a methylene dichloride, and its consumption is 5 times of p-nitrophenyl methanol quality.
Other condition preparation process must be to nitroxyl chloride benzyl formate solid 82.8g, yield 96% all with embodiment 1.Purity is 99.5% (HPLC) after testing, and fusing point is 31.0 ℃～32.0 ℃.
Embodiment 4
Molar ratio changes p-nitrophenyl methyl alcohol into: superpalite: acid binding agent is 1: 0.5: 0.9, and organic solvent is a methylene dichloride, and its consumption is 5 times of p-nitrophenyl methanol quality.
Other condition preparation process must be to nitroxyl chloride benzyl formate solid 81g, yield 94% all with embodiment 1.Purity is 99.0% (HPLC) after testing, and fusing point is 31.0 ℃～32.0 ℃.
Embodiment 5
Molar ratio changes p-nitrophenyl methyl alcohol into: superpalite: acid binding agent is 1: 0.55: 0.9, and organic solvent is a methylene dichloride, and its consumption is 5 times of p-nitrophenyl methanol quality.
Other condition preparation process must be to nitroxyl chloride benzyl formate solid 82.1g, yield 95% all with embodiment 1.Purity is 99.1% (HPLC) after testing, and fusing point is 31.0 ℃～32.0 ℃.
Embodiment 6
Molar ratio changes p-nitrophenyl methyl alcohol into: superpalite: acid binding agent is 1: 0.6: 0.9, and organic solvent is a methylene dichloride, and its consumption is 5 times of p-nitrophenyl methanol quality.
Other condition preparation process must be to nitroxyl chloride benzyl formate solid 82.1g, yield 95% all with embodiment 1.Purity is 99.2% (HPLC) after testing, and fusing point is 31.0 ℃～32.0 ℃.
Embodiment 7
Molar ratio changes p-nitrophenyl methyl alcohol into: superpalite: acid binding agent is 1: 0.8: 0.9, and organic solvent is a methylene dichloride, and its consumption is 5 times of p-nitrophenyl methanol quality.
Other condition preparation process must be to nitroxyl chloride benzyl formate solid 82.5g, yield 94.3% all with embodiment 1.Purity is 99.0% (HPLC) after testing, and fusing point is 31.0 ℃～32.0 ℃.
Embodiment 8
Molar ratio changes p-nitrophenyl methyl alcohol into: superpalite: acid binding agent is 1: 1: 0.9, and organic solvent is a methylene dichloride, and its consumption is 5 times of p-nitrophenyl methanol quality.
Other condition preparation process must be to nitroxyl chloride benzyl formate solid 82.1g, yield 95% all with embodiment 1.Purity is 99.0% (HPLC) after testing, and fusing point is 31.0 ℃～32.0 ℃.
Embodiment 9
Molar ratio changes p-nitrophenyl methyl alcohol into: two (trichloromethyl) carbonic ether: acid binding agent is 1: 0.4: 0.4, and organic solvent is a methylene dichloride, and its consumption is 5 times of p-nitrophenyl methanol quality.
Other condition preparation process must be to nitroxyl chloride benzyl formate solid 82.5g, yield 95.7% all with embodiment 1.Purity is 99.5% (HPLC) after testing, and fusing point is 31.0 ℃～32.0 ℃.
Embodiment 10
Molar ratio changes p-nitrophenyl methyl alcohol into: two (trichloromethyl) carbonic ether: acid binding agent is 1: 0.4: 0.6, and organic solvent is a methylene dichloride, and its consumption is 5 times of p-nitrophenyl methanol quality.
Other condition preparation process must be to nitroxyl chloride benzyl formate solid 82.3g, yield 95.5% all with embodiment 1.Purity is 99.5% (HPLC) after testing, and fusing point is 31.0 ℃～32.0 ℃.
Embodiment 11
Molar ratio changes p-nitrophenyl methyl alcohol into: two (trichloromethyl) carbonic ether: acid binding agent is 1: 0.4: 0.8, and organic solvent is a methylene dichloride, and its consumption is 5 times of p-nitrophenyl methanol quality.
Other condition preparation process must be to nitroxyl chloride benzyl formate solid 82.6g, yield 95.8% all with embodiment 1.Purity is 99.5% (HPLC) after testing, and fusing point is 31.0 ℃～32.0 ℃.
Embodiment 12
Molar ratio changes p-nitrophenyl methyl alcohol into: two (trichloromethyl) carbonic ether: acid binding agent is 1: 0.4: 1, and organic solvent is a methylene dichloride, and its consumption is 5 times of p-nitrophenyl methanol quality.
Other condition preparation process must be to nitroxyl chloride benzyl formate solid 82.3g, yield 95.5% all with embodiment 1.Purity is 99.5% (HPLC) after testing, and fusing point is 31.0 ℃～32.0 ℃.
Embodiment 13
Molar ratio changes p-nitrophenyl methyl alcohol into: two (trichloromethyl) carbonic ether: acid binding agent is 1: 0.4: 0.95, and organic solvent is a methylene dichloride, and its consumption is 5 times of p-nitrophenyl methanol quality.Acid binding agent changes N into, the N-Diethyl Aniline.
Other condition preparation process must be to nitroxyl chloride benzyl formate solid 84g, yield 97.8% all with embodiment 1.Purity is 99.5% (HPLC) after testing, and fusing point is 31.0 ℃～32.0 ℃.
Embodiment 14
Molar ratio changes p-nitrophenyl methyl alcohol into: two (trichloromethyl) carbonic ether: acid binding agent is 1: 0.4: 0.95, and organic solvent is a methylene dichloride, and its consumption is 5 times of p-nitrophenyl methanol quality.Acid binding agent changes N into, dinethylformamide.
Other condition preparation process must be to nitroxyl chloride benzyl formate solid 82.3g, yield 95.5% all with embodiment 1.Purity is 99.5% (HPLC) after testing, and fusing point is 31.0 ℃～32.0 ℃.
Embodiment 15
Molar ratio changes p-nitrophenyl methyl alcohol into: two (trichloromethyl) carbonic ether: acid binding agent is 1: 0.4: 0.95, and organic solvent is a methylene dichloride, and its consumption is 5 times of p-nitrophenyl methanol quality.Acid binding agent changes triethylamine into.
Other condition preparation process must be to nitroxyl chloride benzyl formate solid 81g, yield 93.6% all with embodiment 1.Purity is 99.5% (HPLC) after testing, and fusing point is 31.0 ℃～32.0 ℃.
Embodiment 16
Molar ratio changes p-nitrophenyl methyl alcohol into: two (trichloromethyl) carbonic ether: acid binding agent is 1: 0.4: 0.95, and organic solvent is a methylene dichloride, and its consumption is 5 times of p-nitrophenyl methanol quality.Acid binding agent changes pyridine into.
Other condition preparation process must be to nitroxyl chloride benzyl formate solid 82.3g, yield 95.5% all with embodiment 1.Purity is 99.5% (HPLC) after testing, and fusing point is 31.0 ℃～32.0 ℃.
Embodiment 17
Molar ratio changes p-nitrophenyl methyl alcohol into: two (trichloromethyl) carbonic ether: acid binding agent is 1: 0.4: 0.95, and organic solvent is a methylene dichloride, and its consumption is 5 times of p-nitrophenyl methanol quality.Acid binding agent changes N into, N-Diethyl Aniline and N, the mixture of accelerine (mol ratio is 1: 1).
Other condition preparation process must be to nitroxyl chloride benzyl formate solid 82g, yield 95% all with embodiment 1.Purity is 99.5% (HPLC) after testing, and fusing point is 31.0 ℃～32.0 ℃.
Embodiment 18
Molar ratio changes p-nitrophenyl methyl alcohol into: two (trichloromethyl) carbonic ether: acid binding agent is 1: 0.4: 0.9, and organic solvent is a methylene dichloride, and its consumption is 10 times of p-nitrophenyl methanol quality.
Other condition preparation process must be to nitroxyl chloride benzyl formate solid 82.5g, yield 95.7% all with embodiment 1.Purity is 99.0% (HPLC) after testing, and fusing point is 31.0 ℃～32.0 ℃.
Embodiment 19
Molar ratio changes p-nitrophenyl methyl alcohol into: two (trichloromethyl) carbonic ether: acid binding agent is 1: 0.4: 0.9, and organic solvent is a methylene dichloride, and its consumption is 20 times of p-nitrophenyl methanol quality.
Other condition preparation process must be to nitroxyl chloride benzyl formate solid 83g, yield 96.4% all with embodiment 1.Purity is 99.0% (HPLC) after testing, and fusing point is 31.0 ℃～32.0 ℃.
Embodiment 20
Molar ratio changes p-nitrophenyl methyl alcohol into: two (trichloromethyl) carbonic ether: acid binding agent is 1: 0.4: 0.9, and organic solvent is a methylene dichloride, and its consumption is 40 times of p-nitrophenyl methanol quality.
Other condition preparation process must be to nitroxyl chloride benzyl formate solid 84g, yield 97.8% all with embodiment 1.Purity is 99.0% (HPLC) after testing, and fusing point is 31.0 ℃～32.0 ℃.
Embodiment 21
Molar ratio changes p-nitrophenyl methyl alcohol into: two (trichloromethyl) carbonic ether: acid binding agent is 1: 0.4: 0.9, and organic solvent is a toluene, and its consumption is 5 times of p-nitrophenyl methanol quality.
Other condition preparation process must be to nitroxyl chloride benzyl formate solid 83.5g, yield 95.1% all with embodiment 1.Purity is 99.3% (HPLC) after testing, and fusing point is 31.0 ℃～32.0 ℃.
Embodiment 22
Molar ratio changes p-nitrophenyl methyl alcohol into: two (trichloromethyl) carbonic ether: acid binding agent is 1: 0.4: 0.9, and organic solvent is a toluene, 10 times of its consumption p-nitrophenyl methanol quality.
Other condition preparation process is all with embodiment 1, must be for to nitroxyl chloride benzyl formate solid 82.1g, yield 95%.Purity is 99.0% (HPLC) after testing, and fusing point is 31.0 ℃～32.0 ℃.
Embodiment 23
Molar ratio changes p-nitrophenyl methyl alcohol into: two (trichloromethyl) carbonic ether: acid binding agent is 1: 0.4: 0.9, and organic solvent is a toluene, and its consumption is 25 times of p-nitrophenyl methanol quality.
Other condition preparation process must be to nitroxyl chloride benzyl formate solid 81.5g, yield 94.3% all with embodiment 1.Purity is 99.0% (HPLC) after testing, and fusing point is 31.0 ℃～32.0 ℃.
Embodiment 24
Molar ratio changes p-nitrophenyl methyl alcohol into: two (trichloromethyl) carbonic ether: acid binding agent is 1: 0.4: 0.9, and organic solvent is an ethyl acetate, and its consumption is 5 times of p-nitrophenyl methanol quality.
Other condition preparation process must be to nitroxyl chloride benzyl formate solid 81g, yield 93.6% all with embodiment 1.Purity is 99.0% (HPLC) after testing, and fusing point is 31.0 ℃～32.0 ℃.
Embodiment 25
Molar ratio changes p-nitrophenyl methyl alcohol into: two (trichloromethyl) carbonic ether: acid binding agent is 1: 0.4: 0.9, and organic solvent is an ethyl acetate, and its consumption is 15 times of p-nitrophenyl methanol quality.
Other condition preparation process must be to nitroxyl chloride benzyl formate solid 82.1g, yield 95% all with embodiment 1.Purity is 99.0% (HPLC) after testing, and fusing point is 31.0 ℃～32.0 ℃.
Embodiment 26
Molar ratio changes p-nitrophenyl methyl alcohol into: two (trichloromethyl) carbonic ether: acid binding agent is 1: 0.4: 0.9, and organic solvent is an ethyl acetate, and its consumption is 30 times of p-nitrophenyl methanol quality.
Other condition preparation process must be to nitroxyl chloride benzyl formate solid 82g, yield 95% all with embodiment 1.Purity is 99.0% (HPLC) after testing, and fusing point is 31.0 ℃～32.0 ℃.
Embodiment 27
Molar ratio changes p-nitrophenyl methyl alcohol into: two (trichloromethyl) carbonic ether: acid binding agent is 1: 0.4: 0.9, and organic solvent is a chloroform, and its consumption is 5 times of p-nitrophenyl methanol quality.
Other condition preparation process must be to nitroxyl chloride benzyl formate solid 82.5g, yield 95.7% all with embodiment 1.Purity is 99.0% (HPLC) after testing, and fusing point is 31.0 ℃～32.0 ℃.
Embodiment 28
Molar ratio changes p-nitrophenyl methyl alcohol into: two (trichloromethyl) carbonic ether: acid binding agent is 1: 0.4: 0.9, and organic solvent is a chloroform, and its consumption is 10 times of p-nitrophenyl methanol quality.
Other condition preparation process must be to nitroxyl chloride benzyl formate solid 83g, yield 96.4% all with embodiment 1.Purity is 99.0% (HPLC) after testing, and fusing point is 31.0 ℃～32.0 ℃.
Embodiment 29
Molar ratio changes p-nitrophenyl methyl alcohol into: two (trichloromethyl) carbonic ether: acid binding agent is 1: 0.4: 0.9, and organic solvent is a chloroform, and its consumption is 20 times of p-nitrophenyl methanol quality.
Other condition preparation process must be to nitroxyl chloride benzyl formate solid 84g, yield 97.8% all with embodiment 1.Purity is 99.0% (HPLC) after testing, and fusing point is 31.0 ℃～32.0 ℃.
Embodiment 30
Molar ratio changes p-nitrophenyl methyl alcohol into: two (trichloromethyl) carbonic ether: acid binding agent is 1: 0.4: 0.9, organic solvent is a toluene, its consumption is 5 times of p-nitrophenyl methanol quality, and recrystallization solvent is a sherwood oil, and its consumption is 10 times of p-nitrophenyl methanol quality.
Other condition preparation process must be to nitroxyl chloride benzyl formate solid 78.4g, yield 91% all with embodiment 1.Purity is 99.0% (HPLC) after testing, and fusing point is 31.0 ℃～32.0 ℃.
Embodiment 31
Molar ratio changes p-nitrophenyl methyl alcohol into: two (trichloromethyl) carbonic ether: acid binding agent is 1: 0.4: 0.9, organic solvent is a toluene, its consumption is 5 times of p-nitrophenyl methanol quality, and recrystallization solvent is a sherwood oil, and its consumption is 30 times of p-nitrophenyl methanol quality.
Other condition preparation process must be to nitroxyl chloride benzyl formate solid 83.5g, yield 96.8% all with embodiment 1.Purity is 99.0% (HPLC) after testing, and fusing point is 31.0 ℃～32.0 ℃.
Embodiment 32
Molar ratio changes p-nitrophenyl methyl alcohol into: two (trichloromethyl) carbonic ether: acid binding agent is 1: 0.4: 0.9, organic solvent is a toluene, its consumption is 5 times of p-nitrophenyl methanol quality, and recrystallization solvent is a sherwood oil, and its consumption is 40 times of p-nitrophenyl methanol quality.
Other condition preparation process must be to nitroxyl chloride benzyl formate solid 81.5g, yield 94.3% all with embodiment 1.Purity is 99.0% (HPLC) after testing, and fusing point is 31.0 ℃～32.0 ℃.
Embodiment 33
Molar ratio changes p-nitrophenyl methyl alcohol into: two (trichloromethyl) carbonic ether: acid binding agent is 1: 0.4: 0.9, organic solvent is a toluene, its consumption is 5 times of p-nitrophenyl methanol quality, and recrystallization solvent is a sherwood oil, and its consumption is 60 times of p-nitrophenyl methanol quality.
Other condition preparation process must be to nitroxyl chloride benzyl formate solid 84.4g, yield 97.9% all with embodiment 1.Purity is 99.0% (HPLC) after testing, and fusing point is 31.0 ℃～32.0 ℃.
Embodiment 34
Molar ratio changes p-nitrophenyl methyl alcohol into: two (trichloromethyl) carbonic ether: acid binding agent is 1: 0.5: 0.9, and organic solvent is a tetrahydrofuran (THF), and its consumption is 5 times of p-nitrophenyl methanol quality.
Other condition preparation process must be to nitroxyl chloride benzyl formate solid 81g, yield 93.6% all with embodiment 1.Purity is 99.5% (HPLC) after testing, and fusing point is 31.0 ℃～32.0 ℃.
Embodiment 35
Molar ratio changes p-nitrophenyl methyl alcohol into: two (trichloromethyl) carbonic ether: acid binding agent is 1: 0.5: 0.9, and organic solvent is 1, and 2-ethylene dichloride, its consumption are 5 times of p-nitrophenyl methanol quality.
Other condition preparation process must be to nitroxyl chloride benzyl formate solid 82g, yield 95% all with embodiment 1.Purity is 99.5% (HPLC) after testing, and fusing point is 31.0 ℃～32.0 ℃.
Embodiment 36
Organic solvent changes toluene into, and its consumption is 5 times of p-nitrophenyl methanol quality, and temperature of reaction changes-40 ℃～-30 ℃ into, and the reaction times changes 24 hours into.
Other condition preparation process gets nitroxyl chloride benzyl formate solid 84.4g, yield 97.9% all with embodiment 1.Purity is 99.0% (HPLC) after testing, and fusing point is 31.0 ℃～32.0 ℃.
Embodiment 37
Organic solvent changes toluene into, and its consumption is 5 times of p-nitrophenyl methanol quality, and temperature of reaction changes-30 ℃～-20 ℃ into, and the reaction times changes 20 hours into.
Other condition preparation process must be to nitroxyl chloride benzyl formate solid 84.4g, yield 97.9% all with embodiment 1.Purity is 99.0% (HPLC) after testing, and fusing point is 31.0 ℃～32.0 ℃.
Embodiment 38
Organic solvent changes toluene into, and its consumption is 5 times of p-nitrophenyl methanol quality, and temperature of reaction changes-20 ℃～-10 ℃ into, and the reaction times changes 16 hours into.
Other condition preparation process must be to nitroxyl chloride benzyl formate solid 83g, yield 96.4% all with embodiment 1.Purity is 99.0% (HPLC) after testing, and fusing point is 31.0 ℃～32.0 ℃.
Embodiment 39
Organic solvent changes toluene into, and its consumption is 5 times of p-nitrophenyl methanol quality, and temperature of reaction changes-10 ℃～0 ℃ into, and the reaction times changes 12 hours into.
Other condition preparation process must be to nitroxyl chloride benzyl formate solid 82.5g, yield 95.7% all with embodiment 1.Purity is 99.0% (HPLC) after testing, and fusing point is 31.0 ℃～32.0 ℃.
Embodiment 40
Organic solvent changes toluene into, and its consumption is 5 times of p-nitrophenyl methanol quality, and temperature of reaction changes 5 ℃～10 ℃ into, and the reaction times changes 3 hours into.
Other condition preparation process must be to nitroxyl chloride benzyl formate solid 83.5g, yield 97.1% all with embodiment 1.Purity is 99.0% (HPLC) after testing, and fusing point is 31.0 ℃～32.0 ℃.
Claims (10)
1, a kind of synthetic method to the nitroxyl chloride benzyl formate, comprise the steps: superpalite or two (trichloromethyl) carbonic ether and p-nitrophenyl methyl alcohol under the acid binding agent effect in organic solvent in-40～20 ℃ of reactions, aftertreatment gets described product; Described acid binding agent is for replacing or unsubstituted C
6H
5NR
1 2Or NR
2 3Or HCONR
3 2Or pyridine or pyridine derivate, wherein said R
1, R
2, R
3Independent separately is the alkyl of carbonatoms 1～3.
2, the synthetic method to the nitroxyl chloride benzyl formate as claimed in claim 1, it is characterized in that described acid binding agent is one of following formula or more than one arbitrary combination: Trimethylamine 99, triethylamine, tripropyl amine, pyridine, 2-picoline, 3-picoline, 4-picoline, N, dinethylformamide, N, N-diethylformamide, N, accelerine, N, N-Diethyl Aniline, N, N-dipropyl aniline.
3, the synthetic method to the nitroxyl chloride benzyl formate as claimed in claim 1, it is characterized in that described organic solvent is one of following formula or more than one arbitrary combination: the 1. hydrocarbon compound of carbonatoms 5～10,2. the halohydrocarbon of carbonatoms 1～8,3. the ester compound of carbonatoms 2～8,4. the ketone compounds of carbonatoms 3～8, the 5. ether compound of carbonatoms 4～8.
4, synthetic method to the nitroxyl chloride benzyl formate as claimed in claim 3, it is characterized in that described organic solvent is one of following or more than one arbitrary combination: Skellysolve A, pentamethylene, normal hexane, hexanaphthene, sherwood oil, benzene, toluene, chlorobenzene, dimethylbenzene, methylene dichloride, trichloromethane, tetracol phenixin, 1, the 1-ethylene dichloride, 1, the 2-ethylene dichloride, 1,1, the 1-trichloroethane, 1,1, the 2-trichloroethane, 1,1,2, the 2-tetrachloroethane, methyl acetate, ethyl acetate, propyl acetate, butylacetate, isopropyl acetate, isobutyl acetate, pentyl acetate, Isoamyl Acetate FCC, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, amyl propionate, acetone, butanone, cyclopentanone, pimelinketone, ether, propyl ether, isopropyl ether, butyl ether, tetrahydrofuran (THF), 1, the 4-dioxane.
5, as the described synthetic method of claim 1～4 to the nitroxyl chloride benzyl formate, it is characterized in that described p-nitrophenyl methyl alcohol: two (trichloromethyl) carbonic ether: the molar ratio of acid binding agent is 1: 0.33～1: 0.01～1, and described consumption of organic solvent is 2～20 times of p-nitrophenyl methanol quality.
6, the synthetic method to the nitroxyl chloride benzyl formate as claimed in claim 5 is characterized in that described p-nitrophenyl methyl alcohol: two (trichloromethyl) carbonic ether: the molar ratio of acid binding agent is 1: 0.34～0.4: 0.85～0.9.
7, as the described synthetic method of claim 1～4 to the nitroxyl chloride benzyl formate, it is characterized in that described p-nitrophenyl methyl alcohol: superpalite: acid binding agent is 1: 0.5～1.5: 0.01～1, and described consumption of organic solvent is 2～20 times of p-nitrophenyl methanol quality.
8, the synthetic method to the nitroxyl chloride benzyl formate as claimed in claim 7 is characterized in that described p-nitrophenyl methyl alcohol: superpalite: the molar ratio of acid binding agent is 1: 0.55～0.6: 0.85～0.9.
9, the synthetic method to the nitroxyl chloride benzyl formate as claimed in claim 1 is characterized in that described aftertreatment for reaction solution is joined in the recrystallisation solvent, and cooling, filtration promptly get the pure product of nitroxyl chloride benzyl formate; Described recrystallisation solvent is selected from one of following or more than one arbitrary combination: the 1. hydrocarbon compound of carbonatoms 5～10,2. the halohydrocarbon of carbonatoms 1～8,3. the ester compound of carbonatoms 2～8,4. the ketone compounds of carbonatoms 3～8, the 5. ether compound of carbonatoms 4～8.
10, synthetic method to the nitroxyl chloride benzyl formate as claimed in claim 9, it is characterized in that described recrystallisation solvent is one of following or more than one arbitrary combination: Skellysolve A, pentamethylene, normal hexane, hexanaphthene, sherwood oil, benzene, toluene, chlorobenzene, dimethylbenzene, methylene dichloride, trichloromethane, tetracol phenixin, 1, the 1-ethylene dichloride, 1, the 2-ethylene dichloride, 1,1, the 1-trichloroethane, 1,1, the 2-trichloroethane, methyl acetate, ethyl acetate, propyl acetate, butylacetate, isopropyl acetate, isobutyl acetate, pentyl acetate, Isoamyl Acetate FCC, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, amyl propionate, acetone, butanone, cyclopentanone, pimelinketone, ether, propyl ether, isopropyl ether, butyl ether, tetrahydrofuran (THF), 1, the 4-dioxane; Described recrystallisation solvent consumption is 10～60 times to nitroxyl chloride benzyl formate crude product quality.
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| CN103554072A (en) * | 2013-11-08 | 2014-02-05 | 江苏安邦电化有限公司 | Preparation method of phthalide |
| CN105675743A (en) * | 2015-12-31 | 2016-06-15 | 天津市敬业精细化工有限公司 | Dimethylamine aqueous solution detection method |
| CN109206316A (en) * | 2018-09-14 | 2019-01-15 | 山东金城柯瑞化学有限公司 | The preparation method of amino protecting group benzyl chloroformate |
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| JP4265259B2 (en) * | 2003-03-31 | 2009-05-20 | 住友化学株式会社 | Method for producing chloroformic acid benzyl esters |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103554072A (en) * | 2013-11-08 | 2014-02-05 | 江苏安邦电化有限公司 | Preparation method of phthalide |
| CN105675743A (en) * | 2015-12-31 | 2016-06-15 | 天津市敬业精细化工有限公司 | Dimethylamine aqueous solution detection method |
| CN105675743B (en) * | 2015-12-31 | 2019-03-01 | 天津市敬业精细化工有限公司 | A kind of dimethylamine agueous solution detection method |
| CN109206316A (en) * | 2018-09-14 | 2019-01-15 | 山东金城柯瑞化学有限公司 | The preparation method of amino protecting group benzyl chloroformate |
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